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Publication numberCN1175270 A
Publication typeApplication
Application numberCN 95197595
PCT numberPCT/US1995/016194
Publication date4 Mar 1998
Filing date14 Dec 1995
Priority date15 Dec 1994
Also published asCA2207414A1, CA2207414C, CN1088730C, CN1321708A, CN100351320C, CN101240119A, CN101240119B, DE69527543D1, DE69527543T2, DE69527543T3, DE69536066D1, DE69536111D1, EP0799281A1, EP0799281B1, EP0799281B2, EP1225205A2, EP1225205A3, EP1225205B1, EP1942156A1, EP1942156B1, US5851280, US5900029, US6042643, US6494946, US6740151, US7294185, US20030095914, US20050034629, WO1996018688A1
Publication number95197595.1, CN 1175270 A, CN 1175270A, CN 95197595, CN-A-1175270, CN1175270 A, CN1175270A, CN95197595, CN95197595.1, PCT/1995/16194, PCT/US/1995/016194, PCT/US/1995/16194, PCT/US/95/016194, PCT/US/95/16194, PCT/US1995/016194, PCT/US1995/16194, PCT/US1995016194, PCT/US199516194, PCT/US95/016194, PCT/US95/16194, PCT/US95016194, PCT/US9516194
Inventors詹姆斯A贝尔蒙特, 罗伯特M阿米希, 科林P加洛韦
Applicant卡伯特公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Carbon black reacted with diazonium salts and products
CN 1175270 A
Abstract  translated from Chinese
一种制备炭黑产品的方法,该炭黑产品具有连到该炭黑上的有机基团。 A method for the preparation of carbon black products, the carbon black product having attached to the carbon black organic group. 在一种方法中,在没有足以还原该重氮盐的外加电流下,至少一种重氮盐与炭黑反应。 In one method, there is no sufficient reduction of the diazonium salt of the applied current, at least one diazonium salt with a carbon black reactor. 在另外一种方法中,在质子反应介质中至少一种重氮盐与炭黑反应。 In another method, the at least one protic reaction medium diazonium salt reacted with the carbon black. 本发明介绍了根据本发明方法制备的炭黑产品,以及这些炭黑产品在塑料组合物、橡胶混合物、纸张组合物和织物组合物的应用。 The present invention describes the preparation of carbon black products according to the method of the present invention, and these carbon black products in plastic compositions, rubber mixture, paper compositions and textile compositions application.
Claims(153)  translated from Chinese
1.一种制备炭黑产品的方法,该炭黑产品具有连到该炭黑上的有机基团,该方法包括这样一个步骤:在没有足以还原该重氮盐的外加电流下,至少一种重氮盐与炭黑反应。 1. A method for the preparation of carbon black products, the carbon black products having an organic group attached to the carbon black, the method comprising a step of: in the absence of sufficient reduction of the diazonium salt of the applied current, at least one diazonium salt reacted with the carbon black.
2.权利要求1所述的方法,其中该反应步骤是在非质子传递介质中进行的。 The method according to claim 1, wherein the reaction step is carried out in an aprotic medium in the.
3.权利要求1所述的方法,其中该反应步骤是在质子介质中进行的。 The method according to claim 1, wherein the reacting step is carried out in a protic medium.
4.权利要求1所述的方法,其中该重氮盐是现场制备的。 The method according to claim 1, wherein the diazonium salt is prepared in situ.
5.一种制备炭黑产品的方法,该炭黑产品具有连到该炭黑上的有机基团,该方法包括这样一个步骤:在质子反应介质中至少一种重氮盐与炭黑反应。 A method for preparing a carbon black product of the carbon black products having an organic group attached to the carbon black, the method comprising a step of: at least one diazonium salt reacted with the carbon black in a protic reaction medium.
6.权利要求5所述的方法,其中该重氮盐是从伯胺现场制备的。 The method according to claim 5, wherein the diazonium salt is prepared in situ from a primary amine.
7.权利要求6所述的方法,其中该重氮盐是通过伯胺、至少一种亚硝酸盐和至少一种酸反应现场制备的。 7. The method of claim 6, wherein the diazonium salt by a primary amine, at least one of the at least one nitrite and an acid prepared in situ.
8.权利要求7所述的方法,其中该亚硝酸盐是亚硝酸金属盐,并且该酸与胺以1∶1摩尔比存在。 The method according to claim 7, wherein the nitrite is a metal nitrite, and the acid with an amine in the presence of 1 molar ratio.
9.权利要求6所述的方法,其中该重氮盐是通过伯胺与亚硝酸盐反应现场制备的,且该伯胺含有一个强酸基。 The method according to claim 6, wherein the diazonium salt by reaction of a primary amine with a nitrite prepared in situ, and the primary amine contains a strong acid group.
10.权利要求9所述的方法,其中该伯胺是对-氨基苯磺酸(磺胺酸)。 A method according to claim 1, wherein the primary amine is - amino acid (sulfanilic acid).
11.权利要求6所述的方法,其中该重氮盐是通过该伯胺与二氧化氮的水溶液反应现场制备的。 11. The method according to claim 6, wherein the aqueous solution of the diazonium salt by reaction of nitrogen dioxide with a primary amine prepared in situ.
12.权利要求6所述的方法,其中该质子介质是水性介质,且该伯胺是式AyArNH2的胺,其中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳基上的一个取代基,该取代基选自:一个官能团,该官能团选自R、OR、COR、COOR、OCOR、羧酸盐、卤素、CN、NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X、NR3+X、PR3+X-、SkR、SO2NRR1、SO2SR、SNRR′、SSO3H、SSO3盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基;其中k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数。 12. The method according to claim 6, wherein the protic medium is an aqueous medium, and the primary amine is an amine of the formula AyArNH2 in which: Ar is an aryl or heteroaryl group; A, when y is greater than 1, may be the same or different, is independently a substituent on the aryl group, the substituent is selected from: a functional group, the functional group selected from R, OR, COR, COOR, OCOR, carboxylate, halogen, CN, NR2, SO3H, sulfonate salt, OSO3H, OSO3- salt, NR (COR), CONR2, NO2, OPO3H2, phosphate salts monovalent or divalent salts, PO3H2, acid salts of monovalent or divalent salts, N = NR, N2 + X, NR3 + X, PR3 + X-, SkR, SO2NRR1, SO2SR, SNRR ', SSO3H, SSO3 salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- two alkyl thiophene), 2- (1,3-dithiolane group), SOR and SO2R; and linear, branched or cyclic hydroxy, unsubstituted or substituted with said one or more functional groups; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted arylalkyl; wherein k is an integer from 1 to 8; X- is a halide or from a mineral or organic acid anion derived; y is an integer from 1 to the total number of -CH between the aryl group in the present. Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2 -6.
13.权利要求12所述的方法,其中:Ar是选自苯基、萘基、蒽基、菲基、二苯基和吡啶基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自R、OR、COR、COOR、OCOR、COOLi、COONa、COOK、COO NR4+、卤素、CN、NR2、SO3H、SO3Li、SO3Na、SO3K、SO3-NR4+、NR(COR)、CONR2、NO2、PO3H2、PO3HNa、PO3Na2、N=NR、N2+X-、NR3+X-、PR3+X-、SkR、SOR和SO2R;和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代或取代的烷基芳基;或未取代的或取代的芳基烷基;其中:k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;和y:当Ar是苯基时,为1-5的整数;当Ar是萘基时,为1-7的整数;当Ar是蒽基、菲基或二苯基时,为1-9的整数;当Ar是吡啶基时,为1-4的整数。 13. The method according to claim 12, wherein: Ar is selected from phenyl, an aryl naphthyl, anthryl, phenanthryl, biphenyl, and pyridyl; A, when y is greater than 1, may be the same or different, is independently a substituent group on the aromatic group, the substituent is selected from: a functional group selected from R, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO NR4 +, halogen, CN, NR2, SO3H, SO3Li, SO3Na, SO3K, SO3-NR4 +, NR (COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N = NR, N2 + X-, NR3 + X-, PR3 + X-, SkR, SOR and SO2R; and linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional groups; wherein R is hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl group, an alkenyl group or an alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted arylalkyl; wherein: k is an integer of from 1 to 8; X- is a halide or derived from a mineral or organic acid anion; and y: when Ar is phenyl, a is an integer of 1-5; when Ar is a naphthyl group, a 1 Integer -7; when Ar is anthryl, phenanthryl or diphenyl, the integer is 1-9; when Ar is pyridyl, is an integer of 1-4.
14.权利要求12所述的方法,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、和2-(1,3-二硫戊环基);和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x是1-6,Z是1-6,且w是2-6。 14. The method according to claim 12, wherein: Ar is selected from phenyl, benzothiazolyl and a benzothiadiazole group, an aryl group; A, when y is greater than 1, may be the same or different, are independently is a substituent on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl ) -SR, 2- (1,3- dithianyl), and 2- (1,3-dithiolane ring group); and a linear, branched or cyclic hydrocarbon group, an unsubstituted or a a plurality of said functional groups or substituted; and wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted arylalkyl; y: when Ar is phenyl, 1- an integer of 5; and when Ar is benzothiazolyl time, is an integer of 1-4; and when Ar is benzothiadiazole group, a is an integer of 1-3; k is an integer of 1-8; and Q is (CH2 ) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, Z is 1-6, and w is 2-6.
15.权利要求12的方法,其中R和R′是选自NH2-C6H4、CH2CH2-C6H4-NH2、CH2-C6H4-NH2和C6H5。 15. The method of claim 12, wherein R and R 'are selected from NH2-C6H4, CH2CH2-C6H4-NH2, CH2-C6H4-NH2 and C6H5.
16.权利要求12的方法,其中A是(CH2)qSk(CH2)rAr,式中k是1-8的整数,q是0-4的整数,r是0-4的整数,且Ar是取代的或未取代的芳基或杂芳基。 16. The method of claim 12, wherein A is (CH2) qSk (CH2) rAr, wherein k is an integer of 1-8, q is an integer of 0 to 4, r is an integer from 0-4, and Ar is a substituted unsubstituted aryl or heteroaryl.
17.权利要求6所述的方法,其中该伯胺是氨基苯磺酸或其盐、氨基苯羧酸或其盐、或双-对-H2N-(C6H4)-Sk-(C6H4)-NH2,其中k是2-8的整数。 17. The method according to claim 6, wherein the primary amine is an amino acid or a salt thereof, aminophenyl carboxylic acid or a salt or bis - on -H2N- (C6H4) -Sk- (C6H4) -NH2, wherein k is an integer of 2-8.
18.权利要求17所述的方法,其中该伯胺是对-氨基苯磺酸(磺胺酸)。 18. The method according to claim 17, wherein the primary amine is - aminobutyric acid (sulfanilic acid).
19.权利要求17所述的方法,其中该伯胺是双-对-H2N-(C6H4)-Sk-(C6H4)-NH2且k是2和(对-氨基苯二硫化物)。 19. The method of claim 17 wherein the primary amine is a two - to -H2N- (C6H4) -Sk- (C6H4) -NH2 and k is 2 and (p - aminophenyl disulfide).
20.权利要求6所述的方法,其中该伯胺是H2NArSkAr′,式中k是2-4的整数,Ar是亚苯基,且Ar′是苯并噻唑基。 20. The method according to claim 6, wherein the primary amine is H2NArSkAr ', wherein k is an integer of 2 to 4, Ar is phenylene, and Ar' is benzothiazolyl.
21.权利要求6所述的方法,其中该伯胺是H2NArSkArNH2,式中k是2-4的整数,且Ar是亚苯并噻唑基。 21. The method according to claim 6, wherein the primary amine is H2NArSkArNH2, wherein k is an integer of 2-4, and Ar is benzothiazolyl.
22.权利要求21所述的方法,其中k是2。 22. The method according to claim 21, wherein k is 2.
23.权利要求6所述的方法,其中该伯胺是H2NArSH,式中Ar是亚苯基或亚苯并噻唑基。 23. The method according to claim 6, wherein the primary amine is H2NArSH, wherein Ar is phenylene or benzothiazolyl.
24.权利要求5所述的方法,其中该重氮盐是现场制备的。 24. The method according to claim 5, wherein the diazonium salt is prepared in situ.
25.权利要求5所述的方法,其中该重氮盐是从伯胺通过该反应步骤单独制备的。 25. The method according to claim 5, wherein the diazonium salt from a primary amine separately prepared by the reaction of the step.
26.权利要求25所述的方法,其中该质子介质是水性介质,且该伯胺是式AyArNH2的胺,式中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳族基上的一个取代基,该取代基选自:一个官能团,该官能团选自R、OR、COR、COOR、OCOR、羧酸盐、卤素、CN、 NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X、NR3+X、PR3+X-、SkR、SO2NRR′、SO2SR、SNRR′、SSO3H、SSO3盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基;其中k是1-8的整数;X是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数;Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 26. The method according to claim 25, wherein the protic medium is an aqueous medium, and the primary amine is an amine of the formula AyArNH2, wherein: Ar is an aryl or heteroaryl group; A, when y is greater than 1, may be the same or different, is independently a substituent on an aromatic group, the substituent is selected from: a functional group, the functional group selected from R, OR, COR, COOR, OCOR, carboxylate, halogen, CN, NR2, SO3H, sulfonate, OSO3H, OSO3- salt, NR (COR), CONR2, NO2, OPO3H2, phosphate salts monovalent or divalent salts, PO3H2, acid salts of monovalent or divalent salts, N = NR, N2 + X, NR3 + X, PR3 + X-, SkR, SO2NRR ', SO2SR, SNRR', SSO3H, SSO3 salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1, 3-alkyl thiophene), 2- (1,3-dithiolane group), SOR and SO2R; and linear, branched or cyclic hydroxy, unsubstituted or substituted with one or more of said substituted functional group; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl; unsubstituted or substituted aryl ; unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted arylalkyl; wherein k is an integer of 1-8; X is a halide or a mineral acid or from organic acid anion derived; -CH y is the total number of the aryl group from 1 to the existence of an integer between; Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2-6.
27.权利要求25所述的方法,其中:Ar是选自苯基、萘基、蒽基、菲基、二苯基和吡啶基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自R、OR、COR、COOR、OCOR、COOLi、COONa、COOK、COO-NR4+、卤素、CN、NR2、SO3H、SO3Li、SO3Na、SO3K、SO3-NR4+、NR(COR)、CONR2、NO2、PO3H2、PO3HNa、PO3Na2、N=NR、N2+X-、NR3+X-、PR3+X-、SkR、SOR和SO2R;和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基;其中k是1-8的整数;x-是卤化物或从矿物酸或有机酸衍生的阴离子;和y:当Ar是苯基时,为1-5的整数;当Ar是萘基时,为1-7的整数;当Ar是蒽基、菲基或二苯基时,为1-9的整数;当Ar是吡啶基时,为1-4的整数。 27. The method according to claim 25, wherein: Ar is selected from phenyl, an aryl naphthyl, anthryl, phenanthryl, biphenyl, and pyridyl; A, when y is greater than 1, may be the same or different, is independently a substituent on an aromatic group, the substituent is selected from: a functional group selected from R, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO-NR4 +, halogen, CN, NR2 , SO3H, SO3Li, SO3Na, SO3K, SO3-NR4 +, NR (COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N = NR, N2 + X-, NR3 + X-, PR3 + X-, SkR, SOR and SO2R; and linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional groups; wherein R is hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group; wherein k is an integer of 1-8; x- is a halide or derived from a mineral or organic acid anion; and y: when Ar is phenyl, a is an integer of 1-5; when Ar is a naphthyl group, a integer 1-7; and when Ar is anthryl, phenanthryl or diphenyl, the integer is 1-9; when Ar is pyridyl, is an integer of 1-4.
28.权利要求25所述的方法,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)SR、2-(1,3-二噻烷基)、和2-(1,3-二硫戊环基);和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′,可相同或不同,R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x是1-6,z是1-6,且w是2-6。 28. The method according to claim 25, wherein: Ar is selected from phenyl, an aryl group, and a benzothiazolyl benzothiadiazole group; A, when y is greater than 1, may be the same or different, are independently is a substituent on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl ) SR, 2- (1,3- dithianyl), and 2- (1,3-dithiolane ring group); and a linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or said plurality of functional groups substituted; wherein R and R ', same or different, R is hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted arylalkyl; y: when Ar is phenyl, 1- an integer of 5; and when Ar is benzothiazolyl time, is an integer of 1-4; and when Ar is benzothiadiazole group, a is an integer of 1-3; k is an integer of 1-8; and Q is (CH2 ) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, and w is 2-6.
29.权利要求26的方法,其中R和R′是选自NH2-C6H4、CH2CH2-C6H4-NH2、CH2-C6H4-NH2和C6H5。 29. The method of claim 26, wherein R and R 'are selected from NH2-C6H4, CH2CH2-C6H4-NH2, CH2-C6H4-NH2 and C6H5.
30.权利要求26的方法,其中A是(CH2)qSk(CH2)rAr,式中k是1-8的整数,q是0-4的整数,r是0-4的整数,且Ar是取代的或未取代的芳基或杂芳基。 30. The method of claim 26, wherein A is (CH2) qSk (CH2) rAr, wherein k is an integer of 1-8, q is an integer of 0 to 4, r is an integer from 0-4, and Ar is a substituted unsubstituted aryl or heteroaryl.
31.权利要求25所述的方法,其中该伯胺是氨基苯磺酸或其盐、氨基苯羧酸或其盐、或双-对-H2N-(C6H4)-Sk-(C6H4)-NH2,其中k是2-8的整数。 31. The method according to claim 25, wherein the primary amine is an amino acid or a salt thereof, aminophenyl carboxylic acid or a salt or bis - on -H2N- (C6H4) -Sk- (C6H4) -NH2, wherein k is an integer of 2-8.
32.权利要求31所述的方法,其中该伯胺是对-氨基苯磺酸(磺胺酸)。 32. The method according to claim 31, wherein the primary amine is - amino acid (sulfanilic acid).
33.权利要求31所述的方法,其中该伯胺是双-对-H2N-(C6H4)-Sk-(C6H4)-NH2且k是2和(对-氨基苯二硫化物)。 33. The method according to claim 31, wherein the primary amine is bis - on -H2N- (C6H4) -Sk- (C6H4) -NH2 and k is 2 and (p - aminophenyl disulfide).
34.权利要求25所述的方法,其中该伯胺是H2NArSkAr′,式中k是2-4的整数,Ar是亚苯基,且Ar′是苯并噻唑基。 34. The method according to claim 25, wherein the primary amine is H2NArSkAr ', wherein k is an integer of 2 to 4, Ar is phenylene, and Ar' is benzothiazolyl.
35.权利要求25所述的方法,其中该伯胺是H2NArSkArNH2,式中k是2-4的整数,且Ar是亚苯并噻唑基。 35. The method according to claim 25, wherein the primary amine is H2NArSkArNH2, wherein k is an integer of 2-4, and Ar is benzothiazolyl.
36.权利要求25所述的方法,其中该伯胺是H2NArSH,式中Ar是亚苯基或亚苯并噻唑基。 36. The method according to claim 25, wherein the primary amine is H2NArSH, wherein Ar is phenylene or benzothiazolyl.
37.权利要求5所述的方法,其中该质子反应介质是水性介质。 37. The method according to claim 5, wherein the protic reaction medium is an aqueous medium.
38.权利要求37所述的方法,其中该重氮盐的有机基团是取代的或未取代的并选自:脂族基、环状有机基团或具有脂族部分和环状部分的有机基团。 38. The method according to claim 37, wherein the diazonium salt is an organic group is a substituted or unsubstituted and is selected from: an aliphatic group, a cyclic organic group, or an aliphatic portion and a cyclic portion organic group.
39.权利要求5所述的方法,其中该质子反应介质是水。 39. The method according to claim 5, wherein the protic reaction medium is water.
40.权利要求5所述的方法,其中该质子介质是基于醇的介质。 40. The method according to claim 5, wherein the protic medium is an alcohol-based medium.
41.一种根据权利要求1的方法制备的炭黑产品。 41. A method according to claim 1 for the preparation of carbon black products.
42.一种根据权利要求5的方法制备的炭黑产品。 42. A method according to claim 5 for preparing a carbon black product.
43.一种根据权利要求12的方法制备的炭黑产品。 43. A method according to claim 12 for the preparation of carbon black products.
44.一种根据权利要求13的方法制备的炭黑产品。 44. A method according to claim 13 for the preparation of carbon black products.
45.一种根据权利要求14的方法制备的炭黑产品。 45. A method according to claim 14 for the preparation of carbon black products.
46.权利要求42的炭黑产品,其中该有机基团是取代或未取代的,并选自脂族基、环状有机基团或有脂族部分和环状部分的有机基团。 46. A carbon black product of claim 42, wherein the organic group is a substituted or unsubstituted, and is selected from an aliphatic group, a cyclic organic group, or an aliphatic portion and a cyclic portion organic group.
47.权利要求42的炭黑产品,其中该有机基团是取代的或未取代的芳基。 47. A carbon black product of claim 42, wherein the organic group is a substituted or unsubstituted aryl group.
48.权利要求47的炭黑产品,其中该芳族基的芳香环是芳基。 47 48. A carbon black product of claim wherein the aromatic ring of the aromatic group is an aryl group.
49.权利要求47的炭黑产品,其中该芳族基的芳香环是杂芳基。 47 49. A carbon black product of claim wherein the aromatic ring of the aromatic group is a heteroaryl group.
50.权利要求47的炭黑产品,其中所说的芳族基是式AyAr的基团,其中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳基上的一个取代基,该取代基选自:一个官能团,该官能团选自R、OR、COR、COOR、OCOR、羧酸盐、卤素、CN、NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X、NR3+X、PR3+X-、SkR、SO2NRR′、SO2SR、SNRR′、SSO3H、SSO3盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;其中:k是1-8的整数;X是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数;Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 47 carbon black product of claim 50. wherein said aromatic group is a group of formula AyAr, wherein: Ar is an aryl or heteroaryl; A, when y is greater than 1, may be the same or different and are independently is a substituent on the aryl group, the substituents are selected from: a functional group, the functional group is selected from R, OR, COR, COOR, OCOR, carboxylates, halogens, CN, NR2, SO3H, sulfonate, OSO3H, OSO3- salt, NR (COR), CONR2, NO2, OPO3H2, phosphate salts monovalent or divalent salts, PO3H2, acid salts of monovalent or divalent salts, N = NR, N2 + X, NR3 + X, PR3 + X-, SkR, SO2NRR ', SO2SR, SNRR', SSO3H, SSO3 salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl ), 2- (1,3-dithiolane group), SOR and SO2R; and linear, branched or cyclic hydroxy, unsubstituted or substituted with said one or more functional groups; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group, an arylene group, a heteroarylene group or an arylene group; wherein: k is an integer of from 1 to 8 ; X is a halide or derived from a mineral acid or an organic acid anion; the total number of -CH y is an integer from 1 to the aryl group is present in between; Q is (CH2) w, (CH2) xO (CH2 ) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2-6.
51.权利要求50所述的炭黑产品,其中所说的芳族基是式AyAr的基团,式中:Ar是选自苯基、萘基、蒽基、菲基、二苯基和吡啶基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自R、OR、COR、COOR、OCOR、COOLi、COONa、COOK、COO-NR4+、卤素、CN、NR2、SO3H、SO3Li、SO3Na、SO3K、SO3-NR4+、NR(COR)、CONR2、NO2、PO3H2、PO3HNa、PO3Na2、N=NR、N2+X-、NR3+X-、PR3+X-、SkR、SOR和SO2R;和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基或亚芳基;其中k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;和y:当Ar是苯基时,为1-5的整数;当Ar是萘基时,为1-7的整数;当Ar是蒽基、菲基或二苯基时,为1-9的整数;当Ar是吡啶基时,为1-4的整数。 51. The carbon black products according to claim 50, wherein said aromatic group is a group of the formula AyAr, wherein: Ar is selected from phenyl, naphthyl, anthryl, phenanthryl, biphenyl and pyridine an aryl group; A, when y is greater than 1, may be the same or different, is independently a substituent on an aromatic group, the substituent is selected from: a functional group selected from R, OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO-NR4 +, halogen, CN, NR2, SO3H, SO3Li, SO3Na, SO3K, SO3-NR4 +, NR (COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N = NR, N2 + X-, NR3 + X-, PR3 + X-, SkR, SOR and SO2R; and linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional groups; wherein R is hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkyl aryl; unsubstituted or substituted aryl group or an arylene group; where k is an integer from 1 to 8; X- is a halide or derived from a mineral acid or an organic acid anion; and y: When Ar is a phenyl group, a is an integer of 1-5; when Ar is a naphthyl group, a is an integer of 1-7; when Ar is anthryl, phenanthryl or di-phenyl, a is an integer of 1-9; when Ar is When pyridyl is an integer of 1-4.
52.权利要求50的炭黑产品,其中所说的芳族基是式AyAr的基团,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)和2-(1,3-二硫戊环基);和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x是1-6,z是1-6,且w是2-6。 52. A carbon black product of claim 50, wherein said aromatic group is a group of the formula AyAr, wherein: Ar is selected from phenyl, an aryl group, and a benzothiazolyl group benzothiadiazole; A When y is greater than 1, may be the same or different and are independently substituted on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ , CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl) and 2- (1,3-dithiolane ring group); and a linear, branched, chain or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional group; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group , an arylene group, a heteroarylene group or arylene group; y: when Ar is phenyl, a is an integer of 1-5; when Ar is benzothiazolyl, the integer of 1-4; when Ar is When benzo thiadiazolyl, is an integer of 1 to 3; k is an integer of 1-8; and Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or ( CH2) xS (CH2) z, where x is 1-6, z is 1-6, and w is 2-6.
53.权利要求42的炭黑产品,其中所说的芳族基是苯基或萘基。 53. A carbon black product of claim 42, wherein said aromatic group is phenyl or naphthyl.
54.权利要求47的炭黑产品,其中所说的芳族基是式AyAr的基团,其中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳基上的一个取代基,该取代基选自:一个官能团,该官能团选自OR、COR、COOR、OCOR、羧酸盐、CN、NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X-、NR3+X-、PR3+X、SkR、SO2NRR′、SO2SR、SNRR′、SSO3H、55O3-盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;其中:k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数;Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 47 carbon black product of claim 54, wherein the aromatic group is a group of formula AyAr, wherein: Ar is an aryl or heteroaryl; A, when y is greater than 1, may be the same or different and are independently is a substituent on the aryl group, the substituents are selected from: a functional group, the functional group is selected from OR, COR, COOR, OCOR, carboxylate salt, CN, NR2, SO3H, sulfonate, OSO3H, OSO3- salts, NR (COR), CONR2, NO2, OPO3H2, phosphate salts monovalent or divalent salts, PO3H2, acid salts of monovalent or divalent salts, N = NR, N2 + X-, NR3 + X-, PR3 + X, SkR, SO2NRR ', SO2SR, SNRR', SSO3H, 55O3- salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl), 2- (1,3-dithiolane group), SOR and SO2R; and linear, branched or cyclic hydroxy, unsubstituted or substituted with said one or more functional groups; wherein R and R ' , may be the same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl aryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group, an arylene group, a heteroarylene group or an arylene group; wherein: k is an integer of 1-8; X - is a halide or derived from a mineral acid or an organic acid anion; the total number of -CH y is an integer from 1 to the aryl group is present in between; Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2-6.
55.权利要求54炭黑产品,其中所说的芳族基是式AyAr的基团,其中:Ar是选自苯基、萘基、蒽基、菲基、二苯基和吡啶基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自OR、COR、COOR、OCOR、COOLi、COONa、COOK、COO-NR4+、CN、NR2、SO3H、SO3Li、SO3Na、SO3K、SO3-NR4+、NR(COR)、CONR2、NO2、PO3H2、PO3HNa、PO3Na2、N=NR、N2+X-、NR3+X、PR3+X、SkR、SOR和SO2R;和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;或未取代的或取代的芳基烷基或亚芳基;其中k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;和y:当Ar是苯基时,为1-5的整数;当Ar是萘基时,为1-7的整数;当Ar是蒽基、菲基或二苯基时,为1-9的整数;当Ar是吡啶基时,为1-4的整数。 55. A carbon black product of claim 54, wherein said aromatic group is a group of the formula AyAr, wherein: Ar is selected from phenyl, an aryl naphthyl, anthryl, phenanthryl, biphenyl, and pyridyl group; A, when y is greater than 1, may be the same or different, is independently a substituent on an aromatic group, the substituent is selected from: a functional group selected from OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO-NR4 +, CN, NR2, SO3H, SO3Li, SO3Na, SO3K, SO3-NR4 +, NR (COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N = NR, N2 + X-, NR3 + X, PR3 + X, SkR, SOR and SO2R; and linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional groups; wherein R is hydrogen; branched or unbranched C1 -C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group or an arylene group; where k is an integer from 1 to 8; X- is a halide or derived from a mineral acid or an organic acid anion; and y: When Ar is phenyl, 1-5 integer; when Ar is a naphthyl group, a is an integer of 1-7; when Ar is anthryl, phenanthryl or di-phenyl, a is an integer of 1-9; when Ar is pyridyl, 1 to 4 integer.
56.权利要求54的炭黑产品,其中所说的芳基是式AyAr的基团,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、和2-(1,3-二硫戊环基);和一个线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基、炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;未取代的或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x是1-6,z是1-6,且w是2-6。 56. A carbon black product of claim 54, wherein said aryl group is a group of the formula AyAr, wherein: Ar is selected from phenyl, benzothiazolyl and a benzothiadiazole group, an aryl group; A, When y is greater than 1, may be the same or different and are independently substituted on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl), and 2- (1,3-dithiolane ring group); and a linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional group; wherein R and R 'may be the same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; unsubstituted or substituted aryl group, arylene group, a heteroarylene group or arylene group; y: when Ar is phenyl, a is an integer of 1-5; when Ar is benzothiazolyl time, is an integer of 1-4; and when Ar is phenyl and thiadiazolyl group, is an integer of 1 to 3; k is an integer of 1-8; and Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2 ) xS (CH2) z, where x is 1-6, z is 1-6, and w is 2-6.
57.一种炭黑产品,包括炭黑和至少一种相连的有机基团,该有机基团具有a)一个芳族基,和b)一个pKa小于11的酸基、一个pKa小于11的酸基的盐、和pKa小于11的酸基及其盐的混合物,其中该有机基团的至少一个芳族基直接连到该炭黑上。 57. A carbon black product comprising carbon black and at least one attached organic group, the organic group has a) an aromatic group, and b) a pKa less than the acid group 11, a pKa less than acid 11 base of salt, and pKa less than the acid group and mixtures of salts 11, wherein the organic group of at least one aromatic group is directly attached to the carbon black.
58.权利要求57的炭黑产品,其中该酸基是磺酸基、亚磺酸基、羧酸基或膦酸基。 57 carbon black product of claim 58, wherein the acid group is a sulfonic acid group, sulfinic acid group, a carboxylic acid group or phosphonate.
59.权利要求57的炭黑产品,其中该酸基是SSO3H、OPO3H2或OSO3H。 57 carbon black product of claim 59, wherein the acid group is SSO3H, OPO3H2 or OSO3H.
60.权利要求57的炭黑产品,其中该芳族基是取代的苯基。 60. A carbon black product of claim 57, wherein the aromatic group is a substituted phenyl.
61.权利要求57的炭黑产品,其中该芳族基是取代的萘基。 57 61. A carbon black product of claim, wherein the aromatic group is substituted naphthyl.
62.权利要求57的炭黑产品,其中该有机基团是取代的或未取代的磺苯基或其盐,或该有机基团是取代的或未取代的(多磺基)苯基或其盐。 62. A carbon black product of claim 57, wherein the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof, or the organic group is a substituted or unsubstituted (polysulfo) phenyl, or salt.
63.权利要求57的炭黑产品,其中该有机基团是取代的或未取代的羧苯基或其盐,或该有机基团是取代的或未取代的(多羧基)苯基或其盐。 63. A carbon black product of claim 57, wherein the organic group is a substituted or unsubstituted carboxyphenyl or a salt thereof, or the organic group is a substituted or unsubstituted (polycarboxy) phenyl group or a salt thereof .
64.权利要求57的炭黑产品,其中该有机基团是取代的或未取代的磺萘基或其盐,或该有机基团是取代的或未取代的(多磺基)萘基或其盐。 64. A carbon black product of claim 57, wherein the organic group is a substituted or unsubstituted naphthyl group or a sulfo salt, or the organic group is a substituted or unsubstituted (poly sulfo) naphthyl or salt.
65.权利要求57的炭黑产品,其中该有机基团是取代的或未取代的羧萘基或其盐,或该有机基团是取代的或未取代的(多羧基)萘基或其盐。 57 carbon black product naphthyl group or a salt thereof according to claim 65., wherein the organic group is a substituted or unsubstituted naphthyl group or a carboxylic salt, or the organic group is a substituted or unsubstituted (polycarboxy) .
66.权利要求57的炭黑产品,其中该有机基团是对-磺苯基或其盐。 66. A carbon black product of claim 57, wherein the organic group is - sulfophenyl or a salt thereof.
67.权利要求57的炭黑产品,其中该有机基团是对-羧苯基或其盐。 57 carbon black product of claim 67, wherein the organic group is p - carboxyphenyl or a salt thereof.
68.权利要求57的炭黑产品,其中该有机基团是对-磺苯基的Na盐。 57 carbon black product of claim 68, wherein the organic group is p - sulfophenyl the Na salt.
69.权利要求57的炭黑产品,其中该有机基团是羟基磺苯基。 69. A carbon black product of claim 57, wherein the organic group is a sulfophenyl hydroxy.
70.权利要求69的炭黑产品,其中该有机基团是4-羟基-3-磺苯基。 69 70. A carbon black product of claim, wherein the organic group is 4-hydroxy-3-sulfophenyl.
71.一种炭黑产品,包括炭黑和至少一种有机基团,该有机基团具有a)一个芳族基,和b)一个阳离子基团,其中该有机基团的至少一个芳族基连到该炭黑上。 71. A carbon black product comprising carbon black and at least one organic group, the organic group has a) an aromatic group, and b) a cationic group, wherein the organic group is at least one aromatic group connected to the carbon black.
72.权利要求71的炭黑产品,其中该阳离子基团是季铵基或季磷鎓基。 72. A carbon black product of claim 71, wherein the cationic group is a quaternary ammonium group or quaternary phosphonium group.
73.权利要求71的炭黑产品,其中该芳族基是取代的苯基。 73. A carbon black product of claim 71, wherein the aromatic group is a substituted phenyl.
74.权利要求71的炭黑产品,其中该芳族基是取代的萘基。 74. A carbon black product of claim 71, wherein the aromatic group is substituted naphthyl.
75.权利要求71的炭黑产品,其中该有机基团是X-R3N+(CH2)yAr,其中Ar是亚苯基或亚萘基;R独立地是氢或C1-C20烷基;X-是卤化物或从矿物酸或有机酸衍生的阴离子;且y是0-4的整数。 75. A carbon black product of claim 71, wherein the organic group is X-R3N + (CH2) yAr, wherein Ar is phenylene or naphthylene group; R is independently hydrogen or C1-C20 alkyl; X- is halide or derived from a mineral acid or an organic acid anion; and y is an integer of 0-4.
76.权利要求75的炭黑产品,其中y是0。 75 76. A carbon black product of claim, wherein y is 0.
77.权利要求71的炭黑产品,其中该有机基团是X-R3N+CH2COAr,其中R是取代的或未取代的C1-C10烷基,Ar是亚苯基或亚萘基;且X-是卤化物或从矿物酸或有机酸衍生的阴离子。 77. A carbon black product of claim 71, wherein the organic group is X-R3N + CH2COAr, wherein R is a substituted or unsubstituted C1-C10 alkyl, Ar is phenylene or naphthylene group; and X- It is a halide or derived from a mineral acid or an organic acid anion.
78.权利要求71的炭黑产品,其中该有机基团是N-取代的吡啶鎓基。 78. A carbon black product of claim 71, wherein the organic group is N- substituted pyridinium group.
79.权利要求78的炭黑产品,其中该有机基团是-C5H4N-R+X-,其中R是取代的或未取代的C1-C20烃基,且X-是卤化物或从矿物酸或有机酸衍生的阴离子。 78 79. A carbon black product of claim, wherein the organic group is -C5H4N-R + X-, wherein R is a substituted or unsubstituted C1-C20 hydrocarbon group, and X- is a halide or from a mineral or organic acid acid anion derived.
80.一种炭黑产品,包括一种炭黑和至少一种相连的有机基团,该有机基团是具有a)一个C1-C12烷基,和b)一个pKa小于11的酸基、或pKa小于11的酸基的盐、或pKa小于11的酸基或pKa小于11的酸基的盐的混合物,其中该有机基团的C1-C12烷基直接连到该炭黑上。 80. A carbon black product comprising a carbon black and at least one attached organic group, the organic group having a) a C1-C12 alkyl, and b) a pKa less than the acid group 11, or Salt pKa less than the acid group 11, or less than the acid group pKa pKa of less than 11 or 11 in a mixture of an acid salt group, wherein the organic group of C1-C12 alkyl group directly connected to the carbon black.
81.权利要求80的炭黑产品,其中该有机基团是C2H4SO3H。 80 carbon black product of claim 81. wherein the organic group is C2H4SO3H.
82.一种炭黑产品,包括炭黑和至少一种连到该炭黑上的有机基团Ar(CH2)qSk(CH2)rAr′,其中Ar和Ar′可相同或不同,并选自亚芳基和杂亚芳基;k是1-8的整数;q是0-4的整数;且r是0-4的整数。 82. A carbon black product comprising carbon black and at least one connected to the carbon black organic group Ar (CH2) qSk (CH2) rAr ', where Ar and Ar' may be the same or different and are selected from Asia aryl and heteroaryl arylene group; k is an integer of 1-8; q is an integer from 0 to 4; and r is an integer of 0-4.
83.权利要求82的炭黑产品,其中Ar和Ar′是亚芳基;k是1-8的整数;且q和r是0。 83. The carbon black product of claim 82, wherein Ar and Ar 'are arylene group; k is an integer of 1-8; and q and r are 0.
84.权利要求82的炭黑产品,其中Ar和Ar′是亚苯基,k是2-4的整数;且q和r是0。 84. The carbon black product of claim 82, wherein Ar and Ar 'are phenylene group, k is an integer of 2-4; and q and r are 0.
85.权利要求84的炭黑产品,其中k是2。 84 85. A carbon black product of claim 2 wherein k is.
86.权利要求82的炭黑产品,其中Ar和Ar′是杂亚芳基;k是1-8的整数;且q和r是0。 86. A carbon black product of claim 82, wherein Ar and Ar 'are heteroarylene group; k is an integer of 1-8; and q and r are 0.
87.权利要求82的炭黑产品,其中Ar和Ar′是亚苯并噻唑基;k是2-4的整数;且q和r是0。 87. A carbon black product of claim 82, wherein Ar and Ar 'is an alkylene benzothiazolyl; k is an integer of 2-4; and q and r are 0.
88.权利要求87的炭黑产品,其中k是2。 87 88. A carbon black product of claim 2 wherein k is.
89.一种炭黑产品,包括炭黑和至少一种连到该炭黑上的有机基团Ar(CH2)qSk(CH2)rAr′,其中Ar是亚芳基或杂亚芳基;Ar′是芳基或杂芳基;k是1-8的整数;q是0-4的整数;且r是0-4的整数。 89. A carbon black product comprising carbon black and at least one organic group attached to the carbon black on Ar (CH2) qSk (CH2) rAr ', wherein Ar is an arylene group or a heteroarylene group; Ar' It is aryl or heteroaryl; k is an integer of 1-8; q is an integer from 0 to 4; and r is an integer of 0-4.
90.权利要求89的炭黑产品,其中Ar是亚芳基;Ar′是芳基;k是1-8的整数;且q和r为0。 89 90. A carbon black product of claim, wherein Ar is an arylene group; Ar 'is an aryl group; k is an integer of 1-8; and q and r is 0.
91.权利要求89的炭黑产品,其中Ar是亚苯基;Ar′是苯基;R是2-4的整数;且q和r为0。 89 91. A carbon black product of claim, wherein Ar is phenylene; Ar 'is phenyl; R is an integer of 2-4; and q and r is 0.
92.权利要求89的炭黑产品,其中Ar是亚苯基;Ar′是杂芳基;k是1-8的整数;且q和r为0。 89 92. A carbon black product of claim, wherein Ar is phenylene; Ar 'is heteroaryl; k is an integer of 1-8; and q and r is 0.
93.权利要求89的炭黑产品,其中Ar是亚苯基;Ar′是苯并噻唑基;k是2-4的整数;且q和r为0。 89 93. The carbon black product of claim, wherein Ar is phenylene; Ar 'is benzothiazolyl; k is an integer of 2-4; and q and r is 0.
94.一种炭黑产品,包括炭黑和至少一种连到该炭黑上的有机基团ArSH,其中Ar是亚芳基或杂亚芳基。 94. A carbon black product comprising carbon black and at least one carbon black connected to the organic group ArSH, where Ar is an arylene group or a heteroarylene group.
95.权利要求94的炭黑产品,其中Ar是亚苯基。 94 95. A carbon black product of claim, wherein Ar is phenylene.
96.权利要求94的炭黑产品,其中Ar是亚苯并噻唑基。 94 96. A carbon black product of claim, wherein Ar is benzothiazolyl.
97.权利要求71的炭黑产品,其中该有机基团是ArAr′+X-,其中Ar是取代的或未取代的亚苯基、取代的或未取代的亚萘基;Ar′是取代或未取代的吡啶鎓;且X-是卤化物或从矿物酸或有机酸衍生的阴离子。 97. The carbon black product of claim 71, wherein the organic group is ArAr '+ X-, wherein Ar is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group; Ar' is a substituted or unsubstituted pyridinium; and X- is a halide or derived from a mineral acid or an organic acid anion.
98.权利要求97的炭黑产品,其中该有机基团是-C6H4(NC5H5)+X-。 97 98. The carbon black product of claim, wherein the organic group is -C6H4 (NC5H5) + X-.
99.一种制备炭黑产品的方法,该炭黑产品具有连到该炭黑上的有机基团,该方法包括以下步骤:把炭黑和至少一种重氮盐加到造粒机中;和所说的重氮盐与所说的炭黑反应。 99. A method for the preparation of carbon black products of the carbon black products having an organic group attached to the carbon black, the method comprising the steps of: at least one of carbon black and the diazonium salt was added to a granulator; and he said diazonium salt with said carbon black reaction.
100.权利要求99的方法,其中该重氮盐是在水存在下与炭黑反应。 100. The method of claim 99, wherein the diazonium salt is reacted in the presence of water and carbon black.
101.权利要求99的方法,其中把重氮盐作为水溶液或浆料加入。 101. The method of claim 99, wherein the diazonium salt is added as an aqueous solution or slurry.
102.权利要求99的方法,其中把该炭黑产品造粒。 102. The method of claim 99, wherein the granulated carbon black product.
103.权利要求101的方法,其中把该炭黑产品造粒。 103. The method of claim 101, wherein the granulated carbon black product.
104.一种制备炭黑产品的方法,该炭黑产品具有连到该炭黑上的有机基团,包括下列步骤:在造粒机中在炭黑存在下生成重氮盐;和所说的重氮盐与所说的炭黑反应。 104. A method for the preparation of carbon black products, the carbon black product having attached to the carbon black organic group, comprising the steps of: a granulator diazonium salt in the presence of carbon black; and said diazonium salt with said carbon black reactor.
105.权利要求104的方法,其中在水存在下生成该重氮盐。 105. The method of claim 104, wherein the diazonium salt is generated in the presence of water.
106.权利要求104的方法,其中从至少一种伯胺、至少一种酸和至少一种亚硝酸盐来制备该重氮盐。 The method 104 of them from at least one primary amine, at least one acid and at least one nitrite to prepare the diazonium salt 106. Claim.
107.权利要求105的方法,其中从至少一种伯胺、至少一种酸和至少一种亚硝酸盐来制备该重氮盐。 The method 105 of them from at least one primary amine, at least one acid and at least one nitrite to prepare the diazonium salt 107. Claim.
108.权利要求107的方法,其中把该亚硝酸盐作为水溶液加到造粒机中。 108. The method of claim 107, wherein the nitrite as an aqueous solution is added to the granulator.
109.权利要求107的方法,其中把该胺作为该胺的酸盐的水溶液或浆料加到造粒机中。 109. The method of claim 107, wherein the amine to the amine salt as an aqueous solution or slurry was added to a granulator.
110.权利要求107的方法,其中把该亚硝酸盐作为水溶液加到造粒机中,并把该胺作为该胺的酸盐的水溶液或浆料加到造粒机中。 110. The method of claim 107, wherein the aqueous solution is added to the nitrite as a granulator, and to the amine as the amine salt is added to an aqueous solution or slurry granulator.
111.权利要求107的方法,其中把该胺和该炭黑作为干燥混合物加到造粒机中。 111. The method of claim 107, wherein the amine and the carbon black as the dry mixture is added to the granulator.
112.一种塑料组合物,含有塑料和根据权利要求1的方法制备的炭黑产品。 112. A plastic composition comprising a plastic and a carbon black product prepared according to the method claim.
113.一种塑料组合物,含有塑料和根据权利要求5的方法制备的炭黑产品。 113. A plastic composition comprising a plastic and a carbon black product prepared according to the method of claim 5.
114.一种含有纸浆和炭黑产品的纸张产品,该炭黑产品具有至少一种连到该炭黑上的有机基团,其中该有机基团用离子或可离子化的基团所取代。 114. A carbon black products containing pulp and paper products, the carbon black product having at least one organic group attached to the carbon black, wherein the organic group is substituted with ionic or ionizable group.
115.权利要求114的纸张产品,其中该离子或可离子化的基团是磺酸基或其盐、亚磺酸基或其盐、羧酸基或其盐、膦酸基或其盐、或季铵基。 114 115. The paper product of claim, wherein the ionic or ionizable group is a sulfonic acid group or a salt thereof, sulfinic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphonic acid group or a salt thereof, or quaternary ammonium group.
116.权利要求114的纸张产品,其中该有机基团是取代的或未取代的磺苯基或其盐,或该有机基团是取代的或未取代的(多磺基)苯基或其盐。 114 116. The paper product of claim, wherein the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof, or the organic group is a substituted or unsubstituted (polysulfo) phenyl or a salt thereof .
117.权利要求114的纸张产品,其中该有机基团是取代的或未取代的磺萘基或其盐,或该有机基团是取代的或未取代的(多磺基)萘基或其盐。 114 117. The paper product of claim, wherein the organic group is a substituted or unsubstituted naphthyl group or a sulfo salt, or the organic group is a substituted or unsubstituted (poly sulfo) naphthyl group or a salt thereof .
118.权利要求114的纸张产品,其中该有机基团是对-磺苯基或其盐。 114, 118. The paper product wherein the organic group is - sulfophenyl or a salt thereof.
119一种由混合橡胶和炭黑产品的方法来制备的橡胶混合物,该炭黑产品包括一种炭黑和至少一种连到该炭黑上的有机基团Ar(CH2)qSk(CH2)rAr′,其中Ar和Ar′,可相同或不同,是取代的或未取代的亚芳基或杂亚芳基;k是1-8的整数;q是0-4的整数;且r是0-4的整数。 119 A rubber compound by the method of mixing rubber and carbon black product prepared, the carbon black products include a carbon black and at least one organic group attached to the carbon black on Ar (CH2) qSk (CH2) rAr ', wherein Ar and Ar', the same or different, is a substituted or unsubstituted arylene or heteroarylene group; k is an integer of 1-8; q is an integer from 0 to 4; and r is from 0 Integer 4.
120.权利要求119的橡胶混合物,其中Ar和Ar′是亚芳基;k是1-8的整数;且q和r为0。 120. The rubber mixture of claim 119, wherein Ar and Ar 'are arylene group; k is an integer of 1-8; and q and r is 0.
121.权利要求119的橡胶混合物,其中Ar和Ar′是亚苯基;k是2-4的整数;且q和r为0。 121. The rubber mixture of claim 119, wherein Ar and Ar 'are phenylene; k is an integer of 2-4; and q and r is 0.
122.权利要求121的橡胶混合物,其中k是2。 122. The rubber mixture of claim 121, wherein k is 2.
123.权利要求119的橡胶混合物,其中Ar和Ar′是杂亚芳基;k是1-8的整数;且q和r为0。 123. The rubber compound of claim 119, wherein Ar and Ar 'are heteroarylene group; k is an integer of 1-8; and q and r is 0.
124.权利要求119的橡胶混合物,其中Ar和Ar′是亚苯并噻唑基;k是2-4的整数;且q和r为0。 124. The rubber compound of claim 119, wherein Ar and Ar 'is an alkylene benzothiazolyl; k is an integer of 2-4; and q and r is 0.
125.权利要求124的橡胶混合物,其中k是2。 125. The rubber mixture of claim 124, wherein k is 2.
126.一种由混合橡胶和炭黑产品的方法来制备的橡胶混合物,该炭黑产品包括一种炭黑和至少一种连到该炭黑上的有机基团Ar(CH2)qSk(CH2)rAr′,其中Ar是亚芳基或杂亚芳基;Ar′是芳基或杂芳基;k是1-8的整数;q是0-4的整数;且r是0-4的整数。 126. A rubber compound by the method of mixing rubber and carbon black product prepared, the carbon black products include a carbon black and at least one organic group attached to Ar (CH2) carbon black on qSk (CH2) rAr ', wherein Ar is an arylene group or a heteroarylene group; Ar' is aryl or heteroaryl; k is an integer of 1-8; q is an integer from 0 to 4; and r is an integer of 0-4.
127.权利要求126的橡胶混合物,其中Ar是亚芳基;Ar′是芳基;k是1-8的整数;且q和r为0。 127. The rubber mixture of claim 126, wherein Ar is an arylene group; Ar 'is an aryl group; k is an integer of 1-8; and q and r is 0.
128.权利要求126的橡胶混合物,其中Ar是亚苯基;Ar′是苯基;k是2-4的整数;且q和r为0。 128. The rubber mixture of claim 126, wherein Ar is phenylene; Ar 'is phenyl; k is an integer of 2-4; and q and r is 0.
129.权利要求126的橡胶混合物,其中Ar是亚苯基;Ar′是杂芳基;k是1-8的整数;且q和r为0。 129. The rubber mixture of claim 126, wherein Ar is phenylene; Ar 'is heteroaryl; k is an integer of 1-8; and q and r is 0.
130.权利要求126的橡胶混合物,其中Ar是亚苯基;Ar′是苯并噻唑基;k是2-4的整数;且q和r为0。 130. The rubber mixture of claim 126, wherein Ar is phenylene; Ar 'is benzothiazolyl; k is an integer of 2-4; and q and r is 0.
131.一种由混合橡胶和炭黑产品的方法制备的橡胶混合物,该炭黑产品包括炭黑和连到该炭黑产品上的至少一种有机基团ArSH,其中Ar是亚芳基或杂亚芳基。 131. A rubber compound by the method of mixing of the rubber and the carbon black product prepared, the carbon black product comprising a carbon black and the carbon black product is connected to at least one organic group ArSH, where Ar is an arylene group or a heteroaryl arylene group.
132.权利要求131的橡胶混合物,其中Ar是亚苯基。 132. The rubber compound of claim 131, wherein Ar is phenylene.
133.权利要求131的橡胶混合物,其中Ar是亚苯并噻唑基。 133. The rubber compound of claim 131, wherein Ar is benzothiazolyl.
134.权利要求119的橡胶混合物,是固化的。 119 134. The rubber compound of claim, is cured.
135.权利要求126的橡胶混合物,是固化的。 126 135. The rubber compound of claim, is cured.
136.权利要求131的橡胶混合物,是固化的。 131 136. The rubber compound of claim, is cured.
137.权利要求122的橡胶混合物,是固化的。 122 137. The rubber compound of claim, is cured.
138.一种包括纤维或织物和炭黑产品的纤维或织物组合物,该炭黑产品具有至少一个连到该炭黑上的有机基团,其中该有机基团用离子或可离子化的基团所取代。 138. A comprises fibers or fiber or fabric composite fabric and carbon black products, the carbon black product having at least one organic group attached to the carbon black, wherein the ionic or the use of the group of the organic group Mission replaced.
139.权利要求138的纤维或织物组合物,其中该离子或可离子化的基团是磺酸基或其盐、亚磺酸基或其盐、羧酸基或其盐、膦酸基或其盐、或季铵基。 Fiber or fabric 139. The composition of claim 138, wherein the ionic or ionizable group is a sulfonic acid group or a salt thereof, sulfinic acid group or a salt thereof, a carboxylic acid group or a salt thereof, a phosphonic acid group or salt, or a quaternary ammonium group.
140.权利要求138的纤维或织物组合物,其中该有机基团是取代的或未取代的磺苯基或其盐,或该有机基团是取代的或未取代的(多磺基)苯基或其盐。 Fiber or fabric 140. The composition of claim 138, wherein the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof, or the organic group is a substituted or unsubstituted (polysulfo) phenyl or a salt thereof.
141.权利要求138的纤维或织物组合物,其中该有机基团是取代的或未取代的磺萘基或其盐,或该有机基团是取代的或未取代的(多磺基)萘基或其盐。 Fiber or fabric 141. The composition of claim 138, wherein the organic group is a substituted or unsubstituted naphthyl group or a sulfo salt, or the organic group is a substituted or unsubstituted (poly sulfo) naphthyl or a salt thereof.
142.权利要求138的纤维或织物组合物,其中该有机基团是对-磺苯基或其盐。 138 142. The fiber or fabric composition as claimed in claim wherein the organic group is - sulfophenyl or a salt thereof.
143.一种包括炭黑和至少一种连到该炭黑上的有机基团的炭黑产品,其中该有机基团是式AyAr的芳族基,其中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳基上的一个取代基,该取代基选自:一个官能团,该官能团选自OR、COR、COOR、OCOR、羧酸盐、CN、NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X-、NR3+X-、PR3+X、SkR、SO2NRR′、SO2SR、SNRR′、SSO3H、SSO3-盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基;亚芳基、杂亚芳基或烷基亚芳基,其中k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数。 143. A include carbon black and at least one organic group attached to the carbon black carbon black products on which the organic group is an aromatic group of formula AyAr, wherein: Ar is an aryl or heteroaryl; A, when y is greater than 1, may be the same or different, is independently a substituent on the aryl group, the substituent is selected from: a functional group, the functional group selected from OR, COR, COOR, OCOR, carboxylate, CN , NR2, SO3H, sulfonate, OSO3H, OSO3- salts, NR (COR), CONR2, NO2, OPO3H2, a monovalent phosphoric acid salt or divalent salts, PO3H2, phosphonate salts of monovalent or divalent salt, N = NR , N2 + X-, NR3 + X-, PR3 + X, SkR, SO2NRR ', SO2SR, SNRR', SSO3H, SSO3- salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazine-diyl) - SR, 2- (1,3- dithianyl), 2- (1,3-dithiolane group), SOR and SO2R; and linear, branched or cyclic hydroxy, unsubstituted or replacing said one or more functional groups; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl; not substituted or unsubstituted aryl group; an unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group; an arylene group, heteroarylene group or an alkyl group arylene, where k is an integer from 1 to 8; X- is a halide or derived from a mineral acid or an organic acid anion; the total number of -CH y is an integer from 1 to the aryl group is present in between. Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2 -6.
144.权利要求143的炭黑产品,其中所说的芳基是式AyAr的基团,其中:Ar是选自苯基、萘基、蒽基、菲基、二苯基和吡啶基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自OR、COR、COOR、OCOR、COOLi、COONa、COOK、COO-NR4+、CN、NR2、SO3H、SO3Li、SO3Na、SO3K、SO3-NR4+、NR(COR)、CONR2、NO2、PO3H2、PO3HNa、PO3Na2、N=NR、N2+X-、NR3+X、PR3+X-、SkR、SOR和SO2R;和线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代或取代的烷基芳基;或未取代或取代的芳基烷基或亚芳基;其中:k是1-8的整数;X是卤化物或从矿物酸或有机酸衍生的阴离子;和y:当Ar是苯基时,为1-5的整数;当Ar是萘基时,为1-7的整数;当Ar是蒽基、菲基或二苯基时,为1-9的整数;当Ar是吡啶基时,为1-4的整数。 143 144. The carbon black product of claim wherein said aryl group is a group of the formula AyAr, wherein: Ar is selected from phenyl, an aryl naphthyl, anthryl, phenanthryl, biphenyl, and pyridyl group; A, when y is greater than 1, may be the same or different, is independently a substituent on an aromatic group, the substituent is selected from: a functional group selected from OR, COR, COOR, OCOR, COOLi, COONa, COOK, COO-NR4 +, CN, NR2, SO3H, SO3Li, SO3Na, SO3K, SO3-NR4 +, NR (COR), CONR2, NO2, PO3H2, PO3HNa, PO3Na2, N = NR, N2 + X-, NR3 + X, PR3 + X-, SkR, SOR and SO2R; and linear, branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional groups; wherein R is hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group or an arylene group; where: k is an integer of 1-8; X is a halide or derived from a mineral acid or an organic acid anion; and y: When Ar is phenyl, 1-5 When Ar is a naphthyl group, is an integer of 1-7;; when Ar is anthryl, phenanthryl or di-phenyl, is an integer of 1-9; and when Ar is pyridyl, the integer integer 1-4 .
145.权利要求143的炭黑产品,其中所说的芳族基是式AyAr的基团,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、和2-(1,3-二硫戊环基);和一个线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基、炔基;未取代或取代的芳基;未取代或取代的杂芳基、未取代的或取代的烷基芳基;未取代的或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x是1-6,z是1-6,且w是2-6。 143 145. The carbon black product of claim, wherein said aromatic group is a group of the formula AyAr, wherein: Ar is selected from phenyl, an aryl group, and a benzothiazolyl group benzothiadiazole; A When y is greater than 1, may be the same or different and are independently substituted on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ , CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl), and 2- (1,3-dithiolane ring group); and a linear , branched or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional group; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or a substituted alkyl group, alkenyl group, alkynyl group; an unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl, unsubstituted or substituted alkylaryl; unsubstituted or substituted arylalkyl y; group, an arylene group, a heteroarylene group or arylene group: when Ar is phenyl, a is an integer of 1-5; when Ar is benzothiazolyl time, an integer of 1-4; when Ar is benzo thiadiazolyl, is an integer of 1 to 3; k is an integer of 1-8; and Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z, or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, and w is 2-6.
146.一种由混合橡胶和炭黑的方法制备的橡胶混合物,该炭黑产品具有连到该炭黑产品的有机基团,其中该有机基团是AyAr,其中:Ar是芳基或杂芳基;A,当y大于1时,可相同或不同,独立地是芳基上的一个取代基,该取代基选自:一个官能团,该官能团选自OR、COR、COOR、OCOR、羧酸盐、CN、NR2、SO3H、磺酸盐、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、OPO3H2、磷酸一价盐或二价盐、PO3H2、膦酸一价盐或二价盐、N=NR、N2+X-、NR3+X-、PR3+X、SkR、SO2NRR′、SO2SR、SNRR′、SSO3H、SSO3-盐、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)、2-(1,3-二硫戊环基)、SOR和SO2R;和线性的、支链的或环状的羟基,未取代或用所说的一个或多个官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基或炔基;未取代的或取代的芳基;未取代的或取代的杂芳基;未取代或取代的烷基芳基;或未取代或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;其中:k是1-8的整数;X-是卤化物或从矿物酸或有机酸衍生的阴离子;y是从1到该芳基中所存在的-CH总数之间的一个整数;Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z,其中x为1-6、z为1-6,w为2-6。 146. A rubber mixture from the mixing process for the preparation of rubber and carbon black, which is attached to the carbon black product of the carbon black product having an organic group, wherein the organic group is AyAr, wherein: Ar is an aryl or heteroaryl group; A, when y is greater than 1, may be the same or different, is independently a substituent on the aryl group, the substituent is selected from: a functional group, the functional group selected from OR, COR, COOR, OCOR, carboxylate , CN, NR2, SO3H, sulfonate, OSO3H, OSO3- salt, NR (COR), CONR2, NO2, OPO3H2, phosphate salts monovalent or divalent salts, PO3H2, acid salts of monovalent or divalent salts, N = NR, N2 + X-, NR3 + X-, PR3 + X, SkR, SO2NRR ', SO2SR, SNRR', SSO3H, SSO3- salt, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl ) -SR, 2- (1,3- dithianyl), 2- (1,3-dithiolane-yl), SOR and SO2R; and a linear, branched or cyclic hydroxy, unsubstituted or substituted with said one or more functional groups; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl or alkynyl ; unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; or unsubstituted or substituted aryl group, an arylene group, a heteroarylene group or alkylarylene; where: k is an integer from 1 to 8; X- is a halide or derived from a mineral acid or an organic acid anion; -CH total y is from 1 to the aryl groups present in between an integer; Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2) xS (CH2) z, where x is 1-6, z is 1-6, w is 2-6.
147.权利要求146的橡胶混合物,其中所说的芳族基是式AyAr的基团,其中:Ar是选自苯基、苯并噻唑基和苯并噻二唑基的一个芳基;A,当y大于1时,可相同或不同,独立地是一个芳族基上的取代基,该取代基选自:一个官能团,选自SkR、SSO3H、SO2NRR′、SO2SR、SNRR′、SNQ、SO2NQ、CO2NQ、S-(1,4 哌嗪二基)-SR、2-(1,3-二噻烷基)、和2-(1,3-二硫戊环基);和一个线性的、支链的或环状的烃基,未取代或用一个或多个所述的官能团取代;其中R和R′,可相同或不同,是氢;支化或未支化的C1-C20未取代或取代的烷基、链烯基、炔基;未取代或取代的芳基;未取代或取代的杂芳基;未取代的或取代的烷基芳基;未取代的或取代的芳基烷基、亚芳基、杂亚芳基或烷基亚芳基;y:当Ar是苯基时,为1-5的整数;当Ar是苯并噻唑时,为1-4的整数;当Ar是苯并噻二唑基时,是1-3的整数;k是1-8的整数;和Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z或(CH2)xS(CH2)z、其中x是1-6,z是1-6,且w是2-6。 147. The rubber compound of claim 146, wherein said aromatic group is a group of the formula AyAr, wherein: Ar is selected from phenyl, an aryl group, and a benzothiazolyl benzothiadiazole group; A, When y is greater than 1, may be the same or different and are independently substituted on an aromatic group, the substituent is selected from: a functional group selected from SkR, SSO3H, SO2NRR ', SO2SR, SNRR', SNQ, SO2NQ, CO2NQ, S- (1,4 piperazinediyl) -SR, 2- (1,3- dithianyl), and 2- (1,3-dithiolane ring group); and a linear, branched, chain or cyclic hydrocarbon group, unsubstituted or substituted with one or more of the functional group; wherein R and R ', same or different, are hydrogen; branched or unbranched C1-C20 unsubstituted or substituted alkyl, alkenyl, alkynyl; unsubstituted or substituted aryl; unsubstituted or substituted heteroaryl; unsubstituted or substituted alkylaryl; unsubstituted or substituted aryl group, arylene group, a heteroarylene group or arylene group; y: when Ar is phenyl, a is an integer of 1-5; when Ar is benzothiazolyl time, is an integer of 1-4; and when Ar is phenyl and thiadiazolyl group, is an integer of 1 to 3; k is an integer of 1-8; and Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z or (CH2 ) xS (CH2) z, where x is 1-6, z is 1-6, and w is 2-6.
148.权利要求146的橡胶混合物,是固化的。 146 148. The rubber compound of claim, is cured.
149.权利要求147的橡胶混合物,是固化的。 149. The rubber compound of claim 147, are cured.
150.一种包括炭黑和至少一种连到该炭黑上的有机基团ArNH2的炭黑产品,其中Ar是取代的或未取的亚芳基。 150. A include carbon black and at least one organic group attached to the carbon black ArNH2 on carbon black products, where Ar is a substituted or unsubstituted arylene group.
151.权利要求150的炭黑产品,其中Ar是亚苯基。 150 151. The carbon black product of claim, wherein Ar is phenylene.
152.一种包括炭黑和至少一种有机基团ArQAr′NH2的炭黑产品,其中Ar和Ar′,可相同或不同,是取代的或未取代的亚芳基,且Q是CH2或SO2。 152. comprising carbon black and at least one organic group ArQAr'NH2 carbon black product, wherein Ar and Ar ', the same or different, is a substituted or unsubstituted arylene group, and Q is CH2 or SO2 .
153.权利要求152的炭黑产品,其中Ar和Ar′是亚苯基。 152 153. The carbon black product of claim, wherein Ar and Ar 'are phenylene.
Description  translated from Chinese
与重氮盐反应的炭黑和产品 Carbon black with a diazonium salt and products

本发明是1994年12月15日提交的美国专利申请流水号08/356,660的部分继续申请,上述专利本文引为参考。 The present invention is US patent December 15, 1994 filed portion Serial No. 08 / 356,660 is to continue to apply the above patents are incorporated herein by reference.

本发明涉及一种制备炭黑产品的方法。 The present invention relates to a method for preparing a carbon black product. 该方法涉及重氮盐与炭黑反应生成一种炭黑产品,该炭黑产品具有一个连接到该炭黑上的有机基团。 The method involves the reaction of the diazonium salt with a carbon black product of carbon black, the carbon black product having an organic group is connected to the black on. 本发明也涉及新的炭黑产品和其用途。 The present invention also relates to new carbon black products and their use.

已在过去几十年里做了许多努力来对炭黑的表面化学进行改性。 Over the past few decades we have made many efforts to the surface chemistry of carbon black can be modified. 当物理吸附材料可能沉积到炭黑表面上时,永久改变炭黑的表面化学实质上更困难。 When the physical adsorbent material may be deposited onto the surface of carbon black, permanently changing the surface chemistry of carbon black is substantially more difficult.

已知并商业化使用一些化学改变炭黑表面的方法。 Known and commercial use of some chemical changes in the carbon black surface method. 例如,熟知可用各种处理剂来氧化炭黑表面。 For example, well-known by various treatment agent to oxidize the surface of carbon black. 用表面氧化来制造一些工业产品。 Surface oxidation to produce some industrial products. 用磺酸或氯磺酸磺化和炭黑表面的卤化也是公知的。 Using a sulfonic acid or a halogenated sulfonated carbon black surface it is also known. Tsubakowa在“聚合物科学”(Polym.Sci.)第17卷,第417-470页,1992中,综述了一些把聚合物接枝到炭黑表面上的已知方法。 Tsubakowa in "Polymer Science" (Polym.Sci.) Vol. 17, pp. 417-470, 1992, reviewed some of the polymer grafted to a known method on the surface of carbon black. 也参见美国专利4,014,844,通过把炭黑与聚合物接触并加热,来把聚合物接枝到炭黑上。 See also U.S. Patent No. 4,014,844, by contacting the carbon black with the polymer and heated to the polymer grafted onto carbon black.

美国专利3,479,300介绍了炭黑催化剂组合物和其制备方法。 U.S. Patent 3,479,300 describes silica catalyst compositions and methods for their preparation. 通过用碱或碱土金属处理炭黑粒子并接着用溶剂化的醚处理该生成的碳/金属组合物,来制备这种催化剂组合物。 By treating silica particles with an alkali or alkaline earth metal and subsequently treated with a solvent of ether and the resultant carbon / metal composition, for the preparation of such catalyst compositions. 该催化剂组合物的碳部分可与包括有机化合物的各种反应剂反应,生成炭黑组合物。 The carbon portion of the catalyst composition may include a variety of reactants reacted with an organic compound to produce carbon black compositions.

美国专利3,043,708介绍了改性炭黑,该炭黑具有化学连接到炭黑表面上的烃基。 U.S. Patent No. 3,043,708 describes modified carbon black, carbon black having chemically linked to hydrocarbon on the surface of carbon black. 在弗瑞德-克来福特(Friedel-Crafts)类反应催化剂存在下,炭黑与烷基化剂反应来制备该改性的炭黑。 In Fred - Friedel (Friedel-Crafts) Reaction presence of a catalyst, carbon black and an alkylating agent to prepare the modified carbon black. 据报道可连接到炭黑表面上的烃基包括脂族和芳族基。 It is reported that can be connected to hydrocarbon on the surface of carbon black include aliphatic and aromatic groups. 据报道一种含有连接到炭黑表面上的芳基的改性炭黑可这样制备:在弗瑞德-克来福特类催化剂存在下使卤代的炭黑与芳族烃反应。 It is reported that a modified carbon black having attached to the carbon black surface of the aryl group can be prepared: The Fred - Friedel class halogenated carbon black with an aromatic hydrocarbon reaction in the presence of a catalyst. 美国专利3,025,259介绍了含有美国专利3,043,708中的改性炭黑的橡胶混合物。 U.S. Patent No. 3,025,259 describes a rubber mixture containing U.S. Patent 3,043,708 of the modified carbon black.

美国专利3,335,020介绍了改性炭黑,其中用苯处理炭黑,然后该苯在炭黑上聚合。 U.S. Patent No. 3,335,020 describes modified carbon black, which with benzene-treated carbon black, which is then polymerized onto the benzene carbon black. 为了制备这些改性的炭黑,在无水条件下把苯和炭黑与路易斯酸催化剂混合十分钟。 To prepare these modified carbon blacks, under anhydrous conditions to benzene and carbon black with a Lewis acid catalyst are mixed for ten minutes. 然后该炭黑上的苯通过结合助催化剂氧化剂聚合成对聚苯,并据说由此连接到该炭黑上。 Then benzene on the carbon black by combining oxidant polymerization catalyst pairs co-polystyrene, and thus is said to be attached to the carbon black.

美国专利2,502,254和2,514,236介绍了制备含有炭黑颜料的方法。 U.S. Patents 2,502,254 and 2,514,236 describes methods containing carbon black pigment. 美国专利2,502,254报道:适宜于粘胶丝本体颜料沉积的高分散颜料可在炭黑存在下生成偶氮颜料而得到。 U.S. Patent 2,502,254 reports: suitable for viscose body pigment deposition of highly dispersed pigment can generate azo pigments obtained in the presence of carbon black.

在炭黑存在下,在混合产生偶合的两种水溶液的一种或另一种中,偶合重氮化的胺和另外一种通常为黄、橙或红色颜料的中间体,来制备这种颜料。 In the presence of carbon black, to produce one or the other of two mixing aqueous solutions of the coupling, the coupling diazotized amine and another generally yellow, orange or red pigment intermediates to prepare the pigment . 美国专利2,514,236报道在炭黑存在下通过偶合一个分子比例的四氮化的联苯胺与二个分子比例的芳甲基吡唑啉酮,也可以制备巧克力棕的颜料。 U.S. Patent No. 2,514,236 reports the presence of the carbon black in the proportion of one molecule by coupling tetrazotised benzidine with two molecular proportions of an arylmethyl pyrazolone be prepared chocolate brown pigment.

PCT专利申请WO 92/13983介绍了一种由重氮盐电化学还原来对含碳材料表面进行改性的方法。 PCT patent application WO 92/13983 describes a diazonium salt electrochemically by the original of the carbonaceous material surface modification method. 据报道,该方法可用于,特别是复合材料的碳板和碳纤维。 According to reports, the method can be used, especially carbon composite panels and carbon fiber. 也介绍了由这种方法改性的含碳材料。 This method is also described by the modified carbonaceous material. 在Delmar等人的“美国化学家协会”(J.Am.Chem.Soc.)1992,114,5883-5884,也介绍了电化学还原含官能化芳基的重氮盐来用共价键改性碳表面。 In Delmar et al., "American chemist associations" (J.Am.Chem.Soc.) 1992,114,5883-5884, also introduced electrochemical reduction of diazonium salts containing functionalized aryl radicals to covalently bond change carbon surface.

根据WO 92/13983,对含碳材料表面改性的方法包括通过电化学还原含有一个芳族基团的重氮盐来把这个芳族基接枝到这种材料的表面上。 According to WO 92/13983, of the carbonaceous material surface modification method comprises reducing a diazonium salt containing aromatic groups by electrochemical to this aromatic group grafted onto the surface of this material. 把这种含碳材料在非质子传递溶剂中与重氮盐接触,并相对于也与该重氮盐溶液接触的阳极使其带负电荷。 This carbonaceous material is passed to a solvent in contact with a diazonium salt in an aprotic, and also with respect to contact with the diazonium salt solution so that the anode is negatively charged. 报道使用质子性溶剂使该电化学方法不能生成所要的产物,结果还原了重氮三键,生成了肼。 It reported the use of a protic solvent so that the electrochemical method does not produce the desired product, the results of reducing the diazonium triple bond to form hydrazine.

尽管有上面所讨论的工艺,仍需要改性炭黑的表面化学并赋予炭黑所需要的性能。 Despite the technology discussed above, still need to surface chemical modification of the carbon black and impart desired properties of carbon black.

因此,本发明涉及制备含有一个有机基团炭黑产品的方法,该有机基团连接到该炭黑上。 Accordingly, the present invention relates to an organic group containing carbon black product prepared, the organic group attached to the carbon black. 一个方法包括在没有足以还原该重氮盐的外加电流条件下至少一个重氮盐与炭黑反应的步骤。 In the absence of a sufficient method comprises reducing the diazonium salt impressed current for at least one step reacting the diazonium salt with the carbon black. 另外一个方法包括在质子反应介质中至少一种重氮盐与炭黑反应。 Another method includes at least one diazonium salt reacted with the carbon black in a protic reaction medium.

本发明的其他实施方案涉及新的炭黑产品,这些产品可根据本发明的一个方法而制得。 Other embodiments of the present invention relates to novel carbon black products, which according to the present invention, a method and system. 该炭黑产品可用于与常规炭黑相同的用途。 The carbon black products can be used for the same purpose with conventional carbon black. 这些用途包括,但不局限于:塑料组合物、水性油墨、水性涂料、橡胶混合物、纸张组合物和织物组合物。 These uses include, but are not limited to: plastic compositions, aqueous inks, aqueous coatings, rubber mixture, paper compositions and textile compositions.

下面的说明书介绍了本发明另外一些特征和优点。 The following description describes the present invention further features and advantages. 这些作用通过该说明书介绍更明显,或通过所述的实施本发明可理解这些作用。 These effects are explained in more obvious from the description, or described by the present invention understood these effects. 通过特别是在下面说明书中和所附的权利要求书中指出的方法、产品和组合物,将理解和实现本发明的目的和其他优点。 In particular the book by the method indicated in the following description and appended claims, products and compositions, will understand and implement objectives and other advantages of the present invention. 制备炭黑产品的方法本发明的第一个实施方案提供了制备含有一个有机基团的炭黑产品的方法,该有机基团连到该炭黑上。 The first embodiment of the method of preparing a carbon black product of the present invention provides an organic group containing carbon black product prepared, the organic group attached to the carbon black. 一个方法包括在没有足以还原重氮盐的外加电流下至少一种重氮盐与炭黑反应。 A method comprising at least one diazonium salt with the carbon black in the reaction without reduction of the diazonium salt plus sufficient current. 即,重氮盐和炭黑之间的反应是在没有足以还原该重氮盐的外来电子源的条件下进行的。 That is, when the reaction between the diazonium salt and the carbon black in the absence of external electron source sufficient to reduce the diazonium salt of conditions. 不同重氮盐的混合物可用于本发明的这种方法中。 Mixtures of different diazonium salts may be used in this method of the present invention. 可在各种反应条件下、在任何类型的反应介质中(包括质子和非质子传递溶剂体系或淤浆)进行该方法。 Under various reaction conditions can, in any type of reaction medium (including proton and aprotic solvent systems or slurry) to carry out the method.

在另外一种方法中,在质子反应介质中至少一种重氮盐与炭黑反应。 In another method, the at least one protic reaction medium diazonium salt reacted with the carbon black. 可在本发明的这种方法中使用不同重氮盐的混合物。 Mixtures of different diazonium salts may be used in this method of the present invention. 也可在各种反应条件下进行该方法。 The method can also be carried out under various reaction conditions.

优选,在两个方法中,现场形成该重氮盐。 Preferably, in both processes, the diazonium salt formed in situ. 如果需要的话,在任何一个方法中,可用本领域已知的方法分离和干燥该炭黑产品。 If desired, any one method, by methods known in the art that the carbon black product isolated and dried. 另外,可用已知工艺处理该生成的炭黑产品来除去杂质。 In addition, a known treatment process and the resultant carbon black product to remove impurities. 这些方法的优选实施方案讨论如下并示于实施例中。 Preferred embodiments of these methods are discussed below and shown in the examples.

任何炭黑可用于本发明的这些方法中。 Any carbon black can be used in the method of the present invention. 该生成的炭黑产品可用于常规炭黑所已知的用途中。 The resultant carbon black product can be used in conventional carbon black known applications. 根据所希望的用途选择炭黑的性质。 Selectivity of the carbon black in accordance with the desired use. 更重要的是,可用本发明的方法来制备具有常规炭黑没有的优良性能的炭黑产品。 More importantly, the method of the present invention can be used to prepare carbon black products having excellent properties of the conventional carbon black is not.

可在各种条件下进行该发明的方法并通常不局限于任何特定的条件。 The method of the invention can be carried out under various conditions and is usually not limited to any particular conditions. 反应条件一定是这样的,使得该具体的重氮盐足够稳定以让它与炭黑反应。 The reaction conditions must be such that the particular diazonium salt is sufficiently stable to make it reactive with the carbon black. 因此,可在重氮盐是短时间存在的反应条件下进行这些方法。 Therefore, these methods can be carried out in the presence of the diazonium salt is short reaction conditions. 如下面实施例所示,重氮盐和炭黑之间的反应,例如在很宽的pH范围和温度范围内进行。 As shown in Examples below, the reaction between the diazonium salt and the carbon black, for example, over a wide pH range and temperature range. 可在酸性、中性和碱性pH下进行这些方法。 These methods can be carried out in acidic, neutral and alkaline pH. 优选该pH在约1-9间变化。 Preferably, the pH varied between about 1-9. 该反应温度优选在0℃-100℃范围内。 The reaction temperature is preferably in the range of 0 ℃ -100 ℃.

本领域中已知的重氮盐可通过例如伯胺和亚硝酸水溶液的反应来制备。 Known in the art of the diazonium salt can be prepared by reacting a primary amine such as nitrous acid aqueous solution. 重氮盐和其制备方法的一般性讨论见Morrison和Boyd的“有机化学”(Organic Chemistry),第五版,第937-983页,(Allyn and Bacon,Inc.1987),和March的“高等有机化学:反应、机理和结构”(Advanced OrganicChemistry:Reactions,Mechanisms and Structures),第四版,(Wiley,1992)。 General discussion of diazonium salts and methods for their preparation, see Morrison and Boyd, "Organic Chemistry" (Organic Chemistry), fifth edition, the first 937-983 pages, (Allyn and Bacon, Inc.1987), and March's "Higher Organic Chemistry: Reactions, Mechanisms, and Structure "(Advanced OrganicChemistry: Reactions, Mechanisms and Structures), Fourth Edition, (Wiley, 1992). 根据本发明,重氮盐是具有一个或多个重氮基的有机化合物。 According to the present invention, the diazonium salt is diazonium groups having one or more organic compounds.

在本发明的方法中,该重氮盐可在与炭黑反应之前制得,或更优选使用本领域的已知工艺现场制得。 In the method of the present invention, the diazonium salt may be prepared prior to reaction with the carbon black or, more preferably processes known in the art to use on-site system. “现场”制备也允许使用不稳定的重氮盐如烷基重氮盐,并避免了对该重氮盐进行不必要的处理或操作。 "Field" is also allowed to use for preparing unstable diazonium salts such as alkyl diazonium salts, the diazonium salts and avoids unnecessary handling or operation. 在本发明特别优选的方法中,亚硝酸和重氮盐两个都是现场制备的。 In a particularly preferred method of the present invention, the nitrous acid and the diazonium salt are both prepared in situ. 每一个这些变化都示于下面的实施例中。 Each of these changes are shown in the following examples.

本领域中已知的重氮盐,可通过伯胺、亚硝酸盐和酸反应来制备。 Known in the art diazonium salt, can be prepared by a primary amine, nitrite and acid. 该亚硝酸盐可以是任何亚硝酸金属盐,优选是亚硝酸锂、亚硝酸钠、亚硝酸钾或亚硝酸锌,或任何有机的亚硝酸酯,如亚硝酸异戊酯或亚硝酸乙酯。 The nitrite may be any metal nitrite, preferably lithium nitrite, sodium nitrite, potassium nitrite or zinc, or any organic nitrites, such as amyl nitrite or ethyl nitrite. 该酸可以是在生成该重氮盐中有效的任何无机的或有机的酸。 The acid may be generated in the diazonium salt valid any inorganic or organic acids. 优选的酸包括硝酸HNO3、氢氯酸HCl和硫酸H2SO4。 Preferred acids include HNO3 nitric acid, sulfuric acid, hydrochloric acid HCl and H2SO4.

该重氮盐也可以通过伯胺与二氧化氮水溶液反应来制备。 The diazonium salts can also be prepared by reacting a primary amine with an aqueous solution of nitrogen dioxide. 该二氧化氮的水溶液NO2/H2O,提供了生成该重氮盐所需的亚硝酸。 The aqueous solution of nitrogen dioxide NO2 / H2O, provides the diazonium salt to produce the desired nitrite.

在过量HCl存在下生成重氮盐相比于其他方法来说是不太优选的,因为HCl对不锈钢腐蚀。 In the presence of excess HCl generated compared to other methods diazonium salt is less preferred, because the HCl corrosion of stainless steel. 用NO2/H2O来生成重氮盐具有对通常用于反应容器的不锈钢或其他金属腐蚀性较小的附加优点。 With NO2 / H2O to generate the diazonium salt has corrosive stainless steel or other metals commonly used for reaction vessels smaller additional advantages. 用H2SO4/NaNO2或HNO3/NaNO2制备的腐蚀性也相对小一些。 Corrosion with H2SO4 / NaNO2 or HNO3 / NaNO2 preparation is relatively small.

一般来说,从伯胺、亚硝酸盐和酸生成重氮盐需要基于所用的胺两当量的酸。 In general, from a primary amine, nitrite and acid diazonium salt need based on the use of two equivalents of amine acid. 在一个“现场”法中,可用一当量酸来生成该重氮盐。 In a "live" process, one equivalent of acid can be used to generate the diazonium salt. 当该伯胺含有一个强酸基时,在本发明的方法中没必要加入另外的酸。 When the primary amine contains a strong acid group, in the method of the present invention it is not necessary to add additional acid. 伯胺的一个酸基或多个酸基可提供一个或两个所需的酸的等价物。 A primary amine acid group or more acid groups may provide one or two equivalents of acid required. 当该伯胺含有一个强酸基团时,优选向本发明的方法不加入另外的酸或加入最高达一个当量的其他酸,来现场生成该重氮盐。 When the primary amine contains a strong acid group, preferably the method of the present invention without the addition of additional acid or join up to an equivalent of other acids, to the scene to generate the diazonium salt. 可使用稍稍过量的其他酸。 Other acids may be used in a slight excess. 这种伯胺的一个例子是对-氨基苯磺酸(磺胺酸)。 An example of such a primary amine is - an amino acid (sulfanilic acid). 其他的示于下面的实施例中。 Other embodiments are shown in the following examples.

一般地,重氮盐是热不稳定的。 In general, diazonium salts are thermally unstable. 它们通常是在低温(如0-5℃)溶液中制备的并在盐不分离的情况下使用。 They are typically prepared in solution and used at low temperature (e.g. 0-5 ℃) in the case of the salt is not isolated. 加热一些重氮盐的溶液可放出氮气并在酸性介质中形成相应的醇或在碱性介质中形成有机自由基。 Some diazonium salt solution is heated to release nitrogen and formation of the corresponding alcohols in acidic media or the organic free radicals are formed in alkaline medium.

然而,为了实施本发明的方法,该重氮盐仅需要足够稳定来与炭黑反应就行。 However, for the method of the present invention, the diazonium salt need only be sufficiently stable to reaction with the carbon black on the line. 因此,本发明的方法可用一些在其他情况下认为是不稳定并易于分解的重氮盐来进行。 Thus, the method of the present invention can be used in several other cases considered to be unstable and easily decomposed diazonium salt to. 一些分解过程可与该炭黑和重氮盐之间的反应竞争,并可减少连接到该炭黑上的有机基团的总数。 Some decomposition processes may compete reaction between the carbon black and the diazonium salt with, and reduce the total number of organic groups connected to the black on. 另外,该反应可在较高的温度下进行,这时许多重氮盐易于分解。 Further, the reaction may be carried out at higher temperatures, then many diazonium salts decompose readily. 较高的温度也可有利地增加该重氮盐在反应介质中的溶解性并提高在其该方法中的加工性。 Higher temperatures may also advantageously increase the solubility of the diazonium salt in the reaction medium and improve its workability in the process. 然而,由于其他的分解过程,较高的温度可导致一些重氮盐的损失。 However, due to other decomposition processes, higher temperatures may result in some loss of the diazonium salt.

本发明方法可通过向在反应介质(如水)中的炭黑悬浮液中加入反应剂现场形成重氮盐来实施。 The method of the present invention may be added to the reactants in the reaction medium (water) in the carbon black suspension formed in situ diazonium salt to the embodiment. 因此,待使用的炭黑悬浮液可已经包括一种或多种反应剂来形成重氮盐,且通过加入其余的反应剂就可实施本发明的方法。 Therefore, the carbon black suspension to be used may already comprise one or more reactants to form a diazonium salt, and the method of the present invention by the addition of the remaining reactants can be implemented. 这些方法的一些互换示于下面的实施例。 Some swap these methods are shown in the following examples.

在有机化合物中常见的大量官能团适合于形成重氮盐的反应。 In a large number of organic functional groups commonly adapted to form the diazo salt. 因此,仅有与炭黑反应的重氮盐的可利用性限制了本发明的方法。 Therefore, only the reaction of the diazonium salt and the carbon black may limit the use of the method of the present invention.

本发明的方法可在任何允许重氮盐与炭黑之间反应进行的反应介质中进行。 The method of the present invention may be any of the reaction medium between the diazonium salt with the carbon black allows the reaction be conducted. 优选,该反应介质是基于溶剂的体系。 Preferably, the reaction medium is a solvent-based system. 该溶剂可以是质子性溶剂、非质子传递溶剂、或溶剂的混合物。 The solvent may be a protic solvent, aprotic solvent or mixture of solvents. 质子性溶剂是如水或甲醇的溶剂,含有连接到氧原子或氮原子的氢原子,并因此有足够的酸性形成氢键。 Protic solvent is a solvent such as water or methanol, containing a hydrogen atom connected to an oxygen atom or a nitrogen atom, and therefore sufficiently acidic to form hydrogen bonds. 非质子传递溶剂是不含有上述定义的酸性氢原子的溶剂。 Aprotic solvent is a solvent containing an acidic hydrogen atom as defined above. 非质子传递溶剂包括:例如,如己烷、四氢呋喃(THF)、乙腈和苄腈的溶剂。 Aprotic solvents include: for example, such as hexane, tetrahydrofuran (THF), acetonitrile, and benzonitrile solvent. 对质子和非质子传递溶剂的讨论,参见Morrison和Boyd的“有机化学”(Organic Chemistry),第五版,第228-231页(Allyn and Bacon,Inc.1987)。 To discuss proton and aprotic solvents see Morrison and Boyd, "Organic Chemistry" (Organic Chemistry), Fifth Edition, pp. 228-231 (Allyn and Bacon, Inc.1987).

本发明的方法优选在一种质子性反应介质中进行,即在单独一种质子性溶剂中或含有至少一种质子性溶剂的溶剂混合物中进行。 The method of the invention is preferably in a protic reaction medium, that is, in a protic solvent alone or a solvent mixture containing at least one protic solvent is carried out. 优选的质子性介质包括,但不局限于:水、含有水和其他溶剂的水性介质、醇、和含有醇的任何介质或这些介质的混合物。 Preferred protic media include, but are not limited to: water, an aqueous medium comprising a mixture of water and other solvents, alcohols, and any media containing an alcohol, or these media.

根据本发明的方法,重氮盐与炭黑的反应可用任何种类的炭黑,例如飞扬性的(fluffy)或粒状的炭黑来进行。 The method according to the present invention, the reaction of the diazonium salt with the carbon black by any kind of carbon black, such as carbon black flying property (fluffy) or granular performed. 在一个设计来减少生产成本的实施方案中,在一个形成炭黑粒子的过程中进行该反应。 In one design, to reduce production costs embodiment, the reaction is carried out in a process of formation of carbon black particles. 例如,可在干式转鼓中向炭黑喷重氮盐溶液或浆料来制备本发明的炭黑。 For example, carbon blacks of the present invention can be prepared to black spray diazonium salt solution or slurry in a dry drum. 另外,可通过在溶剂体系(如水)存在下把炭黑造粒来制备该炭黑产品,该溶剂体系含有重氮盐或现场生成重氮盐的数种反应剂。 Further, by the solvent system (e.g., water) is prepared in the presence of a carbon black product of the carbon black granulation, the solvent system comprises a diazonium salt or a diazonium salt generated in situ several reactants. 优选是含水溶剂体系。 Preferably an aqueous solvent system. 因此,本发明另外一个实施方案提供了一个制备粒状炭黑的方法,该方法包括以下步骤:向造粒机中加入炭黑和重氮盐的水性浆料或溶液、该重氮盐与炭黑反应以把有机基团连到该炭黑上、把生成的连有有机基团的炭黑造粒。 Accordingly, another embodiment of the invention provides a method for preparing a particulate carbon black, the method comprising the steps of: adding carbon black to the granulator and the diazonium salt solution or an aqueous slurry of the diazonium salt with the carbon black The reaction to the organic groups attached to the carbon black, even the generated carbon black granulated organic group. 然后可用常规工艺干燥该造粒后的炭黑产品。 Conventional processes can then be granulated after drying the carbon black product.

一般来说,本发明的方法产生了无机副产物,如盐。 In general, the method of the present invention produces a byproduct inorganic, such as salt. 在一些目标用途中,如下面讨论的那些用途,这些副产物可能是不希望有的。 In some target applications, such as those discussed below, use of these by-products may be undesirable. 根据本发明的方法,一些制备炭黑产品而又没有不想要的无机副产物或盐的可行方法如下:首先,用本领域中的已知手段在使用前除去不希望要的无机副产物,来纯化该重氮盐。 The method according to the present invention, a number of possible methods for preparing a carbon black product without unwanted inorganic but-products or salts are as follows: First, using means known in the art prior to use to remove unwanted inorganic by-products, to Purification of the diazonium salt. 第二,用有机亚硝酸酯作为产生相应醇的重氮化试剂,而不是用无机盐,来生成该重氮盐。 Second, with an organic nitrite as the diazotizing agent to produce the corresponding alcohol rather than an inorganic salt, to generate the diazonium salt. 第三,当从含有酸基的胺和水性NO2生成重氮盐时,没有形成无机盐。 Third, when NO2 diazonium salt from an amine and an aqueous acid group-containing, inorganic salt is not formed. 其他一些方法对本领域的熟练技术人员是熟知的。 Some other methods to those skilled in the art are well known.

除了生成无机副产物外,本发明的方法也可产生有机副产物。 In addition to the inorganic by-products, the process of the present invention may also produce organic by-products. 这些有机副产物可通过用有机溶剂萃取除去。 The organic by-products may be removed by extraction with an organic solvent. 其他方法对于本领域熟练技术人员是熟知的。 Other methods for the skilled person is well known. 炭黑产品本发明方法中的重氮盐与炭黑之间的反应形成了具有一个有机基团的炭黑产品,该有机基团连接到炭黑上。 The reaction process of carbon black product of the present invention, a diazonium salt and the carbon black formed between organic group having a carbon black product, the organic group attached to the carbon black. 该重氮盐可含有待连接到炭黑上的有机基团。 The diazonium salt may contain the organic group to be connected to the black on. 因此,本发明涉及含有有机基团的炭黑产品,该有机基团连接到该炭黑上,特别涉及由本发明方法制备的那些炭黑产品。 Accordingly, the present invention relates to compositions containing organic group of carbon black product, the organic group attached to the carbon black, particularly to those of carbon black product prepared by the method of the present invention. 可以通过本领域熟练技术人员知道的其他手段来制备本发明的炭黑。 By other means skilled in the art would know to prepare the carbon black of the present invention.

该有机基团可以是脂族基、环状有机基、或具有脂族部分和环状部分的有机化合物。 The organic group may be an aliphatic group, a cyclic organic group, or an organic compound having an aliphatic portion and a cyclic portion. 如上所述,本发明方法中所使用的重氮盐可以从这样一种伯胺来制备,该伯胺具有一个这样的基团并能形成,甚至非稳定地,一种重氮盐。 As described above, the diazonium salt used in the method of the present invention may be prepared from such a primary amine, the primary amine having one of these groups and can be formed, even non-steady, a diazonium salt. 该有机基可以是取代或未取代的、支化或未支化的。 The organic group may be optionally substituted, branched or unbranched. 脂族基包括:例如,从烷烃、链烯烃、醇类、醚类、醛类、酮类、羧酸类和糖类衍生的基。 Aliphatic groups include: for example, from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and sugars derived group. 环状有机基团包括,但不局限于:脂环烃基(如环烷基、环烯基)、杂环烃基(如吡咯烷基、吡咯啉基、哌啶基、吗啉基等)、芳基(如苯基、萘基、蒽基等)、和杂芳基(如咪唑基、吡唑基、吡啶基、噻吩基、噻唑基、呋喃基、吲哚基等)。 Cyclic organic groups include, but are not limited to: an alicyclic hydrocarbon group (e.g., cycloalkyl, cycloalkenyl), heterocycloalkyl (e.g. pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, etc.), an aryl group (e.g. phenyl, naphthyl, anthryl, etc.), and heteroaryl (e.g., imidazolyl, pyrazolyl, pyridyl, thienyl, thiazolyl, furyl, indolyl, etc.). 当取代的有机基团的空间位阻增加时,从该重氮盐与炭黑反应连接到该炭黑上的有机基团的数目可能减少。 When the space-substituted organic group increases resistance connected from the diazonium salt with the carbon black reaction to the number of organic groups on the carbon black may be reduced.

当该有机基团被取代时,它可含有任何适宜于形成重氮盐的官能团。 When the organic group is substituted, it may contain any suitable form diazonium salt functional groups. 优选的官能团包括、但不局限于:R、OR、COR、COOR、OCOR、羧酸盐(COOLi、COONa、COO NR4+)、卤素、CN、NR2、SO3H、磺酸盐(如SO3Li、SO3Na、SO3K、SO3NR4+)、OSO3H、OSO3-盐、NR(COR)、CONR2、NO2、PO3H2、膦酸盐(如PO3HNa和PO3Na2)、磷酸盐(如OPO3HNa和OPO3Na2)、N=NR、NR3+X、PR3+X、SkR、SSO3H、SSO3-盐、SO2NRR1、SO2SR、SNRR1、SNQ、SO2NQ、CO2NQ、S-(1,4-哌嗪二基)-SR、2-(1,3-二噻烷基)-2-(1,3-二硫戊环基)、SOR和SO2R。 Preferred functional groups include, but are not limited to: R, OR, COR, COOR, OCOR, carboxylate (COOLi, COONa, COO NR4 +), halogen, CN, NR2, SO3H, sulfonates (such as SO3Li, SO3Na, SO3K , SO3NR4 +), OSO3H, OSO3- salts, NR (COR), CONR2, NO2, PO3H2, phosphonates (such as PO3HNa and PO3Na2), phosphates (e.g. OPO3HNa and OPO3Na2), N = NR, NR3 + X, PR3 + X, SkR, SSO3H, SSO3- salts, SO2NRR1, SO2SR, SNRR1, SNQ, SO2NQ, CO2NQ, S- (1,4- piperazinediyl) -SR, 2- (1,3- dithianyl) - 2- (1,3-dithiolane-yl), SOR and SO2R. R和R1,可相同或不同,是独立的氢原子,支化或不支化的、取代或未取代的、饱和或不饱和的C1-C20烃基,如烷基、链烯基、炔基、取代的或非取代的芳基、取代或未取代的杂芳基、取代或未取代的烷基芳基、或取代或未取代的芳基烷基。 R and R1, the same or different and are independently hydrogen atom, branched or why he did not, substituted or unsubstituted, saturated or unsaturated C1-C20 hydrocarbon, such as alkyl, alkenyl, alkynyl, substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aryl group. 整数k在1-8内变化,并优选在2-4间变化。 Changes in the 1-8 integer k, and preferably between 2-4 changes. 阴离子X-是卤化物或从矿物酸或有机酸衍生的阴离子。 X- is a halide anion or derived from a mineral acid or an organic acid anion. Q是(CH2)w、(CH2)xO(CH2)z、(CH2)xNR(CH2)z,或(CH2)xS(CH2)z,其中w是2-6间的整数,x和z是1-6的整数。 Q is (CH2) w, (CH2) xO (CH2) z, (CH2) xNR (CH2) z, or (CH2) xS (CH2) z, where w is an integer between 2-6, x and z is 1 -6 integer.

优选的有机基团是式AyAr-的芳族基,其对应于式AyArNH2的伯胺。 Preferred organic groups are formula AyAr- aromatic group, which corresponds to a primary amine of formula AyArNH2. 在该式中,变量的意义如下:Ar是芳族基,如芳基或杂环芳基。 In this formula, the meaning of the variables as follows: Ar is an aromatic group, an aryl group or heterocyclic aromatic group. 优选,Ar选自苯基、萘基、蒽基、菲基、二苯基、吡啶基、苯并噻二唑基和苯并噻唑基;A是芳族基上独立选自上述优选官能团的取代基,或A是线性、支链的或环状的烃基(优选含有1-20个碳原子)、未取代或用一个或多个那些官能团取代;且y是一个从1到芳族基团中-CH总数的整数。 Preferably, Ar is selected from phenyl, naphthyl, anthryl, phenanthryl, biphenyl, pyridinyl, benzo-thiadiazolyl, and benzothiazolyl; A is independently selected from the above preferred substituent functional groups on the aromatic group group, or A is a linear, branched or cyclic hydrocarbon group (preferably having 1 to 20 carbon atoms), unsubstituted or substituted with one or more of those functional groups; and y is a number from 1 to aromatic groups The total number of -CH integer. 例如,当Ar是苯基时,y是1-5的整数,当Ar是萘基时,y是1-7的整数,当Ar是蒽基时、菲基或二苯基时,y是1-9的整数,或当Ar是吡啶基时,y是1-4的整数。 For example, when Ar is phenyl, y is an integer from 1 to 5, when Ar is naphthyl time, y is an integer from 1-7 when Ar is anthryl group, phenanthryl or di-phenyl, y is 1 -9 integer, or when Ar is a pyridyl group, y is an integer of 1-4.

在上式中,R和R1的具体例子是NH2-C6H4-、CH2CH2-C6H4-NH2、CH2-C6H4-NH2和C6H5。 In the above formula, specific examples of R and R1 is NH2-C6H4-, CH2CH2-C6H4-NH2, CH2-C6H4-NH2 and C6H5.

另外一组可连接到该炭黑上的有机基团是被作为官能团的一个离子或可离子化基团所取代的有机基团。 Another group can be attached to organic groups on the carbon black is used as an ionic functional group or ionizable group substituted organic group. 可离子化基团在所使用的介质中能形成离子基团。 Ionizable groups in the media used can form ionic groups. 该离子基团可以是阴离子基团或阳离子基团,该可离子化的基团可形成阴离子或阳离子。 The ionic groups may be anionic groups or cationic groups, the ionizable group may form an anion or cation.

形成阴离子的可离子化官能团包括:例如,酸基或酸基的盐。 Forming an anion ionizable functional groups include: for example, an acid group or acid salt group. 因此,该有机基团包括从有机酸衍生的基团。 Thus, the organic group include a group derived from an organic acid. 优选当它含有一个形成阴离子的可离子化基团时,这样一个有机基团具有a)一个芳族基团,和b)至少一个具有pKa小于11的酸基,或至少一个具有pKa小于11的酸基的盐,或至少一个具有pKa小于11的酸基和至少一个具有pKa小于11的酸基的盐的混合物。 Preferably, when it contains a form anion ionizable groups, an organic group having such a) an aromatic group, and b) at least one acid group having a pKa of less than 11, or at least having a pKa of less than 11 hydrochloric acid group, or a mixture of at least one acid group pKa of less than 11 and at least one salt of an acid group pKa of less than 11 have have. 该酸基的pKa是指整个有机基团的pKa,而不只是该酸基取代基的。 The acid group pKa pKa refers to the entire organic groups, not just the acid substituent. 更优选,该pKa小于10,且最优选小于9。 More preferably, the pKa is less than 10, and most preferably less than 9. 优选该有机基团的芳族基直接连到该炭黑上。 The aromatic group is preferably the organic group is directly connected to the carbon black. 该芳族基可进一步被取代或未取代,如用烷基。 The aromatic group may be further substituted or unsubstituted, such as with an alkyl. 更优选,该有机基团是苯基或萘基,且该酸基是磺酸基、亚磺酸基、膦酸基或羧酸基。 More preferably, the organic group is a phenyl or naphthyl group, and the acid group is a sulfonic acid group, sulfinic acid group, a phosphonic acid group or a carboxylic acid group. 这些酸基和它们的盐的例子介绍如上。 Examples of these acidic groups and their salts described above. 最优选,该有机基团是取代的或未取代的磺苯基或其盐;取代的或未取代的(多磺基)苯基或其盐;取代的或未取代的磺萘基或其盐;取代的或未取代的(多磺基)萘基或其盐。 Most preferably, the organic group is a substituted or unsubstituted sulfophenyl group or a salt thereof; a substituted or unsubstituted (polysulfo) phenyl or a salt thereof; a substituted or unsubstituted naphthyl group or a sulfo salt ; substituted or unsubstituted (poly sulfo) naphthyl group or a salt thereof. 优选取代的磺苯基是羟基磺苯基或其盐。 Preferred substituted sulfophenyl hydroxy-sulfophenyl or a salt thereof.

具体的具有形成阴离子(和在本发明方法中使用的相应的伯胺)的可离子化官能团的有机基团是:对-磺苯基(对-磺胺酸)、4-羟基-3-磺苯基(2-羟基-5-氨基-苯磺酸)和2-磺乙基(2-氨基乙磺酸)。 Having specific form anions (and the corresponding primary amine in the method of the present invention) is ionizable functional groups organic group are: to - sulfophenyl (p - sulfanilic acid), 4-hydroxy-3-sulfonic benzene group (2-hydroxy-5-amino - acid) and 2-sulfoethyl (2-ethanesulfonic acid). 其他具有形成阴离子的可离子化官能团的有机基团示于下面的实施例中。 Others have formed anion ionizable functional groups organic group shown in the following examples.

胺表示形成阳离子基团的可离子化官能团的例子。 Amine shows an example of forming cationic groups ionizable functional groups. 例如,胺在酸性介质中可质子化形成铵基。 For example, amines may be protonated in acidic media to form ammonium groups. 优选,具有胺基取代基的有机基团的pKb小于5。 PKb Preferably, a substituted amino group having an organic group of less than 5. 季铵基(-NR3+)和季磷鎓基(-PR3+)也表示阳离子基团的例子。 Quaternary ammonium group (-NR3 +) and quaternary phosphonium groups (-PR3 +) also represent examples of cationic groups. 优选,该有机基团含有一个如苯基或萘基的芳族基和一个季铵基或一个季磷鎓基。 Preferably, the organic group comprising a group such as a phenyl group or a naphthyl group and an aromatic quaternary ammonium group or a quaternary phosphonium group. 该芳族基优选直接连到炭黑上。 The aromatic group is preferably directly attached to the carbon black. 季环状胺、甚至季芳香胺,也可用作该有机基团。 Season cyclic amines, and even quaternary aromatic amines, can also be used as the organic group. 因此,N-取代的吡啶鎓化合物,如N-甲基-吡啶基,可用在这方面。 Thus, N- substituted pyridinium compounds, such as N- methyl - pyridyl, can be used in this regard. 有机基团的例子包括, 但不局限于:(C5H4N)C2H5+、C6H4(NC5H5)+、C6H4COCH2N(CH3)3+、C6H4COCH2(NC5H5)+、(C5H4N)CH3+和C6H4CH2N(CH3)3+。 Examples of organic groups include, but are not limited to: (C5H4N) C2H5 +, C6H4 (NC5H5) +, C6H4COCH2N (CH3) 3 +, C6H4COCH2 (NC5H5) +, (C5H4N) CH3 + and C6H4CH2N (CH3) 3+.

具有用离子或可离子化基团取代的连有有机基团的炭黑产品的一个优点是:相对于相应的未处理炭黑,该炭黑产品可提高水分散性。 One advantage of having the use of ionic or substituted with organic groups attached carbon black products are: relative to the corresponding untreated carbon black, the carbon black products may increase water-dispersible. 如实施例所示,炭黑产品的水分散性随着连接到炭黑(具有可离子化的基团)上的有机基团的数目的增加而增加,或随着连接到指定有机基团上的可离子化基团的数目的增加而增加。 As shown in Example, the water dispersible carbon black product with the number of connections to the organic group of carbon black (with ionizable groups) on the increases, or as the connection to the specified organic groups The group may increase in the number of ionization increases. 因此,增加连接到该炭黑产品上的可离子化基团的数目应提高其水分散性,并允许把水分散性控制在一个所希望的水平上。 Therefore, increasing the number of connections on the carbon black products to ionizable group should increase its water dispersibility and permits control of the water-dispersible at a desired level. 应注意:通过酸化水性介质,也可提高含有胺作为连接到该炭黑上的有机基团的炭黑产品的水分散性。 It should be noted: by acidifying the aqueous medium containing an amine can be improved as a connection to the organic groups on the carbon black carbon black product of a water-dispersible.

由于该炭黑产品的水分散性在某种程度上取决于电荷的稳定性,所以优选该水性介质的离子强度小于0.1摩尔浓度。 Because the water dispersibility of carbon black products depends in part on the stability of the charge, it is preferable that the ionic strength of the aqueous medium is less than 0.1 molar. 更优选,该离子强度小于0.01摩尔浓度。 More preferably, the ionic strength is less than 0.01 molar.

当由本发明的方法制备这样一种水分散性炭黑产品时,优选在该反应介质中离子化该离子或可离子化的基团。 When prepared by the method of the present invention, such a water dispersible carbon black products, preferably in the reaction medium ionization of the ionic or group. 该生成的产品溶液或浆料可照原状使用或使用前加以稀释。 The resulting product solution or slurry may be diluted according to the status quo prior to or during use. 另外,该炭黑产品可用常规炭黑所用的工艺进行干燥。 Further, the carbon black product of carbon black by conventional drying processes used. 这些工艺包括,但不局限于:在烘箱或旋转炉中干燥。 These processes include, but are not limited to: dried in an oven or rotary furnace. 然而,过度干燥可引起水分散性程度的损失。 However, excessive drying can cause water-dispersible degree of loss.

除了其水分散性外,具有用离子或可离子化基团所取代的有机基团的炭黑产品也可分散在极性有机溶剂中,如二甲基亚砜(DMSO)和甲酰胺中。 In addition to its water-dispersible, but having with ionic or ionizable groups substituted organic group carbon black products may be dispersed in a polar organic solvent such as dimethyl sulfoxide (DMSO), and formamide. 在如甲醇或乙醇的醇中,使用如冠醚的配位剂,提高了具有含酸基金属盐的有机基团的炭黑产品的分散性。 In such alcohols such as methanol or ethanol, the use of crown ethers as complexing agents, improved metal salt having acid group-containing organic group of carbon black product dispersion.

芳族硫化物是另外一组优选的有机基团。 Aromatic sulfides is another group of preferred organic groups. 具有芳族硫化物基团的炭黑产品特别适宜于橡胶混合物。 An aromatic sulfide group of the carbon black product is especially suitable for rubber mixtures. 这些芳族硫化物可由式Ar(CH2)qSk(CH2)rAr′或A(CH2)qSk(CH2)Ar″表示,其中Ar和Ar′是独立的取代或未取代的亚芳基或杂亚芳基,Ar″是芳基或杂芳基,k是1-8且q和r是0-4。 These aromatic sulfides by the formula Ar (CH2) qSk (CH2) rAr 'or A (CH2) qSk (CH2) Ar ", where Ar and Ar' are independently substituted or unsubstituted arylene or heteroarylene groups, Ar "is an aryl or heteroaryl group, k is 1-8 and q and r are 0-4. 取代的芳基包括取代的烷基芳基。 Substituted aryl groups include substituted alkylaryl groups. 优选的亚芳基包括亚苯基,特别是对-亚苯基、或苯并亚噻唑基。 Preferred arylene groups include phenylene, especially - phenylene, alkylene or benzo-thiazolyl. 存在的硫原子数,由k表示的,优选在2-4范围内。 The presence of sulfur atoms, represented by a k, is preferably in the range of 2-4. 特别优选的芳族硫化物基团是双-对-(C6H4)-S2-(C6H4)-和对-(C6H4)-S2-(C6H5)。 Particularly preferred aromatic sulfide groups are dual - for - (C6H4) -S2- (C6H4) - and - (C6H4) -S2- (C6H5). 这些芳族硫化物基团的重氮盐可从其相应的伯胺H2N-Ar-Sk-Ar′-NH2或H2N-Ar-Sk-Ar″中常规制备。 These aromatic sulfide groups may be conventionally prepared diazonium salt from the corresponding primary amine H2N-Ar-Sk-Ar'-NH2 or H2N-Ar-Sk-Ar "in.

可连到炭黑上的另外一组优选的有机基团是具有氨基苯基的有机基团,如(C6H4)-NH2、(C6H4)-CH2-(C6H4)-NH2、(C6H4)-SO2-(C6H4)-NH2。 Carbon black can be connected to another group of preferred organic group is an organic group having aminophenyl, such as (C6H4) -NH2, (C6H4) -CH2- (C6H4) -NH2, (C6H4) -SO2- (C6H4) -NH2. 炭黑产品的用途本发明的炭黑产品可用于与常规炭黑相同的用途。 The use of carbon black product of carbon black product of the present invention can be used with the same purpose as conventional carbon black. 然而,连到该炭黑上的有机基团可用来改变和提高用于特殊用途的给定炭黑的性能。 However, the organic groups attached to the carbon black can be used to change and improve performance for a particular purpose given carbon black. 如果需要,为了某一特殊用途,也可使用本领域中已知的手段把连到炭黑上的这些有机基团化学改变成另外的基团。 If necessary, in order for a particular purpose, it can also be used means known in the art to connect to the carbon black of these organic groups chemically altered into another group. 例如,可把酸基转化成其盐或其酰胺。 For example, the acid groups can be converted into a salt or an amide.

已制备出本发明的炭黑产品并在许多目标用途中加以评估。 Has prepared carbon black products of the present invention are to be assessed in a number of target applications. 这些用途包括:例如,塑料组合物、水性油墨、水性涂料、橡胶混合物、纸张组合物和织物组合物。 These uses include: for example, plastic compositions, aqueous inks, aqueous coatings, rubber mixture, paper compositions and textile compositions. 下面段落介绍其通常的用途,每个的实施例示于其后。 The following paragraphs describe its normal use, each of the embodiments shown thereafter.

本发明的炭黑产品可在塑料材料中用作颜料或着色剂。 Carbon black product of the present invention can be used as pigments or colorants in a plastic material. 本发明的炭黑组合物也可用来给塑料材料提供导电性。 Carbon black compositions of the present invention can also be used to provide a conductive plastic material. 本发明炭黑产品相对于其相应的未处理炭黑,可提高其分散速率和分散质量。 Carbon black product of the present invention relative to the corresponding untreated carbon black, can increase its distribution rate and dispersion quality. 这些改进分别在塑料制造和成品价值方面具有经济上的优点。 These improvements have economic advantages are in terms of plastic manufacturing and product value. 如实施例42-62中所示,使用本发明的炭黑产品可提高该塑料的冲击强度。 As the embodiment shown 42-62, using carbon black products of the present invention can improve the impact strength of the plastic. 因此,本发明涉及一种改进的塑料组合物,该组合物含有塑料和炭黑,这种改进包括使用本发明的炭黑组合物。 Accordingly, the present invention relates to an improved plastic composition, the composition comprising a plastic and a carbon black, the improvement which comprises the use of carbon black compositions of the present invention.

如与常规炭黑一样,该炭黑产品可与各种塑料一起使用,这些塑料包括、但不局限于从热塑性树脂、热固性树脂、或工程材料如复合材料制成的塑料,热塑性树脂的一般种类包括:(1)丙烯腈-丁二烯-苯乙烯(ABS)树脂;(2)乙缩醛类;(3)丙烯酸类;(4)纤维素类;(5)氯化聚醚类;(6)氟代烃,如聚四氟乙烯(TFE)、聚氯三氟乙烯(CTFE)和四氟乙烯与六氟丙烯共聚物(FEP);(7)尼龙类,如聚酰胺;(8)聚碳酸酯类;(9)聚乙烯类(包括共聚物);(10)聚丙烯类(包括共聚物);(11)聚苯乙烯类;(12)乙烯基类(聚氯乙烯);(13)热塑性聚酯,如聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯;(14)聚苯醚合金;和上述材料和橡胶改性剂的共混物和合金。 As with conventional carbon black as the carbon black products can be used with a variety of plastics, the plastic include, but are not limited to the thermoplastic resins, thermosetting resins, or engineered materials such as plastic composite material, a thermoplastic resin, general categories comprising: (1) acrylonitrile - butadiene - styrene (ABS) resin; (2) acetals; (3) an acrylic; (4) cellulose-based; (5) chlorinated polyethers; ( 6) fluorocarbons, such as polytetrafluoroethylene (TFE), polychlorotrifluoroethylene (CTFE) and tetrafluoroethylene-hexafluoropropylene copolymer (FEP); (7) nylons, such as polyamide; (8) polycarbonates; (9) polyethylenes (including copolymers); (10) polypropylenes (including copolymers); (11) polystyrenes; (12) vinyl (polyvinyl chloride); ( 13) thermoplastic polyesters, such as poly (ethylene terephthalate) or poly (butylene terephthalate); (14) polyphenylene ether alloys; and blends and alloys above materials and rubber modifier. 典型的热固性树脂包括:(1)醇酸树脂类;(2)烯丙基类;(3)氨基类(三聚氰胺和尿素);(4)环氧类;(5)酚醛类;(6)聚酯类;(7)聚硅氧烷类;和(8)聚氨酯类。 Typical thermosetting resins include: (1) alkyds; (2) allyl; (3) amino classes (melamine and urea); (4) an epoxy; (5) phenolic; (6) poly esters; (7) polysiloxanes; and (8) polyurethanes.

一般来说,该炭黑产品可象任何其他颜料一样加入到用来形成塑料预混物的塑料中。 In general, the carbon black product is added like any other pigment to the same plastic used to form a plastic premix. 例如,该操作可在干混合或熔化段中进行。 For example, the operation can be carried out in a dry mixing or melt segment. 本发明的炭黑产品可与其他常规添加剂一起用在塑料组合物中。 Carbon black product of the present invention may be used in conjunction with a plastic composition other conventional additives. 根据本发明,术语塑料组合物包括、但不局限于:任何塑料材料、制品、产品、表面、织物、片材等。 According to the present invention, the term plastic composition includes, but is not limited to: any plastic material, article, goods, surface, fabric, sheet or the like. 例如,塑料材料包括汽车部件、家用挡板、游泳池衬里、屋顶材料、包装材料和任何种类的其他家用或工业用材料。 For example, plastic materials include other household or industrial automobile parts, household baffles, pool liners, roofing materials, packaging materials, and any kind of material.

本发明的炭黑产品也用于水性油墨配方。 Carbon black product of the present invention are also useful for water-based ink formulations. 对于这种用途,上述讨论的水分散性炭黑产品是特别优选的。 For this purpose, water-dispersible carbon black products discussed above are particularly preferred. 因此,本发明提供了一种含有水和炭黑的改性的油墨组合物,这种改性包括使用本发明的炭黑产品。 Accordingly, the present invention provides an ink composition a modified carbon black containing water, including the use of such modified carbon black products of the present invention. 其他已知的油墨添加剂可加入到水性油墨配方中。 Other known ink additives may be added to the aqueous ink formulations.

一般来说,一种油墨由四个基本组份组成:(1)着色剂或颜料,(2)连接料或调墨油,在印刷时起载体作用,(3)提高印刷干燥性的添加剂等,和(4)调节粘度、干燥性和与其他油墨组份相容性的溶剂。 In general, an ink consists of four basic components: (1) a colorant or pigment, (2) the binder or varnish, serving as a support during printing, (3) improve the printing drying additives, etc. , and (4) adjust viscosity, drying and the compatibility with other components of the ink solvent. 对于水性油墨的性能、制备和使用的总体讨论,参见“印刷手册”(The Printing Manual),第五版,Leach等人编辑(Chapman和Hall,1993)。 For the performance of water-based ink, to discuss overall preparation and use, see "Printing Guide" (The Printing Manual), fifth edition, Leach et al. Eds (Chapman and Hall, 1993). 例如,美国专利2,833,736、3,607,813、4,104,833、4,308,061、4,770,706和5,026,755也公开了各种水性油墨组合物。 For example, US Patent 5,026,755 also discloses 2,833,736,3,607,813,4,104,833,4,308,061,4,770,706 and various aqueous ink composition.

本发明的炭黑产品,无论为预分散体还是固体,可用标准工艺把其加入水性油墨配方中。 Carbon black product of the present invention, whether the pre-dispersion or solid, using standard process to add an aqueous ink formulation. 使用本发明的水可分散的炭黑产品,由于减少了或消除了用其他常规炭黑通常所使用的研磨步骤,故具有十分明显的优点并节约了成本。 Use water dispersible carbon black product of the present invention, due to the reduction or elimination of the grinding step is usually used with other conventional carbon blacks, it has very significant advantages and cost savings.

苯胺印刷油墨表示一组油墨组合物。 Flexographic printing inks represent a group of ink compositions. 苯胺印刷油墨通常包括着色剂、粘合剂和溶剂。 Flexographic inks generally include a colorant, a binder and a solvent. 本发明的炭黑产品,特别是水可分散性的炭黑产品,适宜于用作苯胺印刷油墨着色剂。 Carbon black product of the present invention, in particular water dispersible carbon black products, suitable for use as flexographic ink colorants. 实施例101介绍了在水性苯胺印刷油墨配方中使用本发明的炭黑产品。 Example 101 describes the use of the invention in an aqueous flexographic ink formulations carbon black products.

本发明的炭黑产品可用在水性印报用油墨中。 Carbon black product of the present invention can be used in aqueous ink for newspaper printing. 例如,水性印报用油墨组合物可包括水、本发明炭黑产品、树脂和常规添加剂,如防沫剂或表面活性剂。 For example, an aqueous ink composition printed report may include water, carbon black product of the present invention, a resin and conventional additives, such as anti-foaming agents or surfactants.

本发明的炭黑产品也可用在水性涂料组合物中,如涂料或涂饰剂。 Carbon black product of the present invention may also be used in aqueous coating compositions, such as paint or finish. 优选在这些涂料组合物中使用上述的水可分散性炭黑产品。 It said water is preferably used in such coating compositions dispersible carbon black products. 因此,本发明的一个实施方案是一个改进的水性涂料组合物,该组合物包括水、树脂和炭黑,其改进在于使用了本发明的炭黑产品。 Accordingly, one embodiment of the present invention is an improved aqueous coating composition, the composition comprising water, resin and a carbon black, the improvement comprising the use of a carbon black product of the present invention. 可把其他已知的水性涂料添加剂加入到该水性涂料组合物中。 Can the other known aqueous coating additives may be added to the aqueous coating composition. 参见,例如,“科学和技术的McGraw-Hill百科全书”(McGraw-Hill Encclopedia of Science&Technology),第五版(McGraw-Hill,1982)。 See, for example, "science and technology McGraw-Hill Encyclopedia" (McGraw-Hill Encclopedia of Science & amp; Technology), Fifth Edition (McGraw-Hill, 1982). 也可参见美国专利5,051,464、5,319,044、5,204,404、5,051,464、4,692,481、5,356,973、5,314,945、5,266,406和5,266,361。 See also U.S. Patent 5,051,464,5,319,044,5,204,404,5,051,464,4,692,481,5,356,973,5,314,945,5,266,406 and 5,266,361.

本发明的炭黑产品,无论为预分散体还是固体,可用标准工艺把其加入到水性涂料组合物中。 Carbon black product of the present invention, whether the pre-dispersion or solid, using standard process to add to the aqueous coating composition. 使用本发明的水可分散的炭黑产品,由于减少了或消除了用其他常规炭黑通常所使用的研磨步骤,故具有十分明显的优点并节约了成本。 Use water dispersible carbon black product of the present invention, due to the reduction or elimination of the grinding step is usually used with other conventional carbon blacks, it has very significant advantages and cost savings. 下面实施例102和103介绍了在水性汽车顶涂层配方中使用本发明的炭黑产品。 Following examples 102 and 103 describes the use of the present invention in an aqueous automotive topcoat formulations of carbon black products.

本发明的炭黑产品也可用于纸张组合物。 Carbon black product of the present invention may also be used in paper compositions. 用于这种用途的优选炭黑产品是上述的水可分散炭黑产品。 Preferably carbon black products for this use are water dispersible carbon black products discussed above. 因此,本发明涉及一种改进的含有纸浆和炭黑的纸张产品,其改进在于使用本发明的炭黑。 Accordingly, the present invention relates to an improved carbon black containing pulp and paper products, the improvement comprising carbon black of the present invention.

本发明的炭黑产品,无论为固体或预分散体,可用常规炭黑所采用的标准造纸工艺,把其加入到纸浆中。 Carbon black product of the present invention, whether as a solid or pre-dispersion, standard papermaking processes using conventional carbon black is used, to which is added to the pulp. 使用上述的水可分散的炭黑,由于减少或消除了分散其他常规炭黑通常所使用的步骤,因此具有明显的优点并节约了成本。 Carbon black using the above water dispersible, by reducing or eliminating the steps generally disperse other conventional carbon black is used, and thus has a significant cost savings advantage. 实施例100介绍了使用本发明炭黑产品的纸张产品。 Example 100 describes the use of carbon black products of the present invention of paper products.

本发明的纸张产品可加入其他已知的纸张添加剂,如上胶剂、助留剂、固定剂、填料、脱泡剂、抗絮凝剂等。 Paper products of the present invention may incorporate other known paper additives, as sizing agents, retention aids, fixatives, fillers, defoamers, anti-flocculant. 当使用助留剂和酸性或碱性上胶剂时,相比于未处理炭黑,低加入量的上述水可分散性炭黑更有效,这一点是有利的。 When used on retention aids and acidic or alkaline sizing agents, compared to untreated carbon black, low amount of the water-dispersible silica is more effective, and this is advantageous.

本发明的炭黑产品与常规炭黑一样,也可在配合和制备橡胶混合物中用作颜料、填料和增强剂。 Carbon black product of the present invention, as with conventional carbon black, can also be used as pigments, fillers and reinforcing the cooperation and preparation of the rubber mixture. 因此,本发明涉及含有橡胶和炭黑的改进橡胶混合物,其改进在于使用本发明炭黑产品。 Accordingly, the present invention relates to improved rubber compounds containing rubber and carbon black, the improvement comprising the use of a carbon black product of the present invention. 该炭黑的性能在确定含有炭黑的橡胶混合物的性能时是一个很重要的因素。 The properties of carbon black is a very important factor in determining the performance of a rubber mixture containing carbon black when.

例如,炭黑可用于制备橡胶硫化剂,如轮胎中的硫化剂。 For example, carbon black may be used to prepare a rubber vulcanizing agent, such as a tire vulcanizing agent. 在轮胎的制备中通常希望使用产生具有满意耐磨性和滞后性能轮胎的炭黑。 In the preparation of the tire is generally desirable to use the produced carbon black having a satisfactory abrasion resistance and hysteresis performance of the tire. 轮胎的胎面磨耗涉及耐磨性。 It relates to the wear resistance of the tire tread wear. 耐磨性越大,轮胎没有磨损所持续的英里数越长。 Greater wear, tire wear and tear sustained no longer miles. 橡胶混合物的滞后表示在使橡胶混合物变形所施加的能量和当该橡胶混合物回复到初始未变形状态时所释放的能量之间的差。 Rubber compound hysteresis represents the difference between the deformation of the rubber mixture applied energy and energy when the rubber mixture back to the initial non-deformed state of released. 具有低滞后值的轮胎减少了滚动阻力并因此能减少使用该轮胎的汽车的燃料消耗。 Tires having low hysteresis values reduce rolling resistance and therefore reduce the fuel consumption of the vehicle using the tire. 因此,特别需要有能提供轮胎中高耐磨性和低滞后性的炭黑产品。 Thus, in particular, the need to provide high abrasion resistance tires and low hysteresis carbon black products.

本发明的炭黑产品可用于天然和合成橡胶混合物或天然和合成橡胶的混合物中。 Carbon black product of the present invention can be used in natural and synthetic rubber or a mixture of natural and synthetic rubber mixture. 对于这种用途,优选使用上述的含有芳族硫化物作为有机基团的炭黑产品。 For this purpose, it is preferable to use the above-containing aromatic sulfides as the organic group of the carbon black product. 在橡胶混合物中特别优选使用具有相连的式-(C6H4)-Sk-(C6H4)-的芳族硫化物有机基团的炭黑产品,其中k是1-8间的整数,更优选k为2-4。 In particularly preferred rubber compound having the formula attached - (C6H4) -Sk- (C6H4) - aromatic sulfide organic group of carbon black products, where k is an integer between 1-8, more preferably k is 2 -4. 本发明的炭黑产品可用于硫-固化或过氧化物-固化的橡胶混合物中。 Carbon black product of the present invention can be used sulfur - or peroxide curing - the curing of the rubber mixture.

可用通常手段,如混炼,把该炭黑产品和天然或合成橡胶混合。 Typically available means, such as kneading, the carbon black product and natural or synthetic rubber mixed. 通常,为了达到有明显程度的增强,对每100重量份橡胶,可使用约10份-约250重量份的该炭黑产品。 Typically, in order to achieve a significant degree of reinforcement, per 100 parts by weight of rubber, can be used from about 10 parts - about 250 parts by weight of the carbon black product. 然而,对每100重量份橡胶,优选使用约20-约100重量份的炭黑,特别优选是每100重量份橡胶,使用约40-80重量份炭黑。 However, per 100 parts by weight of the rubber, carbon black of about 20 to about 100 parts by weight is preferably used, particularly preferably per 100 parts by weight of the rubber, using about 40 to 80 parts by weight of carbon black.

适宜于与本发明炭黑一起使用的橡胶是天然橡胶和其衍生物,如氯化橡胶。 Rubber and the carbon black suitable for use with the present invention are natural rubber and its derivatives such as chlorinated rubber. 本发明炭黑产品也可与合成橡胶一同使用,如约10-70%(重量)苯乙烯和约90-30%(重量)丁二烯的共聚物,如19份苯乙烯和81份丁二烯的共聚物、30份苯乙烯和70份丁二烯的共聚物、43份苯乙烯和57份丁二烯的共聚物和50份苯乙烯和50份丁二烯的共聚物;共轭二烯的聚合物和共聚物,如聚丁二烯、聚异戊二烯、氯丁橡胶等,以及这些共轭二烯与可与其共聚的含乙烯基单体的共聚物,这些单体如苯乙烯、甲基苯乙烯、氯苯乙烯、丙烯腈、2-乙烯-吡啶、5-甲基 2-乙烯基吡啶、5-乙基-2-乙烯基吡啶、2-甲基-5-乙烯基吡啶、烷基取代的丙烯酸酯、乙烯基酮、甲基异丙烯酮、甲基乙烯基醚、α-亚甲基羧酸和其酯及酰胺(如丙烯酸、二烷基丙烯酸酰胺);也适于此处使用的是乙烯与其他高α链烯(如丙烯、1-丁烯和1-戊烯)的共聚物。 Carbon black product of the present invention may also be used with synthetic rubbers such as about 10 to 70% (by weight) of styrene and about 90-30% (by weight) of butadiene copolymers, such as 19 parts and 81 parts butadiene styrene copolymer, 30 parts of styrene and 70 parts butadiene, 43 parts of styrene and 57 parts of a copolymer of styrene and 50 parts butadiene and 50 parts butadiene; conjugated diene polymers and copolymers such as polybutadiene, polyisoprene, chloroprene rubber, and the conjugated diene and a copolymer therewith containing copolymerizable vinyl monomer, these monomers such as styrene, methyl styrene, chlorostyrene, acrylonitrile, 2-vinyl - pyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, alkyl-substituted acrylates, vinyl ketone, methyl isopropyl ketene, methyl vinyl ether, α- methylene carboxylic acids and esters and amides (e.g., acrylic acid, dialkyl acrylamide); also suitable for this used herein is ethylene and other high α-olefin (such as propylene, 1-butene and 1-pentene) copolymer.

因此,本发明的橡胶混合物包括弹性体、固化剂、增强填料、偶合剂、和任选的各种加工助剂、油增量剂和抗降解剂。 Thus, the rubber mixture of the present invention include elastomers, curing agents, reinforcing filler, a coupling agent, and optionally various processing aids, oil extenders and antidegradants. 除了上述提到的例子外,该弹性体可以是,但不局限于:由1,3-丁二烯、苯乙烯、异戊二烯、异丁烯、2,3-二甲基-1,3-丁二烯、丙烯腈、乙烯、丙烯等制备的聚合物(如均聚物、共聚物和三元共聚物)。 In addition to the above-mentioned examples, the the elastomer can be, but are not limited to: 1,3-butadiene, styrene, isoprene, isobutylene, 2,3-dimethyl-1,3- polymers (e.g., homopolymers, copolymers and terpolymers) of butadiene, acrylonitrile, ethylene, propylene, etc. prepared. 优选这些弹性体由DSC测得的玻璃化转变温度在-120℃-0℃之间。 Preferably, these elastomers measured by DSC glass transition temperature of between -120 ℃ -0 ℃. 这些弹性体的例子包括聚(丁二烯)、聚(苯乙烯-共-丁二烯)和聚(异戊二烯)。 Examples of these elastomers include poly (butadiene), poly (styrene - co - butadiene) and poly (isoprene).

本发明的炭黑产品有利地提高了含有该炭黑产品的橡胶混合物的耐磨性和/或减少了其滞后性。 Carbon black product of the present invention advantageously improve the wear resistance of the carbon black products containing rubber mixtures and / or reduce their lag. 实施例104-116介绍了在各种橡胶混合物中使用本发明炭黑产品和这些组合物的各种性能。 Example 104-116 describes the use of the present invention, various properties of these carbon black products and various rubber compositions in the mixture.

本发明的炭黑产品也可用来使纤维或织物着色。 Carbon black product of the present invention may also be used to make colored fibers or fabrics. 这种用途的优选炭黑产品是上述的水可分散炭黑产品。 Preferably carbon black products for this purpose are water dispersible carbon black products discussed above. 因此,本发明涉及含有纤维或织物和炭黑的改进纤维和织物组合物,其改进在于使用于本发明炭黑。 Accordingly, the present invention relates to a fabric comprising fibers and carbon black or improved fiber and fabric compositions, the improvement wherein the carbon black used in the present invention. 适宜于使用的纤维包括天然和合成纤维,如棉、羊毛、丝、亚麻、聚酯和尼龙。 Suitable for use include natural and synthetic fibers, such as cotton, wool, silk, linen, polyester and nylon. 适宜于使用的织物包括天然和合成纤维,如棉、羊毛、丝、亚麻、聚酯和尼龙。 Suitable for use include natural and synthetic fabrics, such as cotton, wool, silk, linen, polyester and nylon. 优选使用的天然纤维和织物包括棉、羊毛、丝和亚麻。 Preferably natural fibers and fabrics used include cotton, wool, silk and linen.

可用本领域的已知手段使本发明炭黑产品着色,来使纤维和织物着色,如用直接和酸性染料。 Available means known in the art carbon black product of the present invention is colored to make fibers and fabric coloration, such as direct and acid dyes. 关于用染料着色的一般讨论,参见“化学技术的Kirk-Othmer百科全书”(Kirk-Othmer Encyclopedia of Chemical Technology),第8卷,第280-350页,“染料、应用和评价”(Dyes,Application andEvaluation)(John Wiley和Sons,1979)。 For general discussion with dye coloring, see "Chemical Technology Kirk-Othmer Encyclopedia" (Kirk-Othmer Encyclopedia of Chemical Technology), Vol. 8, pp. 280-350, "dye, application and evaluation" (Dyes, Application andEvaluation) (John Wiley and Sons, 1979). 使用上述水可分散的炭黑产品提供了一个用耐光着色剂使这些材料着色的方法。 Using the water dispersible carbon black product provides a light colorant used method for coloring these materials.

下面的实施例是用来说明、但不限制所要求保护的本发明。 The following examples are intended to illustrate, but not to limit the claimed invention.

实施例分析方法除非另外特别说明,用根据ASTM D-4820得到的BET氮气表面积来测定表面积。 EXAMPLES Analytical Methods Unless otherwise specified, BET nitrogen surface area in accordance with ASTM D-4820 was determined surface area. 有时使用CTAB(十六烷基三甲基溴化铵)面积和碘数,并分别根据ASTM D-3765和D-1510得到。 Sometimes the use of CTAB (cetyl trimethyl ammonium bromide) area and iodine number and get in accordance with ASTM D-3765 and D-1510, respectively. 根据ASTM D-2414得到DBPA(邻苯二甲酸正二丁酯)。 To give DBPA (dibutyl phthalate n) according to ASTM D-2414.

如下测定挥发物含量。 Volatile matter content was determined as follows. 在125℃下把炭黑样品干燥至恒重。 At 125 ℃ the carbon black sample was dried to constant weight. 把45ml该干燥炭黑样品置于一个已在950℃干燥的加盖的50ml坩锅中,并在隔焰炉中950℃下加热7分钟。 The 45ml sample of the dried carbon black was placed in a dry 950 ℃ 50ml capped crucible and heated in a muffle furnace at 950 ℃ in 7 minutes. 其挥发物的含量由该炭黑样品失重的百分数来表示。 Volatile matter content of the carbon black sample by the weight loss expressed as a percentage.

在下面的各个实施例中用下面方法来测定本发明炭黑产品和未处理炭黑中的水性残余物。 In the following example using the following method to determine the various embodiments of the present invention and untreated carbon black carbon black products in aqueous residue. 用45g水振荡炭黑产品(5g)5分钟。 45g of carbon black product with water oscillation (5g) 5 minutes. 通过筛子倒出得到的分散液,并用水漂洗直到该洗液无色。 Pouring the dispersion obtained through a sieve and rinsed with water until the washings were colorless. 除非特别说明,使用345目的筛子。 Unless otherwise noted, the use of 345 mesh sieve. 干燥该筛子后,测定在该筛子上残余物的重量,并用该测试中所用炭黑产品的百分数来表示。 After drying the sieve and weighed on the sieve residue, and use the tests used to represent the percentage of carbon black products.

关于涉及橡胶混合物的实施例,根据ASTM D-412来测定模量、拉伸强度和伸长。 About embodiments relate to rubber mixtures, according to ASTM D-412 to determine the modulus, tensile strength and elongation. 根据ASTM D-2240-86测量肖尔A硬度。 Shore A hardness measured according to ASTM D-2240-86.

用根据Lambourn型机器的磨耗试验机来测定橡胶混合物的磨耗数据。 Using a Lambourn abrasion tester according to the machine to determine the wear rubber mixture data. 磨耗速率(立方厘米/运行厘米)是在14%和21%滑移下测定的。 Attrition rate (cc / running cm) was 14% and 21%, measured at slip. 该滑移是基于样品轮和磨石之间的相对速度。 The slip is based on the relative velocity between the sample wheel and grindstone. 在下列的实施例中,磨耗指数是对照组合物的磨耗速率除以由本发明炭黑产品制备的橡胶混合物的磨耗速率的比值。 In the following examples, the abrasion index is the ratio of the abrasion rate of wear rate divided by the control composition of the present invention, the carbon black product prepared in rubber mixtures.

在10Hz恒定频率、恒定温度和应变剪切模式下,用流变动力学分光计RDS-2型测定Tanδ。 At 10Hz constant frequency, constant temperature and strain shear mode, with flow dynamics type RDS-2 spectrometer measured Tanδ. 应变扫描(strain sweeps)在0.2%-120%DSA间进行。 Strain sweep (strain sweeps) between 0.2% -120% DSA performed. 每十次测试5个点并记录最大的Tanδ。 Every ten measurements and record the maximum five points of Tanδ.

如下测试结合橡胶:把0.5g含有橡胶和已知量炭黑的未固化橡胶置于一个钢丝笼中,并在室温下浸入甲苯中。 Bound rubber test as follows: 0.5g of the carbon black-containing rubber and a known amount of uncured rubber placed in a wire cage, and was immersed in toluene at room temperature. 放置一天后,把该样品置于新鲜的甲苯中,并在室温下再放置三天。 Place day later, the sample was placed in the fresh toluene and then placed at room temperature for three days. 然后取出样品,在烘箱中干燥并称重。 Sample was then removed, dried and weighed in an oven. 甲苯处理前后该样品重量减去炭黑的重量,得到每个样品中橡胶的含量。 The weight of the sample before and after toluene treatment subtracting the weight of carbon black, the content of each sample obtained rubber. 甲苯处理后样品的重量,校正成该组合物中炭黑和其他不溶性组份的重量,表示剩余的不溶橡胶的量。 Weight of the sample after toluene treatment, correcting the composition of carbon black and other insoluble component weight, represents the amount of insoluble rubber remaining. 结合橡胶表示为置于甲苯中后该样品中不溶橡胶的重量与初始样品中橡胶重量的比值的百分数。 Bound rubber represents the percentage by weight of insoluble rubber in the sample and the original sample weight ratio of rubber is placed after toluene.

实施例1用预制的重氮盐制备炭黑产品本实施例介绍本发明炭黑产品的制备。 Diazonium salt prepared in Example 1 carbon black products precast embodiment of the present embodiment of the present invention describes the preparation of carbon black products. 使用具有表面积为230m2/g和DBPA为64ml/100g的粒状炭黑。 Having a surface area of 230m2 / g and DBPA particulate carbon black 64ml / 100g of. 由0.688g 4-溴代苯胺、0.300g亚硝酸钠、1.38g浓HCl和2.90g水在<5℃下,制备氯化4-溴代苯重氮水溶液。 The 0.688g 4- bromoaniline, 0.300g sodium nitrite, 1.38g of concentrated HCl and 2.90g of water at <5 ℃, the preparation of 4-bromo-benzene diazonium chloride solution. 在室温下,把该溶液加到10g粒状炭黑在60g水中的悬浮液中。 At room temperature, the solution was added to 60g water 10g pelletized carbon black in suspension. 放出气泡。 Release bubbles. 搅拌60分钟后,通过过滤取出该生成的炭黑,用水洗涤,并用四氢呋喃(THF)进行Soxhlet(索格利特)萃取过夜。 After stirring for 60 minutes, removed by filtration and the resultant carbon black, washed with water and Soxhlet (Soxhlet) extraction overnight with tetrahydrofuran (THF). 萃取后该炭黑产品的分析表明:它含有2.49%溴,与该实施例中使用前未处理粒状炭黑<0.01%相比较。 After extraction of the analysis show that the carbon black product: it contains 2.49 percent bromine, with this embodiment, prior to use of untreated carbon black particulate <0.01% compared. 这相当于连接到该炭黑产品上约78%溴苯基。 This is equivalent to connecting to approximately 78% of the carbon black products bromophenyl. 因此,该炭黑产品含有0.31mmol/g相连的溴苯基。 Therefore, the carbon black product contains 0.31mmol / g attached bromophenyl.

实施例2-4用预制的重氮盐制备炭黑产品这些实施例介绍另外制备本发明炭黑产品的方法。 Diazonium salt Example 2-4 Preparation of a carbon black product with preformed embodiment of these embodiments, the present invention describes the preparation of a carbon black product addition method. 用于实施例1中的粒状炭黑用于实施例2-4。 Pelletized carbon black used in Example 1 for Examples 2-4. 从0.688g4-溴代苯胺、0.300g亚硝酸钠、1.38g浓HCl和2.90g水在<5℃下制备氯化4-溴代苯重氮水溶液。 From 0.688g4- bromoaniline, 0.300g sodium nitrite, 1.38g of concentrated HCl and 2.90g water <Preparation chloride 5 ℃ 4- bromobenzene diazonium solution. 把该溶液在指定温度下加到10g粒状炭黑在60.5g 0.826%NaOH溶液中。 The solution was added to 10g granulated carbon black at a given temperature in 60.5g 0.826% NaOH solution. 放出气泡。 Release bubbles. 搅拌下表所示的时间后,通过过滤取出该生成的炭黑、用水洗涤并用THF进行Soxhlet萃取过夜。 After stirring for the time shown in the following table, the silica removed by filtration, washed with water and subjected to Soxhlet extraction with THF overnight. 萃取后该产品的溴分析表明相当大部分的溴苯基已连到该炭黑产品上。 Bromine of the product after extraction showed that a substantial portion of bromophenyl has been connected to the carbon black product. 这表明可在不同时间、温度和pH下制备本发明的炭黑产品 This indicates that the present invention can be prepared at different time, temperature and pH carbon black products

实施例5用现场生成的重氮盐来制备炭黑产品该实施例进一步介绍制备本发明炭黑产品。 5 with a diazonium salt generated in situ carbon black products prepared Example This example further describes the preparation of a carbon black product of the present invention. 使用具有表面积为560m2/g、DBPA为90ml/100g以及挥发物含量为9.5%的粉末炭黑。 Having a surface area of 560m2 / g, DBPA of 90ml / 100g and a volatile content of 9.5% carbon black powder. 把50g该飞扬性炭黑加到8.83g磺胺酸溶于420g水的溶液中。 The flying of the 50g black sulfa acid was added to 8.83g in 420g water solution. 把该生成的悬浮液冷却到室温。 The resultant suspension was cooled to room temperature. 把二氧化氮(5.16g)溶解于30g冰冷的水中,在几分钟内加入到该飞扬性炭黑悬浮液中,并快速搅拌,来现场制备4-磺基重氮苯内盐,该盐与飞扬性炭黑反应。 The nitrogen dioxide (5.16g) was dissolved in 30g of cold water within a few minutes was added to the suspension of carbon black filled, and rapid stirring, to the salt prepared in situ diazonium 4- sulfo benzene, and the salt Flying carbon black reaction. 该生成的分散液在烘箱中125℃干燥,只留下炭黑产品。 The resulting dispersion was dried in an oven at 125 ℃, leaving only the carbon black product. 该炭黑产品在用乙醇进行Soxhlet萃取过夜后,含有1.94%硫,与未处理炭黑的0.24%硫相比较。 The carbon black product after subjected to Soxhlet extraction overnight with ethanol contained 1.94% sulfur, compared to 0.24% sulfur for the untreated carbon black. 这相当于52%对-C6H4SO3-基团连接到炭黑产品上。 This is equivalent to 52% of -C6H4SO3- group connected to the carbon black product. 因此,该炭黑产品具有0.53mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.53mmol / g attached to -C6H4SO3- group.

实施例6制备炭黑产品该实施例介绍制备本发明炭黑产品的另外一个方法。 Example 6 Preparation of a carbon black product This example describes the preparation of carbon black products of the present invention is another method. 在搅拌和加热下把磺胺酸(2.13g)溶解在90g水中。 In the stirring and heating to sulfa acid (2.13g) was dissolved in 90g water. 加入10g具有CTAB表面积为350m2/g和DBPA为120ml/100g的炭黑。 10g of having a CTAB surface area of 350m2 / g and DBPA carbon black 120ml / 100g of. 把该混合物冷却到室温并加入亚硝酸异丁酯(1.27g)。 The mixture was cooled to room temperature and isobutyl nitrite (1.27g). 放出气泡。 Release bubbles. 现场生成氢氧化4-磺基重氮苯钠盐,并与炭黑反应。 Field generating hydroxide 4- sulfo benzene diazonium salt and reacted with the carbon black. 把该混合物搅拌30分钟,在烘箱中125℃下干燥。 The mixture was stirred for 30 minutes in an oven dried at 125 ℃. 已用乙醇进行整夜Soxhlet萃取的该生成的炭黑产品含有2.02%硫,与未处理炭黑为0.5%相比较。 Has Soxhlet extraction with ethanol overnight the generation of carbon black product contained 2.02% sulfur, 0.5% of the untreated carbon black in comparison. 因此,该炭黑产品含有0.48mmol/g相连的对-C6H4SO3-基。 Therefore, the carbon black product contains 0.48mmol / g attached to -C6H4SO3- group.

实施例7在非质子传递溶液中制备炭黑产品本实施例介绍在非质子传递溶剂中制备本发明的处理的炭黑产品。 Example 7 was prepared in an aprotic carbon black product of the present embodiment describes transfer processing of the present invention, a solvent in the preparation of carbon black products aprotic. 制备约0.1M六氟磷酸四丁基铵在无水乙腈中的溶液,并在3A分子筛中放置过夜。 Preparation of about 0.1M tetrabutylammonium hexafluorophosphate in anhydrous acetonitrile, and placed overnight in a 3A molecular sieve. 制备5.4%六氟磷酸氯重氮苯在无水乙腈中的溶液,并让其在3A分子筛中放置过夜。 5.4% solution of chlorine benzenediazonium hexafluorophosphate in anhydrous acetonitrile was prepared and allowed to stand overnight in a 3A molecular sieve. 表面积为230m2/g、DBPA70ml/100g的炭黑在氮气中150℃下干燥4小时。 A surface area of 230m2 / g, carbon black DBPA70ml / 100g of 150 ℃ under nitrogen for 4 hours. 把该炭黑(10g)搅拌入80ml六氟磷酸四丁基铵溶液中。 The carbon black (10g) was stirred into 80ml tetrabutyl ammonium hexafluorophosphate solution. 加入重氮溶液(21g),并把该混合物搅拌4小时。 Diazonium solution was added (21g), and the mixture was stirred for 4 hours. 通过过滤回收该炭黑产品并用无水乙腈洗涤。 The carbon black product recovered by filtration and washed with dry acetonitrile. 到此以前的所有操作都是在氩气氛中的干燥盒内进行的。 All this before operations are dried in an argon atmosphere box conducted. 已用THF整夜Soxhlet萃取并干燥的该炭黑样品的氯含量为0.76%,与未处理炭黑为0.02%相比较。 Have been extracted with THF overnight and dried Soxhlet chlorine content of the carbon black sample was 0.76%, 0.02% and untreated carbon black in comparison. 因此,该炭黑产品具有0.21mmol/g相连的氯苯基。 Therefore, the carbon black product has 0.21mmol / g attached chlorophenyl.

实施例8在非质子传递溶液中制备炭黑产品该实施例介绍在非质子传递溶剂中制备处理的炭黑产品。 Example 8 was prepared in an aprotic carbon black product This example describes the transfer of carbon black prepared in a solvent-treated product in an aprotic. 把表面积为230m2/g、DBPA为70ml/100g的炭黑在氮气中950℃下加热1小时。 The surface area of 230m2 / g, DBPA of 70ml / 100g carbon black was heated under nitrogen at 950 ℃ 1 hour. 制备0.1M四氟硼酸四丁基铵在无水苄腈中的溶液,并让其在3A分子筛中放置过夜。 Preparation of 0.1M tetrabutylammonium tetrafluoroborate in anhydrous benzonitrile and was allowed to stand overnight in a 3A molecular sieve. 使用在氩气中160℃下干燥的玻璃仪器,把该炭黑(6g)搅拌入50ml四氟硼酸四丁基铵溶液中。 Use dry glassware under argon 160 ℃, the carbon black (6g) was stirred into 50ml tetrabutylammonium tetrafluoroborate solution. 加入四氟硼酸4-溴重氮苯,并搅拌该混合物15分钟。 Diazonium tetrafluoroborate was added 4-bromo-benzene, and the mixture was stirred for 15 minutes. 通过过滤回收该炭黑产品并用苄腈洗两次且用己烷洗两次。 The carbon black product was recovered by filtration and washed twice with benzonitrile and twice with hexane. 除了炭黑的初始干燥外,到此以前的所有步骤都是在氩气氛中的干燥盒内进行的。 In addition to the initial drying of the carbon black, before this step are all in an argon atmosphere dry box conducted. 用THF萃取过夜的并干燥的炭黑产品样品的溴含量为85%,与未处理炭黑的<0.01%相比较。 Extracted with THF overnight and dried bromine content of the carbon black product samples was 85% compared with the untreated carbon black is <0.01%. 因此,该炭黑产品具有0.11mmol/g相连的溴苯基。 Therefore, the carbon black product has 0.11mmol / g attached bromophenyl.

实施例9用现场生成的重氮盐制备炭黑产品该实施例介绍另外一种制备本发明炭黑产品的方法。 9 with a diazonium salt generated in situ preparation of a carbon black product This Example describes another embodiment of the present invention is the preparation of a carbon black product of the method. 使用表面积为560m2/g、DBPA为90ml/100g和挥发物含量为9.5%的飞扬性炭黑。 Use a surface area of 560m2 / g, DBPA of 90ml / 100g and volatile matter content of 9.5% carbon black dust. 把50g该飞扬性炭黑加入到8.83g磺胺酸溶于420g水中的溶液中。 The flying of the 50g of carbon black is added to a solution of 8.83g sulfa acid in 420g of water. 把该生成的悬浮液冷却到30℃并加入4.6g浓硝酸。 The resultant suspension was cooled to 30 ℃ and 4.6g of concentrated nitric acid was added. 然后在搅拌下逐渐加入含有3.51g亚硝酸钠的水溶液,现场生成氢氧化4-磺基重氮苯内盐,该内盐与该飞扬性炭黑反应。 Then gradually added with stirring an aqueous solution containing 3.51g of sodium nitrite, hydroxide, inner field generating 4- sulfo benzene diazonium salt, the reaction of the salt with the carbon black dust. 在烘箱中125℃下干燥该生成的产品,得到该炭黑产品。 In an oven at 125 ℃ drying the resulting product to obtain a carbon black product. 用乙醇整夜Soxhlet萃取后,该炭黑产品含有1.97%硫,与未处理炭黑的为0.24%硫相比较。 Soxhlet extraction with ethanol overnight, the carbon black product contained 1.97% sulfur, compared to 0.24% sulfur in the untreated carbon black. 这相当于该炭黑产品连有53%对-C6H4SO3-基团。 This is equivalent to 53% of the carbon black product of -C6H4SO3- groups. 因此,该炭黑产品具有0.54mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.54mmol / g attached to -C6H4SO3- group.

实施例10用脂族重氮盐制备炭黑产品该实施例介绍另外一种制备本发明炭黑产品的方法。 10 aliphatic carbon black products prepared diazonium salt This Example describes another embodiment of the present invention is a process for preparing a carbon black product of the method. 使用表面积为230m2/g、DBPA为70ml/100g的飞扬性炭黑。 Use a surface area of 230m2 / g, DBPA of flying carbon black 70ml / 100g of. 把20g这种炭黑加到4.9g2-氨基乙磺酸在180g水中的溶液中。 This carbon black was added to 20g 4.9g2- aminoethanesulfonic acid solution 180g of water. 加入浓硝酸(4.32g)。 Was added concentrated nitric acid (4.32g). 搅拌下缓慢加入3.33g亚硝酸钠在15g水中的溶液中,现场形成硝酸2-磺基乙烷重氮物,该重氮物与该飞扬性炭黑反应。 Was added slowly with stirring in a solution of sodium nitrite 3.33g in 15g water, nitric acid is formed in situ diazonium 2- sulfo ethane, which reacted with the diazonium flying carbon black. 放出大量气泡。 Release a lot of bubbles. 在烘箱中135℃下干燥该产品,得到炭黑产品。 And dried in an oven at 135 ℃ the product, to give carbon black products. 用乙醇Soxhlet萃取过夜后该生成的炭黑产品含有1.68%硫,与未处理的粉末炭黑含有0.4%相比较。 Soxhlet extraction with ethanol overnight the resulting carbon black product contained 1.68% sulfur, with the untreated carbon black powder containing 0.4% compared. 这相当于该炭黑产品上连有20%的C2H4SO3-基团。 This is equivalent to the carbon black product even 20% of C2H4SO3- groups. 因此,该炭黑产品有0.40mmol/g相连的C2H4SO3-基团。 Therefore, the carbon black product has 0.40mmol / g attached C2H4SO3- group.

实施例11用苄基重氮盐制备炭黑产品本实施例介绍另外一种制备本发明炭黑产品的方法。 Example 11 Preparation of the diazonium salt with benzyl carbon black product of the present embodiment, the present invention describes a method another carbon black product prepared. 在冰浴中制备0.676g4-溴苄基胺、0.60g浓HCl、30g水和10.22g实施例7中所用的未处理炭黑的悬浮液。 Preparation 0.676g4- bromobenzyl amine in an ice bath, 0.60g of concentrated HCl, 30g of water and 10.22g Example 7 untreated carbon black used in the suspension. 加入含有0.269g亚硝酸钠的水溶液并搅拌该得到的悬浮液15分钟,现场生成氯化4-溴苯基甲烷重氮物,该重氮物与未处理的炭黑反应。 An aqueous solution containing 0.269g of sodium nitrite was added and the resulting suspension was stirred for 15 minutes, 4-bromophenyl chloride generated in situ diazonium methane, reacting the diazo untreated carbon black. 过滤该产品,并用THF进行整夜Soxhlet萃取。 The product was filtered, and Soxhlet extraction overnight with THF conduct. 该生成的炭黑产品含有0.26%溴,与未处理炭黑小于0.01%相比较。 The resulting carbon black product contained 0.26% bromine, less than 0.01% of the untreated carbon black in comparison. 这表明该实施例中所用溴苄基的9%连到了该炭黑产品上。 This indicates that the examples used in 9% of the bromobenzyl to the carbon black product. 因此,该炭黑产品具有0.031mmol/g相连的溴苄基。 Therefore, the carbon black products having 0.031mmol / g attached bromobenzyl groups.

实施例12制备炭黑产品该实施例介绍制备本发明炭黑。 Example 12 Preparation of a carbon black product This example describes the preparation of carbon black of the present invention. 把10g表面积为230m2/g、DBPA为70ml/100的炭黑加到0.8g4-溴苯甲酰胺和90ml丙酮在90g水中的搅拌的溶液中。 10g of the surface area of 230m2 / g, DBPA of 70ml / 100 carbon black was added bromobenzene carboxamide 0.8g4- acetone and 90ml water stirred solution of 90g. 加入浓HCl(0.87g)、接着加入0.33gNaNO2。 Concentrated HCl (0.87g), followed by the addition 0.33gNaNO2. 现场形成BrC6H4CON2+,其与炭黑反应。 Formed in situ BrC6H4CON2 +, which reacted with the carbon black. 搅拌30分钟后,该混合物静置过夜,然后在烘箱中125℃下干燥。 After stirring for 30 minutes, the mixture was allowed to stand overnight, and then dried in an oven at 125 ℃. 已用THF进行了整夜Soxhlet萃取并干燥的该炭黑产品样品含有0.22%溴,与未反应炭黑<0.01%溴相比较。 It has been carried out with THF and dried overnight Soxhlet extraction of the sample containing 0.22% carbon black products bromine, unreacted carbon black and <0.01% compared with bromine.

实施例13在销型造粒机中用预制的重氮盐制备炭黑产品该实施例介绍另外一种制备本发明炭黑产品的方法。 Example 13 pin-type granulator with a preformed diazonium salt prepared carbon black product This example describes the preparation of another method of the present invention, the carbon black product. 销型造粒机中加入400g表面积为80m2/g、DBPA为85ml/100g的飞扬性炭黑。 Pin-type granulator was added 400g surface area of 80m2 / g, DBPA of flying carbon black 85ml / 100g of. 由27.1g磺胺酸的钠盐、10.32g亚硝酸钠、29.0g浓HCl和293.5g水制备氢氧化4-磺基重氮苯的冷悬浮液,并把其加到该造粒机中。 The sodium salt of 27.1g sulfa acid, 10.32g of sodium nitrite, 29.0g 293.5g of concentrated HCl and cold water preparation hydroxide suspension of 4-sulfophthalic benzenediazonium and put it added to the granulator. 造粒2分钟后,取出该样品,并在115℃下干燥至恒重。 Granulated after 2 minutes, the sample was taken, and dried at 115 ℃ to constant weight. 用乙醇整夜Soxhlet萃取,得到含有1.1%硫的炭黑产品,与未处理炭黑的0.8%相比较。 Soxhlet extraction with ethanol overnight, to give a sulfur containing 1.1% carbon black product, compared with 0.8% in the untreated carbon black. 这表明27%的对-C6H4SO3-连到该炭黑产品上。 This indicates that 27% of the carbon black product -C6H4SO3- to. 因此,该炭黑产品具有0.09mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.09mmol / g attached to -C6H4SO3- group.

实施例14在销型造粒机中用现场生成的重氮盐制备炭黑产品该实施例介绍了制备本发明炭黑的另一种方法。 Example 14 pin granulator with diazonium salt generated in situ preparation of a carbon black product This example describes an alternative method of preparing carbon black of the present invention. 销型的造粒机中加入200g CTAB表面积为350m2/g、DBPA为120ml/100g的炭黑。 Pin-type granulator was added 200g CTAB surface area of 350m2 / g, DBPA of the carbon black 120ml / 100g of. 加入44.2g磺胺酸钠在95g70℃水中的溶液,该造粒机运行1分钟。 Join 44.2g sodium sulfa 95g70 ℃ water in the granulator for 1 minute. 加入20g水,然后加入39.6g浓硝酸。 20g of water was added, followed by addition of 39.6g of concentrated nitric acid. 该造粒机再运行1分钟。 The granulator run for 1 minute. 加入20g水、接着加入16.76g亚硝酸钠在35g水中的溶液,现场形成氢氧化4-磺基重氮苯内盐,该内盐与该炭黑反应。 20g of water was added, followed by addition of a solution of 16.76g of sodium nitrite in 35g of water, the hydroxide is formed in situ 4- sulfo benzene diazonium salt, the reaction of the salt with the carbon black. 造粒机运行5分钟后,加入11.22g氢氧化钠在35g水中的溶液。 After running the granulator for 5 minutes in a solution of sodium hydroxide was added 11.22g 35g water. 该造粒机再运行另外两分钟,接着干燥该生成的炭黑产品。 The granulator and then run another two minutes, followed by drying the produced carbon black products. 用乙醇整夜Soxhlet萃取后,得到含有3.3%硫的炭黑产品,与未处理炭黑为0.5%相比较。 Soxhlet extraction with ethanol overnight, to give a sulfur containing 3.3% of carbon black products, the untreated carbon black was 0.5% compared. 这表明77%对-C6H4SO3基团连接到该炭黑产品上。 This indicates that 77% of -C6H4SO3 groups on the carbon black product is connected to. 因此,该炭黑产品具有0.88mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.88mmol / g attached to -C6H4SO3- group.

实施例15 Example 15

在销式造粒机中用现场产生的重氮盐制备炭黑产品该实施例继续介绍本发明炭黑产品的制备。 The pin pelletizer with a diazonium salt generated in situ preparation of a carbon black product of the embodiment of the present invention continue to introduce the carbon black product was prepared. 向销式造粒机中加入200g表面积为560m2/g、DBPA为90ml/100g、挥发物含量为9.5%的炭黑。 The pin granulator was added 200g surface area of 560m2 / g, DBPA of 90ml / 100g, volatile content of 9.5% of carbon black. 顺序加入水(60g)、浓硝酸(25.2g)、磺胺酸(40.4g)和19.7g亚硝酸钠在35g水中的溶液;每次加料后该造粒机运行1分钟。 Sequential addition of water (60g), concentrated nitric acid (25.2g), sulfanilic acid (40.4g) and 19.7g sodium nitrite in 35g of water; granulator run each time the one minute after the addition. 现场生成氢氧化磺基重氮苯内盐,该内盐与该炭黑反应。 Hydroxide inner salt generated in situ sulfo benzenediazonium, the inner salt reacts with the carbon black. 静置5分钟后,在125℃下干燥该生成的炭黑产品。 Stand for 5 minutes at 125 ℃ drying the produced carbon black products. 用乙醇将该炭黑产品样品进行Soxhlet萃取过夜。 The carbon black product with ethanol samples were Soxhlet extraction overnight. 它含有2.15%硫,与未处理炭黑的0.24%相比较。 It contains 2.15% sulfur, compared to 0.24% of the untreated carbon black. 这表明51%的对-C6H4SO3-基连到该炭黑产品上。 This indicates that 51% of -C6H4SO3- group is attached to the carbon black product. 因此,该炭黑产品有0.60mmol/g相连的对-C6H4SO3-基。 Therefore, the carbon black product has 0.60mmol / g attached to -C6H4SO3- group.

实施例16在造粒机中用现场生成的重氮盐制备炭黑产品该实施例介绍了制备本发明炭黑产品的另一个方法。 Example 16 granulator used in the preparation of diazonium salt generated in situ carbon black product This example describes another method for producing carbon black product of the present invention. 把具有表面积为350m2/g、DBPA为120ml/100g的炭黑和42.4g磺胺酸加入销式造粒机中。 To have a surface area of 350m2 / g, DBPA carbon black 120ml / 100g and 42.4g sulfanilic acid added to the pin-type granulator. 混合40秒钟后,加入20.7gNaNO2在150g水中的溶液。 After mixing for 40 seconds, add 20.7gNaNO2 solution in 150g of water. 现场生成氢氧化4-磺基重氮苯内盐,该内盐与炭黑反应。 Field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, the salt and the carbon black in the reaction. 混合45秒后,在烘箱中120℃下干燥该生成的炭黑产品。 Mixed for 45 seconds, in an oven at 120 ℃ the resulting carbon black product was dried. 用乙醇进行过Soxhlet萃取过夜的该炭黑产品样品含有3.47%硫,与未处理炭黑产品的0.5%硫相比较。 Soxhlet extraction with ethanol overnight over the carbon black product contained 3.47% sulfur sample, compared to the untreated carbon black product with 0.5% sulfur. 因此,该炭黑产品具有0.93mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.93mmol / g attached to -C6H4SO3- group.

实施例17用现场生成的重氮盐在连续的销式造粒机中制备炭黑产品该实施例介绍另外一种制备本发明炭黑产品的方法。 17 with a diazonium salt generated in situ preparation of a carbon black product This example describes another embodiment of the present invention is a method for preparing a carbon black product in a continuous pin pelletizer Example. 以每小时100重量份的速率,向连续运行的销式造粒机中,加入CTAB表面积为133m2/g、DBPA为190ml/100g的飞扬性炭黑。 100 parts by weight per hour rate, the continuous operation of a pin granulator, adding CTAB surface area of 133m2 / g, DBPA of carbon black filled 190ml / 100g of. 同时,向该造粒机中加入亚硝酸钠在水中的30%溶液和含有5.43%浓硝酸、8.72%磺胺酸和85.9%水的悬浮液。 At the same time, to the granulator of sodium nitrite 30% solution in water containing 5.43% concentrated nitric acid, 8.72% sulfanilic acid and 85.9% water suspension. 以每小时16重量份的速率加入亚硝酸钠溶液,并以每小时112重量份的速率加入该悬浮液。 16 parts by weight per hour rate of adding sodium nitrite solution, and 112 parts by weight per hour rate was added to the suspension. 现场生成氢氧化4-磺基重氮苯内盐,且它在该造粒机中与该炭黑反应。 Field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, and it is in the granulator reacts with the carbon black. 从造粒机中出来的材料是炭黑产品。 Coming out of the granulator material is carbon black products. 在125℃下干燥该炭黑产品。 At 125 ℃ drying the carbon black product. 用乙醇进行Soxhlet萃取过夜的炭黑产品样品含有1.7%硫,与未处理炭黑的0.42%相比较。 Soxhlet extraction with ethanol overnight carbon black product containing 1.7% sulfur sample, compared to 0.42% for the untreated carbon black. 因此,该炭黑产品有0.40mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.40mmol / g attached to -C6H4SO3- group.

实施例18用现场生成的重氮盐制备炭黑产品该实施例介绍了另外一种制备本发明炭黑产品的方法。 18 with a diazonium salt generated in situ preparation of a carbon black product This Example illustrates the preparation of another embodiment of the present invention is the preparation of a carbon black product of the method. 在该实施例中,用于重氮化反应的酸来自于形成重氮盐的胺,磺胺酸。 In this embodiment, the acid used for diazotization reaction comes from the amine forming the diazonium salt, sulfanilic acid. 结果,不需要添加另外的酸。 As a result, no need to add additional acid. 磺胺酸(2.12g)溶解在70℃的90g水中。 Sulfa acid (2.12g) was dissolved in 90g of water 70 ℃. 把该溶液加到10克CTAB表面积为350m2/g、DBPA为120ml/100g的炭黑中,冷却到室温。 The solution was added to 10 g CTAB surface area of 350m2 / g, DBPA of the carbon black 120ml / 100g, the cooled to room temperature. 在搅拌的同时加入1.04g NaNO2在10g水中的溶液。 While stirring 1.04g NaNO2 solution in 10g water was added. 现场生成氢氧化4-磺基重氮苯内盐,它与该炭黑反应,形成该炭黑产品。 Field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, which reacts with the carbon black to form the carbon black product. 搅拌30分钟后,在烘箱中120℃下干燥该生成的分散液。 After stirring for 30 minutes at 120 ℃ dried in an oven and the resultant dispersion. 用乙醇已进行过Soxhlet萃取过夜的炭黑产品样品含有3.19%硫,与未处理炭黑的0.5%相比较。 Ethanol has been used Soxhlet extraction overnight carbon black product contained 3.19% sulfur samples, compared with 0.5% of the untreated carbon black. 因此,该炭黑产品有0.84mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.84mmol / g attached to -C6H4SO3- group.

实施例19用现场生成的重氮盐制备炭黑产品该实施例介绍了另外一种制备本发明炭黑产品的方法。 19 with a diazonium salt generated in situ preparation of a carbon black product This Example illustrates the preparation of another embodiment of the present invention is the preparation of a carbon black product of the method. 在该实施例中,用于重氮化反应的酸来自于形成重氮盐的胺,磺胺酸。 In this embodiment, the acid used for diazotization reaction comes from the amine forming the diazonium salt, sulfanilic acid. 结果,不需要另外的酸。 As a result, no additional acid. 向2.12g磺胺酸在90g水中的沸腾溶液中,加入10克CTAB表面积为350m2/g、DBPA为120ml/100g的炭黑。 2.12g to 90g sulfanilic acid in boiling water was added 10 g CTAB surface area of 350m2 / g, DBPA of the carbon black 120ml / 100g of. 小心地加入1.04g NaNO2在10g水中的溶液。 Was carefully added a solution of 1.04g NaNO2 in 10g of water. 现场生成氢氧化4-磺基重氮苯内盐,该内盐与该炭黑反应。 Field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, the inner salt reacts with the carbon black. 搅拌约20分钟后,在烘箱中120℃下干燥该生成的分散液。 After stirring for about 20 minutes at 120 ℃ dried in an oven and the resultant dispersion. 用乙醇进行过Soxhlet萃取过夜的炭黑产品样品含有3.16%硫,与未处理炭黑的0.5%硫相比较。 Soxhlet extraction with ethanol overnight over carbon black product contained 3.16% sulfur sample, compared to 0.5% sulfur for the untreated carbon black. 因此,该炭黑产品有0.83mmol/g相连的对-C6H4SO3-基团。 Therefore, the carbon black product has 0.83mmol / g attached to -C6H4SO3- group.

实施例20-30炭黑产品的水分散性这些实施例表明:在前面一些实施例中所介绍的本发明炭黑,比相应的未处理炭黑更容易分散在水中 EXAMPLE 20-30 The water-dispersible carbon black products These examples show: In front of the carbon black of the present invention is described in some embodiments, more readily than the corresponding untreated carbon black dispersed in water

</tables> </ Tables>

实施例31-34炭黑产品的制备和水分散性这些实施例表明:用几种不同的重氮盐制备的炭黑产品比相应的未处理炭黑更易分散在水中。 Preparation and water dispersible carbon black products of Examples 31-34 These examples show: carbon black products in several different diazonium salts prepared more than the corresponding untreated carbon black dispersed in water. 在所有的情况下,用来处理的未处理炭黑的表面积为230m2/g、DBPA为70ml/100g。 In all cases, the surface area of the untreated carbon black used for treatment of 230m2 / g, DBPA of 70ml / 100g. 为了制备炭黑产品,把苯胺衍生物溶于热水中,加入未处理炭黑(CB),并把该混合物冷却到室温。 To prepare the carbon black product, an aniline derivative was dissolved in the hot water, was added untreated carbon black (CB), and the mixture was cooled to room temperature. 加入浓HCl,然后加入亚硝酸钠在水中的溶液,现场生成重氮盐,该重氮盐与未处理炭黑反应。 Addition of concentrated HCl, then a solution of sodium nitrite in water, diazonium salt generated in situ, the diazonium salt is reacted with the untreated carbon black. 搅拌15分钟后,在烘箱中125℃下干燥该生成的分散液。 After stirring for 15 minutes at 125 ℃ dried in an oven and the resultant dispersion. 用上述方法测定残余物。 The residue was measured by the above method. 每一个组份的量和结果示于下表中。 The amount of each component and the results are shown in the following table. 未处理炭黑有94%的残余物。 94% of the untreated carbon black residue.

</tables>实施例35-38炭黑产品的制备和分散性这些实施例介绍了用不同重氮盐制备的并比相应的未处理炭黑更易分散在水中的另外的炭黑产品。 Examples 35-38 Preparation and dispersion of carbon black products These examples </ tables> Preparation of different embodiments described diazonium salt and more than the corresponding untreated carbon black dispersed in water, additional carbon black products. 所有这些实施例使用萘基重氮盐。 All these examples use naphthyl diazonium salts. 在所有的情况下,使用表面积为230m2/g、DBPA为70ml/100g的炭黑。 In all cases, the use of a surface area of 230m2 / g, DBPA of the carbon black 70ml / 100g of. 把7mmol萘胺和0.42g NaNO2在10.83g水中的溶液冷却到<5℃。 The 7mmol naphthylamine and 0.42g NaNO2 in 10.83g water was cooled to <5 ℃. 加入1.63g浓HCl在1.63g水中的冷(5℃)溶液,形成重氮盐。 Concentrated HCl was added 1.63g 1.63g in cold water (5 ℃) solution to form a diazonium salt. 把该反应产物加到10g未处理炭黑在90g水中的搅拌下的浆料中。 The reaction product was added with stirring 10g untreated carbon black slurry 90g of water. 搅拌另外10分钟后,干燥该分散液,留下该炭黑产品。 After stirring for an additional 10 minutes, the dispersion was dried, leaving the carbon black product. 分析用乙醇进行过Soxhlet萃取过夜的炭黑产品样品的硫,来确定相连的萘基数。 Analysis conducted Soxhlet extraction with ethanol overnight sulfur carbon black product samples to determine the base is connected to naphthalene.

实施例39炭黑产品的制备和水分散性该实施例介绍了另外一个制备本发明炭黑产品的方法并表明该炭黑产品比相应的未处理炭黑更易分散在水中。 Example 39 Preparation of carbon black products and water dispersible This example describes another method for preparing a carbon black product of the present invention and show that carbon black products more than the corresponding untreated carbon black dispersed in water. 7-氨基-1,3-萘二磺酸(1.5g)溶解在90g热水中。 7-amino-1,3-naphthalene disulfonic acid (1.5g) was dissolved in 90g of hot water. 加入10g表面积为230m2/g、DBPA为70ml/100g的炭黑,把该混合物冷却到室温。 10g of a surface area of 230m2 / g, DBPA of the carbon black 70ml / 100g, and the mixture was cooled to room temperature. 搅拌下加入0.42gNaNO2在5g水中的溶液。 0.42gNaNO2 solution was added with stirring 5g of water. 现场生成重氮盐,且该重氮盐与该炭黑反应。 Diazonium salt generated in situ, and the diazonium salt is reacted with the carbon black. 释放大量气泡。 Release a lot of bubbles. 在烘箱中125℃下干燥该分散液,得到该炭黑产品。 Drying the dispersion in an oven at 125 ℃ to obtain the carbon black product. 该炭黑产品的残余物为0.85%,与未处理炭黑的94%相比较。 The residue of the carbon black product was 0.85%, compared with 94% of the untreated carbon black.

实施例40炭黑产品的制备和水分散性该实施例表明:用另外重氮盐制备的炭黑产品比相应的未处理炭黑更易分散在水中。 Example 40 Preparation and aqueous dispersibility of a carbon black product This example shows that: the diazonium salt prepared by addition of carbon black products than the corresponding untreated carbon black is easier to disperse in water. 使用的炭黑的表面积为230m2/g、DBPA为70ml/100g。 The surface area of the carbon black used was 230m2 / g, DBPA of 70ml / 100g. 在冰浴中混合5-氨基-2-羟基-3-磺基苯甲酸(2.33g)、10g炭黑和100g水。 Mixed amino-2-hydroxy-3-sulfobenzoic acid (2.33g), 10g carbon black and 100g of water in an ice bath. 加入冷的浓HCl(1.18g)、接着逐渐加入0.85g NaNO2。 Addition of cold concentrated HCl (1.18g), followed by gradual addition of 0.85g NaNO2. 现场制备出重氮盐,并与该炭黑反应。 A diazonium salt prepared in situ, and reacted with the carbon black. 搅拌15分钟后,在烘箱中125℃下干燥该生成的分散液,得到该炭黑产品。 After stirring for 15 minutes, at 125 ℃ dispersion was dried in an oven that was generated to obtain the carbon black product. 该生成的炭黑产品的325目残余物为0.1%,与未处理炭黑的94%相比较。 The resulting carbon black product was a 325 mesh residue of 0.1%, compared with 94% of the untreated carbon black.

实施例41 Example 41

炭黑产品的制备和水分散性该实施例表明:用另外重氮盐制备的炭黑产品比相应的未处理炭黑更容易分散在水中。 Preparation of carbon black products and water dispersible This example shows that: the diazonium salt prepared by addition of carbon black products disperse more easily in water than the corresponding untreated carbon black. 除了使用4-氨基-2′-硝基-4_磺基二苯胺(3.01g)作为重氮前体外,所有方面都按照实施例40的程序。 Except that 4-amino-2'-nitro -4_ sulfo diphenylamine (3.01g) as a diazo before the body, according to an embodiment of all aspects of the program 40. 该生成的炭黑产品的325目残余物为0.18%,与未处理炭黑的94%相比较。 The resulting carbon black product was a 325 mesh residue of 0.18%, compared with 94% of the untreated carbon black.

实施例42炭黑产品的制备和水分散性该实施例介绍了本发明炭黑产品另外的制备,并表明该炭黑产品比相应的未处理炭黑更易分散在水中。 Example 42 Preparation of carbon black products and water dispersible This example describes the preparation of additional carbon black product of the present invention, and shows that the carbon black products more than the corresponding untreated carbon black dispersed in water. 把4-氨基苯基膦酸(0.90g)加到10g冰冷的水中。 The 4-phenyl acid (0.90g) was added to 10g of ice-cold water. 加入NaOH(0.26g)来溶解该固体。 Was added NaOH (0.26g) to dissolve the solid. 加入0.42g NaNO2在5g冷水中的冷溶液。 Cold solution was added 0.42g NaNO2 5g cold water. 加入浓HCl(3.83g)并在<10℃下搅拌该溶液15分钟,形成相应的重氮盐。 Concentrated HCl (3.83g) and the solution was stirred at <10 ℃ for 15 minutes, forming the corresponding diazonium salt. 加入5.02g表面积为230m2/g、DBPA为70ml/100g在36.2g水中的冷悬浮液,并搅拌15分钟。 Was added 5.02g surface area of 230m2 / g, DBPA of 70ml / 100g 36.2g of water in the cold suspension was stirred for 15 minutes. 在真空和室温下浓缩该生成的分散液至干燥状态,得到炭黑产品。 Concentrated under vacuum at room temperature and the resultant dispersion to dryness to give a carbon black product. 该炭黑产品易于在水中分散,并具有2.7%的325目残余物,与未处理炭黑的为94%相比较。 The carbon black products disperse readily in water, and having 2.7% of 325 mesh residue of the untreated carbon black was 94% compared. 在烘箱中125℃下干燥的该炭黑产品样品不分散在水中。 In an oven-dried sample of the carbon black product at 125 ℃ not dispersed in water. 已用THF进行过Soxhlet萃取过夜的该炭黑产品样品含有1.57%亚磷基。 It has been Soxhlet extraction with THF overnight and the carbon black product samples containing 1.57% phosphorous group. 因此,该炭黑产品具有0.51mmol/g相连的对-C6H4PO3=基。 Therefore, the carbon black product has 0.51mmol / g connected to -C6H4PO3 = group.

实施例43炭黑产品的制备和水分散性该实施例介绍在制备本发明炭黑产品中使用含有季铵盐的重氮盐和这种炭黑产品的水分散性。 Example 43 Preparation of carbon black products and water dispersible This Example describes the use of a diazonium salt containing a quaternary ammonium and this carbon black product in the preparation of water-dispersible carbon black product of the present invention. 把硝酸3-氨基 N-甲基-吡啶鎓(11mmol)在30g水中的冷溶液加到11.0g炭黑(表面积230、DBPA 70)在70g小于70℃水中的悬浮液中。 The nitric acid 3-amino-N- methyl - pyridinium (11mmol) in 30g of water was added to a cold solution of 11.0g of carbon black (surface area 230, DBPA 70) in less than 70 ℃ 70g water suspension. 加入浓HCl(2.38g)。 Concentrated HCl (2.38g). 小心加入0.92gNaNO2在10g水中的冷溶液,并把该反应混合物搅拌20分钟。 0.92gNaNO2 cooled solution was carefully added 10g of water, and the reaction mixture was stirred for 20 minutes. 现场生成重氮盐,且该盐与该炭黑反应。 Diazonium salt generated in situ, and the salt reacted with the carbon black. 接着加入0.50gNaOH在10g水中的溶液。 0.50gNaOH solution was then added 10g of water. 在130℃下干燥该样品,得到该炭黑产品。 At 130 ℃ drying the sample to obtain a carbon black product. 该炭黑产品具有0.40%325目残余物,与未处理炭黑产品的94%相比较。 The carbon black product has 0.40% 325 mesh residue, compared with 94% for the untreated carbon black product.

实施例44炭黑产品的制备和水分散性该实施例继续介绍了在制备本发明炭黑产品中使用含有季铵盐的重氮盐和该炭黑产品的水分散性。 Example 44 Preparation of carbon black products and water dispersible went on to explain the embodiment of the present invention used in the preparation of carbon black products containing quaternary ammonium salt of the diazonium salt and the carbon black products of water-dispersible. 使用的方法类似于实施例43,用9.8mmol硝酸4-(氨基苯基)-三甲基铵、10.0g炭黑、2.25g浓HCl、0.83gNaNO2,得到具有325目残余物为0.6%的炭黑产品。 The method used is similar to Example 43, using nitric acid 9.8mmol 4- (aminophenyl) - trimethyl ammonium, 10.0g of carbon black, 2.25g of concentrated HCl, 0.83gNaNO2, having 325 mesh to obtain carbon residue of 0.6% black products. 未处理炭黑的残余物为94%。 The residue of the untreated carbon black was 94%.

实施例45炭黑产品的制备和水分散性该实施例表明用另外重氮盐制备的炭黑产品比相应的未处理炭黑更易分散在水中。 Example 45 Preparation of carbon black products and water dispersible This example shows the preparation of the diazonium salt by addition of carbon black products than the corresponding untreated carbon black is easier to disperse in water. 用来处理的炭黑的表面积为230m2/g、DBPA为70ml/100g。 The surface area of the carbon black is used to treat 230m2 / g, DBPA of 70ml / 100g. 从0.77g4-氨基苯乙酸,9.2g冷水、1.35g冷的浓HCl和0.44g NaNO2制备氯化4-羧甲基重氮苯。 From 0.77g4- amino acid, 9.2g cold water, 1.35g cold concentrated HCl and 0.44g NaNO2 Chlorination 4-carboxymethyl benzenediazonium. 把该重氮物溶液加到搅拌下的5.04g炭黑在35.2g水中的冰冷的悬浮液中。 The diazonium solution was added to a stirred solution of 5.04g in 35.2g of water solution of the carbon black suspension. 释放出大量气泡。 Releasing large amounts of air bubbles. 搅拌20分钟后,把该分散液放置在27℃的水浴中,并搅拌另外20分钟。 After stirring for 20 minutes, to the dispersion was placed in a water bath at 27 ℃, and stirred for an additional 20 minutes. 在烘箱中120℃下干燥该分散液,得到325目残余物含量为2.5%的炭黑产品,与未处理炭黑的94%相比较。 The dispersion was dried in an oven at 120 ℃, to give a 325 mesh residue content of 2.5% of carbon black products, compared with 94% of the untreated carbon black.

实施例46炭黑产品的制备和水分散性该实施例表明:用另外重氮盐处理的炭黑产品比相应的未处理炭黑更易分散在水中。 Example 46 Preparation of carbon black products and water dispersible This example shows that: with the addition of the diazonium salt treated carbon black products than the corresponding untreated carbon black is easier to disperse in water. 用来处理的炭黑的表面积为230m2/g和DBPA为70ml/100g。 The surface area of the carbon black is used to treat 230m2 / g and DBPA of 70ml / 100g. 向销式造粒机中加入200g炭黑。 To pin granulator added 200g of carbon black. 相继向该造粒机中加入80mmol(12.7g)4-氨基苯甲酸钠在45g水中的悬浮液、25.7g浓HCl、7.04gNaNO2在30g水中的溶液,且在前面两个加料后混合1分钟,最后一次加料后混合5分钟。 To this was added sequentially granulator 80mmol (12.7g) 4- amino 45g sodium benzoate in water suspension, 25.7g concentrated HCl, 7.04gNaNO2 solution in 30g water, and, after the addition of two preceding mixing for 1 minute, and finally mixed for 5 minutes after the addition time. 现场生成氯化羧基重氮苯,且它与该炭黑反应。 Benzenediazonium carboxyl chloride generated in situ, and it reacted with the carbon black. 加入7.83gNaOH在30g水中的溶液,并继续混合2分钟。 7.83gNaOH solution was added 30g of water, and mixing was continued for two minutes. 该生成的炭黑产品在120℃下干燥并具有6.4%的325目残余物,与未处理炭黑的94%相比较。 The resultant carbon black product was dried at 120 ℃ and has 6.4 percent of 325 mesh residue, compared with 94% of the untreated carbon black.

实施例47-59炭黑产品的制备和其用作ABS中的着色剂这些实施例介绍了用不同的胺制备本发明炭黑产品和把这些炭黑产品用作ABS中的着色剂。 47-59 Preparation of carbon black products and their use as colorants in ABS These examples introduced ABS colorant in the present invention, the carbon black product prepared using different amines and put these carbon black products used. 在每个实施例中,使用表面积为230m2/g、DBPA为70ml/100g的飞扬性炭黑。 In each embodiment, a surface area of 230m2 / g, DBPA of carbon black filled 70ml / 100g of. 在冰浴中,从指定的化合物、2.2当量的浓HCl和1.0当量NaNO2制备作为9.65M的溶液的重氮盐。 In an ice bath, the compound designated, 2.2 equivalents of concentrated HCl and 1.0 equivalents of NaNO2 as a diazonium salt prepared 9.65M solution. 把该生成的溶液加到200g飞扬性炭黑在3L水中的悬浮液中,并搅拌10-20分钟。 The resultant solution was added 200g of carbon black in 3L of water flying suspension, and stirred for 10-20 minutes. 对该生成的炭黑产品过滤、用水洗涤两次,在约100℃下干燥。 The resulting carbon black product was filtered, washed twice with water, dried at about 100 ℃. 在一些例子中,把在二分之一或四分之一规模下得到的多批量组合在一起,来进行制备。 In some instances, put in half or one-quarter the size of the resulting multi-volume together, be prepared.

在布雷本登(Brabender)混炼机中110℃下熔化183g乙烯-乙酸乙烯聚合物(EVA)1分钟、加入45.8g炭黑产品并混合另外4分钟,来制备母炼胶。 In the Brabender (Brabender) mixer melting at 110 ℃ 183g ethylene - vinyl acetate polymer (EVA) 1 min, and mixed for an additional 45.8g of carbon black products for 4 minutes to prepare a master batch. 通过注塑80g母炼胶、1520g ABS(丙烯腈-丁二烯-苯乙烯共聚物树脂)的混合物,来制备评估用的注塑样品。 By injection masterbatch 80g, 1520g ABS (acrylonitrile - butadiene - styrene copolymer resin) was to assess the injection molded samples prepared with. 在模制样品中该炭黑产品的最终浓度为1%。 In the molded sample of the carbon black product final concentration of 1%.

用悬臂梁式冲击试验仪测定该测量材料的冲击强度;用亨特比色计测定其光学性能。 Determination of the impact strength of the material was measured with an Izod impact tester; Hunter was measured by using a colorimetric optical properties. 得到的冲击强度用所用的未填充ABS的冲击强度的百分数来表示。 The impact strength of the unfilled ABS impact strength by percentage used to represent. 希望的性能是:高的冲击强度、低亨特L值(更黑)(jetter)、亨特a值近于0和亨特b负值更大(更蓝)。 Desired performance are: high impact strength, low Hunter L values (darker) (jetter), Hunter a value close to 0, and more negative Hunter b (bluer). 通常当把炭黑加到ABS中赋予其颜色时,随着黑色的提高,冲击强度受到损失。 Usually when the carbon black is added to ABS to impart color, with black improve the impact strength suffer. 该结果表明本发明的炭黑产品可用作ABS中的着色剂 The results show that carbon black products of the present invention are useful as a colorant in ABS

</tables> </ Tables>

实施例60-62炭黑产品的制备和其用作ABS中的着色剂这些实施例介绍了用不同的处理剂制备本发明的炭黑产品,以及用这些炭黑产品作为ABS中的着色剂。 60-62 Preparation of carbon black products and their use as colorants in ABS These examples introduce the carbon black products with different preparation process of the present invention, and using these carbon black products as a colorant in ABS. 在每个例子中使用表面积为230m2/g、DBPA为70ml/100g的飞扬性炭黑。 In each case a surface area of 230m2 / g, DBPA of carbon black filled 70ml / 100g of. 使用实施例47-59的程序、用60mmol重氮前体来制备该炭黑产品。 Using the procedure of Example 47-59, but using body prepared before 60mmol diazo carbon black product.

在初始温度为210℃的布雷本登混炼机中熔化203.6g ABS、在175℃下加入50.9g炭黑产品并混合另外3分钟。 203.6g ABS melting at an initial temperature of 210 ℃ Brabender mixer, add 50.9g of carbon black product at 175 ℃ and mixed for an additional 3 minutes. 注塑75g母炼胶和1425g ABS的混合物,来制备评估用的注塑样。 Injection mixture 75g of the masterbatch and 1425g ABS, prepared sample evaluated by injection. 在该模制样中该炭黑产品的最终浓度为1%。 In the molded sample of the carbon black products in a final concentration of 1%.

用悬臂梁式冲击试验仪测定该测量材料的冲击强度;用亨特测定计测定其光学性能。 Determination of the impact strength of the material was measured with an Izod impact tester; was measured by their optical properties measured by Hunter. 得到的冲击强度用所用的未填充ABS的冲击强度的百分数来表示。 The impact strength of the unfilled ABS impact strength by percentage used to represent. 希望的性能是:高的冲击强度、低亨特L值(更黑)(jetter)、亨特a值近于0和亨特b负值更大(更蓝)。 Desired performance are: high impact strength, low Hunter L values (darker) (jetter), Hunter a value close to 0, and more negative Hunter b (bluer). 通常当把炭黑加到ABS中赋予其颜色时,随着黑色的提高,冲击强度受到损失。 Usually when the carbon black is added to ABS to impart color, with black improve the impact strength suffer. 该结果表明本发明的炭黑产品可用作ABS中的着色剂。 The results show that carbon black products of the present invention are useful as a colorant in ABS.

</tables>实施例63-65炭黑产品的制备和其用于使聚乙烯着色这些实施例介绍了本发明炭黑产品的制备。 63-65 Preparation of carbon black products </ tables> implementation and for coloring polyethylene These examples illustrate the preparation of carbon black products of the present invention. 使用表面积为140m2/g、DBPA为114ml/100g的炭黑。 A surface area of 140m2 / g, DBPA of the carbon black 114ml / 100g of. 由十四烷基苯胺、浓HCl、NaNO2、异丙醇和水,制备氯化十四苯重氮的冷溶液。 From 14 alkylphenyl amines, concentrated HCl, NaNO2, isopropanol and water, fourteen benzene diazonium chloride was prepared cold solution. 把该重氮溶液加到销式造粒机中的200g炭黑中;并混合一指定时间,加入另外的水#l,并继续混合另外3分钟。 The diazonium solution was added to a pin pelletizer of 200g carbon black; and mixed for a specified time, additional water #l, and mixing was continued for another 3 minutes. 加入更多的水#2和异丙醇#2后,继续混合,在烘箱中干燥生成的炭黑产品。 Add more water # 2 and isopropanol # 2, the mixing was continued in an oven dried resulting carbon black product. 通过在相同的造粒机中混合未处理炭黑和水及异丙醇并干燥,来制备对照样。 By the same granulator mixing the untreated carbon black and water and isopropyl alcohol and dried to prepare a control sample.

在布雷本登混炼机中,85℃下,混合169.34g低密度聚乙烯和72.6g炭黑样品五分钟,来制备母炼胶。 Brabender mixer at 85 ℃, mixing 169.34g low density polyethylene and 72.6g of carbon black sample five minutes, to prepare a master batch. 通过注塑10g母炼胶和1490g高密度聚乙烯的混合物,来制备评估用的瓷花金属板(Plaque)。 10g masterbatch by injection molding of high density polyethylene and 1490g of mixture, prepared evaluate ceramic flower metal plate (Plaque) used. 炭黑产品的最终浓度为0.2%。 The final concentration of carbon black product was 0.2%. 用亨特比色仪测量该瓷花金属板的光学性能。 By Hunter colorimeter measures the optical properties of the metal plate porcelain flower of. 结果表明:该炭黑产品比对照样稍微有点发黑(较低的亨特L值),并可用作聚乙烯的着色剂。 The results showed that: the ratio of carbon black products still little black (lower Hunter L value), and can be used polyethylene colorant.

实施例66在造粒机中制备炭黑产品该实施例介绍了本发明炭黑产品的制备。 Example 66 Preparation of a carbon black product in a pelletizer implementation of this embodiment, the present invention describes the preparation of carbon black products. 向销式造粒机中加入表面积为254m2/g、DBPA为188ml/100g的炭黑和21.2g磺胺酸。 To pin granulator added surface area of 254m2 / g, DBPA of 188ml / 100g of carbon black and 21.2g sulfanilic acid. 混合45秒钟后,加入220g水。 Mixed for 45 seconds, add 220g of water. 混合20秒钟后,加入13.2g浓硝酸。 After 20 seconds mixing, 13.2g of concentrated nitric acid was added. 混合另外20秒钟后,加入10.3g NaNO2在270g水中的溶液。 Mixed for an additional 20 seconds after the addition of 10.3g NaNO2 solution in 270g water. 混合2分钟后,在烘箱中125℃下干燥该生成的炭黑产品。 After mixing for 2 minutes, in an oven at 125 ℃ drying the resulting carbon black product.

实施例67炭黑产品在聚丙烯中的用途该实施例介绍在聚丙烯中使用本发明炭黑产品来赋予聚丙烯导电性。 Example 67 carbon black product in polypropylene This section describes the purpose of the embodiment of the present invention, the carbon black product in polypropylene to impart conductivity polypropylene. 把实施例66中的炭黑产品263.1g和聚丙烯881g的混合物加到在66℃下的布雷本登混炼机中,并混合5分钟。 Example 66 The mixture of carbon black product and polypropylene 881g 263.1g was added at 66 ℃ Brabender mixer and mixed for 5 minutes. 通过与另外的聚丙烯相混和,使该材料样品在一个两辊式轧墨机上下降到20%炭黑产品量。 With the addition of polypropylene and mixed so that the material sample in a two-roll mill ink machine up and down to 20% the amount of carbon black products. 该产品的电阻率为68欧姆-厘米,与用实施例66中用的未处理炭黑制的类似产品的64欧姆-厘米相比较。 This product has a resistivity of 68 ohm - cm, and similar products Example 66 prepared with untreated carbon black 64 ohm - cm compared.

实施例68-76炭黑产品的制备这些实施例介绍了可用来制备本发明炭黑产品的其他重氮化合物。 Example 68-76 Preparation of carbon black products These examples describes other diazonium compounds may be prepared by the present invention, the carbon black product. 该重氮化合物包括在芳香环上的一系列取代形式并具有各种吸电子或供电子取代基。 The diazo compound includes a series of substituents on the aromatic ring and with various forms of electron donating or electron-withdrawing substituents. 在每种情况下,由指定的芳基胺、NaNO2和浓HCl或HNO3制备冷的重氮盐溶液。 In each case, by the specified aryl amines, NaNO2 and concentrated HCl or HNO3 prepared cold diazonium salt solution. 把该重氮溶液加到炭黑在水中的悬浮液中和/或搅拌15-20分钟。 The diazonium solution was added to the carbon black suspension in water and / or stirred for 15 to 20 minutes. 过滤分离该生成的炭黑产品,用水洗涤,并用THF进行Soxhlet萃取过夜。 Was isolated by filtration of the resulting carbon black product was washed with water and subjected to Soxhlet extraction with THF overnight. 从下面所示的各个分析表明:与在适当的未处理炭黑中所含的量相比较,该反应的量增加。 From each analysis shown below show that: the amount in the appropriate untreated carbon black contained as compared to the increase in the amount of reaction. 该结果表明有相当大部分的有机基团连到该炭黑产品上。 The results show that there is a substantial portion of the organic group is attached to the carbon black product.

*CTAB表面积实施例77含有芳基和烷氧基的炭黑产品的制备该实施例介绍了含有芳基和烷氧基的炭黑产品的制备。 * Prepared containing aryl and alkoxy carbon black product of Example 77 CTAB surface area This Example illustrates the embodiment is prepared containing aryl and alkoxy carbon black product. 使用表面积为230m2/g、DBPA为70ml/100g的干燥碳黑样品。 A surface area of 230m2 / g, DBPA dry carbon black sample 70ml / 100g of. 把溴乙醇(30ml)加到3g炭黑和0.34g干燥六氟磷酸氯重氮苯的混合物中。 The bromoethanol (30ml) was added to a mixture of carbon black and 3g 0.34g dried diazonium hexafluorophosphate chloro benzene. 迅速释放大量气泡。 Rapid release of a large number of bubbles. 搅拌30分钟后,过滤该生成的炭黑产品,用THF进行Soxhlet萃取过夜并干燥。 After stirring for 30 minutes, the resulting carbon black product was filtered, subjected to Soxhlet extraction overnight with THF and dried. 该炭黑产品含有0.58%Cl和0.84%Br,与未处理炭黑产品含有0.02%Cl和<0.01%Br相比较。 The carbon black product contained 0.58% Cl and 0.84% Br, and untreated carbon black product contained 0.02% Cl and <0.01% Br compared. 因此,该炭黑产品具有0.16mmol/g相连的氯苯基和0.11mmol/g相连的溴乙氧基。 Therefore, the carbon black products having bromine 0.16mmol / g attached chlorophenyl and 0.11mmol / g connected ethoxy.

实施例78含有芳基和烷氧基的炭黑产品的制备该实施例介绍了含有芳基和烷氧基的炭黑产品的制备。 Preparation of carbon black products of Example 78 containing aryl and alkoxy groups This example describes the preparation of an aryl group and an alkoxy group containing a carbon black product. 使用表面积为230m2/g、DBPA为70ml/100g的干燥碳黑样品。 A surface area of 230m2 / g, DBPA dry carbon black sample 70ml / 100g of. 把氯乙醇(30ml)加到3g炭黑和0.32g干燥四氟硼酸溴重氮苯的混合物中。 The chlorine ethanol (30ml) was added to a mixture of carbon black and 0.32g 3g dried tetrafluoroborate benzenediazonium of bromine. 迅速释放大量气泡。 Rapid release of a large number of bubbles. 搅拌30分钟后,过滤该生成的炭黑产品,用THF进行Soxhlet萃取过夜并干燥。 After stirring for 30 minutes, the resulting carbon black product was filtered, subjected to Soxhlet extraction overnight with THF and dried. 该炭黑产品含有0.58%Cl和0.84%Br,与未处理炭黑产品含有0.02%Cl和<0.01%Br相比较。 The carbon black product contained 0.58% Cl and 0.84% Br, and untreated carbon black product contained 0.02% Cl and <0.01% Br compared. 因此,该炭黑产品具有0.16mmol/g相连的溴苯基和0.11mmol/g相连的氯乙氧基。 Therefore, the carbon black product has 0.16mmol / g attached bromophenyl and 0.11mmol / g attached chloroethoxy.

实施例79含有芳基和烷氧基的炭黑产品的制备该实施例介绍了含有芳基和烷氧基的炭黑产品的另外一种方法。 Preparation containing aryl and alkoxy carbon black product of Example 79 describes the implementation of this embodiment another method comprising aryl and alkoxy carbon black products. 使用表面积为230m2/g、DBPA为70ml/100g干燥炭黑样品。 A surface area of 230m2 / g, DBPA of 70ml / 100g carbon black sample was dried. 在冰浴中从0.69g溴苯胺、0.33gNaNO2、0.86g浓硝酸和约3ml水,制备硝酸4-溴重氮苯。 In an ice bath from 0.69g bromo aniline, 0.33gNaNO2,0.86g about 3ml of concentrated aqueous nitric acid, nitrate prepared 4-bromo-benzene diazonium. 把该重氮溶液加到10g炭黑产品,5g氯乙醇和85g在室温下搅拌的水的悬浮液中。 The diazonium solution was added to 10g of the carbon black products, 5g chloroethanol and stirred at room temperature 85g of aqueous suspension. 搅拌30分钟后,过滤取出该炭黑产品、用THF洗涤、在烘箱中约125℃下干燥。 After stirring for 30 minutes, remove the carbon black product was filtered, THF washed, dried in an oven at about 125 ℃. 已用THF进行过Soxhlet萃取过夜的样品含有1.08%溴和0.16%氯。 Samples have been carried out with THF overnight Soxhlet extraction contained 1.08% bromine and 0.16% chlorine. 对照炭黑样品的制备是:在5.6%氯乙醇/水溶液中搅拌同样的未处理炭黑,用THF洗涤、干燥并用THF萃取。 Control carbon black sample preparation are: stirring the same untreated carbon black at 5.6% chloroethanol / water solution, THF washed, dried and extracted with THF. 该对照样含有<0.02%溴和0.082%氯。 The control sample containing <0.02% 0.082% chlorine and bromine. 因此,该炭黑产品有0.13mmol/g相连的溴苯基和0.022mmol/g相连的氯乙氧基。 Therefore, the carbon black product has 0.13mmol / g attached bromophenyl and 0.022mmol / g attached chloroethoxy.

实施例80 Example 80

炭黑产品的制备该实施例继续介绍了本发明炭黑产品的制备。 Preparation of carbon black products according to this embodiment of the present invention is prepared to continue to introduce the carbon black product. 用40g水稀释浓HCl(16.2g)并加到9.30g 4-氨基苯二硫化物中。 Diluting concentrated HCl (16.2g) was added with 40g of water and 9.30g 4- aminophenyl disulfide. 在冰浴中搅拌该混合物。 In an ice bath and the mixture was stirred. 搅拌下加入6.21gNaNO2在30g水中的冷溶液,使该混合物保持在10℃以下。 6.21gNaNO2 cold solution was added under stirring in 30g water, and the mixture was kept below 10 ℃. 形成二氯化4-重氮苯基二硫化物。 4- diazonium formation phenyl disulfide dichloride. 把该混合物在搅拌下加到250g粒状炭黑(碘值120mg/g、DBPA为125ml/100g)在1.3L、10℃的水中。 The mixture was added with stirring 250g of granular carbon black (iodine number 120mg / g, DBPA of 125ml / 100g) in 1.3L, 10 ℃ of water. 释放大量气泡。 Release a lot of bubbles. 搅拌2.5小时后,过滤该产品,用乙醇洗涤,用另外的水洗涤,然后在125℃下干燥至恒重。 After stirring for 2.5 hours, the product was filtered, washed with ethanol, washed with additional water and then dried at 125 ℃ to constant weight. 用THF萃取过夜并干燥的炭黑产品样品含有1.75%硫,与未处理炭黑含有1.08%相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.75% sulfur, and untreated carbon black containing 1.08% compared to. 因此,该炭黑产品含有0.10mmol/g相连的二硫代二-4,1-亚苯基。 Therefore, the carbon black product containing 0.10mmol / g attached dithiobis 4,1-phenylene.

实施例81炭黑产品的制备该实施例介绍了本发明炭黑产品的制备。 Example 81 Preparation of carbon black product This example describes the preparation of carbon black products of the present invention. 用40g水稀释浓HCl(5.4g)并加到3.1g 4-氨基苯二硫化物中。 Diluting concentrated HCl (5.4g) was added with 40g of water and 3.1g 4- aminophenyl disulfide. 在冰浴中搅拌该混合物,并加入50g另外的冷水。 The mixture was stirred in an ice bath, and add 50g of additional cold water. 搅拌下加入2.07g NaNO2在30g水中的冷溶液,使该混合物保持在10℃以下。 2.07g NaNO2 was added with stirring a cold solution of 30g of water, the mixture was kept below 10 ℃. 形成二氯化4-重氮苯二硫化物。 4- benzenediazonium form disulfide dichloride. 把该混合物在搅拌下加到125g粒状炭黑(碘值120mg/g、DBPA为125ml/100g)在约800g、10℃-15℃的水中。 The mixture was added with stirring 125g of granular carbon black (iodine number 120mg / g, DBPA of 125ml / 100g) at about 800g, 10 ℃ -15 ℃ of water. 释放大量气泡。 Release a lot of bubbles. 搅拌2小时后,过滤该生成的炭黑产品,用乙醇洗涤,用另外的水洗涤,然后在125℃下干燥至恒重。 After stirring for 2 hours, the resulting carbon black product filtered, washed with ethanol, further washed with water, then dried to constant weight at 125 ℃. 用THF萃取过夜并干燥的炭黑产品样品含有1.56%硫,与未处理炭黑含有1.08%相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.56% sulfur, and untreated carbon black containing 1.08% compared to. 因此,该炭黑产品含有0.075mmol/g相连的二硫代二-4,1-亚苯基。 Therefore, the carbon black product containing 0.075mmol / g attached dithiobis 4,1-phenylene.

实施例82炭黑产品的制备该实施例继续介绍本发明炭黑产品的制备。 Example 82 Preparation of carbon black products according to this embodiment of the present invention is prepared to continue to introduce the carbon black product. 使用碘值为120mg/g、DBPA为125ml/100g的粒状炭黑。 Using an iodine value of 120mg / g, DBPA particulate carbon black 125ml / 100g of. 把丁基锂(50ml在己烷中的1.0M溶液)在氮气氛中加到200mL干DMSO(二甲基亚砜)中。 The butyl lithium (50ml 1.0M solution in hexane) was added in a nitrogen atmosphere 200mL dry DMSO (dimethylsulfoxide). 制备11.1g 4-氨基苯二硫化物在100mL干DMSO的溶液,并在氮气氛中在冰浴冷却下加入该溶液。 Preparation of 11.1g 4- aminophenyl disulfide in 100mL dry DMSO solution in a nitrogen atmosphere and the solution was added under ice-cooling. 显出黑紫色。 Showing dark purple. 在10分钟内,搅拌下加入S2Cl2(3.3ml)并继续冷却。 Within 10 minutes, is added with stirring S2Cl2 (3.3ml) and continue to cool. 加入1.7gNaOH在水中的溶液。 Join 1.7gNaOH solution in water. 加入更多的水,用450ml醚萃取该产品。 Add more water, the product was extracted with 450ml ether. 真空除去该醚,该残余物溶解在CH2Cl2、用水洗涤、真空干燥并浓缩,得到油状的4-氨基苯基四硫化物。 The ether was removed in vacuo, the residue was dissolved in CH2Cl2, washed with water, dried and concentrated in vacuo to give an oil of 4-aminophenyl tetrasulfide.

在冰浴中把4-氨基苯基四硫化物(5.85g)和150g水一起搅拌。 In an ice bath to 4-aminophenyl tetrasulfide (5.85g) and 150g water and stir together. 加入8.1g浓HCl在50g水中的冷溶液,接着逐渐加入3.2gNaNO2在40g水中的溶液,形成二氯化4-重氮苯四硫化物。 8.1g was added a solution of 50g concentrated HCl in cold water, and then the solution was gradually added in 40g water 3.2gNaNO2 formed diazonium benzene dichloride 4- tetrasulfide. 搅拌后,把该生成的悬浮液加到搅拌中的125g粒状炭黑在约800g水中的浆料中。 After stirring, to the resulting stirred suspension was added to 125g of granular carbon black in about 800g water slurry. 释放大量气泡。 Release a lot of bubbles. 搅拌2.5小时后,过滤该生成的炭黑产品,用乙醇洗涤、用水洗涤并在140℃下干燥。 After stirring for 2.5 hours, the resulting carbon black product was filtered, washed with ethanol, washed with water and dried at 140 ℃. 已用THF萃取过夜并已干燥的炭黑产品样品含有1.97%硫,与未处理炭黑含有1.08%硫相比较。 It has been extracted with THF overnight and dried sample containing 1.97% carbon black products of sulfur, and the untreated carbon black containing 1.08% sulfur compared. 因此,该炭黑产品具有0.07mmol/g相连的四硫代二-4,1-亚苯基。 Therefore, the carbon black products having a tetrathiocarbonate 0.07mmol / g 4,1-phenylene bis connected.

实施例83炭黑产品的制备该实施例介绍了本发明炭黑产品的制备。 Example 83 Preparation of carbon black product This example describes the preparation of carbon black products of the present invention. 使用碘值120mg/g、DBPA为125ml/100g的炭黑。 Iodine value using 120mg / g, DBPA of the carbon black 125ml / 100g of. 把2.65g浓HCl和30g水的冷溶液加到2.85g4-氨基苯苯二硫化物在50g正在冰浴中搅拌的水中。 The cold solution of 2.65g of concentrated HCl and 30g of water was added to 2.85g4- amino disulfide Benzene is stirred in an ice bath water 50g. 在10分钟时间内,加入1.04gNaNO2在30g水中的冷溶液。 Within 10 minutes, the cold solution was added 1.04gNaNO2 30g water. 形成氯化4-重氮苯苯基二硫化物。 The formation of chlorinated 4- benzenediazonium disulfide. 把该重氮悬浮液加到122g炭黑在约800g在15℃搅拌的水中的悬浮液中。 The diazo suspension was added to 122g of carbon black at about 800g of water at 15 ℃ stirred suspension. 释放大量气泡。 Release a lot of bubbles. 搅拌约二小时后,过滤该炭黑产品、用异丙醇洗涤、用水洗涤、在烘箱中约125℃下干燥。 After stirring for about two hours, the carbon black product was filtered, washed with isopropanol, washed with water and dried in an oven at about 125 ℃. 已用THF进行了Soxhlet萃取过夜并干燥的炭黑产品样品的硫含量为1.32%,与未处理炭黑的1.08%相比较。 Sulfur content has been subjected to Soxhlet extraction with THF overnight and dried carbon black product samples was 1.32%, compared to 1.08% for the untreated carbon black. 因此,该炭黑产品具有0.038mmol/g相连的苯基二硫亚苯基。 Therefore, the carbon black products having 0.038mmol / g of phenyl disulfide linked phenylene.

实施例84炭黑产品的制备该实施例进一步介绍本发明炭黑产品的制备。 Example 84 Preparation of carbon black product This example further describes the preparation of carbon black products of the present invention. 把二氧化氮(4.1g)鼓泡通入在冰浴中冷却的40g水中。 The nitrogen dioxide (4.1g) was bubbled through cooled in an ice bath 40g water. 把该生成的溶液缓慢加入冷的(10℃)搅拌中的4.65g 4-氨基苯二硫化物在100g水中的悬浮液中。 The resultant solution was slowly added to a cold (10 ℃) stirred solution of 4.65g 4- aminophenyl disulfide in 100g of water suspension. 把该生成二硝酸4-重氮苯基二硫化物加入125g炭黑(碘值120mg/g、DBPA为125ml/100g)在800g冷(12-14℃)水中的搅拌的冷悬浮液中。 The resultant diazonium 4- phenyl disulfide dinitrate was added 125g of carbon black (iodine number 120mg / g, DBPA of 125ml / 100g) in 800g cold (12-14 ℃) in water was stirred cold suspension. 该反应混合物搅拌3天,并在该步骤中,让其加热到室温。 The reaction mixture was stirred for three days, and in this step, allowed to warm to room temperature. 过滤回收并干燥该生成的炭黑产品。 Recovered by filtration and drying the produced carbon black products. 用THF萃取过夜的炭黑产品样品具有1.81%硫,与未处理炭黑产品的1.07%硫相比较。 Carbon black was extracted with THF overnight with 1.81% sulfur product samples, compared to 1.07% for the untreated carbon black product sulfur. 因此,该炭黑产品具有0.12mmol/g相连的二硫二-4,1-亚苯基。 Therefore, the carbon black products having disulfide 0.12mmol / g 4,1-phenylene bis connected.

实施例85炭黑产品的制备该实施例继续介绍本发明炭黑产品的制备。 Preparation Example 85 carbon black products according to this embodiment of the present invention is prepared to continue to introduce the carbon black product. 按照实施例80的程序,除了使用碘值为90mg/g、DBPA为114ml/100g的炭黑外,以及除了使用另外50ml水来形成二氢氯化氨基苯基二硫化物悬浮液外。 According to the procedure of Example 80, except that an iodine value of 90mg / g, DBPA of the carbon black 114ml / 100g outside, and in addition to the use of water to form additional 50ml aminophenyl disulfide dihydrochloride suspension outside. 已用THF进行过萃取过夜并干燥的该生成的炭黑产品样品含有2.12%硫,与未处理炭黑含有1.45%硫相比较。 It has been extracted with THF overnight and dried and the resultant carbon black product samples containing 2.12% sulfur, and untreated carbon black containing 1.45% sulfur compared. 因此,该炭黑产品有0.10mmol/g相连的二硫二-4,1-亚苯基。 Therefore, the carbon black product has 0.10mmol / g connected disulphide 4,1-phenylene.

实施例86炭黑产品的制备该实施例介绍本发明炭黑产品的制备。 Preparation of carbon black products of Example 86 This example describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of. 通过把3.59g NaNO2在40g水中的冷溶液加到6.6g 4-氨基-2-氯苯基二硫化物、9.12g浓HCl和约150g在冰浴中搅拌的水中的悬浮液中,来制备二氯化4-重氮-2-氯苯基二硫化物。 By cold solution of 3.59g NaNO2 in 40g of water was added 6.6g 4- amino-2-chlorophenyl disulfide, 9.12g and about 150g of concentrated HCl was stirred in an ice water bath, a suspension, prepared dichloro of 4- diazo-2-chlorophenyl disulfide. 搅拌5分钟后,接着把该重氮溶液加到140g炭黑在1升10-14℃水中的搅拌过的悬浮液中。 After stirring for 5 minutes, and then the diazonium solution was added to 140g of carbon black in 1 liter of water of 10-14 ℃ stirred suspension. 搅拌两小时后,过滤生成的炭黑产品,用乙醇洗涤,用水洗涤,然后在烘箱中125℃下干燥。 After stirring for two hours, the resulting carbon black product was filtered, washed with ethanol, washed with water, and then dried in an oven at 125 ℃. 用THF进行过Soxhlet萃取过夜并干燥的炭黑产品样品的硫含量为1.60%,与未处理炭黑含有1.08%相比较。 Sulfur content Soxhlet extraction with THF been dry overnight and the carbon black product samples was 1.60%, and the untreated carbon black containing 1.08% compared to. 因此,该炭黑产品有0.081mmol/g相连的二硫二-4,1-(3-氯亚苯基)基。 Therefore, the carbon black product has 0.081mmol / g disulfide linked 4,1-bis (3-chloro-phenylene) group.

实施例87用现场生成的重氮盐制备炭黑产品该实施例介绍了用现场生成的重氮盐制备本发明炭黑产品。 Example 87 with a diazonium salt generated in situ preparation of a carbon black product This example describes the use of a diazonium salt generated in situ preparation of a carbon black product of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of. 把4-氨基苯基二硫化物(8.38g)溶解在14.65g浓HC1和约150g水的溶液中,并加入到225g炭黑在约1.4L水中搅拌过的浆料中。 The 4-aminophenyl disulfide (8.38g) was dissolved in 14.65g of concentrated HC1 and about 150g of water solution and added to 225g of carbon black at about 1.4L of water stirred slurry. 加入5.28gNaNO2在约50g水中的溶液,现场形成4-重氮苯基二硫化物,该二硫化物与该炭黑反应。 5.28gNaNO2 about 50g of water was added a solution of 4- diazo diphenyl disulfide formation site, the disulfide is reacted with the carbon black. 搅拌两小时后,过滤取出该生成的炭黑,用乙醇洗涤,用水洗涤,并在约125℃下干燥。 After stirring for two hours, the resulting carbon black is removed by filtration, washed with ethanol, washed with water, and dried at about 125 ℃. 已用THF进行过Soxhlet萃取过夜并干燥的炭黑产品样品含有1.89%硫,与未处理炭黑含有1.08%硫相比较。 It has been Soxhlet extraction with THF overnight and dried sample containing 1.89% carbon black products of sulfur, and the untreated carbon black containing 1.08% sulfur compared. 因此,该炭黑产品具有0.13mmol/g相连的二硫二-4,1-亚苯基。 Therefore, the carbon black products having disulfide 0.13mmol / g 4,1-phenylene bis connected.

实施例88炭黑产品的制备按照实施例80的方法,并用8.38g 4-氨基苯基二硫化物在约100g水中的悬浮液、13.65g浓HCl在40g水中的溶液、5.04gNaNO2在30g水中的溶液和225g相同的炭黑在1.4升水中的浆料,来制备连有二硫二-4,1-亚苯基的炭黑产品。 Example 88 Preparation of carbon black products according to the embodiment of the method of Example 80, and treated with 8.38g 4- aminophenyl disulfide in about 100g of water suspension, 13.65g 40g concentrated HCl in water, 5.04gNaNO2 in 30g water solution and the same carbon black slurry 225g 1.4 liters of water to prepare even have a carbon black product disulphide 4,1-phenylene. 当加入该重氮溶液时,在10-14℃下搅拌该炭黑浆料。 When added to the diazonium solution was added and the black slurry at 10-14 ℃.

实施例89和90对比炭黑产品在这些对比例中,将实施例80和85用的炭黑用水、乙醇和水洗涤,并接着干燥,分别得到实施例88和89的对比炭黑产品。 Example 89 and 90 Comparative carbon black products in these comparative examples, carbon black water, and washed with water Example 80 and 85 will be implemented with ethanol, and then dried, were obtained in Example 88 and 89 comparison carbon black products.

实施例91-99使用不同的炭黑来制备水可分散的炭黑产品该实施例介绍在制备本发明炭黑产品中使用各种炭黑。 Example 91-99 to prepare a water dispersible carbon black product This example describes the preparation of various carbon black in a carbon black product of the present invention to use different carbon black. 该实施例也表明该炭黑产品比相应的未处理炭黑更易分散在水中。 This example also shows that the carbon black products more than the corresponding untreated carbon black dispersed in water. 把磺胺酸溶解在200g热水中。 The sulfanilic acid dissolved in hot water 200g. 加入该炭黑产品(30g)并让该混合物冷却到25-30℃。 Was added to the carbon black product (30g) and allow the mixture to cool to 25-30 ℃. 加入浓HCl(基于所用的磺胺酸为2.15当量),然后加入NaNO2在水中的9.65M溶液(基于所用的磺胺酸为1.2当量),现场形成氢氧化4-磺基重氮苯,该重氮物与炭黑反应。 Concentrated HCl (based on the use of sulfanilic acid was 2.15 equiv.) Was added NaNO2 9.65M solution in water (based on the use of sulfa acid is 1.2 equivalents), formed in situ hydroxide 4- sulfo benzenediazonium the diazonium The reaction with the carbon black. 搅拌30分钟后,在烘箱中100℃下干燥该生成的分散液,得到生成的炭黑产品。 After stirring for 30 minutes, the dispersion in an oven at 100 ℃ The resultant was dried to give the resulting carbon black product.

*通过2(0微米过滤器过滤**CTAB表面积实施例100炭黑产品的制备和其在黑纸(black paper)中的使用该实施例介绍了本发明炭黑产品的制备和该产品在黑纸制备中的应用。把表面积为80m2/g、DBPA为85ml/100g的炭黑(300g)加到有18.2g磺胺酸的销式造粒机中。短暂混合后,相继加入150g水、11.2g浓硝酸、30g水和8.78gNaNO2在35g水中的溶液,每次加料后混合15秒钟。现场生成氢氧化4-磺基重氮苯内盐,且它与该炭黑反应。该生成的炭黑产品在烘箱中125℃下干燥。在实验均化器中把该炭黑产品分散在水中30秒钟,来制得该炭黑产品的分散液。 * By 2 (0 micron filter ** CTAB surface preparation Example 100 carbon black products and their use in black paper (black paper) of the embodiment of the present invention describes the preparation of carbon black product and the product in the dark Application of the paper preparation. The surface area of 80m2 / g, DBPA of the carbon black 85ml / 100g of (300g) was added to 18.2g sulfanilic acid have pin-type granulator. After briefly mixing, 150g of water were added successively, 11.2g concentrated nitric acid, 30g of water and 35g 8.78gNaNO2 solution in water, mixed for 15 seconds after each addition. field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, and it reacts with the carbon black, carbon black and the resultant Product 125 ℃ dried in an oven at. In the experiments in the homogenizer the carbon black product dispersed in water for 30 seconds, to prepare a dispersion of the carbon black product.

在球磨机中在7g木素磺酸盐(lignosulfonate)分散剂,5ml浓NH4OH和770g水的溶液和研磨介质中,研磨200g未反应炭黑4小时,此时赫格曼细度计(Hegman gauge)的读数为7,制得对比分散液。 In a ball mill at 7g lignin sulfonate (lignosulfonate) dispersant, 5ml concentrated NH4OH solution and 770g of water and grinding media, grinding 200g unreacted carbon black 4 hours, then He Geman grind (Hegman gauge) a reading of 7 to prepare comparative dispersion.

把Penobscott漂白的硬木牛皮纸浆(160g)和St.Felician漂白的软木牛皮纸浆(240g)分散在Cowles溶解器内的水中。 The Penobscott bleached hardwood kraft pulp (160g) and St.Felician bleached softwood kraft pulp (240g) were dispersed in water within Cowles dissolver. 把该原料溶液转移到TAPPI((美国)制浆造纸技术协会)标准实验室打浆器中并稀释成体积为23L。 The raw material solution was transferred to TAPPI ((USA) Pulp and Paper Technical Association) standard laboratory beating vessel and diluted to a volume of 23L. 该原料溶液在该打浆器中循环5分钟,然后放置在负荷下并打浆5分钟,到已校正的加拿大标准游离度为355ml。 The feed solution is circulated through the beating device for 5 minutes and then placed under load and beaten five minutes, to a corrected Canadian standard freeness of 355ml.

把足以制造三张2.75g手抄纸的纸浆稀释成3L,并加入适量的炭黑分散液。 The diluted enough to make three 2.75g pulp handsheet into 3L, and add the appropriate amount of carbon black dispersion. 每一个炭黑加入量制备一个悬浮液。 Each addition of carbon black-a suspension. 每一个悬浮液分成三部分。 Each suspension was divided into three parts. 第一部分按原样使用。 The first part was used as is. 分别以每绝干吨80磅和60磅的比率,向第二部分中加入松香和明矾。 Respectively 80 pounds per bone dry tonne ratio and 60 pounds, the second part of rosin and alum. 分别以每绝干吨4磅和3磅的比率,向第三部分加入HERCON79(AKD)胶料和BL 535助留剂。 Respectively, 4 pounds per bone dry tonne ratio and 3 pounds, was added to the third part HERCON79 (AKD) sizing and BL 535 retention aid. 由每个样品制成一张8″8″Noble&amp;Wood手抄纸。 Each sample was made by the one 8 " 8" Noble & amp; Wood handsheet. 用45/0几何形状来评价该生成的手抄纸的TAPPI亮度。 With a 45 / 0 geometry was evaluated the generation of the TAPPI brightness of handsheets.

HERCON是Wilmington DE的Hercules Inc.生产和销售的胶料的注册商标。 HERCON is a registered trademark of Hercules Inc. production and sale of rubber compounds of Wilmington DE. BL 535购自Memphis TN的Buckman Laboratories Inc.。 BL 535 was purchased from Memphis TN of Buckman Laboratories Inc .. 下表示出用该炭黑产品分散液和对照分散液制成的手抄纸的亮度。 The following table shows the brightness with the carbon black product dispersion and the control dispersion was made handsheets. 这些数据表明该炭黑产品可用来使纸张着色。 These data indicate that the carbon black products can be used to make colored paper. 这些数据也表明:当用酸性松香胶料和明矾助留剂时,与未反应炭黑相比较,低加入量时更有效和更有利地保留该炭黑产品。 These data also show that: When acidic alum rosin sizing and retention aid, compared with the unreacted carbon black, more effective and more beneficial to keep the low amount of carbon black product. 这些数据还表明:当该纸张用碱性AKD胶料和BL535助留剂制造时,与未反应炭黑产品相比,低加入量时更有效和有利地保留该炭黑产品。 These data also showed that: when the paper is manufactured with an alkaline AKD retention agent compounds and BL535 aid, compared with the unreacted carbon black products more effectively and advantageously retain the carbon black products at low dosage.

实施例101在制备水性油墨中使用炭黑产品该实施例介绍了在水性油黑配方中使用本发明炭黑产品的优点。 Example 101 water-based ink used in the preparation of a carbon black product This example describes the advantages of using the carbon black product of the present invention in an aqueous black oil formulation. 按如下方法制备油墨组合物A:把3.13份实施例13中的炭黑产品加到一种连结料中,该连结料的制备如下:混合2.92份JONCRYL 61LV树脂、0.21份异丙醇、0.31份ARROWFLEX脱泡剂、7.29份JONCRYL 89树脂和6.98份水;并在涂料振动器中振动组合物A10分钟。 Prepared as follows ink composition A: 3.13 parts of the carbon black in Example 13 was added to a Quick product compound, the binders prepared as follows: mixing 2.92 parts JONCRYL 61LV resin, 0.21 parts isopropanol, 0.31 parts of ARROWFLEX defoamers, 7.29 parts JONCRYL 89 resin and 6.98 parts of water; and vibration in a paint shaker composition A10 minutes. 下表示出了635目残余物的含量。 The table below shows the 635 mesh residue content.

JONCRYL是由WI Racine的SC Johnson Polymer制造和销售的树脂的注册商标。 JONCRYL is a registered trademark manufactured and sold by WI Racine's SC Johnson Polymer resin. ARROWFLEX是由NY New York的Witco制造和销售的脱泡剂的注册商标。 ARROWFLEX is a registered trademark manufactured and sold by Witco NY New York of the degassing agent.

如下制备油墨组合物B:研磨120份实施例13中所用的炭黑产品、112份JONCRYL 61LV树脂、8份异丙醇、4份ARROWFLEX脱泡剂、156份水和400g研磨介质的混合物。 The ink composition was prepared as follows B: 120 parts by polishing as used in Example 13 carbon black product, 112 parts of JONCRYL 61LV resin mixture, 8 parts of isopropanol, 4 parts of ARROWFLEX defoamer, 156 parts of water and 400g of grinding media. 为了检查其研磨程度,定期取出样品到组合物C中,该组合物C含有15.0份炭黑产品、14.0份JONCRYL61LV树脂、1.0份异丙醇、1.7份ARROWFLEX DEFOAMER、35.1份Joncryl 89和33.4份水。 In order to check the degree of grinding, the sample was removed periodically to composition C, the composition C comprising 15.0 parts carbon black product, 14.0 parts of JONCRYL61LV resin, 1.0 parts isopropanol, 1.7 parts ARROWFLEX DEFOAMER, 35.1 parts Joncryl 89 and 33.4 parts of water .

如下制备油墨组合物D:研磨120份实验例13中所用的未处理炭黑、112份JONCRYL 61LV树脂、8份异丙醇、4份ARROWFLEX脱泡剂、156份水和400g研磨介质的混合物。 The ink composition was prepared as follows D: mixture of 120 parts of the untreated carbon black grinding experiment used in Example 13, 112 parts of JONCRYL 61LV resin, 8 parts of isopropanol, 4 parts of ARROWFLEX defoamer, 156 parts of water and 400g of grinding media. 为了检查其研磨程度,定期取出样品到组合物E中,该组合物E含有15.0份炭黑产品、14.0份JONCRYL61LV树脂、1.0份异丙醇、1.7份ARROWFLEX脱泡剂、35.1份JONCRYL89树脂和33.4份水。 In order to check the degree of grinding, the sample was removed periodically to composition E, the composition E containing 15.0 parts carbon black product, 14.0 parts of JONCRYL61LV resin, 1.0 parts isopropanol, 1.7 parts ARROWFLEX defoamer, 35.1 parts resin and 33.4 JONCRYL89 parts of water.

在下表中给出了作为研磨时间的函数的油墨组合物A、C和E中的残余物,并清楚显示:在这些水性油墨中,本发明的炭黑产品比相应的未处理炭黑更易分散。 In the table below as a function of milling time ink composition A, C and E in the residue, and clearly shows that: In these water-based inks, the carbon black product of the present invention is easier to disperse than the corresponding untreated carbon black .

</tables>实施例102在水性涂料的制备中使用炭黑产品本实施例表明:本发明炭黑产品可用于水性涂料的制备。 </ Tables> Example 102 carbon black product in the preparation of the aqueous coating of the present examples show: a carbon black product of the present invention can be prepared for waterborne coatings. 实施例9的炭黑产品(10g)通过搅拌10分钟后分散在90g水中。 Carbon black products of Example 9 (10g) dispersed by stirring for 10 minutes in 90g water. 如下制备涂料组合物A:把4.3g这种分散液搅拌入这样一种混合物,该混合物含有7.53gCARGILL17-7240丙烯酸树脂、0.80g二甲基乙醇胺(DMEA)、19.57g水、0.37gSURFYNOL CT136表面活性剂、1.32gCARGIL 23-2347三聚氰胺树脂、0.53g乙二醇单丁基醚和0.075g BYK-306表面活性剂。 The coating composition was prepared as follows A: 4.3g of the dispersion was stirred into this in such a mixture, the mixture comprising 7.53gCARGILL17-7240 acrylic resin, 0.80g dimethylethanolamine (DMEA), 19.57g water, 0.37gSURFYNOL CT136 surfactant agents, 1.32gCARGIL 23-2347 melamine resin, 0.53g glycol mono-butyl ether and 0.075g BYK-306 surfactant. CARGIL17-7240丙烯酸树脂和CARGILL23-2347三聚氰胺树脂可购自MN,Minneapolis的Cargill Inc.。 CARGIL17-7240 CARGILL23-2347 acrylic resins and melamine resins available from MN, Minneapolis of Cargill Inc .. SURFYNOL CT136是PA Allentown的Air Productsand Chemicals,Inc.生产和销售的表面活性剂的注册商标。 SURFYNOL CT136 is a registered trademark of the production and marketing of surfactants PA Allentown's Air Productsand Chemicals, Inc.. BYK-306是Wallingford的BYK-Chemie USA生产和销售的表面活性剂的注册商标。 BYK-306 is a registered trademark of surfactant BYK-Chemie USA Wallingford's production and sales.

如下制备研磨基料:在一种混合物中研磨氧化炭黑产品(15g)直到它的平均体积粒径为0.18微米,该炭黑产品的表面积为560m2/g、DBPA为80ml/100g、挥发物含量为9%,该混合物含有74.6g CARGILL 17-7240丙烯酸树脂、9.53g DMEA、236.5g水和16.35g CT-136表面活性剂。 Millbase was prepared as follows: A mixture of the product triturated oxidized carbon black (15g) until its mean volume particle size of 0.18 microns, a surface area of the carbon black products of 560m2 / g, DBPA of 80ml / 100g, volatile matter content 9%, the mixture contains 74.6g CARGILL 17-7240 acrylic resin, 9.53g DMEA, 236.5g of water and 16.35g CT-136 surfactant. 如下制备对比涂料组合物:混合24.4g这种研磨基料和17.5lg CARGILL 17-7240丙烯酸树脂、17.4g DMEA、50.56g水、3.97g CARGILL23-2347三聚氰胺树脂、1.59g乙二醇单丁基醚和0.23g BYK-306表面活性剂的混合物。 Comparative coating compositions were prepared as follows: mixing 24.4g This millbase and 17.5lg CARGILL 17-7240 acrylic resin, 17.4g DMEA, 50.56g of water, 3.97g CARGILL23-2347 melamine resin, 1.59g ethylene glycol monobutyl ether and 0.23g BYK-306 surfactant mixture. 涂有组合物A和B的光亮Lenetta纸在350F下干燥10分钟。 Coated with compositions A and B was dried at light Lenetta paper 350 F 10 minutes. 涂透明涂层,并再次干燥这些样品。 Clear coating, and the samples were dried again. 涂有组合物A的纸的亨特L、a、b值分别为1.0、0.01和0.03,与涂有对比组合物B的纸的上述各值分别为1.1、0.01和-0.06相比较。 A paper coated with the composition of the Hunter L, a, b values were 1.0,0.01 and 0.03, and coated with a comparative composition B of the respective values of the paper and -0.06, respectively, compared 1.1,0.01.

实施例103炭黑产品的制备和其在水性涂料中的应用该实施例介绍本发明炭黑产品的制备和这种炭黑产品在水性涂料中的应用。 Preparation and application of carbon black product of Example 103 in the water-based paint in the implementation of the embodiment of the present invention describes the preparation of carbon black product and such carbon black products in waterborne coatings applications. 把CTAB表面积为350m2/g、DBPA为120ml/100g的炭黑加入到搅拌过的42.4g磺胺酸在2800g水中的溶液。 The CTAB surface area of 350m2 / g, DBPA of 120ml / 100g carbon black was added to a stirred solution of 42.4g sulfanilic acid in 2800g of water. 二氧化氮(25.5g)溶解在100g冷水中,并加到该炭黑产品悬浮液中。 Nitrogen dioxide (25.5g) was dissolved in 100g cold water, and added to the carbon black product suspension. 释放大量气泡。 Release a lot of bubbles. 现场生成氢氧化4-磺基重氮苯内盐,该内盐与该炭黑反应。 Field of hydrogen and oxygen within the 4-sulfophthalic benzenediazonium salt, the inner salt reacts with the carbon black. 搅拌5小时后,向该炭黑分散液中直接加入另外5g NO2。 After stirring for 5 hours, directly to the carbon black dispersion was added additional 5g NO2. 把该分散液再搅拌15分钟,放置过夜。 To the dispersion was stirred for 15 minutes and allowed to stand overnight. 在烘箱中135℃下干燥该分散液来回收该生成的炭黑产品。 At 135 ℃ in the dispersion was dried in an oven to recover the resulting carbon black product.

在90g水中搅拌10g该炭黑产品,来制备这种炭黑产品的分散液。 The carbon black product was stirred in 10g 90g water to prepare a dispersion of this carbon black product. 通过把4.3g这种分散液搅拌入下面这种混合物中,来制备涂料组合物C,该混合物含有7.53gCARGILL 17-7240丙烯酸树脂、0.80g DMEA、19.57g水、0.37g SURFYNOL CT136表面活性剂、1.32g CARGILL 23-2347三聚氰胺树脂、0.53g乙二醇单丁基醚和0.075g BYK-306表面活性剂。 By this dispersion 4.3g stirred into this mixture below to prepare a coating composition C, the mixture contains 7.53gCARGILL 17-7240 acrylic resin, 0.80g DMEA, 19.57g of water, 0.37g SURFYNOL CT136 surfactant, 1.32g CARGILL 23-2347 melamine resin, 0.53g ethylene glycol mono-butyl ether and 0.075g BYK-306 surfactant.

如下制备研磨基料:在一种混合物中研磨(在一超微磨碎机中)研磨表面积为560m2/g、DBPA为91ml/100g、挥发物含量为9.5%的氧化炭黑产品(15g)24小时,该混合物含有74.6g CARGILL 17-7240丙烯酸树脂、9.53gDMEA、236.5g水和16.35g SURFYNOL CT-136表面活性剂。 Millbase was prepared as follows: In a mixture of milled (in an attritor) polishing a surface area of 560m2 / g, DBPA of 91ml / 100g, volatile matter content of 9.5% of the oxidized carbon black product (15g) 24 h, the mixture contains 74.6g CARGILL 17-7240 acrylic resin, 9.53gDMEA, 236.5g of water and 16.35g SURFYNOL CT-136 surfactant. 如下制备对比涂料组合物D:混合24.4g这种研磨基料和17.51g CARGILL 17-7240丙烯酸树脂、1.74g DMEA、50.56g水、3.97g CARGILL 23-2347三聚氰胺树脂、1.59g乙二醇单丁基醚和0.23g BYK-306表面活性剂。 Preparation of comparative coating composition as follows D: 24.4g This mill base mix and 17.51g CARGILL 17-7240 acrylic resin, 1.74g DMEA, 50.56g water, 3.97g CARGILL 23-2347 melamine resin, 1.59g of ethylene glycol monobutyl ether and 0.23g BYK-306 surfactant.

涂有组合物A和B的光亮Lenetta纸在350F下干燥10分钟。 Coated with compositions A and B was dried at light Lenetta paper 350 F 10 minutes. 涂布透明涂料,再次干燥这些样品。 Applying a clear coating, drying these samples again. 涂有组合物C的纸亨特L、a、b值分别为1.0、0.01和0.03,与涂有对比组合物D的纸的各值分别为1.1、0.01和-0.06相比较。 Coated with the composition C of paper Hunter L, a, b values were 1.0,0.01 and 0.03, and coated with the respective values of the comparative composition D and -0.06 1.1,0.01 paper for each phase comparison.

实施例104-108在橡胶配方中使用炭黑产品该实施例介绍在橡胶配方中使用实施例80-84和对比例89中的炭黑产品。 Example 104-108 carbon black products in rubber formulations This example describes the use in rubber formulations 80-84 and Comparative Example 89 in the carbon black products. 该聚合物在布雷本登混炼机中100℃下研磨1分钟。 100 ℃ under grinding the polymer in a Brabender mixer for 1 minute. 加入ZnO和该炭黑产品的混合物并混合另外2分钟。 ZnO added to the mixture and the carbon black product and mixed for an additional 2 minutes. 加入硬脂酸和FLEXZONE 7P抗降解剂并再混合2分钟。 Stearic acid and FLEXZONE 7P antidegradants and mix for 2 minutes. 把该样品卸料冷却,并在80℃混合1分钟,加入硫化剂,并继续混合另外1分钟。 The discharge of the sample was cooled, and mixed for 1 minute at 80 ℃, vulcanizing agent was added, and mixing was continued for another 1 minute. 把该样品通过一个两辊轧墨机三次。 The sample is put through a two-roll ink machine three times. 下表给出了每个例子中的配方和性能数据。 The following table gives examples of each recipe and performance data. NS114是化学改性的锡偶合溶液SBR,可购自Japan的Nippon Zeon。 NS114 is a tin coupled solution SBR chemically modified, available from Japan's Nippon Zeon. FLEXZONE是可从CT,Naugatuck的UniroyalChemical购得的抗降解剂的注册商标。 FLEXZONE is a registered trademark of antidegradants available from CT, Naugatuck's UniroyalChemical.

*CBs=环己基苯并噻唑亚磺酰胺**MBT=巯基苯并噻唑 * CBs = cyclohexyl benzothiazole sulfenamide ** MBT = mercaptobenzothiazole thiazole

<p>这些数据表明:本发明炭黑可用于橡胶配方中。 <P> These data show that: the present invention can be used in black rubber formulations. 这些数据还表明:当Tanδ显著减小时,模量、结合橡胶和抗磨损性显著增加。 These data also show that: When Tanδ significantly reduced, modulus, bound rubber and significant increase in anti-wear properties. 该效果的程度取决于该处理量以及连到该炭黑产品上的具体基团。 The extent of the effect depends on the amount of processing and the carbon black product to specific groups.

实施例109-112炭黑产品在橡胶配方中的应用该实施例介绍在几种不同的橡胶配方中使用本发明炭黑产品。 Example 109-112 carbon black products in rubber formulations applied to the embodiment of the present invention describes the use of carbon black products in several different rubber formulations. 从实施例85的炭黑产品和实施例90的对比炭黑产品中,根据实施例104-108所述的方法,使用下面的配方,制备橡胶混合物。 Carbon black product from Example 85 and Example 90 Comparative carbon black products in accordance with the procedure described in Example 104-108, using the following formulation was prepared rubber mixture. DURADENE 715是SBR溶液。 DURADENE 715 is the solution SBR. DURADENE是可购自Akron OH的Firestone的SBR产品的注册商标。 DURADENE is a registered trademark of commercially available from Akron OH Firestone of SBR products.

</tables>下表的性能数据表明:本发明炭黑产品可用于几种不同橡胶配方。 Performance data </ tables> The following table shows that: a carbon black product of the present invention can be used in several different rubber formulations.

100%模量Mpa300%模量Mpa拉伸强度Mpa伸长%肖氏硬度A结合橡胶%Tanδ0℃Tanδ70℃磨耗机指数14%滑移磨耗机指数21%滑移实施例1094.1219.321.93386029.80.2410.15584117比较例3.7017.323.03936228.00.2800.182100100实施例1104.79-14.42336332.40.4770.14681175比较例4.10-16.32826128.60.5440.173100100实施例1113.3215.124.44565539.10.2210.14298135比较例3.4817.127.34685743.60.2400.138100100实施例1123.7715.719.03585833.30.2960.156100176比较例3.3915.423.34415835.10.3350.175100100</table>实施例113处理的炭黑产品在橡胶配方中的应用该实施例介绍了在橡胶配方中使用本发明中处理过的炭黑产品。 100% modulus Mpa300% Modulus Mpa Elongation% Tensile strength Mpa Shore hardness A combination of rubber% Tanδ0 ℃ Tanδ70 ℃ wear machine index 14% 21% slip sliding abrasion machine index Example 1094.1219.321.93386029.80.2410.15584117 Comparative Example 3.7017.323.03936228.00.2800.182100100 1104.79-14.42336332.40.4770.14681175 Comparative Example Example Example 1113.3215.124.44565539.10.2210.14298135 4.10-16.32826128.60.5440.173100100 Comparative Example Example 1123.7715.719.03585833 3.4817.127.34685743.60.2400.138100100 carbon black products .30.2960.156100176 Comparative Example 3.3915.423.34415835.10.3350.175100100 </ table> 113 processing example embodiment of the application in rubber formulations This example describes the use in rubber formulations of the present invention, the treated carbon black products . 从实施例86的处理过的炭黑和实施例89的对比炭黑、根据实施例104-108所述的方法,来制备橡胶混合物。 Treated carbon blacks from Examples 86 through Example 89 and Comparative carbon black, according to the procedure described in Example 104-108, to prepare a rubber mixture. 其配方和性能数据列于下表。 The formulation and performance data are shown in the following table. 这些结果表明:该处理过的炭黑可用于该橡胶配方。 These results indicate that: the treated carbon black may be used in the rubber formulations. NS116是化学改性的锡偶合SBR溶液,并可购自日本的Nippon Zeon。 NS116 is chemically modified tin coupled solution SBR and can be purchased from Japan's Nippon Zeon.

实施例113比较例NS 116100100CB产品实施例8650对照CB实施例8950ZnO33硬脂酸22FLEXZONE 7P产品11CBS1.251.25MBT0.20.2硫1.751.75总计159.2159.2</table> Comparative Example Example 113 8650 NS 116100100CB control product Example Example 8950ZnO33 CB stearate 22FLEXZONE 7P product 11CBS1.251.25MBT0.20.2 sulfur 1.751.75 Total 159.2159.2 </ table>

</tables>实施例114处理的炭黑产品在橡胶配方中的应用该实施例介绍了在橡胶配方中使用本发明中处理过的炭黑产品。 Carbon black products </ tables> 114 processing example embodiment of the application in rubber formulations This example describes the use in rubber formulations of the present invention, the treated carbon black products. 从实施例87的处理过的炭黑产品和实施例89的对比炭黑、根据实施例104-108所述的方法,来制备橡胶混合物。 From Example 87-treated carbon black product of Example 89 and the comparative carbon black of embodiment, according to the procedure described in Example 104-108, to prepare a rubber mixture. 其配方和性能数据列于下表。 The formulation and performance data are shown in the following table. 这些结果表明:该处理过的炭黑产品可用于该橡胶配方。 These results indicate that: the treated carbon black products can be used in the rubber formulations.

</tables>实施例115-116炭黑产品在橡胶配方中的应用这些实施例介绍了在过氧化物固化的两个橡胶配方中使用本发明炭黑产品。 Examples 115-116 carbon black products in rubber formulations applying these embodiments </ tables> embodiment of the present invention describes the use of peroxide-cured rubber formulations both carbon black products. 用实施例88的炭黑产品和碘值为120mg/g、DBPA为125ml/100g的未处理比较炭黑来制备橡胶混合物。 Example 88 carbon black product and an iodine value of 120mg / g, to prepare a rubber mixture DBPA untreated comparative carbon black 125ml / 100g of. 使用实施例104-108中所述的方法及下述配方。 Using the method described in Example and the following formulation 104-108. <tables id="table20" num="020"> <table width="596">实施例115比较例116比较例NS-114100100Duradene715100100CB产品实施例885050对照CB5050ZnO3333硬脂酸2222Flexzone 7P1111过氧化二异丙苯2222总计158158158158</table> </tables>下表的性能数据表明:该炭黑产品可用于过氧化物固化的橡胶配方中。 <Tables id = "table20" num = "020"> <table width = "596"> Comparative Example NS-114100100Duradene715100100CB product of Example 115 Comparative Example 116 Example 885 050 control CB5050ZnO3333 stearate 2222Flexzone 7P1111 dicumylperoxide 2222 Total 158158158158 </ table> </ tables> performance data in the table show that: the carbon black products can be used for peroxide-cured rubber formulations. <tables id="table21" num="021"> <table width="721">100%模量Mpa200%模量Mpa.拉伸强度Mpa伸长%肖氏硬度A结合橡胶%Tanδ℃Tanδ70℃磨耗机指数14%滑移磨耗机指数21%滑移实施例1153.6610.423.9356613.30.2080.11998101比较例2.948.121.839862180.2840.156100100实施例1165.1111.513.92336717.50.2990.1526574比较例4.0711.320.33216122.10.3430.180100100</table> </tables>实施例117应用炭黑产品来使织物着色该实施例介绍使用本发明炭黑产品来使织物着色。 <Tables id = "table21" num = "021"> <table width = "721"> 100% modulus Mpa200% modulus Mpa. Elongation% Tensile strength Mpa Shore hardness A combination of rubber% Tanδ ℃ Tanδ70 ℃ wear machine index 14% 21% slip sliding abrasion machine index 1153.6610.423.9356613.30.2080.11998101 Comparative Example Example Example 1165.1111.513.92336717.50.2990.1526574 2.948.121.839862180.2840.156100100 Comparative Example 4.0711.320.33216122.10.3430.180100100 </ table > </ tables> Application Example 117 carbon black products to make the colored fabric to the embodiment of the present invention describes the use of carbon black products to the fabric coloring. 把织物样品在实施例16的炭黑产品的搅拌的分散液中在100℃、所示的浓度下,放置下表所示的时间,该炭黑产品具有相连的C6H4SO3-基。 The fabric sample was stirred in the dispersion of Example 16, the carbon black product at 100 ℃ concentrations shown, the time shown in the table below is placed, the carbon black product having attached C6H4SO3- groups. 如下调节pH值:取出样品,让其短暂排水,并把其放在热水中、热1MNaCl溶液或热的0.015MAl2(SO4)3中约30秒钟,来进行后处理。 The pH is adjusted as follows: Samples were removed and allowed to drain briefly, and put it on the hot water, heat or hot 1MNaCl solution 0.015MAl2 (SO4) 3 for about 30 seconds and then for processing. 当调节炭黑分散液的pH值时,调节NaCl和Al2(SO4)3后处理液的pH,使其互相匹配。 When adjusting the pH of the carbon black dispersion, adjusting the NaCl and Al2 (SO4) pH of the treatment solution after 3 to match each other. 然后这些样品用水洗涤并干燥。 These samples were then washed with water and dried. 下表的L值表明:这些织物能被该炭黑产品有效着色。 L value in the table show: The carbon black products of these fabrics can be effectively colored. 越低的L值表示越黑的材料。 The lower the L value represents the darker material.

</tables>A:pH未调节炭黑产品实施例118该实施例继续介绍现场制备本发明炭黑。 </ Tables> A: pH unadjusted Example 118 carbon black products continue to introduce the embodiment of the present invention prepared in situ carbon black. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

根据在Brzezinska,E.;Temay,Jr,AL“有机化学杂志”(J.Org.Chem.)1994,59卷第8239-8244页中所述的方法,制备4-氨基苯基-2-苯并噻唑基二硫化物。 According Brzezinska, E;. (. J.Org.Chem) the method described in the first pages 8239-8244 Temay, Jr, AL "Journal of Organic Chemistry" 1994, 59 volumes, Preparation of 4-phenyl-2-amino-benzene and thiazolyl disulfide. 把4-氨基苯基-2-苯并噻唑基二硫化物(9.79g)溶解在75℃下的300ml乙醇中,并加入到一搅拌下的浆料中,该浆料含有225g炭黑颗粒在1升乙醇中和6.37g70%硝酸。 The 4-aminophenyl-2-benzothiazolyl disulfide (9.79g) was dissolved in 300ml of ethanol at 75 ℃, and added to a stirred slurry, the slurry containing the carbon black particles in 225g 1 liter of ethanol and 6.37g70% nitric acid. 向该生成的浆料中加入100ml NaNO2(2.64g)溶液。 To the resulting slurry was added 100ml NaNO2 (2.64g) was added. 放出气体。 Evolution of gas. 搅拌48小时后,大多数乙醇挥发,收集生成的炭黑产品、用水洗涤并在125℃下干燥至恒重。 After stirring for 48 hours, most of the ethanol evaporated, the resulting carbon black product was collected, washed with water and dried to constant weight at 125 ℃.

已用THF萃取过夜并干燥的炭黑产品样品含有1.77%硫,与未处理炭黑含有1.12%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.77% sulfur, and untreated carbon black containing 1.12% sulfur compared. 因此,该炭黑产品有0.07mmol/g相连的-(4-C6H4)-SS-(2-C7H5NS)基。 Therefore, the carbon black product has 0.07mmol / g attached - (4-C6H4) -SS- (2-C7H5NS) group.

实施例119该实施例继续介绍现场制备本发明炭黑产品。 Example 119 This example describes the scene to continue the preparation of carbon black product of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如在实施例118中一样制备4-氨基苯基-2-苯并噻唑基二硫化物(14.1g),并把其溶解在含有10.1g37%HCl、360ml水和560ml丙酮的溶液中。 As prepared in Example 118 as 4-aminophenyl-2-benzothiazolyl disulfide (14.1g), and dissolved in the solution containing 10.1g37% HCl, 360ml water and 560ml acetone. 然后把该橙色溶液加到炭黑颗粒在0.8升水和1.2升丙酮中搅拌下的浆料中。 The orange solution was then added to the carbon black particles at 0.8 liters and 1.2 liters of acetone was stirred slurry. 把NaNO2(3.81g)在60ml和90ml丙酮中的溶液一次性加到该浆料中。 The NaNO2 (3.81g) in 60ml and 90ml disposable solution of acetone was added to the slurry. 放出气体。 Evolution of gas. 将该浆料搅拌过夜并过滤,收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 炭黑产品用水洗涤,过滤收集并在125℃下干燥至恒重。 Carbon black product was washed with water, collected by filtration and dried to constant weight at 125 ℃.

已用THF萃取过夜并干燥的炭黑产品含有1.77%硫,与未处理炭黑含有1.09%相比较。 It has overnight and dried carbon black product extracted with THF containing 1.77% sulfur, and untreated carbon black containing 1.09% compared to. 因此,该炭黑产品有0.07mmol/g相连的-(4-C6H4)-SS-(2-C7H5NS)基。 Therefore, the carbon black product has 0.07mmol / g attached - (4-C6H4) -SS- (2-C7H5NS) group.

实施例120该实施例继续介绍现场制备本发明炭黑产品。 Example 120 This example describes the scene to continue the preparation of carbon black product of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备4-氨基苯基-4′-羟苯基二硫化物。 It was prepared as follows 4-aminophenyl-4'-hydroxyphenyl disulfide. 4-氨基苯基-2-苯并噻唑基二硫化物(14.5g)溶解在325ml氯仿中,产生一橙色溶液。 4-aminophenyl-2-benzothiazolyl disulfide (14.5g) was dissolved in 325ml of chloroform, to produce an orange solution. 在30分钟时间内,滴加4-羟基噻吩(6.78g)在60ml氯仿中的溶液。 Within 30 minutes, a solution of 4-hydroxy-thiophene (6.78g) in 60ml of chloroform was added. 加料完成后,该反应混合物搅拌过夜。 After the addition was completed, the reaction mixture was stirred overnight. 在分液漏斗中用稀释在200ml水中的5.3g 37%HCl萃取该氯仿溶液。 In a separatory funnel with 200ml of water diluted in 5.3g 37% HCl solution was extracted with chloroform. 收集该水相层、用5%NaOH中和并用乙酸乙酯萃取。 The aqueous layer was collected, with 5% NaOH and extracted with ethyl acetate. 分离该乙酸乙酯层、在MgSO4上干燥并过滤。 The ethyl acetate layer was separated, dried over MgSO4 and filtered. 除去乙酸乙酯,得到黄色油状的10.5g 4-氨基苯基-4-羟苯基二硫化物。 Ethyl acetate was removed to give a yellow oil 10.5g 4- aminophenyl-4-hydroxyphenyl disulfide.

向如上述制备的4-氨基苯基-4′-羟苯基二硫化物(8.13g)在300ml水中的搅拌浆料中,加入6.99g 37%HCl在75ml水中的溶液。 As to 4-aminophenyl-4'-hydroxyphenyl disulfide prepared above (8.13g) in 300ml water stirred slurry, was added 6.99g 37% HCl solution in 75ml of water. 把该生成的白色悬浮液加到225g炭黑颗粒在1.5升水的浆料中,把该混合物搅拌5分钟。 The resultant white suspension was added to 1.5 liter of water 225g of carbon black particles in the slurry, and the mixture was stirred for 5 minutes. 把NaNO2(2.64g)在100ml水中的溶液加到该浆料中。 The NaNO2 (2.64g) in a solution of 100ml of water was added to the slurry. 放出气体。 Evolution of gas. 搅拌该浆料过夜,把该炭黑产品过滤分离并用水洗涤。 The slurry was stirred overnight, the carbon black product was isolated by filtration and washed with water. 在125℃下干燥该炭黑产品至恒重。 Dried at 125 ℃ to constant weight carbon black products.

用THF萃取过夜并干燥的炭黑产品样品含有1.67%硫,与未处理炭黑含有1.11%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.67% sulfur, and untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑有0.09mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-OH基。 Therefore, the carbon black has 0.09mmol / g attached - (4-C6H4) -SS- (4-C6H4) -OH group.

实施例121该实施例进一步介绍现场制备本发明炭黑产品。 Example 121 This example further introduce a carbon black product of the present invention prepared in situ. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

向237g炭黑颗粒在1.4g水中的搅拌浆料中加入4.44g 4-氨基噻吩和7.36g 37%HCl在250ml中的溶液。 4.44g 4- aminothiophene and 7.36g 37% HCl solution in 250ml of carbon black particles to 237g of water was added to the stirred slurry of 1.4g. 向所得的浆料中加入NaNO2(2.78g)在75ml水中的溶液。 NaNO2 (2.78g) in a solution of 75ml of water was added to the resulting slurry. 放出气体。 Evolution of gas. 该浆料搅拌2.5小时、过滤、并用水洗涤。 The slurry was stirred for 2.5 hours, filtered, and washed with water. 然后把该炭黑产品在125℃干燥至恒重。 The carbon black product is then dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.63%硫,与未处理炭黑含有1.11%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.63% sulfur, and untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑产品有0.15mmol/g相连的-(4-C6H4)-SH基。 Therefore, the carbon black product has 0.15mmol / g attached - (4-C6H4) -SH groups.

实施例122该实施例进一步介绍本发明炭黑产品的制备。 Example 122 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

向6-氨基-2-巯基噻唑(6.14g)在300ml水中的搅拌浆料中,加入6.99g 37%HCl在75ml水中的溶液。 Of 6-amino-2-mercapto-thiazole (6.14g) in 300ml water stirred slurry, was added 6.99g 37% HCl solution in 75ml of water. 把该生成的浆料冷却到10℃,并加入NaNO2(2.64g)在50ml水中的类似冷却液。 The resultant slurry was cooled to 10 ℃, and added NaNO2 (2.64g) similar to the coolant in 50ml water. 该生成的橙色浆料搅拌30秒钟,然后加到225g炭黑粒子在1.4升水和300g冰的搅拌浆料中。 The resulting orange slurry was stirred for 30 seconds, and then added to 225g of carbon black particles by stirring in 1.4 liters of water and 300g of ice slurry. 放出气体。 Evolution of gas. 该浆料搅拌2.5小时,然后过滤。 The slurry was stirred for 2.5 hours, then filtered. 该炭黑产品用水洗涤并在125℃下干燥至恒重。 The carbon black product was washed with water and dried at 125 ℃ to constant weight.

已用THF萃取过液并干燥的炭黑产品样品含有1.98%硫,与未处理炭黑含有1.11%硫相比较。 It has been extracted with THF overnight and dried sample containing 1.98% carbon black products of sulfur, and the untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑产品含有0.135mmol/g相连的-6-(2-C7H4NS)-SH基。 Therefore, the carbon black product contains 0.135mmol / g attached -6- (2-C7H4NS) -SH groups.

实施例123该实施例进一步介绍现场制备本发明炭黑产品。 Example 123 This example further introduce a carbon black product of the present invention prepared in situ. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双[2-(4-氨基苯基)乙基]二硫化物。 It was prepared as follows bis [2- (4-aminophenyl) ethyl] disulfide. 向4-硝基苯基乙基溴化物(23g)在280ml甲醇、70ml水的混合物中的回流溶液中,加入Na2S2O35H2O(31g)在75ml水中的溶液。 The 4-nitrophenyl ethyl bromide (23g) was refluxed in a mixture of 280ml of methanol, 70ml of water was added Na2S2O3 5H2O (31g) in a solution of 75ml water. 然后向该反应混合物中加入另外60ml水。 The reaction mixture was then added another 60ml of water was added. 回流条件继续5小时。 Reflux continued 5 hours. 让该生成的浅黄色溶液冷却至室温。 Let The resultant pale yellow solution was cooled to room temperature. 在旋转蒸发器中,从该溶液中除去甲醇,得到白色结晶水性浆料。 In a rotary evaporator, the methanol was removed from the solution, to give a white crystalline aqueous slurry. 向该浆料中加入300ml水,生成稍浑浊的溶液。 To this slurry was added 300ml water to produce slightly cloudy solution. 向4-硝基苯乙基硫代硫酸钠的水溶液中,加入Na2S9H2O(120g)在300ml水中的溶液。 To an aqueous solution of ethyl 4-nitrophenyl sodium thiosulfate was added Na2S 9H2O (120g) in 300ml water solution. 该反应混合物迅速变浑浊,并为微黄色,搅拌几分钟后,形成白色沉淀。 The reaction mixture quickly became cloudy and slightly yellow. After stirring for a few minutes, a white precipitate formed. 该浆料加热回流18小时,然后冷却。 The slurry was heated to reflux for 18 hours, then cooled. 出现橙色油,该橙色油用几部分乙酸乙酯萃取。 It appears as an orange oil, orange oil that was extracted with several portions of ethyl acetate. 把乙酸乙酯萃取物合并、在MgSO4上干燥并过滤。 The ethyl acetate extracts were combined, dried over MgSO4 and filtered. 除去乙酸乙酯,生成橙色油状的12g双[2-(4-氨基苯基)乙基]二硫化物。 Ethyl acetate was removed to produce an orange oil 12g bis [2- (4-aminophenyl) ethyl] disulfide.

向如上述所制备的双[2-(4-氨基苯基)乙基]二硫化物(5.02g)在200ml水的搅拌浆料中,加入6.67g 37%HCl在100ml水中的溶液。 As the above prepared bis [2- (4-aminophenyl) ethyl] disulfide (5.02g) in 200ml water stirred slurry, was added 6.67g 37% HCl solution in 100ml of water. 搅拌20分钟后,得到一橙色溶液,并把该橙色溶液加到炭黑颗粒在1升水中的搅拌浆料中。 After stirring for 20 minutes, to give an orange solution, and the orange solution was added to the carbon black particles in 1 liter of water was stirred slurry. 向该生成的浆料中加入NaNO2(2.46g)在100ml水中的溶液。 NaNO2 (2.46g) in a solution of 100ml of water was added to the resulting slurry. 放出气体。 Evolution of gas. 搅拌该浆料过夜后,过滤该炭黑产品,用水洗涤,并在125℃下干燥至恒重。 The slurry was stirred overnight, the carbon black product was filtered, washed with water and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.81%硫,与未处理炭黑含有1.11%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.81% sulfur, and untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑产品有0.11mmol/g相连的-(4-C6H4)-CH2CH2-SS-CH2CH2-(4-C6H4)-基。 Therefore, the carbon black product has 0.11mmol / g attached - (4-C6H4) -CH2CH2-SS-CH2CH2- (4-C6H4) - groups.

实施例124本实施例进一步介绍现场制备本发明炭黑产品。 Further described in Example 124 Examples of carbon black product of the present invention prepared in situ. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双[2-(4-氨基苯基)乙基]三硫化物。 It was prepared as follows bis [2- (4-aminophenyl) ethyl] trisulfide. 向500ml锥瓶中的铁粉(28.4g)在100℃的300ml水的浆料中,加入1.42g FeSO47H2O。 To 500ml Erlenmeyer flasks iron powder (28.4g) in 300ml of water at 100 ℃ slurry, was added 1.42g FeSO4 7H2O. 在5分钟内,把根据实施例123所介绍方法制备的硫代硫酸4-硝基苯基乙酯(29g),以每批1g的方式加入到该铁浆料中,同时保持温度为96-98℃。 Within 5 minutes, to (29g), was added to each batch manner 1g according thiosulfate method described in Example 123 Preparation of 4-nitrophenyl ester to the iron slurry, while maintaining the temperature at 96- 98 ℃. 在加料过程中,用手振动该锥瓶,来保持良好的混合。 During the addition, the hand vibration Erlenmeyer flask, to maintain good mixing. 在完成硫代硫酸4-硝基苯基乙酯的加料后,加入另外9.5g铁,并继续加热5分钟。 After completion of the addition thiosulfate ethyl 4-nitrophenyl group, an additional 9.5g of iron, and heating continued for 5 minutes. 一旦该锥瓶冷却到室温,加入几滴浓的NH4OH来把该反应混合物的pH从5调到9.5。 Once the flasks cooled to room temperature, add a few drops of concentrated NH4OH to the pH of the reaction mixture was adjusted from 5 9.5. 然后过滤该混合物,并用两份50ml水洗涤其铁和铁盐。 The mixture is then filtered and washed with two 50ml its iron and iron salts. 该黄色过滤物用37%HCl酸化到pH为1。 The yellow filtrate was acidified with 37% HCl to a pH of 1. 在pH约为5时,开始形成白色沉淀。 At a pH of about 5:00, a white precipitate began to form. 在5℃下冷却该酸化的过滤物过夜后,过滤收集该固体,用水然后用丙酮洗涤并空气干燥。 At 5 ℃ cooling the acidified filtrate overnight, the solid was collected by filtration, washed with water and then washed with acetone and air dried. 分离出约14.3g S-(4-氨基苯基乙基)硫代硫酸。 Separated about 14.3g S- (4- aminophenyl) thio sulfate.

向16g S-(4-氨基苯基乙基)硫代硫酸在500ml水中的浆料中加入固体NaHCO3来把pH调为8。 To 16g S- (4- aminophenyl) thio sulfate was added solid NaHCO3 in 500ml of water in the slurry to adjust the pH to 8. 当pH升高时,该固体溶解,生成S-(4-氨基苯基乙基)硫代硫酸钠溶液。 When the pH rises, the solid was dissolved to form S- (4- aminophenyl ethyl) sodium thiosulfate solution. 在30分钟时间内,向该溶液中滴加Na2S9H2O(12.3g)在150ml水中的溶液,同时伴随沉淀形成。 Within 30 minutes, this solution was added dropwise Na2S 9H2O (12.3g) in a solution of 150ml of water, accompanied by formation of a precipitate. 完成该加料后,该反应混合物搅拌15分钟,然后先用200ml、接着用100ml乙酸乙酯在分液漏斗中萃取两次。 After completion of the addition, the reaction mixture was stirred for 15 minutes, then first with 200ml, then extracted twice with 100ml of ethyl acetate in a separatory funnel. 把该乙酸乙酯萃取物合并,在MgSO4上干燥。 The The ethyl acetate extracts were combined, dried over MgSO4. 该乙酸乙酯蒸发,得到一黄色固体。 The ethyl acetate was evaporated to give a yellow solid. 双[2-(4-氨基苯基)乙基]三硫化物的最终分离后的产量为11.3g。 Final yield after separation trisulfide bis [(4-aminophenyl) ethyl 2] of 11.3g.

向如上制备的双[2-(4-氨基苯基)乙基]三硫化物(11.3g)在300ml水中的搅拌浆料中,加入稀释在100ml水中的13.7g 37%HCl溶液。 The above-prepared bis [2- (4-aminophenyl) ethyl] trisulfide (11.3g) in 300ml water stirred slurry, was added 13.7g 37% HCl diluted in a solution of 100ml water. 搅拌20分钟后,加入另外200ml水,并把该混合物缓慢加热到45℃,并搅拌15分钟,得到一溶液。 After stirring for 20 minutes, added another 200ml of water, and the mixture was slowly heated to 45 ℃, and stirred for 15 minutes to obtain a solution. 把该生成的溶液冷却到室温,并加入到炭黑粒子(225g)在1.2升水中的搅拌浆料中。 The resultant solution was cooled to room temperature, and added to the carbon black particles (225g) in 1.2 liters of water stirred slurry. 接着,把NaNO2(5.04g)在100ml水中的溶液加到该炭黑浆料中。 Next, NaNO2 (5.04g) in 100ml of water was added to the solution of the carbon black slurry. 放出气体。 Evolution of gas. 把该反应混合物搅拌过夜,把该炭黑产品过滤分离、用水洗涤,并在125℃下干燥至恒重。 The reaction mixture was stirred overnight, the carbon black product was isolated by filtration, washed with water, and dried to constant weight at 125 ℃.

用THF萃取过夜并干燥的炭黑产品样品含有2.09%硫,与未处理炭黑含有1.11%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 2.09% sulfur, and untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑产品有0.10mmol/g相连的-(4-C6H4)-CH2CH2-SSS-CH2CH2-(4-C6H4)-基。 Therefore, the carbon black product has 0.10mmol / g attached - (4-C6H4) -CH2CH2-SSS-CH2CH2- (4-C6H4) - groups.

实施例125该实施例继续介绍现场制备本发明炭黑产品。 Example 125 This example describes the scene to continue the preparation of carbon black product of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

向双(2-氨基苯基)二硫化物在500ml水中的搅拌浆料中,加入13.6g 37%HCl在80ml水中的溶液。 The bis (2-aminophenyl) disulfide in 500ml water stirred slurry, was added 13.6g 37% HCl solution in 80ml of water. 把该生成的浆料加热到65℃,生成一金色溶液和一棕色固体。 The resultant slurry was heated to 65 ℃, generating a golden brown solution and a solid. 过滤该热溶液以除去该固体,然后在搅拌下把该溶液加到炭黑粒子(225g)在1.2升水中的室温浆料中。 The hot solution was filtered to remove the solid, and then the solution was added under stirring to the silica particles (225g) in 1.2 liters of water at room temperature in the slurry. 然后在1分钟时间内把NaNO2(5.04g)在90ml水中的溶液加到该炭黑浆料中。 Then in 1 minute to NaNO2 (5.04g) in 90ml water was added to the solution of the carbon black slurry. 放出气体。 Evolution of gas. 把该混合物搅拌2小时,过滤并用水洗涤,在125℃下干燥至恒重。 The mixture was stirred for 2 hours, filtered and washed with water, dried at 125 ℃ to constant weight.

用THF萃取过夜并干燥的炭黑产品样品含有1.44%硫,与未处理炭黑含有1.12%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.44% sulfur, and untreated carbon black containing 1.12% sulfur compared. 因此,该炭黑产品有0.05mmol/g相连的-(2-C6H4)-SS-(2-C6H4)-基。 Therefore, the carbon black product has 0.05mmol / g attached - (2-C6H4) -SS- (2-C6H4) - groups.

实施例126 Example 126

该实施例继续介绍制备本发明炭黑产品。 This embodiment of the present invention is prepared to continue to introduce a carbon black product. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

双(3-氨基苯基)二硫化物的制备是根据双(3-硝基苯基)二硫化物,按照类似于由WASheppard在“有机合成,胶体”(Organic Syntheses,Coll.),第五卷,第843页中所述的方法来制备的。 Preparation of bis (3-aminophenyl) disulfide according bis (3-nitrophenyl) disulfide, in a manner similar to the WASheppard "Organic Synthesis, colloids" (Organic Syntheses, Coll.), The fifth volume method described on page 843 to be produced. 向13.7g固体状的3-硝基苯磺酰氯中加入46ml 47%氢碘酸(HI),生成黑棕色混合物。 To 13.7g of solid 3-nitrobenzenesulfonyl chloride was added 46ml 47% hydroiodic acid (HI), to generate dark brown mixture. 把该混合物回流2.5小时。 The mixture was refluxed for 2.5 hours. 在该反应过程中,碘副产物升华入水冷凝器中,并在适当间隔除去,来防止该冷凝器阻塞。 In this reaction, the iodine by-product sublimed into the water condenser and was removed at appropriate intervals to prevent blockage of the condenser. 当该反应混合物已冷却时,加入NaHSO3来中和剩下的碘。 When the reaction mixture has cooled, NaHSO3 to neutralize the remaining iodine. 过滤该生成的浆料,收集该固体,并用200ml水洗涤该固体。 The resulting slurry was filtered, the solid was collected, and the solid was washed with 200ml of water. 然后用300ml丙酮在过滤器萃取该固体,得到一橙色溶液。 In 300ml of acetone and then extracted solid was filter to give an orange solution. 除去丙酮,得到橙色固体状的8.4g双(3-硝基苯基)二硫化物。 Acetone was removed to give an orange solid 8.4g bis (3-nitrophenyl) disulfide.

向双(3-硝基苯基)二硫化物(8.4g)在100ml水中的搅拌浆料中加入Na2S9H2O(20.4g)在100ml水中的溶液。 Na2S 9H2O (20.4g) in 100ml of water to a solution of bis (3-nitrophenyl) disulfide (8.4g) was added in 100ml water stirred slurry. 加热该反应混合物至回流,这时得到一黑红色溶液。 The reaction mixture was heated to reflux, then give a dark red solution. 回流18小时后,向该反应混合物中加入另外5gNa2S9H2O,并继续加热2小时。 After 18 hours at reflux, the reaction mixture was added additional 5gNa2S 9H2O, and heating continued for 2 hours. 以滴加方式向该冷却的反应混合物中加入3.5g 30%H2O2。 The reaction mixture was added dropwise to the cooled manner 3.5g 30% H2O2. 用100ml乙酸乙酯萃取形成的白色沉淀两次。 With 100ml ethyl acetate twice white precipitate formed. 把乙酸乙酯萃取物合并并在MgSO4上干燥。 The ethyl acetate extracts were combined and dried over MgSO4. 除去乙酸乙酯,得到5.9g双(3-氨基苯基)二硫化物。 Ethyl acetate was removed to give 5.9g of bis (3-aminophenyl) disulfide.

向如上制备的双(3-氨基苯基)二硫化物(10.2g)在0.7升水中的搅拌浆料中,加入18g 37%HCl在50ml水中的溶液。 The above-prepared bis (3-aminophenyl) disulfide (10.2g) was stirred in 0.7 liters of water slurry, 18g 37% HCl solution was added in 50ml of water. 把该溶液冷却到10℃,然后加入NaNO2(6.1g)在75ml水中的类似冷却的溶液。 The solution was cooled to 10 ℃, followed by addition of NaNO2 (6.1g) in 75ml water cooled solution similar. 然后把该混合物加到炭黑粒子(225g)在1.8升水中的搅拌浆料中。 The mixture was then added to the carbon black particles (225g) in 1.8 liters of water was stirred slurry. 放出气体,搅料2小时后,把该炭黑产品过滤分离,用水洗涤并在115℃下干燥至恒重。 Evolution of gas after mixing feed two hours, the carbon black product was isolated by filtration, washed with water and dried at 115 ℃ to constant weight.

已用THF萃取过夜并干燥过的炭黑产品样品含有1.71%硫,与未处理炭黑含有1.11%硫相比较。 It has been extracted with THF overnight and dried sample containing 1.71% carbon black products of sulfur, and the untreated carbon black containing 1.11% sulfur compared. 因此,该炭黑产品有0.09mmol/g相连的-(3-C6H4)-SS-(3-C6H4)-基。 Therefore, the carbon black product has 0.09mmol / g attached - (3-C6H4) -SS- (3-C6H4) - groups.

实施例127该实施例继续介绍本发明炭黑产品的制备。 Example 127 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

根据在Ward,ER,Poesche,WH;Higgins,D.和Heard,DD“化学学会会刊”(J.Chem.Soc.)1962,第2374-2379页中所述的方法制备6-氨基-1,2,3-苯并噻二唑。 According to Ward, ER, Poesche, WH;. A method according to Higgins, D and Heard, DD "Chemical Society journal" (. J.Chem.Soc) 1962, p. 2374-2379 in the preparation of 6-Amino-1 , 2,3-thiadiazole. 把3.5g HCl在50ml水中的溶液加到固体6-氨基-1,2,3-苯并噻二唑(2.38g)中,并把该生成的溶液冷却到10℃。 The 3.5g HCl in 50ml water was added to solid 6-amino-benzo-1,2,3-thiadiazole (2.38g) in, and to the resulting solution was cooled to 10 ℃. 接着,加入NaNO2(1.1g)在50ml水中的冷溶液,并把该混合物加到炭黑粒子(105g)在500ml水和100g冰的搅拌浆料中。 Then, was added NaNO2 (1.1g) in 50ml of water cooled solution, and the mixture is added to the carbon black particles (105g) in 500ml of water and 100g of ice was stirred slurry. 放出气体。 Evolution of gas. 搅拌该混合物3小时后,把该炭黑产品通过过滤收集,用水和异丙醇洗涤,并空气干燥至恒重。 After the mixture was stirred for 3 hours, the carbon black product was collected by filtration, washed with water and isopropanol, and air dried to constant weight.

用THF萃取过夜并干燥的炭黑产品样品含有1.50%硫,与未处理炭黑含有1.06%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.50% sulfur, and untreated carbon black containing 1.06% sulfur compared. 因此,该炭黑产品有0.14mmol/g相连的-6-(C7H5N2S)基。 Therefore, the carbon black product has 0.14mmol / g attached -6- (C7H5N2S) group.

实施例128该实施例进一步介绍现场制备本发明炭黑产品。 Example 128 This example further introduce a carbon black product of the present invention prepared in situ. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备N-吗啉代-(6-氨基苯并噻唑)-2-亚磺酰胺。 N- morpholino was prepared as follows - (6-amino-benzothiazole) -2-sulfenamide. 向NaI(47g)溶解在150ml水中的水溶液中加入I2(35.5g),来制备NaI3溶液。 To NaI (47g) was dissolved was added I2 (35.5g) in aqueous solution in 150ml of water to prepare NaI3 solution. 接着,把6-氨基-2-巯基苯并噻唑(6.5g)加到由NaOH(2.84g)在50ml水中的溶液中。 Next, 6-amino-2-mercapto-benzothiazole (6.5g) in 50ml water was added to the NaOH (2.84g) in. 搅拌15分钟后,得到红棕色溶液,向其中加入吗啉(9.28g)。 After stirring for 15 minutes to give a red-brown solution, to which was added morpholine (9.28g). 向该混合物中加入预先制备的NaI3溶液。 To this mixture was added a solution previously prepared NaI3. 形成棕色沉淀,并把该浆料搅拌4小时。 Brown precipitate formed and put the slurry was stirred for 4 hours. 该固体过滤分离并空气干燥。 The solid was isolated by filtration and air-dried. 该固体在75ml乙醇和3.34g吗啉中变成浆料。 The solid into a slurry in 75ml of ethanol and 3.34g morpholine. 在20分钟时间内,向该浆料滴加入3.24gI2在60ml乙醇的溶液。 Within 20 minutes, the slurry was added dropwise to the solution in 60ml of ethanol 3.24gI2. 在室温下搅拌该混合物过夜后,在旋转蒸发器中除去该乙醇,并用NaI的水溶液洗涤该残余物来除去未反应的碘。 The mixture was stirred overnight at room temperature, the ethanol was removed on a rotary evaporator, and the residue was washed with an aqueous solution of NaI to remove unreacted iodine. 把该产品过滤收集,用250ml水洗涤,然后在真空烘箱中60℃下干燥6小时。 The product was collected by filtration, washed with 250ml of water, and then in a vacuum oven at 60 ℃ was dried for 6 hours. 分离出9.2g80%纯度的N-吗啉代-(6-氨基苯并噻唑)-2-亚磺酰胺。 Isolated 9.2g80% purity N- morpholino - (6-amino-benzothiazole) -2-sulfenamide.

向含有炭黑粒料(175g)、N-吗啉代-(6-氨基苯并噻唑)-2-亚磺酰胺(7.01g)和NaNO2(1.96g)在1升水中的搅拌浆料中,加入5.43g 37%HCl稀释在75ml水中的溶液。 To a solution containing carbon black pellets (175g), N- morpholino - (6-amino-benzothiazole) -2-sulfonamide (7.01g) and NaNO2 (1.96g) was stirred in 1 liter of water in the slurry, Add 5.43g 37% HCl diluted in 75ml of water was added. 放出气体。 Evolution of gas. 搅拌该浆料48小时后,该炭黑产品过滤,用水洗涤、并在100℃下干燥至恒重。 After the slurry was stirred for 48 hours, the carbon black product was filtered, washed with water and dried at 100 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.62%硫,与未处理炭黑含1.12%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.62% sulfur, and untreated carbon black containing 1.12% sulfur compared. 因此,该炭黑产品有0.08mmol/g相连的-6-(2-C7H4NS)-S-NRR′基团,其中RR′是-CH2CH2OCH2CH2-。 Therefore, the carbon black product has 0.08mmol / g attached -6- (2-C7H4NS) -S-NRR 'group, where RR' is -CH2CH2OCH2CH2-.

实施例129该实施例继续介绍本发明炭黑产品的制备。 Example 129 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双(4-氨基苯基)四硫化物。 It was prepared as follows bis (4-aminophenyl) tetrasulfide. 在氮气氛中,制备9.74g 4-氨基噻吩在 50ml无水四氢呋喃(THF)中的溶液。 In a nitrogen atmosphere, 9.74g 4- aminothiophene prepared in 50ml anhydrous tetrahydrofuran (THF) was added. 然后在干冰/乙醇浴中冷却该溶液。 The solution was then cooled in a dry ice / ethanol bath. 把丁基锂加到烧瓶中,形成深黄色沉淀。 The butyllithium was added to the flask to form a yellow precipitate. 向该烧瓶中加入另外125mlTHF,并把该烧瓶在冰水浴中加热到5℃。 To the flask was added additional 125mlTHF, and the flask was heated to the 5 ℃ in an ice water bath. 在5秒钟内把一氯化硫,S2Cl2(2.80ml)加到该浆料中,生成红色溶液。 Within 5 seconds of the sulfur monochloride, S2Cl2 (2.80ml) was added to the slurry to form a red solution. 在-15℃下放置过夜,把该反应混合物加热到室温,并用旋转蒸发器除去THF。 Left overnight at -15 ℃, the reaction mixture is heated to room temperature and treated with a rotary evaporator remove THF. 把该橙色油再次溶解在CH2Cl2内,用硅藻土过滤来除去不溶的LiCl并在MgSO4上干燥。 The orange oil which was redissolved in CH2Cl2, filtered through Celite to remove insoluble LiCl and dried over MgSO4. 过滤该溶液除去MgSO4后,除去CH2Cl2,生成11.4g橙色油状的双(4-氨基苯基)四硫化物。 After the solution was filtered to remove MgSO4, remove CH2Cl2, generate 11.4g orange oily bis (4-aminophenyl) tetrasulfide.

把13g 37%HCl在75ml水中的溶液加到双(4-氨基苯基)四硫化物(10g)(制备如上)在200ml水中的浆料中,并搅拌生成的混合物15分钟。 The 13g 37% HCl in 75ml water was added to a solution of bis (4-aminophenyl) tetrasulfide (10g) (prepared as above) in 200ml of water in the slurry, and the resulting mixture was stirred for 15 minutes. 把该橙红色悬浮液冷却到10℃,并在1-2分钟内,加入NaNO2(4.8g)在60ml水中的类似冷却液。 The orange to red suspension was cooled to 10 ℃, and within 1-2 minutes, was added NaNO2 (4.8g) in 60ml water was similar coolant. 把该生成的橙黄色浆料和炭黑粒料(213g)在1升水和200g冰的搅拌浆料合并。 The merger and the resultant slurry was stirred orange pulp and carbon black pellets (213g) in 1 liter of water and 200g of ice. 放出气体。 Evolution of gas. 搅拌该混合物过夜,把该炭黑产品过滤分离,用水洗涤,并在120℃下干燥至恒重。 The mixture was stirred overnight, the carbon black product was isolated by filtration, washed with water, and dried to constant weight at 120 ℃.

已用THF萃取过夜并干燥的炭黑产品样品含有2.40%硫,与未反应炭黑含有1.23%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.40% sulfur, unreacted carbon black and containing 1.23% sulfur compared. 因此,该炭黑产品有0.09mmol/g相连的-(4-C6H4)-SSSS-(4-C6H4)-基。 Therefore, the carbon black product has 0.09mmol / g attached - (4-C6H4) -SSSS- (4-C6H4) - groups.

实施例130该实施例继续介绍现场制备本发明炭黑产品。 The implementation of on-site preparation of the present invention, the carbon black product of Example 130 This example continue to introduce. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双(4-氨基苯基)四硫化物。 It was prepared as follows bis (4-aminophenyl) tetrasulfide. 向4-硝基氯苯(59g)在600ml水中的搅拌浆料中,加入溶于200ml水中的Na2S9H2O(240g)溶液中。 The 4-nitro-chlorobenzene (59g) in 600ml water stirred slurry was added dissolved in 200ml of water Na2S 9H2O (240g) solution. 在45分钟内把该生成的混合物加热到回流,并持续17小时。 Within 45 minutes The resultant mixture was heated to reflux and continued for 17 hours. 在17小时结束时,在烧瓶中出现少量油。 At the end of 17 hours, a small amount of oil in the flask. 让该反应混合物冷却到室温后,把该水溶液从该油中滗析出来,然后过滤。 Let the reaction mixture was cooled to room temperature, the aqueous solution from which the oil is decanted and then filtered. 接着,把元素硫粉末(72g)加到该水性过滤物中,并把该生成的浆料加热到回流。 Next, elemental sulfur powder (72g) was added to the aqueous filtrate in, and to the resulting slurry was heated to reflux. 22小时后,在该反应中出现大量橙色油。 After 22 hours, a large number of orange oil present in the reaction. 撤去热,并把该反应混合物冷却到室温。 Heat is removed, and the reaction mixture is cooled to room temperature. 把该橙色油萃取入500ml乙酸乙酯中。 The orange oil that was extracted into 500ml of ethyl acetate. 一旦已把该乙酸乙酯溶液过滤并在MgSO4上过滤,除去乙酸乙酯,得到橙色油状的双(4-氨基苯基)四硫化物。 Once 已把 The ethyl acetate solution was filtered, and filtered over MgSO4, ethyl acetate was removed to give an orange oil of bis (4-aminophenyl) tetrasulfide.

在300ml水中搅拌上述制备的双(4-氨基苯基)四硫化物(10.5g),并向其中加入稀释在100ml水中的13.7g 37%HCl溶液。 300ml of water was stirred in the above prepared bis (4-aminophenyl) tetrasulfide (10.5g), and thereto is added diluted in 13.7g 37% HCl solution, 100ml of water. 搅拌15分钟,加入另外200ml水。 Stirred for 15 minutes, was added another 200ml of water. 搅拌另外45分钟,生成细碎的悬浮液。 Stirred for an additional 45 minutes to produce a finely divided suspension. 过滤该悬浮液以除去该固体,把该过滤物与炭黑粒料(225g)在1.2升水中的搅拌浆料中合并。 The suspension was filtered to remove the solid, the filtrate and the carbon black pellets (225g) in 1.2 liters of water were combined in a stirred slurry. 接着,把NaNO2(5.04g)在50ml水中的溶液加入到该炭黑浆料中。 Next, NaNO2 (5.04g) in a solution of 50ml of water was added to the carbon black slurry. 放出气体,搅拌该混合物过夜,把该炭黑产品过滤分离,用水洗涤并在120℃下干燥至恒重。 Gas evolution, and the mixture was stirred overnight, the carbon black product was isolated by filtration, washed with water and dried to constant weight at 120 ℃.

已用THF萃取过夜并干燥的炭黑产品样品含有2.36%硫,与未处理炭黑含有1.09%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.36% sulfur, and untreated carbon black containing 1.09% sulfur compared. 因此,该炭黑产品有0.10mmol/g相连的-(4-C6H4)-SSSS-(4-C6H4)-基。 Therefore, the carbon black product has 0.10mmol / g attached - (4-C6H4) -SSSS- (4-C6H4) - groups.

实施例131按照实施例130的方法,并使用7.03g 4-氨基苯基四硫化物在200ml水中的悬浮液、9.09g 37%HCl在75ml水中的溶液、3.36g NaNO2在100ml水中的溶液和225g同样炭黑粒料在1.2升水中的浆料,来制备连有-(4-C6H4)-SSSS-(4-C6H4)-基团的炭黑产品。 Example 131 Following the procedure of Example 130, and using 7.03g 4- aminophenyl tetrasulfide in 200ml water suspension, 9.09g 37% HCl solution in 75ml of water, 3.36g NaNO2 solution in 100ml of water and 225g The same slurry of carbon black pellets in 1.2 liters of water to prepare attached - (4-C6H4) -SSSS- (4-C6H4) - groups of carbon black products.

已用THF萃取过夜并干燥的炭黑产品样品含有1.63%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.63% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.05mmol/g相连的-(4-C6H4)-SSSS-(4-C6H4)-基。 Therefore, the carbon black product has 0.05mmol / g attached - (4-C6H4) -SSSS- (4-C6H4) - groups.

实施例132按照实施例130的方法,并使用5.27g 4-氨基苯基四硫化物在200ml水中的悬浮液、6.82g 37%HCl在75ml水中的溶液、2.52g NaNO2在100ml水中的溶液和225g同样炭黑粒料在1.2升水中的浆料,来制备连有-(4-C6H4)-SSSS-(4-C6H4)-基团的炭黑产品。 Example 132 Following the procedure of Example 130, and using 5.27g 4- aminophenyl tetrasulfide in 200ml water suspension, 6.82g 37% HCl solution in 75ml of water, 2.52g NaNO2 solution in 100ml of water and 225g The same slurry of carbon black pellets in 1.2 liters of water to prepare attached - (4-C6H4) -SSSS- (4-C6H4) - groups of carbon black products.

已用THF萃取过夜并干燥的炭黑产品样品含有1.54%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.54% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.03mmol/g相连的-(4-C6H4)-SSSS-(4-C6H4)-基。 Therefore, the carbon black product has 0.03mmol / g attached - (4-C6H4) -SSSS- (4-C6H4) - groups.

实施例133按照实施例130的方法,并使用3.22g 4-氨基苯基四硫化物在200ml水中的悬浮液、4.16g 37%HCl在75ml水中的溶液、1.54g NaNO2在100ml水中的溶液和206g同样炭黑粒料在1.2升水中的浆料,来制备连有-(4-C6H4)-SSSS-(4-C6H4)-基团的炭黑产品。 Example 133 Following the procedure of Example 130, and using 3.22g 4- aminophenyl tetrasulfide in 200ml water suspension, 4.16g 37% HCl solution in 75ml of water, 1.54g NaNO2 solution in 100ml of water and 206g The same slurry of carbon black pellets in 1.2 liters of water to prepare attached - (4-C6H4) -SSSS- (4-C6H4) - groups of carbon black products.

已用THF萃取过夜并干燥的炭黑产品样品含有1.26%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.26% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.02mmol/g相连的-(4-C6H4)-SSSS-(4-C6H4)-基。 Therefore, the carbon black product has 0.02mmol / g attached - (4-C6H4) -SSSS- (4-C6H4) - groups.

实施例134该实施例继续介绍现场制备本发明炭黑产品。 Example 134 This example describes the scene to continue the preparation of carbon black product of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

向把7.33g 37%HCl加到150ml水中以前制备的稀水性酸溶液中,加入液体4-氨基苯乙烯(4.02g)。 Dilute aqueous acid solution of 7.33g 37% HCl was added to 150ml of water previously prepared, was added 4-amino-styrene liquid (4.02g). 搅拌该混合物5分钟,得到一黄色溶液,并把其加到炭黑粒料(225g)在1.2升水中的搅拌浆料中。 The mixture was stirred for 5 minutes, to give a yellow solution, and added to the carbon black pellets (225g) in 1.2 liters of water was stirred slurry. 加入溶于50ml水中的NaNO2(2.94g)溶液,结果生成了气体。 Dissolved in 50ml of water NaNO2 (2.94g) solution, the results generated gas. 搅拌该混合物3小时后,该炭黑产品过滤分离,用水洗涤,并在125℃下干燥至恒重。 After the mixture was stirred for 3 hours, the carbon black product was isolated by filtration, washed with water, and dried to constant weight at 125 ℃.

已用THF萃取过夜并干燥的炭黑产品含有0.46%氢,与未处理炭黑含有0.37%氢相比较。 It has overnight and dried carbon black product extracted with THF containing 0.46% hydrogen, with the untreated carbon black containing 0.37% compared with hydrogen. 因此,本发明炭黑有0.06mmol/g相连的-(4-C6H4)-CH=CH2基。 Therefore, the carbon black of the present invention there is 0.06mmol / g attached - (4-C6H4) -CH = CH2 group.

实施例135该实施例继续介绍现场制备本发明的炭黑产品。 Example 135 This example describes the scene to continue the preparation of the present invention, the carbon black product. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

根据在Tenaka等人在“化学药物通报”(Chem.Pharm.Bull.)1974,第22卷,第2725页中所介绍的方法,制备S-(4-氨基苯基)硫代硫酸,并把其溶解在含有3.50g 37%HCl的600ml水中。 According to the Tenaka et al, "chemicals Bulletin" (Chem.Pharm.Bull.) 1974, Vol. 22, pp. 2725, as described in the preparation S- (4- aminophenyl) thiosulfate, and the It was dissolved in 3.50g 37% HCl containing 600ml of water. 把该溶液加到炭黑粒料(215g)在1.2升水中的搅拌浆料中。 The solution was added to the carbon black pellets (215g) in 1.2 liters of water was stirred slurry. 接着,把NaNO2(2.52g)在30ml水中的水溶液加到该浆料中。 Next, NaNO2 (2.52g) in 30ml of water was added to the aqueous slurry. 放出气体。 Evolution of gas. 搅拌该混合物2小时,然后静置过夜后,把该炭黑产品过滤分离,用水洗涤并在125℃下干燥至恒重。 The mixture was stirred for 2 hours, then after standing overnight, the carbon black product was isolated by filtration, washed with water and dried to constant weight at 125 ℃.

用THF萃取过夜并干燥的炭黑产品样品含有1.58%硫,与未处理炭黑含有1.23%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.58% sulfur, and untreated carbon black containing 1.23% sulfur compared. 因此,该炭黑产品有0.05mmol/g相连的-(4-C6H4)-S-SO3H基。 Therefore, the carbon black product has 0.05mmol / g attached - (4-C6H4) -S-SO3H groups.

实施例136该实施例继续介绍本发明炭黑产品的制备。 Example 136 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双[4-(4′-氨基苯磺酰氨基)苯基]二硫化物。 It was prepared as follows bis [4- (4'-amino-benzenesulfonylamino) phenyl] disulfide. 向室温下丙酮(500ml)中搅拌下的N-乙酰磺胺酰氯(20.0g)中,加入4-氨基苯基二硫化物(10.12g),接着加入吡啶(7.09g)。 To acetone at room temperature (500ml) under stirring N- acesulfame chloride (20.0g) was added 4-aminophenyl disulfide (10.12g), followed by pyridine (7.09g). 把该浑浊的黄-橙色反应混合物搅拌20小时,在这个时间内,形成金黄色溶液。 The turbidity of the yellow - orange reaction mixture was stirred for 20 hours, at this time, golden yellow solution formed. 把7.5ml 37%HCl加到45ml水中,并把该酸溶液加到该反应混合物中。 The 7.5ml 37% HCl was added to 45ml of water, and the acid solution was added to the reaction mixture. 除去丙酮,将剩余的混合物用100ml水稀释,并用乙酸乙酯萃取(2200ml)。 Acetone was removed, the remaining mixture was diluted with 100ml water, extracted with ethyl acetate (2 200ml). 把合并的该结合的乙酸乙酯萃取物用水(5200ml)洗涤,用饱和的盐水溶液(1100ml)洗涤,在硫酸钠上干燥并过滤。 The combined ethyl acetate extracts were washed with water of the binding (5 200ml) and washed with saturated saline solution (1 100ml), dried over sodium sulfate and filtered. 除去乙酸乙酸乙酯,得到29.37g褐色泡沫状的粗产物。 Ethyl acetate was removed to give the crude product was 29.37g tan foam. 将该物质加入到含有THF(150ml)的烧瓶中,并加入2NHCl(150ml)。 This material was added to a flask containing THF (150ml) in, and added 2NHCl (150ml). 将所生产成的浆料加热到回流。 The produced slurry was heated to a reflux. 回流24小时后,加入2NHCl(48ml),并将反应继续回流22小时。 After 24 hours at reflux, was added 2NHCl (48ml), and the reaction was continued at reflux for 22 hours. 将透明的橙色溶液冷却到室温,并用固体NaHCO3小心调至碱性,将所生成的混合物用乙酸乙酯(3200ml)萃取。 The clear orange solution was cooled to room temperature and carefully made basic with solid NaHCO3, the resulting mixture (3 200ml) and extracted with ethyl acetate. 将合并的乙酸乙酯萃取物用水洗涤(4200ml)直到中性;在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were washed with water (4 200ml) until neutral; dried over Na2SO4 and filtered. 除去乙酸乙酯,得到20.2g黄色固体状的所要的产品。 Ethyl acetate was removed to give a yellow solid 20.2g of the desired product.

把前述制备的双[4-(4′-氨基苯磺酰氨基)苯基]二硫化物(18.83g)溶解在500ml水、632.4g丙酮和13.65g 37%HCl的混合物中。 The bis [4- (4'-amino-benzenesulfonylamino) phenyl] disulfide prepared above (18.83g) were dissolved in a mixture of 500ml of water, 632.4g of acetone and 13.65g 37% HCl in. 在冰水浴中冷却该黄色溶液,并加入NaNO2(13.65g),生成含有橙色沉淀的深红色溶液。 Cooled in an ice water bath and the yellow solution was added NaNO2 (13.65g), to generate a deep red solution containing an orange precipitate. 把该混合物一次加入炭黑粒料(225g)在1/1丙酮/水(总计1.5升)的快速搅拌的浆料中。 The mixture was added carbon black pellets (225g) rapidly stirred slurry in 1/1 acetone / water (1.5 liters total) of. 放出气体。 Evolution of gas. 把该浆料搅拌过夜,并过滤收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该炭黑产品用水洗涤、过滤收集,并在125℃下干燥至恒重。 The carbon black product was washed with water, collected by filtration and dried at 125 ℃ to constant weight.

用THF萃取过夜并干燥的炭黑产品样品含有2.21%硫,与未处理炭黑含有1.14%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 2.21% sulfur, and untreated carbon black containing 1.14% sulfur compared. 因此,该炭黑产品有0.084mmol/g相连的-(4-C6H4)-SO2NH-(4-C6H4)-SS-(4-C6H4)-NHSO2-(4-C6H4)-基。 Therefore, the carbon black product has 0.084mmol / g attached - (4-C6H4) -SO2NH- (4-C6H4) -SS- (4-C6H4) -NHSO2- (4-C6H4) - groups.

实施例137该实施例继续介绍本发明炭黑产品的制备。 Example 137 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把对-苯二胺(4.87g)溶于含有9.11g 37%HCl的250ml水中。 The pair - phenylenediamine (4.87g) was dissolved in water containing 250ml of 9.11g 37% HCl. 把其在冰浴中冷却,并加入3.36g NaNO2溶于125ml水中的溶液。 The cooled in an ice bath, and the solution was added 3.36g NaNO2 dissolved in 125ml water. 把该生成的蓝-绿色溶液一次性加入到炭黑粒料(225g)在含有280g冰的2升水中的快速搅拌的浆料中。 The generation of the blue - green solution was added in one portion to a carbon black pellets (225g) in 2 liters of water containing 280g of ice rapidly stirred slurry. 该浆料搅拌过夜并过滤,来收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product was washed with water, collected by filtration and dried at 125 ℃ to constant weight.

实施例138该实施例继续介绍本发明炭黑产品的制备。 Example 138 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把对-苯二胺(2.43g)溶于含有9.11g 37%HCl的250ml水中。 The pair - phenylenediamine (2.43g) was dissolved in water containing 250ml of 9.11g 37% HCl. 把其在冰浴中冷却,并加入3.36g NaNO2溶于125ml水中的溶液。 The cooled in an ice bath, and the solution was added 3.36g NaNO2 dissolved in 125ml water. 把该生成的蓝-绿色溶液一次性加入到炭黑粒料(225g)在含有280g冰的2升水中的快速搅拌的浆料中。 The generation of the blue - green solution was added in one portion to a carbon black pellets (225g) in 2 liters of water containing 280g of ice rapidly stirred slurry. 该浆料搅拌过夜并过滤,来收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product was washed with water, collected by filtration and dried at 125 ℃ to constant weight.

实施例139该实施例继续介绍本发明炭黑产品的制备。 Example 139 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备2,2′-双(6-氨基苯并噻唑基)二硫化物。 Prepared by 2,2'-bis (6-amino-benzothiazolyl) disulfide. 把6-氨基-2-巯基苯并噻唑(15.0g)加入到500ml水中。 The 6-amino-2-mercapto-benzothiazole (15.0g) was added to 500ml of water. 向该浆料中加入NaOH(3.3g)溶于1升水中的溶液,该混合物在室温下搅拌1小时直到大多数硫醇溶解。 To this slurry was added NaOH (3.3g) was dissolved in 1 liter of water was added, and the mixture was stirred for one hour until most of the thiol was dissolved at room temperature. 在强力搅拌的同时,在1.5小时内向该硫醇盐溶液中逐渐加入含有NaI(24.73g)和I2(10.47g)在750ml水中的溶液。 With vigorous stirring, within 1.5 hours of the thiol-containing salt solution was gradually added NaI (24.73g) and I2 (10.47g) in a solution of 750ml water. 在加料过程中,形成含有淡黄色固体的浓浆料。 During the addition, the formation of a thick slurry containing a yellowish solid. 加料后,继续搅拌另外45分钟,过滤分离该固体。 After the addition, stirring was continued for another 45 minutes, the solid was separated by filtration.

把上述制备的2,2′-双(6-氨基苯并噻唑基)-二硫化物加入到含有13.66g 37%HCl的600ml水中。 The 2,2'-bis (6-amino-benzothiazolyl) prepared as described above - disulfide was added to a solution containing 13.66g 37% HCl in 600ml water. 该黄色浆料在冰浴中冷却,并加入5.04gNaNO2溶于50ml水中的溶液。 The yellow slurry was cooled in an ice bath, and 50ml water was added to the solution 5.04gNaNO2 dissolved. 把该生成的黑棕色混合物一次加入到炭黑粒料(225g)在含有280g冰的水中的快速搅拌的浆料中。 The resultant dark brown mixture was added to the carbon black pellets (225g) in water containing 280g of rapidly stirring ice slurry. 将该浆料搅拌过夜并过滤以收集炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水和异丙醇洗涤、过滤收集,并在125℃下干燥至恒重。 The product is washed with water and isopropanol, collected by filtration and dried at 125 ℃ to constant weight.

已用THF萃取并干燥的炭黑产品样品含有1.69%硫,与未处理炭黑含有1.00%硫相比较。 It has been extracted with THF and dried sample containing 1.69% carbon black products of sulfur, and the untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.054mmol/g相连的-6-(2-C6H4NS)-SS-2-(6-C7H4NS)-基。 Therefore, the carbon black product has 0.054mmol / g attached -6- (2-C6H4NS) -SS-2- (6-C7H4NS) - group.

实施例140该实施例继续介绍本发明炭黑产品的制备。 Example 140 This example continue to introduce the carbon black product of the present invention was prepared. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备4-氨基苯基-4-氨基苄基硫化物。 It was prepared as follows 4-aminophenyl-4-amino benzyl sulfide. 把NaOH(7.1g)在水(200ml)中的溶液加到4-氨基噻吩(19.8g)在190ml水中的混合物中。 The NaOH (7.1g) in water (200ml) was added 4-amino-thiophene (19.8g) in a mixture of 190ml of water. 搅拌该混合物直到大多数噻吩溶解。 The mixture was stirred until most of thiophene was dissolved. 在良好搅拌下,向该混合物中分多次加入4-硝基苄基氯(25.8g)。 Under good stirring, to the mixture was added 4-carve times nitrobenzyl chloride (25.8g). 然后该生成的黄色溶液在回流下搅拌1.5小时,在这个时间内分离出深红色的油。 Then the resulting yellow solution was stirred at reflux for 1.5 hours, the dark red oil separated during this time. 在该反应结束时,让该混合物冷却室温,并把该红色油分离成为蜡状固体。 At the end of the reaction, the mixture was allowed to cool to room temperature and the red oil separated to become waxy solid. 该固体用乙酸乙酯萃取(400ml,接着100ml),并把该合并的乙酸乙酯萃取物在Na2SO4上干燥和过滤。 The solid was extracted with ethyl acetate (400ml, then 100ml), and the combined ethyl acetate extracts of the dried and filtered Na2SO4. 除去乙酸乙酯,得到38.65g 4-氨基苯基-4-硝基苄基硫化物。 Ethyl acetate was removed to give 38.65g 4- aminophenyl-4-nitrobenzyl sulfide.

把上面的所有产品溶于乙醇(235ml)和水(780ml)的混合物中。 The above mixture was dissolved in ethanol all products (235ml) and water (780ml) in. 向该溶液中加入37%HCl(27.83g)和铁粉(49.78g),并把该浆料在回流下搅拌3小时。 To this solution was added 37% HCl (27.83g) and iron powder (49.78g), and to the slurry was stirred at reflux for 3 hours. 冷却到室温后,加入200ml水,并把该混合物用乙酸乙酯萃取(600ml,接着200ml)。 After cooling to room temperature, 200ml of water was added, and the mixture was extracted with ethyl acetate (600ml, then 200ml). 该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,得到31.53g所要的产品。 Ethyl acetate was removed to give 31.53g of the desired product.

把上述制备的4-氨基苯基-4-氨基苄基硫化物(7.77g),加入到含有13.7g 37%HCl的250ml水中。 The above-prepared 4-amino-phenyl-4-aminobenzyl sulfide (7.77g), was added to a solution containing 13.7g 37% HCl in 250ml water. 将该生成的溶液在冰浴中冷却,并加入5.04gNaNO2溶于125ml水中的溶液。 The resulting solution was cooled in an ice bath, and water was added to the solution 125ml 5.04gNaNO2 dissolved. 把该生成的溶液一次加入到炭黑粒料(225g)在2升水(含有280g冰)的快速搅拌的浆料中。 The resultant solution was added to the carbon black pellets (225g) in 2 liters of rapidly stirring slurry (containing 280g of ice) in. 该生成的浆料搅拌过夜并过滤,来收集该炭黑产品。 The resulting slurry was stirred overnight and filtered to collect the carbon black product. 该产品过滤收集、用水然后用乙醇洗涤、过滤收集,并在125℃下干燥至恒重。 The product was collected by filtration, washed with water and then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.38%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.38% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.12mmol/g相连的-(4-C6H4)-S-CH2-(4-C6H4)-基。 Therefore, the carbon black product has 0.12mmol / g attached - (4-C6H4) -S-CH2- (4-C6H4) - groups.

实施例141该实施例进一步介绍本发明炭黑产品的制备。 Example 141 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

按照在Leitch,L.、Baker,B.和Brickman,L.的(Can J.Res.Sect.B),1945年,23卷,第139页中所述一种方法的修改方法,来制备双(4-氨基苯基)硫代磺酸酯。 Follow the instructions in Leitch, L., Baker, B. And Brickman, L.'s (Can J.Res.Sect.B), 1945, the 23, p. 139. A method of modifying the method to prepare double (4-aminophenyl) thiosulfonate. 向硫脲(11.4g)在丙酮(175ml)中充分搅拌的混合物中,加入吡啶(16.85ml),接着加入N-乙酰磺胺酰氯(35.05g)。 The thiourea (11.4g) in acetone (175ml) the mixture was sufficiently stirred, pyridine (16.85ml), was added followed by N- acesulfame chloride (35.05g). 呈黄颜色。 Yellow color. 把该混合物加热至回流,并在这些条件下搅拌80分钟。 The mixture was heated to reflux and stirred under these conditions for 80 minutes. 让该反应冷却到室温,并沉淀出松散的固体。 The reaction was cooled to room temperature, and the precipitated solid was loose. 除去丙酮后,加入500ml热水。 After removal of the acetone, water was added 500ml. 形成淡黄色沉淀,将该沉淀过滤收集,生成22.7g双(4-乙酰氨基苯基)硫代磺酸酯。 A pale yellow precipitate formed, the precipitate was collected by filtration, to generate 22.7g bis (4-acetamidophenyl) thiosulfonate.

按照Bere,C.和Smiles,S.的“化学协会会刊”(J.Chem.Soc.)1924,2359所述方法的改性方法制备所要的成品。 According to Bere, C. And Smiles, S. The "Chemical Society journal" (J.Chem.Soc.) Finished preparing the desired method for modifying the method described 1924,2359. 把上述制备所有双-(4-乙酰氨基苯基)硫代磺酸酯(22.7g)溶解在250ml THF中,并加入250ml 2N HCl。 All the above-prepared bis - (4-acetylamino-phenyl) thio-sulfonate (22.7g) was dissolved in 250ml THF, and adding 250ml 2N HCl. 把该混合物加热至回流,并搅拌5小时。 The mixture was heated to reflux and stirred for 5 hours. 让该反应冷却到室温后,除去大多数THF,并小心加入固体NaHCO3,直到看不到气体放出为止。 The reaction was cooled to room temperature, remove most of THF, and the careful addition of solid NaHCO3, until no gas evolution so far. 形成橙色沉淀,过滤分离该沉淀,生成所希望要的双(4-氨基苯基)硫代磺酸酯(10.3g)。 Orange precipitate formed, the precipitate was separated by filtration, to generate the bis (4-aminophenyl) thio-sulfonate (10.3g) desired.

把如上制备的双(4-氨基苯基)硫代磺酸酯(9.46g),加入到含有13.65g 37%HCl的250ml水中,并在冰浴中冷却该浑浊的黄色混合物。 The bis (4-aminophenyl) thio prepared as above sulfonate (9.46g), was added to a solution containing 13.65g 37% HCl in 250ml water, and the cloudy yellow mixture cooled in an ice bath. 向该混合物中加入5.04g NaNO2溶于125ml水中的溶液。 To this mixture was added a solution of 5.04g NaNO2 dissolved in 125ml of water. 形成黄色凝胶悬浮液。 A yellow gel suspension. 把该生成的混合物一次加入到炭黑粒料(225g)在含有280g冰的2升水中的快速搅拌的浆料中。 The resultant mixture was added to the carbon black pellets (225g) in 2 liters of water containing 280g of ice rapidly stirred slurry. 把该浆料搅拌过夜,并过滤收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水洗涤并过滤收集。 The product was washed with water and collected by filtration. 然后该产品用乙醇洗涤、过滤收集、并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.85%硫,与未处理炭黑含有1.30%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.85% sulfur, and untreated carbon black containing 1.30% sulfur compared. 因此,该炭黑产品有0.086mmol/g相连的-(4-C6H4)-SO2-S-(4-C6H4)-基。 Therefore, the carbon black product has 0.086mmol / g attached - (4-C6H4) -SO2-S- (4-C6H4) - groups.

实施例142该实施例进一步介绍本发明炭黑产品的制备。 Example 142 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双(4-氨基苄基)硫化物。 It was prepared as follows bis (4-aminobenzyl) sulfide. 在充分搅拌下,把4-硝基苄基氯(55.0g)在500ml THF的溶液缓慢加到Na2S9H2O(43.2g)在1升水中的溶液。 Under thorough stirring, the 4-nitrobenzyl chloride (55.0g) was slowly added Na2S 9H2O (43.2g) in a solution of 1 liter of water in 500ml THF was added dropwise. 该混合物在室温下搅拌18小时。 The mixture was stirred at room temperature for 18 hours. 除去THF并过滤,得到46.8g双(4-硝基苄基)硫化物。 THF was removed and filtered to give 46.8g of bis (4-nitrobenzyl) sulfide.

将所有这些物质溶于530ml乙醇中。 All of these substances were dissolved in 530ml of ethanol. 加入水(1.1升),接着加入530ml 2NHCl和69.1g铁粉。 Water (1.1 l), followed by addition of 69.1g 530ml 2NHCl and iron. 强烈搅拌的同时,把该混合物在回流下加热3小时。 While strongly stirring, and the mixture was heated under reflux for 3 hours. 冷却到室温后,加入800ml水,并用1900ml乙酸乙酯分成数次萃取该反应混合物。 After cooling to room temperature, 800ml of water was added, and the reaction mixture was extracted several times into 1900ml with ethyl acetate. 将该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,得到28.9g所希望的双(4-氨基苄基)硫化物。 Ethyl acetate was removed to give 28.9g of the desired bis (4-aminobenzyl) sulfide.

把如上述所制备的双(4-氨基苄基)硫化物加到含有21.3g 37%HCl的700ml水中。 The prepared as bis (4-aminobenzyl) sulfide was added to the above containing 700ml of water and 21.3g 37% HCl. 把该生成的溶液搅拌2小时,然后在冰浴中冷却。 The resultant solution was stirred for 2 hours, then cooled in an ice bath. 加入7.84gNaNO2溶于75ml水中的溶液。 75ml water was added to the solution 7.84gNaNO2 dissolved. 把该生成的棕色凝胶悬浮液一次加入到炭黑粒料(350g)在2.5升含有280g冰的水中的快速搅拌的浆料中。 The resultant brown suspension was added to the gel rapidly stirring slurry of carbon black pellets (350g) in 2.5 liters of water containing 280g of ice. 把该浆料搅拌过夜然后过滤,来收集该炭黑产品。 The slurry was stirred overnight and then filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.34%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.34% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.11mmol/g相连的-(4-C6H4)CH2-S-CH2-(4-C6H4)-基。 Therefore, the carbon black product has 0.11mmol / g attached - (4-C6H4) CH2-S-CH2- (4-C6H4) - groups.

实施例143该实施例进一步介绍本发明炭黑产品的制备。 Example 143 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把如上面实施例142制备的双(4-氨基苄基)硫化物(10.99g)加到含有18.2g 37%HCl的700ml水中。 The embodiments as described above in Example 142 Preparation of bis (4-aminobenzyl) sulfide (10.99g) was added to water containing 700ml of 18.2g 37% HCl. 溶液搅拌2小时后,在冰浴中冷却。 After the solution was stirred for 2 hours, cooled in an ice bath. 加入6.72gNaNO2溶于75ml水中的溶液。 75ml water was added to the solution 6.72gNaNO2 dissolved. 把该生成的棕色凝胶悬浮液一次加入到炭黑粒料(225g)在2升含有280g冰的水中的快速搅拌浆料中。 The resultant brown gel was added to a suspension of carbon black pellets (225g) in 2 liters of ice containing a rapidly stirring slurry of 280g of water. 把该浆料搅拌过夜然后过滤,来收集该炭黑产品。 The slurry was stirred overnight and then filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.40%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.40% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.125mmol/g相连的-(4-C6H4)-CH2-S-CH2-(4-C6H4)-基。 Therefore, the carbon black product has 0.125mmol / g attached - (4-C6H4) -CH2-S-CH2- (4-C6H4) - groups.

实施例144该实施例进一步介绍本发明炭黑产品的制备。 Example 144 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双(3-氨基苄基)硫化物。 Prepared by bis (3-aminobenzyl) sulfide. 在充分搅拌下,把3-硝基苄基氯(55.0g)在500ml THF的溶液缓慢加到Na2S9H2O(43.2g)在1升水中的溶液。 Under thorough stirring, the 3-nitrobenzyl chloride (55.0g) was slowly added Na2S 9H2O (43.2g) in a solution of 1 liter of water in 500ml THF was added dropwise. 该混合物在室温下搅拌18小时。 The mixture was stirred at room temperature for 18 hours. 除去THF并过滤,得到45.8g双(3-硝基苄基)硫化物。 THF was removed and filtered to give 45.8g of bis (3-nitrobenzyl) sulfide.

将所有这些物质溶于530ml乙醇中。 All of these substances were dissolved in 530ml of ethanol. 加入水(1.1升),接着加入140ml 2NHCl和67.64g铁粉。 Water (1.1 l), followed by addition of 140ml 2NHCl and 67.64g iron. 强烈搅拌的同时,把该混合物加热到回流4.5小时。 While strongly stirring, and the mixture was heated to reflux for 4.5 hours. 加入更多的铁粉(15.0g),并在回流下继续反应再1小时。 Adding more iron powder (15.0g), and the reaction was continued under reflux for another 1 hour. 冷却到室温后,用乙酸乙酯萃取该取反应混合物数次。 After cooling to room temperature, extracted with ethyl acetate. The reaction mixture was taken several times. 该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,得到33.1g所希望的双(3-氨基苄基)硫化物。 Ethyl acetate was removed to give 33.1g of the desired bis (3-aminobenzyl) sulfide.

把如上述所制备的双(3-氨基苄基)硫化物加到含有18.2g 37%HCl的400ml水中。 The prepared as bis (3-aminobenzyl) sulfide was added to the above containing 400ml of water and 18.2g 37% HCl. 搅拌2小时后,把该溶液在冰浴中冷却。 After stirring for 2 hours, the solution was cooled in an ice bath. 加入6.72g NaNO2溶于75ml水中的溶液。 75ml water was added to a solution of 6.72g NaNO2 dissolved. 把该生成的棕色凝胶悬浮液一次加入到炭黑粒料(225g)在2升含有280g冰的水中的快速搅拌浆料中。 The resultant brown gel was added to a suspension of carbon black pellets (225g) in 2 liters of ice containing a rapidly stirring slurry of 280g of water. 把该浆料搅拌过夜然后过滤,来收集该炭黑产品。 The slurry was stirred overnight and then filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.50%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.50% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.09mmol/g相连的-(3-C6H4)-CH2-S-CH2-(3-C6H4)-基。 Therefore, the carbon black product has 0.09mmol / g attached - (3-C6H4) -CH2-S-CH2- (3-C6H4) - groups.

实施例145该实施例进一步介绍本发明炭黑产品的制备。 Example 145 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把如上面实施例144制备的双(3-氨基苄基)硫化物加到含有27.32g 37%HCl的500ml水中。 Double the embodiments as described above in Example 144 Preparation of (3-aminobenzyl) sulfide containing 500ml of water was added 27.32g 37% HCl for. 把溶液搅拌2小时后,在冰浴中冷却。 After the solution was stirred for 2 hours, cooled in an ice bath. 加入10.1g NaNO2溶于75ml水中的溶液。 Was added a solution of 10.1g NaNO2 dissolved in 75ml of water. 把该生成的棕色凝胶悬浮液一次加入到炭黑粒料(450g)在3升含有300g冰的水中的快速搅拌浆料中。 The resultant brown gel was added to a suspension of carbon black pellets (450g) in 3 liters of ice containing a rapidly stirring slurry of 300g of water. 把该浆料搅拌过夜然后过滤,来收集该炭黑产品。 The slurry was stirred overnight and then filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.30%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.30% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑产品有0.094mmol/g相连的-(3-C6H4)-CH2-S-CH2-(3-C6H4)-基。 Therefore, the carbon black product has 0.094mmol / g attached - (3-C6H4) -CH2-S-CH2- (3-C6H4) - groups.

实施例146该实施例进一步介绍本发明炭黑产品的制备。 Example 146 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125mL/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125mL / 100g of.

如下制备双(4-氨基苄基)二硫化物。 It was prepared as follows bis (4-aminobenzyl) disulfide. 把4-硝基苄基氯(40.0g)在933mL甲醇和233mL水中的混合物加热到形成溶液。 The 4-nitro-benzyl chloride (40.0g) in a mixture of 933mL of methanol and 233mL water is heated to form a solution. 在充分搅拌下,向该溶液中缓慢加入Na2S2O35H2O(72.34g)在233mL水中的溶液。 Under sufficiently stirred, to this solution was slowly added Na2S2O3 5H2O (72.34g) solution in 233mL water. 该混合物在回流下搅拌4小时。 The mixture was stirred at reflux for 4 hours. 冷却到室温后,除去大多数甲醇,并向该水溶液(约300mL)中加入Na2CO3在600mL水中的溶液。 After cooling to room temperature, most of the methanol was removed, and to 600mL Na2CO3 solution in water was added to the aqueous solution (approximately 300mL) in. 该溶液在室温下搅拌18小时,在这个时间内形成膏状有颜色的不透明的混合物。 The solution was stirred for 18 hours at room temperature, the cream colored opaque mixture formed during this time. 该沉淀物过滤分离并用水洗涤,生成37.1g双(4-硝基苄基)二硫化物。 The precipitate was separated by filtration and washed with water to produce 37.1g bis (4-nitrobenzyl) disulfide.

把双(4-硝基苄基)二硫化物(10.0g)溶解在1.5升乙醇(需要加热到约73℃,然后过滤来得到透明的溶液)。 The bis (4-nitrobenzyl) disulfide (10.0g) was dissolved in 1.5 liters of ethanol (requires heating to about 73 ℃, and then filtered to give a clear solution). 向该热溶液中加入0.5L水、30mL 2N HCl和16.4g铁粉。 To the hot solution was added 0.5L of water, 30mL 2N HCl and 16.4g iron. 然后把温度降到约45℃,并在该温度下继续反应8小时。 The temperature was then reduced to about 45 ℃, and the reaction was continued at this temperature for 8 hours. 接着把该反应混合物加热到回流,并让其继续3.5小时。 The reaction mixture was then heated to reflux for 3.5 hours and allowed to continue. 冷却到室温后,该混合物用乙酸乙酯萃取几次。 After cooling to room temperature, the mixture was extracted with ethyl acetate several times. 该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,生成4.69g所希望要的双(4-氨基苄基)二硫化物。 Ethyl acetate was removed, to generate the desired 4.69g of bis (4-aminobenzyl) disulfide.

把如上所制备的双(4-氨基苄基)二硫化物(9.32g)加到250mL含有13.66g 37%HCl的水中。 The above prepared bis (4-aminobenzyl) disulfide (9.32g) was added to 250mL containing 13.66g 37% HCl in water. 搅拌2小时后,该溶液在冰浴中冷却。 After stirring for 2 hours, the solution was cooled in an ice bath. 加入5.04gNaNO2溶解在125mL水中的溶液。 5.04gNaNO2 dissolved in 125mL of water was added dropwise. 把该混合物一次加入到炭黑粒料(225g)在2升含有280g冰的水中的快速搅拌浆料中。 The mixture was added to the carbon black pellets (225g) in 2 liters of ice containing a rapidly stirring slurry of 280g of water. 该浆料搅拌过夜并过滤来收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

用THF萃取过夜并干燥的炭黑产品含有1.55%硫,与未处理炭黑含有1.00%硫相比较。 THF overnight and dried and extracted with a carbon black product containing 1.55% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑有0.086mmol/g相连的-(4-C6H4)-CH2-SS-CH2-(4-C6H4)-基。 Therefore, the carbon black has 0.086mmol / g attached - (4-C6H4) -CH2-SS-CH2- (4-C6H4) - groups.

实施例147该实施例进一步介绍本发明炭黑产品的制备。 Example 147 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双(3-氨基苄基)二硫化物。 Prepared by bis (3-aminobenzyl) disulfide. 在充分搅拌下,向3-硝基苄基氯(40.0g)在933mL甲醇和233mL水中的溶液中缓慢加入Na2S2O35H2O(72.34g)在233mL水中的溶液。 In the thoroughly stirred solution of 3-nitro-benzyl chloride (40.0g) was slowly added Na2S2O3 5H2O (72.34g) solution in 233mL water solution 933mL of methanol and 233mL of water. 该生成的混合物在回流下搅拌4小时。 The resulting mixture was stirred at reflux for 4 hours. 冷却到室温后,除去大多数甲醇,并用乙酸乙酯萃取该水相层。 After cooling to room temperature, most of the methanol was removed, and the aqueous phase extracted with ethyl acetate layer. 从该水相层除去水,得到69.04g3-硝基苄基硫代硫酸酯的钠盐。 The aqueous phase from the water layer was removed, to obtain a sodium salt 69.04g3- nitrobenzyl thiosulfate ester.

在充分搅拌下,把Na2CO3(124.83g)在1升水中的溶液逐渐加入到3-硝基苄基硫代硫酸酯的钠盐(39.21g)在800mL水中的溶液中。 Under thorough stirring, the Na2CO3 (124.83g) in 1 liter of water was gradually added to the sodium salt of 3-nitrobenzyl thiosulfate ester (39.21g) in 800mL water solution. 该溶液在室温下搅拌18小时后,形成膏状有颜色的不透明的混合物。 The solution was stirred at room temperature for 18 hours, the mixture formed a paste opaque color. 该沉淀物过滤分离并用水洗涤,生成16.8g双(3-硝基苄基)二硫化物。 The precipitate was separated by filtration and washed with water to produce 16.8g bis (3-nitrobenzyl) disulfide.

把双(3-硝基苄基)二硫化物(7.5g)溶解在1.5升乙醇(需要加热,然后过滤来得到透明的溶液)。 The bis (3-nitrobenzyl) disulfide (7.5g) was dissolved in 1.5 liters of ethanol (heating is required, and then filtered to give a clear solution). 向该热溶液中加入750mL水、22.5mL2N HCl和12.3g铁粉。 To the hot solution was added 750mL of water, 22.5mL2N HCl and 12.3g iron. 然后把该反应进一步加热到刚低于其回流温度,并继续加热5小时。 The reaction was then further heated to just below its reflux temperature, and heating was continued for 5 hours. 冷却到室温后,加入400ml水,然后该混合物用乙酸乙酯萃取几次。 After cooling to room temperature, 400ml of water was added, and the mixture was extracted several times with ethyl acetate. 该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,生成5.15g所希望要的双(3-氨基苄基)二硫化物。 Ethyl acetate was removed, to generate the desired 5.15g of bis (3-aminobenzyl) disulfide.

把如上所制备的双(3-氨基苄基)二硫化物(9.99g)加到250mL含有14.6g37%HCl的水中。 The above prepared bis (3-aminobenzyl) disulfide (9.99g) was added to 250mL of water containing 14.6g37% HCl. 搅拌2小时后,该溶液在冰浴中冷却。 After stirring for 2 hours, the solution was cooled in an ice bath. 加入5.4g NaNO2溶解在125mL水中的溶液。 Add 5.4g NaNO2 dissolved in 125mL of water was added. 把该混合物一次加入到炭黑粒料(241g)在2升含有280g冰的水中的快速搅拌浆料中。 The mixture was added to the carbon black pellets (241g) in 2 liters of ice containing a rapidly stirring slurry of 280g of water. 该浆料搅拌过夜并过滤以收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用乙醇然后用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product is then washed with ethanol, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品含有1.62%硫,与未处理炭黑含有1.00%硫相比较。 It has overnight and dried carbon black product extracted with THF containing 1.62% sulfur, and untreated carbon black containing 1.00% sulfur compared. 因此,该炭黑有0.097mmol/g相连的-(3-C6H4)-CH2-SS-CH2-(3-C6H4)-基。 Therefore, the carbon black has 0.097mmol / g attached - (3-C6H4) -CH2-SS-CH2- (3-C6H4) - groups.

实施例148该实施例进一步介绍现场制备本发明炭黑产品的方法。 Example 148 This example further describes the method of the present invention prepared in situ carbon black product. 使用碘值为120mg/g、DBPA为125mL/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125mL / 100g of.

如下制备N-吗啉代-(4-氨基苯基)亚磺酰胺。 N- morpholino was prepared as follows - (4-aminophenyl) sulfenamide. 把I2(14.2g)在乙醇(300mL)中的溶液,加到充分搅拌的含有4-二氨基苯基二硫化物(13.9g)和吗啉(24.4g)在乙醇(300mL)中的溶液中。 The I2 (14.2g) in ethanol (300mL) in, added to the well stirred comprising 4-aminophenyl disulfide (13.9g) and morpholine (24.4g) in ethanol (300mL) solution of . 该反应混合物在室温下搅拌3小时。 The reaction mixture was stirred at room temperature for 3 hours. 除去乙醇,得到稠的、近乎黑色的油。 The ethanol was removed to give a thick, nearly black oil. 把该油再次溶解在750mL乙酸乙酯中,并用水洗涤数次。 And the oil was redissolved in 750mL ethyl acetate and washed with water several times. 该乙酸乙酯层在Na2SO4上干燥并过滤。 The ethyl acetate layer was dried over Na2SO4 and filtered. 除去乙酸乙酯,得到19.6g所希望要的N-吗啉代-(4-氨基苯基)亚磺酰胺。 Ethyl acetate was removed to give 19.6g of the desired N- morpholino - (4-aminophenyl) sulfenamide.

把如上述制得的N-吗啉代-(4-氨基苯基)亚磺酰胺(9.46g)加到充分搅拌的炭黑(225g)、冰(280g)和水(2升)的混合物中。 The above prepared N- morpholino - (4-aminophenyl) sulfenamide (9.46g) was added to a stirred solution of carbon black sufficient (225g), ice (280g) and water (2 liters) was . 向该溶液加入3.36gNaNO2溶于75mL水中的溶液,接着加入37%HCl(4.66g)在75mL水中的溶液。 To this solution was added a solution of 75mL 3.36gNaNO2 dissolved in water, followed by addition of 37% HCl (4.66g) in a solution of 75mL of water. 将该浆料搅拌5小时、过滤收集该炭黑产品,并在125℃下干燥至恒重。 The slurry was stirred for 5 hours, filtered to collect the carbon black product, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.26%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.26% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.02mmol/g相连的-(4-C6H4)-S-NRR′基团,其中RR′是-CH2CH2OCH2CH2-。 Therefore, the carbon black product has 0.02mmol / g attached - (4-C6H4) -S-NRR 'group, where RR' is -CH2CH2OCH2CH2-.

实施例149该实施例进一步介绍现场制备本发明炭黑产品的方法。 Example 149 This example further describes the method of the present invention prepared in situ carbon black product. 使用碘值为120mg/g、DBPA为125mL/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125mL / 100g of.

把如上面实施例148制备的N-吗啉代-(4-氨基苯基)亚磺酰胺(9.46g)加到充分搅拌的炭黑(225g)、冰(280g)和水(2升)的混合物中。 The above, as prepared in Example 148 N- morpholino - (4-aminophenyl) sulfenamide (9.46g) was added to a stirred solution of carbon black sufficient (225g), ice (280g) and water (2 liters) mixture. 向该溶液加入3.36gNaNO2溶于75mL水中的溶液,接着加入37%HCl(9.32g)在75mL水中的溶液。 To this solution was added a solution of 3.36gNaNO2 dissolved in 75mL of water, followed by addition of 37% HCl (9.32g) in a solution of 75mL of water. 该浆料搅拌5小时、过滤收集该炭黑产品,并在125℃下干燥至恒重。 The slurry was stirred for 5 hours, filtered to collect the carbon black product, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.34%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.34% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.04mmol/g相连的-(4-C6H4)-S-NRR′基团,其中RR′是-CH2CH2OCH2CH2-。 Therefore, the carbon black product has 0.04mmol / g attached - (4-C6H4) -S-NRR 'group, where RR' is -CH2CH2OCH2CH2-.

实施例150该实施例进一步介绍本发明炭黑产品的制备方法。 Example 150 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备双[2-(4-氨基苯磺酰氨基)乙基]二硫化物。 It was prepared as follows bis [2- (4-amino-benzenesulfonylamino) ethyl] disulfide. 向在冰浴中的充分搅拌的N-乙酰磺胺酰氯(1.26g)在50mLCH2Cl2的溶液中,加入三乙胺(559mg),接着加入胱胺(2,2′-二氨基乙基二硫化物,400mg)。 In an ice bath to a stirred solution of N- sufficiently acesulfame chloride (1.26g) in 50mLCH2Cl2 was added triethylamine (559mg), followed by cystamine (2,2'-aminoethyl disulfide, 400mg). 撤去冰浴,该反应在室温下搅拌18小时。 The ice bath was removed and the reaction was stirred at room temperature for 18 hours. 除去CH2Cl2,得到棕黄色固体,该固体在50mL水中强烈搅拌3小时并过滤,得到1.24g双[2-(4-乙酰氨基苯磺酰氨基)乙基]二硫化物。 Remove CH2Cl2, to give a tan solid which was stirred vigorously in 50mL water for 3 hours and filtered to afford 1.24g bis [2- (4-acetylamino-benzenesulfonylamino) ethyl] disulfide.

把双[2-(4-乙酰氨基苯磺酰氨基)乙基]二硫化物(1.00g)在40mL乙醇和40mL 2N HCl的混合物中加热至回流,并在该温度下搅拌3小时。 The bis [2- (4-acetylamino-benzenesulfonylamino) ethyl] disulfide (1.00g) was heated to reflux in 40mL of ethanol and 40mL 2N HCl the mixture, and stirred at this temperature for 3 hours. 冷却到室温后,加入200mL水,并通过小心加入固体NaHCO3来使该混合物呈碱性。 After cooling to room temperature, was added 200mL of water, and by the careful addition of solid NaHCO3 to make the mixture alkaline. 形成白色沉淀,用乙酸乙酯(2150mL)萃取该碱性水相层来分离该沉淀。 A white precipitate formed, the basic aqueous layer extracted with ethyl acetate (2 150mL) to separate the precipitate. 该合并的乙酸乙酯萃取物在Na2SO4上干燥并过滤。 The combined ethyl acetate extracts were dried and filtered over Na2SO4. 除去乙酸乙酯,得到735mg所希望要的双[2-(4-氨基苯磺酰氨基)乙基]二硫化物。 Ethyl acetate was removed to give 735mg of the desired bis [2- (4-amino-benzenesulfonylamino) ethyl] disulfide.

把如上面制备的双[2-(4-氨基苯磺酰氨基)乙基]二硫化物(15.6g)加到275mL含有13.6g 37%HCl的水中,该混合物在冰浴中冷却。 Bis [2- (4-amino-benzenesulfonylamino) ethyl] disulfide was prepared as the above (15.6g) was added to 275mL water containing 13.6g 37% HCl, and the mixture was cooled in an ice bath. 接着,把5.04gNaNO2溶解在60mL水中的溶液加到该混合物中。 Then, the 5.04gNaNO2 dissolved in 60mL of water was added to the mixture. 把该生成的黄色浆料一次性地加入到炭黑粒料(225g)在1.2升水中的快速搅拌浆料中。 The resultant yellow slurry was added in one portion to the carbon black pellets (225g) in 1.2 liters of water rapidly stirred slurry. 该浆料搅拌过夜并过滤,来收集炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水洗涤、过滤收集,并在100℃下干燥至恒重。 The product was washed with water, collected by filtration and dried at 100 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有2.06%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.06% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.07mmol/g相连的-(4-C6H4)-SO2NH-CH2CH2-SS-CH2CH2-NHSO2-(4-C6H4)-基。 Therefore, the carbon black product has 0.07mmol / g attached - (4-C6H4) -SO2NH-CH2CH2-SS-CH2CH2-NHSO2- (4-C6H4) - groups.

实施例151该实施例进一步介绍本发明炭黑产品的制备。 Example 151 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

按照在Truce,W.、Roberts,F的“有机化学杂志”(J.Org.Chem.)1963,28,961中所述方法的改性方法制备2-(4-氨基苯基)-1,3-二噻烷(dithiane)。 In accordance Truce, W., Roberts, F the "Journal of Organic Chemistry" (J.Org.Chem.) Method of modifying the 1963,28,961 Preparation of 2- (4-aminophenyl) -1, 3- dithiane (dithiane). 向充分搅拌的4-乙酰氨基苯甲醛(12.7g)在200mL乙酸中的混合物中加入MgCl2(5.57g),接着加入1,3-丙二硫醇(8.44g)。 To a well stirred solution of 4-acetylamino-benzaldehyde (12.7g) in a mixture of 200mL of acetic acid was added MgCl2 (5.57g), followed by addition of 1,3-propanedithiol (8.44g). 当加入二硫醇时,该反应混合物变白。 When adding dithiol, the reaction mixture turns white. 该混合物在室温下搅拌2小时。 The mixture was stirred at room temperature for 2 hours. 将该白色沉淀过滤分离,用水洗涤几次并干燥,得到12.5g 2-(4-乙酰氨基苯基)-1,3-二噻烷。 The white precipitate was isolated by filtration, washed several times with water and dried to give 12.5g 2- (4- acetylamino-phenyl) -1,3-dithiane.

全部12.5g 2-(4-乙酰氨基苯基)-1,3-二噻烷溶解在150mL乙醇中。 All 12.5g 2- (4- acetylamino-phenyl) -1,3-dithiane was dissolved in 150mL of ethanol. 加入总量为150mL的2N HCl,把该反应混合物加热至回流。 Was added a total of 150mL of 2N HCl, the reaction mixture is heated to reflux. 在该温度下反应6小时后,让该透明的黄色溶液冷却到室温,然后用稀NaOH溶液使其成碱性。 After the reaction at this temperature for 6 hours, so that the clear yellow solution was cooled to room temperature and then made basic with dilute NaOH solution. 该生成的亮黄色沉淀物过滤分离,用水洗涤至中性,并干燥得到14.8g所希望要的2-(4-氨基苯基)-1,3-二噻烷。 The resulting bright yellow precipitate was separated by filtration, washed with water until neutral, and dried to give 2- (4-aminophenyl) -1,3-dithiane 14.8g desired.

把上述所制备的2-(4-氨基苯基)-1,3-二噻烷(7.13g)加到250mL含有6.83g 37%HCl的水中,并在冰浴中冷却。 The above prepared 2- (4-aminophenyl) -1,3-dithiane (7.13g) was added 6.83g 37% HCl containing 250mL of water, and cooled in an ice bath. 加入2.52gNaNO2溶于125mL水中的溶液。 2.52gNaNO2 dissolved solution was added 125mL of water. 把该混合物一次加入到炭黑粒料(225g)在2升含有200g冰的水中的快速搅拌浆料中。 The mixture was added to the carbon black pellets (225g) in 2 liters of ice containing a rapidly stirring slurry of 200g of water. 该浆料搅拌4.5小时并过滤,来收集该炭黑产品。 The slurry was stirred for 4.5 hours and filtered to collect the carbon black product. 该产品用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product was washed with water, collected by filtration and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.65%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.65% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.07mmol/g相连的-(4-C6H4)-2-(1,3-二噻烷)基。 Therefore, the carbon black product has 0.07mmol / g attached - (4-C6H4) -2- (1,3- dithiane) groups.

实施例152该实施例进一步介绍本发明炭黑产品的制备。 Example 152 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把上面实施例151所制备的2-(4-氨基苯基)-1,3-二噻烷(4.75g)加到250mL含有4.55g 37%HCl的水中。 2- (4-aminophenyl) prepared in Example 151, the above embodiment -1,3-dithiane (4.75g) was added to 250mL containing 4.55g 37% HCl in water. 接着在冰浴中冷却,并加入1.68gNaNO2溶于125mL水中的溶液。 Then cooled in an ice bath, and add 1.68gNaNO2 dissolved in 125mL water was added. 把该混合物一次加入到炭黑粒料(112.5g)在2升含有100g冰的水中的快速搅拌浆料中。 The mixture was added to the carbon black pellets (112.5g) in 2 liters of ice containing a rapidly stirring slurry of 100g of water. 该浆料搅拌4.5小时并过滤,来收集该炭黑产品。 The slurry was stirred for 4.5 hours and filtered to collect the carbon black product. 该产品用水洗涤、过滤收集,并在125℃下干燥至恒重。 The product was washed with water, collected by filtration and dried at 125 ℃ to constant weight.

用THF萃取过夜并干燥的炭黑产品样品含有1.47%硫,与未处理炭黑含有1.21%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.47% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.04mmol/g相连的-(4-C6H4)-2-(1,3-二噻烷)基。 Therefore, the carbon black product has 0.04mmol / g attached - (4-C6H4) -2- (1,3- dithiane) groups.

实施例153该实施例进一步介绍现场制备本发明炭黑产品。 Example 153 This example further introduce a carbon black product of the present invention prepared in situ. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

如下制备N,N′-双(4-氨基苯基)-哌嗪基亚磺酰胺。 Prepared by N, N'- bis (4-aminophenyl) - piperazine sulfenamide. 在室温下,把I2(21.6g)在800mL乙醇中的溶液加到充分搅拌的4,4-二氨基苯基二硫化物(21.3g)和哌嗪(36.7g)在1升乙醇中的溶液中。 At room temperature, I2 (21.6g) in 800mL of ethanol was added to a stirred solution of 4,4-well aminophenyl disulfide (21.3g) and piperazine (36.7g) in 1 liter of ethanol was in. 该黑色反应混合物在该温度下搅拌16小时,然后过滤。 The black reaction mixture was stirred for 16 hours at this temperature, and then filtered. 该膏状有颜色的沉淀用水洗涤并过滤,得到25.1g所要的N,N′-双(4-氨基苯基)-哌嗪基亚磺酰胺。 The cream colored precipitate was washed with water and filtered to give 25.1g of the desired N, N'- bis (4-aminophenyl) - piperazine sulfenamide.

把如上面制备的N,N′-双-(4-氨基苯基)-哌嗪基亚磺酰胺(11.2g)加到充分搅拌的炭黑(225g)、冰(280g)和水(2升)的混合物中。 As described above the preparation of N, N'- bis - (4-aminophenyl) - piperazine sulfenamide (11.2g) was added to a stirred solution of the carbon black sufficiently (225g), ice (280g) and water (2 liters ) mixture. 向该混合物中加入5.04g NaNO2溶于75mL水中的溶液,接着加入37%HCl(13.65g)在75mL水中的溶液。 To this mixture was added 5.04g NaNO2 dissolved in 75mL water was added, followed by addition of 37% HCl (13.65g) in a solution of 75mL of water. 该浆料搅拌过夜并过滤,收集该炭黑产品。 The slurry was stirred overnight and filtered to collect the carbon black product. 该产品用水洗涤、过滤,并在125℃干燥至恒重。 The product was washed with water, filtered and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.91%硫,与未处理炭黑含有1.21%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.91% sulfur, and untreated carbon black containing 1.21% sulfur compared. 因此,该炭黑产品有0.11mmol/g相连的-(4-C6H4)-S-(1,4-C4H8N2)-S-(4-C6H4)-基。 Therefore, the carbon black product has 0.11mmol / g attached - (4-C6H4) -S- (1,4-C4H8N2) -S- (4-C6H4) - groups.

实施例154该实施例进一步介绍本发明炭黑产品的制备。 Example 154 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把双(4-氨基苯基)二硫化物(4.19g)溶于230mL含有7.32g 37%HCl的水中。 The bis (4-aminophenyl) disulfide (4.19g) was dissolved in 230mL containing 7.32g 37% HCl in water. 然后该溶液在冰浴中冷却,并加入2.64g NaNO2溶于40mL水中的溶液。 The solution was then cooled in an ice bath, and the solution was added 2.64g NaNO2 dissolved in 40mL water. 把该混合物一次加到炭黑粒料(225g)在1200mL含有少量冰的水中的快速搅拌浆料中。 The mixture was added to a carbon black pellets (225g) in 1200mL rapidly stirring slurry containing a small amount of ice water. 该浆料搅拌2小时并过滤,来收集该炭黑产品。 The slurry was stirred for 2 hours and filtered to collect the carbon black product. 该产品用乙醇、然后用水洗涤,过滤收集,并在125℃干燥至恒重。 The product with ethanol, then washed with water, collected by filtration, and dried at 125 ℃ to constant weight.

用THF萃取过夜并干燥的炭黑产品样品含有1.55%硫,与未处理炭黑含有1.10%硫相比较。 Dried overnight and the carbon black product extracted with THF sample contained 1.55% sulfur, and untreated carbon black containing 1.10% sulfur compared. 因此,该炭黑产品有0.07mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-基。 Therefore, the carbon black product has 0.07mmol / g attached - (4-C6H4) -SS- (4-C6H4) - groups.

实施例155该实施例进一步介绍本发明炭黑产品的制备。 Example 155 This example further illustrate the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把双(4-氨基苯基)二硫化物(8.55g)溶于180mL含有14.65g 37%HCl的水中。 The bis (4-aminophenyl) disulfide (8.55g) was dissolved in 180mL containing 14.65g 37% HCl in water. 然后该溶液在冰浴中冷却,并加入50mL乙醇,接着加入5.28gNaNO2溶于35mL水中的溶液。 The solution was then cooled in an ice bath, and added 50mL of ethanol, followed by the addition 5.28gNaNO2 dissolved in a solution of 35mL of water. 把该混合物分几次加到炭黑粒料(225g)在1200mL含有少量冰的水中的快速搅拌浆料中。 The mixture was added in several portions carbon black pellets (225g) in 1200mL containing a rapidly stirring slurry of a small amount of ice water. 该浆料搅拌2小时并过滤,来收集该炭黑产品。 The slurry was stirred for 2 hours and filtered to collect the carbon black product. 该产品用乙醇、然后用水洗涤,过滤收集,并在125℃干燥至恒重。 The product with ethanol, then washed with water, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有1.82%硫,与未反应炭黑含有1.10%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 1.82% sulfur, unreacted carbon black and containing 1.10% sulfur compared. 因此,该炭黑产品有0.11mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-基。 Therefore, the carbon black product has 0.11mmol / g attached - (4-C6H4) -SS- (4-C6H4) - groups.

实施例156该实施例进一步介绍本发明炭黑产品的制备。 Example 156 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把双(4-氨基苯基)二硫化物(11.18g)溶于560mL含有19.53g 37%HCl的水中。 The bis (4-aminophenyl) disulfide (11.18g) was dissolved in 560mL containing 19.53g 37% HCl in water. 然后该溶液在冰浴中冷却,并加入7.04g NaNO2溶于60mI水中的溶液。 The solution was then cooled in an ice bath, and the solution was added 7.04g NaNO2 dissolved 60mI water. 加入另外150mL水,并把该混合物一次加到炭黑粒料(225g)在1200mL含有少量冰的水中的快速搅拌浆料中。 Further 150mL water was added, and the mixture was added a carbon black pellets (225g) in 1200mL containing a rapidly stirring slurry of a small amount of ice water. 该浆料搅拌2小时并过滤,来收集该炭黑产品。 The slurry was stirred for 2 hours and filtered to collect the carbon black product. 该产品用乙醇、然后用水洗涤,过滤收集,并在125℃干燥至恒重。 The product with ethanol, then washed with water, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有2.26%硫,与未反应炭黑含有1.10%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.26% sulfur, unreacted carbon black and containing 1.10% sulfur compared. 因此,该炭黑产品有0.18mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-基。 Therefore, the carbon black product has 0.18mmol / g attached - (4-C6H4) -SS- (4-C6H4) - groups.

实施例157该实施例进一步介绍本发明炭黑产品的制备。 Example 157 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把双(4-氨基苯基)二硫化物(13.97g)溶于560mL 含有24.4g 37%HCl的水中。 The bis (4-aminophenyl) disulfide (13.97g) was dissolved in 560mL containing 24.4g 37% HCl in water. 然后该溶液在冰浴中冷却,并加入8.80gNaNO2溶于60mL水中的溶液。 The solution was then cooled in an ice bath, and added 8.80gNaNO2 in solution 60mL water. 加入另外150mL水,并把该生成的混合物一次加到炭黑粒料(225g)在1200mL含有少量冰的水中的快速搅拌浆料中。 Additional 150mL of water, and the resulting mixture was first added to the carbon black pellets (225g) in 1200mL rapidly stirring slurry containing a small amount of ice water. 该浆料搅拌3.5小时并过滤,来收集该炭黑产品。 The slurry was stirred for 3.5 hours and filtered to collect the carbon black product. 该产品用乙醇、然后用水洗涤,过滤收集,并在125℃干燥至恒重。 The product with ethanol, then washed with water, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有2.50%硫,与未反应炭黑含有1.10%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.50% sulfur, unreacted carbon black and containing 1.10% sulfur compared. 因此,该炭黑产品有0.22mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-基。 Therefore, the carbon black product has 0.22mmol / g attached - (4-C6H4) -SS- (4-C6H4) - groups.

实施例158该实施例进一步介绍本发明炭黑产品的制备。 Example 158 This example further describes the preparation of carbon black products of the present invention. 使用碘值为120mg/g、DBPA为125ml/100g的炭黑。 Using an iodine value of 120mg / g, DBPA of the carbon black 125ml / 100g of.

把双(4-氨基苯基)二硫化物(17.1g)溶于175mL含有29.30g 37%HCl的水中。 The bis (4-aminophenyl) disulfide (17.1g) was dissolved in 175mL containing 29.30g 37% HCl in water. 然后该生成的溶液在冰浴中冷却,并加入10.6gNaNO2溶于60mL水中的溶液。 Then, the resulting solution was cooled in an ice bath, and add 10.6gNaNO2 dissolved in 60mL water was added. 加入100mL乙醇,并把该混合物一次加到炭黑粒料(225g)在1200mL含有少量冰的水中的快速搅拌浆料中。 100mL ethanol was added, and the mixture was added a carbon black pellets (225g) in 1200mL rapidly stirring slurry containing a small amount of ice water. 该浆料搅拌2小时并过滤,来收集该炭黑产品。 The slurry was stirred for 2 hours and filtered to collect the carbon black product. 该产品用乙醇、然后用水洗涤,过滤收集,并在125℃干燥至恒重。 The product with ethanol, then washed with water, collected by filtration, and dried at 125 ℃ to constant weight.

已用THF萃取过夜并干燥的炭黑产品样品含有2.55%硫,与未反应炭黑含有1.10%硫相比较。 It has overnight and dried carbon black product extracted with THF sample contained 2.55% sulfur, unreacted carbon black and containing 1.10% sulfur compared. 因此,该炭黑产品有0.23mmol/g相连的-(4-C6H4)-SS-(4-C6H4)-基。 Therefore, the carbon black product has 0.23mmol / g attached - (4-C6H4) -SS- (4-C6H4) - groups.

实施例159对比炭黑产品在该对比例中,把实施例118-158中的炭黑用水、乙醇和水洗涤,接着干燥,来制得对比炭黑产品。 Example 159 Comparative Carbon Black Products In this comparative example, the water, and washed with ethanol and water in the carbon black in Example 118-158, followed by drying, to obtain comparative carbon black product.

实施例160对比炭黑产品在该对比例中,不加改变地使用实施例118-158中所用的炭黑产品,并作为对比炭黑产品。 Example 160 Comparative Carbon Black Products In this comparative example, without change Example 118-158 used in the carbon black products, and as a contrast to carbon black products.

炭黑产品在橡胶配方中的应用实施例118-158中所述的炭黑产品可用在各种弹性体中。 Carbon black products carbon black products in rubber formulations described in Example 118-158 implement applications available in a variety of elastomers. 该弹性体包括,但不局限于下列类型:溶液型SBR(丁苯橡胶)、官能化的(锡偶合和/和化学改性和/或其他官能化作用)溶液型SBR、天然橡胶、乳液SBR、聚丁二烯和三元共聚物。 The elastomers include, but are not limited to the following types: solution type SBR (styrene butadiene rubber), functionalized (tin coupling and / or chemical modification and / or other functionalization) solution type SBR, natural rubber, emulsion SBR , polybutadiene, and terpolymers. 这些弹性体可单独可作为共混物出现在橡胶配方中。 These elastomers may be used alone as a blend appear in rubber formulations.

NS116和NS114是可从日本的Nippon Zeon购得的化学改性的锡偶合的溶液型SBR。 NS116 and NS114 are available from Nippon Zeon of Japan chemically modified tin coupled solution type SBR. Duradene 715是溶液型SBR。 Duradene 715 is the solution type SBR. Duradene是购自Akron OH,Firestone的SBR产品的注册商标。 Duradene is available from Akron OH, Firestone registered trademark of SBR products. S1216是从Akron OH的Goodyear轮胎和橡胶公司买到的溶液型SBR。 S1216 is from Akron OH of Goodyear Tire & Rubber Company available solution type SBR. SBR-1500是购自LA,Baton Rouge,Copolymer Rubber and Chemical Corp.的乳液SBR。 SBR-1500 is available from LA, Baton Rouge, Copolymer Rubber and Chemical Corp. emulsion SBR. SL-574是购自日本的日本合成橡胶公司(Japan Synthetic Rubber Co.)(JSR)的锡偶合的溶液型SBR。 SL-574 is available from Japan Synthetic Rubber Company of Japan (Japan Synthetic Rubber Co.) (JSR) tin coupled solution type SBR. RTC0585和TO0587也是JSR买到的化学改性的SBR。 RTC0585 and TO0587 is available JSR chemically modified SBR. Flexzone是购自CT.Naugatuck,Uniroyal Chemical的抗降解剂产品的注册商标。 Flexzone is available from CT.Naugatuck, antidegradants products registered trademark of Uniroyal Chemical. CBS是N-环己基苯并噻唑基亚磺酰胺,MBT是2-巯基苯并噻唑,以及DTDM是N,N′-二硫代二吗啉。 CBS is N- cyclohexyl benzothiazole sulfenamide, MBT is 2-mercaptobenzothiazole thiazole, and DTDM is N, N'- dithiodimorpholine morpholine.

实施例161-166这些实施例介绍在两种不同的橡胶配方中使用实施例118、121、122和对比例160中的炭黑产品。 This section describes two different rubber formulations Examples 161-166 These examples and Comparative Example 118,121,122 160 carbon black products. 聚合物在布雷本登密炼机中100℃下密炼1分钟。 Polymers Brabender mixer at 100 ℃ mixing for 1 minute. 把该炭黑产品或对比炭黑加入,并密炼另外3分钟,或直到温度达到160℃。 The carbon black product or comparative carbon black was added, and mixing an additional 3 minutes, or until the temperature reaches 160 ℃. 然后该混合物卸料,并通过开炼机3次。 The mixture was then discharge, and through an open mill 3 times. 该混合物在室温放置2小时后,把其转移回布雷本登密炼机中,100℃下混炼1分钟。 After the mixture was left at room temperature for 2 hours, to transfer it back to the Brabender mixer, 100 ℃ kneaded for 1 minute. 1分钟后,加入ZnO和硬脂酸,并混炼2分钟,然后加入Flexzone 7P抗降解剂,并混炼另外1分钟,或直到温度达到160℃。 After 1 minute, ZnO and stearic acid was added, and kneaded for 2 minutes and then Flexzone 7P antidegradants added and kneaded additional 1 minute, or until the temperature reached 160 ℃. 然后卸下样品,通过开炼机三次,并让其在室温下放置2小时。 Then remove the sample through an open mill three times, and allowed to stand at room temperature for 2 hours. 把该样品返回到布雷本登密炼机中并在100℃混炼1分钟。 The sample was returned to the Brabender mixer and kneaded at 100 ℃ for 1 minute. 然后加入硫化剂并混炼1分钟,然后卸下样品,并通过开炼机三次。 Vulcanizing agent is then added and kneaded for 1 minute, then remove the sample and through an open mill three times. 所用的配方选自表I。 The formula used is selected from Table I.

表II的数据表明本发明炭黑产品可用于橡胶配方中。 The data in Table II show that carbon black products of the present invention can be used in rubber formulations. 在使用NS-116和NS-114的共混物的情况下,100%模量、结合橡胶、拉伸强度、硬度和耐磨耗性可显著增加,而Tanδ显著降低。 In the case of NS-116 and NS-114 blends and 100% modulus, bound rubber, tensile strength, hardness and wear resistance can be significantly increased, while Tanδ significantly reduced. 在Duradene 715中,可得到较高的模量、硬度和结合橡胶,同时拉伸强度,断裂伸长率和70℃的Tanδ降低。 In the Duradene 715, a higher modulus, hardness, and bound rubber, while the tensile strength, elongation at break and Tanδ 70 ℃ lower. 效果的程度取决于连到炭黑产品上的具体基。 Even to the extent of the effect depends on the specific product groups on the carbon black.

实施例167-180这些实施例介绍在不同的橡胶配方中使用实施例121-124和对比例160中的炭黑产品。 Example 167-180 These examples are described in Example 121-124 and Comparative carbon black products in 160 different rubber formulations. 除了那些含有DTDM的配方外,根据实施例161-166中所述的方法,使用选自表I的配方制备橡胶混合物。 In addition to those formulations containing DTDM outside, according to the method described in Example 161-166, using formulations selected from Table I was prepared rubber mixture. 对那些含有DTDM的橡胶混合物在混炼程序中有稍稍一些变化。 There are slight changes in the mixing process in a number of rubber compounds containing DTDM of those. 在这种情况下,加入Flexzone 7P之后,把含有DTDM的样品混炼3分钟,之后,按照实施例161-166所述的程序进行混炼。 In this case, after the addition Flexzone 7P, the sample containing DTDM kneaded 3 minutes, after which, according to the procedure described in Example 161-166 was kneaded.

表III的性能数据表明:本发明的炭黑产品可用于不同橡胶配方中。 Table III performance data showed that: a carbon black product of the present invention can be used in different rubber formulations. 具体地,当在配方中使用天然橡胶、SBR-1500或Duradene 715时,实施例4和5所述的炭黑产品降低了70℃的Tanδ。 In particular, when used in the formulation of natural rubber, SBR-1500, or Duradene 715, the carbon black product in Example 4 and 5 the reduced 70 ℃ of Tanδ. 另外,向含有实施例4和5的炭黑产品的橡胶配方中加入0.8phr DTDM得到硫化橡胶,与未加入DTDM的配方相比,具有更高的硬度、模量和结合橡胶。 In addition to the rubber formulations containing carbon black products of Examples 4 and 5 were added 0.8phr DTDM vulcanized rubber, compared with no added DTDM the formula, with higher hardness, modulus and bound rubber. 也造成较低的伸长率和70℃的Tanδ,并且通常得到更大的拉伸强度和提高的耐磨性。 Also results in lower elongation and Tanδ 70 ℃, and typically greater tensile strength and improved wear resistance.

实施例181-188这些实施例介绍在几种不同的橡胶配方中使用实施例120、126、139和140和对比例160中的炭黑产品。 Example 181-188 These examples are described in Example 120,126,139 and 140 and 160 on the proportion of carbon black products in several different rubber formulations. 根据实施例161-166中所述的方法,使用选自表I的配方制备这些橡胶混合物。 The method described in Example 161-166, using formulations selected from Table I, the preparation of these rubber compounds.

表IV的性能数据表明:本发明炭黑可用于几种不同的橡胶配方中。 The performance data in Table IV show that: the present invention can be used in several different black rubber formulations. 具体地,在NS-116和NS-114的共混物中,使用实施例120、126、139和140中的炭黑产品,使结合橡胶增加,70℃的Tanδ显著降低。 Specifically, the NS-116 and NS-114 blends, Example 120,126,139 and 140 carbon black products, the bound rubber increased significantly reduces the Tanδ 70 ℃. 在Duradene中,实施例9和23中所介绍的炭黑产品特别适宜于减少70℃的Tanδ。 In Duradene in Example 9 and 23 in Example described carbon black products are particularly suitable for the reduction Tanδ 70 ℃.

实施例189-196这些实施例介绍在几种不同的橡胶配方中使用实施例123、127、134和136和对比例159中的炭黑产品。 Example 189-196 These examples are described in Example 123,127,134 and 136 and 159 in the proportion of carbon black products in several different rubber formulations. 根据下述方法,使用选自表I的配方来制备这些橡胶混合物。 According to the following method, these rubber compounds were prepared using formulations selected from Table I.

聚合物在布雷本登密炼机中100℃下密炼1分钟。 Polymers Brabender mixer at 100 ℃ mixing for 1 minute. 加入ZnO和该炭黑产品或对比炭黑的混合物,并混炼另外2分钟。 ZnO was added and the mixture of carbon black product or comparative carbon black and mixing an additional 2 minutes. 加入硬脂酸和Flexzone 7P抗降解剂,并混炼另外2分钟。 Add stearic acid and Flexzone 7P antidegradants, and kneaded additional 2 minutes. 把该样品卸料并通过开炼机3次。 The discharge of the sample and through an open mill 3 times. 把该样品冷却,并转移回布雷本登密炼机中,且在100℃下混炼1分钟。 The cooling of the sample, and transferred back to the Brabender mixer and kneaded at 100 ℃ 1 min. 然后加入硫化剂组合物,继续混炼1分钟,并把该样品卸料,然后通过开炼机3次。 Then vulcanizing agent composition continue mixing for 1 minute, and the discharge of the sample, and then through an open mill 3 times.

表V表明:这些炭黑产品可用于几种不同的橡胶配方中,包括官能化和未官能化的溶液型SBR。 Table V shows that: these carbon black products can be used in several different rubber formulations including functionalized and unfunctionalized solution type SBR. 另外,在S-1216、Duradene 715和NS-116中使用实施例123所述的炭黑产品,得到较低的70℃的Tanδ值及较高的结合橡胶。 Further, in the S-1216, Duradene 715 NS-116 and using carbon black product described in Example 123 to give the lower 70 ℃ Tanδ value and higher bound rubber. 当与NS-114配合时,实施例127的炭黑产品具有更高的模量、结合橡胶和耐磨性、更低的伸长率和70℃的Tanδ,以及相等的拉伸强度和硬度。 When the carbon black products with NS-114, Example 127 has a higher modulus, bound rubber and abrasion resistance, lower elongation and Tanδ 70 ℃, and equal tensile strength and hardness.

实施例197-200这些实施例介绍在两个不同的橡胶配方中使用实施例129和135和对比例160中的炭黑产品。 Example 197-200 These examples are described in Example 129, and 135 and 160 on the proportion of carbon black products in two different rubber formulations. 根据实施例189-196中所述的方法,使用选自表I的配方制备橡胶混合物。 The method described in Example 189-196, using formulations selected from Table I was prepared rubber mixture.

表VI表明:这些炭黑产品可用于这些使用官能化或未官能化的溶液型SBR的橡胶配方中。 Table VI shows that: these carbon black products can be used in the use of these functionalized or unfunctionalized solution type SBR rubber formulations. 当使用NS-116和NS-114共混物时,观察到结合橡胶。 When using the NS-116 and NS-114 blends observed bound rubber. 也可看到70℃Tanδ和伸长相当显著地减少。 It can also be seen quite significantly reduced 70 ℃ Tanδ and elongation. 在Duradene 715中,当拉伸强度、断裂时的伸长、70℃的Tanδ全部显著减小时,模量增加。 In Duradene 715, when all significantly reduced tensile strength, elongation, Tanδ 70 ℃ at break, modulus increases.

实施例201-205这些实施例介绍在不同橡胶配方中使用实施例155和对比例160中的炭黑产品。 Example 201-205 These examples are described in Example 155 and 160 of the proportion of carbon black products in different rubber formulations. 根据实施例189-196所述的方法,使用选自表I的配方,制备橡胶混合物。 According to the procedure described in Example 189-196, the formulations selected from Table I, the preparation of the rubber mixture.

表VII表明该炭黑产品可用于许多橡胶配方中,特别是含有NR、乳液SBR或选自SL-574、RCTO-586或TO-587官能化的溶液型SBR。 Table VII shows that this carbon black product can be used in a number of rubber formulations, particularly those containing NR, emulsion SBR, or selected from SL-574, RCTO-586 or TO-587 type functionalized solution SBR.

实施例206-215这些实施例介绍在两个橡胶配方中使用实施例154-158和对比例159中的炭黑产品。 Example 206-215 These examples are described in Example 154-158 and Comparative 159 carbon black products in two rubber formulations. 根据实施例189-196所述的方法、使用选自表I的配方,制备橡胶混合物。 According to the procedure described in Example 189-196, the formulations selected from Table I, the preparation of the rubber mixture.

通过研究下表VIII的数据可知,实施例154-158中的炭黑产品所例举的宽范围处理程度可影响橡胶的性能特征。 Studies by the following data in Table VIII shows that the degree of processing a wide range of embodiments 154-158 exemplified carbon black products may affect the performance characteristics of rubber.

实施例216-221这些实施例介绍在两个橡胶配方中使用实施例137、138和对比例160中的炭黑产品。 Example 216-221 These examples are described in Example 137, 138 and 160 of the proportion of carbon black products in two rubber formulations. 根据实施例161-166所述的方法,使用选自表I的配方制备这些橡胶混合物。 According to the method of Example 161-166 using formulations selected from Table I Preparation of a mixture of these rubbers.

表IX表明:这些炭黑产品可用于包括官能化和未官能化的溶液型SBR的几种橡胶配方中。 Table IX indicates that: These carbon black products can be used to include functional and non-functional solution type SBR several rubber formulations. 具体地,实施例137、138和141的炭黑产品在两个橡胶体系中都显示出较低的70℃的Tanδ和高的结合橡胶。 Specifically, embodiment 137, 138 and 141 in two rubber carbon black product systems have shown Tanδ 70 ℃ lower and higher bound rubber. 另外,实施例137和138的产品也表现出耐磨性的提高。 In addition, the product of Example 137 and 138 also showed improvement of wear resistance.

实施例222-235这些实施例介绍在三个橡胶配方中使用实施例142-147和对比例160中的炭黑产品。 Example 222-235 These examples are described in Example 160, 142-147 and Comparative carbon black products in three rubber formulations. 根据实施例161-166中所述的方法,使用选自表I的配方制备这些橡胶混合物。 The method described in Example 161-166, using formulations selected from Table I, the preparation of these rubber compounds.

表X表明:这些炭黑产品可用于所研究的橡胶配方。 Table X shows that: these carbon black products can be used in rubber formulations studied. 具体的,在官能团化的和具有可比较硬度的未官能化溶液型SBR中,所有被研究的炭黑表现出70℃的Tanδ值的减小和结合橡胶的增加。 Specifically, in functionalized and having comparable hardness unfunctionalized solution type SBR, all carbon blacks studied showed a reduction and bound rubber Tanδ value of 70 ℃ of the increase. 在天然橡胶中测得可比较硬度和70℃的Tanδ值,同时实施例146中的炭黑产品表现出Tanδ上最显著的减少。 Compare the measured value hardness and Tanδ 70 ℃ in natural rubber, while Example 146 carbon black products showed the most significant decrease Tanδ.

实施例236-246这些实施例介绍在两个橡胶配方中使用实施例148-153和对比例160中的炭黑产品。 Example 236-246 These examples are described in Example 160, 148-153 and Comparative carbon black products in two rubber formulations. 根据实施例161-166中所述的方法,使用选自表I的配方,制备这些橡胶混合物。 The method described in Example 161-166, using formulations selected from Table I, a mixture of these rubbers prepared.

表XI表明这些炭黑产品可用于橡胶配方中。 Table XI shows that these carbon black products can be used in rubber formulations. 例如,当实施例148、149和153中的炭黑产品配合在Duradene 715或NS-116和NS-114的70/30共混物中,一般来说,耐磨性不变或提高了,同时降低了70℃的Tanδ值。 For example, when 148, 149 and 153 in the embodiment of the carbon black products fit Duradene 715 or NS-116 and NS-114 70/30 blend, in general, the same or improved abrasion resistance, while Tanδ reduced value of 70 ℃.

实施例247-262这些实施例介绍在各种橡胶配方中使用实施例119、125、128和130-133以及对比例160中的炭黑产品。 Examples 247-262 These examples described in Example 119,125,128 160 and 130-133 and the proportion of carbon black products in various rubber formulations. 根据实施例161-166中所述的方法,使用选自表I的配方,制备这些橡胶混合物。 The method described in Example 161-166, using formulations selected from Table I, a mixture of these rubbers prepared.

表XII表明这些炭黑产品可用于橡胶配方中。 Table XII shows that these carbon black products can be used in rubber formulations. 例如,当实施例119的炭黑产品与Duradene 715、SBR-1 500或NS-116和NS-114的共混物配合时,提高了耐磨性,同时降低了70℃的Tanδ值并增加了结合橡胶的百分数。 For example, when the carbon black product and Duradene 715 Example 119, SBR-1 500 or NS-116 and NS-114 blends with improved abrasion resistance, while reducing Tanδ value of 70 ℃ and increased combined with the percentage of rubber. 在Duradene 715和天然橡胶中使用实施例130-133的炭黑产品表明:这类炭黑的各种处理水平可影响炭黑的性能特征。 The use of natural rubber in Duradene 715 and Example 130-133 carbon black products show: these various processing levels can affect the performance characteristics of carbon black carbon black.

实施例263炭黑产品的制备把表面积为230m2/g、DBPA为70m2/g的10g炭黑加到3.06g溴化3-氨基-N-乙基吡啶鎓在72g水中的搅拌溶液中。 Example 263 Preparation of a carbon black product of the surface area of 230m2 / g, DBPA of 10g carbon black 70m2 / g was added 3.06g -N- ethyl-3-amino-brominated pyridinium stirred solution of 72g of water. 加入浓硝酸(1.62g),并把该混合物搅拌并加热到约70℃。 Was added concentrated nitric acid (1.62g), and the mixture was stirred and heated to about 70 ℃. 在几分钟内,加入1.07g NaNO2在约5g水中的溶液。 Within minutes, was added 1.07g NaNO2 in about 5g of water was added. 现场生成重氮盐N2C5H4N(C2H5)++,该盐与炭黑反应。 Diazonium salt generated in situ N2C5H4N (C2H5) ++, the salt reacted with the carbon black. 在该反应混合物搅拌1小时后,在烘箱中125℃下干燥该样品。 After the reaction mixture was stirred for 1 hour in an oven at 125 ℃ dried sample. 该产品的平均体积粒径为0.18微米。 Volume average particle diameter of the product was 0.18 microns. 该产品有相连的3-C5H4N(C2H5)+基。 The product has connected 3-C5H4N (C2H5) + group.

实施例264制备炭黑产品把3-氨基-N-甲基吡啶鎓碘化物(3.92g)溶解在70g水中。 Example 264 Preparation of a carbon black product of the 3-amino -N- methylpyridinium iodide (3.92g) was dissolved in 70g water. 加入2.58gAgNO3在6g水中的溶液。 2.58gAgNO3 solution was added 6g water. 搅拌15分钟后,过滤除去该沉淀,并加入表面积为230m2/g、DBPA为70m2/g的炭黑。 After stirring for 15 minutes, the precipitate was removed by filtration, and added to a surface area of 230m2 / g, DBPA of 70m2 / g of carbon black. 加入浓硝酸,该混合物搅拌并加热到约70℃。 Concentrated nitric acid was added, and the mixture was stirred and heated to about 70 ℃. 在几分钟内加入1.07g NaNO2在约5g水中的溶液。 1.07g NaNO2 in about 5g of water was added in minutes. 现场生成重氮盐N2C5H4CH2N(CH3)++,该重氮盐与炭黑反应。 Diazonium salt generated in situ N2C5H4CH2N (CH3) ++, the reaction of the diazonium salt with the carbon black. 放出气泡。 Release bubbles. 该反应混合物在70℃下搅拌约40分钟后,然后沸腾约15分钟。 The reaction mixture was stirred at 70 ℃ for about 40 minutes, then boil for about 15 minutes. 该样品在烘箱中125℃下干燥。 125 ℃ dried the sample in an oven. 该产品的平均体积粒径为0.23微米。 Volume average particle diameter of the product was 0.23 microns. 该产品的325目残余物为0.0%,与未处理炭黑的94%相比较。 This product has a 325 mesh residue of 0.0%, compared with 94% of the untreated carbon black. 该炭黑产品有相连的3-C5H4N(CH3)+基。 The carbon black product had attached 3-C5H4N (CH3) + groups.

实施例265 Example 265

炭黑产品的制备在25分钟内,把50g苄基三甲基氯化铵加到90%的冷硝酸中。 Preparation of carbon black products within 25 minutes to 50g of benzyl trimethyl ammonium chloride was added to a cold 90% nitric acid. 该混合物在低于10℃下保持5小时。 The mixture was kept below 10 ℃ at five hours. 加入冰(500g),并用KOH中和该混合物。 Addition of ice (500g), and the mixture was neutralized with KOH. 过滤除去沉淀。 The precipitate was removed by filtration. 加入乙醇(1L)并再次过滤该混合物。 Was added ethanol (1L) and the mixture was filtered again. 从滤液中回收3-硝基苄基三甲基硝酸铵。 Recycling 3-nitrobenzyl trimethyl ammonium nitrate from the filtrate. 由NMR测得该材料的纯度为75%。 Measured by NMR purity of the material was 75%. 把10g 3-硝基苄基三甲基硝酸铵、14g铁屑、2g浓HCl和400g水的混合物沸腾2.5小时。 The mixture 10g 3- nitrobenzyl trimethyl ammonium nitrate, 14g iron, 2g of concentrated HCl and 400g of water boiling for 2.5 hours. 该混合物用KOH中和并过滤,得到硝酸/氯化3-氨基苄基三甲基铵。 The mixture was neutralized with KOH and filtered to give the nitrate / chloride, 3-amino-benzyl trimethyl ammonium.

把14g表面积为230m2/g、DBPA为70m2/g的炭黑加到3.06g硝酸/氯化3-氨基苄基三甲基铵在72g水中的搅拌溶液中。 14g of the surface area of 230m2 / g, DBPA of 70m2 / g of carbon black was added 3.06g nitrate / chloride, 3-amino-benzyl trimethyl ammonium stirred solution of 72g of water. 加入浓硝酸(1.62g),该混合物搅拌并加热到约70℃。 Was added concentrated nitric acid (1.62g), and the mixture was stirred and heated to about 70 ℃. 在几分钟内,加入1.07g NaNO2在约5g水中的溶液。 Within minutes, was added 1.07g NaNO2 in about 5g of water was added. 现场生成重氮盐3-N2C6H4NC(CH3)++,该重氮盐与炭黑反应。 Field diazonium salt 3-N2C6H4NC (CH3) ++, the reaction of the diazonium salt with the carbon black. 该反应混合物搅拌1小时后,在烘箱中125℃干燥该样品。 After the reaction mixture was stirred for 1 hour in an oven dried sample was 125 ℃. 该产品的平均体积粒径为0.18微米。 Volume average particle diameter of the product was 0.18 microns. 该产品连上了3-N2C6H4CH2N(CH3)3+基。 The product on the 3-N2C6H4CH2N (CH3) 3+ groups.

实施例266制备炭黑产品把亚硝酸银(30.9g)加到41.4g氯化N-(4-氨基苯基)吡啶鎓在700g水中的溶液中,并把该混合物在70℃下搅拌1.5小时。 Example 266 Preparation of a carbon black product Silver nitrite to (30.9g) was added to 41.4g chloride N- (4- aminophenyl) pyridinium solution in 700g of water, and the mixture was stirred at 70 ℃ 1.5 小时. 把该混合物过滤,并加入表面积为200m2/g、DBPA为122mL/100g的炭黑。 The mixture was filtered, and added to a surface area of 200m2 / g, DBPA of the carbon black 122mL / 100g of. 加入另外1升水和20g浓HCl。 An additional 1 liter of water and 20g of concentrated HCl. 现场生成重氮盐N2C6H4NC5H5++,该重氮盐与炭黑反应。 Diazonium salt generated in situ N2C6H4NC5H5 ++, the diazonium salt reacted with the carbon black. 放出气泡。 Release bubbles. 该分散液在70-80℃下搅拌2.5小时,然后在烘箱中125℃下干燥。 The dispersion was stirred for 2.5 hours at 70-80 ℃, and then dried in an oven at 125 ℃. 该产品连上了C6H4NC5H5+基。 The product on the C6H4NC5H5 + group.

实施例267炭黑产品的制备在对美国专利2,821,526的方法的一个改进中,在室温下把250g对乙酰氨基苯甲酰甲基氯、65g三甲胺和约600g水的混合物搅拌3天。 Example 267 Preparation of carbon black products in an improvement of U.S. Patent No. 2,821,526 for a method of, at room temperature, the mixture was 250g acetaminophen benzoyl chloride, 65g trimethylamine and about 600g of water was stirred for 3 days. 加入另外5g三甲胺在15g水中的溶液,并在60℃下加热该混合物2小时。 An additional 15g 5g trimethylamine solution in water, and the mixture was heated for 2 hours at 60 ℃. 冷却和过滤后,加入201g浓HCl,把该溶液煮沸1小时。 After cooling and filtration, was added 201g of concentrated HCl, the solution was boiled for 1 hour. 冷却后,加入4L丙酮,收集固体状的氯化4-氨基苯甲酰甲基三甲基铵的盐酸盐。 After cooling, 4L of acetone, collected solid 4-aminobenzoyl chloride trimethyl ammonium hydrochloride. 把氯化4-氨基苯甲酰甲基三甲基胺的盐酸盐(10.1g)悬浮在50mL乙醇中。 The 4-aminobenzoyl chloride hydrochloride trimethyl amine (10.1g) was suspended in 50mL of ethanol. 加入另外4.1g三乙胺,该混合物搅拌40分钟,并在回流下加热1小时。 An additional 4.1g of triethylamine, and the mixture was stirred for 40 minutes, and heated at reflux for 1 hour. 把氯化4-氨基苯甲酰甲基三甲基铵过滤收集并用乙醇洗涤。 The 4-aminobenzoyl chloride trimethyl ammonium collected by filtration and washed with ethanol.

把氯化4-氨基苯甲酰甲基三甲基铵(2.51g)溶解在水中。 The 4-aminobenzoyl chloride trimethyl ammonium (2.51g) was dissolved in water. 加入亚硝酸银(1.69g),该混合物在70℃下加热1小时。 Silver nitrite (1.69g), and the mixture was heated at 70 ℃ 1 hour. 过滤掉沉淀后,加入表面积为230m2/g、DBPA为70ml/100g的炭黑。 The precipitate was filtered off, add a surface area of 230m2 / g, DBPA of the carbon black 70ml / 100g of. 加入水使体积升至约100mL。 Water was added to bring the volume to about 100mL. 加入浓HCl(1.1g),并在搅拌下70℃时加热该分散液1小时。 Concentrated HCl (1.1g), and stirred at 70 ℃ dispersion was heated 1 hour. 现场生成重氮盐N2C6H4COCH2N(CH3)3++,该重氮盐与炭黑反应。 Diazonium salt generated in situ N2C6H4COCH2N (CH3) 3 ++, the reaction of the diazonium salt with the carbon black. 放出气泡。 Release bubbles. 该产品连有C6H4COCH2N(CH3)3+基。 The product has C6H4COCH2N (CH3) 3+ groups.

实施例268炭黑产品的制备把2.12g 4-乙酰氨基苯甲酰甲基氯、0.83g吡啶和6.4g二甲基亚砜的溶液搅拌过夜。 Preparation of carbon black products of Example 268 2.12g 4- acetylamino embodiment the benzoyl chloride, 0.83g of pyridine and 6.4g of dimethylsulfoxide was stirred overnight. 加入另外0.8g吡啶和1g二甲基亚砜后,该溶液搅拌另外5小时。 An additional 0.8g of pyridine and 1g dimethylsulfoxide, the solution was stirred for additional 5 hours. 加入醚(50mL),并过滤收集氯化乙酰氨基苯甲酰甲基吡啶鎓。 Ether (50mL), and collected by filtration acetylamino phenacyl chloride pyridinium. 把氯化乙酰氨基苯甲酰甲基吡啶鎓溶于水中,过滤该溶液,并加入1.7g浓HCl。 The phenacyl chloride acetylamino pyridinium dissolved in water, the solution was filtered, and added 1.7g of concentrated HCl. 该溶液煮沸1小时后,进行冷却,加入丙酮,过滤收集氯化4-氨基苯甲酰甲基吡啶鎓的盐酸盐。 After the solution was boiled for one hour, cooled, acetone was added, 4-aminobenzoyl chloride was collected by filtration methyl pyridinium hydrochloride. 把2g氯化4-氨基苯甲酰甲基吡啶鎓的盐酸盐溶于15g水中,并加入4.5g碱性离子交换树脂(Amberlite IRA400-OH)。 The 4-aminobenzoyl chloride 2g methylpyridinium hydrochloride were dissolved in 15g of water and added to 4.5g basic ion exchange resin (Amberlite IRA400-OH). 搅拌后,过滤除去该树脂,收集水溶液状的4-氨基苯甲酰甲基吡啶鎓氯化物。 After stirring, the resin was removed by filtration, to collect the aqueous solution of 4-aminobenzoyl-methyl pyridinium chloride.

把1.3g 4-氨基苯甲酰甲基吡啶鎓氯化物在25g水中的溶液在回流下和1g亚硝酸银一起加热约90分钟。 The 1.3g 4- aminobenzoyl-methyl-pyridinium chloride solution in 25g water and 1g reflux heated with silver nitrite for about 90 minutes. 过滤除去沉淀。 The precipitate was removed by filtration. 加入5g表面积为200m2/g、DBPA为122mL/100g的炭黑,并把该混合物加热到约80℃。 5g of a surface area of 200m2 / g, DBPA of the carbon black 122mL / 100g and the mixture was heated to about 80 ℃. 加入浓HCl(0.52g),并把该分散液搅拌另外1.5小时。 Concentrated HCl (0.52g), and to the dispersion was stirred for an additional 1.5 hours. 现场生成重氮盐N2C6H4COCH2(NC5H5)++,该重氮盐与炭黑反应。 Diazonium salt generated in situ N2C6H4COCH2 (NC5H5) ++, the reaction of the diazonium salt with the carbon black. 该产品连有C6H4COCH2(NC5H5)+基。 The product has C6H4COCH2 (NC5H5) + group.

表I橡胶配方 Table I rubber formulation

<p>表II <P> Table II

表III Table III

<p>表IV <P> Table IV

<p>表V <P> Table V

实施例炭黑产品配方100%模量Mpa300%模量Mpa拉伸强度Mpa伸长肖氏硬度A结合橡胶Tanδ0℃Tanδ70℃研磨机指数14%滑移研磨机指数21%滑移189123K4.8518.3118.563126530.20.3730.1688599190134K3.8715.5020.653836425.80.3950.1778966比较例159K4.0117.0319.643366227.30.4500.176100100191123E4.25--15.072606232.30.3750.17588110192134E4.6118.5021.803496029.40.4010.1989091比较例159E4.9619.7320.663155930.70.4300.194100100193123B3.62--23.333866930.860.2780.14192104比较例159B3.42--23.414026928.360.2970.146100100194127B4.04--18.5229460350.2890.137110113比较例159B3.2514.0918.363856028.10.3270.173100100195136B3.61--20.944476227.7--0.1655979比较例159B3.53--22.083876324.2--0.157100100196136E5.10--15.572846326.3--0.1714174比较例159E4.54--20.563166321.4--0.179100100</table> </tables> 100% modulus Mpa300% modulus carbon black product formulations embodiment Mpa Tensile strength Mpa Elongation Shore A combination of rubber Tanδ0 ℃ Tanδ70 ℃ grinder index 14% 21% slip grinder index slip 189123K4.8518.3118.563126530.20 .3730.1688599190134K3.8715.5020.653836425.80.3950.1778966 Comparative Comparative Example Example 159K4.0117.0319.643366227.30.4500.176100100191123E4.25--15.072606232.30.3750.17588110192134E4.6118.5021.803496029.40.4010.1989091 159E4.9619.7320.663155930.70.4300.194100100193123B3.62--23.333866930. 860.2780.14192104 159B3.42--23.414026928.360.2970.146100100194127B4.04--18.5229460350.2890.137110113 Comparative Example Comparative Example Comparative Example 159B3.2514.0918.363856028.10.3270.173100100195136B3.61--20.944476227.7--0.1655979 159B3.53--22.083876324 .2--0.157100100196136E5.10--15.572846326.3--0.1714174 Comparative Example 159E4.54--20.563166321.4--0.179100100 </ table> </ tables>

表VII<tables id="table29" num="029"> <table width="1141">实施例炭黑产品配方100%模量Mpa300%模量Mpa拉伸强度Mpa伸长肖氏硬度A结合橡胶Tanδ0℃Tanδ70℃研磨机指数14%滑移研磨机指数21%滑移201155I3.5614.9123.634687433.80.2910.1928385比较例160I3.4015.5726.954927434.20.3270.201100100202155G2.7714.1930.135677234.10.2390.1298784比较例160G3.7617.9131.155047243.20.2410.117100100203155L3.7713.3619.143257539.10.2730.12492114比较例160L2.9613.3921.224307337.30.3000.149100100204155M3.2310.3114.094207417.90.7900.1796873比较例160M2.619.5017.645257117.50.8190.246100100205155N3.2213.1923.1253678330.3320.185104103比较例160N3.8315.0619.544088027.10.3540.225100100</table> </tables> 100% modulus Mpa300% modulus Table VII <tables id = "table29" num = "029"> <table width = "1141"> Example of carbon black product formulations Mpa Tensile strength Mpa Elongation Shore A combination of rubber Tanδ0 ℃ Tanδ70 ℃ mill grinder index 14% slip slip 201155I3.5614.9123.634687433.80.2910.1928385 index 21% Comparative Example Comparative Example 160I3.4015.5726.954927434.20.3270.201100100202155G2.7714.1930.135677234.10.2390.1298784 160G3.7617.9131.155047243.20.2410.117100100203155 L3.7713.3619.143257539.10.2730.12492114 160L2.9613.3921.224307337.30.3000.149100100204155M3.2310.3114.094207417.90.7900.1796873 Comparative Example Comparative Example Comparative Example 160M2.619.5017.645257117.50.8190.246100100205155N3.2213.1923.1253678330.3320.185104103 160N3.8315.0619.544088027.10.3540.225100100 </ table> </ tables>

表VIII Table VIII

p><p>表IX p> <p> Table IX

</tables> </ Tables>

表X Table X

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表XI<tables id="table33" num="033"> <table width="1174">实施例炭黑产品配方100%模量Mpa300%模量Mpa拉伸强度Mpa伸长肖氏硬度A结合橡胶Tanδ0℃Tan δ70℃研磨机指数14%滑移研磨机指数21%滑移236148D3.6518.3621.303397343.60.6030.122120101237149D3.60--17.242877343.70.6350.124120114238150D3.67--15.472807336.70.6470.1208576239151D3.7417.6520.993487338.90.6180.149133115240152D3.3616.5020.773587340.10.6510.14811794241153D3.83--16.082637351.00.5890.111104108比较例160D3.7618.9420.393187338.40.6240.138100100242148E3.5215.2115.872667349.30.4300.13693134243149E3.18--15.402807346.50.4310.145104113244150E3.48--15.572927338.40.4120.1406895245151E2.8114.3519.543827143.50.4460.17295112246153E4.96--10.631737839.80.4060.13653100比较例160E2.79--12.872617045.60.4620.164100100</table> </tables> Table XI <tables id = "table33" num = "033"> <table width = "1174"> 100% modulus carbon black product formulations embodiment Mpa300% modulus Mpa Tensile Strength Mpa Elongation Shore A combination of rubber Tanδ0 ℃ Tan δ70 ℃ grinder index 14% 21% slip grinder index slip 236148D3.6518.3621.303397343.60.6030.122120101237149D3.60--17.242877343.70.6350.124120114238150D3.67--15.472807336.70.6470.1208576239151D3.7417.6520.993487338.90. 6180.149133115240152D3.3616.5020.773587340.10.6510.14811794241153D3.83--16.082637351.00.5890.111104108 Comparative Example 160D3.7618.9420.393187338.40.6240.138100100242148E3.5215.2115.872667349.30.4300.13693134243149E3.18--15.402807346.50.4310.145104113244150E3.48--15.572927338. 40.4120.1406895245151E2.8114.3519.543827143.50.4460.17295112246153E4.96--10.631737839.80.4060.13653100 Comparative Example 160E2.79--12.872617045.60.4620.164100100 </ table> </ tables>

表XII Table XII

<p>实施例269制备炭黑产品把3.56g NaNO2在水中的冷溶液加到10.2g 4,4′-亚甲基二苯胺、140g水和19.7g浓HCl(在冰浴中搅拌下)的溶液中。 <P> Example 269 Preparation of a carbon black product of the cold solution of 3.56g NaNO2 in water was added to 10.2g 4,4'- methylenedianiline, 140g water and 19.7g concentrated HCl (stirring in an ice bath) of solution. 搅拌约15分钟后,把生成的重氮盐溶液加到200g炭黑在1.6L在室温下搅拌的水中的悬浮液中。 After stirring for about 15 minutes, the diazonium salt solution was added 200g of carbon black in 1.6L of water at room temperature with stirring suspension. 该炭黑的表面积为55m2/g、DBPA为46mL/100g。 The surface area of the carbon black is 55m2 / g, DBPA of 46mL / 100g. 搅拌1.5小时后,该混合物用NaOH中和并过滤。 After stirring for 1.5 hours, the mixture was neutralized with NaOH and filtered. 该炭黑产品用水洗涤并在烘箱中125℃下干燥。 The carbon black product was washed with water and dried in an oven at 125 ℃. 用THF进行Soxhlet萃取过夜的炭黑产品含有0.332%氮,与未处理炭黑含有0.081%氮相比较。 Subjected to Soxhlet extraction with THF overnight carbon black product contains 0.332% nitrogen, with the untreated carbon black containing 0.081% nitrogen compared. 因此,该炭黑产品有0.081mmol/g相连的C6H4CH2C6H4NH2基。 Therefore, the carbon black product has 0.081mmol / g attached C6H4CH2C6H4NH2 group.

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Classifications
International ClassificationC09C1/56, C09C3/08, D06M11/74, D01F1/04, D21H17/69, C09D11/00, C09D11/02, C09B39/00, D06P1/44, C09D5/02, D21H21/28, C08K9/04, C09D11/18, C08L21/00, C09C1/58, C09D7/00, D01F11/14, C01B
Cooperative ClassificationC01P2004/62, Y10S524/925, D21H17/69, D06P1/44, C09C3/08, C04B2235/424, C09C1/56, C04B35/63, C09D11/324, D06M11/74, C01P2006/12, C09B39/00, C09D11/037, C09D7/007, C01P2006/19, C09D11/18, C08K9/04, C09D5/028, C04B2235/425, D21H21/285, C09C1/58, D01F11/14, C09C1/565
European ClassificationC08K9/04, C09D11/037, C09D11/324, C09C1/56B, D06P1/44, D01F11/14, C09C3/08, D06M11/74, C09D5/02K8, C09D7/00P, C09C1/56, C09B39/00, C09C1/58, D21H17/69, C09D11/18, C04B35/63
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