CA1252937A - Vulcanizable filled halo rubber with isothiuronium - Google Patents
Vulcanizable filled halo rubber with isothiuroniumInfo
- Publication number
- CA1252937A CA1252937A CA000455215A CA455215A CA1252937A CA 1252937 A CA1252937 A CA 1252937A CA 000455215 A CA000455215 A CA 000455215A CA 455215 A CA455215 A CA 455215A CA 1252937 A CA1252937 A CA 1252937A
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- CA
- Canada
- Prior art keywords
- parts
- rubber
- weight
- mixture according
- halo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/5406—Silicon-containing compounds containing elements other than oxygen or nitrogen
Abstract
ABSTRACT OF THE DISCLOSURE
The present Inventlon relates to vulcanlzable halo-rub-ber mlxtures, whlch contaln sllicon-contalnlng Isothlronlum com-pounds In addltlon to slllcate flllers, and to a process for vul-canlzlng and cross-llnklng these mlxtures. The rubber mlxtures and thelr vulcanlzates are useful in the productlon of Industrlal rubber articles such as cable sheathlngs, tubes, alr tubes, transmlsslon belts, cone belts, conveyor belts, roll covers, gas-kets, electric Insulatlons, llnlngs, Impregnatlons and coatlngs of heat-reslstant fabrlcs, damplng and vlbratlon elements and slmllar artlcles whlch have to satlsfy hlgh requlrements wlth regard to reslstance to hlgh temperatures and oll reslstance.
The present Inventlon relates to vulcanlzable halo-rub-ber mlxtures, whlch contaln sllicon-contalnlng Isothlronlum com-pounds In addltlon to slllcate flllers, and to a process for vul-canlzlng and cross-llnklng these mlxtures. The rubber mlxtures and thelr vulcanlzates are useful in the productlon of Industrlal rubber articles such as cable sheathlngs, tubes, alr tubes, transmlsslon belts, cone belts, conveyor belts, roll covers, gas-kets, electric Insulatlons, llnlngs, Impregnatlons and coatlngs of heat-reslstant fabrlcs, damplng and vlbratlon elements and slmllar artlcles whlch have to satlsfy hlgh requlrements wlth regard to reslstance to hlgh temperatures and oll reslstance.
Description
~Z~i~93'7 The present invention relates to vulcanizable halo-rubber mixtures containing a silicate filler, when re~uired in mix-ture with carbon black, and at least one silicon-containing iso-thiuronium compound and to a process for vulcanizing and cross-linking these mixtures.
It is known that in rubber mixtures vulcanized wi~h sul-phur which are to contain a high proportion of silicate fillers, as for example, precipitated silica, a silane is required as a mix-ture component in order to impart sufficiently good properties to the vulcanizates.
DE-AS 28 19 638 describes that from silicate-filler-con-taining rubber mixtures based on halogen-containing rubber types valuable vulcanization products are forrned when the mixtures con-tain specific halogen-containing silanes.
These mixtures according to the prior art frequently con-tain compounds from the thiourea class as vulcanization accelerators.
It has now been found that vulcanization products having improved properties are surprisingly produced from these known halo-rubber mixtures when a silicon-containing isothiuronium compound is incorporated instead of a halogen-containing silane and an accelera-tor from the thiourea class.
The present invention thus provides vulcanizable rubber mixtures containing at least one halo rubber, a silicate filler and, when required, a halo silane and also contain at least one isothi-uronium compound having the formula ~ NP~ R4 I ~RO)3 n~nSiCmH2mS =C\ 5 6 NR R
in which X~represents chloride, bromide or iodide, m represents a number from 1 to 6, R represents a Cl- to c5-alkyl group, a C5- or C6-cycloalkyl group or the phenyl group, R represents a Cl- to C
alkyl group, a C5- or C6-cycloalkyl group, the ~methoxy-ethyl group~
93~
the phenyl group or the benzyl group, n represents 0, 1 or 2, R , R4, R5 and R6 are identical or dif~erent and represent hydrogen, a .
C~ to C~-alkyl group or R , R5 represent hydrogen, R , R6 are identical or different and represent hydrogen, a C5- to C6-cycloalkyl group, the phenyl group or the benzyl group or R4 and R6 represent a coherent C2- to C4-alkylene chain, in amounts from 0.1 to 5 parts by weight relative to 100 parts by weight of the halo rubber.
The isothiuronium compounds which according to the pre-sent invention must be present in the halo rubber mixtures either singly or in mixuture in amounts of 0.1 to 5 parts by weight, pre-ferably 0.1 to 2.0 parts by weight, relative to 100 parts by weight of halo rubber, include particularly the compounds which, bonded to the silicon atom, contain a triethoxy, trimethoxy, or a diethoxy-methyl, dimethoxy methyl group, wherein Cm~2m is ethyl, propyl or butyl and in which the isothiuronium group on the nitrogen atom is substituted by two methyl or ethyl groups or by a hydrogen atom, a methyl, ethyl, butyl, or phenyl group and wherein the hydrocarbon radicals can be identical or different.
Said organosilanes used according to the present invention are obtained by means of conventional processes ~rom thiourea deri-vatives having the formula II S=C /
where R , R , R5 and R6 are as above and from halo silanes havingthe formula III (RO RlSiC H X
where R7 Rl, X, m and n are as above.
Methods of production a~e described, for example, in U.S.
Patents ~os. 3,215,718 and 3, 314, 982 or in German Patent NQ . 2,120,002.
The composition of basic halo-rubber mixtures is known to a person skilled in the art. By basic mixtures are meant products like those described, for example, in DE-AS 28 19 63a in ignorance of the favourable possibilities of using silicon-containing iso-thiuronium compounds according to formula I. The proportion of the individual mixture components can be varied within wide limits.
When using the silicon-containing isothiuronium compounds the admixture of elementary sulphur as in the above basic mixtures is dispensed with. Furthermore, apart from the isothiuronium com-pounds according to formula I no further accelerators are required.
Free halosilane~ according to formula III can be presentin the vulcani~able mixture according to the present invention in amounts of 0 to 3 parts by weight, but is preferably absent.
The applicable halo rubbers include, for example~ halo-genated butyl rubber, particularly brominated or chlorinated butyl rubber, chloro rubber, rubber hydrochlorides and preferably halo-genated butyl rubber and particularly the polymers of 2-chloro butadlene-1,3. Chloro-sulphonated polyethylene can also be used.
The silicate fillers applicable according to the present invention, also as a mixture of two or more fillers, are fillers which are known in the rubber technology. The term "silicate filler"
is a broad term and relates to fillers compatible with rubber and incorporated in rubber mixtures, i.e., fillers consisting of sili cates or containing silicates and/or containing silicates chemically bonded in the broadest sense. ~he silicate fillers include par~
ticularly: - ~lighly dispersed silica fillers (silicon dioxide) having specific surface areas in the range from approximately 5 to 1000, preferably from 20 to 40 sq. m per gram, and primary particle sizes ranging from approximately 10 to 400 nm. They can be produced, for example, by precipitation from solutions of silicate with in-organic acids, by hydrothermal decomposition, by hydrolytic or oxidative high temperature reac~ion of volatile silicon halides or 12S;~5~3~
by an arc process. When required these silicas can also be in the form of mixed oxides or oxide mixtures wi-th oxides of the metals ; aluminium, magnesium, calcium, barium, zinc, zirconium and/or titanium. - Synthetic silicas, for example, aluminium silicate or alkaline earth metal silicates, such as magnesium or calcium silicate7 having specific surface areas of approximately 20 to 400 sq. m per gram and primary particle sizes of approximately 10 to ~00 nm.
- Natural silicates, for example, kaolins, clays and asbestos, clays as well as natural silicas, as for example, quartz and kieselguhr.
- Glass fibres and glass fibre products such as mats, strands, fabrics and the like as ~ell as microglass beads.
The above silicate fillers are preferably used in amounts of approximately 10 or when required less than 10 parts by weight to approximately 250 parts by weight, relative to 100 parts by weight of the rubber polymer.
5ilicon/kaolin or silica/glass fibres/asbestos as well as blends of the silica-te-containing reinforcing fillers with the con-ventional rubber blacks, for example, silica ISAF blac~ or silica/
glass fibre cord/H~F blacks can be mentioned as filler mixtures.
According to the present invention the highly dispersed or active silicas, particularly the precipitated silicas and pre-ferably in amounts of 5 to 150 parts by weight, relative to 100 parts by weight of rubber, are preferred.
Black can be additionally present in the rubber mixtures according to the present inven~ion not only for obtaining the gray or black coloration of the vulcanizat~s but to attain special valuable vulcanizate properties, the conventional rubber black being preferred. The black is used in the rubber mixutres in amounts of 0 to 150 parts by weight, preferably 0.1 to 80 parts by wei~ht, relative to 100 parts by weight of rubber.
Within the scope of the present invention a lower limit with the number zero means that the mixture component can ~ut^shoul~
~%52~3~
not be present in the rubber mixture. When rubber is present in a mixture the lower limit must be set practically at 0.1 part by weight.
For the case that both a silicate filler and a black are present in the rubber mixtures the total content of filler relative to 100 parts by weight of rubber is limited to a maximum of 250 parts by weight. In general, 150 parts by weight can be regarded as the upper limit.
Conventional stabilizers, particularly those selected from the group of age resisters, fatigue inhibitors, antioxidants, UV
rays absorbing agents and ozone resisters as well as mixtures thereof can be present with advantage in the rubber mixtures according to present invention, that is to say, in amounts of 0.2 to 10 parts by weight relative to 100 parts by weight of the halo rubber.
Furthermore, it can be particularly advantageous when the halo-rubber mi~tures contain plasticizers or plasticizer oils, for example, highly aromatic naphthenic or paraffinic plasticizer oils, with advantage those having low solidifying points of approximately between 0 and -60C. The proportion of plasticizer oil can vary within wide limits. Thus it can be more than 0~5 or 5 parts by weight, particularly more than 10 to approximately 100 parts by weight.
The halo-rubber mixtures preferably contain an organic acid, which is solid at room temperatures and is used in the rubber technology, in amounts of 0.2 to 10 parts by weight, relative to 100 parts by weight of the rubber, pre~erably fatty acids~such as stearic acid or corresponding acids of the homologous series as well as benzoic acid or salicylic acid.
Furthermore, oxides of polyvalent metals like those also used in the rubber technology must be added to the rubb~r mixtures according to the present invention in amounts of 0.1 to 15 parts by weight relative to 100 parts by weight of the rubber~ These metallic lZ~ 37 oxides include primarily zinc oxide, particularly in a finely divi-ded and~or active form. Magnesium oxide and under certain condi-tions lead oxide are also suitable for this purpose. These oxides are preferably used in a finely divided, active or powdered form.
Mixtures of the metallic oxides can also be used.
The halo-rubber mixtures are produced in the following manner. A two-stage mixing cycle is preferred. In the first stage the following ingredients are mixed in a kneader at flow tempera-tures of between 55 and 65C, preferably at 60C: Within the first minute the rubber and the metallic oxide, for example, thus the poly-chloro butadiene and the magnesium oxide, within the subsequent one and a half minutes one half of the silicate filler and the other fillers, within the one and a half minutes thereafter the second half of the silicate filler, when required the halo silane, the plastici2er, for example, the plasticizer oil, and the other ingre-dients of the mixture with the exception of the silicon-containing isothiuronium compound according to formula I and of the zinc oxide, after a total of four and a half minutes the mixture is removed from the kneadex.
In the second mixing stage the zinc oxide and the isothi-uronium compound are admixed with the master batch from the first mixing stage on a pair of rolls at a flow temperature of approxim-ately 45 to 55C, preferably at 50C.
This two-stage mixing process avoids the premature pre-vulcanization of the mixture.
Industrial uses for the des~ribed rubber mixtures and their vulcani~ates are, for example, technical rubber articles such as cable sheathings, tubes~ air tubes, transmission belts, cone belts, conveyor belts, roll covers, gaskets, electric insulations, 3~ linings, impregnatio~s and coatings of heat-resistant fabrics, damp-ing and vibration elements a~d similar articles which have to satis~y high requirements with regard to resistance to high temperatures and riZ93 oil resistanceO
A number of examples of formulations for the halo-rubber mixtures along with test results including the cross-linking pro-ducts, evaluations and comparisons of these results are provided hereafter. Many different terms are repeated so that the following abbreviations are used:
LIST OF ABBREVIATIONS USED
ABBREVIATION _ TE~M MEASURED IN
t5 Mooney sgarch time minutes (130 C) t35 MO(ln3eyocc)re time minutes ML 4 Mooney plasticity -viscosity at 100C, standard rotor, testing time: 4 minutes ZF tensile strength MPa M 100 stress value at 100% MPa .~ 200 stress value at 200% MPa M 300 stress value at 30G% MPa stretch (moduli) BD elongation at break SH Shore-A hardness A abrasion (also referred mm to as "DIN abrasion") CS compresgign set B (2 hours, 70 C) TEST STANDARDS
The physical tests were carried out at room temperatures according to the following standard specifications:
tensile streng-th, elongation at break and stress value on rings of 6 mm thickness DIN 53 504 30 Shore-A hardness DIN 53 505 specific gravity DIN 53 550 Mooney test DIN 53 524 lZSZ~37 abrasion, also reEerred to as DIN 53 516 DIN abrasion determination of the compression - DIN 53 517 set of rubber rheometer test The following isothiuronium compounds are used in the examples: H
Si 70 2 5 3 ( 3 6) C\ I Cl ~ N-CH2 Si 71 like Si 70, but does not contain Cl , it contains Br~3, OS 34 2 5)3~Si(C3H6)-S=C C4Hg ~
OS 81 2 5 3 ( 3 6) S C \ C1~3 E~ ~
I
The cross-linking products and the test samples were pro-duced on a steam-heated gang press at the vulcani2ation temperatures and heating times (cross-linking times) defined.
In the examples the amounts of the mixture ingredients are given in parts by weight; phr means per 100 parts of rubberO
TESTS WITH CHLORO-BUTADIENE_RUBBER
The basic mixture A consists of the following ingredients (in part by weight):
polychloro butadlene rubber (chlorine content approxima.~ely 38%, viscosity 40 to 45 Mooney units): 100 magnesium oxide, finely divided 4 stearic acid petroleum jelly-(ointment-like pure hydrocarbon m.ixture from residues of 30 the petroleum distillation) N-isopropyl-N'phenyl-p-phenylene diamine (age resister) 2 ~ZSZ937 finely divided precipitated silica (VN 3 Ultrasil) 40 zinc oxide, finely divided, active 5 Example 1 The basic mixture A is supplemented in the following manner:
Sample No. 1 2 3 . _ _ chloro-propyl triethoxy silane (Cl-PTES) - 2.5 0.73 Si 70 - - 2.52 ethylenethiourea 0.75 0.75 (ETU) After moulding the samples produced from the mixtures the cross-linking was carried out at 170C in 60 minutes. The tests resulted in the following values:
. __ Sam le No. 1 2 3 P . ~
Dmin,[Nm] 2.34 1.56 1.56 M 300 10.9 13.7 15.1 [MPa]
[mm3] 113 90 78 CS 25.5 14.8 12.2 As compared with the vulcanizates according to the prior art the vulcanizate of the halo-rubber mixture according to the present invention (sample 3) shows distinctly better values with - regard to strength, stress value 300%, abrasion and compression set.
Example 2 The basic mixture A i5 supplemented in the following manner:
Sample No. _ 1 2 3 . _ . . _ . . _ . . .
ClPTES - 2.5 Si 70 ~ - 2.0 ethylene thiourea (ETU) 0.75 0.75 The vulcanization was carried out at 170 C in 120 minutes.
3~7 T~e following ~alues were measured;
Sample No. ~ 1 2 3 min' 1.83 1043 1.41 ZF
~MPa] 13.8 15.7 18.7 M 300~
[MPa] 7.9 14.5 16.8 CS 17.~ 12.7 9.4 While in Example 1 the amount of Si 70 was so computed that the amounts of thiourea and ClPTES contained in the halo-r ~ ber mixture corresponded to the amount of Si 70 in the sample no. 1 and
It is known that in rubber mixtures vulcanized wi~h sul-phur which are to contain a high proportion of silicate fillers, as for example, precipitated silica, a silane is required as a mix-ture component in order to impart sufficiently good properties to the vulcanizates.
DE-AS 28 19 638 describes that from silicate-filler-con-taining rubber mixtures based on halogen-containing rubber types valuable vulcanization products are forrned when the mixtures con-tain specific halogen-containing silanes.
These mixtures according to the prior art frequently con-tain compounds from the thiourea class as vulcanization accelerators.
It has now been found that vulcanization products having improved properties are surprisingly produced from these known halo-rubber mixtures when a silicon-containing isothiuronium compound is incorporated instead of a halogen-containing silane and an accelera-tor from the thiourea class.
The present invention thus provides vulcanizable rubber mixtures containing at least one halo rubber, a silicate filler and, when required, a halo silane and also contain at least one isothi-uronium compound having the formula ~ NP~ R4 I ~RO)3 n~nSiCmH2mS =C\ 5 6 NR R
in which X~represents chloride, bromide or iodide, m represents a number from 1 to 6, R represents a Cl- to c5-alkyl group, a C5- or C6-cycloalkyl group or the phenyl group, R represents a Cl- to C
alkyl group, a C5- or C6-cycloalkyl group, the ~methoxy-ethyl group~
93~
the phenyl group or the benzyl group, n represents 0, 1 or 2, R , R4, R5 and R6 are identical or dif~erent and represent hydrogen, a .
C~ to C~-alkyl group or R , R5 represent hydrogen, R , R6 are identical or different and represent hydrogen, a C5- to C6-cycloalkyl group, the phenyl group or the benzyl group or R4 and R6 represent a coherent C2- to C4-alkylene chain, in amounts from 0.1 to 5 parts by weight relative to 100 parts by weight of the halo rubber.
The isothiuronium compounds which according to the pre-sent invention must be present in the halo rubber mixtures either singly or in mixuture in amounts of 0.1 to 5 parts by weight, pre-ferably 0.1 to 2.0 parts by weight, relative to 100 parts by weight of halo rubber, include particularly the compounds which, bonded to the silicon atom, contain a triethoxy, trimethoxy, or a diethoxy-methyl, dimethoxy methyl group, wherein Cm~2m is ethyl, propyl or butyl and in which the isothiuronium group on the nitrogen atom is substituted by two methyl or ethyl groups or by a hydrogen atom, a methyl, ethyl, butyl, or phenyl group and wherein the hydrocarbon radicals can be identical or different.
Said organosilanes used according to the present invention are obtained by means of conventional processes ~rom thiourea deri-vatives having the formula II S=C /
where R , R , R5 and R6 are as above and from halo silanes havingthe formula III (RO RlSiC H X
where R7 Rl, X, m and n are as above.
Methods of production a~e described, for example, in U.S.
Patents ~os. 3,215,718 and 3, 314, 982 or in German Patent NQ . 2,120,002.
The composition of basic halo-rubber mixtures is known to a person skilled in the art. By basic mixtures are meant products like those described, for example, in DE-AS 28 19 63a in ignorance of the favourable possibilities of using silicon-containing iso-thiuronium compounds according to formula I. The proportion of the individual mixture components can be varied within wide limits.
When using the silicon-containing isothiuronium compounds the admixture of elementary sulphur as in the above basic mixtures is dispensed with. Furthermore, apart from the isothiuronium com-pounds according to formula I no further accelerators are required.
Free halosilane~ according to formula III can be presentin the vulcani~able mixture according to the present invention in amounts of 0 to 3 parts by weight, but is preferably absent.
The applicable halo rubbers include, for example~ halo-genated butyl rubber, particularly brominated or chlorinated butyl rubber, chloro rubber, rubber hydrochlorides and preferably halo-genated butyl rubber and particularly the polymers of 2-chloro butadlene-1,3. Chloro-sulphonated polyethylene can also be used.
The silicate fillers applicable according to the present invention, also as a mixture of two or more fillers, are fillers which are known in the rubber technology. The term "silicate filler"
is a broad term and relates to fillers compatible with rubber and incorporated in rubber mixtures, i.e., fillers consisting of sili cates or containing silicates and/or containing silicates chemically bonded in the broadest sense. ~he silicate fillers include par~
ticularly: - ~lighly dispersed silica fillers (silicon dioxide) having specific surface areas in the range from approximately 5 to 1000, preferably from 20 to 40 sq. m per gram, and primary particle sizes ranging from approximately 10 to 400 nm. They can be produced, for example, by precipitation from solutions of silicate with in-organic acids, by hydrothermal decomposition, by hydrolytic or oxidative high temperature reac~ion of volatile silicon halides or 12S;~5~3~
by an arc process. When required these silicas can also be in the form of mixed oxides or oxide mixtures wi-th oxides of the metals ; aluminium, magnesium, calcium, barium, zinc, zirconium and/or titanium. - Synthetic silicas, for example, aluminium silicate or alkaline earth metal silicates, such as magnesium or calcium silicate7 having specific surface areas of approximately 20 to 400 sq. m per gram and primary particle sizes of approximately 10 to ~00 nm.
- Natural silicates, for example, kaolins, clays and asbestos, clays as well as natural silicas, as for example, quartz and kieselguhr.
- Glass fibres and glass fibre products such as mats, strands, fabrics and the like as ~ell as microglass beads.
The above silicate fillers are preferably used in amounts of approximately 10 or when required less than 10 parts by weight to approximately 250 parts by weight, relative to 100 parts by weight of the rubber polymer.
5ilicon/kaolin or silica/glass fibres/asbestos as well as blends of the silica-te-containing reinforcing fillers with the con-ventional rubber blacks, for example, silica ISAF blac~ or silica/
glass fibre cord/H~F blacks can be mentioned as filler mixtures.
According to the present invention the highly dispersed or active silicas, particularly the precipitated silicas and pre-ferably in amounts of 5 to 150 parts by weight, relative to 100 parts by weight of rubber, are preferred.
Black can be additionally present in the rubber mixtures according to the present inven~ion not only for obtaining the gray or black coloration of the vulcanizat~s but to attain special valuable vulcanizate properties, the conventional rubber black being preferred. The black is used in the rubber mixutres in amounts of 0 to 150 parts by weight, preferably 0.1 to 80 parts by wei~ht, relative to 100 parts by weight of rubber.
Within the scope of the present invention a lower limit with the number zero means that the mixture component can ~ut^shoul~
~%52~3~
not be present in the rubber mixture. When rubber is present in a mixture the lower limit must be set practically at 0.1 part by weight.
For the case that both a silicate filler and a black are present in the rubber mixtures the total content of filler relative to 100 parts by weight of rubber is limited to a maximum of 250 parts by weight. In general, 150 parts by weight can be regarded as the upper limit.
Conventional stabilizers, particularly those selected from the group of age resisters, fatigue inhibitors, antioxidants, UV
rays absorbing agents and ozone resisters as well as mixtures thereof can be present with advantage in the rubber mixtures according to present invention, that is to say, in amounts of 0.2 to 10 parts by weight relative to 100 parts by weight of the halo rubber.
Furthermore, it can be particularly advantageous when the halo-rubber mi~tures contain plasticizers or plasticizer oils, for example, highly aromatic naphthenic or paraffinic plasticizer oils, with advantage those having low solidifying points of approximately between 0 and -60C. The proportion of plasticizer oil can vary within wide limits. Thus it can be more than 0~5 or 5 parts by weight, particularly more than 10 to approximately 100 parts by weight.
The halo-rubber mixtures preferably contain an organic acid, which is solid at room temperatures and is used in the rubber technology, in amounts of 0.2 to 10 parts by weight, relative to 100 parts by weight of the rubber, pre~erably fatty acids~such as stearic acid or corresponding acids of the homologous series as well as benzoic acid or salicylic acid.
Furthermore, oxides of polyvalent metals like those also used in the rubber technology must be added to the rubb~r mixtures according to the present invention in amounts of 0.1 to 15 parts by weight relative to 100 parts by weight of the rubber~ These metallic lZ~ 37 oxides include primarily zinc oxide, particularly in a finely divi-ded and~or active form. Magnesium oxide and under certain condi-tions lead oxide are also suitable for this purpose. These oxides are preferably used in a finely divided, active or powdered form.
Mixtures of the metallic oxides can also be used.
The halo-rubber mixtures are produced in the following manner. A two-stage mixing cycle is preferred. In the first stage the following ingredients are mixed in a kneader at flow tempera-tures of between 55 and 65C, preferably at 60C: Within the first minute the rubber and the metallic oxide, for example, thus the poly-chloro butadiene and the magnesium oxide, within the subsequent one and a half minutes one half of the silicate filler and the other fillers, within the one and a half minutes thereafter the second half of the silicate filler, when required the halo silane, the plastici2er, for example, the plasticizer oil, and the other ingre-dients of the mixture with the exception of the silicon-containing isothiuronium compound according to formula I and of the zinc oxide, after a total of four and a half minutes the mixture is removed from the kneadex.
In the second mixing stage the zinc oxide and the isothi-uronium compound are admixed with the master batch from the first mixing stage on a pair of rolls at a flow temperature of approxim-ately 45 to 55C, preferably at 50C.
This two-stage mixing process avoids the premature pre-vulcanization of the mixture.
Industrial uses for the des~ribed rubber mixtures and their vulcani~ates are, for example, technical rubber articles such as cable sheathings, tubes~ air tubes, transmission belts, cone belts, conveyor belts, roll covers, gaskets, electric insulations, 3~ linings, impregnatio~s and coatings of heat-resistant fabrics, damp-ing and vibration elements a~d similar articles which have to satis~y high requirements with regard to resistance to high temperatures and riZ93 oil resistanceO
A number of examples of formulations for the halo-rubber mixtures along with test results including the cross-linking pro-ducts, evaluations and comparisons of these results are provided hereafter. Many different terms are repeated so that the following abbreviations are used:
LIST OF ABBREVIATIONS USED
ABBREVIATION _ TE~M MEASURED IN
t5 Mooney sgarch time minutes (130 C) t35 MO(ln3eyocc)re time minutes ML 4 Mooney plasticity -viscosity at 100C, standard rotor, testing time: 4 minutes ZF tensile strength MPa M 100 stress value at 100% MPa .~ 200 stress value at 200% MPa M 300 stress value at 30G% MPa stretch (moduli) BD elongation at break SH Shore-A hardness A abrasion (also referred mm to as "DIN abrasion") CS compresgign set B (2 hours, 70 C) TEST STANDARDS
The physical tests were carried out at room temperatures according to the following standard specifications:
tensile streng-th, elongation at break and stress value on rings of 6 mm thickness DIN 53 504 30 Shore-A hardness DIN 53 505 specific gravity DIN 53 550 Mooney test DIN 53 524 lZSZ~37 abrasion, also reEerred to as DIN 53 516 DIN abrasion determination of the compression - DIN 53 517 set of rubber rheometer test The following isothiuronium compounds are used in the examples: H
Si 70 2 5 3 ( 3 6) C\ I Cl ~ N-CH2 Si 71 like Si 70, but does not contain Cl , it contains Br~3, OS 34 2 5)3~Si(C3H6)-S=C C4Hg ~
OS 81 2 5 3 ( 3 6) S C \ C1~3 E~ ~
I
The cross-linking products and the test samples were pro-duced on a steam-heated gang press at the vulcani2ation temperatures and heating times (cross-linking times) defined.
In the examples the amounts of the mixture ingredients are given in parts by weight; phr means per 100 parts of rubberO
TESTS WITH CHLORO-BUTADIENE_RUBBER
The basic mixture A consists of the following ingredients (in part by weight):
polychloro butadlene rubber (chlorine content approxima.~ely 38%, viscosity 40 to 45 Mooney units): 100 magnesium oxide, finely divided 4 stearic acid petroleum jelly-(ointment-like pure hydrocarbon m.ixture from residues of 30 the petroleum distillation) N-isopropyl-N'phenyl-p-phenylene diamine (age resister) 2 ~ZSZ937 finely divided precipitated silica (VN 3 Ultrasil) 40 zinc oxide, finely divided, active 5 Example 1 The basic mixture A is supplemented in the following manner:
Sample No. 1 2 3 . _ _ chloro-propyl triethoxy silane (Cl-PTES) - 2.5 0.73 Si 70 - - 2.52 ethylenethiourea 0.75 0.75 (ETU) After moulding the samples produced from the mixtures the cross-linking was carried out at 170C in 60 minutes. The tests resulted in the following values:
. __ Sam le No. 1 2 3 P . ~
Dmin,[Nm] 2.34 1.56 1.56 M 300 10.9 13.7 15.1 [MPa]
[mm3] 113 90 78 CS 25.5 14.8 12.2 As compared with the vulcanizates according to the prior art the vulcanizate of the halo-rubber mixture according to the present invention (sample 3) shows distinctly better values with - regard to strength, stress value 300%, abrasion and compression set.
Example 2 The basic mixture A i5 supplemented in the following manner:
Sample No. _ 1 2 3 . _ . . _ . . _ . . .
ClPTES - 2.5 Si 70 ~ - 2.0 ethylene thiourea (ETU) 0.75 0.75 The vulcanization was carried out at 170 C in 120 minutes.
3~7 T~e following ~alues were measured;
Sample No. ~ 1 2 3 min' 1.83 1043 1.41 ZF
~MPa] 13.8 15.7 18.7 M 300~
[MPa] 7.9 14.5 16.8 CS 17.~ 12.7 9.4 While in Example 1 the amount of Si 70 was so computed that the amounts of thiourea and ClPTES contained in the halo-r ~ ber mixture corresponded to the amount of Si 70 in the sample no. 1 and
2, in sample 5 2 phr Si 70 were applied as compared with 2.5 phr ClPTES alone to which 0.75 phr ETU were also added.
Despite lower consumption of active substance distinctly higher values for the -tensile strength and stress as well as a lower compression set (sample 5) were also obtained in this case.
Example 5 The basic mixture was supplemented in the following manner:
TABI,E 6 Sam le No. 6 7 8 9 10 11 . P . ~
ClPTES - 2.5 - - - -dibutyl thiourea 0.75 0.75 OS 34 - - 1 1.5 2 2.5 After a vulcani~ation temperature of 170 C and vulcaniza-tion times of 60 and 120 minutes the following values were measured:
Sample No. 6- 7 8 9 10 11 . _ . . _ . . _ _ . _ _ vulcaniza~ion time 60 60 80 60 60 60 (min.) 120 120 120 120 120 120 ZF 18.5 18.7 23.6 21.0 19.4 22.7 rMpa~ 17.1 24.6 23~4 24.8 19=3 23.7 :~2~ 37 T~BLE 7 (con't) Sam~le No. 6 7 8 9 10 11 ,.
M 100~ 1.92.3 2.2 2.5 2.8 3.1 LMpa] 2.32.5 3.1 3.0 3.4 3.2 M 200% 4.46.1 6.0 7.1 8.1 8.8 ~MPaJ 5.17.0 8.0 8.5 9.4 9.5 M 300% 8.112.0 11.5 13.6 15.5 16.5 ~MPa~ 8.813.3 14.1 15.8 17.1 17.9 ~ 520480 460 440 320 380 23C ~7 69 72 72 72 72 mm 124 83 84 73 67 62 It can be seen that as the OS 34 concentration increases the superority of the halo-rubber mixtures 8 to 11 according to the present invention also increases.
In order to attain the properties of a mixture according to the prior art which contains 2.5 phr ClPTES and 0~75 phr BPTU
(sample 7), according to the present invention 1 phr OS 34 in a halo-rubber mixture is sufficient.
Example 4 The basic mixture A is supplemented in the following manner:
Sample No. 12 13 14 15 16 17 18 ClPTES - 2.5 Rhenocure CA 0.75 0.75 OS ~1 - - 0.5 1 1.5 2 2.5 A strong viscosity-reducing effect of the OS 81 is obt-ained as compared with the comparison mixtures 12 and 13. This isequivalent to a lower energy consump~ion in the production of the mixtures.
~Z~ 937 Rheometer Test (Monsanto type MPV) strain amplitude: 3 degrees testing frequency: 3 cycles per minute running time: 2 hours test temperature: 170C
Sample No. 12 13 14 15 16 _ 17 18 Dmin [Nm] 2.56 1.83 2.28 2.17 2.27 2O26 1.87 Dmax [Nm]
10 Dmax-Dmin [Nm]
D120' [Nm] 9.32 12.02 9.59 9.76 10.94 11.45 10.24 D120'-Dmin [Nm] 6.76 10.19 7.31 7.60 8.67 9.20 8.38 D120'-D60' (~ 16.4 13.2 20.3 20.2 18.1 16.6 11.6 D120'-Dmin The testing of the halo-rubber mixtures vulcanized at 170C resulted in the following values:
Sam le No. 12 13 14 15 16 17 18 P .. _ . _ _ .. _ ... _ . . . _ .. _ ... .. _ vulcanization ,60 60 60 60 60 60 60 time (min.) 120 120 120 120 120 120 120 ZF 17.3 16.9 20.0 21.2 20.8 22.2 23.2 [MPa] 15.2 20.4 21.2 21.8 22.4 24.7 23.5 [mm ] 111 78 103 79 79 70 62 The mixture containing the silica-containing isothiuronium compound shows a distinct superiority fox the parameters tensile strength and a~rasion. This is also observed when only 0.5 phr OS 81 are present in the mixture (sample 14) as compared with 2.5 phr ClPTE~ and 0.75 phr Rhenocure CA (sample 13).
(Rhenocure CA - diphenyl thiourea).
Exa~le 5 In the basic mlxture A ~0 parts of the sillca are replaced by 20 parts of black ~supplied under the trademark Corax N 330) and the mixture ~s further ~upplemented as follows:
T~BLE 11 Sam~le No. 19 20 21 Ultrasil VN 3 (a trademark)30 30 30 CORAX N 330 (a trademark) 20 20 20 Naftolen ZD (a trademark) 10 10 10 Cl-PTES - 2.5 OS 81 - - 1.0 diphenyl thiourea 0.75 0,75 After the vulcanization for 60 minutes at 170 C the follow-10 ing values were obtained:
Sample No. 19 _ 20 21 ZF 17.3 21.1 20.4 [MPa]
M 300 8.9 12.7 12.2 [MPa]
(~) CS 15.3 8.4 ~.8 In the mixtures partially filled with black the efficiency of the silica-containing iso-thiuronium compound (sample 21) thus is also evident even though it is applied in distinctly lower amounts than the starting substances (in sample 20) forming said compound.
Example 6 In the basic mixture A the silica is replaced by 80 parts of Suprex Clay and the mixture is supplemented as follows:
Sam le No. 22 23 24 25 26 27 Suprex Clay 80 80 80 80 80 80 Naftolen ZD 10 10 10 10 10 10 Cl PTES - 2.5 OS 34 - - 0.5 1 1 3 dibutyl thiourea 0.75 0~75 ~LZ~29~"~
Af~er the vulcanization for 20 minutes at 170 C the follow-ing results were obtained:
Sample No. 22 23 24 25 26 27 .L 4 57 52 58 55 51 51 Z~ 12.012.112.3 12.7 12.9 11.6 [MPa]
M 300% 4.39.8 7.8 9.3 9.9 10.3 [MPa]
(%) CS
22 h 70C 12.67.5 902 8.0 7.4 7.8 70 h 100C 38.426.526.3 24.7 24.7 24.5 These tests once more show the superiority of the halo-rubber mixtures containing the silica-containing isothiuronium compounds according to formula I over the mixtures according to the prior art. This is also the case when a larger amount of halosilane and thiourea derivative is applied in the comparison mixtures than is required for the formation of the isothiuronium compound used in the demonstration mixture. However, this means that with the use of silica-containing isothiuronium compounds a saving of raw materials is attained.
Example ?
The basic mixture ~ is supplemented in the following manner:
_ . _ Sample No. 28 29 3031 . _ _ . . . . .
Despite lower consumption of active substance distinctly higher values for the -tensile strength and stress as well as a lower compression set (sample 5) were also obtained in this case.
Example 5 The basic mixture was supplemented in the following manner:
TABI,E 6 Sam le No. 6 7 8 9 10 11 . P . ~
ClPTES - 2.5 - - - -dibutyl thiourea 0.75 0.75 OS 34 - - 1 1.5 2 2.5 After a vulcani~ation temperature of 170 C and vulcaniza-tion times of 60 and 120 minutes the following values were measured:
Sample No. 6- 7 8 9 10 11 . _ . . _ . . _ _ . _ _ vulcaniza~ion time 60 60 80 60 60 60 (min.) 120 120 120 120 120 120 ZF 18.5 18.7 23.6 21.0 19.4 22.7 rMpa~ 17.1 24.6 23~4 24.8 19=3 23.7 :~2~ 37 T~BLE 7 (con't) Sam~le No. 6 7 8 9 10 11 ,.
M 100~ 1.92.3 2.2 2.5 2.8 3.1 LMpa] 2.32.5 3.1 3.0 3.4 3.2 M 200% 4.46.1 6.0 7.1 8.1 8.8 ~MPaJ 5.17.0 8.0 8.5 9.4 9.5 M 300% 8.112.0 11.5 13.6 15.5 16.5 ~MPa~ 8.813.3 14.1 15.8 17.1 17.9 ~ 520480 460 440 320 380 23C ~7 69 72 72 72 72 mm 124 83 84 73 67 62 It can be seen that as the OS 34 concentration increases the superority of the halo-rubber mixtures 8 to 11 according to the present invention also increases.
In order to attain the properties of a mixture according to the prior art which contains 2.5 phr ClPTES and 0~75 phr BPTU
(sample 7), according to the present invention 1 phr OS 34 in a halo-rubber mixture is sufficient.
Example 4 The basic mixture A is supplemented in the following manner:
Sample No. 12 13 14 15 16 17 18 ClPTES - 2.5 Rhenocure CA 0.75 0.75 OS ~1 - - 0.5 1 1.5 2 2.5 A strong viscosity-reducing effect of the OS 81 is obt-ained as compared with the comparison mixtures 12 and 13. This isequivalent to a lower energy consump~ion in the production of the mixtures.
~Z~ 937 Rheometer Test (Monsanto type MPV) strain amplitude: 3 degrees testing frequency: 3 cycles per minute running time: 2 hours test temperature: 170C
Sample No. 12 13 14 15 16 _ 17 18 Dmin [Nm] 2.56 1.83 2.28 2.17 2.27 2O26 1.87 Dmax [Nm]
10 Dmax-Dmin [Nm]
D120' [Nm] 9.32 12.02 9.59 9.76 10.94 11.45 10.24 D120'-Dmin [Nm] 6.76 10.19 7.31 7.60 8.67 9.20 8.38 D120'-D60' (~ 16.4 13.2 20.3 20.2 18.1 16.6 11.6 D120'-Dmin The testing of the halo-rubber mixtures vulcanized at 170C resulted in the following values:
Sam le No. 12 13 14 15 16 17 18 P .. _ . _ _ .. _ ... _ . . . _ .. _ ... .. _ vulcanization ,60 60 60 60 60 60 60 time (min.) 120 120 120 120 120 120 120 ZF 17.3 16.9 20.0 21.2 20.8 22.2 23.2 [MPa] 15.2 20.4 21.2 21.8 22.4 24.7 23.5 [mm ] 111 78 103 79 79 70 62 The mixture containing the silica-containing isothiuronium compound shows a distinct superiority fox the parameters tensile strength and a~rasion. This is also observed when only 0.5 phr OS 81 are present in the mixture (sample 14) as compared with 2.5 phr ClPTE~ and 0.75 phr Rhenocure CA (sample 13).
(Rhenocure CA - diphenyl thiourea).
Exa~le 5 In the basic mlxture A ~0 parts of the sillca are replaced by 20 parts of black ~supplied under the trademark Corax N 330) and the mixture ~s further ~upplemented as follows:
T~BLE 11 Sam~le No. 19 20 21 Ultrasil VN 3 (a trademark)30 30 30 CORAX N 330 (a trademark) 20 20 20 Naftolen ZD (a trademark) 10 10 10 Cl-PTES - 2.5 OS 81 - - 1.0 diphenyl thiourea 0.75 0,75 After the vulcanization for 60 minutes at 170 C the follow-10 ing values were obtained:
Sample No. 19 _ 20 21 ZF 17.3 21.1 20.4 [MPa]
M 300 8.9 12.7 12.2 [MPa]
(~) CS 15.3 8.4 ~.8 In the mixtures partially filled with black the efficiency of the silica-containing iso-thiuronium compound (sample 21) thus is also evident even though it is applied in distinctly lower amounts than the starting substances (in sample 20) forming said compound.
Example 6 In the basic mixture A the silica is replaced by 80 parts of Suprex Clay and the mixture is supplemented as follows:
Sam le No. 22 23 24 25 26 27 Suprex Clay 80 80 80 80 80 80 Naftolen ZD 10 10 10 10 10 10 Cl PTES - 2.5 OS 34 - - 0.5 1 1 3 dibutyl thiourea 0.75 0~75 ~LZ~29~"~
Af~er the vulcanization for 20 minutes at 170 C the follow-ing results were obtained:
Sample No. 22 23 24 25 26 27 .L 4 57 52 58 55 51 51 Z~ 12.012.112.3 12.7 12.9 11.6 [MPa]
M 300% 4.39.8 7.8 9.3 9.9 10.3 [MPa]
(%) CS
22 h 70C 12.67.5 902 8.0 7.4 7.8 70 h 100C 38.426.526.3 24.7 24.7 24.5 These tests once more show the superiority of the halo-rubber mixtures containing the silica-containing isothiuronium compounds according to formula I over the mixtures according to the prior art. This is also the case when a larger amount of halosilane and thiourea derivative is applied in the comparison mixtures than is required for the formation of the isothiuronium compound used in the demonstration mixture. However, this means that with the use of silica-containing isothiuronium compounds a saving of raw materials is attained.
Example ?
The basic mixture ~ is supplemented in the following manner:
_ . _ Sample No. 28 29 3031 . _ _ . . . . .
3-bromopropyl triethoxy silane - 2.5 Si 71 - - 1 2 ETU 0.75 0.75 After the vulcanization the followillg values were obtained:
~
Sample - No. ~ 28 29 - 3031 - vulcanization 60 60 6060 time (min.) 120 120 120120 TABLE 16 (con't) ~5~937 Sample No. 28 29 30 31 ZF 16~8 16.8 21.7 20.5 ~MPa] 15.6 19.0 20.7 20.4 stress value 200% 6.4 8.3 5.9 7.7 ~MPa] 5.9 7.4 7.2 8.7 . M 300 10.0 14.6 10.9 13.7 [MPa] 9.3 14.1 12.6 15.4 abrasion 119 97 85 81 [mm3] , 138 101 95 86 This case also shows the superority of the vulcanizates con-taining the silica-containing isothiuronium compounds over the vulcanizate containing ethylene thiourea (ETU) and 3-bromopropyl triethoxy silane (BrPTES) (sample 29) although the proportions of Si 71 are distinctly below the sum of the amounts of BrPTES and ETU applied in sample 27.
~
Sample - No. ~ 28 29 - 3031 - vulcanization 60 60 6060 time (min.) 120 120 120120 TABLE 16 (con't) ~5~937 Sample No. 28 29 30 31 ZF 16~8 16.8 21.7 20.5 ~MPa] 15.6 19.0 20.7 20.4 stress value 200% 6.4 8.3 5.9 7.7 ~MPa] 5.9 7.4 7.2 8.7 . M 300 10.0 14.6 10.9 13.7 [MPa] 9.3 14.1 12.6 15.4 abrasion 119 97 85 81 [mm3] , 138 101 95 86 This case also shows the superority of the vulcanizates con-taining the silica-containing isothiuronium compounds over the vulcanizate containing ethylene thiourea (ETU) and 3-bromopropyl triethoxy silane (BrPTES) (sample 29) although the proportions of Si 71 are distinctly below the sum of the amounts of BrPTES and ETU applied in sample 27.
Claims (39)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A vulcanizable rubber mixture containing at least one halo rubber, a silicate filler from 0.1 to 15 parts based on the weight of the rubber of a of a polyvalent metal oxide and at least one isothiuronium compound having the formula in amounts of 0.1 to 5 parts by weight, relative to 100 parts by weight of the halo rubber wherein X - represents chloride, bro-mide or iodide, m represents a number from 1 to 6, Rl represents a Cl-C5-alkyl group, a C5- or C6-cycloalkyl group or the phenyl group, R represents a Cl- to C5- alkyl group, a C5- or C6-cycloalkyl group, the B-methoxy-ethyl group, the phenyl group or the benzyl group, n is 0, 1 or 2, R3, R4, R5, R6 are identical or d1fferent and represent hydrogen, a Cl- to C5-alkyl group, or R3, R5 represent hydrogen, R4, R6 are identical or different and represent a C5- to C6-cycloalkyl group, the phenyl group or the benzyl group or R4 and R6 represent a coherent C2- to C4-alkylene chain.
2. A mixture according to claim 17 in which the isothiuronium compounds bonded to the silicon atom contain a triethoxy, trimethoxy, or a diethoxy-methyl, or dimethoxy methyl group, wherein CmH2m is ethyl, propyl or butyl and in which the isothiuronium group on the nitrogen atom is substituted by two methyl or ethyl groups or by a hydrogen atom, a methyl, ethyl, butyl or phenyl group.
3. A mixture according to claim 1, in which the isoth-iuronium compound is selected from
4. A mixture according to claim l, 2 or 3 which contains 0.1 to 2.0 parts by weight of isothuronium compound relative to lO0 parts by weight of halo rubber.
5. A mixture according to claim l, 2 or 3 which contains a halosilane.
6. A mixture according to claim l, 2 or 3 which contains a halosilane in an amount up to 3 parts by weight.
7. A mixture according to claim l, 2 or 3 in which the halo rubber is selected from halogenated butyl rubber, chloro rubber, and rubber hydrochloride.
8. A mixture according to claim l, 2 or 3 in which the halo rubber is halogenated butyl rubber.
9. A mixture according to claim 1, 2 or 3 in which the halo rubber is chlorinated or brominated rubber.
10. A mixture according to claim l, 2 or 3 in which the halo rubber is a polymer,of 2-chloro butadiene 1,3.
11. A mixture according to claim l, 2 or 3 in which the silicate filler is selected from highly dispersed silica fillers having specific surface areas in the range from about 5 to 1000 sq. m and primary particle sizes in the range of about 10to 400 nm.
12, A mixture according to claim 1, 2 or 3 in which the silicate filler is selected from synthetic silicas having specific surface areas of approximately 20 to 400 sq.m per gram and pri-mary particle sizes of approximately 10to 400 nm.
13. A mixture according to claim 1, 2 or 3 in which the silicate filler is selected from aluminum silicate and alkaline earth metal silicatss having specific surface areas of approximately 20 to 400 sq. m per gram and primary particle sizes of approximately 10 to 400 nm.
14. A mixture according to claim 1, 2 or 3 in which the silicate filler is selected from natural silicates.
15. A mixture according to claim 1, 2 or 3 in which the silicate filler is selected from glass fibres and glass fibre products.
16. A mixture according to claim 1, 2 or 3 which contains 10 to 250 parts by weight of silicate filler relative to 100 parts by weight of halo rubber.
17. A mixture according to claim 1, 2 or 3 which contains precipitated silicas in an amount of 5 to 150 parts by weight relative to 100 parts by weight of the halo rubber.
18. A mixture according to claim 1, 2 or 3 which contains carbon black in an amount up to 150 parts by weight relative to 100 parts by weight of halo rubber.
19. A mixture according to claim 1, 2 or 3 which contains carbon black in an amount of 0.1 to 80 parts by weight relative to 100 parts by weight of the halo rubber.
20. A mixture according to claim 1, 2 or 3 which contains an agent selected from age resistors, fatigue inhibitors, antioxi-dants, UV rays absorbing agents and ozone resisters as well as mixtures thereof in an amount of 0.2 to 10 parts by weight of the halo rubber.
21. A mixture according to claim 1, 2 ox 3 which contains plasticizers or plasticizer oils in an amount of 10 to 100 parts by weight.
22. A mixture according to claim 1, 2 or 3 which contains an organic acid which is solid at room temperature in an amount of 0.2 to 10 parts by weight relative to 100 parts by weight of the rubber.
23 A mixture according to claIm 1, 2 or 3, which con-tains a fatty acld, benzolc acld or sallcyllc acld whlch Is solld at room temperature In an amount of 0.2 to 10 Parts by welght relative to 100 parts by weight of the rubber.
24. A compositlon accordlng to clalm 1 free from a halosllane.
25. A composition accordling to clalm 1, wherein R1 Is C1 to C5 alkyl and R Is C1 to C5 alkyl.
26. A composition according to claim 25 where n Is 0.
27. A composition according to clalm 26 where m Is 2 or 3.
28. A composltlon accordlng to claim 27 containing 10 to 250 parts of silicate filter, 0 to 3 parts of halosllane, 0 to 150 parts of carbon black, 0.1 to 15 parts of magnesium oxide, lead oxide or zinc oxide.
29. A composition according to claim 1 contalining 10 to 250 parts of silicate f IIler, 0 to 3 parts of halosltane, 0 to 150 parts of carbon black, 0.1 to 15 parts of magnesium oxide, lead oxide or zinc oxide.
30. A composition accordlng to claim 29, whereln the halogen contalnlng rubber is polychlorobutadlene, chlorobutyl rubber or bromobutyl rubber.
31. A composltlon accordlng to claIm 30, whereln the slllcate Is precipitated silica.
32. A composition according to claim 31 containing mag-neslum oxlde.
33. A composition according to clalm 1, wherein the Isothluronlum compound Is eIther
34. A process for vulcanizing and cross-linking halo-rubber mlxtures according to claim 1 which comprises heating the mixtures, after mounding, to temperatures of between 100 and 200°C during a period of between 1 and 200 minutes.
35. The vulcanized product obtained by vulcanizing the composition of claim 1, 2 or 3.
36. The vulcanized product obtained by vulcanizing the composition of claim 2.4, 25 or 26.
37. The vulcanized product obtained by vulcanizing the composition of claim 27, 28 or 29.
38. The vulcanized product obtained by vulcanizing the composition of claim 30, 31 or 32.
39. The vulcanized product obtained by vulcanizing the composition of claim 33.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3319251.0 | 1983-05-27 | ||
| DE3319251A DE3319251C1 (en) | 1983-05-27 | 1983-05-27 | Vulcanizable halogen rubber compounds and methods for vulcanizing or crosslinking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1252937A true CA1252937A (en) | 1989-04-18 |
Family
ID=6200022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000455215A Expired CA1252937A (en) | 1983-05-27 | 1984-05-25 | Vulcanizable filled halo rubber with isothiuronium |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4517335A (en) |
| EP (1) | EP0126870B1 (en) |
| JP (1) | JPS59232133A (en) |
| KR (1) | KR910008802B1 (en) |
| AT (1) | ATE27707T1 (en) |
| AU (1) | AU571230B2 (en) |
| BR (1) | BR8402467A (en) |
| CA (1) | CA1252937A (en) |
| DE (2) | DE3319251C1 (en) |
| ES (1) | ES532361A0 (en) |
| IN (1) | IN162947B (en) |
| ZA (1) | ZA841948B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3821463A1 (en) * | 1988-06-25 | 1989-12-28 | Degussa | VULCANIZABLE ORGANIC LYSYLYL FUNCTIONAL THINOCARES CONTAINING HALOGENIC RUBBER MIXTURES |
| US5162409B1 (en) * | 1991-08-02 | 1997-08-26 | Pirelli Armstrong Tire Corp | Tire tread rubber composition |
| US5830930A (en) * | 1995-05-22 | 1998-11-03 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| HUP9802554A3 (en) * | 1995-05-22 | 1999-04-28 | Cabot Corp | Elastomeric compounds incorporating partially coated carbon blacks |
| US6028137A (en) * | 1995-05-22 | 2000-02-22 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US6323273B1 (en) | 1995-05-22 | 2001-11-27 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US6008272A (en) * | 1995-05-22 | 1999-12-28 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks |
| US5622557A (en) * | 1995-05-22 | 1997-04-22 | Cabot Corporation | Mineral binders colored with silicon-containing carbon black |
| US5877238A (en) * | 1995-05-22 | 1999-03-02 | Cabot Corporation | Elastomeric compounds incorporating silicon-treated carbon blacks and coupling agents |
| US5948835A (en) * | 1995-09-15 | 1999-09-07 | Cabot Corporation | Silicon-treated carbon black/elastomer formulations and applications |
| WO1997047382A1 (en) | 1996-06-14 | 1997-12-18 | Cabot Corporation | Modified carbon adsorbents and processes for adsorption using the same |
| US5747562A (en) * | 1996-06-14 | 1998-05-05 | Cabot Corporation | Ink and coating compositions containing silicon-treated carbon black |
| US20020056686A1 (en) * | 1996-06-14 | 2002-05-16 | Agathagelos Kyrlidis | Chromatography and other adsorptions using modified carbon adsorbents |
| US5919855A (en) * | 1997-02-11 | 1999-07-06 | Cabot Corporation | Use of modified carbon black in gas-phase polymerizations |
| US6448322B1 (en) | 1997-03-06 | 2002-09-10 | Exxon Mobil Chemical Patents Inc. | Stabilization of halogenated rubber |
| US6230773B1 (en) * | 1998-03-17 | 2001-05-15 | The Goodyear Tire & Rubber Company | Tire with sidewall carcass reinforcement |
| DE19858706A1 (en) * | 1998-12-18 | 2000-06-21 | Pulver Kautschuk Union Gmbh | Rubber powder (compounds) and process for their preparation |
| EP2246355B1 (en) * | 2008-02-22 | 2015-12-23 | Bridgestone Corporation | Organic silicon compound, and rubber compositions, tires, primer compositions, paint compositions, and adhesives using same |
| JP5513010B2 (en) * | 2009-05-20 | 2014-06-04 | 株式会社ブリヂストン | Organosilicon compound, and rubber composition, tire, primer composition, coating composition and adhesive using the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3215718A (en) * | 1961-11-24 | 1965-11-02 | Dow Corning | Sulfur-containing organosilicon compounds and method of preparation |
| US3637779A (en) * | 1970-04-23 | 1972-01-25 | Dow Corning | Preparation of beta-silathiuronium salts |
| DE2536674C3 (en) * | 1975-08-18 | 1979-09-27 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Crosslinkable mixtures based on rubber, organosilanes and silicate fillers |
| DE2819638C3 (en) * | 1978-05-05 | 1986-11-13 | Degussa Ag, 6000 Frankfurt | Vulcanizable halogen rubber compounds |
| SU740762A1 (en) * | 1978-07-12 | 1980-06-15 | Сумский Филиал Харьковского Ордена Ленина Политехнического Института Им. В.И.Ленина | Method of preparing s-alkylisothiuronium chloride |
| DE3220712A1 (en) * | 1982-06-02 | 1983-12-15 | Degussa Ag, 6000 Frankfurt | Water-containing solutions of silicon-containing isothiuronium compounds, process for the preparation and their use |
-
1983
- 1983-05-27 DE DE3319251A patent/DE3319251C1/en not_active Expired
-
1984
- 1984-03-14 EP EP84102750A patent/EP0126870B1/en not_active Expired
- 1984-03-14 AT AT84102750T patent/ATE27707T1/en not_active IP Right Cessation
- 1984-03-14 DE DE8484102750T patent/DE3464141D1/en not_active Expired
- 1984-03-15 ZA ZA841948A patent/ZA841948B/en unknown
- 1984-05-10 ES ES532361A patent/ES532361A0/en active Granted
- 1984-05-16 IN IN338/CAL/84A patent/IN162947B/en unknown
- 1984-05-23 BR BR8402467A patent/BR8402467A/en not_active IP Right Cessation
- 1984-05-24 AU AU28568/84A patent/AU571230B2/en not_active Ceased
- 1984-05-25 CA CA000455215A patent/CA1252937A/en not_active Expired
- 1984-05-26 KR KR1019840002937A patent/KR910008802B1/en not_active IP Right Cessation
- 1984-05-28 JP JP59106709A patent/JPS59232133A/en active Granted
- 1984-06-18 US US06/621,626 patent/US4517335A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0126870B1 (en) | 1987-06-10 |
| AU2856884A (en) | 1984-11-29 |
| US4517335A (en) | 1985-05-14 |
| KR910008802B1 (en) | 1991-10-21 |
| ES8502714A1 (en) | 1985-01-16 |
| ZA841948B (en) | 1984-11-28 |
| DE3319251C1 (en) | 1984-04-19 |
| ES532361A0 (en) | 1985-01-16 |
| KR840009319A (en) | 1984-12-26 |
| BR8402467A (en) | 1985-04-02 |
| JPS59232133A (en) | 1984-12-26 |
| EP0126870A1 (en) | 1984-12-05 |
| DE3464141D1 (en) | 1987-07-16 |
| IN162947B (en) | 1988-07-23 |
| AU571230B2 (en) | 1988-04-14 |
| ATE27707T1 (en) | 1987-06-15 |
| JPH0214370B2 (en) | 1990-04-06 |
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