CN1665874A - 间同立构聚苯乙烯共混物 - Google Patents
间同立构聚苯乙烯共混物 Download PDFInfo
- Publication number
- CN1665874A CN1665874A CN03815997.XA CN03815997A CN1665874A CN 1665874 A CN1665874 A CN 1665874A CN 03815997 A CN03815997 A CN 03815997A CN 1665874 A CN1665874 A CN 1665874A
- Authority
- CN
- China
- Prior art keywords
- poly
- blend
- syndiotactic polystyrene
- arylene ether
- described blend
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- 229920010524 Syndiotactic polystyrene Polymers 0.000 title claims abstract description 68
- -1 poly(arylene ether Chemical compound 0.000 claims abstract description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 64
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000945 filler Substances 0.000 claims description 9
- 239000004609 Impact Modifier Substances 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 239000005995 Aluminium silicate Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 235000012211 aluminium silicate Nutrition 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001955 polyphenylene ether Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000010445 mica Substances 0.000 description 3
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- 150000003440 styrenes Chemical class 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- HDYFAPRLDWYIBU-UHFFFAOYSA-N 1-silylprop-2-en-1-one Chemical compound [SiH3]C(=O)C=C HDYFAPRLDWYIBU-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical class OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- MYPXYQMABPTFFN-UHFFFAOYSA-N 4-phenoxybenzenesulfonic acid Chemical group C1=CC(S(=O)(=O)O)=CC=C1OC1=CC=CC=C1 MYPXYQMABPTFFN-UHFFFAOYSA-N 0.000 description 1
- 108700015862 A-B-A triblock copolymer Proteins 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000198134 Agave sisalana Species 0.000 description 1
- 235000011624 Agave sisalana Nutrition 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RTJUWEUCUSQYAV-UHFFFAOYSA-N C(C)(C)(C)C=1C=C(C=C(C1O)CN)CCC(=O)O Chemical compound C(C)(C)(C)C=1C=C(C=C(C1O)CN)CCC(=O)O RTJUWEUCUSQYAV-UHFFFAOYSA-N 0.000 description 1
- 101100232929 Caenorhabditis elegans pat-4 gene Proteins 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
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- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
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- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
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- XGNZNBRDPPLKTC-UHFFFAOYSA-N aluminium diboride Chemical compound [Al]1B=B1 XGNZNBRDPPLKTC-UHFFFAOYSA-N 0.000 description 1
- 229940059260 amidate Drugs 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
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- 230000003078 antioxidant effect Effects 0.000 description 1
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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- 150000004054 benzoquinones Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
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- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000010434 nepheline Substances 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000005461 organic phosphorous group Chemical group 0.000 description 1
- 125000002092 orthoester group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种间同立构聚苯乙烯共混物,含有间同立构聚苯乙烯和聚亚芳基醚,其中聚亚芳基醚在25℃的氯仿中测量时,其特性粘度小于约0.25克/分升(g/dl)。
Description
背景技术
本发明涉及间同立构聚苯乙烯和聚亚芳基醚的共混物。
间同立构聚苯乙烯由于它的结晶形态而显然是具有优异的耐热和耐化学性。聚亚芳基醚与间同立构聚苯乙烯是高度互溶的,然而,聚亚芳基醚的存在可能损害间同立构聚苯乙烯结晶度的水平和比率。而结晶度的降低可能又使耐热和耐化学性都降低。
此外,基于其熔融温度和降解温度一般只有约30℃的差别这个事实,间同立构聚苯乙烯具有很小的加工温度范围。人们已经试图通过掺入添加剂,特别是流动促进剂,来改善这么窄的加工温度范围,以提高间同立构聚苯乙烯的可加工性。这些添加剂可能会削弱间同立构聚苯乙烯某些需要的物理性质,例如耐化学性、耐湿性和热变形温度。
发明概述
一种间同立构聚苯乙烯共混物,含有间同立构聚苯乙烯和聚亚芳基醚,其中聚亚芳基醚在25℃的氯仿中测量时,其特性粘度小于约0.25克/分升(g/dl)。
附图说明
图1是间同立构聚苯乙烯和间同立构聚苯乙烯共混物粘度的对比图。
图2是表明在间同立构聚苯乙烯共混物的粘度与其聚亚芳基醚含量的关系。
图3是表明在间同立构聚苯乙烯共混物中聚亚芳基醚的含量与结晶度数值的关系。
图4是表明含有高特性粘度聚亚芳基醚或低特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物中结晶度与冷却速率的关系。
详细说明
一种间同立构聚苯乙烯共混物,含有间同立构聚苯乙烯和聚亚芳基醚,其中聚亚芳基醚在25℃的氯仿中测量时,其特性粘度小于约0.25克/分升(g/dl)。间同立构聚苯乙烯共混物具有比间同立构聚苯乙烯更低的熔融粘度,从而可以降低加工过程的降解量。间同立构聚苯乙烯共混物的熔融粘度优选小于或等于间同立构聚苯乙烯熔融粘度的约95%,更优选为小于或等于约90%,最优选为小于或等于约85%。熔融粘度越低,可能导致加工时间越短,同时还可以减少剪切生热。
采用低特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物证明比对应的采用高特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物具有更高水平的结晶度。这里所用的低特性粘度聚亚芳基醚定义为在25℃的氯仿中测量时,其特性粘度小于约0.25g/dl的聚亚芳基醚。高特性粘度聚亚芳基醚定义为在25℃的氯仿中测量时,其特性粘度大于约0.25g/dl的聚亚芳基醚。
含有低特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物优选为具有大于或等于约30%的结晶度,更优选为大于或等于约40%的结晶度,最优选为大于或等于约50%的结晶度。与采用高特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物不同,含有低特性粘度聚亚芳基醚的间同立构聚苯乙烯共混物即使快速冷却时也能具有高水平的结晶度。高水平的结晶度是需要的,因为结晶度水平一般与在高温下的耐化学性和尺寸稳定性直接相关。此外,当使低特性粘度聚亚芳基醚功能化后,间同立构聚苯乙烯共混物表现出与填充材料更好的黏结性,并且与其它热塑性材料(例如聚酰胺)的相容性和形态都得到了改善。
间同立构聚苯乙烯是一种具有高度规则立体化学结构的聚苯乙烯,也就是说,高度间同立构的构象。换句话说,侧基的苯基基团和取代的苯基基团是在相对于主聚合链的交替位置上。在立体化学结构中的立构规整度可以通过采用碳同位素(13C)的核磁共振(13C-NMR)来定量地确定。通过13C-NMR方法测得的立构规整度可以显示出序列的内容,其中在序列中特定数目的组成单元连在一起,例如,二单元组在序列中有两个组成单元连在一起,三单元组在序列中有三个组成单元连在一起,五单元组在序列中有五个组成单元连在一起。这里的间同立构聚苯乙烯定义为聚苯乙烯、聚烷基苯乙烯、聚卤代苯乙烯、聚卤代烷基苯乙烯、聚烷氧基苯乙烯、聚乙烯基苯甲酸酯、这些聚合物的氢化衍生物、含有上述聚合物之一的共混物、或者含有这些聚合物的组成单元作为主要组分的共聚物,它们一般具有的间同规整度根据外消旋二单元组的含量表示为75%或更大,优选为85%或更大,或者根据外消旋五单元组的含量表示为30%或更大,优选为50%或更大。
聚烷基苯乙烯的例子包括,但不限于,聚甲基苯乙烯、聚乙基苯乙烯、聚异丙基苯乙烯、聚叔丁基苯乙烯、聚苯基苯乙烯、聚乙烯基亚萘基、和聚乙烯基苯乙烯。聚卤代苯乙烯的例子包括聚氯代苯乙烯、聚溴代苯乙烯、和聚氟代苯乙烯。聚卤代烷基苯乙烯的例子包括聚氯代甲基苯乙烯。聚烷氧基苯乙烯的例子包括聚甲氧基苯乙烯和聚乙氧基苯乙烯。
间同立构聚苯乙烯的特别优选的例子包括聚苯乙烯、聚对甲基苯乙烯、聚间甲基苯乙烯、聚对叔丁基苯乙烯、聚对氯代苯乙烯、聚间氯代苯乙烯、聚对氟代苯乙烯、氢化苯乙烯,含有包括上述聚合物单元的共聚物和包括上述间同立构聚苯乙烯之一的组合物。
苯乙烯聚合物的分子量没有特别地限制。重均分子量优选为大于或等于约10,000,且优选为大于或等于约50,000。分子量分布没有特别地限制,可以采用具有各种各样的分子量分布的间同立构聚苯乙烯。
间同立构聚苯乙烯可以通过使苯乙烯基单体(与间同立构聚苯乙烯中重复单元相对的单体)在惰性烃溶剂中或者在不含溶剂条件下采用钛化合物和水与三烷基铝的缩聚产物作为催化剂进行聚合来制备。
间同立构聚苯乙烯一般用量为基于共混物总重量的大于或等于约40wt%,优选为大于或等于约50wt%,更优选为大于或等于约70wt%,以及用量小于或等于约99wt%,优选为小于或等于约98wt%,更优选为小于或等于约95wt%。
术语“聚亚芳基醚”包括聚苯醚(PPE)和聚亚芳基醚共聚物、接枝共聚物、聚亚芳基醚醚离子键共聚物;以及链烯基芳香族化合物、乙烯基芳香族化合物和聚亚芳基醚等的嵌段共聚物;以及含有前述化合物至少一种的组合。聚亚芳基醚本身是含有许多如式(I)结构单元的公知聚合物:
其中对于每一个结构单元,每一个Q1独立地为卤原子、伯或仲低级烷基(例如,含有直到7个碳原子的烷基)、苯基、卤代烷基、氨基烷基、烃氧基、卤原子和氧原子之间至少隔两个碳原子的卤代烃氧基等,以及每一个Q2独立地为氢、卤原子、伯或仲低级烷基、苯基、卤代烷基、烃氧基、卤原子和氧原子之间至少隔两个碳原子的卤代烃氧基等。优选地,每一个Q1为烷基或苯基,尤其是C1-4烷基,而每一个Q2为氢。
聚亚芳基醚既包括它的均聚物,也包括它的共聚物。优选的均聚物为那些含有2,6-二甲基聚亚芳基醚单元的化合物。适合的共聚物包括含有例如,与2,3,6-三甲基-1,4-苯基醚单元结合的这样的单元的无规共聚物,或者由2,6-二甲基苯酚与2,3,6-三甲基苯酚共聚合而衍生的共聚物。同样包括含有通过乙烯基单体或聚合物(例如苯乙烯)接枝而制备的基团的聚亚芳基醚,以及偶联的聚亚芳基醚,其中偶联剂(例如低分子量聚碳酸酯、苯醌、杂环化合物和甲醛)以公知的方式与两个聚亚芳基醚链的羟基基团反应生成更高分子量的聚合物。本发明的聚亚芳基醚还包括含有至少一种上述化合物的组合。
聚亚芳基醚一般具有数均分子量为约2,000-约12,000原子质量单位(amu),重均分子量为约5,000-约25,000amu,通过凝胶渗透色谱测定。聚亚芳基醚的特性粘度在25℃氯仿中测量为小于约0.25分升/克(dl/g),优选为小于约0.15dl/g,更优选为约0.12dl/g。
聚亚芳基醚一般通过至少一个单羟基芳香族化合物(例如2,6-二甲苯酚或2,3,6-三甲苯酚)的氧化偶联来制备。对于这样的偶联一般采用催化剂体系,它们一般含有至少一种重金属化合物,例如铜、锰或钴化合物,常常与其它各种各样的物质配合使用。
聚苯基醚共聚物也可以具有不同的端基,例如含有氨基烷基的端基和4-羟基联苯端基,一般通过在氧化偶联反应合成时插入。聚苯基醚树脂可以通过端基功能化或封端,这样可以使聚合物增加更多的反应活性并在某些情况下还可能提供额外的与添加剂和其它聚合物树脂(可以用来制备合金或共混物)的相容性。例如,聚苯基醚可以通过将聚苯基醚共聚物与本领域公知的功能化试剂,用环氧端基、磷酸盐端基、丙烯酸酯或甲基丙烯酸酯端基或者原酸酯端基来功能化。
很显然对于本领域的熟练技术人员来说,通过上述说明,预想的聚亚芳基醚包括所有那些已经公知的化合物,而不考虑其结构单元或附属化学特征的变化。
一般聚亚芳基醚的用量为基于共混物总重量的大于或等于约1wt%,优选为大于或等于约2wt%,更优选为大于或等于约5wt%,以及用量为小于或等于约60wt%,优选为小于或等于约50wt%,更优选为小于或等于约30wt%。
间同立构聚苯乙烯共混物还可以包括一种或多种填料,包括低纵横比的填料、纤维状填料和聚合填料。填料的非限制性的例子包括二氧化硅粉末,如熔凝二氧化硅、结晶二氧化硅、天然石英砂、和各种硅烷涂层的二氧化硅;氮化硼粉末和硅酸硼粉末;氧化铝和氧化镁;硅灰石包括表面处理的;硫酸钙(例如,其无水物、二水合物或三水合物);碳酸钙包括白垩、石灰、大理石和人造石、沉淀碳酸钙,一般是磨碎的颗粒形式,通常含98+%的CaCO3和其余为无机物如碳酸镁、氧化铁和硅酸铝;表面处理的碳酸钙;滑石,包括纤维状、块状、针状和片状的滑石;玻璃球,中空或实心,及表面处理的玻璃球,一般具有偶联剂如硅烷偶联剂和/或含有导电涂层;高岭土包括硬质、软质、煅烧高岭土、和含有各种本领域公知的涂层以促进其分散性和相容性的高岭土;云母,包括金属化云母和表面用氨基硅烷或丙烯酰硅烷涂料处理的云母;钾长石和霞石正长石;硅酸盐球;烟道灰;煤胞;fillite;硅酸铝(armosphere),包括硅烷化和金属化的硅酸铝;石英;石英岩;珍珠岩;硅藻土;碳化硅;硫化钼;硫化锌;硅酸铝(莫来石);合成硅酸钙;硅酸锆;钛酸钡;铁酸钡;硫酸钡和重晶石;颗粒状或纤维状铝、青铜、锌、铜和镍;碳黑,包括导电碳黑;石墨,如石墨粉;片状填料和增强材料,如玻璃片、片状碳化硅、二硼化铝、铝片和钢片;加工过的矿物纤维,如那些由含有硅酸铝、氧化铝、氧化镁和硫酸钙半水合物中至少一种的共混物衍生的化合物;天然纤维包括木粉、纤维素、棉花、剑麻、黄麻、淀粉、软木粉、木质素、花生壳和谷壳;合成的增强纤维,包括聚酯纤维例如聚对苯二甲酸乙二醇酯纤维、聚乙烯醇纤维、芳香族聚酰胺纤维、聚苯并咪唑纤维、聚酰亚胺纤维、聚苯硫醚纤维、聚醚醚酮纤维、硼纤维、陶瓷纤维(如碳化硅)、以及由混合的铝、硼和硅的氧化物得到的纤维;单晶纤维或“晶须”包括碳化硅纤维、氧化铝纤维、碳化硼纤维、铁纤维、镍纤维、铜纤维;玻璃纤维,包括织物状玻纤如E、A、C、ECR、R、S、D和NE玻璃、及石英;以及气相生长的碳纤维包括那些具有平均直径为约3.5纳米-500纳米的碳纤维,如Tibbetts等人的美国专利US4,565,684和US 5,024,818、Arakawa的美国专利US 4,572,813、Tennent的美国专利US 4,663,230和US 5,165,909、Komatsu等人的美国专利US4,816,289、Arakawa的美国专利US 4,876,078、Tennent申请的美国专利US5,589,152和Nahass等人的美国专利US 5,591,382。优选的纤维为玻璃纤维。
填料,如果存在,一般用量为基于组合物总重量的大于或等于约1wt%,优选为大于或等于约5wt%,更优选为大于或等于约10wt%,以及用量为小于或等于约50wt%,优选为小于或等于约40wt%,更优选为小于或等于约30wt%。
间同立构聚苯乙烯共混物还可以包括抗冲击改良剂。特别适合的热塑性抗冲击改良剂为嵌段共聚物,例如,具有一个或两个链烯基芳香族嵌段A(一般为苯乙烯嵌段)和一个橡胶嵌段B(一般为异戊二烯或丁二烯)的A-B二嵌段共聚物和A-B-A三嵌段共聚物。丁二烯嵌段可以是部分氢化的。这些二嵌段和三嵌段共聚物的混合物特别有用。
适合的A-B和A-B-A共聚物包括但不限于聚苯乙烯-聚丁二烯、聚苯乙烯-聚(乙烯-丙烯)、聚苯乙烯-聚异戊二烯、聚(α-甲基苯乙烯)-聚丁二烯、聚苯乙烯-聚丁二烯-聚苯乙烯(SBS)、聚苯乙烯-聚(乙烯-丙烯)-聚苯乙烯、聚苯乙烯-聚异戊二烯-聚苯乙烯和聚(α-甲基苯乙烯)-聚丁二烯-聚(α-甲基苯乙烯),以及它们选择性氢化的产物等。上述嵌段共聚物的混合物同样有用。这样的A-B和A-B-A嵌段共聚物市场上可以通过多种来源得到,包括来自Phillips Petroleum(菲利普石油)的商标为SOLPRENE的产品、来自ShellChemical Co.(壳牌化学公司)的商标为KRATON的产品、来自Dexco(德克斯哥)的商标为VECTOR的产品和来自Kuraray(库拉雷)的商标为SEPTON的产品。
抗冲击改良剂一般用量为基于组合物总重量的大于或等于约1wt%,优选为大于或等于约5wt%,更优选为大于或等于约10wt%,以及用量为小于或等于约50wt%,优选为小于或等于约40wt%,更优选为小于或等于约30wt%。
间同立构聚苯乙烯共混物可以任选地含有各种添加剂,例如抗氧化剂,如有机亚磷酸酯,如三(壬基苯基)亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、二(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯或二硬脂酰基季戊四醇二亚磷酸酯、烷基化的一元酚、多元酚和多元酚与二烯的烷基化反应产物例如四[亚甲基-(3,5-二叔丁基-4-羟基苯基丙酸酯)]甲烷、3,5-二叔丁基-4-羟基苯基丙酸酯基十八烷基、2,4-二叔丁基苯基亚磷酸酯、对甲苯酚与二环戊二烯的丁基化反应产物、烷基化的氢醌、羟基化的硫代二苯基醚、亚烷基-二苯酚、苄基化合物、β-(3,5-二叔丁基-4-羟基苯基)丙酸与单羟基或多羟基醇的酯、β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与单羟基或多羟基醇的酯;硫代烷基或硫代芳基化合物的酯,例如硫代丙酸酯二(十八烷基)酯、硫代丙酸酯二(月桂醇)酯、硫代二丙酸酯二(十三烷基)酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸的酰胺化物;以及其它添加剂如脱模剂、UV吸收剂、稳定剂(如光稳定剂和其它稳定剂)、润滑剂、增塑剂、颜料、染料、着色剂、抗静电剂、发泡剂、阻燃剂等等。
将间同立构聚苯乙烯、低特性粘度聚亚芳基醚和其它可任选含的组分组合并混合在一起形成最终的共混物。该混合的方法并不限于一种特定的方式,例如按添加的顺序。该混合物优选加热到间同立构聚苯乙烯的熔融温度之上、降解温度之下。间同立构聚苯乙烯共混物可以先形成粒状,随后由颗粒来形成制品或者也可以立即加工成制品。当由间同立构聚苯乙烯共混物形成制品时,该制品可以快速冷却而结晶度没有显著降低。这里快速冷却定义为每分钟温度下降大于约50℃。
所有专利在这里作为参考文献引用。本发明还通过下面的具体实施例进一步说明,但这些实施例并不是要限制本发明。
实施例1
将重均分子量(Mw)为250,000原子质量单位的间同立构聚苯乙烯与30重量百分数(wt%)的特性粘度为0.12dl/g或0.40dl/g的聚亚芳基醚结合。随后采用平行板动态粘度计在280℃下测量熔融粘度。从图1可以看出,含有特性粘度为0.40dl/g的聚亚芳基醚的共混物比未共混的间同立构聚苯乙烯具有更高的熔融粘度,而含有特性粘度为0.12dl/g的聚亚芳基醚的共混物比未共混的间同立构聚苯乙烯的熔融粘度低。
实施例2
将间同立构聚苯乙烯、含有30wt%玻璃纤维的间同立构聚苯乙烯、和含有抗冲击改良剂的间同立构聚苯乙烯与不同含量的特性粘度为0.12dl/g或0.40dl/g的聚亚芳基醚结合。在290℃下测量毛细管粘度。从图2可以看出,含有特性粘度为0.12dl/g的聚亚芳基醚的共混物比间同立构聚苯乙烯或者间同立构聚苯乙烯与特性粘度为0.40dl/g的聚亚芳基醚的共混物明显具有更低的粘度。
实施例3
将间同立构聚苯乙烯、含有30wt%玻璃纤维的间同立构聚苯乙烯、和含有抗冲击改良剂的间同立构聚苯乙烯与不同含量的特性粘度为0.12dl/g或0.40dl/g的聚亚芳基醚结合。共混物和间同立构聚苯乙烯从熔融态以受控的冷却速率(20℃/分钟)重结晶。通过差示扫描量热法(DSC)测定结晶度。如图3所示的结果表明在给定水平的聚亚芳基醚的情况下,含有特性粘度为0.12dl/g的聚亚芳基醚的共混物比含有特性粘度为0.40dl/g的聚亚芳基醚的共混物具有更高水平的结晶度。这种差别在含有填料的共混物和含有大于30wt%聚亚芳基醚的共混物中特别明显。
实施例4
共混物含有间同立构聚苯乙烯和20wt%的具有特性粘度为0.12dl/g的聚亚芳基醚或者20wt%的具有特性粘度为0.40dl/g的聚亚芳基醚。随后将这些共混物从熔融态以不同的(冷却)速率重结晶,通过DSC测定最终的结晶度。从图4可以看出,在高冷却速率的条件下,含有特性粘度为0.12dl/g的聚亚芳基醚的共混物比含有特性粘度为0.40dl/g的聚亚芳基醚的共混物具有更高水平的结晶度。
通过上述实施例可以看出,含有低粘度聚亚芳基醚的间同立构聚苯乙烯共混物比间同立构聚苯乙烯或间同立构聚苯乙烯与高粘度聚亚芳基醚的共混物具有更低的粘度。此外,含有低粘度聚亚芳基醚的共混物比含有高粘度聚亚芳基醚的共混物具有更高水平的结晶度。
在已经显示和说明了本发明优选的一些实施方案的同时,还可以对其作出不偏离本发明构思和范围的各种各样修改和替换。因此,本发明应当被理解为已经是通过举例性而不是限制性的方式作了说明。
Claims (15)
1.一种间同立构聚苯乙烯共混物,含有间同立构聚苯乙烯和聚亚芳基醚,其中聚亚芳基醚在25℃的氯仿中测量时的特性粘度小于0.25克/分升(g/dl)。
2.权利要求1所述的共混物,其中该共混物的熔融粘度小于或等于该间同立构聚苯乙烯熔融粘度的约95%。
3.权利要求1所述的共混物,其中该共混物具有大于或等于30%的结晶度。
4.权利要求1所述的共混物,其中该聚亚芳基醚是功能化的。
5.权利要求1所述的共混物,其中该间同立构聚苯乙烯具有的间同规整度为30%或更大,根据外消旋五单元组的含量来表示。
6.权利要求1所述的共混物,其中该间同立构聚苯乙烯具有的间同规整度为75%或更大,根据外消旋二单元组的含量来表示。
7.权利要求1所述的共混物,其中该间同立构聚苯乙烯具有的重均分子量大于约10,000。
8.权利要求1所述的共混物,其中该间同立构聚苯乙烯存在的量是基于共混物总重量的约40wt%到约99wt%之间。
9.权利要求1所述的共混物,其中该聚亚芳基醚在25℃的氯仿中测量时的特性粘度小于0.15g/dl。
10.权利要求1所述的共混物,其中该聚亚芳基醚存在的量是基于共混物总重量的约1wt%到约60wt%之间。
11.权利要求1所述的共混物,还含有填料。
12.权利要求11所述的共混物,其中该填料包括玻璃纤维。
13.权利要求11所述的共混物,其中该填料存在的量是基于组合物总重量的约1wt%到约50wt%之间。
14.权利要求1所述的共混物,还含有抗冲击改良剂。
15.权利要求11所述的共混物,其中该抗冲击改良剂存在的量是基于组合物总重量的约1wt%到约50wt%之间。
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2002
- 2002-05-20 US US10/063,853 patent/US6894102B2/en not_active Expired - Fee Related
-
2003
- 2003-05-13 CN CNB03815997XA patent/CN1325554C/zh not_active Expired - Fee Related
- 2003-05-13 EP EP03734015A patent/EP1507827A1/en not_active Withdrawn
- 2003-05-13 JP JP2004508171A patent/JP2005526894A/ja not_active Withdrawn
- 2003-05-13 WO PCT/US2003/015036 patent/WO2003099923A1/en active Application Filing
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN104098886A (zh) * | 2014-07-08 | 2014-10-15 | 安徽宁国市高新管业有限公司 | 一种耐水耐热阻燃的电缆护套材料 |
CN106189173A (zh) * | 2015-06-01 | 2016-12-07 | 旭化成株式会社 | 风扇成型品 |
TWI636868B (zh) * | 2015-06-01 | 2018-10-01 | 旭化成股份有限公司 | 風扇成型品 |
Also Published As
Publication number | Publication date |
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EP1507827A1 (en) | 2005-02-23 |
US20030216503A1 (en) | 2003-11-20 |
JP2005526894A (ja) | 2005-09-08 |
CN1325554C (zh) | 2007-07-11 |
US6894102B2 (en) | 2005-05-17 |
WO2003099923A1 (en) | 2003-12-04 |
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