CN104558415B - A kind of rubber composition and vulcanization rubber - Google Patents
A kind of rubber composition and vulcanization rubber Download PDFInfo
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- CN104558415B CN104558415B CN201310512797.9A CN201310512797A CN104558415B CN 104558415 B CN104558415 B CN 104558415B CN 201310512797 A CN201310512797 A CN 201310512797A CN 104558415 B CN104558415 B CN 104558415B
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- Prior art keywords
- olefin polymer
- rubber
- rubber composition
- composition according
- structural unit
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 110
- 239000005060 rubber Substances 0.000 title claims abstract description 109
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000004073 vulcanization Methods 0.000 title claims abstract description 23
- 150000001993 dienes Chemical class 0.000 claims abstract description 57
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 239000011574 phosphorus Substances 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 229920000098 polyolefin Polymers 0.000 claims description 159
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 55
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000003999 initiator Substances 0.000 claims description 28
- 239000004636 vulcanized rubber Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 15
- 238000009826 distribution Methods 0.000 claims description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012744 reinforcing agent Substances 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 claims description 2
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 238000005096 rolling process Methods 0.000 abstract description 22
- 229910000077 silane Inorganic materials 0.000 abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000010276 construction Methods 0.000 abstract 3
- 239000005864 Sulphur Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 34
- 238000012360 testing method Methods 0.000 description 34
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 28
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000000034 method Methods 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 125000003396 thiol group Chemical group [H]S* 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 14
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 14
- -1 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy Chemical group 0.000 description 14
- 239000006229 carbon black Substances 0.000 description 13
- 235000019241 carbon black Nutrition 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical group CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 3
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical group C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
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- 230000006835 compression Effects 0.000 description 2
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
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- 230000009477 glass transition Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical group [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- QHDCFDQKXQIXLF-UHFFFAOYSA-N sulfuric acid sulfurous acid Chemical compound OS(O)=O.OS(O)(=O)=O QHDCFDQKXQIXLF-UHFFFAOYSA-N 0.000 description 2
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
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- 239000011787 zinc oxide Substances 0.000 description 2
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- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 description 1
- VBCKYDVWOPZOBA-UHFFFAOYSA-N 2-(oxolan-2-ylmethoxymethyl)oxolane Chemical compound C1CCOC1COCC1CCCO1 VBCKYDVWOPZOBA-UHFFFAOYSA-N 0.000 description 1
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- YBYVZXAEQRHBPY-UHFFFAOYSA-N 4-(morpholin-4-yltetrasulfanyl)morpholine Chemical compound C1COCCN1SSSSN1CCOCC1 YBYVZXAEQRHBPY-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 241001441571 Hiodontidae Species 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 229950005499 carbon tetrachloride Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MHEMRIIGLWLYQA-UHFFFAOYSA-N diazanium sulfurous acid sulfate Chemical compound [NH4+].[NH4+].OS(O)=O.[O-]S([O-])(=O)=O MHEMRIIGLWLYQA-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- OSPOKMCEHIMIRN-UHFFFAOYSA-L dipotassium sulfuric acid sulfite Chemical compound S(=O)([O-])[O-].[K+].S(=O)(=O)(O)O.[K+] OSPOKMCEHIMIRN-UHFFFAOYSA-L 0.000 description 1
- GXMCPHJLTWJFLD-UHFFFAOYSA-L disodium sulfurous acid sulfate Chemical compound S(=O)(=O)([O-])[O-].[Na+].S(=O)(O)O.[Na+] GXMCPHJLTWJFLD-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940024464 emollients and protectives zinc product Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a kind of rubber composition and it is well mixed by the rubber composition and is vulcanized obtained vulcanization rubber.The rubber composition contains modified olefine polymer, contain at least one monovinylarene construction unit and at least two conjugated diene construction units in the strand of the modified olefine polymer, and also contain formula in the strand of the modified olefine polymer(Ⅰ)Shown silane coupler construction unit, the number-average molecular weight of the modified olefine polymer is 50,000 100 ten thousand;R1‑R4For C1‑C20Straight or branched alkyl or contain heteroatomic C1‑C20Straight or branched alkyl, one or more of the hetero atom in halogen, oxygen, sulphur, silicon and phosphorus.The rubber composition can be between active balance anti-slippery and rolling resistance relation.
Description
Technical Field
The present invention relates to a rubber composition and a vulcanized rubber obtained by uniformly mixing and vulcanizing the rubber composition.
Background
In recent years, with the development of the automobile industry and the rising of the oil price, people pay more attention to the safety and energy saving of automobiles, and tires having high wet skid resistance and low rolling resistance are required. However, it is often difficult to achieve both improved wet skid resistance and reduced rolling resistance. Therefore, according to different use requirements, an optimum balance between high wet skid resistance and low rolling resistance needs to be found.
For producing a tire with low rolling resistance, the anion-polymerized solution-polymerized butylbenzene has more remarkable advantages than emulsion-polymerized butylbenzene because the anion solution polymerization can effectively adjust the content and the glass transition temperature of a conjugated diene structural unit with a double bond in a side chain. This advantage is advantageous for balancing the relationship between the wet skid resistance and the rolling resistance of the tire. Further, studies have shown that the addition of a silane coupling agent during the kneading of a rubber composition can promote the dispersion of a filler in the raw rubber to some extent and improve the relationship between the wet skid resistance and the rolling resistance of the rubber to some extent, but the reactivity of the silane coupling agent with the raw rubber and carbon black is lowered by the influence of other additives during the kneading of the rubber composition. Further, addition of the silane coupling agent during the kneading of the rubber composition also causes an unpleasant odor. It is disclosed in EP447066 that a silane having a structure represented by formula (1) can be used as a modifier to improve wet skid resistance and reduce rolling resistance of styrene-butadiene rubber:
USi(OR')jR''4-i-jthe compound of the formula (1),
wherein U is halogen, R 'and R' are C1-C20J is an integer from 1 to 4, i is an integer from 0 to 2, and the sum of i and j is from 2 to 4. The silane having the structure represented by formula (1) can be bonded to a polymer molecular chain by reacting a halogen with a catalyst residue at the end of the polymer molecular chain, however, usually, one polymer molecular chain can be bonded with only one silane molecule, and only a small influence is exerted on the interaction between the polymer molecular chains, and the wet skid resistance of rubber cannot be effectively improved and the rolling resistance is reducedDynamic resistance.
Disclosure of Invention
The invention aims to overcome the defect that the relation between the wet skid resistance and the rolling resistance of rubber cannot be effectively improved by the conventional method, and provides a rubber composition which has high wet skid resistance and low rolling resistance and vulcanized rubber obtained by uniformly mixing and vulcanizing the rubber composition.
The invention provides a rubber composition, which contains olefin rubber, a vulcanizing agent, a vulcanization accelerator, a reinforcing agent and an activator, wherein the olefin rubber contains a modified olefin polymer, the molecular chain of the modified olefin polymer contains at least one monovinylarene structural unit and at least two conjugated diene structural units, the molecular chain of the modified olefin polymer also contains a silane coupling agent structural unit shown in a formula (I), and the number average molecular weight of the modified olefin polymer is 5-100 ten thousand;
wherein R is1-R4Is C1-C20A straight or branched hydrocarbon group or C containing a hetero atom1-C20The heteroatom is selected from one or more of halogen, oxygen, sulfur, silicon and phosphorus.
The invention also provides vulcanized rubber obtained by uniformly mixing and vulcanizing the rubber composition.
As described above, in the prior art, the silane coupling agent is generally added during the kneading of the rubber composition to improve the wet skid resistance of the rubber and to reduce the rolling resistance thereof, but in this case, the reactivity of the silane coupling agent with the raw rubber and the carbon black is reduced, and it is difficult to significantly improve the relationship between the wet skid resistance and the rolling resistance of the rubber and an unpleasant odor is generated. The present inventors have made intensive studies and, as a result, have found that by chemically bonding a silane coupling agent to an olefin polymer and using the resulting modified olefin polymer as a whole as a part or whole of a rubber-based rubber, it is possible to avoid the problem of a decrease in the reactivity of the silane coupling agent with raw rubber and carbon black caused during the mixing of a rubber composition, and to effectively balance the relationship between wet skid resistance and rolling resistance of a tire made of the rubber composition, and also to improve the unpleasant odor caused by the use of the silane coupling agent during the mixing of the rubber composition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The rubber composition provided by the invention contains olefin rubber, a vulcanizing agent, a vulcanization accelerator, a reinforcing agent and an activator, wherein the olefin rubber contains a modified olefin polymer, the molecular chain of the modified olefin polymer contains at least one monovinylarene structural unit and at least two conjugated diene structural units, the molecular chain of the modified olefin polymer also contains a silane coupling agent structural unit shown in a formula (I), and the number average molecular weight of the modified olefin polymer is 5-100 ten thousand;
wherein R is1-R4Is C1-C20A straight or branched hydrocarbon group or C containing a hetero atom1-C20A linear or branched hydrocarbon group of (a),the heteroatom is selected from one or more of halogen, oxygen, sulfur, silicon and phosphorus; preferably, R1-R3Is C1-C5A linear or branched alkyl group or a linear or branched alkoxy group of R4Is C1-C5Linear or branched alkylene groups of (a).
Said C is1-C5Specific examples of the linear or branched alkyl group of (a) include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl and neopentyl; said C is1-C5Specific examples of the linear or branched alkoxy group of (a) include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and neopentoxy; said C is1-C5Specific examples of the linear or branched alkylene group of (a) include, but are not limited to: methylene, ethylene, propylene, butylene, and pentylene.
The content of the modified olefin polymer in the olefin rubber is not particularly limited in the present invention, and for example, the content of the modified olefin polymer in the olefin rubber may be 50 to 100% by weight, preferably 80 to 100% by weight, based on the total weight of the olefin rubber.
On the molecular chain of the modified olefin polymer, a monovinylarene structural unit and a conjugated diene structural unit form a main chain of the polymer, and a silane coupling agent structural unit shown in a formula (I) is bonded to the conjugated diene structural unit on the main chain.
Particularly preferably, in the formula (I), R1-R3Is methoxy, R4Is propylene, in this case, the silane coupling agent corresponding to the structural unit of the silane coupling agent represented by formula (I) is gamma-mercaptopropyltrimethoxysilane; or, R1-R3Is ethoxy, R4In this case, the silane coupling agent corresponding to the structural unit of the silane coupling agent represented by the formula (I) is gamma-mercaptopropyl triethoxy siliconAn alkane; or, R1-R3Is methyl, R4In this case, the silane coupling agent corresponding to the structural unit of the silane coupling agent represented by the formula (I) is 2-trimethylsilylethylthiol.
The content of the monovinylarene structural unit, the conjugated diene structural unit and the silane coupling agent structural unit in the modified olefin polymer is not particularly limited and may be adjusted according to the amount of monovinylarene, conjugated diene and silane coupling agent used during the preparation, but in order to provide a rubber composition with higher wet skid resistance and lower rolling resistance, the total content of the monovinylarene structural unit and the conjugated diene structural unit is preferably 90 to 99.99 wt%, more preferably 98 to 99.8 wt%, and the content of the silane coupling agent structural unit is preferably 0.01 to 10 wt%, more preferably 0.2 to 2 wt%, based on the total weight of the modified olefin polymer. Further, the weight ratio of the monovinylarene structural units to the conjugated diene structural units may be from 5:95 to 60:40, preferably from 20:80 to 40: 60.
The number average molecular weight and the molecular weight distribution of the modified olefin polymer are not particularly limited in the present invention, and for example, the number average molecular weight may be 5 to 100 ten thousand, preferably 15 to 20 ten thousand, and the molecular weight distribution may be 1 to 4, preferably 1 to 1.5. The number average molecular weight and the molecular weight distribution were both determined by Gel Permeation Chromatography (GPC) with a model LC-10AT from Shimadzu, THF as the mobile phase, narrow-distribution polystyrene as the standard, and a test temperature of 25 ℃.
According to the invention, the monovinylarene structural units are structural units derived from monovinylarenes, i.e. structural units formed by the polymerization of monovinylarenes. The monovinylarene may be any of the various arene monomers commonly used in the art having a vinyl substituent on the aromatic ring, and generally has the structure shown in formula (iii):
wherein R is5Can be C6-C20Is preferably phenyl and substituted or unsubstituted aryl, preferably by one or more C1-C5Alkyl-substituted phenyl of (a).
According to the invention, said C6-C20Specific examples of substituted or unsubstituted aryl groups of (a) include, but are not limited to: phenyl, tolyl, ethylphenyl, tert-butylphenyl, dodecylphenyl, di-n-butylphenyl (including o-di-n-butylphenyl, m-di-n-butylphenyl and p-di-n-butylphenyl), n-propylphenyl and diethylphenyl (including o-di-n-ethylphenyl, m-di-n-ethylphenyl and p-di-n-ethylphenyl).
according to the invention, the monovinyl aromatic hydrocarbon is particularly preferably at least two of styrene, vinyltoluene, α -methylstyrene, 4-tert-butylstyrene and 4-methylstyrene.
According to the present invention, the conjugated diene structural unit is a structural unit derived from a conjugated diene, that is, a structural unit formed by polymerization of a conjugated diene. The conjugated diolefins are various unsaturated chain hydrocarbons having a conjugated double bond (i.e., -C = C-) in the molecular structure. The conjugated diene may be conventionally selected in the art, is not particularly limited, and may be appropriately selected according to the application of the finally obtained modified olefin polymer, and for example, may be selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, and is preferably butadiene and/or isoprene.
According to the present invention, the modified olefin polymer may be prepared by various methods known to those skilled in the art, for example, the preparation method may include: contacting an olefin polymer comprising at least one monovinylarene structural unit and at least two conjugated diene structural units with a silane coupling agent in an inert atmosphere and in the presence of an initiator, under conditions such that said silane coupling agent is chemically bonded to said olefin polymer; the number average molecular weight of the olefin polymer is 5-100 ten thousand, and the content of the conjugated diene structural unit of which the side chain contains double bonds in the olefin polymer is 15-85 wt%, preferably 30-60 wt%, based on the total weight of the conjugated diene structural unit in the olefin polymer, and the silane coupling agent has a structure represented by formula (II):
wherein R is1-R4Is C1-C20A straight or branched hydrocarbon group or C containing a hetero atom1-C20The heteroatom is selected from one or more of halogen, oxygen, sulfur, silicon and phosphorus; preferably, R1-R3Is C1-C5A linear or branched alkyl group or a linear or branched alkoxy group of R4Is C1-C5Linear or branched alkylene groups of (a).
The content of the conjugated diene structural unit with the side chain containing double bonds can be measured by a nuclear magnetic resonance spectrometer of AVANCE DRX400MHz, which is purchased from Bruker company of Switzerland, wherein, the solvent is deuterated chloroform. Specific assay methods are well known to those skilled in the art and will not be described herein.
Particularly preferably, in the formula (II), R1-R3Is methoxy, R4Is propylene, in which case the corresponding silane coupling agent is gamma-mercaptopropyltrimethoxysilane; or, R1-R3Is ethoxy, R4Is propylene, in which case the corresponding silane coupling agent is gamma-mercaptopropyltriethoxysilane; or, R1-R3Is methyl, R4In the case of ethylene, the corresponding silane coupling agent is 2-trimethylsilylethylthiol.
According to the present invention, the olefin polymer can be produced by various methods known in the art, for example, according to the following method: at least one monovinylarene and at least two conjugated dienes are polymerized in a solvent in an inert atmosphere and in the presence of an initiator under conditions such that the resulting olefin polymer has a number average molecular weight of from 5 to 100 ten thousand and contains, based on the total weight of the conjugated diene structural units in the olefin polymer, from 15 to 85% by weight, preferably from 30 to 60% by weight, of conjugated diene structural units having double bonds in the side chains.
According to the invention, the inert atmosphere refers to any gas or gas mixture that does not chemically react with the reactants and products, such as one or more of nitrogen and a gas from group zero of the periodic table of the elements. The inert atmosphere may be maintained by introducing any one or a mixture of the above gases which do not chemically react with the reactants and the products into the reaction system.
According to the present invention, the initiator may be any of various initiators capable of initiating polymerization of the monovinylarene and the conjugated diene in the preparation of the olefin polymer, and for example, may be an organolithium initiator. The organolithium initiator may be, for example, a mono-organolithium initiator of the formula RLi, wherein R is a linear or branched alkyl, cycloalkyl or aryl group. Specifically, the mono-organolithium initiator may be selected from one or more of ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, hexyllithium, cyclohexyllithium, phenyllithium, methylphenyllithium, and naphthyllithium, preferably n-butyllithium and/or sec-butyllithium. In addition, dilithium initiators, such as trimethylenedilithium and/or tetramethylenedilithium, may also be employed in the present invention. The amount of the initiator used in the present invention is not particularly limited and may be appropriately selected depending on the designed molecular weight. It will be readily understood by those skilled in the art that when it is desired to prepare olefin polymers having a relatively large molecular weight, the amount of initiator used may be reduced, but the rate of polymerization will be correspondingly reduced; when it is desired to produce an olefin polymer having a smaller molecular weight, the amount of the initiator to be used may be increased, but the polymerization rate is increased accordingly. Therefore, in view of the combination of the polymerization rate and the molecular weight of the resulting olefin polymer, it is preferable to use the initiator in an amount of 0.15 to 2.5mmol, based on 100g of the total weight of the monovinylarene and the conjugated diene.
The amount of monovinylarene and conjugated diene used in accordance with the present invention may be selected and varied over a wide range and may be chosen appropriately according to the olefin polymer to be obtained, for example, the weight ratio of monovinylarene to conjugated diene may be from 5:95 to 60:40, preferably from 20:80 to 40: 60.
The conditions for the polymerization reaction in the present invention are not particularly limited, and generally include polymerization temperature, polymerization pressure and polymerization time. Among them, in order to more facilitate the polymerization reaction, the polymerization temperature is preferably 10 to 160 ℃, more preferably 40 to 80 ℃, and the polymerization pressure is preferably 0.05 to 1MPa, more preferably 0.1 to 0.3 MPa. Generally, the extension of the polymerization time is advantageous for the improvement of the conversion of the reactant and the yield of the reaction product, but the extension of the polymerization time is not significant for the improvement of the conversion of the reactant and the yield of the reaction product, and therefore, the polymerization time is preferably 0.5 to 10 hours, more preferably 0.5 to 2 hours, in view of the combination of the polymerization efficiency and effect.
In the present invention, the pressures are gauge pressures.
According to the present invention, the solvent may be various substances capable of acting as a reaction medium in the preparation of the olefin polymer, and for example, may be a hydrocarbon solvent and/or an ether solvent. The hydrocarbon solvent may be C5-C7And (3) one or more of cycloalkanes, aromatics and isoparaffins. Specific examples of the hydrocarbon solvent may include, but are not limited to: one or more of benzene, toluene, pentane, heptane, n-hexane, and cyclohexane. The ether solvent may be C4-C15Monoethers and/or polyethers. Specific examples of the ether solvent may includeIncluding but not limited to: t-butoxyethoxyethane and/or tetrahydrofuran. These solvents may be used alone or in combination. The amount of the solvent to be used may be appropriately selected depending on the amount of the monomer, and for example, the amount of the solvent to be used may be such that the total concentration of the monovinylarene and the conjugated diene is from 1 to 30% by weight, preferably from 5 to 20% by weight.
According to the present invention, after the polymerization reaction is completed, a coupling agent may also be added to the polymerization system to couple at least a part of the olefin polymers together. The kind of the coupling agent is well known to those skilled in the art, and may be, for example, one or more of polyvinyl compounds, halides, ethers, aldehydes, ketones, esters, and the like. Specifically, the coupling agent may be selected from one or more of divinylbenzene, tetravinylsilane, tetrachloromethane, silicon tetrachloride, tin tetrachloride, dimethyl terephthalate, and epoxidized soybean oil, and preferably from one or more of divinylbenzene, silicon tetrachloride, and tin tetrachloride. When the coupling agent is a silane compound, the silane compound is different from the silane coupling agent having the structure represented by formula (ii).
The amount of the coupling agent used in the present invention is not particularly limited, and may be suitably selected depending on the amount of the initiator used, and for example, the molar ratio of the coupling agent to the initiator may be 0.1 to 2:1, preferably 0.1 to 1: 1.
According to the present invention, it is preferable that a structure modifier is further added during the preparation of the olefin polymer, so that the microstructure of the olefin polymer can be effectively controlled. The structure modifier may be any of various existing substances capable of modifying the microstructure of an olefin polymer, and may be, for example, one or more selected from the group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, crown ether, tetrahydrofurfuryl alcohol diethyl ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium tert-amylate, potassium laurate, potassium alkylbenzenesulfonate and sodium alkylbenzenesulfonate. Generally, the molar ratio of the structure-modifying agent to the initiator used for the preparation of the olefin polymer may be from 1 to 100:1, preferably from 80 to 100: 1.
Generally, anionic polymerization systems do not have significant termination and transfer reactions, and the reactive sites remain when all of the monomer is consumed. Therefore, after the polymerization reaction is completed, the resulting polymer solution should be contacted with a terminating agent to inactivate the active centers. The amount of the terminator to be used may be appropriately selected depending on the amount of the initiator to be used for producing the olefin polymer, and in general, the molar ratio of the terminator to the initiator to be used for producing the olefin polymer may be from 0.1 to 1: 1. The terminator may be any of various agents capable of inactivating the anionic active sites, and may be, for example, one or more selected from the group consisting of water, methanol, ethanol and isopropanol, preferably isopropanol.
The conditions for contacting the olefin polymer with the silane coupling agent are not particularly limited in the present invention as long as the silane coupling agent can be chemically bonded to the olefin polymer, and for example, the contacting conditions generally include a contacting temperature, a contacting pressure and a contacting time. Generally, in order to facilitate chemical bonding of the silane coupling agent to the olefin polymer, the contact temperature is preferably 20 to 150 ℃, more preferably 70 to 90 ℃, the contact pressure is preferably 0.01 to 1MPa, more preferably 0.1 to 0.5MPa, and the contact time is preferably 0.1 to 24 hours, more preferably 0.5 to 5 hours.
According to the present invention, in order to achieve both the initiation rate and the molecular weight of the modified olefin polymer when the olefin polymer is contacted with the silane coupling agent, the amount of the initiator is preferably 0.01 to 0.1% by weight, more preferably 0.01 to 0.08% by weight, based on the total weight of the olefin polymer and the silane coupling agent having a structure represented by formula (II). The initiator may be one or more of radical initiators such as azo-type initiators, peroxide-type initiators, and redox-type initiators, which are well known to those skilled in the art.
The azo initiator may be selected from one or more of dimethyl azobisisobutyrate, azobisisobutyramidine hydrochloride, azobisformamide, azobisisopropylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
The peroxide initiator may be selected from one or more of hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, benzoyl peroxide, and benzoyl peroxide tert-butyl ester.
The redox initiator may be selected from one or more of sulfate-sulfite, persulfate-thiourea, persulfate-organic salt and ammonium persulfate-fatty amine. Specifically, the sulfate-sulfite may be selected from one or more of sodium sulfate-sodium sulfite, potassium sulfate-potassium sulfite, and ammonium sulfate-ammonium sulfite; the persulfate-thiourea can be one or more selected from sodium persulfate-thiourea, potassium persulfate-thiourea and ammonium persulfate-thiourea; the persulfate-organic salt can be selected from one or more of sodium persulfate-potassium acetate, potassium persulfate-potassium acetate and ammonium persulfate-ammonium acetate; the ammonium persulfate-fatty amine can be ammonium persulfate-N, N-tetramethylethylenediamine and/or ammonium persulfate-diethylamine.
The amount of the olefin polymer and the silane coupling agent having the structure represented by the formula (II) used in the present invention is not particularly limited, and for example, the amount of the silane coupling agent may be 0.01 to 10g, preferably 0.1 to 5g, more preferably 0.2 to 2g, based on 100g of the olefin polymer.
According to the present invention, various additives may also be selectively added to the resulting modified olefin polymer after the preparation of the modified olefin polymer is completed. The additive may be, for example, an antioxidant, which enables the resulting modified olefin polymer to have good aging resistance. The kind and amount of the antioxidant can be selected conventionally in the field, and will not be described in detail herein.
According to the present invention, after the anti-aging agent is added, the modified olefin polymer may be precipitated from the solution by purification precipitation, centrifugation, filtration, decantation, hot water coagulation, etc., or the solvent in the reaction system may be removed by gas stripping, which is known to those skilled in the art and will not be described herein.
According to the present invention, the olefin rubber may further contain a mixed rubber. The mixed rubber may be selected from one or more of natural rubber, polybutadiene rubber, styrene-butadiene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber and ethylene-propylene-diene rubber. The compounded rubber may be obtained commercially or may be prepared according to various methods known to those skilled in the art, and will not be described herein.
The contents of the modified olefin polymer, the compounded rubber, the vulcanizing agent, the vulcanization accelerator, the reinforcing agent and the activator contained in the rubber composition may be conventionally selected in the art, and for example, the compounded rubber may be contained in an amount of 10 to 40 parts by weight, the vulcanizing agent may be contained in an amount of 1 to 3 parts by weight, the vulcanization accelerator may be contained in an amount of 3 to 5 parts by weight, the reinforcing agent may be contained in an amount of 70 to 90 parts by weight, and the activator may be contained in an amount of 3 to 4 parts by weight, based on 100 parts by weight of the modified olefin polymer.
According to the invention, the vulcanizing agent can be various conventional vulcanizing agents, for example, one or more of insoluble sulfur, dithiomorphine and dimorpholine tetrasulfide, and preferably insoluble sulfur. Wherein the insoluble sulfur is an allotrope of sulfur, which is insoluble in sulfur dioxide and other solvents, and insoluble in rubber, and exists in a dispersed state in the rubber; when reaching the vulcanization temperature, the insoluble sulfur dispersed in the rubber has an activation stage, namely, chain depolymerization, so that the vulcanization speed is accelerated, the sulfur consumption is reduced, and the aging performance of the rubber is improved.
According to the present invention, the vulcanization accelerator may be any of various conventional vulcanization accelerators capable of shortening the vulcanization time, lowering the vulcanization temperature, reducing the amount of a vulcanizing agent used, and improving the physical and mechanical properties of rubber, but in order to obtain a rubber composition having more excellent environmental protection properties, it is preferable that the vulcanization accelerator is a sulfenamide vulcanization accelerator and/or a guanidine vulcanization accelerator; the sulfenamide vulcanization accelerator is preferably one or more selected from the group consisting of N-tert-butyl-2-benzothiazyl sulfenamide, N-cyclohexyl-2-benzothiazyl sulfenamide and N-oxydiethylene-2-benzothiazyl sulfenamide; the guanidine vulcanization accelerator is preferably diphenylguanidine and/or di-o-tolylguanidine. The N-tert-butyl-2-benzothiazyl sulfenamide is a vulcanization accelerator with excellent performance and the commercial name of the N-tert-butyl-2-benzothiazyl sulfenamide is TBBS or NS, and the structural formula of the vulcanization accelerator is shown as the formula (IV):
according to the invention, the type of reinforcing agent is known to the person skilled in the art, and the reinforcing agent may be carbon black and/or white carbon, for example. The carbon black may be any of various existing carbon blacks that can be used in rubber compositions, and may be selected from one or more of industrial reference carbon black # 7, high abrasion furnace black N330, and medium ultra abrasion furnace black N220, for example. The white carbon black can be various existing white carbon blacks capable of improving the strength of the rubber composition, and the white carbon black can be obtained commercially, for example, the white carbon black with the mark number of 115GR from Degussa company.
The type of activator may also be chosen conventionally in the art according to the present invention, and may be, for example, stearic acid and/or zinc oxide.
In addition, the rubber composition of the present invention may optionally contain an antioxidant and/or a silane coupling agent as the case may be, to further enhance the anti-aging property and the wet skid resistance of the rubber composition and to reduce the rolling resistance. The antioxidant may be the same as or different from the antioxidant added in the process of preparing the modified olefin polymer. Further, the silane coupling agent described herein is generally a silane coupling agent containing no mercapto group, unlike the silane coupling agent having a structure represented by formula (II) used in the production process of the modified olefin polymer, and may be, for example, one or more of bis- [ γ - (triethoxysilyl) propyl ] -tetrasulfide, tetravinylsilane, and silicon tetrachloride. The amounts of the antioxidant and the silane coupling agent used herein may be conventionally selected in the art and will not be described herein.
The invention also provides vulcanized rubber obtained by uniformly mixing and vulcanizing the rubber composition.
The main improvement of the present invention is to provide a new rubber composition, and the method for mixing and vulcanizing the rubber composition can be selected conventionally in the field, and it is known to those skilled in the art, and will not be described herein again.
The present invention will be described in detail below by way of examples.
In the following preparations and comparative preparations, the mercapto conversion was measured by agilent 7890A gas chromatograph under the following test conditions: chromatographic column SPB-560m 0.32mm 1.0um capillary column, column flow rate 2.0ml/min, column temperature 220 ℃, gasification chamber temperature 220 ℃, detection chamber temperature 250 ℃, split ratio 50: 1, the sample amount is 0.3 ul. The content of the conjugated diene structural unit with the double bond in the side chain, the content of the monovinylarene structural unit and the content of the conjugated diene structural unit are measured by an AVANCE DRX400MHz nuclear magnetic resonance spectrometer of Bruker company of Switzerland, and the solvent is deuterated chloroform. The number average molecular weight and molecular weight distribution were determined by means of an ALLIANCE model 2690 Gel Permeation Chromatograph (GPC) from WATERS, USA, with THF as the mobile phase and narrow-distribution polystyrene as the standard, at a temperature of 25 ℃. The Mooney viscosity was measured by the method specified in GB/T1232-92 using a Mooney viscometer model SMV-300 from Shimadzu, Japan. The content of the silane coupling agent = charge amount of the silane coupling agent × mercapto conversion ÷ (charge amount of monovinylarene + charge amount of conjugated diene + charge amount of the silane coupling agent × mercapto conversion) × 100%.
Preparation example 1
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 31.20g of styrene, 51.60g of butadiene, 51.20g of isoprene and 1.05g of tetrahydrofurfuryl alcohol ether are added under the protection of high purity nitrogen, then 1.1mmol of n-butyllithium is added after heating to 50 ℃, and the reaction is initiated for 2 hours with the pressure controlled at 0.2MPa to obtain a solution containing an olefin polymer; the number average molecular weight of the olefin polymer was 18.0 ten thousand, and based on the total weight of conjugated diene structural units in the olefin polymer, the content of conjugated diene structural units having double bonds in side chains in the olefin polymer was 41.01 wt%, the content of styrene structural units was 23.28 wt%, the content of butadiene structural units was 38.51 wt%, and the content of isoprene structural units was 38.21 wt%.
(2) 0.8ml (0.836 g) of gamma-mercaptopropyltrimethoxysilane was added to the product obtained in the step (1) and immediately sampled for mercapto group testing, and then 6.5mg of azobisisobutyronitrile was added after heating to 75 ℃ and reacted for 3 hours under a pressure of 0.2MPa to obtain a modified olefin polymer and sampled for mercapto group testing. To the above-mentioned modified olefin polymer was added 0.2g of an antioxidant Irganox1520, and dried under vacuum at 60 ℃ for 24 hours. Wherein the mercapto group conversion rate is 78%, the Mooney viscosity of the modified olefin polymer is 43, the number average molecular weight is 18.0, and the molecular weight distribution is 1.08; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 0.49% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Preparation example 2
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 31.20g of vinyltoluene, 82.30g of butadiene, 30.00g of isoprene and 0.65g of tetrahydrofuran were added under the protection of high purity nitrogen, and then heated to 40 ℃ and 1.0mmol of n-butyllithium was added and the reaction was initiated under a pressure of 0.1MPa for 2 hours to obtain a solution containing an olefin polymer; the number average molecular weight of the olefin polymer was 18.3 ten thousand, and based on the total weight of conjugated diene structural units in the olefin polymer, the content of conjugated diene structural units having double bonds in side chains in the olefin polymer was 33.02% by weight, the content of vinyl toluene structural units was 21.74% by weight, the content of butadiene structural units was 57.35% by weight, and the content of isoprene structural units was 20.91% by weight.
(2) 0.6ml (0.627 g) of gamma-mercaptopropyltrimethoxysilane was added to the product obtained in the step (1), and immediately sampling was conducted for mercapto group testing, then after heating to 80 ℃ 29mg of azobisisobutyronitrile was added and reaction was conducted for 5 hours while controlling the pressure at 0.1MPa to obtain a modified olefin polymer, and sampling was conducted for mercapto group testing. To the above-mentioned modified olefin polymer was added 0.2g of an antioxidant Irganox1520, and dried under vacuum at 60 ℃ for 2 hours. Wherein the mercapto group conversion rate is 82%, the Mooney viscosity of the modified olefin polymer is 49, the number average molecular weight is 18.3, and the molecular weight distribution is 1.08; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 0.35% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Preparation example 3
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of hexane, 32.00g of styrene, 42.30g of butadiene, 70.00g of isoprene and 2.0g of tetrahydrofurfuryl ether were added under the protection of high purity nitrogen, and then heated to 45 ℃ and 1.0mmol of n-butyllithium was added and the reaction was initiated under a pressure of 0.3MPa for 0.5 hour to obtain a solution containing an olefin polymer; the number average molecular weight of the olefin polymer was 19.2 ten thousand, and based on the total weight of conjugated diene structural units in the olefin polymer, the content of conjugated diene structural units having double bonds in side chains in the olefin polymer was 53.02 wt%, the content of styrene structural units was 22.18 wt%, the content of butadiene structural units was 29.31 wt%, and the content of isoprene structural units was 48.51 wt%.
(2) 1.06ml (1.045 g) of gamma-mercaptopropyltriethoxysilane was added to the product obtained in step (1), and immediately sampled for mercapto group testing, then heated to 90 ℃ and added with 30mg of azobisisobutyronitrile, and reacted for 0.5 hour under a pressure of 0.5MPa to obtain a modified olefin polymer, and sampled for mercapto group testing. To the above-mentioned modified olefin polymer was added 0.2g of an antioxidant Irganox1520, and dried under vacuum at 60 ℃ for 24 hours. Wherein the mercapto group conversion rate is 89%, the Mooney viscosity of the modified olefin polymer is 54, the number average molecular weight is 19.2, and the molecular weight distribution is 1.09; the content of the gamma-mercaptopropyltriethoxysilane structural unit was 0.64% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Preparation example 4
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
(1) Adding 2288g of tetrahydrofuran, 20.00g of styrene, 110.00g of butadiene, 25.00g of isoprene and 0.9g of tetrahydrofurfuryl alcohol ether into a 5-liter stainless steel stirring kettle under the protection of high-purity nitrogen, then heating to 80 ℃, adding 1.0mmol of n-butyl lithium, and controlling the pressure at 0.25MPa to initiate the reaction for 1 hour to obtain a product containing an olefin polymer; the number average molecular weight of the olefin polymer was 19.6 ten thousand, and based on the total weight of conjugated diene structural units in the olefin polymer, the content of conjugated diene structural units having double bonds in side chains in the olefin polymer was 51.01 wt%, the content of styrene structural units was 12.90 wt%, the content of butadiene structural units was 70.97 wt%, and the content of isoprene structural units was 16.13 wt%.
(2) To the product obtained in step (1), 3.0ml (3.135 g) of gamma-mercaptopropyltrimethoxysilane was added and immediately sampled for mercapto group testing, and then after heating to 80 ℃ 30mg of azobisisobutyronitrile was added and the pressure was controlled at 0.3MPa for 1 hour of reaction to obtain a modified olefin polymer and sampled for mercapto group testing. To the above-mentioned modified olefin polymer was added 0.2g of an antioxidant Irganox1520, and dried under vacuum at 60 ℃ for 24 hours. Wherein the mercapto group conversion rate is 78%, the Mooney viscosity of the modified olefin polymer is 55, the number average molecular weight is 19.6, and the molecular weight distribution is 1.09; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 1.55% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Preparation example 5
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 62.40g of styrene, 128.60g of butadiene, 120.00g of isoprene and 1.5g of tetrahydrofurfuryl alcohol ether were added under the protection of high purity nitrogen, and then 1.1mmol of n-butyllithium was added at 70 ℃ and the reaction was initiated under a pressure of 0.2MPa for 1.2 hours to obtain a solution containing an olefin polymer; the number average molecular weight of the olefin polymer was 19.1 ten thousand, and based on the total weight of conjugated diene structural units in the olefin polymer, the content of conjugated diene structural units having double bonds in side chains in the olefin polymer was 47.30% by weight, the content of styrene structural units was 20.06% by weight, the content of butadiene structural units was 41.35% by weight, and the content of isoprene structural units was 38.59% by weight.
(2) To the product obtained in step (1), 1.9ml (1.986 g) of gamma-mercaptopropyltrimethoxysilane was added and immediately sampled for mercapto group testing, and then after heating to 70 ℃ 10mg of azobisisobutyronitrile was added and the pressure was controlled at 0.25MPa for 1.2 hours to obtain a modified olefin polymer and sampled for mercapto group testing. To the above-mentioned modified olefin polymer was added 0.4g of an antioxidant Irganox1520, and dried under vacuum at 60 ℃ for 24 hours. Wherein the mercapto group conversion rate is 82%, the Mooney viscosity of the modified olefin polymer is 49, the number average molecular weight is 19.1, and the molecular weight distribution is 1.08; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 0.53% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Preparation example 6
This preparation example is intended to illustrate the modified olefin polymer and the process for producing the same provided by the present invention.
A modified olefin polymer was prepared as in preparation example 4, except that the gamma-mercaptopropyltrimethoxysilane was replaced with the same parts by weight of 2-trimethylsilylethylthiol to obtain a modified olefin polymer. Wherein the mercapto group conversion rate is 65%, the Mooney viscosity of the modified olefin polymer is 51, the number average molecular weight is 18.9, and the molecular weight distribution is 1.09; the content of 2-trimethylsilylethylthiol structural unit was 1.30% by weight based on the total weight of the modified olefin polymer. The polymer has no unpleasant odor.
Comparative preparation example 1
This comparative preparation example is intended to illustrate a reference olefin polymer and a process for producing the same.
An olefin polymer was prepared according to the method of preparation example 1, except that the step (2) was not included, to obtain an olefin polymer. To the above olefin polymer was added 0.4g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein the olefin polymer has a Mooney viscosity of 48, a number average molecular weight of 18.0, and a molecular weight distribution of 1.08; the content of styrene structural units was 23.28% by weight, the content of butadiene structural units was 38.51% by weight, and the content of isoprene structural units was 38.21% by weight, based on the total weight of the olefin polymer.
Comparative preparation example 2
This comparative preparation example is intended to illustrate a reference olefin polymer and a process for producing the same.
(1) 1500g of cyclohexane, 20g of butadiene and 2.7g of tetrahydrofurfuryl alcohol ether are added in a 5 l stainless steel stirred tank under the protection of high-purity nitrogen, and then after heating to 40 ℃ 12mmol of n-butyllithium are added and the reaction is initiated for 1 hour with the pressure being controlled at 0.4MPa to give a solution containing the olefin polymer. The number average molecular weight of the olefin polymer was 1000, and the content of a conjugated diene structural unit having a double bond in a side chain in the olefin polymer was 67% by weight based on the weight of the conjugated diene structural unit in the olefin polymer.
(2) To the product obtained in step (1), 20g of gamma-mercaptopropyltrimethoxysilane was added and immediately sampled for mercapto group testing, then 1g of lauroyl peroxide was added after heating to 100 ℃ and the pressure was controlled at 0.4MPa for 5 hours to obtain a modified olefin polymer and sampled for mercapto group testing. Finally dried in vacuum at 80 ℃ for 24 h. Wherein the modified olefin polymer had a mercapto group conversion of 80% and a number average molecular weight of 1788. The content of the gamma-mercaptopropyltrimethoxysilane structural unit was 44.4% by weight based on the total weight of the modified olefin polymer.
Examples 1 to 5
Examples 1 to 5 are provided to illustrate the vulcanized rubber provided by the present invention and the method for producing the same.
(1) Preparation of rubber compound:
100 parts by weight of the modified olefin polymer prepared in each of preparation examples 1 to 5, 1 part by weight of stearic acid (SA 1801, hong Kong Stevens chemical Co., Ltd.), 10 parts by weight of highly abrasion-resistant furnace black N330 (Tianjin Jinqiu Shikui carbon black chemical Co., Ltd.), and 60 parts by weight of white carbon black 115GR (Germany) were uniformly mixed and subjected to Haake heat treatment at a temperature of 150 ℃ at a rotation speed of 30rpm for 7 minutes. After completion of the heat treatment, the above mixture was charged into an open mill, and 2.5 parts by weight of zinc oxide (zinc products, Liuzhou Co., Ltd.), 1 part by weight of stearic acid (Hongkong Shi chemical Co., Ltd., SA 1801), 2 parts by weight of an antioxidant 4020, 1.4 parts by weight of N-cyclohexyl-2-benzothiazolesulfenamide (available from He mura Binhao chemical Co., Ltd., CZ), 0.75 part by weight of diphenylguanidine (Cangzhou Liang Dow rubber raw materials trade Co., Ltd., DPG) and 6 parts by weight of a silane coupling agent Si69 (Texaco Co., Ltd.) were added and kneaded at 50. + -. 5 ℃ for 60 minutes to obtain a kneaded compound H1-H5.
(2) And (3) vulcanization:
and (2) respectively carrying out vulcanization treatment on the mixed rubber H1-H5 obtained in the step (1) on a flat vulcanizing machine for 40 minutes at 150 ℃ and 12MPa to obtain vulcanized rubber S1-S5.
Example 6
This example serves to illustrate the vulcanizates provided by this invention and their method of preparation.
A vulcanized rubber was prepared by following the procedures of examples 1 to 5, except that 100 parts by weight of the modified olefin polymer prepared in examples 1 to 5 was replaced with a mixture of 80 parts by weight of the modified olefin polymer prepared in preparation example 6 and 20 parts by weight of a natural rubber (Shanghai Yuntai rubber Co., Ltd.), to give a vulcanized rubber S6.
Comparative example 1
This comparative example serves to illustrate the preparation of a reference vulcanizate.
A vulcanized rubber was prepared by following the procedure of example 1 except that the modified olefin polymer prepared in production example 1 was replaced with the olefin polymer prepared in comparative production example 1 and the amount of the olefin polymer added was 99.51 parts by weight, and further, during the preparation of the rubber compound, 0.49 parts by weight of gamma-mercaptopropyltrimethoxysilane was added to obtain a reference vulcanized rubber DS 1.
Comparative example 2
This comparative example serves to illustrate the preparation of a reference vulcanizate.
A vulcanized rubber was prepared by following the procedure of example 1 except that the modified olefin polymer obtained in production example 1 was replaced with a mixture of 98.9 parts by weight of the olefin polymer obtained in comparative production example 1 and 1.1 parts by weight of the modified olefin polymer obtained in comparative production example 2, to obtain a reference vulcanized rubber DS 2.
Test examples 1 to 6
Test examples 1 to 6 are intended to illustrate the tests of wet skid resistance and rolling resistance properties containing the vulcanized rubbers S1 to S6 provided by the present invention.
(1) Testing of glass transition temperature (Tg):
the measurement is carried out by adopting a MDSC2910 Differential Scanning Calorimetry (DSC) instrument of TA company in America, wherein the modulation period is 60s, the modulation amplitude is +/-1.5 ℃, the heating rate is 10 ℃/min, the nitrogen protection is carried out, and the flow rate is 50 mL/min. The results obtained are shown in table 1.
(2) Testing of mechanical properties:
vulcanized rubbers S1 to S6 were each prepared into a vulcanized rubber sheet having a thickness of 2mm, and the obtained vulcanized rubber sheets were cut into dumbbell-shaped standard sheets by a type 1 dumbbell cutter as specified in GB/T528 to 1998, and the mechanical properties of the vulcanized rubber sheets were tested by a rubber tensile machine (AG-20 KNG, manufactured by Shimadzu corporation, Japan) at a test temperature of 25 ℃ and a pulling speed of 500 mm/min to obtain the tensile strength and elongation at break of the vulcanized rubbers, and the results are shown in Table 1.
(3) Test of shore a hardness:
the results obtained were shown in Table 1, and tested according to the method specified in GB/T531-1999.
(4) And (3) testing the deformation resistance:
vulcanized rubbers S1 to S6 were cut into dumbbell-shaped standard pieces by a type 1 dumbbell cutter as specified in GB/T528-92, and the test pieces were pulled apart at a test temperature of 25 ℃ and a pulling speed of 500 mm/min. Placing the sample after tensile fracture for 3min, then jointing the two fractured parts together, measuring the distance between two parallel lines after jointing, and calculating the permanent deformation value after breaking according to the following formula:
Sb=100(Lt-L0)/L0wherein S isbPermanent deformation at break,%; l istThe distance between two parallel lines after the sample is anastomosed is mm; l is0Initial test length, mm. The results obtained are shown in table 1.
(5) And (3) heat buildup property test:
the measurement was carried out using a compression heat generation tester model Y3000E from Beijing Yongshen electronics, wherein the test temperature was 55 ℃, the test time was 25 minutes, and the compression frequency was 30 times/sec. The results obtained are shown in table 1.
(6) Wet skid resistance and rolling resistance test:
the wet-skid resistance and rolling resistance of vulcanized rubber S1-S6 were measured by a DMA-2980 type viscoelastic spectrometer manufactured by TA of America, wherein the test frequency was 2Hz, the temperature rise rate was 5 ℃/min, the test temperature was 100 ℃, and the sample size was 40mm × 5mm × 1 mm. The wet skid resistance of the vulcanized rubber is represented by tan delta at 0 ℃, and the larger tan delta, the better the wet skid resistance of the vulcanized rubber is represented; the rolling resistance of the vulcanized rubber is represented by tan delta at 60 ℃, and the smaller tan delta, the smaller the rolling resistance of the vulcanized rubber; the dispersion of the filler in the rubber is characterized by the value Tan delta (0 ℃ C.)/Tan delta (60 ℃ C.), higher values indicating better dispersion of the filler. The results obtained are shown in table 1.
Comparative test examples 1 to 2
Comparative test examples 1-2 are intended to illustrate the testing of the properties of the reference rubber.
The reference vulcanizates DS1 and DS2 obtained from comparative examples 1 and 2 were tested for their properties according to the methods of test examples 1-6 and the results are shown in Table 1.
TABLE 1
From the above results, it can be seen that the rubber composition provided by the present invention is effective in improving the relationship between wet skid resistance and rolling resistance.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (25)
1. A rubber composition contains olefin rubber, a vulcanizing agent, a vulcanization accelerator, a reinforcing agent and an activator, and is characterized in that the olefin rubber contains a modified olefin polymer, the molecular chain of the modified olefin polymer contains at least one monovinylarene structural unit and at least two conjugated diene structural units, the molecular chain of the modified olefin polymer also contains a silane coupling agent structural unit shown in a formula (I), the monovinylarene structural unit and the conjugated diene structural unit form a main chain of the polymer on the molecular chain of the modified olefin polymer, the silane coupling agent structural unit shown in the formula (I) is bonded to the conjugated diene structural unit on the main chain, and the number average molecular weight of the modified olefin polymer is 5-100 ten thousand;
wherein R is1-R4Is C1-C20A straight or branched hydrocarbon group or C containing a hetero atom1-C20The heteroatom is selected from one or more of halogen, oxygen, sulfur, silicon and phosphorus.
2. The rubber composition according to claim 1, wherein R1-R3Is C1-C5A linear or branched alkyl group or a linear or branched alkoxy group of R4Is C1-C5Linear or branched alkylene groups of (a).
3. The rubber composition according to claim 1 or 2, wherein the content of the modified olefin polymer in the olefin rubber is from 50 to 100% by weight based on the total weight of the olefin rubber.
4. The rubber composition according to claim 3, wherein the content of the modified olefin polymer in the olefin rubber is from 80 to 100% by weight, based on the total weight of the olefin rubber.
5. The rubber composition according to claim 1 or 2, wherein the olefin rubber further contains a mixed rubber selected from one or more of natural rubber, polybutadiene rubber, styrene-butadiene rubber, polyisoprene rubber, chloroprene rubber, butyl rubber and ethylene-propylene-diene rubber.
6. The rubber composition according to claim 5, wherein the compounded rubber is contained in an amount of 10 to 40 parts by weight, the vulcanizing agent is contained in an amount of 1 to 3 parts by weight, the vulcanization accelerator is contained in an amount of 3 to 5 parts by weight, the reinforcing agent is contained in an amount of 70 to 90 parts by weight, and the activator is contained in an amount of 3 to 4 parts by weight, based on 100 parts by weight of the modified olefin polymer.
7. The rubber composition according to claim 1, wherein the total content of the monovinylarene structural unit and the conjugated diene structural unit is 90 to 99.99 wt% and the content of the silane coupling agent structural unit is 0.01 to 10 wt%, based on the total weight of the modified olefin polymer.
8. The rubber composition according to claim 7, wherein the total content of the monovinylarene structural unit and the conjugated diene structural unit is 98 to 99.8 wt% based on the total weight of the modified olefin polymer.
9. The rubber composition according to claim 7, wherein the content of the silane coupling agent structural unit is 0.2 to 2% by weight.
10. The rubber composition according to claim 1 or 7, wherein in the formula (I),
R1-R3is methoxy, R4Is propylene; or,
R1-R3is ethoxy, R4Is propylene; or,
R1-R3is methyl, R4Is an ethylene group.
11. The rubber composition according to claim 1 or 7, wherein the modified olefin polymer has a number average molecular weight of 15 to 20 ten thousand and a molecular weight distribution of 1 to 4.
12. The rubber composition according to claim 11, wherein the modified olefin polymer has a molecular weight distribution of 1 to 1.5.
13. The rubber composition according to claim 1, wherein the modified olefin polymer is produced by: contacting an olefin polymer comprising at least one monovinylarene structural unit and at least two conjugated diene structural units with a silane coupling agent in an inert atmosphere and in the presence of an initiator, said contacting conditions being such that said silane coupling agent is chemically bonded to said olefin polymer; the number average molecular weight of the olefin polymer is 5-100 ten thousand, and the content of the conjugated diene structural unit of which the side chain contains double bonds in the olefin polymer is 15-85 wt% based on the total weight of the conjugated diene structural unit in the olefin polymer, and the silane coupling agent has a structure shown in a formula (II):
wherein R is1-R4Is C1-C20A straight or branched hydrocarbon group or C containing a hetero atom1-C20The heteroatom is selected from one or more of halogen, oxygen, sulfur, silicon and phosphorus.
14. The rubber composition according to claim 13, wherein the content of the conjugated diene structural unit having a double bond in a side chain in the olefin polymer is 30 to 60% by weight based on the total weight of the conjugated diene structural unit in the olefin polymer.
15. The rubber composition of claim 13, wherein R1-R3Is C1-C5A linear or branched alkyl group or a linear or branched alkoxy group of R4Is C1-C5Linear or branched alkylene groups of (a).
16. The rubber composition according to claim 13 or 15, wherein the olefin polymer is prepared by: at least one monovinyl aromatic hydrocarbon and at least two conjugated dienes are polymerized in a solvent in an inert atmosphere and in the presence of an initiator, the polymerization conditions are such that the obtained olefin polymer has a number average molecular weight of 5-100 ten thousand, and the content of the conjugated diene structural units with double bonds in the side chains in the olefin polymer is 15-85 wt% based on the total weight of the conjugated diene structural units in the olefin polymer.
17. The rubber composition according to claim 16, wherein the content of the conjugated diene structural unit having a double bond in a side chain in the olefin polymer is 30 to 60% by weight based on the total weight of the conjugated diene structural unit in the olefin polymer.
18. The rubber composition according to claim 16, wherein the polymerization conditions include a polymerization temperature of 10 to 160 ℃, a polymerization pressure of 0.05 to 1MPa, and a polymerization time of 0.5 to 10 hours.
19. The rubber composition according to claim 18, wherein the polymerization conditions include a polymerization temperature of 40 to 80 ℃, a polymerization pressure of 0.1 to 0.3MPa, and a polymerization time of 0.5 to 2 hours.
20. The rubber composition according to any one of claims 13 to 15 and 17 to 19, wherein the conditions for contacting the olefin polymer with the silane coupling agent include a contact temperature of 20 to 150 ℃, a contact pressure of 0.01 to 1MPa, and a contact time of 0.1 to 24 hours.
21. The rubber composition according to claim 20, wherein the conditions for contacting the olefin polymer with the silane coupling agent include a contact temperature of 70 to 90 ℃, a contact pressure of 0.1 to 0.5MPa, and a contact time of 0.5 to 5 hours.
22. The rubber composition according to any one of claims 13 to 15 and 17 to 19, wherein the silane coupling agent is used in an amount of 0.01 to 10g based on 100g of the olefin polymer.
23. The rubber composition according to claim 22, wherein the silane coupling agent is used in an amount of 0.1 to 5g, based on 100g of the olefin polymer.
24. The rubber composition according to claim 23, wherein the silane coupling agent is used in an amount of 0.2 to 2g, based on 100g of the olefin polymer.
25. A vulcanized rubber obtained by uniformly mixing and vulcanizing the rubber composition according to any one of claims 1 to 24.
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CN201310512797.9A CN104558415B (en) | 2013-10-25 | 2013-10-25 | A kind of rubber composition and vulcanization rubber |
US14/523,113 US9296840B2 (en) | 2013-10-25 | 2014-10-24 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
FR1460262A FR3012455B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENE POLYMER, PROCESS FOR PREPARING THE SAME, AND RUBBER COMPOSITION COMPRISING SAME |
BE2014/0796A BE1022183B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
DE201410221690 DE102014221690A1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
RU2014142923/04A RU2599641C2 (en) | 2013-10-25 | 2014-10-24 | Functional polydiene, method for production thereof and rubber composition containing same |
KR1020140146390A KR101660856B1 (en) | 2013-10-25 | 2014-10-27 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
SG10201407122YA SG10201407122YA (en) | 2013-10-25 | 2014-10-31 | Functional diene polymer, preparation method thereof, and rubber composition comprising the same |
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