CN104558414A - Modified alkadiene polymer as well as preparation method and application thereof - Google Patents
Modified alkadiene polymer as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104558414A CN104558414A CN201310512238.8A CN201310512238A CN104558414A CN 104558414 A CN104558414 A CN 104558414A CN 201310512238 A CN201310512238 A CN 201310512238A CN 104558414 A CN104558414 A CN 104558414A
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- CN
- China
- Prior art keywords
- diene polymer
- structural unit
- modified
- coupling agent
- silane coupling
- Prior art date
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- Granted
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 272
- 229920000642 polymer Polymers 0.000 title claims abstract description 218
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 62
- 229920001971 elastomer Polymers 0.000 claims abstract description 37
- 239000005060 rubber Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 33
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims description 37
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 4
- 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
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 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 20
- 239000005864 Sulphur Substances 0.000 abstract 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 238000010074 rubber mixing Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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 16
- 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
- -1 methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy Chemical group 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 125000003396 thiol group Chemical group [H]S* 0.000 description 12
- 239000004636 vulcanized rubber Substances 0.000 description 12
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 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
- 239000000126 substance Substances 0.000 description 6
- 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 5
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 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
- 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
- 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
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 125000001979 organolithium group Chemical group 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 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
- 230000003712 anti-aging effect Effects 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
- 238000004898 kneading Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000178 monomer Substances 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
- 230000009257 reactivity Effects 0.000 description 3
- 238000010058 rubber compounding Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-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
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000006872 improvement 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
- 230000004048 modification Effects 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 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
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000008117 stearic acid Substances 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
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 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
- PGZISVXTYZWYPK-UHFFFAOYSA-N 2-(butoxymethyl)oxolane Chemical compound CCCCOCC1CCCO1 PGZISVXTYZWYPK-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- TVKQVMQEOOKKMN-UHFFFAOYSA-N [Li]CCC[Li] Chemical compound [Li]CCC[Li] TVKQVMQEOOKKMN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 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
- 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
- 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
- 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
- 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
- 239000006232 furnace black Substances 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
- 238000002156 mixing Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-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
- 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
- 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
- 229920003048 styrene butadiene rubber Polymers 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
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a modified alkadiene polymer, a preparation method of the modified alkadiene polymer and application of the modified alkadiene polymer as base rubber. A molecular chain of the modified alkadiene polymer comprises a monovinyl aromatic hydrocarbon structure unit, a conjugated alkadiene structure unit and a silane coupling agent shown in a formula (I), wherein the number-average molecular weight of the modified alkadiene polymer is 50000-1000,000; R1-R4 is C1-C20 linear chain or branched chain alkyl or heteroatom-containing C1-C20 linear chain or branched chain alkyl; the heteroatoms are selected from one or more of halogen, oxygen, sulphur, silicon and phosphorus. The modified alkadiene polymer can be used for effectively balancing the relation between wet-skid resistance and rolling resistance and can also be used for improving unpleasant odor generated by using the silane coupling agent in the rubber mixing process. The formula (I) is as shown in the description.
Description
Technical Field
The invention relates to a modified diene polymer, a preparation method of the modified diene polymer, the modified diene polymer prepared by the method, and application of the modified diene polymer as rubber-based rubber.
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 the rubber cannot be effectively improved and the rolling resistance is reduced.
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 adopting the conventional method, and provides a modified diene polymer with high wet-skid resistance and low rolling resistance, a preparation method of the modified diene polymer, the modified diene polymer prepared by the method and application of the modified diene polymer.
The invention provides a modified diene polymer, wherein a molecular chain of the modified diene polymer contains a monovinylarene structural unit and a conjugated diene structural unit, wherein the molecular chain of the modified diene polymer also contains a silane coupling agent structural unit shown in a formula (I), and the number average molecular weight of the modified diene 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 present invention also provides a process for preparing a modified diene polymer, wherein the process comprises contacting a diene polymer comprising monovinylarene structural units and conjugated diene structural units with a silane coupling agent in an inert atmosphere and in the presence of an initiator, under conditions such that the silane coupling agent is chemically bonded to the diene polymer; the number average molecular weight of the diene polymer is 5-100 ten thousand, and the content of the conjugated diene structural unit with double bonds in the side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt%, based on the weight of the conjugated diene structural unit in the diene 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.
The invention also provides another preparation method of the modified diene polymer, wherein the method comprises the following steps:
(1) in an inert atmosphere and in the presence of an initiator, carrying out polymerization reaction on monovinylarene and conjugated diene in a solvent to obtain a reaction product containing a diene polymer, wherein the polymerization reaction conditions enable the number average molecular weight of the obtained diene polymer to be 5-100 ten thousand, and the content of a conjugated diene structural unit with a double bond in a side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt% based on the weight of the conjugated diene structural unit in the diene polymer;
(2) contacting the reaction product containing the diene polymer obtained in step (1) with a silane coupling agent in an inert atmosphere and in the presence of an initiator, said contacting being under conditions such that said silane coupling agent is chemically bonded to said diene polymer, said silane coupling agent having the 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.
The invention also provides the modified diene polymer prepared by the method.
In addition, the invention also provides the application of the modified diene polymer as rubber-based rubber.
As described above, in the prior art, the silane coupling agent is generally added during the mixing of the rubber mixture to improve the wet skid resistance of the rubber and to reduce the rolling resistance thereof, but the reactivity of the silane coupling agent with the raw rubber and the carbon black is reduced at this time, 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 have found that, by chemically bonding a silane coupling agent to a diene polymer and using the resulting modified diene 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 a raw rubber and carbon black caused during rubber compounding, and to effectively balance the relationship between wet skid resistance and rolling resistance of a tire made of the modified diene polymer, and also to improve an unpleasant odor caused by the use of the silane coupling agent during rubber compounding.
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 molecular chain of the modified diene polymer provided by the invention contains a monovinylarene structural unit and a conjugated diene structural unit, wherein the molecular chain of the modified diene polymer also contains a silane coupling agent structural unit shown in a formula (I), and the number average molecular weight of the modified diene 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; 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).
Wherein, the C1-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.
On the molecular chain of the modified diene 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, 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-mercaptopropyltriethoxysilane; 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 and the conjugated diene structural unit and the silane coupling agent structural unit in the modified diene is not particularly limited and may be adjusted according to the amount of the monovinylarene and the conjugated diene and the silane coupling agent used during the preparation, but in order to provide the modified diene polymer 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% by weight, more preferably 98 to 99.8% by weight, and the content of the silane coupling agent structural unit is preferably 0.01 to 10% by weight, more preferably 0.2 to 2% by weight, based on the total weight of the modified diene 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 diene polymer in the present invention are not particularly limited, 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-C20Is substituted orSpecific examples of unsubstituted aryl groups 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 one or more of styrene, vinyltoluene, alpha-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 diene polymer, and for example, the conjugated diene may be selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene, with butadiene and/or isoprene being particularly preferred.
The preparation method of the modified diene polymer comprises the steps of contacting a diene polymer containing a monovinylarene structural unit and a conjugated diene structural unit with a silane coupling agent in an inert atmosphere and in the presence of an initiator, wherein the contacting condition is that the silane coupling agent is chemically bonded to the diene polymer; the number average molecular weight of the diene polymer is 5-100 ten thousand, and the content of the conjugated diene structural unit with double bonds in the side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt%, based on the weight of the conjugated diene structural unit in the diene 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; 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 double bond in the side chain in the diene polymer can be measured by adopting a nuclear magnetic resonance spectrometer which is purchased from Bruker company of Switzerland and has the model of AVANCE DRX400MHz, 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 diene polymer can be prepared by various methods known in the art, for example, the preparation method may include: in an inert atmosphere and in the presence of an initiator, carrying out polymerization reaction on monovinylarene and conjugated diene in a solvent to obtain a reaction product containing a diene polymer, wherein the polymerization reaction conditions enable the number average molecular weight of the obtained diene polymer to be 5-100 ten thousand, and the content of the conjugated diene structural unit with a double bond in a side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt%, based on the weight of the conjugated diene structural unit in the diene polymer.
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 diene polymer, and for example, may be an organolithium initiator. The organolithium initiator may be any of a variety of organolithium initiators known to those skilled in the art that are capable of initiating anionic polymerization, for example, the organolithium initiator may be 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 a diene polymer having a relatively large molecular weight, the amount of initiator used can be reduced, but the rate of polymerization will be correspondingly reduced; when it is desired to prepare a diene polymer having a smaller molecular weight, the amount of the initiator 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 diene polymer, it is preferred that the amount of the initiator is 0.15 to 2.5mmol, based on 100g of the total weight of the monovinylarene and the conjugated diene.
The amount of the monovinylarene and the conjugated diene used in the present invention is not particularly limited and may be appropriately selected according to the intended diene polymer, and for example, the weight ratio of the monovinylarene to the conjugated diene may be 5:95 to 60:40, preferably 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 any of various substances capable of acting as a reaction medium in the preparation of the diene 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 include, but are 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 invention, after the polymerization has been completed, a coupling agent may also be added to the polymerization system in order to couple together at least part of the diene polymers. 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 diene polymer, so that the microstructure of the diene polymer can be effectively controlled. The structure modifier may be any of various existing substances capable of modifying the microstructure of the diene 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 diene 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 preparing the diene polymer, and in general, the molar ratio of the terminator to the initiator to be used for preparing the diene 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 diene polymer with the silane coupling agent in the present invention are not particularly limited as long as the silane coupling agent can be chemically bonded to the diene polymer, and for example, the contacting conditions generally include a contacting temperature, a contacting pressure and a contacting time. Generally, in order to facilitate the chemical bonding of the silane coupling agent to the diene polymer, the contact temperature is preferably from 20 to 150 ℃, more preferably from 70 to 90 ℃, the contact pressure is preferably from 0.01 to 1MPa, more preferably from 0.1 to 0.5MPa, and the contact time is preferably from 0.1 to 24 hours, more preferably from 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 diene polymer when the diene polymer is brought into contact with the silane coupling agent, it is preferable to use the initiator in an amount of 0.01 to 0.1% by weight, more preferably 0.01 to 0.08% by weight, based on the total weight of the diene polymer and the silane coupling agent having the 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. Wherein 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 diene polymer and the silane coupling agent having a structure represented by 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 diene polymer.
In addition, the present invention provides another process for preparing a modified diene polymer, wherein the process comprises the steps of:
(1) in an inert atmosphere and in the presence of an initiator, carrying out polymerization reaction on monovinylarene and conjugated diene in a solvent to obtain a reaction product containing a diene polymer, wherein the polymerization reaction conditions enable the number average molecular weight of the obtained diene polymer to be 5-100 ten thousand, and the content of a conjugated diene structural unit with a double bond in a side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt% based on the weight of the conjugated diene structural unit in the diene polymer;
(2) contacting the reaction product containing the diene polymer obtained in step (1) with a silane coupling agent in an inert atmosphere and in the presence of an initiator, said contacting being under conditions such that said silane coupling agent is chemically bonded to said diene polymer, said silane coupling agent having the 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 kinds and amounts of the substances in steps (1) and (2) and the conditions of the polymerization reaction and the contacting conditions can be reasonably selected according to the above description, and will not be described again.
According to the present invention, various additives may be optionally added to the resulting modified diene polymer after the preparation of the modified diene polymer is completed. The additive may be, for example, an anti-aging agent, which enables the resulting modified diene polymer to have good anti-aging properties. 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 diene polymer can be precipitated from the solution by purification precipitation, centrifugation, filtration, decantation, hot water coagulation, etc., or the solvent in the reaction system can be removed by gas stripping, which is known to those skilled in the art and will not be described herein.
The invention also provides the modified diene polymer prepared by the method.
In addition, the invention also provides the application of the modified diene polymer as rubber-based rubber.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the mercapto conversion was measured using an agilent 7890A gas chromatograph under the following test conditions: the chromatographic column is an SPB-560m multiplied by 0.32mm multiplied by 1.0um capillary column, the flow rate of the column is 2.0ml/min, the column temperature is 220 ℃, the gasification chamber temperature is 220 ℃, the detection chamber temperature is 250 ℃, and the split ratio is 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, molecular weight distribution and coupling efficiency were determined using an ALLIANCE model 2690 Gel Permeation Chromatograph (GPC) from WATERS, USA, with THF as the mobile phase, narrow distribution polystyrene as the standard and 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%.
Example 1
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
(1) In a 5-liter stainless steel stirred tank, 2288g of cyclohexane, 31.2g of styrene, 112.3g of butadiene and 1.1g of tetrahydrofurfuryl alcohol ether were added under protection of high purity nitrogen, and then, after heating to 50 ℃, 1.1mmol of n-butyllithium was added and the reaction was initiated with the pressure being controlled at 0.2MPa for 2 hours to obtain a solution containing a diene polymer. The number average molecular weight of the diene polymer was 18.2 ten thousand, and based on the weight of the conjugated diene structural unit in the diene polymer, the content of the conjugated diene structural unit having a double bond in a side chain in the diene polymer was 43.02 wt%, the content of the styrene structural unit was 21.74 wt%, and the content of the butadiene structural unit was 78.26 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 after heating to 80 ℃ 6.7mg of azobisisobutyronitrile was added and the pressure was controlled at 0.2MPa for reaction for 3 hours, a modified diene polymer was obtained and sampled for mercapto group testing. To the above modified diene polymer was added 0.2g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein, in the modified diene polymer, the mercapto conversion rate is 79 percent, the Mooney viscosity is 45, the number average molecular weight is 18.2 ten thousand, and the molecular weight distribution is 1.1; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 0.46% by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 2
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 31.2g of vinyltoluene, 112.32g of isoprene and 0.65g of tetrahydrofuran were added under the protection of high purity nitrogen, then heated to 45 ℃ and 1.0mmol of n-butyllithium was added and the reaction was initiated with controlling the pressure at 0.1MPa for 2 hours to obtain a solution containing a diene polymer, and then 0.06mmol of tin tetrachloride was added and reacted at 60 ℃ for 30 minutes to obtain a polymer having a coupling efficiency of 27%. The number average molecular weight of the diene polymer was 19.4 ten thousand, and based on the weight of the conjugated diene structural unit in the diene polymer, the content of the conjugated diene structural unit having a double bond in a side chain in the diene polymer was 33.03 wt%, the content of the vinyl toluene structural unit was 21.74 wt%, and the content of the isoprene structural unit was 78.26 wt%.
(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 ℃ and adding 30mg of azobisisobutyronitrile, and after reaction for 5 hours with the pressure controlled at 0.1MPa, a modified diene polymer was obtained, and sampling was conducted for mercapto group testing. To the above modified diene polymer was added 0.2g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein, in the modified diene polymer, the mercapto conversion rate is 82 percent, the Mooney viscosity is 47, the number average molecular weight is 19.4 ten thousand, and the molecular weight distribution is 1.07; the content of the gamma-mercaptopropyltrimethoxysilane structural unit is 0.36 percent by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 3
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 31.2g of styrene, 112.3g of butadiene and 0.9g of tetrahydrofurfuryl alcohol ether were added under high purity nitrogen protection, followed by heating to 80 ℃ and then adding 1.0mmol of n-butyllithium and initiating the reaction for 0.5 hour with the pressure being controlled at 0.3MPa to obtain a solution containing a diene polymer. The number average molecular weight of the diene polymer was 19.4 ten thousand, and based on the weight of the conjugated diene structural unit in the diene polymer, the content of the conjugated diene structural unit having a double bond in a side chain in the diene polymer was 40.02% by weight, the content of the styrene structural unit was 21.74% by weight, and the content of the butadiene structural unit was 78.26% by weight.
(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 90 ℃ and addition of 30mg of azobisisobutyronitrile, the modified diene polymer was obtained after reaction for 0.5 hour with the pressure controlled at 0.5MPa and sampled for mercapto group testing. To the above modified diene polymer was added 0.2g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein, in the modified diene polymer, the mercapto conversion rate is 89%, the Mooney viscosity is 55, the number average molecular weight is 19.4 ten thousand, and the molecular weight distribution is 1.09; the content of the gamma-mercaptopropyltrimethoxysilane structural unit is 1.91 percent by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 4
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of cyclohexane, 62.4g of styrene, 248.6g of butadiene and 1.3g of tetrahydrofurfuryl alcohol ether were added under protection of high purity nitrogen, and then 1.1mmol of n-butyllithium was added at 50 ℃ and the reaction was initiated under a pressure of 0.25MPa for 1 hour to obtain a solution containing a diene polymer. The number average molecular weight of the diene polymer was 20.5 ten thousand, and based on the weight of the conjugated diene structural unit in the diene polymer, the content of the conjugated diene structural unit having a double bond in a side chain in the diene polymer was 51.05 wt%, the content of the styrene structural unit was 20.06 wt%, and the content of the butadiene structural unit was 79.94 wt%.
(2) 1.9ml (1.986 g) of gamma-mercaptopropyltrimethoxysilane was added to the product obtained in the step (1), and immediately sampled for mercapto group testing, and then 13mg of azobisisobutyronitrile was added after heating to 80 ℃ and reacted for 1 hour under a pressure of 0.3MPa to obtain a modified diene polymer, and sampled for mercapto group testing. To the above modified diene polymer was added 0.4g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein, in the modified diene polymer, the mercapto conversion rate is 78%, the Mooney viscosity is 59, the number average molecular weight is 20.5 ten thousand, and the molecular weight distribution is 1.1; the content of the gamma-mercaptopropyltrimethoxysilane structural unit is 0.50 percent by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 5
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
(1) In a 5 liter stainless steel stirring tank, 2288g of hexane, 62.4g of styrene, 248.5g of butadiene and 1.3g of tetrahydrofurfuryl butyl ether were added under protection of high purity nitrogen, and then, after heating to 70 ℃, 1.1mmol of n-butyllithium was added and the reaction was initiated with controlling the pressure at 0.2MPa for 1.2 hours to obtain a solution containing a diene polymer. The number average molecular weight of the diene polymer was 19.0 ten thousand, and based on the weight of the conjugated diene structural unit in the diene polymer, the content of the conjugated diene structural unit having a double bond in a side chain in the diene polymer was 46.80% by weight, the content of the styrene structural unit was 20.07% by weight, and the content of the butadiene structural unit was 79.93% by weight.
(2) 2.02ml (1.990 g) of gamma-mercaptopropyltriethoxysilane was added to the product obtained in step (1), and immediately sampled for mercapto group testing, then heated to 75 ℃ and 30mg of azobisisobutyronitrile was added, and reacted for 1.2 hours under a pressure of 0.25MPa to obtain a modified diene polymer, and sampled for mercapto group testing. To the above modified diene polymer was added 0.2g of an antioxidant Irganox1520 and dried under vacuum at 60 ℃ for 24 hours. Wherein, in the modified diene polymer, the mercapto conversion rate is 82 percent, the Mooney viscosity is 50, the number average molecular weight is 19.0 ten thousand, and the molecular weight distribution is 1.1; the content of the gamma-mercaptopropyltriethoxysilane structural unit was 0.52 wt% based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 6
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
A modified diene polymer was prepared according to the method of example 4, except that the amount of gamma-mercaptopropyltrimethoxysilane added was 7.3ml (7.629 g), to obtain a modified diene polymer. Wherein, in the modified diene polymer, the mercapto conversion rate is 63 percent, the Mooney viscosity is 54, the number average molecular weight is 20.7 ten thousand, and the molecular weight distribution is 1.1; the content of the gamma-mercaptopropyltrimethoxysilane structural unit was 1.52% by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Example 7
This example serves to illustrate the modified diene polymer and the process for its preparation provided by the present invention.
A modified diene polymer was prepared according to the procedure of example 4, except that the gamma-mercaptopropyltrimethoxysilane was replaced with the same parts by weight of 2-trimethylsilylethylthiol to obtain a modified diene polymer. Wherein, in the modified diene polymer, the conversion rate of sulfydryl is 65 percent, the Mooney viscosity is 52, the number average molecular weight is 20.3 ten thousand, and the molecular weight distribution is 1.1; the content of 2-trimethylsilylethylthiol structural unit was 0.41% by weight based on the total weight of the modified diene polymer. The polymer has no unpleasant odor.
Comparative example 1
This comparative example serves to illustrate a reference diene polymer and a process for its preparation.
A diene polymer was prepared by following the procedure of example 4 except that the step (2) was not included to obtain a diene polymer. Wherein, in the diene polymer, the Mooney viscosity is 48, the number average molecular weight is 19.0 ten thousand, and the molecular weight distribution is 1.1. The content of styrene structural units was 20.06 wt% and the content of butadiene structural units was 79.94 wt%, based on the total weight of the diene polymer.
Comparative example 2
This comparative example serves to illustrate a reference diene polymer and a process for its preparation.
(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 a diene polymer. The number average molecular weight of the diene polymer is 1000, and the content of the conjugated diene structural unit of which the side chain contains double bonds in the diene polymer is 67% by weight based on the weight of the conjugated diene structural unit in the diene polymer.
(2) Adding 20g of gamma-mercaptopropyltrimethoxysilane into the product obtained in the step (1), immediately sampling for a mercapto group test, then heating to 100 ℃, adding 1g of lauroyl peroxide, reacting for 5 hours under the pressure of 0.4MPa to obtain a modified diene polymer, and sampling for a mercapto group test. Finally dried in vacuum at 80 ℃ for 24 h. Wherein the modified diene polymer has a mercapto 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 diene polymer.
Examples 8 to 14
This example serves to illustrate the process for the preparation of a rubber containing the modified diene polymer of the present invention.
(1) Preparation of rubber compound:
100 parts by weight of the modified diene polymer prepared in examples 1 to 7, 1 part by weight of stearic acid (hong kong swern chemical limited, SA 1801), 10 parts by weight of medium-high wear-resistant furnace black N220 (tianjin jinqiuzu carbon black chemical limited), and 60 parts by weight of white carbon black 115GR (degussa) were uniformly mixed and subjected to Haake heat treatment at a temperature of 150 ℃, a rotation speed of 30rpm, and a time of 7 min. 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 St. 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 parts by weight of diphenylguanidine (Cangzhou Liang. mechanical Large rubber raw materials trade Co., Ltd., DPG) and 6 parts by weight of a silane coupling agent Si69 (Texaco) were added and mixed at 50. + -. 5 ℃ for 60 minutes to obtain a mixed rubber H1-H7.
(2) And (3) vulcanization:
and (2) respectively carrying out vulcanization treatment on the mixed rubber H1-H7 obtained in the step (1) on a flat vulcanizing machine for 45 minutes at 150 ℃ and 12MPa to obtain vulcanized rubber S1-S7.
Comparative example 3
This comparative example serves to illustrate the preparation of a rubber containing a reference diene polymer.
A rubber was prepared by following the procedure of example 8 except that the modified diene polymer obtained in example 1 was replaced with the diene polymer obtained in comparative example 1 and the amount of the added diene polymer was 99.54 parts by weight, and further, during the preparation of the rubber compound, 0.46 part by weight of gamma-mercaptopropyltrimethoxysilane was added to obtain a reference vulcanized rubber DS 1.
Comparative example 4
This comparative example serves to illustrate the preparation of a reference vulcanizate.
A vulcanized rubber was prepared by following the procedure of example 8 except that the modified diene polymer obtained in production example 1 was replaced with a mixture of 98.96 parts by weight of the diene polymer obtained in comparative example 1 and 1.04 parts by weight of the modified diene polymer obtained in comparative example 2 to obtain a reference vulcanized rubber DS 2.
Test examples 1 to 7
Test examples 1-7 are provided to illustrate tests of properties of S1-S7 containing the vulcanizates provided by this 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 S7 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 S7 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-S7 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 at 0 ℃, and the larger the tan is, the better the wet skid resistance of the vulcanized rubber is represented; tan at 60 ℃ represents the rolling resistance of the vulcanized rubber, and the smaller tan represents the smaller rolling resistance of the vulcanized rubber; the dispersion of the filler in the rubber is characterized by the value Tan (0 ℃ C.)/Tan (60 ℃ C.), a higher value indicating a 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 presented to illustrate the testing of properties with reference rubbers.
The reference vulcanizates DS1 and DS2 obtained from comparative example 3 and comparative example 4 were tested for their properties according to the methods of test examples 1-7 and the results are shown in Table 1.
TABLE 1
From the above results, it can be seen that the modified diene polymer provided by the present invention is not only effective in improving the relationship between wet skid resistance and rolling resistance, but also in improving the unpleasant odor caused by the use of a silane coupling agent during rubber compounding.
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 (16)
1. A modified diene polymer, the molecular chain of which contains a monovinylarene structural unit and a conjugated diene structural unit, is characterized in that the molecular chain of the modified diene polymer also contains a silane coupling agent structural unit shown in a formula (I), and the number average molecular weight of the modified diene 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; 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).
2. The modified diene polymer according to claim 1, wherein the total content of the monovinylarene structural unit and the conjugated diene structural unit is 90 to 99.99% by weight and the content of the silane coupling agent structural unit is 0.01 to 10% by weight, based on the total weight of the modified diene polymer.
3. The modified diene polymer according to claim 2, wherein the total content of the monovinylarene structural unit and the conjugated diene structural unit is 98 to 99.8% by weight and the content of the silane coupling agent structural unit is 0.2 to 2% by weight, based on the total weight of the modified diene polymer.
4. A modified diene polymer according to any one of claims 1 to 3, wherein in the formula (I), R is1-R3Is methoxy, R4Is propylene; or,
R1-R3is ethoxy, R4Is propylene;
R1-R3is methyl, R4Is an ethylene group.
5. A modified diene polymer according to any one of claims 1 to 3, wherein the weight ratio of monovinylarene structural units to conjugated diene structural units is from 5:95 to 60:40, preferably from 20:80 to 40: 60.
6. The modified diene polymer of claim 5, wherein the monovinylarene structural units are structural units derived from monovinylarenes selected from one or more of styrene, vinyl toluene, alpha-methyl styrene, 4-tert-butyl styrene, and 4-methyl styrene; preferably, the conjugated diene structural unit is a structural unit derived from a conjugated diene selected from one or more of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene.
7. A modified diene polymer according to any one of claims 1 to 3, wherein the modified diene polymer has a number average molecular weight of from 15 to 20 ten thousand and a molecular weight distribution of from 1 to 4, preferably from 1 to 1.5.
8. A process for the preparation of a modified diene polymer, which process comprises contacting a diene polymer comprising monovinylarene structural units and conjugated diene structural units with a silane coupling agent in an inert atmosphere and in the presence of an initiator, said contacting being under conditions such that said silane coupling agent is chemically bonded to said diene polymer; the number average molecular weight of the diene polymer is 5-100 ten thousand, and the content of the conjugated diene structural unit with double bonds in the side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt%, based on the weight of the conjugated diene structural unit in the diene 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-C20Straight or branched chain ofA hydrocarbon group, the heteroatom being 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).
9. The process according to claim 8, wherein the diene polymer is obtained by: in an inert atmosphere and in the presence of an initiator, carrying out polymerization reaction on monovinylarene and conjugated diene in a solvent to obtain a reaction product containing a diene polymer, wherein the polymerization reaction conditions enable the number average molecular weight of the obtained diene polymer to be 5-100 ten thousand, and the content of the conjugated diene structural unit with a double bond in a side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt%, based on the weight of the conjugated diene structural unit in the diene polymer.
10. A process for the preparation of a modified diene polymer, characterized in that it comprises the following steps:
(1) in an inert atmosphere and in the presence of an initiator, carrying out polymerization reaction on monovinylarene and conjugated diene in a solvent to obtain a reaction product containing a diene polymer, wherein the polymerization reaction conditions enable the number average molecular weight of the obtained diene polymer to be 5-100 ten thousand, and the content of a conjugated diene structural unit with a double bond in a side chain in the diene polymer is 15-85 wt%, preferably 30-60 wt% based on the weight of the conjugated diene structural unit in the diene polymer;
(2) contacting the reaction product containing the diene polymer obtained in step (1) with a silane coupling agent in an inert atmosphere and in the presence of an initiator, said contacting being under conditions such that said silane coupling agent is chemically bonded to said diene polymer, said silane coupling agent having the 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).
11. The method of claim 8, 9 or 10, wherein the silane coupling agent is selected from one or more of gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, and 2-trimethylsilylethylthiol.
12. The production method according to claim 9 or 10, wherein the polymerization conditions include a polymerization temperature of 10 to 160 ℃, preferably 40 to 80 ℃, a polymerization pressure of 0.05 to 1MPa, preferably 0.1 to 0.3MPa, and a polymerization time of 0.5 to 10 hours, preferably 0.5 to 2 hours.
13. The production process according to claim 8, 9 or 10, wherein the conditions for contacting the diene polymer with the silane coupling agent include a contact temperature of 20 to 150 ℃, preferably 70 to 90 ℃, a contact pressure of 0.01 to 1MPa, preferably 0.1 to 0.5MPa, and a contact time of 0.1 to 24 hours, preferably 0.5 to 5 hours.
14. The production process according to claim 8, 9 or 10, wherein the silane coupling agent is used in an amount of 0.01 to 10g, preferably 0.1 to 5g, more preferably 0.2 to 2g, based on 100g of the diene polymer.
15. A modified diene polymer prepared by the process of any one of claims 8 to 14.
16. Use of a modified diene polymer as claimed in any one of claims 1 to 7 and 15 as a rubber-based gum.
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| CN201310512238.8A CN104558414B (en) | 2013-10-25 | 2013-10-25 | A kind of modified diene polymer and its preparation method and application |
| RU2014142923/04A RU2599641C2 (en) | 2013-10-25 | 2014-10-24 | Functional polydiene, method for production thereof and rubber composition containing same |
| DE201410221690 DE102014221690A1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| BE2014/0796A BE1022183B1 (en) | 2013-10-25 | 2014-10-24 | FUNCTIONAL DIENPOLYMER, MANUFACTURING METHOD AND RUBBER COMPOSITION THEREOF CONTAINING THIS |
| 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 |
| 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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