CN105164170B - 末端改性聚合物的制造方法 - Google Patents
末端改性聚合物的制造方法 Download PDFInfo
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- CN105164170B CN105164170B CN201480011000.XA CN201480011000A CN105164170B CN 105164170 B CN105164170 B CN 105164170B CN 201480011000 A CN201480011000 A CN 201480011000A CN 105164170 B CN105164170 B CN 105164170B
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- China
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- modified polymers
- manufacture method
- mms
- polymerisation
- titanium compound
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- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 23
- 229920001971 elastomer Polymers 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000005060 rubber Substances 0.000 claims abstract description 35
- 150000001993 dienes Chemical class 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 21
- -1 alkoxy titanium compound Chemical class 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000129 anionic group Chemical group 0.000 claims abstract description 10
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 29
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229920003244 diene elastomer Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002900 organolithium compounds Chemical class 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 54
- 239000000377 silicon dioxide Substances 0.000 abstract description 27
- 239000004615 ingredient Substances 0.000 abstract description 10
- 238000013329 compounding Methods 0.000 abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 239000000806 elastomer Substances 0.000 description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000001294 propane Substances 0.000 description 10
- 238000012856 packing Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 7
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000012805 post-processing Methods 0.000 description 7
- 229920003048 styrene butadiene rubber Polymers 0.000 description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910003978 SiClx Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 210000003754 fetus Anatomy 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000002156 mixing Methods 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
- 239000003921 oil Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical class CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical class CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical class C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical class CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical class CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000006240 Fast Extruding Furnace Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000006238 High Abrasion Furnace Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical class CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000006236 Super Abrasion Furnace Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical class [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002118 epoxides 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical class CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular 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
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical class CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- HUMLQUKVJARKRN-UHFFFAOYSA-M sodium;n,n-dibutylcarbamodithioate Chemical compound [Na+].CCCCN(C([S-])=S)CCCC HUMLQUKVJARKRN-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- PIZNQHDTOZMVBH-UHFFFAOYSA-N thionylimide Chemical class N=S=O PIZNQHDTOZMVBH-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—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
- C08F236/04—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
- C08F236/10—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 with vinyl-aromatic monomers
-
- 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
- C08C19/26—Incorporating metal 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
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Abstract
在阴离子性聚合引发剂的存在下,使乙烯基芳香族单体、共轭二烯烃单体或它们两者聚合反应,然后,于其中添加烷氧基钛化合物来使聚合反应终止,从而制造末端改性聚合物。或者,通过在代替烷氧基钛化合物添加卤化钛化合物来使聚合反应终止后,添加碳数1~4的低级醇,也可以制造末端改性聚合物。所得到的末端改性聚合物可改善用作汽车用充气轮胎用橡胶组合物的配合剂等的二氧化硅的分散性。
Description
技术领域
本发明涉及末端改性聚合物的制造方法。更具体地,涉及使用作汽车用充气轮胎用橡胶组合物的配合剂等的二氧化硅的分散性改善的末端改性聚合物的制造方法。
背景技术
作为汽车用充气轮胎所要求的各种性能,要求滚动阻力的减轻、在湿润路面的稳定性等。作为能够使这些性质并存的方法,进行了在轮胎用橡胶组合物中配合二氧化硅作为增强用填充剂。然而,发现如下的课题:即使要在轮胎用橡胶组合物中配合二氧化硅,二氧化硅在橡胶组合物中的分散性也低,例如即使能够将其大量地添加,其效果也不能充分地发挥。
专利文献1中,记载了在弹性体·主体(Host)材料内,由强化用填充材料的前体现场形成强化用填充材料,由此制造均匀分散而包含强化用填充材料的、作为轮胎的构成部件等有用的弹性体/填充材料复合材料的方法,这种情况下,为了复合二氧化硅作为填充材料,由填充剂前体出发的反应被视为必要。
专利文献2中,记载了一种弹性体/填充材料复合材料的制造方法,其中,将填充材料前体、缩合反应促进剂及弹性体主体(A)或(B)在密闭式搅拌机中混合来引发填充材料前体的缩合反应,关于弹性体主体(A)及根据情况的弹性体主体(B),在缩合反应结束前,将有机硅烷材料和填充材料/填充材料前体添加到密闭式搅拌机中并使之反应,对所得到的弹性体/填充材料复合材料进行回收。并且记述了将该复合材料用作轮胎用橡胶组合物、特别是轮胎胎面用橡胶组合物的有效成分。
在此,据记载,弹性体主体(A)是共轭二烯烃的均聚物或共轭二烯烃与乙烯基芳香族单体的共聚物,弹性体主体(B)是基于至少一种烷氧基金属末端官能团化二烯烃的弹性体,该基于二烯烃的弹性体以如下通式表示(权利要求5,段落[0014])
弹性体-X-(OR)n
弹性体:共轭二烯烃的均聚物或共轭二烯烃与乙烯基芳香族单体的共聚物
X:包含Si、Ti、Al或B的金属
R:C1~C4的烷基
n:Si、Ti的情况下为3,Al、B的情况下为2。
然而,专利文献2的各实施例中,只有在锂基催化剂的存在下,于有机溶剂中将苯乙烯和1,3-丁二烯共聚,接着对弹性体进行回收这样的记载,未见关于导入了-X-(OR)n基作为弹性体末端基的末端改性聚合物的制造方法的记载。
现有技术文献
专利文献
专利文献1:日本特开2000-273191号公报
专利文献2:日本特开2000-143881号公报。
发明内容
发明要解决的课题
本发明的目的在于,提供使用作汽车用充气轮胎用橡胶组合物的配合剂等的二氧化硅的分散性改善的末端改性聚合物的制造方法。
解决课题的手段
这样的本发明的目的通过以下方法实现,即,在阴离子性聚合引发剂的存在下,使乙烯基芳香族单体、共轭二烯烃单体或它们两者聚合反应,然后,于其中添加烷氧基钛化合物来使聚合反应终止,从而制造末端改性聚合物的方法。或者,通过在代替烷氧基钛化合物添加卤化钛化合物来使聚合反应终止后,添加碳数1~4的低级醇,也可以制造末端改性聚合物。
发明效果
就通过本发明方法制造的末端改性聚合物而言,通过将烷氧基钛化合物或相当于其的化合物用作聚合反应的终止剂,可以容易地将烷氧基钛基导入到聚合物末端。
将所得到的末端改性聚合物作为二氧化硅配合充气轮胎用橡胶组合物中的一个成分进行配合时,橡胶组合物中所配合的二氧化硅的分散性得到改善,可以充分满足二氧化硅本来所具有的滚动阻力的减轻和在湿润路面的稳定性的并存这一课题。
具体实施方式
末端基被改性的聚合物作为乙烯基芳香族单体、共轭二烯烃单体或它们两者的聚合物而形成。作为乙烯基芳香族单体,可举出苯乙烯、α-甲基苯乙烯、p-甲基苯乙烯、o-甲基苯乙烯、2,4,6-三甲基苯乙烯、1-乙烯基萘等,优选使用苯乙烯。作为共轭二烯烃单体,例如可举出1,3-丁二烯、异戊二烯、1,3-戊二烯、2,3-二甲基-1,3-丁二烯、1,3-己二烯、氯丁二烯等,优选使用1,3-丁二烯或异戊二烯。这些乙烯基芳香族单体和共轭二烯烃单体两者能够以任意混合比例并用,优选使用苯乙烯和1,3-丁二烯或异戊二烯两者。使用它们两者时,所得到的聚合物通常为无规共聚物,不过其也可以是嵌段共聚物。
聚合反应是通过使用阴离子性聚合引发剂的阴离子聚合法进行的。作为阴离子性聚合引发剂,可以使用有机锂化合物,优选使用烷基锂或芳基锂。
作为烷基锂,例如可举出甲基锂、乙基锂、丙基锂、正丁基锂、仲丁基锂、叔丁基锂、异丁基锂、己基锂、辛基锂、四亚甲基二锂、m-二异丙烯基苯二锂等,作为芳基锂,例如可举出苯基锂、甲苯基锂等。它们既可以单独使用也可以将2种以上并用,从操作性及工业上的经济性的观点出发,优选正丁基锂、仲丁基锂、叔丁基锂,从与单体的反应性的观点出发,更优选正丁基锂、仲丁基锂。
这些有机锂化合物通常以相对于投料单体(混合物)量约0.0001~10摩尔%的比例使用,优选以约0.0005~6摩尔%的比例使用。
聚合反应体系中,添加并使用相对于所使用的引发剂的摩尔量,以约10~300摩尔%的比例、优选以约40~200摩尔%的比例使用的2,2-二(四氢呋喃基)丙烷、N,N,N',N',-四甲基乙二胺、二乙醚、单甘醇二甲醚、二甘醇二甲醚、二甲氧基乙烷、四氢呋喃等。这些化合物在聚合反应时,作为在使用了环己烷、甲基环己烷等非极性溶剂的情况下的阴离子引发剂及生长种的活化剂或在共聚反应中的无规剂(Randomizer)而起作用。
聚合反应是例如使用环己烷、甲基环己烷、甲苯、四氢呋喃等烃类溶剂,以约-100~100℃、通常约0~70℃的条件进行约1~5小时左右,之后进行将烷氧基钛化合物加入到聚合反应体系中,使聚合反应终止。烷氧基钛化合物的量是对于导入生成聚合物的末端基充分的量,例如相对于所使用的阴离子性聚合引发剂的摩尔量,以约100~1000摩尔%的比例使用,优选以约200~400摩尔%的比例使用。
作为烷氧基钛化合物,可以使用四甲氧基钛、四乙氧基钛、四异丙氧基钛、四正丙氧基钛、四正丁氧基钛等四烷氧基钛,优选使用四甲氧基钛。
添加四氯化钛等卤化钛化合物代替烷氧基钛化合物,也可以使聚合反应终止,在聚合物末端形成来源于卤化钛化合物的基团之后,也可以使甲醇、乙醇、异丙醇、正丁醇等低级醇反应而形成烷氧基。
所使用的卤化钛化合物的量,与烷氧基钛化合物的情况同样,为对于导入生成聚合物的末端基充分的量,例如相对于所使用的阴离子性聚合引发剂的摩尔量,以约25~1000摩尔%的比例使用,优选以约100~400摩尔%的比例使用。这里所使用的阴离子聚合是按照以下的过程进行的聚合方法。
1) 引发剂对单体进行亲核攻击,由此产生生长种。
2) 该生长种进一步对单体进行亲核攻击,并重复此过程,由此产生具有生长末端的聚合物。
3) 聚合物末端的生长种对终止剂进行亲核攻击,聚合终止。
其结果,于一条聚合物链中分别导入了引发末端和终止末端各1个。因此,本来相对于引发剂理想的是以1:1即100%的比例使用终止剂,但是考虑到这次所使用的终止剂是TiX4即4价,将其下限值设为约25摩尔%。另外,用于形成烷氧基的低级醇的量为对于使作为末端基而导入的卤基完全转化为烷氧基充分的量。
烷氧基钛化合物至少使Ti(OR)3基形成于聚合物分子末端。例如将苯乙烯和1,3-丁二烯用作共聚单体(Comonomer)、或将1,3-丁二烯单独用作单体的情况下,反应如下式进行,形成在具有-[Ti(OR)2O]n-键(n:0~40)的同时、具有末端Ti(OR)3基的改性聚合物。
所得到的末端改性聚合物被配合于二烯系橡胶、特别是含有二氧化硅的二烯系橡胶中。末端改性聚合物在与二烯系橡胶的合计量100质量份中,以0.1~30质量份的比例使用,优选以1~10质量份的比例使用。若末端改性聚合物的比例使用得比这还少,则不能得到所希望的改性效果,另一方面若以这以上的比例使用,则未硫化橡胶的加工性会降低。
作为二烯系橡胶,将天然橡胶(NR)、异戊二烯橡胶(IR)、丁二烯橡胶(BR)、氯丁二烯橡胶(CR)、丁基橡胶(IIR)、丁腈橡胶(NBR)、苯乙烯丁二烯橡胶(SBR)等单独使用或者作为共混橡胶使用,优选使用NR、BR或它们的共混橡胶。作为SBR,可以使用乳液聚合SBR(E-SBR)、溶液聚合SBR(S-SBR)中的任一种。特别优选地使用与用于末端改性的、在分子中具有双键的聚合物相同的二烯系橡胶。
在二烯系橡胶组合物中,相对于每100质量份含有末端改性聚合物的二烯系橡胶,添加并使用10~150质量份、优选30~150质量份的二氧化硅、或二氧化硅与炭黑两者。这些填充剂、特别是二氧化硅的添加,虽然使滚动阻力等降低,但是若以这以上的比例使用,反而会使滚动阻力等恶化。
作为二氧化硅,使用BET比表面积(依据ASTM D1993-03)为70~200m2/g、优选为70~190m2/g的二氧化硅。这些二氧化硅是通过卤化硅或有机硅化合物的热分解法等制造的干法二氧化硅,或者是通过硅酸钠的基于酸的分解法等制造的湿法二氧化硅等,从成本及性能的方面考虑,优选使用湿法二氧化硅。实际上,可以直接使用作为橡胶工业用而上市的市售品。
为了提高二氧化硅所要求的特性及与二烯系橡胶的分散性(二氧化硅具有如下性质:与橡胶聚合物的亲和性不足,且在橡胶中二氧化硅彼此通过硅醇基生成氢键,降低二氧化硅在橡胶中的分散性),相对于每100质量份的含有硫酯改性聚合物的二烯系橡胶,配合1~20质量份、优选3~18质量份左右的硅烷偶联剂。作为硅烷偶联剂,可以优选使用具有与二氧化硅表面的硅醇基反应的烷氧基甲硅烷基和与聚合物反应的硫链的双(三烷氧基甲硅烷基丙基)硫化物:
(RO)3Si(CH2)3-(S)n-(CH2)3Si(OR)3
R:碳数1~2的烷基
n:1~4的整数
例如优选使用双(3-三乙氧基甲硅烷基丙基)四硫化物、双(2-三乙氧基甲硅烷基乙基)四硫化物、双(3-三甲氧基甲硅烷基丙基)四硫化物、双(3-三乙氧基甲硅烷基丙基)二硫化物等。
作为炭黑,一般可以使用SAF、ISAF、HAF、FEF、GPF、SRF等的炉黑。作为在充气轮胎的胎面部、特别是胎冠胎面部的形成时的有效成分的这些炭黑,与二氧化硅一起,相对于每100质量份的含有末端改性聚合物的二烯系橡胶以3~120质量份的比例使用。
在将以上各成分作为必须成分的橡胶组合物中,可配合如下物质使用:作为硫化剂的硫及噻唑类(MBT、MBTS、ZnMBT等)、亚磺酰胺类(CBS、DCBS、BBS等)、胍类(DPG、DOTG、OTBG等)、秋兰姆类(TMTD、TMTM、TBzTD、TETD、TBTD等)、二硫代氨基甲酸盐类(ZTC、NaBDC等)、黄原酸盐类(ZnBX等)等的硫化促进剂中的任意一种以上,优选配合使用含硫硫化促进剂。进而,可根据需要适当配合并使用作为橡胶的配合剂通常使用的其他的配合剂,例如滑石、粘土、石墨、硅酸钙等增强剂或者填充剂,硬脂酸等加工助剂,氧化锌,软化剂,增塑剂,防老剂等。
组合物的制备可通过使用捏合机、班伯里密炼机等混炼机或混合机及开炼机(open roll)等以一般的方法混炼而进行,所获得的组合物被成型成规定形状以后,在与所用的二烯系橡胶、硫化剂、硫化促进剂的种类及其配合比例相应的硫化温度下进行硫化,形成充气轮胎的胎面部等。
实施例
接着,就实施例来说明本发明。
实施例1
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷(关东化学制品) 7ml
2,2-二(四氢呋喃基)丙烷 0.279g(1.51毫摩尔)
(东京化成制品)
n-BuLi的正己烷溶液 2ml(3.28毫摩尔)
(关东化学制品;浓度1.64摩尔/L)。
在0℃向该溶液中滴入
苯乙烯(同公司制品) 5.69g(54.6毫摩尔)
搅拌3小时后,向其中加入
四甲氧基钛(同公司制品) 1.13g(6.57毫摩尔)
的10ml四氢呋喃的溶液,由此使聚合反应终止。
将从所得到的反应混合物中蒸馏除去挥发成分的残渣溶解于30ml的四氢呋喃中。将该溶液滴入到200ml的甲醇中,分离成可溶性成分和不溶性成分,将同样的操作重复2次后,蒸馏除去挥发成分,由此得到白色固体状的末端改性聚苯乙烯5.35g(收率94%)。
Mn:5160、2530(是作为双峰性的SEC数据观察到的;下同)
Mn(数均分子量)是由SEC(体积排阻色谱)测定、并将该值作为聚苯乙烯换算的分子量而估算的
PDI:1.1
PDI(多分散度)是用由SEC测定的Mw(重均分子量)和Mn的值,作为Mw/Mn计算而得,该PDI的值越接近1,则表示越可获得分子量分布受控制的聚合物
Rf:0.57
Rf值是由二氧化硅板的TLC(薄层色谱)测定的,其值越小则表示与二氧化硅的亲和性越高
。
实施例2
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.281g(1.52毫摩尔)
n-BuLi的正己烷溶液(浓度1.50摩尔/L) 1ml(1.50毫摩尔)。
在0℃向该溶液中滴入
苯乙烯 5.55g(53.3毫摩尔)
搅拌3小时后,向其中加入
四氯化钛(Aldrich公司制品) 1.43g(7.54毫摩尔)
,由此使聚合反应终止。进而向该混合溶液中加入10ml甲醇。
将从所得到的反应混合物中蒸馏除去挥发成分的残渣溶解于30ml的四氢呋喃中。将该溶液滴入到200ml的甲醇中,分离成可溶性成分和不溶性成分,将同样的操作重复2次后,蒸馏除去挥发成分,由此得到白色固体状的末端改性聚苯乙烯5.05g(收率91%)。
。
实施例3
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.282g(1.53毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
苯乙烯 5.39g(51.8毫摩尔)
搅拌3小时后,向其中加入
四氯化钛(Aldrich公司制品) 1.35g(7.12毫摩尔)
,由此使聚合反应终止。进而向该混合溶液中加入10ml乙醇。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到白色固体状的末端改性聚苯乙烯4.96g(收率92%)。
。
实施例4
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.284g(1.50毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 16.50g(46.6毫摩尔)
(Aldrich公司制品)
搅拌3小时后,向其中加入
四甲氧基钛 1.15g(6.69毫摩尔)
的10ml四氢呋喃的溶液,由此使聚合反应终止。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性聚丁二烯2.20g(收率89%)。
。
实施例5
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.276g(1.50毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 17.3g(48.0毫摩尔)
搅拌3小时后,向其中加入
四氯化钛 1.36g(7.17毫摩尔)
由此使聚合反应终止。进而向该混合溶液中加入10ml甲醇。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性聚丁二烯2.36g(收率91%)。
。
实施例6
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.320g(1.74毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 17.5g(44.4毫摩尔)
搅拌3小时后,向其中加入
四氯化钛 1.34g(7.06毫摩尔)
由此使聚合反应终止。进而向该混合溶液中加入10ml乙醇。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性聚丁二烯2.28g(收率87%)。
。
实施例7
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.294g(1.60毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 10.5g(29.1毫摩尔)
苯乙烯 2.62g(25.2毫摩尔)
搅拌3小时后,向其中加入
四甲氧基钛 1.13g(6.57毫摩尔)
由此使聚合反应终止。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性苯乙烯-丁二烯共聚物3.57g(收率85%)。
。
实施例8
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.261g(1.42毫摩尔)
n-BuLi的正己烷溶液(浓度1.50摩尔/L) 2ml(3.00毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 16.2g(44.9毫摩尔)
苯乙烯 3.43g(32.9毫摩尔)
搅拌3小时后,向其中加入
四氯化钛 1.62g(8.54毫摩尔)
由此使聚合反应终止。进而向该混合溶液中加入10ml甲醇。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性苯乙烯-丁二烯共聚物5.27g(收率90%)。
。
实施例9
在容量100ml的双颈烧瓶中于室温条件下加入
环己烷 7ml
2,2-二(四氢呋喃基)丙烷 0.255g(1.38毫摩尔)
n-BuLi的正己烷溶液(浓度1.64摩尔/L) 2ml(3.28毫摩尔)。
在0℃向该溶液中滴入
1,3-丁二烯的15重量%正己烷溶液 10.5g(29.1毫摩尔)
苯乙烯 2.86g(27.5毫摩尔)
搅拌3小时后,向其中加入
四氯化钛 1.35g(7.12毫摩尔)
由此使聚合反应终止。进而向该混合溶液中加入10ml乙醇。
对于所得到的反应混合物,施以与实施例1同样的后处理,得到无色粘性液体状的末端改性苯乙烯-丁二烯共聚物3.73g(收率84%)。
。
实施例10
称量4.35kg环己烷、300g苯乙烯及715g丁二烯,投入到聚合用高压釜中,于50℃进行搅拌。向该混合溶液中加入0.858g四甲基乙二胺、进而加入4ml正丁基锂(1.60mol/L),于50℃搅拌3小时。然后,加入2.20g四甲氧基钛的THF(30mL)悬浊液,于50℃搅拌3小时,由此终止聚合。从该聚合物溶液中蒸馏除去挥发成分后,进行将聚合物成分投入到甲醇(6.5kg)中的再沉淀处理,分离聚合物成分。进而,在减压下从该聚合物成分中蒸馏除去了挥发成分。结果,得到了末端改性聚合物954g(收率94%)。
。
实施例11
实施例10中所得到的末端改性苯乙烯- 80.00质量份
丁二烯共聚物
BR(日本Zeon制品BR1220) 20.00"
二氧化硅 80.00"
(Rhodia operations制品Zeosil Premium 200MP)
炭黑(Tokai Carbon Co., Ltd.制品SeastKHP) 5.00"
硬脂酸(NOF Corporation制品YR) 2.00"
脂肪酸酯(Schill&Seilacher制品HT207) 1.00"
防老剂(Solutia Europe制品6ppd) 1.50"
偶联剂(Evonik Degussa制品Si69) 6.40"
操作油(昭和Shell石油制品Extra4号S) 30.00"
氧化锌(正同化学制品氧化锌3种) 3.00"
硫化促进剂A 2.00"
(住友化学制品Soxinol D-G)
硫化促进剂B 1.70"
(大内新兴化学工业制品Nocceler CZ-G)
硫(轻井泽制炼所制品油处理硫) 1.50"
以上各成分中,将除硫化促进剂及硫之外的各成分于1.7L密闭式班伯里密炼机中混炼5分钟,将混炼物放出到混合机外并冷却至室温后,使用相同班伯里密炼机,对硫化促进剂及硫进行混合。将所得到的未硫化的橡胶组合物于150℃加压硫化30分钟,得到硫化橡胶。
对于未硫化橡胶组合物测定了门尼粘度,另外对于硫化物分别测定了RPA(硫化佩恩(Payne)效应)、拉伸强度、回弹性(40℃)、全自动拉伸及高温度拉伸。关于所得到的测定值,用将使用了未改性苯乙烯-丁二烯共聚物(Mn:293,000)的情况设为100的指标表示。
门尼粘度(粘度ML1+4[M]):99
依照JIS K6300
通常指标越小则粘度越低、加工性优异,但是本次取了倒数,因此越大越优异
RPA(硫化佩恩效应):103
依照ISO 11345
指标越小佩恩效应越大,二氧化硅的分散性越良好
拉伸强度:101
依照JIS K6251
回弹性(40℃):100
依照JIS K6255
全自动拉伸:108
高温度拉伸:115
均依照对应于ISO 48的JIS K6251/6301:2006
指标越大橡胶的伸长率越好
由以上结果可知,得到了加工性比较良好、佩恩效应高、拉伸特性及回弹性优异的二烯系橡胶组合物。
Claims (7)
1.末端改性聚合物的制造方法,其特征在于,在阴离子性聚合引发剂的存在下,使乙烯基芳香族单体、共轭二烯烃单体或它们两者聚合反应,于其中添加卤化钛化合物来使聚合反应终止后,添加碳数1~4的低级醇。
2.权利要求1所述的末端改性聚合物的制造方法,其中,作为卤化钛化合物使用四氯化钛。
3.权利要求1所述的末端改性聚合物的制造方法,其中,形成了于末端部位具有来源于烷氧基钛化合物的基团的聚合物。
4.权利要求1所述的末端改性聚合物的制造方法,其中,作为乙烯基芳香族单体使用苯乙烯或其衍生物。
5.权利要求1所述的末端改性聚合物的制造方法,其中,作为共轭二烯烃单体使用1,3-丁二烯或异戊二烯。
6.权利要求1所述的末端改性聚合物的制造方法,其中,作为阴离子性聚合引发剂使用有机锂化合物。
7.二烯系橡胶组合物,其为将用权利要求1所述的方法制造的末端改性聚合物配合于二烯系橡胶中而得的二烯系橡胶组合物。
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