TWI659999B - 具有良好加工特性之經降低冷流的聚合物 - Google Patents
具有良好加工特性之經降低冷流的聚合物 Download PDFInfo
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- TWI659999B TWI659999B TW103114449A TW103114449A TWI659999B TW I659999 B TWI659999 B TW I659999B TW 103114449 A TW103114449 A TW 103114449A TW 103114449 A TW103114449 A TW 103114449A TW I659999 B TWI659999 B TW I659999B
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- polymer
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- item
- alkaryl
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- 229920000642 polymer Polymers 0.000 title claims abstract description 97
- 238000012545 processing Methods 0.000 title abstract description 18
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 16
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 16
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims abstract description 8
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 8
- 125000000000 cycloalkoxy group Chemical group 0.000 claims abstract description 8
- 125000000962 organic group Chemical group 0.000 claims abstract description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 73
- 239000005060 rubber Substances 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 56
- 239000000945 filler Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
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- 239000003795 chemical substances by application Substances 0.000 claims description 11
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- 239000000539 dimer Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
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- 239000003381 stabilizer Substances 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 abstract description 14
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- 238000006243 chemical reaction Methods 0.000 description 21
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- 230000000052 comparative effect Effects 0.000 description 17
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- 239000006229 carbon black Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
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- 239000000377 silicon dioxide Substances 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
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- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 6
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
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- 229910052719 titanium Inorganic materials 0.000 description 4
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- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229920000459 Nitrile rubber Polymers 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960000541 cetyl alcohol Drugs 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 125000006686 (C1-C24) alkyl group Chemical group 0.000 description 2
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- QRMPKOFEUHIBNM-UHFFFAOYSA-N 1,4-dimethylcyclohexane Chemical compound CC1CCC(C)CC1 QRMPKOFEUHIBNM-UHFFFAOYSA-N 0.000 description 2
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- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
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- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
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- 244000043261 Hevea brasiliensis Species 0.000 description 1
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
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- AKJDBMXGGIRWMV-UHFFFAOYSA-N [Li]C(C=C)N(Cc1ccccc1)Cc1ccccc1 Chemical compound [Li]C(C=C)N(Cc1ccccc1)Cc1ccccc1 AKJDBMXGGIRWMV-UHFFFAOYSA-N 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000001342 alkaline earth metals Chemical class 0.000 description 1
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DEYSDTBRAVABGB-UHFFFAOYSA-N benzene;ethene Chemical compound C=C.C=C.C1=CC=CC=C1 DEYSDTBRAVABGB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 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
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229940035422 diphenylamine Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 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 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- DLENDKSMPIEGPF-UHFFFAOYSA-N lithium piperidine Chemical compound [Li+].C1CCNCC1 DLENDKSMPIEGPF-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- DWNRISLZVCBTRN-UHFFFAOYSA-N lithium;piperidin-1-ide Chemical compound [Li]N1CCCCC1 DWNRISLZVCBTRN-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- FJDQVJUXXNIHNB-UHFFFAOYSA-N lithium;pyrrolidin-1-ide Chemical compound [Li+].C1CC[N-]C1 FJDQVJUXXNIHNB-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C08F236/14—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 containing elements other than carbon and hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
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- 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
- C08C19/34—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups
- C08C19/36—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with oxygen or oxygen-containing groups with carboxy radicals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
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- 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
- C08K3/045—Fullerenes
Abstract
本發明係關於一種具有良好加工特性之經降低冷流的聚合物,其在聚合物鏈之末端具有式(I)的含矽烷之羧基
其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,較佳為O、N、S或Si,R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,較佳為O、N、S或Si,A係為二價有機基團,其可含有一或多個雜原子,較佳為O、N、S或Si,以及C和H。
Description
本發明係關於具有良好加工特性之經降低冷流、端基官能化之聚合物、及其製備與用途。
輪胎胎面所欲之重要性質包括在乾溼表面上之良好附著、低滾動阻力及高耐磨損性。非常困難係改良輪胎的防滑性而同時無使滾動阻力及耐磨損性更差。低滾動阻力對於低燃料消耗係重要的,以及高耐磨損性對於輪胎長的使用壽命係重要因素。
輪胎胎面的防濕滑性及滾動阻力極大取決於橡膠的動力/機械性質,其係使用於摻混製造中。為降低滾動阻力,在較高溫度(60℃至100℃)下具有高彈性之橡膠係使用於輪胎胎面。另一方面,為改良防濕滑性,具有在低溫下(0至23℃)之高阻尼因子或者在0℃至23℃範圍中之低彈性的橡膠係有利的。為實現此需求複雜的輪廓,使用不同橡膠之混合物於輪胎中。通常,使用一或多種具有相當高玻璃轉移溫度之橡膠(像是苯乙烯-丁二烯橡膠)以及一或多種具有相當低玻璃轉移溫度之橡膠(像是具有高1,4-順式含量之聚丁二烯或者具有低苯乙烯與低乙烯基含量之苯乙烯丁二烯橡膠或者在溶液中製備以及具有適度的1,4-順式與低乙烯基含量之聚丁二烯)之混合物。
含有雙鍵之陰離子聚合溶液橡膠,像是溶液聚丁二烯以及溶液苯乙烯-丁二烯橡膠,就具有低滾動阻力之輪胎胎面而言,其相較於對應的乳液橡膠具有優點。該等優點尤其是在乙烯基含量以及有關之玻璃轉移溫度以及分子分支之可控制性。在實際使用中,此些引起特別優點在於輪胎的防濕滑性及滾動阻力之關係。能量散逸以及因此輪胎胎面之滾動阻力之重要原因係產生自聚合物鏈之游離端以及產生自可逆的建構(buildup)與藉由使用於輪胎胎面混合物之填料(通常為矽石及/或碳黑)所形成之填料網絡的降解。在聚合物鏈之末端及/或聚合物鏈之開始處引入官能基能使此些鏈的末端及/或開始處物理或化學連接至填料表面。此限制其移動性以及因此降低在輪胎胎面上動態應力下之能量散逸。同時,此些官能基可改良輪胎胎面中之填料的分散,其可導致減弱的填料網絡且因此進一步降低滾動阻力。
為此目的,已發展數個用於端基改質之方法。例如:EP0180141A1描述使用4,4’-雙(二甲基胺基)二苯基酮或者N-甲基己內醯胺作為官能化試劑(functionalizing reagents)。環氧乙烷以及N-乙烯基吡咯啶酮的使用亦已知自EP0864606A1。數個另外可能的官能化試劑係詳述於US4417029。藉由官能陰離子聚合起始劑在聚合物鏈的開始處引入官能基之方法係描述,例如於EP0513217A1及EP0675140A1(具有經保護羥基之起始劑),US20080308204A1(含硫醚之起始劑)以及於US5792820、EP0590490A1與EP0594107A1(作為聚合起始劑之二級胺的鹼金屬醯胺)。
作為強極性雙牙配位子之羧基可特別與橡膠混合物中之矽石填料表面良好反應。沿著溶液製備之二烯橡膠的聚合物鏈引入羧基之方
法係已知且描述,例如,於DE2653144A1、EP1000971A1、EP1050545A1、WO2009034001A1。此些方法具有數個缺點,例如需要長反應時間,僅不完全地轉換官能化試劑,以及發生聚合物鏈的改變導致像是分支之副反應。此外,此些方法並不能特別有效地官能化聚合物鏈之末端。
在二烯橡膠之鏈端引入羧基同樣地已描述例如於US3242129,其係藉由聚合物鏈之陰離子端與CO2之反應。此方法具有聚合物溶液必須與氣態CO2接觸之缺點,其發現係困難的因為高黏度及所產生差的混合。此外,因為在CO2之碳原子處聚合物鏈的超過一個末端的反應發生控制困難之偶合反應。此偶合可藉由聚合物鏈之碳陰離子端先與環氧乙烷或環氧丙烷連續反應、接著現為烷氧化的(alkoxidic)聚合物鏈之末端與環酸酐反應而避免(US4465809)。然而,此處亦是有一氣態及同時非常毒的環氧乙烷或環氧丙烷必須被引入高黏度橡膠溶液之缺點。此外,烷氧化的鏈端與環酸酐之反應形成易水解酯鍵,其可在加工及後續使用過程中分開。
尤其是具有在矽上總共至少兩個氫及/或烷氧基及/或芳氧基取代基之矽烷類及環矽氧烷係對二烯橡膠的端基官能化良好的適合性,因為在矽原子上之該等取代基中之一個係可在對於聚合物鏈的陰離子二烯端之快速取代反應中立即交換以及該等在Si上之另外上述取代基係可視情況在水解後作為可與輪胎胎面混合物的填料反應之官能基。此類型矽烷之實例係可發現於US3244664、US4185042、EP0778311A1及US20050203251A1中。
此些矽烷類一般具有直接聯結至矽原子或者經由間隔物聯結至Si以及可與橡膠混合物中之矽石填料的表面反應之官能基。此些官能基
通常係直接在Si上之烷氧基或者鹵素,以及經由間隔物聯結至Si之三級胺基取代基。此些矽烷之缺點係經由矽烷分子之複數個聚合物鏈的陰離子端的可能反應,消除令人煩惱的成分以及在加工及儲存過程中偶合以形成Si-O-Si鍵。藉由此些矽烷引入羧基尚未被描述。
WO2012/065908A1係描述1-氧雜-2-矽矽雜環烷作為官能化試劑,用於在二烯聚合物中引入羥基端基。此些1-氧雜-2-矽雜環烷並不具有上段描述之矽烷的缺點,像是經由矽烷分子之複數個聚合物鏈的陰離子端的反應,消除令人煩惱的成分以及在加工及儲存過程中偶合以形成Si-O-Si鍵。然而,此些官能化試劑亦不能夠在聚合物鏈的末端處引入羧基。
因此,所強調之問題係提供不具先前技術缺點的經羧基封端之聚合物,且更特別係能夠利用具有聚合物鏈陰離子端之矽烷的良好反應性。
此問題通過具有在聚合物鏈末端處之式(I)含矽烷的羧基之端基官能化聚合物的建議而解決
其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,較佳為O、N、S或Si,
R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,較佳為O、N、S或Si,A係為二價有機基團,其可含有一或多個雜原子,較佳為O、N、S或Si,以及C和H,較佳地,本發明經端基官能化之聚合物可呈具有式(II)端基之羧酸鹽的形式:
其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,較佳為O、N、S或Si,R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,較佳為O、N、S或Si,A係為二價有機基團,其可含有一或多個雜原子,較佳為O、N、S或Si,以及C和H,n係1至4的整數,M係一至四價的金屬或半金屬,較佳為Li、Na、K、Mg、Ca、Zn、Fe、Co、Ni、Al、Nd、Ti、Sn、Si、Zr、V、Mo、W。
用於製備本發明經端基官能化之聚合物之較佳聚合物係二烯聚合物,以及可藉由二烯類與乙烯基芳族共聚單體之共聚合而獲得之二
烯共聚物。
較佳二烯類係1,3-丁二烯、異戊二烯、1,3-戊二烯、2,3-二甲基丁二烯、1-苯基-1,3-丁二烯及/或1,3-己二烯。特佳係使用1,3-丁二烯及/或異戊二烯。
乙烯基芳族共聚單體可例如為苯乙烯、o-、m-及/或p甲基苯乙烯、p-三級-丁基苯乙烯、α-甲基苯乙烯、乙烯基萘、二乙烯基苯、三乙烯基苯及/或二乙烯基萘。特佳係使用苯乙烯。
此些聚合物較佳地藉由陰離子溶液聚合或者藉由配位觸媒方式之聚合而製備。在此背景中,配位觸媒被理解為意指戚[格勒]-納[他(Ziegler-Natta)觸媒或者單金屬觸媒系統。較佳的配位觸媒係以Ni、Co、Ti、Zr、Nd、V、Cr、Mo、W或Fe為基質的那些。
用於陰離子溶液聚合之起始劑係那些以鹼金屬或鹼土金屬為基質者,例如甲基鋰、乙基鋰、異丙基鋰、n-丁基鋰、二級-丁基鋰、戊基鋰、n-己基鋰、環己基鋰、辛基鋰、癸基鋰、2-(6-鋰-n-己氧基)四氫哌喃、3-(三級-丁基二甲基矽氧基)-1-丙基鋰、苯基鋰、4-丁基苯基鋰、1-萘基鋰、p-甲苯基鋰以及衍生自三級N-烯丙基胺類之烯丙基鋰化合物,像是[1-(二甲基胺基)-2-丙烯基]鋰、[1-[雙(苯基甲基)胺基]-2-丙烯基]鋰、[1-(二苯基胺基)-2-丙烯基]鋰、[1-(1-吡咯啶基)-2-丙烯基]鋰、二級胺類的鋰醯胺,像是鋰吡咯啶(pyrrolidide)、鋰哌啶(lithium piperidide)、鋰六亞甲基醯亞胺、鋰1-甲基咪唑啶(lithium 1-methylimidazolidide)、鋰1-甲基哌嗪醯胺、嗎福啉醯胺鋰(lithium morpholide)、鋰二環己基醯胺、鋰二苄基醯胺、鋰二苯基醯胺。此些烯丙基鋰化合物以及此些鋰醯胺亦可原位藉由有機鋰化合物與分
別的三級N-烯丙基胺類或者與分別的二級胺類反應而製備。此外,亦可能使用二-及多官能有機鋰化合物,例如:1,4-二鋰基丁烷(1,4-dilithiobutane)、二鋰哌嗪醯胺(dilithium piperazide)。較佳使用n-丁基鋰以及二級丁基鋰。
此外,亦可能使用已知隨機試劑(randomizers)以及用於聚合物微結構之控制劑,例如二乙基醚、二-n-丙基醚、二異丙基醚、二-n-丁基醚、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二-n-丁基醚、乙二醇二-三級-丁基醚、二伸乙基二醇二甲基醚、二伸乙基二醇二乙基醚、二伸乙基二醇二-n-丁基醚、二伸乙基二醇二-三級-丁基醚、2-(2-乙氧基乙氧基)-2-甲基丙烷、三伸乙基二醇二甲基醚、四氫呋喃、乙基四氫糠基醚、己基四氫糠基醚、2,2-雙(2-四氫呋喃基)丙烷、二烷、三甲基胺、三乙基胺、N,N,N’,N’-四甲基伸乙基二胺、N-甲基啉、N-乙基啉、1,2-二哌啶基基乙烷、1,2-二吡咯啶基乙烷、1,2-二啉基乙烷以及醇類、酚類、羧酸類、磺酸類之鉀鹽及納鹽。
這樣的溶液聚合係已知的且描述例如於I.Franta,Elastomers and Rubber Compounding Materials;Elsevier 1989,第113-131頁;於Houben-Weyl,Methoden der Organischen Chemie[Methods of Organic Chemistry],Thieme Verlag,Stuttgart,1961,卷XIV/1,第645至673頁或者卷E 20(1987),第114至134頁以及第134至153頁;以及於Comprehensive Polymer Science,卷4,第II部分(Pergamon Press Ltd.,Oxford 1989),第53-108頁。
較佳的二烯均聚物以及二烯共聚物之製備較佳發生於溶劑中。使用於聚合之溶劑較佳係惰性非質子性溶劑,例如石蠟烴類,像是異
構的丁烷、戊烷、己烷、庚烷、辛烷、癸烷、環戊烷、甲基環戊烷、環己烷、甲基環己烷、乙基環己烷或1,4-二甲基環己烷;或者烯烴類,像是1-丁烯;或者芳族烴類,像是苯、甲苯、乙基苯、二甲苯、二乙基苯或丙基苯。此些溶劑可各別地或組合使用。較佳係環己烷、甲基環戊烷及n-己烷。以極性溶劑摻混係同樣可能的。
再根據本發明之方法中,溶劑之量典型地係在100至1000g範圍中、較佳在200至700g範圍中,其以100g之所使用單體總量為基準。然而,亦可能在缺少溶劑下聚合所使用之單體。
聚合係可以初始裝載單體及溶劑以及隨後藉由添加起始劑或觸媒開始聚合這樣的方式進行。亦可能在饋料程序中聚合,其中藉由添加單體及溶劑填充聚合反應器,起始劑或觸媒係初始裝載或者與單體和溶劑添加。亦可能變體,像是初始裝載溶劑於反應器中、添加起始劑或觸媒以及接著添加單體。此外,聚合可以連續模式操作。在所有的情況中,亦可能在聚合過程中或者結束時進一步添加單體及溶劑。
聚合時間可在幾分鐘至幾小時寬廣限制中變化。典型地,聚合係在10分鐘高至8小時,較佳20分鐘至4小時期間中進行。其可在標準壓力下或是增高壓力下(1至10巴)進行。
以驚訝地發現使用一或多種矽雜內酯作為官能化試劑可製造經羧基封端之聚合物,其不具先前技術之缺點。
矽雜內酯係式(III)之化合物
其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,較佳為O、N、S或Si,R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,較佳為O、N、S或Si,A係為二價有機基團,其可含有一或多個雜原子,較佳為O、N、S或Si,以及C和H,其中較佳R1、R2係為相同或不同以及各自為H、(C1-C24)-烷基、(C1-C24)-烷氧基、(C3-C24)-環烷基、(C3-C24)-環烷氧基、(C6-C24)-芳基、(C6-C24)-芳氧基、(C6-C24)-烷芳基、(C6-C24)-烷芳基氧基、(C6-C24)-芳烷基或(C6-C24)-芳烷氧基,其可含有一或多個雜原子,較佳為O、N、S或Si,以及R3、R4係為相同或不同以及各自為H、(C1-C24)-烷基、(C3-C24)-環烷基、(C6-C24)-芳基、(C6-C24)-烷芳基或(C6-C24)-芳烷基,其可含有一或多個雜原子,較佳為較佳O、N、S或Si。
式(III)化合物之實例係:2,2-二甲基-1-氧雜-2-矽雜環己烷-6-酮(1)、2,2,4-三甲基-1-氧雜-2-矽雜環己烷-6-酮(2)、2,2,5-三甲基-1-氧雜-2-矽雜環己烷-6-酮(3)、
2,2,4,5-四甲基-1-氧雜-2-矽雜環己烷-6-酮(4)、2,2-二乙基-1-氧雜-2-矽雜環己烷-6-酮(5)、2,2-二乙氧基-1-氧雜-2-矽雜環己烷-6-酮(6)、2,2-二甲基-1,4-二氧雜-2-矽雜環己烷-6-酮(7)、2,2,5-三甲基-1,4-二氧雜-2-矽雜環己烷-6-酮(8)、2,2,3,3-四甲基-1,4-二氧雜-2-矽雜環己烷-6-酮(9)、2,2-二甲基-1-氧雜-4-噻-2-矽雜環己烷-6-酮(10)、2,2-二乙基-1-氧雜-4-噻-2-矽雜環己烷-6-酮(11)、2,2-二苯基-1-氧雜-4-噻-2-矽雜環己烷-6-酮(12)、2-甲基-2-乙烯基-1-氧雜-4-噻-2-矽雜環己烷-6-酮(13)、2,2,5-三甲基-1-氧雜-4-噻-2-矽雜環己烷-6-酮(14)、2,2-二甲基-1-氧雜-4-吖-2-矽雜環己烷-6-酮(15)、2,2,4-三甲基-1-氧雜-4-吖-2-矽雜環己烷-6-酮(16)、2,4-二甲基-2-苯基-1-氧雜-4-吖-2-矽雜環己烷-6-酮(17)、2,2-二甲基-4-三甲基矽基-1-氧雜-4-吖-2-矽雜環己烷-6-酮(18)、2,2-二乙氧基-4-甲基-1-氧雜-4-吖-2-矽雜環己烷-6-酮(19)、2,2,4,4-四甲基-1-氧雜-2,4-二矽雜環己烷-6-酮(20)、3,4-二氫-3,3-二甲基-1H-2,3-苯氧雜矽(benzoxasilin)-1-酮(21)、2,2-二甲基-1-氧雜-2-矽雜環戊烷-5-酮(22)、2,2,3-三甲基-1-氧雜-2-矽雜環戊烷-5-酮(23)、2,2-二甲基-4-苯基-1-氧雜-2-矽雜環戊烷-5-酮(24)、2,2-二(三級丁基)-1-氧雜-2-矽雜環戊烷-5-酮(25)、2-甲基-2-(2-丙烯-1-基)-1-氧雜-2-矽雜環戊烷-5-酮(26)、1,1-二甲基-2,1-苯氧雜矽醇(benzoxasilol)-3(1H)-酮(27)、2,2-二甲基-1-氧雜-2-矽雜環庚烷-7-酮(28)。
這樣矽雜內酯之合成係描述例如於US 2,635,109;M.Wieber,M.Schmidt,Chemische Berichte 1963,96(10),2822-5;J.M.Wolcott,F.K.Cartledge,Journal of Organic Chemistry 1974,39(16),2420-4;M.P.Sibi,J.W.Christensen,Tetrahedron Letters 1995,36(35),6213-6;T.Linker,M.Maurer,F.Rebien,Tetrahedron Letters 1996,37(46),8363-6;M.Shindo等人,Angewandte Chemie,International Edition 2004,43(1),104-6。
已發現本發明經端基官能化之聚合物可藉由聚合物鏈之反應性末端與矽雜內酯之反應以及任選接著用於製造羧基端基之羧酸鹽端基的質子化作用而製備。
因此,本發明亦提供矽雜內酯作為官能化試劑用於製備具有式(I)或(II)端基之本發明經端基官能化之聚合物之用途。
當具有聚合物鏈的非常反應性親核末端之聚合物係與式(III)之矽雜內酯反應時,該聚合物鏈不能僅連接在官能化試劑之矽原子上;此外,連接可附加地發生於羰基碳原子上。此導致不具有任何式(I)或(II)官能端基的聚合物鏈之線性偶合。此些偶合產物在應用背景中係稱為“二聚物”。聚合物鏈線性偶合的一個實例係顯示於反應式1,以及亦可形成另外的二聚物,其取決於矽雜內酯之開環。通常對於所有二聚物形成之特徵係其具有一或多種衍生自式(III)矽雜內酯之結構單元,較佳為式(IV)之結構單元
在聚合物的製備中,官能化試劑的添加引起包含經端基官能化之聚合物的聚合物混合物以及含有一或多種衍生自式(III)矽雜內酯之結構單元的二聚物。具有聚合物鏈的非常反應性親核末端之聚合物係例如二烯均聚物及二烯共聚物,其係藉由陰離子聚合或與配位觸媒而製備。
聚合物:具有反應性鏈端之聚合物鏈
M+:相對離子,例如L+
反應式1
聚合物混合物中之二聚物含量代表性地係在10至90%重量比之範圍中,其以聚合物之總量為基準。此類之偶合反應在某些情形下可為所欲的,以增加多分散性以及以此方式影響聚合物混合物之流變性質,像是慕尼黏度、冷流以及加工特性。
本發明聚合物混合物較佳具有10 000至2 000 000g/mol,較佳100 000至1 000 000g/mol之平均莫耳質量(數量平均,Mn)以及-110℃至+20℃,較佳-110℃至0℃之玻璃轉移溫度,以及10至200,較佳30至150,慕尼單位之慕尼黏度[ML 1+4(100℃)]。
本發明進一步提供一種製備本發明經端機官能化之聚合物之方法,其中添加一或多種式(III)化合物,其作為純物質、溶液或懸浮液,
以提供具有聚合物鏈之反應性末端之聚合物。添加較佳跟隨聚合之結束但亦可在完全單體轉化前。式(III)矽雜內酯與具有聚合物鏈之反應性末端之聚合物的反應係在慣常使用於聚合之溫度下實現。對於式(III)矽雜內酯與聚合物鏈的反應性末端之反應的反應時間可介於幾分鐘及數小時之間。
此些化合物之數量可選擇至使得聚合物鏈之所有反應性末端係與式(III)矽雜內酯反應,或者可能使用缺乏此些化合物。所使用式(III)化合物之數量可涵蓋一寬廣範圍。較佳的數量係介於0.005至2%重量比之範圍、更佳介於0.01至1%重量比之範圍,其以聚合物之數量為基準。
除了式(III)之矽雜內酯,亦可能使用典型用於與聚合物鏈的反應性末端之反應的陰離子二烯聚合的偶合試劑。這樣偶合試劑之實例係為四氯化矽、甲基三氯矽烷、二甲基二氯矽烷、錫四氯化物、二丁基錫二氯化物、四烷氧基矽烷、乙二醇二環氧丙基醚、1,2,4-參(氯甲基)苯。這樣的偶合試劑可在式(III)矽雜內酯之前、一起或者之後添加。
在本發明含矽烷、經羧酸鹽封端之聚合物的加工(workup)之前或過程中,在完成添加式(III)矽雜內酯以及視情況的偶合試劑上,較佳地添加慣常的老化穩定劑,像是立體受阻酚類、芳族胺類、亞磷酸鹽類、硫醚。此外,可能添加使用於二烯橡膠之慣常填充油(extender oils),像是DAE(Distillate Aromatic Extract)、TDAE(Treated Distillate Aromatic Extract)、MES(Mild Extraction Solvates)、RAE(Residual Aromatic Extract)、TRAE(Treated Residual Aromatic Extract)、環烷油及重環烷油。亦可能添加填料,像是碳黑以及矽石、橡膠及橡膠輔助劑。
溶劑可藉由慣常方法像是蒸餾、以蒸汽汽提或者視情況在提
高溫度下施加減壓,自聚合程序中移除。
本發明進一步提供本發明經端基官能化之聚合物用於製造可硫化橡膠組成物之之用途。
此些可硫化橡膠組成物較佳包含進一步的橡膠、填料、橡膠化學品、加工助劑及填充油。
另外的橡膠係例如天然及合成橡膠。若存在,其量係較佳介於0.5至95%重量比之範圍,較佳在10至80%%重量比範圍中,其以混合物中聚合物總量為基準。
附加地添加橡膠之數量係再藉由本發明混合物的個別終端使用而引導。此種合成橡膠之實例係為BR(聚丁二烯)、丙烯酸-烷基酯共聚物、IR(聚異戊二烯)、E-SBR(藉由乳化聚合製備之苯乙烯-丁二烯共聚物)、S-SBR(藉由溶液聚合製備之苯乙烯-丁二烯共聚物)、IIR(異丁烯-異戊二烯共聚物)、NBR(丁二烯-丙烯腈共聚物)、HNBR(部分氫化或全部氫化之NBR橡膠)、EPDM(乙烯-丙烯-二烯三元聚合物)以及此些橡膠之混合物。為了製造汽車輪胎、特別是天然橡膠,具有高於-60℃玻璃轉移溫度之E-SBR及S-SBR、具有高順式含量(>90%)以及使用以Ni、Co、Ti或Nd為基質之觸媒製備之聚丁二烯橡膠,以及具有高至80%乙烯基含量之聚丁二烯橡膠以及其混合物係有利的。
用於本發明橡膠組成物之有用填料包括所有已知使用於橡膠工業之填料。此些包括活性或非活性填料。
以下以示例方式提及:
- 經細分之矽石,其係例如藉由矽酸鹽溶液之沉澱或者具有5-1000(較
佳20-400)m2/g(BET表面積)比表面積以及10-400nm一次粒徑之矽鹵化物的火焰水解而製得。該等矽石亦可視情況地作為與其他金屬氧化物(像是Al、Mg、Ca、Ba、Zn、Zr、Ti)之混合氧化物而存在。
- 合成矽酸鹽,像是矽酸鋁,鹼土金屬矽酸鹽像是矽酸鎂或矽酸鈣,其具有20-400m2/g之BET表面積以及10-400nm之一次粒徑;
- 天然矽酸鹽,像是高嶺土、蒙脫石及其他自然產生的矽石;
- 玻璃纖維及玻璃纖維產品(mats、strands)或玻璃微球;
- 金屬氧化物,像是氧化鋅、氧化鈣、氧化鎂、氧化鋁;
- 金屬碳酸鹽,像是碳酸鎂、碳酸鈣、碳酸鋅;
- 金屬氫氧化物,例如氫氧化鋁、氫氧化鎂;
- 金屬硫酸鹽,像是硫酸鈣、硫酸鋇;
- 碳黑:此處待使用之碳黑係燈黑、槽黑、爐黑、氣黑、熱碳黑、乙炔黑或弧光方法製得之碳黑,以及具有9-200m2/g之BET表面積,例如SAF、SAF-LS、ISAF-HM、ISAF-LM、ISAF-HS、CF、SCF、HAF-LS、HAF、HAF-HS、FF-HS、PF、XCF、FEF-LS、FEF、FEF-HS、GPF-HS、GPF、APF、SRF-LS、SRF-LM、SRF-HS、SRF-HM以及MT碳黑,或者ASTM N110、N219、N220、N231、N234、N242、N294、N326、N327、N330、N332、N339、N347、N351、N356、N358、N375、N472、539、N550、N568、N650、N660、N754、N762、N765、N774、N787以及N990碳黑。
- 橡膠凝膠,特別是那些具有5至1000nm之粒子尺寸以BR、E-SBR及/或聚氯平為基質者。
所使用之填料較佳為經細分之矽石及/或碳黑。
所提及之填料係可單獨或以混合物形式使用。在一特佳具體實例中,橡膠組成物包含,作為填料之淺色填料(像是經細分之矽石)與碳黑之混合物,該淺色填料對碳黑之混合比率係0.01:1至50:1,較佳0.05:1至20:1。
此處,填料係以10至500重量份範圍中之數量使用,其以100重量份之橡膠為基準。較佳地,使用20至200重量份範圍間之數量。
在一另外的本發明具體實例中,橡膠組成物亦可包含橡膠輔助劑,其例如改良橡膠組成物之加工性質、用於交鏈橡膠組成物、改良本發明橡膠組成物所製得之硫化橡膠對於其特定最終用途的物理性質、改良橡膠與填料之交互作用或者用於將橡膠附著至填料。
橡膠輔助劑係例如交鏈劑(例如硫或提供硫之化合物)以及還有反應加速劑、老化穩定劑、熱穩定劑、光穩定劑、抗臭氧劑、加工助劑、增塑劑、增稠劑、發泡劑、染料、顏料、蠟、增效劑(extenders)、有機酸、矽烷、阻滯劑(retardants)、金屬氧化物、填充油(例如DAE(Distillate Aromatic Extract)、TDAE(Treated Distillate Aromatic Extract)、MES(Mild Extraction Solvates)、RAE(Residual Aromatic Extract)、TRAE(Treated Residual Aromatic Extract)、環烷油及重環烷油)以及活化劑。
橡膠輔助劑之總量係在1至300重量份中,其以100重量份之總橡膠為基準。較佳使用在5至150重量份的橡膠輔助劑範圍中之量。
可硫化橡膠組成物可以單階段或多階段方法製得,較佳為2至3個混合階段。例如硫或加速劑係可添加於分開的混合階段,例如在輥(roller)上,較佳的溫度係於30至90℃的範圍中。較佳地,在最後混合階段
添加硫及加速劑。
適用於製造可硫化橡膠組成物之設備的實例包括輥、捏合機、密閉混合器或混合擠製機。
因此,本發明進一步提供可硫化橡膠組成物,其包含具有式(I)或(II)端基之經端基官能化之聚合物。
本發明聚合物或其橡膠混合物結合低冷流、良好動力性質及良好加工特性。
本發明進一步提供本發明可硫化橡膠組成物之用途,其用於製造橡膠硫化物,尤其是製造輪胎,特別是具有特低滾動阻力加上高的防濕滑性及耐磨損性之輪胎胎面。
本發明可硫化橡膠組成物亦適用於製造模製物,例如用於製造電纜護套、軟管、傳動皮帶、輸送帶、輥護罩(roll covers)、鞋底(shoe soles)、墊圈及阻尼元件。
以下實例係用於說明本發明但不具有限制效果。
輪胎胎面組成物2a-e及6a-e之擠製型材(Extrusion profiles)3a-e及7a-e。
惰性化之20公升反應器係裝載8.5kg之己烷、1185g之1,3-丁二烯、315g之苯乙烯、8.6mmol之2,2-雙(2-四氫呋喃基)丙烷以及11.3
mmol之丁基鋰,並且將成分加熱至60℃。進行聚合同時在60℃攪拌25分鐘。接著,添加11.3mmol之鯨臘醇以封蓋聚合物鏈之陰離子端,排出橡膠溶液並藉由添加3g之Irganox® 1520(2,4-雙(辛基硫基甲基)-6-甲基酚)穩定化,以及藉由蒸氣汽提移除溶劑。將橡膠碎屑(crumbs)在降低壓力於65℃下乾燥。
程序係如於實例1a。然而,代替鯨臘醇,添加與丁基鋰數量等莫耳之2,2-二甲基-1-氧雜-4-噻-2-矽雜環己烷-6-酮的數量(作為溶液於甲苯中)以及隨後將反應器組分加熱至60℃額外的20分鐘。
程序係如於實例1b。然而,在添加丁基鋰之前,添加與丁基鋰數量等莫耳之吡咯啶的數量。
程序係如於實例1b。然而,代替矽雜內酯,添加與丁基鋰數量等莫耳之ε-己內酯的數量。
程序係如於實例1b。然而,代替矽雜內酯,添加與丁基鋰數量等莫耳之2,2,4-三甲基-1-氧雜-4-吖-2-矽雜環己烷的數量(作為溶液於甲苯
中)。
實例1a-e之苯乙烯-丁二烯共聚物的聚合物性質係歸納於表1。
製造包含實例1a-e的苯乙烯-丁二烯共聚物之輪胎胎面橡膠組成物。該組成係列示於表2。橡膠組成物(除硫及加速劑之外)係於1.5公升之捏合機製造。該硫及加速劑組成接著在40℃於滾筒(roller)混合。
為評估實例2a-e橡膠組成物之加工特性,使用在120℃之實驗級擠製機以製造擠製型材(Garvey profiles)(Brabender PV 301擠製機(16mm),模直徑(die diameter)14.5mm,S08口型,螺桿速度每分鐘50轉)。此些Garvey profiles係顯示於附錄,圖1/3a-e。
a)藉由FTIR測定乙烯基以及苯乙烯含量
b)藉由DSC測定玻璃轉移溫度
c)藉由GPC(PS校正)測定波峰分子量MP1及MP2與偶合度
d)在100℃測定慕尼黏度
e)在50℃測定冷流
根據表2實例2a-e之輪胎胎面橡膠組成物係在160℃硫化20分鐘。對應的硫化橡膠之性質係作為實例4a-e列於表3。包含未官能化之苯乙烯-丁二烯共聚物自比較例4a之硫化實例的硫化橡膠性質係提供指數100。表3中所有大於100之數值意指在個別測試性質中之對應改良百分比。
橡膠之冷流數值係在儲存過程中測量橡膠的流動特性。未硫化橡膠混合物的Garvey profiles係用於評估橡膠混合物的加工特性。在硫化輪胎胎面混合物的情況下,在60℃之彈性、在60℃之動力阻尼tanδ、在振幅掃描之tanδ最大值以及在振幅掃描中介於低及高應變之模組差G*係為輪胎滾動阻力的指示物。在0℃之動力阻尼tanδ係為輪胎防濕滑性的指示物。DIN磨損係為輪胎胎面耐磨損性的指示物。
如藉由圖1/3a-e之說明,所有輪胎胎面橡膠組成物2a-e顯示良好加工特性(smooth Garvey profiles 3a-e)。然而,如表1之顯而易見的,僅實例1b及1c之本發明聚合物之特徵在於非常低冷流數值。由表3顯而易見包含本發明聚合物1b及1c之硫化輪胎胎面混合物4b及3c以及包含比較例聚合物1e之硫化輪胎胎面混合物4e係還具有對於滾動阻力、防濕滑性及耐磨損性之特別有利的測試值。
惰性化之20公升反應器係裝載8.5kg之己烷、1185g之1,3-丁二烯、315g之苯乙烯、8.6mmol之2,2-雙(2-四氫呋喃基)丙烷以及9.5mmol之丁基鋰,並且將成分加熱至60℃。進行聚合同時在60℃攪拌25分鐘。接著,添加9.5mmol之鯨臘醇以封蓋聚合物鏈之陰離子端,排出橡膠溶液並藉由添加3g之Irganox® 1520(2,4-雙(辛基硫基甲基)-6-甲基酚)穩定化,以及藉由蒸氣汽提移除溶劑。將橡膠碎屑在降低壓力於65℃下乾燥。
程序係如於實例1b。
程序係如於實例1d。然而,使用10mmol之丁基鋰以及等莫耳量之ε-己內酯。
程序係如於實例1e。然而,使用9.5mmol之丁基鋰以及等莫耳數量之2,2,4-三甲基-1-氧雜-4-吖-2-矽雜環己烷。
程序係如於實例5d。然而,代替2,2,4-三甲基-1-氧雜-4-吖-2-矽雜環己烷,添加與丁基鋰數量等莫耳之六甲基環三矽氧烷的數量。
實例5a-e之苯乙烯-丁二烯共聚物的聚合物性質係歸納於表4。
製造包含實例5a-e苯乙烯-丁二烯共聚物之輪胎胎面橡膠組成物。該組成係列於表5中。橡膠組成物(除硫及交聯劑之外)係於1.5公升之捏合機製造。該硫及加速劑組成接著在40℃於滾筒混合。
為評估實例6a-e橡膠組成物之加工特性,如上所述,藉由在120℃之實驗級擠製機製造擠製型材(Garvey profiles)。此些Garvey profiles係顯示於附錄,圖1/7a-e。
a)藉由FTIR測定乙烯基以及苯乙烯含量
b)藉由DSC測定玻璃轉移溫度
c)藉由GPC(PS校正)測定波峰分子量MP1及MP2與偶合度
d)在100℃測定慕尼黏度
e)在50℃測定冷流
根據表5實例6a-e之輪胎胎面橡膠組成物係在160℃硫化20分鐘。對應的硫化橡膠之性質係作為實例8a-e列於表6。包含未官能化之苯乙烯-丁二烯共聚物自比較例6a之硫化實例的硫化橡膠性質係提供指數100。表6中所有大於100之數值意指在個別測試性質中之對應改良百分比。
如表4之顯而易見的,所有實例5a-e之聚合物的特徵在於低冷流。如圖1/7a-e之說明,包含實例5a(比較例)、5b(本發明)及5c(比較例)聚合物之輪胎胎面橡膠組成物6a、6b及6c顯示良好加工特性(平滑的Garvey輪廓(Garvey profiles)7a、7b、7c)。相反地,包含比較性聚合物5d及5e之輪胎胎面橡膠組成物6d及6e具有較差之加工特性(粗糙Garvey輪廓7d、7e)。表6顯而易見的包含本發明聚合物5b之硫化輪胎胎面混合物8b以及包含比較例聚合物5d及5e之硫化輪胎胎面混合物8d及8e,具有對於滾動阻力、防濕滑性及耐磨損性之特別有利的測試值。
實例使得清楚僅本發明聚合物可結合低冷流數值、對應的輪胎胎面組成物的良好加工特性以及對應的硫化橡膠之良好輪胎胎面性質。
在測試系列1a-e中之本發明聚合物1b及1c具有相較於此系列之比較性聚合物遠高的ML數值。
測試系列5a、5c、5d及5e之比較性聚合物亦具有高ML數值,且因此低冷流數值。然而,包含測試系列5a-e的此些比較性聚合物之橡膠混合物顯示更差動力性質(5a、5c)或更差加工特性(5d、5e)。因此,本發明之聚合物或其橡膠混合物結合低冷流、良好動力性質以及良好加工特性。
Claims (16)
- 一種聚合物混合物,其包含a)一經端基官能化之聚合物,其在聚合物鏈之末端具有一式(I)的含矽烷之羧基,其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,A係為二價有機基團,其除C和H還可含有一或多個雜原子,以及b)二聚物,其具有一或多種衍生自式(III)矽雜內酯之結構單元,其中R1、R2係為相同或不同以及各自為H、烷基、烷氧基、環烷基、環烷氧基、芳基、芳基氧基、烷芳基、烷芳基氧基、芳烷基或芳烷氧基,其可含有一或多個雜原子,R3、R4係為相同或不同以及各自為H、烷基、環烷基、芳基、烷芳基或芳烷基,其可含有一或多個雜原子,A係為二價有機基團,其除C和H外還可含有一或多個雜原子。
- 如申請專利範圍第1或2項之聚合物混合物,其特徵在於該聚合物係二烯聚合物,或者可藉由二烯類與乙烯基芳族單體共聚合而獲得之二烯共聚物。
- 如申請專利範圍第1項之聚合物混合物,其特徵在於該聚合物係可藉由該聚合物鏈的反應性末端與一或多種呈矽雜內酯形式的官能化試劑(functionalizing reagents)之反應而獲得。
- 如申請專利範圍第1項之聚合物混合物,其特徵在於該聚合物具有10 000至2 000 000g/mol1之平均莫耳質量(數量平均,Mn)。
- 如申請專利範圍第6項之聚合物混合物,其特徵在於該聚合物具有-110℃至+20℃之玻璃轉移溫度。
- 一種矽雜內酯之用途,其係作為用於製備如申請專利範圍第1至7項中任一項之經端基官能化之聚合物的官能化試劑。
- 一種用於製備如申請專利範圍第1至7項中任一項之經端基官能化之聚合物之方法,其特徵在於一或多種矽雜內酯係以化學計量呈過量或缺乏添加,以提供具有聚合物鏈的反應性末端之聚合物。
- 一種用於製備如申請專利範圍第10項之經端基官能化之聚合物之方法,其中一或多種矽雜內酯係以化學計量呈過量或缺乏添加,以在聚合結束後提供具有聚合物鏈的反應性末端之聚合物。
- 如申請專利範圍第10項之方法,其特徵在於官能化試劑之量係0.005至2%重量比,其以聚合物之量為基準。
- 一種如申請專利範圍第1至7項中任一項之聚合物混合物之用途,其係用於製造可硫化橡膠組成物。
- 一種可硫化橡膠組成物,其包含a)如申請專利範圍第1至7項中任一項之聚合物混合物以及b)老化穩定劑、油類、填料、橡膠及/或另外的橡膠輔助劑。
- 一種如申請專利範圍第13項之可硫化橡膠組成物之用途,其係用於製造模製物。
- 一種模製物,其可由如申請專利範圍第14項之用途獲得。
- 一種模製物,其可由如申請專利範圍第13項之可硫化橡膠組成物獲得。
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Patent Citations (2)
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JPS60172992A (ja) * | 1983-12-23 | 1985-09-06 | ダウ コ−ニング コ−ポレ−シヨン | シララクトンおよびその製法 |
JPS6210137A (ja) * | 1985-07-09 | 1987-01-19 | Nippon Oil & Fats Co Ltd | 分子の両末端にペルオキシエステル基を有するポリシロキサン化合物 |
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EP2989145A1 (de) | 2016-03-02 |
BR112015026744B1 (pt) | 2020-07-21 |
BR112015026744A2 (pt) | 2017-07-25 |
ES2758749T3 (es) | 2020-05-06 |
KR20160004336A (ko) | 2016-01-12 |
CN105143315A (zh) | 2015-12-09 |
SA515370031B1 (ar) | 2017-11-22 |
SG11201508456PA (en) | 2015-11-27 |
JP6212202B2 (ja) | 2017-10-11 |
HUE046634T2 (hu) | 2020-03-30 |
RU2015150061A (ru) | 2017-05-29 |
TW201504321A (zh) | 2015-02-01 |
KR102170842B1 (ko) | 2020-10-27 |
CN105143315B (zh) | 2018-01-09 |
MX2015014854A (es) | 2016-03-09 |
WO2014173707A1 (de) | 2014-10-30 |
PL2989145T3 (pl) | 2020-04-30 |
US20160083495A1 (en) | 2016-03-24 |
EP2796485A1 (de) | 2014-10-29 |
EP2989145B1 (de) | 2019-10-09 |
US9969833B2 (en) | 2018-05-15 |
RU2658908C2 (ru) | 2018-06-26 |
HK1222188A1 (zh) | 2017-06-23 |
MX366116B (es) | 2019-06-27 |
JP2016518493A (ja) | 2016-06-23 |
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