JP6154891B2 - 1,4‐シス単位含有量が高い分岐ポリブタジエンの調製方法 - Google Patents
1,4‐シス単位含有量が高い分岐ポリブタジエンの調製方法 Download PDFInfo
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- JP6154891B2 JP6154891B2 JP2015510906A JP2015510906A JP6154891B2 JP 6154891 B2 JP6154891 B2 JP 6154891B2 JP 2015510906 A JP2015510906 A JP 2015510906A JP 2015510906 A JP2015510906 A JP 2015510906A JP 6154891 B2 JP6154891 B2 JP 6154891B2
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- Prior art keywords
- polybutadiene
- branched
- halogen atom
- aluminum
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- 229920002857 polybutadiene Polymers 0.000 title claims description 82
- 239000005062 Polybutadiene Substances 0.000 title claims description 77
- 238000004519 manufacturing process Methods 0.000 title description 18
- 238000000034 method Methods 0.000 claims description 71
- -1 neodymium carboxylate Chemical class 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 42
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 40
- 229910052779 Neodymium Inorganic materials 0.000 claims description 38
- 229910052782 aluminium Inorganic materials 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 150000002895 organic esters Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 27
- 238000009826 distribution Methods 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 14
- 239000000806 elastomer Substances 0.000 description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 7
- SJMLNDPIJZBEKY-UHFFFAOYSA-N ethyl 2,2,2-trichloroacetate Chemical compound CCOC(=O)C(Cl)(Cl)Cl SJMLNDPIJZBEKY-UHFFFAOYSA-N 0.000 description 7
- 229920005669 high impact polystyrene Polymers 0.000 description 7
- 239000004797 high-impact polystyrene Substances 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000569 multi-angle light scattering Methods 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001206 Neodymium Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-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
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
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- 150000002924 oxiranes Chemical class 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001370 static light scattering Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- LGBYJXBCVZKJBL-UHFFFAOYSA-N 1-[(2-oxoazepan-1-yl)disulfanyl]azepan-2-one Chemical compound O=C1CCCCCN1SSN1C(=O)CCCCC1 LGBYJXBCVZKJBL-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
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- HZLPTRNNTNQXDM-UHFFFAOYSA-N 2-ethenyl-2,3,3-trimethyloxirane Chemical compound CC1(C)OC1(C)C=C HZLPTRNNTNQXDM-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
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- 239000002879 Lewis base Substances 0.000 description 1
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- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- ICKSOVDWLBHVCG-UHFFFAOYSA-N bis(4-methylpentyl)alumane Chemical compound C(CCC(C)C)[AlH]CCCC(C)C ICKSOVDWLBHVCG-UHFFFAOYSA-N 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
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- 238000004364 calculation method Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
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- UBCPEZPOCJYHPM-UHFFFAOYSA-N dimethoxy-methyl-octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](C)(OC)OC UBCPEZPOCJYHPM-UHFFFAOYSA-N 0.000 description 1
- ORHSGYTWJUDWKU-UHFFFAOYSA-N dimethoxymethyl(ethenyl)silane Chemical compound COC(OC)[SiH2]C=C ORHSGYTWJUDWKU-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 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
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KGNDVXPHQJMHLX-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)cyclohexanamine Chemical compound CO[Si](OC)(OC)CCCNC1CCCCC1 KGNDVXPHQJMHLX-UHFFFAOYSA-N 0.000 description 1
- AGVKXDPPPSLISR-UHFFFAOYSA-N n-ethylcyclohexanamine Chemical compound CCNC1CCCCC1 AGVKXDPPPSLISR-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic 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
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VALAJCQQJWINGW-UHFFFAOYSA-N tri(propan-2-yl)alumane Chemical compound CC(C)[Al](C(C)C)C(C)C VALAJCQQJWINGW-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- UWSYCPWEBZRZNJ-UHFFFAOYSA-N trimethoxy(2,4,4-trimethylpentyl)silane Chemical compound CO[Si](OC)(OC)CC(C)CC(C)(C)C UWSYCPWEBZRZNJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
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- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/06—Butadiene
-
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- 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
- C08F236/16—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 containing halogen
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- 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
- C08F36/06—Butadiene
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
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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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
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- 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
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- C08K3/02—Elements
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- 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
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Description
a)in situで調製した触媒系であって、
(a1)少なくとも一種のネオジムカルボキシレート、
(a2)アルミニウムの少なくとも一種のアルキル化合物、及び
(a3)少なくとも一種のハロゲン原子を含むアルミニウムの少なくとも一種のアルキル化合物
を含む触媒系と、
b)少なくとも一種のハロゲン原子を含む少なくとも一種の有機エステルと
の存在下で、ブタジエンを重合させるステップを含む。
Al(R)3 (I)
AlH(R)2 (II)
[式中、Rは炭素数1〜10の直鎖状又は分岐状のアルキル基である。]
AlXnR3-n (III)
[式中、Rは炭素数1〜10の直鎖状又は分岐状のアルキル基であり、Xは例えば塩素、臭素、フッ素、ヨウ素等のハロゲン原子、好ましくは塩素であり、nは1又は2である。]
R1、R2、及びR3は、互いに同一又は異なるものであり、例えば塩素、フッ素、臭素、ヨウ素等のハロゲン原子、好ましくは塩素であり、又は炭素数1〜10の直鎖状又は分岐状のアルキル基、並びに炭素数2〜10の直鎖状又は分岐状のアルケニル基、アリール基、シクロアルキル基、エステル基のうちから選択され、ただしR1、R2、及びR3の少なくとも1つはハロゲン原子であり、
R4は、炭素数1〜10の直鎖状又は分岐状のアルキル基、並びに炭素数2〜10の直鎖状又は分岐状のアルケニル基及びアリール基のうちから選択される。]
・1,4‐シス単位含有量:92%以上、好ましくは95%〜99%
・ムーニー粘度:30〜70、好ましくは35〜65
・分岐指数(gm):1未満、好ましくは0.4〜0.9
・多分散性指数Mw/Mn:1.9〜4、好ましくは2〜3
この方法は、1,4‐トランス及び1,2‐ビニル異性体に起因する各バンドの強度と、1312cm−1の基準バンド(内部標準)の強度との比の計算に基づく(この方法に関する詳細はL. J. Bellamy, “The Infrared Spectra of Complex Molecules” (1975), Vol. 1, Third Ed. Chapman and Hallを参照)。1,4‐シス単位含有量は100の補数で判定した。試料の調製は、KBr窓板上で溶液を蒸発させることで得られたポリブタジエンフィルム上で行った。
ASTM D 1646規格に従ってムーニー粘度(100℃におけるML1+4)を判定した。特に、得られたポリブタジエンの粘度測定は、温度:100℃、予加熱時間:1分、測定時間:4分の条件下で大型ローター(L)を用いて行った。
多分散指数(すなわちMw/Mn比)の根拠ともなる分子量分布(MWD)を、溶媒:テトラヒドロフラン(THF)、温度:25℃、カラム:PL-MIXED A (X4)のSEC(GPC)を介して通常使用される方法に従って判定した。分子量は、ユニバーサルキャリブレーション法(k=0.000457dL/g及びα=0.693)に従って判定した。
質量平均分子量(Mw)及び分岐指数(gm)は、“Application Note” (1996), No. 9, Wyatt Technology and by Pavel Kratochvil, “Classical Light Scattering from Polymer Solutions” (1987), Polymer Science Library, 5, Elsevier Science Publishers B. V.に記載されている研究から導いた内部方法に従って判定した。
K*は、使用する光の波長、ポリマーの屈折率(dn/dc)、及び使用する溶媒に依存する光学定数であり、
Mwは、質量平均分子量であり、
cは、重合体溶液の濃度であり、
Rθは、角度θで測定した散乱光の強度であり、
Pθは、測定角度θ=0のとき1となる、散乱光の変動を記述する関数である。]
(1)回転半径と重量平均分子量(Mw)との相関曲線の傾きを表すパラメータαの値から定性的に導く方法。同一の分析条件下で、この値が直鎖状のマクロ構造に対して減少する場合は、分岐状のマクロ構造を有するポリマーが存在し、テトラヒドロフラン(THF)を溶媒とするとき、1,4‐シス単位含有量が高いポリブタジエンに典型的な値は0.58〜0.60である。
(2)分岐状高分子(<r2>b)の平均二乗回転半径と直鎖状高分子(<r2>l)の平均二乗回転半径との比として高分子毎に定義される分岐指数(gm)を推定することにより定性的に導く方法。これと同じ分子量が次式(3)で表される(Miは「i番目の」分子の重量平均分子量(Mw)を表すものとする)。
<1,4‐シス単位含有量が高い分岐ポリブタジエンの調製>
攪拌器付き1.5L反応器に、シクロヘキサン584g(d=0.78g/ml)、1,3‐ブタジエン(BDE)(Versalis spa社)68g、エチルトリクロロアセテート(ETA)(VIO Chemicals社)をシクロヘキサン0.0014Mに溶かした溶液0.1ml(0.0325mg、0.00017mmol)、ジ‐イソブチルアルミニウムハイドライド(DIBAH)(Akzo Nobel社)をシクロヘキサン0.12Mに溶かした溶液1.2ml(145.06mg、1.02mmol)、及びジエチルアルミニウムクロライド(DEAC)(純度:98.5%、Al/Clモル比:1(Albemarle社))をシクロヘキサン1Mに溶かした溶液0.51ml(61.49mg、0.51mmol)を投入した。この反応器を60℃の温度まで加熱した。次いで、RCOOH/Ndモル比:0.3のネオジムバーサテート[Nd(versatate)3](Rhodia社)をシクロヘキサン0.6M(DEAC/Ndモル比:3、DIBAH/Ndモル比:6、ETA/Ndモル比:0.001)に溶かした溶液0.4ml(0.17mmol)を加えた。
・1,4‐シス単位含有量:96%
・ムーニー粘度(100℃におけるML1+4):40
・分岐指数(gm):0.6
・多分散指数(Mw/Mn比):2.5
Claims (13)
- 1,4‐シス単位含有量が高い分岐ポリブタジエンの調製方法であり、少なくとも一種の有機溶媒の存在下、かつ
a)in situで調製した触媒系であって、
(a1)少なくとも一種のネオジムカルボキシレート、
(a2)アルミニウムの少なくとも一種のアルキル化合物、及び
(a3)少なくとも一種のハロゲン原子を含むアルミニウムの少なくとも一種のアルキル化合物
を含む触媒系と、
b)少なくとも一種のハロゲン原子を含む少なくとも一種の有機エステルと
の存在下で、ブタジエンを重合させるステップを含み、
前記有機エステルが、下記一般式(IV)を有する化合物のうちから選択される、方法。
R1、R2、及びR3は、互いに同一又は異なるものであり、塩素、フッ素、臭素、ヨウ素等のハロゲン原子であり、又は炭素数1〜10の直鎖状又は分岐状のアルキル基、並びに炭素数2〜10の直鎖状又は分岐状のアルケニル基、アリール基、シクロアルキル基、エステル基のうちから選択され、ただしR1、R2、及びR3の少なくとも1つはハロゲン原子であり、
R4は、炭素数1〜10の直鎖状又は分岐状のアルキル基、並びに炭素数2〜10の直鎖状又は分岐状のアルケニル基及びアリール基のうちから選択される。] - 請求項1に記載の1,4‐シス単位含有量が高い分岐ポリブタジエンの調製方法であって、前記ブタジエンは、前記有機溶媒の総質量に対して5質量%〜40質量%の量で存在する方法。
- 請求項1又は2に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記有機溶媒は、ブタン、n‐ペンタン、n‐ヘキサン、n‐ヘプタン、若しくはその混合物等の飽和脂肪族炭化水素;シクロヘキサン、シクロペンタン、若しくはその混合物等の飽和脂環式炭化水素;1‐ブテン、2‐ブテン、若しくはその混合物等のモノオレフィン;塩化メチレン、クロロホルム、四塩化炭素、トリクロロエチレン、ペルクロロエチレン、1,2‐ジクロロエタン、クロロベンゼン、ブロモベンゼン、クロロトルエン、若しくはその混合物等のハロゲン化炭化水素;又はこれらの混合物のうちから選択される方法。
- 請求項1〜3のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記ネオジムカルボキシレート(a1)は、ネオジムバーサテート[Nd(versatate)3]である方法。
- 請求項1〜4のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記ネオジムカルボキシレートは、重合対象であるブタジエン1,000g当たり0.1mmol〜10mmolの量で使用される方法。
- 請求項1〜5のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記アルミニウムのアルキル化合物(a2)は、下記一般式(I)又は(II)を有する化合物のうちから選択される方法。
Al(R)3 (I)
AlH(R)2 (II)
[式中、Rは炭素数1〜10の直鎖状又は分岐状のアルキル基である。] - 請求項1〜6のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記少なくとも一種のハロゲン原子を含むアルミニウムのアルキル化合物(a3)は、下記一般式(III)を有する化合物のうちから選択される方法。
AlXnR3-n (III)
[式中、Rは炭素数1〜10の直鎖状又は分岐状のアルキル基であり、Xは塩素、臭素、フッ素、ヨウ素等のハロゲン原子であり、nは1又は2である。] - 請求項1〜7のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記ネオジムカルボキシレート(a1)と前記アルミニウムのアルキル化合物(a2)とのモル比は、1/1〜1/30である方法。
- 請求項1〜8のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記ネオジムカルボキシレート(a1)と前記少なくとも一種のハロゲン原子を含むアルミニウムのアルキル化合物(a3)とのモル比は、1/1.5〜1/6である方法。
- 請求項1〜9のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記少なくとも一種のハロゲン原子を含むアルミニウムの化合物(a3)は、該化合物(a3)中に存在するハロゲンと前記アルミニウムのアルキル化合物(a2)との比が0.5〜5となるような量で使用される方法。
- 請求項1〜10のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、前記少なくとも一種のハロゲン原子を含む有機エステル(b)と前記ネオジムカルボキシレート(a1)とのモル比は、1/0.00001〜1/0.1である方法。
- 請求項1〜11のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、20℃〜120℃の温度範囲で実行される方法。
- 請求項1〜12のいずれか一項に記載の1,4‐シス単位の含有量が高い分岐ポリブタジエンの調製方法であって、1bar〜10bar(105Pa〜106Pa)の圧力範囲で実行される方法。
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PCT/IB2013/053230 WO2013168039A1 (en) | 2012-05-11 | 2013-04-24 | Process for the preparation of branched polybutadiene having a high content of 1,4-cis units |
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IT201800005841A1 (it) * | 2018-05-30 | 2019-11-30 | Procedimento per la preparazione di copolimeri random butadiene-isoprene ad elevato contenuto di unita’ 1,4-cis | |
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