JPS635401B2 - - Google Patents
Info
- Publication number
- JPS635401B2 JPS635401B2 JP18698383A JP18698383A JPS635401B2 JP S635401 B2 JPS635401 B2 JP S635401B2 JP 18698383 A JP18698383 A JP 18698383A JP 18698383 A JP18698383 A JP 18698383A JP S635401 B2 JPS635401 B2 JP S635401B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- hydrogenation
- living
- conjugated diene
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 193
- 238000005984 hydrogenation reaction Methods 0.000 claims description 147
- 239000003054 catalyst Substances 0.000 claims description 57
- 150000001993 dienes Chemical class 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- -1 bis(cyclopentadienyl) titanium Chemical compound 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 239000002685 polymerization catalyst Substances 0.000 claims description 10
- 125000001979 organolithium group Chemical group 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 59
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 39
- 229910052744 lithium Inorganic materials 0.000 description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 31
- 229920001577 copolymer Polymers 0.000 description 29
- 125000002897 diene group Chemical group 0.000 description 28
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 25
- 230000000694 effects Effects 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 21
- 229920002554 vinyl polymer Polymers 0.000 description 20
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 14
- 229920001400 block copolymer Polymers 0.000 description 14
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 9
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000003609 titanium compounds Chemical class 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 229920002725 thermoplastic elastomer Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002815 homogeneous catalyst Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZYBZLPTXDDWJFH-UHFFFAOYSA-N CCC(C)CC(C)([Li])C1=CC=CC(C([Li])(C)CC(C)CC)=C1 Chemical compound CCC(C)CC(C)([Li])C1=CC=CC(C([Li])(C)CC(C)CC)=C1 ZYBZLPTXDDWJFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005336 allyloxy 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- UREWAKSZTRITCZ-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UREWAKSZTRITCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BIOCRZSYHQYVSG-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-diethylethanamine Chemical compound CCN(CC)CCC1=CC=C(C=C)C=C1 BIOCRZSYHQYVSG-UHFFFAOYSA-N 0.000 description 1
- OHDSHGBRKMRPHC-UHFFFAOYSA-N 2-(4-ethenylphenyl)-n,n-dimethylethanamine Chemical compound CN(C)CCC1=CC=C(C=C)C=C1 OHDSHGBRKMRPHC-UHFFFAOYSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- VIKKNRHJFUMVND-UHFFFAOYSA-M C1(C=CC=C1)[Ti](Cl)(OCC)C1C=CC=C1 Chemical compound C1(C=CC=C1)[Ti](Cl)(OCC)C1C=CC=C1 VIKKNRHJFUMVND-UHFFFAOYSA-M 0.000 description 1
- SXRLRTAOSJEJCG-UHFFFAOYSA-N C=1C=CC=CC=1C(C=1C=CC=CC=1)([Li])CCC([Li])(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)([Li])CCC([Li])(C=1C=CC=CC=1)C1=CC=CC=C1 SXRLRTAOSJEJCG-UHFFFAOYSA-N 0.000 description 1
- VTVJHXZEIJHZPJ-UHFFFAOYSA-N CCC(C)CC(C)([Li])C1=CC=C(C([Li])(C)CC(C)CC)C=C1 Chemical compound CCC(C)CC(C)([Li])C1=CC=C(C([Li])(C)CC(C)CC)C=C1 VTVJHXZEIJHZPJ-UHFFFAOYSA-N 0.000 description 1
- LFWLSTNMTRMPLX-UHFFFAOYSA-N CCO[Ti](OCC)(C1C=CC=C1)C1C=CC=C1 Chemical compound CCO[Ti](OCC)(C1C=CC=C1)C1C=CC=C1 LFWLSTNMTRMPLX-UHFFFAOYSA-N 0.000 description 1
- CAGJXJQLKVAYGN-UHFFFAOYSA-N CO[Ti](OC)(C1C=CC=C1)C1C=CC=C1 Chemical compound CO[Ti](OC)(C1C=CC=C1)C1C=CC=C1 CAGJXJQLKVAYGN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- HIGZGRCLEZNBMJ-UHFFFAOYSA-L O(c1ccccc1)[Ti](Oc1ccccc1)(C1C=CC=C1)C1C=CC=C1 Chemical compound O(c1ccccc1)[Ti](Oc1ccccc1)(C1C=CC=C1)C1C=CC=C1 HIGZGRCLEZNBMJ-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- MFRXMZYAKSRDMT-UHFFFAOYSA-L [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 Chemical compound [Br-].[Br-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 MFRXMZYAKSRDMT-UHFFFAOYSA-L 0.000 description 1
- WJIAEZWFAXURJL-UHFFFAOYSA-L [Cl-].C1(C=CC=C1)[Ti+](OC1=CC=CC=C1)C1C=CC=C1 Chemical compound [Cl-].C1(C=CC=C1)[Ti+](OC1=CC=CC=C1)C1C=CC=C1 WJIAEZWFAXURJL-UHFFFAOYSA-L 0.000 description 1
- IPTJKFGGRLMTIC-UHFFFAOYSA-L [I-].[I-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 Chemical compound [I-].[I-].C1(C=CC=C1)[Ti+2]C1C=CC=C1 IPTJKFGGRLMTIC-UHFFFAOYSA-L 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical group CC=C=C QNRMTGGDHLBXQZ-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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- WDGICGVEWQIMTQ-UHFFFAOYSA-L cyclopentane;difluorotitanium Chemical compound F[Ti]F.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 WDGICGVEWQIMTQ-UHFFFAOYSA-L 0.000 description 1
- ZEFNMRMJJKIGBT-UHFFFAOYSA-N dilithium;pentane Chemical compound [Li+].[Li+].[CH2-]CCC[CH2-] ZEFNMRMJJKIGBT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- WTTUTKBXMMXKBQ-UHFFFAOYSA-N lithium;stilbene Chemical compound C=1C=CC=CC=1C([Li])C([Li])C1=CC=CC=C1 WTTUTKBXMMXKBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は共役ジエンからなるポリマーに耐候
性、耐酸化性、耐熱性等を付与するための接触水
添方法に関し、さらに詳しくは有機リチウムを重
合触媒として得られる共役ジエンリビングポリマ
ーを特定のチタニウム化合物の存在下、温和な水
添条件下にてポリマーの共役ジエン単位の不飽和
二重結合を優先的に水添する新規な方法に関する
ものである。
本発明で用いるリビングポリマーなる語は、有
機リチウムを重合触媒として得られる共役ジエン
ホモポリマーおよびコポリマーの両方を意味し、
かつポリマー末端にリチウムを有し、さらにモノ
マーを重合させて成長する能力を有するポリマー
を意味する。具体的には、共役ジエン単独リビン
グポリマー、２種以上の共役ジエンのランダムお
よび／またはブロツクリビングコポリマー、およ
び少なくとも１種の共役ジエンと少なくとも１種
の共役ジエンとリビング共重合可能な他のモノマ
ーとのランダムおよび／またはブロツクリビング
コポリマーを包含する。
一般に共役ジエンを重合または共重合して得ら
れるポリマーはエラストマーとして広く工業的に
利用されている。しかし、これらポリマーはポリ
マー鎖中に不飽和二重結合が残存しているので、
加硫等に有利に利用される反面、かかる二重結合
は耐候性、耐酸化性等の安定性に劣る欠点を有し
ている。特に、共役ジエンとビニル置換芳香族炭
化水素とから得られるブロツクコポリマーは、熱
可塑性エラストマーや透明な耐衝撃性樹脂とし
て、あるいは、スチレン系樹脂やオレフイン系樹
脂の改質材として加硫せずに使用されるが、ポリ
マー鎖中の不飽和二重結合のために耐候性、耐酸
化性、耐オゾン性が劣り、かかる性能が要求され
る外装材分野等では問題となり用途が限定され
る。
これらの安定性に劣る欠点は、ポリマーを水添
してポリマー鎖中の不飽和二重結合をなくすこと
によつて著しく改善される。かかる目的で不飽和
二重結合を有する炭化水素ポリマーを水添する方
法は数多く提案されており、これらのポリマー水
添反応に用いられる触媒には、(1)ニツケル、白
金、パラジウム、ルテニウム等の金属を一般にカ
ーボン、シリカ、アルミナ、シリカ・アルミナ、
ケイソウ土等の担体に担持させた担持型不均一触
媒と、(2)ニツケル、コバルト、鉄、クロム等の有
機酸塩またはアセチルアセトン塩と有機アルミニ
ウム等の還元剤を溶媒中で反応して得られるいわ
ゆるチーグラー型の均一触媒とが一般に知られて
いる。
前者の担持型不均一触媒は、チーグラー型均一
触媒と比べると一般に活性が低く、水添反応を行
なうためには高温、高圧の厳しい条件が必要であ
る。また、被水添物が触媒と接触することによつ
て水添反応が進行するので、ポリマーを水添する
場合には低分子化合物の水添に比べて、反応系の
粘度やポリマー鎖の立体障害等の影響を受けて触
媒と接触しにくくなる。従つて、ポリマーを効率
良く水添するためには多量の触媒を要し不経済に
なると共に、より高温、高圧での水添反応が必要
となるので、ポリマーの分解やゲル化が起こり易
くなると共にエネルギーコストも高くなる。ま
た、共役ジエンとビニル置換炭化水素とのコポリ
マーの水添においては、通常芳香刻部分も水添さ
れ、共役ジエン単位の不飽和二重結合のみ選択的
に水添しにくくなる等の欠点がある。
一方、後者のチーグラー型均一触媒は、通常均
一系で水添反応が進行するので、担持型不均一触
媒と比べると一般に活性が高く、触媒使用量は少
なくて済み、より低温、低圧で水添反応できる特
徴がある。また、水添条件を選択すれば共役ジエ
ンとビニル置換芳香族炭化水素とのコポリマーの
共役ジエン単位の不飽和二重結合をかなりの程度
優先的に水添することも可能であり、工業的にも
利用されている。しかしながら、チーグラー型均
一触媒は一般にあらかじめ触媒成分を混合して還
元してから使用しないと水添活性が発現しにく
く、また再現性も劣り、さらに還元された触媒自
体の安定性が悪いために、水添反応の都度反応直
前に触媒を調整する必要がある等の問題点があ
る。また、特に共役ジエンとビニル置換芳香族炭
化水素とのコポリマーを水添する場合、芳香核部
分に対する共役ジエン単位の不飽和二重結合の水
添選択性もいまだ十分達成されていない。例え
ば、共役ジエン単位の不飽和二重結合を完全に水
添する条件では、芳香核部分がある程度水添され
てしまうのは避けられず、逆に芳香核部分の水添
を完全に抑える条件では共役ジエン単位の不飽和
二重結合の水添率が上がらなくなる。従つて、共
役ジエン単位の不飽和二重結合のみを選択的に水
添する触媒の開発が強く望まれているのが現状で
ある。
さらに、現状のチーグラー型水添触媒は高価で
あり、かつ水添後触媒残渣を除去するために複雑
な脱灰工程を要する欠点があり、経済的に有利に
水添するためには、脱灰の不要な程度の使用量で
活性を示す高活性水添触媒、あるいは極めて容易
に脱灰できる触媒の開発が強く望まれている。
本発明者らは、かかる状況に鑑み、共役ジエン
ポリマーまたはコポリマーに対して、共役ジエン
単位の不飽和二重結合のみを水添する高選択性水
添触媒について鋭意検討した結果、ビス（シクロ
ペンタジエニル）チタニウムジクロライドとアル
キルリチウム化合物からなる触媒が該ポリマーに
対して、少量の使用で再現性良く極めて高い活性
を有し、特に極めて良好な共役ジエン単位の不飽
和二重結合水添選択性を有することを見出し、す
でに特許出願した（特願昭58―6718号）。
本発明者らは、この先願ポリマー水添触媒系の
活性をさらに向上させ、効率的かつ経済的にポリ
マーを水添する方法につき、さらに鋭意検討した
結果、驚くべきことに、ポリマーとして有機リチ
ウムを重合触媒として得られたリビングポリマー
を用いると、水添触媒としてチタニウム化合物と
アルキルリチウム化合物の如き還元性金属化合物
とを組み合わせて使用しなくても、ビス（シクロ
ペンタジエニル）チタニウム化合物を単独で少量
存在させるだけで、極めて高いポリマー水添活性
および共役ジエン単位の不飽和二重結合水添選択
性を示すことを見出し、本発明を完成するに至つ
たものである。
すなわち、本発明は、不活性有機溶媒中にてリ
ビングポリマーを水添する方法において、
(A) 有機リチウムを重合触媒として共役ジエンを
重合または共役ジエンと共役ジエンと共重合可
能なモノマーを共重合して得られるリビングポ
リマー、を
(B) 一般式
The present invention relates to a catalytic hydrogenation method for imparting weather resistance, oxidation resistance, heat resistance, etc. to polymers made of conjugated dienes, and more specifically relates to a catalytic hydrogenation method for imparting weather resistance, oxidation resistance, heat resistance, etc. The present invention relates to a novel method for preferentially hydrogenating unsaturated double bonds in conjugated diene units of a polymer under mild hydrogenation conditions in the presence of. The term living polymer as used in the present invention refers to both conjugated diene homopolymers and copolymers obtained using organolithium as a polymerization catalyst,
It also means a polymer that has lithium at the end of the polymer and has the ability to grow by polymerizing monomers. Specifically, living polymers of conjugated dienes alone, random and/or blocked copolymers of two or more conjugated dienes, and at least one conjugated diene and at least one conjugated diene with other monomers capable of living copolymerization. random and/or blocked copolymers of Generally, polymers obtained by polymerizing or copolymerizing conjugated dienes are widely used industrially as elastomers. However, these polymers have unsaturated double bonds remaining in the polymer chain, so
Although they are advantageously used for vulcanization and the like, such double bonds have the disadvantage of poor stability such as weather resistance and oxidation resistance. In particular, block copolymers obtained from conjugated dienes and vinyl-substituted aromatic hydrocarbons can be used as thermoplastic elastomers, transparent impact-resistant resins, or as modifiers for styrene resins and olefin resins without vulcanization. However, due to the unsaturated double bonds in the polymer chain, it has poor weather resistance, oxidation resistance, and ozone resistance, which is a problem in the field of exterior materials that require such performance, which limits its use. These disadvantages of poor stability can be significantly improved by hydrogenating the polymer to eliminate unsaturated double bonds in the polymer chain. Many methods have been proposed for hydrogenating hydrocarbon polymers having unsaturated double bonds for this purpose, and the catalysts used for these polymer hydrogenation reactions include (1) nickel, platinum, palladium, ruthenium, etc.; Metals are generally carbon, silica, alumina, silica/alumina,
Obtained by reacting a supported heterogeneous catalyst supported on a carrier such as diatomaceous earth with (2) an organic acid salt such as nickel, cobalt, iron, or chromium or an acetylacetone salt and a reducing agent such as organic aluminum in a solvent. A so-called Ziegler type homogeneous catalyst is generally known. The former supported type heterogeneous catalyst generally has lower activity than the Ziegler type homogeneous catalyst, and requires severe conditions of high temperature and high pressure to carry out the hydrogenation reaction. In addition, since the hydrogenation reaction progresses when the hydrogenated substance comes into contact with the catalyst, when hydrogenating polymers, the viscosity of the reaction system and the steric structure of the polymer chains are more important than when hydrogenating low-molecular compounds. It becomes difficult to contact the catalyst due to the influence of obstacles, etc. Therefore, in order to efficiently hydrogenate a polymer, a large amount of catalyst is required, which is uneconomical, and the hydrogenation reaction is required at higher temperatures and pressures, which makes it easier for polymer decomposition and gelation to occur. At the same time, energy costs also increase. Furthermore, when hydrogenating a copolymer of a conjugated diene and a vinyl-substituted hydrocarbon, the aromatic part is usually also hydrogenated, making it difficult to selectively hydrogenate only the unsaturated double bonds of the conjugated diene unit. . On the other hand, the latter Ziegler-type homogeneous catalyst usually performs the hydrogenation reaction in a homogeneous system, so it generally has higher activity than supported-type heterogeneous catalysts, requires less catalyst, and performs hydrogenation at lower temperatures and pressures. It has the ability to react. In addition, if hydrogenation conditions are selected, it is possible to hydrogenate the unsaturated double bonds of the conjugated diene units of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon to a considerable degree preferentially. is also used. However, Ziegler-type homogeneous catalysts generally have difficulty in developing hydrogenation activity unless the catalyst components are mixed in advance and reduced before use, and reproducibility is poor, and furthermore, the reduced catalyst itself has poor stability. There are problems such as the need to adjust the catalyst immediately before each hydrogenation reaction. In addition, particularly when hydrogenating a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon, hydrogenation selectivity of the unsaturated double bond of the conjugated diene unit with respect to the aromatic nucleus moiety has not yet been sufficiently achieved. For example, under conditions that completely hydrogenate the unsaturated double bonds of a conjugated diene unit, it is inevitable that the aromatic nucleus will be hydrogenated to some extent, and conversely, under conditions that completely suppress the hydrogenation of the aromatic nucleus, The hydrogenation rate of unsaturated double bonds in conjugated diene units no longer increases. Therefore, there is currently a strong desire to develop a catalyst that selectively hydrogenates only the unsaturated double bonds of conjugated diene units. Furthermore, the current Ziegler-type hydrogenation catalyst is expensive and requires a complicated deashing process to remove catalyst residue after hydrogenation. There is a strong desire to develop a highly active hydrogenation catalyst that exhibits activity even when used in an unnecessary amount, or a catalyst that can be deashed extremely easily. In view of this situation, the present inventors have conducted intensive studies on highly selective hydrogenation catalysts that hydrogenate only unsaturated double bonds in conjugated diene units for conjugated diene polymers or copolymers. A catalyst consisting of (dienyl) titanium dichloride and an alkyl lithium compound has extremely high activity for the polymer with good reproducibility even when used in small amounts, and in particular has extremely good hydrogenation selectivity for unsaturated double bonds in conjugated diene units. We have already applied for a patent (Patent Application No. 58-6718). The inventors of the present invention have conducted further intensive studies on a method for efficiently and economically hydrogenating polymers by further improving the activity of this prior application's polymer hydrogenation catalyst system. By using the obtained living polymer as a polymerization catalyst, bis(cyclopentadienyl)titanium compounds can be reacted alone without using a combination of a titanium compound and a reducing metal compound such as an alkyllithium compound as a hydrogenation catalyst. The inventors have discovered that even when present in a small amount, the polymer exhibits extremely high hydrogenation activity and hydrogenation selectivity for unsaturated double bonds in conjugated diene units, and has completed the present invention. That is, the present invention provides a method for hydrogenating a living polymer in an inert organic solvent, in which (A) a conjugated diene is polymerized using an organolithium as a polymerization catalyst, or a conjugated diene and a monomer copolymerizable with the conjugated diene are copolymerized. The living polymer obtained by (B) has the general formula
【式】（但し、Ｒ，R′は
炭素原子数１〜８個のアルキル基、アリル基、ア
ルコキシ基、アリロキシ基、ハロゲン基、カルボ
ニル基から選択された基で、Ｒ，R′は同一でも
異なつていてもよい。）で示されるビス（シクロ
ペンタジエニル）チタニウム化合物の少なくとも
１種からなる水添触媒、
の存在下に水素と接触させ、該リビングポリマー
中の共役ジエン単位の不飽和二重結合を選択的に
水添することを特徴とするリビングポリマーの接
触水添方法に関するものである。
本発明で用いる水添触媒に係るビス（シクロペ
ンタジエニル）チタニウム化合物を還元性有機金
属化合物と組み合わせて用いる触媒が低分子有機
化合物の不飽和二重結合に対して水添活性を有す
ることはすでに知られている（例えば、M.F.
Sloanら、J.Am.Chem.Soc.、第85巻、4014〜
4018頁（1965年）、Y.Tajimaら、J.org.Chem.、
第33巻、1689〜1690頁（1968年）等）。しかし、
これらのチタニウム化合物単独では水添活性がな
く、まして還元性有機金属化合物としてリビング
ポリマーを用いる例はなく、その使用を示唆する
先行技術も全く開示されていない。
しかるに、本発明のポリマー水添方法の利点
は、被水添ポリマーとして還元性リチウムを有す
るリビングポリマーを用いることにより、ビス
（シクロペンタジエニル）チタニウム化合物を単
独で少量存在させるだけで水添活性が発現し水添
が進行すること、従つて新たに加える触媒成分が
１種類ですむこと、しかも前述のアルキルアルミ
ニウムの如き還元性有機化合物と組み合わせて用
いる系より活性が高く、共役ジエン単位の不飽和
二重結合に対する水添選択性が極めて高いこと、
さらに重合後のポリマーを単離せずに連続的に水
添することが可能で、重合触媒成分であるリチウ
ムを水添触媒成分として生かせること等であり、
効率的かつ経済的にポリマーを水添することが可
能となつたことは驚くべきことである。
本発明は有機リチウムで重合され、かつポリマ
ー中に不飽和二重結合を有する炭化水素リビング
ポリマーの全てに適用することができるが、好ま
しい実施態様は共役ジエンを重合または共重合し
て得られる共役ジエンリビングポリマーである。
かかる共役ジエンリビングポリマーとしては、共
役ジエンホモポリマーおよび共役ジエン相互ある
いは共役ジエンの少なくとも１種と共役ジエンと
リビング共重合可能なオレフインモノマーの少な
くとも１種とを共重合して得られるリビングコポ
リマー等が包含される。
かかる共役ジエンリビングポリマーの製造に用
いられる重合触媒としては、分子中に少なくとも
１個のリチウム原子を結合した炭化水素が用いら
れ、例えば、ｎ―プロピルリチウム、イソプロピ
ルリチウム、ｎ―ブチルリチウム、sec―ブチル
リチウム、tert―ブチルリチウム、ｎ―ペンチル
リチウム、ベンジルリチウム等の如きモノリチウ
ム、あるいは１，４―ジリチオ―ｎ―ブタン、
１，５―ジリチオペンタン、１，２―ジリチオジ
フエニルエタン、１，４―ジリチオ―１，１，
４，４―テトラフエニルブタン、１，３―または
１，４―ビス（１―リチオ―１，３―ジメチルペ
ンチル）ベンゼン、１，３―または１，４―ビス
（１―リチオ―３―メチルペンチル）ベンゼン等
のジリチウムが好適に用いられ、重合触媒がこれ
ら有機リチウムによつて得られたリチウムオリゴ
マーやα，ω―ジリチウムオリゴマーであつても
良い。特に一般的なものとしては、ｎ―ブチルリ
チウム、sec―ブチルリチウム等が挙げられる。
これらの有機リチウムは１種または２種以上混合
して使用しても良いし、重合時１回のみならず、
２回以上分割して重合途中で添加しても良い。有
機リチウムの使用量は所望するポリマーの分子量
に応じて適宜選択して用いられるが、一般的には
全使用モノマー量に対して0.005ないし５モル％
である。
本発明の水添に供する共役ジエンリビングポリ
マーの製造に用いられる共役ジエンとしては、一
般的には４〜約12個の炭素原子を有する共役ジエ
ンが挙げられ、具体的な例としては、１，３―ブ
タジエン、イソプレン、２，３―ジメチル―１，
３―ブタジエン、１，３―ペンタジエン、２―メ
チル―１，３―ペンタジエン、１，３―ヘキサジ
エン、４，５―ジエチル―１，３―オクタジエ
ン、３―ブチル―１，３―オクタジエン等が挙げ
られる。工業的に有利に展開でき、物性の優れた
エラストマーを得る上からは、１，３―ブタジエ
ン、イソプレンが特に好ましく、ブタジエンリビ
ングポリマー、イソプレンリビングポリマー、ブ
タジエン／イソプレンリビングコポリマーの如き
エラストマーが本発明の実施に特に好ましい。か
かるリビングポリマーにおいては、ポリマー鎖の
ミクロ構造は特に制限されず、いかなるものも好
適に使用できるが、１，２―ビニル結合が少ない
と水添後の重合体の溶解性が低下し、均一に水添
を行なうためには溶媒が限定されるので、該結合
を約30％以上含有するリビングポリマーがより好
ましい。
一方、本発明の方法は共役ジエンの少なくとも
１種と共役ジエンと共重合可能なモノマーの少な
くとも１種とを共重合して得られるリビングコポ
リマーの水添に特に好適に用いられる。かかるリ
ビングコポリマーの製造に用いられる好適な共役
ジエンとしては、前記共役ジエンが挙げられ、一
方のモノマーとしては、共役ジエンとリビング共
重合可能な全てのモノマーが挙げられるが、特に
ビニル置換芳香族炭化水素が好ましい。すなわ
ち、共役ジエン単位の不飽和二重結合のみを選択
的に水添する本発明の効果を十分発揮し、工業的
に有用で価値の高いエラストマーや熱可塑性エラ
ストマーを得るためには、共役ジエンとビニル置
換芳香族炭化水素とのリビングコポリマーが特に
重要である。かかるリビングコポリマーの製造に
用いられるビニル置換芳香族炭化水素の具体例と
しては、スチレン、ｔ―ブチルスチレン、α―メ
チルスチレン、ｏ―メチルスチレン、ｐ―メチル
スチレン、ジビニルベンゼン、１，１―ジフエニ
ルエチレン、ビニルナフタレン、Ｎ，Ｎ―ジメチ
ル―ｐ―アミノエチルスチレン、Ｎ，Ｎ―ジエチ
ル―ｐ―アミノエチルスチレン等が挙げられ、特
にスチレンが好ましい。具体的なリビングコポリ
マーの例としては、ブタジエン／スチレンリビン
グコポリマー、イソプレン／スチレンリビングコ
ポリマー等が工業的価値の高い水添コポリマーを
与えるので最も好適である。
かかるリビングコポリマーにおいては、ビニル
置換芳香族炭化水素含有量５重量％ないし95重量
％が好ましく、この範囲外では熱可塑性エラスト
マーとしての特徴が得られにくくなる。
本発明の方法に係るリビングコポリマーにおい
ては、モノマーはポリマー鎖全体に統計的に分布
しているランダムコポリマー、漸減ブロツクコポ
リマー、完全ブロツクコポリマー、グラフトコポ
リマーが含まれる。工業的に有用な熱可塑性エラ
ストマーを得るためには、共役ジエンポリマーブ
ロツクを少なくとも１個、かつビニル置換芳香族
炭化水素ポリマーブロツクを少なくとも１個有す
るリビングブロツクコポリマーが特に重要であ
る。かかるリビングブロツクコポリマーにおいて
は、ビニル置換芳香族炭化水素ポリマーブロツク
含有率(a)がポリマー全体に対して10重量％以上な
いし90重量％以下であるブロツクコポリマーが特
に好適である。10重量％未満あるいは90重量％以
上では物性の良好な熱可塑性エラストマーもしく
は熱可塑性樹脂が得られにくくなる。
ビニル置換芳香族炭化水素ポリマーブロツク含
有率(a)は、L.M.Kolthoffら、J.Polymer Sci.，
第１巻、429頁（1946年）の方法に従つて測定し、
含有率(a)は全ポリマー中のブロツクポリマーの含
有率で表わしたものである。
前記リビングブロツクコポリマーにおいては、
共役ジエンポリマーブロツクに少量のビニル置換
芳香族炭化水素が含まれていてもよいし、また、
ビニル置換炭化水素ポリマーブロツクに少量の共
役ジエンが含まれていてもよい。かかるリビング
ブロツクコポリマーは直鎖型の他に、カツプリン
グ剤で一部カツプリングした、いわゆる分岐型、
ラジアル型あるいは星型のブロツクコポリマーも
ポリマー鎖中にリビングリチウムが残存している
限りにおいて包含される。
さらに、本発明に好ましく使用される前記リビ
ングブロツクコポリマーは、共役ジエンブロツク
のミクロ構造が１，２―ビニル結合30〜70重量
％、１，４―結合（シス結合とトランス結合）70
〜30重量％が特に好ましい。かかる範囲にあるブ
ロツクポリマーは、水添反応後オレフイン部分が
良好なゴム弾性を有するため、工業的に有用であ
るばかりでなく、水添反応後の溶媒に対する溶解
性が良好で溶液粘度も低く、水添ポリマーの回収
や溶媒除去が容易で経済的に水添ポリマーを製造
することができる。
ポリマー中の共役ジエン単位の１，２―ビニル
結合含有率(b)は、赤外線吸収スペクトルを用い、
ハンプトン法（R.R.Hampton、Anal.Chem.第29
巻、923頁（1949年））によつて、共役ジエン単位
中の１，２―ビニル結合の割合を重量比率で表わ
したものである。使用した波長はブタジエン／ス
チレン・コポリマーの場合、ブタジエンのシス―
１，４（724cm-1）、トランス―１，４（967cm-1）、
１，２―ビニル（911cm-1）、スチレン（699cm-1）
であり、これにより各成分の濃度が求められる。
本発明の水添反応に用いるリビングポリマーの
分子量は特に制限されるものではないが、一般的
には数平均分子量約1000ないし約100万を有する
もので、リビングポリマーである限り公知のいか
なる重合方法で製造されたものであつてもよい。
本発明に係るリビングポリマーの水添反応に用
いる水添触媒は、一般式[Formula] (However, R and R' are groups selected from an alkyl group having 1 to 8 carbon atoms, an allyl group, an alkoxy group, an allyloxy group, a halogen group, and a carbonyl group, and R and R' may be the same. ) is contacted with hydrogen in the presence of a hydrogenation catalyst consisting of at least one bis(cyclopentadienyl) titanium compound represented by The present invention relates to a method for catalytic hydrogenation of living polymers, which is characterized by selectively hydrogenating double bonds. The hydrogenation catalyst used in the present invention, which uses a bis(cyclopentadienyl) titanium compound in combination with a reducing organometallic compound, has hydrogenation activity toward unsaturated double bonds in low-molecular-weight organic compounds. Already known (e.g. MF
Sloan et al., J.Am.Chem.Soc., Volume 85, 4014~
4018 pages (1965), Y. Tajima et al., J.org.Chem.
Volume 33, pp. 1689-1690 (1968), etc.). but,
These titanium compounds alone have no hydrogenation activity, and there are no examples of using living polymers as reducing organometallic compounds, and no prior art suggesting the use thereof has been disclosed at all. However, the advantage of the polymer hydrogenation method of the present invention is that by using a living polymer having reducible lithium as the hydrogenated polymer, hydrogenation activity can be achieved with just the presence of a small amount of bis(cyclopentadienyl)titanium compound alone. is expressed and hydrogenation progresses, and therefore only one type of catalyst component is required to be newly added.Moreover, the activity is higher than the system used in combination with a reducing organic compound such as the alkyl aluminum mentioned above, and the hydrogenation of the conjugated diene unit is higher. Extremely high hydrogenation selectivity for saturated double bonds;
Furthermore, it is possible to continuously hydrogenate the polymer after polymerization without isolating it, and lithium, which is a polymerization catalyst component, can be used as a hydrogenation catalyst component.
It is surprising that it has become possible to hydrogenate polymers efficiently and economically. Although the present invention can be applied to all hydrocarbon living polymers polymerized with organolithium and having unsaturated double bonds in the polymer, a preferred embodiment is a conjugated diene obtained by polymerizing or copolymerizing a conjugated diene. It is a diene living polymer.
Such conjugated diene living polymers include living copolymers obtained by copolymerizing a conjugated diene homopolymer and a conjugated diene with each other or with at least one conjugated diene and at least one olefin monomer capable of living copolymerization with the conjugated diene. Included. As the polymerization catalyst used in the production of such conjugated diene living polymers, hydrocarbons having at least one lithium atom bonded in the molecule are used, such as n-propyllithium, isopropyllithium, n-butyllithium, sec- Monolithium such as butyllithium, tert-butyllithium, n-pentyllithium, benzyllithium, etc., or 1,4-dilithio-n-butane,
1,5-dilithiopentane, 1,2-dilithiodiphenylethane, 1,4-dilithio-1,1,
4,4-tetraphenylbutane, 1,3- or 1,4-bis(1-lithio-1,3-dimethylpentyl)benzene, 1,3- or 1,4-bis(1-lithio-3- Dilithium such as methylpentyl)benzene is preferably used, and the polymerization catalyst may be a lithium oligomer or an α,ω-dilithium oligomer obtained using these organic lithium. Particularly common examples include n-butyllithium, sec-butyllithium, and the like.
These organolithiums may be used alone or in combination of two or more, and may be used not only once during polymerization, but also in combinations of two or more types.
It may be added in two or more portions during the polymerization. The amount of organic lithium to be used is selected as appropriate depending on the molecular weight of the desired polymer, but is generally 0.005 to 5 mol% based on the total amount of monomers used.
It is. Conjugated dienes used in the production of the conjugated diene living polymers to be subjected to hydrogenation of the present invention generally include conjugated dienes having from 4 to about 12 carbon atoms, and specific examples include 1, 3-butadiene, isoprene, 2,3-dimethyl-1,
Examples include 3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, etc. It will be done. From the viewpoint of obtaining an elastomer that can be industrially advantageously developed and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as butadiene living polymer, isoprene living polymer, and butadiene/isoprene living copolymer are used in the present invention. Particularly preferred for implementation. In such a living polymer, the microstructure of the polymer chain is not particularly limited, and any structure can be suitably used. However, if there are too few 1,2-vinyl bonds, the solubility of the polymer after hydrogenation will decrease, and it will not be possible to uniformly distribute the polymer chain. Since solvents are limited in order to carry out hydrogenation, living polymers containing about 30% or more of such bonds are more preferred. On the other hand, the method of the present invention is particularly suitably used for hydrogenating a living copolymer obtained by copolymerizing at least one conjugated diene and at least one monomer copolymerizable with the conjugated diene. Suitable conjugated dienes used in the production of such living copolymers include the conjugated dienes described above, and one monomer includes all monomers that can be living copolymerized with the conjugated diene, especially vinyl-substituted aromatic carbonized Hydrogen is preferred. In other words, in order to fully exhibit the effect of the present invention of selectively hydrogenating only the unsaturated double bonds of the conjugated diene unit, and to obtain industrially useful and valuable elastomers and thermoplastic elastomers, it is necessary to Of particular interest are living copolymers with vinyl-substituted aromatic hydrocarbons. Specific examples of vinyl-substituted aromatic hydrocarbons used in the production of such living copolymers include styrene, t-butylstyrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, Examples include enylethylene, vinylnaphthalene, N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene, and styrene is particularly preferred. As specific examples of living copolymers, butadiene/styrene living copolymers, isoprene/styrene living copolymers, etc. are the most preferred since they provide hydrogenated copolymers with high industrial value. In such a living copolymer, the vinyl-substituted aromatic hydrocarbon content is preferably 5% to 95% by weight; outside this range, it becomes difficult to obtain the characteristics of a thermoplastic elastomer. Living copolymers according to the method of the invention include random copolymers, tapering block copolymers, fully block copolymers, and graft copolymers in which the monomers are statistically distributed throughout the polymer chain. Living block copolymers having at least one conjugated diene polymer block and at least one vinyl-substituted aromatic hydrocarbon polymer block are particularly important for obtaining industrially useful thermoplastic elastomers. Among such living block copolymers, particularly preferred are block copolymers in which the vinyl-substituted aromatic hydrocarbon polymer block content (a) is from 10% by weight to 90% by weight based on the total polymer. If it is less than 10% by weight or more than 90% by weight, it becomes difficult to obtain a thermoplastic elastomer or thermoplastic resin with good physical properties. Vinyl-substituted aromatic hydrocarbon polymer block content (a) was determined by LMKolthoff et al., J. Polymer Sci.
Measured according to the method of Volume 1, page 429 (1946),
The content (a) is expressed as the content of block polymer in the total polymer. In the living block copolymer,
The conjugated diene polymer block may contain a small amount of vinyl-substituted aromatic hydrocarbon, and
Small amounts of conjugated dienes may also be included in the vinyl substituted hydrocarbon polymer blocks. In addition to linear type living block copolymers, there are so-called branched type copolymers partially coupled with coupling agents, and so-called branched type copolymers.
Radial or star block copolymers are also included as long as living lithium remains in the polymer chain. Furthermore, the living block copolymer preferably used in the present invention has a conjugated diene block microstructure of 30 to 70% by weight of 1,2-vinyl bonds and 70% by weight of 1,4-bonds (cis and trans bonds).
~30% by weight is particularly preferred. Block polymers within this range are not only industrially useful because the olefin portion has good rubber elasticity after the hydrogenation reaction, but also have good solubility in the solvent after the hydrogenation reaction and low solution viscosity. Hydrogenated polymers can be easily recovered and solvent removed, and hydrogenated polymers can be produced economically. The 1,2-vinyl bond content (b) of the conjugated diene units in the polymer is determined using an infrared absorption spectrum,
Hampton method (RRHampton, Anal.Chem. No. 29)
Vol., p. 923 (1949)), the proportion of 1,2-vinyl bonds in the conjugated diene unit is expressed as a weight ratio. In the case of butadiene/styrene copolymers, the wavelengths used were
1,4 (724cm -1 ), transformer 1,4 (967cm -1 ),
1,2-vinyl (911cm -1 ), styrene (699cm -1 )
From this, the concentration of each component can be determined. The molecular weight of the living polymer used in the hydrogenation reaction of the present invention is not particularly limited, but it generally has a number average molecular weight of about 1,000 to about 1 million, and any known polymerization method can be used as long as it is a living polymer. It may be manufactured by. The hydrogenation catalyst used in the living polymer hydrogenation reaction according to the present invention has the general formula
【式】（但
し、Ｒ，R′は炭素原子数１〜８個のアルキル基、
アリル基、アルコキシ基、アリロキシ基、ハロゲ
ン基、カルボニル基から選択された基で、Ｒ，
R′は同一でも異なつていても良い。）で示される
ビス（シクロペンタジエニル）チタニウム化合物
の少なくとも１種である。かかるチタニウム化合
物の具体的な例としては、ビス（シクロペンタジ
エニル）チタニウムジメチル、ビス（シクロペン
タジエニル）チタニウムジエチル、ビス（シクロ
ペンタジエニル）チタニウムジ―ｎ―ブチル、ビ
ス（シクロペンタジエニル）チタニウムジ―sec
―ブチル、ビス（シクロペンタジエニル）チタニ
ウムジメトキシド、ビス（シクロペンタジエニ
ル）チタニウムジエトキシド、ビス（シクロペン
タジエニル）チタニウムジプトキシド、ビス（シ
クロペンタジエニル）チタニウムジフエニル、ビ
ス（シクロペンタジエニル）チタニウムジフエノ
キシド、ビス（シクロペンタジエニル）チタニウ
ムジフルオライド、ビス（シクロペンタジエニ
ル）チタニウムジクロライド、ビス（シクロペン
タジエニル）チタニウムジブロマイド、ビス（シ
クロペンタジエニル）チタニウムジイオダイド、
ビス（シクロペンタジエニル）チタニウムジカル
ボニル、ビス（シクロペンタジエニル）チタニウ
ムクロライドメチル、ビス（シクロペンタジエニ
ル）チタニウムクロライドエトキサイド、ビス
（シクロペンタジエニル）チタニウムクロライド
フエノキシド等が挙げられ、単独あるいは相互に
組み合わせて用いてもリビングポリマーの共役ジ
エン単位の不飽和二重結合を選択的に水添するこ
とが可能である。これらチタニウム化合物のう
ち、ポリマー水添活性が高く少量の使用ですみ、
かつ温和な条件で共役ジエン単位の不飽和二重結
合を極めて良好に選択的に水添するためには、ビ
ス（シクロペンタジエニル）チタニウムジメチ
ル、ビス（シクロペンタジエニル）チタニウムジ
―ｎ―ブチル、ビス（シクロペンタジエニル）チ
タニウムジクロライド、ビス（シクロペンタジエ
ニル）チタニウムジカルボニルが好適に用いられ
る。かかるチタニウム化合物は一般的に不安定な
ものが多く、空気、酸素や光、熱に対して分解性
であり、工業的使用においては不活性雰囲気下、
冷暗所で取扱う必要があるが、ビス（シクロペン
タジエニル）チタニウムジクロライドは安定性が
高く、ポリマー水添活性、選択性にも優れ、最も
好適に用いられる。
本発明の水添反応の好ましい実施態様は、リビ
ングポリマーを不活性有機溶媒に溶解した溶液に
おいて行なわれ、より好ましくは不活性溶媒中に
て共役ジエン等を重合して得られたリビングポリ
マー溶液をそのまま水添反応に用いて連続的に行
なわれる。「不活性有機溶媒」とは溶媒が重合や
水添反応のいかなる関与体とも反応しないものを
意味する。好適な溶媒は、例えばｎ―ペンタン、
ｎ―ヘキサン、ｎ―ヘプタン、ｎ―オクタンの如
き脂肪族炭化水素類、シクロヘキサン、シクロヘ
プタンの如き脂環族炭化水素類、ジエチルエーテ
ル、テトラヒドロフランの如きエーテル類の単独
もしくは混合物である。また、ベンゼン、トルエ
ン、キシレン、エチルベンゼンの如き芳香族炭化
水素も、選択された水添反応条件下で芳香族性二
重結合が水添されない時に限つて使用することが
できる。本発明の水添反応は、溶媒に対するリビ
ングポリマー濃度１〜50重量％、好ましくは３〜
25重量％で行なわれ、水添反応に供するリビング
ポリマーが溶媒中の水分や不純物によつて全て失
活せず、リチウムを保持していることが必要であ
る。
本発明の水添反応は、一般的にはリビングポリ
マー溶液を所定の温度に保持し、撹拌下または不
撹拌下にて水添触媒を添加し、次いで水素ガスを
導入して所定圧に加圧することによつて実施され
る。水添触媒はそのままリビングポリマー溶液に
加えてもよいし、前記の如き不活性有機溶媒の溶
液として加えてもよい。水添反応を均一に、速や
かに進行させるためには溶液として加えるのが好
ましい。
また、水添触媒は不活性雰囲気下で取扱うこと
が必要である。不活性雰囲気とは、例えばヘリウ
ム、ネオン、アルゴン等の水添反応のいかなる関
与体とも反応しない雰囲気下を意味する。空気や
酸素は水添触媒を酸化したり、分解したりして触
媒の失活を招くので好ましくない。
さらに、リビングポリマー溶液に水添触媒を加
える際は、水素雰囲気下で行なうのが水添活性を
最も高め、ポリマーの水添反応を速やかに均一に
進行させる上で好ましい実施態様である。
一方、水添触媒の添加量はリビングポリマー
100ｇ当り0.005〜10ミリモルの範囲が好適であ
る。この添加量範囲であればリビングポリマーの
共役ジエン単位の不飽和二重結合を優先的に水添
することが可能であり、芳香核二重結合の水添は
実質的に起こらないので、極めて高い水添選択性
が実現される。10ミリモル以上の添加においても
リビングポリマーの水添は可能であり、その使用
を制限するものではないが、10ミリモル以上添加
しても水添の効果は実質的に変りなく、むしろ逆
に必要以上の触媒使用は不経済であるばかりでな
く、水添反応後触媒の脱灰や除去が必要となりプ
ロセスが複雑になる等の不利を招く。また、
0.005ミリモル以下では触媒が不純物等で失活し
たりし易く定量的水添が進行しにくくなる。より
好ましい水添触媒添加量はリビングポリマー100
ｇ当り0.01〜２ミリモルの範囲である。
また、本発明に係るリビングポリマーの水添反
応においては、リビングポリマー中のリチウムと
水添触媒中のチタニウムとの比率（以下Li／Ti
モル比）も水添活性に影響を与える。リビングポ
リマー中のリチウム含有率はリビングポリマーの
分子量、重合触媒に用いる有機リチウムの官能
数、さらにはリビングの失活率等によつて異な
り、従つて、Li／Tiモル比は水添反応に用いる
リビングポリマーの性状と前記触媒添加量に応じ
て一義的に決定されるが、高い水添活性と共役ジ
エン単位の不飽和二重結合に対する高い水添選択
性を実現するためには、Li／Tiモル比＝0.1〜100
の範囲が好適である。さらにLi／Tiモル比＝２
〜20の範囲は水添活性を著しく向上するので最も
好適である。このLi／Tiモル比を実現するため
には、場合によつてはリビングポリマーの一部を
水やアルコール、ハロゲン化物等であらかじめ失
活させたり、リビングポリマー中に重合触媒とし
て用いる有機リチウムを水添前に加えたりしてリ
ビングポリマー溶液中のリチウム濃度を調整して
もよい。
本発明の水添反応は元素状水素を用いて行なわ
れ、より好ましくはガス状でリビングポリマー溶
液中に導入される。水添反応は撹拌下行なわれる
のがより好ましく、導入された水素を十分迅速に
ポリマーと接触させることができる。水添反応は
一般的に−20℃〜100℃の温度範囲で実施される。
−20℃以下では触媒の活性が低下し、かつ水添速
度も遅くなり多量の触媒を要するので経済的でな
く、また、水添ポリマーが不溶化して析出し易
い。一方、100℃以上では触媒の失活を招いたり、
ポリマーの分解やゲル化を併発し易くなり、かつ
芳香核部分の水添も起こり易くなつて水添選択性
が低下するので好ましくない。さらに好ましく
は、20〜80℃の範囲である。
水添反応に使用される水素の圧力は特に制限す
るものではないが、１〜100Kg／cm2が好適である。
１Kg／cm2以下では水添速度が遅くなつて実質的に
頭打ちとなるので水添率を上げるのが難しくな
り、100Kg／cm2以上では昇圧と同時に水添反応が
ほぼ完了し実質的に意味がなく、不必要な副反応
やゲル化を招くので好ましくない。より好ましい
水添水素圧力は２〜30Kg／cm2であるが、触媒添加
量等水添条件との相関で最適水素圧力は選択さ
れ、実質的には水添触媒量が少量になるに従つて
水素圧力は高圧側を選択して実施するのが好まし
い。
本発明の水添反応時間は通常数秒ないし50時間
である。他の水添反応条件の選択によつて水添反
応時間は上記範囲内で適宜選択して実施される。
本発明の水添反応はバツチ式、連続式等のいか
なる方法で実施してもよい。水添反応の進行は水
素吸収量を追跡することによつて把握することが
できる。
本発明の方法によつて、ポリマーの共役ジエン
単位の不飽和二重結合が50％以上、好ましくは90
％以上水添された水添ポリマーを得ることができ
る。また、より好ましくは共役ジエンとビニル置
換芳香族炭化水素とのコポリマーを水添した場
合、共役ジエン単位の不飽和二重結合の水添率が
50％以上、好ましくは90％以上、かつ芳香核部分
の水添率が10％以下の選択的に水添された水添コ
ポリマーを得ることができる。共役ジエン単位の
水添率が50％未満であると耐候性、耐酸化性、耐
熱性の改良効果が十分でない。また、共役ジエン
とビニル置換芳香族炭化水素とのコポリマーの場
合には、芳香核部分が水添されても顕著な物性改
良効果は認められず、特にブロツクコポリマーの
場合は本来の優れた加工性、成形性が悪くなる。
さらに芳香核部分の水添には多量の水素が消費さ
れ、高温、高圧、長時間の水添反応が必要となり
経済的に実施しにくくなる。本発明に係るポリマ
ー水添触媒は極めて選択性に優れ、実質的に芳香
核部分は水添されないので工業上極めて有利であ
る。
上記ポリマーの水添率は、芳香核部分を含む場
合は紫外線吸収スペクトルおよび赤外線吸収スペ
クトルの測定により、また芳香核部分を含まない
場合は赤外線吸収スペクトルの測定により求める
ことができる。すなわち、芳香核部分の水添率は
紫外線吸収スペクトルの芳香核部分の吸収（例え
ば、スチレンの場合は250ｍμ）よりポリマー中
の芳香核部分の含有量を測定し、次式から算出さ
れる。
ポリマー中の芳香核部分の水添率（％）＝（１−水添
反応後のポリマー中の芳香核含量／水添反応前のポリマ
ー中の芳香核含量）×100
また、共役ジエン単位の水添率は赤外線吸収ス
ペクトルより、前記ハンプトン法によつて不飽和
部分、すなわち、共役ジエン単位からなる部分
（シス、トランス、ビニル各結合の合計）と芳香
核部分のポリマー中の濃度比ｒと、紫外線吸収ス
ペクトルで求めた水添前後の芳香核含量から計算
される。
ｒ＝水添反応後のポリマー中の共役ジエン単位含量／
水添反応後のポリマー中の芳香核含量
ポリマー中の共役ジエン単位水添率（％）
＝（１−水添反応後のポリマー中の共役ジエン単位
含量／水添反応前のポリマー中の共役ジエン単位含量）
×100
＝〔１−ｒ×（水添反応後の芳香核含量）／（１−
水添反応前の芳香核含量）〕×100
本発明の方法により水添反応を行なつたポリマ
ー溶液からは必要に応じて触媒残渣を除去し、水
添されたポリマーを溶液から容易に単離すること
ができる。例えば、水添後の反応液にアセトンま
たはアルコール等の水添ポリマーに対する貧溶媒
となる極性溶媒を加えてポリマーを沈殿せしめ回
収する方法、反応液を撹拌下熱湯中に投入後、溶
媒と共に蒸留回収する方法、または直接反応液を
加熱して溶媒を留去する方法等で行なうことがで
きる。本発明の水添方法は使用する水添触媒量が
少量である特徴を有する。従つて、水添触媒がそ
のままポリマー中に残存しても得られる水添ポリ
マーの物性に著しい影響を及ぼさず、かつ水添ポ
リマーの単離過程において触媒の大部分が分解、
除去されポリマーより除かれるので、触媒を脱灰
したり除去したりするための特別な操作は必要と
せず、極めて簡単なプロセスで実施することがで
きる。
以上のように本発明によつて、共役ジエンポリ
マーを高活性な触媒によつて温和な条件で水添す
ること、特に共役ジエンとビニル置換芳香族炭化
水素とのコポリマーの共役ジエン単位の不飽和二
重結合を極めて選択的に水添することが可能とな
つた。さらに本発明の方法においては、リビング
ポリマーを原料とするので、重合に続いて同一反
応器で連続的に水添が可能なこと、添加する触媒
成分が１種類でよく、かつ少量の添加で極めて高
い活性を示すこと、従つて水添後触媒の脱灰を要
しないこと等経済的かつ簡単なプロセスにて効率
的に実施することが可能となり工業上極めて有用
である。
また、本発明の方法によつて得られる水添ポリ
マーは、耐候性、耐酸化性の優れたエラストマ
ー、熱可塑性エラストマーもしくは熱可塑性樹脂
として使用され、また紫外線吸収剤、オイル、フ
イラー等の添加剤を加えたり、他のエラストマー
や樹脂とブレンドして使用され、工業上極めて有
用である。
以下実施例により本発明を具体的に説明する
が、本発明はこれらに限定されるものではない。
実施例に用いた各リビングポリマーの合成例を
以下の参考例に示した。
参考例 １
２のオートクレーブ中にシクロヘキサン500
ｇ、１，３―ブタジエンモノマー100ｇ、ｎ―ブ
チルリチウム0.05ｇを加え、撹拌下60℃にて３時
間重合しリビングポリブタジエンを合成した。得
られたリビングポリブタジエンはポリマー100ｇ
当り0.67ミリモルのリビングリチウムを有し、一
部単離して分析したところ、１，２―ビニル結合
を13％含有し、GPCで測定した数平均分子量は
約15万のリビングポリブタジエンであつた。
参考例 ２
１，３―ブタジエンの代りにイソプレンを用い
た以外は参考例１と同様に重合し、リビングポリ
マー100ｇ当り0.66ミリモルのリビングリチウム
を有し、１，２―ビニル結合10％、数平均分子量
約15万のリビングポリイソプレンを得た。
参考例 ３
参考例１において、さらにテトラヒドロフラン
をｎ―ブチルリチウムに対し40倍モル加えた以外
は同様に重合しリビングポリブタジエンを合成し
た。このものはポリマー100ｇ当り0.66ミリモル
のリビングリチウムを有し、１，２―ビニル結合
43％、数平均分子量約15万のものであつた。
参考例 ４
シクロヘキサン400ｇ、１，３―ブタジエンモ
ノマー70ｇ、スチレンモノマー30ｇ、ｎ―ブチル
リチウム0.03ｇおよびテトラヒドロフラン0.9ｇ
を同時にオートクレーブに加え、40℃で２時間重
合した。
得られたポリマーはブタジエン／スチレンの完
全ランダムリビングコポリマーで、ポリマー100
ｇ当り0.48ミリモルのリビングリチウムを有し、
ブタジエン単位の１，２―ビニル結合含有率50
％、数平均分子量20万を有するものであつた。
参考例 ５
オートクレーブ中にシクロヘキサン400ｇ、ス
チレンモノマー15ｇとｎ―ブチルリチウム0.11ｇ
を加え、60℃で３時間重合し、次いで１，３―ブ
タジエンモノマーを70ｇ加えて60℃で３時間重合
した。最後にスチレンモノマー15ｇを添加し、60
℃で３時間重合し、結合スチレン含有量30％、ブ
ロツクスチレン含有量29.5％、ブタジエン単位の
１，２―ビニル結合含有量13％（全重合体換算９
％）の数平均分子量が約６万であるスチレン―ブ
タジエン―スチレン型リビングブロツクポリマー
を得た。このポリマー中のリビングリチウムは
1.65ミリモル／ポリマー100ｇであつた。
参考例 ６
スチレンモノマー量を各々40ｇ（合計80ｇ）、
１，３―ブタジエンモノマー量を20ｇとする以外
は参考例５と同じ方法で、高スチレン量のリビン
グブロツクコポリマーを合成した。得られたスチ
レン―ブタジエン―スチレン型のリビングブロツ
クコポリマーは、結合スチレン含有量80％、ブロ
ツクスチレン含有量78％、ブタジエン単位の１，
２―ビニル結合含有量15％（全重合体換算３％）、
数平均分子量約６万であり、リビングリチウムを
1.65ミリモル／ポリマー100ｇ有するものであつ
た。
参考例 ７
参考例５において、さらにテトラヒドロフラン
をｎ―ブチルリチウムに対して35倍モル加えた以
外は全く同様に重合し、結合スチレン含量30％、
ブロツクスチレン含量25％、ブタジエン単位の
１，２―ビニル結合含量38％の数平均分子量が約
６万であるスチレン―ブタジエン―スチレン型リ
ビングブロツクポリマーを合成した。このポリマ
ー中のリビングリチウム含量は1.65ミリモル／ポ
リマー100ｇであつた。
参考例 ８
容積１で高さ／直径＝４の撹拌器付ベツセル
型反応器に、シクロヘキサンを1200ｇ／hr、１，
３―ブタジエンモノマー210ｇ／hr、ｎ―ブチル
リチウム（ｎ―BuLi）1.33ｇ／hr、テトラヒド
ロフラン（THF）〔ｎ―BuLi／THF＝30モル
比〕を反応器の底より連続的に供給し、また反応
器の上部よりスチレンモノマー90ｇ／hr供給して
重合温度100℃、平均滞留時間25分で重合し、リ
ビングポリマー溶液を連続的に反応器より取り出
した。
得られたリビングコポリマーはブタジエン―ス
チレン型構造を有し、結合スチレン含有量30％、
ブロツクスチレン含有量10.2％、ブタジエン単位
の１，２―ビニル結合含有量40％（全重合体換算
28％）、数平均分子量約18万であつた。なおこの
ものはポリマー100ｇ当りリビングリチウムを
0.55ミリモル有するものであつた。
参考例 ９
オートクレーブ中にシクロヘキサン400ｇ、１，
３―ブタジエンモノマー13ｇ、ｎ―ブチルリチウ
ム0.15ｇおよびテトラヒドロフランをモル比でｎ
―BuLi／THF＝40の割合で加え、70℃で45分重
合し、次いでスチレンモノマー20ｇを加えて30
分、次いで１，３―ブタジエンモノマー47ｇを加
えて75分、そして最後にスチレンモノマー20ｇを
加えて30分重合し、ブタジエン―スチレン−ブタ
ジエン―スチレン型リビングブロツクポリマーを
合成した。
このものは結合スチレン含有量40％、ブロツク
スチレン含有量33％、ブタジエン単位の１，２―
ビニル結合含有量35％（全重合体換算30％）、数
平均分子量約６万で、リビングポリマー100ｇ当
り1.65ミリモルのリビングリチウムを有するもの
であつた。
参考例 10
１，３―ブタジエンの代りにイソプレンを用い
た以外は参考例５と全く同じ方法で、スチレン―
イソプレン―スチレン型リビングブロツクコポリ
マーを合成した。
このものはリビングポリマー100ｇ当り1.65ミ
リモルのリビングリチウムを有し、結合スチレン
含有量は30％、ブロツクスチレン含有量は29.5
％、イソプレン単位の１，２―ビニル結合含有量
は10％（全重合体換算７％）、数平均分子量は約
６万であつた。
参考例 11
sec―ブチルリチウム0.5モルを含むシクロヘキ
サン溶液にトリエチルアミン0.5モルを加え室温
で１時間撹拌した。次いでｍ―ジイソプロペニル
ベンゼン0.25モルを室温で３時間かけて撹拌下滴
下し、さらに室温で24時間撹拌を続け１，３―ビ
ス（１―リチオ―１，３―ジメチルペンチル）ベ
ンゼンのシクロヘキサン溶液を得た。このジリチ
ウムの純度は98.7％、活性リチウム濃度は2.00ミ
リモル／ｇであつた。
オートクレーブ中にシクロヘキサン400ｇ、１，
３―ブタジエンモノマー70ｇと前記で合成したジ
リチウム触媒溶液1.40ｇ（活性リチウムとして
2.80ミリモル）を加え60℃で３時間重合した。次
いでスチレンモノマー30ｇを加えて60℃で３時間
重合し、結合スチレン含有量30％、ブロツクスチ
レン含有量29％、ブタジエン単位の１，２―ビニ
ル結合含有量20％で、数平均分子量約８万である
スチレン―ブタジエン―スチレン型ジリビングブ
ロツクポリマーを得た。このポリマー中のリビン
グリチウムは、2.50ミリモル／ポリマー100ｇで
あつた。
参考例 12
オートクレーブ中にシクロヘキサン400ｇ、１，
３―ブタジエンモノマー100ｇおよび参考例11に
示した１，３―ビス（１―リチオ―１，３―ジメ
チルペンチル）ベンゼンのシクロヘキサン溶液
20.0ｇ（活性リチウムとして40ミリモル）を加
え、撹拌下60℃にて３時間重合しジリビングポリ
ブタジエンを合成した。このものは数平均分子量
約6000、１，２―ビニル結合35％を有し、ポリマ
ー100ｇ当りのリビングリチウムは33.0ミリモル
であつた。
実施例 １〜12
参考例１と２で得られた各リビングポリマー溶
液を精製乾燥したトルエンにて希釈し、また参考
例３〜12で得られた各リビングポリマー溶液を精
製乾燥したシクロヘキサンで希釈し、リビングポ
リマー濃度５重量％に調整して水添反応に供し
た。
十分に乾燥した容量２の撹拌器付オートクレ
ーブに上記リビングポリマー溶液1000ｇ（リビン
グポリマー量50ｇ）を仕込み、減圧脱気後水素置
換し、撹拌下40℃に保持した。
次いで水添触媒として濃度1.0ミリモル／100ml
のビス（シクロペンタジエニル）チタニウムジク
ロライドのトルエン溶液20.0ml（触媒量0.20ミリ
モル）をオートクレーブ中へ仕込み、5.0Kg／cm2
の乾燥したガス状水素を供給し撹拌下２時間水添
反応を行なつた。いずれも30分以内に実質的な水
素吸収は完了し、反応液は微黒〜灰黒色の均一低
粘度溶液であつた。反応液を常温常圧に戻してオ
ートクレーブより取り出し、多量のメタノールを
加えてポリマーを沈殿させ、別後乾燥し、白色
の水素ポリマーを得た。水添条件および得られた
水添ポリマーの水添率、性状を表１にまとめた。
表１に示した如く、いずれのポリマーも共役ジ
エン単位は定量的に水添され、かつスチレン単位
はほとんど水添されず極めて良好な活性と選択性
を示した。[Formula] (where R and R' are alkyl groups having 1 to 8 carbon atoms,
A group selected from an allyl group, an alkoxy group, an allyloxy group, a halogen group, and a carbonyl group, R,
R′ may be the same or different. ) is at least one type of bis(cyclopentadienyl) titanium compound represented by: Specific examples of such titanium compounds include bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium diethyl, bis(cyclopentadienyl)titanium di-n-butyl, and bis(cyclopentadienyl)titanium di-n-butyl. enyl) titanium di-sec
-Butyl, bis(cyclopentadienyl) titanium dimethoxide, bis(cyclopentadienyl) titanium diethoxide, bis(cyclopentadienyl) titanium diptoxide, bis(cyclopentadienyl) titanium diphenyl, bis( cyclopentadienyl) titanium diphenoxide, bis(cyclopentadienyl) titanium difluoride, bis(cyclopentadienyl) titanium dichloride, bis(cyclopentadienyl) titanium dibromide, bis(cyclopentadienyl) titanium diiodide,
Bis(cyclopentadienyl) titanium dicarbonyl, bis(cyclopentadienyl) titanium chloride methyl, bis(cyclopentadienyl) titanium chloride ethoxide, bis(cyclopentadienyl) titanium chloride phenoxide, etc. , alone or in combination with each other, it is possible to selectively hydrogenate the unsaturated double bonds of the conjugated diene units of the living polymer. Among these titanium compounds, they have high polymer hydrogenation activity and can be used in small amounts.
In order to hydrogenate the unsaturated double bonds of the conjugated diene unit very selectively under mild conditions, bis(cyclopentadienyl)titanium dimethyl, bis(cyclopentadienyl)titanium di-n- Butyl, bis(cyclopentadienyl) titanium dichloride, and bis(cyclopentadienyl) titanium dicarbonyl are preferably used. Many of these titanium compounds are generally unstable and decomposable in the presence of air, oxygen, light, and heat, and in industrial use they cannot be used under an inert atmosphere.
Although it is necessary to handle it in a cool and dark place, bis(cyclopentadienyl)titanium dichloride is highly stable and has excellent polymer hydrogenation activity and selectivity, so it is most preferably used. A preferred embodiment of the hydrogenation reaction of the present invention is carried out in a solution in which a living polymer is dissolved in an inert organic solvent, and more preferably in a living polymer solution obtained by polymerizing a conjugated diene or the like in an inert solvent. The hydrogenation reaction is carried out continuously as it is. "Inert organic solvent" means a solvent that does not react with any participant in the polymerization or hydrogenation reaction. Suitable solvents include, for example, n-pentane,
These include aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane and cycloheptane, and ethers such as diethyl ether and tetrahydrofuran, singly or in mixtures. Aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can also be used as long as aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions. In the hydrogenation reaction of the present invention, the living polymer concentration relative to the solvent is 1 to 50% by weight, preferably 3 to 50% by weight.
It is necessary that the living polymer subjected to the hydrogenation reaction is not completely deactivated by moisture or impurities in the solvent and retains lithium. The hydrogenation reaction of the present invention is generally performed by maintaining a living polymer solution at a predetermined temperature, adding a hydrogenation catalyst with or without stirring, and then introducing hydrogen gas to increase the pressure to a predetermined pressure. It is carried out by The hydrogenation catalyst may be added to the living polymer solution as it is, or may be added as a solution in an inert organic solvent as described above. In order for the hydrogenation reaction to proceed uniformly and quickly, it is preferable to add it as a solution. Furthermore, it is necessary to handle the hydrogenation catalyst under an inert atmosphere. An inert atmosphere means an atmosphere that does not react with any participants in the hydrogenation reaction, such as helium, neon, argon, and the like. Air and oxygen are not preferred because they oxidize or decompose the hydrogenation catalyst, leading to deactivation of the catalyst. Furthermore, when adding the hydrogenation catalyst to the living polymer solution, it is a preferred embodiment to do so in a hydrogen atmosphere in order to maximize the hydrogenation activity and allow the hydrogenation reaction of the polymer to proceed quickly and uniformly. On the other hand, the amount of hydrogenation catalyst added is
A range of 0.005 to 10 mmol per 100 g is preferred. Within this addition amount range, it is possible to preferentially hydrogenate the unsaturated double bonds of the conjugated diene units of the living polymer, and hydrogenation of the aromatic nucleus double bonds does not substantially occur, so the hydrogenation rate is extremely high. Hydrogenation selectivity is achieved. Hydrogenation of the living polymer is possible even when 10 mmol or more is added, and its use is not limited, but the hydrogenation effect does not substantially change even when 10 mmol or more is added, and on the contrary, it is possible to hydrogenate the living polymer even if it is added in an amount of 10 mmol or more. The use of a catalyst is not only uneconomical, but also causes disadvantages such as complicating the process as it requires deashing and removal of the catalyst after the hydrogenation reaction. Also,
If the amount is less than 0.005 mmol, the catalyst is likely to be deactivated due to impurities, etc., making it difficult to proceed with quantitative hydrogenation. A more preferable amount of hydrogenation catalyst added is Living Polymer 100
It ranges from 0.01 to 2 mmol per g. In addition, in the living polymer hydrogenation reaction according to the present invention, the ratio of lithium in the living polymer to titanium in the hydrogenation catalyst (hereinafter referred to as Li/Ti
molar ratio) also influences hydrogenation activity. The lithium content in the living polymer varies depending on the molecular weight of the living polymer, the functional number of the organolithium used as a polymerization catalyst, and the deactivation rate of the living polymer. Therefore, the Li/Ti molar ratio used in the hydrogenation reaction Although it is uniquely determined depending on the properties of the living polymer and the amount of catalyst added, Li/Ti Molar ratio = 0.1~100
A range of is suitable. Furthermore, Li/Ti molar ratio = 2
A range of 20 to 20 is most preferred because it significantly improves hydrogenation activity. In order to achieve this Li/Ti molar ratio, it may be necessary to deactivate part of the living polymer in advance with water, alcohol, halide, etc., or to add organic lithium used as a polymerization catalyst to the living polymer in water. The lithium concentration in the living polymer solution may be adjusted by adding it before addition. The hydrogenation reaction of the present invention is carried out using elemental hydrogen, more preferably introduced in gaseous form into the living polymer solution. More preferably, the hydrogenation reaction is carried out under stirring, so that the introduced hydrogen can be brought into contact with the polymer quickly enough. The hydrogenation reaction is generally carried out at a temperature range of -20°C to 100°C.
Below -20°C, the activity of the catalyst decreases and the hydrogenation rate becomes slow, requiring a large amount of catalyst, which is not economical, and the hydrogenated polymer tends to become insolubilized and precipitate. On the other hand, temperatures above 100℃ may cause deactivation of the catalyst.
This is not preferable because it tends to cause decomposition and gelation of the polymer, and hydrogenation of the aromatic nucleus portion also tends to occur, resulting in a decrease in hydrogenation selectivity. More preferably, the temperature is in the range of 20 to 80°C. Although the pressure of hydrogen used in the hydrogenation reaction is not particularly limited, it is preferably 1 to 100 kg/cm 2 .
Below 1 Kg/cm 2 , the hydrogenation rate slows down and practically reaches a plateau, making it difficult to increase the hydrogenation rate, while above 100 Kg/cm 2 , the hydrogenation reaction is almost completed at the same time as the pressure is increased, making it virtually meaningless. This is not preferable because it causes unnecessary side reactions and gelation. A more preferable hydrogenation pressure is 2 to 30Kg/ cm2 , but the optimum hydrogen pressure is selected in correlation with the hydrogenation conditions such as the amount of catalyst added, and in practice, as the amount of hydrogenation catalyst becomes smaller, It is preferable to select a high pressure side for hydrogen pressure. The hydrogenation reaction time of the present invention is usually several seconds to 50 hours. The hydrogenation reaction time is appropriately selected within the above range by selecting other hydrogenation reaction conditions. The hydrogenation reaction of the present invention may be carried out in any manner such as a batch method or a continuous method. The progress of the hydrogenation reaction can be monitored by tracking the amount of hydrogen absorbed. By the method of the present invention, the unsaturated double bonds in the conjugated diene units of the polymer are 50% or more, preferably 90% or more.
% or more hydrogenated polymer can be obtained. More preferably, when a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon is hydrogenated, the hydrogenation rate of the unsaturated double bond of the conjugated diene unit is
It is possible to obtain a selectively hydrogenated hydrogenated copolymer having a hydrogenation rate of 50% or more, preferably 90% or more, and 10% or less of the aromatic nucleus portion. If the hydrogenation rate of the conjugated diene unit is less than 50%, the effects of improving weather resistance, oxidation resistance, and heat resistance will not be sufficient. Furthermore, in the case of a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon, no remarkable effect of improving physical properties is observed even if the aromatic nucleus moiety is hydrogenated, and especially in the case of a block copolymer, the originally excellent processability , moldability deteriorates.
Furthermore, hydrogenation of the aromatic nucleus portion consumes a large amount of hydrogen and requires a hydrogenation reaction at high temperature, high pressure, and for a long time, making it difficult to carry out economically. The polymer hydrogenation catalyst according to the present invention has extremely excellent selectivity, and the aromatic nucleus portion is not substantially hydrogenated, so it is extremely advantageous industrially. The hydrogenation rate of the polymer can be determined by measuring the ultraviolet absorption spectrum and infrared absorption spectrum when the polymer contains an aromatic nucleus moiety, or by measuring the infrared absorption spectrum when the polymer does not contain an aromatic nucleus moiety. That is, the hydrogenation rate of the aromatic nucleus portion is calculated from the following formula by measuring the content of the aromatic nucleus portion in the polymer from the absorption of the aromatic nucleus portion in the ultraviolet absorption spectrum (for example, 250 mμ in the case of styrene). Hydrogenation rate (%) of the aromatic nucleus portion in the polymer = (1-aromatic nucleus content in the polymer after hydrogenation reaction/aromatic nucleus content in the polymer before hydrogenation reaction) × 100 In addition, the water in the conjugated diene unit The addition rate is calculated from the infrared absorption spectrum using the Hampton method as the concentration ratio r of the unsaturated portion, that is, the portion consisting of conjugated diene units (total of cis, trans, and vinyl bonds) and the aromatic nucleus portion, in the polymer. It is calculated from the aromatic nucleus content before and after hydrogenation determined by ultraviolet absorption spectrum. r=Conjugated diene unit content in the polymer after hydrogenation reaction/
Aromatic nucleus content in the polymer after the hydrogenation reaction Conjugated diene unit hydrogenation rate in the polymer (%) = (1 - Conjugated diene unit content in the polymer after the hydrogenation reaction / Conjugated diene in the polymer before the hydrogenation reaction unit content)
×100 = [1-r×(aromatic nucleus content after hydrogenation reaction)/(1-
Aromatic nucleus content before hydrogenation reaction)〕×100 Catalyst residues are removed as necessary from the polymer solution subjected to hydrogenation reaction by the method of the present invention, and the hydrogenated polymer can be easily isolated from the solution. can do. For example, a method in which a polar solvent such as acetone or alcohol, which is a poor solvent for the hydrogenated polymer, is added to the reaction solution after hydrogenation to precipitate and recover the polymer, or a method in which the reaction solution is poured into boiling water with stirring and then distilled and recovered together with the solvent. This can be carried out by a method of directly heating the reaction solution and distilling off the solvent. The hydrogenation method of the present invention is characterized in that the amount of hydrogenation catalyst used is small. Therefore, even if the hydrogenation catalyst remains in the polymer, it does not significantly affect the physical properties of the hydrogenated polymer obtained, and most of the catalyst decomposes and decomposes during the isolation process of the hydrogenated polymer.
Since the catalyst is removed and removed from the polymer, no special operations are required to deash or remove the catalyst, and it can be carried out in an extremely simple process. As described above, according to the present invention, a conjugated diene polymer can be hydrogenated under mild conditions using a highly active catalyst, and in particular, unsaturation of conjugated diene units in a copolymer of a conjugated diene and a vinyl-substituted aromatic hydrocarbon can be achieved. It has become possible to hydrogenate double bonds extremely selectively. Furthermore, in the method of the present invention, since a living polymer is used as a raw material, hydrogenation can be carried out continuously in the same reactor following polymerization, and only one type of catalyst component is required, and even a small amount can be added. It is extremely useful industrially because it exhibits high activity and does not require deashing of the catalyst after hydrogenation, allowing it to be carried out efficiently in an economical and simple process. In addition, the hydrogenated polymer obtained by the method of the present invention can be used as an elastomer, thermoplastic elastomer, or thermoplastic resin with excellent weather resistance and oxidation resistance, and can also be used as an additive for ultraviolet absorbers, oils, fillers, etc. It is used by adding or blending with other elastomers and resins, making it extremely useful industrially. EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Synthesis examples of each living polymer used in Examples are shown in the Reference Examples below. Reference example: 500 ml of cyclohexane in the autoclave of 1 and 2.
g, 100 g of 1,3-butadiene monomer, and 0.05 g of n-butyllithium were added, and the mixture was polymerized at 60° C. for 3 hours with stirring to synthesize living polybutadiene. The living polybutadiene obtained is 100g of polymer.
It contained 0.67 mmol of living lithium per polybutadiene, and when a portion was isolated and analyzed, it was found to be living polybutadiene containing 13% of 1,2-vinyl bonds and having a number average molecular weight of about 150,000 as measured by GPC. Reference Example 2 Polymerization was carried out in the same manner as in Reference Example 1 except that isoprene was used instead of 1,3-butadiene, and the living polymer had 0.66 mmol of living lithium per 100 g of living polymer, 10% of 1,2-vinyl bonds, and a number average Living polyisoprene with a molecular weight of approximately 150,000 was obtained. Reference Example 3 Living polybutadiene was synthesized by polymerizing in the same manner as in Reference Example 1, except that tetrahydrofuran was further added in a molar amount 40 times that of n-butyllithium. It has 0.66 mmol of living lithium per 100 g of polymer and has 1,2-vinyl bonds.
43%, with a number average molecular weight of approximately 150,000. Reference example 4 400 g of cyclohexane, 70 g of 1,3-butadiene monomer, 30 g of styrene monomer, 0.03 g of n-butyllithium, and 0.9 g of tetrahydrofuran
were simultaneously added to the autoclave and polymerized at 40°C for 2 hours. The resulting polymer is a completely random living copolymer of butadiene/styrene, with polymer 100
with 0.48 mmol living lithium per g;
1,2-vinyl bond content of butadiene unit 50
% and a number average molecular weight of 200,000. Reference example 5 400g of cyclohexane, 15g of styrene monomer and 0.11g of n-butyllithium in an autoclave
was added and polymerized at 60°C for 3 hours, then 70g of 1,3-butadiene monomer was added and polymerized at 60°C for 3 hours. Finally, add 15g of styrene monomer and
Polymerization was carried out at ℃ for 3 hours, and the content of bound styrene was 30%, the content of blocked styrene was 29.5%, and the content of 1,2-vinyl bonds in butadiene units was 13% (calculated as 9% in terms of total polymer).
A styrene-butadiene-styrene type living block polymer having a number average molecular weight of about 60,000 (%) was obtained. The living lithium in this polymer is
The amount was 1.65 mmol/100 g of polymer. Reference example 6 The amount of styrene monomer is 40g each (total 80g),
A living block copolymer containing a high amount of styrene was synthesized in the same manner as in Reference Example 5 except that the amount of 1,3-butadiene monomer was changed to 20 g. The resulting living block copolymer of the styrene-butadiene-styrene type contained 80% bound styrene content, 78% blocked styrene content, and 1,
2-vinyl bond content 15% (3% in terms of total polymer),
It has a number average molecular weight of approximately 60,000 and contains living lithium.
It had 1.65 mmol/100 g of polymer. Reference Example 7 Polymerization was carried out in exactly the same manner as in Reference Example 5, except that 35 times the mole of tetrahydrofuran was added to n-butyllithium, and the bound styrene content was 30%.
A styrene-butadiene-styrene type living block polymer was synthesized, which contained 25% blocked styrene, 38% 1,2-vinyl bonds in butadiene units, and had a number average molecular weight of about 60,000. The living lithium content in this polymer was 1.65 mmol/100 g of polymer. Reference Example 8 Cyclohexane was added at 1200 g/hr, 1,
3-butadiene monomer 210 g/hr, n-butyl lithium (n-BuLi) 1.33 g/hr, and tetrahydrofuran (THF) [n-BuLi/THF = 30 molar ratio] were continuously fed from the bottom of the reactor, and Styrene monomer was supplied from the upper part of the reactor at a rate of 90 g/hr, and polymerization was carried out at a polymerization temperature of 100° C. and an average residence time of 25 minutes, and a living polymer solution was continuously taken out from the reactor. The living copolymer obtained has a butadiene-styrene type structure, with a bound styrene content of 30%,
Blocked styrene content: 10.2%, butadiene unit 1,2-vinyl bond content: 40% (based on total polymer)
28%), and the number average molecular weight was approximately 180,000. This product contains living lithium per 100g of polymer.
It had 0.55 mmol. Reference example 9 400g of cyclohexane in an autoclave, 1,
13 g of 3-butadiene monomer, 0.15 g of n-butyllithium and tetrahydrofuran in a molar ratio of n
- Add BuLi/THF at a ratio of 40, polymerize at 70℃ for 45 minutes, then add 20g of styrene monomer and polymerize for 30 minutes.
Then, 47 g of 1,3-butadiene monomer was added and polymerized for 75 minutes, and finally 20 g of styrene monomer was added and polymerized for 30 minutes to synthesize a butadiene-styrene-butadiene-styrene type living block polymer. This product contains 40% bound styrene, 33% blocked styrene, and 1,2-butadiene units.
It had a vinyl bond content of 35% (30% based on total polymer), a number average molecular weight of about 60,000, and a living lithium content of 1.65 mmol per 100 g of living polymer. Reference Example 10 Styrene-
An isoprene-styrene living block copolymer was synthesized. It has 1.65 mmol of living lithium per 100 g of living polymer, with a bound styrene content of 30% and a blocked styrene content of 29.5
%, the 1,2-vinyl bond content of isoprene units was 10% (7% in terms of total polymer), and the number average molecular weight was about 60,000. Reference Example 11 0.5 mol of triethylamine was added to a cyclohexane solution containing 0.5 mol of sec-butyllithium, and the mixture was stirred at room temperature for 1 hour. Next, 0.25 mol of m-diisopropenylbenzene was added dropwise while stirring at room temperature for 3 hours, and stirring was continued for 24 hours at room temperature to form a cyclohexane solution of 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene. I got it. The purity of this dilithium was 98.7%, and the active lithium concentration was 2.00 mmol/g. 400 g of cyclohexane in an autoclave, 1,
70 g of 3-butadiene monomer and 1.40 g of the dilithium catalyst solution synthesized above (as active lithium)
2.80 mmol) was added and polymerized at 60°C for 3 hours. Next, 30 g of styrene monomer was added and polymerized at 60°C for 3 hours, resulting in a number average molecular weight of approximately 80,000, with a bound styrene content of 30%, a blocked styrene content of 29%, and a 1,2-vinyl bond content of butadiene units of 20%. A styrene-butadiene-styrene type diliving block polymer was obtained. The living lithium in this polymer was 2.50 mmol/100 g of polymer. Reference example 12 400g of cyclohexane in an autoclave, 1.
100 g of 3-butadiene monomer and a cyclohexane solution of 1,3-bis(1-lithio-1,3-dimethylpentyl)benzene shown in Reference Example 11
20.0 g (40 mmol as active lithium) was added and polymerized at 60° C. for 3 hours with stirring to synthesize diliving polybutadiene. This product had a number average molecular weight of about 6000, 35% 1,2-vinyl bonds, and 33.0 mmol of living lithium per 100 g of polymer. Examples 1 to 12 Each living polymer solution obtained in Reference Examples 1 and 2 was diluted with purified and dried toluene, and each living polymer solution obtained in Reference Examples 3 to 12 was diluted with purified and dried cyclohexane. The living polymer concentration was adjusted to 5% by weight and subjected to hydrogenation reaction. 1000 g of the living polymer solution (living polymer amount: 50 g) was charged into a sufficiently dried autoclave with a capacity of 2 and equipped with a stirrer, and the autoclave was degassed under reduced pressure, replaced with hydrogen, and maintained at 40° C. with stirring. Then, as a hydrogenation catalyst, the concentration was 1.0 mmol/100ml.
20.0 ml of a toluene solution (catalytic amount 0.20 mmol) of bis(cyclopentadienyl) titanium dichloride was charged into an autoclave at a rate of 5.0 Kg/cm 2
A hydrogenation reaction was carried out under stirring for 2 hours by supplying dry gaseous hydrogen. In all cases, hydrogen absorption was substantially completed within 30 minutes, and the reaction solution was a homogeneous, low-viscosity solution with a slightly black to gray-black color. The reaction solution was returned to normal temperature and pressure and taken out from the autoclave, and a large amount of methanol was added to precipitate the polymer, which was separated and dried to obtain a white hydrogen polymer. Table 1 summarizes the hydrogenation conditions, hydrogenation rate, and properties of the obtained hydrogenated polymer. As shown in Table 1, the conjugated diene units of all polymers were quantitatively hydrogenated, and the styrene units were hardly hydrogenated, indicating extremely good activity and selectivity.
【表】
実施例13〜19および比較例１，２
参考例７で合成したスチレン―ブタジエン―ス
チレン型リビングコポリマーを精製乾燥したシク
ロヘキサンで希釈しポリマー濃度10重量％とした
リビングポリマー溶液1000ｇ（ポリマー量100ｇ）
を乾燥した２オートクレーブに仕込み、乾燥水
素ガスで系内を置換し40℃に保持した。
次いで水添触媒として表２に示した各種チタニ
ウム化合物のトルエン溶液をリビングポリマー
100ｇに対して水添触媒量が0.50ミリモルになる
様に加えた後（リビングLi／Tiモル比＝3.3）、
5.0Kg／cm2の乾燥水素ガスを供給し、撹拌下40℃
にて１時間水添反応を行なつた。
水添後、実施例１と同様に処理し水添ポリマー
の性状等を調べた。
一方、比較例としてビス（シクロペンタジエニ
ル）チタニウム化合物以外のチタニウム化合物を
用いて同様に水添反応を行なつた。結果を表２に
示した。[Table] Examples 13 to 19 and Comparative Examples 1 and 2 The styrene-butadiene-styrene living copolymer synthesized in Reference Example 7 was diluted with purified and dried cyclohexane to give a polymer concentration of 10% by weight (1000 g of living polymer solution (polymer amount 100g)
was charged into a dry autoclave, and the system was purged with dry hydrogen gas and maintained at 40°C. Next, a toluene solution of various titanium compounds shown in Table 2 was added as a hydrogenation catalyst to a living polymer.
After adding the hydrogenation catalyst amount to 0.50 mmol per 100 g (living Li/Ti molar ratio = 3.3),
Supply 5.0Kg/cm 2 of dry hydrogen gas and heat at 40℃ with stirring.
The hydrogenation reaction was carried out for 1 hour. After hydrogenation, the polymer was treated in the same manner as in Example 1, and the properties of the hydrogenated polymer were examined. On the other hand, as a comparative example, a hydrogenation reaction was similarly carried out using a titanium compound other than the bis(cyclopentadienyl) titanium compound. The results are shown in Table 2.
【表】
実施例 20〜24
参考例５で合成したスチレン―ブタジエン―ス
チレン型リビングブロツクポリマーを乾燥したシ
クロヘキサンで希釈して濃度５重量％とし、実施
例１と同様の方法で水添した。
但し、水添触媒として用いたビス（シクロペン
タジエニル）チタニウムジクロライドの量は表３
に示した如くである。結果を表３に示した。[Table] Examples 20 to 24 The styrene-butadiene-styrene type living block polymer synthesized in Reference Example 5 was diluted with dry cyclohexane to a concentration of 5% by weight, and hydrogenated in the same manner as in Example 1. However, the amount of bis(cyclopentadienyl)titanium dichloride used as a hydrogenation catalyst is shown in Table 3.
As shown in The results are shown in Table 3.
【表】
実施例 25〜30
参考例９で合成したブタジエン―スチレン−ブ
タジエン―スチレン型リビングブロツクポリマー
を乾燥シクロヘキサンで希釈して濃度10重量％と
し、このリビングポリマー溶液1000ｇ（ポリマー
量100ｇ）を乾燥オートクレーブに仕込み、実施
例１と同様にして表４に示した各種条件で水添し
た。結果を表４に示した。[Table] Examples 25 to 30 The butadiene-styrene-butadiene-styrene type living block polymer synthesized in Reference Example 9 was diluted with dry cyclohexane to a concentration of 10% by weight, and 1000 g of this living polymer solution (polymer amount 100 g) was dried. The mixture was charged into an autoclave and hydrogenated in the same manner as in Example 1 under various conditions shown in Table 4. The results are shown in Table 4.
【表】【table】
【表】
実施例 31
参考例５と全く同様にしてスチレン―ブタジエ
ン―スチレン型リビングブロツクポリマーを合成
した。このリビングポリマーの一部をオートクレ
ーブから抜き出し分析したところ、結合スチレン
含有量30％、ブロツクスチレン含有量29％、ブタ
ジエン単位の１，２―ビニル結合13％で、数平均
分子量が約６万であつた。
重合後のリビングポリマーをオートクレーブ中
60℃、撹拌下に保持し、これに水添触媒として濃
度1.0ミリモル／100mlのビス（シクロペンタジエ
ニル）チタニウムジクロライドのトルエン溶液を
40.0ml仕込み（リビングLi／Ti比≒4.1）、直ちに
5.0Kg／cm2の乾燥水素ガスを供給し、60℃、撹拌
下２時間水添反応を行なつた。実質的な水素吸収
は約15分で終了し、反応液は微灰黒色の均一粘稠
溶液であつた。反応液を実施例１と同様に処理
し、白色の硬い熱可塑性エラストマー状のポリマ
ーを得た。水添率を測定したところ、ブタジエン
単位の水添率99％、スチレン単位の水添率１％以
下で分子量約６万の水添ポリマーであつた。本実
施例に示した如く、重合に続いて連続的にポリマ
ー水添を行なつても水添活性およびブタジエン単
位の水添選択性は何ら変らない結果を示した。
実施例 32
参考例５で合成したスチレン―ブタジエン―ス
チレン型リビングブロツクポリマーを乾燥シクロ
ヘキサンで希釈し濃度５重量％としたリビングポ
リマー溶液1000ｇ（ポリマー量50ｇ）を乾燥した
２オートクレーブに仕込み、乾燥水素ガスで置
換した。
これに濃度5.0ミリモル／100mlのベンジルクロ
ライドのシクロヘキサン溶液12.5mlを加え室温で
約10分撹拌して、リビングリチウム0.40ミリモ
ル／ポリマー100ｇのリビングポリマーを得た。
次いで実施例21と全く同様の方法で水添した。
但し、水添反応時のリビングLi／Tiモル比は約
４であつた。水添後実施例１と同様に処理し、白
色のポリマーを得た。このもののブタジエン単位
の水添率は98％、スチレン単位の水添率は１％以
下であり、リビングリチウムの一部を失活させて
も水添が可能である結果を示した。また実施例21
と比較してブタジエン単位の水添率は向上してお
り、水添時のリビングLi／Tiモル比が活性に影
響していることを示した。
比較例 ３
参考例７で得られたスチレン―ブタジエン―ス
チレン型リビングブロツクポリマーを乾燥シクロ
ヘキサンで希釈しポリマー濃度10％としたリビン
グポリマー溶液1000ｇ（ポリマー量100ｇ）を乾
燥した２オートクレーブに仕込み、乾燥水素ガ
スで系内を置換した。
これに濃度5.0ミリモル／100mlのベンジルクロ
ライドのシクロヘキサン溶液50mlを加え室温で約
10分撹拌した。ポリマー溶液の黄赤色なリビング
色は直ちに失色し微黄色透明となつた。このポリ
マーを分析したところ、すでにリビングリチウム
は全く失活したものであつた。
次いで実施例16と全く同様に水添反応を行な
い、実施例１と同様に処理して白色のポリマーを
得た。このもののブタジエン単位の水添率は１％
以下、スチレン単位の水添率も１％以下で、リビ
ングリチウムを保有しないポリマーは本発明のチ
タニウム化合物では水添されない結果を示した。[Table] Example 31 A styrene-butadiene-styrene type living block polymer was synthesized in exactly the same manner as in Reference Example 5. When a part of this living polymer was extracted from the autoclave and analyzed, it was found that the content of bound styrene was 30%, the content of blocked styrene was 29%, the 1,2-vinyl bond of the butadiene unit was 13%, and the number average molecular weight was approximately 60,000. Ta. Living polymer after polymerization in autoclave
The temperature was maintained at 60°C with stirring, and a toluene solution of bis(cyclopentadienyl)titanium dichloride at a concentration of 1.0 mmol/100 ml was added as a hydrogenation catalyst.
Prepare 40.0ml (living Li/Ti ratio≒4.1), immediately
Dry hydrogen gas of 5.0 kg/cm 2 was supplied, and the hydrogenation reaction was carried out at 60° C. for 2 hours with stirring. Substantial hydrogen absorption was completed in about 15 minutes, and the reaction solution was a slightly grayish black homogeneous viscous solution. The reaction solution was treated in the same manner as in Example 1 to obtain a white hard thermoplastic elastomer polymer. When the hydrogenation rate was measured, the hydrogenation rate of butadiene units was 99%, the hydrogenation rate of styrene units was 1% or less, and the hydrogenated polymer had a molecular weight of about 60,000. As shown in this example, the hydrogenation activity and hydrogenation selectivity of butadiene units did not change at all even if the polymerization was followed by continuous polymer hydrogenation. Example 32 The styrene-butadiene-styrene type living block polymer synthesized in Reference Example 5 was diluted with dry cyclohexane to give a concentration of 5% by weight. 1000 g of a living polymer solution (polymer amount 50 g) was charged into a dry autoclave and heated with dry hydrogen gas. Replaced with. To this was added 12.5 ml of a cyclohexane solution of benzyl chloride at a concentration of 5.0 mmol/100 ml, and the mixture was stirred at room temperature for about 10 minutes to obtain a living polymer containing 0.40 mmol of living lithium/100 g of polymer. Hydrogenation was then carried out in exactly the same manner as in Example 21.
However, the living Li/Ti molar ratio during the hydrogenation reaction was approximately 4. After hydrogenation, the same treatment as in Example 1 was carried out to obtain a white polymer. The hydrogenation rate of the butadiene unit in this product was 98%, and the hydrogenation rate of the styrene unit was 1% or less, indicating that hydrogenation was possible even if part of the living lithium was deactivated. Also Example 21
Compared to this, the hydrogenation rate of butadiene units was improved, indicating that the living Li/Ti molar ratio during hydrogenation affects the activity. Comparative Example 3 The styrene-butadiene-styrene type living block polymer obtained in Reference Example 7 was diluted with dry cyclohexane to give a polymer concentration of 10%. 1000 g of a living polymer solution (polymer amount 100 g) was charged into a dry autoclave and heated with dry hydrogen. The system was replaced with gas. Add 50 ml of a cyclohexane solution of benzyl chloride with a concentration of 5.0 mmol/100 ml to this and let it cool at room temperature.
Stir for 10 minutes. The yellow-red living color of the polymer solution immediately discolored and became slightly yellow and transparent. When this polymer was analyzed, it was found that living lithium had already been completely deactivated. Next, a hydrogenation reaction was carried out in exactly the same manner as in Example 16, and the same treatment as in Example 1 was carried out to obtain a white polymer. The hydrogenation rate of butadiene units in this product is 1%
Hereinafter, the hydrogenation rate of styrene units was also 1% or less, and the results showed that polymers that do not have living lithium are not hydrogenated with the titanium compound of the present invention.
Claims (1)
添する方法において、 (A) 有機リチウムを重合触媒として共役ジエンを
重合、または共役ジエンと共役ジエンと共重合
可能なモノマーを共重合して得られるリビング
ポリマー、を、 (B) 一般式【式】（但し、Ｒ，R′は 炭素原子数１〜８個のアルキル基、アリル基、ア
ルコキシ基、アリロキシ基、ハロゲン基、カルボ
ニル基から選択された基で、Ｒ，R′は同一でも
異なつていてもよい。）で示されるビス（シクロ
ペンタジエニル）チタニウム化合物の少なくとも
１種からなる水添触媒、 の存在下に水素と接触させ、該リビングポリマー
中の共役ジエン単位の不飽和二重結合を選択的に
水添することを特徴とするリビングポリマーの接
触水添方法。[Scope of Claims] 1. A method of hydrogenating a living polymer in an inert organic solvent, wherein (A) a conjugated diene is polymerized using an organolithium as a polymerization catalyst, or a conjugated diene and a monomer copolymerizable with the conjugated diene are used as a polymerization catalyst. The living polymer obtained by copolymerization has the following general formula: In the presence of a hydrogenation catalyst consisting of at least one bis(cyclopentadienyl) titanium compound represented by a group selected from carbonyl groups, R and R' may be the same or different. 1. A method for catalytic hydrogenation of a living polymer, comprising selectively hydrogenating unsaturated double bonds of conjugated diene units in the living polymer by bringing the living polymer into contact with hydrogen.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18698383A JPS6079005A (en) | 1983-10-07 | 1983-10-07 | Hydrogenation of living polymer |
| GB08400305A GB2134909B (en) | 1983-01-20 | 1984-01-06 | Catalytic hydrogenation of conjugated diene polymer |
| US06/568,692 US4501857A (en) | 1983-01-20 | 1984-01-06 | Method for hydrogenation of polymer |
| FR8400820A FR2539745B1 (en) | 1983-01-20 | 1984-01-19 | PROCESS FOR HYDROGENATION OF A CONJUGATED DIENE POLYMER |
| DE3448317A DE3448317C2 (en) | 1983-01-20 | 1984-01-20 | |
| DE19843401983 DE3401983A1 (en) | 1983-01-20 | 1984-01-20 | METHOD FOR SELECTIVE HYDROGENATION OF POLYMERS OR COPOLYMERS OF CONJUGATED SERVES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18698383A JPS6079005A (en) | 1983-10-07 | 1983-10-07 | Hydrogenation of living polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6079005A JPS6079005A (en) | 1985-05-04 |
| JPS635401B2 true JPS635401B2 (en) | 1988-02-03 |
Family
ID=16198143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18698383A Granted JPS6079005A (en) | 1983-01-20 | 1983-10-07 | Hydrogenation of living polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6079005A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806312B2 (en) | 2001-06-20 | 2004-10-19 | Asahu Kasei Kabushiki Kaisha | Thermoplastic resin composition |
| WO2008041356A1 (en) | 2006-10-03 | 2008-04-10 | Techno Polymer Co., Ltd. | Thermoplastic resin composition and resin molded article |
| WO2008062779A1 (en) | 2006-11-22 | 2008-05-29 | Techno Polymer Co., Ltd. | Resin composition for metal plating, molded article thereof, and metal-plated molded article |
| WO2014112411A1 (en) | 2013-01-16 | 2014-07-24 | 旭化成ケミカルズ株式会社 | Method for producing polymer |
| WO2015111674A1 (en) | 2014-01-23 | 2015-07-30 | 旭化成ケミカルズ株式会社 | Adhesive composition and adhesive tape |
| WO2015111675A1 (en) | 2014-01-23 | 2015-07-30 | 旭化成ケミカルズ株式会社 | Block copolymer and adhesive composition |
| WO2022176316A1 (en) | 2021-02-22 | 2022-08-25 | テクノＵｍｇ株式会社 | Thermoplastic resin composition for foam molding, and foam molded article thereof |
| WO2022195972A1 (en) | 2021-03-17 | 2022-09-22 | テクノＵｍｇ株式会社 | Thermoplastic composition and molded product thereof |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01101357A (en) * | 1987-10-14 | 1989-04-19 | Asahi Chem Ind Co Ltd | Block copolymer composition |
| JP3020807B2 (en) * | 1994-07-22 | 2000-03-15 | 三菱化学株式会社 | Airbag storage cover |
| JP2006199930A (en) | 2004-12-24 | 2006-08-03 | Advanced Plastics Compounds Co | Thermoplastic elastomer and molded product thereof |
| US20090312449A1 (en) * | 2006-02-13 | 2009-12-17 | Shigeru Sasaki | Hydrogenated block copolymer, resin composition comprising the hydrogenated block copolymer, and crosslinked product and crosslinked foamed product thereof |
| JP4921849B2 (en) * | 2006-05-09 | 2012-04-25 | 台橡股▲ふん▼有限公司 | Method for hydrogenating conjugated diene polymers |
| US20090152754A1 (en) | 2007-12-12 | 2009-06-18 | Sumitomo Chemical Company, Limited | Thermoplastic elastomer composition for foam injection molding, foam body, and process for producing foam body |
| US20090155537A1 (en) | 2007-12-12 | 2009-06-18 | Sumitomo Chemical Company, Limited | Process for producing thermoplastic elastomer composition foam body, and thermoplastic elastomer composition for foam injection molding |
| US8394892B2 (en) | 2009-09-14 | 2013-03-12 | Sumitomo Chemical Company, Ltd. | High performance thermoplastic elastomer composition |
| JP2011184503A (en) | 2010-03-05 | 2011-09-22 | Sumitomo Chemical Co Ltd | Thermoplastic elastomer composition |
| JP6663096B2 (en) | 2015-02-19 | 2020-03-11 | 住友化学株式会社 | Thermoplastic elastomer composition |
| EP3425003B1 (en) | 2016-03-03 | 2020-05-27 | MCPP Innovation LLC | Elastomer composition and medical container stopper formed by molding same |
| KR20180121911A (en) | 2016-03-18 | 2018-11-09 | 니폰 제온 가부시키가이샤 | METHOD FOR MANUFACTURING OBJECTS OF ORGANIC ELECTRONIC DEVICES |
| WO2018110590A1 (en) | 2016-12-14 | 2018-06-21 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer composition, extrusion-molded article, and medical tube |
| JP7196404B2 (en) | 2017-03-17 | 2022-12-27 | Ｍｃｐｐイノベーション合同会社 | Thermoplastic elastomer for adhesive lamination of carbon fiber reinforced plastics |
| EP4276149A1 (en) | 2021-01-07 | 2023-11-15 | Sumitomo Chemical Company, Limited | Thermoplastic resin composition and molded body |
-
1983
- 1983-10-07 JP JP18698383A patent/JPS6079005A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6806312B2 (en) | 2001-06-20 | 2004-10-19 | Asahu Kasei Kabushiki Kaisha | Thermoplastic resin composition |
| WO2008041356A1 (en) | 2006-10-03 | 2008-04-10 | Techno Polymer Co., Ltd. | Thermoplastic resin composition and resin molded article |
| WO2008062779A1 (en) | 2006-11-22 | 2008-05-29 | Techno Polymer Co., Ltd. | Resin composition for metal plating, molded article thereof, and metal-plated molded article |
| WO2014112411A1 (en) | 2013-01-16 | 2014-07-24 | 旭化成ケミカルズ株式会社 | Method for producing polymer |
| WO2015111674A1 (en) | 2014-01-23 | 2015-07-30 | 旭化成ケミカルズ株式会社 | Adhesive composition and adhesive tape |
| WO2015111675A1 (en) | 2014-01-23 | 2015-07-30 | 旭化成ケミカルズ株式会社 | Block copolymer and adhesive composition |
| WO2022176316A1 (en) | 2021-02-22 | 2022-08-25 | テクノＵｍｇ株式会社 | Thermoplastic resin composition for foam molding, and foam molded article thereof |
| WO2022195972A1 (en) | 2021-03-17 | 2022-09-22 | テクノＵｍｇ株式会社 | Thermoplastic composition and molded product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6079005A (en) | 1985-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS635401B2 (en) | ||
| JPS634841B2 (en) | ||
| JPH0137970B2 (en) | ||
| JP2718059B2 (en) | Polymer hydrogenation method and catalyst | |
| KR100201228B1 (en) | Process for hydrogenating living polymers | |
| JP3484155B2 (en) | Process for selective hydrogenation of polymers containing conjugated dienes | |
| JP2783791B2 (en) | Method for selective hydrogenation of conjugated diene polymers | |
| JPH0153851B2 (en) | ||
| JPH029041B2 (en) | ||
| KR100267080B1 (en) | Method for hydrogenation of conjugated diene polymer | |
| JPH0116401B2 (en) | ||
| JPH029043B2 (en) | ||
| EP0397026B1 (en) | Process for hydrogenation of polymers | |
| JPS635402B2 (en) | ||
| JPH029042B2 (en) | ||
| JP2609534B2 (en) | Method for hydrogenating olefinically unsaturated polymers | |
| JP2903471B1 (en) | Method for hydrogenating conjugated diene polymers | |
| JPH0496904A (en) | Hydrogenation of olefinic compound | |
| KR100295599B1 (en) | Hydrogenation of conjugated diene polymer | |
| KR100221358B1 (en) | New catalyst for hydrogenation of living polymer and hydrogenation process using it | |
| JP3651931B2 (en) | Hydrogenation of alkyl-substituted conjugated diene polymers | |
| KR100295601B1 (en) | Process for selective hydrogenation of conjugated diene polymer | |
| KR100332464B1 (en) | The selective hydrogenation catalyst for conjugated diene polymers and hydrogenation process using the same | |
| KR100356533B1 (en) | Method for the selective hydrogenation of the conjugated diene polymer | |
| KR100264514B1 (en) | Process for hydrogenation of conjugated diene polymer |