JPH02172537A - Hydrogenation catalyst and hydrogenation process - Google Patents
Hydrogenation catalyst and hydrogenation processInfo
- Publication number
- JPH02172537A JPH02172537A JP32599888A JP32599888A JPH02172537A JP H02172537 A JPH02172537 A JP H02172537A JP 32599888 A JP32599888 A JP 32599888A JP 32599888 A JP32599888 A JP 32599888A JP H02172537 A JPH02172537 A JP H02172537A
- Authority
- JP
- Japan
- Prior art keywords
- bis
- compound
- cyclopentagenyl
- hydrogenation
- component
- 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.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 90
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 229920000642 polymer Polymers 0.000 claims abstract description 100
- -1 olefin compound Chemical class 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 13
- CBKDTJXMXIYANY-UHFFFAOYSA-N cyclopentane;hafnium Chemical class [Hf].[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 CBKDTJXMXIYANY-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 23
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052735 hafnium Inorganic materials 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 13
- 150000002902 organometallic compounds Chemical class 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005336 allyloxy group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- MXVFWIHIMKGTFU-UHFFFAOYSA-N C1=CC=CC1[Hf] Chemical compound C1=CC=CC1[Hf] MXVFWIHIMKGTFU-UHFFFAOYSA-N 0.000 claims 1
- 150000002900 organolithium compounds Chemical class 0.000 claims 1
- 150000002901 organomagnesium compounds Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 21
- 150000002736 metal compounds Chemical class 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 13
- 150000001993 dienes Chemical class 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 6
- KSFCHHFBQJDGFF-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C1C=CC=C1.C1C=CC=C1 KSFCHHFBQJDGFF-UHFFFAOYSA-L 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 150000002363 hafnium compounds Chemical class 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UISYCPJKBYQJAD-UHFFFAOYSA-L Cl(=O)[O-].C(C)[Al+2].Cl(=O)[O-] Chemical compound Cl(=O)[O-].C(C)[Al+2].Cl(=O)[O-] UISYCPJKBYQJAD-UHFFFAOYSA-L 0.000 description 2
- OTBYHEYCZDPUAQ-UHFFFAOYSA-L Cl(=O)[O-].Cl(=O)[O-].[Ti+2] Chemical compound Cl(=O)[O-].Cl(=O)[O-].[Ti+2] OTBYHEYCZDPUAQ-UHFFFAOYSA-L 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 2
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 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
- LGAQJENWWYGFSN-PLNGDYQASA-N (z)-4-methylpent-2-ene Chemical compound C\C=C/C(C)C LGAQJENWWYGFSN-PLNGDYQASA-N 0.000 description 1
- CDQRAMODHKWJNN-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene-2,3-dicarbonitrile Chemical compound C1C2C=CC1C(C)(C#N)C2(C)C#N CDQRAMODHKWJNN-UHFFFAOYSA-N 0.000 description 1
- ZJBWPHQFMMXGBV-UHFFFAOYSA-N 2,6-dibutyl-6-methylcyclohexa-1,3-dien-1-ol Chemical compound CCCCC1=C(O)C(C)(CCCC)CC=C1 ZJBWPHQFMMXGBV-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- RSCIDCVEEKEQCR-UHFFFAOYSA-N 2-methylbicyclo[2.2.1]hept-5-ene-3-carbonitrile Chemical compound C1C2C=CC1C(C)C2C#N RSCIDCVEEKEQCR-UHFFFAOYSA-N 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-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
- DRWRVXAXXGJZIO-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl acetate Chemical compound C1C2C(OC(=O)C)CC1C=C2 DRWRVXAXXGJZIO-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UHFFFAOYSA-N 826-62-0 Chemical compound C1C2C3C(=O)OC(=O)C3C1C=C2 KNDQHSIWLOJIGP-UHFFFAOYSA-N 0.000 description 1
- ZRRIWXCJNWEKIZ-UHFFFAOYSA-M C(CCC)C1=C(O[Li])C(=CC(=C1)C)CCCC Chemical compound C(CCC)C1=C(O[Li])C(=CC(=C1)C)CCCC ZRRIWXCJNWEKIZ-UHFFFAOYSA-M 0.000 description 1
- JGACQGUYAONLLA-UHFFFAOYSA-M CCO[Ti]Cl Chemical compound CCO[Ti]Cl JGACQGUYAONLLA-UHFFFAOYSA-M 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- DCFDBASCBDIDJV-UHFFFAOYSA-L O([Hf]Oc1ccccc1)c1ccccc1 Chemical compound O([Hf]Oc1ccccc1)c1ccccc1 DCFDBASCBDIDJV-UHFFFAOYSA-L 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XYYOZIJFRRHUDN-UHFFFAOYSA-L [Br-].[Br-].C1(C=CC=C1)[Hf+2]C1C=CC=C1 Chemical compound [Br-].[Br-].C1(C=CC=C1)[Hf+2]C1C=CC=C1 XYYOZIJFRRHUDN-UHFFFAOYSA-L 0.000 description 1
- SZSUFWGDQRJYAH-UHFFFAOYSA-L [Br-].[Br-].[Hf+2] Chemical compound [Br-].[Br-].[Hf+2] SZSUFWGDQRJYAH-UHFFFAOYSA-L 0.000 description 1
- KUNZSLJMPCDOGI-UHFFFAOYSA-L [Cl-].[Cl-].[Hf+2] Chemical compound [Cl-].[Cl-].[Hf+2] KUNZSLJMPCDOGI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- ZTUUVDYQBLRAAC-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxamide Chemical compound C1C2C(C(=O)N)CC1C=C2 ZTUUVDYQBLRAAC-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 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
- 239000004020 conductor Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZOLLIQAKMYWTBR-UHFFFAOYSA-N cyclododeca-1,5,9-triene Chemical compound C1CC=CCCC=CCCC=C1 ZOLLIQAKMYWTBR-UHFFFAOYSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GWWKZPLMVIATIO-UHFFFAOYSA-L dibromozirconium Chemical compound Br[Zr]Br GWWKZPLMVIATIO-UHFFFAOYSA-L 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ZARLDNIZTZBEDV-UHFFFAOYSA-N dodeca-5,7-diene Chemical compound CCCCC=CC=CCCCC ZARLDNIZTZBEDV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229920006015 heat resistant resin Polymers 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
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 description 1
- OONWLILMXMWOMG-UHFFFAOYSA-M lithium;4-methylphenolate Chemical compound [Li+].CC1=CC=C([O-])C=C1 OONWLILMXMWOMG-UHFFFAOYSA-M 0.000 description 1
- LTRVAZKHJRYLRJ-UHFFFAOYSA-N lithium;butan-1-olate Chemical compound [Li+].CCCC[O-] LTRVAZKHJRYLRJ-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- UUPFWVQZXYTRSK-UHFFFAOYSA-N lithium;heptan-1-olate Chemical compound [Li+].CCCCCCC[O-] UUPFWVQZXYTRSK-UHFFFAOYSA-N 0.000 description 1
- PPXOATAYFFLLBM-UHFFFAOYSA-N lithium;hexan-1-olate Chemical compound [Li+].CCCCCC[O-] PPXOATAYFFLLBM-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- VVKLZHZYBZPWIN-UHFFFAOYSA-N lithium;pentan-1-olate Chemical compound [Li]OCCCCC VVKLZHZYBZPWIN-UHFFFAOYSA-N 0.000 description 1
- XAVQZBGEXVFCJI-UHFFFAOYSA-M lithium;phenoxide Chemical compound [Li+].[O-]C1=CC=CC=C1 XAVQZBGEXVFCJI-UHFFFAOYSA-M 0.000 description 1
- WVHPRHPUFLPMMM-UHFFFAOYSA-N lithium;phenylmethanolate Chemical compound [Li]OCC1=CC=CC=C1 WVHPRHPUFLPMMM-UHFFFAOYSA-N 0.000 description 1
- MXIRPJHGXWFUAE-UHFFFAOYSA-N lithium;propan-1-olate Chemical compound [Li+].CCC[O-] MXIRPJHGXWFUAE-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000010551 living anionic polymerization reaction Methods 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- AEBDJCUTXUYLDC-UHFFFAOYSA-N methyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C)CC1C=C2 AEBDJCUTXUYLDC-UHFFFAOYSA-N 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DHMDYNNHVASVMA-UHFFFAOYSA-N n,n-diethylbicyclo[2.2.1]hept-2-ene-5-carboxamide Chemical compound C1C2C(C(=O)N(CC)CC)CC1C=C2 DHMDYNNHVASVMA-UHFFFAOYSA-N 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 125000002734 organomagnesium group Chemical group 0.000 description 1
- WLVPQQDEYVVXJF-UHFFFAOYSA-N phenyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C(C=C2)CC2C1C(=O)OC1=CC=CC=C1 WLVPQQDEYVVXJF-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- HDORWHHGSNVCBS-UHFFFAOYSA-L titanium(2+);diphenoxide Chemical compound [Ti+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HDORWHHGSNVCBS-UHFFFAOYSA-L 0.000 description 1
- QUOXUNGHPAHJIL-UHFFFAOYSA-J titanium(4+) tetrachlorite Chemical compound [Ti+4].[O-][Cl]=O.[O-][Cl]=O.[O-][Cl]=O.[O-][Cl]=O QUOXUNGHPAHJIL-UHFFFAOYSA-J 0.000 description 1
- WDVUXWDZTPZIIE-UHFFFAOYSA-N trichloro(2-trichlorosilylethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC[Si](Cl)(Cl)Cl WDVUXWDZTPZIIE-UHFFFAOYSA-N 0.000 description 1
- LQUJCRPJNSUWKY-UHFFFAOYSA-N trichloro(dichloromethyl)silane Chemical compound ClC(Cl)[Si](Cl)(Cl)Cl LQUJCRPJNSUWKY-UHFFFAOYSA-N 0.000 description 1
- YWUUHVWMPSPGQO-UHFFFAOYSA-N trichloro(trichloromethyl)silane Chemical compound ClC(Cl)(Cl)[Si](Cl)(Cl)Cl YWUUHVWMPSPGQO-UHFFFAOYSA-N 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- BIBZKNXZTAKPDB-UHFFFAOYSA-N trichloro-(2,3-dichlorophenyl)silane Chemical compound ClC1=CC=CC([Si](Cl)(Cl)Cl)=C1Cl BIBZKNXZTAKPDB-UHFFFAOYSA-N 0.000 description 1
- CLXMTJZPFVPWAX-UHFFFAOYSA-N trichloro-[dichloro(trichlorosilyloxy)silyl]oxysilane Chemical compound Cl[Si](Cl)(Cl)O[Si](Cl)(Cl)O[Si](Cl)(Cl)Cl CLXMTJZPFVPWAX-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- HBHGYYRJPVXCQQ-UHFFFAOYSA-L zirconium(2+);diphenoxide Chemical compound [Zr+2].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 HBHGYYRJPVXCQQ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は水素添加触媒およびこれを用いた水素添加方法
に関し、詳しくは触媒調製後長時間触媒自体が安定し、
高い水添活性を持続し、さらにオレフィン性不飽和二重
結合金有ポリマーの水添反応に用いて優れた耐候性、耐
熱性、耐酸性等を付与することのできる水素添加触媒お
よびこれを用いた水素添加方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a hydrogenation catalyst and a hydrogenation method using the same, and specifically, the catalyst itself is stable for a long time after catalyst preparation,
A hydrogenation catalyst that maintains high hydrogenation activity and can be used in the hydrogenation reaction of olefinically unsaturated double bond gold-containing polymers to impart excellent weather resistance, heat resistance, acid resistance, etc., and the use thereof. The present invention relates to a hydrogenation method.
［従来の技術］
オレフィン性不飽和二重結合金有ポリマーに耐候性、耐
熱性、耐酸性等を付与する目的で該ポリマーの水添に用
いる触媒としては、ニッケル、コバルト、チタン等の有
機金属化合物等と有機アルミニウム、有機マグネシウム
、有機リチウム等の還元性化合物とを溶媒中で反応して
得られる均一系触媒が一般に知られている。この均−一
系触媒は不均一系触媒に較べて活性が高く、触媒の使用
ｔ１が少なくて済み、より温和な条件で水添できるとい
う特徴がある。[Prior Art] Organic metals such as nickel, cobalt, and titanium are used as catalysts for hydrogenation of olefinically unsaturated double-bonded gold-containing polymers for the purpose of imparting weather resistance, heat resistance, acid resistance, etc. to the polymers. Homogeneous catalysts obtained by reacting compounds and reducing compounds such as organoaluminum, organomagnesium, organolithium, etc. in a solvent are generally known. This homogeneous catalyst has higher activity than a heterogeneous catalyst, requires less catalyst usage t1, and can perform hydrogenation under milder conditions.
［発明が解決しようとしている課題Ｊ
しかし、約−系触媒はその触媒成分を混合し還元した際
の還元状態によっては水添活性が十分に発現しない場合
があった。更に、反応系中に存在する不純物により触媒
成分が容易に単語性化されるため触媒の安定性に欠ける
ので、繰り返し水添反応を行った場合の再現性が低いと
いう欠点を有していた。[Problem to be Solved by the Invention J] However, the hydrogenation activity of the about-type catalyst may not be sufficiently expressed depending on the reduction state when the catalyst components are mixed and reduced. Furthermore, impurities present in the reaction system easily convert the catalyst components into monomers, resulting in a lack of catalyst stability, which has the disadvantage of low reproducibility when repeated hydrogenation reactions are carried out.
また、水添反応の再現性が低いためオレフィン性不飽和
二重結合金有ポリマーに優れた耐候性、耐熱性、耐酸性
を有効に付与することが困難であった。Furthermore, because the reproducibility of the hydrogenation reaction is low, it has been difficult to effectively impart excellent weather resistance, heat resistance, and acid resistance to the olefinically unsaturated double bond gold-containing polymer.
従って、本発明の目的は、高い水添活性を有し、しかも
触媒自体の安定性に優れて長時間高い活性を持続する水
素添加触媒、およびこれを用いた水素添加方法を提供す
ることにある。本発明の他の目的は、オレフィン性不飽
和二重結合金有ポリマーの水添に用いて、優れ耐候性、
耐熱性、１１酸ｆ１笠を付与する水素添触媒、およびこ
れを用いた水素添加方法を提供することにある。Therefore, an object of the present invention is to provide a hydrogenation catalyst that has high hydrogenation activity and maintains high activity for a long time due to the excellent stability of the catalyst itself, and a hydrogenation method using the same. . Another object of the present invention is to provide excellent weather resistance,
It is an object of the present invention to provide a hydrogenation catalyst that imparts heat resistance and 11 acid f1 capacity, and a hydrogenation method using the same.
［課題を解決するための手段］
本発明者は、均一系触媒の萌述の欠点を改良し一定性状
水添ボリマーが得られる触媒に関して鋭意検討した結果
、オレフィン化合物とビス（シクロベンジェニル）チタ
ニウム化合物等と還元性有機金属化合物とからなる触媒
成分を混合することにより得られた触媒が極めて高い活
性を長時間持続し、しかも再現性良く、高速度で安定し
て高水添ポリマーを与えることを見い出し、本発明に至
ったものである。[Means for Solving the Problems] As a result of intensive studies on catalysts that can improve the disadvantages of homogeneous catalysts and obtain hydrogenated polymers with constant properties, the present inventors discovered that an olefin compound and bis(cyclobengenyl) titanium It was discovered that a catalyst obtained by mixing a catalyst component consisting of a compound, etc. and a reducing organometallic compound maintains extremely high activity for a long time, and can stably produce highly hydrogenated polymers with good reproducibility and at high speed. , which led to the present invention.
すなわち１本発明は、（Ａ）オレフィン化合物の少なく
とも１種、（Ｂ）ビス（シクロペンタジェニル）チタニ
ウム化合物、ビス（シクロペンタジェニル）ジルコニウ
ム化合物、ビス（シクロペンタジェニル）ハフニウム化
合物の少なくとも１種、および（Ｃ）還元性有機金属化
合物の少なくとも１種を混合してなり、好ましくは（Ａ
）成分の二重結合含有１ｉｔ／（Ｂ）成分（モル比）が
２０／１以上でかつ、（Ｃ）成分／（Ｂ）成分（モル比
）が０．５／Ｉ〜２０／Ｉである水素添加触媒、並びに
ト記触媒を用いて２０〜１００℃、水素圧４〜２０ ｋ
ｇ／ ｃｍ”下で反応させるオレフィン性二重結合含有
ポリマーの水素添加方法である。That is, 1 the present invention provides at least one of (A) an olefin compound, (B) a bis(cyclopentagenyl) titanium compound, a bis(cyclopentagenyl) zirconium compound, and a bis(cyclopentagenyl) hafnium compound. and (C) at least one reducing organometallic compound, preferably (A
) The double bond content of component 1it/(B) component (molar ratio) is 20/1 or more, and the (C) component/(B) component (molar ratio) is 0.5/I to 20/I. 20 to 100°C and hydrogen pressure of 4 to 20 k using a hydrogenation catalyst and the above catalyst
This is a method for hydrogenating polymers containing olefinic double bonds in which the reaction is carried out under 100 g/cm”.
本発明の水素添加触媒について具体的に説明する。The hydrogenation catalyst of the present invention will be specifically explained.
本発明においては触媒（Ａ）成分のオレフィン化合物と
してオレフィンモノマー、オレフィンポリマーのいずれ
も用いられる。In the present invention, both olefin monomers and olefin polymers can be used as the olefin compound of the catalyst (A) component.
オレフィンモノマーとしては炭素数５〜８の千ノオレフ
ィンが好ましく具体例としては、シクロベンゾン、シク
ロヘキセン、シクロオクデン、２−ペンテン２２−ヘキ
セン、３−ヘキセン。As the olefin monomer, olefins having 5 to 8 carbon atoms are preferable, and specific examples thereof include cyclobenzone, cyclohexene, cycloocdene, 2-pentene, 22-hexene, and 3-hexene.
２−ヘプテン、３−ヘプテン、２−メチル−２−ブテン
、４−メチル−２−ペンテンが挙げられる。Examples include 2-heptene, 3-heptene, 2-methyl-2-butene, and 4-methyl-2-pentene.
また、オレフィンポリマーの具体例としては。Also, as a specific example of olefin polymer.
ポリブタジェン、ポリイソプレン、ポリジメチルブタジ
ェン、ブタジェン−スチレンランダムコポリマー、ブタ
ジエンーイソブレンランダムフボリマー、ブタジェン−
アクリルニトリルランダムコポリマー、ブタジェン−ａ
−メチルスチレンセンダ１１コポリマー、スチレン−ブ
タジェン−スチレンブロックコポリマー、スチレン−イ
ソプレン−スチレンブロックコポリマーが挙げられる。Polybutadiene, polyisoprene, polydimethylbutadiene, butadiene-styrene random copolymer, butadiene-isoprene random fubolymer, butadiene-
Acrylonitrile random copolymer, butadiene-a
-Methylstyrene sender 11 copolymer, styrene-butadiene-styrene block copolymer, and styrene-isoprene-styrene block copolymer.
（Ａ）成分の添加けは、後述の触媒（Ｂ）成分に対して
、好ましくは（Ａ）成分の二用結合金有量／（Ｂ）成分
＝２０／１ （モル比）以上、実用トより好ましくは＋
ｏｏ ／ １〜２００口／！である。Component (A) is preferably added to the catalyst (B) component described below, preferably at a ratio of dual bond content of component (A)/component (B) = 20/1 (molar ratio) or more. More preferably +
oo / 1-200 mouths /! It is.
２０／＋ （モル比）未満では、触媒活性が不充分で
ポリマーの水添が困難になる傾向がある。If the molar ratio is less than 20/+, the catalyst activity tends to be insufficient and hydrogenation of the polymer tends to become difficult.
なお、（Ａ）成分の二重結合含有Ｒｔとはオレフィンモ
ノマーを用いた場合はその使用ミリモル数、オレフィン
ポリマーを用いた場合はポリマー中に二重結合を付与し
た千ツマ−のミリモル数を指す６
次に、本発明の触媒（Ｂ）成分に用いられるビス（シク
ロペンタジェニル）チタニウム化合物、ビス（シクロペ
ンタジェニル）ジルコニウム化合物、ビス（シクロペン
タジェニル）ハフニウム化合物は、〜最大（１）
％式％（１）
［式中、Ｍは１”ｉ、Ｚｒまたは１１「であり、Ｒ１■
＜２はハロゲン原子、炭化水素基、アリロキシＪｌｌ、
、アルコキシ基またはカルボニル基であり、Ｒ’、１１
”は同一であっても異っていてもよい］で示される化合
物である。In addition, the double bond content Rt of component (A) refers to the number of millimoles used when an olefin monomer is used, and the number of millimoles of double bonds added to the polymer when an olefin polymer is used. 6 Next, the bis(cyclopentadienyl) titanium compound, bis(cyclopentajenyl) zirconium compound, and bis(cyclopentajenyl) hafnium compound used in the catalyst (B) component of the present invention has a maximum of (1 ) %Formula%(1) [In the formula, M is 1"i, Zr or 11", and R1■
<2 is a halogen atom, a hydrocarbon group, an allyloxy Jll,
, is an alkoxy group or a carbonyl group, and R', 11
” may be the same or different].
（Ｂ）成分に用いられるビス（シクロペンタジェニル）
チタニウム化合物の具体例としては、ビス（シクロペン
タジェニル）チタニウムジメチル、ビス（シクロペンタ
ジェニル）チタニウムジエチル、ビス（シクロペンタジ
ェニル）チタニウムジ−ローブチル、ビス（シクロペン
タジェニル）チタニウムジー５ｅｃ−ブチル、ビス（シ
クロペンタジェニル）チタニウムジエチル、ビス（シク
ロペンタジェニル）チタニウムジオクチル、ビス（シク
ロペンタジェニル）チタニウムジェトキシド、ビス（シ
クロペンタジェニル）チタニウムジェトキシド、ビス（
シクロペンタジェニル）チタニウムジェトキシド、ビス
（シクロペンタジェニル）チタニウムジフェニル、ビス
（シクロペンタジェニル）チタニウムジ−ｍ−トリル、
ビス（シクロペンタジェニル）チタニウムジ−ｐ−トリ
ル、ビス（シクロペンタジェニル）チタニウムジーｍ、
ｐ−キシリル、ビス（シクロペンタジェニル）チタニウ
ムジー４−エチルフェニル、ビス（シクロペンタジェニ
ル）チタニウムジー４−ブチルフェニル、ビス（シクロ
ペンタジェニル）チタニウムジー４−へキシルフェニル
。Bis(cyclopentagenyl) used in component (B)
Specific examples of titanium compounds include bis(cyclopentagenyl)titanium dimethyl, bis(cyclopentagenyl)titanium diethyl, bis(cyclopentagenyl)titanium di-robethyl, and bis(cyclopentagenyl)titanium di-5ec. -butyl, bis(cyclopentagenyl)titanium diethyl, bis(cyclopentagenyl)titanium dioctyl, bis(cyclopentagenyl)titanium jetoxide, bis(cyclopentagenyl)titanium jetoxide, bis(
cyclopentagenyl) titanium jetoxide, bis(cyclopentagenyl) titanium diphenyl, bis(cyclopentagenyl) titanium di-m-tolyl,
bis(cyclopentagenyl) titanium di-p-tolyl, bis(cyclopentagenyl) titanium di-m,
p-xylyl, bis(cyclopentagenyl) titanium di-4-ethylphenyl, bis(cyclopentagenyl) titanium di-4-butylphenyl, bis(cyclopentagenyl) titanium di-4-hexylphenyl.
ビス（シクロペンタジェニル）ヂタニウムジフェノキシ
ド、ビス（シクロペンタジェニル）チタニウムジクロラ
イト、ビス（シクロペンタジェニル）チタニウムジクロ
ライト、ビス（シクロペンタジェニル）グ・タニウムブ
ロマイド、ビス（シクロペンタジェニル）ヂタニウムジ
イオダ・イド、ビス（シクロペンタジェニル）チタニウ
ムジカルボニル、ビス（シクロペンタジェニル）チタニ
ウムクロライトメデル、ビス（シクロペンタジェニル）
チタニウムクロライドエトキサイド、ビス（シクロペン
タジェニル）チタニウムクロライドフェノキシト、ビス
（シクロペンタジェニル）チタニウムベンジル等が挙げ
られ、単独あるいは相互に組み合わせて用いることがで
きる。これらビス（シクロペンタジェニル）チタニウム
化合物のうち、ポリマー中のオレフィン性不飽和二重結
合に対する水添活性が高く、かつ温和な条件で不飽和二
重結合を良好に選択的に水添する好ましいものとしては
、ビス（シクロペンタジェニル）チタニウムジメチル、
ビス（シクロペンタジェニル）チタニウムジ−ｎ−ブチ
ル、ビス（シクロペンタジェニル）チタニウムジクロラ
イト、ビス（シクロペンタジェニル）チタニウムジフェ
ニル、ビス（シクロペンタジェニル）チタニウムジ−ｐ
−トリル、ビス（シクロペンタジェニル）チタニウムジ
カルボニル、ビス（シクロペンタジェニル）チタニウム
ジベンジルが挙げられ、最も好ましいものはビス（シク
ロペンタジェニル）チタニウムジクロライトである。Bis(cyclopentagenyl) titanium diphenoxide, bis(cyclopentagenyl) titanium dichlorite, bis(cyclopentagenyl) titanium dichlorite, bis(cyclopentagenyl) titanium bromide, bis( cyclopentagenyl) ditanium diiodide, bis(cyclopentagenyl) titanium dicarbonyl, bis(cyclopentagenyl) titanium chlorite medel, bis(cyclopentagenyl)
Examples include titanium chloride ethoxide, bis(cyclopentagenyl)titanium chloride phenoxyto, bis(cyclopentagenyl)titanium benzyl, and the like, which can be used alone or in combination with each other. Among these bis(cyclopentagenyl) titanium compounds, preferred are those that have high hydrogenation activity toward olefinically unsaturated double bonds in the polymer and can selectively hydrogenate unsaturated double bonds under mild conditions. Examples include bis(cyclopentagenyl)titanium dimethyl,
Bis(cyclopentagenyl)titanium di-n-butyl, bis(cyclopentagenyl)titanium dichlorite, bis(cyclopentagenyl)titanium diphenyl, bis(cyclopentagenyl)titanium di-p
-tolyl, bis(cyclopentagenyl)titanium dicarbonyl, bis(cyclopentagenyl)titanium dibenzyl, and the most preferred one is bis(cyclopentagenyl)titanium dichlorite.
（Ｂ）成分に用いられるビス（シクロペンタジエニｌし
）ジルコニウム化合物の具体例としては。Specific examples of the bis(cyclopentadienyl)zirconium compound used in component (B) include:
ビス（シクロペンタジェニル）ジルコニウムジメチル、
ビス（シクロペンタジェニル）ジルコニウムジエチル、
ビスくシクロペンタジェニル）ジルコニウムジー〇−ブ
ヂル、ビス（シクロペンタジェニル）ジルコニウムジー
５ｅｃ−ブチル、ビス（シクロペンタジェニル）ジルコ
ニウムジオクチル、ビス（シクロペンタジェニル）ジル
コニウムジオクチル、ビス（シクロペンタジェニル）ジ
ルコニウムジェトキシド、ビス（シクロペンタジェニル
）ジルコニウムジェトキシド、ビス（シクロペンタジェ
ニル）ジルコニウムジェトキシド、ビス（シクロペンタ
ジェニル）ジルコニウムジフェニル、ビス（シクロペン
タジェニル）ジルコニウムジ−ｍ−トリル、ビス（シク
ロペンタジェニル）ジルコニウムジ−ｐ−トリル、ビス
（シクロペンタジェニル）ジルコニウムジーｍ、ｐ−キ
シリル、ビス（シクロペンタジェニル）ジルコニウムジ
ー４−エチルフェニル、ビス（シクロペンタジェニル）
ジルコニウムジフェノキシド、ビス（シクロペンタジェ
ニル）ジルコニウムジフル才うイト、ビス（シクロペン
タジェニル）ジルコニウムジクロライド、ビス（シクロ
ペンタジェニル）ジルコニウムジブロマイド、ビス（シ
クロペンタジェニル）ジルコニウムジオクチル、ビス（
シクロペンタジェニル）ジルコニウムジカルボニル、ビ
ス（シクロペンタジェニル）ジルコニウムクロライドメ
チル、等が挙げられ、単独あるいは相互に絹み合わせて
用いることができる。これらビス（シクロペンタジェニ
ル）ジルコニウム化合物のうち、ポリマー中のオレフィ
ン性不飽和二重結合に対する水添活性が高く、かつ温和
な条件で不飽和二重結合を良好に選択的に水添する好ま
しいものとしては、ビス（シクロペンタジェニル）ジル
コニウムジメチル、ビス（シクロペンタジェニル）ジル
コニウムジ−ｎ−ブチル、ビス（シクロペンタジェニル
）ジルコニウムジクロライド、ビス（シクロペンタジェ
ニル）ジルコニウムジブロマイド、ビス（シクロペンタ
ジェニル）ジルコニウムジフェニル、ビス（シクロペン
タジェニル）ジルコニウムジ−ｐ−トリル、ビス（シク
ロペンタジェニル）ジルコニウムジカルボニルが挙げら
れる。さらに安定に取り扱え、（Ｃ）成分の還元性金属
化合物と組み合わせた場合、最も活性の発現しやすいよ
り好ましいものはビス（シクロペンタジェニル）ジルコ
ニウムジクロライド、ビス（シクロペンタジェニル）ジ
ルコニウムジブロマイド、ビス（シクロペンタジェニル
）ジルコニウムジフェニル、ビス（シクロペンタジェニ
ル）ジルコニウムジ−ｍ−トリルであり、ビス（シクロ
ペンタジェニル）ジルコニウムジーｐ−）リルは溶解性
にも優れるので最も好ましい。bis(cyclopentadienyl)zirconium dimethyl,
bis(cyclopentadienyl)zirconium diethyl,
Bis(cyclopentadienyl)zirconium di-butyl, bis(cyclopentadienyl)zirconium di-5ec-butyl, bis(cyclopentadienyl)zirconiumdioctyl, bis(cyclopentadienyl)zirconiumdioctyl, bis(cyclopentagenyl)zirconiumdioctyl bis(cyclopentadienyl)zirconium jetoxide, bis(cyclopentajenyl)zirconium jetoxide, bis(cyclopentajenyl)zirconium diphenyl, bis(cyclopentajenyl)zirconium di-m -Tolyl, bis(cyclopentagenyl)zirconium di-p-tolyl, bis(cyclopentagenyl)zirconium di-m,p-xylyl, bis(cyclopentagenyl)zirconium di-4-ethylphenyl, bis(cyclopentadienyl)zirconium di-4-ethylphenyl, Genil)
Zirconium diphenoxide, bis(cyclopentagenyl) zirconium difluorite, bis(cyclopentagenyl) zirconium dichloride, bis(cyclopentagenyl) zirconium dibromide, bis(cyclopentagenyl) zirconium dioctyl, bis(
Examples include cyclopentagenyl) zirconium dicarbonyl, bis(cyclopentagenyl) zirconium chloride methyl, and the like, which can be used alone or in combination with each other. Among these bis(cyclopentagenyl) zirconium compounds, preferred are those that have high hydrogenation activity toward olefinically unsaturated double bonds in the polymer and can selectively hydrogenate unsaturated double bonds under mild conditions. Examples include bis(cyclopentagenyl)zirconium dimethyl, bis(cyclopentagenyl)zirconium di-n-butyl, bis(cyclopentagenyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dibromide, bis(cyclopentagenyl)zirconium dibromide, (Cyclopentagenyl)zirconium diphenyl, bis(cyclopentagenyl)zirconium di-p-tolyl, and bis(cyclopentagenyl)zirconium dicarbonyl. The more preferred ones are bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentagenyl)zirconium dibromide, which can be handled more stably and exhibit the most activity when combined with the reducing metal compound of component (C). These are bis(cyclopentagenyl)zirconium diphenyl and bis(cyclopentagenyl)zirconium di-m-tolyl, and bis(cyclopentagenyl)zirconium di-p-)lyl is the most preferred because it has excellent solubility.
（Ｂ）成分に用いられるビス（シクロペンタジェニル）
ハフニウム化合物の具体例としては、ビス（シクロペン
タジェニル）ハフニウムジメチル、ビス（シクロペンタ
ジェニル）ハフニウムジエチル、ビス（シクロペンタジ
ェニル）ハフニウムジー〇−ブヂル、ビス（シクロペン
タジェニル）ハフニウムジー５ＣＣ−ブチル、ビス（シ
クロペンタジェニル）ジヘキシル、ビス（シクロペンタ
ジェニル）ハフニウムジェトキシド、ビス（シクロペン
タジェニル）ハフニウムジェトキシド。Bis(cyclopentagenyl) used in component (B)
Specific examples of hafnium compounds include bis(cyclopentagenyl) hafnium dimethyl, bis(cyclopentagenyl) hafnium diethyl, bis(cyclopentagenyl) hafnium di-butyl, and bis(cyclopentagenyl) hafnium dimethyl. 5CC-butyl, bis(cyclopentagenyl) dihexyl, bis(cyclopentagenyl) hafnium jetoxide, bis(cyclopentagenyl) hafnium jetoxide.
ビス（シクロペンタジェニル）ハフニウムジェトキシド
、ビス（シクロペンタジェニル）ハフニウムジフェニル
、ビス（シクロペンタジェニル）ハフニウムジ−ｍ−ト
リル、ビス（シクロペンタジェニル）ハフニウムジ−ｐ
−１−リル、ビス（シクロペンタジェニル）ハフニウム
ジーｍ。ｐ−キシリル、ビス（シクロペンタジェニル）
ハフニウムジフェノキシド、ビス（シクロペンタジェニ
ル）ハフニウムジクロライト、ビス（シクロペンタジェ
ニル）ハフニウムジクロライト、ビス（シクロペンタジ
ェニル）ハフニウムジクロライト、ビス（シクロペンタ
ジェニル）ハフニウムジイ才ダイド、ビス（シクロペン
タジェニル）ハフニウムジカルボニル、ビス（シクロペ
ンタジェニル）ハフニウムクロライドメチル、等が挙げ
られ、単独あるいは相仔に組み合わせて用いることがで
きる。これらビス（シクロペンタジェニル）ハフニラ１
１化合物のうち、ポリマー中のオレフィン性不飽和二屯
結合に対する水添活性が高く、かつ温和な条件で不飽和
二重結合を良好に選択的に水添する好ましいものとして
は、ビス（シクロペンタジェニル）ハフニウムジメチル
、ビス（シクロペンタジエニル）ハフニウムジ−ｎ−ブ
チル、ビス（シクロペンタジェニル）ハフニウムジクロ
ライト、ビス（シクロペンタジェニル）ハフニウムジブ
ロマイド、ビス（シクロペンタジェニル）ハフニウムジ
フェニル、ビス（シクロペンタジェニル）ハフニウムジ
−ｐ−トリル、ビス（シクロペンタジェニル）ハフニウ
ムジカルボニルが挙げられる。さらに安定に取扱え、（
Ｃ）成分の還元性金属化合物と組み合わせた場合最も活
性の発現しやすいより好ましいものはビス（シクロペン
タジェニル）ハフニウムジクロライド、ビス（シクロペ
ンタジェニル）ハフニウムジブロマイド、ビス（シクロ
ペンタジェニル）ハフニウムジフェニル、ビス（シクロ
ペンタジェニル）ハフニウムジー１）−トリルであり、
ビス（シクロペンタジェニル）へフニウムジーｐ−トリ
ルは溶解性にも優れるので彼も好ましい。Bis(cyclopentagenyl)hafnium jetoxide, bis(cyclopentagenyl)hafnium diphenyl, bis(cyclopentagenyl)hafnium di-m-tolyl, bis(cyclopentagenyl)hafnium di-p
-1-lyl, bis(cyclopentagenyl) hafnium di-m. p-xylyl, bis(cyclopentagenyl)
Hafnium diphenoxide, bis(cyclopentagenyl) hafnium dichlorite, bis(cyclopentagenyl) hafnium dichlorite, bis(cyclopentagenyl) hafnium dichlorite, bis(cyclopentagenyl) hafnium dihydride, bis Examples include (cyclopentagenyl) hafnium dicarbonyl, bis(cyclopentagenyl) hafnium chloride methyl, and the like, which can be used alone or in combination. These bis(cyclopentadienyl) hafnira 1
Among the compounds, bis(cyclopentane) is a preferable compound that has high hydrogenation activity toward olefinic unsaturated double bonds in the polymer and can selectively hydrogenate unsaturated double bonds under mild conditions. bis(cyclopentadienyl) hafnium dimethyl, bis(cyclopentadienyl) hafnium di-n-butyl, bis(cyclopentadienyl) hafnium dichlorite, bis(cyclopentadienyl) hafnium dibromide, bis(cyclopentadienyl) hafnium diphenyl , bis(cyclopentagenyl) hafnium di-p-tolyl, and bis(cyclopentagenyl) hafnium dicarbonyl. It can be handled more stably, (
The preferred compounds that exhibit the most activity when combined with the reducing metal compound of component C) are bis(cyclopentagenyl) hafnium dichloride, bis(cyclopentagenyl) hafnium dibromide, and bis(cyclopentagenyl). hafnium diphenyl, bis(cyclopentagenyl) hafnium di-1)-tolyl,
Bis(cyclopentagenyl)hefnium di-p-tolyl is also preferred because it has excellent solubility.
次に、還元能力を有する有機金属化合物を触媒（Ｃ）成
分として加える。Next, an organometallic compound having reducing ability is added as the catalyst (C) component.
この還元性有機金属化合物として、アルミニウム化合物
、亜鉛化合物、マグネシウム化合物を（Ｃ）成分のチタ
ニウム等の化合物／（Ｂ）成分の還元性有機金属化合物
（モル比）＝０．５／Ｉ〜２０／ｌの割合で加えると、
さらに一定の高水添ポリマーが得られる。As the reducing organometallic compound, an aluminum compound, a zinc compound, a magnesium compound, a compound such as titanium as the component (C)/a reducing organometallic compound as the component (B) (molar ratio) = 0.5/I to 20/ When added at the rate of l,
Furthermore, certain highly hydrogenated polymers are obtained.
（Ｃ）成分に用いられるアルミニウム化合物の具体例と
しては、トリメデルアルミニウム、トリエチルアルミニ
ウム、トリイソブチルアルミニウム、トリフェニルアル
ミニウム、ジエチルアルミニウムクロリド、エチルアル
ミニウムジクロライト、メチルアルミニウムセスキクロ
リド、エチルアルミニウムセスキクロリド、ジエチルア
ルミニウムヒドリド、ジイソブチルアルミニウムヒドリ
ド、トリフェニルアルミニウム、トリ（２−エヂルヘキ
シル）アルミニウム等が挙げられる。Specific examples of the aluminum compound used as component (C) include trimedel aluminum, triethyl aluminum, triisobutyl aluminum, triphenyl aluminum, diethylaluminium chloride, ethyl aluminum dichlorite, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, diethyl Examples include aluminum hydride, diisobutylaluminum hydride, triphenylaluminum, tri(2-edylhexyl)aluminum, and the like.
（Ｃ）成分に用いられるＩＩｊ鉛化合物としては。As the IIj lead compound used as component (C).
ジエブール亜鉛、ビス（シクロペンタジェニル）亜鉛、
ジフェニル１１ｒ：鉛等が挙げられる。Diebourg zinc, bis(cyclopentagenyl)zinc,
Diphenyl 11r: Examples include lead.
（Ｃ）成分に用いられるマグネシウム化合物としては、
ジメチルマグネシウム、ジエチルマグネシウム、メチル
マグネシウムブロマイド、メチルマグネシウムクロライ
ド、エチルマグネシウムブロマイド、エチルマグネシウ
ムクロライド、フェニルマグネシウムブロマイド、フェ
ニルマグネシウムクロライド、ジメチルマグネシウム、
ｔ、−ブチルマグネシウムクロライド等が挙げられる。As the magnesium compound used for component (C),
Dimethylmagnesium, diethylmagnesium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, phenylmagnesium bromide, phenylmagnesium chloride, dimethylmagnesium,
Examples include t,-butylmagnesium chloride.
これらの他にリチウムアルミニウムヒドライドの如き還
元性金属を２秤以Ｆ含も化合物も色合される。In addition to these, compounds containing reducing metals such as lithium aluminum hydride containing 2 or more F are also tinted.
１某」−の人手難易度、取扱いの容易性などを加味する
と、トリエチルアルミニウム、トリイソブチルアルミニ
ウム、ジエチルアルミニウムクロリド、エチルアルミニ
ウムジクロライトが好ましい。In consideration of the degree of manual labor and ease of handling, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, and ethylaluminum dichlorite are preferred.
（Ｃ）成分に用いられる有機リチウム化合物としては、
アルコキシリチウム化合物を除き、メチルリチウム、エ
ヂルリチウム、ｎ−プロピルリチウム、ｎ−ブチルリチ
ウム、５ｅｃ−ブチルリチウム、イソブチルリチウム、
ｎ−ヘキシルリチウム、フェニルリチウム、ｐ−１リル
リチウム、キシリルリチウム、鉛活性末端リチウム等が
挙げられる。As the organic lithium compound used for component (C),
Excluding alkoxylithium compounds, methyllithium, edyllithium, n-propyllithium, n-butyllithium, 5ec-butyllithium, isobutyllithium,
Examples include n-hexyllithium, phenyllithium, p-1lyllithium, xylyllithium, lead active terminal lithium, and the like.
特に（Ｂ）成分と好ましい組み合わせはｎ−プリルリチ
ウム、ｓｅｃブチルリチウムである。Particularly preferred combinations with component (B) are n-prilyllithium and sec-butyllithium.
叉、（Ｃ）成分に用いられるアルコキシリチウム化合物
の具体例としては、メトキシリチウム、エトキシリチウ
ム、ｎ−プロポキシリチウム。Specific examples of the alkoxylithium compound used for component (C) include methoxylithium, ethoxylithium, and n-propoxylithium.
ｉ−プロポキシリチウム、ｎ−ブトキシリチウム、 ５
ｅｃ−ブトキシリチウム、Ｌ−ブトキシリチウム、ペン
チルオキシリチウム、ヘキシルオキシリチウム、ヘプチ
ルオキシリチウム、オクチルオキシリチウム、フェノキ
シリチウム、４−メチルフェノキシリチウム、２．６−
ジーし一ブチルー４−メチルフェノキシリチウム、ベン
ジルオキシリチウム、更にはアルキルリヂウム化合物と
アルコール性化合物又はフェノール性水酸基化合物との
反応生成物界が挙げられる。i-propoxylithium, n-butoxylithium, 5
ec-butoxylithium, L-butoxylithium, pentyloxylithium, hexyloxylithium, heptyloxylithium, octyloxylithium, phenoxylithium, 4-methylphenoxylithium, 2.6-
Examples include di-butyl-4-methylphenoxylithium, benzyloxylithium, and the reaction product world of an alkylridium compound and an alcoholic compound or a phenolic hydroxyl group compound.
触媒（Ｃ）成分と組み合わせた場合最も活性の発現しや
すいより好ましいものは、２．６−シーしブチル−４−
メチル−フェノキシリチウムである。A more preferable compound that exhibits the most activity when combined with the catalyst (C) component is 2,6-butyl-4-
Methyl-phenoxylithium.
触媒（Ｃ）成分／触媒（Ｂ）成分のモル比が０．５／１
〜２０／ｌであることが好ましい。触媒（Ｃ）成分が（
Ｂ）成分１モルに対し０．５モル未満では触媒活性が不
充分で温和な条件下でのポリマーの水添が難しくなり好
ましくない。一方、２０モルを越えると水添の触媒活性
は保有しているが、実質的に活性向上に関与しないで触
媒（Ｃ）成分を多情に用いることになり不経済であるば
かりでなく、ポリマーのゲル化や副反応を招くので好ま
しくない。好適な触媒（Ｃ）成分／触媒（Ｂ）成分のモ
ル比はＩ／Ｉ〜１０／ｌである。The molar ratio of catalyst (C) component/catalyst (B) component is 0.5/1
It is preferable that it is 20/l. The catalyst (C) component is (
If it is less than 0.5 mole per mole of component B), the catalyst activity will be insufficient and it will be difficult to hydrogenate the polymer under mild conditions, which is not preferred. On the other hand, if the amount exceeds 20 moles, although the hydrogenation catalytic activity is retained, the catalyst (C) component will be used liberally without substantially contributing to the improvement of the activity, which is not only uneconomical but also increases the polymer's performance. This is not preferable because it causes gelation and side reactions. A preferred catalyst (C) component/catalyst (B) component molar ratio is I/I to 10/l.
次に、本発明の触媒を用いて水添するオレフィン性不飽
和二１ｎ結合金有ポリマーについて説明する。Next, the olefinically unsaturated di1n-bonded gold-containing polymer that is hydrogenated using the catalyst of the present invention will be described.
本発明で用いるオレフィン性不飽和二用結合金有ポリマ
ーなる語は、ポリマー鎖中あるいは側鎖中にオレフィン
性の炭素−炭素不飽和二重結含有するポリマーは全て包
含される。好ましい伐倒として共役ジエンポリマーある
いは共役ジエンとオレフィンモノマーとのランダム、ブ
ロックグラフトコポリマー等が挙げられる。The term olefinically unsaturated divalent bond-containing polymer used in the present invention includes all polymers containing an olefinic carbon-carbon unsaturated double bond in the polymer chain or side chain. Preferred examples include conjugated diene polymers and random and block graft copolymers of conjugated dienes and olefin monomers.
かかる共役ジエンポリマーとしては、共役ジエンホモポ
リマー及び共役ジエン相１ｊあるいは共役ジエンの少な
くとも１種と共役ジエンと共電可能なオレフィンモノマ
ーの少なくとも１種とを共重合して得られるコポリマー
等が包含される。かかる共役ジエン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−ブタジェン、イソプレン、２３−ジ
メチル−１，３−ブタジェン、１．３−ペンタジェン、
２−メチル−１，３−ペンタジェン、１．３−へキサジ
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、クロロブレン等が挙げ
られる。Such conjugated diene polymers include a conjugated diene homopolymer, a conjugated diene phase 1j, or a copolymer obtained by copolymerizing at least one conjugated diene and at least one olefin monomer capable of cocharging with the conjugated diene. Ru. Conjugated dienes used in the preparation of such conjugated diene polymers generally include conjugated dienes having from 4 to about 12 carbon atoms, specific examples include 1,3-butadiene, isoprene, 23 -dimethyl-1,3-butadiene, 1,3-pentadiene,
2-Methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-
Examples include butyl-1,3-octadiene and chlorobrene.
Ｔ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−ブタジェン、イソプレンが特に
好ましく、ポリブタジェン、ポリイソプレン、ブタジェ
ン／イソプレンポリマーの如き弾性体が本発明の実施に
特に好ましい。かかるポリマーにおいては、ポリマー類
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ポ
リマーの溶解性が低下し、均一・に水添を行う為には溶
媒が限定されるので該結合を約ｌＯ％以に含イ１するポ
リマーより好ましい。From the standpoint of obtaining an elastomer that can be advantageously developed in the T industry and has excellent physical properties, 1,3-butadiene and isoprene are particularly preferred, and elastomers such as polybutadiene, polyisoprene, and butadiene/isoprene polymers are suitable for carrying out the present invention. Particularly preferred. In such a polymer, the microstructure of the polymer is not particularly limited and any structure can be suitably used. However, if there are few 1,2-vinyl bonds, the solubility of the polymer after hydrogenation will decrease, making it difficult to hydrogenate uniformly and uniformly. Since solvents are limited in order to carry out this process, it is preferable to use polymers containing about 10% or more of such bonds.
本発明の水添反応に用いるポリマーは、一般的には分子
量約１０００〜約１００万を有するもので、直鎖型の他
に、カップリング剤でカッ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ックコポリマーが包含
される。The polymer used in the hydrogenation reaction of the present invention generally has a molecular weight of about 1,000 to about 1,000,000, and in addition to the linear type, the so-called branched type coupled with a coupling agent, the radial type, or the star type. block copolymers are included.
カップリング剤の具体例としては、（ジクロロメチル）
トリクロロシラン、（ジクロロフェニル）トリクロロシ
ラン、１．２−ビス（トリクロロシリル）エタン、ヘキ
サクロロジシラン、１，２゜３４、７．７−へキサクロ
ロ−６−メチルジクロロシリル−２−ノルボルネン、オ
クタクロロトリシロキサン、トリクロロメチルトリクロ
ロシランなどが挙げられる。Specific examples of coupling agents include (dichloromethyl)
Trichlorosilane, (dichlorophenyl)trichlorosilane, 1,2-bis(trichlorosilyl)ethane, hexachlorodisilane, 1,2゜34,7.7-hexachloro-6-methyldichlorosilyl-2-norbornene, octachlorotrisiloxane , trichloromethyltrichlorosilane, and the like.
また、リビングアニオン重合において、末端な極ｆト基
で修飾したポリマー、およびその他の手段でポリマーを
極性基で修飾したポリマーも包含される。修飾される極
性基としては、水酸基、カルボギシ基、エステル基、イ
ソシアナート基、ウレタン基、アミド基、尿素基、チオ
ウレタン基などが挙げられる。In living anionic polymerization, polymers modified with terminal polar groups and polymers modified with polar groups by other means are also included. Examples of the polar group to be modified include a hydroxyl group, a carboxy group, an ester group, an isocyanate group, a urethane group, an amide group, a urea group, and a thiourethane group.
その他公知のいかなる重合方法、例えばアニオンｉ９合
法、カチオン重合法、配位重合法、ラジカル小合法、あ
るいは溶液車合法、エマルジョン巾合法等で製造される
ポリマーを用いることができる。Polymers produced by any other known polymerization methods, such as anionic i9 method, cationic polymerization method, coordination polymerization method, radical polymerization method, solution vehicle method, emulsion width method, etc., can be used.
史にはＭｏ、Ｗ等のメタセシス触媒を用いて開ｈＪ 重
合により得られるノルボルネン誘導体の重合体も本発明
で用いられるオレフィン性不飽和二重結合を有するポリ
マーに包含される。Historically, polymers of norbornene derivatives obtained by open hJ polymerization using metathesis catalysts such as Mo and W are also included in the polymers having olefinically unsaturated double bonds used in the present invention.
かかる重合体の＋Ｎｉ体の具体例として、シクロブテン
、シクロペンテン、シクロオクテン、１．５−シクロオ
クタジエン、１，５．９−シクロドデカトリエン、ノル
ボルネン、５−メチル−ノルボルネンなどのシクロアル
ケン、５−ノルボルネン−２カルボン酸メヂル、５−ノ
ルボルネン−２−カルボン酸工°チル、５−ノルボルネ
ン−２−カルボン酸フェニル、２−メチル−５−ノルボ
ルネン−２−カルボン酸メチル、３−フェニル−５−ノ
ルボルネン−２−カルボン酸ブチル、５−ノルボルネン
２．３−ジカルボン酸ジメチル、５−ノルボルネン−２
−カルボン酸シクロヘキシル、５−ノルボルネン−２−
カルボン酸アリール、５−ノルボルネン−２イルアセテ
ート、５−ノルボルネン２−ニトリル、３−メチル−５
−ノルボルネン２ニトリル、２．３−ジメチル−５ノル
ボルネン２．３−ジニトリル、５−ノルボルネン−２−
カルボン酸アミド、Ｎ−メチル−５ノルボルネンー２カ
フボン酸アミド、Ｎ、Ｎ−ジエチル−５ノルボルネン−
２−カルボン酸アミド、Ｎ、Ｎ−ジメチル２−メヂルー
５−ノルボルネン−２，３−ジカルボン酸ジアミド、５
−ノルボルネン−２，３−ジカルボン酸無水物（無水ハ
イミック酸１．２．３−ジメチル−５−ノルボルネン−
２，３−ジカルボン酸イミド、Ｎ−フェニル−２−メチ
ル−５−ノルボルネン−２，３−ジカルボン酸イミド、
５−メチル−５−カルボキシシクロへキシルビシクロ［
２，２゜１］−２−ヘブデン、５−メヂルー５−カルボ
キシ（４−ＬｅｒＬ−ブチルシクロヘキシル）ビシクロ
［２，２，１］ −］２−ヘプテン８−メチル−８−カ
ルボキシシクロへキシルテトラシクロ［４，４，０１２
・６．１７・１０］ ａ−ドデセン、５−メチル−５
−カルボキシトリシクロ［５，２，１，０”・６］デシ
ル−８゛−ビシクロ［２°、２．ｌ ］ −］２−ヘブ
デなどのノルボルネン語導体が使用できる。Specific examples of +Ni forms of such polymers include cycloalkenes such as cyclobutene, cyclopentene, cyclooctene, 1.5-cyclooctadiene, 1,5.9-cyclododecatriene, norbornene, and 5-methyl-norbornene; Methyl norbornene-2-carboxylate, methyl 5-norbornene-2-carboxylate, phenyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 3-phenyl-5-norbornene -2-butyl carboxylate, 5-norbornene-2,3-dicarboxylic acid dimethyl, 5-norbornene-2
-cyclohexyl carboxylate, 5-norbornene-2-
Aryl carboxylate, 5-norbornene-2yl acetate, 5-norbornene-2-nitrile, 3-methyl-5
-Norbornene 2-nitrile, 2,3-dimethyl-5-norbornene 2,3-dinitrile, 5-norbornene-2-
Carboxylic acid amide, N-methyl-5-norbornene-2-cafboxylic acid amide, N,N-diethyl-5-norbornene-
2-carboxylic acid amide, N,N-dimethyl 2-medy-5-norbornene-2,3-dicarboxylic acid diamide, 5
-Norbornene-2,3-dicarboxylic anhydride (himic anhydride 1.2.3-dimethyl-5-norbornene-
2,3-dicarboxylic imide, N-phenyl-2-methyl-5-norbornene-2,3-dicarboxylic imide,
5-Methyl-5-carboxycyclohexylbicyclo[
2,2゜1]-2-hebdene, 5-medyl-5-carboxy(4-LerL-butylcyclohexyl)bicyclo[2,2,1]-]2-heptene8-methyl-8-carboxycyclohexyltetracyclo [4,4,012
・6.17・10] a-dodecene, 5-methyl-5
Norbornene conductors such as -carboxytricyclo[5,2,1,0''.6]decyl-8'-bicyclo[2', 2.1] -]2-Hebde can be used.
以−ヒに述べた（Ａ）成分のオレフィン化合物。The olefin compound of component (A) described below.
（Ｂ ）成分のビス（シクロペンタジェニル）チタニウ
ム化合物等、（Ｃ）成分の還元性有機金属化合物を含有
してなる触媒は、再現性良く、長時間高い水素添加活性
を持続する。（Ａ）成分のオレフィン性化合物と触媒（
Ｂ）、（Ｃ）成分をあらかじめ混合する場合は不活性雰
囲気下の他に水素雰囲気下で行うことができる。本発明
での触媒を用いた水添反応は２０〜１００℃において４
〜２０ｋｇ／ｒｎ”の水素圧下で行うとポリマー中のオ
レフィン系不飽和二重結合を選択的に好適に水素添加す
ることが可能である。A catalyst containing a reducing organometallic compound as component (C), such as a bis(cyclopentagenyl) titanium compound as component (B), maintains high hydrogenation activity for a long time with good reproducibility. (A) component olefinic compound and catalyst (
When components B) and (C) are mixed in advance, it can be carried out not only under an inert atmosphere but also under a hydrogen atmosphere. The hydrogenation reaction using the catalyst in the present invention is carried out at 20 to 100°C.
When carried out under a hydrogen pressure of ~20 kg/rn'', it is possible to selectively and suitably hydrogenate olefinically unsaturated double bonds in the polymer.
水素添加後に水素添加されたポリマーからの触媒の除去
は極めて容易である。すなわち、アルコールなどの極性
溶媒と水素添加後のポリマーを接触させることにより、
又触媒除去をより効果的に行う場合は極性溶剤に少量の
酸を添加して使用することにより除去可能である。Removal of the catalyst from the hydrogenated polymer after hydrogenation is very easy. That is, by bringing the hydrogenated polymer into contact with a polar solvent such as alcohol,
Further, in order to remove the catalyst more effectively, it is possible to remove the catalyst by adding a small amount of acid to a polar solvent.
本発明の触媒はＬ業的に使用する際、特にバッチ式、連
続式水素添加プロセスにおいて安定した高い活性の触媒
を長時間持続できるので工業−１，きわめて有利である
。The catalyst of the present invention is extremely advantageous in industrial use, especially in batch and continuous hydrogenation processes, since it can maintain a stable and highly active catalyst for a long period of time.
次に１本発明の水素添加触媒を用いた水素添加方法につ
いて説明する。Next, a hydrogenation method using the hydrogenation catalyst of the present invention will be explained.
本発明の水添反応は、オレフィン性不飽和二重結合金有
ポリマーを不活性有機溶媒に溶解した溶液において行わ
れる。「不活性有機溶媒」とは溶媒が水添反応のいかな
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−へブタン、ｎ−オクタンの
如き脂肪族炭化水素類、シクロペンタン、シクロヘキサ
ン、シクロへブタンの如き脂環族炭化水素類、ジエチル
ニーデル、テトラヒドロフランの如きニーデル類の１１
独もしくは混合物である。また、ベンセン、トルエン、
キシレン、エチルベンセ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ぞうく二重結合が水添さ
れない時に限って使用することができる。より好ましく
は１本発明に使用する水添用ポリマーを、水添反応に使
用する溶媒と同一の溶媒中で重合し、その重合溶液をそ
のまま水添反応に用いるのがｆｊ利である６本発明の水
添反応はポリマーを溶液に対して１〜５０ Ｔｎ ｎｔ
％、好ましくは１０〜３０重量％の濃度に溶解した溶液
中で行われる。The hydrogenation reaction of the present invention is carried out in a solution of an olefinically unsaturated double bond gold-containing polymer dissolved in an inert organic solvent. "Inert organic solvent" means a solvent that does not react with any participant in the hydrogenation reaction. Suitable solvents include, for example, aliphatic hydrocarbons such as n-pentane, n-hebutane, n-octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclohebutane, diethyl needle, tetrahydrofuran, etc. Needle class 11
It is either unique or a mixture. Also, benzene, toluene,
Aromatic hydrocarbons such as xylene and ethylbenzene can also be used provided that the aromatic double bonds are not hydrogenated under the selected hydrogenation reaction conditions. More preferably, it is fj advantageous to polymerize the hydrogenation polymer used in the present invention in the same solvent as the solvent used in the hydrogenation reaction, and use the polymerization solution as it is in the hydrogenation reaction.6 The present invention Hydrogenation reaction of 1 to 50 Tn nt of polymer to solution
%, preferably 10 to 30% by weight.
本発明の水添反応は、−・般的には上記ポリマー溶液を
所定の温度に保持し、攪拌下または不攪拌士にて所定圧
に加圧することによって実施される。The hydrogenation reaction of the present invention is generally carried out by maintaining the polymer solution at a predetermined temperature and pressurizing it to a predetermined pressure with stirring or with a non-stirrer.
触媒（Ａ）、（Ｂ）、（Ｃ）をあらかじめ混合した後系
中へ加える。Catalysts (A), (B), and (C) are mixed in advance and then added to the system.
また、各々の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、例えば窒素、ヘリウム、ネ
オン、アルゴン等の水添反応のいかなる関ｒｙ体とも反
応しない雰囲気Ｆを意味する。空気や酸をは触媒を酸化
したりして触媒の失ｒ＾を招くので好ましくない。Additionally, each catalyst needs to be handled under an inert atmosphere. The inert atmosphere means an atmosphere F that does not react with any of the participants in the hydrogenation reaction, such as nitrogen, helium, neon, argon, and the like. Air and acid are not preferred because they oxidize the catalyst and cause loss of the catalyst.
触媒をあらかじめ混合する場合は、不活性雰囲気下の他
の水素雰囲気丁で行うことができる。If the catalyst is premixed, this can be done in another hydrogen atmosphere under an inert atmosphere.
本発明における触媒の好ましい添加量は、ポリマー１０
０ｇに対し、触媒（Ａ）成分の（１１で２０ミリモル以
−トである。The preferred amount of catalyst added in the present invention is polymer 10
The amount of catalyst (A) component (11) is 20 mmol or more per 0 g.
この添加量範囲であれば、ポリマー中の不飽和二、１結
合を優先的に水添することが０１能で、芳香核二重結合
の水添は実質的に起こらないで、極めて高活性に水添反
応が進行し、高水添率のポリマーが得られる。また繰返
し、実施した時の出現性も極めて良い。With this addition amount range, it is possible to preferentially hydrogenate unsaturated di- and mono-bonds in the polymer, and hydrogenation of aromatic double bonds does not substantially occur, resulting in extremely high activity. The hydrogenation reaction proceeds and a polymer with a high hydrogenation rate is obtained. Also, the appearance when repeated is very good.
本発明の水添反応は元素状水素を用いて行ｔ）れ、より
好ましくはガス状でポリマー溶液中に導入される。水添
反応は攪拌上行われるのがより好ましく、導入された水
素を充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０〜１２０℃の温度範囲で実施される
。０℃未満では触媒の活性が低トし、かつ水添速度も遅
くなり多τ、ｔの触媒を要するので経済的でなく、また
１２０℃を越えると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やすくなって水
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２０〜１００℃の範囲である。The hydrogenation reaction according to the invention is carried out using elemental hydrogen, more preferably introduced into the polymer solution in gaseous form. More preferably, the hydrogenation reaction is carried out with 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 0 to 120°C. If it is below 0°C, the activity of the catalyst will be low and the hydrogenation rate will be slow, requiring a catalyst with a large amount of τ and t, which is not economical, and if it exceeds 120°C, polymer decomposition and gelation will easily occur. , and hydrogenation of the aromatic nucleus portion also tends to occur, resulting in a decrease in hydrogenation selectivity, which is not preferable. More preferably, the temperature is in the range of 20 to 100°C.
水添反応に使用される水素の圧力は１〜１００ｋｇ／ｃ
ｍ’が好適である。Ｉｋｇ／ａｍ″未満では水添速度遅
くなって実質的に頭打ちとなるので水素率をｌ−けるの
が難しくなり、１００ｋｇ／ｃゴを越えると、５１！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４〜２０ｋｇ／ｃｍ″であるが
、触媒添加量等との相関で最適水素圧力は選択され、実
質的には前記好適触媒量が夕晴になるに従って水素ｎ〜
力は高圧側を選択して実施するのが好ましい。The pressure of hydrogen used in hydrogenation reaction is 1 to 100 kg/c
m' is preferred. If it is less than 1kg/am'', the hydrogenation rate slows down and practically reaches a plateau, making it difficult to maintain the hydrogen rate.If it exceeds 100kg/cm, the hydrogenation reaction is almost completed at the same time as 51!pressure. , practically meaningless;
This is not preferable because it causes unnecessary side reactions and gelation. A more preferable hydrogenation pressure is 4 to 20 kg/cm'', but the optimum hydrogen pressure is selected in correlation with the amount of catalyst added, etc., and substantially the preferable amount of catalyst increases as the evening weather increases.
It is preferable to select the high pressure side and apply the pressure.
本発明の水添反応時間は通常数秒ないし２０時間である
。他の水添反応はバッチ式、連続式等のいかなる方法で
実施しても良い。水添反応の進１−ｒは水素吸収Ｍを追
跡することによって把握することができる。The hydrogenation reaction time of the present invention is usually several seconds to 20 hours. Other hydrogenation reactions may be carried out by any method such as a batch method or a continuous method. The progress of the hydrogenation reaction 1-r can be grasped by tracking hydrogen absorption M.
本発明の方法によって、ポリマー中の不飽和ニ重結合の
任意の割合を水添させることができる。By the method of the invention any proportion of unsaturated double bonds in the polymer can be hydrogenated.
本発明の水添触媒を用いればきｔ）めて高速度にＦＩＧ
現性良く高水添ポリマーが得られるので１漬１゛たいへ
／υ有利である。If the hydrogenation catalyst of the present invention is used, the FIG.
Since highly hydrogenated polymers with good developability can be obtained, it is advantageous to 1゜/υ per dipping.
又、本発明の水添触媒はスゲ川ノンなとのオレフィン類
の水添にも用いることが可能である。Furthermore, the hydrogenation catalyst of the present invention can also be used for the hydrogenation of olefins such as Sugegawa nonnato.
本発明のノＪ法により水添反応を打ったポリマ溶液から
は触媒の残渣を除去し、水添されたポリマーを溶液から
容易にり１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など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
める方法。または反応液を熱湯中に攪拌上投入した後、
溶媒と共に蒸留することによって溶媒を除去する方法等
で行うことができる。これらの水添ポリマーの単離過程
においても触媒も大部分が分解、除去され、ポリマーよ
り除かれる。従って触媒を脱蔵、除去するだめの特別な
操作は必要としないが、触媒除去をより効果的に実施す
る場合は、酸性の極性溶媒または水をポリマー水添反応
液に加えることが６ｒましい。Catalyst residues can be removed from a polymer solution subjected to a hydrogenation reaction by the NoJ method of the present invention, and the hydrogenated polymer can be easily separated from the solution. 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 the polymer. Or, after stirring the reaction solution into boiling water,
This can be carried out by a method in which the solvent is removed by distillation together with the solvent. In the process of isolating these hydrogenated polymers, most of the catalyst is also decomposed and removed and removed from the polymer. Therefore, no special operations are required to devolatilize or remove the catalyst, but if you want to remove the catalyst more effectively, it is preferable to add an acidic polar solvent or water to the polymer hydrogenation reaction solution. .
［実施例］
以［・、実施例により本発明を具体的に説明するが１本
発明はこれらに限定されるものではない。[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.
尚、実施例中の共役ジエン系ポリマー中の１．２ビニル
結合金イｆ率は赤外吸収スペクトルを用い、ハンプトン
法（Ｒ，Ｒ，ＨａｍｐＬｏｍ、＾ｎａ １． Ｃｈｃｍ
、 、第２９巻９２３自（１９４９年）］によって測定
した。In addition, the 1.2 vinyl bond gold f ratio in the conjugated diene polymer in the examples was determined using an infrared absorption spectrum using the Hampton method (R, R, HampLom, ^na 1. Chcm
, Vol. 29, 923 (1949)].
実施例１．２
下に示した各ポリマーを精製乾燥したシクロヘキサンに
溶解しポリマー濃度２０？Ｉ’ｊｆｆｆ％に調整した。Example 1.2 Each polymer shown below was dissolved in purified and dried cyclohexane to give a polymer concentration of 20? It was adjusted to I'jfff%.
Ａ ： ＪＳＲＳＬ ５５２ （日本合成ゴム社製）・
・・スチレン／ブタジェン分岐ランダムポリマー、結合
スチレン量２４％、ブタジェン部の１．２結合」４３９
％
Ｂ：クレイトンＩ）−１１０１（シェル社製）・・・ス
チレン−ブタジェン−スチレンブロックポリマー
このポリマー溶液５ｋｇを乾燥した１０ｇオートクレー
ブに仕込み、７０℃に攪拌、保持した。次いでビス（シ
クロペンタジェニル）チタニウムジクロリド１ミリモル
とＩｇ（１１，３ミリモル）のジエヂルアルミニウムク
ロリドを含むトルエン溶液５０ｍＪ２に混合し更にシク
ロヘキセン１００ｍε（９８７ミリモル）を混合した後
１時間放置したものを１０２オートクレーブに仕込み、
乾燥した水素ガスをｌｏｋｇ／ｃｍ″Ｇの圧力で供給し
攪拌下１時間反応を行った。反応液を常温常圧に戻して
オートクレーブより汲出し水中に攪拌、投入後、溶媒を
水蒸気蒸留除去することによって白色の水添ポリマーを
得た。得られた水添ポリマーの水添率を赤外吸収スペク
トルより求め表−１に示した。A: JSRSL 552 (manufactured by Japan Synthetic Rubber Co., Ltd.)
...Styrene/butadiene branched random polymer, bound styrene content 24%, butadiene moiety 1.2 bonds"439
% B: Kraton I)-1101 (manufactured by Shell) Styrene-butadiene-styrene block polymer 5 kg of this polymer solution was charged into a dry 10 g autoclave, stirred and maintained at 70°C. Next, 1 mmol of bis(cyclopentadienyl)titanium dichloride and Ig (11.3 mmol) were mixed in 50 mJ2 of a toluene solution containing diethyl aluminum chloride, and then 100 mε (987 mmol) of cyclohexene was mixed and left for 1 hour. 102 Prepared in autoclave,
Dry hydrogen gas was supplied at a pressure of 100 kg/cm''G and the reaction was carried out with stirring for 1 hour.The reaction solution was returned to normal temperature and pressure, was pumped out from the autoclave, stirred and poured into water, and the solvent was removed by steam distillation. As a result, a white hydrogenated polymer was obtained.The hydrogenation rate of the obtained hydrogenated polymer was determined from an infrared absorption spectrum and is shown in Table 1.
比較例１〜４
実施例１と同様に各ポリマーを調整棟７０℃に攪拌保持
した０次いで、ビス（シクロペンタジェニル）チタニウ
ムジクロリド１ミリモルと１ｇのジエチルアル趣ニウム
クロリドを含むトルエン溶液５０ｍ℃を混合した後放置
時間を変えたものを各々ｌ０Ｉ２オートクレブに仕込み
水添反応を行なった。その結果得られた水添ポリマーの
水添率を表−１に示した。Comparative Examples 1 to 4 In the same manner as in Example 1, each polymer was stirred and maintained at 70°C in a control building.Next, a toluene solution containing 1 mmol of bis(cyclopentadienyl)titanium dichloride and 1 g of diethylarzinium chloride was prepared at 50m°C. After mixing, the mixtures were left to stand for different times and were charged into a 10I2 autoclave to perform a hydrogenation reaction. Table 1 shows the hydrogenation rate of the hydrogenated polymer obtained as a result.
表−１
＊オレフィン性不疎…にｉ℃、−合の水添率（以Ｆ同じ
、Ｃ’ｊ味に用いる）実施例３
１０βオートクレーブに脱気脱水したシクロヘキサン５
ｋｇ、スチレン１５０ｇを仕込み、テトラヒドロフラン
５ｇ。ｎ−ブチルリチウム０．８ｇを加えて３０℃から
の断熱重合を行なった。３０分後にブタジェン７００ｇ
を仕込み３０分間重合を行なった後、スチレン１５０ｇ
を加え更に３０分間重合を行なった。得られたポリマー
の一部を窒素雰囲気下で容器に２００ｍ Ａ （５５６
ミリモル）採取し、１ミリモルのビス（シクロペンタジ
ェニル）チタニウムジクロリドとジエヂルアルミニー１
ムクロリド６ミリモルを含むトルエン溶液５０ｍρに混
合し、容器内でポリマーと更に混合した後１昼夜放置し
たものをオートクレーブに加え、攪拌ド水素ガスを１５
ｋｇ／ｃｍ” Ｇの圧力で供給し１時間反応を行なっ
た。その結果得られたポリマーの水添率を表−２に示し
た
比較例５．６
実施例３と同様に重合を行なった後反応液を４０℃に保
ち、１ミリモルのビス（シクロペンタジェニル）チタニ
ウムジクロリドとジエチルアルミニウムクリロド６ミリ
モルを含むトルエン溶液５０ｍｊ２を混合した後放置時
間を変えたものを各々ＩＯ氾オートクレーブに仕込み水
添反応を行なった。その結果得られたポリマーの水添率
を表−２に示した。Table-1 *Hydrogenation rate at i℃ for olefinic inhomophobicity (hereinafter the same as F, used for C'j taste) Example 3 Cyclohexane 5 degassed and dehydrated in a 10β autoclave
kg, 150g of styrene, and 5g of tetrahydrofuran. 0.8 g of n-butyllithium was added and adiabatic polymerization was carried out from 30°C. Butadiene 700g after 30 minutes
After charging and polymerizing for 30 minutes, add 150g of styrene.
was added and polymerization was further carried out for 30 minutes. A portion of the obtained polymer was placed in a container under a nitrogen atmosphere at 200 mA (556
1 mmol of bis(cyclopentadienyl)titanium dichloride and diethyl aluminum 1
The mixture was mixed with 50 mρ of a toluene solution containing 6 mmol of muchloride, further mixed with the polymer in a container, and then left for 1 day and night.
Comparative Example 5.6 After polymerization in the same manner as in Example 3, the hydrogenation rate of the resulting polymer is shown in Table 2. The reaction solution was maintained at 40°C, and 50 mj2 of toluene solution containing 1 mmol of bis(cyclopentagenyl)titanium dichloride and 6 mmol of diethylaluminum dichloride was mixed, and the solutions were left to stand for different periods of time, then each was charged into an IO flooding autoclave and water was added. An addition reaction was carried out. The hydrogenation rate of the resulting polymer is shown in Table 2.
表−２
実施例４
ＪＳＩ（５Ｌ５５２をテトラヒドロフラン３． ｏｏｏ
ｐｐｍを含むシクロヘキサンに溶解しポリマー濃度２０
重１１１％に調整した。このポリマー溶液５ｋｇを乾燥
した１０℃オートクレーブに仕込み、ｒｌ−ブチルリチ
ウムを１０ミリモルを加え、９ミリモルの２，６−シー
し一ブチルーｐ−クレゾールを仕込み１０分間反応を行
った後４０℃に攪拌保持した。次いでこのポリマーの一
部を窒素雰囲気下で容器に２０Ｏｎ＋１２（５５６ミリ
モル）採取し、１．５ミリモルのビス（シクロペンタジ
ェニル）チタニウジクロリドとジエチルアルミニウムク
ロリド５ミリモルをあらかじめ窒素トで５Ｏｎ＋４２の
トルエン中で混合したものを加えた後１２時間放置した
ものをオートクレーブに加え、攪拌上水素ガスを１５ｋ
ｇ／ｃｍ”Ｇの圧力で供給し１時間反応を行なった。Table 2 Example 4 JSI (5L552 was added to tetrahydrofuran 3.ooo
Polymer concentration 20 when dissolved in cyclohexane containing ppm
The weight was adjusted to 111%. 5 kg of this polymer solution was placed in a dry autoclave at 10°C, 10 mmol of RL-butyllithium was added, 9 mmol of 2,6-cyone-butyl-p-cresol was added, the reaction was carried out for 10 minutes, and the temperature was stirred at 40°C. held. Next, a part of this polymer was collected in a container under a nitrogen atmosphere (20 On+12 (556 mmol)), and 1.5 mmol of bis(cyclopentadienyl) titanium dichloride and 5 mmol of diethylaluminum chloride were added in advance to 5 On+42 of toluene under a nitrogen atmosphere. After adding the mixture in the autoclave and leaving it for 12 hours, add it to the autoclave and add 15k of hydrogen gas while stirring.
The reaction was carried out for 1 hour by supplying at a pressure of g/cm''G.
得られた水添ポリマーの水添率を表−３に示した。Table 3 shows the hydrogenation rate of the obtained hydrogenated polymer.
比較例７．８
実施例４と同様にポリマーを調整した後、このポリマー
溶ｌ＆５ｋｇを乾燥したｌＯβオートクレーブに仕込み
、１１−ブチルリチウムを１０ミリモル加え、９ミリモ
ルの２−６−シーし一ブチルーｐ−クレゾールを仕込み
、１０分間反応させた後４０℃に攪拌、保持した。次い
で１．５ミリモルのビス（ジクロペンタジェニル）チタ
ニウムジクロリドとジエチルアルミニウムクロリド５ミ
リモルをトルエン溶液に混合した後放置時間を変えたも
のを各々オートクレーブに仕込み、攪拌上水素ガスを１
５ ｋｇ／ｃｍ”の圧力で供給し１時間反応を行なった
。得られた水添ポリマーの水添率を表−３に示した。Comparative Example 7.8 After preparing a polymer in the same manner as in Example 4, 5 kg of this polymer solution was charged into a dry lOβ autoclave, 10 mmol of 11-butyllithium was added, and 9 mmol of 2-6-cy and 1-butyl lithium was added. -Cresol was charged and reacted for 10 minutes, then stirred and maintained at 40°C. Next, 1.5 mmol of bis(diclopentagenyl)titanium dichloride and 5 mmol of diethylaluminium chloride were mixed in a toluene solution, and the mixtures were charged into an autoclave for different standing times.
The reaction was carried out for 1 hour by supplying at a pressure of 5 kg/cm''. The hydrogenation rate of the obtained hydrogenated polymer is shown in Table 3.
表−３
実施例５
１Ｏρオートクレーブに脱気脱水したシクロヘキサン５
ｋｇ、スチレン３００ｇ、ブタジェン７００ｇを仕込ん
だ後、テトラヒドロフラン５ｇ。Table-3 Example 5 Cyclohexane 5 degassed and dehydrated in a 1Oρ autoclave
After charging 300 g of styrene, 700 g of butadiene, and 5 g of tetrahydrofuran.
ｎ−プチルリチム０．７ｇを加えて３０℃から９０℃の
Ｗ温市合を行なった。転化率がほぼ１００％となった後
、２，６−シーし一ブチルー４−メチルフェノキシリチ
ウム１．５ミリモルを加え攪拌した。0.7 g of n-butyllithium was added, and the mixture was heated at 30°C to 90°C. After the conversion rate reached approximately 100%, 1.5 mmol of 2,6-cy-monobutyl-4-methylphenoxylithium was added and stirred.
次いでビス（シクロペンタジェニル）チタニウムジクロ
リド０．８ミリモルを含むトルエン溶液５０ｍβを混合
し、更に、上記ポリマーの一部１００ｍで（２１７ミリ
モル）を窒素雰囲気ドで汲出し、混合した後２時間放置
したものを１０βオートクレーブに仕込み１反応γルを
４０ ’ＣＩ’１２拌Ｆで乾燥した水素ガスをＩ Ｏｋ
ｇ／ｃｒｎ” （Ｅの１「カドで攪拌１１時間反応した
。得られた水添ポリマーに水添率は９８％であった。Next, 50 mβ of a toluene solution containing 0.8 mmol of bis(cyclopentagenyl)titanium dichloride was mixed, and a 100 m portion (217 mmol) of the above polymer was pumped out in a nitrogen atmosphere, and after mixing, it was left for 2 hours. The resulting mixture was put into a 10β autoclave, and the hydrogen gas was dried at 40'CI'12 F for 1 reaction.
The mixture was stirred and reacted for 11 hours under E. g/crn. The hydrogenation rate of the obtained hydrogenated polymer was 98%.
実施例「５
実施例５と同様に１ｎ合を行なった後、２．６−シーし
一ブチルー４−メチルフェノキシリチウ１１５ミリモル
を加え攪拌した後、ビス（シクロペンタジェニル）チタ
ニウムジクロリド０．８ミリモルを含むトルエン溶液５
０ｎ＋Ｑ及びシクロヘキセン＋００ｍｊ２ （９８７ミ
リモル）を混合し直ちにオートクレーブに仕込んだ後、
−・昼夜放置した。Example 5 After carrying out a 1n reaction in the same manner as in Example 5, 115 mmol of 2,6-cy-butyl-4-methylphenoxylithium was added and stirred, followed by 0.8 mmol of bis(cyclopentadienyl)titanium dichloride. Toluene solution containing mmol 5
After mixing 0n+Q and cyclohexene+00mj2 (987 mmol) and immediately charging the autoclave,
-・Leave it alone day and night.
この反応液を４０℃攪拌下で乾燥した水素ガスを１０
ｋｇ／ｃｍ’ Ｇの圧カドで１時間反応した。得られた
水添ポリマーの水添率は９９％であった。This reaction solution was dried under stirring at 40°C, and hydrogen gas was added for 10 minutes.
The reaction was carried out under a pressure of kg/cm'G for 1 hour. The hydrogenation rate of the obtained hydrogenated polymer was 99%.
実施例７
実施例１と同様にポリマーを調整後５０℃に攪拌保持し
、５ｅｃ−ブチルリチウム２０ミリモルを添加し、２０
分間反応を行なった。次いでトルエンｌ容ｉ夜１００ｍ
βにシクロペンテン１００ｍｆｆ（１１３２ミリモル）
とビス（シクロペンタジェニル）チタニウムジクロリド
２ミリモルと２．６−ジーし一ブチルー４−メチルフェ
ノキシリチウム１ミ１ノモルを加えた後５時間数１νｔ
したものをオートクレーブに仕込み、攪拌−ドで乾燥し
た水素を供給し２０ ｋｇ／ｃｍ″Ｇで３０分間水添し
た。得られた水添ポリマーの水添率は９８％であった。Example 7 After preparing the polymer in the same manner as in Example 1, it was stirred and maintained at 50°C, and 20 mmol of 5ec-butyllithium was added.
The reaction was carried out for minutes. Then add toluene at 100m
Cyclopentene 100 mff (1132 mmol) in β
5 hours after adding 2 mmol of bis(cyclopentadienyl) titanium dichloride and 1 mmol of 2,6-di-butyl-4-methylphenoxylithium.
The resulting product was charged into an autoclave, and dried hydrogen was supplied with stirring at a pressure of 20 kg/cm''G for 30 minutes.The hydrogenation rate of the obtained hydrogenated polymer was 98%.
実施例８
１０氾オートクレーブに脱気脱水したシクロヘキサン５
ｋｇ、スチレン３００ ｇ、ブタジェン７００ｇを仕
込んだ後、デトラヒドロフラン５ｇ。Example 8 Cyclohexane 5 degassed and dehydrated in a 10-flood autoclave
After charging 300 g of styrene, 700 g of butadiene, and 5 g of detrahydrofuran.
ｎ−プチルリヂウム０．７ｇを加えて３０℃から９０℃
の昇温重合を行なった。転化率がほぼ１００％となった
後、 ４．４’−ジフェニルメタジイソシアネート２．
６ｇを加えポリマー末端をイソシアナートで修飾した。Add 0.7g of n-butylridium and heat from 30℃ to 90℃
Temperature-rising polymerization was carried out. After the conversion rate is approximately 100%, 4.4'-diphenylmethadiisocyanate2.
6 g was added to modify the polymer terminals with isocyanate.
この時一部カツブリングが起こり、カップリングポリマ
ーと未カップリングポリマーの比率がほぼ半々となった
。このポリマー溶液を４０℃にし、ｎ−ブヂルリヂウム
０．８ｇと２，６−ジし一ブチルー■）−クレゾール１
．５ｇを加えた。−・部このポリマーを窒素雰囲気下で
容器に２００＋ｎＪ２（５５６ミリモル）採取し１次に
ビス（ジクロペンタジェニル）チタニウムジクロリド１
ミリモルとトリイソブチルアルミニウム１，５ｇをトル
エン溶液５０ｍ１に混合したものを更に混合し６時間放
置後オートクレーブに仕込み、攪拌下で乾燥した水素ガ
スを供給し、水素圧２０ ｋｇ／ｃｒｒｌ″Ｇで３０分
間水添した。得られた水添ポリマーの水添率は１００％
であった。At this time, some clumping occurred, and the ratio of the coupled polymer to the uncoupled polymer became almost equal. This polymer solution was heated to 40°C, and 0.8 g of n-butylridium and 2,6-dibutyl-cresol 1
．． Added 5g. -・Part 200+nJ2 (556 mmol) of this polymer was collected in a container under a nitrogen atmosphere, and then bis(diclopentagenyl)titanium dichloride 1
A mixture of mmol and 1.5 g of triisobutylaluminum in 50 ml of toluene solution was further mixed, left for 6 hours, then charged into an autoclave, supplied with dry hydrogen gas under stirring, and heated at a hydrogen pressure of 20 kg/crrl''G for 30 minutes. Hydrogenated.The hydrogenation rate of the obtained hydrogenated polymer was 100%.
Met.
実施例９
実施例１と同様にポリマーを調整後５０℃に攪拌保持し
、ｎ−ブチルリチウム２０ミリモルを添加し、２０分間
反応を行なった０次いでトルエン溶液１００ｍｆｉにシ
クロオクテン１００ｍＱとビス（シクロペンタジェニル
）ハフニウムジクロライト２ミリモル及び２．６−ジー
し一ブチルー４−メチルフェノキシリチウム１ミリモル
を加えた後５時間放置したものをオートクレーブに仕込
み、攪拌下で乾燥した水素を供給し’ ５ ｋｇ／ｃｒ
ｎ” Ｇで３０分間水添した。得られた水添ポリマーの
水添率は９９％であった。Example 9 After preparing a polymer in the same manner as in Example 1, it was stirred and held at 50°C, 20 mmol of n-butyllithium was added, and the reaction was carried out for 20 minutes.Next, 100 mQ of cyclooctene and bis(cyclopentane) were added to 100 mfi of toluene solution. After adding 2 mmol of hafnium dichlorite and 1 mmol of 2.6-di-1-butyl-4-methylphenoxylithium, the mixture was left to stand for 5 hours, and the mixture was charged into an autoclave, and dried hydrogen was supplied with stirring to produce 5 kg. /cr
Hydrogenation was carried out for 30 minutes at n''G. The hydrogenation rate of the obtained hydrogenated polymer was 99%.
実施例１０
実施例１と同様にポリマーを調整後５０℃に攪拌保（つ
し、５ｅｃ−ブチルリチウム１８ミリモルを添加し、２
０分間反応を行なった。次いでトルエン溶ｉ夜１００ｍ
尼に上記ポリマー１００ｍＪＢとビス（シクロペンタジ
ェニル）ジルコニウムジクロライト２ミリモル及び２．
６−ジーｔ、−ブチル−４−メチルフェノキシリチウム
１ミリモルを加えた後１０時間放７７７１．たものをオ
ートクレーブに仕込み、攪拌下で乾燥した水素を供給し
Ｉ Ｏｋｇ／ｃｍ″（］で！時間水添した。得られた水
添ポリマーの水添率は９７％であった。Example 10 After preparing a polymer in the same manner as in Example 1, it was stirred and kept at 50°C (18 mmol of 5ec-butyllithium was added,
The reaction was carried out for 0 minutes. Then, dissolve in toluene for 100m.
100 mJB of the above polymer, 2 mmol of bis(cyclopentadienyl)zirconium dichlorite, and 2.
7771. After adding 1 mmol of 6-di-t,-butyl-4-methylphenoxylithium, it was released for 10 hours. The mixture was charged into an autoclave, and dried hydrogen was supplied under stirring to perform hydrogenation at I kg/cm'' (] for ! hours. The hydrogenation rate of the obtained hydrogenated polymer was 97%.
［発明の効果］
本発明の水素添加触媒は調製後長時間を経ても調製直後
とほぼ同等の活性を持続し、オレフィン性不飽和二ｉｒ
結合金有ポリマーを温和な条件下で極めて高速度に高転
化率に水添することが可能である。[Effects of the Invention] The hydrogenation catalyst of the present invention maintains almost the same activity as immediately after preparation even after a long period of time after preparation, and has an olefinically unsaturated diir.
It is possible to hydrogenate bonded metal polymers under mild conditions at extremely high rates and with high conversions.
添加するオレフィン化合物（ポリマー叉は千ツマ−）と
して水添１１１１のポリマーも用いることができるので
触媒を経済的かつ簡１１′Ｌに調製することがｒｉ（能
となり、得られる水添ポリマーは耐候性、−４熱性、ｔ
４１酸性のイｑれたエラストマー、熱ｉＴ ｆｆ！性エ
ラストマーもしくは熱＋ｊＪ ｉｌｌ性樹脂として使用
され、また紫外線吸収剤、オイル、フライヤー笠の添加
剤を加えたり、他のエラストマー、樹脂とブレンドして
使用され工業上有用である。Since a hydrogenated 1111 polymer can also be used as the olefin compound (polymer or polymer) to be added, it is possible to prepare the catalyst economically and easily, and the resulting hydrogenated polymer has good weather resistance. -4 fever, t
41 Acidic elastomer, heat iT ff! It is used as a heat-resistant elastomer or heat-resistant resin, and is industrially useful by adding ultraviolet absorbers, oils, and fryer shade additives, or by blending it with other elastomers and resins.
Claims (1)
ビス（シクロペンタジエニル）チタニウム化合物、ビス
（シクロペンタジエニル）ジルコニウム化合物、ビス（
シクロペンタジエニル）ハフニウム化合物の少なくとも
１種、および（Ｃ）還元性有機金属化合物の少なくとも
１種を混合してなる水素添加触媒。 ２、（Ａ）成分の二重結合含有量／（Ｂ）成分（モル比
）が２０／１以上でかつ、（Ｃ）成分／（Ｂ）成分（モ
ル比）が０．５／１〜２０／１である請求項１記載の水
素添加触媒。 ３、（Ｂ）成分のビス（シクロペンタジエニル）チタニ
ウム化合物、ビス（シクロペンタジエニル）ジルコニウ
ム化合物、ビス（シクロペンタジエニル）ハフニウム化
合物が下記一般式（ I ）で示される化合物である請求
項１記載の水素添加触媒。 ▲数式、化学式、表等があります▼（ I ） ［式中、ＭはＴｉ、ＺｒまたはＨｆでありＲ＾１、Ｒ＾
２はハロゲン原子、炭化水素基、アリロキシ基、アルコ
キシ基またはカルボニル基であり、Ｒ＾１、Ｒ＾２は同
一であっても異っていてもよい］４、還元性有機金属化
合物が有機アルミニウム化合物、有機亜鉛化合物、有機
マグネシウム化合物、有機リチウム化合物またはアルコ
キシリチウム化合物である請求項１記載の水素添加触媒
。 ５、請求項１記載の触媒を用いて２０〜１００℃、水素
圧４〜２０ｋｇ／ｃｍ＾２下で反応させるオレフィン性
二重結合含有ポリマーの水素添加方法。[Claims] 1. (A) at least one olefin compound; (B)
Bis(cyclopentadienyl) titanium compounds, bis(cyclopentadienyl) zirconium compounds, bis(
A hydrogenation catalyst comprising a mixture of at least one (cyclopentadienyl) hafnium compound and (C) at least one reducing organometallic compound. 2. Double bond content of component (A)/component (B) (molar ratio) is 20/1 or more, and component (C)/component (B) (molar ratio) is 0.5/1 to 20 The hydrogenation catalyst according to claim 1, wherein the hydrogenation catalyst is: /1. 3. A claim that the bis(cyclopentadienyl) titanium compound, bis(cyclopentadienyl) zirconium compound, or bis(cyclopentadienyl) hafnium compound of component (B) is a compound represented by the following general formula (I) Item 1. Hydrogenation catalyst according to item 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, M is Ti, Zr or Hf, and R^1, R^
2 is a halogen atom, a hydrocarbon group, an allyloxy group, an alkoxy group, or a carbonyl group, and R^1 and R^2 may be the same or different] 4. The reducing organometallic compound is an organoaluminum The hydrogenation catalyst according to claim 1, which is a compound, an organozinc compound, an organomagnesium compound, an organolithium compound or an alkoxylithium compound. 5. A method for hydrogenating an olefinic double bond-containing polymer, which comprises reacting the catalyst according to claim 1 at 20 to 100°C and under a hydrogen pressure of 4 to 20 kg/cm^2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32599888A JP2658328B2 (en) | 1988-12-26 | 1988-12-26 | Hydrogenation catalyst and hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32599888A JP2658328B2 (en) | 1988-12-26 | 1988-12-26 | Hydrogenation catalyst and hydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02172537A true JPH02172537A (en) | 1990-07-04 |
| JP2658328B2 JP2658328B2 (en) | 1997-09-30 |
Family
ID=18182957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32599888A Expired - Lifetime JP2658328B2 (en) | 1988-12-26 | 1988-12-26 | Hydrogenation catalyst and hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2658328B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5244980A (en) * | 1992-12-07 | 1993-09-14 | Shell Oil Company | Selective hydrogenation of conjugated diolefin polymers with Tebbe's reagent |
| KR100247948B1 (en) * | 1991-10-30 | 2000-03-15 | 오노 알버어스 | Depolymerization of conjugated diene polymers |
| JP2011094139A (en) * | 2009-10-30 | 2011-05-12 | Tsrc Corp | Catalyst composition and hydrogenation method using the same |
| WO2014046016A1 (en) | 2012-09-21 | 2014-03-27 | 旭化成ケミカルズ株式会社 | Hydrogenation catalyst composition and hydrogenation method using said hydrogenation catalyst composition |
| WO2014046017A1 (en) | 2012-09-21 | 2014-03-27 | 旭化成ケミカルズ株式会社 | Catalyst composition for hydrogenation and hydrogenation method using catalyst composition for hydrogenation |
| WO2014065283A1 (en) | 2012-10-24 | 2014-05-01 | 旭化成ケミカルズ株式会社 | Method of producing hydrogenation catalyst composition and hydrogenation catalyst composition |
| WO2017090714A1 (en) | 2015-11-27 | 2017-06-01 | 旭化成株式会社 | Catalyst composition for hydrogenation, method for producing same, hydrogenated polymer and method for producing hydrogenated polymer |
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-
1988
- 1988-12-26 JP JP32599888A patent/JP2658328B2/en not_active Expired - Lifetime
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100247948B1 (en) * | 1991-10-30 | 2000-03-15 | 오노 알버어스 | Depolymerization of conjugated diene polymers |
| US5244980A (en) * | 1992-12-07 | 1993-09-14 | Shell Oil Company | Selective hydrogenation of conjugated diolefin polymers with Tebbe's reagent |
| US5334566A (en) * | 1992-12-07 | 1994-08-02 | Shell Oil Company | Selective hydrogenation of conjugated diolefin polymers with Tebbe's reagent |
| JP2011094139A (en) * | 2009-10-30 | 2011-05-12 | Tsrc Corp | Catalyst composition and hydrogenation method using the same |
| RU2608996C2 (en) * | 2012-09-21 | 2017-01-30 | Асахи Касеи Кемикалз Корпорейшн | Catalyst composition for hydrogenation and hydrogenation method using same |
| US9522393B2 (en) | 2012-09-21 | 2016-12-20 | Asahi Kasei Chemicals Corporation | Catalyst composition for hydrogenation and method for hydrogenation using the same |
| US10016749B2 (en) | 2012-09-21 | 2018-07-10 | Asahi Kasei Chemicals Corporation | Catalyst composition for hydrogenation and method for hydrogenation using the same |
| KR20150038472A (en) | 2012-09-21 | 2015-04-08 | 아사히 가세이 케미칼즈 가부시키가이샤 | Hydrogenation catalyst composition and hydrogenation method using said hydrogenation catalyst composition |
| KR20150038473A (en) | 2012-09-21 | 2015-04-08 | 아사히 가세이 케미칼즈 가부시키가이샤 | Catalyst composition for hydrogenation and hydrogenation method using catalyst composition for hydrogenation |
| CN104640629A (en) * | 2012-09-21 | 2015-05-20 | 旭化成化学株式会社 | Catalyst composition for hydrogenation and hydrogenation method using catalyst composition for hydrogenation |
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| JPWO2014046016A1 (en) * | 2012-09-21 | 2016-08-18 | 旭化成株式会社 | Hydrogenation catalyst composition and hydrogenation method using the hydrogenation catalyst composition |
| JPWO2014046017A1 (en) * | 2012-09-21 | 2016-08-18 | 旭化成株式会社 | Hydrogenation catalyst composition and hydrogenation method using the hydrogenation catalyst composition |
| WO2014046017A1 (en) | 2012-09-21 | 2014-03-27 | 旭化成ケミカルズ株式会社 | Catalyst composition for hydrogenation and hydrogenation method using catalyst composition for hydrogenation |
| RU2609020C2 (en) * | 2012-09-21 | 2017-01-30 | Асахи Касеи Кемикалз Корпорейшн | Catalyst composition for hydrogenation and hydrogenation method using same |
| WO2014046016A1 (en) | 2012-09-21 | 2014-03-27 | 旭化成ケミカルズ株式会社 | Hydrogenation catalyst composition and hydrogenation method using said hydrogenation catalyst composition |
| KR20150058460A (en) | 2012-10-24 | 2015-05-28 | 아사히 가세이 케미칼즈 가부시키가이샤 | Method of producing hydrogenation catalyst composition and hydrogenation catalyst composition |
| WO2014065283A1 (en) | 2012-10-24 | 2014-05-01 | 旭化成ケミカルズ株式会社 | Method of producing hydrogenation catalyst composition and hydrogenation catalyst composition |
| US10144004B2 (en) | 2012-10-24 | 2018-12-04 | Asahi Kasei Chemicals Corporation | Method for producing catalyst composition for hydrogenation and catalyst composition for hydrogenation |
| WO2017090714A1 (en) | 2015-11-27 | 2017-06-01 | 旭化成株式会社 | Catalyst composition for hydrogenation, method for producing same, hydrogenated polymer and method for producing hydrogenated polymer |
| KR20180070690A (en) | 2015-11-27 | 2018-06-26 | 아사히 가세이 가부시키가이샤 | Catalyst composition for hydrogenation, production method thereof, and hydrogenated polymer and production method thereof |
| WO2023038095A1 (en) | 2021-09-13 | 2023-03-16 | 日本エラストマー株式会社 | Crosslinked rubber composition, method for producing crosslinked rubber composition |
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