JP4956956B2 - Hydrogenation catalyst and method for producing hydrogenated polymer - Google Patents
Hydrogenation catalyst and method for producing hydrogenated polymer Download PDFInfo
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- JP4956956B2 JP4956956B2 JP2005297654A JP2005297654A JP4956956B2 JP 4956956 B2 JP4956956 B2 JP 4956956B2 JP 2005297654 A JP2005297654 A JP 2005297654A JP 2005297654 A JP2005297654 A JP 2005297654A JP 4956956 B2 JP4956956 B2 JP 4956956B2
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- palladium
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- 239000003054 catalyst Substances 0.000 title claims description 151
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 84
- 229920000642 polymer Polymers 0.000 title claims description 83
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 organic acid salt Chemical class 0.000 claims description 147
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 118
- 150000001875 compounds Chemical class 0.000 claims description 50
- 229910052763 palladium Inorganic materials 0.000 claims description 49
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 28
- 238000007142 ring opening reaction Methods 0.000 claims description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 15
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 15
- 150000001639 boron compounds Chemical class 0.000 claims description 14
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical group C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 12
- 150000002941 palladium compounds Chemical class 0.000 claims description 11
- 150000004820 halides Chemical class 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 9
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 9
- 150000007524 organic acids Chemical class 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 7
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical group C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 5
- 150000002900 organolithium compounds Chemical class 0.000 claims description 4
- 150000002901 organomagnesium compounds Chemical class 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 4
- 229920001577 copolymer Polymers 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 28
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 24
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 12
- HIPQYVJOMHDTRF-UHFFFAOYSA-N deca-2,7-diene Chemical compound CCC=CCCCC=CC HIPQYVJOMHDTRF-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000002834 transmittance Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 11
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- WLTSXAIICPDFKI-UHFFFAOYSA-N 3-dodecene Chemical compound CCCCCCCCC=CCC WLTSXAIICPDFKI-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000004645 aluminates Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- PXFLQFVYDGCREE-UHFFFAOYSA-N methyl 2-propyldec-7-enoate Chemical compound CCCC(CCCCC=CCC)C(=O)OC PXFLQFVYDGCREE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 3
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- IWYAFGRAMUCVCN-UHFFFAOYSA-N 2-propyldec-7-enoic acid Chemical compound CCCC(C(O)=O)CCCCC=CCC IWYAFGRAMUCVCN-UHFFFAOYSA-N 0.000 description 2
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 description 2
- KLAWFKRMCIXRFS-UHFFFAOYSA-N 5-ethenylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C=C)CC1C=C2 KLAWFKRMCIXRFS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 2
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 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
- QMPMMTQPOQXFKB-UHFFFAOYSA-N (2,4,6-trifluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C=C1F QMPMMTQPOQXFKB-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-M 1-naphthoate Chemical compound C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-M 0.000 description 1
- LAZHUUGOLCHESB-UHFFFAOYSA-N 2,3-dimethylbicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(C)C(C)C1C=C2 LAZHUUGOLCHESB-UHFFFAOYSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical group CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- XDRAKJQFCQVBMP-UHFFFAOYSA-N 2-but-2-enyl-3-methylbutanedioic acid Chemical compound CC=CCC(C(O)=O)C(C)C(O)=O XDRAKJQFCQVBMP-UHFFFAOYSA-N 0.000 description 1
- WXZYUEVSKZXZMY-UHFFFAOYSA-N 2-butyloxaluminane Chemical compound CCCC[Al]1CCCCO1 WXZYUEVSKZXZMY-UHFFFAOYSA-N 0.000 description 1
- WPGIANFVQQICQL-UHFFFAOYSA-L 2-ethylhexanoate;palladium(2+) Chemical compound [Pd+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WPGIANFVQQICQL-UHFFFAOYSA-L 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- KVYAQQCJQHSQOE-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enyl(trimethyl)silane Chemical compound C1C2C([Si](C)(C)C)CC1C=C2 KVYAQQCJQHSQOE-UHFFFAOYSA-N 0.000 description 1
- YHESWXAODSYVCO-UHFFFAOYSA-N 5-but-1-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=CCC)CC1C=C2 YHESWXAODSYVCO-UHFFFAOYSA-N 0.000 description 1
- LVXDMUDXBUNBQY-UHFFFAOYSA-N 5-cyclohexylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1CCCCC1 LVXDMUDXBUNBQY-UHFFFAOYSA-N 0.000 description 1
- VTWPBVSOSWNXAX-UHFFFAOYSA-N 5-decylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCCCC)CC1C=C2 VTWPBVSOSWNXAX-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はオレフィン性不飽和結合を有する化合物の水素化触媒および水素化重合体の製造方法に関する。 The present invention relates to a hydrogenation catalyst for a compound having an olefinically unsaturated bond and a method for producing a hydrogenated polymer.
オレフィン性不飽和結合を有する低分子量あるいは高分子量の有機化合物の水素化触媒は従来から知られており、例えば下記の水素化触媒が挙げられる。
１)Ｐｄ、Ｐｔ、Ｎｉ、酸化Ｒｕなどの金属を活性炭、シリカ、ケイソウ土、アルミナ
、ゼオライトなどの担体上に担持した触媒。(非特許文献１、２)
２)Ｒｕ、Ｒｈ、Ｉｒ、Ｐｄなどの錯体触媒。(非特許文献１、３、４、５)
３)Ｔｉ、Ｚｒ、Ｈｆなどのシクロペンタジエニル化合物、Ｎｉ、Ｃｏ、Ｐｄなどのベ
ータジケトン化合物またはカルボン酸塩とＬｉ、Ａｌなどの有機金属化合物、またはヒドリド化合物との組み合わせの触媒。(非特許文献１、４)
重合体に関しては、水素化は耐熱劣化性を向上するために有用である。しかしながら、水素化反応後に触媒が重合体中に残留すると、高温における酸化劣化や分子切断を引き起こし、機械的性質の低下や着色をまねくことがあった。このため、水素化触媒を多量に使用した場合には、触媒残さを除去しなければならず、そのために多くの労力を要するという問題があった。
Conventionally, hydrogenation catalysts for low molecular weight or high molecular weight organic compounds having an olefinically unsaturated bond are known. Examples thereof include the following hydrogenation catalysts.
1) A catalyst in which a metal such as Pd, Pt, Ni, and oxidized Ru is supported on a support such as activated carbon, silica, diatomaceous earth, alumina, or zeolite. (Non-Patent Documents 1 and 2)
2) Complex catalysts such as Ru, Rh, Ir and Pd. (Non-Patent Documents 1, 3, 4, 5)
3) A catalyst comprising a combination of a cyclopentadienyl compound such as Ti, Zr or Hf, a beta diketone compound or carboxylate such as Ni, Co or Pd and an organometallic compound such as Li or Al, or a hydride compound. (Non-Patent Documents 1 and 4)
For polymers, hydrogenation is useful to improve heat resistance. However, if the catalyst remains in the polymer after the hydrogenation reaction, it may cause oxidative degradation and molecular cleavage at high temperatures, resulting in deterioration of mechanical properties and coloring. For this reason, when a large amount of the hydrogenation catalyst is used, the catalyst residue must be removed, which requires a lot of labor.
また水素化に際し高い水素圧力が要求されるため、高圧仕様の反応器が必要となる、余剰の水素の回収に多くのエネルギーを要するなど、経済性に欠けるという問題点もあった。 In addition, since a high hydrogen pressure is required for hydrogenation, a high-pressure reactor is required, and a large amount of energy is required to recover surplus hydrogen.
さらに、水素化触媒としてＲｕ，Ｒｈなどを含むものを用いた場合、１４０℃以上の高温条件が必要となり、その際に分子切断が起こるという問題点があった。
このため、より低温・低圧で水素化可能な触媒として、パラジウムの有機酸塩が共役ジエン系重合体の水素化に関して提案されている。さらにパラジウム原子を含む水素化触媒の活性向上のために、分子状の水素、ヒドラジン、トリアルキルアルミニウム、メチルアルモキサンなどによって処理することも提案されている(非特許文献４、特許文献１、２)。しかしながら、９０％を超えるオレフィン性不飽和結合の水素化率を達成するには、依然として、重合体に対し、Ｐｄ原子に換算して１００ppm以上の触媒が必要であった。
Furthermore, when a catalyst containing Ru, Rh or the like is used as a hydrogenation catalyst, a high temperature condition of 140 ° C. or higher is required, and there is a problem that molecular cleavage occurs at that time.
For this reason, an organic acid salt of palladium has been proposed for hydrogenating conjugated diene polymers as a catalyst that can be hydrogenated at a lower temperature and a lower pressure. Furthermore, in order to improve the activity of the hydrogenation catalyst containing a palladium atom, treatment with molecular hydrogen, hydrazine, trialkylaluminum, methylalumoxane and the like has also been proposed (Non-patent Document 4, Patent Documents 1 and 2). ). However, in order to achieve a hydrogenation rate of olefinic unsaturated bonds exceeding 90%, a catalyst of 100 ppm or more in terms of Pd atoms was still required for the polymer.
このように、比較的、低圧でかつ、少ない触媒量で水素化可能であり、しかも高活性な水素化触媒が求められている。
本発明はオレフィン性不飽和結合を有する化合物、特にオレフィン性不飽和結合を有す
る重合体の水素化に有用であり、比較的、低圧でかつ、少ない触媒量で水素化できる高活性な水素化触媒を提供するものである。
The present invention is useful for hydrogenation of a compound having an olefinically unsaturated bond, particularly a polymer having an olefinically unsaturated bond, and is a highly active hydrogenation catalyst capable of hydrogenation at a relatively low pressure and with a small amount of catalyst. Is to provide.
そこで、本発明者らは、従来の水素化触媒における問題点を解消すべく鋭意検討した。その結果、パラジウム化合物とともに、特定のホスフィン化合物、およびイオン性のホウ素化合物またはイオン性のアルミニウム化合物を併用することで、低圧かつ少ない触媒量であっても重合体中のオレフィン性不飽和結合を効率的に水素化できることを見出し、本発明を完成するに至った。 Therefore, the present inventors have intensively studied to solve the problems in the conventional hydrogenation catalyst. As a result, by using a specific phosphine compound and an ionic boron compound or an ionic aluminum compound together with a palladium compound, the olefinic unsaturated bond in the polymer is efficiently produced even at a low pressure and with a small catalyst amount. As a result, the present invention was completed.
本発明の構成は以下の通りである。
［１］下記触媒成分(ａ)〜(ｃ)を含む混合物から得られてなることを特徴とする、オレフィン性不飽和結合を有する化合物の水素化触媒：
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ)式(２)で表されるホスフィン化合物
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、
シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、
ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基
からそれぞれ独立に選ばれた置換基〕
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物。
［２］さらに、触媒成分として(ｄ)有機アルミニウム化合物、有機マグネシウム化合物および有機リチウム化合物なる群からから選ばれる少なくとも１種の化合物を含む［１］の水素化触媒。
［３］触媒成分として、ｅ)ビシクロ[２．２．１]ヘプタ−２−エン構造またはビシクロ[２．２．１]ヘプタ−２，５−ジエン構造を有する多環状オレフィン化合物を含む［１］
および[２]の水素化触媒。
［４］触媒成分(ａ)および(ｂ)として、下記式(３)で表されるパラジウム錯体を用いる［１］〜［３］の水素化触媒。
The configuration of the present invention is as follows.
[1] A hydrogenation catalyst for a compound having an olefinically unsaturated bond, which is obtained from a mixture containing the following catalyst components (a) to (c):
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) A phosphine compound represented by formula (2)
P (R 1 ) 3 Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, a 3-methylcyclopentyl group,
Cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group,
Substituents independently selected from i-propyl, t-butyl, 2-methylphenyl, and pentafluorophenyl groups]
(c) A compound selected from an ionic boron compound or an ionic aluminum compound.
[2] The hydrogenation catalyst according to [1], further comprising (d) at least one compound selected from the group consisting of an organoaluminum compound, an organomagnesium compound, and an organolithium compound as a catalyst component.
[3] The catalyst component includes e) a polycyclic olefin compound having a bicyclo [2.2.1] hept-2-ene structure or a bicyclo [2.2.1] hepta-2,5-diene structure [1] ]
And the hydrogenation catalyst of [2].
[4] The hydrogenation catalyst of [1] to [3] using a palladium complex represented by the following formula (3) as the catalyst components (a) and (b).
Ｐｄ(Ｘ)k・〔Ｐ(Ｒ1)3〕m …式(３)
〔式(３)でＰｄはパラジウム原子、Ｘは有機酸アニオン、ベータジケトンアニオン、ハロゲン化物アニオン、Ｐ(Ｒ1)3は式(２)と同じ、ｋおよびｍは１または２を示す。〕
［５］Ｐｄ(Ｘ)2で表されるパラジウム化合物が、パラジウムの有機カルボン酸塩および
ベータジケトン化合物から選ばれる少なくとも１種の化合物であることを特徴とする［１］〜［４］の水素化触媒。
［６］式(２)で表されるホスフィン化合物がトリシクロペンチルホスフィン、トリシクロヘキシルホスフィンから選ばれたホスフィン化合物である［１］〜［５］の水素化触媒。［７］触媒成分(ｃ)が、カルベニウムカチオンを有するイオン性ホウ素化合物であることを特徴とする［１］〜［６］の水素化触媒。
［８］上記触媒成分(ａ)〜(ｃ)を用いることにより、
共役ジエン化合物の付加重合体、環状オレフィンの付加重合体、環状オレフィンの開環重合体であって、重量平均分子量が１，０００〜１，０００，０００の範囲にある高分子重合体中のオレフィン性不飽和結合を水素化することを特徴とする水素化重合体の製造方法。
Pd (X) k · [P (R 1 ) 3 ] m ... Formula (3)
[In formula (3), Pd is a palladium atom, X is an organic acid anion, beta diketone anion, halide anion, P (R 1 ) 3 is the same as in formula (2), and k and m are 1 or 2. ]
[5] The hydrogen of [1] to [4], wherein the palladium compound represented by Pd (X) 2 is at least one compound selected from an organic carboxylate of palladium and a beta diketone compound. Catalyst.
[6] The hydrogenation catalyst according to [1] to [5], wherein the phosphine compound represented by the formula (2) is a phosphine compound selected from tricyclopentylphosphine and tricyclohexylphosphine. [7] The hydrogenation catalyst according to [1] to [6], wherein the catalyst component (c) is an ionic boron compound having a carbenium cation.
[8] By using the catalyst components (a) to (c),
Addition polymers of conjugated diene compounds, addition polymers of cyclic olefins, ring-opening polymers of cyclic olefins, and olefins in high molecular weight polymers having a weight average molecular weight in the range of 1,000 to 1,000,000 A method for producing a hydrogenated polymer, characterized by hydrogenating a polymerizable unsaturated bond.
本発明のパラジウム系水素化触媒を用いることにより、少ない触媒量で水素化された化合物が得られる。高分子量の重合体においては残存するパラジウム触媒量が少なく、触媒の除去が容易で耐熱劣化性に優れた、色相が良好な水素化された重合体が得られる。 By using the palladium hydrogenation catalyst of the present invention, a hydrogenated compound can be obtained with a small catalyst amount. In the high molecular weight polymer, the amount of the remaining palladium catalyst is small, and a hydrogenated polymer with good hue can be obtained which is easy to remove the catalyst and excellent in heat deterioration resistance.
以下、本発明について詳細に説明する。
水素化触媒
本発明にかかる水素化触媒は、下記触媒成分(ａ)、触媒成分(ｂ)、触媒成分(ｃ)を含む水素化触媒である。
触媒成分(ａ)
触媒成分(ａ)として、式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物が使用される。
Hereinafter, the present invention will be described in detail.
Hydrogenation Catalyst The hydrogenation catalyst according to the present invention is a hydrogenation catalyst comprising the following catalyst component (a), catalyst component (b), and catalyst component (c).
Catalyst component (a)
As the catalyst component (a), an organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1) is used.
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
このようなパラジウム化合物としては、式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物およびハロゲン化物から選ばれた化合物の具体例として、酢酸パラジウム、トリフルオロ酢酸パラジウム、ブタン酸パラジウム、２−エチルヘキサン酸パラジウム、ドデカン酸パラジウム、オクタデカ−９−エン酸パラジウム、シクロヘキサンカルボン酸パラジウム、シクロヘキサン−１，２−ジカルボン酸パラジウム、ビシクロ[２
．２．１]ヘプタ−２−エン−５，６−ジカルボン酸パラジウム、安息香酸パラジウム、
３−メチル安息香酸パラジウム、４−メチル安息香酸パラジウム、ナフタレンカルボン酸パラジウム、メタンスルホン酸パラジウム、トリフルオロメタンスルホン酸パラジウム、ｐ−トルエンスルホン酸パラジウム、ベンゼンスルホン酸パラジウム、ナフタレンスルホン酸パラジウム、ドデシルベンゼンスルホン酸パラジウム、パラジウムビス(アセチルア
セトネート)、ビス(１−エトキシ−１，３−ブタンジオナート)パラジウム、パラジウム
ビス(ヘキサフルオロアセチルアセトネート)、パラジウムビス(２，２，６，６−テトラ
メチルヘプタ−３，５−ジオナート)、ビス(トリシクロヘキシルホスフィン)パラジウム
ジクロライド、ビス(トリシクロヘキシルホスフィン)パラジウムジブロマイド、ビス(ト
リシクロペンチルホスフィン)パラジウムジクロライド、ビス(トリシクロペンチルホスフィン)パラジウムジブロマイドなどが用いられる。
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
Examples of such a palladium compound include palladium acetate, palladium trifluoroacetate, butane as specific examples of compounds selected from organic acid salts of palladium (II) represented by formula (1), beta diketone compounds and halides. Palladium oxide, palladium 2-ethylhexanoate, palladium dodecanoate, palladium octadec-9-enoate, palladium cyclohexanecarboxylate, palladium cyclohexane-1,2-dicarboxylate, bicyclo [2
. 2.1] palladium hept-2-ene-5,6-dicarboxylate, palladium benzoate,
Palladium 3-methylbenzoate, palladium 4-methylbenzoate, palladium naphthalenecarboxylate, palladium methanesulfonate, palladium trifluoromethanesulfonate, palladium p-toluenesulfonate, palladium benzenesulfonate, palladium naphthalenesulfonate, dodecylbenzenesulfone Palladium acid, palladium bis (acetylacetonate), bis (1-ethoxy-1,3-butanedionate) palladium, palladium bis (hexafluoroacetylacetonate), palladium bis (2,2,6,6-tetramethyl Hepta-3,5-dionate), bis (tricyclohexylphosphine) palladium dichloride, bis (tricyclohexylphosphine) palladium dibromide, bis (tricyclopentylphosphine) paradiu Dichloride, and bis (tricyclopentylphosphine) palladium dibromide is used.
本発明では、前記式(１)Ｐｄ(Ｘ)kで表されるパラジウム化合物が、パラジウムのカル
ボン酸塩およびベータジケトン化合物から選ばれる少なくとも１種の化合物であることが好ましい。かかる化合物を使用することにより、炭化水素溶媒、ハロゲン化炭化水素溶媒、カルボニル基を有する溶媒等への溶解性が良好で、さらには水素化触媒として優れた活性を示すものになる。特に好ましいのはパラジウムの炭素数が２〜１５の脂肪族または脂環族のカルボン酸塩である。
触媒成分(ｂ)
触媒成分(ｂ)としては、式(２)で表されるホスフィン化合物が使用される。
In the present invention, the palladium compound represented by the formula (1) Pd (X) k is preferably at least one compound selected from a palladium carboxylate and a beta diketone compound. By using such a compound, solubility in a hydrocarbon solvent, a halogenated hydrocarbon solvent, a solvent having a carbonyl group, etc. is good, and further, an excellent activity as a hydrogenation catalyst is exhibited. Particularly preferred is an aliphatic or alicyclic carboxylate having 2 to 15 carbon atoms of palladium.
Catalyst component (b)
As the catalyst component (b), a phosphine compound represented by the formula (2) is used.
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、
シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、
ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基
からそれぞれ独立に選ばれた置換基〕
式(２)で表されるホスフィン化合物の具体例として、
トリシクロペンチルホスフィン、ジシクロペンチル(イソプロピル)ホスフィン、トリ(
３−メチルシクロペンチル)ホスフィン、ジシクロペンチル(３−メチルシクロペンチル)
ホスフィン、ジシクロペンチルフェニルホスフィン、ジシクロペンチル(シクロヘキシル)ホスフィン、トリシクロヘキシルホスフィン、ジシクロヘキシル(イソプロピル)ホスフィン、ジシクロペンチル(ｔ−ブチル)ホスフィン、ジシクロヘキシル(３−メチルシクロヘ
キシル)ホスフィン、ジシクロヘキシル(２−メチルフェニル)ホスフィン、トリ(ｔ−ブチル)ホスフィン、トリイソプロピルホスフィン、トリ(２−メチルフェニル)ホスフィン、
トリ(ペンタフルオロフェニル)ホスフィンなどが挙げられる。
P (R 1 ) 3 Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, a 3-methylcyclopentyl group,
Cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group,
Substituents independently selected from i-propyl, t-butyl, 2-methylphenyl, and pentafluorophenyl groups]
As a specific example of the phosphine compound represented by the formula (2),
Tricyclopentylphosphine, dicyclopentyl (isopropyl) phosphine, tri (
3-methylcyclopentyl) phosphine, dicyclopentyl (3-methylcyclopentyl)
Phosphine, dicyclopentylphenylphosphine, dicyclopentyl (cyclohexyl) phosphine, tricyclohexylphosphine, dicyclohexyl (isopropyl) phosphine, dicyclopentyl (t-butyl) phosphine, dicyclohexyl (3-methylcyclohexyl) phosphine, dicyclohexyl (2-methylphenyl) phosphine , Tri (t-butyl) phosphine, triisopropylphosphine, tri (2-methylphenyl) phosphine,
And tri (pentafluorophenyl) phosphine.
これらホスフィン化合物の中でトリシクロペンチルホスフィン、トリシクロヘキシルホスフィンが、水素化触媒として活性が高いことや、パラジウム化合物とで形成される錯体の溶解性が良好である点で好ましい。
触媒成分(ａ＋ｂ)
本発明においては触媒成分(ａ)の特定のパラジウム化合物と触媒成分(ｂ)の特定のホスフィン化合物とを独立して用いてもよく、また、触媒成分(ａ)と触媒成分(ｂ)とを予め反応させ、錯体としたものを用いてもよい。当該錯体は下記式(３)で表されるパラジウム錯体である(以下、かかるパラジウム錯体を触媒成分(ａ＋ｂ)ということもある)。
Among these phosphine compounds, tricyclopentylphosphine and tricyclohexylphosphine are preferable because of their high activity as a hydrogenation catalyst and good solubility of complexes formed with palladium compounds.
Catalyst component (a + b)
In the present invention, the specific palladium compound of the catalyst component (a) and the specific phosphine compound of the catalyst component (b) may be used independently, and the catalyst component (a) and the catalyst component (b) may be used. You may make it react beforehand and use it as the complex. The complex is a palladium complex represented by the following formula (3) (hereinafter, this palladium complex may be referred to as a catalyst component (a + b)).
Ｐｄ(Ｘ)k・〔Ｐ(Ｒ1)3〕m …式(３)
〔式(３)でＰｄはパラジウム原子、Ｘは有機酸アニオン、ベータジケトンアニオン、ハロゲン化物アニオン、Ｐ(Ｒ1)3は式(２)と同じ、ｋ、ｍは１または２を示す。〕
具体的なパラジウム錯体として
トリシクロヘキシルホスフィンパラジウムジ(アセテート)、ビス(トリシクロヘキシル
ホスフィン)パラジウムジ(アセテート)、トリシクロペンチルホスフィンパラジウムジ(アセテート)、ビス(トリシクロペンチルホスフィン)パラジウムジ(アセテート)、ビス〔ジ
シクロペンチル(２−メチルフェニル)ホスフィン〕パラジウムジ(アセテート)、ビス〔ジシクロヘキシル(ｔ−ブチル)ホスフィン〕パラジウムジ(アセテート)、ビス(トリシクロ
ペンチルホスフィン)パラジウムジ(トリフルオロアセテート)、ビス(トリシクロヘキシルホスフィン)パラジウムジ(トリフルオロアセテート)、ビス(トリシクロペンチルホスフィン)パラジウムジ(プロパノエ−ト)、ビス(トリシクロヘキシルホスフィン)パラジウムジ(プロパノエート)、ビス(トリシクロペンチルホスフィン)パラジウムビス(２−エチルヘキサノエート)、ビス(トリシクロヘキシルホスフィン)パラジウムビス(シクロヘキサンカルボキシレート)、ビス(トリシクロヘキシルホスフィン)パラジウムジ(オクタノエート)、
ビス(トリシクロヘキシルホスフィン)パラジウムジ(ベンゾエート)などが挙げられる。
触媒成分(ｃ)
ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合
物としては、式(４)で表されるイオン性のホウ素化合物、または式(５)で表されるイオン性のアルミニウム化合物から選ばれる化合物が使用される。
Pd (X) k · [P (R 1 ) 3 ] m ... Formula (3)
[In formula (3), Pd is a palladium atom, X is an organic acid anion, beta diketone anion, halide anion, P (R 1 ) 3 is the same as in formula (2), and k and m are 1 or 2. ]
Specific palladium complexes include tricyclohexylphosphine palladium di (acetate), bis (tricyclohexylphosphine) palladium di (acetate), tricyclopentylphosphine palladium di (acetate), bis (tricyclopentylphosphine) palladium di (acetate), bis [ Dicyclopentyl (2-methylphenyl) phosphine] palladium di (acetate), bis [dicyclohexyl (t-butyl) phosphine] palladium di (acetate), bis (tricyclopentylphosphine) palladium di (trifluoroacetate), bis (tricyclohexyl Phosphine) palladium di (trifluoroacetate), bis (tricyclopentylphosphine) palladium di (propanoate), bis (tricyclohexylphosphine) palladium di (propanoate) Bis (tricyclopentylphosphine) palladium bis (2-ethylhexanoate), bis (tricyclohexylphosphine) palladium bis (cyclohexanecarboxylate), bis (tricyclohexylphosphine) palladium di (octanoate),
And bis (tricyclohexylphosphine) palladium di (benzoate).
Catalyst component (c)
c) As an ionic boron compound or a compound selected from ionic aluminum compounds, an ionic boron compound represented by formula (4) or an ionic aluminum compound represented by formula (5) A compound selected from is used.
〔Ｒ2〕+〔Ｂ(Ｒ3)4〕- …式(４)
〔Ｒ2〕+〔Ａl(Ｒ3)4〕- …式(５)
〔式(４)および式(５)でＲ2はカルボニウムカチオン、ホスフォニウムカチオン、アンモ
ニウムカチオン、アニリニウムカチオンから選ばれた炭素数１〜２５の有機カチオン、Ｒ3はフッ素原子置換またはフッ化アルキル置換のフェニル基、Ｂはホウ素原子、Ａｌはア
ルミニウム原子を示す。〕
イオン性ホウ素化合物の具体例としては、トリフェニルカルベニウムテトラキス(ペン
タフルオロフェニル)ボレート、トリ(ｐ-トリル)カルベニウムテトラキス(ペンタフルオ
ロフェニル)ボレート、ジフェニル(メチル)カルベニウムテトラキス(ペンタフルオロフェニル)ボレート、ビス(ジフェニル)メチルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート、トリフェニルカルベニウムテトラキス［３，５−ビス(トリフルオロメチル
)フェニル］ボレート、トリフェニルカルベニウムテトラキス(２，４，６−トリフルオロフェニル)ボレート、トリフェニルカルベニウムテトラフェニルボレート等のカルベニウ
ムカチオンを有する化合物；
トリフェニルホスホニウムテトラキス(ペンタフルオロフェニル)ボレート、ジフェニルホスホニウムテトラキス(ペンタフルオロフェニル)ボレート等のホスホニウムカチオンを有する化合物；
トリブチルアンモニウムテトラキス(ペンタフルオロフェニル)ボレート等のアンモニウムカチオンを有する化合物；
Ｎ，Ｎ−ジメチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート、Ｎ，Ｎ−ジエチルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート、Ｎ，Ｎ−ジフェニルアニリニウムテトラキス(ペンタフルオロフェニル)ボレート等のアニリニウムカチオンを有する化合物；
リチウムテトラキス［３，５−ビス(トリフルオロメチル)フェニル］ボレート、リチウムテトラキス(ペンタフルオロフェニル)ボレート等のリチウムカチオンを有する化合物などが挙げられる。
[R 2] + [B (R 3) 4] - Equation (4)
[R 2] + [Al (R 3) 4] - Equation (5)
[In the formulas (4) and (5), R 2 is an organic cation having 1 to 25 carbon atoms selected from a carbonium cation, a phosphonium cation, an ammonium cation and an anilinium cation, and R 3 is a fluorine atom substituted or fluorinated group. Alkyl-substituted phenyl group, B represents a boron atom, and Al represents an aluminum atom. ]
Specific examples of ionic boron compounds include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (p-tolyl) carbeniumtetrakis (pentafluorophenyl) borate, diphenyl (methyl) carbeniumtetrakis (pentafluorophenyl) Borate, bis (diphenyl) methylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl)
) Phenyl] borate, triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) borate, triphenylcarbenium tetraphenylborate and other compounds having a carbenium cation;
Compounds having a phosphonium cation such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, diphenylphosphonium tetrakis (pentafluorophenyl) borate;
Compounds having an ammonium cation such as tributylammonium tetrakis (pentafluorophenyl) borate;
Anilinium cations such as N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diphenylanilinium tetrakis (pentafluorophenyl) borate Having a compound;
Examples thereof include compounds having a lithium cation such as lithium tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and lithium tetrakis (pentafluorophenyl) borate.
イオン性アルミニウム化合物の具体例としては、
トリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)アルミナート、トリフェニルカルベニウムテトラキス［３，５−ビス(トリフルオロメチル)フェニル］アルミナート、トリフェニルカルベニウムテトラキス(２，４，６−トリフルオロフェニル)アルミナート、トリフェニルカルベニウムテトラフェニルアルミナート等のカルベニウムカチオンを有する化合物などが挙げられる。
As a specific example of the ionic aluminum compound,
Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, triphenylcarbenium tetrakis [3,5-bis (trifluoromethyl) phenyl] aluminate, triphenylcarbenium tetrakis (2,4,6-trifluorophenyl) Examples thereof include compounds having a carbenium cation such as aluminate and triphenylcarbenium tetraphenylaluminate.
特にカルベニウムカチオンを有するイオン性ホウ素化合物を使用すると、水素化触媒としての活性が特に優れたものになるため好ましい。
本発明では触媒成分として、触媒成分(ａ)、触媒成分(ｂ)および触媒成分(ｃ)以外に、必要に応じて触媒成分(ｄ)として、有機アルミニウム化合物、有機マグネシウム化合物および有機リチウム化合物からなる群から選ばれる少なくとも1種の有機金属化合物を用い
ることができる。
触媒成分(ｄ)
触媒成分(ｄ)の添加により、水素化触媒の活性向上や、反応系に存在する微量に存在する活性阻害物質を除去することができる。
In particular, the use of an ionic boron compound having a carbenium cation is preferable because the activity as a hydrogenation catalyst is particularly excellent.
In the present invention, as the catalyst component, in addition to the catalyst component (a), the catalyst component (b) and the catalyst component (c), if necessary, the catalyst component (d) is composed of an organoaluminum compound, an organomagnesium compound and an organolithium compound. At least one organometallic compound selected from the group can be used.
Catalyst component (d)
By adding the catalyst component (d), it is possible to improve the activity of the hydrogenation catalyst and remove the activity-inhibiting substance present in a trace amount in the reaction system.
有機アルミニウム化合物としては、少なくとも１つのアルミニウム−アルキル結合を有するアルミニウム化合物が用いることができ、例えば、メチルアルモキサン、エチルアルモキサン、ブチルアルモキサンなどのアルキルアルモキサン化合物、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウムなどのトリアルキルアルミニウム化合物、ジエチルアルミニウムヒドリド、ジブ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、ジエチルアルミニウムクロライド、ジイソブチルアルミニウムクロライドなどのジアルキルアルミニウムハライドあるいはヒドリド化合物を用いることができる。 As the organoaluminum compound, an aluminum compound having at least one aluminum-alkyl bond can be used. For example, alkylalumoxane compounds such as methylalumoxane, ethylalumoxane, and butylalumoxane, trimethylaluminum, triethylaluminum, trimethylaluminum, and the like. A trialkylaluminum compound such as isobutylaluminum, a dialkylaluminum halide such as diethylaluminum hydride, dibutylaluminum hydride, diisobutylaluminum hydride, diethylaluminum chloride, diisobutylaluminum chloride or a hydride compound can be used.
有機マグネシウム化合物として、少なくとも１つのマグネシウム−アルキル結合を有するマグネシウム化合物を用いることができ、例えば、ジメチルマグネシウム、ジエチルマグネシウム、ジブチルマグネシウム、メチルマグネシウムクロライド、エ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、ブチルマグネシウムクロライドなどが挙げられる。 As the organic magnesium compound, a magnesium compound having at least one magnesium-alkyl bond can be used. For example, dimethyl magnesium, diethyl magnesium, dibutyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, butyl magnesium chloride and the like. Can be mentioned.
有機リチウム化合物としては例えば、メチルリチウム、エチルリチウム、プロピルリチウム、ブチルリチウム、ヘキシルリチウム、１，４−ジリチオブタン、１，４−ビス(リ
チオイソプロピル)ベンゼンなどが挙げられる。
また、本発明では水素化触媒の成分として触媒成分(ａ)、(ｂ)および(ｃ)以外に、触媒成分(ｅ)として極性基を含まない環状オレフィン化合物を存在させることで、水素化触媒の活性を向上させることができる。
Examples of the organic lithium compound include methyl lithium, ethyl lithium, propyl lithium, butyl lithium, hexyl lithium, 1,4-dilithiobutane, 1,4-bis (lithioisopropyl) benzene, and the like.
Further, in the present invention, a hydrogenation catalyst is obtained by allowing a cyclic olefin compound not containing a polar group as the catalyst component (e) in addition to the catalyst components (a), (b) and (c) as components of the hydrogenation catalyst. The activity of can be improved.
このような環状オレフィン化合物はビシクロ[２．２．１]ヘプタ−２−エン構造またはビシクロ[２．２．１]ヘプター２，５−ジエン構造を有する化合物である。具体的には、ビシクロ[２．２．１]ヘプタ−２−エン、５−メチルビシクロ[２．２．１]ヘプタ−２−エン、５−エチルビシクロ[２．２．１]ヘプタ−２−エン、５−ブチルビシクロ[２．２
．１]ヘプタ−２−エン、５−ヘキシルビシクロ[２．２．１]ヘプタ−２−エン、５−オ
クチルビシクロ[２．２．１]ヘプタ−２−エン、５−デシルビシクロ[２．２．１]ヘプタ−２−エン、５−シクロヘキシルビシクロ[２．２．１]ヘプタ−２−エン、５−ビニルビシクロ[２．２．１]ヘプタ−２−エン、５−フェニルビシクロ[２．２．１]ヘプタ−２−エン、５−トリメチルシリルビシクロ[２．２．１]ヘプタ−２−エン、５、６−ジメチルビシクロ[２．２．１]ヘプタ−２−エン、５、６−ジベンゾビシクロ[２．２．１]ヘプタ−２−エン、ビシクロ[２．２．１]ヘプタ−２、５−ジエン、ビス〔ビシクロ[２．２．
１]ヘプタ−５−エン−２−イル〕ジメチルシラン、トリシクロ[５．２．１．０2,6]デカ−８−エン、トリシクロ[５．２．１．０2,6]デカ−３，８−ジエン、テトラシクロ[６．２．１．１3,6．０2,7]ドデカ−９−エン、４−エチルテトラシクロ[６．２．１．１3,6
．０2,7]ドデカ−９−エンなどの環状オレフィン化合物が挙げられる。
Such a cyclic olefin compound is a compound having a bicyclo [2.2.1] hept-2-ene structure or a bicyclo [2.2.1] hepter 2,5-diene structure. Specifically, bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hepta-2 -Ene, 5-butylbicyclo [2.2
. 1] Hept-2-ene, 5-hexylbicyclo [2.2.1] hept-2-ene, 5-octylbicyclo [2.2.1] hept-2-ene, 5-decylbicyclo [2.2 .1] Hept-2-ene, 5-cyclohexylbicyclo [2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, 5-phenylbicyclo [2. 2.1] hept-2-ene, 5-trimethylsilylbicyclo [2.2.1] hept-2-ene, 5,6-dimethylbicyclo [2.2.1] hept-2-ene, 5,6- Dibenzobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hepta-2,5-diene, bis [bicyclo [2.2.
1] hept-5-en-2-yl] dimethylsilane, tricyclo [5.2.1.0 2,6 ] dec-8-ene, tricyclo [5.2.1.0 2,6 ] dec-3 , 8-diene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, 4-ethyltetracyclo [6.2.1.1 3,6
. And cyclic olefin compounds such as 0 2,7 ] dodec-9-ene.
これらのなかでも、好ましくはビシクロ[２．２．１]ヘプタ−２−エン、またはアルキル基の炭素数が１〜６の５−アルキルビシクロ[２．２．１]ヘプタ−２−エンが用いられる。 Among these, Preferably, bicyclo [2.2.1] hept-2-ene or 5-alkylbicyclo [2.2.1] hept-2-ene having 1 to 6 carbon atoms in the alkyl group is used. It is done.
触媒成分(ａ)と(ｂ)とを組み合わせたのみ、あるいは触媒成分(ａ)と(ｃ)とを組み合わせたのみでは水素化触媒としての活性は低いのに対し、(ａ)〜(ｃ)を必須成分とすることで、活性を大幅に向上できる。さらに、触媒成分(ｄ)を触媒成分(ａ)〜(ｃ)の組み合わせに添加すると水素化触媒として活性のさらなる向上と反応系に存在する活性阻害物質を除去することができる。また、触媒成分(ｅ)を特に触媒成分(ａ)〜(ｃ)の組み合わせに添加すると、水素化反応の誘導期間がなく、水素化触媒としての活性をさらに向上できる。
組成
これら触媒成分は、以下の範囲の使用量で用いられる。
While only the combination of the catalyst components (a) and (b) or the combination of the catalyst components (a) and (c) has low activity as a hydrogenation catalyst, (a) to (c) As an essential component, the activity can be greatly improved. Further, when the catalyst component (d) is added to the combination of the catalyst components (a) to (c), it is possible to further improve the activity as a hydrogenation catalyst and to remove the activity inhibitory substance present in the reaction system. Further, when the catalyst component (e) is added to the combination of the catalyst components (a) to (c), there is no induction period for the hydrogenation reaction, and the activity as a hydrogenation catalyst can be further improved.
Composition These catalyst components are used in the following amounts.
触媒成分(ａ)は、水素化対象化合物に対して、Ｐｄ原子として１〜１００ｐｐｍ、好ましくは３〜７０ｐｐｍの範囲で用いられる。
触媒成分(ｂ)は、触媒成分(ａ)のパラジウム化合物１モル当たり、０．２〜５モル、好ましくは０．５〜２．０モルの量で用いられる。
The catalyst component (a) is used in the range of 1 to 100 ppm, preferably 3 to 70 ppm as Pd atoms with respect to the hydrogenation target compound.
The catalyst component (b) is used in an amount of 0.2 to 5 mol, preferably 0.5 to 2.0 mol, per mol of the palladium compound of the catalyst component (a).
触媒成分(ｃ)は、触媒成分(ａ)のパラジウム化合物１モル当たり、０．５〜１０モルの範囲で、好ましくは０．７〜２モルの範囲で用いられる。
触媒成分(ｄ)を添加する場合、触媒成分(ｄ)は触媒成分(ａ)のパラジウム化合物の１モル当たり、０．５〜２００モル、好ましくは５〜５０モルの範囲で用いられる。
触媒成分(ｅ)を添加する場合、触媒成分(ｅ)は触媒成分ａ)のパラジウム化合物１モル当
たり、０．５〜５０モル、好ましくは１〜１０モルの範囲で使用される。
The catalyst component (c) is used in the range of 0.5 to 10 mol, preferably in the range of 0.7 to 2 mol, per mol of the palladium compound of the catalyst component (a).
When the catalyst component (d) is added, the catalyst component (d) is used in the range of 0.5 to 200 mol, preferably 5 to 50 mol, per mol of the palladium compound of the catalyst component (a).
When the catalyst component (e) is added, the catalyst component (e) is used in an amount of 0.5 to 50 mol, preferably 1 to 10 mol, per mol of the palladium compound of the catalyst component a).
触媒成分の添加方法は特に制約はないが、通常、
１)水素化の反応基質と溶媒の混合物に触媒成分(ａ)および触媒成分(ｂ)、または触媒成
分(ａ＋ｂ)、および触媒成分(ｃ)の順に添加する方法、
２)水素化の反応基質と溶媒の混合物に、触媒成分(ａ)、触媒成分(ｂ)および触媒成分(ｃ
)の順に添加する方法、
３)予め、触媒成分(ａ)、(ｂ)および(ｃ)を混合接触したものを反応基質と溶媒の混合物
に添加する方法、などの方法が用いられる。
The method for adding the catalyst component is not particularly limited,
1) A method in which the catalyst component (a) and the catalyst component (b), or the catalyst component (a + b), and the catalyst component (c) are added to the hydrogenation reaction substrate and solvent mixture in this order,
2) Catalyst component (a), catalyst component (b) and catalyst component (c) are added to the hydrogenation reaction substrate and solvent mixture.
) Order of addition,
3) A method such as a method in which the catalyst components (a), (b), and (c) are mixed and contacted in advance is added to the mixture of the reaction substrate and the solvent.
なお、触媒成分(ｄ)および(ｅ)の添加順にも制限はなく、触媒成分(ａ)〜(ｃ)より先に、あるいは後に加えてよく、あるいは他の成分と予め混合して用いてもよい。
本発明の水素化触媒は粉体のまま、あるいは溶媒に溶解して使用することも可能であり、また、ペレット、ビーズ、ハニカムなどの所望の形状に成形してもよい。
The order in which the catalyst components (d) and (e) are added is not limited, and may be added before or after the catalyst components (a) to (c), or may be mixed in advance with other components. Good.
The hydrogenation catalyst of the present invention can be used in the form of powder or dissolved in a solvent, and may be formed into a desired shape such as pellets, beads, and honeycombs.
本発明の水素化触媒はシリカ、アルミナ、ケイソウ土、粘土鉱物および活性炭などの固体に担持して用いることもできる。担持量は担体に対して、水素化触媒のパラジウム原子当たり、０．１〜５重量％の範囲で用いられる。触媒を担持することにより、反応生成物の水素化物からの触媒の分離が容易なものとなる。 The hydrogenation catalyst of the present invention can also be used by being supported on a solid such as silica, alumina, diatomaceous earth, clay mineral and activated carbon. The supported amount is in the range of 0.1 to 5% by weight per palladium atom of the hydrogenation catalyst with respect to the support. By supporting the catalyst, the catalyst can be easily separated from the hydride of the reaction product.
水素化方法は水素化触媒の存在下で不活性溶媒中、水素ガス圧０．１〜１５ＭＰａ、反応温度２０〜１５０℃で水素化が行われる。芳香族のオレフィン性不飽和結合の水素化は５０〜１８０℃、水素圧３〜１５ＭＰａの条件で行われる。反応様式は、水素化触媒が、反応基質と接触すれば特に制限されるものではなく、流動床であっても、固定床であってもよい。 In the hydrogenation method, hydrogenation is performed in an inert solvent at a hydrogen gas pressure of 0.1 to 15 MPa and a reaction temperature of 20 to 150 ° C. in the presence of a hydrogenation catalyst. Hydrogenation of the aromatic olefinically unsaturated bond is performed under conditions of 50 to 180 ° C. and a hydrogen pressure of 3 to 15 MPa. The reaction mode is not particularly limited as long as the hydrogenation catalyst comes into contact with the reaction substrate, and may be a fluidized bed or a fixed bed.
水素化反応に用いられる溶媒としては、例えば、ヘキサン、ヘプタン、オクタン、ドデカンなどの炭素数５〜１４の脂肪族炭化水素、シクロヘキサン、シクロヘプタン、シクロデカン、メチルシクロヘキサンなどの炭素数５〜１４の脂環族炭化水素が挙げられる。また芳香環を水素化しない条件であれば、ベンゼン、トルエン、キシレン、エチルベンゼンなどの炭素数６〜１４の芳香族炭化水素も使用することができる。 Examples of the solvent used in the hydrogenation reaction include aliphatic hydrocarbons having 5 to 14 carbon atoms such as hexane, heptane, octane and dodecane, and fatty acids having 5 to 14 carbon atoms such as cyclohexane, cycloheptane, cyclodecane and methylcyclohexane. A cyclic hydrocarbon is mentioned. Also, aromatic hydrocarbons having 6 to 14 carbon atoms such as benzene, toluene, xylene and ethylbenzene can be used as long as the aromatic ring is not hydrogenated.
なお、本発明においては、これら溶媒を２種以上使用した混合溶媒も用いることができる。溶媒は水素化の反応基質１００重量部当たり、０〜２０００重量部の範囲で用いることができる。なお、反応基質が低分子化合物である場合は上記の溶媒は必ずしも必要としない。 In the present invention, a mixed solvent using two or more of these solvents can also be used. The solvent can be used in the range of 0 to 2000 parts by weight per 100 parts by weight of the reaction substrate for hydrogenation. In addition, when the reaction substrate is a low molecular compound, the above solvent is not necessarily required.
本発明においては、必要に応じて水素化反応後の混合物から触媒残さを除去してよい。例えば反応後の溶液を、塩酸、硝酸、硫酸、シュウ酸、乳酸、グリコール酸、オキシプロピオン酸、オキシ酪酸、エチレンジアミン四酢酸などの酸や、トリエタノールアミン、ジアルキルエタノールアミン、トリメルカプトトリアジン、チオ尿素などを用いて処理するか、珪藻土、シリカ、アルミナ、活性炭などの吸着剤を用いて処理することなどが行われる。また高分子化合物の水素化においては、メタノール、エタノール、プロパノールなどのアルコール類やアセトン、メチルエチルケトンなどのケトンを用いて凝固することによって、残さを低減してもよい。低分子化合物の水素化においては、蒸留、昇華などにより精製してもよい。これらの操作により、残留するパラジウムを５ｐｐｍ以下、好ましくは１ｐｐｍ以下、さらに好ましくは０．５ｐｐｍ以下にすることができる。 In this invention, you may remove a catalyst residue from the mixture after a hydrogenation reaction as needed. For example, the solution after the reaction may be acid such as hydrochloric acid, nitric acid, sulfuric acid, oxalic acid, lactic acid, glycolic acid, oxypropionic acid, oxybutyric acid, ethylenediaminetetraacetic acid, triethanolamine, dialkylethanolamine, trimercaptotriazine, thiourea Or using an adsorbent such as diatomaceous earth, silica, alumina, activated carbon, or the like. In the hydrogenation of the polymer compound, the residue may be reduced by coagulation using alcohols such as methanol, ethanol, and propanol, and ketones such as acetone and methyl ethyl ketone. In hydrogenation of a low molecular weight compound, it may be purified by distillation, sublimation or the like. By these operations, the residual palladium can be reduced to 5 ppm or less, preferably 1 ppm or less, more preferably 0.5 ppm or less.
本発明に係る水素化重合体の製造方法は、上記触媒成分(ａ)〜(ｃ)を用いることにより、共役ジエン化合物の付加重合体、環状オレフィンの付加重合体、環状オレフィンの開環重合体であって、重量平均分子量が１，０００〜１，０００，０００の範囲にある高分子重合体中のオレフィン性不飽和結合を水素化することを特徴としている。
反応基質
前記した本発明の水素化触媒は、オレフィン性不飽和結合を有する化合物の水素化あるいは部分水素化に好ましく用いられる。反応基質としては以下の低分子あるいは高分子化合物が挙げられる。
Ａ)低分子化合物
反応基質としては直鎖または分岐を有するオレフィン化合物、環状オレフィン化合物、芳香族化合物であり、オレフィン化合物はモノエンであってもポリエンであってもよく、共役であっても非共役であってもよい。置換基には特に制限はないが、炭素数１から３０の有機基が好ましい。
Ｂ)高分子化合物
反応基質が高分子化合物である場合、ゲルパーミエーションクロマトグラフィーによって測定される重量平均分子量が５００から１，０００，０００のオレフィン性不飽和結合を有する重合体がこのましい。
The method for producing a hydrogenated polymer according to the present invention uses the above catalyst components (a) to (c) to add an addition polymer of a conjugated diene compound, an addition polymer of a cyclic olefin, and a ring-opening polymer of a cyclic olefin. The olefinic unsaturated bond in the high molecular weight polymer having a weight average molecular weight in the range of 1,000 to 1,000,000 is hydrogenated.
Reaction Substrate The hydrogenation catalyst of the present invention described above is preferably used for hydrogenation or partial hydrogenation of a compound having an olefinically unsaturated bond. Examples of the reaction substrate include the following low-molecular or high-molecular compounds.
A) Low-molecular-weight compound reaction substrates include straight-chain or branched olefin compounds, cyclic olefin compounds, and aromatic compounds. The olefin compounds may be monoenes or polyenes, and may be conjugated or non-conjugated. It may be. Although there is no restriction | limiting in particular in a substituent, A C1-C30 organic group is preferable.
B) When the polymer compound reaction substrate is a polymer compound, a polymer having an olefinically unsaturated bond having a weight average molecular weight of 500 to 1,000,000 as measured by gel permeation chromatography is preferable.
Ｂ−１)共役ジエン化合物の付加重合体
ポリブタジエン、ブタジエン・スチレン共重合体、ブタジエン・イソプレン共重合体、ブタジエン・１，３−ペンタジエン共重合体、エチレン・ブタジエン共重合体、プロピレン・ブタジエン共重合体、イソブチレン・イソプレン共重合体、ポリイソプレン、ポリクロロプレン、ブタジエン・アクリロニトリル共重合体、ブタジエン・メタクリロニトリル共重合体、ブタジエン・アクリル酸メチル共重合体、ブタジエン・メタクリル酸メチル共重合体などが挙げられるが、これらに制限されない。
B-1) Addition polymer of conjugated diene compound Polybutadiene, butadiene / styrene copolymer, butadiene / isoprene copolymer, butadiene / 1,3-pentadiene copolymer, ethylene / butadiene copolymer, propylene / butadiene copolymer Polymers, isobutylene / isoprene copolymer, polyisoprene, polychloroprene, butadiene / acrylonitrile copolymer, butadiene / methacrylonitrile copolymer, butadiene / methyl acrylate copolymer, butadiene / methyl methacrylate copolymer, etc. But are not limited to these.
Ｂ−２)芳香族炭化水素化合物の重合体
ポリスチレン、ポリｐ−メチルスチレン、ポリビニルナフタレン、エチレン・スチレン共重合体、スチレン・ビシクロ［２．２．１］ヘプタ−２−エン共重合体等が挙げられるが、これらに制限されない。
B-2) Polymer of aromatic hydrocarbon compound Polystyrene, poly-p-methylstyrene, polyvinyl naphthalene, ethylene / styrene copolymer, styrene / bicyclo [2.2.1] hept-2-ene copolymer, etc. But are not limited to these.
Ｂ−３)環状オレフィンの重合体
ａ)環状オレフィン化合物の開環(共)重合体
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、ビシクロ［２．２．１］ヘプタ−２−エン、５−ブチルビシクロ［２．２．１］ヘプタ−２−エン、ビシクロ［２．２．１］ヘプタ−２−エン・５−ブチルビシクロ［２．２．１］ヘプタ−２−エン、５−ビニリデンビシクロ［２．２．１］ヘプタ−２−エン、５−ビニルビシクロ［２．２．１］ヘプタ−２−エン、トリシクロ［５．２．１．０2,6］デカ−３，８−ジエン、
トリシクロ［５．２．１．０2,6］デカ−８−エン、テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン、４−メチルテトラシクロ［６．２．１．１3,6．０2,7］ドデ
カ−９−エン、４−トリエトキシシリルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン、４−トリメチルシリルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン、テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン−４−カルボン酸メチル、４−メチルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン−４−カルボン酸メチル、ビシクロ［２．２．１］ヘプタ−２−エン・４−メチルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エン−４−カルボン酸メチル、トリシクロ［５．２．１．０2,6］デカ−３，８−ジエン・４−メチルテトラシクロ［６．２．１
．１3,6．０2,7］ドデカ−９−エン−４−カルボン酸メチルなどの環状オレフィンを開環(共)重合して得られる重合体を挙げることができる。
ｂ)重合鎖の末端、置換基、あるいは環骨格内にオレフィン性不飽和結合を有する環状オ
レフィン付加(共)重合体
重合鎖の末端にオレフィン性不飽和結合を有する環状オレフィン付加(共)重合体は、ビシクロ［２．２．１］ヘプタ−２−エンなどの環状オレフィンを付加(共)重合するに際して、連鎖移動剤としてα−オレフィン化合物、シクロペンテン類の化合物およびシクロオクタ−１，５−ジエンから選ばれた化合物を用いることにより製造される。
B-3) Polymer of cyclic olefin a) Ring-opening (co) polymer of cyclic olefin compound As specific examples, cyclobutene, cyclopentene, cyclooctene, bicyclo [2.2.1] hept-2-ene, 5-butyl Bicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene, 5-butylbicyclo [2.2.1] hept-2-ene, 5-vinylidenebicyclo [ 2.2.1] hept-2-ene, 5-vinylbicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8-diene,
Tricyclo [5.2.1.0 2,6 ] dec-8-ene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, 4-methyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, 4-triethoxysilyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, 4-trimethylsilyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-9-ene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 3,6 . 0,7 ] methyl dodec-9-ene-4-carboxylate, bicyclo [2.2.1] hept-2-ene.4-methyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] methyl dodeca-9-ene-4-carboxylate, tricyclo [5.2.1.0 2,6 ] deca-3,8-diene-4-methyltetracyclo [6.2.1
. 1 3,6 . And a polymer obtained by ring-opening (co) polymerizing a cyclic olefin such as methyl 0 2,7 ] dodec-9-ene-4-carboxylate.
b) Cyclic olefin addition (co) polymer having an olefinically unsaturated bond in the terminal, substituent or ring skeleton of the polymer chain Cyclic olefin addition (co) polymer having an olefinically unsaturated bond at the terminal of the polymer chain In addition (co) polymerization of a cyclic olefin such as bicyclo [2.2.1] hept-2-ene, a chain transfer agent is selected from an α-olefin compound, a cyclopentene compound and cycloocta-1,5-diene. Manufactured by using selected compounds.
置換基あるいは環骨格内にオレフィン性不飽和結合を有する環状オレフィン付加(共)重合体は、５−ビニルビシクロ［２．２．１］ヘプタ−２−エン、５−イソプロペニルビシ
クロ［２．２．１］ヘプタ−２−エン、５−(１−ブテニル)ビシクロ［２．２．１］ヘプタ−２−エン、５−ビニリデンビシクロ［２．２．１］ヘプタ−２−エン、５−エチリデンビシクロ［２．２．１］ヘプタ−２−エン、５−イソプロピリデンビシクロ［２．２．１］ヘプタ−２−エン、トリシクロ［５．２．１．０2,6］デカ−３，８−ジエン、ビシ
クロ［２．２．１］ヘプタ−２，５−ジエン、テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−４，９−ジエンなど重合に関与しないオレフィン性不飽和結合を有する環状オレフィン化合物を付加(共)重合体することにより製造される。また、シクロヘキサ−１，３−ジエン、シクロペンタジエンなどシクロアルカジエン化合物を付加(共)重合することによっても製造される。
Cyclic olefin addition (co) polymers having an olefinically unsaturated bond in the substituent or ring skeleton include 5-vinylbicyclo [2.2.1] hept-2-ene and 5-isopropenylbicyclo [2.2. .1] Hept-2-ene, 5- (1-butenyl) bicyclo [2.2.1] hept-2-ene, 5-vinylidenebicyclo [2.2.1] hept-2-ene, 5-ethylidene Bicyclo [2.2.1] hept-2-ene, 5-isopropylidenebicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 2,6 ] deca-3,8 -Diene, bicyclo [2.2.1] hepta-2,5-diene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodeca-4,9-diene is produced by addition (co) polymerization of a cyclic olefin compound having an olefinically unsaturated bond not involved in polymerization. It can also be produced by addition (co) polymerization of cycloalkadiene compounds such as cyclohexa-1,3-diene and cyclopentadiene.
本発明の水素化触媒は有機化学工業の薬品、医薬・農薬の中間体の合成におけるオレフィン性不飽和結合を有する低分子化合物の水素化用に好適に使用される。
また、本発明の水素化触媒は石油樹脂、透明樹脂、低誘電材料および絶縁材料などの耐酸化劣化性、耐熱性の向上のために、分子量５００〜１，０００，０００のオレフィン性不飽和結合を有する高分子化合物の水素化用に使用される。
The hydrogenation catalyst of the present invention is suitably used for hydrogenation of low molecular weight compounds having an olefinically unsaturated bond in the synthesis of intermediates of chemicals, pharmaceuticals and agricultural chemicals in the organic chemical industry.
Further, the hydrogenation catalyst of the present invention is an olefinically unsaturated bond having a molecular weight of 500 to 1,000,000 in order to improve oxidation resistance and heat resistance of petroleum resins, transparent resins, low dielectric materials and insulating materials. It is used for hydrogenation of polymer compounds having
特に、共役ジエン化合物の付加重合体、環状オレフィンの付加重合体、環状オレフィンの開環重合体であって、重量平均分子量が１，０００〜１，０００，０００の範囲にある高分子重合体中のオレフィン性不飽和結合を水素化する場合にその効果が顕現される。
［実施例］
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれら実施例によって何ら制限を受けるものではない。
１．水素化率の測定：
２７０ＭＨｚの1Ｈ−ＮＭＲ(プロトン核磁気共鳴装置)を用い、ベンゼン−ｄ6またはクロロホルム−ｄ中、５．０〜６．５ｐｐｍのオレフィン性プロトンおよび６．６〜７．５ｐｐｍの芳香族性プロトンの吸収を用い求めた。
Particularly, in a high molecular polymer having an addition polymer of a conjugated diene compound, an addition polymer of a cyclic olefin, a ring-opening polymer of a cyclic olefin, and a weight average molecular weight in the range of 1,000 to 1,000,000. This effect is manifested when hydrogenating the olefinically unsaturated bonds of.
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples.
1. Measurement of hydrogenation rate:
Using 270 MHz 1 H-NMR (proton nuclear magnetic resonance apparatus), 5.0 to 6.5 ppm olefinic proton and 6.6 to 7.5 ppm aromatic proton in benzene-d 6 or chloroform-d. The absorption was determined.
低分子化合物においては、上記の1Ｈ−ＮＭＲの測定またはガスクロマトグラフィーに
よって定量した。
２．高分子重合体の耐熱劣化試験
膜厚１００μｍのフィルムを空気中で各指定の温度下で９０分間保持したフィルムについて、波長４００ｎｍにおける光線透過率、イエローインデックス(ＹＩ)で評価した。
３．透明性(光線透過率、ヘイズ)の測定
膜厚１００μｍのフィルムを可視ＵＶスペクトロメーターHITACHI U-2010 Spectrophotometerを用いて、波長４００ｎｍの光線透過率を測定した。また、ヘイズはビックケミージャパン製「Haze-Gard plus ＢＫＹ Gardner」を用いて、JIS K7105-1981に準じて測定
した。
４．イエローインデックス(ＹＩ)の測定法
BKY-Gardner社製TCSII分光測色計を用い、ＡＳＴＭＤ１９２５に準じて測定した。
［参考例１］ オレフィン性不飽和結合を有する環状オレフィン付加重合体の合成
３００ｍｌのガラス製反応器に窒素雰囲気下で溶媒のトルエンを５０ｍｌ、単量体のビシクロ［２．２．１］ヘプタ−２−エンを６０ｍｍｏｌ、およびendo体が９８％のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンを３０ｍｍｏｌ、分子量調節剤の１−
ヘキセンを１．５ｍｍｏｌを仕込み、次に重合触媒として２−エチルヘキサン酸ニッケルのトルエン溶液を０．０２５ｍｍｏｌ、トリフェニルカルベニウムテトラキス(ペンタフ
ルオロフェニル)ボレートのトルエン溶液を０．０３０ｍｍｏｌ、およびトリエチルアル
ミニウムを０．１２５mmol添加して、付加共重合を３０℃で行った。
The low molecular weight compound was quantified by the above-mentioned 1 H-NMR measurement or gas chromatography.
2. Heat resistance deterioration test of high molecular weight film A film having a film thickness of 100 μm held in air at each specified temperature for 90 minutes was evaluated by light transmittance at a wavelength of 400 nm and yellow index (YI).
3. Measurement of transparency (light transmittance, haze) Light transmittance at a wavelength of 400 nm was measured for a film having a film thickness of 100 μm using a visible UV spectrometer HITACHI U-2010 Spectrophotometer. The haze was measured according to JIS K7105-1981 using “Haze-Gard plus BKY Gardner” manufactured by Big Chemie Japan.
4). Measurement method of yellow index (YI)
Measurement was performed according to ASTM D1925 using a TCSII spectrocolorimeter manufactured by BKY-Gardner.
Reference Example 1 Synthesis of Cyclic Olefin Addition Polymer Having Olefinically Unsaturated Bond In a 300 ml glass reactor, 50 ml of solvent toluene under a nitrogen atmosphere and monomeric bicyclo [2.2.1] hepta 60 mmol of 2-ene, and 30 mmol of tricyclo [5.2.1.0 2,6 ] deca-3,8-diene having 98% endo isomer,
Next, 1.5 mmol of hexene was charged, and then 0.025 mmol of toluene solution of nickel 2-ethylhexanoate, 0.030 mmol of toluene solution of triphenylcarbenium tetrakis (pentafluorophenyl) borate, and triethylaluminum were used as polymerization catalysts. Addition of 0.125 mmol and addition copolymerization was carried out at 30 ° C.
重合開始後、３０分および６０分後にそれぞれ単量体のビシクロ［２．２．１］ヘプタ−２−エンを５ｍｍｏｌ添加した。付加共重合を３０℃で合計３時間行ったところ、付加
共重合体への転化率は９６％であった。付加共重合体溶液に酸化防止剤のペンタエリスリチルテトラキス〔３−(３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル)プロピオネート〕を付加共重合体１００重量部当たり、０．３重量部を添加した後、乳酸０．５mmol入りのイソプロパノール１Ｌへ注いで凝固した。得られた付加共重合体をさらにイソプロパノールで洗浄し、８０℃で１７時間乾燥して付加共重合体のビシクロ［２．２．１］ヘプタ−２−エン／トリシクロ［５．２．１．０2,6］デカ−３，８−ジエンの共重合体を回
収した。付加共重合体中のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエン由来
の構造単位の割合は1ＨＮＭＲ分析から２８モル％、ゲルパ−ミエ−ションクロマトグラ
ム測定から、重量平均分子量(Ｍｗ)２２０，０００、数平均分子量(Ｍｎ)は８８，０００であった。
［参考例２］ オレフィン性不飽和結合を有する開環重合体
１０００ｍｌのガラス製反応器にトルエン３００ｍｌ、単量体の４−メチルテトラシクロ[６．２．１．１3,6．０2,7]ドデカ−９−エン−４−カルボン酸メチル２００mmol、分子量調節剤のヘキサ−１−エンを４０ｍｍｏｌ仕込み、最後に触媒成分の六塩化タングステンをトルエン溶液で０．０１ｍｍｏｌ、メタノールを０．０１ｍｍｏｌ、およびトリエチルアルミニウムを０．１ｍｍｏｌ添加して７０℃で重合を５時間行った。
After 30 minutes and 60 minutes from the start of polymerization, 5 mmol of monomeric bicyclo [2.2.1] hept-2-ene was added. When the addition copolymerization was carried out at 30 ° C. for a total of 3 hours, the conversion to the addition copolymer was 96%. An antioxidant, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], is added to the addition copolymer solution at 0.3 parts by weight per 100 parts by weight of the addition copolymer. Was added to 1 L of isopropanol containing 0.5 mmol of lactic acid to coagulate. The resulting addition copolymer was further washed with isopropanol and dried at 80 ° C. for 17 hours to give the addition copolymer bicyclo [2.2.1] hept-2-ene / tricyclo [5.2.1.0]. 2,6 ] Deca-3,8-diene copolymer was recovered. The proportion of structural units derived from tricyclo [5.2.1.0 2,6 ] deca-3,8-diene in the addition copolymer was 28 mol% from 1 HNMR analysis, from gel permeation chromatogram measurement. The weight average molecular weight (Mw) was 220,000, and the number average molecular weight (Mn) was 88,000.
Reference Example 2 Ring-Opening Polymer Having Olefinically Unsaturated Bond 1000 ml of glass reactor and 300 ml of toluene, monomer 4-methyltetracyclo [6.2.1.1 3,6 . 0,7 ] methyl dodeca-9-ene-4-carboxylate 200 mmol, molecular weight regulator hexa-1-ene 40 mmol, finally catalyst component tungsten hexachloride 0.01 ml in toluene solution, methanol 0 Polymerization was performed at 70 ° C. for 5 hours by adding 0.01 mmol and 0.1 mmol of triethylaluminum.
開環重合体への転化率は９７％であった。開環重合体溶液に酸化防止剤のペンタエリスリチルテトラキス〔３−(３，５−ジ−ｔ−-ブチル−４−ヒドロキシフェニル)プロピオ
ネート〕を付加共重合体１００重量部当たり、０．３重量部を添加した後、１Ｌの乳酸０．５mmol入りのイソプロパノールに入れて凝固した。イソプロパノールで凝固した付加共重合体を洗浄して、８０℃で１７時間、乾燥して開環重合体の４−メチルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ−９−エンの重合体を回収した。
Conversion to ring-opening polymer was 97%. 0.3 wt. Per 100 parts by weight of addition copolymer of pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant in the ring-opening polymer solution After adding 1 part, it was coagulated in 1 L of isopropanol containing 0.5 mmol of lactic acid. The addition copolymer coagulated with isopropanol was washed, dried at 80 ° C. for 17 hours, and the ring-opening polymer 4-methyltetracyclo [6.2.1.1 3,6 . The polymer of [ 0,7 ] dodec-9-ene was recovered.
開環重合体の重量平均分子量(Ｍｗ)は９２，０００、数平均分子量(Ｍｎ)は３８，０００であった。
［参考例３］ オレフィン性不飽和結合を有するジエン系重合体
２Lのガラス製耐圧容器に窒素雰囲気下で脱水されたテトラヒドロフランを３０００ppm含むシクロヘキサン８００ｍｌ、スチレン３０ｇを仕込み、ｎ−ブチルリチウム０．０２４ｍｍｏｌを用いて５０℃で３０分重合した。
The weight average molecular weight (Mw) of the ring-opening polymer was 92,000, and the number average molecular weight (Mn) was 38,000.
[Reference Example 3] Diene Polymer Having Olefinically Unsaturated Bond A 2 L glass pressure vessel is charged with 800 ml of cyclohexane containing 3000 ppm of tetrahydrofuran dehydrated in a nitrogen atmosphere and 30 g of styrene, and 0.024 mmol of n-butyllithium is added. Polymerized at 50 ° C. for 30 minutes.
引き続き１，３−ブタジエンを１４０ｇ添加して、５０℃で１時間重合した。さらにスチレン３０ｇを添加して４０分間重合し、少量のメタノールで重合を停止した。このスチレン／ブタジエンブロック共重合体溶液に酸化防止剤としてペンタエリスリチルテトラキス〔３−(３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル)プロピオネート〕を付加重合体１００重量部当たり、０．３重量部添加した後、５Ｌのメタノールで凝固し、さらに分離した。このブロック共重合体を８０℃で１７時間、真空乾燥機で乾燥し回収した。 Subsequently, 140 g of 1,3-butadiene was added and polymerized at 50 ° C. for 1 hour. Further, 30 g of styrene was added and polymerized for 40 minutes, and the polymerization was stopped with a small amount of methanol. To this styrene / butadiene block copolymer solution, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant is added in an amount of 0. After adding 3 parts by weight, the solution was solidified with 5 L of methanol and further separated. The block copolymer was recovered by drying with a vacuum dryer at 80 ° C. for 17 hours.
この共重合体におけるスチレン含有量は1ＨＮＭＲ分析から３０重量％と定量された。
また、数平均分子量(Ｍｎ)１３８，０００、重量平均分子量(Ｍｗ)は１４９，０００であった。
［参考例４］
２Lのガラス製耐圧容器に窒素雰囲気下で脱水されたテトラヒドロフランを３０００ｐ
ｐｍ含むシクロヘキサン１０００ｍｌ、スチレン１０４ｇを仕込み、ｎ−ブチルリチウム０．０５ｍｍｏｌを用いて５０℃で６０分重合し、少量のメタノールで重合を停止した。
The styrene content in this copolymer was determined to be 30% by weight from 1 HNMR analysis.
The number average molecular weight (Mn) was 138,000 and the weight average molecular weight (Mw) was 149,000.
[Reference Example 4]
3000p of tetrahydrofuran dehydrated in a 2L glass pressure vessel under nitrogen atmosphere
1000 ml of cyclohexane containing pm and 104 g of styrene were charged, polymerized at 50 ° C. for 60 minutes using 0.05 mmol of n-butyllithium, and the polymerization was stopped with a small amount of methanol.
このスチレン重合体溶液に２，６−ジ−ｔ−ブチル−４−メチルフェノールを重合体１００重量部当たり、０．３重量部添加した後、５Ｌのメタノールで凝固し、さらに分離した。このブロック共重合体を８０℃で１７時間、真空乾燥機で乾燥し回収した。 To this styrene polymer solution, 0.36 parts by weight of 2,6-di-t-butyl-4-methylphenol per 100 parts by weight of the polymer was added, then solidified with 5 L of methanol and further separated. The block copolymer was recovered by drying with a vacuum dryer at 80 ° C. for 17 hours.
このスチレン重合体は数平均分子量(Ｍｎ)２０５００、重量平均分子量(Ｍｗ)は２４，０００であった。
［実施例１］
参考例１の付加重合体７ｇをトルエン７０ｇ、シクロヘキサン３０ｇの混合溶媒に溶解し、触媒成分(ａ)の酢酸パラジウムを上記共重合体に対して２．６４×１０-3ｍｍｏｌ(
パラジウム原子として４０ｐｐｍ)、および触媒成分(ｂ)のトリシクロペンチルホスフィ
ン２．６４×１０-3ｍｍｏｌを仕込んだ。さらに２分後、トリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレートを３．０×１０-3ｍｍｏｌ仕込んだ。水素圧８.０ＭＰａで、９０℃で５時間、水素化反応を行った。
This styrene polymer had a number average molecular weight (Mn) of 20500 and a weight average molecular weight (Mw) of 24,000.
[Example 1]
7 g of the addition polymer of Reference Example 1 was dissolved in a mixed solvent of 70 g of toluene and 30 g of cyclohexane, and palladium acetate of the catalyst component (a) was 2.64 × 10 −3 mmol with respect to the copolymer.
40 ppm as palladium atoms) and 2.64 × 10 −3 mmol of the catalyst component (b) tricyclopentylphosphine were charged. Two more minutes later, 3.0 × 10 −3 mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate was charged. The hydrogenation reaction was performed at 90 ° C. for 5 hours under a hydrogen pressure of 8.0 MPa.
水素化された重合体溶液にトリオクチルアミン１．５×１０-3ｍｍｏｌを添加して、水素化触媒を活性炭で吸着し、１ミクロンのフィルターでろ過をした。さらにその溶液を、濃塩酸２ｍｌを含む３Ｌのイソプロピルアルコールに入れて水素化された重合体を凝固し、乾燥して重合体を回収した。 Trioctylamine 1.5 × 10 −3 mmol was added to the hydrogenated polymer solution, the hydrogenation catalyst was adsorbed with activated carbon, and filtered through a 1 micron filter. Further, the solution was put into 3 L of isopropyl alcohol containing 2 ml of concentrated hydrochloric acid to coagulate the hydrogenated polymer and dried to recover the polymer.
水素化された重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来
するオレフィン性不飽和結合は９９％水素化されていた。
水素化された付加共重合体をキャスト法で膜厚１００μｍのフィルムにした。このフィルムの４００ｎｍの光線透過率は９０％、Ｈａｚｅ値は０．４％、ＹＩは０．５であった。このフィルムを空気中１５０℃、９０分の熱処理を行った結果、４００ｎｍの光線透過率は９０％、ＹＩは０．６であり、ほとんど変化なかった。
［実施例２］
実施例１にて参考例１の付加共重合体の代わりに参考例２の開環重合体７ｇを用いる以外、実施例１と同様に行った。
The olefinically unsaturated bonds derived from the hydrogenated polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene were 99% hydrogenated.
The hydrogenated addition copolymer was formed into a film having a thickness of 100 μm by a casting method. This film had a light transmittance of 90% at 400 nm, a haze value of 0.4%, and a YI of 0.5. As a result of heat-treating the film at 150 ° C. for 90 minutes in the air, the light transmittance at 400 nm was 90%, and YI was 0.6, showing almost no change.
[Example 2]
The same procedure as in Example 1 was performed except that 7 g of the ring-opened polymer of Reference Example 2 was used instead of the addition copolymer of Reference Example 1 in Example 1.
開環重合体のオレフィン性不飽和結合の９９．９％が水素化されていた。水素化された開環重合体をＣＨ2Ｃl2溶媒に溶解し、キャスト法で膜厚１００μｍのフィルムを作成し
た。このフィルムを８０℃、９０分空気下で熱処理を行ったが、４００ｎｍの光線透過率９０％、ＹＩ値０．５であった。
［実施例３］
実施例１にて参考例１の付加共重合体の代わりに参考例３のスチレン・ブタジエンブロック共重合体７ｇを用い、触媒成分として、さらにトリエチルアルミニウム１３．２×１０-3ｍｍｏｌ、およびビシクロ[２．２．１]ヘプタ−２−エンを１３．２×１０-3ｍｍｏｌ添加する以外、実施例１と同様に行った。
99.9% of the olefinically unsaturated bonds of the ring-opening polymer were hydrogenated. The hydrogenated ring-opening polymer was dissolved in a CH 2 Cl 2 solvent, and a film having a thickness of 100 μm was prepared by a casting method. This film was heat-treated at 80 ° C. for 90 minutes under air, and had a light transmittance of 90% at 400 nm and a YI value of 0.5.
[Example 3]
In Example 1, 7 g of the styrene / butadiene block copolymer of Reference Example 3 was used instead of the addition copolymer of Reference Example 1, and as the catalyst component, 13.2 × 10 −3 mmol of triethylaluminum, and bicyclo [ 2.2.1] Same as Example 1 except that 13.2 × 10 −3 mmol of hepta-2-ene was added.
ブタジエンに由来する構造単位のオレフィン性不飽和結合の９９．８％が水素化されており、一方、スチレン由来の芳香環は５％が水素化されていた。ゲル・パーミエションクロマトグラム分析で低分子領域にあらたなピークの生成はなく、分子鎖の切断はなかった。
［実施例４］
窒素雰囲気下で１Ｌの反応器に参考例４のポリスチレン７０ｇをシクロヘキサン６００ｇに５０℃で溶解し、最後に、水素化触媒成分(ａ)としてパラジウムビス(アセチルアセ
トネート)を０．０３４ｍｍｏｌ、触媒成分(ｂ)としてトリペンチルホスフィンを０．０
３４ｍｍｏｌ、触媒成分(ｃ)としてトリフェニルカルベニウムテトラキス(ペンタフルオ
ロフェニル)ボレート０．０３４ｍｍｏｌ、最後にトリエチルアルミニウムを０．３４ｍ
ｍｏｌを添加して、１３０℃で、水素圧８．０ＭＰａで５時間、水素化を行った。
1Ｈ−ＮＭＲによって測定されるポリスチレンの芳香環の水素化率は８９％であった。
［実施例５］
乳化重合で得られたアクリロニトリル・ブタジエン共重合体(結合アクリロニトリル量
３５ｗｔ％、ムーニー粘度ＭＬ1+4＝３０)７ｇをメチルエチルケトン１００ｇに溶解し、
予め、触媒成分(ａ)の酢酸パラジウム４．６２×１０-3ｍｍｏｌ(パラジウム原子として
７０ｐｐｍ)、および触媒成分(ｂ)のトリシクロヘキシルホスフィン４．６２×１０-3ｍ
ｍｏｌ、トリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレート５．０×１０-3ｍｍｏｌを混合し、シリカ上に担持した触媒(Pd原子として０．２wt％)とビシクロ[２．２．１]ヘプタ−２−エン１３.２ｍｍｏｌを仕込み、水素圧８．０ＭＰａ、９０
℃で５時間、水素化反応を行った。
99.8% of the olefinically unsaturated bonds of the structural units derived from butadiene were hydrogenated, while 5% of the aromatic rings derived from styrene were hydrogenated. In gel permeation chromatogram analysis, no new peak was generated in the low molecular region, and no molecular chain was broken.
[Example 4]
Under a nitrogen atmosphere, 70 g of the polystyrene of Reference Example 4 was dissolved in 600 g of cyclohexane at 50 ° C. in a 1 L reactor, and finally 0.034 mmol of palladium bis (acetylacetonate) as a hydrogenation catalyst component (a), catalyst component (b) Tripentylphosphine as 0.0
34mmol, 0.034mmol of triphenylcarbenium tetrakis (pentafluorophenyl) borate as catalyst component (c), and finally 0.34m of triethylaluminum
Molten was added, and hydrogenation was performed at 130 ° C. and a hydrogen pressure of 8.0 MPa for 5 hours.
The hydrogenation rate of the aromatic ring of polystyrene measured by 1 H-NMR was 89%.
[Example 5]
7 g of acrylonitrile-butadiene copolymer obtained by emulsion polymerization (bound acrylonitrile amount 35 wt%, Mooney viscosity ML 1 + 4 = 30) was dissolved in 100 g of methyl ethyl ketone,
In advance, 4.62 × 10 −3 mmol of palladium acetate as the catalyst component (a) (70 ppm as palladium atom) and 4.62 × 10 −3 m of tricyclohexylphosphine as the catalyst component (b).
mol, triphenylcarbenium tetrakis (pentafluorophenyl) borate 5.0 × 10 −3 mmol mixed, catalyst supported on silica (0.2 wt% as Pd atom) and bicyclo [2.2.1] hepta -2-ene 13.2 mmol, hydrogen pressure 8.0 MPa, 90
The hydrogenation reaction was performed at 5 ° C. for 5 hours.
水素化された重合体の溶液をフィルターでろ過した後、１Ｌのイソプロピルアルコールに注いで凝固し、真空乾燥して重合体を得た。水素化された重合体の１，３−ブタジエンに由来するオレフィン性不飽和結合は９９％水素化されていた。
[実施例６]
実施例１にて触媒成分(ａ)、(ｂ)、(ｃ)を仕込んだ後、ビシクロ[２．２．１]ヘプタ−２−エンを２．６４×１０-2ｍｍｏｌ添加し、水素化の反応時間を３時間で行った。重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来するオレフィン性不
飽和結合の水素化率は９９％であった。
[実施例７]
実施例１にて溶媒としてピリジンを０．１ｐｐｍ含むトルエン７０ｇを用い、触媒成分(ａ)、(ｂ)、(ｃ)を仕込む前に、トリエチルアルミニウムを２．６４×１０-2ｍｍｏｌを添加した以外、実施例１と同様の操作を行った。重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来するオレフィン性不飽和結合の水素化率は実施例１と同
様に９９％であった。
［比較例１］
実施例１にて水素化触媒として本発明のパラジウム系触媒の代わりに、酢酸パラジウムを４×１０-3ｍｍｏｌ(パラジウム原子として重合体に対して４０ｐｐｍ)、トリエチルアルミニウムを２６．４×１０-3ｍｍｏｌを用いる以外、実施例１と同様に行った。
The hydrogenated polymer solution was filtered through a filter, poured into 1 L of isopropyl alcohol, solidified, and vacuum dried to obtain a polymer. The olefinically unsaturated bonds derived from the hydrogenated polymer 1,3-butadiene were 99% hydrogenated.
[Example 6]
After the catalyst components (a), (b), and (c) were charged in Example 1, 2.64 × 10 −2 mmol of bicyclo [2.2.1] hept-2-ene was added and hydrogenated. The reaction time was 3 hours. The hydrogenation rate of the olefinically unsaturated bond derived from the polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene was 99%.
[Example 7]
In Example 1, 70 g of toluene containing 0.1 ppm of pyridine was used as a solvent, and 2.64 × 10 −2 mmol of triethylaluminum was added before the catalyst components (a), (b), and (c) were charged. Except that, the same operation as in Example 1 was performed. The hydrogenation rate of the olefinically unsaturated bond derived from the polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene was 99% as in Example 1.
[Comparative Example 1]
In Example 1, instead of the palladium-based catalyst of the present invention as a hydrogenation catalyst, 4 × 10 −3 mmol of palladium acetate (40 ppm as a palladium atom with respect to the polymer) and 26.4 × 10 −3 of triethylaluminum were used. The same operation as in Example 1 was performed except that mmol was used.
水素化された重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来
するオレフィン性不飽和結合は７０％水素化されていた。水素化された付加共重合体を溶液流延法で膜厚１００μｍのフィルムにした。このフィルムの４００ｎｍの光線透過率は９０％、Ｈａｚｅ値は０．４％、ＹＩは０．５であった。
このフィルムを空気中１５０℃、９０分の熱処理を行ったが、４００ｎｍの光線透過率は８５％、ＹＩは１．６で、やや黄変していた。
[比較例２]
実施例１にて、トリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)ボレートを用いなかった以外は、実施例１と同様の操作を行った。
The olefinically unsaturated bonds derived from the hydrogenated polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene were 70% hydrogenated. The hydrogenated addition copolymer was formed into a film having a thickness of 100 μm by a solution casting method. This film had a light transmittance of 90% at 400 nm, a haze value of 0.4%, and a YI of 0.5.
This film was heat-treated in air at 150 ° C. for 90 minutes. The light transmittance at 400 nm was 85% and YI was 1.6, which was slightly yellowed.
[Comparative Example 2]
The same operation as in Example 1 was performed except that triphenylcarbenium tetrakis (pentafluorophenyl) borate was not used in Example 1.
重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来するオレフィ
ン性不飽和結合の水素化率は４０％であった。
[比較例３]
実施例１にて、トリシクロペンチルホスフィン２．６４×１０-3ｍｍｏｌを用いない以外、実施例１と同様に行った。
The hydrogenation rate of the olefinically unsaturated bond derived from the polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene was 40%.
[Comparative Example 3]
The same procedure as in Example 1 was performed except that 2.64 × 10 −3 mmol of tricyclopentylphosphine was not used in Example 1.
重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来するオレフィ
ン性不飽和結合の水素化率は４５％であった。
［比較例４］
実施例１にてトリシクロペンチルホスフィン２．６４×１０-3ｍｍｏｌにかえてトリフェニルホスフィン２．６４×１０-3ｍｍｏｌを用いた以外は、実施例１と同様の操作にて水素化を行なった。
The hydrogenation rate of the olefinically unsaturated bond derived from the polymer tricyclo [5.2.1.0 2,6 ] deca-3,8-diene was 45%.
[Comparative Example 4]
Hydrogenation was carried out in the same manner as in Example 1, except that 2.64 × 10 −3 mmol of triphenylphosphine was used instead of 2.64 × 10 −3 mmol of tricyclopentylphosphine in Example 1. .
水素化された重合体のトリシクロ［５．２．１．０2,6］デカ−３，８−ジエンに由来
する二重結合の水素化率は７９％であった。
水素化された付加共重合体を溶液流延法で膜厚１００μｍのフィルムにした。このフィルムの４００ｎｍの光線透過率は９０％、Ｈａｚｅ値は０．４％、ＹＩは０．５であった。
The hydrogenation rate of the double bond derived from tricyclo [5.2.1.0 2,6 ] deca-3,8-diene in the hydrogenated polymer was 79%.
The hydrogenated addition copolymer was formed into a film having a thickness of 100 μm by a solution casting method. This film had a light transmittance of 90% at 400 nm, a haze value of 0.4%, and a YI of 0.5.
このフィルムを空気中１５０℃、９０分の熱処理を行った結果、４００ｎｍの光線透過率は８０％、ＹＩも３．６と黄色に変色した。
［比較例５］
実施例２において水素化触媒として、ＲｕＨ・Ｃl(ＣＯ)(ＰＰｈ3)3を開環重合体に対
してルテニウム原子として４０ｐｐｍを用いた以外は、実施例２と同様の操作を行った。その結果、実施例２と同じ９０℃では開環重合体のオレフィン性不飽和結合の３７％が水素化されたのみであった。
As a result of heat-treating the film at 150 ° C. for 90 minutes in the air, the light transmittance at 400 nm was 80% and YI was also changed to 3.6 and yellow.
[Comparative Example 5]
The same operation as in Example 2 was carried out except that RuH · Cl (CO) (PPh 3 ) 3 was used as a ruthenium atom with respect to the ring-opened polymer as 40 ppm as a hydrogenation catalyst in Example 2. As a result, at 90 ° C. as in Example 2, only 37% of the olefinically unsaturated bond of the ring-opening polymer was hydrogenated.
水素化された開環重合体をＣＨ2Ｃl2に溶解し、キャスト法によって膜厚１００μｍの
フィルムを作成した。このフィルムを８０℃、９０分空気下で熱処理を行うと、４００ｎｍの光線透過率は８０％、ＹＩ値は４．５で、茶色に変色していた。
［比較例６］
水素化触媒として、２−エチルヘキサン酸ニッケル３．５６×１０-3ｍｍｏｌ(ニッケ
ル原子として、スチレン・ブタジエンブロック共重合体に対して３０ｐｐｍ)トリエチル
アルミニウム１０．７×１０-3ｍｍｏｌに変更して用いる以外、実施例３と同様に行った。
The hydrogenated ring-opening polymer was dissolved in CH 2 Cl 2 and a film having a thickness of 100 μm was prepared by a casting method. When this film was heat-treated at 80 ° C. for 90 minutes in the air, the light transmittance at 400 nm was 80%, the YI value was 4.5, and the film turned brown.
[Comparative Example 6]
As a hydrogenation catalyst, nickel 2-ethylhexanoate was changed to 3.56 × 10 −3 mmol (as nickel atoms, 30 ppm relative to the styrene / butadiene block copolymer) and triethylaluminum 10.7 × 10 −3 mmol. The same operation as in Example 3 was carried out except that it was used.
ブタジエン由来の１，２結合および１，４結合のオレフィン性不飽和結合の８８．８％が水素化されていたが、スチレン由来の芳香環は水素化されてなかった。ゲル・パーミエションクロマトグラム分析で低分子領域にあらたなピークの生成はなく、分子鎖の切断はなかった。 Although 88.8% of the 1,2-bond and 1,4-bond olefinically unsaturated bonds derived from butadiene were hydrogenated, the aromatic rings derived from styrene were not hydrogenated. In gel permeation chromatogram analysis, no new peak was generated in the low molecular region, and no molecular chain was broken.
水素化された開環重合体をトルエン溶媒に溶解し、キャスト法で膜厚１００μｍのフィルムにした。このフィルムを空気中７０℃、９０分間熱処理を行った結果、４００ｎｍの光線透過率は８７％、ＹＩは２．７であった。
［実施例８］〜［実施例１２］
１００ｍｌの耐圧反応器に窒素雰囲気下でトルエン５０ｍｌ、表１に示す反応基質を１００ｍｍｏｌ、触媒成分(ａ＋ｂ)としてビス(トリシクロペンチルホスフィン)パラジウムビス(アセテート)５．０×１０-4ｍｍｏｌ、触媒成分(ｃ)のトリフェニルカルベニウムテトラキス(ペンタフルオロフェニル)アルミナート５．２×１０-4ｍｍｏｌを仕込み、８０℃に加温して、水素圧０．５ＭＰａで１時間、水素化を行った。内容物を蒸留で分離し、ガスクロマトグラムによる基質と生成物の分析で水素化率を求めた。結果を表１に示す。
The hydrogenated ring-opening polymer was dissolved in a toluene solvent and formed into a film having a thickness of 100 μm by a casting method. This film was heat-treated in air at 70 ° C. for 90 minutes. As a result, the light transmittance at 400 nm was 87% and the YI was 2.7.
[Example 8] to [Example 12]
In a 100 ml pressure-resistant reactor, 50 ml of toluene in a nitrogen atmosphere, 100 mmol of the reaction substrate shown in Table 1, bis (tricyclopentylphosphine) palladium bis (acetate) 5.0 × 10 −4 mmol as catalyst component (a + b), catalyst component (c) Triphenylcarbenium tetrakis (pentafluorophenyl) aluminate (5.2 × 10 −4 mmol) was charged, heated to 80 ° C., and hydrogenated at a hydrogen pressure of 0.5 MPa for 1 hour. The contents were separated by distillation, and the hydrogenation rate was determined by analyzing the substrate and product by gas chromatogram. The results are shown in Table 1.
Claims (10)
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ)式(２)で表されるホスフィン化合物
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基からそれぞれ独立に選ばれた置換基〕
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物
(ｄ)有機アルミニウム化合物、有機マグネシウム化合物および有機リチウム化合物なる群からから選ばれる少なくとも１種の化合物。 A hydrogenation catalyst for a compound having an olefinically unsaturated bond, which is obtained from a mixture containing the following catalyst components (a) to (d) :
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) Phosphine compound P (R 1 ) 3 represented by formula (2) Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, i-propyl group, t-butyl group, 2- Substituents independently selected from methylphenyl and pentafluorophenyl groups]
(c) a compound selected from an ionic boron compound or an ionic aluminum compound
(d) At least one compound selected from the group consisting of organoaluminum compounds, organomagnesium compounds, and organolithium compounds.
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ)式(２)で表されるホスフィン化合物
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基からそれぞれ独立に選ばれた置換基〕
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物
(ｅ)ビシクロ[２．２．１]ヘプタ−２−エン構造またはビシクロ[２．２．１]ヘプタ−２，５−ジエン構造を有する環状オレフィン化合物。 A hydrogenation catalyst for a compound having an olefinically unsaturated bond, which is obtained from a mixture containing the following catalyst components (a) to (c) and (e) :
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) Phosphine compound P (R 1 ) 3 represented by formula (2) Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, i-propyl group, t-butyl group, 2- Substituents independently selected from methylphenyl and pentafluorophenyl groups]
(c) a compound selected from an ionic boron compound or an ionic aluminum compound
(e) A cyclic olefin compound having a bicyclo [2.2.1] hept-2-ene structure or a bicyclo [2.2.1] hepta-2,5-diene structure.
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ) トリシクロペンチルホスフィン、トリシクロヘキシルホスフィンから選ばれたホスフィン化合物
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物。 A hydrogenation catalyst for a compound having an olefinically unsaturated bond, which is obtained from a mixture containing the following catalyst components (a) to (c):
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) A phosphine compound selected from tricyclopentylphosphine and tricyclohexylphosphine
(c) A compound selected from an ionic boron compound or an ionic aluminum compound.
Ｐｄ(Ｘ)k・〔Ｐ(Ｒ1)3〕m …式(３)
〔式(３)でＰｄはパラジウム原子、Ｘは有機酸アニオン、ベータジケトンアニオン、ハロゲン化物アニオン、Ｐ(Ｒ1)3は式(２)と同じ、ｋおよびｍは１または２を示す。〕 The hydrogenation catalyst according to claim 1 or 2, wherein a palladium complex represented by the following formula (3) is used as the catalyst components (a) and (b).
Pd (X) k · [P (R 1 ) 3 ] m ... Formula (3)
[In formula (3), Pd is a palladium atom, X is an organic acid anion, beta diketone anion, halide anion, P (R 1 ) 3 is the same as in formula (2), and k and m are 1 or 2. ]
Ｐｄ(Ｘ)k・〔Ｐ(Ｒ1)3〕m …式(３’)
〔式(３’)でＰｄはパラジウム原子、Ｘは有機酸アニオン、ベータジケトンアニオン、ハロゲン化物アニオン、Ｒ 1 はすべてがシクロペンチル基ないしシクロヘキシル基を示し、ｋおよびｍは１または２を示す。〕 The hydrogenation catalyst according to claim 3, wherein a palladium complex represented by the following formula (3 ') is used as the catalyst components (a) and (b).
Pd (X) k · [P (R 1 ) 3 ] m Equation (3 ′)
[In the formula (3 ′) , Pd is a palladium atom, X is an organic acid anion, a betadiketone anion, a halide anion, R 1 is a cyclopentyl group or a cyclohexyl group, and k and m are 1 or 2. ]
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ)式(２)で表されるホスフィン化合物
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基からそれぞれ独立に選ばれた置換基〕
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物
(ｄ)有機アルミニウム化合物、有機マグネシウム化合物および有機リチウム化合物なる群からから選ばれる少なくとも１種の化合物。 By using the following catalyst components (a) to (d) , an addition polymer of a conjugated diene compound, an addition polymer of a cyclic olefin, and a ring-opening polymer of a cyclic olefin having a weight average molecular weight of 1,000 to 1 A method for producing a hydrogenated polymer, comprising hydrogenating an olefinically unsaturated bond in a polymer in the range of 1,000,000.
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) Phosphine compound P (R 1 ) 3 represented by formula (2) Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, i-propyl group, t-butyl group, 2- Substituents independently selected from methylphenyl and pentafluorophenyl groups]
(c) a compound selected from an ionic boron compound or an ionic aluminum compound
(d) At least one compound selected from the group consisting of organoaluminum compounds, organomagnesium compounds, and organolithium compounds .
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ)式(２)で表されるホスフィン化合物
Ｐ(Ｒ1)3 …式(２)
〔式(２)でＰはリン原子、Ｒ1はシクロペンチル基、３−メチルシクロペンチル基、シクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、ｉ−プロピル基、ｔ−ブチル基、２−メチルフェニル基、ペンタフルオロフェニル基からそれぞれ独立に選ばれた置換基〕
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物。
(ｅ)ビシクロ[２．２．１]ヘプタ−２−エン構造またはビシクロ[２．２．１]ヘプタ−２，５−ジエン構造を有する環状オレフィン化合物。 By using the following catalyst components (a) to (c) and (e) , an addition polymer of a conjugated diene compound, an addition polymer of a cyclic olefin, and a ring-opening polymer of a cyclic olefin, each having a weight average molecular weight of 1 A method for producing a hydrogenated polymer, comprising hydrogenating an olefinically unsaturated bond in a polymer having a molecular weight in the range of 1,000 to 1,000,000.
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) Phosphine compound P (R 1 ) 3 represented by formula (2) Formula (2)
[In the formula (2), P is a phosphorus atom, R 1 is a cyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, i-propyl group, t-butyl group, 2- Substituents independently selected from methylphenyl and pentafluorophenyl groups]
(c) A compound selected from an ionic boron compound or an ionic aluminum compound.
(e) A cyclic olefin compound having a bicyclo [2.2.1] hept-2-ene structure or a bicyclo [2.2.1] hepta-2,5-diene structure.
(ａ)式(１)で表されるパラジウム(II)の有機酸塩、ベータジケトン化合物またはハロゲン化物：
Ｐｄ(Ｘ)k …式(１)
〔式(１)中、Ｘは有機酸のアニオン、ベータジケトンアニオン、ハロゲン化物アニオンを示す。ｋは１または２を示す。〕
(ｂ) トリシクロペンチルホスフィン、トリシクロヘキシルホスフィンから選ばれたホスフィン化合物
(ｃ)イオン性のホウ素化合物、またはイオン性のアルミニウム化合物から選ばれた化合物。 By using the following catalyst components (a) to (c), an addition polymer of a conjugated diene compound, an addition polymer of a cyclic olefin, and a ring-opening polymer of a cyclic olefin having a weight average molecular weight of 1,000 to 1 A method for producing a hydrogenated polymer, comprising hydrogenating an olefinically unsaturated bond in a polymer in the range of 1,000,000.
(a) An organic acid salt, beta-diketone compound or halide of palladium (II) represented by the formula (1):
Pd (X) k Formula (1)
[In the formula (1), X represents an anion of an organic acid, a beta diketone anion, or a halide anion. k represents 1 or 2. ]
(b) A phosphine compound selected from tricyclopentylphosphine and tricyclohexylphosphine
(c) A compound selected from an ionic boron compound or an ionic aluminum compound.
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