TWI483958B - A catalyst composition for hydrogenation, and a hydrogenation method using the catalyst composition for hydrogenation - Google Patents
A catalyst composition for hydrogenation, and a hydrogenation method using the catalyst composition for hydrogenation Download PDFInfo
- Publication number
- TWI483958B TWI483958B TW102133519A TW102133519A TWI483958B TW I483958 B TWI483958 B TW I483958B TW 102133519 A TW102133519 A TW 102133519A TW 102133519 A TW102133519 A TW 102133519A TW I483958 B TWI483958 B TW I483958B
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- TW
- Taiwan
- Prior art keywords
- hydrogenation
- bis
- compound
- titanium
- acid
- Prior art date
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 193
- 239000003054 catalyst Substances 0.000 title claims description 104
- 239000000203 mixture Substances 0.000 title claims description 87
- 238000000034 method Methods 0.000 title claims description 23
- -1 titanocene compound Chemical class 0.000 claims description 110
- 150000001875 compounds Chemical class 0.000 claims description 67
- 229920000642 polymer Polymers 0.000 claims description 59
- 150000001993 dienes Chemical class 0.000 claims description 30
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 17
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 150000002430 hydrocarbons Chemical group 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002900 organolithium compounds Chemical class 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 150000002902 organometallic compounds Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 description 48
- 229910052719 titanium Inorganic materials 0.000 description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 37
- 230000000694 effects Effects 0.000 description 25
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 21
- 238000003860 storage Methods 0.000 description 19
- 150000004678 hydrides Chemical class 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 18
- 239000002184 metal Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000004383 yellowing Methods 0.000 description 6
- ZATJSNLHOCRDEW-UHFFFAOYSA-N 2-chlorophenol titanium Chemical compound [Ti].OC1=CC=CC=C1Cl ZATJSNLHOCRDEW-UHFFFAOYSA-N 0.000 description 5
- MBMKFKOVXPKXCV-UHFFFAOYSA-N CCO[Ti]OCC Chemical compound CCO[Ti]OCC MBMKFKOVXPKXCV-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- YOBCTIIWHLYFII-UHFFFAOYSA-L difluorotitanium Chemical compound F[Ti]F YOBCTIIWHLYFII-UHFFFAOYSA-L 0.000 description 5
- XXLOICMXOBKOLH-UHFFFAOYSA-L diiodotitanium Chemical compound I[Ti]I XXLOICMXOBKOLH-UHFFFAOYSA-L 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 230000005764 inhibitory process Effects 0.000 description 5
- COEYXIBLSAIEKV-UHFFFAOYSA-N titanium dihydride Chemical compound [TiH2] COEYXIBLSAIEKV-UHFFFAOYSA-N 0.000 description 5
- 229910000048 titanium hydride Inorganic materials 0.000 description 5
- AUZMWGNTACEWDV-UHFFFAOYSA-L titanium(2+);dibromide Chemical compound Br[Ti]Br AUZMWGNTACEWDV-UHFFFAOYSA-L 0.000 description 5
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- ZBTMRBYMKUEVEU-UHFFFAOYSA-N 1-bromo-4-methylbenzene Chemical compound CC1=CC=C(Br)C=C1 ZBTMRBYMKUEVEU-UHFFFAOYSA-N 0.000 description 4
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
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- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-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
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
- IZWIPIIVPHXLTN-UHFFFAOYSA-N potassium;cyclopenta-1,3-diene Chemical compound [K+].C1C=CC=[C-]1 IZWIPIIVPHXLTN-UHFFFAOYSA-N 0.000 description 1
- FZWIBIHTJMCHGT-UHFFFAOYSA-N potassium;diphenylmethylbenzene Chemical compound [K+].C1=CC=CC=C1[C-](C=1C=CC=CC=1)C1=CC=CC=C1 FZWIBIHTJMCHGT-UHFFFAOYSA-N 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 229960000380 propiolactone Drugs 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- UJJLJRQIPMGXEZ-UHFFFAOYSA-N tetrahydro-2-furoic acid Chemical compound OC(=O)C1CCCO1 UJJLJRQIPMGXEZ-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- BZVJOYBTLHNRDW-UHFFFAOYSA-N triphenylmethanamine Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(N)C1=CC=CC=C1 BZVJOYBTLHNRDW-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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Description
本發明係關於一種氫化用觸媒組合物、及使用該氫化用觸媒組合物將含有烯烴性不飽和雙鍵之化合物(以下亦有時僅記載為烯烴化合物)選擇性地氫化(以下有時僅記載為「氫化」)之方法。
先前以來,作為對烯烴化合物進行之氫化步驟中所使用之氫化觸媒,通常已知有非均相觸媒及均相觸媒。
前者之非均相觸媒廣泛利用於工業上,但與後者之均相觸媒相比,通常活性較低,為進行所需之氫化反應而需要大量觸媒,進而,要於高溫高壓下進行,因此有不經濟之問題。
另一方面,後者之均相觸媒由於通常在均一體系中進行氫化反應,故而與非均一體系相比活性較高,具有觸媒使用量較少,可於更低溫、低壓下進行氫化之特徵,但反面有觸媒製備較為繁雜且觸媒本身之穩定性亦不可謂之為充分,再現性亦較差,且容易一併發生副反應之缺點。又,亦有於將具有位阻之經烷基取代之烯烴性不飽和雙鍵氫化之情形時,無法獲得充分之氫化活性之問題。
因此,現狀為強烈期待開發一種高活性且容易操作之氫化觸媒。
另一方面,含有烯烴性不飽和雙鍵之聚合物雖不飽和雙鍵可有利地利用於硫化等,但因具有上述雙鍵,而有耐熱性、耐氧化性等穩定性較差之缺點。此種穩定性較差之缺點可藉由將聚合物氫化使聚合
物鏈中之不飽和雙鍵消失而明顯地改善。
然而,於將聚合物氫化之情形時,與將低分子化合物氫化之情形相比,由於受到反應體系之黏度或聚合物鏈之位阻等之影響,故而難以進行氫化。進而,有於氫化結束後,極難物理性地去除觸媒,而無法實質上完全分離等缺點。
如上所述,先前以來以獲得如下之氫化觸媒為課題:無需大量使用而於經濟上較為有利,儲存穩定性亦較高,且即便於將具有位阻之烯烴系不飽和雙鍵氫化之情形時亦可發揮充分之氫化活性,且氫化後之分離去除較為容易。
鑒於上述課題,專利文獻1及2中揭示有組合特定之二茂鈦化合物與烷基鋰而將烯烴化合物氫化之方法,專利文獻3及4中揭示有組合茂金屬化合物與有機鋁、鋅、及鎂而將烯烴性不飽和(共)聚合物氫化之方法,專利文獻5及6中揭示有組合特定之二茂鈦化合物與烷基鋰而將含有烯烴性不飽和基之活性聚合物氫化之方法。
又,專利文獻7中揭示有組合特定之二茂鈦化合物與烷氧基鋰而將含有烯烴性不飽和雙鍵之聚合物中之烯烴性雙鍵氫化的方法。再者,於該方法中進而必需烷氧基鋰以外之昂貴之有機金屬化合物作為還原劑。
進而,專利文獻8中揭示有組合特定之二茂鈦化合物、烯烴化合物及還原劑而將含有烯烴性不飽和雙鍵之聚合物氫化之方法。
進而,又於專利文獻9中揭示有組合具有將環戊二烯基之5個氫全部取代為甲基而成之五甲基環戊二烯基的茂金屬化合物與還原劑而將烯烴化合物氫化的方法。
又,進而於專利文獻10及11中揭示有利用包含特定之二茂鈦化合物、還原劑、含有烯烴性不飽和雙鍵之聚合物、及極性化合物之氫化用觸媒組合物將烯烴化合物氫化的方法。
又,專利文獻12中揭示有藉由包含特定之茂金屬化合物、以及選自共軛二烯單體、乙炔系化合物及乙炔系單體中之化合物的氫化用觸媒組合物而將烯烴化合物氫化的方法。
[專利文獻1]日本專利特開昭61-33132號公報
[專利文獻2]日本專利特開平1-53851號公報
[專利文獻3]日本專利特開昭61-28507號公報
[專利文獻4]日本專利特開昭62-209103號公報
[專利文獻5]日本專利特開昭61-47706號公報
[專利文獻6]日本專利特開昭63-5402號公報
[專利文獻7]日本專利特開平1-275605號公報
[專利文獻8]日本專利特開平2-172537號公報
[專利文獻9]日本專利特開平4-96904號公報
[專利文獻10]日本專利特開平08-33846號公報
[專利文獻11]日本專利特開平08-41081號公報
[專利文獻12]日本專利特開2004-269665號公報
然而,上述先前提出之技術中,作為氫化用觸媒於特性上均尚不充分。
因此,本發明之目的在於提供一種氫化用觸媒組合物,其可於經濟上有利地將含有烯烴性不飽和雙鍵之化合物(包括含有烯烴性不飽和雙鍵之聚合物)氫化,且儲存穩定性優異,給料性良好,並且可藉由氫化步驟而製造無色性優異之聚合物。
為解決上述先前技術之課題,本發明者等人反覆進行努力研究,結果發現藉由在含有(A)特定之二茂鈦化合物、(B)含有特定元素之化合物、(C)特定之不飽和化合物、(D)特定之極性化合物的氫化用觸媒組合物中,特定上述(C)成分與上述(A)成分之質量比((C)/(A))之範圍、及上述(D)成分與上述(A)成分之質量比((D)/(A))之範圍,而可解決上述先前技術之課題,從而完成本發明。
即,本發明係如下所述。
[1]
一種氫化用觸媒組合物,其係包含下述(A)、(B)、(C)、(D)者,且(C)與(A)之質量比(=(C)/(A))為0.1~4.0,(D)與(A)之質量比(=(D)/(A))為0.01~1.00。
(A):下述通式(1)所表示之二茂鈦化合物
上述通式(1)中,R5
、R6
表示選自由氫、C1~C12之烴基、芳氧基、烷氧基、鹵基、及羰基所組成之群之任一基,R5
、R6
可相同亦可不同。R1
、R2
表示選自由氫及C1~C12之烴基所組成之群之任一基,R1
、R2
可相同亦可不同。但,R1
及R2
均為氫或均為C1~C12之烴基之情況除外。
(B):含有選自由Li、Na、K、Mg、Zn、Al、Ca元素所組成之群之一種以上元素之化合物
(C):分子量為400以下之不飽和化合物
(D):極性化合物
[2]
如上述[1]之烯烴化合物之氫化用觸媒組合物,其中上述(C)中之不飽和基量於該(C)每1mol中為2mol以上。
[3]
如上述[1]或[2]之氫化用觸媒組合物,其中上述(B)為有機鋰化合物。
[4]
一種氫化方法,其係於如上述[1]至[3]中任一項之氫化用觸媒組合物之存在下,使含有烯烴性不飽和雙鍵之化合物於惰性有機溶劑中與氫接觸。
[5]
如上述[4]之氫化方法,其中上述含有烯烴性不飽和雙鍵之化合物為共軛二烯系聚合物、或共軛二烯與乙烯基芳香族烴之共聚物。
根據本發明,可提供一種氫化活性較高,給料性良好,儲存穩定性較高,且可製造無色性優異之氫化烯烴化合物的氫化用觸媒組合物。
以下,對用以實施本發明之形態(以下稱為「本實施形態」)詳細地進行說明。
以下之本實施形態係用以說明本發明之例示,並非旨在將本發明限定於以下內容。本發明可於其主旨之範圍內適當地變形而實施。
本實施形態之氫化用觸媒組合物係包含下述(A)、(B)、(C)、(D)者,且下述(C)與下述(A)之質量比(=(C)/(A))為0.1~4.0之範圍,下述(D)與下述(A)之質量比(=(D)/(A))為0.01~1.00之範圍。
(構成氫化用觸媒組合物之成分)
以下,對構成本實施形態之氫化用觸媒組合物之成分詳細地進行說明。
(A)成分:二茂鈦化合物(本說明書中,亦有時僅記載為(A)成分、(A))係如下述通式(1)所示。
上述通式(1)中,R5
、R6
表示選自由氫、C1~C12之烴基、芳氧基、烷氧基、鹵基及羰基所組成之群之任一基,R5
、R6
可相同亦可不同。
R1
、R2
表示選自由氫及C1~C12之烴基所組成之群之任一基,R1
、R2
可相同亦可不同。但,R1
、R2
均為氫或均為C1~C12之烴基之情況除外。
上述通式(1)中,作為R1
、R2
、R5
、R6
之C1~C12之烴基,例如,亦包含下述通式(2)所表示之取代基。
再者,R7
~R9
表示氫或C1~C4之烷基烴基,R7
~R9
中之至少任一者為氫,n=0或1。
作為(A)成分:二茂鈦化合物,並不限定於以下之例,例如可列舉:雙(η(5)-甲基環戊二烯基)二氫化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二氫化鈦、雙(η(5)-乙基環戊二烯基)二氫化鈦、雙(η(5)-丙基環戊二烯基)二氫化鈦、雙(η(5)-正丁基環戊二烯基)二氫化鈦、雙(η(5)-甲基環戊二烯基)二甲基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二甲基鈦、雙(η(5)-乙基環戊二烯基)二甲基鈦、雙(η(5)-丙基環戊二烯基)二甲基鈦、雙(η(5)-正丁基環戊二烯基)二甲基鈦、雙(η(5)-甲基環戊二烯基)二乙基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二乙基鈦、雙(η(5)-乙基環戊二烯基)二乙基鈦、雙(η(5)-丙基環戊二烯基)二乙基鈦、雙(η(5)-正丁基環戊二烯基)二乙基鈦、雙(η(5)-甲基環戊二烯基)二第二丁基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二第二丁基鈦、雙(η(5)-乙基環戊二烯基)二第二丁基鈦、雙(η(5)-丙基環戊二烯基)二第二丁基鈦、雙(η(5)-正丁基環戊二烯基)二第二丁基鈦、雙(η(5)-甲基環戊二烯基)二己基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二己基鈦、雙(η(5)-乙基環戊二烯基)二己基鈦、雙(η(5)-丙基環戊二烯基)二己基鈦、雙(η(5)-正丁基環戊二烯基)二己基鈦、雙(η(5)-甲基環戊二烯基)
二辛基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二辛基鈦、雙(η(5)-乙基環戊二烯基)二辛基鈦、雙(η(5)-丙基環戊二烯基)二辛基鈦、雙(η(5)-正丁基環戊二烯基)二辛基鈦、雙(η(5)-甲基環戊二烯基)二甲醇鈦、雙(η(5)-1,3-二甲基環戊二烯基)二甲醇鈦、雙(η(5)-乙基環戊二烯基)二甲醇鈦、雙(η(5)-丙基環戊二烯基)二甲醇鈦、雙(η(5)-正丁基環戊二烯基)二甲醇鈦、雙(η(5)-甲基環戊二烯基)二乙醇鈦、雙(η(5)-1,3-二甲基環戊二烯基)二乙醇鈦、雙(η(5)-乙基環戊二烯基)二乙醇鈦、雙(η(5)-丙基環戊二烯基)二乙醇鈦、雙(η(5)-正丁基環戊二烯基)二乙醇鈦、雙(η(5)-甲基環戊二烯基)二丙醇鈦、雙(η(5)-二甲基環戊二烯基)二丙醇鈦、雙(η(5)-乙基環戊二烯基)二丙醇鈦、雙(η(5)-丙基環戊二烯基)二丙醇鈦、雙(η(5)-正丁基環戊二烯基)二丙醇鈦、雙(η(5)-甲基環戊二烯基)二丁醇鈦、雙(η(5)-1,3-二甲基環戊二烯基)二丁醇鈦、雙(η(5)-乙基環戊二烯基)二丁醇鈦、雙(η(5)-丙基環戊二烯基)二丁醇鈦、雙(η(5)-正丁基環戊二烯基)二丁醇鈦、雙(η(5)-甲基環戊二烯基)二苯基鈦、雙(η(5)-1,3-甲基環戊二烯基)二苯基鈦、雙(η(5)-乙基環戊二烯基)二苯基鈦、雙(η(5)-丙基環戊二烯基)二苯基鈦、雙(η(5)-正丁基環戊二烯基)二苯基鈦、雙(η(5)-甲基環戊二烯基)二(間甲苯基)鈦、雙(η(5)-1,3-甲基環戊二烯基)二(間甲苯基)鈦、雙(η(5)-乙基環戊二烯基)二(間甲苯基)鈦、雙(η(5)-丙基環戊二烯基)二(間甲苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(間甲苯基)鈦、雙(η(5)-甲基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-1,3-甲基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-乙基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-丙基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-甲基環戊二烯基)二(間,對二甲苯基)鈦、雙(η(5)-1,3-二甲基環戊
二烯基)二(間,對二甲苯基)鈦、雙(η(5)-乙基環戊二烯基)二(間,對二甲苯基)鈦、雙(η(5)-丙基環戊二烯基)二(間,對二甲苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(間,對二甲苯基)鈦、雙(η(5)-甲基環戊二烯基)二(4-乙基苯基)鈦、雙(η(5)-1,3-二甲基環戊二烯基)二(4-乙基苯基)鈦、雙(η(5)-乙基環戊二烯基)二(4-乙基苯基)鈦、雙(η(5)-丙基環戊二烯基)二(4-乙基苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(4-乙基苯基)鈦、雙(η(5)-甲基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-1,3-二甲基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-乙基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-丙基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-甲基環戊二烯基)二苯氧化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二苯氧化鈦、雙(η(5)-乙基環戊二烯基)二苯氧化鈦、雙(η(5)-丙基環戊二烯基)二苯氧化鈦、雙(η(5)-正丁基環戊二烯基)二苯氧化鈦、雙(η(5)-正丁基環戊二烯基)二(4-己基苯基)鈦、雙(η(5)-甲基環戊二烯基)二氟化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二氟化鈦、雙(η(5)-乙基環戊二烯基)二氟化鈦、雙(η(5)-丙基環戊二烯基)二氟化鈦、雙(η(5)-正丁基環戊二烯基)二氟化鈦、雙(η(5)-甲基環戊二烯基)二氯化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二氯化鈦、雙(η(5)-乙基環戊二烯基)二氯化鈦、雙(η(5)-丙基環戊二烯基)二氯化鈦、雙(η(5)-正丁基環戊二烯基)二氯化鈦、雙(η(5)-甲基環戊二烯基)二溴化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二溴化鈦、雙(η(5)-乙基環戊二烯基)二溴化鈦、雙(η(5)-丙基環戊二烯基)二溴化鈦、雙(η(5)-正丁基環戊二烯基)二溴化鈦、雙(η(5)-甲基環戊二烯基)二碘化鈦、雙(η(5)-1,3-二甲基環戊二烯基)二碘化鈦、雙(η(5)-乙基環戊二烯基)二碘化鈦、雙(η(5)-丙
基環戊二烯基)二碘化鈦、雙(η(5)-正丁基環戊二烯基)二碘化鈦、雙(η(5)-甲基環戊二烯基)氯甲烷鈦、雙(η(5)-1,3-二甲基環戊二烯基)氯甲烷鈦、雙(η(5)-乙基環戊二烯基)氯甲烷鈦、雙(η(5)-丙基環戊二烯基)氯甲烷鈦、雙(η(5)-正丁基環戊二烯基)氯甲烷鈦、雙(η(5)-甲基環戊二烯基)氯乙醇鈦、雙(η(5)-1,3-二甲基環戊二烯基)氯乙醇鈦、雙(η(5)-乙基環戊二烯基)氯乙醇鈦、雙(η(5)-丙基環戊二烯基)氯乙醇鈦、雙(η(5)-正丁基環戊二烯基)氯乙醇鈦、雙(η(5)-甲基環戊二烯基)氯苯酚鈦、雙(η(5)-1,3-二甲基環戊二烯基)氯苯酚鈦、雙(η(5)-乙基環戊二烯基)氯苯酚鈦、雙(η(5)-丙基環戊二烯基)氯苯酚鈦、雙(η(5)-正丁基環戊二烯基)氯苯酚鈦、雙(η(5)-甲基環戊二烯基)二苄基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二苄基鈦、雙(η(5)-乙基環戊二烯基)二苄基鈦、雙(η(5)-丙基環戊二烯基)二苄基鈦、雙(η(5)-正丁基環戊二烯基)二苄基鈦、雙(η(5)-甲基環戊二烯基)二羰基鈦、雙(η(5)-1,3-二甲基環戊二烯基)二羰基鈦、雙(η(5)-乙基環戊二烯基)二羰基鈦、雙(η(5)-丙基環戊二烯基)二羰基鈦、雙(η(5)-正丁基環戊二烯基)二羰基鈦等。
該等可僅單獨使用1種,亦可組合2種以上而使用。
該等具有經烷基取代之環戊二烯基之二茂鈦化合物並不限定於上述例,亦可較佳地使用上述以外之環戊二烯基環之烷基之取代數為2、3、4者。
藉由使用上述各種二茂鈦化合物,本實施形態之氫化用觸媒組合物係將烯烴化合物(含有烯烴性不飽和雙鍵之化合物,以下有時僅記載為烯烴化合物)之烯烴性不飽和雙鍵氫化至高位,且氫化後之烯烴化合物之耐熱性優異。尤其,為獲得對共軛二烯系聚合物或共軛二烯與乙烯基芳香族烴之共聚物中之烯烴性不飽和雙鍵的氫化活性較高、且於較廣之溫度區域中選擇性地將不飽和雙鍵氫化至高位之氫化
用觸媒組合物,作為(A)二茂鈦化合物,較佳為以下化合物。例如可列舉:雙(η(5)-甲基環戊二烯基)二氯化鈦、雙(η(5)-乙基環戊二烯基)二氯化鈦、雙(η(5)-丙基環戊二烯基)二氯化鈦、雙(η(5)-正丁基環戊二烯基)二氯化鈦、雙(η(5)-甲基環戊二烯基)二甲基鈦、雙(η(5)-乙基環戊二烯基)二甲基鈦、雙(η(5)-丙基環戊二烯基)二甲基鈦、雙(η(5)-正丁基環戊二烯基)二甲基鈦、雙(η(5)-甲基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-乙基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-丙基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-甲基環戊二烯基)二苯基鈦、雙(η(5)-乙基環戊二烯基)二苯基鈦、雙(η(5)-丙基環戊二烯基)二苯基鈦、雙(η(5)-正丁基環戊二烯基)二苯基鈦。
進而,就於空氣中亦可穩定地進行操作之觀點而言,作為(A)二茂鈦化合物,並不限定於以下,作為較佳之例,例如可列舉:雙(η(5)-甲基環戊二烯基)二氯化鈦、雙(η(5)-正丁基環戊二烯基)二氯化鈦、雙(η(5)-甲基環戊二烯基)二苯基鈦、雙(η(5)-正丁基環戊二烯基)二苯基鈦、雙(η(5)-甲基環戊二烯基)二(對甲苯基)鈦、雙(η(5)-正丁基環戊二烯基)二(對甲苯基)鈦。
上述(A)成分:二茂鈦化合物例如可藉由使包含具有烷基取代基之環戊二烯基之四價二茂鈦鹵素化合物與芳基鋰反應而合成。合成之二茂鈦化合物之結構可藉由1H-NMR、MS光譜而特定。
作為含有特定之元素之化合物(B)(本說明書中,亦有時僅記載為(B)成分、(B)),於具有使上述(A)成分之二茂鈦化合物還原之能力的公知之有機金屬化合物、含金屬化合物之中,使用含有選自由Li、Na、K、Mg、Zn、Al、Ca元素所組成之群之一種以上元素的化合物。
作為(B)成分:含有特定之元素之化合物,可列舉:有機鋰化合物、有機鈉化合物、有機鉀化合物、有機鋅化合物、有機鎂化合物、有機鋁化合物、有機鈣化合物等。該等可僅單獨使用1種,亦可併用2種以上。
作為(B)成分之有機鋰化合物並不限定於以下,例如可列舉:甲基鋰、乙基鋰、正丙基鋰、異丙基鋰、正丁基鋰、第二丁基鋰、異丁基鋰、第三丁基鋰、正戊基鋰、正己基鋰、苯基鋰、環戊二烯基鋰、間甲苯基鋰、對甲苯基鋰、二甲苯基鋰、二甲基胺基鋰、二乙基胺基鋰、甲氧基鋰、乙氧基鋰、正丙氧基鋰、異丙氧基鋰、正丁氧基鋰、第二丁氧基鋰、第三丁氧基鋰、戊氧基鋰、己氧基鋰、庚氧基鋰、辛氧基鋰、苯氧基鋰、4-甲基苯氧基鋰、苄氧基鋰、4-甲基苄氧基鋰等。
又,作為(B)成分,亦可使用使酚系穩定劑與上述各種烷基鋰反應而獲得之酚基鋰化合物。
作為上述酚系穩定劑,並不限定於以下,例如可列舉:1-氧基-3-甲基-4-異丙基苯、2,6-二第三丁基苯酚、2,6-二第三丁基-4-乙基苯酚、2,6-二第三丁基-對甲酚、2,6-二第三丁基-4-正丁基苯酚、4-羥基甲基-2,6-二第三丁基苯酚、丁基羥基苯甲醚、2-(1-甲基環己基)-4,6-二甲基苯酚、2,4-二甲基-6-第三丁基苯酚、2-甲基-4,6-二壬基苯酚、2,6-二第三丁基-α-二甲基胺基-對甲酚、亞甲基-雙-(二甲基-4,6-苯酚)、2,2'-亞甲基-雙-(4-甲基-6-第三丁基苯酚)、2,2'-亞甲基-雙-(4-甲基-6-環己基苯酚)、2,2'-亞甲基-雙-(4-乙基-6-第三丁基苯酚)、4,4'-亞甲基-雙-(2,6-二第三丁基苯酚)、2,2'-亞甲基-雙-(6-α-甲基-苄基-對甲酚)等。
上述具體例之中,可尤佳地使用最通用之使2,6-二第三丁基-對甲酚之羥基成為-OLi的2,6-二第三丁基-4-甲基苯氧基鋰。
又,作為(B)成分之有機鋰化合物,除上述以外,亦可列舉:三甲基矽烷基鋰、二乙基甲基矽烷基鋰、二甲基乙基矽烷基鋰、三乙基矽烷基鋰、三苯基矽烷基鋰等有機矽鋰化合物。
作為(B)成分之有機鈉化合物,並不限定於以下,例如可列舉:甲基鈉、乙基鈉、正丙基鈉、異丙基鈉、正丁基鈉、第二丁基鈉、異丁基鈉、第三丁基鈉、正戊基鈉、正己基鈉、苯基鈉、環戊二烯基鈉、間甲苯基鈉、對甲苯基鈉、二甲苯基鈉、萘鈉等。
作為(B)成分之有機鉀化合物,並不限定於以下,例如可列舉:甲基鉀、乙基鉀、正丙基鉀、異丙基鉀、正丁基鉀、第二丁基鉀、異丁基鉀、第三丁基鉀、正戊基鉀、正己基鉀、三苯基甲基鉀、苯基鉀、苯基乙基鉀、環戊二烯基鉀、間甲苯基鉀、對甲苯基鉀、二甲苯基鉀、萘鉀等。
作為(B)成分之上述有機鹼金屬化合物、有機鹼土金屬化合物之一部分亦可作為共軛二烯化合物及/或乙烯基芳香族烴化合物之活性陰離子聚合起始劑而使用,但於作為被氫化物之烯烴化合物為具有該等金屬之活性末端之共軛二烯系聚合物、或共軛二烯與乙烯基芳香族烴之共聚物(活性聚合物)之情形時,該等活性末端亦作為(B)成分發揮作用。
作為(B)成分之有機鋅化合物,並不限定於以下,例如可列舉:二乙基鋅、雙(η(5)-環戊二烯基)鋅、二苯基鋅等。
作為(B)成分之有機鎂化合物,並不限定於以下,例如可列舉:二甲基鎂、二乙基鎂、二丁基鎂、乙基丁基鎂、甲基溴化鎂、乙基氯化鎂、乙基溴化鎂、乙基氯化鎂、苯基溴化鎂、苯基氯化鎂、第三丁基氯化鎂、第三丁基溴化鎂等。
作為(B)成分之有機鋁化合物,並不限定於以下,例如可列舉:三甲基鋁、三乙基鋁、三異丁基鋁、三苯基鋁、二乙基氯化鋁、二甲
基氯化鋁、乙基二氯化鋁、甲基倍半氯化鋁、乙基倍半氯化鋁、二乙基氫化鋁、二異丁基氫化鋁、三苯基鋁、三(2-乙基己基)鋁、(2-乙基己基)二氯化鋁、甲基鋁氧烷、乙基鋁氧烷等。
除該等以外,作為(B)成分,例如亦可使用:氫化鋰、氫化鉀、氫化鈉、氫化鈣等鹼(土)金屬氫化物,或氫化鈉鋁、氫化鉀鋁、二異丁基氫化鈉鋁、三(第三丁氧基)氫化鋁、三乙基氫化鈉鋁、二異丁基氫化鈉鋁、三乙基氫化鈉鋁、三乙氧基氫化鈉鋁、三乙基氫化鋰鋁等含有2種以上金屬之氫化物。
又,藉由使上述有機鹼金屬化合物與有機鋁化合物預先反應而合成之錯合物、藉由使有機鹼金屬化合物與有機鎂化合物預先反應而合成之錯合物(酸根型錯合物)等亦可作為(B)成分而使用。
再者,作為(B)含有特定之元素之化合物之有機金屬化合物、含金屬化合物,就較高之氫化活性之觀點而言,較佳為含有Li、Al之化合物。就更高之氫化活性之方面而言,更佳為有機鋰化合物。
所謂不飽和化合物(C)(本說明書中,有時僅記載為(C)成分、(C)),係指分子中具有1個以上不飽和基之分子量400以下之化合物。
就氫化用觸媒組合物於儲存後之給料性之觀點而言,(C)成分之分子量設為400以下,分子量較佳為300以下,更佳為200以下,進而較佳為150以下。
於(C)成分:不飽和化合物為聚合物之情形時,可藉由使特定之單體聚合而製造。
作為上述單體,並不限定於以下,例如可列舉:1,3-丁二烯、異戊二烯、2,3-二甲基丁二烯、1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、4,5-二乙基-1,3-辛二烯、3-丁基-1,3-辛二烯等通常具有4~約12個烴之共軛二烯、單萜、乙烯基芳香族化合物、降二烯、環戊二
烯、環己二烯、2,3-二氫二環戊二烯、乙炔類。
關於該等單體,該等可單獨使用,亦可使兩種以上進行共聚合。
就本實施形態之氫化用觸媒組合物於儲存後之給料性、使用本實施形態之氫化用觸媒組合物而氫化之烯烴化合物之聚合物之黃變較小之觀點而言,不飽和化合物(C)中之不飽和基量係規定較佳之範圍。
即,就較高之氫化活性或給料性之觀點而言,(C)中之不飽和基量較佳為相對於(C)1mol為2mol以上。就較高之氫化活性或聚合物之黃變抑制之觀點而言,較佳為5mol以下。更佳為2mol以上且4mol以下之範圍,進而較佳為2mol以上且3mol以下之範圍,進而更佳為3mol。
(C)成分中之不飽和基量可藉由NMR而測定。
進而,就該氫化活性、儲存後之給料性之觀點而言,本實施形態之氫化用觸媒組合物之(C)成分與(A)成分之質量比(=(C)/(A))設為0.1以上,就本實施形態之氫化用觸媒組合物之氫化活性、與給料性相關之儲存穩定性、經濟性、經氫化之烯烴化合物之聚合物之黃變抑制之觀點而言,設為4.0以下。
(C)成分與(A)成分之質量比(=(C)/(A))較佳為0.5~3.0之範圍,更佳為1.0~2.5之範圍。
進而,又,就本實施形態之氫化用觸媒組合物於儲存後之給料性之觀點而言,(C)不飽和化合物之不飽和基量與上述(A)二茂鈦化合物的莫耳比(=(C)之不飽和基量/(A))較佳為0.1以上,就本實施形態之氫化用觸媒組合物之與給料性相關之儲存穩定性、經濟性、聚合物之黃變抑制、較高之氫化活性之觀點而言,較佳為25以下。
上述(C)之不飽和基量/(A)更佳為0.6~20之範圍,進而較佳為1.0
~10之範圍。
如上所述,藉由(C)不飽和化合物之分子量為400以下,本實施形態之氫化用觸媒組合物可獲得較高之儲存後之給料性,藉由(C)成分與(A)成分之質量比(=(C)/(A))為0.1~4.0,可獲得較高之氫化活性、儲存後之給料性、經氫化之烯烴化合物之聚合物黃變抑制效果,進而,藉由(C)之不飽和基量與(A)成分之莫耳比為上述範圍,可減少對作為氫化對象之聚合物中之烯烴性不飽和雙鍵以外之氫化量,而獲得較高之氫化活性。
所謂(D)成分:極性化合物(本說明書中,有時僅記載為(D)成分、(D)),係指具有N、O或S之化合物,並不限定於以下,例如可列舉:醇化合物、醚化合物、硫醚化合物、酮化合物、亞碸化合物、羧酸化合物、羧酸酯化合物、醛化合物、內醯胺化合物、內酯化合物、胺化合物、醯胺化合物、腈化合物、環氧化合物及肟化合物。
作為該等極性化合物,可列舉以下化合物作為具體例。
作為上述醇化合物,並不限定於以下,例如可列舉:甲醇、乙醇、丙醇、正丁醇、第二丁醇、異丁醇、第三丁醇、正戊醇、異戊醇、己醇及其異構物、庚醇及其異構物、辛醇及其異構物、辛醇、壬醇及其異構物、癸醇及其異構物、苄醇、苯酚、甲酚、2,6-二第三丁基-對甲酚等一元醇,乙二醇、丙二醇、丁二醇、戊二醇、己二醇、庚二醇及該等之異構物即二醇(二元醇)等。又,亦可為甘油等三元醇或乙醇胺、縮水甘油醇等一分子中具有其他官能基之醇化合物。
作為上述醚化合物,並不限定於以下,例如可列舉:二甲醚、二乙醚、二正丙醚、二異丙醚、二正丁醚、二第二丁醚、二苯醚、甲基乙基醚、乙基丁基醚、丁基乙烯基醚、苯甲醚、乙基苯基醚、乙二醇二甲醚、乙二醇二乙醚、乙二醇二丁醚、二乙二醇二甲醚、二乙二
醇二乙醚、呋喃、四氫呋喃、α-甲氧基四氫呋喃、吡喃、四氫吡喃、二烷等。
又,亦可為如四氫呋喃羧酸之分子中具有其他官能基之化合物。
作為上述硫醚化合物,並不限定於以下,例如可列舉:二甲硫醚、二乙硫醚、二正丁硫醚、二第二丁硫醚、二第三丁硫醚、二苯硫醚、甲基乙基硫醚、乙基丁基硫醚、硫代苯甲醚、乙基苯基硫醚、噻吩、四氫噻吩等。
作為上述酮化合物,並不限定於以下,例如可列舉:丙酮、二乙基酮、二正丙基酮、二異丙基酮、二正丁基酮、二第二丁基酮、二第三丁基酮、二苯甲酮、甲基乙基酮、苯乙酮、苄基苯基酮、苯丙酮、環戊酮、環己酮、二乙醯、乙醯丙酮、苯甲醯丙酮等。
作為上述亞碸化合物,並不限定於以下,例如可列舉:二甲基亞碸、二乙基亞碸、四亞甲基亞碸、五亞甲基亞碸、二苯基亞碸、二苄基亞碸、對甲苯基亞碸等。
作為上述羧酸化合物,並不限定於以下,例如可列舉:甲酸、乙酸、丙酸、丁酸、己酸、月桂酸、棕櫚酸、硬脂酸、環己基丙酸、環己基己酸、苯甲酸、苯基乙酸、鄰甲苯甲酸、間甲苯甲酸、對甲苯甲酸、丙烯酸、甲基丙烯酸等一元酸,草酸、順丁烯二酸、丙二酸、反丁烯二酸、琥珀酸、己二酸、庚二酸、辛二酸、癸二酸、伊康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘二甲酸、聯苯二甲酸等二元酸,除此以外,亦可列舉:偏苯三甲酸、均苯四甲酸及該等之衍生物。又,例如,亦可為如羥基苯甲酸之一分子中具有官能基之化合物。
作為上述羧酸酯,並不限定於以下,例如可列舉:甲酸、乙酸、丙酸、丁酸、己酸、月桂酸、棕櫚酸、硬脂酸、環己基丙酸、環
己基己酸、苯甲酸、苯基乙酸、鄰甲苯甲酸、間甲苯甲酸、對甲苯甲酸、丙烯酸、甲基丙烯酸等一元酸,草酸、順丁烯二酸、丙二酸、反丁烯二酸、琥珀酸、己二酸、庚二酸、辛二酸、癸二酸、伊康酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、萘二甲酸、聯苯二甲酸等二元酸,與甲醇、乙醇、丙醇、正丁醇、第二丁醇、異丁醇、第三丁醇、正戊醇、異戊醇、己醇及其異構物、庚醇及其異構物、辛醇(octyl alcohol)及其異構物、正辛醇(capryl alcohol)、壬醇及其異構物、癸醇及其異構物、苄醇、苯酚、甲酚、縮水甘油醇等醇類的酯,乙醯乙酸甲酯、乙醯乙酸乙酯等β-酮酯。
作為上述內酯化合物,並不限定於以下,例如可列舉:β-丙內酯、δ-戊內酯、ε-己內酯及與下述酸對應之內酯化合物。
即,作為上述酸,可列舉:2-甲基-3-羥基丙酸、3-羥基壬烷或3-羥基壬酸、2-十二烷基-3-羥基丙酸、2-環戊基-3-羥基丙酸、2-正丁基-3-環己基-3-羥基丙酸、2-苯基-3-羥基十三酸、2-(2-乙基環戊基)-3-羥基丙酸、2-甲基苯基-3-羥基丙酸、3-苄基-3-羥基丙酸、2,2-二甲基-3-羥基丙酸、2-甲基-5-羥基戊酸、3-環己基-5-羥基戊酸、4-苯基-5-羥基戊酸、2-庚基-4-環戊基-5-羥基戊酸、3-(2-環己基乙基)-5-羥基戊酸、2-(2-苯基乙基)-4-(4-環己基苄基)-5-羥基戊酸、苄基-5-羥基戊酸、3-乙基-5-異丙基-6-羥基己酸、2-環戊基-4-己基-6-羥基己酸、2-環戊基-4-己基-6-羥基己酸、3-苯基-6-羥基己酸、3-(3,5-二乙基-環己基)-5-乙基-6-羥基己酸、4-(3-苯基-丙基)-6-羥基己酸、2-苄基-5-異丁基-6-羥基己酸、7-苯基-6-羥基-辛烯酸、2,2-二(1-環己烯基)-5-羥基-5-庚烯酸、2,2-二丙烯基-5-羥基-5-庚烯酸、2,2-二甲基-4-丙烯基-3-羥基-3,5-庚二烯酸等。
作為上述胺化合物,並不限定於以下,例如可列舉:甲基胺、乙基胺、異丙基胺、正丁基胺、第二丁基胺、第三丁基胺、正戊基
胺、第二戊基胺、第三戊基胺、正己基胺、正庚基胺、苯胺、苄基胺、鄰甲氧苯胺、間甲氧苯胺、對甲氧苯胺、α-萘基胺、二甲基胺、二乙基胺、二正丙基胺、二異丙基胺、二正丁基胺、二第二丁基胺、二異丁基胺、二第三丁基胺、二正戊基胺、二異戊基胺、二苄基胺、N-甲基苯胺、N-乙基苯胺、N-乙基-鄰甲苯胺、N-乙基-間甲苯胺、N-乙基-對甲苯胺、三乙基胺、三正丙基胺、三正丁基胺、三正戊基胺、三異戊基胺、三正己基胺、三苄基胺、三苯基甲基胺、N,N-二甲基苄基胺、N,N-二甲基苯胺、N,N-二乙基苯胺、N,N-二乙基-鄰甲苯胺、N,N-二乙基-間甲苯胺、N,N-二乙基-對甲苯胺、N,N-二甲基-α-萘基胺、N,N,N',N'-四甲基乙二胺、N,N,N',N'-四乙基乙二胺、吡咯啶、哌啶、N-甲基吡咯啶、N-甲基哌啶、吡啶、哌、2-乙醯吡啶、N-苄基哌、喹啉、啉等。
上述醯胺化合物係分子中具有至少一個-C(=O)-N<或-C(=S)-N<鍵之化合物,並不限定於以下,例如可列舉:N,N-二甲基甲醯胺、N-二甲基乙醯胺、N-甲基吡咯啶酮、乙醯胺、丙醯胺、苯甲醯胺、乙醯苯胺、苯甲醯苯胺、N-甲基乙醯苯胺、N,N-二甲基硫代甲醯胺、N,N-二甲基-N,N'-(對二甲基胺基)苯甲醯胺、N-伸乙基-N-甲基-8-喹啉甲醯胺基、N,N-二甲基煙鹼醯胺、N,N-二甲基甲基丙烯醯胺、N-甲基鄰苯二甲醯亞胺、N-苯基鄰苯二甲醯亞胺、N-乙醯-ε-己內醯胺、N,N,N',N'-四甲基鄰苯二甲醯胺、10-乙醯啡、3,7-雙(二甲基胺基)-10-苯甲醯啡噻、10-乙醯啡噻、3,7-雙(二甲基胺基)-10-苯甲醯啡噻、N-乙基-N-甲基-8-喹啉甲醯胺基等,除此以外,亦可列舉:N,N'-二甲基脲、N,N'-二乙基脲、N,N'-二甲基伸乙基脲、N,N,N',N'-四甲基脲、N,N-二甲基-N',N'-二乙基脲、N,N-二甲基-N',N'-二苯基脲等直鏈狀脲化合物。
作為上述環氧化合物,並不限定於以下,例如可列舉:1,3-環氧
丁烯、1,3-丁二烯氧化物、1,2-環氧丁烷、2,3-環氧丁烷、環氧環己烷、1,2-環氧環十二烷、1,2-環氧癸烷、1,2-環氧二十烷、1,2-環氧庚烷、1,2-環氧十六烷、1,2-環氧十六烷、1,2-環氧十八烷、1,2-環氧辛烷、乙二醇二縮水甘油醚、1,2-環氧十四烷、環氧己烷、環氧異丁烷、1,7-辛二烯環氧化物、2-苯基環氧丙烷、環氧丙烷、反茋氧化物、環氧苯乙烷、環氧化1,2-聚丁二烯、環氧化亞麻仁油、縮水甘油基甲醚、縮水甘油基正丁醚、縮水甘油基烯丙醚、甲基丙烯酸縮水甘油酯、丙烯酸縮水甘油酯等。
作為上述肟化合物,並不限定於以下,例如可列舉:丙酮肟、甲基乙基酮肟、二乙基酮肟、苯乙酮肟、二苯甲酮肟、苄基苯基酮肟、環戊酮肟、環己酮肟、苯甲醛肟等。
上述(D)成分:極性化合物可僅單獨使用1種,亦可併用2種以上。
作為極性化合物,較佳為胺化合物或醚化合物。就較高之氫化活性或氫化用觸媒組合物之較高之給料性之方面而言,更佳為胺化合物。
就本實施形態之氫化用觸媒組合物之氫化活性、或與給料性相關之儲存穩定性之觀點而言,上述(D)成分與上述(A)成分之質量比(=(D)/(A))設為0.01以上,就本實施形態之氫化用觸媒組合物之氫化活性、與給料性相關之儲存穩定性、經濟性之觀點而言,設為1.00以下。
上述(D)成分與上述(A)成分之質量比(=(D)/(A))較佳為0.015~0.500之範圍,更佳為0.020~0.300之範圍。
本實施形態之氫化用觸媒組合物可藉由視需要使用特定之溶劑
將上述(A)成分、(B)成分、(C)成分及(D)成分混合而製造。
就較高之氫化活性、較高之給料性、無色性之觀點而言,本實施形態之氫化用觸媒組合物之製造方法較佳為於(A)成分、(C)成分及(D)成分之共存下,最後添加上述(A)成分、(B)成分、(C)成分及(D)成分中的(B)成分。此時,上述(A)成分、(C)成分、(D)成分之添加順序為任意,並無特別限定。
氫化用觸媒組合物可預先於與被氫化物之反應體系不同之觸媒槽中製備之後,導入至反應體系中,亦可分別向反應體系中導入氫化用觸媒組合物之成分。
本實施形態之氫化用觸媒組合物之黏度較低、給料性良好、且儲存穩定性優異,因此適合於另一觸媒槽中製備之後,導入至氫化反應體系的方法。尤其,較佳為連續地供給被氫化物、及預先製備之氫化用觸媒組合物的氫化方法(連續氫化)。
於被氫化物為共軛二烯系聚合物或共軛二烯與乙烯基芳香族烴之共聚物之情形時,且於該聚合物或共聚物藉由以有機鹼金屬或有機鹼土金屬為起始劑之活性陰離子聚合而獲得之情形時,向上述反應體系中導入氫化用觸媒組合物之成分時,聚合物或共聚物之活性末端亦可為作為上述(B)成分而利用一部分或全部。
又,亦可於作為被氫化物之聚合物或共聚物之聚合後,藉由聚合失活劑使活性末端之一部分或全部失活。
亦可較佳地使用過量之醇或酮化合物等作為聚合失活劑。於向反應體系中分別導入氫化用觸媒組合物之成分之情形時,且於過多量失活劑存在於反應體系中之情形時,該等亦可被視為(D)成分、或(D)成分之一部分。再者,於此情形是,上述(D)成分與(A)成分之質量比(=(D)/(A))係將過多量之失活劑視為(D)成分而算出。
製備本實施形態之氫化用觸媒組合物之環境可為惰性氣體環
境,亦可為氫氣環境。
製備溫度及儲存溫度較佳為-50℃~50℃之範圍,更佳為-20℃~30℃。
製備需要之時間亦根據調製溫度而不同,於25℃之條件下為數秒至60日,較佳為1分鐘至20日。
於預先於與被氫化物之反應體系不同之觸媒槽中製造本實施形態之氫化用觸媒組合物之情形時,構成本實施形態之氫化用觸媒組合物之(A)成分、(B)成分、(C)成分、及(D)成分於以溶解於惰性有機溶劑中之溶液之形式使用時容易處理,故而較佳。
作為上述惰性有機溶劑,使用與氫化反應之任何關聯物均不反應之溶劑。較佳為與氫化反應中使用之溶劑相同之溶劑。
於預先於與被氫化物之反應體系不同之觸媒槽中製造本實施形態之氫化用觸媒組合物之情形時,於進行氫化時,必須將所製造之氫化用觸媒組合物移送至收容有被氫化物之氫化反應器(氫化槽)中,此時較佳為於氫氣環境下進行。
移送時之溫度較佳為-30℃~100℃之溫度,更佳為於-10℃~50℃之溫度下恰於氫化反應前添加。
用以表現較高之氫化活性及氫化選擇性之各成分之混合比率較佳為以成分(B)之金屬莫耳數與成分(A)之金屬(Ti)莫耳數之比率(以下記為金屬(Metal)(B)/金屬(A)莫耳比)計,約為20以下之範圍。
於金屬(B)/金屬(A)之莫耳比=0、即不存在金屬(B)之情形時,亦可藉由熱還原而進行定量的氫化,但需要更高溫、長時間、高觸媒量,因此較佳為存在金屬(B)。
藉由金屬(B)/金屬(A)莫耳比為20以下,可防止過量地使用與實質上之活性提高無關之昂貴之觸媒成分(B),於經濟上較為優異,可防止不必要之副反應。
藉由選擇如金屬(B)/金屬(A)莫耳比=0.5~10之範圍之成分(A)與成分(B)之混合比率,可提高氫化用觸媒組合物之氫化活性,因此最佳為該莫耳比。
於被氫化物為以活性陰離子聚合獲得之活性聚合物之情形時,活性末端作為還原劑發揮作用,因此將具有活躍的活性末端之聚合物氫化時,達成上述最佳之金屬(B)/金屬(A)莫耳比,因此較佳為利用具有各種活性氫或鹵素之化合物使活躍的活性末端失活。
作為上述具有活性氫之化合物,可列舉:水及甲醇、乙醇、正丙醇、正丁醇、第二丁醇、第三丁醇,1-戊醇、2-戊醇、3-戊醇、1-己醇、2-己醇、3-己醇、1-庚醇、2-庚醇、3-庚醇、4-庚醇、辛醇、壬醇、癸醇、十一醇、月桂醇、烯丙醇、環己醇、環戊醇、苄醇等醇類,苯酚、鄰甲酚、間甲酚、對甲酚、對烯丙基苯酚、2,6-二第三丁基-對甲酚、二甲苯酚、二氫蒽醌、二羥基香豆素、1-羥基蒽醌、間羥基苄醇、間苯二酚、白金精等酚類。
又,作為酸,可列舉:乙酸、丙酸、丁酸、異乙酸、戊酸、己酸、庚酸、癸酸、肉豆蔻酸、硬脂酸、山萮酸、苯甲酸等有機羧酸等。
又,作為具有鹵素之化合物,可列舉:氯化苄基、氯化(溴化)三甲基矽烷基、氯化(溴化)第三丁基矽烷基、氯化(溴化)甲基、氯化(溴化)乙基、氯化(溴化)丙基、氯化(溴化)正丁基等。
該等可僅單獨使用1種,亦可併用2種以上。
本實施形態係藉由於上述之本實施形態之氫化用觸媒組合物之存在下,使含有烯烴性不飽和雙鍵之化合物與氫接觸而進行氫化。
本實施形態之氫化用觸媒組合物可用於進行具有烯烴性不飽和雙鍵之全部化合物之氫化的步驟中。
作為具有烯烴性不飽和雙鍵之化合物,並不限定於以下,例如可列舉:乙烯、丙烯、丁烯、戊烯、己烯、庚烯、辛烯等之異構物等脂肪族烯烴;環戊烯、甲基環戊烯、環戊二烯、環己烯、甲基環己烯、環己二烯等脂環式烯烴;苯乙烯、丁二烯、異戊二烯等單體類;不飽和脂肪酸及其衍生物、不飽和液狀低聚物等分子中含有至少一個烯烴性不飽和雙鍵的低分子聚合物等。
又,本實施形態之氫化用觸媒組合物亦可用於共軛二烯系聚合物、共軛二烯與烯烴單體之共聚物之烯烴性不飽和雙鍵之選擇性氫化。
此處所謂之選擇性氫化,係指將共軛二烯系聚合物、共軛二烯與烯烴單體之共聚物之共軛二烯部分之烯烴性不飽和雙鍵選擇性地氫化,具體而言,於使用乙烯基芳香族化合物、例如乙烯基芳香族烴作為上述烯烴單體之情形時,芳香環之碳-碳雙鍵實質上意指未進行氫化。
共軛二烯系聚合物、共軛二烯與烯烴單體之共聚物之烯烴性不飽和雙鍵之選擇性氫化物係作為彈性體或熱塑性彈性體而於工業上較為有用。
作為上述作為被氫化物之共軛二烯系聚合物之製造中使用之共軛二烯,通常,可列舉具有4~約12個碳原子之共軛二烯。
並不限定於以下,例如可列舉:1,3-丁二烯、異戊二烯、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、2-甲基-1,3-戊二烯、1,3-己二烯、4,5-二乙基-1,3-辛二烯、3-丁基-1,3-辛二烯等。
就可於工業上有利地開展,獲得物性優異之彈性體之觀點而言,較佳為1,3-丁二烯、異戊二烯。
丁二烯部分之微結構中存在1,2鍵與1,4鍵(順式+反式),但本實施形態之氫化用觸媒組合物中,任一者均可定量地進行氫化。
又,異戊二烯部分係於1,2鍵、3,4鍵之側鏈與1,4鍵(順式+反式)之主鏈上存在烯烴性不飽和鍵,但藉由本實施形態之製造方法獲得之氫化用觸媒組合物中,任一者均可定量地進行氫化。
藉由本實施形態之氫化用觸媒組合物進行氫化而成之化合物之結構及氫化率可藉由1H-NMR而測定。
若藉由使用本實施形態之氫化用觸媒組合物之氫化方法,則尤其可將丁二烯部分之1,2鍵、1,4鍵、及異戊二烯部分之1,2鍵、3,4鍵之側鏈選擇性地氫化。
於選擇1,3-丁二烯作為以氫化用觸媒組合物進行氫化而成之共軛二烯系聚合物之主成分之情形時,尤其於低溫至室溫下表現出彈性體彈性時,作為被氫化物之丁二烯單元部分之微結構,1,2鍵之量較佳為8%以上,更佳為20%以上,進而較佳為之範圍為30~80%。
又,於選擇異戊二烯作為以氫化用觸媒組合物進行氫化而成之被氫化物之共軛二烯系聚合物之主成分之情形時,藉由相同之原因,作為異戊二烯單元之微結構,1,4鍵之量較佳為50%以上,更佳為75%以上。
為充分地發揮僅選擇性地將共軛二烯單元之不飽和雙鍵氫化之效果,獲得於工業上較為有用且價值較高之彈性體或熱塑性彈性體,作為被氫化物,尤佳為共軛二烯與乙烯基芳香族烴之共聚物。作為可與至少一種共軛二烯進行共聚合之乙烯基芳香族烴,例如可列舉:苯乙烯、第三丁基苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、二乙烯苯、1,1-二苯乙烯、N,N-二甲基-對胺基乙基苯乙烯、N,N-二乙基-對胺基乙基苯乙烯等,尤佳為苯乙烯及/或α-甲基苯乙烯。
作為具體之共聚物之例,丁二烯/苯乙烯共聚物、異戊二烯/苯乙烯共聚物、丁二烯/異戊二烯/苯乙烯共聚物等提供工業上價值較高之氫化共聚物,故而較佳。該等共聚物為無規、嵌段、遞變嵌段共聚物
等,並無特別限定。
若使用本實施形態之氫化用觸媒組合物,選擇下述較佳之氫化條件,則上述共聚物中之乙烯基芳香族烴單元之碳-碳雙鍵(芳香環)之氫化實質上並未發生。
使用本實施形態之氫化用觸媒組合物之氫化反應較佳為將具有烯烴性不飽和雙鍵之化合物於溶解於惰性有機溶劑之溶液中與氫接觸而進行。
此處所謂之「惰性有機溶劑」,係指溶劑與氫化反應之任何關聯物均不反應。並不限定於以下,例如可列舉:正戊烷、正己烷、正庚烷、正辛烷之類的脂肪族烴類,環己烷、環庚烷、環庚烷之類的脂環式烴類,二乙醚、四氫呋喃之類的醚類的單獨或混合物。又,苯、甲苯、二甲苯、乙基苯之類的芳香族烴只要於所選擇之氫化條件下、於芳香族雙鍵未氫化時亦可使用。
氫化反應通常藉由於氫氣或惰性環境下將上述被氫化物溶液保持為特定之溫度,於攪拌下或不攪拌下添加氫化用觸媒組合物,繼而導入氫氣,加壓至特定壓而實施。所謂惰性環境,例如係指氮氣、氦氣、氖、氬等不與氫化反應之任何關聯物反應之環境。空氣或氧氣係對觸媒成分進行氧化而導致氫化用觸媒組合物之失活,故而欠佳。
本實施形態之氫化用觸媒組合物之黏度較低、給料性良好、且儲存穩定性優異,因此較佳為向氫化反應器中連續地供給被氫化物與氫化用觸媒組合物的氫化方法(連續氫化)。
氫化步驟中,氫化用觸媒組合物之添加量以成分(A)之莫耳量換算較佳為相對於被氫化物100g為0.001~20毫莫耳之範圍。
若為該添加量範圍,則可優先將被氫化物之烯烴性不飽和雙鍵氫化,且實質上不引起共聚物中之芳香環之雙鍵之氫化,因此可實現極高之選擇性氫化。
於添加以成分(A)之莫耳量換算相對於被氫化物100g超過20毫莫耳之量之氫化用觸媒組合物之情形時,氫化反應亦可進行,但必要以上之觸媒使用會導致變得不經濟,氫化反應後之觸媒去灰分、去除變得複雜等。
又,於所選擇之條件下將聚合物之共軛二烯單元之不飽和雙鍵定量地氫化,其較佳之氫化用觸媒組合物之添加量以成分(A)之莫耳量換算相對於被氫化物100g為0.01~5毫莫耳。
氫化反應更佳為於攪拌下進行,藉此可使所導入之氫足夠迅速地與被氫化物接觸。
氫化反應較佳為於0~200℃之溫度範圍內實施。
藉由於0℃以上進行,可以充分之氫化速度進行,可防止需要大量觸媒。又,藉由於200℃以下進行,可防止副反應、分解反應、凝膠化、或該等之一併發生,進而可防止氫化用觸媒組合物之失活、氫化活性降低。
更佳之溫度範圍為20~180℃。
氫化反應中使用之氫之壓力較佳為1~100kgf/cm2
。
若未達1kgf/cm2
,則有氫化速度變慢,無法獲得充分之氫化率之虞,若為超過100kgf/cm2
之壓力,則與升壓同時,氫化反應幾乎結束,而有導致不必要之副反應或凝膠化之虞。
更佳之氫化氫氣壓力為2~30kgf/cm2
,與氫化用觸媒組合物添加量等相關地選擇最佳氫氣壓力,實質上隨著上述氫化用觸媒組合物量變為少量,氫氣壓力較佳為選擇高壓側而實施。
又,氫化反應時間通常為數秒~50小時。
氫化反應時間及氫化壓力係根據所需之氫化率於上述範圍內適當選擇而實施。
藉由上述之氫化步驟,烯烴化合物之烯烴性不飽和雙鍵、共軛
二烯系共聚物及共軛二烯與乙烯基芳香族烴之共聚物中之烯烴性不飽和雙鍵可根據目的而獲得任意之氫化率。
使用本實施形態之氫化用觸媒組合物進行氫化反應後,可藉由蒸餾、沈澱等化學或物理方法將氫化物自含有氫化物之溶液中容易地分離。
尤其,於被氫化物為聚合物之情形時,可自進行氫化反應之聚合物溶液中視需要去除氫化用觸媒組合物之殘渣,使所氫化之聚合物自溶液分離。
作為分離之方法,例如可列舉:於氫化後之反應液中添加對丙酮或醇等氫化聚合物為不良溶劑之極性溶劑,使氫化聚合物沈澱而回收的方法;於攪拌下將反應液投入至熱水中後,將氫化聚合物與溶劑一併蒸餾回收的方法;或者直接加熱反應液將溶劑蒸餾去除而回收氫化聚合物的方法等。
以下,舉出具體之實施例及比較例對本發明詳細地進行說明,但本發明並不限定於以下實施例。
將實施例及比較例中使用之氫化用觸媒組合物之構成成分表示如下。
<(A-1):雙(η(5)-環戊二烯基)二(對甲苯基)鈦之合成>
於具備攪拌機、滴液漏斗、及回流冷卻器之1L容量之三口燒瓶中添加無水醚200mL。
利用乾燥氦氣使裝置乾燥,將小枚鋰絲17.4g(2.5莫耳)切落至燒瓶中,於室溫下滴加少量醚300mL、對溴甲苯171g(1莫耳)之溶液後,於回流下緩緩地添加全部對溴甲苯之醚溶液。
反應結束後,於氦氣環境下將反應溶液過濾,獲得無色透明之
對甲苯基鋰溶液。
於具備經乾燥氦氣置換之攪拌機、滴液漏斗之2L三口燒瓶中添加雙(η(5)-環戊二烯基)二氯化鈦99.6g(0.4莫耳)、及無水醚500mL。
於室溫攪拌下滴加先前合成之對甲苯基鋰之醚溶液約2小時。
於空氣中將反應混合物過濾分離,以二氯甲烷將不溶部洗淨後,於減壓下將濾液及洗淨液與溶劑一併去除。
使殘留物溶解於少量二氯甲烷後,添加石油醚進行再結晶。
將所獲得之結晶過濾分離,再次將濾液濃縮並反覆進行上述操作,而獲得雙(η(5)-環戊二烯基)二(對甲苯基)鈦。
產率為87%。
所獲得之結晶為橙黃色針狀,對甲苯、環己烷之溶解性良好,且溶點為145℃,元素分析值:C為80.0,H為6.7,Ti為13.3。
<(A-2):雙(η(5)-環戊二烯基)二(苯基)鈦之合成>
使用溴苯157g(1莫耳)代替上述(A-1)中使用之對溴甲苯,除此以外,與上述(A-1)同樣地進行合成,獲得苯基鋰。使用該苯基鋰,藉由與上述(A-1)相同之步驟,獲得雙(η(5)-環戊二烯基)二苯基鈦。產量為120g(產率90%)。
所獲得之結晶為橙黃色針狀,對甲苯、環己烷之溶解性略微良好,且溶點為147℃,元素分析值:C為79.5,H為6.1,Ti為14.4。
<(A-3):雙(η(5)-環戊二烯基)二(3,4-二甲苯基)鈦之合成>
使用4-溴-鄰二甲苯(1莫耳)代替上述(A-1)中使用之對溴甲苯,除此以外,與上述(A-1)同樣地進行合成,獲得雙(η(5)-環戊二烯基)二(3,4-二甲苯基)鈦。產率為83%。
所獲得之結晶為黃色針狀晶,對甲苯、環己烷之溶解性良好,且溶點為155℃,元素分析值:C為80.6,H為7.2,Ti為12.2。
<(A-4):雙(η(5)-1,3-二甲基環戊二烯基)二氯化鈦>
使用使Nippon Fine Chemical公司製造之試劑於二氯甲烷中再結晶而成者。
(B-1):三乙基鋁;直接使用己烷溶液(Tosoh Akzo公司製造)。
(B-2):第二丁基鋰;於惰性環境下將己烷溶液(關東化學製造之試劑)過濾分離,使用黃色透明之部分。
下述(C-1)~(C-4)使用市售之特級試劑。
(C-1):月桂烯(分子量136,相對於(C-1)1莫耳之不飽和基數為3莫耳)
(C-2):異戊二烯(分子量68,相對於(C-2)1莫耳之不飽和基數為2莫耳)
(C-3):辛烯(分子量112,相對於(C-3)1莫耳之不飽和基數為1莫耳)
(C-4):1,7-辛二烯(分子量110,相對於(C-4)1莫耳之不飽和基數為2莫耳)
(C-5):聚異戊二烯(藉由GPC測得之數量平均分子量3100,相對於(C-5)1莫耳之不飽和基數為46莫耳)
均使用市售之特級試劑。
(D-1):四氫呋喃
(D-2):乙酸乙酯
(D-3):N,N,N',N'-四甲基乙二胺
以下述表1所示之比率,以成為最終濃度為5質量%之環己烷溶液之方式添加(A)、(B)、(C)、(D)成分。
作為各成分之添加順序,於(A)成分、(C)成分、(D)成分之共存下,最後添加(B)成分。
於7L之高壓釜中添加環己烷4000g、苯乙烯單體150g、正丁基鋰1.10g及四氫呋喃25g,於攪拌下、於60℃下聚合3小時,繼而添加1,3-丁二烯單體700g,於60℃下聚合3小時。
最後添加苯乙烯單體150g,於60℃下聚合3小時。
以水使活性末端失活,於60℃下進行12小時真空乾燥。
所獲得之苯乙烯-丁二烯-苯乙烯嵌段共聚物為完全嵌段共聚物,且鍵結苯乙烯含量30質量%、丁二烯單元之1,2-乙烯基鍵含有率45mol%,以GPC(聚苯乙烯換算分子量)測得之重量平均分子量約為6萬。
再者,1,2-乙烯基鍵量係以NMR進行測定。
如下述之氫化聚合物之製造例即[製造例1~15]、[比較製造例1~5]所示,進行聚合物之氫化反應,利用下述NMR測定所獲得之氫化聚合物之氫化率。
對剛製備後(初期)使用實施例1~15、比較例1~5之氫化用觸媒組合物之情況,及製備後於30℃下保管30日後使用之情況兩者進行評價。
同時,氫化率較高者較佳,將99.5%以上設為◎,將99.0%以上且未達99.5%設為○,將97.0%以上且未達99.0%設為△,將未達97%設為×。
共軛二烯中之1,2-乙烯基鍵含量與不飽和基之氫化率係藉由核磁共振光譜解析(NMR)於下述條件下測定。
藉由於氫化反應後沈澱於大量甲醇中,而回收氫化聚合物,繼而進行丙酮萃取、真空乾燥,進行1H-NMR測定。
測定機器:JNM-LA400(JEOL製造)
溶劑:氘氯仿
測定樣品:將聚合物氫化前後之抽檢品
樣品濃度:50mg/mL
觀測頻率:400MHz
化學位移基準:TMS(四甲基矽烷)
脈衝延遲:2.904秒
掃描次數:64次
脈衝寬度:45°
測定溫度:26℃
於製備實施例1~15、比較例1~7之氫化用觸媒組合物後,於30℃下保管30日後,使用1升之分液漏斗(SPC29,柴田科學製造)使1升氫化用觸媒組合物流動,而對給料性進行評價。
無堵塞而連續地流動者為良好,設為○,將間斷地流動之情況設為△,將堵塞之情況設為×。
使用製備後於30℃溫度環境下保管30日之氫化用觸媒組合物,於與上述<氫化率>相同之條件下進行氫化反應。即,如下述之氫化聚合物之製造例即[製造例1~15]、[比較製造例1~5]所示,進行聚合物之氫化反應。其後,添加甲醇水,繼而添加作為穩定劑之3-(3,5-二第三丁基-4-羥基苯基)丙酸十八烷基酯相對於如上所述製造之氫化聚
合物100質量份為0.3質量份,使溶劑乾燥。以目視觀察於200℃下將所獲得之氫化聚合物加壓成型10分鐘時之變色。
未著色者為良好而設為○,將著色之情況設為×。
將如上所述製造之[聚合物]:苯乙烯-丁二烯-苯乙烯嵌段共聚物以分別成為80g之方式,以經純化乾燥之環己烷溶液之形式添加至經氫氣置換之1000mL之耐壓高壓釜中(溶液濃度10質量%)。
將如上所述製造之實施例1~15、比較例1~5之氫化用觸媒組合物以相對於上述聚合物Ti量成為150ppm之方式打入耐壓高壓釜中,以氫氣壓力5kgf/cm2
加壓。
於攪拌下,於100℃下進行20分鐘氫化反應。
使用實施例1~15、比較例1~5之氫化用觸媒組合物,分別將如上所述製造之氫化聚合物製成製造例1~15、比較製造例1~5之聚合物。
下述表1中分別表示製造例1~15、比較製造例1~5之氫化聚合物之氫化率、實施例1~15、比較例1~5之氫化用觸媒組合物之給料性、上述製造例1~15、製造比較例1~5之氫化聚合物之黃變抑制之評價。
將表1中所示之氫化用觸媒組合物之構成成分表示如下。
(A)成分
(A-1):雙(η(5)-環戊二烯基)二(對甲苯基)鈦
(A-2):雙(η(5)-環戊二烯基)二(苯基)鈦
(A-3):雙(η(5)-環戊二烯基)二(3,4-二甲苯基)鈦
(A-4):雙(η(5)-1,3-二甲基環戊二烯基)二氯化鈦
(B)成分
(B-1):三乙基鋁
(B-2):第二丁基鋰
(C)成分
(C-1):月桂烯
(C-2):異戊二烯
(C-3):辛烯
(C-4):1,7-辛二烯
(C-5):聚異戊二烯
(D)成分
(D-1):四氫呋喃
(D-2):乙酸乙酯
(D-3):N,N,N',N'-四甲基乙二胺
由上可知,包含(A)成分、(B)成分、(C)成分、(D)成分,且(C)成分與(A)成分之質量比(=(C)/(A))為0.1~4.0、(D)與(A)之質量比(=(D)/(A))為0.01~1.00之範圍的實施例1~15之氫化用觸媒組合物之氫化活性較高、給料性良好、儲存穩定性較高、且可製造無色性優異之氫化烯烴化合物。
本申請案係基於2012年9月21日向日本專利廳提出申請之日本專利申請案(日本專利特願2012-208283)者,其內容作為參照併入本文。
本發明之氫化用觸媒組合物係作為於用以製造用作聚丙烯或聚乙烯之改質劑之氫化聚合物化合物之氫化步驟中使用的氫化用觸媒組合物,而具有產業上之可利用性。
Claims (5)
- 一種氫化用觸媒組合物,其係包含下述(A)、(B)、(C)、(D)者,且(C)與(A)之質量比(=(C)/(A))為0.1~4.0,(D)與(A)之質量比(=(D)/(A))為0.01~1.00,(A):下述通式(1)所表示之二茂鈦化合物
- 如請求項1之烯烴化合物之氫化用觸媒組合物,其中上述(C)中之不飽和基量於該(C)每1mol中為2mol以上。
- 如請求項1或2之氫化用觸媒組合物,其中上述(B)為有機鋰化合物。
- 一種氫化方法,其係於如請求項1至3中任一項之氫化用觸媒組合物之存在下,使含有烯烴性不飽和雙鍵之化合物於惰性有機溶劑中與氫接觸。
- 如請求項4之氫化方法,其中上述含有烯烴性不飽和雙鍵之化合物為共軛二烯系聚合物、或共軛二烯與乙烯基芳香族烴之共聚物。
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US10016749B2 (en) | 2018-07-10 |
JPWO2014046017A1 (ja) | 2016-08-18 |
IN2015DN01779A (zh) | 2015-05-29 |
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WO2014046017A8 (ja) | 2015-03-12 |
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EP2898950A4 (en) | 2015-09-02 |
KR101684198B1 (ko) | 2016-12-07 |
JP6215214B2 (ja) | 2017-10-18 |
RU2608996C2 (ru) | 2017-01-30 |
EP2898950A1 (en) | 2015-07-29 |
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MY169989A (en) | 2019-06-19 |
EP2898950B1 (en) | 2017-11-08 |
US20150273459A1 (en) | 2015-10-01 |
CN104640629A (zh) | 2015-05-20 |
CN104640629B (zh) | 2017-05-24 |
SG11201501532YA (en) | 2015-05-28 |
TW201420623A (zh) | 2014-06-01 |
KR20150038473A (ko) | 2015-04-08 |
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