CN1159813A - 间同立构的前手性链烯烃聚合方法 - Google Patents
间同立构的前手性链烯烃聚合方法 Download PDFInfo
- Publication number
- CN1159813A CN1159813A CN95195467A CN95195467A CN1159813A CN 1159813 A CN1159813 A CN 1159813A CN 95195467 A CN95195467 A CN 95195467A CN 95195467 A CN95195467 A CN 95195467A CN 1159813 A CN1159813 A CN 1159813A
- Authority
- CN
- China
- Prior art keywords
- alkyl
- octahydrofluorenyl
- metal complexes
- boric acid
- catalyzer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 title description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- -1 phosphino- Chemical class 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 239000003426 co-catalyst Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 11
- 239000002585 base Substances 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000002879 Lewis base Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-UHFFFAOYSA-N 0.000 claims description 3
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 229920001576 syndiotactic polymer Polymers 0.000 abstract 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 31
- 150000002500 ions Chemical class 0.000 description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 17
- 239000004327 boric acid Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000003115 supporting electrolyte Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 7
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 150000001399 aluminium compounds Chemical class 0.000 description 4
- 229910000085 borane Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 150000001639 boron compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CMSUNVGIWAFNBG-UHFFFAOYSA-N 2,4-dimethylpenta-1,3-diene Chemical compound CC(C)=CC(C)=C CMSUNVGIWAFNBG-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OXUCOTSGWGNWGC-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2-] OXUCOTSGWGNWGC-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
- 229940094989 trimethylsilane Drugs 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
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 3-methylpenta-1,3-diene Chemical compound CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- GNYHCDALQLVPFH-UHFFFAOYSA-N C1(=C(C=CC=C1)OC1=C(C=CC=C1)C)C.B(O)(O)O Chemical compound C1(=C(C=CC=C1)OC1=C(C=CC=C1)C)C.B(O)(O)O GNYHCDALQLVPFH-UHFFFAOYSA-N 0.000 description 1
- MFFLHSOMUHHGKG-UHFFFAOYSA-N CC(C)NC(C)C.OB(O)O Chemical compound CC(C)NC(C)C.OB(O)O MFFLHSOMUHHGKG-UHFFFAOYSA-N 0.000 description 1
- BWOMHUALSIOVHY-UHFFFAOYSA-N CC(C=CC=C1)=C1SC1=C(C)C=CC=C1.OB(O)O Chemical compound CC(C=CC=C1)=C1SC1=C(C)C=CC=C1.OB(O)O BWOMHUALSIOVHY-UHFFFAOYSA-N 0.000 description 1
- UYCNEZKHTFHYGI-UHFFFAOYSA-N C[O-].C[O-].C[O-].CC=CC=C[Ti+3] Chemical compound C[O-].C[O-].C[O-].CC=CC=C[Ti+3] UYCNEZKHTFHYGI-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UMAPFJZTGMTFIR-UHFFFAOYSA-N [2,3,5,6-tetrafluoro-4-tri(propan-2-yl)silylphenoxy]boronic acid Chemical compound CC(C)[Si](C(C)C)(C(C)C)C1=C(F)C(F)=C(OB(O)O)C(F)=C1F UMAPFJZTGMTFIR-UHFFFAOYSA-N 0.000 description 1
- QQZWQOQLMGMKDC-UHFFFAOYSA-N [4-[tert-butyl(dimethyl)silyl]-2,3,5,6-tetrafluorophenoxy]boronic acid Chemical compound CC(C)(C)[Si](C)(C)C1=C(F)C(F)=C(OB(O)O)C(F)=C1F QQZWQOQLMGMKDC-UHFFFAOYSA-N 0.000 description 1
- YFIBHBUXBBYTES-UHFFFAOYSA-K [Cl-].[Cl-].O(C1=CC=CC=C1)[Ti+2] Chemical compound [Cl-].[Cl-].O(C1=CC=CC=C1)[Ti+2] YFIBHBUXBBYTES-UHFFFAOYSA-K 0.000 description 1
- MFWDFTZSKUUNLN-UHFFFAOYSA-N [O].FC=1C(=C(C(=C(C1)F)F)F)F Chemical compound [O].FC=1C(=C(C(=C(C1)F)F)F)F MFWDFTZSKUUNLN-UHFFFAOYSA-N 0.000 description 1
- ABXDUVOCXLVBNG-UHFFFAOYSA-M [Ti]OC1=CC=CC=C1 Chemical compound [Ti]OC1=CC=CC=C1 ABXDUVOCXLVBNG-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
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- 229910000941 alkaline earth metal alloy Inorganic materials 0.000 description 1
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- 229910052763 palladium Inorganic materials 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
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- 125000005353 silylalkyl group Chemical group 0.000 description 1
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
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- 239000000725 suspension Substances 0.000 description 1
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- 238000012360 testing method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Abstract
八氢芴基钛金属配合物或环状取代的八氢芴基钛金属配合物，其中金属为+2，+3或+4价氧化态，使用活性助催化剂或活化技术生产用于聚合前手性链烯烃形成高度间同立构的聚合物的催化剂。
Description
本发明涉及一种制备前手性链烯烃，尤其是乙烯基芳族单体聚合物的方法。所得的聚合物具有间同立体结构。更具体地说，本方法可以高效地制备该聚合物并使之具有所需要的低于500000的低分子量。
以前已知在本技术领域可以通过使用含有一个环戊二烯基或取代环戊二烯基基团的钛配合物和包括烷基铝氧烷、形成非配位离子的惰性化合物、路易斯酸及其混合物的一种活性助催化剂来制备高度间同立构的乙烯基芳族聚合物和其它前手性链烯烃。该现有技术方法公开于US-A-5,045,517，5,066,741或5,206,197和WO92/05823中。
通常，借助Ziegler-Natta(齐格勒纳塔)金属茂催化剂制备较低分子量的聚合物比制备较高分子量的聚合物更困难。以前所用的聚合方法是通过使用多种链转移剂干扰聚合过程而控制所得聚合物的分子量形成低分子量聚合物。在制备间同立构的乙烯基芳族单体聚合物时，已经证明通常用于脂族烯烃聚合的链转移剂对用于所需的反应设备来说是不起作用或是不合适的。在没有链转移剂的情况下，通常制得的间同立构链烯烃聚合物分子量大于500,000并常常是大于600,000。由于高温这种聚合物很难有效地加工而没有所不需要的降解。因此，在本技术领域需要一种有效、高度可生产性的方法来制备分子量减小的间同立构链烯烃聚合物，尤其是间同立构的乙烯基芳族聚合物。
本发明提供了一种制备高度立构规整和分子量低于500,000的前手性链烯烃单体的聚合物的方法，包括将单体与催化剂相互接触，催化剂含有：
1)至少一种对应于下式的金属配合物：
AMXpX’q其中，M是+2、+3或+4价表观氧化态的钛、锆或铪；
A是一个八氢芴基或是一个由1-9个烃基取代的八氢芴基，每个烃基具有的碳原子可达10个；
X是除环状、离域、π-结合配位体之外的阴离子配位体，具有高达40个原子；
X’在每种情况下为独立的中性路易斯碱配位化合物，具有高达20个原子；
p为1，2或3，并比M的表观氧化态少1；
q为0，1或2；和
2)活性助催化剂
1)和2)的摩尔比率为1∶10,000至100∶1，或者
与使用活化技术将1)转化成活性催化剂所形成的反应产物相互接触。
本方法在很宽范围的聚合条件下高效制得高度间同立构的聚合物。
特别是已经发现此方法适合用于制备高度间同立构的单亚乙烯基芳族聚合物。
在此所有提及的元素周期表指的是CRC Press，Inc.在1989年公布并拥有版权的元素周期表。另外，所提及的任何族应为使用IUPAC编族法在此元素周期表中所指的族。
在此所用的前手性链烯烃为C3-20的脂族或芳族化合物，其中含有乙烯基不饱和基团并含有不对称取代的碳原子，能够制备立构规整的聚合物。
在此所用的术语“间同立构”指的是由13C核磁共振光谱测得的含有的间同立构外消旋三单元组(triad)大于50％，优选大于75％的立构规整的聚合物。该聚合物可用于由压模法、注模法或其它合适的技术制备制品和物件，所得制品有很高的抗由于温度影响而产生的形变的能力。
X’基团优选一氧化碳；膦类，特别是三甲基膦、三乙基膦、三苯基膦和双(1，2-二甲基膦基)乙烷；P(OR)3，其中R如前面所定义的；醚，尤其是四氢呋喃；胺，尤其是吡啶、联吡啶、四甲基亚乙基二胺(TMEDA)和三乙胺；及共轭二烯烃，尤其是末端双取代1，3-丁二烯。本发明所用的配位化合物优选对应于下式的配合物：其中：R在每种情况下为独立的氢或C1-10烷基；
X为阴离子配位体，选自卤化物、烃基、烃氧基、二(烃基)酰胺基、二(烃基)膦基、烃硫基、甲硅烷基卤代烃基、卤代甲硅烷基、二(烃基)胺基取代的烃基、烃氧基取代的烃基和二(羟基)膦基取代的烃基，所说的X基含有高达20个非氢原子。更优选X基为氯化物，R’、OR、或NR’2，其中R’为C1-10烃基。X的例子包括氯、甲基、甲氧基、苯氧基、异丙氧基、二甲基酰胺基、烯丙基、甲基取代的烯丙基、戊二烯基、3-甲基戊二烯基和2，4-二甲基戊二烯基。
用于本发明的配位化合物最优选对应于下式的八氢芴基配合物：
其中X是氯化物、C1-4烷氧化物或酚盐。
上述金属配合物的例子包括：八氢芴基三氯化钛(IV)、八氢芴基三甲氧基钛(IV)、八氢芴基三苯氧基钛(IV)、八氢芴基二氯苯氧基钛(IV)、八氢芴基二甲氧基钛(III)、八氢芴基甲基(2-二甲基胺基苄基)钛(III)、八氢芴基烯丙基(S-顺式-二苯基丁二烯)钛(II)和八氢芴基2，4-二甲基戊二烯基钛(II)。这里所定义的其它各种取代配合物对本领域技术人员来说是显而易见的。
非常优选的金属配合物是八氢芴基三氯化钛(IV)和八氢芴基三甲氧基钛(IV)。
总之，可以通过将八氢芴基三甲基硅烷(或其环状取代衍生物)与式MXp+1X’q的化合物结合起来制备本发明的配合物。X配位体还可以由格里雅(Grignard)反应取代。任选使用还原剂以得到低氧化态的配合物。在-100至300℃，优选-78至100℃，更优选0-50℃温度下在合适的非干扰溶剂中进行反应。这里术语“还原剂”指的是在还原条件下，使得金属M由高氧化态还原到低氧化态的金属或化合物。合适的金属还原剂的例子是：碱金属、碱土金属、铝和锌、碱金属和碱土金属合金诸如钠/汞合金和钠/钾合金。合适的还原剂化合物的例子是萘基钠、石墨化钾(pottassium graphite)、烷基钾、链二烯基锂或链二烯基钾；和格里雅试剂。最优选的还原剂为碱金属或碱土金属，尤其是锂和镁金属。
用于形成本发明配合物的合适的反应介质包括：脂肪烃和芳香烃、醚和环醚、特别是支链烃诸如异丁烷、丁烷、戊烷、己烷、庚烷、辛烷及其混合物；环烃和脂环烃诸如环己烷、环庚烷、甲基环己烷、甲基环庚烷及其混合物；芳族和烃基取代的芳族化合物诸如苯、甲苯和二甲苯、C1-4二烷基醚、(聚)烷二醇的C1-4二烷基醚衍生物和四氢呋喃。上述物质的混合物也是适合的。
通过与活性助催化剂结合或使用活化技术使配合物变为催化活性。在此所用的合适的活性助催化剂包括聚合或低聚铝氧烷，特别是甲基铝氧烷、三异丁基铝改性的甲基铝氧烷、或异丁基铝氧烷；中性路易斯酸，诸如C1-30烃基取代的13族化合物，特别是三(烃基)铝或三(烃基)硼化合物和其卤代(包括全卤代)衍生物，每个烃基或卤代烃基上具有1-10个碳原子，更优选全氟代三(芳基)硼化合物，最优选三(五氟苯基)硼烷；非聚合的、相容的、非配位的、形成离子的化合物(包括在氧化条件下使用这些化合物)，特别是使用相容的、非配位的阴离子的铵盐、鏻盐、氧鎓盐、碳鎓盐、甲硅烷鎓盐、锍盐，或相容的、非配位的阴离子的二茂铁鎓盐；整体电解(bulk electrolysis)(以下将作更详细的解释)及上述活性助催化剂和活化技术结合使用。对于不同金属配合物来说，上述活性助催化剂和活化技术在下列参考文献中已有介绍：EP-A-277,003，US-A-5,153,157，US-A-5,064,802，EP-A-468,651，EP-A-520,732和WO93/03250。
特别理想的活性助催化剂为中性路易斯酸，特别是每个烷基上具有1-4个碳原子的三烷基铝化合物和每个烃基上有1-20个碳的卤代三(烃基)硼化合物、尤其是三(五氟苯基)硼烷，另外还有该类路易斯酸混合物与聚合的或低聚的铝氧烷结合，及一种路易斯酸，特别是三(五氟苯基)硼烷与聚合的或低聚的铝氧烷结合。
本发明的一个实施方案中用作助催化剂的合适的形成离子的化合物含有阳离子(它是一种能够供给质子的布朗斯台德酸)和可相容的非配位的阴离子A-。在此所用的术语“非配位的”指的是一种阴离子或物质，它不能配位到含有前体配合物和其催化剂衍生物的第4族金属上，或者仅与该配合物很弱地配位因此保持有充分的不稳定以被中性路易斯碱所代替。具体地说非配位阴离子指的是阴离子在用在阳离子金属中作为电荷平衡阴离子时，不会将阴离子取代基或其片段转移到该阳离子上从而形成中性配合物。“相容性阴离子”是指阴离子在初始形成的配合物降解时不会降解到中性并对所需的后面的聚合或配合物的其它用途是非惰性的。
那些含有一个包括带电荷的金属或非金属芯的配位化合物的阴离子是优选的。该阴离子能够平衡当两种组分结合时形成的活性催化剂(金属阳离子)的电荷。该阴离子还应该有足够的不稳定性以被烯属、二烯属或炔属不饱和化合物或其它中性路易斯碱如醚或腈所代替。适合的金属包括但并不局限于铝、金和铂。合适的非金属包括但并不局限于硼、磷和硅。含有由含一个金属或非金属原子的配位化合物组成的阴离子的化合物已众所周知并且许多都可以由市场得到，尤其是那些阴离子部分含有一个硼原子的化合物。
优选下面通式所表示的助催化剂：
(L*-H)+ d(Ad-)其中，L*为中性路易斯碱；
(L*-H)+为布朗斯台德酸；
Ad-为带有d-电荷的非配位的相容性阴离子，而d为1-3的整数。
更优选Ad-相应于通式〔M’k+Qn〕d-，其中，
k为1-3的整数；
n’为2-6的整数；
n--k＝d；
M’是选自元素周期表第13族的一种元素；
而Q在每种情况下独立地选自氢化物、二烷基酰胺基、卤化物、烃基、烃基氧化物、卤代烃基、卤代烃氧基和卤代甲硅烷烃基(包括全卤代烃基、全卤代烃氧基和全卤代甲硅烷基烃基)，所述的Q具有的碳原于可达20个，但须在不止一种情况下Q为卤化物。合适的烃基氧化物Q的例子已在US-A-5,296,433中公开。
在更优选的实施方案中，d为1，就是说，反离子具有一个负电荷A-。含硼的反离子，这在制备本发明的催化剂中非常有用，可由下面通式表示：(BQ4)-其中：B是3价的硼；
Q是烃基、烃氧基、氟代烃基、氟代烃氧基或氟代甲硅烷烃基，其非氢原子可达20个，但须在不止一种情况下Q为烃基。
最优选Q在每种情况下都为氟代芳基，特别是五氟苯基。
可在制备本发明的改进催化剂中作为活性助催化剂的硼化合物例举但非限制性的例子为三取代铵盐诸如：
1)四苯基硼酸三甲铵，
2)四苯基硼酸三乙铵，
3)四苯基硼酸三丙铵，
4)四苯基硼酸三正丁铵，
5)四苯基硼酸三叔丁铵，
6)四苯基硼酸N，N-二甲基苯胺，
7)四苯基硼酸N，N-二乙基苯胺，
8)四苯基硼酸N，N-二甲基-2，4，6-三甲基苯胺，
9)四(五氟苯基)硼酸三甲铵，
10)四(五氟苯基)硼酸三乙基铵，
11)四(五氟苯基)硼酸三丙铵，
12)四(五氟苯基)硼酸三正丁铵，
13)四(五氟苯基)硼酸三仲丁基铵，
14)四(五氟苯基)硼酸N，N-二甲基苯胺，
15)正丁基三(五氟苯基)硼酸N，N-二甲基苯胺，
16)苄基三(五氟苯基)硼酸N，N-二甲基苯胺，
17)四(4-(叔丁基二甲基甲硅烷基)-2，3，5，6-四氟苯基)硼酸N，N-二甲基苯胺，
18)四(4-(三异丙基甲硅烷基)-2，3，5，6-四氟苯基)硼酸N，N-二甲基苯胺，
19)五氟苯氧基三(五氟苯基)硼酸N，N-二甲基苯胺，
20)四(五氟苯基)硼酸N，N-二乙基苯胺，
21)四(五氟苯基)硼酸N，N-二甲基-2，4，6-三甲基苯胺，
22)四(2，3，4，6-四氟苯基)硼酸三甲铵，
23)四(2，3，4，6-四氟苯基)硼酸三乙铵，
24)四(2，3，4，6-四氟苯基)硼酸三丙铵，
25)四(2，3，4，6-四氟苯基)硼酸三正丁铵，
26)四(2，3，4，6-四氟苯基)硼酸二甲基叔丁铵，
27)四(2，3，4，6-四氟苯基)硼酸N，N-二甲基苯胺，
28)四(2，3，4，6-四氟苯基)硼酸N，N-二乙基苯胺，及
29)四(2，3，4，6-四氟苯基)硼酸N，N-二甲基-2，4，6-三甲基苯胺；
二烷基铵盐诸如：
四(五氟苯基)硼酸二异丙铵，和
四(五氟苯基)硼酸二环己铵；
三取代鏻盐诸如：
四(五氟苯基)硼酸三苯鏻，
四(五氟苯基)硼酸三邻甲苯鏻，和
四(五氟苯基)硼酸三(2，6-二甲基苯基)鏻；
二取代氧鎓盐诸如：
四(五氟苯基)硼酸二苯基氧鎓，
四(五氟苯基)硼酸二邻甲苯基氧鎓，和
四(五氟苯基)硼酸二(2，6-二甲基苯基)氧鎓；
二取代锍盐诸如：
四(五氟苯基)硼酸二苯基锍，
四(五氟苯基)硼酸二邻甲苯基锍，和
四(五氟苯基)硼酸双(2，6-二甲基苯基)锍。
(L*-H)+阳离子优选N，N-二甲基苯胺离子和三丁基铵离子。
另一种适合的形成离子的活性助催化剂包含一种阳离子氧化剂和一种非配位的相容性阴离子的盐，它由下式表示：
(Oxe+)d(Ad-)e其中：Oxe+为带e+电荷的阳离子氧化剂；
e为1-3的整数，
Ad-和d如前面所定义。
阳离子氧化剂的例子包括：二茂铁鎓、烃基取代的二茂铁鎓、Ag+或Pb2+。Ad-优选的实施例为前面对于含活性助催化剂，尤其是四(五氟苯基)硼酸盐的布朗斯台德酸所定义的那些阴离子。
另一种适合的形成离子的活性助催化剂包括一种碳鎓离子和一种非配位的相容性的阴离子的盐化合物，可由下式代表：+A-其中：+为C1-20碳鎓离子，
A-如前所定义。优选的碳鎓离子为三苯甲游基阳离子，三苯基甲基鎓。
另一适合的形成离子的活性助催化剂包含一种甲硅烷基翁离子和一种非配位的相容性阴离子的盐化合物，由下式表示：
R3Si(X’)q +A-其中：R为C1-10烃基，X’，q和A-如前定义。
甲硅烷基鎓盐活性助催化剂优选四(五氟苯基)硼酸三甲基甲硅烷鎓、四(五氟苯基)硼酸三乙基甲硅烷鎓及其醚取代的加合物。甲硅烷鎓盐以前已公开于J.Chem.Soc.Chem.Comm，1933，383、384和Lambert，J.B.，et al.，Organometallics，1994，13，2430-2443。
醇、硫醇、硅烷醇和肟与三(五氟苯基)硼烷的某些配合物也是有效的催化剂活化剂并可用于本发明。该类助催化剂公开于US-A-5,296,433中。
整体电解技术涉及到在含非配位的惰性阴离子支持电解质存在时在电解条件下金属配合物的电化学氧化。在此技术中，使用了用于电解的溶剂、支持电解质和电解势，从而在反应过程中基本上不形成使得金属配合物催化活性失效的电解副产物。特别是，适合的溶剂为这样的材料：在电解条件下(通常温度为0-100℃)能够溶解支持电解质的惰性液体。“惰性液体”是那些在用于电解的反应条件下不还原或不氧化的液体。从所需的电解反应的观点出发，选择不受用于所需电解的电解势影响的溶剂和支持电解质通常是可能的。优选的溶剂包括二氟代苯(所有的异构体)、二甲氧基乙烷(DME)及其混合物。
可以在含有一个阳极和一个阴极(也分别指工作电极和反电极)的标准电解池中进行电解。用于构成电解池的合适的材料为玻璃、塑料、陶瓷和玻璃涂覆金属。电极由惰性导电材料制成，这意味着导电材料不受反应混合物或反应条件的影响。铂或钯为优选的惰性导电材料。通常离子渗透膜如细玻璃料将电解池分成分离室、工作电极室和反电极室。工作电极浸入含待活化金属配合物、溶剂、支持电解质和用于减缓电解或稳定所得配合物的其它任何所需材料的反应介质中。反电极浸入到溶剂和支持电解质的混合物中。通过使用参比电极如银电极浸入电解室电解质中清扫电解室由理论计算或试验可测定所需电压。也可测定本底电解室电流，该电流是在没有所需电解时产生的。当电流由所需水平降至本底水平时电解完成。这样，初始的金属配合物的完全转换可以很容易地测得。
适合的支持电解质为含阳离子和相容的非配位阴离子A-的盐。优选的支持电解质为对应于式G+A-的盐，其中：
G+为不与起始和最终的配合物反应的盐，
A-如前所规定。
阳离子G+的例子包括四烃基取代的铵或鏻阳离子，其非氢原子可达40个。优选的阳离子为四正丁基铵或四乙基铵阳离子。
在通过整体电解使本发明的配合物活化的过程中，支持电解质的阳离子通过反电极而A-偏移至工作电极变为所得氧化产物的阴离子。溶剂或支持电解质的阳离子在反电极还原，其摩尔量与工作电极上形成的氧化金属配合物的量相等。优选的支持电解质为四(五氟芳基)硼酸的四烃基铵盐，每个烃基或全氟代芳基上有1-10个碳，特别优选四(五氟苯基)硼酸四正丁基铵。
最近还发现的产生活性助催化剂的电化学技术为在非配位的相容性阴离子存在的条件下二硅烷化合物电解。
上述活化技术和形成离子的助催化剂还优选与以下物质结合使用：每个烃基上有1-4个碳的三烃基铝或三烃基硼烷化合物、低聚或聚合的铝氧烷化合物、或每个烃基上有1-4个碳的三烃基铝化合物和聚合或低聚铝氧烷的混合物。
所用的催化剂/助催化剂的摩尔比率优选范围是1∶10,000至100∶1，更优选1∶5000至10∶1，最优选1∶1000至1∶1。在本发明一个特别优选的实施方案中，助催化剂可以与每个烃基上有1-10个碳的三烃基铝化合物结合使用。活性助催化剂的混合物也可以使用。也可能利用这些铝化合物有利的能力来清除聚合混合物中的杂质诸如氧气、水和醛。优选的铝化合物包括在每个烷基上含有2-6个碳的三烷基铝化合物，特别是那些其中烷基为以下基团的：甲基、乙基、丙基、异丙基、正丁基、异丁基、戊基、新戊基、或异戊基。优选的铝氧烷化合物为甲基铝氧烷、改性甲基铝氧烷(即，与三异丁基铝反应改性的甲基铝氧烷)(MMAO)和异丁基铝氧烷。金属配合物与铝化合物的摩尔比率优选1∶10,000至100∶1，更优选1∶1000至10∶1，最优选1∶500至1∶1。
最优选的活性助催化剂包括烷基铝氧烷，特别是甲基铝氧烷、异丙基铝氧烷或异丙基铝改性的铝氧烷与每个烷基上有1-4个碳的三烷基铝化合物，特别是三丁基铝结合的混合物。三烷基铝化合物与烷基铝氧烷的优选比率为0.1∶1至10∶1，更优选0.25∶1至1∶1。
本方法可单独或结合用于聚合具有3-20个碳原子的烯属不饱和单体。优选单体包括单亚乙烯基芳香单体，4-乙烯基环己烯、乙烯基环己烷和C3-10脂肪α-链烯(特别是丙烯、异丁烯、1-丁烯、1-已烯、3-甲基-1-戊烯、4-甲基-1-戊烯和1-辛烯)及其混合物。最优选的单体为苯乙烯和C1-4烷基取代的苯乙烯。
通常，可在众所周知的Ziegler-Natta或Kaminsky-Sinn型聚合反应的现有技术条件下完成聚合，就是说，在0至250℃温度下，优选30至85℃和大气压至10,000大气压的压力下。如果需要，悬浮液、溶液、浆液、气相、固态粉末聚合或其它工艺条件都可以使用。可以使用载体，特别是硅石、矾土或聚合物(特别是聚(四氟乙烯)或聚烯烃)。理想地是当催化剂用于气相聚合工艺时进行使用。载体使用量优选催化剂(以金属为基计)与载体的重量比率为1∶100,000至1∶10，更优选1∶50,000至1∶20，最优选1∶10,000至1∶30。
在大多数聚合反应中催化剂与所用的聚合化合物的摩尔比率为10-12∶1至10-1∶1，更优选10-9∶1至10-5∶1。
用于聚合的适合的溶剂为惰性液体。例子包括：直链和支链烃诸如：异丁烷、丁烷、戊烷、己烷、庚烷、辛烷及其混合物；环状或脂环烃诸如：环己烷、环庚烷、甲基环己烷、甲基环辛烷及其混合物；全氟代烃诸如：全氟代C4-10烷烃和芳族及烷基取代的芳族化合物诸如苯、甲苯、二甲苯、乙苯。适合的溶剂还包括可以充当单体或共聚单体的液体链烯烃，包括乙烯、丙烯、丁二烯、环戊烯、1-己烯、1-己烷、4-乙烯基环己烷、乙烯基环己烷、3-甲基-1-戊烯、4-甲基-1-戊烯、1，4-己二烯、1-辛烯、1-癸烯、苯乙烯、二乙烯基苯、烯丙基苯和乙烯基甲苯(包括所有的单独异构体或异构体混合物)。上述化合物的混合物也适合。
催化剂还可以与至少一种另外的均相或非均相聚合催化剂结合使用，在串连或并联的独立的反应器中制备具有所需性能的聚合物共混物。WO94/00500中公开了该方法的一个例子。
理想的是通过让单体和催化剂组合物接触进行聚合，从而制得分子量为200,000至450,000的聚合物。测定该分子量在此所用的技术为在135℃用1，3，5-三氟苯进行的溶液粘度测定法，利用无规立构聚苯乙烯标准用凝胶色谱渗透法进行校准。得数是反映重均分子量Mw的无单位值。本方法的效用通常足以得到在聚合1小时后转化百分数至少为30％重量，优选至少50％重量，最优选至少60％重量。
熟练的技术工人可以理解在此所公开的本发明可以在任何没有特别公开的组分不存在的情况下实施。下列实施例将对本发明作进一步说明而不限制本发明。除非另有说明，所有的份数和百分数都以重量为基来表示。
实施例1：
八氢芴基三氯化钛
八氢芴基三甲基硅烷(由甲硅烷基氯化物和八氢芴锂在四氢呋喃(THF)中结合而制备)(0.74g，3.0mmol，在10ml THF中)在25℃左右逐滴加入到20ml含有0.57g(3.0mmol)四氯化钛的甲苯中。搅拌溶液1小时。此后减压除去溶剂。将10ml己烷加入到残余物中并将溶液冷却至20℃3小时。得到暗红色的沉淀。用己烷冲洗固体得到兰色粉末，将其过滤除去。浓缩液体，通过冷却得到桔红色粉末，由1HNMR分光计鉴定为八氢芴基三氯化钛。产率为0.263g，27％。
聚合：
苯乙烯单体、甲基铝氧烷、三异丁基铝和金属聚合物(八氢芴基三氯化钛(OTT)或对比金属配合物)以233,000∶200∶100∶1的摩尔比率装入小玻璃瓶中。将玻璃瓶密封分别放入加热到50℃和70℃的水浴中。1小时后移去玻璃瓶，测定转化百分率和分子量。由脱去挥发份后的重量损失测定转化百分率。由溶液粘度测定法测定聚合物分子量。对比金属配合物为五甲基环戊二烯基三氯化钛(PTT)，(1，3-二甲基四氢茚基)三氯化钛(LTT)和四甲基环戊二烯基三甲氧基钛(TTT)。结果见表1。
表1配合物 50℃ 50℃ 70℃ 70℃
转化率(％) Mw 转化率(％) Mw
OTT 64.5 410,000 53.9 260,000
PTT 61 805,000 59 650,000
ITT 46.3 445,000 33 230,000
TTT 59 500,000 48 350,000
参阅表1的结果，可以看出使用八氢芴基三氯化钛金属配合物产生了较高效率(50℃和70℃下1小时后转化率大于50％)而同时聚合物分子量小于500,000，优选小于450,000。
Claims (8)
1.一种制备具有高度立构规整和分子量小于500,000的前手性链烯烃单体的聚合物的方法，包括将单体与催化剂接触，催化剂含有：
1)至少一种相应于下式的金属配合物：
AMXpX’q其中：M为+2+，+3或+4价表观氧化态的钛、锆或铪；
A是八氢芴基或是由1-9个羟基取代的八氢芴基，每个烃基具有的碳原子可达10个；
X为除了环状、离域、π-结合配位体之外的阴离子配位体，具有高达40个原子；
X’独立地在每种情况下为中性路易斯碱配位化合物，具有高达20个原子；
p为1，2或3，并比M的表观氧化态少1，
q为0，1或2；和
2)活性助催化剂
1)和2)的摩尔比率为1∶10,000至100∶1，或者与使用活化技术将1)转化成活性催化剂所形成的反应产物相接触。
2.根据权利要求1的方法，其中金属配合物相应于下式：
其中：R在每种情况下独立地为氢或C1-10烷基；和
X为阴离子配位体，选自：卤化物、烃基、烃氧基、二(烃基)酰胺基、二(烃基)膦基、烃硫基、甲硅烷基卤代烃基、卤代甲硅烷基、二(烃基)胺基取代的烃基、烃氧基取代的烃基和二(烃基)膦基取代的烃基，所说的X基含有高达20个非氢原子。
3.根据权利要求1的方法，其中金属配合物相应于下式：
其中X为氯化物，C1-4烷氧化物或酚盐。
4.根据权利要求1的方法，其中金属配合物为八氢芴基三氯化钛或八氢芴基三甲氧基钛。
5.根据权利要求1的方法，其中单体选自C3-10脂族α-链烯烃、单亚乙烯基芳族单体、4-乙烯基环己烯、乙烯基环己烷及其混合物。
6.根据权利要求5的方法，其中单体为单亚乙烯基芳族单体，聚合物具有至少50％的外消旋三单元组的闸同立构。
7.根据权利要求6的方法，其中催化剂被载体化。
8.根据权利要求1的方法，其中催化剂与单体的摩尔比率为10-12∶1至10-1∶1。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/316,748 US5536797A (en) | 1994-10-03 | 1994-10-03 | Syndiotactic prochiral olefin polymerization process |
| US08/316,748 | 1994-10-03 |
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| CN1159813A true CN1159813A (zh) | 1997-09-17 |
| CN1082057C CN1082057C (zh) | 2002-04-03 |
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| Country | Link |
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| US (1) | US5536797A (zh) |
| EP (1) | EP0784639B1 (zh) |
| JP (1) | JPH10506932A (zh) |
| KR (1) | KR100357358B1 (zh) |
| CN (1) | CN1082057C (zh) |
| BR (1) | BR9509493A (zh) |
| CA (1) | CA2200956A1 (zh) |
| DE (1) | DE69507626T2 (zh) |
| MX (1) | MX9702453A (zh) |
| TW (1) | TW371305B (zh) |
| WO (1) | WO1996010592A1 (zh) |
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| CN100337751C (zh) * | 2001-06-29 | 2007-09-19 | 纳幕尔杜邦公司 | 应用锆催化剂羟基化β－二羰基化合物的方法 |
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| US5670680A (en) * | 1996-04-26 | 1997-09-23 | The Dow Chemical Company | Method for producing octahydrofluorenyl metal complexes |
| US6100352A (en) * | 1996-05-29 | 2000-08-08 | Idemitsu Kosan Co., Ltd. | Process for producing polymer |
| EP1084163B1 (en) | 1998-04-07 | 2005-06-01 | Dow Global Technologies Inc. | Improved syndiotactic vinylidene aromatic polymerization process |
| US6232414B1 (en) * | 1999-03-31 | 2001-05-15 | Phillips Petroleum Company | Process to make a monovinylaromatic polymer and said monovinylaromatic polymer |
| US6232415B1 (en) * | 1999-03-31 | 2001-05-15 | Phillips Petroleum Company | Process to produce a monovinylaromatic/ monoolefin polymer and said monovinylaromatic/monoolefin polymer |
| WO2004108775A1 (en) * | 2003-06-05 | 2004-12-16 | Dow Global Technologies Inc. | Activated multinuclear transition metal catalyst compositions |
| US20110054122A1 (en) * | 2009-08-31 | 2011-03-03 | Jerzy Klosin | Catalyst and process for polymerizing an olefin and polyolefin prepared thereby |
| US11542350B2 (en) | 2018-03-30 | 2023-01-03 | Dow Global Technologies Llc | Binuclear olefin polymerization activators |
| WO2019191440A1 (en) | 2018-03-30 | 2019-10-03 | Dow Global Technologies Llc | Highly soluble bis-borate as binuclear co-catalysts for olefin polymerizations |
| CN111971311B (zh) | 2018-03-30 | 2024-01-23 | 陶氏环球技术有限责任公司 | 高度可溶的烷基取代的碳鎓硼酸盐作为烯烃聚合的助催化剂 |
| WO2019191068A1 (en) * | 2018-03-30 | 2019-10-03 | Dow Global Technologies Llc | Olefin polymerization activators |
| WO2019191098A1 (en) | 2018-03-30 | 2019-10-03 | Dow Global Technologies Llc | Olefin polymerization activators |
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| US5153157A (en) * | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| US5241025A (en) * | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| PL276385A1 (en) * | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
| US5045517A (en) * | 1987-06-17 | 1991-09-03 | The Dow Chemical Company | Catalyst and process for preparation of syndiotactic polystyrene |
| US5026798A (en) * | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
| US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
| US5066741A (en) * | 1990-03-22 | 1991-11-19 | The Dow Chemical Company | Process for preparation of syndiotactic vinyl aromatic polymers |
| JP2545006B2 (ja) * | 1990-07-03 | 1996-10-16 | ザ ダウ ケミカル カンパニー | 付加重合触媒 |
| US5252677A (en) * | 1990-11-20 | 1993-10-12 | Mitsubishi Petrochemical Company Limited | Functionalized olefin polymers |
| US5206197A (en) * | 1991-03-04 | 1993-04-27 | The Dow Chemical Company | Catalyst composition for preparation of syndiotactic vinyl aromatic polymers |
| US5721185A (en) * | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
| US5886117A (en) * | 1991-08-05 | 1999-03-23 | The Dow Chemical Company | Process using borane derived catalysts for preparation of syndiotactic vinyl aromatic polymers |
| US5374696A (en) * | 1992-03-26 | 1994-12-20 | The Dow Chemical Company | Addition polymerization process using stabilized reduced metal catalysts |
| US5296433A (en) * | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
| US5350723A (en) * | 1992-05-15 | 1994-09-27 | The Dow Chemical Company | Process for preparation of monocyclopentadienyl metal complex compounds and method of use |
| WO1994000500A1 (en) * | 1992-06-26 | 1994-01-06 | Exxon Chemical Patents Inc. | Solution phase polymerization process utilizing metallocene catalyst with production of olefin polymers |
| DE69307472T2 (de) * | 1992-11-10 | 1997-05-15 | Mitsubishi Chem Corp | Verfahren zur Herstellung von Alpha-Olefinpolymeren |
| EP0659774B1 (en) * | 1993-12-27 | 1999-03-03 | Idemitsu Kosan Company Limited | Process for producing styrenic polymer |
| DE69505293T2 (de) * | 1994-03-31 | 1999-03-11 | Idemitsu Kosan Co. Ltd., Tokio/Tokyo | Verfahren zur Herstellung eines Styrolpolymers |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100337751C (zh) * | 2001-06-29 | 2007-09-19 | 纳幕尔杜邦公司 | 应用锆催化剂羟基化β－二羰基化合物的方法 |
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| Publication number | Publication date |
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| DE69507626D1 (de) | 1999-03-11 |
| MX9702453A (es) | 1997-06-28 |
| US5536797A (en) | 1996-07-16 |
| KR100357358B1 (ko) | 2003-01-24 |
| CA2200956A1 (en) | 1996-04-11 |
| BR9509493A (pt) | 1997-10-14 |
| DE69507626T2 (de) | 1999-09-30 |
| CN1082057C (zh) | 2002-04-03 |
| EP0784639A1 (en) | 1997-07-23 |
| TW371305B (en) | 1999-10-01 |
| EP0784639B1 (en) | 1999-01-27 |
| KR970706319A (ko) | 1997-11-03 |
| WO1996010592A1 (en) | 1996-04-11 |
| JPH10506932A (ja) | 1998-07-07 |
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