CN1460688A - 用于烯烃聚合的催化剂组分 - Google Patents
用于烯烃聚合的催化剂组分 Download PDFInfo
- Publication number
- CN1460688A CN1460688A CN03128652A CN03128652A CN1460688A CN 1460688 A CN1460688 A CN 1460688A CN 03128652 A CN03128652 A CN 03128652A CN 03128652 A CN03128652 A CN 03128652A CN 1460688 A CN1460688 A CN 1460688A
- Authority
- CN
- China
- Prior art keywords
- catalyst component
- polyolefin catalyst
- catalyst
- alkyl
- polymerization
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 229920000098 polyolefin Polymers 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012968 metallocene catalyst Substances 0.000 claims description 9
- 229910052726 zirconium Chemical group 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims 1
- 230000003213 activating effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 48
- 239000000243 solution Substances 0.000 description 31
- 239000000543 intermediate Substances 0.000 description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- 239000012190 activator Substances 0.000 description 22
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- -1 aluminum halides Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000017858 demethylation Effects 0.000 description 3
- 238000010520 demethylation reaction Methods 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DWPLEOPKBWNPQV-UHFFFAOYSA-N 1-(2-methoxyphenyl)ethanone Chemical compound COC1=CC=CC=C1C(C)=O DWPLEOPKBWNPQV-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IJGRUMAEYZWBQI-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 IJGRUMAEYZWBQI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 1
- AKUQXFHQPACGKR-UHFFFAOYSA-N 2-bromo-6-tert-butyl-4-methylphenol Chemical compound CC1=CC(Br)=C(O)C(C(C)(C)C)=C1 AKUQXFHQPACGKR-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- HPDNGBIRSIWOST-UHFFFAOYSA-N 2-pyridin-2-ylphenol Chemical compound OC1=CC=CC=C1C1=CC=CC=N1 HPDNGBIRSIWOST-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- NGDGQUOKSIMCEE-UHFFFAOYSA-N B(O)(O)O.CC1=CC(=CC(=C1)N)C Chemical compound B(O)(O)O.CC1=CC(=CC(=C1)N)C NGDGQUOKSIMCEE-UHFFFAOYSA-N 0.000 description 1
- WKQXWKDCPCRGGV-UHFFFAOYSA-N BrC1=C(C(=C(C(=C1[B])Br)Br)Br)Br Chemical compound BrC1=C(C(=C(C(=C1[B])Br)Br)Br)Br WKQXWKDCPCRGGV-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241001443715 Fusarium oxysporum f. sp. conglutinans Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- MGYZYLGWXRQUPL-UHFFFAOYSA-L [Cl-].[Cl-].C=1C=CC=CC=1C[Zr+2]CC1=CC=CC=C1 Chemical compound [Cl-].[Cl-].C=1C=CC=CC=1C[Zr+2]CC1=CC=CC=C1 MGYZYLGWXRQUPL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
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Abstract
本发明公开了式I所示的化合物,其中,R1-R11各自独立地选自包含1-20个碳原子的烃基、取代的烃基、杂烃基、和取代的杂烃基,且R1-R11中的两个或多个可以连接起来形成环;R1-R11还选自氢、卤素、公认的给体和受体基团;E是第16族元素(包括氧);M是选自第3-10族元素(包括钛和锆)和镧系元素的金属;m是金属的氧化态;X是键合到M上的单价原子或基团;Y是配位键合到M上的单或双齿分子,n是0或最高达5的整数。这些催化剂,当与适合的活化剂结合时,对于烯烃的聚合具有活性。
Description
技术领域
本发明涉及一种由含吡啶的金属化合物和适合的活化剂组成的非茂金属催化剂体系,其在烯烃聚合过程中具有高活性。
背景技术
聚烯烃主要是使用通用的齐格勒催化剂体系制备的,所述催化剂体系通常由过渡金属卤化物和一种或多种有机铝卤化物组成。虽然这些催化剂并不昂贵,但它们却存在许多问题,包括活性低、残余催化剂会染色且不稳定、分子量分布宽、以及引入共单体的效率低。近些年来,已经开始用茂金属基催化剂替代齐格勒催化剂。茂金属催化剂,它是带有一个或多个环戊二烯基[Cp]环配体的过渡金属(尤其是钛和锆)化合物,通常与作为活化剂的铝氧烷一起使用以给出非常高的活性。茂金属聚烯烃催化剂能对齐格勒催化剂中碰到的许多问题提供解决方法;且在本领域中是众所周知的。
烯烃聚合用茂金属催化剂的商业化在非茂金属均相催化剂的设计中已经产生了很大的兴趣。新一代的催化剂可以显示出优良的活性并为已知的聚烯烃提供更简易的合成路线,同时还导致产生了在茂金属催化剂能力之外的方法和产品。另外,非环戊二烯基配体和化合物的取代同系物可能相对易于合成,因此非茂金属催化剂可能会更经济。
多齿阴离子的氧和氮基基团作为非茂金属聚烯烃催化剂已经引起了大家的注意。就二齿配体而言,已经有人报道了吡啶氧基和喹啉氧基配体(如美国专利5637660、5852146、6020493;Bei等,Organometallics,1997,17,3282;Tshukahara等,Organometallics,1997,17,3303)。
一系列含有胺-双(酚盐)基团(酚盐是芳羟基基团)的四齿阴离子配体最近已经由Kol,Goldschmidt和其同事应用于聚烯烃催化剂(美国专利6333423,Tshuva等,Chem.Commun.,2000,379和Chem.Commun.,2001,2120)。但是,这些公开物说明,第四配位部分或额外的给体臂对于高活性催化剂来说是很必要的,并且没有给体臂的化合物显示出差的催化活性。另外,这些公开物主要集中于1-己烯的聚合,没有给出较低级烯烃聚合的信息。Shao等(Organometallics,2000,19,509)描述了作为聚烯烃催化剂的螯合胺-双(醇盐)(醇盐是脂族羟基基团)的锆配合物,但观察到的活性非常低。
含有至少一个酚盐基团的聚烯烃催化剂在本领域中是众所周知的(美国专利4452914,5079205)。美国专利5840646、6034190、EP0606125和WO87/02370公开了用于烯烃聚合的二齿双(酚盐)钛和锆催化剂。
日本未审专利6-192330描述了双(酚盐)加上吡啶-双(醇盐)钛和锆催化剂。作为第4族金属聚烯烃催化剂配体的吡啶-双(醇盐)基团的另外的例子业已公开(JP9-012582和Mack等,J.Chem.Soc.Dalton.Trans.,1998,917),但观察到的乙烯聚合活性仅仅是中等的。
因此,在本领域中需要新的烯烃聚合催化剂,尤其是包含吡啶-酚盐类多齿配体的催化剂。在本领域中也需要新的包含不对称配体的聚烯烃催化剂,因为这可以导致1-烯烃(α-烯烃)的立体选择性聚合并得到具有与众不同的形态和性能的聚烯烃。
发明内容
本发明涉及一种聚烯烃催化剂体系,其包含带有三齿含吡啶配体的第3-10族或镧系金属(包括钛和锆)化合物和适合的活化剂。
附图简述
图1示出吡啶-双(酚盐)锆配合物1的X-射线晶体结构。
图2示出吡啶-双(酚盐)钛配合物4的X-射线晶体结构。
本发明的具体实施方式
本发明涉及聚烯烃催化剂体系,其包含带有三齿含吡啶配体的第3-10族或镧系金属(包括钛和锆)化合物和适合的活化剂。
本发明也涉及如下式I所示的非茂金属催化剂:其中,R1-R11各自独立地选自氢、卤素、公认的给体和受体基团、包含1-20个碳原子的烃基、取代的烃基、杂烃基和取代的杂烃基,且R1-R11中的两个或多个可以连接起来形成环;E是第16族(也称第VI B族)元素(包括氧);M是选自第3-10族元素(包括钛和锆)和镧系元素的金属;m是金属的氧化态;X是键合到M上的单价原子或基团;Y是配位键合到M上的单或双齿分子,n是0或最高达5的整数。当与适合的活化剂结合(combined)时,这些催化剂在用于烯烃的聚合时是具有活性的。
在式I聚烯烃催化剂的一个实施方案中,基团R1-R5和R7-R11独立地选择并具有以下特征:R1=R11、R2=R10、R3=R9、R4=R8和R5=R7。这意味着三齿配体是对称的。在另一个实施方案中,基团R1-R5和R7-R11独立地选择并具有以下一种特征或其组合:R1≠R11(即,R1不等同于R11)、R2≠R10、R3≠R9、R4≠R8和R5≠R7。这意味着三齿配体是不对称的并可以实现立体选择性聚合。
在式I聚烯烃催化剂的一个示例性实施方案中,M选自钛和锆,E是氧,这样三齿吡啶-双(酚盐)配体与M配位。
在式I聚烯烃催化剂的一个优选实施方案中,X选自卤化物基团(包括氯化物)和烷基(包括苄基),Y不存在或选自中性O-给体、P-给体和N-给体分子。可以与M形成配位键的O-给体分子的例子包括醚(如四氢呋喃、二乙醚)和酮(如苯乙酮、二苯甲酮)。可以与M形成配位键的P-给体分子的例子包括PRaRbRc,其中Ra-c各自独立地选自氢、卤素、公认的给体和受体基团、包含1-20个碳原子的烃基、取代的烃基、杂烃基、和取代的杂烃基(如三甲基膦、三乙基膦、二甲基苯基膦)。
目标配体的制备可以通过文献中所述方法的改性而实现。例如,对称的吡啶-2,6-二(苯酚)底物可通过来自于氧-保护取代苯酚的格氏试剂与2,6-二溴吡啶反应制得。使用熔融氯化吡啶鎓盐来完成脱保护。用于合成不对称吡啶-2,6-二(苯酚)底物的方法采用的是Silva等人的方法(Tetrahedron,1997,53,11645),其描述了2,6-二(2’-羟苯基)吡啶的合成,包括两分子的2’-甲氧基苯乙酮分子的加成。在本发明中,当使用两种不同的取代2’-甲氧基苯乙酮,随后脱甲基化,那么所得吡啶-2,6-二(苯酚)底物是不对称的。
含酸性质子的取代吡啶-2,6-二(苯酚)底物的金属化可以通过与碱性金属试剂,如四苄基锆(IV)和四氯化钛(IV)反应,分别消去甲苯和氯化氢而实现。或者,可以用如正丁基锂的试剂对配体去质子化,然后用金属卤化物,如四氯化锆处理。所得金属配合物包含一个以三齿子午线向方式螯合的吡啶-2,6-二(酚盐)配体。中性O-(如四氢呋喃或二乙醚)、P-(如三烷基膦或三芳基膦)、或N-给体溶剂或底物被加入到反应混合物中以有利于配合物的分离,在某些情况下,以其溶剂化/加合形式。如1H NMR波谱和某些情况下X-射线结晶学所测定的,两个残余的卤化物配体为顺式构型,并且这对于将这些配合物作为聚烯烃催化剂使用是很重要的。
本发明涉及一种催化剂体系,其包含金属催化剂和活化剂。一般情况下,活化剂将配合物转化为阳离子活性种。适合的活化剂在本领域中是公知的。其例子包括三甲基铝(TMA)、三乙基铝(TEA)、三异丁基铝(TIBA)、三正辛基铝、二氯化甲基铝、二氯化乙基铝、氯化二甲基铝、氯化二乙基铝、铝氧烷等。铝氧烷在本领域中通常公知为低聚化合物,其可以通过将水控制加成到烷基铝化合物,如三甲基铝中而制备。铝氧烷化合物的例子包括甲基铝氧烷(MAO)、改性甲基铝氧烷(MMAO)、乙基铝氧烷、和二异丁基铝氧烷。在本发明中,优选烷基铝氧烷,如甲基铝氧烷(MAO)。
烷基铝氧烷与三烷基铝化合物的混合物是特别优选的,如MAO与TMA或TIBA的混合。在本发明的上下文中,应当注意,在说明书中使用的术语“烷基铝氧烷”包括可商购的烷基铝氧烷,其可以包含一部分,通常约10wt%,但任选最高达50wt%的相应的三烷基铝;例如,商品MAO通常包含约10wt%的三甲基铝(TMA),而商品MMAO既包含TMA,又包含TIBA。本发明引用的烷基铝氧烷的量包括这种三烷基铝混杂物,因此,本发明引用的三烷基铝化合物的量,当其存在时被认为包括式AlR3的化合物,包括引入到烷基铝氧烷中的任意的AlR3化合物。
适合的活化剂也包括含有非亲核阴离子的酸盐。这些化合物通常由连接到硼或铝上的庞大的配体组成。其例子包括四(五氟苯基)硼酸锂、四(五氟苯基)硼酸二甲基苯基铵、四(五氟苯基)硼酸三苯甲基酯等。适合的活化剂还包括三烷基或三芳基硼化合物,如三(五氟苯基)硼、三(五溴苯基)硼等。其他适合的活化剂描述于,例如美国专利5064802和5599761中。
在本发明催化剂的制备中,活化剂的使用量要根据试验来决定。发现,使用量为每分子金属化合物0.1-20000原子、优选1-2000原子铝或硼,特别是当使用铝氧烷活化剂时。
在一个优选的实施方案中,一种或多种式I的聚烯烃催化剂与一种或多种上述活化剂或其混合物结合以形成对烯烃聚合过程来说具有活性的催化剂体系。
所述催化剂和催化剂体系对于烯烃聚合(包括均聚和共聚)是特别有价值的。适合的烯烃包括一种或多种乙烯、丙烯、丁烯、戊烯、己烯、辛烯、苯乙烯、1,3-丁二烯、降冰片烯等或其组合。优选的烯烃是乙烯、丙烯及其与1-烯烃,如1-丁烯、1-己烯和1-辛烯的混合物。在一个实施方案中,制备了乙烯均聚物。
本发明的催化剂体系也可以包括一种或多种其他过渡金属化合物,如通用的齐格勒催化剂、茂金属催化剂、受限的几何催化剂、或热活化的负载氧化铬(如Phillips型)催化剂。
所述催化剂和催化剂体系在有或没有无机固体或有机聚合物载体的存在下使用。适合的载体包括二氧化硅、氧化铝、氧化镁、二氧化钛、粘土、沸石、聚合物载体,如聚乙烯、聚丙烯、聚苯乙烯、官能化的聚苯乙烯等。载体可以经热或化学预处理以提高催化剂生产量或产品性能。催化剂和/或活化剂可以以任何希望的方式沉积于载体上。例如,可以将催化剂溶于溶剂中,与载体混合并汽提。或者,可以使用初始润湿技术。此外,可以简单地将催化剂与载体分别引入到反应器中。
催化剂可以用于各种公知的烯烃聚合方法中,包括气相、高压液相、浆液、本体、溶液或悬浮相技术及其组合。液相方法包括以下步骤:在适合的聚合溶剂中令烯烃单体与催化剂体系接触,在所述催化剂体系存在下在足以产生聚烯烃的温度和压力下,令所述单体反应一段时间。使用的压力通常为约10psi-约15000psi。聚合温度为约-100℃-约300℃,更优选约-50℃-约200℃,最优选约0℃-约150℃。
本发明的聚合方法以高产率得到聚合物,尤其是聚乙烯。这意味着在聚合过程中消耗极少量的催化剂。这也意味着在聚合过程之后,聚合物中的催化剂或残余物的量极少,这样在聚合物回收过程中就可以不需要催化剂分离步骤。
在一个实施方案中,本发明的乙烯聚合过程的活性可以大于5kg聚合物每mmol催化剂每小时每大气压乙烯,这相当于催化剂转换频率(TOF)大于1.8×105每小时每大气压乙烯。这样的高活性和TOF值需非常稀的催化剂溶液以防止出现传质受限速率。对于聚合运行来说,在一定时间间隔之后,可以观察到反应器的温度升高,因此,观察到的活性将由于所述传质受限速率而降低。但是,在这种放热条件下,本发明的聚合方法寿命长,并仍然以高产率得到聚合物。
不论什么时候,一旦形成,本发明的单个催化剂体系组分以及催化剂体系均要进行保护以免受到氧和水分的影响。因此,反应在无氧和无水气氛中进行,其中催化剂体系在无氧和无水气氛中单独回收,因此优选,反应在惰性干燥气体,如氦气或氮气的存在下进行。
以下实施例仅仅阐明本发明。本领域技术人员将认识到的许多变化均在本发明的精神中并属于所述权利要求的范围。
实施例
所有的实验均在氮气气氛中,使用标准Schlenk技术或在Braun干燥箱内进行。1H和13C NMR谱是在Bruker Avance600、500DRX、400或300FT-NMR波谱仪(ppm)上测定。质谱(EI)是在Finnigan MAT95质谱仪上获得。聚合物的熔点通过差示扫描量热计在Perkin Elmer DSC7上测定。催化剂活性以克每毫摩尔催化剂每小时每大气压计。甲基铝氧烷(MAO,10wt%的甲苯溶液)购自Aldrich(Schlenk,Braun,Bruker,Finnigan,Perkin Elmer和Aldrich均为商标)。
中间体1
根据通用的甲基化方法制备中间体1(如参见Org.Synth.Coll.Vol.4,836(1963))。在一个装有回流冷凝器和氯化钙干燥管的250ml圆底烧瓶中,于80ml丙酮中放入2-溴-4-甲基-6-叔丁基苯酚(按Nakayama等,Organometallics 2000,19,2498的方法合成,6.3g,26mmol)、无水碳酸钾(3.6g,26mmol)和碘甲烷(2.5ml,40mmol)。使混合物在60-70℃下回流20小时。在蒸馏除去丙酮后,用稀硫酸将残余液体酸化,然后用二氯甲烷(3×30ml)萃取。用水洗涤混合的有机萃取物并用硫酸镁干燥。蒸发溶剂,得到黄色油状物,使用正己烷∶乙酸乙酯(50∶1)作为洗脱剂,通过硅胶快速色谱纯化,得到浅黄色固体。收率:6.1g,91%。
1H NMR(300MHz,CDCl3):1.37(s,9,tBu),2.25(s,3,Me),3.89(s,3,OMe),7.04(s,1,Ar),7.23(s,1,Ar).正EI-MS(m/z):258[M+].1.2中间体2的合成
中间体2
根据以下文献方法的改进方法制备中间体2:Holligan等,J.Chem.Soc.Dalton Trans.,1992,3345。通过在四氢呋喃(THF,40ml)中将中间体1(4.82g,18.7mmol)和镁屑(0.90g,37.0mmol)回流2小时制备所需的格氏试剂。在冷却到室温条件下,将所得混合物在N2下过滤,并于0℃下滴加到2,6-二溴吡啶(2.02g,8.53mmol)与[Ni(dppe)Cl2](dppe=Ph2PCH2CH2PPh2,0.30g,0.57mmol)在干燥THF(20ml)中形成的混合物中,使混合物升温到室温,然后在回流下搅拌12小时。然后通过加入氯化铵水溶液猝灭反应,用HCl酸化,并在减压下除去挥发性物质,用二氯甲烷CH2Cl2(3×20ml)洗涤酸性水溶液,用氢氧化钾水溶液中和,并用CH2Cl2(3×20ml)萃取。通过硫酸镁干燥合并的有机萃取液,除去溶剂得到红色油状物。使用正己烷∶乙酸乙酯(9∶1)作为洗脱剂,通过硅胶快速色谱纯化,得到桔黄色固体。收率:2.8g,77%。
1H NMR(300MHz,CDCl3):1.43(s,18,tBu),2.36(s,6,Me),3.37(s,6,OMe),7.15(s,2,Ar),7.42(s,2,Ar),7.68-7.76(m,3,py).正EI-MS(m/z):431[M+].1.3中间体3的合成
中间体3
根据Dietrich-Buchecker等(Tetrahedron,1990,46,503)的方法,于N2气氛,210℃下,在熔融的氯化吡啶鎓盐(12.0g,104mmol)中将中间体2(3.0g,6.96mmol)脱甲基化得到中间体3,浅黄色固体,可以在正己烷中重结晶。收率:1.6g,57%。
1H NMR(300MHz,CDCl3):1.45(s,18,tBu),2.35(s,6,Me),7.18(s,2,Ar),7.30(s,2,Ar),7.62(d,2,J=8.0Hz,py-H3,5),7.96(t,1,J=8.0Hz,py-H4),10.52(brs,2,OH).正EI-MS(m/z):403[M+].1.4配合物1的合成
配合物1
在-78℃下将正丁基锂(0.70ml,2.5M)的己烷溶液加入到中间体3(0.345g,0.86mmol)的甲苯(25ml)中。使黄色溶液在室温下搅拌1小时,然后在-78℃下缓慢加入甲苯(15ml)和四氢呋喃(THF,8ml)中的四氯化锆(IV)(0.200g,0.86mmol)。所得黄色溶液在-78℃搅拌1小时,然后在室温下搅拌12小时。将混合物过滤、浓缩得到浅黄色固体,通过甲苯重结晶,得到大的黄色晶体。收率:0.39g,66%。测定配合物1的X-射线晶体结构(图1)。1H NMR(500MHz, C6D6):0.76(br,4,thf),1.79(s,18,tBu),2.22(s,6,Me),3.46(br,4,thf),6.81(s,2,Ar-H6),7.01-7.04(t,1,J=7.6Hz,py-H4),7.09-7.11(d,2,J=7.6Hz,py-H3,5),7.34(s,2,Ar-H4).正EI-MS(m/z):563(100%)[M+-thf].
配合物2
采用配合物1的合成方法,使用二乙醚代替甲苯和四氢呋喃作为反应溶剂。得到浅黄色固体,收率55%。
1H NMR(300MHz,C6D6):0.93(br,6,Et2O),1.78(s,18,tBu),2.20(s,6,Me),3.28-3.35(br q,4,Et2O),6.78(s,2,Ar-H6),7.09-7.18(m,3,py-H3-5),7.33(s,2,Ar-H4).
配合物3
在-78℃下,将中间体3(0.230g,0.57mmol)的二乙醚(15ml)溶液慢慢地加入到四苄基锆(IV)(0.260g,0.57mmol)的二乙醚(15ml)溶液中,所得混合物在-78℃搅拌30分钟,之后在室温下搅拌10小时,得到亮黄色浊溶液。将此溶液在-78℃下过滤、浓缩和贮存12小时,得到亮黄色晶体固体。收率:0.24g,62%。
1H NMR(600MHz,C6D6):1.74(s,18,tBu),2.27(s,6,Me),2.67(s,4,CH2),6.58-6.61(t,2,J=7.3Hz,Ph-H4),6.75-6.77(m,6,Ph-H3 and Ar-H6),6.79-6.81(t,1,J=7.8Hz,py-H4),6.91-6.93(d,2,J=7.8Hz,py-H3,5),7.00-7.01(d,4,J=7.3Hz,Ph-H2),7.35(s,2,Ar-H4).
实施例4配合物4的合成
配合物4
在-78℃下,将中间体3(0.420g,1.04mmol)的二乙醚(15ml)和四氢呋喃(5ml)溶液慢慢地加入到二乙醚(10ml)和四氢呋喃(10ml)中的四氯-双(四氢呋喃)钛(IV)(0.348g,1.04mmol)。所得混合物在-78℃搅拌10分钟,在室温下搅拌1小时。得到深红色溶液并沉淀出深红色微晶固体,收集并真空干燥。收率:0.51g,83%。测定配合物4的X-射线晶体结构(图2)
1H NMR(400MHz,C6D6):0.87(br,4,thf),1.88(s,18,tBu),2.23(s,6,Me),3.41(br,4,thf),6.93(s,2,Ar-H6),7.03-7.07(t,1,J=7.9Hz,py-H4),7.19-7.21(d,2,J=7.9Hz,py-H3,5),7.34(s,2,Ar-H4).正EI-MS(m/z):519(100%)[M+-thf].
实施例55.1中间体4的合成
中间体4
通过以下文献方法的改进制备中间体4:Silva等,Tetrahedron 1997,53,11654。将3,5-二叔丁基-2-甲氧基苯乙酮(3.12g,12mmol)和叔丁醇钾(2.71g,24mmol)的四氢呋喃(THF,15ml)溶液在室温下搅拌2小时得到黄色悬浮液。然后加入1-N,N-二甲基氨基-3-(2’-甲氧基萘基)-3-氧代-1-丙烯(通过Silva等在Tetrahedron 1997,53,11654的改进从1-甲氧基-2-萘乙酮制备;3.05g,12mmol)的THF(20ml)溶液,并将混合物在室温下搅拌12小时,得到深红色溶液。向混合物中加入乙酸铵(9.18g,119mmol)的乙酸(60ml)溶液。通过蒸馏2小时除去THF,残余物经真空干燥。加入二氯甲烷(30ml)得到红色溶液,用饱和的碳酸氢钠溶液中和,然后用CH2Cl2(3×20ml)萃取。用水和盐水洗涤合并的有机萃取液,经硫酸钠干燥,除去溶剂,得到红色油状物。使用正己烷∶乙酸乙酯(20∶1)作为洗脱剂,通过硅胶快速色谱纯化,得到浅黄色固体。收率:1.9g,68%。
1H NMR(300MHz,CDCl3):1.37(s,9,tBu),1.45(s,9,tBu),3.40(s,3,OMe),3.77(s,3,OMe),7.40(s,1,Ar),7.52-7.56(m,2,Nap),7.63(s,1,Ar),7.73-7.89(m,4,py and Nap),8.03-8.12(m,2,py和Nap),8.25-8.28(d,1,J=8.4Hz,Nap).5.2中间体5的合成
中间体5
根据Dietrich-Buchecker等(Tetrahedron 1990,46,503)所述的方法,于N2气氛,220℃下,在熔融的氯化吡啶鎓盐(10.0g,86.5mol)中将中间体4(1.91g,4.21mol)脱甲基化得到中间体5,浅黄色固体,可以在正己烷中重结晶。收率:1.12g,63%。
1H NMR(400MHz,C6D6):1.37(s,9,tBu),1.65(s,9,tBu),7.04-7.09,7.27-7.32,7.42-7.48,7.63-7.66(m,10,Ar),8.72-8.75(d,1,J=8.4Hz,Ar),9.50(brs,1,OH),12.78(brs,1,OH).正EI-MS(m/z):425[M+].5.3配合物5的合成
配合物5
采用合成配合物4的合成方法,使用中间体5代替中间体3。向深红色反应混合物中加入正己烷得到深红色微晶固体沉淀,收集并真空干燥。收率:69%。
1H NMR(500MHz,C6D6):0.78(br,4,thf),1.33(s,9,5-tBu),1.88(s,9,3-tBu),3.37(br,4,thf),7.07-7.11(t,1,J=7.9Hz,py-H4),7.24-7.25(d,1,J=7.5Hz,py-H3),7.27-7.34(m,4,Nap),7.47-7.49(d,1,J=7.8Hz,py-H5),7 52(s,1,Ar-H6),7.59-7.60(d,1,J=7.2Hz,Nap),7.73(s,1,Ar-H4),9.08-9.10(d,1,J=8.0Hz,Nap).正EI-MS(m/z):541(100%)[M+-thf].聚合试验
使用下面的方法进行以下描述的聚合试验。在大气压下,在甲苯中,在100ml含有磁力搅拌棒的玻璃反应器中进行乙烯聚合。将甲苯(40ml)引入到含有催化剂的反应器中并搅拌。该溶液淹没在所需聚合温度的液体浴中30分钟并用乙烯吹扫15分钟。通过加入甲基铝氧烷(MAO)的甲苯溶液引发聚合,将反应器保持在1大气压(atm)乙烯下,时间为聚合的持续时间。在上述时间后,加入HCl-酸化的甲醇(40ml)以终止聚合,停止乙烯气进料。通过过滤收集所得固体聚合物,用酸化甲醇洗涤并真空干燥至恒重。实施例6
使用配合物1(3mg,4.72μmol)作为催化剂,与MAO(4.7ml,7.08mmol,10wt%的甲苯溶液,1500当量)活化剂一起,在20℃下进行乙烯聚合20分钟。分离出的聚合物收率为5.42g,相当于活性为3448g/mmol h atm,聚合物的熔点为126.7℃。
实施例7
使用配合物1(3mg,4.72μmol)作为催化剂,与MAO(3.1ml,4.72mmol,10wt%的甲苯溶液,1000当量)活化剂一起,在20℃下进行乙烯聚合6分钟。分离出的聚合物收率为3.32g,相当于活性为7029g/mmol h atm,聚合物的熔点为127.0℃。
实施例8
使用配合物1(2mg,3.15μmol)作为催化剂,与MAO(4.2ml,6.29mmol,10wt%的甲苯溶液,2000当量)活化剂一起,在20℃下进行乙烯聚合5分钟。分离出的聚合物收率为2.07g,相当于活性为7880g/mmol h atm,聚合物的熔点为125.4℃。
实施例9
使用配合物1(3mg,4.72μmol)作为催化剂,与MAO(3.1ml,4.72mmol,10wt%的甲苯溶液,1000当量)活化剂一起,在1℃下进行乙烯聚合2分钟。分离出的聚合物收率为0.23g,相当于活性为1447g/mmol h atm,聚合物的熔点为134.0℃。
实施例10
使用配合物1(3mg,4.72μmol)作为催化剂,与MAO(3.1ml,4.72mmol,10wt%的甲苯溶液,1000当量)活化剂一起,在65℃下进行乙烯聚合2分钟。分离出的聚合物收率为0.31g,相当于活性为1987g/mmol h atm,聚合物的熔点为111.0℃。
实施例11配合物6的合成
配合物6
在-78℃下将中间体3(0.200g,0.50mmol)的甲苯(20ml)溶液慢慢加入到二苄基二氯化锆[Zr(CH2Ph)2Cl2(Et2O)(二噁烷)0.5](0.230g,0.50mmol)和过量的三乙基膦(PEt3)的20ml甲苯溶液中。所得混合物在-78℃搅拌10分钟,在室温下搅拌5小时,得到包含浅黄色沉淀的黄色溶液。收集黄色固体,使用二氯甲烷和己烷的混合物进行重结晶,得到浅黄色晶体,真空干燥。收率:0.24g,71%。
1H NMR(500MHz,CD2Cl2):1.21(dt,9,J=19.9,7.7Hz,PCH2CH3),1.55(s,18,tBu),2.18(br,6,PCH2CH3),2.33(s,6,Me),7.09(s,2),7.22(s,2),7.73(d,2,J=7.9Hz,py-H3,5),7.97(t,1,J=7.9Hz,py-H4).31P NMR(162MHz,CD2Cl2):20.36.正EI-MS(m/z):563[M+-PEt3].
实施例12
使用配合物6(8mg,12.2μmol)作为催化剂,与MAO(4.0ml,6.1mmol,10wt%的甲苯溶液,500当量)活化剂一起,在1℃下进行乙烯聚合10分钟。分离出的聚合物收率为2.76g,相当于活性为1358g/mmol h atm,聚合物的熔点为132.7℃。
从以上一般性说明和具体实施方案显而易见,虽然已经阐明并描述了本发明的形式,但在不背离本发明范围和精神的情况下可以做出各种变化,因此,并不想由此来限定本发明。
已经引用了许多参考文献,其全文在此引入作为参考。
Claims (9)
2.根据权利要求1的聚烯烃催化剂组分,其中基团R1-R5和R7-R11独立地选择并具有以下特征:R1=R11、R2=R10、R3=R9、R4=R8和R5=R7。
3.根据权利要求1的聚烯烃催化剂组分,其中基团R1-R5和R7-R11独立地选择并具有以下一种特征或其组合:R1≠R11、R2≠R10、R3≠R9、R4≠R8和R5≠R7。
4.根据权利要求1的聚烯烃催化剂组分,其中M选自钛和锆。
5.根据权利要求1的聚烯烃催化剂组分,其中E是氧。
6.根据权利要求1的聚烯烃催化剂组分,其中X选自卤化物和烷基。
7.根据权利要求1的聚烯烃催化剂组分,其中Y选自中性O-给体分子。
8.根据权利要求1的聚烯烃催化剂组分,其中Y选自中性P-给体分子。
9.根据权利要求1的聚烯烃催化剂组分,其中Y不存在或选自中性N-给体分子。
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US5852146A (en) | 1996-06-27 | 1998-12-22 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US6020493A (en) | 1999-05-06 | 2000-02-01 | Equistar Chemicals, Lp | Single-site catalyst preparation |
US6333423B1 (en) | 1999-09-10 | 2001-12-25 | Ramot University Authority For Applied Research And Industrial Development Ltd. | Ultra-high activity non-metallocene pre-catalyst and method for catalytic polymerization of alpha-olefin monomers |
-
2003
- 2003-03-28 US US10/402,816 patent/US6825296B2/en not_active Expired - Lifetime
- 2003-03-29 CN CNB031286526A patent/CN1239526C/zh not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102597016A (zh) * | 2009-10-28 | 2012-07-18 | 埃克森美孚化学专利公司 | 催化剂化合物和它们的用途 |
CN102597015A (zh) * | 2009-10-28 | 2012-07-18 | 埃克森美孚化学专利公司 | 催化剂化合物和它们的用途 |
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CN1239526C (zh) | 2006-02-01 |
US20030191015A1 (en) | 2003-10-09 |
US6825296B2 (en) | 2004-11-30 |
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