TWI585095B - 新1環戊[B]茀基過渡金屬化合物,包含該化合物之催化劑組合物,以及使用該化合物製備乙烯同元聚合物或乙烯及α-烯烴之共聚物之方法 - Google Patents
新1環戊[B]茀基過渡金屬化合物,包含該化合物之催化劑組合物,以及使用該化合物製備乙烯同元聚合物或乙烯及α-烯烴之共聚物之方法 Download PDFInfo
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- TWI585095B TWI585095B TW101120458A TW101120458A TWI585095B TW I585095 B TWI585095 B TW I585095B TW 101120458 A TW101120458 A TW 101120458A TW 101120458 A TW101120458 A TW 101120458A TW I585095 B TWI585095 B TW I585095B
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- Prior art keywords
- methyl
- alkyl
- group
- aryl
- ethylene
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- -1 cyclopenta[b]fluorenyl transition metal compound Chemical class 0.000 title claims description 416
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 81
- 239000005977 Ethylene Substances 0.000 title claims description 81
- 239000000203 mixture Substances 0.000 title claims description 60
- 239000003054 catalyst Substances 0.000 title claims description 55
- 239000004711 α-olefin Substances 0.000 title claims description 34
- 229920001519 homopolymer Polymers 0.000 title claims description 21
- 229920001577 copolymer Polymers 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 88
- 125000003118 aryl group Chemical group 0.000 claims description 57
- 239000000126 substance Substances 0.000 claims description 38
- 150000003623 transition metal compounds Chemical class 0.000 claims description 26
- 229910052723 transition metal Inorganic materials 0.000 claims description 25
- 150000003624 transition metals Chemical class 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 16
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 83
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 52
- 238000003756 stirring Methods 0.000 description 30
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 28
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 21
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 239000012044 organic layer Substances 0.000 description 20
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000003039 volatile agent Substances 0.000 description 15
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 14
- 235000019341 magnesium sulphate Nutrition 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 10
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 10
- 229910003002 lithium salt Inorganic materials 0.000 description 10
- 159000000002 lithium salts Chemical class 0.000 description 10
- 125000001624 naphthyl group Chemical group 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- ZCBSOTLLNBJIEK-UHFFFAOYSA-N silane titanium Chemical compound [SiH4].[Ti] ZCBSOTLLNBJIEK-UHFFFAOYSA-N 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 125000000814 indol-3-yl group Chemical group [H]C1=C([H])C([H])=C2N([H])C([H])=C([*])C2=C1[H] 0.000 description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 8
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004305 biphenyl Chemical group 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 5
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical group NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 5
- 241000208340 Araliaceae Species 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 5
- 235000003140 Panax quinquefolius Nutrition 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 235000008434 ginseng Nutrition 0.000 description 5
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 5
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 5
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 5
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical group CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000011345 viscous material Substances 0.000 description 5
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 4
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 4
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 4
- 125000000593 indol-1-yl group Chemical group [H]C1=C([H])C([H])=C2N([*])C([H])=C([H])C2=C1[H] 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 125000004222 fluoren-1-yl group Chemical group [H]C1=C([H])C2=C(C([H])=C1[H])C([H])([H])C1=C(*)C([H])=C([H])C([H])=C21 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
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- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 1
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- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 125000005484 neopentoxy group Chemical group 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
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- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
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- 239000002574 poison Substances 0.000 description 1
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- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
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- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
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- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
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- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- UJGFGHBOZLCAQI-UHFFFAOYSA-N tris(phosphanyl) borate Chemical compound POB(OP)OP UJGFGHBOZLCAQI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Description
本發明係關於一種以環戊[b]茀基為基礎的新穎過渡金屬化合物、一種包含該化合物且對於製備乙烯同元聚合物或乙烯及α-烯烴之共聚物具有高催化活性的過渡金屬催化劑組合物、一種使用該化合物製備乙烯同元聚合物或乙烯及α-烯烴之共聚物的方法、以及由此製得的乙烯同元聚合物或乙烯及α-烯烴之共聚物。更特定言之,本發明係關於一種過渡金屬化合物,其具有一結構,其中一作為核心金屬之元素週期表中之第4族過渡金屬係與一具有剛性平面結構之環戊[b]茀基連結,即使其並非位於一雜環中,因此有利於獲得高效率及高分子量之乙烯系(ethylene-based)聚合物;其具有廣泛未定域化的豐富電子;且經由一經矽基取代的醯胺基,在其第9位置能容易誘導一有助於溶解度及性能改良的取代基;關於一種用於製備乙烯同元聚合物或乙烯與至少一α-烯烴之共聚物的過渡金屬催化劑組合物,其包含作為主要催化劑的過渡金屬化合物、以及作為共催化劑的鋁化合物、硼化合物或其混合物;關於一種使用該化合物製備乙烯同元聚合物或乙烯及α-烯烴之共聚物的方法;以及關於由此製得乙烯同元聚合物或乙烯及α-烯烴之共聚物。
於先前技術中,所謂齊格勒-納他催化劑(Ziegler-Natta catalyst)已被廣泛的使用於製備乙烯同元聚合物或乙烯及α-烯烴共聚物,其係由作為主要催化劑組分之鈦或釩化合物及作為共催化劑組分
之烷基鋁化合物所組成。雖然齊格勒-納他催化劑系統在乙烯聚合反應中展現高度活性,但該催化劑系統之缺點在於,由於不均勻的催化劑活化點分布造成所製得聚合物的分子量分布廣,尤其,在乙烯及α-烯烴共聚物中,其組成分布不均。
最近,已有發展所謂茂金屬催化劑系統,其係由元素週期表中第4族過渡金屬(諸如鈦、鋯及鉿)的茂金屬化合物與作為共催化劑之甲基鋁氧烷所組成。該茂金屬催化劑系統為一具有一單型態催化劑活化點的均質催化劑,因此可供製備與既有齊格勒-納他催化劑系統相較具更窄的分子量分布及更均質的組成分布的聚乙烯。舉例言之,歐洲專利早期公開第320,762及372,632號、日本專利早期公開第昭63-092621號、第平02-84405號及第平03-2347號報告了可透過以甲基鋁氧烷作為共催化劑,活化茂金屬(諸如Cp2TiCl2、Cp2ZrCl2、Cp2ZrMeCl、Cp2ZrMe2、乙烯(IndH4)2ZrCl2),以高活性聚合乙烯,以製備分子量分布(Mw/Mn)範圍為1.5至2.0的聚乙烯。然而,難以透過使用上述催化劑系統以獲得高分子量聚合物,此外,當溶液聚合反應於100℃或更高的溫度中進行時,聚合活性突然下降,且β-脫氫反應佔有優勢。因此,已知該系統不適用於製備平均分子量(Mw)為100,000或更高的高分子量聚合物。
同時,亦有報導所謂構形限制非茂金屬系催化劑(geo-restrictive non-metallocene based catalysts)(亦稱為單活化點催化劑),於其中過渡金屬係以環狀連結,用於在溶液聚合反應狀態下之乙烯同元聚合物反應或乙烯及α-烯烴共聚物反應中作為催化劑,以製
造具高催化活性之高分子量聚合物。歐洲專利第0416815及0420436號提供一實施例,其中胺基以環狀連結到一環戊二烯配位基上,且歐洲專利第0842939號顯示一催化劑的實施例,其中作為電子供體化合物之酚系配位基係以環狀連結到一環戊二烯配位基上。此構形限制催化劑因催化劑本身較低的立體阻礙效應,可顯著的改進與高碳α-烯烴(higher α-olefins)的反應性,但於商業應用上有許多困難。因此,考量經濟可行性,即,優良的高溫活性、與較高α-烯烴的優良反應性、與製備高分子量聚合物的能力,在所需商業化催化劑中獲得更加有競爭性的催化劑系統是重要的。
為克服先前技術的問題,本發明人進行了廣泛的研究,並發現一種過渡金屬化合物,其結構中作為中心金屬之具有元素週期表第4族過渡金屬與一具有剛性平面結構之環戊[b]茀基連結,即使其並非位於一雜環中;其具有廣泛未定域化的豐富電子;且經由一經矽基取代的醯胺基,在其第9位置能容易誘導一有助於溶解度及性能改良的取代基,該過渡金屬化合物係有利於在乙烯及烯烴聚合反應中獲得高效率與高分子量之聚合物,從而完成本發明。
本發明之一目的在於提供一種可作為製備乙烯同元聚合物或乙烯及α-烯烴共聚物之催化劑的過渡金屬化合物,及提供一種包含該化合物的催化劑組合物。
於商業觀點下,本發明之另一目的在於提供一種使用包含該過
渡金屬化合物的催化劑組合物來經濟地製備乙烯同元聚合物或乙烯及α-烯烴共聚物方法。
本發明之又一目在於提供乙烯系聚合物,其係選自由上述方法所製得之乙烯同元聚合物及乙烯與α-烯烴共聚物。
為實現以上目的之本發明一方面提供了一由以下化學式1所示之以環戊[b]茀基為基礎的新穎過渡金屬化合物。更特定言之,本發明係關於一種過渡金屬化合物,其具有一結構,其中一作為核心金屬之元素週期表中之第4族過渡金屬係與一具有剛性平面結構之環戊[b]茀基連結,即使其並非位於一雜環中,因此有利於獲得高效率及高分子量之乙烯系(ethylene-based)聚合物;其具有廣泛未定域化的豐富電子;且經由一經矽基取代的醯胺基,在其第9位置能容易誘導一有助於溶解度及性能改良的取代基。
於化學式1中,M為元素週期表中之第4族過渡金屬;n為整數1或2,當n為2時,各R1可為相同或不同;R1為氫、(C1-C50)烷基、鹵(C1-C50)烷基、(C3-C50)環烷基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)
烷基(C6-C30)芳基)(C1-C50)烷基、-NRaRb、-SiRcRdRe、或含至少一氮原子的五至七員N-雜環烷基;R2及R3各自獨立為氫、(C1-C50)烷基、(C1-C50)烷氧基、鹵(C1-C50)烷基、(C3-C50)環烷基、(C6-C30)芳基、(C6-C30)芳基氧基、(C1-C50)烷基(C6-C30)芳基氧基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基、-NRaRb或-SiRcRdRe;R4、R5、R10、R11以及R12各自獨立為(C1-C50)烷基、鹵(C1-C50)烷基、(C3-C50)環烷基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基、-NRaRb、或-siRcRdRe,且R11與R12可經由(C4-C7)伸烷基連結成一環;R6、R7、R8、及R9各自獨立為氫、(C1-C50)烷基、鹵(C1-C50)烷基、(C3-C50)環烷基、(C1-C50)烷氧基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基、(C6-C30)芳基氧基、(C1-C50)烷基(C6-C30)芳基氧基、N-咔唑基、-NRaRb、或-SiRcRdRe,或可經由(C4-C7)伸烷基連結至一相鄰取代基以形成一環,且該伸烷基之至少一個-CH2-可經由一選自-O-、-S-及-NR'-的雜原子所取代,且該伸烷基可進一步經(C1-C50)烷基取代;R1至R12之芳基可進一步經至少一選自以下群組之取代基取代:(C1-C50)烷基、鹵(C1-C50)烷基、(C1-C50)烷氧基、(C6-C30)芳基氧基、(C6-C30)芳基、(C1-C50)烷基(C6-C30)芳基、及(C6-C30)芳基(C1-C50)烷基;R'與Ra至Re各自獨立為(C1-C50)烷基、或(C6-C30)芳基;
以及X1與X2各獨立為鹵素、(C1-C5O)烷基、(C2-C50)烯基、(C3-C50)環烷基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基、(C1-C50)烷氧基、(C6-C30)芳基氧基、(C1-C50)烷基(C6-C30)芳基氧基、(C1-C50)烷氧基(C6-C30)芳基氧基、(C1-C50)亞烷基、或一除氫以外包含N、P、O、S、Si及鹵素且由60個或更少的原子所構成的陰離子或雙陰離子配位基,其中當X1與X2之一者為雙陰離子配位基時,另一者則忽略。
由以上化學式1所示之以環戊[b]茀基為基礎的新穎過渡金屬化合物的一實例包含一由以下化學式2或3所示的過渡金屬化合物:
於化學式2及3中,M、R2至R12、X1與X2具有與化學式1中相同的定義;R21及R22各自獨立為氫、(C1-C50)烷基、鹵(C1-C50)烷基、(C3-C50)環烷基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基、-NRaRb、-SiRcReRe、或含至少一氮原子之五至七員的N-雜環烷基,R1之芳基可進一步經至少一選自以下群組之取代基取代:鹵素、(C1-C50)烷基、鹵(C1-C50)烷基、(C1-C50)烷氧基、(C6-C30)芳基氧基、(C6-C30)芳基、(C1-C50)烷基(C6-C30)芳基、及(C6-C30)芳基(C1-C50)烷基,且Ra至Re各自獨立為(C1-C50)烷基或(C6-C30)芳基。
為實現本發明之目的,本發明另一方面提供一種過渡金屬催化劑組合物,包含該過渡金屬化合物以及一選自一鋁化合物、一硼化合物、或其混合物之共催化劑。
為實現本發明之目的,本發明另一方面提供一種利用該過渡金屬化合物或該過渡金屬催化劑組合物製備乙烯系聚合物的方法,該乙烯系聚合物係選自乙烯同元聚合物及乙烯及α-烯烴之共聚物;以及所製得的乙烯同元聚合物或乙烯及α-烯烴之共聚物
於下文中,將更詳細描述本發明。
元素週期表的第4族過渡金屬M,較佳地為鈦(Ti)、鋯(Zr)、或鉿(Hf)。
此處描述的名詞「烷基」包含直鏈型或支鏈型。
此處描述的名詞「芳基」為一有機自由基,其由芳香族碳氫化
合物脫除一個氫原子所得到,且可以包含一含有適當的4至7個環原子、且較佳為5或6個環原子的單環或稠環。其具體實例包含苯基、萘基、聯苯基、蒽基、茀基、菲基、聯三苯基(triphenyl)、芘基、苝基、[草(之上)+快]基(chrysenyl)、稠四苯基、丙二烯合茀基等,但並不限於此。
舉例言之,(C1-C50)烷基可為甲基、乙基、正丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、正十四基、正十六基、正十五基、正十八基、正二十基、或正二十二基;(C3-C50)環烷基可為例如環丙基、環丁基、環戊基、環己基、環庚基、環辛基、環癸基、或環十二基;(C6-C30)芳基或(C1-C50)烷基(C6-C30)芳基可為例如苯基、2-甲苯基、3-甲苯基、4-甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,4-二甲苯基、3,5-二甲苯基、2,3,4-三甲基苯基、2,3,5-三甲基苯基、2,3,6-三甲基苯基、2,4,6-三甲基苯基、3,4,5-三甲基苯基、2,3,4,5-四甲基苯基、2,3,4,6-四甲基苯基、2,3,5,6-四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二基苯基、正十四基苯基、聯苯基、茀基、三苯基、萘基、或蒽基(anthracenyl);(C6-C30)芳基(C1-C50)烷基或((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基可為例如苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲基苯基)甲
基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、或蒽基甲基;且(C1-C50)烷氧基可為例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、二級丁氧基、三級丁氧基、正戊基氧基、新戊基氧基、正己基氧基、正辛基氧基、正十二基氧基、正十五基氧基、或正二十基氧基。
較佳地,各R1係獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、苯基、萘基、聯苯基、2-異丙基苯基、3,5-二甲苯基、2,4,6-三甲基苯基、苄基、二甲胺基、或吡咯烷基(pyrrolidino);較佳地,R2與R3各自獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、苯基、萘基、聯苯基、2-異丙基苯基、3,5-二甲苯基、2,4,6-三甲基苯基、苄基、甲氧基、乙氧基、異丙氧基、苯氧基、4-三級丁基苯氧基、或萘氧基;較佳地,R4與R5各自獨立為甲基、乙基、正丙基、異丙基、正丁基、異丁基、2-甲基丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、正十四基、正十六基、正十五基、正十八基、正二十基、正二十二基、苯基、
2-甲苯基、3-甲苯基、4-甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,4-二甲苯基、3,5-二甲苯基、2,3,4-三甲基苯基、2,3,5-三甲基苯基、2,3,6-三甲基苯基、2,4,6-三甲基苯基、3,4,5-三甲基苯基、2,3,4,5-四甲基苯基、2,3,4,6-四甲基苯基、2,3,5,6-四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二基苯基、正十四基苯基、聯苯基、茀基、三苯基、萘基、蒽基、苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲基苯基)甲基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、蒽基甲基、4-甲氧基苯基、3,4-二甲氧基苯基、或4-(己基氧基)-3,5-二甲基苯基;較佳地,R6到R9各自獨立為氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、2-甲基丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、
正十五基、苯基、2-甲苯基、3-甲苯基、4-甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,4-二甲苯基、3,5-二甲苯基、2,3,4-三甲基苯基、2,3,5-三甲基苯基、2,3,6-三甲基苯基、2,4,6-三甲基苯基、3,4,5-三甲基苯基、2,3,4,5-四甲基苯基、2,3,4,6-四甲基苯基、2,3,5,6-四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二基苯基、正十四基苯基、聯苯基、茀基、2,7-二-三級丁基-9-對-甲苯基-9氫-茀-9-基(2,7-di-tert-butyl-9-p-tolyl-9H-fluoren-9-yl)、三苯基、萘基、蒽基、苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲基苯基)甲基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、蒽基甲基、4-甲氧基苯基、3,4-二甲氧基苯基、甲氧基、乙氧基、異丙氧基、
正丁氧基、正己氧基、2-甲基丁基、苯氧基、4-三級丁基苯氧基、萘氧基、三甲基矽基、三苯基矽基、二甲基胺基、二苯基胺基、或9氫-咔唑-9基(9H-carbazol-9-yl)、或可經由、或連結至一相鄰取代基以形成一環,其中L1及L2各自獨立為-O-、-S-或-NR'-(各R'係獨立為(C1-C50)烷基或(C6-C30)芳基),R31至R34各自獨立為與R4與R5具有相同定義,且更佳為氫、甲基、或正十四基;較佳地,R11及R12各自獨立為甲基、乙基、正丙基、異丙基、正丁基、異丁基、2-甲基丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、正十五基、苯基、2-甲苯基、3-甲苯基、4-甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,4-二甲苯基、3,5-二甲苯基、2,3,4-三甲基苯基、2,3,5-三甲基苯基、2,3,6-三甲基苯基、2,4,6-三甲基苯基、3,4,5-三甲基苯基、2,3,4,5-四甲基苯基、2,3,4,6-四甲基苯基、2,3,5,6-四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二基苯基、正十四基苯基、聯苯基、茀基、三苯基、萘基、蒽基、苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲
基苯基)甲基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、蒽基甲基、4-甲氧基苯基、或3,4-二甲氧基苯基,或者R11及R12可經由伸丁基或伸戊基相連結以形成一環;R10為甲基、乙基、正丙基、異丙基、正丁基、異丁基、2-甲基丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、正十五基、環己基、苯基、2-甲苯基、3-甲苯基、4-甲苯基、2,3-二甲苯基、2,4-二甲苯基、2,5-二甲苯基、2,6-二甲苯基、3,4-二甲苯基、3,5-二甲苯基、2,3,4-三甲基苯基、2,3,5-三甲基苯基、2,3,6-三甲基苯基、2,4,6-三甲基苯基、3,4,5-三甲基苯基、2,3,4,5-四甲基苯基、2,3,4,6-四甲基苯基、2,3,5,6-四甲基苯基、五甲基苯基、乙基苯基、正丙基苯基、異丙基苯基、正丁基苯基、二級丁基苯基、三級丁基苯基、正戊基苯基、新戊基苯基、正己基苯基、正辛基苯基、正癸基苯基、正十二基苯基、正十四基苯基、聯苯基、茀基、三苯基、萘基、蒽基、苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二
甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲基苯基)甲基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基-苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、蒽基甲基、2-甲氧基苯基、或3,4-二甲氧基苯基。
於取代基X1及X2的定義中,鹵素原子的實例可包含氟、氯、溴、及碘原子;(C1-C50)烷基的實例可包含甲基、乙基、正丙基、異丙基、正丁基、二級丁基、三級丁基、正戊基、新戊基、戊基、正己基、正辛基、正癸基、正十二基、正十五基、及正二十基;(C3-C50)環烷基的實例可包含環丙基、環丁基、環戊基、環己基、環庚基、及金剛烷基(adamantyl);(C6-C30)芳基的實例可包含苯基及萘基;(C6-C30)芳基(C1-C50)烷基或((C1-C50)烷基(C6-C30)芳基)(C1-C50)烷基的實例可包含,苄基、(2-甲基苯基)甲基、(3-甲基苯基)甲基、(4-甲基苯基)甲基、(2,3-二甲基苯基)甲基、(2,4-二甲基苯基)甲基、(2,5-二甲基苯基)甲基、(2,6-二甲基苯基)甲基、(3,4-二甲基苯基)甲基、(4,6-二甲基苯基)甲基、(2,3,4-三甲基苯基)甲基、(2,3,5-三甲基苯基)甲基、(2,3,6-三甲基苯基)甲基、(3,4,5-三甲基苯基)甲基、(2,4,6-
三甲基苯基)甲基、(2,3,4,5-四甲基苯基)甲基、(2,3,4,6-四甲基苯基)甲基、(2,3,5,6-四甲基苯基)甲基、(五甲基苯基)甲基、(乙基苯基)甲基、(正丙基苯基)甲基、(異丙基苯基)甲基、(正丁基苯基)甲基、(二級丁基苯基)甲基、(三級丁基苯基)甲基、(正戊基苯基)甲基、(新戊基苯基)甲基、(正己基苯基)甲基、(正辛基苯基)甲基、(正癸基苯基)甲基、(正十四基苯基)甲基、萘基甲基、及蒽基甲基;(C1-C50)烷氧基的實例可包含甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、二級丁氧基、三級丁氧基、正戊基氧基、新戊基氧基、正己基氧基、正辛基氧基、正十二基氧基、正十五基氧基、及正二十基氧基;(C6-C30)芳基氧基的實例可包含苯氧基、4-三級丁基苯氧基、或4-甲氧基苯氧基,除氫以外包含N、P、O、S、Si及鹵素且由60或更少原子所構成之陰離子或雙陰離子配位基可為-OSiRfRgRh、-SRi(Rf至Ri各自獨立為(C1-C50)烷基、(C6-C30)芳基、(C3-C50)環烷基)、-NRjRk、或-PRlRm(Rj至Rm各自獨立為(C1-C50)烷基、(C6-C30)芳基、(C6-C30)芳基(C1-C50)烷基、(C3-C50)環烷基、三(C1-C50)烷基矽基、或三(C6-C30)芳基矽基)。-OSiRfRgRh的實例可包含三甲基矽氧基、三乙基矽氧基、三正丙基矽氧基、三異丙基矽氧基、三正丁基矽氧基、三二級丁基矽氧基、三三級丁基矽氧基、三異丁基矽氧基、三級丁基二甲基矽氧基、三正戊基矽氧基、三正己基矽氧基、或三環己基矽氧基;-NRjRk的實例可包含二甲胺基、二乙胺基、二正丙胺基、二異丙胺基、二正丁胺基、二二級丁胺基、二三級丁胺基、二異丁胺基、三級丁基異丙基胺基(tert-butylisopropylamino)、二正己
基胺基、二正辛基胺基、二正癸基胺基、二苯基胺基、二苄基胺基、甲基乙基胺基、甲基苯基胺基、苄基己基胺基(benzylhexylamino)、雙(三甲基矽基)胺基(bis(trimethylsilyl)amino)、或雙(三級丁基二甲基矽基)胺基(bis(tert-butyldimethylsilyl)amino);-PRlRm的實例可包含二甲基膦、二乙基膦、二正丙基膦、二異丙基膦、二正丁基膦、二二級丁基膦、二三級丁基膦、二異丁基膦、三級丁基異丙基膦、二正己基膦、二正辛基膦、二正癸基膦、二苯基膦、二苄基膦、甲基乙基膦、甲基苯基膦、苄基己基膦、雙(三甲基矽基)膦(bis(trimethylsilyl)phosphine)、及雙(三級丁基二甲基矽基)膦(bis(tert-butyldimethylsilyl)phosphine);-SRi的實例可包含甲基硫基、乙基硫基、丙基硫基、異丙基硫基、丁基硫基、或異戊基硫基。
X1及X2各自獨立為氟、氯、溴、甲基、乙基、異丙基、戊基、苄基、甲氧基、乙氧基、異丙氧基、三級丁氧基、苯氧基、4-三級丁基苯氧基、三甲基矽氧基、三級丁基二甲基矽氧基、二甲基胺基、二苯基胺基、二甲基膦、二乙基膦、二苯基膦、乙基硫基、或異丙基硫基。
本發明之過渡元素金屬化合物可選自以下結構之化合物,但不限於此:
M為Ti、Zr、或Hf;且X1與X2各自具有與上述化學式1中相同的定義。
其中,為了要成為用於製備選自乙烯同元聚合物及乙烯與α-烯烴共聚物之乙烯系聚合物的活性催化劑成分,本發明的過渡金屬化合物可較佳與一作為共催化劑之鋁氧烷化合物、硼化合物、或其混合物併用,其可自該過渡金屬錯合物中脫去一配位基X1或X2以使中心金屬陽離子化,並作為一鍵結強度弱的相對離子,即,一陰離子,且包含該過渡金屬化合物及該共催化劑的催化劑組合物亦包含於本發明的範圍中。
可於本發明中作為共催化劑的硼化合物已見於美國專利第5,198,401號,且可選自由以下化學式4至6所示的硼化合物:[化學式4]B(R41)3
[化學式5][R42]+[B(R41)4]-
[化學式6]
[(R43)pZH]+[B(R41)4]-
於化學式4至6中,B為一硼原子;R41為苯基,該苯基可進一步由3到5個選自氟原子、經或未經氟原子取代之(C1-C50)烷基、或經或未經氟原子取代之(C1-C50)烷氧基的取代基取代;R42為(C5-C7)芳香自由基(aromatic radical)或(C1-C50)烷基(C6-C20)芳基自由基、(C6-C30)芳基(C1-C50)烷基自由基,例如,三苯甲基自由基;Z為一氮或磷原子;R43為(C1-C50)烷基自由基、或經一個氮原子及二個(C1-C50)烷基基團取代的苯胺自由基;且p為整數2或3。
硼系共催化劑的較佳實例包含參(五氟苯基)硼烷、參(2,3,5,6-四氟苯基)硼烷、參(2,3,4,5-四氟苯基)硼烷、參(3,4,5-三氟苯基)硼烷、參(2,3,4-三氟苯基)硼烷、苯基雙(五氟苯基)硼烷、肆(五氟苯基)硼酸酯(tetrakis(pentafluorophenyl)borate)、肆(2,3,5,6-四氟苯基)硼酸酯(tetrakis(2,3,5,6-pentafluorophenyl)borate)、肆(2,3,4,5-四氟苯基)硼酸酯(tetrakis(2,3,4,5-pentafluorophenyl)borate)、肆(3,4,5-三氟苯基)硼酸酯(tetrakis(3,4,5-trifluorophenyl)borate)、肆(2,2,4-三氟苯基)硼酸酯(tetrakis(2,2,4-trifluorophenyl)borate)、苯基雙(五氟苯基)硼酸酯(phenylbis(pentafluorophenyl)borate)、及肆(3,5-雙三氟甲基苯基)硼酸酯(tetrakis(3,5-bistrifluoromethylphenyl)borate)。此外,其特定多元
(compounded)實例包含肆(五氟苯基)硼酸二茂鐵(ferrocenium tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸1,1'-二甲基二茂鐵(1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸酯(tetrakis(pentafluorophenyl)borate)、肆(五氟苯基)硼酸三苯基甲基酯(triphenylmethyl tetrakis(pentafluorophenyl)borate)、肆(3,5-雙三氟甲基苯基)硼酸三苯基甲基酯(triphenylmethyl tetrakis(3,5-bistrifluoromethylphenyl)borate)、肆(五氟苯基)硼酸三乙基銨、肆(五氟苯基)硼酸三丙基銨、肆(五氟苯基)硼酸三正丁基銨、肆(3,5-雙三氟甲基苯基)硼酸三正丁基銨、肆(五氟苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸-N,N-二乙基苯銨、肆(五氟苯基)硼酸-N,N-2,4,6-五甲基苯銨、肆(3,5-雙三氟甲基苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸二異丙基苯銨、肆(五氟苯基)硼酸二環己基苯銨、肆(五氟苯基)硼酸三苯基鏻、肆(五氟苯基)硼酸三(甲基苯基)鏻、及肆(五氟苯基)硼酸三(二甲基苯基)鏻。其中,較佳為肆(五氟苯基)硼酸-N,N-二甲基苯銨、肆(五氟苯基)硼酸三苯基甲基酯、及參(五氟苯基)硼烷。
於本發明中,可作為共催化劑的鋁化合物可選自化學式7或8所示的鋁氧烷化合物、化學式9所示的有機鋁化合物、或化學式10或11所示的有機鋁碳氫氧化合物(organic aluminum hydrocarbyloxide):[化學式7]
(-Al(R51)-O-)m
[化學式8](R51)2Al-(-O(R51)-)q-(R51)2
[化學式9](R52)rAl(E)3-r
[化學式10](R53)2AlOR54
[化學式11]R53Al(OR54)2
於化學式7至11中,R51為(C1-C50)烷基,較佳為甲基或異丁基;m及q各自獨立為5至20的整數;R52及R53各自獨立為(C1-C50)烷基;E為一氫原子或鹵素原子;r為一1至3的整數;且R54為(C1-C50)烷基或(C6-C30)芳基。
鋁化合物的特定實例包含鋁氧烷化合物,例如甲基鋁氧烷、修飾甲基鋁氧烷、四異丁基鋁氧烷;有機鋁化合物,例如三烷基鋁,包含三甲基鋁、三乙基鋁、三丙基鋁、三異丁基鋁、及三己基鋁;氯化二烷基鋁,包含氯化二甲基鋁、氯化二乙基鋁、氯化二丙基鋁、氯化二異丁基鋁、及氯化二己基鋁;二氯化烷基鋁,包含二氯化甲基鋁、二氯化乙基鋁、二氯化丙基鋁、二氯化異丁基鋁、及二氯化己基鋁;以及氫化二烷基鋁,包含氫化二甲基鋁、氫化二乙基鋁、氫化二丙基鋁、氫化二異丁基鋁、及氫化二己基鋁。
其中,較佳為三烷基鋁,更佳為三乙基鋁及三異丁基鋁。
在用於製備選自乙烯同元聚合物及乙烯及α-烯烴共聚物之乙烯系聚合物之本發明含共催化劑的過渡金屬催化劑組合物中,該過渡金屬化合物與共催化劑之過渡金屬(M):硼原子(B):鋁原子(Al)的莫耳比較佳為1:0至100:1至2000,且更佳為1:0.5至5:10至500。上述的比例使得乙烯同元聚合物或乙烯及α-烯烴共聚物得以製備,且該比例範圍可隨反應的純度而改變。
根據本發明的另一方面,使用過渡金屬催化劑組合物製備乙烯系聚合物的方法可在適當有機溶劑存在下,藉由使過渡金屬催化劑、共催化劑、及乙烯或α-烯烴共單體相接觸而進行。於此,該過渡金屬化合物與該共催化劑組分可分別供給至反應器,或者該等組分可預先混合後再供給至反應器。混合的條件(例如供給的順序、溫度、或濃度)並沒有特別限制。
可用於該製備方法的有機溶劑的較佳實例包含(C3-C20)碳氫化合物,且其特定實例包含丁烷、異丁烷、戊烷、己烷、庚烷、辛烷、異辛烷、壬烷、癸烷、十二烷、環己烷、甲基環己烷、苯、甲苯、二甲苯等。
特定言之,於乙烯同元聚合物製備中,乙烯可單獨作為單體使用。於此,適當的乙烯壓力為1至1000大氣壓,且更佳為6至150大氣壓。且有效地,聚合反應溫度可為25℃至200℃,且較佳為50℃至180℃。
此外,於製備乙烯及α-烯烴共聚物時,可使用選自直鏈或支鏈
(C3-C18)α-烯烴、(C5-C20)環烯烴、苯乙烯、及苯乙烯衍生物之至少一者作為共單體,與乙烯一起使用。(C3-C18)α-烯烴的較佳實例可選自以下群組:丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯、及1-十八烯;(C5-C20)環烯烴的較佳實例可選自以下群組:環戊烯、環己烯、降莰烯、及苯基降莰烯;且苯乙烯及其衍生物的較佳實例可選自以下群組:苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、及3-氯甲基苯乙烯。於本發明中,上述烯烴可與乙烯共聚,或二或更多種的烯烴可與乙烯共聚。於此,較佳的乙烯壓力及聚合反應溫度係與製備乙烯同元聚合物的情況相同。根據本發明的方法所製得的共聚物的乙烯含量可為30重量%或更多,較佳為60重量%或更多,更佳為60至99重量%。
如上所述,當使用本發明的催化劑時,可由適當使用乙烯及作為共單體之(C4-C10)α-烯烴,而簡單且經濟地製備具有0.850克/立方公分至0.960克/立方公分之密度及0.001至15公釐/分鐘(dg/min)之熔流指數之從彈性體至高密度聚乙烯(HDPE)的聚合物。尤其,當使用本發明的催化劑時,可使用乙烯及1-丁烯來以高產率製備密度為0.850至0.910克/立方公分的共聚物。
此外,可使用本發明的催化劑極佳地製備乙烯/丙烯(EP)彈性體。
此外,於製備根據本發明的乙烯同元聚合物或共聚物時,可使用氫作為分子量調節劑,以調節分子量。其重量平均分子量(Mw)通常為5,000至1,000,000克/莫耳。
由於本發明所提出的催化劑組合物在聚合反應器中係處於均質狀態,因此該催化劑組合物可較佳地使用於在溫度高於相應聚合物熔點下進行的溶液聚合反應法。然而,如美國專利第4,752,597號所揭露,可將過渡金屬化合物與共催化劑承載(support)在一多孔性金屬氧化物承載物上,以用於漿料聚合反應或氣相聚合反應法,作為非勻相催化劑組合物。
此外,本發明可包含由以下化學式12及13所示的化合物,作為製備化學式1之過渡金屬化合物的中間物。
R1至R9及n各具有與化學式1中相同的定義,其中不包含R1、R2、R3、R6、R7、R8、及R9均為氫的狀況。
R1至R9及n各具有與化學式1中相同的定義。
本發明的過渡金屬化合物或包含該過渡金屬化合物的催化劑組合物可經濟地以高合成產率輕易製得。此外,本發明的過渡金屬化合物或催化劑組分與其他烯烴具有極佳共聚合反應性,同時由於其極佳的熱穩定性,而在高溫時仍保持高催化活性,並得以以高產率製備高分子量聚合物,從而獲致比已知的茂金屬系及非茂金屬系單活性點催化劑更高的商業實用性。因此,本發明的過渡金屬催化劑組合物可有用地用於製備具各種物理性質之選自乙烯同元聚合物及乙烯和α-烯烴共聚物的乙烯系聚合物。
於下文中,將參考所附實施例詳細描述本發明的實施態樣,其並非用以限制本發明的範圍。
除非另外提及,所有合成配位基與催化劑的實驗皆藉由標準舒倫克(Schlenk)或手套箱(glove-box)技術於氮氣氛圍下進行。反應中使用的有機溶劑迴流(reflux)經鈉金屬及二苯甲酮以除去水分,並在使用前立即蒸餾。合成的配位基與催化劑之質子核磁共振光譜(1H-NMR)分析由Bruker 500兆赫(MHz)光譜儀於室溫進行。
於使用前,作為聚合反應溶劑的正庚烷係通過裝有5埃(Å)分子篩及活化氧化鋁的管,通以高純度氮氣起泡以充分除去水氣、氧及其他催化劑毒物。所聚合的聚合物由以下描述的測量方法分析。
1.熔流指數(melt flow index,MI)
根據ASTM D 2839進行測量。
2.密度
根據ASTM D 1505,使用密度梯度管進行測量。
3.熔點
在氮氣氛圍下,於速率為10℃/分鐘之二次加熱情況下,使用Dupont DSC 2910進行測量。
4.分子量及分子量分布
在1,2,3-三氯苯溶劑中,於135℃以1.0毫升/分鐘之流速使用配置有PL Mixed-BX2+preCol的PL210 GPC進行測量,且分子量以PL聚苯乙烯標準品校正。
5.共聚物中α-烯烴含量(重量%)
於Bruker DRX500核磁共振光譜儀中,於125兆赫茲(MHz)、碳13核磁共振光譜(13C-NMR)模式、120℃下,使用1,2,4-三氯苯/六氘苯(重量比7/3)混合溶劑進行測量。(參考文獻:Randal,J.C.JMS-Rev.Macromol.Chem.Phys. 1980,C29,201)
EP聚合物中之乙烯與α-烯烴含量的比例係以紅外線光譜儀定量。
[實施例1]錯合物1及錯合物2之混合物的製備
9,9-二己基-9氫-茀之合成
於2000毫升圓底燒瓶中置入9氫-茀(50克,300.1毫莫耳)與三級丁醇鉀(77.0克,721.9毫莫耳),之後緩慢注入700毫升二甲亞碸(DMSO)。在氮氣氛圍下,由滴液漏斗緩慢加入1-溴己烷(119克,721.9毫莫耳)。將混合物在室溫下攪拌24小時後,加入500毫升蒸餾水以終止反應。將以正己烷萃取所收集到的有機層以硫酸鎂乾燥,接著除去揮發物質,而後以正己烷用矽膠管柱層析法純化之,之後乾燥並在室溫下長期儲存,以獲得90.0克的9,9-二己基-9氫-茀固體(產率72.40%)。
1H NMR(500兆赫茲,CDCl3,ppm):δ=0.625-0.628(m,4H),
0.759-0.785(m,6H),1.050-1.125(m,12H),1.953-1.983(t,4H),7.293-7.340(m,6H),7.706-7.720(d,2H)
9,9-二己基-2-甲基-2,3-二氫環戊[b]茀-1(9氫)-酮(9,9-dihexyl-2-methyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one)之合成
於2000毫升圓底燒瓶中置入9,9-二己基-9氫-茀(79克,236.2毫莫耳)與2-溴-2-甲基丙醯溴(54.3克,236.2毫莫耳),然後加入600毫升二硫化碳溶解,接著以冰水冷卻反應器。於氮氣氛圍下,將三氯化鋁(78.7克,590.4毫莫耳)分為十批,以兩小時緩慢加入其中。將混合物在室溫下攪拌8小時後,加入500毫升蒸餾水以終止反應,接著以500毫升蒸餾水萃洗三次。將有機層以硫酸鎂乾燥,接著除去揮發性物質並乾燥,如此獲得89.0克之9,9-二己基-2-甲基-2,3-二氫環戊[b]茀-1(9氫)-酮的高黏性油體(產率93.6%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.601-0.627(m,4H),0.741-0.774(m,6H),1.000-1.126(m,12H),1.366-1.380(d,3H),1.961-2.202(m,4H),2.789-2.801(d,2H),3.445-3.498(m,1H),7,375-7.383(m,3H),7.731(s,2H),7.764-7.779(d,1H)
9,9-二己基-2-甲基-1,2,3,9-四氫環戊[b]茀-1-醇(9,9-dihexyl-2-methyl-1,2,3,9-tetrahydrocyclopenta[b]fluoren-1-ol)之合成
於1000毫升圓底燒瓶中,將9,9-二己基-2-甲基-2,3-二氫環戊[b]
茀-1(9氫)-酮(85克,211.1毫莫耳)溶於400毫升四氫呋喃(THF)及400毫升乙醇中,接著攪拌。將硼氫化鈉(NaBH4)(10克,265.0毫莫耳)分為五批加入反應產物,而後攪拌12小時。所得的混合物在除去溶劑後將其溶於乙酸乙酯中,接著以水萃洗三次。將有機層以硫酸鎂乾燥,接著除去揮發性物質並乾燥,以獲得82.0克之9,9-二己基-2-甲基-1,2,3,9-四氫環戊[b]茀-1-醇(兩種異構物)的高黏性油體(產率96.0%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.628-0.631(m,8H),0.762-0.788(m,12H),1.109-1.136(m,24H),1.198-1.212(d,3H),1.314-1.327(d,3H),1.522-1.535(d,1H),1.830-1.846(d,1H),1.956-1.963(m,8H),2.323-2.352(m,1H),2.525-2.572(m,1H),2.628-2.655(m,1H),2.733-2.779(m,1H),3.011-3.057(m,1H),3.164-3.210(m,1H),4.783-4.812(t,1H),5.052-5.077(t,1H),7,289-7.380(m,8H),7.525(s,1H),7.558(s,1H),7.672-7.685(d,2H)
9,9-二己基-2-甲基-3,9-二氫環戊[b]茀(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluorene)之合成
於500毫升圓底燒瓶中,將9,9-二己基-2-甲基-1,2,3,9-四氫環戊[b]茀-1-醇(80克,197.7毫莫耳)和對甲苯磺酸(0.2克)溶於320毫升甲苯,而後在迪安-斯塔克(Dean-Stark)蒸餾裝置中迴流以完全除水。將所得的物質冷卻至室溫,然後注入氯化銨水溶液(150毫升)及200毫升乙醚,而後分離有機層。將以乙醚萃取剩餘物所收集得到的有機層以硫酸鎂除水,接著除去揮發性材料,
之後以矽膠管柱層析管純化,以獲得74.0克之9,9-二己基-2-甲基-3,9-二氫環戊[b]茀(產率96.8%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.611-0.671(m,4H),0.755-0.784(m,6H),1.041-1.140(m,12H),1.943-1.976(m,4H),2.200(s,3H),3.373(s,2H),6.556(s,1H),7.208-7.381(m,4H),7.653-7.668(d,1H),7.700(s,1H)
N-三級丁基-1-(9,9-二己基-2-甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺(N-tert-butyl-1-(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamine)及N-三級丁基-1-(9,9-二己基-2-甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(N-tert-butyl-1-(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine)之合成
於500毫升圓底燒瓶中,將9,9-二己基-2-甲基-3,9-二氫環戊[b]茀(40.0克,103.5毫莫耳)溶於320毫升乙醚中,隨後將溫度降至-78℃。接著緩慢注入正丁基鋰(2.5M己烷溶液,42毫升),而後於室溫攪拌12小時。在真空除去揮發性物質後,將350毫升正己烷加入至混合物中以將反應器溫度降至-78℃,接著加入二氯二甲基矽烷(40克)。再次將溫度升至室溫,接著攪拌24小時,之後過濾除去鹽類。然後以真空除去揮發性物質。將產物再次加入一500毫升圓底燒瓶中,並溶於320毫升乙醚。將溫度降至-78℃並加入三級丁基胺(22.7克,310.4毫莫耳)。將溫度升至室溫,接著攪拌12小時,然後以真空完全除去揮發性物質。之後,加入
200毫升正己烷以溶解所得到的物質,並過濾除去鹽類。除去溶劑,以獲得48克之N-三級丁基-1-(9,9-二己基-2-甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(9,9-二己基-2-甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(比例約1:1)之混合物的黏性物質(產率88.9%)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.132(s,3H),0.177-0.198(d,6H),0.270(s,3H),0.804-0.879(m,12H),0.973-1.295(m,50H),2.170-2.348(m,14H),3.398-3.428(d,2H),6.745(s,2H),7.337-7.434(m,6H),7.518-7.908(m,6H)
(三級丁基胺)二甲基(9,9-二己基-2-甲基-3,9-二氫環戊[b]茀-3-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(9,9-dihexyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl)(錯合物1)及(三級丁基胺)二甲基(9,9-二己基-2-甲基-1,9-二氫環戊[b]茀-1-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(9,9-dihexyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl)(錯合物2)之合成
於500毫升圓底燒瓶中,將N-三級丁基-1-(9,9-二己基-2-甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(9,9-二己基-2-甲基-1,9-二氫環五戊[b]茀-1-基)-1,1-二甲基矽胺(比例約1:1)的混合物(8.64克,16.75毫莫耳)溶於130毫升乙醚中,然後將溫度降至-78℃。之後緩慢注入甲基鋰(1.5M乙醚溶液,49.4
毫升),將溫度升至室溫,接著攪拌12小時以製備鋰鹽。此外,於乾燥箱中將四氯化鈦(16.75毫莫耳)及150毫升無水正己烷加入一500毫升圓底燒瓶中並將溫度降至-78℃,然後緩慢加入所製得的鋰鹽。將溫度再升至室溫,接著攪拌4小時,並以真空除去溶劑,將所得的物質以正己烷溶解,隨後以過濾萃取濾液。再次以真空除去溶劑,以獲得8.1克之錯合物1與錯合物2之混合物的固體(比例約1:1)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.079-0.091(d,6H),0.623-0.645(d,6H),0.813-1.336(m,56H),1.601-1.619(d,18H),2.071-2.514(m,14H),7.025-7.035(d,2H),7.330-8.099(m,12H)
[實施例2]錯合物3及錯合物4之混合物的製備
9,9-二甲基-9氫-茀之合成
於2000毫升圓底燒瓶中置入9氫-茀(50克,300.1毫莫耳)與三級丁醇鉀(77.0克,721.9毫莫耳),之後緩慢注入700毫升DMSO。在氮氣氛圍下,由滴液漏斗緩慢加入碘甲烷(113.5克,800毫莫耳),同時將反應器溫度維持在10℃或更低。將混合物在室溫下攪拌24小時後,加入500毫升蒸餾水以終止反應。以正己烷萃取,收集有機層,並將所得有機層以硫酸鎂乾燥,之後除去揮發物質,然後以正己烷用矽膠管柱層析管純化之,接著乾燥以獲得47.5克之9,9-二甲基-9氫-茀的白色固體(產率81.50%)。
1H-NMR(500MHz,CDCl3,ppm):δ=1.547(s,6H),7.368-7.393(t,4H),7.488-7.499(d,2H),7.777-7.791(d,2H)
2,9,9-三甲基-2,3-二氫環戊[b]茀-1(9氫)-酮(2,9,9-trimethyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one)之合成
於2000毫升圓底燒瓶中置入9,9-二甲基-9氫-茀(50克,257.4毫莫耳)與2-溴-2-甲基丙醯溴(61.0克,265.1毫莫耳),之後注入700毫升之二硫化碳以溶解之。然後,將反應器以冰水冷卻。於氮氣氛圍下,將三氯化鋁(85.8克,643.4毫莫耳)分為十批,以兩小時緩慢加入其中。將混合物在室溫下攪拌8小時後,加入500毫升蒸餾水以終止反應。將所得混合物加入500毫升氯甲烷稀釋,並以500毫升蒸餾水萃洗三次。有機層以硫酸鎂乾燥,接著除去揮發性物質並乾燥,然後以氯甲烷及甲醇使其再結晶,以獲得64.0克之2,9,9-三甲基-2,3-二氫環戊[b]茀-1(9氫)-酮的白色
固體(產率94.8%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=1.354-1.369(d,3H),1.517(s,6H),2.784-2.811(d,2H),3.444-3.496(m,1H),7.376-7.429(m,2H),7,471-7.485(d,2H),7.763(s,1H),7.795-7.808(d,2H),7.832(s,1H)
2,9,9-三甲基-3,9-二氫環戊[b]茀(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluorene)之合成
於1000毫升圓底燒瓶中,將2,9,9-三甲基-2,3-二氫環戊[b]茀-1(9氫)-酮(50克,190.6毫莫耳)以400毫升四氫呋喃及400毫升乙醇溶解,而後攪拌。硼氫化鈉(NaBH4)(9.4克,247.8毫莫耳)分為五批加入反應產物中,而後攪拌12小時。將所得混合物在除去溶劑後溶於乙酸乙酯中,接著以水萃洗三次。將有機層以硫酸鎂乾燥,而後除去揮發性物質。將經乾燥的反應產物溶於320毫升甲苯,然後放入一500毫升圓底燒瓶。之後,放入對甲苯磺酸(0.2克),而後在Dean-Stark蒸餾裝置中迴流以完全去除水。將所得到物質冷卻至室溫,而後注入氯化銨水溶液(150毫升)及200毫升乙醚,接著分離有機層。將以乙醚萃取剩餘物所收集到的有機層以硫酸鎂乾燥,接著除去揮發性物質,之後以矽膠管柱層析法純化,以獲得42.0克之2,9,9-三甲基-3,9-二氫環戊[b]茀(產率89.42%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=1.515(s,6H),2.203(s,3H),3.375(s,2H),6.559(s,1H),7.279-7.332(m,3H),7.425-7.440(d,1H),7.697-7.711(d,1H),7.740(s,1H)
N-三級丁基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺(N-tert-butyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamine)及N-三級丁基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(N-tert-butyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine)之合成
於500毫升圓底燒瓶中,將2,9,9-三甲基-3,9-二氫環戊[b]茀(15.0克,60.9毫莫耳)溶於300毫升乙醚中,然後將溫度降至-78℃。之後,緩慢注入丁基鋰(2.5M己烷溶液,24.8毫升),接著於室溫攪拌12小時。以真空除去揮發性材料後,將350毫升正己烷加入混合物中以將反應器溫度降至-78℃,接著加入二氯二甲基矽烷(23克)。將溫度再升至室溫,接著攪拌24小時,然後過濾除去鹽類。之後,以真空除去揮發性物質。將產物再次置入一500毫升圓底燒瓶中,並溶於320毫升乙醚。將溫度降至-78℃,並加入三級丁基胺(16.1克,152.2毫莫耳)。將溫度升至室溫,接著攪拌12小時。而後以真空完全除去揮發性物質。之後,加入200毫升甲苯以溶解所得物質,並以過濾除去鹽類。除去溶劑,以獲得21.0克之N-三級丁基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺之混合物的黏性物質(產率91.8%)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.085-0.098(d,6H),0.229-0.253(d,6H),0.555(s,2H),1.161-1.179(d,18H),
1.534-1.559(d,12H),2.304(s,6H),3.385-3.422(d,2H),6.747(s,2H),7.303-8.049(m,12H)
(三級丁基胺)二甲基(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl)(錯合物3)及(三級丁基胺)二甲基(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl)(錯合物4)之合成
於250毫升圓底燒瓶中,將N-三級丁基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺的混合物(10.4克,27.69毫莫耳)溶於200毫升乙醚中,然後將溫度降至-78℃,之後,緩慢注入甲基鋰(1.5M乙醚溶液,75.6毫升)。將溫度升至室溫,接著攪拌12小時以製備鋰鹽。此外,於乾燥箱中將四氯化鈦(5.25克,27.69毫莫耳)及150毫升無水正己烷加入一500毫升圓底燒瓶中,然後將溫度降至-78℃。之後,緩慢加入所製得的鋰鹽。再將溫度升至室溫,接著攪拌4小時,並以真空除去溶劑。所得材料再溶於甲苯中,以過濾去除未溶解部分。再次以真空除去甲苯,以獲得10.8克之錯合物3與錯合物4的混合物固體。
1H-NMR(500兆赫茲,C6D6,ppm):δ=-0.019 - -0.010(d,6H),
0.641-0.647(d,6H),0.794-2.212(m,48H),7.004-7.025(d,2H),7.106-8.092(m,12H)
[實施例3]錯合物5及錯合物6之混合物的製備
N-環己基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺(N-cyclohexyl-1-(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamine)及N-環己基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(N-cyclohexyl-1-(2,9,9-trimethyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine)之合成
於圓底燒瓶中,將2,9,9-三甲基-3,9-二氫環戊[b]茀(7.5克,30.5毫莫耳)溶於300毫升乙醚中,然後將溫度降至-78℃。
之後,緩慢注入丁基鋰(2.5M己烷溶液,12.4毫升),接著於室溫攪拌12小時。以真空除去揮發性物質後,將200毫升正己烷加入混合物中以將反應器溫度降至-78℃,接著加入二氯二甲基矽烷(11.8克,91.4毫莫耳)。將溫度再升至室溫,接著攪拌24小時,然後過濾除去鹽類。之後,以真空除去揮發性物質。將產物再次置入一200毫升圓底燒瓶中,並溶於150毫升乙醚。將溫度降至-78℃,並加入環己烷胺(9.05克,91.4毫莫耳)。將溫度升至室溫,接著攪拌12小時,然後以真空完全除去揮發性物質。之後,加入100毫升甲苯以溶解所得物質,並過濾除去鹽類。將溶劑去除,以獲得10.6克之N-環己基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-環己基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺之混合物的黏性物質。
(環己基胺)二甲基(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)二甲基矽烷鈦(IV)((cyclohexylamido)dimethyl(2,9,9-trimethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl)(錯合物5)及(環己基胺)二甲基(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)二甲基矽烷鈦(IV)((cyclohexylamido)dimethyl(2,9,9-trimethyl-1,9-dihydrocyclochloropenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl)(錯合物6)之合成
於250毫升三頸圓底燒瓶中,將經徹底乾燥的N-環己基-1-(2,9,9-三甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-環
己基-1-(2,9,9-三甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺的混合物(10.6克,26.39毫莫耳)溶於200毫升乙醚中,並將溫度降至-78℃。之後,緩慢注入甲基鋰(1.5M乙醚溶液,72.1毫升),使溫度升至室溫,接著攪拌12小時以製備鋰鹽。此外,於乾燥箱中將四氯化鈦(5.00克,26.39毫莫耳)及150毫升無水正己烷置入一500毫升圓底燒瓶中,接著將溫度降至-78℃。然後,將所製得的鋰鹽緩慢加入。再次將溫度升至室溫,接著攪拌4小時,並以真空除去溶劑。將所得物質再以甲苯溶解,然後以過濾除去未溶解部分。再次以真空除去甲苯,以獲得11.5克之錯合物5與錯合物6之混合物固體。
1H-NMR(500兆赫茲,C6D6,ppm):δ=-0.070 - -0.049(d,6H),0.628-0.634(d,6H),0.764-2.195(m,50H),4.779(m,2H),6.985-7.002(d,2H),7.100-8.095(m,12H)
[實施例4]錯合物7及錯合物8之混合物的製備
9,9-二十四基-9氫-茀之合成
於2000毫升圓底燒瓶中置入9氫-茀(15克,90.24毫莫耳)與三級丁醇鉀(21.2克,198.5毫莫耳),之後緩慢注入300毫升DMSO。在氮氣氛圍下,由滴液漏斗緩慢滴入1-溴十四烷(54克,198.5毫莫耳),同時將反應器溫度維持在10℃或更低。將混合物在室溫下攪拌24小時後,加入500毫升蒸餾水以終止反應。以正己烷萃取,收集有機層,並將所得有機層以硫酸鎂乾燥,接著除去揮發物質,然後以正己烷用矽膠管柱層析管純化,接著乾燥以獲得42.0克之9,9-二十四基-9氫-茀的白色固體(產率83.26%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.616-0.634(m,4H),0.881-0.909(m,6H),1.051-1.323(m,44H),1.951-1.984(t,4H),7.292-7.355(m,6H),7.708-7.722(d,2H)
2-甲基-9,9-二十四基-2,3-二氫環戊[b]茀-1(9氫)-酮(2-methyl-9,9-ditetradecyl-2,3-dihydrocyclopenta[b]fluoren-1(9H)-one)之合成
於5000毫升圓底燒瓶中,置入9,9-二十四基-9氫-茀(30克,53.7毫莫耳)與2-溴-2-甲基丙醯溴(12.7克,55.3毫莫耳),之後加入300毫升二硫化碳以溶解之。之後,將反應器以冰水冷卻。於氮氣氛圍下,將三氯化鋁(15.7克,118.1毫莫耳)分為十批,以兩小時緩慢加入。將混合物在室溫下攪拌8小時後,加入100毫升蒸餾水以終止反應,接著以500毫升蒸餾水萃洗三次。將有機層以硫酸鎂乾燥,接著除去揮發性物質並乾燥,以獲得30.0克之2-甲基-9,9-二十四基-2,3-二氫環戊[b]茀-1(9氫)-酮的高黏性油體(產率89.1%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.590(m,4H),0.867-0.895(m,6H),1.024-1.295(m,44H),1.367-1.382(d,3H),1.963-2.204(t,4H),2.792-2.826(d,2H),3.448-3.500(m,1H),7.372-7.400(m,3H),7.726-7.780(m,3H)
2-甲基-9,9-二十四基-3,9-二氫環戊[b]茀之合成
於500毫升圓底燒瓶中,將2-甲基-9,9-二十四基-2,3-二氫環戊[b]茀-1(9氫)-酮(20克,31.9毫莫耳)溶於150毫升THF及150毫升乙醇中,接著攪拌。將硼氫化鈉(NaBH4)(1.8克,47.8毫莫耳)分為五批加入反應物,隨後攪拌12小時。將所得混合物在除去溶劑後溶於乙酸乙酯中,而後以水萃洗三次。將有機層以硫酸鎂乾燥,接著除去揮發性物質。將經乾燥的反應物以150毫
升甲苯溶解,然後置入一圓底燒瓶。之後,於其中置入對甲苯磺酸(0.08克),而後在Dean-Stark蒸餾裝置中迴流以完全除水。將所得物質冷卻至室溫,而後注入氯化銨水溶液(100毫升)及200毫升乙醚,接著分離有機層。將以乙醚萃取萃取剩餘物所得的有機層以硫酸鎂乾燥,接著除去揮發性物質,之後以矽膠管柱層析法純化,以獲得15.3克之2-甲基-9,9-二十四基-3,9-二氫環戊[b]茀(產率78.5%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=0.649-0.665(m,4H),0.891-0.918(m,6H),1.059-1.319(m,44H),1.953-1.986(t,4H),2.206(s,3H),3.378(s,2H),6.562(s,1H),7.237-7.332(m,4H),7.663-7.678(d,1H),7.710(s,1H)
N-三級丁基-1-(9,9-二十四基-2-甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺(N-tert-butyl-1-(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)-1,1-dimethylsilanamine)及N-三級丁基-1-(9,9-二十四基-2-甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(N-tert-butyl-1-(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)-1,1-dimethylsilanamine)之合成
於250毫升圓底燒瓶中,將2-甲基-9,9-二十四基-3,9-二氫環戊[b]茀(4.9克,8.0毫莫耳)溶於100毫升無水乙醚中,然後將溫度降至-78℃。之後,緩慢注入丁基鋰(1.6M己烷溶液,5.5毫升),接著於室溫攪拌12小時。以真空除去揮發性材料後,對混合物加入100毫升正己烷以將反應器溫度降至-78℃,接著加入二氯二甲
基矽烷(2.9克)。將溫度再升至室溫,接著攪拌24小時,然後過濾除去鹽類。之後,以真空除去揮發性物質。將產物再次加入一250毫升圓底燒瓶中,並溶於100毫升乙醚中。將溫度降至-78℃,並加入三級丁基胺(1.8克,24.1毫莫耳)。將溫度升至室溫,接著攪拌12小時,而後以真空完全除去揮發性物質。之後,加入200毫升正己烷以溶解所得物質,並過濾除去鹽類。將溶劑除去,以獲得5.5克之N-三級丁基-1-(9,9-2-甲基-二十四基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(9,9-二十四基-2-甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(比例約1:1)之混合物的黏性物質(產率92.7%)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.145(s,3H),0.183-0.204(d,6H),0.290(s,3H),0.552(s,1H),0.603(s,1H),0.998-1.370(m,126H),2.228-2.301(m,14H),3.408-3.435(d,2H),6.749-6.760(d,2H),7.353-7.461(m,6H),7.546-8.073(m,6H)
(三級丁基胺)二甲基(9,9-二十四基-2-甲基-3,9-二氫環戊[b]茀-3-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl)(錯合物7)及(三級丁基胺)二甲基(9,9-二十四基-2-甲基-1,9-二氫環戊[b]茀-1-基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(9,9-ditetradecyl-2-methyl-1,9-dihydrocyclopenta[b]fluoren-1-yl)silanetitanium(IV)dimethyl)(錯合物8)
之合成
於250毫升圓底燒瓶中,將N-三級丁基-1-(9,9-二十四基-2-甲基-3,9-二氫環戊[b]茀-3-基)-1,1-二甲基矽胺及N-三級丁基-1-(9,9-二十四基-2-甲基-1,9-二氫環戊[b]茀-1-基)-1,1-二甲基矽胺(比例約1:1)的混合物(5.0克,6.8毫莫耳)溶於100毫升乙醚中,並將溫度降至-78℃。之後,緩慢注入甲基鋰(1.5M乙醚溶液,18.5毫升)。將溫度升至室溫,接著攪拌12小時以製備鋰鹽。此外,於乾燥箱中將四氯化鈦(16.75毫莫耳)及50毫升無水正己烷置入一250毫升圓底燒瓶中,並將溫度降至-78℃,然後,緩慢加入所製得的鋰鹽。再將溫度升至室溫,接著攪拌4小時,並以真空除去溶劑。將所得物質以正己烷溶解,並過濾萃取濾液。再次以真空除去溶劑,以獲得5.2克之錯合物7與錯合物8的混合物固體(比例約1:1)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.093-0.104(d,6H),0.630-0.647(d,6H),0.856-1.392(m,120H),1.609-1.643(d,18H),2.095-2.214(m,14H),7.023-7.041(d,2H),7.305-8.097(m,12H)
[實施例5]錯合物9的製備
1,2,9,9-四甲基-3,9-二氫環戊[b]茀之合成
於1000毫升圓底燒瓶中,將2,9,9-三甲基-2,3-二氫環戊[b]茀-1(9氫)-酮(50克,190.6毫莫耳)溶於400毫升甲苯中,而後溫度降至0℃。之後,緩慢注入76毫升3M溴化甲基鎂(THF溶液),接著於室溫攪拌12小時。將反應產物倒入200毫升1N氫氯酸水溶液與200克冰的混合物中。攪拌混合物1小時,接著以甲苯萃取,之後將有機層以硫酸鎂乾燥,接著除去揮發性物質。將經乾燥的反應產物溶於320毫升甲苯中,然後置入一500毫升圓底燒瓶。之後,於其中置入對甲苯磺酸(0.2克),而後在Dean-Stark蒸餾裝置中迴流以完全除水。將所得材料冷卻至室溫,而後注入氯化銨水溶液(150毫升)及200毫升乙醚,接著分離有機層。將以乙醚萃取剩餘物所收集得到的有機層以硫酸鎂乾燥,接著除去揮發性物質,然後以矽膠管柱層析法純化,以獲得42.0克1,2,9,9-四甲基-3,9-二氫環戊[b]茀(產率84.6%)。
1H-NMR(500兆赫茲,CDCl3,ppm):δ=1.547-1.568(d,6H),
2.123(s,6H),3.352(s,2H),7.273-7.363(m,3H),7.442-7.456(d,1H),7.711-7.45723(m,2H)
N-三級丁基-1,1-二甲基-1-(1,2,9,9-四甲基-3,9-二氫環戊[b]茀-3-基)矽胺(N-tert-butyl-1,1-dimethyl-1-(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanamine)之合成
於500毫升圓底燒瓶中,1,2,9,9-四甲基-3,9-二氫環戊[b]茀(15.0克,57.6毫莫耳)溶於300毫升乙醚中,然後將溫度降至-78℃。之後,緩慢注入丁基鋰(2.5M己烷溶液,25.4毫升),接著於室溫攪拌12小時。以真空除去揮發性物質後,將350毫升正己烷加入混合物以將反應器溫度降至-78℃,接著加入二氯二甲基矽烷(23克)。溫度再升至室溫,接著攪拌24小時,之後過濾除去鹽類。然後以真空除去揮發性物質。產物再次置入一500毫升圓底燒瓶中,並以320毫升乙醚溶解之。將溫度降至-78℃,並加入三級丁基胺(10.5克,144.0毫莫耳)。將溫度升至室溫,接著攪拌12小時,而後以真空完全除去揮發性物質。之後,加入200毫升甲苯以溶解所得物質,並過濾除去鹽類。將溶劑去除,以獲得20.0克之N-三級丁基-1,1-二甲基-1-(1,2,9,9-四甲基-3,9-二氫環戊[b]茀-3-基)矽胺的黏性物質(產率89.1%)。
1H-NMR(500兆赫茲,C6D6,ppm):δ=0.166(s,3H),0.222(s,3H),0.610(s,1H)1.239(s,9H),1.618-1.651(d,6H),2.256(s,6H),3.437(s,1H),7.361-7.466(m,3H),7.590(s,1H),7.958-7.973(d,1H),8.128(s,1H)
(三級丁基胺)-1,1-二甲基-1-(1,2,9,9-四甲基-3,9-二氫環戊[b]茀-3-基)二甲基矽烷鈦(IV)((t-butylamido)-1,1-dimethyl(1,2,9,9-tetramethyl-3,9-dihydrocyclopenta[b]fluoren-3-yl)silanetitanium(IV)dimethyl)(錯合物9)之合成
於250毫升圓底燒瓶中,N-三級丁基-1,1-二甲基-1-(1,2,9,9-四甲基-3,9-二氫環戊[b]茀-3-基)矽胺(10.8克,27.7毫莫耳)溶於200毫升乙醚中,並將溫度降至-78℃。之後,緩慢注入甲基鋰(1.5M乙醚溶液,75.76毫升)。將溫度升至室溫,接著攪拌12小時以製備鋰鹽。此外,於乾燥箱中將四氯化鈦(5.26克,27.7毫莫耳)及150毫升無水正己烷加入一500毫升圓底燒瓶中,並將溫度降至-78℃。然後,緩慢加入所製得的鋰鹽。再將溫度升至室溫,接著攪拌4小時,並以真空除去溶劑。將所得物質再溶於甲苯中,並以過濾除去未溶解部分。再次以真空除去甲苯,以獲得10.8克之錯合物9的固體。
1H-NMR(500兆赫茲,C6D6,ppm):δ=-0.018(s,3H),0.677(s,3H),0.819(s,3H),0.875(s,3H),1.562-1.584(m,15H),2.104(s,3H),2.423(s,3H),7.091-7.407(m,3H),7.680-7.712(m,2H),8.141(s,1H)
[比較製備實施例i](三級丁基胺)二甲基(四甲基環戊二烯基)二甲基矽烷鈦(IV)((t-butylamido)dimethyl(tetramethylcyclopentadienyl)silanetitanium(IV)dimethyl)的製備
透過以下方式製備(三級丁基胺)二甲基(四甲基環戊二烯基)二甲基矽烷鈦(IV)化合物:將購自美國Boulder Scientific公司的(三級丁基胺)二甲基(四甲基環戊二烯基)二氯矽烷鈦(IV)溶於乙醚中,將溫度降至-78℃,而後將其與2當量鋰金屬反應。
乙烯與1-辛烯的共聚反應
[實施例6至12及比較實施例1及2]利用連續溶液聚合反應法之乙烯與1-辛烯共聚合反應
使用以下連續型聚合反應裝置進行乙烯與1-辛烯的共聚反應。
使用實施例1至5及比較實施例1合成的催化劑作為單活性點催化劑,並使用環己烷作為溶劑。催化劑的用量係如下表1所示。Ti、Al、及B分別表示單活性點催化劑、作為共催化劑的三異丁基鋁、及肆(五氟苯基)硼酸三苯基甲基酯。個別的催化劑係溶於甲苯以0.2克/升的濃度注入,且係使用1-辛烯作為共單體進行合成。反應器的轉化率可由在各自反應條件下由聚合反應製備聚合物時,反應器中的反應條件與溫度梯度來估算。於單活性點催化劑的情況下,分子量係以反應器溫度與1-辛烯含量的函數來控制,且詳細的聚合條件及聚合結果係如以下表1所示。
-Ti:單活性點催化劑中的鈦
-Al:作為共催化劑的三異丁基鋁
-B:作為共催化劑的肆(五氟苯基)硼酸三苯基甲基酯
由實施例6至12及比較實施例1及2可見,相較於比較實施例1及2,在使用本發明所發展的催化劑的實施例6至12中,可輕易製得具有高乙烯轉化率(即使在高溫條件(100℃或更高)下)、低密度、及代表高分子量的低MI值的聚合物。
乙烯與1-丁烯的共聚反應
[實施例13至15]利用連續溶液聚合反應法之乙烯與1-丁烯共聚合反應
如下所示,乙烯與1-丁烯的共聚反應由一連續型聚合反應裝置進行,且使用與實施例6至12中提到之利用連續溶液聚合反應的乙烯與1-辛烯共聚反應相同的方法,惟使用1-丁烯作為共單體。詳細的聚合條件及聚合結果係如下表2所示。
-Ti:單活性點催化劑中的鈦
-Al:作為共催化劑的三異丁基鋁
-B:作為共催化劑肆(五氟苯基)硼酸三苯基甲基酯
由上表2可見,在使用本發明所發展的催化劑之實施例13至15
中,可輕易以高產率獲得具有高乙烯轉化率(即使在高溫(100℃或更高)條件下)及高分子量(即使用少量1-丁烯(1-C4/C2莫耳比=0.4))的超低密度彈性體進行催化反應。
以上已參照實施例詳細描述本發明,但本發明所屬技術領域技藝人士可在不背離本發明之精神及後附申請專利範圍的所定範圍下,進行各種修改。因此,對本發明之實施例的替換與修改並不脫本發明之技術。
Claims (12)
- 一種由以下化學式1表示之過渡金屬化合物:
- 如請求項1之過渡金屬化合物,該過渡金屬化合物係由以下化學式2或3表示:
- 如請求項2之過渡金屬化合物,其係選自以下化合物:
- 一種用於製備乙烯同元聚合物或乙烯與α-烯烴之共聚物的過渡金屬催化劑組合物,該過渡金屬催化劑組合物包含如請求項1至3中任一項所述之過渡金屬化合物;以及一選自以下群組之共催化劑:一鋁化合物、一硼化合物、及其混合物。
- 如請求項4之過渡金屬催化劑組合物,其中該過渡金屬化合 物與該共催化劑之過渡金屬(M):硼原子(B):鋁原子(Al)的莫耳比為1:0至100:1至2,000。
- 如請求項5之過渡金屬催化劑組合物,其中該過渡金屬化合物與該共催化劑之過渡金屬(M):硼原子(B):鋁原子(Al)的莫耳比為1:0.5至5:10至500。
- 一種使用如請求項4所述之過渡金屬催化劑組合物製備乙烯同元聚合物或乙烯與α-烯烴之共聚物之方法。
- 如請求項7之方法,其中與乙烯聚合之α-烯烴係選自以下群組之至少一者:丙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯、1-辛烯、1-癸烯、1-十一烯、1-十二烯、1-十四烯、1-十六烯、1-十八烯、環戊烯、環己烯、降莰烯、苯降莰烯、苯乙烯、α-甲基苯乙烯、對甲基苯乙烯、及3-氯甲基苯乙烯,且於該乙烯與α-烯烴之共聚物中,乙烯的含量為30至99重量%。
- 如請求項8之方法,其中供進行乙烯同元聚合反應或乙烯單體與α-烯烴之共聚合反應之反應器中的壓力為1至1000大氣壓,且聚合反應溫度為25至200℃。
- 如請求項9之方法,其中供進行乙烯同元聚合反應或乙烯單體與α-烯烴之共聚合反應之反應器中的壓力為6至150大氣壓,且聚合反應溫度為50至180℃。
- 一種由以下化學式12表示之化合物:[化學式12]
- 一種由以下化學式13表示之化合物:
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