CN102791750B - 乙烯-α-烯烃共聚物及成型体 - Google Patents
乙烯-α-烯烃共聚物及成型体 Download PDFInfo
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- CN102791750B CN102791750B CN201180013772.3A CN201180013772A CN102791750B CN 102791750 B CN102791750 B CN 102791750B CN 201180013772 A CN201180013772 A CN 201180013772A CN 102791750 B CN102791750 B CN 102791750B
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- Prior art keywords
- zirconium dichloride
- cyclopentadienyl
- hydrochloride
- fluorenyl
- diphenylmethylene
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- 239000004711 α-olefin Substances 0.000 title claims abstract description 118
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims abstract description 88
- 238000002844 melting Methods 0.000 claims abstract description 27
- 230000008018 melting Effects 0.000 claims abstract description 27
- 238000005227 gel permeation chromatography Methods 0.000 claims abstract description 20
- 239000000155 melt Substances 0.000 claims abstract description 18
- 238000009826 distribution Methods 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 106
- 238000000034 method Methods 0.000 claims description 79
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 61
- 238000001125 extrusion Methods 0.000 claims description 28
- 238000000113 differential scanning calorimetry Methods 0.000 abstract description 2
- -1 1-dodecene Carbene, 4-methyl-1-pentene Chemical compound 0.000 description 403
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 87
- 150000001875 compounds Chemical class 0.000 description 85
- 239000005977 Ethylene Substances 0.000 description 59
- 238000006116 polymerization reaction Methods 0.000 description 59
- 150000003623 transition metal compounds Chemical class 0.000 description 58
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 52
- 125000001183 hydrocarbyl group Chemical group 0.000 description 47
- 229920001577 copolymer Polymers 0.000 description 46
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 31
- 229910052739 hydrogen Inorganic materials 0.000 description 31
- 239000001257 hydrogen Substances 0.000 description 31
- 125000000217 alkyl group Chemical group 0.000 description 30
- 239000000178 monomer Substances 0.000 description 30
- 239000002734 clay mineral Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 28
- 239000011949 solid catalyst Substances 0.000 description 26
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 25
- 238000005259 measurement Methods 0.000 description 24
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910052782 aluminium Inorganic materials 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 19
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 239000001273 butane Substances 0.000 description 17
- 238000000465 moulding Methods 0.000 description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 16
- 230000000737 periodic effect Effects 0.000 description 16
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- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 15
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 15
- 150000001639 boron compounds Chemical class 0.000 description 14
- 125000005843 halogen group Chemical group 0.000 description 14
- 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 14
- 238000005482 strain hardening Methods 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
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- 229920000642 polymer Polymers 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
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- 238000004519 manufacturing process Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
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- 125000003277 amino group Chemical group 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 11
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 10
- 125000001309 chloro group Chemical group Cl* 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- LMNJIRLUFGKYMP-UHFFFAOYSA-L C[Si](C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[Si](C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 LMNJIRLUFGKYMP-UHFFFAOYSA-L 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 238000005342 ion exchange Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000012968 metallocene catalyst Substances 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- SVHPGKHHBXQFLQ-UHFFFAOYSA-L Cl[Zr](Cl)(C1C=CC=C1)(C1c2ccccc2-c2ccccc12)=C(c1ccccc1)c1ccccc1 Chemical compound Cl[Zr](Cl)(C1C=CC=C1)(C1c2ccccc2-c2ccccc12)=C(c1ccccc1)c1ccccc1 SVHPGKHHBXQFLQ-UHFFFAOYSA-L 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 150000002170 ethers Chemical class 0.000 description 7
- 238000005187 foaming Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 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 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001448 anilines Chemical class 0.000 description 6
- 150000001450 anions Chemical group 0.000 description 6
- 125000004104 aryloxy group Chemical group 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 238000012685 gas phase polymerization Methods 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000003624 transition metals Chemical group 0.000 description 6
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
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- 230000000052 comparative effect Effects 0.000 description 5
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- 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 5
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- 150000002500 ions Chemical class 0.000 description 5
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- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 5
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical group COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
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- 229910052740 iodine Inorganic materials 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
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- 239000010410 layer Substances 0.000 description 4
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
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- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
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- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 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
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
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- 229910052796 boron Inorganic materials 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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Abstract
本发明提供乙烯-α-烯烃共聚物,其具有860-950kg/m3的密度,0.01-100g/10分的熔体流动速率,在通过凝胶渗透色谱法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,特征松弛时间满足式(1)的关系,并且存在由差示扫描量热计所测定的多个熔融峰。40.2×MFR-0.606<τ<71.8×MFR-0.175 式(1)。
Description
技术领域
本发明涉及乙烯-α-烯烃共聚物及将该乙烯-α-烯烃共聚物挤出成型所获得的成型品。
背景技术
乙烯-α-烯烃共聚物利用各种的成型方法被成型为膜、片材、瓶子等,并且被用于食品包装材料等的各种用途。
在乙烯-α-烯烃共聚物中,已知使用金属茂催化剂进行聚合而成的共聚物在冲击强度、拉伸强度等机械强度方面是优异的。因此,使用此类共聚物时,因为它的厚度能够减小,而从采用非金属茂催化剂的催化剂所聚合的乙烯-α-烯烃共聚物形成的成型品所具有的机械强度得以保持,并且能够预期成型品的重量减轻和成本节约,因此,研究了该共聚物在各种用途中的使用。然而,使用先前的金属茂催化剂所聚合的乙烯-α-烯烃共聚物在挤出加工时具有高挤出负荷,熔融张力小,因此要求对其成型加工性进行改进。另外,使用金属茂催化剂所得到的乙烯-α-烯烃共聚物通常具有窄的共聚单体组成分布,由于晶体具有均一的熔融温度,因此存在可热封的温度范围变窄等二次加工性差的倾向。
针对于此,现在,研究了新型的金属茂催化剂,并且提出由该催化剂聚合的、成型加工性得到改进的乙烯-α-烯烃共聚物。例如,专利文献1描述了通过使用金属茂催化剂所聚合的乙烯-α-烯烃共聚物,该金属茂催化剂包括:具有配位体(其中具有环戊二烯型阴离子骨架的两个基团经由桥连基团键合)的过渡金属化合物、具有彼此不键合的两个基团(其具有取代的环戊二烯型阴离子骨架)的过渡金属化合物、和活化用的助催化剂成分。另外,专利文献2描述了通过使用助催化剂成分和金属茂催化剂所聚合的乙烯-α-烯烃共聚物,所述助催化剂成分通过使硅石、六甲基二硅氮烷、二乙基锌、五氟苯酚和水接触所获得,所述金属茂催化剂包括三异丁基铝和外消旋-亚乙基双(1-茚基)锆二苯酚盐。另外,专利文献3描述了通过使用金属茂催化剂和载体所聚合的乙烯-α-烯烃共聚物,该金属茂催化剂包括:具有配位体(其中具有环戊二烯型阴离子骨架的两个基团经由桥连基团键合)的过渡金属化合物与具有配位体(其中具有环戊二烯型阴离子骨架的基团和具有芴基型阴离子骨架的基团经由桥连基团键合)的过渡金属化合物的组合;所述载体通过将甲基铝氧烷作为助催化剂担载于多孔硅石的处理所获得。
专利文献1:日本特开 2003-96125 公报
专利文献2:日本特开
2004-149761 公报
专利文献3:日本特开 2006-233206
公报。
然而,虽然在描述于专利文献1和2中的乙烯-α-烯烃共聚物中,与使用先前的金属茂催化剂所聚合的乙烯-α-烯烃共聚物相比在成型加工时的挤出负荷减少,但是,仍然需要挤出负荷的进一步降低。描述于专利文献3中的乙烯-α-烯烃共聚物在其主链中未导入足够的长链分支,在应变硬化特性及成型时的卷取性能方面不能令人十分满意。
发明内容
在这种情况下,本发明所要解决的问题是提供挤出负荷低,熔融张力高,并且熔融的共聚物在恒定的张力条件下被卷取时的卷取性能优异、应变硬化特性优异、且二次加工性优异的乙烯-α-烯烃共聚物,以及将该共聚物挤出成型所获得的成型品。
本发明的第一项发明涉及乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,密度(d)为860-950 kg/m3,熔体流动速率(MFR)为0.01-100 g/10分,在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,特征松弛时间(τ)满足式(1)的关系,并且存在由差示扫描量热计(DSC)所观测的多个熔融峰。
40.2×MFR-0.606<τ<71.8×MFR-0.175 式(1)。
本发明的第二项发明涉及乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,密度(d)为860-950 kg/m3,熔体流动速率(MFR)为0.01-100 g/10分,在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,通过NMR测定的碳原子数5以上的分支数(NLCB)为0.1以上,并且存在由差示扫描量热计(DSC)所观测的多个熔融峰。
本发明的第三项发明涉及将上述乙烯-α-烯烃共聚物挤出成型而获得的成型体。
具体实施方式
本发明的第一实施方式涉及乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,密度(d)为860-950 kg/m3,熔体流动速率(MFR)为0.01-100 g/10分,在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,特征松弛时间(τ)满足式(1)的关系,并且存在由差示扫描量热计(DSC)所观测的多个熔融峰。
40.2×MFR-0.606<τ<71.8×MFR-0.175 式(1)。
本发明的第二实施方式涉及乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,密度(d)为860-950 kg/m3,熔体流动速率(MFR)为0.01-100 g/10分,在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,通过NMR测定的碳原子数5以上的分支数(NLCB)为0.1以上,并且由差示扫描量热计(DSC)所观测的多个熔融峰。
首先,对第一实施方式和第二实施方式所共同的要素进行详细说明。
本发明的乙烯-α-烯烃共聚物是具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元的乙烯-α-烯烃共聚物。该α-烯烃的例子可举出丙烯、1-丁烯、1-戊烯、1-己烯、1-庚烯、1-辛烯、1-壬烯、1-癸烯、1-十二碳烯、4-甲基-1-戊烯、4-甲基-1-己烯等,并且这些可以单独使用,或可以将它们中的两种以上组合使用。α-烯烃优选的是1-丁烯、1-己烯、4-甲基-1-戊烯、1-辛烯,更优选的是1-己烯、4-甲基-1-戊烯、1-辛烯。
除了上述基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元之外,本发明的乙烯-α-烯烃共聚物还可在不损害本发明效果的范围内具有基于其它单体的单体单元。其它单体的例子例如可举出共轭二烯(例如丁二烯、异戊二烯)、非共轭二烯(例如1,4-戊二烯)、丙烯酸、丙烯酸酯(例如丙烯酸甲酯、丙烯酸乙酯)、甲基丙烯酸、甲基丙烯酸酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯)、乙酸乙烯酯等。
在本发明的乙烯-α-烯烃共聚物中,基于乙烯的单体单元的含量相对于乙烯-α-烯烃共聚物的总重量(100 重量%)通常是50-99.5 重量%。另外,基于α-烯烃的单体单元的含量相对于乙烯-α-烯烃共聚物的总重量(100 重量%)通常是0.5-50 重量%。
本发明的乙烯-α-烯烃共聚物优选是具有基于乙烯的单体单元和基于碳原子数4-20的α-烯烃的单体单元的共聚物,更优选是具有基于乙烯的单体单元和基于碳原子数5-20的α-烯烃的单体单元的共聚物,进一步优选是具有基于乙烯的单体单元和基于碳原子数6-8的α-烯烃的单体单元的共聚物。
作为本发明的乙烯-α-烯烃共聚物,例如可举出乙烯-1-丁烯共聚物、乙烯-1-己烯共聚物、乙烯-4-甲基-1-戊烯共聚物、乙烯-1-辛烯共聚物、乙烯-1-丁烯-1-己烯共聚物、乙烯-1-丁烯-4-甲基-1-戊烯共聚物、乙烯-1-丁烯-1-辛烯共聚物、乙烯-1-己烯-1-辛烯共聚物等,优选是乙烯-1-己烯共聚物、乙烯-4-甲基-1-戊烯共聚物、乙烯-1-丁烯-1-己烯共聚物、乙烯-1-丁烯-1-辛烯共聚物、乙烯-1-己烯-1-辛烯共聚物。
本发明的乙烯-α-烯烃共聚物的密度(以下,有时记载为”d”)是860-950 kg/m3。从所得成型体的机械强度增强的观点考虑,密度优选是940 kg/m3以下,更优选935 kg/m3以下。此外,从所得成型体的刚性增强的观点考虑,密度优选是870
kg/m3以上,更优选880 kg/m3以上,进一步优选890 kg/m3以上,特别优选900
kg/m3以上。该密度是,在经过JIS K6760-1995中所述的退火之后,根据在JIS K7112-1980的方法A中规定的方法来测定的。乙烯-α-烯烃共聚物的密度能够通过在乙烯-α-烯烃共聚物中基于乙烯的单体单元的含量来改变。
本发明的乙烯-α-烯烃共聚物的熔体流动速率(以下,有时记载为“MFR”)通常是0.01-100 g/10分。从成型加工时的挤出负荷降低的观点考虑,该熔体流动速率优选是0.1 g/10分以上。此外,从所得成型体的机械强度增强的观点考虑,优选是50 g/10分以下,更优选30 g/10分以下,进一步优选15 g/10分以下。该熔体流动速率是在JIS K7210-1995中规定的方法中,在190℃的温度、21.18 N的载荷的条件下,由方法A所测定的值。乙烯-α-烯烃共聚物的熔体流动速率能够通过在下述的制造方法中的例如氢气浓度或聚合温度来改变,并且若氢气浓度或聚合温度升高,则乙烯-α-烯烃共聚物的熔体流动速率增大。
本发明的乙烯-α-烯烃共聚物显示出在高分子量侧具有宽分布的分子量分布,在由凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,在分子量177000的位置的GPC曲线的高度(H)是5%以上且30%以下,优选10%以上且25%以下。满足这种条件的本发明的乙烯-α-烯烃共聚物的挤出负荷低,并且应变硬化特性优异。当最高峰位置的分子量太高时,挤出负荷增大。乙烯-α-烯烃共聚物的最高峰位置的分子量在10000-20000的范围时,若在分子量177000的位置的GPC曲线的高度(H)低于5%,则高分子量成分少,不能表现出充分的应变硬化特性。
本发明的乙烯-α-烯烃共聚物是这样的共聚物,其中,在从该乙烯-α-烯烃共聚物的差示扫描量热测定获得的熔融曲线中,在25℃到熔融完成温度的范围内存在的熔融峰有多个。存在多个熔融峰表示在乙烯-α-烯烃共聚物的熔融曲线中存在着多个与最高熔融峰(具有最大峰高度的熔融峰)不同的熔融峰,并且意指乙烯-α-烯烃共聚物的组成分布(乙烯-α-烯烃共聚物中所含的各聚合物成分之间的单体单元的含有比例的分布)是宽的。本发明的乙烯-α-烯烃共聚物所具有的熔融峰的数量通常是2-5,优选是2-3。熔融峰的数量多的共聚物与同一密度的共聚物相比,可热封的温度范围变宽等,二次加工性优异。
应予说明,乙烯-α-烯烃共聚物的熔融曲线是采用差示扫描量热计(例如由Perkin
Elmer制造的差示扫描量热计DSC-7型)通过例如以下(4)的测定获得的差示扫描量热曲线得到的:将约10 mg的样品密封在铝盘中,(1)在150℃下保持5分钟,(2)以5℃/分钟从150℃降低至20℃,(3)在20℃下保持2分钟,(4)以5℃/分钟从20℃升温至熔融完成温度+约20℃(通常约150℃)。
本发明的乙烯-α-烯烃共聚物的重均分子量(以下,有时记载为“Mw”)与数均分子量(以下,有时记载为“Mn”)的比率(以下,有时记载为“Mw/Mn”)优选是4-30,Z均分子量(以下,有时记载为“Mz”)与重均分子量(Mw)的比率(以下,有时记载为“Mz/Mw”)优选是5-15。若Mw/Mn太小,则成型加工时的挤出负荷可能变高。Mw/Mn更优选是4.5以上,进一步优选5.5以上,特别优选6以上。若Mw/Mn太大或Mz/Mw太大,则所得成型体的机械强度可能变低。Mw/Mn优选是25以下,更优选是20以下,进一步优选是18以下。应予说明,该Mw/Mn和该Mz/Mw是通过GPC方法测定数均分子量(Mn)、重均分子量(Mw)和Z均分子量(Mz),将Mw除以Mn,将Mz除以Mw而获得的。该Mw/Mn能够通过在后面描述的制造方法中的例如氢气浓度来改变,并且若氢气浓度提高,则乙烯-α-烯烃共聚物的Mw/Mn变小。该Mz/Mw能够通过在后面描述的制造方法中的例如过渡金属化合物(B1)与过渡金属化合物(B2)的使用比率来改变。
为了抑制使用T模头将该共聚物挤出成型来制造膜时的缩幅,本发明的乙烯-α-烯烃共聚物的膨胀比(以下,有时记载为“SR”)优选是1.8以上。从提高挤出成型时的卷取性能的观点考虑,SR优选是3.2以下,更优选3.0以下。膨胀比是在测定熔体流动速率(MFR)时,将在190℃的温度、21.18 N的载荷的条件下以15-20 mm左右的长度从口型挤出的乙烯-α-烯烃共聚物的线料在空气中冷却,对于所得固体状线料,在距挤出上游侧前端约5 mm的位置测定线料的直径D(单位:mm),将该直径D除以口型直径2.095 mm(D0)所获得的值(D/D0)。膨胀比能够通过在后面描述的制造方法中的例如聚合时氢气浓度、乙烯压力或给电子性化合物浓度来改变,若提高氢气浓度,或降低乙烯压力时,乙烯-α-烯烃共聚物的膨胀比变大。此外,膨胀比能够通过在聚合时进行预聚合等来控制。
本发明的乙烯-α-烯烃共聚物的表示应变硬化的强度的拉伸粘度非线性指数k优选大于0.4,更优选大于0.7,进一步优选大于0.9,最优选大于1.1。若k小,则表示没有显示出足够的应变硬化,有可能在各种成型中产生不良情况。
拉伸粘度非线性指数k是对于曲线在t=1.5秒至2.5秒间的lnα(t)的斜率所计算的值,该曲线是:
α(t)=σ1(t)/σ0.1(t) (6)
通过将当在130℃的温度和1 s-1的Hencky速率下拉伸时熔融树脂的粘度-时间曲线σ1(t)除以当在130℃的温度和0.1 s-1的Hencky速率下拉伸时熔融树脂的粘度-时间曲线σ0.1(t)所获得的。
使用粘弹性测定装置(例如由TA Instrument制造的ARES等)进行熔融树脂的粘度-时间曲线σ(t)的测定。应予说明,测定在氮气氛下进行。
本发明的乙烯-α-烯烃共聚物的拉伸粘度非线性指数比k1/k2(在高应变区域中应变硬化的强度与在低应变区域中应变硬化的强度的比率)优选是0.8-1.1的范围。
在这里,k1是在时间t=2.0秒至2.5秒期间的lnα(t)的斜率,k2是在时间t=1.5秒至2.0秒期间的lnα(t)的斜率。即,当在高应变区域也显示出足够的应变硬化时,拉伸粘度非线性指数比k1/k2变成大的值,并且当在高应变区域中应变硬化不够时,其变成小的值。在先前的乙烯-α-烯烃共聚物中,在高应变区域中的应变硬化是不够的,但在本发明的乙烯-α-烯烃共聚物中,在高应变区域中可保持高的应变硬化特性。本发明的聚合物的k1/k2值更优选是0.9-1.1的范围。k1/k2能够通过调整氢气浓度等调节分子量来控制,当k1/k2为小的值时,能够通过提高氢气浓度,使分子量降低到合适的范围来提高k1/k2。
本发明的第一实施方式中,乙烯-α-烯烃共聚物的特征松弛时间(以下,有时记载为“τ”)满足以下关系式(1):
40.2×MFR-0.606<τ<71.8×MFR-0.175
式(1)
更优选满足式(1)’的关系式,进一步优选满足式(1)’’的关系式。
45.9×MFR-0.606<τ<66.3×MFR-0.175
式(1)’
51.7×MFR-0.606<τ<60.8×MFR-0.175
式(1)’’。
通常,已知存在足够络合的高分子满足下式。
τ=G・η0
式(2)。
在P.M.Wood-Adams等的论文(Macromolecules,
33, 7489 (2000))的Figure14中报道,在含有长链分支的茂金属聚乙烯中,η0与Mw的log-log作图能够用直线来表征。即,这强烈地暗示,含有长链分支的聚乙烯满足下式。
η0=H・Mwε 式(3)。
当将式(3)代入到式(2)中时,能够导出下式(4)。
τ=G’・MFRε 式(4)。
这里,使用表计算软件(例如,Microsoft Excel),针对在过渡金属化合物(B1):过渡金属化合物(B2)=12.5:1下并使氢气浓度以外的聚合条件基本上统一为一定的实施例的τ和MFR的标绘图,由(4)式进行拟合,并将拟合获得的G’值乘以1.3倍(在(1)’中将G’值乘以1.2倍,在(1)’’中将G’值乘以1.1倍),并且ε直接使用拟合所得到的结果,得到式(1)、(1)’和(1)’’的右边。另外,使用表计算软件(Microsoft
Excel),针对在无氢气条件下,在(B1):(B2)=12.5:1-60:1的范围内改变过渡金属化合物(B1)与过渡金属化合物(B2)的比值聚合而得到的乙烯-α-烯烃共聚物(也就是改变高分子量成分和低分子量成分之比而得到的乙烯-α-烯烃共聚物)的实施例的τ和MFR的标绘图,用(4)式进行拟合,并将拟合获得的G’值乘以0.7倍(在(1)’中将G’值乘以0.8倍,在(1)’’中将G’值乘以0.9倍),并且ε直接使用拟合所得到的结果,得到式(1)、(1)’和(1)’’的左边。
特征松弛时间(τ)是与乙烯-α-烯烃共聚物所具有的长链分支的长度和长链分支的量有关的数值,当长链分支短(或者长链分支量少)时,特征松弛时间变成小的值,当长链分支长(或者长链分支量多)时,特征松弛时间变成大的值。为了获得高熔融张力、高应变硬化特性,需要在分子链中导入足够量、或者足够长度的长链分支,并且优选的是具有恒定以上的弛豫时间。另一方面,具有过长的弛豫时间的聚合物虽然应变硬化特性高,但在相同的熔融张力下进行比较时,熔融树脂的最大卷取速率变慢。特征松弛时间能够通过例如氢气浓度、乙烯压力等聚合条件,或过渡金属化合物(B1)与过渡金属化合物(B2)的使用比率来改变,当过渡金属化合物(B2)的使用比率减少时,可以延长乙烯-α-烯烃共聚物的特征松弛时间。
特征松弛时间是基于温度-时间叠加原理而作成的,是从在190℃下显示熔融复数粘度(单位:Pa・sec)的角频率(单位:rad/sec)依赖性的主曲线所计算的数值。具体地说,这是通过如下所计算的值:基于温度-时间叠加原理,将在130℃、150℃、170℃和190℃的各温度(T,单位:℃)下乙烯-α-烯烃共聚物的熔融复数粘度-角频率曲线(熔融复数粘度的单位是Pa・sec,角频率的单位是rad/sec)重叠在190℃的熔融复数粘度-角频率曲线上以作成主曲线,并由下式(5)估算所得主曲线。
η=η0/[1+(τ×ω)n] (5)
η:熔融复数粘度(单位:Pa・sec)
ω:角频率(单位:rad/sec)
τ:特征松弛时间(单位:sec)
η0:对于每一种乙烯-α-烯烃共聚物所求出的常数(单位:Pa・sec)
n:对于每一种乙烯-α-烯烃共聚物所求出的常数。
上述计算可使用商购的计算软件,计算软件可以举出由Rheometrics社制造的Rhios V.4.4.4等。
通常在下列条件下使用粘弹性测定装置(例如由Rheometrics社制造的Rheometrics Mechanical Spectrometer RMS-800等)进行熔融复数粘度-角频率曲线的测定:几何结构:平行板,板直径:25mm,板间隔:1.5-2mm,应变:5%、角频率:0.1-100 rad/sec。应予说明,在氮气氛下进行测定,优选的是,预先将合适量(例如1000
ppm)的抗氧化剂配合到测定样品中。
本发明的第二实施方式中,从成型加工时的挤出负荷进一步降低的观点考虑,乙烯-α-烯烃共聚物的碳原子数5以上的分支数(以下,有时记载为“NLCB”)优选是0.1/1000碳(以下,将1000碳记作1000C)以上,更优选0.12/1000C以上。从所得成型体的机械强度增强的观点考虑,优选是1/1000C以下,更优选0.7/1000C以下,进一步优选0.5/1000C以下。乙烯-α-烯烃共聚物的NLCB能够通过在后述的制造方法中的例如给电子性化合物的浓度或过渡金属化合物(B1)与过渡金属化合物(B2)的使用比率来改变。另外,也能够通过进行预聚合来控制。
将在5-50 ppm观察到的全部峰面积的总和记为1000,通过由碳核磁共振(13C-NMR)方法测定的13C-NMR谱中求出由5个以上碳原子的分支所链合的次甲基碳所衍生的峰的面积,从而获得NLCB。在约38.2 ppm处观察到由5个以上碳原子的分支所键合的次甲基碳所衍生的峰(参见学术文献“Macromolecules”,(USA),American
Chemical Society,1999,vol. 32,p. 3817-3819)。由5个以上碳原子的分支所键合的次甲基碳所衍生的峰的位置有可能根据测定装置和测定条件而发生偏移,通常,通过对于每个测定装置和测定条件进行标准样品的测定来确定。对于光谱分析,优选将负指数函数用作窗口函数。
本发明的乙烯-α-烯烃共聚物是通过使用催化剂使乙烯和α-烯烃共聚所得到,该催化剂是通过在下列成分(A)存在下,使下列成分(B1)、下列成分(B2)、下列成分(C)和下列成分(D)接触所形成的。
成分(B1)与成分(B2)的摩尔比率((B1)/(B2))通常是1-90。
成分(A):乙烯和/或α-烯烃
成分(B1):由下列通式(1)表示的过渡金属化合物
其中M1表示在元素周期表中第4族的过渡金属原子;J1表示元素周期表中第14族的原子;m表示1-5的整数;X1、R1和R2是各自相同的或不同的,并且表示氢原子、卤素原子、可取代的碳原子数1-20的烃基、可取代的碳原子数1-20的烃氧基、碳原子数1-20的烃基甲硅烷基或碳原子数1-20的烃基氨基;多个X1彼此可以是相同或不同的;多个R1彼此可以是相同或不同的;多个R2彼此可以是相同或不同的。
成分(B2):由下列通式(2)表示的过渡金属化合物,
其中M2表示元素周期表中第4族的过渡金属原子;J2表示元素周期表中第14族的原子;n表示1-5的整数;X2、R3、R4和R5是各自相同或不同的,并且表示氢原子、卤素原子、可取代的碳原子数1-20的烃基、可取代的碳原子数1-20的烃氧基、碳原子数1-20的烃基甲硅烷基或碳原子数1-20的烃基氨基;多个X2彼此可以是相同或不同的;多个R3彼此可以是相同或不同的;多个R4彼此可以是相同或不同的;多个R5彼此可以是相同或不同的。
成分(C):下列成分(C-1)和/或下列成分(C-2)
成分(C-1):通过使下列成分(a)和下列成分(b)接触所形成的固体状催化剂成分
成分(a):选自(a-1)元素周期表第13族的有机金属化合物、(a-2)有机铝氧化合物、和(a-3)硼化合物中的至少一种化合物
成分(b):固体状载体
成分(C-2):使有机化合物和粘土矿物接触所形成的改性粘土矿物
成分(D):有机铝化合物。
成分(A)是用于聚合的单体,是乙烯和/或α-烯烃。α-烯烃碳原子数3-20的烯烃,例如可举出丙烯,1-丁烯,1-戊烯,1-己烯,1-庚烯,1-辛烯,1-壬烯,1-癸烯,1-十二碳烯,4-甲基-1-戊烯,4-甲基-1-己烯等。它们可以单独使用,或将两种以上结合使用。
这些当中,优选的是将乙烯与选自1-丁烯、1-己烯、4-甲基-1-戊烯和1-辛烯中的一种以上结合使用。
通式(1)中的M1和通式(2)中的M2表示元素周期表中第4族的过渡金属原子,例如可举出钛原子、锆原子、铪原子等。
通式(1)中的J1和通式(2)中的J2表示元素周期表中第14族的原子。优选的是碳原子或硅原子。
通式(1)中的m和通式(2)中的n是1-5的整数。m优选是1-2。N优选是1-2。
通式(1)中的X1、R1、R2,通式(2)中的X2、R3、R4和R5可以是彼此相同或不同的,是氢原子,卤素原子,可取代的碳原子数1-20的烃基,可取代的碳原子数1-20的烃氧基,碳原子数1-20的烃基甲硅烷基或碳原子数1-20的烃基氨基,多个X1彼此可以是相同或不同的,多个R1、R2彼此可以是相同或不同的,多个X2彼此可以是相同或不同的,多个R3、R4彼此可以是相同或不同的。
作为X1,R1,R2,X2,R3,R4和R5的卤素原子,可以举出氟原子、氯原子、溴原子、碘原子等。
作为X1,R1,R2,X2,R3,R4和R5的可取代的碳原子数1-20的烃基,可以举出碳原子数1-20的烷基,碳原子数1-20的卤代烷基,碳原子数7-20的芳烷基,碳原子数6-20的芳基等。
作为碳原子数1-20的烷基,例如可以举出甲基,乙基,正丙基,异丙基,正丁基,仲丁基,叔丁基,正戊基,新戊基,异戊基,正己基,正庚基,正辛基,正癸基,正壬基,正癸基,正十二烷基,正十二烷基,正十三烷基,正十四烷基,正十五烷基,正十六烷基,正十七烷基,正十八烷基,正十九烷基,正二十烷基等。
作为碳原子数1-20的卤代烷基,例如可以举出氟甲基,二氟甲基,三氟甲基,氯甲基,二氯甲基,三氯甲基,溴甲基,二溴甲基,三溴甲基,碘甲基,二碘甲基,三碘甲基,氟乙基,二氟乙基,三氟乙基,四氟乙基,五氟乙基,氯乙基,二氯乙基,三氯乙基,四氯乙基,五氯乙基,溴乙基,二溴乙基,三溴乙基,四溴乙基,五溴乙基,全氟丙基,全氟丁基,全氟戊基,全氟己基,全氟辛基,全氟十二烷基,全氟十五烷基,全氟二十烷基,全氯丙基,全氯丁基,全氯戊基,全氯己基,全氯辛基,全氯十二烷基,全氯十五烷基,全氯二十烷基,全溴丙基,全溴丁基,全溴戊基,全溴己基,全溴辛基,全溴十二烷基,全溴十五烷基,全溴二十烷基等。
作为碳原子数7-20的芳烷基,例如可以举出苄基,(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,(异丙基苯基)甲基,(正丁基苯基)甲基,(仲丁基苯基)甲基,(叔丁基苯基)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,(正癸基苯基)甲基,(正十四烷基苯基)甲基,萘基甲基,蒽基甲基,苯基乙基,苯基丙基,苯基丁基,二苯基甲基,二苯基乙基,二苯基丙基,二苯基丁基等。另外,可以举出这些芳烷基被氟原子,氯原子,溴原子或碘原子等卤素原子取代而成的卤代芳烷基等。
作为碳原子数6-20的芳基,例如可以举出苯基,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,二乙基苯基,三乙基苯基,正丙基苯基,异丙基苯基,正丁基苯基,仲丁基苯基,叔丁基苯基,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,正十二烷基苯基,正十四烷基苯基,萘基,蒽基等。另外,可以举出这些芳基被氟原子,氯原子,溴原子或碘原子等卤素原子取代而得的卤代芳基等。
作为可取代的碳原子数1-20的烃基,可以举出被烃基甲硅烷基取代的烃基,被烃基氨基取代的烃基,被烃氧基取代的烃基等。
作为被烃基甲硅烷基取代的烃基,可以举出三甲基甲硅烷基甲基,三甲基甲硅烷基乙基,三甲基甲硅烷基丙基,三甲基甲硅烷基丁基,三甲基甲硅烷基苯基,双(三甲基甲硅烷基)甲基,双(三甲基甲硅烷基)乙基,双(三甲基甲硅烷基)丙基,双(三甲基甲硅烷基)丁基,双(三甲基甲硅烷基)苯基,三苯基甲硅烷基甲基等。
作为被烃基氨基取代的烃基,可以举出二甲基氨基甲基,二甲基氨基乙基,二甲基氨基丙基,二甲基氨基丁基,二甲基氨基苯基,双(二甲基氨基)甲基,双(二甲基氨基)乙基,双(二甲基氨基)丙基,双(二甲基氨基)丁基,双(二甲基氨基)苯基,苯基氨基甲基,二苯基氨基甲基,二苯基氨基苯基等。
作为被烃氧基取代的烃基,可以举出甲氧基甲基,乙氧基甲基,正丙氧基甲基,异丙氧基甲基,正丁氧基甲基,仲丁氧基甲基,叔丁氧基甲基,苯氧基甲基,甲氧基乙基,乙氧基乙基,正丙氧基乙基,异丙氧基乙基,正丁氧基乙基,仲丁氧基乙基,叔丁氧基乙基,苯氧基乙基,甲氧基-正丙基,乙氧基-正丙基,正丙氧基-正丙基,异丙氧基-正丙基,正丁氧基-正丙基,仲丁氧基-正丙基,叔丁氧基-正丙基,苯氧基-正丙基,甲氧基异丙基,乙氧基异丙基,正丙氧基异丙基,异丙氧基异丙基,正丁氧基异丙基,仲丁氧基异丙基,叔丁氧基异丙基,苯氧基异丙基,甲氧基苯基,乙氧基苯基,正丙氧基苯基,异丙氧基苯基,正丁氧基苯基,仲丁氧基苯基,叔丁氧基苯基,苯氧基苯基等。
作为X1,R1,R2,X2,R3,R4和R5的可取代的碳原子数1-20的烃氧基,可以举出碳原子数1-20的烷氧基,碳原子数7-20的芳烷氧基,碳原子数6-20的芳氧基等。
作为碳原子数1-20的烷氧基,例如可以举出甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,仲丁氧基,叔丁氧基,正戊氧基,新戊氧基,正己氧基,正辛氧基,正壬氧基,正癸氧基,正十一烷氧基,正十二烷氧基,正十三烷氧基,正十四烷氧基,正十五烷氧基,正十六烷氧基,正十七烷氧基,正十七烷氧基,正十八烷氧基,正十九烷氧基,正二十烷氧基等。另外,可以举出这些烷氧基被氟原子,氯原子,溴原子或碘原子等卤素原子取代而得的卤代烷氧基等。
作为碳原子数7-20的芳烷氧基,例如可以举出苄基氧基,(2-甲基苯基)甲氧基,(3-甲基苯基)甲氧基,(4-甲基苯基)甲氧基,(2,3-二甲基苯基)甲氧基,(2,4-二甲基苯基)甲氧基,(2,5-二甲基苯基)甲氧基,(2,6-二甲基苯基)甲氧基,(3,4-二甲基苯基)甲氧基,(3,5-二甲基苯基)甲氧基,(2,3,4-三甲基苯基)甲氧基,(2,3,5-三甲基苯基)甲氧基,(2,3,6-三甲基苯基)甲氧基,(2,4,5-三甲基苯基)甲氧基,(2,4,6-三甲基苯基)甲氧基,(3,4,5-三甲基苯基)甲氧基,(2,3,4,5-四甲基苯基)甲氧基,(2,3,4,6-四甲基苯基)甲氧基,(2,3,5,6-四甲基苯基)甲氧基,(五甲基苯基)甲氧基,(乙基苯基)甲氧基,(正丙基苯基)甲氧基,(异丙基苯基)甲氧基,(正丁基苯基)甲氧基,(仲丁基苯基)甲氧基,(叔丁基苯基)甲氧基,(正己基苯基)甲氧基,(正辛基苯基)甲氧基,(正癸基苯基)甲氧基,(正十四烷基苯基)甲氧基,萘基甲氧基,蒽基甲氧基等。另外,可以举出这些芳烷氧基被氟原子,氯原子,溴原子或碘原子等卤素原子取代而得的卤代芳烷氧基等。
作为碳原子数6-20的芳氧基,例如可以举出苯氧基,2-甲基苯氧基,3-甲基苯氧基,4-甲基苯氧基,2,3-二甲基苯氧基,2,4-二甲基苯氧基,2,5-二甲基苯氧基,2,6-二甲基苯氧基,3,4-二甲基苯氧基,3,5-二甲基苯氧基,2,3,4-三甲基苯氧基,2,3,5-三甲基苯氧基,2,3,6-三甲基苯氧基,2,4,5-三甲基苯氧基,2,4,6-三甲基苯氧基,3,4,5-三甲基苯氧基,2,3,4,5-四甲基苯氧基,2,3,4,6-四甲基苯氧基,2,3,5,6-四甲基苯氧基,五甲基苯氧基,乙基苯氧基,正丙基苯氧基,异丙基苯氧基,正丁基苯氧基,仲丁基苯氧基,叔丁基苯氧基,正己基苯氧基,正辛基苯氧基,正癸基苯氧基,正十四烷基苯氧基,萘氧基,蒽氧基等。另外,可以举出这些芳氧基被氟原子,氯原子,溴原子或碘原子等卤素原子取代而得的卤代芳氧基等。
X1,R1,R2,X2,R3,R4和R5的碳原子数1-20的烃基甲硅烷基是被碳原子数1-20的烃基取代的甲硅烷基,作为碳原子数1-20的烃基,可以举出碳原子数1-20的烷基,碳原子数6-20的芳基等。作为碳原子数1-20的烃基甲硅烷基,例如可以举出碳原子数1-20的单烃基甲硅烷基,碳原子数2-20的二烃基甲硅烷基,碳原子数3-20的三烃基甲硅烷基等,作为碳原子数1-20的单烃基甲硅烷基,例如可以举出甲基甲硅烷基,乙基甲硅烷基,正丙基甲硅烷基,异丙基甲硅烷基,正丁基甲硅烷基,仲丁基甲硅烷基,叔丁基甲硅烷基,异丁基甲硅烷基,正戊基甲硅烷基,正己基甲硅烷基,苯基甲硅烷基等,作为碳原子数2-20的二烃基甲硅烷基,例如可以举出二甲基甲硅烷基,二乙基甲硅烷基,二正丙基甲硅烷基,二异丙基甲硅烷基,二正丁基甲硅烷基,二仲丁基甲硅烷基,二叔丁基甲硅烷基,二异丁基甲硅烷基,二苯基甲硅烷基等,作为碳原子数3-20的三烃基甲硅烷基,例如可以举出三甲基甲硅烷基,三乙基甲硅烷基,三正丙基甲硅烷基,三异丙基甲硅烷基,三正丁基甲硅烷基,三仲丁基甲硅烷基,三叔丁基甲硅烷基,三异丁基甲硅烷基,叔丁基二甲基甲硅烷基,三正戊基甲硅烷基,三正己基甲硅烷基,三环己基甲硅烷基,三苯基甲硅烷基等。
X1,R1,R2,X2,R3,R4和R5的碳原子数1-20的烃基氨基是被碳原子数1-20的烃基取代的氨基,作为碳原子数1-20的烃基,可以举出碳原子数1-20的烷基,碳原子数6-20的芳基,碳原子数7-20的芳烷基等。作为碳原子数1-20的烃基氨基,例如可以举出碳原子数1-20的单烃基氨基,碳原子数2-20的二烃基氨基等,作为碳原子数1-20的单烃基氨基,例如可以举出甲基氨基,乙基氨基,正丙基氨基,异丙基氨基,正丁基氨基,仲丁基氨基,叔丁基氨基,异丁基氨基,正己基氨基,正辛基氨基,正癸基氨基,苯基氨基,苄基氨基等,作为碳原子数2-20的二烃基氨基,例如可以举出二甲基氨基,二乙基氨基,二正丙基氨基,二异丙基氨基,二正丁基氨基,二仲丁基氨基,二叔丁基氨基,二异丁基氨基,叔丁基异丙基氨基,二正己基氨基,二正辛基氨基,二正癸基氨基,二苯基氨基,二苄基氨基,叔丁基异丙基氨基,苯基乙基氨基,苯基丙基氨基,苯基丁基氨基,吡咯基,吡咯烷基,哌啶基,咔唑基,二氢异吲哚基等。
X1优选是氯原子,甲基,乙基,正丙基,异丙基,正丁基,甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,三氟甲氧基,苯基,苯氧基,2,6-二叔丁基苯氧基,3,4,5-三氟苯氧基,五氟苯氧基,2,3,5,6-四氟-4-五氟苯基苯氧基,苄基。
R1优选是氢原子,碳原子数1-6的烷基,更优选氢原子,碳原子数1-4的烷基,进一步优选氢原子。
R2优选是碳原子数1-6的烷基,更优选碳原子数1-4的烷基。
X2优选是氯原子,甲基,乙基,正丙基,异丙基,正丁基,甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,三氟甲氧基,苯基,苯氧基,2,6-二叔丁基苯氧基,3,4,5-三氟苯氧基,五氟苯氧基,2,3,5,6-四氟-4-五氟苯基苯氧基,苄基。
R3优选是氢原子,碳原子数1-6的烷基,更优选氢原子,碳原子数1-4的烷基,进一步优选氢原子。
R4优选是氢原子,碳原子数1-6的烷基,更优选氢原子,碳原子数1-4的烷基,进一步优选氢原子。
R5优选是碳原子数1-6的烷基,更优选碳原子数1-4的烷基。
作为由通式(1)表示的成分(B1)的过渡金属化合物,当M1是锆原子、X1是氯原子时,可以举出:
二氯化亚甲基双(环戊二烯基)锆,
二氯化异丙叉基双(环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(环戊二烯基)锆,
二氯化二苯基亚甲基双(环戊二烯基)锆,
二氯化亚乙基双(环戊二烯基)锆,
二氯化亚甲基双(甲基环戊二烯基)锆,
二氯化异丙叉基双(甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(甲基环戊二烯基)锆,
二氯化二苯基亚甲基双(甲基环戊二烯基)锆,
二氯化亚乙基双(甲基环戊二烯基)锆,
二氯化亚甲基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化异丙叉基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二苯基亚甲基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化亚乙基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化亚甲基双(2,3-二甲基环戊二烯基)锆,
二氯化亚甲基双(2,4-二甲基环戊二烯基)锆,
二氯化亚甲基双(2,5-二甲基环戊二烯基)锆,
二氯化亚甲基双(3,4-二甲基环戊二烯基)锆,
二氯化异丙叉基双(2,3-二甲基环戊二烯基)锆,
二氯化异丙叉基双(2,4-二甲基环戊二烯基)锆,
二氯化异丙叉基双(2,5-二甲基环戊二烯基)锆,
二氯化异丙叉基双(3,4-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(2,3-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(2,4-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(2,5-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)亚甲基双(3,4-二甲基环戊二烯基)锆,
二氯化二苯基亚甲基双(2,3-二甲基环戊二烯基)锆,
二氯化二苯基亚甲基双(2,4-二甲基环戊二烯基)锆,
二氯化二苯基亚甲基双(2,5-二甲基环戊二烯基)锆,
二氯化二苯基亚甲基双(3,4-二甲基环戊二烯基)锆,
二氯化亚乙基双(2,3-二甲基环戊二烯基)锆,
二氯化亚乙基双(2,4-二甲基环戊二烯基)锆,
二氯化亚乙基双(2,5-二甲基环戊二烯基)锆,
二氯化亚乙基双(3,4-二甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(环戊二烯基)锆,
二氯化二乙基硅烷二基双(环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(环戊二烯基)锆,
二氯化二异丙基硅烷二基双(环戊二烯基)锆,
二氯化二环己基硅烷二基双(环戊二烯基)锆,
二氯化二苯基硅烷二基双(环戊二烯基)锆,
二氯化二(对甲苯基)硅烷二基双(环戊二烯基)锆,
二氯化二乙烯基硅烷二基双(环戊二烯基)锆,
二氯化二烯丙基硅烷二基双(环戊二烯基)锆,
二氯化(甲基)(乙烯基)硅烷二基双(环戊二烯基)锆,
二氯化(烯丙基)(甲基)硅烷二基双(环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(环戊二烯基)锆,
二氯化(环己基)(甲基)双(环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(环戊二烯基)锆,
二氯化二甲基硅烷二基双(甲基环戊二烯基)锆,
二氯化二乙基硅烷二基双(甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基双(甲基环戊二烯基)锆,
二氯化二环己基硅烷二基双(甲基环戊二烯基)锆,
二氯化二苯基硅烷二基双(甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(甲基环戊二烯基)锆,
二氯化(环己基)(甲基)双(甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(甲基环戊二烯基)锆,
二氯化二甲基硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二乙基硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二环己基硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二苯基硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(环己基)(甲基)(环戊二烯基)(甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基(环戊二烯基)(甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二甲基硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化二乙基硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二乙基硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二乙基硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二乙基硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二(正丙基)硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二异丙基硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化二环己基硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二环己基硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二环己基硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二环己基硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化二苯基硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化二苯基硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化二苯基硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化二苯基硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化(乙基)(甲基)硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化(甲基)(正丙基)硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化(甲基)(异丙基)硅烷二基双(3,4-二甲基环戊二烯基)锆,
二氯化(环己基)(甲基)双(2,3-二甲基环戊二烯基)锆,
二氯化(环己基)(甲基)双(2,4-二甲基环戊二烯基)锆,
二氯化(环己基)(甲基)双(2,5-二甲基环戊二烯基)锆,
二氯化(环己基)(甲基)双(3,4-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(2,3-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(2,4-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(2,5-二甲基环戊二烯基)锆,
二氯化(甲基)(苯基)硅烷二基双(3,4-二甲基环戊二烯基)锆等。
对于在以上例子中的η5-环戊二烯基的取代体,在桥连基团处于1-位时,若为单取代体,可,包括2-位,3-位,4-位,和5-位的取代体,即使桥连位置是除1-位以外的其它位置时,类似地包括所有组合。同样地对于二取代体以上的情况,包括取代基和桥连位置的全部组合。另外,其可以例举这样的化合物,其中将过渡金属化合物的X1的二氯变更为二氟,二溴,二碘,二甲基,二乙基,二异丙基,二甲醇盐,二乙醇盐,二丙醇盐,二丁醇盐,双(三氟甲醇盐),二苯基,二苯酚盐,双(2,6-二叔丁基苯酚盐),双(3,4,5-三氟苯酚盐),双(五氟苯酚盐),双(2,3,5,6-四氟-4-五氟苯基苯酚盐),二苄基等。此外,可以例举将过渡金属化合物的M1的锆变更为钛或铪所得的化合物。
由通式(1)表示的成分(B1)的过渡金属化合物优选是二氯化二甲基硅烷二基双(环戊二烯基)锆,二氯化异丙叉基双(环戊二烯基)锆。
作为由通式(2)表示的成分(B2)的过渡金属化合物,当M2是锆原子、X2是氯原子、桥连基团[-(J2(R5)2)n-]是二苯基亚甲基时,可以举出:
二氯化二苯基亚甲基(1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-二甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-二甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-二甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四甲基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-二乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-二乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-二乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四乙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-二正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-二正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-二正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四正丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-二异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-二异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-二异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四异丙基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-二苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-二苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-二苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四苯基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2-三甲基甲硅烷基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3-三甲基甲硅烷基-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,4-双(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,5-双(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4-双(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四(三甲基甲硅烷基)-1-环戊二烯基)(9-芴基)锆,
二氯化二苯基亚甲基(1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四甲基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四乙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四正丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四异丙基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四苯基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2-三甲基甲硅烷基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3-三甲基甲硅烷基-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二甲基-9-芴基)锆,
二氯化二苯基亚甲基(1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四甲基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四乙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四正丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四异丙基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四苯基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2-三甲基甲硅烷基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3-三甲基甲硅烷基-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二乙基-9-芴基)锆,
二氯化二苯基亚甲基(1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四甲基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四乙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四正丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四异丙基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-二苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-二苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-二苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四苯基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2-三甲基甲硅烷基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3-三甲基甲硅烷基-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,5-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4-双(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(3,4,5-三(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆,
二氯化二苯基亚甲基(2,3,4,5-四(三甲基甲硅烷基)-1-环戊二烯基)(2,7-二叔丁基-9-芴基)锆等。
还可以例举这样的化合物,其中将上述过渡金属化合物的X2的二氯变更为二氟,二溴,二碘,二甲基,二乙基,二异丙基,二甲醇盐,二乙醇盐,二丙醇盐,二丁醇盐,双(三氟甲醇盐),二苯基,二苯酚盐,双(2,6-二叔丁基苯酚盐),双(3,4,5-三氟苯酚盐),双(五氟苯酚盐),双(2,3,5,6-四氟-4-五氟苯基苯酚盐),二苄基等。另外,还可以例举这样的化合物,其中将上述过渡金属化合物的桥连基团[-(J2(R5)2)n-]的二苯基亚甲基变更为亚甲基,亚乙基,异丙叉基,甲基苯基亚甲基,二甲基硅烷二基,二苯基硅烷二基,硅杂环丁烷二基,硅杂环己烷二基等。此外,还可以例举将上述过渡金属化合物的M2的锆变更为钛或铪而得的化合物。
由通式(2)表示的成分(B2)的过渡金属化合物优选是二氯化二苯基亚甲基(1-环戊二烯基)(9-芴基)锆。
成分(C)是上述成分(C-1)和/或上述成分(C-2)。
成分(C-1)是使上述成分(a)与上述成分(b)接触所形成的固体状催化剂成分。
成分(a)中使用的成分(a-1)的元素周期表第13族的有机金属化合物优选是有机铝化合物。作为有机铝化合物,例如可以举出三烷基铝,二烷基氯化铝,烷基二氯化铝,二烷基氢化铝,烷基(二烷氧基)铝,二烷基(烷氧基)铝,烷基(二芳氧基)铝,二烷基(芳氧基)铝等。
作为三烷基铝,例如可以举出三甲基铝,三乙基铝,三正丙基铝,三正丁基铝,三异丁基铝,三正己基铝,三正辛基铝等。
作为二烷基氯化铝,例如可以举出二甲基氯化铝,二乙基氯化铝,二正丙基氯化铝,二正丁基氯化铝,二异丁基氯化铝,二正己基氯化铝等。
作为烷基二氯化铝,例如可以举出甲基二氯化铝,乙基二氯化铝,正丙基二氯化铝,正丁基二氯化铝,异丁基二氯化铝,正己基二氯化铝等。
作为二烷基氢化铝,例如可以举出二甲基氢化铝,二乙基氢化铝,二正丙基氢化铝,二正丁基氢化铝,二异丁基氢化铝,二正己基氢化铝等。
作为烷基(二烷氧基)铝,例如可以举出甲基(二甲氧基)铝,甲基(二乙氧基)铝,甲基(二叔丁氧基)铝等。
作为二烷基(烷氧基)铝,例如可以举出二甲基(甲氧基)铝,二甲基(乙氧基)铝,甲基(叔丁氧基)铝等。
作为烷基(二芳氧基)铝,例如可以举出甲基(二苯氧基)铝,甲基双(2,6-二异丙基苯氧基)铝,甲基双(2,6-二苯基苯氧基)铝等。
作为二烷基(芳氧基)铝,例如可以举出二甲基(苯氧基)铝,二甲基(2,6-二异丙基苯氧基)铝,二甲基(2,6-二苯基苯氧基)铝等。
可以使用这些有机铝化合物中的单独一种,或可以将它们中的两种以上结合使用。
有机铝化合物优选是三烷基铝,更优选三甲基铝,三乙基铝,三正丁基铝,三异丁基铝,三正己基铝或三正辛基铝,进一步优选三异丁基铝或三正辛基铝。
作为成分(a)中使用的成分(a-2)的有机铝氧化合物,例如可以举出下列式[1]表示的环状铝氧烷,下列式[2]表示的线状铝氧烷等。
{-Al(R6)-O-}i
[1]
其中,R6表示烃基,多个R6彼此可以是相同或不同的。i表示2以上的整数。
R7{-Al(R7)-O-}jAlR7 2
[2]
其中,R7表示烃基,多个R7彼此可以是相同或不同的。j表示1以上的整数。
式[1]中的R6和式[2]中的R7的烃基优选是碳原子数1-8的烃基,更优选碳原子数1-8的烷基。作为碳原子数1-8的烷基,例如可以举出甲基,乙基,正丙基,异丙基,正丁基,异丁基,正戊基,新戊基等,优选是甲基或异丁基。
式[1]中的i优选是2-40的整数,式[2]中的j优选是1-40的整数。
式[1]表示的环状铝氧烷和式[2]表示的线状铝氧烷能够通过各种方法来制造。它们的制造方法没有特别限定,可以是公知的制造方法。作为制造方法,可以举出:使将三甲基铝这样的三烷基铝溶解在苯和脂肪烃这样的适当的有机溶剂中而得到的溶液与水接触来制造的方法,将三甲基铝这样的三烷基铝与硫酸铜水合物这样的含有结晶水的金属盐接触来制造的方法。这些有机铝氧化合物可以单独使用一种,或将两种以上结合使用。优选的是由三甲基铝或三异丁基铝制备的有机铝氧化合物。
成分(a)中使用的成分(a-3)硼化合物使用的是选自(c-1)通式BQ1Q2Q3表示的硼化合物,(c-2)通式G+(BQ1Q2Q3Q4)-表示的硼化合物,(c-3)通式(L-H)+(BQ1Q2Q3Q4)-表示的硼化合物中的一种以上硼化合物。
在通式BQ1Q2Q3表示的硼化合物(c-1)中,B是3价的原子价状态的硼原子,Q1-Q3是卤素原子,烃基,卤代烃基,取代甲硅烷基,烷氧基,或2取代氨基,它们可以是相同或不同的。Q1-Q3优选的是卤素原子,包含1-20个碳原子的烃基,包含1-20个碳原子的卤代烃基,包含1-20个碳原子的取代甲硅烷基,包含1-20个碳原子的烷氧基,或包含2-20个碳原子的氨基,更优选的Q1-Q3是卤素原子,包含1-20个碳原子的烃基、或包含1-20个碳原子的卤代烃基。
更优选是Q1-Q4分别为包含至少一个氟原子的碳原子数1-20的氟化烃基,特别优选是Q1-Q4分别为包含至少一个氟原子的碳原子数6-20的氟代芳基。
作为化合物(c-1)的具体例子,可以列举三(五氟苯基)硼烷,三(2,3,5,6-四氟苯基)硼烷,三(2,3,4,5-四氟苯基)硼烷,三(3,4,5-三氟苯基)硼烷,三(2,3,4-三氟苯基)硼烷,苯基双(五氟苯基)硼烷等,最优选是三(五氟苯基)硼烷。
在通式G+(BQ1Q2Q3Q4)-表示的硼化合物(c-2)中,G+是无机或有机的阳离子,B是3价的原子价状态的硼原子,Q1-Q4与上述(c-1)中的Q1-Q3相同。
通式G+(BQ1Q2Q3Q4)-表示的化合物中,作为无机阳离子G+的具体例子,可以列举二茂铁阳离子,烷基取代二茂铁阳离子,银阳离子等,作为有机阳离子G+,可以举出三苯基甲基阳离子等。G+优选是碳正离子,特别优选是三苯基甲基阳离子。作为(BQ1Q2Q3Q4)-,可以举出四(五氟苯基)硼酸酯、四(2,3,5,6-四氟苯基)硼酸酯、四(2,3,4,5-四氟苯基)硼酸酯、四(3,4,5-三氟苯基)硼酸酯、四(2,3,4-三氟苯基)硼酸酯、苯基三(五氟苯基)硼酸酯、四(3,5-双三氟甲基苯基)硼酸酯等。
作为它们的具体的组合,可以举出二茂铁四(五氟苯基)硼酸盐、1,1’-二甲基二茂铁四(五氟苯基)硼酸盐、四(五氟苯基)硼酸银、三苯基甲基四(五氟苯基)硼酸酯、三苯基甲基四(3,5-双三氟甲基苯基)硼酸酯等,最优选是三苯基甲基四(五氟苯基)硼酸酯。
另外,在通式(L-H)+(BQ1Q2Q3Q4)-表示的硼化合物(c-3)中,L是中性路易斯碱,(L-H)+是布朗斯台德酸,B是3价的原子价状态的硼原子,Q1-Q4与上述的路易斯酸(c-1)中的Q1-Q3相同。
通式(L-H)+(BQ1Q2Q3Q4)-表示的化合物中的布朗斯台德酸(L-H)+的具体例子可以举出三烷基取代铵,N,N-二烷基苯胺盐,二烷基铵,三芳基鏻等,作为(BQ1Q2Q3Q4)-,可以举出与上述相同的基团。
作为它们的具体的组合,可以举出三乙基铵四(五氟苯基)硼酸酯,三丙基铵四(五氟苯基)硼酸盐,三(正丁基)铵四(五氟苯基)硼酸盐,三(正丁基)铵四(3,5-双三氟甲基苯基)硼酸盐,N,N-二甲基苯胺四(五氟苯基)硼酸盐,N,N-二乙基苯胺四(五氟苯基)硼酸盐,N,N-2,4,6-五甲基苯胺四(五氟苯基)硼酸盐,N,N-二甲基苯胺四(3,5-双三氟甲基苯基)硼酸盐,二异丙基铵四(五氟苯基)硼酸盐,二环己基铵四(五氟苯基)硼酸盐,三苯基鏻四(五氟苯基)硼酸盐,三(甲基苯基)鏻四(五氟苯基)硼酸盐,三(二甲基苯基)鏻四(五氟苯基)硼酸盐等,最优选是三(正丁基)铵四(五氟苯基)硼酸盐,或N,N-二甲基苯胺四(五氟苯基)硼酸盐。
成分(a)优选是成分(a-2)的有机铝氧化合物。
成分(b)中使用的固体状载体是无机或有机化合物,并且是颗粒状或微粒状的固体,上述这样的各种成分被担载于下列固体状载体。
其中,无机化合物例如有多孔氧化物、无机氯化物、粘土、粘土矿物,或离子交换性层状化合物,优选可以使用后面描述的多孔氧化物、无机氯化物。
多孔氧化物具体可以使用SiO2,Al2O3,MgO,ZrO,TiO2,B2O3,CaO,ZnO,BaO,ThO2等,或包含它们的复合物或混合物,可以使用例如天然或合成沸石,SiO2-MgO,SiO2-Al2O3,SiO2-TiO2,SiO2-V2O5,SiO2-Cr2O3,SiO2-TiO2-MgO等。它们之中,优选以SiO2为主要成分。
应予说明,上述无机氧化物还可以包含少量的Na2CO3,K2CO3,CaCO3,MgCO3,Na2SO4,Al2(SO4)3,BaSO4,KNO3,Mg(NO3)2,Al(NO3)3,Na2O,K2O,Li2O等碳酸盐,硫酸盐,硝酸盐,氧化物成分。
此类多孔氧化物根据其种类和制造方法的不同,其性状也不同,本发明优选使用的载体的粒径是0.2-300 μm,优选是1-200 μm,其比表面积在50-1200 m2/g,优选在100-1000 m2/g的范围,其孔容优选在0.3-30
cm3/g的范围。此类载体根据需要在100-1000℃,优选在150-700℃下烧成后使用。
无机氯化物可使用MgCl2,MgBr2,MnCl2,MnBr2等。无机氯化物可以直接使用,也可以通过球磨,振动磨粉碎后使用。此外,还可以使用将无机氯化物溶解在醇等溶剂中之后利用析出剂析出成微粒状的无机氯化物。
本发明中使用的粘土通常以粘土矿物为主要成分所构成。本发明中使用的离子交换性层状化合物是具有由离子键等构成的面相互之间以弱的键合力平行堆叠而成的晶体结构的化合物,并且所含有的离子能够交换。大部分粘土矿物是离子交换性层状化合物。此类粘土,粘土矿物,离子交换性层状化合物并不限于使用天然产物,也可以使用人工合成物。
粘土,粘土矿物或离子交换性层状化合物可以列举出粘土,粘土矿物,或六方致密堆积型,锑型,CdCl2型,CdI2型等具有层状的晶体结构的离子结晶性化合物等。
作为此类粘土、粘土矿物,可以举出高岭土,膨润土,木节粘土,蛙目粘土(gairome clay),铝英石(allophone),黑高岭土,叶蜡石,云母类,蒙脱土类,蛭石,绿泥石类,坡缕石,高岭石,珍珠陶土,地开石,埃洛石等,作为离子交换性层状化合物,可以举出α-Zr(HAsO4)2・H2O,α-Zr(HPO4)2,α-Zr(KPO4)2・3H2O,α-Ti(HPO4)2,α-Ti(HAsO4)2・H2O,α-Sn(HPO4)2・H2O,γ-Zr(HPO4)2,γ-Ti(HPO4)2,γ-Ti(NH4PO4)2・H2O等多价金属的结晶性酸性盐等。
这些粘土、粘土矿物或离子交换性层状化合物优选是利用水银压入法测定的半径20 Å以上的孔容为0.1 cc/g以上的物质,特别优选是0.3-5 cc/g。这里,孔容是通过利用水银测孔仪的水银压入法对细孔半径20-3×104
Å范围进行测定的值。
使用半径20 Å以上的孔容小于0.1 cc/g的粘土、粘土矿物或离子交换性层状化合物作为载体时,存在难以获得高聚合活性的倾向。
优选对本发明使用的粘土、粘土矿物实施化学处理。化学处理可以使用除去附着在表面的杂质的表面处理,对粘土的晶体结构赋予影响的处理等任何处理。化学处理的具体例子可例举酸处理,碱处理,盐类处理,有机物处理等。酸处理除了去除表面杂质的处理之外,还包括通过使晶体结构中的Al,Fe,Mg等的阳离子溶出来增加表面积。碱处理会使粘土的晶体结构破坏,从而使粘土的结构发生变化。盐类处理、有机物处理可形成离子复合体、分子复合体、有机衍生物等,从而改变表面积、层间距离。
本发明中使用的离子交换性层状化合物可以是通过利用离子交换性,将层间的交换性离子与其它大体积的离子进行交换而使层间扩大的状态的层状化合物。此类大体积离子承担支撑层状结构的支柱性的作用,通常被称为支柱。另外,将如此向层状化合物的层间导入其它物质的方法称为插入(intercalation)。作为进行插入的客体化合物,可以举出TiCl4,ZrCl4等阳离子性无机化合物,Ti(OR)4,Zr(OR)4,PO(OR)3,B(OR)3等金属烷氧化物(R是烃基等),[Al13O4(OH)24]7+,[Zr4(OH)14]2+,[Fe3O(OCOCH3)6]+等金属氢氧化物离子等。这些化合物可以单独使用一种,或将两种以上结合使用。此外,在将这些化合物进行插入时,还可以使Si(OR)4,Al(OR)3,Ge(OR)4等金属烷氧化物(R是烃基等)等水解所得到的聚合物、SiO2等胶体状无机化合物等共存。作为支柱,可以举出在层间插入上述金属氢氧化物离子后通过加热脱水而生成的氧化物等。
本发明中使用的粘土、粘土矿物、离子交换性层状化合物可以直接使用,也可以在进行球磨,筛分等处理后使用。还可以重新添加并附着水,或者在进行了加热脱水处理之后使用。此外,上述粘土、粘土矿物、离子交换性层状化合物可以单独使用一种,或将两种以上结合使用。
其中,优选的是粘土或粘土矿物,特别优选的是蒙脱土,蛭石,针钠钙石,黑铜矿,和合成云母。
作为有机化合物,可以举出粒径在10-300 μm范围的颗粒状或微粒状固体。具体可以列举以乙烯,丙烯,1-丁烯,4-甲基-1-戊烯等碳原子数2-14的烯烃为主要成分而生成的(共)聚合物或者以乙烯基环己烷,苯乙烯为主要成分而生成的(共)聚合物,以及它们的改性物。
成分(a)与成分(b)的接触时,通过成分(a)中的反应部位与成分(b)中的反应部位之间的反应而发生化学键合,从而形成成分(a)与成分(b)的接触产物。成分(a)与成分(b)之间的接触时间通常为20小时以下,优选是10小时以下,接触温度通常是-50-200℃,优选是-20-120℃。成分(a)与成分(b)的初期接触剧烈进行时,由其反应放热、反应能导致成分(b)破坏,所得到的固体状催化剂成分的形态学(morphology)发生恶化,在将其用于聚合时由于聚合物形态学不良而导致难以连续运转的情况较多。因此,为了抑制反应放热,优选是成分(a)与成分(b)的接触初期在低温下接触,或者使其缓慢进行反应。成分(a)与成分(b)的接触摩尔比(成分(a)/成分(b))可以任意选择,该摩尔比高时可以使成分(B1)与成分(B2)的总接触量增加,还可以提高单位固体状催化剂成分的活性,因此优选。
优选的范围是成分(a)与成分(b)的摩尔比[=成分(a)的摩尔量/成分(b)的摩尔量]通常为0.2-2.0,特别优选是0.4-2.0。
作为成分(C-1),优选是有机铝氧化合物与二氧化硅接触所形成的固体状催化剂成分,更优选是上述式[1]表示的环状的铝氧烷或上述式[2]表示的线状的铝氧烷与二氧化硅接触所形成的固体状催化剂成分。
成分(C-2)是有机化合物与粘土矿物接触所形成的改性粘土矿物。粘土矿物可以列举与上述成分(b)的粘土矿物所列举的同样的物质。
作为成分(C-2)中使用的有机化合物,例如可以举出下列式[3],下列式[4],或下列式[5]表示的化合物。这些当中,优选是下列通式[3]表示的化合物。
[R8R9 x-1M3H]m1[A1]n1
[3]。
式中,[A1]表示阴离子,[R8R9 x-1M3H]表示阳离子,M3表示元素周期表第15族或第16族的原子,R8表示烃基,R9各自独立地表示氢原子或烃基。当M3是第15族元素时,x表示3,当M3是第16族元素时,x表示2。m1和n1表示为使电荷平衡而选择的整数。
[C]m2[A2]n2
[4]。
(式中,[A2]表示阴离子,[C]表示碳阳离子或阳离子。m2和n2表示为使电荷平衡而选择的整数)。
[M4L3 y]m3[A3]n3
[5]。
式中,[A3]表示阴离子,M4表示锂原子,铁原子或银原子的阳离子,L3各自独立地表示路易斯碱,或者取代或未取代的环戊二烯基。Y表示0≤y≤2。m3和n3表示为使电荷平衡而选择的整数。
作为A1-A3的阴离子,例如可以举出氟离子,氯离子,溴离子,碘离子,硫酸根离子,硝酸根离子,磷酸根离子,高氯酸根离子,草酸根离子,柠檬酸根离子,苹果酸根离子,四氟硼酸离子,六氟磷酸根离子等。
作为M3的元素周期表第15族的原子,例如可以举出氮原子,磷原子等。作为M3的元素周期表第16族的原子,例如可以举出氧原子,硫原子等。
M3的R8和R9的烃基优选是碳原子数1-20的烃基。作为碳原子数1-20的烃基,例如可以举出甲基,乙基,正丙基,异丙基,烯丙基,正丁基,异丁基,仲丁基,叔丁基,正戊基,异戊基,2-甲基丁基,1-甲基丁基,1-乙基丙基,新戊基,叔戊基,环戊基,正己基,异己基,3-甲基戊基,4-甲基戊基,新己基,2,3-二甲基丁基,2,2-二甲基丁基,4-甲基-2-戊基,3,3-二甲基-2-丁基,1,1-二甲基丁基,2,3-二甲基-2-丁基,环己基,正庚基,环庚基,2-甲基环己基,3-甲基环己基,4-甲基环己基,正辛基,异辛基,1,5-二甲基己基,1-甲基庚基,2-乙基己基,叔辛基,2,3-二甲基环己基,2-(1-环己烯基)乙基,正壬基,正癸基,异癸基,香叶基,正十一烷基,正十二烷基,环十二烷基,正十三烷基,正十四烷基,正十五烷基,正十六烷基,正十七烷基,正十八烷基,正十九烷基,正二十烷基,正二十一烷基,正二十二烷基,正二十三烷基,油烯基,山萮基,苯基,邻甲苯基,间甲苯基,对甲苯基,2-乙基苯基,3-乙基苯基,4-乙基苯基,2-异丙基苯基,3-异丙基苯基,4-异丙基苯基,2-叔丁基苯基,4-正丁基苯基,4-仲丁基苯基,4-叔丁基苯基,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,2,6-二乙基苯基,2-异丙基-6-甲基苯基,2-氯苯基,3-氯苯基,4-氯苯基,2-溴苯基,3-溴苯基,4-溴苯基,2-甲氧基苯基,3-甲氧基苯基,4-甲氧基苯基,2-乙氧基苯基,3-乙氧基苯基,4-乙氧基苯基,1-萘基,2-萘基,1-芴基,2-芴基,3-芴基,4-芴基,2,3-二氢茚-5-基,2-联苯基,4-联苯基,对-三甲基甲硅烷基苯基等。另外,R8与R9也可以相互键合。
由上述式[3]表示的化合物中,当M3表示氮原子时,其例子包括例如甲基胺盐酸盐,乙基胺盐酸盐,正丙胺盐酸盐,异丙胺盐酸盐,正丁胺盐酸盐,异丁胺盐酸盐,叔丁胺盐酸盐,正戊基胺盐酸盐,异戊基胺盐酸盐,2-甲基丁基胺盐酸盐,新戊基胺盐酸盐,叔戊基胺盐酸盐,正己基胺盐酸盐,异己基胺盐酸盐,正庚基胺盐酸盐,正辛基胺盐酸盐,正壬基胺盐酸盐,正癸基胺盐酸盐,正十一烷基胺盐酸盐,正十二烷基胺盐酸盐,正十四烷基胺盐酸盐,正十六烷基胺盐酸盐,正十八烷基胺盐酸盐,烯丙基胺盐酸盐,环戊基胺盐酸盐,二甲基胺盐酸盐,二乙基胺盐酸盐,二烯丙基胺盐酸盐,三甲基胺盐酸盐,三正丁基胺盐酸盐,三烯丙基胺盐酸盐,己基胺盐酸盐,2-氨基庚烷盐酸盐,3-氨基庚烷盐酸盐,正庚基胺盐酸盐,1,5-二甲基己基胺盐酸盐,1-甲基庚基胺盐酸盐,正辛基胺盐酸盐,叔辛基胺盐酸盐,壬基胺盐酸盐,癸基胺盐酸盐,十一烷基胺盐酸盐,十二烷基胺盐酸盐,十三烷基胺盐酸盐,十四烷基胺盐酸盐,十五烷基胺盐酸盐,十六烷基胺盐酸盐,十七烷基胺盐酸盐,十八烷基胺盐酸盐,十九烷基胺盐酸盐,环己基胺盐酸盐,环庚基胺盐酸盐,2-甲基环己基胺盐酸盐,3-甲基环己基胺盐酸盐,4-甲基环己基胺盐酸盐,2,3-二甲基环己基胺盐酸盐,环十二烷基胺盐酸盐,2-(1-环己烯基)乙基胺盐酸盐,香叶基胺盐酸盐,N-甲基己基胺盐酸盐,二己基胺盐酸盐,双(2-乙基己基)胺盐酸盐,二辛基胺盐酸盐,二癸基胺盐酸盐,N-甲基环己基胺盐酸盐,N-乙基环己基胺盐酸盐,N-异丙基环己基胺盐酸盐,N-叔丁基环己基胺盐酸盐,N-烯丙基环己基胺盐酸盐,N,N-二甲基辛基胺盐酸盐,N,N-二甲基十一烷基胺盐酸盐,N,N-二甲基十二烷基胺盐酸盐,N,N-二甲基-正十四烷基胺盐酸盐,N,N-二甲基-正十六烷基胺盐酸盐,N,N-二甲基-正十八烷基胺盐酸盐,N,N-二甲基-正二十烷基胺盐酸盐,N,N-二甲基-正二十二烷基胺盐酸盐,N,N-二甲基油烯基胺盐酸盐,N,N-二甲基山萮基胺盐酸盐,三己基胺盐酸盐,三异辛基胺盐酸盐,三辛基胺盐酸盐,三异癸基胺盐酸盐,三十二烷基胺盐酸盐,N-甲基-正十八烷基-1-十八烷基胺盐酸盐,N,N-二甲基环己基胺盐酸盐,N,N-二甲基环己基甲基胺盐酸盐,N,N-二乙基环己基胺盐酸盐,吡咯烷盐酸盐,哌啶盐酸盐,2,5-二甲基吡咯烷盐酸盐,2-甲基哌啶盐酸盐,3-甲基哌啶盐酸盐,4-甲基哌啶盐酸盐,2,6-二甲基哌啶盐酸盐,3,3-二甲基哌啶盐酸盐,3,5-二甲基哌啶盐酸盐,2-乙基哌啶盐酸盐,2,2,6,6-四甲基哌啶盐酸盐,1-甲基吡咯烷盐酸盐,1-甲基哌啶盐酸盐,1-乙基哌啶盐酸盐,1-丁基吡咯烷盐酸盐,1,2,2,6,6-五甲基哌啶盐酸盐等脂肪族胺的盐酸盐;苯胺盐酸盐,N-甲基苯胺盐酸盐,N-乙基苯胺盐酸盐,N-烯丙基苯胺盐酸盐,邻甲苯胺盐酸盐,间甲苯胺盐酸盐,对甲苯胺盐酸盐,N,N-二甲基苯胺盐酸盐,N-甲基邻甲苯胺盐酸盐,N-甲基间甲苯胺盐酸盐,N-甲基对甲苯胺盐酸盐,N-乙基邻甲苯胺盐酸盐,N-乙基间甲苯胺盐酸盐,N-乙基对甲苯胺盐酸盐,N-烯丙基邻甲苯胺盐酸盐,N-烯丙基间甲苯胺盐酸盐,N-烯丙基对甲苯胺盐酸盐,N-丙基邻甲苯胺盐酸盐,N-丙基间甲苯胺盐酸盐,N-丙基对甲苯胺盐酸盐,2,3-二甲基苯胺盐酸盐,2,4-二甲基苯胺盐酸盐,2,5-二甲基苯胺盐酸盐,2,6-二甲基苯胺盐酸盐,3,4-二甲基苯胺盐酸盐,3,5-二甲基苯胺盐酸盐,2-乙基苯胺盐酸盐,3-乙基苯胺盐酸盐,4-乙基苯胺盐酸盐,N,N-二乙基苯胺盐酸盐,2-异丙基苯胺盐酸盐,4-异丙基苯胺盐酸盐,2-叔丁基苯胺盐酸盐,4-正丁基苯胺盐酸盐,4-仲丁基苯胺盐酸盐,4-叔丁基苯胺盐酸盐,2,6-二乙基苯胺盐酸盐,2-异丙基-6-甲基苯胺盐酸盐,2-氯苯胺盐酸盐,3-氯苯胺盐酸盐,4-氯苯胺盐酸盐,2-溴苯胺盐酸盐,3-溴苯胺盐酸盐,4-溴苯胺盐酸盐,邻甲氧基苯胺盐酸盐,间甲氧基苯胺盐酸盐,对甲氧基苯胺盐酸盐,邻乙氧基苯胺盐酸盐,间乙氧基苯胺盐酸盐,对乙氧基苯胺盐酸盐,1-氨基萘盐酸盐,2-氨基萘盐酸盐,1-氨基芴盐酸盐,2-氨基芴盐酸盐,3-氨基芴盐酸盐,4-氨基芴盐酸盐,5-氨基茚满盐酸盐,2-氨基联苯基盐酸盐,4-氨基联苯基盐酸盐,N,2,3-三甲基苯胺盐酸盐,N,2,4-三甲基苯胺盐酸盐,N,2,5-三甲基苯胺盐酸盐,N,2,6-三甲基苯胺盐酸盐,N,3,4-三甲基苯胺盐酸盐,N,3,5-三甲基苯胺盐酸盐,N-甲基-2-乙基苯胺盐酸盐,N-甲基-3-乙基苯胺盐酸盐,N-甲基-4-乙基苯胺盐酸盐,N-甲基-6-乙基-邻甲苯胺盐酸盐,N-甲基-2-异丙基苯胺盐酸盐,N-甲基-4-异丙基苯胺盐酸盐,N-甲基-2-叔丁基苯胺盐酸盐,N-甲基-4-正丁基苯胺盐酸盐,N-甲基-4-仲丁基苯胺盐酸盐,N-甲基-4-叔丁基苯胺盐酸盐,N-甲基-2,6-二乙基苯胺盐酸盐,N-甲基-2-异丙基-6-甲基苯胺盐酸盐,N-甲基对甲氧基苯胺盐酸盐,N-乙基-2,3-甲氧基苯胺盐酸盐,N,N-二甲基邻甲苯胺盐酸盐,N,N-二甲基间甲苯胺盐酸盐,N,N-二甲基对甲苯胺盐酸盐,N,N,2,3-四甲基苯胺盐酸盐,N,N,2,4-四甲基苯胺盐酸盐,N,N,2,5-四甲基苯胺盐酸盐,N,N,2,6-四甲基苯胺盐酸盐,N,N,3,4-四甲基苯胺盐酸盐,N,N,3,5-四甲基苯胺盐酸盐,N,N-二甲基-2-乙基苯胺盐酸盐,N,N-二甲基-3-乙基苯胺盐酸盐,N,N-二甲基-4-乙基苯胺盐酸盐,N,N-二甲基-6-乙基邻甲苯胺盐酸盐,N,N-二甲基-2-异丙基苯胺盐酸盐,N,N-二甲基-4-异丙基苯胺盐酸盐,N,N-二甲基-2-叔丁基苯胺盐酸盐,N,N-二甲基-4-正丁基苯胺盐酸盐,N,N-二甲基-4-仲丁基苯胺盐酸盐,N,N-二甲基-4-叔丁基苯胺盐酸盐,N,N-二甲基-2,6-二乙基苯胺盐酸盐,N,N-二甲基-2-异丙基-6-甲基苯胺盐酸盐,N,N-二甲基-2-氯苯胺盐酸盐,N,N-二甲基-3-氯苯胺盐酸盐,N,N-二甲基-4-氯苯胺盐酸盐,N,N-二甲基-2-溴苯胺盐酸盐,N,N-二甲基-3-溴苯胺盐酸盐,N,N-二甲基-4-溴苯胺盐酸盐,N,N-二甲基邻甲氧基苯胺盐酸盐,N,N-二甲基间甲氧基苯胺盐酸盐,N,N-二甲基对甲氧基苯胺盐酸盐,N,N-二甲基邻乙氧基苯胺盐酸盐,N,N-二甲基间乙氧基苯胺盐酸盐,N,N-二甲基对乙氧基苯胺盐酸盐,N,N-二甲基-1-氨基萘盐酸盐,N,N-二甲基-2-氨基萘盐酸盐,N,N-二甲基-1-氨基芴盐酸盐,N,N-二甲基-2-氨基芴盐酸盐,N,N-二甲基-3-氨基芴盐酸盐,N,N-二甲基-4-氨基芴盐酸盐,N,N-二甲基-5-氨基茚满盐酸盐,N,N-二甲基-2-氨基联苯基盐酸盐,N,N-二甲基-4-氨基联苯基盐酸盐,N,N-二甲基-对-三甲基甲硅烷基苯胺盐酸盐等芳族胺的盐酸盐,和将上述化合物的盐酸盐用氢氟酸盐,氢溴酸盐,氢碘酸盐或硫酸盐替换而得的化合物等。
上述式[3]表示的化合物中,当M3表示磷原子时,其例子包括例如三苯基膦盐酸盐,三(邻甲苯基)膦盐酸盐,三(对甲苯基)膦盐酸盐,三莱基膦盐酸盐等化合物,和将上述化合物的盐酸盐用氢氟酸盐,氢溴酸盐,氢碘酸盐或硫酸盐替换而得的化合物等。
上述式[3]表示的化合物中,当M3表示氧原子时,其例子包括例如甲基醚盐酸盐,乙基醚盐酸盐,正丁基醚盐酸盐,四氢呋喃盐酸盐、苯基醚盐酸盐等化合物,和将上述化合物的盐酸盐用氢氟酸盐,氢溴酸盐,氢碘酸盐或硫酸盐替换而得的化合物等。
上述式[3]表示的化合物中,当M3表示硫原子时,其例子包括例如氟化二乙基锍,氯化二乙基锍,溴化二乙基锍,碘化二乙基锍,氟化二甲基锍,氯化二甲基锍,溴化二甲基锍,碘化二甲基锍等。
作为上述式[4]表示的化合物,可以举出例如三苯甲基溴、三苯甲基氯、三苯甲基四氟硼酸酯、三苯甲基六氟磷酸酯、溴化、氯化、四氟硼酸、六氟磷酸等。
作为L3的路易斯碱,可以举出例如醚类,脂肪胺类,芳族胺类,膦类等。
作为上述式[5]表示的化合物,可以举出例如溴化二茂铁,氯化二茂铁,四氟硼酸二茂铁,六氟磷酸二茂铁等。
在成分(C-2)中的有机化合物与粘土矿物接触时,优选选择粘土矿物的浓度为0.1-30
重量%,接触温度为0-150℃的条件进行接触。有机化合物可以制成固体溶解在溶剂中使用,也可以通过在溶剂中的化学反应制成有机化合物的溶液后直接使用。对于粘土矿物与有机化合物的反应量比,优选使用粘土矿物的可交换的阳离子的当量以上的有机化合物。作为接触溶剂,可以举出例如脂肪烃类,芳香烃类,醇类,醚类,卤代烃类,酮类,水等。作为脂肪烃类,可以举出例如戊烷,己烷,庚烷等。作为芳香烃类,可以举出例如苯,甲苯等。作为醇类,可以举出例如乙醇,甲醇等。作为醚类,可以举出例如乙醚,正丁基醚,四氢呋喃、1,4-二噁烷等。作为卤代烃类,可以举出例如二氯甲烷,氯仿等。作为酮类,可以举出例如丙酮等。
这些接触溶剂可以单独使用一种,或将两种以上结合使用。这些接触溶剂中,优选是醇类或水。
成分(C)优选是有机铝氧化合物与二氧化硅接触所形成的固体状催化剂成分或有机化合物与粘土矿物接触所形成的改性粘土矿物,更优选是有机铝氧化合物与二氧化硅接触所形成的固体状催化剂成分,或上述式[3]、上述式[4]或上述式[5]表示的化合物与粘土矿物接触所形成的改性粘土矿物,进一步优选是有机铝氧化合物与二氧化硅接触所形成的固体状催化剂成分,特别优选是上述式[1]表示的环状的铝氧烷或上述式[2]表示的线状的铝氧烷与二氧化硅接触所形成的固体状催化剂成分。
相对于1g的成分(C),成分(B1)和成分(B2)的总用量优选是1×10-6-1×10-3 mol,更优选是5×10-6-1×10-4
mol。
本发明的乙烯-α-烯烃共聚物可以使用以下的成分(A)-(D)来制造。使用成分(A)-(D)来生产本发明的乙烯-α-烯烃共聚物时,使成分(B1)及成分(B2)和成分(C)以何种状态接触是重要的。成分(D)与其它成分接触的顺序是任意的。
为了生产本发明的乙烯-α-烯烃共聚物,需要在成分(A)存在下使成分(B1)及成分(B2)和成分(C)接触。即,在不存在成分(A)的状态下,不能使成分(B1)或成分(B2)与成分(C)预先接触。
成分(A):作为单体的乙烯和/或α-烯烃
成分(B1):下列通式(1)表示的过渡金属化合物
式中,M1表示元素周期表第4族的过渡金属原子,J1表示元素周期表第14族的原子,m表示1-5的整数,X1,R1和R2彼此相同或不同,表示氢原子,卤素原子,可取代的碳原子数1-20的烃基,可取代的碳原子数1-20的烃氧基,碳原子数1-20的烃基甲硅烷基或碳原子数1-20的烃基氨基,多个X1彼此可以是相同或不同的,多个R1彼此可以是相同或不同的,多个R2彼此可以是相同或不同的。
成分(B2):下列通式(2)表示的过渡金属化合物
式中,M2表示元素周期表第4族的过渡金属原子,J2表示元素周期表第14族的原子,n表示1-5的整数,X2,R3,R4和R5彼此相同或不同,表示氢原子,卤素原子,可取代的碳原子数1-20的烃基,可取代的碳原子数1-20的烃氧基,碳原子数1-20的烃基甲硅烷基或碳原子数1-20的烃基氨基,多个X2彼此可以是相同或不同的,多个R3彼此可以是相同或不同的,多个R4彼此可以是相同或不同的,多个R5彼此可以是相同或不同的。
成分(C):下列成分(C-1)和/或下列成分(C-2)
成分(C-1):下列成分(a)与下列成分(b)接触所形成的固体状催化剂成分
成分(a):选自(a-1)元素周期表第13族的有机金属化合物,(a-2)有机铝氧化合物,和(a-3)硼化合物中的至少一种化合物
成分(b):固体状载体
成分(C-2):有机化合物与粘土矿物接触所形成的改性粘土矿物
成分(D):有机铝化合物。
作为在成分(A)存在下使成分(B1),成分(B2)和成分(C)接触的方法,具体地可举出下列接触方法。
(1) 使成分(B1)和成分(B2)与存在有成分(A)的成分(C)接触的接触方法。
(2) 使成分(C)与存在有成分(A)的成分(B1)和成分(B2)接触的接触方法。
(3) 使存在有成分(A)的成分(B1)和成分(B2)与存在有成分(A)的成分(C)接触的接触方法。
(4) 使存在有成分(A)的成分(B1),存在有成分(A)的成分(B2),和成分(C)接触的接触方法。
(5) 使成分(B2),存在有成分(A)的成分(B1),和存在有成分(A)的成分(C)接触的接触方法。
(6) 使成分(B1),存在有成分(A)的成分(B2),和存在有成分(A)的成分(C)接触的接触方法。
在成分(A),成分(B1),成分(B2),成分(C)和成分(D)的接触时,成分(D)与其它成分的接触顺序是任意的,可以使成分(D)与成分(A),成分(B1),成分(B2)或成分(C)各自预先接触,也可以使存在有成分(A)的成分(B1)与成分(D)接触,还可以使存在有成分(A)的成分(B2)与成分(D)接触,还可以使存在有成分(A)的成分(B1)及成分(B2),和成分(D)接触,还可以使存在有成分(A)的成分(C)与成分(D)接触,还可以使存在有成分(A)的成分(B1)、成分(B2)和成分(C)的接触产物与成分(D)接触。
具体地,可以列举下列接触方法。
(1) 使存在有成分(A)的成分(B1)和成分(B2)与成分(C)接触,再进一步与成分(D)接触的接触方法。
(2) 使存在有成分(A)的成分(B1)和成分(B2)与成分(D)接触,再进一步与成分(C)接触的接触方法。
(3) 使存在有成分(A)的成分(C)与成分(B1)和成分(B2)接触,再进一步与成分(D)接触的接触方法。
(4) 使存在有成分(A)的成分(C)与成分(D)接触,再进一步与成分(B1)和成分(B2)接触的接触方法。
(5) 使存在有成分(A)的成分(D)与成分(B1)和成分(B2)接触,再进一步与成分(C)接触的接触方法。
(6) 使存在有成分(A)的成分(D)与成分(C)接触,再进一步与成分(B1)和成分(B2)接触的接触方法。
(7) 使成分(B1)、成分(B2)和成分(D)的接触产物与成分(C)在成分(A)存在下接触的接触方法。
(8) 使成分(C)和成分(D)的接触产物与成分(B1)和成分(B2)在成分(A)存在下接触的接触方法。
这些接触方法中,优选的是如上述(5)或(6)那样的使成分(B1),(B2)和(C)与存在有成分(A)的成分(D)以任意的顺序进行接触的方法。
作为成分(D)的有机铝化合物,可以举出例如三烷基铝,二烷基氯化铝,烷基二氯化铝,二烷基氢化铝,烷基(二烷氧基)铝,二烷基(烷氧基)铝,烷基(二芳氧基)铝,二烷基(芳氧基)铝等。
作为三烷基铝,可以举出例如三甲基铝,三乙基铝,三正丙基铝,三正丁基铝,三异丁基铝,三正己基铝,三正辛基铝等,作为二烷基氯化铝,可以举出例如二甲基氯化铝,二乙基氯化铝,二正丙基氯化铝,二正丁基氯化铝,二异丁基氯化铝,二正己基氯化铝等,作为烷基二氯化铝,可以举出例如甲基二氯化铝,乙基二氯化铝,正丙基二氯化铝,正丁基二氯化铝,异丁基二氯化铝,正己基二氯化铝等,作为二烷基氢化铝,可以举出例如二甲基氢化铝,二乙基氢化铝,二正丙基氢化铝,二正丁基氢化铝,二异丁基氢化铝,二正己基氢化铝等,作为烷基(二烷氧基)铝,可以举出例如甲基(二甲氧基)铝,甲基(二乙氧基)铝,甲基(二叔丁氧基)铝等,作为二烷基(烷氧基)铝,可以举出例如二甲基(甲氧基)铝,二甲基(乙氧基)铝,甲基(叔丁氧基)铝等,作为烷基(二芳氧基)铝,可以举出例如甲基(二苯氧基)铝,甲基双(2,6-二异丙基苯氧基)铝,甲基双(2,6-二苯基苯氧基)铝等,作为二烷基(芳氧基)铝,可以举出例如二甲基(苯氧基)铝,二甲基(2,6-二异丙基苯氧基)铝,二甲基(2,6-二苯基苯氧基)铝等。
这些有机铝化合物可以单独使用一种,或者可以将两种以上结合使用。
有机铝化合物优选是三烷基铝,更优选是三甲基铝,三乙基铝,三正丁基铝,三异丁基铝,三正己基铝,三正辛基铝,进一步优选是三异丁基铝,三正辛基铝。
相对于成分(B1)和成分(B2)的过渡金属原子的总摩尔数,成分(D)的用量以成分(D)有机铝化合物的铝原子的摩尔比(D)/((B1)+(B2))计优选是0.01-10000,更优选是0.1-5000,最优选是1-2000。
另外,在生产上述催化剂时,可以使用给电子性化合物(成分(E))。这样的给电子性化合物优选是包含氮原子,磷原子,氧原子或硫原子的化合物,可例举含氧化合物,含氮化合物,含磷化合物,含硫化合物,其中优选的是含氧化合物或含氮化合物。作为含氧化合物,可以举出烷氧基硅类,醚类,酮类,醛类,羧酸类,有机酸或无机酸的酯类,有机酸或无机酸的酰胺类,酸酐类等,其中优选是烷氧基硅类或醚类。作为含氮化合物,可以举出胺类,腈类,异氰酸酯类等,优选是胺类。
烷氧基硅类优选是下列式[6]表示的烷氧基硅化合物。
R10 kSi(OR11)4-k
[6]。
式中,R10表示碳原子数1-20的烃基,氢原子或含有杂原子的取代基,R11表示碳原子数1-20的烃基,k表示满足0≤k≤3的整数。具有多个R10时,多个R10可以是相同或不同的。具有多个OR11时,多个OR11可以是相同的或不同的。
作为R10和R11的碳原子数1-20的烃基,可以举出例如甲基,乙基,丙基,丁基,戊基等直链烷基,异丙基,仲丁基,叔丁基,叔戊基等支链烷基,环戊基,环己基等环烷基,环戊烯基等环烯基,苯基,甲苯基等芳基等。
作为R10的含有杂原子的取代基的杂原子,可以举出氧原子,氮原子,硫原子,磷原子。具体的,可以举出二甲基氨基,甲基乙基氨基,二乙基氨基,乙基正丙基氨基,二正丙基氨基,吡咯基,吡啶基,吡咯烷基,哌啶基,全氢吲哚基,全氢异吲哚基,全氢喹啉基,全氢异喹啉基,全氢咔唑基,全氢吖啶基,呋喃基,吡喃基,全氢呋喃基,噻吩基等。优选R10和R11是烷基,更优选R10和R11是烷基,且i为2或3。
作为上述烷氧基硅类的具体例子,可以举出四甲氧基硅烷,甲基三甲氧基硅烷,乙基三甲氧基硅烷,正丙基三甲氧基硅烷,异丙基三甲氧基硅烷,正丁基三甲氧基硅烷,异丁基三甲氧基硅烷,仲丁基三甲氧基硅烷,叔丁基三甲氧基硅烷,正戊基三甲氧基硅烷,叔戊基三甲氧基硅烷,二甲基二甲氧基硅烷,二乙基二甲氧基硅烷,二正丁基二甲氧基硅烷,二异丁基二甲氧基硅烷,二叔丁基二甲氧基硅烷,甲基乙基二甲氧基硅烷,甲基正丙基二甲氧基硅烷,甲基正丁基二甲氧基硅烷,甲基异丁基二甲氧基硅烷,叔丁基甲基二甲氧基硅烷,叔丁基乙基二甲氧基硅烷,叔丁基正丙基二甲氧基硅烷,叔丁基异丙基二甲氧基硅烷,叔丁基正丁基二甲氧基硅烷,叔丁基异丁基二甲氧基硅烷,叔戊基甲基二甲氧基硅烷,叔戊基乙基二甲氧基硅烷,叔戊基正丙基二甲氧基硅烷,叔戊基正丁基二甲氧基硅烷,异丁基异丙基二甲氧基硅烷,二环丁基二甲氧基硅烷,环丁基甲基二甲氧基硅烷,环丁基乙基二甲氧基硅烷,环丁基异丙基二甲氧基硅烷,环丁基正丁基二甲氧基硅烷,环丁基异丁基二甲氧基硅烷,环丁基-叔丁基二甲氧基硅烷,二环戊基二甲氧基硅烷,环戊基甲基二甲氧基硅烷,环戊基正丙基二甲氧基硅烷,环戊基异丙基二甲氧基硅烷,环戊基正丁基二甲氧基硅烷,环戊基异丁基二甲氧基硅烷,环戊基-叔丁基二甲氧基硅烷,二环己基二甲氧基硅烷,环己基甲基二甲氧基硅烷,环己基乙基二甲氧基硅烷,环己基正丙基二甲氧基硅烷,环己基异丙基二甲氧基硅烷,环己基正丁基二甲氧基硅烷,环己基异丁基二甲氧基硅烷,环己基叔丁基二甲氧基硅烷,环己基环戊基二甲氧基硅烷,环己基苯基二甲氧基硅烷,二苯基二甲氧基硅烷,苯基甲基二甲氧基硅烷,苯基乙基二甲氧基硅烷,苯基正丙基二甲氧基硅烷,苯基异丙基二甲氧基硅烷,苯基正丁基二甲氧基硅烷,苯基异丁基二甲氧基硅烷,苯基叔丁基二甲氧基硅烷,苯基环戊基二甲氧基硅烷,2-降冰片烷甲基二甲氧基硅烷,双(全氢喹啉基)二甲氧基硅烷,双(全氢异喹啉基)二甲氧基硅烷,(全氢喹啉基)(全氢异喹啉基)二甲氧基硅烷,(全氢喹啉基)甲基二甲氧基硅烷,(全氢异喹啉基)甲基二甲氧基硅烷,(全氢喹啉基)乙基二甲氧基硅烷,(全氢异喹啉基)乙基二甲氧基硅烷,(全氢喹啉基)(正丙基)二甲氧基硅烷,(全氢异喹啉基)(正丙基)二甲氧基硅烷,((全氢喹啉基)(叔丁基)二甲氧基硅烷,(全氢异喹啉基)(叔丁基)二甲氧基硅烷,三甲基甲氧基硅烷,三乙基甲氧基硅烷,三正丙基甲氧基硅烷,三异丙基甲氧基硅烷,三正丁基甲氧基硅烷,三异丁基甲氧基硅烷,三叔丁基甲氧基硅烷等。还可以列举将这些化合物的甲氧基用乙氧基,丙氧基,正丁氧基,异丁氧基,叔丁氧基,苯氧基替换而得的化合物。优选是二烷基二烷氧基硅烷或三烷基单烷氧基硅烷,更优选是三烷基单烷氧基硅烷。
作为醚类的例子,可以举出二烷基醚,烷基芳基醚,二芳基醚,二醚化合物,环状醚类和环状二醚类。
其具体例子可以举出二甲醚,二乙醚,二正丙基醚,二异丙基醚,二正丁基醚,二异丁基醚,二叔丁基醚,二环己基醚,二苯基醚,甲基乙基醚,甲基正丙基醚,甲基异丙基醚,甲基正丁基醚,甲基异丁基醚,甲基叔丁基醚,甲基环己基醚,甲基苯基醚,环氧乙烷,环氧丁烷,氧杂环丁烷,四氢呋喃,2,5-二甲基四氢呋喃,四氢吡喃,1,2-二甲氧基乙烷,1,2-二乙氧基乙烷,1,2-二异丁氧基乙烷,2,2-二甲氧基丙烷,1,3-二甲氧基丙烷,2,2-二异丁基-1,3-二甲氧基丙烷,2-异丙基-2-异戊基-1,3-二甲氧基丙烷,2,2-双(环己基甲基)-1,3-二甲氧基丙烷,2-异丙基-2-3,7-二甲基辛基-1,3-二甲氧基丙烷,2,2-二异丙基-1,3-二甲氧基丙烷,2-异丙基-2-环己基甲基-1,3-二甲氧基丙烷,2,2-二环己基-1,3-二甲氧基丙烷,2-异丙基-2-异丁基-1,3-二甲氧基丙烷,2,2-二异丙基-1,3-二甲氧基丙烷,2,2-二丙基-1,3-二甲氧基丙烷,2-异丙基-2-环己基-1,3-二甲氧基丙烷,2-异丙基-2-环戊基-1,3-二甲氧基丙烷,2,2-二环戊基-1,3-二甲氧基丙烷,2-庚基-2-戊基-1,3-二甲氧基丙烷,1,2-二甲氧基苯,1.3-二甲氧基苯,1,4-二甲氧基苯,1,3-二氧杂戊环,1,4-二噁烷,1,3-二噁烷等。优选是二乙醚,二正丁基醚,甲基正丁基醚,甲基苯基醚,四氢呋喃,1,3-二噁烷,1,4-二噁烷,1,3-二氧杂戊环,更优选是二乙醚,二正丁基醚或四氢呋喃。
作为羧酸酯类的具体例子,可以举出一元和多元羧酸酯,其例子可以举出饱和脂肪族羧酸酯,不饱和脂肪族羧酸酯,脂环式羧酸酯,芳香族羧酸酯。其具体例可以举出乙酸甲酯,乙酸乙酯,乙酸正丁酯,乙酸异丁酯,乙酸-叔丁酯,乙酸苯酯,丙酸甲酯,丙酸乙酯,丁酸乙酯,戊酸乙酯,丙烯酸乙酯,甲酯丙烯酸甲酯,苯甲酸甲酯,苯甲酸乙酯,苯甲酸正丁酯,苯甲酸异丁酯,苯甲酸叔丁酯,甲苯酸甲酯,甲苯酸乙酯,茴香酸甲酯,茴香酸乙酯,丁二酸二甲酯,丁二酸二乙酯,丁二酸二正丁酯,丙二酸二甲酯,丙二酸二乙酯,丙二酸二正丁酯,马来酸二甲酯,马来酸二丁酯,衣康酸二乙酯,衣康酸二正丁酯,邻苯二甲酸单乙酯,邻苯二甲酸二甲酯,邻苯二甲酸甲酯乙酯,邻苯二甲酸二乙酯,邻苯二甲酸二正丙酯,邻苯二甲酸二异丙酯,邻苯二甲酸二正丁酯,邻苯二甲酸二异丁酯,邻苯二甲酸二叔丁酯,邻苯二甲酸二戊酯,邻苯二甲酸二正己酯,邻苯二甲酸二庚酯,邻苯二甲酸二正辛酯,邻苯二甲酸二(2-乙酯己酯),邻苯二甲酸二异癸酯,邻苯二甲酸二环己酯,邻苯二甲酸二苯酯,间苯二甲酸二甲酯,间苯二甲酸二乙酯,间苯二甲酸二正丁酯,间苯二甲酸二异丁酯,间苯二甲酸二叔丁酯,对苯二甲酸二甲酯,对苯二甲酸二乙酯,对苯二甲酸二正丁酯,对苯二甲酸二异丁酯,对苯二甲酸二叔丁酯等。优选是乙酸甲酯,乙酸乙酯,苯甲酸甲酯,苯甲酸乙酯,邻苯二甲酸二甲酯,邻苯二甲酸二乙酯,邻苯二甲酸二正丁酯,邻苯二甲酸二异丁酯,对苯二甲酸二甲酯或对苯二甲酸二乙酯,更优选是苯甲酸甲酯,邻苯二甲酸二甲酯,邻苯二甲酸二乙酯,邻苯二甲酸二异丁酯或对苯二甲酸二甲酯。
作为胺类的示例化合物,可举出三氢乙胩(trihydrocarbylamine),可举出三甲基胺,三乙基胺,三丙基胺,三正丁基胺,三异丁基胺,三己基胺,三辛基胺,三(十二烷基)胺,三苯基胺。优选是三乙基胺或三辛基胺。
另外,上述给电子性化合物(E)可以使用具有活性氢的化合物。具有活性氢的化合物中,可以使用醇类、酚类、羧酸类、硫醇类、硫酚类、硫代羧酸类、磺酸类、氨、伯胺类、仲胺类、苯胺类、亚胺类、酰胺类、吡咯类、吡咯烷类、哌啶类、羟胺类、硅烷醇类。这些当中,优选使用具有N-H键的化合物,更优选使用氨,伯胺,仲胺,苯胺类,吡咯烷类或哌啶类,特别优选使用伯胺,仲胺或苯胺类。
作为伯胺的具体例子,可以列举甲基胺,乙基胺,正丙胺,异丙胺,正丁胺,异丁胺,叔丁胺,己基胺,辛基胺,十二烷基胺。
作为仲胺的具体例子,可以列举二甲基胺,二乙基胺,二正丙基胺,二异丙基胺,二正丁基胺,二异丁基胺,二叔丁基胺,二己基胺,二辛基胺,二(十二烷基)胺,二苯基胺,乙基甲基胺等。
使用具有N-H键的苯胺类作为苯胺类时,其具体例子可以列举苯胺,N-甲基苯胺,N-乙基苯胺,4-甲基苯胺,2,6-二甲基苯胺。
使用具有N-H键的吡咯烷类作为吡咯烷类时,其具体例子可以列举吡咯烷,2,5-二甲基吡咯烷,2,2,5,5-四甲基吡咯烷等,使用具有N-H键的哌啶类作为哌啶类时,其具体例子可以列举哌啶,4-甲基哌啶,2,6-二甲基哌啶,2,2,6,6-四甲基哌啶等。
这些具有活性氢的化合物的示例化合物中,更优选使用甲基胺,乙基胺,二甲基胺,二乙基胺,苯胺,N-甲基苯胺,2,5-二甲基吡咯烷,或2,6-二甲基哌啶,特别优选使用乙基胺,二乙基胺,或N-甲基苯胺。
给电子性化合物(E)优选使用烷氧基硅类,醚类或胺类。更优选使用胺类。此类给电子性化合物(E)可以仅使用一种,也可以将两种以上结合使用。
本发明的乙烯-α-烯烃共聚催化剂的制造方法是使上述成分(A),上述成分(B1)和上述成分(B2),上述成分(C),和上述成分(D)接触来生产乙烯-α-烯烃共聚催化剂的方法,该接触包含在上述成分(A)存在下,使上述成分(B1)和上述成分(B2)与上述成分(C)接触的工序。
作为使上述各成分接触的方法,可以举出例如通过将上述各成分装入到聚合器内在聚合器内进行接触的方法,在聚合器外使上述各成分在惰性溶剂中混合接触的方法等。
作为乙烯-α-烯烃共聚催化剂的制备中所使用的惰性烃介质的例子,具体可以举出丙烷,丁烷,戊烷,己烷,庚烷,辛烷,癸烷,十二碳烷,煤油等脂肪烃;环戊烷,环己烷,甲基环戊烷等脂环族烃;苯,甲苯,二甲苯等芳族烃;氯乙烯,氯苯,二氯甲烷等卤代烃,或它们的混合物等。
本发明的乙烯-α-烯烃共聚物的制造方法是在上述乙烯-α-烯烃共聚催化剂存在下使乙烯与α-烯烃共聚的方法。
作为聚合方法,可以举出气相聚合方法,淤浆聚合方法,本体聚合方法等。优选的是气相聚合方法,更优选的是连续气相聚合方法。用于该聚合方法中的气相聚合反应装置通常是具有流化床型反应罐的装置,优选具有包含扩大部分的流化床型反应罐的装置。搅拌叶片可以设置在反应罐内。
当乙烯和α-烯烃进行气相聚合时,聚合温度通常低于乙烯-α-烯烃共聚物熔融的温度,优选是0-150℃,更优选是30-100℃。可以将惰性气体引入到聚合反应罐中,也可以引入作为分子量调节剂的氢气。另外,也可以引入给电子性化合物。
另外,在乙烯和α-烯烃的聚合中,也可以根据需要将其它单体引入到聚合反应罐中,在不损害本发明效果的范围内使该其它单体共聚。作为其它单体,可以举出例如共轭二烯(例如丁二烯、异戊二烯),非共轭二烯(例如1,4-戊二烯),丙烯酸,丙烯酸酯(例如丙烯酸甲酯、丙烯酸乙酯),甲基丙烯酸,甲基丙烯酸酯(例如甲基丙烯酸甲酯、甲基丙烯酸乙酯),乙酸乙烯酯等。
在本发明的烯烃聚合物的制造方法中,优选下面的方法:在制备乙烯-α-烯烃共聚催化剂时,使用少量成分(A)的烯烃,并使其与成分(A),成分(B1),成分(B2),成分(C),和根据需要的成分(D)和/或成分(E)接触,得到预聚合固体催化剂成分(以下,称为预聚合),并使用所得到的预聚合固体催化剂成分作为聚合催化剂成分或聚合催化剂来进行烯烃的聚合。
作为预聚合中使用的烯烃,可以举出乙烯,丙烯,1-丁烯,1-戊烯,1-己烯,1-辛烯,4-甲基-1-戊烯,环戊烯,环己烯等。这些烯烃可以使用一种,或者将其中的两种以上结合使用。优选的是仅使用乙烯,或者将乙烯与α-烯烃结合使用,更优选仅使用乙烯,或者将选自1-丁烯,1-己烯和1-辛烯中的至少一种α-烯烃与乙烯结合使用。
相对于1 g的成分(C),预聚合固体催化剂成分中进行了预聚合的聚合物的含量优选是0.01-1000 g,更优选0.05-500 g,进一步优选0.1-200
g。
预聚合方法可以是连续聚合方法,也可以是间歇聚合方法,例如是间歇淤浆聚合方法,连续淤浆聚合方法,连续气相聚合方法。作为将成分(A),成分(B1),成分(B2),成分(C),和根据需要的成分(D)和/或成分(E)加入到进行预聚合的聚合反应罐中的方法,通常使用利用氮气、氩气等惰性气体,氢气,乙烯等以没有水分的状态加入的方法,将各成分溶解或稀释在溶剂中并以溶液或淤浆状态加入的方法。
当采用淤浆聚合方法进行预聚合时,作为溶剂,通常使用饱和脂肪烃化合物,例如可以举出丙烷,正丁烷,异丁烷,正戊烷,异戊烷,正己烷,环己烷,庚烷等。这些可以单独使用,或将它们中的两种以上结合使用。作为饱和脂肪烃化合物,优选在常压下沸点为100℃以下的饱和脂肪烃化合物,更优选在常压下沸点为90℃以下的饱和脂肪烃化合物,进一步优选丙烷,正丁烷,异丁烷,正戊烷,异戊烷,正己烷,环己烷。
当采用淤浆聚合方法进行预聚合时,作为淤浆浓度,相对于每1升溶剂,成分(C)的量通常是0.1-600 g,优选0.5-300 g。预聚合温度通常是-20-100℃,优选0-80℃。
在预聚合过程中,聚合温度可以适当地变化,引发预聚合的温度优选是45℃以下,更优选40℃以下。在预聚合过程中在气相部分中烯烃类的分压通常是0.001-2 MPa,优选0.01-1 MPa。预聚合时间通常是2分钟-15小时。
作为将预聚合的预聚合固体催化剂成分供应到聚合反应罐中的方法,通常,使用利用氮气、氩气等惰性气体,氢气,乙烯等以没有水分的状态进行供给的方法,将各成分溶解或稀释在溶剂中并以溶液或淤浆状态进行供给的方法。
根据需要,本发明的乙烯-α-烯烃共聚物可含有已知的添加剂。作为添加剂,可以举出例如抗氧剂,耐气候剂,润滑剂,防结块剂,抗静电剂,防雾剂,防滴剂,颜料,填料等。
本发明的乙烯-α-烯烃共聚物是通过已知的成型方法,例如吹模成型法和T口模膜成型法(flat
die process)等挤出成型法,中空成型法,注射成型法,压缩成型法等来进行成型。作为成型方法,适宜使用挤出成型法和中空成型法,更适宜使用挤出成型法,特别适宜使用T口模膜成型法。另外,本发明的乙烯-α-烯烃共聚物能够适宜用于各种发泡用途中,如电子束交联发泡,过氧化物交联发泡,挤出非交联发泡等。
本发明的乙烯-α-烯烃共聚物被成型成各种形式使用。成型品的形式没有特别限制,可用于膜,片材,容器(盘子,瓶子等)。该成型品也适宜用于食品包装材料;药品包装材料;用于包装半导体产品等的电子部件包装材料;表面防护材料的用途。
如上所述,本发明的乙烯-α-烯烃共聚物具有低挤出负荷、高熔融张力,并且熔融的共聚物在张力恒定的条件下卷取时的卷取性优异,应变硬化特性也优异,并且可热封的温度范围宽。
本发明的乙烯-α-烯烃共聚物也能够以合适量共混到以往的乙烯系聚合物中以便改善缩幅较差的乙烯系聚合物的缩幅。例如,通过将合适量的本发明的乙烯-α-烯烃共聚物共混到如线性低密度聚乙烯等的乙烯系聚合物中,缩幅能够显著地得到改善。
本发明的乙烯-α-烯烃共聚物也能够适量地共混到以往的乙烯系聚合物中以便改善发泡性能较差的乙烯系聚合物的发泡性能。例如,通过将合适量的本发明的乙烯-α-烯烃共聚物共混到如线性低密度聚乙烯等乙烯系聚合物中,发泡性能能够显著地得到改善。
实施例
以下,通过实施例和比较例对本发明进行说明。
在实施例和比较例中的物性根据下列方法来测定。
(1)密度(d,单位:Kg/m3)
根据在JIS K7112-1980中的A中规定的方法测定密度。应予说明,对样品进行在JIS
K6760-1995中所述的退火。
(2)熔体流动速率(MFR,单位:g/10分)
熔体流动速率是在JIS K7210-1995中规定的方法中,在21.18N的载荷、190℃的温度条件下,由方法A所测定的。
(3)膨胀比(SR)
在(2)的熔体流动速率的测定中,在190℃的温度、21.18N的载荷的条件下将以约15-20mm的长度从口型挤出的乙烯-α-烯烃共聚物的线料在空气中冷却而获得固体状的线料。然后,在距该线料的挤出上游侧前端约5mm的位置测定线料的直径D(单位:mm),计算由将其直径D除以口型直径2.095mm(D0)所获得的值(D/D0),将其作为膨胀比。
(4)分子量分布(Mw/Mn,Mz/Mw)
通过使用凝胶渗透色谱(GPC)法,在下列条件(1)-(8)下,测定Z均分子量(Mz),重均分子量(Mw)和数均分子量(Mn),求出Mw/Mn和Mz/Mw。在色谱仪上的基线是通过将保留时间与样品溶出峰的出现相比足够短的稳定的水平区域的点与保留时间与观察到溶剂溶出峰相比足够长的稳定的水平区域的点相连所获得的直线。分子量分布的峰位置的分子量是通过校正,并换算成聚乙烯而获得的值。
(1)装置:由Waters制造的Waters150C
(2)分离柱:TOSOH TSKgel GMH6-HT
(3)测定温度:140℃
(4)载体:邻二氯苯
(5)流量:1.0 mL/min
(6)注入量:500 μL
(7)检测器:差示折射
(8)分子量标准物质:标准聚苯乙烯。
(5)碳原子数5以上的分支数(NLCB,单位:1/1000 C)
通过碳核磁共振法,通过下面的测定条件,测定碳核磁共振谱(13C-NMR),由下列计算方法获得碳原子数5以上的分支数。
<测定条件>
装置:由Bruker制造的AVANCE600
测定溶剂:1,2-二氯苯/1,2-二氯苯-d4=75/25(体积比)的混合溶液
测定温度:130℃
测定方法:质子去偶方法
脉冲宽度:45度
脉冲重复时间:4秒
测定标准:三甲基硅烷
窗口函数:负指数函数。
<计算方法>
将在5-50 ppm处观察到的所有峰的总和记作1000,获得了在38.22~38.27 ppm附近具有峰顶的峰的峰面积。该峰的峰面积为,由在高磁场侧与相邻的峰的谷的化学位移至在低磁场侧与相邻的峰的谷的化学位移的范围的信号面积。应予说明,在本条件下,对于乙烯-1-辛烯共聚物的测定,从碳原子数6的分支所键合的次甲基碳衍生的峰的峰顶位置是38.21
ppm。
(6)熔融复数粘度(η*,单位:Pa・sec)
使用粘弹性测定装置(由Rheometrics制造的Rheometrics Mechanical Spectrometer RMS-800),下列测定条件下,测定在190℃下的熔融复数粘度-角频率曲线,获得了在角频率100rad/sec下测定的熔融复数粘度。该熔融复数粘度越低,挤出成型时的挤出负荷越优异。
<测定条件>
几何结构:平行板
板直径:25 mm
板间隔:1.5-2 mm
应变 :5%
角频率:0.1-100 rad/sec
测定气氛:氮气。
(7)熔融树脂的拉伸粘度测定
使用拉伸粘度测定装置(由TA
Instrument制造的ARES),并在0.1 s-1和1 s-1的Hencky速率下,测定在130℃下熔融树脂的拉伸粘度-时间曲线。作为测定试验片,使用通过加压成型所获得的0.7 mm厚度的18 mm×10 mm的片材。
(8)熔融张力(MT,单位:cN)
使用東洋精机制作所制造的熔融张力试验机,在190℃的温度和0.32 g/min的挤出速率下,从直径2.095
mm、长度8 mm的口型中熔融挤出乙烯-α-烯烃共聚物,将该挤出的熔融的乙烯-α-烯烃共聚物以6.3(m/min)/min的卷取提升速率由卷取辊以长丝状卷取,测定在卷取时的张力。从卷取起始到长丝状的乙烯-α-烯烃共聚物断裂为止的最大张力作为熔融张力。
(9)最大卷取速率(MTV,单位:m/min)
将在(8)的熔融张力的测定中,当长丝状的乙烯-α-烯烃共聚物断裂时的卷取速率为最大卷取速率。该值越高,挤出成型时的卷取性越优异。
(10)特征松弛时间(τ)(sec)
使用粘弹性测定装置(Rheometrics制造的Rheometrics Mechanical Spectrometer RMS-800),在下列测定条件下,测定在130℃,150℃,170℃和190℃下的熔融复数粘度-角频率曲线,然后,使用Rheometrics制造的计算软件Rhios V.4.4.4从所得到的熔融复数粘度-角频率曲线作成在190℃下熔融复数粘度-角频率曲线的主曲线,求出特征松弛时间(τ)。
<测定条件>
几何结构:平行板
板直径:25 mm
板间隔:1.5-2 mm
应变 :5%
角频率:0.1-100 rad/sec
测定气氛:氮气。
实施例1
(1)固体催化剂成分(S)的制备
在装有搅拌器的经过了氮气置换的50 升的反应器中加入9.68
kg的在氮气流通下于300℃加热处理过的硅石(由Debison制造的Sylopol 948;平均粒径=55 μm;孔容=1.67 ml/g;比表面积=325
m2/g) 作为成分(b)固体状载体。加入100 升的甲苯后,冷却到2℃。将甲基铝氧烷(methylalumoxane)的甲苯溶液(2.9
M) 26.3 升用一个小时滴加进去。在5℃搅拌30分钟后,用90分钟加热到95℃,并进行4小时搅拌。然后,冷却至40℃后静置40分钟,使固体成分沉降,除去上层的淤浆部分。作为洗涤操作,将100 升的甲苯加入,搅拌10分钟后,停止搅拌并进行静置,使固体成分沉降,同样地除去上层的淤浆部分。上面的洗涤操作总计重复3次。加入100升甲苯并进行搅拌,然后停止搅拌,同时进行过滤。再重复进行一次该操作,然后加入110升己烷,利用同样的方法进行过滤。再重复进行一次该操作。然后,通过在氮气流通下于70℃干燥7小时,获得12.6 kg的固体状催化剂成分。元素分析的结果是Al=4.4 mmol/g。
(2)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入180 ml 的1-己烯650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6 MPa,并使该体系稳定。在其中加入0.9
ml的浓度调节至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加3.125 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和0.5
ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入104.6
mg在上述(1)中获得的固体催化剂成分(S)。在聚合过程中,连续地供应乙烯,同时在70℃下进行60分钟聚合。此后,清除丁烷、乙烯,得到43 g的乙烯-1-己烯共聚物。
所得到的共聚物的物性示于表1中。
实施例2
(1)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入氢气以使其分压变成0.0025 MPa,加入180
ml 的1-己烯、650 g的作为聚合溶剂的丁烷,升温至70℃。此后,添加乙烯,以使得其分压变成1.6
MPa,并使该体系稳定。在其中加入0.9 ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加6.25 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和1 ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入210.8
mg的在上述实施例1(1)中获得的固体催化剂成分。在聚合过程中,连续地供应乙烯,同时在70℃下进行60分钟聚合。此后,清除丁烷、乙烯,得到86 g的乙烯-1-己烯共聚物。所得到的共聚物的物性示于表1中。
实施例3
(1)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入氢气以使其分压变成0.005 MPa,加入180
ml 的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6
MPa,并使该体系稳定。在其中加入0.9 ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加6.25 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和1.0
ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入105.8
mg的在上述实施例1(1)中获得的固体催化剂成分(S)。在聚合过程中,连续地供应乙烯/氢气混合气体(氢气=0.043 mol%),同时在70℃下进行90分钟聚合。此后,清除丁烷、乙烯和氢气,得到42 g的乙烯-1-己烯共聚物。所得到的共聚物的物性示于表1中。
实施例4
(1)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入180 ml 的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6 MPa,并使该体系稳定。在其中加入0.9
ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加3 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和0.1
ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入91.1
mg的在上述实施例1(1)中获得的固体催化剂成分。在聚合过程中,连续地供应乙烯气体,同时在70℃下进行60分钟聚合。此后,清除丁烷、乙烯,得到34 g的乙烯-1-己烯共聚物。所得到的共聚物的物性示于表1中。
实施例5
(1)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空、加入180 ml 的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6 MPa,并使该体系稳定。在其中加入0.9
ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加5 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和0.25
ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入207.8
mg的在上述实施例1(1)中获得的固体催化剂成分。在聚合过程中,连续地供应乙烯气体,同时在70℃下进行60分钟聚合。此后,清除丁烷、乙烯,得到77 g的乙烯-1-己烯共聚物。
所得到的共聚物的物性示于表1中。
实施例6
(1)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空、加入180 ml 的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6 MPa,并使该体系稳定。在其中加入0.9
ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,添加5 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和0.5
ml的浓度调节至1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后,加入209
mg的在上述实施例1(1)中获得的固体催化剂成分。
在聚合过程中,连续地供应乙烯气体,同时在70℃下进行60分钟聚合。此后,清除丁烷、乙烯,得到82 g的乙烯-1-己烯共聚物。所得到的共聚物的物性示于表1中。
比较例1
(1)淤浆状催化剂成分(Cat-1)的制备
在氮气置换过的100 ml的玻璃制茄形烧瓶中加入200
mg的实施例1(1)中制备的淤浆状催化剂成分(S)。然后,添加12.5 ml的浓度调节至2 μmol/ml的二氯化二甲基硅烷二基双(环戊二烯基)锆[相当于过渡金属化合物(B1)]的甲苯溶液和1 ml的浓度调节至2 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,边搅拌边在室温下反应5分钟。此后,通过倾析除去上清液,然后将其用己烷洗涤两次,获得6 ml的己烷淤浆。
(2)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入180 ml的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。然后,加入乙烯/氢气混合气体(氢气=0.33 mol%),以使混合气体的分压变成1.6
MPa,并使体系稳定。作为气相色谱分析的结果,体系中气体组成是氢气=0.15 mol%。在其中加入0.9 ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。然后,加入6 ml的在上述(2)中制备的淤浆状催化剂成分(Cat-1)。在聚合过程中,连续地供应乙烯/氢气混合气体(氢气=0.33 mol%),在70℃下进行60分钟聚合。此后,清除丁烷、乙烯和氢气,得到71 g的乙烯-1-己烯共聚物。所得到的共聚物的物性示于表2中。
比较例2
(1)固体催化剂成分的制备
在装有搅拌器的氮气置换过的反应器中加入2.8 kg的已经在氮气流下于300℃进行了加热处理的硅石(由Debison制造的Sylopol 948;50%体积平均粒径=55 μm;孔容=1.67 ml/g;比表面积=325 m2/g)和24 kg的甲苯,进行搅拌。然后,在冷却到5℃后,将反应器的温度保持在5℃,同时用30分钟滴加0.9 kg的1,1,1,3,3,3-六甲基二硅氮烷和1.4
kg的甲苯的混合溶液。滴加完成后,在5℃下搅拌1小时,然后升温至95℃,在95℃下搅拌3小时,进行过滤。所得固体产物用20.8 kg的甲苯洗涤6次。然后,添加7.1 kg的甲苯,形成淤浆,并静置一夜。
在上述获得的淤浆中加入1.73 kg的二乙基锌的己烷溶液(二乙基锌浓度:50 重量%)和1.02 kg的己烷,并进行搅拌。然后,在冷却至5℃后,将反应器的温度保持在5℃,同时用60分钟滴加0.78 kg的3,4,5-三氟苯酚和1.44 kg的甲苯的混合溶液。滴加完成后,在5℃下搅拌1小时,此后,升温至40℃,并在40℃下搅拌1小时。然后冷却至22℃,将反应器的温度保持在22℃,同时用1.5小时滴加0.11 kg的H2O。滴加完成后,在22℃下搅拌1.5小时,然后升温至40℃,在40℃下搅拌2小时,再升温至80℃,并在80℃下搅拌2小时。搅拌后,在室温下抽出上清液,使得残留量为16 L,加入11.6 kg的甲苯,然后升温至95℃,搅拌4小时。
搅拌后,在室温下抽出上清液,得到固体产物。将所得的固体产物用20.8 kg的甲苯洗涤4次,用24升的己烷洗涤3次。然后,通过干燥获得固体催化剂成分。
(2)聚合
将装有搅拌器的、在减压干燥之后用氩气置换了的3 升内容积的高压釜排真空,加入氢气以使得其分压变成0.025 MPa,加入180
ml 的1-己烯、650 g的作为聚合溶剂的丁烷,并且升温至70℃。此后,添加乙烯,以使得其分压变成1.6
MPa,并使该体系稳定。作为气相色谱分析的结果,体系中气体组成是氢气=1.56 mol%。在其中加入0.9 ml的浓度调整至1 mol/l的作为有机铝化合物(C)的三异丁基铝的己烷溶液。此后,加入0.2
ml的浓度调节至2 μmol/ml的外消旋-亚乙基双(1-茚基)锆二苯酚盐的甲苯溶液和0.3 ml的浓度调节至0.1 μmol/ml的二氯化二苯基亚甲基(环戊二烯基)(9-芴基)锆[相当于过渡金属化合物(B2)]的甲苯溶液,然后加入18.8
mg的在比较例2(1)中获得的固体催化剂成分。在聚合过程中,连续地供应乙烯/氢气混合气体(氢气=0.22 mol%),同时在70℃下进行180分钟聚合。此后,清除丁烷、乙烯和氢气,得到179 g的乙烯-1-己烯共聚物。所得到的共聚物的物性评价结果示于表2中。
[表1]
[表2]
产业实用性
根据本发明,可提供挤出负荷低、熔融张力高、并且当熔融的共聚物在恒定张力的条件下卷取时的卷取性优异、应变硬化特性优异、并且二次加工性优异的乙烯-α-烯烃共聚物,以及将该共聚物挤出成型所获得的成形体。
Claims (3)
1. 乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,具有860-950
kg/m3的密度(d),0.01-100
g/10分的熔体流动速率(MFR),在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,特征松弛时间(τ)满足式(1)的关系,并且存在由差示扫描量热计(DSC)所测定的多个熔融峰,
40.2×MFR-0.606<τ<71.8×MFR-0.175
式(1)。
2. 乙烯-α-烯烃共聚物,其具有基于乙烯的单体单元和基于碳原子数3-20的α-烯烃的单体单元,具有860-950
kg/m3的密度(d),0.01-100
g/10分的熔体流动速率(MFR),在通过凝胶渗透色谱(GPC)法测定的分子量分布曲线中,在分子量10000-20000的范围具有最高峰,将该最高峰的高度设为100%时,分子量177000位置的峰高度为5%以上且30%以下,通过NMR测定的碳原子数5以上的分支数(NLCB)为0.1以上,并且存在由差示扫描量热计(DSC)所测定的多个熔融峰。
3. 通过将权利要求1或2的乙烯-α-烯烃共聚物挤出成型而得到的成型体。
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