JP2001247579A - Transition metal compound, catalyst for polymerizing olefins, and method of producing olefinic polymer - Google Patents
Transition metal compound, catalyst for polymerizing olefins, and method of producing olefinic polymerInfo
- Publication number
- JP2001247579A JP2001247579A JP2000058499A JP2000058499A JP2001247579A JP 2001247579 A JP2001247579 A JP 2001247579A JP 2000058499 A JP2000058499 A JP 2000058499A JP 2000058499 A JP2000058499 A JP 2000058499A JP 2001247579 A JP2001247579 A JP 2001247579A
- Authority
- JP
- Japan
- Prior art keywords
- group
- transition metal
- metal compound
- compound
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 47
- 150000003623 transition metal compounds Chemical class 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 7
- 229920000642 polymer Polymers 0.000 title abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 239000002685 polymerization catalyst Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000003624 transition metals Chemical group 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000003610 charcoal Substances 0.000 claims 1
- -1 polypropylene Polymers 0.000 description 99
- 125000004432 carbon atom Chemical group C* 0.000 description 34
- 150000002430 hydrocarbons Chemical group 0.000 description 30
- 239000000203 mixture Substances 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- 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 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 21
- 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 19
- 239000002904 solvent Substances 0.000 description 19
- 239000004743 Polypropylene Substances 0.000 description 15
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 150000003613 toluenes Chemical class 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 150000008040 ionic compounds Chemical class 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000003808 silyl group Chemical class [H][Si]([H])([H])[*] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- AEJOEPSMZCEYJN-HXUWFJFHSA-N 2-(3,4-dichlorophenyl)-N-methyl-N-[(1S)-1-phenyl-2-(1-pyrrolidinyl)ethyl]acetamide Chemical compound C([C@@H](N(C)C(=O)CC=1C=C(Cl)C(Cl)=CC=1)C=1C=CC=CC=1)N1CCCC1 AEJOEPSMZCEYJN-HXUWFJFHSA-N 0.000 description 2
- VRLOTVSORLJHQJ-UHFFFAOYSA-N 4-methyl-2-trimethylsilylphenol Chemical compound CC1=CC=C(O)C([Si](C)(C)C)=C1 VRLOTVSORLJHQJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CUKOBQBTUKUHJW-UHFFFAOYSA-N CC1=CC(=C(C=C1)O[Si](C)(C)C)Br Chemical compound CC1=CC(=C(C=C1)O[Si](C)(C)C)Br CUKOBQBTUKUHJW-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910018287 SbF 5 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 150000008282 halocarbons Chemical group 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 150000002738 metalloids Chemical group 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical class [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 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 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
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- 125000004915 dibutylamino group Chemical group C(CCC)N(CCCC)* 0.000 description 1
- RBMCKUNBFWVWQJ-UHFFFAOYSA-N dichloro-(2,3,4,5,6-pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(B(Cl)Cl)C(F)=C1F RBMCKUNBFWVWQJ-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GRYISIJQPOEWPF-UHFFFAOYSA-N diethyl(fluoro)borane Chemical compound CCB(F)CC GRYISIJQPOEWPF-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
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- AYIZUGQPPRPVJJ-UHFFFAOYSA-N difluoro(methyl)borane Chemical compound CB(F)F AYIZUGQPPRPVJJ-UHFFFAOYSA-N 0.000 description 1
- WATLWUFSKRFBOD-UHFFFAOYSA-N difluoro(phenyl)borane Chemical compound FB(F)C1=CC=CC=C1 WATLWUFSKRFBOD-UHFFFAOYSA-N 0.000 description 1
- IAAKXIPQVRCQAY-UHFFFAOYSA-N difluoro-(2,3,4,5,6-pentafluorophenyl)borane Chemical compound FB(F)C1=C(F)C(F)=C(F)C(F)=C1F IAAKXIPQVRCQAY-UHFFFAOYSA-N 0.000 description 1
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- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- XWMDCRPECVJIGR-UHFFFAOYSA-N fluoro(diphenyl)borane Chemical compound C=1C=CC=CC=1B(F)C1=CC=CC=C1 XWMDCRPECVJIGR-UHFFFAOYSA-N 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 239000011572 manganese Substances 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
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- PHUUEJUSWPFFOG-UHFFFAOYSA-N methyl(triphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 PHUUEJUSWPFFOG-UHFFFAOYSA-N 0.000 description 1
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- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical compound C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006247 phenyl propyl amino group Chemical group [H]N(*)C([H])([H])C([H])([H])C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000109 phenylethoxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003395 phenylethylamino group Chemical group [H]N(*)C([H])([H])C([H])([H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
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- 239000011949 solid catalyst Substances 0.000 description 1
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- 238000010558 suspension polymerization method Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- FIONWRDVKJFHRC-UHFFFAOYSA-N trimethyl(2-phenylethenyl)silane Chemical class C[Si](C)(C)C=CC1=CC=CC=C1 FIONWRDVKJFHRC-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- ZNEOHLHCKGUAEB-UHFFFAOYSA-N trimethylphenylammonium Chemical compound C[N+](C)(C)C1=CC=CC=C1 ZNEOHLHCKGUAEB-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-O triphenylazanium Chemical compound C1=CC=CC=C1[NH+](C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-O 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- SNWNTXNSTNPQAY-UHFFFAOYSA-N tris(1,1,2,2,2-pentafluoroethyl)borane Chemical compound FC(F)(F)C(F)(F)B(C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)F SNWNTXNSTNPQAY-UHFFFAOYSA-N 0.000 description 1
- IIXXWFUECRRGPO-UHFFFAOYSA-N tris(1,1,2,2,3,3,4,4,4-nonafluorobutyl)borane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)B(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F IIXXWFUECRRGPO-UHFFFAOYSA-N 0.000 description 1
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- CWBUXUFJSQBQEQ-UHFFFAOYSA-N tris(fluoromethyl)borane Chemical compound FCB(CF)CF CWBUXUFJSQBQEQ-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- BPKXQSLAVGBZEM-UHFFFAOYSA-N tris[3,5-bis(trifluoromethyl)phenyl]borane Chemical compound FC(F)(F)C1=CC(C(F)(F)F)=CC(B(C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)=C1 BPKXQSLAVGBZEM-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical class C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、遷移金属化合物、
それを用いたオレフィン類重合用触媒及びオレフィン系
重合体の製造方法に関する。さらに詳しくは、本発明
は、立体規則性のポリプロピレンなどを製造し得る高活
性で安価なオレフィン類重合用均一系触媒を与えるキレ
ート型配位子を有する新規な遷移金属化合物、それを用
いた上記性能を有するオレフィン類重合用触媒及びこの
重合用触媒を用い、分子量分布が狭く、かつ立体規則性
を有するオレフィン系重合体を効率よく製造する方法に
関するものである。The present invention relates to a transition metal compound,
The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, the present invention relates to a novel transition metal compound having a chelate type ligand which provides a highly active and inexpensive homogeneous catalyst for olefin polymerization capable of producing stereoregular polypropylene and the like, The present invention relates to an olefin polymerization catalyst having high performance and a method for efficiently producing an olefin polymer having a narrow molecular weight distribution and stereoregularity using the polymerization catalyst.
【0002】[0002]
【従来の技術】従来、高活性可溶系オレフィン重合用触
媒としては、遷移金属化合物とアルミノキサンとの組合
せからなるものが知られている(特開昭58−1930
9号公報、特開昭60−217209号公報)。また、
可溶系オレフィン重合触媒の活性種としてはカチオン種
が有効であることが報告されている〔「J.Am.Ch
em.Soc.」第81巻、第81ぺージ(1959
年)。同誌第82巻、第1953ぺージ(1960年)
同誌第107巻、第7219ページ(1986年)〕。
また、この活性種を単離し、オレフィン重合に適用した
例としては「J.Am.Chem.Soc.」第108
巻、第7410ページ(1986年)、特表平1−50
2636号公報、特開平3−139504号公報、ヨー
ロッパ公開特許第46851号などを挙げることがで
き、さらにこの活性種に有機アルミニウム化合物を併用
した例として、特開平3−207704号公報、国際特
許公開92−1723号などを挙げることができる。と
ころで、メタロセン触媒より得られるポリプロピレン
は、該触媒の単一な活性点に起因して狭い分子量分布を
有し、またTREF(昇温分別クロマトグラフ)におけ
る常温可溶部量が低いなどの特性を有することから、繊
維,フィルムなどへの展開が図られているが、該メタロ
セン触媒は比較的高価であるという問題を有し、普及の
足かせとなっている。2. Description of the Related Art Heretofore, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (JP-A-58-1930).
No. 9, JP-A-60-217209). Also,
It is reported that a cationic species is effective as an active species of a soluble olefin polymerization catalyst [“J. Am. Ch.
em. Soc. 81, page 81 (1959)
Year). Vol. 82, 1953 (1960)
107, 7219 (1986)].
An example in which this active species is isolated and applied to olefin polymerization is described in "J. Am. Chem. Soc."
Vol. 7410 (1986), Tokiohei 1-50
No. 2,636, JP-A-3-139504, European Patent Publication No. 46851, and the like. Further, as examples in which an organic aluminum compound is used in combination with this active species, JP-A-3-207704, International Patent Publication No. 92-1723. By the way, polypropylene obtained from a metallocene catalyst has characteristics such as a narrow molecular weight distribution due to a single active site of the catalyst and a low amount of a soluble part at room temperature in TREF (temperature rising fractionation chromatography). Therefore, the metallocene catalyst has a problem that it is relatively expensive, which has hindered its spread.
【0003】近年、高活性可溶系オレフィン重合用触媒
として、キレート型触媒が報告されている(特開平11
−199592号公報、特開平11−199593号公
報、特開平11−240907号公報、「83th C
ATSJ MeetingAbstracts」第41
巻、第2号、第85ページ(1999年)、「Macr
omol.Rapid Commun」第19巻、第5
97ページ(1998年)」。しかしながら、これらの
キレート型触媒は、プロピレンの重合に適用した場合、
活性が全くないか、あるいは活性があったとしても、得
られるポリプロピレンは、アタクチックポリプロピレン
とアイソタクチックポリプロピレンとの混合物となり、
したがって、アイソタクチックポリプロピレンを得るに
は、該混合物にヘキサンやジエチルエーテルなどの溶媒
を用いて精製処理を施す必要がある。In recent years, chelate type catalysts have been reported as highly active soluble olefin polymerization catalysts (Japanese Patent Laid-Open No.
-19952, JP-A-11-199593, JP-A-11-240907, and "83th C
ATSJ MeetingAbstracts "No. 41
Vol. 2, No. 85, (1999), "Macr
omol. Rapid Commun "Vol. 19, No. 5
97 pages (1998). " However, these chelating catalysts, when applied to the polymerization of propylene,
If there is no activity, or even if there is activity, the resulting polypropylene will be a mixture of atactic polypropylene and isotactic polypropylene,
Therefore, in order to obtain isotactic polypropylene, it is necessary to subject the mixture to a purification treatment using a solvent such as hexane or diethyl ether.
【0004】[0004]
【発明が解決しようとする課題】本発明は、このような
状況下で、立体規則性のポリプロピレンなどを製造し得
る高活性で安価なオレフィン類重合用均一系触媒を与え
るキレート型配位子を有する新規な遷移金属化合物、そ
れを用いた上記性能を有するオレフィン類重合用触媒及
びこの重合用触媒を用い、分子量分布が狭く、かつ立体
規則性を有するオレフィン系重合体を効率よく製造する
方法を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention provides a chelating ligand which provides a highly active and inexpensive homogeneous catalyst for olefin polymerization capable of producing stereoregular polypropylene and the like under such circumstances. A novel transition metal compound having the above-mentioned performance, a catalyst for olefin polymerization having the above performance, and a method for efficiently producing an olefin polymer having a narrow molecular weight distribution and stereoregularity using the polymerization catalyst. It is intended to provide.
【0005】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、周期律表第3
〜11族の遷移金属原子を有する特定構造の芳香族イミ
ン系錯体が、遷移金属化合物としてのその目的に適合し
得ることを見出した。本発明は、かかる知見に基づいて
完成したものである。すなわち、本発明は、(1)一般
式(I)Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the periodic table 3
It has been found that an aromatic imine-based complex having a specific structure having a transition metal atom of Groups 11 to 11 can be suitable for the purpose as a transition metal compound. The present invention has been completed based on such findings. That is, the present invention relates to (1) a compound represented by the general formula (I):
【0006】[0006]
【化3】 Embedded image
【0007】〔式中、Mは周期律表第3〜11族の遷移
金属原子、mは1〜3の整数、Xは酸素原子,イオウ原
子,セレン原子又はNR3 、AはD2 R4 3又は[Wherein, M is a transition metal atom of Groups 3 to 11 of the periodic table, m is an integer of 1 to 3, X is an oxygen atom, sulfur atom, selenium atom or NR 3 , A is D 2 R 4 3 or
【0008】[0008]
【化4】 Embedded image
【0009】で表される基、D1 及びD2 は、それぞれ
周期律表第14族の原子を示す。R1〜R5 は、それぞ
れ独立して炭素数1〜20の炭化水素基、R6 は水素原
子又は炭素数1〜20の炭化水素基を示し、R2 及びR
4 は、それぞれにおいて2個がたがいに連結して環を形
成していてもよく、また、mが2又は3の場合、1つの
配位子に含まれるR1 〜R6 のうちの1個の基と他の配
位子に含まれるR1 〜R 6 のうちの1個の基とが結合さ
れていてもよく、R1 同士,R2 同士,R3 同士,R4
同士,R5 同士及びR6 同士はたがいに同一でも異なっ
ていてもよい。Zは水素原子,ハロゲン原子,炭化水素
基,酸素含有基,窒素含有基,ホウ素含有基,アルミニ
ウム含有基,リン含有基,ハロゲン含有基,ケイ素含有
基,ゲルマニウム含有基又はスズ含有基、nは(Mの原
子価−m)の値を示し、nが2以上の場合には、Zで示
される複数の基は、たがいに同一でも異なっていてもよ
く、またたがいに連結して環を形成していてもよい。〕
で表される遷移金属化合物、A group represented by the formula:1And DTwoRespectively
Shows the atoms of Group 14 of the periodic table. R1~ RFiveEach
Independently a hydrocarbon group having 1 to 20 carbon atoms, R6Is hydrogen field
A hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;TwoAnd R
FourRepresents a ring formed by connecting two of each other
And when m is 2 or 3, one m
R contained in the ligand1~ R6One of the groups and the other
R contained in the ligand1~ R 6Is bonded to one of the groups
May be R1Each other, RTwoEach other, RThreeEach other, RFour
Each other, RFiveEach other and R6Each other is the same but different
May be. Z is a hydrogen atom, a halogen atom, a hydrocarbon
Group, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum
Containing group, phosphorus containing group, halogen containing group, silicon containing
Group, germanium-containing group or tin-containing group, n is (M
(N) is indicated by Z when n is 2 or more.
Are different from each other, they may be the same or different.
And may be connected to each other to form a ring. ]
A transition metal compound represented by
【0010】(2)(A)上記一般式(I)で表される
遷移金属化合物、及び(B)該(A)成分の遷移金属化
合物と反応してイオン性の錯体を形成し得る化合物を接
触させてなるオレフィン類重合用触媒、(3)(A)上
記一般式(I)で表される遷移金属化合物、(B)該
(A)成分の遷移金属化合物と反応してイオン性の錯体
を形成し得る化合物、及び(C)有機アルミニウム化合
物を接触させてなるオレフィン類重合用触媒、及び
(4)上記(2)又は(3)のオレフィン類重合用触媒
の存在下、オレフィン類を重合させることを特徴とする
オレフィン系重合体の製造方法、を提供するものであ
る。(2) (A) a transition metal compound represented by the above general formula (I), and (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A). (3) (A) a transition metal compound represented by the above general formula (I), and (B) an ionic complex which reacts with the transition metal compound of the component (A). And (C) an olefin polymerization catalyst obtained by contacting an organoaluminum compound, and (4) polymerization of olefins in the presence of the above-mentioned (2) or (3) olefin polymerization catalyst. And a method for producing an olefin-based polymer.
【0011】[0011]
【発明の実施の形態】本発明の遷移金属化合物は、一般
式(I)BEST MODE FOR CARRYING OUT THE INVENTION The transition metal compound of the present invention has the general formula (I)
【0012】[0012]
【化5】 Embedded image
【0013】で表される構造を有するキレート型の周期
律表第3〜11の遷移金属化合物である。一般式(I)
において、Mは周期律表第3〜11族の遷移金属原子を
示す。この遷移金属原子の例としては、チタニウム,ジ
ルコニウム,ハフニウム,バナジウム,クロム,マンガ
ン,ニッケル,コバルト,パラジウムなどを挙げること
ができ、これらの中で、触媒活性の点から、周期律表第
4族の遷移金属原子が好ましい。mは1〜3の整数、X
は酸素原子,イオウ原子,セレン原子又はNR3 、Aは
D2 R4 3又はA transition metal compound having a structure represented by the following formula: General formula (I)
In the above, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table. Examples of the transition metal atom include titanium, zirconium, hafnium, vanadium, chromium, manganese, nickel, cobalt, palladium, etc. Among them, from the viewpoint of catalytic activity, Group 4 of the periodic table Are preferred. m is an integer of 1 to 3, X
Oxygen atom, sulfur atom, selenium atom or NR 3, A is D 2 R 4 3, or
【0014】[0014]
【化6】 Embedded image
【0015】で表される基を示す。D1 及びD2 は、そ
れぞれ周期律表第14族の原子を示し、その具体例とし
ては、炭素,ケイ素,ゲルマニウム,スズ原子などが挙
げられるが、これらの中で、特に炭素原子及びケイ素原
子が好ましい。R1 〜R5 は、それぞれ独立して炭素数
1〜20の炭化水素基、R6 は水素原子又は炭素数1〜
20の炭化水素基を示し、R2 及びR4 は、それぞれに
おいて2個がたがいに連結して環を形成していてもよ
く、また、mが2又は3の場合、1つの配位子に含まれ
るR1 〜R6 のうちの1個の基と他の配位子に含まれる
R 1 〜R6 のうちの1個の基とが結合されていてもよ
く、R1 同士,R2 同士,R 3 同士,R4 同士,R5 同
士及びR6 同士はたがいに同一でも異なっていてもよ
い。And a group represented by the formula: D1And DTwoIs
Indicate atoms of Group 14 of the Periodic Table, respectively.
Include carbon, silicon, germanium, and tin atoms.
Of these, carbon atoms and silicon
Children are preferred. R1~ RFiveAre carbon numbers independently
1 to 20 hydrocarbon groups, R6Is a hydrogen atom or carbon number 1
20 hydrocarbon groups;TwoAnd RFourIs for each
Two may be connected to each other to form a ring
And when m is 2 or 3, it is contained in one ligand
R1~ R6Contained in one of the groups and other ligands
R 1~ R6May be bonded to one of the groups
K, R1Each other, RTwoEach other, R ThreeEach other, RFourEach other, RFivesame
And R6Each other may be the same or different
No.
【0016】Zは水素原子,ハロゲン原子,炭化水素
基,酸素含有基,窒素含有基,ホウ素含有基,アルミニ
ウム含有基,リン含有基,ハロゲン含有基,ケイ素含有
基,ゲルマニウム含有基又はスズ含有基、nは(Mの原
子価−m)の値を示す。nが2以上の場合には、Zで示
される複数の基は、たがいに同一でも異なっていてもよ
く、またたがいに連結して環を形成していてもよい。一
般式(I)におけるハロゲン原子としては、塩素原子,
フッ素原子,臭素原子,ヨウ素原子が挙げられる。炭素
数1〜20の炭化水素基としては、具体的には、メチル
基,エチル基,プロピル基,ブチル基,ヘキシル基,シ
クロヘキシル基,オクチル基などのアルキル基;ビニル
基,プロペニル基,シクロヘキセニル基などのアルケニ
ル基;ベンジル基,フェニルエチル基,フェニルプロピ
ル基などのアリールアルキル基;フェニル基,トリル
基,ジメチルフェニル基,トリメチルフェニル基,エチ
ルフェニル基,プロピルフェニル基,ビフェニル基,ナ
フチル基,メチルナフチル基,アントラセニル基,フェ
ナントニル基などのアリール基が挙げられる。なかでも
メチル基,エチル基,プロピル基などのアルキル基やフ
ェニル基などのアリール基が好ましい。Z is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group. , N represents the value of (valence of M−m). When n is 2 or more, the plurality of groups represented by Z may be the same or different, and may be linked to each other to form a ring. As the halogen atom in the general formula (I), a chlorine atom,
Examples include a fluorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; vinyl group, propenyl group and cyclohexenyl group. Alkenyl groups such as benzyl group, phenylethyl group, phenylpropyl group, etc .; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group, And aryl groups such as methylnaphthyl group, anthracenyl group, and phenanthonyl group. Among them, an alkyl group such as a methyl group, an ethyl group, and a propyl group and an aryl group such as a phenyl group are preferable.
【0017】Zのうちの炭化水素基,酸素含有基,窒素
含有基,ホウ素含有基,アルミニウム含有基,リン含有
基,ハロゲン含有基,ケイ素含有基,ゲルマニウム含有
基及びスズ含有基としては、それぞれ炭素数1〜20の
炭化水素基,炭素数1〜20の酸素含有炭化水素基,炭
素数1〜20の窒素含有炭化水素基,炭素数1〜20の
ホウ素含有炭化水素基,炭素数1〜20のアルミニウム
含有炭化水素基,炭素数1〜20のリン含有炭化水素
基,炭素数1〜20のハロゲン含有炭化水素基,炭素数
1〜20のケイ素含有炭化水素基,炭素数1〜20のゲ
ルマニウム含有炭化水素基及び炭素数1〜20のスズ含
有炭化水素基が好ましい。The hydrocarbon group, oxygen-containing group, nitrogen-containing group, boron-containing group, aluminum-containing group, phosphorus-containing group, halogen-containing group, silicon-containing group, germanium-containing group and tin-containing group in Z are as follows: A hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a boron-containing hydrocarbon group having 1 to 20 carbon atoms, 20 aluminum-containing hydrocarbon groups, 1 to 20 carbon-containing phosphorus-containing hydrocarbon groups, 1 to 20 carbon-containing halogen-containing hydrocarbon groups, 1 to 20 carbon-containing silicon-containing hydrocarbon groups, 1 to 20 carbon atoms Germanium-containing hydrocarbon groups and tin-containing hydrocarbon groups having 1 to 20 carbon atoms are preferred.
【0018】ここで、炭素数1〜20の炭化水素基は前
述のとおりである。炭素数1〜20の酸素含有炭化水素
基の例としては、メトキシ基,エトキシ基,プロピルオ
キシ基,ブトキシ基,ヘキシルオキシ基,シクロヘキシ
ルオキシ基,オクチルオキシ基などのアルキルオキシ
基;ビニルオキシ基,プロペニルオキシ基,シクロヘキ
セニルオキシ基などのアルケニルオキシ基;ベンジルオ
キシ基,フェニルエチルオキシ基,フェニルプロピルオ
キシ基などのアリールアルキルオキシ基;フェノキシ
基,トリルオキシ基,ジメチルフェニルオキシ基,トリ
メチルフェニルオキシ基,エチルフェニルオキシ基,プ
ロピルフェニルオキシ基,ビフェニルオキシ基,ナフチ
ルオキシ基,メチルナフチルオキシ基,アントラセニル
オキシ基,フェナントニルオキシ基などのアリールオキ
シ基などが挙げられる。炭素数1〜20の窒素含有炭化
水素基の例としては、ジメチルアミノ基,ジエチルアミ
ノ基,ジプロピルアミノ基,ジブチルアミノ基,ジシク
ロヘキシルアミノ基,メチルエチルアミノ基等のアルキ
ルアミノ基;ジビニルアミノ基,ジプロペニルアミノ
基,ジシクロヘキセニルアミノ基などのアルケニルアミ
ノ基;ジベンジルアミノ基,フェニルエチルアミノ基,
フェニルプロピルアミノ基などのアリールアルキルアミ
ノ基;ジフェニルアミノ基,ジナフチルアミノ基などの
アリールアミノ基などが挙げられる。炭素数1〜20の
ハロゲン含有炭化水素基の例としては、前記炭化水素基
にハロゲン原子が置換したハロゲン化炭化水素基が挙げ
られる。炭素数1〜20の珪素含有炭化水素基として
は、メチルシリル基,フェニルシリル基などのモノ炭化
水素置換シリル基;ジメチルシリル基、ジフェニルシリ
ル基などのジ炭化水素置換シリル基;トリメチルシリル
基,トリエチルシリル基,トリプロピルシリル基,トリ
シクロヘキシルシリル基,トリフェニルシリル基,ジメ
チルフェニルシリル基,メチルジフェニルシリル基,ト
リトリルシリル基,トリナフチルシリル基などのトリ炭
化水素置換シリル基;トリメチルシリルエーテル基など
の炭化水素置換シリル基のシリルエーテル基;トリメチ
ルシリルメチル基などのケイ素置換アルキル基;トリメ
チルシリルフェニル基などのケイ素置換アリール基など
が挙げられる。前記一般式(I)で表される遷移金属化
合物の具体例としては、周期律表の第4族の例を示せ
ば、Here, the hydrocarbon group having 1 to 20 carbon atoms is as described above. Examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkyloxy groups such as methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, cyclohexyloxy group and octyloxy group; vinyloxy group and propenyl Alkenyloxy groups such as oxy group and cyclohexenyloxy group; arylalkyloxy groups such as benzyloxy group, phenylethyloxy group and phenylpropyloxy group; phenoxy group, tolyloxy group, dimethylphenyloxy group, trimethylphenyloxy group, and ethyl And an aryloxy group such as a phenyloxy group, a propylphenyloxy group, a biphenyloxy group, a naphthyloxy group, a methylnaphthyloxy group, an anthracenyloxy group, and a phenanthonyloxy group. Examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include an alkylamino group such as a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dicyclohexylamino group, and a methylethylamino group; a divinylamino group; Alkenylamino groups such as dipropenylamino group and dicyclohexenylamino group; dibenzylamino group, phenylethylamino group,
An arylalkylamino group such as a phenylpropylamino group; and an arylamino group such as a diphenylamino group and a dinaphthylamino group. Examples of the halogen-containing hydrocarbon group having 1 to 20 carbon atoms include a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group. Examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group and triethylsilyl Group, tripropylsilyl group, tricyclohexylsilyl group, triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, tritolylsilyl group, trinaphthylsilyl group and other trihydrocarbon-substituted silyl groups; trimethylsilyl ether group and the like A silyl ether group of a hydrocarbon-substituted silyl group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; and a silicon-substituted aryl group such as a trimethylsilylphenyl group. As a specific example of the transition metal compound represented by the general formula (I), if an example of Group 4 of the periodic table is shown,
【0019】[0019]
【化7】 Embedded image
【0020】[0020]
【化8】 Embedded image
【0021】などを挙げることができる。本発明のオレ
フィン類重合用触媒は、(A)前記一般式(I)で表さ
れる遷移金属化合物,(B)該(A)成分の遷移金属化
合物と反応してイオン性の錯体を形成し得る化合物、及
び場合により(C)有機アルミニウム化合物を接触させ
てなるものである。上記(B)成分である、(A)成分
の遷移金属化合物と反応してイオン性の錯体を形成し得
る化合物としては、例えば(B−1)イオン性の錯体を
形成するイオン性化合物、(B−2)アルミノキサン及
び(B−3)ルイス酸を挙げることができる。And the like. The olefin polymerization catalyst of the present invention reacts with (A) the transition metal compound represented by the general formula (I) and (B) the transition metal compound of the component (A) to form an ionic complex. The compound obtained by contacting the obtained compound and, if necessary, (C) an organoaluminum compound. Examples of the compound which can form an ionic complex by reacting with the transition metal compound of the component (A), which is the component (B), include (B-1) an ionic compound which forms an ionic complex, B-2) aluminoxanes and (B-3) Lewis acids.
【0022】ここで、(B−1)成分のイオン性の錯体
を形成するイオン性化合物としては、前記(A)成分の
遷移金属化合物と反応してイオン性の錯体を形成するイ
オン性化合物であれば、いずれのものでも使用できる
が、特に効率的に重合活性点を形成できるなどの点か
ら、次の一般式(II),(III) (〔L1 −R7 〕h+)a (〔Z〕- )b ・・・(II) (〔L2 h+)a (〔Z〕- )h ・・・(III) (ただし、L2 はM1 ,R8 R9 M2 ,R10 3 C又はR
11M2 である。)で表されるものを好適に使用すること
ができる。上記一般式(II),(III) において、L1 はル
イス塩基、〔Z〕- は、非配位アニオン〔Z1 〕- 又は
〔Z2 〕- 、ここで〔Z1 〕- は複数の基が元素に結合
したアニオンすなわち〔M3 G1 G3 ・・・Gf 〕(こ
こで、M3 は周期律表第5〜15族元素、好ましくは周
期律表第13〜15族元素を示す。G1 〜Gf はそれぞ
れ水素原子,ハロゲン原子,炭素数1〜20のアルキル
基,炭素数2〜40のジアルキルアミノ基,炭素数1〜
20のアルコキシ基,炭素数6〜20のアリール基,炭
素数6〜20のアリールオキシ基,炭素数7〜40のア
ルキルアリール基,炭素数7〜40のアリールアルキル
基,炭素数1〜20のハロゲン置換炭化水素基,炭素数
1〜20のアシルオキシ基,有機メタロイド基、又は炭
素数2〜20のヘテロ原子含有炭化水素基を示す。G1
〜Gf のうち2つ以上が環を形成していてもよい。fは
〔(中心金属M3 の原子価)+1〕の整数を示す。)、
〔Z2 〕- は、酸解離定数の逆数の対数(pKa )が−
10以下のブレンステッド酸単独又はブレンステッド酸
及びルイス酸の組合わせの共役塩基、あるいは一般的に
超強酸と定義される共役塩基を示す。また、ルイス塩基
が配位していてもよい。また、R7 は水素原子,炭素数
1〜20のアルキル基,炭素数6〜20のアリール基,
アルキルアリール基又はアリールアルキル基を示し、R
8 及びR9はそれぞれシクロペンタジエニル基,置換シ
クロペンタジエニル基,インデニル基、置換インデニル
基、フルオレニル基又は置換フルオレニル基、R10は炭
素数1〜20のアルキル基,アリール基,アルキルアリ
ール基又はアリールアルキル基を示す。R11はテトラフ
ェニルポルフィリン,フタロシアニンなどの大環状配位
子を示す。hは〔L1 −R7 〕,〔L2 〕のイオン価数
で1〜3の整数、aは1以上の整数、b=(h×a)で
ある。M1 は、周期律表第1〜3、11〜13、17族
元素を含むものであり、M2 は、周期律表第7〜12族
元素を示す。〕Here, the ionic compound forming the ionic complex of the component (B-1) is an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A). Any one can be used as long as it has any of the following general formulas (II) and (III) ([L 1 -R 7 ] h + ) a ([ Z] -) b ··· (II) ([L 2 h +) a ([Z] -) h ··· (III) (provided that, L 2 is M 1, R 8 R 9 M 2, R 10 3 C or R
11 is an M 2. ) Can be suitably used. In the above general formulas (II) and (III), L 1 is a Lewis base, [Z] − is a non-coordinating anion [Z 1 ] − or [Z 2 ] − , where [Z 1 ] − is a plurality of groups bound anions i.e. [M 3 G 1 G 3 ··· G f ] (here an element, M 3 is the periodic table 5-15 group element, preferably periodic table 13-15 group element G 1 to G f are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, and 1 to 1 carbon atoms, respectively.
An alkoxy group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms, and having 1 to 20 carbon atoms It represents a halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms. G 1
Two or more may form a ring of ~G f. f represents an integer of [(valence of central metal M 3) +1]. ),
[Z 2] - is the reciprocal of the acid dissociation constant logarithm (pKa) is -
A conjugate base of 10 or less Brönsted acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. R 7 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms,
An alkylaryl group or an arylalkyl group;
8 and R 9 are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, and R 10 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl. Or an arylalkyl group. R 11 represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is the ionic valence of [L 1 -R 7 ] and [L 2 ], and is an integer of 1 to 3, a is an integer of 1 or more, and b = (h × a). M 1 is one comprising at periodic table Group 1~3,11~13,17 element, M 2 denotes a periodic table 7-12 group element. ]
【0023】ここで、L1 の具体例としては、アンモニ
ア,メチルアミン,アニリン,ジメチルアミン,ジエチ
ルアミン,N−メチルアニリン,ジフェニルアミン,
N,N−ジメチルアニリン,トリメチルアミン,トリエ
チルアミン,トリ−n−ブチルアミン,メチルジフェニ
ルアミン,ピリジン,p−ブロモ−N,N−ジメチルア
ニリン,p−ニトロ−N,N−ジメチルアニリンなどの
アミン類、トリエチルホスフィン,トリフェニルホスフ
ィン,ジフェニルホスフィンなどのホスフィン類、テト
ラヒドロチオフェンなどのチオエーテル類、安息香酸エ
チルなどのエステル類、アセトニトリル,ベンゾニトリ
ルなどのニトリル類などを挙げることができる。Here, specific examples of L 1 include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.
【0024】R7 の具体例としては水素,メチル基,エ
チル基,ベンジル基,トリチル基などを挙げることがで
き、R8 ,R9 の具体例としては、シクロペンタジエニ
ル基,メチルシクロペンタジエニル基,エチルシクロペ
ンタジエニル基,ペンタメチルシクロペンタジエニル基
などを挙げることができる。R10の具体例としては、フ
ェニル基,p−トリル基,p−メトキシフェニル基など
を挙げることができ、R11の具体例としてはテトラフェ
ニルポルフィン,フタロシアニン,アリル,メタリルな
どを挙げることができる。また、M1 の具体例として
は、Li,Na,K,Ag,Cu,Br,I,I3 など
を挙げることができ、M2 の具体例としては、Mn,F
e,Co,Ni,Znなどを挙げることができる。ま
た、〔Z1 〕- ,すなわち〔M3 G1 G2 ・・・Gf 〕
において、M3 の具体例としてはB,Al,Si,P,
As,Sbなど、好ましくはB及びAlが挙げられる。
また、G1 ,G2 〜Gf の具体例としては、ジアルキル
アミノ基としてジメチルアミノ基,ジエチルアミノ基な
ど、アルコキシ基若しくはアリールオキシ基としてメト
キシ基,エトキシ基,n−ブトキシ基,フェノキシ基な
ど、炭化水素基としてメチル基,エチル基,n−プロピ
ル基,イソプロピル基,n−ブチル基,イソブチル基,
n−オクチル基,n−エイコシル基,フェニル基,p−
トリル基,ベンジル基,4−t−ブチルフェニル基,
3,5−ジメチルフェニル基など、ハロゲン原子として
フッ素,塩素,臭素,ヨウ素,ヘテロ原子含有炭化水素
基としてp−フルオロフェニル基,3,5−ジフルオロ
フェニル基,ペンタクロロフェニル基,3,4,5−ト
リフルオロフェニル基,ペンタフルオロフェニル基,
3,5−ビス(トリフルオロメチル)フェニル基,ビス
(トリメチルシリル)メチル基など、有機メタロイド基
としてペンタメチルアンチモン基、トリメチルシリル
基,トリメチルゲルミル基,ジフェニルアルシン基,ジ
シクロヘキシルアンチモン基,ジフェニル硼素などが挙
げられる。Specific examples of R 7 include hydrogen, methyl group, ethyl group, benzyl group and trityl group. Specific examples of R 8 and R 9 include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R 10 include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group, and specific examples of R 11 include a tetraphenylporphine, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M 1 include Li, Na, K, Ag, Cu, Br, I, and I 3. Specific examples of M 2 include Mn, F
e, Co, Ni, Zn and the like. Also, [Z 1 ] − , that is, [M 3 G 1 G 2 ... G f ]
In the above, specific examples of M 3 include B, Al, Si, P,
As and Sb, preferably B and Al.
Specific examples of G 1 , G 2 to G f include dimethylamino and diethylamino as dialkylamino groups, methoxy, ethoxy, n-butoxy, phenoxy and the like as alkoxy or aryloxy groups. As hydrocarbon groups, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
n-octyl group, n-eicosyl group, phenyl group, p-
Tolyl group, benzyl group, 4-t-butylphenyl group,
Fluorine, chlorine, bromine, iodine as a halogen atom, a p-fluorophenyl group, a 3,5-difluorophenyl group, a pentachlorophenyl group, a 3,4,5 -Trifluorophenyl group, pentafluorophenyl group,
Examples of organic metalloid groups such as 3,5-bis (trifluoromethyl) phenyl group and bis (trimethylsilyl) methyl group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group, and diphenylboron. Can be
【0025】また、非配位性のアニオンすなわちpKa
が−10以下のブレンステッド酸単独又はブレンステッ
ド酸及びルイス酸の組合わせの共役塩基〔Z2 〕- の具
体例としてはトリフルオロメタンスルホン酸アニオン
(CF3 SO3 )- ,ビス(トリフルオロメタンスルホ
ニル)メチルアニオン,ビス(トリフルオロメタンスル
ホニル)ベンジルアニオン,ビス(トリフルオロメタン
スルホニル)アミノ,過塩素酸アニオン(ClO4
)- ,トリフルオロ酢酸アニオン(CF3 CO2 )-,
ヘキサフルオロアンチモンアニオン(SbF5 )- ,フ
ルオロスルホン酸アニオン(FSO3 )- ,クロロスル
ホン酸アニオン(ClSO3 )- ,フルオロスルホン酸
アニオン/5−フッ化アンチモン(FSO3 /Sb
F5 )- ,フルオロスルホン酸アニオン/5−フッ化砒
素(FSO3 /AsF5 )- ,トリフルオロメタンスル
ホン酸/5−フッ化アンチモン(CF3 SO3 /SbF
5 )- などを挙げることができる。Further, a non-coordinating anion, ie, pKa
Specific examples of the conjugated base [Z 2 ] − of a Brönsted acid alone or a combination of a Brönsted acid and a Lewis acid having a -10 or less are trifluoromethanesulfonic acid anion (CF 3 SO 3 ) − , bis (trifluoromethanesulfonyl) ) Methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amino, perchlorate anion (ClO4
) - , Trifluoroacetate anion (CF 3 CO 2 ) - ,
Hexafluoroantimony anion (SbF 5 ) − , fluorosulfonic acid anion (FSO 3 ) − , chlorosulfonic acid anion (ClSO 3 ) − , fluorosulfonic acid anion / 5-antimony fluoride (FSO 3 / Sb)
F 5) -, fluorosulfonic acid anion / 5- fluoride arsenic (FSO 3 / AsF 5) - , trifluoromethanesulfonic acid / antimony pentafluoride (CF 3 SO 3 / SbF
5) - and the like.
【0026】このような前記(A)成分の遷移金属化合
物と反応してイオン性の錯体を形成するイオン性化合
物、すなわち(B−1)成分化合物の具体例としては、
テトラフェニル硼酸トリエチルアンモニウム,テトラフ
ェニル硼酸トリ−n−ブチルアンモニウム,テトラフェ
ニル硼酸トリメチルアンモニウム,テトラフェニル硼酸
テトラエチルアンモニウム,テトラフェニル硼酸メチル
(トリ−n−ブチル)アンモニウム,テトラフェニル硼
酸ベンジル(トリ−n−ブチル)アンモニウム,テトラ
フェニル硼酸ジメチルジフェニルアンモニウム,テトラ
フェニル硼酸トリフェニル(メチル)アンモニウム,テ
トラフェニル硼酸トリメチルアニリニウム,テトラフェ
ニル硼酸メチルピリジニウム,テトラフェニル硼酸ベン
ジルピリジニウム,テトラフェニル硼酸メチル(2−シ
アノピリジニウム),テトラキス(ペンタフルオロフェ
ニル)硼酸トリエチルアンモニウム,テトラキス(ペン
タフルオロフェニル)硼酸トリ−n−ブチルアンモニウ
ム,テトラキス(ペンタフルオロフェニル)硼酸トリフ
ェニルアンモニウム,テトラキス(ペンタフルオロフェ
ニル)硼酸テトラ−n−ブチルアンモニウム,テトラキ
ス(ペンタフルオロフェニル)硼酸テトラエチルアンモ
ニウム,テトラキス(ペンタフルオロフェニル)硼酸ベ
ンジル(トリ−n−ブチル)アンモニウム,テトラキス
(ペンタフルオロフェニル)硼酸メチルジフェニルアン
モニウム,テトラキス(ペンタフルオロフェニル)硼酸
トリフェニル(メチル)アンモニウム,テトラキス(ペ
ンタフルオロフェニル)硼酸メチルアニリニウム,テト
ラキス(ペンタフルオロフェニル)硼酸ジメチルアニリ
ニウム,テトラキス(ペンタフルオロフェニル)硼酸ト
リメチルアニリニウム,テトラキス(ペンタフルオロフ
ェニル)硼酸メチルピリジニウム,テトラキス(ペンタ
フルオロフェニル)硼酸ベンジルピリジニウム,テトラ
キス(ペンタフルオロフェニル)硼酸メチル(2−シア
ノピリジニウム),テトラキス(ペンタフルオロフェニ
ル)硼酸ベンジル(2−シアノピリジニウム),テトラ
キス(ペンタフルオロフェニル)硼酸メチル(4−シア
ノピリジニウム),テトラキス(ペンタフルオロフェニ
ル)硼酸トリフェニルホスホニウム,テトラキス〔ビス
(3,5−ジトリフルオロメチル)フェニル〕硼酸ジメ
チルアニリニウム,テトラフェニル硼酸フェロセニウ
ム,テトラフェニル硼酸銀,テトラフェニル硼酸トリチ
ル,テトラフェニル硼酸テトラフェニルポルフィリンマ
ンガン,テトラキス(ペンタフルオロフェニル)硼酸フ
ェロセニウム,テトラキス(ペンタフルオロフェニル)
硼酸(1,1'−ジメチルフェロセニウム),テトラキ
ス(ペンタフルオロフェニル)硼酸デカメチルフェロセ
ニウム,テトラキス(ペンタフルオロフェニル)硼酸
銀、テトラキス(ペンタフルオロフェニル)硼酸トリチ
ル,テトラキス(ペンタフルオロフェニル)硼酸リチウ
ム,テトラキス(ペンタフルオロフェニル)硼酸ナトリ
ウム,テトラキス(ペンタフルオロフェニル)硼酸テト
ラフェニルポルフィリンマンガン,テトラフルオロ硼酸
銀,ヘキサフルオロ燐酸銀,ヘキサフルオロ砒素酸銀,
過塩素酸銀,トリフルオロ酢酸銀,トリフルオロメタン
スルホン酸銀などを挙げることができる。この(B−
1)成分である、該(A)成分の遷移金属化合物と反応
してイオン性の錯体を形成するイオン性化合物は一種用
いてもよく、また二種以上を組み合わせて用いてもよ
い。一方、(B−2)成分のアルミノキサンとしては、
下記一般式(IV) で示される鎖状アルミノキサン、及び
一般式(V)で示される環状アルミノキサンを挙げるこ
とができる。Specific examples of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, ie, the compound of the component (B-1), include:
Triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyltetraphenylborate (tri-n- Butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyl 2-phenylopyridinium Triethylammonium, tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate ) Tri-n-butylammonium borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Benzyl (tri-n-butyl) ammonium borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, methylanilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Dimethylanilinium fluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, tetrakis Methylpyridinium pentafluorophenyl) borate, benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, tetrakis ( Methyl pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate, ferrocenium tetraphenylborate, tetraphenyl Silver borate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, tetrakis (pentafluorophenyl) borate Rosenium, tetrakis (pentafluorophenyl)
(1,1'-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) Lithium borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate,
Silver perchlorate, silver trifluoroacetate, silver trifluoromethanesulfonate and the like can be mentioned. This (B-
The ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex, which is the component 1), may be used alone or in combination of two or more. On the other hand, as the aluminoxane of the component (B-2),
A chain aluminoxane represented by the following general formula (IV) and a cyclic aluminoxane represented by the general formula (V) can be exemplified.
【0027】[0027]
【化9】 Embedded image
【0028】(式中、R12は、それぞれ炭素数1〜2
0、好ましくは1〜8のアルキル基を示し、それらは同
じであっても異なっていてもよい。また、pは2<p≦
40、rは1<r≦50の整数である。) 具体的には、メチルアルミノキサン、エチルアルミノキ
サン、イソブチルアルミノキサン等のアルミノキサン等
が挙げられる。前記アルミノキサンの製造法としては、
アルキルアルミニウムと水などの縮合剤とを接触させる
方法が挙げられるが、その手段については特に限定はな
く、公知の方法に準じて反応させればよい。例えば有機
アルミニウム化合物を有機溶剤に溶解しておき、これを
水と接触させる方法、重合時に当初有機アルミニウム化
合物を加えておき、後に水を添加する方法、金属塩など
に含有されている結晶水、無機物や有機物への吸着水を
有機アルミニウム化合物と反応させる方法、テトラアル
キルジアルミノキサンにトリアルキルアルミニウムを反
応させ、さらに水を反応させる方法などがある。なお、
アルミノキサンとしては、トルエン不溶性のものであっ
てもよい。(Wherein, each of R 12 has 1 to 2 carbon atoms.
It represents 0, preferably 1-8 alkyl groups, which may be the same or different. Also, p is 2 <p ≦
40 and r are integers satisfying 1 <r ≦ 50. Specific examples include aluminoxanes such as methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. As a method for producing the aluminoxane,
A method of contacting an alkylaluminum with a condensing agent such as water may be mentioned, but the method is not particularly limited, and the reaction may be performed according to a known method. For example, a method of dissolving an organic aluminum compound in an organic solvent and bringing it into contact with water, a method of adding an organic aluminum compound initially during polymerization and adding water later, water of crystallization contained in a metal salt and the like, There are a method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water. In addition,
The aluminoxane may be toluene-insoluble.
【0029】これらのアルミノキサンは一種用いてもよ
く、二種以上を組み合わせて用いてもよい。(B−3)
成分のルイス酸については特に制限はなく、有機化合物
でも固体状無機化合物でもよい。有機化合物としては、
硼素化合物やアルミニウム化合物などが、無機化合物と
してはマグネシウム化合物,アルミニウム化合物などが
効率的に活性点を形成できる点から好ましく用いられ
る。該アルミニウム化合物としては例えばビス(2,6
−ジ−t−ブチル−4−メチルフェノキシ)アルミニウ
ムメチル,(1,1−ビ−2−ナフトキシ)アルミニウ
ムメチルなどが、マグネシウム化合物としては例えば塩
化マグネシウム,ジエトキシマグネシウムなどが、アル
ミニウム化合物としては酸化アルミニウム,塩化アルミ
ニウムなどが、硼素化合物としては例えばトリフェニル
硼素,トリス(ペンタフルオロフェニル)硼素,トリス
〔3,5−ビス(トリフルオロメチル)フェニル〕硼
素,トリス〔(4−フルオロメチル)フェニル〕硼素,
トリメチル硼素,トリエチル硼素,トリ−n−ブチル硼
素,トリス(フルオロメチル)硼素,トリス(ペンタフ
ルオロエチル)硼素,トリス(ノナフルオロブチル)硼
素,トリス(2,4,6−トリフルオロフェニル)硼
素,トリス(3,5−ジフルオロ)硼素,トリス〔3,
5−ビス(トリフルオロメチル)フェニル〕硼素,ビス
(ペンタフルオロフェニル)フルオロ硼素,ジフェニル
フルオロ硼素,ビス(ペンタフルオロフェニル)クロロ
硼素,ジメチルフルオロ硼素,ジエチルフルオロ硼素,
ジ−n−ブチルフルオロ硼素,ペンタフルオロフェニル
ジフルオロ硼素,フェニルジフルオロ硼素,ペンタフル
オロフェニルジクロロ硼素,メチルジフルオロ硼素,エ
チルジフルオロ硼素,n−ブチルジフルオロ硼素などが
挙げられる。These aluminoxanes may be used alone or in combination of two or more. (B-3)
The component Lewis acid is not particularly limited, and may be an organic compound or a solid inorganic compound. As organic compounds,
Boron compounds and aluminum compounds are preferably used because inorganic compounds such as magnesium compounds and aluminum compounds can efficiently form active sites. Examples of the aluminum compound include bis (2,6
-Di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-naphthoxy) aluminum methyl and the like; magnesium compounds such as magnesium chloride and diethoxymagnesium; Examples of boron compounds include aluminum, aluminum chloride, and the like. For example, triphenylboron, tris (pentafluorophenyl) boron, tris [3,5-bis (trifluoromethyl) phenyl] boron, and tris [(4-fluoromethyl) phenyl] boron,
Trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl) boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, Tris (3,5-difluoro) boron, tris [3
5-bis (trifluoromethyl) phenyl] boron, bis (pentafluorophenyl) fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron,
Examples thereof include di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoroboron, ethyldifluoroboron, and n-butyldifluoroboron.
【0030】これらのルイス酸は一種用いてもよく、ま
た二種以上を組み合わせて用いてもよい。本発明の重合
用触媒における(A)触媒成分と(B)触媒成分との使
用割合は、(B)触媒成分として(B−1)化合物を用
いた場合には、モル比で好ましくは10:1〜1:10
0、より好ましくは2:1〜1:10の範囲が望まし
く、上記範囲を逸脱する場合は、単位重量ポリマーあた
りの触媒コストが高くなり、実用的でない。また(B−
2)化合物を用いた場合には、モル比で好ましくは1:
1〜1:1000000、より好ましくは1:10〜
1:10000の範囲が望ましい。この範囲を逸脱する
場合は単位重量ポリマーあたりの触媒コストが高くな
り、実用的でない。前記(A)触媒成分と(B−3)触
媒成分との使用割合は、モル比で、好ましくは10:1
〜1:2000、より好ましくは5:1〜1:100
0、さらに好ましくは2:1〜1:500の範囲が望ま
しく、この範囲を逸脱する場合は単位重量ポリマーあた
りの触媒コストが高くなり、実用的でない。また、触媒
成分(B)としては(B−1),(B−2),(B−
3)などを単独または二種以上組み合わせて用いること
もできる。These Lewis acids may be used alone or in combination of two or more. When the (B) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component and the (B) catalyst component in the polymerization catalyst of the present invention is preferably 10: 1-1: 10
0, more preferably in the range of 2: 1 to 1:10, and if it is outside the above range, the catalyst cost per unit weight polymer increases, which is not practical. Also, (B-
2) When a compound is used, the molar ratio is preferably 1:
1-1: 1,000,000, more preferably 1:10
A range of 1: 10000 is desirable. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. The use ratio of the catalyst component (A) to the catalyst component (B-3) is preferably 10: 1 by molar ratio.
1 : 1: 2000, more preferably 5: 1 to 1: 100
0, more preferably in the range of 2: 1 to 1: 500. If the ratio deviates from this range, the catalyst cost per unit weight polymer increases, which is not practical. The catalyst component (B) includes (B-1), (B-2), and (B-
3) and the like can be used alone or in combination of two or more.
【0031】本発明の重合用触媒は、前記の(A)成分
及び(B)成分を主成分として含有するものであっても
よいし、また、(A)成分、(B)成分及び(C)有機
アルミニウム化合物を主成分として含有するものであっ
てもよい。ここで、(C)成分の有機アルミニウム化合
物としては、一般式(VI) R13 V AlQ3-V ・・・(VI) (式中、R13は炭素数1〜10のアルキル基、Qは水素
原子、炭素数1〜20のアルコキシ基,炭素数6〜20
のアリール基又はハロゲン原子を示し、vは1〜3の実
数である)で示される化合物が用いられる。The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C). ) An organic aluminum compound may be contained as a main component. Here, as the organoaluminum compound of the component (C), a general formula (VI) R 13 V AlQ 3-V (VI) (wherein, R 13 is an alkyl group having 1 to 10 carbon atoms, and Q is Hydrogen atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
And v is a real number of 1 to 3).
【0032】前記一般式(VI) で示される化合物の具体
例としては、トリメチルアルミニウム,トリエチルアル
ミニウム,トリイソプロピルアルミニウム,トリイソブ
チルアルミニウム,ジメチルアルミニウムクロリド,ジ
エチルアルミニウムクロリド,メチルアルミニウムジク
ロリド,エチルアルミニウムジクロリド,ジメチルアル
ミニウムフルオリド,ジイソブチルアルミニウムヒドリ
ド,ジエチルアルミニウムヒドリド,エチルアルミニウ
ムセスキクロリド等が挙げられる。これらの有機アルミ
ニウム化合物は一種用いてもよく、二種以上を組合せて
用いてもよい。前記(A)触媒成分と(C)触媒成分と
の使用割合は、モル比で好ましくは1:1〜1:100
00、より好ましくは1:5〜1:2000、さらに好
ましくは1:10ないし1:1000の範囲が望まし
い。該(C)触媒成分を用いることにより、遷移金属当
たりの重合活性を向上させることができるが、あまり多
い場合、特に上記範囲を逸脱する時は有機アルミニウム
化合物が無駄になるとともに、重合体中に多量に残存
し、また少ない場合は充分な触媒活性が得られず、好ま
しくない場合がある。Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethylaluminum. Aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like. These organoaluminum compounds may be used alone or in combination of two or more. The molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 100.
00, more preferably 1: 5 to 1: 2000, even more preferably 1:10 to 1: 1000. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, when the amount is too large, especially when it is out of the above range, the organoaluminum compound is wasted and the polymer is not contained in the polymer. If the amount is large and the amount is small, sufficient catalytic activity cannot be obtained, which may be undesirable.
【0033】また、本発明においては各成分の接触に際
し、または接触後、ポリエチレン、ポリプロピレン等の
重合体、シリカ、アルミナ等の無機酸化物を共存または
接触させてもよい。担体に担持するにあたっては、ポリ
マー上に担持するのが好ましく、このような担体ポリマ
ーとしては、その粒径は1〜300μm、好ましくは1
0〜200μm、より好ましくは20〜100μmであ
る。この粒径が1μmよりも小さいと重合体中の微紛が
増大し、300μmを超えるものであると重合体中の粗
大粒子が増大し、嵩密度の低下や製造工程でのホッパー
つまりの原因となる。この場合の担体の比表面積は、1
〜1,000m2 /g、好ましくは50〜500m2 /
gであり、細孔容積は0.1〜5m3 /g、好ましくは
0.3〜3m3 /gである。 接触は、窒素等の不活性
気体中、ペンタン、ヘキサン、ヘプタン、トルエン、キ
シレン等の炭化水素中で行なってもよい。各成分の添加
または接触は、重合温度下で行うことができることはも
ちろん、−30℃〜各溶媒の沸点、特に室温から溶媒の
沸点の間で行なうのが好ましい。In the present invention, a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or be brought into contact with or after the contact of each component. When supported on a carrier, it is preferable to support the polymer on a polymer. Such a carrier polymer has a particle size of 1 to 300 μm, preferably 1 to 300 μm.
It is 0 to 200 μm, more preferably 20 to 100 μm. When the particle size is smaller than 1 μm, fine powder in the polymer increases, and when the particle size is larger than 300 μm, coarse particles in the polymer increase, which causes a decrease in bulk density and a hopper clogging in a manufacturing process. Become. The specific surface area of the carrier in this case is 1
~1,000m 2 / g, preferably 50~500m 2 /
g, and the pore volume is 0.1 to 5 m 3 / g, preferably 0.3 to 3 m 3 / g. The contact may be performed in an inert gas such as nitrogen or a hydrocarbon such as pentane, hexane, heptane, toluene, or xylene. The addition or contact of each component can be carried out at a polymerization temperature, and it is preferable that the addition or contact be carried out at -30 ° C to the boiling point of each solvent, particularly between room temperature and the boiling point of the solvent.
【0034】本発明のオレフィン系重合体の製造方法
は、前記(A)成分の一般式(I)で表される遷移金属
化合物、(B)該(A)成分の遷移金属化合物と反応し
てイオン性の錯体を形成しうる化合物及び必要に応じて
(C)有機アルミニウム化合物を接触させてなるオレフ
ィン類重合用触媒の存在下、オレフィンを単独重合また
は共重合させる方法である。なお、(C)成分の有機ア
ルミニウム化合物としては、前記一般式(VI) で表され
る化合物が用いられるが、好ましくは、トリアルキルア
ルミニウム化合物である。中でも、トリメチルアルミニ
ウム、トリイソブチルアルミニウムが好ましい。本発明
のオレフィン系重合体の製造方法においては、(C)成
分の有機アルミニウム化合物は予め(A)成分及び/又
は(B)成分と接触させて用いてもよいし、反応器中に
(C)成分を投入しておき(A)成分、(B)成分と接
触させて用いてもよい。(C)成分の用いる量は前記の
オレフィン類重合用触媒と同様である。本発明のオレフ
ィン系重合体の製造方法によれば、上述した重合用触媒
を用いて、オレフィン類の単独重合、またはオレフィン
と他のオレフィン類及び/または他の単量体との共重合
(つまり、異種のオレフィン類相互との共重合、オレフ
ィン類と他の単量体との共重合、或いは異種のオレフィ
ン類相互と他の単量体との共重合)を好適に行うことが
できる。The process for producing an olefin polymer of the present invention comprises reacting the component (A) with the transition metal compound represented by the general formula (I), and (B) reacting with the transition metal compound of the component (A). In this method, an olefin is homopolymerized or copolymerized in the presence of a compound capable of forming an ionic complex and, if necessary, (C) an olefin polymerization catalyst obtained by contacting an organoaluminum compound. As the organoaluminum compound as the component (C), a compound represented by the general formula (VI) is used, and a trialkylaluminum compound is preferable. Among them, trimethylaluminum and triisobutylaluminum are preferable. In the method for producing an olefin polymer of the present invention, the organoaluminum compound as the component (C) may be used in contact with the component (A) and / or the component (B) in advance, or (C) )) Component may be charged and used in contact with component (A) and component (B). The amount of the component (C) is the same as in the olefin polymerization catalyst. According to the method for producing an olefin polymer of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers using the polymerization catalyst described above (that is, , Copolymerization of different olefins with each other, copolymerization of olefins with other monomers, or copolymerization of different olefins with other monomers).
【0035】該オレフィン類については特に制限はない
が、炭素数2〜20のα―オレフィンが好ましい。この
α―オレフィンとしては、例えばエチレン、プロピレ
ン、1−ブテン、1−ペンテン、1−ヘキセン、1−ヘ
プテン、1−オクテン、1−ノネン、1−デセン、4−
フェニル−1−ブテン、6−フェニル−1−ヘキセン、
3−メチル−1−ブテン、4−メチル−1−ブテン、3
−メチル−1−ペンテン、4−メチル−1−ヘキセン、
5−メチル−1−ヘキセン、3, 3−ジメチル−1−ペ
ンテン、3, 4−ジメチル−1−ペンテン、4,4−ジ
メチル−1−ペンテン、ビニルシクロヘキサン等のα−
オレフィン類、1, 3−ブタジエン、1,4−ペンタジ
エン、1, 5−ヘキサジエン等のジエン類、ヘキサフル
オロプロペン、テトラフルオロエチレン、2−フルオロ
プロペン、フルオロエチレン、1,1−ジフルオロエチ
レン、3−フルオロプロペン、トリフルオロエチレン、
3,4−ジクロロ−1−ブテン等のハロゲン置換α−オ
レフィン、シクロペンテン、シクロヘキセン、ノルボル
ネン、5−メチルノルボルネン、5−エチルノルボルネ
ン、5−プロピルノルボルネン、5, 6−ジメチルノル
ボルネン、5−ベンジルノルボルネン等の環状オレフィ
ン類、さらにはスチレン、p−メチルスチレン、p−エ
チルスチレン、p−プロピルスチレン、p−イソプロピ
ルスチレン、p−ブチルスチレン、p−tert−ブチ
ルスチレン、p−フェニルスチレン、o−メチルスチレ
ン、o−エチルスチレン、o−プロピルスチレン、o−
イソプロピルスチレン、m−メチルスチレン、m−エチ
ルスチレン、m−イソプロピルスチレン、m−ブチルス
チレン、メシチルスチレン、2,4−ジメチルスチレ
ン、2,5−ジメチルスチレン、3,5−ジメチルスチ
レン等のアルキルスチレン類、p−メトキシスチレン、
o−メトキシスチレン、m−メトキシスチレン等のアル
コキシスチレン類、p −クロロスチレン、m−クロロス
チレン、o−クロロスチレン、p−ブロモスチレン、m
−ブロモスチレン、o−ブロモスチレン、p−フルオロ
スチレン、m−フルオロスチレン、o−フルオロスチレ
ン、o−メチル−p−フルオロスチレン等のハロゲン化
スチレン類、更にはトリメチルシリルスチレン、ビニル
安息香酸エステル、ジビニルベンゼン等が挙げられる。
また、上述した他のオレフィン類についても、上記オレ
フィン類の中から適宜選定すれば良い。The olefin is not particularly limited, but is preferably an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-
Phenyl-1-butene, 6-phenyl-1-hexene,
3-methyl-1-butene, 4-methyl-1-butene, 3
-Methyl-1-pentene, 4-methyl-1-hexene,
Α- such as 5-methyl-1-hexene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene and vinylcyclohexane;
Olefins, 1,3-butadiene, 1,4-pentadiene, dienes such as 1,5-hexadiene, hexafluoropropene, tetrafluoroethylene, 2-fluoropropene, fluoroethylene, 1,1-difluoroethylene, 3-ene Fluoropropene, trifluoroethylene,
Halogen-substituted α-olefins such as 3,4-dichloro-1-butene, cyclopentene, cyclohexene, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 5-benzylnorbornene and the like Cyclic olefins, furthermore, styrene, p-methylstyrene, p-ethylstyrene, p-propylstyrene, p-isopropylstyrene, p-butylstyrene, p-tert-butylstyrene, p-phenylstyrene, o-methylstyrene , O-ethylstyrene, o-propylstyrene, o-
Alkyl such as isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m-butylstyrene, mesitylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene and 3,5-dimethylstyrene Styrenes, p-methoxystyrene,
Alkoxystyrenes such as o-methoxystyrene and m-methoxystyrene, p-chlorostyrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m
Halogenated styrenes such as -bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl-p-fluorostyrene, furthermore, trimethylsilylstyrene, vinyl benzoate, divinyl Benzene is exemplified.
The other olefins described above may be appropriately selected from the olefins.
【0036】本発明においては、上記オレフィン類は一
種用いてもよいし、二種以上を組み合わせてもよい。二
種以上のオレフィンの共重合を行う場合、上記オレフィ
ン類を任意に組み合わせることができる。また、本発明
においては、上記オレフィン類と他の単量体とを共重合
させてもよく、この際用いられる他の単量体としては、
例えば1,4,5,8―ジメタノー1,2,3,4,4
a,5,8,8a−オクタヒドロナフタレン等の多環状
オレフィン類、ノルボルナジエン、5−エチリデンノル
ボルネン、5−ビニルノルボルネン、ジシクロペンタジ
エンなどの環状ジオレフィン類、アクリル酸エチル、メ
タクリル酸メチルなどの不飽和エステル類などを挙げる
事ができる。本発明においては、このオレフィン類とし
て、特にプロピレンが好適である。また、オレフィン類
を重合させる方法については特に制限はなく、スラリー
重合法、溶液重合法、気相重合法、塊状重合法、懸濁重
合法など、任意の重合法を採用することができる。In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined. Further, in the present invention, the above olefins and other monomers may be copolymerized, as other monomers used in this case,
For example, 1,4,5,8-dimethano 1,2,3,4,4
polycyclic olefins such as a, 5,8,8a-octahydronaphthalene; cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene; and non-cyclic olefins such as ethyl acrylate and methyl methacrylate. Saturated esters and the like can be mentioned. In the present invention, propylene is particularly preferred as the olefin. The method for polymerizing olefins is not particularly limited, and any polymerization method such as a slurry polymerization method, a solution polymerization method, a gas phase polymerization method, a bulk polymerization method, and a suspension polymerization method can be employed.
【0037】重合溶媒を用いる場合には、その溶媒とし
ては、ベンゼン、トルエン、キシレン、n−ヘキサン、
n−ヘプタン、シクロヘキサン、塩化メチレン、クロロ
ホルム、1,2−ジクロロエタン、クロロベンセン等の
炭化水素類やハロゲン化炭化水素類などが挙げられる。
これらは一種用いてもよく、二種以上を組み合わせて用
いてもよい。また、重合に用いるモノマーもその種類に
よっては使用することができる。 また、重合反応にお
ける触媒の使用量は、溶媒1リットル当たり、(A)成
分が、通常0.5〜100マイクロモル、好ましくは2
〜25マイクロモルの範囲になるように選ぶのが重合活
性および反応器効率の面から有利である。重合条件につ
いては、圧力は、通常、常圧〜200MPa・Gの範囲
で選択される。また、反応温度は、通常−50℃〜25
0℃の範囲である。重合体の分子量の調節方法として
は、各触媒成分の種類、使用量、重合温度の選択および
水素の導入などが挙げられる。When a polymerization solvent is used, the solvent may be benzene, toluene, xylene, n-hexane,
Examples include hydrocarbons such as n-heptane, cyclohexane, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, halogenated hydrocarbons, and the like.
These may be used alone or in combination of two or more. Further, the monomers used for the polymerization may be used depending on the type. The amount of the catalyst used in the polymerization reaction is such that the component (A) is used in an amount of usually 0.5 to 100 μmol, preferably 2 to 1 liter of the solvent.
It is advantageous to select from the range of 2525 μmol from the viewpoint of polymerization activity and reactor efficiency. As for the polymerization conditions, the pressure is usually selected from the range of normal pressure to 200 MPa · G. The reaction temperature is usually -50 ° C to 25 ° C.
It is in the range of 0 ° C. Examples of the method for controlling the molecular weight of the polymer include the type and amount of each catalyst component, the selection of the polymerization temperature, and the introduction of hydrogen.
【0038】さらに、本発明におけるオレフィン類の重
合時には、上記触媒を用いて予備重合を行うことができ
る。この予備重合は、固体触媒成分に少量のオレフィン
を接触させて行うことができ、この場合の反応温度は、
−20〜100℃、好ましくは−10〜70℃、特に好
ましくは0〜50℃である。また、この予備重合に際し
て用いる溶媒としては、不活性炭化水素、脂肪族炭化水
素、芳香族炭化水素、モノマーが用いられるが、特に脂
肪族炭化水素が好ましい。この予備重合を無溶媒で行う
こともできる。また、予備重合生成物は、その極限粘度
〔η〕(135℃、デカリン中での測定)が0.2デシ
リットル/g、好ましくは0,5デシリットル/g以上
となるように行うのがよく、触媒中の遷移金属成分1ミ
リモルあたりの予備重合生成物の量が、1〜10,00
0g、好ましくは10〜1,000gとなるように条件
を調整することが好ましい。Further, in the polymerization of olefins in the present invention, preliminary polymerization can be carried out using the above catalyst. This prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component.
The temperature is -20 to 100C, preferably -10 to 70C, particularly preferably 0 to 50C. As a solvent used in the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, or a monomer is used, and an aliphatic hydrocarbon is particularly preferable. This prepolymerization can also be performed without a solvent. The prepolymerized product is preferably subjected to an intrinsic viscosity [η] (measured at 135 ° C. in decalin) of 0.2 deciliter / g, preferably 0.5 deciliter / g or more. The amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is from 1 to 10,000.
It is preferable to adjust the conditions so as to be 0 g, preferably 10 to 1,000 g.
【0039】[0039]
【実施例】次に、本発明を実施例により、さらに詳しく
説明するが、本発明は、これらの例によってなんら限定
されるものではない。1H−NMRの測定には、日本電
子(株)製JEOL−EX90を使用した。 実施例1 (1)錯体(A−1)の製造 (イ)3−ブロモ−4−トリメチルシリルオキシトルエ
ンの合成 ジムロート管,50ミリリットル滴下ロート付きの50
0ミリリットル三つ口フラスコに、2−ブロモ−p−ク
レゾール25g(0.134モル)及び脱水エーテル15
0ミリリットル,トリメチルシリルクロリド17.1ミリ
リットル(0.134モル)を投入した。次いで、滴下し
たロートにトリエチルアミン18.7ミリリットル(0.1
34モル)及び脱水エーテル50ミリリットルを投入
し、トリエチルアミンのエーテル溶液を氷冷下でゆっく
りと滴下した。滴下終了後、室温で30分間攪拌した。
その後、飽和炭酸水素ナトリウム水溶液600ミリリッ
トルを投入しエーテル抽出を行った。その抽出溶液に無
水硫酸マグネシウムを加え、ろ過後、溶媒留去すること
により、目的化合物33.9g(収率98%)を得た。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. For 1 H-NMR measurement, JEOL-EX90 manufactured by JEOL Ltd. was used. Example 1 (1) Production of Complex (A-1) (a) Synthesis of 3-bromo-4-trimethylsilyloxytoluene A Dimroth tube with a 50 ml dropping funnel was used.
In a 0 ml three-necked flask, 25 g (0.134 mol) of 2-bromo-p-cresol and 15 parts of dehydrated ether 15 were added.
0 ml and 17.1 ml (0.134 mol) of trimethylsilyl chloride were charged. Then, 18.7 ml (0.1 ml) of triethylamine was added to the dropping funnel.
34 mol) and 50 ml of dehydrated ether, and an ether solution of triethylamine was slowly added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes.
Thereafter, 600 ml of a saturated aqueous solution of sodium hydrogencarbonate was added, and ether extraction was performed. Anhydrous magnesium sulfate was added to the extracted solution, and after filtration, the solvent was distilled off, thereby obtaining 33.9 g (yield 98%) of the target compound.
【0040】(ロ)4−メチル−2−トリメチルシリル
フェノールの合成 50ミリリットル滴下ロート付きの500ミリリットル
三つ口フラスコに3−ブロモ−4−トリメチルシリルオ
キシトルエン33.9g(0.131モル)及び脱水テトラ
ヒドロフラン150ミリリットルを投入した。次に、滴
下ロートにt−ブチルリチウム1.5モル/リットル濃度
のシクロヘキサン溶液87ミリリットル(0.131モ
ル)を投入し、−40〜−30℃でゆっくりと滴下し
た。30分後、飽和塩化アンモニウム水溶液150ミリ
リットルを投入し、エーテル抽出を行った。その抽出溶
液に無水硫酸マグネシウムを加え、ろ過後、溶媒留去す
ることにより、目的化合物23.3g(収率99%)を得
た。(B) Synthesis of 4-methyl-2-trimethylsilylphenol In a 500 ml three-necked flask equipped with a 50 ml dropping funnel, 33.9 g (0.131 mol) of 3-bromo-4-trimethylsilyloxytoluene and dehydrated tetrahydrofuran were added. 150 milliliters were charged. Next, 87 ml (0.131 mol) of a cyclohexane solution having a concentration of 1.5 mol / liter of t-butyllithium was put into the dropping funnel, and the mixture was slowly dropped at -40 to -30 ° C. After 30 minutes, 150 ml of a saturated aqueous ammonium chloride solution was added, and ether extraction was performed. Anhydrous magnesium sulfate was added to the extracted solution, and after filtration, the solvent was distilled off, thereby obtaining 23.3 g (yield: 99%) of the target compound.
【0041】(ハ)4−メチル−6−トリメチルシリル
サリチルアルデヒドの合成 ジムロート管、50ミリリットル滴下ロート付きの50
0ミリリットル三つ口フラスコに脱水ジエチルエーテル
100ミリリットルおよびマグネシウム粉3.3g、ヨウ
素0.05gを投入した。滴下ロートにエチルブロミド1
4.6g(0.134モル)および脱水ジエチルエーテル5
0ミリリットルを投入し、穏やかに還流する程度にゆっ
くりと滴下した。滴下終了後、室温で30分間攪拌した。
次に、滴下ロートに4−メチル−2−トリメチルシリル
フェノール23.3g(0.129モル)および脱水ジエチ
ルエーテル50ミリリットルを投入し、ゆっくりと滴下
した。滴下終了後、溶媒を減圧留去し得られた残留物中
に脱水トルエン400ミリリットルおよびパラホルムア
ルデヒド8.1g,ヘキサメチルホスホラスアミド24g
(0.134モル)を投入し、4時間、加熱還流した。反
応溶液を室温まで冷却した後、分液ロートを用いて飽和
硫酸銅溶液100ミリリットルで3回洗浄した。有機相
に無水硫酸マグネシウムを加え、ろ過後、溶媒留去し残
留物を得た。得られた残留物をカラム精製することによ
り目的化合物を5.4g(収率20%)を得た。(C) Synthesis of 4-methyl-6-trimethylsilylsalicylaldehyde A 50-ml Dimroth tube with a 50 ml dropping funnel was used.
100 ml of dehydrated diethyl ether, 3.3 g of magnesium powder and 0.05 g of iodine were put into a 0 ml three-necked flask. Ethyl bromide 1 in dropping funnel
4.6 g (0.134 mol) and dehydrated diethyl ether 5
0 ml was added, and the mixture was slowly added dropwise so as to cause gentle reflux. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes.
Next, 23.3 g (0.129 mol) of 4-methyl-2-trimethylsilylphenol and 50 ml of dehydrated diethyl ether were charged into the dropping funnel and slowly dropped. After completion of the dropwise addition, the solvent was distilled off under reduced pressure, and 400 ml of dehydrated toluene, 8.1 g of paraformaldehyde and 24 g of hexamethylphosphoramide were added to the residue obtained.
(0.134 mol) and heated under reflux for 4 hours. After cooling the reaction solution to room temperature, it was washed three times with 100 ml of a saturated copper sulfate solution using a separating funnel. Anhydrous magnesium sulfate was added to the organic phase, and after filtration, the solvent was distilled off to obtain a residue. The obtained residue was purified by column to obtain 5.4 g (yield: 20%) of the target compound.
【0042】(ニ)配位子(A−1−a)の合成(D) Synthesis of ligand (A-1-a)
【0043】[0043]
【化10】 Embedded image
【0044】100ミリリットルフラスコにメタノール
30ミリリットルおよび4−メチル−6−トリメチルシ
リルサリチルアルデヒド1.0g(4.8 ミリモル)、ぎ酸
(1滴)を投入した。さらに攪拌しながら、室温下でt
−ブチルアミン0.36g(4.8 ミリモル)を滴下したの
ち、2時間攪拌した。反応終了後、水50ミリリットル
を投入しジエチルエーテル100ミリリットルで抽出し
た。分液ロートで有機相を分取し、有機相に無水硫酸マ
グネシウムを加え、ろ過後、溶媒留去し残留物を得た。
得られた残留物をカラム精製することにより目的化合物
を1.0g(収率80%)を得た。A 100 ml flask was charged with 30 ml of methanol, 1.0 g (4.8 mmol) of 4-methyl-6-trimethylsilylsalicylaldehyde and one drop of formic acid. With further stirring, t
After dropwise adding 0.36 g (4.8 mmol) of -butylamine, the mixture was stirred for 2 hours. After completion of the reaction, 50 ml of water was added, and the mixture was extracted with 100 ml of diethyl ether. The organic phase was separated by a separating funnel, anhydrous magnesium sulfate was added to the organic phase, and the mixture was filtered and the solvent was distilled off to obtain a residue.
The obtained residue was purified by a column to obtain 1.0 g (yield: 80%) of the target compound.
【0045】(ホ)錯体(A−1)の合成Synthesis of (e) complex (A-1)
【0046】[0046]
【化11】 Embedded image
【0047】窒素置換した200ミリリットルシュレン
クに、上記(ニ)で合成した配位子(A−1−a)1.0
g(3.8ミリモル)及び脱水ヘキサン40ミリリットル
を投入した。その溶液にn−ブチルリチウム1.50モル
/リットル濃度のヘキサン溶液2.6ミリリットル(3.9
ミリモル)を−78℃で滴下した。滴下終了後、室温で
8時間攪拌した。そして、溶媒を減圧留去した後、脱水
トルエン25ミリリットルを加え、−78℃に冷却し、
四塩化ジルコニウム0.44g(1.9ミリモル)の脱水ト
ルエン25ミリリットル懸濁液を滴下した。滴下終了
後、室温で6時間攪拌した。反応終了後、カヌラーでろ
過し、ろ液を濃縮し脱水ヘキサンを加えた。生じた沈澱
物をろ別、乾燥することにより、目的化合物を0.5g得
た(収率40%)。このものについて、プロトン核磁気
共鳴分光( 1H−NMR)測定を行った結果、 1H−N
MR(δppm/CDCl3 ):8.23(s,2H),
7.15−6.90(m,4H),2.21(s,6H),1.
20(s,18H),0.26(s,18H)であった。The ligand (A-1-a) 1.0 synthesized in the above (d) was added to 200 ml of Schlenk purged with nitrogen.
g (3.8 mmol) and 40 ml of dehydrated hexane. 2.6 ml of a hexane solution having a concentration of 1.50 mol / l of n-butyllithium (3.9 ml) was added to the solution.
Mmol) at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours. After distilling off the solvent under reduced pressure, 25 ml of dehydrated toluene was added, and the mixture was cooled to -78 ° C.
A suspension of 0.44 g (1.9 mmol) of zirconium tetrachloride in 25 ml of dehydrated toluene was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was collected by filtration and dried to obtain 0.5 g of the desired compound (yield: 40%). This thing, proton nuclear magnetic resonance spectroscopy (1 H-NMR) results measured Been, 1 H-N
MR (δ ppm / CDCl 3 ): 8.23 (s, 2H),
7.15-6.90 (m, 4H), 2.21 (s, 6H), 1.
20 (s, 18H) and 0.26 (s, 18H).
【0048】(2)プロピレンのスラリー重合 攪拌装置付き1リットルステレンレス製耐圧オートクレ
ーブを80℃に加熱し、充分減圧乾燥した後、乾燥窒素
で大気圧に戻し室温まで冷却した。乾燥窒素気流下、乾
燥脱酸素ヘプタン400ミリリットル、トリイソブチル
アルミニウム2.0モル/リットル濃度のヘプタン溶液0.
25ミリリットル(0.5ミリモル)を投入し、350r
pmでしばらく攪拌した。その後、メチルアルミノキサ
ン2.0モル/リットル濃度のトルエン溶液5.0ミリリッ
トル(10.0ミリモル)及び錯体(A−1)10ミリモ
ル/リットル濃度のヘプタンスラリー1.0ミリリットル
(10.0マイクロモル)をオートクレーブに素早く投入
した。(2) Slurry Polymerization of Propylene A 1-liter pressure-resistant autoclave made of sterylene-less with a stirrer was heated to 80 ° C., dried sufficiently under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. 400 ml of dry deoxygenated heptane, 2.0 mol / l of triisobutylaluminum in a heptane solution having a concentration of 2.0 mol / l in a dry nitrogen stream.
Charge 25 ml (0.5 mmol), 350 r
Stirred at pm for a while. Thereafter, 5.0 ml (10.0 mmol) of a toluene solution having a concentration of 2.0 mol / l of methylaluminoxane and 1.0 ml (10.0 micromol) of a heptane slurry having a concentration of 10 mmol / l of a complex (A-1) were obtained. Was quickly charged into the autoclave.
【0049】その後、1200rpmで攪拌を開始し
た。次に、プロピレンを全圧0.7 MPaに3分間かけて昇
圧し、同時に温度を50℃まで昇温したのち、60分間
重合を実施した。反応終了後、メタノール20ミリリッ
トルをオートクレーブに投入し、未反応のプロピレンを
脱圧により除去した。そして、生じた沈殿物をろ過によ
り取り除き、ろ液の溶媒を減圧留去することによりポリ
プロピレンを得た。このポリプロピレンの立体規則性を
調べるために、同位体炭素核磁気共鳴分光(13C−NM
R)によるアイソタクチックペンタッド分率〔mmm
m〕を測定したところ、41%であった。なお、〔mm
mm〕は、任意の連続する5つのプロピレン単位で構成
される炭素一炭素結合による主鎖に対して、側鎖である
5つのメチル基がいずれも同方向に位置する立体構造の
割合を意味する。 実施例2 (1)錯体(A−2)の製造 (イ)配位子(A−2−a)の合成Thereafter, stirring was started at 1200 rpm. Next, propylene was pressurized to a total pressure of 0.7 MPa over 3 minutes, and simultaneously, the temperature was raised to 50 ° C., and then polymerization was performed for 60 minutes. After completion of the reaction, 20 ml of methanol was charged into the autoclave, and unreacted propylene was removed by depressurization. The resulting precipitate was removed by filtration, and the solvent in the filtrate was distilled off under reduced pressure to obtain polypropylene. In order to examine the stereoregularity of this polypropylene, isotope carbon nuclear magnetic resonance spectroscopy ( 13 C-NM
R) isotactic pentad fraction [mmm
m] was 41%. In addition, [mm
mm] means the ratio of the three-dimensional structure in which all five methyl groups as side chains are located in the same direction with respect to a main chain formed by carbon-carbon bonds composed of any five consecutive propylene units. . Example 2 (1) Production of complex (A-2) (A) Synthesis of ligand (A-2-a)
【0050】[0050]
【化12】 Embedded image
【0051】100ミリリットルフラスコにメタノール
30ミリリットルおよび4−メチル−6−トリメチルシ
リルサリチルアルデヒド1.0g(4.8 ミリモル)、ぎ酸
(1滴)を投入した。さらに攪拌しながら、室温下で2-
イソプロピルアニリン0.70g(5.2 ミリモル)を滴下
したのち、2時間攪拌した。反応終了後、水50ミリリ
ットルを投入しジエチルエーテル100ミリリットルで
抽出した。分液ロートで有機相を分取し、有機相に無水
硫酸マグネシウムを加え、ろ過後、溶媒留去し残留物を
得た。得られた残留物をカラム精製することにより目的
化合物を0.7g(収率45%)を得た。 (ロ)錯体(A−2)の合成A 100 ml flask was charged with 30 ml of methanol, 1.0 g (4.8 mmol) of 4-methyl-6-trimethylsilylsalicylaldehyde and one drop of formic acid. With further stirring, at room temperature
After dropping 0.70 g (5.2 mmol) of isopropylaniline, the mixture was stirred for 2 hours. After completion of the reaction, 50 ml of water was added, and the mixture was extracted with 100 ml of diethyl ether. The organic phase was separated by a separating funnel, anhydrous magnesium sulfate was added to the organic phase, and the mixture was filtered and the solvent was distilled off to obtain a residue. The obtained residue was purified by column to obtain 0.7 g (yield: 45%) of the target compound. (B) Synthesis of complex (A-2)
【0052】[0052]
【化13】 Embedded image
【0053】窒素置換した200ミリリットルシュレン
クに、上記(イ)で合成した配位子(A−2−a)0.7
g(2.2ミリモル)及び脱水ヘキサン40ミリリットル
を投入した。その溶液にn−ブチルリチウム1.50モル
/リットル濃度のヘキサン溶液1.5ミリリットル(2.3
ミリモル)を−78℃で滴下した。滴下終了後、室温で
8時間攪拌した。そして、溶媒を減圧留去した後、脱水
トルエン25ミリリットルを加え、−78℃に冷却し、
四塩化ジルコニウム0.25g(1.1ミリモル)の脱水ト
ルエン25ミリリットル懸濁液を滴下した。滴下終了
後、室温で6時間攪拌した。反応終了後、カヌラーでろ
過し、ろ液を濃縮し脱水ヘキサンを加えた。生じた沈澱
物をろ別、乾燥することにより、目的化合物を0.2g得
た(収率22%)。このものについて、1 H−NMR測
定を行った結果、1 H−NMR(δppm/CDCl3 ):9.40(s,
2H),7.20−6.80(m,12H),3.20(m,
2H),2.20(s,6H),1.22(d,12H),
0.20(s,18H)であった。The ligand (A-2-a) 0.7 synthesized in the above (a) was added to 200 ml of Schlenk purged with nitrogen.
g (2.2 mmol) and 40 ml of dehydrated hexane. 1.5 ml of a hexane solution having a concentration of 1.50 mol / liter of n-butyllithium (2.3 ml) was added to the solution.
Mmol) at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours. After distilling off the solvent under reduced pressure, 25 ml of dehydrated toluene was added, and the mixture was cooled to -78 ° C.
A suspension of 0.25 g (1.1 mmol) of zirconium tetrachloride in 25 ml of dehydrated toluene was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was separated by filtration and dried to obtain 0.2 g of the desired compound (yield: 22%). As a result of 1 H-NMR measurement of this product, 1 H-NMR (δ ppm / CDCl 3 ): 9.40 (s,
2H), 7.20-6.80 (m, 12H), 3.20 (m,
2H), 2.20 (s, 6H), 1.22 (d, 12H),
0.20 (s, 18H).
【0054】(2)プロピレンのスラリー重合 実施例1(2)において、錯体(A−1)の代わりに錯
体(A−2)を用いた以外は、実施例1と同様にしてポ
リプロピレンを得た。このポリプロピレンの立体規則性
を調べるためにアイソタクチックペンタッド分率〔mm
mm〕を測定したところ、39%であった。 比較例1 (1)錯体(A−3)の製造 (イ)配位子(A−3−a)の合成(2) Slurry polymerization of propylene A polypropylene was obtained in the same manner as in Example 1 (2) except that the complex (A-2) was used instead of the complex (A-1). . In order to examine the stereoregularity of this polypropylene, an isotactic pentad fraction [mm
mm] was 39%. Comparative Example 1 (1) Production of Complex (A-3) (A) Synthesis of Ligand (A-3-a)
【0055】[0055]
【化14】 Embedded image
【0056】100ミリリットルフラスコにメタノール
30ミリリットルおよび3−t−ブチル−2−ヒドロキ
シベンズアルデヒド2.0g(11.2ミリモル),ぎ酸
(1滴)を投入した。さらに攪拌しながら、室温下で2
−イソプロピルアニリン1.60g(11.9ミリモル)を
滴下したのち、2時間攪拌した。反応終了後、水50ミ
リリットルを投入しジエチルエーテル100ミリリット
ルで抽出した。分液ロートで有機相を分取し、有機相に
無水硫酸マグネシウムを加え、ろ過後、溶媒留去し残留
物を得た。得られた残留物をカラム精製することにより
目的化合物2.1g(収率62%)を得た。 (ロ)錯体(A−3)の合成A 100 ml flask was charged with 30 ml of methanol, 2.0 g (11.2 mmol) of 3-t-butyl-2-hydroxybenzaldehyde and one drop of formic acid. With further stirring, at room temperature
After dropwise adding 1.60 g (11.9 mmol) of -isopropylaniline, the mixture was stirred for 2 hours. After completion of the reaction, 50 ml of water was added, and the mixture was extracted with 100 ml of diethyl ether. The organic phase was separated by a separating funnel, anhydrous magnesium sulfate was added to the organic phase, and the mixture was filtered and the solvent was distilled off to obtain a residue. The obtained residue was purified by column to give 2.1 g (yield 62%) of the desired compound. (B) Synthesis of complex (A-3)
【0057】[0057]
【化15】 Embedded image
【0058】窒素置換した200ミリリットルシュレン
クに、上記(イ)で合成した配位子(A−3−a)1.0
g(3.4ミリモル)及び脱水ヘキサン40ミリリットル
を投入した。その溶液にn−ブチルリチウム1.50モル
/リットル濃度のヘキサン溶液2.3ミリリットル(3.5
ミリモル)を−78℃で滴下した。滴下終了後、室温で
8時間攪拌した。そして、溶媒を減圧留去した後、脱水
トルエン25ミリリットルを加え、−78℃に冷却し、
四塩化ジルコニウム0.40g(1.7ミリモル)の脱水ト
ルエン25ミリリットル懸濁液を滴下した。滴下終了
後、室温で6時間攪拌した。反応終了後、カヌラーでろ
過し、ろ液を濃縮し脱水ヘキサンを加えた。生じた沈殿
物をろ別、乾燥することにより、目的化合物を0.3g得
た(収率39%)。このものについて、1 H−NMR測
定を行った結果、1 H−NMR(δppm/CDCl3 ):8.25(s,
2H),7.61−6.50(m,14H),3.20(m,
2H),1.12−1.40(m,12H),1.10(s,
18H)であった。 (2)プロピレンスラリー重合 実施例1(2)において、錯体(A−1)の代わりに、
錯体(A−3)を用いた以外は、実施例1と同様にして
ポリプロピレンを得た。このポリプロピレンの立体規則
性を調べるためにアイソタクチックペンタッド分率〔m
mmm〕測定しようとしたが、2,1−挿入(2,1−
ins)が非常に多く定量が不可能であった。The ligand (A-3-a) 1.0 synthesized in the above (a) was added to 200 ml of Schlenk purged with nitrogen.
g (3.4 mmol) and 40 ml of dehydrated hexane. 2.3 ml (3.5 ml) of a hexane solution having a concentration of 1.50 mol / l n-butyllithium was added to the solution.
Mmol) at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours. After distilling off the solvent under reduced pressure, 25 ml of dehydrated toluene was added, and the mixture was cooled to -78 ° C.
A suspension of 0.40 g (1.7 mmol) of zirconium tetrachloride in 25 ml of dehydrated toluene was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was separated by filtration and dried to obtain 0.3 g of the target compound (yield: 39%). As a result of 1 H-NMR measurement of this product, 1 H-NMR (δ ppm / CDCl 3 ): 8.25 (s,
2H), 7.61-6.50 (m, 14H), 3.20 (m,
2H), 1.12-1.40 (m, 12H), 1.10 (s,
18H). (2) Propylene slurry polymerization In Example 1 (2), instead of complex (A-1),
A polypropylene was obtained in the same manner as in Example 1, except that the complex (A-3) was used. To examine the stereoregularity of this polypropylene, an isotactic pentad fraction [m
mm]], but 2,1-inserted (2,1-
(ins) were too large to quantify.
【0059】[0059]
【発明の効果】本発明の遷移金属化合物はキレート型配
位子を有する化合物であって、立体規則性のポリプロピ
レンなどを製造し得る高活性で安価なオレフィン類重合
用均一系触媒を与えることができる。この触媒を用いる
ことにより、分子量分布の狭い立体規則性オレフィン系
重合体を効率よく製造することができる。The transition metal compound of the present invention is a compound having a chelating ligand and can provide a highly active and inexpensive homogeneous catalyst for olefin polymerization capable of producing stereoregular polypropylene and the like. it can. By using this catalyst, a stereoregular olefin polymer having a narrow molecular weight distribution can be efficiently produced.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) // C07F 7/00 C07F 7/00 A Fターム(参考) 4H049 VN01 VN06 VP03 VQ02 VQ75 VQ83 VR23 VU14 VW01 4J028 AA01A AB01A AC01A AC18A AC26A AC37A AC42A AC45A AC47A AC48A BA00A BA02B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC19B BC25B BC27B CA27C CA28C EA01 EB01 EB02 EB04 EB05 EB07 EB08 EB09 EB10 EB13 EB16 EB17 EB18 EB21 EB22 EB24 EC01 EC02 FA01 FA02 FA03 FA04 FA06 FA07 GA12──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (reference) // C07F 7/00 C07F 7/00 A F term (reference) 4H049 VN01 VN06 VP03 VQ02 VQ75 VQ83 VR23 VU14 VW01 4J028 AA01A AB01A AC01A AC18A AC26A AC37A AC42A AC45A AC47A AC48A BA00A BA02B BB00A BB01B BB02B BC12B BC15B BC16B BC17B BC19B BC25B BC27B CA27C CA28C EA01 EB01 EB02 EB04 EB05 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB07 EB08
Claims (6)
は1〜3の整数、Xは酸素原子,イオウ原子,セレン原
子又はNR3 、AはD2 R4 3又は 【化2】 で表される基、D1 及びD2 は、それぞれ周期律表第1
4族の原子を示す。R1〜R5 は、それぞれ独立して炭
素数1〜20の炭化水素基、R6 は水素原子又は炭素数
1〜20の炭化水素基を示し、R2 及びR4 は、それぞ
れにおいて2個がたがいに連結して環を形成していても
よく、また、mが2又は3の場合、1つの配位子に含ま
れるR1 〜R6 のうちの1個の基と他の配位子に含まれ
るR1 〜R 6 のうちの1個の基とが結合されていてもよ
く、R1 同士,R2 同士,R3 同士,R4 同士,R5 同
士及びR6 同士はたがいに同一でも異なっていてもよ
い。Zは水素原子,ハロゲン原子,炭化水素基,酸素含
有基,窒素含有基,ホウ素含有基,アルミニウム含有
基,リン含有基,ハロゲン含有基,ケイ素含有基,ゲル
マニウム含有基又はスズ含有基、nは(Mの原子価−
m)の値を示し、nが2以上の場合には、Zで示される
複数の基は、たがいに同一でも異なっていてもよく、ま
たたがいに連結して環を形成していてもよい。〕で表さ
れる遷移金属化合物。1. A compound of the general formula (I)[Wherein, M is a transition metal atom of Groups 3 to 11 of the periodic table, m
Is an integer of 1 to 3, X is an oxygen atom, a sulfur atom, a selenium atom
Child or NRThree, A is DTwoRFour ThreeOrA group represented by1And DTwoIs the first of the periodic table
Shows Group 4 atoms. R1~ RFiveAre each independently charcoal
A hydrocarbon group having a prime number of 1 to 20, R6Is a hydrogen atom or carbon number
1 to 20 hydrocarbon groups;TwoAnd RFourEach
Even if two of them are linked to each other to form a ring
Well, when m is 2 or 3, contained in one ligand
R1~ R6Of one of the groups and other ligands
R1~ R 6May be bonded to one of the groups
K, R1Each other, RTwoEach other, RThreeEach other, RFourEach other, RFivesame
And R6Each other may be the same or different
No. Z is hydrogen atom, halogen atom, hydrocarbon group, oxygen
Base, nitrogen-containing, boron-containing, aluminum-containing
Group, phosphorus-containing group, halogen-containing group, silicon-containing group, gel
A manium-containing group or a tin-containing group, n is (valence of M−
m), and when n is 2 or more, it is indicated by Z
The groups may be the same or different, and
They may be linked to each other to form a ring. ]
Transition metal compound.
化合物、及び(B)該(A)成分の遷移金属化合物と反
応してイオン性の錯体を形成し得る化合物を接触させて
なるオレフィン類重合用触媒。2. Contacting (A) a transition metal compound represented by the general formula (I) with (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A). Olefin polymerization catalyst.
化合物、(B)該(A)成分の遷移金属化合物と反応し
てイオン性の錯体を形成し得る化合物、及び(C)有機
アルミニウム化合物を接触させてなるオレフィン類重合
用触媒。(A) a transition metal compound represented by the general formula (I), (B) a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A), and (C) ) An olefin polymerization catalyst obtained by contacting an organoaluminum compound.
用触媒の存在下、オレフィン類を重合させることを特徴
とするオレフィン系重合体の製造方法。4. A method for producing an olefin polymer, comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization according to claim 2 or 3.
成分の有機アルミニウム化合物がトリアルキルアルミニ
ウムである請求項4記載のオレフィン系重合体の製造方
法。5. The olefin polymerization catalyst (C)
5. The process for producing an olefin polymer according to claim 4, wherein the organoaluminum compound is trialkylaluminum.
4又は5記載のオレフィン系重合体の製造方法。6. The method for producing an olefin polymer according to claim 4, wherein the olefin is propylene.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080515A (en) * | 2000-07-04 | 2002-03-19 | Mitsui Chemicals Inc | Method for manufacturing polar olefin copolymer and polar olefin copolymer obtained by the method |
JP2012077284A (en) * | 2010-09-10 | 2012-04-19 | Showa Denko Kk | Catalyst for polymerization of norbornene-based monomer and method for producing norbornene-based polymer |
CN110612313A (en) * | 2017-03-23 | 2019-12-24 | 埃克森美孚化学专利公司 | Catalyst system and methods of making and using the same |
-
2000
- 2000-03-03 JP JP2000058499A patent/JP2001247579A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080515A (en) * | 2000-07-04 | 2002-03-19 | Mitsui Chemicals Inc | Method for manufacturing polar olefin copolymer and polar olefin copolymer obtained by the method |
JP2012077284A (en) * | 2010-09-10 | 2012-04-19 | Showa Denko Kk | Catalyst for polymerization of norbornene-based monomer and method for producing norbornene-based polymer |
CN110612313A (en) * | 2017-03-23 | 2019-12-24 | 埃克森美孚化学专利公司 | Catalyst system and methods of making and using the same |
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