JP5393456B2 - 3−メチルブテ−1−エンからポリマーを製造する方法 - Google Patents
3−メチルブテ−1−エンからポリマーを製造する方法 Download PDFInfo
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- JP5393456B2 JP5393456B2 JP2009518805A JP2009518805A JP5393456B2 JP 5393456 B2 JP5393456 B2 JP 5393456B2 JP 2009518805 A JP2009518805 A JP 2009518805A JP 2009518805 A JP2009518805 A JP 2009518805A JP 5393456 B2 JP5393456 B2 JP 5393456B2
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- methylbut
- ene
- catalyst
- copolymerization
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- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 title claims description 138
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 title claims description 132
- 229920000642 polymer Polymers 0.000 title description 29
- 238000004519 manufacturing process Methods 0.000 title description 15
- 239000003054 catalyst Substances 0.000 claims description 140
- 229920001577 copolymer Polymers 0.000 claims description 85
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 72
- 238000007334 copolymerization reaction Methods 0.000 claims description 68
- 230000008569 process Effects 0.000 claims description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 43
- 239000000178 monomer Substances 0.000 claims description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 20
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical class C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 9
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 8
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- IWTBVKIGCDZRPL-LURJTMIESA-N 3-Methylbutanol Natural products CC[C@H](C)CCO IWTBVKIGCDZRPL-LURJTMIESA-N 0.000 claims description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
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- 239000001273 butane Substances 0.000 claims description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 43
- 229910007926 ZrCl Inorganic materials 0.000 description 36
- 238000002844 melting Methods 0.000 description 35
- 230000008018 melting Effects 0.000 description 35
- 239000000203 mixture Substances 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 31
- -1 polyethylene Polymers 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 29
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
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- 238000005984 hydrogenation reaction Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 16
- 230000007423 decrease Effects 0.000 description 15
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- 238000002360 preparation method Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 12
- 238000010348 incorporation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000001419 dependent effect Effects 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000007037 hydroformylation reaction Methods 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000012968 metallocene catalyst Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical class C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 125000005595 acetylacetonate group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
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- 238000004821 distillation Methods 0.000 description 3
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- BAZQYVYVKYOAGO-UHFFFAOYSA-M loxoprofen sodium hydrate Chemical compound O.O.[Na+].C1=CC(C(C([O-])=O)C)=CC=C1CC1C(=O)CCC1 BAZQYVYVKYOAGO-UHFFFAOYSA-M 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
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- 125000004122 cyclic group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
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- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
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- HSTAGCWQAIXJQM-UHFFFAOYSA-N 2,5-dichloro-2,5-dimethylhexane Chemical compound CC(C)(Cl)CCC(C)(C)Cl HSTAGCWQAIXJQM-UHFFFAOYSA-N 0.000 description 1
- KZDCMKVLEYCGQX-UDPGNSCCSA-N 2-(diethylamino)ethyl 4-aminobenzoate;(2s,5r,6r)-3,3-dimethyl-7-oxo-6-[(2-phenylacetyl)amino]-4-thia-1-azabicyclo[3.2.0]heptane-2-carboxylic acid;hydrate Chemical compound O.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1.N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 KZDCMKVLEYCGQX-UDPGNSCCSA-N 0.000 description 1
- UBDFJZYVAOTVDA-UHFFFAOYSA-N 2-[2-(1h-inden-2-yl)propan-2-yl]-1h-indene Chemical compound C1=CC=C2CC(C(C)(C=3CC4=CC=CC=C4C=3)C)=CC2=C1 UBDFJZYVAOTVDA-UHFFFAOYSA-N 0.000 description 1
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- POKBBTHLULVRMF-UHFFFAOYSA-N OP(O)O.OP(O)O.O.O.O Chemical compound OP(O)O.OP(O)O.O.O.O POKBBTHLULVRMF-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 235000011449 Rosa Nutrition 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical class [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013480 data collection Methods 0.000 description 1
- 238000011157 data evaluation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- DWWZPYPYUFXZTL-UHFFFAOYSA-N lithium;2h-inden-2-ide Chemical compound [Li+].C1=CC=C2[CH-]C=CC2=C1 DWWZPYPYUFXZTL-UHFFFAOYSA-N 0.000 description 1
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000000196 viscometry Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
はっきりと記載されてはいない。
Yは置換又は非置換のシクロペンタジエニル−、インデニル−、テトラヒドロインデニル−、オクタヒドロフルオレニル−及びフルオレニル−基から選択されるシクロペンタジエニル−タイプの基又は窒素、燐、酸素又は硫黄及び20個までの水素ではない原子を含有しているアニオンリガンド基であり、この際、YとCp*とは場合により共有結合して又は1個の基Zを介して相互に結合していてよい、
Xは相互に無関係に、ハロゲン原子、偽ハロゲン、水素原子、シリル基、ホスフィド、スルフィド又は有機基であり、かつ
mはMの原子価標をXで飽和するために充分である数である]の触媒及び助触媒としてのアルミニウム又はホウ素を有する化合物の存在下に実施することを特徴としている、但し、この方法がモノマーとしてのエテン及び3−メチルブテ−1−エンをベースとするコポリマーの製造法であり、殊に30℃の温度で実施される場合には、式Iの化合物として、[Me2C(3−MeCp)(Flu)]ZrCl2又は[Me2Si(Ind)(Flu)]ZrCl2を使用しないことを条件としている。
Yは置換又は非置換のシクロペンタジエニル−、インデニル−、テトラヒドロインデニル−、オクタヒドロフルオレニル−及びフルオレニル−基から選択されるシクロペンタジエニル−タイプの基又は窒素、燐、酸素又は硫黄及び20個までの水素ではない原子を含有しているアニオンリガンド基であり、この際、YとCp*とは場合により共有結合して又は1個の基Zを介して相互に結合していてよい、
Mは、元素周期律表のスカンジウムを除く第3族〜第10族の、有利には第4〜第6族の又はランタノイドの金属であり、
Xは相互に無関係に、ハロゲン原子、偽ハロゲン、例えばシアニド又はアジド、水素原子、シリル基、ホスフィド、スルフィド又は有機基、例えばアルキル−、アリール−、アミド−、アリールオキシ−、アルコキシ−、アセチル−又はアセチルアセトナート−基、殊に炭素原子数1〜20を有する有機基であり、かつ
mはMの原子価標をXで飽和するために充分である数値である]の触媒及び助触媒としてのアルミニウム又はホウ素を有する化合物の存在下に実施することを特徴としている、但し、この方法がモノマーとしてのエテン及び3−メチルブテ−1−エンをベースとするコポリマーの製造法であり、かつ殊に30℃の温度で実施される場合には、式Iの化合物として「Me2C(3−MeCp)(Flu)]ZrCl2又は[Me2Si(Ind)(Flu)]ZrCl2を使用しないことを条件としている。式Iの触媒中に1個以上のXが存在する場合には、存在するXは同じであることが有利である。本発明による触媒が金属Mとして、Zr、Ti又はHfを有することが有利である。シクロペンタジエニル−、インデニル−、テトラヒドロインデニル−、オクタヒドロフルオレニル−及びフルオレニル−基に付く可能な置換基は、殊にアルキル−、アリール−、アルキルアリール−、アラルキル−又はシリル−基であることができる。好ましい置換基は、アルキル基、例えばメチル−、エチル−、プロピル−又はt−ブチル−基である。
Zはホウ素又は元素周期律表の第14族の元素を有し、20個までの水素ではない原子を有する基である]の触媒(化合物Ia)の存在下に実施するのが有利である。式中のZがCR2R3−又はSiR2R3−基であり、R2及びR3は同一又は異なるもので、水素又は芳香族、脂肪−芳香族、芳香−脂肪族又は脂肪族基である、触媒を使用するのが好ましい。芳香族基としてはヘテロ芳香族基も好適である。脂肪族基としては、直線状、分枝した又は環状の脂肪族基も存在することができる。基R2及びR3がC1〜C6−アルキル−基、殊にメチル−又はエチル−又はフェニル−基であることが特別好ましい。
a)イソブテンをヒドロホルミル化して3−メチルブタナールにする工程、
b)3−メチルブタナールを水素化して3−メチルブタノールにする工程及び
c)3−メチルブタノールから水分離する工程
によって得られる3−メチルブテ−1−エンを使用する(この際、工程c)から得られる3−メチルブテ−1−エンは、特に化学的精製工程の実施なしに直接使用される)ことが特別有利である。
下記の共重合を、Firma Buechiの1リットル−ガラスオートクレーブ(この中で、0.6MPaまでの圧力で気密に操作できる)中で、半連続的に実施した。磁気カップリングにより間接的に作動されるプロペラ攪拌機を用い、500U/minで、充分に撹拌した。この装置の正確な構成は、図1から知ることができる。図1中に示されている重合装置は、温度計ケース1、隔壁密封球弁2、アルゴン/真空−接続及び排出弁3、攪拌機4、圧力計5、トルエン供給管6、流量調節器7、精製カラム8、アルケン圧縮容器9、制御系及びデータ検出装置10並びに接続ガスボトル/3−メチルブテ−1−エンを有するレクチャ−ボトルへの結合部11を有している。
各々の共重合の前に、オートクレーブを減圧下(油ポンプ真空)に95℃で少なくとも1時間加熱し、この際に、アルゴンで数回パージした。所望の実験温度の調節の後に、メチルアルモキサン(MAO)400mg及びトルエン200mlの充填を行った。このMAOは、10質量%トルエン溶液(Firma Crompton)から、濾過及び引き続く溶剤及び場合により存在する残留トリメチルアルミニウムの濃縮除去によって得られた固体として使用された。引き続き、反応器を改めて真空にした。次いでこの装置に、3−メチルブテ−1−エンを吹き込んだ。アルゴンで再び常圧を形成させる前に、重量コントロールを介して所望量の3−メチルブテ−1−エンをトルエン中に溶かした。引き続き、所望のアルケン圧(エテン−又はプロペン圧)で飽和させた。このためにアルケン圧を、更なるモノマーが後から流れないように、即ち重合開始までにもはやモノマー流が現れないように調節した。重合を、隔壁を通す噴入による気密スプレーを用いる触媒トルエン溶液の注入によって開始させた。プロペン/3−メチルブテ−1−エン−共重合の場合には、0.03MPa又は0.07MPaの圧力に、かつエテン/3−メチルブテ−1−エン−共重合の場合には、0.025〜0.4MPaの圧力に調節した。
触媒残分の溶出のために、反応溶液を、濃塩酸、エタノール及び水を1対2対7の質量比で有しているエタノール−水性塩酸溶液と共に一晩撹拌した。引き続き、−トルエン可溶性ポリマーもトルエン不溶性ポリマーも−5質量%炭酸水素ナトリウム水溶液で中和し、最後に脱鉱水で3回洗浄して中性にした。引き続きトルエン不溶性ポリマーを濾過し、エタノールで洗浄した。トルエン可溶性ポリマーの場合には、回転蒸発器で約50mlまで濃縮させ、かつ−可能な場合には−エタノールで沈殿させた。引き続き、同様にブフナーロートを通して濾過し、エタノールで洗浄した。ポリマーを真空乾燥機中、40℃で恒量になるまで乾燥させた。
プロペンとの重合系列のために、触媒[Me2C(Cp)(Flu)]ZrCl2(式II)(例Ia)及びrac−[Me2C(Ind)2]ZrCl2(式III)(例Ib)を使用した。これらの化合物は、例えば、Boulder又はAldrichから入手することができる。式IIの触媒は、J.A.Ewen,R.L.Jones,A.RazaviによるJ.Am.Chem.Soc.,1988,110,6255中又はEP0354391中の記載と同様に製造することもできる。式IIIの触媒は、W.Spaleck,M.Antberg,V.Dolle,R.Klein,J.Rohrmann and A.Winter による New J.Chem.,14,6(1990)499中の記載と同様に製造することもできる。実施例Ia及びIb中の濃度系列及び温度系列が実施される反応条件は、第1表中から知ることができる。
次の第2及び第3表中に、触媒としての[Me2C(Cp)(Flu)]ZrCl2の存在下での3−メチルブテ−1−エンとプロペンとの共重合の結果が記載されている。
共重合
次の第4表及び第5表中には、触媒としてのrac−[Me2C(Ind)2]ZrCl2の存在下での3−メチルブテ−1−エンとプロペンとの共重合の結果が記載されている。
例2a〜2cで、3種の異なる触媒の使用下に実験系列2a〜2cを実施し、この場合に、3−メチルブテ−1−エンの割合を変えた。第6表から、例2a〜2cの反応条件を知ることができる。
エテンとの重合系列のために、触媒[Me2Si(Me4Cp)(NtertBu)]TiCl2(式IV)を用いた。実験2aを実施した条件は、第6表から知ることができる。式IVによる触媒は、例えばJ.OkudaによるChem.Ber.1990,123,1649中の記載又はF.Amor und J.OkudaによるJ.Organomet.Chem.1996,520,245中の記載又はEP0416815又はUP5026798中の記載と同様に製造することができる。実験系列2aで測定された結果は、次の第7表から知ることができる。
PD=多分散性
Mn=数平均分子量。
エテンとの重合系列のために、触媒[Ph2Si(OctHFlu)(Ind)]ZrCl2(式V)を用いた。第6表から、実験2bを実施した条件を知ることができる。次の第8表から、実験2bで測定された結果を知ることができる。
Mn=数平均分子量。
エテンとの重合系列のために、触媒rac−[Me2C(Ind)2]ZrCl2(式III)を使用した。実験2cを実施することのできた条件は、第6表から知ることができる。実験系列2cに関して測定された結果は、次の第9表から知ることができる。
Mn=数平均分子量。
Claims (12)
- 共重合を、式IIによる触媒の金属と助触媒のアルミニウムとのモル比1:0.1〜1:100000で実施することを特徴とする、請求項1に記載の方法。
- 共重合を、モノマーと式IIの触媒とのモル比1×1010:1〜100:1で実施することを特徴とする、請求項1または2に記載の方法。
- 共重合を、ブタン、ヘキサン、ヘプタン、トルエン、キシレン及びエチルベンゼンから選択される溶剤中で実施することを特徴とする、請求項1から3までのいずれか1項に記載の方法。
- 共重合を、−30℃〜250℃の温度で実施することを特徴とする、請求項1から4までのいずれか1項に記載の方法。
- 共重合を、0.1〜1MPaの圧力で実施することを特徴とする、請求項1から5までのいずれか1項に記載の方法。
- 3−メチルブテ−1−エン及びエテン及びプロペンのモノマーの合計に対する反応混合物中の3−メチルブテ−1−エンモノマーのモル割合は、少なくとも20%であることを特徴とする、請求項1から6までのいずれか1項に記載の方法。
- 割合は40〜80%であることを特徴とする、請求項7に記載の方法。
- プロペンと3−メチルブテ−1−エンとを共重合させることを特徴とする、請求項1から8までのいずれか1項に記載の方法。
- エテンと3−メチルブテ−1−エンとを共重合させることを特徴とする、請求項10に記載の方法。
- a)イソブテンをヒドロホルミル化して3−メチルブタナールにする工程、
b)3−メチルブタナールを水素化して3−メチルブタノールにする工程及び
c)3−メチルブタノールから水を分離する工程
によって得られる3−メチルブテ−1−エンを使用する、この際、工程c)から得られる3−メチルブテ−1−エンを、化学的精製工程を実施せずに直接使用することを特徴とする、請求項1から11までのいずれか1項に記載の方法。
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DE102006031960A DE102006031960A1 (de) | 2006-07-11 | 2006-07-11 | Verfahren zur Herstellung von Polymeren aus 3-Methylbut-1-en |
PCT/EP2007/054580 WO2008006636A1 (de) | 2006-07-11 | 2007-05-11 | Verfahren zur herstellung von polymeren aus 3-methylbut-1-en |
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DE102006031960A1 (de) | 2006-07-11 | 2008-01-17 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Polymeren aus 3-Methylbut-1-en |
JP5787769B2 (ja) * | 2009-01-23 | 2015-09-30 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | 3置換c4−10アルケンとのポリオレフィン気相重合 |
EP2382247B1 (en) * | 2009-01-23 | 2012-10-24 | Evonik Oxeno GmbH | Pe mib slurry polymerization |
ES2401763T3 (es) | 2009-01-23 | 2013-04-24 | Evonik Oxeno Gmbh | Película de PE-MIB preparada con ayuda de Zn/Cr |
SG173101A1 (en) * | 2009-01-23 | 2011-08-29 | Evonik Oxeno Gmbh | Film |
DE102009026582A1 (de) | 2009-05-29 | 2010-12-02 | Evonik Oxeno Gmbh | Aufbereitung eines 3-Methyl-1-buten-haltigen Gemisches |
US8431729B2 (en) * | 2011-08-04 | 2013-04-30 | Chevron Phillips Chemical Company Lp | High activity catalyst compositions containing silicon-bridged metallocenes with bulky substituents |
KR101609503B1 (ko) | 2012-03-28 | 2016-04-05 | 미쓰이 가가쿠 가부시키가이샤 | 프로필렌·α-올레핀 공중합체 및 그의 용도 |
US8867874B2 (en) * | 2012-12-06 | 2014-10-21 | Finisar Sweden Ab | Method for modifying the combining or splitting ratio of a multimode interference coupler |
EP2759554A1 (en) | 2013-01-23 | 2014-07-30 | Total Research & Technology Feluy | Process for producing olefin / 3-methyl-1-butene copolymers |
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US20090203858A1 (en) | 2009-08-13 |
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