JPH023405B2 - - Google Patents
Info
- Publication number
- JPH023405B2 JPH023405B2 JP57062340A JP6234082A JPH023405B2 JP H023405 B2 JPH023405 B2 JP H023405B2 JP 57062340 A JP57062340 A JP 57062340A JP 6234082 A JP6234082 A JP 6234082A JP H023405 B2 JPH023405 B2 JP H023405B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst component
- contact
- compound
- polymerization
- magnesium
- 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.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 claims description 79
- 239000011777 magnesium Substances 0.000 claims description 48
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- 150000001875 compounds Chemical class 0.000 claims description 37
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 23
- 150000003609 titanium compounds Chemical class 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 14
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 24
- 239000005977 Ethylene Substances 0.000 description 23
- -1 aluminum halide Chemical class 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 150000002430 hydrocarbons Chemical group 0.000 description 21
- 150000003377 silicon compounds Chemical class 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 19
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000010936 titanium Substances 0.000 description 13
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 229930195733 hydrocarbon Natural products 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 150000008282 halocarbons Chemical class 0.000 description 9
- 150000002681 magnesium compounds Chemical class 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 239000011343 solid material Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 6
- 239000005052 trichlorosilane Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 125000003342 alkenyl group Chemical group 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 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
- 239000004711 α-olefin Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- WHFQAROQMWLMEY-UHFFFAOYSA-N propylene dimer Chemical group CC=C.CC=C WHFQAROQMWLMEY-UHFFFAOYSA-N 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- KWOIDDOVDJYZLT-UHFFFAOYSA-L dichlorotitanium;phenol Chemical compound Cl[Ti]Cl.OC1=CC=CC=C1.OC1=CC=CC=C1 KWOIDDOVDJYZLT-UHFFFAOYSA-L 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl o-methoxybenzoate Natural products CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 2
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N iodoform Chemical compound IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- HFTSQAKJLBPKBD-UHFFFAOYSA-N magnesium;butan-1-olate Chemical compound [Mg+2].CCCC[O-].CCCC[O-] HFTSQAKJLBPKBD-UHFFFAOYSA-N 0.000 description 2
- WNJYXPXGUGOGBO-UHFFFAOYSA-N magnesium;propan-1-olate Chemical compound CCCO[Mg]OCCC WNJYXPXGUGOGBO-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VBYLGQXERITIBP-UHFFFAOYSA-N n-[dimethylamino(methyl)silyl]-n-methylmethanamine Chemical compound CN(C)[SiH](C)N(C)C VBYLGQXERITIBP-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- UDWASUCJIKKBLS-NSCUHMNNSA-N (3e)-1,1,2,3,4,5-hexachloropenta-1,3-diene Chemical compound ClC\C(Cl)=C(/Cl)C(Cl)=C(Cl)Cl UDWASUCJIKKBLS-NSCUHMNNSA-N 0.000 description 1
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- POJPQMDDRCILHJ-UHFFFAOYSA-N 1,1,1,2,2,2-hexabromoethane Chemical compound BrC(Br)(Br)C(Br)(Br)Br POJPQMDDRCILHJ-UHFFFAOYSA-N 0.000 description 1
- QQAHAGNPDBPSJP-UHFFFAOYSA-N 1,1,1,2,2,3,3,3-octachloropropane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl QQAHAGNPDBPSJP-UHFFFAOYSA-N 0.000 description 1
- IGDVFIQVQXDOFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,4-decabromobutane Chemical compound BrC(Br)(Br)C(Br)(Br)C(Br)(Br)C(Br)(Br)Br IGDVFIQVQXDOFA-UHFFFAOYSA-N 0.000 description 1
- ZDUOUNIIAGIPSD-UHFFFAOYSA-N 1,1,1-tribromoethane Chemical compound CC(Br)(Br)Br ZDUOUNIIAGIPSD-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- BASDZFQDZBHCAV-UHFFFAOYSA-N 1,1,1-triiodoethane Chemical compound CC(I)(I)I BASDZFQDZBHCAV-UHFFFAOYSA-N 0.000 description 1
- ZFMWDTNZPKDVBU-UHFFFAOYSA-N 1,2,3,4-tetrachlorocyclopentane Chemical compound ClC1CC(Cl)C(Cl)C1Cl ZFMWDTNZPKDVBU-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- GBBZLMLLFVFKJM-UHFFFAOYSA-N 1,2-diiodoethane Chemical compound ICCI GBBZLMLLFVFKJM-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- MFHPYLFZSCSNST-UHFFFAOYSA-N 1-chloro-2-(trichloromethyl)benzene Chemical compound ClC1=CC=CC=C1C(Cl)(Cl)Cl MFHPYLFZSCSNST-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical class NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 1
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- 125000000094 2-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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 1
- OJPSFJLSZZTSDF-UHFFFAOYSA-N 3-ethoxyprop-1-ene Chemical compound CCOCC=C OJPSFJLSZZTSDF-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 101000837626 Homo sapiens Thyroid hormone receptor alpha Proteins 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 102100028702 Thyroid hormone receptor alpha Human genes 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- WEDLYHNDZPHFLT-UHFFFAOYSA-M bis(2-methylpropyl)-phenoxyalumane Chemical compound [O-]C1=CC=CC=C1.CC(C)C[Al+]CC(C)C WEDLYHNDZPHFLT-UHFFFAOYSA-M 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JOHCVVJGGSABQY-UHFFFAOYSA-N carbon tetraiodide Chemical compound IC(I)(I)I JOHCVVJGGSABQY-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- VEZNCHDBSQWUHQ-UHFFFAOYSA-N chlorocyclopropane Chemical compound ClC1CC1 VEZNCHDBSQWUHQ-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical compound CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 description 1
- YSAVZVORKRDODB-WDSKDSINSA-N diethyl tartrate Chemical compound CCOC(=O)[C@@H](O)[C@H](O)C(=O)OCC YSAVZVORKRDODB-WDSKDSINSA-N 0.000 description 1
- UWAMTZZJXXCIOH-UHFFFAOYSA-M diethyl(phenoxy)alumane Chemical compound CC[Al+]CC.[O-]C1=CC=CC=C1 UWAMTZZJXXCIOH-UHFFFAOYSA-M 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- PPQUYYAZSOKTQD-UHFFFAOYSA-M diethylalumanylium;iodide Chemical compound CC[Al](I)CC PPQUYYAZSOKTQD-UHFFFAOYSA-M 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- TUTOKIOKAWTABR-UHFFFAOYSA-N dimethylalumane Chemical compound C[AlH]C TUTOKIOKAWTABR-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- XOCWTYIVWYOSGQ-UHFFFAOYSA-N dipropylalumane Chemical compound C(CC)[AlH]CCC XOCWTYIVWYOSGQ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 1
- MNLMLEWXCMFNFO-UHFFFAOYSA-K ethanol;trichlorotitanium Chemical compound CCO.Cl[Ti](Cl)Cl MNLMLEWXCMFNFO-UHFFFAOYSA-K 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 0.000 description 1
- MNFTYNIMQNJVJI-UHFFFAOYSA-N ethoxy(dipropyl)alumane Chemical compound CC[O-].CCC[Al+]CCC MNFTYNIMQNJVJI-UHFFFAOYSA-N 0.000 description 1
- XGAIERUWZADBAO-UHFFFAOYSA-N ethoxy-bis(2-methylpropyl)alumane Chemical compound CCO[Al](CC(C)C)CC(C)C XGAIERUWZADBAO-UHFFFAOYSA-N 0.000 description 1
- LIQWHXBLFOERRD-UHFFFAOYSA-N ethyl 4-tert-butylbenzoate Chemical compound CCOC(=O)C1=CC=C(C(C)(C)C)C=C1 LIQWHXBLFOERRD-UHFFFAOYSA-N 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- XCTLDQQOHIEUCJ-UHFFFAOYSA-N ethyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC)=CC=CC2=C1 XCTLDQQOHIEUCJ-UHFFFAOYSA-N 0.000 description 1
- NARCMUVKZHPJHP-UHFFFAOYSA-L ethyl(diiodo)alumane Chemical compound [I-].[I-].CC[Al+2] NARCMUVKZHPJHP-UHFFFAOYSA-L 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- JLYXXMFPNIAWKQ-GNIYUCBRSA-N gamma-hexachlorocyclohexane Chemical compound Cl[C@H]1[C@H](Cl)[C@@H](Cl)[C@@H](Cl)[C@H](Cl)[C@H]1Cl JLYXXMFPNIAWKQ-GNIYUCBRSA-N 0.000 description 1
- 229940093920 gynecological arsenic compound Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- VFDYKPARTDCDCU-UHFFFAOYSA-N hexachloropropene Chemical group ClC(Cl)=C(Cl)C(Cl)(Cl)Cl VFDYKPARTDCDCU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229960002809 lindane Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
技術分野
本発明はオレフイン重合用触媒成分の製造方法
に関し、さらに詳しくは高立体規則性で嵩密度の
高いオレフイン重合体を高収率で製造し得る触媒
成分の製造方法に関する。
背景技術
ハロゲンを含まないマグネシウム化合物とチタ
ン化合物との接触物が、オレフイン重合用触媒成
分として有効であることは知られているが、その
触媒性能は低く、その改良法として、一般式SiXl
R4-lのハロゲン化シラン又は該ハロゲン化シラン
と電子供与性化合物の存在下、Mg（OR）2と四ハ
ロゲン化チタンを接触させる方法（特開昭52−
98076号公報）、Mg―Ｏ―Ｒ結合を有するマグネ
シウム化合物と一般式XnSiRoのケイ素化合物の
ようなハロゲン化剤を接触させる際、又は接触さ
せた後、電子供与性化合物を存在させて接触させ
る方法（特開昭53−43094号公報）等で触媒成分
を製造する試みがなされている。またハロゲン化
アルミニウム、Si―Ｏ結合を有する有機化合物お
よびマグネシウムアルコラートの固体状生成物に
少なくとも１個のハロゲン原子を有する４価のチ
タン化合物を接触させる方法（特開昭53−78287
号公報）や、マグネシウム化合物、チタン化合物
およびケイ素化合物を反応させて得られる反応物
と、少なくとも１種のハロゲン化アルミニウム化
合物とを反応させる方法（特開昭56−155205号公
報）のようにハロゲン化アルミニウムを必須反応
成分として固体触媒成分を製造する試みもなされ
ている。
しかしながら、これらの方法で得られた触媒成
分は、触媒活性が低く、立体規則性に劣り又得ら
れる重合体の嵩密度が低い等の問題点がある。
更に、(1)マグネシウム化合物(2)電子供与性化合
物(3)Si―Ｈ結合を有するケイ素化合物及び(4)チタ
ンハロゲン化合物を接触させてなるオレフイン重
合用触媒成分が提案されている。（特開昭57−
92009号公報）が、この提案におけるマグネシウ
ム化合物は、実質的にハロゲン化マグネシウム化
合物であり、かつケイ素化合物とチタンハロゲン
化合物は同時に用いて接触させるものであつて、
その触媒性能も満足したものではない。
発明の開示
発明の目的
本発明は、出発原料としてハロゲンを含まない
マグネシウム化合物を用いて高立体規則性及び高
活性を示し、嵩密度の高いオレフイン重合体を製
造し得る触媒成分を提供することを目的とするも
であり、本発明者らは鋭意研究を行つた結果、マ
グネシウムアルコキシドと水素―珪素結合を有す
る珪素化合物を接触させた後、チタン化合物と接
触させてなる接触物、又はマグネシウムアルコキ
シドと該珪素化合物を接触させた後、電子供与性
化合物と接触させ、更にチタン化合物と接触させ
てなる接触物がオレフイン重合用触媒成分として
優れた性能を発揮することを見出して本発明を完
成した。
発明の要旨
本発明は、
(1) (A)マグネシウムジアルコキシドと(B)一般式
HmRnSiXr〔但し、Ｒは炭化水素基、R1O―若
しくはR2R3N―、Ｘはハロゲン原子を示し、
１ｍ３，０ｒ３，ｍ＋ｎ＋ｒ＝４であ
る。R1，R2及びR3はそれぞれ炭化水素基を示
す。〕の珪素化合物を接触させ、得られた固体
生成物を(C)一般式TiXo（OR）4-o〔但し、Ｘは
ハロゲン原子、Ｒは炭化水素基を示し、０ｎ
４である。〕のチタン化合物と接触させるこ
とからなるオレフイン重合用触媒成分の製造方
法。
(2) (A)マグネシウムジアルコキシドと(B)一般式
HmRnSiXr〔但し、Ｒは炭化水素基、R1O―若
しくはR2R3N―、Ｘはハロゲン原子を示し、
１ｍ３，０ｒ３，ｍ＋ｎ＋ｒ＝４であ
る。R1，R2及びR3はそれぞれ炭化水素基を示
す。〕の珪素化合物を接触させ、得られた固体
生成物を(D)電子供与性化合物と接触させ、次い
で(C)一般式TiXo（OR）4-o〔但し、Ｘはハロゲ
ン原子、Ｒは炭化水素基を示し、０ｎ４で
ある。〕のチタン化合物と接触させることから
なるオレフイン重合用触媒成分の製造方法を要
旨とする。
触媒成分調製の原料
本発明の触媒成分を調製する際に用いる各原料
について説明する。
(A) マグネシウムジアルコキシド
本発明で用いられるマグネシウムアルコキシ
ドは、一般式Mg（OR）（OR′）で表わされるも
のである。式においてＲ及びR′は炭素数１〜
20個、望ましくは１〜10個のアルキル、アルケ
ニル、シクロアルキル、アリール、アルアルキ
ル基である。又、Ｒと同じR′も同じでも異つ
てもよい。
これら化合物を例示すると、Mg（OCH3）2，
Mg（OC2H5）2，Mg（OCH3）（OC2H5），Mg（Oi
―C3H7）2，Mg（OC3H7）2，Mg（OC4H9）2，Mg
（Oi―C4H9）2，Mg（OC4H9）（Oi―C4H9），Mg
（OC4H9）（Osec―C4H9），Mg（OC6H13）2，
Mg（OC8H17）2，Mg（OC6H11）2，Mg
（OC6H5）2，Mg（OC6H4CH3）2，Mg
（OCH2C6H5）2等を挙げることができる。
これらマグネシウムアルコキシドは使用する
際に、乾燥するのが望ましく、特に減圧下での
加熱乾燥が望ましい。さらに、これらマグネシ
ウムアルコキシドは、市販品を用いてもよく、
公知の方法で合成したものを用いてもよい。
このマグネシウムジアルコキシドは、無機或
いは有機の不活性な固体物質として接触させて
使用することも可能である。
無機の固体物質としては、硫酸塩、水酸化
物、炭酸塩、リン酸塩、ケイ酸塩のような金属
化合物が適しており、例えば、Mg（OH）2，
BaCO3，Ca3（PO4）2等が挙げられる。
有機の固体物質としては、デユレン、アント
ラセン、ナフタレン、ジフエニルのような芳香
族炭化水素等の低分子量化合物が挙げられる。
又、ポリエチレン、ポリプロピレン、ポリビニ
ルトルエン、ポリスチレン、ポリメチルメタク
リレート、ポリアミド、ポリエステル、ポリ塩
化ビニル等の高分子量化合物も用いることがで
きる。
(B) 珪素化合物
本発明で用いられる珪素化合物は、一般式
HnRoSiXrで表わされる式において、Ｒは炭
化水素基、R′O―（R′は炭化水素基）、
R2R3N―（R2，R3は炭化水素基）である。Ｘ
はハロゲン原子、１ｍ３、０ｒ３，ｍ
＋ｎ＋ｒ＝４をそれぞれ示す。又、ｎが１を超
える場合はＲは同じでも異つてもよい。
Ｒ，R1，R2，R3で示される炭化水素基とし
ては、炭素数１〜16個のアルキル、アルケニ
ル、シクロアルキル、アリール、アルアルキル
等を挙げることができる。アルキルとしては、
メチル、エチル、プロピル、ｎ―ブチル、イソ
ブチル、ｎ―ヘキシル、ｎ―オクチル、２―エ
チルヘキシル、ｎ―デシル等が、アルケニルと
しては、ビニル、アリル、イソプロペニル、プ
ロペニル、ブテニル等が、シクロアルキルとし
ては、シクロペンチル、シクロヘキシル等が、
アリールとしては、フエニル、トリル、キシリ
ル等が、アルアキルとしては、ベンジル、フエ
ネチル、フエニルプロピル等が挙げられる。
これらの中でもメチル、エチル、プロピル、
イソプロピル、ｎ―ブチル、イソブチル、ｔ―
ブチル等の低級アルキル及びフエニル、トリル
等のアリールが望ましい。
Ｘは塩素、臭素、ヨウ素等のハロゲン原子で
あり、望ましくは塩素原子である。
珪素化合物を例示すると、HSiCl3，
H2SiCl2，H3SiCl，HCH3SiCl2，HC2H5SiCl2，
Ｈ（ｔ―C4H9）SiCl2，HC6H5SiCl2，Ｈ
（CH3）2SiCl，Ｈ（ｉ―C3H7）2SiCl，
H2C2H5SiCl，H2（ｎ―C4H9）SiCl，H2
（C6H4CH3）SiCl，HSi（CH3）3，HSiCH3
（OCH3）2，HSiCH3（OC2H5）2HSi（OCH3）3，
（C2H5）2SiH2，HSi（CH3）2（OC2H5），HSi
（CH3）2〔Ｎ（CH3）2〕，HSiCH3（C2H5）2，
HSiC2H5（OC2H5）2，HSiCH3〔Ｎ（CH3）2〕2，
C6H5SiH3，HSi（C2H5）3，HSi（OC2H5）3，
HSi（CH3）2〔Ｎ（C2H5）2〕，HSi〔Ｎ（CH3）2〕3，
C6H5CH3SiH2，C6H5（CH3）2SiH，（ｎ―
C3H7）3SiH，HSiCl（C6H5）2，H2Si（C6H5）2，
HSi（C6H5）2CH3，（ｎ―C5H11O）3SiH，HSi
（C6H5）3，（ｎ―C5H11）3SiH等を挙げることが
できる。これら中でも、HSiCl3，HSi（CH3）
Cl2，HSi（CH3）2Cl，HSi（C2H5）3等が特に望
ましい。
(C) チタン化合物
チタン化合物は、一般式TiXo（OR）4-oで表
わされる。この式において、Ｘは塩素、臭素等
のハロゲン原子を示し、Ｒは、好ましくは炭素
数１〜８個の、アルキル基、アリール基等の炭
化水素基を示す。又、ｎは０ｎ４の範囲の
任意の数である。それら化合物を例示すると、
四塩化チタン、四臭化チタン、トリクロルエト
キシチタン、トリクロルブトキシチタン、ジク
ロルジエトキシチタン、ジクロルジブトキシチ
タン、ジクロルジフエノキシチタン、クロルト
リエトキシチタン、クロルトリブトキシチタ
ン、テトラブトキシチタン等を挙げることがで
きる。これらの中でも、四塩化チタン、トリク
ロルエトキシチタン、ジクロルジブトキシチタ
ン、ジクロルジフエノキシチタン等のチタンハ
ロゲン化物が望ましく、特に四塩化チタンが望
ましい。
触媒成分の調製法
本発明に係る触媒成分は、(1)マグネシウムジア
ルコキシド（Ａ成分）と前記一般式の珪素化合物
（Ｂ成分）を接触させ、得られた固体生成物を前
記一般式のチタン化合物（Ｃ成分）と接触させる
こと、(2)Ａ成分とＢ成分を接触させ、得られた固
体生成物を電子供与性化合物（Ｄ成分）と接触さ
せ、次いでＣ成分と接触させること、によつて製
造することができる。
以下、それらの方法について説明する。
マグネシウムジアルコキシドと珪素化合物と
の接触
マグネシウムジアルコキシドと珪素化合物と
の接触は、両者を炭化水素及び／又はハロゲン
化炭化水素の存在下又は不存在下に、混合撹拌
する方法、機械的に共粉砕する方法等により達
成される。
炭化水素としては、ヘキサン、ヘプタン、オ
クタン、シクロヘキサン、ベンゼン、トルエ
ン、キシレン等が、ハロゲン化炭化水素として
は、１，２―ジクロルエタン、１，２―ジクロ
ルプロパン、四塩化炭素、塩化ブチル、塩化イ
ソアミル、ブロムベンゼン、クロルトルエン等
が挙げられる。
マグネシウムジアルコキシドと珪素化合物の
接触割合は、マグネシウムジアルコキシド１モ
ル当り、珪素化合物0.5〜10モル、望ましくは
１〜５モルである。
機械的共粉砕により両者を接触する場合は、
粉砕物を得るために用いられる通常の粉砕機を
用いて行えばよく、その粉砕機として例えば回
転ボールミル、振動ボールミル、衝撃ミル等を
挙げることができる。共粉砕処理は必要に応じ
て、減圧下又は不活性ガスの雰囲気中で、かつ
水分、酸素等が実質的に存在しない状態で行う
ことができる。
機械的共粉砕する場合の接触温度は、０〜
200℃、接触時間は0.5〜100時間である。又、
単に撹拌する接触方法の場合の接触温度は、０
〜200℃、接触時間は0.5〜100時間である。珪
素化合物は一種に限らず同時に二種以上用いて
もよい。
本発明の第二の発明は、マグネシウムジアル
コキシドと珪素化合物との接触物を更に電子供
与性化合物と接触させるものである。用い得る
電子供与性化合物としては、カルボン酸類、カ
ルボン酸エステル類、アルコール類、エーテル
類、ケトン類、アミン類、アミド類、ニトリル
類、アルデヒド類、アルコレート類、有機基と
炭素もしくは酸素を介して結合した燐、ヒ素お
よびアンチモン化合物、ホスホアミド類、チオ
エーテル類、チオエステル類、炭酸エステル類
が挙げられるが、これらのうち好ましく使用さ
れるものとしてはカルボン酸エステル類、アル
コール類、エーテル類である。
カルボン酸エステルの具体例としては、ギ酸
ブチル、酢酸エチル、酢酸ブチル、アクリル酸
エチル、酪酸エチル、イソ酪酸イソブチル、メ
タクリル酸メチル、マレイン酸ジエチル、酒石
酸ジエチル、シクロヘキサンカルボン酸エチ
ル、安息香酸エチル、ｐ―メトキシ安息香酸エ
チル、ｐ―メチル安息香酸メチル、ｐ―第三級
ブチル安息香酸エチル、フタル酸ジブチル、フ
タル酸ジアリル、α―ナフトエ酸エチル等が挙
げられるが、これらに限定されるものではな
い。これらの中でも芳香族カルボン酸のアルキ
ルエステル、特に安息香酸またはｐ―メチル安
息香酸、ｐ―メトキシ安息香酸などの核置換安
息香酸の炭素数１〜８個のアルキルエステルが
好ましく用いられる。アルコール類は、一般式
ROHで表わされる。式においてＲは炭素数１
〜12個のアルキル、アルケニル、シクロアルキ
ル、アリール、アルアルキルである。その具体
例としては、メタノール、エタノール、プロパ
ノール、イソプロパノール、ブタノール、イソ
ブタノール、ペンタノール、ヘキサノール、オ
クタノール、２―エチルヘキサノール、シクロ
ヘキサノール、ベンジルアルコール、アリルア
ルコール等である。エーテル類は、一般式
ROR′で表わされる。式においてＲ，R′は炭素
数１〜12個のアルキル、アルケニル、シクロア
ルキル、アリール、アルアルキルであり、Ｒと
R′は同じでも異つてもよい。その具体例とし
ては、ジエチルエーテル、ジイソプロピルエー
テル、ジブチルエーテル、ジイソブチルエーテ
ル、ジイソアミルエーテル、ジ―２―エチルヘ
キシルエーテル、ジアリルエーテル、エチルア
リルエーテル、ブチルアリルエーテル、ジフエ
ニルエーテル、アニソール、エチルフエニルエ
ーテル等である。
マグネシウムアルコキシドと珪素化合物との
接触物と、電子供与性化合物との接触は、両者
を不活性な炭化水素の存在下又は不存在に、混
合撹拌する方法、機械的に共粉砕する方法等に
より達成される。不活性な炭化水素としては、
ヘキサン、ヘプタン、オクタン、シクロヘキサ
ン、ベンゼン、トルエン、キシレン等が挙げら
れる。
機械的共粉砕による接触の場合の接触温度
は、０〜100℃、接触時間は0.1〜100時間であ
る。又、単に撹拌する接触方法の場合の接触温
度は、０〜150℃、接触時間は0.5〜10時間であ
る。
電子供与性化合物は、マグネシウムジアルコ
キシドと珪素化合物との接触物中のマグネシウ
ム１グラム原子当り0.01〜10グラムモル、特に
0.05〜１グラムモルの範囲で用いるのが望まし
い。
チタン化合物との接触
マグネシウムジアルコキシドと珪素化合物と
の接触物又はさらに電子供与性化合物との接触
物（以下、これらを該接触物という）は、次い
でチタン化合物と接触させて本発明に係る触媒
成分とする。該接触物はチタン化合物と接触さ
せる前に、適当な洗浄剤、例えば前記の不活性
の炭化水素、で洗浄してもよい。
該接触物とチタン化合物との接触は、両者を
そのまま接触させてもよいが、炭化水素及び／
又はハロゲン化炭化水素の存在下、両者を混合
撹拌する方法、機械的に共粉砕する方法等で行
うのが望ましい。
炭化水素としては、ヘキサン、ヘプタン、オ
クタン、シクロヘキサン、ベンゼン、トルエ
ン、キシレン等の炭素数６〜12個の飽和脂肪
族、飽和脂環式及び芳香族炭化水素が望まし
い。又、ハロゲン化炭化水素としては、炭素数
１〜12個の飽和又は不飽和の脂肪族、脂環式及
び芳香族炭化水素のモノ及びポリハロゲン置換
体である。それら化合物の具体的な例は、脂肪
族化合物では、メチルクロリド、メチルブロミ
ド、メチルアイオダイド、メチレンクロリド、
メチレンブロミド、メチレンアイオダイド、ク
ロロホルム、ブロモホルム、ヨードホルム、四
塩化炭素、四臭化炭素、四沃化炭素、エチルク
ロリド、エチルブロミド、エチルアイオダイ
ド、１，２―ジクロルエタン、１，２―ジブロ
ムエタン、１，２―ジヨードエタン、メチルク
ロロホルム、メチルブロモホルム、メチルヨー
ドホルム、１，１，２―トリクロルエチレン、
１，１，２―トリブロムエチレン、１，１，
２，２―テトラクロルエチレン、ペンタクロル
エタン、ヘキサクロルエタン、ヘキサブロムエ
タン、ｎ―プロピルクロリド、１，２―ジクロ
ルプロパン、ヘキサクロルプロピレン、オクタ
クロルプロパン、デカブロムブタン、塩素化パ
ラフインが、脂環式化合物ではクロルシクロプ
ロパン、テトラクロルシクロペンタン、ヘキサ
クロルペンタジエン、ヘキサクロルシクロヘキ
サンが、芳香族化合物ではクロルベンゼン、ブ
ロムベンゼン、ｏ―ジクロルベンゼン、ｐ―ジ
クロルベンゼン、ヘキサクロルベンゼン、ヘキ
サブロムベンゼン、ベンゾトリクロリド、ｐ―
クロルベンゾトリクロリド等が挙げられる。こ
れらの化合物は、一種のみならず二種以上用い
てもよい。
該接触物とチタン化合物との接触における両
者の使用割合は、該接触物中のマグネシウム１
グラム原子当り、チタン化合物0.1グラムモル
以上、望ましくは１〜50グラムモルである。
又、その接触条件は、炭化水素及び／又はハロ
ゲン化炭化水素の存在下で行う場合、０〜200
℃で0.5〜20時間、望ましくは60〜150℃で１〜
５時間である。
炭化水素及び／又はハロゲン化炭化水素の使
用量は、該接触物が液体物質（炭化水素及び／
又は液状のハロゲン化炭化水素並びに液状のチ
タン化合物）１当り、10〜300ｇとなるよう
に用いるのが望ましい。チタン化合物との接触
は必要に応じて２回以上行つてもよい。
上記のようにして得られた固体状物質は、液状
物質から分離し、必要に応じてヘキサン、ヘプタ
ン、オクタン、シクロヘキサン、ベンゼン、トル
エン、キシレン等の不活性な炭化水素で洗浄し、
乾燥することによつて本発明に係る触媒成分とす
る。
本発明に係る触媒成分は、ベツト（BET）法
で液体窒素の吸着温度において測定した比表面積
が50〜650m2／ｇ、細孔容積が0.05〜0.4c.c.／ｇで
あり、その粒度分布も狭くて大きさが揃つてい
る。又、その組成はマグネシウム原子が10〜25重
量％、チタン原子が１〜10重量％、ハロゲン原子
が40〜60重量％であり、その他有機化合物等を含
む。又、触媒成分を調製する際にハロゲン化炭化
水素及び／又は電子供与性化合物を用いた場合
は、その物質中にはハロゲン化炭化水素、電子供
与性化合物及び／又はそれらの変換物質が少量含
まれる場合がある。
オレフインの重合触媒
本発明に係る触媒成分は、有機アルミニウム化
合物と組合せてオレフインの単独重合又は他のオ
レフインとの共重合用の触媒とする。
有機アルミニウム化合物
オレフインを重合する際に触媒成分と組合せる
有機アルミニウム化合物は、一般式RoAlX3-o（但
し、Ｒはアルキル基又はアリール基、Ｘはハロゲ
ン原子、アルコキシ基又は水素原子を示し、ｎは
１ｎ３の範囲の任意の数である。）で示され
るものであり、例えばトリアルキルアルミニウ
ム、ジアルキルアルミニウムモノハライド、モノ
アルキルアルミニウムジハライド、アルキルアル
ミニウムセスキハライド、ジアルキルアルミニウ
ムモノアルコキシド及びジアルキルアルミニウム
モノハライドなどの炭素数１ないし18個、好まし
くは炭素数２ないし６個のアルキルアルミニウム
化合物又はその混合物もしくは錯化合物が特に好
ましい。具体的には、トリメチルアルミニウム、
トリエチルアルミニウム、トリプロピルアルミニ
ウム、トリイソブチルアルミニウム、トリヘキシ
ルアルミニウムなどのトリアルキルアルミニウ
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、ジエチルアルミニウムブロ
ミド、ジエチルアルミニウムアイオダイド、ジイ
ソブチルアルミニウムクロリドなどのジアルキル
アルミニウムモノハライド、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、エ
チルアルミニウムジブロミド、エチルアルミニウ
ムジブロミド、エチルアルミニウムジアイオダイ
ド、イソブチルアルミニウムジクロリドなどのモ
ノアルキルアルミニウムジハライド、エチルアル
ミニウムセスキクロリドなどのアルキルアルミニ
ウムセスキハライド、ジメチルアルミニウムメト
キシド、ジエチルアルミニウムエトキシド、ジエ
チルアルミニウムフエノキシド、ジプロピルアル
ミニウムエトキシド、ジイソブチルアルミニウム
エトキシド、ジイソブチルアルミニウムフエノキ
シドなどのジアルキルアルミニウムモノアルコキ
シド、ジメチルアルミニウムハイドライド、ジエ
チルアルミニウムハイドライド、ジプロピルアル
ミニウムハイドライド、ジイソブチルアルミニウ
ムハイドライドなどのジアルキルアルミニウムハ
イドライドが挙げられる。
これらの中でも、トリアルキルアルミニウム
が、特にトリエチルアルミニウム、トリイソブチ
ルアルミニウムが望ましい。又、これらトリアル
キルアルミニウムは、その他の有機アルミニウム
化合物、例えば、工業的に入手し易いジエチルア
ルミニウムクロリド、エチルアルミニウムジクロ
リド、エチルアルミニウムセスキクロリド、ジエ
チルアルミニウムエトキシド、ジエチルアルミニ
ウムハイドライド又はこれらの混合物若しくは錯
化合物等と併用することができる。
さらに、有機アルミニウム化合物は、単独で用
いてもよいが、電子供与性化合物と組合せて用い
てもよい。電子供与性化合物としては、前記触媒
成分調製時の、マグネシウムジアルコキシドと珪
素化合物との接触物に必要に応じて接触させる電
子供与性化合物ならば、どの化合物も用いること
ができるが、中でもカルボン酸エステル類、アル
コール類、エーテル類、ケトン類が望ましい。こ
れら電子供与性化合物は、有機アルミニウム化合
物を触媒成分と組合せて用いる際に用いてもよ
く、予め有機アルミニウム化合物と接触させた上
で用いてもよい。
本発明に係る触媒成分に対する有機アルミニウ
ム化合物の使用量は、該触媒成分中のチタン１グ
ラム原子当り、通常１〜2000グラムモル、特に20
〜500グラムモルが望ましい。
又、有機アルミニウム化合物と電子供与性化合
物の比率は、電子供与性化合物１モルに対して有
機アルミニウム化合物がアルミニウムとして0.1
〜40、好ましくは１〜25グラム原子の範囲で選ば
れる。
オレフインの重合
上記のようにして得られた触媒成分と有機アル
ミニウム化合物（及び電子供与性化合物）からな
る触媒は、モノオレフインの単独重合又は他のモ
ノオレフイン若しくはジオレフインとの共重合の
触媒として有用であるが、特にα―オレフイン、
特に炭素数３ないし６個のα―オレフイン、例え
ばプロピレン、１―ブテン、４―メチル―１―ペ
ンテン、１―ヘキセン等の単独重合又は上記のα
―オレフイン相互及び／又はエチレンとのランダ
ム及びブロツク共重合の触媒、エチレンの単独重
合又はエチレンと炭素数３〜10個のα―オレフイ
ン、例えばプロピレン、１―ブテン、４―メチル
―１―ペンテン、１―ヘキセン、１―オクテン等
とのランダム若しくはブロツク共重合の触媒とし
て極めて優れた性能を示す。
重合反応は、気相、液相のいずれでもよく、液
相で重合させる場合は、ノルマルブタン、イソブ
タン、ノルマルペンタン、イソペンタン、ヘキサ
ン、ヘプタン、オクタン、シクロヘキサン、ベン
ゼン、トルエン、キシレン等の不活性炭化水素中
及び液状モノマー中で行うことができる。重合温
度は、通常−80℃〜＋150℃、好ましくは40〜120
℃の範囲である。重合圧力は、例えば１〜60気圧
でよい。又、得られる重合体の分子量の調節は、
水素若しくは他の公知の分子量調節剤を存在せし
めることにより行なわれる。又、共重合において
オレフインに共重合させる他のオレフインの量
は、オレフインに対して通常30重量％迄、特に
0.3〜15重量％の範囲で選ばれる。本発明の触媒
系による重合反応は、連続又はバツチ式反応で行
ない、その条件は通常用いられる条件でよい。
又、共重合反応は一段で行つてもよく、二段以上
で行つてもよい。
発明の効果
本発明に係る触媒成分は、ポリオレフイン、特
にアイソタクチツクポリプロピレン、エチレンと
プロピレンとのランダム共重合体及びエチレンと
プロピレンとのブロツク共重合体を製造する場合
の触媒成分として有効である。
本発明に係る触媒成分を用いた重合触媒は、重
合活性及び立体規則性が高く、しかもその高い重
合活性を重合時に長時間持続することができると
共に、得られたオレフイン重合体粉末は嵩密度が
高い。又、この重合体粉末は流動性に富んでい
る。
実施例
次に、本発明を実施例及び応用例により具体的
に説明する。但し、本発明は実施例のみにより限
定されるものではない。なお、実施例及び応用例
に示したパーセント（％）は、特に断らない限り
重量による。
触媒成分の比表面積（S.A.）及び細孔容積（P.
V.）は、CARLO ERBA製SORPTOMATIC
1810型装置を用いて測定した。重合活性Kcは触
媒成分１ｇ当りのポリマー生成量（ｇ）、Ktは触
媒成分中のTi1ｇ当りのポリマー生成量（Kg）で
ある。触媒比活性は、触媒成分１ｇ、重合時間１
時間、重合時のモノマーの分圧１Kg／cm2当りの重
合体の生成量（ｇ）を示す。
ポリマー中の結晶性ポリマーの割合を示すヘプ
タン不溶分（以下H.I.と略称する。）は、改良型
ソツクスレー抽出器で沸騰ｎ―ヘプタンにより６
時間抽出した場合の残量である。メルトフローレ
イト（MFR）及びメルトインデツクス（MI）は
ASTM―D1238に従つて測定した。又嵩密度は
ASTM―D1895―69メソツドＡに従つて測定し
た。
実施例 １
マグネシウムジエトキシドとトリクロルシラン
の接触
還流凝縮器、滴下ロート及び撹拌機を取付けた
500mlのガラス製反応器を充分に窒素ガスで置換
する。この反応器に市販のマグネシウムジエトキ
シド30.2ｇ（0.26モル）及びｎ―ヘプタン100ml
を入れた後、室温で撹拌しながらトリクロルシラ
ン75ｇ（0.55モル）とｎ―ヘプタン30mlの混合溶
液を滴下ロートから45分間で滴下し、さらに70℃
で２時間撹拌した。この間反応混合物からガスが
発生した。そのガスを分析したところエチルクロ
リド、エチレン、水素、エタンであつた。得られ
た固体を70℃で別し、65℃のｎ―ヘキサン各
300mlで５回洗浄した後、減圧下60℃で30分間乾
燥して固体成分（）を得た。固体成分（）
は、マグネシウムを14％、珪素を11％、塩素を51
％含み、又その表面積は20m2／ｇ、細孔容積0.05
c.c.／ｇであつた。
この固体成分（）15.1ｇを、直径12mmのステ
ンレス（SUS316）製ボール100個を収容した内
容積300mlのステンレス（SUS316）製ミルポツ
トに窒素ガス雰囲気下で入れ、次いで安息香酸エ
チル3.8ｇを加え、このミルポツトを振とう器に
装着した後、１時間振とうして接触を行い、固体
成分（）を得た。
四塩化チタン処理
固体成分（）8.5ｇを、撹拌機を取付けた200
mlのガラス製反応器に窒素ガス雰囲気下で入れ、
次いでトルエン40ml、四塩化チタン60ml加え、90
℃で２時間撹拌した。得られた固体状物質を90℃
で別し、各100mlのｎ―ヘキサンにて65℃で７
回洗浄した後、減圧下60℃で30分間乾燥してチタ
ン含有量2.6％、マグネシウム含有量19.0％、塩
素含有量53.6％、珪素含有量2.7％、安息香酸エ
チル含有量13.7％の触媒成分を6.1ｇ得た。この
触媒成分は、比表面積210m2／ｇ、細孔容積0.17
c.c.／ｇであつた。
実施例 ２
マグネシウムジエトキシド〔Mg（OEt）2〕とト
リクロルシラン（HSiCl3）の接触時の両者の使
用割合をHSiCl3／Mg（OEt）2＝1.5（モル比）とし
た以外は、実施例１と同様にして触媒成分を調製
した。得られた触媒成分の組成及び物性は第１表
の通りであつた。
実施例 ３
実施例１において、固体成分（）と安息香酸
エチルとの共粉砕処理の際、固体成分（）と安
息香酸エチルの重量比を７：３とした以外は、実
施例１と同様にして触媒成分を調製した。得られ
た触媒成分の組成及び物性は第１表の通りであつ
た。
実施例 ４
マグネシウムジエトキシドの調製
還流凝縮器、撹拌機を取付けた１のガラス製
反応器を充分に窒素ガスで置換する。これにマグ
ネシウム金属片13.6ｇ、エタノール150ml、ｎ―
ヘプタン300mlを入れ、さらにヨウ素のヨウ化メ
チル溶液（ヨウ素２ｇ／ヨウ化メチル25ｇ）0.5
mlを加え室温で反応を開始した。その後70℃で15
時間反応させた。得られた固体物質を分離し、各
300mlのｎ―ヘキサンにより65℃で５回洗浄し、
次いで減圧下60℃で乾燥してマグネシウムジエト
キシド59ｇを得た。
触媒成分の調製
上記で得られたマグネシウムジエトキシドを市
販のマグネシウムジエトキシドに代えて用いた以
外は、実施例１と同様にして、第１表に示す組成
及び物性を有する触媒成分を調製した。
実施例 ５〜９
実施例１において、マグネシウムジエトキシド
と接触する際に用いたトリクロルシランの代り
に、メチルジクロルシラン（実施例５）、ジメチ
ルクロルシラン（実施例６）、トリエチルシラン
（実施例７）、ジエトキシメチルシラン（実施例
８）、ビス（ジメチルアミノ）メチルシラン（実
施例９）を用いた以外は、実施例１と同様にして
第１表に示す組成及び物性を有する触媒成分を調
製した。
比較例 １，２
実施例１において、マグネシウムジエトキシド
と接触する際に用いたトリクロルシランの代り
に、テトラクロルシラン（比較例１）、メチルト
リクロルシラン（比較例２）を用いた以外は、実
施例１と同様にして第１表に示す組成及び物性を
有する固体物質を調製した。なお、マグネシウム
ジエトキシドとテトラクロルシラン及びメチルト
リクロルシランの接触時に、共にガスの発生は見
られなかつた。
比較例 ３
実施例１において、マグネシウムジエトキシド
をトリクロルシランと接触しなかつた以外は、実
施例１と同様にして第１表に示す組成及び物性を
有する固体物質を調製した。
実施例 10，11
実施例１又は実施例５において、固体成分
（）を安息香酸エチルと接触しなかつた以外は、
実施例１と同様にして触媒成分を調製した。得ら
れた触媒成分の組成及び物性は第１表の通りであ
つた。
比較例 ４
実施例１において用いたミルポツトに窒素ガス
雰囲気下に、市販のマグネシウムジエトキシド
13.6ｇ、安息香酸エチル4.1ml、四塩化珪素2.0ml
を入れ、このミルポツトを振とう器に装着した
後、15時間振とうした。
得られた粉砕固体8.6ｇを200mlの撹拌機付きガ
ラス容器に窒素ガス雰囲気下に入れ、これに四塩
化チタン50mlを加え、80℃で２時間撹拌した。得
られた固体状物質を80℃で別し、各100mlのｎ
―ヘキサンにて65℃で７回洗浄した後、減圧下60
℃で30分間乾燥して第１表に示す組成及び物性を
有する触媒成分を調製した。
比較例 ５
還流凝縮器、撹拌機を取付けた１のガラス製
反応器を充分に窒素ガスで置換する。これに市販
のマグネシウムジエトキシド6.3ｇ、安息香酸エ
チル1.5ml、四塩化珪素100mlを入れ、60℃で24時
間撹拌した。余剰の液状物を棄て、65℃でｎ―ヘ
キサン各90mlを用い固体状物質を５回洗浄した。
次に四塩化チタン90mlを加え、90℃で２時間接触
させた後、同温度で固体状物質を別し、新らた
に四塩化チタン90mlを加えて90℃で２時間接触し
た。固体状物質を90℃で別し、65℃でｎ―ヘキ
サン各90mlを用い７回洗浄した後、減圧下60℃で
30分間乾燥して、第１表に示す組成及び物性を有
する触媒成分を調製した。
比較例 ６
実施例１の四塩化チタン処理における固体成分
（）を市販のマグネシウムジエトキシド〔Mg
（OEt）2〕に変えた以外は、実施例１と同様にし
てMg（OEt）2と四塩化チタンを接触させ、第１表
に示す組成及び物性を有する触媒成分を調製し
た。
TECHNICAL FIELD The present invention relates to a method for producing a catalyst component for olefin polymerization, and more particularly to a method for producing a catalyst component that can produce an olefin polymer with high stereoregularity and high bulk density in high yield. BACKGROUND ART Although it is known that a halogen-free contact product of a magnesium compound and a titanium compound is effective as a catalyst component for olefin polymerization, its catalytic performance is low, and as an improvement method, the general formula SiX l
A method of bringing Mg(OR) 2 into contact with titanium tetrahalide in the presence of a halogenated silane of R 4-l or the halogenated silane and an electron-donating compound (JP-A-52-1989-1).
98076), when or after contacting a magnesium compound having an Mg-O-R bond with a halogenating agent such as a silicon compound of the general formula X n SiR o , an electron-donating compound is present. Attempts have been made to produce a catalyst component by a contact method (Japanese Unexamined Patent Publication No. 53-43094). Furthermore, a method of bringing a tetravalent titanium compound having at least one halogen atom into contact with a solid product of an aluminum halide, an organic compound having a Si--O bond, and a magnesium alcoholate (Japanese Unexamined Patent Publication No. 53-78287
(Japanese Unexamined Patent Publication No. 155205/1989), and a method in which a reaction product obtained by reacting a magnesium compound, a titanium compound, and a silicon compound is reacted with at least one type of aluminum halide compound (Japanese Patent Laid-Open No. 155205/1983). Attempts have also been made to produce solid catalyst components using aluminum chloride as an essential reaction component. However, catalyst components obtained by these methods have problems such as low catalytic activity, poor stereoregularity, and low bulk density of the resulting polymer. Furthermore, a catalyst component for olefin polymerization has been proposed, which is formed by contacting (1) a magnesium compound, (2) an electron-donating compound, (3) a silicon compound having an Si--H bond, and (4) a titanium halogen compound. (Unexamined Japanese Patent Publication No. 1983-
92009), the magnesium compound in this proposal is essentially a halogenated magnesium compound, and the silicon compound and the titanium halogen compound are used simultaneously and contacted,
Its catalytic performance is also not satisfactory. DISCLOSURE OF THE INVENTION OBJECTS OF THE INVENTION The present invention aims to provide a catalyst component that exhibits high stereoregularity and high activity and can produce an olefin polymer with high bulk density using a halogen-free magnesium compound as a starting material. As a result of intensive research, the present inventors have found that a contact product obtained by contacting magnesium alkoxide with a silicon compound having a hydrogen-silicon bond and then contacting it with a titanium compound, or a contact product formed by contacting magnesium alkoxide with a silicon compound having a hydrogen-silicon bond, The present invention was completed by discovering that a contact product obtained by contacting the silicon compound, then contacting an electron-donating compound, and then contacting a titanium compound exhibits excellent performance as a catalyst component for olefin polymerization. Summary of the Invention The present invention provides (1) (A) magnesium dialkoxide and (B) general formula
HmRnSiXr [However, R is a hydrocarbon group, R 1 O- or R 2 R 3 N-, X is a halogen atom,
1m3,0r3,m+n+r=4. R 1 , R 2 and R 3 each represent a hydrocarbon group. ], and the resulting solid product is (C) with the general formula TiX o (OR) 4-o [where X is a halogen atom, R is a hydrocarbon group, and 0n
It is 4. ] A method for producing a catalyst component for olefin polymerization, which comprises bringing it into contact with a titanium compound. (2) (A) Magnesium dialkoxide and (B) general formula
HmRnSiXr [However, R is a hydrocarbon group, R 1 O- or R 2 R 3 N-, X is a halogen atom,
1m3,0r3,m+n+r=4. R 1 , R 2 and R 3 each represent a hydrocarbon group. ], the obtained solid product is brought into contact with (D) an electron-donating compound, and then (C) with the general formula TiX o (OR) 4-o [where X is a halogen atom and R is It shows a hydrocarbon group and is 0n4. The gist is a method for producing a catalyst component for olefin polymerization, which comprises contacting the catalyst component with a titanium compound. Raw Materials for Preparing Catalyst Component Each raw material used in preparing the catalyst component of the present invention will be explained. (A) Magnesium dialkoxide The magnesium alkoxide used in the present invention is represented by the general formula Mg(OR)(OR'). In the formula, R and R' have 1 or more carbon atoms.
20, preferably 1 to 10 alkyl, alkenyl, cycloalkyl, aryl, aralkyl groups. Furthermore, R', which is the same as R, may be the same or different. Examples of these compounds include Mg(OCH 3 ) 2 ,
Mg(OC 2 H 5 ) 2 , Mg(OCH 3 )(OC 2 H 5 ), Mg(Oi
―C 3 H 7 ) 2 , Mg (OC 3 H 7 ) 2 , Mg (OC 4 H 9 ) 2 , Mg
(Oi-C 4 H 9 ) 2 , Mg (OC 4 H 9 ) (Oi-C 4 H 9 ), Mg
(OC 4 H 9 ) (Osec-C 4 H 9 ), Mg (OC 6 H 13 ) 2 ,
Mg (OC 8 H 17 ) 2 , Mg (OC 6 H 11 ) 2 , Mg
(OC 6 H 5 ) 2 , Mg (OC 6 H 4 CH 3 ) 2 , Mg
(OCH 2 C 6 H 5 ) 2 and the like. When these magnesium alkoxides are used, it is desirable to dry them, and it is particularly desirable to dry them by heating under reduced pressure. Furthermore, these magnesium alkoxides may be commercially available products,
Those synthesized by known methods may also be used. The magnesium dialkoxide can also be used in contact as an inert solid inorganic or organic substance. Suitable inorganic solid substances are metal compounds such as sulphates, hydroxides, carbonates, phosphates, silicates, for example Mg(OH) 2 ,
Examples include BaCO 3 and Ca 3 (PO 4 ) 2 . Organic solid materials include low molecular weight compounds such as aromatic hydrocarbons such as durene, anthracene, naphthalene, and diphenyl.
Further, high molecular weight compounds such as polyethylene, polypropylene, polyvinyltoluene, polystyrene, polymethyl methacrylate, polyamide, polyester, and polyvinyl chloride can also be used. (B) Silicon compound The silicon compound used in the present invention has the general formula
In the formula represented by H n R o SiX r , R is a hydrocarbon group, R′O—(R′ is a hydrocarbon group),
R 2 R 3 N—(R 2 and R 3 are hydrocarbon groups). X
is a halogen atom, 1m3,0r3,m
+n+r=4 respectively. Further, when n exceeds 1, R may be the same or different. Examples of the hydrocarbon group represented by R, R1 , R2 , and R3 include alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 16 carbon atoms. As an alkyl,
Methyl, ethyl, propyl, n-butyl, isobutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-decyl, etc. are used as alkenyl, vinyl, allyl, isopropenyl, propenyl, butenyl, etc. are used as cycloalkyl. are cyclopentyl, cyclohexyl, etc.
Examples of aryl include phenyl, tolyl, xylyl, etc., and examples of aralkyl include benzyl, phenethyl, phenylpropyl, etc. Among these, methyl, ethyl, propyl,
Isopropyl, n-butyl, isobutyl, t-
Lower alkyls such as butyl and aryls such as phenyl and tolyl are preferred. X is a halogen atom such as chlorine, bromine, or iodine, preferably a chlorine atom. Examples of silicon compounds include HSiCl 3 ,
H 2 SiCl 2 , H 3 SiCl, HCH 3 SiCl 2 , HC 2 H 5 SiCl 2 ,
H ( t- C4H9 ) SiCl2 , HC6H5SiCl2 , H
(CH 3 ) 2 SiCl, H(i-C 3 H 7 ) 2 SiCl,
H 2 C 2 H 5 SiCl, H 2 (n-C 4 H 9 )SiCl, H 2
(C 6 H 4 CH 3 )SiCl, HSi(CH 3 ) 3 , HSiCH 3
(OCH 3 ) 2 , HSiCH 3 (OC 2 H 5 ) 2 HSi(OCH 3 ) 3 ,
(C 2 H 5 ) 2 SiH 2 , HSi(CH 3 ) 2 (OC 2 H 5 ), HSi
(CH 3 ) 2 [N(CH 3 ) 2 ], HSiCH 3 (C 2 H 5 ) 2 ,
HSiC 2 H 5 (OC 2 H 5 ) 2 , HSiCH 3 [N(CH 3 ) 2 ] 2 ,
C6H5SiH3 , HSi( C2H5 ) 3 , HSi ( OC2H5 ) 3 ,
HSi(CH 3 ) 2 [N(C 2 H 5 ) 2 ], HSi[N(CH 3 ) 2 ] 3 ,
C 6 H 5 CH 3 SiH 2 , C 6 H 5 (CH 3 ) 2 SiH, (n-
C 3 H 7 ) 3 SiH, HSiCl(C 6 H 5 ) 2 , H 2 Si(C 6 H 5 ) 2 ,
HSi(C 6 H 5 ) 2 CH 3 , (n-C 5 H 11 O) 3 SiH, HSi
Examples include (C 6 H 5 ) 3 and (n-C 5 H 11 ) 3 SiH. Among these, HSiCl 3 , HSi(CH 3 )
Particularly preferred are Cl 2 , HSi(CH 3 ) 2 Cl, HSi(C 2 H 5 ) 3 and the like. (C) Titanium compound A titanium compound is represented by the general formula TiX o (OR) 4-o . In this formula, X represents a halogen atom such as chlorine or bromine, and R represents a hydrocarbon group such as an alkyl group or an aryl group, preferably having 1 to 8 carbon atoms. Further, n is an arbitrary number in the range of 0n4. Examples of these compounds are:
Examples include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorbutoxytitanium, dichlordiethoxytitanium, dichlordibutoxytitanium, dichlorodiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, etc. be able to. Among these, titanium halides such as titanium tetrachloride, trichlorethoxytitanium, dichlorodibutoxytitanium, and dichlorodiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred. Method for Preparing Catalyst Component The catalyst component according to the present invention is prepared by (1) bringing magnesium dialkoxide (component A) into contact with a silicon compound (component B) having the above general formula, and mixing the obtained solid product with titanium dialkoxide having the above general formula. (2) contacting the A component with the B component, and contacting the obtained solid product with an electron donating compound (D component), and then contacting with the C component; Therefore, it can be manufactured. These methods will be explained below. Contact between magnesium dialkoxide and silicon compound Magnesium dialkoxide and silicon compound can be brought into contact by mixing and stirring them in the presence or absence of a hydrocarbon and/or halogenated hydrocarbon, or by mechanical co-pulverization. This can be achieved by methods such as Examples of hydrocarbons include hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. Examples of halogenated hydrocarbons include 1,2-dichloroethane, 1,2-dichloropropane, carbon tetrachloride, butyl chloride, and chloride. Examples include isoamyl, bromobenzene, chlorotoluene, and the like. The contact ratio between the magnesium dialkoxide and the silicon compound is 0.5 to 10 mol, preferably 1 to 5 mol, of the silicon compound per 1 mol of magnesium dialkoxide. When the two are brought into contact by mechanical co-pulverization,
This may be carried out using a common pulverizer used to obtain a pulverized product, and examples of the pulverizer include a rotary ball mill, a vibrating ball mill, and an impact mill. The co-pulverization treatment can be carried out, if necessary, under reduced pressure or in an inert gas atmosphere, and in a state where moisture, oxygen, etc. are substantially absent. The contact temperature in the case of mechanical co-pulverization is 0 to
200°C, contact time is 0.5-100 hours. or,
In the case of a contact method of simply stirring, the contact temperature is 0.
~200°C, contact time is 0.5-100 hours. The silicon compound is not limited to one type, and two or more types may be used at the same time. The second aspect of the present invention is to further contact the contact material of magnesium dialkoxide and a silicon compound with an electron-donating compound. Examples of electron-donating compounds that can be used include carboxylic acids, carboxylic acid esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, and compounds that bond to organic groups via carbon or oxygen. Examples include phosphorus, arsenic, and antimony compounds, phosphoamides, thioethers, thioesters, and carbonate esters, and among these, carboxylic acid esters, alcohols, and ethers are preferably used. Specific examples of carboxylic acid esters include butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl butyrate, isobutyl isobutyrate, methyl methacrylate, diethyl maleate, diethyl tartrate, ethyl cyclohexanecarboxylate, ethyl benzoate, p - Examples include, but are not limited to, ethyl methoxybenzoate, methyl p-methylbenzoate, ethyl p-tertiary butylbenzoate, dibutyl phthalate, diallyl phthalate, ethyl α-naphthoate, etc. . Among these, alkyl esters of aromatic carboxylic acids, particularly alkyl esters of benzoic acid or nuclear substituted benzoic acids having 1 to 8 carbon atoms such as p-methylbenzoic acid and p-methoxybenzoic acid, are preferably used. Alcohols are general formula
Represented by ROH. In the formula, R is carbon number 1
~12 alkyl, alkenyl, cycloalkyl, aryl, aralkyl. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, and the like. Ethers have the general formula
It is expressed as ROR′. In the formula, R and R' are alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 12 carbon atoms;
R′ may be the same or different. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, butyl allyl ether, diphenyl ether, anisole, and ethyl phenyl ether. etc. Contact between the contact material of the magnesium alkoxide and the silicon compound and the electron-donating compound is achieved by a method of mixing and stirring the two in the presence or absence of an inert hydrocarbon, a method of mechanical co-pulverization, etc. be done. As an inert hydrocarbon,
Examples include hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and the like. In the case of contact by mechanical co-grinding, the contact temperature is 0 to 100°C and the contact time is 0.1 to 100 hours. Further, in the case of a contact method of simply stirring, the contact temperature is 0 to 150°C and the contact time is 0.5 to 10 hours. The electron-donating compound may be present in an amount of 0.01 to 10 g mol per gram atom of magnesium in the contact between magnesium dialkoxide and silicon compound, in particular
It is desirable to use it in a range of 0.05 to 1 gram mole. Contact with a titanium compound The contact material of magnesium dialkoxide and a silicon compound or the contact material with an electron-donating compound (hereinafter referred to as the contact material) is then brought into contact with a titanium compound to form a catalyst component according to the present invention. shall be. The contact article may be cleaned with a suitable cleaning agent, such as the inert hydrocarbons mentioned above, before contacting with the titanium compound. The contact material and the titanium compound may be brought into contact with each other as they are;
Alternatively, it is desirable to carry out a method of mixing and stirring the two in the presence of a halogenated hydrocarbon, a method of mechanically co-pulverizing them, or the like. As the hydrocarbon, saturated aliphatic, saturated alicyclic, and aromatic hydrocarbons having 6 to 12 carbon atoms such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene are preferable. Examples of halogenated hydrocarbons include mono- and polyhalogen-substituted saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons having 1 to 12 carbon atoms. Specific examples of these compounds include methyl chloride, methyl bromide, methyl iodide, methylene chloride,
Methylene bromide, methylene iodide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon tetraiodide, ethyl chloride, ethyl bromide, ethyl iodide, 1,2-dichloroethane, 1,2-dibromoethane, 1 , 2-diiodoethane, methylchloroform, methylbromoform, methyliodoform, 1,1,2-trichloroethylene,
1,1,2-tribromoethylene, 1,1,
2,2-tetrachlorethylene, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, decabromobutane, chlorinated paraffin, Alicyclic compounds include chlorocyclopropane, tetrachlorocyclopentane, hexachloropentadiene, and hexachlorocyclohexane; aromatic compounds include chlorobenzene, bromobenzene, o-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, and hexachlorobenzene. Brombenzene, benzotrichloride, p-
Examples include chlorobenzotrichloride. Not only one kind but also two or more kinds of these compounds may be used. The ratio of use of both the contact material and the titanium compound in contact is 1% magnesium in the contact material.
The amount of titanium compound per gram atom is 0.1 gram mol or more, preferably 1 to 50 gram mol.
In addition, the contact conditions are 0 to 200 when carried out in the presence of hydrocarbons and/or halogenated hydrocarbons.
0.5-20 hours at ℃, preferably 1-20 hours at 60-150℃
It is 5 hours. The amount of hydrocarbon and/or halogenated hydrocarbon to be used is determined when the contact material is a liquid substance (hydrocarbon and/or
(or liquid halogenated hydrocarbon or liquid titanium compound) is preferably used in an amount of 10 to 300 g. Contact with the titanium compound may be performed two or more times as necessary. The solid substance obtained as described above is separated from the liquid substance, and if necessary, washed with an inert hydrocarbon such as hexane, heptane, octane, cyclohexane, benzene, toluene, or xylene.
The catalyst component according to the present invention is obtained by drying. The catalyst component according to the present invention has a specific surface area of 50 to 650 m 2 /g, a pore volume of 0.05 to 0.4 cc/g, and a narrow particle size distribution, as measured by the BET method at the adsorption temperature of liquid nitrogen. They are all the same size. The composition is 10 to 25% by weight of magnesium atoms, 1 to 10% by weight of titanium atoms, 40 to 60% by weight of halogen atoms, and contains other organic compounds. In addition, if a halogenated hydrocarbon and/or an electron-donating compound is used in preparing the catalyst component, the substance may contain a small amount of the halogenated hydrocarbon, electron-donating compound, and/or their conversion substance. There may be cases where Olefin Polymerization Catalyst The catalyst component according to the present invention is used in combination with an organoaluminum compound to form a catalyst for homopolymerization of olefin or copolymerization with other olefins. Organoaluminum compound The organoaluminum compound to be combined with the catalyst component when polymerizing olefin has the general formula R o AlX 3-o (where R is an alkyl group or an aryl group, and X is a halogen atom, an alkoxy group, or a hydrogen atom). , n is an arbitrary number in the range of 1n3), such as trialkyl aluminum, dialkyl aluminum monohalide, monoalkyl aluminum dihalide, alkyl aluminum sesquihalide, dialkyl aluminum monoalkoxide, and dialkyl aluminum monohalide. Particularly preferred are alkyl aluminum compounds having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms, such as halides, or mixtures or complexes thereof. Specifically, trimethylaluminum,
Trialkylaluminum such as triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, dialkylaluminum monohalide such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide, diethylaluminium iodide, diisobutylaluminum chloride, methylaluminum dichloride , ethylaluminum dichloride, ethylaluminum dibromide, ethylaluminum dibromide, ethylaluminum diiodide, monoalkylaluminum dihalides such as isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide, diethylaluminum Ethoxide, dialkyl aluminum monoalkoxide such as diethyl aluminum phenoxide, dipropyl aluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum phenoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride, etc. Dialkyl aluminum hydride is mentioned. Among these, trialkylaluminum is preferred, particularly triethylaluminum and triisobutylaluminum. In addition, these trialkylaluminums may be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminium hydride, or mixtures or complex compounds thereof. Can be used in combination with etc. Furthermore, the organoaluminum compound may be used alone or in combination with an electron-donating compound. As the electron-donating compound, any electron-donating compound can be used as long as it is brought into contact with the contact material of magnesium dialkoxide and silicon compound during the preparation of the catalyst component, as required, but among them, carboxylic acid Esters, alcohols, ethers, and ketones are preferable. These electron-donating compounds may be used when the organoaluminum compound is used in combination with a catalyst component, or may be used after being brought into contact with the organoaluminum compound in advance. The amount of organoaluminum compound used in the catalyst component according to the present invention is usually 1 to 2000 g mol, especially 200 g mol per 1 gram atom of titanium in the catalyst component.
~500 gmol is desirable. In addition, the ratio of the organoaluminum compound to the electron-donating compound is 0.1 as aluminum per 1 mole of the electron-donating compound.
~40, preferably 1 to 25 gram atoms. Polymerization of olefins The catalyst composed of the catalyst component and the organoaluminum compound (and electron-donating compound) obtained as described above is useful as a catalyst for homopolymerization of monoolefins or copolymerization with other monoolefins or diolefins. However, especially α-olefin,
In particular, homopolymerization of α-olefins having 3 to 6 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, or the above α-olefins
- Catalysts for random and block copolymerization of olefins with each other and/or with ethylene, homopolymerization of ethylene or ethylene with α-olefins having 3 to 10 carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, It shows extremely excellent performance as a catalyst for random or block copolymerization with 1-hexene, 1-octene, etc. The polymerization reaction may be performed in either a gas phase or a liquid phase. When polymerizing in a liquid phase, inert carbonization of normal butane, isobutane, normal pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, etc. It can be carried out in hydrogen and in liquid monomers. The polymerization temperature is usually -80°C to +150°C, preferably 40 to 120°C.
℃ range. The polymerization pressure may be, for example, 1 to 60 atmospheres. In addition, the molecular weight of the obtained polymer can be adjusted by
This is done in the presence of hydrogen or other known molecular weight modifiers. In addition, the amount of other olefins to be copolymerized with olefin in the copolymerization is usually up to 30% by weight based on the olefin, especially
It is selected in the range of 0.3 to 15% by weight. The polymerization reaction using the catalyst system of the present invention may be carried out in a continuous or batch reaction, and the conditions may be those commonly used.
Further, the copolymerization reaction may be carried out in one stage, or may be carried out in two or more stages. Effects of the Invention The catalyst component according to the present invention is effective as a catalyst component in the production of polyolefins, particularly isotactic polypropylene, random copolymers of ethylene and propylene, and block copolymers of ethylene and propylene. The polymerization catalyst using the catalyst component according to the present invention has high polymerization activity and stereoregularity, and can maintain the high polymerization activity for a long time during polymerization, and the obtained olefin polymer powder has a low bulk density. expensive. Moreover, this polymer powder has high fluidity. EXAMPLES Next, the present invention will be specifically explained using examples and application examples. However, the present invention is not limited only to the examples. Note that the percentages (%) shown in Examples and Application Examples are based on weight unless otherwise specified. Specific surface area (SA) and pore volume (P.
V.) is SORPTOMATIC manufactured by CARLO ERBA
Measurements were made using a model 1810 device. The polymerization activity Kc is the amount of polymer produced (g) per gram of catalyst component, and Kt is the amount of polymer produced per gram of Ti in the catalyst component (Kg). The catalyst specific activity is 1g of catalyst component, 1g of polymerization time.
The amount of polymer produced (g) per time and monomer partial pressure of 1 kg/cm 2 during polymerization is shown. The heptane insoluble content (hereinafter abbreviated as HI), which indicates the proportion of crystalline polymer in the polymer, was determined by boiling n-heptane using a modified Soxhlet extractor.
This is the remaining amount when time is extracted. Melt flow rate (MFR) and melt index (MI) are
Measured according to ASTM-D1238. Also, the bulk density is
Measured according to ASTM-D1895-69 Method A. Example 1 Contact of magnesium diethoxide and trichlorosilane A reflux condenser, dropping funnel and stirrer were installed.
A 500 ml glass reactor is thoroughly purged with nitrogen gas. In this reactor, 30.2 g (0.26 mol) of commercially available magnesium diethoxide and 100 ml of n-heptane were added.
After that, a mixed solution of 75 g (0.55 mol) of trichlorosilane and 30 ml of n-heptane was added dropwise from the dropping funnel over 45 minutes while stirring at room temperature, and then the mixture was heated to 70°C.
The mixture was stirred for 2 hours. During this time gas evolved from the reaction mixture. Analysis of the gas revealed that it was ethyl chloride, ethylene, hydrogen, and ethane. The obtained solid was separated at 70°C, and then added to n-hexane at 65°C.
After washing 5 times with 300 ml, it was dried under reduced pressure at 60°C for 30 minutes to obtain a solid component (). solid component ()
contains 14% magnesium, 11% silicon, and 51% chlorine.
%, and its surface area is 20m 2 /g, pore volume 0.05
It was cc/g. 15.1 g of this solid component () was placed in a stainless steel (SUS316) mill pot with an internal volume of 300 ml containing 100 stainless steel (SUS316) balls with a diameter of 12 mm under a nitrogen gas atmosphere, and then 3.8 g of ethyl benzoate was added. This mill pot was attached to a shaker, and the mixture was shaken for 1 hour and brought into contact to obtain a solid component (2). Titanium tetrachloride treatment 8.5g of the solid component (200g) was
ml in a glass reactor under nitrogen gas atmosphere,
Next, add 40 ml of toluene and 60 ml of titanium tetrachloride, and add 90 ml of titanium tetrachloride.
Stirred at ℃ for 2 hours. The obtained solid substance was heated to 90℃
Separate with 100ml of n-hexane at 65℃ for 7 hours.
After washing twice, the catalyst components were dried at 60°C under reduced pressure for 30 minutes to obtain a catalyst component with a titanium content of 2.6%, magnesium content of 19.0%, chlorine content of 53.6%, silicon content of 2.7%, and ethyl benzoate content of 13.7%. Obtained 6.1g. This catalyst component has a specific surface area of 210 m 2 /g and a pore volume of 0.17
It was cc/g. Example 2 The same procedure was carried out except that the ratio of magnesium diethoxide [Mg(OEt) 2 ] and trichlorosilane (HSiCl 3 ) used during contact with each other was HSiCl 3 /Mg(OEt) 2 = 1.5 (molar ratio). A catalyst component was prepared in the same manner as in Example 1. The composition and physical properties of the catalyst component obtained were as shown in Table 1. Example 3 The same procedure as in Example 1 was carried out except that the weight ratio of the solid component (2) and ethyl benzoate was 7:3 during the co-pulverization treatment of the solid component (2) and ethyl benzoate. A catalyst component was prepared. The composition and physical properties of the catalyst component obtained were as shown in Table 1. Example 4 Preparation of magnesium diethoxide A glass reactor equipped with a reflux condenser and a stirrer was sufficiently purged with nitrogen gas. To this, 13.6 g of magnesium metal pieces, 150 ml of ethanol, n-
Add 300ml of heptane, and add 0.5g of iodine in methyl iodide solution (2g of iodine/25g of methyl iodide).
ml was added to start the reaction at room temperature. Then 15 at 70℃
Allowed time to react. Separate the resulting solid material and separate each
Washed 5 times with 300 ml of n-hexane at 65°C,
Then, it was dried at 60° C. under reduced pressure to obtain 59 g of magnesium diethoxide. Preparation of catalyst component A catalyst component having the composition and physical properties shown in Table 1 was prepared in the same manner as in Example 1, except that the magnesium diethoxide obtained above was used in place of commercially available magnesium diethoxide. did. Examples 5 to 9 In Example 1, methyldichlorosilane (Example 5), dimethylchlorosilane (Example 6), and triethylsilane (Example 6) were used instead of the trichlorosilane used when contacting with magnesium diethoxide. Example 7), diethoxymethylsilane (Example 8), and bis(dimethylamino)methylsilane (Example 9) were used, but the catalyst component had the composition and physical properties shown in Table 1 in the same manner as in Example 1. was prepared. Comparative Examples 1 and 2 In Example 1, tetrachlorosilane (Comparative Example 1) and methyltrichlorosilane (Comparative Example 2) were used instead of the trichlorosilane used when contacting with magnesium diethoxide. A solid material having the composition and physical properties shown in Table 1 was prepared in the same manner as in Example 1. In addition, no gas generation was observed when magnesium diethoxide was brought into contact with tetrachlorosilane and methyltrichlorosilane. Comparative Example 3 A solid material having the composition and physical properties shown in Table 1 was prepared in the same manner as in Example 1, except that magnesium diethoxide was not brought into contact with trichlorosilane. Examples 10, 11 In Example 1 or Example 5, except that the solid component () was not contacted with ethyl benzoate.
A catalyst component was prepared in the same manner as in Example 1. The composition and physical properties of the catalyst component obtained were as shown in Table 1. Comparative Example 4 Commercially available magnesium diethoxide was added to the mill pot used in Example 1 under a nitrogen gas atmosphere.
13.6g, ethyl benzoate 4.1ml, silicon tetrachloride 2.0ml
The millpot was placed in a shaker and shaken for 15 hours. 8.6 g of the obtained crushed solid was placed in a 200 ml glass container equipped with a stirrer under a nitrogen gas atmosphere, and 50 ml of titanium tetrachloride was added thereto, followed by stirring at 80° C. for 2 hours. The solid material obtained was separated at 80°C and 100 ml of each
- After washing 7 times with hexane at 65℃, 60℃ under reduced pressure.
A catalyst component having the composition and physical properties shown in Table 1 was prepared by drying at ℃ for 30 minutes. Comparative Example 5 The glass reactor No. 1 equipped with a reflux condenser and a stirrer was sufficiently purged with nitrogen gas. 6.3 g of commercially available magnesium diethoxide, 1.5 ml of ethyl benzoate, and 100 ml of silicon tetrachloride were added to this, and the mixture was stirred at 60° C. for 24 hours. The excess liquid was discarded and the solid material was washed five times with 90 ml each of n-hexane at 65°C.
Next, 90 ml of titanium tetrachloride was added and the mixture was kept in contact at 90°C for 2 hours.The solid material was separated at the same temperature, and another 90 ml of titanium tetrachloride was added, followed by contact at 90°C for 2 hours. The solid substance was separated at 90°C, washed 7 times with 90ml of n-hexane at 65°C, and then heated at 60°C under reduced pressure.
After drying for 30 minutes, a catalyst component having the composition and physical properties shown in Table 1 was prepared. Comparative Example 6 The solid component () in the titanium tetrachloride treatment of Example 1 was mixed with commercially available magnesium diethoxide [Mg
(OEt) 2 ] was used in the same manner as in Example 1, except that Mg(OEt) 2 was brought into contact with titanium tetrachloride to prepare a catalyst component having the composition and physical properties shown in Table 1.
【表】
実施例 12〜20
実施例１〜９の触媒成分の調製時の四塩化チタ
ン処理をそれぞれ２回行つた以外は、実施例１〜
９と同様にして触媒成分を調製した。すなわち、
実施例１〜９における四塩化チタンによる90℃、
２時間の処理物を、傾瀉して上澄液を除去した
後、新らたに、トルエン40ml、四塩化チタン60ml
を加え、90℃で２時間撹拌した。得られた固体状
物質を90℃で別し、各100mlのｎ―ヘキサンに
て65℃で７回洗浄した後、減圧下60℃で30分間乾
燥して、第２表に示す組成及び物性を有する触媒
成分を調製した。[Table] Examples 12 to 20 Examples 1 to 20 except that the titanium tetrachloride treatment was performed twice during the preparation of the catalyst components in Examples 1 to 9.
A catalyst component was prepared in the same manner as in Example 9. That is,
90°C with titanium tetrachloride in Examples 1 to 9,
After removing the supernatant by decanting the treated material for 2 hours, add 40 ml of toluene and 60 ml of titanium tetrachloride.
was added and stirred at 90°C for 2 hours. The obtained solid substance was separated at 90°C, washed 7 times with 100ml of n-hexane at 65°C, and then dried at 60°C under reduced pressure for 30 minutes to obtain the composition and physical properties shown in Table 2. A catalyst component having the following properties was prepared.
【表】【table】
【表】
実施例 21，22
市販のマグネシウムジエトキシドの代りに、市
販のマグネシウムジｎ―ブトキシド44.2ｇ（実施
例21）又は市販のマグネシウムジｎ―プロポキシ
ド36.9ｇ（実施例22）を用いた以外は、実施例１
と同様にして第３表に示す組成の触媒成分を調製
した。
実施例 23
安息香酸エチルの代りに、フタル酸ジｎ―ブチ
ルを用いた以外は、実施例１と同様にして第３表
に示す組成の触媒成分を調製した。
実施例 24
実施例１と同様にして得た固体成分（）10.0
ｇ及びトルエン25mlを、撹拌機を取り付けた200
mlのガラス製反応器に窒素ガス雰囲気下で入れ、
更に安息香酸エチル24mlとトルエン15mlの混合溶
液を加えた。
60℃で２時間撹拌した後、60℃に加熱した四塩
化チタン60mlを加えた。90℃で２時間撹拌した
後、得られた固体状物質を実施例１と同様に
別、洗浄して触媒成分を調製した。得られた触媒
成分の組成を第３表に示す。
実施例 25
安息香酸エチルの代りにフタル酸ジｎ―ブチル
を用いた以外は、実施例24と同様にして、第３表
に示す組成の触媒成分を調製した。[Table] Examples 21, 22 44.2 g of commercially available magnesium di-n-butoxide (Example 21) or 36.9 g of commercially available magnesium di-n-propoxide (Example 22) was used instead of commercially available magnesium diethoxide. Example 1 except that
Catalyst components having the compositions shown in Table 3 were prepared in the same manner as above. Example 23 A catalyst component having the composition shown in Table 3 was prepared in the same manner as in Example 1, except that di-n-butyl phthalate was used instead of ethyl benzoate. Example 24 Solid component obtained in the same manner as Example 1 () 10.0
g and 25 ml of toluene in a 200 g
ml in a glass reactor under nitrogen gas atmosphere,
Furthermore, a mixed solution of 24 ml of ethyl benzoate and 15 ml of toluene was added. After stirring at 60°C for 2 hours, 60ml of titanium tetrachloride heated to 60°C was added. After stirring at 90° C. for 2 hours, the obtained solid material was separated and washed in the same manner as in Example 1 to prepare a catalyst component. The composition of the catalyst component obtained is shown in Table 3. Example 25 A catalyst component having the composition shown in Table 3 was prepared in the same manner as in Example 24, except that di-n-butyl phthalate was used instead of ethyl benzoate.
【表】
比較例 ７
マグネシウムジエトキシドの代りに、市販の無
水塩化マグネシウム24.8ｇ（0.26モル）用いた以
外は、実施例１と同様にして、チタン含有量3.0
％、マグネシウム含有量21.1％、塩素含有量67.2
％、安息香酸エチル含有量7.2％の触媒成分を8.4
ｇ得た。この触媒成分は、比表面積51m2／ｇ、細
孔容積0.08c.c.／ｇであつた。
比較例 ８
内容積１のステンレス製ポツトに直径12.7mm
のステンレス製ボールを見掛け体積で800ml充て
んし、無水MgCl21.0モルおよびｎ―ブタノール
を次に示す方法で封入して振動ミルで合計96時間
粉砕した。この場合にｎ―ブタノールは24時間毎
に粉砕を止めて0.2モルづつ逐次添加し、合計で
0.8モルのｎ―ブタノールを封入した。
粉砕後の固体５ｇを窒素ガス置換した0.5の
フラスコに入れ、ついで脱水したｎ―ヘプタン50
ml、四塩化チタン1.25mlおよびHSiCl34.8mlをそ
れぞれ導入し、温度を90℃に上げ２時間撹拌し
た。反応終了後、固体成分をｎ―ヘプタンで洗浄
し、固体触媒成分とした。この固体触媒成分中の
Ti含量は6.2％であつた。
比較例 ９
無水MgCl2の代りに、市販のマグネシウムジエ
トキシド1.0モルを用いた以外は、比較例８と同
様にしてTi含量6.5％の固体触媒成分を得た。
応用例 １
プロピレンの重合
撹拌器を設けた内容積1.5のステンレス
（SUS32）製オートクレーブに、窒素ガス雰囲気
下、実施例１で得られた触媒成分22.1mg、ｎ―ヘ
プタン１中に１モルのトリエチルアルミニウム
（以下TEALと略称する。）を含むｎ―ヘプタン溶
液を触媒成分中のチタン１グラム原子当りアルミ
ニウムとして310グラム原子に相当する3.7ml及び
該TEAL中のアルミニウム１グラム原子当り0.30
モルに相当するｐ―メトキシ安息香酸エチル0.20
mlを混合し５分間保持したものを仕込んだ。次い
で、分子量制御剤として水素ガス0.6並びに液
化プロピレン0.8を圧入した後、反応系を70℃
に昇温して、１時間、プロピレンの重合を行つ
た。重合終了後、未反応のプロピレンをパージ
し、HI（ポリマー中の結晶性ポリマーの割合を示
すヘプタン不溶分）95.3％、MFR（メルトフロー
レイト）2.9、嵩密度0.39ｇ／cm3の白色のポリプ
ロピレンの粉末を311.2ｇ（Kc（触媒１ｇ当りの
ポリマー生成量）＝14000、Kt（触媒中のTi1ｇ当
りのポリマー生成Kg量）＝540）得た。
同様にして重合時間を1.5時間としたプロピレ
ンの重合実験を行つた結果、HI93.9％、
MFR4.2、嵩密度0.40ｇ／cm3、Kc／15800、Kt608
であつた。更に重合時間を３時間とした重合実験
を行つた結果、HI92.3％、MFR5.9、嵩密度0.41
ｇ／cm3、Kc／19800、Kt760であつた。
応用例 ２〜14
プロピレンの重合
実施例２〜９及び比較例１〜５で得られた触媒
成分をそれぞれ用いた以外は、応用例１と同様に
してプロピレンの重合を行つた。その結果を第４
表に示した。[Table] Comparative Example 7 A titanium content of 3.0 was prepared in the same manner as in Example 1, except that 24.8 g (0.26 mol) of commercially available anhydrous magnesium chloride was used instead of magnesium diethoxide.
%, magnesium content 21.1%, chlorine content 67.2
8.4%, ethyl benzoate content 7.2% catalyst component
I got g. This catalyst component had a specific surface area of 51 m 2 /g and a pore volume of 0.08 cc/g. Comparative example 8 A stainless steel pot with an internal volume of 1 and a diameter of 12.7 mm.
A stainless steel ball was filled with an apparent volume of 800 ml, and 1.0 mol of anhydrous MgCl 2 and n-butanol were sealed in the ball as described below, and the mixture was ground in a vibrating mill for a total of 96 hours. In this case, stop grinding and add n-butanol in 0.2 mol increments every 24 hours.
0.8 mol of n-butanol was sealed. 5 g of the crushed solid was placed in a 0.5 flask purged with nitrogen gas, and then dehydrated n-heptane 50
ml, 1.25 ml of titanium tetrachloride, and 4.8 ml of HSiCl 3 were respectively introduced, the temperature was raised to 90° C., and the mixture was stirred for 2 hours. After the reaction was completed, the solid component was washed with n-heptane to obtain a solid catalyst component. in this solid catalyst component.
The Ti content was 6.2%. Comparative Example 9 A solid catalyst component having a Ti content of 6.5% was obtained in the same manner as in Comparative Example 8, except that 1.0 mol of commercially available magnesium diethoxide was used instead of anhydrous MgCl 2 . Application example 1 Polymerization of propylene In a stainless steel (SUS32) autoclave with an internal volume of 1.5 and equipped with a stirrer, 22.1 mg of the catalyst component obtained in Example 1 and 1 mole of triethyl in 1 part of n-heptane were placed in a nitrogen gas atmosphere. An n-heptane solution containing aluminum (hereinafter abbreviated as TEAL) is 3.7 ml, which corresponds to 310 gram atoms of aluminum per gram atom of titanium in the catalyst component, and 0.30 ml per gram atom of aluminum in the TEAL.
Ethyl p-methoxybenzoate equivalent to 0.20 mole
ml was mixed and held for 5 minutes. Next, after pressurizing 0.6 of hydrogen gas and 0.8 of liquefied propylene as molecular weight control agents, the reaction system was heated to 70°C.
Polymerization of propylene was carried out for 1 hour. After the polymerization is completed, unreacted propylene is purged to produce white polypropylene with HI (heptane insoluble content, which indicates the proportion of crystalline polymer in the polymer) of 95.3%, MFR (melt flow rate) of 2.9, and bulk density of 0.39 g/ cm3. 311.2 g of powder (Kc (amount of polymer produced per 1 g of catalyst) = 14000, Kt (amount of Kg of polymer produced per 1 g of Ti in the catalyst) = 540) was obtained. A propylene polymerization experiment was conducted in the same manner with a polymerization time of 1.5 hours, and the results showed that HI93.9%,
MFR4.2, bulk density 0.40g/ cm3 , Kc/15800, Kt608
It was hot. Furthermore, as a result of conducting a polymerization experiment with a polymerization time of 3 hours, HI92.3%, MFR5.9, bulk density 0.41
g/cm 3 , Kc/19800, and Kt760. Application Examples 2 to 14 Polymerization of Propylene Propylene was polymerized in the same manner as Application Example 1, except that the catalyst components obtained in Examples 2 to 9 and Comparative Examples 1 to 5 were used, respectively. The result is the fourth
Shown in the table.
【表】
応用例 15
エチレンの重合
撹拌機を設けた内容積1.5のステンレス
（SUS32）製のオートクレーブに、窒素ガス雰囲
気下、実施例10で得られた触媒成分12.0mg、トリ
イソブチルアルミニウム0.7ミリモル及びイソブ
タン700mlを仕込み、重合系を85℃に昇温した。
次に水素分圧が２Kg／cm2になる迄水素を導入した
後、エチレン分圧が５Kg／cm2になる迄エチレンを
導入した。重合系の全圧が一定になるように、エ
チレンを連続的に供給しながら60分間重合を行つ
た。重合終了後、重合系の溶媒、未反応のエチレ
ンをパージし、白色粉末状の重合体を取出し、減
圧下に70℃で10時間乾燥を行ない、MT1.10、嵩
密度0.34ｇ／c.c.のポリエチレン粉末を234ｇ（触
媒活性Kc19500、触媒比活性3900）得た。
応用例 16，17
エチレンの重合
実施例11及び比較例６で得られた触媒成分をそ
れぞれ用いた以外は、応用例15と同様にしてエチ
レンの重合を行つた。その結果を第５表に示し
た。[Table] Application example 15 Polymerization of ethylene In a stainless steel (SUS32) autoclave with an internal volume of 1.5 and equipped with a stirrer, 12.0 mg of the catalyst component obtained in Example 10, 0.7 mmol of triisobutylaluminum, and 700 ml of isobutane was charged, and the temperature of the polymerization system was raised to 85°C.
Next, hydrogen was introduced until the hydrogen partial pressure became 2 Kg/cm 2 , and then ethylene was introduced until the ethylene partial pressure became 5 Kg/cm 2 . Polymerization was carried out for 60 minutes while continuously supplying ethylene to keep the total pressure of the polymerization system constant. After the polymerization, the polymerization solvent and unreacted ethylene were purged, and the white powdery polymer was taken out and dried at 70°C under reduced pressure for 10 hours to obtain polyethylene with an MT of 1.10 and a bulk density of 0.34 g/cc. 234 g of powder (catalytic activity Kc 19500, catalytic specific activity 3900) was obtained. Application Examples 16 and 17 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as Application Example 15, except that the catalyst components obtained in Example 11 and Comparative Example 6 were used, respectively. The results are shown in Table 5.
【表】
応用例 18
エチレンと１―ブテンの共重合
応用例15で用いたオートクレーブに、窒素ガス
雰囲気下、実施例10で得られた触媒成分11.5mg、
トリイソブチルアルミニウム0.7ミリモル及びイ
ソブタン700mlを入れ、重合系を80℃に昇温した。
次に、水素分圧が1.2Kg／cm2になる迄水素を導入
した後、エチレン分圧が３Kg／cm2になる迄エチレ
ンを導入し、更に１―ブテンを20ｇ加えた。重合
系の全圧が一定になるように、エチレンを連続し
て供給しながら１時間重合を行つた。重合終了
後、重合系の溶媒、未反応のエチレンをパージ
し、粉末状のエチレン―１―ブテン共重合体173
ｇ（触媒比活性5000）を得た。得られた共重合体
の嵩密度0.33ｇ／c.c.、真密度0.924ｇ／c.c.、MI2.1
であつた。
応用例 19〜27
プロピレンの重合
実施例12〜20で得られた触媒成分をそれぞれ用
いた以外は、応用例１と同様にしてプロピレンの
重合を行つた。その結果を第６表に示した。[Table] Application example 18 Copolymerization of ethylene and 1-butene 11.5 mg of the catalyst component obtained in Example 10 was placed in the autoclave used in Application example 15 under a nitrogen gas atmosphere.
0.7 mmol of triisobutylaluminum and 700 ml of isobutane were added, and the temperature of the polymerization system was raised to 80°C.
Next, hydrogen was introduced until the hydrogen partial pressure became 1.2 kg/cm 2 , then ethylene was introduced until the ethylene partial pressure became 3 kg/cm 2 , and then 20 g of 1-butene was added. Polymerization was carried out for 1 hour while continuously supplying ethylene so that the total pressure of the polymerization system was kept constant. After the polymerization is completed, the polymerization solvent and unreacted ethylene are purged, and the powdered ethylene-1-butene copolymer 173
g (catalyst specific activity 5000) was obtained. The obtained copolymer had a bulk density of 0.33 g/cc, a true density of 0.924 g/cc, and an MI of 2.1.
It was hot. Application Examples 19 to 27 Polymerization of Propylene Propylene was polymerized in the same manner as in Application Example 1, except that the catalyst components obtained in Examples 12 to 20 were used, respectively. The results are shown in Table 6.
【表】
応用例 28〜32
プロピレンの重合
実施例21〜25で得られた触媒成分をそれぞれ用
いた以外は、応用例１と同様にしてプロピレンの
重合を行つた。その結果を第７表に示した。[Table] Application Examples 28 to 32 Polymerization of propylene Propylene was polymerized in the same manner as in Application Example 1, except that the catalyst components obtained in Examples 21 to 25 were used, respectively. The results are shown in Table 7.
【表】
応用例 33
プロピレンの重合
比較例７で得られた触媒成分を用いた以外は、
応用例１と同様にしてプロピレンの重合を１時間
行つた。その結果、Kc＝5800、Kt＝193、HI＝
91.1％、MFR＝6.8、嵩密度＝0.33であつた。
応用例 34
エチレンの重合
撹拌装置を有する内容積１のステンレス製オ
ートクレーブに真空―エチレン置換を数回くり返
した後、充分に脱水、脱酸素したｎ―ヘプタンを
0.5導入し、続いてTEAL100mg及び比較例８で
調製した固体触媒成分を2.5mg導入した。次いで
85℃に昇温し、水素分圧4.5Kg／cm2、さらにエチ
レン分圧4.5Kg／cm2にまで水素およびエチレンを
導入し、全圧で９Kg／cm2Ｇとして３時間重合し
た。
重合終了後、エチレン及び水素をパージした後
オートクレーブより内容物を取り出し、このポリ
マースラリーを過して真空乾燥機で８時間乾燥
した。74.8ｇの白色重合体が得られた。Kcは
29900であり、又、ポリマーのMIは4.8、嵩密度
は0.31であつた。
応用例 35
エチレンの重合
比較例９で得られた固体触媒成分を用いた以外
は、応用例34と同様にしてエチレンの重合を行つ
た。その結果、Kc＝31500、MI＝3.5、嵩密度＝
0.32であつた。[Table] Application example 33 Polymerization of propylene Except for using the catalyst component obtained in Comparative example 7,
Polymerization of propylene was carried out for 1 hour in the same manner as in Application Example 1. As a result, Kc=5800, Kt=193, HI=
It was 91.1%, MFR = 6.8, and bulk density = 0.33. Application example 34 Polymerization of ethylene After repeating vacuum-ethylene displacement several times in a stainless steel autoclave with an internal volume of 1 and equipped with a stirring device, thoroughly dehydrated and deoxidized n-heptane was added.
Then, 100 mg of TEAL and 2.5 mg of the solid catalyst component prepared in Comparative Example 8 were introduced. then
The temperature was raised to 85° C., and hydrogen and ethylene were introduced to a hydrogen partial pressure of 4.5 Kg/cm 2 and further to an ethylene partial pressure of 4.5 Kg/cm 2 , and polymerization was carried out for 3 hours at a total pressure of 9 Kg/cm 2 G. After the polymerization was completed, ethylene and hydrogen were purged and the contents were taken out from the autoclave, and the polymer slurry was filtered and dried in a vacuum dryer for 8 hours. 74.8 g of white polymer was obtained. Kc is
29900, the MI of the polymer was 4.8, and the bulk density was 0.31. Application Example 35 Ethylene Polymerization Ethylene polymerization was carried out in the same manner as Application Example 34 except that the solid catalyst component obtained in Comparative Example 9 was used. As a result, Kc=31500, MI=3.5, bulk density=
It was 0.32.
第１図は、本発明の方法で製造される触媒成分
の調製工程を示すフローチヤート図である。
FIG. 1 is a flowchart showing the steps for preparing a catalyst component produced by the method of the present invention.
Claims (1)
HmRnSiXr〔但し、Ｒは炭化水素基、R1O―若し
くはR2R3N―、Ｘはハロゲン原子を示し、１
ｍ３，０ｒ３，ｍ＋ｎ＋ｒ＝４である。
R1，R2及びR3はそれぞれ炭化水素基を示す。〕の
珪素化合物を接触させ、得られた固体生成物を(C)
一般式TiXo（OR）4-o〔但し、Ｘはハロゲン原子、
Ｒは炭化水素基を示し、０ｎ４である。〕の
チタン化合物と接触させることからなるオレフイ
ン重合用触媒成分の製造方法。 ２ (A)マグネシウムジアルコキシドと(B)一般式
HmRnSiXr〔但し、Ｒは炭化水素基、R1O―若し
くはR2R3N―、Ｘはハロゲン原子を示し、１
ｍ３，０ｒ３，ｍ＋ｎ＋ｒ＝４である。
R1，R2及びR3はそれぞれ炭化水素基を示す。〕の
珪素化合物を接触させ、得られた固体生成物を(D)
電子供与性化合物と接触させ、次いで(C)一般式
TiXo（OR）4-o〔但し、Ｘはハロゲン原子、Ｒは
炭化水素基を示し、０ｎ４である。〕のチタ
ン化合物と接触させることからなるオレフイン重
合用触媒成分の製造方法。[Claims] 1 (A) Magnesium dialkoxide and (B) general formula
HmRnSiXr [However, R is a hydrocarbon group, R 1 O- or R 2 R 3 N-, X is a halogen atom, and 1
m3, 0r3, m+n+r=4.
R 1 , R 2 and R 3 each represent a hydrocarbon group. ] and the resulting solid product (C)
General formula TiX o (OR) 4-o [However, X is a halogen atom,
R represents a hydrocarbon group and is On4. ] A method for producing a catalyst component for olefin polymerization, which comprises bringing it into contact with a titanium compound. 2 (A) Magnesium dialkoxide and (B) general formula
HmRnSiXr [However, R is a hydrocarbon group, R 1 O- or R 2 R 3 N-, X is a halogen atom, and 1
m3, 0r3, m+n+r=4.
R 1 , R 2 and R 3 each represent a hydrocarbon group. ] and the resulting solid product (D)
Contact with an electron donating compound, then (C) general formula
TiX o (OR) 4-o [However, X represents a halogen atom, R represents a hydrocarbon group, and is On4. ] A method for producing a catalyst component for olefin polymerization, which comprises bringing it into contact with a titanium compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6234082A JPS58198503A (en) | 1982-04-16 | 1982-04-16 | Catalytic component for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6234082A JPS58198503A (en) | 1982-04-16 | 1982-04-16 | Catalytic component for olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58198503A JPS58198503A (en) | 1983-11-18 |
| JPH023405B2 true JPH023405B2 (en) | 1990-01-23 |
Family
ID=13197289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6234082A Granted JPS58198503A (en) | 1982-04-16 | 1982-04-16 | Catalytic component for olefin polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58198503A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5747595A (en) * | 1995-03-28 | 1998-05-05 | Tonen Corporation | Catalyst for the polymerization of olefines and processes for the polymerization of olefines using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792009A (en) * | 1980-11-29 | 1982-06-08 | Mitsubishi Petrochem Co Ltd | Solid catalytic component for polymerizing olefin |
-
1982
- 1982-04-16 JP JP6234082A patent/JPS58198503A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5792009A (en) * | 1980-11-29 | 1982-06-08 | Mitsubishi Petrochem Co Ltd | Solid catalytic component for polymerizing olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58198503A (en) | 1983-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0655780B2 (en) | Olefin polymerization catalyst component | |
| JPH072775B2 (en) | Method for producing catalyst component for olefin polymerization | |
| JPH0377801B2 (en) | ||
| US4552858A (en) | Catalyst component for polymerization of olefins | |
| JPH0655782B2 (en) | Olefin polymerization catalyst component | |
| EP0127487B1 (en) | Catalyst component for polymerization of olefins | |
| EP0136113B1 (en) | Catalyst component for polymerization of olefins | |
| US4550095A (en) | Catalyst component for polymerization of olefins | |
| US4678768A (en) | Catalyst component for polymerization of olefins | |
| EP0227455B1 (en) | Process for producing catalyst ingredient for use in olefin polymerization | |
| EP0193281B1 (en) | Catalyst component for olefin polymerization | |
| JPS6247446B2 (en) | ||
| JPH0153884B2 (en) | ||
| US4652541A (en) | Catalyst component for polymerization of olefins | |
| JPH023405B2 (en) | ||
| JPH0153883B2 (en) | ||
| JPS6247447B2 (en) | ||
| US5093442A (en) | Method for producing a homopolymer or copolymer of an α-olefin | |
| US4625003A (en) | Catalyst component for polymerization of olefins (P-1026) | |
| JPS637202B2 (en) | ||
| JPH0322889B2 (en) | ||
| JPS6247443B2 (en) | ||
| JPH0149293B2 (en) |