JPH0425287B2 - - Google Patents
Info
- Publication number
- JPH0425287B2 JPH0425287B2 JP17412483A JP17412483A JPH0425287B2 JP H0425287 B2 JPH0425287 B2 JP H0425287B2 JP 17412483 A JP17412483 A JP 17412483A JP 17412483 A JP17412483 A JP 17412483A JP H0425287 B2 JPH0425287 B2 JP H0425287B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon atoms
- formula
- alkyl group
- solid
- catalyst component
- 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
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- 239000011949 solid catalyst Substances 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 Aluminum halide Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 22
- 238000006116 polymerization reaction Methods 0.000 description 21
- 239000003960 organic solvent Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LDDOSDVZPSGLFZ-UHFFFAOYSA-N ethyl cyclopropanecarboxylate Chemical compound CCOC(=O)C1CC1 LDDOSDVZPSGLFZ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 2
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- DIZKLZKLNKQFGB-UHFFFAOYSA-N 1-methylcyclopropane-1-carboxylic acid Chemical compound OC(=O)C1(C)CC1 DIZKLZKLNKQFGB-UHFFFAOYSA-N 0.000 description 1
- IKBFHCBHLOZDKH-UHFFFAOYSA-N 2-chloroethyl(triethoxy)silane Chemical compound CCO[Si](CCCl)(OCC)OCC IKBFHCBHLOZDKH-UHFFFAOYSA-N 0.000 description 1
- CASYTJWXPQRCFF-UHFFFAOYSA-N 2-chloroethyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCl CASYTJWXPQRCFF-UHFFFAOYSA-N 0.000 description 1
- HIFPMSPZVIIQON-UHFFFAOYSA-N 3-methylbutoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCCC(C)C)C1=CC=CC=C1 HIFPMSPZVIIQON-UHFFFAOYSA-N 0.000 description 1
- VJPGPCCOXUQRLT-UHFFFAOYSA-N 4-chlorobutyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCCl VJPGPCCOXUQRLT-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KHCFOLCKMHPPOQ-UHFFFAOYSA-N bis(3-methylbutoxy)-bis(2-methylpropyl)silane Chemical compound CC(C)CCO[Si](CC(C)C)(CC(C)C)OCCC(C)C KHCFOLCKMHPPOQ-UHFFFAOYSA-N 0.000 description 1
- CQAOCKWBSIQRRR-UHFFFAOYSA-N bis(3-methylbutoxy)-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](OCCC(C)C)(OCCC(C)C)C1=CC=CC=C1 CQAOCKWBSIQRRR-UHFFFAOYSA-N 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
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- DGPFXVBYDAVXLX-UHFFFAOYSA-N dibutyl(diethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)CCCC DGPFXVBYDAVXLX-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- MIKCMZCEJLHQSO-UHFFFAOYSA-N diethyl-bis(3-methylbutoxy)silane Chemical compound CC(C)CCO[Si](CC)(CC)OCCC(C)C MIKCMZCEJLHQSO-UHFFFAOYSA-N 0.000 description 1
- BOSRFJJSELFGNV-UHFFFAOYSA-N dimethyl-bis(3-methylbutoxy)silane Chemical compound CC(C)CCO[Si](C)(C)OCCC(C)C BOSRFJJSELFGNV-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- BQOHGKXVHXIPTN-UHFFFAOYSA-N dioctoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCCCCCCCC)(OCCCCCCCC)C1=CC=CC=C1 BQOHGKXVHXIPTN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- STBFUFDKXHQVMJ-UHFFFAOYSA-N ethoxy(tripropyl)silane Chemical compound CCC[Si](CCC)(CCC)OCC STBFUFDKXHQVMJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- ZVZCPNOTWZTICU-UHFFFAOYSA-N ethyl-tris(3-methylbutoxy)silane Chemical compound CC(C)CCO[Si](CC)(OCCC(C)C)OCCC(C)C ZVZCPNOTWZTICU-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CHYCGNMYMRDZJE-UHFFFAOYSA-N hexyl cyclopropanecarboxylate Chemical compound CCCCCCOC(=O)C1CC1 CHYCGNMYMRDZJE-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- GBRJQTLHXWRDOV-UHFFFAOYSA-M magnesium;hexane;chloride Chemical compound [Mg+2].[Cl-].CCCCC[CH2-] GBRJQTLHXWRDOV-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BKXVGDZNDSIUAI-UHFFFAOYSA-N methoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC)C1=CC=CC=C1 BKXVGDZNDSIUAI-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
- 229940095102 methyl benzoate Drugs 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- OKSRWSKLFGGINT-UHFFFAOYSA-N methyl-tris(3-methylbutoxy)silane Chemical compound CC(C)CCO[Si](C)(OCCC(C)C)OCCC(C)C OKSRWSKLFGGINT-UHFFFAOYSA-N 0.000 description 1
- WBNJGVBMXDWVLX-UHFFFAOYSA-N methyl-tris(6-methylheptoxy)silane Chemical compound CC(C)CCCCCO[Si](C)(OCCCCCC(C)C)OCCCCCC(C)C WBNJGVBMXDWVLX-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- ISTGAWZGAGOYJK-UHFFFAOYSA-N propyl cyclopropanecarboxylate Chemical compound CCCOC(=O)C1CC1 ISTGAWZGAGOYJK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- LKLQQUNAWIWESF-UHFFFAOYSA-N tributoxy(3-methylbutyl)silane Chemical compound CCCCO[Si](CCC(C)C)(OCCCC)OCCCC LKLQQUNAWIWESF-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- ZQJYXISBATZORI-UHFFFAOYSA-N tributyl(ethoxy)silane Chemical compound CCCC[Si](CCCC)(CCCC)OCC ZQJYXISBATZORI-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- XYNHSIKVRCOMSV-UHFFFAOYSA-N triethoxy(3-methylbutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(C)C XYNHSIKVRCOMSV-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UCUKUIPXDKEYLX-UHFFFAOYSA-N triethyl(propan-2-yloxy)silane Chemical compound CC[Si](CC)(CC)OC(C)C UCUKUIPXDKEYLX-UHFFFAOYSA-N 0.000 description 1
- OEZONJBFNSCSLS-UHFFFAOYSA-N trihexoxy(methyl)silane Chemical compound CCCCCCO[Si](C)(OCCCCCC)OCCCCCC OEZONJBFNSCSLS-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZQINJXJSYYRJIV-UHFFFAOYSA-N trimethyl(2-methylpropoxy)silane Chemical compound CC(C)CO[Si](C)(C)C ZQINJXJSYYRJIV-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- PJEMIBXFOHYKMS-UHFFFAOYSA-N tris(2-methylpropoxy)-phenylsilane Chemical compound CC(C)CO[Si](OCC(C)C)(OCC(C)C)C1=CC=CC=C1 PJEMIBXFOHYKMS-UHFFFAOYSA-N 0.000 description 1
- GSKGAYNDQMCNKC-UHFFFAOYSA-N tris(3-methylbutoxy)-phenylsilane Chemical compound CC(C)CCO[Si](OCCC(C)C)(OCCC(C)C)C1=CC=CC=C1 GSKGAYNDQMCNKC-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】 本発明はα−オレフインの重合法に関する。[Detailed description of the invention] The present invention relates to a method for polymerizing α-olefins.
マグネシウム化合物にチタンハロゲン化物を担
持させた固体触媒成分、有機アルミニウム化合物
および芳香族カルボン酸エステルから得られる触
媒の存在下に、炭素数３以上のａ−オレフインを
重合する方法に関して多くの提案がされている。 Many proposals have been made regarding methods for polymerizing a-olefins having 3 or more carbon atoms in the presence of a solid catalyst component in which a titanium halide is supported on a magnesium compound, an organoaluminum compound, and a catalyst obtained from an aromatic carboxylic acid ester. ing.
本出願人は上記ａ−オレフインの重合法に関し
て既にいくつかの提案をした（特開昭56−45909
号公報、同56−76411号公報、同56−163102号公
報参照）。 The present applicant has already made several proposals regarding the polymerization method of the a-olefin (Japanese Patent Application Laid-Open No. 56-45909
(See Japanese Publication No. 56-76411, Publication No. 56-163102).
本発明は、本出願人の提案になる方法を改良す
るものであり、重合に使用する固体触媒成分当り
より大きい収量で高立体規則性ポリーａ−オレフ
インを得ることができるａ−オレフインの重合法
を提供する。 The present invention is an improvement on the process proposed by the applicant, and is a process for polymerizing α-olefins, which allows highly stereoregular poly α-olefins to be obtained in higher yields per solid catalyst component used in the polymerization. I will provide a.
本発明は、
(1) ハロゲン化アルミニウムを
式 R1 nSi（OR2）4-n
（式中、R1はハロゲン置換又は未置換の炭
素数１〜８のアルキル基又はフエニル基を示
し、R2は炭素数１〜８のアルキル基を示し、
ｍは０，１，２又は３である。）で表わされる
ケイ素化合物と反応させ、
(2) 反応生成物を
式 R3MgX
（式中、R3は炭素数１〜８のアルキル基を
示し、Ｘはハロゲン原子を示す。）で表わされ
るグリニヤール化合物と反応させ、
(3) 得られる担持を四ハロゲン化チタンと接触さ
せ、
(4) 接触固体を
式
（式中、R4は炭素数１〜８のアルキル基を示
す。）で表わされるシクロプロパンカルボン酸
エステルで処理し、
(5) 処理固体を四ハロゲン化チタンと接触させて
得られる固体触媒成分〔Ａ〕、
式 AlR5 3
（式中、R5は炭素数１〜６のアルキル基を
示す。）で表わされる有機アルミニウム化合物
〔Ｂ〕、及び芳香族カルボン酸エステル〔Ｃ〕か
ら得られる触媒の存在下に、炭素数３以上のａ
−オレフインを重合することを特徴とするａ−
オレフインの重合法である。 The present invention provides (1) aluminum halide having the formula R 1 n Si(OR 2 ) 4-n (wherein R 1 represents a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a phenyl group, R 2 represents an alkyl group having 1 to 8 carbon atoms,
m is 0, 1, 2 or 3. ), and (2) the reaction product is expressed by the formula R 3 MgX (wherein R 3 represents an alkyl group having 1 to 8 carbon atoms, and X represents a halogen atom). (3) contacting the resulting support with titanium tetrahalide; (4) converting the contacted solid to the formula (In the formula, R 4 represents an alkyl group having 1 to 8 carbon atoms.) (5) A solid catalyst component obtained by contacting the treated solid with titanium tetrahalide. [A], an organoaluminum compound represented by the formula AlR 5 3 (in the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms) [B], and an aromatic carboxylic acid ester [C]. in the presence of a having 3 or more carbon atoms
- a characterized by polymerizing an olefin -
This is a method for polymerizing olefin.
本発明において、固体触媒成分の調製および重
合は、すべて窒素、アルゴンなどの不活性ガス雰
囲気下に、行なわれる。また、固体触媒成分の調
製原料は実質的に無水であることが望ましい。 In the present invention, the preparation and polymerization of the solid catalyst component are all carried out under an inert gas atmosphere such as nitrogen or argon. Further, it is desirable that the raw material for preparing the solid catalyst component is substantially anhydrous.
本発明におけるハロゲン化アルミニウムの具体
例としては、塩化アルミニウム、臭化アルミニウ
ム、沃化アルミニウムを挙げることができ、中で
も塩化アルミニウムが好適に使用される。 Specific examples of aluminum halide in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, among which aluminum chloride is preferably used.
ケイ素化合物の具体例としては、テトラメトキ
シシラン、テトラエトキシシラン、テトラ−ｎ−
プロポキシシラン、テトラ−ｎ−ブトキシシラ
ン、テトラ−イソペントキシシラン、テトラ−ｎ
−ヘキソキシシラン、メチルトリメトキシシラ
ン、メチルトリエトキシシラン、メチルトリ−ｎ
−ブトキシシラン、メチルトリイソペントキシシ
ラン、メチルトリ−ｎ−ヘキソキシシラン、メチ
ルトリイソオクトキシシラン、エチルトリエトキ
シシラン、エチルトリイソプロポキシシラン、エ
チルトリイソペントキシシラン、ｎ−ブチルトリ
エトキシシラン、イソブチルトリエトキシシラ
ン、イソペンチルトリエトキシシラン、イソペン
チルトリ−ｎ−ブトキシシラン、ジメチルジエト
キシシラン、ジメチルジ−ｎ−ブトキシシラン、
ジメチルジイソペントキシシラン、ジエチルジエ
トキシシラン、ジエチルジイソペントキシシラ
ン、ジ−ｎ−ブチルジエトキシシラン、ジイソブ
チルジイソペントキシシラン、トリメチルメトキ
シシラン、トリメチルエトキシシラン、トリメチ
ルイソブトキシシラン、トリエチルイソプロポキ
シシラン、トリ−ｎ−プロピルエトキシシラン、
トリ−ｎ−ブチルエトキシシラン、トリイソペン
チルエトキシシラン、フエニルトリエトキシシラ
ン、フエニルトリイソブトキシシラン、フエニル
トリイソペントキシシラン、ジフエニルジエトキ
シシラン、ジフエニルジイソペントキシシラン、
ジフエニルジオクトキシシラン、トリフエニルメ
トキシシラン、トリフエニルエトキシシラン、ト
リフエニルイソペントキシシラン、クロロエチル
トリメトキシシラン、クロロエチルトリエトキシ
シラン、及びクロロブチルトリエトキシシランが
挙げられる。 Specific examples of silicon compounds include tetramethoxysilane, tetraethoxysilane, and tetra-n-
Propoxysilane, Tetra-n-butoxysilane, Tetra-isopentoxysilane, Tetra-n
-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n
-butoxysilane, methyltriisopentoxysilane, methyltri-n-hexoxysilane, methyltriisooctoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopentoxysilane, n-butyltriethoxysilane, isobutyl Triethoxysilane, isopentyltriethoxysilane, isopentyltri-n-butoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane,
Dimethyldiisopentoxysilane, diethyldiethoxysilane, diethyldiisopentoxysilane, di-n-butyldiethoxysilane, diisobutyldiisopentoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisobutoxysilane, triethyliso Propoxysilane, tri-n-propylethoxysilane,
Tri-n-butylethoxysilane, triisopentylethoxysilane, phenyltriethoxysilane, phenyltriisobutoxysilane, phenyltriisopentoxysilane, diphenyldiethoxysilane, diphenyldiisopentoxysilane,
Examples include diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxysilane, triphenylisopentoxysilane, chloroethyltrimethoxysilane, chloroethyltriethoxysilane, and chlorobutyltriethoxysilane.
反応に共するハロゲン化アルミニウムの割合
は、ケイ素化合物１モル当り、0.1〜10モル、特
に0.3〜２モルであることが好ましい。 The proportion of aluminum halide involved in the reaction is preferably 0.1 to 10 mol, particularly 0.3 to 2 mol, per mol of silicon compound.
ハロゲン化アルミニウムとケイ素化合物との反
応は、通常、両化合物を不活性有機溶媒中で、−
50〜100℃の範囲の温度で0.1〜２時間攪拌するこ
とによつて行なわれる。反応は発熱を伴なつて進
行し、反応生成物は不活性有機溶媒溶液として得
られる。反応生成物は不活性有機溶媒溶液として
グリニヤール化合物との反応に供される。 The reaction between aluminum halide and a silicon compound is usually carried out by combining both compounds in an inert organic solvent with -
This is carried out by stirring for 0.1 to 2 hours at a temperature in the range of 50 to 100°C. The reaction proceeds with exotherm, and the reaction product is obtained as a solution in an inert organic solvent. The reaction product is subjected to the reaction with the Grignard compound as a solution in an inert organic solvent.
グリニヤール化合物の中でもＸが塩素原子であ
るアルキルマグネシウムクロライドが好適に使用
され、その具体例としては、メチルマグネシウム
クロライド、エチルマグネシウムクロライド、ｎ
−ブチルマグネシウムクロライド、ｎ−ヘキシル
マグネシウムクロライドが挙げられる。 Among Grignard compounds, alkylmagnesium chlorides in which X is a chlorine atom are preferably used, and specific examples include methylmagnesium chloride, ethylmagnesium chloride, n
-butylmagnesium chloride and n-hexylmagnesium chloride.
グリニヤール化合物の使用量は、反応生成物の
調整に使用されたハロゲン化アルミニウム１モル
当り、0.05〜４モル、特に１〜３モルであること
が好ましい。 The amount of Grignard compound used is preferably 0.05 to 4 mol, particularly 1 to 3 mol, per mol of aluminum halide used for preparing the reaction product.
反応生成物とグリニヤール化合物とを反応させ
る方法については特に制限はないが、反応生成物
の不活性有機溶媒溶液に、グリニヤール化合物の
エーテル溶液またはエーテルと芳香族炭化水素と
の混合溶媒溶液を徐々に添加することにより、ま
たはこれとは逆の順序で添加することによつて行
なうのが便利である。上記のエーテルとしては、
式 R6−Ｏ−R7
（式中、R6及びR7はそれぞれ炭素数２〜８の
アルキル基を示す。）で表わされる化合物が好適
に使用され、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−ｎ−ブチル
エーテル、及びジイソアミルエーテが挙げられ
る。 There is no particular restriction on the method of reacting the reaction product with the Grignard compound, but an ether solution of the Grignard compound or a mixed solvent solution of ether and an aromatic hydrocarbon is gradually added to the solution of the reaction product in an inert organic solvent. Conveniently this is done by addition or addition in the reverse order. As the above ether, a compound represented by the formula R 6 -O-R 7 (in the formula, R 6 and R 7 each represent an alkyl group having 2 to 8 carbon atoms) is preferably used, and specific examples thereof are as follows. These include diethyl ether, diisopropyl ether, di-n-butyl ether, and diisoamyl ether.
反応温度は通常−50〜100℃、好ましくは−20
〜25℃である。反応時間については特に制限はな
いが、通常５分以上である。反応の進行に伴なつ
て白色の担持が析出してくる。こうして得られる
担持は反応混合物としてつぎの処理に供すること
もできるが、予め担体を分離し、不活性有機溶媒
で洗浄した後、つぎの処理に供することが好まし
い。 The reaction temperature is usually -50 to 100℃, preferably -20℃
~25℃. There is no particular restriction on the reaction time, but it is usually 5 minutes or more. As the reaction progresses, a white support begins to precipitate. The support thus obtained can be used as a reaction mixture for the next treatment, but it is preferable to separate the support in advance and wash it with an inert organic solvent before using it for the next treatment.
四ハロゲン化チタンの具体例としては、四塩化
チタン、四臭化チタンおよび四沃化チタンが挙げ
られ、中でも四塩化チタンが好ましく使用され
る。四ハロゲン化チタンの使用量は、担体の調製
時に使用したグリニヤール化合物１モル当り、１
モル以上、特に２〜100モルであることが好まし
い。 Specific examples of titanium tetrahalide include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, of which titanium tetrachloride is preferably used. The amount of titanium tetrahalide used is 1 mole of Grignard compound used in preparing the carrier.
The amount is preferably 2 to 100 moles or more, particularly 2 to 100 moles.
担体と四ハロゲン化チタンとの接触は、不活性
有機溶媒の存在下又は不存在下に、20〜200℃、
好ましくは60〜140℃の温度で0.5〜３時間行なわ
れる。得られる接触固体は不活性有機溶媒で洗浄
した後、次の処理に供される。 The support and the titanium tetrahalide are brought into contact at 20 to 200°C in the presence or absence of an inert organic solvent.
It is preferably carried out at a temperature of 60 to 140°C for 0.5 to 3 hours. The resulting contact solid is washed with an inert organic solvent and then subjected to the next treatment.
シクロプロパンカルボン酸エステルの具体例と
しては、シクロプロパンカルボン酸のメチル−、
エチル−、プロピル−、ブチル−、ヘキシル−、
及びオクチルエステルが挙げられる。シクロプロ
パンカルボン酸エステルの使用量は接触固体１ｇ
当り0.1〜10ミリモルであることが好ましい。 Specific examples of cyclopropanecarboxylic acid esters include methyl cyclopropanecarboxylic acid,
Ethyl, propyl, butyl, hexyl,
and octyl esters. The amount of cyclopropane carboxylic acid ester used is 1g of contact solid.
The amount is preferably 0.1 to 10 mmol.
接触固体をシクロプロパンカルボン酸エステル
で処理する方法については特に制限はないが、接
触固体を不活性有機媒液に懸濁させ、この懸濁液
にシクロプロパンカルボン酸エステルを加えて攪
拌する方法が便利に採用される。処理温度は０〜
200℃、特に５〜150℃であることが好ましい。処
理時間については特に制限はないが、通常５分以
上である。得られる処理固体は不活性有機溶媒で
洗浄した後、再度四ハロゲン化チタンと接触させ
る。 There are no particular restrictions on the method of treating the contact solid with the cyclopropane carboxylic acid ester, but a method of suspending the contact solid in an inert organic medium, adding the cyclopropane carboxylic acid ester to this suspension, and stirring the mixture is recommended. conveniently adopted. Processing temperature is 0~
The temperature is preferably 200°C, particularly 5 to 150°C. There is no particular restriction on the processing time, but it is usually 5 minutes or more. The resulting treated solid is washed with an inert organic solvent and then brought into contact with titanium tetrahalide again.
処理固体と四ハロゲン化チタンとの接触は、担
体と四ハロゲン化チタンとの接触と同様にして行
なうことができる。 Contacting the treated solid with titanium tetrahalide can be carried out in the same manner as contacting the carrier with titanium tetrahalide.
こうして得られる固体触媒成分〔Ａ〕を含む混
合物から固体触媒成分〔Ａ〕を過、傾斜などに
よつて分別し、不活性有機溶媒で洗浄する。固体
触媒成分〔Ａ〕中にはチタンが0.5〜５重量％含
有されている。 The solid catalyst component [A] is separated from the thus obtained mixture containing the solid catalyst component [A] by filtration, decanting, etc., and washed with an inert organic solvent. The solid catalyst component [A] contains 0.5 to 5% by weight of titanium.
本発明において、固体触媒成分〔Ａ〕、有機ア
ルミニウム化合物〔Ｂ〕および芳香族カルボン酸
エステル〔Ｃ〕から得られる触媒の存在下に、炭
素数３以上のａ−オレフインを重合する。 In the present invention, an a-olefin having 3 or more carbon atoms is polymerized in the presence of a catalyst obtained from a solid catalyst component [A], an organoaluminum compound [B], and an aromatic carboxylic acid ester [C].
有機アルミニウム化合物〔Ｂ〕の具体例として
は、トリメチルアルミニウム、トリエチルアルミ
ニウム、トリイソブチルアルミニウム、及びトリ
−ｎ−ヘキシルアルミニウムが挙げられる。有機
アルミニウム化合物〔Ｂ〕の使用量は、固体触媒
成分〔Ａ〕中のチタン１グラム原子当り、通常１
〜1000モルである。 Specific examples of the organic aluminum compound [B] include trimethylaluminum, triethylaluminum, triisobutylaluminum, and tri-n-hexylaluminum. The amount of organoaluminum compound [B] used is usually 1 gram atom of titanium in the solid catalyst component [A].
~1000 mol.
芳香族カルボン酸エステルとしては、
〔式中、R8は炭素数１〜６のアルキル基を示
し、Ｙは水素原子、炭素数１〜４のアルキル基ま
たは−OR9（R9は炭素数１〜４のアルキル基を示
す。）を示す。〕で表わされる化合物が好適に使用
され、その具体例としては、安息香酸メチル、安
息香酸エチル、トルイル酸メチル、トルイル酸エ
チル、アニス酸メチル、及びアニス酸エチルが挙
げられる。芳香族カルボンピンエステル〔Ｃ〕の
使用量は、有機アルミニウム化合物〔Ｂ〕１モル
当り、0.01〜１モル、特に0.05〜0.5モルであるこ
とが好ましい。 As aromatic carboxylic acid ester, [In the formula, R 8 represents an alkyl group having 1 to 6 carbon atoms, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -OR 9 (R 9 represents an alkyl group having 1 to 4 carbon atoms). ) is shown. ] Compounds represented by the following are preferably used, and specific examples thereof include methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate. The amount of aromatic carbonpine ester [C] used is preferably 0.01 to 1 mol, particularly 0.05 to 0.5 mol, per 1 mol of organoaluminum compound [B].
炭素数３以上のａ−オレフインの具体例として
は、プロピレン、ブテン−１，４−メチルペンテ
ン−１、及びヘキセン−１が挙げられる。本発明
においては、上記ａ−オレフインの単独または共
重合を行なうことができ、さらに上記ａ−オレフ
インとエチレンとの共重合を行なうこともでき
る。 Specific examples of the a-olefin having 3 or more carbon atoms include propylene, butene-1,4-methylpentene-1, and hexene-1. In the present invention, the a-olefin described above can be used alone or copolymerized, and the a-olefin described above and ethylene can also be copolymerized.
重合反応は、通常のチーグラー・ナツタ型触媒
によるａ−オレフインの重合反応と同様にして行
なうことができる。 The polymerization reaction can be carried out in the same manner as the polymerization reaction of a-olefin using a usual Ziegler-Natsuta type catalyst.
重合反応は液相または気相で行うことができ
る。 The polymerization reaction can be carried out in liquid phase or gas phase.
重合反応は液相で行なう場合、不活性有機溶媒
を重合溶媒として使用してもよく、液状のａ−オ
レフイン自体を重合溶媒としてもよい。重合溶媒
中の触媒濃度については特に制限はないが、一般
には、重合溶媒１当り、固体触媒成分〔Ａ〕に
ついてはチタン金属換算で0.001〜１ミリグラム
原子であり、有機アルミニウム化合物〔Ｂ〕につ
いては0.01〜100ミリモルである。 When the polymerization reaction is carried out in a liquid phase, an inert organic solvent may be used as the polymerization solvent, or the liquid a-olefin itself may be used as the polymerization solvent. There is no particular restriction on the catalyst concentration in the polymerization solvent, but in general, the solid catalyst component [A] is 0.001 to 1 milligram atom in terms of titanium metal per polymerization solvent, and the organoaluminum compound [B] is 0.01-100 mmol.
この発明において、固体触媒成分〔Ａ〕の調製
時、場合により重合反応時に使用される不活性有
機溶媒としては、ヘキサン、ヘプタンのような脂
肪族炭化水素、トルエン、ベンゼン、キシレンの
ような芳香族炭化水素、及びこれら炭化水素のハ
ロゲン化物が挙げられる。 In this invention, the inert organic solvent used during the preparation of the solid catalyst component [A] and optionally during the polymerization reaction includes aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene, benzene, and xylene. Examples include hydrocarbons and halides of these hydrocarbons.
重合反応は水分および酸素を実質的に絶つた状
態で行なわれる。 The polymerization reaction is carried out in the substantial absence of moisture and oxygen.
重合温度は通常30〜100℃であり、重合圧力は
通常１〜８Kg／cm2である。 The polymerization temperature is usually 30 to 100°C, and the polymerization pressure is usually 1 to 8 kg/cm 2 .
この発明の方法で得られるａ−オレフイン重合
体分子量は、重合系に水素を添加することによつ
て容易に調節することができる。 The molecular weight of the a-olefin polymer obtained by the method of this invention can be easily adjusted by adding hydrogen to the polymerization system.
つぎに実施例を示す。以下の記載において、
「重合活性」とは、重合反応に使用した固体触媒
成分１ｇ当り、重合時間１時間当りの重合体収量
ｇであり、「H.I」とは、生成重合体を沸騰ｎ−
ヘプタンで20時間抽出したときの抽出残留分の全
重合体に対する重量百分率である。実施例におい
て、固体触媒成分の調製はすべて乾燥した窒素ガ
ス雰囲気中で行なつた。 Next, examples will be shown. In the following description,
"Polymerization activity" is the polymer yield in g per 1 hour of polymerization time per 1 g of solid catalyst component used in the polymerization reaction, and "HI" is the polymer yield in g per 1 hour of polymerization time.
This is the weight percentage of the extraction residue based on the total polymer when extracted with heptane for 20 hours. In the Examples, all solid catalyst components were prepared in a dry nitrogen gas atmosphere.
実施例 １
(1) 固体触媒成分の調製
無水塩化アルミニウム15.8ミリモルを含むトル
エン30mlにメチルトリエトキシシラン15ミリモル
のトルエン溶液15mlを添加し、攪拌下に、25℃で
１時間反応させた。Example 1 (1) Preparation of solid catalyst component 15 ml of a toluene solution containing 15 mmol of methyltriethoxysilane was added to 30 ml of toluene containing 15.8 mmol of anhydrous aluminum chloride, and the mixture was reacted with stirring at 25° C. for 1 hour.
反応混合物を−10℃に冷却し、ｎ−ブチルマグ
ネシウムクロライド27ミリモルのジイソプロピル
エーテル溶液21.4mlを、攪拌下に、反応混合物に
１時間で加えた。反応系の温度は−10℃に保つ
た。同温度で１時間反応を続けた。析出した担体
を別し、トルエンで洗浄した。 The reaction mixture was cooled to -10 DEG C. and 21.4 ml of a solution of 27 mmol of n-butylmagnesium chloride in diisopropyl ether was added to the reaction mixture over 1 hour while stirring. The temperature of the reaction system was maintained at -10°C. The reaction was continued for 1 hour at the same temperature. The precipitated carrier was separated and washed with toluene.
担体のトルエン懸濁液30mlに四塩化チタン150
ミリモルを加えた後90℃に昇温し、攪拌下に１時
間担体と四塩化チタンとを接触させた。90℃で接
触固体を別し、トルエンついでｎ−ヘプタンで
洗浄した。 150 titanium tetrachloride in 30 ml of toluene suspension of carrier
After adding millimoles of titanium tetrachloride, the temperature was raised to 90°C, and the support and titanium tetrachloride were brought into contact with each other for 1 hour while stirring. The contact solid was separated at 90°C and washed with toluene and then n-heptane.
接触固体のトルエン懸濁液30mlにシクロプロパ
ンカルボン酸エチル6.3ミリモルを加え、攪拌下
90℃に１時間保持した。同温度で処理固体を別
し、トルエンついでｎ−ヘプタンで洗浄した。 Add 6.3 mmol of ethyl cyclopropanecarboxylate to 30 ml of toluene suspension of the contact solid, and stir.
It was held at 90°C for 1 hour. The treated solid was separated at the same temperature and washed with toluene and then with n-heptane.
処理固体のトルエン懸濁液30mlに四塩化チタン
150ミリモルを加え、攪拌下に90℃に１時間保持
した。得られた固体触媒成分を90℃で別し、ト
ルエンついでｎ−ヘプタンで洗浄した。固体触媒
成分3.3ｇをｎ−ヘプタン80mlに懸濁させて、固
体触媒成分スリラーを調製した。固体触媒成分の
チタン含有率は2.6重量％であつた。 Titanium tetrachloride in 30 ml of toluene suspension of treated solids
150 mmol was added and kept at 90° C. for 1 hour while stirring. The obtained solid catalyst component was separated at 90°C and washed with toluene and then with n-heptane. A solid catalyst component thriller was prepared by suspending 3.3 g of the solid catalyst component in 80 ml of n-heptane. The titanium content of the solid catalyst component was 2.6% by weight.
(2) 重合
攪拌機付の内容積２のオートクレーブ内に固
体触媒成分のスラリ−（固体触媒成分として13.6
mg）を封入したガラスアンプルを取り付けた後、
オートクレーブ内の空気を窒素で置換した。ｐ−
トルイル酸メチル0.37ミリモルのｎ−ヘプタン溶
液４ml、ついでトリエチルアルミニウム1.48ミリ
モルのｎ−ヘプタン溶液1.5mlをオートクレーブ
に仕込んだ。液体プロピレン1200mlをオートクレ
ーブに導入し、オートクレーブを振とうした。オ
ートクレーブ内容物を65℃に昇温した後、攪拌を
開始して上記ガラスアンプルを破砕し、65℃で１
時間プロピレンを重合させた。重合反応終了後、
未反応のプロピレンを放出し、ガラス破片を取り
除き、生成ポリプロピレンを50℃で20時間減圧乾
燥した。白色の粉末状ポリプロポレン251ｇを得
た。重合活性は18，456，H.I.は95.4％であつた。(2) Polymerization A slurry of the solid catalyst component (13.6 mm as the solid catalyst component) was placed in an autoclave with an internal volume of 2 and equipped with a stirrer.
After attaching the glass ampoule containing mg),
The air in the autoclave was replaced with nitrogen. p-
4 ml of a solution of 0.37 mmol of methyl toluate in n-heptane and then 1.5 ml of a solution of 1.48 mmol of triethylaluminum in n-heptane were charged into the autoclave. 1200 ml of liquid propylene was introduced into the autoclave and the autoclave was shaken. After heating the contents of the autoclave to 65°C, stirring was started to crush the glass ampoule, and the contents were heated to 65°C for 1 hour.
Time propylene was polymerized. After the polymerization reaction is complete,
Unreacted propylene was released, glass fragments were removed, and the resulting polypropylene was dried under reduced pressure at 50°C for 20 hours. 251 g of white powdered polypropylene was obtained. The polymerization activity was 18,456, and the HI was 95.4%.
実施例 ２
シクロプロパンカルボン酸エチルに代えてシク
ロプロパンカルボン酸ｎ−プロピル6.3ミリモル
を使用した以外は実施例１におけると同様にし
て、固体溶媒成分を調製した。固体触媒成分のチ
タン含有率は2.8重量％であつた。Example 2 A solid solvent component was prepared in the same manner as in Example 1, except that 6.3 mmol of n-propyl cyclopropanecarboxylate was used in place of ethyl cyclopropanecarboxylate. The titanium content of the solid catalyst component was 2.8% by weight.
この固体触媒成分13.6mgを使用した以外は実施
例１におけると同様にしてプロピレンを重合し
た。 Propylene was polymerized in the same manner as in Example 1 except that 13.6 mg of this solid catalyst component was used.
H.I.9.5.1％のポリプロピレンが18740の重合活
性で得られた。 Polypropylene with HI 9.5.1% was obtained with a polymerization activity of 18740.
実施例 ３
シクロプロパンカルボン酸エチルに代えてシク
ロプロパンカルボン酸ｎ−ヘキシル6.3ミリモル
を使用した以外は実施例１におけると同様にし
て、固体溶媒成分を調製した。固体溶媒成分のチ
タン含有率は2.7重量％であつた。Example 3 A solid solvent component was prepared in the same manner as in Example 1 except that 6.3 mmol of n-hexyl cyclopropanecarboxylate was used in place of ethyl cyclopropanecarboxylate. The titanium content of the solid solvent component was 2.7% by weight.
この固体溶媒成分11mgを使用した以外は実施例
１におけると同様にしてプロピレンを重合した。 Propylene was polymerized in the same manner as in Example 1 except that 11 mg of this solid solvent component was used.
HI95.3％のポリプロピレンが18300の重合活性
で得られた。 Polypropylene with HI 95.3% was obtained with a polymerization activity of 18300.
実施例 ４
ｐ−トルイル酸メチルの使用量を0.42ミリモル
に変えた以外は実施例１を繰返した。Example 4 Example 1 was repeated except that the amount of methyl p-toluate used was changed to 0.42 mmol.
H.I.9.5.3％のポリプロピレンが18470の重合活
性で得られた。 Polypropylene with HI 9.5.3% was obtained with a polymerization activity of 18470.
実施例 ５
液体プロピレンの導入に先立ち、水素をその分
圧が0.4Kg／cm2になる迄オートクレーブに圧入し
た以外は実施例１を繰返した。Example 5 Example 1 was repeated except that prior to the introduction of liquid propylene, hydrogen was pressurized into the autoclave until its partial pressure was 0.4 Kg/cm 2 .
H.I.94.7％，M.I.1.8ｇ／10分のポリプロピレン
が18040の重合活性で得られた。 Polypropylene with a HI of 94.7% and an MI of 1.8 g/10 min was obtained with a polymerization activity of 18040.
第１図は本発明の触媒調製のフローチヤートを
示す。
FIG. 1 shows a flowchart for preparing the catalyst of the present invention.
Claims (1)
素数１〜８のアルキル基又はフエニル基を示
し、R2は炭素数１〜８のアルキル基を示し、
ｍは０，１，２又は３である。）で表わされる
ケイ素化合物と反応させ、 (2) 反応生成物を 式R3MgX （式中、R3は炭素数１〜８のアルキル基を
示し、Ｘはハロゲン原子を示す。）で表わされ
るグリニヤール化合物と反応させ、 (3) 得られる担体を四ハロゲン化チタンと接触さ
せ、 (4) 接触固体を 式 （式中、R4は炭素数１〜８のアルキル基を示
す。） で表わされるシクロプロパンカルボン酸エステ
ルで処理し、 (5) 処理固体を四ハロゲン化チタンと接触させて
得られる固体触媒成分〔Ａ〕、 式 AlR5 3 （式中、R5は炭素数１〜６のアルキル基を
示す。） で表わされる有機アルミニウム化合物〔Ｂ〕、
及び芳香族カルボン酸エステル〔Ｃ〕から得ら
れる触媒の存在下に、炭素数３以上のα−オレ
フインを重合することを特徴とするα−オレフ
インの重合法。[Claims] 1 (1) Aluminum halide with the formula R 1 n Si(OR 2 ) 4-n (wherein R 1 is a halogen-substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or a phenyl group) , R 2 represents an alkyl group having 1 to 8 carbon atoms,
m is 0, 1, 2 or 3. ), and (2) the reaction product is expressed by the formula R 3 MgX (wherein R 3 represents an alkyl group having 1 to 8 carbon atoms, and X represents a halogen atom). (3) contacting the resulting support with titanium tetrahalide; (4) converting the contacted solid to the formula (In the formula, R 4 represents an alkyl group having 1 to 8 carbon atoms.) (5) A solid catalyst component obtained by contacting the treated solid with titanium tetrahalide. [A], an organoaluminum compound represented by the formula AlR 5 3 (in the formula, R 5 represents an alkyl group having 1 to 6 carbon atoms) [B],
A method for polymerizing α-olefin, which comprises polymerizing α-olefin having 3 or more carbon atoms in the presence of a catalyst obtained from aromatic carboxylic acid ester [C].
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17412483A JPS6067507A (en) | 1983-09-22 | 1983-09-22 | Polymerization of alpha-olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17412483A JPS6067507A (en) | 1983-09-22 | 1983-09-22 | Polymerization of alpha-olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6067507A JPS6067507A (en) | 1985-04-17 |
| JPH0425287B2 true JPH0425287B2 (en) | 1992-04-30 |
Family
ID=15973068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17412483A Granted JPS6067507A (en) | 1983-09-22 | 1983-09-22 | Polymerization of alpha-olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6067507A (en) |
-
1983
- 1983-09-22 JP JP17412483A patent/JPS6067507A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6067507A (en) | 1985-04-17 |
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