JPS6123209B2 - - Google Patents
Info
- Publication number
- JPS6123209B2 JPS6123209B2 JP13760877A JP13760877A JPS6123209B2 JP S6123209 B2 JPS6123209 B2 JP S6123209B2 JP 13760877 A JP13760877 A JP 13760877A JP 13760877 A JP13760877 A JP 13760877A JP S6123209 B2 JPS6123209 B2 JP S6123209B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- polymerization
- olefin polymer
- compound
- 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
Links
- 238000006116 polymerization reaction Methods 0.000 claims description 77
- 229910052719 titanium Inorganic materials 0.000 claims description 72
- 239000010936 titanium Substances 0.000 claims description 72
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 70
- 239000011949 solid catalyst Substances 0.000 claims description 45
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229920000098 polyolefin Polymers 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 22
- 150000001336 alkenes Chemical class 0.000 claims description 19
- 150000002681 magnesium compounds Chemical class 0.000 claims description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 16
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 4
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 5
- 238000004581 coalescence Methods 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 55
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 48
- -1 ethylene, propylene Chemical group 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 150000001733 carboxylic acid esters Chemical class 0.000 description 23
- 238000003756 stirring Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 239000007787 solid Substances 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 239000000843 powder Substances 0.000 description 11
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- 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 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229920006125 amorphous polymer Polymers 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 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 5
- 239000000047 product Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- NWPWRAWAUYIELB-UHFFFAOYSA-N ethyl 4-methylbenzoate Chemical compound CCOC(=O)C1=CC=C(C)C=C1 NWPWRAWAUYIELB-UHFFFAOYSA-N 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 4
- QSSJZLPUHJDYKF-UHFFFAOYSA-N methyl 4-methylbenzoate Chemical compound COC(=O)C1=CC=C(C)C=C1 QSSJZLPUHJDYKF-UHFFFAOYSA-N 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 2
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-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
- 241000282326 Felis catus Species 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OLLPXZHNCXACMM-CMDGGOBGSA-N Propyl cinnamate Chemical compound CCCOC(=O)\C=C\C1=CC=CC=C1 OLLPXZHNCXACMM-CMDGGOBGSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 2
- 239000001405 butyl (E)-3-phenylprop-2-enoate Substances 0.000 description 2
- PFMFULUTMUJMMV-UHFFFAOYSA-N butyl 2-(dimethylamino)acetate Chemical compound CCCCOC(=O)CN(C)C PFMFULUTMUJMMV-UHFFFAOYSA-N 0.000 description 2
- HTYCJCQPUKZKTD-UHFFFAOYSA-N butyl 2-(n-phenylanilino)acetate Chemical compound C=1C=CC=CC=1N(CC(=O)OCCCC)C1=CC=CC=C1 HTYCJCQPUKZKTD-UHFFFAOYSA-N 0.000 description 2
- OHHIVLJVBNCSHV-KTKRTIGZSA-N butyl cinnamate Chemical compound CCCCOC(=O)\C=C/C1=CC=CC=C1 OHHIVLJVBNCSHV-KTKRTIGZSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- XSBSXJAYEPDGSF-UHFFFAOYSA-N diethyl 3,5-dimethyl-1h-pyrrole-2,4-dicarboxylate Chemical compound CCOC(=O)C=1NC(C)=C(C(=O)OCC)C=1C XSBSXJAYEPDGSF-UHFFFAOYSA-N 0.000 description 2
- BGCNBOFPABQGNG-UHFFFAOYSA-N ethyl 2-(dimethylamino)acetate Chemical compound CCOC(=O)CN(C)C BGCNBOFPABQGNG-UHFFFAOYSA-N 0.000 description 2
- ATRXRURAIJZUOT-UHFFFAOYSA-N ethyl 2-(n-phenylanilino)acetate Chemical compound C=1C=CC=CC=1N(CC(=O)OCC)C1=CC=CC=C1 ATRXRURAIJZUOT-UHFFFAOYSA-N 0.000 description 2
- ZPUKPAPWEWUPTC-UHFFFAOYSA-N ethyl 4-ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(CC)C=C1 ZPUKPAPWEWUPTC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- RNHXTCZZACTEMK-UHFFFAOYSA-N methyl 4-ethoxybenzoate Chemical compound CCOC1=CC=C(C(=O)OC)C=C1 RNHXTCZZACTEMK-UHFFFAOYSA-N 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 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
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- LZRFQYZCMVMADF-UHFFFAOYSA-N phenyl 2-methoxybenzoate Chemical compound COC1=CC=CC=C1C(=O)OC1=CC=CC=C1 LZRFQYZCMVMADF-UHFFFAOYSA-N 0.000 description 2
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 2
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 2
- 229940049953 phenylacetate Drugs 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000001572 propyl (E)-3-phenylprop-2-enoate Substances 0.000 description 2
- ZHDCHCTZRODSEN-HWKANZROSA-N propyl (e)-but-2-enoate Chemical compound CCCOC(=O)\C=C\C ZHDCHCTZRODSEN-HWKANZROSA-N 0.000 description 2
- SDRUOGAFMUPTQU-UHFFFAOYSA-N propyl 2-(dimethylamino)acetate Chemical compound CCCOC(=O)CN(C)C SDRUOGAFMUPTQU-UHFFFAOYSA-N 0.000 description 2
- WDYZSLQVKDHVME-UHFFFAOYSA-N propyl 4-ethylbenzoate Chemical compound CCCOC(=O)C1=CC=C(CC)C=C1 WDYZSLQVKDHVME-UHFFFAOYSA-N 0.000 description 2
- WEHMFTWWOGBHCR-UHFFFAOYSA-N propyl 4-methoxybenzoate Chemical compound CCCOC(=O)C1=CC=C(OC)C=C1 WEHMFTWWOGBHCR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CBJILYZAALBXKE-UHFFFAOYSA-N butyl 4-butylbenzoate Chemical compound CCCCOC(=O)C1=CC=C(CCCC)C=C1 CBJILYZAALBXKE-UHFFFAOYSA-N 0.000 description 1
- ZHSXGLBHFVIEPT-UHFFFAOYSA-N butyl 4-ethylbenzoate Chemical compound CCCCOC(=O)C1=CC=C(CC)C=C1 ZHSXGLBHFVIEPT-UHFFFAOYSA-N 0.000 description 1
- YWPROEQSNYMONU-UHFFFAOYSA-N butyl 4-hexylbenzoate Chemical compound CCCCCCC1=CC=C(C(=O)OCCCC)C=C1 YWPROEQSNYMONU-UHFFFAOYSA-N 0.000 description 1
- UYGHRCCJWWYXMY-UHFFFAOYSA-N butyl 4-methylbenzoate Chemical compound CCCCOC(=O)C1=CC=C(C)C=C1 UYGHRCCJWWYXMY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NKAVJELRFJVPEE-UHFFFAOYSA-N ethyl 4-butylbenzoate Chemical compound CCCCC1=CC=C(C(=O)OCC)C=C1 NKAVJELRFJVPEE-UHFFFAOYSA-N 0.000 description 1
- GQRZXKALRVNWOI-UHFFFAOYSA-N ethyl 4-hexylbenzoate Chemical compound CCCCCCC1=CC=C(C(=O)OCC)C=C1 GQRZXKALRVNWOI-UHFFFAOYSA-N 0.000 description 1
- POSWANCOKFTNQZ-UHFFFAOYSA-N ethyl 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C(=O)OCC)C=C1 POSWANCOKFTNQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- FNODWEPAWIJGPM-UHFFFAOYSA-N ethyl o-methoxybenzoate Natural products CCOC(=O)C1=CC=CC=C1OC FNODWEPAWIJGPM-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- FSMGSEAKDZNSAS-UHFFFAOYSA-N hexyl 4-butylbenzoate Chemical compound CCCCCCOC(=O)C1=CC=C(CCCC)C=C1 FSMGSEAKDZNSAS-UHFFFAOYSA-N 0.000 description 1
- WWCOVCJCTORFJV-UHFFFAOYSA-N hexyl 4-ethylbenzoate Chemical compound CCCCCCOC(=O)C1=CC=C(CC)C=C1 WWCOVCJCTORFJV-UHFFFAOYSA-N 0.000 description 1
- AWYIEWURDDNCJR-UHFFFAOYSA-N hexyl 4-hexylbenzoate Chemical compound CCCCCCOC(=O)C1=CC=C(CCCCCC)C=C1 AWYIEWURDDNCJR-UHFFFAOYSA-N 0.000 description 1
- PELWVATUYGIRES-UHFFFAOYSA-N hexyl 4-methylbenzoate Chemical compound CCCCCCOC(=O)C1=CC=C(C)C=C1 PELWVATUYGIRES-UHFFFAOYSA-N 0.000 description 1
- DXGRDPOKEXFGAO-UHFFFAOYSA-N hexyl 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C(=O)OCCCCCC)C=C1 DXGRDPOKEXFGAO-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- XJRYQLPELPLPHZ-UHFFFAOYSA-N methyl 4-butylbenzoate Chemical compound CCCCC1=CC=C(C(=O)OC)C=C1 XJRYQLPELPLPHZ-UHFFFAOYSA-N 0.000 description 1
- CAABRJFUDNBRJZ-UHFFFAOYSA-N methyl 4-ethylbenzoate Chemical compound CCC1=CC=C(C(=O)OC)C=C1 CAABRJFUDNBRJZ-UHFFFAOYSA-N 0.000 description 1
- RTTGTHPEVMEHEK-UHFFFAOYSA-N methyl 4-hexylbenzoate Chemical compound CCCCCCC1=CC=C(C(=O)OC)C=C1 RTTGTHPEVMEHEK-UHFFFAOYSA-N 0.000 description 1
- NKSKNAWLKUQLNY-UHFFFAOYSA-N methyl 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C(=O)OC)C=C1 NKSKNAWLKUQLNY-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 1
- WOHCEFXPFWWXKJ-UHFFFAOYSA-N octyl 4-butylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(CCCC)C=C1 WOHCEFXPFWWXKJ-UHFFFAOYSA-N 0.000 description 1
- PXGCAPRMDJWYHP-UHFFFAOYSA-N octyl 4-ethylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(CC)C=C1 PXGCAPRMDJWYHP-UHFFFAOYSA-N 0.000 description 1
- VBDCUVDAJYAVEK-UHFFFAOYSA-N octyl 4-hexylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(CCCCCC)C=C1 VBDCUVDAJYAVEK-UHFFFAOYSA-N 0.000 description 1
- MGRDBXFNMFBCLH-UHFFFAOYSA-N octyl 4-methylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C)C=C1 MGRDBXFNMFBCLH-UHFFFAOYSA-N 0.000 description 1
- QHJVVZLZLOACPN-UHFFFAOYSA-N octyl 4-octylbenzoate Chemical compound CCCCCCCCOC(=O)C1=CC=C(CCCCCCCC)C=C1 QHJVVZLZLOACPN-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 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
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- ORTOXYFZAPIBPJ-UHFFFAOYSA-N propyl 2-(n-phenylanilino)acetate Chemical compound C=1C=CC=CC=1N(CC(=O)OCCC)C1=CC=CC=C1 ORTOXYFZAPIBPJ-UHFFFAOYSA-N 0.000 description 1
- KWGVHDSKXOIFNY-UHFFFAOYSA-N propyl 4-butylbenzoate Chemical compound CCCCC1=CC=C(C(=O)OCCC)C=C1 KWGVHDSKXOIFNY-UHFFFAOYSA-N 0.000 description 1
- LRNBWFXCDULFQF-UHFFFAOYSA-N propyl 4-methylbenzoate Chemical compound CCCOC(=O)C1=CC=C(C)C=C1 LRNBWFXCDULFQF-UHFFFAOYSA-N 0.000 description 1
- SKNREWLKHODPNM-UHFFFAOYSA-N propyl 4-octylbenzoate Chemical compound CCCCCCCCC1=CC=C(C(=O)OCCC)C=C1 SKNREWLKHODPNM-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920000576 tactic polymer Polymers 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
- 125000005425 toluyl group Chemical group 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
本発明は、オレフイン重合体の製造方法に関す
るものである。
更に詳しくは、本発明は、高重合活性を有する
担体付触媒成分と有機アルミニウム化合物とカル
ボン酸エステルとを組み合せてなる触媒系の存在
下、エチレン、プロピレン、プテン−１などのオ
レフインを多段で重合して、オレフイン重合体を
製造する方法に関するものである。
従来、高重合活性で、かつ高立体規則性重合体
を与える担体付オレフイン重合用触媒が種々提案
されている。例えば、特開昭47−9342、同48−
16986、同50−108385、同51−57789及び同51−
20297には、マグネシウムハロゲン化物、ハロゲ
ン化チタン及び電子供与性化合物を接触させて得
られる固体触媒をα−オレフインの重合に使用す
ることが提案されている。また本発明者等も、さ
きに、グリニヤール化合物と、水、アルコール、
シラノール又はポリシラノール等とを反応させて
得られるマグネシウム化合物にハロゲン化チタン
及び電子供与性化合物を接触させて得られる固体
触媒成分をα−オレフインの重合に使用すること
を提案した。
これらの触媒は高活性で且つ高立体規則性の重
合体を与える触媒ではあるが、副生する非晶性重
合体の量は充分少いとは言えず、このことは原料
モノマーから結晶性重合体への転化率が低い、あ
るいは非晶性重合体によるスラリー状態の悪化
等、好ましくない結果をもたらす。また、この非
晶性重合体を除去しない場合には、重合体の射
出、押出成型品、フイルム等の機械的物性が不足
するなど、その立体規則性はいまだ充分なものと
は言えなかつた。また、重合体中に残存する触媒
成分を除去しないと、残存する触媒成分（特にハ
ロゲン）による成型装置の腐食、あるいは成型品
の安定性、色相が低下するなど、その活性は充分
なものとは言えなかつた。
立体規則性を向上させる為には、重合中に電子
供与性化合物を第３成分として添加することが効
果的であることが一般に知られている。しかしな
がら、立体規則性と活性とはしばしば相反する挙
動を示し、電子供与性化合物を第３成分として添
加することによつて立体規則性は向上するが、活
性が大巾に低下するというのが常であつた。
そこで本発明者等は、そのような欠点を解決す
べく鋭意検討した結果、グリニヤール化合物と、
水、アルコール、シラノール及びポリシラノール
のうちから選ばれた少くとも１種の化合物とを反
応させて得られたマグネシウム化合物、四ハロゲ
ン化チタン並びにカルボン酸エステルを接触させ
て得られるチタン含有固体触媒成分と、有機アル
ミニウム化合物と、特定の第３成分とからなる触
媒系を用いて特定の重合条件にオレフインを多段
重合することにより、触媒の活性をより高くし、
オレフイン重合体の立体規則性を高く保持し、か
つオレフイン重合体の嵩密度を向上させ得ること
を見出し、本発明を達成した。
すなわち本発明の要旨は、
(A) (a) グリニヤール化合物と、水、アルコー
ル、シラノール及びポリシラノールのうちか
ら選ばれた少くとも１種の化合物とを、反応
させて得られたマグネシウム化合物、
(b) 四ハロゲン化チタン及び
(c) カルボン酸エステルを
接触させて得られるチタン含有固体触媒成分
と、
(B) 有機アルミニウム化合物と、
(C) カルボン酸エステル
とからなる触媒系を使用してオレフインを多段で
重合する方法であつて、１段目の重合条件を、
(A)チタン含有固体触媒成分中のチタンに対する
(B)有機アルミニウム化合物のモル比を２段目以
降におけるモル比よりも小さくし、
(C)カルボン酸エステルは使用しないか又は使用
する場合には(A)チタン含有固体触媒成分中のチ
タンに対する(C)カルボン酸エステルのモル比を
２段目以降におけるモル比よりも小さくし、
重合時間は２段目以降の重合時間の合計以下と
し、
１段目で生成するオレフイン重合体量を、(A)チ
タン含有固体触媒成分１グラム当り10000グラ
ム以下とし、且つ全体で生成するオレフイン重
合体量に対し重量比で0.6以下とすることを特
徴とするオレフイン重合体の製造方法に存す
る。
更に本発明を詳細に説明するに、本発明におい
て触媒の第１成分として用いられるチタン含有固
体触媒成分（以下においては、「(A)成分」と略称
する。）はマグネシウム化合物、四ハロゲン化チ
タン及びカルボン酸エステルを反応させて得られ
るものである。
(A)成分を製造するに用いられるこれら各成分に
ついて説明する。
(a) マグネシウム化合物
用いられるマグネシウム化合物は、グリニヤ
ール化合物と、水、アルコール、シラノール及
びポリシラノールのうちから選ばれた少くとも
１種の化合物とを反応させて得られるものであ
る。
ここで、グリニヤール化合物としては、一般
式R1MgX（式中、R1は炭化水素基を表わしＸ
はハロゲン原子を表わす。）で表わされるも
の、具体的には、R1が炭素数20までのアルキ
ル、アリール、アラルキル基等であるようなも
のが使用される。特に、R1がメチル、エチ
ル、プロピル、ブチル、アミル、ヘキシル等の
アルキル基、フエニル等のアリール基、ベンジ
ル等のアラルキル基であるようなものが好まし
い。また、Ｘとしては塩素、臭素、ヨウ素等が
挙げられる。これらのグリニヤール化合物は、
通常エーテル溶液またはエーテル付加体として
使用される。かかるエーテルとしては、ジエチ
ルエーテル、ジブチルエーテル、ジヘキシルエ
ーテル、ジオクチルエーテル、テトラヒドロフ
ラン等のエーテルが挙げられる。
アルコールとしては、多価アルコールであつ
てもよいが、通常は一般式、R2OH（式中R2は
炭化水素基を表わす）で表わされる一価のアル
コールが用いられる。具体的にはR2としては
炭素数20までの炭化水素基、例えばアルキル基
が挙げられる。例を挙げると、メチル、エチ
ル、プロピル、ブチル、アミル、ヘキシル、オ
クチル、２−エチルヘキシル、ノニル、デシル
等のアルキル基、である。
シラノールとしては、一般式、R3nSi
（OH）4-o（式中、R3は炭化水素基を表わし、ｎ
は１、２又は３）で表わされる。シラノール
は、例えば、次式に示すように、対応するハロ
ゲン化物を加水分解することによつて容易に合
成することができる。
（C6H5）3SiCl＋H2O→（C6H5）3SiOH＋
HCl
具体的には、R3としては炭素数20までのアル
キル、シクロアルキル、シクロアルケニル、ア
リール、アラルキル、アルカリール及びシクロ
アラルキル基等が挙げられる。特に、メチル、
エチル、プロピル、ブチル、アミル、ヘキシ
ル、ヘプチル、オクチル、デシル等のアルキル
基、フエニル等のアリール基、ベンジル等のア
ラルキル基が好ましい。また、ｎは１、２又は
３をとりうるが、シラノールの安定性からみて
ｎが３のもの、ｎが２でR3がアリール基のも
のが好ましい。
ポリシラノールとしては、シラノールＲ４ ２Si
（OH）2又はR4Si（OH）3（式中、R4は炭化水素
基を表わす。）が縮合した、シロキサン結合を
有する化合物であり、その構造については、鎖
状、環状、三次元網目構造などいずれであつて
もよいが、ヒドロキシル基含有量については、
少くとも１分子当り１個以上のヒドロキシル基
を有するものが用いられる。ポリシラノール中
のヒドロキシル基含有量が４〜14m mol／ｇで
あるのが好ましい。このようなポリシラノール
は、例えば対応する有機ハロシランを適当な条
件下に加水分解することによつて容易に得るこ
とができる。例えば、一般式R4SiX3又はＲ４ ２
SiX2（式中、R4は炭化水素基を表わし、Ｘは
ハロゲン原子を表わす。）で示される有機トリ
ハロシラン及び／又は有機ジハロシランの１種
又は２種以上をヘプタン、シクロヘキサン、ベ
ンゼン、トルエンのような不活性炭化水素溶媒
中−50℃〜100℃、好ましくは、−50℃〜20℃付
近の温度で、有機ハロシラン中のハロゲンに対
し当量以上の水又はアルカリ水溶液と反応さ
せ、次いで得られた溶液を洗液が中性になる迄
水洗し、乾燥することにより、ポリシラノール
の溶液を得ることができる。この際ポリシラノ
ールの重合度は加水分解温度、アルカリ濃度に
より制御することができる。この溶液から溶媒
を留去してポリシラノールを単離して用いても
よいが、溶液をそのまま用いてもよい。またポ
リシラノールは、一般式Ｒ４ ２Si（OH）2（式中、
R4は炭化水素基を表わす。）で表わされるシラ
ノールの１種又は２種以上を、望ましくはアル
コール中でアルカリ存在下に50℃以上に加熱す
ることで容易に目的とするポリシラノールを得
ることができる。ポリシラノール、有機トリハ
ロシラン、有機ジハロシラン及びシラノールの
前示一般式中のR4としては、炭素数20までの
アルキル、シクロアルキル、シクロアルケニ
ル、アリール、アラルキル、アルカリール及び
シクロアラルキル基等が挙げられる。特に、メ
チル、エチル、プロピル、ブチル、アミル、ヘ
キシル、ヘプチル、オクチル、デシル等のアル
キル基、フエニル等のアリール基、ベンジル等
のアラルキル基が好ましい。
グリニヤール化合物と、水、アルコール、シ
ラノール及びポリシラノールのうちから選ばれ
た少くとも１種の化合物との反応は、−50〜100
℃で両成分を接触させ、次いで20〜200℃、好
ましくは、20〜150℃、とくに好ましくは、50
〜80℃で数時間反応させることによつておこな
われる。両成分の使用割合は、水又はアルコー
ルの場合には、水又はアルコール／グリニヤー
ル化合物中のMg−Ｃ結合の比（モル比）で
0.01〜２、好ましくは0.5〜1.5であり、シラノ
ール又はポリシラノールの場合には、シラノー
ル又はポリシラノール中のヒドロキシル基／グ
リニヤール化合物中のMg−Ｃ結合の比（モル
比）で0.1〜10好ましくは１〜２である。接触
反応は、溶媒中でおこなうことが好ましく、例
えば水は、ジエチルエーテル、ジブチルエーテ
ル、テトラヒドロフラン等のエーテル溶媒に溶
解して、アルコール、シラノール及びポリシラ
ノールは、ベンゼン、トルエン等の芳香族炭化
水素、ｎ−ヘプタン、ｎ−ヘキサン等の飽和脂
肪族炭化水素、シクロヘキサン、メチルシクロ
ヘキサン等の脂環式炭化水素、ジエチルエーテ
ル、ジブチルエーテル等のエーテルに溶解し
て、反応させる。接触反応後得られた反応混合
物は、そのまま用いてもよいが、反応混合物か
ら過又は傾瀉により固体を分解して或は気化
により未反応物又は溶媒を除去してのち、用い
てもよい。
(b) 四ハロゲン化チタン
四塩化チタル、四臭化チタン、四ヨウ化チタ
ン等が挙げられるが、特に、四塩化チタンが好
ましい。
(c) カルボン酸エステル
カルボン酸エステルにおいては、カルボン酸
残基の炭化水素基はアミノ基、アルコキシ基の
ような置換基を有していてもよい。そのような
例としては、アミノ酸エステルが挙げられる。
カルボン酸エステルの具体例は、安息香酸メチ
ル、安息香酸エチル、安息香酸プロピル、安息
香酸ブチル、安息香酸フエニル、ｐ−メトキシ
安息香酸メチル、ｐ−メトキシ安息香酸エチ
ル、ｐ−メトキシ安息香酸プロピル、ｍ−メト
キシ安息香酸ブチル、ｏ−メトキシ安息香酸フ
エニル、ｐ−トルイル酸メチルエステル、ｐ−
トルイル酸エチル、ｐ−エチル安息香酸エチ
ル、ｐ−エチル安息香酸プロピル、ｐ−ブチル
安息香酸エチル、ｐ−ブチル酸安息香酸ブチ
ル、ｐ−エトキシ安息香酸メチル、ｐ−エトキ
シ安息香酸エチル、酢酸フエニル、プロピオン
酸フエニル、クロトン酸エチル、クロトン酸プ
ロピル、クロトン酸ブチル、ケイ皮酸エチル、
ケイ皮酸ブロピル、ケイ皮酸ブチル、ジメチル
グリシンエチルエステル、ジメチルグリシンプ
ロピルエステル、ジメチルグリシンブチルエス
テル、ジフエニルグリシンエチルエステル、ジ
フエニルグリシンブチルエステル、ｐ−ジメチ
ルアミノ安息香酸エチルエステル、が挙げられ
る。
しかして、本発明においては、上記(a)、(b)及び
(c)成分を適宜の順序で接触させてチタン含有固体
触媒成分を得る。しかし、好ましい方法は次の
(イ)、(ロ)及び(ハ)である。
(イ) (a)マグネシウム化合物に、(c)カルボン酸エス
テルを添加して処理し、次いで(b)四ハロゲン化
チタンで処理する方法。
(ロ) (a)マグネシウム化合物を(b)四ハロゲン化チタ
ンで処理すると同時に或いは処理後(c)カルボン
酸エステルで処理する方法。
(ハ) (c)カルボン酸エステルの存在下に(a)マグネシ
ウム化合物を合成し、次いで(b)四ハロゲン化チ
タンで処理する方法。
これら(a)、(b)及び(c)成分を接触させる方法に於
て、接触条件は無溶媒でもよく、また適当な溶媒
で希釈した溶液状態でもよい。溶媒としては、ベ
ンゼン、トルエン等の芳香族炭化水素、ｎ−ペン
タン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタ
ン、ｎ−デカン、流動パラフイン等の飽和脂肪族
炭化水素、シクロヘキサン、メチルシクロヘキサ
ン等の脂環式炭化水素、ジエチルエーテル、ジブ
チルエーテル等のエーテルなどが挙げられる。
更に具体的に、チタン含有固体触媒成分の調製
方法を、上記(イ)〜(ハ)の場合について説明する。
(イ) (a)成分のマグネシウム化合物に、例えば−50
℃〜100℃で(c)成分のカルボン酸エステル又は
その溶液を添加し、次いで好ましくは、60℃〜
200℃に昇温して、さらに0.1時間以上、好まし
くは0.1〜10時間、特に好ましくは１〜５時間
処理する。処理は溶媒中でおこなわれることが
好ましい。このような溶媒としては、トルエ
ン、キシレン等の芳香族炭化水素、ヘキシン、
ヘプタン等の脂肪族炭化水素が用いられる。次
いで、反応混合物そのまま或は過、傾瀉によ
り固体成分を得て或いは気化により未反応物、
溶媒を除去したのち、(b)成分の四ハロゲン化チ
タンを添加し、60〜300℃好ましくは100℃〜
200℃で0.01時間以上好ましくは0.05〜10時間
処理する。この処理も上述と同様な溶媒中でお
こなうことも可能である。処理後、反応混合物
から固体触媒成分を分離し、次いで不活性炭化
水素溶媒で洗浄する。
(ロ) 上記(イ)と同様にして、(a)成分のマグネシウム
化合物を(b)成分の四ハロゲン化チタンで処理す
ると同時に或いは処理後(c)成分のカルボン酸エ
ステルで処理し、分離、洗浄する。
(ハ) (c)成分のカルボン酸エステルの存在下に(a)成
分のマグネシウム化合物を調製する。この場
合、(a)成分のマグネシウム化合物の生成反応が
おきるまえにグリニヤール化合物とカルボン酸
エステルが反応しないようにするのが好まし
い。従つて低温たとえば−30℃〜室温で(a)成分
のマグネシウム化合物を生成させ次いで60〜
200℃に昇温して、(a)成分のマグネシウム化合
物と(c)成分のカルボン酸エステルとを反応させ
る。次いで反応混合物そのまま或は固体成分を
分離後、(イ)と同様にして(b)成分の四ハロゲン化
チタンで処理し、分離洗浄する。しかして、こ
れら(a)、(b)及び(c)成分の使用量は次の範囲から
選ばれる。
(c)カルボン酸エステル／(a)マグネシウム原子＝
0.01〜10
好ましくは 0.05〜２（モル比）
(b) 四ハロゲン化チタン／(a)マグネシウム原子＝
0.1〜50
好ましくは １〜30（モル比）
かくして、チタン含量0.1〜20重量％、好ましく
は0.1〜10重量％のチタン含有固体触媒成分を得
ることができ、前述したようにこれを不活性炭化
水素溶媒で洗浄して、オレフインの重合に供す
る。不活性炭化水素溶媒としては、ベンゼン、ト
ルエン等の芳香族炭化水素、ｎ−ベンゼン、ｎ−
ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−ド
デカン、流動パラフイン等の飽和脂肪族炭化水
素、シクロヘキサン、メチルシクロヘキサン等の
脂環式炭化水素等が使用される。
次に、助触媒としての有機アルミニウム化合物
〔以下において「(B)成分(チ)と略称する。〕として
は、例えば、一般式AlR5mX3−ｍ（式中R3は炭
素数１〜８のアルキル基を表わし、R5が２個以
上あるときは、それぞれ異つていてもよい。ｍは
１〜３の数、Ｘはハロゲン原子を示す。）で表わ
されるものが使用される。特に、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
プチルアルミニウム、トリヘキシルアルミニウ
ム、トリオクチルアルミニウム等のトリアルキル
アルミニウムが好ましい。
しかして、本発明は、前記(A)成分のチタン含有
固体触媒成分と上記(B)成分の有機アルミニウム化
合物に更に第３成分としてカルボン酸エステル
（以下において「(C)成分」と略称する。）を加えた
触媒系を用いてオレフインを重合する。このよう
なカルボン酸エステルとしては、鎖式カルボン酸
エステル、芳香族カルボン酸エステル、カルボン
酸残基の炭化水素基にアミノ基、アルコキシ基の
ような置換基があるエステル（例えば、アミノ酸
エステル等が用いられるが、好ましくは一般式
The present invention relates to a method for producing an olefin polymer. More specifically, the present invention involves the multistage polymerization of olefins such as ethylene, propylene, and putene-1 in the presence of a catalyst system that combines a supported catalyst component with high polymerization activity, an organoaluminum compound, and a carboxylic acid ester. The present invention relates to a method for producing an olefin polymer. Hitherto, various supported catalysts for olefin polymerization have been proposed which provide polymers with high polymerization activity and high stereoregularity. For example, JP-A-47-9342, JP-A-48-
16986, 50-108385, 51-57789 and 51-
No. 20297 proposes the use of a solid catalyst obtained by contacting a magnesium halide, a titanium halide, and an electron-donating compound for the polymerization of α-olefin. The present inventors also previously discovered that a Grignard compound, water, alcohol,
It was proposed to use a solid catalyst component obtained by contacting a titanium halide and an electron-donating compound with a magnesium compound obtained by reacting silanol or polysilanol, etc. for the polymerization of α-olefin. Although these catalysts are highly active and give polymers with high stereoregularity, the amount of by-product amorphous polymer is not sufficiently small, and this means that the crystalline polymer is separated from the raw material monomer. This brings about unfavorable results, such as a low conversion rate to amorphous polymers, or deterioration of the slurry state due to the amorphous polymer. Furthermore, if this amorphous polymer is not removed, the stereoregularity of the polymer cannot be said to be sufficient, as the mechanical properties of injection molded polymers, extrusion molded products, films, etc. are insufficient. Furthermore, if the catalyst components remaining in the polymer are not removed, the remaining catalyst components (particularly halogens) may cause corrosion of the molding equipment, or the stability and color of the molded product may deteriorate, resulting in insufficient activity. I couldn't say it. In order to improve the stereoregularity, it is generally known that it is effective to add an electron-donating compound as a third component during polymerization. However, stereoregularity and activity often exhibit contradictory behavior, and although stereoregularity is improved by adding an electron-donating compound as a third component, activity is usually significantly reduced. It was hot. Therefore, as a result of intensive study to solve such drawbacks, the present inventors have developed a Grignard compound and
A titanium-containing solid catalyst component obtained by contacting a magnesium compound obtained by reacting with at least one compound selected from water, alcohol, silanol, and polysilanol, titanium tetrahalide, and a carboxylic acid ester. By performing multi-stage polymerization of olefin under specific polymerization conditions using a catalyst system consisting of an organoaluminium compound and a specific third component, the activity of the catalyst is increased,
The present invention was achieved by discovering that it is possible to maintain high stereoregularity of an olefin polymer and to improve the bulk density of the olefin polymer. That is, the gist of the present invention is as follows: (A) (a) A magnesium compound obtained by reacting a Grignard compound with at least one compound selected from water, alcohol, silanol, and polysilanol; Olefin production using a catalyst system consisting of a titanium-containing solid catalyst component obtained by contacting b) titanium tetrahalide and (c) a carboxylic acid ester, (B) an organoaluminum compound, and (C) a carboxylic acid ester. This is a multi-stage polymerization method in which the first stage polymerization conditions are: (A) relative to titanium in the titanium-containing solid catalyst component;
(B) The molar ratio of the organoaluminum compound is made smaller than the molar ratio in the second and subsequent stages, and (C) the carboxylic acid ester is not used, or if used, (A) the titanium in the titanium-containing solid catalyst component is (C) The molar ratio of the carboxylic acid ester is made smaller than the molar ratio in the second and subsequent stages, the polymerization time is less than or equal to the total polymerization time in the second and subsequent stages, and the amount of olefin polymer produced in the first stage is A) A method for producing an olefin polymer, characterized in that the amount is 10,000 grams or less per gram of the titanium-containing solid catalyst component, and the weight ratio is 0.6 or less relative to the total amount of olefin polymer produced. To further explain the present invention in detail, the titanium-containing solid catalyst component (hereinafter abbreviated as "component (A)") used as the first component of the catalyst in the present invention is a magnesium compound, titanium tetrahalide. and a carboxylic acid ester. Each of these components used to produce component (A) will be explained. (a) Magnesium Compound The magnesium compound used is obtained by reacting a Grignard compound with at least one compound selected from water, alcohol, silanol, and polysilanol. Here, the Grignard compound has the general formula R 1 MgX (wherein R 1 represents a hydrocarbon group and
represents a halogen atom. ), specifically, those in which R 1 is an alkyl, aryl, aralkyl group, etc. having up to 20 carbon atoms are used. Particularly preferred are those in which R 1 is an alkyl group such as methyl, ethyl, propyl, butyl, amyl, hexyl, etc., an aryl group such as phenyl, or an aralkyl group such as benzyl. Moreover, examples of X include chlorine, bromine, and iodine. These Grignard compounds are
Usually used as an ether solution or ether adduct. Such ethers include ethers such as diethyl ether, dibutyl ether, dihexyl ether, dioctyl ether, and tetrahydrofuran. The alcohol may be a polyhydric alcohol, but usually a monohydric alcohol represented by the general formula R 2 OH (wherein R 2 represents a hydrocarbon group) is used. Specifically, R 2 includes a hydrocarbon group having up to 20 carbon atoms, such as an alkyl group. Examples include alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, and the like. As a silanol, the general formula, R 3 nSi
(OH) 4-o (wherein R 3 represents a hydrocarbon group, n
is represented by 1, 2 or 3). Silanol can be easily synthesized, for example, by hydrolyzing a corresponding halide, as shown in the following formula. (C 6 H 5 ) 3 SiCl+H 2 O→(C 6 H 5 ) 3 SiOH+
HCl Specifically, R 3 includes alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl, and cycloaralkyl groups having up to 20 carbon atoms. In particular, methyl
Preferred are alkyl groups such as ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, and decyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. Furthermore, n can be 1, 2, or 3, but in view of the stability of the silanol, it is preferable that n is 3, or that n is 2 and R 3 is an aryl group. As the polysilanol, silanol R 4 2 Si
(OH) 2 or R 4 Si(OH) 3 (in the formula, R 4 represents a hydrocarbon group) is a condensed compound having a siloxane bond, and its structure can be linear, cyclic, or three-dimensional. It may have any structure such as a network structure, but regarding the hydroxyl group content,
Those having at least one hydroxyl group per molecule are used. It is preferred that the hydroxyl group content in the polysilanol is 4 to 14 mmol/g. Such polysilanols can be easily obtained, for example, by hydrolyzing the corresponding organic halosilane under appropriate conditions. For example, general formula R 4 SiX 3 or R 4 2
SiX 2 (In the formula, R 4 represents a hydrocarbon group and The organic halosilane is reacted with water or an aqueous alkali solution in an amount equivalent to or more of the halogen in the organohalosilane at a temperature of -50°C to 100°C, preferably around -50°C to 20°C, in an inert hydrocarbon solvent such as A polysilanol solution can be obtained by washing the solution with water until the washing liquid becomes neutral and drying. At this time, the degree of polymerization of polysilanol can be controlled by the hydrolysis temperature and alkali concentration. The polysilanol may be isolated and used by distilling off the solvent from this solution, or the solution may be used as it is. Moreover, polysilanol has the general formula R 4 2 Si(OH) 2 (wherein,
R 4 represents a hydrocarbon group. The desired polysilanol can be easily obtained by heating one or more of the silanols represented by ) to 50° C. or higher, preferably in an alcohol in the presence of an alkali. R 4 in the above general formula of polysilanol, organic trihalosilane, organic dihalosilane and silanol includes alkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkaryl and cycloaralkyl groups having up to 20 carbon atoms. . Particularly preferred are alkyl groups such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, and decyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. The reaction between the Grignard compound and at least one compound selected from water, alcohol, silanol, and polysilanol is -50 to 100
Both components are brought into contact at a temperature of 20-200°C, preferably 20-150°C, particularly preferably 50°C.
This is done by reacting at ~80°C for several hours. In the case of water or alcohol, the ratio of both components used is the ratio (molar ratio) of Mg-C bonds in the water or alcohol/Grinard compound.
0.01 to 2, preferably 0.5 to 1.5, and in the case of silanol or polysilanol, the ratio (mole ratio) of hydroxyl group in silanol or polysilanol/Mg-C bond in Grignard compound is preferably 0.1 to 10. 1 to 2. The catalytic reaction is preferably carried out in a solvent; for example, water is dissolved in an ether solvent such as diethyl ether, dibutyl ether, tetrahydrofuran, etc., and alcohol, silanol, and polysilanol are dissolved in an aromatic hydrocarbon such as benzene, toluene, etc. It is dissolved in saturated aliphatic hydrocarbons such as n-heptane and n-hexane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and ethers such as diethyl ether and dibutyl ether, and reacted. The reaction mixture obtained after the contact reaction may be used as it is, but it may also be used after decomposing solids from the reaction mixture by evaporation or decantation, or removing unreacted substances or solvent by vaporization. (b) Titanium tetrahalide Examples include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, and titanium tetrachloride is particularly preferred. (c) Carboxylic acid ester In the carboxylic acid ester, the hydrocarbon group of the carboxylic acid residue may have a substituent such as an amino group or an alkoxy group. Such examples include amino acid esters.
Specific examples of carboxylic acid esters include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, methyl p-methoxybenzoate, ethyl p-methoxybenzoate, propyl p-methoxybenzoate, m -butyl methoxybenzoate, phenyl o-methoxybenzoate, p-toluic acid methyl ester, p-
Ethyl toluate, ethyl p-ethylbenzoate, propyl p-ethylbenzoate, ethyl p-butylbenzoate, butyl p-butyrate benzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, phenyl acetate, Phenyl propionate, ethyl crotonate, propyl crotonate, butyl crotonate, ethyl cinnamate,
Examples include propyl cinnamate, butyl cinnamate, dimethylglycine ethyl ester, dimethylglycine propyl ester, dimethylglycine butyl ester, diphenylglycine ethyl ester, diphenylglycine butyl ester, and p-dimethylaminobenzoic acid ethyl ester. Therefore, in the present invention, the above (a), (b) and
The components (c) are brought into contact in an appropriate order to obtain a titanium-containing solid catalyst component. However, the preferred method is as follows
(a), (b) and (c). (a) A method in which (a) a magnesium compound is treated by adding (c) a carboxylic acid ester, and then (b) treated with titanium tetrahalide. (b) A method in which (a) a magnesium compound is treated with (b) titanium tetrahalide and (c) a carboxylic acid ester at the same time or after the treatment. (c) A method in which (a) a magnesium compound is synthesized in the presence of a carboxylic acid ester, and then (b) is treated with titanium tetrahalide. In the method of bringing these components (a), (b) and (c) into contact, the contacting conditions may be in the absence of a solvent or in a solution state diluted with an appropriate solvent. Examples of solvents include aromatic hydrocarbons such as benzene and toluene, saturated aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, and liquid paraffin, and cyclohexane and methylcyclohexane. Examples include alicyclic hydrocarbons and ethers such as diethyl ether and dibutyl ether. More specifically, the method for preparing the titanium-containing solid catalyst component will be described for cases (a) to (c) above. (a) For example, -50
The carboxylic acid ester of component (c) or its solution is added at a temperature of 100°C to 100°C, and then preferably 60°C to 100°C.
The temperature is raised to 200°C, and the treatment is further carried out for 0.1 hour or more, preferably 0.1 to 10 hours, particularly preferably 1 to 5 hours. Preferably, the treatment is carried out in a solvent. Such solvents include aromatic hydrocarbons such as toluene and xylene, hexene,
Aliphatic hydrocarbons such as heptane are used. Next, the reaction mixture may be used as it is, or solid components may be obtained by filtration or decantation, or unreacted substances may be removed by vaporization.
After removing the solvent, add component (b), titanium tetrahalide, and heat at 60 to 300°C, preferably 100°C to
Process at 200°C for 0.01 hour or more, preferably 0.05 to 10 hours. This treatment can also be carried out in the same solvent as described above. After treatment, the solid catalyst component is separated from the reaction mixture and then washed with an inert hydrocarbon solvent. (b) In the same manner as in (a) above, the magnesium compound (a) is treated with the titanium tetrahalide (b) component and at the same time or after the treatment is treated with the carboxylic acid ester (c) component, and separated. Wash. (c) A magnesium compound as component (a) is prepared in the presence of a carboxylic acid ester as component (c). In this case, it is preferable to prevent the Grignard compound from reacting with the carboxylic acid ester before the reaction for producing the magnesium compound (a) takes place. Therefore, the magnesium compound of component (a) is produced at a low temperature, for example, from -30°C to room temperature, and then at 60°C to room temperature.
The temperature is raised to 200°C, and the magnesium compound (a) component and the carboxylic acid ester (c) component are reacted. Next, the reaction mixture as it is or after separating the solid component is treated with titanium tetrahalide as component (b) in the same manner as in (a), and separated and washed. Therefore, the amounts of these components (a), (b) and (c) to be used are selected from the following ranges. (c) Carboxylic acid ester / (a) Magnesium atom =
0.01-10 preferably 0.05-2 (molar ratio) (b) Titanium tetrahalide/(a) Magnesium atom =
0.1-50 Preferably 1-30 (molar ratio) Thus, a titanium-containing solid catalyst component having a titanium content of 0.1-20% by weight, preferably 0.1-10% by weight can be obtained, which is inertly carbonized as described above. It is washed with a hydrogen solvent and used for olefin polymerization. Examples of inert hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene, n-benzene, n-
Saturated aliphatic hydrocarbons such as hexane, n-heptane, n-octane, n-dodecane, and liquid paraffin, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are used. Next, as an organoaluminum compound [hereinafter abbreviated as "(B) component (H)]" as a cocatalyst, for example, the general formula AlR 5 mX 3 -m (wherein R 3 is a carbon number of 1 to 8 and when there are two or more R 5 s, they may be different. m is a number from 1 to 3, and X represents a halogen atom. , triethylaluminum, tripropylaluminum, triisoptylaluminum, trihexylaluminum, trioctylaluminum, and the like are preferred.The present invention provides a method for combining the titanium-containing solid catalyst component of component (A) with the titanium-containing solid catalyst component of component (B). Olefin is polymerized using a catalyst system in which a carboxylic acid ester (hereinafter abbreviated as "component (C)") is further added as a third component to an organoaluminum compound as component (). Such carboxylic esters include chain carboxylic esters, aromatic carboxylic esters, and esters in which the hydrocarbon group of the carboxylic acid residue has a substituent such as an amino group or an alkoxy group (for example, amino acid esters, etc.). used, but preferably the general formula
【式】（式中、R6は水素又はメ
トキシ、エトキシ、プロポキシ、ブトキシ等の炭
素数１〜４のアルコキシ基又はメチル、エチル、
プロピル、ブチル、ペンチル、ヘキシル、ヘプチ
ル、オクチル等の炭素数１〜10のアルキル基を示
し、R7はメチル、エチル、プロピル、ブチル、
ペンチル、ヘキシル、ヘプチル、オクチル等の炭
素数１〜10のアルキル基又はフエニル、トルイル
等の炭素数12以下のアリール基を示す。）で表わ
される化合物が用いられる。カルボン酸エステル
の例としては、安息香酸メチル、安息香酸エチ
ル、安息香酸プロピル、安息香酸ブチル、安息香
酸フエニル、Ｐ−メトキシ安息香酸メチル、ｐ−
メトキシ安息香酸エチル、ｐ−メトキシ安息香酸
プロピル、ｍ−メトキシ安息香酸ブチル、ｏ−メ
トキシ安息香酸フエニル、ｐ−エトキシ安息香酸
メチル、ｐ−エトキシ安息香酸エチル、酢酸フエ
ニル、プロピオン酸フエニル、アクリル酸エチ
ル、メタクリル酸メチル、クロトン酸エチル、ク
ロトン酸プロピル、クロトン酸ブチル、ケイ皮酸
エチル、ケイ皮酸プロピル、ケイ皮酸ブチル、ジ
メチルグリシンエチルエステル、ジメチルグリシ
ンプロピルエステル、ジメチルグリシンブチルエ
ステル、ジフエニルグリシンエチルエステル、ジ
フエニルグリシンプロピルエステル、ジフエニル
グリシンブチルエステル、ｐ−ジメチルアミノ安
息香酸エチルエステル、ｐ−トルイル酸メチル、
ｐ−トルイル酸エチル、ｐ−トルイル酸プロピ
ル、ｐ−トルイル酸ブチル、ｐ−トルイル酸ヘキ
シル、ｐ−トルイル酸オクチル、ｐ−エチル安息
香酸メチル、ｐ−エチル安息香酸エチル、ｐ−エ
チル安息香酸プロピル、ｐ−エチル安息香酸ブチ
ル、ｐ−エチル安息香酸ヘキシル、ｐ−エチル安
息香酸オクチル、ｐ−ブチル安息香酸メチル、ｐ
−ブチル安息香酸エチル、ｐ−ブチル安息香酸プ
ロピル、ｐ−ブチル安息香酸ブチル、ｐ−ブチル
安息香酸ヘキシル、ｐ−ブチル安息香酸オクチ
ル、ｐ−ヘキシル安息香酸メチル、ｐ−ヘキシル
安息香酸エチル、ｐ−ヘキシル安息香酸プロピ
ル、ｐ−ヘキシル安息香酸ブチル、ｐ−ヘキシル
安息香酸ヘキシル、ｐ−ヘキシル安息香酸オクチ
ル、ｐ−オクチル安息香酸メチル、ｐ−オクチル
安息香酸エチル、ｐ−オクチル安息香酸プロピ
ル、ｐ−オクチル安息香酸ブチル、ｐ−オクチル
安息香酸ヘキシル、ｐ−オクチル安息香酸オクチ
ル等が挙げられる。
触媒を調整するに際しての(A)成分、(B)成分及び
(C)成分の添加順序は、とくに制限はなく、(A)成分
と(B)成分の混合系に(C)成分を添加する方法もしく
はその逆の方法、(A)成分と(C)成分の混合系に(B)成
分を添加する方法もしくはその逆の方法、(B)成分
と(C)成分の混合系に(A)成分を添加する方法もしく
はその逆の方法、或いは(A)成分、(B)成分、(C)成分
を同時に混合する方法などいずれでもよい。
しかして、本発明方法においては、上記３成分
系触媒を使用してオレフインを多段で重合し、し
かもその際の一段目の重合条件を下記の(1)〜(4)を
満足するように定める。
(1) (A)成分中のチタンに対する(B)成分のモル比
（以下、(B)／(A)と略称する）を２段目以降の
(B)／(A)に比較して小さくする。
(2) (C)成分は使用しないか、又は使用する場合で
も(A)成分中のチタンに対する(C)成分のモル比
（以下、(C)／(A)と略称する）を２段目以降の
(C)／(A)に比較して小さくする。
(3) 重合時間は２段目以降の重合時間の合計以下
とする。
(4) １段目で生成するオレフイン重合体量を(A)成
分１グラム当り10000グラム以下、例えば１〜
10000グラム、好ましくは５〜5000グラムで且
つ全段で生成するオレフイン重合体量に対し重
量比で0.6以下とする。
１段目の(B)／(A)が２段目以降の(B)／(A)に比較し
て大きくなると、得られたオレフイン重合体の立
体規則性が低下する。従つて１段目の(B)／(A)は２
段目以降の(B)／(A)に比較して0.1以上小さいこと
が好ましい。
また１段目の(C)／(A)が２段目以降の(C)／(A)に比
較して大きくなると、触媒の重合活性が低下す
る。従つて１段目の(C)／(A)は２段目以降の(C)／(A)
に比較して0.1以上小さいことが好ましい。
なお、本明細書において２段目以降の各段にお
ける(A)〜(C)の各成分の使用量は、前段までの使用
量に当該段における使用量を加算したものとして
定義される。
具体的に各成分の使用比率を例示すると、(B)成
分の使用量は(A)成分のチタン1mol当りで示せ
ば、１段目は0.5〜100mol好ましくは１〜20mol
の範囲から選ばれ、２段目以降は１段目より多く
１〜1000mol好ましくは10〜300molの範囲から選
ばれる。また(C)成分の使用量は同様に(A)成分のチ
タン1mol当りで示せば、１段目は０〜2.0mol好
ましくは０〜1.0molの範囲から選ばれ、２段目以
降は１段目より多く0.1〜200mol好ましくは１〜
10molの範囲から選ばれ、かつ(C)成分の使用量は
(B)成分1mol当り１段目が０〜0.1molで、２段目
以降が0.1〜0.3molの範囲から選ばれる。この
際、(B)成分に対する(C)成分のモル比（以下、(C)／
(B)と略称する）については、１段目の(C)／(B)が２
段目以降の(C)／(B)に比較して小さくなるように選
ばれることが好ましい。１段目の(C)／(B)の方が大
きくなると、触媒の重合活性が低下する。
重合温度は、１段目が０℃〜100℃好ましくは
20〜80℃、特に好ましくは25℃〜75℃から選ば
れ、２段目以降は30℃〜100℃好ましくは50〜80
℃の範囲から選ばれるが、好ましくは１段目の重
合温度は２段目以降の重合温度を超えないように
する。１段目の重合温度が２段目以降の重合温度
を超えると、触媒の重合活性が低下する。また重
合圧力は、通常0.1〜50気圧の範囲から選ばれ
る。重合時間は、１段目は１時間以下とすること
が好ましく、かつ２段目以降の重合時間の合計以
下とする。１段目の重合時間が２段目以降の重合
時間の合計を超えると、得られるオレフイン重合
体の立体規則性の低下をもたらし好ましくない。
更に１段目の重合で得られるオレフイン重合体
の生成量は、(A)成分１グラム当り10000グラム以
下、例えば１〜10000グラム、好ましくは５〜
5000グラムであり、かつ全体のオレフイン重合体
生成量に対し重量比で0.6以下となるようにす
る。前者が10000グラムを超えると、得られるオ
レフイン重合体の立体規則性が低下し後者が0.6
を超えると同様に立体規則性が低下する。
しかして、本発明方法においては、上記重合条
件下に、２段又は３段以上の多段で、オレフイン
を重合し、好適には(A)成分中のチタン単位グラム
当り50000グラム以上とくに100000グラム以上の
オレフイン重合体を製造する。２段で重合する際
の具体的な手法を例示すれば、先ず、前記３成分
系触媒を用いて前記重合条件下にオレフインを重
合し、次いで必要があれば昇温、昇圧してのち、
(B)成分及び(C)成分を追加添加して、更にオレフイ
ンを重合する。重合反応は、不活性炭化水素又は
液化プロピレン溶媒存在下での溶液重合、あるい
はスラリー重合、そして無溶媒下での気相重合等
の方式で、連続又はバツチ方式で行なわれる。ま
た重合帯域に水素を存在させることによつて、生
成する重合体の分子量を容易に調節することがで
きる。
使用されるオレフインとしては、エチレン、プ
ロピレン、ブテン−１等のα−オレフインが挙げ
られ、本発明になる触媒系を使用し、それらの単
独重合、２種以上のランダム共重合または同ブロ
ツク共重合などを行つて、有利にそれらのオレフ
イン重合体を得ることができる。本発明に係る触
媒系は、特に、高立体規則性重合体の製造に好適
であり、従つてプロピレンの単独重合体又は90重
量％以上のプロピレンと10重量％以下の他のα−
オレフインからなる共重合体の製造に好適であ
る。
以上詳述したように、本発明方法に従えば、立
体規則性の良好なオレフイン重合体を容易に得る
ことができる。そして得られたオレフイン重合体
の立体規則性が高いので、重合体からの非結晶性
重合体の除去を省略することができる。更に、本
発明で使用するチタン含有固体触媒成分は、本発
明の重合条件下では重合活性を高く保持するので
得られたオレフイン重合体からの触媒残留物除去
工程も省略できる利点がある。またポリマーの嵩
密度が向上し工業的に非常に有益である。更に本
発明方法によつて得られる重合体中のハロゲン含
有量は極めて少なく製品物性上のメリツトは極め
て大きい。
次に、本発明を実施例及び比較例を挙げて説明
するが、本発明はこれらによつて何ら限定される
ものではない。
なお、実施例および比較例において、アイソタ
クチツクインデツクス（以下「II」と略称する。
単位％）は、改良型ソツクスレー抽出器で沸騰ｎ
−ヘプタンで６時間抽出後の固体残留を乾燥し重
量％で表わした。また、メルトフロ−インデツク
ス（以下、「MFI」と略称する。単位ｇ／10分）
は、ASTM−D1238に準じて測定した値を示し
た。嵩密度（以下、ρBと略称する。）はJIS−
6721により測定した値を示した。
実施例 １
〔〕 ポリフエニルシラノールの合成
500mlの４つ口フラスコに純水3.2ｇとトルエ
ン170mlを入れ、反応容器は磁気撹拌しながら
−20℃に保冷した。このトルエン懸濁液にフエ
ニルトリクロロシラン25ｇ（0.118mol）の70ml
トルエン溶液を滴下ロートを用いて１時間で滴
下した。滴下終了後、反応混合物を０℃まで昇
温し、更に30分撹拌を継続した。次いで、氷水
で洗液が中性になるまで洗滌した。得られたト
ルエン溶液を無水硫酸ナトリウムで脱水乾燥
後、過し、その液を担体調製用の原料とし
て使用した。このトルエン溶液の水酸基濃度を
後述する方法によつて定量したところ8.1m
mol／ｇであつた。
上記ポリシラノールの水酸基の定量は次のよ
うに行つた。水酸基に対して過剰になるように
適当量のグリニヤール化合物を入れ100℃、１
時間加熱・撹拌して反応を完了せしめた。次に
使用したグリニヤール化合物のモル数だけベル
ジルプロミドを添加して100℃、１時間加熱撹
拌を継続した。次いで、反応容器を室温に戻し
てから純水を加えて加水分解し、得られたアル
カリ成分を適当な指示薬の共存下で塩酸又は硫
酸で滴定した。この場合には指示薬としてフエ
ノールフタレンアルコール溶液を、酸としては
0.1N塩酸水溶液を用いた。
〔〕 チタン含有固体触媒成分の調製
乾燥窒素置換した500mlの四つ口フラスコ
に、〔〕で合成したポリフエニルシラノール
の水酸基当り0.34mol／のトルエン溶液130ml
を仕込み、これに3.9mol／の塩化−ｎ−ブチ
ルマグネシウムのジ−ｎ−ブチルエーテル溶液
11.3mlを25℃にて充分撹拌下にゆつくり滴下し
た。滴下終了後、110℃にて１時間撹拌し熟成
した。
次いでトルエン及びジ−ｎ−ブチルエーテル
を減圧留去、乾燥して白色粉末を得た。次いで
粉末を撹拌下に135℃に昇温して四塩化チタン
840m molを添加し四塩化チタン還流下で次い
で2mol／のｐ−トルイル酸メチルエステル
のトルエン溶液を4.4ml添加した。135℃で１時
間撹拌処理を行い約70℃に冷却後、ｎ−ヘプタ
ン200mlを添加し沈澱物を上澄液より分離し
た。ｎ−ヘプタン200mlで６回同様に行い洗浄
し淡黄褐色固体を得た。得られた固体のチタン
含有率は2.7％でありCl含有率は39.2％であつ
た。
〔〕 オレフインの重合
上記〔〕で調製した触媒成分を用いて、オ
レフインの２段重合を下記の手法で行つた。
乾燥窒素置換した500ml四つ口フラスコにｎ
−ヘプタン300ml、トリエチルアルミニウム50
μmol及び上記〔〕で調製したチタン含有固
体触媒成分30.1mgを仕込んだ。
次いで、撹拌下32℃で、常圧でプロピレンガ
スを導入した。32℃でプロピレンを５分間流通
後、脱酸素、脱水した精製窒素でプロピレンを
置換し、70℃に昇温後、トリエチルアルミニウ
ム190μmol及びｐ−トルイル酸メチルエステ
ル30μmolを添加し直ちにプロピレンを常圧で
流通し２時間重合を行つた後、少量のメタノー
ルを添加して重合を停止した。内容物をメタノ
ール中に注入した後、分離、乾燥して白色粉末
状ポリプロピレン23.8ｇを得た。重合活性はＫ
T1〔ポリマー（ｇ）／チタン（ｇ）・時間
（hr）・プロピレン圧（Kg／cm）、以下において
も同意義を有する。〕は24，400でありIIは96.6
％であつた。
尚１段目の重合でのポリマー生成量はチタン
含有固体触媒成分１ｇ当り16.4ｇであつた。１
段目ポリマー量／全体ポリマー量は0.02であつ
た。
比較例 １
実施例１の〔〕に於て、１段で重合を行なつ
た。
即ち、同一装置でｎ−ヘプタン300ml、トリエ
チルアルミニウム240μmol、ｐ−トルイル酸エ
チルエステル30μmol及び実施例１の〔〕で得
たチタン含有固体触媒成分30.1mgを仕込み、撹拌
下、70℃に昇温後、常圧でプロピレンガスを導入
し２時間重合し、以下、実施例１と同様にして重
合したところ、
ＫT1＝17，640、II＝94.4％であつた。
実施例 ２
実施例１の〔〕で得たチタン含有固体触媒成
分を用いて高圧重合を行なつた。触媒供給管２本
を内装した２電磁誘導式撹拌器を有するオート
クレーブを充分に乾燥アルゴン置換した。オート
クレーブ中にｎ−ヘキサン0.35を入れ、次いで
これにトリエチルアルミニウム127μmol及びｐ
−トルイル酸エチルエステル6.4μmolを加えた。
触媒供給管２本中、１本に実施例１の〔〕で得
た触媒22.5mgを含むｎーヘキサンスラリーを入
れ、残り１本にｎーヘキサンスラリーで稀釈した
トリエチルアルミニウム720μmolとｐ−トルイ
ル酸エチルエステル122μmolを入れた。次いで
撹拌下、オートクレーブを60℃に昇温し、チタン
含有固体触媒成分をオートクレーブ内に供給後、
直ちにプロピレンを供給しその圧力17Kg／cm2（ゲ
ージ）に保ち重合を開始した。60℃で20分重合後
直ちに供給管よりトリエチルアルミニウムとｐ−
トルイル酸エチルエステルのｎ−ヘキサン混合液
をオートクレーブ内に供給し、同温度で同一プロ
ピレン圧力で40分重合を続けた。次いで少量のメ
タノールを添加して重合を停止し、未反応モノマ
ーをパージ後、内容物を全てバツトに取り出し乾
燥して白色粉末状ポリプロピレン316ｇを得た。
得られたポリプロピレンのチタン含有固体触媒成
分１グラム当りのポリマー生成量（グラム）（以
下、CECATと略す）は14，040であり同じくチタ
ン１グラム当りのポリマー生成量（グラム）（以
下、CET1と略す）は520，000であり重合活性は
Ｋcat〔ポリマー（ｇ）／触媒（ｇ）・時間
（hr）・プロピレン圧（Kg／cm）、以下においても
同意義を有する〕は825、ＫT1は30，600であつ
た。又IIは95.2％であり、ρBは0.36ｇ／c.c.であつ
た。尚１段目の重合は同一条件下での別個の重合
によりCEcatは４，800であつた。
比較例 ２
実施例２での２段重合をやめ１段で重合を行な
つた。即ち同一オートクレーブに実施例の重合終
了時と同じ触媒系組成比、即ちｎ−ヘキサン0.35
、トリエチルアルミニウム847μmol、ｐ−ト
ルイル酸エチルエステル128μmolを添加し、触
媒供給管にチタン含有固体触媒成分22.5mgを含む
ｎ−ヘキサンスラリーを入れ、撹拌下60℃に昇温
後、触媒をオートクレーブ内に供給し、直ちにプ
ロピレンを供給してその圧力を17Kg／cm（ゲー
ジ）として１時間重合を行なつた。１時間後実施
例２と同様にして下記の結果を得た。
CECAT＝12700
CET1＝470370
Ｋcat＝747
ＫT1＝27670
II＝91.4％
ρB＝0.31ｇ／c.c.
実施例 ３
〔〕 チタン含有固体触媒成分の調製
乾燥窒素置換した容量500mlの四つ口フラス
コに、トリフエニルシラノール40m molとトル
エン100mlを仕込み、これに3.2m mol／ml塩化
−ｎ−ブチルマグネシウムのジ−ｎ−ブチルエ
ーテル溶液12.5mlを25℃にて充分撹拌下にゆつ
くり添加した。添加終了後、25℃、１時間撹拌
し、次いで70℃昇温して更に１時間撹拌を続け
た。次いでトルエン及びジ−ｎ−ブチルエーテ
ルを減圧留去、乾燥して白色粉末を得た。次い
で粉末を撹拌下に135℃に昇温し四塩化チタン
800m molを加え、四塩化チタンリフラツクス
下、次いで、1.0m mol／ml安息香酸エチルエ
ステルのトルエン溶液８mlを添加した。135℃
で１時間撹拌処理を行ない、１時間後70℃に冷
却し、ｎ−ヘプタン200mlを加え、沈澱物を洗
浄した。洗浄はｎ−ヘプタン200mlで５回行な
い、淡黄褐色固体を得た。得られた固体のチタ
ン含有量は3.1％であつた。
〔〕 オレフインの重合
実施例１において実施例１の〔〕のチタン
含有固体触媒成分の代わりに上記〔〕で得ら
れた、チタン含有固体触媒成分を用いる以外は
実施例１の〔〕と同様にして、プロピレンを
重合した結果を表１に示した。
比較例 ３
比較例１において実施例１の〔〕のチタン含
有固体触媒成分の代わりに実施例３の〔〕で得
られた、チタン含有固体触媒成分を用いる以外は
比較例１と同様にしてプロピレンを重合した結果
を表−１に示した。
実施例 ４及び５
実施例３で１段目重合でのCECATを変えて重合
し結果を表１に示した。尚重合手法は実施例３と
同じで１段目の重合時間を変えてCECATを変更し
た。[Formula] (wherein R 6 is hydrogen or an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, or methyl, ethyl,
Represents an alkyl group having 1 to 10 carbon atoms such as propyl, butyl, pentyl, hexyl, heptyl, octyl, etc., and R 7 is methyl, ethyl, propyl, butyl,
It represents an alkyl group having 1 to 10 carbon atoms such as pentyl, hexyl, heptyl, and octyl, or an aryl group having 12 or less carbon atoms such as phenyl and toluyl. ) is used. Examples of carboxylic acid esters include methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, phenyl benzoate, methyl p-methoxybenzoate, p-
Ethyl methoxybenzoate, propyl p-methoxybenzoate, butyl m-methoxybenzoate, phenyl o-methoxybenzoate, methyl p-ethoxybenzoate, ethyl p-ethoxybenzoate, phenyl acetate, phenyl propionate, ethyl acrylate , methyl methacrylate, ethyl crotonate, propyl crotonate, butyl crotonate, ethyl cinnamate, propyl cinnamate, butyl cinnamate, dimethylglycine ethyl ester, dimethylglycine propyl ester, dimethylglycine butyl ester, diphenylglycine Ethyl ester, diphenylglycine propyl ester, diphenylglycine butyl ester, p-dimethylaminobenzoic acid ethyl ester, p-methyl toluate,
Ethyl p-toluate, propyl p-toluate, butyl p-toluate, hexyl p-toluate, octyl p-toluate, methyl p-ethylbenzoate, ethyl p-ethylbenzoate, propyl p-ethylbenzoate , butyl p-ethylbenzoate, hexyl p-ethylbenzoate, octyl p-ethylbenzoate, methyl p-butylbenzoate, p
-Ethyl butylbenzoate, propyl p-butylbenzoate, butyl p-butylbenzoate, hexyl p-butylbenzoate, octyl p-butylbenzoate, methyl p-hexylbenzoate, ethyl p-hexylbenzoate, p- Propyl hexylbenzoate, butyl p-hexylbenzoate, hexyl p-hexylbenzoate, octyl p-hexylbenzoate, methyl p-octylbenzoate, ethyl p-octylbenzoate, propyl p-octylbenzoate, p-octyl Examples include butyl benzoate, hexyl p-octylbenzoate, octyl p-octylbenzoate, and the like. (A) component, (B) component and
There are no particular restrictions on the order of addition of component (C), including adding component (C) to a mixed system of components (A) and (B), or vice versa, or adding component (A) and component (C). A method of adding component (B) to a mixed system of (B) and vice versa, a method of adding component (A) to a mixed system of components (B) and (C), or vice versa, or a method of adding component (A) to a mixed system of components (B) and (C). , (B) component, and (C) component simultaneously. Therefore, in the method of the present invention, olefin is polymerized in multiple stages using the above three-component catalyst, and the polymerization conditions for the first stage are determined to satisfy the following (1) to (4). . (1) Adjust the molar ratio of component (B) to titanium in component (A) (hereinafter abbreviated as (B)/(A)) in the second and subsequent stages.
Make it smaller compared to (B)/(A). (2) Component (C) is not used, or even if it is used, the molar ratio of component (C) to titanium in component (A) (hereinafter abbreviated as (C)/(A)) is determined in the second stage. subsequent
Make it smaller compared to (C)/(A). (3) The polymerization time shall be less than the total polymerization time from the second stage onwards. (4) The amount of olefin polymer produced in the first stage is 10,000 grams or less per gram of component (A), e.g.
The amount is 10,000 grams, preferably 5 to 5,000 grams, and the weight ratio is 0.6 or less relative to the amount of olefin polymer produced in all stages. When (B)/(A) in the first stage becomes larger than (B)/(A) in the second and subsequent stages, the stereoregularity of the obtained olefin polymer decreases. Therefore, (B)/(A) in the first row is 2
It is preferable that it is 0.1 or more smaller than (B)/(A) in the subsequent rows. Further, when (C)/(A) in the first stage becomes larger than (C)/(A) in the second stage and thereafter, the polymerization activity of the catalyst decreases. Therefore, (C)/(A) in the first row is (C)/(A) in the second and subsequent rows.
It is preferable that it is smaller than 0.1. In this specification, the usage amount of each component (A) to (C) in each of the second and subsequent stages is defined as the sum of the usage amount in the previous stage and the usage amount in the relevant stage. To specifically illustrate the usage ratio of each component, the amount of component (B) used is 0.5 to 100 mol, preferably 1 to 20 mol in the first stage, per 1 mol of titanium of component (A).
In the second and subsequent stages, the amount is selected from the range of 1 to 1000 mol, preferably 10 to 300 mol, compared to the first stage. In addition, the amount of component (C) to be used is similarly expressed per 1 mol of titanium as component (A), and the first stage is selected from the range of 0 to 2.0 mol, preferably 0 to 1.0 mol, and the second stage and subsequent stages are selected from the range of 0 to 1.0 mol. 0.1 to 200 mol more than the eye, preferably 1 to 200 mol
selected from the range of 10 mol, and the amount of component (C) used is
(B) The first stage is 0 to 0.1 mol per mol of component, and the second and subsequent stages are selected from the range of 0.1 to 0.3 mol. At this time, the molar ratio of component (C) to component (B) (hereinafter, (C)/
(abbreviated as (B)), the first row (C)/(B) is 2
It is preferable to select a value smaller than (C)/(B) in the subsequent stages. When (C)/(B) in the first stage becomes larger, the polymerization activity of the catalyst decreases. The polymerization temperature is preferably 0°C to 100°C in the first stage.
Selected from 20 to 80℃, particularly preferably 25 to 75℃, and 30 to 100℃ for second and subsequent stages, preferably 50 to 80℃.
The polymerization temperature is selected from a range of 0.degree. C., but preferably the polymerization temperature in the first stage does not exceed the polymerization temperature in the second and subsequent stages. When the polymerization temperature of the first stage exceeds the polymerization temperature of the second and subsequent stages, the polymerization activity of the catalyst decreases. Moreover, the polymerization pressure is usually selected from the range of 0.1 to 50 atm. The polymerization time is preferably 1 hour or less in the first stage and less than the total polymerization time in the second and subsequent stages. If the polymerization time in the first stage exceeds the total polymerization time in the second and subsequent stages, the stereoregularity of the resulting olefin polymer will deteriorate, which is undesirable. Furthermore, the amount of olefin polymer produced in the first stage polymerization is 10,000 grams or less, for example 1 to 10,000 grams, preferably 5 to 10,000 grams per gram of component (A).
5,000 grams, and the weight ratio to the total amount of olefin polymer produced is 0.6 or less. When the former exceeds 10,000 grams, the stereoregularity of the obtained olefin polymer decreases, and the latter decreases to 0.6 grams.
If it exceeds , the stereoregularity similarly decreases. Therefore, in the method of the present invention, the olefin is polymerized in two or more stages under the above polymerization conditions, preferably at least 50,000 grams, particularly at least 100,000 grams, per gram of titanium in component (A). olefin polymer is produced. To illustrate a specific method for two-stage polymerization, first, the olefin is polymerized using the three-component catalyst under the polymerization conditions, and then, if necessary, after increasing the temperature and pressure,
Component (B) and component (C) are further added to further polymerize the olefin. The polymerization reaction is carried out continuously or in batches by solution polymerization or slurry polymerization in the presence of an inert hydrocarbon or liquefied propylene solvent, and gas phase polymerization without a solvent. Furthermore, by allowing hydrogen to exist in the polymerization zone, the molecular weight of the produced polymer can be easily controlled. Examples of the olefins used include α-olefins such as ethylene, propylene, butene-1, etc., and using the catalyst system of the present invention, homopolymerization, random copolymerization of two or more types, or block copolymerization of these can be carried out. These olefin polymers can be advantageously obtained by performing the following steps. The catalyst system according to the invention is particularly suitable for the production of highly stereoregular polymers, thus producing homopolymers of propylene or more than 90% by weight of propylene and less than 10% by weight of other α-
Suitable for producing copolymers consisting of olefins. As detailed above, according to the method of the present invention, an olefin polymer with good stereoregularity can be easily obtained. Since the obtained olefin polymer has high stereoregularity, removal of the amorphous polymer from the polymer can be omitted. Furthermore, since the titanium-containing solid catalyst component used in the present invention maintains high polymerization activity under the polymerization conditions of the present invention, it has the advantage that the step of removing catalyst residue from the obtained olefin polymer can be omitted. Moreover, the bulk density of the polymer is improved, which is very useful industrially. Furthermore, the halogen content in the polymer obtained by the method of the present invention is extremely low, and the benefits in terms of product properties are extremely large. Next, the present invention will be explained by giving Examples and Comparative Examples, but the present invention is not limited by these in any way. In the Examples and Comparative Examples, an isotactic index (hereinafter abbreviated as "II") was used.
Unit %) is boiling n in a modified Soxhlet extractor.
- The solid residue after extraction with heptane for 6 hours was dried and expressed in % by weight. In addition, melt flow index (hereinafter abbreviated as "MFI", unit: g/10 minutes)
indicates the value measured according to ASTM-D1238. Bulk density (hereinafter abbreviated as ρ B ) is JIS−
The values measured by 6721 are shown. Example 1 [] Synthesis of polyphenylsilanol 3.2 g of pure water and 170 ml of toluene were placed in a 500 ml four-necked flask, and the reaction vessel was kept cool at -20°C with magnetic stirring. Add 25 g (0.118 mol) of phenyltrichlorosilane to 70 ml of this toluene suspension.
A toluene solution was added dropwise using a dropping funnel over a period of 1 hour. After the dropwise addition was completed, the reaction mixture was heated to 0° C., and stirring was continued for an additional 30 minutes. Next, it was washed with ice water until the washing solution became neutral. The obtained toluene solution was dehydrated and dried over anhydrous sodium sulfate, filtered, and the resulting solution was used as a raw material for preparing a carrier. The hydroxyl group concentration of this toluene solution was determined by the method described below and was 8.1 m
It was mol/g. The amount of hydroxyl groups in the polysilanol was determined as follows. Add an appropriate amount of Grignard compound so that it is in excess of the hydroxyl group, and heat at 100℃ for 1 hour.
The reaction was completed by heating and stirring for an hour. Next, verzyl bromide was added in an amount equal to the number of moles of the Grignard compound used, and heating and stirring at 100° C. was continued for 1 hour. Next, after returning the reaction vessel to room temperature, pure water was added for hydrolysis, and the resulting alkaline component was titrated with hydrochloric acid or sulfuric acid in the presence of an appropriate indicator. In this case, use phenolphthalene alcohol solution as the indicator and as the acid.
A 0.1N hydrochloric acid aqueous solution was used. [] Preparation of titanium-containing solid catalyst component In a 500 ml four-neck flask purged with dry nitrogen, add 130 ml of a toluene solution of 0.34 mol/hydroxyl group of the polyphenylsilanol synthesized in [].
3.9 mol/n-butylmagnesium chloride di-n-butyl ether solution
11.3 ml was slowly added dropwise at 25°C with sufficient stirring. After the dropwise addition was completed, the mixture was stirred and aged at 110°C for 1 hour. Next, toluene and di-n-butyl ether were distilled off under reduced pressure and dried to obtain a white powder. Next, the powder was heated to 135°C while stirring to form titanium tetrachloride.
840 mmol of titanium tetrachloride was added thereto, and then 4.4 ml of a 2 mol/toluene solution of p-toluic acid methyl ester was added. After stirring at 135°C for 1 hour and cooling to about 70°C, 200ml of n-heptane was added and the precipitate was separated from the supernatant. Washing was carried out in the same manner six times with 200 ml of n-heptane to obtain a pale yellowish brown solid. The titanium content of the obtained solid was 2.7% and the Cl content was 39.2%. [] Polymerization of olefin Using the catalyst component prepared in [] above, two-stage polymerization of olefin was carried out in the following manner. In a 500ml four-necked flask purged with dry nitrogen.
- 300ml heptane, 50ml triethylaluminum
μmol and 30.1 mg of the titanium-containing solid catalyst component prepared in [] above were charged. Then, propylene gas was introduced at normal pressure at 32° C. while stirring. After flowing propylene at 32°C for 5 minutes, the propylene was replaced with deoxygenated and dehydrated purified nitrogen, and after raising the temperature to 70°C, 190 μmol of triethylaluminum and 30 μmol of p-toluic acid methyl ester were added, and propylene was immediately poured at normal pressure. After 2 hours of polymerization under flowing conditions, a small amount of methanol was added to stop the polymerization. The contents were poured into methanol, separated and dried to obtain 23.8 g of white powdery polypropylene. Polymerization activity is K
T1 [Polymer (g)/Titanium (g), time (hr), propylene pressure (Kg/cm), the following has the same meaning. ] is 24,400 and II is 96.6
It was %. The amount of polymer produced in the first stage polymerization was 16.4 g per 1 g of the titanium-containing solid catalyst component. 1
The ratio of step polymer amount/total polymer amount was 0.02. Comparative Example 1 In [ ] of Example 1, polymerization was carried out in one stage. That is, in the same apparatus, 300 ml of n-heptane, 240 μmol of triethylaluminum, 30 μmol of p-toluic acid ethyl ester, and 30.1 mg of the titanium-containing solid catalyst component obtained in [] of Example 1 were charged, and the temperature was raised to 70°C under stirring. , propylene gas was introduced at normal pressure and polymerization was carried out for 2 hours, followed by polymerization in the same manner as in Example 1. K T1 =17,640, II = 94.4%. Example 2 High-pressure polymerization was carried out using the titanium-containing solid catalyst component obtained in [] of Example 1. An autoclave equipped with two electromagnetic induction stirrers and equipped with two catalyst supply pipes was sufficiently purged with dry argon. 0.35 n-hexane was placed in an autoclave, and then 127 μmol of triethylaluminum and p
- 6.4 μmol of toluic acid ethyl ester was added.
Of the two catalyst supply tubes, one was filled with the n-hexane slurry containing 22.5 mg of the catalyst obtained in [] of Example 1, and the other was filled with 720 μmol of triethylaluminum diluted with the n-hexane slurry and p-toluic acid. 122 μmol of ethyl ester was added. Next, while stirring, the temperature of the autoclave was raised to 60°C, and after feeding the titanium-containing solid catalyst component into the autoclave,
Immediately, propylene was supplied and the pressure was kept at 17 Kg/cm 2 (gauge) to start polymerization. Immediately after polymerizing at 60℃ for 20 minutes, add triethylaluminum and p-
A mixed solution of toluic acid ethyl ester in n-hexane was fed into the autoclave, and polymerization was continued for 40 minutes at the same temperature and the same propylene pressure. Next, a small amount of methanol was added to stop the polymerization, and after purging unreacted monomers, the entire contents were taken out into a vat and dried to obtain 316 g of white powdery polypropylene.
The amount of polymer produced (grams) per gram of titanium-containing solid catalyst component (hereinafter referred to as CE CAT) of the obtained polypropylene was 14,040, and the amount of polymer produced per gram of titanium (grams) (hereinafter referred to as CE CAT ) was 14,040. The polymerization activity is 825, K T1 was 30,600. Also, II was 95.2%, and ρ B was 0.36 g/cc. The first stage polymerization was a separate polymerization under the same conditions and had a CE cat of 4,800. Comparative Example 2 The two-stage polymerization in Example 2 was replaced with one-stage polymerization. That is, in the same autoclave, the same catalyst system composition ratio as at the end of the polymerization in Example, that is, n-hexane 0.35
, 847 μmol of triethylaluminum, and 128 μmol of p-toluic acid ethyl ester were added, and an n-hexane slurry containing 22.5 mg of the titanium-containing solid catalyst component was added to the catalyst supply pipe, and after raising the temperature to 60°C with stirring, the catalyst was placed in an autoclave. Immediately after supplying propylene, polymerization was carried out for 1 hour at a pressure of 17 kg/cm (gauge). After 1 hour, the following results were obtained in the same manner as in Example 2. CE CAT = 12700 CE T1 = 470370 K cat = 747 K T1 = 27670 II = 91.4% ρ B = 0.31 g/cc Example 3 [] Preparation of titanium-containing solid catalyst component 500 ml capacity four-necked flask purged with dry nitrogen 40 mmol of triphenylsilanol and 100 ml of toluene were charged, and 12.5 ml of a 3.2 mmol/ml di-n-butylmagnesium chloride solution in di-n-butyl ether was slowly added at 25°C with thorough stirring. After the addition was completed, the mixture was stirred at 25°C for 1 hour, then the temperature was raised to 70°C, and stirring was continued for an additional hour. Next, toluene and di-n-butyl ether were distilled off under reduced pressure and dried to obtain a white powder. Next, the temperature of the powder was raised to 135°C while stirring, and titanium tetrachloride was added.
800 mmol was added, and under titanium tetrachloride reflux, 8 ml of a 1.0 mmol/ml toluene solution of benzoic acid ethyl ester was added. 135℃
After 1 hour, the mixture was stirred at 70° C., and 200 ml of n-heptane was added to wash the precipitate. Washing was carried out five times with 200 ml of n-heptane to obtain a pale yellowish brown solid. The titanium content of the obtained solid was 3.1%. [] Polymerization of olefin The same procedure as in [] of Example 1 was carried out except that the titanium-containing solid catalyst component obtained in [] above was used in place of the titanium-containing solid catalyst component in [] of Example 1 in Example 1. Table 1 shows the results of polymerizing propylene. Comparative Example 3 Propylene was prepared in the same manner as in Comparative Example 1, except that the titanium-containing solid catalyst component obtained in [] of Example 3 was used instead of the titanium-containing solid catalyst component in [] of Example 1. The results of polymerization are shown in Table 1. Examples 4 and 5 Polymerization was carried out in Example 3 by changing the CE CAT in the first stage polymerization, and the results are shown in Table 1. The polymerization method was the same as in Example 3, except that the first stage polymerization time was changed and CE CAT was changed.
【表】
実施例 ６
〔〕 チタン含有固体触媒成分の調製
乾燥窒素で置換した容量500mlの四つ口フラ
スコに、3.2m mol／ml濃度の塩化−ｎ−ブチ
ルマグネシウムのジ−ｎ−ブチルエーテル溶液
32mlを仕込み、これに水100m molを含有した
テトラヒドロフラン溶液150mlを25℃に保ちな
がら、撹拌下に30分で滴下した。温度を60℃に
昇温して１時間撹拌を続けた。反応生成物の白
色沈澱物をｎ−ヘプタンで十分に洗浄し、減圧
下、溶媒を溜出し乾燥粉末7.8ｇを得た。得ら
れた粉末のCl／Mg原子比は0.92であつた。
上記粉末1.00ｇのｎ−ヘプタン18ml溶液に、
ｐ−トルイル酸エチルエステル6.8m mol四塩
化ケイ素13.6m molを加え、60℃で１時間処理
した。次いでｎ−ヘプタン100mlで５回洗滌
し、減圧下で溶媒を溜出し、Cl／Mg原子比で
1.56の白色粉末を得た。次いで、四塩化チタン
30mlを加え、135℃に昇温し１時間反応をおこ
なつた。その後、この系にトルエンを添加し、
100mlで２回洗浄し更にｎ−ヘプタン100mlで３
回洗浄して淡黄緑色の固体を得た。得られた固
体のチタン含有量は3.0重量％であつた。
〔〕 オレフインの重合
実施例１において実施例１の〔〕のチタン
含有固体触媒成分の代わりに上記〔〕で得ら
れた、チタン含有固体触媒成分を用いる以外
は、実施例１の〔〕と同様にしてプロピレン
の重合を行い表２に示す結果を得た。
比較例 ４
比較例１において実施例１の〔〕のチタン含
有固体触媒成分の代わりに実施例６の〔〕で得
られたチタン含有固体触媒成分を用いる以外は比
較例１と同様に重合を行ない表２に示す結果を得
た。[Table] Example 6 [] Preparation of titanium-containing solid catalyst component In a 500 ml four-necked flask purged with dry nitrogen, a di-n-butyl ether solution of n-butylmagnesium chloride at a concentration of 3.2 mmol/ml was added.
To this, 150 ml of a tetrahydrofuran solution containing 100 mmol of water was added dropwise over 30 minutes while stirring while maintaining the temperature at 25°C. The temperature was raised to 60°C and stirring was continued for 1 hour. The white precipitate of the reaction product was thoroughly washed with n-heptane, and the solvent was distilled off under reduced pressure to obtain 7.8 g of dry powder. The Cl/Mg atomic ratio of the obtained powder was 0.92. In a solution of 1.00 g of the above powder in 18 ml of n-heptane,
6.8 mmol of p-toluic acid ethyl ester and 13.6 mmol of silicon tetrachloride were added, and the mixture was treated at 60°C for 1 hour. Next, it was washed 5 times with 100 ml of n-heptane, the solvent was distilled off under reduced pressure, and the Cl/Mg atomic ratio was
A white powder of 1.56 was obtained. Next, titanium tetrachloride
30 ml was added, the temperature was raised to 135°C, and the reaction was carried out for 1 hour. Then, toluene was added to this system,
Wash twice with 100 ml and then 3 times with 100 ml of n-heptane.
After washing twice, a pale yellow-green solid was obtained. The titanium content of the obtained solid was 3.0% by weight. [] Olefin polymerization Same as in Example 1 [] except that in Example 1, the titanium-containing solid catalyst component obtained in [] above was used instead of the titanium-containing solid catalyst component in [] in Example 1. Polymerization of propylene was carried out using the following methods, and the results shown in Table 2 were obtained. Comparative Example 4 Polymerization was carried out in the same manner as in Comparative Example 1, except that the titanium-containing solid catalyst component obtained in [] of Example 6 was used instead of the titanium-containing solid catalyst component in [] of Example 1. The results shown in Table 2 were obtained.
【表】
実施例 ７
〔〕 チタン含有固体触媒成分の調製
乾燥窒素で置換した容量500mlの４つ口フラ
スコに、トルエン150ml及び2.5m mol／mlの濃
度の塩化−ｎ−ブチルマグネシウム（ｎ−
C4H9MgCl）のジ−ｎ−ブチルエーテル溶液40
mlを仕込み、これにエタノール5.8ml（100m
mol）を25℃に保ちながら強撹拌下に滴下し
た。C2H5OH／ｎ−BuMgClモル比は1.0であ
る。添加終了後25℃で１時間撹拌し、ついで80
℃に昇温し、同温度で１時間撹拌を続けた。こ
の反応生成物をヘプタン150mlで５回洗浄を行
つた後、減圧下でヘプタンを留去し乾燥を行
い、白色の固体粉末を得た。この固体を分析し
たところ組成は（C2H5O）0.98MgCl0.93であ
つた。
次いで上記粉末にトルエン150ml及び安息香
酸エチルエステル2.9ml（20m mol）を25℃で
添加した。安息香酸エチルエステルのMgに対
するモル比は0.2である。添加終了後110℃に昇
温し同温度で１時間撹拌を続けた。反応生成物
から減圧下でトルエンを留去し乾燥を行い、白
色の固体粉末を得た。
次いで四塩化チタン（TiCl4）220ml
（2mol）を撹拌下25℃で添加した。TiCl4／Mg
モル比は20である。添加終了後130℃に昇温
し、同温度で１時間撹拌を続けた。しかる後反
応懸濁液を熱時傾瀉し、残存固体をヘプタンで
洗浄液中に塩素の存在が認められなくなる迄洗
浄を繰返し、淡黄褐色のチタン含有固体触媒成
分を得た。得られた固体のチタン含有量は2.7
重量％であつた。
〔〕 オレフインの重合
実施例１において〔〕のチタン含有固体触
媒成分の代わりに上記〔〕で得られたチタン
含有固体触媒成分を用いる以外は、実施例１の
〔〕と同様にしてプロピレンを重合した結果
を表５に示した。
比較例 ５
比較例１においてチタン含有固体触媒成分を実
施例７の〔〕で得たものを用いる以外は比較例
１と同様にしてプロピレンを重合した結果を表−
３に示した。[Table] Example 7 [] Preparation of titanium-containing solid catalyst component 150 ml of toluene and n-butylmagnesium chloride (n-
C 4 H 9 MgCl) di-n-butyl ether solution 40
ml and add 5.8 ml of ethanol (100 m
mol) was added dropwise under strong stirring while maintaining the temperature at 25°C. The C2H5OH /n-BuMgCl molar ratio is 1.0. After the addition was complete, stir at 25°C for 1 hour, then stir at 80°C.
The temperature was raised to °C, and stirring was continued at the same temperature for 1 hour. After washing the reaction product five times with 150 ml of heptane, the heptane was distilled off under reduced pressure and the product was dried to obtain a white solid powder. When this solid was analyzed, its composition was (C 2 H 5 O) 0.98 MgCl 0.93 . Then, 150 ml of toluene and 2.9 ml (20 mmol) of benzoic acid ethyl ester were added to the above powder at 25°C. The molar ratio of benzoic acid ethyl ester to Mg is 0.2. After the addition was completed, the temperature was raised to 110°C, and stirring was continued at the same temperature for 1 hour. Toluene was distilled off from the reaction product under reduced pressure and the product was dried to obtain a white solid powder. Then 220ml of titanium tetrachloride (TiCl 4 )
(2 mol) was added under stirring at 25°C. TiCl 4 /Mg
The molar ratio is 20. After the addition was completed, the temperature was raised to 130°C, and stirring was continued at the same temperature for 1 hour. Thereafter, the reaction suspension was decanted under heat, and the remaining solid was washed repeatedly with heptane until no chlorine was detected in the washing solution, to obtain a pale yellowish brown titanium-containing solid catalyst component. The titanium content of the obtained solid is 2.7
It was in weight%. [] Polymerization of olefin Propylene was polymerized in the same manner as in Example 1 [] except that the titanium-containing solid catalyst component obtained in [] above was used instead of the titanium-containing solid catalyst component in [] in Example 1. The results are shown in Table 5. Comparative Example 5 In Comparative Example 1, propylene was polymerized in the same manner as in Comparative Example 1 except that the titanium-containing solid catalyst component obtained in [ ] of Example 7 was used. The results are shown in Table 1.
Shown in 3.
【表】
実施例８及び比較例６
実施例２及び比較例２に於て各々実施例３の
〔〕で得たチタン含有固体触媒成分を用いた以
外は同一条件で重合し表４に示す結果を得た。
実施例９及び比較例７
実施例２及び比較例２に於て各々実施例６の
〔〕で得たチタン含有固体触媒成分を用いた以
外は同一条件で重合し表４に示す結果を得た。
実施例10及び比較例８
実施例２、比較例２に於て各々実施例７の
〔〕で得たチタン含有固体触媒成分を用いた以
外は同一条件で重合し表−４に示す結果を得た。[Table] Example 8 and Comparative Example 6 In Example 2 and Comparative Example 2, polymerization was carried out under the same conditions except that the titanium-containing solid catalyst component obtained in [ ] of Example 3 was used, and the results are shown in Table 4. I got it. Example 9 and Comparative Example 7 In Example 2 and Comparative Example 2, polymerization was carried out under the same conditions except that the titanium-containing solid catalyst component obtained in [ ] of Example 6 was used, and the results shown in Table 4 were obtained. . Example 10 and Comparative Example 8 In Example 2 and Comparative Example 2, polymerization was carried out under the same conditions except that the titanium-containing solid catalyst component obtained in [] of Example 7 was used, and the results shown in Table 4 were obtained. Ta.
【表】【table】
【表】
比較例 ９
実施例２に於て、１段目の重合を60℃で60分間
のみ行い、（２段目の重合は行なわない。）次の結
果を得た。
CECAT＝10900
CET1＝403700
II＝85.7％
ρB＝0.26ｇ／c.c.
比較例 10
実施例２に於て１段目の重合時間を45分とし２
段目の重合を15分行い以下の結果を得た。
CECAT＝11600
CET1＝429630
II＝882％
ρB＝0.28
１段目CECAT＝8520
１段目生成量／全体収量＝0.73
比較例 11
実施例１の〔〕に於て１段目の重合を行つて
のち、70℃に昇温してトリエチルアルミニウム、
ｐ−トルイル酸メチルエステルを添加せずに１段
目の触媒系組成比のままで重合を70℃で２時間行
い同様にして以下の結果を得た。
ＫT1＝8960
II＝90.3％[Table] Comparative Example 9 In Example 2, the first stage polymerization was carried out at 60°C for only 60 minutes (the second stage polymerization was not carried out), and the following results were obtained. CE CAT = 10900 CE T1 = 403700 II = 85.7% ρ B = 0.26 g/cc Comparative Example 10 In Example 2, the first stage polymerization time was 45 minutes.
The stage polymerization was carried out for 15 minutes and the following results were obtained. CE CAT = 11600 CE T1 = 429630 II = 882% ρ B = 0.28 1st stage CE CAT = 8520 1st stage production amount/total yield = 0.73 Comparative example 11 1st stage polymerization in [] of Example 1 After that, the temperature was raised to 70℃ and triethylaluminum,
Polymerization was carried out at 70° C. for 2 hours without adding p-toluic acid methyl ester and with the same composition ratio of the first stage catalyst system, and the following results were obtained in the same manner. K T1 = 8960 II = 90.3%
Claims (1)
ール、シラノール及びポリシラノールのうち
から選ばれた少くとも１種の化合物とを、反
応させて得られたマグネシウム化合物、 (b) 四ハロゲン化チタン及び (c) カルボン酸エステルを 接触させて得られるチタン含有固体触媒成分
と、 (B) 有機アルミニウム化合物と、 (C) カルボン酸エステル とからなる触媒系を使用してオレフインを多段と
重合する方法であつて一段目の重合条件を、 (A)チタン含有固体触媒成分中のチタンに対する
(B)有機アルミニウム化合物のモル比を２段目以
降におけるモル比よりも小さくし、(C)カルボン
酸エステルは使用しないか又は使用する場合に
は(A)チタン含有固体触媒成分中のチタンに対す
る(C)カルボン酸エステルのモル比２段目以降に
おけるモル比よりも小さくし、 重合時間は２段目以降の重合時間の合計以下と
し、 １段目で生成するオレフイン重合体量を、(A)チ
タン含有固体触媒成分１グラム当り、10000グ
ラム以下とし、且つ全体で生成するオレフイン
重合体量に対し重量比で0.6以下とすることを
特徴とするオレフイン重合体の製造方法。 ２ １段目における(B)有機アルミニウム化合物に
対する(C)カルボン酸エステルのモル比が２段目以
降におけるモル比に比較して小さいことを特徴と
する特許請求の範囲第１項記載のオレフイン重合
体の製造方法。 ３ １段目における重合温度が２段日以降の重合
温度以下であることを特徴とする特許請求の範囲
第１項又は第２項記載のオレフイン重合体の製造
方法。 ４ オレフインがプロピレンであることを特徴と
する特許請求の範囲第１項ないし第３項のいずれ
かに記載のオレフイン重合体の製造方法。 ５ オレフインがプロピレンと他のα−オレフイ
ンとの混合物であることを特徴とする特許請求の
範囲第１項ないし第３項のいずれかに記載のオレ
フイン重合体の製造方法。 ６ マグネシウム化合物が、ポリシラノールとグ
リニヤール化合物との反応生成物であることを特
徴とする特許請求の範囲第１項ないし第５項のい
ずれかに記載のオレフイン重合体の製造方法。 ７ マグネシウム化合物がシラノールとグリニヤ
ール化合物との反応生成物であることを特徴とす
る特許請求の範囲第１項ないし第５項のいずれか
に記載のオレフイン重合体の製造方法。 ８ マグネシウム化合物が水とグリニヤール化合
物との反応生成物であることを特徴とする特許請
求の範囲第１項ないし第５項のいずれかに記載の
オレフイン重合体の製造方法。 ９ マグネシウム化合物がアルコールとグリニヤ
ール化合物との反応生成物であることを特徴とす
る特許請求の範囲第１項ないし第５項のいずれか
に記載のオレフイン重合体の製造方法。[Scope of Claims] 1 (A) (a) A magnesium compound obtained by reacting a Grignard compound with at least one compound selected from water, alcohol, silanol, and polysilanol, ( Olefin production using a catalyst system consisting of a titanium-containing solid catalyst component obtained by contacting b) titanium tetrahalide and (c) a carboxylic acid ester, (B) an organoaluminum compound, and (C) a carboxylic acid ester. In this method, the first stage polymerization conditions are: (A) relative to the titanium in the titanium-containing solid catalyst component;
(B) The molar ratio of the organoaluminum compound is made smaller than the molar ratio in the second and subsequent stages, and (C) the carboxylic acid ester is not used or, if used, (A) relative to the titanium in the titanium-containing solid catalyst component. (C) The molar ratio of the carboxylic acid ester is made smaller than the molar ratio in the second and subsequent stages, the polymerization time is less than or equal to the total polymerization time in the second and subsequent stages, and the amount of olefin polymer produced in the first stage is reduced to (A ) A method for producing an olefin polymer, characterized in that the amount is 10,000 grams or less per gram of a titanium-containing solid catalyst component, and the weight ratio is 0.6 or less relative to the total amount of olefin polymer produced. 2. The olefin polymer according to claim 1, wherein the molar ratio of the carboxylic acid ester (C) to the organoaluminum compound (B) in the first stage is smaller than the molar ratio in the second and subsequent stages. Method of manufacturing coalescence. 3. The method for producing an olefin polymer according to claim 1 or 2, wherein the polymerization temperature in the first stage is lower than the polymerization temperature in the second and subsequent stages. 4. The method for producing an olefin polymer according to any one of claims 1 to 3, wherein the olefin is propylene. 5. The method for producing an olefin polymer according to any one of claims 1 to 3, wherein the olefin is a mixture of propylene and another α-olefin. 6. The method for producing an olefin polymer according to any one of claims 1 to 5, wherein the magnesium compound is a reaction product of a polysilanol and a Grignard compound. 7. The method for producing an olefin polymer according to any one of claims 1 to 5, wherein the magnesium compound is a reaction product of a silanol and a Grignard compound. 8. The method for producing an olefin polymer according to any one of claims 1 to 5, wherein the magnesium compound is a reaction product of water and a Grignard compound. 9. The method for producing an olefin polymer according to any one of claims 1 to 5, wherein the magnesium compound is a reaction product of an alcohol and a Grignard compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13760877A JPS5470390A (en) | 1977-11-16 | 1977-11-16 | Production of olefin polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13760877A JPS5470390A (en) | 1977-11-16 | 1977-11-16 | Production of olefin polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5470390A JPS5470390A (en) | 1979-06-06 |
| JPS6123209B2 true JPS6123209B2 (en) | 1986-06-04 |
Family
ID=15202654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13760877A Granted JPS5470390A (en) | 1977-11-16 | 1977-11-16 | Production of olefin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5470390A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5984905A (en) * | 1982-08-27 | 1984-05-16 | フイリツプス・ペトロリユ−ム・コンパニ− | Olefin polymerization catalyst, manufacture and use |
| JPH0791331B2 (en) * | 1987-12-26 | 1995-10-04 | 三井東圧化学株式会社 | Olefin Polymerization Method |
-
1977
- 1977-11-16 JP JP13760877A patent/JPS5470390A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5470390A (en) | 1979-06-06 |
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