JPH01126306A - Production of olefin polymer - Google Patents
Production of olefin polymerInfo
- Publication number
- JPH01126306A JPH01126306A JP62283989A JP28398987A JPH01126306A JP H01126306 A JPH01126306 A JP H01126306A JP 62283989 A JP62283989 A JP 62283989A JP 28398987 A JP28398987 A JP 28398987A JP H01126306 A JPH01126306 A JP H01126306A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst component
- prepolymerization
- olefin
- methylbutene
- compound
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229920000098 polyolefin Polymers 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 11
- 150000002367 halogens Chemical class 0.000 claims abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims description 35
- 239000011949 solid catalyst Substances 0.000 claims description 33
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 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 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 239000011777 magnesium Substances 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 150000002681 magnesium compounds Chemical class 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 15
- 239000004711 α-olefin Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 abstract description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 abstract description 2
- 229940093471 ethyl oleate Drugs 0.000 abstract description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 abstract 2
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 1
- 229910001629 magnesium chloride Inorganic materials 0.000 abstract 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- -1 polypropylene Polymers 0.000 description 11
- 230000037048 polymerization activity Effects 0.000 description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- WHFQAROQMWLMEY-UHFFFAOYSA-N propylene dimer Chemical group CC=C.CC=C WHFQAROQMWLMEY-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical compound NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000755266 Kathetostoma giganteum Species 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- OUZCDRGUTZLAGO-UHFFFAOYSA-N ethyl 2-ethoxybenzoate Chemical compound CCOC(=O)C1=CC=CC=C1OCC OUZCDRGUTZLAGO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QAYQKAPOTVSWLS-UHFFFAOYSA-N methyl 2-ethoxybenzoate Chemical compound CCOC1=CC=CC=C1C(=O)OC QAYQKAPOTVSWLS-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はオレフィン重合体の製造方法に関する。詳しく
は、特定のα−オレフィンを前重合し、ついでプロピレ
ンなどのα−オレフィンの本重合を行って、透明性や剛
性に優れ、また立体規則性や嵩密度の高いα−オレフィ
ン重合体を高活性で得る方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing olefin polymers. Specifically, a specific α-olefin is prepolymerized, and then an α-olefin such as propylene is main-polymerized to produce an α-olefin polymer with excellent transparency and rigidity, as well as stereoregularity and bulk density. Concerning the method of obtaining activity.
従来、三塩化チタンや、マグネシウム化合物を担体とし
たチタン含有固体触媒成分を用いて炭素数3以上のα−
オレフィンを重合するに先立ち、少量のα−オレフィン
を用いて、比較的低温で前重合する方法はよく知られて
いる。Conventionally, titanium trichloride or a titanium-containing solid catalyst component with a magnesium compound as a carrier was used to prepare α-
Prior to polymerizing olefins, it is well known to prepolymerize small amounts of alpha-olefins at relatively low temperatures.
特公昭タフ−フタ2111フ号公報においては、マグネ
シウム化合物に担持されたチタン含有固体触媒成分と有
機アルミニウム化合物から成で得る方法が提示されてい
る。しかし、この方法では、プロピレン重合体の透明性
は殆んど改良され得ない。Japanese Patent Publication No. 2111-F discloses a method of obtaining a titanium-containing solid catalyst component supported on a magnesium compound and an organoaluminum compound. However, with this method the transparency of propylene polymers can hardly be improved.
一方、特公昭<43−−321730号公報においては
、三塩化チタンと有機アルミニウム化合物から成る触媒
を少量の3−メチルブテン−7で前重合した後、プロピ
レンとヘキセン−7の如き炭素数かり以上のα−オレフ
ィンを共重合することによって、透明性の良好なプロピ
レン共重合体を得る方法が、また特開昭A/−/!;/
2011号公報においても、三塩化チタンと有機アルミ
ニウム化合物から成る触媒を少量の3−メチルブテン−
1で前重合した後プロビレ体粉末を得る方法が提示され
ている。On the other hand, in Japanese Patent Publication No. 43-321730, after prepolymerizing a catalyst consisting of titanium trichloride and an organoaluminum compound with a small amount of 3-methylbutene-7, A method of obtaining a propylene copolymer with good transparency by copolymerizing an α-olefin was also disclosed in Japanese Patent Application Laid-Open No. 2003-120002. ;/
2011 also discloses that a catalyst consisting of titanium trichloride and an organoaluminum compound is mixed with a small amount of 3-methylbutene
A method for obtaining a compound powder after prepolymerization in 1 is proposed.
しかしながら、これらの方法では、プロピレン重合体の
物性が改良される反面、触媒成分として重合活性の低い
三塩化チタンを用いている。However, although these methods improve the physical properties of the propylene polymer, they use titanium trichloride, which has low polymerization activity, as a catalyst component.
為、重合後の触媒残渣の除去工程が必須となり、工業的
に充分満足しうる方法とは言い難いものであった。Therefore, a step for removing catalyst residue after polymerization is essential, and this method cannot be said to be industrially fully satisfactory.
従って、マグネシウム、チタン、ハロゲン及び電子供与
性化合物を必須成分とする固体触媒成分を用いる重合で
、これら種々の効果を同時に兼ね備えた重合体の製造方
法の開発が望まれている。Therefore, it is desired to develop a method for producing a polymer that simultaneously has these various effects through polymerization using a solid catalyst component containing magnesium, titanium, halogen, and an electron-donating compound as essential components.
本発明者らは、かかる従来技術の問題点を解決すべく鋭
意検討を重ねた結果、マグネシウム、チタン、ハロゲン
および電子供与性化合物を必須成分とする触媒成分と有
機アルミニウム化合物から成る触媒を、3−メチルブテ
ン−11好ましくは、3−メチルブテン−lと炭素数3
〜コ0の他のα−オレフィ゛ンの混合物で前重合するこ
とによって透明性や剛性が優れ、立体規則性や嵩密度が
良好なプロピレン重合体が得られることを見い出し、本
発明に到達した。As a result of intensive studies to solve the problems of the prior art, the present inventors have developed a catalyst consisting of an organoaluminum compound and a catalyst component whose essential components are magnesium, titanium, halogen, and an electron-donating compound. -Methylbutene-11 Preferably, 3-methylbutene-1 and 3 carbon atoms
The present inventors have discovered that a propylene polymer with excellent transparency and rigidity, good stereoregularity, and bulk density can be obtained by prepolymerizing with a mixture of other α-olefins of 0 to 0, and have arrived at the present invention. .
すなわち本発明の要旨は、マグネシウム、チタン、ハロ
ゲン及び電子供与性化合物を必須成分とする固体触媒成
分(ロ)と周期律表第1〜■族の金属の有機金属化合物
伯)よシ成る触媒の存在下に、3−メチルブテン−11
もしくは3−メチルブテン−7と炭素数3以上のオレフ
ィンとの混合物を前重合させ、次いで炭素数3以上のオ
レフィンを単独重合または共重合させることを特徴とす
るオレフィン重合体の製造方法に存する。That is, the gist of the present invention is to provide a catalyst consisting of a solid catalyst component (b) whose essential components are magnesium, titanium, halogen, and an electron-donating compound, and an organometallic compound of metals from groups 1 to 2 of the periodic table. In the presence of 3-methylbutene-11
Alternatively, there is a method for producing an olefin polymer, which comprises prepolymerizing a mixture of 3-methylbutene-7 and an olefin having 3 or more carbon atoms, and then homopolymerizing or copolymerizing the olefin having 3 or more carbon atoms.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明における固体触媒成分に)は、少なくともマグネ
シウム化合物とチタン化合物および電子供与性化合物、
更に必要に応じてケイ素化合物、ハロゲン化剤等の助剤
とを一時的、または段階的に接触、反応させて得られる
従来公知の全てのマグネシウム、チタン、ハロゲン、電
子供与性化合物を含有する複合固体が用いられる。The solid catalyst component in the present invention) includes at least a magnesium compound, a titanium compound, and an electron-donating compound,
Further, if necessary, a composite containing all conventionally known magnesium, titanium, halogen, and electron-donating compounds obtained by contacting and reacting temporarily or stepwise with an auxiliary agent such as a silicon compound or a halogenating agent. Solids are used.
具体的には、
(1) ジアルコキシマ、グネシウム、チタン化合物
及び電子供与性化合物を任意の順序で反応させた後、液
状炭化水素で適宜洗浄する方法(2)塩化マグネシウム
、チタン化合物及び電子供与性化合物を任意の順序で接
触、反応させた後、液状炭化水素で適宜洗浄する方法(
3)有機マグネシウム化合物と、水、アルコール、フェ
ノールあるいはシラノールとの反応生成物、チタン化合
物及び電子供与性化合物を任意の順序で反応させた後、
液状炭化水素で適宜洗浄する方法
等の方法によって製造される。Specifically, (1) A method of reacting a dialkoximer, magnesium, a titanium compound, and an electron-donating compound in any order, and then washing as appropriate with a liquid hydrocarbon. (2) A method of reacting a dialkoximer, magnesium, a titanium compound, and an electron-donating compound. A method of contacting and reacting in any order and then washing as appropriate with liquid hydrocarbon (
3) After reacting an organomagnesium compound with a reaction product of water, alcohol, phenol or silanol, a titanium compound and an electron-donating compound in any order,
It is produced by a method such as washing with a liquid hydrocarbon as appropriate.
更に、これらの反応時にケイ素化合物、/Sロゲン化合
物、アルコール、あるいは不活性固体、例L id’
Sio2、Al2oz 、ポリプロピレン、ポリエチレ
ン、ポリ−3メチルブテン−71ポリ−qメチルペンテ
ン−/、TiO2、B2O3、CaC03等を添加して
もよい。Furthermore, during these reactions, silicon compounds, /S rogene compounds, alcohols, or inert solids, e.g.
Sio2, Al2oz, polypropylene, polyethylene, poly-3methylbutene-71poly-qmethylpentene-/, TiO2, B2O3, CaC03, etc. may be added.
該固体触媒成分(4)として好ましいものは、−般弐M
g(OR’)z−nxn C式中R1はフルキル基、ア
リール基またはアラルキル基を示し、Xはハロゲン、n
はO≦n≦コを示す。)で表わされるマグネシウム化合
物、一般式Ti(OR2)mX4−mX4−m(式中R
2はアルキル基、アリール基またはアラルキル基を示し
、Xは)10ゲン、mはO≦m≦qを示す。)で表わさ
れるチタン化合物及び電子供与性化合物を反応させて得
られるマグネシウム、チタン、ハロゲン及び電子供与性
化合物を含有する複合固体である。The solid catalyst component (4) is preferably -General NiM
g(OR')z-nxn C In the formula, R1 represents a furkyl group, an aryl group, or an aralkyl group, X is a halogen, n
indicates O≦n≦ko. ), a magnesium compound represented by the general formula Ti(OR2)mX4-mX4-m (wherein R
2 represents an alkyl group, an aryl group, or an aralkyl group, X represents )10, and m represents O≦m≦q. ) is a composite solid containing magnesium, titanium, halogen, and an electron donating compound obtained by reacting a titanium compound and an electron donating compound.
一般式ME (OR’ ) z −n xnで表わされ
るマグネシウム化合物としては、具体的には、MgCl
2、MJI(OCH3)Ct、 M、!1l(QC2H
,)Ct、 M#(QC8H7)CL%Mi(OC4H
*’)CL s MJi’(OCgHs)Ct、 Mj
’(OCH3)2、MJ1(OQtHs)z、MJ9(
OCsHy)z、MS(QC:、H,)2、MII(O
CsHs)z、111L9(OCH2Cs Hs )
z、MJil(QC2H,)(OC4H11)、Mli
F(OC1H5)(QC,H,)、MJ(○C4H9)
(OCsHs)、111L9(OC6H4CHz )
2等を挙げることカテきる。これらは混合して用いるこ
ともできる。Specifically, the magnesium compound represented by the general formula ME (OR') z -n xn includes MgCl
2, MJI (OCH3) Ct, M,! 1l (QC2H
,)Ct, M#(QC8H7)CL%Mi(OC4H
*')CL s MJi'(OCgHs)Ct, Mj
'(OCH3)2, MJ1(OQtHs)z, MJ9(
OCsHy)z, MS(QC:,H,)2, MII(O
CsHs)z, 111L9(OCH2CsHs)
z, MJil (QC2H,) (OC4H11), Mli
F (OC1H5) (QC, H,), MJ (○C4H9)
(OCsHs), 111L9 (OC6H4CHz)
It's a good idea to win second place. These can also be used in combination.
また、この他担体原料として、有機マグネシウム化合物
、MJilOlMy(oH)、、M#(OH)C’t、
M、9カーボネート、有機酸のW塩、目シリケート1
、MJ9アルミネート等を用いることもできる。In addition, as carrier raw materials, organomagnesium compounds, MJilOlMy(oH), M#(OH)C't,
M, 9 carbonate, W salt of organic acid, 1 silicate
, MJ9 aluminate, etc. can also be used.
°−一般式Ti(OR2)mx、−0で表わされるチタ
ン化合物として゛は、具体的には、TiCl2、TiB
r 、、TiI、、Ti (OCH3)CL3、T1(
oc2H,)cz3、’I’i (QC、H,)CL3
、’I’1(QC6H,)CA3、Ti(OCH3)2
Ct。°- As a titanium compound represented by the general formula Ti(OR2)mx, -0, specifically, TiCl2, TiB
r,,TiI,,Ti(OCH3)CL3,T1(
oc2H,)cz3,'I'i (QC,H,)CL3
,'I'1(QC6H,)CA3,Ti(OCH3)2
Ct.
’ri(oc2a、)2cz、、Ti(QC,Ho)2
Ct2、’ri(QC,H,)2ct2、Ti(o(R
3)、Ct、 Ti(○C,H,)3CL、 Ti
(0(!。'ri(oc2a,)2cz,,Ti(QC,Ho)2
Ct2,'ri(QC,H,)2ct2,Ti(o(R
3), Ct, Ti (○C, H,)3CL, Ti
(0(!.
Ho)3Ct、 Ti(QC,H,)3C2,Ti(O
CH3)、、Ti(QC2H8)いTi(OC4H*)
a、Ti(QC,R5)、 等を挙げることができる
。また、この他に一般式
Ti(OR2)mX4−LXz−7(式中R3はアルキ
ル基、アリール基またはアラルキル基、Xは))ロゲン
、tはO≦t≦3を示す。)で表わされるチタン化合物
を用いることもできる。これらは混合して用いてもよい
。Ho)3Ct, Ti(QC,H,)3C2,Ti(O
CH3), Ti (QC2H8) Ti (OC4H*)
a, Ti(QC, R5), etc. In addition, the general formula Ti(OR2)mX4-LXz-7 (wherein R3 is an alkyl group, an aryl group, or an aralkyl group, and X is)) rogene, and t represents O≦t≦3. ) can also be used. These may be used in combination.
電子供与性化合物としては、一般に含リン化合物、含酸
素化合物、含硫黄化合物、含窒素化合物等が挙げられる
。このうち好ましくは、含酸素化合物が挙げられる。Examples of the electron-donating compound generally include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, nitrogen-containing compounds, and the like. Among these, oxygen-containing compounds are preferred.
含酸素化合物としては、例えばエーテル類、エステル類
、ケトン類、酸無水物等が挙げられる。Examples of oxygen-containing compounds include ethers, esters, ketones, and acid anhydrides.
好ましくは、酢酸エチル、プロピレン酸メチル、アクリ
ル酸エチル、オレイン酸エチル、ステアリン酸エチル、
フェニル酢酸エチル、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、トルイル酸メチ
ル、トルイル酸エチル、トルイル酸フロビル、トルイル
酸ブチル、エチル安息香酸メチル、エチル安息香酸エチ
ル、キシレンカルボン酸エチル、アニス酸メチル、アニ
ス酸エチル1.エトキシ安息香酸メチル、エトキシ安息
香酸エチル、ケイ皮酸エチル、フタル酸ジエチル、フタ
ル酸ジブチル、フタル酸ジイソブチル、フタル酸ジヘキ
シル、フタル酸ジオクチルの様なカルボン酸のエステル
類あるいはr−ブチルラクトンの様な環状エステル類及
び無水マレイン酸、無水フタル酸等の酸無水物等が挙げ
られる。また、5i−OR’、Si−〇〇OR’又は8
i−NR二結合を有するケイ素化合物(式中、R4は炭
素数1〜20個の炭化水素基を示す)も好適に用いられ
る。Preferably, ethyl acetate, methyl propylate, ethyl acrylate, ethyl oleate, ethyl stearate,
Ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, furovir toluate, butyl toluate, methyl ethyl benzoate, ethyl ethyl benzoate, ethyl xylene carboxylate , methyl anisate, ethyl anisate 1. Esters of carboxylic acids such as methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate or r-butyl lactone. Examples include cyclic esters and acid anhydrides such as maleic anhydride and phthalic anhydride. Also, 5i-OR', Si-○○OR' or 8
A silicon compound having an i-NR double bond (in the formula, R4 represents a hydrocarbon group having 1 to 20 carbon atoms) is also preferably used.
チタン含有固体触媒成分の組成としては、ノ・ロダン/
チタン(モル比)が/−!;000.電子供与性化合物
/チタン(モル比)が0./ −t、チタン/マグネシ
ウム(モル比)が0.0 /〜i、o、固体触媒成分中
のチタン含量(重量qb)が0.07−20の範囲、好
ましくはノ・ロダン/チタン(モル比)が3〜ioo、
電子供与性化合物/チタン(モル比)が0.3〜3、チ
タン/マグネシウム(モル比)が0.02〜O,S;、
固体触媒成分中のチタン含量(重量%)が0./〜10
の範囲にある。The composition of the titanium-containing solid catalyst component is No. Rodan/
Titanium (molar ratio) is /-! ;000. Electron-donating compound/titanium (molar ratio) is 0. / -t, titanium/magnesium (mole ratio) is in the range of 0.0 /~i, o, titanium content (weight qb) in the solid catalyst component is in the range of 0.07-20, preferably no. ratio) is 3 to ioo,
Electron-donating compound/titanium (molar ratio) is 0.3 to 3, titanium/magnesium (molar ratio) is 0.02 to O, S;
The titanium content (wt%) in the solid catalyst component is 0. /~10
within the range of
周期律表第ト4族の金属の有機金属化合物(6)として
は、好ましくは、一般式h1n3 x、−jで表わされ
る化合物が挙げられる。上式においてR5は炭素数l−
20個の炭化水素基を示し、特に脂肪族炭化水素基が好
ましい。Xはハロゲン、jはコ〜3の数を示す。この有
機アルミニウム化合物の具体例としてはトリエチルアル
ミニウム、トリプロピルアルミニウム、トリブチルアル
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、ジエチルアルミニウムモノクロライド等が
挙げられるが、好ましくは、トリアルキルアルミニウム
が用いられる。また、0またはN原子を介して結合した
一個またはそれ以上のA/、原子を含有する有機アルミ
ニウム化合物も使用することができる。Preferably, the organometallic compound (6) of a metal in Group To4 of the periodic table includes a compound represented by the general formula h1n3 x, -j. In the above formula, R5 is the carbon number l-
20 hydrocarbon groups are shown, with aliphatic hydrocarbon groups being particularly preferred. X represents halogen, and j represents the number of 3. Specific examples of the organoaluminum compound include triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminium monochloride, etc., but trialkylaluminum is preferably used. Organoaluminum compounds containing one or more A/ atoms bonded via 0 or N atoms can also be used.
更に、ジアルキルアルミニウムハイドライド、ジアルキ
ルアルミニウムアルコキシド、アルキルアルミニウムセ
スキアルコキシド等も用いられる。Furthermore, dialkyl aluminum hydride, dialkyl aluminum alkoxide, alkylaluminium sesquialkoxide, etc. can also be used.
必要に応じて使用される電子供与性化合物C)としては
、チタン含有固体触媒成分@の製造において使用された
電子供与性化合物群の中から選ばれるが、好ましくは芳
香族カルボン酸エステル、5i−0−C結合を含有する
ケイ素化合物、At−0−8i−C結合を含有するケイ
素化合物等である。The electron-donating compound C) used as necessary is selected from the group of electron-donating compounds used in the production of the titanium-containing solid catalyst component, but preferably aromatic carboxylic acid esters, 5i- These include silicon compounds containing 0-C bonds, silicon compounds containing At-0-8i-C bonds, and the like.
前重合は、前記固体触媒成分(ロ)と周期律表第1−1
族の金属の有機金属化合物(ロ)及び必要に応じて電子
供与性化合物(C)よ)成る触媒と、通常は不活性炭化
水素や液化α−オレフィン等の溶媒中で3−メチルブテ
ン−11もしくは3−メチルブテン−/と炭素数3〜2
θのα−オレフィン、好ましくはプロピレン、ブテン−
l。The prepolymerization is carried out using the solid catalyst component (b) and the periodic table No. 1-1.
3-methylbutene-11 or 3-methylbutene-11 or 3-methylbutene-/ and carbon number 3-2
α-olefin of θ, preferably propylene, butene-
l.
ヘキセン−11オクテン−1等との混合物を接触させる
ことによって行なわれる。ここで3−メチルブテン−1
のみで前重合を行なうと、3−メチルブテン−lの重合
速度が非常に低い為、通常前重合時間を長くする必要が
あシ、さらにそれに引き続いて行なわれるプロピレン重
合の活性も低下する傾向におるが、3−メチルブテン−
7と炭素数3〜−〇の他のα−オレフィンとの混合物で
前重合すれば、前重合時間も少くて済み、それに引き続
いて行なわれるプロピレン重合の活性もさほど低下しな
いので、より好ましい。This is carried out by contacting a mixture with hexene-11 octene-1 and the like. where 3-methylbutene-1
If the prepolymerization is carried out with only 3-methylbutene-l, the polymerization rate of 3-methylbutene-l is very low, so it is usually necessary to lengthen the prepolymerization time, and the activity of the propylene polymerization that follows also tends to decrease. is 3-methylbutene-
It is more preferable to carry out prepolymerization with a mixture of 7 and other α-olefins having 3 to -0 carbon atoms, since the prepolymerization time can be shortened and the activity of the subsequent propylene polymerization will not be significantly reduced.
該混合物の組成としては、3−メチルブテン−7/他の
α−オレフィン(モル比)が0.0 /〜10000.
好ましくはo、t Ni0001よシ好ましくは/−1
00の範囲である。前重合の温度は通常θ〜100℃、
好ましくは20〜go℃、よシ好ましくはり0℃を超え
る温度であり、前重合量は、通常、固体触媒成分(A)
/ /i当り 0.0 / −/ 001 s全重合
量に対して0.00 /〜30重量%の範囲から選ばれ
る。この様な範囲の外では本発明の効果が充分得ること
が出来ず、好ましくない。The composition of the mixture is 3-methylbutene-7/other α-olefin (molar ratio) of 0.0/~10000.
Preferably o, t Ni0001, preferably /-1
The range is 00. The temperature of prepolymerization is usually θ~100℃,
Preferably the temperature is 20 to 0°C, more preferably over 0°C, and the amount of prepolymerization is usually the solid catalyst component (A).
/ /i 0.0 / - / 001 s Selected from the range of 0.00 / - 30% by weight based on the total polymerization amount. Outside this range, the effects of the present invention cannot be obtained sufficiently, which is not preferable.
触媒各成分の前重合時の使用割合は特に制限はないが、
通常、触媒成分(ト)中のチタン対の)成分中の金属対
(C)成分の電子供与性化合物のモル比がi:oJNt
o:o N/(7,好ましくはl: O,S〜3:O〜
3になるように選ばれる。There is no particular restriction on the proportion of each catalyst component used during prepolymerization, but
Usually, the molar ratio of the titanium pair in the catalyst component (G) to the metal in the component (C) and the electron donating compound of the component (C) is i:oJNt
o:o N/(7, preferably l:O,S~3:O~
Selected to be 3.
前重合後、該重合体含有固体触媒成分は不活性炭化水素
で洗浄、もしくは洗浄せずにオレフィンの本重合に供さ
れる。After the prepolymerization, the polymer-containing solid catalyst component is washed with an inert hydrocarbon or is subjected to the main polymerization of olefin without washing.
重合するオレフィンとしては、エチレン、プロピレン、
ブテン−1%3−メチルブテン−11弘−メチルペンテ
ン−7等が挙げられ、好ましくは炭素数3以上のα−オ
レフィン、特にプロピレンが挙げられる。また重合は単
独重合のほか通常公知のランダムまたはブロック共重合
にも好適に適用できる。例えばブロック共重合に適用す
ると、その剛性と耐衝撃性のバランスが改良されるので
特に好適である。Polymerizable olefins include ethylene, propylene,
Examples thereof include butene-1% 3-methylbutene-11-methylpentene-7, and preferred α-olefins having 3 or more carbon atoms, particularly propylene. In addition to homopolymerization, commonly known random or block copolymerization can also be suitably applied. For example, it is particularly suitable when applied to block copolymerization because the balance between rigidity and impact resistance is improved.
触媒各成分の使用割合は、触媒成分に)中のチタン対(
ト))成分の金属対(C)成分の電子供与性化合物のモ
ル比がl:3〜りoo:o Ntoo、好ましくはlニ
ー0〜200:3〜りOになるように選ばれる。The usage ratio of each catalyst component is the ratio of titanium in (to catalyst component) to (
The molar ratio of the metal of component (g)) to the electron-donating compound of component (C) is selected to be 1:3 to 0:0, preferably 1:0 to 200:3 to 0.
重合反応は、ブタン、ペンタン、ヘキサン、ヘプタン、
トルエン等の不活性炭化水素や液化α−オレフィン等の
溶媒の存在下あるいは不存在下に行なわれる。温度はe
o−ioo℃、好ましくはり0〜90℃であり、圧力は
特に制限されないが、通常大気圧〜100気圧の範囲内
から選ばれる。Polymerization reactions include butane, pentane, hexane, heptane,
This is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as toluene or a liquefied α-olefin. The temperature is e
The temperature is o-ioo°C, preferably 0 to 90°C, and the pressure is not particularly limited, but is usually selected from within the range of atmospheric pressure to 100 atm.
また重合系内に分子量調節剤として水素を存在させるこ
ともできる。Further, hydrogen can also be present in the polymerization system as a molecular weight regulator.
その他、α−オレフィンの単独重合、共重合に当って通
常様られる手段を本発明に適用することもできる。In addition, means commonly used for homopolymerization and copolymerization of α-olefins can also be applied to the present invention.
次に実施例によって本発明を更に具体的に説明するが、
本発明はその要旨を逸脱しない限シこれら実施例によっ
て制約を受けるものでない。Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited by these embodiments unless it departs from the gist thereof.
なお、声流側忙おいて、触媒効率(CEとして示す)は
固体触媒成分に)illクシポリマーの生成量(9)で
あシ、重合活性(Kとして示す)は1時間につきα−オ
レフィン圧t kg / d当シ固体触媒成分(Aty
当シのポリマー生成量(19)である。アイソタクチッ
クインデックス(IIとして示す)は改良型ソックスレ
ー抽出器で沸騰n−へブタンによシロ時間抽出した場合
の残量(重量%)である。嵩密度(ρBとして示す。In addition, on the voice stream side, the catalytic efficiency (shown as CE) is the amount of ill-combined polymer produced (9) in the solid catalyst component, and the polymerization activity (shown as K) is the α-olefin pressure per hour. t kg/d per solid catalyst component (Aty
This is the amount of polymer produced (19). Isotactic index (denoted as II) is the amount (% by weight) remaining after extraction with boiling n-hebutane in a modified Soxhlet extractor for a period of time. Bulk density (expressed as ρB).
単位はJil/cc)はJIS−に−47コl に従っ
て測定した。メルトフローインデックス(MFI、!−
して示す)はASTM−D−123g に従って測定し
た。The unit (Jil/cc) was measured according to JIS-47. Melt flow index (MFI,!-
) was measured according to ASTM-D-123g.
透明性の評価は、270℃でプレス成形した穿
厚l!1wIIのプレスフィルムを目から10crn離
し、このフィルムを通してみたフィルム背後の景色の鮮
明さで行った。ここで鮮明に見えるものは○、ぼやけて
見えるものはΔとした。剛性は第1降伏強度y s (
kg/d )と曲げ弾性率(kg/d)で示し、第1降
伏強度YSはASTMD63g−7−に準拠し、厚さへ
θ鵡のプレスシートから打抜いたダンベル片の引張試験
によって求め、曲げ弾性率はASTM D−790−A
&に従って測定した。Transparency evaluation was performed using press molding at 270°C with a perforation thickness of 1! I held a 1wII press film 10 crn away from my eyes and looked at the clarity of the scenery behind the film when I looked through it. Here, those that appear clearly are marked as ○, and those that appear blurry are marked as Δ. The stiffness is the first yield strength y s (
kg/d) and flexural modulus (kg/d), and the first yield strength YS is determined in accordance with ASTM D63g-7- by a tensile test of a dumbbell piece punched from a press sheet with a thickness of θ. Flexural modulus is ASTM D-790-A
Measured according to &.
実施例1
囚 固体触媒成分の製造
攪拌機、温度計を備えたりOO−フラスコに精製N2シ
ール下、市販Mg(QC2H,)2をS/30℃で1時
間反応させた。その後、1000Cに降温してフェノー
ルざ、コIのトルエン溶液を滴下した。滴下後昇温し1
30℃で1時間反応させ、黄色固体のスラリー状反応物
を得た。Example 1 Preparation of solid catalyst component Commercially available Mg(QC2H,)2 was reacted at S/30°C for 1 hour in an OO flask equipped with a stirrer and a thermometer under a seal of purified N2. Thereafter, the temperature was lowered to 1000C, and a toluene solution of phenol powder I was added dropwise. After dropping, raise the temperature 1
The reaction was carried out at 30° C. for 1 hour to obtain a slurry-like reaction product as a yellow solid.
このものに精製トルエンA’7mlを添加した後、−2
0℃まで冷却し、−20℃においてTiC242j 、
V 1を添加した。添加後徐々に昇温し、ざ0℃に昇温
後安息香酸エチル/、J 9を添加し、同温度で1時間
保持した。その後、精製トルエンで洗浄し、固体生成物
を得た。After adding 7 ml of purified toluene A' to this, -2
TiC242j at -20°C,
V1 was added. After the addition, the temperature was gradually raised to 0° C., then ethyl benzoate/J9 was added, and the temperature was maintained for 1 hour. Thereafter, it was washed with purified toluene to obtain a solid product.
次いでTiC4,l: J f/ 、安息香酸エチルi
、3 gを添加し、gθ℃において1時間固体生成物を
処理した。その後、室温において精製トルエン−〇〇−
で9回洗浄して固体触媒成分に)ulg gを得た。こ
の固体中のTi含量は2.1重量%であった。Then TiC4,l: J f/ , ethyl benzoate i
, 3 g was added and the solid product was treated for 1 hour at gθ°C. After that, purified toluene -〇〇-
A solid catalyst component (ulg) was obtained by washing with water 9 times. The Ti content in this solid was 2.1% by weight.
俤)前重合
精製アルゴンで充分置換した/lの誘導攪拌式オートク
レーブに1アルゴンシール下、室温でトリエチルアルミ
ニウムo、s gミリモルを添加し、更に液体3−メチ
ルブテン−/ 、yisgと液体プロピレンク!1を
仕込んだ。次いで、タタ℃に昇温し、実施例/(A)で
得られた固体触媒成分囚/lを添加して20分間前重合
を行なった。その後、室温において精製ノルマルヘキサ
ン200−で3回洗浄し、前重合触媒成分を得た。忤) Pre-polymerization purification Into a /l induction stirring autoclave which was sufficiently purged with argon, under a 1 argon seal, 0, sg mmol of triethylaluminum was added at room temperature, and then liquid 3-methylbutene-/, yisg and liquid propylene were added. I prepared 1. Next, the temperature was raised to 50° C., and the solid catalyst component/l obtained in Example/(A) was added to carry out prepolymerization for 20 minutes. Thereafter, the mixture was washed three times with 200 ml of purified normal hexane at room temperature to obtain a prepolymerization catalyst component.
この前重合触媒成分は、固体触媒成分(A)/I当当型
重合体3077含んでいた。This prepolymerization catalyst component contained solid catalyst component (A)/I equivalent type polymer 3077.
(C) プロピレンの重合
精製アルゴンで充分置換した2tの誘導攪拌式オートク
レーブにアルゴンシール下、室温でトリエチMアルミニ
ウム1.Oミリモル、パラメチル安息香酸メチル0.3
ミリモルを添加し、更に室温でH,ft/、Okg/c
dになるように加え、液体プロピレン700gを仕込ん
だ。(C) Polymerization of propylene Purified Triethyl M aluminum 1. O mmol, methyl paramethylbenzoate 0.3
Add mmol and further increase H, ft/, Okg/c at room temperature.
d, and 700 g of liquid propylene was charged.
次いで70℃に昇温し、上記の)で得られた前重合触媒
成分を固体触媒成分(ト)として/1■添加し、70℃
で1時間重合を行った。Then, the temperature was raised to 70°C, and the prepolymerization catalyst component obtained in the above step) was added as a solid catalyst component (g), and the temperature was raised to 70°C.
Polymerization was carried out for 1 hour.
その後余剰のプロピレンをパージして、粉末ポリプロピ
レンコブoyを得た。触媒効率CEは/ 9.3ooy
−pp/g−cat、、重合活性にはt、SOであった
。得られた重合体のpBはOoぐ71/ccであシ、I
Iは97.コチ、MFIは3.0であった。このものの
透明性の評価は○であり、第1降伏強度YSは3tr
o ky/crls曲げ弾性率はi r、 i o o
tcg / crlであった。各種測定結果を表−1
にまとめた。Thereafter, excess propylene was purged to obtain powdered polypropylene cob. Catalyst efficiency CE is / 9.3ooy
-pp/g-cat, and the polymerization activity was t, SO. The pB of the obtained polymer was 71/cc, I
I is 97. Flathead, MFI was 3.0. The transparency evaluation of this product is ○, and the first yield strength YS is 3tr.
o ky/crls flexural modulus is i r, i o o
It was tcg/crl. Table 1 shows various measurement results.
summarized in.
実施例コ
(6)前重合
実施例1の(B)において、プロピレンの仕込み量を3
gに変え、前重合時間をpo分に変えた以外は実施例1
の(B)と同様な方法で前重合を行なった。Example 6 (6) Prepolymerization In (B) of Example 1, the amount of propylene charged was 3
Example 1 except that the prepolymerization time was changed to g and po minutes.
Prepolymerization was carried out in the same manner as in (B).
得られた前重合触媒成分は固体触媒成分(4)ig当ク
シ重合体2りl含んでいた。The obtained prepolymerization catalyst component contained 2 g of solid catalyst component (4) and 2 l of comb polymer.
(C) プロピレンの重合
実施例2(B)で得られた前重合触媒成分を用いること
以外は実施例1の(C)と同様にしてプロピレンの重合
を行なったところ、触媒効率cE=ttr、ooo 1
−pp/y−cat、重合活性に=l、00.II=9
7.0チ、ρB=0.す6I/cc 、 M F I
= 3.tlであった。(C) Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 (C) except that the prepolymerization catalyst component obtained in Example 2 (B) was used, and the catalyst efficiency cE = ttr. ooo 1
-pp/y-cat, polymerization activity=l, 00. II=9
7.0chi, ρB=0. 6I/cc, MFI
= 3. It was tl.
各種測定結果を表−7に示した。Various measurement results are shown in Table-7.
実施例3
(B)前重合
実施例1の(B)において、前重合の温度と時間をそれ
ぞれコタ℃および1時間に変えた以外は実施例1の0)
と同様な方法で前重合を行なった。得られた前重合触媒
成分は固体触媒成分囚/、g当シ重合体をコig含んで
いた。Example 3 (B) Prepolymerization 0) of Example 1, except that in (B) of Example 1, the temperature and time of prepolymerization were changed to 0.degree. C. and 1 hour, respectively.
Prepolymerization was carried out in the same manner as above. The obtained prepolymerization catalyst component contained a solid catalyst component and a polymer.
(C) プロピレンの重合
実施例3(B)で得られた前重合触媒成分を用層ること
以外は実施例1の(C)と同様にしてプロピレンの重合
を行なったところ、触媒効率CE = 1Zuoo !
j−pp/y−cai 、重合活性に=3KO1II=
97.0チ、ρB=0.’ll、1/cc s M F
I =J、、2であった。(C) Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 (C) except that the prepolymerization catalyst component obtained in Example 3 (B) was used, and the catalyst efficiency CE = 1 Zuoo!
j-pp/y-cai, polymerization activity=3KO1II=
97.0chi, ρB=0. 'll, 1/cc s M F
I = J, 2.
各種測定結果を表−1に示した。Various measurement results are shown in Table-1.
実施例V
03) 前重合
実施例1の(ロ)において前重合の時間を3分に変えた
以外は実施例1の(ト))と同様な方法で前重合を行な
った。得られた前重合触媒成分は固体触媒成分(A)7
g当シ重合体をりl含んでいた。Example V 03) Prepolymerization Prepolymerization was carried out in the same manner as in (g) of Example 1, except that in (b) of Example 1, the prepolymerization time was changed to 3 minutes. The obtained prepolymerization catalyst component is solid catalyst component (A) 7
It contained 1 g of polymer.
(C) プロピレンの重合
実施例& 03)で得られた前重合触媒成分を用いる以
外は実施例1の(C)と同様にしてプロピレンの重合を
行なったところ、触媒効率CE=/ A、コ001−p
p/I−Cat 、重合活性K = S’IO。(C) Polymerization of propylene Propylene was polymerized in the same manner as in Example 1 (C) except that the prepolymerization catalyst component obtained in Example &03) was used, and the catalyst efficiency CE=/A, Co. 001-p
p/I-Cat, polymerization activity K = S'IO.
II=?if%、pB = 0.11 !;i/cc、
M F I=q、2であった。II=? if%, pB = 0.11! ;i/cc,
M F I = q, 2.
各種測定結果は表−/に示した。Various measurement results are shown in Table-/.
実施例!
0)前重合
実施例/の(6)において、前重合時の七ツマ−を3−
メチルブテン−7のみにし、前重合時間t−/時間にし
た以外は実施例1のΦ)と同様な方法で前重合を行なっ
た。得られた前重合触媒成分は固体触媒成分(4:i、
i当シ重合体を20g含んでいた。Example! 0) In (6) of Prepolymerization Example/, the seven polymers at the time of prepolymerization were changed to 3-
Prepolymerization was carried out in the same manner as in Example 1 (Φ) except that only methylbutene-7 was used and the prepolymerization time was t-/hour. The obtained prepolymerization catalyst component was a solid catalyst component (4:i,
It contained 20g of the polymer.
(C) プロピレンの重合
実施例りΦ)で得られた前重合触媒成分を用いる以外は
実施例1の(C)と同様にしてプロピレンの重合を行な
ったところ、触媒効率CE= / 26o o y−p
p/ g−cat 、重合活性に一’720゜I 工
=9 AJ%、ρB = 0.IIl、 fi/c
c 、 MFI=31gであった。(C) Propylene polymerization example Propylene polymerization was carried out in the same manner as in Example 1 (C) except that the prepolymerization catalyst component obtained in Φ) was used, and the catalyst efficiency CE = / 26o o y -p
p/g-cat, polymerization activity = 9 AJ%, ρB = 0. IIl, fi/c
c, MFI=31 g.
各種測定結果は表−1に示した。Various measurement results are shown in Table-1.
実施例6
(ト)固体触媒成分の製造
実施例1と同様にして、市販MIICt、 t−uJ、
1ilr採取し、精製ノルマルデカン2S−およびコー
エチルヘキサノール23.!; ml f 添加し、攪
拌下昇温して130℃で2時間反応させた。Example 6 (g) Production of solid catalyst component In the same manner as in Example 1, commercially available MIICt, tuJ,
1ilr was collected and purified normal decane 2S- and coethylhexanol 23. ! ml f was added, and the temperature was raised while stirring, and the reaction was carried out at 130° C. for 2 hours.
を得た。I got it.
この溶液を一2θ℃に冷却したTiCt、 3(Itl
に1時間かけて滴下した。滴下後徐々に昇温し、q時間
後に//(76Cまで昇温させた。TiCt, 3 (Itl
It was added dropwise over a period of 1 hour. After dropping, the temperature was gradually raised to 76C after q hours.
iio℃においてジイソブチルフタレート2、g 9r
を添加し、同温度で2時間反応させた。Diisobutyl phthalate 2, g 9r at iio°C
was added and reacted at the same temperature for 2 hours.
次いでこのものを熱ろ過して固体部を採取し、TiCt
43 u !r firに懸濁させた後/100Cに昇
温し110℃でコ時間反応させた。その後熱ノルマルデ
カン200−でコ回洗浄し、更に室温において、精製ノ
ルマルヘキサンコθθ−でタロ洗浄して固体触媒成分(
4)3.りIrを得た。Next, this material was heat filtered to collect the solid part, and TiCt
43 u! After suspending in r fir, the temperature was raised to 100C and reacted at 110C for 1 hour. Thereafter, the solid catalyst component (
4)3. Ir was obtained.
このもののT1含量は3.コ重fkチであった。The T1 content of this product is 3. It was heavy fk chi.
(B) 前重合
実施例6(ト)で得られた固体触媒成分を用い実施例/
CB)と同様にして前重合を行りて、前重合触媒成分
を得た。この前重合触媒成分は、固体触媒成分(A)/
、g当シ重合体2011含んでいた。(B) Example/using the solid catalyst component obtained in Prepolymerization Example 6 (g)
Prepolymerization was carried out in the same manner as in CB) to obtain a prepolymerization catalyst component. This prepolymerization catalyst component is solid catalyst component (A)/
, g of the polymer 2011 was contained.
(C) プロピレンの重合
実施例1(C)において、実施例& CB)で得られた
前重合触媒成分を用いたことと、パラメチル安息香酸メ
チルに代えて、フェニル) IJエトキシシラン0.0
5ミリモルを用いたこと、およびH2ヲθ、J kg
/ (−14にした以外は実施例/(C)と同様にして
プロピレンの重合を行い、粉末ポリプロピレン2301
!’l得た。触媒効率CEは/ に 、? 009−p
p / g−Cat 、重合活性にはりlOであり、ρ
Bは0.lI!; 9/cc 、 IIは97、タチ、
MFIはlO0夕であった。このものの透明性の評価は
○であシ、第1降伏強度YSは3り:lkQ/(−d、
曲げ弾性率は/ 7.200kq / adであった。(C) Polymerization of propylene In Example 1 (C), the prepolymerization catalyst component obtained in Example & CB) was used, and in place of methyl paramethylbenzoate, phenyl) IJ ethoxysilane 0.0
5 mmol was used, and H2woθ, J kg
/ (Propylene was polymerized in the same manner as in Example/(C) except that it was changed to -14, and powder polypropylene 2301
! 'l got it. What is the catalyst efficiency CE? 009-p
p/g-Cat, polymerization activity is lO, and ρ
B is 0. lI! ; 9/cc, II is 97, Tachi,
MFI was lO0 evening. The transparency evaluation of this product is ○, and the first yield strength YS is 3: lkQ/(-d,
The flexural modulus was /7.200kq/ad.
比較例1
(ト))前重合
精製N2で充分置換した/1の誘導攪拌式ガラスオート
クレーブにN2シール下、室温でノルマルヘキサン/f
d、)ジエチルアルミニウム1.λミ9
施例1の囚で得られた固体触媒成分(4)/iを添加し
た。その後、2!;℃に保持して、プロピレンガスを3
分間流通させることにより前重合を行なった。前重合終
了後、ノルマルヘキサン/20−を加え、精製N2で充
分置換した200艷のフラスコに全量移して本重合に使
用した。ここで得られた前重合触媒成分は固体触媒成分
(A)/g当シボリプロビレンをion含んでいた。Comparative Example 1 (g)) Pre-polymerization Purification N-hexane/f was placed at room temperature under a N2 seal in a /1 induction stirring glass autoclave which had been sufficiently purged with N2.
d.) Diethyl aluminum 1. λmi9 The solid catalyst component (4)/i obtained in Example 1 was added. After that, 2! ; Keep at ℃ and add propylene gas at 3℃.
Prepolymerization was carried out by flowing for a minute. After the prepolymerization was completed, normal hexane/20- was added, and the entire amount was transferred to a 200-bar flask that had been sufficiently purged with purified N2, and used for the main polymerization. The prepolymerization catalyst component obtained here contained ions of solid catalyst component (A)/g of civoripropylene.
(C) プロピレンの重合
比較例1@で得られた前重合触媒成分を用いる以外は実
施例1の(C)と同様にしてプロピレンの重合を行なっ
たところ、触媒効率CE= / 9 t 0 0 、9
’−pp / I−Cat s重合活性に=440、I
I= タ り、コ チ、 ρB = 0.’l 7
fj/ccM F I = ’1.2であった。(C) Polymerization of propylene Polymerization of propylene was carried out in the same manner as in (C) of Example 1, except that the prepolymerization catalyst component obtained in Comparative Example 1 was used, and the catalyst efficiency CE = / 9 t 0 0 ,9
'-pp/I-Cats polymerization activity = 440, I
I=Tari, Kochi, ρB=0. 'l 7
fj/ccMF I = '1.2.
各種測定結果は表−/に示した。Various measurement results are shown in Table-/.
このものの透明性の評価は、ぼやけてみえることからΔ
であシ、第1降伏強度YSは.330kfl / cr
l 、曲げ弾性率は/ j / 0 01c9/(−1
71であった。The evaluation of the transparency of this item is Δ because it looks blurry.
Yes, the first yield strength YS is. 330kfl/cr
l, the flexural modulus is /j/0 01c9/(-1
It was 71.
以上の結果から、3−メチルブテン−lもしくは3−メ
チルブテン−1とプロピレンの混合物で前重合させた前
重合触媒成分を用いて本重合することにより、透明性お
よび剛性の優れた重合体が得られることが明らかとなグ
た◇〔発明の効果〕
本発明の方法によれば、透明性や剛性に優れ、嵩密度の
高いプロピレン重合体が得られるだけでなく、重合活性
及び立体規則性が高いので、重合後の触媒残渣や非品性
重合体の除去工程が不要となり、工業的にも有利である
。From the above results, a polymer with excellent transparency and rigidity can be obtained by main polymerization using a prepolymerization catalyst component prepolymerized with 3-methylbutene-1 or a mixture of 3-methylbutene-1 and propylene. [Effects of the Invention] According to the method of the present invention, not only a propylene polymer with excellent transparency and rigidity and high bulk density can be obtained, but also with high polymerization activity and stereoregularity. Therefore, a process for removing catalyst residues and non-quality polymers after polymerization becomes unnecessary, which is also advantageous from an industrial perspective.
Claims (7)
化合物を必須成分とする固体触媒成分(A)と周期律表
第 I 〜III族の金属の有機金属化合物(B)より成る触
媒の存在下に、3−メチルブテン−1、もしくは3−メ
チルブテン−1と炭素数3以上のオレフィンとの混合物
を前重合させ、次いで炭素数3以上のオレフィンを単独
重合または共重合させることを特徴とするオレフィン重
合体の製造方法。(1) In the presence of a catalyst consisting of a solid catalyst component (A) whose essential components are magnesium, titanium, halogen, and an electron-donating compound and an organometallic compound (B) of a metal from Groups I to III of the periodic table, An olefin polymer characterized in that 3-methylbutene-1 or a mixture of 3-methylbutene-1 and an olefin having 3 or more carbon atoms is prepolymerized, and then an olefin having 3 or more carbon atoms is homopolymerized or copolymerized. Production method.
前重合させることを特徴とする、特許請求の範囲第1項
記載の方法。(2) The method according to claim 1, characterized in that a mixture of 3-methylbutene-1 and propylene is prepolymerized.
C)を存在させることを特徴とする特許請求の範囲第1
項記載の方法。(3) Electron-donating compound (
C)
The method described in section.
特許請求の範囲第1項記載の方法。(4) The method according to claim 1, characterized in that the temperature of the prepolymerization exceeds 50°C.
.01〜100gであることを特徴とする特許請求の範
囲第1項記載の方法。(5) The amount of polymerization in the prepolymerization is 0 per 1 g of solid catalyst component (A)
.. 2. The method according to claim 1, wherein the amount is 0.01 to 100 g.
量%であることを特徴とする特許請求の範囲第1項記載
の方法。(6) The method according to claim 1, wherein the amount of polymerization in the prepolymerization is 0.001 to 30% by weight of the total amount of polymerization.
_2−nXn(式中R^1はアルキル基、アリール基ま
たはアラルキル基を示し、Xはハロゲン、nは 0≦n≦2を示す。)で表わされるマグネシウム化合物
、一般式Ti(OR^2)_mX_4_−_m(式中R
^2はアルキル基、アリール基またはアラルキル基を示
し、Xはハロゲン、mは0≦m≦4を示す。)で表わさ
れるチタン化合物及び電子供与性化合物を反応させて得
られることを特徴とする、特許請求の範囲第1項記載の
方法。(7) The solid catalyst component (A) has the general formula Mg (OR^1)
Magnesium compound represented by _2-nXn (wherein R^1 represents an alkyl group, aryl group, or aralkyl group, X represents a halogen, and n represents 0≦n≦2), general formula Ti (OR^2) _mX_4_-_m (in the formula R
^2 represents an alkyl group, an aryl group, or an aralkyl group, X represents a halogen, and m represents 0≦m≦4. 2. The method according to claim 1, characterized in that it is obtained by reacting a titanium compound represented by () and an electron-donating compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62283989A JPH0830095B2 (en) | 1987-11-10 | 1987-11-10 | Process for producing olefin polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62283989A JPH0830095B2 (en) | 1987-11-10 | 1987-11-10 | Process for producing olefin polymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01126306A true JPH01126306A (en) | 1989-05-18 |
JPH0830095B2 JPH0830095B2 (en) | 1996-03-27 |
Family
ID=17672842
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62283989A Expired - Fee Related JPH0830095B2 (en) | 1987-11-10 | 1987-11-10 | Process for producing olefin polymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0830095B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03163110A (en) * | 1988-09-14 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Prepolymerized catalyst component for olefin polymerization, olefin polymerization catalyst, and method of polymerization therewith |
JPH03170511A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Polypropylene film |
JPH03170512A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Injection molded article of polypropylene |
-
1987
- 1987-11-10 JP JP62283989A patent/JPH0830095B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03163110A (en) * | 1988-09-14 | 1991-07-15 | Mitsui Petrochem Ind Ltd | Prepolymerized catalyst component for olefin polymerization, olefin polymerization catalyst, and method of polymerization therewith |
JPH03170511A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Polypropylene film |
JPH03170512A (en) * | 1989-08-11 | 1991-07-24 | Mitsui Petrochem Ind Ltd | Injection molded article of polypropylene |
Also Published As
Publication number | Publication date |
---|---|
JPH0830095B2 (en) | 1996-03-27 |
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