JPH0780949B2 - Process for producing olefin polymer - Google Patents
Process for producing olefin polymerInfo
- Publication number
- JPH0780949B2 JPH0780949B2 JP29376987A JP29376987A JPH0780949B2 JP H0780949 B2 JPH0780949 B2 JP H0780949B2 JP 29376987 A JP29376987 A JP 29376987A JP 29376987 A JP29376987 A JP 29376987A JP H0780949 B2 JPH0780949 B2 JP H0780949B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- represented
- group
- general formula
- halogen
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims description 37
- 229920000098 polyolefin Polymers 0.000 title description 8
- 239000010936 titanium Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000011777 magnesium Substances 0.000 claims description 38
- 239000011949 solid catalyst Substances 0.000 claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims description 28
- 150000003609 titanium compounds Chemical class 0.000 claims description 24
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- 150000003377 silicon compounds Chemical class 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 150000002681 magnesium compounds Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000012265 solid product Substances 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 claims description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 4
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- MQHSFMJHURNQIE-UHFFFAOYSA-N tetrakis(2-ethylhexyl) silicate Chemical compound CCCCC(CC)CO[Si](OCC(CC)CCCC)(OCC(CC)CCCC)OCC(CC)CCCC MQHSFMJHURNQIE-UHFFFAOYSA-N 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- QVRHUEBADCVHJB-UHFFFAOYSA-N tetrakis(4-methylphenyl) silicate Chemical compound C1=CC(C)=CC=C1O[Si](OC=1C=CC(C)=CC=1)(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 QVRHUEBADCVHJB-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 150000003739 xylenols Chemical class 0.000 claims description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 72
- 239000002245 particle Substances 0.000 description 55
- 229920000642 polymer Polymers 0.000 description 40
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 36
- -1 Ethylene, propylene Chemical group 0.000 description 29
- 239000000843 powder Substances 0.000 description 28
- 238000006116 polymerization reaction Methods 0.000 description 27
- 239000004743 Polypropylene Substances 0.000 description 25
- 230000037048 polymerization activity Effects 0.000 description 25
- 238000009826 distribution Methods 0.000 description 24
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000002002 slurry Substances 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 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
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NHFRGTVSKOPUBK-UHFFFAOYSA-N 4-phenylbutanal Chemical compound O=CCCCC1=CC=CC=C1 NHFRGTVSKOPUBK-UHFFFAOYSA-N 0.000 description 1
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 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
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- KKNLETZIKBOKKL-UHFFFAOYSA-N ethenyl(diethyl)alumane Chemical compound CC[Al](CC)C=C KKNLETZIKBOKKL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 description 1
- 229940093471 ethyl oleate Drugs 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 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
- 229940017219 methyl propionate Drugs 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規な固体触媒成分を用いたオレフィン重合
体の製造方法に関する。更に詳しくは、重合活性に優
れ、立体規則性、および粒子性状に優れた重合体を与え
る新規な担体付触媒成分と周期律表第Ｉ〜III族金属の
有機金属化合物、及び必要に応じて電子供与性化合物と
からなる触媒を用いた、エチレン、プロピレン、ブテン
−１、４−メチルペンテン−１、３−メチルブテン−１
等のα−オレフィン重合体の製造方法に関するものであ
る。TECHNICAL FIELD The present invention relates to a method for producing an olefin polymer using a novel solid catalyst component. More specifically, a novel catalyst component with a carrier that gives a polymer having excellent polymerization activity, stereoregularity, and particle properties, an organometallic compound of Group I to Group III metal of the periodic table, and, if necessary, an electron Ethylene, propylene, butene-1,4-methylpentene-1,3-methylbutene-1 using a catalyst composed of a donor compound
The present invention relates to a method for producing an α-olefin polymer such as
特には、炭素数３以上のα−オレフィンに対して、高活
性で、高立体規則性かつ粒子性状の良好な重合体を製造
する方法に関する。In particular, it relates to a method for producing a polymer having high activity, high stereoregularity, and good particle properties with respect to an α-olefin having 3 or more carbon atoms.
従来、担体付触媒で炭素数３以上のα−オレフィンに対
し、高活性でかつ高立体規則性の重合体を与える触媒の
製造法については、数多くの提案があるが、それらの多
くは、重合活性や立体規則性の面で充分満足すべきもの
ではなく、一層の改良が望まれている。また、得られる
重合体の粒子性状の点においても不充分であり、改良が
望まれている。Conventionally, there have been many proposals for a method for producing a catalyst which gives a highly active and highly stereoregular polymer to an α-olefin having 3 or more carbon atoms by a supported catalyst, but most of them are polymerized. It is not sufficiently satisfactory in terms of activity and stereoregularity, and further improvement is desired. Further, the particle properties of the resulting polymer are insufficient, and improvement is desired.
粒子性状は、スラリー重合や気相重合等においては、き
わめて重要な因子であり、粒子性状が悪い場合、重合槽
内での付着や重合体の抜出し不良、あるいは配管の閉塞
等のトラブルの原因となる。The particle property is an extremely important factor in slurry polymerization, gas phase polymerization, etc., and if the particle property is poor, it may cause problems such as adhesion in the polymerization tank or poor extraction of the polymer, or blockage of the pipe. Become.
例えば、特開昭52-98076号、特開昭53-2580号ではマグ
ネシウムアルコキシド、チタンハロゲン化物、電子供与
体の三成分の接触反応生成物を触媒成分として用いる方
法が開示されているが、重合活性、立体規則性、生成ポ
リマーの粒子性状共、不十分なものであった。For example, JP-A-52-98076 and JP-A-53-2580 disclose a method in which a catalytic reaction product of three components of magnesium alkoxide, titanium halide and electron donor is used as a catalyst component. The activity, stereoregularity, and particle properties of the produced polymer were inadequate.
特開昭56-120711号では、上記三成分に加えてチタンテ
トラアルコキシドを用いる方法が開示されている。JP-A-56-120711 discloses a method of using titanium tetraalkoxide in addition to the above three components.
即ち、マグネシウムアルコキシドをヘプタン中でチタン
テトラアルコキシドで処理し得られた処理固体を有機酸
エステル、チタンハロゲン化物で処理するものである。
この方法も、重合活性（チタン1g当り、１時間当り、プ
ロピレン圧1kg/cm2当りのポリマー収量）は、高々10,00
0g・PP/g・Ti・kg/cm2ppy・hr強であり、アイソタクテ
ィックインデックスも最も高いもので94％、更に嵩密度
も0.30g/c.c.近辺と充分に高い性能を示すものではなか
った。That is, the treated solid obtained by treating magnesium alkoxide with titanium tetraalkoxide in heptane is treated with organic acid ester and titanium halide.
Also in this method, the polymerization activity (polymer yield per 1 g of titanium, per hour, propylene pressure of 1 kg / cm 2 ) is at most 10,00.
0g ・ PP / g ・ Ti ・ kg / cm 2 ppy ・ hr +, the highest isotactic index is 94%, and the bulk density is not higher than 0.30g / cc. It was
また、特開昭59-120603号においては、マグネシウムア
ルコキシド及び／又はマンガンアルコキシドをチタンテ
トラアルコキシドと接触せしめることにより液体を形成
し、該液体をハロゲン化剤を含んで成る流体と反応せし
めること、及び電子供与体で処理することによって処理
された固体を形成し、そして、該固体を遷移金属ハライ
ドで後処理する段階を含んで成る方法が開示されてい
る。Further, in JP-A-59-120603, a liquid is formed by contacting a magnesium alkoxide and / or a manganese alkoxide with a titanium tetraalkoxide, and the liquid is reacted with a fluid containing a halogenating agent, and A method is disclosed which comprises the steps of forming a treated solid by treating with an electron donor and post-treating the solid with a transition metal halide.
同方法は、狭くそして高い粒子直径の分布を有し、重合
体中の微粒子成分が最小であるポリオレフィンを供する
触媒成分を製造することを重要な目的としている。粒径
分布に関しては、大粒子が多く必ずしも分布が狭いとは
言い難いが、微粒に関しては相当程度減少している事が
認められる。しかし、特に立体規則性に関しては、改良
効果が充分高いとは言えず、アイソタクティックインデ
ックスは90％以下である。The method has the important aim of producing a catalyst component which gives a polyolefin having a narrow and high particle diameter distribution and having a minimum of fines components in the polymer. Regarding the particle size distribution, it cannot be said that there are many large particles and the distribution is not necessarily narrow, but it is recognized that the particle size is considerably reduced. However, especially with regard to stereoregularity, the improvement effect cannot be said to be sufficiently high, and the isotactic index is 90% or less.
その他マグネシウムの酸素含有有機化合物を用いるもの
としては、特開昭57-34103、同58-127708、同60-8121
0、同60-81211、同60-170603、同60-192709、同61-2113
08、同61-211310、同57-159806、同59-182806、またチ
タニウムアルコキシドを用いるものとしては、特開昭59
-206408、同55-62907、同56-30406、同57-131205、同50
-34084またマグネシウムアルコキシドとチタニウムアル
コキシドを組合せたものについては、特開昭56-16620
5、同57-190004、同57-200407、同60-32804、同60-2487
05、同58-183706、同46-6111、同47-32081、同54-318
4、同58-96613、同48-66178、同54-16393、同62-1840
5、またケイ素化合物を用いるものとしては、特開昭56-
151704、同56-155205、同60-262806、同61-296006、同6
2-508、その他Mg担持型触媒に関するものとして、特開
昭52-151691、同56-152810、同58-83006が挙げられる。Other examples of magnesium-containing organic compounds containing oxygen include those disclosed in JP-A-57-34103, JP-A-58-127708, and JP-A-60-8121.
0, 60-81211, 60-170603, 60-192709, 61-2113
08, 61-211310, 57-159806, 59-182806, and those using titanium alkoxide are disclosed in JP-A-59-59
-206408, 55-62907, 56-30406, 57-131205, 50
JP-A-56-16620 discloses a combination of magnesium alkoxide and titanium alkoxide.
5, Same 57-190004, Same 57-200407, Same 60-32804, Same 60-2487
05, 58-183706, 46-6111, 47-32081, 54-318
4, the same 58-96613, the same 48-66178, the same 54-16393, the same 62-1840
5, and those using a silicon compound are disclosed in JP-A-56-
151704, 56-155205, 60-262806, 61-296006, 6
Examples of 2-508 and other Mg-supported catalysts include JP-A-52-151691, JP-A-56-152810, and JP-A-58-83006.
本発明者らは、先に特願昭62-122336号において、マグ
ネシウムジアルコキシドを電子供与性化合物、ケイ素テ
トラアルコキシド及び四塩化チタン等のチタン化合物で
処理する事により、重合活性、立体規則性及び粒子性状
に優れた触媒成分の製造法を提案しているが、粒子性状
については、更に一層の改良が望まれていた。The present inventors previously disclosed that in Japanese Patent Application No. 62-122336, by treating a magnesium dialkoxide with an electron donating compound, a silicon compound such as silicon tetraalkoxide and titanium tetrachloride, polymerization activity, stereoregularity and Although a method for producing a catalyst component having excellent particle properties has been proposed, further improvement in particle properties has been desired.
本発明者らは、上述の触媒系の高活性、高立体規則性を
維持しながら、かつ粒子性状の一層優れた重合体を与え
る固体触媒成分を得るべくその製法について鋭意検討し
た結果、本発明に到達した。即ち、本発明の要旨は、一
般式Mg(OR1)n(OR2)2-n（式中、R1、R2はアルキル基、ア
リール基またはアラルキル基を示し、R1とR2は同一でも
異なってもよい。ｎは２≧ｎ≧０を示す。）で表わされ
るマグネシウム化合物（a1）、一般式Ti(OR3)4（式中、
R3はアルキル基、アリール基またはアラルキル基を示
す。）で表わされるチタン化合物（a2）及び一般式Si(O
R4)4（式中、R4はアルキル基、アリール基またはアラル
キル基を示す。）で表わされるケイ素化合物（a3）およ
び必要に応じて一般式R5OH（式中、R5はアルキル基、ア
リール基またはアラルキル基を示す。）（a4）を加熱反
応させ、次いで該反応生成物（ａ）を一般式TiXP(OR9)
4-P（式中、R9はアルキル基を示し、Ｘはハロゲン、Ｐ
は０＜Ｐ≦４を示す。）で表わされるハロゲン含有チタ
ン化合物（ｂ）および電子供与性化合物（ｃ）で接触処
理することによって得られる固体触媒成分（Ａ）と一般
式▲AlR8 m▼X3-m（式中、R8は炭素数１〜20個の炭化水
素基を示し、Ｘはハロゲン、ｍは２〜３の数を示す。）
で表わされる有機アルミニウム化合物（Ｂ）、および必
要に応じて電子供与性化合物（Ｃ）とより成る触媒の存
在下にオレフィンを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。The present inventors have earnestly studied about the production method for obtaining a solid catalyst component which gives a polymer having more excellent particle properties while maintaining the high activity and high stereoregularity of the above-mentioned catalyst system. Reached That is, the gist of the present invention is the general formula Mg (OR 1 ) n (OR 2 ) 2-n (wherein R 1 and R 2 represent an alkyl group, an aryl group or an aralkyl group, and R 1 and R 2 are They may be the same or different, n is 2 ≧ n ≧ 0, and the magnesium compound (a 1 ) represented by the general formula Ti (OR 3 ) 4 (in the formula,
R 3 represents an alkyl group, an aryl group or an aralkyl group. ) Titanium compound (a 2 ) and the general formula Si (O
R 4 ) 4 (in the formula, R 4 represents an alkyl group, an aryl group or an aralkyl group) and a silicon compound (a 3 ) represented by the general formula R 5 OH (wherein R 5 is an alkyl group). A group, an aryl group or an aralkyl group) (a 4 ) is reacted by heating, and then the reaction product (a) is converted to the general formula TiX P (OR 9 )
4-P (In the formula, R 9 represents an alkyl group, X is halogen, P
Indicates 0 <P ≦ 4. ) And a solid catalyst component (A) obtained by contact treatment with a halogen-containing titanium compound (b) and an electron-donating compound (c) represented by the general formula ▲ AlR 8 m ▼ X 3-m (wherein R 8 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and m represents a number of 2 to 3.)
A method for producing an olefin polymer, characterized in that an olefin is polymerized or copolymerized in the presence of a catalyst consisting of an organoaluminum compound (B) represented by the formula (1) and optionally an electron donating compound (C). .
本発明を詳述すれば、 （ａ）一般式Mg(OR1)n(OR2)2-nで示されるマグネシウム
化合物（a1）と一般式Ti(OR3)4で示されるチタン化合物
（a2）と一般式Si(OR4)4で示されるケイ素化合物
（a3）、および必要に応じて一般式R5OHで示される化合
物（a4）の加熱反応生成物を （ｂ）一般式TiXP(OR9)4-P（式中、R9はアルキル基を示
し、Ｘはハロゲン、Ｐは０＜Ｐ≦４を示す。）で表わさ
れるハロゲン含有チタン化合物と （ｃ）電子供与性化合物で 接触処理することによって得られる固体触媒成分（Ａ）
と一般式▲AlR8 m▼X3-m（式中、R8は炭素数１〜20個の
炭化水素基を示し、Ｘはハロゲン、ｍは２〜３の数を示
す。）で表わされる有機アルミニウム化合物（Ｂ）とを
必須成分とし、更に適宜電子供与性化合物（Ｃ）を組合
せた触媒を用いて、オレフィンを重合または共重合する
ことを特徴とするオレフィン重合体の製造方法である。To explain the present invention in detail, (a) a magnesium compound (a 1 ) represented by the general formula Mg (OR 1 ) n (OR 2 ) 2-n and a titanium compound (a) represented by the general formula Ti (OR 3 ) 4 ( a 2 ) and a silicon compound (a 3 ) represented by the general formula Si (OR 4 ) 4 and, if necessary, a heating reaction product of the compound (a 4 ) represented by the general formula R 5 OH, (b) A halogen-containing titanium compound represented by the formula TiX P (OR 9 ) 4-P (wherein R 9 represents an alkyl group, X represents halogen, and P represents 0 <P ≦ 4), and (c) electron donation Catalyst component (A) obtained by contact treatment with a hydrophilic compound
And a general formula ▲ AlR 8 m ▼ X 3-m (wherein, R 8 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents halogen, and m represents a number of 2 to 3). A method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin with a catalyst comprising an organoaluminum compound (B) as an essential component and an electron donating compound (C) in combination as appropriate.
本発明で使用する一般式Mg(OR1)n(OR2)2-nで示されるマ
グネシウム化合物（a1）を具体的に示すと、Mg(OC
H3)2、Mg(OC2H5)2、Mg(OC3H7)2、Mg(OC4H9)2、Mg(OC
6H5)2、Mg(OCH2C6H5)2、Mg(OC2H5)(OC4H9)、Mg(OC6H5)
(OC4H9)、Mg(OC2H5)(OC6H5)、Mg(OC6H4CH3)2等のジアル
コキシマグネシウム、ジアリールオキシマグネシウム、
ジアラルキルオキシマグネシウム、アルキルオキシアリ
ールオキシマグネシウムを挙げることができる。これら
は混合して用いることもできる。Specific examples of the magnesium compound (a 1 ) represented by the general formula Mg (OR 1 ) n (OR 2 ) 2-n used in the present invention include Mg (OC 1
H 3) 2, Mg (OC 2 H 5) 2, Mg (OC 3 H 7) 2, Mg (OC 4 H 9) 2, Mg (OC
6 H 5 ) 2 , Mg (OCH 2 C 6 H 5 ) 2 , Mg (OC 2 H 5 ) (OC 4 H 9 ), Mg (OC 6 H 5 ).
(OC 4 H 9 ), Mg (OC 2 H 5 ) (OC 6 H 5 ), Mg (OC 6 H 4 CH 3 ) 2 etc. dialkoxy magnesium, diaryloxy magnesium,
Diaralkyloxy magnesium and alkyloxy aryloxy magnesium can be mentioned. These can also be mixed and used.
一般式Ti(OR3)4で示されるチタン化合物（a2）として
は、Ti(OCH3)4、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC
4H9)4、Ti(OC6H5)4、Ti(OCH2C6H5)4等が挙げられる。こ
れらは混合して用いることもできる。Examples of the titanium compound (a 2 ) represented by the general formula Ti (OR 3 ) 4 are Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC
4 H 9) 4, Ti ( OC 6 H 5) 4, Ti (OCH 2 C 6 H 5) 4 and the like. These can also be mixed and used.
一般式Si(OR4)4で示されるケイ素化合物（a3）として
は、テトラメトキシシラン、テトラエトキシシラン、テ
トラプロポキシシラン、テトラブトキシシラン、テトラ
（２−エチルヘキソキシ）シラン、テトラフェノキシシ
ラン、テトラ（ｐ−メチルフェノキシ）シラン等が挙げ
られる。これらは混合して用いることもできる。Examples of the silicon compound (a 3 ) represented by the general formula Si (OR 4 ) 4 include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetra (2-ethylhexoxy) silane, tetraphenoxysilane, tetra ( p-methylphenoxy) silane etc. are mentioned. These can also be mixed and used.
一般式R5OHで示される化合物（a4）としては、エタノー
ル、イソプロパノール、プロパノール、ブタノール、イ
ソブタノール、ヘキサノール、オクタノール、２エチル
ヘキサノール、ベンジルアルコール等のアルコール類；
フェノール、クレゾール、キシレノール、ブチルフェノ
ール等のフェノール類が挙げられる。Examples of the compound (a 4 ) represented by the general formula R 5 OH include alcohols such as ethanol, isopropanol, propanol, butanol, isobutanol, hexanol, octanol, 2ethylhexanol and benzyl alcohol;
Phenols such as phenol, cresol, xylenol and butylphenol can be mentioned.
これらのうち、マグネシウム化合物、チタン化合物、ケ
イ素化合物、R5OHで示される化合物のいずれかがOR基
（式中、Ｒはアルキル基、アリール基またはアラルキル
基を示す。）としてアリールオキシ基を含むものが好ま
しい。Of these, any of a magnesium compound, a titanium compound, a silicon compound and a compound represented by R 5 OH contains an aryloxy group as an OR group (wherein R represents an alkyl group, an aryl group or an aralkyl group). Those are preferable.
マグネシウム化合物（a1）とチタン化合物（a2）とケイ
素化合物（a3）および必要に応じてR5OHで示される化合
物（a4）の３ないし４種化合物からの反応物（ａ）を得
る方法としては、（a1）、（a2）、（a3）および必要に
応じて（a4）を同時に接触させて反応させる方法、
（a1）、（a2）、（a3）を反応させた後（a4）を反応さ
せる方法、（a1）と（a2）を反応させた後、（a3）およ
び必要に応じて（a4）を反応させる方法、（a1）、
（a2）および必要に応じて（a4）を反応させた後、
（a3）を反応させる方法、あるいは（a1）、（a3）およ
び必要に応じて（a4）を反応させた後（a2）を反応させ
る方法等が挙げられる。また反応時にヘキサン、ヘプタ
ン、ペンタン、ブタン、トルエン、キシレン等の不活性
炭化水素溶媒を存在させてもよい。反応温度は60℃〜20
0℃、好ましくは100℃〜150℃であり、反応時間は、0.5
〜４時間程度である。各成分の使用量をモル比で表わす
と通常次のとおりである。A reaction product (a) from a magnesium compound (a 1 ), a titanium compound (a 2 ), a silicon compound (a 3 ) and, if necessary, a compound (a 4 ) represented by R 5 OH from 3 to 4 compounds is used. As a method of obtaining, (a 1 ), (a 2 ), (a 3 ) and optionally (a 4 ) are simultaneously contacted and reacted,
(A 1 ), (a 2 ), (a 3 ) and then (a 4 ) are reacted, (a 1 ) and (a 2 ) are reacted, then (a 3 ) and, if necessary, Depending on the method of reacting (a 4 ), (a 1 ),
After reacting (a 2 ) and (a 4 ) if necessary,
Examples thereof include a method of reacting (a 3 ), a method of reacting (a 1 ), (a 3 ) and, if necessary, (a 4 ) and then (a 2 ). In addition, an inert hydrocarbon solvent such as hexane, heptane, pentane, butane, toluene, xylene may be present during the reaction. Reaction temperature is 60 ℃ ~ 20
0 ℃, preferably 100 ℃ ~ 150 ℃, the reaction time is 0.5
It is about 4 hours. The molar ratio of the amount of each component used is usually as follows.
Mg(OR1)n(OR2)2-n 1 Ti(OR3)4 0.05〜４、好ましくは0.2〜１ Si(OR4)4 0.1〜５、好ましくは0.2〜２ R5OH 0.1〜５、好ましくは１〜３ 本発明におけるマグネシウム化合物（a1）とチタン化合
物（a2）とケイ素化合物（a3）および必要に応じてR5OH
で示される化合物（a4）の加熱反応生成物（ａ）は
（a1）、（a2）、（a3）および必要に応じて（a4）の三
者あるいは四者の組成比により液状物を得る事も可能で
あるが、固体状生成物を含むスラリー状のものを使用す
る場合、良好な結果が得られる事が多い。Mg (OR 1 ) n (OR 2 ) 2-n 1 Ti (OR 3 ) 4 0.05-4, preferably 0.2-1 Si (OR 4 ) 4 0.1-5, preferably 0.2-2 R 5 OH 0.1-5 , Preferably 1-3 magnesium compound (a 1 ), titanium compound (a 2 ), silicon compound (a 3 ) and optionally R 5 OH in the present invention.
In compound represented by (a 4) heating the reaction product of (a) is (a 1), (a 2 ), the tripartite or four-party composition ratio of (a 3) and optionally (a 4) Although it is possible to obtain a liquid product, good results are often obtained when a slurry product containing a solid product is used.
液状である場合には、後述するチタンハロゲン化物との
反応の際に均一液状物を経るが、その後、固体成分が生
成しにくい傾向がある。When it is in a liquid state, it undergoes a uniform liquid substance during the reaction with the titanium halide described later, but thereafter, a solid component tends not to be easily produced.
本発明においては、上記のようにして得られる加熱反応
生成物（ａ）をヘキサン、ヘプタン、ペンタン、ブタ
ン、トルエン等の不活性炭化水素溶媒の存在下または不
存在下においてハロゲン含有チタン化合物（ｂ）および
電子供与性化合物（ｃ）で接触処理することによって固
体触媒成分（Ａ）を得る。In the present invention, the heating reaction product (a) obtained as described above is treated with a halogen-containing titanium compound (b) in the presence or absence of an inert hydrocarbon solvent such as hexane, heptane, pentane, butane or toluene. ) And an electron-donating compound (c), the solid catalyst component (A) is obtained.
ここで用いるハロゲン含有チタン化合物（ｂ）として
は、四塩化チタン、四臭化チタン、四沃化チタン及びチ
タンハロゲン・アルコレート化合物等が挙げられる。こ
のうち好ましくは、四塩化チタン及びチタンハロゲン・
アルコレート化合物が用いられる。Examples of the halogen-containing titanium compound (b) used here include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and titanium halogen / alcolate compounds. Of these, titanium tetrachloride and titanium halogen
An alcoholate compound is used.
電子供与性化合物（ｃ）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、含窒素化合物が挙げ
られる。このうち好ましくは含酸素化合物が用いられ
る。Examples of the electron-donating compound (c) generally include phosphorus-containing compounds, oxygen-containing compounds, sulfur-containing compounds, and nitrogen-containing compounds. Of these, oxygen-containing compounds are preferably used.
含酸素化合物としては、例えば下記一般式 （式中、R6、R7はアルコキシ基で置換されていてもよい
炭化水素基を示し、相互に結合して環状基を形成してい
てもよい。またｋは１〜３の数を示す。）で表わされる
化合物が挙げられる。具体的にはジエチルエーテル、ジ
プロピルエーテル、ジエチレングリコール、ポリプロピ
レングリコール、エチレンオキシド、プロピレンオキシ
ド、フランのようなエーテル類；アセトン、ジエチルケ
トン、メチルエチルケトン、メチルイソブチルケトン、
フェニルプロピルケトンのようなケトン類；酢酸エチ
ル、プロピオン酸メチル、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、トルイル酸プロピル、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、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
エチルの様なカルボン酸のエステル類あるいはγ−ブチ
ルラクトンの様な環状エステル類が挙げられ、また、安
息香酸−β−トリメトキシシリルエチル等のケイ素含有
カルボン酸エステル類も挙げられるが、好ましくはカル
ボン酸エステルが用いられ、特に好ましくは芳香族カル
ボン酸エステルが用いられる。As the oxygen-containing compound, for example, the following general formula (In the formula, R 6 and R 7 represent a hydrocarbon group which may be substituted with an alkoxy group, and may be bonded to each other to form a cyclic group. K represents a number of 1 to 3. ). Specifically, ethers such as diethyl ether, dipropyl ether, diethylene glycol, polypropylene glycol, ethylene oxide, propylene oxide and furan; acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as phenylpropyl ketone; ethyl acetate, methyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenylacetate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, methyl ethyl benzoate, ethyl ethyl benzoate, ethyl xylenecarboxylate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethoxybenzoate Examples thereof include esters of carboxylic acids such as ethyl acidate and ethyl cinnamate or cyclic esters such as γ-butyl lactone, and silicon-containing carboxylic acid esters such as benzoic acid-β-trimethoxysilylethyl. Among them, a carboxylic acid ester is preferably used, and an aromatic carboxylic acid ester is particularly preferably used.
本発明方法において、前記（ａ）、（ｂ）、（ｃ）成分
の接触処理方法としては、（ａ）を（ｂ）＋（ｃ）で処
理する方法、（ａ）と（ｂ）を予め接触させた後（ｃ）
で処理する方法、（ａ）と（ｃ）を予め接触させた後
（ｂ）で処理する方法等があるが、反応物（ａ）を調製
する際（ｃ）を共存させて反応させ、その後（ｂ）で処
理する方法も用いることができる。また、（ｂ）および
（ｃ）での処理工程を少くとも２回以上繰り返す方法も
好ましくとり得る。In the method of the present invention, as the contact treatment method of the components (a), (b) and (c), (a) is treated with (b) + (c), and (a) and (b) are previously treated. After contact (c)
There is a method of treating with (a) and (c) in advance and a method of treating with (b), etc., but when preparing the reaction product (a), (c) is allowed to coexist and then reacted. The method of processing in (b) can also be used. Further, a method in which the treatment steps of (b) and (c) are repeated at least twice or more can be preferably used.
処理後、不活性炭化水素溶媒で洗浄し、溶媒への可溶成
分を除去して、固体触媒成分（Ａ）が得られる。After the treatment, the solid catalyst component (A) is obtained by washing with an inert hydrocarbon solvent and removing the component soluble in the solvent.
触媒製造工程で使用する（ｂ）、（ｃ）各成分の１つの
工程での使用量を（ａ）成分中のマグネシウム化合物１
モルに対してモル比で表わすと通常次のとおりである。The amount of each of the components (b) and (c) used in the catalyst production step in one step is the magnesium compound 1 in the component (a).
It is usually as follows in terms of molar ratio with respect to mol.
ハロゲン含有チタン化合物（ｂ） 0.1〜100、 好ましくは１〜40 電子供与性化合物（ｃ） 0.01〜10、 好ましくは0.1〜
１、 そして、得られる固体触媒成分（Ａ）中のチタン含量が
0.1〜10重量％、好ましくは0.5〜５重量％になるように
上記各成分の使用量を調節する。Halogen-containing titanium compound (b) 0.1 to 100, preferably 1 to 40 electron donating compound (c) 0.01 to 10, preferably 0.1 to
1, and the titanium content in the obtained solid catalyst component (A) is
The amount of each component used is adjusted so as to be 0.1 to 10% by weight, preferably 0.5 to 5% by weight.
接触処理温度は通常−70℃〜200℃、好ましくは−30℃
〜150℃である。具体的には、例えば（ａ）成分と
（ｂ）成分、次いで（ｃ）成分を接触処理させる場合に
は、（ａ）成分と（ｂ）成分を−70℃〜50℃、好ましく
は−30℃〜30℃で接触させ、ついで（ｃ）成分を50℃〜
200℃、好ましくは70℃〜150℃で接触させて処理する
か、あるいは（ａ）成分と（ｂ）成分、及び（ｃ）成分
を同時に接触させる場合には−70℃〜50℃、好ましくは
−30℃〜30℃で接触させ、次いで50℃〜200℃、好まし
くは70℃〜150℃に加熱昇温させ処理すると良好な結果
が得られる。Contact treatment temperature is usually -70 ℃ ~ 200 ℃, preferably -30 ℃
~ 150 ° C. Specifically, for example, when the components (a) and (b), and then the component (c) are contact-treated, the components (a) and (b) are -70 ° C to 50 ° C, preferably -30 ° C. Contact at ℃ ~ 30 ℃, then (c) component 50 ℃ ~
The treatment is carried out by contacting at 200 ° C, preferably 70 ° C to 150 ° C, or when the components (a), (b), and (c) are simultaneously contacted, -70 ° C to 50 ° C, preferably Good results can be obtained by contacting at -30 ° C to 30 ° C, followed by heating to 50 ° C to 200 ° C, preferably 70 ° C to 150 ° C for heating.
接触温度を上記の如く低くすると、（ａ）成分と（ｂ）
成分及び場合によって同時に（ｃ）成分を接触処理する
際一度全体が均一の液状となり易く、この均一液状物を
加熱昇温して固体を析出せしめる事により、粒子性状良
好な固体触媒成分を得る事が出来る。When the contact temperature is lowered as described above, the components (a) and (b)
When the components and, if necessary, the component (c) are contact-treated at the same time, the whole is likely to become a uniform liquid, and by heating and heating this uniform liquid to precipitate a solid, a solid catalyst component having good particle properties can be obtained. Can be done.
処理する際は、不活性溶媒の存在下または不存在下で行
うことが出来、処理時間は0.5〜６時間程度である。The treatment can be carried out in the presence or absence of an inert solvent, and the treatment time is about 0.5 to 6 hours.
かくして得られる固体触媒成分（Ａ）と周期律表第Ｉ〜
III族の金属の有機金属化合物（Ｂ）、更に必要に応じ
て電子供与性化合物（Ｃ）を混合してなる触媒系を用い
て、オレフィンの重合または共重合を行ってポリオレフ
ィンを製造する。The solid catalyst component (A) thus obtained and Periodic Table I-
A polyolefin is produced by polymerizing or copolymerizing an olefin by using a catalyst system in which an organometallic compound (B) of a group III metal and, if necessary, an electron donating compound (C) are mixed.
この触媒系で用いられる一般式▲AlR8 m▼X3-m（式中、R
8は炭素数１〜20個の炭化水素基を示し、Ｘはハロゲ
ン、ｍは２〜３の数を示す。）で表わされる有機アルミ
ニウム化合物（Ｂ）は、上式においてR8は好ましく脂肪
族炭化水素基であり、この有機アルミニウム化合物
（Ｂ）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、トリイソブチルアルミニウ
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、モノビニルジエチルアルミニウム、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。General formula used in this catalyst system ▲ AlR 8 m ▼ X 3-m (where R
8 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen, and m represents a number of 2 to 3. In the above formula, R 8 is preferably an aliphatic hydrocarbon group, and specific examples of the organoaluminum compound (B) include triethylaluminum, tripropylaluminum and triisobutylaluminum. , Trihexylaluminum, trioctylaluminum, monovinyldiethylaluminum, diethylaluminummonochloride, etc., but trialkylaluminum is preferably used.
また、電子供与性化合物（Ｃ）としては、固体触媒成分
（Ａ）製造時に用いた（ｃ）成分が用いられるが、好ま
しくはカルボン酸エステルであり、特に好ましくは、芳
香族カルボン酸エステルである。As the electron-donating compound (C), the component (c) used in the production of the solid catalyst component (A) is used, but it is preferably a carboxylic acid ester, and particularly preferably an aromatic carboxylic acid ester. .
触媒各成分の使用割合は、触媒成分（Ａ）中のチタン対
（Ｂ）成分のアルミニウム化合物対（Ｃ）成分の電子供
与性化合物のモル比が 1:3〜500:0〜100 好ましくは、 1:20〜200:3〜50 になるように選ばれる。The ratio of each catalyst component used is such that the molar ratio of titanium in the catalyst component (A) to the aluminum compound of the component (B) to the electron-donating compound of the component (C) is 1: 3 to 500: 0 to 100, preferably Selected to be 1:20 to 200: 3 to 50.
重合または共重合に供され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−
１、４−メチルペンテン−１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ランダムまたはブロ
ック共重合にも適用できる。As the olefin to be polymerized or copolymerized, ethylene, propylene, butene-1,3-methylbutene-
1,4-methylpentene-1 and the like are preferable, and α-olefins having 3 or more carbon atoms are preferable, and propylene is particularly preferable. The polymerization can be applied to not only homopolymerization but also random or block copolymerization.
重合反応は不活性炭化水素、例えばヘキサン、ヘプタ
ン、トルエン、ペンタン、ブタン或いはこれらの混合
物、または重合を受けるα−オレフィンの液化物を溶媒
とするスラリー重合方式や気相中で重合を行なわせる気
相重合方式で行なうことができる。The polymerization reaction is carried out in a slurry polymerization system using an inert hydrocarbon such as hexane, heptane, toluene, pentane, butane or a mixture thereof, or a liquefaction product of an α-olefin to be polymerized as a solvent, or in a gas phase. It can be performed by a phase polymerization method.
温度は50〜100℃、好ましくは60〜90℃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。The temperature is 50 to 100 ° C, preferably 60 to 90 ° C, and the pressure is not particularly limited, but is usually selected from 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、これによりメルトフローインデックス（MFI,
ASTM-D1238で測定）を容易に変えることができる。It is also possible to allow hydrogen to be present as a molecular weight regulator in the polymerization system, which allows the melt flow index (MFI,
(Measured by ASTM-D1238) can be easily changed.
その他それぞれのα−オレフィンの重合、共重合に当っ
て通常採られる手段を本発明方法に適用することもでき
る。例えば前記触媒３成分（Ａ）、（Ｂ）、（Ｃ）また
は（Ａ）、（Ｂ）２成分を用いてα−オレフィンを前重
合させ、次いで前重合温度より高い温度でα−オレフィ
ンを本重合させる方法である。この際前重合量は、触媒
成分（Ａ）1g当り約0.1〜100g程度から選ばれるが、一
般的には約１〜3g程度で充分である。得られた前重合触
媒成分は、ヘキサン等の不活性炭化水素で洗浄した後本
重合に用いてもまた洗浄せずにそのまま用いてもよい。In addition, means generally used for the polymerization and copolymerization of each α-olefin can be applied to the method of the present invention. For example, the catalyst 3 components (A), (B), (C) or (A), (B) 2 components are used to prepolymerize an α-olefin, and then the α-olefin is converted to a main component at a temperature higher than the prepolymerization temperature. It is a method of polymerizing. At this time, the prepolymerization amount is selected from about 0.1 to 100 g per 1 g of the catalyst component (A), but generally about 1 to 3 g is sufficient. The obtained prepolymerization catalyst component may be used for the main polymerization after washing with an inert hydrocarbon such as hexane, or may be used as it is without washing.
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りこれら実施例によっ
て何ら制約を受けるものではない。Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited by these examples without departing from the gist thereof.
また、第１図は本発明に含まれる技術内容の理解を助け
るためのフローチャート図であり、本発明はその要旨を
逸脱しない限り、フローチャート図によって何ら制約を
受けるものではない。Further, FIG. 1 is a flow chart for facilitating the understanding of the technical contents included in the present invention, and the present invention is not restricted by the flow chart unless it deviates from the gist thereof.
なお、実施例において、重合活性（Ｋとして示す）は１
時間につきα−オレフィン圧1kg/cm2当り、固体触媒成
分（Ａ）1g当りのポリマー生成量（ｇ）であり、触媒効
率（CEとして示す）は固体触媒成分（Ａ）1g当りのポリ
マーの生成量（ｇ）である。In the examples, the polymerization activity (shown as K) is 1
The amount of polymer produced (g) per 1 g of solid catalyst component (A) per 1 kg / cm 2 of α-olefin pressure per hour, and the catalyst efficiency (shown as CE) is the production of polymer per 1 g of solid catalyst component (A). The amount (g).
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−ヘプタンにより６時間
抽出した場合の残量（重量％）である。The isotactic index (denoted as II) is the residual amount (% by weight) after extraction with boiling n-heptane for 6 hours in a modified Soxhlet extractor.
嵩密度（ρBとして示す。単位はg/c.c.）はJIS-K-6721
に従って測定した。メルトフローインデックス（MFIと
して示す）はASTM-D-1238に従って測定した。Bulk density (shown as ρ B. Unit is g / cc) is JIS-K-6721
Was measured according to. Melt flow index (shown as MFI) was measured according to ASTM-D-1238.
重合体の粒度分布は、三田村理研社の標準ふるいを用い
て測定した。The particle size distribution of the polymer was measured using a standard sieve manufactured by Mitamura Riken.
実施例１ （１）触媒成分（Ａ）の製造 攪拌機、温度計を備えた500mlのフラスコを精製N2で充
分置換した後、精製N2シール下、市販Mg(OC2H5)2を5g採
取し、Ti(OC4H9)47.4gおよびテトラフェノキシシラン8.
8gのトルエン溶液を添加し、攪拌下昇温して、130℃で
２時間反応させ黄色スラリー状の反応物（ａ）を得た。Example 1 (1) Production of catalyst component (A) After thoroughly replacing a 500 ml flask equipped with a stirrer and a thermometer with purified N 2 , 5 g of commercially available Mg (OC 2 H 5 ) 2 under purified N 2 seal. Collected, 7.4 g of Ti (OC 4 H 9 ) 4 and tetraphenoxysilane 8.
8 g of a toluene solution was added, the temperature was raised with stirring, and the mixture was reacted at 130 ° C. for 2 hours to obtain a reaction product (a) in the form of a yellow slurry.
反応後精製トルエン87mlを添加した後、−20℃まで冷却
し、−20℃においてTiCl441gを添加した。添加後全体は
均一溶液状となった。添加後徐々に昇温し、80℃に昇温
後安息香酸エチル1.3g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 the reaction, 87 ml of purified toluene was added, then cooled to -20 ° C, and 41 g of TiCl 4 was added at -20 ° C. After the addition, the whole solution became a uniform solution. After the addition, the temperature was gradually raised, and after the temperature was raised to 80 ° C., 1.3 g of ethyl benzoate was added, and the temperature was maintained for 1 hour. Then, it was washed with purified toluene to obtain a solid product.
次いで、TiCl482g、安息香酸エチル1.3gを添加し、80℃
において２時間固体生成物を処理した後、精製トルエン
で充分洗浄して固体触媒成分4.8gを得た。このものの担
持Ti量は、2.9重量％であった。Next, 82 g of TiCl 4 and 1.3 g of ethyl benzoate were added, and the temperature was 80 ° C.
After treating the solid product for 2 hours in (1), it was thoroughly washed with purified toluene to obtain 4.8 g of a solid catalyst component. The supported Ti amount was 2.9% by weight.
（２）プロピレンの重合 精製アルゴンで充分置換した2lの誘導攪拌式オートクレ
ーブに、アルゴンシール下、室温でトリエチルアルミニ
ウム1.0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H2を1.0kg/cm2になるように加
え、液体プロピレン700gを仕込んだ。次いで、上記固体
触媒15mgを添加した後、70℃に昇温し、１時間の重合を
行った。その後余剰のプロピレンをパージし、粉末ポリ
プロピレン383gを得た。触媒効率CEは25500g-PP/g-Ca
t、重合活性Ｋは850であった。ρBは0.43g/c.c.であ
り、II96.0％、MFIは4.8であった。得られた重合体の粒
度分布は非常に狭く、500μｍ〜250μｍの粒径をもつ粉
末体は全体の98％、100μｍ以下の微粉量は０％であっ
た。(2) Polymerization of propylene To a 2 liter induction stirring autoclave sufficiently replaced with purified argon, 1.0 mmol of triethylaluminum and 0.3 mmol of methyl paramethylbenzoate were added at room temperature under a blanket of argon, and 1.0 kg of H 2 was further added at room temperature. It was added to be cm 2, and 700 g of liquid propylene was charged. Then, after adding 15 mg of the above solid catalyst, the temperature was raised to 70 ° C. and polymerization was carried out for 1 hour. After that, excess propylene was purged to obtain 383 g of powder polypropylene. Catalytic efficiency CE is 25500g-PP / g-Ca
t, the polymerization activity K was 850. ρ B was 0.43 g / cc, II 96.0%, MFI was 4.8. The particle size distribution of the obtained polymer was very narrow, and 98% of the entire powders had a particle size of 500 to 250 μm, and the amount of fine powder of 100 μm or less was 0%.
実施例２ （１）触媒成分（Ａ）の製造 市販Mg(OC2H5)25g、Ti(OC4H9)43.7g、テトラ（２−エチ
ルヘキソキシ）シラン6gを用い、150℃で２時間反応さ
せて反応物（ａ）を得た。Example 2 (1) Preparation of commercially available catalyst component (A) Mg (OC 2 H 5) 2 5g, Ti (OC 4 H 9) 4 3.7g, using tetra (2-ethylhexoxy) silane 6 g, 2 at 0.99 ° C. The reaction was carried out for a time to obtain a reaction product (a).
反応物（ａ）に精製トルエンを添加し、０℃においてTi
Cl483gを添加した後、徐々に昇温し100℃において安息
香酸エチル1.3gを添加し同温度で２時間保持した。その
他は実施例１と同様な操作によって固体触媒成分を得
た。担持Ti量は2.7重量％であった。Purified toluene was added to the reaction product (a), and Ti was added at 0 ° C.
After adding 83 g of Cl 4 , the temperature was gradually raised, 1.3 g of ethyl benzoate was added at 100 ° C., and the mixture was kept at the same temperature for 2 hours. Others were the same as in Example 1 to obtain a solid catalyst component. The amount of supported Ti was 2.7% by weight.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝28,500g-PP/g-Cat、重合活性Ｋ
＝950、ρB＝0.39g/c.c.、II＝95.0％、MFI＝5.7であっ
た。また、重合体の粒度分布を測定した結果、250μｍ
〜74μｍの粒径をもつ粉末体は全体の96％であり、74μ
以下の微粉量は0.2％であった。(2) Polymerization of propylene When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 28,500 g-PP / g-Cat, and the polymerization activity was K.
= 950, ρ B = 0.39 g / cc, II = 95.0%, MFI = 5.7. In addition, as a result of measuring the particle size distribution of the polymer, 250 μm
96% of the powder body has a particle size of ~ 74μm.
The amount of fine powder below was 0.2%.
実施例３ （１）触媒成分（Ａ）の製造 市販Mg(OC2H5)25g、Ti(OC4H9)43.7g、テトラブトキシシ
ラン7gを用い、130℃で１時間反応させ反応物（ａ）を
得た。反応物（ａ）に精製トルエンを添加し、−10℃に
おいてTiCl483gを添加した後徐々に昇温し100℃におい
て安息香酸エチル1.3gを添加して同温度で２時間保持し
た。その他は実施例１と同様な操作によって固体触媒成
分を得た。担持Ti量は2.5重量％であった。Using Example 3 (1) Preparation of commercially available catalyst component (A) Mg (OC 2 H 5) 2 5g, Ti (OC 4 H 9) 4 3.7g, tetrabutoxysilane 7 g, the reaction was 1 hour at 130 ° C. The product (a) was obtained. Purified toluene was added to the reaction product (a), 83 g of TiCl 4 was added at −10 ° C., the temperature was gradually raised, 1.3 g of ethyl benzoate was added at 100 ° C., and the temperature was maintained at the same temperature for 2 hours. Others were the same as in Example 1 to obtain a solid catalyst component. The amount of supported Ti was 2.5% by weight.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝22,500g-PP/g-Cat、重合活性Ｋ
＝750、II＝96.5％、ρB＝0.40g/c.c.、MFI＝2.7であっ
た。重合体の粒度分布は、1000μｍ〜350μｍの粒径を
もつ粉末体は全体の90％であり、100μｍ以下の微粉量
は、0.3％であった。(2) Polymerization of Propylene When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 22,500 g-PP / g-Cat, and the polymerization activity was K.
= 750, II = 96.5%, ρ B = 0.40 g / cc, MFI = 2.7. The particle size distribution of the polymer was such that 90% of the powders had a particle size of 1000 μm to 350 μm, and the amount of fine powder of 100 μm or less was 0.3%.
実施例４ （１）触媒成分（Ａ）の製造 実施例１と同様の手法で、市販Mg(OC2H5)25gに、Ti(OC4
H9)47.4gを混合し、攪拌下昇温し、130℃で２時間反応
させ、液体生成物を得た。ここに、トルエンに溶解した
テトラフェノキシシラン8.8gを添加し、130℃で更に反
応を続行した。添加後、しばらくして反応系は均一溶液
からスラリー状となりテトラフェノキシシランの添加に
より新たな固体状生成物が生成していることが認められ
た。In Example 4 (1) same manner as in Production Example 1 of the catalyst component (A), commercially available Mg (OC 2 H 5) in 2 5 g, Ti (OC 4
H 9 ) 4 ( 7.4 g) was mixed, the temperature was raised with stirring, and the mixture was reacted at 130 ° C. for 2 hours to obtain a liquid product. To this, 8.8 g of tetraphenoxysilane dissolved in toluene was added, and the reaction was further continued at 130 ° C. It was confirmed that, after a while, the reaction system became a slurry form from a homogeneous solution and a new solid product was produced by the addition of tetraphenoxysilane.
このスラリー状生成物全量を用いる以外は実施例１と全
く同様に固体触媒成分を調製した。A solid catalyst component was prepared in exactly the same manner as in Example 1 except that the whole amount of this slurry product was used.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝25,800g-PP/g-Cat、重合活性Ｋ
＝860、II＝95.7％、ρB＝0.41g/c.c.、MFI＝6.5であっ
た。(2) Polymerization of propylene When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 25,800 g-PP / g-Cat and the polymerization activity was K.
= 860, II = 95.7%, ρ B = 0.41 g / cc, MFI = 6.5.
重合体の粒度分布は500μｍ〜177μｍの粒径をもつ粉末
体は全体の90％で、100μｍ以下の微粉量は0.5％であっ
た。Regarding the particle size distribution of the polymer, 90% of the powdered particles had a particle size of 500 μm to 177 μm, and the amount of fine powder of 100 μm or less was 0.5%.
実施例５ 実施例１の（２）において、パラメチル安息香酸メチル
に代えてアニス酸メチルを用いた以外は実施例１の
（２）と同様にして重合を行ったところ触媒効率CE＝2
1,000g-PP/g-Cat、重合活性Ｋ＝700、ρB＝0.44g/c.
c.、II＝97.2％、MFI＝3.6であった。Example 5 Polymerization was conducted in the same manner as in (2) of Example 1 except that methyl anisate was used in place of methyl paramethylbenzoate in (2) of Example 1, and the catalyst efficiency CE = 2.
1,000g-PP / g-Cat, polymerization activity K = 700, ρ B = 0.44g / c.
c., II = 97.2%, MFI = 3.6.
また得られた重合体の粒度分布は、実施例１の（２）と
ほぼ同等であった。The particle size distribution of the obtained polymer was almost the same as that in (2) of Example 1.
実施例６ （１）触媒成分（Ａ）の製造 Mg(OC6H5)29.2g、Ti(OC4H9)47.4g、テトラエトキシシラ
ン4.6gを用いて130℃で２時間反応させて反応物（ａ）
を得た。反応物（ａ）は黄色固体状であった。Example 6 (1) Production of catalyst component (A) Mg (OC 6 H 5 ) 2 9.2 g, Ti (OC 4 H 9 ) 4 7.4 g and tetraethoxysilane 4.6 g were used and reacted at 130 ° C. for 2 hours. Reaction product (a)
Got The reaction product (a) was a yellow solid.
この反応物（ａ）を用いた以外は実施例１の（１）と同
様な操作によって固体触媒成分を得た。担持Ti量は2.8
重量％であった。A solid catalyst component was obtained by the same operation as in (1) of Example 1 except that this reaction product (a) was used. The amount of Ti supported is 2.8
% By weight.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝21,000g-PP/g-Cat、重合活性Ｋ
＝700、II＝97％、ρB＝0.42g/c.c.、MFI＝3.5であっ
た。得られた重合体の粒度分布は500μｍ〜250μｍの粒
径を有するものが全体の96％と非常に狭く、100μｍ以
下の微粉量は0.4％であった。(2) Polymerization of propylene When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 21,000 g-PP / g-Cat, and the polymerization activity was K.
= 700, II = 97%, ρ B = 0.42 g / cc, MFI = 3.5. The particle size distribution of the obtained polymer was very narrow with 96% of the whole having a particle size of 500 μm to 250 μm, and the amount of fine powder of 100 μm or less was 0.4%.
実施例７ （１）触媒成分（Ａ）の製造 攪拌機、温度計を備えた500mlフラスコを精製N2で充分
置換した後、精製N2シール下、市販Mg(OC2H5)2を5g採取
し、Ti(OC4H9)47.4g、テトラエトキシシラン4.6gおよび
フェノール8.2gのトルエン溶液を添加し、攪拌下昇温し
て100℃で１時間反応させた。更に130℃で２時間反応さ
せ黄色固体スラリー状の反応物（ａ）を得た。Example 7 (1) Production of catalyst component (A) After thoroughly replacing a 500 ml flask equipped with a stirrer and a thermometer with purified N 2 , 5 g of commercially available Mg (OC 2 H 5 ) 2 was collected under a purified N 2 seal. Then, a toluene solution of 7.4 g of Ti (OC 4 H 9 ) 4 , 4.6 g of tetraethoxysilane and 8.2 g of phenol was added, and the temperature was raised with stirring to react at 100 ° C. for 1 hour. The reaction was further performed at 130 ° C. for 2 hours to obtain a reaction product (a) in the form of a yellow solid slurry.
反応後精製トルエン87mlを添加した後、−20℃まで冷却
し、−20℃においてTiCl425gを添加した。添加後全体は
均一溶液状となった。添加後徐々に昇温し、80℃に昇温
後安息香酸エチル1.3g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 the reaction, 87 ml of purified toluene was added, then cooled to -20 ° C, and 25 g of TiCl 4 was added at -20 ° C. After the addition, the whole solution became a uniform solution. After the addition, the temperature was gradually raised, and after the temperature was raised to 80 ° C., 1.3 g of ethyl benzoate was added, and the temperature was maintained for 1 hour. Then, it was washed with purified toluene to obtain a solid product.
次いで得られた固体生成物に、TiCl482g、安息香酸エチ
ル1.3gを添加し、80℃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で洗浄して固
体触媒成分5.0gを得た。このものの担持Ti量は2.7重量
％であった。Next, 82 g of TiCl 4 and 1.3 g of ethyl benzoate were added to the obtained solid product, and the solid product was treated at 80 ° C. for 1 hour. Then, it was washed with purified toluene at room temperature to obtain 5.0 g of a solid catalyst component. The amount of supported Ti was 2.7% by weight.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行な
い、粉末ポリプロピレン293gを得た。(2) Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in (2) of Example 1 to obtain 293 g of powder polypropylene.
触媒効率CEは19,500g-PP/g-Cat、重合活性Ｋは650あっ
た。得られた重合体のρBは0.42g/c.c.であり、IIは97.
0％、MFIは4.5であった。また、重合体の粒度分布は、5
00μｍ〜250μｍの粒度をもつ重合体が、全体の97％、1
00μｍ以下の微粉量が0.5％と非常に狭いものであっ
た。The catalyst efficiency CE was 19,500 g-PP / g-Cat, and the polymerization activity K was 650. The obtained polymer ρ B is 0.42 g / cc, II is 97.
0%, MFI was 4.5. The particle size distribution of the polymer is 5
Polymers with a particle size of 00 μm to 250 μm account for 97% of the total, 1
The amount of fine powder of 00 μm or less was 0.5%, which was very narrow.
実施例８ 実施例７の（１）と同様の手法で、市販Mg(OC2H5)25g、
Ti(OC4H9)47.4gおよびテトラエトキシシラン4.6gを混合
し、攪拌下昇温して130℃で１時間反応させた。次いで1
00℃まで降温し、フェノール8.2gのトルエン溶液を添加
した。添加後再び昇温して130℃で１時間反応させ、黄
色固体スラリー状の反応物（ａ）を得た。得られた反応
物（ａ）を用いて、以下は実施例７の（１）と同様にし
て固体触媒成分を得た。このものの担持Ti量は2.6重量
％であった。In the same manner as (1) of Example 8 Example 7, a commercially available Mg (OC 2 H 5) 2 5g,
7.4 g of Ti (OC 4 H 9 ) 4 and 4.6 g of tetraethoxysilane were mixed, the temperature was raised with stirring and the reaction was carried out at 130 ° C. for 1 hour. Then 1
The temperature was lowered to 00 ° C, and a toluene solution of 8.2 g of phenol was added. After the addition, the temperature was raised again and the reaction was carried out at 130 ° C. for 1 hour to obtain a reaction product (a) in the form of a yellow solid slurry. The reaction product (a) thus obtained was used to obtain a solid catalyst component in the same manner as in Example 7, (1). The supported Ti amount was 2.6% by weight.
実施例１の（２）と同様にして、プロピレンの重合を行
ったところ、触媒効率CE＝22,500g-PP/g-Cat、重合活性
Ｋ＝750、ρB＝0.43g/c.c.、II＝96.8％、MFI＝6.3であ
った。得られた重合体の粒度分布は、400μｍ〜150μｍ
の粒度を持つ重合体が全体の99％で、100μｍ以下の微
粉量が0.5％であった。Polymerization of propylene was carried out in the same manner as in (2) of Example 1, and the catalyst efficiency CE = 22,500 g-PP / g-Cat, polymerization activity K = 750, ρ B = 0.43 g / cc, II = 96.8. %, MFI = 6.3. The particle size distribution of the obtained polymer is 400 μm to 150 μm.
The polymer having a particle size of 99% was 99% of the whole, and the amount of fine powder of 100 μm or less was 0.5%.
実施例９ 実施例８において、チタン化合物としてTi(OC4H9)43.7g
を用い、精製トルエンの添加量を51mlとした以外は、実
施例８と同様にして固体触媒成分を得た。このものの担
持Ti量は2.9重量％であった。実施例１の（２）と同様
にしてプロピレンの重合を行ったところ、触媒効率CE＝
21,000g-PP/g-Cat、重合活性Ｋ＝700、ρB＝0.41g/c.
c.、II＝97.0％、MFI＝5.4であった。重合体の粒度分布
は、500μｍ〜200μｍの粒度をもつ重合体が全体の99％
で、100μｍ以下の微粉量が0.1重量％であった。Example 9 In Example 8, as a titanium compound, Ti (OC 4 H 9 ) 4 3.7 g
A solid catalyst component was obtained in the same manner as in Example 8 except that the amount of purified toluene added was 51 ml. The supported Ti amount was 2.9% by weight. When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE =
21,000g-PP / g-Cat, polymerization activity K = 700, ρ B = 0.41g / c.
c., II = 97.0%, MFI = 5.4. As for the particle size distribution of the polymer, 99% of the whole polymer has a particle size of 500 μm to 200 μm.
The amount of fine powder of 100 μm or less was 0.1% by weight.
実施例10 実施例８において、チタン化合物としてTi(OC2H5)45gを
用い、精製トルエンの添加量を62mlとした以外は、実施
例８と同様にして固体触媒成分を得た。このものの担持
Ti量は2.7重量％であった。実施例１の（２）と同様に
してプロピレンの重合を行った結果、触媒効率CE＝22,5
00g-PP/g-Cat、重合活性Ｋ＝750、ρB＝0.43g/c.c.、II
＝97.0％、MFI＝7.3であった。また、粒度分布は、600
μｍ〜350μｍの粒度をもつ重合体が全体の99％で100μ
ｍ以下の微粉量が0.3重量％であった。In Example 10 Example 8, using Ti (OC 2 H 5) 4 5g as titanium compounds, except for changing the amount of purified toluene was 62 ml, to obtain a solid catalyst component in the same manner as in Example 8. Carry this thing
The amount of Ti was 2.7% by weight. Polymerization of propylene was carried out in the same manner as in (2) of Example 1, and as a result, catalyst efficiency CE = 22,5
00g-PP / g-Cat, Polymerization activity K = 750, ρ B = 0.43g / cc, II
= 97.0%, MFI = 7.3. The particle size distribution is 600
Polymer with particle size of μm-350μm is 100μ in 99% of the whole
The amount of fine powder of m or less was 0.3% by weight.
実施例11 実施例７の（１）と同様な手法で、市販Mg(OC2H5)25g、
Ti(OC4H9)47.4gおよびフェノール8.2gのトルエン溶液を
室温において混合し、攪拌下昇温して110℃で１時間、
更に130℃で１時間反応させた。反応中にエタノールの
留出が認められた。In the same manner as in (1) of Example 11 Example 7 approach, commercially available Mg (OC 2 H 5) 2 5g,
A toluene solution of 7.4 g of Ti (OC 4 H 9 ) 4 and 8.2 g of phenol was mixed at room temperature, and the temperature was raised with stirring at 110 ° C. for 1 hour.
Further, the reaction was carried out at 130 ° C. for 1 hour. Distillation of ethanol was observed during the reaction.
次いで、テトラエトキシシラン4.6gを130℃において添
加し、同温度で１時間反応させて黄色固体スラリー状の
反応物（ａ）を得た。Then, 4.6 g of tetraethoxysilane was added at 130 ° C., and the mixture was reacted at the same temperature for 1 hour to obtain a reaction product (a) in the form of a yellow solid slurry.
得られた反応物（ａ）に精製トルエン87mlを添加した
後、−20℃まで冷却し、TiCl425gを添加した。添加後徐
々に昇温し、110℃に昇温後安息香酸エチル1.3g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 87 ml of purified toluene to the obtained reaction product (a), it was cooled to −20 ° C. and 25 g of TiCl 4 was added. After the addition, the temperature was gradually raised, and after the temperature was raised to 110 ° C, 1.3 g of ethyl benzoate was added and the temperature was maintained at the same temperature for 1 hour. Then, it was washed with purified toluene to obtain a solid product.
得られた固体生成物を用い、以降は、実施例７の（１）
と同様にして固体触媒成分を得た。このもののTi含量は
2.8重量％であった。The obtained solid product was used, and thereafter, (1) of Example 7 was used.
A solid catalyst component was obtained in the same manner as in. The Ti content of this product is
It was 2.8% by weight.
実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝31,500g-PP/g-Cat、重合活性Ｋ
＝1050、ρB＝0.45g/c.c.、II＝96.5％、MFI＝5.8であ
った。また、得られた重合体の粒度分布は350μｍ〜150
μｍの粒度をもつ重合体が全体の99％で、100μｍ以下
の微粉量が0.3％であった。When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 31,500 g-PP / g-Cat and the polymerization activity was K.
= 1050, ρ B = 0.45 g / cc, II = 96.5%, MFI = 5.8. The particle size distribution of the obtained polymer is 350 μm to 150 μm.
The polymer having a particle size of μm was 99% of the whole, and the fine powder amount of 100 μm or less was 0.3%.
実施例12 実施例11において、フェノールの代わりにｎ−ブタノー
ル6.5gを用い、ケイ素化合物として、テトラフェノキシ
シラン8.8gを用いた以外は、実施例11と同様にして反応
物（ａ）を得た。Example 12 A reaction product (a) was obtained in the same manner as in Example 11 except that 6.5 g of n-butanol was used in place of phenol and 8.8 g of tetraphenoxysilane was used as a silicon compound. .
得られた反応物（ａ）を用い、精製トルエンの添加量を
175mlとした以外は、実施例７の（１）と同様にして固
体触媒成分を得た。このもののTi含量は2.6重量％であ
った。Using the obtained reaction product (a), the amount of purified toluene added was
A solid catalyst component was obtained in the same manner as in Example 7, (1) except that the amount was 175 ml. The Ti content of this product was 2.6% by weight.
実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝21,300g-PP/g-Cat、重合活性Ｋ
＝710、ρB＝0.40g/c.c.、II＝97.2％、MFI＝4.5であ
り、重合体の粒度分布は、350μｍ〜150μｍの粒度をも
つ重合体が全体の98％で、100μｍ以下の微粉量が0.8％
であった。When propylene was polymerized in the same manner as in (2) of Example 1, the catalyst efficiency CE was 21,300 g-PP / g-Cat, and the polymerization activity K was K.
= 710, ρ B = 0.40 g / cc, II = 97.2%, MFI = 4.5, and the particle size distribution of the polymer is 98% of the polymer having a particle size of 350 μm to 150 μm, and the amount of fine powder of 100 μm or less. Is 0.8%
Met.
実施例13 実施例11において、チタン化合物としてTi(OC2H5)45gを
用い、精製トルエンの添加量を62mlとした以外は、実施
例11と同様にして固体触媒成分を得た。このもののTi含
量は2.7重量％であった。In Example 13 Example 11, using Ti (OC 2 H 5) 4 5g as titanium compounds, except for changing the amount of purified toluene was 62 ml, to obtain a solid catalyst component in the same manner as in Example 11. The Ti content of this product was 2.7% by weight.
実施例１の（２）と同様にしてプロピレンの重合を行
い、触媒効率CE＝30,000g-PP/g-Cat、重合活性Ｋ＝100
0、ρB＝0.43g/c.c.、II＝97.0％、MFI＝6.5という結果
であった。また重合体の粒度分布は、500μｍ〜200μｍ
の粒度をもつ重合体が全体の98％で、100μｍ以下の微
粉量が0.1％であった。Polymerization of propylene was carried out in the same manner as in (2) of Example 1, and the catalyst efficiency CE = 30,000 g-PP / g-Cat and the polymerization activity K = 100.
The results were 0, ρ B = 0.43 g / cc, II = 97.0%, and MFI = 6.5. The particle size distribution of the polymer is 500 μm to 200 μm.
98% of the polymer had a particle size of 0.1%, and the amount of fine powder of 100 μm or less was 0.1%.
実施例14 実施例11において、ケイ素化合物としてテトラフェノキ
シシラン8.8gを用い、精製トルエンの添加量を58mlとし
た以外は、実施例11と同様にして固体触媒成分を得た。
このもののTi含量は2.5重量％であった。Example 14 A solid catalyst component was obtained in the same manner as in Example 11 except that 8.8 g of tetraphenoxysilane was used as the silicon compound and the amount of purified toluene added was 58 ml.
The Ti content of this product was 2.5% by weight.
実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝28,500g-PP/g-Cat、重合活性Ｋ
＝950、ρB＝0.43g/c.c.、II＝96.7％、MFI＝6.7であ
り、重合体の粒度分布は、400μｍ〜200μｍの粒度をも
つ重合体が全体の98％で100μｍ以下の微粉量が0.2％で
あった。When propylene was polymerized in the same manner as in (2) of Example 1, catalyst efficiency CE = 28,500 g-PP / g-Cat and polymerization activity K
= 950, ρ B = 0.43 g / cc, II = 96.7%, MFI = 6.7, and the particle size distribution of the polymer is such that 98% of the polymers having a particle size of 400 μm to 200 μm have a fine powder amount of 100 μm or less. It was 0.2%.
実施例15 （１）プロピレン前重合 精製N2シール下、室温において、１オートクレーブ
に、精製ノルマルヘキサン300ml、トリエチルアルミニ
ウム1.0ミリモル、パラメチル安息香酸メチル0.3ミリモ
ルおよび実施例１の（１）で得られた固体触媒成分1.5g
を添加した。添加後25℃で５分間プロピレンを供給して
前重合を行った。得られた前重合触媒成分は、3.5gのポ
リプロピレンを含有していた。Example 15 (1) Propylene prepolymerization Purified normal hexane (300 ml), triethylaluminum (1.0 mmol), paramethyl benzoate (0.3 mmol) and (1) of Example 1 were obtained in one autoclave at room temperature under a purified N 2 seal. Solid catalyst component 1.5g
Was added. After the addition, propylene was fed for 5 minutes at 25 ° C. to carry out prepolymerization. The obtained prepolymerization catalyst component contained 3.5 g of polypropylene.
（２）プロピレンの本重合 実施例１の（２）と同様な手法で、２オートクレーブ
に、トリエチルアルミニウム1.0ミリモル、パラメチル
安息香酸メチル0.3ミリモル、H21.0kg/cm2、液体プロピ
レン700gを仕込んだ。次いで70℃に昇温し、昇温後上記
（１）で得られた前重合触媒成分を固体触媒成分として
15mg添加し、70℃で１時間重合を行った。その後余剰の
プロピレンをパージし粉末ポリプロピレン315gを得た。
触媒効率CEは21,000g-PP/g-Cat、重合活性Ｋは700であ
った。ρBは0.47g/c.c.であり、IIは97.2％、MFIは7.5
であった。得られた重合体の粒度分布は非常に狭く、50
0μｍ〜250μｍの粒径をもつ粉末体は、全体の99％、10
0μｍ以下の微粉量は０％であった。(2) Main Polymerization of Propylene In the same manner as in (2) of Example 1, 2 mmol of autoclave was charged with 1.0 mmol of triethylaluminum, 0.3 mmol of methyl paramethylbenzoate, 1.0 kg / cm 2 of H 2 and 700 g of liquid propylene. . Then, the temperature is raised to 70 ° C., and after the temperature is raised, the prepolymerization catalyst component obtained in (1) above is used as a solid catalyst component.
After adding 15 mg, polymerization was carried out at 70 ° C. for 1 hour. After that, excess propylene was purged to obtain 315 g of powder polypropylene.
The catalyst efficiency CE was 21,000 g-PP / g-Cat, and the polymerization activity K was 700. ρ B is 0.47 g / cc, II is 97.2%, MFI is 7.5
Met. The resulting polymer has a very narrow particle size distribution, 50
The powder body with a particle size of 0 μm to 250 μm is 99% of the total, 10
The amount of fine powder of 0 μm or less was 0%.
実施例16 （１）プロピレン前重合 実施例15の（１）と同様な手法で、１オートクレーブ
に精製ノルマルヘキサン60ml、トリエチルアルミニウム
3.6ミリモルおよび実施例４の（１）で得られた固体触
媒成分3.0gを添加した。添加後25℃で３分間プロピレン
を供給して前重合を行った。得られた前重合触媒成分は
6.2gのポリプロピレンを含有していた。Example 16 (1) Prepolymerization of propylene In the same manner as in (1) of Example 15, 1 autoclave was charged with 60 ml of purified normal hexane and triethylaluminum.
3.6 mmol and 3.0 g of the solid catalyst component obtained in (1) of Example 4 were added. After the addition, propylene was supplied at 25 ° C. for 3 minutes to carry out prepolymerization. The obtained prepolymerization catalyst component is
It contained 6.2 g of polypropylene.
（２）プロピレンの本重合 実施例15の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝20,000g-PP/g-Cat、重合活性Ｋ
＝670、II＝97.6％、ρB＝0.48g/c.c.、MFI＝6.8であっ
た。(2) Main Polymerization of Propylene When propylene was polymerized in the same manner as in (2) of Example 15, the catalyst efficiency CE was 20,000 g-PP / g-Cat, and the polymerization activity was K.
= 670, II = 97.6%, ρ B = 0.48 g / cc, MFI = 6.8.
重合体の粒度分布は500μｍ〜177μｍの粒径をもつ粉末
体は全体の95％で、100μｍ以下の微粉量は０％であっ
た。The particle size distribution of the polymer was 95% of the whole powder having a particle size of 500 μm to 177 μm, and the amount of fine powder of 100 μm or less was 0%.
実施例17 実施例15の（１）で得られた前重合触媒成分を精製ノル
マルヘキサンで洗浄したものを用いた以外は、実施例15
の（２）と同様にしてプロピレンの重合を行った。その
結果、触媒効率CE＝19,500g-PP/g-Cat、重合活性Ｋ＝65
0、II＝97.5％、ρB＝0.47g/c.c.、MFI＝7.0であった。
得られた重合体の粒度分布は、実施例15の（２）とほぼ
同等であった。Example 17 Example 15 was repeated except that the prepolymerized catalyst component obtained in (1) of Example 15 was washed with purified normal hexane.
Polymerization of propylene was carried out in the same manner as in (2). As a result, catalyst efficiency CE = 19,500 g-PP / g-Cat, polymerization activity K = 65
0, II = 97.5%, ρ B = 0.47 g / cc, MFI = 7.0.
The particle size distribution of the obtained polymer was almost the same as in Example 15 (2).
実施例18 実施例１の（１）で得られた固体触媒成分を用い、実施
例15の（２）と同様にしてプロピレンの重合を行った。
その結果触媒効率CE＝18,000g-PP/g-Cat、重合活性Ｋ＝
600、II＝94.5％、ρB＝0.42g/c.c.、MFI＝6.6であっ
た。また得られた重合体の粒度分布は、500μｍ〜250μ
ｍの粒径をもつ粉末体が全体の97％、100μｍ以下の微
粉量は0.1％であった。Example 18 Using the solid catalyst component obtained in (1) of Example 1, propylene was polymerized in the same manner as in (2) of Example 15.
As a result, catalyst efficiency CE = 18,000g-PP / g-Cat, polymerization activity K =
It was 600, II = 94.5%, ρ B = 0.42 g / cc, and MFI = 6.6. The particle size distribution of the obtained polymer is 500 μm to 250 μm.
97% of the whole had a particle size of m, and the amount of fine powder of 100 μm or less was 0.1%.
比較例１ 市販Mg(OC2H5)25g、Ti(OC4H9)47.4gを用い、130℃で２
時間反応させ、液状生成物を得た。Comparative Example 1 A commercially available Mg (OC 2 H 5) 2 5g, Ti (OC 4 H 9) using 4 7.4 g, 2 at 130 ° C.
After reacting for a time, a liquid product was obtained.
この液状生成物を精製トルエン87mlに溶解させた後、−
20℃まで冷却し、−20℃においてTiCl441gを添加した。
TiCl4の添加と同時に析出が認められ、その後もスラリ
ー状のままであった。After dissolving this liquid product in 87 ml of purified toluene,
After cooling to 20 ° C., 41 g of TiCl 4 was added at −20 ° C.
Precipitation was observed at the same time as TiCl 4 was added, and thereafter it remained in a slurry state.
その他は、実施例１の（１）と同様な操作によって固体
触媒成分を得た。Other than that, the solid catalyst component was obtained by the same operation as in (1) of Example 1.
この固体触媒成分を用い、実施例１の（２）と同様にし
てプロピレンの重合を行い、重合体を得た。得られた重
合体の粒度分布は2000μｍ〜250μｍの粒径をもつ粉末
体が全体の66％と非常に広く、かつ100μｍ以下の微粉
量は12％と多いものであった。Using this solid catalyst component, propylene was polymerized in the same manner as in (2) of Example 1 to obtain a polymer. The particle size distribution of the obtained polymer was as wide as 66% of the whole powder having a particle size of 2000 μm to 250 μm, and the amount of fine powder of 100 μm or less was 12%.
比較例２ （１）触媒成分（Ａ）の製造 精製ｎ−ヘプタン100ml、市販Mg(OC2H5)22.26g、Ti(OC4
H9)40.67gを混合し、攪拌下昇温して80℃で２時間反応
させ、固体状の反応生成物を得た。次いで、安息香酸エ
チル0.59gを添加し98℃で１時間反応を行った。その後
室温にてTiCl445mlを滴下し、昇温後98℃で2.5時間反応
させ、80℃で上澄液を抜き出した後、精製ｎ−ヘプタン
で充分洗浄して、固体触媒成分2.2gを得た。このものの
担持Ti量は3.4重量％であった。Comparative Example 2 (1) Production of catalyst component (A) Purified n-heptane 100 ml, commercially available Mg (OC 2 H 5 ) 2 2.26 g, Ti (OC 4
H 9 ) 4 ( 0.67 g) was mixed, the temperature was raised with stirring, and the mixture was reacted at 80 ° C. for 2 hours to obtain a solid reaction product. Then, 0.59 g of ethyl benzoate was added and the reaction was carried out at 98 ° C for 1 hour. After that, 45 ml of TiCl 4 was added dropwise at room temperature, the temperature was raised, the reaction was carried out at 98 ° C. for 2.5 hours, and the supernatant liquid was extracted at 80 ° C., followed by thorough washing with purified n-heptane to obtain 2.2 g of solid catalyst component It was The supported Ti amount was 3.4% by weight.
（２）プロピレンの重合 実施例１の（２）と同様にしてプロピレンの重合を行っ
たところ、触媒効率CE＝3000g-PP/g-Cat、重合活性Ｋ＝
100、II＝91.7％、MFI＝10.5、ρB＝0.26と、重合活
性、立体規則性、嵩密度ともに低いものであった。また
得られた重合体の粒度分布は2000μｍ〜250μｍの粒径
をもつ粉末体が全体の80％と非常に広く、100μｍ以下
の微粉量は1.5％であった。(2) Polymerization of Propylene Polymerization of propylene was carried out in the same manner as in (2) of Example 1, and the catalyst efficiency CE = 3000 g-PP / g-Cat and the polymerization activity K =
Polymerization activity, stereoregularity, and bulk density were low, with 100, II = 91.7%, MFI = 10.5, and ρ B = 0.26. The particle size distribution of the obtained polymer was 80% of the whole powder body having a particle size of 2000 μm to 250 μm, which was very wide, and the amount of fine powder of 100 μm or less was 1.5%.
本発明によると、立体規則性および粒子性状に優れたα
−オレフィンの重合体を高重合活性で得ることができる
ため、工業的に有用である。According to the present invention, α having excellent stereoregularity and particle properties
-It is industrially useful because an olefin polymer can be obtained with high polymerization activity.
第１図は、本発明の一態様を示すフローチャート図であ
る。FIG. 1 is a flowchart showing one embodiment of the present invention.
Claims (15)
R1、R2はアルキル基、アリール基またはアラルキル基を
示し、R1とR2は同一でも異なっても良い。ｎは２≧ｎ≧
０を示す。）で表わされるマグネシウム化合物（a1）、
一般式Ti(OR3)4（式中、R3はアルキル基、アリール基ま
たはアラルキル基を示す。）で表わされるチタン化合物
（a2）および一般式Si(OR4)4（式中、R4はアルキル基、
アリール基またはアラルキル基を示す。）で表わされる
ケイ素化合物（a3）を加熱反応させ、ついで該反応生成
物（ａ）を一般式TiXP(OR9)4-P（式中、R9はアルキル基
を示し、Ｘはハロゲン、Ｐは０＜Ｐ≦４を示す。）で表
わされるハロゲン含有チタン化合物（ｂ）および電子供
与性化合物（ｃ）で接触処理することによって得られる
固体触媒成分と、 （Ｂ）一般式▲AlR8 m▼X3-m（式中、R8は炭素数１〜20
個の炭化水素基を示し、Ｘはハロゲン、ｍは２〜３の数
を示す。）で表わされる有機アルミニウム化合物より成
る触媒の存在下にオレフィンを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。(A) General formula Mg (OR 1 ) n (OR 2 ) 2-n (wherein
R 1 and R 2 represent an alkyl group, an aryl group or an aralkyl group, and R 1 and R 2 may be the same or different. n is 2 ≧ n ≧
Indicates 0. ) A magnesium compound (a 1 ),
A titanium compound (a 2 ) represented by the general formula Ti (OR 3 ) 4 (wherein R 3 represents an alkyl group, an aryl group or an aralkyl group) and a general formula Si (OR 4 ) 4 (in the formula, R 4 is an alkyl group,
An aryl group or an aralkyl group is shown. ) Is reacted with a silicon compound (a 3 ) by heating, and then the reaction product (a) is converted to the general formula TiX P (OR 9 ) 4-P (wherein R 9 represents an alkyl group and X represents a halogen). , P represents 0 <P ≦ 4), and a solid catalyst component obtained by contact treatment with a halogen-containing titanium compound (b) represented by the formula (b) and an electron-donating compound (c); 8 m ▼ X 3-m (In the formula, R 8 has 1 to 20 carbon atoms.
Is a hydrocarbon group, X is halogen, and m is a number of 2 to 3. ) Polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound represented by the formula (1).
（a2）、ケイ素化合物（a3）を加熱反応させる際に、R5
OH（式中、R5はアルキル基、アリール基、アラルキル基
を示す。）で表わされる化合物（a4）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。2. When a magnesium compound (a 1 ), a titanium compound (a 2 ) and a silicon compound (a 3 ) are heated and reacted, R 5
The method according to claim 1, wherein a compound (a 4 ) represented by OH (wherein R 5 represents an alkyl group, an aryl group or an aralkyl group) is present.
ン化合物（ｂ）及び電子供与性化合物（ｃ）で処理する
際、一度均一系を経たのち固体を生成させることを特徴
とする特許請求の範囲第１項又は第２項記載の方法。3. A method of treating a heated reaction product (a) with a halogen-containing titanium compound (b) and an electron-donating compound (c), which is subjected to a homogeneous system once to form a solid. The method according to claim 1 or 2.
ン化合物（ｂ）及び電子供与性化合物（ｃ）で処理する
際、（ａ）成分と（ｂ）成分を−70℃〜50℃で接触さ
せ、次いで（ｃ）成分を50℃〜200℃で接触させて処理
する、または（ａ）、（ｂ）、（ｃ）成分を同時に−70
℃〜50℃で接触させ、次いで50℃〜200℃で処理するこ
とを特徴とする、特許請求の範囲第１項または第２項に
記載の方法。4. When the heating reaction product (a) is treated with the halogen-containing titanium compound (b) and the electron-donating compound (c), the components (a) and (b) are treated at -70 ° C to 50 ° C. Contacting and then treating the component (c) by contacting it at 50 ° C to 200 ° C, or simultaneously treating the components (a), (b) and (c) at -70.
The method according to claim 1 or 2, characterized in that the contact is carried out at 50 ° C to 50 ° C, followed by treatment at 50 ° C to 200 ° C.
チタン、ケイ素及びOR基（式中、Ｒはアルキル基、アリ
ール基またはアラルキル基を示す。）よりなる固体状生
成物を含むことを特徴とする特許請求の範囲第１項また
は第２項に記載の方法。5. The heating reaction product (a) is magnesium,
The solid product comprising titanium, silicon and an OR group (wherein R represents an alkyl group, an aryl group or an aralkyl group), and a solid product is contained therein. the method of.
（a2）、ケイ素化合物（a3）およびR5OHで表わされる化
合物（a4）の少くともいずれかがアリールオキシ基を含
むことを特徴とする特許請求の範囲第１項または第２項
に記載の方法。6. A magnesium compound (a 1 ), a titanium compound (a 2 ), a silicon compound (a 3 ) and at least one of the compounds (a 4 ) represented by R 5 OH contains an aryloxy group. Method according to claim 1 or 2 characterized.
ン化合物（ｂ）及び電子供与性化合物（ｃ）による処理
を二回以上繰り返すことを特徴とする特許請求の範囲第
１項または第２項に記載の方法。7. The method according to claim 1 or 2, wherein the treatment of the heated reaction product (a) with the halogen-containing titanium compound (b) and the electron-donating compound (c) is repeated twice or more. The method described in the section.
ネシウム化合物（a1）が、ジアルコキシマグネシウム、
ジアリールオキシマグネシウム、ジアラルキルオキシマ
グネシウム、アルキルオキシアリールオキシマグネシウ
ムから選ばれることを特徴とする、特許請求の範囲第１
項または第２項に記載の方法。8. A magnesium compound (a 1 ) represented by the general formula Mg (OR 1 ) n (OR 2 ) 2-n is dialkoxy magnesium,
Claim 1 characterized in that it is selected from diaryloxymagnesium, diaralkyloxymagnesium, alkyloxyaryloxymagnesium.
The method according to Item 2 or Item 2.
（a3）が、テトラメトキシシラン、テトラエトキシシラ
ン、テトラプロポキシシラン、テトラブトキシシラン、
テトラ（２−エチルヘキソキシ）シラン、テトラフェノ
キシシラン、テトラ（ｐ−メチルフェノキシ）シランか
ら選ばれることを特徴とする、特許請求の範囲第１項ま
たは第２項に記載の方法。9. A silicon compound (a 3 ) represented by the general formula Si (OR 4 ) 4 is tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane,
The method according to claim 1 or 2, wherein the method is selected from tetra (2-ethylhexoxy) silane, tetraphenoxysilane, and tetra (p-methylphenoxy) silane.
ステルであることを特徴とする、特許請求の範囲第１項
または第２項に記載の方法。10. The method according to claim 1, wherein the electron-donating compound (c) is a carboxylic acid ester.
物が、Ti(OCH3)4、Ti(OC2H5)4、Ti(OC3H7)4、Ti(OC4H9)
4、Ti(OC6H5)4、Ti(OCH2C6H5)4から選ばれることを特徴
とする、特許請求の範囲第１項または第２項のいずれか
に記載の方法。11. A titanium compound represented by the general formula Ti (OR 3 ) 4 is Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 ) 4 , Ti (OC 4 H 9 )
4. The method according to claim 1, wherein the method is selected from the group consisting of 4 , Ti (OC 6 H 5 ) 4 and Ti (OCH 2 C 6 H 5 ) 4 .
ノール、イソプロパノール、プロパノール、ブタノー
ル、イソブタノール、ヘキサノール、オクタノール、２
エチルヘキサノール、ベンジルアルコール等のアルコー
ル類；フェノール、クレゾール、キシレノール、ブチル
フェノール等のフェノール類から選ばれることを特徴と
する、特許請求の範囲第２項に記載の方法。12. A compound represented by the general formula R 5 OH is ethanol, isopropanol, propanol, butanol, isobutanol, hexanol, octanol, or 2.
The method according to claim 2, which is selected from alcohols such as ethylhexanol and benzyl alcohol; phenols such as phenol, cresol, xylenol and butylphenol.
ル基を示し、Ｘはハロゲン、Ｐは０＜Ｐ≦４を示す。）
で表わされるハロゲン含有チタン化合物（ｂ）が、四塩
化チタンであることを特徴とする、特許請求の範囲第１
項または第２項に記載の方法。13. The general formula TiX P (OR) 4-P (wherein R represents an alkyl group, X represents halogen, and P represents 0 <P ≦ 4).
The halogen-containing titanium compound (b) represented by the formula (1) is titanium tetrachloride.
The method according to Item 2 or Item 2.
物（a2）、ケイ素化合物（a3）およびR5OHで表わされる
化合物（a4）の少なくともいずれかがアリールオキシ基
を含む（a1）、（a2）、（a3）及び場合によっては
（a4）の加熱反応生成物（ａ）を、四塩化チタン（ｂ）
及びカルボン酸エステル（ｃ）で処理する際、（ａ）成
分と（ｂ）成分を−70℃〜50℃で接触させ、次いで
（ｃ）成分を50℃〜200℃で接触させて処理し、一度均
一系を経たのち固体を生成させることを特徴とする、特
許請求の範囲第１項または第２項に記載の方法。14. At least one of a magnesium compound (a 1 ), a titanium compound (a 2 ), a silicon compound (a 3 ) and a compound (a 4 ) represented by R 5 OH contains an aryloxy group (a 1 ), (A 2 ), (a 3 ) and optionally (a 4 ) the heated reaction product (a) is converted into titanium tetrachloride (b)
And when treated with the carboxylic acid ester (c), the component (a) and the component (b) are contacted at -70 ° C to 50 ° C, and then the component (c) is contacted at 50 ° C to 200 ° C, and then treated. The method according to claim 1 or 2, characterized in that the solid is produced after once passing through a homogeneous system.
フィンを重合または共重合させることを特徴とする特許
請求の範囲第１項または第２項に記載の方法。15. The method according to claim 1 or 2, wherein the olefin is polymerized or copolymerized in the presence of the electron-donating compound (C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29376987A JPH0780949B2 (en) | 1986-11-20 | 1987-11-20 | Process for producing olefin polymer |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61-277361 | 1986-11-20 | ||
| JP27736186 | 1986-11-20 | ||
| JP62-111994 | 1987-05-08 | ||
| JP11199487 | 1987-05-08 | ||
| JP29376987A JPH0780949B2 (en) | 1986-11-20 | 1987-11-20 | Process for producing olefin polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6454007A JPS6454007A (en) | 1989-03-01 |
| JPH0780949B2 true JPH0780949B2 (en) | 1995-08-30 |
Family
ID=27312151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29376987A Expired - Fee Related JPH0780949B2 (en) | 1986-11-20 | 1987-11-20 | Process for producing olefin polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0780949B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925268B (en) * | 2022-04-02 | 2025-08-08 | 中国石油化工股份有限公司 | Catalyst component for ethylene polymerization and preparation method, catalyst and application thereof |
-
1987
- 1987-11-20 JP JP29376987A patent/JPH0780949B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6454007A (en) | 1989-03-01 |
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