KR0169718B1 - Preparation method of olefin polymerization catalyst and ethylene copolymer - Google Patents
Preparation method of olefin polymerization catalyst and ethylene copolymer Download PDFInfo
- Publication number
- KR0169718B1 KR0169718B1 KR1019900006484A KR900006484A KR0169718B1 KR 0169718 B1 KR0169718 B1 KR 0169718B1 KR 1019900006484 A KR1019900006484 A KR 1019900006484A KR 900006484 A KR900006484 A KR 900006484A KR 0169718 B1 KR0169718 B1 KR 0169718B1
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- polymerization catalyst
- olefin polymerization
- titanium
- catalyst according
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 25
- 239000002685 polymerization catalyst Substances 0.000 title claims description 25
- 229920001038 ethylene copolymer Polymers 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title description 3
- 229920000642 polymer Polymers 0.000 claims description 78
- -1 ester compound Chemical class 0.000 claims description 57
- 239000010936 titanium Substances 0.000 claims description 50
- 150000001875 compounds Chemical class 0.000 claims description 44
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 41
- 239000012265 solid product Substances 0.000 claims description 41
- 239000011949 solid catalyst Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 36
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 30
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 22
- 150000002430 hydrocarbons Chemical group 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 150000002681 magnesium compounds Chemical class 0.000 claims description 16
- 150000003609 titanium compounds Chemical class 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 14
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 13
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 239000000460 chlorine Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- 229910018557 Si O Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 claims description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 2
- 150000004796 dialkyl magnesium compounds Chemical class 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- 239000003054 catalyst Substances 0.000 description 50
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- 238000006116 polymerization reaction Methods 0.000 description 45
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- 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 16
- 229910052786 argon Inorganic materials 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000011343 solid material Substances 0.000 description 13
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 229930195733 hydrocarbon Natural products 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 4
- MQHNKCZKNAJROC-UHFFFAOYSA-N dipropyl phthalate Chemical compound CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002901 organomagnesium compounds Chemical class 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 2
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- HGERXYZHJFOFNE-UHFFFAOYSA-N 2-o-ethyl 1-o-methyl benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OC HGERXYZHJFOFNE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XPVATDCOZDHQNL-UHFFFAOYSA-N CC(C)(C)[Mg]C(C)(C)C Chemical compound CC(C)(C)[Mg]C(C)(C)C XPVATDCOZDHQNL-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- QWDBCIAVABMJPP-UHFFFAOYSA-N Diisopropyl phthalate Chemical compound CC(C)OC(=O)C1=CC=CC=C1C(=O)OC(C)C QWDBCIAVABMJPP-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 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 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- OGVXYCDTRMDYOG-UHFFFAOYSA-N dibutyl 2-methylidenebutanedioate Chemical compound CCCCOC(=O)CC(=C)C(=O)OCCCC OGVXYCDTRMDYOG-UHFFFAOYSA-N 0.000 description 2
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 description 2
- 229960002097 dibutylsuccinate Drugs 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
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 2
- 229940093499 ethyl acetate Drugs 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- QUXHCILOWRXCEO-UHFFFAOYSA-M magnesium;butane;chloride Chemical compound [Mg+2].[Cl-].CCC[CH2-] QUXHCILOWRXCEO-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- YWWHKOHZGJFMIE-UHFFFAOYSA-N monoethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(O)=O YWWHKOHZGJFMIE-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000002894 organic compounds Chemical class 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
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- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
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- PGRDNHQIURCHPZ-UHFFFAOYSA-N cyclohexyloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1CCCCC1 PGRDNHQIURCHPZ-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- ACIRMTDSYZCTAP-UHFFFAOYSA-N dibutyl(dibutylalumanyloxy)alumane Chemical compound CCCC[Al](CCCC)O[Al](CCCC)CCCC ACIRMTDSYZCTAP-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
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- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- AVBCBOQFOQZNFK-UHFFFAOYSA-N dipropoxy(dipropyl)silane Chemical compound CCCO[Si](CCC)(CCC)OCCC AVBCBOQFOQZNFK-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DFJDZTPFNSXNAX-UHFFFAOYSA-N ethoxy(triethyl)silane Chemical compound CCO[Si](CC)(CC)CC DFJDZTPFNSXNAX-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UKZCGMDMXDLAGZ-UHFFFAOYSA-M magnesium;2-methylpropane;bromide Chemical compound [Mg+2].[Br-].C[C-](C)C UKZCGMDMXDLAGZ-UHFFFAOYSA-M 0.000 description 1
- CQRPUKWAZPZXTO-UHFFFAOYSA-M magnesium;2-methylpropane;chloride Chemical compound [Mg+2].[Cl-].C[C-](C)C CQRPUKWAZPZXTO-UHFFFAOYSA-M 0.000 description 1
- WRYKIHMRDIOPSI-UHFFFAOYSA-N magnesium;benzene Chemical compound [Mg+2].C1=CC=[C-]C=C1.C1=CC=[C-]C=C1 WRYKIHMRDIOPSI-UHFFFAOYSA-N 0.000 description 1
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- LWLPYZUDBNFNAH-UHFFFAOYSA-M magnesium;butane;bromide Chemical compound [Mg+2].[Br-].CCC[CH2-] LWLPYZUDBNFNAH-UHFFFAOYSA-M 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- DQZLQYHGCKLKGU-UHFFFAOYSA-N magnesium;propane Chemical compound [Mg+2].C[CH-]C.C[CH-]C DQZLQYHGCKLKGU-UHFFFAOYSA-N 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000007613 slurry method Methods 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- WILBTFWIBAOWLN-UHFFFAOYSA-N triethyl(triethylsilyloxy)silane Chemical compound CC[Si](CC)(CC)O[Si](CC)(CC)CC WILBTFWIBAOWLN-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- KHQZLUVCZCAMFU-UHFFFAOYSA-N tripropyl(tripropylsilyloxy)silane Chemical compound CCC[Si](CCC)(CCC)O[Si](CCC)(CCC)CCC KHQZLUVCZCAMFU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
내용 없음.No content.
Description
제1도는 본 발명의 이해를 용이하게 하는 흐름도이다.1 is a flow chart to facilitate understanding of the present invention.
본 발명은 올레핀 중합 촉매 및 에틸렌 공중합체의 제조법에 관한 것이다. 더욱 상세하게는, 본 발명은 기상 중합 및 슬러리 중합법에 있어서 전이 금속 당의 활성이 매우 높은 고체 촉매 성분을 함유하는 올레핀 중합 촉매 및 이 촉매를 사용하여 분자량 분포가 협소하고, 저분자량 성분이 적은 에틸렌 공중합체를 제조하는 방법에 관한 것이다. 또한, 본 발명은 고체 촉매 성분의 입자 형상을 매우 양호하게 제어하고, 벌크 밀도가 높으며, 미분함량이 적고, 유동성이 양호한 에틸렌 공중합체의 제조 방법에 관한 것이다.The present invention relates to a process for the preparation of olefin polymerization catalysts and ethylene copolymers. More specifically, the present invention relates to an olefin polymerization catalyst containing a solid catalyst component having a very high activity of transition metal sugars in the gas phase polymerization and slurry polymerization methods, and an ethylene having a narrow molecular weight distribution and a low molecular weight component using the catalyst. It relates to a method of producing a copolymer. The present invention also relates to a method for producing an ethylene copolymer having very good control of the particle shape of the solid catalyst component, high bulk density, low fine powder content and good fluidity.
에틸렌 공중합체를 제조하는 경우에 사용하는 촉매의 활성(단위 촉매당의 중합량), 특히 전이 금속당의 활성이 높은 것은 중합후에 수득되는 중합체로부터 촉매 잔사를 제거할 필요가 없으며, 중합체의 제조 공정을 간략화 시키므로 공업적으로 극히 이용 가치가 높은 것은 말할 필요도 없다.The high activity of the catalyst used in the production of ethylene copolymers (polymerization amount per unit catalyst), especially the transition metal sugar, does not need to remove the catalyst residue from the polymer obtained after polymerization, and simplifies the process of producing the polymer. Needless to say, industrial use is extremely valuable.
한편, 중합조에 부착되는 중합체는 조업상 각종의 장해를 발생시켜 조업 효율을 저하시키는 원인이 되기 때문에 중합조에 대한 중합체의 부착을 최소화시키는 것이 바람직하다. 따라서, 조업의 안정성 및 조업 효율면에서 볼 때 중합체 분말의 벌크 밀도가 높고, 입도 분포가 협소하며, 유동성이 양호한 것이 바람직하다.On the other hand, it is preferable to minimize the adhesion of the polymer to the polymerization tank because the polymer attached to the polymerization tank causes various obstacles in operation and causes a decrease in the operation efficiency. Therefore, from the viewpoint of operation stability and operation efficiency, it is preferable that the bulk density of the polymer powder is high, the particle size distribution is narrow, and the fluidity is good.
또한, 분자량 분포 및 저분자량 성분의 유무는 가공품의 투명성, 내충격성, 블록킹성을 지배하는 인자이며, 분자량 분포가 협소하고, 저분자량 성분의 적은 에틸렌 공중합체를 제조하는 것이 바람직하다.In addition, the presence or absence of a molecular weight distribution and a low molecular weight component is a factor which governs the transparency, impact resistance, and blocking property of a workpiece | work, It is preferable that a molecular weight distribution is narrow and manufactures the ethylene copolymer of a low molecular weight component.
최근에 사염화 티탄 등의 담체상에 지지되는 전이 금속 화합물로 제조된 촉매가 개발되었다. (벨기에 공화국 특허원 제759,601호, 일본국 특공소 47-46,269호 공보, 일본국 특공소 47-26,383호 공보 등). 이런 형태의 촉매는 종전 촉매보다 중합 활성이 높지만, 이들은 전이 금속당 촉매 활성의 면에서 아직 불충분하다.Recently, catalysts made of transition metal compounds supported on a carrier such as titanium tetrachloride have been developed. (Belgium Patent Application No. 759,601, JP 47-46,269, JP 47-26,383, etc.). Although catalysts of this type have higher polymerization activity than previous catalysts, they are still insufficient in terms of catalytic activity per transition metal.
한편, 티탄 화합물을 유기 마그네슘으로 환원시켜 제조한 고체 생성물로부터 제조된 촉매계로서, 그리냐르 시약 및 사염화 티탄 또는 알콕시-함유 할로겐화 티탄으로 이루어진 고체 촉매 성분(일본국 특개소 46-4,391호 공보, 일본국 특공소 제47-40,959호 공보, 일본국 특공소 제50-30,102호 공보 등) 및 그리냐르 시약과 알콕시-함유 할로겐화 티탄을 반응시켜 반응 생성물을 사염화티탄으로 처리하여 제조한 고체 촉매 성분(일본국 특공소 57-24,361호 공보, 일본국 특개소 56-115,302호 공보 등)이 보고되어 있다. 하지만, 이들 촉매는 고체 촉매 성분의 입자 특성 및 전이 금속당 촉매 활성에서 아직 불충분하다.On the other hand, as a catalyst system prepared from a solid product prepared by reducing a titanium compound with organic magnesium, a solid catalyst component consisting of Grignard reagent and titanium tetrachloride or alkoxy-containing halogenated titanium (Japanese Patent Application Laid-Open No. 46-4,391, Japan Japanese Patent Application No. 47-40,959, Japanese Patent Application No. 50-30,102, etc.) and a solid catalyst component prepared by treating a reaction product with titanium tetrachloride by reacting a Grignard reagent with an alkoxy-containing titanium halide. Japanese Unexamined Patent Application Publication No. 57-24,361 and Japanese Unexamined Patent Application Publication No. 56-115,302. However, these catalysts are still insufficient in the particle properties of the solid catalyst component and in the catalytic activity per transition metal.
한편, 다공성 무기 담체상에 지지된 수개의 촉매성분이 문헌(일본국 특개소 54-148,093호 공보, 56-24,409호 공보, 58-179,207호 공보 등)에 개시되어 있다. 하지만, 이들은 중합조에 대한 접착성 및 촉매 활성의 면에서 아직 불충분하다.On the other hand, several catalyst components supported on a porous inorganic carrier are disclosed in Japanese Patent Application Laid-Open Nos. 54-148,093, 56-24,409, 58-179,207, and the like. However, they are still insufficient in terms of adhesion to the polymerization bath and catalytic activity.
상기 현상에 있어서, 본 발명에 의하여 해결하고자 하는 문제점, 즉 본 발명의 목적은 상기 촉매를 사용하여 분자량 분포가 협소하고, 저분자량 성분이 적으며, 벌크 밀도가 높으며, 미분이 적으며, 유동성이 양호한 에틸렌 공중합체를 제조하는 방법 및 불필요한 촉매 잔사를 제거하기 위하여 전이 금속당 촉매 활성이 매우 높은 고체 촉매 성분을 제공함에 있다.In the above phenomenon, the problem to be solved by the present invention, that is, the object of the present invention using the catalyst is a narrow molecular weight distribution, low molecular weight components, high bulk density, low fine powder, fluidity A method of preparing a good ethylene copolymer and providing a solid catalyst component with very high catalytic activity per transition metal to remove unwanted catalyst residues.
본 발명은The present invention
(A) 유기 다공성 중합체와 Si-O 결합을 갖는 유기 규소 화합물의 존재하에서 유기 마그네슘 화합물로 하기 일반식 (II)로 표시되는 티탄 화합물로 환원시키고, 생성되는 고체 생성물을 에스테르 화합물로 처리한 후, 이를 사염화 티탄 또는 사염화 티탄과 전자 공여성 화합물의 혼합물과 반응시켜 수득한 하기 일반식 (I)로 표시되는 3가 티탄을 함유하는 고체 촉매 성분 및(A) reducing the organic magnesium compound to a titanium compound represented by the following general formula (II) in the presence of an organic silicon compound having an Si-O bond with an organic porous polymer, and treating the resulting solid product with an ester compound, Solid catalyst component containing trivalent titanium represented by the following general formula (I) obtained by reacting this with titanium tetrachloride or a mixture of titanium tetrachloride and an electron donating compound, and
(B) 유기 알루미늄 화합물을 함유하는 올레핀 중합촉매를 제공하며, 또한 이 중합 촉매를 사용하여 탄소수 3개 이상을 갖는 하나 이상의 알파-올레핀과 에틸렌을 공중합체 시킴을 특징으로 하는 에틸렌 공중합체의 제조 방법에 관한 것이다.(B) A process for producing an ethylene copolymer comprising providing an olefin polymerization catalyst containing an organoaluminum compound, and further copolymerizing ethylene with at least one alpha-olefin having 3 or more carbon atoms using the polymerization catalyst. It is about.
(상기 식에서, R은 탄소수 1 내지 20의 탄화수소기이고, X는 할로겐이고, ED는 전자공여성 화합물이며, m, n, p 및 q는 각각 1≤m≤51, 0n≤5, 5≤p≤106 및 0.2≤q≤2를 만족하는 수이다).Wherein R is a hydrocarbon group of 1 to 20 carbon atoms, X is a halogen, ED is an electron-donating compound, and m, n, p and q are each 1 ≦ m ≦ 51, 0n ≦ 5, 5 ≦ p ≦ 106 and 0.2 ≦ q ≦ 2).
(상기 식에서, R1은 탄소수 1 내지 20의 탄화수소기이고, X는 할로겐원자이며, a는 0a≤4를 만족하는 수이다).(Wherein R 1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and a is a number satisfying 0a ≦ 4).
에틸렌 공중합체를 제조하는 본 발명의 방법에 있어서, 형성되는 중합체 중의 촉매 잔사량은 매우 적어 전이 금속당의 높은 촉매 활성 때문에 촉매 제거 공정이 생략될 수 있다. 중합조에 대한 중합체의 접착이 중합시에는 적으며, 생성되는 중합체는 입도 분포가 협소하고, 거의 구형 또는 잡아늘인 구형이며, 벌크 밀도가 높으며, 유동성이 양호하므로 펠레트화 공정이 생략될 수 있다. 따라서, 본 발명의 방법은 중합 및 작업성 효율 면에서 매우 우수하다. 또한, 이는 분자량 분포가 협소하며, 저분자량 성분량이 적은 공중합체가 제조되게 한다.In the process of the present invention for producing ethylene copolymers, the catalyst residue in the polymer formed is so small that the catalyst removal process can be omitted due to the high catalytic activity of the transition metal sugars. The adhesion of the polymer to the polymerization bath is small during the polymerization, and the resulting polymer is narrow in particle size distribution, almost spherical or narrow in spherical shape, high in bulk density and good in fluidity, so that the pelletization process can be omitted. Thus, the process of the present invention is very good in terms of polymerization and workability efficiency. In addition, this results in a narrow molecular weight distribution and allows copolymers with a low amount of low molecular weight components to be produced.
제1도는 본 발명의 이해를 용이하게 하는 흐름도이다. 이 흐름도는 단지 본 발명의 태양의 대표예이며, 이로 인하여 본 발명이 제한되는 것은 아니다.1 is a flow chart to facilitate understanding of the present invention. This flowchart is merely a representative of aspects of the present invention, which do not limit the present invention.
다음, 본 발명은 하기한 것에 의하여 구체적으로 예시된다.Next, the present invention is specifically illustrated by the following.
(a) 티탄 화합물(a) titanium compound
본 발명에서 사용되는 티탄 화합물이 하기 일반식(I)에 의하여 나타내어진다:The titanium compound used in the present invention is represented by the following general formula (I):
(상기 식에서, R1은 탄소수 1 내지 20의 탄화수소기를 나타내고, X는 할로겐 원자를 나타내며, a는 0a≤4를 만족하는 수를 나타낸다).(Wherein R 1 represents a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom, and a represents a number satisfying 0a ≦ 4).
R1의 구체예에는 메틸, 에틸, 프로필, 이소-프로필, 부틸, 이소-부틸, 아밀, 이소-아밀, 헥실, 헵틸, 옥틸, 데실, 도데실 등의 알킬기; 페닐, 크레실, 크실릴, 나프틸 등의 아릴기; 시클로헥실, 시클로펜틸 등의 시클로알킬기; 프로페닐 등의 알릴기; 베질 등의 아르알킬기가 있다.Specific examples of R 1 include alkyl groups such as methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, amyl, iso-amyl, hexyl, heptyl, octyl, decyl and dodecyl; Aryl groups such as phenyl, cresyl, xylyl and naphthyl; Cycloalkyl groups such as cyclohexyl and cyclopentyl; Allyl groups such as propenyl; Aralkyl groups such as benzyl.
상기 기들 중에서, 탄소수 2 내지 18의 알킬기 및 탄소수 6 내지 18의 아릴기가 바람직하며, 탄소수 2 내지 18의 직쇄 알킬기가 특히 바람직하다. 또 한 두 개 이상의 상이한 OR1기를 갖는 티탄 화합물을 사용하는 것도 가능하다.Among the above groups, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable, and a straight alkyl group having 2 to 18 carbon atoms is particularly preferable. It is also possible to use titanium compounds having two or more different OR 1 groups.
X로 표시되는 할로겐 원자의 예에는 염소, 브롬, 요오드 등이 있으며, 이 중에서 염소는 특히 양호한 결과를 제공한다.Examples of halogen atoms represented by X include chlorine, bromine, iodine and the like, of which chlorine provides particularly good results.
Ti(OR1)aX4-a로 표시되는 티탄 화합물에서 a는 0a≤4, 바람직하게는 2≤a≤4, 특히 a=4를 만족하는 값이다.In the titanium compound represented by Ti (OR 1 ) a X 4-a , a is a value satisfying 0a ≦ 4, preferably 2 ≦ a ≦ 4, particularly a = 4.
Ti(OR1)aX4-a(0a≤4)로 표시되는 화합물을 합성하는 방법으로서 특정의 공지 방법이 사용될 수 있다.As a method for synthesizing a compound represented by Ti (OR 1 ) a X 4-a (0a ≦ 4 ), a specific known method may be used.
예를 들면, Ti(OR1)4와 TiX4를 적절한 비율로 반응시키는 방법 또는 TiX4와 대응 알코올을 적절한 비율로 반응시키는 방법이 적용될 수 있다.For example, a method of reacting Ti (OR 1 ) 4 with TiX 4 at an appropriate ratio or a method of reacting TiX 4 with a corresponding alcohol at an appropriate ratio may be applied.
(b) Si-O 결합을 갖는 유기 규소 화합물(b) organosilicon compounds with Si-O bonds
본 발명에서 사용되는 Si-O 결합을 갖는 유기 규소 화합물은 하기 일반식(III)으로 나타내어진다:Organosilicon compounds having Si—O bonds used in the present invention are represented by the following general formula (III):
R5(R6 2SiO)cSiR7 3(III)R 5 (R 6 2 SiO) c SiR 7 3 (III)
(R8 2SiO)d (R 8 2 SiO) d
(상기 식에서, R3은 탄소수 1 내지 20의 탄화수소기를 나타내고, R4, R5, R6, R7및 R8은 각각 탄소수 1 내지 20의 탄화수소기 또는 할로겐 원자를 나타내며,(Wherein R 3 represents a hydrocarbon group having 1 to 20 carbon atoms, R 4 , R 5 , R 6 , R 7 and R 8 each represent a hydrocarbon group or halogen atom having 1 to 20 carbon atoms,
b는 0b≤4를 만족하는 수이며,b is a number satisfying 0b≤4,
c는 1 내지 1,000의 정수이고,c is an integer from 1 to 1,000,
d는 2 내지 1,000의 정수이다).d is an integer from 2 to 1,000).
유기 규소 화합물의 구체예에는 다음과 같은 것이 있다:Specific examples of organosilicon compounds include the following:
테트라메톡시실란, 디메틸디메톡시실란, 테트라에톡시실란, 트리에톡시에틸실란, 디에톡시디에틸실란, 에톡시트리에틸실란, 테트라-이소-프로폭시실란, 디-이소-프로폭시-디-이소-프로필실란, 테트라프로폭시실란, 디프로폭시디프로필실란, 테트라부톡시실란, 디부톡시디부틸실란, 디시클로펜톡시디에틸실란, 디에톡시페닐실란, 시클로헥실옥시트리메틸실란, 펜톡시트리메틸실란, 테트라페톡시실란, 트리에톡시페닐실란, 헥사메틸디실록산, 헥사에틸디실록산, 헥사프로필디실록산, 옥타에틸트리실록산, 디메틸폴리실록산, 디페닐폴리실록산, 메틸히드로폴리실록산, 페닐히드로폴리실록산 등.Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetra-iso-propoxysilane, di-iso-propoxy-di- Iso-propylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxyphenylsilane, cyclohexyloxytrimethylsilane, pentoxytrimethylsilane Tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, and the like.
이들 유기 규소 화합물 중에서, 일반식 Si(OR3)bR4 4-b로 표시되는 알록시실란 화합물이 바람직하며, 이 때 1≤b≤4인 것이 더욱 바람직하며, b가 4인 테트라알콕시실란 화합물이 특히 바람직하다.Of these organosilicon compounds, the oxysilane compounds represented by the general formula Si (OR 3 ) b R 4 4-b are preferred, and in this case, it is more preferable that 1 ≦ b ≦ 4, and b is a tetraalkoxysilane. Particular preference is given to compounds.
(c) 유기 마그네슘 화합물(c) organo magnesium compounds
다음, 유기 마그네슘 화합물로서 마그네슘-탄소 결합을 갖는 특정 형태의 유기 마그네슘 화합물이 사용될 수 있다.Next, as the organic magnesium compound, a specific type of organic magnesium compound having a magnesium-carbon bond can be used.
특히, 일반식 R9MgX(여기에서, R9는 탄소수 1 내지 20의 탄화수소기를 나타내고, X는 할로겐을 나타낸다)로 표시되는 그리냐르 화합물 및 일반식 R10R11Mg(여기에서, R10및 R11은 각각 탄소수 1 내지 20의 탄화수소를 나타낸다)로 표시되는 디아릴마그네슘 화합물 또는 디알킬마그네슘 화합물이 바람직하게 사용된다.In particular, the Grignard compound represented by the general formula R 9 MgX (wherein R 9 represents a hydrocarbon group having 1 to 20 carbon atoms and X represents a halogen) and the general formula R 10 R 11 Mg (here, R 10 and R 11 is used, each represents a hydrocarbon group having 1 to 20 carbon atoms), a diaryl magnesium compound or the dialkyl magnesium compound preferably represented by the following.
여기에서 R9및 R10은 동일하거나 상이하고, 메틸, 에틸, 프로필, 이소-프로필, 부틸, 2차-부틸, 3차-부틸, 아밀, 이소-아밀, 헥실, 옥틸, 2-에틸헥실, 페닐, 벤질 등의 탄소수 1 내지 20의 알킬, 아릴, 아르알킬 또는 알케닐기를 나타낸다.Wherein R 9 and R 10 are the same or different and are methyl, ethyl, propyl, iso-propyl, butyl, secondary-butyl, tert-butyl, amyl, iso-amyl, hexyl, octyl, 2-ethylhexyl, Alkyl, aryl, aralkyl or alkenyl groups having 1 to 20 carbon atoms such as phenyl and benzyl.
상기 그리냐르 화합물의 구체예에는 메틸마그네슘 클로라이드, 에틸마그네슘 클로라이드, 에틸마그네슘 브로마이드, 에틸마그네슘 요오다이드, 프로필마그네슘 클로라이드, 프로필마그네슘 브로마이드, 부틸마그네슘 클로라이드, 부틸마그네슘 브로마이드, 2차-부틸마그네슘 클로라이드, 2차-부틸마그네슘 브로마이드, 3차-부틸마그네슘 클로라이드, 3차-부틸마그네슘 브로마이드, 아밀마그네슘 클로라이드, 이소-아밀 마그네슘 클로라이드, 페닐마그네슘 클로라이드, 페닐마그네슘 브로마이드 등이 있다.Specific examples of the Grignard compound include methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, propylmagnesium chloride, propylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, secondary-butylmagnesium chloride, 2 Tea-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, amylmagnesium chloride, iso-amyl magnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide and the like.
R10R11Mg로 표시되는 화합물의 구체예에는 디에틸마그네슘, 디프로필마그네슘, 디이소프로필마그네슘, 디부틸마그네슘, 디-2차-부틸마그네슘, 디-3차-부틸마그네슘, 부틸-2차-부틸마그네슘, 디아밀 마그네슘, 디페닐 마그네슘 등이 있다.Specific examples of the compound represented by R 10 R 11 Mg include diethylmagnesium, dipropylmagnesium, diisopropylmagnesium, dibutylmagnesium, di-tert-butylmagnesium, di-tert-butylmagnesium, butyl-secondary Butyl magnesium, diamyl magnesium, diphenyl magnesium, and the like.
상기 유기 마그네슘 화합물의 합성시에 디에틸 에테르, 디프로필 에테르, 디-이소-프로필 에테르, 디부틸 에테르, 디-이소-부틸 에테르, 디아밀 에테르, 디-이소-아밀 에테르, 디헥실 에테르, 디옥틸 에테르, 디페닐 에테르, 디벤질 에테르, 페네톨, 아니솔, 테트라히드로푸란, 테트라히드로피란 등의 에테르성 용매가 사용될 수 있다. 헥산, 헵탄, 옥탄, 시클로 헥산, 메틸시클로헥산, 벤젠, 톨루엔, 크실렌 등의 탄화수소 용매 및 이들 에테르성 용매와 탄화수소 용매로 이루어진 용매 혼합물도 사용 가능하다. 바람직하게는 유기 마그네슘 화합물이 에테르성 용액의 상태로 사용된다. 이러한 목적을 위하여, 분자 중에 탄소수 6 이상을 갖는 에테르 화합물 또는 환식 구조를 갖는 에테르 화합물이 사용된다.Diethyl ether, dipropyl ether, di-iso-propyl ether, dibutyl ether, di-iso-butyl ether, diamyl ether, di-iso-amyl ether, dihexyl ether, di in the synthesis of the organic magnesium compound Ethereal solvents such as octyl ether, diphenyl ether, dibenzyl ether, phentol, anisole, tetrahydrofuran, tetrahydropyran and the like can be used. Hydrocarbon solvents such as hexane, heptane, octane, cyclo hexane, methylcyclohexane, benzene, toluene, xylene, and solvent mixtures consisting of these ethereal and hydrocarbon solvents can also be used. Preferably the organic magnesium compound is used in the form of an ethereal solution. For this purpose, ether compounds having 6 or more carbon atoms in the molecule or ether compounds having a cyclic structure are used.
촉매 성능의 관점에서, R9MgCl 로 표시되는 그리냐르 화합물을 에테르 용액의 상태로 사용하는 것이 특히 바람직하다.In view of catalyst performance, it is particularly preferable to use the Grignard compound represented by R 9 MgCl in the state of an ether solution.
상기 유기 마그네슘 화합물과 유기 금속 화합물 간에 형성되는 탄화수소-가용성 복합체도 또한 사용 가능하다. 유기 금속 화합물의 예로서 Li, Be, B, Al 및 Zn의 유기 화합물이 언급될 수 있다.Hydrocarbon-soluble complexes formed between the organo magnesium compound and the organometallic compound can also be used. As examples of the organometallic compounds, organic compounds of Li, Be, B, Al and Zn may be mentioned.
(d) 유기 다공질 중합체(d) organic porous polymer
본 발명에서 사용되는 유기 다공질 중합체의 예로서, 중합체의 폴리스티렌형, 폴리아크릴산 에스테르형, 폴리메타크릴산 에스테르형, 폴리아크릴로니트릴형, 폴라비닐클로라이드형 및 폴리올레핀 형으로 제조되는 다공질 중합체 비이드가 언급될 수 있다. 상기 중합체의 구체예에는 폴리스티렌, 스티렌-디비닐벤젠 공중합체, 스티렌-N, N'-알킬렌 디메타크릴아미드 공정합체, 스티렌-에틸렌글리콜-디(메틸 메타크릴레이트) 공중합체, 폴리메틸 아크릴레이트, 폴리에틸 아크릴레이트, 메틸 아크릴레이트-디비닐벤젠 공중합체, 에틸 아크릴레이트-디비닐벤젠 공중합체, 폴리메틸 메타크릴레이트, 메틸 메타크릴레이트-디비닐벤젠 공중합체, 폴리에틸렌글리콜-디(메틸메타크릴레이트), 폴리아크릴로니트릴, 아크릴로니트릴-디비닐벤젠 공중합체, 폴리비닐 클로라이드, 폴리비닐피롤리딘, 폴리비닐피리딘, 에틸비닐벤젠-디비닐벤젠 공중합체, 폴리에틸렌, 에틸렌-메타크릴레이트 공중합체, 폴리프로필렌 등이 있다.Examples of the organic porous polymer used in the present invention include porous polymer beads made of polystyrene type, polyacrylic acid ester type, polymethacrylic acid ester type, polyacrylonitrile type, polyvinylchloride type and polyolefin type of the polymer. May be mentioned. Specific examples of the polymer include polystyrene, styrene-divinylbenzene copolymer, styrene-N, N'-alkylene dimethacrylamide copolymer, styrene-ethylene glycol-di (methyl methacrylate) copolymer, polymethyl acrylic Latex, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyethylene glycol-di (methyl Methacrylate), polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-methacryl Latex copolymer, polypropylene, and the like.
이들 유기 다공질 중합체 담체 중에서, 폴리스티렌형, 폴리비닐 클로라이드형, 폴리올레핀형 및 폴리아크릴로니트릴형의 다공질 중합체 비이드가 바람직하며, 폴리스티렌, 스티렌-디비닐벤젠 공중합체 및 폴리비닐클로라이드가 더욱 바람직하다.Among these organic porous polymer carriers, porous polymer beads of polystyrene type, polyvinyl chloride type, polyolefin type and polyacrylonitrile type are preferable, and polystyrene, styrene-divinylbenzene copolymer and polyvinyl chloride are more preferable.
유기 다공질 중합체 담체의 평균 입경은 5 내지 1,000㎛, 바람직하게는 10 내지 500㎛ 및 특히 15 내지 200㎛이다. 세공 반경 범위 100 내지 5,000 옹스트롱에서 자체의 세공 용적은 0.1cc/g 이상, 바람직하게는 0.2cc/g 이상, 특히 0.3cc/g 이상이다. 유기 다공질 중합체 담체의 세공 용적이 너무 작을 경우, 촉매 성분은 그 속으로 효율적으로 함침될 수 없다. 유기 다공질 중합체 담체의 세공 용적이 0.1cc/g 이상일지라도 상기 세공 반경이 100 내지 5,000 옹스트롱의 범위를 넘을 경우에 촉매 성분은 효율적으로 함침될 수 없다.The average particle diameter of the organic porous polymer carrier is 5 to 1,000 mu m, preferably 10 to 500 mu m and in particular 15 to 200 mu m. Its pore volume in the pore radius range of 100 to 5,000 Angstroms is at least 0.1 cc / g, preferably at least 0.2 cc / g, in particular at least 0.3 cc / g. If the pore volume of the organic porous polymer carrier is too small, the catalyst component cannot be impregnated efficiently into it. Even if the pore volume of the organic porous polymer carrier is at least 0.1 cc / g, the catalyst component cannot be impregnated efficiently when the pore radius exceeds the range of 100 to 5,000 Angstroms.
(e) 에스테르 화합물(e) ester compounds
본 발명에서 사용되는 에스테르 화합물로서, 지방족 카르복실산 에스테르류, 올레핀계 카르복실산 에스테르류, 지환족 카르복실산 에스테르류 및 방향족 카르복실산 에스테르류를 포함하는 일- 및 다-가 카르복실산류의 에스테르류가 사용된다. 에스테르 화합물의 구체예에는 메틸 아세테이트, 에틸아세테이트, 페닐아세테이트, 메틸프로피오네이트, 에틸프로피오네이트, 에틸부티레이트, 에틸발레레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 메틸 메타크릴레이트, 에틸 벤조에이트, 부틸 벤조에이트, 메틸 톨루에이트, 에틸 톨루에이트, 에틸 아니세이트, 디에틸 숙신에이트, 디부틸 숙신에이트, 디에틸 말로네이트, 디부틸 말로네이트, 디메틸 말리에이트, 디부틸 말리에이트, 디에틸 아타콘에이트, 디부틸이타콘에이트, 모노에틸프탈레이트, 디메틸프탈레이트, 메틸에틸프탈레이트, 디에틸프탈레이트, 디프로필프탈레이트, 디이소프로필프탈레이트, 디부틸프탈레이트, 디이소부틸프탈레이트, 디헵틸 프탈레이트, 디옥틸 프탈레이트, 디페닐 프탈레이트 등이 있다.As the ester compound used in the present invention, mono- and polyvalent carboxylic acids including aliphatic carboxylic acid esters, olefinic carboxylic acid esters, alicyclic carboxylic acid esters and aromatic carboxylic acid esters Esters are used. Specific examples of the ester compound include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl Benzoate, methyl toluate, ethyl toluate, ethyl aniseate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl ataconate, Dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, diphenyl phthalate Etc.
이들 에스테르 화합물 중에서 프탈산 에스테르 및 말레산 에스테르 및 메타크릴산 에스테르 등의 올레핀계 카르복실산 에스테르가 바람직하며, 프탈산 디에테르가 특히 바람직하다.Among these ester compounds, olefinic carboxylic acid esters such as phthalic ester, maleic ester and methacrylic ester are preferable, and phthalic acid diether is particularly preferable.
(f) 전자 공여성 화합물(f) electron donating compounds
본 발명은 전자 공여성 화합물로서, 에스테르 화합물, 에테르 화합물, 케톤 화합물 등이 사용된다.In the present invention, as the electron donating compound, an ester compound, an ether compound, a ketone compound and the like are used.
에스테르 화합물로서, 지방족 카르복실산 에스테르, 올레핀계 카르복실산 에스테르, 지환족 카르복실산 에스테르 및 방향족 카르복실산 에스테르를 포함하는 일- 및 다-가 카르복실산의 에스테르가 사용된다. 에스테르 화합물의 구체예는 메틸 아세테이트, 에틸 아세테이트, 페닐 아세테이트, 메틸 프로피오네이트, 에틸 프로피오네이트, 에틸 부티레이트, 에틸 발레레이트, 메틸 아크릴레이트, 에틸 아크릴레이트, 메틸 메타크릴레이트, 에틸 벤조에이트, 부틸 벤조에이트, 메틸 톨루에이트, 에틸 톨루에이트, 에틸 아니세이트, 디에틸 숙신에이트, 디부틸 숙신에이트, 디에틸말로네이트, 디부틸말로네이트, 디메틸말리에이트, 디부틸말리에이트, 디에틸 이타콘에이트, 디부틸 이타콘에이트, 모노 에틸 프탈레이트, 디메틸 프탈레이트, 메틸 에틸 프탈레이트, 디에틸 프탈레이트 디프로필 프탈레이트, 디이소프로필 프탈레이트, 디부틸프탈레이트, 디이소부틸프탈레이트, 디헵틸 프탈레이트, 디옥틸프탈레이트, 디페닐 프탈레이트 등이 있다.As ester compounds, esters of mono- and polyhydric carboxylic acids including aliphatic carboxylic acid esters, olefinic carboxylic acid esters, cycloaliphatic carboxylic acid esters and aromatic carboxylic acid esters are used. Specific examples of the ester compounds include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl Benzoate, methyl toluate, ethyl toluate, ethyl aniseate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate, diethyl itaconate, Dibutyl itaconate, mono ethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, diphenyl phthalate, etc. There is this.
이들 에스테르 화합물 중에서, 프탈산 에스테르 및 말레산 에스테르 및 메타크릴산 에스테르 등의 올레핀계 카르복실산 에스테르가 바람직하며, 프탈산 디에스테르가 특히 바람직하다.Among these ester compounds, olefinic carboxylic acid esters such as phthalic acid ester, maleic acid ester and methacrylic acid ester are preferable, and phthalic acid diester is particularly preferable.
에테르 화합물로서 디에틸 에테르, 디프로필 에테르, 디이소프로필 에테르, 디부틸 에테르, 디아밀 에테르, 디-이소-아밀 에테르, 디네오펜틸 에테르, 디헥실 에테르, 디옥틸 에테르, 메틸부틸 에테르, 메틸 이소-아밀 에테르, 에틸 이소-부틸 에테르 등과 같은 디알킬 에테르류가 바람직하다.As ether compound, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, di-iso-amyl ether, diopentyl ether, dihexyl ether, dioctyl ether, methylbutyl ether, methyl iso Dialkyl ethers such as amyl ether, ethyl iso-butyl ether and the like are preferred.
이들 중에서, 디부틸 에테르 및 디-이소-아밀 에테르가 특히 바람직하다.Of these, dibutyl ether and di-iso-amyl ether are particularly preferred.
케톤 화합물로서, 아세톤, 메틸 에틸 케톤, 디에틸 케톤, 아세톤 페논, 프로피오페논, 벤조페논, 시클로헥사논, 2,4-펜타디온, 1-페닐-1,3-부탄디온 등이 언급될 수 있다.As the ketone compound, acetone, methyl ethyl ketone, diethyl ketone, acetone phenone, propiophenone, benzophenone, cyclohexanone, 2,4-pentadione, 1-phenyl-1,3-butanedione and the like can be mentioned. have.
이들 전자 공여상 화합물은 단독으로 또는 다른 화합물과의 혼합물의 형태로 사용될 수 있다.These electron donor phase compounds may be used alone or in the form of mixtures with other compounds.
(g) 티탄 촉매 성분의 합성(g) Synthesis of Titanium Catalyst Components
Si-O 결합을 갖는 유기 규소 화합물 및 유기 다공질 중합체의 존재하에서 유기 마그네슘 화합물로 일반식 Ti(OR1)aX4-a으로 표시되는 티탄 화합물을 환원시켜 고체 생성물을 수득한 후, 생성된 고체 생성물을 에스테르 화합물 및 이어서 사염화 티탄 또는 염화 티탄과 전자 공여성 화합물의 혼합물로 처리하여 본 발명의 티탄 촉매 성분을 합성한다. 이 때, 환원시에 유기 다공질 중합체의 입자 상에 고체를 석출시키고, 고체 생성물은 미세 분말의 형성없이 유기 다공질 중합체의 형태로 보유한다.The titanium compound represented by the general formula Ti (OR 1 ) a X 4-a was reduced with an organic magnesium compound in the presence of an organosilicon compound having an Si-O bond and an organic porous polymer to obtain a solid product, which was then produced. The product is treated with an ester compound followed by titanium tetrachloride or a mixture of titanium chloride and an electron donating compound to synthesize the titanium catalyst component of the present invention. At this time, a solid is precipitated on the particles of the organic porous polymer upon reduction, and the solid product is retained in the form of the organic porous polymer without formation of fine powder.
유기 마그네슘 화합물로 티탄 화합물을 환원시키는 방법으로서, 티탄 화합물, 유기 규소 화합물 및 유기 다공질 중합체의 혼합물에 유기 마그네슘 화합물을 첨가함이 언급될 수 있다.As a method of reducing the titanium compound with the organic magnesium compound, mention may be made of adding the organic magnesium compound to the mixture of the titanium compound, the organosilicon compound and the organic porous polymer.
바람직하게는, 티탄 화합물, 유기 규소 화합물 및 유기 다공질 중합체를 적절한 용매로 용해시키거나 희석시킨 후 사용한다.Preferably, the titanium compound, the organosilicon compound and the organic porous polymer are used after being dissolved or diluted with a suitable solvent.
상기 용매로서, 헥산, 헵탄, 옥탄, 데칸 등의 지방족 탄화수소, 톨루엔, 크실렌 등의 방향족 탄화수소, 시클로헥산, 메틸 시클로헥산, 데칼린 등의 지환족 탄화수소, 디에틸 에테르, 디부틸 에테르, 디이소아밀 에테르 테트라하이드로 푸란 등의 에테르가 사용될 수 있다.As the solvent, aliphatic hydrocarbons such as hexane, heptane, octane, decane, aromatic hydrocarbons such as toluene, xylene, alicyclic hydrocarbons such as cyclohexane, methyl cyclohexane, decalin, diethyl ether, dibutyl ether, diisoamyl ether Ethers such as tetrahydrofuran can be used.
환원 반응의 온도는 -50℃ 내지 70℃, 바람직하게는 -30℃ 내지 50℃ 및 특히 -25℃ 내지 35℃이다.The temperature of the reduction reaction is -50 ° C to 70 ° C, preferably -30 ° C to 50 ° C and especially -25 ° C to 35 ° C.
적하 시간은 제한이 없을지라도 통상적으로 약 30분 내지 6시간이다. 환원 반응의 완결 후에, 후반응을 20℃ 내지 120℃에서 부가적으로 수행할 수 있다.The dropping time is usually about 30 minutes to 6 hours, although there is no limitation. After completion of the reduction reaction, the post reaction may additionally be carried out at 20 ° C to 120 ° C.
유기 규소 화합물의 사용량은 티탄 원자에 대한 규소 원자의 원자비(Si/Ti)로 표현하여 1 내지 50, 바람직하게는 1 내지 30 및 특히 3 내지 25이다.The amount of the organosilicon compound used is 1 to 50, preferably 1 to 30 and especially 3 to 25, expressed as an atomic ratio of silicon atoms to titanium atoms (Si / Ti).
유기 마그네슘 화합물의 사용량은 마그네슘 워자에 대한 티탄 워자와 규소 원자의 합의 원자비로 표현하여 0.1 내지 10, 바람직하게는 0.2 내지 5.0 및 특히 0.5 내지 2.0이다. 즉, 티탄 화합물, 유기 규소 화합물 및 유기 마그네슘 화합물의 양은 티탄 촉매 성분의 조성식 MgmTi(OR)nXp(ED)q에서 Mg/Ti 의 몰비를 나타내는 m의 값이 1 내지 51, 바람직하게는 2 내지 31 및 특히 4 내지 26이 되도록 결정될 수 있다.The amount of the organo magnesium compound used is 0.1 to 10, preferably 0.2 to 5.0 and especially 0.5 to 2.0, expressed in terms of the atomic ratio of the titanium wo and the silicon atoms to the magnesium wo. That is, the amount of the titanium compound, the organosilicon compound, and the organic magnesium compound is 1 to 51, preferably m, indicating the molar ratio of Mg / Ti in the compositional formula Mg m Ti (OR) n X p (ED) q of the titanium catalyst component. Can be determined to be from 2 to 31 and in particular from 4 to 26.
유기 다공질 중합체의 양은 고체 생성물 중의 그의 비율로 표현하여 20 내지 90 중량 %, 바람직하게는 30 내지 80 중량 %이다.The amount of organic porous polymer is 20 to 90% by weight, preferably 30 to 80% by weight, expressed in its proportion in the solid product.
환원 반응에 의하여 수득한 고체 생성물을 액체로부터 분리시키고, 헥산, 헵탄 등의 불활성 탄화수소 용매로 수회 세척한다.The solid product obtained by the reduction reaction is separated from the liquid and washed several times with an inert hydrocarbon solvent such as hexane, heptane.
이렇게 수득한 고체 생성물은 3 가 티탄, 마그네슘 및 히드로카르빌옥시기를 함유하며 통상적으로 비결정성 또는 매우 약한 결정성을 나타낸다. 특히, 비결정성 구조가 촉매 성능의 관점에서 바람직하다.The solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups and typically exhibits amorphous or very weak crystallinity. In particular, an amorphous structure is preferred in view of catalyst performance.
다음, 상기 수득한 고체 촉매를 에스테르 화합물로 처리한다.Next, the obtained solid catalyst is treated with an ester compound.
에스테르 화합물의 사용량은 고체 생성물 중에서 타탄 원자 1몰당 0.1 내지 50몰, 바람직하게는 0.3 내지 20몰 및 특히 0.5 내지 10몰이다. 환원하면, 에스테르 화합물의 양은 (전자 공여성 화합물)/Ti 의 몰비를 나타내는 티탄 촉매 성분의 조성식 MgmTi(OR)nXp(ED)q에서 q의 값이 0.2 내지 2가 되도록 결정될 수 있다.The amount of ester compound used is 0.1 to 50 moles, preferably 0.3 to 20 moles and especially 0.5 to 10 moles per mole of tartan atoms in the solid product. In other words, the amount of the ester compound can be determined so that the value of q is 0.2 to 2 in the compositional formula Mg m Ti (OR) n X p (ED) q of the titanium catalyst component representing the molar ratio of (electron donating compound) / Ti. .
고체 생성물 중의 마그네슘 원자 1몰당 에스테르 화합물의 양은 0.01 내지 1.0몰, 바람직하게는 0.03 내지 0.5몰이다.The amount of ester compound per mole of magnesium atom in the solid product is 0.01 to 1.0 mole, preferably 0.03 to 0.5 mole.
고체 생성물을 에스테르 화합물로 처리함은 슬러리법, 보올밀을 사용하는 기계적 분쇄 등의 양자를 접촉시킬 수 있는 특정 방법에 의하여 수행될 수 있다.Treatment of the solid product with the ester compound may be carried out by a specific method capable of contacting both a slurry method and a mechanical grinding using a bowl mill.
하지만 기계적 분쇄는 고체 촉매 성분 중에 다량의 미분을 형성하여 입도 분포를 확장시킨다. 따라서, 공업적 관점에서 바람직하지 못하다. 바람직하게는 희석제의 존재하에서 양자가 접촉되어야 한다.Mechanical grinding, however, forms a large amount of fine powder in the solid catalyst component to expand the particle size distribution. Therefore, it is not preferable from an industrial point of view. Preferably both should be contacted in the presence of a diluent.
희석제로서, 펜탄, 헥산, 헵탄, 옥탄 등의 지방족 탄화수소, 벤젠, 톨루엔; 크실렌 등의 방향족 탄화수소, 시클로헥산, 시클로펜탄 등의 지환족 탄화수소 및 1,2-디클로로에탄, 모노클로로벤젠 등의 할로겐화 탄화수소가 사용될 수 있다.As a diluent, Aliphatic hydrocarbons, such as pentane, hexane, heptane, an octane, benzene, toluene; Aromatic hydrocarbons such as xylene, alicyclic hydrocarbons such as cyclohexane and cyclopentane, and halogenated hydrocarbons such as 1,2-dichloroethane and monochlorobenzene can be used.
희석제의 사용량은 고체 생성물 1g당 0.1ml 내지 1,000ml, 바람직하게는 1ml 내지 100ml이다. 처리 온도는 -50℃ 내지 150℃, 바람직하게는 0℃ 내지 120℃이다. 처리 시간은 10분 이상, 바람직하게는 30분 내지 3시간이다. 처리의 완결 후, 혼합물을 정치시켜 고체를 액체로부터 분리시킨 후, 고체를 불활성 탄화수소 용매로 수회 세척하여 에스테르 처리된 고체를 수득한다.The amount of diluent used is 0.1 ml to 1,000 ml, preferably 1 ml to 100 ml per gram of solid product. The treatment temperature is from -50 deg. C to 150 deg. C, preferably from 0 deg. C to 120 deg. The treatment time is 10 minutes or more, preferably 30 minutes to 3 hours. After completion of the treatment, the mixture is allowed to stand to separate the solid from the liquid and the solid is washed several times with an inert hydrocarbon solvent to give an ester treated solid.
이어서, 상기 방법으로 수득된 고체생성물을 사염화 티탄으로 처리한다. 경우에 따라, 이 처리를 전자 공여성 화합물의 존재하에서 수행할 수 있다. 예를 들면, 상기 처리가 에테르 화합물 및 사염화 티탄의 혼합물 또는 에테르 화합물, 에스테르 화합물 및 사염화 티탄의 혼합물과 함께 수행될 수 있다.The solid product obtained by the above method is then treated with titanium tetrachloride. If desired, this treatment can be carried out in the presence of an electron donating compound. For example, the treatment can be carried out with a mixture of ether compounds and titanium tetrachloride or with a mixture of ether compounds, ester compounds and titanium tetrachloride.
사염화 티탄을 사용하는 고체 생성물의 처리를 바람직하게는 슬러리의 상태에서 수행한다. 슬러리의 형성용으로 사용되는 용매로서, 펜탄, 헥산, 옥탄, 데칸 등의 지방족 탄화수소, 톨루엔, 크실렌 등의 방향족 탄화수소, 데칼린, 시클로헥산, 메틸시클로헥산 등의 지환족 탄화수소 및 디클로로에탄, 트리클로로에탄, 트리클로로에틸렌, 모노클로로벤젠, 디클로로벤젠, 트리클로로벤젠 등과 같은 할로겐화 탄화수소가 언급될 수 있다.Treatment of the solid product with titanium tetrachloride is preferably carried out in the form of a slurry. Examples of the solvent used for the formation of the slurry include aliphatic hydrocarbons such as pentane, hexane, octane and decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as decalin, cyclohexane and methylcyclohexane, and dichloroethane and trichloroethane. And halogenated hydrocarbons such as trichloroethylene, monochlorobenzene, dichlorobenzene, trichlorobenzene and the like can be mentioned.
슬러리의 농도는 0.05 내지 0.5g 고체/ml 용매 및 특히 0.1 내지 0.3g 고체/ml 용매이다.The concentration of the slurry is from 0.05 to 0.5 g solids / ml solvent and in particular from 0.1 to 0.3 g solids / ml solvent.
반응 온도는 30℃ 내지 150℃, 바람직하게는 45℃ 내지 120℃, 특히 60℃내지 100℃이다.The reaction temperature is 30 ° C to 150 ° C, preferably 45 ° C to 120 ° C, in particular 60 ° C to 100 ° C.
반응 시간에 대하여 특히 제한은 없지만, 통상적으로 30분 내지 6시간이다.There is no restriction | limiting in particular about reaction time, Usually, it is 30 minutes-6 hours.
고체 생성물 및 사염화 티탄을 첨가하는 방법은 사염화 티탄을 고체 생성물에 첨가하는 방법 및 고체 생성물을 사염화 티탄 용액 중에 첨가하는 방법 중의 하나일 수 있다.The method of adding the solid product and the titanium tetrachloride may be one of a method of adding titanium tetrachloride to the solid product and a method of adding the solid product in the titanium tetrachloride solution.
고체 생성물에 전자 공여성 화합물 및 사염화 티탄을 첨가하는 방법에 있어서, 사염화 티탄과 전자 공여성 화합물을 혼합한 후, 이 혼합물을 고체 생성물에 첨가하는 방법 및 전자 공여성 화합물 및 사염화 티탄을 고체 생성물에 동시에 첨가하는 방법이 특히 바람직하다.A method of adding an electron donating compound and titanium tetrachloride to a solid product, wherein the titanium tetrachloride and the electron donating compound are mixed and then the mixture is added to the solid product and the electron donating compound and titanium tetrachloride are added to the solid product. Particularly preferred is a method of adding at the same time.
고체 생성물과 사염화 티탄 간의 반응을 2회 이상 반복할 수 있다.The reaction between the solid product and titanium tetrachloride can be repeated two or more times.
사염화 티탄의 양은 고체 생성물 중에 함유된 티탄 원자 1몰당 1 내지 1,000몰, 바람직하게는 3 내지 500몰 및 특히 10 내지 300몰이다. 에테르 화합물 1몰당 사염화 티탄의 양은 1 내지 100몰, 바람직하게는 1.5 내지 75몰 및 특히 2 내지 50몰이다.The amount of titanium tetrachloride is 1 to 1,000 moles, preferably 3 to 500 moles and especially 10 to 300 moles per mole of titanium atoms contained in the solid product. The amount of titanium tetrachloride per mole of ether compound is 1 to 100 moles, preferably 1.5 to 75 moles and especially 2 to 50 moles.
전자 공여성 화합물의 양은 고체 생성물 중에 함유된 티탄 원자 1몰당 0.01 내지 100몰, 바람직하게는 0.05 내지 50몰 및 특히 0.1 내지 20몰이다.The amount of electron donating compound is from 0.01 to 100 moles, preferably from 0.05 to 50 moles and in particular from 0.1 to 20 moles per mole of titanium atoms contained in the solid product.
환원하면, 사염화 티탄과 전자 공여성 화합물의 양은 티탄 촉매 성분의 조성식 MgTi(OR)nXp(ED)q에서 (RO기)/Ti 의 몰비는 나타내는 n의 값이 0 내지 5가 되며, 상기 조성식에서 (전자 공여성 화합물)/Ti 의 몰비를 나타내는 q의 값이 0.2 내지 2가 되도록 결정될 수 있다.In other words, the amount of titanium tetrachloride and the electron donating compound is 0 to 5, wherein the molar ratio of (RO group) / Ti in the composition formula MgTi (OR) n X p (ED) q of the titanium catalyst component is 0 to 5. The value of q representing the molar ratio of (electron donating compound) / Ti in the composition formula may be determined to be 0.2 to 2.
상기 방법으로 수득한 3가 티탄-함유 고체 촉매 성분을 액체로부터 분리시키고, 헥산, 헵탄 등의 불활성 탄화수소 용매로 수회 세척한 후, 중합시에 사용한다.The trivalent titanium-containing solid catalyst component obtained by the above method is separated from the liquid, washed several times with an inert hydrocarbon solvent such as hexane, heptane and then used in the polymerization.
또 하나의 허용되는 태양에 있어서, 3가 티탄-함유 고체 촉매 성분을 액체로부터 분리시키고, 다량의 모노클로로벤젠 등의 할로겐화 탄화수소 용매 또는 톨루엔, 크실렌 등의 방향족 탄화수소 용매로 온도 50℃ 내지 120℃에서 1회 이상 세척한 후, 헥산 등의 지방족 탄화수소 용매로 수회 세척한 후, 중합시에 사용한다.In another acceptable embodiment, the trivalent titanium-containing solid catalyst component is separated from the liquid and is used at a temperature of 50 ° C. to 120 ° C. with a large amount of halogenated hydrocarbon solvents such as monochlorobenzene or aromatic hydrocarbon solvents such as toluene and xylene. After washing one or more times, washing several times with an aliphatic hydrocarbon solvent such as hexane is used at the time of polymerization.
상기 방법으로 수득한 고체를 티탄 촉매 성분으로서 사용한다.The solid obtained by the above method is used as the titanium catalyst component.
(h) 유기 알루미늄 화합물(h) organoaluminum compounds
상기 티탄 촉매 성분과 배합되어 본 발명에서 사용되는 유기 알루미늄 화합물은 분자속에 하나 이상의 Al-탄소 결합을 가지고 있다.The organoaluminum compound used in the present invention in combination with the titanium catalyst component has at least one Al-carbon bond in the molecule.
이의 대표예는 다음과 같다:Representative examples are as follows:
R12
R13R14Al-O-AlR15R16 R 13 R 14 Al-O-AlR 15 R 16
(상기 식에서, R12, R13, R14, R15및 R16은 각각 탄소수 1 내지 8의 탄화수소기를 나타내고 Y는 할로겐, 수소 또는 알콕시기를 나타내며
유기 알루미늄 화합물의 구체예에는 트리에틸 알루미늄, 트리이소부틸 알루미늄, 트리헥실 알루미늄 등의 트리알킬 알루미늄, 디에틸알루미늄 히드라이드, 디이소부틸알루미늄 히드라이드 등의 디알킬알루미늄 히드라이드, 디에틸알루미늄 클로라이드 등의 디알킬알루미늄 할라이드, 트리알킬알루미늄 및 디알킬알루미늄 할라이드의 혼합물 및 테트라에틸디알루목산, 테트라부틸디알루목산 등의 알킬 알루목산이 있다.Specific examples of the organoaluminum compound include dialkylaluminum hydrides such as trialkylaluminum such as triethylaluminum, triisobutylaluminum and trihexyl aluminum, diethylaluminum hydride and diisobutylaluminum hydride, diethylaluminum chloride and the like. And a mixture of dialkylaluminum halides, trialkylaluminum and dialkylaluminum halides, and alkyl alumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.
이들 유기 알루미늄 화합물 중에서, 트리알킬 알루미늄, 트리알킬알루미늄 및 디알킬 알루미늄 할라이드의 혼합물 및 알킬알루목산이 바람직하며, 트리에틸알루미늄, 트리이소부틸알루미늄, 트리에틸알루미늄과 디에틸알루미늄 클로라이드 혼합물 및 테트라 에틸디알루목산이 특히 바람직하다.Among these organoaluminum compounds, mixtures of trialkylaluminum, trialkylaluminum and dialkylaluminum halides and alkylalumoxanes are preferred, triethylaluminum, triisobutylaluminum, triethylaluminum and diethylaluminum chloride mixtures and tetraethyldi Alumoxane is particularly preferred.
유기 알루미늄 화합물의 양은 적절하게는 넓은 범위에서 선택될 수 있다. 예를 들면, 고체 촉매 중에서 티탄 원자 1몰당 1 내지 1,000몰 및 바람직하게는 5 내지 600몰의 범위에서 선택될 수 있다.The amount of the organoaluminum compound may suitably be selected in a wide range. For example, it may be selected in the range of 1 to 1,000 moles and preferably 5 to 600 moles per mole of titanium atoms in the solid catalyst.
(i) 예비 중합(i) prepolymerization
에틸렌을 공중합 시키기 전에, 본 발명의 티탄 촉매 성분을 예비 중합시킬 수 있다. 예비 중합을 상기한 유기 알루미늄 화합물 및 올레핀과 티탄 촉매 성분을 접촉시켜 수행한다. 올레핀으로서 에틸렌, 프로필렌, 부텐-1 등이 사용될 수 있다.Before copolymerizing ethylene, the titanium catalyst component of the present invention may be prepolymerized. Prepolymerization is carried out by contacting the organoaluminum compound and olefin described above with a titanium catalyst component. Ethylene, propylene, butene-1 and the like can be used as the olefin.
예비 중합은 단독 중합 및 공중합 중의 어느 하나일 수 있다.The prepolymerization can be either homopolymerization or copolymerization.
예비 중합을 전자 공여성 화합물 및 수소 등의 존재하에서 수행하여 고결정성 예비 중합체를 수득할 수 있다.Prepolymerization can be carried out in the presence of an electron donating compound and hydrogen or the like to obtain a highly crystalline prepolymer.
이 목적용으로 사용되는 전자 공여성 화합물로서, R이 탄소수 1 내지 20의 탄화수소기를 나타내는 Si-OR 결합을 갖는 유기 화합물이 바람직하다.As an electron donating compound used for this purpose, the organic compound which has Si-OR bond which R represents a C1-C20 hydrocarbon group is preferable.
바람직하게는, 본 발명의 티탄 촉매 성분을 슬러리 상태에서 예비 중합시킨다. 슬러리 형성용으로 사용되는 용매로서, 부탄, 펜탄, 헥산, 헵탄 등의 지방족 탄화수소 및 톨루엔, 크실렌 등의 방향족 탄화수소가 언급될 수 있다.Preferably, the titanium catalyst component of the present invention is prepolymerized in a slurry state. As the solvent used for slurry formation, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and aromatic hydrocarbons such as toluene and xylene may be mentioned.
슬러리의 농도는 바람직하게는 0.001 내지 0.5g 고체/ml 용매 및 특히 0.01 내지 0.3g 고체/ml 용매이다. 바람직하게는, 유기 알루미늄 화합물을 Al/Ti 몰비가 0.1 내지 100 및 특히 1 내지 10의 양이 되도록 사용한다.The concentration of the slurry is preferably 0.001 to 0.5 g solids / ml solvent and in particular 0.01 to 0.3 g solids / ml solvent. Preferably, the organoaluminum compound is used such that the Al / Ti molar ratio is from 0.1 to 100 and in particular from 1 to 10.
예비 중합 온도가 바람직하게는 -30℃ 내지 80℃ 및 특히 -10℃ 내지 50℃이다.The prepolymerization temperature is preferably -30 ° C to 80 ° C and in particular -10 ° C to 50 ° C.
바람직하게는, 예비 중합을 수행하여 고체 촉매 성분 1g 당 중합체 0.1 내지 100g, 특히 0.5 내지 50g을 형성한다.Preferably, prepolymerization is carried out to form 0.1 to 100 g, in particular 0.5 to 50 g, of polymer per g of solid catalyst component.
(j) 에틸렌 공중합체의 제조(j) Preparation of Ethylene Copolymer
본 발명은 예비 중합시킨 티탄 촉매 성분 또는 상기한 티탄 촉매 성분 및 유기 알루미늄 화합물을 사용하여 하나 이상의 알파-올레핀(들) 및 에틸렌을 공중합시키는 방법을 제공한다.The present invention provides a process for copolymerizing one or more alpha-olefin (s) and ethylene using a prepolymerized titanium catalyst component or the above-described titanium catalyst component and an organoaluminum compound.
이제, 중합의 태양을 더욱 구체적으로 하기할 것이다.Now, the aspect of polymerization will be more specifically described.
티탄 촉매 성분 및 유기 알루미늄 화합물을 중합조 중으로 공급하는 방법은 수소, 에틸렌, 프로필렌 등의 존재하에서, 또는 질소, 아르곤 가스 등의 불활성 가스의 존재하에서 수분이 없는 상태로 공급함을 제외하고는, 특히 제한된 조건은 없다.The method of supplying the titanium catalyst component and the organoaluminum compound into the polymerization tank is particularly limited except that the titanium catalyst component and the organoaluminum compound are supplied in the absence of water in the presence of hydrogen, ethylene, propylene or the like or in the presence of an inert gas such as nitrogen or argon gas. There is no condition.
티탄 촉매 성분 및 유기 알루미늄 화합물은 분리하여 또는 사전에 상호 접촉시킨 후에 공급될 수 있다.The titanium catalyst component and the organoaluminum compound can be supplied separately or after mutual contact.
중합 반응은 통상의 기상, 중합, 슬러리 중합 등의 공지 방법으로 수행될 수 있다.The polymerization reaction can be carried out by known methods such as conventional gas phase, polymerization, slurry polymerization, and the like.
중합 조건은 하기와 같다. 따라서, 중합이 압력은 상압 내지 40kg/cm2, 온도는 중합체의 용융 온도 이하의 온도, 바람직하게는 20℃ 내지 100℃ 및 특히 40℃ 내지 90℃에서 수행됨이 바람직하다. 또한, 공중합 공정에서 최종 생성물의 용융 유동성을 조절하기 위한 목적용 중합계에 수소가 첨가될 수 있다. 중합법을 연속식으로나 회분식으로 수행할 수 있다.Polymerization conditions are as follows. Accordingly, the polymerization is preferably carried out at atmospheric pressure to 40 kg / cm 2 , at a temperature below the melting temperature of the polymer, preferably at 20 ° C. to 100 ° C. and especially at 40 ° C. to 90 ° C. In addition, hydrogen may be added to the desired polymerization system for controlling the melt flowability of the final product in the copolymerization process. The polymerization process can be carried out continuously or batchwise.
본 발명은 탄소수 3 이상의 알파-올레핀에 적용될 수 있다. 더욱 구체적으로 말하면, 본 발명에 적용 가능한 알파-올레핀에는 프로필렌, 부텐-1, 펜텐-1, 헥센-1, 3-메틸-펜텐-1, 4-메틸펜텐-1 등이 있는데, 본 발명이 이들 올레핀에 의하여 제한되는 것은 결코 아니다. 본 발명의 중합법에 따라 에틸렌 및 하나 이상의 알파-올레핀의 혼합물을 촉매와 접촉시켜 에틸렌 공중합체를 제조할 수 있다.The present invention can be applied to alpha-olefins having 3 or more carbon atoms. More specifically, the alpha-olefins applicable to the present invention include propylene, butene-1, pentene-1, hexene-1, 3-methyl-pentene-1, 4-methylpentene-1, and the like. It is by no means limited by olefins. According to the polymerization process of the present invention, a mixture of ethylene and one or more alpha-olefins may be contacted with a catalyst to prepare an ethylene copolymer.
다음, 본 발명의 방법은 하기 실시예에 의하여 더욱 상세하게 예시될 것이다. 본 발명이 이들 실시예에 의하여 제한되는 것을 결코 아니다.Next, the method of the present invention will be illustrated in more detail by the following examples. The present invention is in no way limited by these examples.
실시예에서 중합체의 특성을 하기 방법으로 측정하였다.The properties of the polymers in the examples were measured by the following method.
밀도는 JIS K-6760에 따라 측정하였다.Density was measured according to JIS K-6760.
융용 지수는 JIS K-6760에 따라 190℃에서 측정하였다.The melt index was measured at 190 ° C. according to JIS K-6760.
벌크 밀도를 JIS K-6721에 따라 측정하였다.Bulk density was measured according to JIS K-6721.
용융 유동성의 척도로서 유출량비(MFR)를 채용하였다. 여기에서, MFR은 ASTM1238-57T에 따라 측정(용융 지수 MI의 측정)한, 하중 2.160kg 시의 유출량에 대한 하중 21.60kg 시의 유출량의 비로 표현된다:The flow rate ratio (MFR) was employed as a measure of melt flowability. Here, MFR is expressed as the ratio of the flow rate at 21.60 kg load to the flow rate at 2.160 kg load, measured according to ASTM1238-57T (measurement of melt index MI):
MFR = (하중 21.60kg 시의 유출량)/하중 2.160kg 시의 유출량.MFR = (flow rate at 21.60 kg load) / flow rate at 2.160 kg load.
통상적으로 분자량 분포가 넓은 것이 MFR의 값이 큰 것을 제공함은 공지되어 있다.It is generally known that a wide molecular weight distribution provides for a large value of MFR.
[실시예 1]Example 1
[(A) 유기 마그네슘 화합물의 합성][(A) Synthesis of Organic Magnesium Compound]
교반기, 환류 냉각기, 적하 깔때기 및 온도계를 장착한 1ℓ 용적의 플라스크의 내부 분위기를 아르곤 가스로 대체한 후, 그리냐르 반응용 삭상 금속 마그네슘 32.0g을 플라스크 중으로 투입한다.After replacing the internal atmosphere of the 1 L volume flask with stirrer, reflux cooler, dropping funnel and thermometer with argon gas, 32.0 g of Grinnard reaction grinding metal magnesium were introduced into the flask.
부틸 클로라이드 120g 및 디부틸 에테르 500ml를 적하 깔때기 중으로 충전시킬 후, 이들 혼합물 약 30ml를 플라스크 중의 마그네슘 상에 적하하여 반응을 개시시킨다. 반응 개시 후, 4시간에 걸쳐 50℃에서 적하를 계속한다. 적하를 완결시킨 후, 반응을 추가의 1시간 동안 60℃에서 계속한다. 이어서, 반응 혼합물을 실온까지 냉각시키고, 고체 물질을 여과하여 제거한다.After 120 g of butyl chloride and 500 ml of dibutyl ether are charged into the dropping funnel, about 30 ml of these mixtures are added dropwise onto magnesium in the flask to initiate the reaction. After the start of the reaction, dropping is continued at 50 ° C over 4 hours. After completion of dropping, the reaction is continued at 60 ° C. for an additional hour. The reaction mixture is then cooled to room temperature and the solid material is filtered off.
디부틸 에테르 중에 용해시킨 부틸 마그네슘 클로라이드를 1N 황산으로 가수분해하고, 1N 수산화나트륨 수용액으로 역적정하여 농도를 측정하는데, 이 때 지시약으로서 페놀프탈레인을 사용한다. 결과로서, 이의 농도는 2.0몰/ℓ 이었다.Butyl magnesium chloride dissolved in dibutyl ether was hydrolyzed with 1N sulfuric acid and back titrated with 1N aqueous sodium hydroxide solution to measure the concentration, at which time phenolphthalein was used as an indicator. As a result, its concentration was 2.0 mol / l.
[(B) 고체 생성물의 합성][B Synthesis of Solid Product]
교반기 및 적하 깔때기를 장착한 1,000ml의 용적을 갖는 플라스크의 내부 대기를 아르곤 가스로 대체한 후, 감압하, 80℃에서 5시간 건조시킨 스티렌-디비닐 벤젠 공중합체 [이의 평균 입경은 50㎛이고, 포로시미터로 측정한 세공 반경 범위 100 내지 5,000 옹스트롱 (이하 dVp로서 언급함)에서의 이의 세공 용량(cc/g)은 1.05cc/g이다.] 51.0g, 헵탄 250ml, 테트라부톡시티탄 4.5g(13.2mmol) 및 테트라에톡시실란 47.5g (228mmol)을 플라스크 중으로 충전시키고, 45분간 30℃에서 교반시킨다.A styrene-divinyl benzene copolymer dried at 80 ° C. for 5 hours under reduced pressure after replacing the internal atmosphere of the flask having a volume of 1,000 ml equipped with a stirrer and a dropping funnel with an average particle diameter of 50 μm , Its pore capacity (cc / g) in the pore radius range of 100 to 5,000 angstroms (hereinafter referred to as dVp) is 1.05 cc / g.] 51.0 g, 250 ml heptane, tetrabutoxytitanium 4.5 g (13.2 mmol) and 47.5 g (228 mmol) of tetraethoxysilane are charged into the flask and stirred at 30 ° C. for 45 minutes.
이어서, (A)에서 합성한 유기 마그네슘 화합물을 플라스크 내부 온도를 5℃로 유지하면서 45분에 걸쳐 적하 깔때기로부터 적하한다. 적하 후, 생성되는 혼합물을 5℃에서 45분간 교반한 후, 30℃에서 45분간 교반하고, 이어서 각각 헥산 300ml로 2회 세정하고, 감압하에서 건조시켜 갈색의 고체 생성물 85.2g을 수득하였다.Subsequently, the organic magnesium compound synthesized in (A) is added dropwise from the dropping funnel over 45 minutes while maintaining the flask internal temperature at 5 ° C. After dropping, the resulting mixture was stirred at 5 ° C. for 45 minutes, then at 30 ° C. for 45 minutes, then washed twice with 300 ml each of hexane and dried under reduced pressure to give 85.2 g of a brown solid product.
[(C) 고체 촉매 성분의 합성][(C) Synthesis of Solid Catalyst Component]
500ml 용적의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 환원 반응(B)에서 합성한 고체 생성물 57.3g, 톨루엔 191ml 및 디이소부틸 프탈레이트 16.0ml(60mmol)를 플라스크 중으로 충전시키고, 95℃에서 30분간 반응시킨다.After replacing the inner atmosphere of the 500 ml volume flask with argon gas, 57.3 g of the solid product synthesized in the reduction reaction (B), 191 ml of toluene and 16.0 ml (60 mmol) of diisobutyl phthalate were charged into the flask, React for a minute.
반응 종료 후, 고체 물질을 액체로부터 분리시키고, 각각 톨루엔 200ml로 2회 세정한다.After completion of the reaction, the solid material is separated from the liquid and washed twice with 200 ml of toluene each.
세정 후, 톨루엔 191ml, 부틸 에테르 1.2ml(7mmol) 및 사염화 티탄 17.2ml(156mmol)을 플라스크에 가하고, 95℃에서 2시간 반응시킨다. 반응 후, 95℃에서 고체 물질을 액체로부터 분리시키고, 상기 온도에서 각각 톨루엔 200ml로 2회 세정한다.After washing, 191 ml of toluene, 1.2 ml (7 mmol) of butyl ether and 17.2 ml (156 mmol) of titanium tetrachloride were added to the flask and allowed to react at 95 ° C for 2 hours. After the reaction, the solid material is separated from the liquid at 95 ° C. and washed twice with 200 ml of toluene each at this temperature.
추가로 각각 헥산 200ml로 세정한 후, 감압하에서 건조시켜 갈색의 고체 촉매 성분 52.8g을 수득하였다.Further, each was washed with 200 ml of hexane and dried under reduced pressure to give 52.8 g of a brown solid catalyst component.
유기 다공질 중합체 담체 중에 함유되어 있는 촉매 성분의 조성은 하기와 같았다:The composition of the catalyst component contained in the organic porous polymer carrier was as follows:
Mg17.2Ti(OR)4.0Cl33.4(ED)0.5 Mg 17.2 Ti (OR) 4.0 Cl 33.4 (ED) 0.5
[(D) 중합][(D) polymerization]
교반기를 장착한 5ℓ 용적의 오토클레이브의 내부 분위기를 아르곤 가스로 충분히 대체시킨 후, 충분히 건조시킨 고밀도 폴리에틸렌 200g을 분산제로서 공급한다. 내압을 감소시킨 후, 충분히 건조시킨 고밀도 폴리에틸렌 200g을 분산제로서 공급한다. 내압을 감소시킨 후, 22g의 부텐-1을 가하고, 80℃ 까지 가열한다. 이어서, 전압이 2.3kg/cm2에 도달될 때까지 수소를 공급한 후, 전압이 8.8kg/cm2에 도달될 때까지 에틸렌을 공급한다. 이어서 (C)에서 수득한 촉매 성분 12.1mg, 트리에틸 알루미늄 2.5mmol 및 헥산 15ml를 아르곤 압하에서 공급시켜 중합을 개시한다. 이어서, 기상 중합을 80℃에서 2시간, 에틸렌/부텐-2 혼합물 가스(에틸렌 함량 92 중량 %)를 계속 공급하면서 일정한 전압에서 계속 행한다.After sufficiently replacing the internal atmosphere of the 5 liter volume autoclave equipped with the stirrer with argon gas, 200 g of sufficiently dried high density polyethylene was supplied as a dispersant. After the internal pressure was reduced, 200 g of sufficiently dried high density polyethylene was fed as a dispersant. After the internal pressure was reduced, 22 g of butene-1 was added and heated to 80 ° C. Then, the supply of ethylene until the voltage reached after supply of hydrogen, the voltage is 8.8kg / cm 2 until it reached 2.3kg / cm 2. Subsequently, 12.1 mg of the catalyst component obtained in (C), 2.5 mmol of triethyl aluminum and 15 ml of hexane were fed under argon pressure to initiate the polymerization. Subsequently, gas phase polymerization is continued at a constant voltage for 2 hours at 80 ° C. while continuously supplying the ethylene / butene-2 mixture gas (92% by weight of ethylene content).
중합의 완결 후, 미반응 단량체를 퍼지시키고, 분산제로서 사용되는 고밀도 폴리에틸렌을 제거하여 미분 및 조압자가 없으며, 양호한 분말 특성을 갖는 중합체 102.1g을 수득한다. 오토클레이브 및 교반기의 내벽 전체 상에 어떠한 중합체의 부착도 관측되지 못하였다.After completion of the polymerization, the unreacted monomer is purged and the high density polyethylene used as the dispersant is removed to give 102.1 g of polymer having fine powder and no coarse powder and having good powder properties. No adhesion of polymer was observed throughout the inner wall of the autoclave and stirrer.
티탄 원자 1g당 중합체의 생성량(g) 즉, 촉매 활성은 1,690,000g 중합체/g 티탄 원자이었다.The amount of polymer produced (g) per gram of titanium atom, i.e., the catalytic activity was 1,690,000g polymer / g titanium atom.
이 중합체의 밀도는 0.921이고, 이의 MI는 0.98g/10분, 이의 MFR은 27.5 및 이의 벌크 밀도는 0.46g/cm3이었다. 전체 중합체 수득량 중에 냉크실렌-가용된 성분의 비율(이하에서 CXS로 언급함)은 6.4%이었다.The polymer had a density of 0.921, its MI of 0.98 g / 10 min, its MFR of 27.5 and its bulk density of 0.46 g / cm 3 . The proportion of cold xylene-soluble components in the total polymer yield (hereinafter referred to as CXS) was 6.4%.
중합체 분말의 형상은 거의 구형이었으며, 입도 분포는 협소하였고, 유동성은 양호하였다. 125㎛이하의 크기를 갖는 어떠한 미세 중합체도 생성되지 않았다.The shape of the polymer powder was almost spherical, the particle size distribution was narrow, and the fluidity was good. No fine polymer was produced with a size of 125 μm or less.
[비교예 1]Comparative Example 1
실시예 1(B)에서 수득한 고체 생성물(조성식 Mg17.9Ti(OR)20.9Cl17.9(ED)0.4350mg을 촉매 성분으로 사용함을 제외하고는, 실시예 1(D)와 동일한 방법으로 중합을 수행한다.The polymerization was carried out in the same manner as in Example 1 (D), except that 350 mg of the solid product obtained in Example 1 (B) (formula Mg 17.9 Ti (OR) 20.9 Cl 17.9 (ED) 0.4 350 mg) was used as a catalyst component. do.
결과로서, 소량의 중합체만이 수득되었다.As a result, only a small amount of polymer was obtained.
[비교예 2]Comparative Example 2
[(A) 고체 생성물의 합성][(A) Synthesis of Solid Product]
교반기 및 적하 깔때기를 장착한 용적 300ml의 플라스크의 내부 대기를 아르곤 가스로 대체한 후, 감압하에서 1시간 동안 80℃에서 건조시킨 실시예 1(B)의 스티렌-디비닐벤젠 공중합체 20.1g, 헵탄 100ml 및 테트라 부톡시티탄 7.2g(21.2mmol)을 플라스크 중으로 충전시키고, 30℃에서 45분간 교반시킨다.20.1 g of the styrene-divinylbenzene copolymer of Example 1 (B), which was replaced with argon gas after replacing the internal atmosphere of a 300 ml flask with a stirrer and a dropping funnel with argon gas for 1 hour under reduced pressure, heptane 100 ml and 7.2 g (21.2 mmol) of tetra butoxytitanium are charged into the flask and stirred at 30 ° C. for 45 minutes.
이어서, 실시예 1(A)에서 합성한 유기 마그네슘 화합물 10.6ml를 플라스크 내부 온도를 5℃로 유지하면서 20분에 걸쳐 적하 깔때기로부터 적하시킨다. 적하 후, 생성되는 혼합물을 5℃에서 45분간, 이어서 30℃에서 45분간 교반시킨 후, 고체 물질을 각각 헵탄 100ml로 3회 세척하고, 감압하에서 건조시켜 갈색의 고체 생성물 29.8g을 수득하였다.Subsequently, 10.6 ml of the organic magnesium compound synthesized in Example 1 (A) was added dropwise from the dropping funnel over 20 minutes while maintaining the flask internal temperature at 5 ° C. After dropping, the resulting mixture was stirred at 5 ° C. for 45 minutes and then at 30 ° C. for 45 minutes, then the solid material was washed three times with 100 ml of heptane each and dried under reduced pressure to give 29.8 g of a brown solid product.
[(B) 고체 촉매 성분의 합성][B Synthesis of Solid Catalyst Component]
용적 100ml의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 환원 반응(A)에서 합성한 고체 생성물 9.0g, 톨루엔 45.0ml 및 디이소부틸 프탈레이트 2.5ml(9.5mmol)를 플라스크 중에 충전시키고, 95℃에서 30분간 반응시킨다.After replacing the internal atmosphere of the volume 100 ml flask with argon gas, 9.0 g of the solid product synthesized in the reduction reaction (A), 45.0 ml of toluene and 2.5 ml (9.5 mmol) of diisobutyl phthalate were charged into the flask, and 95 ° C. React for 30 minutes at.
반응 종료 후, 고체 물질을 액체로부터 분리시키고, 각각 톨루엔 30ml로 2회 세정한다.After completion of the reaction, the solid material is separated from the liquid and washed twice with 30 ml of toluene each.
세정 후, 톨루엔 30.0ml, 부틸 에테르 0.19ml(0.64mmol) 및 사염화 티탄 2.7ml(25mmol)를 가하고, 95℃에서 3시간 반응시킨다. 반응 후, 고체 물질을 95℃에서 액체로부터 분리시키고, 상기 온도에서 각각 툴루엔 30ml로 2회 세정하고, 추가로 각각 헵탄 30ml로 2회 세정하며, 감압하에서 건조시켜 적갈색의 고체 28.1g을 수득하였다.After washing, 30.0 ml of toluene, 0.19 ml (0.64 mmol) of butyl ether and 2.7 ml (25 mmol) of titanium tetrachloride were added, and the mixture was reacted at 95 ° C for 3 hours. After the reaction, the solid material was separated from the liquid at 95 ° C., washed twice with 30 ml of toluene each at this temperature, further washed twice with 30 ml of heptane each, and dried under reduced pressure to give 28.1 g of a reddish brown solid. .
유기 다공질 중합체 담체 중에 함유되어 있는 촉매 성분의 조성은 하기와 같았다:The composition of the catalyst component contained in the organic porous polymer carrier was as follows:
Mg0.9Ti(OR)1.9Cl2.2(ED)0.4 Mg 0.9 Ti (OR) 1.9 Cl 2.2 (ED) 0.4
[(C) 중합][(C) polymerization]
촉매 성분으로서 상기 고체 촉매 4.2mg을 사용함을 제외하고는, 실시예 1(D)와 동일한 방법으로 중합을 수행한다.The polymerization was carried out in the same manner as in Example 1 (D), except that 4.2 mg of the solid catalyst was used as the catalyst component.
결과로서 중합체 64.0g이 수득되었다. 촉매 활성은 실시예 1 보다 훨씬 낮은 270,000g 중합체/g 티탄 원자이었다.As a result, 64.0 g of a polymer was obtained. The catalytic activity was 270,000 g polymer / g titanium atom, much lower than Example 1.
[비교예 3]Comparative Example 3
[(A) 고체 촉매 성분의 합성][(A) Synthesis of Solid Catalyst Component]
용량 100ml의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 실시예 1(B)에서 수득한 고체 생성물 8.3g, 톨루엔 45ml, 부틸 에테르 0.2.ml(1,2mmol) 및 사염화 티탄 2.5ml(22.7mmol)를 플라스크에 충전시키고 95℃에서 3시간 반응시킨다. 반응 후, 고체 물질을 95℃에서 액체로부터 분리시키고, 각각 톨루엔 50ml로 상기 온도에서 2회 세척하며, 추가로 각각 헥산 50ml로 2회 세척하고, 감압하에서 건조시켜 갈색의 고체 촉매 성분 8.5g을 수득하였다.After replacing the internal atmosphere of a 100 ml flask with argon gas, 8.3 g of solid product obtained in Example 1 (B), 45 ml of toluene, 0.2.ml (1,2 mmol) butyl ether and 2.5 ml (22.7 mmol) titanium tetrachloride ) Is charged to the flask and reacted at 95 ° C for 3 hours. After the reaction, the solid material was separated from the liquid at 95 ° C., washed twice at this temperature with 50 ml of toluene each, further washed twice with 50 ml of hexane each and dried under reduced pressure to give 8.5 g of a brown solid catalyst component. It was.
유기 다공질 중합체 담체 중에 함유되어 있는 촉매 성분의 조성은 하기와 같았다:The composition of the catalyst component contained in the organic porous polymer carrier was as follows:
Mg3.6Ti(OR)1.0Cl9.9(ED)0 Mg 3.6 Ti (OR) 1.0 Cl 9.9 (ED) 0
[(B) 중합][(B) polymerization]
상기 고체 촉매 5.7mg을 촉매 성분으로서 사용함을 제외하고는, 실시예 1(D)와 동일한 방법으로 중합을 수행한다. 결과로서, 중합체 103g이 수득되었다.The polymerization was carried out in the same manner as in Example 1 (D), except that 5.7 mg of the solid catalyst was used as the catalyst component. As a result, 103 g of polymer was obtained.
오트클레이브의 내벽 및 교반기 상에 중합체의 부착이 관찰되었다. 촉매 활성은 450,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.918, 이의 MI는 1.72g/10분, 이의 MFR은 33.1 및 이의 벌크 밀도는 0.41g/cm3이었다. 이의 CXS는 15.9%이었다.Adhesion of the polymer was observed on the inner wall of the oatclave and on the stirrer. The catalytic activity was 450,000 g polymer / g titanium atom. The polymer had a density of 0.918, its MI of 1.72 g / 10 min, its MFR of 33.1 and its bulk density of 0.41 g / cm 3 . Its CXS was 15.9%.
실시예 1에서 수득한 중합체와 비교하여 이 중합체는 분자량 분포가 더 넓으며, 저 분자량 생성물의 양이 더 많았다.Compared with the polymer obtained in Example 1, this polymer has a broader molecular weight distribution and a higher amount of low molecular weight product.
[비교예 4][Comparative Example 4]
[(A) 고체 생성물의 합성][(A) Synthesis of Solid Product]
교반기 및 적하 깔대기를 장착한 용적 300ml의 플라스크의 분위기를 아르곤 가스로 대체시킨 후, 헵탄 200ml, 테트라 부톡시티탄 2.5g(7.4mmol) 및 테트라에톡시실란 26.0g(125mmol)을 플라스크에 충전시킨다. 이들을 균일 용액이 되게 하고, 실온에서 30분간 교반시킨다.After replacing the atmosphere of a 300 ml volumetric flask equipped with a stirrer and a dropping funnel with argon gas, 200 ml of heptane, 2.5 g (7.4 mmol) of tetra butoxytitanium and 26.0 g (125 mmol) of tetraethoxysilane were charged to the flask. These are brought into a homogeneous solution and stirred for 30 minutes at room temperature.
이어서, 실시예 1(A)에서 합성한 유기 마그네슘 화합물 66.7ml를 플라스크의 내부 온도를 5℃로 유지하면서 1시간에 걸쳐 적하 깔대기로부터 서서히 적하시킨다. 적하 후, 생성되는 혼합물을 실온에서 1시간 교반시킨다. 고체 물질을 액체로부터 분리시키고, 각각 헵탄 200ml로 3회 세정하며, 감압하에서 건조시켜 갈색 고체 생성물 21.5g을 수득하였다.Subsequently, 66.7 ml of the organic magnesium compound synthesized in Example 1 (A) was slowly added dropwise from the dropping funnel over 1 hour while maintaining the internal temperature of the flask at 5 ° C. After the dropwise addition, the resulting mixture is stirred at room temperature for 1 hour. The solid material was separated from the liquid, washed three times with 200 ml each of heptane and dried under reduced pressure to give 21.5 g of a brown solid product.
[(B) 고체 촉매 성분의 합성][B Synthesis of Solid Catalyst Component]
용적 200ml의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 환원 반응(A)에서 합성한 고체 생성물 13.8g, 톨루엔 69ml 및 디이소부틸 프탈레이트 10.1ml(37.7mmol)를 플라스크 중에 충전시키고, 95℃에서 1시간 반응시킨다.After replacing the internal atmosphere of the volume 200 ml flask with argon gas, 13.8 g of solid product synthesized in the reduction reaction (A), 69 ml of toluene and 10.1 ml (37.7 mmol) of diisobutyl phthalate were charged into the flask and at 95 ° C. React for 1 hour.
반응 후, 고체 물질을 액체로부터 분리시키고, 각각 톨루엔 69ml로 2회 세정한다.After the reaction, the solid material is separated from the liquid and washed twice with 69 ml of toluene each.
세정 후, 톨루엔 69ml, 부틸 에테르 1.0ml(6mmol) 및 사염화 티탄 13.6ml(124mmol)를 가하고, 95℃에서 3시간 반응시킨다. 반응 종료 후, 고체 물질을 95℃에서 액체로부터 분리시키고, 이 온도에서 각각 툴루엔 69ml로 2회 세정하고, 추가로 각각 n-헵탄 69ml로 2회 세정하며, 감압하에서 건조시켜 갈색의 고체 촉매 성분 10.4g을 수득하였다.After washing, 69 ml of toluene, 1.0 ml (6 mmol) of butyl ether, and 13.6 ml (124 mmol) of titanium tetrachloride were added and reacted at 95 ° C for 3 hours. After completion of the reaction, the solid material was separated from the liquid at 95 ° C., washed twice with 69 ml of toluene each at this temperature, further washed twice with 69 ml of n-heptane each, and dried under reduced pressure to give a brown solid catalyst component 10.4 g were obtained.
[(C) 중합][(C) polymerization]
상기한 고체 촉매를 사용하여, 실시예 1(D)와 동일한 방법으로 중합을 수행한다.Using the solid catalyst described above, polymerization was carried out in the same manner as in Example 1 (D).
이 시험에서 고체 촉매 성분은 다공질 중합체 담체 중에 함침되지 않기 때문에, 생성물의 입자 특성은 양호하지 못하다. 오트클레이브를 열고, 그의 내부를 검사하니 중합체 입자의 일부가 교반기 등에 부착되어 있었다. 또한 생성물은 입도 125㎛ 이하의 미세 중합체 1.5 중량 %를 함유하였다.Since the solid catalyst component is not impregnated in the porous polymer carrier in this test, the particle properties of the product are poor. When the oatclave was opened and its interior was inspected, some of the polymer particles were attached to the stirrer or the like. The product also contained 1.5% by weight of a fine polymer having a particle size of 125 μm or less.
[실시예 2]Example 2
[(A) 고체 촉매 성분의 예비 중합][(A) Prepolymerization of Solid Catalyst Components]
교반기를 장착한 용적 1ℓ의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 실시예 1(C)에서 수득한 고체 촉매 성분 3.8g, 부탄 500ml 및 트리에틸 알루미늄 2.5mmol을 플라스크 중에 충전시킨다. 이어서, 압력이 1kg/cm2게이지가 될 때까지 수소가스를 도입한다. 이어서, 6g/g 고체 촉매-시간의 비로 에틸렌을 공급하면서, 반응을 3시간 계속시킨다. 반응 종료 후, 부탄을 퍼지시키고, 예비 중합 촉매 72.2g을 수득하였다. 이 촉매는 270ppm의 티탄 원자를 함유하였다.After replacing the internal atmosphere of a 1 L flask equipped with a stirrer with argon gas, 3.8 g of solid catalyst component obtained in Example 1 (C), 500 ml butane and 2.5 mmol of triethyl aluminum were charged into the flask. Subsequently, hydrogen gas is introduced until the pressure becomes 1 kg / cm 2 gauge. The reaction is then continued for 3 hours while feeding ethylene at a ratio of 6 g / g solid catalyst-hours. After the reaction was completed, butane was purged to give 72.2 g of a prepolymerization catalyst. This catalyst contained 270 ppm of titanium atoms.
[(B) 중합][(B) polymerization]
상기 유동상형 기상 중합조에서 제조한 고체 촉매 성분을 사용하여, 에틸렌과 부텐-1의 랜덤 공중합을 수행한다.Random copolymerization of ethylene and butene-1 is carried out using the solid catalyst component prepared in the fluidized bed gas phase polymerization tank.
중합조를 85℃까지 가열한 후, 미리 감압하에서 건조시킨 고밀도 폴리에틸렌 분말 300g을 분산제로서 가한 후, 상기 제조한 고체 촉매 성분 0.22g 및 트리에틸 알루미늄 5.34g을 소량의 헥산 압력을 적용하면서 상기조 중으로 충전시킨다. 에틸렌/부텐-1/수소의 몰비가 69/24/7이 되도록 제조한 에틸렌, 부텐-1 및 수소로 이루어진 가스상 혼합물을 9 내지 9.5kg/cm2G의 압력에서 중합조 중에서 측정한 것으로서 0.3m/초의 유속으로 순환시킨다. 에틸렌/부텐-1/수소의 비가 소정 값을 벗어날 경우, 필요 성분이 추가로 가해져서 몰비가 조절된다. 이러한 조건하에서, 유동상 기상 공중합을 2시간 수행하여 중합조 중의 중합체 높이/중합조 직경비(ℓ/d)가 2 내지 4의 값을 유지케 한다. 중합 종료 후, 생성 중합체의 양에 비교되는 중합체의 양을 상기 반응조로부터 회수하고, 반응 중에 잔류하는 중합체를 다음 중합용 분산제로서 사용한다. 상기 절차를 6회 반복하여, 중합체 중에 초기에 공급되는 고밀도 폴리에틸렌 분말의 비율은 무시할 수 있을 정도로 작게 되었다.After heating the polymerization tank to 85 ° C., 300 g of the high-density polyethylene powder previously dried under reduced pressure was added as a dispersant, and then 0.22 g of the solid catalyst component prepared above and 5.34 g of triethyl aluminum were applied to the tank while applying a small amount of hexane pressure. Charge it. 0.3 m as measured in a polymerization tank of a gaseous mixture of ethylene, butene-1 and hydrogen prepared so that the molar ratio of ethylene / butene-1 / hydrogen is 69/24/7 at a pressure of 9 to 9.5 kg / cm 2 G Circulate at a flow rate of / sec. When the ratio of ethylene / butene-1 / hydrogen deviates from a predetermined value, the necessary component is further added to control the molar ratio. Under these conditions, the fluid phase gas phase copolymerization is carried out for 2 hours so that the polymer height / polymerization tank diameter ratio (l / d) in the polymerization tank is maintained at a value of 2 to 4. After completion of the polymerization, the amount of the polymer compared with the amount of the produced polymer is recovered from the reaction tank, and the polymer remaining in the reaction is used as a dispersant for the next polymerization. By repeating the above procedure six times, the proportion of the high density polyethylene powder initially fed into the polymer was negligibly small.
중합 종료 후, 중합체를 회수하고, 이로부터 촉매 활성을 측정하였다. 결과로서, 촉매 활성은 1,540,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.921, 이의 MI는 1.15g/10분, 이의 MFR은 27.0, 이의 벌크 밀도는 0.46g/cm3, 및 이의 CXS는 6.2%이었다. 실시예 1과 유사하게, 생성 중합체의 입자 특성은 양호하였으며, 반응조 벽에의 부착은 거의 관측되지 않았다.After the completion of the polymerization, the polymer was recovered, and the catalytic activity was measured therefrom. As a result, the catalytic activity was 1,540,000 g polymer / g titanium atom. The polymer had a density of 0.921, its MI of 1.15 g / 10 min, its MFR of 27.0, its bulk density of 0.46 g / cm 3 , and its CXS of 6.2%. Similar to Example 1, the particle properties of the resulting polymer were good and little adhesion to the reactor walls was observed.
[실시예 3]Example 3
[(A) 고체 촉매 성분의 합성][(A) Synthesis of Solid Catalyst Component]
용적 100ml의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, 실시예 1(B)의 환원 반응에서 합성한 고체 생성물 8.2g, 톨루엔 27.3ml 및 디이소부틸 프탈레이트 1.2ml(4.3mmol)를 플라스크 중에 충전시키고, 95℃에서 30분간 반응시킨다.After replacing the internal atmosphere of the volume 100 ml flask with argon gas, 8.2 g of solid product synthesized in the reduction reaction of Example 1 (B), 27.3 ml of toluene and 1.2 ml (4.3 mmol) of diisobutyl phthalate were charged into the flask. And reacted at 95 ° C for 30 minutes.
반응 종료 후, 고체 물질을 액체로부터 분리시키고, 각각 톨루엔 40ml로 2회 세정한다.After completion of the reaction, the solid material is separated from the liquid and washed twice with 40 ml of toluene each.
세정 후, 톨루엔 40ml, 디이소부틸 프탈레이트 0.1ml(0.4mmol), 부틸 에테르 0.3ml(1.8mmol) 및 사염화 티탄 4.9ml(45mmol)를 플라스크에 가하고, 95℃에서 3시간 반응시킨다. 반응 종료 후, 고체 물질을 95℃에서 액체로부터 분리시키고, 이 온도에서 각각 툴루엔 50ml로 2회 세정한다.After washing, 40 ml of toluene, 0.1 ml (0.4 mmol) of diisobutyl phthalate, 0.3 ml (1.8 mmol) of butyl ether and 4.9 ml (45 mmol) of titanium tetrachloride were added to the flask and allowed to react at 95 ° C for 3 hours. After completion of the reaction, the solid material is separated from the liquid at 95 ° C. and washed twice with 50 ml of toluene each at this temperature.
또한 이를 각각 헥산 50ml로 2회 세정하고, 감압하에서 건조시켜 갈색의 고체 촉매 성분 8.0g을 수득하였다.It was also washed twice with 50 ml each of hexane and dried under reduced pressure to give 8.0 g of a brown solid catalyst component.
유기 다공질 중합체 중에 함유되어 있는 촉매 성분의 조성은 하기와 같았다:The composition of the catalyst component contained in the organic porous polymer was as follows:
Mg17.7Ti(OR)1.7Cl26.7(ED)1.7 Mg 17.7 Ti (OR) 1.7 Cl 26.7 (ED) 1.7
[(B) 고체 촉매 성분의 예비 중합][(B) Prepolymerization of Solid Catalyst Components]
교반기를 장착한 용적 1ℓ의 플라스크의 내부 분위기를 아르곤 가스로 대체시킨 후, (A)에서 수득한 고체 촉매 성분 3.8g, 부탄 500ml, 트리에틸 알루미늄 2.5mmol 및 이소-부틸트리에톡시실란 0.38mmol을 충전한다.After replacing the internal atmosphere of a 1 L flask equipped with a stirrer with argon gas, 3.8 g of the solid catalyst component obtained in (A), 500 ml of butane, 2.5 mmol of triethyl aluminum and 0.38 mmol of iso-butyltriethoxysilane were added. To charge.
프로필렌을 6g/g 고체 촉매-시간의 비로 계속 공급하면서 반응을 4시간 계속시킨다. 반응 종료 후, 부탄을 퍼지시키고, 예비 종합 촉매 72.3g을 수득하였다. 이는 티탄 원자 262ppm을 포함하였다.The reaction is continued for 4 hours while propylene is continuously supplied at a 6 g / g solid catalyst-hour ratio. After the reaction was completed, butane was purged to give 72.3 g of a preliminary comprehensive catalyst. It contained 262 ppm of titanium atoms.
[(C) 중합][(C) polymerization]
에틸렌/부텐-1/수소의 몰비를 65/23/12로 변경시킴을 제외하고는, 상기 제조한 고체 촉매 성분을 사용하여 실시예 2(B)와 동일한 방법으로 중합을 수행한다.The polymerization was carried out in the same manner as in Example 2 (B), except that the molar ratio of ethylene / butene-1 / hydrogen was changed to 65/23/12.
촉매 활성은 720,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.920, 이의 MI는 0.71g/10분, 이의 MFR은 26.8, 이의 벌크 밀도는 0.45g/cm3및 이의 CXS는 8.1%이었다.The catalytic activity was 720,000 g polymer / g titanium atom. The polymer had a density of 0.920, its MI of 0.71 g / 10 min, its MFR of 26.8, its bulk density of 0.45 g / cm 3 and its CXS of 8.1%.
실시예 1과 유사하게, 생성되는 중합체의 입자 특성은 양호하였으며, 반응조 벽에의 부착은 거의 관측되지 않았다.Similar to Example 1, the resulting polymer had good particle properties and little adhesion to the reactor walls was observed.
[비교예 5][Comparative Example 5]
[(A) 고체 촉매 성분의 합성][(A) Synthesis of Solid Catalyst Component]
용적 100ml의 플라스크의 내부 분위기를 아르곤 가스로 대체한 후, 실시예 1(B)의 환원 반응에서 합성한 고체 생성물 6.1g, 톨루엔 30ml, 디이소부틸 프탈레이트 0.7ml(2.5mmol), 부틸 에테르 2.6ml(15.4mmol) 및 사염화 티탄 33.6ml(333mmol)를 플라스크 중에 충전시키고, 95℃에서 3시간 반응시킨다.After replacing the internal atmosphere of the volume 100 ml flask with argon gas, 6.1 g of the solid product synthesized in the reduction reaction of Example 1 (B), 30 ml of toluene, 0.7 ml (2.5 mmol) of diisobutyl phthalate, 2.6 ml of butyl ether (15.4 mmol) and 33.6 ml (333 mmol) of titanium tetrachloride were charged into the flask and allowed to react at 95 ° C for 3 hours.
반응 종료 후, 고체 물질을 95℃에서 액체로부터 분리시키고, 이 온도에서 각각 톨루엔 50ml로 2회 세정한다.After completion of the reaction, the solid material is separated from the liquid at 95 ° C. and washed twice with 50 ml of toluene each at this temperature.
또한, 이를 각각 헥산 50ml로 2회 세정하고, 감압하에서 건조시켜 갈색의 고체 촉매 성분 6.2g을 수득하였다.Furthermore, it was washed twice with 50 ml each of hexane and dried under reduced pressure to give 6.2 g of a brown solid catalyst component.
유기 다공질 중합체 담체 중에 함유되어 있는 촉매 성분의 조성은 하기와 같았다:The composition of the catalyst component contained in the organic porous polymer carrier was as follows:
Mg7.9Ti(OR)0.2Cl19.3(ED)2.7 Mg 7.9 Ti (OR) 0.2 Cl 19.3 (ED) 2.7
[(B) 고체 촉매 성분의 예비 중합][(B) Prepolymerization of Solid Catalyst Components]
(A)에서 수득한 촉매 3.2g을 사용함을 제외하고는, 실시예 3(B)와 동일한 방법으로 프로필렌의 예비 중합을 수행한다. 결과로서, 예비 중합 촉매 57.6g이 수득되었다. 이는 티탄 원자 830ppm을 함유하였다.The prepolymerization of propylene is carried out in the same manner as in Example 3 (B), except that 3.2 g of the catalyst obtained in (A) is used. As a result, 57.6 g of prepolymer catalyst were obtained. It contained 830 ppm titanium atom.
[(C) 중합][(C) polymerization]
상기 제조한 고체 촉매 성분을 사용함을 제외하고는 실시예 3(C)와 동일한 방법으로 중합을 수행한다.The polymerization was carried out in the same manner as in Example 3 (C), except that the solid catalyst component prepared above was used.
촉매 활성은 230,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.920, 이의 MI는 0.77g/10분, 이의 MFR은 30, 이의 벌크 밀도는 0.43g/cm3및 이의 CXS는 9.1%이었다.The catalytic activity was 230,000 g polymer / g titanium atom. The polymer had a density of 0.920, its MI of 0.77 g / 10 min, its MFR of 30, its bulk density of 0.43 g / cm 3 and its CXS of 9.1%.
이 촉매는 촉매 활성에서 실시예 3의 것보다 더 낮았다.This catalyst was lower in catalyst activity than that of Example 3.
[실시예 4]Example 4
가스 혼합물의 조성(에틸렌/부텐-1/수소의 몰비)이 75/18/7임을 제외하고는, 실시예 2(B)와 동일한 방법으로 중합을 수행한다.The polymerization was carried out in the same manner as in Example 2 (B) except that the composition of the gas mixture (molar ratio of ethylene / butene-1 / hydrogen) was 75/18/7.
촉매 활성은 780,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.927, 이의 MI는 2.21g/10분, 이의 MFR은 27.1, 이의 벌크 밀도는 0.45g/cm3및 이의 CXS는 3.7%이었다.The catalytic activity was 780,000 g polymer / g titanium atom. The polymer had a density of 0.927, its MI of 2.21 g / 10 min, its MFR of 27.1, its bulk density of 0.45 g / cm 3 and its CXS of 3.7%.
이렇게 수득한 중합체의 입자 특성은 양호하고, 분자량 분포는 협소하며, 저 분자량 성분의 함량은 적었다.The particle characteristics of the polymer thus obtained were good, the molecular weight distribution was narrow, and the content of the low molecular weight component was small.
[실시예 5]Example 5
가스상 혼합물이 60/34/6의 조성(에틸렌/부텐-1/수소의 몰비)을 가짐을 제외하고는, 실시예 2(B)와 동일한 방법으로 중합을 수행한다.The polymerization is carried out in the same manner as in Example 2 (B), except that the gaseous mixture has a composition of 60/34/6 (molar ratio of ethylene / butene-1 / hydrogen).
촉매 활성은 620,000g 중합체/g 티탄 원자이었다. 이 중합체의 밀도는 0.911, 이의 MI는 1.20g/10분, 이의 MFR은 27.5 및 이의 벌크 밀도는 0.42g/cm3이었다.The catalytic activity was 620,000 g polymer / g titanium atom. The polymer had a density of 0.911, its MI of 1.20 g / 10 minutes, its MFR of 27.5 and its bulk density of 0.42 g / cm 3 .
이것이 초 저밀도 중합체일지라도, 이의 입자 특성은 양호하였으며, 분자량 분포도 협소하였다.Although this is an ultra low density polymer, its particle properties were good and the molecular weight distribution was narrow.
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| JP1-115672 | 1989-05-08 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087820A1 (en) * | 2004-03-11 | 2005-09-22 | Sk Corporation | Method for preparing ethylene polymerization catalysts |
| WO2006004296A1 (en) * | 2004-07-01 | 2006-01-12 | Samsung Total Petrochemicals Co., Ltd. | Method of polymerization of olefin and olefin/ alpha-olefin using aryloxy-based olefin- (co)polymerization catalyst |
| KR20140054202A (en) * | 2011-08-25 | 2014-05-08 | 도호 티타늄 가부시키가이샤 | Method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
-
1990
- 1990-05-08 SG SG1996000165A patent/SG44400A1/en unknown
- 1990-05-08 KR KR1019900006484A patent/KR0169718B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005087820A1 (en) * | 2004-03-11 | 2005-09-22 | Sk Corporation | Method for preparing ethylene polymerization catalysts |
| WO2006004296A1 (en) * | 2004-07-01 | 2006-01-12 | Samsung Total Petrochemicals Co., Ltd. | Method of polymerization of olefin and olefin/ alpha-olefin using aryloxy-based olefin- (co)polymerization catalyst |
| KR20140054202A (en) * | 2011-08-25 | 2014-05-08 | 도호 티타늄 가부시키가이샤 | Method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
| US10364304B2 (en) | 2011-08-25 | 2019-07-30 | Toho Titanium Co., Ltd. | Method for producing solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
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| KR900018150A (en) | 1990-12-20 |
| SG44400A1 (en) | 1997-12-19 |
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