KR101126918B1 - 폴리올레핀 중합용 촉매의 제조방법, 이에 따른 촉매 및 이를 이용한 폴리올레핀의 제조방법 - Google Patents
폴리올레핀 중합용 촉매의 제조방법, 이에 따른 촉매 및 이를 이용한 폴리올레핀의 제조방법 Download PDFInfo
- Publication number
- KR101126918B1 KR101126918B1 KR1020090132240A KR20090132240A KR101126918B1 KR 101126918 B1 KR101126918 B1 KR 101126918B1 KR 1020090132240 A KR1020090132240 A KR 1020090132240A KR 20090132240 A KR20090132240 A KR 20090132240A KR 101126918 B1 KR101126918 B1 KR 101126918B1
- Authority
- KR
- South Korea
- Prior art keywords
- catalyst
- magnesium
- compound
- weight
- magnesium halide
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 102
- 239000011777 magnesium Substances 0.000 claims abstract description 102
- -1 magnesium halide Chemical class 0.000 claims abstract description 89
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 35
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 33
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 150000004820 halides Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000011147 magnesium chloride Nutrition 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000010960 commercial process Methods 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N hydroxymethyl benzene Natural products OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 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 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- LNQAEJCFMOFVCH-UHFFFAOYSA-N 2-ethylperoxycarbonylbenzoic acid Chemical compound O(CC)OC(C=1C(C(=O)O)=CC=CC1)=O LNQAEJCFMOFVCH-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NFOQRIXSEYVCJP-UHFFFAOYSA-N 2-propoxycarbonylbenzoic acid Chemical compound CCCOC(=O)C1=CC=CC=C1C(O)=O NFOQRIXSEYVCJP-UHFFFAOYSA-N 0.000 description 1
- FJZBADSJNSFVDO-UHFFFAOYSA-N 3,3-bis(methoxymethyl)-2,4-dimethylpentane Chemical compound COCC(C(C)C)(C(C)C)COC FJZBADSJNSFVDO-UHFFFAOYSA-N 0.000 description 1
- PVWCLOAAEFMTLH-UHFFFAOYSA-N 4,4-bis(methoxymethyl)-2,6-dimethylheptane Chemical compound COCC(COC)(CC(C)C)CC(C)C PVWCLOAAEFMTLH-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- BZCJJERBERAQKQ-UHFFFAOYSA-N diethyl(dipropoxy)silane Chemical compound CCCO[Si](CC)(CC)OCCC BZCJJERBERAQKQ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- JVUVKQDVTIIMOD-UHFFFAOYSA-N dimethoxy(dipropyl)silane Chemical compound CCC[Si](OC)(OC)CCC JVUVKQDVTIIMOD-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 description 1
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-M phenylacetate Chemical compound [O-]C(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-M 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- MQHNKCZKNAJROC-UHFFFAOYSA-N phthalic acid dipropyl ester Natural products CCCOC(=O)C1=CC=CC=C1C(=O)OCCC MQHNKCZKNAJROC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 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
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
실시예1 | 실시예2 | 실시예3 | 실시예4 | 비교예1 | 비교예2 | 비교예3 | |
중합활성 (kg-PP/g-cat,hr) |
39.1 | 42.8 | 40.1 | 40.8 | 32.2 | 34.9 | 23.8 |
겉보기 밀도 (g/mL) | 0.50 | 0.50 | 0.47 | 0.48 | 0.40 | 0.42 | 0.36 |
입체규칙성(XIS) | 98.2 | 98.3 | 97.9 | 98.0 | 97.7 | 97.5 | 96.2 |
Claims (12)
- a) 마그네슘 할라이드를 하기 화학식 2로 표시되는 알코올(a)과 탄소수 6 ~ 20인 지방족 탄화수소(b)에 용해시킨 후 하기 화학식 1로 표시되는 알콕시실란 화합물을 첨가하여 알콕시실란 화합물이 함유된 마그네슘 할라이드 전구체 용액을 제조하는 단계;b) 할로겐 분자, 알킬 할라이드 화합물, 아실 할라이드 화합물 및 금속 할라이드 화합물 중에서 선택된 할로겐 화합물의 존재 하에, 금속 마그네슘과 하기 화학식 3으로 표시되는 알코올(c)을 반응시켜 디알콕시마그네슘 담체를 제조하는 단계;c) 상기 알콕시실란 화합물이 함유된 마그네슘 할라이드 전구체 용액 및 상기 디알콕시마그네슘 담체를, 탄소수 6 ~ 12인 지방족 탄화수소 및 탄소수 6 ~ 12인 방향족 탄화수소 중에서 선택된 탄화수소의 존재하에 사염화티타늄과 반응시켜 고체 생성물을 형성하는 단계; 및d) 상기 고체 생성물을, 탄소수 6 ~ 12인 지방족 탄화수소 및 탄소수 6 ~ 12인 방향족 탄화수소 중에서 선택된 탄화수소의 존재하에 프탈레이트계 화합물, 카르복실산에스테르 화합물 및 다이에테르 화합물로 이루어진 군에서 선택된 내부전자공여체 및 사염화티타늄과 반응시키는 단계를 포함하는 폴리올레핀 중합용 촉매의 제조방법:[화학식 1]Si(OR1)nR2(4-n)(상기 화학식 1에서 R1 및 R2는 탄소수 1 ~ 5의 알킬기이고, n은 1 ~ 4의 자연수임);[화학식 2]ROH(상기 화학식 2에서, R은 탄소수 1 ~ 12의 지방족 탄화수소 또는 탄소수 6 ~ 12의 방향족 탄화수소임);[화학식 3]R'OH(상기 화학식 3에서, R'는 탄소수 1 ~ 6의 지방족 탄화수소 또는 탄소수 6의 방향족 탄화수소임).
- 삭제
- 제1항에 있어서,상기 a) 단계에서, 상기 알콕시실란 화합물이 함유된 마그네슘 할라이드 전구체 용액에 포함되는 상기 알콕시실란 화합물의 함유량은 상기 마그네슘 할라이드 1중량부에 대하여 0.1 ~ 10중량부인 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 c) 단계의 마그네슘 할라이드 전구체 용액에 포함되는 상기 마그네슘 할라이드의 함유량은 상기 디알콕시마그네슘 담체 1중량부에 대하여 0.01 ~ 5중량부인 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 제1항에 있어서,상기 a) 단계에서 상기 알콕시실란 화합물이 함유된 마그네슘 할라이드 전구체 용액에 포함되는 상기 알코올(a)의 함유량은 상기 마그네슘 할라이드 1중량부에 대하여 1 ~ 10중량부이며, 상기 탄화수소(b)의 함유량은 상기 마그네슘 할라이드 1중량부에 대하여 1 ~ 20중량부인 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 삭제
- 삭제
- 제1항에 있어서,상기 b) 단계는 상기 금속 마그네슘 1중량부에 대하여 상기 할로겐 화합물 0.01 ~ 10중량부와 상기 알코올(c) 5 ~ 50중량부를 사용하는 것을 특징으로 하는 폴리올레핀 중합용 촉매의 제조방법.
- 삭제
- 삭제
- 제1항, 제3항 내지 제5항 및 제8항 중 어느 한 항에 따른 제조방법에 의해 제조된 폴리올레핀 중합용 촉매.
- 제11항의 폴리올레핀 중합용 촉매를 사용하는 것을 특징으로 하는 폴리올레핀의 제조방법.
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KR1020090132240A KR101126918B1 (ko) | 2009-12-28 | 2009-12-28 | 폴리올레핀 중합용 촉매의 제조방법, 이에 따른 촉매 및 이를 이용한 폴리올레핀의 제조방법 |
CN201080059669.8A CN102741298B (zh) | 2009-12-28 | 2010-12-28 | 聚烯烃聚合用催化剂的制备方法、根据其的催化剂及利用其的聚烯烃的制备方法 |
US13/519,545 US20120289398A1 (en) | 2009-12-28 | 2010-12-28 | Preparation method of catalyst for polymerization of polyolefin, catalyst prepared thereby and preparation method of polyolefin using the catalyst |
EP10841237.0A EP2520592B8 (en) | 2009-12-28 | 2010-12-28 | Production method for a catalyst for polyolefin polymerisation, a catalyst obtained by means of the same, and a production method for polyolefins by using the same |
JP2012547014A JP5478736B2 (ja) | 2009-12-28 | 2010-12-28 | ポリオレフィン重合用触媒の製造方法及びこれにより製造される触媒、並びにこれを用いたポリオレフィンの製造方法 |
PCT/KR2010/009420 WO2011081405A2 (ko) | 2009-12-28 | 2010-12-28 | 폴리올레핀 중합용 촉매의 제조방법, 이에 따른 촉매 및 이를 이용한 폴리올레핀의 제조방법 |
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KR1020090132240A KR101126918B1 (ko) | 2009-12-28 | 2009-12-28 | 폴리올레핀 중합용 촉매의 제조방법, 이에 따른 촉매 및 이를 이용한 폴리올레핀의 제조방법 |
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KR20110075716A KR20110075716A (ko) | 2011-07-06 |
KR101126918B1 true KR101126918B1 (ko) | 2012-03-20 |
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US (1) | US20120289398A1 (ko) |
EP (1) | EP2520592B8 (ko) |
JP (1) | JP5478736B2 (ko) |
KR (1) | KR101126918B1 (ko) |
CN (1) | CN102741298B (ko) |
WO (1) | WO2011081405A2 (ko) |
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KR101373775B1 (ko) * | 2012-11-23 | 2014-03-13 | 롯데케미칼 주식회사 | 폴리올레핀 합성용 촉매의 제조방법 및 이를 이용한 폴리올레핀의 제조방법 |
JP6914095B2 (ja) * | 2017-05-01 | 2021-08-04 | 東邦チタニウム株式会社 | ジアルコキシマグネシウムの製造方法、オレフィン類重合用触媒成分の製造方法、オレフィン類重合用触媒の製造方法、及びオレフィン類重合体の製造方法 |
KR102327008B1 (ko) * | 2017-11-30 | 2021-11-16 | 롯데케미칼 주식회사 | 폴리에틸렌 접착제 |
KR102539409B1 (ko) * | 2021-01-25 | 2023-06-05 | 에쓰대시오일 주식회사 | 자일렌 용해도가 향상된 호모 폴리프로필렌 수지 조성물 및 그 제조방법 |
CN116041577A (zh) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | 烯烃聚合催化剂组分、催化剂体系及应用和烯烃聚合方法 |
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US5028671A (en) * | 1987-03-13 | 1991-07-02 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of olefins and polymerization catalyst |
KR20010033585A (ko) * | 1997-12-23 | 2001-04-25 | 보레알리스 테크놀로지 오와이. | 마그네슘, 티타늄, 할로겐 원소 및 전자 주게 물질을함유하는 촉매 성분 및 그의 제조 방법과 용도 |
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JPS5883006A (ja) * | 1981-11-13 | 1983-05-18 | Mitsui Petrochem Ind Ltd | オレフインの重合方法 |
JPH06104693B2 (ja) | 1986-01-06 | 1994-12-21 | 東邦チタニウム株式会社 | オレフイン類重合用触媒 |
US5108972A (en) * | 1989-10-16 | 1992-04-28 | Akzo Nv | Process of making halide/alkoxy-containing magnesium complex |
US6410663B2 (en) * | 1992-06-08 | 2002-06-25 | Fina Technology, Inc. | Electron donors in a Ziegler-Natta catalyst for the production of high melt flow copolymers |
US5459116A (en) * | 1993-05-07 | 1995-10-17 | Samsung General Chemicals Co., Ltd. | Highly active catalyst for the polymerization of olefins and method for the preparation of the same |
FI991069A0 (fi) * | 1999-05-10 | 1999-05-10 | Borealis As | Katalysaattorikomponentti, joka käsittää magnesiumia, titaania, halogeenia ja elektronidonorin, sen valmistus ja käyttö |
JP4170667B2 (ja) * | 2002-05-24 | 2008-10-22 | 出光興産株式会社 | マグネシウム化合物、オレフィン重合用固体触媒成分、オレフィン重合用触媒及びポリオレフィンの製造方法 |
KR100466511B1 (ko) * | 2003-10-23 | 2005-01-15 | (주) 디엔에프솔루션 | 폴리올레핀 제조용 고활성 실리카 담지 중합촉매의제조방법 및 그 제조방법에 의해 제조된 신규한 중합촉매 |
KR100640275B1 (ko) * | 2004-10-14 | 2006-11-01 | 대한유화공업 주식회사 | 에틸렌 중합 및/또는 에틸렌 공중합용 고체 촉매의 제조방법 |
KR20100007076A (ko) * | 2008-07-11 | 2010-01-22 | 삼성토탈 주식회사 | 올레핀 중합 촉매용 구형 담체의 크기를 조절하는 방법 |
-
2009
- 2009-12-28 KR KR1020090132240A patent/KR101126918B1/ko active IP Right Grant
-
2010
- 2010-12-28 EP EP10841237.0A patent/EP2520592B8/en active Active
- 2010-12-28 WO PCT/KR2010/009420 patent/WO2011081405A2/ko active Application Filing
- 2010-12-28 CN CN201080059669.8A patent/CN102741298B/zh active Active
- 2010-12-28 JP JP2012547014A patent/JP5478736B2/ja active Active
- 2010-12-28 US US13/519,545 patent/US20120289398A1/en not_active Abandoned
Patent Citations (2)
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US5028671A (en) * | 1987-03-13 | 1991-07-02 | Mitsui Petrochemical Industries, Ltd. | Process for polymerization of olefins and polymerization catalyst |
KR20010033585A (ko) * | 1997-12-23 | 2001-04-25 | 보레알리스 테크놀로지 오와이. | 마그네슘, 티타늄, 할로겐 원소 및 전자 주게 물질을함유하는 촉매 성분 및 그의 제조 방법과 용도 |
Also Published As
Publication number | Publication date |
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WO2011081405A2 (ko) | 2011-07-07 |
US20120289398A1 (en) | 2012-11-15 |
EP2520592B1 (en) | 2015-04-01 |
CN102741298A (zh) | 2012-10-17 |
WO2011081405A3 (ko) | 2011-11-10 |
JP2013515832A (ja) | 2013-05-09 |
KR20110075716A (ko) | 2011-07-06 |
EP2520592A4 (en) | 2013-10-09 |
CN102741298B (zh) | 2014-07-09 |
EP2520592B8 (en) | 2015-06-03 |
JP5478736B2 (ja) | 2014-04-23 |
EP2520592A2 (en) | 2012-11-07 |
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