CN107880163A - Catalytic component and its preparation and application for olefinic polymerization - Google Patents
Catalytic component and its preparation and application for olefinic polymerization Download PDFInfo
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- CN107880163A CN107880163A CN201610872786.5A CN201610872786A CN107880163A CN 107880163 A CN107880163 A CN 107880163A CN 201610872786 A CN201610872786 A CN 201610872786A CN 107880163 A CN107880163 A CN 107880163A
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- compound
- catalytic component
- logical formula
- catalyst
- alkyl
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000004793 Polystyrene Substances 0.000 claims abstract description 21
- 229920002223 polystyrene Polymers 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 21
- -1 hydroxyl class compound Chemical class 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 13
- 150000002901 organomagnesium compounds Chemical class 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 210000003746 feather Anatomy 0.000 claims abstract description 9
- 244000144992 flock Species 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000002002 slurry Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 31
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 229940091250 magnesium supplement Drugs 0.000 description 3
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- WVINUQQXXQBYSG-UHFFFAOYSA-N 4-chlorobutylboron Chemical compound [B]CCCCCl WVINUQQXXQBYSG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000271566 Aves Species 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VBGXZCWPDTXWMA-UHFFFAOYSA-N [B]OCCCl Chemical compound [B]OCCCl VBGXZCWPDTXWMA-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- SEANWWIVRHMMMF-UHFFFAOYSA-N butoxy(dichloro)borane Chemical compound CCCCOB(Cl)Cl SEANWWIVRHMMMF-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LNZBSVNIMBHSAG-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(methylamino)hexan-1-one Chemical compound CCCCC(NC)C(=O)c1ccc2OCOc2c1 LNZBSVNIMBHSAG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XHKIJCOQPXFXEO-UHFFFAOYSA-N 2,2-dichloroethylboron Chemical compound [B]CC(Cl)Cl XHKIJCOQPXFXEO-UHFFFAOYSA-N 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- RTAQCQOZRWKSTQ-UHFFFAOYSA-N CC(C)C[Mg]CC(C)C Chemical compound CC(C)C[Mg]CC(C)C RTAQCQOZRWKSTQ-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000010210 aluminium Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- UWJOGBWYZJHGOH-UHFFFAOYSA-N dichloromethylboron Chemical compound [B]C(Cl)Cl UWJOGBWYZJHGOH-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- ZXSSXAUYKUTLBP-UHFFFAOYSA-N hexane;trichloroborane Chemical compound ClB(Cl)Cl.CCCCCC ZXSSXAUYKUTLBP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- KMYFNYFIPIGQQZ-UHFFFAOYSA-N magnesium;octane Chemical compound [Mg+2].CCCCCCC[CH2-].CCCCCCC[CH2-] KMYFNYFIPIGQQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 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 1
- PVSCLHDHWOAWGV-UHFFFAOYSA-N oxygen;toluene Chemical compound [O].CC1=CC=CC=C1 PVSCLHDHWOAWGV-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000047 product 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
- 230000003362 replicative effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F110/02—Ethene
-
- 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
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
- C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
-
- 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
- C08F4/658—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657
- C08F4/6585—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657 and aluminium or compounds thereof
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)
- Emergency Medicine (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to a kind of catalytic component for olefinic polymerization, and it is the reaction product for including at least one organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl class compound, at least one chloride organoboron compound and at least one additive；Wherein, the additive is that polystyrene block PEO is birdsed of the same feather flock together compound.Catalytic component provided by the invention, not only its catalytic activity is high, the hydrogen response of catalyst is good, resulting polymers bulk densities are high, and corresponding catalyst also has good particle shape and distribution, so as to be more beneficial for use of the catalyst on the polymerization technique device such as gas phase, slurry.
Description
Technical field
The invention belongs to catalytic component and its preparing technical field, and in particular to a kind of catalyst for olefinic polymerization
Component and its preparation and application.
Background technology
From after Efficient polyolefin catalyst development success the 1970s, there occurs great change for world's polyolefin industry.Closely
Over more than 20 years, with the development of olefin polymetiation process, the catalyst to match with polymerization technique has also got significant progress, its
Middle effective catalyst still occupies by its excellent polymerization and ripe application technology in polyolefin catalyst field
Consequence.By exploratory development for many years, the preparation method of Mg-Ti systems effective catalyst is also by being co-mulled and made into method, suspending and soak
Stain method develops into chemical reaction method.
In chemical reaction method, many prior arts are related to using organic metal magnesium compound, chlorinating agent and transition metal
The chemical raw materials such as titanium compound, a variety of different types of catalyst are prepared with this kind of reactant.In such Mg-Ti
In catalyst, have one it is fatal the shortcomings that be unmanageable forming step, so as to unmanageable prepared catalyst particle
Form.Recent development is in the dispersion that catalyst precarsor includes magnesium titanium compound, adds some similar to emulsifying agent
Material, it is allowed to form emulsion, then reaction precipitation goes out catalyst granules again, can so improve the granulated of gained catalyst
State.But these method forming steps are complicated, it is difficult to control, gained catalyst granules form is not easy to control, and is used
Material price it is high, it is difficult to obtain.
, will for preparing higher performance although having done substantial amounts of research work in Ziegler-Natta catalyst field
The Ziegler-Natta catalyst asked, it is still desirable to some new or improved methods.Therefore, the problem of presently, there are is to be badly in need of
Research and develop that a kind of preparation method is simple, and particle shape is preferable, and the catalyst with higher catalytic activity and hydrogen response.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned the deficiencies in the prior art, there is provided one kind is used for olefinic polymerization
Catalytic component and its preparation and application.The present inventor is in catalyst component for olefin polymerization and its preparation and application skill
Art field has carried out experimental study extensively and profoundly, sends out in the preparation process for the catalytic component for being currently used for olefinic polymerization and uses
Additive polystyrene block PEO is birdsed of the same feather flock together compound, and not only the particle of corresponding catalyst component is more uniform, and it is to alkene
The control of the particle size and form of polymerized hydrocarbon product can be more preferable, and the catalytic activity and hydrogen response of corresponding catalyst
It is high.
Therefore, first aspect present invention provides a kind of catalytic component for olefinic polymerization, it is to include at least one
Kind organo-magnesium compound, at least one titanium-containing compound, at least one hydroxyl class compound, at least one chloride organoboration
The reaction product of compound and at least one additive；
Wherein, the chloride organoboron compound is logical formula (IV) BR4 qCl3-qShown compound, in logical formula (IV),
R4For C2-C20Alkyl or alkoxy, 0≤q ＜ 3；
The additive is that polystyrene block PEO is birdsed of the same feather flock together compound.
According to the present invention, the organo-magnesium compound is logical formula (I) MgR1 nCl2-nShown compound, in logical formula (I),
R1For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl, 0 ＜ n≤2.It is preferred that
The organo-magnesium compound includes dibutylmagnesium, diisobutyl magnesium, dioctyl magnesium, fourth octyl group magnesium, ethyl-magnesium-chloride and chlorination fourth
One or more in base magnesium.
According to the present invention, the titanium-containing compound is logical formula (II) Ti (OR2)mCl4-mShown compound, in logical formula (II)
In, R2For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl, 0≤m≤4；Cause
Generally it is in a liquid state at normal temperatures for tetravalent titanium compound, and it is also fine with the compatibility of some solvents.It is preferred that described contain titanizing
Compound includes the one or more in titanium tetrachloride, tetraethyl titanate and butyl titanate, more preferably titanium tetrachloride.
According to the present invention, the hydroxyl class compound is logical formula (III) HOR3Shown compound, in logical formula (III)
In, R3For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or closed chain C3-C20Alkyl.It is preferred that described contain
Hydroxy kind compound includes fatty alcohol and/or aromatic alcohol；More preferably described hydroxyl class compound include n-butanol, n-hexyl alcohol,
One or more in isooctanol, phenmethylol and benzyl carbinol.
According to the present invention, the chloride organoboron compound include dichloromethyl boron, Dichloroethyl boron, two chlorobutyl boron,
At least one of dichloro methoxyl group boron, two chloroethoxy boron, boron chloride and dichloro butoxy boron, preferably two chlorobutyl boron,
At least one of dichloro methoxyl group boron, two chloroethoxy boron, boron chloride and dichloro butoxy boron.
According to the present invention, the additive polystyrene block PEO (PS-b-POE) birds of the same feather flock together compound include it is two embedding
Section and three block and its derivative；It is preferred that the polystyrene block PEO is birdsed of the same feather flock together, the block type of compound is optionally line
Shape, band branch chain or star form.The content of polystyrene is in the polystyrene block PEO birdss of the same feather flock together compound
5wt%-95wt%, preferably 10wt%-90wt%.
Second aspect of the present invention provides a kind of preparation method of catalytic component as described in the first aspect of the invention, and it is wrapped
Include：
Step A, organo-magnesium compound and hydroxyl class compound are reacted, obtain clear solution；
Step B, additive is dispersed in C4-C20Alkane or C6-C20Aromatic solvent in, formed solution, then with step A
Obtained clear solution reaction, obtains mixed liquor；
Step C, chloride organoboron compound and titanium-containing compound are added sequentially in the mixed liquor that step B is obtained, obtained
To catalytic component suspension, reclaim solid particle therein and obtain the catalytic component.
According to the inventive method, in terms of every mole of organo-magnesium compound, the titanium-containing compound is 0.01-10 moles, institute
Hydroxyl class compound is stated as 0.1-20 moles, the chloride organoboron compound is 0.1-50 moles, and the additive is anti-
It is 0.001-100 grams/L to answer the concentration in system.It is preferred that the titanium-containing compound is 0.05-5 moles, the hydroxyl class chemical combination
Thing is 0.2-10 moles, and the chloride organoboron compound is 0.5-20 moles, concentration of the additive in reaction system
For 0.01-50 grams/L.
According to the inventive method, in step, the reaction temperature of organo-magnesium compound and hydroxyl class compound is typically selected
Select and carry out at a higher temperature advantageously, preferably below the boiling temperature of reactant, temperature is normally no higher than 90 DEG C, and one
As be not higher than 70 DEG C.Reaction time depend on reactant property and operating condition, required time typically at 5 minutes to 2 hours,
It is preferred that 10 minutes to 1 hour.After organo-magnesium compound and the reaction of hydroxyl class compound, the solution of formation can be dilute with inertia
Release agent to be used in mixed way, inert diluent is generally selected from aliphatic hydrocarbon or aromatic hydrocarbon atent solvent, such as iso-butane, penta
Alkane, hexane, heptane, hexamethylene, benzene,toluene,xylene and its mixture, general hexane, heptane or toluene are proper
Atent solvent.
According to the inventive method, in stepb, additive is dispersed in C4-C20Alkane or aromatic solvent in, preferably divide
It is dispersed in hexane, heptane or toluene and its admixture solvent, forms solution, then is sufficiently mixed with the obtained clear solutions of step A,
Obtain mixed liquor.According to the species of additive and property difference, its C4-C20Alkane or arene solution configuration concentration control be
0.1-100 g/l, preferably 1-50 g/l, the amount of addition is so that concentration of the additive in reaction system is 0.001-100
G/l, preferably 0.01-50 g/l.Mixing temperature will typically be less than the boiling temperature of system, for convenience, be typically chosen
Between 0-90 DEG C, preferably between 10-50 DEG C.Both incorporation times are typically chosen 0.5 minute to 5 hours, preferably 10 points
Clock was to 1 hour.
According to the inventive method, in step C, the uniform mixing of all substances is quickly completed at a certain temperature, first
The solution system that first two steps are obtained is reduced to certain temperature, and solution still keeps clear at such a temperature, is unlikely to
Existing muddy or precipitation, temperature can be controlled between -90 to 30 DEG C, preferably between -70 to 0 DEG C, then by chloride organic boron
Compound and titanium-containing compound are progressively slowly added to successively, are generally sufficiently stirred in favor of various materials during charging
Be sufficiently mixed, charging rate generally selects that substantially heating is defined not cause significant reaction or system., can be with after being sufficiently mixed
Heated up using any of suitable method, such as slowly, progressively, rapidly or temperature programming, different temperature-rising methods can
To obtain the totally different catalyst of performance characteristics.In temperature-rise period, system can be changed into muddiness by clarification, precipitation be separated out, at this
In precipitation reaction step, the reaction time of settling step should be long enough to obtain complete precipitation, and the reaction time can last 1 point
Clock was to 10 hours, preferably 3 minutes to 5 hours.
Experiment is found, after settling step, a period of time of reaction at a certain temperature carries out maturation process to catalyst
Particle shape than advantageous, it can improve the intensity of catalyst particle, be broken so as to reduce the particle of catalyst in the course of the polymerization process
Broken phenomenon.The final temperature of the temperature of maturation process generally greater than or equal to precipitation reaction, the time of slaking reaction can control
In 0.5-10 hours, preferably 1-5 hours.
After maturation process is carried out, typically to be washed, to remove shape in excessive reactant and preparation process
Into accessory substance, any atent solvent is used equally for this washing step, such as can select iso-butane, pentane, hexane, heptan
Alkane, hexamethylene, toluene or various aromatic hydrocarbons and its mixture etc., are generally selected after washing twice with toluene, then use hexane in experiment
Fully washing.After washing, it is dried under the protection of catalyst suspension nitrogen, to obtain catalyst fines.
Third aspect present invention provides a kind of catalyst for alkene homopolymerization or combined polymerization, and it is included such as the present invention
Catalytic component or the catalytic component of method preparation, and at least one as described in respect of the second aspect of the invention described in first aspect
Logical formula (V) AlR5 hX3-hShown organo-aluminum compound, in logical formula (V), R5For C that is identical or differing1-C8Alkyl, X is
Halogen, 1≤h≤3.It is preferred that the organo-aluminum compound includes triethyl aluminum (AlEt3), triisobutyl aluminium (Al (iso-Bu)3)、
Tri-n-hexyl aluminum (Al (n-C6H13)3), tri-n-octylaluminium (Al (n-C8H17)3) and diethylaluminum chloride (AlEt2Cl one kind in)
It is or a variety of.
Catalyst of the present invention can make according to the well-known way of this area olefinic polymerization Ziegler-Natta catalyst
With, such as it is used together with another co-catalyst or electron donor, can also be neat by the catalyst of the present invention and one or more
Ge Le-Natta catalyst or non-Ziegler-Natta catalyst are used in mixed way.
Fourth aspect present invention provides a kind of catalytic component as described in the first aspect of the invention, such as present invention second
Catalytic component prepared by aspect methods described or the catalyst as described in third aspect present invention are in alkene homopolymerization or copolymerization
Close the application in reaction.
Catalytic component and catalyst of the present invention are applied to the various any alkene that can carry out coordination poly-merization
Hydrocarbon, including a kind of homopolymerization of alkene or the combined polymerization of a variety of alkene.It is preferred that the alkene include the α such as ethene, propylene, butylene-
Alkene, or the mixture of ethene, propylene, butylene and one or more alpha-olefins.Preferable comonomer is C4-C10Alkene, such as
1- butylene, isobutene, 1- amylenes, 1- hexenes, 1- heptene, 1- octenes, 1- nonenes, 1- decene and 4-methyl-1-pentene, diene is such as
Butadiene, Isosorbide-5-Nitrae-hexadiene and 1,7- octadiene, cyclenes such as ENB, and their any mixture.
Catalyst of the present invention can be gathered in one or more polymer reactors using typical polymerization technology
Reaction is closed, can be gas phase, slurry or bulk polymerization, polymerisation can be intermittently or serially polymerization process.
To slurry or bulk reaction device, reaction temperature is typically at 40-130 DEG C, preferably 60-110 DEG C；Reactor pressure one
As in 0.2-8MPa, preferably 1-6MPa；Residence time is typically in 0.2-6 hours, preferably 0.5-3 hours.It is typically chosen boiling
Point uses in the aliphatic hydrocarbon of -70 to 100 DEG C of scopes as diluent；If desired, polymerisation can be at supercritical conditions
Carry out.
For Gas-phase reactor, reaction temperature is typically at 60-130 DEG C, preferably 70-110 DEG C；Reactor pressure typically exists
0.5-4MPa, preferably 1-3MPa；Residence time is typically in 0.5-10 hours, preferably 1-8 hours.If desired, selection is closed
Suitable aliphatic hydrocarbon is used as diluent, and polymerisation can be carried out under the conditions of frozen state.
Catalyst amount is generally dependent on property, type of reactor and the operating condition of catalyst and to polymerizate
The requirement of energy, can use conventional catalyst dosage.
Catalyst of the present invention has higher catalytic activity and preferable hydrogen response, polymerizate form energy
Enough particle shapes for preferably replicating catalyst, i.e., so-called " print effect ", therefore the catalyst have excellent comprehensive
Energy.
Embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment, these embodiments are only
Serve illustrative, it is not limited to application of the invention.
The method of testing used in the present invention is as follows：
(1) size distribution of carrier and catalyst uses MASTERSIZE particles distribution instruments, and n-hexane is surveyed as dispersant
It is 0.02-2000 μm to measure scope.
(2) relative weight percents of metal (mainly titanium, magnesium) use plasma emission spectrum in catalyst system
(ICP) measure.
(3) melt index (MI2.16) determined using ASTM-D 1238.
(4) bulk density (BD) is determined using DIN-53194.
Embodiment
Embodiment 1
The preparation of catalytic component：Take successively 30mL toluene, 3.15mL dibutylmagnesium hexane solution (1M) and 1.0mL
Isooctanol, 50 DEG C of maintenance stirring reaction half an hour are warming up to, obtain clear solution, then add polystyrene diblock polycyclic oxygen
Toluene solution (10g/L) 3mL of ethane copolymer A (polystyrene content 42wt%), is cooled to -50 DEG C, sequentially adds
The toluene solution (1M) and 0.35mL titanium tetrachlorides of 3.15mL boron chlorides, after maintaining low-temp reaction half an hour, slowly rise naturally
Temperature, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours.Catalyst suspension temperature is down to room temperature, stood, sedimentation, uses first
Benzene washs three times, and the dosage of each toluene is 50mL, dry that brown solid mobility powder is catalyst group after the completion of washing
Point, its average grain diameter is measured as 26.5 μm.Elementary analysis (ICP)：Ti:8.55wt%, Mg:18.89wt%.
Vinyl polymerization is evaluated：1L hexanes, 1mmol triethyl aluminums and a certain amount of catalytic component are added to 2L stainless steels
In stirred tank, temperature is then brought up to 85 DEG C, the disposable hydrogen for adding 0.18MPa, then with ethene by the stagnation pressure of system
Power maintains 1.03MPa and carries out polymerisation, after reacting 2 hours, stops adding ethene, cooling, pressure release, polyethylene powder claims
Weight, calculates the activity of catalyst, tests the bulk density of polyethylene powder and the melt index under 2.16Kg loads, as a result see
Table 1.
Embodiment 2
The preparation method of catalytic component is with embodiment 1, and difference is, by catalytic component preparation process
0.35mL titanium tetrachlorides are changed to 1mL titanium tetrachlorides.Its average grain diameter is measured as 29.6 μm.Elementary analysis (ICP)：Ti:
11.72wt%, Mg:22.47wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Embodiment 3
The preparation method of catalytic component is with embodiment 1, and difference is, by catalytic component preparation process
1.0mL isooctanol is changed to 0.6mL n-butanols, and by polystyrene block polyethylene oxide copolymer A, (polystyrene content is
Toluene solution (10g/L) 3mL 42wt%) is changed to polystyrene diblock polyethylene oxide copolymer A, and (polystyrene content is
Toluene solution (10g/L) 10mL 42wt%).Its average grain diameter is measured as 15.6 μm.Elementary analysis (ICP)：Ti:
9.39wt%, Mg:20.18wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 1
With embodiment 1, difference is the preparation method of catalytic component, is added without in catalytic component preparation process
" polystyrene diblock polyethylene oxide copolymer A (polystyrene content 42wt%) toluene solution ".It is average to measure it
Particle diameter is 68.53 μm, and size distribution is very wide, with the presence of multiple peaks.Elementary analysis (ICP)：Ti:10.26wt%, Mg:
14.18wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Comparative example 2
The preparation of catalytic component：Take 30mL hexanes, 3.15mL dibutylmagnesium hexane solution (1M) and 1.0mL different successively
Octanol, 50 DEG C of maintenance stirring reaction half an hour are warming up to, obtain clear solution, then add Kraton FG1901 hexane solutions
(10g/L) 3ml, is cooled to -50 DEG C, sequentially adds 3.15 milliliters of boron chloride hexane solution (1M) and the chlorinations of 0.35ml tetra-
Titanium, after maintaining low-temp reaction half an hour, slowly heating naturally, after being warmed to room temperature, heating maintains 50 DEG C to react 2 hours.Will catalysis
Agent suspension temperature is down to room temperature, stands, and sedimentation, is washed three times with hexane, and the dosage of each hexane is 50 milliliters, and washing is completed
Afterwards, it is dry that brown solid mobility powder, its average grain diameter are 17.4 μm.Elementary analysis (ICP)：Ti:10.62wt%, Mg:
14.73wt%.
For the ethene slurry polymerization evaluation method of catalyst with embodiment 1, polymerization result is shown in Table 1.
Table 1
The experimental data of embodiment and comparative example can be seen that from table 1 uses in the preparation process of catalytic component
Polystyrene block PEO is birdsed of the same feather flock together compound additive, and obtained catalyst and the particle shape of polymer is good, and ethene gathers
It is high to close activity, the bulk density of polymer resin is higher, catalyst high comprehensive performance.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of catalytic component for olefinic polymerization, it is to include at least one organo-magnesium compound, at least one titaniferous
The reaction of compound, at least one hydroxyl class compound, at least one chloride organoboron compound and at least one additive
Product；Wherein, the additive is that polystyrene block PEO is birdsed of the same feather flock together compound.
2. catalytic component according to claim 1, it is characterised in that the organo-magnesium compound is logical formula (I)
MgR1 nCl2-nShown compound, in logical formula (I), R1For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or
The C of closed chain3-C20Alkyl, 0 ＜ n≤2.
3. the catalytic component according to claim 1, it is characterised in that the titanium-containing compound is logical formula (II) Ti
(OR2)mCl4-mShown compound, in logical formula (II), R2For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl
Or the C of closed chain3-C20Alkyl, 0≤m≤4.
4. catalytic component according to claim 1, it is characterised in that the hydroxyl class compound is logical formula (III)
HOR3Shown compound, in logical formula (III), R3For saturation or the C of undersaturated straight chain or side chain2-C20Alkyl or ring
The C of shape chain3-C20Alkyl.
5. catalytic component according to claim 1, it is characterised in that the chloride organoboron compound is logical formula (IV)
BR4 qCl3-qShown compound, in logical formula (IV), R4For C2-C20Alkyl or alkoxy, 0≤q ＜ 3.
6. according to the catalytic component described in any one in claim 1-5, it is characterised in that the polystyrene block gathers
Ethylene oxide polymer includes diblock and three block and its derivative；It is preferred that the polystyrene block PEO class
The block type of polymer is optionally linear, band branch chain or star form；The polystyrene block PEO is birdsed of the same feather flock together
The content of polystyrene is 5wt%-95wt%, preferably 10wt%-90wt% in compound.
7. the preparation method of catalytic component as described in any one in a kind of 1-6 such as claim, it includes：
Step A, organo-magnesium compound and hydroxyl class compound are reacted, obtain clear solution；
Step B, additive is dispersed in C4-C20Alkane or C6-C20Aromatic solvent in, form solution, then obtained with step A
Clear solution reaction, obtain mixed liquor；
Step C, chloride organoboron compound and titanium-containing compound are added sequentially in the mixed liquor that step B is obtained, urged
Agent ingredients suspension liquid, reclaim solid particle therein and obtain the catalytic component.
8. preparation method according to claim 7, it is characterised in that in terms of every mole of organo-magnesium compound, the titaniferous
Compound is 0.01-10 moles, and the hydroxyl class compound is 0.1-20 moles, and the chloride organoboron compound is 0.1-
50 moles, concentration of the additive in reaction system is 0.001-100 grams/L；It is preferred that the titanium-containing compound is 0.05-5
Mole, the hydroxyl class compound is 0.2-10 moles, and the chloride organoboron compound is 0.5-20 moles, the addition
Concentration of the agent in reaction system is 0.01-50 grams/L.
9. a kind of catalyst for alkene homopolymerization or combined polymerization, it is included as described in any one in claim 1-6
Catalytic component or the catalytic component such as the preparation of the methods described of claim 7 or 8, and at least one logical formula (V) AlR5 hX3-hInstitute
The organo-aluminum compound shown, in logical formula (V), R5For C that is identical or differing1-C8Alkyl, X is halogen, 1≤h≤3.
10. prepared by the catalytic component, such as methods described of claim 7 or 8 in a kind of 1-6 such as claim as described in any one
The application in alkene homopolymerization or copolymerization of catalytic component or catalyst as claimed in claim 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR78845E (en) * | 1957-07-20 | 1962-09-14 | Normande De Matieres Plastique | Improvements to ethylene polymerization processes |
| KR20070065506A (en) * | 2005-12-20 | 2007-06-25 | 삼성토탈 주식회사 | Method for preparing a catalyst for producing polyolefin having a narrow molecular weight distribution |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
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2016
- 2016-09-30 CN CN201610872786.5A patent/CN107880163B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR78845E (en) * | 1957-07-20 | 1962-09-14 | Normande De Matieres Plastique | Improvements to ethylene polymerization processes |
| KR20070065506A (en) * | 2005-12-20 | 2007-06-25 | 삼성토탈 주식회사 | Method for preparing a catalyst for producing polyolefin having a narrow molecular weight distribution |
| CN102453169A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and preparation method thereof |
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