KR970015606A - 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법 - Google Patents
폴리올레핀 중합용 메탈로센 담지촉매의 제조방법 Download PDFInfo
- Publication number
- KR970015606A KR970015606A KR1019950028603A KR19950028603A KR970015606A KR 970015606 A KR970015606 A KR 970015606A KR 1019950028603 A KR1019950028603 A KR 1019950028603A KR 19950028603 A KR19950028603 A KR 19950028603A KR 970015606 A KR970015606 A KR 970015606A
- Authority
- KR
- South Korea
- Prior art keywords
- bis
- cyclopentadienyl
- dimethyl
- inorganic carrier
- metallocene
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract 14
- 238000000034 method Methods 0.000 title claims abstract 12
- 229920000098 polyolefin Polymers 0.000 title abstract 6
- 238000006116 polymerization reaction Methods 0.000 title abstract 5
- 150000001875 compounds Chemical class 0.000 claims abstract 16
- -1 polyethylene Polymers 0.000 claims abstract 10
- 239000003960 organic solvent Substances 0.000 claims abstract 9
- 239000011148 porous material Substances 0.000 claims abstract 7
- 238000004519 manufacturing process Methods 0.000 claims abstract 6
- 239000011261 inert gas Substances 0.000 claims abstract 3
- 229910052751 metal Inorganic materials 0.000 claims abstract 2
- 239000002184 metal Substances 0.000 claims abstract 2
- 239000002808 molecular sieve Substances 0.000 claims 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 6
- 239000010457 zeolite Substances 0.000 claims 6
- 229910021536 Zeolite Inorganic materials 0.000 claims 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 5
- 229910052782 aluminium Inorganic materials 0.000 claims 4
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- IZYHZMFAUFITLK-UHFFFAOYSA-N 1-ethenyl-2,4-difluorobenzene Chemical compound FC1=CC=C(C=C)C(F)=C1 IZYHZMFAUFITLK-UHFFFAOYSA-N 0.000 claims 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 238000009835 boiling Methods 0.000 claims 2
- QOXHZZQZTIGPEV-UHFFFAOYSA-K cyclopenta-1,3-diene;titanium(4+);trichloride Chemical compound Cl[Ti+](Cl)Cl.C=1C=C[CH-]C=1 QOXHZZQZTIGPEV-UHFFFAOYSA-K 0.000 claims 2
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 claims 2
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- ZBFBXTFQCKIUHU-UHFFFAOYSA-L 1,2,3,5,5-pentamethylcyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].CC1=[C-]C(C)(C)C(C)=C1C.CC1=[C-]C(C)(C)C(C)=C1C ZBFBXTFQCKIUHU-UHFFFAOYSA-L 0.000 claims 1
- WCGXJPFHTHQNJL-UHFFFAOYSA-N 1-[5-ethyl-2-hydroxy-4-[6-methyl-6-(2H-tetrazol-5-yl)heptoxy]phenyl]ethanone Chemical compound CCC1=CC(C(C)=O)=C(O)C=C1OCCCCCC(C)(C)C1=NNN=N1 WCGXJPFHTHQNJL-UHFFFAOYSA-N 0.000 claims 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims 1
- PNZJHMTVFFXLAX-UHFFFAOYSA-N C1=CC2=CC=CC=C2C1[Hf]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound C1=CC2=CC=CC=C2C1[Hf]([SiH](C)C)C1C2=CC=CC=C2C=C1 PNZJHMTVFFXLAX-UHFFFAOYSA-N 0.000 claims 1
- XJTQEAXBIXXILJ-UHFFFAOYSA-L CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 Chemical compound CC(C)=[Zr](Cl)(Cl)(C1C=CC=C1)C1=CC=CC2=C1CC1=CC=CC=C21 XJTQEAXBIXXILJ-UHFFFAOYSA-L 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- BKPOJAOURAWSTR-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 BKPOJAOURAWSTR-UHFFFAOYSA-L 0.000 claims 1
- FJMJPZLXUXRLLD-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Zr+2]([SiH](C)C)C1C2=CC=CC=C2C=C1 FJMJPZLXUXRLLD-UHFFFAOYSA-L 0.000 claims 1
- GHNLLKNVWYRCCG-UHFFFAOYSA-L [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Hf+2]C1C2=CC=CC=C2C=C1 GHNLLKNVWYRCCG-UHFFFAOYSA-L 0.000 claims 1
- WAMLIEMGVVKCMU-UHFFFAOYSA-L [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 WAMLIEMGVVKCMU-UHFFFAOYSA-L 0.000 claims 1
- QSZGOMRHQRFORD-UHFFFAOYSA-L [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C=C.C1=CC2=CC=CC=C2C1[Zr+2]C1C2=CC=CC=C2C=C1 QSZGOMRHQRFORD-UHFFFAOYSA-L 0.000 claims 1
- XRMLSJOTMSZVND-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++]C1(C)C=CC=C1C Chemical compound [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++]C1(C)C=CC=C1C XRMLSJOTMSZVND-UHFFFAOYSA-L 0.000 claims 1
- SRDOMKALHPEHIJ-UHFFFAOYSA-L [Cl-].[Cl-].C[SiH](C)[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 Chemical compound [Cl-].[Cl-].C[SiH](C)[Zr+2](C1=CC=CC=2C3=CC=CC=C3CC1=2)C1C=CC=C1 SRDOMKALHPEHIJ-UHFFFAOYSA-L 0.000 claims 1
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- ZHFFGBNOSGNGDM-UHFFFAOYSA-N carbanide hafnium(4+) inden-3a-id-1-yl-inden-1-id-1-yl-dimethylsilane Chemical group [CH3-].[CH3-].[Hf+4].C[Si](C)([c-]1ccc2ccccc12)[c-]1ccc2ccccc12 ZHFFGBNOSGNGDM-UHFFFAOYSA-N 0.000 claims 1
- KDKNVCQXFIBDBD-UHFFFAOYSA-N carbanide;1,2,3,4,5-pentamethylcyclopentane;zirconium(2+) Chemical group [CH3-].[CH3-].[Zr+2].C[C]1[C](C)[C](C)[C](C)[C]1C.C[C]1[C](C)[C](C)[C](C)[C]1C KDKNVCQXFIBDBD-UHFFFAOYSA-N 0.000 claims 1
- 229940125904 compound 1 Drugs 0.000 claims 1
- JAGHDVYKBYUAFD-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C1C=CC=[C-]1.C1C=CC=[C-]1 JAGHDVYKBYUAFD-UHFFFAOYSA-L 0.000 claims 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 1
- MIILMDFFARLWKZ-UHFFFAOYSA-L dichlorozirconium;1,2,3,4,5-pentamethylcyclopentane Chemical compound [Cl-].[Cl-].CC1=C(C)C(C)=C(C)C1(C)[Zr+2]C1(C)C(C)=C(C)C(C)=C1C MIILMDFFARLWKZ-UHFFFAOYSA-L 0.000 claims 1
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 claims 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000012968 metallocene catalyst Substances 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000329 molecular dynamics simulation Methods 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 238000004381 surface treatment Methods 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract 3
- 150000001336 alkenes Chemical class 0.000 abstract 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000000704 physical effect Effects 0.000 abstract 1
- 229920000573 polyethylene Polymers 0.000 abstract 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- 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
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- 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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- 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
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- 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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- 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
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명은 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법에 관한 것이다. 좀 더 구체적으로, 본 발명은 고활성을 지녀 올레핀의 중합반응시 조촉매의 사용량을 대폭적으로 감소시킬 수 있으며 폴리올레핀 고분자의 물성을 개선할 수 있는 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법에 관한 것이다. 본 발명의 메탈로센 담지촉매 제조방법은 불활성가스 분위기하에서 7 내지 100Å의 결정성 기공을 지닌 무기담체에 유기용매 및 유기 알루미늄 화합물을 가하고 일정한 온도에서 반응시켜 무기담체를 표면처리하고 건조시키는 공정; 및 전기 공정에서 수득한 표면처리된 무기담체에 유기용매와 전기한 무기담체의 기공직경보다 분자의 동력학적 직경이 큰 메탈로센 화합물을 가하고 일정한 온도에서 반응시켜 메탈로센 화합물을 담지시키고 건조시키는 공정을 포함한다. 본 발명에 의해 높은 촉매활성을 지녀 폴리에틸렌을 고수율로 제조할 수 있고, 올레핀의 중합반응시 조촉매의 사용량을 대폭적으로 감소시킬 수 있으며, 입자 형상 등 고분자의 제반물성이 개선된 폴리올레핀을 제조할 수 있는 동시에, 생성된 고분자 내의 금속등의 잔류량을 대폭적으로 감소시킴으로써, 경제적으로 고품질의 폴리올레핀을 제조할 수 있는 메탈로센 담지촉매를 얻을 수 있다.
Description
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Claims (12)
- (ⅰ) 불활성가스 분위기하에서 7 내지 100Å의 결정성 기공을 지닌 무기담체에 유기용매 및 유기 알루미늄 화합물을 가하고 일정한 온도에서 반응시켜 무기담체를 표면처리하고 건조시키는 공정; 및 (ⅱ) 전기 공정에서 수득한 표면처리된 무기담체에 유기용매와 전기한 무기담체의 기공직경보다 분자의 동력학적 직경이 큰 메탈로센 화합물을 가하고 일정한 온도에서 반응시켜 메탈로센 화합물을 담지시키고 건조시키는 공정을 포함하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 무기담체로는 7 내지 15Å의 미세기공을 지닌 제올라이트 또는 15 내지 100Å의 기공을 지닌 중간기공형 분자체를 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제2항에 있어서, 제올라이트로는 린데형 엑스, 린데형 와이, 사포-37, 씨에스지-3, 엘지-210의 포자사이트계 제올라이트; 브이피아이-5; 알코-8엠; 클로버라이트; 및, 카코제나이트로 구성된 그룹으로부터 선택된 1종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제2항에 있어서, 중간기공형 분자체로는 엠시엠-41, 엠시엠-48, 엠시엠-22, 엠시엠-49, 엠시엠-56 및 엠시엠-56의 엠41에스계 분자체; 사포계 분자체; 및, 엠이아포계 분자체로 구성된 그룹으로부터 선택된 1종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 유기 알루미늄 화합물로는 메틸 알루미녹산; 에틸 알루미녹산; 알킬 알루미늄; 및, 일반식 A1RiXj(이때, R은 알킬기를 나타내고, X는 할로겐 원소를 나타내며, i+j=3이다)로 표시되는 할로알킬 알루미늄으로 구성된 그룹으로부터 선택된 1종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제2항에 있어서, 무기담체가 포자사이트계 제올라이트일 때, 메탈로센 화합물로는 비스(시클로펜타디에닐)지르코늄 디클로라이드, 비스(시클로펜타디에닐)지르코늄 디메틸, 비스(시클로펜타디에닐)티타늄 디클로라이드, 비스(시클로펜타디에닐)티타늄 디메틸, 비스(시클로펜타디에닐)하프늄 디클로라이드, 비스(시클로펜타디에닐)하프늄 디메틸, 시클로펜타디에닐티타늄 트리클로라이드 및 시클로펜타디에닐티타늄 트리메틸로 구성된 그룹으로부터 선택된 1종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제2항에 있어서, 무기담체가 브이피아이-5계 제올라이트 및 중간기공형 분자체일 때, 메탈로센 화합물로는 비스(시클로펜타디에닐)지르코늄 디클로라이드, 비스(시클로펜타디에닐)지르코늄 디메틸, 비스(시클로펜타디에닐)티타늄 디클로라이드, 비스(시클로펜타디에닐)티타늄 디메틸, 비스(시클로펜타디에닐)하프늄 디클로라이드, 비스(시클로펜타디에닐)하프늄 디메틸, 시클로펜타디에닐티타늄 트리클로라이드, 시클로펜타디에닐티타늄 트리메틸, 에틸렌 비스(인데닐)지르코늄 디클로라이드, 에틸렌 비스(인데닐)지르코늄 디메틸, 디메틸실릴 비스(인데닐)지르코늄 디클로라이드, 디메틸실릴 비스(인데닐)지르코늄 디메틸, 디메틸실릴 비스(인데닐)티타늄 디클로라이드, 디메틸실릴 비스(인데닐)티타늄 디메틸, 디메틸실릴 비스(인데닐)하프늄 디클로라이드, 디메틸실릴 비스(인데닐)하프늄 디메틸, 에틸렌 비스(인데닐)티타늄 디클로라이드, 에틸렌 비스(인테닐)티타늄 디메틸, 에틸렌 비스(인데닐)하프늄 디클로라이드, 에틸렌 비스(인데닐)하프늄 디메틸, 비스(펜타메틸 시클로펜타디에닐)지르코늄 디클로라이드, 비스(펜타메틸 시클로펜타디에닐)지르코늄 디메틸, 비스(펜타메틸 시클로펜타디에닐)티타늄 디클로라이드, 비스(펜타메틸 시클로펜타디에닐)티타늄 디메틸, 비스(펜타메틸 시클로펜타디에닐)하프늄 디클로라이드, 비스(펜타메틸 시클로펜타디에닐)하프늄 디메틸, 비스(인데닐)지르코늄 디클로라이드, 비스(인데닐)지르코늄 디메틸, 비스(디메틸시클로펜타디에닐)지르코늄 디클로라이드, 비스(디메틸시클로펜타디에닐)지르코늄 디메틸, 이소프로필리덴(시클로펜타디에닐)(플루오레닐)지르코늄 디클로라이드, 이소프로필리덴(시클로펜타디에닐)(플루오레닐)지그코늄 디메틸, 디메틸실릴(시클로펜타디에닐)(플루오레닐)지르코늄 디클로라이드, 디메틸실릴(시콜로펜타디에닐)(플루오레닐)지르코늄 디메틸, (t-부틸아미노)디메틸(테트라메틸-η5-시클로펜타디에닐)실란티타늄 디메틸, (t-부틸아미노)디메틸(테트라메틸-η5-시클로펜타디에닐)실란지르코늄 디클로라이드 및 (t-부틸아미노)디메틸(테트라메틸-η5-시클로펜타디에닐)실란지르코늄 디메틸로 구성된 그룹으로부터 선택된 1종 이상을 사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 유기용매는 톨루엔, 헥산, 헵탄, 옥탄 및 크실렌을 단독사용하거나 전기한 유기용매를 1종 이상 혼합사용하는 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 무기담체의 표면처리시 반응온도는 0℃ 내지 유기용매의 끓는점인 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 메탈로센 화합물의 담지시 반응온도는 20℃ 내지 유기용매의 끓는점이며, 반응시간은 0.5 내지 72시간인 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 제1항에 있어서, 무기담체와 메탈로센 화합물 및 알루미늄 화합물의 첨가량은 중량비로 무기담체: 메탈로센 화합물의 촉매금속: 알루미늄 화합물의 알루미늄이 1 내지 0.001:1 내지 0.001:1인 것을 특징으로 하는 메탈로센 담지촉매의 제조방법.
- 불활성가스 분위기하에서 7 내지 100Å의 결정성 기공을 지닌 무기담체에 유기용매 및 유기 알루미늄 화합물을 가하고 일정한 온도에서 반응시켜 무기담체를 표면처리하고 건조시킨 다음, 표면처리된 무기담체에 유기용매와 전기한 무기담체의 기공직경보다 분자의 동력학적 직경이 큰 메탈로센 화합물을 가하고 일정한 온도에서 반응시켜 메탈로센 화합물을 담지시키고 건조시키고 건조시켜 제조된 메탈로센 담지촉매.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019950028603A KR970015606A (ko) | 1995-09-01 | 1995-09-01 | 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법 |
| US08/697,978 US5869417A (en) | 1995-09-01 | 1996-09-03 | Process for preparing metallocene catalyst for polyolefin polymerization |
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| KR1019950028603A KR970015606A (ko) | 1995-09-01 | 1995-09-01 | 폴리올레핀 중합용 메탈로센 담지촉매의 제조방법 |
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| DE19745905A1 (de) * | 1997-10-17 | 1999-04-22 | Hoechst Ag | Trägerkatalysatoren mit hoher Sinterstabilität und Verfahren zu deren Herstellung |
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| CN100587962C (zh) * | 2003-07-03 | 2010-02-03 | 泰塞拉技术匈牙利公司 | 用于封装集成电路器件的方法和设备 |
| CN100537614C (zh) * | 2006-01-16 | 2009-09-09 | 中国石油化工股份有限公司 | 原位合成负载型非茂金属聚乙烯催化剂的方法 |
| WO2008101691A1 (en) * | 2007-02-22 | 2008-08-28 | Saudi Basic Industries Corporation | A supported catalyst for the preparation of (co)polymers ethylenically unsaturated monomers |
| CN101255204B (zh) * | 2007-02-28 | 2010-05-19 | 中国石油化工股份有限公司 | 一种负载型非茂金属烯烃聚合催化剂的制备方法 |
| US8299188B2 (en) * | 2007-05-18 | 2012-10-30 | Fina Technology, Inc. | Supported metallocene catalysts |
| BRPI0815807B1 (pt) * | 2007-08-29 | 2021-05-11 | W.R.Grace & Co.-Conn | composição de ativadores de catalisador de aluminoxanos derivados dos agentes precursores do cátion dialquilalumínio, processos para fazer os mesmos, e sua utilização em catalisadores e polimerização de olefinas. |
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| SG186271A1 (en) * | 2010-08-20 | 2013-01-30 | Exxonnmobil Chemical Patents Inc | Process for producing cycloalkylaromatic compounds |
| US8759597B2 (en) | 2012-04-18 | 2014-06-24 | Uop Llc | Methods for producing zeolite catalysts and methods for producing alkylated aromatic compounds using the zeolite catalysts |
| CN115073629B (zh) * | 2021-03-15 | 2023-09-26 | 中国石油天然气股份有限公司 | 负载型茂金属催化剂体系及其制备方法与应用 |
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1995
- 1995-09-01 KR KR1019950028603A patent/KR970015606A/ko not_active Application Discontinuation
-
1996
- 1996-09-03 US US08/697,978 patent/US5869417A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5869417A (en) | 1999-02-09 |
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