WO2015016423A1 - 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법 - Google Patents
메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법 Download PDFInfo
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- WO2015016423A1 WO2015016423A1 PCT/KR2013/009157 KR2013009157W WO2015016423A1 WO 2015016423 A1 WO2015016423 A1 WO 2015016423A1 KR 2013009157 W KR2013009157 W KR 2013009157W WO 2015016423 A1 WO2015016423 A1 WO 2015016423A1
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- WIPO (PCT)
- Prior art keywords
- group
- formula
- catalyst composition
- metallocene compound
- halogen
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 107
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 229920000642 polymer Polymers 0.000 claims description 38
- -1 triethylsilyl Chemical group 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 26
- 229910052736 halogen Inorganic materials 0.000 claims description 23
- 150000002367 halogens Chemical class 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
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- 125000000217 alkyl group Chemical group 0.000 claims description 12
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- 238000000034 method Methods 0.000 claims description 12
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- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
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- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
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- 125000003368 amide group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052732 germanium Chemical group 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 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 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
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- 125000001412 tetrahydropyranyl group Chemical group 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
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- 108010013554 leupin Proteins 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
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- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
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- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 claims description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 claims 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 1
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- 230000000694 effects Effects 0.000 abstract description 17
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- 230000009257 reactivity Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 84
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- 239000000243 solution Substances 0.000 description 27
- 239000003446 ligand Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 19
- 235000011089 carbon dioxide Nutrition 0.000 description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 16
- 239000005977 Ethylene Substances 0.000 description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
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- 229910007926 ZrCl Inorganic materials 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 11
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 11
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- 238000005481 NMR spectroscopy Methods 0.000 description 10
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- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
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- WFZSIVNWLIYDJZ-UHFFFAOYSA-N dichloro-methyl-[6-[(2-methylpropan-2-yl)oxy]hexyl]silane Chemical compound CC(C)(C)OCCCCCC[Si](C)(Cl)Cl WFZSIVNWLIYDJZ-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
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- C07F17/00—Metallocenes
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- 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
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- 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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- 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
- C08F4/65927—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 two cyclopentadienyl rings being mutually bridged
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- 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
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
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- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
Definitions
- Metallocene compound, catalyst composition comprising the same and method for producing olefin polymer using same
- the present invention relates to a novel metallocene compound, a catalyst composition comprising the same, and a method for preparing an olefinic polymer using the same.
- CGC Constrained-Geometry Catalyst
- US Pat. No. 5,064,802 The superiority of CGC in comparison to metallocene catalysts known to the prior art in the copolymerization of and alpha-olepin can be summarized into two main categories: (1) high molecular weight with high activity even at high polymerization temperature (2) the copolymerization of alpha-lelephine with high steric hindrance, such as 1-nuxene and 1-octene, is also very good. Efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively carried out in academia and industry.
- the Group 4 transition metal compound having one or two cyclopentadienyl groups as a ligand can be activated as methylaluminoxane or boron compound to be used as a catalyst for olepin polymerization.
- Such catalysts exhibit unique properties that conventional Ziegler-Natta catalysts cannot realize.
- the polymer obtained using such a catalyst has a narrow molecular weight distribution, has better reaction properties with respect to a second monomer such as an alpha olefin or a cyclic olefin, and the second monomer distribution of the polymer is also uniform.
- a second monomer such as an alpha olefin or a cyclic olefin
- the second monomer distribution of the polymer is also uniform.
- the substituent of the cyclopentadienyl ligand in the metallocene catalyst to the alpha olefin
- the stereoselectivity of the polymer can be controlled, and the degree of copolymerization, molecular weight, and distribution of the second monomer can be easily adjusted when copolymerizing ethylene and other olefins.
- bridged catalysts generally have good reactivity with the second monomer.
- the bridged catalysts studied so far can be classified into three types according to the type of the bridge.
- One is the reaction of two cyclopentadienyl ligands with alkylenedi by electrophiles such as alkyl halides and reaction with indene or fluorene.
- a bridged catalyst the second is a silicon bridged catalyst connected by -SiR 2-
- the third is a methylene bridged catalyst obtained from reaction of fulbene with indene, fluorene and the like.
- the present invention provides a metallocene compound having excellent activity and capable of producing a high molecular weight olefin-based polymer, a catalyst composition comprising the same, a method for producing an olefinic polymer using the same, and using the same. It is to provide a olefin-based polymer prepared by.
- a metallocene compound which exhibits high polymerization activity even when supported on a carrier, maintains high activity even in the presence of hydrogen, and can polymerize ultra high molecular weight olefin polymers, a catalyst composition comprising the same, It is to provide a method for producing an olefin polymer using the same and an olefin polymer prepared using the same.
- the present invention is a metallocene compound represented by the formula (1)
- A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group,
- C6 to C20 aryl group C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 alkoxyalkyl group, C3 to C20 heterocycloalkyl group, or C5 to C20 hetero Aryl group;
- D is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;
- L is a C1 to C10 straight or branched chain alkylene group
- B is carbon, silicon or germanium
- Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group;
- M is a Group 4 transition metal
- Xi and X 2 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, A C1 to C20 alkoxy group or a C1 to C20 sulfonate group;
- C 2 are the same as or different from each other, and are each independently represented by one of Formula 2a or Formula 2b:
- R to R 9 and I to R 9 ′ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, an alkenyl group of C2 to C20, and an alkyl of C1 to C20 Silyl group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group.
- the present invention also provides a catalyst composition comprising the metallocene compound.
- the present invention provides a method for producing an olefin-based polymer, comprising the step of polymerizing an olefinic monomer in the presence of the catalyst composition.
- the present invention provides an olefinic polymer prepared according to the above production method.
- the metallocene compound or the catalyst composition comprising the same according to the present invention can be used in the preparation of an olefin polymer, has excellent activity, and can produce a high molecular weight olepin polymer.
- the metallocene compound according to the present invention exhibits high polymerization activity even when supported on a carrier, and maintains high activity even in the presence of hydrogen due to low hydrogen reactivity, thereby allowing the polymerization of ultrahigh molecular weight olepin-based polymers.
- the catalyst has a long life time, so that the activity can be maintained even during a long residence time in the reaction vessel.
- first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
- each layer or element when each layer or element is referred to as being formed “on” or “on” of each layer or element, it means that each layer or element is formed directly on each layer or element, or It is meant that a layer or element can additionally be formed between each layer, on the object, the substrate.
- Metallocene compound according to the invention is characterized in that represented by the formula (1).
- A is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, a C3 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
- D is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to An alkyl group of C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20;
- L is a C1 to C10 straight or branched chain alkylene group
- B is carbon, silicon or germanium
- Q is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group,
- M is a Group 4 transition metal
- Xi and 3 ⁇ 4 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, C1 To C20 alkoxy group, or C1 to C20 sulfonate group;
- d and c 2 are the same as or different from each other, and are each independently represented by one of the following Formulas 2a or 2b:
- Ri to R 9 and R 9 ′ are the same as or different from each other, and each independently hydrogen, halogen, an alkyl group of C1 to C20, an alkenyl group of C2 to C20, and an alkylsilyl of C1 to C20 Group, C1 to C20 silylalkyl group, C1 to C20 alkoxysilyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group.
- the alkyl group of C1 to C20 includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nucleosil group, heptyl group, Octyl group etc. can be mentioned, It is not limited to this.
- the alkenyl group of C2 to C20 includes a straight or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.
- the aryl group of the C6 to C20 is a monocyclic or condensed aryl group And a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like, but are not limited thereto.
- the heteroaryl group of C5 to C20 includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl
- the group, triazine group, tetrahydropyranyl group, tetrahydrofuranyl group, etc. are mentioned, but it is not limited to this.
- alkoxy group for C 1 to C 20 examples include, but are not limited to, mesophilic, ethoxy, phenyloxy, and cyclonucleooxy groups.
- Group 4 transition metal examples include titanium, zirconium, and hafnium, but are not limited thereto.
- Ri to R 9 and IV to R 9 ′ of Formulas 2a and 2b are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert -Butyl group, pentyl group, nucleosil group, heptyl group, octyl group : phenyl group, halogen, trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl group, triisopropylsilyl, trimethylsilylmethyl group, mesophilic or special It is more preferable to be a season, but it is not limited thereto.
- L in Chemical Formula 1 is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto.
- the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.
- a in Formula 1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, mesoxymethyl group, tert-butoxymethyl group, It is preferable that it is a 1-ethoxyethyl group, the 1-methyl-1- methoxyethyl group, the tetrahydropyranyl group, or the tetrahydrofuranyl group, but it is not limited to this.
- B in Chemical Formula 1 is preferably silicon, but is not limited thereto.
- the compound of Formula 2a Specific examples include compounds represented by one of the following structural formulas,
- specific examples of the compound represented by Chemical Formula 2b include a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
- the metallocene compound according to the present invention has excellent activity and can polymerize olefin polymer of high molecular weight.
- high polymerization activity can be exhibited even when used on a carrier. Therefore, when used as a supported catalyst, ultra high molecular weight Olefin-based polymers can be prepared.
- the metallocene compound according to the present invention has a non-covalent electron pair capable of acting as a Lewis base in the ligand structure, and thus is efficiently supported on the surface having the Lewis acid characteristic of the carrier, thereby exhibiting high polymerization activity.
- the activity is high, due to the proper steric hindrance and the electronic effect of the ligand is not only low hydrogen reactivity but also maintains high activity even in the presence of hydrogen.
- the beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno indole derivative is grown is stabilized by hydrogen bonds, thereby inhibiting beta-hydrogen elimination, thereby polymerizing ultra high molecular weight oleflene-based polymers.
- the metallocene compound of Chemical Formula 1 may be obtained by connecting an indenoindole derivative (CI, C2) to a bridge compound to prepare a ligand compound, and then performing metallation by adding a metal precursor compound. It is not limited to this.
- an indenoindole derivative (CI, C2) is reacted with an organolithium compound such as n-BuLi to prepare a lithium salt, and a halogenated compound of the bridge compound is mixed therein, and then these mixtures are reacted.
- organolithium compound such as n-BuLi
- a halogenated compound of the bridge compound is mixed therein, and then these mixtures are reacted.
- a ligand compound The metallocene compound represented by Formula 1 above by mixing the ligand compound or a lithium salt thereof with a metal precursor compound and reacting the reaction mixture for about 12 hours to about 24 hours until the reaction is completed and then drying the reaction product under filtration and reduced pressure. Can be obtained.
- the present invention also provides a catalyst composition comprising the metallocene compound.
- the catalyst composition according to the present invention may further include one or more of the cocatalyst compounds represented by the following Formula 3, Formula 4, or Formula 5 in addition to the metallocene compound.
- R10 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
- n is an integer of 2 or more
- R 10 is as defined in Formula 3 above;
- J is aluminum or boron
- ⁇ is neutral or divalent Lewis acid
- ⁇ is a hydrogen atom
- ⁇ is a Group 13 element
- a ′ may be the same or different from each other, and each independently one or more hydrogen atoms are unsubstituted or substituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy, having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. to be.
- Examples of the compound represented by the formula (3) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.
- Examples of the compound represented by Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-S-butyl aluminum, tricyclopentyl aluminum , Tripentylaluminum, triisopentylaluminum, trinuclear silaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-setrial aluminum, dimethylaluminum methoxide, dimethylaluminum hydroxyoxide, Trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
- Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P-lryl) Boron, trimethylammonium tetra ( ⁇ , ⁇ - dimethylphenyl) boron, tributyl ammonium tetra ( ⁇ -trifluoromethylphenyl) boron, trimethylammonium tetra (J) -trifluoromethylphenyl) boron
- alumoxane can be used, more preferably methylalumoxane (MAO) which is alkylalumoxane.
- MAO methylalumoxane
- Catalyst composition according to the present invention comprising the steps of 1) contacting the metallocene compound represented by the formula (1) and the compound represented by the formula (3) or formula (4) to obtain a mixture; And 2) adding the compound represented by Chemical Formula 5 to the mixture.
- the catalyst composition according to the present invention may be prepared by contacting the metallocene compound represented by Formula 1 with the compound represented by Formula 3 as a second method.
- the molar ratio of the metallocene compound represented by Formula 1 / the compound represented by Formula 3 or Formula 4 is preferably 1 / 5,000 to 1/2, More preferably, it is 1 / 1,000-1/10, Most preferably, it is 1/500-1/20.
- the amount of the alkylating agent is so small that the alkylation of the metal compound may not be fully performed.
- the molar ratio of the metallocene compound represented by Chemical Formula 1 / the compound represented by Chemical Formula 5 is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 /. 5 to 1.
- the amount of the activator is relatively small, so that the activation of the metal compound may not be completed.
- the activity is inferior, and the molar ratio is less than 1/25, the activation of the metal compound is completely made, but there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the remaining excess activator .
- the molar ratio of the metallocene compound represented by Formula 1 / Compound 3 is preferably 1 / 10,000 to 1/10, more preferably 1 / 5,000 to 1/100, and most preferably 1 /. 3,000 and 1/500. If the molar ratio is greater than 1/10, the amount of the activator is relatively small, so that the activation of the metal compound is not fully performed, and thus the activity of the resulting catalyst composition is inferior. Although the activation is complete, there is a problem that the unit cost of the catalyst composition is not economical or the purity of the resulting polymer is inferior with the excess activator remaining.
- a hydrocarbon solvent such as pentane, nucleic acid, heptane, or the like, or an aromatic solvent such as benzene, toluene, or the like may be used.
- the metallocene compound and the cocatalyst compound may be used in a form supported on silica or alumina.
- the metallocene compound and the promoter compound are used in a supported form
- the metallocene compound may be included in an amount of about 0.5 to about 20 parts by weight
- the promoter may be included in an amount of about 1 to about 1,000 parts by weight, based on 100 parts by weight of the carrier.
- the metallocene compound may be included in an amount of about 1 to about 15 parts by weight
- a promoter may be included in an amount of about 10 to about 500 parts by weight, and most preferably, about 100 parts by weight of the carrier
- the metallocene compound may be included in an amount of about 1 to about 100 parts by weight, and the promoter may be included in an amount of about 40 to about 150 parts by weight.
- the carrier is not particularly limited as long as it is a kind of metal, metal salt or metal oxide that is usually used for the supported catalyst. Specifically, it may be in a form including any one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.
- the carriers can be dried at high temperatures, and they can typically comprise oxides, carbonates, sulfates or nitrates of metals such as Na 2 O, 2 C0 3 , BaS0 4 and Mg (N0 3 ) 2 .
- the amount of the hydroxy group can be controlled by the preparation method and preparation conditions of the carrier and drying conditions (temperature, time, drying method, etc.), and is preferably 0.1 to 10 mmol / g, more preferably 0.1 to 1 mmol / g. More preferably 0.1 to 0.5 mmol / g.
- a carrier having a large amount of semi-permanent siloxane groups participating in the support may be used while chemically removing the hydroxyl group.
- the present invention provides a method for producing an olefinic polymer that polymerizes an olefinic monomer in the presence of a catalyst composition comprising the metallocene compound, and an olefinic polymer prepared from the method.
- the polymerization reaction may be carried out by homopolymerizing one olepin monomer or copolymerizing two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
- the polymerization of the olefinic monomers may be performed by reacting at a temperature of about 25 to about 500 ° C. and about 1 to about 100 kgf / cm 2 for about 1 to about 24 hours. Specifically, the polymerization of the olefinic monomers may be carried out at a temperature of about 25 to about 5001, preferably about 25 to about 200 ° C, more preferably about 50 to about 100 ° C. The reaction pressure may also be carried out at about 1 to about 100 kgf / cm 2 , preferably about 1 to about 50 kgf / cm 2 , more preferably about 5 to about 40 kg cm 2 .
- olefin monomers are ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1 -Octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-atocene, and the like, and these may be copolymers in which two or more kinds thereof are mixed and copolymerized.
- the olefin polymer may be a polyethylene polymer, but is not limited thereto.
- the content of the alpha monomer, which is the comonomer is not particularly limited, and may be appropriately selected according to the use, purpose, and the like of the olefin polymer. More specifically, it may be more than 0 and 99 mol% or less.
- the produced lelpine-based polymer may exhibit a high molecular weight.
- the weight average molecular weight (Mw) of the olefinic polymer may be about 20,000 to about 3,000,000 g / mol, or about 30,000 To about 2,000,000 g / mol.
- Mw weight average molecular weight
- the olefin polymer is prepared using the catalyst composition in a form in which the metallocene compound is supported on a carrier, about 500,000 g / mol or more, for example, about 500,000 to about 3,000,000 g / mol, or about 500,000 to A high molecular weight olepin-based polymer of about 2,000,000 g / mol can be prepared.
- the molecular weight distribution (Mw / Mn) of the olefin polymer may be about 1.5 to about 15, preferably about 2.0 to about 10.
- the density of the olefinic polymer may be about 0.85 to about 0.96 g cm 3 , preferably, about 90 to about 0.95 ⁇ cm 3 .
- the leupin-based polymer according to the present invention exhibits ultra high molecular weight can be variously applied according to its use.
- the reaction solution was filtered to remove LiCl, and the filtrate was dried in vacuo and sonicated with hexane.
- the slurry was filtered to obtain 3.44 g (yield 92.6 mol%) of a metal violet compound of dark violet as a filtered solid.
- the reaction solution was filtered to remove LiCl, and the filtrate was dried in vacuo, and hexane was added to sonication.
- the slurry was filtered to obtain 3.40 g (yield 71.1 mol%) of a metal violet compound of dark violet as a filtered solid.
- Toluene slurry of ZrCl 4 (THF) 2 was transferred to litiated ligand in a dryice / acetone bath. It stirred at room temperature overnight and it changed into violet color. The reaction solution was filtered to remove LiCl, and the filtrate was dried in vacuo and sonicated. The slurry was filtered to obtain 4.0 g (yield 57.6 mol%) of a metal violet compound of dark violet as a filtered solid.
- Silica (SYLOPOL 948, manufactured by Grace Davison) was dehydrated under vacuum at a temperature of 400 ° C. for 12 hours to prepare a silica carrier.
- the supported catalyst was prepared in the same manner as in Preparation Example 6, except that 0.5 mm of the metallocene compound prepared in Preparation Example 2 was used. Prepared.
- a 300 mL Andrew bottle was prepared, assembled with an impeller part, and replaced with argon in a glove box. 180 mL of toluene was added to the Andrew bottle, and 10 mL of MAO (10 wt% in toluene) solution was added thereto. 20 ⁇ of the metallocene compound catalyst of Preparation Example 1 was added to a separately prepared 100 mL flask, dissolved in 20 mL of toluene, 5 mL (5 ⁇ ) of the catalyst solution was injected into an Andrew bottle, and stirred for 5 minutes. .
- the top of the bottle was fixed to a mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ° C.
- the ethylene valve was opened and slowly pressurized to 50 psig.
- the mechanical stirrer was operated and reacted for 30 minutes at 500 rpm while ethylene was supplied continuously to maintain the pressure as consumed ethylene.
- the ethylene valve was closed, the stirring was stopped, and the pressure in the reaction vessel was slowly vented.
- a 300 mL Andrew bottle was prepared, assembled with an impeller part, and replaced with argon in a glove box. 180 mL of toluene was added to the Andrew bottle, and 10 mL of MAO (10 wt% in toluene) solution was added thereto. 20 ⁇ of the metallocene compound catalyst of Preparation Example 1 was added to a separately prepared 100 mL flask, dissolved in 20 mL of toluene, 5 mL (5 ⁇ 1) of the catalyst solution was injected into an Andrew bottle, and stirred for 5 minutes. After the Andrew bottle was soaked in an oil bath heated to 90 ° C, the top of the bottle was fixed to the mechanical stirrer and stirred for 5 minutes until the reaction solution reached 90 ° C.
- Example 7 The polymer obtained was weighed to calculate the activity of the catalyst therefrom and used for further analysis.
- Examples 7 to 10 Except that the metallocene compound catalysts of Preparation Examples 2 to 5 were used, ethylene-1-nuxene copolymerization was performed in the same manner as in Example 6, and the obtained polymers were analyzed.
- the catalytic activity of the Examples 1 to 10, the molecular weight and distribution of the obtained polymer are shown in Table 1 below.
- This reaction contains 1.0 mmol triethylakra inum.
- 1.2 L of the nucleic acid was injected, and the prepared supported catalyst was introduced into the reactor without air contact, and then polymerized for 1 hour while continuously adding a gas ethylene monomer at a pressure of 40 bar at 80 ° C. Termination of the polymerization was completed by first stopping stirring and then evacuating and removing ethylene. The polymer obtained therefrom was filtered off to remove most of the polymerization solvent and then dried for 12 hours in an 80 ° C vacuum Aubon.
- the polymerization was carried out in the same manner as in Example 11, except that the supported catalyst prepared in Preparation Comparative Example 2 was used.
- the catalytic activity of the Examples 11 to 12 and Comparative Examples 1 and 2 the molecular weight and distribution of the obtained polymer are shown in Table 2 below.
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US14/908,819 US9725472B2 (en) | 2013-08-01 | 2013-10-14 | Metallocene compound, a catalyst composition comprising the same, and a method of preparing an olefinic polymer by using the same |
CN201380078688.9A CN105473601B (zh) | 2013-08-01 | 2013-10-14 | 茂金属化合物、包含其的催化剂组合物及使用其制备烯烃聚合物的方法 |
JP2016527902A JP6272477B2 (ja) | 2013-08-01 | 2013-10-14 | メタロセン化合物、これを含む触媒組成物およびこれを用いるオレフィン系重合体の製造方法 |
EP13890843.9A EP3012262B1 (en) | 2013-08-01 | 2013-10-14 | Metallocene compound, catalyst composition comprising same, and method for producing olefin polymer using catalyst composition |
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CN105985368A (zh) * | 2015-02-06 | 2016-10-05 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
EP3106474A4 (en) * | 2014-06-03 | 2017-08-30 | LG Chem, Ltd. | Method of preparing polyolefin and polyolefin prepared by said method |
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EP3138846B1 (en) | 2015-01-28 | 2019-03-06 | LG Chem, Ltd. | Metallocene compound, catalyst composition comprising same, and method for preparing olefin-based polymer using same |
US9994652B2 (en) * | 2015-01-28 | 2018-06-12 | Lg Chem, Ltd. | Metallocene compound, catalyst composition including the same, and method of preparing polyolefin using the same |
KR20160134464A (ko) | 2015-05-15 | 2016-11-23 | 주식회사 엘지화학 | 혼성 담지 촉매계, 및 이를 이용한 폴리올레핀의 제조방법 |
KR101768194B1 (ko) | 2015-05-15 | 2017-08-16 | 주식회사 엘지화학 | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 |
EP3243847B1 (en) | 2015-05-15 | 2020-08-26 | LG Chem, Ltd. | Catalytic composition and method of preparing polyolefin using same |
KR102002983B1 (ko) | 2016-02-24 | 2019-07-23 | 주식회사 엘지화학 | 혼성 담지 메탈로센 촉매 및 이를 이용한 폴리올레핀의 제조 방법 |
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US9988469B2 (en) | 2014-06-03 | 2018-06-05 | Lg Chem, Ltd. | Method for preparing polyolefin and polyolefin prepared thereby |
WO2016124157A1 (zh) * | 2015-02-06 | 2016-08-11 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
CN105985368A (zh) * | 2015-02-06 | 2016-10-05 | 中国石油天然气股份有限公司 | 含杂原子的π-配体的茂金属络合物及其制备方法、其催化剂体系和催化剂体系的应用 |
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EP3012262B1 (en) | 2018-10-03 |
US9725472B2 (en) | 2017-08-08 |
JP6272477B2 (ja) | 2018-01-31 |
EP3012262A4 (en) | 2017-03-01 |
KR101623485B1 (ko) | 2016-05-23 |
CN105473601B (zh) | 2018-07-10 |
US20160159828A1 (en) | 2016-06-09 |
EP3012262A1 (en) | 2016-04-27 |
CN105473601A (zh) | 2016-04-06 |
JP2016525125A (ja) | 2016-08-22 |
KR20150015791A (ko) | 2015-02-11 |
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