US10385146B2 - Metallocene compound - Google Patents

Metallocene compound Download PDF

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US10385146B2
US10385146B2 US15/557,775 US201615557775A US10385146B2 US 10385146 B2 US10385146 B2 US 10385146B2 US 201615557775 A US201615557775 A US 201615557775A US 10385146 B2 US10385146 B2 US 10385146B2
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metallocene compound
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halogen
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US20180072822A1 (en
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Kyung Jin Cho
Ki Soo Lee
Sung Min Lee
Bog Ki HONG
Min Seok Cho
Se Young Kim
Chang Woan HAN
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LG Chem Ltd
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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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 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
    • C08F4/61927—Component covered by group C08F4/60 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07F7/30—Germanium compounds
    • 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
    • C08F10/02—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
    • 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
    • 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
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • CGC Constrained-Geometry Catalyst
  • Dow Co. U.S. Pat. No. 5,064,802
  • the CGC is superior to commonly known metallocene catalysts in a copolymerization reaction of ethylene and alpha-olefin as follows: (1) At a high polymerization temperature, high activity is shown and a polymer having a high molecular weight is produced, and (2) the copolymerization ability of alpha-olefin having large steric hindrance such as 1-hexene and 1-octene is excellent.
  • a variety of characteristics of CGC upon polymerization are becoming gradually known, and thus thorough research into synthesis of derivatives thereof to serve as a polymerization catalyst is ongoing in academic and industrial fields.
  • a Group 4 transition metal compound having one or two cyclopentadienyl groups as a ligand may be used as a catalyst for olefin polymerization by activating it with methylaluminoxane or a boron compound.
  • Such catalyst shows unique characteristics that traditional Zeigler-Natta catalyst does not have.
  • a polymer obtained by using such catalyst has a narrow molecular weight distribution and higher reactivity for a second monomer such as alpha-olefin or cycloolefin, and distribution of the second monomer in the polymer is even. Furthermore, it is possible to control the stereoselectivity of the polymer in the polymerization of alpha-olefin by changing the substituent of the cyclopentadienyl ligand in the metallocene catalyst, and it is easy to control the degree of copolymerization, the molecular weight, and the distribution of the second monomer upon copolymerization of ethylene and other olefins.
  • the metallocene catalyst is more expensive than Zeigler-Natta catalyst, it must have good activity for its economic value. If the metallocene catalyst has high reactivity for the second monomer, there is an advantage that a polymer including a large amount of the second monomer may be obtained by using only a small amount of the second monomer.
  • the bridged catalyst developed until now may be classified into three types according to the type of the bridge.
  • the first type of the bridged catalyst is a catalyst of which two cyclopentadienyl ligands are connected to an alkylene dibridge by the reaction of an electrophile, such as an alkyl halide, indene or fluorene.
  • the second is a silicone-bridged catalyst of which the ligands are connected to —SiR2-
  • the third is a methylene-bridged catalyst which is obtained by the reaction of fulvene, indene or fluorene.
  • the present disclosure provides a metallocene compound which has excellent activity and is capable of producing an olefin-based polymer having a high molecular weight.
  • the present disclosure provides a metallocene compound which maintains a high activity even in the presence of hydrogen because of its low hydrogen reactivity, and may polymerize an olefin-based polymer having a high molecular weight.
  • the present disclosure provides a metallocene compound represented by the following Chemical Formula 1.
  • a metallocene compound according to the present disclosure may be used for the preparation of an olefin-based polymer, may have excellent activity, and may produce an olefin-based polymer having a relatively high molecular weight compared with the case of using a catalyst composition having a similar structure due to the structural and electrical steric hindrance effect.
  • the activity of the catalyst may be maintained for a long residence time in a reactor because of its long life time.
  • the terms “the first”, “the second”, and the like are used to describe a variety of components, and these terms are merely employed to differentiate a certain component from other components.
  • a metallocene compound according to the present disclosure is characterized in that it is represented by the following Chemical Formula 1.
  • the C1 to C20 alkyl group may include a linear or branched alkyl group, and specifically, it may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or the like, but is not limited thereto.
  • the C2 to C20 alkenyl group may include a linear or branched alkenyl group, and specifically, it may be an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or the like, but is not limited thereto.
  • the C6 to C20 aryl group may include a single ring aryl group or a condensed ring aryl group, and specifically, it may be a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, or the like, but is not limited thereto.
  • the C5 to C20 heteroaryl group may include a single ring heteroaryl group or a condensed ring heteroaryl group, and specifically, it may be 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 group, a triazine group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or the like, but is not limited thereto.
  • the C1 to C20 alkoxy group may be a methoxy group, an ethoxy group, a phenyloxy group, a cyclohexyloxy group, a tert-butoxyhexyl group, or the like, but is not limited thereto.
  • the Group 4 transition metal may be titanium, zirconium, hafnium, or the like, but is not limited thereto.
  • R 1 to R 5 are each independently hydrogen, halogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an ethylene group, a propylene group, a butylene group, a phenyl group, a benzyl group, a naphthyl group, a halogen group, an ether group, a dimethyl ether group, a methoxy group, an ethoxy group, or a tert-butoxyhexyl group, and R 6 to R 32 are each independently hydrogen, halogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group
  • Q 1 and Q 2 in Chemical Formula 1 are each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a tert-butoxymethyl group, a 1-ethoxyethyl group, a 1-methyl-1-methoxyethyl group, a tert-butoxyhexyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group, but is not limited thereto.
  • B 1 in Chemical Formula 1 is preferably silicon, but is not limited thereto.
  • the metallocene compound of the Chemical Formula 1 is characterized in that the substituent of the Chemical Formula 2a includes a silylalkyl group such as trimethylsilyl methyl.
  • the indene derivative of the Chemical Formula 2a has a silylalkyl group at the 2-position carbon of the indene, the vicinity of the active site is opened only in one direction due to the steric effect by the substituent, and thereby the polymer can be grown only in one direction.
  • chain elongation can occur relatively strongly because access to monomers or reagents that cause chain transfer is difficult and beta-elimination of the beta site is difficult in the molecule itself. Therefore, the olefin polymer having a relatively high molecular weight can be polymerized with high activity as compared with the case of using another metallocene compound having a similar structure.
  • the compound since the compound has the indenyl group represented by the above Chemical Formula 2a containing a silylalkyl group at 2-position carbon only on one side, it has smaller steric hindrance effect than the compound having a silylalkyl group on both sides. Therefore, when the ethylene-alpha olefin copolymerization proceeds, the content of the comonomer can be effectively increased even when a relatively large alpha-olefin such as 1-hexene, 1-heptene or 1-octene is used.
  • the compound forms a structure in which the indeno indole derivative represented by the following Chemical Formula 2b, the fluorenyl derivative represented by the following Chemical Formula 2c, the indene derivative represented by the following Chemical Formula 2d, and the cyclopentadiene derivative represented by the following Chemical Formula 2e are cross-linked by a bridge, and exhibits a high polymerization activity by having a non-covalent electron pair capable of acting as a Lewis base in a ligand structure.
  • a specific example of the compound represented by Chemical Formula 2a may be a compound represented by any one of the following structural formulae, but is not limited thereto.
  • a specific example of the compound represented by Chemical Formula 2b may be a compound represented by any one of the following structural formulae, but is not limited thereto.
  • a specific example of the compound represented by Chemical Formula 2c may be a compound represented by any one of the following structural formulae, but is not limited thereto.
  • a specific example of the compound represented by Chemical Formula 2d may be a compound represented by any one of the following structural formulae, but is not limited thereto.
  • a specific example of the compound represented by Chemical Formula 2e may be a compound represented by any one of the following structural formulae, but is not limited thereto.
  • the metallocene compound according to the present disclosure may have excellent activity and may polymerize an olefin-based polymer having a high molecular weight.
  • the metallocene compound according to the present disclosure may polymerize an olefin-based polymer having a high molecular weight with still high activity because of its low hydrogen reactivity, even when the polymerization reaction is carried out in the presence of hydrogen in order to prepare an olefin-based polymer having a high molecular weight and a wide molecular weight distribution at the same time. Therefore, the metallocene compound may prepare an olefin-based polymer satisfying the high molecular characteristic without a decrease in activity even when the metallocene compound is heterogeneously used together with a catalyst having different characteristics, and thus the olefin-based polymer having a high molecular weight and a wide molecular weight distribution may be easily prepared.
  • the metallocene compound of Chemical Formula 1 may be obtained by connecting the indene derivative and the cyclopentadiene derivative with a bridge compound to prepare a ligand compound, and carrying out a metallation by adding a metal precursor compound, but is not limited to thereto.
  • a halogenated compound of a bridge compound is mixed therewith and then this mixture is reacted to prepare the ligand compound.
  • the reaction mixture may be filtered and dried under reduced pressure to obtain the metallocene compound represented by Chemical Formula 1.
  • the present disclosure also provides a method of preparing an olefin copolymer using the metallocene compound.
  • the metallocene compound represented by the Chemical Formula 1 may be used in the preparation of the polyolefin polymer, alone or in combination with a cocatalyst as a catalyst composition.
  • a cocatalyst as a catalyst composition.
  • an olefin homopolymer or an olefin copolymer may be provided by contacting the catalyst composition including the metallocene compound represented by the Chemical formula 1 with an olefin-based monomer to carry out a polymerization process.
  • the catalyst composition may further include one or more of cocatalyst compounds represented by the following Chemical Formula 3, Chemical Formula 4, and Chemical Formula 5, in addition to the metallocene compound: —[Al(R 50 )—O] m — [Chemical Formula 3]
  • Examples of the compound represented by Chemical Formula 3 may include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane or the like, and a more preferred compound may be methylaluminoxane.
  • Examples of the compound represented by Chemical Formula 4 may include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminummethoxide, dimethylaluminumethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron or the like, and a more preferred compound may be selected from trimethylaluminum, trie
  • Examples of the compound represented by Chemical Formula 5 may include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, trimethylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetrapentafluorophenylboron, N,N-diethylanilinium tetraphenylboron, N,N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrap
  • Alumoxane may be preferably used, and methylalumoxane (MAO) which is an alkyl alumoxane may be more preferably used.
  • MAO methylalumoxane
  • the catalyst composition may be prepared by a first method including the steps of 1) contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 3 or Chemical Formula 4 to obtain a mixture; and 2) adding the compound represented by Chemical Formula 5 to the mixture.
  • the catalyst composition may be prepared by a second method of contacting the metallocene compound represented by Chemical Formula 1 with the compound represented by Chemical Formula 3.
  • a hydrocarbon solvent such as pentane, hexane, heptane, etc., or an aromatic solvent such as benzene, toluene, etc., may be used.
  • An olefin-based polymer may be prepared by polymerizing olefin-based monomers in the presence of the catalyst composition including the metallocene compound.
  • the polymerization reaction may be carried out according to a solution polymerization process, a slurry process, or a gas phase process by using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor. Furthermore, the reaction may be a homopolymerization of an olefin-based monomer or copolymerization of two or more monomers.
  • the polymerization of the olefin-based monomer may be carried out at a temperature of about 25 to about 500° C. and at a pressure of about 1 to about 100 kgf/cm 2 for about 1 to about 24 hours. Specifically, the polymerization of the olefin-based monomer may be carried out at a temperature of about 25 to about 500° C., preferably about 25 to about 200° C., and more preferably, about 50 to about 100° C. Furthermore, the reaction pressure may be about 1 to about 100 kgf/cm 2 , preferably about 1 to about 50 kgf/cm 2 , and more preferably about 5 to about 40 kgf/cm 2 .
  • the olefin-based monomer may include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene or the like, and the olefin-based monomer may be a copolymer prepared by copolymerizing two or more of the monomers.
  • the olefin-based polymer may be a polyethylene polymer, but is not limited to thereto.
  • the olefin-based polymer is a copolymer of ethylene/alpha-olefin
  • the content of a comonomer, alpha-olefin is not particularly limited, and it may be adequately selected according to the use or purpose of the olefin-based polymer. More specifically, the content may be more than 0 mole % and 99 mole % or less.
  • the olefin-based polymer prepared by the method may exhibit a high molecular weight compared with the case of using an organometallic compound having a similar structure as a catalyst.
  • a weight average molecular weight (Mw) of the olefin-based polymer may be about 100,000 to about 1,000,000 g/mol, more preferably about 100,000 to about 600,000 g/mol.
  • a molecular weight distribution (Mw/Mn, PDI) of the olefin-based polymer may be about 1 to about 10, more preferably about 3 to about 6.
  • the olefin-based polymer according to the present disclosure shows a high molecular weight, thereby being applied to a variety of fields according to its use.
  • Synthesized Composition 1-2 was added to the Synthesized Composition 1-1 dropwise in a dry ice/acetone bath, the reaction mixture was slowly warmed up to room temperature, and then stirred for 24 hours.
  • the obtained ligand compound was used for the preparation of the metallocene compound.
  • the resulting product was stored in a toluene solution.
  • Synthesized Composition 2-2 was added to the Synthesized Composition 2-1 dropwise in a dry ice/acetone bath, the reaction mixture was slowly warmed up to room temperature, and then stirred for 24 hours.
  • the obtained ligand compound was used for the preparation of the metallocene compound.
  • Synthesized Composition 3-2 was added to the Synthesized Composition 3-1 dropwise in a dry ice/acetone bath, the reaction mixture was slowly warmed up to room temperature, and then stirred for 24 hours.
  • the obtained ligand compound was used for the preparation of the metallocene compound.
  • the resulting product was stored in a toluene solution.
  • Synthesized Composition 4-2 was added to the Synthesized Composition 4-1 dropwise in a dry ice/acetone bath, the reaction mixture was slowly warmed up to room temperature, and then stirred for 24 hours.
  • the obtained ligand compound was used for the preparation of the metallocene compound.
  • Hexane was added in about 5 times volume of the remaining toluene thereto and recrystallized.
  • the mixture was filtered without contacting with the outside air to give a metallocene compound in a dark red powder phase.
  • the resulting filter cake in the upper portion of the filter was washed using a little Hexane, and then weighed in the glove box to identify the synthesis.
  • Synthesized Composition 5-2 was added to the Synthesized Composition 5-1 dropwise in a dry ice/acetone bath, the reaction mixture was slowly warmed up to room temperature, and then stirred for 24 hours.
  • the obtained ligand compound was used for the preparation of the metallocene compound.
  • a 100 mL Andrew bottle was prepared and assembled with an impeller part, and then air in the bottle was replaced by argon in a glove box. After adding 70 mL of toluene containing a small amount of TMA to the Andrew bottle, 10 mL of an MAO (10 wt % in toluene) solution was added thereto. 5 mL of a catalyst/toluene solution (5 ⁇ mol of catalyst), which was prepared by dissolving the metallocene compound of the Examples in toluene, was injected into the Andrew bottle.
  • the Andrew bottle was immersed in an oil bath heated to 90° C.
  • the top of the bottle was fixed to a mechanical stirrer, and then, the reaction solution was stirred for 5 minutes until it reached to 90° C.
  • the air in the bottle was purged with ethylene gas 3 times, and pressure was slowly raised up to 50 psig by opening an ethylene valve.
  • the reaction was allowed to continue for 30 min while operating the mechanical stirrer at 500 rpm while maintaining the pressure by continuously providing ethylene of as much as was consumed.
  • the gas in the reactor was slowly vented after locking the ethylene valve and stopping agitation.
  • a 100 mL Andrew bottle was prepared and assembled with an impeller part, and then air in the bottle was replaced by argon in a glove box. After adding 70 mL of toluene containing a small amount of TMA to the Andrew bottle, 10 mL of an MAO (10 wt % in toluene) solution was added thereto. 5 mL of a catalyst/toluene solution (5 ⁇ mol of catalyst), which was prepared by dissolving the metallocene compound of the Examples in toluene, was injected into the Andrew bottle.

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KR101926833B1 (ko) 2019-03-07
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