US10385146B2 - Metallocene compound - Google Patents

Metallocene compound Download PDF

Info

Publication number
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
Authority
US
United States
Prior art keywords
group
chemical formula
metallocene compound
compound
halogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US15/557,775
Other languages
English (en)
Other versions
US20180072822A1 (en
Inventor
Kyung Jin Cho
Ki Soo Lee
Sung Min Lee
Bog Ki HONG
Min Seok Cho
Se Young Kim
Chang Woan HAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority claimed from PCT/KR2016/005924 external-priority patent/WO2016195423A1/ko
Assigned to LG CHEM, LTD. reassignment LG CHEM, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHO, MIN SEOK, HAN, CHANG WOAN, HONG, BOG KI, KIM, SE YOUNG, LEE, KI SOO, LEE, SUNG MIN, CHO, KYUNG JIN
Publication of US20180072822A1 publication Critical patent/US20180072822A1/en
Application granted granted Critical
Publication of US10385146B2 publication Critical patent/US10385146B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
US15/557,775 2015-06-05 2016-06-03 Metallocene compound Active US10385146B2 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2015--0080018 2015-06-05
KR10-2015-0080018 2015-06-05
KR20150080018 2015-06-05
KR10-2016-0069064 2016-06-02
KR1020160069064A KR101926833B1 (ko) 2015-06-05 2016-06-02 메탈로센 화합물
PCT/KR2016/005924 WO2016195423A1 (ko) 2015-06-05 2016-06-03 메탈로센 화합물

Publications (2)

Publication Number Publication Date
US20180072822A1 US20180072822A1 (en) 2018-03-15
US10385146B2 true US10385146B2 (en) 2019-08-20

Family

ID=57575526

Family Applications (1)

Application Number Title Priority Date Filing Date
US15/557,775 Active US10385146B2 (en) 2015-06-05 2016-06-03 Metallocene compound

Country Status (5)

Country Link
US (1) US10385146B2 (ja)
EP (1) EP3252064B1 (ja)
JP (1) JP6470847B2 (ja)
KR (1) KR101926833B1 (ja)
CN (1) CN107428788B (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101973191B1 (ko) 2015-06-05 2019-04-26 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조 방법
US10882925B2 (en) 2017-11-29 2021-01-05 Exxonmobil Chemical Patents Inc. Catalysts that produce polyethylene with broad, bimodal molecular weight distribution
CN112745366B (zh) * 2019-10-30 2024-05-24 中国石油化工股份有限公司 硅基桥联的茂金属化合物及其制备方法、应用

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5360921A (en) 1993-03-22 1994-11-01 Mitsui Petrochemical Industries, Ltd. Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
JPH07304829A (ja) 1994-05-09 1995-11-21 Mitsubishi Chem Corp 重合体の製造法
JPH09132584A (ja) 1995-07-28 1997-05-20 Hoechst Ag メタロセン化合物
WO1997040075A1 (fr) 1996-04-22 1997-10-30 Japan Polyolefins Co., Ltd. Procede de production de polyolefine et catalyseur approprie
JPH09512848A (ja) 1994-05-06 1997-12-22 デーエスエム ナムローゼ フェンノートシャップ エチレン、α−オレフィン及び付加的なジエンからの弾性ポリマーの製法
JPH107692A (ja) 1996-03-29 1998-01-13 Phillips Petroleum Co 置換インデニル未架橋メタロセン
US5763700A (en) 1992-09-16 1998-06-09 British Technology Group Limited Pesticidal fluoroolefins
JP2001508822A (ja) 1997-01-28 2001-07-03 ボレアリス エイ／エス メタロセン化合物用の新規な活性化剤系
US6277778B1 (en) 1996-01-30 2001-08-21 Borealis A/S Heteroatom substituted metallocene compounds for olefin polymerization catalyst systems and methods for preparing them
WO2003050131A1 (en) 2001-12-10 2003-06-19 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2003102042A1 (en) 2002-05-31 2003-12-11 Equistar Chemicals, Lp High-temperature olefin polymerisation process in solution
KR20050024287A (ko) 2002-05-31 2005-03-10 에퀴스타 케미칼즈, 엘피 용액 상태의 고온 올레핀 중합 방법
KR20060021476A (ko) 2004-09-03 2006-03-08 주식회사 엘지화학 담지 메탈로센 촉매, 그 제조방법 및 이를 이용한폴리올레핀의 제조방법
US20060154804A1 (en) 2002-01-08 2006-07-13 Basell Polyolefine Gmbh Preparation of dialkyl-ansa-metallocenes
KR20100067627A (ko) 2008-12-11 2010-06-21 주식회사 엘지화학 혼성 담지 메탈로센 촉매, 이의 제조방법 및 이를 이용한 올레핀계 중합체의 제조방법
KR20100101092A (ko) 2007-10-25 2010-09-16 루머스 노보렌 테크놀로지 게엠베하 메탈로센 화합물, 이를 포함하는 촉매, 이 촉매를 사용한 올레핀 폴리머생산방법, 및 올레핀 호모- 및 코폴리머
JP2013100481A (ja) 2011-10-10 2013-05-23 Japan Polypropylene Corp メタロセン予備重合触媒の製造方法
JP5466826B2 (ja) 2008-02-08 2014-04-09 日本ポリプロ株式会社 プロピレン／エチレン−αオレフィン系ブロック共重合体の製造方法
KR20150058054A (ko) 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법
KR20170076642A (ko) 2013-12-06 2017-07-04 주식회사 엘지화학 메탈로센 화합물

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6015306B2 (ja) * 2012-09-28 2016-10-26 日本ポリエチレン株式会社 メタロセン化合物、それを含むオレフィン重合用触媒成分およびオレフィン重合用触媒、並びにそのオレフィン重合用触媒を用いたオレフィン重合体の製造方法
WO2015047031A1 (ko) * 2013-09-30 2015-04-02 주식회사 엘지화학 폴리프로필렌의 제조방법 및 이로부터 수득되는 폴리프로필렌

Patent Citations (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5064802A (en) 1989-09-14 1991-11-12 The Dow Chemical Company Metal complex compounds
US5763700A (en) 1992-09-16 1998-06-09 British Technology Group Limited Pesticidal fluoroolefins
US5360921A (en) 1993-03-22 1994-11-01 Mitsui Petrochemical Industries, Ltd. Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
JPH09512848A (ja) 1994-05-06 1997-12-22 デーエスエム ナムローゼ フェンノートシャップ エチレン、α−オレフィン及び付加的なジエンからの弾性ポリマーの製法
US5902867A (en) 1994-05-06 1999-05-11 Dsm Nv Process for the preparation of an elastomeric polymer from ethylene, alpha-olefine and optionally diene
JPH07304829A (ja) 1994-05-09 1995-11-21 Mitsubishi Chem Corp 重合体の製造法
JPH09132584A (ja) 1995-07-28 1997-05-20 Hoechst Ag メタロセン化合物
US6277778B1 (en) 1996-01-30 2001-08-21 Borealis A/S Heteroatom substituted metallocene compounds for olefin polymerization catalyst systems and methods for preparing them
JP4051089B2 (ja) 1996-01-30 2008-02-20 ボレアリス・エイ／エス オレフィン重合触媒系用ヘテロ原子置換メタロセン化合物およびそれらの調製法
JPH107692A (ja) 1996-03-29 1998-01-13 Phillips Petroleum Co 置換インデニル未架橋メタロセン
US5780659A (en) 1996-03-29 1998-07-14 Phillips Petroleum Company Substituted indenyl unbridged metallocenes
US6037427A (en) 1996-03-29 2000-03-14 Schmid; Claudia Polymerization with substituted indenyl cyclopentadienyl metallocenes
WO1997040075A1 (fr) 1996-04-22 1997-10-30 Japan Polyolefins Co., Ltd. Procede de production de polyolefine et catalyseur approprie
US6121182A (en) 1996-04-22 2000-09-19 Japan Polyolafins Co., Ltd. Polyolefin production catalyst and method of preparing polyolefins
JP2001508822A (ja) 1997-01-28 2001-07-03 ボレアリス エイ／エス メタロセン化合物用の新規な活性化剤系
US6380332B1 (en) 1997-01-28 2002-04-30 Borealis Technology Oy Activator system for metallocene compounds
WO2003050131A1 (en) 2001-12-10 2003-06-19 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
JP2005511751A (ja) 2001-12-10 2005-04-28 エクソンモービル・ケミカル・パテンツ・インク メタロセン類、及びそれらから誘導される触媒組成物
US20060154804A1 (en) 2002-01-08 2006-07-13 Basell Polyolefine Gmbh Preparation of dialkyl-ansa-metallocenes
WO2003102042A1 (en) 2002-05-31 2003-12-11 Equistar Chemicals, Lp High-temperature olefin polymerisation process in solution
KR20050024287A (ko) 2002-05-31 2005-03-10 에퀴스타 케미칼즈, 엘피 용액 상태의 고온 올레핀 중합 방법
US6756455B2 (en) 2002-05-31 2004-06-29 Equistar Chemicals, Lp High-temperature solution process for polyolefin manufacture
KR20060021476A (ko) 2004-09-03 2006-03-08 주식회사 엘지화학 담지 메탈로센 촉매, 그 제조방법 및 이를 이용한폴리올레핀의 제조방법
US8124557B2 (en) 2004-09-03 2012-02-28 Lg Chem, Ltd. Supported metallocene catalyst, method of preparing the catalyst and method of preparing polyolefin using the catalyst
US20120329964A1 (en) 2007-10-25 2012-12-27 Lummus Novolen Technology Gmbh Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
KR20100101092A (ko) 2007-10-25 2010-09-16 루머스 노보렌 테크놀로지 게엠베하 메탈로센 화합물, 이를 포함하는 촉매, 이 촉매를 사용한 올레핀 폴리머생산방법, 및 올레핀 호모- 및 코폴리머
JP2011500800A (ja) 2007-10-25 2011-01-06 ルムス・ノボレン・テクノロジー・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング メタロセン化合物、それを含む触媒、その触媒を使用するオレフィンポリマーの製造プロセス、ならびにオレフィンホモポリマーおよびコポリマー
US8299287B2 (en) 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
JP5466826B2 (ja) 2008-02-08 2014-04-09 日本ポリプロ株式会社 プロピレン／エチレン−αオレフィン系ブロック共重合体の製造方法
KR20100067627A (ko) 2008-12-11 2010-06-21 주식회사 엘지화학 혼성 담지 메탈로센 촉매, 이의 제조방법 및 이를 이용한 올레핀계 중합체의 제조방법
EP2374822A2 (en) 2008-12-11 2011-10-12 LG Chem, Ltd. Hybrid supported metallocene catalyst, method for preparing the same, and method for preparing polyolefin polymers using same
JP2013100481A (ja) 2011-10-10 2013-05-23 Japan Polypropylene Corp メタロセン予備重合触媒の製造方法
KR20150058054A (ko) 2013-11-18 2015-05-28 주식회사 엘지화학 메탈로센 담지 촉매 및 이를 이용하는 폴리올레핀의 제조방법
KR20170076642A (ko) 2013-12-06 2017-07-04 주식회사 엘지화학 메탈로센 화합물

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Andreas C. Moller, et al., Synthesis, structure, and ethene polymerisation catalysis of 1- or 2-silyl substituted . . . , Dalton Trans., 2004, pp. 1578-1589.
Reko Leino, et al., Syndiospecific Propylene Polymerization . . . , Macromolecules 2001, 34, 2072-2082.

Also Published As

Publication number Publication date
KR20160143551A (ko) 2016-12-14
US20180072822A1 (en) 2018-03-15
EP3252064A1 (en) 2017-12-06
EP3252064A4 (en) 2018-10-24
EP3252064B1 (en) 2021-05-26
CN107428788A (zh) 2017-12-01
JP2018513126A (ja) 2018-05-24
KR101926833B1 (ko) 2019-03-07
JP6470847B2 (ja) 2019-02-13
CN107428788B (zh) 2020-03-10

Similar Documents

Publication Publication Date Title
JP6236155B2 (ja) 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
US9725472B2 (en) Metallocene compound, a catalyst composition comprising the same, and a method of preparing an olefinic polymer by using the same
US9994652B2 (en) Metallocene compound, catalyst composition including the same, and method of preparing polyolefin using the same
US10774160B2 (en) Supported hybrid catalyst system for ethylene slurry polymerization and method for preparing ethylene polymer with the catalyst system
US10450390B2 (en) Metallocene compound, metallocene-supported catalyst, and method of preparing polyolefin using the same
US9994653B2 (en) Metallocene compound, catalyst composition including the same, and method of preparing olefin-based polymer using the same
KR101743327B1 (ko) 신규한 리간드 화합물 및 전이금속 화합물
US10385146B2 (en) Metallocene compound
KR20150066344A (ko) 메탈로센 화합물, 이를 포함하는 촉매 조성물 및 이를 이용하는 올레핀계 중합체의 제조방법
US10604596B2 (en) Metallocene supported catalyst and method for preparing polyolefin using the same
WO2016195423A1 (ko) 메탈로센 화합물

Legal Events

Date Code Title Description
AS Assignment

Owner name: LG CHEM, LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHO, KYUNG JIN;LEE, KI SOO;LEE, SUNG MIN;AND OTHERS;SIGNING DATES FROM 20170816 TO 20170818;REEL/FRAME:043565/0837

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: AWAITING TC RESP., ISSUE FEE NOT PAID

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4