WO2020174346A1 - Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant - Google Patents

Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant Download PDF

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WO2020174346A1
WO2020174346A1 PCT/IB2020/051519 IB2020051519W WO2020174346A1 WO 2020174346 A1 WO2020174346 A1 WO 2020174346A1 IB 2020051519 W IB2020051519 W IB 2020051519W WO 2020174346 A1 WO2020174346 A1 WO 2020174346A1
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alkyl
group
aryl
ethylene
olefin
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PCT/IB2020/051519
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Korean (ko)
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신동철
오연옥
김미지
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사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
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Priority claimed from KR1020200020828A external-priority patent/KR20200105409A/ko
Application filed by 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 filed Critical 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority to JP2021532373A priority Critical patent/JP7164929B2/ja
Priority to US17/433,268 priority patent/US20220089790A1/en
Priority to EP20762870.2A priority patent/EP3904360A4/fr
Priority to CN202080008790.1A priority patent/CN113677686A/zh
Priority to CA3120265A priority patent/CA3120265C/fr
Publication of WO2020174346A1 publication Critical patent/WO2020174346A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/64—Quaternary ammonium compounds having quaternised nitrogen atoms bound to carbon atoms of six-membered aromatic rings
    • 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
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • 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
    • C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
    • 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
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Definitions

  • the present invention relates to a tetraaryl borate compound, a catalyst composition comprising the same, and a method for producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) using the same.
  • the main catalyst component of titanium or vanadium compounds and alkyl aluminum In general, the main catalyst component of titanium or vanadium compounds and alkyl aluminum
  • the so-called Ziegler-Natta catalyst system which is composed of the co-catalyst component of the compound, has been used.
  • the Zeigler-Natta catalyst system exhibits high activity against ethylene polymerization, but due to the non-uniform catalytic activity point, the molecular weight distribution of the resulting polymer is generally wide.
  • the copolymer of ethylene and (X-olefin there was a disadvantage that the crude composition was not uniform.
  • Metallocene of transition metals in Group 4 of the periodic table such as titanium, zirconium, and hafnium recently
  • the so-called metallocene catalyst system was developed, consisting of a compound and a co-catalyst, methylaluminoxane (1st high school 61; 11) ⁇ 11111111100116). Because the metallocene catalyst system is a homogeneous catalyst having a single catalytic activity point, the existing Ziegler- Compared to the Natta catalyst system, the molecular weight distribution is narrow and it has the characteristics of being able to produce polyethylene having a uniform composition. For example, in Patent Documents 1 to 1, ethylene is highly active by activating a metallocene compound with the co-catalyst methylaluminoxane.
  • Patent Documents 14 to 17 a catalyst system including a cocatalyst provided in the form of a slurry is disclosed.
  • the cocatalyst disclosed in these is supplied to the reactor as a cocatalyst solution including a toluene solution, etc., and is continuously or discontinuous with the metallocene compound.
  • the supply device such as a pump used in a production process carried out at a mass scale may be disturbed, preventing stable operation.
  • problems due to the solubility problem of the catalyst system Since an aromatic hydrocarbon-based solvent such as toluene must be used, problems such as residual ethylene alone polymerization or a copolymer of ethylene and (X-olefin, etc.), which are the final products, cause odor, and additional processes are involved to remove them.
  • Patent Document 1 European Patent Publication No. 320, 762 (1989.06.21)
  • Patent Document 2 European Patent Publication No. 372, 632 (1990.06.13)
  • Patent Document 3 Japanese Patent Application No. 63-092621 (1988.04.23)
  • Patent Document 4 Japanese Patent Laid-Open No. 02-84405 (1990.03.26)
  • Patent Document 5 Unexamined Patent Publication No. 03-2347 (1991.01.08)
  • Patent Document 6 European Patent No. 0416815 (1991.03.13)
  • Patent Document 7 European Patent No. 0420436 (1991.04.03)
  • Patent Document 8 European Patent No. 0842939 (1998.05.20)
  • Patent Document 9 ⁇ 0 98/06728 (1998.02.19)
  • Patent Document 10 O 01/42315 (2001.06.14)
  • Patent Document 11 European patent system (Shoo 16715 No. (1997.08.13)
  • Patent Document 12 European Patent No. 0420436 (1996.08.14)
  • Patent Document 14 European Patent No. 0889062 (1999.01.07)
  • Patent Document 16 US Patent No. 6613850 (2003.09.02)
  • Patent Document 1 US Patent No. 6660816 (2001.07.19)
  • the present inventors conducted extensive research, and as a result of using a tetraarylborate compound containing a cation having an alkylidene anilinium structure as a co-solvent, the solubility of an aliphatic hydrocarbon-based solvent was determined.
  • the present invention was completed by discovering that it can effectively improve the activity of a single active point catalyst.
  • One object of the present invention is to provide a new tetraarylborate compound useful as a cocatalyst for the production of an ethylene homopolymer or a copolymer of ethylene and (X-olefin), and to provide a catalyst composition containing this and a single active point catalyst. There is.
  • One object of the present invention is to provide a method for economically producing an ethylene homopolymer or a copolymer of ethylene and (X-olefin) from a commercial point of view by using the above catalyst composition.
  • Tetraarylborate compounds are provided.
  • Tetraarylborate compounds An ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and (X-olefin) containing a single active point catalyst containing a group 4 transition metal; and an aluminum compound is provided.
  • a method for preparing a copolymer of ethylene and (X-olefin is provided.
  • the tetraaryl borate compound according to the present invention is used for a hydrocarbon-based solvent.
  • the tetraarylborate compound can be completely soluble in an aliphatic hydrocarbon-based solvent, so it may not be limited in its usage due to its solubility.
  • the solution-type cocatalyst provided through it can operate a commercial process.
  • alkyl used in the present specification means a monovalent linear or branched saturated hydrocarbon radical composed of only carbon and hydrogen atoms.
  • alkyl include methyl, ethyl, propyl, butyl, pentyl, nuclears, heptyl, Including, but not limited to, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, etc.
  • aryl in this specification is aromatic by the removal of one hydrogen.
  • the fused ring system may contain an aliphatic ring such as a saturated or partially saturated ring, and must contain one or more aromatic rings.
  • the aliphatic ring also contains nitrogen, oxygen, sulfur, carbonyl, etc. in the ring.
  • the aryl radical include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrycenyl, naphthacenyl,
  • cycloalkyl refers to a monovalent saturated carbocyclic radical composed of one or more rings. Examples of cycloalkyl radicals are
  • halo or halogen used in this specification mean fluorine, chlorine, bromine or iodine atoms.
  • haloalkyl refers to an alkyl substituted with one or more halogens, and examples include, but are not limited to, trifluoromethyl.
  • fluorine substituted aryl in this specification means that one or more fluorine atoms
  • arylalkyl refers to alkyl substituted with one or more aryls.
  • alkoxy and aryloxy used in this specification mean *-0 -alkyl radical and *-0 -aryl radical, respectively, where “alkyl” and “aryl” are as defined above.
  • catalyst activator in this specification can be interpreted as having the same meaning as a co-catalyst, and the catalyst activator specifically described in this specification may be a compound represented by the following formula (1).
  • monomers for the production of ethylene-based polymers such as ethylene homopolymers or copolymers of ethylene and (X-olefin) are aliphatic in order to reduce the miscibility with solvents and the content of aromatic hydrocarbons in the resulting ethylene-based polymer.
  • ethylene-based polymers such as ethylene homopolymers or copolymers of ethylene and (X-olefin) are aliphatic in order to reduce the miscibility with solvents and the content of aromatic hydrocarbons in the resulting ethylene-based polymer.
  • the compound has a high solubility in both linear aliphatic hydrocarbon-based solvents as well as cyclic aliphatic hydrocarbon-based solvents. Therefore, it is suitable for use in continuous solution processes where it is necessary to control a specific amount of catalyst activator. In particular, when it contains it
  • the tetraarylborate compound having an alkylidene anilinium structure cation has excellent high-temperature stability, so it exhibits excellent effects on catalyst activation even at high temperature polymerization temperatures of 160° or higher, and makes it possible to operate commercially, so it is used industrially. The value is high.
  • the tetraaryl borate compound according to an embodiment of the present invention may be represented by the following formula (1).
  • the tetraaryl borate compound has the use of a catalyst activator for activating the main catalyst for the production of an ethylene homopolymer or a copolymer of ethylene and (X-olefin).
  • the tetraaryl borate compound has the use of a catalyst activator.
  • the compound is an aliphatic hydrocarbon system improved by containing a cations of an alkylidene anilinium structure. 2020/174346 7 ? €1/162020/051519
  • the tetraarylborate compound is the following formula (2) or
  • II 11 to II 15 are each independently hydrogen, (0 30) alkyl, halo ((:1 30) alkyl or (06 30) aryl((:1 30) alkyl.]
  • II 11 to II 15 are each independently hydrogen, (0-030) alkyl, halo ((:1 30) alkyl, or 979 56 88 (06 30) aryl((:1 30) alkyl;
  • II is an integer selected from 2 to 6;
  • II 21 and II 22 are each independently hydrogen, (0 30) alkyl, (0 ⁇ 30) alkoxy, halo (0 30) alkyl, 3 30) cycloalkyl, (0 30) alkyl 6 30) aryl,
  • At least one selected from II 1 and II 2 may be a long-chain alkyl, that is, (8 30) alkyl.
  • II 11 to II 15 are each independently hydrogen or (0 30) alkyl; II 1 and! At least one selected from 1 2 may be a long-chain alkyl, wherein II 1 hydrogen or ⁇ 8 30) alkyl, and II 2 may be ((:1 30) alkyl.
  • II 11 to II 15 are each independently hydrogen or
  • ((:1 7) is alkyl; at least one selected from II 1 and! 1 2 is a long-chain alkyl, wherein II 1 is hydrogen or ⁇ 8 30) alkyl, and II 2 is ⁇ 8 30) alkyl. Thing 2020/174346 8 ? €1/162020/051519
  • II 11 to II 15 are each independently hydrogen, methyl or ethyl; At least one selected from Yo! and Yo 2 is a long-chain alkyl, and II 1 hydrogen or ( 8 30) alkyl, and II 2 may be (8 30) alkyl.
  • II 11 to II 15 are each independently hydrogen or
  • ((:1 30)alkyl; II is an integer selected from 2 to 4;
  • the elements 21 and II 22 may each independently be hydrogen or (08-030) alkyl.
  • II 11 to II 15 are each independently hydrogen or
  • ((:1 7) is alkyl; said II is an integer of 3 or 4; said i and II 22 are each independently hydrogen or 8 30) may be alkyl.
  • II 11 to II 15 are each independently hydrogen or
  • ((:1 7)alkyl ((:1 7)alkyl;
  • the above II is an integer of 3 or 4;
  • the above and II 22 may each independently be hydrogen or ((:1 7) alkyl.
  • II 11 to II 15 are each independently hydrogen, methyl or ethyl, and II is an integer of 3 or 4, and II 21 and II 22 are each independently hydrogen or (8 30) May be alkyl.
  • II 11 to II 15 are each independently hydrogen, methyl or ethyl; 1 ⁇ 1 and 2 may be (02 30) alkyl.
  • Formula 3 is II 11 to II 15 are each independently hydrogen, methyl or ethyl, and II is an integer of 3 or 4, and II 21 and II 22 are each independently hydrogen or (02 ⁇ 30) alkyl, and at least one of II 21 and II 22 is
  • one specific compound of the tetraarylborate compound represented by Formula 1 is methyl-methylideneanilinium tetrakis (pentafluorophenyl) borate, 4 -methyl-N-octadecyl-N-octade Silideneanilinium
  • Tetradecyl-tetradecylideneanilinium tetrakis (pentafluorophenyl) borate, hexadecyl-hexadecylideneanilinium tetrakis (pentafluorophenyl) borate and octadecyl-N-octadecylideneanilinium
  • Tetrakis (pentafluorophenyl) borate etc., but are not limited thereto. 2020/174346 9 ? €1/162020/051519
  • Tetrakis (pentafluorophenyl) borate etc., more preferably
  • Tetradecyl-tetradecylideneanilinium tetrakis (pentafluorophenyl) borate, hexadecyl-hexadecylideneanilinium tetrakis (pentafluorophenyl) borate and octadecyl-N-octadecylideneanilinium
  • the tetraarylborate compound according to an embodiment of the present invention may be used as a catalyst activator for preparing an ethylene homopolymer and an ethylene-based copolymer selected from ethylene and a copolymer of ethylene (X-olefin, etc.).
  • Arylborate compounds have remarkably high solubility in aliphatic hydrocarbon-based solvents as well as aromatic hydrocarbon-based solvents. Furthermore, since they can be uniformly dissolved and used even in aliphatic hydrocarbon-based solvents, the realization of more improved catalytic activity is of course
  • the tetraarylborate compound according to an embodiment of the present invention may be prepared by reacting a compound represented by the following formula (4) and a compound represented by the following formula (5) in a hydrocarbon-based solvent.
  • the tetraaryl borate compound may be prepared by reacting the compound represented by the following formula (5).
  • the borate compound can be used as a catalyst activator without separation and purification.
  • [105] 6 is a boron atom
  • element 1 is hydrogen or ((:1 30) alkyl
  • [109] II is ((:1 30) alkyl, but the number of carbons in II is one greater than the number of carbons in II'£]
  • 11 2 is ((:1 30) alkyl, or can be linked to II 1 to form a ring, and the ring is (0 30) alkyl, (0 30) alkoxy, halo((:1 30) alkyl ,(0030)cycloalkyl, (()1 30)alkyl(6 30)aryl,(06 30)aryl,(06 30)aryloxy,
  • the hydrocarbon-based solvent is 11-pentane, pentane, !!-nucleic acid, nucleic acid, 11-heptane, 1-heptane, 11-octane, octane, 11-nonane, nonane, 11-decane and decane, etc.
  • Cyclic aliphatic hydrocarbon-based solvent selected from cyclopentane, cyclonucleic acid, methylcyclonucleic acid, dimethylcyclonucleic acid, ethylcyclonucleic acid, imentane and decahydronaphthalene; and benzene, toluene, xylene, etc. It may be one or two or more mixed solvents selected from aromatic hydrocarbon-based solvents.
  • reaction may be carried out under a temperature condition of 0 to 50 o (:.
  • the reaction may be performed for 10 to 120 minutes, but is not limited as long as it is a point at which the solution in a dispersed or slurry state is completely dissolved during the reaction.
  • the tetraarylborate compound according to an embodiment of the present invention exhibits an excellent effect in activating a single active point catalyst.
  • the single active point catalyst may be a metallocene catalyst.
  • the single active point catalyst may contain a transition metal of Group 4 on the periodic table, and these transition metals may exist in a +2, +3, or +4 type oxidation state.
  • a ligand suitable for the single active point catalyst is anionic non-localized
  • -It may include a bonded group, and the anionic delocalized -bonded group may include a cyclic compound selected from cyclopentadienyl derivatives, indenyl derivatives and fluorenyl derivatives.
  • transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and «-olefin according to an embodiment of the present invention is described above.
  • Tetraarylborate compounds may contain a single active point catalyst containing a group 4 transition metal; and an aluminum compound.
  • the single active point catalyst may be represented by the following chemical formula.
  • This is a transition metal compound based on an indenyl ((1 ⁇ , etc.) group introduced with a nitrogen-containing substituent, and is the core metal as the 4 in the periodic table.
  • the foot transition metal has a solid (]) planar structure, rich in electrons and widely delocalized, and has a structure connected by an indene or its derivative introduced with a nitrogen-containing substituent; an amido group substituted with a silyl group; In particular, indene or its nitrogen-containing substituent 2020/174346 11 ? €1/162020/051519
  • the silyl group connecting the derivative group and the amido group contains both an alkyl group or an alkenyl group and an aryl group that induces a narrow molecular weight distribution rather than a wide molecular weight distribution, which is a disadvantage of diastereomerism and improved solubility in general hydrocarbon-based solvents. It has the structural characteristics of the present invention, and is advantageous in obtaining an ethylene-based copolymer having an increased catalyst efficiency and high molecular weight by combining with a catalyst activator or a catalyst activating composition according to the present invention at high temperatures.
  • M is a transition metal of Group 4 on the periodic table
  • [124] Buy ! Is (06 30) aryl, and the above ! £]aryl may be further substituted with one or more substituents selected from ((:1 30) alkyl, halo(0 30) alkyl and (6 30) aryl(0 30) alkyl;
  • II 2 to II 5 are each independently hydrogen, (0 30) alkyl, (0 30) alkoxy,
  • ((0 30)alkyl(6 30)aryl)(0 30)alkyl, or the 11 2 to 11 5 can be linked with adjacent substituents to form a fused ring, and the fused ring is (0 30) alkyl, (0 30) alkoxy, halo (0 30) alkyl, (3 20) cycloalkyl,
  • ((0 30) alkyl( 6 30) aryl) (0 30) may be further substituted with one or more substituents selected from alkyl and the like;
  • [126] II 9 is ((:1 30) alkyl, 3 20) cycloalkyl or (6 30) aryl ((:1 30) alkyl;
  • Yo ⁇ and II 7 are each independently (0 30) alkyl, halo (0 30) alkyl,
  • ((:1 30)alkoxy(6 30)aryl or(6 30)aryl(0 30)alkyl, or the above 6 and II 7 can be linked to each other to form a ring, and the ring is((:1 30) Alkyl, Halo (C1-C30)alkyl, (C6-C30)aryl (C1-C30)alkyl, (C1-C30)alkoxy,
  • R 8 is hydrogen or (C1-C30)alkyl
  • X 1 and X 2 are each independently halogen, (C1-C30)alkyl, (C2-C20)alkenyl,
  • R a to R d are each independently (C1-C30)alkyl, (C6-C20)aryl,
  • R e to R h are each independently (C1-C30)alkyl, (C6-C20)aryl,
  • the indene-based transition metal compound of the present invention is a single active point catalyst having a structural characteristic including an alkyl group or an alkenyl group and an aryl group at the same time in the silyl group connecting the indenyl group and the amido group into which a nitrogen-containing substituent is introduced. And an aryl group having good injectability of an alkyl group or an alkenyl group and a higher alpha-olefin which is advantageous in terms of solubility.
  • there are two structural features including an alkyl group or an alkenyl group and an aryl group at the same time in the silyl group.
  • the presence of diastereomers was confirmed by H i -NMR.
  • the catalysts developed in the present invention were produced in a ratio of 1:1 to 1:8 despite the presence of diastereomers, and a polymer having a narrow molecular weight distribution was produced, and at high temperatures. In addition, it exhibits properties such as high activity, and is more synergistic when combined with the catalyst activator or catalytic activator composition of the present invention described above. Conventionally, indenyl groups and amido groups have diastereomers connected by silyl groups. It has been reported that the molecular weight distribution has a wide characteristic.
  • the indene-based transition metal compound of the present invention when used in combination with a catalyst activator or a catalytic activator composition, an ethylene-based copolymer with a narrower molecular weight distribution is obtained at high temperatures.
  • a catalyst activator or a catalytic activator composition by various combinations with the above-described catalyst activator or catalyst activator composition, the formation of isomers that make polymerization control difficult is suppressed, and the molecular weight distribution is narrow and the composition composition is narrow. Ethylene-based copolymers of molecular weight can be obtained, and the molecular weight distribution is narrow.
  • Chemical Composition Distribution can be said to be of great commercial value because it can obtain an ethylene-based copolymer with a wide range of properties.
  • the indene-based transition metal compound of the above chemical formula may be represented by the following formula: 8:
  • Alkenylene or 4 7) Alkadienylene can form a fused ring, and the fused ring is (0 30) alkyl, (0 30) alkoxy, halo ((:1 30) alkyl, 3 20) Cycloalkyl, ((1 30) alkyl 6 30) aryl, (06 30) aryl,
  • the indene-based transition metal compound of the above chemical formula is a transition metal of Group 4 on the periodic table, specifically titanium (13 ⁇ 4, zirconium () ⁇ ) or hafnium ⁇ ! 7 )Can be, and more specifically, titanium (II) or zirconium ] ⁇ ).
  • alkyl group for example, methyl group, ethyl group, II-propyl group, isopropyl group, 11-butyl group, isobutyl group, -butyl group, butyl group, 11-pentyl group, neo Pentyl group, amyl group,
  • the (2 20) alkenyl group is, for example, a vinyl group or an allyl group
  • Cycloalkyl group for example, cyclopropyl group, cyclobutyl group, It is a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, or a cyclododecyl group; the (C6-C30) aryl group or
  • (C1-C30) Alkyl (C6-C30) aryl group for example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2, 3-xylyl group, 2, 4 -xylyl group, 2, 5 -xylyl group, 2, 6 -xylyl group, 3, 4 -xylyl group,
  • Biphenyl group fluorenyl group, triphenyl group, naphthyl group or anthracenyl group;
  • Anthracenylmethyl group for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group,
  • tert-butoxy group n-pentoxy group, neopentoxy group, n-nuclear group, n-octoxy group, n-dodecyl group, n-pentadesoxy group, or n -eicosoxy group.
  • R 6 and R 7 are each independently (C1-C30) alkyl
  • (C3-C20) cycloalkyl or (C6-C30) aryl, or the above 11 6 and 11 7 can be linked by (C3-C7) alkylene with or without aromatic rings to form a ring, and the formed ring Is (C1-C30) alkyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C30) alkyl ( C6-C30) aryl and
  • transition metal catalyst composition for preparing a copolymer in the transition metal catalyst composition for preparing a copolymer, in the indene-based transition metal compound of the above chemical formula, II ((:1 30) alkyl, (2 20) alkenyl or
  • Alkyl 6 30 May be aryl; the II 2 to II 5 are each independently hydrogen, ((1 30) alkyl, ((1 30) alkoxy, (0-030) alkyl 6 30 )Aryl,( 6 30)aryl, (6 30)aryloxy, ((:1 30)alkyl( 6 30)aryloxy or
  • aryl ((:1 30) alkyl, or II 2 to II 5 above are (03 7) alkylene, 3 7) alkenylene or (04 7) with or without adjacent substituents and aromatic rings )Can form a fusion ring by connecting with alkadienylene,
  • the fused ring is (0 30) alkyl, (0 30) alkyl 6 30) aryl, (06 30) aryl,
  • (6 30)aryl((:1 30)alkyl, or the above II 6 and II 7 may be linked by alkylene with or without aromatic ring (03 7) to form a ring, and the ring is (0- 030) Alkyl, 6 30) Aryl (0 30) Alkyl, (0 30) Alkoxy, (0020) Cycloalkyl, (6 20) Aryl, ((:1 30) Alkyl (6 30) Aryl and (6 20) It may be further substituted with one or more substituents selected from aryloxy and the like; and II 8 may be hydrogen or (0 30) alkyl.
  • II 1 is more specifically a methyl group, ethyl group, 11 -propyl group, isopropyl group, II -butyl group, vinyl group, allyl group Or it may be a benzyl group; above shows] 1 is more specifically a phenyl group, naphthyl group, biphenyl group, tolyl group, trimethylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, octylphenyl group, decylphenyl group, dodecylphenyl group or
  • the II 2 to II 5 are each independently hydrogen, methyl group, ethyl group, II -propyl group, isopropyl group, II -butyl group, phenyl group, naphthyl group, biphenyl group,
  • the 11 21 to 11 24 are each independently hydrogen, methyl group, ethyl group, I! -Propyl group, isopropyl group, 11 -butyl group, isobutyl group, 2020/174346 16 ? €1/162020/051519
  • It may be a naphthylmethyl group or an anthracenylmethyl group; 11 9 is an isopropyl group,
  • II ⁇ and II 7 are each independently a methyl group, an ethyl group, a II-propyl group,
  • 11-pentadecyl group phenyl group, 2 -tolyl group, 3 -tolyl group, 4 -tolyl group, 2, 3 -xylyl group, 2, 4 -xylyl group,
  • the 11 31 to 11 35 , 11 41 and 11 42 are each independently hydrogen, a methyl group, an ethyl group, I! -Propyl group, isopropyl group, 11 -butyl group, isobutyl group, 2 -methylbutyl group, 8 -butyl group, butyl group, II -pentyl group, neopentyl group, amyl group, II -nuxyl group, II- Octyl group, II -decyl group, II -dodecyl group, II -pentadecyl group, phenyl group,
  • the halogen atom may be exemplified by a fluorine, chlorine, bromine or iodine atom
  • the (0 30) alkyl group is a methyl group, an ethyl group, II-propyl group, isopropyl group, 11- Butyl group, 8 -butyl group, butyl group, 11-pentyl group, neopentyl group, amyl group, 11-nuxyl group, II-octyl group, II-decyl group, II-dodecyl group, II-pentadecyl group or!
  • !- may be exemplified by an eicosyl group; 3 20)
  • the cycloalkyl group may be exemplified by a cyclopropane group, a cyclobutyl group, a cyclopentyl group, a cyclohexanyl group, a cycloheptyl group or an adamantyl group;
  • the above (6 30 )Aryl group may be exemplified by a phenyl group or a naphthyl group; the above (6 30) aryl ((:1 30) an alkyl group
  • the (0 30) alkoxy is a methoxy group, an ethoxy group, an 11-propoxy group, an isopropoxy group, an 11-butoxy group, an 8-butoxy group, a 1631-butoxy group , II-pentoxy group, neopentoxy group, II-nuclear group, II-octoxy group, II-dodecoxy group,! ! -Pentade deception or !! -It can be exemplified as an Echo period;
  • Aryloxy may be exemplified by a phenoxy group, a 4-]1-butylphenoxy group, or a 4-methoxyphenoxy group;
  • Examples of -0 ⁇ 11 3 ⁇ 4 3 ⁇ 4 ⁇ include a trimethylsiloxy group,
  • Triethylsiloxy group tri-propylsiloxy group, triipropylsiloxy group,
  • Dibutylamino group diisobutyla Propyl amino group, di- ! -Hexylamino group, dioctylamino group, di-decylamino group, diphenylamino group, dibenzylamino group, methylethylamino group, methylphenylamino group, benzyl hexylamino group, bistri
  • X 1 and X 2 are each independently halogen, ((1 30) alkyl, 3 20) cycloalkyl, (06 30)aryl,(06 30)aryl(0 30)alkyl, ((:1 30)alkoxy, (6 30)aryloxy ,((:1 30)alkyl( 6 30) Aryloxy,-F 3 ⁇ 4 3 ⁇ 4 2020/174346 19 ? €1/162020/051519
  • Said II-II 11 may be independently (0 30) alkyl or ⁇ 6 20) aryl.
  • X 1 and X 2 is independently fluorine, chlorine, bromine, methyl group, ethyl group, isopropyl group, amyl group, benzyl group, methoxy group, ethoxy group, Nylamino group, dimethylphosphine group, diethylphosphine group, diphenylphosphine group, ethylthio group or
  • It may be an isopropylthio group.
  • the transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and (X-olefin according to an embodiment of the present invention in the indene-based transition metal compound of Formula 8, most specifically, the silver tetravalent Titanium, zirconium or hafnium; II 1 is (0 30) alkyl; II relieveto II 15 are each independently hydrogen or (0-030) alkyl; 11 2 to II 5 are each independently hydrogen or
  • the II 31 to II 35 , II 41 and II 42 are each independently hydrogen or (0 ⁇ 30)alkyl;
  • the III and II are each independently an integer of 1 to 4;
  • the II 9 is (0 30) alkyl or (0020) cycloalkyl; wherein X 1 and 2 are as described in the paragraph above; above, 3 ⁇ 4 are each independently (0 30 ) alkyl or
  • the indene-based transition metal compound of the above formula: 8 may be selected from compounds of the following structure, but is not limited thereto.
  • [153] IV! is tetravalent titanium, zirconium or hafnium
  • X 1 and X 2 are each independently fluorine, chlorine, bromine, methyl group, ethyl group, isopropyl group, amyl group, benzyl group, methoxy group, ethoxy group, isopropoxy group, butoxy group, phenoxy group, 2020/174346 21 ? €1/162020/051519
  • the indene-based transition metal compound according to the present invention is preferably an active catalyst component used in the production of an ethylene homopolymer and an ethylene-based polymer selected from copolymers of ethylene and (X-olefin). While cationizing the core metal by extracting the X I or X 2 ligand in the metal complex, an aluminum compound, a boron compound, or a mixture thereof that can act as an anion can act together as a cocatalyst.
  • Various combinations of the above-described indene-based transition metal compound, the group activator or the group activator composition, and an aluminum compound, a boron compound, or a mixture thereof are also within the scope of the present invention.
  • the aluminum compound may be used as a cocatalyst, and specifically, the following chemical formula 0 or It may be one or two or more selected from the alumina oxide compound of the formula (I); an organic aluminum compound of the formula £; and an organic aluminum oxide compound of the chemical formula or formula 0;
  • 11 51 is (0 30) alkyl, preferably a methyl group or an isobutyl group, and is an integer selected from 5 to 20;
  • II 52 and II 53 are each independently ((:1 30) alkyl;
  • £ is hydrogen or halogen;
  • ] ⁇ is an integer selected from 0 to 3;
  • Yn 54 is ((:1 30) alkyl or ⁇ 6 30) aryl.]
  • the aluminum compound may be specifically, one or a mixture of two or more selected from alkylaluminoxane and organic aluminum.
  • alkyl aluminoxane methyl aluminoxane, modified methyl aluminoxane, or
  • Alkyl aluminum dichloride including isobutyl aluminum dichloride and hexyl aluminum dichloride; dimethyl aluminum hydride,
  • Dialkyl aluminum hydride and the like.
  • the aluminum compound is more specifically, alkylaluminoxane and
  • Trimethyl aluminum triethyl aluminum, trioctyl aluminum, and
  • It may be one or a mixture of two or more selected from triisobutyl aluminum and the like.
  • the aluminum compound can serve as a scavenger to remove impurities that act as poisons to the reaction medium.
  • the preferred range of the ratio between the indene-based transition metal compound of the present invention and the catalyst activator, tetraarylborate compound is the transition metal (M): boron atom (a molar ratio of 1: 0.1 to 100 Can be
  • the preferred range of the ratio between the indene-based transition metal compound of the present invention and the cocatalyst aluminum compound is 1: 1 based on the molar ratio of the transition metal (M): aluminum atom (A1). It can be ⁇ 2,000 days.
  • the indene-based transition metal compound, the tetraaryl borate compound and the aluminum compound of the present invention A preferred range of the ratio of liver is the molar ratio of the central metal (M): boron atom (B): aluminum atom (A1), and may be in the range of 1: 0.1-100: 1 to 2,000, preferably 1: 0.5-30: It may be in the range of 10 to 1,000, more preferably in the range of 1: 0.5-5: W 500.
  • the ratio between the aluminum compounds is out of the above range, the amount of cocatalyst is relatively small, so that the activation of the transition metal compound may not be fully accomplished, so that the catalyst activity of the indene-based transition metal compound may not be sufficient, or a cocatalyst more than necessary is used to produce it.
  • the problem of a significant increase in cost can arise. It exhibits excellent catalytic activity for producing an ethylene homopolymer or a copolymer of ethylene and O C -olefin within the above range, but within the above range depending on the purity of the reaction. 2020/174346 23 ? €1/162020/051519
  • the range of rates may vary.
  • It relates to a method for producing an ethylene homopolymer and an ethylene-based polymer selected from a copolymer of ethylene and (X-olefin) using a homopolymer or a transition metal group composition for preparing a copolymer of ethylene and (X-olefin).
  • the method for producing an ethylene-based polymer using the ethylene homopolymer or a transition metal catalyst composition for producing a copolymer of ethylene and (X-olefin) is in the presence of an appropriate organic solvent, the indene-based transition metal catalyst, catalyst activator, Cocatalyst, and ethylene or
  • the indene-based transition metal catalyst, the catalyst activator, and the cocatalyst component, etc. can be separately introduced into the reactor, or each component can be mixed in advance and introduced into the reactor. Mixing conditions such as sequence, temperature, or concentration are not particularly limited.
  • the catalyst activator may include a tetraaryl borate compound represented by Chemical Formula 1, and the cocatalyst is an aluminum compound and a boron compound described above. It may be one or a mixture of two or more selected from, etc.
  • a method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention is specifically, ⁇
  • Injecting a catalyst activator composition containing the organic solvent used in the manufacturing step without separating; Injecting a single active point catalyst solution containing a non-Group 4 transition metal; Injecting the aluminum compound solution; And (1) Injecting ethylene; may include.
  • the method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention is in a state in which the tetraarylborate compound is dissolved in the organic solvent used in the manufacturing step Because it is injected into the furnace, it is advantageous for continuous solution processing, can solve the drawbacks of solid catalyst activators, and can avoid the use of aromatic hydrocarbon-based solvents such as toluene.
  • the method for producing an ethylene homopolymer or a copolymer of ethylene and an X-olefin according to an embodiment of the present invention may further include the step of injecting this 01 -olefin.
  • a preferred organic solvent that can be used in the above manufacturing method may be an aliphatic hydrocarbon-based solvent, and is hydrocarbon, and specific examples thereof include butane, isobutane, pentane, nucleic acid, heptane, octane, isooctane, nonane, decane, It may be one or two or more mixed solvents selected from linear aliphatic hydrocarbon-based solvents such as dodecane; and cyclic aliphatic hydrocarbon-based solvents such as cyclopentane, methylcyclopentane, cyclonucleic acid, and methylcyclonucleic acid.
  • the organic solvent that can be used in the manufacturing method may be an aromatic hydrocarbon-based solvent.
  • the suitable ethylene pressure is 1 to 1,000 atm, and more preferably 6 to 150 atm.
  • the polymerization reaction temperature is between 25 °0 and 220 °0,
  • preferred examples of the (X-olefins of 03-08 above include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene , 1 -octene, 1 -decene, 1 -dodecene, 1 -hexadecene and 1 -octadecene, etc.
  • Preferred examples of the 04 ⁇ 20 diolefin (D0 no & 1) are 1,3 -butadiene,
  • It may be selected from 1,4 -pentadiene and 2 -methyl-1,3-butadiene, and preferred examples of the 05 ⁇ 20 cycloolefin or cyclodiolefin include cyclopentene,
  • VNB 5-vinylidene-2-norbornene
  • MNB 5-methylene-2-norbornene
  • the above-described olefins can be single-polymerized or two or more kinds of olefins can be co-polymerized.
  • the preferred ethylene pressure and polymerization reaction temperature are as described above. It may be the same as the case of manufacturing an ethylene homopolymer, and the ethylene-based copolymer manufactured according to the method of the present invention usually contains 30% by weight or more of ethylene, preferably 60% by weight or more, and more preferably 60 to 99% by weight. Included in the range of %.
  • a comonomer As a comonomer, it has a density of 3 ⁇ (:10 (X-olefin is used appropriately and has a density of 0.85 / ⁇ 0.960/ ⁇ , and 0.001 ⁇ 2,000 (3/4 of high-density polyethylene from an elastomer with a melting flow rate of 3 ⁇ 4/min)) It can be manufactured easily and economically up to the domain.
  • Hydrogen can be used as a molecular weight control agent to control, usually 5,000 to
  • Mw weight average molecular weight
  • transition metal catalyst composition presented in the present invention exists in a uniform form in the polymerization reactor, it is preferable to apply it to a solution polymerization process conducted at a temperature above the melting point of the polymer.
  • U.S. Patent Nos. 4, 752, 597 As disclosed in the issue, the indene-based transition metal compound, catalyst activator, and co-catalyst are supported on a porous metal oxide support so that it can be used for slurry polymerization or gas phase polymerization as a non-uniform catalyst system. 2020/174346 25? 1/162020/051519
  • the polymerized polymer was analyzed by the method described below.
  • Tetrakis (pentafluorophenyl) borate 3 (3.25 11111101) was added. Then, 300 silver cyclonucleic acid was added to the round bottom flask and stirred at room temperature to prepare a yellow suspension. Dioctane as a solid in the suspended solution Decylaniline 1.95 (3.26_01) was added and stirred at room temperature for 30 minutes. The suspended solution became clear. 2020/174346 27 ? €1/162020/051519
  • the complex 1 synthesized in Preparation Example 1 was used, the solvent used was cyclonucleic acid, and the amount of catalyst used was as described in Table 1 below.
  • the input amount of II is the amount of complex 1 synthesized in Preparation Example 1, the amount of new input is the amount of triisobutylaluminum, and the amount of the catalyst activator is octadecyl octadecylideneanilinium synthesized in Example!
  • the 02 conversion rate of the reactor can be estimated through the reaction conditions and the temperature gradient in the reactor when polymerization into one polymer under each reaction condition.
  • the molecular weight was controlled as a function of the reactor temperature and 1-octene content, and the conditions are shown in Table 1 below. The results are described.
  • Example 2 As shown in Table 1 above, Example 2, which was polymerized using the catalyst composition according to the present invention, exhibited a high conversion rate of ethylene even under high temperature (180 or more) conditions, and low density and high molecular weight. It was confirmed that a high molecular weight ethylene-based copolymer having an MI value could be easily prepared. In addition, Example 2 showed the same level of ethylene conversion even with a small amount of catalyst compared to Comparative Example 1. It was confirmed that the catalyst composition according to the invention exerts an excellent effect on the activation of a single active point catalyst.
  • the new tetraarylborate compound according to the present invention is soluble in aliphatic hydrocarbon-based solvents such as cyclonucleic acid, not aromatic hydrocarbon-based solvents, depending on the selection of the cations of the alkylideneanilinium structure.
  • the transition metal catalyst composition according to the present invention provides a solution-type catalyst activator containing an aliphatic hydrocarbon-based solution to facilitate the operation of commercial processes and can be a means of solving the disadvantages of the solid catalyst activator. have. 2020/174346 29 ? €1/162020/051519

Abstract

La présente invention concerne un nouveau composé de tétraarylborate, une composition de catalyseur le contenant, et un procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfines l'utilisant. Le composé de tétraarylborate présente une excellente stabilité thermique et peut être complètement dissous dans un solvant à base d'hydrocarbure aliphatique, ce qui facilite le fonctionnement de procédés commerciaux et induit de manière efficace l'activation d'un catalyseur monosite. La présente invention utilise le composé de tétraarylborate en tant qu'activateur de catalyseur, ce qui permet d'avoir une activité catalytique élevée et peut fournir des homopolymères d'éthylène de poids moléculaire élevé et des copolymères à base d'éthylène choisis parmi des copolymères d'éthylène, d'alpha-oléfine, et analogues.
PCT/IB2020/051519 2019-02-28 2020-02-24 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant WO2020174346A1 (fr)

Priority Applications (5)

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JP2021532373A JP7164929B2 (ja) 2019-02-28 2020-02-24 新規なテトラアリールボレート化合物、これを含む触媒組成物、およびこれを用いたエチレン単独重合体またはエチレンとα‐オレフィンの共重合体の製造方法
US17/433,268 US20220089790A1 (en) 2019-02-28 2020-02-24 Tetraarylborate Compound, Catalyst Composition Comprising Same, and Method for Preparing Ethylene Homopolymers or Copolymers of Ethylene and a-Olefin by Using Same
EP20762870.2A EP3904360A4 (fr) 2019-02-28 2020-02-24 Nouveau composé de tétraarylborate, composition de catalyseur le contenant, et procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfine l'utilisant
CN202080008790.1A CN113677686A (zh) 2019-02-28 2020-02-24 新的四芳基硼酸盐化合物、包含其的催化剂组合物、以及通过使用其制备乙烯均聚物或乙烯和α烯烃的共聚物的方法
CA3120265A CA3120265C (fr) 2019-02-28 2020-02-24 Nouveau compose de tetraarylborate, composition de catalyseur le contenant, et procede de preparation d'homopolymeres ou de copolymeres d'ethylene et d'alpha-olefine l'utilisant

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KR1020200020828A KR20200105409A (ko) 2019-02-28 2020-02-20 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
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Cited By (1)

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CN114478605A (zh) * 2022-03-07 2022-05-13 万华化学集团股份有限公司 一种高度易溶、高位阻的三核硼酸盐及其制备方法、催化剂体系和烯烃聚合方法

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