WO2018122693A1 - NOUVEAU COMPOSÉ À BASE DE MÉTAL DE TRANSITION DE CYCLOPENTA[B]THIOPHÉNYL, COMPOSITION DE CATALYSEUR À BASE DE MÉTAL DE TRANSITION, PROCÉDÉ DE PRÉPARATION D'HOMOPOLYMÈRES OU DE COPOLYMÈRES D'ÉTHYLÈNE ET DE α-OLÉFINES L'UTILISANT - Google Patents

NOUVEAU COMPOSÉ À BASE DE MÉTAL DE TRANSITION DE CYCLOPENTA[B]THIOPHÉNYL, COMPOSITION DE CATALYSEUR À BASE DE MÉTAL DE TRANSITION, PROCÉDÉ DE PRÉPARATION D'HOMOPOLYMÈRES OU DE COPOLYMÈRES D'ÉTHYLÈNE ET DE α-OLÉFINES L'UTILISANT Download PDF

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WO2018122693A1
WO2018122693A1 PCT/IB2017/058243 IB2017058243W WO2018122693A1 WO 2018122693 A1 WO2018122693 A1 WO 2018122693A1 IB 2017058243 W IB2017058243 W IB 2017058243W WO 2018122693 A1 WO2018122693 A1 WO 2018122693A1
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alkyl
ethylene
transition metal
aryl
compound
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Korean (ko)
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한용규
오연옥
김명일
함형택
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사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
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Publication of WO2018122693A1 publication Critical patent/WO2018122693A1/fr

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    • 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
    • C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
    • 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
    • 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
    • C08F210/02—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
    • 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
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • 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 invention cyclopenta [b] thiophenyl (cyclopenta [b] thiophenyl) groups based novel transition metal compound, the transition with the ethylene homopolymer or ethylene and one or more high catalytic activity for the production of ⁇ - olefin copolymer containing the same It relates to a metal catalyst composition and a method for producing an ethylene homopolymer or a copolymer of ethylene and an ⁇ -olefin using the same.
  • Ziegler-Natta catalyst systems composed of a main catalyst component of a titanium or vanadium compound and a cocatalyst component of an alkylaluminum compound have been generally used for preparing a homopolymer of ethylene or a copolymer of? -Olefin.
  • the Ziegler-Natta catalyst system exhibits high activity against ethylene polymerization, but due to its heterogeneous catalytic activity, the molecular weight distribution of the resulting polymer is generally wide, and in particular, the composition distribution is not uniform in the copolymer of ethylene and ⁇ -olefin. There was this.
  • the metallocene catalyst system composed of a metallocene compound of Group 4 transition metal such as titanium, zirconium, and hafnium and methylaluminoxane as a promoter is a homogeneous catalyst having a single catalytic activity point.
  • polyethylene has narrower molecular weight distribution and uniform composition distribution.
  • the Group 4 transition metal on the periodic table has a rigid planar structure and is rich in electrons and is widely delocalized.
  • a thiophenyl (cyclopenta [b] thiophenyl) group cyclopenta [b] thiophenyl) group; and a substituent to help improve solubility and performance is linked by a fluorenyl or phenoxy group substituted with a carbazole, which can be easily introduced; It has been found that a transition metal compound having a structure in which a cyclopenta [b] thiophenyl group and a phenoxy group are connected by silyl shows excellent catalytic activity in the polymerization of ethylene and olefins.
  • Another object of the present invention is to provide a method for economically preparing an ethylene homopolymer or a copolymer of ethylene and an -olefin using a catalyst composition comprising the transition metal compound from a commercial point of view.
  • Another object of the present invention is a simple synthesis route, which is very economical in terms of catalytic synthesis, and has a high activity in olefin polymerization, and an ethylene homopolymer or ethylene and ⁇ - having various physical properties.
  • An object of the present invention is to provide a polymerization method in which copolymers of olefins can be economically produced from a commercial point of view.
  • One aspect of the present invention for achieving the above object relates to a novel transition metal compound based on a cyclopenta [b] thiophenyl group represented by the following formula (1). More specifically, a cyclopenta [b] thiophenyl group, in which the Group 4 transition metal on the periodic table as a central metal has a rigid planar structure and is rich in electrons and widely delocalized; and Fluorenyl or carbazole-substituted phenoxy groups, which are easily introduced with substituents that help improve solubility and performance, are linked by the cyclopenta [b] thiophenyl group and phenoxy group by silyl It relates to a transition metal compound having a linked structure.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 ;
  • R 5 and R 6 are each independently (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) Aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 5 and R 6 May be linked with (C 4 -C 7) alkylene to form a ring;
  • R 7 to R 9 are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 7 to R 9 can be linked to a (C4-C7) alkenylene with or without adjacent substituents and an aromatic ring to form a fused ring;
  • R a1 to R a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;
  • Ar 1 is fluorenyl or N-carbazole, wherein the fluorenyl or carbazole of Ar 1 may be further substituted with (C1-C20) alkyl;
  • X 1 and X 2 are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C20) ) Aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) Aryloxy, -OSiR a R b R c , -SR d , -NR e R f , -PR g R h or (C 1 -C 20) alkylidene;
  • R a to R d independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;
  • R e to R h are independently of each other (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, ( C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20) arylsilyl;
  • the heteroaryl includes one or more hetero atoms selected from N, O and S.
  • Another aspect of the present invention for achieving the above object is a transition metal compound of Formula 1; And a cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof.
  • the present invention relates to a transition metal catalyst composition for preparing an ethylene homopolymer or a copolymer of ethylene and an ⁇ -olefin.
  • Another aspect of the present invention for achieving the above object relates to a method for producing an ethylene homopolymer or a copolymer of ethylene and ⁇ -olefin using the catalyst composition.
  • the transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by a simple method of high yield and economical method due to the simple synthesis process, and also has excellent thermal stability of the catalyst and high catalytic activity even at high temperature. While maintaining a good copolymerization reactivity with other olefins and can produce a high molecular weight polymer in high yield, it is commercially viable compared to the known metallocene and non-metallocene-based single-site catalyst. Therefore, the transition metal and the catalyst composition including the same according to the present invention can be usefully used for the preparation of ethylene homopolymer or copolymer with ⁇ -olefin having various physical properties.
  • Example 1 1-Production of 100 mg of polymer using the catalyst of Example 1 (1), Example 2 (2), Example 3 (3) and Example 4 (4) and Comparative Example 1 ( ⁇ ) of the present invention
  • the transition metal compound according to one embodiment of the present invention is a transition metal compound based on a cyclopenta [b] thiophenyl group represented by the following Chemical Formula 1, and a Group 4 transition metal on the periodic table as a central metal is Fluent, which has a rigid planar structure, an electron-rich, widely delocalized cyclopenta [b] thiophenylyl group, and a substituent which can easily introduce a substituent to improve solubility and performance.
  • Orenyl or carbazole is substituted by a phenoxy (phenoxy) group; the cyclopenta [b] thiophenyl group has a structure in which the phenoxy group is connected by silyl, high efficiency and high molecular weight ethylene polymer It has an advantageous structural advantage in obtaining.
  • M is a transition metal of Group 4 on the periodic table
  • R 1 to R 4 are each independently hydrogen, (C1-C20) alkyl, (C6-C20) aryl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6 ;
  • R 5 and R 6 are each independently (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C20) alkyl (C6-C20) Aryl, (C6-C20) aryl (C1-C20) alkyl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 5 and R 6 May be linked with (C 4 -C 7) alkylene to form a ring;
  • R 7 to R 9 are each independently hydrogen, (C1-C20) alkyl, halo (C1-C20) alkyl, halogen, (C6-C20) aryl, (C3-C20) heteroaryl, -OR a1 , -SR a2 , -NR a3 R a4 or -PR a5 R a6, or R 7 to R 9 can be linked to a (C4-C7) alkenylene with or without adjacent substituents and an aromatic ring to form a fused ring;
  • R a1 to R a6 are each independently (C1-C20) alkyl or (C6-C20) aryl;
  • Ar 1 is fluorenyl or N-carbazole, wherein the fluorenyl or carbazole of Ar 1 may be further substituted with (C1-C20) alkyl;
  • X 1 and X 2 are each independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl (C1-C20) alkyl, ((C1-C20) alkyl (C6-C20) ) Aryl) (C1-C20) alkyl, (C1-C20) alkoxy, (C6-C20) aryloxy, (C1-C20) alkyl (C6-C20) aryloxy, (C1-C20) alkoxy (C6-C20) Aryloxy, -OSiR a R b R c , -SR d , -NR e R f , -PR g R h or (C 1 -C 20) alkylidene;
  • R a to R d independently of one another are (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl or ( C3-C20) cycloalkyl;
  • R e to R h are independently of each other (C1-C20) alkyl, (C6-C20) aryl, (C6-C20) ar (C1-C20) alkyl, (C1-C20) alkyl (C6-C20) aryl, ( C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20) arylsilyl;
  • the heteroaryl includes one or more hetero atoms selected from N, O and S.
  • alkyl refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, examples of which alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl , Pentyl, hexyl, octyl, nonyl, and the like.
  • aryl refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, wherein a single or fused ring contains 4 to 7, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a system, including a form in which a plurality of aryl is connected by a single bond.
  • Fused ring systems can include aliphatic rings, such as saturated or partially saturated rings, and necessarily include one or more aromatic rings.
  • the aliphatic ring may include nitrogen, oxygen, sulfur, carbonyl, and the like in the ring.
  • aryl radical examples include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, 9,10-dihydro Anthracenyl and the like.
  • heteroaryl refers to an aryl group containing 1 to 4 heteroatoms selected from N, O and S as the aromatic ring skeleton atom, and wherein the remaining aromatic ring skeleton atom is carbon.
  • heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected by a single bond.
  • heteroaryl group examples include pyrrole, quinoline, isoquinoline, pyridine, pyrimidine, oxazole, thiazole, thiadiazole, triazole, imidazole, benzoimidazole, isoxazole, benzoisoxazole, thiophene, Benzothiophene, furan, benzofuran and the like.
  • cycloalkyl herein refers to a monovalent saturated carbocyclic radical composed of one or more rings.
  • examples of cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • halo or halogen refers to a fluorine, chlorine, bromine or iodine atom.
  • haloalkyl refers to alkyl substituted with one or more halogens, and examples thereof include trifluoromethyl and the like.
  • alkoxy and aryloxy refer to -O-alkyl radicals and -O-aryl radicals, where “alkyl” and “aryl” are as defined above.
  • the transition metal compound based on the cyclopenta [b] thiophenyl group of Chemical Formula 1 may be a transition metal compound represented by the following Chemical Formula 2 or 3:
  • R 5 and R 6 are each independently (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or (C 6 -C 20) aryl;
  • R 8 and R 9 are each independently hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or halogen, or R 8 and R 9 are , , or Connected to form a fused ring;
  • R 11 and R 12 are each independently (C 1 -C 20) alkyl
  • R 13 , R 14 and R 15 are each independently hydrogen or (C 1 -C 20) alkyl.
  • M of the transition metal compound is a transition metal of Group 4 on the periodic table, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf), more preferably Titanium.
  • R 1 to R 4 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl Neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, phenyl, pyridyl, methoxy, ethoxy, butyl Methoxy, methylthio, ethylthio, dimethylamino, methylethylamino, diethylamino, diphenylamino, dimethylphosphine, diethylphosphine or diphenylphosphine.
  • R 1 is (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl
  • R 2 is hydrogen
  • R 3 and R 4 are each independently hydrogen, (C 1 -C20) alkyl, preferably (C1-C10) alkyl, (C1-C20) alkoxy, preferably (C1-C10) alkoxy or di (C1-C20) alkylamino, preferably di (C1-C10) Alkylamino.
  • R 1 , R 3 and R 4 are each independently (C 1 -C 10) alkyl, R 2 may be hydrogen.
  • R 1 , R 3 and R 4 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl, R 2 is hydrogen Can be.
  • R 1 is (C1-C10) alkyl
  • R 2 and R 3 are hydrogen
  • R 4 is (C1-C10) alkyl, (C1-C10) alkoxy or di (C1) -C10) alkylamino.
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl
  • R 2 and R 3 are hydrogen
  • R 4 is a methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl
  • sec-butyl may be a methoxy, ethoxy, butoxy, dimethylamino, methyl-ethylamino or diethylamino-butyl, tert .
  • R 1 is (C 1 -C 10) alkyl
  • R 2 and R 4 are hydrogen
  • R 3 is (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy or di (C 1) -C10) alkylamino.
  • R 1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl or tert -butyl
  • R 2 and R 4 are hydrogen
  • R 3 may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, methoxy, ethoxy, butoxy, dimethylamino, methylethylamino or diethylamino .
  • the R 5 and R 6 are each independently selected from methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec - butyl, tert - butyl, n- pentyl, neo Pentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoromethyl, trifluoromethyl, perfluoroethyl, Perfluoropropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, tolyl, xylyl, trimethylphenyl, t
  • R 5 and R 6 are each independently (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) alkyl, preferably halo (C 1) -C10) alkyl or (C6-C20) aryl, preferably (c6-C12) aryl.
  • R 5 and R 6 may be each independently methyl, ethyl or phenyl.
  • R 7 to R 9 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl , Neopentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, fluoromethyl, trifluoromethyl, perfluoro Ethyl, perfluoropropyl, chloro, fluoro, bromo, phenyl, biphenyl, fluorenyl, triphenyl, naphthyl, anthracenyl, benzyl, naphthylmethyl, anthracenylmethyl, pyridyl,
  • R 7 to R 9 are each independently hydrogen, (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) alkyl, preferably halo It may be (C1-C10) alkyl or halogen.
  • R 7 to R 9 may be each independently hydrogen, methyl, ethyl, tert -butyl or fluoro.
  • R 7 is hydrogen
  • R 8 and R 9 are each independently hydrogen, (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl, halo (C 1 -C 20) Alkyl, preferably halo (C1-C10) alkyl or halogen, wherein R 8 and R 9 are , , or Can be connected to form a fused ring.
  • R 7 and R 9 are hydrogen, R 8 is (C1-C10) alkyl or halogen, or R 8 and R 9 is Can be connected to form a fused ring.
  • R 7 and R 9 are hydrogen
  • R 8 may be methyl, ethyl, tert -butyl or fluoro, wherein R 8 and R 9 are Can be connected to form a fused ring.
  • R 11 and R 12 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neo Pentyl, amyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-pentadedecyl;
  • R 13 , R 14 and R 15 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec -butyl, tert -butyl, n-pentyl, neopentyl, amyl, n -Hexyl, n-oct
  • R 11 and R 12 is (C1-C20) alkyl
  • R 13 , R 14 and R 15 may be each independently hydrogen or (C1-C10) alkyl.
  • X 1 and X 2 are each independently fluoro, chloro, bromo, methyl, ethyl, isopropyl, amyl, cyclopropyl, cyclobutyl, cyclopentyl, cichlorohexyl, phenyl , Naphthyl, benzyl, methoxy, ethoxy, isopropoxy, tert -butoxy, phenoxy, 4-tert-butylphenoxy, trimethylsiloxy, tert -butyldimethylsiloxy, dimethylamino, diphenylamino, Dimethylphosphine, diethylphosphine, diphenylphosphine, ethylthio or isopropylthio.
  • X 1 and X 2 may be (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl or halogen.
  • the X 1 and X 2 may be a methyl or chloro.
  • R 11 , R 12 , R 14 and R 15 are each independently (C 1 -C 20) alkyl, preferably (C 1 -C 10) alkyl; R 13 may be hydrogen.
  • the transition metal compound may be selected from compounds having the following structure, but is not limited thereto.
  • the transition metal compound according to the present invention is preferably X 1 and X in the transition metal complex in order to be an active catalyst component used in the preparation of an ethylene polymer selected from ethylene homopolymers and copolymers of ethylene and ⁇ -olefins.
  • 2 Ligands can be catalyzed to the central metal and catalyze the counterion with weak binding ability, that is, an aluminum compound, a boron compound, or a mixture thereof, which can act as an anion, and act as a cocatalyst.
  • a catalyst composition comprising a is also within the scope of the present invention.
  • the aluminum compound which may be used as a promoter may be specifically an aluminoxane compound of Formula 4 or 5, an organoaluminum compound of Formula 6 or an organoaluminum oxide of Formula 7 or Formula 8 It may be one or two or more selected from compounds.
  • R 51 is (C1-C20) alkyl, preferably methyl or isobutyl, m and q are each an integer of 5 to 20; R 52 and R 53 are each (C1-C20) alkyl; E is hydrogen or halogen; r is an integer from 1 to 3; R 54 is (C1-C20) alkyl or (C6-C20) aryl.
  • the aluminum compound which may be used include methyl aluminoxane, improved methyl aluminoxane and tetraisobutyl aluminoxane;
  • organoaluminum compounds include trialkylaluminum, dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum
  • Dialkyl aluminum chloride including diisobutyl aluminum chloride, and dihexyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, propyl aluminum dichloride, isobutyl aluminum dichloride, and alkyl including hexyl aluminum dichloride
  • Dialkyl aluminum hydrides including aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydr
  • the aluminum compound is preferably one or two or more mixtures selected from alkylaluminoxane compounds and trialkylaluminum, more preferably methylaluminoxanes, improved methylaluminoxanes, tetraisobutylalumina Or a mixture of two or more selected from noxic acid, trimethylaluminum, triethylaluminum trioctylaluminum and triisobutylaluminum.
  • Boron compounds that can be used as cocatalysts in the present invention have been known in US Pat. No. 5,198,401, and may be selected from boron compounds represented by the following formulas (9) to (11).
  • B is a boron atom
  • R 41 is phenyl, said phenyl being 3 to 5 substituents selected from fluoro, (C1-C20) alkyl unsubstituted or substituted with fluoro, and (C1-C20) alkoxy unsubstituted or substituted with fluoro; May be further substituted
  • R 42 represents a (C5-C7) aromatic radical or a (C1-C20) alkyl (C6-C20) aryl radical, a (C6-C20) aryl (C1-C20) alkyl radical, for example triphenylmethylium Radical
  • Z is nitrogen or phosphorus atom
  • R 43 is a (C1-C50) alkyl radical or an anninium radical substituted with two (C1-C10) alkyl with a nitrogen atom
  • p is an integer of 2 or 3.
  • Preferred examples of the boron-based cocatalysts include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro Phenyl) borane, tris (3,4,5-trifluorophenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis (3,4 , 5-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phen
  • ferrocenium tetrakis (pentafluorophenyl) borate 1,1'- dimethyl ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, and triphenyl Methylinium tetrakis (pentafluorophenyl) borate, triphenylmethyl tetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis ( Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-bistri
  • the cocatalyst may serve as a scavenger to remove impurities that act as poisons to the catalyst in the reactants.
  • the preferred range of the ratio between the transition metal compound and the promoter of the present invention is based on the molar ratio ratio of the transition metal (M) to the aluminum atom (Al). 1: 10 to 5,000.
  • the preferred range of the ratio between the transition metal compound and the promoter of the present invention is a transition metal (M): boron atom on a molar ratio basis.
  • the molar ratio of (B): aluminum atom (Al) may be in the range of 1: 0.1 to 100: 10 to 3,000, more preferably in the range of 1: 0.5 to 5: 100 to 3,000.
  • the ratio between the transition metal compound and the promoter of the present invention is out of the above range, the amount of the promoter is relatively small so that the activation of the transition metal compound may not be completed, and thus the catalytic activity of the transition metal compound may not be sufficient, or more than necessary.
  • the use of cocatalysts can lead to a significant increase in production costs. It shows excellent catalytic activity for producing ethylene homopolymer or copolymer of ethylene and ⁇ -olefin within the above range, and the range of the ratio will vary depending on the purity of the reaction.
  • a method for preparing an ethylene polymer using the transition metal catalyst composition may be carried out by contacting the transition metal catalyst, the promoter, and ethylene or, if necessary, an ⁇ -olefin comonomer in the presence of a suitable organic solvent.
  • the transition metal catalyst and the cocatalyst component may be separately introduced into the reactor, or each component may be previously mixed and introduced into the reactor, and mixing conditions such as the order of input, temperature or concentration are not particularly limited.
  • Preferred organic solvents that can be used in the preparation method are (C3-C20) hydrocarbons, specific examples of which are butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclo Hexane, benzene, toluene, xylene, etc. are mentioned.
  • ethylene when preparing the ethylene homopolymer, ethylene is used alone as a monomer, wherein a suitable pressure of ethylene is 1 to 1000 atm and more preferably 10 to 150 atm. Moreover, it is effective that polymerization reaction temperature is 25-200 degreeC, Preferably it is 50-180 degreeC, More preferably, it is 100-180 degreeC, More preferably, it is 130-180 degreeC.
  • At least one selected from C3 to C18 ⁇ -olefins, C5 to C20 cycloolefins, styrene and derivatives of styrene may be used as a comonomer together with ethylene.
  • Preferred examples of the ⁇ -olefin of ⁇ C18 include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, It may be selected from the group consisting of 1- tetradecene, 1- hexadecene and 1-octadecene, preferred examples of C5-C20 cycloolefins are cyclopentene, cyclohexene, norbonene and phenylnorbornene Styrene and its derivatives may be selected from styrene, alpha-methylstyrene, p-methylstyrene and 3-chloromethylstyrene.
  • ethylene may be polymerized alone or copolymerized with two or more kinds of olefins, and more preferably 1-butene, 1-hexene, 1-octene or 1-decene and ethylene may be copolymerized.
  • the preferred ethylene pressure and polymerization temperature may be the same as in the case of preparing the ethylene homopolymer, and the copolymer prepared according to the method of the present invention usually contains 30 wt% or more of ethylene, and preferably 60 wt%. It contains at least% ethylene, more preferably in the range of 60 to 99% by weight.
  • the catalyst of the present invention when used, it has a density of 0.850 g / cc to 0.960 g / cc and a melt flow rate of 0.001 to 15 dg / min using ethylene and a C-C18 ⁇ -olefin as a comonomer. It can be easily and economically produced from the elastomer having a high density polyethylene (HDPE) region.
  • HDPE high density polyethylene
  • hydrogen may be used as a molecular weight regulator to control the molecular weight in the preparation of the ethylene homopolymer or copolymer according to the present invention, and generally has a weight average molecular weight (Mw) in the range of 5,000 to 1,000,000 g / mol.
  • the catalyst composition presented in the present invention is present in a uniform form in the polymerization reactor, it is preferable to apply to the solution polymerization process carried out at a temperature above the melting point of the polymer.
  • it may be used in slurry polymerization or gas phase polymerization in the form of a heterogeneous catalyst composition obtained by supporting the transition metal catalyst and the promoter on a porous metal oxide support.
  • Cyclohexane a polymerization solvent
  • a polymerization solvent was used after passing through a tube filled with molecular sieve 5 ⁇ and activated alumina and bubbling with high purity nitrogen to sufficiently remove moisture, oxygen, and other catalyst poisons.
  • the polymerized polymer was analyzed by the method described below.
  • Freeslate Rapid GPC was used to measure the solvent at 1,2,3-trichlorobenzene at 135 ° C. at a rate of 1.0 mL / min, and molecular weight was corrected using PL polystyrene standards.
  • the ratio of ethylene and ⁇ -olefin of the copolymer was quantified using an infrared spectrometer.
  • PolymerChar A-CEF was used to measure the AF (amorphous fraction) of the polymer by branching distribution analysis of the polymer.
  • the reaction was cooled to room temperature and then the solvent was removed in vacuo under a nitrogen atmosphere. After removal of the solvent, warm methylcyclohexane was added to separate the byproducts through a celite filter. The filtrate obtained from the filter was dried in vacuo and a mixed solvent of methylcyclohexane and hexane was added to give a reddish brown precipitate at ⁇ 30 ° C. to obtain the title compound C in solid form.
  • p-cresol (30.0 g, 277 mmol, 1 equiv) was dissolved in MeCN (3000 mL).
  • p-TSA p-Toluenesulfonic acid monohydrate
  • NIS N-iodosuccinimide
  • the formed product was extracted with ether (200 mL ⁇ 2), and the recovered organics were treated with aqueous Na 2 SO 3 solution and distilled water, and then dried over anhydrous Na 2 SO 4 to remove the solvent.
  • the resulting compound (2-iodo-4-methylphenol; 56.5 g, 87% yield) was used for the next reaction without further purification.
  • 2-iodo-4-methylphenol (56.5 g, 240 mmol, 1 equiv) was dissolved in anhydrous THF (250 mL) under a nitrogen atmosphere.
  • DIPEA N, N-Diisopropylethylamine
  • MOMCl Chloromethyl methyl ether
  • the organic layer was extracted with toluene (100 mL ⁇ 3), then treated with distilled water and anhydrous Na 2 SO 4 , and dried to obtain a crude product.
  • the crude product was purified by Kugelrohr distillation to give the target compound Compound E6 as a black oil (32.2g, 85% yield).
  • n- BuLi 2.5 M in hexanes, 91 mmol
  • compound G6 70 mmol
  • toluene 200 mL
  • dichlorodiethylsilane 210 mmol
  • the inorganic salts were removed through celite filtration, and after removing the solvent, excess dichlorodiethylsilane was removed in vacuo to obtain the target compound H6 (99% yield), which was used in the next reaction without further purification.
  • n- BuLi 2.5 M in hexanes, 31.6 mmol
  • the reaction mixture was raised to room temperature and then stirred for 2 hours. After stirring was complete, the mixture was cooled to -78 ° C, and then a toluene (14 mL) solution of compound H6 (33.1 mmol) was added through a syringe.
  • the reaction mixture solution was raised to room temperature, stirred for 3 hours, and added to distilled water (200 mL) to terminate the reaction.
  • Comparative Catalyst 1 was prepared using the method of Examples 1 to 5.
  • Comparative catalyst 2 was prepared using the method of Examples 1 to 5.
  • the reaction solution was transferred to a pressure vessel, followed by Pd (dba) 2 (0.83 g, 1.00 mmol, 0.01 equiv), RuPhos [S. Buchwald, J. Am. Chem . Soc . , 2004 , 126 (40), 13028-13032] (1.92 g, 4.00 mmol, 0.04 equiv) and 2-bromo-1- (methoxymethoxy) -4-methylbenzene (23.7 g, 103 mmol, 1equiv) It was added in turn.
  • the reaction solution was diluted with THF (50 mL) and NMP (100 mL). After stirring the reaction solution at 100 ° C.
  • the obtained white solid (23.1 g, 74.0 mmol) was dissolved in a mixed solution of methanol (220 mL) and THF (220 mL), and HCl (aq) (12M, 2.2 mL) was added thereto, followed by stirring at 60 ° C. for 12 hours. Distilled water (1000 mL) was added to terminate the reaction. After completion of the reaction, the product was extracted by treatment with ether (200 mL x 2), and then treated with distilled water, dried over anhydrous Na 2 SO 4 and the solvent was removed to give the compound a in the form of a white solid (19.3 g, 97% ).
  • Comparative Catalyst 3 was prepared in the same manner as Compound 6 of Example 6 (91% yield).
  • the polymerization reaction proceeded for 1 to 5 minutes, or the polymerization was terminated at a time when the resulting polymer did not exceed 100 to 200 mg.
  • the reactor temperature was cooled to room temperature and ethylene in the reactor was slowly evacuated to remove. The resulting polymer was then dried in vacuo.
  • the copolymerization of ethylene and 1-hexene using the catalyst of Examples 1 to 5 of the present invention has a copolymerization characteristic compared to the case of using the catalyst of Comparative Examples 1, 2 and 3 Can be.
  • the activity is higher than the comparative example.
  • the catalytic activity is slightly lower than that of Comparative Example 4, but it is found that the copolymerization characteristics are very excellent compared to Comparative Example 4 due to the very high content of comonomer 1-hexene in the copolymer. Can be.
  • Example at the polymerization temperature of 150 °C showed about 2 to 45 times higher than the catalyst of Comparative Example 1, about 10 to 213 times compared to the catalyst of Comparative Example 2, about 1.7 to 33 times higher than the catalyst of Comparative Example 3 .
  • the catalyst of the present invention when used as a polymerization catalyst, it can be seen that a copolymer having a high comonomer content can be prepared while maintaining high polymerization activity at a high polymerization temperature of 150 ° C.
  • the transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by a simple method of high yield and economical method due to the simple synthesis process, and also has excellent thermal stability of the catalyst and high catalytic activity even at high temperature. While maintaining a good copolymerization reactivity with other olefins and can produce a high molecular weight polymer in high yield, it is commercially viable compared to the known metallocene and non-metallocene-based single-site catalyst. Therefore, the transition metal and the catalyst composition including the same according to the present invention can be usefully used for the preparation of ethylene homopolymer or copolymer with ⁇ -olefin having various physical properties.

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Abstract

La présente invention concerne un nouveau composé de métal de transition basé sur un groupe cyclopenta[b]thiophényl, une composition de catalyseur à base de métal de transition, comprenant celui-ci et ayant une activité catalytique élevée, pour la préparation d'homopolymères ou de copolymères d'éthylène et d'une ou de plusieurs alpha-oléfines, et un procédé de préparation d'homopolymères ou de copolymères d'éthylène et d'alpha-oléfines l'utilisant.
PCT/IB2017/058243 2016-12-30 2017-12-21 NOUVEAU COMPOSÉ À BASE DE MÉTAL DE TRANSITION DE CYCLOPENTA[B]THIOPHÉNYL, COMPOSITION DE CATALYSEUR À BASE DE MÉTAL DE TRANSITION, PROCÉDÉ DE PRÉPARATION D'HOMOPOLYMÈRES OU DE COPOLYMÈRES D'ÉTHYLÈNE ET DE α-OLÉFINES L'UTILISANT WO2018122693A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114315916A (zh) * 2021-12-30 2022-04-12 山东京博石油化工有限公司 一种桥连含氧、硫杂环结构的茂金属化合物及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141690B2 (en) * 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
US20100267908A1 (en) * 2004-08-27 2010-10-21 Mitsui Chemicals, Inc. Catalyst for olefin polymerization, process for producing olefin polymer, olefin copolymer, novel transition metal compound, and process for producing transition metal compound
JP2011084508A (ja) * 2009-10-15 2011-04-28 Sumitomo Chemical Co Ltd 遷移金属錯体
WO2015183017A1 (fr) * 2014-05-29 2015-12-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de métal de transition, composition de catalyseur de métal de transition pour la polymérisation d'oléfine contenant ledit composé, et procédé de préparation d'homopolymère d'éthylène ou de copolymère d'éthylène et d'une alpha-oléfine utilisant cette composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7141690B2 (en) * 2002-02-08 2006-11-28 Sumitomo Chemical Company, Limited Transition metal complexes, ligands, polymerization catalysts for olefins, and process for production of olefin polymers
US20100267908A1 (en) * 2004-08-27 2010-10-21 Mitsui Chemicals, Inc. Catalyst for olefin polymerization, process for producing olefin polymer, olefin copolymer, novel transition metal compound, and process for producing transition metal compound
JP2011084508A (ja) * 2009-10-15 2011-04-28 Sumitomo Chemical Co Ltd 遷移金属錯体
WO2015183017A1 (fr) * 2014-05-29 2015-12-03 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 Nouveau composé de métal de transition, composition de catalyseur de métal de transition pour la polymérisation d'oléfine contenant ledit composé, et procédé de préparation d'homopolymère d'éthylène ou de copolymère d'éthylène et d'une alpha-oléfine utilisant cette composition

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KIM, S. H.: "Preparation of Thiophene-Fused and Tetrahydroquinoline- Linked Cyclopentadienyl Titanium Complexes for Ethylene/ a-Olefin Copolymerization", CATALYSTS, 6 February 2013 (2013-02-06), pages 104 - 124, XP008166053, Retrieved from the Internet <URL:DOI:10.3390/catal3010104> *
SENDA, T.: "Titanium Complexes of Silicon-Bridged Cyclopentadienyl- Phenoxy Ligands Modified with Fused-Thiophene: Synthesis, Characterization, and Their Catalytic Performance in Copolymerization of Ethylene and 1-Hexene", ORGANOMETALLICS, 2009, pages 6915 - 6926, XP055090319 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114315916A (zh) * 2021-12-30 2022-04-12 山东京博石油化工有限公司 一种桥连含氧、硫杂环结构的茂金属化合物及其应用
CN114315916B (zh) * 2021-12-30 2023-11-07 山东京博石油化工有限公司 一种桥连含氧、硫杂环结构的茂金属化合物及其应用

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