WO2019064247A1 - Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition - Google Patents

Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition Download PDF

Info

Publication number
WO2019064247A1
WO2019064247A1 PCT/IB2018/057534 IB2018057534W WO2019064247A1 WO 2019064247 A1 WO2019064247 A1 WO 2019064247A1 IB 2018057534 W IB2018057534 W IB 2018057534W WO 2019064247 A1 WO2019064247 A1 WO 2019064247A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
group
aryl
transition metal
ethylene
Prior art date
Application number
PCT/IB2018/057534
Other languages
English (en)
Korean (ko)
Inventor
신동철
오연옥
Original Assignee
사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180115040A external-priority patent/KR102643986B1/ko
Application filed by 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 filed Critical 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디
Priority to EP18862289.8A priority Critical patent/EP3689884A4/fr
Priority to CA3075240A priority patent/CA3075240A1/fr
Priority to RU2020114610A priority patent/RU2783400C2/ru
Priority to US16/650,848 priority patent/US10919992B2/en
Priority to CN201880063246.XA priority patent/CN111148748B/zh
Priority to JP2020516841A priority patent/JP7177148B2/ja
Publication of WO2019064247A1 publication Critical patent/WO2019064247A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/28—Titanium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/20—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • 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 novel transition metal catalyst composition having a high catalytic activity for the production of a novel indene-based transition metal compound, an ethylene homopolymer containing the same, or a copolymer of ethylene and at least one alpha -olefin, an ethylene homopolymer or an ethylene- Olefins and copolymers of ethylene homopolymers or copolymers of ethylene and? -Olefins.
  • the so-called Ziegler-Natta catalyst system composed of the main catalyst component of a titanium or vanadium compound and the cocatalyst component of an alkyl aluminum compound has been generally used for preparing a copolymer of ethylene with a homopolymer or an? -Olefin.
  • the Ziegler-Natta catalyst system exhibits high activity for ethylene polymerization, the molecular weight distribution of the resulting polymer is generally broad due to the uneven catalytic activity point, and in particular, the disadvantage that the composition distribution is not uniform in the copolymer of ethylene and? .
  • metallocene catalyst system comprising a metallocene compound of Group 4 transition metal such as titanium, zirconium, and hafnium and a promoter, methylaluminoxane. Since the metallocene catalyst system is a homogeneous catalyst having a catalytic activity point of a single species, it is characterized in that polyethylene having a narrow molecular weight distribution and uniform composition distribution can be produced as compared with the conventional Ziegler-Natta catalyst system.
  • the polymerization activity is rapidly decreased and the? -Hydrogenolysis reaction predominates and the weight average molecular weight (Mw) Are not suitable for preparing high molecular weight polymers of 100,000 or more.
  • a so-called geometrically constrained nonmetalocene catalyst (Aka single-site catalyst).
  • EP 0416815 and EP 0420436 disclose an example in which an amide group is linked in the form of a ring to one cyclopentadiene ligand.
  • EP 0842939 a phenol-based ligand as an electron donor compound is reacted with a cyclopentadiene ligand An example of a catalyst in the form of a ring is shown.
  • a transition metal of the group 4 on the periodic table has a rigid planar structure and is rich in electrons and widely separated,
  • An alkyl group or an alkenyl group and an aryl group at the same time to a silyl group having a structure in which an indene or its derivative group is bonded to an amido group substituted with a silyl group,
  • Transition metal compound having a structural characteristic that is excellent in high temperature activity in the polymerization of ethylene and olefins and has excellent solubility in solvents such as n-hexane and cyclohexane,
  • the catalysts developed in the present invention despite the presence of diastereomeric properties Jaryang distribution is produced polymer is narrow, even in a high temperature, thereby completing the present invention and found to have the properties such as showing a high activity.
  • Another object of the present invention is to provide a process for economically producing an ethylene homopolymer or a copolymer of ethylene and an? -Olefin from a commercial standpoint using a catalyst composition comprising the above transition metal compound.
  • Another object of the present invention is to provide a method for producing a copolymer of ethylene and an? -Olefin, wherein the transition metal compound is used as a graph showing a chemical composition distribution of a single-pole or double-pole graph.
  • the present invention relates to a method for producing a transition metal compound, which comprises, as a center metal, an indene or a derivative thereof having a quadruple transition metal on the periodic table having a rigid plane structure and being electron-
  • the present invention relates to a transition metal compound having a structure which has a structure linked by a halogen atom, a halogen atom, a halogen atom, a halogen atom, a halogen atom, a halogen atom, a halogen atom, will be.
  • M is a transition metal of Group 4 on the Periodic Table
  • R 1 is (C 1 -C 20) alkyl or (C 2 -C 20) alkenyl and the alkyl or alkenyl of R 1 is halogen, (C 6 -C 30) aryl and (C 6 -C 20) Lt; / RTI > may be further substituted with one or more substituents selected from the group consisting of;
  • Ar 1 is (C6-C30) aryl, and the aryl of Ar 1 is a (C1-C20) alkyl, halo (C1-C20) alkyl and (C6-C30) aryl (C1-C20) is selected from the group consisting of alkyl Which may be further substituted with one or more substituents;
  • R 2 to R 5 are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl, (C6-C30) aryloxy, (CrC20) C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, wherein R 2 to R 5 may be connected to an adjacent substituent may form a fused ring, wherein the formed fused ring is (C1-C20) alkyl, (C6-C30) aryl, (C6-C30) aryloxy, (C6-C30) alkoxy, halo (C1- C20) alkyl, (C3- C20) cycloalkyl, (C 1 -C 20) alkyl (C 6
  • R 9 is (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 6 -C 30) aryl (C 1 -C 20) alkyl;
  • R 6 and R 7 are independently selected from the group consisting of (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, aryl, (C1-C20) alkoxy (C6-C30) aryl or (C6-C30) aryl (C1-C20) alkyl or, wherein R 6 and R 7 are connected to each other may form a ring, the formed ring is (C1-C60) alkyl, (C6-C60) aryl, (C6-C60) (C1-C20) alkyl (C6-C30) aryl and (C6-C20) aryloxy;
  • R < 8 &gt is hydrogen or (C1-C20) alkyl
  • X 1 and X 2 are independently of each other selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl ((C 1 -C 20) alkyl (C 6 -C 30) aryl) ) aryloxy, (C1-C20) alkoxy (C6-C30) aryloxy, -OSiR a R b R c, -SR d, -NR e R f, -PR g R h , or (C1-C20) alkylidene and ;
  • R a to R d are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) C3-C20) cycloalkyl;
  • R e to R h are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20) arylsilyl;
  • a transition metal compound represented by Formula 1 represented by Formula 1; And a cocatalyst selected from an aluminum compound, a boron compound or a mixture thereof, or a transition metal catalyst composition for preparing a copolymer of ethylene and an? -Olefin.
  • a method for preparing a copolymer of ethylene homopolymer or ethylene and an alpha -olefin using the transition metal catalyst composition is provided.
  • R 1 to R 9 and Ar 1 are the same as defined in the above formula (1).
  • a transition metal compound for use in producing a copolymer of ethylene and an? -Olefin having a GPC graph of a single rod is provided.
  • a method for preparing a copolymer of ethylene and an -olefin wherein the transition metal compound is used as a graph showing a chemical composition distribution of a monobon or a bimodal curve.
  • the transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by a high synthesis rate and an economical method and is excellent in thermal stability of the catalyst,
  • the present invention has commercial utility in comparison with the already known metallocene and non-metallocene single-site catalysts since it can produce a polymer having a high copolymerization reactivity with a high molecular weight and a high molecular weight.
  • the present invention has developed catalysts that exhibit narrow molecular weight distribution characteristics, such as single-site catalysts, despite the fact that they are diastereomeric catalysts depending on the control of the ligand.
  • the copolymer prepared by using the transition metal compound according to the present invention as a catalyst at high temperature and high activity can easily produce copolymers having a narrow molecular weight distribution and a narrow chemical composition distribution (CCD) Has a unique advantage of being able to manufacture a narrow (2peak) chemical composition distribution. Therefore, the transition metal catalyst composition according to the present invention can be advantageously used in the production of an ethylene polymer selected from copolymers of ethylene and an? -Olefin having various physical properties.
  • the transition metal compound according to one embodiment of the present invention is a transition metal compound based on an indenyl group into which a nitrogen-containing substituent represented by the following general formula (1) is introduced.
  • the transition metal compound is a rigid, An indene having a planar structure and rich in electrons and being broadly segmented and having a structure in which a nitrogen-containing substituent is introduced, or an amide group substituted with a silyl group, Or a silyl group connecting a derivative group thereof and an amido group, an alkyl or alkenyl group and an aryl group which induce a high molecular weight distribution, not a broad molecular weight distribution, which is a disadvantage of a diastereomer, , Which is a high-efficiency and high molecular weight ethylene Which has the advantage of being advantageous in obtaining the polymer at high temperature.
  • M is a transition metal of Group 4 on the Periodic Table
  • R 1 is (C 1 -C 20) alkyl or (C 2 -C 20) alkenyl and the alkyl or alkenyl of R 1 is halogen, (C 6 -C 30) aryl and (C 6 -C 20) Lt; / RTI > may be further substituted with one or more substituents selected from the group consisting of;
  • Ar 1 is (C6-C30) aryl, and the aryl of Ar 1 is a (C1-C20) alkyl, halo (C1-C20) alkyl and (C6-C30) aryl (C1-C20) is selected from the group consisting of alkyl Which may be further substituted with one or more substituents;
  • R 2 to R 5 are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl, (C6-C30) aryloxy, (CrC20) C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, wherein R 2 to R 5 may be connected to an adjacent substituent may form a fused ring, wherein the formed fused ring is (C1-C20) alkyl, (C6-C30) aryl, (C6-C30) aryloxy, (C6-C30) alkoxy, halo (C1- C20) alkyl, (C3- C20) cycloalkyl, (C 1 -C 20) alkyl (C 6
  • R 9 is (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 6 -C 30) aryl (C 1 -C 20) alkyl;
  • R 6 and R 7 are independently selected from the group consisting of (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, aryl, (C1-C20) alkoxy (C6-C30) aryl or (C6-C30) aryl (C1-C20) alkyl or, wherein R 6 and R 7 are connected to each other may form a ring, the formed ring is (C1-C60) alkyl, (C6-C60) aryl, (C6-C60) (C1-C20) alkyl (C6-C30) aryl and (C6-C20) aryloxy;
  • R < 8 &gt is hydrogen or (C1-C20) alkyl
  • X 1 and X 2 are independently of each other selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 1 -C 20) alkyl, (C 1 -C 20) alkyl ((C 1 -C 20) alkyl (C 6 -C 30) aryl) ) aryloxy, (C1-C20) alkoxy (C6-C30) aryloxy, -OSiR a R b R c, -SR d, -NR e R f, -PR g R h , or (C1-C20) alkylidene and ;
  • R a to R d are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) C3-C20) cycloalkyl;
  • R e to R h are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl, (C 6 -C 20) aryl (C 6 -C 20) C3-C20) cycloalkyl, tri (C1-C20) alkylsilyl or tri (C6-C20) arylsilyl;
  • the transition metal compound of the present invention is a catalyst having a structural feature that simultaneously contains an alkyl group or an alkenyl group and an aryl group in a silyl group linking an indenyl group and an amido group into which a nitrogen-containing substituent is introduced.
  • the transition metal compound is an alkyl group or an alkenyl Terephthalic acid, and terephthalic acid.
  • H 1 -NMR it was confirmed by H 1 -NMR that two diastereomers are present as shown in FIG. 1 due to the structural characteristic that the silyl group simultaneously contains an alkyl group or an alkenyl group and an aryl group.
  • the catalysts developed in the present invention exhibit such properties that a polymer having a narrow molecular weight distribution is produced and exhibits high activity even at a high temperature, despite the existence of diastereomeric properties at a ratio of 1: 1 to 1: 8. It has been reported that, in the case of catalysts having a diastereomer in which an indenyl group and an amido group are linked by a silyl group, the molecular weight distribution has a broad characteristic. However, in the case of the catalysts developed in the present invention, a polymer having a narrow molecular weight distribution could be obtained at high temperature and high efficiency.
  • a polymer having a narrow molecular weight distribution and a narrow composition distribution can be obtained, and a polymer having broad characteristics can be obtained with a narrow molecular weight distribution and a chemical composition distribution, It can be said that the value is great.
  • alkyl &quot refers to a monovalent straight-chain or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms.
  • alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, nonyl, and the like.
  • " aryl " refers to an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, with a single or fused ring containing from 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond.
  • Fused ring systems may include aliphatic rings, such as saturated or partially saturated rings, and necessarily contain one or more aromatic rings.
  • the aliphatic ring may also contain nitrogen, oxygen, sulfur, carbonyl or the like in the ring.
  • aryl radical examples include phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, crycenyl, naphthacenyl, 9,10-dihydro Anthracenyl, and the like.
  • " cycloalkyl " as used herein means a monovalent saturated carbocyclic radical consisting of one or more rings.
  • cycloalkyl radicals include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
  • " halo " or " halogen " as used herein means a fluorine, chlorine, bromine or iodine atom.
  • &quot alkyl substituted by one or more halogens, such as trifluoromethyl.
  • " alkoxy " and " aryloxy " refer to an -O-alkyl radical and an -O-aryl radical, respectively, wherein alkyl and aryl are as defined above.
  • the transition metal compound of Formula 1 may be a transition metal compound represented by Formula 2:
  • M, R 1 , R 6 , R 7 , R 9 , X 1, and X 2 are the same as defined in Formula 1;
  • R 2 to R 5 are independently of each other hydrogen, (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C6-C30) aryl, (C6-C30) aryl, (C6-C30) aryloxy, (CrC20) C20) alkyl (C6-C30) aryl) (C1-C20) alkyl, wherein R 2 to R 5 is with or without an adjacent substituent via the aromatic ring (C3-C7) alkylene, (C3-C7) alkenyl (C1-C20) alkoxy, halo (C1-C20) alkyl, (C3-C60) alkynyl, (C6-C30) aryl, (C6-C30) aryloxy, (C1-C20) alkyl (C6-C30) ary
  • R 11 to R 15 are independently of each other hydrogen, (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl or (C 6 -C 30) aryl (C 1 -C 20) alkyl.
  • M of the transition metal compound is preferably a transition metal of Group 4 in the periodic table, preferably titanium (Ti), zirconium (Zr) or hafnium (Hf), more preferably titanium ) Or zirconium (Zr).
  • (C1-C20) alkyl groups is, for example, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec - butyl, tert - butyl group, n- pentyl group, A neopentyl group, an amyl group, an n-hexyl group, an n-octyl group, a n-decyl group, an n-dodecyl group or an n-pentadecyl group; (C2-C20) alkenyl group is, for example, a vinyl group or an allyl group; (C3-C20) cycloalkyl group is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclo
  • R 6 and R 7 are independently (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6-C30) aryl, wherein R 6 and R each other 7 may be linked by a (C3-C7) alkylene containing or not containing an aromatic ring to form a ring, and the ring formed may be substituted by (C1-C20) alkyl, (C6-C30) aryl (C6-C60) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C1- Or more.
  • R 1 can be (C 1 -C 20) alkyl, (C 2 -C 20) alkenyl or (C 6 -C 30) aryl (C 1 -C 20) alkyl;
  • Ar 1 can be (C6-C30) aryl or (C1-C20) alkyl (C6-C30) aryl;
  • R 2 to R 5 are each independently hydrogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C1-C20) alkyl (C6-C30) aryl, (C6-C30) aryl, (C6-C30) (C6-C30) aryloxy or (C6-C30) aryl (C1-C20) alkyl, or wherein R 2 to R 5 contain an aromatic ring with or without adjacent substituents C3-C7) alkylene, (C3-C7) alkenylene or (C4-C7) alkadienylene to form
  • the R One Is more specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a vinyl group, an allyl group Or a benzyl group;
  • the Ar One May be more specifically a phenyl group, a naphthyl group, a biphenyl group, a tolyl group, a trimethylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, an octylphenyl group, a decylphenyl group, a dodecylphenyl group or a tetradecylphenyl group;
  • the R 2 To R 5 Is independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, A phenyl group, a naph
  • R 31 to R 35, R 41 and R 42 are each independently hydrogen, methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, 2-methyl butyl group, a sec - butyl group, tert - butyl group, n- pentyl group, neopentyl group, amyl, n- hexyl, n- octyl group, n- decyl group, n- dodecyl group, n- penta decyl group, a phenyl group, a 2-tolyl group, Xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, Xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
  • the halogen atom may be exemplified by a fluorine, chlorine, bromine or iodine atom
  • the (C 1 -C 20) alkyl group may be a methyl group, group, an isopropyl group, n- butyl group, sec - butyl, tert - butyl group, n- pentyl group, neopentyl group, amyl, n- hexyl, n- octyl group, n- decyl group, n- A dodecyl group, an n-pentadecyl group or an n-eicosyl group;
  • the (C3-C20) cycloalkyl group may be exemplified by a cyclopropane group, a cyclobutyl group, a cyclopentyl group, a cyclo
  • X 1 and X 2 are independently halogen, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C30) aryl, (C6-C30) aralkyl (C1 each other -C20) alkyl, (C1-C20) alkoxy, (C6-C30) aryloxy, (C1-C20) alkyl -OSiR (C6-C30) aryloxy, a R b R c, -SR d, -NR e R f or -PR g R h ; R a to R h independently of one another can be (C 1 -C 20) alkyl or (C 6 -C 20) aryl.
  • X 1 and X 2 independently represent fluorine, chlorine, bromine, methyl, ethyl, isopropyl, A tertiary butyl group, a tert -butyl group, a tert -butoxy group, a phenoxy group, a 4-tert-butylphenoxy group, a trimethylsilyl group, a tert- butyldimethylsilyl group, a dimethylamino group, a diphenylamino group, a dimethylphosphine group, a diethylphosphine group, , Ethylthio group or isopropylthio group.
  • M in the formula (2) is tetravalent titanium, zirconium or hafnium;
  • R < 1 > is (C1-C20) alkyl;
  • R 11 to R 15 independently from each other are hydrogen or (C 1 -C 20) alkyl;
  • R 2 to R 5 independently from each other are hydrogen or (C 1 -C 20) alkyl, or R 2 to R 5 are adjacent substituents and , or To form a fused ring;
  • R 21 to R 24 independently from each other are hydrogen or (C 1 -C 20) alkyl;
  • R 6 and R 7 are independently (C1-C20) alkyl each other, wherein R 6 and R 7 is , , , , , , , or To form a ring;
  • R 31 to R 35 , R 41 and R 42 independently of one another are hydrogen or (C 1 -C 20) alkyl;
  • m and n are each independently an integer of 1 to 4;
  • the transition metal compound may be selected from compounds having the following structures, but is not limited thereto.
  • X 1 and X 2 are each independently selected from the group consisting of halogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) aryl, (C 6 -C 30) (C6-C30) aryloxy, (C6-C30) aryloxy, -OSiR a R b R c , -SR d , -NR e R f or -PR g R h ;
  • R a to R h are, independently of each other, (C 1 -C 20) alkyl or (C 6 -C 20) aryl.
  • the transition metal compounds according to the invention are ethylene homopolymers and ethylene and to the ⁇ - olefin is an active catalytic component used in ethylene polymer produced is selected from the copolymer, and preferably X 1 or X of the transition metal complex 2 ligand may be extracted to cationize the center metal while acting as a co-catalyst with an aluminum compound, a boron compound, or a mixture thereof capable of acting as a counterion having a weak bonding force, that is, an anion, Catalyst compositions comprising catalysts are also within the scope of the present invention.
  • a transition metal catalyst composition comprising the transition metal compound and a cocatalyst selected from an aluminum compound, a boron compound, or a mixture thereof.
  • the aluminum compound which can be used as a cocatalyst is selected from an aluminoxane compound represented by Chemical Formula 3 or 4, an organoaluminum compound represented by Chemical Formula 5, or an organoaluminum oxide compound represented by Chemical Formula 6 or Chemical Formula 7 Lt; / RTI >
  • R 51 is (C 1 -C 20) alkyl, preferably a methyl group or an isobutyl group, and p is an integer of 5 to 20;
  • R 52 and R 53 are each (C 1 -C 20) alkyl;
  • E is hydrogen or halogen;
  • r is an integer from 0 to 3;
  • R < 54 > is (C1-C20) alkyl or (C6-C30)
  • the aluminum compound examples include aluminoxane compounds such as methylaluminoxane, modified methylaluminoxane, and tetraisobutylaluminoxane;
  • organoaluminum compound examples include trialkylaluminum including trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum;
  • Dialkyl aluminum chlorides including dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum chloride and dihexyl aluminum chloride;
  • Alkylaluminum dichlorides including methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride;
  • Dialkylaluminum hydrides including dimethylaluminum hydride, die
  • the aluminum compound is preferably one or a mixture of two or more selected from alkyl aluminoxane compounds or trialkyl aluminum, more preferably methyl aluminoxane, modified methyl aluminoxane, tetraisobutyl aluminum Naphthoic acid, niobic acid, trimethylaluminum, triethylaluminum, trioctylaluminum and triisobutylaluminum, or a mixture of two or more thereof.
  • boron compounds which can be used as cocatalysts are known from U.S. Patent No. 5,198,401 and can be selected from the compounds represented by the following formulas (8) to (10).
  • B is a boron atom
  • R 61 is a phenyl group and the phenyl group is substituted with 3 to 5 substituents selected from fluoro, (C1-C20) alkyl unsubstituted or substituted by fluoro, and (C1-C20) alkoxy unsubstituted or substituted with fluoro ≪ / RTI &gt
  • R 62 is a (C 5 -C 7) aromatic radical or a (C 1 -C 20) alkyl (C 6 -C 20) aryl radical or a (C 6 -C 30) aryl (C 1 -C 20) alkyl radical such as triphenylmethylium, Radical
  • Z is a nitrogen or phosphorus atom
  • R 63 is a (C 1 -C 20) alkyl radical and Ar 2 is a (C 5 -C 7) aromatic radical substituted with a phenyl or (C 1
  • boron-based co-catalyst include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluoro (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tetrakis (triphenylphosphine) borane, (Pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluorophenyl) borate, tetrakis , 5,6-tetrafluorophenyl) borate, tetrakis (2,2,4-trifluorophenyl) borate, phenylbis (pentafluorophenyl) borate
  • these compounds include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1'-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, triphenyl (Pentafluorophenyl) borate, triphenylmethyleniumtetrakis (3,5-bistrifluoromethylphenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetra (Pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (Pentafluorophenyl) borate, tri (n-butyl) ammonium t
  • the cocatalyst may serve as a scavenger for removing impurities acting as a poison 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 the ratio of the center metal (M) to the boron atom (B) May be in the range of 1: 0.1 to 100: 1 to 2,000, preferably 1: 0.5 to 30: 10 to 1,000, more preferably 1: 0.5 to 1: ⁇ 5: 10 ⁇ 500.
  • the ratio of the transition metal compound of the present invention to the cocatalyst is out of the above range, the amount of the cocatalyst is relatively small, so that the transition metal compound is not fully activated and the catalytic activity of the transition metal compound may not be sufficient, There may arise a problem that the production cost is greatly increased due to the use of co-catalyst. Within this range, it exhibits excellent catalytic activity for producing a homopolymer of ethylene or a copolymer of ethylene and? -Olefin, and the range of the ratio varies depending on the purity of the reaction.
  • a method for producing an ethylene polymer selected from a homopolymer of ethylene and a copolymer of ethylene and an? -Olefin using the transition metal compound or the transition metal catalyst composition will be.
  • a copolymerization method of copolymerizing ethylene, propylene and optionally a nonconjugated diene using the transition metal compound or the transition metal catalyst composition is provided.
  • the process for preparing the ethylene polymer using the transition metal catalyst composition can be carried out by contacting the transition metal catalyst, the cocatalyst, and the ethylene or? -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 the components may be premixed and introduced into the reactor, and the mixing conditions such as the order of introduction, temperature, and concentration are not limited.
  • Preferred organic solvents that can be used in the above production process are (C3-C20) hydrocarbons. Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, Hexane, benzene, toluene, xylene, and the like.
  • ethylene when ethylene homopolymer is prepared, ethylene alone is used as a monomer, and the pressure of ethylene is suitably 1 to 1000 atm, and more preferably 6 to 150 atm. It is also effective that the polymerization reaction is carried out at a temperature of from 25 ° C to 220 ° C, preferably from 70 ° C to 220 ° C, more preferably from 100 ° C to 220 ° C.
  • a copolymer of ethylene and? -Olefin When a copolymer of ethylene and an? -Olefin is prepared, a copolymer of ethylene and? -Olefin, C4 to C20 diolefin, C5 to C20 cycloolefin or cycloolefin or styrene 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-hexene, and the like.
  • C4-C20 diolefins include 1,3-butadiene, 1,4-pentadiene and 2- Methyl-1,3-butadiene
  • preferred examples of the C5-C20 cycloolefin or the cyclodiolefin include cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, Vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB) and 5-ethylidene- Bonenen (ENB).
  • the above olefins can be homopolymerized or two or more olefins can be copolymerized.
  • preferred ethylene pressure and polymerization reaction temperature may be the same as in the case of the ethylene homopolymer production, and the copolymer prepared according to the method of the present invention usually contains not less than 30% by weight of ethylene, preferably 60% % Ethylene, more preferably from 60 to 99 wt%, based on the total weight of the composition.
  • a C3-C10 alpha -olefin is appropriately used as ethylene and a comonomer, and a melt flow rate of 0.001 to 2000 dg / min with a density of 0.850 g / cc to 0.960 g / Can easily and economically be manufactured from an elastomer having a high density polyethylene (HDPE) region.
  • HDPE high density polyethylene
  • the ethylene / propylene (EP) elastomer and the ethylene / propylene / diene (EPDM) elastomer can be advantageously prepared using the catalyst of the present invention.
  • EP ethylene / propylene
  • EPDM ethylene / propylene / diene
  • hydrogen may be used as a molecular weight modifier and has a weight average molecular weight (Mw) generally 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 a polymerization reactor, it is preferable to apply to a solution polymerization process carried out at a temperature above the melting point of the polymer.
  • the transition metal compound and cocatalyst may be supported on a porous metal oxide support as disclosed in U.S. Patent No. 4,752,597, and used as slurry polymerization or gas-phase polymerization processes as non-uniform catalyst systems.
  • the present invention also includes a compound represented by the following formula (Int-1) as an intermediate for preparing the transition metal compound of the above formula (1).
  • R 1 to R 9 and Ar 1 are the same as defined in the above formula (1).
  • the present invention also relates to a transition metal compound of the above formula (1) for use in producing a copolymer of ethylene and an? -Olefin having a GPC graph of a single rod, and a TGIC analysis using the same, To a method for producing a copolymer of ethylene and an? -Olefin.
  • Cyclohexane a polymerization solvent
  • the polymerized polymer was analyzed by the method described below.
  • MI Melt Flow Index
  • the content ratio of unreacted ethylene and nitrogen as a reference material was measured by gas chromatography (GC).
  • N - tert - butyl-1-chloro-1-methyl-1-phenyl-amine silane 7.16 g, 31.4 mmol was added to and dissolved in tetrahydrofuran (THF) (50 mL) was stirred at room temperature for 12 hours.
  • THF tetrahydrofuran
  • the solvent was removed in vacuo, dissolved in normal hexane (150 mL) and the solids were removed with a filter filled with dried celite. The solvent was removed to give compound 1-c, which was viscous oil (10.0 g, yield 90.8%, diastereomeric ratio 1: 1).
  • the compound 1-d (4.0 g, 11.0 mmol) was dissolved in diethyl ether (50 mL) in a 250 mL three-necked round-bottomed flask under nitrogen atmosphere, and the temperature was lowered to -78 ° C. Then, 1.5 M methyl lithium (14.7 mL, 22.1 mmol ) was slowly added thereto, and a solution of tetrachlorotitanium (TiCl 4 ) (2.1 g, 11.0 mmol) in anhydrous n-hexane (30 mL) was slowly added at -78 ° C. After stirring at room temperature for 3 hours, the solvent was removed in vacuo.
  • Compound 2-a was prepared by the method for preparation of US 6268444 B1.
  • the compound 2-b (4.14 g, 11.0 mmol) was dissolved in diethyl ether (50 mL) in a 250 mL three-necked round-bottomed flask under nitrogen atmosphere. The temperature was lowered to -78 ° C., and 1.5 M methyl lithium (29.4 mL, 44.2 mmol ) Is slowly injected, the temperature is raised to room temperature and stirred for 6 hours. The reaction mixture was cooled to -78 ° C, and a solution of tetrachlorotitanium (TiCl 4 ) (2.1 g, 11.0 mmol) in anhydrous n-hexane (30 mL) was slowly added at -78 ° C.
  • TiCl 4 tetrachlorotitanium
  • Copolymerization of ethylene with 1-octene was carried out using a continuous polymerization apparatus as follows.
  • the catalysts synthesized in Preparation Examples 1-3 and Comparative Preparation Example 1 were used as single-site catalysts, and cyclohexane was used as a solvent.
  • the amount of catalyst used is as shown in Table 1 below.
  • Ti represents a catalyst
  • Al represents triisobutylaluminum
  • B represents N, N-dioctadecyl anilinium tetrakis (pentafluorophenyl) borate as a cocatalyst.
  • the catalyst was dissolved in toluene at a concentration of 0.1 g / L, and the synthesis was carried out using 1-octene as the comonomer.
  • the conversion rate of the reactor could be estimated through the reaction conditions and the temperature gradient in the reactor when polymerizing with one polymer under each reaction condition.
  • the molecular weight was controlled by a function of the reactor temperature and the 1-octene content, and the conditions and results are shown in Tables 1 and 2 below.
  • -Ti means Ti in the catalyst.
  • Examples 1 to 7 which were obtained by polymerizing the catalysts developed in the present invention, exhibited a higher temperature (150 ° C. or higher) than Comparative Examples 1 and 2 Polymers with low MI values indicating a high conversion of ethylene and a low density and a high molecular weight were easily obtained.
  • the catalyst of the present invention exhibited a high ethylene conversion despite the use of a small amount of catalyst as compared with the catalyst of Comparative Example 2, indicating that the catalyst of the present invention is superior in catalytic activity. Also, in Example 4, a copolymer having a low density and a high molecular weight was easily produced even at a polymerization temperature of 181 degrees.
  • a copolymer having a high ethylene conversion of 77% or more, a low density of 0.893 g / cc or less, and an MI value of less than 5 can be produced at high temperature polymerization of 150 ° C or higher.
  • GPC graphs of the copolymers prepared in Examples 5 and 6 are shown in FIG. 2, and the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution index (MWD) are shown in Table 3 below.
  • GPC graphs of copolymers prepared by catalyzing diastereomers have broad molecular weight distributions in a wide or two peak graph shape.
  • the complexes of Preparation Example 2 of the present invention and Preparation Example 3 The copolymer prepared in Example 5 and Example 6 exhibited a narrow molecular weight distribution of a single rod uniquely on the GPC graph.
  • the copolymer of Example 5 (Polymer 2) had a molecular weight distribution of 2.33
  • the copolymer of Example 6 (Polymer 3) had a molecular weight distribution of 2.2, all of which showed a narrow molecular weight distribution of a single rod.
  • FIG. 3 shows a TGIC (Thermal Gradient Interaction Chromatography) graph for examining the chemical composition distribution (CCD) of the copolymers prepared in Examples 5 and 6. From FIG. 3, it can be seen that the copolymer (Polymer 2) prepared using the complex 2 of Preparation Example 2 in Example 5 exhibits a narrow distribution of single peaks characteristic of a typical single-site catalyst, It can be seen that the copolymer (Polymer 3) prepared in Example 6 using the complex 3 of Production Example 3 as a polymerization catalyst exhibits a wide chemical composition distribution with a double peak which is difficult to obtain from a typical single-site catalyst.
  • TGIC Thermal Gradient Interaction Chromatography
  • Copolymerization of ethylene with 1-octene was carried out using a batch polymerization apparatus as follows.
  • the catalyst activity was significantly increased as compared with the case of using the complex C of Comparative Preparation Example 4 in which a nitrogen-containing substituent was not introduced in indene.
  • the polymers prepared using the complex B of Comparative Preparation Example 3 in which the diphenyl group was substituted were used as the polymerization catalysts, although the molecular weight was larger than that of the polymer prepared using the complex C of Comparative Preparation Example 4 as the polymerization catalyst The molecular weight distribution was remarkably narrow.
  • the complex according to the present invention a complex having a structure in which an indene and an amido group introduced with a nitrogen-containing substituent are connected with an alkyl group and an aryl group-substituted silyl group,
  • a high-temperature highly active diastereomeric catalyst capable of producing a copolymer having a narrow molecular weight distribution and a narrow chemical composition distribution, or having a narrow molecular weight distribution useful for the development of new products and having a wide chemical composition distribution, As shown in FIG.
  • the complex according to the present invention a complex having a structure in which an indene and an amido group introduced with a nitrogen-containing substituent are linked by an alkyl group or an alkenyl group and a silyl group substituted with an aryl group is easy to produce, It can be said that a copolymer having a narrow molecular weight distribution and a narrow molecular weight distribution and a copolymer having a narrow molecular weight distribution and a wide chemical composition distribution can be easily produced by simply changing a substituent, have.
  • the transition metal compound or the catalyst composition comprising the transition metal compound according to the present invention can be easily produced by a high synthesis rate and an economical method and is excellent in thermal stability of the catalyst,
  • the present invention has commercial utility in comparison with the already known metallocene and non-metallocene single-site catalysts since it can produce a polymer having a high copolymerization reactivity with a high molecular weight and a high molecular weight.
  • the present invention has developed catalysts that exhibit narrow molecular weight distribution characteristics, such as single-site catalysts, despite the fact that they are diastereomeric catalysts depending on the control of the ligand.
  • the copolymer prepared by using the transition metal compound according to the present invention as a catalyst at high temperature and high activity can easily produce copolymers having a narrow molecular weight distribution and a narrow chemical composition distribution (CCD) Has a unique advantage of being able to manufacture a narrow (2peak) chemical composition distribution. Therefore, the transition metal catalyst composition according to the present invention can be advantageously used in the production of an ethylene polymer selected from copolymers of ethylene and an? -Olefin having various physical properties.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un nouveau composé de métal de transition à base d'indène ; une composition de catalyseur de métal de transition le comprenant et présentant une activité catalytique élevée pour la préparation d'un homopolymère ou d'un copolymère d'éthylène et une ou plusieurs α-oléfines ; un procédé de préparation d'un homopolymère d'éthylène ou d'un copolymère d'éthylène et d'une α-oléfine en utilisant cette composition de catalyseur de métal de transition ; et un homopolymère d'éthylène ou un copolymère d'éthylène et une α-oléfine préparés à l'aide de ce procédé.
PCT/IB2018/057534 2017-09-29 2018-09-28 Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition WO2019064247A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP18862289.8A EP3689884A4 (fr) 2017-09-29 2018-09-28 Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition
CA3075240A CA3075240A1 (fr) 2017-09-29 2018-09-28 Nouveau compose de metal de transition a base d'indene, composition de catalyseur de metal de transition le contenant, et procede de preparation d'homopolymere ou de copolymere d'ethylene et d'.alpha.-olefine en utilisant cette composition
RU2020114610A RU2783400C2 (ru) 2017-09-29 2018-09-28 НОВОЕ СОЕДИНЕНИЕ ПЕРЕХОДНОГО МЕТАЛЛА НА ОСНОВЕ ИНДЕНА, КАТАЛИТИЧЕСКАЯ КОМПОЗИЦИЯ НА ОСНОВЕ ПЕРЕХОДНОГО МЕТАЛЛА, СОДЕРЖАЩАЯ УКАЗАННОЕ СОЕДИНЕНИЕ, И СПОСОБ ПОЛУЧЕНИЯ ГОМОПОЛИМЕРА ЭТИЛЕНА ИЛИ СОПОЛИМЕРА ЭТИЛЕНА И α-ОЛЕФИНА С ИСПОЛЬЗОВАНИЕМ УКАЗАННОЙ КОМПОЗИЦИИ
US16/650,848 US10919992B2 (en) 2017-09-29 2018-09-28 Indene-based transition metal compound, transition metal catalyst composition comprising same, and method for preparing ethylene homopolymer or copolymer of ethylene and alpha-olefin by using same
CN201880063246.XA CN111148748B (zh) 2017-09-29 2018-09-28 新的基于茚的过渡金属化合物、包含其的过渡金属催化剂组合物、以及通过使用其制备乙烯均聚物或乙烯与α-烯烃的共聚物的方法
JP2020516841A JP7177148B2 (ja) 2017-09-29 2018-09-28 新規のインデン系遷移金属化合物、これを含む遷移金属触媒組成物、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‐オレフィンとの共重合体の製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0127528 2017-09-29
KR20170127528 2017-09-29
KR10-2018-0115040 2018-09-27
KR1020180115040A KR102643986B1 (ko) 2017-09-29 2018-09-27 신규한 인덴계 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법

Publications (1)

Publication Number Publication Date
WO2019064247A1 true WO2019064247A1 (fr) 2019-04-04

Family

ID=65902338

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2018/057534 WO2019064247A1 (fr) 2017-09-29 2018-09-28 Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition

Country Status (1)

Country Link
WO (1) WO2019064247A1 (fr)

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6392621A (ja) 1986-10-08 1988-04-23 Mitsubishi Petrochem Co Ltd エチレン共重合体の製造法
US4752597A (en) 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
EP0320762A2 (fr) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Procédé pour la préparation d'un composé métallocène chiral stéréorigide
JPH0284405A (ja) 1988-09-20 1990-03-26 Mitsubishi Petrochem Co Ltd エチレン重合体の製造法
EP0372632A1 (fr) 1988-12-02 1990-06-13 Shell Internationale Researchmaatschappij B.V. Procédé de conversion d'hydrocarbures
JPH032347A (ja) 1989-02-22 1991-01-08 Sumitomo Electric Ind Ltd 窒素含有サーメット合金
EP0416815A2 (fr) 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0420436A1 (fr) 1989-09-13 1991-04-03 Exxon Chemical Patents Inc. Catalyseurs pour la polymérisation d'oléfines
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
EP0842939A1 (fr) 1995-07-14 1998-05-20 Sumitomo Chemical Company, Limited Complexe a base de metal de transition, procede de preparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procede de production de polymeres d'olefines
KR20000029833A (ko) * 1996-08-08 2000-05-25 그레이스 스티븐 에스. 3-헤테로원자치환된사이클로펜타디에닐-함유금속착체및올레핀중합방법
WO2001042315A1 (fr) 1999-12-10 2001-06-14 Dow Global Technologies Inc. Complexes metalliques groupe 4 substitues, catalyseurs et procede de polymerisation olefinique
US6555634B1 (en) * 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
KR20040083922A (ko) * 2003-03-25 2004-10-06 재단법인서울대학교산학협력재단 벤즈[에프]인덴계 리간드를 함유한 메탈로센 유도체 및 그제조방법
KR101002620B1 (ko) * 2002-03-14 2010-12-21 다우 글로벌 테크놀로지스 인크. 치환된 인데닐 금속 착물 및 중합방법

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4752597A (en) 1985-12-12 1988-06-21 Exxon Chemical Patents Inc. New polymerization catalyst
JPS6392621A (ja) 1986-10-08 1988-04-23 Mitsubishi Petrochem Co Ltd エチレン共重合体の製造法
US5198401A (en) 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
EP0320762A2 (fr) 1987-12-18 1989-06-21 Hoechst Aktiengesellschaft Procédé pour la préparation d'un composé métallocène chiral stéréorigide
JPH0284405A (ja) 1988-09-20 1990-03-26 Mitsubishi Petrochem Co Ltd エチレン重合体の製造法
EP0372632A1 (fr) 1988-12-02 1990-06-13 Shell Internationale Researchmaatschappij B.V. Procédé de conversion d'hydrocarbures
JPH032347A (ja) 1989-02-22 1991-01-08 Sumitomo Electric Ind Ltd 窒素含有サーメット合金
EP0416815A2 (fr) 1989-08-31 1991-03-13 The Dow Chemical Company Catalyseurs de polymérisation d'addition à géométrie restreinte, leur procédé de préparation, les précurseurs, procédés d'utilisation et polymères obtenus
EP0420436A1 (fr) 1989-09-13 1991-04-03 Exxon Chemical Patents Inc. Catalyseurs pour la polymérisation d'oléfines
EP0842939A1 (fr) 1995-07-14 1998-05-20 Sumitomo Chemical Company, Limited Complexe a base de metal de transition, procede de preparation dudit complexe, catalyseur de polymerisation pour des olefines le contenant et procede de production de polymeres d'olefines
KR20000029833A (ko) * 1996-08-08 2000-05-25 그레이스 스티븐 에스. 3-헤테로원자치환된사이클로펜타디에닐-함유금속착체및올레핀중합방법
US6268444B1 (en) 1996-08-08 2001-07-31 Dow Chemical Company 3-heteroatom substituted cyclopentadienyl-containing metal complexes and olefin polymerization process
US6555634B1 (en) * 1999-05-13 2003-04-29 The Dow Chemical Company Di- and tri-heteroatom substituted indenyl metal complexes
WO2001042315A1 (fr) 1999-12-10 2001-06-14 Dow Global Technologies Inc. Complexes metalliques groupe 4 substitues, catalyseurs et procede de polymerisation olefinique
KR20050112135A (ko) * 1999-12-10 2005-11-29 다우 글로벌 테크놀로지스 인크. 치환된 4족 금속 착체, 촉매 및 올레핀 중합 방법
KR101002620B1 (ko) * 2002-03-14 2010-12-21 다우 글로벌 테크놀로지스 인크. 치환된 인데닐 금속 착물 및 중합방법
KR20040083922A (ko) * 2003-03-25 2004-10-06 재단법인서울대학교산학협력재단 벤즈[에프]인덴계 리간드를 함유한 메탈로센 유도체 및 그제조방법

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 174, 2001, pages 35 - 49
See also references of EP3689884A4 *

Similar Documents

Publication Publication Date Title
WO2017155149A1 (fr) Composition de catalyseur hybride, son procédé de préparation, et polyoléfine préparée en l'utilisant
WO2017176074A1 (fr) Résine à base d'un copolymère de propylène-diène présentant une remarquable tension de fusion
WO2013133595A1 (fr) Catalyseur métallocène supporté hybride, son procédé de préparation et procédé de préparation d'une polyoléfine à l'aide de celui-ci
EP2718304A2 (fr) Procédé de préparation d'un copolymère éthylène- -oléfine-diène
WO2019038605A1 (fr) Nouveau composé de métal de transition, composition de catalyseur le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine l'utilisant
WO2010053264A2 (fr) Procédé de fabrication de copolymères élastomères de l'éthylène et d'α-oléfines
WO2017003261A1 (fr) Composé de métal de transition et composition de catalyseur le contenant
WO2019093630A1 (fr) Procédé de préparation d'une résine de polypropylène à haute résistance à l'état fondu
WO2017026605A1 (fr) Composé de métal de transition, composition de catalyseur à base de métal de transition pour la polymérisation d'oléfines le comprenant, et procédé de production de polymère à base d'oléfine l'utilisant
KR101889978B1 (ko) 다환기가 치환된 신규의 전이금속 화합물, 이를 포함한 전이금속 촉매 조성물 및 이를 이용한 에틸렌과 α-올레핀 공중합체 또는 에틸렌과 올레핀-디엔 공중합체의 제조방법
WO2010079906A2 (fr) Procédé de production d'un copolymère éthylène/propylène/diène
KR20080039794A (ko) 전이금속 촉매계 및 이를 이용한 에틸렌 단독중합체 또는에틸렌과 올레핀의 공중합체 제조방법
KR20090075969A (ko) 전이금속 화합물, 이를 포함하는 전이금속 촉매 조성물, 및이를 이용한 에틸렌 단독중합체 또는 에틸렌과α-올레핀의 공중합체의 제조방법
WO2018097468A1 (fr) Catalyseur de polyoléfine et procédé de préparation d'une polyoléfine l'utilisant
WO2015183017A1 (fr) 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
TWI754776B (zh) 新穎之基於茚的過渡金屬複合物、包含其之催化組成物以及使用其製備乙烯均聚物或乙烯與α-烯烴之共聚物的方法
WO2023191519A1 (fr) Composé de métal de transition pour catalyseur de polymérisation d'oléfine, catalyseur de polymérisation d'oléfine le comprenant et polyoléfine polymérisée l'utilisant
WO2017003262A1 (fr) Composé de métal de transition et composition de catalyseur le contenant
KR20150138042A (ko) 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
WO2018127772A1 (fr) Nouveau composé de métal de transition, composition de catalyseur contenant celui-ci, procédé de production d'homopolymère d'éthylène ou de copolymère d'éthylène et d'une alpha-oléfine l'utilisant
WO2019064247A1 (fr) Nouveau composé de métal de transition à base d'indène, composition de catalyseur de métal de transition le contenant, et procédé de préparation d'homopolymère ou de copolymère d'éthylène et d'alpha-oléfine en utilisant cette composition
KR101142122B1 (ko) 새로운 전이금속 촉매계 및 이를 이용한 에틸렌 단독중합체또는 에틸렌과 α-올레핀의 공중합체 제조방법
WO2012176946A1 (fr) SYSTÈME DE CATALYSEUR DE MÉTAUX DE TRANSITION PRÉSENTANT UNE EXCELLENTE COPOLYMÉRISATION ET PROCÉDÉ DE PRÉPARATION D'UN HOMOPOLYMÈRE D'ÉTHYLÈNE OU D'UN COPOLYMÈRE D'ÉTHYLÈNE ET D'α-OLÉFINE UTILISANT CE SYSTÈME
KR101889980B1 (ko) 퀴놀린-1(2Ｈ)-일기를 갖는 새로운 전이금속 화합물, 이를 포함한 올레핀 중합용 전이금속 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법
WO2018122693A1 (fr) 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

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18862289

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3075240

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2020516841

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2018862289

Country of ref document: EP

Effective date: 20200429