WO1996004317A1 - Compose de metal de transition, catalyseur de polymerisation d'olefine, polymere d'olefine obtenu au moyen du catalyseur et procede de production du polymere - Google Patents

Compose de metal de transition, catalyseur de polymerisation d'olefine, polymere d'olefine obtenu au moyen du catalyseur et procede de production du polymere Download PDF

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Publication number
WO1996004317A1
WO1996004317A1 PCT/JP1995/001530 JP9501530W WO9604317A1 WO 1996004317 A1 WO1996004317 A1 WO 1996004317A1 JP 9501530 W JP9501530 W JP 9501530W WO 9604317 A1 WO9604317 A1 WO 9604317A1
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catalyst
compound
transition metal
group
polymerization
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PCT/JP1995/001530
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English (en)
Japanese (ja)
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Takuji Okamoto
Masatoshi Uemura
Masami Watanabe
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Idemitsu Kosan Co., Ltd.
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Publication of WO1996004317A1 publication Critical patent/WO1996004317A1/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
    • C07F17/00—Metallocenes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not

Definitions

  • the present invention relates to a transition metal compound, an orphan polymerization catalyst, an orphan polymer using the catalyst, and a method for producing the same.
  • the present invention relates to a transition metal compound, a novel catalyst for polymerization of olefin, an olefin polymer using the catalyst, and a method for producing the same. More specifically, the present invention relates to a transition metal compound useful as a component of an olefin polymerization catalyst, and an olefin polymer containing the transition metal compound having a narrow molecular weight distribution and a relatively wide composition distribution. Or a highly active polymerization catalyst that gives highly regular polypropylene, an olefin homopolymer or copolymer obtained using the polymerization catalyst, and an olefin polymer. It relates to a method for efficiently manufacturing. Background art
  • a catalyst comprising a combination of a transition metal compound and an aluminoxane is known (Japanese Patent Application Laid-Open No. 58-19309). And Japanese Patent Application Laid-open No. Sho 60-217720).
  • cationic species are useful as active species in soluble polymerization catalysts [Journal of Ob-A-American, Chemical, and Society]. Am. Chem. Soc.) ”, Volume 81, Page 81 (1959), Volume 82, Page 195 (1960), Volume 107, Volume 7 Page (1985)].
  • the present invention provides a novel transition metal compound useful as a component of an orefene polymerization catalyst, an orefin-based polymer having a narrow molecular weight distribution and a relatively wide composition distribution, or a highly ordered polymer.
  • a highly active polymerization catalyst for giving polypropylene, and an olefin polymer or copolymer having a narrow molecular weight distribution and a relatively wide composition distribution obtained by using the polymerization catalyst and
  • the purpose of the present invention is to provide a polypropylene polymer having a high melting point because there is almost no heterogeneous bond due to 2,1-insertion in the chain.
  • the present inventors have conducted intensive studies to achieve the above object, and consequently found that a novel transition metal compound having a specific structure is useful as a component of a catalyst for polymerization of olefins, and that the transition metal A polymerization catalyst containing a compound and an activation co-catalyst, for example, a compound capable of forming an ionic complex by reacting with the transition metal compound or a derivative thereof, and optionally an organic aluminum compound has high activity. Having a narrow molecular weight distribution and a relatively broad composition distribution. It was found that the pyrene was given efficiently. The present invention has been completed based on such findings.
  • the present invention provides a compound represented by the general formula (I):
  • M is a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanoid series
  • X represents a ⁇ -binding ligand bonded to M, and when there are a plurality of Xs, They may be the same or different, and may be crosslinked with an indenyl ring or ⁇ .
  • ⁇ represents a Lewis base, and when there are a plurality of ⁇ , a plurality of ⁇ may be the same or different and may be cross-linked to an indenyl ring or X.
  • ⁇ represents a crosslinking group
  • p is an integer of 1 to 20
  • q is an integer of 1 to 5
  • r is an integer of 0 to 3.
  • R 1 to R 8 each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a heteroatom-containing group. However, they may be the same or different, or may form a ring with an adjacent group. Also, three R 4 's may be the same or different, and three R 8 ' s may be the same or different. ]
  • A a transition metal compound represented by the general formula (I) and an activating co-catalyst, for example, ( B) a compound characterized by containing a compound capable of forming an ionic complex by reacting with the transition metal compound of the component (A) or a derivative thereof, and optionally (C) an organic aluminum compound.
  • An object of the present invention is to provide a polymerization catalyst, and an olefin-based polymer obtained by using these polymerization catalysts for an olefin.
  • the orefin-based polymer of the present invention may be obtained by homopolymerizing orefins with orefins and other orefins and / or other monomers in the presence of the above-mentioned catalyst for orefin polymerization. It can be produced by copolymerization.
  • FIG. 1 is a chart of the proton nuclear magnetic resonance ('H-NMR) of compound group A1 obtained in Example 1 (1)
  • FIG. 2 is a chart of Example 1 (2)
  • Fig. 3 is a chart of the proton nuclear magnetic resonance ('H-NMR) of the obtained compound group A2.
  • Fig. 3 shows the compound group A3 proton nuclear magnetic resonance obtained in Example 1 (3).
  • FIG. 4 is a chart of proton nuclear magnetic resonance ( ⁇ -NMR) of compound group A4 obtained in Example 1 (4).
  • the transition metal compound of the present invention has the general formula (I)
  • M represents a metal element belonging to Groups 3 to 10 of the periodic table or a lanthanide series, and specific examples include titanium, zirconium, hafnium, and y. Examples include tritium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanide-based metals. Among them, catalysts for polymerization of olefins are group 4 elements. Certain titanium, zirconium and hafnium are preferred. X represents a sigma-binding ligand bonded to M.
  • the plurality of Xs may be the same or different, and may be cross-linked to an indenyl ring or ⁇ .
  • Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and a carbon atom.
  • ⁇ represents a Lewis base, and when there are a plurality of ⁇ , a plurality of ⁇ may be the same or different and may be cross-linked to an indenyl ring or X.
  • examples of this type include amines, ethers, phosphines, thioethers, esters, and nitriles.
  • ⁇ examples include ammonia, methylamine, aniline, Chillamine, Jethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, trin-butylamine, methyldiphenylamine , Pyridine, amines such as p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine Examples include phosphines such as quinine, teaters such as tetrahydrothiophene, esters such as ethyl benzoate, and nitriles such as acetonitrile and benzonitrile. be able to.
  • phosphines such as quinine
  • teaters such as tetrahydrothiophene
  • esters such as ethyl benzoate
  • A represents a cross-linking group, and a specific structure is represented by the formula (R'nQ).
  • Q is an atom selected from the 13th, 14th, 14th, 15th and 16th groups of the periodic table, and n is 2 when the Q force is 14 the group, 1 when the 13th and 15th groups are 1, 0 when the group is 6
  • R '2 C, R' 2 S i, R '2 G e, R' 2 S n, R 'A 1, R' P, R 'N, oxygen (- 0 -), sulfur (-S-), selen (-Se-) [where R 'is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, silicon When n is 2, R's may be the same or different.
  • (A) p represents an integer of 1 to 20.
  • Examples of the above are methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylidene, dimethylsilylene, tetramethyldisilylene, dimethylgermiene.
  • R 1 to R 8 each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero atom-containing group, They may be the same or different, or may form a ring with an adjacent group. Also, three R 4 's may be the same or different, and three R 8 ' s may be the same or different.
  • R ′, R 1 to R 8 include, in addition to a hydrogen atom, a halogen atom such as C 1, Br, F, I, methyl, ethyl, n-propyl, n-butyl, C1-C20 hydrocarbon groups such as isopropyl, isobutyl, and n-decyl; halogen-containing hydrocarbon groups such as trifluoromethyl; trimethylsilyl and dimethyl (t-butyl) silyl; Examples include a silicon-containing group, a heteroatom-containing group such as methoxy, ethoxyquin, and dimethylamino.
  • a halogen atom such as C 1, Br, F, I, methyl, ethyl, n-propyl, n-butyl, C1-C20 hydrocarbon groups such as isopropyl, isobutyl, and n-decyl
  • halogen-containing hydrocarbon groups such as trifluoromethyl
  • transition metal compound represented by the general formula (I) include rac — [and 2-ethylenebis (7 — (4-t-butylindenyl))] zirconium dichloride, rac — [ 1,2—ethylenebis (71- (4-methylindenyl))] zirconium dichloride, rac— [1,2—ethylenebis (7— (2,4—dimethylindenyl))] zirconium dichloride, rac — [shi 2 -ethylenebis (6 — (2,3-dimethylindenyl))] zirconium dichloride, rac 1 [shi 2 -ethylenbis (7 — (shi 4 -dimethylindenyl)) Zirconium dichloride, rac— [isopropylidenebis (7— (4-t-butylindul))] zirconium dichloride, rac—isopropylidenebis (7— (4—1 Methylindenyl)))) Zirconium dichloride
  • the catalyst for polymerization of olefins of the present invention comprises (A) a transition metal compound represented by the above general formula (I) and an activation co-catalyst, for example, (B) a transition metal compound of the component (A) or a derivative thereof. It is a catalyst containing a compound capable of forming an ionic complex by reacting with an organism and, if necessary, (C) an organic aluminum compound.
  • the transition metal compound represented by the general formula (I) used as the component (A) may be used alone or in combination of two or more.
  • the component (A) and the activating cocatalyst are used.
  • the activation promoter There is no particular limitation on the activation promoter,
  • the component (B) a transition metal compound of the component (A) or a compound capable of forming an ionic complex by reacting with a derivative thereof is used.
  • the component (B) includes (B-1) an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), (B-2) luminoxane, (B-3) Lewis acids can be mentioned.
  • any of ionic compounds capable of forming an ionic complex by reacting with the transition metal compound of the component (A) can be used. II), (III)
  • L 2 is M 2, R, 0 R 1 ' ⁇ 3, R' 2 3 C or R 13 M 3 o
  • L ′ represents a Lewis base
  • [Z] ⁇ represents a non-coordinating dione [ ⁇ ′] ⁇ or [ ⁇ 2 ] ⁇ .
  • [ ⁇ ']- is an anion in which multiple groups are bonded to an element, that is, [IV! 1 G 1 G 2 ⁇ ⁇ ⁇ G f )-
  • M ' is fifth to 1 V element of the periodic table, preferably a first 3-1 V element of the periodic table.
  • G' ⁇ G f are each a hydrogen atom, a halogen atom, Alkyl group having 2 to 20 carbon atoms, dialkylamino group having 2 to 40 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, carbon Alkyl aryl group having 7 to 40 carbon atoms, aryl alkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy group having 1 to 20 carbon atoms, organic metalloid group Or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms, wherein two or more of G 1 to G f may form a ring, and f is [(atom of central metal M ′ ) + 1], and [Z 2
  • R e represents a hydrogen atom, an alkyl group having 1 to 2 0 carbon atoms, the number of 6-2 0 ⁇ Li Lumpur group carbon, Arukirua Li Lumpur groups or ⁇ Li Ruarukiru group, R 1 * "and R 11 is a cyclopentenyl group, a substituted cyclopentenyl group, an indenyl group or a fluorenyl group, and R 12 is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group.
  • R 13 represents a macrocyclic ligand such as tetrafdinyl porphyrin, phthalocyanine, etc.
  • k represents the ionic valence of [L 1 -R 9 ], CL 2 ].
  • a is an integer of 1 or more
  • b a (k X a).
  • M 2 is one comprising a first, periodic table 3, 1 1 to 1 3, 1 7 group elements
  • M 3 represents an element in Groups 7 to 12 of the periodic table.]
  • L ′ examples include ammonia, methylamine, aniline, dimethylamine, getylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, Trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, ⁇ -bromo-N, N-dimethylaniline, p—dinitro-N, N-dimethylaniline Amines, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiothiophene, esters such as ethyl benzoate, and acetates. Examples include nitriles such as tonitrile and benzonitrile.
  • R 9 include hydrogen, methyl group, ethyl group, benzyl group, and trityl group.
  • R 1 G and R 1 ′ include: Examples include cyclopentenyl group, methylcyclopentenyl group, ethylcyclopentenyl group, and pentamethylcyclopentagenenyl group.
  • R 12 include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group.
  • R 13 include tetraphenylborfyl Phthalocyanine, aryl, and methallyl.
  • M 2 include Li, Na, K, Ag, C g, Br, I, and I 3.
  • Specific examples of M 3 include Can be listed as Mn, Fe, Co, Ni, and Zn.
  • [Zeta '] - namely [M' 'in, ⁇ G 1 G 2 ⁇ ⁇ ⁇ ]' is a specific example of ⁇ , A 1, Si, P , A s, such as S b, preferred Or B1 and A1.
  • G ' ⁇ G f Jimechirua Mi cyano group as a Jiarukirua Mi amino group, etc.
  • Jechirua Mi amino group an alkoxy group Wakashi Ku is main butoxy group and a ⁇ re Ruokishi group, Ethoxy, n-butoxy, phenoxy and other hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n- Octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl, etc.
  • Bromine, iodine, and heteroatom-containing hydrocarbon groups such as P-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, 3,4,5-trifluorophenyl, and pentafluorophenyl Group, 3, 5—Bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group, and other organic methyl groups such as pentamethylantimony, trimethylnyl, and trimethylgermyl groups , Diphenylarsine group, dicyclohexylantimony group, diphenylboron and the like.
  • heteroatom-containing hydrocarbon groups such as P-fluorophenyl, 3,5-difluorophenyl, pentachlorophenyl, 3,4,5-trifluorophenyl, and pentafluorophenyl Group, 3, 5—Bis (trifluoromethyl) phenyl group, bis (trimethylsilyl) methyl group,
  • non-coordinating anion that is, the conjugated salt group [Z 2 ] ⁇ of a blended acid alone or a combination of a blended acid and a Lewis acid having a pKa of ⁇ 10 or less are given below.
  • An example of such an ionic compound which reacts with the transition metal compound of the component (A) to form an ionic complex that is, a specific example of the compound of the component (B-1) is triethyl tetraphenylborate.
  • Tri-n-borate Tri-n-borate, butylammonium, tetrakis (fluorene phenyl) Triphenylborate, tetrakis (fluorene pentyl) Tetra n-borate, n-butylammonium, tetrakis Pentaphenylammonium borate, tetraethylammonium borate, tetraxammonium (phenylphenylphenyl) benzoyl borate (tri-n-butyl) ammonium, tetrakis (phenylphenylammonium), methyldiphenylammonium borate , Tetrakis (pentafluorophenyl) triphenyl (methyl) ammonium borate, tetrax (phenylfluorophenyl) methylanilinium borate, tetrakis (pentaphenylphenyl) phenyldimethylbor
  • the component (B-1), an ionic compound which forms an ionic complex by reacting with the transition metal compound of the component (A), may be used alone or in combination of two or more. Is also good.
  • R 14 represents a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or a halogen atom having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
  • w represent the degree of polymerization and are usually integers of 3 to 50, preferably 7 to 40. Note that each R 14 may be the same or different. ].
  • Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water.
  • the reaction is not particularly limited, and may be carried out according to a known method. For example, (1) a method in which an organic aluminum compound is dissolved in an organic solvent and brought into contact with water, (2) a method in which an organic aluminum compound is initially added during polymerization and water is added later, and (3) a metal salt is contained. Reaction of the water of crystallization, water adsorbed on organic or organic substances with organic aluminum compounds, and reaction of tetraalkylaluminum with trialkylaluminoxane and further reaction with water. is there. In addition, toluene may be insoluble in aluminum.
  • aluminoxanes may be used alone or in combination of two or more.
  • the Lewis acid as the component (B-3) is not particularly limited, and may be an organic compound or a solid inorganic compound.
  • a boron compound or an aluminum compound is preferably used, and as the inorganic compound, a magnesium compound or an aluminum compound is preferably used.
  • the aluminum compound for example, bis (2,6-di-t-butyl-4-methylphenoxy) aluminum-methyl, (shi-11-b2-naphthoxy) aluminummethyl, etc.
  • the aluminum compound include magnesium chloride and magnesium magnesium
  • examples of the aluminum compound include aluminum oxide and aluminum chloride
  • examples of the boron compound include triphenylboron and trisium.
  • One of these Lewis acids may be used, or two or more may be used in combination.
  • the use ratio of the (A) catalyst component to the (B) catalyst component is preferably 1 mole in the case of using the (B-1) compound as the (B) catalyst component.
  • the ratio is preferably in the range of 0: 1 to 1: 100, more preferably in the range of 2: 1 to 1:10, and when the compound (B-2) is used, the molar ratio is preferably 1: 1: A range of 1-1: 1.000,000, more preferably 1: 10-1: 100,000 is desirable.
  • the use ratio of the catalyst component (A) to the catalyst component (B-3) is preferably from 1: 0.1 to 1: 200, more preferably from 1: 0.2, in a molar ratio. 1: 100, more preferably in the range of 1: 0.5 to 1: 500.
  • the catalyst cost per unit weight of the polymer increases, which is not practical.
  • the catalyst component (B), (B-1), (B-2), (B-3) and the like can be used alone or in combination of two or more.
  • the polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C) organic components. It contains aluminum compound as a main component and is excellent
  • the organoaluminum compound of the component (c) is represented by the general formula (VI)
  • R 1 S represents an alkyl group having 1 to 10 carbon atoms
  • J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom.
  • V is an integer of 1 to 3.
  • Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, tributylbutylaluminum, dimethylaluminum chloride. , Getyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, getyl aluminum hydride, ethyl aluminum sesquichloride, etc. No.
  • organoaluminum compounds may be used alone or in combination of two or more.
  • the molar ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10.00000, more preferably 1: 5 to 1: 2. , 0000, more preferably in the range of 1:10 to 1: 1,000.
  • At least one of the catalyst components can be used by being supported on a suitable carrier.
  • the type of the carrier is not particularly limited, and any of an inorganic oxide carrier, other inorganic carriers and an organic carrier can be used. Particularly, from the viewpoint of morphology control, the inorganic oxide carrier and the like can be used. Or other inorganic carriers are preferred.
  • Is an inorganic oxide support specifically, S i 0 2, A 1 2 0 3, M g 0, Z r 02, T i 02, F e 2 0 3, B 2 0 3, C a O, ZnO, BaO, Th02 and mixtures thereof, for example, silica alumina, zeolite, bright, glass fiber and the like.
  • the inorganic oxide carrier may contain a small amount of a carbonate, a nitrate, a sulfate, or the like.
  • M g C l 2, U g C ⁇ (0 C 2 H 5), M g (0 C 2 H 5) one represented by magnesium compounds such as 2 general formula such as M g R 16 x X 'magnesium represented by y compound or a complex salt can and Ageruko.
  • R 16 is an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms
  • Each R 16 and each X 1 may be the same or different.
  • organic carrier examples include polymers such as polystyrene, styrene-divinyl benzene copolymer, polyethylene, polypropylene, substituted polystyrene, and polyarylate, and starch and carbon. And so on.
  • the carrier used in the present invention M g C l 2, g C 1 (0 C 2 H 5), M g (OC 2 H 5) 2, S i 02, A 1 2 0 3 , etc. is good or arbitrary .
  • the properties of the carrier vary depending on the type and manufacturing method, but the average particle size is usually l to 300 ⁇ m, preferably 10 to 200 ⁇ m, and more preferably 20 to 100 ⁇ m. 0 / zm.
  • the ratio surface ⁇ of carrier is usually 1 ⁇ 1 0 0 O m 2 Zg, favored properly is 5 0 ⁇ 5 0 0 m 2 Zg , pore volume is usually 0. 1 ⁇ 5 cm 3 Zg, preferred and rather Is 0.3 to 3 cm 3 Zg.
  • the specific surface area and pore volume can be determined, for example, from the volume of nitrogen gas adsorbed according to the BET method. (Journal of “OB”, “American”, “Chemical” Society, Vol. 60 , P. 309 (see 1983).
  • the above-mentioned carrier is used after being calcined usually at 150 to 1000, preferably at 200 to 800'C.
  • At least one of the catalyst components is supported on the carrier, at least one of (A) the catalyst component and (B) the catalyst component, preferably both (A) the catalyst component and (B) the catalyst component are used. It is desirable to carry it.
  • the method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited.
  • the method of mixing at least one of the component (A) and the component (B) with the carrier is not limited.
  • the carrier and (A) A method of reacting the component and the component (B) with the organoaluminum compound or the halogen-containing gayne compound; 4 After the component (A) or the component (B) is supported on a carrier, the component (B) or ⁇ A method of mixing the contact product of the component (A) with the component (B) with the carrier, 6 A method of coexisting the carrier in the contact reaction of the component (A) with the component (B). Etc. can be used.
  • an organic aluminum compound as the component (C) may be added.
  • the catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is.
  • a catalyst can be produced by carrying out loading operation of at least one of the components (A) and (B) on a carrier in a polymerization system.
  • a carrier for example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added, and a olefin such as ethylene is added at normal pressure to 20 kg / cm 2 ,
  • a method in which prepolymerization is performed at 120 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.
  • the use ratio of the compound (B-1) component and the carrier is preferably 1: 5 to 1: 100, more preferably 1:10 to 1: 1, by weight.
  • the ratio is preferably 500, and the ratio of the component (B-2) to the carrier is preferably 1: 0.5 to 1: 100, more preferably 1: 1, by weight.
  • the ratio of the component (B-3) to the carrier is preferably 1: 5 to 1: 10000, more preferably 1: 1 by weight. 0 to 1: It is desirable to set it to 500.
  • the ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10,000, more preferably 1:10 to 1: 500, by weight. It is desirable.
  • the (B) component If the proportion of the component (B-1), the component (B-2) or the component (B-3), and the carrier, or the proportion of the component (A) and the carrier deviates from the above range, the activity is reduced. May drop.
  • the average particle size of the polymerization catalyst of the present invention thus prepared is usually from 2 to 200 m ⁇ .
  • homopolymerization of olefins, or olefins and other olefins using the polymerization catalyst described above.
  • Copolymerization with Z or another monomer for example, copolymerization of different olefins with each other, copolymerization of olefins with other monomers, or (Copolymerization between fins and other monomers) can be suitably performed.
  • the olefins are not particularly limited, but ⁇ -olefins having 2 to 20 carbon atoms are preferred.
  • This one-year-old refin includes, for example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1— Octene, 1-decene, 1-dodecene, 1-tetradecen, 1-hexadecene, 1-octadecene, 1 eicosene, styrene, ⁇ -methylstyrene, isopropylstyrene, t-butylstyrene, etc. Can be mentioned.
  • the above-described other classes may be appropriately selected from the above-mentioned classes.
  • the above-mentioned orifices may be used alone or in combination of two or more.
  • the above-mentioned orifices can be arbitrarily combined.
  • propylene and ethylene, or ethylene and ⁇ -olefin having 3 to 10 carbon atoms are copolymerized, propylene and ethylene, or ethylene and carbon are used.
  • the co-polymerization ratio (molar ratio) with ⁇ -olefin of Formulas 3 to 10 is usually 99.9: 0.1 to 0.1: 99.9, preferably 99.5: 0. 5-75.0: Selected in the range of 25.0.
  • the above-mentioned olefins and other monomers may be copolymerized, and the other monomers used in this case include, for example, Bugen Gen: Isoprene. 1,5—Chain diolefins such as hexadiene; norbornane; 1,4,5,8 —Dimethanones 2,3,4,4a, 5,8,8a — Cytahydronaphthalene; cyclic olefins such as 2-norbornene, norbornadiene, 5-bornyldenenoruborene, 5-vinylvinylnorbornene, and cyclic cycloolefins such as dicyclopentene, acrylic.
  • Bugen Gen Isoprene. 1,5—Chain diolefins such as hexadiene; norbornane; 1,4,5,8 —Dimethanones 2,3,4,4a, 5,8,8a — Cytahydronaphthalene; cyclic o
  • Unsaturated esters such as ethyl ester and methyl methacrylate
  • lactones such as / S-propiolactone, / S-butyrolactone and 7-butyrolactone , £ Ichiriki Pro Lactum, ⁇ Arm, epoxy propane; 1, 2 - epoxy pigs emissions of which epoxides and the like can and Ageruko.
  • the polymerization catalyst of the present invention can be used not only for the polymerization of the above-mentioned olefins, but also for polymerization of other than the olefins.
  • the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Polymerization and gas phase polymerization are particularly preferred.
  • the polymerization 'condition, the polymerization temperature is usually one 1 0 0 ⁇ 2 5 0 e C , Shi preferred Te Ku Her 5 0-2 0 0, more preferred properly is 0 ⁇ 1 3 0 e C.
  • the proportion of the catalyst to the reaction raw material, the raw material monomer Z component (A) (molar ratio) is preferable properly 1 to 1 0 8, in particular 1 0 0-1 0 5 become this and is favored arbitrary.
  • the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to SOO kgZcm 2 G, particularly preferably normal pressure to 100 kg / cm 2 G.
  • Methods for adjusting the molecular weight of the polymer include selection of the type and amount of each catalyst component used, the polymerization temperature, and polymerization in the presence of hydrogen.
  • a polymerization solvent for example, aromatic hydrocarbons such as benzene, toluene, quinylene, and ethylbenzene, alicyclic hydrocarbons such as cyclo ⁇ -pentane, cyclohexane, and methylcyclohexane, pentane, hexane Aliphatic hydrocarbons such as octane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used.
  • aromatic hydrocarbons such as benzene, toluene, quinylene, and ethylbenzene
  • alicyclic hydrocarbons such as cyclo ⁇ -pentane, cyclohexane, and methylcyclohexane
  • pentane hexane
  • Aliphatic hydrocarbons such as octane, heptane and octane
  • the molecular weight of the polymer obtained in this way is not particularly limited, but the intrinsic viscosity [7?] (Measured in 135′C decalin) is 0.1 deciliter / g.
  • the above is preferable, and in particular, 0.2 g / g or more Zg or more is preferable.
  • preliminary polymerization can be performed using the polymerization catalyst.
  • the prepolymerization can be carried out by bringing a small amount of an orifice into contact with the solid catalyst component, for example, but the method is not particularly limited, and a known method can be used.
  • the orifice used in the prepolymerization there is no particular limitation on the orifice used in the prepolymerization, and the same as those exemplified above, for example, Examples thereof include ethylene, one-year-old olefin having 3 to 20 carbon atoms, and a mixture thereof. It is advantageous to use the same olefin as used in the polymerization.
  • the prepolymerization temperature is usually from 120 to 200, preferably from -10 to 130, more preferably from 0 to 80.
  • an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Further, the prepolymerization may be performed without a solvent.
  • the intrinsic viscosity [7?] (Measured in 135 ° C decalin) of the prepolymerized product is more than 0.2 deciliters, especially more than 0.5 deciliters, in the catalyst. It is desirable to adjust the conditions so that the amount of the prepolymerized product per 1 mol of the transition metal component is 1 to 1000 g, particularly 100 to 100 g.
  • the olefin polymer of the present invention having a narrow molecular weight distribution and a relatively wide composition distribution can be efficiently obtained.
  • Fig. 2 shows the ⁇ -NMR chart.
  • FIG. 3 shows the 'H-NMR chart.
  • FIG. 4 shows the ⁇ -NMR chart.
  • compound A12 which is considered to be a meso form, was obtained as a yellow powder by extraction with dichloromethane 20 milliliters.
  • Example 3 6 mmol of methylaluminoxane was used in place of 1 mmol of TIBA, and N, N-dimethylanilinium tetratetrakis (pentylfluorophenyl) borate was not used. Except for, the procedure was performed in the same manner as in Example 2. Table 1 shows the results.
  • Example 3 was carried out in the same manner as in Example 3 except that toluene was used at 400 milliliters and that 1-octene 40 milliliter was not used. Table 1 shows the results.
  • Example 4 was carried out in the same manner as in Example 4 except that toluene was used at 400 milliliters and that 1-octene 40 milliliter was not used. Table 1 shows the results. Table 1 1
  • compound B12 which is considered to be a racemic body, was obtained as a yellow powder by extraction with dichloromethane 20 milliliters.
  • reaction product is poured into a methanol-hydrochloric acid solution, stirred sufficiently, separated, washed thoroughly with methanol and dried, and then dried. 8 g were obtained. It had a melting point of 159 and a pentad-meso fraction CmnimnO of 90.2%. No peak of 2,1 insertion was observed from the NMR chart.
  • Ventatsu meso fraction [mmmm] is attributed to the pen mesomethod out of the total area of the nine signals appearing between 19 and 22 ppm out of 13 C of the volimer. It was measured as the ratio of the area occupied by the 1.545 ppm signal.
  • compound D12 which is considered to be a racemate, was obtained as a yellow powder from the extracted residue by extraction with hexane 20 milliliters.
  • Example 9 was carried out in the same manner as in Example 9 except that D11 was used instead of Catalyst B11. Table 2 shows the results.
  • Example 9 was carried out in the same manner as in Example 9 except that E11 was used instead of the catalyst B11. Table 2 shows the results.
  • Example 9 was carried out in the same manner as in Example 9 except that F11 was used instead of the catalyst B11. Table 2 shows the results.
  • the transition metal compound of the present invention is a novel compound and is useful as a catalyst component for olefin polymerization. Further, the olefin polymer catalyst of the present invention has high activity, and by using the catalyst, an olefin polymer having a narrow molecular weight distribution and a relatively wide composition distribution can be efficiently obtained. In addition, since there is almost no heterogeneous bond due to 2,1-insertion in the polypropylene chain, a propylene polymer having a high melting point can be obtained. Industrial applicability
  • the transition metal compound of the present invention is useful as a component of an olefin polymerization catalyst.
  • the polymerization catalyst containing the transition metal compound is highly active, and gives an olefin-based polymer having a narrow molecular weight distribution and a relatively wide composition distribution, or a highly regular polypropylene. Can be. Further, by using this polymerization catalyst, an olefin homopolymer or a copolymer can be efficiently produced.

Abstract

Nouveau composé de métal de transition représenté par la formule générale (I) (dans laquelle chaque symbole correspond à sa définition dans le texte) et catalyseur de polymérisation d'oléfine contenant (A) le composé de métal de transition (I), (B) un co-catalyseur actif, tel qu'un composé capable de réagir avec le composé de métal ou un de ses dérivés, pour donner un complexe ionique et, si nécessaire, (C) un composé d'organoaluminium: (I). Le composé de métal de transition est efficace en tant que constituant du catalyseur de polymérisation d'oléfine et le polymère d'oléfine, obtenu par l'intermédiaire dudit catalyseur possède un poids moléculaire à répartition étroite par rapport à une composition à répartition large.
PCT/JP1995/001530 1994-08-02 1995-08-02 Compose de metal de transition, catalyseur de polymerisation d'olefine, polymere d'olefine obtenu au moyen du catalyseur et procede de production du polymere WO1996004317A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996038458A1 (fr) * 1995-05-30 1996-12-05 Montell Technology Company B.V. Metallocenes pontes, procedes pour les preparer et leur utilisation comme catalyseurs pour la polymerisation d'olefines
JP2001247611A (ja) * 1999-12-27 2001-09-11 Sumitomo Chem Co Ltd 付加重合用触媒成分、付加重合用触媒および付加重合体の製造方法
US7538168B2 (en) 2005-12-14 2009-05-26 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7550544B2 (en) 2005-12-14 2009-06-23 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7557171B2 (en) 2004-12-16 2009-07-07 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7667064B2 (en) 2005-12-14 2010-02-23 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7763562B2 (en) 2005-12-14 2010-07-27 Exxonmobil Chemical Patents Inc. Heteroatom bridged metallocene compounds for olefin polymerization
US7812104B2 (en) 2008-01-18 2010-10-12 Exxonmobil Chemical Patents Inc. Production of propylene-based polymers
US7868197B2 (en) 2005-12-14 2011-01-11 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
CN112661785A (zh) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 一种萘氧基单茂过渡金属化合物、包含其的催化剂组合物与应用

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JPH0543618A (ja) * 1990-11-30 1993-02-23 Idemitsu Kosan Co Ltd オレフイン系重合体の製造方法
JPH0551414A (ja) * 1991-08-28 1993-03-02 Mitsui Toatsu Chem Inc 新規プロピレン系共重合体およびその製造方法
JPH05140227A (ja) * 1991-05-27 1993-06-08 Hoechst Ag 広い分子量分布を有するポリオレフインの製造方法

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JPH0543618A (ja) * 1990-11-30 1993-02-23 Idemitsu Kosan Co Ltd オレフイン系重合体の製造方法
JPH05140227A (ja) * 1991-05-27 1993-06-08 Hoechst Ag 広い分子量分布を有するポリオレフインの製造方法
JPH0551414A (ja) * 1991-08-28 1993-03-02 Mitsui Toatsu Chem Inc 新規プロピレン系共重合体およびその製造方法

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369254B1 (en) 1995-05-30 2002-04-09 Basell Technology Company Bv Bridged metallocene compounds, processes for the preparation thereof and use thereof in catalysts for the polymerization of olefins
WO1996038458A1 (fr) * 1995-05-30 1996-12-05 Montell Technology Company B.V. Metallocenes pontes, procedes pour les preparer et leur utilisation comme catalyseurs pour la polymerisation d'olefines
JP2001247611A (ja) * 1999-12-27 2001-09-11 Sumitomo Chem Co Ltd 付加重合用触媒成分、付加重合用触媒および付加重合体の製造方法
US7709670B2 (en) 2004-12-16 2010-05-04 Exxonmobil Chemical Patents Inc. Process for producing substituted metallocene compounds for olefin polymerization
US9163046B2 (en) 2004-12-16 2015-10-20 Exxonmobil Chemical Patents Inc. Process for producing substituted metallocene compounds for olefin polymerization
US7557171B2 (en) 2004-12-16 2009-07-07 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7763562B2 (en) 2005-12-14 2010-07-27 Exxonmobil Chemical Patents Inc. Heteroatom bridged metallocene compounds for olefin polymerization
US7667064B2 (en) 2005-12-14 2010-02-23 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7550544B2 (en) 2005-12-14 2009-06-23 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7868197B2 (en) 2005-12-14 2011-01-11 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
US8173828B2 (en) 2005-12-14 2012-05-08 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
US8546595B2 (en) 2005-12-14 2013-10-01 Exxonmobil Chemical Patents Inc. Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
US7538168B2 (en) 2005-12-14 2009-05-26 Exxonmobil Chemical Patents Inc. Halogen substituted metallocene compounds for olefin polymerization
US7812104B2 (en) 2008-01-18 2010-10-12 Exxonmobil Chemical Patents Inc. Production of propylene-based polymers
CN112661785A (zh) * 2019-10-15 2021-04-16 中国石油化工股份有限公司 一种萘氧基单茂过渡金属化合物、包含其的催化剂组合物与应用
CN112661785B (zh) * 2019-10-15 2022-10-21 中国石油化工股份有限公司 一种萘氧基单茂过渡金属化合物、包含其的催化剂组合物与应用

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