WO1998028341A1 - Procede pour preparer des polymeres d'olefine - Google Patents
Procede pour preparer des polymeres d'olefine Download PDFInfo
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- WO1998028341A1 WO1998028341A1 PCT/JP1997/004717 JP9704717W WO9828341A1 WO 1998028341 A1 WO1998028341 A1 WO 1998028341A1 JP 9704717 W JP9704717 W JP 9704717W WO 9828341 A1 WO9828341 A1 WO 9828341A1
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
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- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
Definitions
- the present invention relates to a method for producing an olefin polymer. More specifically, the present invention relates to a method for producing an olefin polymer using a transition metal compound represented by a metallocene complex, which does not require the use of an aromatic hydrocarbon as a solvent.
- the olefin polymer includes a homopolymer of olefin and a copolymer of plural types of olefins.
- Transition metal compounds especially a diimine complex, a transition metal complex having two or one group having a cyclopentene anion skeleton, a so-called non-meta-open complex or a meta-open complex and a polymerization catalyst using an aluminoxane
- a diimine complex e.g., a diimine complex
- a transition metal complex having two or one group having a cyclopentene anion skeleton e.g., a so-called non-meta-open complex or a meta-open complex
- a polymerization catalyst using an aluminoxane has been reported to exhibit high activity in the polymerization of olefins.
- meta-metacene complexes when meta-metacene complexes are used, they exhibit extremely useful characteristics industrially, such as formation of olefin polymers with narrow molecular weight distribution and composition distribution. Therefore, many reports have been made in recent years (eg, Japanese Patent Publication No. 58-19
- transition metal compounds for example, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentagenenyl) (fluorenyl) zirconium dichloride, dimethylsilyl (tert-butylamide) (tetramethylcyclopentagenenyl) titanium Since dichloride and the like are soluble in aromatic hydrocarbon solvents such as toluene, but hardly soluble in aliphatic hydrocarbon solvents, they were usually treated as a solution of aromatic hydrocarbon solvent.
- the boron compound is a particulate solid and is soluble to some extent in an aromatic hydrocarbon solvent such as toluene, but has a very low solubility in other solvents, especially in aliphatic hydrocarbon solvents.
- an aromatic hydrocarbon solvent such as toluene.
- Such solvents are a major problem because they can remain in the polymer product and cause odor. Disclosure of the invention
- An object of the present invention is to provide a method for producing an olefin polymer using a transition metal compound, which method does not require the use of an aromatic hydrocarbon solvent which may remain in a polymer as a product and cause odor. is there.
- an olefin polymerization catalyst comprising the following (A) and (C) as a catalyst component, or an olefin polymerization catalyst comprising the following (A), (B) and (C) as a catalyst component:
- the present invention relates to a method for producing an olefin polymer by homopolymerizing or copolymerizing olefin in the presence of a catalyst.
- (B) A compound selected from the following (B1) to (B3) dissolved, suspended, or slurried in an aliphatic hydrocarbon compound
- E 1 to E 3 are each a hydrocarbon group having 1 to 8 carbon atoms, and all E ′′, all E 2 and all E 3 are different even if they are the same.
- Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
- a is a number satisfying 0 ⁇ a ⁇ 3
- b is an integer of 2 or more
- c represents an integer of 1 or more.
- (C 3) A boron compound represented by the general formula (L—H) + (BQ′Q 2 Q 3 Q 4 ) — (In each of the above general formulas, ⁇ represents a boron atom in a trivalent valence state.
- Q 1 to Q 4 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, a halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl containing 1 to 20 carbon atoms. group, an alkoxy group or 2-20 carbon atoms containing from 1 to 20 carbon atoms are including amino groups, they may be different even in the same.
- G + is was inorganic or organic Where L is a neutral Lewis base and (L—H) + is prensted acid.)
- the component (A) and the component (C) constituting the catalyst for polymerization of olefins of the present invention or the component (B) do not require an aromatic hydrocarbon compound as a solvent.
- An aliphatic hydrocarbon solvent is used as a solvent for dissolving, suspending or slurrying these catalyst components.
- the component (A) of the catalyst for polymerization of olefin used in the present invention is a transition metal compound dissolved, suspended or slurried in an aliphatic hydrocarbon compound.
- the transition metal compound is preferably a compound of a transition metal belonging to Groups 3 to 12 or a lanthanoid group of the Periodic Table of Elements (1993, I UPAC), and a transition metal compound having various olefin polymerization activities.
- Meta-mouthed cene complexes Non-meta-mouthed cene complexes are available. More preferably, it is a transition metal compound of the group 4 or lanthanide series, and further preferably, a transition metal compound having at least one group having a cyclopentene dianion skeleton, i.e., a meta-opencene transition metal compound. .
- the meta-mouthed transition metal compound is, for example, a compound represented by the following general formula (3).
- M is a transition metal atom belonging to Group 4 of the periodic table of the element (1993, IUPAC) or a lanthanide series. Specific examples thereof include a titanium atom, a zirconium atom, and a hafnium atom as transition metal atoms of Group 4 of the periodic table, and a samarium atom as a lanthanide-based transition metal atom. Can be Preferably, it is a titanium atom, a zirconium atom or a hafnium atom.
- L is a group having a cyclopentene anion skeleton or a group containing a hetero atom, and at least one is a cyclopentene anion skeleton. Group.
- a plurality of L may be the same or different, and may be cross-linked to each other.
- Shikuropen Yuji Eniru group 7 5 - - Shikuropen evening Gen-shaped 77 5 as a base having an Anion skeleton?
- 5 -Substituted cyclopentenyl group as a substituent, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms And the like.
- a polycyclic group having a cyclopentene anion skeleton 7? 5- indenyl group ⁇ v 5- fluorenyl group and the like.
- the hetero atom in the group containing a hetero atom includes a nitrogen atom, a phosphorus atom, an oxygen atom, a sulfur atom and the like.
- Examples of such a group containing a hetero atom include a hydrocarbon amino group, a hydrocarbon phosphino group, a hydrocarbon oxy group, a hydrocarbon thio group, and the like, and preferably, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group.
- 5 -substituted cyclopentagenenyl groups include 7] 5 -methylcyclopentenyl group, 7] 5- ethylcyclopentenyl group, 7? 5 - normal professional building sheet Kuropen evening Jeniru group, 7] 5 - isopropyl building cyclopentadienyl group, 7 5 -? Nor
- polycyclic group having a Shikuropen evening Jen shaped Anion skeleton 77 5 - indenyl group, 7 5 -? 2-methylindenyl group, 77 5 _ 4-methylindenyl group, 77 5 - 4, 5, 6, 7-tetrahydroindenyl group, 7 5 -? Furuoreniru group.
- the group containing a hetero atom examples include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group, a methylthio group, a dimethylamino group, a methylamino group, a dipropylamino group, a dibutylamino group, a diphenylamino group, Examples thereof include an alkyl group and a dimethylphosphino group.
- Groups having a cyclopentene anion skeleton, or groups having a cyclopentenyl skeleton and a group containing a hetero atom may be cross-linked, in which case, an alkylene group such as an ethylene group or a propylene group, A substituted alkylene group such as a dimethylmethylene group or a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a tetramethyldisilylene group may be present.
- R 3 in the general formula (3) representing the meta-mouthed transition metal compound is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- a is a number satisfying 0 ⁇ a ⁇ p
- P is the valence of the transition metal atom M.
- R 3 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a carbon atom having 1 to 20 carbon atoms as a halogen atom. 6
- hydride group examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a phenyl group, and a benzyl group.
- R 3 is preferably a chlorine atom, a methyl group or a benzyl group.
- transition metal atom M is a zirconium atom
- transition metal atom M is a zirconium atom
- zirconium is replaced with titanium or ha.
- Compounds substituted with phenyl can also be exemplified.
- One of these meta-acene-based transition metal compounds may be used alone, or two or more thereof may be used in combination.
- the component (A) of the catalyst for polymerization of olefin used in the present invention is a transition metal compound dissolved, suspended or slurried in an aliphatic hydrocarbon compound, and is preferably dissolved in an aliphatic hydrocarbon compound. Transition metal compounds are used.
- transition metal compounds soluble in such aliphatic hydrocarbon compounds include isopropylidene (cyclopentenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclohexane) Pennil genyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride.
- the component (B) used in the present invention is a compound selected from the following (B1) to (B3) dissolved, suspended or slurried in an aliphatic hydrocarbon compound.
- E ′ to E 3 are each a hydrocarbon group having 1 to 8 carbon atoms, and all E 2 and all E 3 may be the same or different.
- Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different.
- a is a number satisfying 0 ⁇ a ⁇ 3
- b is an integer of 2 or more
- c is Represents an integer of 1 or more.
- An organoaluminum compound represented by the general formula A 1 Z 3 _ a Specific examples of (B 1), trimethyl aluminum, tri-E chill aluminum, Toripuropirua Rumi two ⁇ beam, triisobutyl aluminum, trialkyl aluminum, such as hexyl aluminum to tri Dimethylaluminum chloride, getylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum Dialkylaluminum chlorides such as chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride; dimethylaluminum hydride, getylaluminum Examples thereof include dialkylaluminum hydrides such as hydride, dipropylaluminum hydride, diisobuty
- it is a trialkylaluminum, more preferably, triethyl aluminum or triisobutylaluminum.
- E 2 and E 3 in the linear aluminoxane (B 3) having a structure represented by the following are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Examples thereof include an alkyl group such as an isobutyl group, an n-pentyl group, and a neopentyl group.
- b is an integer of 2 or more
- c is an integer of 1 or more.
- E 2 and E 3 are a methyl group or an isobutyl group, b is 2-40 and c is 1-40.
- the above aluminoxanes are made by various methods.
- the method is not particularly limited, and may be made according to a known method.
- a solution prepared by dissolving a trialkylaluminum (eg, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, etc.) is brought into contact with water.
- a method in which a trialkylaluminum (eg, trimethylaluminum) is brought into contact with a metal salt containing water of crystallization (eg, copper sulfate hydrate) can be exemplified.
- one or more boron compounds selected from the following (C1) to (C3) are used.
- Preferred Q 1 to Q 3 are a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, and a halogenated hydrocarbon group containing 1 to 20 carbon atoms.
- the compound (C 1) include tris (pentafluorophenyl) poran, tris (2,3,5,6-tetrafluorophenyl) borane, and tris (2,3,4,5-tetrafluorophenyl) Borane, tris (3,4,5-trifluorene phenyl) borane, tris (2,3,4-trifluorophenyl) borane, phenylbis (pentafluorophenyl) porane, etc., most preferably tris (Penyu fluorophenyl) It is borane.
- G + is an inorganic or organic cation
- B is a boron atom in a trivalent valence state
- Q ′ to Q 4 are the same as Q ′ to Q 3 in (C 1) above.
- the inorganic cation G + includes a phenium cation, an alkyl-substituted phenium cation, and a silver cation.
- G + which is an organic cation includes a triphenylmethyl cation and the like.
- Preferred as G + is carbenidum cation.
- (BQ 'Q 2 Q 3 Q 4 ) includes tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate and tetrakis (2,3,4,5-tetra Fluorophenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) porate, tetrakis (3,5) —Bistrifluoromethylphenyl) borate and the like.
- Fluorophenyl) borate 1,1'-Dimethyl ferrocenedium tetrakis (vinyl fluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, triphenylmethyltetrakis (pentafluorofluorophenyl) porate, tritium Examples thereof include refenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.
- Component (C) is preferably (C 2) or (C 3), particularly preferably triphenylmethyltetrakis (pentafluorophenyl) porate or ⁇ , ⁇ -dimethylanilinium tetrakis (pentafluorophenyl) ) Porates, and most preferably ⁇ , ⁇ _dimethylaniliniumtetrakis (pentafluorofluorenyl) porate.
- the olefin polymerization catalyst comprising the above ( ⁇ ⁇ ⁇ ) and (C) as the catalyst component, or the above (A), () and (C) as the catalyst component Olefin polymerization catalyst.
- a part or all of each of the above-mentioned catalyst components is continuously supplied to a catalyst preparation device to prepare an olefin polymerization catalyst, or each of the above-mentioned catalyst components is continuously supplied to the olefin polymerization device.
- the olefin polymerization catalyst prepared in this manner is used.
- the respective catalyst components can be charged and used in an arbitrary order, and any combination thereof may be used after contacting them in advance.
- each catalyst component may be used in a state of being suspended or slurryed in an aliphatic hydrocarbon compound.
- the state of being suspended or slurried in a solvent refers to a state in which a solid is not completely dissolved in a solvent and solid particles are dispersed in the solvent.
- the suspended state and the slurry state are not particularly distinguished.
- each of the above catalyst components when supplied in a suspended or slurry state in a solvent, for example, the catalyst components are suspended or slurried so as not to deposit in the pipe. It is preferable that the sedimentation velocity of each catalyst component is lower than the flow velocity in the pipe.
- the solvent used for dissolving, suspending or slurrying in the solvent includes: It is not particularly limited as long as it is an aliphatic hydrocarbon compound that does not cause a problem when using each catalyst component, and examples thereof include butane, hexane, heptane, octane, cyclohexane, dodecane, and liquid paraffin.
- a solvent having a high viscosity so that the sedimentation speed of each catalyst component in a suspended or slurry state becomes slower than the flow rate in the pipe.
- the solvent preferably has a viscosity of 0.8 cp (centipoise) or more, more preferably 1.4 to 1200 cp, and still more preferably 1.6 to 50 cp.
- high-viscosity solvents include dodecane, various liquid paraffins, and the like, and mixed solvents of these with other solvents.
- liquid paraffin for example, commercially available liquids having various viscosities of about 2 to 2000 cp can be used.
- the viscosity here refers to the viscosity at 20 ° C.
- Such a high-viscosity solvent is particularly preferably used as a solvent for the above component (C), and more preferably as a solvent for the above components (C) and (A).
- a solvent for the above component (C) is particularly preferably used as a solvent for the above component (C), and more preferably as a solvent for the above components (C) and (A).
- the pipe diameter of the pipe when the pipe is used there is no particular limitation on the pipe diameter of the pipe when the pipe is used, but 0.5 to 100 mm, preferably:! 5050 mm, more preferably 1.5-30 mm.
- the concentration of each catalyst component is appropriately selected depending on conditions such as the performance of a device for supplying each catalyst component to the polymerization reactor.
- the component (A) power is usually 0.01 to 500 ⁇ mol / g.
- each component is used in a range of 0.05 to 200 / mol / g, more preferably 0.05 to: I00mo1 / g.
- the above component (C) and many components (A) are soluble to some extent in aromatic hydrocarbon compounds such as toluene, the solubility in aliphatic hydrocarbon compounds is low, and the above components contained in the solution ( C) is a small amount, but each catalyst component is suspended or
- the method in which the components (C) are supplied in a separated state is particularly preferable because the component (C) can be supplied in a large amount and in a smaller volume.
- the ratio of the amount of the component (C) to the amount of the solvent can be supplied as 0.0001 to 800 mmol Z liter as the number of moles of the boron compound with respect to the solvent volume. Can be supplied at 0.001 to 500 mmol / l.
- each catalyst component used in the catalyst for polymerization of olefins used in the present invention is such that the molar ratio of component (B) to component (A) is 0.1 to: L0000, preferably 5 to 200.
- Component (C) It is desirable to use each component such that the molar ratio of the Z component (A) is in the range of 0.01 to: L00, preferably in the range of 0.5 to 10.
- any of the olefins having 2 to 20 carbon atoms can be used, and two or more types of the olefins can be used at the same time.
- Specific examples of such olefins include ethylene; linear ⁇ -olefins such as propylene, butene-11, pentene-11, hexene_1, heptene-11, octene-1, nonene-1, decene-11; 3-methylbutene-1, 3-methylpentene-11, 4-methylpentene-11, 5-methyl-2-pentene_1, etc .; branched olefins; vinylcyclohexane, etc .; It should not be limited to compounds.
- the combination of monomers when performing the copolymerization include ethylene and propylene, ethylene and butene-11, ethylene and hexene-1, ethylene and octene-11, propylene and butene-11, and the like.
- the present invention is not intended to be limited to these combinations.
- the present invention particularly relates to the copolymerization of ethylene with propylene, butene-11, 4-methylpentene-11, hexene-11, octene-1 and the like. Effectively applicable to polymer production.
- the polymerization method is not particularly limited, for example, solvent polymerization or slurry polymerization using an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, or the like as a solvent, without solvent, under high temperature and high pressure High-pressure ionic polymerization, gas-phase polymerization in gaseous monomers, etc. are possible. But it is possible.
- a preferred polymerization method in the present invention is to polymerize the olefin under the conditions of 120 to 250 ° C. and 5 to 50 kg Zcm 2 at which the polymer melts using a solvent such as cyclohexane.
- This is a high-temperature solution method or a high-pressure ionic polymerization method in which a polymer that forms a supercritical fluid state olefin under a high temperature and high pressure without solvent is polymerized in a molten state.
- the polymerization preferably 3 5 0 to 3 5 0 0 kg Z cm 2 of pressure, at least 1 3 0 ° C, preferably 1 3 5-3 5 0 temperature I do.
- the polymerization system may be either a batch system or a continuous system, but is preferably performed in a continuous system.
- a stirred tank reactor or a tubular reactor can be used as the reactor.
- the polymerization may be carried out in a single reaction zone, but may be carried out by dividing one reactor into a plurality of reaction zones, or by connecting a plurality of reactors in series or in parallel.
- any combination of a tank type-tank type or a tank type single tube type may be used.
- Each catalyst component is usually fed to the reactor by a high pressure pump.
- the catalyst is injected into the high-pressure section by a pump, so if the catalyst is in a liquid state, is uniformly dissolved in a solvent, or is a solid that is insoluble in the solvent, the particle size is small. Those which are small and have good dispersibility in a solvent are preferred.
- the particle size at that time is usually preferably such that the maximum particle size is 50 m or less, more preferably 30 jLt m or less, particularly preferably 10 zm or less, most preferably 5 zx m or less. is there.
- a method such as pulverization or a method in which a solution dissolved in toluene or the like is dropped into an aliphatic hydrocarbon solvent such as heptane and precipitated can be applied.
- the catalyst solution is usually handled in an atmosphere of an inert gas such as nitrogen or argon so as not to come into contact with water and air.
- an inert gas such as nitrogen or argon
- the polymerization time is appropriately determined depending on the kind of a target polymer and a reaction apparatus, and there is no particular condition to be limited.
- a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the copolymer.
- FIG. 1 is a flowchart for helping the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this embodiment.
- BEST MODE FOR CARRYING OUT THE INVENTION is a representative example of the embodiment of the present invention, and the present invention is not limited to this embodiment.
- the properties of the polymers in the examples were measured by the following methods.
- Melt index (MFR) was measured at 190 ° C according to the method specified in JIS K-6760.
- the density was determined according to JIS K-6760.
- the density value described as density (without annealing) is a value measured without annealing treatment in JISK-6760
- the density value described as density (with annealing) is a measurement value after annealing treatment. It is.
- Heating Heating up to 150 ° C, holding until the change in heat becomes stable
- ⁇ -lean refine content Determined from the characteristic absorption of ethylene and ⁇ -lelefin using an infrared spectrophotometer (FT-IR7300, manufactured by JASCO Corporation), the number of short-chain branches per 1000 carbons (SCB).
- Molecular weight and molecular weight distribution The molecular weight and molecular weight distribution were determined using a gel permeation chromatograph (150, C, manufactured by Otters Corporation) under the following conditions.
- the mixture obtained above was added dropwise at 140 ° C. to a solution composed of dichlorodimethylsilane (131 g) and hexane (306 ml). The resulting mixture was heated to room temperature over 2 hours, and further stirred at room temperature for 12 hours.
- the mixture obtained above was added dropwise to a toluene solution (5 Oml) of titanium tetrachloride (4.82 g) at 0 ° C under a nitrogen atmosphere, and then the temperature was raised to room temperature over 1 hour. Heated to reflux for an hour.
- ethylene and Ten-11 was continuously supplied into the reactor to perform polymerization.
- the polymerization conditions were set such that the total pressure was 800 kgZcm 2 G, the butene-11 concentration was 29 mol%, and the hydrogen concentration was 0.12 mol%.
- N, N-dimethylaniliniumtetrakis (pentafluorophenyl) porate (finely divided by reprecipitation method using toluene and heptane. Particle size is 2-3 m; 10 / m or more Prepare 2 mollZg) in separate containers and supply them at 300 gZh, 360 gZh and 750 gZh at a feed rate of 3.175 mm in diameter.
- the reactor was continuously fed through a tube.
- the polymerization reaction temperature was set to 230 ° C, the molar ratio of A1 atom to Ti atom was set to 60, and the ratio of boron atom to Ti atom was set to 4.4.
- Ethylene and butene-11 were continuously fed into the reactor using a 1-liter internal volume autoclave reactor equipped with stirring blades to carry out polymerization.
- the polymerization conditions were set such that the total pressure was 800 kgZcm 2 G and the butene-1 concentration was 45.9 mol%.
- the ratio of boron atom to Ti atom is as follows:
- the particle diameter is 2 to 3 m and the particle of 10 tm or more is not observed.
- This mixed suspension Solution and triisobutylaluminum heptane solution (5.47 xmol Zg) were prepared in separate containers, and each was supplied with a tube diameter of 3.17 gZ and 240 g / h at a feed rate of 3.17 5
- the reactor was continuously fed through mm tubing.
- the polymerization reaction temperature was adjusted to 205 e C, and the molar ratio of A 1 atom to Ti atom was adjusted to 61.7.
- the density (without annealing) was 0.873 g / cm 3
- the MFR was 6.8 g Z 10 minutes
- the molecular weight (Mw) was 720
- the molecular weight distribution (MwZMn) was 1.7 Was produced at a rate of 98.4 ton per mole of Ti atom per hour.
- Ethylene and butene-11 were continuously fed into the reactor using an autoclave type reactor equipped with stirring blades having an inner volume of 1 liter to carry out polymerization.
- the polymerization conditions were set such that the total pressure was 800 kgZcm 2 G and the butene-11 concentration was 47.0 mol%.
- Dimethylsilyl (tetramethylcyclopentagenyl) (3-tert-butyl _) in a mixture of heptane and liquid paraffin (Cristol 2022, manufactured by Etsuso Oil Co., Ltd.) (volume ratio heptane: liquid paraffin 1: 4) 5-Methyl-2-phenoxy) titanium dichloride was dissolved (0.066 umol / g), and N, N-dimethylanilinium tetrakis (pentafluorophenyl) porate (toluene and heptane) was dissolved in the solution.
- Particles having a particle size of 2 to 3 m and particles of 10 m or more are not observed.
- the polymerization reaction temperature was adjusted to 206 ° C., and the molar ratio of A 1 atom to Ti atom was adjusted to 63.3.
- the ratio between boron atoms and Ti atoms was adjusted to be 6.0.
- the reactor was continuously fed through a pipe having a diameter of 3.175 mm.
- the polymerization reaction temperature was adjusted to 205 ° C., and the molar ratio of A1 atom to Ti atom was adjusted to 77.2.
- an ethylene-butene-1 copolymer having an MFR of 13.3 gZl0 min was produced at 104.5 ton per mole of Ti atom per hour.
- Ethylene and hexane-11 were continuously fed into the reactor using a 1-liter internal volume autoclave reactor equipped with stirring blades to carry out polymerization.
- the polymerization conditions were set such that the total pressure was 7996 kgZcm 2 G and the hexene-1 concentration was 29.7 mo 1%.
- an ethylene-hexene-1 copolymer having an MFR of 3.8 gZlO and a density (without anneal) of 0.889 g / cm 3 was applied for 1 hour to 28 ton / mol of Ti atom. Manufactured.
- Ethylene and hexane-11 were continuously fed into the reactor using a 1-liter internal volume autoclave reactor equipped with stirring blades to carry out polymerization.
- the polymerization conditions were set such that the total pressure was 796 kgZcm 2 G and the hexene-11 concentration was 31.6 mo 1%.
- the concentration of A is 1 mol of Smol and 200 mol of Zg, respectively, and the molar ratio of A1 atom to Ti atom is 100).
- the polymerization reaction temperature was adjusted to 220 ° C, and the ratio of boron atoms to Ti atoms was adjusted to 7.6.
- an ethylene-hexene-one copolymer having an MFR of 5.8 gZlO, a density (without annealing) of 0.888 g / cm 3 , a melting point of 69.8 ° C, and an SCB of 32.6 was obtained.
- the coalescence was produced at 11 ton per mole of Ti atom per hour.
- Ethylene and hexane-11 were continuously fed into the reactor using a 1-liter autoclave reactor equipped with stirring blades to carry out polymerization.
- the polymerization conditions were set such that the total pressure was 796 kgZcm 2 G and the hexene_1 concentration was 31.1 mo 1%.
- an ethylene-hexene-1-copolymer having an MFR of 55 g / 10 min and a density (without anneal) of 0.886 gZcm 3 was 13 t per mole of Ti atom per hour. on manufactured.
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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DE69736631T DE69736631T2 (de) | 1996-12-20 | 1997-12-19 | Verfahren zur Herstellung von Olefinpolymeren |
EP97949175A EP0887355B1 (en) | 1996-12-20 | 1997-12-19 | Process for preparing olefin polymers |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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JP8/341988 | 1996-12-20 | ||
JP34198896 | 1996-12-20 | ||
JP9/5034 | 1997-01-14 | ||
JP503397 | 1997-01-14 | ||
JP503497 | 1997-01-14 | ||
JP9/5033 | 1997-01-14 | ||
JP17969397 | 1997-07-04 | ||
JP9/179693 | 1997-07-04 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US09125519 A-371-Of-International | 1998-08-20 | ||
US09/797,705 Continuation US6660816B2 (en) | 1996-12-20 | 2001-03-05 | Process for preparing olefin polymers |
Publications (1)
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WO1998028341A1 true WO1998028341A1 (fr) | 1998-07-02 |
Family
ID=27454215
Family Applications (3)
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PCT/JP1997/004716 WO1998028343A1 (fr) | 1996-12-20 | 1997-12-19 | Procede d'alimentation en composes au bore, fines particules desdits composes, constituants catalyseurs pour polymerisation d'olefines a base des memes composes, et procedes d'elaboration des particules |
PCT/JP1997/004717 WO1998028341A1 (fr) | 1996-12-20 | 1997-12-19 | Procede pour preparer des polymeres d'olefine |
PCT/JP1997/004713 WO1998028342A1 (fr) | 1996-12-20 | 1997-12-19 | Polymere d'olefine, pellicules ou feuilles de ce materiau, et procede de fabrication dudit polymere |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP1997/004716 WO1998028343A1 (fr) | 1996-12-20 | 1997-12-19 | Procede d'alimentation en composes au bore, fines particules desdits composes, constituants catalyseurs pour polymerisation d'olefines a base des memes composes, et procedes d'elaboration des particules |
Family Applications After (1)
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PCT/JP1997/004713 WO1998028342A1 (fr) | 1996-12-20 | 1997-12-19 | Polymere d'olefine, pellicules ou feuilles de ce materiau, et procede de fabrication dudit polymere |
Country Status (6)
Country | Link |
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US (2) | US6613850B1 (ja) |
EP (4) | EP0889062B1 (ja) |
KR (1) | KR19990087052A (ja) |
CN (1) | CN1216553A (ja) |
DE (3) | DE19781602T1 (ja) |
WO (3) | WO1998028343A1 (ja) |
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US6489261B1 (en) * | 1997-12-01 | 2002-12-03 | Dsm N.V. | Catalyst composition comprising a reduced transition metal complex and a cocatalyst |
SG73641A1 (en) * | 1998-05-20 | 2000-06-20 | Sumitomo Chemical Co | Ethylene-alpha-olefin-nonconjugated polyrene random |
SG72966A1 (en) * | 1998-07-08 | 2000-05-23 | Sumitomo Chemical Co | Transition metal compound olefin polymerization catalyst component olefin polymerization catalyst and process for producing olefin polymer |
DE19951277A1 (de) * | 1998-10-27 | 2000-05-04 | Sumitomo Chemical Co | Polymer auf Ethylenbasis |
FR2787795B1 (fr) * | 1998-12-25 | 2003-10-17 | Sumitomo Chemical Co | Copolymere de l'ethylene et d'un compose alcenylaromatique, son procede de production et produit moule obtenu a partir de celui-ci |
CN100358988C (zh) * | 1999-03-30 | 2008-01-02 | 三井化学株式会社 | 用于润滑油和润滑油组合物的粘度改性剂 |
SG93255A1 (en) * | 1999-08-31 | 2002-12-17 | Sumitomo Chemical Co | Olefin polymerization catalyst and process for producing olefin polymer |
WO2001053356A1 (de) * | 2000-01-17 | 2001-07-26 | Basell Polyolefine Gmbh | Katalysatorsystem mit ausgewähltem übergangsmetall: cokatalysator-verhältnis |
JP2001253908A (ja) * | 2000-03-10 | 2001-09-18 | Sumitomo Chem Co Ltd | オレフィン重合用触媒およびオレフィン重合体の製造方法 |
SG99905A1 (en) | 2000-06-21 | 2003-11-27 | Sumitomo Chemical Co | Transition metal compound, catalyst for addition polymerization, and process for producing addition polymer |
JP2008244362A (ja) * | 2007-03-28 | 2008-10-09 | Seiko Epson Corp | 半導体装置の製造方法、半導体装置、半導体回路、電気光学装置および電子機器 |
WO2009121374A1 (en) * | 2008-03-31 | 2009-10-08 | Dsm Ip Assets B.V. | Suspension of catalyst components |
JP5902094B2 (ja) | 2009-11-11 | 2016-04-13 | ボレアリス エージー | ポリマー組成物およびそれを含む電力ケーブル |
BR112012011265B1 (pt) | 2009-11-11 | 2020-12-01 | Borealis Ag | cabo e processo de produção do mesmo |
KR101844815B1 (ko) | 2009-11-11 | 2018-04-03 | 보레알리스 아게 | 고압 공정에서 제조된 폴리올레핀을 포함하는 중합체 조성물, 고압 공정 및 제품 |
MX348463B (es) | 2009-11-11 | 2017-06-14 | Borealis Ag | Composicion polimerica reticutable y cable con propiedades electricas ventajosas. |
PT2619357T (pt) * | 2010-09-23 | 2019-11-29 | Total Res & Technology Feluy | Relva artificial |
ES2750266T3 (es) | 2010-11-03 | 2020-03-25 | Borealis Ag | Una composición de polímero y un cable de alimentación que comprende la composición de polímero |
CN104254546B (zh) | 2012-04-26 | 2016-11-02 | 三井化学株式会社 | 烯烃聚合物的制造方法 |
KR102305868B1 (ko) | 2017-03-06 | 2021-09-27 | 더블유.알. 그레이스 앤드 캄파니-콘. | 지글러-나타 전촉매 제조용 전자 공여체 및 올레핀 중합용 촉매 시스템 |
WO2020174346A1 (ko) | 2019-02-28 | 2020-09-03 | 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 | 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법 |
KR20200105409A (ko) | 2019-02-28 | 2020-09-07 | 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 | 신규한 테트라아릴보레이트 화합물, 이를 포함하는 촉매 조성물, 및 이를 이용한 에틸렌 단독중합체 또는 에틸렌과 α-올레핀의 공중합체의 제조방법 |
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- 1997-12-19 DE DE19781602T patent/DE19781602T1/de not_active Withdrawn
- 1997-12-19 EP EP97949174A patent/EP0889062B1/en not_active Expired - Lifetime
- 1997-12-19 US US09/125,518 patent/US6613850B1/en not_active Expired - Lifetime
- 1997-12-19 EP EP97949175A patent/EP0887355B1/en not_active Expired - Lifetime
- 1997-12-19 WO PCT/JP1997/004716 patent/WO1998028343A1/ja active IP Right Grant
- 1997-12-19 US US09/125,520 patent/US6184319B1/en not_active Expired - Fee Related
- 1997-12-19 EP EP05007953.2A patent/EP1582525B1/en not_active Expired - Lifetime
- 1997-12-19 EP EP10012390.0A patent/EP2324918A3/en not_active Withdrawn
- 1997-12-19 CN CN97193855A patent/CN1216553A/zh active Pending
- 1997-12-19 WO PCT/JP1997/004717 patent/WO1998028341A1/ja active IP Right Grant
- 1997-12-19 KR KR1019980706437A patent/KR19990087052A/ko not_active Application Discontinuation
- 1997-12-19 DE DE69733883T patent/DE69733883T2/de not_active Expired - Lifetime
- 1997-12-19 WO PCT/JP1997/004713 patent/WO1998028342A1/ja not_active Application Discontinuation
- 1997-12-19 DE DE69736631T patent/DE69736631T2/de not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
DE69733883T2 (de) | 2006-06-01 |
EP2324918A3 (en) | 2013-12-04 |
DE69736631T2 (de) | 2007-09-13 |
EP0889062A4 (en) | 2002-05-15 |
EP0889062B1 (en) | 2005-08-03 |
KR19990087052A (ko) | 1999-12-15 |
WO1998028342A1 (fr) | 1998-07-02 |
EP0887355B1 (en) | 2006-09-06 |
EP0889062A1 (en) | 1999-01-07 |
US6184319B1 (en) | 2001-02-06 |
US6613850B1 (en) | 2003-09-02 |
DE69733883D1 (de) | 2005-09-08 |
EP2324918A2 (en) | 2011-05-25 |
CN1216553A (zh) | 1999-05-12 |
EP0887355A4 (en) | 2001-10-24 |
EP1582525B1 (en) | 2014-12-17 |
EP1582525A2 (en) | 2005-10-05 |
DE19781602T1 (de) | 1999-03-11 |
EP1582525A3 (en) | 2006-06-07 |
EP0887355A1 (en) | 1998-12-30 |
DE69736631D1 (de) | 2006-10-19 |
WO1998028343A1 (fr) | 1998-07-02 |
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