WO1999010389A1 - Particules modifiees, vehicule prepare a partir de ces particules, constituant de catalyseur de polymerisation d'olefine ainsi prepare, catalyseur de polymerisation d'olefine ainsi prepare et procede de preparation d'un polymere d'olefine - Google Patents
Particules modifiees, vehicule prepare a partir de ces particules, constituant de catalyseur de polymerisation d'olefine ainsi prepare, catalyseur de polymerisation d'olefine ainsi prepare et procede de preparation d'un polymere d'olefine Download PDFInfo
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- WO1999010389A1 WO1999010389A1 PCT/JP1998/003680 JP9803680W WO9910389A1 WO 1999010389 A1 WO1999010389 A1 WO 1999010389A1 JP 9803680 W JP9803680 W JP 9803680W WO 9910389 A1 WO9910389 A1 WO 9910389A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- 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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- 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
- B01J31/143—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 of aluminium
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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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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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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
- B01J31/122—Metal aryl or alkyl compounds
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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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
- C08F4/619—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
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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
- C08F4/619—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
- C08F4/61927—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 two cyclopentadienyl rings being mutually bridged
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- the present invention relates to particles useful as a carrier and further a catalyst component for polymerization of olefin, a catalyst for polymerization of olefin using the same, and a method for producing an olefin polymer using the catalyst for polymerization of olefin.
- Japanese Patent Publication No. 58-19309 discloses an olefin polymer using bis (cyclopentagenenyl) zirconium dimethyldichloride and methylaluminoxane. Is disclosed.
- Japanese Patent Application Laid-Open No. 1-520203 discloses a method for producing an olefin polymer using bis (pentamethylcyclopentenyl) zirconium dimethyl and n-butylammoniumtetraxphenylphenylate. I have. Also, in Japanese Patent Application Laid-Open No.
- Catalysts using these transition metal compounds are soluble in the reaction system, When used in polymerization accompanied by the formation of polymer particles (eg, slurry polymerization, gas phase polymerization, etc.), the shape of the polymer formed is irregular, and the formation of coarse polymer particles, bulk polymers, fine polymer particles, etc. This leads to a decrease in bulk density and adhesion of the polymer to the polymerization reactor wall. Then, these factors contribute to poor heat transfer and poor heat removal in the reactor, leading to a problem that stable operation is difficult and productivity is reduced.
- polymer particles eg, slurry polymerization, gas phase polymerization, etc.
- transition metal compound in order to apply the transition metal compound to polymerization involving the formation of polymer particles (eg, slurry polymerization, gas phase polymerization, etc.), not only a sufficient polymerization activity is exhibited but also a polymer having excellent shape and particle properties. It is necessary to obtain a coalescence, and to solve the problem, a method of supporting a transition metal compound on a carrier has been proposed.
- polymer particles eg, slurry polymerization, gas phase polymerization, etc.
- a soluble Disclosed is a method of depositing and adhering on a typical support, for example, silica, alumina, polyethylene, etc., converting it to a supported heterogeneous catalyst, and combining it with an aluminoxane for slurry polymerization or gas phase polymerization. ing.
- Japanese Patent Application Laid-Open No. 61-108610 discloses a process in which bis (cyclopentene genyl) zirconium dimethyl dichloride and silica which has been calcinated in the presence of a reaction product of trimethylaluminum and water are added. A method for producing an olefin polymer using the obtained solid catalyst component is disclosed.
- Japanese Patent Application Laid-Open No. 61-276805 discloses that an organic aluminum component containing an inorganic oxide obtained by reacting a mixture of methylaluminoxane and trimethylaluminum with silica and bis (cyclopentenyl). A method for producing an olefin polymer using zirconium dichloride is disclosed.
- Japanese Unexamined Patent Publication (Kokai) No. 61-296608 discloses that silica is methylaluminoxane and then bis (cyclopentene G)
- a method for producing an olefin polymer by treating with zirconium dichloride and using a solid catalyst containing aluminum and zirconium is disclosed.
- a solid catalyst component in which all or a part of a catalyst component such as a meta-aluminum complex or methylaluminoxane is immobilized and supported on an inorganic metal oxide carrier such as silica, and an aluminoxane or an organic catalyst are further supported.
- a method using an aluminum and a method using a prepolymerized catalyst that has been prepolymerized have been reported.
- JP-A-63-51407 discloses an olefin polymer using methylaluminoxane and a solid catalyst component obtained by treating silica with methylaluminoxane and then bis (cyclopentenylgen) zirconium dichloride. There is disclosed a method for producing the same.
- Japanese Patent Application Laid-Open No. 63-89555 discloses a solid catalyst component obtained by treating silica with methylaluminoxane and then bis (cyclopentyl genenyl) zirconium dichloride and tri-isobutyl aluminum.
- a method for producing a polymer or a method for producing an olefin polymer using a solid catalyst component preliminarily polymerized using the solid catalyst component and tri-is-butyl aluminum is disclosed.
- aluminoxane In the above prior art, the use of aluminoxane is essential. This aluminoxane requires a separate synthesis, and its steps are numerous and complicated. Aluminoxane is unstable and expensive.
- the solid catalyst component obtained by combining aluminoxane with an inorganic metal oxide carrier such as silica had a large amount of aluminum used and a low activity per mole of A atom.
- organic aluminum and water are reacted in the presence of an inorganic metal oxide carrier such as silica to produce aluminoxane, a solid catalyst component is produced, and an olefin polymer is produced using the solid catalyst component. Manufacturing methods have been reported.
- Japanese Unexamined Patent Publication (Kokai) No. 61-314404 discloses that water, trimethylaluminum, and bis (cyclopentenyl) zirconium dichloride are successively added to silica to form a catalyst, and an olefin polymer is added.
- a method of making is disclosed.
- Japanese Unexamined Patent Application Publication No. 1-207303 discloses a method in which undehydrated silica gel containing water is added to trimethyl aluminum and then treated with bis (n-butylcyclopentenyl) zirconium dichloride.
- JP-A-3-234710 discloses that silica, water, trimethylaluminum dimethyl, and bis (methylcyclopentenyl) zirconium dichloride are sequentially added to silica, and further pre-polymerized by adding ethylene.
- a method is disclosed in which a solid catalyst is prepared and an olefin polymer is produced using the solid catalyst and tri-iso-butylaluminum.
- a method for producing an olefin polymer using a supported catalyst obtained in addition to a porous alumina is disclosed.
- Japanese Unexamined Patent Publication No. Hei 6-333650 discloses that silica is treated with triethyl aluminum.
- the solid catalyst component obtained from the supported carrier, ethylenebisindenyl zirconium dichloride, and N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, and furthermore, tri-iso-butylaluminum A method for producing a polymer is disclosed.
- the boron compounds used in these prior arts require a separate synthesis, and the steps are numerous and complicated.
- the amount of these boron compounds incorporated in a carrier such as silica is generally small, and the reaction product of a meta-acene-based transition metal compound and a boron compound is generally unstable. The activity when the olefin was polymerized was low.
- Japanese Unexamined Patent Publication No. 6-329713 discloses that a solid component of an aluminum compound having an electron-withdrawing group, which is obtained by reacting trimethylaluminum with penfluorofluorophenol, and bis (cyclopentenyl) titanium A method for producing an olefin polymer using dichloride is disclosed. Further, it is described that an aluminum compound into which a special group has been introduced can be supported on an inorganic carrier, and in some cases, on an organic carrier. However, there is no example of actually supporting an aluminum compound having an electron-withdrawing group, which is obtained by reacting trimethylaluminum with pentafluorophenol, and using a solid catalyst component supported as described. polymerization active '1 1 students in the case of stomach been filed Teire, in mono.
- modified clays obtained by treating clay minerals with a compound capable of introducing cation into the interlayer, and a catalyst for polymerization of olefins consisting of metallocene complexes and organoaluminum compounds.
- Japanese Unexamined Patent Publication No. Hei 7-22410 discloses that Hue mouth, concentrated sulfuric acid, And modified high-purity montmorillonite to prepare modified clay,
- a method for producing an olefin polymer using iso-butylaluminum and ethylenebis (indenyl) zirconium dichloride is disclosed.
- many clay minerals are irregular in shape, particle size, and particle properties, and many of the olefin polymers obtained by using them are also irregular in particle properties.
- the preparation of the modified clay in an aqueous solution to introduce cations between the layers of the clay mineral is described, but water is essentially an inhibitor of olefin polymerization and complete water from the modified clay is Removal was necessary, but difficult. Disclosure of the invention
- an object of the present invention is to use a transition metal compound to polymerize an olefin polymerization catalyst using a transition metal compound together with the formation of polymer particles.
- a transition metal compound to polymerize an olefin polymerization catalyst using a transition metal compound together with the formation of polymer particles.
- particles that can provide a polymer having high activity and excellent particle properties, a carrier comprising the particles, and an olefin polymerization comprising the particles.
- the present inventors have intensively studied a method for producing an olefin polymer using a transition metal compound, particularly a method for producing an olefin polymer by polymerization accompanied by formation of polymer particles. Have been. As a result, they have found modified particles obtained by bringing dried particles into contact with a specific compound, and have completed the present invention.
- the present invention relates to a method comprising bringing a dried particle (a) into contact with an organometallic compound (b), then contacting a functional group having active hydrogen or a non-proton donating Lewis basic functional group, and a compound having an electron-withdrawing group.
- (C) relates to the modified particles obtained by contacting with (c).
- the present invention provides a catalyst composition for olefin polymerization comprising the particles, the particles (A) and the transition metal compound (B), or further using the organic metal compound (C).
- the present invention relates to a catalyst for polymerization of olefins, and a method for producing an olefin polymer using the catalyst for polymerization of olefins.
- the modified particles of the present invention are prepared by bringing the dried particles (a) into contact with the organometallic compound (b), and then contacting a functional group having active hydrogen or a non-proton-donating Lewis salt functional group and an electron absorbing material. It is obtained by contacting the compound (c) having a bow I group, but the particles (a) used here are dry, substantially free of water, and free from trialkylaluminum. Aluminoxane is not substantially produced by the contact.
- the particles (a) those generally used as a carrier are preferably used, and a material having a uniform particle size and a large number of mosquitoes is preferable, and an inorganic substance or an organic polymer is suitably used.
- Examples of the inorganic substance that can be used for the particles (a) of the present invention include an inorganic oxide / magnesium compound and the like. Clays and clay minerals can be used as long as they do not interfere. These may be used as a mixture.
- the inorganic oxide Si0 2, A 120 a, Mg_ ⁇ , Zr0 2, Ti ⁇ 2, B 2 0 3, CaO , ZnO, BaO, Th0 2 , etc., and mixtures thereof, for example, Si_ ⁇ 2-MgO, Si0 2 - Al 2 ⁇ 3, SiOs- Ti0 2, Si0 2 one V 2 0 5, S i 02- C r 20 Si_ ⁇ 2 - Ti_ ⁇ 2 - MgO etc. can exemplified child.
- these inorganic oxides preferably Si_ ⁇ 2 and / or A 1 2 03.
- the above inorganic oxide is a small amount of Na 2 CO 3, K 2 C0 3, CaC 0 3 ⁇ MgC0 3 ⁇ N a 2 S 0 4> A1 2 (S0 4) 3 ⁇ BaS0 4 ⁇ KN0 3 ⁇ Mg ( N0 3) 2, Al (N0 3) 3, Na 2 0, K 2 0, Li 2 0 , etc. carbonates, sulfates, It may contain a nitrate or an oxidant component.
- Magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, is ⁇ -propoxy magnesium chloride, butoxy salt ⁇ : magnesium, octoxy Alkoxy magnesium halides such as magnesium salt; aryloxy magnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; ethoxymagnesium, iso-propoxymagnesium, butoxymagnesium, n-tactoxymagnesium phenoxymagnesium, dimethylphenoki Aryloxima magnesium such as magnesium; magnesium carbohydrate such as magnesium laurate and magnesium stearate And the like.
- magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride
- methoxy magnesium chloride, ethoxy magnesium chloride is ⁇ -propoxy magnesium chloride, butoxy salt ⁇ : magnesium, oct
- halogenated magnesium or alkoxymagnesium preferred are halogenated magnesium or alkoxymagnesium, and more preferred are magnesium chloride or butoxymagnesium.
- Clays or clay minerals include kaolin, bentonite, kibushi clay, gairome clay, alofen, hisingelite, bilofilite, talc, pummo group, montmorillonite group, vermiculite, lyocudi stone group, palygorskite, ryolidite , Nacrite, dickite, halloysite and the like.
- smectite, montmorillonite, hectorite, labonite and savonite are preferred, and montmorillonite and hectorite are more preferred.
- These inorganic substances need to be dried to substantially remove water, and are preferably dried by heat treatment.
- the heat treatment is usually carried out at a temperature of 100 to 150 ° C, preferably at 100 to: L0000 ° C, and more preferably at a temperature of 200 to 800 ° C.
- a method of flowing a dried inert gas eg, nitrogen or argon, etc.
- a constant flow rate for several hours or reducing the pressure for several hours
- the method is not limited.
- the average particle diameter of the inorganic substance is preferably from 5 to 100 ⁇ m, more preferably from 10 to 500 ⁇ m, and still more preferably from 10 to 100 ⁇ m.
- the pore volume is preferably at least 0.1 ml / g, more preferably 0.3 to 10 ml / g. L 0 Om 2 / g, more preferably 100 to 100;
- any organic polymer may be used, and a plurality of kinds of organic polymers may be used as a mixture.
- the organic polymer is preferably an organic polymer having a functional group capable of reacting with the organometallic compound (b). Examples of such a functional group include a functional group having an active hydrogen and a non-proton donating Lewis basic functional group.
- An organic polymer that can be used for the particle (a) includes a functional group having an active hydrogen. A polymer having a group or a non-proton donating Lewis basic functional group is preferred.
- the functional group having active hydrogen is not particularly limited as long as it has active hydrogen, and specific examples thereof include a primary amino group, a secondary amino group, an imino group, an amide group, a hydrazide group, an amidino group, and a hydroxy group. , Hydroperoxy, carboxyl, formyl, phorbamoyl, sulfonic, sulfinic, sulfenic, thiol, thioformyl, pyrrolyl, imidazolyl, piperidyl, indazolyl sorbazolyl And the like.
- the non-proton-donating Lewis base is not particularly limited as long as it has a Lewis base moiety having no active hydrogen atom.
- Specific examples thereof include a pyridyl group, an N-substituted imidazolyl N- Substituted indazolyl group, nitrile group, azide group, N-substituted imino group, N, N-substituted amino group ⁇ N, N-substituted aminooxy group, N, N, N-substituted hydrazino group, nitroso group, nitro group nitroxy group, furyl group, carbonyl group, thiocarbonyl group, Examples include an alkoxy group, an alkyloxycarbonyl group, an N, N-substituent rubamoyl group, a thioalkoxy group, a substituted sulfinyl group, a substituted sulfonyl group, and a substituted sulfonic
- a heterocyclic group is preferable, and an aromatic heterocyclic group having an oxygen atom and / or a nitrogen atom in the ring is more preferable.
- Particularly preferred are a pyridyl group, an N-substituted imidazolyl group, and an N-substituted indazyl group, most preferably a pyridyl group.
- These groups may be substituted with a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- the amount of the functional group having an active hydrogen or the non-proton-donating Lewis basic functional group is not particularly limited, but preferably, the molar amount of the functional group per unit gram of the organic polymer is 0.01 to 5O. mmo1 / g, and more preferably 0.1 to 2 Ommo1 / g.
- the organic polymer having such a functional group can be obtained, for example, by copolymerizing a monomer having a functional group having an active hydrogen or a non-proton-donating Lewis basic functional group, or another monomer. It can. At this time, it is preferable to copolymerize a crosslinked polymerizable monomer having two or more polymerizable unsaturated groups at any time.
- Examples of the monomer having an active hydrogen-containing functional group or an aprotic donating Lewis basic functional group include the above-described functional group having an active hydrogen and the monomer having a polymerizable unsaturated group, or the above-described active hydrogen.
- Examples of the monomer include a functional group having a Lewis base moiety having no atom and a monomer having a polymerizable unsaturated group.
- Examples of such polymerizable unsaturated groups include alkenyl groups such as bier groups and aryl groups, and alkynyl groups such as ethyne groups.
- Examples of the monomer having a functional group having an active hydrogen and a polymerizable unsaturated group include a vinyl-containing primary amine, a vinyl-containing secondary amine, a vinyl-containing amide compound, and a vinyl-containing hydroxy compound.
- N— (1-ethenyl) amine N— (2-propenyl) amine, N— (1-ethenyl) -1-N-methylamine, N— (2-propyl) -1-N— Methylamine, 1-ethenylamide, 2-propenylamide, N-methyl- (1-ethenyl) amide, N-methyl- (2-propenyl) amide, vinyl alcohol, 2-propen-1-ol, 3-butene-1 —Alls are listed.
- the monomer having a functional group having a Lewis base moiety having no active hydrogen atom and a polymerizable unsaturated group include vinylpyridine, vinyl (N-substituted) imidazole, and vinyl (N-substituted) indazole. Can be mentioned.
- the other monomer having a polymerizable unsaturated group include ethylene and HITACHI REFINE. Specific examples include ethylene, propylene, butene-1, hexene-1, 4-methyl-1-pentene-1 And styrene. Preferred is ethylene or styrene. Two or more of these monomers may be used.
- crosslinkable polymerizable monomer having two or more polymerizable unsaturated groups include divinylbenzene.
- the average particle diameter of the organic polymer is preferably from 5 to 1000 m, more preferably from 10 to 500 / m.
- the pore volume is preferably at least 0.1 ml / g, more preferably 0.3 to 10 ml / g.
- the specific surface area is preferably from 10 to: L 000 m2 / g, more preferably from 50 to 500 m2 / g.
- the organometallic compound (b) used in the present invention is an organometallic compound represented by the following general formula (1).
- R 1 is a hydrocarbon group having 1 to 20 carbon atoms. Or a hydrocarbonoxy group having 1 to 20 carbon atoms, wherein R 1 is In this case, Ri may be the same or different.
- X is a halogen atom or a hydrogen atom.
- n is a number satisfying 0 ⁇ n ⁇ q, and q is the valence of the metal atom.
- A is preferably a boron atom, an aluminum atom, a magnesium atom, a zinc atom or the like.
- R 1 is preferably the above-mentioned hydrocarbon group.
- Specific examples include trialkylborane such as trimethylborane, triethylborane, tripropylborane, tributylborane, and triphenylborane; dimethylchloroborane; getylchloroborane; Dialkyl halide boranes such as propyl chloroborane, dibutyl chloroborane, diphenylchloroborane, dimethyl hydride borane, dimethyl borohydride, dipropyl hydrido borane, dialkyl hydride borane such as dibutyl hydride borane, diphenyl hydrido borane, methyl dichloro borane, methyl dichloro borane Alkyl dihalide borane such as borane, propyldichloroborane, butyldichloro
- R 1 is preferably the above-mentioned hydrocarbon group, and specific examples include trimethylaluminum, triethylaluminum, tri-n-propyl aluminum, tri-iso-propyl aluminum, and tri-n-butyl Aluminum, tri-iso-butyl aluminum, tri-alkyl aluminum such as tri-n-hexyl aluminum, dimethyl aluminum chloride, dimethyl aluminum chloride, g-propyl aluminum chloride, di-isopropyl aluminum Dialkylaluminum halides such as chloride, di-n-butylaluminum chloride, diiSo-butylaluminum chloride, di-n-hexylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride Ride, n-propylaluminum dichloride, iso-propylaluminum dichloride, n-butylaluminum dichloride, Alkyl aluminum dihalides
- trialkylaluminums are preferred, and more preferred are trimethylaluminum, triethylaluminum, triiso-butylaluminum, tri-n-butylaluminum, and tri-n-hexylaluminum. Particularly preferred are trimethylaluminum, triethylaluminum, and tri-iso-butylaluminum.
- A is magnesium
- the above-mentioned hydrocarbon group is preferable, and specific examples include methyl magnesium, di-n-butyl magnesium and the like, and examples thereof include di-n-butoxy magnesium which is the above-mentioned hydrocarbon oxy group.
- R i is preferably the above-mentioned hydrocarbon group, and getyl zinc and the like are exemplified.
- the organometallic compound (b) is an organoaluminum compound or an organic borane compound, and most preferably an organoaluminum compound.
- the active hydrogen-containing functional group or the aprotic donating Lewis base 14 functional group of the compound (c) used in the present invention usually reacts with an organometallic compound.
- the functional group having an active hydrogen and the non-proton donating Lewis basic functional group are the same as those described above.
- the compound (c) has an electron-withdrawing group.
- the index of the electron-withdrawing group may be a Hammett's rule, such as a substituent constant ⁇ , and a functional group having a Hammett's rule, the substituent constant ⁇ is positive. Corresponds to an electron-withdrawing group.
- the electron-withdrawing group examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, Examples include a cyano group, a nitro group, a phenyl group, an acetyl group, a carbonyl group, a thionyl group, a sulfone group, and a carboxyl group.
- the non-proton-donating Lewis basic functional group and the electron-withdrawing group may be the same.
- compound (c) may have only one such functional group.
- the compound (c) may have a plurality of and / or a plurality of active hydrogen-containing functional groups or non-proton donating Lewis basic functional groups and electron-withdrawing groups. .
- Examples of such a compound (c) include amines, phosphines, alcohols, phenols, thiols, thiophenols, carboxylic acids, sulfonic acids and the like having an electron-absorbing I group.
- the compound (c) is preferably a compound represented by the following general formula (2).
- R 2 represents an electron-withdrawing group or a group containing an electron-absorbing I group
- ⁇ represents an atom of Group 15 or 16 of the periodic table
- ⁇ represents a hydrogen atom
- ⁇ is the valence of ⁇ and is 2 or 3, and when ⁇ is 2, m is 1 and when z is 3, m is 1 or 2.
- Examples of the group containing an electron-withdrawing group for R 2 in the general formula (2) include a halogenated alkyl group, a halogenated aryl group, a cyanated aryl group, a nitrated aryl group, and an ester group. .
- halogenated alkyl group examples include fluoromethyl group, chloromethyl group, bromomethyl group, odomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, iodomethyl group, trifluoromethyl group, trichloromethyl group, and tribromomethyl.
- halogenated aryl group examples include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl.
- cyanoaryl group examples include 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl and the like.
- nitrated aryl groups include 2-nitrophenyl, 3-nitrophenyl, and 4-nitrophenyl. And the like.
- ester group examples include a methoxycarbonyl group, an ethoxycarbonyl group, a normal propyloxycarbonyl group, is 0-propyloxycarbonyl group, a phenoxycarbonyl group, a trifluoromethyloxycarbonyl group, and a pentafluoromouth phenyl. And a carbonyl group.
- R 2 in the general formula (2) is preferably a halogenated alkyl group or a halogenated aryl group, more preferably a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group.
- 2,2,3,3,3-pentanofluoropropyl group 2,2,2-trifluoro-1-trifluoromethylethyl group, 1,1,1,3,3,3_hexafluoro-2-trifluoromethylpropyl group ,
- Z represents an atom of Group 15 or 16 of the periodic table, and H represents a hydrogen atom.
- H represents a hydrogen atom.
- z is the valency of Z; for example, z is 3 when Z is a nitrogen atom or a phosphorus atom, and z is 2 when Z is an oxygen or sulfur atom. And when z is 2, m is 1 and when z is 3, m is 1 or 2.
- amines such as di (fluoromethyl) amine, di (chloromethyl) amine, di (bromomethyl) amine, di (iodomethyl) amine, di (difluoromethyl) amine, Di (dichloromethyl) amine, di (Dibromomethyl) amine, di (jodomethyl) amine, di (trifluoromethyl) amine, di (trichloromethyl) amine, di (tripromomethyl) amine, di (triiodomethyl) amine, di (2,2) 2-Trifluoroethyl) amine, di (2,2,2-trichloroethyl) amine, di (2,2,2-tripromethyl) amine, di (2,2,2-triethyl) amine, Di (2,2,3,3,3-pentanofluoropropyl) amine, di (2,2,3,3,3-pentachloropropyl) amine, di (2,2,3,3,3-pentachloropropyl)
- phosphine compound in which a nitrogen atom is substituted by a phosphorus atom can also be exemplified.
- These phosphine compounds are compounds and the like represented by rewriting amine to phosphine in the above specific examples.
- the compound (c) include alcohols such as fluorenol, chloromethanol, bromomethanol, ethanol, difluorenol, dichloromethanol, dibromomethanol, methodanol, and trifluoromethane.
- thiol conjugates in which an oxygen atom is substituted by a sulfur atom can be similarly exemplified.
- These thiol compounds are, for example, the compounds described above by converting methanol to methanethiol, ethanol to ethanethiol, and propanol to propanethiol.
- the compound (c) include phenols such as 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, and 2-bromophenol. , 3-bromophenol, 4-bromophenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 2,6-difluorophenol, 3,5-difluorophenol, 2 , 6-Dichlorophenol, 3,5-dichlorophenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,6-jodophenol, 3,5-jodophenol, 2,4 6-trifluorophenol, 2,4,6-trichloromouth phenol, 2,4,6-tribromophenol,
- thiophenol compound in which an oxygen atom is substituted by a sulfur atom can be exemplified in the same manner. Those thiophenol compounds are described above. Specific examples include compounds represented by replacing phenol with thiophenol.
- carboxylic acids examples include 2-fluorobenzoic acid, 3-fluorobenzoic acid, 4-fluorobenzoic acid, 2,3-difluorobenzoic acid, 2,4-difluorobenzoic acid and 2,4-difluorobenzoic acid.
- the compound (c) include sulfonic acids such as fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, penfluorofluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1,1 3,3,3-hexafluoro-2-propanesulfonic acid and the like.
- sulfonic acids such as fluoromethanesulfonic acid, difluoromethanesulfonic acid, trifluoromethanesulfonic acid, penfluorofluoroethanesulfonic acid, heptafluoropropanesulfonic acid, 1,1,1,1 3,3,3-hexafluoro-2-propanesulfonic acid and the like.
- the amines include di (trifluoromethyl) amine, di (2,2,2-trifluoroethyl) amine, and di (2,2,3,3,3-pentafluoroamine) Oropropyl) amine, di (2,2,2-trifluoro-1-trifluoromethylethyl) amine, di (1,1,1,3,3,3-hexafluoro) Romethylpropyl) amine, di (pentafluorophenyl) amine, and alcohols such as trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentanol Fluoropropanol, 2,2,2-trifluoro-1-trifluoromethylethanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol, phenols are 2 —Fluorophenol, 3-fluorophenol, 4-Fluoropheno —, 2,6-difluorophenol, 3,5-
- the compound (c) is di (trifluoromethyl) amine, di (dimethylfluorophenyl) amine, trifluorophenol, 2,2,2-trifluoroethyl 1-trifluoromethylethanol, 1,1 , 1,3,3,3-hexafluoro-2-trifluoromethylpropanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6-trifluorophenol, pentafluorophenol And 4- (trifluoromethyl) phenol, 2,6-di (trifluoromethyl) phenol, and 2,4,6-tri (trifluoromethyl) phenol, and more preferably, penfluorofluorophenol. , Or 1,1,1,3,3,3-hexafluoro-2-trifluoromethylpropanol (common name: perfluoro-tert-butanol) A.
- the modified particles of the present invention are obtained by bringing the dried particles (a) into contact with the organometallic compound (b), and then contacting a functional group having active hydrogen or a non-proton-donating Lewis basic functional group with an electron-withdrawing property. It is obtained by contacting a compound having a group (c).
- the contact treatment between (a) and (b) and then the contact treatment with (c) are preferably carried out in an inert atmosphere.
- the processing temperature is usually from 80 ° C to 200 ° C, preferably from 120 ° C to 150 ° C, more preferably from 0 ° C to: 00 ° C.
- the treatment time is usually 1 minute to 48 hours, preferably 10 minutes to 24 hours. Dissolution It is preferred to use a solvent, but the solvent used is preferably an aliphatic or aromatic hydrocarbon solvent which is inert to (a), (b) and (c).
- Examples of the aliphatic hydrocarbon solvent include butane, pentane, hexane, heptane, and octane, and examples of the aromatic hydrocarbon solvent include benzene, toluene, and xylene. Alternatively, a mixture of these hydrocarbon solvents arbitrarily can be used.
- the method of contacting (a) and (b) and the method of contacting (c) after that are the same. Or different.
- the contact-treated particles at each contacting step may or may not be subjected to the isolation operation.
- the isolation method include a method of decanting the supernatant of the reaction solution, a method of washing the treated particles with an inert solvent after filtration, and a method of washing the treated particles with an inert solvent after filtration, and then using a lower or inert gas.
- the particles obtained in the reaction solution may be suspended in an inert solvent and used for the polymerization reaction.
- the amount of (b) used with respect to (a) is selected from the group consisting of the organometallic compound contained in the particles obtained by contacting (a) and (b).
- the metal atom of b) is preferably at least 0.1 lmmo 1 and more preferably 0.5 to 2 Ommo 1 in terms of moles of metal atom contained in 1 g of the dried particles.
- the amount of (c) used may be a functional group having an active hydrogen or a non-proton donating Lewis basic functional group or a non-proton donating Lewis basic functional group for the metal atom of the organic metal compound (b) contained in 1 g of the dried particles.
- the molar ratio (c) / (b) of the compound (c) having an attractive group is from 0.01 to; preferably L00, more preferably from 0.05 to 5, and from 0.1 to 5. More preferably, it is 2.
- the modified particles of the present invention contain a catalyst component for olefin polymerization such as a transition metal compound. It can be used as a carrier to be supported, and is suitably used for polymerization accompanied by formation of polymer particles. Further, the modified particles of the present invention can function as a catalyst component for polymerization of olefins.
- the catalyst for olefin polymerization using the modified particles of the present invention includes those using the modified particles (A) and the transition metal compound (B), or those using the modified particles (A) and the transition particles. Examples thereof include those using a metal compound (B) and an organometallic compound (C).
- transition metal compound used in the present invention any transition metal compound having an olefin polymerization activity can be used.
- the periodic table of elements (1993, IUPAC) Group 4 or lanthanide series transition metals are preferred. More preferably, the transition metal compound is a meth-based transition metal compound.
- the meta-mouthed transition metal compound is, for example, a compound represented by the following general formula (3).
- L is a group or a group having a cyclopentene anion skeleton
- a group containing a terrorist atom, at least one of which is a group having a cyclopentene anion skeleton, and a plurality of Ls may be the same or different, and may be cross-linked to each other
- R 3 is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, a is 0 and a number that satisfies a ⁇ p, and p is the valence of the transition metal atom M.
- 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 a transition metal atom of Group 4 of the periodic table, and a samarium atom as a lanthanide-based transition metal atom.
- titani Atom, zirconium atom or hafnium atom are preferred.
- L is a group having a cyclopentene anion skeleton or a group containing a hetero atom, and at least one is a cyclopentadiene anion. It is a group having a skeleton.
- a plurality of L may be the same or different, and may be cross-linked to each other. Examples of the group having a Shikurobe down evening Gen shaped Anion skeleton 7 5 -? Shikuropen evening Jeniru group, V 5 - substituted Shikuropen evening Jeniru group or polycyclic group having Shikuropen evening Jen shaped Anion skeleton, and the like.
- the substituent of the substituted cyclopentagenenyl group is 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.
- 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.
- an alkoxy group, an aryloxy group, an alkylthio group, an aryl group It is a monothio group, a dialkylamino group, a diarylamino group, a dialkylphosphino group or a diarylphosphino group.
- polycyclic group having a cyclopentadiene-type adione skeleton include: 7) 5 monoindenyl group 77 5 —2-methylindenyl group, 7? 5-4 monomethylindenyl group, 77 5- 4, 5, 6, 7-tetrahydroindenyl group and 7-5-fluorenyl group.
- group containing a hetero atom examples include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, thiomethoxy group, dimethylamino group, ethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, and pyrrolyl. And a dimethylphosphino group.
- Groups having a cyclopentene anion skeleton, or a group 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, or dimethyl group.
- an alkylene group such as an ethylene group or a propylene group, or dimethyl group.
- a substituted alkylene group such as a methylene group or a diphenylmethylene group, or a substituted silylene group such as a silylene group, a dimethylsilylenediphenylsilylene 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 as a halogen atom, a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group as a hydrocarbon group having 1 to 20 carbon atoms.
- 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 may be used in combination.
- component (C) organoaluminum compound used in the present invention a known organic aluminum compound can be used.
- the general formula (4) R ⁇ A l Y 3 -b (where, R 4 is 1-8 amino hydrocarbon group having carbon atoms, A 1 represents an aluminum atom.
- Y represents a hydrogen atom and / or halogen atom , And b represent a number satisfying 0 ⁇ b ⁇ 3.))
- R 4 in the general formula (4) representing an organoaluminum compound include methyl, ethyl, n-propyl, n-butyl, iso-butyl, n-hexyl and 2-methyl.
- examples thereof include a xyl group and an n-octyl group, and preferably an ethyl group, an n-butyl group, an iso-butyl group and an n-hexyl group.
- Y is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom.
- the catalyst for polymerization of olefins of the present invention comprises the modified particles (A), the transition metal compound (B), and further the organometallic compound (C), and the amount of the component (B) used is a) to 1 g of usually 1 X 10-6 ⁇ 1 X 10-3mo 1, rather preferably is 5x 10-6 ⁇ 5x 10- 4 mo 1.
- the amount of the organometallic compound of component (C) is 0 as the molar ratio of metal atom of component (C) organometallic compound to transition metal atom of component (B) transition metal compound. It is preferably from 01 to 10,000, more preferably from 0.1 to 5,000, and most preferably from 1 to 2,000.
- component (A) and component (B) or, furthermore, component (C) can be put into a reactor in any order and used at the time of polymerization, and these optional components can be used in any combination. May be used after being brought into contact with the reactor in advance.
- the monomer used for the polymerization any of olefin and diolefin having 2 to 20 carbon atoms can be used, and two or more monomers can be used at the same time. Such monomers are exemplified below, but the present invention should not be limited to the following compounds.
- olefins include ethylene, propylene, butene-11, pentene1-1, hexene1-1, heptene
- examples thereof include 3- to 20-carbon olefins such as octene-1, octene-1, nonene-1, decene-1,4-methyl-11-pentene and the like, and olefins such as vinylcyclohexane.
- diolefin compounds include conjugated and non-conjugated. Specific examples of such compounds include 1,5-hexadiene, 1,4-hexadiene, 1,4-pentadiene, and 1,7-nonadiene.
- conjugated diene examples include 1,3-butadiene, isoprene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclodioxane, and 1,3-diene. It can be exemplified Kisaji E down like the filtration.
- a combination of the monomers constituting the copolymer a combination of ethylene and the above-mentioned monoolefin (for example, ethylene and propylene, ethylene and butene-11, and ethylene and hexene-1) is preferable.
- a combination of propylene and butene 11 is also exemplified, but the present invention should not be limited to the above compounds.
- an aromatic vinyl compound can also be used as a monomer.
- the aromatic biel compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, and the like.
- the polymerization method is not particularly limited, and gas-phase polymerization in a gaseous monomer, solution polymerization using a solvent, slurry polymerization, and the like are possible.
- Solvent polymerization or slurry-Examples of solvents used for polymerization include aliphatic hydrocarbon solvents such as butane, pentane, heptane, and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbon solvents such as methylene chloride. Or Orefin himself It is also possible to use as a solvent.
- the polymerization method may be either batch polymerization or continuous polymerization, and the polymerization may be performed in two or more stages under different reaction conditions.
- the polymerization time is generally determined as appropriate depending on the type of the intended olefin polymer and the reaction apparatus, but can range from 1 minute to 20 hours.
- the present invention is particularly suitably applied to polymerization involving formation of polymer particles (for example, slurry polymerization, gas phase polymerization, etc.).
- Slurry polymerization may be performed according to known slurry polymerization methods and polymerization conditions, but is not limited thereto.
- the preferred method of polymerization in the slurry process is to continuously add monomers (and comonomers), feeds, diluents, etc. as needed, and to continuously or at least periodically remove the polymer product.
- a type reactor is included. Examples of the reactor include a method using a loop reactor, a different reactor, a plurality of stirred reactors having different reaction conditions in series or in parallel, or a combination thereof.
- an inert diluent such as paraffin, cycloparaffin or aromatic hydrocarbon
- the temperature of the polymerization reactor or reaction zone can usually range from about 50 ° C to about 100 ° C, preferably from 60 ° C to 80 ° C.
- the pressure can usually be varied from about 0.1 1 ⁇ & to about 10 MPa, preferably from 0.5 MPa to 5 MPa.
- the catalyst can be maintained in suspension, the medium and at least some of the monomers and comonomers can be maintained in a liquid phase, and a pressure can be provided to allow contact of the monomers and comonomers.
- the medium, temperature, and pressure may be selected so that the olefin polymer is produced as solid particles and recovered in that form.
- the molecular weight of the olefin polymer can be controlled by various known means such as adjusting the temperature of the reaction zone and introducing hydrogen.
- Each catalyst component and monomer (and comonomers) can be added to the reactor or reaction zone in any known manner and in any order. For example, adding each catalyst component, monomer (and comonomer) to the reaction zone simultaneously, Method or the like can be used. If desired, each catalyst component can be pre-contacted in an inert atmosphere before contacting with the monomers (and comonomers).
- the gas phase polymerization may be carried out according to a known gas phase polymerization method and polymerization conditions, but is not limited thereto.
- a fluidized bed type reaction vessel preferably a fluidized bed type reaction vessel having an enlarged portion is used. There is no problem even with a reactor equipped with stirring blades in the reaction tank.
- each component As a method of supplying each component to the polymerization tank, supply it in a water-free state using an inert gas such as nitrogen or argon, hydrogen, ethylene, or the like, or dissolve or dilute it in a solvent or in a solution or slurry state.
- an inert gas such as nitrogen or argon, hydrogen, ethylene, or the like
- dissolve or dilute it in a solvent or in a solution or slurry state can be used.
- Each catalyst component may be supplied individually, or any components may be supplied in contact with each other in any order in advance.
- the temperature is not higher than the temperature at which the polymer melts, preferably from 20 ° C to: L00 ° C, particularly preferably from 40 ° C (to 90 ° C.
- the pressure is 0.1 l.
- the range is preferably from MPa to 5 MPa, more preferably from 0.3 MPa to 4 MPa, and hydrogen may be added as a molecular weight regulator for the purpose of controlling the melt fluidity of the final product.
- an inert gas may be present in the mixed gas during the polymerization.
- 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 olefin polymer in the examples were measured by the following methods.
- characteristic absorption derived from sodium olefin was used, for example, using 1375 cm -1 (propylene) and 772 cm -1.
- the infrared absorption spectrum was measured using an infrared spectrophotometer (FT-IR7300 manufactured by JASCO Corporation).
- the degree of short chain branching (SCB) was expressed as the number of short chain branches per 1000 carbons.
- Heating 40. From C to 150. C (10 ° C / min), hold for 5 minutes
- Intrinsic viscosity Dissolve 10 Omg of the obtained copolymer in 50 ml of tetralin at 135 ° C, and use an Ubbelohde viscometer set in a water bath maintained at 135 ° C. It was determined from the falling speed of the tetralin solution in which the sample was dissolved.
- MFR Measured at 190 ° C according to the method specified in JIS K6760.
- Density determined according to JIS K-6760. However, density (without anil) Is a value measured without annealing treatment, and a density value described as density (with annealing) is a measured value after annealing treatment. Unit: g / cm 3 Wei Example 1
- a 200 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried with H, and then purged with nitrogen.
- 51 samples were collected. Thereto was added 10 Oml of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath, and 11.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was ffi-dried and then purged with nitrogen. 1.05 g of the solid compound obtained in the above (1) was collected in the flask. Thereto was added 5 Oml of toluene to form a slurry, and 2.1 ml of a toluene solution of fluorophenol having a concentration adjusted to lmmo 1 / m1 was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C.
- the autoclave with a stirrer with an inner volume of 40 Oml was replaced with argon.
- the inside of the tube was evacuated, and 95 g of butane and 5 g of butene-1 were charged and heated to 70 ° C. Thereafter, ethylene was added to adjust the partial pressure to 6 kg, cm 2 to stabilize the system, and 0.25 ml of a triiso-butyl aluminum heptane solution adjusted to a concentration of lmmo 1 / ml was added.
- a 100 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then purged with nitrogen.
- 2.00 g of unheated silica (ES 70X manufactured by Crossfield) was collected.
- 50 ml of toluene was added 50 ml of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath, and then 8.0 ml of a toluene solution of trimethylaluminum adjusted to a concentration of lmmo 1 / m 1 was gradually dropped. At that time, gas generation was observed. After stirring at 5 ° C.
- the solid compound obtained in the above (1) was considered to have reacted with the water remaining in the silicide force and the trimethylaluminum to produce methylaluminoxane (a supplementary test of JP-A-11-207703), and was dried. Unlike Comparative Example 1 using silica, the polymer exhibited a polymerization activity, but the polymerization activity was lower than that of Example 1.
- a 500 ml four-necked flask equipped with a stirrer, a dropping funnel and a Jg meter was dried and then purged with nitrogen.
- 45.0 g of silica (Crossfield ES 70X) that had been heated at 300 ° C. for 5 hours under a nitrogen stream was collected.
- 250 ml of toluene was added thereto to form a slurry, and the mixture was cooled to 5 ° C. using an ice bath, and then 90.0 ml of a toluene solution of trimethylaluminum adjusted to a concentration of 1 mmo 1 / m 1 was slowly added dropwise. At that time, gas generation was observed.
- a 500 ml four-necked flask equipped with a stirrer was ffi-dried and then purged with nitrogen.
- 37.2 g of the solid compound obtained in the above (1) was collected.
- 50 ml of toluene was added to form a slurry, and 37.2 ml of a toluene solution of ammonium fluorophenol adjusted to a concentration of 2 mmo1 / ml was slowly dropped. At that time, gas generation was observed.
- a 100 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then purged with nitrogen. 2.10 g of the solid compound obtained in the above (1) was collected in the flask. Thereto was added 50 ml of toluene to form a slurry, and 4.2 ml of a toluene solution of penfluorofluorophenol adjusted to a concentration of lmmo 1 / ml was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was dried under reduced pressure, and then purged with nitrogen. 0.76 g of the solid compound obtained in the above (1) was collected in the flask. 50 ml of toluene was added thereto to form a slurry, and 1.5 ml of a toluene solution of 2,3,5,6-tetrafluorophenol adjusted to a concentration of lmmo 1 / ml was slowly added. At that time, gas generation was observed.
- Example 10 A 100 ml four-necked flask equipped with a stirrer and a thermometer was dried and then purged with nitrogen. 0.83 g of the solid compound obtained in (1) of Example 10 was collected in the flask. Thereto, 50 ml of toluene was added to make a slurry, and 1.70 ml of 4-fluorophenol was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C for 2 hours, the supernatant was filtered, and the remaining solid compound was washed four times with 50 ml of toluene and twice with 50 ml of hexane. Thereafter, the solid compound was dried by JE to obtain 0.88 g of a fluid solid compound.
- a 200 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried under reduced pressure, and then purged with nitrogen. 4.92 g of silica (Crossfield ES 70X) that had been heat-treated at 300 ° C. for 5 hours under a nitrogen flow was collected in the flask. Thereto was added 50 ml of toluene to form a slurry, which was cooled to 5 ° C. using an ice bath, and then 10.0 ml of a toluene solution of trimethylaluminum adjusted to a concentration of 1 mmol / ml was gradually added dropwise. At that time, gas generation was observed. After stirring at 5 ° C.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was dried under reduced pressure, and then purged with nitrogen. 3.19 g of the solid compound obtained in the above (1) was collected in the flask. 100 ml of toluene was added thereto to form a slurry, and 3.2 ml of a toluene solution of pentafluorophenol adjusted to a concentration of 2 mmol / ml was slowly added. At that time, gas generation was observed. After stirring at room temperature for 3 hours, the supernatant was filtered and the remaining solid compound was washed four times with 50 ml of toluene and twice with 50 ml of hexane. Thereafter, the solid compound was dried by drying to obtain 3.63 g of a solid conjugate having fluidity.
- Example 13 1.0 ml of a toluene solution of dimethylsilyl (tetramethylcyclopentagenenyl) (tert-butylamide) titanium dichloride having a concentration of 1 mo1 / ml was added, and then obtained in Example 13, (2). 20 mg of the obtained solid compound was added as a solid catalyst component. Polymerization was carried out at 70 ° C while feeding ethylene so as to keep the total pressure constant. After 30 minutes, the polymerization was stopped by adding 3 ml of ethanol. 1.40 g of olefin polymer was obtained.
- the polymerization activity per transition metal atom was 2.8 ⁇ 106 g / mo 1 Zr hours, and the polymerization activity per solid catalyst component was 140 g / g hours.
- Ma The obtained olefin polymer had an SCB of 27.1, a melting point of 77.3 ° C, and a temperature of 113.5 ° C.
- a 200-ml four-necked flask equipped with a stirrer, a dropping funnel and a meter was dried with 3 ⁇ 4E, and then purged with nitrogen.
- 9.26 g of silica (ES70X manufactured by Crossfield) which had been heated at 300 ° C. for 5 hours under a nitrogen flow was collected in the flask.
- 92.6 ml of toluene was added to form a slurry, which was cooled to 5 ° C. using an ice bath, and 18.5 ml of a trimethylaluminum toluene solution adjusted to a concentration of lmmo 1 / ml was gradually added dropwise. At that time, gas generation was observed.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was dried with S, and then purged with nitrogen. 5.45 g of the solid compound obtained in the above (1) was collected in the flask. Thereto was added 135 ml of toluene to form a slurry, and 10.9 ml of a toluene solution of pentafluorophenol adjusted to a concentration of lmmo 1 / ml was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C.
- the contents of the autoclave were washed with water and dried to obtain 39 g of an olefin polymer.
- the polymerization activity per transition metal atom was 2.0x10? G / mo 1 Zr hours, and the polymerization activity per solid catalyst component was 428 g / g hours.
- a 100 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was dried and then purged with nitrogen.
- Example 16 (2) 1 ml of a toluene solution of ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride whose concentration was adjusted to 1 zmo1 / ml was added, and then the solution obtained in Example 16 (2) was obtained. 32.5 mg of the solid compound was charged as a solid catalyst component. Polymerization was carried out at 70 ° C for 60 minutes while feeding ethylene so as to keep the total pressure constant. 43.5 g of the olefin polymer were obtained. The polymerization activity per transition metal atom was 4.4 x 10? G / molZr hours, and the polymerization activity per solid catalyst component was 134 Og / g hours.
- Example 16 (2) 1 ml of a toluene solution of dimethylsilylenebis (2-methyl-indenyl) zirconium dichloride adjusted to a concentration of 1 mo 1 / ml was added thereto, followed by the solid compound obtained in Example 16 (2) above.
- Omg was charged as a solid catalyst component.
- Polymerization was performed at 70 ° C for 60 minutes.
- 65 g of the olefin polymer were obtained.
- the polymerization activity per transition metal atom was 6.5 ⁇ 107 g / mo 1 Zr hours, and the polymerization activity per solid catalyst component was 232 Og / g hours.
- Example 16 (2) 1 ml of a toluene solution of bis (n-butylcyclopentene genyl) zirconium dichloride adjusted to a concentration of 1 mo1 / ml was added, and then the solid obtained in Example 16 (2) above was added. Compound 35.3 mg was charged as a solid catalyst component. Polymerization was carried out at 70 ° C for 60 minutes while feeding ethylene so as to keep the total pressure constant. 45.5 g of an olefin polymer were obtained. The polymerization activity per transition metal atom was 4.6 ⁇ 107 g / mo 1 Zr hours, and the polymerization activity per solid catalyst component was 1290 g / g hours.
- a 200 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was ffi-dried and then purged with nitrogen.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was dried by JE and then purged with nitrogen. 2.6 g of the solid conjugate obtained in the above (1) was collected in the flask. To this was added 50 ml of toluene to form a slurry, and 2.6 ml of a toluene solution of fluorophenol having a concentration adjusted to 2 mmo1 / ml was slowly added. At that time, gas generation was observed. After stirring at room temperature for 30 minutes and at 80 ° C.
- the BE was dried in a 300 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer, followed by purging with nitrogen.
- a 100 ml four-necked flask equipped with a stirrer and a thermometer was dried and then purged with nitrogen. 1.76 g of the solid compound obtained in the above (1) was collected in the flask. Thereto was added 50 ml of toluene to form a slurry, and 3.5 ml of a toluene solution of pentafluorophenol adjusted to a concentration of lmmo 1 / ml was slowly added. At that time, gas generation was observed.
- the obtained olefin polymer had an SCB of 21.1 and a melting point of 99.2, 110.3.
- a transition metal compound and an olefin polymerization catalyst using a transition metal compound in a polymerization involving formation of polymer particles for example, slurry polymerization, gas phase polymerization, etc.
- particles which can provide a polymer having high activity and excellent particle properties.
- a carrier composed of the particles, an olefin polymerization catalyst component composed of the particles, an olefin polymerization catalyst composed of the particles, and an olefin polymer having a high molecular weight and a narrow distribution using the olefin polymerization catalyst.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB988015404A CN1264869C (zh) | 1997-08-21 | 1998-08-20 | 改性粒子 ,用其制成的载体 ,用其制成的烯烃聚合用催化剂成分 ,用其制成的烯烃聚合用催化剂以及烯烃聚合物制备方法 |
DE69812884T DE69812884T2 (de) | 1997-08-21 | 1998-08-20 | Modifizierte teilchen, daraus hergestellter träger, daraus hergestellte polymerisationskatalysatorkomponente sowie polymerisationskatalysator und verfahren zur herstellung von olefinpolymeren |
EP98938902A EP0949273B1 (en) | 1997-08-21 | 1998-08-20 | Modified particles, carrier prepared therefrom, olefin polymerization catalyst component prepared therefrom, olefin polymerization catalyst prepared therefrom, and process for preparing olefin polymer |
US09/284,798 US6482765B1 (en) | 1997-08-21 | 1998-08-20 | Modified particles, carrier prepared therefrom, olefin polymerization catalyst component prepared therefrom, olefin polymerization catalyst prepared therefrom, and process for preparing olefin polymer |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/225066 | 1997-08-21 | ||
JP22506697 | 1997-08-21 |
Publications (1)
Publication Number | Publication Date |
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WO1999010389A1 true WO1999010389A1 (fr) | 1999-03-04 |
Family
ID=16823511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/003680 WO1999010389A1 (fr) | 1997-08-21 | 1998-08-20 | Particules modifiees, vehicule prepare a partir de ces particules, constituant de catalyseur de polymerisation d'olefine ainsi prepare, catalyseur de polymerisation d'olefine ainsi prepare et procede de preparation d'un polymere d'olefine |
Country Status (6)
Country | Link |
---|---|
US (1) | US6482765B1 (ja) |
EP (2) | EP1325934B1 (ja) |
KR (1) | KR20000068804A (ja) |
CN (1) | CN1264869C (ja) |
DE (2) | DE69829423T2 (ja) |
WO (1) | WO1999010389A1 (ja) |
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EP1054025A1 (en) * | 1999-05-19 | 2000-11-22 | Union Carbide Chemicals & Plastics Technology Corporation | Method for controlling molecular weight and molecular weight distribution in polymers produced using a single site catalyst |
JP2003105017A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 立体規則性α−オレフィン重合体の製造方法 |
JP2003105011A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 改質された粒子、担体、付加重合用触媒成分、付加重合用触媒、並びに付加重合体の製造方法 |
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US10940460B2 (en) | 2015-05-11 | 2021-03-09 | W. R. Grace & Co.-Conn. | Process to produce modified clay, modified clay produced and use thereof |
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ES2572756T3 (es) * | 1998-05-18 | 2016-06-02 | Chevron Phillips Chemical Company Lp | Proceso para la polimerización de un monómero con una composición de catalizador que contiene un compuesto organometálico, un compuesto de organoaluminio y un compuesto de óxido sólido tratado |
EP1153938A4 (en) * | 1999-09-29 | 2004-03-17 | Sumitomo Chemical Co | CATALYST FOR THE STEREOREGULAR POLYMERIZATION OF ALPHA OLEFINES AND METHOD FOR THE PRODUCTION OF STEREOREGULAR ALPHA OLEFIN POLYMER |
US6395666B1 (en) | 1999-09-29 | 2002-05-28 | Phillips Petroleum Company | Organometal catalyst compositions |
SG90762A1 (en) * | 1999-12-27 | 2002-08-20 | Sumitomo Chemical Co | Catalyst component for addition polymerization, catalyst for addition polymerization, and process for producing addition polymer |
SG83223A1 (en) * | 1999-12-27 | 2001-09-18 | Sumitomo Chemical Co | Modified particles, catalyst for olefin polymerization using the same, and process of producing olefin polymer |
CN1196716C (zh) * | 2000-12-26 | 2005-04-13 | 住友化学工业株式会社 | 改性粒子、载体、加成聚合用催化剂成分、加成聚合用催化剂及加成聚合物的制法 |
DE10163457A1 (de) * | 2001-12-21 | 2003-07-03 | Merck Patent Gmbh | Heterogenisierung von katalytischen Komponenten |
SG130016A1 (en) | 2002-09-24 | 2007-03-20 | Sumitomo Chemical Co | Modified particle, catalyst component for addition polymerization, catalyst for addition polymerization and process for producing addition polymer |
SG131120A1 (en) * | 2003-10-22 | 2007-04-26 | Sumitomo Chemical Co | Process for producing modified particle, carrier or catalyst component for addition polymerization, pre-polymerized catalyst component therefor, catalyst therefor, and addition polymer |
WO2005063831A2 (en) | 2003-12-23 | 2005-07-14 | Basell Polyolefine Gmbh | Preparation of supported cocatalysts |
CN100482695C (zh) * | 2004-04-30 | 2009-04-29 | 住友化学株式会社 | 改性粒子、加聚用催化剂组分或催化剂的制法及加聚物的制法 |
KR102285140B1 (ko) * | 2018-12-03 | 2021-08-02 | 한화솔루션 주식회사 | 올레핀 중합용 촉매의 제조방법 |
KR102287064B1 (ko) * | 2018-12-11 | 2021-08-05 | 한화솔루션 주식회사 | 올레핀 중합용 촉매의 제조방법 |
WO2020128668A1 (en) * | 2018-12-17 | 2020-06-25 | King Abdullah University Of Science And Technology | Heterogenized ru amine or imine catalysts for hydrogen generation from formic acid |
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- 1998-08-20 US US09/284,798 patent/US6482765B1/en not_active Expired - Fee Related
- 1998-08-20 EP EP03004898A patent/EP1325934B1/en not_active Expired - Lifetime
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1054024A1 (en) * | 1999-05-19 | 2000-11-22 | Union Carbide Chemicals & Plastics Technology Corporation | Inert particulate material passivation for single-site catalyst in EPDM production |
EP1054025A1 (en) * | 1999-05-19 | 2000-11-22 | Union Carbide Chemicals & Plastics Technology Corporation | Method for controlling molecular weight and molecular weight distribution in polymers produced using a single site catalyst |
JP2003105017A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 立体規則性α−オレフィン重合体の製造方法 |
JP2003105011A (ja) * | 2001-09-27 | 2003-04-09 | Sumitomo Chem Co Ltd | 改質された粒子、担体、付加重合用触媒成分、付加重合用触媒、並びに付加重合体の製造方法 |
US10940460B2 (en) | 2015-05-11 | 2021-03-09 | W. R. Grace & Co.-Conn. | Process to produce modified clay, modified clay produced and use thereof |
CN111589472A (zh) * | 2020-04-22 | 2020-08-28 | 齐齐哈尔大学 | 一种含羧基共轭微孔聚合物/TiO2复合材料的制备方法 |
CN111589472B (zh) * | 2020-04-22 | 2022-11-29 | 齐齐哈尔大学 | 一种含羧基共轭微孔聚合物/TiO2复合材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE69829423D1 (de) | 2005-04-21 |
DE69812884D1 (de) | 2003-05-08 |
EP0949273A1 (en) | 1999-10-13 |
CN1264869C (zh) | 2006-07-19 |
DE69829423T2 (de) | 2006-04-13 |
KR20000068804A (ko) | 2000-11-25 |
CN1242779A (zh) | 2000-01-26 |
EP1325934A1 (en) | 2003-07-09 |
US6482765B1 (en) | 2002-11-19 |
DE69812884T2 (de) | 2004-01-29 |
EP0949273B1 (en) | 2003-04-02 |
EP0949273A4 (en) | 2001-07-18 |
EP1325934B1 (en) | 2005-03-16 |
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