WO2008066200A1 - Composant de catalyseur pour la polymérisation d'oléfines et catalyseur et procédé servant à produire un polymère d'oléfine utilisant celui-ci - Google Patents

Composant de catalyseur pour la polymérisation d'oléfines et catalyseur et procédé servant à produire un polymère d'oléfine utilisant celui-ci Download PDF

Info

Publication number
WO2008066200A1
WO2008066200A1 PCT/JP2007/073427 JP2007073427W WO2008066200A1 WO 2008066200 A1 WO2008066200 A1 WO 2008066200A1 JP 2007073427 W JP2007073427 W JP 2007073427W WO 2008066200 A1 WO2008066200 A1 WO 2008066200A1
Authority
WO
WIPO (PCT)
Prior art keywords
component
bis
catalyst
group
carbon atoms
Prior art date
Application number
PCT/JP2007/073427
Other languages
English (en)
Japanese (ja)
Inventor
Takefumi Yano
Motoki Hosaka
Original Assignee
Toho Catalyst Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toho Catalyst Co., Ltd. filed Critical Toho Catalyst Co., Ltd.
Priority to JP2008547074A priority Critical patent/JP5394747B2/ja
Publication of WO2008066200A1 publication Critical patent/WO2008066200A1/fr

Links

Classifications

    • 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

Definitions

  • the present invention is capable of maintaining a high degree of stereoregularity and catalytic activity of a polymer, and also provides an effect of obtaining a high melt flow rate by adding a small amount of hydrogen, a so-called catalyst component for polymerizing olefins having a good hydrogen response. And a catalyst, and a method for producing a polymer of olefins using the same.
  • Patent Document 2 Japanese Patent Laid-Open No. 5-9209 discloses that an unsaturated cyclic compound acetal compound is effective as a donor for expanding the molecular weight distribution.
  • Patent No. 2 5 5 0 6 1 discloses that a cyclocycloalkoxy derivative is effective as a donor. 73427 4 « H
  • non-patent literature 1 Poly ymer B ulletin 54, 3 7 7-3 8 5
  • the silacyclodialkoxy derivatives have the same level of performance as existing high performance donors.
  • these methods are effective for obtaining highly stereoregular polymers with high catalytic activity, but from the viewpoint of the efficiency of controlling the molecular weight with hydrogen (hydrogen response) while maintaining these properties.
  • the polymer obtained by using the catalyst as described above is used for various applications such as containers and films in addition to molded articles such as automobiles or home appliances. They melt polymer powder produced by polymerization and are molded by various molding machines. Especially when manufacturing large molded products by injection molding, the fluidity of the molten polymer (melt flow rate, MFR) In order to reduce the cost of highly functional block copolymers for automotive materials, in the copolymerization reactor, an olefin-based thermoplastic elastomer (hereinafter referred to as “TPO”) is required.
  • Melt flow rate is highly dependent on the molecular weight of the polymer.
  • hydrogen when producing a low molecular weight polymer, that is, producing a high melt flow rate polymer.
  • a large amount of hydrogen is added in order to achieve ⁇ / ⁇ 2007 / 0 '3427.
  • the pressure resistance of the reactor is limited due to its safety, and the amount of hydrogen that can be added is also limited.
  • Patent Document 4 (WO 20 04- 1 6 6
  • Patent Document 1 Japanese Patent Application Laid-Open No. Sho 5 7 _ 6 3 3 10 (Claims)
  • Patent Document 2 Japanese Patent Application Laid-Open No. Hei 5-9209 (Patents)
  • Patent Document 3 Japanese Patent No. 2 5 5 7 0 6 1 (Claims)
  • Patent Document 4 WO 20 04-1 6 6 6 2 (Claims) (Non-Patent Document 1)] P o lyme r B u l e ret 54, 3
  • the object of the present invention is to polymerize olefins that can maintain a high degree of stereoregularity and catalytic activity of the polymer, and have a high melt flow rate by adding a small amount of hydrogen, so-called hydrogen response. It is an object of the present invention to provide a method for producing a catalyst component and catalyst for use, and an olefin polymer using the catalyst component. Disclosure of the invention
  • the present inventors have conducted intensive studies, and as a result, the catalyst for polymerizing olefins formed with a specific silacycloalkane compound as an essential component, or magnesium, titanium, halogen and electron donating compounds.
  • a catalyst formed from a solid catalyst component containing an organoaluminum compound and a silacycloalkane having an amino specific structure having a secondary amino group is more suitable as a catalyst for the polymerization of olefins than the conventional catalysts described above.
  • the present invention has been completed.
  • X is a secondary amino residue having 1 to 10 carbon atoms, a tertiary amino residue, an alkoxy group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group.
  • R 1 represents a straight or branched alkyl group having 1 to 10 carbon atoms, a cyclyl alkyl group, an aralkyl group or an aryl group
  • R 2 , R 3 , R 4 and R 5 represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, an alkyl group, an aralkyl group or an aryl group
  • n is an integer of 1 to 20
  • R 2 and R 3 or R 4 and R 5 may be bonded to each other to form a ring, and 1 to! ⁇ 5 may be the same or different.
  • R 4 , R 5 and R 6 are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups, and aralkyl groups. . or indicates Ariru group, 1 1 Oyopi 1 4 to 1 6 may be made different in co -) or the following general formula (3);
  • R 6 and R 7 are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aralkyl group or an aryl group.
  • RR 6 and R 7 may be the same or different, and provide a catalyst component for polymerizing olefins, which is represented by the following formula.
  • the present invention also provides an olefins polymerization catalyst formed using the olefins polymerization catalyst component as an essential component.
  • the present invention provides (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound,
  • the present invention also provides a method for producing an olefin polymer comprising polymerizing an olefin in the presence of the catalyst for olefin polymerization.
  • the catalyst for polymerizing olefins of the present invention is capable of maintaining a high degree of catalytic activity and high catalytic activity as compared with conventional catalysts, and has the effect of obtaining a high melt flow rate by adding a small amount of hydrogen (hereinafter simply “ Sometimes referred to as “hydrogen response”. Therefore, the ability to reduce the amount of hydrogen used in the polymerization, the high activity of the catalyst, and the ability to maintain the activity can provide general-purpose polyolefins at a low cost, and the weight of highly functional olefins can be reduced. Usefulness is expected in the production of coalescence. Brief Description of Drawings
  • FIG. 1 is a flow chart showing the steps for preparing the catalyst component and the polymerization catalyst of the present invention.
  • the component for olefins polymerization catalyst of the present invention is a compound of the general formula (1), the general formula (2) or the general formula (3). These can be used alone or in combination of two.
  • X is a linear or branched alkyl group having 1 to 10 carbon atoms or a secondary amino group in which a cycloalkyl group having 4 to 10 carbon atoms is bonded to an N atom, and 1 to 10 carbon atoms.
  • the compounds represented by the general formula (1) are more specifically described as follows: 1,1 bis (alkylamino) -2, n-bis (alkyl) silacycloalkyls, 1,1 bis (alkylamino) 1 2 , N-dialkylsilacycloalkanes, 1,1 bis (alkylamino) -2, n-trialkylsilacycloalkanes, 1,1 bis (alkylamino) — 2, n-tetraalkylsilacycloalkanes, 1, 1 1 Bis (alkylamino) 1 2, n-Tetrakis (alkyl) silacycloalkanes, 1-(alkylamino) — 1 1 (alkylalkoxy) 1 2, n-dialkyl silicic alkanes, 1 — ( Alkylamino) 1 1 1 (alkoxy) 1 2, n-trialkylsilacycloalkanes, 1 1 (alkylamino)
  • n- refers to the 2nd and nth positions, and the nth position refers to the position of the carbon atom facing the 2nd position adjacent to the key atom.
  • X is a secondary amino group in which a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 4 to 10 carbon atoms is bonded to the N atom, or 1 carbon atom
  • a linear or branched alkyl group having ⁇ 10 or an alkoxy group having a C 1-4O alkyl group bonded to an oxygen atom and a linear or branched chain having ⁇ to ⁇ 0 carbon atoms.
  • R 4 to R ⁇ 3 ⁇ 4 each of which is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and n is preferably an integer of 2 to 8.
  • R 4 and R 5 are preferably bonded to each other to form a ring.
  • the compound of the general formula (2) is more specifically described as follows: 1, 1-bis (alkylamino) 1 2-alkyl, n-aza (N-alkyl) silacycloalkanes, 1, 1 bis ( Alkylamino) _ 2-dialkyl, n-aza (N-alkyl) silacycloalkanes, 1, 1 bis (alkylamino) 1 2-dialkyl, n-aza (N-cycloalkyl) silicic al 1 1 (alkylamino) 1 1 1 (alkylalkoxy) — 2 -alkyl, n-aza (N-alkyl) silicic one, 1-(alkylamino) 1 1-(alkylanoleco) Xyl) 1-dialkyl, n-aza (N-alkyl) silacycloalkanes, 1 _ (alkylamino) 1 1 1 (analkyloxy) 1 2-anolequinole, n-aza (N-cycloalkyl)
  • X is a secondary amino group having 1 to 10 carbon atoms or a straight chain or branched alkyl group having 4 to 10 carbon atoms or a quaternary alkyl group having 4 to 10 carbon atoms bonded to the N atom
  • a linear or branched alkyl group having 1 to 10 carbon atoms or an alkoxy group having an alkyl group having 4 to 10 carbon atoms bonded to an oxygen atom is preferred
  • R 1 is a linear or branched chain having 1 to 10 carbon atoms.
  • R 6 and R 7 are each preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and n is preferably an integer of 2 to 8.
  • the compound of general formula (3) is more specifically described as follows: 1,1-bis (alkylamino) 1, 2, n_diaza (N, N, monodialkyl) silacycloalkanes, 1,1-bis (alkylamino) 1) 2-aza (N-alkyl), n-aza (N—H) silacycloalkanes, 1,1-bis (alkylamino) 1-2-aza (N-alkyl), n-a
  • Xyl 1, ⁇ -diaza ( ⁇ ⁇ , -dialkyl) silacycloalkanes, 1 1 (alkylamino) 1 1- (alkylalkoxy) 1 2-aza ( ⁇ -alkyl), ⁇ -aza ( ⁇ — ⁇ ) Silacycloalkanes, 1- (alkylamino) 1-2-aza ( ⁇ -alkyl), ⁇ -aza ( ⁇ -cycloalkyl) sila cycloalkanes, Among these compounds, particularly preferred compounds are The following compounds 5 8 1 3 1 may be mentioned, but are not limited thereto. '
  • the catalyst for olefins polymerization of the present invention is one or more silacycloalkane compounds selected from the above general formulas (1) to (3) (hereinafter sometimes referred to as “component (C)”).
  • component (C) silacycloalkane compounds selected from the above general formulas (1) to (3)
  • component (C) solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) and organoaluminum compound (B) (hereinafter simply referred to as “component (B)”) It is formed from).
  • Component (A) J of the catalyst for polymerizing olefins of the present invention contains magnesium, titanium, halogen and an electron-donating compound, and includes (a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) An electron donor compound can be obtained by contact.
  • the component (a) may include dihalide magnesium, disimagnesium, diallyloxymagnesium, halogenated alkoxymagnesium or fatty acid magnesium.
  • magnesium dihalide a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, dialkoxymagnesium is particularly preferable, and specifically, dimethoxymagnesium, diethoxymagnesium, Examples include dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnesium, and the like, and methoxymagnesium is particularly preferable.
  • dialkoxymagnesiums may be obtained by reacting magnesium metal with alcohol in the presence of a halogen-containing organic metal or the like.
  • the above dialkoxymagnesium can be used alone or in combination of two or more.
  • dialkoxymagnesium that is preferably used is in the form of granules or powder, and the shape may be indefinite or spherical.
  • dialkoxymagnesium when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution can be obtained, and the handling operability of the resulting polymer powder during the polymerization operation is improved. Problems such as clogging of the filter in the polymer separator caused by the fine powder contained in the water are solved.
  • the spherical dialkoxymagnet is not necessarily spherical, and an elliptical or potato-shaped one can also be used.
  • the particle shape is such that the ratio of the major axis diameter L to the minor axis diameter W (L / W) is 3 or less, preferably 1 to 2, more preferably 1 to 1.5. is there. a
  • the average particle diameter of the dialkoxymagnesium may be 1 to 200 m. Preferably, it is 5 to 1500 ⁇ m . In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 ⁇ m, preferably 5 to 50 ⁇ , and more preferably 10 to 40 ⁇ m.
  • the particle size it is preferable to use a particle having a small particle size distribution and a small particle size distribution. Specifically, the particle size of 5 ⁇ m or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 ⁇ m or more is 10% or less, preferably 5% or less. Further, the particle size distribution is expressed as D 90 / D 10 (where D 90 is the cumulative particle size at 90%, and D 10 is the cumulative particle size at 10%). Less than, preferably less than 2.
  • the tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used in the preparation of component (A) in the present invention is represented by the general formula T i (OR 9 ) mX 4 — m ( In the formula, R 9 represents an alkyl group having carbon number !! ⁇ 4, X represents a halogen atom, and m is an integer of 0 ⁇ m ⁇ 4.) Titanium halide or alkoxy titanium halide group represented by One or more compounds selected from the group consisting of
  • titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other titanium tetrahalides are used as titanium halides
  • methoxytitanium trichloride and ethoxytitanium trichloride are used as alkoxytitanium halides.
  • Examples include _n_butoxy titanium chloride. Of these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable. These titanium compounds can be used alone or in combination of two or more.
  • the electron-donating compound (hereinafter sometimes simply referred to as “component (c)”) used in the preparation of the solid catalyst component (A) in the present invention is an organic compound containing an oxygen atom or a nitrogen atom.
  • component (c) an organic compound containing an oxygen atom or a nitrogen atom.
  • organic compound containing an oxygen atom or a nitrogen atom for example, alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, isocyanates, S i—o _ c bonds or S i Organosilicon compounds containing one N—C bond.
  • alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol monole, methyl ether, ethyl ether, propyl ether, petitnole etherenole, aminole Etherol, diphenenole etherol, 9,9_bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1, ethers such as 3-dimethoxypropane, methyl formate, ethyl acetate, butyl acetate, Propyl acetate, Otyl acetate, Cyclohexyl acetate, Ethyl propionate, Ethyl butyrate, Ethyl benzoate, Propyl benzoate, Ptyl benzoate, Octyl benzoate, Cyclohexyl benzoate, p-toluic acid Methyl, p-toluic
  • Nitryls such as methyl isocyanate, ethyl isocyanate, etc., phenolalenorecoxysilane, anoloxyalkyloxysilane, phenylalkylanolecoxysilane, cycloanolenoquinolenorecoxysilane , Cycloanolenoquinoaylalkylalkoxy
  • Organosilicon compounds containing Si—O—C bonds such as silane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamino) dialkoxysilane, alkyl (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, An organosilicon compound containing a Si 1 N—C bond such as a cycloalkylaminotrialkoxysilane can be given.
  • esters, especially aromatic dicar ⁇ A> 1 Bonic acid diester is preferably used, and phthalic acid diester and phthalic acid diester derivatives are particularly preferred.
  • Specific examples of these phthalic acid diesters include dimethyl phthalate, jetyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisoptyl phthalate, ethylmethyl phthalate, phthalate Methyl isopate pill, Ethyl phthalate (n-propyl), Ethyl phthalate (n-butyl), Ethyl butyl phthalate, Di-n-pentyl phthalate, Diisopentinole phthalate, Dineopentyl phthalate, Phthalic acid Dihexyl, di-n-heptyl phthalate, di_n-octyl phthalate, bis (2,2-dimetheno
  • one or two hydrogen atoms of the benzene ring to which the two ester groups of the above phthalic acid diester are bonded are alkyl groups having 1 to 5 carbon atoms, or chlorine, bromine and fluorine. original And those substituted with a halogen atom such as a child.
  • the solid catalyst component prepared using the phthalate ester derivative as an electron-donating compound can further improve the effect of hydrogen amount on the melt flow rate, that is, the hydrogen response. Hydrogen added during polymerization Even if the amount is the same or small, the melt flow rate of the polymer can be improved.
  • Examples include: 4) dineopentyl 4-methylphthalate, 4) dineopentylol, 4-ethyl phthalate, 4-5, dineopentyl dimethylphthalate, 4, 5 Di-1- n- butyl, 4-necropentine dineopentyl phthalate, 4-dichlorobutyl phthalate, diisohexyl 4-chloro phthalate, 4-diisooctinole phthalenophthalate, 4-zetinore 4-bromophthalenoate, 4-dibromo phthalenoate di- Butinole, 4-bromophthalenoic acid dineopentinole, 4-bromophthalenoic acid disobutenole, 4-monobromophthalenoic acid disohexenole, 4-monobromophthalic acid diisooctyl, 4,5-dichlorophthalic acid diethyl, 4,5-dichlorophthalic acid di-n-
  • esters it is also preferable to use a combination of two or more of the above esters.
  • the total number of carbon atoms of the alkyl group of the ester used is 4 or more compared to that of other esters, the esters are combined. This is desirable.
  • component (d) a hydrocarbon compound (hereinafter sometimes simply referred to as “component (d)”.
  • this component (d) has a boiling point such as toluene, xylene, ethylbenzene, hexane, octane, decane, cyclohexane, etc.
  • a hydrocarbon compound of 50 to 1500C is preferably used. These may be used alone or in combination of two or more.
  • a particularly preferred method for preparing component (A) in the present invention is to form a suspension from component (a), component (c), and hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • a preparation method by bringing the mixed solution formed from b) and component (d) into contact with the suspension and then reacting it can be mentioned.
  • component (e) a polysiloxane
  • component (e) a polysiloxane
  • the stereoregularity or crystallinity of the produced polymer can be improved, and further the fine powder of the produced polymer can be reduced.
  • Polysiloxane is a polymer that has a siloxane bond (one S i—O bond) in the main chain, but is also referred to as silicone oil, and its viscosity at 25 ° C is 0.02 to 100 cm 2 / s (2 to 1 000 centistos), liquid or viscous chain at room temperature, partially hydrogenated, cyclic or modified polysiloxane.
  • chain polysiloxane dimethylpolysiloxane and methylphenylpolysiloxane are used.
  • partially hydrogenated polysiloxane methylhydrene polysiloxane having a hydrogenation rate of 10 to 80% is used.
  • cyclic polysiloxane hexamethylsiloxane is used.
  • Trisiloxane, otamethylcyclotetrasiloxane, decamethylcyclopentanesiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes are high-grade fats.
  • Examples include fatty acid group-substituted dimethylsiloxanes, epoxy group-substituted dimethylsiloxanes, and polyoxyalkylene group-substituted dimethylsiloxanes. Of these, decamethylenocyclopentasiloxane and dimethinorepolysiloxane are preferred, and decamethyl cyclopentasiloxane is particularly preferred.
  • the component (a), (b), and (c), and if necessary, the component (d) or the component (e) are brought into contact with each other to form the component (A). The preparation method of component (A) is described.
  • the magnesium compound (a) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (b) or a hydrocarbon compound (d), and an electron-donating property such as phthalic acid diester.
  • a spherical component having a sharp particle size distribution (A) can be obtained by using a spherical magnesium compound, and without using a spherical magnesium compound, for example, a solution or By forming particles by the so-called spray-drying method in which the suspension is sprayed and dried, the component (A) having a spherical shape and a sharp particle size distribution can be obtained.
  • the contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture is removed.
  • the contact temperature is the temperature at the time of contacting each component when contacting each component, and may be the same temperature as the reaction temperature or a different temperature.
  • the contact temperature may be a relatively low temperature range around room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for denaturation treatment. When obtaining the above, a temperature range of 40 to 1300 ° C is preferable. If the temperature during the reaction is less than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if the temperature exceeds 130 ° C, the solvent used will evaporate. Is obvious
  • the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
  • a preferred method for preparing component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d).
  • Method of preparing component (A) by reacting, or component (a) suspended in component (d), then contacting component (c) and then contacting component (b)
  • a method for preparing the component (A) can be mentioned. Further, the component (A) thus prepared may be contacted with the component (b) or the component (b) and the component (c) again or multiple times to improve the performance of the final solid catalyst component. it can. In this case, it is desirable to carry out in the presence of the hydrocarbon compound (d).
  • a preferred method for preparing component (A) in the present invention is to form a suspension from component (a), component (c), and hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. ) And component (d) are brought into contact with the suspension, followed by reaction.
  • Preferred methods for preparing component (A) in the present invention include the following methods.
  • a suspension is formed from the component (a), the component (c), and the hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • a mixed solution is formed from the component (c) and the hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • the suspension is added to the mixed solution. Thereafter, the temperature of the obtained mixed solution is raised and the reaction process (primary reaction process) is performed. After completion of the reaction, the obtained solid substance is washed with a liquid hydrocarbon compound at room temperature, and the washed solid substance is used as a solid product.
  • the washed solid substance is further added with a component (b) and a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. — Operation at 20 to 100 ° C, raising the temperature, performing a reaction process (secondary reaction process), and washing with a liquid hydrocarbon compound at room temperature after the reaction is completed.
  • Component (A) can be obtained by repeating 10 times.
  • dialkoxymagnesium (a) is suspended in a hydrocarbon compound (d) having a boiling point of 50 to 150 ° C.
  • the tetravalent titanium halogen compound (b) is brought into contact with this suspension, followed by reaction treatment.
  • one or more of the electron donating compounds (c) such as phthalic acid diester is used.
  • the ratio of each component used in preparing the solid catalyst component (A) varies depending on the preparation method-it cannot be roughly determined.
  • the content of titanium, magnesium, halogen atom, and electron donating compound in the solid catalyst component (A) in the present invention is not particularly limited, but preferably 0.5 to 8.0% by weight of titanium, preferably 1.0 to 8.0 by weight 0/0, more this Masoku is 2.0 to 8.0 wt 0/0 magnesium 1 0-7 0% by weight, more preferably 1 0-5 0% by weight, particularly preferably 1 5-4 0 weight 0/0, more preferably 1 5 to 2 5% by weight, a halogen atom 20-90 wt%, more preferably 30-8 5 wt.
  • / 0 particularly preferably 40 to 80% by weight, more preferably 45 to '75% by weight, and the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight. %, Particularly preferably 2 to 20% by weight in total.
  • organic aluminum Niumu compound used in forming the Orefin polymerization catalyst of the present invention (B)
  • compounds der lever represented by the above general formula (2) is not particularly limited, as R 8 is And Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, p is preferably 2 or 3, and 3 is particularly preferred.
  • Specific examples of such an organic aluminum compound (B) include triethylaluminum, jetylaluminum chloride, triisoptylaluminum, jetylalluminum promide, and jetylaluminum hydride. Two or more types can be used. Preferred are triethyl aluminum and triisobutyl aluminum.
  • Olefins include ethylene, propylene, 1-pentene, 1-pentene, 4-methyl / n H in H 1—pentene, bullcyclohexane, etc., and these olefins
  • Propylene and 1-butene are preferably used. Particularly preferred is propylene
  • the olefins to be copolymerized include ethylene, 1-butene,
  • these olefins can be used alone or in combination.
  • Copolymerization of ethylene with other olefins includes propylene and a small amount of ethylene.
  • a so-called propylene / ethylene block copolymer is typically used.
  • the catalyst of the present invention formed from the above component (A), component (B) and component (C) is also effective,
  • di-n-propyldimethyloxysilane diisopropyl
  • the component (D) described above is mixed and used, or the component (C) and the component (D) are separated in a block copolymerization multistage polymerization tank. It can also be used.
  • known electron donating compounds such as alcohols, oxygen gas or ketones can be added to the polymerization system.
  • the alcohols include ethyl alcohol, isopropyl alcohol, and the like.
  • the amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (B).
  • component (B) is 1 mol of titanium atom in component (A). It is used in the range of 1 to 200,000 moles, preferably 50 to 100,000 moles.
  • component (C) is used in the range of 0.002 to: L 0 mol, preferably 0.01 to 2 mol, particularly preferably 0.0: to 0.5 mol, per mol of component (B). .
  • component (D) When component (D) is used in combination, 0.02 to 10 moles, preferably 0.01 to 2 moles, particularly preferably 0.01 to 0.5 moles per mole of component (B) In addition, it is used in a range of 0.001 to 10 mol, preferably 0.01 to 10 mol, particularly preferably 0.01 to 2 mol, per mol of component (C).
  • each component is arbitrary, but the organoaluminum compound (B) is first charged in the polymerization system, and then the component (C) represented by the general formula (1) is contacted or mixed in advance. It is desirable to bring the solid catalyst component (A) into contact by contacting the component (C) with the component (D), or with the component (C) and the component (D) in any order. Alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are brought into contact with each other in advance.
  • component (A) and component (C) or component (C) and component (D) are charged into the polymerization system to form a contact catalyst.
  • the hydrogen response of the catalyst and the crystallinity of the polymer produced can be improved. This can be further improved.
  • the polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and an olefin monomer such as propylene can be used for polymerization in any state of gas and liquid.
  • the polymerization temperature is 20 ° C. or lower, preferably 100 ° C. or lower
  • the polymerization pressure is 1 OMPa or lower, preferably 6 MPa or lower. Both continuous polymerization and patch polymerization are possible.
  • the polymerization reaction may be performed in one stage, or may be performed in two or more stages.
  • component (A), the component (B) and the component (C) in the present invention also referred to as “main polymerization”
  • main polymerization catalytic activity, stereoregularity
  • component (A;), component (B) and / or component (C) are contacted in the presence of olefins, and 0.1 to 100 g of polyolefin per 1 g of component (A) is reserved.
  • component (B) and / or component (C) is contacted to form a catalyst.
  • component (D) is used in combination, component (A), component (B) and component (D) are brought into contact with each other in the presence of olefins during the preliminary polymerization, and component (C) is used in the main polymerization. You can also.
  • the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set in an inert gas atmosphere or a gas atmosphere in which propylene is polymerized. Then, after contacting component (C) and Z or component (D) and then contacting component (A), olefins such as propylene and Z or one or more other olefins Contact
  • the prepolymerization temperature is arbitrary, , «»
  • ⁇ / ⁇ 27 Although there is no particular limitation, it is preferably in the range of 1 ° C to 7 ° C, more preferably in the range of 0 ° C to 50 ° C.
  • component (C) improves the catalytic activity and stereoregularity compared to the case where a conventional catalyst is used. That is, when the catalyst of the present invention is used for the polymerization of olefins, the structure of component (C) maintains high stereoregularity, improves hydrogen response, and improves catalytic activity and stereoregularity. Was confirmed.
  • 1, 1 bis (methoxy) 1, 2, 6-dimethyl silaic hexane Take 0.05 ml of toluene solution containing 0.5 mol of toluene and replace with nitrogen gas, cool to o ° c, Using a syringe, 0.1 mol slurry of the prepared lithium salt of ethylamine was gradually added under a nitrogen stream. After the addition was completed, the reaction temperature was gradually raised, and the reaction was carried out at 60 ° C for 3 hours. After completion of the reaction, the reaction mixture is separated into a solid and a solution by centrifugation.
  • Example 2 The same method as in Example 1 except that the THF solution of methylamine was used instead of the THF solution of ethylamine and that the reaction was performed at 60 ° C for 2 hours instead of the reaction at 60 ° C for 3 hours.
  • THF solution of methylamine was used instead of the THF solution of ethylamine and that the reaction was performed at 60 ° C for 2 hours instead of the reaction at 60 ° C for 3 hours.
  • Elemental analysis of C, H, and N of the obtained fraction was performed, and the following results were obtained.
  • Figures in parentheses are theoretical values. C; 58. 0 1% (58. 00%), H; 1 1. 92% (1 1. 90%), N; 1 5. 00% (1 5. 03%)
  • 1-methyl-1-trimethoxysilyl-3-methylaminopropan was purified by distillation, dehydrated while being kept in a molecular sieve (3A) under a nitrogen stream, and dried.
  • 3A molecular sieve
  • 0.1 mol was slowly poured into a nitrogen atmosphere using a dropping funnel. Thereafter, the temperature was gradually raised and reacted at 40 ° C for 2 hours. After the reaction, the solid and the solution were separated by centrifugation under a nitrogen stream.
  • a methyllithium monolithium salt is obtained by reacting a hexane solution of butyllithium with a THF solution of methylamine.
  • 02 moles were prepared. 1. Prepare a toluene solution containing 1,1 bis (methoxy) _2 methinoleol 5-aza (N-methinole) silacyclopentane 0.01 mole synthesized above, and fully replace with nitrogen gas The flask was taken up and cooled to o ° C under a nitrogen atmosphere. To this cooling liquid, 0.02 mol of methylamine monolithium salt was gradually added. After the addition was completed, the temperature was gradually raised and the reaction was carried out at 70 ° C for 3 hours.
  • 1, 3 _bis (methylamino) monopropane A THF solution containing 0.1 mol of 10 Oml was placed in a flask thoroughly substituted with nitrogen gas under a nitrogen atmosphere. Cooled to C. Then 0.2 mol of commercially available butyl lithium The hexane solution contained was gradually added dropwise using a dropping funnel. After completion of the dropwise addition, the temperature was gradually raised and reacted at 30 ° C. for 2 hours to prepare a 0.1 mol slurry of lithium salt of 1,3-bis (methylamino) monopropane.
  • methylamine monolithium salt was prepared by a reaction between a hexane solution of butyllithium and a THF solution of methylamine.
  • 70 ml of toluene solution containing 0.02 mol of synthesized 1,1-bis (methoxy) -1,2,6-diaza (N, N, -dimethyl) siloxane hexane was sufficiently substituted with nitrogen gas Take to flask and cool to 0 ° C.
  • 0.04 mol of methylamine monolithium salt slurry was gradually added dropwise under a nitrogen gas atmosphere using a syringe.
  • 1, 1 bis (ethoxy) 1, 2, 5- ethinoresilacyclopentane 0.05 Take a toluene solution containing monole in a flask thoroughly purged with nitrogen gas, cool to o ° c, then syringe Then, 0.05 mol slurry of the prepared lithium salt of ethylamine was gradually added under a nitrogen stream. After the addition was completed, the reaction temperature was gradually raised, and the reaction was carried out at 50 ° C for 3 hours. After completion of the reaction, the reaction mixture was separated into a solid and a solution by centrifugation, and the solvent was distilled off by distillation under reduced pressure under a nitrogen atmosphere, and the temperature was raised.
  • a 0.05 mol slurry of monolithium salt of ethylamine was prepared by a reaction between a hexane solution of butyl lithium and a THF solution of ethylamine.
  • 0.05 mole slurry of ethyl salt of ethylamine was gradually added under a nitrogen atmosphere using a syringe. After the addition, the temperature was gradually raised and reacted at 40 ° C for 3 hours. After completion of the reaction, the solid was separated from the solution by centrifugation under a nitrogen stream, and the solution part was separated.
  • a round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas and having a volume of 200 Oml was charged with 150 g of methoxymagnesium and 750 ml of toluene to form a suspended state.
  • the suspension was then added to a solution of 450 ml toluene and 300 ml titanium tetrachloride pre-loaded in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. did.
  • the suspension was then reacted for 1 hour at 5 ° C. Thereafter, 21.5 ml of di-n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by reaction treatment with stirring for 2 hours.
  • the catalytic activity is indicated by the amount of polymer produced per hour (g) of the polymerization time per 1 g of the solid catalyst component. Calculated by the following formula.
  • Catalytic activity polymer produced (F) g / solid catalyst component g / 1 hour
  • HI (weight%) (H) g / (G) gxl
  • Ml melt index
  • the molecular weight distribution of the polymer is the ratio of the weight average molecular weight Mw and the number average molecular weight ⁇ determined by cross-fraction chromatography (CFC) (Mitsubishi Chemical Corporation CF CT-1 50 ⁇ ) under the following conditions: MwZMn Evaluated by.
  • Example 2 1, 1-bis (ethylamino) 1, 2, 6-dimethyl silicic acid hexane Instead of 1, 1, 1-bis (methylamino) 1, 2, 6-dimethyl silicic acid hexane synthesized in Example 2 was used. The experiment was performed in the same manner as in Example 8 except that. The results obtained are shown in Table 1.
  • a 500 ml round bottom flask equipped with a stirrer and thoroughly replaced with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol. And reacted at 30 ° C for 2 hours to obtain a homogeneous solution.
  • 1.1 g of phthalic anhydride was added to the homogeneous solution and reacted at 1300C for 1 hour.
  • the solution was then charged into 200 ml of titanium tetrachloride equipped with a stirrer and fully charged with nitrogen gas, charged in a 500 ml round bottom flask and maintained at 20 ° C. The whole amount was dropped over 1 hour.
  • the mixed solution was heated to 110 ° C. over 4 hours, and 2.68 ml of diisobutyl phthalate was added thereto and reacted for 2 hours. After completion of the reaction, the liquid part is removed by filtration, and the remaining solid component is washed at 110 ° C until no free titanium compound is detected with decane and hexane, filtered and dried to obtain a powdery solid Catalyst formation Got the minute. When the titanium content in this solid catalyst component was measured, 3.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The results obtained are shown in Table 1.
  • a round bottom flask having a capacity of 100 Om 1 and equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 3 2 g of ground magnesium for Grignard.
  • a mixed solution of 120 g of butyl chloride and 500 ml of dibutyl ether was added dropwise to the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour.
  • the reaction solution was cooled to room temperature, and the solid content was removed by filtration to obtain a magnesium compound solution.
  • a polymerization catalyst was formed and polymerized in the same manner as in Example 8 except that the solid catalyst component obtained above was used. The results obtained are shown in Table 1.
  • Example 8 49, 100 97. 9 0. 44 150 4.3
  • Example 10 46, 000 98. 0 0 44 90 4.9
  • Example 11 42, 800 85. 0 0. 44 280 4.5
  • Example 12 49, 500 97. 1 0. 44 78 5.
  • Example 16 40, 100 97. 2 0. 44 140 5 . 1
  • the olefin-based polymerization catalyst of the present invention is able to maintain the high degree of catalytic activity of the polymer and the hydrogen response better than conventional catalysts. Therefore, the ability to reduce the amount of hydrogen used in the polymerization, the high activity of the catalyst, and the ability to maintain the activity can provide general-purpose polyolefins at a low cost, and the weight of highly functional olefins can be reduced. Usefulness is expected in the production of coalescence.

Landscapes

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

Abstract

En utilisant un catalyseur pour la polymérisation d'oléfines composé de (A) un composant de catalyseur solide contenant du magnésium, du titane, un halogène et un composé donneur d'électrons, (B) un composé organique de l'aluminium représenté par la formule générale suivante : R8pAlQ3-p et (C) un composé silacycloalcane contenant un groupe amino secondaire, on peut obtenir un polymère ayant une activité catalytique élevée et une tacticité élevée. Le catalyseur pour la polymérisation d'oléfines a une bonne réponse à l'hydrogène.
PCT/JP2007/073427 2006-11-29 2007-11-28 Composant de catalyseur pour la polymérisation d'oléfines et catalyseur et procédé servant à produire un polymère d'oléfine utilisant celui-ci WO2008066200A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008547074A JP5394747B2 (ja) 2006-11-29 2007-11-28 オレフィン類重合用触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-321371 2006-11-29
JP2006321371 2006-11-29

Publications (1)

Publication Number Publication Date
WO2008066200A1 true WO2008066200A1 (fr) 2008-06-05

Family

ID=39467981

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/073427 WO2008066200A1 (fr) 2006-11-29 2007-11-28 Composant de catalyseur pour la polymérisation d'oléfines et catalyseur et procédé servant à produire un polymère d'oléfine utilisant celui-ci

Country Status (2)

Country Link
JP (1) JP5394747B2 (fr)
WO (1) WO2008066200A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7619049B1 (en) 2009-04-13 2009-11-17 Formosa Plastics Corporation, U.S.A. Cyclic organosilicon compounds as electron donors for polyolefin catalysts
US7790819B1 (en) 2009-04-13 2010-09-07 Formosa Plastics Corporation, U.S.A. Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
JP2012506147A (ja) * 2008-10-20 2012-03-08 ダウ コーニング コーポレーション Ｃｖｄ前駆体
WO2019097809A1 (fr) * 2017-11-17 2019-05-23 東邦チタニウム株式会社 Constituant catalytique solide pour une utilisation dans la polymérisation d'oléfines, procédé de production de constituant catalytique solide pour une utilisation dans la polymérisation d'oléfines, catalyseur pour une utilisation dans la polymérisation d'oléfines et procédé de production d'un polymère d'oléfine

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083215A (ja) * 1994-04-22 1996-01-09 Ube Ind Ltd α−オレフィンの重合方法
JP2000109514A (ja) * 1998-10-05 2000-04-18 Tokuyama Corp オレフィン重合用触媒及びこれを用いるオレフィンの重合方法
JP2002518404A (ja) * 1998-06-15 2002-06-25 ビーエーエスエフ アクチェンゲゼルシャフト 遷移金属錯体
WO2004016662A1 (fr) * 2002-08-19 2004-02-26 Ube Industries, Ltd. Catalyseurs de polymerisation ou de copolymerisation d'$g(a)-olefines, elements constituant ces catalyseurs et procedes servant a polymeriser des $g(a)-olefines au moyen de ces catalyseurs
WO2007018280A1 (fr) * 2005-08-08 2007-02-15 Toho Catalyst Co., Ltd. Composant catalytique et catalyseur de polymérisation d’oléfine et procédé de fabrication de polymère oléfine à l’aide de ceux-ci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083215A (ja) * 1994-04-22 1996-01-09 Ube Ind Ltd α−オレフィンの重合方法
JP2002518404A (ja) * 1998-06-15 2002-06-25 ビーエーエスエフ アクチェンゲゼルシャフト 遷移金属錯体
JP2000109514A (ja) * 1998-10-05 2000-04-18 Tokuyama Corp オレフィン重合用触媒及びこれを用いるオレフィンの重合方法
WO2004016662A1 (fr) * 2002-08-19 2004-02-26 Ube Industries, Ltd. Catalyseurs de polymerisation ou de copolymerisation d'$g(a)-olefines, elements constituant ces catalyseurs et procedes servant a polymeriser des $g(a)-olefines au moyen de ces catalyseurs
WO2007018280A1 (fr) * 2005-08-08 2007-02-15 Toho Catalyst Co., Ltd. Composant catalytique et catalyseur de polymérisation d’oléfine et procédé de fabrication de polymère oléfine à l’aide de ceux-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KIM S.-J. ET AL.: "Sterically Controlled Silacycloalkyl Diamide Complexes of Titanium (IV): Synthesis, Structure, and Catalytic Behavior of (cycl)Si(NBut)2TiCl2 [(cycl)Si = Silacyclobutane, Silacyclopentane, Silacyclopentene, and Silacyclohexane]", ORGANOMETALLICS, vol. 20, no. 11, 28 May 2001 (2001-05-28), pages 2136 - 2144, XP002414876, DOI: doi:10.1021/om000740g *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012506147A (ja) * 2008-10-20 2012-03-08 ダウ コーニング コーポレーション Ｃｖｄ前駆体
JP2014017502A (ja) * 2008-10-20 2014-01-30 Dow Corning Corp Ｃｖｄ前駆体
US8772524B2 (en) 2008-10-20 2014-07-08 Dow Corning Corporation CVD precursors
US7619049B1 (en) 2009-04-13 2009-11-17 Formosa Plastics Corporation, U.S.A. Cyclic organosilicon compounds as electron donors for polyolefin catalysts
US7790819B1 (en) 2009-04-13 2010-09-07 Formosa Plastics Corporation, U.S.A. Bicyclic organosilicon compounds as electron donors for polyolefin catalysts
JP2012523490A (ja) * 2009-04-13 2012-10-04 フオルモサ・プラステイクス・コーポレイシヨン・ユー・エス・エイ ポリオレフィン触媒のための電子供与体としての環式有機ケイ素化合物
WO2019097809A1 (fr) * 2017-11-17 2019-05-23 東邦チタニウム株式会社 Constituant catalytique solide pour une utilisation dans la polymérisation d'oléfines, procédé de production de constituant catalytique solide pour une utilisation dans la polymérisation d'oléfines, catalyseur pour une utilisation dans la polymérisation d'oléfines et procédé de production d'un polymère d'oléfine
JP2019094361A (ja) * 2017-11-17 2019-06-20 東邦チタニウム株式会社 オレフィン類重合用固体触媒成分、オレフィン類重合用固体触媒成分の製造方法、オレフィン類重合用触媒およびオレフィン類重合体の製造方法
JP7021915B2 (ja) 2017-11-17 2022-02-17 東邦チタニウム株式会社 オレフィン類重合用固体触媒成分の製造方法、オレフィン類重合用触媒の製造方法およびオレフィン類重合体の製造方法

Also Published As

Publication number Publication date
JP5394747B2 (ja) 2014-01-22
JPWO2008066200A1 (ja) 2010-03-11

Similar Documents

Publication Publication Date Title
JP5348888B2 (ja) オレフィン類重合用触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法
JP5158856B2 (ja) アミノシラン化合物、オレフィン類重合用触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法
WO2007026903A1 (fr) Composant catalyseur solide pour la polymérisation des oléfines, catalyseur et procédé de production d'un polymère oléfinique en utilisant ce catalyseur
JP5797661B2 (ja) オレフィン類重合用触媒およびオレフィン類重合体の製造方法
JP5623760B2 (ja) オレフィン類重合用固体触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法
JP5785809B2 (ja) オレフィン類重合用固体触媒成分、その製造方法、オレフィン類重合触媒およびオレフィン類重合体の製造方法
WO2001081434A1 (fr) Composant catalytique solide et catalyseur de polymerisation d'olefines
WO2006064718A1 (fr) Composant de catalyseur solide et catalyseur pour la polymérisation d'une oléfine, et procédé servant à produire un polymère ou un copolymère d'une oléfine en utilisant celui-ci
WO2016121551A1 (fr) Composant catalytique solide pour la polymérisation d'oléfines, procédé de production d'un catalyseur de polymérisation d'oléfines, et procédé de production d'un polymère d'oléfine
JP5110589B2 (ja) オレフィン類重合用固体触媒成分、その製造方法、触媒及びこれを用いたオレフィン類重合体の製造方法
JP2006169283A (ja) オレフィン類重合用固体触媒成分および触媒並びにこれを用いたオレフィン類重合体又は共重合体の製造方法
WO2008066200A1 (fr) Composant de catalyseur pour la polymérisation d'oléfines et catalyseur et procédé servant à produire un polymère d'oléfine utilisant celui-ci
JP2007224097A (ja) オレフィン類重合用触媒及びこれを用いたオレフィン類重合体の製造方法
JP5235673B2 (ja) エチレン・プロピレンブロック共重合体の製造方法
JP4775908B2 (ja) オレフィン類重合用触媒およびこれを用いたオレフィン類重合体の製造方法
JP4947632B2 (ja) オレフィン類重合用触媒及びこれを用いたオレフィン類重合体の製造方法
JP5968888B2 (ja) オレフィン類重合用固体触媒成分の製造方法、オレフィン類重合用触媒およびオレフィン類重合体の製造方法
JP4276554B2 (ja) オレフィン類重合用触媒
WO2010079701A1 (fr) Composant catalyseur solide pour polymérisation d'oléfines, procédé de fabrication associé, catalyseur et procédé de polymérisation d'oléfines
JP4841362B2 (ja) オレフィン類重合用触媒成分、触媒およびこれを用いたオレフィン類重合体の製造方法
JP4841361B2 (ja) オレフィン類重合用触媒成分、触媒及びこれを用いたオレフィン類重合体の製造方法
JP5143472B2 (ja) オレフィン類重合用触媒及びこれを用いたオレフィン類重合体の製造方法
JP4947622B2 (ja) オレフィン類重合用触媒及びこれを用いたオレフィン類重合体の製造方法
JP4993968B2 (ja) オレフィン類重合用触媒成分、触媒およびこれを用いたオレフィン類重合体の製造方法
JP2007224250A (ja) オレフィン類重合用固体触媒成分および触媒並びにこれを用いたオレフィン類重合体の製造方法

Legal Events

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

Ref document number: 07850075

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008547074

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07850075

Country of ref document: EP

Kind code of ref document: A1