WO2006064718A1 - 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 - Google Patents
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 Download PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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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
- C08F4/658—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657
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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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Definitions
- the present invention provides an olefin-based polymer that can maintain a high degree of stereoregularity and yield of a polymer, has a large effect on the hydrogen amount of menoleto flow rate, has a so-called hydrogen response, and has a wider molecular weight distribution.
- the present invention relates to a solid catalyst component for polymerization of olefins that can be obtained and a method for producing a polymer or copolymer of olefins using the catalyst as well as the catalyst.
- Patent Document 1 Japanese Patent Laid-Open No. Sho 5 7-6 3 3
- Patent Document 2 Japanese Patent Laid-Open No.
- Sho 5 7-6 3 3 1 1) a magnesium compound, a titanium compound and A method of polymerizing olefins having 3 or more carbon atoms in particular has been proposed using a catalyst comprising a combination with an organic key compound having a Si 1 O—C bond.
- Patent Document 3 Japanese Patent Laid-Open No. 63-310 10
- it is obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon compound and titanium halide.
- a propylene polymerization catalyst comprising a solid catalyst component prepared by heat-treating the product in a powder state, an organoaluminum compound and an organosilicon compound, and a method for polymerizing propylene has been proposed.
- Patent Document 4 Japanese Patent Laid-Open No. Hei 3-2 3470
- a Ziegler type solid catalyst component for ⁇ -year-old lefin polymerization obtained by contacting a organometallic compound of group IV (iv) is disclosed. Propylene polymerization methods have been proposed.
- the polymer obtained by using the catalyst as described above is used in various applications such as containers and films in addition to molded products such as automobiles or home appliances. They melt polymer powder produced by polymerization and are molded by various molding machines. Especially when producing large molded products by injection molding, the fluidity of the molten polymer (melt flow rate, MFR) may be required to be high.
- MFR melt flow rate
- TPO Plastic elastomer
- the melt flow rate in the homopolymerization stage is kept in order to keep the melt flow rate of the final product sufficiently large and facilitate injection molding.
- a value of 200 or more is required, so much research has been conducted to increase the melt flow rate of the polymer.
- Melt flow rate is highly dependent on the molecular weight of the polymer.
- hydrogen when producing a polymer having a low molecular weight, that is, in order to produce a polymer having a high melt flow rate, usually a large amount of hydrogen is added.
- the amount of hydrogen that can be added is also limited.
- the partial pressure of the monomer to be polymerized must be reduced, and in this case, productivity is lowered.
- the use of a large amount of hydrogen also causes cost problems.
- Patent Document 5 Japanese Patent Application Laid-Open No. 1-600 discloses a solid catalyst component for olefins polymerization containing dialkoxymagnesium, titanium tetrachloride and diptyl phthalate. By polymerizing propylene in the presence of, a stereoregular polymer can be obtained in high yield. It is effective to some extent. By the way, it has been pointed out that the polymer obtained by using the catalyst as described above has a molecular weight distribution which is not sufficiently wide when producing a biaxially oriented polypropylene film (BOP P).
- Patent Document 6 Japanese Patent Laid-Open No.
- Patent Document 7 Japanese Patent Publication No. 2002-542 34 7 discloses that the molecular weight distribution can be broadened while maintaining the activity by using succinic acid diester as the solid catalyst component. .
- this method does not have sufficient stereoregularity, and further improvements are required.
- Patent Document 1 JP-A-5 7-6 3 3 1 0 (Claims)
- Patent Document 2 JP-A 5 7-6 3 3 1 1 (Claims)
- Patent Document 3 Japanese Patent Application Laid-Open No. 6-3 30 10 (Claims)
- Patent Document 4 Japanese Patent Application Laid-Open No. 3-234 707 (Claims)
- Patent Document 5 Japanese Patent Application Laid-Open No. 11-6006 No. (Claims)
- Patent Document 6 Japanese Patent Application Laid-Open No. 2001-240634 (Claims)
- Patent Document 7 Special Table 200 2-54 2 34 7 (Claims, paragraph 00 24)
- the object of the present invention is to maintain the polymer's stereoregularity and yield at a high level, and have a great effect on the melt flow rate of the hydrogen amount, so-called good hydrogen response, and a broad molecular weight distribution.
- An object of the present invention is to provide a solid catalyst component and a catalyst for the polymerization of olefins capable of obtaining a polymer, and a method for producing an olefin polymer using the same. Disclosure of the invention
- the present inventors have conducted extensive studies, and as a result, the solid component containing magnesium, titanium, halogen, and an electron donating compound
- the present inventors have found that it is more suitable as a catalyst for the polymerization and copolymerization of olefins than the conventional catalysts described above, and has completed the present invention.
- the present invention provides a solid component (a) containing magnesium, titanium, halogen, and an electrophilic compound, the following general formula (1):
- R 1 represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, a bur group, a aralkyl group, or an aralkyl group
- R 2 represents a hydrogen atom, or a carbon number of 1 to 1 2 linear or branched alkyl groups, cycloalkyl groups, aryl groups, vinyl groups, aryl groups, aralkyl groups, R 1 and R 2 may be the same or different, and are formed by bonding to each other.
- R 5 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, An alkyl group, a phenyl group, a vinyl group, or a halogen atom, which may be the same or different, n is 0 or an integer of 1 to 5, and q is an integer of 1 to 4; However, when q is 1, at least one of 'R 5 is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group, an aryl group, a vinyl group, or a halogen atom.
- the present invention provides a solid catalyst component for polymerizing olefins, which is obtained by contacting d).
- the present invention also provides: (A) the solid catalyst component and (B) the following general formula (3); R 6 r A 1 Q 3 — r (3)
- the present invention provides a catalyst for polymerizing olefins characterized in that it is formed from
- the present invention provides a method for producing an olefin polymer or copolymer, which comprises polymerizing olefins in the presence of the catalyst for olefin polymerization.
- the catalyst using the catalyst component for polymerizing olefins of the present invention can maintain the stereoregularity and yield of the polymer at a higher level than the conventional catalyst, and has a great effect on the amount of hydrogen in the melt flow rate (hereinafter simply referred to as “the catalyst”). "Hydrogen response" is sometimes obtained. Therefore, it is possible to provide low-cost general-purpose polyolefins by functions such as reducing the amount of hydrogen used in polymerization and high catalyst activity, and it is useful in the production of highly functional olefin polymers. Be expected.
- FIG. 1 is a flowchart showing steps for preparing a catalyst component and a polymerization catalyst according to the present invention.
- the solid catalyst component (A) of the present invention is a solid component (a) containing magnesium, titanium, halogen and an electron-donating compound (hereinafter referred to as “component”).
- component (A) ”) may be referred to as an organic silicon compound (b) represented by the general formula (1) (hereinafter also referred to as“ component (b) ”), the general formula (2) (C) (hereinafter referred to as “component (c) J”) and organoaluminum compound (d) represented by the general formula (3) (hereinafter referred to as “component ( d) Sometimes referred to as “component ( d) Sometimes referred to as “component ( d) Sometimes referred to as “component ( d) Sometimes referred to as “component ( d) Sometimes referred to as J)).
- the solid component (a) includes a magnesium compound (i) (hereinafter sometimes referred to as “component (i)”) and a titanium compound (ii) (hereinafter also referred to as “component (ii)”). And an electron donating compound (Mi) (hereinafter sometimes referred to as “component (iii)”).
- component (iii) an electron donating compound
- the solid component (a) includes the component (i), the component (ii) and the component (iii) as well as the aromatic hydrocarbon compound (iv) (Hereinafter also referred to as “component (iv)”) can also be obtained by contact.
- magnesium compound (i) used for the preparation of the solid component examples include dihalogen magnesium, dianoloxy.noregmagnesium, halogenoalkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, and halogenated alkoxymagnesium. Or fatty acid magnesium.
- dihalogenated magnesium a mixture of dihalogenated magnesium and dianoloxymagnesium, dialkoxymagnesium are preferable, dialkoxymagnesium is particularly preferable, and specifically, dimethoxymagnesium, jetoxymagnesium.
- dialkoxymagnesiums may be obtained by reacting metal magnesium 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 thereof may be indefinite or spherical.
- spherical dialkoxymagnesium when spherical dialkoxymagnesium is used, a polymer powder having a better particle shape and a narrow particle size distribution is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separator caused by fine powder contained in the powder are solved.
- the spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an oval shape or a potato shape 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.
- the dialkoxymagnesium having an average particle size of 1 to 200 ⁇ can be used. Preferably it is 5-1550 in. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 / zm, preferably 5 to 50 ⁇ m, and more preferably 10 to 40 ⁇ .
- the particle size it is preferable to use one having a small amount of fine powder and coarse powder and a narrow particle size distribution.
- the particle size of 5 ⁇ or less is 20% or less, and preferably 10% or less.
- the particle size of 100 ⁇ m or more is 10% or less, preferably 5% or less.
- the particle size distribution is represented by D 9 O / D 10 (where D 90 is the particle size at 90% of the integrated particle size, and D 10 is the particle size at 10% of the integrated particle size). And preferably 2 or less.
- the production method of the above spherical dialkoxymagnesium is disclosed in, for example, Japanese Patent Application Laid-Open No. Sho 5 8-4 1 3 2, Japanese Patent Application Laid-Open No. 6 2-5 1 6 3 3, Japanese Patent Application Laid-Open No. Hei 3-74 34 1 No. 4, Japanese Patent Laid-Open No. Hei 4 3 6 8 3 91, Japanese Patent Laid-Open No. 8-7 3 3 8 8 and the like.
- the titanium compound (ii) used for the preparation of the solid component (a) has the general formula: T i (OR 7 ) n X 4 _ n (wherein R 7 represents an alkyl group having 1 to 4 carbon atoms, X Represents a halogen atom, and n is an integer of 0 ⁇ n ⁇ 4.)
- R 7 represents an alkyl group having 1 to 4 carbon atoms
- X Re represents a halogen atom
- n is an integer of 0 ⁇ n ⁇ 4.
- titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are exemplified as titanium halides, and methoxytitanium tricide rides and ethoxy as alkoxytitanium halides.
- 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 (iii) is an organic compound containing an oxygen atom or a nitrogen atom, for example, alcohols, phenols, ethers, esters, ketones, acids. Halides, aldehydes, amines, amides, nitriles, isocyanates, organic silicon compounds containing Si—O—C bonds or Si 1 N—C bonds, and the like.
- alcohols such as methanol, ethanol, n-propanol, and 2-ethenorehexanol
- phenols such as phenol and cresonole, methyl ether, ethyl ether, propyl ether, petitenole ether, and amyl ether
- Diphenyl ether 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-1-2-isopentyl-1,3-dimethoxypropane and other ethers, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate , Cyclohexyl acetate, ethyl propionate, ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl p-toluate,
- esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid ester derivatives are particularly preferable.
- 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), Ethanolate isobutyl phthalate, Di-n-pentyl phthalate, Diisopentyl phthalate, Phineolene dineopentinole, Phthal Dihexynole acid, di-n-heptyl phthalate, di-n-octyl phthalate, bis-phthalate
- the above phthalic acid diester derivative the above phthalic acid diester 1 or 2 hydrogen atoms in the benzene ring to which the two ester groups are bonded are substituted with alkyl groups having 1 to 5 carbon atoms or halogen atoms such as chlorine atoms, bromine atoms and fluorine atoms.
- alkyl groups having 1 to 5 carbon atoms or halogen atoms such as chlorine atoms, bromine atoms and fluorine atoms.
- the solid catalyst component prepared using the phthalate ester derivative as an electron-donating compound can further improve the effect of the hydrogen amount on the melt flow rate, that is, the hydrogen response. Hydrogen added during polymerization Even with the same amount or a small amount, the melt flow rate of the polymer can be improved.
- 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.
- the components (i), (ii), and ( ⁇ ) are aromatic
- the method of preparing the solid component (a) by contacting it in the presence of the hydrocarbon compound () is a preferred embodiment.
- the component (iv) has a boiling point of 5 such as toluene, xylene, and ethylbenzene.
- Aromatic hydrocarbon compounds at 0 to 150 ° C. are preferably used. These may be used alone or in combination of two or more.
- a suspension is prepared from the component (i), the component (iii) and the aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C.
- a preparation method may be mentioned by forming and contacting a mixed solution formed from component (ii) and component (iv) with the suspension, followed by reaction.
- polysiloxane (V) J polysiloxane (hereinafter sometimes simply referred to as “component (V) J”) in addition to the above components. It is possible to improve the stereoregularity or crystallinity of the polymer produced and to reduce the fine powder of the produced polymer
- Polysiloxane has a siloxane bond (_S i in the main chain).
- a polymer having an O bond which is also collectively referred to as silicone oil, and having a viscosity at 25 ° C. of 0.02 to 100 cm 2 / s (2 to 100 centistokes), It is a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.
- chain polysiloxane dimethyl polysiloxane and methylphenyl polysiloxane are used.
- partially hydrogenated polysiloxane methyl hydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used.
- cyclic polysiloxane Oxamethyl cyclotrisiloxane, Octamethyl cyclotetrasiloxane, Decamethyl cyclopentasiloxane, 2, 4, 6-trimethylcyclotrisiloxane, 2, 4, 6, 8-tetramethyl
- cyclotetrasiloxane and the modified polysiloxane include higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane.
- decamethylolecic pentasiloxane and dimethylpolysiloxane are preferred, and decamethyl pentapentasiloxane is particularly preferred.
- the above components (i), (ii), and (iii) and, if necessary, the component (iv) or the component (V) are brought into contact with each other to form a solid component (a).
- the method for preparing the solid component (a) is described. Specifically, the magnesium compound (i) is suspended in a tetravalent titanium halogen compound (ii) or an aromatic hydrocarbon compound (iv), and an electron donating compound (iii) such as a phthalic acid diester is further required.
- a method of obtaining a solid component (a) by contacting a tetravalent titanium halogen compound (ii) can be mentioned.
- a solid component (a) having a spherical shape and a sharp particle size distribution can be obtained, and without using a spherical magnesium compound, for example, using a spray device.
- a solid component (a) having a spherical shape and a sharp particle size distribution can be obtained by forming particles by so-called spray drying, in which the solution or suspension is sprayed and dried.
- 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 near room temperature when the mixture is simply brought into contact with stirring and mixed, or is dispersed or suspended for modification, but the product is reacted after contact. When obtaining the above, a temperature range of 40 to 1300 ° C is preferable.
- the reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.
- the component (i) is suspended in the component (iv), and then the component (ii) is contacted and then the component ( ⁇ ) and the component (iv) are contacted.
- a method of preparing the solid component (a) by reacting, or suspending the component (i) in the component (iv) and then contacting the component (iii) and then contacting the component (ii) And a method of preparing the solid component (a) by reacting them.
- the solid component (a) thus prepared is contacted with the component (ii) or the component (ii) and the component () again or more times to improve the final solid catalyst. be able to.
- a suspension is formed from the component (i), the component ( ⁇ ), and the aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C.
- the preparation method by making the mixed solution formed from component (ii) and component (iv) contact this suspension, and making it react after that can be mentioned.
- Preferred methods for preparing the solid component (a) in the present invention include the methods shown below.
- a suspension is formed from the component (i), the component (iii) and the aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C.
- a mixed solution is formed from the component (iii) and the aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C., and the suspension is added to the mixed solution. Then, the obtained mixed solution is heated and subjected to a reaction process (first reaction process). 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 The substance is further brought into contact with component (ii) and an aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C at a temperature of 20 to 100 ° C, and the temperature is raised.
- the solid component (a) can be obtained by repeating the operation of washing with a liquid hydrocarbon compound at room temperature 1 to 10 times.
- a suspension is formed from the component (i) and the component (iv), and the component (ii) and the component ( There is a method in which the mixed solution formed from iv) is added, the component (iii) is added to the obtained mixed solution, the temperature is raised, and the reaction treatment (1) is performed to obtain the solid component (a).
- the solid product obtained after the reaction treatment (1) is washed with the aromatic hydrocarbon compound used as component (iv), and is further brought into contact with the mixed solution formed from component (ii) and component (iv). More preferably, the temperature is raised and the reaction treatment (2) is performed to obtain the solid component (a).
- dialkoxymagnesium (i) is suspended in an aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C. Then, the suspension was brought into contact with a mixed solution of a tetravalent titanium halogen compound ( ⁇ ) and an aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C. I do. At this time, before or after contacting the mixed solution of the tetravalent titanium halogen compound (ii) and the aromatic hydrocarbon compound (iv) having a boiling point of 50 to 150 ° C.
- This solid product (1) is a hydrocarbon compound which is liquid at room temperature, preferably an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C.
- the tetravalent titanium halogen compound (ii) is contacted again in the presence of the aromatic hydrocarbon compound at ⁇ 20 to 100 ° C. Processing is performed to obtain a solid product (2). If necessary, the intermediate washing and the second reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid component (a).
- the ratio of the amount of each component used in preparing the solid component (a) varies depending on the preparation method and cannot be specified unconditionally.
- electrophilic compound (iii) is 0.0 1 to 10 mol, preferably 0 0 1 to 1 mol, more preferably 0.02 to 0.6 mol, aromatic hydrocarbon compound () force S 0.001 to 500 mol, preferably 0.00 1 to 100 mol , More preferably 0.0005 to 10 moles, and polysiloxane (V) is 0.01 to: L 00 g, preferably 0.05 to 80 g, more preferably 1 to 50 g. .
- the titanium in the solid component (a) in the present invention, magnesium, halo gen is not content particular provision of the electron-donating compound, preferably titanium from 1.0 to 8.0 weight 0/0, preferably 2.0 to 8.0 wt 0/0, yo Ri is preferably 3.0 to 8.0 wt% magnesium 1 0-70 weight 0/0, more preferably 1 0-5 0% by weight, particularly preferably 15 to 40% by weight, more preferably 15 to 25% by weight, halogen 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, 4 to 75 to 5% by weight, and the total amount of electron-donating compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight, and particularly preferably 2 to 20% by weight.
- the electron-donating compound preferably titanium from 1.0 to 8.0 weight 0/0, preferably 2.0 to 8.0 wt 0/0
- yo Ri is preferably 3.0 to 8.0 wt% magnesium 1 0-70 weight 0
- Examples of the organic silicon compound (b) represented by the above general formula (1) constituting the olefins polymerization angle solid catalyst component of the present invention include the following general formula (4); (R 3 ) 4 _ t S i ( OR 4 ) t (4)
- examples of the organic silicon compound (b 1) represented by the general formula (4) include alkyl alkoxy silanes, alkyl (alkoxy alkyl) alkoxy silanes, cyclo alkenyl alkenyl silanes, phenol alkenyl silanes, Alkyl (phenyl) alkoxysilane, Alkyl (alkylamino) alkoxysilane, Alkylaminoalkoxysilane, Cycloalkynole (alkylamino) Alkoxysilane, Alkyl (cycloalkylamino) Alkoxysilane, Polycyclic aminoalkoxysilane, Alkyl (Polycyclic amino) ) Alkoxysilanes can be mentioned.
- R 3 is preferably an alkyl group such as a methyl group, an ethyl group, an isopropyl group, an isobutyl group, or a t-butyl group, a cyclopentyl group, or a cyclohexyl group, a secondary carbon or It is more preferable that it is an alkyl group containing a tertiary carbon, and it is particularly preferable that the carbon directly bonded to Si is a secondary carbon or a tertiary carbon.
- R 4 is preferably a methyl group or an ethyl group. A dialkoxysilane having t of 2 is preferred.
- a specific example of the above organic silicon compound (bl) is as follows: Oral pyrdimethyoxysilane, diisopropyldimethyoxysilane, di-n-butyldimethyoxysilane, di-n-butylmethoxysilane, tert-butyl (methyl) dimethyoxysilane, tert-butyl (ethyl) dimethyoxysilane, dicyclohexyldimethoxysilane, cyclohexinole ( Methyl / Le) Dimethoxysilane, Dicyclopentyl Dimethoxysilane, Cyclopentyl (Methyl) Jetoxysilane, Cyclopentyl (Ethyl) Dimethoxysilane, Cyclopentyl (Cyclohexyl) Dimethoxysilane, 3-Methylcycline Hexinore Dimethyoxysilane, 4-met
- Examples of the organic silicon compound represented by the general formula (5). (B 2) include, for example, alkyl (alkylamino) alkoxysilane, cycloalkyl (alkylamino) alkoxysilane, alkyl (cycloalkylamino) alkoxysilane, cycloalkyl ( Examples include alkylsilanes, alkoxysilanes, alkylaminoalkoxysilanes, cycloalkylaminoalkoxysilanes, polycyclic aminoalkylalkoxysilanes, and polycyclic aminoalkoxysilanes. Examples of the polycyclic aminoalkoxysilane include bisperhydroquinolinodialkoxysilane and bisperhydroisoquinolinodialkoxysilane.
- R 1 represents an alkyl group such as a methyl group, an ethyl group, an isopropyl group, an isobutyl group, or a tert-butyl group
- N2 and cyclohexyl groups are preferred
- R 2 is preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isoptyl group, a tert_butyl group or the like, a cyclopentyl group, or a cyclohexyl group
- R 1 and R 2 are bonded to each other to form a ring, and preferably a polycyclic amino group containing a nitrogen atom bonded to Si, an alkyl group or polycyclic containing a secondary carbon or tertiary carbon More preferred is an amino group.
- R 3 is preferably a methyl group, an ethyl group, an isopropyl group, an isoptyl group, an arenoquinole group such as a tert-ptynole group, a cyclopentyl group, or a cyclohexynole group, and more preferably an alkyl group containing a secondary carbon or a tertiary carbon.
- the carbon directly bonded to Si is a secondary carbon or a tertiary carbon.
- organic key compound (b 2) examples include bis (jetylamino) dimethyloxysilane, bis (dipropylamino) dimethyloxysilane, bis (disisopropylamino) dimethyloxysilane, bis (dibutylamino) dimethyl.
- Toxisilane Bis (disisobutylamino) Dimethoxysilane, Bis (di-tert-butylamino) Dimethoxysilane, Bis (dicyclopentylamino) Dimethoxysilane, Bis (dicyclohexylamino) Dimethoxysilane, Bis 2-Methylcyclohexylamino) Dimethoxysilane, Bisperhydroisoquino linodimethoxysilane, Bisperhydroquinolinodimethoxysilane, Bis (ethylpropylamino) Dimethoxysilane, Bis (ethylisopropylamino) dimetho Sisilane, bis (ethyl butylylamino) dimethoxysilane, bis (ethylisobutylamino) dimethyloxysilane, bis (ethyl tert-butylamino) dimethyloxysilane, bis
- Examples of the organic compound (c) constituting the solid catalyst component for olefins polymerization of the present invention include the following general formula (6):
- alkenyl group-containing alkyl silane alkenyl group-containing alkyl silane, alkenyl group-containing alkyl silane, alkenyl group-containing phenyl silane, alkenyl group-containing butyl silane, alkenyl group-containing alkyl halogenated silane, alkenyl group Containing halogenated silanes.
- Examples of the compound (c 2) of the general formula (7) include vinyl group-containing alkyl silanes, bur group-containing cycloalkyl silanes, bur group-containing vinyl silanes, vinyl group-containing halogenated silanes, Examples include butyl group-containing alkylhalogenated silanes.
- preferred compounds when used in combination with the organic key compound (bl) include the organic key compound (cl),
- Examples include alkenyl group-containing alkyl silanes, alkenyl group-containing cycloalkyl silanes, alkenyl group-containing silanes, alkenyl group-containing vinyl silanes, alkenyl group-containing alkyl halogenated silanes, and alkenyl group-containing halogenated silanes.
- Preferred compounds for use in combination with the key compound (b 2) include organic key compounds (c 1) and (c 2) (hereinafter, in the case of the combined use of (c 1) and (c 2), c), that is, vinyl group-containing alkyl silanes, vinyl group-containing cycloalkyl silanes, bull group-containing vinyl silanes, bull group-containing halogenated silanes, vinyl group-containing alkyl halogenated silanes, alkenyl group-containing alkyl silanes.
- alkenyl group-containing cycloalkylsilane alkenyl group-containing fuel silane, alkenyl Containing vinylsilane, an alkenyl group-containing alkyl Ruharogen silane, and an alkenyl group-containing silane halide.
- R 5 is preferably a methyl group, an ethyl group, a bur group, or a chlorine atom
- q is preferably a dialkenyl silane or trialkenyl silane having 2 or 3 and n is 1.
- Particularly preferred compounds are vinyl trialkyl silane, dibuty dialkyl silane, allyl vinyl dialkyl silane, allyl trialkyl silane, diaryl dialkyl silane, diaryl dihalide, and triaryl alkyl silane.
- an olefin polymer having a wider molecular weight distribution can be obtained.
- organic silicon compound (c) examples include: allyltriethyl silane, 'allyltributyl silane, allylmethyl divinyl silane, Rildimethylolene vinyl silane, allylmethyl dichlorosilane, allyl trichloro silane, allyl tribromo silane, dialyl dimethyl silane, dialyl decyl silane, dialyl dibi silane, dialyl methyl vinyl silane, dialyl methyl chloro silane , Di-arinoresyl chlorosilane, diaryl dib silane silane, triallyl methyl silane, triallyl ethyl silane, triaryl vinyl silane, triaryl silane silane, triaryl promo silane, tetraaryl silane, di-3-butyl silane dimethino silane, di-3-pteni ⁇ / Silane Getinoresilane, Di-3-Buteninosilane Divinylsilane, di
- the compound represented by formula der lever (3) is not particularly limited, as R 6 is An ethyl group and an isoptyl group are preferred, and Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, r is preferably 2 or 3, and 3 is particularly preferred.
- Specific examples of such an organic aluminum compound (d) include triethylaluminum, jet aluminum lid, triisobutylaluminum, jetyla. Luminumbum mouth, Jetil aluminum hydride,
- the solid catalyst component (A) of the present invention is prepared by using an organosilicon compound (bl) as the compound of the general formula (1) (Preparation Method 1) Solid Catalyst Component (A 1) (hereinafter “Component” (A l) ”) and an organic compound (b 2) (Preparation method 2) Solid catalyst component (A 2) (hereinafter“ Component (A2) ”) This will be explained separately.
- the solid catalyst component (A 1) contains magnesium, titanium, halogen, the above component (b 1) and a polymer of the above component (c 1) or component (c 1). It can be obtained by contacting the component (a) with the component (b 1), the component (c 1) and the component (d). Component (c 1) can be finally contained in the solid catalyst component in the form of a polymer, but when contacting components (a), (b 1), (c 1) and (d), Ingredient (c 1) is polymerized and contained.
- the contact of components (a), (b 1), (c 1) and (d) is carried out in the presence of an inert solvent in view of ease of operation.
- an inert solvent aliphatic hydrocarbon compounds such as hexane, heptane, and cyclohexane, and aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene are used.
- the order of contacting the components is not particularly limited, but the following order of contact is preferable.
- the component (a) is first contacted with the component (b 1) or the component (c 1) and then the component (d) is contacted, and the component (a) is mixed with the component (c 1). More desirable is a method of contacting, and then contacting component (b 1) and component (d).
- the component (d) is first brought into contact with the component (a)
- it is brought into contact in the presence of the component (b 1) or the component (c 1).
- an inert solvent such as heptane in order to remove unnecessary components.
- component (d) remains in the solid catalyst component, it becomes a source of deterioration over time such as a decrease in catalyst activity.
- the component (a) is brought into contact with the component (b 1), the component (c 1) and the component (d), and then again the component (b 1), the component (c 1) and the component (d) Can be contacted once or twice or more.
- the organic compound (b 1), the organic compound (c 1) and the organoaluminum compound (d) are brought into contact with the solid component (a)
- the polysiloxane (e) is brought into contact with the solid component (a). It is preferable because the molecular weight distribution of the produced polymer can be widened, the stereoregularity or crystallinity can be improved, and the fine powder of the produced polymer can be reduced.
- polysiloxane (e) examples include those similar to the polysiloxane (V) used in preparing the solid component (a).
- the ratio of the amount used when contacting each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited.
- the usual component (b 1) and the component (c 1) Is used in the range of 0.5 to 10 moles, preferably 1 to 5 moles per mole of titanium atom in component (a).
- Component (d) is 1 to 15 mol, preferably 3 to 10 mol, per mol of component (a), Particularly preferably, it is used in the range of 4 to 7 mol.
- the temperature at which the above components are brought into contact is 110 to 100 ° C, preferably 0 to 80 ° C, and particularly preferably 25 to 75 ° C.
- the contact time is 1 minute to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 2 hours.
- the component (c 1) is polymerized into a polymer depending on the conditions for contacting the component (c 1).
- the contact temperature is 30 ° C or higher, the polymerization of the component (cl) starts and becomes a polymer, and the resulting olefin polymers are improved in crystallinity and catalytic activity.
- the above preparation method 1 and the obtained solid catalyst component (A 1) contain magnesium, titanium, halogen, component (b 1) and component (c 1) or a polymer thereof, and the content of each component the magnesium 1 0-7 0 by weight%, preferably 1 0-5 0% by weight, titanium 1.0 to 8.0 wt 0/0, preferably from 2.0 to 8.0 wt%, halogen 20 to 90% by weight, preferably 30 to 85% by weight, component (bl) is 1.0 to 50% by weight, preferably 1.0 to 30% by weight, component (c 1) or The polymer content is 1.0 to 50% by weight, preferably 1.0 to 30% by weight.
- the solid catalyst component (A 2) is composed of a solid component (a) containing magnesium, titanium, halogen and an electrophilic compound, an organic key compound (b 2), and an organic compound represented by the general formula (2). It can be obtained by the preparation method 2 in which the silicon compound (c) and the organoaluminum compound (d) represented by the general formula (3) are contacted.
- Examples of the organic silicon compound (c) preferably used in Preparation Method 2 include vinyl trimethylenosilane, butyltriethyl silane, vinyl retino chlorosilane, vinino trichlorosilane, vininotrib mouth silane, dibi nitroresin chinole silane, divinyl jetino les.
- the solid catalyst component (A 2) of the present invention is obtained by bringing the component (b 2), the component (c) and the component (d) into contact with the solid component (a). , (B 2), (c) and (d) contacts are considered for ease of operation.
- an inert solvent aliphatic hydrocarbon compounds such as tan, hexane and hexane, and aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene are used.
- the order of contacting the components is not particularly limited, but the following order of contact is preferable.
- component (a) is first contacted with component (b 2) or component (c).
- the component (d) is then contacted, and when the component (a) is contacted with the component (c) and then the component (c) and the component (d) are contacted, the component (b 2) or Contact is made in the presence of component (c).
- component (b 2) is washed with an inert solvent such as heptane in order to remove unnecessary components.
- component (d) remains in the solid catalyst component, it may cause deterioration over time, such as a decrease in catalyst activity.
- component (b 2), component (c) and component (d) are repeated again. It can be contacted once or more than once.
- the ratio of the amount used when contacting each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited.
- component (c) is used in the range of 0.2 to 10 mol, preferably 0.5 to 5 mol, per mol of titanium atom in component (a).
- Component (d) is used in the range of 0.5 to 15 mol, preferably 1 to 10 mol, particularly preferably 1.5 to 7 mol, per mol of titanium atom in component (a).
- the temperature at which each of the above components is brought into contact is _10 ° C to 100 ° C, preferably 0 to 90 ° 0, particularly preferably 20 ° C to 80 ° C.
- Contact time is 1 Minutes to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 30 minutes to 2 hours.
- component (c) may overlap to form a polymer. is there. When the contact temperature is 30 ° C or higher, the polymerization of component (c) starts and part or all of it becomes a polymer, and the resulting olefins polymer crystallinity and catalytic activity are improved.
- the solid catalyst component (A2) obtained by Preparation Method 2 as described above contains magnesium, titanium, halogen, component (b 2) and component (c) or a polymer thereof, and each component is contained. amounts, magnesium 1 0-7 0% by weight, preferably 1 0 to 50 wt%, titanium from 1.0 to 8 2.0 wt%, preferably 2.0 to 8.0 wt 0/0, halogen 20 90 wt%, preferred properly 30 to 85 weight 0/0, the component (b 2) is from 1.0 to 50 weight 0/0, preferably rather is from 1.0 to 30% by weight, the component (c) 1. 0 to 50% by weight, preferably 1.0 to 30% by weight.
- organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention the same organoaluminum compound as the component (d) described above is used, preferably triethylaluminum, Sobutylaluminum.
- an organic silicon compound (C) (hereinafter referred to as “component (C)”) ) Can be used.
- component (C) organic silicon compound
- this component (C) is used in combination with component (A 1) or (A2) and component (B), it can maintain high activity and high stereoregularity without being used to form a catalyst for polymerization of olefins. Furthermore, high catalytic activity and stereoregularity can be expressed.
- component (C) the same compound as the component (b) or the component (e) described above can be used.
- ethyl (t-pylamino) dimethyoxysilane ethyl (t-ptylamino) jetoxysila.
- olefins of the present invention In the presence of the catalyst for polymerizing olefins of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out.
- the monomers of olefins used in the polymerization are ethylene, propylene, 1-butene, 1 pentene, 4-methylolene 11. pentene, vinylinosic hexane, etc. Or two or more can be used together.
- ethylene, propylene, and 1-pentene are preferably used.
- propylene is particularly preferred.
- copolymerization with one or more other olefin monomers can be preferably carried out.
- the olefin monomers to be copolymerized include ethylene, propylene, 1-pentene, 1-pentene, 4-methinole 1-pentene, vinylenocyclohexane, and the like. Two or more types can be used in combination. In particular, ethylene and 1-pentene are preferably used.
- Copolymerization of propylene with other olefin monomers includes random copolymerization in one stage using propylene and a small amount of ethylene as a comonomer, and homopolymerization of propylene in the first stage (first polymerization tank).
- propylene-ethylene block copolymerization is typically performed in which propylene and ethylene are copolymerized in the second stage (second polymerization tank) or more in multiple stages (multistage polymerization tank).
- the catalyst of the present invention comprising the above component (A 1) or (A 2) and component (B), or component (C) is effective and has catalytic activity, In addition to good stereoregularity and Z or hydrogen response, the copolymerization properties and the properties of the resulting copolymer are also good.
- a copolymer having an ethylene content of 5 to 10% by weight and a high ethylene content and good randomness can be obtained.
- a copolymer having a high rubber content can be obtained.
- alcohols can be added to the polymerization system in order to prevent the formation of diels in the final product, especially when shifting from homopolymerization of propylene to block copolymerization.
- specific examples of the alcohols include ethyl alcohol, isopropyl alcohol, and the like.
- the amount used is 0.01 to 10 moles, preferably 0.1 to 2 moles, relative to 1 mole of component (B).
- the amount ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited.
- the component (B) is usually contained in the component (A 1) or (A2). It is used in the range of 1 to 2000 moles, preferably 50 to 1000 moles per mole of titanium atom.
- Component (C) is used in the range of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.1 to 0.5 mol, per mol of component (B).
- the order of contacting the components is arbitrary, it is desirable to first introduce the organoaluminum compound (B) into the polymerization system and contact the solid catalyst component component (A 1) or (A2).
- component (C) the organoaluminum compound (B) is first charged into the polymerization system, then component (C) is charged, and then the solid catalyst component component (A1) or (A2) is contacted. .
- 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 200 ° 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 batch polymerization are possible.
- the polymerization reaction may be performed in one stage, or two or more stages. It may be performed in multiple stages.
- the catalyst when polymerizing olefins using a catalyst formed from component (A 1) or (A2) and component (B), or component (C) (also referred to as “main polymerization”), the catalyst.
- component (A 1) or (A2) and component (B), or component (C) also referred to as “main polymerization”
- the catalyst In order to further improve the activity, stereoregularity, and particle properties to be generated, it is desirable to perform prepolymerization prior to the main polymerization.
- the same olefins as in the main polymerization or monomers such as styrene can be used.
- component (A 1) or (A2) and component (B) or component (C) are contacted in the presence of olefins, and 0.1 per lg of component (A1) or (A 2) ⁇ 100 g of polyolefin is preliminarily polymerized, and then component (B) and Z or component (C) are contacted to form a catalyst.
- the order of contacting the respective components and monomers is arbitrary.
- the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for performing polymerization such as propylene.
- the component (A 1) or (A2) is then contacted, and then an olefin such as propylene and / or one or more other olefins are contacted.
- the prepolymerization temperature is arbitrary and is not particularly limited, but is preferably in the range of 10 ° C to 70 ° C, more preferably in the range of 0 ° C to 50 ° C.
- the catalyst activity indicating the amount of polymer produced (F) g per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.
- Catalytic activity polymer produced (F) g / solid catalyst component gZl time
- the xylene-soluble component (XS: wt%) of the polymer was measured by the following method.
- Method for measuring xylene-dissolved component 4.0 g of polymer was charged into 200 ml of para-xylene, and the polymer was dissolved at the boiling point of toluene (138 ° C) for 2 hours. Thereafter, the mixture was cooled to 23 ° C, and insoluble components and dissolved components were separated by filtration. The solvent of the dissolved component was distilled off, followed by drying by heating. The obtained polymer was used as a xylene-soluble component, and the relative value (XS, wt%) relative to the produced polymer (F) was shown.
- melt index (M l) indicating the melt flow rate of the polymer was measured according to AS TM D 1 238 and J I S K 72 10.
- a polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the polymerization catalyst was formed and polymerized by using diallyl dimethyl silane instead of diaryldimethylsilane. The results obtained are shown in Table 3.
- a polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the polymerization catalyst was formed and polymerized using gallium dimethylvinylsilane instead of diallyldimethylsilane. The results obtained are shown in Table 3.
- a polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the polymerization catalyst was formed and polymerized by using allyltriethylsilane instead of diallyldimethylsilane. The results obtained are shown in Table 3.
- the polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the polymerization catalyst was formed and polymerized using hexylmethyldimethyoxysilane instead of 1-methyl ester / resimethoxysilane. The results obtained are shown in Table 3.
- the mixture was separated into solid and liquid at 95 ° C, and the solid content was washed twice with 48 ml of toluene. This was washed 8 times with 48 ml, filtered and dried to obtain a powdered solid catalyst component.
- the titanium content in the solid catalyst component was measured and found to be 2.1% by weight.
- a solid catalyst component was prepared in the same manner as in Example 1 except that the solid component obtained above was used.
- a polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The results obtained are shown in Table 3.
- a solid catalyst component was prepared in the same manner as in Example 1 except that the solid component obtained above was used.
- the polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that the polymerization catalyst was formed and polymerized using gallium trimethylsilane instead of diaryldimethylsilane. The results obtained are shown in Table 3.
- a polymerization catalyst was formed and polymerized under the same conditions as in Example 1 except that vinyltrimethylsilane was used instead of diallyldimethylsilane to form a polymerization catalyst and perform polymerization.
- the results obtained are shown in Table 3.
- a round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 150 g of methoxymagnesium and 700 ml of toluene, and suspended. did.
- the suspension was then equipped with a stirrer and thoroughly substituted with nitrogen gas, preloaded in a 200 ml round-bottomed flask with 45 ml toluene and 300 ml titanium tetrachloride. Added in ml solution.
- the suspension was then reacted at 5 ° C for 1 hour.
- 22.5 ml of diethyl n-butyl phthalate was added and the temperature was raised to 100 ° C. Thereafter, the first reaction treatment was performed for 2 hours with stirring.
- the product was washed 4 times with 1300 ml of 80 ° C toluene, and 1 200 ml of toluene and 300 ml of titanium tetrachloride were newly added and stirred.
- a second reaction treatment was performed at 10 ° C. for 2 hours. The intermediate wash and the second reaction treatment were repeated once more.
- the product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to give a powdered solid component.
- the titanium content in the solid component was measured and found to be 2.9 weight. /. Met.
- the solid component (12 g) obtained above was suspended in titanium tetrachloride (25 ml) and heptane (10 Om) and reacted at 100 ° C for 2 hours. After completion of the reaction, the supernatant was removed by decantation, diallyldimethylsilane 2 2 mm o 1 and heptane 30 m 1 were introduced, and the reaction was carried out at 80 ° C for 2 hours. Next, the reaction solution is cooled to 50 ° C, t-butyl ether dimethoxysilane 22 mm o 1 and heptane-diluted triethyl aluminum 37 mmo 1 are added and contacted with stirring at 50 ° C for 2 hours. I let you.
- a solid catalyst component was prepared, a polymerization catalyst was formed and polymerized under the same conditions as in Example 10, except that triarylmethylsilane was used instead of diallyldimethylsilane. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was carried out under the same conditions as in Example 10, except that diaryl dimethyl silane was used instead of diaryl dimethyl silane. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was performed under the same conditions as in Example 10, except that gallium dimethylvinylsilane was used instead of dialyldimethylsilane. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was performed under the same conditions as in Example 10, except that allyltriethylsilane was used instead of diallyldimethylsilane. The results obtained are shown in Table 4.
- the mixture was separated into solid and liquid at 95 ° C, the solid was washed twice with 48 ml of toluene, and then treated with the above mixture of disoptyl phthalate and titanium tetrachloride under the same conditions. Wash 8 times with 8 ml, filter and dry to obtain powdered solid catalyst component: ⁇ .
- the titanium content in the solid catalyst component was measured and found to be 2.1% by weight.
- a solid catalytic component was prepared in the same manner as in Example 10, except that the solid component obtained above was used as the solid component.
- a polymerization catalyst was formed and polymerized in the same manner as in Example 10 except that the solid catalyst component obtained above was used as the solid catalyst component. The results obtained are shown in Table 4.
- a solid catalyst component was prepared in the same manner as in Example 10, except that the solid component obtained above was used as the solid component.
- a polymerization catalyst was formed and polymerized in the same manner as in Example 10, except that the solid catalyst component obtained above was used as the solid catalyst component. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was carried out under the same conditions as in Example 10, except that gallytrimethylsilane was used instead of dialyldimethylsilane. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, a polymerization catalyst was formed and polymerized under the same conditions as in Example 10, except that vinyltrimethylsilane was used instead of diallyldimethylsilane. The results obtained are shown in Table 4.
- a solid catalyst component was prepared, and a polymerization catalyst was formed and polymerized under the same conditions as in Example 10, except that dibulyldimethylsilane was used instead of diaryldimethylsilane. The results obtained are shown in Table 4.
- the polydispersity index value (PI) is the dynamics of Rheometrics. Measurements were taken with a stress rheometer using a 1.O mm thick disc. Example 2 0
- Example 19 The solid component was prepared in the same manner as in Example 19 except that the solid component prepared in Example 9 was used and the amount of bisperhydroisoquinolinodidimethyloxysilane was changed from 3.9 grams to 1.9 grams when preparing the solid catalyst component A catalyst component was prepared, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.2% by weight. The polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in 9 except that 2.9 g of tert-butylaminodimethyoxysilane was used instead of 3.9 g of bisperhydroisoquinolinodidimethyloxysilane when preparing the solid catalyst component. Prepared a solid catalyst component in the same manner as in Example 19, and further formed and polymerized a polymerization catalyst. As a result, the titanium content in the obtained solid catalyst component was 2.7% by weight. The polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in 9 except that 2.3 grams of ethyl (tert-butylamino) ethoxy silane was used in place of 3.9 grams of bisperhydroisoquinolinodidimethyloxysilane when preparing the solid catalyst component. Prepared a solid catalyst component in the same manner as in Example 19, and further formed and polymerized a polymerization catalyst. The titanium content in the obtained solid catalyst component was 2.6% by weight. The polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in 9 except that 3.9 grams of bisperhydro-droquino-linodimethoxysilane was used instead of 3.9 grams of bisperhydroisoquinolinodidimethyloxysilane when preparing the solid catalyst component. Prepared a solid catalyst component in the same manner as in Example 19, and further formed a polymerization catalyst and polymerized. The titanium content in the obtained solid catalyst component was 2.0% by weight. The polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in Example 19, except that 0.4 gram of allyldimethylvinylsilane was used instead of 0.5 gram of diaryldimethylsilane in preparing the solid catalyst component.
- a solid catalyst component was prepared in the same manner as described above, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.1% by weight. The polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in Example 19, except that 0.6 gram of triarylmethylsilane was used instead of 0.5 gram of diaryldimethylsilane in preparing the solid catalyst component.
- a solid catalyst component was prepared in the same manner as described above, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.0% by weight. The polymerization results are shown in Table 5.
- Example 2 6
- Example 19 Using the solid component prepared in 9 and using 2.3 grams of ethyl (tert-ptylamino) diethoxysilane in place of 3.9 grams of bisperhydroisoquinolinodidimethyloxysilane when preparing the solid catalyst component. Further, a solid catalyst component was prepared in the same manner as in Example 19 except that 0.6 gram of dilinole dichlorosilane was used instead of 0.5 gram of diallyldimethylsilane, and a polymerization catalyst was formed and polymerized. . The titanium content in the obtained solid catalyst component was 2.7% by weight. The polymerization results are shown in Table 5.
- Example 2 7 Example 19 Using the solid component prepared in 9 and using 2.3 grams of ⁇ til (tert-butylamino) diethoxysilane instead of 3.9 grams of bisperhydroisoquinolinodimethoxysilane in preparing the solid catalyst component Further, a solid catalyst component was prepared in the same manner as in Example 19 except that 0.5 g of aryltriethylsilane was used instead of 0.5 g of diallyldimethylsilane, and a polymerization catalyst was formed and polymerized. . The titanium content in the obtained solid catalyst component was 2.6% by weight. The polymerization results are shown in Table 5.
- a solid component and a solid catalyst component were prepared in the same manner as in Example 19 except that 2.5 grams of diisoptyl phthalate was used instead of 2.5 grams of di-n-butyl phthalate when preparing the solid components. Further, a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.0 weight. /. Met. The polymerization results are shown in Table 5.
- Polymerization was carried out in the same manner as in Example 19 except that in the formation of the polymerization catalyst, 0.03 mmol of cyclohexylmethyldimethoxysilane was further added to carry out the polymerization.
- the polymerization results are shown in Table 5.
- Example 19 Using the solid component prepared in 9 and using 2.3 grams of ethyl (tert-butylamino) jetoxysilane in place of 3.9 grams of bisperhydroisoquinolinodidimethyloxysilane when preparing the solid catalyst component Except for the above, a solid catalyst component was prepared in the same manner as in Example 24, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.7% by weight. The polymerization results are shown in Table 5.
- Example 3 1 Using a solid component prepared in Example 2 0, Bisupahi in the preparation of the solid catalyst component Doroi Soki Norino dimethyl Tokishishiran 3 9 g instead Echiru of.. (T e rt - Puchiruamino) diethoxy silane 2 3 g using the A solid catalyst component was prepared in the same manner as in Example 25 except that the polymerization catalyst was formed. The titanium content in the obtained solid catalyst component was 2.7% by weight. The polymerization results are shown in Table 5.
- Example 19 and Example 19 except that 0.4 grams of divinyldimethylsilane was used instead of 0.5 grams of diallyldimethylsilane in preparing the solid catalyst component using the solid component prepared in Example 19. Similarly, a solid catalyst component was prepared, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.2% by weight. The polymerization results are shown in Table 5.
- Example 3 3
- Example 19 Similar to Example 9 except that 0.4 grams of vinyltrimethylsilane was used in place of 0.5 grams of diallyldimethylsilane when preparing the solid catalyst component using the solid component prepared in 9 A solid catalyst component was prepared, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.1% by weight. The polymerization results are shown in Table 5.
- Example 3 4
- Example 23 Using Example 23, except that 0.4 g of butyltrimethylsilane was used instead of 0.5 g of diallyldimethylsilane in preparing the solid catalyst component using the solid component prepared in 9 Similarly, a solid catalyst component was prepared, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 2.3% by weight. The polymerization results are shown in Table 5. Comparative Example 7
- Example 2 Example 1 9 except that 2.0 grams of cyclohexylmethyldimethyoxysilane was used in place of 3.9 grams of bisperhydroisoquinolinodimethoxysilane when preparing the solid catalyst component using the solid component prepared in Example 8.
- a solid catalyst component was prepared in the same manner as described above, and a polymerization catalyst was formed and polymerized. The titanium content in the obtained solid catalyst component was 1.9% by weight. The polymerization results are shown in Table 5.
- a solid catalyst component was prepared in the same manner as in Example 19 except that the solid component prepared in Example 19 was used and no diallyldimethylsilane was used when preparing the solid catalyst component. Was formed and polymerized. The titanium content in the obtained solid catalyst component was 1.9% by weight. The polymerization results are shown in Table 5.
- T i and TEAL The molar ratio of T i and TEAL (T i / TEAL) was 1600.
- the autoclave was supplied at a flow rate of mol Z, the temperature inside the system was raised to 70 ° C, and copolymerization was carried out at 0.4 MPaG for 120 minutes while maintaining the temperature at 70 ° C.
- the obtained suspension of the copolymer was separated from the insoluble content and the soluble content, and the insoluble content, ethylene content, Ml, and melting point were measured for the insoluble content.
- the soluble content was measured for the soluble content. The measurement results are shown in Table 6.
- a propylene / ethylene random copolymer was produced in the same manner as in Example 35 except that the solid catalyst component prepared in Comparative Example 1 was used. The obtained results are shown in Table 6.
- Table 7 shows the results obtained by producing a propylene / ethylene random copolymer in the same manner as in Example 36 except that the solid catalyst component prepared in Comparative Example 1 was used.
- Homopolymer M I (g / 10 min) 160 150
- Example 11 An autoclave with an internal volume of 2.0 liters with a stirrer completely replaced with nitrogen gas was charged with 70 Oml of n-heptane and maintained in a mixed gas atmosphere of ethylene and propylene while maintaining triethyl aluminum (TEAL ) And Example 11 The solid catalyst component prepared in 1 was charged with 0.0035 mmol as titanium atoms to form a polymerization catalyst. At this time, the molar ratio of Ti and TEAL (T i / TEAL) in the solid catalyst component was set to 1Z600. First, prepolymerize with propylene only at 20 ° C, 0.
- Comparative Example 1 2 A solid propylene / ethylene random copolymer was produced in the same manner as in Example 37 except that the solid catalyst component prepared in Comparative Example 4 was used as the solid catalyst component. Table 8 shows the obtained results. It was.
- T i and TEAL molar ratio (T i ZTEAL) in the solid catalyst component was set to 1/700.
- Hydrogen gas (200 mmol) and liquefied propylene (1.2 liter) were charged, and prepolymerization was performed at 20 ° C for 5 minutes. Thereafter, a propylene pulc polymerization reaction was carried out at 70 ° C for 1 hour.
- Homopolymerization activity (g / g-cat.) 66, 400 38, 500
- Homopolymer M I (g / 10 min) 150 145
- Copolymer MI (g / 10 min) 20 .22
- the random copolymer has a high techylene content under the same polymerization conditions and A polymer with high randomness can be obtained, and for a block copolymer, a polymer with a high EPR content can be obtained under the same polymerization conditions.
- the stereoregularity and yield of the polymer are higher than those of conventional catalysts. It can be maintained at a high rate and has an excellent hydrogen response, so it can provide general-purpose polyolefins at low cost. It is also expected to be useful in the production of highly functional polymers of olefins. In addition, since an olefin polymer having a broad molecular weight distribution can be obtained, a polymer suitable for production of a biaxially stretched polypropylene film can be provided.
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Abstract
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US11/721,557 US20090253873A1 (en) | 2004-12-13 | 2005-12-02 | Solid catalyst component and catalyst for polymerization of olefin, and method for producing polymer or copolymer of olefin using the same |
EP05814411A EP1829898A4 (en) | 2004-12-13 | 2005-12-02 | SOLID CATALYST COMPONENT AND CATALYST FOR POLYMERIZING OLEFIN AND METHOD FOR PRODUCING OLEFINE POLYMER OR COPOLYMER THEREWITH |
BRPI0518990-0A BRPI0518990A2 (pt) | 2004-12-13 | 2005-12-02 | componente de catalisador sàlido, catalisador para a polimerizaÇço de olefinas, e, processo para produzir um polÍmero ou copolÍmero de olefina |
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JP2004359720A JP4803636B2 (ja) | 2004-12-13 | 2004-12-13 | 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 |
JP2004-359720 | 2004-12-13 | ||
JP2005010178A JP4749726B2 (ja) | 2005-01-18 | 2005-01-18 | オレフィン類重合用固体触媒成分の製造方法 |
JP2005-010178 | 2005-01-18 | ||
JP2005-229423 | 2005-08-08 | ||
JP2005229423A JP2007045881A (ja) | 2005-08-08 | 2005-08-08 | 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 |
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US (1) | US20090253873A1 (ja) |
EP (1) | EP1829898A4 (ja) |
KR (1) | KR20070093059A (ja) |
BR (1) | BRPI0518990A2 (ja) |
SG (1) | SG158131A1 (ja) |
TW (1) | TWI341845B (ja) |
WO (1) | WO2006064718A1 (ja) |
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US20120004378A1 (en) * | 2009-03-17 | 2012-01-05 | Toho Titanium Co., Ltd | Solid catalyst component and catalyst for polymerization of olefins, and process for production of olefin polymers using same |
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KR101234427B1 (ko) | 2005-05-31 | 2013-02-18 | 도호 티타늄 가부시키가이샤 | 아미노실란 화합물, 올레핀류 중합용 촉매 성분 및 촉매 및이것을 이용한 올레핀류 중합체의 제조 방법 |
CN105837714B (zh) | 2012-07-18 | 2018-07-20 | 东邦钛株式会社 | 烯烃类聚合用固体催化剂成分的制造方法、烯烃类聚合用催化剂以及烯烃类聚合物的制造方法 |
JP6293726B2 (ja) | 2013-02-27 | 2018-03-14 | 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 |
KR102103486B1 (ko) | 2013-02-27 | 2020-04-22 | 도호 티타늄 가부시키가이샤 | 올레핀류 중합용 고체 촉매 성분, 올레핀류 중합용 촉매 및 올레핀류 중합체의 제조 방법 |
CN104640886B (zh) | 2013-02-27 | 2018-04-27 | 东邦钛株式会社 | 用于聚合烯烃的固体催化剂组分的制造方法、用于聚合烯烃的催化剂和聚合烯烃的制造方法 |
CN105585644B (zh) * | 2014-11-03 | 2018-06-01 | 中国石油天然气股份有限公司 | 一种用于烯烃聚合的齐格勒-纳塔催化剂组分及其催化剂 |
CN108368192B (zh) | 2015-12-18 | 2020-09-11 | 日本聚丙烯株式会社 | α-烯烃聚合用固体催化剂组分的制造方法和使用其的α-烯烃聚合物的制造方法 |
CN112759672B (zh) * | 2019-10-21 | 2023-04-11 | 中国石油化工股份有限公司 | 一种烯烃聚合用固体催化剂组分、催化剂及其应用 |
CN115806636B (zh) * | 2021-09-15 | 2024-02-13 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂体系和烯烃聚合方法 |
CN115806637B (zh) * | 2021-09-15 | 2024-03-26 | 中国石油化工股份有限公司 | 一种用于烯烃聚合的催化剂体系和烯烃聚合方法 |
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2005
- 2005-12-02 WO PCT/JP2005/022596 patent/WO2006064718A1/ja active Application Filing
- 2005-12-02 KR KR1020077011683A patent/KR20070093059A/ko not_active Application Discontinuation
- 2005-12-02 SG SG200908254-6A patent/SG158131A1/en unknown
- 2005-12-02 US US11/721,557 patent/US20090253873A1/en not_active Abandoned
- 2005-12-02 BR BRPI0518990-0A patent/BRPI0518990A2/pt not_active IP Right Cessation
- 2005-12-02 EP EP05814411A patent/EP1829898A4/en not_active Withdrawn
- 2005-12-06 TW TW094142860A patent/TWI341845B/zh not_active IP Right Cessation
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US20120004378A1 (en) * | 2009-03-17 | 2012-01-05 | Toho Titanium Co., Ltd | Solid catalyst component and catalyst for polymerization of olefins, and process for production of olefin polymers using same |
US8426537B2 (en) * | 2009-03-17 | 2013-04-23 | Toho Titanium Co., Ltd. | Solid catalyst component and catalyst for polymerization of olefins, and process for production of olefin polymers using same |
Also Published As
Publication number | Publication date |
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TWI341845B (en) | 2011-05-11 |
KR20070093059A (ko) | 2007-09-17 |
SG158131A1 (en) | 2010-01-29 |
EP1829898A4 (en) | 2011-06-01 |
EP1829898A1 (en) | 2007-09-05 |
BRPI0518990A2 (pt) | 2008-12-16 |
TW200628504A (en) | 2006-08-16 |
US20090253873A1 (en) | 2009-10-08 |
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