JP4276554B2 - Olefin polymerization catalyst - Google Patents

Description

  The present invention relates to a catalyst for polymerization of olefins having good hydrogen activity.

  Conventionally, in the polymerization of olefins such as propylene, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many methods for polymerizing or copolymerizing olefins in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound have been proposed. For example, in Patent Document 1 (Japanese Patent Laid-Open No. 57-63310) and Patent Document 2 (Japanese Patent Laid-Open No. 57-63311), a solid catalyst component containing a magnesium compound, a titanium compound and an electron donor, and organic There has been proposed a method for polymerizing olefins having 3 or more carbon atoms in particular using a catalyst comprising a combination of an aluminum compound and an organosilicon compound having a Si—O—C bond. However, these methods are not always satisfactory for obtaining a high stereoregularity polymer in a high yield, and further improvement has been desired.

  On the other hand, in Patent Document 3 (Japanese Patent Laid-Open No. 63-3010), a product obtained by contacting dialkoxymagnesium, aromatic dicarboxylic acid diester, aromatic hydrocarbon compound and titanium halide is in a powder state. A propylene polymerization catalyst comprising a solid catalyst component, an organoaluminum compound, and an organosilicon compound prepared by heat treatment with a propylene polymerization method and propylene polymerization method have been proposed.

  Moreover, in patent document 4 (Unexamined-Japanese-Patent No. 1-315406), titanium tetrachloride is made to contact the suspension formed with diethoxymagnesium and alkylbenzene, and it is made to react by adding phthalic acid dichloride then. A catalyst for propylene polymerization comprising a solid catalyst component, an organoaluminum compound and an organosilicon compound prepared by obtaining a solid product and further catalytically reacting the solid product with titanium tetrachloride in the presence of alkylbenzene Propylene polymerization methods in the presence have been proposed.

  Each of the above prior arts has such a high activity that the purpose of removing a catalyst residue such as chlorine and titanium remaining in the produced polymer can be omitted, and at the same time, a stereoregular polymer. The focus is on improving yield and sustaining the catalytic activity during polymerization, each with excellent results.

  By the way, the polymer obtained by using the catalyst as described above is used for various uses such as containers and films in addition to molded articles such as automobiles and home appliances. These melt polymer powders produced by polymerization and are molded by various molding machines. Especially when manufacturing large molded products such as injection molding, the melted polymer has fluidity (melt flow rate). Higher values may be required, so much work has been done to increase the melt flow rate of the polymer.

Melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is a common practice to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. At this time, in order to produce a low molecular weight polymer, that is, in order to produce a polymer having a high melt flow rate, a large amount of hydrogen is usually added. However, the pressure resistance of the reactor is limited due to its safety, and hydrogen that can be added. There is also a limit on the amount. For this reason, in order to add more hydrogen, the partial pressure of the monomer to be polymerized must be lowered, and in this case, productivity is lowered. Further, since a large amount of hydrogen is used, there is a problem of cost. Therefore, it has been desired to develop a catalyst with a higher hydrogen activity than a conventional catalyst so that a polymer with a high melt flow rate can be produced with a smaller amount of hydrogen. It was not enough.
JP-A-57-63310 (Claims) JP-A-57-63311 (Claims) JP 63-3010 A (Claims) JP-A-1-315406 (Claims)

  That is, an object of the present invention is to provide an olefin polymerization catalyst having a higher hydrogen activity than the conventional catalysts described above.

  Under such circumstances, the present inventors have conducted extensive studies, and as a result, obtained a solid catalyst component, an organoaluminum compound, and a specific structure using a magnesium compound, a tetravalent titanium halide, and an electron donating compound as raw materials. The present inventors have found that a catalyst comprising an aminosilane compound having higher hydrogen activity than the conventional catalyst described above has led to the completion of the present invention.

That is, the present invention comprises (A) a solid catalyst component prepared by contacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c),
(B) The following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) Provided is a catalyst for olefin polymerization, which is formed from cyclopentylaminotrialkoxysilane or cyclohexylaminotrialkoxysilane .

  The olefin polymerization catalyst of the present invention has a significantly higher hydrogen activity than conventional catalysts. Therefore, since the amount of hydrogen used in the polymerization can be reduced, general-purpose polyolefin can be provided at low cost, and usefulness is expected in the production of a polymer of olefins having high functionality.

  In the preparation of the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) among the olefin polymerization catalysts of the present invention, a magnesium compound (a), a tetravalent titanium halogen compound (b). And a solid product forming step of contacting the electron donating compound (c) to form a solid product. Magnesium compounds used in the solid product forming step (hereinafter, simply referred to as “component (a)”) include magnesium dihalide, dialkylmagnesium, alkylmagnesium halide, dialkoxymagnesium, diaryloxymagnesium, alkoxyalkoxy halides. Among these magnesium compounds, dialkoxymagnesium is preferable, specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxy. And ethoxymagnesium, etc., and particularly preferred is diethoxymagnesium. Magnesium is the metallic magnesium may be one obtained by reacting an alcohol in the presence of a halogen and halogen-containing metal compound. In addition, dialkoxy magnesium may be used either individually or in combination of two or more.

  Furthermore, the dialkoxymagnesium suitably used in the preparation of the component (A) solid product forming step is in the form of granules or powder, and the shape thereof may be indefinite or spherical. For example, 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 produced polymer powder during the polymerization operation is improved. Problems such as blockage caused by the contained fine powder are solved.

  The spherical dialkoxymagnesium does not necessarily need to be a true sphere, and an elliptical or potato-shaped one can also be used. Specifically, the particle shape is such that the ratio (l / w) of the major axis diameter l to the minor axis diameter 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 μm can be used. Preferably it is 5 to 150 μm. In the case of spherical dialkoxymagnesium, the average particle diameter is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. As for the particle size, it is desirable to use one having a small particle size distribution and a small amount of fine powder and coarse powder. Specifically, the particle size of 5 μm or less is 20% or less, preferably 10% or less. On the other hand, the particle size of 100 μm or more is 10% or less, preferably 5% or less. Further, when the particle size distribution is expressed by ln (D90 / D10) (where D90 is the cumulative particle size and the particle size at 90%, D10 is the cumulative particle size and the particle size at 10%), it is preferably 3 or less, preferably 2 or less.

  For example, JP-A-58-41832, JP-A-62-51633, JP-A-3-74341, JP-A-4-368391, JP-A-4-36891 can be used for producing spherical dialkoxymagnesium as described above. It is illustrated in the 8-73388 gazette etc.

The tetravalent titanium halogen compound (b) (hereinafter sometimes referred to as “component (b)”) used for the preparation of the component (A) in the present invention is represented by the general formula Ti (OR ⁴ ) _n X _4-n ( In the formula, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4) selected from the group of titanium halides or alkoxy titanium halides 1 type or 2 types or more of a compound to be made.

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide as titanium halide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride as alkoxytitanium halide. Examples include chloride, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, di-n-butoxy titanium dichloride, trimethoxy titanium chloride, triethoxy titanium chloride, tripropoxy titanium chloride, tri-n-butoxy titanium chloride. The 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, such as alcohols. Phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, organosilicon compounds containing a Si—O—C bond, and the like.

  Specifically, alcohols such as methanol, ethanol, n-propanol and 2-ethylhexanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9- Ethers such as bis (methoxymethyl) fluorene and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate , Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, anisic acid Monocarboxylic acid esters such as chill, diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl isobutyl bromomalonate , Diethyl diisopropylmalonate, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl diisopentylmalonate, diethyl isopropylisobutylmalonate, dimethyl isopropylisopentylmalonate, diethyl (3-chloro-n-propyl) malonate, bis (3-Bromo-n-propyl) diethyl malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, adipine Dibutyl esters such as dibutyl, diisodecyl adipate, dioctyl adipate, phthalate diester, phthalate diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, phthalate dichloride, terephthalate dichloride, etc. Aldehydes such as acid halides, acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine, amides such as oleic acid amide, stearic acid amide, acetonitrile, Nitriles such as benzonitrile and tolunitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, phenylalkoxysilane, An organosilicon compound containing a Si—O—C bond such as alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and the like can be given.

  Among the above electron donating compounds, esters, particularly aromatic dicarboxylic acid diesters are preferably used, and phthalic acid diesters and phthalic acid diester derivatives are particularly preferable. Specific examples of these phthalic acid diesters include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, and di-iso-butyl phthalate. , Ethyl methyl phthalate, methyl phthalate (iso-propyl), ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate (iso-butyl), di-n-pentyl phthalate, Di-iso-pentyl phthalate, di-neo-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, phthalic acid Bis (2-ethylhexyl), di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl phthalate) ), N-butyl phthalate (iso-hexyl), n-butyl phthalate (2-ethylhexyl), n-pentylhexyl phthalate, n-pentyl phthalate (iso-hexyl), iso-pentyl phthalate (heptyl) N-pentyl (2-ethylhexyl) phthalate, n-pentyl phthalate (iso-nonyl), iso-pentyl phthalate (n-decyl), n-pentyl undecyl phthalate, iso-pentyl phthalate (iso- Hexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (2-ethylhexyl), n-hexyl phthalate (iso-nonyl), n-hexyl phthalate (n-decyl), N-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (iso-nonyl), n-phthalate Heptyl (neo-decyl), is phthalate 2-ethylhexyl (an iso-nonyl) is exemplified, these phthalic diester one or two or more kinds are used.

  As the phthalic acid diester derivative, one or two hydrogen atoms of the benzene ring to which the two alkoxycarbonyl groups of the above phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, a chlorine atom, or a bromine atom. And those substituted with a halogen atom such as a fluorine atom. The solid catalyst component prepared by using the phthalic acid diester derivative as the electron donating compound (c1) can further improve the hydrogen activity or the hydrogen response. Even if the amount of hydrogen added during the polymerization is the same or small, the polymer The melt flow rate can be improved. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, dineopentyl 4,5-dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-butyl 4-chlorophthalate , Dineopentyl 4-chlorophthalate, di-iso-butyl 4-chlorophthalate, di-iso-hexyl 4-chlorophthalate, di-iso-octyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n 4-bromophthalate -Butyl, dineopentyl 4-bromophthalate, di-iso-butyl 4-bromophthalate, di-iso-hexyl 4-bromophthalate, di-iso-octyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, 4, Di-n-butyl 5-dichlorophthalate, 4, -Dineopentyl dichlorophthalate, di-iso-hexyl 4,5-dichlorophthalate, di-iso-octyl 4,5-dichlorophthalate, among which dineopentyl 4-bromophthalate, di-bromophthalate di- n-Butyl and di-iso-butyl 4-bromophthalate are preferable, and two alkoxycarbonyl groups of dineopentyl phthalate such as dineopentyl 4-chlorophthalate, dineopentyl 4-bromophthalate, and dineopentyl 4,5-dichlorophthalate are bonded to each other. Particularly preferred is a dineopentyl phthalate derivative in which one or two hydrogen atoms of the benzene ring are substituted with halogen atoms.

  In addition, it is also preferable to use the above esters in combination of two or more, and the ester is used so that the difference between the total carbon number of the alkyl group of the ester used and the total carbon number of the other ester is 4 or more. It is desirable to combine classes.

  In the present invention, the components (a), (b), and (c) are contacted in the presence of an aromatic hydrocarbon (d) (hereinafter sometimes referred to simply as “component (d)”). The method of preparing the component (A) by the above is a preferred embodiment of the preparation method, and specifically, the component (d) is preferably an aromatic hydrocarbon having a boiling point of 50 to 150 ° C. such as toluene, xylene, ethylbenzene, etc. Used. Moreover, these may be used independently or may be used in mixture of 2 or more types.

  As a particularly preferred method for preparing the solid product in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the component (b And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.

In the solid product formation step in the preparation of the solid catalyst component (A) of the present invention, it is preferable to use a polysiloxane (hereinafter sometimes simply referred to as “component (e)”) in addition to the above components. By using 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 having a siloxane bond (—Si—O— bond) in the main chain, and is also collectively referred to as silicone oil, and has a viscosity at 25 ° C. of 0.02 to 100 cm ² / s ( ^{2 to} 10,000 centistokes). ), More preferably 0.03 to ⁵ cm ² / s (3 to 500 centistokes), a liquid or viscous chain, partially hydrogenated, cyclic or modified polysiloxane at room temperature.

  As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used. As the partially hydrogenated polysiloxane, methylhydrogen polysiloxane having a hydrogenation rate of 10 to 80% is used. As the cyclic polysiloxane, hexamethylcyclotrimethyl is used. Siloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxanes include higher fatty acid groups. Examples thereof include substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane. Among these, decamethylcyclopentasiloxane and dimethylpolysiloxane are preferable, and decamethylcyclopentasiloxane is particularly preferable.

  In the present invention, the above components (a), (b) and (c) and, if necessary, the component (d) or the component (e) are contacted to form a solid product. A method for preparing the product will be described. Specifically, the magnesium compound (a) is suspended in an alcohol, a halogenated hydrocarbon solvent, a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and electron donation such as phthalic acid diester is performed. A method of obtaining a solid component by contacting the functional compound (c) and / or the tetravalent titanium halogen compound (b). In the method, a spherical solid catalyst component having a sharp particle size distribution can be obtained by using a spherical magnesium compound, and without using the spherical magnesium compound, for example, a solution or suspension can be obtained using a spray device. By forming the particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid product 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 and the like are removed. The contact temperature is a temperature at the time of contact of 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 dispersed or suspended for modification, but the product is allowed to react after contact. When obtaining, the temperature range of 40-130 degreeC 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 component, and if it exceeds 130 ° C., the evaporation of the solvent used becomes remarkable. , It becomes difficult to control the reaction. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

  A preferred method for preparing the solid product of the present invention is to suspend component (a) in component (d), then contact component (b), then contact component (c) and react to form a solid. A method for preparing the product, or preparing a solid product by suspending component (a) in component (d), then contacting component (c), then contacting component (b) and reacting The method of doing can be mentioned. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (b) or the component (b) and the component (c) into contact with the solid product thus prepared again or multiple times. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon (d).

  As a particularly preferred method for preparing the solid product in the present invention, a suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C., and the component (b And a mixed solution formed from the component (d) is brought into contact with the suspension and then reacted.

  The most preferable method for preparing the solid product in the present invention includes the following methods. A suspension is formed from the component (a), the component (c), and the aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. A mixed solution is formed from the component (b) and the aromatic hydrocarbon compound (d) 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 solid substance after washing is used as a solid product. Thereafter, the washed solid material is further brought into contact with component (b) and an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. at −20 to 100 ° C., and the temperature is raised. A solid product can also be obtained by repeating the reaction treatment (secondary reaction treatment) and washing with a hydrocarbon compound that is liquid at room temperature after completion of the reaction 1 to 10 times.

  Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present invention is to suspend dialkoxymagnesium (a) in an aromatic hydrocarbon compound (d) having a boiling point of 50 to 150 ° C. After bringing the tetravalent titanium halogen compound (b) into contact with the suspension, a reaction treatment is performed. At this time, before or after the tetravalent titanium halogen compound (b) is brought into contact with the suspension, one or more electron donating compounds (c) such as phthalic acid diesters are added at −20 to 20 It is made to contact at 130 degreeC, and also polysiloxane (e) is made to contact as needed, a reaction process is performed, and a solid product (1) is obtained. In this case, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more electron donating compounds. After washing this solid product (1) with a hydrocarbon compound that is liquid at room temperature (intermediate washing), the tetravalent titanium halogen compound (b) is again added in the presence of the aromatic hydrocarbon compound in the range of -20 to 100. The mixture is contacted at 0 ° C. and subjected to a reaction treatment to obtain a solid reaction product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid reaction product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid catalyst component (A).

  The amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method and cannot be specified unconditionally. For example, a tetravalent titanium halogen compound (b) per mole of the magnesium compound (a) Is 0.5 to 100 mol, preferably 0.5 to 50 mol, more preferably 1 to 10 mol, and the electron donating compound (c) is 0.01 to 10 mol, preferably 0.01 to 1 mol. More preferably, it is 0.02 to 0.6 mol, and the aromatic hydrocarbon compound (d) is 0.001 to 500 mol, preferably 0.001 to 100 mol, more preferably 0.005 to 10 mol. The polysiloxane (e) is 0.01 to 100 g, preferably 0.05 to 80 g, more preferably 1 to 50 g.

  In the present invention, the content of titanium, magnesium, a halogen atom, and an electron donating compound in the solid catalyst component (A) or (A) is not particularly defined, but preferably 1.0 to 8.0% by weight of titanium. , Preferably 2.0 to 8.0 wt%, more preferably 3.0 to 8.0 wt%, magnesium 10 to 70 wt%, more preferably 10 to 50 wt%, particularly preferably 15 to 40 wt%. %, More preferably 15 to 25% by weight, halogen atoms 20 to 90% by weight, more preferably 30 to 85% by weight, particularly preferably 40 to 80% by weight, still more preferably 45 to 75% by weight, and electron donation The total amount of the active compounds is 0.5 to 30% by weight, more preferably 1 to 25% by weight, and particularly preferably 2 to 20% by weight.

The organoaluminum compound (B) (hereinafter sometimes simply referred to as “component (B)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (1). As long as R ¹ is not particularly limited, R ¹ is preferably an ethyl group or isobutyl group, Q is preferably a hydrogen atom, a chlorine atom or a bromine atom, and p is preferably 2 or 3, particularly preferably 3. . Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more can be used. Triethylaluminum and triisobutylaluminum are preferable.

  As the aminosilane compound (C) (hereinafter sometimes simply referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention, the compound represented by the above general formula (2) may be used. Used. This aminosilane compound is a compound in which an N atom is directly bonded to a Si atom, and a compound containing a secondary amino group in which the N atom is bonded to a hydrogen atom and a cycloalkyl group or a derivative group thereof. Examples of such aminosilane compounds include cycloalkylaminotrialkoxysilanes, alkyl-substituted cycloalkylaminotrialkoxysilanes, halogen-substituted cycloalkylaminotrialkoxysilanes, and cycloalkylalkylaminotrialkoxysilanes.

R ^{2 in the} general formula (2) is preferably a cycloalkyl group having 3 to 12 carbon atoms, specifically, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 2-methylcyclopentyl group, or 3-methyl. Cyclopentyl group, 2-ethylcyclopentyl group, 3-propylcyclopentyl group, 3-isopropylcyclopentyl group, 3-butylcyclopentyl group, 3-isobutylcyclopentyl group, 3-t-butylcyclopentyl group, 2,2-dimethylcyclopentyl group, 2 , 3-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 2-ethylcyclohexyl group, 3-propylcyclohexyl group, 3-isopropylcyclohexyl group, 3-butylcyclohexyl group Sil group, 3-isobutylcyclohexyl group, 3-t-butylcyclohexyl group, 2,2-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 1-cyclopentylmethyl group, cyclopentylmethyl group 1-cyclopentylethyl group, 1-cyclopentylpropyl group, menthyl group, mentenyl group, 2-chlorocyclopentyl group, 2-bromocyclopentyl group, 2-chlorocyclohexyl, 2-bromocyclohexyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are particularly preferable.

R ^{3 in the} general formula (2) is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. , T-butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. Among these, a methyl group and an ethyl group are particularly preferable.

  Specific examples of such aminosilane compounds include cyclopentylaminotrimethoxysilane, cyclopentylaminotriethoxysilane, cyclohexylaminotrimethoxysilane, cyclohexylaminotriethoxysilane, 2-methylcyclopentylaminotrimethoxysilane, and 2-methylcyclopentylamino. Triethoxysilane, 2-ethylcyclopentylaminotrimethoxysilane, 2-ethylcyclopentylaminotriethoxysilane, 2-chlorocyclopentylaminotrimethoxysilane, 2-chlorocyclopentylaminotriethoxysilane, 2-bromocyclopentylaminotrimethoxysilane, 2 -Bromocyclopentylaminotriethoxysilane, 2-methylcyclohexylaminotrimethoxysilane, 2-methyl Cyclohexylaminotriethoxysilane, 2-ethylcyclohexylaminotrimethoxysilane, 2-ethylcyclohexylaminotriethoxysilane, 2-chlorocyclohexylaminotrimethoxysilane, 2-chlorocyclohexylaminotriethoxysilane, 2-bromocyclohexylaminotrimethoxysilane 2-bromocyclohexylaminotriethoxysilane, cyclopentylmethylaminotrimethoxysilane, cyclopentylmethylaminotriethoxysilane, 1-cyclopentylethylaminotrimethoxysilane, 1-cyclopentylethylaminotriethoxysilane, etc. More than species can be used. Among these, preferred are cyclopentylaminotrimethoxysilane, cyclopentylaminotriethoxysilane, cyclohexylaminotrimethoxysilane, and cyclohexylaminotriethoxysilane.

In the olefin polymerization catalyst of the present invention, an organic silicon compound other than the above-mentioned aminosilane compound (hereinafter sometimes simply referred to as “component (D)”) can be used in addition to the above components. As such an organosilicon compound (D), the following general formula (3);
R ⁵ _q Si (OR ⁶ ) _4-q (3)
(Wherein, R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, R ⁶ is 1 to carbon atoms 4 represents an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and q is an integer represented by 0 ≦ q ≦ 3. Specific examples include silicon compounds, and specific examples include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane.

  Specific examples of the organosilicon compound (D) include di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t. -Butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxy Silane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyl Diethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound ( D) can be used by 1 type, and can also be used in combination of 2 or more type.

  When the component (D) is used in combination, preferred combinations with the component (C) include diethylaminotriethoxysilane and di-iso-propyldimethoxysilane, diethylaminotriethoxysilane and di-iso-butyldimethoxysilane, and diethylaminotriethoxy. Examples include silane and cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane and dicyclopentyldimethoxysilane, diethylaminotriethoxysilane and cyclohexylcyclopentyldimethoxysilane.

  Polymerization or copolymerization of olefins is carried out in the presence of the olefin polymerization catalyst of the present invention. Examples of olefins include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. Can do. In particular, ethylene, propylene and 1-butene are preferably used. Particularly preferred is propylene. In the case of polymerization of propylene, copolymerization with other olefins can also be performed. Examples of olefins to be copolymerized include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. These olefins can be used alone or in combination of two or more. can do. In particular, ethylene and 1-butene are preferably used. Copolymerization of propylene with other olefins includes random copolymerization in which polymerization is performed in one stage using propylene and a small amount of ethylene as a monomer, and polymerization of only propylene in the first stage (first polymerization tank). A typical example is so-called propylene-ethylene block copolymerization in which propylene and ethylene are copolymerized in the (first polymerization tank). Also in such random copolymerization and block copolymerization, the catalyst of the present invention comprising the above-mentioned component (A), component (B) and component (C) is effective and not only has good antihydrogen activity. The copolymerization properties and the properties of the resulting copolymer are also considered to be good. In particular, the component (D) described above can be mixed and used in addition to the component (C) which is the catalyst component of the present invention, and the component (C) and the component (D) can be used in two polymerization stages of block copolymerization. Can also be used separately.

  The use 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. Usually, the component (B) is used per 1 mole of the titanium atom in the component (A). , 1 to 2000 mol, preferably 50 to 1000 mol. Component (C) is used in an amount of 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, per mol of component (B). When component (D) is used in combination, 0.002 to 10 mol, preferably 0.01 to 2 mol, particularly preferably 0.01 to 0.5 mol, is used per mol of component (B). Moreover, it is used in the range of 0.01 to 100 mol, preferably 0.1 to 10 mol, particularly preferably 0.1 to 1 mol, per mol of the component (C).

  The order of contact of each component is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, and then the aminosilane compound (C) is contacted or premixed with the component (C) and the component (D ), Or the components (C) and (D) are contacted in any order, and the solid catalyst component (A) is further contacted. 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 previously brought into contact with each other. It is also a preferred embodiment to form a catalyst by charging (A) and component (C) or component (C) and component (D) into the polymerization system. As described above, the component (A) and the component (C) or the component (C) and the component (D) are previously brought into contact with each other for treatment, thereby further improving the hydrogen-to-hydrogen activity of the catalyst and the crystallinity of the produced polymer. Is possible.

  The polymerization method in the present invention can be carried out in the presence or absence of an organic solvent, and the olefin monomer such as propylene can be used in any state of gas and liquid. The polymerization temperature is 200 ° C. or lower, preferably 100 ° C. or lower, and the polymerization pressure is 10 MPa or lower, preferably 5 MPa or lower. Moreover, any of a continuous polymerization method and a batch type polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage or in two or more stages.

  Further, in the present invention, when an olefin is polymerized using a catalyst formed from the component (A), the component (B) and the component (C) (also referred to as main polymerization), the catalytic activity, stereoregularity, and heavy weight to be generated. In order to further improve the particle properties and the like of the coalescence, it is desirable to perform prepolymerization prior to the main polymerization. In the prepolymerization, the same olefins as in the main polymerization or monomers such as styrene can be used. Specifically, 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 preliminarily polymerized. Further, the component (B) and / or the component (C) is further contacted to form a catalyst. When 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 during the main polymerization. You can also.

  In carrying out the prepolymerization, the order of contacting the components and the monomers is arbitrary, but preferably, the component (B) is first placed in a prepolymerization system set to an inert gas atmosphere or a gas atmosphere for carrying out polymerization such as propylene. Then, after contacting component (A), an olefin such as propylene and / or one or more other olefins are contacted.

  When olefins are polymerized in the presence of the catalyst for olefin polymerization of the present invention, the melt flow rate (MI) of the produced polymer is improved several times with the same amount of hydrogen as compared with the case of using a conventional catalyst. In addition, the stereoregularity of the polymer produced is equivalent to or better than that of conventional catalysts. That is, it was confirmed that when the catalyst of the present invention was used for the polymerization of olefins, the activity against hydrogen was dramatically improved.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

<Preparation of solid catalyst component>
A 2000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspension. The suspension was then added to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride pre-charged in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. The suspension was then reacted at 5 ° C. for 1 hour. Thereafter, 22.5 ml of di-n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by a reaction treatment for 2 hours with stirring. After completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C., 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and the reaction treatment was performed at 110 ° C. for 2 hours with stirring. Thereafter, the intermediate washing and the second treatment were repeated once more. Subsequently, the product was washed 7 times with 1300 ml of heptane at 40 ° C., filtered and dried to obtain a powdered solid catalyst component (A1). The titanium content in the solid catalyst component was measured and found to be 3.1% by weight.

<Formation and polymerization of polymerization catalyst>
An autoclave with a stirrer having an internal volume of 2.0 liters, completely substituted with nitrogen gas, was charged with 1.32 mmol of triethylaluminum, 0.13 mmol of cyclopentylaminotriethoxysilane and 0.0026 mmol of the solid catalyst component as titanium atoms. A polymerization catalyst was formed. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, preliminarily polymerized at 20 ° C. for 5 minutes, then heated up, and polymerized at 70 ° C. for 1 hour. The polymer obtained was measured for polymerization activity, heptane-insoluble content (HI), melt index (MI) and xylene-soluble component (XS). The results are shown in Table 1.

The polymerization activity per gram of the solid catalyst component was calculated by the following formula.
Polymerization activity = produced polymer (F) (g) / solid catalyst component (g)
Further, when this polymer was extracted with boiling n-heptane for 6 hours, the polymer (G) insoluble in n-heptane was measured, and the ratio of boiling n-heptane insoluble matter (HI) in the polymer was expressed by the following formula. Calculated by
HI = (G) (g) / (F) (g)
The xylene-soluble component (XS) of the polymer was measured by the following method.
Method for measuring xylene-soluble component: 4.0 g of the polymer was charged into 200 ml of para-xylene, and the polymer was dissolved at a boiling point (138 ° C.) over 2 hours. Thereafter, the mixture was cooled to 23 ° C., and the dissolved component and the insoluble component were separated by filtration. The dissolved component was dried by heating, and the resulting polymer was defined as xylene-soluble component (XS) (% by weight). The melt index value (MI) of the polymer was measured according to ASTM D 1238 and JIS K 7210.

  Experiments were conducted in the same manner as in Example 1 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.

  The experiment was performed in the same manner as in Example 1 except that cyclohexylaminotriethoxysilane was used instead of cyclopentylaminotriethoxysilane. The obtained results are shown in Table 1.

Experiments were conducted in the same manner as in Example 1 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.
Comparative Example 1

A solid catalyst component was prepared in the same manner as in Example 1 except that cyclohexylmethyldimethoxysilane was used instead of cyclopentylaminotriethoxysilane to form and polymerize, and the polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.
Comparative Example 2

  Experiments were performed in the same manner as in Comparative Example 1 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.

<Preparation of solid catalyst component>
A 2000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 150 g of diethoxymagnesium and 750 ml of toluene to form a suspension. The suspension was then added to a solution of 450 ml of toluene and 300 ml of titanium tetrachloride pre-charged in a 2000 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. The suspension was then reacted at 5 ° C. for 1 hour. Thereafter, 22.5 ml of di-n-butyl phthalate was added and the temperature was raised to 100 ° C., then 30 ml of cyclic polysiloxane (decamethylcyclopentasiloxane, TFS-405 made by Toshiba Silicon) was added, and further 100 ° C. The mixture was heated up to 2 hours and reacted for 2 hours with stirring. After completion of the reaction, the product was washed four times with 1300 ml of toluene at 80 ° C., 1200 ml of toluene and 300 ml of titanium tetrachloride were newly added, and the reaction treatment was performed at 110 ° C. for 2 hours with stirring. Thereafter, the intermediate washing and the second treatment were repeated once more. Next, the product was washed 7 times with 1300 ml of heptane at 40 ° C., filtered and dried to obtain a powdered solid catalyst component (A). The titanium content in the solid catalyst component was measured and found to be 3.1% by weight.

  A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. The obtained results are shown in Table 1.

Experiments were conducted in the same manner as in Example 5 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation of the polymerization catalyst and the polymerization. The obtained results are shown in Table 1.
Comparative Example 3

A solid catalyst component was prepared in the same manner as in Example 5 except that cyclohexylmethyldimethoxysilane was used instead of cyclopentylaminotriethoxysilane to form and polymerize, and the polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.
Comparative Example 4

  Experiments were performed in the same manner as in Comparative Example 3 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.

  A solid catalyst component was prepared in the same manner as in Example 1 except that dineopentyl 4-bromophthalate was used instead of di-n-butyl phthalate, and a polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1. The titanium content in the solid catalyst component was measured and found to be 2.9% by weight.

The experiment was performed in the same manner as in Example 7 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation of the polymerization catalyst and the polymerization. The obtained results are shown in Table 1.
Comparative Example 5

A solid catalyst component was prepared in the same manner as in Example 7 except that cyclohexylmethyldimethoxysilane was used instead of cyclopentylaminotriethoxysilane to form and polymerize, and polymerization catalyst was formed and polymerized. The obtained results are shown in Table 1.
Comparative Example 6

  The experiment was conducted in the same manner as in Comparative Example 5 except that 1.5 liters of hydrogen gas was changed to 4.0 liters in the formation and polymerization of the polymerization catalyst. The obtained results are shown in Table 1.

  From the above results, when the catalyst of the present invention is used at the time of polymerization, the polymer obtained in the region where the MI value is high and the MI value is 100 or more is high even though the hydrogen amount is the same as the conventional catalyst shown in the comparative example. It can be seen that the decrease in stereoregularity is not significant.

It is a flowchart figure which shows the process of preparing the catalyst component and polymerization catalyst of this invention.

Claims (2)

(A) a solid catalyst component prepared by contacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c);
(B) The following general formula (1); R ¹ _p AlQ _3-p (1)
(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, and p is a real number of 0 <p ≦ 3), and (C) A catalyst for olefin polymerization characterized by being formed from cyclopentylaminotrialkoxysilane or cyclohexylaminotrialkoxysilane .   The electron donating compound (c) is a dineopentyl phthalate derivative in which one or two hydrogen atoms of a benzene ring to which two alkoxycarbonyl groups of dineopentyl phthalate are bonded are substituted with a halogen atom. The olefin polymerization catalyst according to claim 1.

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