JP2006063281A - Catalyst for olefin polymerization and manufacturing method of olefin polymer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for olefin polymerization which has high activity retention, gives a highly stereoregular polymer in a good yield and exhibits a good hydrogen response, and a manufacturing method of the olefin polymer using the same. <P>SOLUTION: The catalyst for olefin polymerization comprises (A) a solid catalyst component, obtained by contacting (a) a magnesium compound with (b) a tetravalent titanium halogen compound and (c) a monocarboxylate, (B) an organoaluminum compound represented by general formula (1): R<SP>1</SP><SB>p</SB>AlQ<SB>3-p</SB>and (C) an organosilicon compound represented by general formula (2): (R<SP>2</SP>R<SP>3</SP>N)<SB>q</SB>R<SP>4</SP><SB>r</SB>Si(OR<SP>5</SP>)<SB>4-q-r</SB>. The manufacturing method of the olefin polymer comprises polymerization in the presence of the catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a catalyst for olefin polymerization and a method for producing an olefin polymer, which can obtain a polymer having high activity durability and high stereoregularity, and which has a good hydrogen response.

  Conventionally, in the polymerization of olefins, solid catalyst components containing magnesium, titanium, an electron donating compound and halogen as essential components are known. Many olefin polymerization methods have been proposed in which an olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound and an organosilicon compound. For example, in Patent Document 1 (Japanese Patent Application Laid-Open No. 59-142206), alkoxymagnesium is suspended in an aromatic hydrocarbon compound in the presence of a monocarboxylic acid monoester such as ethyl benzoate or methyl acetate. A catalyst component for olefin polymerization obtained by contacting a titanium halide such as titanium chloride is disclosed.

  Patent Document 2 (Japanese Patent Laid-Open No. Sho 62-158704) discloses that a composition obtained by suspending alkoxymagnesium in an aromatic hydrocarbon compound and then contacting with titanium halide is further added to a titanium halide. A catalyst for olefin polymerization comprising a solid catalyst component, an organoaluminum compound and an organosilicon compound obtained by contacting with a diester of an aromatic dicarboxylic acid such as a phthalic acid diester at any point in time is disclosed. Yes.

  Further, Patent Document 3 (Japanese Patent Application Laid-Open No. 9-169808) discloses olefins polymerization prepared using alkoxymagnesium, titanium compounds, diesters of aromatic dicarboxylic acids such as phthalic acid diesters, and cyclic or chain polysiloxanes. A catalyst component is disclosed.

  The above prior art has such a high activity that the purpose of removing the so-called demineralization step of removing catalyst residues such as chlorine and titanium remaining in the produced polymer can be omitted, and also the yield of the stereoregular polymer. It has focused on improving the durability of the catalyst and increasing the sustainability of the catalytic activity during polymerization, and each has achieved excellent results.

  As an electron donating compound (so-called internal donor) contained in the solid catalyst component for olefin polymerization, particularly a solid catalyst component for olefin polymerization, a monocarboxylic acid monoester such as ethyl benzoate is initially used as in the above prior art, As the electron donating compound (so-called external donor) added at the time of polymerization, a catalyst in which the same monocarboxylic acid monoester is combined is mainly used. After that, due to problems such as catalyst activity persistence and odor of the polymer produced, a catalyst using a solid catalyst component using an aromatic dicarboxylic acid diester such as phthalic acid diester as an internal donor and an organosilicon compound as an external donor Is now mainstream.

  The solid catalyst component using the above aromatic dicarboxylic acid diester as an internal donor has a narrow molecular weight distribution of the resulting olefin polymer, and therefore has a low melt viscoelasticity when processing the polymer. There is a problem that its use is limited to some extent, for example, formability or appearance is impaired. Therefore, industrial use of catalysts using conventional monocarboxylic acid monoesters as the internal electron donating compound as the solid catalyst component and the external electron donating compound during polymerization is being reviewed.

  However, the above-mentioned monocarboxylic acid monoester catalyst has low activity sustainability compared to the current aromatic dicarboxylic acid diester catalyst, and the production efficiency is improved when used for propylene / ethylene block copolymerization in which polymerization is performed in two stages. It is difficult to produce a high-quality block copolymer because the resulting polymer is low and the stereoregularity of the resulting polymer is low. Therefore, it has been desired to develop a catalyst suitable for propylene / ethylene block copolymer having the characteristics of an aromatic dicarboxylic acid diester catalyst while maintaining the advantages of the conventional monocarboxylic acid monoester catalyst.

  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, there is a demand for the development of a catalyst that can produce a polymer with a high melt flow rate with a smaller amount of hydrogen, that has a higher so-called hydrogen response than a conventional catalyst, and that can maintain the tacticity and yield of the polymer at a high level. However, the above prior art is not sufficient to solve the problem.
JP 59-142206 A (Claim 1) JP 62-158704 A (Claim 1) JP-A-9-169808 (Claim 1)

  Accordingly, an object of the present invention is to use a solid catalyst component for olefin polymerization using a monocarboxylic acid monoester as an internal donor, and to obtain a high yield of highly stereoregular olefin polymers while maintaining high activity sustainability. It is an object of the present invention to provide a catalyst for olefin polymerization that can be obtained at a high rate and has a good hydrogen response, and a method for producing an olefin polymer using the same.

  As a result of intensive studies to solve the problems remaining in the prior art, the present inventors have found that a catalyst using an aminosilane compound as a solid catalyst component of a conventional monocarboxylic acid monoester has a high sustained activity. In particular, when it was used for the polymerization of propylene, it was found that a highly stereoregular olefin polymer was obtained in a high yield and the hydrogen response was high, and the present invention was completed.

That is, the present invention provides (A) a solid catalyst component containing magnesium, titanium, a halogen atom and a monocarboxylic acid monoester,
(B) The following general formula (1); R ¹ _p AlQ _3-p (1)
(In the formula, 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) the following general formula (2); (R ² R ³ N) _q R ⁴ _r Si (OR ⁵ ) _4-qr (2)
(In the formula, R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, or a hydrogen atom; ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and R ² and R ³ may be the same. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different, and R ⁵ represents a carbon number. 1 to 4 alkyl group, C 3 to C 6 cycloalkyl group, phenyl group, vinyl group, allyl group, or aralkyl group, which may be the same or different, q is 1, 2 or 3, r is 0, 1 or 2, 1 q + a r ≦ 3.) aminosilane compound represented by the
The present invention provides a catalyst for olefin polymerization, characterized in that it is formed from

  The present invention also provides a method for producing an olefin polymer, which is carried out in the presence of the olefin polymerization catalyst.

  The catalyst for olefin polymerization of the present invention exhibits high activity durability even when using the conventional monoester solid catalyst component, and can obtain a high stereoregularity polymer in a high yield, and has a hydrogen response. It is good. Therefore, a general-purpose polyolefin having a wide molecular weight distribution and excellent processability can be provided at low cost, and usefulness is expected in the production of copolymers of olefins having high functionality.

  Among the olefin polymerization catalysts of the present invention, the solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) contains magnesium, titanium, a halogen atom, and a monocarboxylic acid monoester. Specifically, (a) a magnesium compound, (b) a tetravalent titanium halogen compound, and (c) a monocarboxylic acid monoester can be obtained by contact. Examples of the magnesium compound (hereinafter sometimes simply referred to as “component (a)”) include dihalogenated magnesium, dialkylmagnesium, halogenated alkylmagnesium, dialkoxymagnesium, diaryloxymagnesium, halogenated alkoxymagnesium, and fatty acid magnesium. Among these magnesium compounds, dialkoxymagnesium is preferable, and specific examples include dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium. Ethoxymagnesium is particularly preferred, and these dialkoxymagnesiums contain metallic magnesium, The presence of such a androgenic or a halogen-containing metal compound may be one obtained by reacting an alcohol. Also, dialkoxy magnesium may be used either individually or in combination of two or more.

  Furthermore, the dialkoxymagnesium suitable for the preparation of the component (A) in the present invention 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 has the general formula;
Ti (OR ⁸ ) _n Cl _4-n
(Wherein R ⁸ represents an alkyl group having 1 to 4 carbon atoms, and n is 0 or an integer of 1 to 3). One kind of a compound selected from the group consisting of a titanium halide and an alkoxy titanium halide group Or it is 2 or more types.

  Specifically, titanium tetrachloride such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide is exemplified as the titanium halide, and methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n- Butoxy titanium trichloride, 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, etc. Is exemplified. 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 monocarboxylic acid monoester (c) (hereinafter sometimes referred to as “component (c)”) used for the preparation of the component (A) in the present invention is an aliphatic monocarboxylic acid ester or an aromatic monocarboxylic acid ester. Specifically, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzoic acid Octyl, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, ethyl p-methoxybenzoate, ethyl p-ethoxybenzoate, methyl anisate, methyl anisate and the following general formula ( 3); (R ⁶ ) ₃ CCOOR ⁷ (3)
(Wherein R ⁶ represents an alkyl group having 1 to 3 carbon atoms, which may be the same or different, and R ⁷ represents an alkyl group having 1 to 12 carbon atoms). And the like.

In the general formula (3), R ⁶ is a methyl group, an ethyl group, a propyl group or an isopropyl group, preferably a methyl group. The compound in which R ⁶ is a methyl group is an ester of pivalic acid (or an ester of trimethylacetic acid). R ⁷ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group, particularly preferably a methyl group or an ethyl group. Specific compounds include methyl trimethyl acetate (methyl pivalate), ethyl trimethyl acetate (ethyl pivalate), propyl trimethyl acetate (propyl pivalate), isopropyl trimethyl acetate (isopropyl pivalate), butyl trimethyl acetate (butyl pivalate) ), Isobutyl trimethyl acetate (isobutyl pivalate), t-butyl trimethyl acetate (t-butyl pivalate), methyl triethyl acetate, ethyl triethyl acetate, propyl triethyl acetate, isopropyl triethyl acetate, butyl triethyl acetate, isobutyl triethyl acetate, triethyl acetate t-butyl, methyl tripropyl acetate, ethyl tripropyl acetate, propyl tripropyl acetate, isopropyl tripropyl acetate, butyl tripropyl acetate, isobutyl tripropyl acetate, tripropyl acetate Propyl acetate t- butyl, triisopropyl methyl acetate, triisopropyl ethyl acetate, triisopropyl propyl acetate, triisopropyl isopropyl acetate, butyl triisopropyl acid, triisopropyl isobutyl acetate, tri isopropyl acetate t- butyl.

  Among the above monocarboxylic acid esters, ethyl benzoate, ethyl p-ethoxybenzoate, ethyl anisate, methyl trimethyl acetate (methyl pivalate) and ethyl trimethyl acetate (ethyl pivalate) are preferred. These monocarboxylic acid esters can be used alone or in combination of two or more.

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

  Below, the preparation method of the component (A) of this invention is described. Specifically, dialkoxymagnesium (a) is suspended in a tetravalent titanium halogen compound (b) or an aromatic hydrocarbon compound (d), and a monocarboxylic acid monoester (c) such as a pivalic acid ester and The method of contacting a tetravalent titanium halogen compound (b) as needed and obtaining a solid component is mentioned. 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 particles by a so-called spray drying method in which the liquid is sprayed and dried, a solid catalyst component 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.

  As a preferable method for preparing the solid catalyst component (A) of the present invention, the component (a) is suspended in the component (d), and then the component (b) is contacted and then the component (c) is contacted and reacted. A method of preparing the solid catalyst component (A), or by suspending the component (a) in the component (d) and then contacting the component (c) and then contacting the component (b) and reacting The method of preparing a solid catalyst component (A) can be mentioned.

Below, the preferable contact order at the time of preparing the solid catalyst component (A) of this invention is illustrated more concretely.
(1) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(2) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) >> → final washing → solid catalyst component (A)
(3) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(4) (a) → (d) → (b) → (c) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)
(5) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (b) → (c) >> → final washing → solid catalyst component (A)
(6) (a) → (d) → (c) → (b) → << intermediate washing → (d) → (c) → (b) >> → final washing → solid catalyst component (A)

  In each of the contact methods described above, the activity in the parentheses (<<) is further improved by repeating the process a plurality of times as necessary. In addition, the component (b) used in the steps in <<> may be newly added or may be the residue of the previous step. In addition to the washing steps shown in (1) to (6) above, the product obtained in each contact stage can be washed with a hydrocarbon compound that is liquid at room temperature.

  Based on the above, a particularly preferred method for preparing the solid catalyst component (A) in the present application 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 liquid, 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 kind or two or more kinds of monocarboxylic acid ester (c) such as ethyl benzoate are treated with -20 to 20%. Contact at 130 ° C. and further contact with the monocarboxylic acid monoester (c) to carry out the reaction treatment to obtain the solid reaction product (1). At this time, it is desirable to carry out the aging reaction at a low temperature before or after contacting one or more of the monocarboxylic acid monoesters. After washing this solid reaction product (1) with a liquid hydrocarbon compound at room temperature (intermediate washing), tetravalent titanium halogen compound (b) is again added in the presence of an aromatic hydrocarbon compound in the range of −20 to 20 The contact treatment is performed at 100 ° C. 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 (final washing) to obtain a solid catalyst component (A).

Preferred conditions for the above treatment or washing are as follows.
Low temperature aging reaction: −20 to 70 ° C., preferably −10 to 60 ° C., more preferably 0 to 30 ° C., 1 minute to 6 hours, preferably 5 minutes to 4 hours, particularly preferably 10 minutes to 3 hours. .
Reaction treatment: 40 to 130 ° C., preferably 70 to 120 ° C., particularly preferably 80 to 115 ° C., 0.5 to 6 hours, preferably 0.5 to 5 hours, particularly preferably 1 to 4 hours.
Washing: 0 to 110 ° C., preferably 30 to 100 ° C., particularly preferably 30 to 90 ° C., 1 to 20 times, preferably 1 to 15 times, particularly preferably 1 to 10 times.

  The hydrocarbon compound used for washing is preferably an aromatic or saturated hydrocarbon compound that is liquid at room temperature. Specifically, toluene, xylene, ethylbenzene, etc. as the aromatic hydrocarbon compound, and hexane as the saturated hydrocarbon compound. , Heptane, cyclohexane and the like. Preferably, an aromatic hydrocarbon compound is used in the intermediate cleaning, and a saturated hydrocarbon compound is used in the final cleaning.

  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 monocarboxylic acid ester (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. is there.

  Further, the content of titanium, magnesium, halogen atom and monocarboxylic acid monoester in the solid catalyst component (A) in the present invention is not particularly defined, but preferably, titanium is 1.0 to 8.0% by weight, preferably 2.0-8.0 wt%, more preferably 3.0-8.0 wt%, magnesium 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, Preferably 15 to 25% by weight, halogen atom 20 to 85% 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 monocarboxylic acid monoester Is 0.5 to 30% by weight in total, 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). Is not particularly limited, but R ¹ is preferably an ethyl group or an 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.

  The aminosilane compound (C) (hereinafter sometimes simply referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention is a compound represented by the above general formula (2). This aminosilane compound is a compound in which N atoms are directly bonded to Si atoms. Examples of such aminosilane compounds include alkylaminotrialkoxysilane, bis (alkylamino) dialkoxysilane, and alkyl (alkylamino) dialkoxysilane. , Cycloalkylaminotrialkoxysilane, alkyl-substituted cycloalkylaminotrialkoxysilane, halogen-substituted cycloalkylaminotrialkoxysilane, cycloalkylalkylaminotrialkoxysilane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamine) Killamino) dialkoxysilane, bis (alkyl substituted cycloalkylamino) dialkoxysilane, bis (halogen substituted cycloalkylamino) dialkoxysilane, bis (cycloalkylalkylamino) dialkoxysilane, cycloalkylaminoalkyl dialkoxysilane, etc. Can be mentioned.

In the general formula (2), a methyl group as R ^2, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t- butyl group, a cyclohexyl group, preferably a cyclopentyl group and a hydrogen atom, as R ³ is A methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, cyclohexyl group and cyclopentyl group are preferred. R ⁴ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group or a t-butyl group. R ⁵ is preferably a methyl group or an ethyl group. In the general formula (2), when q and r are each 1, R ⁴ is preferably an alkyl group having 1 to 5 carbon atoms, particularly an alkyl group having 1 to 5 carbon atoms.

  Specific examples of such aminosilane compounds include dimethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxysilane, methyl (n -Propyl) aminotriethoxysilane, t-butylaminotriethoxysilane, ethyl (n-propyl) aminotriethoxysilane, ethyl (iso-propyl) aminotriethoxysilane, methylethylaminotriethoxysilane, cyclopentylaminotrimethoxysilane , Cyclopentylaminotriethoxysilane, cyclohexylaminotrimethoxysilane, cyclohexylaminotriethoxysilane, 2-methylcyclopentylaminotrimethoxysilane 2-methylcyclopentylaminotriethoxysilane, 2-ethylcyclopentylaminotrimethoxysilane, 2-ethylcyclopentylaminotriethoxysilane, 2-chlorocyclopentylaminotrimethoxysilane, 2-chlorocyclopentylaminotriethoxysilane, 2-bromocyclopentyl Aminotrimethoxysilane, 2-bromocyclopentylaminotriethoxysilane, 2-methylcyclohexylaminotrimethoxysilane, 2-methylcyclohexylaminotriethoxysilane, 2-ethylcyclohexylaminotrimethoxysilane, 2-ethylcyclohexylaminotriethoxysilane, 2-chlorocyclohexylaminotrimethoxysilane, 2-chlorocyclohexylaminotriethoxysilane, 2-bromosilane Rohexylaminotrimethoxysilane, 2-bromocyclohexylaminotriethoxysilane, cyclopentylmethylaminotrimethoxysilane, cyclopentylmethylaminotriethoxysilane, 1-cyclopentylethylaminotrimethoxysilane, 1-cyclopentylethylaminotriethoxysilane, bis ( Methylamino) dimethoxysilane, bis (methylamino) diethoxysilane, bis (ethylamino) dimethoxysilane, bis (ethylamino) diethoxysilane, bis (propylamino) dimethoxysilane, bis (propylamino) diethoxysilane, bis (Isopropylamino) dimethoxysilane, bis (isopropylamino) diethoxysilane, bis (butylamino) dimethoxysilane, bis (butylamino) diethoxy Silane, bis (isobutylamino) dimethoxysilane, bis (isobutylamino) diethoxysilane, bis (t-butylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis (cyclopentylamino) dimethoxysilane, bis ( Cyclopentylamino) diethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (cyclohexylamino) diethoxysilane, bis (2-methylcyclopentylamino) dimethoxysilane, bis (2-methylcyclopentylamino) diethoxysilane, bis (2 -Ethylcyclopentylamino) dimethoxysilane, bis (2-ethylcyclopentylamino) diethoxysilane, bis (2-chlorocyclopentylamino) dimethoxysilane, bis (2-chlorocyclopene) Ruamino) diethoxysilane, bis (2-bromocyclopentylamino) dimethoxysilane, bis (2-bromocyclopentylamino) diethoxysilane, bis (2-methylcyclohexylamino) dimethoxysilane, bis (2-methylcyclohexylamino) diethoxy Silane, bis (2-ethylcyclohexylamino) dimethoxysilane, bis (2-ethylcyclohexylamino) diethoxysilane, bis (2-chlorocyclohexylamino) dimethoxysilane, bis (2-chlorocyclohexylamino) diethoxysilane, bis ( 2-bromocyclohexylamino) dimethoxysilane, bis (2-bromocyclohexylamino) diethoxysilane, bis (cyclopentylmethylamino) dimethoxysilane, bis (cyclopentylmethyl) Amino) diethoxysilane, bis (1-cyclopentylethylamino) dimethoxysilane, bis (1-cyclopentylethylamino) ditriethoxysilane, methyl (isopropylamino) dimethoxysilane, ethyl (isopropylamino) dimethoxysilane, n-propyl (amino) Dimethoxysilane, isopropyl (isopropylamino) dimethoxysilane, Sec-butyl (isopropylamino) dimethoxysilane, t-butyl (isopropylamino) dimethoxysilane, cyclopentyl (isopropylamino) dimethoxysilane, cyclohexyl (isopropylamino) dimethoxysilane, methyl (n -Butylamino) dimethoxysilane, ethyl (n-butylamino) dimethoxysilane, n-propyl (n-butylamino) dimethoxy Sisilane, isopropyl (n-butylamino) dimethoxysilane, Sec-butyl (n-butylamino) dimethoxysilane, t-butyl (n-butylamino) dimethoxysilane, cyclopentyl (n-butylamino) dimethoxysilane, cyclohexyl (n- Butylamino) dimethoxysilane, methyl (n-butylamino) dimethoxysilane, methyl (n-butylamino) dimethoxysilane, methyl (sec-butylamino) dimethoxysilane, ethyl (sec-butylamino) dimethoxysilane, n-propyl (sec -Butylamino) dimethoxysilane, isopropyl (sec-butylamino) dimethoxysilane, Sec-butyl (n-butylamino) dimethoxysilane, t-butyl (n-butylamino) dimethoxysilane, cyclopentyl (sec-butyl) Mino) dimethoxysilane, cyclohexyl (sec-butylamino) dimethoxysilane, methyl (t-butylamino) dimethoxysilane, ethyl (t-butylamino) dimethoxysilane, n-propyl (t-butylamino) dimethoxysilane, isopropyl (t- Butylamino) dimethoxysilane, n-butyl (t-butylamino) dimethoxysilane, Sec-butyl (t-butylamino) dimethoxysilane, t-butyl (t-butylamino) dimethoxysilane, cyclopentyl (t-butylamino) dimethoxy Silane, 2-methylcyclopentyl (t-butylamino) dimethoxysilane, cyclohexyl (t-butylamino) dimethoxysilane, 2-methylcyclohexyl (t-butylamino) dimethoxysilane, methyl (cyclopentyla) B) dimethoxysilane, ethyl (cyclopentylamino) dimethoxysilane, n-propyl (cyclopentylamino) dimethoxysilane, isopropyl (cyclopentylamino) dimethoxysilane, Sec-butyl (cyclopentylamino) dimethoxysilane, t-butyl (cyclopentylamino) dimethoxysilane, Cyclopentyl (cyclopentylamino) dimethoxysilane, cyclohexyl (cyclopentylamino) dimethoxysilane, methyl (cyclohexylamino) dimethoxysilane, ethyl (cyclohexylamino) dimethoxysilane, n-propyl (cyclohexylamino) dimethoxysilane, isopropyl (cyclohexylamino) dimethoxysilane, Sec -Butyl (cyclohexylamino) dimethoxysilane, t-butyl Examples thereof include ru (cyclohexylamino) dimethoxysilane, cyclopentyl (cyclohexylamino) dimethoxysilane, cyclohexyl (cyclohexylamino) dimethoxysilane, and the like.

  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. 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, vinylcyclohexane, and the like, and these olefins can be used alone or in combination of two or more. In particular, ethylene and 1-butene are preferably used.

  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).

  The order of contacting the components is arbitrary, but the organoaluminum compound (B) is first charged into the polymerization system, then the organosilicon compound (C) is contacted, and then the solid catalyst component (A) is contacted.

  The method for producing an olefin polymer in the present invention uses the olefin polymerization catalyst and can be carried out in the presence or absence of an organic solvent. The olefin monomer such as propylene is a gas. It can be used in both liquid and liquid states. 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.

  Furthermore, in polymerizing an olefin using a catalyst containing the component (A) and the component (B) or the component (C) in the present invention (also referred to as main polymerization), catalytic activity, stereoregularity and generated heavy 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) or component (C) is contacted in the presence of olefins, 0.1 to 100 g of polyolefin per 1 g of component (A) is preliminarily polymerized, and Component (B) or component (C) is contacted to form a catalyst.

  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, a polymer having high activity and high stereoregularity can be obtained in a high yield as compared with the case of using a conventional catalyst. The effect of being able to be confirmed was confirmed.

  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.

Examples 1-4
<Preparation of solid catalyst component>
A 200 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 10 g of diethoxymagnesium and 40 ml of toluene to form a suspended state. The suspension was then added to a solution of 10 ml of toluene and 50 ml of titanium tetrachloride, pre-charged in a 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas. Next, the suspension was reacted at −5 ° C. for 2 hours (low temperature aging treatment). Thereafter, 5.1 g of ethyl benzoate was added, the temperature was further raised to 90 ° C., and then a reaction treatment (first treatment) was performed for 2 hours with stirring. After completion of the reaction, the product was washed once with 100 ml of toluene at 70 ° C., and further washed with 100 ml of n-heptane at 70 ° C. four times (intermediate washing), and 50 ml of titanium tetrachloride was newly added and stirred. A reaction treatment (second treatment) was performed at 100 ° C. for 1 hour. Further, 50 ml of titanium tetrachloride was added, and a reaction treatment (third treatment) was performed at 100 ° C. for 1 hour with stirring. Subsequently, the product was washed 7 times with 100 ml of heptane at 40 ° C., filtered and dried to obtain a powdery solid catalyst component (A). The titanium content in the solid catalyst component was measured and found to be 4.98% by weight.

[Formation and polymerization of polymerization catalyst]
First, 700 ml of n-heptane was charged into a stainless steel autoclave with a stirrer having an internal volume of 1800 ml that had been thoroughly dried with nitrogen gas and then replaced with propylene gas, and was first maintained at 2.10 mmol of triethylaluminum while maintaining the propylene gas atmosphere. Then, 0.21 mmol of diethylaminotriethoxysilane was charged, and then 0.0053 mmol of Ti as the solid catalyst component was charged to form a polymerization catalyst. Next, a preliminary polymerization was carried out at 20 ° C. for 30 minutes while applying propylene pressure of 0.2 MPa and keeping stirring. Thereafter, 120 ml of hydrogen was charged, and the polymerization was continued for 15 to 180 minutes as shown in Table 1 at 70 ° C. with a propylene pressure in the system of 0.7 MPa. In addition, the pressure which falls as superposition | polymerization advances was supplemented by supplying only propylene continuously, and was kept at the constant pressure during superposition | polymerization. According to the above polymerization method, propylene was polymerized, and the produced polymer was filtered and dried under reduced pressure to obtain a solid polymer. On the other hand, the filtrate is condensed to obtain a polymer dissolved in the polymerization solvent, the amount of which is (M), and the amount of the solid polymer is (N). The obtained solid polymer is extracted with boiling n-heptane for 6 hours to obtain a polymer insoluble in n-heptane, and this amount is defined as (P). The polymerization activity (Y) per solid catalyst component is represented by the following formula.
(Y) = [(M) + (N)] (g) / solid catalyst component amount (g)
The total polymer (HI) insoluble in n-heptane is represented by the following formula.
(HI) = {(P) (g) / [(M) + (N)] (g)} × 100
Furthermore, when the melt flow rate (MI) and bulk specific gravity (BD) of the produced solid polymer were measured, the results shown in Table 1 were obtained.

  The melt flow rate value (MI) of the produced solid polymer (N) was measured according to ASTM D 1238 and JIS K 7210.

Examples 5-8
Experiments were performed in the same manner as in Examples 1 to 4 except that cyclopentylaminotriethoxysilane was used instead of diethylaminotriethoxysilane. The results are shown in Table 1.

Examples 9-12
Experiments were performed in the same manner as in Examples 1 to 4 except that cyclohexylaminotriethoxysilane was used instead of diethylaminotriethoxysilane. The results are shown in Table 1.

Examples 13-16
Experiments were performed in the same manner as in Examples 1 to 4, except that bis (t-butylamino) dimethoxysilane was used instead of diethylaminotriethoxysilane. The results are shown in Table 1.

Examples 17-20
Experiments were performed in the same manner as in Examples 1 to 4, except that ethyl (t-butylamino) dimethoxysilane was used instead of diethylaminotriethoxysilane. The results are shown in Table 1.

Comparative Examples 1-4
Experiments were performed in the same manner as in Examples 1 to 4 except that ethyl p-ethoxybenzoate was used instead of diethylaminotriethoxysilane. The obtained results are shown in Table 1.

Comparative Examples 5-8
Experiments were performed in the same manner as in Examples 1 to 4 except that cyclohexylmethyldimethoxysilane was used instead of diethylaminotriethoxysilane. The obtained results are shown in Table 1.

  From the above results, a catalyst using an aminosilane compound as a conventional monocarboxylic acid monoester-based solid catalyst component exhibits high activity sustainability, and a highly stereoregular polymer can be obtained with good yield, and hydrogen. It can be seen that the response is good.

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

Claims (7)

(A) a solid catalyst component containing magnesium, titanium, a halogen atom and a monocarboxylic acid monoester;
(B) The following general formula (1); R ¹ _p AlQ _3-p (1)
(In the formula, 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) the following general formula (2); (R ² R ³ N) _q R ⁴ _r Si (OR ⁵ ) _4-qr (2)
(In the formula, R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, an aralkyl group, or a hydrogen atom; ³ represents a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and R ² and R ³ may be the same. R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, and may be the same or different, and R ⁵ represents a carbon number. 1 to 4 alkyl group, C 3 to C 6 cycloalkyl group, phenyl group, vinyl group, allyl group, or aralkyl group, which may be the same or different, q is 1, 2 or 3, r is 0, 1 or 2, 1 q + a r ≦ 3.) aminosilane compound represented by the
A catalyst for olefin polymerization, characterized in that it is formed from   The olefin polymerization according to claim 1, wherein the solid catalyst component is obtained by contacting (a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c) a monocarboxylic acid monoester. Catalyst.   The catalyst for olefin polymerization according to claim 2, wherein the magnesium compound is alkoxymagnesium.   2. The aminosilane compound (C) is alkylaminotrialkoxysilane, bis (alkylamino) dialkoxysilane, alkyl (alkylamino) dialkoxysilane, or cycloalkylaminotrialkoxysilane. Catalyst for polymerization of olefins.   The olefin polymerization catalyst according to claim 1, wherein the aminosilane compound (C) is diethylaminotriethoxysilane.   A method for producing an olefin polymer, which is carried out in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 5. The method for producing an olefin polymer according to claim 6, wherein the olefin polymer is a propylene polymer.

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