JP2007224097A - Catalyst for polymerizing olefins and method for producing olefin polymer with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst which is used for polymerizing olefins, can give polymers having high stereoregularity in high catalyst activity and in good yields, and has good hydrogen response, and to provide a method for producing an olefin polymer in the presence of the catalyst. <P>SOLUTION: This catalyst for polymerizing the olefin contains, as active ingredients, (A) a solid catalyst component comprising magnesium, titanium, a halogen and an electron-donating compound, (B) an organic aluminum compound represented by the general formula: R<SP>4</SP><SB>p</SB>AlQ<SB>3-p</SB>, and (C) an aminosilane compound represented by the general formula: R<SP>1</SP><SB>m</SB>HSi(NR<SP>2</SP>R<SP>3</SP>)<SB>4-m</SB>. And the method for producing the olefin polymer in the presence of the catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

   The present invention provides a catalyst catalyst for polymerization of olefins, which can maintain a high degree of stereoregularity and yield of a polymer and obtain a high melt flow rate by adding a small amount of hydrogen, that is, a so-called good hydrogen response. The present invention relates to a method for producing a polymer of olefins.

   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 magnesium compound, a titanium compound, and an organosilicon compound having a Si—O—C bond are used. In particular, a method for polymerizing olefins having 3 or more carbon atoms using a catalyst composed of a combination has been proposed. 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 prepared by heat treatment with, an organoaluminum compound and an organosilicon compound, and a method for polymerizing propylene 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 the alkylbenzene, and phthalic acid chloride is then added and made to react. A solid catalyst component prepared by obtaining a solid product and further contacting the solid product with titanium tetrachloride in the presence of an alkylbenzene, a catalyst for propylene comprising an organoaluminum compound and an organosilicon compound, and the catalyst 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 so-called deashing step for removing catalyst residues such as chlorine and titanium remaining in the produced polymer can be omitted. Although efforts have been made to improve the yield and to increase the sustainability of the catalyst activity during the polymerization, each of them has achieved results, but improvement of the catalyst for such purpose is still desired.

  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 products such as automobiles and home appliances. These melt the polymer powder produced by polymerization and are molded by various molding machines. Especially when producing large molded products by injection molding, the fluidity of the molten polymer (melt flow rate, MFR) Is required to be high. In particular, in order to reduce the cost of highly functional block copolymers for automotive materials, we produce as many copolymers as necessary for the production of olefinic thermoplastic elastomers (hereinafter referred to as “TPO”) in the copolymerization reactor. However, in the production of TPO directly in a polymerization reactor without adding a newly synthesized copolymer after production, that is, in the production of reactor-made TPO by “direct weight” in the industry, the final product In order to keep the melt flow rate sufficiently large and facilitate injection molding, the melt flow rate at the homopolymerization stage is required to be 200 or more. Therefore, many studies have been made to increase the melt flow rate while maintaining high stereoregularity of the polymer.

The melt flow rate is highly dependent on the molecular weight of the polymer. In the industry, it is common to add hydrogen as a molecular weight regulator for the polymer produced in the polymerization of propylene. At this time, when producing a low molecular weight polymer, that is, a polymer having a high melt flow rate, it is usually necessary to add a large amount of hydrogen. However, in a bulk polymerization apparatus, the pressure resistance of the reactor is limited due to its safety, and the addition is limited. There is a limit to the amount of hydrogen that can be made. In the case of gas phase polymerization, in order to add a large amount of hydrogen, the partial pressure of the monomer to be polymerized must be reduced, resulting in a decrease in productivity. In addition, the use of a large amount of hydrogen also causes a problem that the manufacturing cost increases. In order to solve this problem, Patent Document 5 (WO 2004-16662) discloses a high melt flow by using a compound represented by Si (OR ¹ ) ₃ (NR ² R ³ ) as a catalyst component for the polymerization of olefins. It is disclosed that a polymer having a high rate and a high degree of stereoregularity is produced, and has given a certain effect.

However, it is not sufficient to fundamentally solve the problem of TPO production by direct weight as described above, and further improvement has been desired.
JP-A-57-63310 (Claims) JP-A-57-63311 (Claims) JP 63-3010 A (Claims) JP-A-1-315406 (Claims) WO 2004-16662 (Claims)

  Therefore, an object of the present invention is to maintain a high degree of stereoregularity and yield of a polymer and to obtain a high melt flow rate by adding a small amount of hydrogen, that is, a catalyst for polymerization of olefins having a good hydrogen response. Another object of the present invention is to provide a process for producing an olefin polymer using the same.

  In such a situation, as a result of intensive studies, the inventors of the present invention have not heretofore been known as the use of the aminosilane compound represented by the general formula (1) as a catalyst for olefin polymerization, The catalyst for olefin polymerization containing the aminosilane compound as an active ingredient has been found to be able to maintain a high degree of stereoregularity and yield of the polymer and have good hydrogen response, and has completed the present invention. .

That is, the present invention provides the following general formula (1): R ¹ _m HSi (NR ² R ³ ) _3-m (1)
(Wherein, m is an integer of 0 or 1 and 2, R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, An alkylsilyl group, an aminoalkylsilyl group, which may contain a hetero atom, and may be the same or different, and when m is 2, two R ¹ may be bonded to each other to form a ring; R ² and R ³ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, a trialkylsilyl group, the same or They may be different, and R ² and R ³ may combine with each other to form a ring.) An olefin polymerization catalyst comprising an aminosilane compound represented by the following formula as an active ingredient is provided.

Further, the present invention provides (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound, (B) the following general formula (2);
R ³ _p AlQ _3−p (2)
(Wherein R ³ 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) An olefin polymerization catalyst characterized by being formed from an aminosilane compound represented by the general formula (1).

  Furthermore, the present invention provides a method for producing an olefin polymer, characterized in that olefins are polymerized in the presence of the olefin polymerization catalyst.

  The catalyst for polymerization of olefins of the present invention can maintain a higher degree of polymer stereoregularity and yield than conventional catalysts, and can obtain a high melt flow rate by adding a small amount of hydrogen (hereinafter simply referred to as “hydrogen response”). Is sometimes obtained). Therefore, it is possible to provide a general-purpose polyolefin at a low cost due to functions such as reduction in the amount of hydrogen used in the polymerization and high activity of the catalyst, and it is expected to be useful in the production of olefin polymers having high functionality. The

  The olefin polymerization catalyst of the present invention contains an aminosilane compound represented by the general formula (1) as an active ingredient. That is, the aminosilane can be used as an electron donating compound (internal donor) of a solid catalyst component that is a constituent element of an olefin polymerization catalyst and an electron donating compound (external donor) of an olefin polymerization catalyst, Among these, when used as an electron donating compound (external donor) of an olefin polymerization catalyst, the effect of the present invention is particularly prominent.

   This aminosilane compound is a compound in which an N atom and a hydrogen atom are directly bonded to a Si atom. Examples of such an aminosilane compound include tris (alkylamino) silane, bis (alkylamino) (dialkylamino) silane, and tris (dialkylamino). ) Silane, bis (alkylamino) alkylsilane, bis (alkylamino) (dialkylamino) silane, bis (dialkylamino) alkylsilane, bis (alkylamino) perhydroisoquinolinosilane, bis (alkylamino) perhydroquinolyl Nosilane, bis (trialkylsilylamino) (alkylamino) silane, and the like.

The alkylamino group is a secondary amino residue in which one alkyl group and a hydrogen atom are bonded to N, and the dialkylamino group is a tertiary amino residue. In the aminosilane compound used in the present invention, in the general formula (1), when m is 0 or 1, at least one of two or three —NR ² R ³ groups is either R ² or R ^3. Is a secondary amino residue in which is a hydrogen atom. When m is 2, one —NR ² R ³ group is preferably a secondary amino residue in which either R ² or R ³ is a hydrogen atom.

In the general formula (1), examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a silicon atom. In general formula (1), R ¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aminoalkylsilyl group, and particularly a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, and an aminoalkylsilyl group are preferred. R ² and R ³ are a linear or branched alkyl group having 1 to 10 carbon atoms, an aminoalkylsilyl group, or a cycloalkyl group.

Although it does not restrict | limit especially as an aminosilane compound represented by General formula (1), The example is shown below. That is, tris (methylamino) silane, tris (ethylamino) silane, tris (dimethylamino) silane, tris (diethylamino) silane, (methylamino) (2-methoxyethyl) ethylsilane, (methylamino) (2-methoxyethyl) ) Iso-propylsilane, (methylamino) (2-methoxyethyl) iso-butylsilane, (methylamino) (2-methoxyethyl) sec-butylsilane, (methylamino) (2-methoxyethyl) t-butylsilane, (methyl Amino) (2-methoxyethyl) cyclopentylsilane, (methylamino) (2-methoxyethyl) cyclohexylsilane, (methylamino) (2-methoxyethyl) texylsilane, (methylamino) (2-methoxyethyl) phenylsilane, ( Methylamino (2-methoxyethyl) benzyl silane,
(Ethylamino) (2-methoxyethyl) ethylsilane, (ethylamino) (2-methoxyethyl) iso-propylsilane, (ethylamino) (2-methoxyethyl) iso-butylsilane, (ethylamino) (2-methoxyethyl) ) Sec-butylsilane, (ethylamino) (2-methoxyethyl) t-butylsilane, (ethylamino) (2-methoxyethyl) cyclopentylsilane, (ethylamino) (2-methoxyethyl) cyclohexylsilane, (ethylamino) ( 2-methoxyethyl) texylsilane, (ethylamino) (2-methoxyethyl) phenylsilane, (ethylamino) (2-methoxyethyl) benzylsilane,

  Bis (dimethylamino) (2-methylaminoethyl) silane, bis (dimethylamino) (2-ethylaminoethyl) silane, bis (dimethylamino) [2,2-bis (methylamino) ethyl] silane, bis (dimethyl) Amino) [2,2-bis (ethylamino) ethyl] silane, bis (dimethylamino) (2,2-diethylaminoethyl) silane,

  Bis (diethylamino) (2-methylaminoethyl) silane, bis (diethylamino) (2-ethylaminoethyl) silane, bis (diethylamino) [2,2-bis (methylamino) ethyl] silane, bis (diethylamino) [2 , 2-bis (ethylamino) ethyl] silane, bis (diethylamino) (2,2-diethylaminoethyl) silane,

  Di (trimethylsilylamino) (methylamino) ethylsilane, di (trimethylsilylamino) (methylamino) n-propylsilane, di (trimethylsilylamino) (methylamino) iso-propylsilane, di (trimethylsilylamino) (methylamino) iso- Butylsilane, di (trimethylsilylamino) (methylamino) t-butylsilane,

  Di (trimethylsilylamino) (ethylamino) ethylsilane, di (trimethylsilylamino) (ethylamino) n-propylsilane, di (trimethylsilylamino) (ethylamino) iso-propylsilane, di (trimethylsilylamino) (ethylamino) iso- Butylsilane, di (trimethylsilylamino) (ethylamino) t-butylsilane,

  Bis (methylamino) ethylsilane, bis (methylamino) n-propylsilane, bis (methylamino) iso-propylsilane, bis (methylamino) iso-butylsilane, bis (methylamino) sec-butylsilane, bis (methylamino) t-butylsilane, bis (methylamino) cyclopentylsilane, bis (methylamino) cyclohexylsilane, bis (methylamino) perhydronaphthylsilane,

  Bis (ethylamino) ethylsilane, bis (ethylamino) n-propylsilane, bis (ethylamino) iso-propylsilane, bis (ethylamino) iso-butylsilane, bis (ethylamino) sec-butylsilane, bis (ethylamino) t-butylsilane, bis (ethylamino) cyclopentylsilane, bis (ethylamino) cyclohexylsilane, bis (ethylamino) perhydronaphthylsilane,

  Bis (n-propylamino) ethylsilane, bis (n-propylamino) n-propylsilane, bis (n-propylamino) iso-propylsilane, bis (n-propylamino) iso-butylsilane, bis (n-propylamino) ) Sec-butylsilane, bis (n-propylamino) t-butylsilane, bis (n-propylamino) cyclopentylsilane, bis (n-propylamino) cyclohexylsilane, bis (n-propylamino) perhydronaphthylsilane,

  (Methylamino) diethylsilane, (methylamino) di-n-propylsilane, (methylamino) diiso-propylsilane, (methylamino) diiso-butylsilane, (methylamino) disec-butylsilane, (methylamino) di t-butylsilane, (methylamino) dicyclopentylsilane, (methylamino) dicyclohexylsilane,

(Methylamino) ethylmethylsilane, (methylamino) ethyl n-propylsilane, (methylamino) ethyl iso-propylsilane, (methylamino) n-propyliso-butylsilane, (methylamino) ethyl sec-butylsilane, (methyl Amino) n-propyl t-butylsilane, (methylamino) cyclopentylcyclohexylsilane, (methylamino) ethylcyclohexylsilane,
(Ethylamino) diethylsilane, (ethylamino) di-n-propylsilane, (ethylamino) diiso-propylsilane, (ethylamino) diiso-butylsilane, (ethylamino) disec-butylsilane, (ethylamino) di t-butylsilane, (ethylamino) dicyclopentylsilane, (ethylamino) dicyclohexylsilane,

(Ethylamino) ethylmethylsilane, (ethylamino) ethyl n-propylsilane, (ethylamino) ethyl iso-propylsilane, (ethylamino) n-propyliso-butylsilane, (ethylamino) ethyl sec-butylsilane, (ethyl Amino) n-propyl t-butylsilane, (ethylamino) cyclopentylcyclohexylsilane, (ethylamino) ethylcyclohexylsilane,
Bis (methylamino) (diethylamino) silane, bis (methylamino) (di-n-propylamino) silane, bis (methylamino) (diiso-propylamino) silane, bis (methylamino) (diiso-butylamino) Silane, bis (methylamino) (disec-butylamino) silane, bis (methylamino) (di-t-butylamino) silane, bis (methylamino) (dicyclohexylamino) silane, bis (methylamino) (dicyclopentylamino) ) Silane, bis (methylamino) (ditrimethylsilylamino) silane, bis (methylamino) (ditriethylsilylamino) silane,

  Bis (ethylamino) (diethylamino) silane, bis (ethylamino) (di-n-propylamino) silane, bis (ethylamino) (diiso-propylamino) silane, bis (ethylamino) (diiso-butylamino) Silane, bis (ethylamino) (disec-butylamino) silane, bis (ethylamino) (di-t-butylamino) silane, bis (ethylamino) (dicyclohexylamino) silane, bis (ethylamino) (dicyclopentylamino) ) Silane, bis (ethylamino) (ditrimethylsilylamino) silane, bis (ethylamino) (ditriethylsilylamino) silane,

  Bis (n-propylamino) (diethylamino) silane, bis (n-propylamino) (di-n-propylamino) silane, bis (n-propylamino) (diiso-propylamino) silane, bis (n-propylamino) ) (Diiso-butylamino) silane, bis (n-propylamino) (disec-butylamino) silane, bis (n-propylamino) (di-t-butylamino) silane, bis (n-propylamino) ( Dicyclohexylamino) silane, bis (n-propylamino) (dicyclopentylamino) silane, bis (n-propylamino) (ditrimethylsilylamino) silane, bis (n-propylamino) (ditriethylsilylamino) silane,

  Bis (diethylamino) (methylamino) silane, bis (di-n-propylamino) (methylamino) silane, bis (diiso-propylamino) (methylamino) silane, bis (diiso-butylamino) (methylamino) Silane, bis (diiso-butylamino) (methylamino) silane, bis (disec-butylamino) (methylamino) silane, bis (di-t-butylamino) (methylamino) silane, bis (dicyclopentylamino) (Methylamino) silane, bis (dicyclohexylamino) (methylamino) silane, bis (ditrisilylmethylamino) (methylamino) silane, bis (ditrisilylethylamino) (methylamino) silane,

  Bis (diethylamino) (ethylamino) silane, bis (di-n-propylamino) (ethylamino) silane, bis (diiso-propylamino) (ethylamino) silane, bis (diiso-butylamino) (ethylamino) Silane, bis (diiso-butylamino) (ethylamino) silane, bis (disec-butylamino) (ethylamino) silane, bis (di-t-butylamino) (ethylamino) silane, bis (dicyclopentylamino) (Ethylamino) silane, bis (dicyclohexylamino) (ethylamino) silane, bis (ditrisilylmethylamino) (ethylamino) silane, bis (ditrisilylethylamino) (ethylamino) silane,

  Bis (diethylamino) (n-propylamino) silane, bis (di-n-propylamino) (n-propylamino) silane, bis (diiso-propylamino) (n-propylamino) silane, bis (diiso-butyl) Amino) (n-propylamino) silane, bis (diiso-butylamino) (n-propylamino) silane, bis (disec-butylamino) (n-propylamino) silane, bis (di-t-butylamino) (N-propylamino) silane, bis (dicyclopentylamino) (n-propylamino) silane, bis (dicyclohexylamino) (n-propylamino) silane, bis (ditrisilylmethylamino) (n-propylamino) silane, Bis (ditrisilylethylamino) (n-propylamino) silane,

  Bis (methylamino) perhydroisoquinolinosilane, bis (methylamino) perhydroquinolinosilane, bis (methylamino) tetrahydroquinolinosilane, bis (methylamino) octamethyleneiminosilane, bis (ethylamino) perhydroiso Quinolinosilane, bis (ethylamino) perhydroquinolinosilane, bis (ethylamino) tetrahydroquinolinosilane, bis (ethylamino) octamethyleneiminosilane, bis (n-propylamino) perhydroisoquinolinosilane, bis ( n-propylamino) perhydroquinolinosilane, bis (n-propylamino) tetrahydroquinolinosilane, bis (n-propylamino) octamethyleneiminosilane and the like.

  Examples of the synthesis of these compounds include known synthesis methods such as a chlorine exchange method, a method using an organic lithium compound, and a method using a Grignard reagent. Alternatively, the synthesis can be performed by a method combining these known methods.

  The catalyst for olefin polymerization of the present invention includes a solid catalyst component (A) (hereinafter sometimes referred to as “component (A)”) and an organic aluminum compound in addition to the aminosilane compound of the above general formula (1). . Known solid catalyst components (A) and organic aluminum compounds can be used.

 Among the olefin polymerization catalysts of the present invention, the solid catalyst component (A) contains magnesium, titanium, halogen and an electron donor compound, but (a) a magnesium compound, (b) a tetravalent titanium halogen compound and (c). ) It can be obtained by contacting an electron donor compound.

  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, magnesium dihalide, a mixture of magnesium dihalide and dialkoxymagnesium, dialkoxymagnesium is preferable, dialkoxymagnesium is particularly preferable, specifically, dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, Butoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, butoxyethoxymagnes Um, and the like, diethoxy magnesium is particularly preferred.

  These dialkoxymagnesium may be obtained by reacting metal magnesium with alcohol in the presence of a halogen-containing organic metal or the like. The above dialkoxymagnesium can be used alone or in combination of two or more.

 Furthermore, dialkoxymagnesium that is preferably used 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 is obtained, and the handling operability of the produced polymer powder during the polymerization operation is improved. Problems such as filter clogging in the polymer separation apparatus due to the fine powder contained are solved.

  The spherical dialkoxymagnesium does not necessarily have a true spherical shape, and may have an elliptical cross-sectional shape or a potato shape. 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 5-150 micrometers. In the case of spherical dialkoxymagnesium, the average particle size is 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40 μm. Moreover, about the particle size, it is preferable to use a thing with few fine powder and coarse powder and a narrow particle size distribution. 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 represented by D90 / D10 (where D90 is the integrated particle size at 90%, D10 is the integrated particle size at 10%), it is 3 or less, preferably 2 or less. .

 For example, JP-A-58-4132, 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 a general formula Ti (OR ⁵ ) nX _4-n (formula R ⁵ represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen atom, and n is an integer of 0 ≦ n ≦ 4. Or one or more compounds.

  Specifically, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide as titanium halides, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n-butoxy as alkoxy titanium halides. 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. Illustrated. 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, for example, Organics containing alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, Si—O—C bonds or Si—N—C bonds Examples thereof include silicon compounds.

  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, amyle ether, diphenyl ether, 9, Ethers such as 9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, Ethyl butyrate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, methyl anisate, ethyl anisate, etc. Carboxylic acid esters, diethyl malonate, dipropyl malonate, dibutyl malonate, diisobutyl malonate, dipentyl malonate, dineopentyl malonate, diethyl isopropyl bromomalonate, diethyl butyl bromomalonate, diethyl diisobutyl bromomalonate, diisopromalon Diethyl diethyl, diethyl dibutylmalonate, diethyl diisobutylmalonate, diethyl diisopentylmalonate, diethyl isopropylbutylmalonate, dimethyl isopropylisopentylmalonate, diethyl bis (3-chloro-n-propyl) malonate, bis (3 -Bromo-n-propyl) diethyl malonate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dipropyl adipate, Dicarboxylic acid diesters such as dibutyl dipinate, diisodecyl adipate, dioctyl adipate, diphthalic acid diester, phthalic acid diester derivatives, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetophenone, benzophenone, phthalic acid dichloride, terephthalic acid dichloride Acid chlorides such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde and other aldehydes, methylamine, ethylamine, tributylamine, piperidine, aniline, pyridine and other amines, oleic acid amide, stearic acid amide and other amides, Nitriles such as acetonitrile, benzonitrile and tolylnitrile, isocyanates such as methyl isocyanate and ethyl isocyanate, Organosilicon compounds containing Si—O—C bonds such as alkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, bis (alkylamino) dialkoxysilane, bis (cycloalkylamino) Examples thereof include organosilicon compounds containing a Si—N—C bond such as dialkoxysilane, alkyl (alkylamino) dialkoxysilane, dialkylaminotrialkoxysilane, and cycloalkylaminotrialkoxysilane.

  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-isopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, ethyl methyl phthalate, Methyl isopropyl phthalate, ethyl phthalate (n-propyl), ethyl phthalate (n-butyl), ethyl phthalate-isobutyl, di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate, dihexyl phthalate, phthalate Di-n-heptyl phthalate, di-n-octyl phthalate, bis (2,2-dimethylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-isodecyl phthalate, Bis (2,2-dimethylheptyl) phthalate, n-butyl phthalate (isohexyl) N-butyl phthalate (2-ethylhexyl), n-pentyl phthalate (hexyl), n-pentyl phthalate (isohexyl), isopentyl phthalate (heptyl), n-pentyl phthalate (2-ethylhexyl), n-phthalate -Pentyl (isononyl), isopentyl phthalate (n-decyl), n-pentyl phthalate (undecyl), isopentyl phthalate (isohexyl), n-hexyl phthalate (2,2-dimethylhexyl), n-hexyl phthalate (Isononyl), n-hexyl phthalate (n-decyl), n-heptyl phthalate (2-ethylhexyl), n-heptyl phthalate (isononyl), n-heptyl phthalate (neo-decyl), 2-phthalic acid 2- Ethylhexyl (isononyl) is exemplified, and there is one of these phthalic acid diesters The 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 ester groups of the phthalic acid diester are bonded are an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, and Examples thereof include those substituted with a halogen atom such as a fluorine atom. The solid catalyst component prepared using the phthalic diester derivative as an electron donating compound can further improve the hydrogen response, and the polymer melt flow rate can be improved even when the amount of hydrogen added during polymerization is the same or small. be able to. Specifically, dineopentyl 4-methylphthalate, dineopentyl 4-ethylphthalate, 4,5, dineopentyl dimethylphthalate, dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-chlorochlorophthalate Butyl, dineopentyl 4-chlorophthalate, diisobutyl 4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl 4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl 4-bromophthalate, dineopentyl 4-bromophthalate, 4- Diisobutyl bromophthalate, diisohexyl 4-bromophthalate, diisooctyl 4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl 4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate It includes 4,5-dichloro phthalic acid diisooctyl, of which 4-bromophthalic acid dineopentyl, 4-bromophthalic di -n- butyl, and 4-bromophthalic acid diisobutyl are preferred.

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

  In the present invention, when the above (a), (b) and (c) are brought into contact with each other, they are contacted in the presence of the aromatic hydrocarbon compound (d) (hereinafter sometimes simply referred to as “component (d)”). The method of making it preferable is. Specifically, an aromatic hydrocarbon compound having a boiling point of 50 to 150 ° C. such as toluene, xylene or ethylbenzene is preferably used as the component (d). Moreover, these may be used independently or may be used in mixture of 2 or more types.

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. As a result, 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, but 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). It is 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, decamethylcyclopentanesiloxane, 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 component (A) is formed by contacting the components (a), (b), and (c) and, if necessary, the component (d) or the component (e). By using a spherical magnesium compound as the component (a), a spherical component (A) having a sharp particle size distribution can be obtained, and without using a spherical magnesium compound, for example, a solution or By forming the particles by a so-called spray drying method in which the suspension is sprayed and dried, the component (A) having a spherical shape and a sharp particle size distribution can be obtained.

  The contact of each component is performed with stirring in a container equipped with a stirrer in an inert gas atmosphere and in a state where moisture 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 is 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 catalyst component, and if it exceeds 130 ° C, evaporation of the solvent used becomes remarkable. Therefore, 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 component (A) of the present invention is to suspend component (a) in component (d), then contact component (b), and then contact component (c) and component (d). A method of preparing component (A) by reacting, suspending component (a) in component (d), then contacting component (c) and then contacting component (b) and reacting A method for preparing component (A), or a suspension formed from component (a), component (c) and component (d), and a mixed solution formed from component (b) and component (d) Mention may be made of a preparation method in which the suspension is brought into contact and then reacted. Moreover, the performance of the final solid catalyst component can be improved by bringing the component (A) thus prepared into contact with the component (b) or the component (b) and the component (c) again or multiple times. it can. At this time, it is desirable to carry out in the presence of the aromatic hydrocarbon (d).

  Preferred methods for preparing component (A) in the present invention include the methods shown below. 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 treatment (first reaction treatment). 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. It is also possible to obtain a component (A) obtained by repeating a reaction treatment (secondary reaction treatment) and washing with a liquid hydrocarbon compound 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 Contact at 130 ° C. and contact with component (e) as necessary to carry out a reaction treatment to obtain a solid product (1). At this time, it is desirable to conduct the aging reaction at a low temperature before or after contacting one or more of the electron donating compounds. This solid product (1) was washed with a liquid hydrocarbon compound at room temperature (intermediate washing), and then the tetravalent titanium halogen compound (b) was again -20 to 100 ° C in the presence of the aromatic hydrocarbon compound. To obtain a solid product (2). If necessary, intermediate cleaning and reaction treatment may be repeated a plurality of times. Next, the solid product (2) is washed with a hydrocarbon compound that is liquid at room temperature by decantation to obtain the solid catalyst component (A).

  The ratio of the amount of each component used in preparing the solid catalyst component (A) varies depending on the preparation method, and thus cannot be determined 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.

  Further, the content of titanium, magnesium, halogen atom and electron donating compound in the solid catalyst component (A) in the present invention is not particularly defined, but preferably 0.5 to 8.0% by weight, preferably 1% of titanium. 0.0-8.0 wt%, preferably 2.0-8.0 wt%, magnesium is 10-70 wt%, more preferably 10-50 wt%, particularly preferably 15-40 wt%, still more preferably 15 to 25% by weight, halogen atom 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 the total amount of electron donating compounds is 0 0.5 to 30% by weight, more preferably 1 to 25% by weight, 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 (2). As long as there is no particular limitation, R ⁴ 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, and 3 is particularly preferable. Specific examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, and diethylaluminum hydride, and one or more of these can be used. Triethylaluminum and triisobutylaluminum are preferable.

  As the aminosilane compound (C) (hereinafter sometimes referred to as “component (C)”) used in forming the olefin polymerization catalyst of the present invention, a compound represented by the above general formula (1) is used. . Specific examples of the compound include those described above.

  In the olefin polymerization catalyst of the present invention, in addition to the above components (A), (B), and (C), electron donation such as organosilicon compounds or ether compounds other than the aminosilane compounds described above in order to further improve the catalyst performance. (Hereinafter sometimes simply referred to as “component (D)”) can be used.

  Examples of organosilicon compounds other than aminosilane compounds include di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyl (methyl) dimethoxysilane, t- Butyl (ethyl) dimethoxysilane, dicyclohexyl dimethoxysilane, cyclohexyl (methyl) dimethoxysilane, dicyclopentyl dimethoxysilane, cyclopentyl (methyl) diethoxysilane, cyclopentyl (ethyl) dimethoxysilane, cyclopentyl (cyclohexyl) dimethoxysilane, 3-methylcyclohexyl ( Cyclopentyl) dimethoxysilane, 4-methylcyclohexyl (cyclopentyl) dimethoxysilane, 3,5-dimethylcyclohexyl (cyclopentyl) Dimethoxysilane, bis (diethylamino) dimethoxysilane, bis (di-n-propylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t-butylamino) dimethoxysilane, bis (dicyclopentyl) Amino) dimethoxysilane, bis (dicyclohexylamino) dimethoxysilane, bis (di-2-methylcyclohexylamino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (ethyl- n-propylamino) dimethoxysilane, bis (ethylisopropylamino) dimethoxysilane, bis (ethyl-n-butylamino) dimethoxysilane, bis (ethylisobutylamino) dimethoxysilane, bis (ethyl-t- Tilamino) dimethoxysilane, bis (isobutyl-n-propylamino) dimethoxysilane, bis (ethylcyclopentylamino) dimethoxysilane, bis (ethylcyclohexylamino) dimethoxysilane, ethyl (diethylamino) dimethoxysilane, n-propyl (diisopropylamino) dimethoxy Silane, isopropyl (di-t-butylamino) dimethoxysilane, cyclohexyl (diethylamino) dimethoxysilane, ethyl (di-t-butylamino) dimethoxysilane, ethyl (perhydroisoquinolino) dimethoxysilane, n-propyl (perhydro) Isoquinolino) dimethoxysilane, isopropyl (perhydroisoquinolino) dimethoxysilane, n-butyl (perhydroisoquinolino) dimethoxysilane, ethyl Hydroquinolino) dimethoxysilane, n-propyl (perhydroquinolino) dimethoxysilane, isopropyl (perhydroquinolino) dimethoxysilane, n-butyl (perhydroquinolino) dimethoxysilane, bis (diethylamino) diethoxysilane, bis (di-n- Propylamino) diethoxysilane, bis (di-n-butylamino) diethoxysilane, bis (di-t-butylamino) diethoxysilane, bis (dicyclopentylamino) diethoxysilane, bis (dicyclohexylamino) diethoxy Silane, bis (di-2-methylcyclohexylamino) diethoxysilane, bis (perhydroisoquinolino) diethoxysilane, bis (perhydroquinolino) diethoxysilane, bis (ethyl-n-propylamino) diethoxysilane Bis (ethylisopropylamino) diethoxysilane, bis (ethyl-n-butylamino) diethoxysilane, bis (ethyl-isobutylamino) diethoxysilane, bis (ethyl-t-butylamino) diethoxysilane, bis (isobutyl) -N-propylamino) diethoxysilane, bis (ethylcyclopentylamino) diethoxysilane, bis (ethylcyclohexylamino) diethoxysilane, n-propyl (diisopropylamino) diethoxysilane, ethyl (perhydroisoquinolino) di Ethoxysilane, n-propyl (perhydroisoquinolino) diethoxysilane, isopropyl (perhydroisoquinolino) diethoxysilane, n-butyl (perhydroisoquinolino) diethoxysilane, ethyl (perhydroquinolino) dieto Sisilane, n-propyl (perhydroquinolino) diethoxysilane, isopropyl (perhydroquinolino) diethoxysilane, n-butyl (perhydroquinolino) diethoxysilane, texyltrimethoxysilane, diethylaminotrimethoxysilane, di-n -Propylaminotrimethoxysilane, di-n-butylaminotrimethoxysilane, di-t-butylaminotrimethoxysilane, dicyclopentylaminotrimethoxysilane, dicyclohexylaminotrimethoxysilane, di-2-methylcyclohexylaminotrimethoxysilane Perhydroisoquinolinotrimethoxysilane, perhydroquinolinotrimethoxysilane, diethylaminotriethoxysilane, di-n-propylaminotriethoxysilane, di-n-butylaminotri Ethoxysilane, ethyl-t-butylaminotriethoxysilane, ethyl-sec-butylaminotriethoxysilane, dicyclopentylaminotriethoxysilane, dicyclohexylaminotriethoxysilane, di-2-methylcyclohexylaminotriethoxysilane, perhydroiso Quinolinotriethoxysilane, perhydroquinolinotriethoxysilane, bis (t-butylamino) dimethoxysilane, bis (cyclohexylamino) dimethoxysilane, bis (t-butylamino) diethoxysilane, bis (cyclohexylamino) diethoxysilane , Trivinylmethylsilane, and tetravinylsilane.

  Examples of the ether compound include methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, diphenyl ether, 9,9-bis (methoxymethyl) fluorene, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane and the like. Can be mentioned. These electron donating compounds (D) can be used alone or in combination of two or more.

  In the presence of the olefin polymerization catalyst of the present invention, homopolymerization, random copolymerization or block copolymerization of olefins is carried out. 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 propylene, copolymerization with other olefins can be performed. Examples of the olefin 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. Copolymerization of propylene and other olefins includes random copolymerization in one stage using propylene and a small amount of ethylene as a comonomer, and homopolymerization of propylene in the first stage (first polymerization tank). The so-called propylene-ethylene block copolymerization in which propylene and ethylene are copolymerized in a stage (second polymerization tank) or more stages (multistage polymerization tank) is typical. Even in such random copolymerization and block copolymerization, the catalyst of the present invention comprising the component (A), the component (B) and the component (C) is effective, and has catalytic activity, stereoregularity and / or hydrogen. Not only is the response good, but the copolymerization properties and the properties of the resulting copolymer are also good.

  In the homopolymerization, random copolymerization or block copolymerization of the above olefins, the component (D) described above may be mixed and used in addition to the component (C) which is the catalyst component of the present invention. The component (C) and the component (D) can be used separately in the polymerization tank.

  Also, when shifting from homopolymerization of propylene to block copolymerization, known electron donating compounds such as alcohols, oxygen gas or ketones should be added to the polymerization system in order to prevent gel formation in the final product. Can do. Specific examples of alcohols include ethyl alcohol, isopropyl alcohol and the like, and the amount used is 0.01 to 10 mol, preferably 0.1 to 2 mol, per 1 mol of component (B).

  The amount of each component used is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, component (B) is used per 1 mole of titanium atom in 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 0.1 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). Further, it is used in an amount of 0.001 to 10 mol, preferably 0.01 to 10 mol, particularly preferably 0.01 to 2 mol, per mol of the component (C).

  The order of contact of each component is arbitrary, but first, the organoaluminum compound (B) is charged into the polymerization system, and then the aminosilane compound (C) is contacted or premixed with the component (C) and the component (D It is desirable to contact the solid catalyst component (A) by contacting the component (C) and the component (D) in any order. Alternatively, the organoaluminum compound (B) is first charged into the polymerization system, while the component (A) and the component (C), or the component (C) and the component (D) are previously contacted and contacted. It is also a preferred embodiment that (A) and component (C) or component (C) and component (D) are charged into and contacted with each other to form a catalyst. Thus, it is possible to further improve the hydrogen response of the catalyst and the crystallinity of the produced polymer by previously treating the component (A) with the component (B) or the component (C) and the component (D). Become.

  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 for polymerization 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 6 MPa or lower. In addition, either a continuous polymerization method or a batch polymerization method is possible. Furthermore, the polymerization reaction may be performed in one stage, or may be performed in two or more stages.

  Furthermore, in polymerizing olefins using the catalyst formed from component (A), component (B) and component (C) in the present invention (also referred to as “main polymerization”), catalytic activity, stereoregularity and production In order to further improve the particle properties and the like, 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. And then contact component (C) and / or component (D), then contact component (A), and then contact olefin such as propylene and / or one or more other olefins. Let The prepolymerization temperature is arbitrary and is not particularly limited, but is preferably in the range of -10 ° C to 70 ° C, more preferably in the range of 0 ° C to 50 ° C.

  When olefins are polymerized in the presence of the olefin polymerization catalyst of the present invention, high stereoregularity is maintained and hydrogen response is improved as compared with the case where a conventional catalyst is used. Moreover, compared with the case where the conventional catalyst is used resulting from the specific structure of a component (C), catalyst activity and stereoregularity are improving. That is, when the catalyst of the present invention is used for the polymerization of olefins, the structure of component (C) maintains high stereoregularity, improves hydrogen response, and improves catalytic activity and stereoregularity. Was confirmed.

  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.

Reference example 1
<Synthesis of Aminosilane Compound>
Into a three-necked flask thoroughly purged with nitrogen gas, 70 ml of a toluene solution containing 0.1 mol of trichlorosilane was poured under a nitrogen stream, and the mixture was cooled to −10 ° C. with stirring. 50 ml of a THF solution containing 0.1 mol of t-BtMgCl was gradually added dropwise to the cooling liquid using a dropping funnel. After completion of dropping, the reaction was performed at 40 ° C. for 2 hours to complete the reaction. Next, the solid and the solution were separated using a centrifugal separation method under a nitrogen stream. The solid was washed twice with an additional 20 ml of toluene and added to the solution.

  Next, 50 ml of a THF solution containing 0.4 mol of methylamine was poured into a three-necked flask thoroughly purged with nitrogen gas under a nitrogen stream and cooled to −10 ° C. with stirring. The solution of the reaction mixture obtained by the above reaction was gradually added dropwise to the cooled solution using a dropping funnel. After completion of the dropwise addition, the reaction was completed with stirring at 10 ° C. for 3 hours. The resulting amine hydrochloride was separated by centrifugation under a nitrogen stream to obtain a solution of the reaction mixture.

  The solvent and excess methylamine were distilled off under reduced pressure, and the main product, bis (methylamino) t-butylsilane, was purified by distillation under reduced pressure. The product was identified from C, H, N elemental analysis. As a result, C was 49.30% (49.26%), H was 12.32% (12.40%), and N was 19.09% (19.15%). Theoretical amount).

Reference example 2
<Synthesis of aminosilane compound>
Into a three-necked flask thoroughly purged with nitrogen gas, 70 ml of a toluene solution containing 0.1 mol of ditrimethylsilylamine was poured under a nitrogen stream, and the mixture was cooled to −10 ° C. with stirring. Next, 50 ml of a diisopropyl ether solution containing 0.1 mol of BuMgCl was gradually added dropwise to the amine solution using a dropping funnel. After completion of the dropwise addition, the mixture was reacted at 50 ° C. for 2 hours to obtain a slurry of magnesium salt of ditrimethylsilylamine.

  Next, 70 ml of a toluene solution containing 0.1 mol of trichlorosilane was poured into a three-necked flask sufficiently purged with nitrogen gas under a nitrogen stream and cooled to −10 ° C. with stirring. Under stirring, the whole amount of the slurry of ditrisilylmethylamine magnesium salt was added to the cooling liquid using a dropping funnel. The solid and the solution were separated by centrifugation under a nitrogen stream, the solid was washed twice with 20 ml of toluene, and the washing solution was added to the above solution.

  Next, 50 ml of a THF solution containing 0.4 mol of ethylamine was poured into a three-necked flask thoroughly purged with nitrogen gas under a nitrogen stream and cooled to −10 ° C. with stirring. Next, the solution of the reaction mixture obtained by the above reaction was gradually dropped into this cooling solution using a dropping funnel. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 50 ° C. for 3 hours. The produced ethylamine hydrochloride was separated under a nitrogen stream, the solvent was distilled off from the reaction solution by distillation under reduced pressure, and the main product bis (ethylamino) ditrimethylsilylaminosilane was purified and separated by distillation under reduced pressure. The product was identified from elemental analysis of C, H and N streams. As a result, C was 43.30% (43.26%), H was 11.32% (11.25%), and N was 15.10% (15.14%). Theoretical amount).

Reference example 3
<Synthesis of aminosilane compound>
Under a nitrogen stream, 60 ml of a toluene solution containing 0.05 mol of perhydroisoquinoline was poured into a three-necked flask thoroughly purged with nitrogen gas, and cooled to −10 ° C. with stirring. A commercially available butyllithium hexane solution was diluted with hexane, and 60 ml of a hexane solution containing 0.1 mol of butyllithium was gradually added to a toluene solution cooled to −10 ° C. under a nitrogen stream using a dropping funnel. It was dripped in. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 60 ° C. for 2 hours. Thus, a slurry of lithium salt of perhydroisoquinoline was obtained.

  Next, 50 ml of a toluene solution containing 0.05 mol of trichlorosilane was poured into a three-necked flask thoroughly purged with nitrogen gas under a nitrogen stream and cooled to −10 ° C. with stirring. The whole amount of the perhydroisoquinoline lithium salt slurry was added to the cooling liquid with stirring using a dropping funnel. After completion of dropping, the reaction was carried out at 60 ° C. for 3 hours. After completion of the reaction, the solid and the solution were separated by centrifugation under a nitrogen stream, the solid was washed twice with 20 ml of toluene, and the washing solution was added to the above solution.

  Next, 50 ml of a THF solution containing 0.2 mol of ethylamine was poured into a three-necked flask thoroughly purged with nitrogen gas under a nitrogen stream and cooled to −10 ° C. with stirring. The solution of the reaction mixture obtained by the above reaction was gradually added dropwise to the cooled solution using a dropping funnel. After completion of the dropwise addition, the temperature was gradually raised and the reaction was carried out at 60 ° C. for 3 hours. The produced ethylamine hydrochloride was separated under a nitrogen stream, the reaction solution was distilled under reduced pressure, the solvent was distilled off, and the main product bis (ethylamino) perhydroisoquinolinosilane was purified and separated by vacuum distillation. . The product was identified from elemental analysis of C, H and N streams. As a result, C was 61.10% (61.12%), H was 11.32% (11.44%), and N was 16.32% (16.45%). Theoretical amount).

<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 n-butyl phthalate was added and the temperature was raised to 100 ° C., followed by reaction treatment with stirring for 2 hours. 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. The intermediate wash and the second treatment were repeated once more. The product was then washed 7 times with 1300 ml of 40 ° C. heptane, filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid component was measured and found to be 3.1% by weight.

<Formation and polymerization of polymerization catalyst>
In an autoclave equipped with a stirrer with an internal volume of 2.0 liters completely substituted with nitrogen gas, 1.32 mmol of triethylaluminum, 0.13 mmol of bis (methylamino) t-butylsilane obtained in Reference Example 1 and the solid catalyst component were added. As a titanium atom, 0.0026 mmol was charged to form a polymerization catalyst. Thereafter, 4 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. With respect to the obtained polymer, the catalyst activity, bulk specific gravity (BD, g / ml), heptane insoluble content (HI, wt%), and melt flow rate according to ASTM are melt index (MI, g-PP / 10 min). It showed in. The molecular weight distribution of the polymer was also measured. The results are shown in Table 1.

  The catalytic activity indicating the amount of polymer produced (F) g per hour of the polymerization time per 1 g of the solid catalyst component was calculated by the following equation.

Catalytic activity = product polymer (F) g / solid catalyst component g / 1 hour

  Further, after the polymer was continuously extracted with boiling n-heptane for 6 hours, the polymer (G) insoluble in n-heptane was dried and weighed, and the insoluble content of boiling heptane in the polymer (HI, % By weight) was calculated from the following formula.

HI (% by weight) = (G) g / (F) g × 100

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

The molecular weight distribution of the polymer is determined by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn obtained by measurement under the following conditions in a cross fractionation chromatograph (CFC) (CFC T-150B manufactured by Mitsubishi Chemical Corporation). evaluated.
Solvent: o-dichlorobenzene (ODCB)
Temperature: 140 ° C (SEC)
Column: Shodex GPC UT-806M
Sample concentration: 4g / liter-ODCB (200mg / 50ml-ODCB)
Injection volume: 0.5ml
Flow rate: 1.0ml / min
Measurement range: 0 ° C-140 ° C

  An experiment was conducted in the same manner as in Example 1 except that bis (ethylamino) ditrimethylsilylaminosilane obtained in Reference Example 2 was used instead of bis (methylamino) t-butylsilane. The obtained results are shown in Table 1.

  The experiment was performed in the same manner as in Example 1 except that bis (ethylamino) perhydroisoquinolinosilane obtained in Reference Example 3 was used instead of bis (methylamino) t-butylsilane. The obtained results are shown in Table 1.

<Preparation of solid catalyst component>
A 500 ml round bottom flask equipped with a stirrer and thoroughly substituted with nitrogen gas was charged with 4.76 g of anhydrous magnesium chloride, 25 ml of decane and 23.4 ml of 2-ethylhexyl alcohol, and at 130 ° C. for 2 hours. Reaction was performed to obtain a homogeneous solution. Next, 1.11 g of phthalic anhydride was added to the homogeneous solution and reacted at 130 ° C. for 1 hour. Next, the entire amount of the solution was dropped into 200 ml of titanium tetrachloride equipped with a stirrer and sufficiently substituted with nitrogen gas and charged at a volume of 500 ml and maintained at −20 ° C. over 1 hour. did. Subsequently, after heating up this mixed solution to 110 degreeC over 4 hours, 2.68 ml of diisobutyl phthalate was added and it was made to react for 2 hours. After completion of the reaction, the liquid part is removed by filtration, and the remaining solid component is washed with decane and hexane at 110 ° C. until no free titanium compound is detected, filtered and dried to obtain a powdered solid catalyst component. It was. The titanium content in the solid catalyst component was measured and found to be 3.1% by weight.

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

<Preparation of solid catalyst component>
32 g of ground magnesium for Grignard was charged into a 1000 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas. Next, a mixed liquid of 120 g of butyl chloride and 500 ml of dibutyl ether was dropped into the magnesium over 4 hours at 50 ° C., and then reacted at 60 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to room temperature and solid content was removed by filtration to obtain a magnesium compound solution. Next, a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas was charged with 240 ml of hexane, 5.4 g of tetrabutoxytitanium and 61.4 g of tetraethoxysilane to obtain a homogeneous solution. The magnesium compound solution (150 ml) was added dropwise at 5 ° C. over 4 hours to react, and then stirred at room temperature for 1 hour. Next, the reaction solution was filtered at room temperature to remove the liquid portion, and then the remaining solid was washed with 240 ml of hexane 8 times and dried under reduced pressure to obtain a solid product. Then, 8.6 g of the solid product was charged into a 100-ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas, and further 48 ml of toluene and 5.8 ml of diisobutyl phthalate were added. The reaction was carried out at 1 ° C. for 1 hour. Thereafter, the liquid part was removed by filtration, and the remaining solid was washed 8 times with 85 ml of toluene. After completion of washing, 21 ml of toluene, 0.48 ml of diisobutyl phthalate and 12.8 ml of titanium tetrachloride were added to the flask and reacted at 95 ° C. for 8 hours. After completion of the reaction, solid-liquid separation is performed at 95 ° C., and the solid content is washed twice with 48 ml of toluene. Then, the treatment with the above mixture of diisobutyl phthalate and titanium tetrachloride is performed again under the same conditions, and washed with 48 ml of hexane eight times. Filtered and dried to obtain a powdered solid catalyst component. The titanium content in the solid catalyst component was measured and found to be 2.1% by weight.

<Formation and polymerization of polymerization catalyst>
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that the solid catalyst component obtained above was used. The 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 in place of bis (methylamino) t-butylsilane to form a polymerization catalyst, and the polymerization catalyst was formed and polymerized. Went. The obtained results are shown in Table 1.

Comparative Example 2
A solid catalyst component was prepared in the same manner as in Example 1 except that bis (diethylamino) dimethoxy was used in place of bis (methylamino) t-butylsilane to form a polymerization catalyst, and the polymerization catalyst was formed. Polymerization was performed. The obtained results are shown in Table 1.

Comparative Example 3
A polymerization catalyst was formed and polymerized in the same manner as in Example 1 except that diisopropylaminotriethoxysilane was used instead of bis (methylamino) t-butylsilane to form and polymerize the polymerization catalyst. The obtained results are shown in Table 1.

  From the above results, it can be seen that when an aminosilane compound is used at the time of polymerization, a polymer with high stereoregularity can be obtained in good yield and the hydrogen response is good. Moreover, it turns out that the molecular weight distribution of the polymer obtained with an aminosilane compound becomes wide.

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

Claims (5)

The following general formula (1);
R ¹ _m HSi (NR ² R ³ ) _3-m (1)
(Wherein, m is an integer of 0 or 1 and 2, R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, An alkylsilyl group, an aminoalkylsilyl group, which may contain a hetero atom, and may be the same or different, and when m is 2, two R ¹ may be bonded to each other to form a ring; R ² and R ³ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, a trialkylsilyl group, the same or And R ² and R ³ may be bonded to each other to form a ring.) An olefin polymerization catalyst comprising an aminosilane compound represented by (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound;
(B) the following general formula (2);
R ⁴ _p AlQ _3−p (2)
(Wherein R ⁴ 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 (1);
R ¹ _m HSi (NR ² R ³ ) _3-m (1)
(Wherein, m is an integer of 0 or 1 and 2, R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, An alkylsilyl group, an aminoalkylsilyl group, which may contain a hetero atom, and may be the same or different, and when m is 2, two R ¹ may be bonded to each other to form a ring; R ² and R ³ are a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group and derivatives thereof, a vinyl group, an allyl group, an aralkyl group, a trialkylsilyl group, the same or And R ² and R ³ may be bonded to each other to form a ring.)
Olefin polymerization catalyst formed from   2. The olefin according to claim 1, wherein the solid catalyst component is obtained by contacting a magnesium compound (a), a tetravalent titanium halogen compound (b) and an electron donating compound (c). Polymerization catalyst.   A method for producing an olefin polymer, comprising polymerizing olefins in the presence of the olefin polymerization catalyst according to any one of claims 2 and 3.   The method for producing an olefin polymer according to claim 4, wherein the olefin polymer is a propylene polymer.

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