JP3444730B2 - Solid catalyst components and catalysts for olefin polymerization - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymer having high stereoregularity and excellent particle properties when subjected to polymerization of olefins, and particularly having high bulk specific gravity and low fine powder content. The present invention relates to a solid catalyst component for olefin polymerization obtained in high yield and an olefin polymerization catalyst formed using the solid catalyst component, and further, in the block copolymerization of olefin, the production ratio of a rubber-like polymer is The present invention relates to a solid catalyst component for olefin polymerization and a catalyst that can obtain a copolymer having excellent particle properties in a high yield even if it is increased.

[0002]

2. Description of the Related Art A solid catalyst component containing a titanium halogen compound, a magnesium compound and an electron-donating compound as essential components, and a catalyst formed from a third component such as the solid catalyst component, an organoaluminum compound and a silicon compound are used. As to the method for polymerizing olefins, many proposals have been made and are well known.

Further, a solid catalyst component prepared by using dialkoxymagnesium and titanium tetrachloride as main starting materials, and an olefin polymerization for forming with the solid catalyst component and a third component such as an organoaluminum compound and a silicon compound. As for the catalyst, for example, JP-A-63-3010, JP-A-1-221405, JP-A-1-315406, JP-A-3-227309, JP-A-3-70711, and JP-A-4-70141. There are many disclosures in addition to the publication such as the 8709 publication, which are known.

Each of the above-mentioned prior arts has such a high activity that it can eliminate a so-called deashing step of removing catalyst residues such as chlorine and titanium remaining in the produced polymer when used as a catalyst for propylene polymerization. It started with the development of catalyst components, and also focused on improving the yield of stereoregular polymers and increasing the sustainability of polymerization activity during polymerization. Has achieved results.

However, when olefins are polymerized by using a polymerization catalyst having a composition of this type of highly active catalyst component and an electron donating compound represented by an organoaluminum compound and a silicon compound, a solid catalyst component is obtained. Because of the fine powder of itself or the particle destruction due to the reaction heat during polymerization, the resulting polymer contains a large amount of fine powder, and the particle size distribution is broadened,
As a result, there was a tendency that the bulk specific gravity of the produced polymer was lowered. If the amount of this fine powder polymer increases, it may hinder the continuation of a uniform reaction, cause blockage of the piping in the polymerization process, or cause troubles in the polymer separation and drying steps, which is a problem to be improved. In addition, when the particle size distribution is widened, it adversely affects the molding and processing of the polymer, and when the bulk specific gravity is decreased, there is a problem that the productivity is significantly decreased. This is a factor that seeks a polymer having a small amount of coalescence and a high bulk specific gravity.

As means for solving this problem, a solid catalyst component containing a magnesium compound such as a magnesium dihalide or an alkyl magnesium compound, a titanium compound, an electron-donating compound and polysiloxane as essential components, and the solid catalyst component, organoaluminum Many proposals have been made for well known methods of polymerizing olefins using a catalyst formed of a compound and a third component such as a silicon compound.

For example, in JP-A-61-204202, for the olefin polymerization, a contact product of magnesium dihalide, titanium tetraalkoxide and hydrogenated polysiloxane, an acid halogen compound and a halogen compound of silicon are contacted. A catalyst component is disclosed. Further, in Japanese Patent Laid-Open No. 56-152811,
Disclosed is a method for producing a polyolefin, which comprises polymerizing an olefin in the presence of a catalyst containing a combination of a titanium-containing solid catalyst component derived from an alkyl magnesium compound, a polysiloxane, an organic acid ester and a titanium compound and an organometallic compound. There is.

On the other hand, in JP-A-6-157659, a mixed solution of aromatic hydrocarbon and titanium tetrachloride is used.
A catalyst for the polymerization of olefins has been proposed which comprises a solid catalyst component obtained by adding a spherical suspension of dialkoxy magnesium, an aromatic hydrocarbon and a phthalic acid diester to a reaction and then reacting it with titanium tetrachloride. There is.

Further, in JP-A-6-287225, a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic acid diester is added to a mixed solution of aromatic hydrocarbon and titanium tetrachloride. An olefin characterized by being obtained by reacting, washing the obtained reaction product with an aromatic hydrocarbon, again reacting with titanium tetrachloride to obtain a solid component, and then drying the solid component, followed by a fine powder removing treatment step. Solid catalyst components for polymerization have been proposed.

Further, in JP-A-6-287217, a suspension of spherical dialkoxymagnesium, an aromatic hydrocarbon and a phthalic acid diester is added to a mixed solution of an aromatic hydrocarbon and titanium tetrachloride to carry out a reaction. The resulting reaction product is washed with an aromatic hydrocarbon, and the solid component obtained by reacting it with titanium tetrachloride again is dried and subjected to a fine powder removal treatment. There has been proposed a solid catalyst component for olefin polymerization, which is obtained through a treatment step of adding an agent.

Although each of the above-mentioned prior arts has the effect of removing fine powder of the solid catalyst component itself and reducing the amount of fine powder of the polymer produced as a result, as described above, particularly during the polymerization reaction. The fine powder generated by particle destruction due to the reaction heat in the initial stage has not yet been controlled, and the fine powder still exists in the produced polymer.

Further, the polymers produced in these prior arts have good morphology, but their bulk specific gravity is low, and in the production of polyolefin, the production amount of the polymer per unit volume in the polymerization tank is small, There is still a problem that the productivity of the entire polyolefin production is lowered as a result of the limitation of the throughput of the polymer transportation or pelletizing step. Further, even if a polymer having a relatively high bulk specific gravity is obtained, there is a problem that the polymerization activity is lowered or the stereoregularity is lowered. By the way, in order to save energy or save resources related to global environmental problems in recent years, it has been strongly desired to reduce the weight of plastics used in automobiles, home electric appliances and the like. In order to solve this problem, it is necessary to reduce the thickness of the plastic molded product while maintaining mechanical strength such as impact resistance, which further improves the stereoregularity and crystallinity of the resin and increases its rigidity. Therefore, there is a demand for the development of a catalyst for producing a polyolefin capable of obtaining improved stereoregularity or crystallinity.

On the other hand, in the presence of various conventional types of solid catalyst components or catalysts as described above, a crystalline polymer of propylene homopolymer is produced in the first step, and the propylene homopolymer of the propylene homopolymer is produced in the second step. Propylene and other olefins in the coexistence,
For example, it is known to produce a block copolymer of propylene by copolymerizing ethylene, 1-butene and the like. Since such a block copolymer contains a rubbery copolymer in a proportion thereof, impact resistance is improved while having excellent rigidity of crystalline polypropylene, for example, container, bumper, etc. Auto parts,
It is used in many applications such as films requiring low-temperature heat-sealing properties.

In order to further improve the impact resistance of this block copolymer, it is necessary to increase the proportion of the rubbery copolymer (eg ethylene-propylene rubber) formed in the block copolymer. is there. However, as the production ratio of the rubbery copolymer increases, the tackiness of the produced block copolymer particles increases. For this reason, in the gas phase polymerization process or the bulk polymerization process, the fluidity of the produced polymer particles is extremely deteriorated, and further, the produced polymer particles adhere to each other to cause aggregation, adhesion to the inner wall of the polymerization apparatus, etc. It causes a big trouble.

For the purpose of improving the fluidity of the produced block copolymer particles, the adhesion of particles to each other, and the adhesion in the apparatus, for example, JP-A-61-69821 and JP-A-61-69822. In the publication, there is proposed a method of supplying an active hydrogen compound such as ethanol or an oxygen-containing compound such as oxygen gas to the polymerization system in the polymerization in the second step, that is, the step of producing a rubbery copolymer. . However, such an active hydrogen compound or an oxygen-containing compound originally lowers the activity of the catalyst in olefin polymerization, and it is necessary to strictly control the supply amount in the process as well, and improvement in the equipment is required. is necessary.

[0016]

SUMMARY OF THE INVENTION The present invention has been made to solve the various problems remaining in the prior art as described above. That is, the object of the present invention, when subjected to the polymerization of olefins, while maintaining a high polymerization activity and a high stereoregular polymer yield, a polymer having a high bulk specific gravity and a small fine powder content is obtained. To provide a solid catalyst component and a catalyst.

Still another object of the present invention is to increase the production ratio of rubbery copolymer in block copolymerization,
An object of the present invention is to provide a solid catalyst component and a catalyst for olefin polymerization capable of maintaining good particle properties.

[0018]

Means for Solving the Problems The solid catalyst component (A) for olefin polymerization according to the present invention for achieving the above object is constituted by using the following components (a) to (d): Characterize above. (a) General formula Mg (OR ¹ ) ₂ (In the formula, R ¹ has 1 to ¹ carbon atoms.
4 represents an alkyl group or an aryl group. ) A dialkoxymagnesium or diaryloxymagnesium, (b) a general formula Ti (OR ² ) _p X _4-p (in the formula, R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen element, p is 0
Alternatively, it is an integer of 1 to 3. ), A titanium compound (c), an aromatic dicarboxylic acid diester, and (d) a cyclic polysiloxane represented by the following general formula (1) or a general formula (2) below. Chain polysiloxane

[Chemical 3] (In the formula, R ⁶ to R ¹¹ are each independently a methyl group.
Or an ethyl group, and n is an integer of 1 to 20.
It )

[Chemical 4] (In the formula, x represents an average degree of polymerization, and is 2 to 30,000.
There, the subject of R ¹³ and R ¹⁸ are methyl groups, R ^12, R
¹⁴ to R ¹⁷ and a part of R ¹⁹ are phenyl groups and higher fatty acid residues
Group, epoxy-containing group, polyoxyalkylene group substituted
Including those )

The olefin polymerization catalyst according to the present invention is characterized in that it is formed by the above solid catalyst component (A) and the following components (B) and (C). (B) General formula R ³ _q AlY _3-q (In the formula, R ³ has 1 carbon atom.
To 4 alkyl groups, Y is any of hydrogen, chlorine, bromine, and iodine, and q is a real number satisfying 0 <q ≦ 3. ), And (C) the general formula R ⁴ _r Si (OR ⁵ ) _4-r (wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, an allyl group). , a vinyl group, in any of the aralkyl group may .R ⁵ be the same or different is 1 to carbon atoms
4 alkyl groups, cycloalkyl groups, phenyl groups, vinyl groups, allyl groups and aralkyl groups, which may be the same or different. r is 0 or an integer of 1 to 3. ) An organosilicon compound represented by:

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Components constituting the solid catalyst component (A) of the present invention (hereinafter sometimes referred to as "component (A)").
The general formula Mg (OR ¹ ) _{2 of} (a) (wherein R ¹ is a carbon number 1
4 represents an alkyl group or an aryl group. ) Dialkoxymagnesium or diaryloxymagnesium (hereinafter sometimes referred to as “component (a)”)
As, dimethoxy magnesium, diethoxy magnesium, di-n-propoxy magnesium, di-iso
-Propoxymagnesium, di-n-butoxymagnesium, di-iso-butoxymagnesium, diphenoxymagnesium, ethoxymethoxymagnesium, ethoxy-n-propoxymagnesium, n-butoxyethoxymagnesium, iso-butoxyethoxymagnesium and the like, or 2 There can be more than one species,
Among them, diethoxy magnesium or di-n-propoxy magnesium is preferably used.

Further, the dialkoxymagnesium or diaryloxymagnesium may be in the form of granules or powder, and the shape thereof may be amorphous or spherical. When spherical dialkoxymagnesium or diaryloxymagnesium 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. However, troubles such as clogging caused by the fine powder contained in the produced polymer powder are eliminated.

The spherical dialkoxymagnesium or diaryloxymagnesium described above does not necessarily have to be a true sphere, and those having an elliptical or potato-like shape are used. Specifically, the degree of spherical shape of the particle is
The ratio (l / w) of the major axis diameter 1 to the minor axis diameter w is 3 or less, preferably 1 to 2, and more preferably 1 to 1.5.

The average particle size of the dialkoxymagnesium or diaryloxymagnesium may be from 1 to 200 microns, but is preferably from 5 to 150 microns. Further, the specific surface area was 50 m ² / g from 5 m ² / g, preferably 10 m ²
/ g to 40 m ² / g, more preferably 15 m ² / g to 30 m ² / g
Is.

The average particle size of the spherical dialkoxymagnesium or diaryloxymagnesium is 1 μm to 100 μm, preferably 5 to 50 μm, more preferably 10 to 40 μm. Regarding the particle size, it is desirable to use one having a small particle size or coarse powder and a sharp particle size distribution. Specifically, 5μ
Particles of m or less are 20% or less, preferably 10% or less, and particles of 100 μm or more are 10% or less, preferably 5% or less.
% Or less. Furthermore, the particle size distribution is calculated as ln (D90 /
D10) (where D90 is the particle size at 90% of the integrated particle size and D10 is the particle size at 10% of the integrated particle size) is 3 or less, preferably 2 or less.

Further, when spherical dialkoxymagnesium or diaryloxymagnesium is used, J
The bulk specific gravity measured according to ISK6721 is usually 0.2.
0 to 0.35 g / ml is used. Generally, when olefin polymerization is performed using a solid catalyst component prepared by using spherical bulky dialkoxy magnesium or diaryloxy magnesium having a high bulk specific gravity, a polymer having a higher bulk specific gravity is obtained, but in the present invention, for example, 0.25g /
Even if spherical dialkoxy magnesium or diaryloxy magnesium having a relatively low bulk specific gravity of less than ml is used,
The bulk specific gravity of the obtained polymer does not decrease, and a polymer having a high bulk specific gravity can be obtained.

Next, the component (b) used in preparing the solid catalyst component (A) of the present invention is represented by the general formula Ti (OR ² ) _p X _4-p
(In the formula, R ² is an alkyl group having 1 to 4 carbon atoms, X is a halogen element, and p is 0 or an integer of 1 to 3.) A titanium compound (hereinafter referred to as “component (b)”). And a titanium halide or an alkoxytitanium halide. Specifically, as titanium tetrahalide, TiCl ₄ , TiBr ₄ , TiI
₄ , as an alkoxy titanium halide, Ti (OC
H ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (OC
₃ H ₇ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti
_{(OCH 3) 2 Cl 2,} Ti (OC 2 H 5) 2 Cl 2, Ti
_{(OC 3 H 7) 2 Cl} 2, Ti (On-C 4 H 9) 2 C
l ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ C
_{l, Ti (OC 3 H 7} ) 3 Cl, Ti (On-C 4 H 9) 3
Cl etc. are illustrated. Among them, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable. You may use these titanium compounds 1 type (s) or 2 or more types.
Further, these components (b) may be dissolved in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane, and may be diluted before use.

The aromatic dicarboxylic acid diester of component (c) used in preparing the solid catalyst component (A) of the present invention (hereinafter sometimes referred to as "component (c)") is particularly carbon of phthalic acid. Linear or branched alkyl diesters of the formulas 1 to 12 are preferred. Specific examples of the diester of phthalic acid include dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate and di-is.
o-propyl phthalate, di-n-butyl phthalate,
Di-iso-butyl phthalate, ethyl methyl phthalate, butyl ethyl phthalate, methyl (iso-propyl) phthalate, ethyl (n-propyl) phthalate, ethyl (n-butyl) phthalate, di-n-pentyl phthalate, di-iso -Pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-
n-octyl phthalate, bis (2-methylhexyl)
Phthalate, bis (2-ethylhexyl) phthalate,
Di-n-nonyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl) phthalate,
n-butyl (iso-hexyl) phthalate, ethyl (iso-octyl) phthalate, n-butyl (iso)
-Octyl) phthalate, n-pentylhexylphthalate, n-pentyl (iso-hexyl) phthalate,
iso-pentyl (heptyl) phthalate, n-pentyl (iso-octyl) phthalate, n-pentyl (i
so-nonyl) phthalate, iso-pentyl (n-decyl) phthalate, n-pentyl (undecyl) phthalate, iso-pentyl (iso-hexyl) phthalate, n-hexyl (iso-octyl) phthalate, n
-Hexyl (iso-nonyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (iso-)
Octyl) phthalate, n-heptyl (iso-nonyl) phthalate, n-heptyl (neo-decyl) phthalate, iso-octyl (iso-nonyl) phthalate, dicyclohexyl phthalate, butylbenzyl phthalate are exemplified, and one or two of them are exemplified. More than one seed is used. Of these, diethyl phthalate, di-n-
Propyl phthalate, di-n-butyl phthalate, di-
Iso-butyl phthalate and bis (2-ethylhexyl) phthalate are preferably used.

In the present invention, when two or more kinds of the above-mentioned component (c) are used, at least two kinds of the total carbon numbers of the two alkyl groups in the aromatic dicarboxylic acid diester are 4 or more. It is preferable to use an aromatic dicarboxylic acid diester (hereinafter, an aromatic dicarboxylic acid diester having two alkyl groups and a large total carbon number is used as the component (c1),
The smaller one may be referred to as the component (c2). ).

Preferably, two or more kinds of phthalic acid diesters are used, and the total carbon number of two alkyl groups of one phthalic acid diester and the total carbon number of two alkyl groups of another phthalic acid diester. It is preferable to select and combine so that the difference is 4 or more. A specific example of the combination is as follows.

[0030]         Component (c1) Component (c2) (1) Di-n-butyl phthalate and diethyl phthalate (2) Di-iso-butyl phthalate and diethyl phthalate (3) Bis (2-ethylhexyl) phthalate and diethyl phthalate (4) Di-n-octyl phthalate and diethyl phthalate (5) Di-iso-decyl phthalate and diethyl phthalate (6) Butylbenzyl phthalate and diethyl phthalate (7) Di-n-hexyl phthalate and diethyl phthalate (8) Di-iso-hexyl phthalate and diethyl phthalate (9) Bis (2-ethylhexyl) phthalate and di-n-propyl phthalate (10) Di-n-octyl phthalate and di-n-propyl phthalate (11) Di-iso-decyl phthalate and di-n-propyl phthalate (12) Butylbenzyl phthalate and di-n-propyl phthalate (13) Di-n-hexyl phthalate and di-n-propyl phthalate (14) Di-iso-hexyl phthalate and di-n-propyl phthalate (15) Bis (2-ethylhexyl) phthalate and di-iso-butyl phthalate (16) Di-n-octyl phthalate and di-iso-butyl phthalate (17) Di-iso-decyl phthalate and di-iso-butyl phthalate (18) Butylbenzyl phthalate and di-iso-butyl phthalate (19) Di-n-hexyl phthalate and di-iso-butyl phthalate (20) Di-iso-hexyl phthalate and di-iso-butyl phthalate (21) Bis (2-ethylhexyl) phthalate and di-n-butyl phthalate (22) Di-n-octyl phthalate and di-n-butyl phthalate (23) Di-iso-decyl phthalate and di-n-butyl phthalate (24) Butylbenzyl phthalate and di-n-butyl phthalate (25) Di-n-hexyl phthalate and di-n-butyl phthalate (26) Di-iso-hexyl phthalate and di-n-butyl phthalate (27) Bis (2-ethylhexyl) phthalate and diethyl phthalate and di-n- Butyl phthalate (28) Bis (2-ethylhexyl) phthalate and diethylphthalate and di-is o-butyl phthalate

As described above, it is preferable to use a combination of at least two kinds of phthalic acid diesters in which the difference in the total carbon number of the two alkyl groups of the phthalic acid diester is 4 or more, and among them, the component (c1 ) As a phthalic acid diester in which the total carbon number of two alkyl groups is 10 or more,
Further, the total carbon number of the two alkyl groups as the component (c2) is 8
It is particularly preferable to use the following phthalic acid diesters in combination.

As the electron-donating compound used for preparing the solid catalyst component (A), other than the above-mentioned aromatic dicarboxylic acid diester as an essential component, another electron-donating compound may be used in combination. As the electron-donating compound, an organic compound containing oxygen or nitrogen can be used, and examples thereof include alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides and nitriles. , Isocyanates, Si-
Examples thereof include an organosilicon compound containing an O—C bond.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol, phenols such as phenol and cresol, methyl ether, ethyl ether,
Propyl ether, butyl ether, amyl ether,
Ethers such as diphenyl ether, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, p
-Ethyl toluate, methyl anisate, monocarboxylic acid esters such as ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate,
Dicarboxylic acid esters such as diisodecyl adipate and dioctyl adipate, acetone, methyl ethyl ketone,
Ketones such as methyl butyl ketone, acetophenone and benzophenone, acid halides such as phthalic acid dichloride and terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octyl aldehyde and benzaldehyde, methylamine, ethylamine, tributylamine, piperidine, aniline, Examples thereof include amines such as viridine and nitriles such as acetonitrile, benzonitrile and tolunitrile.

Further, as the organosilicon compound containing a Si--O--C bond, trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane. , Tri-iso-butylmethoxysilane, tri-t-butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxy. Silane, di-iso-propyldimethoxysilane, di-n-propyldiethoxysilane, di-
iso-propyldiethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, bis (2 -Ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane Silane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, Clopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, Cyclohexyl (n-propyl) dimethoxysilane, cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxy Silane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldi Chill silane, cyclohexyl dimethyl ethoxysilane, cyclohexyl diethyl methoxysilane, cyclohexyl diethyl ethoxysilane, 2-ethylhexyl trimethoxysilane, 2-ethylhexyl triethoxysilane, methyl trimethoxysilane, methyl triethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxysilane Silane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane and the like.

In the cyclic or chain polysiloxane of the component (d) used for preparing the solid catalyst component (A) of the present invention (hereinafter sometimes referred to as "component (d)"), the cyclic polysiloxane is One or more cyclic polysiloxanes represented by the following general formula (1) are used.

[0036]

[Chemical 5]

The formula, the R ⁶ R ¹¹ are each independently a methyltransferase or ethyl, n is an integer of 1 to 20.

Among the cyclic polysiloxanes represented by the above general formula (1) , n is preferably 1 to 10, more preferably 1 to 6 cyclic polysiloxane.

Specifically, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane. Are exemplified, and one kind or two or more kinds are used.

As the chain polysiloxane, one or more chain polysiloxanes represented by the following general formula (2) are used.

[0041]

[Chemical 6]

In the above general formula (2) , x represents an average degree of polymerization and is 2 to 30000, and R ¹³ and R ^{18 are}
Is a methyl group, and R ¹² , R ¹⁴ to R ¹⁷ and R ¹⁹
Some of these include those substituted with phenyl groups, higher fatty acid residues, epoxy-containing groups, polyoxyalkylene groups.

The polysiloxane, which is also called silicone oil, has a viscosity at 25 ° C. of 2 to 10000 centistokes, preferably 2 to 1000 centistokes.
More preferably, it is a chain polysiloxane which is liquid or viscous at room temperature and has 3 to 500 centistokes.

Examples of the chain polysiloxane include dimethylpolysiloxane, methylphenylpolysiloxane, higher fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane.

Specific examples of each polysiloxane include trade names TSF400, TSF401, TSF404, and TSF.
405, TSF4045, TSF410, TSF41
1, TSF433, TSF437, TSF4420, T
SF451-5A, TSF451-10A, TSF45
1-50A, TSF451-100, TSF483, T
SF484 (all manufactured by Toshiba Silicone Co., Ltd.),
KF96, KF96L, KF96H, KF69, KF9
2, KF961, KF965, KF56, KF99, K
F94, KF995, KF105, KF351, HIV
AC-F4 and HIVAC-F5 (all of which are manufactured by Shin-Etsu Chemical Co., Ltd.) correspond to these.

By combining one or more of the above chain polysiloxanes with other components (a), (b) and (c) and subjecting them to a catalytic reaction, high activity and high stereoregularity can be obtained. It is possible to prepare a solid catalyst component for polymerization of olefins which has a very small amount of fine powder and can produce a polymer having a high bulk specific gravity. It should be noted that the above-mentioned cyclic polysiloxane can be dissolved in an organic solvent such as toluene, xylene, hexane, or heptane before use.

The solid catalyst component (A) of the present invention comprises the component (a)
, Component (b), component (c), and component (d) are contacted. This contact can be treated in the absence of an inert organic solvent, but it is preferable to treat it in the presence of the solvent in consideration of ease of operation. As the inert organic solvent used, hexane, heptane, saturated hydrocarbon such as cyclohexane, benzene,
Examples thereof include aromatic hydrocarbons such as toluene, xylene and ethylbenzene, halogenated hydrocarbons such as ortho-dichlorobenzene, methylene chloride, carbon tetrachloride and dichloroethane, and among them, aromatic hydrocarbons having a boiling point of about 90 to 150 ° C. A class, specifically, toluene, xylene and ethylbenzene are preferably used.

The ratio of the amount of each component used is 0.1 to 200 ml, preferably 0.5, of the component (b) to 1 g of the component (a).
To 100 ml, and component (c) is 0.01 to 3.0 g
, Preferably 0.1 to 1.5 g, component (d) 0.01 to 20 g, preferably 0.05 to 10.0
It is g. Further, as described above, the ratio of the amount used when using at least two kinds of the component (c) is 1 g of the component (a),
The component (c1) is 0.01 to 2.0 g, preferably 0.1 to 1.0 g, and the component (c2) is 0.01 to 1.0 g, preferably 0.1 to 0.5 g. The amount of the inert organic solvent used is not particularly limited, but considering the operational problems, the volume ratio to the component (b) is preferably 0.1 to 10. In addition, these components may be dividedly added at the time of contact, or one kind or two or more kinds may be selected and used.

The contact of each component is carried out in an inert gas atmosphere, with water and the like removed, in a container equipped with a stirrer while stirring. The contact temperature may be a relatively low temperature range around room temperature when simply contacting and stirring and mixing, or when dispersing or suspending and carrying out a modification treatment, but when reacting after contacting to obtain a product. The temperature range of 40 to 130 ° C. is preferable. If the temperature during the reaction is lower than 40 ° C, the reaction does not proceed sufficiently, resulting in insufficient performance of the prepared solid catalyst component, and if the temperature exceeds 130 ° C, the evaporation of the solvent used becomes remarkable. Then, the reaction control becomes unstable. The reaction time is 1 minute or longer, preferably 10 minutes or longer, more preferably 30 minutes or longer.

When the solid catalyst component (A) of the present invention is prepared, the order of contacting the component (a), the component (b), the component (c) and the component (d) is not particularly limited and is arbitrary. An example of the contact order of each component is as follows. (1) The components (a), (b), (c) and (d) are simultaneously contacted. (2) The component (d) is contacted with the solid product obtained by contacting the components (a), (b) and (c). (3) Component (a), (b) and (c) solid product obtained by contacting in advance, the component (d) is contacted, repeated component (b)
To contact. (4) Components (b) and (d) are contacted with the solid product obtained by previously contacting components (a) and (c). (5) The components (b) and (d) are contacted with the solid product obtained by previously contacting the components (a) and (c), and then the component (b) is repeatedly contacted. (6) Components (c) and (d) are contacted with the solid product obtained by previously contacting components (a) and (b), and then component (b) is repeatedly contacted. (7) Components (c) and (d) are contacted with the solid product obtained by previously contacting components (a) and (b), and then components (b) and (c) are repeatedly contacted. (8) Component (c) is contacted with the solid product obtained by contacting components (a) and (b) in advance, and then repeated components are added.
After contacting (b), component (d) is contacted. (9) Components (c) and (d) are contacted with the solid product obtained by previously contacting components (a) and (b), and then components (b) and (d) are repeatedly contacted.

In contacting each of the above components, the contacting order of the component (d) is arbitrary, but the solid product obtained by previously contacting the components (a), (b) and (c) is contacted. It is preferable to increase the bulk specific gravity of the produced polymer and reduce the fine powder content in the polymer. Further, in the above contact, the contact condition when the resulting solid product is contacted with the repeating component (b) is in the temperature range of 40 to 130 ° C. for 1 minute or more, preferably 5 minutes or more, more preferably 10 minutes. Hold for more than a minute.
At this time, there are a method of adding the component (b) as it is and a method of appropriately diluting with the above-mentioned inert organic solvent, and the latter method is preferably used. In addition, it is also one of preferred embodiments to wash the solid product obtained by the contacting / reacting in the preceding step with the above-mentioned inert organic solvent and then repeatedly contact with the component (b).

Further, a solid product obtained by contacting the components (a), (b) and (c), or the components (a) and (b)
When the suspension of the solid product obtained by contacting with each other is heated to bring the component (c) and / or the component (d) into contact with each other to proceed the reaction, The temperature rise from the temperature to the reaction is 0.1 to 2 at an average heating rate.
The temperature is set to 0 ° C./minute, more preferably 0.2 to 10 ° C./minute, and particularly preferably 0.3 to 8 ° C./minute. If the temperature rise is too slow, the bulk specific gravity of the polymer produced using the solid catalyst component will be insufficient, and conversely, if the temperature rise rate is too fast, the particles will be destroyed by the heat of reaction and the prepared solid The fine powder of the catalyst component is increased, and as a result, the fine powder of the polymer produced by using the solid catalyst component is increased.

Furthermore, when two or more kinds of the component (c) are used, it is necessary to first contact the component (c1) and then the component (c2) in contact with the component (a). At this time, it is preferable to contact the component (c2) after the contact of the component (a), the component (b) and the component (c1). At this time, the component (c1) and the component (c2) may be added and contacted at once, or may be added separately. Further component (c1) and component
It is also possible to use two or more of each of (c2).

The contact sequence of each component when two or more components (c) are used is exemplified as follows. 1. Component (d) is contacted with the solid product obtained by contacting components (a), (b) and (c1) and then component (c2). 2. The solid product obtained by contacting the components (a), (b) and (c1) and then the component (c2) is contacted with the component (d) and repeatedly contacted with the component (b). 3. Component (b), components (c2) and (d) are contacted with the solid product obtained by contacting components (a) and (c1) in advance. 4. The solid product obtained by contacting the components (a) and (c1) in advance is contacted with the component (b), the components (c2) and (d), and then repeatedly contacted with the component (b). 5. The solid product obtained by contacting the components (a) and (b) in advance is contacted with the component (c1) and then the component (c2).
Contact (d) and then repeatedly contact component (b). 6. Components (c1) and (d) are contacted with the solid product obtained by contacting components (a) and (b) in advance, and then components (b) and (c2) are contacted. 7.The solid product obtained by contacting components (a) and (b) in advance is contacted with component (c1), and then repeatedly contacted with component (b), followed by components (c2) and (d). ) Contact. 8.The components (c1) and (d) are contacted with the solid product obtained by contacting the components (a) and (b) in advance, and then the repeating components (b), (c2) and (d) are added. Contact.

The contact temperature of the component (c) is not particularly limited, but is preferably 130 ° C. or lower, and when two or more kinds are used, the component (c1) is lower than 70 ° C., preferably 0 to 5
5 ° C, component (c2) is 70 to 130 ° C, but component (c1)
The contact temperature of the component (c2) is not particularly limited as long as it is after the contact with.

Thus, two or more kinds of aromatic dicarboxylic acid diesters are used, especially those having a large total carbon number of the two ester substituents, especially those having a total carbon number of 10 or more, and those having a small total carbon number, especially It is possible to prevent agglomeration of solid particles at the time of preparation by preparing the solid catalyst component in the order of 8 or less as described above, that is, contacting the component (c1) and then the component (c2). Can reduce the fines in the finally obtained solid catalyst component. As a result, by using the solid catalyst component thus prepared, it is possible to produce a polymer having less coarse powder and fine powder and high bulk specific gravity.

The solid catalyst component (A) according to the present invention will be described below.
A specific example of the method for preparing is shown. Example 1: Component (a) in an aromatic hydrocarbon solvent such as toluene
Diethoxy magnesium as a temperature range from -10 to 30
Suspend at 0 ° C. and add titanium tetrachloride as component (b) into the suspension. At this time, the amount of titanium tetrachloride is preferably 1/2 or less in volume ratio with respect to the solvent in which the component (a) is suspended. Subsequently, dibutyl phthalate as component (c) is added to the suspension. The component (c) is preferably added at the same temperature as when the component (a) is suspended in toluene. Then the suspension is heated to 50 to 100 ° C.
Decamethylcyclopentasiloxane or dimethylpolysiloxane is added as component (d) in the temperature range of. Then, the temperature is maintained at 100 to 120 ° C. for 30 minutes to 3 hours to cause a reaction to obtain a solid product. The solid product is washed with toluene, and the condition at this time is 1 minute or more in the temperature range of 40 to 130 ° C. Further, toluene and titanium tetrachloride are added to and brought into contact with the solid product, the temperature is raised, and the temperature is kept at 100 to 120 ° C. for 30 minutes to 3 hours for reaction. Finally, the solid product is washed with heptane to obtain a solid catalyst component (A). Example 2: Diethoxymagnesium as component (a) in an aromatic hydrocarbon solvent such as toluene in the temperature range of -10 to 30 ° C.
And the titanium tetrachloride is added as the component (b).
At this time, the amount of titanium tetrachloride is preferably 1/2 or less in volume ratio with respect to the solvent in which the component (a) is suspended. Then, di-iso-octyl phthalate as a component (c1) was added to the suspension at a temperature range of 30 to 60 ° C., and diethyl phthalate as a component (c2) was added at a temperature range of 60 to 80.
Add at ° C. Thereafter, the temperature of the suspension is raised, decamethylcyclopentasiloxane or dimethylpolysiloxane is added as the component (d) at a temperature range of 80 to 110 ° C., and then the temperature is maintained at 100 to 120 ° C. for 30 minutes to 3 hours,
React to give a solid product. The solid product is washed with titanium tetrachloride diluted in toluene and then with toluene. The cleaning time is 1 minute or more in the temperature range of 40 to 130 ° C. Next, toluene and titanium tetrachloride are added to and brought into contact with the solid product, and then the temperature is raised and the temperature is maintained at 100 to 120 ° C. for 30 minutes to 3 hours to cause reaction, and the solid product obtained is washed with heptane. To obtain a solid catalyst component (A).

Example 3; Diethoxymagnesium as component (a) and component (c1) in an aromatic hydrocarbon solvent such as toluene.
After contacting with di-iso-decyl phthalate, titanium tetrachloride is added as the component (b) in the temperature range of -10 to 30 ° C. At this time, the amount of titanium tetrachloride is preferably 1/2 or less in volume ratio with respect to the solvent in which the component (a) is suspended. The temperature of the suspension is raised and the components (c
As 2) add di-iso-butyl phthalate. Thereafter, as the component (d), decamethylcyclopentasiloxane or dimethylpolysiloxane was added in the temperature range of 80 to 11
Add at 0 ℃, then in the temperature range 100 to 120 ℃ 3
Hold for 0 minutes to 3 hours to react to obtain a solid product. The solid product is washed with titanium tetrachloride diluted in toluene and then with toluene. The temperature at this time is 40
It is 1 minute or more in the temperature range from to 130 ° C. Next, toluene, titanium tetrachloride and diethyl phthalate are added to the solid product and brought into contact with each other, and the temperature is raised to a temperature range of 100 to 120.
The reaction is carried out by holding at 30 ° C. for 30 minutes to 3 hours, and the solid product is washed with heptane to obtain a solid catalyst component (A).

The solid catalyst component (A) of the present invention prepared as described above is preferably washed with an inert organic solvent such as heptane in order to remove unreacted substances. Alternatively, the catalyst for olefin polymerization according to the present invention is formed by combining the components (B) and (C) described below after the washing as it is.

The organoaluminum compound (B) used in forming the olefin polymerization catalyst of the present invention includes the general formula R ³ _q AlY _3-q (wherein R ³ is an alkyl group having 1 to 4 carbon atoms). The group, Y is any one of hydrogen, chlorine, bromine and iodine, and q is a real number satisfying 0 <q ≦ 3.). Examples of such an organoaluminum compound (B) include triethylaluminum, diethylaluminum chloride and tri-aluminum.
Iso-butylaluminum, diethylaluminum bromide, diethylaluminum hydride and the like can be mentioned, and one or more can be used. Preferred are triethylaluminum and tri-iso-butylaluminum.

The organosilicon compound (C) used in forming the olefin polymerization catalyst of the present invention has the general formula R ⁴ _r Si (OR ⁵ ) _4-r (wherein R ⁴ has 1 to 1 carbon atoms). 12 alkyl groups, cycloalkyl groups, phenyl groups,
They may be the same or different in any of a vinyl group, an allyl group and an aralkyl group. R ⁵ is 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. r is 0 or an integer of 1 to 3. ) An organosilicon compound represented by As such an organosilicon compound (C), phenylalkoxysilane,
Examples thereof include alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and alkoxysilane.

Specific examples of the above component (C) are as follows:
Trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, tri-iso-butylmethoxysilane, tri-t-
Butylmethoxysilane, tri-n-butylethoxysilane, tricyclohexylmethoxysilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-
n-propyldiethoxysilane, di-iso-propyldiethoxysilane, di-n-butyldimethoxysilane,
Di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane,
n-butylmethyldimethoxysilane, bis (2-ethylhexyl) dimethoxysilane, bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane , Cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexyl (iso-propyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane,
Cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclopentyl (iso-
Propyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) dimethoxysilane, cyclohexyl (n-pentyl) diethoxysilane, cyclopentyl (iso-butyl) dimethoxysilane, cyclohexyl (n-propyl) dimethoxysilane , Cyclohexyl (n-propyl) diethoxysilane, cyclohexyl (n-butyl)
Dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (iso-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldi Ethoxysilane,
Cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i
so-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane,
iso-butyltrimethoxysilane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane , 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane,
Cyclohexylcyclopentyldipropoxysilane, 3
-Methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane Examples thereof include silane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethylcyclohexylcyclohexyldimethoxysilane, and bis (3,5-dimethylcyclohexyl) dimethoxysilane.

Among the above, di-n-propyldimethoxysilane, di-iso-propyldimethoxysilane, di-n-butyldimethoxysilane, di-iso-butyldimethoxysilane, di-t-butyldimethoxysilane, di-n. -Butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldiethoxysilane, Cyclopentylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxy Run, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (C) may be one kind or Two or more kinds can be used in combination.

In the polymerization method of the present invention, olefins are polymerized or copolymerized in the presence of a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). The ratio of the amount of each component used is arbitrary as long as it does not affect the effects of the present invention and is not particularly limited, but usually the organoaluminum compound (B) is titanium in the solid catalyst component (A). The molar ratio is 1 to 1,000, preferably 50 to 500, per mol of atoms, and the organosilicon compound (C) is 0.0020 to 2, preferably 0.01 to the molar ratio of component (B). Used in the range of 0.5 to 0.5.

The olefin polymerization catalyst of the present invention is composed of the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C) shown above. As the external electron donor, an organic compound containing oxygen or nitrogen together with the above-mentioned organosilicon compound (C) can be used. Specific examples thereof include alcohols, phenols, ethers,
Esters, ketones, acid halides, aldehydes,
Amines, amides, nitriles, isocyanates,
And so on.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol and dodecanol, phenols such as phenol and cresol, methyl ether, ethyl ether and propyl. Ethers such as ether, butyl ether, amyl ether, diphenyl ether, methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, Octyl benzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethyl p-toluate, p
-Methoxyethyl benzoate, p-ethoxyethyl benzoate, ethyl anisate, monocarboxylic acid esters such as ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate,
Dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, phthalic acid Dicarboxylic acid esters such as dinonyl and didecyl phthalate, ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetone phenone and benzophenone,
Acid halides such as phthalic acid dichloride and terephthalic acid dichloride, aldehydes such as acetaldehyde, propionaldehyde, octyl aldehyde and benzaldehyde, amines such as methylamine, ethylamine, tributylamine, piperidine, aniline and pyridine, acetonitrile, benzonitrile, tolunitrile Examples thereof include nitriles and the like.

The olefins homopolymerized or copolymerized by using the catalyst of the present invention include ethylene, propylene and 1
-Butene, 4-methyl-1-pentene and the like, which are particularly suitable for the polymerization of propylene.

Furthermore, in the present invention, the olefin polymerization (also referred to as "main polymerization") is carried out using a catalyst comprising the above solid catalyst component (A), organoaluminum compound (B) and organosilicon compound (C). , Catalytic activity,
In order to further improve the stereoregularity and the particle properties of the resulting polymer, it is preferable to carry out preliminary polymerization prior to polymerization. As a monomer for prepolymerization, ethylene,
It is possible to use not only propylene but also monomers such as styrene and vinylcyclohexane.

The polymerization is carried out by slurry polymerization, liquefaction polymerization or gas phase polymerization, and it is possible to use hydrogen as a molecular weight modifier during the polymerization. The polymerization temperature is 200 ° C or lower, preferably 100 ° C or lower, and the polymerization pressure is 10 MPa or lower,
It is preferably 5 MPa or less, more preferably 2.5 MPa or less.

[0070]

EXAMPLES The present invention will be specifically described below based on examples. However, the scope of the present invention is not limited to these examples.

Example 1 <Preparation of solid catalyst component> A round-bottomed flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, had a bulk specific gravity of 0.23 g / ml and a specific surface area of 21.5 m ² / g. Sphericity (l / w)
1.10, average particle size 28 μm, particle size distribution 1n (D90 / D10)
10 g of diethoxymagnesium having a fine powder content of 1.10 or less and 5 μm or less and 5% and 90 ml of toluene were charged, and the suspension was cooled to 3 ° C. This suspension was added to a solution of 30 ml of toluene and 20 ml of titanium tetrachloride, and 3.6 ml of di-n-butyl phthalate was added to the suspension while maintaining the temperature of 3 ° C. in suspension. Add, then average 1
The temperature was raised to 100 ° C. at a temperature rising rate of ° C./min. Then, after adding 3.0 ml of decamethylcyclopentasiloxane, the temperature in the system was further raised to 110 ° C. and the reaction was carried out for 2 hours. After completion of the reaction, the supernatant was removed and the residue was washed with 80 ml of toluene at 110 ° C. four times. Then toluene 80
ml and titanium tetrachloride (20 ml) were added, and the mixture was treated at 110 ° C. for 2 hours with stirring and treated with 40 ° C. n-heptane 10
The solid catalyst component was obtained by washing 8 times with 0 ml. When the Ti content in this solid catalyst component was measured, it was 1.90% by weight.
Met.

<Formation and Polymerization of Polymerization Catalyst> 1.32 mmol of triethylaluminum was added to an autoclave equipped with a stirrer and having an internal volume of 2000 ml, which was sufficiently replaced with nitrogen gas.
0.13 mmol of cyclohexylmethyldimethoxysilane and 0.0033 of the solid catalyst component as titanium atom
mmol was charged to form a polymerization catalyst. Then, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged and a polymerization reaction was carried out at 70 ° C. for 1 hour to obtain a solid polymer. Table 1 shows the obtained catalyst performance and the particle properties of the polymer.

The properties of the polymers shown in Table 1 are as follows: After the completion of the polymerization reaction, the amount of the produced solid polymer is (a), and this is extracted with boiling n-heptane for 6 hours to obtain n-heptane. An insoluble polymer was obtained, and this amount was designated as (b). Polymerization activity (Y)
And the yield (t-II) of the total crystalline polymer was determined by the following formula. (Y) = (a) (g) / amount of solid catalyst component (g) The yield (t-II) of the total crystalline polymer is determined by the following formula. (T-II) = (b) (g) / (a) (g) × 100 (%) Further, melt index (MI), bulk specific gravity (BD)
The fine powder generation index (FI) obtained by the following method is also shown in Table 1.

The fine powder generation index (FI) was 18 after fully dried with nitrogen gas and then replaced with propylene gas.
In a stainless steel autoclave with a stirring device of 00 ml,
Charge 700 ml of n-heptane and keep 2.10 mmol of triethylaluminum and 0.21 mm of cyclohexylmethyldimethoxysilane while maintaining in a propylene gas atmosphere.
Charged ol. Then, the temperature inside the system was raised to 75 ° C., and the solid catalyst component obtained above was converted to 0.007 mm as titanium atom.
ol charged. Then, 150 mmol of hydrogen was charged, the propylene pressure in the system was set to 0.7 MPa, and the polymerization was continued for 3 hours. The pressure that decreases as the polymerization proceeds is
It was supplemented by continuous feeding of propylene only and kept at a constant pressure during the polymerization. Polymerization of propylene was performed according to the above-mentioned polymerization method, and the produced polymer was separated by filtration and dried under reduced pressure to obtain a solid polymer. The fine powder generation index (FI) was calculated by the following formula.

[0075] In the above formula, the particle size ^* is the particle size with an integrated particle size of 4%. Therefore, the fine powder generation index (FI) is an index representing the generation of fine powder particularly during polymerization, and the smaller the value is 1 or less, the more fine powder is generated.

Example 2 Example 1 except that octamethylcyclotetrasiloxane was used instead of decamethylcyclopentasiloxane.
The solid catalyst component was prepared and polymerized in the same manner as in.
The Ti content in the obtained solid catalyst component was measured and found to be 1.73% by weight. The catalytic performance and polymer particle properties according to this example are also listed in Table 1.

Example 3 Preparation of a solid catalyst component was carried out in the same manner as in Example 1 except that dimethylpolysiloxane (viscosity 100 centistokes, TSF-451 manufactured by Toshiba Silicone Co., Ltd.) was used in place of decamethylcyclopentasiloxane. Polymerization was carried out. The Ti content in the obtained solid catalyst component was measured and found to be 1.56% by weight. The catalytic performance and polymer particle properties according to this example are also listed in Table 1.

Example 4 A solid catalyst component was prepared and polymerized in the same manner as in Example 1 except that dimethylpolysiloxane (viscosity 10 centistokes) was used instead of decamethylcyclopentasiloxane. The Ti content in the obtained solid catalyst component was measured and found to be 1.73% by weight. The catalytic performance and polymer particle properties according to this example are also listed in Table 1.

Comparative Example 1 A solid catalyst component was prepared and polymerized in the same manner as in Example 1 except that decamethylcyclopentasiloxane was not used. The Ti content in the obtained solid catalyst component was measured and found to be 2.06% by weight. The catalytic performance and polymer particle properties according to this example are also listed in Table 1.

[0080]

[Table 1]

Example 5 <Preparation of solid catalyst component (A)> A solid catalyst component was prepared in the same manner as in Example 1. <Formation of Polymerization Catalyst and Block Copolymerization of Propylene and Ethylene> Internal volume 2 completely replaced with nitrogen gas
In a liter autoclave equipped with a stirrer, triethylaluminum (1.51 mmol), cyclohexylmethyldimethoxysilane (0.151 mmol) and the solid catalyst component (0.0030 mmol) were charged as titanium atoms to form a polymerization catalyst. Thereafter, 6.5 l of hydrogen gas and 700 ml of liquefied propylene were charged, and after preliminary polymerization was carried out at 20 ° C. for 5 minutes, the temperature was raised to 70 ° C. and a polymerization reaction was carried out for 20 minutes (first stage polymerization). After the completion of the first-stage polymerization, unreacted propylene was purged from the autoclave and replaced with nitrogen gas. Thereafter, the temperature was raised to 65 ° C., and a 1: 1 mixed gas of propylene and ethylene was supplied at 1.2 l / min to carry out polymerization for 1 hour (second-stage polymerization). The obtained catalyst performance and polymer properties are shown in Table 2. The polymerization activity was determined by the same method as in Example 1, and the ethylene content in the obtained copolymer was quantified by 13 C-NMR.

The content of the ethylene propylene rubber component (EPR) in the copolymer obtained here was measured by the following method. In a 1 liter flask equipped with a stirrer and cooling tube, about 2.5 g of the copolymer, 2,6-di-t-butyl-p
-Cresol 8 mg and p-xylene 250 ml were added, and the mixture was stirred at the boiling point until the copolymer was completely dissolved. Next, the flask was cooled to room temperature and left for 15 hours to precipitate a solid. This was separated into a solid matter and a liquid phase portion by a centrifuge. Then, the separated solid matter was put into a beaker, 500 ml of acetone was inserted thereinto, the mixture was stirred at room temperature for 15 hours, the solid matter was filtered and dried, and then the weight was measured (this weight is referred to as A). The separated liquid phase portion was also subjected to the same operation to deposit a solid substance and measure its weight (this weight is referred to as B). The content of ethylene propylene rubber component (EPR) in this copolymer was calculated by the following formula. EPR (% by weight) = {B (g) / (A (g) + B (g))} x 10
0 The fluidity of the copolymer obtained above was evaluated by the following method. Using the apparatus shown in FIG. 2, first, 50 g of the polymer obtained above was inserted into the funnel of 1. Then 2
The damper was removed, the polymer was dropped into the receiver of 3, and the time taken for all the polymers to fall was measured. This operation was carried out for the copolymer and the propylene homopolymer polymerized using the same solid catalyst component as that used for the polymerization of this copolymer (polymer obtained in Example 2), and the falling time was changed respectively. Let T1 and T2 be the fluidity at this time expressed by the following formula. Liquidity = T1 / T2

Example 6 Block copolymerization of propylene and ethylene was carried out in the same manner as in Example 5 except that the solid catalyst component prepared in Example 3 was used. The obtained catalyst performance and polymer properties are also shown in Table 2.

Comparative Example 2 An experiment was conducted in the same manner as in Example 5 except that the solid catalyst component prepared in Comparative Example 1 was used. The obtained results are also shown in Table 2. The propylene homopolymer used for the evaluation of fluidity was the polymer obtained in Comparative Example 1.

[0085]

[Table 2]

Example 7 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were placed in a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, to obtain a suspension state. 20 ml of titanium tetrachloride at room temperature was added to this, the temperature was raised to 50 ° C with stirring, 5.2 ml of di-iso-octyl phthalate was added, and the temperature was further raised to 70 ° C.
Then, 1.0 ml of diethyl phthalate was added, and then 4.0 ml of dimethylpolysiloxane (viscosity 100 centistokes, TSF-451 manufactured by Toshiba Silicone Co., Ltd.) was added. Further, the temperature in the system was raised to 112 ° C. and the reaction was carried out for 2 hours. After the reaction was completed, the supernatant was removed and toluene 8
15 ml at 100 ° C with 0 ml and 20 ml of titanium tetrachloride
It was subjected to a minute treatment and further washed with 100 ml of toluene at 100 ° C. three times. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was treated at 100 ° C. for 2 hours with stirring, and then washed with 100 ml of n-heptane at 40 ° C. eight times to obtain a solid catalyst component. The Ti content in this solid catalyst component was measured and found to be 2.2 wt%.

<Formation and Polymerization of Polymerization Catalyst> 20 ml of n-heptane was charged into an autoclave equipped with a stirrer and having an internal volume of 2 liter, which was sufficiently dried with nitrogen gas and then replaced with propylene gas, and a propylene gas atmosphere was added. While keeping the above, 1.31 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane, and 0.0026 mmo of the solid catalyst component as titanium atom.
1 was charged to form a polymerization catalyst. Then hydrogen gas 30
00 ml and 1.4 l of liquefied propylene were charged and preliminary polymerization was carried out at 20 ° C. for 5 minutes while stirring. Immediately thereafter, the temperature was raised and a polymerization reaction was carried out at 70 ° C. for 1 hour to obtain a solid polymer. Table 3 shows the obtained catalyst performance and polymer properties.

Example 8 <Preparation of solid catalyst component> 10 g of diethoxymagnesium, 80 ml of toluene and di-iso-in a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
2.5 ml of decyl phthalate was charged to make a suspension.
20 ml of room temperature titanium tetrachloride was added to this, and the temperature was raised to 80 ° C. with stirring, and di-iso-butyl phthalate 1.
After adding 2 ml, dimethylpolysiloxane (viscosity 1
00 centistokes, TS manufactured by Toshiba Silicone Co., Ltd.
4.0 ml of F-451) was added. Further, the temperature in the system was raised to 112 ° C. and the reaction was carried out for 2 hours. After the reaction was completed, the supernatant liquid was removed and toluene 80 ml, titanium tetrachloride 20 ml
And charged with 0.25 ml of diethyl phthalate, 110
It was treated at 30 ° C. for 30 minutes. After removing the supernatant, it was washed three times with 100 ml of toluene at 100 ° C. After that, 80 ml of toluene and 20 ml of titanium tetrachloride are newly added, and
The mixture was treated at 0 ° C. for 2 hours with stirring, and then washed with 100 ml of 40 ° C. n-heptane 8 times to obtain a solid catalyst component.
When the Ti content in this solid catalyst component was measured,
It was 2.1 wt%.

<Formation and Polymerization of Polymerization Catalyst> Polymerization was carried out in the same manner as in Example 7 using the solid catalyst component obtained as described above. The obtained catalyst performance and polymer properties are also shown in Table 3.

Example 9 <Preparation of solid catalyst component> 10 g of diethoxymagnesium, 80 ml of toluene and di-iso- were placed in a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer.
1.0 ml of octyl phthalate was charged into a suspension. 20 ml of room temperature titanium tetrachloride was added to this, the temperature was raised to 50 ° C. with stirring, 4.2 ml of di-iso-octyl phthalate was added, and then 1.0 ml of diethyl phthalate was added at 70 ° C. Dimethyl polysiloxane (TSF-405 manufactured by Toshiba Silicone Co., Ltd.) 3.0 at ℃
ml was added. Further, the temperature in the system was raised to 112 ° C. and the reaction was carried out for 2 hours. After the reaction was completed, the supernatant liquid was removed, and 80 ml of toluene and 20 ml of titanium tetrachloride were charged and the temperature was 110 ° C.
For 30 minutes. After removing the supernatant liquid, toluene 1
Wash 3 times with 100 ml at 100 ° C. After that, 80 ml of toluene, 20 ml of titanium tetrachloride and 0.25 ml of diethyl phthalate were newly added, and the mixture was treated at 100 ° C for 2 hours with stirring, and then treated with 100 ml of n-heptane at 40 ° C for 8 hours.
It was washed twice to obtain a solid catalyst component. The Ti content in this solid catalyst component was measured and found to be 2.3 wt%.

<Formation and Polymerization of Polymerization Catalyst> Polymerization was carried out in the same manner as in Example 7 using the solid catalyst component obtained as described above. The obtained catalyst performance and polymer properties are also shown in Table 3.

Example 10 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were placed in a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, to obtain a suspension state. 20 ml of room temperature titanium tetrachloride was added to this, the temperature was raised to 50 ° C. with stirring, 3.0 ml of butylbenzyl phthalate was added, and the temperature was further raised, and 1.0 ml of diethyl phthalate was added at 70 ° C. Then, 4.0 ml of dimethylpolysiloxane (viscosity 100 centistokes, TSF-451 manufactured by Toshiba Silicone Co., Ltd.) was added. Further, the temperature in the system was raised to 112 ° C. and the reaction was carried out for 2 hours. After the reaction was completed, the supernatant liquid was removed and toluene 80
ml and 20 ml of titanium tetrachloride for 15 minutes at 100 ° C, and 100 ml of toluene for 3 minutes at 100 ° C.
Washed twice. Then 80 ml of toluene and titanium tetrachloride 2
Fresh 0 ml was added, the mixture was treated at 100 ° C. for 2 hours with stirring, and then washed with 100 ml of 40 ° C. n-heptane 8 times to obtain a solid catalyst component. The Ti content in this solid catalyst component was measured and found to be 2.0 wt%.

<Formation and Polymerization of Polymerization Catalyst> Polymerization was carried out in the same manner as in Example 7 using the solid catalyst component obtained as described above. The obtained catalyst performance and polymer properties are also shown in Table 3.

Example 11 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were placed in a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, to obtain a suspension state. 20 ml of titanium tetrachloride at room temperature was added to this, the temperature was raised to 50 ° C with stirring, 5.2 ml of di-iso-octyl phthalate was added, and the temperature was further raised to 70 ° C.
1.0 ml of di-n-propyl phthalate was added, and then dimethylpolysiloxane (viscosity 100 centistokes, TSF-451 manufactured by Toshiba Silicone Co., Ltd.) 4.0.
ml was added. Further, the temperature in the system was raised to 112 ° C. and the reaction was carried out for 2 hours. After completion of the reaction, the supernatant liquid was removed and 100 ml was added using 80 ml of toluene and 20 ml of titanium tetrachloride.
Treat at 15 ° C for 15 minutes, then add 100 ml of toluene to 1
It was washed twice at 00 ° C. Then 80 ml of toluene and di
Add 0.3 ml of -n-propyl phthalate, and add 3 at 105 ° C.
It was treated with stirring for 0 minutes. After that, 80 ml of toluene,
20 ml of titanium tetrachloride and 4.0 ml of dimethylpolysiloxane (TSF-451 manufactured by Toshiba Silicone Co., Ltd.) were newly added, and the mixture was treated at 100 ° C. for 2 hours with stirring, and then washed with 100 ml of n-heptane at 40 ° C. 8 times. To obtain a solid catalyst component. The Ti content in this solid catalyst component was measured and found to be 1.8 wt%.

<Formation and Polymerization of Polymerization Catalyst> Polymerization was carried out in the same manner as in Example 7 using the solid catalyst component obtained as described above. The obtained catalyst performance and polymer properties are also shown in Table 3.

Comparative Example 3 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were put into a round bottom flask having a capacity of 500 ml, which was sufficiently replaced with nitrogen gas and equipped with a stirrer, to make a suspension state. 20 ml of titanium tetrachloride at room temperature was added to this, the temperature was raised to 90 ° C with stirring, 3.5 ml of di-n-butyl phthalate was added, and then the temperature in the system was raised to 112 ° C for 2 hours. It was made to react. After completion of the reaction, the supernatant was removed, treated with 80 ml of toluene and 20 ml of titanium tetrachloride at 100 ° C. for 15 minutes, and further washed with 100 ml of toluene at 100 ° C. three times. After that, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and the mixture was treated at 100 ° C for 2 hours with stirring, and then n-heptane 1 at 40 ° C was added.
The solid catalyst component was obtained by washing 8 times with 00 ml. The Ti content in this solid catalyst component was measured and found to be 3.5 wt%.

<Formation and Polymerization of Polymerization Catalyst> Polymerization was carried out in the same manner as in Example 7 using the solid catalyst component obtained as described above. The obtained catalyst performance and polymer properties are also shown in Table 3.

[0098]

[Table 3]

[0099]

EFFECT OF THE INVENTION The catalytic activity of olefins, especially propylene, is sufficiently high when the catalyst of the present invention is used. As a result, the amount of catalyst residue present in the produced polymer can be suppressed to an extremely low amount, and therefore the amount of residual chlorine in the produced polymer can be reduced to such an extent that a deashing step is not required at all. Moreover, since the yield of the stereoregular polypropylene produced is extremely high and the bulk specific gravity is also high, an excellent polymer can be efficiently produced. Further, when the polymerization is carried out in the presence of the catalyst according to the present invention, fine powder in the produced polymer can be reduced, so that troubles in process operation due to the fine powder polymer can be prevented in advance. Further, according to the catalyst of the present invention, even if the production ratio of the rubber-like copolymer in the block copolymerization is increased, the particle properties of the produced copolymer, particularly the fluidity, are excellent. It is possible to eliminate operational troubles.

[Brief description of drawings]

FIG. 1 is a flowchart showing a preparation process of a catalyst for olefin polymerization according to the present invention.

FIG. 2 is a schematic explanatory view of an apparatus used for measuring fluidity of a copolymer in Examples.

[Explanation of symbols]

1 funnel 2 damper 3 receiver

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-6-166716 (JP, A) JP-A-60-115610 (JP, A) JP-A-57-92009 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (3)

(57) [Claims] 1. A solid catalyst component (A) for olefin polymerization, which is prepared using the following components (a) to (d). (a) General formula Mg (OR ¹ ) ₂ (In the formula, R ¹ has 1 to ¹ carbon atoms.
4 represents an alkyl group or an aryl group. ) A dialkoxymagnesium or diaryloxymagnesium, (b) a general formula Ti (OR ² ) _p X _4-p (wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen element, p is 0
Alternatively, it is an integer of 1 to 3. ), A titanium compound (c), an aromatic dicarboxylic acid diester, and (d) a cyclic polysiloxane represented by the following general formula (1) or a general formula (2) below. Chain polysiloxane [Chemical formula 1] (In the formula, R ⁶ to R ¹¹ are each independently a methyl group.
Or an ethyl group, and n is an integer of 1 to 20.
It ) [Chemical 2] (In the formula, x represents an average degree of polymerization, and is 2 to 30,000.
There, the main body of R ¹³ and R ¹⁸ are methyl groups, R ^12, R
¹⁴ to R ¹⁷ and a part of R ¹⁹ are phenyl groups and higher fatty acid residues
Group, epoxy-containing group, polyoxyalkylene group substituted
Including those ) 2. The aromatic dicarboxylic acid diester of the component (c) is a combination of the following phthalic acid diesters (1) to (1).
The solid catalyst component (A) for olefin polymerization according to claim 1, which is one or more selected from (28 ). (1) Di-n-butyl phthalate and diethyl phthalate (2) Di-iso-butyl phthalate and diethyl phthalate
Preparative (3) bis (2-ethylhexyl) phthalate and diethyl
Phthalate (4) Di-n-octyl phthalate and diethyl phthalate (5) Di-iso-decyl phthalate and diethyl phthalate
Preparative (6) Butyl benzyl phthalate and diethyl phthalate (7) di -n- hexyl phthalate and diethyl phthalate (8) di -iso- hexyl phthalate and Jiechirufutare
Over preparative (9) Bis (2-ethylhexyl) phthalate and di -n-
Propyl phthalate (10) Di-n-octyl phthalate and di-n- propyl phthalate
Thallate (11) di-iso-decyl phthalate and di-n-propyl
Phthalate (12) butylbenzyl phthalate and di-n-propyl phthalate
Rate (13) di-n-hexyl phthalate and di-n-propyl phthalate
Thallate (14) di-iso-hexyl phthalate and di-n-propyi
Ruphthalate (15) bis (2-ethylhexyl) phthalate and di-is
o-Butyl phthalate (16) Di-n-octyl phthalate and di-iso-butyl
Phthalates (17) Di-iso-decyl phthalate and di-iso-butyrate
Ruphthalate (18) butylbenzyl phthalate and di-iso-butyl phthalate
Thallate (19) di-n-hexyl phthalate and di-iso-butyl
Phthalate (20) di-iso-hexyl phthalate and di-iso-bu
Tyl phthalate (21) bis (2-ethylhexyl) phthalate and di-n-
Butyl phthalate (22) Di-n-octyl phthalate and di-n -butyl phthalate
Rate (23) di-iso-decyl phthalate and di-n-butyl phthalate
Talate (24) butylbenzyl phthalate and di-n-butyl phthalate
Over door (25) di -n- hexyl phthalate and di -n- Buchirufuta
Rate (26) di-iso-hexyl phthalate and di-n-butyl
Phthalate (27) Bis (2-ethylhexyl) phthalate and diethyl
Phthalate and di-n-butyl phthalate (28) bis (2-ethylhexyl) phthalate and diethyl
Phthalate and di-iso-butyl phthalate 3. A catalyst for olefin polymerization, which is formed from the following components (A), (B) and (C). (A) The solid catalyst component according to claim 1, (B) the general formula R ³ _q AlY _3-q (wherein R ³ has 1 carbon atom).
To 4 alkyl groups, Y is any of hydrogen, chlorine, bromine, and iodine, and q is a real number satisfying 0 <q ≦ 3. ), And (C) the general formula R ⁴ _r Si (OR ⁵ ) _4-r (wherein R ⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, an allyl group). , a vinyl group, in any of the aralkyl group may .R ⁵ be the same or different is 1 to carbon atoms
4 alkyl groups, cycloalkyl groups, phenyl groups, vinyl groups, allyl groups and aralkyl groups, which may be the same or different. r is 0 or an integer of 1 to 3. ) An organosilicon compound represented by: