JPH11147909A - Solid catalyst component and catalyst for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to obtain, in good yield, a granular or spherical polymer with a narrow particle size distribution, high in stereoregularity and bulk specific wt., by conducting a catalytic reaction of a suspension comprising a specific dialkoxy magnesium and a titanium compd., and two specific types of phthalic diester under a specific condition. SOLUTION: A suspension is obtd. by contacting a dialkoxy magnesium having the formula: Mg(OR<1> )2 (wherein R<1> is a 1-4C alkyl, an aryl) and a tetravalent titanium halide compd. having the formula: Ti(OR<2> )m X4m (wherein R<2> is a 1-4C alkyl; X is a halogen; and (m) is 0-3) under agitation with a peripheral speed at the tip of the agitating blade of 0.5-10 m/sec at a temp. of <=30 deg.C, followed by aging reaction at a temp. of <=50 deg.C for 1 min to 10 hr. After addn. of a phthalic diester having a combined carbon no. of the two alkyl groups being 10 or more and a phthalic diester having a combined carbon no. of the two alkyl group being smaller than 10 in a state wherein the suspension is kept at a temp. in the range of lower than 60 deg.C, the suspension is heated to be reacted at the rate of 0.3-10.0 deg.C/min up to 90 deg.C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid catalyst component for the polymerization of olefins and a catalyst capable of obtaining a polymer having high stereoregularity and excellent particle properties in a high yield. More specifically, the present invention relates to a solid catalyst component and a catalyst for olefin polymerization capable of obtaining a polymer having a uniform particle size and a uniform particle size and a good flowability in a high yield in the polymerization of olefins.

[0002]

2. Description of the Related Art Conventionally, in the polymerization of olefins,
A solid catalyst component for olefin polymerization containing magnesium, titanium, an electron-donating compound and a halogen as essential components, an olefin polymerization catalyst comprising the solid catalyst component, an organoaluminum compound, an organosilicon compound and the like, and the presence of the catalyst Many olefin polymerization methods for polymerizing or copolymerizing olefins have been proposed below (for example, JP-A-57-63310 and JP-A-5-63310).
7-63311). However, these methods are not always satisfactory for obtaining a high stereoregular polymer in a high yield.

[0003] In JP-A-63-3010, a product obtained by contacting a dialkoxymagnesium, an aromatic dicarboxylic acid diester, an aromatic hydrocarbon and a titanium halide is heat-treated in a powder state. Thus, there has been proposed a catalyst for olefin polymerization comprising a solid catalyst component prepared as described above, an organoaluminum compound and an organosilicon compound, and a method for polymerizing olefins in the presence of the catalyst.

In Japanese Patent Application Laid-Open No. Hei 1-315406, titanium tetrachloride is brought into contact with a suspension formed of diethoxymagnesium and alkylbenzene, and then phthalic acid dichloride is added and reacted to form a solid. And a solid catalyst component prepared by contacting the solid product with titanium tetrachloride in the presence of alkylbenzene, and a catalyst for olefin polymerization comprising an organoaluminum compound and an organosilicon compound; Methods for polymerizing olefins in the presence have been proposed.

The above prior arts have a high activity enough to omit a so-called deashing step for removing a catalyst residue such as chlorine or titanium remaining in a produced polymer, and also have a stereoregularity. It focuses on improving the yield of the polymer and increasing the sustainability of the catalyst activity during the polymerization, and has each produced excellent results.

However, when olefins are polymerized using a polymerization catalyst having a composition comprising such a highly active catalyst component and an electron donating compound represented by an organoaluminum compound and a silicon compound, a solid catalyst component is obtained. A large amount of fine powder was contained in the resulting polymer due to the fine powder contained therein and the destruction of particles due to the heat of reaction during polymerization, and the particle size distribution tended to be broad. When the amount of the finely divided polymer increases, it may hinder the continuation of a uniform reaction or cause process obstruction such as blockage of a pipe at the time of transferring the polymer. Undesirable effects up to. For this reason, the amount of the finely divided polymer was as small as possible, and this was a factor for seeking a polymer having a uniform particle size and a narrow particle size distribution.

As means for solving the problems of fluidity and particle size distribution of the formed polymer, JP-A-56-811 and JP-A-58-83006 disclose a hydrocarbon solution of a magnesium compound and a liquid titanium compound. To form a solid product, or to form a solid product after forming a hydrocarbon solution of a magnesium compound and a titanium compound, wherein the solid product is formed by coexistence of an electron donor. Disclosed below is a solid titanium catalyst component obtained by supporting an electron donor such as a polyvalent carboxylic acid ester on the solid product during or after the formation of the solid product.

However, from the industrial viewpoint that the above method dissolves a magnesium compound such as magnesium chloride in a solvent such as alcohol to form a uniform solution, and then precipitates a solid substance, the method uses a large amount of raw materials and auxiliaries. Must be a very complicated process.

On the other hand, as means for solving the problems such as particle size distribution while simplifying the preparation process, JP-A-6-15
No. 7659, a spherical dialkoxymagnesium is added to a mixed solution of an aromatic hydrocarbon and titanium tetrachloride,
There has been proposed an olefin polymerization catalyst comprising a solid catalyst component obtained by adding, reacting, and reacting a suspension of an aromatic hydrocarbon and a phthalic acid diester with titanium tetrachloride.

In JP-A-6-287225, a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic diester is added to a mixed solution of aromatic hydrocarbon and titanium tetrachloride. Olefin obtained by washing the obtained reaction product with an aromatic hydrocarbon, drying the solid component obtained by reacting again with titanium tetrachloride, and subjecting to a fine powder removal treatment step. Solid catalyst components for class polymerization have been proposed.

Further, in JP-A-6-287217, a suspension of spherical dialkoxymagnesium, aromatic hydrocarbon and phthalic acid diester is added to a mixed solution of aromatic hydrocarbon and titanium tetrachloride. After the reaction, the obtained reaction product is washed with an aromatic hydrocarbon, the solid component obtained by reacting again with titanium tetrachloride is dried, fine powder is removed, and then the powdered nonionic interface is removed. There has been proposed a solid catalyst component for olefins polymerization, which is obtained through a treatment step of adding an activator.

[0012]

The above technique has the effect of removing fine powder contained in the solid catalyst component itself and reducing the amount of fine powder of the resulting polymer.
However, the generation of fine powder due to particle destruction due to the heat of reaction during the polymerization has not been controlled yet, and fine powder still exists in the produced polymer. In addition, the polymer produced in this technique is close to a sphere, and a good morphology can be obtained.However, the particle shape or particle size of the polymer depends on the dialkoxymagnesium used as the raw material. You need to control morphology.
Furthermore, the bulk specific gravity of the produced polymer is low, and in the production of polyolefin, the production amount per unit volume of the polymer in the polymerization tank is small, and the throughput of the polymer in the transport or pelletizing step is limited. The problem of reduced overall production productivity still remains.

The present inventors have conducted various studies to solve the problems left in the prior art, and as a result, a special raw material, an auxiliary agent and a special particle size adjusting process (for example, Solid catalyst component prepared under specific preparation conditions without using the fine powder removal step), and in the presence of a catalyst containing the solid catalyst component and formed with a specific organosilicon compound and an organoaluminum compound. It has been confirmed that the above problems can be effectively solved by polymerizing olefins, and the present invention has been completed.

Accordingly, an object of the present invention is to provide a solid catalyst and a catalyst for olefin polymerization which can obtain a granular or spherical polymer having a high stereoregularity, a narrow particle size distribution and a high bulk specific gravity in a high yield. Is to provide.

[0015]

In order to achieve the above object, the present invention provides a solid catalyst component (A) for olefin polymerization.
(Hereinafter sometimes referred to as “component (A)”) is represented by (a) a general formula Mg (OR ¹ ) ₂ (wherein R ¹ represents an alkyl group or an aryl group having 1 to 4 carbon atoms). A dialkoxymagnesium represented by: (b) a general formula Ti (OR ² ) _m X _4-m (wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen element, and m represents 0 or 1 (C) a phthalic acid diester in which the total number of carbon atoms of two alkyl groups is 10 or more, and (d) a total of less than 10 carbon atoms in two alkyl groups. A solid catalyst component for the polymerization of olefins comprising phthalic acid diester, wherein a suspension formed during aging and after aging formed from the components (a) and (b) is maintained in a temperature range of less than 60 ° C. The component (c) is contact-reacted in the above state, and at least up to 90 ° C. after aging, At a heating rate of an average 0.3 ~10.O
It is characterized in that the temperature is raised at a rate of ° C./min and the stirring speed of the reaction vessel is adjusted at a tip peripheral speed of the stirring blade of 0.5 to 10 m / sec or more.

Further, the catalyst for polymerization of olefins of the present invention comprises:
It is characterized by being formed from the above component (A), and the following components (B) and (C). (B) General formula R ³ _n AlY _3-n (wherein, R ³ is an alkyl group having 1 to 4 carbon atoms, Y is any one of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom, and n is 0 <n ≦ 3 in a real number.) an organoaluminum compound and (C) represented by the general formula R ⁴ _p Si (oR ⁵⁾ in _4-p (wherein, R ⁴ is an alkyl group having 1 to 12 carbon atoms, cycloalkyl R ⁵ is an alkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and R ⁵ is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, or an allyl group. Or an aralkyl group which may be the same or different, and p is 0 or an integer of 1 to 3.).

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The dialkoxymagnesium (hereinafter sometimes referred to as "component (a)") constituting the solid catalyst component (A) of the present invention includes dimethoxymagnesium.
Diethoxy magnesium, di-n-propoxy magnesium, di-iso-propoxy magnesium, di-n-butoxy magnesium, di-iso-butoxy magnesium, diphenoxy magnesium, ethoxy methoxy magnesium,
One or more of ethoxy-n-propoxymagnesium, n-butoxyethoxymagnesium, iso-butoxyethoxymagnesium and the like can be mentioned, and among them, diethoxymagnesium or di-n-propoxymagnesium is preferably used.

Next, a tetravalent titanium halide (hereinafter referred to as “component”) used in preparing the solid catalyst component (A) of the present invention.
(b) ". ) Is titanium tetrahalide or alkoxytitanium halide. Specifically, as titanium tetrahalide, TiCl ₄ , TiB
r ₄ , TII ₄ , and alkoxytitanium halide, T
i (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , T
_{i (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 Cl ₂ , Ti (OCH ₃ ) ₃ Cl, Ti (O
C ₂ H ₅ ) ₃ Cl, Ti (OC ₃ H ₇ ) ₃ Cl, Ti
_{(On-C 4 H 9)} 3 Cl , and the like. Among these, titanium tetrahalide is preferable, and TiCl ₄ is particularly preferable. One or more of these titanium compounds may be used.

Specific examples of phthalic acid diesters (hereinafter sometimes referred to as "component (c)") in which the total number of carbon atoms of two alkyl groups used in preparing the solid catalyst component (A) of the present invention is 10 or more. Examples include di-n-pentyl phthalate, di-iso-pentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-iso-heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate. , Bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-iso-nonyl phthalate, di-n-decyl phthalate, di-iso-decyl phthalate, bis (2,2-dimethylheptyl) Phthalate, n-butyl (iso-hexyl) phthalate, ethyl (iso-octyl) phthalate, n-butyl (i o- octyl) phthalates - door,
n-pentylhexyl phthalate, n-pentyl (is
o-hexyl) phthalate, iso-pentyl (heptyl) phthalate, n-pentyl (iso-octyl) phthalate, n-pentyl (iso-nonyl) phthalate, iso-pentyl (n-decyl) phthalate, n-
Pentyl (undecyl) phthalate, iso-pentyl (iso-hexyl) phthalate, n-hexyl (is
o-octyl) phthalate, n-hexyl (iso-nonyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (iso-octyl) phthalate,
Examples thereof include n-heptyl (iso-nonyl) phthalate, n-heptyl (neo-decyl) phthalate, iso-octyl (iso-nonyl) phthalate, and dicyclohexyl phthalate, and one or more of these are used.

Of these, particularly, phthalic acid having 5 carbon atoms
Di-n-pentyl phthalate, di-is is preferred.
o-pentyl phthalate, dihexyl phthalate, di-
n-heptyl phthalate, di-iso-heptyl phthalate, di-n-octyl phthalate, bis (2-methylhexyl) phthalate, bis (2-ethylhexyl) phthalate, di-n-nonyl phthalate, di-iso -Nonyl phthalate, di-n-decyl phthalate, di-is
O-decyl phthalate is particularly preferably used.

A specific example of a phthalic acid diester (hereinafter, sometimes referred to as "component (d)") in which the total number of carbon atoms of two alkyl groups used for preparing the solid catalyst component (A) of the present invention is less than 10 is used. Examples include dimethyl phthalate, diethyl phthalate, ethyl methyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, ethyl (n-propyl) phthalate, ethyl (iso-propyl) phthalate, di-n-butyl phthalate , Di-iso-butyl phthalate, ethyl (n-butyl) phthalate, ethyl (is
o-butyl) phthalate, n-propyl (n-butyl) phthalate, n-propyl (iso-butyl) phthalate, iso-propyl (n-butyl) phthalate, iso-propyl (iso-butyl) phthalate, ethyl (n- (Pentyl) phthalate, ethyl (iso-pentyl) phthalate, n-propyl (n-pentyl) phthalate, iso-propyl (iso-pentyl) phthalate, n-butyl (n-pentyl) phthalate, iso-butyl (iso-pentyl) Phthalate is exemplified and these 1
Species or two or more are used.

Of these, in particular, phthalic acid has 2 carbon atoms.
Preferred are diesters of straight-chain or branched alkyl of from 4 to 4, diethyl phthalate, di-n-propyl phthalate, di-iso-propyl phthalate, di-n-butyl phthalate, di-iso-butyl phthalate, Ethyl (n-butyl) phthalate and ethyl (iso-butyl) phthalate are particularly preferably used.

As a method for preparing the solid catalyst component (A) of the present invention, the suspension formed during and after aging formed from the components (a) and (b) is heated to a temperature range of less than 60 ° C. The component (c) is contact-reacted in the held state, and at least up to 90 ° C after aging, the temperature is raised at an average rate of 0.3 to 10.0 ° C / min. There is no particular limitation as long as the blade tip speed is adjusted at a peripheral speed of 0.5 to 10 m / sec or more, and in particular, it is preferably carried out under the following conditions (i) to (iii).

(I) The component (a) and the component (b) are first placed at 30 ° C.
Hereinafter, preferably −20 to 30 ° C., particularly preferably 0 to 30 ° C.
It is desirable to carry out a so-called aging reaction in which the contact is carried out at a temperature in the range of 20 ° C, and then the reaction is carried out at a temperature of 50 ° C or lower, preferably 0 to 50 ° C, particularly preferably 10 to 40 ° C. The reaction time at this time is 1 minute to 10 hours, preferably 3 minutes.
0 minutes to 5 hours. (ii) after ripening to 90 ° C, an average of 0.3 ° C / minute or more;
Preferably 0.3-10 ° C / min, particularly preferably 0.3-5 ° C
/ Minute, and the same conditions are applied from 90 ° C. or higher to the end of the reaction. (iii) During the aging of (i) or after the aging of (ii), the component (c) is added at a temperature of less than 60 ° C, preferably 50 ° C or more and less than 60 ° C. ) Is usually 60
It is added at a temperature of at least 70 ° C, preferably at least 70 ° C, and then reacted at at least 90 ° C. The reaction time at this time is 1 minute to 1
0 hours, preferably 30 minutes to 5 hours.

Further, the above steps (i) to (iii) are carried out with stirring at a tip peripheral speed of the stirring blade of 0.5 m / sec or more, preferably in the range of 0.5 to 10 m / sec, particularly preferably in the range of 0.5 to 5 m / sec. Do it below. The stirring blade is not particularly limited, and examples thereof include a paddle type, a turbine type, a crescent type and a so-called propeller type. The total length of the stirring blade is preferably about 1/3 to 4/5 of the maximum inner diameter of the stirring tank.

When the above components (a), (b), (c) and (d) are brought into contact with each other to prepare a solid catalyst component, a hydrocarbon solvent which is liquid at room temperature can be used. In particular,
Aliphatic and alicyclic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cymene; dichloroethane, dichloropropane, Examples thereof include halogenated hydrocarbons such as trichloroethylene, carbon tetrachloride, chlorobenzene, and dichlorobenzene. Among them, aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, and cymene are particularly preferably used.

The solid catalyst component of the present invention as described above
(A) is prepared, after the step (iii), the obtained solid component is washed with an aromatic hydrocarbon solvent such as toluene, ethylbenzene and xylene, or an aliphatic hydrocarbon solvent such as hexane and heptane, or The component (b) or the component (b) diluted with an aromatic hydrocarbon solvent or an aliphatic hydrocarbon solvent may be repeatedly contacted with the solid product at least once or more to improve the performance of the obtained solid catalyst component. This is one of the preferred embodiments.

Further, in the preparation of the solid catalyst component (A) of the present invention, an aluminum compound or an organosilicon compound having a Si--O bond may be used in addition to the components (a), (b), (c) and (d). Can be used.

The aluminum compound is at least one selected from a group of aluminum compounds represented by the following general formulas (1) and (2).

[0030] _{^{Al (OR 6) q X 1}} 3 -q (1) ( wherein, R ⁶ is 2 substituents from 1 alkyl group having 3 alkyl group or a phenyl group, or 1 carbon atoms having 1 to 4 carbon atoms When q is 2 or more, R ⁶ is the same or different, X ¹ represents a halogen element, and q is 0 ≦
q is an integer of 3 or less. )

[0031] ^{_{7 r AlX 2 3 -r (2}} ) ( wherein R, R ⁷ is an alkyl group having 1 to 4 carbon atoms, X ² represents a hydrogen atom or a halogen element, r is is 0 <r ≦ 3 .)

The aluminum compound represented by the general formula (1) includes aluminum trihalide, alkoxyaluminum dihalide, dialkoxyaluminum halide, and trialkoxyaluminum. Specific examples thereof include aluminum trichloride, aluminum tribromide. , Aluminum triiodide,
Diethoxyaluminum chloride, diisopropoxyaluminum chloride, dibutoxyaluminum chloride, ethoxyaluminum dichloride, isopropoxyaluminum dichloride, butoxyaluminum dichloride, trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, Examples thereof include aluminum triisobutoxy, and among them, preferred substances are aluminum trichloride, diisopropoxy aluminum chloride, isopropoxy aluminum dichloride, triethoxy aluminum, and triisopropoxy aluminum.

The aluminum compound represented by the general formula (1) includes trialkylaluminum, dialkylhydride, dialkylaluminum halide and alkylaluminum dihalide, and specific examples thereof include triethylaluminum, triisobutylaluminum, diethylaluminum. Hydride, diisobutyl hydride, diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum dichloride, propylaluminum dichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride and the like, among which, preferably, triethylaluminum, diethylaluminumchloride, ethylaluminum Dichloride, ethyl aluminum Musesquichloride.

As the above-mentioned aluminum compound, one or more kinds selected from the compound group of the above-mentioned general formulas (1) and (2) can be used. The compound is
It may be used by bringing it into direct contact with other components or by dissolving and diluting it in an organic solvent such as an aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as hexane or heptane.

Specific examples of the organosilicon compound having a Si—O bond include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, and 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, cyclohexylethyldimethoxy 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 (iso-propyl) diethoxysilane, cyclohexyl (n-butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl ( iso-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyl Ethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethylsilane Methoxysilane, methyltriethoxysilane,
Ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-propyltrimethoxysilane, iso-propyltriethoxysilane, n-butyltrimethoxysilane, iso-butyltrimethoxy Silane, t-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldi Ethoxysilane, cyclohexylcyclopentyldipropoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane,
Bis (3-methylcyclohexyl) dimethoxysilane,
4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxy Silane, tetrabutoxysilane and the like.

In addition to the above, polysiloxane may be used as the organosilicon compound. As the polysiloxane, general formula (3):

[0037]

Embedded image

(Wherein l represents the average degree of polymerization, and
30,000, and the main constituent of R ⁸ to R ¹⁵ is a methyl group;
Sometimes a portion of R ⁸ to R ¹⁵ is substituted with a phenyl group, hydrogen, a higher fatty acid residue, an epoxy-containing group, or a polyoxyalkylene group, and in the compound of the above general formula, R ¹¹ and R ¹² are methyl groups. And those forming a cyclic polysiloxane of the formula (1). 1) of the polysiloxane represented by
Species or two or more species.

The polysiloxane is also generically referred to as silicone oil and has a viscosity at 25 ° C. of 2 to 10,000 centistokes, preferably 2 to 1,000 centistokes, more preferably 3 to 500 centistokes, and is a liquid or viscous liquid at room temperature. It is a linear, partially hydrogenated, cyclic or modified polysiloxane.

As the chain polysiloxane, dimethylpolysiloxane and methylphenylpolysiloxane are used as partially hydrogenated polysiloxane, methylhydrogenpolysiloxane having a hydrogenation rate of 10 to 80%, and as cyclic polysiloxane, hexamethylcyclosiloxane is used. Trisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and modified polysiloxane are higher grades. Examples thereof include fatty acid group-substituted dimethylsiloxane, epoxy group-substituted dimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxane.

These polysiloxanes can be used by dissolving them in an organic solvent such as toluene, xylene, hexane or heptane.

In the preparation of the solid catalyst component (A) of the present invention, the use ratio of each component is not particularly limited and is optional. Preferably, component (b) is used in an amount of 0.1 to 200 ml per 1 g of component (a).
, More preferably 0.5 to 100 ml, component (c) is 0.01 to 2 g, more preferably 0.1 to 2 g, and component (d) is 0.01 to 2 g.
The organic solvent which is 2 g, more preferably 0.1 to 2 g, and liquid at room temperature, is 1 to 100 ml, more preferably 3 to 50 ml.

When the above-mentioned optional organic silicon compound or aluminum compound is used,
Usually, the amount of the organosilicon compound is 0.01 to 10 g, preferably 0.05 to 5 g, and the amount of the aluminum compound is 0.01 to 10 g, preferably 0.05 to 2 g, per 1 g of the component (a).

As described above, the solid catalyst component of the present invention does not use a special solvent for dissolving a magnesium compound such as an alcohol, a tetraalkoxytitanium compound or carbon dioxide as in the prior art, and does not use a raw material. Regardless of the particle size and shape of the alkoxymagnesium, it can be prepared without grinding, sieving or spray-drying to further control the particle size and shape,
An olefin polymer or copolymer having a uniform particle size and particle size distribution and having good fluidity can be obtained.

Next, the organoaluminum compound (B) (hereinafter sometimes referred to as “component (B)”) used in the present invention is represented by the general formula: R ³ _n AlY _3-n (wherein R ³ Is an alkyl group having 1 to 4 carbon atoms, Y is any one of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom, and n is a real number satisfying 0 <n ≦ 3.) Can be

Such an organoaluminum compound (B)
As, triethylaluminum, diethylaluminum chloride, tri-iso-butylaluminum,
Examples thereof include diethylaluminum bromide and ethylaluminum hydride, and one or more of them can be used. Preferably triethylaluminum, tri-iso
-Butyl aluminum.

The halogen-containing organosilicon compound (C) (hereinafter sometimes referred to as “component (C)”) used in the present invention has a general formula: R ⁴ _p Si (OR ⁵ ) _4-p ( In the formula, R ⁴ is an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group having 1 to 12 carbon atoms, which may be the same or different, and R ⁵ has 1 to 4 carbon atoms. Wherein p is an integer of 0 or 1 to 3, which may be the same or different from any one of an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, and an aralkyl group. Is used.

Examples of such an organosilicon compound (C) include phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, and alkoxysilane.

Specific examples of the organosilicon compound (C) include trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, -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, cyclohexylethyldimethoxy Silane, cyclohexyl (is
o-propyl) dimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, 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 (iso-propyl) diethoxysilane, cyclohexyl (n- Butyl) dimethoxysilane, cyclohexyl (n-butyl) diethoxysilane, cyclohexyl (i
(so-butyl) dimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylethyldimethoxysilane, phenylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexyldimethylethoxysilane, cyclohexyldiethyl Methoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, 2-ethylhexyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane,
n-propyltrimethoxysilane, n-propyltriethoxysilane, iso-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, bis (4-methylcyclohexyl) dimethoxysilane, 3,5-dimethoxycyclohexylcyclohexyldimethoxysilane, bis (3,5-dimethylcyclohexyl) dimethoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-iso- And propoxysilane.

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, dicyclopentyldimethoxysilane, dicyclopentyldimethoxysilane, Cyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cycle Hexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3,5-dimethylcyclohexylcyclopentyldimethoxysilane are preferably used, and the organosilicon compound (D) is One type or a combination of two or more types can be used.

In the polymerization method of the present invention, polymerization or copolymerization of olefins is carried out in the presence of the catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C). The use ratio of each component is arbitrary as long as it does not affect the effect of the present invention, and is not particularly limited. Usually, the organoaluminum compound (B) is contained in the solid catalyst component (A). Per mole of titanium atom, in a molar ratio of 1 to 1,000, preferably
The organosilicon compound (C) is used in a molar ratio of 0.002 to 2, preferably 0.01 to 0.5, per mol of the component (B).

The olefin polymerization catalyst of the present invention comprises the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C) described above.
As an electron donor (external electron donor) at the time of polymerization, an organic compound containing oxygen or nitrogen in addition to 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 the like.

More specifically, alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, phenols such as phenol and cresol, methyl ether, ethyl ether, propyl Ethers such as ether, butyl ether, amyl ether and 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 Monocarboxylic acid esters such as P-ethoxyethyl benzoate, methyl anisate, ethyl anisate, diethyl maleate, dibutyl maleate, dimethyl adipate, diethyl adipate, dipropyl adipate, dibutyl adipate, dimethyl adipate, adipic acid Dicarboxylic acid esters such as diisodecyl, dioctyl adipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate, dioctyl phthalate, dinonyl phthalate, didecyl phthalate Ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, acetone phenone and benzophenone; acid halides such as phthalic dichloride and terephthalic dichloride; acetaldehyde; Examples include aldehydes such as propionaldehyde, octylaldehyde, and benzaldehyde; amines such as methylamine, ethylamine, tributylamine, piperidine, aniline, and pyridine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile.

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

Further, in the present invention, in the polymerization of olefin (also referred to as main polymerization) using a catalyst comprising the solid catalyst component (A), the organoaluminum compound (B) and the organosilicon compound (C), In order to further improve the activity, stereoregularity, and particle properties of the produced polymer, it is preferable to carry out preliminary polymerization prior to polymerization. As monomers for the prepolymerization, not only ethylene and propylene but also monomers such as styrene and vinylcyclohexane can be used.

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 regulator 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 at most 5 MPa, more preferably at most 2.5 MPa.

[0057]

EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. Example 1 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were charged into a 500 ml round bottom flask equipped with a stirrer and sufficiently substituted with nitrogen gas.
It was made into a suspension state at ℃. 20 ml of titanium tetrachloride was charged therein, and the mixture was stirred at 30 ° C. while stirring at a tip peripheral speed of 1.2 m / sec.
And kept for 1 hour (aging treatment). Then, 0.
The temperature was raised to 50 ° C. at a rate of 44 ° C./min, and 4.7 ml of bis (2-ethylhexyl) phthalate was added.
The temperature was raised at a rate of one minute, and when the temperature reached 70 ° C., 1.0 ml of diethyl phthalate was added. Further, the inside of the system was heated to 112 ° C. at a rate of 0.44 ° C./min and reacted for 2 hours. After the 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. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added,
The mixture was treated with stirring at 100 ° C. for 2 hours.
Was washed eight times with 100 ml of n-heptane to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 1.8 wt%.

<Formation and Polymerization of Polymerization Catalyst> In a 2-liter autoclave equipped with a stirrer completely replaced with nitrogen gas, 1.32 mmol of triethylaluminum was placed.
1, cyclohexylmethyldimethoxysilane 0.13m
mol and the solid catalyst component is 0.0
026 mmol was charged to form a polymerization catalyst. Thereafter, 3 l of hydrogen gas and 1.4 l of liquefied propylene were charged,
Preliminary polymerization was performed at 20 ° C. for 5 minutes with stirring. Thereafter, the temperature was raised 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 properties of the polymer.
It was shown to.

The properties of the polymer shown in Table 1 were obtained by setting the weight of the produced polymer to (a) g after the completion of the polymerization reaction, and extracting the polymer in boiling n-heptane for 6 hours. The weight of the polymer was defined as (b) g, and the polymerization activity and the yield of the polymer made of all crystals were determined by the following formulas.

Polymerization activity (Y) = (a) / solid catalyst component Yield of all crystalline polymer (HI)% = (b) × 100 / (a)

Further, the melt index of the produced polymer
(MI), bulk specific gravity (BD), average particle size, particle size distribution ((D 90-D
10) / D50, where D90 is the particle size at an integrated particle size of 90 wt%, D10 is the particle size at an integrated particle size of 10 wt%, and D50 is the particle size at an integrated particle size of 50 wt%. Express. Table 1 shows the amount of the polymer having a particle size of 100 μm or less.

Example 2 Example 1 except that 2.5 ml of diisodecyl phthalate was used instead of bis (2-ethylhexyl) phthalate.
An experiment was performed in the same manner as described above, and the obtained results are also shown in Table 1. When the Ti content in the solid catalyst component was measured,
1.7 wt%.

Example 3 <Preparation of solid catalyst component> 10 g of diethoxymagnesium, 80 ml of toluene and 80 ml of bis (2-) were placed in a 500 ml round bottom flask equipped with a stirrer and sufficiently purged with nitrogen gas.
1.0 ml of ethylhexyl) phthalate was charged and suspended at 10 ° C. 20 ml of titanium tetrachloride was charged therein, the temperature was raised to 30 ° C. while stirring at a peripheral speed of the stirring blade of 1.2 m / sec, and the temperature was maintained for 1 hour (aging treatment). Then 0.44
The temperature was raised to 50 ° C. at a rate of 50 ° C./min, and 5.2 ml of bis (2-ethylhexyl) phthalate was added. Then, the temperature was further raised at a rate of 0.44 ° C./min. And then at 85 ° C. 3.0 ml of tetraethoxysilane were added. Further, at a rate of 0.44 ° C./min, 11
The temperature was raised to 2 ° C., and the reaction was performed for 2 hours. After the completion of the reaction, the supernatant was removed and treated with 80 ml of toluene and 20 ml of titanium tetrachloride at 100 ° C. for 15 minutes.
Washing was performed 3 times at 100 ° C. using ml. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added, and 100 ° C.
For 2 hours while stirring, and then washed 8 times with 100 ml of n-heptane at 40 ° C. to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 1.8 wt%.

<Formation and Polymerization of Polymerization Catalyst> A polymerization catalyst was formed and polymerization was carried out in the same manner as in Example 1 except that the solid catalyst component obtained as described above was used. It is also shown in Table 1.

Example 4 An experiment was conducted in the same manner as in Example 3 except that 1.2 ml of di-n-propyl phthalate was used instead of diethyl phthalate. The results obtained are shown in Table 1. When the Ti content in the solid catalyst component was measured, it was 2.2 wt%.

Examples 5 to 7 Experiments were carried out in the same manner as in Example 1 except that the peripheral speed of the tip of the stirring blade during stirring and the rate of temperature increase after the aging treatment were performed under the conditions shown in Table 1, respectively. The obtained results are also shown in Table 1.

Comparative Example 1 <Preparation of a solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were put into a 500 ml round bottom flask equipped with a stirrer and sufficiently replaced with nitrogen gas, and suspended. 20 ml of titanium tetrachloride at room temperature was added thereto, and the mixture was stirred at 70 ° C. while stirring at a tip peripheral speed of a stirring blade of 1.2 m / sec.
After heating at 1 ° C./min to 5.2 ml of bis (2-ethylhexyl) phthalate, the temperature was further raised to 112 ° C. and reacted for 2 hours. After completion of the reaction, the supernatant was removed and the mixture was heated to 100 ° C. using 80 ml of toluene and 20 ml of titanium tetrachloride.
And further treated with 100 ml of toluene for 10 minutes.
Washed three times at 0 ° C. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added and treated while stirring at 100 ° C. for 2 hours, and then 100 ml of n-heptane at 40 ° C.
8 times to obtain a solid catalyst component. When the Ti content in this solid catalyst component was measured, it was 3.6 wt%.

<Formation and Polymerization of Polymerization Catalyst> Example 1 was repeated except that the solid catalyst component obtained as described above was used.
A polymerization catalyst was formed and polymerization was carried out in the same manner as described above, and the obtained results are shown in Table 1.

Comparative Example 2 <Preparation of solid catalyst component> 10 g of diethoxymagnesium and 80 ml of toluene were put into a 500 ml round bottom flask equipped with a stirrer, which was sufficiently substituted with nitrogen gas.
A suspension was formed at 0 ° C. In this, room temperature titanium tetrachloride 2
After 0 ml was charged and 3.5 ml of di-n-butyl phthalate was added, the temperature was raised to 112 ° C. at 5 ° C./min with stirring at a peripheral speed of the stirring blade of 1.2 m / sec for 2 hours of reaction. After the 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. Thereafter, 80 ml of toluene and 20 ml of titanium tetrachloride were newly added,
Treat with stirring at 100 ° C. for 2 hours and then at 40 ° C.
The solid catalyst component was obtained by washing 8 times with 100 ml of n-heptane. When the Ti content in this solid catalyst component was measured,
It was 4.8 wt%.

<Formation and Polymerization of Polymerization Catalyst> Example 1 was repeated except that the solid catalyst component obtained as described above was used.
A polymerization catalyst was formed and polymerization was carried out in the same manner as described above, and the obtained results are shown in Table 1.

Comparative Example 3 After the aging treatment, a solid catalyst component was prepared, a polymerization catalyst was formed, and polymerization was carried out in the same manner as in Example 1 except that the temperature was raised at a rate of 0.2 ° C./min. The results are shown in Table 1. When the Ti content in this solid catalyst component was measured,
It was 2.2 wt%.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

According to the present invention, when olefins are polymerized in the presence of the catalyst for olefin polymerization of the present invention, the catalytic activity and the stereoregularity of the produced polymer are maintained at a higher level than when a conventional catalyst is used. As it is, a granular or spherical polymer having a narrow particle size distribution and a high bulk specific gravity can be obtained in high yield.

[Brief description of the drawings]

FIG. 1 is a flow chart showing steps for preparing a catalyst component and a polymerization catalyst of the present invention.

Claims (2)

[Claims] ( ¹ ) A compound represented by the general formula Mg (OR ¹ ) _{2 wherein} R
¹ represents an alkyl group or an aryl group having 1 to 4 carbon atoms. (B) a general formula Ti (OR ² ) _m X _4-m (wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, X represents a halogen element, and m represents 0 or A titanium compound represented by the following formula: (c) a phthalic acid diester in which the total number of carbon atoms of two alkyl groups is 10 or more, and (d) a total of 10 carbon atoms of two alkyl groups. A solid catalyst component for the polymerization of olefins comprising a phthalic acid diester of less than 60%, wherein the suspension formed during aging and after aging formed from component (a) and component (b) is in a temperature range below 60 ° C. The above component (c) is contact-reacted in the held state, and at least up to 90 ° C. after aging, the rate of temperature increase is 0.3 to 10.0 on average.
A solid catalyst component for olefins polymerization, which is obtained by raising the temperature at a rate of ° C / min and adjusting the stirring speed of the reaction vessel to a peripheral speed of the tip of the stirring blade of 0.5 to 10 m / sec or more. 2. A catalyst for polymerization of olefins, which is formed from the following components (A), (B) and (C). (A) The solid catalyst component according to claim 1, (B) a general formula R ³ _n AlY _3-n (wherein, R ³ is an alkyl group having 1 to 4 carbon atoms, Y is a hydrogen atom, a chlorine atom, or a bromine. An organic aluminum compound represented by the formula: R ⁴ _p Si (OR ⁵ ) _4-p (wherein n is a real number satisfying 0 <n ≦ 3). R ⁴ is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group, which may be the same or different, and 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, which may be the same or different, and p is 0 or an integer of 1 to 3).