JPH0714975B2 - Method for producing α-olefin polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing an α-olefin polymer. More specifically, in processes such as slurry polymerization, bulk polymerization, and gas phase polymerization, it is not necessary to remove the catalyst residue and the amorphous polymer by using a solid catalyst component having high activity per transition metal and high stereoregularity. It also relates to a method for producing an α-olefin polymer having a high bulk density and a small amount of fine powder by controlling the particle shape of the solid catalyst component very well.

<Prior Art> Generally, as a method for producing an α-olefin polymer such as propylene or butene-1, a so-called transition metal compound of Group IV to VI and an organometallic compound of Group I to III of the periodic table is used. The use of Ziegler-Natta catalysts is well known.

In particular, titanium trichloride catalysts are widely used when industrially producing α-olefin polymers.

However, in this production method, an amorphous polymer is produced as a by-product in addition to the highly stereoregular α-olefin polymer which is industrially highly valuable.

This amorphous polymer has little industrial utility value and has a great adverse effect on the mechanical properties when the α-olefin polymer is processed into a film, a fiber or other processed products and used.

In addition, the production of the above-mentioned amorphous polymer causes a loss of raw material monomers, and at the same time, the production equipment necessary for removing the amorphous polymer is indispensable, which causes a great disadvantage from an industrial viewpoint.

Therefore, if such an amorphous polymer is not produced at all, or if it is present, it is very advantageous if it is extremely small.

On the other hand, a catalyst residue remains in the α-olefin polymer obtained by such a polymerization method, and this catalyst residue causes problems in various points such as the stability and processability of the α-olefin polymer, and the catalyst residue is removed. And the equipment for stabilization is needed.

This drawback can be ameliorated by increasing the catalytic activity represented by the weight of the α-olefin polymer produced per unit weight of the catalyst, and the equipment for removing the catalyst residue is not required, so that the production of the α-olefin polymer is possible. It is possible to reduce the production cost required for

The present inventors previously mentioned that in JP-A-61-287904, in the coexistence of A) an organosilicon compound having a Si—O bond,
A titanium compound represented by the general formula Ti (OR ¹ ) nX _4- n (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is a number of 0 <n ≦ 4) A solid product obtained by reduction with an organomagnesium compound is treated with an ester compound and a mixture of an ether compound and titanium tetrachloride, a solid catalyst component containing a trivalent titanium compound, B) an organoaluminum compound, C) It has been found that a catalyst system composed of a silicon compound having a Si-OR ² bond (R ² is a hydrocarbon group having 1 to 20 carbon atoms) exhibits high activity and regularity in the polymerization of α-olefin. .

However, when the solid catalyst such as the Ziegler-Natta catalyst is subjected to industrial practical use, its particle shape is very important for controlling the bulk density, particle size, and fluidity of the polymer. The particle shape of the catalyst is still unsatisfactory.

Regarding the improvement of the particle shape, in the polymerization of ethylene, an attempt has been made to overcome such a problem by using a solid catalyst in which a titanium-magnesium compound is supported on silica gel (JP-A-54-148098). , JP-A-56-47407).

In addition, the present inventors also, in the polymerization of polypropylene,
It was proposed that the particle properties could be significantly improved by using a solid catalyst obtained by impregnating silica gel with a titanium-magnesium compound (Japanese Patent Application No. 61-21109). According to these methods, the particle shape is surely extremely improved, but since a large amount of the silica gel used as the carrier remains in the product, fish
It causes eye and is not good in quality.

<Problems to be Solved by the Invention> Under the present circumstances, the problems to be solved by the present invention, that is, the object of the present invention is to have a sufficiently high catalytic activity such that removal of a catalyst residue and an amorphous polymer is unnecessary. It is to provide a method for producing an α-olefin polymer having stereoregularity, a high bulk density and a small amount of fine powder, and further containing no inorganic oxide such as silica gel which causes fish eyes in film applications. .

<Means for Solving Problems> The present invention includes: A) an organosilicon compound having a SiO bond and a pore radius 1
In the coexistence of porous polymer beads having a pore volume of 0.1 cc / g or more at 00 to 5,000 Å, the general formula Ti (OR ¹ ) nX _4- n (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X Is a halogen atom, n is 0
<N ≦ 4 is represented. ), A solid product obtained by reducing a titanium compound represented by an organomagnesium compound with an ester compound, and a trivalent titanium compound-containing solid catalyst component obtained by treating the mixture with an ether compound and titanium tetrachloride, The present invention relates to a method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using a catalyst system comprising B) an organoaluminum compound and C) an electron-donating compound.

The use of the present catalyst system achieves the above objectives.

Hereinafter, the present invention will be specifically described.

(A) Titanium Compound The titanium compound used in the present invention has a general formula of Ti (OR
¹ ) nX _4- n (R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, and n is a number of 0 <n ≦ 4). Specific examples of R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-amyl, isoamyl, n-hexyl, n-heptyl, n-.
Alkyl groups such as octyl, n-decyl, n-dodecyl,
Examples thereof include aryl groups such as phenyl, cresyl, xylyl and naphthyl, cycloalkyl groups such as cyclohexyl and cyclopentyl, allyls such as propenyl and aralkyl groups such as benzyl.

An alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferable. Particularly, a linear alkyl group having 2 to 18 carbon atoms is preferable.

It is also possible to use titanium compounds having two or more different OR ¹ groups.

Examples of the halogen atom represented by X include chlorine, bromine and iodine. Especially chlorine gives favorable results.

The value of n of the titanium compound represented by the general formula Ti (OR ¹ ) nX _4- n is 0 <n ≦ 4, preferably 2 ≦ n ≦ 4, and particularly preferably n = 4.

As a method for synthesizing the titanium compound represented by the general formula Ti (OR ¹ ) nX _4- n (0 <n ≦ 4), a known method can be used.
For example, a method of reacting Ti (OR ¹ ) ₄ and TiX ₄ in a predetermined ratio, or a method of reacting TiX ₄ and a corresponding alcohol in a predetermined amount can be used.

(B) Organosilicon Compound Having Si-O Bond The organosilicon compound having a Si-O bond used in the synthesis of component A) of the present invention is represented by the following general formula.

Si (OR ³ ) mR ⁴ _4- m R ⁵ (R ⁶ ₂ SiO) pSiR ⁷ ₃ or (R ⁸ ₂ SiO) q where R ³ is a hydrocarbon group having 1 to 20 carbon atoms, R ⁴ and R ⁵ , R ⁶ , R
⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms or hydrogen atoms, m is a number of 0 <m ≦ 4, and p is 1 to 1,00.
It is an integer of 0 and q is an integer of 2 to 1,000.

Specific examples of the organic silicon compound include the following.

Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxydiisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetra-n -Butoxysilane, di-n-butoxydi-n-butylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octaethyltrisiloxane , Dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, and the like.

Preferred of these organosilicon compounds are those of the general formula
An alkoxysilane compound represented by Si (OR ³ ) mR ⁴ _4- m, preferably 1 ≦ m ≦ 4, and a tetraalkoxysilane compound having m = 4 is particularly preferable.

(C) Organomagnesium compound Next, as the organomagnesium used in the present invention, any type of organomagnesium compound containing a magnesium-carbon bond can be used. In particular, a Grignard compound represented by the general formula R ⁹ MgX (wherein R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents halogen) and a general formula R ¹⁰ R ¹¹ Mg (in the formula, R ¹⁰ And R ¹¹ represents a hydrocarbon group having 1 to 20 carbon atoms), and a dialkyl magnesium compound or a diaryl magnesium compound represented by the formula (I) is preferably used. Here, R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, isoamyl, n-hexyl. , N-octyl, 2-
1 to 20 carbon atoms such as ethylhexyl, phenyl and benzyl
Represents an alkyl group, an aryl group, an aralkyl group, or an alkenyl group.

Specifically, as the Grignard compound, methyl magnesium chloride, ethyl magnesium chloride, ethyl magnesium bromide, ethyl magnesium iodide, n-propyl magnesium chloride, n-propyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, sec-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-amylmagnesium chloride, isoamylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc.
As the compound represented by R ¹⁰ R ¹¹ Mg, diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, di-n-butyl magnesium, di-sec-
Butylmagnesium, di-tert-butylmagnesium,
Examples include n-butyl-sec-butylmagnesium, di-n-amylmagnesium, diphenylmagnesium and the like.

As a synthetic solvent for the above organomagnesium compound, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-n-amyl ether, diisoamyl ether, di-n-hexyl ether. , Di-n-octyl ether, diphenyl ether, dibenzyl ether,
Ether solvents such as phenetole, anisole, tetrahydrofuran and tetrahydropyran can be used. Further, a hydrocarbon solvent such as hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, or a mixed solvent of an ether solvent and a hydrocarbon solvent may be used. The organomagnesium compound is preferably used in the state of an ether solution. In this case, as the ether compound, an ether compound having 6 or more carbon atoms in the molecule or an ether compound having a cyclic structure is used.

In particular, it is preferable to use the Grignard compound represented by R ⁹ MgCl in the state of an ether solution from the viewpoint of catalytic performance.

It is also possible to use a hydrocarbon-soluble complex of the above-mentioned organomagnesium compound and an organometallic compound. Examples of organic metal compounds include organic compounds of Li, Be, B, Al or Zn.

(D) Porous Polymer Beads Examples of the porous polymer beads used as the component A) of the present invention include polystyrene type, polyacrylic acid ester type, polymethacrylic acid ester type, polyacrylonitrile type, polyvinyl chloride type. , And polyolefin-based porous polymer beads and the like. Specific examples include polystyrene, styrene-divinylbenzene copolymer, styrene-N, N'alkylenedimethacrylamide copolymer,
Styrene-ethylene glycol dimethyl methacrylate copolymer, methyl polyacrylate, polyethyl acrylate, methyl acrylate-divinylbenzene copolymer, ethyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate -Divinylbenzene copolymer, polyethylene glycol dimethacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, ethylene-acrylic Examples thereof include methyl acid copolymer and polypropylene.

Among these porous polymer beads, polystyrene-based, polyvinyl chloride-based, polyolefin-based, polyacrylonitrile-based porous polymer beads are preferably used, and more preferably polystyrene, styrene-divinylbenzene copolymer, polyvinyl chloride. Is used.

The average particle size of the porous polymer beads is 5 to 1,000 μ, preferably 10 to 600 μ, and particularly preferably 15 to 500 μ.
The pore volume between the pore radius of 100 to 5,000Å is 0.1c.
c / g or more, preferably 0.2 cc / g or more, particularly preferably 0.25
cc / g or more.

Furthermore, it is preferable to use a porous polymer from which adsorbed water is excluded. Specifically, there may be mentioned a method of drying under reduced pressure at a temperature of about 80 ° C. or higher, or a method in which the product dried at a temperature of about 60 ° C. or higher is treated with an organometallic compound such as organomagnesium and used.

(E) Ester Compound In the present invention, the ester compound used in the synthesis of the component A) is a mono- or polyvalent carboxylic acid ester, which is an aliphatic carboxylic acid ester, an olefin carboxylic acid ester, or an alicyclic carboxylic acid ester. , Aromatic carboxylic acid esters are used. Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate,
Ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate. , Diethyl malonate, dibutyl malonate, dimethyl maleate, dibutyl maleate,
Diethyl itaconate, dibutyl itaconate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate,
Examples include diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, and diphenyl phthalate. be able to.

Among these ester compounds, methacrylic acid ester,
Olefin carboxylic acid esters such as maleic acid esters and phthalic acid esters are preferred, and phthalic acid diesters are particularly preferred.

(F) Ether Compound Next, as an ether compound used in the present invention, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, diisoamyl ether, dineopentyl. Dialkyl ethers such as ether, di-n-hexyl ether, di-n-octyl ether, methyl-n-butyl ether, methyl isoamyl ether and ethyl isobutyl ether are preferred.

Di-n-butyl ether and diisoamyl ether are particularly preferred.

(G) Synthesis of Solid Catalyst Component A) The solid catalyst component A) of the present invention is a solid product obtained by reducing a titanium compound with an organomagnesium compound in the coexistence of an organosilicon compound and porous polymer beads, to produce an ester. It is synthesized by treating with a compound and a mixture of an ether compound and titanium tetrachloride. Preferably, the solid product obtained by reduction is treated with an ester compound and then treated with a mixture of an ether compound and titanium tetrachloride to synthesize.

All synthesis reactions are carried out in an atmosphere of an inert gas such as nitrogen or argon.

That is, the solid product is synthesized by reducing the titanium compound with the organomagnesium compound in the coexistence of the organosilicon compound and the porous polymer beads, in which case the precipitation of the solid by the reduction reaction occurs on the porous polymer bead particles, It is preferable that the solid product retains the shape of the porous polymer beads and does not generate fine powder.

Examples of the method of reducing the titanium compound with the organomagnesium compound include a method of adding the organomagnesium compound to a mixture of the titanium compound, the organosilicon compound and the porous polymer beads.

The titanium compound, the organosilicon compound and the porous polymer beads are preferably dissolved or diluted in a suitable solvent before use.

Such solvents include hexane, heptane, octane,
Aliphatic hydrocarbons such as decane, aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, diethyl ether,
Examples thereof include ether compounds such as dibutyl ether, diisoamyl ether and tetrahydrofuran.

The reduction reaction temperature is -50 to 70 ° C, preferably -30 to 50 ° C,
Particularly preferably, the temperature is -25 to 35 ° C.

The dropping time is not particularly limited, but is usually about 10 minutes to 6 hours. After completion of the reduction reaction, a post reaction may be further carried out at a temperature of 20 to 120 ° C.

The amount of the organic silicon compound used is an atomic ratio of silicon atoms to titanium atoms in the titanium compound, Si / Ti = 1 to 50,
The range is preferably 3 to 30, particularly preferably 5 to 25.

The amount of organomagnesium compound used is Ti + Si based on the sum of titanium and silicon atoms and the atomic ratio of magnesium atoms.
/Mg=0.1-10, preferably 0.2-5.0, particularly preferably 0.
It is in the range of 5 to 2.0.

The amount of the porous polymer beads used is such that the weight thereof in the solid product is 20 to 95% by weight, preferably 80 to 85% by weight.
Is the range.

The solid product obtained by the reduction reaction is subjected to solid-liquid separation, and washed with an inert hydrocarbon solvent such as hexane and heptane several times.

Next, the solid product obtained by the above method is treated with an ester compound.

The amount of the ester compound used is 0.1 to 50 mol, more preferably 0.3 to 20 mol, particularly preferably 0.5 to 10 mol, per 1 mol of titanium atom in the solid product.

In addition, the amount of the ester compound used per 1 mol of magnesium atom in the solid product is 0.01 to 1.0 mol, preferably
It is 0.03 to 0.5 mol.

The treatment of the solid product with the ester compound can be carried out by any known method such as a slurry method or a mechanical milling means such as a ball mill capable of bringing them into contact with each other. A large amount is generated and the particle size distribution is widened, which is not preferable from an industrial viewpoint. It is preferable to contact both in the presence of a diluent.

As the diluent, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, benzene, toluene, aromatic hydrocarbons such as xylene, cyclohexane, alicyclic hydrocarbons such as cyclopentane, 1,2-dichloroethane,
Halogenated hydrocarbons such as monochlorobenzene can be used. Among these, halogenated hydrocarbons and aromatic hydrocarbons are particularly preferable.

The amount of diluent used is 0.1 ml to 1,000 ml per gram of solid product. It is preferably 1 ml to 100 ml per 1 g. The processing temperature is −
It is 50 to 150 ° C, preferably 0 to 120 ° C. The treatment time is 10 minutes or longer, preferably 30 minutes to 8 hours. After the completion of the treatment, the mixture is allowed to stand, and solid-liquid separation is carried out, followed by washing with an inert hydrocarbon solvent several times to obtain an ester-treated solid.

Further, the treatment with the ester compound can be carried out at the same time when the ester compound is allowed to coexist during the subsequent treatment with the mixture of the ether compound and titanium tetrachloride.

Next, the treatment of the ester-treated solid with the mixture of the ether compound and titanium tetrachloride is preferably performed in a slurry state. The solvent used to make the slurry, pentane, hexane, heptane, octane, aliphatic hydrocarbons such as decane, toluene, aromatic hydrocarbons such as xylene, cyclohexane, methylcyclohexane, alicyclic hydrocarbons such as decalin, Examples thereof include halogenated hydrocarbons such as dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene and trichlorobenzene.

Slurry concentration is 0.05-0.5g solid / ml solvent, especially 0.1-0.4g
Solid / ml solvent is preferred.

The reaction temperature is 30 to 150 ° C, preferably 45 to 120 ° C, particularly preferably 60 to 100 ° C.

The reaction time is not particularly limited, but normally 30 minutes to 6 hours is suitable.

The method for adding the ester-treated solid, the ether compound and the titanium tetrachloride includes a method for adding the ether compound and the titanium tetrachloride to the ester-treated solid, and a method for adding the ester-treated solid to the solution of the ether compound and the titanium tetrachloride. Either method may be used.

In the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, a method of adding titanium tetrachloride after adding the ether compound or a method of simultaneously adding the ether compound and titanium tetrachloride is preferable. A method of adding a mixture with titanium chloride is particularly preferable.

The reaction of the ester-treated solid with the ether compound and titanium tetrachloride may be repeated twice or more. From the viewpoint of catalytic activity and stereoregularity, it is preferable to repeat the reaction with the mixture of the ether compound and titanium tetrachloride at least twice.

The amount of the ether compound used is 0.1 to 100 mol, preferably 0.1 to 1 mol of the titanium atom contained in the solid product.
It is 5 to 50 mol, particularly preferably 1 to 20 mol.

The amount of titanium tetrachloride added is 2 to 2,000 mol, preferably 10 per mol of titanium atom contained in the solid product.
~ 1,000 mol, particularly preferably 30-800 mol.

The addition amount of titanium tetrachloride to 1 mol of the ether compound is 1 to 100 mol, preferably 1.5 to 75 mol, and particularly preferably 2 to 50 mol.

The trivalent titanium compound-containing solid catalyst component obtained by the above method is subjected to solid-liquid separation, washed with an inert hydrocarbon solvent such as hexane or heptane several times, and then used for polymerization.

After solid-liquid separation, the above-mentioned aromatic hydrocarbon such as toluene or halogenated hydrocarbon solvent such as monochlorobenzene is washed with an excess amount at least once at a temperature of 50 to 120 ° C., and then aliphatic carbonization such as hexane is performed. It is preferable to use it for polymerization after repeating washing with a hydrogen solvent several times, from the viewpoint of catalytic activity and stereoregularity.

(H) Organoaluminum Compound B) In the present invention, the organoaluminum compound B) used in combination with the above-mentioned solid catalyst component A) has at least one Al-carbon bond in the molecule. A typical one is shown below by a general formula.

R ¹² _γ AlY _3-γ R ¹³ R ¹⁴ Al-O-AlR ¹⁵ R ¹⁶ Here, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrocarbon groups having 1 to 8 carbon atoms, Y Represents halogen, hydrogen or an alkoxy group. γ is a number represented by 2 ≦ γ ≦ 3.

Specific examples of the organic aluminum compound, triethyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, diethyl aluminum hydride, dialkyl aluminum hydride such as diisobutyl aluminum hydride, a mixture of trialkyl aluminum and dialkyl aluminum halide, tetraethyl dihydrate. Alumoxane,
An alkyl alumoxane such as tetrabutyl dialumoxane can be exemplified.

Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, alkylalumoxane is preferable, and especially triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are preferable. preferable.

The amount of the organoaluminum compound used can be selected within a wide range such as 1 to 1,000 mol per 1 mol of titanium atom in the solid catalyst, but the range of 5 to 600 mol is particularly preferable.

(I) Electron-donating compound C) In the present invention, the electron-donating compound used as the catalyst component C) during the polymerization includes a Si-OR ² bond (R ² has 1 carbon atom
~ 20 hydrocarbon groups. ) Or an organosilicon compound having a Si—N—C bond, an aromatic carboxylic acid ester compound and sterically hindered amines.

As the organosilicon compound, a compound represented by the general formula R ¹⁷ tSi (OR ² ) _4- t
(R ¹⁷ and R ² are hydrocarbon groups having 1 to 20 carbon atoms, and t is 0
Represents a number ≤t≤3. An alkoxysilane compound represented by the formula (4) is preferably used.

As the aromatic carboxylic acid ester compound, methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Ethyl anisate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, Examples thereof include di-n-octyl phthalate and diphenyl phthalate.

Examples of the sterically hindered amines include 2,6-substituted piperidines, 2,5-substituted pyrrolidines, and substituted methylenediamine compounds such as N, N, N ', N'-tetramethylmethylenediamine. .

Of these electron-donating compounds, the general formula R ¹⁷ tSi (OR
² ) An alkoxysilane compound represented by _4- t gives favorable results.

Specific examples of the alkoxysilane compound include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, and ethyltriethoxy. Examples thereof include silane, vinyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, butyltriethoxysilane, tetrabutoxysilane, vinyltributoxysilane and diethyldiethoxysilane.

The amount of the electron-donating compound used is from 0.01 to 1 mol per aluminum atom of the organoaluminum compound which is the component B).
5 mol, preferably 0.03 to 3 mol, particularly preferably 0.05
~ 1.0 mol.

(J) Polymerization Method of α-Olefin As a method of supplying each catalyst component for polymerization, there is no particular limitation except that the catalyst component is supplied in an inert gas such as nitrogen or argon in a water-free state.

The catalyst components A), B) and C) may be supplied individually or may be supplied by contacting any two of them in advance.

The polymerization can be carried out over -30 to 200 ° C, but in the region of temperature lower than 0 ° C, the polymerization rate is lowered,
Further, at 100 ° C. or higher, it is usually preferable to carry out in the range of 0 to 100 ° C. for the reason that a polymer having a high stereoregularity cannot be obtained. The polymerization pressure is not particularly limited, but it is 3 to 100 from the viewpoint of being industrial and economical.
A pressure of around atmospheric pressure is desirable. The polymerization method may be either continuous or batch. Further, slurry polymerization with an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, octane, liquid phase polymerization without solvent, or gas phase polymerization is also possible.

Next, the alpha-olefin applicable to the present invention has 3 or more carbon atoms, and specific examples thereof include propylene, butene-1, pentene-1, hexene-1, 3-methyl-pentene-1, 4 -Methyl-pentene-1 and the like, but the present invention is not limited to the above compounds. The polymerization according to the present invention may be either homopolymerization or copolymerization (including copolymerization with ethylene).

Upon copolymerization, a copolymer can be obtained by contacting two or more kinds of olefins in a mixed state.

Further, heteroblock copolymerization in which the polymerization is carried out in two or more stages can be easily carried out.

It is also possible to add a chain transfer agent such as hydrogen to control the molecular weight of the polymer.

<Example> Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (A) Synthesis of Organomagnesium Compound After a flask having an inner volume of 1 equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was replaced with argon, 32.0 g of milled magnesium for Grignard was added.

A dropping funnel was charged with 120 g of n-butyl chloride and 500 ml of di-n-butyl ether, and about 30 ml was added dropwise to magnesium in the flask to start the reaction. After the reaction was started, the dropping was continued at 50 ° C for 4 hours, and after the dropping was completed, the dropping was continued at 60 ° C for another
The reaction continued for an hour. Then, the reaction solution was cooled to room temperature,
Solids were separated. Hydrolysis of n-butylmagnesium chloride in di-n-butyl ether with 1N sulfuric acid,
When the concentration was determined by back titration with 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2.0 mol /.

(B) Synthesis of solid product After replacing a flask with an internal volume of 200 ml equipped with a stirrer and a dropping funnel with argon, a styrene-divinylbenzene copolymer (result of porosimeter measurement: pore radius 100-5,000Å
The pore volume in the space (hereinafter abbreviated as dVp (cc / g)) is dVp =
It was 0.91 cc / g. ) Dried under reduced pressure at 80 ℃ for 30 minutes
5.0 g and 20 ml of n-butyl ether were added, and 14.0 ml of the organomagnesium compound synthesized in (A) while stirring.
While maintaining the temperature in the flask at 80 ℃, from the dropping funnel
The solution was added dropwise over 10 minutes and further treated at the same temperature for 1 hour.
Then, with 20 ml of n-butyl ether twice, n-heptane 20
After repeatedly washing twice with ml, the product was dried under reduced pressure to obtain 5.0 g of an organomagnesium-treated product.

Next, after replacing the flask with an internal volume of 100 ml equipped with a stirrer and a dropping funnel with argon, 5.0 g of the organomagnesium-treated product synthesized above, 25 ml of n-heptane, 0.44 g (1.3 mmol) of tetrabutoxytitanium, and tetraethoxy Silane 4.
5 g (21.6 mmol) was added and the mixture was stirred at 30 ° C for 30 minutes.

Then, add 4.6 ml of the organomagnesium compound synthesized in (A) from the dropping funnel while maintaining the temperature in the flask at 5 ° C.
It dripped over time. After completion of the dropping, the mixture was stirred at 5 ° C. for 1 hour and further at room temperature for 1 hour, and then washed repeatedly with 25 ml of n-heptane 3 times and dried under reduced pressure to obtain 6.2 g of a brown solid product.

The solid product contained 0.4% by weight of titanium atoms and 3.9% by weight of magnesium atoms.

(C) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
6.0 g of a solid product synthesized by the reduction reaction of (B), 30.0 ml of monochlorobenzene and 0.41 of diisobutyl phthalate.
ml (1.5 mmol) was added and the reaction was carried out at 80 ° C. for 1 hour.

After the reaction, solid-liquid separation was carried out, and the mixture was washed twice with 30 ml of n-heptane.

After washing, add 30.0 ml of monochlorobenzene to the flask.
-Butyl ether (0.53 ml, 3.1 mmol) and titanium tetrachloride (9.6 ml, 87.3 mmol) were added, and the reaction was carried out at 80 ° C for 3 hours. After completion of the reaction, solid-liquid separation was carried out at 80 ° C., and then washed with 30 ml of monochlorobenzene at the same temperature twice. The above-mentioned treatment with the mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and n-heptane 30
After repeatedly washing twice with ml, the solid was dried under reduced pressure to obtain 5.4 g of a brown solid catalyst component.

The solid catalyst component contained 0.5% by weight of titanium atom, 4.3% by weight of magnesium atom, and 0.7% by weight of phthalate ester.

(D) Polymerization of propylene After a stainless steel autoclave with a magnetic stirrer having an inner volume of 130 ml was replaced with argon, 0.57 mmol of triethylaluminum, 0.057 mmol of phenyltriethoxysilane and 45.0 mg of the solid catalyst component obtained in the above (C) , And liquefied propylene 80 ml were charged into the autoclave.

The autoclave was kept at 60 ° C for 1 hour with stirring. After releasing excess propylene, the resulting polypropylene was air dried overnight. 11.7 g of polypropylene was obtained.

Therefore, the yield (g) of polypropylene per 1 g of titanium contained in the solid catalyst component (hereinafter abbreviated as PP / Ti) is PB / Ti = 5.
It was 2,000.

The percentage of the residue obtained by extracting the obtained polypropylene powder with boiling n-heptane for 6 hours (hereinafter abbreviated as IY (%)) is IY =
It was 93.9%. The bulk density of the polypropylene powder (hereinafter abbreviated as BD (g / ml)) was BD = 0.43 g / ml.

(E) Measurement of particle size distribution of polypropylene powder The polypropylene powder obtained in (D) above is opened with 0.125 mesh openings.
It was classified using a JIS standard mesh sieve of ~ 3.36 mm. Next, the weight of the polymer remaining on each sieve was measured, and its ratio to the weight of the total polymer was determined and accumulated from the small particle size side. The results of the cumulative fraction (% by weight) by sieving are shown in Table-1 and Figure-I. The bulk density (BD) is also shown in Table-1.

Comparative Example 1 (A) Synthesis of solid product After replacing a flask having an inner volume of 1 equipped with a stirrer and a dropping funnel with argon, 600 ml of n-heptane, 7.6 g (22.2 mmol) of tetrabutoxytitanium and tetraethoxysilane 78.1 g (375 mmol) was added to make a uniform solution, and the mixture was stirred at room temperature for 30 minutes. Next, 200 ml of the organomagnesium compound synthesized in (A) of Example 1 was gradually added dropwise from the dropping funnel over 3 hours while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was further stirred at room temperature for 1 hour, solid-liquid separated at room temperature, repeatedly washed with 600 ml of n-heptane three times and dried under reduced pressure to obtain 64.5 g of a brown solid product.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 200 ml with argon,
17.10 g of a solid product synthesized by the reduction reaction of (A), 85.5 ml of monochlorobenzene and diisobutyl phthalate 3.
76 ml (14.0 mmol) was added and the reaction was carried out at 80 ° C. for 1 hour.

After the reaction, solid-liquid separation was performed, and the solid was washed twice with 90 ml of n-heptane.

After washing, add 85.5 ml of monochlorobenzene to the flask.
-Butyl ether 5.64 ml (33.3 mmol) and titanium tetrachloride 100.9 ml (918 mmol) were added, and the reaction was carried out at 80 ° C for 3 hours. After completion of the reaction, solid-liquid separation was carried out at 80 ° C., and then 90 ml of monochlorobenzene was washed twice at the same temperature.

The above treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing with 90 ml of n-heptane was repeated twice, followed by drying under reduced pressure to obtain 14.4 g of a brown solid catalyst component.

The solid catalyst component contained 2.7% by weight of titanium atom, 21% by weight of magnesium atom and 9.7% by weight of phthalate ester.

(C) Polymerization Using the above solid catalyst, propylene was polymerized in the same manner as in (D) of Example 1.

PP / Ti = 153,000, IY = 96.4%, BD = 0.30 g / ml.

Moreover, the particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1, and the results shown in Table 1 and FIG. 1 were obtained.

Compared with Example 1, the bulk density of the polymer is significantly lower when not supported on the porous polymer beads. Also 500
An extremely large amount of fine powder of μ or less is produced.

Example 2 (A) Synthesis of solid product A flask having an internal volume of 200 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then a styrene-divinylbenzene copolymer (dVp = 1.05 cc / g) was added at 80 ° C. for 1 hour. Dried under reduced pressure for 9.9g, n-heptane 49.5ml, tetrabutoxy titanium 0.
90 g (2.6 mmol), tetraethoxysilane 9.49 g (45.
(5 mmol) was added and the mixture was stirred at 30 ° C. for 45 minutes.

Next, 24.0 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 45 minutes and further at 30 ° C for 45 minutes, and then n-heptane 50 ml.
The product was dried 3 times under reduced pressure and dried under reduced pressure to give a brown solid product 1.
5.9 g was obtained.

The solid product contained 0.54% by weight of titanium atoms and 4.2% by weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask containing 100 ml of the content catalyst with argon,
6.8 g of a solid product synthesized by the reduction reaction of (A), 22.7 ml of toluene and 1.8 ml (6.7 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 23 ml of toluene.

After washing, add 22.7 ml of toluene, 1.5 ml of n-butyl ether (8.9 mmol) and 26.5 ml of titanium tetrachloride to the flask.
(241 mmol) was added and the reaction was carried out at 95 ° C for 3 hours. After completion of the reaction, solid-liquid separation was carried out at 95 ° C., and then 23 ml of toluene was washed twice at the same temperature. The above treatment with the mixture of n-butyl ether and titanium tetrachloride was carried out again for one hour, and the washing with 23 ml of n-heptane was repeated twice, followed by drying under reduced pressure to obtain 5.5 g of a brown solid catalyst component.

The solid catalyst component contained 0.46% by weight of titanium atoms, 5.4% by weight of magnesium atoms, and 1.5% by weight of phthalates.

(C) Polymerization Using the solid catalyst component synthesized in (B) above, propylene was polymerized under the same conditions as in (D) of Example 1.

PP / Ti = 233,000, IY = 95.7%, BD = 0.35 g / ml.

Moreover, when the particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1, the results shown in Table 1 and FIG. 1 were obtained.

Example 3 (A) Synthesis of solid product After replacing a flask having an inner volume of 200 ml equipped with a stirrer and a dropping funnel with argon, a styrene-divinylbenzene copolymer (dVp = 0.91 cc / g) was added at 80 ° C. for 1 hour. After 7.0 g of the product dried under reduced pressure and 28 ml of n-butyl ether were added, 20.0 ml of the organomagnesium compound synthesized in (A) of Example 1 was added to the mixture through a dropping funnel while maintaining the temperature in the flask at 80 ° C while stirring. The mixture was added dropwise over a period of minutes and further treated at the same temperature for 1 hour. And 28 ml of n-butyl ether twice, n
-Washing was repeated twice with 28 ml of heptane and then dried under reduced pressure to obtain 7.0 g of an organomagnesium-treated product.

Next, after replacing the flask with an inner volume of 100 ml equipped with a stirrer and a dropping funnel with argon, 7.0 g of the organomagnesium-treated product synthesized above and 85 ml of n-heptane, 0.62 g (1.8 mmol) of tetrabutoxytitanium, and tetraethoxy Silane 6.
81 g (30.3 mmol) was added and the mixture was stirred at 30 ° C for 30 minutes.

Next, 16.0 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1 hour and further at room temperature for 1 hour, and then n-heptane 35 ml.
The product was dried 3 times under reduced pressure and dried under reduced pressure to give a brown solid product.
11.6 g was obtained.

The solid product contained 0.46% by weight of titanium atoms and 5.1% by weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
4.22 g of a solid product synthesized by the reduction reaction of (A), 14.0 ml of toluene and 0.94 ml of diisobutyl phthalate (3.5
Was added and the reaction was carried out at 95 ° C. for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 20 ml of toluene.

After washing, toluene 14.0 ml, n-butyl ether 0.93 ml (5.1 mmol) and titanium tetrachloride 16.4 m in the flask.
l (149 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours.
After completion of the reaction, solid-liquid separation was performed at 95 ° C, and then toluene was added at the same temperature.
It was washed twice with 20 ml. The above treatment with the mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 20 ml of n-heptane and then dried under reduced pressure to obtain 3.65 g of a brown solid catalyst component.

The solid catalyst component contained 0.41% by weight of titanium atoms, 5.2% by weight of magnesium atoms, and 1.0% by weight of phthalates.

(C) Polymerization Using the solid catalyst component synthesized in (B) above, propylene was polymerized under the same conditions as in (D) of Example 1. The results were PP / Ti = 124,000, IY = 93.9%, BD = 0.45 g / ml.

Further, the particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1, and the results shown in Table 1 were obtained.

Comparative Example 2 (A) Synthesis of Solid Product A flask having an inner volume of 200 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then a styrene-divinylbenzene copolymer (dVp = 0.08 cc / g (pore radius 100Å Below and 5,000
The pore volume including the above was 0.93 cc / g). ) 80
5.0g of n-heptane 25.0 after vacuum drying at ℃ for 1 hour
ml, tetrabutoxy titanium 0.23 g (0.67 mmol), tetraethoxysilane 2.42 g (11.6 mmol)
Stir for 45 minutes at ° C.

Next, 6.1 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 45 minutes and then at 30 ° C for 45 minutes, and then n-heptane 30 ml.
Repeatedly washed 3 times with and dried under reduced pressure to give a brown solid product 5.
I got 7g.

The solid product contained 0.3% by weight of titanium atoms and 2.5% by weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
5.6 g of a solid product synthesized by the reduction reaction of (A), 18.7 ml of toluene and 0.50 ml (1.9 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 18.7 ml of toluene.

After completion of washing, the flask was charged with 18.7 ml of toluene, n-butyl ether, 1.24 ml (7.3 mmol) and titanium tetrachloride.
9 ml (199 mmol) was added and the reaction was carried out at 95 ° C for 3 hours. After completion of the reaction, solid-liquid separation was carried out at 95 ° C., and washing with 18.7 ml of toluene was carried out twice at the same temperature. The above-mentioned treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 18.7 ml of n-heptane and then dried under reduced pressure to obtain 4.7 g of a reddish solid.

As a result of analysis of the solid catalyst component, a trace amount of titanium atom was detected, and a magnesium atom and phthalate ester were not detected.

(C) Polymerization Propylene was polymerized under the same conditions as in (D) of Example 1 using the solid catalyst component synthesized in (B) above.
No polymer was obtained.

Compared with Examples 1, 2 and 3, even in the case of porous polymer beads, when the pore volume in the pore radius range of 100 to 5,000Å, that is, dVp is small, the catalyst component having polymerization activity is used as the porous polymer. It cannot be retained internally and does not serve as an effective propylene polymerization catalyst.

Example 4 (A) Synthesis of solid product A flask having an inner volume of 300 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then polyvinyl chloride (dVp = 0.27 cc /
g) was dried under reduced pressure at 80 ° C. for 1 hour, 20.7 g and 68 ml of n-butyl ether were added, and 68 ml of the organomagnesium compound synthesized in (A) of Example 1 was heated to 30 ° C. while stirring. While maintaining the temperature, the solution was dropped from the dropping funnel in 1 minute, and further treated at the same temperature for 1 hour.

Then, twice with 42 ml of n-butyl ether, 85 of n-heptane
After repeatedly washing with ml twice, it was dried under reduced pressure to obtain 20.3 g of an organomagnesium-treated product.

Next, after replacing the flask with an internal volume of 100 ml equipped with a stirrer and a dropping funnel with argon, 9.3 g of the organomagnesium-treated product synthesized above and 46 ml of n-heptane, 0.32 g of tetrabutoxytitanium (0.94 mmol) and tetraethoxy Silane
3.3 g (16 mmol) was added and the mixture was stirred at 30 ° C for 45 minutes.

Next, 8.4 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1 hour and further at room temperature for 1 hour, and then n-heptane 46 ml.
The product was dried 3 times under reduced pressure and dried under reduced pressure to give a brown solid product.
10.5 g was obtained.

The solid product contained 0.2% by weight of titanium atoms and 2.4% by weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
5.1 g of a solid product synthesized by the reduction reaction of (A), 17.0 ml of toluene and 0.43 ml (1.6 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 17 ml of toluene.

After washing, toluene 17.0 ml, n-butyl ether 1.12 ml (6.6 mmol) and titanium tetrachloride 20.0 m in the flask.
l (182 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours.
After completion of the reaction, solid-liquid separation was carried out at 95 ° C., followed by washing twice with 17 ml of toluene at the same temperature. The above treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 17 ml of n-heptane and dried under reduced pressure to obtain 3.8 g of a brown solid catalyst component.

The solid catalyst component contained 0.1% by weight of titanium atoms, 1.5% by weight of magnesium atoms, and 0.4% by weight of phthalates.

(C) Polymerization Using the solid catalyst component synthesized in (B) above, propylene was polymerized under the same conditions as in (D) of Example 1. The results were PP / Ti = 100,000, IY = 95.5%, BD = 0.34 g / ml. Further, the particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1, and the results shown in Table 1 were obtained.

Example 5 (B) Synthesis of solid catalyst component After a flask having an inner volume of 3 equipped with a stirrer and a dropping funnel was replaced with argon, porous polymer beads (dvp = 1.77) made of a copolymer of styrene and divinylbenzene were replaced. c
c / g, average particle size 156 μm) acid-air dried at 80 ° C
234 g, toluene 2.34, tetrabutoxy titanium 15 ml (44
150 mmol (673 mmol) of tetraethoxysilane and stirred at 30 ° C. for 45 minutes.

Next, 339 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and further at room temperature for 1 hour, and then washed with 200 ml of toluene three times to obtain a brown solid product.

(C) Synthesis of solid catalyst component After replacing a flask having an internal volume of 3 with argon, (B)
The total amount of solid product synthesized by the reduction reaction of
8 ml and 105.4 ml (394 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C. for 30 minutes.

After the reaction, solid-liquid separation was performed, and washing with toluene 1.65 was performed twice.

After washing, add 658 ml of toluene, 10.5 ml (62 mmol) of n-butyl ether and 1317 ml of titanium tetrachloride to the flask.
(12.0 mol) was added and the reaction was carried out at 95 ° C for 3 hours. After completion of the reaction, solid-liquid separation was performed at 95 ° C, and then toluene 16 was added at the same temperature.
It was washed twice with 50 ml. The above treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 1650 ml of n-hexane and then dried under reduced pressure to obtain 283 g of a brown solid catalyst component.

The solid catalyst component contained 0.3% by weight of titanium atom and 2.83% by weight of phthalate ester. The average particle size of this solid catalyst component was 156 μm.

(D) Polymerization of propylene After a stainless steel autoclave of a stirring system with a magnetic stirrer having an internal volume of 130 ml was replaced with argon, triethylaluminum 0.57 mmol, 2,2,6,6-
0.057 mmol of tetramethylpiperidine, 10.4 mg of the solid catalyst component obtained in the above (C), and 80 ml of liquefied propylene were charged into an autoclave.

The autoclave was kept at 60 ° C for 1 hour with stirring. After releasing excess propylene, the resulting polypropylene was air dried overnight. 5.0 g of polypropylene was obtained. PP / Ti = 160,000 and polypropylene powder
IY = 94.3% and BD = 0.38 g / ml.

The particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1 and the results shown in Table 1 were obtained.

Example 6 Polymerization was carried out in the same manner as in Example 5 except that 58 mg of the solid catalyst component and 0.057 mmol of diisobutyl phthalate were used instead of 2,2,6,6-tetramethylpiperidine, and the polymerization time was 3 hours. , 6.15 g of polypropylene was obtained. PP / Ti
= 35,000. In addition, IY of polypropylene powder = 9
It was 0.4% and BD = 0.36 g / ml.

The particle size distribution of the obtained polypropylene powder was measured in the same manner as in (E) of Example 1 and the results shown in Table 1 were obtained.

Example 7 (A) Polymerization in liquefied propylene A stirring autoclave made of stainless steel with an internal volume of 3 was replaced with argon, and 2.6 mmol of triethylaluminum, 0.39 mmol of phenyltrimethoxysilane and 31.9 mg of the solid catalyst component synthesized in Example 2 were added. Preparation, 0.12kg
Hydrogen was added corresponding to a partial pressure of / cm ² . Then, 780 g of liquefied propylene was charged, the temperature of the autoclave was raised to 80 ° C, and the polymerization was continued at 80 ° C for 2 hours.

After the polymerization was completed, unreacted monomers were purged. The produced polymer was dried under reduced pressure at 60 ° C. for 2 hours to obtain 118 g of polypropylene powder.

Therefore, PP / Ti = 804,000. Further, the ratio of atactic components soluble in cold xylene in the total polymer yield (abbreviated as CXS (%)) was CXS = 2.0% by weight.
In addition, BD was 0.36 g / ml.

(B) Preparation of biaxially stretched film Using a bench test press, preheating at 230 ° C. for 5 minutes, pressurizing to 80 kg / cm ² G over 3 minutes, and then 80 kg / cm
^The polymer obtained in (A) above was formed into a sheet having a thickness of 500μ under the condition that the pressure was held at ² G for 1 minute. 90x9 this sheet
It was cut into a size of 0 mm and biaxially stretched under the following conditions. Biaxial stretching is performed by using a table-top biaxial stretching machine under the conditions of preheating at a temperature of 155 ° C for 3.5 minutes and then stretching at a speed of 5 m / min to a length of 5 times each in the length and width directions to obtain a biaxially stretched film. It was

Microscopic observation of this film revealed no fish eyes.

Comparative Example 3 (A) Synthesis of solid product After replacing a flask having an internal volume of 200 ml equipped with a stirrer and a dropping funnel with argon, silica gel (dVp = 0.83 cc / g) was added to 1
15.0g dried under reduced pressure at 00 ℃ and n-butyl ether 45.
While adding 5 ml and stirring, 42 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 10 minutes while maintaining the temperature in the flask at 30 ° C., and at the same temperature for 2 hours. Processed.

Then, with 20 ml of n-butyl ether twice, 40 ml of n-heptane
After repeating washing twice with ml, it was dried under reduced pressure to obtain 14.8 g of an organomagnesium-treated product.

Next, after a flask having an internal volume of 300 ml equipped with a stirrer and a dropping funnel was replaced with argon, 13.8 g of the organomagnesium-treated product synthesized earlier, 69 ml of n-heptane, 0.77 g (2.3 mmol) of tetrabutoxytitanium, and tetraethoxy Silane
8.0 g (38.6 mmol) was added and the mixture was stirred at 30 ° C for 30 minutes.

Next, 22.6 ml of the organomagnesium compound synthesized in (A) of Example 1 was dropped from the dropping funnel over a period of time while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1 hour and then at room temperature for 1 hour, and then n-heptane 60 ml.
The product was dried 3 times under reduced pressure and dried under reduced pressure to give a brown solid product.
21.1 g was obtained.

The solid product contained 0.53% by weight of titanium atoms and 5.9% by weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
5.6 g of a solid product synthesized by the reduction reaction of (A), 18.8 ml of toluene and 0.74 ml (2.8 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 18.8 ml of toluene.

After washing, toluene 18.8 ml, n-butyl ether 0.65 ml (3.8 mmol) and titanium tetrachloride 11.6 m in the flask.
l (106 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours.
After completion of the reaction, solid-liquid separation was performed at 95 ° C., and then 18.8 ml of toluene was washed twice at the same temperature. The above treatment with the mixture of n-butyl ether and titanium tetrachloride is repeated once.
The reaction was carried out for 2 hours, washing with 18.8 ml of n-heptane was repeated twice and drying under reduced pressure to obtain 4.8 g of a brown solid catalyst component.

The solid catalyst component contained 1.1% by weight of titanium atoms, 7.8% by weight of magnesium atoms, and 1.5% by weight of phthalates.

(C) Polymerization Using the above solid catalyst, propylene was collected in the same manner as in (A) of Example 7. The result is PP / Ti = 153,00
0, CXS = 2.5% by weight, BD = 0.42 g / ml.

(D) Preparation of Biaxially Stretched Film A biaxially stretched film was obtained in the same manner as in Example 7 using the polymer obtained in (C) above. When this film was observed under a microscope, 43 fish eyes were observed per cm ² .

In comparison with Example 7, when silica gel is used as a carrier, many fish eyes are generated in the film.

<Effects of the Invention> As described above, the following effects can be obtained by using the catalyst system of the present invention.

(1) Since the catalytic activity per titanium atom is very high,
The content of halogen atoms and titanium atoms, which are closely related to the coloring, stability and corrosiveness of the polymer, is extremely low even without any special catalyst residue removing operation. That is, the equipment for removing the catalyst residue becomes unnecessary, and the production cost of the α-olefin polymer can be reduced.

(2) By using the catalyst system of the present invention, it becomes possible to produce an α-olefin polymer having very high stereoregularity. Therefore, since the amount of the amorphous polymer produced as a by-product is extremely small, the α value which is excellent in mechanical properties without removing the amorphous polymer is obtained.
-Olefin polymers can be produced.

(3) Since the production of a polymer having a low stereoregularity possible in the polymerization medium is extremely small, there is no process problem such as the adhesion of the polymer to the reaction tank, piping, flash hopper and the like. Further, since the amount of soluble polymer produced is extremely small, the raw material monomer can be effectively utilized.

(4) By using the catalyst system of the present invention, it becomes possible to produce an α-olefin polymer having a very high bulk density. Therefore, manufacturing equipment such as a reaction tank can be downsized, and extremely high productivity can be obtained.

(5) In the catalyst system of the present invention, the shape of the porous polymer beads can be reflected in the shape of the solid catalyst. This means that the shape and size of the α-olefin polymer having a similar relationship to the solid catalyst can be easily manipulated by changing the shape and size of the porous polymer beads.

(6) By using the catalyst system of the present invention, the amount of fine powder of the α-olefin polymer can be extremely reduced. Therefore, it is possible to prevent problems such as clogging in the piping and the like caused by the fine powder.

(7) By using the catalyst system of the present invention, the effects of (5) and (6) above can be achieved without including an inorganic oxide that causes quality problems such as fish eyes in the α-olefin polymer. be able to.

[Brief description of drawings]

FIG. 1 shows a particle size distribution curve of polypropylene powder.
Here, (A), (B) and (C) show the particle size distribution curves of the polypropylene powders obtained in Example 1, Example 2 and Comparative Example 1, respectively. FIG. 2 is a flowchart for facilitating the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (2)

[Claims] 1. A) An organosilicon compound having a Si--O bond and a pore volume in the range of 100 to 5,000Å of a pore radius of 0.1 cc /
In the presence of porous polymer beads of g or more, the general formula Ti (O
^{_{R 1) n -. X 4-}} n (R 1 is hydrocarbon group of 1 to 20 carbon atoms, X is a halogen atom, n represents 0 <represents a number n ≦ 4) an organomagnesium compound a titanium compound represented by The trivalent titanium compound-containing solid catalyst component obtained by treating the solid product obtained by the reduction with an ester compound and a mixture of an ether compound and titanium tetrachloride, B) an organoaluminum compound, C) Si- It is selected from an organosilicon compound having an OR ² bond (R ² is a hydrocarbon group having 1 to 20 carbon atoms) or a Si—N—C bond, an aromatic carboxylic acid ester compound, and a sterically hindered amine. A method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using a catalyst system comprising an electron-donating compound. 2. A solid catalyst component A) containing a trivalent titanium compound.
However, in the coexistence of an organosilicon compound having a Si-O bond and a porous polymer bead with a pore volume in the range of 100 to 5,000Å and a pore volume of 0.1 cc / g or more, the general formula Ti (OR ¹ ) nX _4- n (R ¹
Is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, n
Represents a number of 0 <n ≦ 4. ) A trivalent titanium compound-containing solid obtained by treating a solid product obtained by reducing a titanium compound represented by) with an organomagnesium compound with an ester compound, and then treating the mixture with an ether compound and titanium tetrachloride. The method for producing an α-olefin polymer according to claim 1, which is a catalyst.