JPH0739449B2 - 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, the production of an α-olefin polymer excellent in mechanical properties and processability by using a novel catalyst system having a very high catalytic activity per solid catalyst and titanium atom, and having very little catalyst residue and amorphous polymer. Regarding the method.

<Prior Art> Generally, as a method for producing an α-olefin polymer such as propylene or butene-1, a so-called group consisting of a 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 the 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 fiber or other processed product and used.

Further, the production of the above-mentioned amorphous polymer causes a loss of raw material monomers, and at the same time, a manufacturing facility necessary for removing the amorphous polymer is indispensable.

Therefore, if there is no formation of such an amorphous polymer, or if there is very little, it can be a great advantage.

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 removal Equipment for stabilization is required.

This drawback can be ameliorated by increasing the catalytic activity represented by the weight of the α-olefin polymer produced per unit weight of catalyst, and the facility 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 strike necessary for

As a method for producing titanium trichloride, titanium tetrachloride is reduced by 1) hydrogen and then activated by pulverizing with a ball mill.
2) Activated by ball milling after reduction with metallic aluminum. 3) -30 to 30 with organoaluminum compound
The reduced solid obtained by reduction at a temperature of ℃ 120
There is heat treatment at a temperature of ~ 180 ° C.

However, the titanium trichloride is not sufficiently satisfactory in terms of catalytic activity and stereoregularity.

Further, a method of treating a reduced solid produced by reducing titanium tetrachloride with an organoaluminum compound with a complexing agent and further reacting it with titanium tetrachloride (Japanese Patent Publication No. 53-3356), and the applicant of the present invention General formula Ti (OR) nX _4-
A titanium catalyst represented by n is reduced with an organoaluminum compound and then treated with a mixture of an ether compound and titanium tetrachloride (JP-A-59-126401), which comprises a solid catalyst component and an organoaluminum compound. When α-olefin is polymerized using a catalyst system, the obtained α-olefin polymer has high stereoregularity, but the catalytic activity is not high enough.

As a method for producing titanium trichloride, it is also known to synthesize titanium tetrachloride by reducing titanium tetrachloride with an organomagnesium compound such as a Grignard reagent.

The applicant has previously proposed a method of treating a reaction solid obtained by reducing titanium tetrachloride with an organomagnesium compound with a Lewis acid (Japanese Patent Publication No. 57-24361).

However, even if the catalyst obtained by such a method is used,
-Although the catalytic activity in the polymerization of olefins is high, the stereoregularity of the obtained α-olefin polymers is not yet sufficiently high.

<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 and stereoregularity so that removal of catalyst residue and amorphous polymer becomes unnecessary. To provide a method for producing an α-olefin polymer having properties.

<Means for Solving Problems> The present invention includes: A) the general formula Si (OR ¹¹ ) mR ¹² _4- m, R ¹³ (R ¹⁴ ₂ SiO) pSiR
¹⁵ ₃ or (R ¹⁶ ₂ SiO) q (wherein R ¹¹ has 1 to 20 carbon atoms)
Hydrocarbon ^{group, R 12, R 13, R} 14, R 15 and R ¹⁶ is a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, m is 0 <m ≦
4 is a number, p is an integer of 1 to 1000, and q is 2
It is an integer of 1000. ) In the coexistence of an organosilicon compound having a Si-O bond, 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 reducing the titanium compound with an organomagnesium compound A trivalent titanium compound-containing solid catalyst component obtained by treating a compound with an ester compound and a mixture of an ether compound and titanium tetrachloride, B) an organoaluminum compound, C) a general formula (However, when n = 2 or 3, R ² is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R ^{3 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyl group.). A method for producing an α-olefin polymer by using a catalyst system consisting of a heterocyclic compound having a structure described below.

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 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). Specific examples of R ¹ include methyl, ethyl, n-
Propyl, iso-propyl, n-butyl, iso-butyl,
Alkyl groups such as n-amyl, iso-amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, aryl groups such as phenyl, cresyl, xylyl, naphthyl, cyclohexyl, cyclopentyl and the like. Examples thereof include an alkyl group, an allyl group such as propenyl, and an aralkyl group 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.

N of the titanium compound represented by the general formula Ti (OR ¹ ) nX _4- n
The value of 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 at a predetermined ratio, or a method of reacting TiX ₄ and a corresponding alcohol with 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 the component (A) of the present invention is represented by the following general formula.

Si (OR ¹¹ ) mR ¹² _4- m R ¹³ (▲ R ¹⁴ ₂ ▼ SiO) pSi ▲ R ¹⁵ ₃ ▼ or (R ¹⁶ ₂ SiO) q where R ¹¹ is a hydrocarbon having 1 to 20 carbon atoms. Group, R ¹² , R ¹³ , R
¹⁴ , R ¹⁵ and R ¹⁶ 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 10
Is an integer of 00, and q is an integer of 2 to 1000.

The following can be illustrated as specific examples of the organosilicon compound.

Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, diisopropoxydiisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetra-n -Butoxysilane, di-
n-butoxydi-n-butylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane, octa Examples thereof include ethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane and the like.

Preferred of these organosilicon compounds are those of the general formula
An alkoxysilane compound represented by Si (OR ¹¹ ) mR ¹² _4- m, preferably 1 ≦ m ≦ 4, and particularly m = 4
The tetraalkoxysilane compound of is 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. Particularly, a Grignard compound represented by the general formula R ¹⁷ MgX (wherein R ¹⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom) and the general formula R ¹⁸ R ¹⁹ Mg (wherein R ¹⁸ and R ¹⁹ each 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 ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-.
Amyl, iso-amyl, n-hexyl, n-octyl,
2-ethylhexyl, phenyl, benzyl, etc. having 1 carbon atom
To 20 alkyl groups, aryl groups, aralkyl groups and alkenyl groups.

Specifically, as the Grignard compound, methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium chloride, n-butylmagnesium bromide, sec-butylmagnesium chloride, sec-butylmagnesium bromide, tert-butylmagnesium chloride, tert-butylmagnesium bromide, n-amylmagnesium chloride, iso-amylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc. Is diethyl magnesium, a compound represented by R ¹⁸ R ¹⁹ Mg, di-n-
Propyl magnesium, di-iso-propyl magnesium, di-n-butyl magnesium, di-sec-butyl magnesium, di-tert-butyl magnesium, n-butyl-sec-butyl magnesium, di-n-amyl magnesium, diphenyl magnesium, etc. Is mentioned.

As a synthetic solvent for the above-mentioned organomagnesium compound, diethyl ether, di-n-propyl ether, di-iso
-Propyl ether, di-n-butyl ether, di-is
o-butyl ether, di-n-amyl ether, di-iso
-Amyl ether, di-n-hexyl ether, di-n
Ethers such as octyl ether, diphenyl ether, dibenzyl ether, phenetole, anisole, tetrahydrofuran, tetrahydropyran can be used. Also, hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene,
A hydrocarbon such as xylene, or a mixed solvent of ether and hydrocarbon may be used. The organomagnesium compound is preferably used in the form of an ether solution. As the ether compound in this case, 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 ¹⁷ MgCl in the state of an ether solution from the viewpoint of catalytic performance.

The hydrocarbon-soluble complex which is a reaction product of the organomagnesium compound and the organometallic compound may be dissolved in hydrocarbon and used. Examples of organic metal compounds include organic compounds of Li, Be, B, Al or Zn.

(D) 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. Esters, aromatic carboxylic acid esters and the like 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 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, diethyl phthalate, di-phthalate
n-propyl, diisopropyl phthalate, di-phthalate
n-butyl, diisobutyl phthalate, di-n-phthalate
Examples thereof include heptyl, di-n-octyl phthalate, diphenyl phthalate and the like.

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

(E) 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.

Of these, di-n-butyl ether and diisoamyl ether are particularly preferable.

(F) 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, with an ester compound and an ether compound. And treated with a mixture of titanium tetrachloride and. 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.

First, as a method of reducing a titanium compound with an organomagnesium compound, a method of adding an organomagnesium compound to a mixture of a titanium compound and an organosilicon compound, or conversely, a titanium compound and an organosilicon compound in a solution of the organomagnesium compound. A mixture of compounds may be added.
A method of adding an organomagnesium compound to a mixture of a titanium compound and an organosilicon compound is preferable from the viewpoint of catalytic activity.

The titanium compound and the organosilicon compound 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 range is -25 to 35 ° C. If the reduction reaction temperature is too high, the catalytic activity will decrease.

The dropping time is not particularly limited, but is usually about 30 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, which is 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 solid product obtained by the reduction reaction is subjected to solid-liquid separation, and washed several times with an inert hydrocarbon solvent such as hexane and heptane.

The solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits amorphous or extremely weak crystallinity. From the viewpoint of catalytic performance, an amorphous structure is particularly preferable.

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

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

The amount of the ester compound used is 0.01 to 1.0 mol, preferably 0.0 per mol of magnesium atom in the solid product.
It is 3 to 0.5 mol. If the amount of the ester compound used is too large, the particles will disintegrate.

The solid product can be treated with the ester compound by any known method such as mechanical pulverizing means such as a slurry ball mill which can bring both into contact with each other. However, mechanical pulverization causes a large amount of fine powder in the solid catalyst component. Occurs 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.

Examples of diluents include aliphatic hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cyclopentane, 1,2-dichloroethane and monochlorobenzene. Halogenated hydrocarbons such as

Of these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable.

The amount of diluent used is 0.1 ml to 1000 ml per gram of solid product. It is preferably 1 ml to 1000 ml per 1 g. The treatment temperature is -50 to 150 ° C, preferably 0 to 120 ° C. The treatment time is 10 minutes or more, preferably 30 minutes to 3 hours. After the treatment is completed, the mixture is allowed to stand, and solid-liquid separation is performed, followed by washing with an inert hydrocarbon solvent several times to obtain an ester-treated solid.

During the subsequent treatment with a mixture of an ether compound and titanium tetrachloride, it is possible to coexist with an ester compound and simultaneously perform the treatment.

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, and aromatic hydrocarbons and halogenated hydrocarbons are particularly preferable.

Slurry concentration is 0.05-0.5g solid / ml solvent, especially 0.1-0.3g
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.

As a method for adding the ester-treated solid, the ether compound and titanium tetrachloride, a method for adding the ester-treated solid ether compound and titanium tetrachloride, or conversely, a method for adding the ester-treated solid in a solution of the ether compound and titanium tetrachloride. Method is also acceptable.

In the method of adding the ether compound and titanium tetrachloride to the ester-treated solid, a method of previously mixing the ether and titanium tetrachloride, or a method of adding the ether compound and titanium tetrachloride at the same time is particularly preferable.

The reaction between the ester-treated solid 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 1 to 1000 mol, preferably 3 to 1 mol, per 1 mol of titanium atom contained in the solid product.
It is 500 mol, particularly preferably 10 to 300 mol. Further, the addition amount of titanium tetrachloride to 1 mol of the ether compound is 1 to
100 mol, preferably 1.5 to 75 mol, particularly preferably 2 to
It is 50 mol.

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

After solid-liquid separation, wash with a large amount of aromatic hydrocarbon solvent such as toluene or xylene, or halogenated hydrocarbon solvent such as monochlorobenzene at a temperature of 50 to 120 ° C once or more, and further, aliphatic hydrocarbon solvent such as hexane. It is preferable to use it for the polymerization after repeating washing several times in the point of catalytic activity and stereoregularity.

(G) 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 ²⁰ rAlY _3- r R ²¹ R ²² Al-O-AlR ²³ R ²⁴ Here, R ²⁰ , R ²¹ , R ²² , R ²³ and R ²⁴ are hydrocarbon groups having 1 to 8 carbon atoms, and Y is It represents a halogen atom, a hydrogen atom or an alkoxy group. r is a number represented by 2 ≦ r ≦ 3.

Specific examples of the organic aluminum compound include 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 and alkylalumoxane are preferable, and triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride and tetraethyldialumoxane are particularly preferable.

The amount of the organoaluminum compound used can be selected in a wide range such as 1 to 1000 mol per 1 mol of the titanium atom in the solid catalyst, but the range of 5 to 600 mol is particularly preferable.

(H) Heterocyclic compound C) In the present invention, a compound represented by the general formula as a catalyst component C) is used at the time of polymerization. (However, when n = 2 or 3, R ² is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, R ^{3 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group. When one of the above substituents is a secondary or tertiary hydrocarbon group, the other may be a hydrogen atom).

Specific compounds include: 2,5- and 2,5, N-substituted pyrrolidines such as 2,6- and 2,6, N-substituted piperidines such as 2,6-substituted tetrahydrofuran such as 2,6-substituted tetrahydropyrans such as are effective.

Among these compounds, 2,6 diisopropylpiperidine, 2,2 ', 6,6'-tetramethylpiperidine, 2,2', 5,
Compounds such as 5'-tetramethylpiperidine, 2,5-diisopropylpyrrolidine, 2,2 ', 5,5'-tetramethyltetrahydrofuran and 2,2', 5,5'-tetramethylpyran are preferable, and especially 2, 2 ', 6,6'-Tetramethylpiperidine is preferred. The component (C) is used in an amount of 0.0001 to 5.0 mol, preferably 0.0005 to 3.0 mol, and particularly preferably 0.001 to 1.0 mol, based on 1 mol of the organoaluminum as the component B).

(I) Polymerization Method of α-Olefin There are no particular restrictions on the method of supplying each catalyst component to the polymerization tank, except that the catalyst component is supplied in an inert gas such as nitrogen or argon without water.

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 up to −30 to 200 ° C., but in the temperature range lower than 0 ° C., the polymerization rate decreases, and
It is usually preferable to carry out the heating in the range of 0 to 100 ° C. for the reason that a polymer having high stereoregularity cannot be obtained at 100 ° C. or higher. The polymerization pressure is not particularly limited, but a pressure of about 3 to 100 atm is desirable from the viewpoint of being industrial and economical. The polymerization method may be either continuous or batch. Also propane, butane, pentane,
Slurry polymerization with an inert hydrocarbon solvent such as hexane, heptane, or octane, or liquid phase polymerization or gas phase polymerization without solvent is also possible.

Next, the alpha olefin applicable to the present invention has 3 or more carbon atoms, and specific examples include propylene,
Examples thereof include butene-1, pentene-1, hexene-1, 3-methyl-pentene-1, 4-methyl-pentene-1, 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 bringing two or more kinds of olefins into contact with each other in a mixed state.

Also, 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.

The valence of the titanium compound in the examples was determined from the polarogram measurement.

(Polarogram measurement conditions) Device: POLAROGRAPHIC ANALYZER P-1100 (Yanagimoto Seisakusho) Sample: Prepared by dissolving about 70 mg of a catalyst in about 30 ml of a basic solution consisting of an aqueous solution of peptic acid at a concentration of 1.5 mol / l and 1N sulfuric acid.

Measurement method: direct current method Example 1 (A) Synthesis of organomagnesium compound After replacing a flask having an internal volume of 1 equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer with argon, 32.0 g of scraped magnesium for Grignard Was thrown in. Add 120 g of n-butyl chloride and 500 m of di-n-butyl ether to the dropping funnel.
About 30 ml was added dropwise to magnesium in the flask to start the reaction. After starting the reaction, the dropping was continued at 50 ° C. for 4 hours, and after the dropping was completed, the reaction was continued at 60 ° C. for another hour. Then, the reaction solution was cooled to room temperature, and the solid content was separated.

N-Butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid, and the concentration was determined by back titration with 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator). The concentration was 2.2 mol. /
Met.

(B) Synthesis of solid product After a flask having an inner volume of 500 ml equipped with a stirrer and a dropping funnel was replaced with argon, 300 ml of n-heptane, 4.1 g (12.1 mmol) of tetrabutoxytitanium and 42.9 g (206 mmol of tetraethoxysilane) were added. ) Was added to make a uniform solution. Next, 100m of organomagnesium compound synthesized in (A)
While keeping the temperature in the flask at 5 ° C., 1 was gradually added dropwise from the dropping funnel over 2 hours. After completion of dropping, the mixture was further stirred at room temperature for 1 hour, solid-liquid separated at room temperature, repeatedly washed with 300 ml of n-heptane three times and dried under reduced pressure.
32.0 g of a dark brown solid product was obtained. The valence of the titanium atom contained in the solid product was trivalent as determined by polarogram measurement.

1.7% by weight of trivalent titanium atoms, 18.2% by weight of magnesium atoms, 2.2% by weight of silicon atoms in the solid product,
It contained 0.8% by weight of n-butyl ether, 33.5% by weight of ethoxy groups, and 2.4% by weight of butoxy groups.

In addition, no clear diffraction peak was observed in the wide-angle X-ray diffraction pattern of this solid product by Cu-Kα line, and the solid product had an amorphous structure.

(C) Synthesis of ester-treated solid After replacing a flask having an internal volume of 200 ml with argon,
15 g of solid product synthesized in (B), 90 m of monochlorobenze
1 and 2.7 ml of diisobutyl phthalate were added, and the reaction was carried out at 80 ° C. for 1 hour.

After the reaction, solid-liquid separation was carried out and washing with 120 ml of n-heptane was carried out three times. The ester-treated solid contained 6.2% of phthalic acid ester.

(D) Synthesis of solid catalyst component After completion of washing in (C) above, 90 ml of monochlorobenzene, 6.6 ml (32.6 mmol) of diisoamyl ether and 49.3 ml (450 mmol) of titanium tetrachloride were added to the flask, and 8
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, solid-liquid separation was carried out at 80 ° C., and then washed twice with 90 ml of monochlorobenzene at the same temperature, and then further washed with 120 ml of n-heptane at room temperature.
Repeated washing twice.

The above treatment with the mixture of n-butyl ether and titanium tetrachloride was repeated once more under the same conditions to obtain 18.0 g of an ocher solid catalyst component.

The valence of the titanium atom contained in the solid catalyst component was trivalent as measured by polarogram.

In the solid catalyst component, 1.8% by weight of titanium atom, 21.1% by weight of magnesium atom, 0.2% by weight of silicon atom, 0.3% by weight of butoxy group, 1.1% by weight of ethoxy group, 6.2% by weight of phthalate ester, It contained 0.2% by weight of isoamyl ether and 66.7% by weight of chlorine.

(E) Polymerization of Propylene After replacing the stirring autoclave made of stainless with a magnetic stirrer with an internal volume of 130 ml with argon,
0.57 mmol of triethylaluminum, 1.71 mmol of 2,2,6,6-tetramethylpiperidine, 1.5 mg of the solid catalyst component obtained in the above (D), 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. 5.66 g of polypropylene were obtained.

Therefore, the yield of polypropylene per 1 g of the solid catalyst component (g) or less (abbreviated as PP / cat) was PP / cat / 3770.

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 = 95.5%.

Example 2 Polymerization was performed in the same manner as in (E) of Example 1 except that 0.57 mmol of 2,2,6,6-tetramethylpiperidine and 1.7 mg of a solid catalyst component were used. As a result, 9.7 g of polypropylene was obtained. Therefore PP / cat = 5760 and IY = 9
It was 4.0%.

Example 3 In place of 2,2,6,6-tetramethylpiperidine of (E) of Example 1, 0.57 mmol of 2,2,5,5-tetramethyltetrahydrofuran was used, and 3.8 mg of a solid catalyst component was used. Polymerization was performed in the same manner as in (E) of Example 1 except that As a result, 10.2 g of polypropylene was obtained. Therefore, PP / CAT = 2680 and IY = 80.4%.

<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 catalyst activity per solid catalyst and titanium atom is very high, a halogen atom, which is closely related to the coloration, stability and corrosiveness of the polymer, without any special catalyst residue removal operation, The content of titanium atoms is extremely low. That is, the equipment for removing the catalyst residue becomes unnecessary, and α
-The production cost of the 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
-Olefin polymers can be produced.

(3) Since the generation of a polymer having a low stereoregularity that is soluble in the polymerization medium is extremely small, no process problems such as the adhesion of the polymer to the reaction tank, piping, flash hopper, etc. occur. Further, since the amount of soluble polymer produced is extremely small, the raw material monomers can be effectively utilized.

[Brief description of drawings]

FIG. 1 is a flow chart 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.

 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Ken Ehara 5-1 Anezaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Hirofumi Johoji 1-5 Anesaki Kaigan, Ichihara, Chiba Sumitomo Chemical Co., Ltd. Business

Claims (2)

[Claims] 1. A) General formula Si (OR ¹¹ ) mR ¹² _4- m, R ¹³ (R ¹⁴ ₂
SiO) pSiR ¹⁵ ₃ or (R ¹⁶ ₂ SiO) q (wherein R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have 1 carbon atoms. To 20 hydrocarbon groups or hydrogen atoms, m is a number 0 <m ≦ 4, p is an integer from 1 to 1000, and q
Is an integer of 2 to 1000. ) In the presence of an organosilicon compound having a Si-O bond represented by the general formula Ti (OR ¹ ) nX
Obtained by reducing a titanium compound represented by _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) with an organomagnesium compound The solid product obtained by treating the solid product 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) a general formula (However, when n = 2 or 3, R ² is hydrogen or a hydrocarbon group having 1 to 4 carbon atoms, and R ^{3 to} R ¹⁰ are hydrogen, a hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group.). A method for producing an α-olefin polymer, which comprises homopolymerizing or copolymerizing an α-olefin using a catalyst system comprising a heterocyclic compound having the structure shown. 2. A solid catalyst component A) containing a trivalent titanium compound.
Has the general formula Si (OR ¹¹ ) mR ¹² _4- m, R ¹³ (R ¹⁴ ₂ SiO) pSiR ¹⁵ ₃
Or (R ¹⁶ ₂ SiO) q (wherein R ¹¹ is a hydrocarbon group having 1 to 20 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ have 1 to 2 carbon atoms.
It is a hydrocarbon group of 0 or a hydrogen atom, m is a number of 0 <m ≦ 4, p is an integer of 1 to 1000, and q is an integer of 2 to 1000. In the coexistence of an organosilicon compound having a Si—O bond represented by the formula ( ¹ ), a compound represented by the general formula Ti (OR ¹ ) nX _4- n (R ¹ is a hydrocarbon having 1 to 20 carbon atoms) Group, X is a halogen atom, and n is a number of 0 <n ≦ 4.) A solid product obtained by reducing a titanium compound represented by an organomagnesium compound is treated with an ester compound and then treated with an ether compound. The method for producing an α-olefin polymer according to claim 1, which is a solid catalyst component containing a trivalent titanium compound obtained by treating with a mixture with titanium tetrachloride.