JPS63235307A - Preparation of alpha-olefin polymer - Google Patents

Abstract

PURPOSE:To prepare a highly stereoregular polymer in a high productivity, by (co)polymerizing an alpha-olefin in the presence of a catalyst system consisting of a specified trivalent titanium compound-containing solid catalyst ingredient, an organoaluminum compound and an organosilicon compound. CONSTITUTION:An organosilicon compound having an Si-O bond, a titanium compound of formula I (where R<1> is a 1-20C hydrocarbon group; X is a halogen; 0<n<=4) and an organomagnesium compound are reacted. The resulting solid reaction product is treated with a compound of formula II or III (where R<2> and R<3> are each 1-20C hydrocarbon group) and then with a mixture of an ether compound and titanium tetrachloride. An olefin is (co)polymerized in the presence of a catalyst system consisting of the resulting trivalent titanium compound-containing solid catalyst ingredient, an organoaluminum compound (e.g. triethylaluminum) and a silicon compound (e.g. tetramethoxysilane) having an Si-OR<4> bond (where R<4> is a 1-20C hydrocarbon group) to give a polymer.

Description

[Detailed description of the invention] <Industrial application field> The present invention relates to a method for producing an α-olefin polymer.

%+, in detail, using a new catalyst system with extremely high catalytic activity per solid catalyst and per titanium atom, resulting in extremely low levels of catalyst residue and amorphous polymers, excellent mechanical properties and processability. Regarding the manufacturing method 1ζ.

<Prior art> General 1. As a method for producing α-olefin polymers such as propylene and butene-1, from transition metal compounds of groups ■ to ■ of the periodic table and organometallic compounds of groups I to ■ It is well known to use the so-called Ziegler-Natsuta catalyst.

In particular, when producing α-olefin polymers industrially, titanium trichloride catalysts are often used. -Amorphous polymers are produced as by-products in addition to olefin polymers.

This amorphous polymer has little industrial utility value and has a large adverse effect on mechanical properties when the α-olefin polymer is processed into films, fibers, and other processed products.

In addition, the production of the #foot-shaped polymer causes a loss of raw material monomers, and at the same time, production equipment necessary for removing the amorphous polymer is required, resulting in extremely large disadvantages from an industrial perspective.

Therefore, it would be a great advantage if such amorphous polymers were not produced prematurely, or if only to a very small extent.

On the other hand, catalyst residue remains in the α-olefin polymer obtained by this polymerization method, and this catalyst residue causes various problems such as stability and processability of the α-olefin polymer, and the catalyst Equipment for residue removal and stabilization will be required.

This drawback can be improved by increasing the catalytic activity expressed by the weight of the α-olefin polymer produced per unit weight of catalyst.Furthermore, equipment for removing the catalyst residue is no longer required, and the α-olefin polymer It will also be possible to reduce the necessary production costs for manufacturing fζ.

The method for producing titanium trichloride includes 1) reducing titanium tetrachloride with hydrogen, and then pulverizing and activating it with a ball ITV.

2) After reduction with metal aluminum, it is activated by ball milling. 8) Organoaluminum compound - 80~
For example, a reduced solid obtained by reduction at a temperature of 80°C is heat-treated at a temperature of 120 to 180°C.

However, the above-mentioned titanium trichloride is not fully satisfactory in terms of both catalytic activity and stereoregularity.

In addition, a method in which a reduced solid produced by reducing titanium tetrachloride with an organoaluminum compound is treated with a complexing agent and further reacted with titanium tetrachloride (Japanese Patent Publication No. 68-8856
Publication No.), and the general formula Ti (
OR) A method in which a titanium compound represented by n
When α-olefin polymerization is carried out using a catalyst system consisting of a solid catalyst component and an organoaluminum compound obtained in JP 01, etc., although the stereoregularity of the resulting α-olefin polymer is high, the catalytic activity is low. It's not high enough to satisfy me.

It is also known that titanium trichloride is synthesized by reducing titanium tetrachloride with an organomagnesium compound, such as a Grignyl V-reagent.

The present applicant previously proposed a method in which a reaction solid obtained by reducing titanium tetrachloride with an organomagnesium compound is treated with a Lewis acid (Japanese Patent Publication No. 57-24861).

However, even when using the catalyst obtained by this method, α
-Although the catalytic activity for olefin polymerization is high, the stereoregularity of the obtained α-olefin polymer is still not high enough to satisfy.

<Problems to be Solved by the Invention> Such Current Status] In this situation, the problems to be solved by the present invention, that is, the purpose of the present invention is to achieve a sufficiently high catalytic activity so that the removal of catalyst residues and amorphous polymers is unnecessary. An object of the present invention is to provide a method for producing an α-olefin polymer having stereoregularity.

Means for Solving the Problems> The present invention provides the following features: A) In the coexistence of an organosilicon compound having a Si-0 bond,
General formula Ti (OR1)nXa-n (R1 is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen atom, n is 0 <
Represents a number where n≦4. ) A solid product obtained by reducing a titanium compound represented by
represents a hydrocarbon group. ), or general formula R3(COX), (R3+ with carbon number 1 to 20 (7
) Hydrocarbon group, X represents a halogen atom. ) and a trivalent titanium compound-containing solid catalyst component obtained by treatment with a mixture of an ether compound and titanium tetrachloride; B) an organoaluminum compound; This is a method for producing an α-olefin polymer by using a catalyst system made of a silicon compound having a hydrocarbon group having 1 to 20 carbon atoms.

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

The present invention will be explained in detail below.

(al Titanium compound The titanium compound used in the present invention has the general formula Ti
(OR')nX4-n (R1 has 1 to 2G carbon atoms
is a hydrocarbon group, X is a halogen atom, and n is a number satisfying o<n≦4. ). Specific examples of R1 include methyl, ethyl, n-propyl, 1so-propyl, n-
Alkyl groups such as butyl, 1so-butyl, n-amyl, 1so-amyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-dodecyl, aryl groups such as phenyl, cresyl, xylyl, naphthyl, Examples include cycloalkyl groups such as cyclohexyl and cyclopentyl, allyl groups such as propenyl, and aralkyl groups such as benzyl. Among these, an alkyl group having 2 to 18 carbon atoms and an aryl group having 6 to 18 carbon atoms are preferred. Special number carbon number 2~
18 straight chain alkyl groups are preferred. It is also possible to use titanium compounds having two or more different OR1 groups.

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

General formula T 1 (0R1) nX4-21 The value of n in the Wasarell titanium compound is o<n≦4, preferably 2≦n≦4, particularly preferably n −4.

General formula T 1 (OR7) nXa −n (0<
A known method can be used to synthesize the titanium compound represented by n≦4). For example, a method of reacting Ti(ORI)4 and TiX4 at a predetermined ratio, or a method of reacting Ti(ORI)4 and TiX4
A method of reacting a predetermined amount of 4 with the corresponding alcohol can be used.

(Organotin compound having a blsi-0 bond Synthesis of component A) of the present invention: ζ The organotin compound having a 5i-0 bond to be used is represented by the following general formula.

S i (OR') mR--m R7 (Sio to R) ps iR'.

or (R”tSiO)q where R5 is a hydrocarbon X group having 1 to 20 carbon atoms, R11
, Rf , Ra , R' and R1' tt Charcoal X number 1 ~
20 hydrocarbon groups or hydrogen atoms, m is o<m≦4
, p is an integer from 1 to 1000, and q is 2
It is an integer between ~1000.

Specific examples of organosilicon compounds include the following.

Tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetralinepropoxysilane, diisopropoxydiisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetra-n -butoxysilane, di-
n-Butoxydi-n-butylsilane, dicyclopentoxydiethylsilane, jetoxydiphenylsilane, cyclohexyloxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisiloxane, hexaethyldisiloxane, hexapropyldisiloxane , octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, and the like.

Among these organosilicon compounds, preferred are alkoxysilane compounds represented by the general formula S i (OR')mR', -m, preferably 1≦m≦
4, particularly preferred is a tetraalkoxysilane compound with m w 4.

(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. Especially the general formula RllMg
X (wherein R11 is a hydrocarbon group having 1 to 20 carbon atoms,
X represents a halogen atom. ) and a dialkylmagnesium compound or diarylmagnesium compound represented by the general formula R12RL3Mg (wherein R12 and R13 represent a hydrocarbon group having 1 to 20 carbon atoms) are preferably used. Rlm here
, R12 and R13 may be the same or different,
Methyl, ethyl, n-propyl, 1so-propyl, n
-butyl, 5ec-butyl, tert-butyl, n-amyl, 1so-amyl, n-hexyl, n-octyl,
1 carbon number such as 2-ethylhexyl, phenyl, benzyl, etc.
~20 alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

Specifically, Grignard compounds include methylmagnesium chloride, ethylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium iodide, n-propylmagnesium chloride, n-propylmagnesium bromide, n-butylmagnesium chloride, n- Butylmagnesium chloride, n-butylmagnesium bromide, 5ec-butylmagnesium chloride, 5eC-butylmagnesium bromide, tert-
Butylmagnesium chloride, tert-butylmagnesium bromide, n-amylmagnesium chloride, 1
SO-amylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc.
Compounds represented by It RII Mg include diethylmagnesium, di-n-propylmagnesium, di-1SO-propylmagnesium, di-n-butylmagnesium, di-5ec-butylmagnesium, di-t
Examples include ert-butylmagnesium, n-butyl-8eC-butylmagnesium, di-n-amylmagnesium, diphenylmagnesium, and the like.

As the synthesis solvent for the above organomagnesium compound, diethyl ether, di-n-propyl ether, di-18
0-propyl ether, di-n-butyl ether, di-1so-butyl ether, di-n-amyl ether, di-1SO-amyl ether, di-n-hexyl ether, di-n-octyl ether, diphenyl ether, dibenzyl ether, phenetol , anisole, tetrahydrofuran, tetrahydropyran, and the like can be used. or,. hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene,
Toluene, xylene, etc. (7) A hydrocarbon 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 containing 6 or more carbon atoms or an ether compound having a cyclic structure is used.

In particular, it is preferable to use a Grignard compound represented by RIIMg (J) in the form of an ether solution from the viewpoint of catalytic performance.

A hydrocarbon-soluble complex, which is a reaction product of the above organomagnesium compound and an organometallic compound, can also be used by dissolving it in a hydrocarbon. Examples of organometallic compounds include Li and Be.

Examples include organic compounds of B, /J or Zn.

(dl acid anhydride or acid) 1ride According to the present invention, the general formula R used in the synthesis of component A)
"Rias hydrate represented by (GO) tO (R2 represents a hydrocarbon group having 1 to 20 carbon atoms), or the general formula R"
(COX), (R3Gt is a hydrocarbon group having 1 to 20 carbon atoms, X represents a halogen atom). This can be done as a specific example.

stomach.

(el Ether Compounds Next, the ether compounds used in the present invention are Teha, diethyl ether, di-n-propyl ether, diinpropyl ether, di-n-butyl ether, di-n-amyl ether, diynamyl ether, diynamyl ether , di-n-hexyl ether, di-n-octyl ether, methyl-n-butyl ether, methyl-in-amyl ether, ethyl-in-butyl ether and the like are preferred.

Among these, di-n-butyl ether and diynamyl ether are particularly preferred.

(fl) 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 a mixture of an ether compound and titanium tetrachloride, preferably by treating a solid product obtained by reduction with an acid anhydride or an acid halide, and then a mixture of an ether compound and titanium tetrachloride. processed and synthesized.

All synthetic reactions are carried out under an inert gas atmosphere such as nitrogen or argon.

First, as a method for the reduction reaction of 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,
Alternatively, a mixture of a titanium compound and an organosilicon compound may be added to a solution of an organomagnesium compound. A method in which an organomagnesium compound is added to a mixture of a titanium compound and an organosilicon compound is preferred from the viewpoint of catalytic activity.

The titanium compound and the organosilicon compound are preferably used after being dissolved or diluted in a suitable solvent.

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

The reduction reaction temperature is -50 to 70°C, preferably -80 to
50C1 is particularly preferably in the temperature range of -25 to 85°C. If the reduction reaction temperature is too high, the catalyst activity will decrease.

The dropping time is not particularly limited, but is usually about 80 minutes to 6 hours. After the reduction reaction is completed, a post-reaction may be further carried out at a temperature of 20 to 120°C.

The amount of the organosilicon compound used is the atomic ratio of silicon atoms to titanium atoms in the titanium compound, and Si/Ti = 1 to 1.
60, preferably 8-80, particularly preferably 5-25.

In addition, the amount of organic magnesium compound used is the atomic ratio of the sum of titanium atoms and silicon atoms to the magnesium atom, and Ti+
Si/Mg=o, 1-10, preferably 0.2-5. O
1 is particularly preferably in the range of 0.6 to 2.0.

The solid product obtained by the reduction reaction is separated into solid and liquid, and washed several times with an inert hydrocarbon solvent such as hexane or heptane.

The solid product thus obtained contains trivalent titanium, magnesium and hydrocarbyloxy groups and generally exhibits poor quality or very weak crystallinity. In view of catalytic performance, an amorphous structure is particularly preferred.

Next, the solid product obtained by the above method is treated with an acid anhydride or an acid halide.

The amount of acid anhydride or acid halide used is 1.0 to 60 mol, more preferably 0.8 to 20 mol, particularly preferably 0.11 to 10 mol, per mol of titanium atom in the solid product.

The amount of acid anhydride or acid halide used per mol of magnesium atom in the solid product is 0.01 to 1.0 mol, preferably 0.08 to 0.6 mol. If too much acid anhydride or acid halide is used, particle disintegration will occur.

Treatment of solid products with acid anhydrides or acid halides is as follows:
This can be carried out by any known method that allows the two to come into contact, such as a slurry method or mechanical pulverization using a ball mill, etc. However, when mechanical pulverization is performed, a large amount of fine powder is generated in the solid catalyst component, resulting in a wide particle size distribution. , which is unfavorable from an industrial point of view. Preferably, the two are brought into contact in the presence of a diluent.

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 halogenated hydrocarbons can be used.

Among these, aromatic hydrocarbons and halogenated hydrocarbons are particularly preferred.

The amount of diluent used is 0.1 ml −1 per 12 solid products.
000ml. Preferably 1m/-100 per IP
− is. The treatment temperature is -50 to 150°C, preferably 0 to 120°C. The treatment time is 10 minutes or more, preferably 80 minutes to 8 hours. After completion of the treatment, the mixture is allowed to stand and separated into solid and liquid, and then washed several times with an inert hydrocarbon solvent to obtain an acid anhydride or acid nolide treated solid.

During the subsequent treatment with a mixture of an ether compound and titanium tetrachloride, it is also possible to carry out the treatment simultaneously with an acid anhydride or a 7% acid acid ride.

Next, the treatment of the acid anhydride or acid halide treated solid with the mixture of the ether compound and titanium tetrachloride is preferably carried out in a slurry state. Solvents used for slurrying include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and decane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin; Examples include halogenated hydrocarbons such as dichloroethane, trichloroethane, trichloroethylene, monochlorobenzene, dichlorobenzene, and trichlorobenzene, and aromatic hydrocarbons and halogenated hydrocarbons are particularly preferred.

The slurry concentration is preferably 0.05 to 0.57 solids/d solvent, particularly 0.1 to 0.8 f solids/d solvent.

Reaction temperature is 80-150°C, preferably 46-120°C
, particularly preferably 60 to ioo°C.

There is no particular restriction on the reaction time, but 80 minutes to 6 hours is usually suitable.

The method of adding an acid anhydride or acid halide treated solid, an ether compound and titanium tetrachloride includes a method of adding an ether compound and titanium tetrachloride to an acid anhydride or acid halide treated solid, and conversely, a method of adding an ether compound and a titanium tetrachloride. Any method may be used, such as adding an acid anhydride or acid halide treated solid to a titanium chloride solution.

In method number ζ of adding an ether compound and titanium tetrachloride to an acid anhydride or acid halide treated solid, the ether and titanium tetrachloride are mixed in advance and then added, or the ether compound and titanium tetrachloride are added at the same time. The method is particularly preferred.

The reaction of the acid anhydride or acid halide-treated solid with the ether compound and titanium tetrachloride may be repeated two or more times. From the viewpoint of catalytic activity and stereoregularity, it is preferable to repeat the reaction with a 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 0.5 to 50 mol, particularly preferably 1 to 20 mol, per 1 mol of titanium atoms contained in the solid product.

The amount of titanium tetrachloride added is 1 to 1000 mol, preferably 8 to 500 mol, particularly preferably 10 to 800 mol, per 1 mol of titanium atoms contained in the solid product. The amount of titanium tetrachloride added per mole of the ether compound is 1-100 moles, preferably 1.6 to 75 moles, particularly preferably 2 to 50 moles.

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

After solid-liquid separation, wash with a large amount of aromatic hydrocarbon such as toluene or xylene or halogenated hydrocarbon such as monochlorobenzene at a temperature of 60 to 120°C once or more, and then wash with aliphatic hydrocarbon such as hexane. From the viewpoint of catalytic activity and stereoregularity, it is preferable to use it for polymerization after repeated washing with a solvent several times.

g) Organoaluminum compound B) In the present invention, the organoaluminum compound B) used in combination with the solid catalyst component A) described above has at least one /J-carbon bond in the molecule. Typical examples are shown below as general formulas.

R14rA5Y, -r R18R+11Ad Q-AeR17R18 Kokote, R
I4, RII, R16, R17 and R' represent a hydrocarbon group having 1 to 8 carbon atoms, and Y represents a hydrogen atom, a hydrogen atom or an alkoxy group. r is a number expressed as 2≦r≦8.

Specific examples of organoaluminum compounds include trialkylaluminiums such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum hydrides such as diethylaluminium hydride and diisobutylaluminum hydride, mixtures of trialkylaluminum and dialkylaluminum halides, Examples include alkylalumoxanes such as tetraethyldialumoxane and tetrabutyldialumoxane.

Among these organoaluminum compounds, trialkylaluminum, a mixture of trialkylaluminium and dialkylaluminum halide, and alkylalumoxane are preferred, and triethylaluminum, triinbutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, and tetraethyldialumoxane are particularly preferred. .

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

(Dimine compound C having hl 5i-OR' bond)
5i used as catalyst component C) during polymerization in the present invention
A dimine compound having an -OR' bond (R4 is a hydrocarbon group having 1 to 20 carbon atoms) has the general formula R"asi(O
R') a 21 (R' and R19 have 1 to 1 carbon atoms
20 hydrocarbon groups, a represents a number of 0≦a≦8. )
An alkoxysilane compound represented by is preferably used.

In particular, R4 is a linear alkyl group having 1 to 10 carbon atoms,
Preferred are alkoxysilane compounds in which at least one of RI9 is an aryl group.

Specific examples include tetramethoxysilane, methyltrimethoxysilane, diethyljethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Examples include vinyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyljethoxysilane butyltriethoxysilane, tetrabutoxysilane, vinyltributoxysilane, diethyljethoxysilane and the like.

The amount of silicon compound having 5i-OR' bond is B
0.01 to 5 moles of Si atoms, preferably 0.08 to 8 moles, particularly preferably 0.05 to 1.0 moles of Si atoms per mole of aluminum atoms in the organoaluminum compound which is the component ().
It is a mole.

(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 it is supplied in an inert gas such as nitrogen or argon without moisture.

Catalyst components A), B), and C) may be supplied individually, or any two may be brought into contact with each other beforehand and supplied.

Polymerization can be carried out at temperatures ranging from -80 to 200°C, but temperatures lower than 0°C may result in a decrease in the polymerization rate, and temperatures above 100°C may not produce highly stereoregular polymers. For some reason, it is usually preferable to carry out the heating in the range of θ to 100°C. There is no particular restriction on the polymerization pressure, but from the viewpoint of industrial and economical pressure, it is 8 to 10.
A pressure of about 0 atmospheres is desirable. The polymerization method can be carried out either continuously or batchwise. Slurry polymerization using an inert hydrocarbon solvent such as propane, butane, pentane, hexane, heptane, or octane, liquid phase polymerization without a solvent, or gas phase polymerization is also possible.

Next, the alpha olefin to which the present invention can be applied is one having a carbon number of 8 or more, and specific examples include propylene, butene-1, pentene-11hexenite, a-methyl-pentene-1,4-methyl -pentene-1, etc., but the present invention is not limited to the above compounds. The polymerization according to the present invention can be either homopolymerization or copolymerization (including copolymerization with ethylene).

During copolymerization, a copolymer can be obtained by bringing two or more types of olefins into contact in a mixed state.

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

It is also possible to add a chain transfer agent such as 1ζ hydrogen to adjust the molecular weight of the polymer.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

The valence of the titanium compounds in the examples was determined from polarogram measurements.

(Polarogram measurement conditions) Equipment: POLAROGRAPHICANALYZER
R-1100 (Yanagimoto Seisakusho) Sample = Prepared by dissolving catalytic 70q in 80 sl of a basic composition consisting of an aqueous solution of tartaric acid and IN sulfuric acid at a concentration of 1.5 mol/e.

Measurement method: Direct current method Example 1 4. Synthesis of organomagnesium compound After purging a flask with an internal volume of 1e equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer with argon, a ground magnesium grinder for Grignard grade 82. I put in Of. A dropping funnel was charged with 120 F of n-butyl chloride and 500 wt of di-n-butyl ether, and the mixture was dropped onto the magnesium in the flask for about 80 d to start the reaction.

After the reaction started, the dropwise addition was continued at 60°C over 4 hours, and after the dropwise addition was completed, the reaction was further continued at 60°C for 1 hour.

Thereafter, the reaction solution was cooled to room temperature and the solid content was separated.

When n-butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid and the concentration was determined by back titration with a 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2. It was .2 mol/e.

(Bl Synthesis of solid product After purging a flask with an internal volume of 500 tel equipped with a stirrer and a dropping funnel with argon, 800 g of n-heptane/
, tetrabutoxytitanium 4.1r (12.1 mmol)
and 42.9f (206 mmol) of tetraethoxysilane were added to form a homogeneous solution. Next, 100 ml of the organomagnesium compound synthesized in (-) was gradually added dropwise from the dropping funnel over a period of 2 hours while maintaining the temperature inside the flask at 5°C. After the addition was completed, the mixture was stirred for an additional hour at room temperature. , solid-liquid separation was performed at room temperature, washed 8 times with 800 tJ of n-heptane, and then dried under reduced pressure to obtain a brown solid product 82, Of.The valence of the titanium atoms contained in the solid product was The number was octavalent as determined by polarogram measurement.

The solid product contains 1.7% trivalent titanium atoms, 18.2% magnesium atoms, and 2.2% silicon atoms.
It contained 0.8% by weight of n-butyl ether, 83.5% by weight of ethoxy groups, and 2.4% by weight of butoxy groups.

In addition, α rays (wide-angle xa
No clear diffraction peaks were observed in the diffraction diagram, indicating an amorphous structure.

C) Synthesis contents of acid anhydride-treated solid al After purging a 200 ml flask with argon, solid product 8F synthesized with TBI, toluene 27
M! Then, 8.8 ml of phthalic anhydride was added and the reaction was carried out at 96°C for 1 hour.

Separate the post-reaction liquid and add 27 ml of n-hebutane. '8
Washed twice and washed completely.

(DJ Synthesis of Solid Catalyst Component After washing with Gl above, add 27WI of toluene to the flask.
t, dibutyl ether 27m? (15.9 mmol) and 47.8 ml (485.2 mmol) of titanium tetrachloride were added, and the reaction was carried out at 96° C. for 1 hour. After completion of reaction 9
After solid-liquid separation at 5°C, it was washed twice with 27ml of toluene at the same temperature, and then washed with 27ml of n-hebutane 4x at room temperature.
Washing was repeated twice.

The treatment with the mixture of n-butyl ether and titanium tetrachloride described above was repeated once again under the same conditions to obtain ocher solid catalyst components 6 and 14 f.

The valence of one titanium atom contained in the solid catalyst component was 8 as determined by polarogram measurement.

The solid catalyst component contained 1.8% by weight of titanium atoms and 21.0% by weight of magnesium atoms.

However, a stainless steel autoclave with a stirring system using a magnetic stirrer with a propylene polymerization internal volume of 180 ml was heated with argon ffi.
After conversion, triethylaluminum 0. loa mmol,
0.0157 mmol of phenyltriethoxysilane, 5.6 q of the solid catalyst component dissolved above, and 80 d of liquefied propylene were charged into an autoclave.

The autoclave was kept at 60C for 1 hour while stirring. After releasing the excess propylene, the resulting polypropylene was air-dried overnight.

16.2F polypropylene was obtained.

Therefore, the yield of polypropylene per 11 solid catalyst components is 1
1(f) (hereinafter abbreviated as PP/cat) is PP/cat
=2890.

Also, the value expressed as a percentage of the amount of residue obtained by extracting the obtained polypropylene powder with boiling mn-hebutane for 6 hours (hereinafter referred to as IY
Abbreviated as N. ) was IY-92.8%.

Comparative Example 1 A solid catalyst component was synthesized in the same manner as in Example 1, except that the acid anhydride treatment in C) of Example 1 was not performed. The solid catalyst component contained 8.9% by weight of titanium atoms.

Polymerization of propylene was carried out in the same manner as in Example 1 (El) using the above solid catalyst component.

PP/cat=8J70, IY=80.8%.

Example 2 In the synthesis of the acid anhydride-treated solid of Example 1 (C1),
A solid catalyst component was synthesized in the same manner as in Example 1 except that 2.84% of phthalic anhydride was used. The solid catalyst contained 6.2% by weight of titanium atoms.

Polymerization of propylene was carried out in the same manner as in C) of Example 1 using the above solid catalyst component.

PP/cat=1,940. IY=91.8%.

Example 8 A solid catalyst component was synthesized in the same manner as in Example 1 except that 0.82 ml of terephthaloyl chloride was used instead of phthalic anhydride in the synthesis of the acid anhydride-treated solid in q of Example 1. 3.5% by weight of titanium atoms in the solid catalyst component
It was contained.

Polymerization of propylene was carried out in the same manner as in Example 1 (El) using the above solid catalyst component.

PP/cat=2,840, IY=90.4% tear ivy.

Example 4 A solid catalyst component was synthesized in the same manner as in Example 1 except that 8.2 ml of terephthaloyl chloride was used instead of phthalic anhydride in the synthesis of the acid anhydride-treated solid of Example 1. The solid catalyst component contained 8.6% by weight of titanium atoms.

Polymerization of propylene was carried out in the same manner as in Example 1 (El) using the above solid catalyst component.

PP/cat=1,280, IY=91.2%.

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

+11 Because the catalytic activity per solid catalyst and per titanium atom is extremely high, halogen atoms and titanium atoms, which are closely related to the coloring, stability, and corrosion properties of polymers, can be removed without any special catalyst residue removal operation. The content of is extremely low. In other words, there is no need for equipment to remove catalyst residue, and α
- It becomes possible to reduce the production cost of olefin polymers.

(2) By using the catalyst system of the present invention, it becomes possible to produce α-olefin polymers with extremely high stereoregularity. Therefore, since the formation of by-product amorphous polymer is extremely small, it is not necessary to remove the amorphous polymer (α-
Olefin polymers can be produced.

(8) Since the production of polymers with low stereoregularity soluble in the polymerization medium is extremely small, process problems such as polymer adhesion to reaction vessels, piping, flash hoppers, etc. do not occur. Furthermore, since the amount of soluble polymer produced is extremely small, raw material monomers can be used effectively.

[Brief explanation of drawings]

FIG. 1 is a flowchart diagram to aid 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 thereto. Procedural amendment (formality) July 7, 1986 Mr. Kunio Ogawa, Commissioner of the Patent Office
, -3-1, Indication of the case 1988 Patent Application No. 70987 2 Name of the invention Process for producing α-olefin polymer 8 Relationship with the person making the amendment Patent applicant address 6 Kitahama, Higashi-ku, Osaka 15-chome name (2
09) Sumitomo Chemical Co., Ltd. June 1980, 6, Drawing 7 to be amended, Contents of the amendment As per the engraving and attached sheet of the drawing originally attached to the application (no change in content). that's all

Claims (2)

[Claims] (1) A) In the coexistence of an organosilicon compound having a Si-O bond, 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 solid product obtained by reducing a titanium compound represented by or an acid anhydride with the general formula R^3(COX)_2 (R^3 represents a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom.)
A solid catalyst component containing a trivalent titanium compound obtained by treatment with an acid halide represented by the formula and a mixture of an ether compound and titanium tetrachloride, B) an organoaluminum compound, C) a Si-OR^4 bond (R^4 is a hydrocarbon group having 1 to 20 carbon atoms.) is a hydrocarbon group having 1 to 20 carbon atoms. (2) Trivalent titanium compound-containing solid catalyst component (A) is S
In the coexistence of an organosilicon compound having an i-O bond, the general formula Ti(OR^1)nX_4-n (R^1 has 1 to 1 carbon atoms)
20 hydrocarbon groups, X is a halogen atom, n is 0<n≦4
represents the number of ) A solid product obtained by reducing a titanium compound represented by acid anhydride, or general formula R
After treatment with an acid halide represented by ^3(COX)_2 (R^3 is a hydrocarbon group having 1 to 20 carbon atoms, and X represents a halogen atom), a mixture of an ether compound and titanium tetrachloride is used. Claim 1, characterized in that it is a solid catalyst containing a trivalent titanium compound obtained by further processing.
A method for producing an α-olefin polymer as described in 1.