JPS643207B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for highly active polymerization or copolymerization of α-olefins with good stereoregularity using a novel catalyst.

Catalysts consisting of titanium halides and organoaluminum compounds have been known as highly stereoregular polymerization catalysts for α-olefins. However, in polymerization using this catalyst system, although a highly stereoregular polymer can be obtained, the catalyst activity is low, so it is necessary to remove catalyst residues from the produced polymer.

In recent years, many proposals have been made to improve the activity of catalysts. According to these proposals
It has been shown that a highly active catalyst can be obtained by using a catalyst component in which titanium tetrachloride is supported on an inorganic solid support such as MgCl ₂ .

However, in the production of polyolefins, it is preferable that the catalyst activity be as high as possible, and catalysts with even higher activity have been desired. It is also important that the amount of atactic moieties formed in the polymer be as small as possible.

As a result of intensive research on these points, the present inventors have discovered a novel catalyst here. That is, the present invention relates to a method for producing extremely highly active and highly stereoregular polyolefin using a novel catalyst. By using the catalyst of the present invention, the monomer partial pressure during polymerization is low and Due to the short polymerization time, the amount of catalyst residue in the produced polymer is extremely small, so the catalyst removal step can be omitted in the polyolefin manufacturing process, and the amount of attic moieties produced in the produced polymer is also extremely small. Effects can be obtained. The present invention will be explained in detail below.

The present invention consists of (1) magnesium dihalide (hereinafter abbreviated as magnesium halide), (2) general formula Si
(OR) _n X _4-n (where R is a hydrocarbon residue having 1 to 24 carbon atoms,
) and (3) aluminum trihalide (hereinafter abbreviated as aluminum halide) to a solid substance obtained by contacting titanium tetrahalide and/or titanium tetrahalide (hereinafter abbreviated as titanium compound). A solid catalyst component obtained by supporting an addition compound of an organic acid ester (abbreviated as ) and an organic acid ester, and a catalyst obtained by combining a mixture or addition compound of an organoaluminum compound (hereinafter abbreviated as an organometallic compound) and an organic acid ester. The present invention relates to a method for producing polyolefins with extremely high activity and stereoregularity by polymerizing or copolymerizing α-olefins having 3 to 8 carbon atoms using the present invention.

In the present invention, (1) magnesium halide,
(2) A compound represented by the general formula Si( _OR ) _n A method of reacting in the presence or absence of heating at a temperature of 20 to 400 °C, preferably 50 to 300 °C, usually for 5 minutes to 20 hours, a method of reacting by co-pulverization treatment, or a method of reacting by co-pulverization treatment, or The reaction may be carried out by appropriately combining these methods.

Furthermore, there is no particular restriction on the reaction order of components (1) to (3), and the three components may be reacted simultaneously, or the two components may be reacted at the same time.
After reacting the components, the remaining component may then be reacted.

The inert solvent used at this time is not particularly limited, and hydrocarbon compounds and/or derivatives thereof that do not normally inactivate the Ziegler type catalyst can be used. Specific examples of these include propane, butane, pentane, hexane,
Various aliphatic saturated hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons such as heptane, octane, benzene, toluene, xylene, and cyclohexane, and alcohols such as ethanol, diethyl ether, tetrahydrofuran, ethyl acetate, and ethyl benzoate; Examples include ethers and esters.

Co-pulverization is usually carried out using equipment such as ball mills, vibration mills, rod mills, impact mills, etc.
At a temperature of 200℃, preferably 20-100℃, 0.5-30
It is preferable to do it for an hour.

In the present invention, a method of obtaining a solid carrier by co-pulverizing components (1) to (3) is particularly preferably employed.

In the present invention, the ratio of component (1 ₎ aluminum halide to component (2) compound represented by the general formula Si(OR) _n 1:0.001-10, preferably 1:0.01-1.
The molar ratio of component (3) aluminum halide is component (1) to component (3) of 1:0.001 to 10, preferably 1:0.01 to 1.

A solid catalyst component is obtained by supporting a titanium compound and/or an addition compound of a titanium compound and an organic acid ester on the thus obtained solid support.

A known method can be used to support the titanium compound and/or the addition compound of the titanium compound and the organic acid ester on the carrier.
For example, this can be carried out by bringing the solid support into contact with an excess of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester under heating in the presence or absence of an inert solvent. , both in the presence of an inert solvent such as n-hexane at 50-300°C, preferably 100-300°C.
This is conveniently carried out by heating to 150°C. The reaction time is not particularly limited, but is usually 5
Although it is not necessary, there is no problem with contacting for a long time. For example, processing times can range from 5 minutes to 10 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. After the completion of the reaction, the method for removing unreacted titanium compounds and/or adducts of titanium compounds and organic acid esters is not particularly limited, and the method of removing the unreacted titanium compound and/or the adduct of the titanium compound and the organic acid ester is not particularly limited. A solid powder can be obtained by evaporation under Another preferred method includes a method of co-pulverizing a solid support and a required amount of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester.

In the present invention, a co-pulverization method is particularly preferably used in which the washing and removal step can be omitted by adding a required amount of a titanium compound and/or an addition compound of a titanium compound and an organic acid ester.

In the present invention, the equipment used for co-pulverization is not particularly limited, but typically includes a ball mill, vibration mill, rod mill, impact mill, etc., and is usually from 0°C to
200℃ preferably 20℃~100℃ temperature for 0.5 hours~
The catalyst component of the present invention can be produced by co-milling for 30 hours. Of course, the co-grinding operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.

The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred.

General formula Si(OR) _n used in the present invention
X _4-n (Here, R is a hydrocarbon residue such as an alkyl group, aryl group, or aralkyl group having 1 to 24 carbon atoms,
represents a halogen atom, m is 0≦m≦4)
Examples of compounds represented by include silicon tetrachloride, monomethoxytrichlorosilane, monoethoxytrichlorosilane, monoisopropoxytrichlorosilane, mono n-butoxytrichlorosilane, monopentoxytrichlorosilane, monooctoxytrichlorosilane, monostearoxytrichlorosilane, Chlorosilane, monophenoxytrichlorosilane, monop
-Methylphenoxytrichlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane,
Diisopropoxydichlorosilane, di-n-butoxydichlorosilane, dioctoxydichlorosilane, trimethoxymonochlorosilane, triethoxymonochlorosilane, triisopropoxymonochlorosilane, tri-n-butoxymonochlorosilane, trisec-butoxymonochlorosilane, tetramethoxy Examples include silane, tetraethoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetrasec-butoxysilane, tetrapentoxysilane, and tetraphenoxysilane.

Examples of the aluminum halide used in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, with aluminum chloride being particularly preferred.

As the titanium compound used in the present invention, titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are preferable.

The addition compound of a titanium compound and an organic acid ester preferably has a molar ratio of titanium compound:organic acid ester of 2:1 to 1:2. These addition compounds include TiCl ₄・C ₆ H ₅ COO ₂ H ₅ ,
TiCl ₄・2C ₆ H ₅ COOC ₂ H ₅ , TiCl ₄・p—
Examples include CH ₃ OC ₆ H ₅ COOC ₂ H ₅ .

In the present invention, the amount of the titanium compound and/or the addition compound of the titanium compound and the organic acid ester used is not particularly limited, but usually the amount of the titanium compound contained in the solid product is 0.5 to 20% by weight,
It is preferable to adjust the amount to preferably 1 to 10% by weight.

Examples of organometallic compounds used in the present invention include general formulas R ₃ Al, R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl
There is an organoaluminum compound of (OR)X and R _{3 Al 2} ,in particular,
Triethylaluminum, triisopropylaluminium, triisobutylaluminum, tri-
Examples include sec-butylaluminum, tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof.

In the present invention, the organometallic compound component is used as a mixture or addition compound of the organometallic compound and the organic acid ester.

When the organometallic compound and the organic acid ester are used as a mixture, the organic acid ester is usually used in an amount of 0.1 to 1 mol, preferably 0.2 to 0.5 mol, per 1 mol of the organometallic compound. When used as an addition compound of an organometallic compound and an organic acid ester, the molar ratio of organometallic compound:organic acid ester is preferably 2:1 to 1:2.

In the present invention, the amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound.

The organic acid ester used in the present invention is an ester of a saturated or unsaturated monobasic or dibasic organic carboxylic acid having 1 to 24 carbon atoms and an alcohol having 1 to 30 carbon atoms. Specifically, methyl formate, ethyl acetate, amyl acetate, phenyl acetate, octyl acetate, methyl methacrylate, ethyl stearate, methyl benzoate, ethyl benzoate, n-propyl benzoate, di-propyl benzoate, benzoic acid. Butyl, hexyl benzoate, cyclopentyl benzoate, cyclohexyl benzoate, phenyl benzoate, 4-tolyl benzoate, methyl salicylate, ethyl salicylate, methyl p-oxybenzoate, ethyl p-oxybenzoate, phenyl salicylate, p- Cyclohexyl oxybenzoate, benzyl salicylate, ethyl α-resorcinate, methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, p-
Methyl toluate, p-ethyl toluate, p-
Phenyl toluate, ethyl o-toluate, m
Examples include ethyl toluate, methyl p-aminobenzoate, ethyl p-aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, methyl naphthoate, and ethyl naphthoate.

Among these, benzoic acid, o
- or alkyl esters of p-toluic acid or p-anisic acid, and methyl esters and ethyl esters thereof are particularly preferred.

The olefin polymerization reaction using the catalyst of the present invention is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out substantially in the absence of oxygen, water, etc., in the gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent. The polymerization conditions for olefins include a temperature of 20 to 300°C, preferably 40 to 300°C.
The temperature is 180℃, the pressure is normal pressure to 70Kg/ ^cm2・G,
Preferably it is 2 to 60 kg/cm ² ·G. Molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio.
This is effectively carried out by adding hydrogen into the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.

In the present invention, it can be particularly effectively used to polymerize or copolymerize α-olefins having 3 to 8 carbon atoms with good stereoregularity. Such α-olefins include propylene, 1-butene, 4-methylpentene-1, and the like. Other olefins such as ethylene, dienes, etc. can also be copolymerized with these α-olefins.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Synthesis of catalyst components 10 g of anhydrous magnesium chloride and 6 ml of tetraethoxysilane were placed in a 400 ml stainless steel pot containing 25 stainless steel balls each having a diameter of 1/2 inch, and the mixture was heated to room temperature under a nitrogen atmosphere. After performing ball milling for 16 hours at
ml was added and ball milling was performed for 16 hours at room temperature under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 35 mg of titanium.

(b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, and 1000 ml of hexane was added, followed by 5 mmol of triethylaluminum and ethyl benzoate.
Add 1.4 mmol and 100 mg of the above solid powder;
The temperature was raised to 50°C while stirring. The vapor pressure of hexane was 0.5 kg/cm ² G in the system, and then propylene was continuously introduced so that the total pressure was 7 kg/cm ² G, and polymerization was carried out for 1 hour.

After the polymerization was completed, excess propylene was discharged, cooled, and the contents were taken out and dried to obtain 165 g of white polypropylene. This is the total amount of the product, including the amorphous material.

Catalytic activity is 250g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 7300g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue rate with boiling n-heptane was 90.2%.
It was hot.

Comparative Example 1 In Example 1, when the catalyst component was synthesized and polymerized in the same manner as in Example 1 except that anhydrous aluminum trichloride was not used, only 16 g of polypropylene was obtained. .

Comparative Example 2 In Example 1, catalyst components were synthesized and polymerized in the same manner as in Example 1, except that tetraethoxysilane was not used, and 80 g of polypropylene was obtained.

Catalytic activity is 120g polypropylene/g solid.
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue rate with boiling n-heptane was 81.3%.
It was hot.

Example 2 In Example 1, 1:1 (molar ratio) of titanium tetrachloride and ethyl benzoate was used instead of titanium tetrachloride.
A solid powder was synthesized in the same manner as in Example 1 except that 3.6 g of the adduct was used, and 1 g of the obtained solid powder contained 20 mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 104 g of white polypropylene was obtained.

Catalytic activity is 160g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 8000g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue with boiling n-heptane was 92.5%.

Example 3 In Example 1, 9 ml of tetraethoxysilane
A solid powder was synthesized in the same manner as in Example 1 except that the obtained solid powder 1
g contained 31 mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 140 g of white polypropylene was obtained.

Catalytic activity is 220g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 6900g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue with boiling n-heptane was 89.5%.

Example 4 In Example 1, 9 g of anhydrous aluminum chloride
A solid powder was synthesized in the same manner as in Example 1 except that 1 g of the obtained solid powder contained 31 mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 169 g of white polypropylene was obtained.

Catalytic activity is 260g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 8400g polypropylene/gTi・
hr.C ₃ H ₆ , and the total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 86.5%.

Example 5 A solid powder was synthesized in the same manner as in Example 1, except that 12 g of anhydrous aluminum tribromide was used instead of anhydrous aluminum trichloride, and 1 g of the obtained solid powder was synthesized. 28 to
Contains mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 121 g of white polypropylene was obtained.

Catalytic activity is 190g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 6600g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue rate with boiling n-heptane was 87.6%.
It was hot.

Example 6 A solid powder was synthesized in the same manner as in Example 1 except that 4 ml of monoethoxytrichlorosilane was used instead of tetraethoxysilane, and 1 g of the obtained solid powder contained , contained 36mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 183 g of white polypropylene was obtained.

Catalytic activity is 280g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 7800g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The total extraction residue rate with boiling n-heptane was 88.1%.
It was hot.

Example 7 A solid powder was synthesized in the same manner as in Example 1 except that 5 ml of triethoxymonochlorosilane was used instead of tetraethoxysilane. Contains 35mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 174 g of white polypropylene was obtained.

Catalytic activity is 270g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 7600g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 89.5%.

Example 8 Polymerization of propylene was carried out in the same manner as in Example 1, except that 1.4 mmol of ethyl p-anisate and 5.0 mmol of triisobutylaluminum were used instead of ethyl benzoate and triethylaluminum. As a result, 160 g of white polypropylene was obtained.

Catalytic activity is 250g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 7000g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 91.3%.

Example 9 10 g of anhydrous magnesium chloride and 6 ml of tetraethoxysilane were placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls, and heated at room temperature under a nitrogen atmosphere for 16 hours.
After ball milling for an hour, 6 g of anhydrous aluminum trichloride was added and the mixture was heated for 16 hours at room temperature under a nitrogen atmosphere.
The crushed material obtained by time ball milling is
Transfer to a 300ml round bottom flask and add titanium tetrachloride.
Add 50 ml and 100 ml of n-heptane and heat at 100℃ for 2 hours.
Stir for hours. Next, it was washed nine times with 100 ml of n-hexane to remove unreacted titanium tetrachloride, and then vacuum dried to obtain a solid powder. 1 g of solid powder obtained
contained 43mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1, except that 100 mg of the above solid powder was used, and 200 g of white polypropylene was obtained.

Catalytic activity is 300g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 7200g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 90.5%.

Example 10 300ml of 10g of anhydrous magnesium chloride, 6ml of tetraethoxysilane, and 6g of anhydrous aluminum trichloride
Place in a round bottom flask, add 100ml of n-heptane, stir at 100℃ for 2 hours, then add titanium tetrachloride.
50 ml was added and stirred at 100°C for 2 hours. Next n-
After washing with 100 ml of hexane nine times to remove unreacted titanium tetrachloride, vacuum drying was performed to obtain a solid powder. 1 g of the obtained solid powder contained 37 mg of titanium.

Polymerization of propylene was carried out in the same manner as in Example 1 except that 100 mg of the above solid powder was used, and 113 g of white polypropylene was obtained.

Catalytic activity is 170g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 4600g polypropylene/gTi・
hr・C ₃ H ₆ pressure, including solvent-soluble polymers,
The residual rate after extraction with boiling n-heptane was 88.9%.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the steps for preparing a catalyst used in the method of the present invention.

Claims (1)

[Claims] 1 Magnesium dihalide, (2) General formula Si
(OR) _n X _4-n (where R is a hydrocarbon residue having 1 to 24 carbon atoms,
) and (3) a solid substance obtained by contacting aluminum trihalide with titanium tetrahalide and/or an addition compound of titanium tetrahalide and an organic acid ester. A polyolefin characterized in that the polymerization or copolymerization of an α-olefin having 3 to 8 carbon atoms is carried out using a catalyst formed by a combination of a solid catalyst component, and a mixture or addition compound of an organoaluminum compound and an organic acid ester. manufacturing method.