JPS6410530B2 - - 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 it is also important that the amount of atactic moieties produced 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.

Furthermore, the catalyst system used in the present invention has the effect that the amount of halogen contained in the produced polymer is extremely small compared to a catalyst system that uses MgCl ₂ as a carrier.

In the present invention, titanium tetrahalide is added to a solid material obtained by co-pulverizing magnesium monohalide represented by the general formula MgX (X represents a halogen atom) and a phosphorus compound selected from phosphorus halides and phosphorus oxyhalides. and/or a solid catalyst component obtained by supporting an addition compound of titanium tetrahalide (hereinafter abbreviated as a titanium compound) and an organic acid ester, and an organic aluminum compound (hereinafter abbreviated as an organometallic compound) and an organic acid ester This 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 a catalyst formed by combining a mixture with or an addition compound.

The essence of the present invention is to use a solid material obtained by co-pulverizing magnesium monohalide and a phosphorus compound selected from phosphorus halides and phosphorus oxyhalides as a carrier. Co-milling is carried out under an inert gas atmosphere and substantially in the absence of solvent.

The ratio of magnesium monohalide and phosphorus compound used at this time is preferably 0.01 to 100 mol, particularly 0.1 to 10 mol, of the phosphorus compound per 1 mol of magnesium monohalide.

The equipment used for co-grinding is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used, and those skilled in the art can easily determine the conditions such as the grinding temperature and grinding time depending on the grinding method. It is determined. Generally, the crushing temperature is 0
The temperature is about ℃~50℃, and the grinding time is 0.5~50 hours.
Preferably it is 1 to 30 hours.

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. , in the absence of an inert solvent such as n-hexane, at 50 to 300°C, preferably at 100°C.
This is conveniently done by heating to ~150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. 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. The equipment used for co-pulverization is not particularly limited, but ball mills, vibration mills, rod mills, impact mills, etc. are usually used.
The catalyst component of the present invention can be produced by co-milling preferably at a temperature of 20°C to 100°C for 0.5 to 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.

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.

Examples of the magnesium monohalide used in the present invention include monomagnesium chloride, monomagnesium bromide, and monomagnesium iodide, with monomagnesium chloride being particularly preferred.

Various methods are known for producing magnesium monohalide. For example, it can be obtained by subjecting a Grignard compound of magnesium (RMgX) to a vacuum of about 300°C.

2RMgX → 2MgX + R _2This reaction is e.g. Chemische Berichte 85
(1952), pp. 593 and 598-599.
The present invention is not limited to these.

The phosphorus compound selected from phosphorus halides and phosphorus oxyhalides used in the present invention includes:
Examples include phosphorus pentachloride, phosphorus pentabromide, phosphorus pentaiodide, phosphorus trichloride, phosphorus tribromide, phosphorus triiodide, phosphorus oxytrichloride, phosphorus oxytribromide, etc. Preferred are phosphorus chloride and phosphorus oxytrichloride.

As the titanium compound used in the present invention, titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are preferable. Also, the general formula Ti(OR _{) n} A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by .

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 COOC 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 used is not particularly limited, but the amount of the titanium compound contained in the solid product is usually 0.5 to 20% by weight, preferably 1% by weight.
It is preferable to adjust the amount 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, diethylaluminium chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, and mixtures thereof.

One of the features of the present invention is that the organometallic compound component is used as a mixture or addition compound of the organometallic compound and the organic acid ester.

At this time, when the organometallic compound and the organic acid ester are used as a mixture, the organic acid ester is usually 0.1 to 1 mole per 1 mole of the organometallic compound.
Preferably 0.2 to 0.5 mol is used. 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-benzoate, phenyl salicylate, cyclohexyl p-oxybenzoate,
Benzyl salicylate, ethyl α-resorcylate,
Methyl anisate, ethyl anisate, phenyl anisate, benzyl anisate, ethyl o-methoxybenzoate, methyl p-ethoxybenzoate, methyl p-toluate, ethyl p-toluate, phenyl p-toluate, o- Ethyl toluate, m-ethyl toluate, methyl p-aminobenzoate, p
- Examples include ethyl aminobenzoate, vinyl benzoate, allyl benzoate, benzyl benzoate, 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 (1) Synthesis of catalyst components Magnesium monochloride 5g and phosphorus pentachloride 13.9g
was placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls with a diameter of 1/2 inch, and heated at room temperature under a nitrogen atmosphere for 16 hours.
After ball milling for an hour, titanium tetrachloride and ethyl benzoate were added in a 1:1 (molar ratio)
7.5 g of the adduct compound was added and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 37 mg of titanium.

(2) 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 3 mmol of triethylaluminum, 1 mmol of ethyl benzoate, and the above solid powder.
Add 80mg and further hydrogen at a gas phase partial pressure of 0.025
After charging so that the amount is 50 kg/cm ² ,
The temperature was raised to ℃. The vapor pressure of hexane is 0.5
Kg/cm ² ·G, then propylene was charged until the total pressure reached 7Kg/cm ² ·G to start polymerization. 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 71 g of white powdery polypropylene. The solvent soluble polypropylene was 2.7g.

Catalytic activity is 140g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 3800g polypropylene/gTi・
hr・C ₃ H ₆ pressure, and the boiling n-heptane extraction residual rate of this powdered polypropylene was 94.0%.
The total extraction residue with boiling n-heptane, including the solvent-soluble polymer, was 90.6%.

Example 2 In (1) of Example 1, titanium tetrachloride 2.0 was used instead of the addition compound of titanium tetrachloride and ethyl benzoate.
A catalyst component was synthesized in the same manner as in Example 1 except that ml was used.

80 mg of the above catalyst components, 1000 ml of n-hexane,
Example 1 Using 1 mmol of an addition compound of 1 mol of triethylaluminum and 1 mol of ethyl benzoate and 1 mmol of triisobutylaluminum
When propylene was polymerized in the same manner as above, 93 g of white polypropylene was obtained. The solvent soluble polypropylene was 3.7g. Catalyst activity is 190g
Polypropylene/gcat・hr・C ₃ H ₆ pressure, 5140g polypropylene/gTi・hr・C ₃ H ₆ pressure, and the boiling n-heptane extraction residual rate of powdered polypropylene is
91.5%, while solvent-soluble polymers also contain n-
The total extraction residue rate with heptane was 88.0%.

Example 3 In (1) of Example 1, the amount of phosphorus pentachloride used was
The catalyst component was synthesized in the same manner as in Example 1, except that the amount of the addition compound of titanium tetrachloride and ethyl benzoate was changed to 2.6 g, and the polymerization of propylene was carried out in the same manner as in Example 1. As a result, 67 g of white polypropylene was obtained. The solvent soluble polypropylene was 2.7g.

Catalytic activity is 135g polypropylene/g solid・hr・
C ₃ H ₆ pressure, 3720g polypropylene/gTi・hr・C ₃ H ₆
The percentage of this polypropylene extracted with boiling n-heptane is 93.8%, while the total percentage of residue extracted with boiling n-heptane, including the solvent-soluble polymer, is 93.8%.
It was 90.2%.

Example 4 In (1) of Example 1, the amount of phosphorus pentachloride used was
The catalyst component was synthesized in the same manner as in Example 1, except that the amount of the addition compound of titanium tetrachloride and ethyl benzoate was changed to 26 g and 12 g, and propylene was polymerized in the same manner as in Example 1. 77g of white polypropylene was obtained. The solvent-soluble polypropylene was 3.0 g.

Catalytic activity is 150g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 4530g polypropylene/gTi・hr・
The _pressure was _C3H6 , and the residual rate of this powdered polypropylene after extraction with boiling n-heptane was 93.0%, and the total residual rate of extraction including the solvent-soluble polymer was 89.5%.

Comparative Example 1 The same method as Example 1 except that in (1) of Example 1, phosphorus pentachloride was not used and the amount of the addition compound of titanium tetrachloride and ethyl benzoate was 2.0 g. A catalyst component was synthesized, and propylene was polymerized in the same manner as in Example 1, yielding 10 g of white polypropylene.

Catalytic activity is 20g polypropylene/g solids・hr・
C ₃ H ₆ pressure, 530g polypropylene/gTi・hr・C ₃ H ₆
The n-heptane extraction residue of powdered polypropylene was 95.0%, and the total extraction residue was 90%.

Comparative Example 2 When propylene was polymerized in the same manner as in Example 1 except that ethyl benzoate was not used in (2) of Example 1, the solvent became viscous due to a considerable amount of adduct. It contained white polypropylene. The obtained white polypropylene was 110 g, and the solvent-soluble polypropylene was 24 g. The boiling n-heptane extraction residue of this polypropylene is 69%, while the total extraction residue with boiling n-heptane, including solvent-soluble polymers, is 56.5%.
It was hot.

Catalytic activity is 260g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 6800g polypropylene/gTi・hr・
The pressure was C ₃ H ₆ .

Comparative Example 3 After thoroughly drying a 300ml three-necked flask equipped with a stirrer, a ball condenser, and a thermometer,
100 ml of dehydrated n-heptane, 5 g of magnesium monochloride, and 13 g of phosphorus pentachloride were added, and the mixture was reacted under reflux for 3 hours. After the reaction was completed, n-heptane was removed by distillation and then dried to obtain 17.5 g of solid.
A catalyst component was synthesized in the same manner as in Example 1 (1) using 5 g of this solid and 2 g of a 1:1 (molar ratio) addition compound of titanium tetrachloride and ethyl benzoate. Polymerization of propylene was carried out using the same method, and 15 g of white polypropylene was obtained. Solvent soluble polypropylene was 0.5g.

Catalytic activity is 30g polypropylene/g solids・hr・
C ₃ H ₆ pressure, 830g polypropylene/gTi・hr・C ₃ H ₆
The n-heptane extraction residue of powdered polypropylene was 93.1%, and the total extraction residue was 90.0%.

Example 5 Example 1 except that in (1) of Example 1, 8.7 g of magnesium monobromide was used instead of magnesium monochloride, and the amount of the addition compound of titanium tetrachloride and ethyl benzoate was 7.0 g. A catalyst component was synthesized in the same manner as in Example 1, and propylene was polymerized in the same manner as in Example 1. White polypropylene was obtained.
Got 65g. The solvent soluble polypropylene was 2.2g.

Catalytic activity is 130g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 3400g polypropylene/gTi・hr・
The _pressure was _C3H6 , and the residual rate of this powdered polypropylene after extraction with boiling n-heptane was 94.1%, and the total residual rate of extraction including the solvent-soluble polymer was 91.0%.

Example 6 Example 1 except that ethyl o-toluate was used instead of ethyl benzoate in (2) of Example 1.
When propylene was polymerized in the same manner as above, 70 g of white polypropylene was obtained. The solvent soluble polypropylene was 2.6g.

Catalytic activity is 140g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 3770g polypropylene/gTi・hr・
The _pressure was _C3H6 , and the residual rate of this powdered polypropylene after extraction with boiling n-heptane was 94.6%, and the total residual rate of extraction including the solvent-soluble polymer was 91.0%.

Example 7 Same as Example 1 except that in (1) of Example 1, 9.2 g of phosphorus trichloride was used instead of phosphorus pentachloride, and the amount of the addition compound of titanium tetrachloride and ethyl benzoate was 2.3 g. A catalyst component was synthesized in the same manner as in Example 1, and propylene was polymerized in the same manner as in Example 1 to obtain 35 g of white polypropylene. The solvent-soluble polypropylene was 1.1 g.

Catalytic activity is 70g polypropylene/g solids・hr・
C ₃ H ₆ pressure, 3500g polypropylene/gTi・hr・C ₃ H ₆
The residual ratio of this polypropylene after extraction with boiling n-heptane was 95.1%, and the total extraction ratio including the solvent-soluble polymer was 92.0%.

Example 8 Same as Example 1 except that in (1) of Example 1, 10.3 g of phosphorus oxychloride was used instead of phosphorus pentachloride, and the amount of the addition compound of titanium tetrachloride and ethyl benzoate was 6 g. A catalyst component was synthesized, and propylene was polymerized in the same manner as in Example 1, yielding 68 g of white polypropylene. The solvent soluble polypropylene was 2.6g.

Catalytic activity is 135g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 3600g polypropylene/gTi・hr・
C ₃ H ₆ pressure and the boiling point n of this polypropylene
-The heptane extraction residue rate was 94.0%, and the total extraction residue rate including the solvent-soluble polymer was 90.5%.

The stainless steel autoclave equipped with an electromagnetic induction stirrer from Example 9 2 was thoroughly dried and purged with nitrogen, and then 25 mg of the solid powder used in Example 1, 5.0 mmol of triethylaluminum, 2 mmol of ethyl benzoate, and 500 g of liquid propylene were charged. The polymerization was carried out at 60°C for 1 hour.

After the polymerization was completed, the propylene was purged, the product was taken out, and the polymer was dried under reduced pressure, yielding 80 g.
of polypropylene was obtained. The residual rate of polypropylene extracted with boiling n-heptane was 88.7%.

Catalytic activity is 145g polypropylene/g solid.
hr・C ₃ H ₆ pressure, 3800g polypropylene/gTi・hr・
The pressure was C ₃ H ₆ .

Example 10 Solid powder in the polymerization of propylene of Example 9
Polymerization of propylene was carried out for 3 hours in the same manner as in Example 9 except that 30 mg was used. Thereafter, excess propylene was discharged to normal pressure at 60°C. Next, 20 g of ethylene was pressurized with gas, and polymerization was carried out for 30 minutes. After the polymerization was completed, excess ethylene was released and the resulting copolymer was dried to obtain 320 g of white powdery propylene copolymer.

Catalytic activity is 160g polymer/g solid・hr・C ₃ H ₆
The pressure was 4200 g polymer/g solids.hr.C ₃ H ₆ pressure. The ethylene content in the obtained block copolymer was 9.9 mol%, and the boiling n-heptane extraction rate was
It was 86.0%.

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1 A solid substance obtained by co-pulverizing magnesium monohalide represented by the general formula MgX (X represents a halogen atom) and a phosphorus compound selected from phosphorus halide and phosphorus oxyhalide is added with titanium tetrahalide and/or Alternatively, using a solid catalyst component obtained by supporting an addition compound of titanium tetrahalide and an organic acid ester, and a catalyst formed by combining a mixture or an addition compound of an organoaluminum compound and an organic acid ester, a catalyst having 3 to 8 carbon atoms can be used. A method for producing a polyolefin, which comprises polymerizing or copolymerizing an α-olefin.