JPS58168604A - Production of poly-alpha-olefin - Google Patents

Abstract

PURPOSE:To produce a low Q-value poly-alpha-olefin in high yields, by polymerizing an alpha-olefin in the presence of a catalyst prepared from a specified solid catalytic component, an organoaluminum compound and an aromatic carboxylate ester. CONSTITUTION:A poly-alpha-olefin is produced by polymerizing 3 C or higher alpha- olefin in the presence of a catalyst prepared from (A) a solid catalytic component obtained by contacting a titanium tetrahalide with a contact solid obtained either by contacting a carrier with a Ti compound of formula III (wherein R<4> is a 1-6C alkyl, or phenyl, X<2> is a halogen and m is 1-3) and then with an aromatic carboxylate ester, or by contacting it with both a compound of formula III and an aromatic carboxylate ester, said carrier being prepared by reacting an aluminum halide with a silicon compound of formulaI(wherein R<1> is a 1-8C alkyl or phenyl, R<2> is a 1-8C alkyl and n is 0-3) and reacting the reaction product with a Grignard compound of formula II (wherein R<3> is a 1-8C alkyl and X<1> is a halogen), (B) an organoaluminum compound of formula IV (wherein R<5> is a 2-6C alkyl) and (C) an aromatic carboxylate ester.

Description

[Detailed description of the invention] The present invention relates to a method for producing poly-α-olefins.

Regarding a method for polymerizing α-olefins having 6 or more carbon atoms in the presence of a catalyst obtained from a solid catalyst component consisting of magnesium, titanium, halogen, and an electron donor, an organoaluminum compound, and an aromatic carboxylic acid ester. , many proposals have been made.

The present applicant has developed a support obtained by reacting a Grignard compound with a reaction product of an aluminum halide and a silicon compound to produce titanium tetrahalide.

A method of polymerizing an α-olefin having 6 or more carbon atoms in the presence of an organic acid ester and a catalyst consisting of a solid catalyst component obtained by treatment with titanium tetrahalide, an organoaluminum compound, and an organic acid ester, Already proposed (Japanese Unexamined Patent Publication No. 56-45909, Unexamined Japanese Patent Application No. 56+-1631)
No. 02, Japanese Patent Application No. 140362/1982). The molecular weight distribution of poly-α-olefins obtained by these methods is relatively wide, i.e. 1 weight average molecule it (MW)
/number average molecular weight (Mn)” (hereinafter this ratio is referred to as Q value)
is 11-14. Therefore, the above poly-α-olefin is suitable as a polymer for blow molding and extrusion molding. By the way, polymers for injection molding are desired to have a small Q value.

The present invention provides a process for producing poly-alpha-olefins with low Q values in significantly higher yields per solid catalyst component.

In other words, one aspect of the present invention is.

(1) Aluminum halide formula R1n51(OR2)4-n
[I] (wherein R1 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, R2 represents an alkyl group having 1 to 8 carbon atoms, and n is 0, 1.2 or 0); react with a silicon compound.

(2) The reaction product is expressed by the formula R3MfX1 [
(2)] (In the formula, R3 represents an alkyl group having 1 to 8 carbon atoms.

Xl represents a halogen atom).

(3) The resulting carrier.

0) Formula (R40)mTiX24-m [■] (in the formula
H4 represents an alkyl group having 1 to 6 carbon atoms or a phenyl group; +X2 represents a halogen atom;

or (b) contact with a titanium compound represented by formula [11[) and an aromatic carboxylic acid ester.

(4) A solid catalyst component (A) obtained by contacting a contact solid with titanium tetrahalide.

In the presence of an organoaluminum compound (B) represented by the formula AtR = [■] (in the formula + R5 represents an alkyl group having 2 to 6 carbon atoms) and a catalyst obtained from an aromatic carboxylic acid ester (0) This is a method for producing poly-α-olefin, which is characterized by polymerizing α-olefin having 6 or more carbon atoms.

According to the present invention, poly-α-olefins having a Q value of 5 to 7 can be obtained in high yield. Therefore, the operation of removing catalyst residue from the poly-α-olefin produced can be omitted, and the poly-α-olefin produced can be suitably used as a polymer for injection molding.

In the present invention, solid catalyst components are prepared using substantially anhydrous compounds under an inert gas atmosphere such as nitrogen, argon, etc.

Specific examples of aluminum halides in the present invention include aluminum chloride, aluminum bromide, and aluminum iodide, among which aluminum chloride is preferably used.

Specific examples of silicon compounds represented by formula [I] include:
Tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-isopentoxysilane, tetra-n-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane.

Methyltri-n-butoxysilane, methyltriisopentoxysilane, methyltri-n-hexoxysilane, methyltriisooctoxysilane, ethyltriethoxysilane, ethyltriisoflohoquine silane, ethyltriisopentoxysilane.

n-butyltriethoxysilane, isobutyltriethoxysilane, isopentyltriethoxysilane, isopentyltri-n-butoxysilane, dimethylethoxysilane, dimethyldi-n-butoxysilane, dimethyldiisopentoxysilane.

Diethyljethoxysilane, diethyldiisopentoxysilane, di-n-butyljethoxysilane.

Diisobutyldiisopentoxysilane, trimethylmethoxysilane, trimethylethoxysilane.

Trimethylisobutoxysilane, triethylisopropoxysilane, tri-n-propylethoxysilane, tri-n-butylethoxysilane, triisopentylethoxysilane, phenyltriethoxysilane, phenyltriisobutoxysilane.

Examples include phenyltriisopentoxysilane, diphenyljethoxysilane, diphenyldiynepentoxysilane, diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and triphenylisopentoxysilane.

What is the proportion of aluminum halogenide used in the reaction?

0.1 to 10 mol, especially 0, per mol of silicon compound
! The amount is preferably 1 to 2 mol.

The reaction between aluminum halide and a silicon compound is usually carried out by combining both compounds in an inert organic solvent.

This is carried out by stirring for 0.1 to 2 hours at a temperature in the range of -50 to 100°C. The reaction proceeds exothermically and the two reaction products are obtained as a solution in an inert organic solvent.

In addition, when using a tetraalkoxysilane in which n is 0 in formula 2 CI).

Insoluble matter of small elm may be formed. This insoluble matter does not inhibit the polymerization activity of the final catalyst, but
In order to facilitate the preparation operation of the solid catalyst component, it is desirable to separate the solid catalyst components from the two reaction product mixtures. The reaction product is subjected to the reaction with the Grignard compound as a solution in an inert organic solvent.

Among the Grignard compounds represented by formula [11], X
Alkylmagnesium chlorides in which l is a chlorine atom are preferably used, and specific examples thereof include.

Examples include methylmagnesium chloride, ethylmagnesium chloride, n-butylmagnesium chloride, and n-hexylmagnesium chloride.

The amount of Grignard compound used was 0.0 per mole of aluminum chloride used in the preparation of the reaction product.
It is preferably 5 to 4 mol, especially 1 to 6 mol.

There is no particular restriction on the method of reacting the reaction product and the Grignard compound, but it is possible to add an ether solution of the Grignard compound or a mixed solvent solution of ether and an aromatic hydrocarbon to a solution of the two reaction products in an inert organic solvent. Conveniently this is done by gradual addition or by addition in the reverse order. As for the ether above.

A compound represented by the formula R'-0-R' (in which R6 and R7 represent an alkyl group having 2 to 8 carbon atoms) is preferably used, and specific examples thereof include diethyl ether, diimpropyl ether, and diimpropyl ether. Examples include n-butyl ether and diisoamyl ether.

The reaction temperature is usually -50 to 100°C, preferably -20 to
The temperature is 25°C. There is no particular restriction on the reaction time, but9
Usually it is 5 minutes or more. As the reaction progresses, the carrier precipitates out. Although the carrier thus obtained can be subjected to the next treatment as a reaction product mixture, it is preferable to wash the produced carrier with an inert organic solvent before subjecting it to the treatment.

The carrier is then treated by the method (a) or (b) below.

The rat support is heated at 20-200°C, preferably 60-140°C, in the presence or absence of an inert organic solvent.
Contact with a titanium compound represented by Formula 1 [■] at a temperature of 0.5 to 3 hours, after which solids are separated from the reaction mixture and washed with an inert organic solvent if necessary, and then,
The titanium-contacted solid in the presence or absence of an inert organic solvent at a temperature of 20-200<0>C, preferably 60-140<0>C.

A method of treatment with an aromatic carboxylic acid ester for 0.5 to 3 hours.

(1)) A titanium compound represented by formula (1) and an aromatic carboxylic acid ester are used as a carrier in the presence or absence of an inert organic solvent at 20 to 200°C.

Preferably, the method is carried out at a temperature of 60 to 140°C for 0.5 to 3 sowing intervals.

Specific examples of the titanium compound represented by formula [111) include methoxytrichlortitanium, dimethoxydichlortitanium, trimethoxychlortitanium, ethoxytrichlortitanium, jetoxydichlortitanium, propoxytrichlortitanium, dipropoxydichlortitanium, butoxytrichlortitanium. Titanium, dibutoxydichlorotitanium, phenoxytrichlortitanium, diphenoxinechlortitanium, methoxytribromotitanium, phenoxytribromotitanium.

Examples include methoxytriiodotitanium and phenoxytriiodotitanium. The amount of titanium compound used is 1 mole of Grignard compound used in preparing the carrier.
The amount is preferably 2 to 100 moles or more, particularly 2 to 100 moles.

As an aromatic carboxylic acid ester.

[In the formula, R8 represents an alkyl group having 1 to 6 carbon atoms, Y is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 10R9,
(R9 represents an alkyl group having 1 to 4 carbon atoms.)

] Compounds represented by the following are preferably used; specific examples thereof include methyl benzoate, ethyl benzoate, methyl toluate, and ethyl toluate.

Examples include methyl anisate and ethyl anisate. The amount of aromatic carboxylic acid ester used is: 5 to 50% of the carrier
Preferably it is 30% by weight, especially 15-25% by weight.

The treated solid thus obtained is separated from the treated mixture;
Wash with inert organic solvent if necessary.

The treated solid is then contacted with titanium tetrahalide in the presence or absence of an inert organic solvent.

Specific examples of titanium tetrahalide include titanium tetrachloride,
Examples include titanium tetrabromide and titanium tetraiodide, of which titanium tetrachloride is preferably used.

The amount of titanium tetrahalide used is 1 mol or more, especially 2 mol or more, per 1 mol of Grignard compound used for the preparation of the carrier.
It is preferable that it is 100 mol. Contact temperature is 20~
The temperature is 200°C, preferably 60-140°C, and the contact time is usually 0.5-5 hours.

The solid catalyst component (A) is separated from the mixture by filtration, decanting, etc. and washed with an inert organic solvent. Solid catalyst component (
The titanium content in A) is 0.5-5% by weight.

In the present invention, an α-olefin having 6 or more carbon atoms is polymerized in the presence of a solid catalyst component (A), an organoaluminum compound (B) represented by formula [IV], and a catalyst obtained from an aromatic carboxylic acid ester. let

Specific examples of the organoaluminum compound (B) include:

Examples include triethylaluminum, triisobutylaluminum, and tri-hexylaluminum, among which triethylaluminum and triisobutylaluminum are preferably used.

The amount of organoaluminum compound (B) used is usually 1 to 100 per gram atom of titanium in the solid catalyst component (A).
It is 0 mole.

The amount of the aromatic carboxylic acid ester (C) is preferably 0.05 to 0.6 mol per 1 mol of the treated solid swelling compound (B).

Specific examples of the α-olefin having 3 or more carbon atoms to be polymerized by the method of the present invention include propylene, 1-phthene, 4-methyl-1-pentene, and 1-bequin-1=one. Furthermore, in the present invention.

A mixture of α-olefins having 6 or more carbon atoms or α-olefins having 6 or more carbon atoms
- It is also possible to copolymerize olefins and ethylene.

In the present invention, the double polymerization reaction can be carried out in the same manner as the polymerization reaction of α-olefins using a conventional Ziegler-Natsuta type catalyst.

The polymerization reaction can be carried out in liquid phase or gas phase.

When the polymerization reaction is carried out in a liquid phase, an inert organic solvent may be used as the polymerization solvent, or the liquid α-olefin itself may be used as the polymerization solvent. There are no particular restrictions on the catalyst concentration in the polymerization solvent, but in general, 1 part of the double polymerization solvent is used, and the solid catalyst component (A) is 0.00% in terms of titanium metal.
1 to 1 milligram atom, and 0.01 to 100 mmol for the organic aluminum compound (B).

In this invention, during the preparation of the solid catalyst component (A).

Examples of the inert organic solvent used in the polymerization reaction include aliphatic hydrocarbons such as hexane and heptane, toluene, benzene, xylene, nanoaromatic hydrocarbons, and halides of these hydrocarbons.

The polymerization reaction is carried out in the substantial absence of moisture and oxygen.

The polymerization temperature is usually 30 to 100°C, and the polymerization pressure is usually 1 to 8 kg/-.

The molecular weight of the α-olefin polymer obtained by the method of the present invention can be easily adjusted by adding hydrogen to the dipolymerization system.

Next, Examples and Comparative Examples will be shown. In the following description, "polymerization activity" refers to the polymer yield (f
), [a, , x, j are the weight percentages of the extraction residue when the produced polymer is extracted with boiling n-hebutane for 20 hours, based on the total polymer.

The melt flow index was measured at 2301 under a load of 2.16 kg/-. In the Examples and Comparative Examples, all solid catalyst components (A) were prepared in a dry nitrogen gas atmosphere.

Example 1 (1) Preparation of solid catalyst component To 30 tnl of a suspension of 15.7 mmol of anhydrous aluminum chloride in toluene was added 14.0 tnl of phenyltriethoxysilane.
After adding 5 mmol of toluene solution 1oIIL, the temperature was raised to 60°C and the reaction was allowed to proceed for 1 hour while stirring.

After cooling the reaction product mixture to -10°C, the n-
A solution of 27 mmol of butylmagnesium chloride in diynamyl ether 18111 was added dropwise into the reaction product mixture over a period of 40 minutes. The temperature of the reaction system was maintained at =10°C. After the dropping was completed, the temperature was raised to 60°C.

The reaction continued for 1 hour. The precipitated carrier was separated from each other and washed with toluene. 30 m of toluene suspension of the obtained carrier
After adding a solution of 137 mmol of n-butoxytrichlortitanium in toluene 501111 to e.

The temperature was raised to 90°C, and the mixture was brought into contact with the carrier for 1 hour while stirring.

At the same temperature, the contact solid was separated and washed with toluene. 0.74 mJ of ethyl benzoate was added to a toluene suspension of 3.52 f of contact solid at 6°WLg, and the mixture was kept at 90°C for 1 hour with stirring. The treated solids were washed separately at 90°C with n-hebutane and then toluene. 15% of titanium tetrachloride was added to 50ml of a toluene suspension of the treated solid, and the mixture was stirred at 90°C for 1 hour.

The treated solid was contacted with titanium tetrachloride. The obtained solid catalyst component was separated at the same temperature and washed with n-hebutane.

6.11 of the solid catalyst component thus obtained was suspended in 80 ml of n-hebutane. The titanium content of the solid catalyst component was 2.68% by weight.

(2) A glass ampoule containing a slurry of 12.0~ of solid catalyst components was attached to an autoclave with an internal volume of 2 tons equipped with a stirrer, and the air in the autoclave was replaced with nitrogen. triethylaluminum 1.34 mmol l'l
-6.4ml of heptane solution! , then 4.5all of a solution of 0.34 mmol of methyl p-toluate in n-hebutane.
was introduced into the autoclave.

After introducing 1200 ml of liquid propylene, the autoclave was shaken and the contents were then heated to 65°C. Start stirring, crush the glass ampoule, and stir at 65°C for 1 hour.
Time propylene was polymerized.

After the polymerization was completed, unreacted propylene was discharged, glass fragments were removed, and the resulting polymer was dried under reduced pressure at 50° C. for 20 hours.

Powdered polypropylene 198f was obtained. Polymerization activity is 16
500. H,1, was 95.3%. Gel permeation chromatography [manufactured by Waters, 150
CALC/GPC using 0-dichlorobenzene as a solvent.

The Q value measured at 135°C was 7.1.

Example 2 and Example 1 was repeated except that the amount of methyl p-toluate used was varied as described in Table 1. The results are shown in Table 1.

Examples 4 and 5 Hydrogen was brought to a partial pressure of 0.5 K prior to the introduction of liquid propylene.
Examples 2 and 3 were repeated, respectively, except that p/-.G was introduced into the autoclave. Second result
Shown in the table.

Table 2 Example 6 Solid catalyst component obtained by using 100 mmol of phenoxytrichlortitanium in place of n-butoxytrichlortitanium (titanium content: 2.50 weight $313.87v)
Example 1 was repeated except that a slurry of .

Polymerization activity is 13800. H, r: Blood was 95.8 cm, Q value was 7.2.

Example 7 As a method for preparing the treated solid, 30 m of toluene suspension of the carrier was prepared.
/, 50 ml of a toluene solution of 137 mmol of n-butoxytrichlorotitanium and 0.74 ml of ethyl benzoate.
Example 1 was repeated, except that a method of contacting with e at 90° C. for 1 hour was adopted.

Polymerization activity is 16,700. H, engineering, coefficient was 95.4, and Q value was 7.2.

Example 8 Example 1 was repeated, except that 14.5 mmol of methyltriethoxysilane was used instead of phenyltriethoxysilane.

Polymerization activity is 16800. H,1, had a ratio of 95.1 and a Q value of 7.0.

Comparative Example 1 Titanium tetrachloride 1 instead of n-butoxytrichlortitanium
A solid catalyst component having a titanium content of 2.75% by weight was prepared by repeating Example 1-(1) except that 37 mmol was used.

Example 1-(2 ) was repeated.

Polymerization activity is 16300. H, ■, coefficient was 95.6, and Q value was 13.6.

Patent applicant: Ube Industries Co., Ltd.

Claims (4)

[Claims] (1) Aluminum halide with the formula R',,51(oR2)4-n
CI ) (wherein R1 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, R2 represents an alkyl group having 1 to 8 carbon atoms, and n is 0, 1.2 or 6). react with a compound. (2) The reaction product is expressed by the formula R3MgX Violet
[H] (in the formula, + R3 represents an alkyl group having 1 to 8 carbon atoms; Xl represents a halogen atom) and is reacted with a Kriniyal compound. (3) The resulting carrier.・(A) Represented by the formula (R40) mTIX241 [■] (in the formula, +R' represents an alkyl group or phenyl group having 1 to 6 carbon atoms, X2 represents a halogen atom, and 2m is 1.2 or self) titanium compound, and then contacted with an aromatic carboxylic acid ester. or (b) contact with a titanium compound represented by the formula [1[[] and an aromatic carboxylic acid ester; (4) A solid catalyst component (A) obtained by contacting a contact solid with titanium tetrahalide. Formula AIR Mi [■]
(in the formula, R5 represents an alkyl group having 2 to 6 carbon atoms) and a catalyst obtained from an aromatic carboxylic acid ester (C). - A method for producing a poly-α-olefin, which comprises polymerizing an olefin.