JPS646642B2 - - Google Patents

Description

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

A method of polymerizing an α-olefin having 3 or more carbon atoms in the presence of a solid catalyst component in which a titanium halide is supported on a magnesium compound, an organoaluminum compound, and an aromatic carboxylic acid ester is known. According to this method,
This is an excellent method in that α-olefin polymers with high stereoregularity can be obtained in extremely high yields, so that the operation for removing residual catalyst residues from the produced α-olefin polymers is not necessary or can be significantly simplified. effect is achieved. However, the α-olefin polymer obtained by this method generates an odor due to compounds attributable to the aromatic carboxylic acid ester added to the polymerization system. In particular, when the above polymer is molded, a strong odor is generated and the working environment is significantly polluted, which is a major obstacle to the industrial implementation of the above method. As a method to remove this odor, a method has been proposed in which the above polymer is treated with steam (Japanese Unexamined Patent Application Publication No. 1983-1999-1).
Publication No. 24407). According to the proposed method, the odor of α-olefin polymer can be almost eliminated, but it requires the use of a large amount of steam;
Furthermore, there is a drawback that a large amount of heat and time are required to dry the polymer after steam treatment.

An object of the present invention is to provide a method for polymerizing α-olefin that is odorless and can obtain a highly stereoregular α-olefin polymer in high yield.

The purpose of the present invention is to (1) convert aluminum halide into a compound having the formula R ¹ mSi(OR ² ) _4-n [] (wherein R ¹ represents an alkyl group or phenyl group having 1 to 8 carbon atoms, and R ² represents an alkyl group having 1 to 8 carbon atoms, and m is 0, 1, 2 or 3), (2) the reaction product is reacted with a silicon compound represented by the formula R ³ MgX [] (in the formula, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X represents a halogen atom. or (b) contact with titanium tetrahalide and aromatic carboxylic acid ester, (4) solid catalyst component A obtained by contacting the contacted solid with titanium tetrahalide, formula AlR ⁴ ₃ [ ] Organoaluminum compound B represented by (wherein R ⁴ represents an alkyl group having 2 to 6 carbon atoms),
and Eq. This is achieved by polymerizing an α-olefin having 3 or more carbon atoms in the presence of a catalyst obtained from a piperidine derivative C represented by the formula (where n is an integer of 1 to 12).

According to the present invention, odorless α-olefin polymers can be obtained in extremely high yields, so that the excellent effect of omitting the deodorizing operation of the produced polymer and the removal operation of catalyst residues is achieved. In addition, in the present invention, an aromatic carboxylic acid ester is used when preparing the solid catalyst component A, but since only a small amount of this is incorporated into the solid catalyst component A, an odor is generated in the produced α-olefin polymer. Never.

FIG. 1 shows the method for polymerizing α-olefin of the present invention and the process for preparing the catalyst used in the polymerization.

In the present invention, the preparation and polymerization of the solid catalyst component are all carried out under an inert gas atmosphere such as nitrogen or argon. Further, it is desirable that the raw material for preparing the solid catalyst component is substantially anhydrous.

The solid catalyst component A used in the present invention is:
Japanese Patent Application Laid-Open No. 56-45909 filed by the present applicant,
It can be prepared according to the method described in JP-A-56-163102 and Japanese Patent Application No. 56-140361.

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

Specific examples of silicon compounds include tetramethoxysilane, tetraethoxysilane, and tetra-n-
Propoxysilane, Tetra-n-butoxysilane, Tetra-isopentoxysilane, Tetra-n
-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n
-butoxysilane, methyltriisopentoxysilane, methyltri-n-hexoxysilane, methyltriisooctoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopentoxysilane, n-butyltriethoxysilane, isobutyl Triethoxysilane, isopentyltriethoxysilane, isopentyltri-n-butoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane,
Dimethyldiisopentoxysilane, diethyldiethoxysilane, diethyldiisopentoxysilane, di-n-butyldiethoxysilane, diisobutyldiisopentoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisobutoxysilane, triethyliso Propoxysilane, tri-n-propylethoxysilane,
Tri-n-butylethoxysilane, triisopentylethoxysilane, phenyltriethoxysilane, phenyltriisobutoxysilane, phenyltriisopentoxysilane, diphenyldiethoxysilane, diphenyldiisopentoxysilane,
Examples include diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxysilane, and triphenylisopentoxysilane.

The proportion of aluminum halide used in the reaction is preferably 0.1 to 10 mol, particularly 0.3 to 2 mol, per mol of silicon compound.

The reaction between aluminum halide and a silicon compound is usually carried out by combining both compounds in an inert organic solvent with -
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 with exotherm, and the reaction product is obtained as a liquid in an inert organic solvent. Note that when using a tetraalkoxysilane in which n is 0 in the formula [], a small amount of insoluble matter may be generated. Although this insoluble material does not inhibit the polymerization activity of the final catalyst, it is used to facilitate the preparation of the solid catalyst component.
It is desirable to separate it from the reaction product mixture. 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 the formula [], alkylmagnesium chlorides in which X is a chlorine atom are preferably used, and specific examples thereof include methylmagnesium chloride, ethylmagnesium chloride, n-butylmagnesium chloride, and n-hexylmagnesium chloride. Examples include.

The amount of Grignard compound used is preferably 0.05 to 4 mol, especially 1 to 3 mol, per mol of aluminum halide used for the preparation of the reaction product.

There is no particular restriction on the method of reacting the reaction product with the Grignard compound, but an ether solution of the Grignard compound or a solution of a mixed solvent of ether and an aromatic hydrocarbon is gradually added to the solution of the reaction product in an inert organic solvent. Conveniently this is done by addition or addition in the reverse order. As the above-mentioned ether, a compound represented by the formula R ⁵ -0-R ⁶ (in the formula, R ⁵ and R ⁶ represent an alkyl group having 2 to 8 carbon atoms) is preferably used, and specific examples thereof include: Examples include diethyl ether, diisopropyl ether, di-n-butyl ether, and diisoamyl ether.

The reaction temperature is usually -50 to 100℃, preferably -20℃
~25℃. There is no particular restriction on the reaction time, but it is usually 5 minutes or more. As the reaction progresses, a white carrier precipitates out. Although the carrier thus obtained can be used as a reaction mixture for the next treatment, it is preferable to separate the carrier in advance and wash it with an inert organic solvent before using it for the next treatment.

In the present invention, the carrier is then selected from the following (a) or
Contact with titanium tetrahalide and aromatic carboxylic acid ester by method (b).

(b) The support is brought into contact with titanium tetrahalide in the presence or absence of an inert organic solvent at a temperature of 20 to 200°C, preferably 60 to 140°C, for 0.5 to 3 hours, and the resulting solid is After separation and washing, an aromatic carboxylic acid ester is added to a suspension of the solid in an inert organic solvent, and the mixture is brought into contact with the suspension at a temperature of 0 to 200°C, preferably 5 to 150°C, for 5 minutes or more.

(b) Contacting the support with titanium tetrahalide and aromatic carboxylic acid ester at a temperature of 20 to 200°C, preferably 60 to 140°C, for 0.5 to 3 hours in the presence or absence of an inert organic solvent. How to do it.

Specific examples of titanium tetrahalide include titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide, of which titanium tetrachloride is preferably used. The amount of titanium tetrahalide 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 aromatic carboxylic acid ester, [In the formula, R ⁷ 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 -OR ⁸ (R ⁸ represents an alkyl group having 1 to 4 carbon atoms) Compounds represented by the following are preferably used, and specific examples thereof include methyl benzoate, ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, and ethyl anisate.

The contact solid obtained by the method (a) or (b) above,
Solid catalyst component A is prepared by contacting with titanium tetrahalide again. Conditions such as the amount of titanium tetrahalide used, contact temperature, and contact time are the same as those for preparing the contact solid.

The solid catalyst component A is separated from the thus obtained mixture containing the solid catalyst component A by filtration, decanting, etc., and washed with an inert organic solvent. Solid catalyst component A contains 0.5 to 5% by weight of titanium.

In the present invention, solid catalyst component A, formula []
An α-olefin having 3 or more carbon atoms is polymerized in the presence of a catalyst obtained from an organoaluminum compound B represented by the formula [ ] and a piperidine derivative C represented by the formula [ ].

Specific examples of organoaluminum compound B include:
Examples include triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and the like, among which triethylaluminum and triisobutylaluminum are preferably used. The amount of organoaluminum compound B used is usually 1 gram atom of titanium in solid catalyst component A.
~1000 mol.

Specific examples of piperazine derivative C include bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(2,2,6,6-tetramethyl-4-piperidyl)adipate, bis(2 , 2,6,6-tetramethyl-4-piperidyl) sebacate, and the like. The amount of piperidine derivative C used is the organoaluminum compound B1
Preferably it is 0.01 to 1 mol, especially 0.05 to 0.5 mol per mol.

Specific examples of α-olefins having 3 or more carbon atoms include propylene, butene-1,4-methylpentene-1, hexene-1, and the like. In the present invention, the above α-olefin can be used alone or copolymerized, and the α-olefin and ethylene can also be copolymerized.

The polymerization reaction can be carried out in the same manner as the polymerization reaction of α-olefin using a usual 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, the solid catalyst component A is 0.001 to 1 milligram atom in terms of titanium metal, and the organoaluminum compound B is 0.001 to 1 milligram atom per polymerization solvent.
0.01-100 mmol.

In this invention, when preparing the solid catalyst component A,
Examples of the inert organic solvent that may be used in the polymerization reaction include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene, benzene, and xylene, 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 80 kg/cm ² .

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

Next, examples will be shown. In the following description,
"Polymerization activity" is the polymer yield (g) per 1 hour of polymerization time per 1 g of solid catalyst component used in the polymerization reaction.
- It is the weight percentage of the extraction residue based on the total polymer when extracted with heptane for 20 hours. In the Examples, all solid catalyst components were prepared in a dry nitrogen gas atmosphere.

Example 1 (1) Preparation of solid catalyst component 15 mmol of methyltriethoxysilane was added to 40 ml of toluene containing 15 mmol of anhydrous aluminum chloride, reacted for 30 minutes at 25°C with stirring, and then the reaction mixture was heated to 60°C. The temperature was raised and the reaction was continued at the same temperature for 1 hour.

The reaction mixture was cooled to -5 DEG C. and 18 ml of diisoamyl ether containing 27 mmol of n-butylmagnesium chloride were added to the reaction mixture over 30 minutes while stirring. The temperature of the reaction system was maintained at -5°C. The temperature of the reaction mixture was raised to 30°C, and the reaction was continued at the same temperature for 1 hour. The precipitated carrier was separated and washed with toluene.

150 mmol of titanium tetrachloride was added to 25 ml of a suspension of 4.9 g of carrier in toluene, and the mixture was maintained at 90° C. for 1 hour while stirring. Add 6.5 mmol of ethyl benzoate to 25 ml of toluene suspension of the obtained solid and heat at 90°C with stirring.
It was held for 1 hour. The resulting contact solid was separated at 90°C and washed with n-heptane and then toluene.

Titanium tetrachloride in 25 ml of toluene suspension of contact solids
150 mmol was added and kept at 90° C. for 1 hour under stirring. The obtained solid catalyst components were separated at 90°C and
- Washed with heptane. 3.5g of solid catalyst component
- A solid catalyst component slurry was prepared by suspending it in 80 ml of heptane. The titanium content of the solid catalyst component is
It was 2.62% by weight.

(2) Polymerization 0.009 mmol of bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate and 200 ml of n-heptane were added to a separable flask with an internal volume of 500 ml under a nitrogen gas atmosphere, and the contents of the flask were The temperature was raised to 60°C. After bubbling propylene gas into the flask to saturate the propylene with n-heptane, 1 ml of a solution of 0.15 mmol of triethylaluminum in n-heptane was added. After 10 minutes, a slurry of 27.7 mg of the solid catalyst component was added to the flask, and propylene polymerization was carried out for 1 hour. During the polymerization reaction, propylene was continuously supplied (propylene pressure: 0.72 Kg/cm ² ), and the polymerization temperature was maintained at 60°C.

After the polymerization reaction was completed, the contents of the flask were poured into 1 part of isopropanol, stirred for 10 minutes, and then the produced polymer was separated. The polymer was dried under reduced pressure at 60° C. for 20 hours to obtain 24.6 g of powdered polypropylene.
The polymerization activity was 889 and the HI was 94.0%.

Example 2 Example 1 was repeated except that the amount of bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate used was changed to 0.018 mmol.

The polymerization activity was 720, and the H.I. was 96.0%.

Example 3 Example 1 was repeated, except that 25.6 mg of a slurry of solid catalyst component (titanium content: 2.84% by weight) obtained by substituting 15 mmol of tetraethoxysilane for methyltriethoxysilane was used.

The polymerization activity was 860, and the H.I. was 93.9%.

Example 4 A glass ampoule containing 9.4 mg of the solid catalyst component slurry prepared in Example 1 was placed in an autoclave with an internal volume of 2 and equipped with a stirrer, and the air in the autoclave was replaced with nitrogen.

A solution of 0.13 mmol of bis(2,2,6,6-tetramethyl-4-piperazine) sebacate and 0.51 mmol of triethylaluminum in n-heptane.
1.5 ml and then 1200 ml of liquid propylene were introduced into the autoclave and the autoclave was shaken.
After heating the contents of the autoclave to 65°C, stirring was started to crush the glass ampoule, and propylene was polymerized at 65°C for 1 hour. After the polymerization reaction is complete,
Unreacted propylene was released, glass fragments were removed, and the resulting polypropylene was dried under reduced pressure at 50° C. for 20 hours.

136 g of polypropylene was obtained. Polymerization activity is
14500, HI was 94.2%.

Example 5 150 mmol of titanium tetrachloride and 5.9 mmol of ethyl benzoate were added to a toluene suspension of the carrier.
Example 1 was repeated except that the contact solid was prepared by holding at 90° C. for 1 hour.

The polymerization activity was 870, and the H.I. was 93.6%.

The polypropylenes obtained in Examples 1 to 5 were odorless and did not emit any odor even when heated and melted at 230°C.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing the method for polymerizing α-olefin of the present invention.

Claims (1)

[Claims] 1 (1) Aluminum halide has the formula R ¹ mSi(OR ² ) _4-n (wherein, R ¹ represents an alkyl group having 1 to 8 carbon atoms or a phenyl group, and R ² represents a carbon (2) The reaction product is reacted with a silicon compound represented by the formula R ³ MgX (where R ³ is carbon (3) The resulting carrier is contacted with (a) titanium tetrahalide and then with an aromatic carboxylic acid ester. or (b) contact with titanium tetrahalide and an aromatic carboxylic acid ester, (4) a solid catalyst component A obtained by contacting the contacted solid with titanium tetrahalide, formula AlR ⁴ ₃ (wherein R ⁴ represents an alkyl group having 2 to 6 carbon atoms), and an organoaluminum compound B represented by the formula (wherein n is an integer of 1 to 12) in the presence of a catalyst obtained from a piperidine derivative C represented by legal.