JPS646647B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a solid catalyst component for α-olefin polymerization. The applicant has discovered that α-olefins can be used in the polymerization of α-olefins in combination with organoaluminum compounds and organic carboxylic acid esters to provide highly stereoregular poly-α-olefins in significantly higher yields. We have already proposed several methods for producing solid catalyst components for olefin polymerization (Japanese Unexamined Patent Publication No. 56
-45909 Publication, 56-163102 Publication, Patent Application 1987
- Specification No. 140360). The poly-α-olefins obtained using the proposed solid catalyst component have a relatively high bulk specific gravity. For example, JP-A-1986-
According to the method described in Publication No. 45909, the bulk specific gravity is approximately
0.34 poly-α-olefin was obtained. Considering the transportation and storage of powdered poly-α-olefin produced in a polymerization reaction, a solid catalyst component that can provide poly-α-olefin having a higher bulk specific gravity is desired. It is an object of the present invention to maintain the excellent polymerization activity of the proposed solid catalyst component and to
An object of the present invention is to provide a method for producing a solid catalyst component that provides α-olefin. The above object of the present invention is to (1) convert aluminum halide into a (wherein, X ¹ represents a hydrogen atom or a halogen atom) and a compound represented by the formula (X ² R ¹ ) _n Si (OR ² X ³ ) _4-n (wherein, R ¹ and R ² are Each represents an alkylene group or a phenylene group having 1 to 8 carbon atoms, X ² and X ³ each represent a hydrogen atom or a halogen atom, and m is 1, 2 or 3. However, X ² and X ³ are both halogen atoms, X ² and X ³ are both hydrogen atoms, and R ² is an alkylene group.) is reacted with a silicon compound selected from the group consisting of compounds represented by ( 2) Reacting the reaction product with a Grignard compound represented by the formula R ³ MgX ⁴ (wherein R ³ represents an alkyl group having 1 to 8 carbon atoms and X ⁴ represents a halogen atom), (3) The resulting support is treated with (a) a titanium tetrahalide and then an aromatic carboxylic acid ester, or (b) a titanium tetrahalide and an aromatic carboxylic acid ester, and (4) the treated solid is treated with a titanium tetrahalide and an aromatic carboxylic acid ester. This is achieved by contacting with titanium halides. By combining the solid catalyst component obtained in the present invention with an organoaluminum compound and using it in the polymerization of α-olefin, poly-α-olefin having a large bulk specific gravity can be obtained in a significantly high yield.
Therefore, it is possible to omit the operation of removing catalyst residues from the produced poly-α-olefin, and furthermore, the produced poly-olefin can be efficiently transported and stored. FIG. 1 shows a method for producing a solid catalyst component for α-olefin polymerization according to the present invention and a process for polymerizing α-olefin using this solid catalyst component. 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 include tetraphenoxysilane, tetrakis(chlorophenoxy)silane, tris(chlorophenoxy)methylsilane, tris(bromophenoxy)methylsilane,
Tris(chlorophenoxy)ethylsilane, tris(bromophenoxy)ethylsilane, tris(iodophenoxy)ethylsilane, tris(chloroethoxy)methylsilane, tris(chlorophenoxy)phenylsilane, tris(bromophenoxy)phenylsilane, bis(chlorophenoxy)dimethylsilane, Bis(bromophenoxy)
Dimethylsilane, bis(chlorophenoxy)diethylsilane, bis(bromophenoxy)diethylsilane, chlorophenoxytrimethylsilane, bromophenoxytrimethylsilane, iodophenoxytrimethylsilane, chlorophenoxytriethylsilane, bromophenoxytriethyl Silane, chlorophenoxytriphenylsilane, bromophenoxytriphenylsilane, chlorophenoxytrioctylsilane, chloroethyltrimethoxysilane, bromoethyltrimethoxysilane,
Iodoethyltrimethoxysilane, chloroethyltriethoxysilane, bromoethyltriethoxysilane, chloromethyltripropoxysilane, chloromethyltributoxysilane, chloromethyltriphenoxysilane, bis(chloromethyl)diethoxysilane, bis(chloromethyl) ) diethoxysilane, bis(chloromethyl)diphenoxysilane, bis(bromomethyl)diphenoxysilane,
Examples include tris(chloromethyl)methoxysilane, tris(chloromethyl)ethoxysilane, tris(chloromethyl)phenoxysilane, and the like. 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 solution in an inert organic solvent. The reaction product is subjected to reaction with the Grignard compound as a solution in an inert organic solvent. Among Grignard compounds, alkylmagnesium chlorides in which X ⁴ is a chlorine atom are preferably used, and specific examples include methylmagnesium chloride, ethylmagnesium chloride,
Examples include n-butylmagnesium chloride and n-hexylmagnesium chloride. 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 mixed solvent solution 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. The above ether has the formula R ⁴ --O--R ⁵ (wherein R ⁴ and R ⁵ represent an alkyl group having 2 to 8 carbon atoms). Compounds represented by are preferably used, and specific examples thereof include diethyl ether, diisopropyl ether, di-n-butyl ether, diisoamyl ether, and the like. 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, 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 method (a) or (b) below. (a) contacting the support 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; The support is separated from the reaction mixture, optionally washed with an inert organic solvent, and then the titanium-contacted solid is heated at 20-200°C, preferably at 60-140°C, in the presence or absence of an inert organic solvent. A method of treatment with an aromatic carboxylic acid ester at a temperature of 0.5 to 3 hours. (b) The support is heated at 20-200°C, preferably at 60°C, with titanium tetrahalide and aromatic carboxylic acid ester in the presence or absence of an inert organic solvent.
A method of processing at a temperature of ~140°C for 0.5 to 3 hours. 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 preferably 1 mol or more, particularly 2 to 100 mol, per 1 mol of the Grignard compound used in preparing the carrier. As an aromatic carboxylic acid ester, the formula [In the formula, R ⁶ represents an alkyl group having 1 to 6 carbon atoms, and Y represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or -OR ⁷ (R ⁷ represents an alkyl group having 1 to 4 carbon atoms). ) is shown. 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 amount of aromatic carboxylic acid ester used is preferably 5 to 30% by weight, particularly 15 to 25% by weight, based on the carrier. The treated solid thus obtained is separated from the treatment mixture and optionally washed with an inert organic solvent. The treated solid is then contacted again with titanium tetrahalide. The amount of titanium tetrahalide used, contact temperature and contact time are the same as those in preparing the treated solid. The solid catalyst component is separated from the mixture by filtration, decanting, etc., and washed with an inert organic solvent. The titanium content of the solid catalyst component is 0.5 to 5% by weight. The solid catalyst component obtained in the present invention is used as a polymerization catalyst for α-olefin in combination with trialkylaluminium and optionally an electron donor. A specific example of trialkyl aluminum is
Examples include triethylaluminum, triisobutylaluminum, trihexylaluminum, and the like. The amount of trialkylaluminum used is 1 to 1 per gram atom of titanium in the solid catalyst component.
It is 1000 moles. Specific examples of α-olefin include ethylene,
Examples include propylene, butene-1,4-methyl-pentene-1, hexene-1, and the like. These α-olefins may be used alone or in combination for polymerization. When an α-olefin having 3 or more carbon atoms is polymerized, it is desirable to use an electron donor in combination in order to improve the stereoregularity of the resulting polymer. As the electron donor, aromatic carboxylic acid esters, phenyl carbinols, pyridine carboxylic acid esters, cinnamate esters, etc. are used. Among these, aromatic carboxylic acid esters used in preparing the treated solid are preferably used. The amount of electron donor used is preferably 0.05 to 0.6 mol per mol of trialkylaluminum. The polymerization reaction can be carried out in the same manner as the polymerization reaction of α-olefin 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, it is 0.001 to 1 milligram atom per polymerization solvent for solid catalyst components, and 0.01 to 1 milligram atom for organoaluminum compounds in terms of titanium metal.
100 mmol. Inert organic solvents used in the preparation of the solid catalyst component and in some cases during the polymerization reaction include aliphatic hydrocarbons such as hexane and heptane, toluene,
Examples include aromatic hydrocarbons such as 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 poly-α-olefin can be easily adjusted by adding hydrogen to the polymerization system. Next, Examples and polymerization examples will be shown. In the following description, "polymerization activity" refers to the polymer yield (g) per 1 hour of polymerization time per 1 g of solid catalyst component used in the polymerization reaction, and "HI" refers to the polymer yield (g) per 1 hour of polymerization time. This 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 15 mmol of anhydrous aluminum chloride was added to 40 mmol of toluene.
ml, then 15 mmol of chloromethyltriethoxysilane was added, and the mixture was reacted for 0.5 hour at 25°C with stirring, and then heated to 60°C and further reacted for 1 hour. After cooling the reaction mixture to -5°C, n-butylmagnesium chloride was added under stirring.
18 ml of diisoamyl ether containing 27 mmol
It was added dropwise into the reaction product mixture in 0.5 hours. The temperature of the reaction system was maintained at -5°C. After the dropwise addition was completed, the temperature was raised to 30°C and the reaction was continued for 1 hour. The precipitated carrier was separated and washed with toluene. 4.8 g of the obtained carrier was suspended in 25 ml of toluene, 150 mmol of titanium tetrachloride was added to this suspension, the temperature was raised to 90°C, and the carrier and titanium tetrachloride were brought into contact for 1 hour with stirring. I let it happen. At the same temperature, separate the contact solid, n-heptane,
It was then washed with toluene. 4.0 g of the contact solid was suspended in 25 ml of toluene, 6.5 mmol of ethyl benzoate was added to this suspension, and the mixture was heated to 90°C for 1 hour with stirring.
It kept time. The treated solids were separated at 90°C and washed with n-heptane and then toluene. The treated solid was suspended in 25 ml of toluene, 150 mmol of titanium tetrachloride was added to this suspension, 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-heptane. 3.1g of the solid catalyst component thus obtained
was suspended in 80 ml of n-heptane. The titanium content of the solid catalyst component was 2.6% by weight. Examples 2-4 Example 1 was repeated, except that instead of chloromethyltriethoxysilane, the silicon compounds listed in Table 1 were used. Table 1 shows the titanium content of the solid catalyst components. Polymerization Examples 1 to 4 A suspension of the solid catalyst component prepared in each example (an n-heptane solution containing 10.4 mg as the solid catalyst component) was placed in a 2-inner volume autoclave equipped with a stirrer.
After attaching a glass ampoule containing 0.5ml), the air in the autoclave was replaced with nitrogen.
5.8 ml of n-heptane solution containing 0.14 mmol of methyl P-tolylate, followed by triethylaluminum.
1.5 ml of n-heptane solution containing 0.56 mmol was charged to the autoclave. liquid propylene 1200ml
was introduced into the autoclave, and the autoclave was shaken. After heating the contents of the autoclave to 65°C, stirring was started, the glass ampoule was crushed, and propylene was polymerized at 65°C for 1 hour. After the polymerization reaction is complete, unreacted propylene is released, glass fragments are removed, and the resulting polypropylene is heated at 50℃.
It was dried under reduced pressure for 20 hours. A white powdered polypropylene was obtained. Polymerization activity, HI and bulk specific gravity are shown in Table 1.

Table: Polymerization Examples 5 and 6 Polymerization Example 1 was repeated except that prior to introducing liquid propylene, hydrogen was introduced into the autoclave to the pressure (gauge pressure) listed in Table 2. The results are shown in Table 2.

[Table] Example 5 Using titanium tetrachloride as a carrier as a method for preparing treated solids
Example 1 was repeated, except that a treatment with 150 mmol and 6.5 mmol of benzoic acid at 90° C. for 1 hour was employed. The titanium content of the obtained solid catalyst component was 2.1% by weight. Polymerization Example 7 Polymerization Example 1 was repeated except that 12.9 mg of the solid catalyst component obtained in Example 5 was used. Polymerization activity is 14100, HI is 94.7%, bulk specific gravity is 0.38
It was hot.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing a method for producing a solid catalyst component for α-olefin polymerization according to the present invention.

Claims (1)

[Claims] 1 Aluminum halide with the formula (In the formula, X ¹ represents a hydrogen atom or ^a halogen atom.) Compounds represented by the formula ( ^{X 2 R 1} ) _{n Si} ( ^{OR 2} Each has 1 carbon number
~8 alkylene group or phenylene group,
X ² and X ³ each represent a hydrogen atom or a halogen atom, and m is 1, 2 or 3. However, when X ² and X ³ are both halogen atoms, and when X ² and X ³ are both hydrogen atoms,
Except when R ² is an alkylene group. ) is reacted with a silicon compound selected from the group consisting of compounds represented by the formula R ³ MgX ⁴ (wherein, R ³ represents an alkyl group having 1 to 8 carbon atoms, and X ⁴ is a halogen atom). ), and the resulting support is treated with (a) titanium tetrahalide and then an aromatic carboxylic acid ester, or (b) titanium tetrahalide and an aromatic carboxylic acid ester. 4. A method for producing a solid catalyst component for α-olefin polymerization, characterized by contacting the treated solid with titanium tetrahalide.