JPH0429686B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing poly-α-olefin, and more specifically, the present invention relates to a method for producing poly-α-olefin, in which α-olefin is polymerized using a specific activated titanium catalyst component and a catalyst containing an organoaluminum compound as a main component. The present invention relates to a method for obtaining highly active poly-α-olefin having stereoregularity, good particle size distribution, and high bulk density. Conventionally, various methods have been proposed for producing polyα-olefins with high stereoregularity from α-olefins using catalysts consisting of solid catalyst components containing magnesium and titanium and organoaluminum compounds. Publication No. 56-74103, Japanese Patent Application Publication No. 56-99207, Publication No. 115301-1980,
There are methods disclosed in JP-A-56-120711, JP-A-56-166205, JP-A-57-63308, and the like. However, in any of these methods, in order to produce polyα-olefin with high stereoregularity, it is necessary to consume a large amount of titanium compound in preparing the catalyst used.
For this reason, large amounts of expensive titanium compounds are used, and preparations for processing the titanium compounds discharged during catalyst preparation or olefin polymerization are essential, which increases the production cost of polyolefins and increases industrial production. Various problems arose. Therefore, the present inventors solved the above-mentioned problems of the conventional method and used a catalyst that consumes less titanium compounds in the preparation stage, thereby achieving sufficient titanium compounds in terms of stereoregularity, particle size distribution, and bulk density. Satisfactory poly α-
We conducted extensive research to develop a method to efficiently produce olefin. As a result, the objective can be achieved by using a solid product obtained by reacting a magnesium compound and a titanium compound under specific conditions with thionyl chloride as a component of the polymerization catalyst. I found out. The present invention was completed based on this knowledge. That is, the present invention provides α
- In a method for producing a polyα-olefin having stereoregularity by polymerizing an olefin, the general formula
Mg(OR ¹ ) _o X ¹ _2-o [In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, n is a real number from 0 to 2,
X ¹ represents a halogen atom. ] in the presence of an electron-donating compound,
Poly α-, characterized in that a solid product obtained by reacting with titanium tetrahalide and then treating with thionyl chloride is used as the component (A) of the above catalyst.
A method for producing olefin is provided. The magnesium compound used in the present invention has the general formula
It is expressed as Mg(OR ¹ ) _o X ¹ _2-o . here
R ¹ represents a linear or side chain alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.
In addition, X ¹ represents a halogen atom such as chlorine or bromine,
Further, n represents a real number between 0 and 2.0. Specifically, these magnesium compounds include magnesium dimethoxide, magnesium diethoxide,
Examples include magnesium dialkoxides such as magnesium dipropoxide and magnesium dibutoxide, and magnesium monohalogenated monoalkoxides such as magnesium monochloromonomethoxide, magnesium monochloromonoethoxide, and magnesium monochloromonopropoxide. In the present invention, the above magnesium compound is reacted with a titanium compound in the presence of an electron donating compound. The electron donating compound used here is usually an organic compound containing oxygen, nitrogen, phosphorus or sulfur. Specifically, examples include amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, organic acids, etc. . More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and p-toluic anhydride; acetone, methyl ethyl ketone, Methyl isobutyl ketone, acetophenone,
3 or more carbon atoms such as benzophenone and benzoquinone
15 ketones; aldehydes with 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate,
Octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, Ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, anis C2-18 esters such as ethyl acid, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether,
Ethers with 2 to 20 carbon atoms such as tetrahydrofuran, anisole, diphenyl ether, and ethylene glycol butyl ether; Acid amides such as acetic acid amide, benzoic acid amide, and toluic acid amide; Tributylamine, N,N'-dimethylpiperazine, and Examples include amines such as livenzylamine, aniline, pyridine, picoline, and tetramethylethylenediamine; nitrites such as acetonitrile, benzonitrile, and trinitrile; tetramethylurea, nitrobenzene, and lithium butyrate. Among these, esters; ethers, ketones, acid anhydrides, etc. are preferred. In particular, alkyl esters of aromatic carboxylic acids having 1 to 4 carbon atoms such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, and toluic acid are preferred, and alkyl esters of aromatic carboxylic acids such as benzoquinone are particularly preferred. Also preferred are aromatic ketones, aromatic carboxylic acid anhydrides such as benzoic anhydride, and ethers such as ethylene glycol butyl ether. Furthermore, in the present invention, titanium tetrahalide is used as the titanium compound. Here, titanium tetrahalide is represented by the general formula TiX ² ₄ . In the formula, X ² represents a halogen atom such as a chlorine atom, a bromine atom, or an iodine atom. Specific examples of these include TiCl ₄ , TiBr ₄ , TiI ₄ , etc.
In particular, it is preferable to use titanium tetrachloride (TiCl ₄ ). In the method of the present invention, first, the above-mentioned magnesium compound and titanium tetrahalide are reacted in the presence of an electron-donating compound. The conditions for this reaction are not particularly limited, but usually 0.01 to 10 mol, preferably 0.05 to 5 mol, of an electron donating compound are added to 1 mol of the magnesium compound, and titanium tetrahalide is added to 1 mol of the magnesium compound. 0.1 to 20 mol, preferably 5 to 10 mol, and heated at 20 to 200°C for 0.5 to 10 hours, preferably 50 to
React at 150°C for 1 to 5 hours. According to the method of the present invention, the intended purpose can be sufficiently achieved with the amount used as described above. Furthermore, an inert hydrocarbon such as pentane, hexane, heptane, etc. can be added to this reaction system as a solvent, if necessary. The method of the invention requires a further treatment with thionyl chloride after the above reaction. In this thionyl chloride treatment, the product of the above reaction is generally washed to remove impurities with an inert solvent such as heptane, and thionyl chloride is added at a rate of 0.1 per mole of magnesium compound in the product. ~20 mol, preferably in the range of 5 to 10 mol, 20 to
0.5-10 hours at 200℃, preferably 1 at 50-150℃
Run the reaction for ~5 hours. In the method of the present invention, by performing such a treatment with thionyl chloride, the amount of the above-mentioned tetrahalogenation used can be reduced. this is,
This is believed to be because thionyl chloride causes abstraction and rearrangement of titanium atoms that do not participate in active sites, resulting in an increase in effective titanium concentration and improved activity. In the method of the present invention, the solid product obtained by the above-mentioned thionyl chloride treatment is thoroughly washed with an inert solvent such as heptane, and then the solid product is washed with a catalyst.
Component (A) (solid catalyst component). On the other hand, various types of organoaluminum compounds can be considered as component (B) of the catalyst used in the present invention, but those represented by the general formula AlR ⁴ lX ³ _3-l are usually widely used. Here R ⁴ has 1 to 10 carbon atoms
is an alkyl group, cycloalkyl group or aryl group, 1 is a real number between 1 and 3, and X ³ represents a halogen atom such as chlorine or bromine. Specifically, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminium, triisobutylaluminum, and trioctylaluminum, and dialkyl compounds such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, and dioctylaluminum monochloride. Aluminum monohalide is preferred, and mixtures thereof are also preferred. The catalyst of the present invention basically consists of the above components (A) and (B), and an electron-donating compound can be added as component (C) if necessary. This electron-donating compound is the same as that mentioned in the preparation of component (A) of the catalyst described above, and may be the exact same compound as that used in the preparation of component (A). It may be different. In the method of the present invention, α-olefin is polymerized using a catalyst comprising the above-mentioned components. The α-olefin that can be used here usually has the general formula R ³ −CH
= CH ₂ (R ³ represents hydrogen or an alkyl group or cycloalkyl group having 1 to 20 carbon atoms), such as linear chains such as ethylene, propylene, butene-1, hexene-1, octene-1, etc. Including monoolefins, 4-methyl-pentene-
Examples include branched monoolefins such as 1, etc., dienes such as butadiene, and various others, and the present invention can be effectively utilized for homopolymerization of these or copolymerization of various α-olefins. When polymerizing α-olefin, the reaction system
A dispersion of the solid product as component (A), an organoaluminum compound as component (B), and if necessary
Component (C), an electron-donating compound, is added, and then an α-olefin is introduced into the system. The polymerization method and conditions are not particularly limited, and solution polymerization, suspension polymerization, gas phase polymerization, etc. are all possible, and both continuous polymerization and discontinuous polymerization are possible. For example, in the case of solution polymerization or suspension polymerization, the amount of the catalyst component added is 0.001 to 5 mmol/l, preferably 0.001 to 5 mmol/l in terms of titanium atoms of component (A).
The amount of component (B) is 1 to 1000 (mole ratio), preferably 10 to 500 (mole ratio) to the titanium atoms in component (A). Further, when adding component (C), the amount added should be 0.01 to 100 (mole ratio), preferably 0.1 to 50 (mole ratio) relative to the titanium atoms in component (A). Further, the α-olefin pressure in the reaction system is preferably normal pressure to 50 kg/cm ² G, and the reaction temperature is 30 to 200°C, preferably 50 to 150°C. Molecular weight adjustment during polymerization can be carried out by known means, such as hydrogen. The reaction time may be appropriately selected from 10 minutes to 10 hours, preferably from 30 minutes to 5 hours. According to the method of the present invention, the activity of the catalyst used is extremely high, the stereoregularity of the obtained polyα-olefin is large, the bulk density and particle size distribution are good, and the product value is high. . Furthermore, since the amount of titanium compound consumed can be reduced during catalyst preparation, there is no need to treat waste titanium compounds, and as a result, the catalyst can be produced at a lower cost than before. Therefore, the method of the present invention enables poly-α-olefin to be obtained with high activity polymerization and high stereoregularity, and it is possible to simplify or omit the catalyst removal step and the extraction step of amorphous poly-α-olefin. In addition, from an economical point of view, very efficient polymerization can be carried out. Next, examples of the present invention will be shown. Note that all operations in the following examples were performed under an argon stream. In addition, the catalytic activity, stereoregularity coefficient (II), and total stereoregularity coefficient (total II) determined in the examples
was defined as follows. Catalyst activity: 70℃, 2 hours, propylene partial pressure 7
Weight (Kg) of total polymer produced per 1g of titanium atom during polymerization under conditions of Kg/ ^cm2 . II = Boiling of polymer insoluble in solvent during polymerization Weight of n-heptane insoluble polymer / Weight of polymer insoluble in solvent during polymerization x 100 (%) Total II = Boiling of polymer insoluble in solvent during polymerization n-heptane insoluble polymer weight/weight of total polymer produced x 10
0 (%) Example 1 (1) Preparation of solid catalyst component In a dry 500 ml separable flask, 150 ml of dehydrated n-heptane, 10 g (88 mmol) of magnesium diethoxide, and 3.14 g (17.6 g) of n-butyl benzoate were added. 83.5 g (440 mmol) of titanium tetrachloride was added thereto, heated to 40°C, and
was added dropwise, and the reaction was carried out at 110°C for 2 hours.
After washing the obtained reaction product with n-heptane at 70°C, 52.4 g (440 mmol) of thionyl chloride was added and the reaction was carried out at 85°C for 1 hour. The resulting product was then washed with n-heptane at 70°C to prepare a solid catalyst component. The amount of titanium supported on this solid catalyst component was measured by a colorimetric method and was found to be 21 mg-Ti/g-support. (2) Production of polypropylene N refined into a 1L stainless steel autoclave
- 400 ml of heptane, 2.0 mmol of triethylaluminum (TEA), 2.0 mmol of diethylaluminum monochloride, methyl p-toluate
0.75 mmol and 0.02 mmol of the solid catalyst component prepared in (1) above as titanium were added, and the temperature was raised to 70°C. Next, add 0.3Kg/hydrogen to the autoclave.
cm ² G, and then propylene was continuously introduced to make the total pressure 8.0 Kg/cm ² G, and the polymerization reaction was carried out for 2 hours. Unreacted monomers were purged to obtain 192.2 g of polypropylene. The results are shown in Table 1. Example 2 (1) Preparation of solid catalyst component In Example 1 (1), the amount of thionyl chloride used was
A solid catalyst component was prepared in the same manner as in Example 1(1) except that the amount was 31.1 g (261 mmol). The amount of titanium supported in this solid catalyst component is 20mg-Ti/g-
It was a carrier. (2) Production of polypropylene In Example 1 (2), the above solid catalyst component was
A propylene polymerization reaction was carried out in the same manner as in Example 1 (2) except that the solid catalyst component prepared in (1) was used to obtain 143.0 g of polypropylene. Results first
Shown in the table. Example 3 (1) Preparation of solid catalyst component In Example 1 (1), ethyl benzoate was used instead of n-butyl benzoate as the electron donating compound.
A solid catalyst component was prepared in the same manner as in Example 1(1) except that 2.7 g (17.6 mmol) was used. The amount of titanium supported in this solid catalyst component is 25mg-Ti/g-
It was a carrier. (2) Production of polypropylene In Example 1 (2), the above solid catalyst component was
A propylene polymerization reaction was carried out in the same manner as in Example 1 (2) except that the solid catalyst component prepared in (1) was used to obtain 135.0 g of polypropylene. Results first
Shown in the table. Comparative Example 1 (1) Preparation of Solid Catalyst Component A solid catalyst component was prepared in the same manner as in Example 1(1) except that the treatment with thionyl chloride was not performed. The amount of titanium supported on this solid catalyst component was 51 mg-Ti/g-support. (2) Production of polypropylene In Example 1 (2), the above solid catalyst component was
A propylene polymerization reaction was carried out in the same manner as in Example 1 (2) except that the solid catalyst component prepared in (1) was used to obtain 67.3 g of polypropylene. The results are shown in Table 1. Comparative Example 2 (1) Preparation of solid catalyst component A solid catalyst component was prepared in the same manner as in Example 3(1) except that the treatment with thionyl chloride was not performed in Example 3(1). The amount of titanium supported on this solid catalyst component was 40 mg-Ti/g-support. (2) Production of polypropylene In Example 1 (2), the above (1) was used as the solid catalyst component.
Example 1 except that the solid catalyst component prepared in Example 1 was used.
A propylene polymerization reaction was carried out in the same manner as in (2) to obtain 82.4 g of polypropylene. The results are shown in Table 1. 【table】

[Brief explanation of drawings]

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

Claims (1)

[Claims] 1. α-olefin is polymerized using (A) a reaction product of a magnesium compound and titanium tetrahalide and (B) a catalyst containing an organoaluminum compound as a main component, and has stereoregularity. In the method for producing poly-α-olefin, the general formula Mg(OR ¹ ) _o X ¹ _2-o
[In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms,
n is a real number from 0 to 2, and X ¹ represents a halogen atom. ) is reacted with titanium tetrahalide in the presence of an electron-donating compound, and then treated with thionyl chloride to obtain a solid product, which is used as component (A) of the above catalyst. Characteristic method for producing polyα-olefin. 2. The method according to claim 1, wherein the electron donating compound is an aromatic carboxylic acid ester. 3 α-olefin has the general formula R ³ −CH=CH ₂
2. The method according to claim 1, which is a compound represented by the following formula: (wherein ^R3 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group).