JPS6142516A - Production of ethylene copolymer - Google Patents

Abstract

PURPOSE:To obtain a particulate ethylene copolymer which can be easily handled in good efficiency, by copolymerizing ethylene with an (alpha-substituted) acrylate ester in the presence of a Lewis acid and hydrogen by using a specified catalyst. CONSTITUTION:Ethylene is copolymerized with an acrylate and/or an alpha-substituted acrylate ester in the presence of a Lewis acid and hydrogen by using a catalyst which comprises (A) a transition metal compound of the formula (wherein M<1> is V, Ti, Zr or Hf, R<1> is a 1-20C alkyl or the like, X<1> is a halogen, Y is O or the like and i, m and n are each 0-5), (B) a reaction product obtained by a reaction among (a) an organometallic compound in which the metal is an element of Groups I -III in the periodic table, (b) a carboxylic acid or the like, (c) an electron-donating compound, (d) a Lewis acid compound containing an element of Group II-V in the periodic table, and (e) a compound of a metal of Group I b or the like in the periodic table and (C) an organometallic compound in which the metal is an element of Groups I -III in the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer, and more specifically, the present invention relates to a method for producing an ethylene copolymer, and more particularly, the present invention relates to a method for producing an ethylene copolymer, in which ethylene and an acrylic ester and/or an α-substituted acrylic ester are mixed in the presence of hydrogen using a Lewis acid and a specific catalyst component. This invention relates to a highly efficient method for producing easily-handled granular ethylene copolymers by copolymerizing them with

Traditionally, polyethylene is water and chemical resistant.

It has excellent electrical properties and is used for various purposes. However, because it is chemically inert, it has poor adhesion, printability, and dyeability, which limits its use in applications that require these properties. Furthermore, in order to improve these properties, it is known that ethylene is modified by copolymerizing ethylene with an unsaturated compound copolymerizable with ethylene. For example, Japanese Patent Publication No. 49-23317 proposes a method of copolymerizing ethylene with an acrylic ester or the like in the presence of a Lewis acid compound. However, this method has the disadvantage that the copolymerization activity is low and the composition cannot be controlled arbitrarily. Also, Japanese Patent Publication No. 48-37755 and Japanese Patent Application Publication No. 59-430
The method described in Publication No. 03 has a problem in that the content of acrylic esters and the like in the resulting copolymer is very low. Furthermore, in copolymerization by these conventional methods, there is a problem that the produced copolymer forms a film or a lump, and adheres to the walls of the reactor and the stirrer. As described above, a fully satisfactory method for producing an ethylene copolymer has not yet been proposed.

Therefore, the present inventors have conducted extensive research in order to develop an extremely efficient method for producing an ethylene copolymer that solves the above problems. As a result, they found that the above object can be achieved by carrying out the copolymerization reaction of ethylene using a Lewis acid and a specific metal-containing compound in the presence of hydrogen, and based on this knowledge, they completed the present invention.

That is, the present invention copolymerizes ethylene and an acrylic ester and/or an α-substituted acrylic ester using a catalyst in the presence of a Lewis acid to produce an ethylene copolymer. M'(OR
凰), X', Y, (wherein Ml is vanadium, titanium, zirconium or hafnium, and R' is an alkyl group having 1 to 20 carbon atoms.

cycloalkyl group, aryl group or aralkyl group,
XI represents a halogen atom, Y represents a cylindrical atom, a cyclopentagenyl group or an acetylacetonate group, l,
m and n each represent a real number from θ to 5. ] and CB) (a) an organic metal-containing compound of Groups I to III of the periodic table.

(b) Each metal salt of carboxylic acid, alcohol, and/or organic phosphoric acid, (c) Electron-donating compound, (d
) Lewis acid compounds of groups II to V of the periodic table.

and (e) a reaction product obtained by reacting at least one compound selected from metal compounds of group 1b or group 1 of the periodic table, and [C) metal compounds of groups I to II of the periodic table.
The present invention provides a method for producing an ethylene copolymer, characterized in that a Group I organometallic compound is used and the copolymerization is carried out in the presence of hydrogen.

The catalyst used in the method of the present invention consists of a reaction product of [A] and (B), and component (c). here〔
A] The component has the general formula Ml(OR1)iXlmY,... (I
) is a transition metal compound represented by In the general formula (1), Ml represents vanadium, titanium, zirconium or hafnium. Also, R1 has 1 to 20 carbon atoms.
, preferably 1 to 10 alkyl groups.

Cycloalkyl! N represents an aryl group or an aralkyl group. Specific examples of R1 include a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, an octyl group, and a 2-ethylhexyl group.

Examples include cyclopentyl group, cyclohexyl group, phenyl group, and benzyl group. Xl is a halogen atom, ie, chlorine, bromine, iodine, etc., and chlorine is particularly preferred. Y represents an oxygen atom, a cyclopentagenyl group or an acetylacetonate group. Furthermore, l, m, and n are each real numbers of 0 to 5.

The transition metal compound represented by the above general formula (1) is M
Vanadium compounds depending on the metal indicated by l.

It becomes a titanium compound, a zirconium compound, or a hafnium compound. Among these, specific examples of vanadium compounds include vanadium chloride iV such as VCla and VCh.
OCl3. Vanadium oxychloride such as VOCh:
V(0-n-CJw)4+VO(OCJs):++ V
Vanadium alkoxides such as O(0·n-C4,llJ,
Mention may be made of vanadium acetylacetonate compounds such as ac)3+ VO(acac)z. In addition,
Here, acac represents an acetylacetonate group, that is, an acetylacetone ion.

Next, the titanium compound is specifically TiC1.

TfBr4. Tetrahalogenated titanium such as TiIn; Ti(OClh)CI+, Ti(OCzlls)C
1s, Ti(0·n-C411q)C1z.

T! (OCJs) Trihalogenated monoalkoxytitanium such as Br3 1Ti(OClh)zClz,T
i(OCzHs)zclz+Ti(0' n -C41
19) Dihalogenated dialkoxytitanium such as 2CIZI Ti(OCzHs)zBrz; Ti(OCHa
)zCl.

Ti(OCJs)iCl, Ti((l n-C4
Monohalogenated trialkoxytitanium such as 11J3C1, Ti(OCJs) Jr;
)<, Ti(OCzlls)t, Ti(OCJt)4°Ti(0·n-C4HJ4) and other tetraalkoxytitaniums and dicyclopentadienyltitanium dichlorides.

Mention may be made of cyclopentagenyl titanium derivatives such as dimethyldicyclopentagenyl titanium.

Further, as specific examples of the zirconium compound, as well as the above titanium compound, zirconium tetrahalide;
Examples include trihalogenated monoalkoxyzirconium; dihalogenated dialkoxyzirconium; monohalogenated trialkoxyzirconium; tetraalkoxyzirconium; Genyl zirconium derivatives can be mentioned as suitable ones.

Further, specific examples of hafnium compounds include tetrahalogenated hafnium; trihalogenated monoalkoxyhafnium; dihalogenated sialkoni-1-cyhafnium; monohalogenated trialkoxyhafnium; tetraalkoxyhafnium, dicyclopentadienyl hafnium dichloride, dimethyldicyclo Examples include cyclopentagenyl hafnium derivatives such as pentagenyl titanium.

The transition metal compound that is component [A] of the catalyst used in the method of the present invention is the vanadium compound described above.

One or more compounds selected from titanium compounds, zirconium compounds, and hafnium compounds may be used, and vanadium compounds are particularly preferred.

Next, the (B) component to be reacted with the above [A] component is (a)
, (b), (c), (d) and (e). Here, the compound (a) is an organic metal-containing compound of Groups I to III of the periodic table, and among them, a compound represented by the general formula R"qM"X"p-11... (II) is preferable. R2 in this general formula (II) represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms. Specific examples of R2 include a methyl group and an ethyl group.

Examples include propyl group, butyl group, hexyl group, and the like.

Further, M a represents linawa, sodium, potassium, zinc, cadmium, aluminum, boron, or gallium. Furthermore, X2 represents a halogen atom, ie, chlorine, bromine, iodine, etc. p is the valence of M2 and is usually 1.2 or 3. q is a real number satisfying Q<q≦p and indicates various values.

Specific examples of this (a) compound include methyllithium,
Examples include alkyllithiums such as ethyllithium, propyllithium, butyllithium, dialkylzincs such as dimethylzinc, diethylzinc, dipropylzinc, and dibutylzinc, and alkylgallium compounds such as trimethylgallium, triethylgallium, tripropylgallium, and tributylgallium. . Furthermore, there are various examples of compounds where ylg is aluminum, specifically trimethylaluminum, triethylaluminum, and triisopropylaluminium.

Trialkylaluminum compounds such as triisobutylaluminum and trioctylaluminum, and dialkylaluminum monochloride such as diethylaluminum monochloride, diethylaluminum monopromide, diethylaluminium monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride, etc. Preferred are halides or alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquipromidoride, and mixtures thereof. Furthermore, alkyl group-containing aluminoxane produced by the reaction of alkyl aluminum and water can also be used.

Compound (b) is a metal salt of at least one compound selected from the group consisting of carboxylic acids, alcohols, and organic phosphoric acids. The carboxylic acid constituting this metal salt may be either saturated or unsaturated, and preferably has 1 or more carbon atoms, particularly 8 or more carbon atoms. Specifically, for example, capric acid.

Higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid are preferably used. In the present invention, metal salts of these carboxylic acids, particularly magnesium salts. Calcium salt.

Manganese salt is preferably used. The alcohol constituting the alcohol metal salt is not particularly limited and may be any of aliphatic alcohols, alicyclic alcohols, and aromatic alcohols, but aliphatic alcohols are preferably used. Furthermore, in this case, it may be either saturated or unsaturated, and those having 1 or more carbon atoms, especially 8 or more carbon atoms, are preferable. Specifically, for example, decanol, lauryl alcohol, myristyl alcohol. Higher alcohols such as cetyl alcohol and stearyl alcohol are preferably used. In the present invention, metal salts of these alcohols, particularly magnesium salts and calcium salts. Manganese salts are preferably used.

Furthermore, the phosphoric acid constituting the metal salt of organic phosphoric acid may be phosphorous acid, and mono- or dialkyl esters of phosphoric acid or phosphorous acid (R'OIIIzOs, (R'O)
zPHOi, R'OPIhO□nato) and mono- or dialkyl (R'PII□0,).

Examples include R'zPH (h.R'Plh (h, etc.).
Kokote RS indicates an alkyl group. The phosphoric acid preferably has an aliphatic hydrocarbon group, particularly an aliphatic hydrocarbon group having 1 or more carbon atoms, more preferably 8 or more carbon atoms. Here, the aliphatic hydrocarbon group may be either a saturated or unsaturated group. Specific examples of these include hexyl group, heptyl group, octyl group, 2-ethyl-hexyl group, and nonyl group. Examples include decyl group, lauryl group, myristyl group, heptadecyl group, stearyl group, and octadecenyl group. In the present invention, metal salts of these phosphoric acids, especially magnesium salts are used.

Calcium salts and manganese salts are preferably used.

These (b) compounds are carboxylic acids, alcohols, or metal salts of Wamilin, specifically magnesium salts,
Calcium salts, manganese salts, etc. can be obtained by various methods, and commercially available products may be dried and used as they are. The above magnesium salt is a combination of carboxylic acid, alcohol, or phosphoric acid and butylethylmagnesium,
It can be easily produced from alkylmagnesiums such as dibutylmagnesium. Furthermore, the above-mentioned magnesium salt. Calcium salts, manganese salts, etc. (i.e.
The carboxylates, alcohol salts, or organic phosphates of magnesium, calcium, manganese, etc.) may form double salts with other metals.

Next, the electron-donating compound (c) in component (B) is an organic compound or olefin containing oxygen, nitrogen, phosphorus or sulfur.

Specifically, organic compounds such as amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, etc. can give. .

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 and methyl ethyl ketone.

Ketones having 3 to 15 carbon atoms such as methyl isobutyl ketone, acetophenone, benzophenone, and benzoquinone;
Acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde.

2-1 carbon atoms such as tolualdehyde and nathaldehyde
5 aldehydes; methyl formate, methyl acetate.

Ethyl acetate, vinyl acetate, propyl acetate, octyl acetate/
lz, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, benzoin Methyl acid, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, anisic acid Carbon number of methyl, dithyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate, ethyl naphthoate, r-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. 2 to 18 esters; acetyl chloride, benzyl chloride, toluic acid chloride,
Acid halides having 2 to 15 carbon atoms, such as anisyl chloride; Ethers; Acetamide, Benzoic acid amide,
Acid amides such as toluic acid amide; triethylamine, tributylamine, N,N'-dimethylpiperazine,
tribenzylamine, aniline, pyridine, picoline.

Amines such as tetramethylethylenediamine; Nitriles such as acetonitrile, benzonitrile, tolnitrile; Tetramethylurea, nitrobetones, amines,
These include acid anhydrides. Particularly preferred are alkyl esters of aromatic carboxylic acids, such as 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; aromatic ketone, ammonium anhydride
- Aromatic carboxylic acid anhydrides such as zoic acid, tetrahydrofuran, dioxane, ethers such as ethylene glycol butyl ether, etc. are also preferred.

Examples of the olefin include monoolefins and diolefins having 1 to 20 carbon atoms such as ethylene, propylene, butene, phytadiene, hexene, and octene, and styrene (mH).

Furthermore, the Lewis acid compounds of Groups 1 to V of the periodic table, which are compounds (d) in component (B), include aluminum, boron, zinc, tin, and magnesium.

Halogenated compounds such as antimony, eg aluminum chloride, ethylaluminum dichloride.

Diethylaluminum chloride, boron trichloride.

Zinc chloride, tin tetrachloride, alkyltin chloride.

Examples include alkyltinbromide, magnesium chloride, antimony pentachloride, and antimony trichloride. Among these, aluminum chloride and ethylaluminum dichloride are particularly preferred.

In addition, the compound (e) in the component CB) is found in the periodic table 1b.
It is a metal compound of Group 1 or Group Ⅰ. Here, a specific example of the compound (e) is chloride 111 (AgC1).

Cuprous chloride (cuC1), -'-7kel chloride (NiC1)
z), halides such as ferrous chloride (FeC1z),
Nickel diacetylacetonate, iron diacetylacetonate, tris(triphenylphosphine)nickel (
Complex compounds such as Ni (P(c,Hs)z) 3), nickel chloride permanent (NiC1□ ・1120), complex of ferrous chloride and triphenylphosphine (FeC1z
Examples include coordination complexes such as (P(c6H5)3)z) and organic salts such as nickel acetate.

The catalyst used in the method of the present invention is a reaction product of the above-mentioned component [A] and component (B).

Here, component [A] is the transition metal compound represented by the above-mentioned general formula (1), and component (B) is the above-mentioned (a).
), (b), (c).

It is one or more of the compounds (d) and (e). For this reaction between component CA) and component (B), conditions may be set as appropriate depending on the type of component [A] and component (B) used, but usually the temperature is 0 to 200°C.
, preferably at 20-80"C for 0.1 minutes to 20 hours,
Preferably, the reaction may be carried out for 1 minute to 10 hours. In addition, the usage amounts of both components are (B) component/[A] component = 0. OO1～
50 (molar ratio), preferably in the range of 0.1 to 10 (molar ratio). Furthermore, this reaction proceeds even in the absence of a solvent, but with hexane.

Preferably, the reaction is carried out in an inert catalyst such as heptane, benzene, toluene, xylene or the like.

The catalyst used in the method of the present invention comprises the above-mentioned [A] component and (B
The reaction product of component () is used as one component, and the organometallic compound of Groups 1 to 2 of the periodic table, which is component (c), is used as another component. Here, (c) component I to III of the periodic table
Although various organic metal compounds can be used, the same compounds as the compound (a), which is one of the components (B) mentioned above, are suitable. That is, the general formula (n
) are used as the component (c,), and among these, organoaluminum compounds in which the metal is aluminum are particularly preferred. Specific examples of organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminium, and triisobutylaluminum.

Trialkylaluminum compounds such as trioctylaluminum, diethylaluminum monochloride, diethylaluminum monopromide.

Dialkyl aluminum monohalides such as diethylaluminum monoiodide, diisopropylaluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride.

Alkylaluminum sesquihalides such as ethylaluminum sesquipromide and butylaluminum sesquichloride are preferred, and mixtures thereof are also preferred. Furthermore, alkyl group-containing aluminoxane produced by the reaction of alkyl aluminum and water can also be used.

In the method of the present invention, as described above, a catalyst comprising a reaction product of component [A] and component (B) and component (c) is used.

Here, the ratio of the reaction product to the component (c) is not particularly limited, but usually the metal atom in the component (c) is relative to the transition metal atom in the component [A] in the reaction product. 0.
The ratio may be 1 to 5,000, preferably 1 to 2,000 (molar ratio).

According to the method of the present invention, ethylene and an acrylic ester and/or an α-substituted acrylic ester are copolymerized in the presence of a Lewis acid using the above catalyst.

Examples of the Lewis acid include Lewis acid compounds capable of forming a chain with a lone electron pair of a polar group, such as halogenated compounds of Groups 1 to 1 or Group 2 of the periodic table. Especially halogenated compounds such as aluminum, boron, zinc, tin, magnesium, antimony, e.g. aluminum chloride,
Preferred are ethylaluminum dichloride, diethylaluminum chloride, boron trichloride, zinc chloride, tin tetrachloride, alkyltin halides, magnesium chloride, antimony pentachloride, antimony trichloride, and particularly preferred are aluminum chloride, ethylaluminum dichloride, etc. .

The acrylic ester and/or α-substituted acrylic ester to be copolymerized with ethylene is not particularly limited, but a compound represented by the general formula % (%) is usually used. In the formula, R3 is hydrogen.

Represents a halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, etc., and R4 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aral group, an aralkyl group, etc. . Specific examples of acrylic esters include methyl acrylate, ethyl acrylate, and propyl acrylate.

Examples include butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and benzyl acrylate. In addition, specific examples of α-substituted acrylic esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, methyl α-chloroacrylate, and α-chloroacrylate. Examples include ethyl.

In the present invention, what is subjected to copolymerization with Si 11 and ethylene may be either one or both of the above-mentioned acrylic ester and α-substituted acrylic ester.

The ratio of the above-mentioned acrylic ester and/or α-substituted acrylic ester to ethylene may be arbitrarily selected depending on the physical properties required of the intended copolymer.

Furthermore, the ratio of the Lewis acid and the acrylic ester and/or α-substituted acrylic ester used is 10 or less (molar ratio) of the Lewis acid, preferably 0.2 to 1 (molar ratio) to 1 of these esters. ).

Next, the method of the present invention is characterized in that hydrogen is present when copolymerizing ethylene, acrylic acid ester, etc. using the above catalyst. When hydrogen is used in the copolymerization reaction together with the above catalyst, the molecular weight of the resulting copolymer can be adjusted to a desired range, and at the same time, the shape of the resulting copolymer does not become film-like or lump-like, and the diameter is 100 to 1000 μm.
It becomes somewhat granular. Therefore, there are no problems such as adhesion to the reactor wall or clogging of pipes, and handling such as extraction and transportation of the copolymer is extremely easy.

The amount of hydrogen to be used may be 5000 or less (volume ratio), preferably 0.002 to 200 (volume ratio) to ethylene.

There are no particular restrictions on the type of polymerization, and slurry polymerization is used.

Either solution polymerization, gas phase polymerization, etc. are possible, and both continuous polymerization and discontinuous polymerization are possible.

In this case, aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons are used as the polymerization solvent. Polymerization conditions include reaction temperature of -30 to 130°C, preferably 0 to 100°C.
The reaction pressure is from normal pressure to 100 kg/cal G, preferably from normal pressure to 30 kg/cal G.

The reaction time may be appropriately selected from 1 minute to 20 hours, preferably from 1 minute to 10 hours.

In the method of the present invention, specific [A] as described above,
CB) By using a catalyst consisting of the reaction product of both components and component (c) together with a Lewis acid, it is possible to carry out copolymerization with high activity, and the conversion rate of acrylic acid ester etc. can be improved. Further, by allowing hydrogen to be present in the copolymerization reaction together with these catalysts, the shape of the obtained copolymer becomes granular with a diameter of about 100 to 1000 μm.

Therefore, conventional problems such as forming gel-like or film-like substances and adhering to reactor walls and stirring blades, or clogging pipes, valves, etc., are solved. Furthermore, since it is granular, post-processing is easy.

Therefore, the present invention is extremely efficient and dyeable.

Ethylene copolymers with excellent printability, adhesive properties, etc. can be produced.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 (1) Preparation of catalyst components After purging a 300 ml flask equipped with a dropping funnel and a stirring bar with argon, 100 mj of heptane was added to it.
! and 0.5 ml of vanadium tetrachloride at 5°C!
A hebutane solution of (4.7 mmol) and dioxane (4.7 mmol) was added dropwise over 5 minutes and stirred for 1 hour. then 2
By raising the temperature to 0℃, tri-n-butyl gallium 1.56
Millimolar hebutane solution was added dropwise over 5 minutes, and reaction was allowed to proceed for 3 hours with stirring. The supernatant liquid of the obtained pale purple solid product was extracted, and the solid product was washed with heptane.

The precipitation rate of solid product was 46 mol%.

(2) Copolymer production In an autoclave with an internal volume of 11, add 400 mj of hexane +
and 2.67 g (20 mmol) of finely ground aluminum chloride and 2.0 g (20 mmol) of ethyl acrylate.
The autoclave was heated to 50°C and stirred for 10 minutes.Hydrogen was then introduced into the autoclave at a rate of 0.5 kg/cdG, and ethylene was further introduced until the rate was 5 kg/aJG, and the total pressure was reduced to 6 kg. The solid product (vanadium-containing catalyst component) prepared in (1) above was adjusted to 0.0.
A #r mixture of 0.5 mmol and 2.5 mmol of triethylaluminum was placed in an autoclave, and ethylene was continuously supplied to maintain a total pressure of 6 kg/cJG to carry out a reaction for 1 hour.

After the reaction was completed, the interior of the autoclave was inspected and no copolymer was found to be attached to the vessel walls or stirring blades. The obtained copolymer was deashed and washed with a hydrochloric acid-methanol mixture, and then dried under reduced pressure at 80°C. The yield of the copolymer was 8.2 g, and the activity was 3.2 kg/g vanadium. The particle size distribution of the obtained copolymer particles was 10
5 to 250μ range, 5-t%, 250 to 500μ range 55.2gt%, 500 to 1000μ range 34.
3wt%, 9.0wt% of 1000μ or more, and the particle size was uniform. Further, this copolymer was extracted with acetone for 5 hours, and the extracted copolymer was dried under reduced pressure at 80° C. for 2 hours. Infrared absorption spectrum analysis (IR analysis) using a film formed from the copolymer obtained by drying revealed that there was an absorption based on carbonyl group at 1730ai-' and an absorption based on ether bond at 1160 (J-'). Absorption was observed. Furthermore, the content of ethyl acrylate determined from the absorbance ratio of methylene chains and carbonyl groups was 5.4 ht%.

Example 2 (1) Preparation of catalyst components 300mj with argon substitution! 100 mj+ of heptane was placed in a 20° C. flask, and at 20°C, 0.5 ml' (4.7 mmol) of vanadium tetrachloride and 4.7 mmol of ball-milled aluminum trichloride were added and stirred for 1 hour. gallium 1.5
A 6 mmol hebutane solution was added dropwise over 30 minutes, and the reaction was carried out for 3 hours.

The supernatant of the obtained purple solid product was removed, and the solid product was washed with heptane. The precipitation rate of solid product is 49
．． It was 3 mol%.

(2) Production of copolymer 13.9 g of a copolymer was obtained in the same manner as in Example 1 (2) except that the vanadium-containing catalyst component obtained in the above (11) was used. Catalyst Activity is 5.46kg/g
・It was vanadium. The particle size distribution of the obtained copolymer was 0.2wt% below 105μ, 5.9wt% in the range of 105 to 250μ, and 50.9wt% in the range of 250 to 500μ.
%, range 500-1000μ 42.1wt%, 1oo
The particle size was 1.0% or more, and the particle size was uniform. Furthermore, the IR analysis results and the adhesion of the copolymer to the autoclave were the same as in Example 1(2). Note that the content of ethyl acrylate in the copolymer was 2.1 wt%.

Example 3 (1) Preparation of catalyst components A 300 ml flask purged with argon was charged with 100 mff1 of heptane, and at 20°C 1.18 mmol of dioctyl phosphate and 1.1 mmol of butylethyl magnesium were added.
18 mmol was added, the temperature was raised to the boiling point of heptane, and the mixture was reacted for 3 hours. Then, the temperature was lowered to 50°C, and 1.1% of oxytriethylvanadate (VO(OCzHs) 3) was added.
The reaction product obtained by adding 8 mmol and stirring for 3 hours was soluble in hebutane and had a reddish brown color.

(2) Production of copolymer Example 1 (2 ), 6.5 g of copolymer
I got it. Catalytic activity was 6.4 kg/g.vanadium. Moreover, the particle size distribution of the obtained copolymer was 105 to 2
50μ range 0.61%, 250-500μ range 12
．． 7 tsuba t%, 500-1000μ range 69.5 t%
, 1000μ or more 1B, 2wt%, and the particle size is large (
They were all there. Furthermore, the IR analysis results and the adhesion of the copolymer to the autoclave were the same as in Example 1(2). The content of ethyl acrylate in the copolymer is 2.1 w
It was t%.

Example 4 (1) Preparation of catalyst components 300 mA with argon substitution! In a volumetric flask, add 0.90 g (7 mmol) of nickel chloride and 80 m7 of hexane.
! and vanadium oxychloride (VOCj!3) 0
．． Add 66 mjt (7 mmol) and heat at 50°C for 2 hours.
A time reaction was performed. Next, a hexane solution of 0.66 mmol of tri-n-butyl gallium was added dropwise to this at 40° C. over 10 minutes, and the reaction was carried out for 3 hours. The supernatant of the obtained solid product was extracted and washed with hexane to obtain a vanadium-containing catalyst component.

(2) Production of copolymer The process was carried out except that the vanadium-containing catalyst component obtained in (1) above was used, the amount of triethylaluminum used was 2.1 mmol, and the hydrogen pressure was 1 kg/aJG. Similarly to Example 1 (2), copolymer 16.9
I got g. Catalytic activity was 6.6 kg/g.vanadium. In addition, the particle size distribution of the obtained copolymer was 0.2 wt% below 105μ, 0.2t% in the range of 105 to 250μ,
250-500μ range 12.6wt%, 500-10
00μ range 85.9wt%, 1000μ or more 1.1w
t%, and the particle sizes were extremely uniform. Further I
The results of R analysis and the adhesion to the autoclave are shown in Example 1.
It was the same as (2). The content of ethyl acrylate in the copolymer was 9 wt%.

Example 5 (1) Preparation of catalyst components In a 200 ml flask purged with argon, 80 ml of hexane and 0.66 ml of vanadium oxytrichloride (7
mmol), and then add a hexane solution of tri-n-butyl gallium (0.17 mmol/mβ) 3
．． 9mj! was added dropwise over 30 minutes. Next, 20℃
The reaction was carried out for 3 hours, and the produced solid catalyst component was washed with hexane to obtain a vanadium-containing catalyst component.

(2) Production of copolymer In the same manner as in Example 1 (2) except that the vanadium-containing catalyst component obtained in (1) above was used,
8.2 g of copolymer was obtained. Catalytic activity is 3.2kg/g・
It was vanadium. In addition, the particle size distribution of the obtained copolymer was in the range of 105 to 250μ, 2 & 4t%, and 250 to 500μ.
μ range 54wt%, 5oo~1000μ range 35w
t%, 1000μ or more was 9wt%. The content of ethyl acrylate in this copolymer was 9 wt%. I
The R analysis results and the adhesion of the copolymer to the autoclave were the same as in Example 1(2).

Comparative Example 1 The same procedure as in Example 1 (2) was carried out except that hydrogen was not introduced in Example 1 (2). When the autoclave was opened after the reaction was completed, significant adhesion of the copolymer to the vessel walls and stirring blades was observed. The obtained copolymer was a mixture of lumps and films, the yield was 10.4 g, and the weight activity was 4.08 kg/g.vanadium. The content of acrylic ester in the copolymer was 5.3 wt%.

Comparative Example 2 The same procedure as in Example 3 (2) was carried out except that hydrogen was not introduced in Example 3 (2). In this case as well, similar to Comparative Example 1, significant adhesion of the copolymer was observed on the inner wall of the autoclave and the stirring blade. The obtained copolymer was a mixture of lumps and films, the yield was 12.1 g, and the catalytic activity was 11.9 kg/g.vanadium. The content of acrylic ester in the copolymer was 2.0 wt%.

Claims (4)

[Claims] (1) Ethylene and acrylic ester and/or α
- In producing an ethylene copolymer by copolymerizing a substituted acrylic ester using a catalyst in the presence of a Lewis acid, [A] general formula M^1 (OR^1)_1X^ is used as a catalyst.
1_mY_n [wherein M^1 is vanadium, titanium, zirconium or hafnium, R^1 is carbon number 1-2
0 alkyl group, cycloalkyl group, aryl group or aralkyl group, X^1 is a halogen atom, Y is an oxygen atom, a cyclopentadienyl group or an acetylacetonate group, 1, m and n are each 0-5 indicates the real number of ] and [B] (a) an organic metal-containing compound of Groups I to III of the periodic table, (b) each metal salt of carboxylic acid, alcohol, and/or organic phosphoric acid, (c) Electron-donating compounds, (d) Periodic Table II to V
and (e) a reaction product obtained by reacting at least one compound selected from metal compounds of Group Ib or Group VIII of the Periodic Table; A method for producing an ethylene copolymer, which comprises using an organometallic compound of groups I to III and carrying out copolymerization in the presence of hydrogen. (2) [A] The production method according to claim 1, wherein the transition metal compound is a vanadium compound. (3) [B] (a) The organometallic compound of Groups I to III of the periodic table has the general formula R^2_qM^2X^2_p_-_
q [In the formula, R^2 is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, M^
2 is lithium, sodium, potassium, zinc, cadmium, aluminum, boron or gallium, X^2 is a halogen atom, p is the valence of X^2, and q is 0<q
Indicates a real number that satisfies ≦p. ] The manufacturing method according to claim 1, which is a compound represented by: (4) Acrylic esters and/or α-substituted acrylic esters have the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^3 is a hydrogen atom, a halogen atom, or a carbon number of 1 to
20 alkyl group, cycloalkyl group, aryl group, or aralkyl group; R^4 represents an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms; ] The manufacturing method according to claim 1, which is a compound represented by: