JPS60262808A - Production of ethylene copolymer - Google Patents

Abstract

PURPOSE:To produce an ethylene copolymer of a high content of an (alpha-substituted) acrylate in good efficiency at a high conversion of these esters into the copolymer, by using a specified transition metal-containing component as a catalyst component. CONSTITUTION:Ethylene is copolymerized with an acrylate and/or an alpha-substituted acrylata of the formula (wherein R' is a halogen, H, a 1-20C alkyl, cycloalkyl, aryl, or aralkyl, R<2> is a 1-20C alkyl, cycloalkyl, aryl, or aralkyl) by using a catalyst comprising (A) a transition metal-containing component and (B) an organometallic compound of a Group I -III metal in the presence of a Lewis acid compound, wherein component A comprises a reaction product among a transition metal compound (e.g., VCl or TiCl4), an electro-donating compound (e.g., benzoic acid) and an organometallic compound of a Group I -III metal (e.g., trimethylgallium). It is possible to improve the conversion of an (alpha-substituted) acrylate into a copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION 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, and in particular, a method for producing an ethylene copolymer that achieves a high conversion rate of an acrylic ester and/or α-substituted acrylic ester into a copolymer, and that The present invention relates to a method for efficiently producing an ethylene copolymer having a high content of α-substituted acrylic ester.

Generally, polyethylene is a resin with excellent properties, but because it is chemically inert, it has poor adhesion, printability, and dyeability. Therefore, in order to eliminate such drawbacks that polyethylene has.

A method of copolymerizing an unsaturated compound copolymerizable with ethylene has been considered. As such a method, for example, Japanese Patent Publication No. 49-23317 proposes a method in which ethylene and acrylic acid ester are copolymerized in the presence of a Lewis acid compound. However, in this case, the copolymerization activity is insufficient and the composition cannot be controlled arbitrarily. Also, Japanese Patent Publication No. 4B-37755 and Japanese Unexamined Patent Publication No. 59-43
The method described in Publication No. 003 has a problem in that the content of unsaturated carboxylic ester in the olefin-unsaturated carboxylic ester copolymer is low.

Furthermore, the conversion rate of the unsaturated carboxylic acid ester into a copolymer is not sufficient.

The present inventors have conducted various studies to solve the problems in the conventional methods described above, and as a result, we have developed a method in which a transition metal compound is treated with an electron-donating compound and an organometallic compound of Groups 1 to 2 of the periodic table. It is a component of the catalyst, and this and the periodic table ■
It has been discovered that the mono-copolymerization activity and the conversion rate of acrylic esters and/or α-substituted acrylic esters into copolymers can be improved by using organometallic compounds of groups ~■ in combination as catalysts, The present invention has now been completed. That is, the present invention uses (
A) a transition metal-containing component and (B) an organometallic compound of Groups 1 to [■ of the periodic table, and ethylene and the general formula % formula % in the presence of a Lewis acid compound) (in the formula, R1 is a halogen, hydrogen , represents an alkyl group having 1 to 20 carbon atoms, /chloroalkyl group, aryl group or aralkyl group, R2 is an alkyl group having 1 to 20 carbon atoms, /
Indicates a chloroalkyl group, aryl group or aralkyl group. ) In producing an ethylene copolymer by copolymerizing an acrylic ester and/or an α-substituted acrylic ester represented by (A), (a) is used as a transition metal-containing component.
) transition metal compound, (b) electron donating compound and (c
) Provides a method for producing an ethylene copolymer, which is characterized by using a reaction product of an organometallic compound of group 1-fil of the periodic table.

The catalyst component [A) in the present invention is a transition metal-containing component, and is a reaction product of C1a) a transition metal compound, (b) an electron-donating compound, and (c) an organometallic compound of Groups 1 to 2 of the periodic table. is used.

Here, (a) the transition metal compound is not particularly limited, but usually has the general formula %) [In the formula, Ml represents vanadium 2 titanium, zirconium or hafnium, and R1 is an alkyl group having 1 to 2 degrees of carbon atoms. , represents a cycloalkyl group, an aryl group or an aralkyl group, and XI represents a halogen atom. Further, Y represents oxygen, cyclopentagenyl or acetylacetonate, t, m and n are each real numbers of 0 or more and less than 5, and are 1, and the sum of these represents the valence of Ml. ], specifically the above general formula (
2] are vanadium compounds, titanium compounds, zirconium compounds, or hafnium compounds.

Here, specific examples of vanadium compounds include VCl2
, vanadium chloride A I VOC'3 such as VCl2
+ Vanadium oxychloride such as VOC72; VCO-
n-C4H9)4゜VO(OC2Hs)3, VO
Nohanadium alkoxides such as (On-CnR9)3;
Cyclopentadienylvanadium derivatives such as dicyclopentadienylvanadium chloride; V(acac)
Vanadium acylacetonate compounds such as 3 and VO(acac)a can be mentioned. Note that here, acac represents an acetylacetone group, that is, an acetylacetone ion.

Next, as a titanium compound, specifically TICt4゜Ti
Tetrahalogen/titanium oxide with Br4, Ti14;
Ti (OCH3)C13, Ti (OC21-1s
)Cl3,Ti (0-n-C4tb+)C4゜T
i(OC2Hs)Br3nato trihalogenated monoalcoquine titanium; Ti(OCH3)2 C12,T
i (OC2Hs)2C12.

Ti(()n-C<R9)2012, Ti(OC
Dihalogenated dialkoxytitanium such as 2H5)2Br2: Ti(OCH3)3C1.

Ti (OC2H5)3 C1,'ri (On-C4
Hs) 3ct.

Monohalogenated trialkoxotitane such as Ti(OC2Hs)3Br; and also Ti(OCH3)4
, Ti(OC2H5)4.

'ri(OC+H7)4. Ti (○・n-C4Hs)
Examples include tetraalkoxytitaniums such as 4, dicyclopentadienyltitanium dichloride, and cyclopentadienyltitanium derivatives such as dimethyldicyclopentadienyltitanium.

Further, as specific examples of the zirconium compound, similar to the titanium compounds mentioned above, tetrano-rogenated zirconium; trihalogenated monoalcoquine zirconium; dihalogenated dialkoxyzirconium; monohalogenated trialkoxy/zirconium; and tetraalkoxyzirconium. However, dicyclopentadienylzirconium dichloride, dimethyldi/clopentanenylzirconium natonocyclopentacyenylzirconium derivatives can also be mentioned as suitable ones.

Further, specific examples of hunium compounds include tetrahalogenated hafnium; trihalogenated monoalkoxyhafnium; dihalogenated dialkoxyhafnium; monohalogenated trialkoxy/no-hunium; tetraalkoxyhafnium and dinoclopentagenyl hafnium dichloride; Mention may be made of dimethyldicyclopentadienylhafnium natononeclobentadienylhafnium derivatives.

The transition metal compound used in the present invention is the vanadium compound, titanium compound, zirconium compound or...
- One or more compounds selected from among the phunium compounds may be used, but ..nanium compounds are particularly preferred.

Next, component (b) used in the preparation of catalyst component (A) is an electron-donating compound.

Here, the electron-donating compound (b) is an organic compound or olefin containing oxygen, nitrogen, and/or sulfur. Specifically, amines and amides.

Examples include ketones, nitriles, phosphines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid...rides, aldehydes, and organic acids.

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 I)-toluic anhydride; acetone and methyl ethyl ketone. .

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

2-1 carbon atoms such as tolualdehyde and naphthaldehyde
Aldehydes of No. 5; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate.

Methyl methacrylate, ethyl crotonate, ethyl pivalate, dimethyl maleate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid/chlorohexyl/benzoic acid Phenyl, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethyl ethyl benzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate, Esters having 2 to 18 carbon atoms such as ethyl naphthoate, r-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethylene carbonate; acetyl chloride, benzyl chloride, toluic acid chloride.

Acid halides with 2 to 15 carbon atoms such as anisyl chloride; 2 to 15 carbon atoms such as methyl ether, ethyl ether, inopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, dioxane, aninol, diphenyl ether, and ethylene glycol butyl ether 20 ethers; acetic acid amide, benzoic acid amide,
Acid amides such as toluic acid amide; triethylamine.

Tributylamine, N,N'-dimethylpiperazine.

tribenzylamine, aniline, pyridine, picoline,
Examples include amines such as tetramethylethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; tetramethylurea, nitrobenzene, and lithium butyrate. Among these, esters, ethers, ketones, 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 ketones such as, aromatic carboxylic acid anhydrides such as benzoic anhydride, tetrahydrofuran, dioxane.

Ethers such as ethylene glycol butyl ether are also preferred. Note that olefins include ethylene,
Examples include monoolefins and diolefins having an R prime number of 1 to 20, such as propylene, butene, butadiene, hexene, and octene, and styrene derivatives.

Subsequently, the fc) component used in the preparation of the catalyst component (A) is an organometallic compound belonging to Groups 1 to 1 of the Periodic Table.

Here, the organometallic compound of groups 1 to 2 of the periodic table has the general formula % formula % (3) [wherein 1M2 represents a metal of groups 1 to 2 of the periodic table, and R2
1jJ prime number 1 to 20 alkyl group, cycloalkyl group,
Indicates an aryl group or an aralkyl group.

x2 represents a halogen atom. Further, p indicates the valence of M2, and q is a real number satisfying the relationship O<q<p. ]. Examples of metals in Groups 1 to 1 of the periodic table include lithium, sodium, potassium, zinc, cadmium, aluminum, and boron.

There are gallium, magne7ium, etc., but especially gallium,
Boron and magne/ram are preferred.

Specific examples of organometallic compounds of Groups 1 to 2 of the periodic table include alkyl gallium compounds such as trimethyl gallium, triethyl gallium, tripropyl gallium, and tributyl gallium; alkyl magnet compounds such as ethylbutylmagnesium and dibutylmagnesium; Examples include 7um compounds; alkyllithium compounds such as methyllithium, ethyllithium, propyllithium, and butyllithium; dialkylzinc compounds such as dimethylzinc, diethylzinc, diglobylzinc, and diptylzinc.

The catalyst component [A] used in the method of the present invention is the above (a)
, (bl, (c)) are prepared by reacting the components, but these reactions are usually carried out at -50 to 100°C,
Preferably at a temperature of 0 to 80°C for 0.1 minutes to 20 hours,
Preferably, it may be carried out for 1 minute to 10 hours. Here, the usage of each component is (b) component/(a) component = 0. OO1~20
(molar ratio), preferably 0.1 to 5 (molar ratio),
Component (C)/component (a) = 0.001 to 50 (molar ratio), preferably 0.1 to 5 (molar ratio).

Next, in the present invention, an organometallic compound belonging to Groups 1 to III of the periodic table is used as the catalyst component (B). Here, the organometallic compounds of Groups 1 to 2 of the periodic table are those mentioned above,
It may be the same as that used in preparing the catalyst component (A) or may be different, but organoaluminum compounds are particularly preferred. A specific example of this organic aluminum compound is trimethylaluminum.

Trialkylaluminium compounds such as triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, and diethylaluminum monochloride, diethylaluminum monopromide, diethylaluminium monoiodide, diisopropylaluminum monochloride, cyinobutylaluminum monochloride, dioctyl Dialkyl aluminum monohalides such as aluminum monochloride or alkyl aluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquipromide, butylaluminum sesquichloride are preferred, and mixtures thereof are also preferred. can give. Furthermore, alkyl group-containing aluminoxane produced by the reaction of alkyl aluminum and water can also be used.

The usage ratio of the catalyst component (A) and catalyst component (B) is 0.1 to 5000°, preferably 1 to 5000°, preferably 1. The ratio may be 2000 to 2000 (molar ratio).

According to the method of the present invention, ethylene and acrylic ester and/or α-
A substituted acrylic acid ester is copolymerized to produce an ethylene copolymer.

Here, the Lewis acid compound is a Lewis acid compound that can form a chain with a lone pair of electrons of a polar group, for example, a Lewis acid compound from 1-V of the periodic table.
Examples include 2- and 2-group compounds. Especially aluminum, boron, zinc, tin, magnesium,
No-loginated compounds such as antimony, such as aluminum chloride, ethylaluminum dichloride, diethylaluminium chloride, boron trichloride, zinc chloride, tin tetrachloride.

Preferred are alkyl tin halides, magnesium chloride, antimono pentachloride, antimono trichloride, and particularly preferred are aluminum chloride, ethylaluminum dichloride, and the like.

In addition, the acrylic ester and/or α-substituted acrylic ester to be copolymerized with ethylene has the general formula % (wherein R1 is a halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or R2 represents an aralkyl group, and R2 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-octyl acrylate, 2-acrylate
Examples include acrylic esters such as ethylhexyl, phenyl acrylate, and benzyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and phenyl methacrylate.

The ratio of the Lewis acid compound to the acrylic ester and/or α-substituted acrylic ester is 0.1 to 10 (molar ratio), preferably 0.2 to 1, of the Lewis acid compound to 1 of these esters. (molar ratio).

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, aromatic hydrocarbons, logenated hydrocarbons, etc. are used as the polymerization solvent. The polymerization conditions include a reaction temperature of 0 to 200°C, preferably 20 to 100°C.

The reaction pressure is normal pressure to 50 H/cm2G, preferably normal pressure to 30 H/cm2G. Molecular weight adjustment during polymerization may be carried out by known means, such as hydrogen.

The reaction time may be appropriately selected from 0.1 minute to 20 hours, preferably from 1 minute to 10 hours.

In the present invention, a transition metal compound is used as a catalyst.

The reaction product of an electron-donating compound and an organometallic compound of Groups 1 to III of the periodic table is
Since it is used in combination with an organometallic compound of the group, copolymerization activity can be improved.

Moreover, according to the method of the present invention, it is possible to improve the conversion rate of acrylic ester and/or α-substituted acrylic ester into a copolymer, and also to improve the conversion rate of acrylic ester and/or α-substituted acrylic ester to a copolymer. A copolymer with a high content of acid ester is obtained.

Therefore, the present invention can be effectively utilized for manufacturing materials that require adhesiveness, printability, dyeability, etc.

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

Example 1 (1) Preparation of catalyst component (A) A 300i four-bottle flask equipped with a dropping funnel and a stirrer was purged with argon, and then 100 ml of heptane was added thereto at 5°C with vanadium tetrachloride 0.5 +d (4, 7
A solution of ethyl benzoate in hebutane (0.47 mmol/m) as an electron-donating compound was added dropwise over 5 minutes, and the mixture was allowed to react for 1 hour. Next, the liquid temperature was raised to 20° C., and a solution of tri-n-butylgallium in hebutane (0,156 mmol/1) 10° was added dropwise over 5 minutes, and the reaction was carried out for 3 hours. The supernatant of the obtained dark green solid product was washed with Hepta/5 times to obtain a solid catalyst component.

(2) Production of copolymer 300 ml of hexane was placed in a pressure-resistant container with a stirrer and replaced with argon.
A hexane slurry of 0.87 i (8 mmol) of ethyl acrylate and 8 mmol of ball-milled aluminum chloride as the Lewis acid compound was added sequentially. Next, the temperature was raised to 50°C, and ethylene was added at 1 #/c.
m2G, followed by 25 mt of a hexane solution of triethylaluminum (2 mmol/mt) and 0.05 mI of the catalyst component [A] obtained in (1) above.
J mol was added. Next, add ethylene to the reaction vessel until the total pressure is 2.
The polymerization was carried out for 3 hours while stirring by continuously introducing the solution so as to maintain the kg/cm2G. After the polymerization reaction was completed, methanol 100- was added and stirred, and the obtained copolymer was
It was collected separately, washed and deashed with a mixture of hydrochloric acid and methanol, and then extracted with acetone for 5 hours.

The copolymer remaining after the acetate extraction was dried under reduced pressure at 80° C. for 2 hours to obtain a white copolymer 5.86r.

The activity of this catalyst is 2.3 kg7?・It was vanadium. As a result of infrared absorption spectrum analysis (IR analysis) of the obtained copolymer, it was found that 1730 cm-'
Absorption due to ester bonds was observed at 1160 cm-', and the content of ethyl acrylate in the copolymer was determined from the absorbance ratio of methylene chains and carbonyl groups to be 2.0.
% by weight. Also, the conversion rate of ethyl acrylate is 14
．． It was 6chi.

Example 2 Copolymer 14.5F was prepared in the same manner as in (2) of Example 1, except that the amounts of ethyl acrylate and aluminum chloride used in (2) of Example 1 were each 16 mmol.
I got it.

The activity of this catalyst was 5.7 kf/f.vanadium. In addition, the results of the IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 3.9% by weight,
The conversion rate of ethyl acrylate was 28.3%.

Example 3 Copolymer 3.57f was prepared in the same manner as in (2) of Example 1, except that the amounts of ethyl acrylate and aluminum chloride used in (2) of Example 1 were each 40 mmol.
I got it.

The activity of this catalyst was 1.4 kg7 tovanadium. Further, the results of the IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 9.7% by weight and 1% by weight, and the conversion rate of ethyl acrylate was 8.6%.

Example 4 (1) Preparation of catalyst component (A) A light purple solid catalyst component was obtained in the same manner as in Example 1 (1) except that 4.7 mlJ mole of dioxane was used as the electron donating compound. Ta.

(2) Production of copolymer The amount of aluminum acrylate t-tA used in (2) of Example 1 was 20 mmol, and the solid catalyst component (A) was the one obtained in - (2). Copolymer 7.90f was obtained in the same manner as in Example 1 (2). The activity of this catalyst is 3.1 kg
7?・It was vanadium. The results of JR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 6.0% by weight, and the conversion rate of ethyl acrylate was 1-1.
．． It was 23.7%.

Example 5 Copolymer 6.11r was prepared in the same manner as in (2) of Example 4, except that the amounts of ethyl acrylate and aluminum chloride used in (2) of Example 4 were each 40 mmol.
I got it.

The activity of this catalyst was 2.4 kg/9·vanadium. Moreover, the results of IR analysis were the same as those in Example].

The content of ethyl acrylate in the copolymer was 11.0% by weight, and the conversion rate of ethyl acrylate was 16.8%.

Example 6 (1) Preparation of catalyst component [A] A purple solid catalyst component was obtained in the same manner as +1) of Example 1, except that 4.7 mmol of hexene-1 was used as the electron-donating compound. .

(2) Production of copolymer Example 1 except that in (2) of Example 1, the solid catalyst component (A) obtained in (1) above was used.
Copolymer 6.627 was obtained in the same manner as in (2). The activity of this catalyst was 2.6 kg/9.vanadium.

The results of the IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 1.3% by weight, and the conversion rate of ethyl acrylate was 10.8%.

Example 7 (1) Preparation of catalyst component (A) A purple solid catalyst component was obtained in the same manner as in Example 1 (1), except that 4.7 ml J mole of vinyl acetate was used as the electron donating compound. Ta.

(2) Production of copolymer Example 1 except that in (2) of Example 1, the solid catalyst component (A) obtained in (1) above was used.
Copolymer 8.66F was obtained in the same manner as in (2). The activity of this catalyst is 3.4 kg/?・It was vanadium.

However, the results of the IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 17% by weight, and the conversion rate of ethyl acrylate was 18.4%.

Example 8 (1) Preparation of catalyst component (A) 4.1 ml of tetrahydrofuran as an electron-donating compound
) A pale purple solid catalyst component was obtained in the same manner as in (1) of Example 1 except that molar amount was used.

(2) Production of copolymer Example 1 except that in (2) of Example 1, the solid catalyst component (A) obtained in (1) above was used.
Copolymer 11.215' was obtained in the same manner as in (2).

The activity of this catalyst was 4.4 H/f/·vanadium. The results of the IR analysis were the same as in Example 1; the content of ethyl acrylate in the copolymer was 1.2% by weight, and the conversion rate of ethyl acrylate was 16.8%.

Example 9 (1) Preparation of catalyst component (A) Triethylamine was used as an electron donating compound (4.7 mm). j
A blackish-brown solid catalyst component was obtained in the same manner as in Example 1 (1) except that moles were used.

(2) Production of copolymer Example 1 except that in (2) of Example 1, the solid catalyst component (A) obtained in (1) above was used.
Copolymer 5.095' was obtained in the same manner as in (2). The activity of this catalyst was 2 to 97 V vanadium. The results of the IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 1.6% by weight, and the conversion rate of ethyl acrylate was 10.2%.

Example 10 In Example 1 (2), 8 mmol of methyl methacrylate was used instead of ethyl acrylate, and the catalyst component (A
) Copolymer 8.52 was prepared in the same manner as in Example 1 (2) except that the material obtained in Example 4 (1) was used. The activity of this catalyst is 3.3 Af/?・It was vanadium. The results of IR analysis are the same as in Example 1, and the content of methyl tutaacrylate in the copolymer is 5.2
The conversion rate of methyl methacrylate was 30.7% by weight.

Comparative Example 1 A copolymer was produced in the same manner as in (2) of Example 1, except that 0.05 mmol of vanadium tetrachloride was used in place of the solid catalyst component (A) in (2) of Example 1. 3.82
I got a 9. The activity of this catalyst was 1.5 dirt/9.vanadium. The results of the deep IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 1.0% by weight, and the conversion rate of ethyl acrylate was 4.8%, both of which were low. there were.

Procedural amendment stamp button June 27, 1985 Manabu Shiga, Commissioner of the Patent Office 1. Indication of the case Patent application 118176/1982 2. Name of the invention Process for producing ethylene copolymer 3. Person making the amendment Relationship with the case Patent Applicant: Idemitsu Kosan Co., Ltd. 4, Agent: 1-1-10-5, Kyobashi, Chuo-ku, Tokyo 104, Claims column and Detailed Description of the Invention column 6 of the specification to be amended; Contents (1) The scope of claims is amended as shown in the attached sheet.

(2) In the middle of page 4 of the specification [General formula %formula% (3) In the middle of page 16 of the same i-general formula %formula%) ] [general formula I I O” Correct.

(hereinafter referred to as "2") Claims (1) Using (A) a transition metal-containing component and (B) an organometallic compound of Groups 1 to 2 of the periodic table as a catalyst, ethylene and dihydrogen are used in the presence of a Lewis acid compound. (Momme R'' CH2= C-C-0-R2 1 (wherein, R1 is a halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group.

It represents an aryl group or an aralkyl group, and R2 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. ) In producing an ethylene copolymer by copolymerizing an acrylic ester and/or an α-substituted acrylic ester represented by (A), (a) is used as a transition metal-containing component.
) transition metal compound, (b) electron donating compound and (C
) A method for producing an ethylene copolymer, characterized by using a reaction product of an organometallic compound of Groups 1 to 1 of the Periodic Table.

(2) (a) The transition metal compound is titanium, vanadium,
The manufacturing method according to claim 1, which is a zirconium or hafnium compound.

(3) The method according to claim 1, wherein the organometallic compound of Groups 1 to 1 of the periodic table is an organic compound of lithium, sodium, potassium, zinc, cadmium, aluminum, boron, or gallium.

65-

Claims (3)

[Claims] (1) As a catalyst, (A) a transition metal-containing component and CB) an organometallic compound of groups ■ to ■ of the periodic table are used, and in the presence of a Lewis acid compound, ethylene and the general formula % formula % (in the formula, R1 is ...represents rogene, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, R2 is an alkyl group having 1 to 20 carbon atoms,
Indicates a cycloalkyl group, aryl group or aralkyl group. ) In producing an ethylene copolymer by copolymerizing an acrylic ester and/or an α-substituted acrylic ester represented by CA) (a) as a transition metal-containing component.
) transition metal compound, (b) electron donating compound and (c
) A method for producing an ethylene copolymer, characterized by using a reaction product of an organometallic compound of Groups 1 to 1 of the Periodic Table. (2) (a) The transition metal compound is titanium or vanadium. It is a compound of zirconium or hafnium. A manufacturing method according to claim 1. (3) The method according to claim 1, wherein the organometallic compound of Groups 1 to 1 of the Periodic Table is an organic compound of lithium, sodium, potassium, zinc, cadmium, aluminum, boron, or gallium.