JPH0699520B2 - Method for producing ethylene copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer, and more specifically, it has a high copolymerization activity and a high content of acrylic ester in the obtained copolymer. The present invention relates to a method for producing an ethylene copolymer having an improved conversion rate to a polymer.

Polyethylene is a resin having excellent properties, but it is chemically inactive, and therefore has poor adhesiveness, printability, and dyeability. Therefore, in order to eliminate such drawbacks of polyethylene, a method of copolymerizing an unsaturated compound copolymerizable with ethylene has been considered. As such a method, for example, JP-B-49-23317 proposes a method of copolymerizing ethylene with an acrylate ester in the presence of a Lewis acid compound. However, in this case, the copolymerization activity is not sufficient, and the composition cannot be arbitrarily controlled. Further, the methods described in JP-B-48-37755 and JP-A-59-43003 have a problem that the content of unsaturated carboxylic acid ester in the olefin-unsaturated carboxylic acid ester copolymer is low. . Furthermore, the conversion of unsaturated carboxylic acid ester into a copolymer is not sufficient.

As a result of various studies to solve the problems in the above conventional methods, the present inventors have found that (a) a reaction product of a vanadium compound as a transition metal compound and (b) a specific metal salt, or Furthermore, both and (c) Periodic Table I
To a group III organometallic compound (provided that it contains an alkyl group) as a component of the catalyst,
The inventors have found that the problems in the above-mentioned conventional techniques can be solved by using a combination of this and an organoaluminum compound as an organometallic component as a catalyst, and completed the present invention.

That is, firstly, the present invention uses [A] a transition metal-containing component and [B] an organometallic compound of Group I to III of the periodic table as a catalyst, and ethylene and a general formula are used in the presence of a Lewis acid compound. (In the formula, R ¹ represents halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group. Or an aralkyl group.) When an ethylene copolymer is produced by copolymerizing an acrylic ester and / or an α-substituted acrylic ester represented by
From (a) a vanadium compound and (b) a metal salt of an organic carboxylic acid having 8 or more carbon atoms, a metal salt of an organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and a metal salt of an alcohol having 8 or more carbon atoms Using a reaction product with one or more selected compounds, and [B] an organoaluminum compound as an organometallic compound of Groups I to III of the periodic table, and a halogen-containing aluminum compound as a Lewis acid compound. The present invention provides a method for producing an ethylene copolymer characterized by the above.

Secondly, the present invention uses a [A] transition metal-containing component and [B] an organometallic compound of Group I to III of the periodic table as a catalyst, and ethylene and a general formula in the presence of a Lewis acid compound. (In the formula, R ¹ represents halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group. Or an aralkyl group.) When an ethylene copolymer is produced by copolymerizing an acrylic ester and / or an α-substituted acrylic ester represented by
From (a) a vanadium compound and (b) a metal salt of an organic carboxylic acid having 8 or more carbon atoms, a metal salt of an organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and a metal salt of an alcohol having 8 or more carbon atoms One or more selected compounds and (c) an organometallic compound of Groups I to III of the periodic table (provided that
Limited to those containing an alkyl group. And a halogen-containing aluminum compound as a Lewis acid compound, as well as an organoaluminum compound as an organometallic compound of Group I to III of the periodic table [B]. A method for producing a polymer is provided.

First, the first aspect of the present invention will be described below.

The catalyst component [A] in the first aspect of the present invention is a transition metal-containing component, and comprises (a) a vanadium compound and (b) a carbon number of 8
The above metal salts of organic carboxylic acids, metal salts of organic phosphoric acids having an aliphatic hydrocarbon group having 8 or more carbon atoms, and 8 carbon atoms
A reaction product with one or more compounds selected from the above metal salts of alcohol is used.

The vanadium compound which is the component (a) used for the preparation of the catalyst component [A] is represented by the general formula M ¹ (OR ³ ) lX ¹ mYn [I] [wherein M ¹ represents vanadium and R ³ represents the number of carbon atoms. 1 to 20 represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and X ¹ represents a halogen atom. Y represents oxygen, cyclopentadienyl or acetylacetonate, l, m and n are each a real number of 0 or more and less than 5, and the sum of these is the valence of M ¹ . ] The compound represented by the general formula [I]
It is a vanadium compound represented by.

Here, if a concrete example of a vanadium compound is given, VCl ₄ , VCl ₂
Such as vanadium chloride; VOCl ₃ , VOCl ₂ such as vanadium oxychloride; V (O ・ nC ₄ H ₉ ) ₄ , VO (OC ₂ H ₅ ) ₃ , VO (O ・ nC
Examples thereof include vanadium alkoxides such as ₄ H ₉ ) ₃ ; cyclopentadienyl vanadium derivatives such as dicyclopentadienyl vanadium chloride; and vanadium acetylacetonate compounds such as V (acac) ₃ and VO (acac) ₂ . Here, acac is an acetylacetonate group,
That is, it represents an acetylacetone ion.

Next, the component (b) used for preparing the catalyst component [A] is a metal salt of an organic carboxylic acid having 8 or more carbon atoms, a metal salt of an organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and a carbon number. One or more compounds selected from metal salts of 8 or more alcohols.

Here, the organic carboxylic acid constituting the metal salt of the organic carboxylic acid may be saturated or unsaturated, and one having 8 or more carbon atoms is used. Specifically, for example, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid are preferably used. In the present invention, metal salts of these organic carboxylic acids, particularly magnesium salts, calcium salts and manganese salts are preferably used. As the organic carboxylic acid metal salt, magnesium stearate is particularly preferable.

Further, the phosphoric acid constituting the organic metal phosphate may be phosphorous acid, and phosphoric acid or a mono- or dialkyl ester of phosphorous acid (R ⁴ OPH ₂ O ₃ , (R ⁴ O) ₂ PHO ₂ , R ⁴ OPH ₂ O ₂ etc.) or mono- or dialkyl (phosphite) (R ⁴ PH ₂ O ₃ ,
R ⁴ ₂ PHO ₂ , R ⁴ PH ₂ O _{2 and the} like). Here, R ⁴ represents an alkyl group. The phosphoric acid has 8 carbon atoms.
Those having the above aliphatic hydrocarbon groups are used. Here, the aliphatic hydrocarbon group may be either a saturated or unsaturated group. Specific examples of these include a hexyl group,
Examples thereof include heptyl group, octyl group, 2-ethyl-hexyl group, nonyl group, decyl group, lauryl group, myristyl group, heptadecyl group, stearyl group, octadecenyl group and the like. In the present invention, these metal salts of phosphoric acid, particularly magnesium salt, calcium salt and manganese salt are preferably used.

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

Metal salts of these organic carboxylic acids, organic phosphoric acids or alcohols, specifically magnesium salts, calcium salts,
Manganese salts and the like can be obtained by various methods, and commercially available products may be dried and used as they are. The magnesium salt can be easily produced from organic carboxylic acid, organic phosphoric acid or alcohol, and alkyl magnesium such as butylethyl magnesium and dibutyl magnesium. Furthermore, the above-mentioned magnesium salt, calcium salt, manganese salt, etc. (that is, organic carboxylate salts, organic phosphate salts or alcohol salts of magnesium, calcium, manganese, etc.) form a double salt with another metal. May be.

In the first aspect of the present invention, the metal salt of an organic carboxylic acid having 8 or more carbon atoms, the metal salt of organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and the metal salt of alcohol having 8 or more carbon atoms. A catalyst component [A] is prepared from the above-mentioned components (a) and (b) by using one or more compounds selected from the above as the component (b).

The reaction between the component (a) and the component (b) is usually 0 to 200.
C., preferably 20-80.degree. C. for 0.1 minutes-20 hours, preferably 1 minute-10 hours. Here, the amount of each component used is (b) component / (a) component = 0.001 to 50 (molar ratio),
It is preferably 0.1 to 10 (molar ratio).

The reaction product thus obtained is used as the catalyst component [A].

Next, in the present invention, an organoaluminum compound is used as the catalyst component [B].

Here, the organoaluminum compound is represented by the general formula R ⁵ qAlX ² p _- q [II] [wherein R ⁵ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X ² is Indicates a halogen atom. Further, p represents the valence of aluminum, and q is a real number that satisfies the relationship of 0 <q ≦ p. ] Is represented.

Here, specific examples of the organoaluminum compound include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum,
Trialkyl aluminum compounds such as trioctyl aluminum and dialkyl aluminum monohalides such as diethyl aluminum monochloride, diethyl aluminum monobromide, diethyl aluminum monoiodide, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum monochloride or methyl aluminum sesqui Alkylaluminum sesquihalides such as chloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide and butylaluminum sesquichloride are preferable, and a mixture thereof is also preferable. Furthermore, an alkyl group-containing aluminoxane produced by the reaction of alkylaluminum and water can also be used.

The catalyst component [A] and the catalyst component [B] are used in a ratio of 0.1 to 5000 metal atom of the organometallic compound of the catalyst component [B] to metal atom of the transition metal compound of the catalyst component [A].
(Atomic ratio), preferably 1 to 2000 (atomic ratio).

According to the method of the present invention, ethylene and an acrylate ester and / or an α-substituted compound are used in the presence of a halogen-containing aluminum compound as a Lewis acid compound by using a catalyst comprising the catalyst component [A] and the catalyst component [B]. An acrylic acid ester is copolymerized to produce an ethylene copolymer.

Here, as the Lewis acid compound, a halogen-containing aluminum compound, which is a Lewis acid compound capable of forming a complex with a lone pair of polar groups, is used. Specific examples of the halogen-containing aluminum compound include aluminum chloride, ethylaluminum dichloride, diethylaluminum chloride and the like.

Further, the acrylic acid ester and / or α-substituted acrylic acid ester copolymerized with ethylene are represented by the general formula (In the formula, R ¹ represents halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group. Alternatively, it represents an aralkyl group.). Specifically, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, and methyl methacrylate. , Ethyl methacrylate, butyrate methacrylate, methacrylic acid
Examples thereof include methacrylic acid esters such as 2-ethylhexyl and phenyl methacrylate.

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

The type of polymerization is not particularly limited, and slurry polymerization, solution polymerization, gas phase polymerization, etc. are all possible, and continuous polymerization,
Any discontinuous polymerization is possible. In this case, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and halogenated hydrocarbons 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 atmospheric pressure to 50 kg / cm ² G, preferably atmospheric pressure to 30 kg / c.
m ² G. Molecular weight control during polymerization is a known means,
For example, hydrogen may be used. The reaction time may be appropriately selected from 0.1 minutes to 20 hours, preferably 1 minute to 10 hours.

Thus, according to the first aspect of the present invention, an ethylene copolymer can be produced.

Next, a second aspect of the present invention is the same as the first aspect of the present invention, in which [A]
In addition to the components (a) and (b) as the transition metal-containing component, an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group) is used as the component (c). The reaction products of the components (a), (b) and (c) are used as a catalyst in combination with the catalyst component [B] to produce an ethylene copolymer.

Here, in the second aspect of the present invention, the organometallic compound of Group I to III of the Periodic Table, which is the component (c) used for the preparation of the catalyst component [A] (provided that it contains an alkyl group).
Has the general formula R ⁵ qM ² X ² p _- in q [wherein, M ² represents a periodic table I~III metals, R ⁵ represents an alkyl group having 1 to 20 carbon atoms, X ² is Indicates a halogen atom. Further, p represents the valence of M ² , and q is a real number satisfying the relationship of 0 <q ≦ p. ] Is represented. Examples of the metals of groups I to III of the periodic table include lithium, sodium, potassium, zinc, cadmium, aluminum, boron, gallium and magnesium.

Examples of the organoaluminum compound include those exemplified as the catalyst component [B]. Furthermore, an alkyl group-containing aluminoxane produced by the reaction of alkylaluminum and water can also be used. In addition to the organoaluminum compounds described above, alkylgallium compounds such as trimethylgallium, triethylgallium, tripropylgallium, and tributylgallium; alkylmagnesium compounds such as ethylbutylmagnesium and dibutylmagnesium; methyllithium;
Alkyllithium compounds such as ethyllithium, propyllithium and butyllithium; dialkylzinc compounds such as dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc and the like, and especially trimethylgallium, triethylgallium, tripropylgallium, tributylgallium. Alkyl gallium compounds such as

The components (a) and (b) used for preparing the catalyst component [A] in the second aspect of the present invention are the same as those described in the first aspect of the present invention. In the second aspect of the present invention, the reaction products of the components (a), (b) and (c) are used as the catalyst component [A].

Here, the catalyst component [A] is prepared by mixing the above components (a), (b) and (c) at a temperature of 50 to 200 ° C., preferably 20 to 80 ° C. for 0.5 to 20 hours, preferably 5 minutes to It is carried out by reacting for 5 hours. The amount of each component used is (b) component / (a) component = 0.001 to 50 (molar ratio), preferably 0.1 to
10 (molar ratio), (c) component / (a) component = 0.01-
It is 50 (molar ratio), preferably 0.1 to 5 (molar ratio).

In the second aspect of the present invention, an ethylene copolymer is produced in the same manner as in the first aspect of the present invention except that the reaction product thus obtained is used as the catalyst component [A].

According to the first aspect of the present invention as described above, the copolymerization activity can be improved in the production of the ethylene copolymer. Moreover, according to the first aspect of the present invention, the content of acrylic acid ester or the like in the obtained copolymer can be increased. Further, according to the first aspect of the present invention, the conversion rate of a copolymer such as an acrylic ester can be improved.

Furthermore, according to the second aspect of the present invention, the copolymerization activity can be further improved, and the content of acrylic acid ester or the like in the resulting copolymer can be further increased, and the copolymerization of acrylic acid ester can be increased. The conversion rate to coalescence can be further improved.

Therefore, the present invention can be effectively used for the production of materials required to have adhesiveness, printability, dyeability and the like.

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

Example 1 (1) Preparation of catalyst component [A] In a 300 ml four-necked flask equipped with a dropping funnel and a stirrer, 200 ml of heptane and 0.76 ml (7.1 mmol) of vanadium tetrachloride under reduced pressure at 20 ° C. under an argon stream. 12.6 g (21.3 mmol) of dried magnesium stearate was added, the temperature was raised to 50 ° C., and the reaction was carried out for 3 hours while stirring. The obtained solid slurry product had a pale blue color and was used as a catalyst component [A] without separating a solid liquid.

(2) Manufacture of copolymer 300 ml of hexane was placed in a 500 ml pressure vessel equipped with a stirrer, which had been replaced with argon, and after sufficiently replacing with argon, 0.87 ml (8 mmol) of ethyl acrylate and 8 mmol of ball-milled aluminum chloride. Hexane slurry was added. Next, raise the temperature of the reaction vessel to 50 ° C and add 1 k
After introducing so as to be g / cm ² G, 2.5 mmol of triethylaluminum as the catalyst component [B] and the catalyst component [A] obtained in the above (1) were converted to vanadium in an amount of 0.1.
05 mmol was injected. Next, ethylene was continuously introduced into the reaction vessel so that the total pressure was maintained at ² kg / cm ² G, and polymerization was carried out for 3 hours while stirring. After completion of the polymerization reaction, 100 ml of methanol was added and stirred, and the obtained copolymer was separated and recovered, further washed and decalcified with a mixed solution of hydrochloric acid and methanol, and then extracted with acetone for 5 hours. The copolymer remaining after extraction with acetone was dried under reduced pressure at 80 ° C. for 2 hours to obtain 4.07 g of the copolymer.

The activity of this catalyst was 1.6 kg / g.vanadium. The results of the obtained copolymer analyzed by infrared absorption spectrum (IR analysis) the were line summer, absorption by carbonyl group 1730 cm ^-1, absorption by ether bond 1160 cm ^-1 was observed. The ethyl acrylate content determined from the absorbance ratio between the methylene chain and the carbonyl group was 3.7% by weight. The conversion of ethyl acrylate was 19.2%.

Example 2 2.56 g of a copolymer was obtained 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 20 mmol.

The activity of this catalyst was 1 kg / g.vanadium. Also, I
The results of the R analysis are the same as in Example 1, the content of ethyl acrylate is 9.8% by weight, and the conversion of ethyl acrylate is 1
It was 2.8%.

Example 3 (1) Preparation of catalyst component [A] In a four-neck flask similar to that used in (1) of Example 1 except that a reflux tube was provided, 100 ml of heptane and 1 mmol of dioctyl phosphate were added at 20 ° C. A heptane solution containing 1 mmol of butylethylmagnesium was added, the temperature was raised with stirring, and the mixture was reacted under reflux for 3 hours. Then, the temperature was lowered to 50 ° C., 1 mmol of vanadium tetrachloride was added, and the mixture was reacted for 3 hours under stirring to obtain a reddish brown solution.

(2) Production of Copolymer 5.4 g of a copolymer was prepared in the same manner as in (2) of Example 1 except that the solution obtained in the above (1) was used as the catalyst component [A] in an amount of 0.05 mmol in terms of vanadium. Obtained.

The activity of this catalyst was 2.12 kg / g.vanadium. The results of IR analysis were the same as in Example 1, the content of ethyl acrylate was 2.3% by weight, and the conversion of ethyl acrylate was 15.2%.

Example 4 3.7 g of a copolymer was obtained in the same manner as in (2) of Example 3 except that the amounts of ethyl acrylate and aluminum chloride used were each 20 mmol.

The activity of this catalyst was 1.45 kg / g.vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate was 5.8% by weight, and the conversion rate of ethyl acrylate was 10.7%.

Example 5 (1) Preparation of catalyst component [A] To a flask similar to that used in Example 1 (1) at 20 ° C. was added a heptane solution containing 100 ml of heptane, 2.35 mmol of stearyl alcohol and 1.18 mmol of butylethylmagnesium, The reaction was allowed to proceed for 3 hours with stirring at ° C. Then, the temperature was lowered to 50 ° C, and vanadium tetrachloride 2.
35 mmol was added and the mixture was reacted for 3 hours with stirring to obtain a brownish brown solution.

(2) Production of Copolymer 5.9 g of a copolymer was prepared in the same manner as in (2) of Example 1 except that the solution obtained in (1) above was used as the catalyst component [A] in an amount of 0.05 mmol in terms of vanadium. Obtained.

The activity of this catalyst was 2.32 kg / g.vanadium. The results of IR analysis were the same as in Example 1, the content of ethyl acrylate was 7.2% by weight, and the conversion of ethyl acrylate was 53.1%.

Example 6 (1) Preparation of catalyst component [A] In a flask similar to that used in (1) of Example 1, 100 ml of heptane and 1.18 of magnesium stearate were added at 20 ° C.
Mmol and oxytriethylvanadate (VO (OC ₂ H
₅ ) ₃ ) 1.18 mmol of 1.18 mmol was sequentially added, and the temperature was raised to 50 ° C. and the reaction was carried out for 3 hours while stirring. As a result, a yellow slurry catalyst component was obtained.

(2) Manufacture of copolymer Conducted except that 0.02 mmol of the slurry obtained in (1) above was used as the catalyst component [A] in terms of vanadium and 0.4 mmol of diethylaluminum chloride was used as the catalyst component [B]. A copolymer (4.85 g) was obtained in the same manner as in (2) of Example 1.

The activity of this catalyst was 4.76 kg / g.vanadium. The results of IR analysis were the same as in Example 1, with an ethyl acrylate content of 9.4% by weight and an ethyl acrylate conversion of 57.0%.

Example 7 (1) Preparation of catalyst component [A] In a flask similar to that used in (1) of Example 3, 100 ml of heptane, a dioctyl phosphate 1.18 mmol, and a butylethylmagnesium 1.18 mmol heptane solution were sequentially added at 20 ° C. In addition, the mixture was reacted under reflux with stirring for 3 hours. Then, the temperature is lowered to 50 ° C and oxytriethylvanadate is added.
1.18 mmol was added and reacted for 3 hours with stirring.
As a result, a reddish brown solution was obtained.

(2) Manufacture of copolymer 4.6 g of copolymer as in (2) of Example 6 except that 0.02 mmol of vanadium equivalent was used as the catalyst component [A] in the solution obtained in (1) above. Got

The activity of this catalyst was 4.52 kg / g.vanadium. The results of the IR analysis were the same as in Example 1. The content of ethyl acrylate was 12.1% by weight, and the conversion rate of ethyl acrylate was 69.5%.

Example 8 (1) Preparation of catalyst component [A] In a flask similar to that used in Example 1 (1), heptane 200 ml, vanadium tetrachloride 0.76 ml (7.1 mmol) and magnesium stearate 12.6 g ( 21.3
Mmol) was added, the temperature was raised to 50 ° C., and the reaction was carried out for 3 hours with stirring. Then, the temperature was lowered to 20 ° C., a hexane solution of 2.4 mmol of trinormal butyl gallium was added, and the reaction was carried out for 3 hours. As a result, a pale blue slurry-like catalyst component was obtained.

(2) Production of copolymer Except that the slurry obtained in (1) above was used as the catalyst component [A] in an amount of 0.05 mmol in terms of vanadium, and the amounts of ethyl acrylate and aluminum chloride used were each 20 mmol. 6.88 g of a copolymer was obtained in the same manner as in (2) of Example 1.

The activity of this catalyst was 2.7 kg / g. Vanadium. The results of IR analysis were the same as in Example 1, with the content of ethyl acrylate being 12.7 wt% and the conversion of ethyl acrylate being 43.3%.

Example 9 (1) Preparation of catalyst component [A] At 20 ° C., 100 ml of heptane, 1 mmol of dioctyl phosphate and 1 mmol of butylethylmagnesium were added to the same flask as used in (1) of Example 3 and stirred. While reacting for 3 hours. After completion of the reaction, the temperature was lowered to 50 ° C., 1 mmol of vanadium tetrachloride was added, and the reaction was carried out for 3 hours with stirring. Next, by adding 0.33 mmol of tri-n-butylbutyl gallium and reacting for 3 hours under stirring,
A pale green solution was obtained.

(2) Production of Copolymer Except that the solution obtained in (1) above was used as the catalyst component [A] in an amount of 0.05 mmol in terms of vanadium, and the amounts of ethyl acrylate and aluminum chloride used were each 20 mmol. Copolymer in the same manner as in (2) of Example 1.
I got 0g.

The activity of this catalyst was 1.18 kg / g.vanadium. The results of IR analysis were the same as in Example 1, with the content of ethyl acrylate being 6.8% by weight and the conversion of ethyl acrylate being 10.2%.

Example 10 In place of ethyl acrylate in (2) of Example 7,
4.7 g of a copolymer was obtained in the same manner as in Example 7, except that 8 mmol of methyl methacrylate was used. Catalytic activity
It was 4.6 kg / g-vanadium, and the content of methyl methacrylate was 5.2% by weight. The conversion of methyl methacrylate was 30.7%.

Comparative Example 1 A copolymer (3.28 g) was obtained in the same manner as in (2) of Example 1 except that 0.05 mmol of vanadium tetrachloride was used as the catalyst component [A].

The activity of this catalyst was 1.5 kg / g.vanadium. Further, the content of ethyl acrylate was 1.0% by weight, and the conversion rate of ethyl acrylate was 4.8%, which were both low values.

Comparative Example 2 Oxytriethylvanadate 0.02 as catalyst component [A]
4.28 g of a copolymer was obtained in the same manner as in (2) of Example 6 except that mmol was used.

The activity of this catalyst was 4.2 kg / g.vanadium. The ethyl acrylate content was 4.0% by weight, and the ethyl acrylate conversion rate was 23.4%.

Example 11 (1) Preparation of catalyst component [A] 300 ml equipped with a dropping funnel and a stirrer as in Example 1.
In a four-necked flask of (1) under an argon stream at 200C, 200 ml of heptane, 0.76 ml (7.1 mmol) of vanadium tetrachloride, and 12.9 g of calcium stearate (21.
3 mmol) was added, the temperature was raised to 50 ° C., and the reaction was carried out for 3 hours while stirring. The resulting solid slurry product is
This was used as the catalyst component [A] without decomposing the solid-liquid.

(2) Manufacture of copolymer 3.5 g of copolymer as in (2) of Example 1 except that the solution obtained in (1) above was used as the catalyst component [A] in an amount of 0.05 mmol in terms of vanadium. Got

The activity of this catalyst was 1.38 kg / g.vanadium. The results of IR analysis were the same as in Example 1, the content of ethyl acrylate was 3.9% by weight, and the conversion of ethyl acrylate was 17.1%.

[Brief description of drawings]

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

Claims (3)

[Claims] 1. A catalyst comprising [A] a transition metal-containing component and [B] an organometallic compound of Group I to III of the periodic table as a catalyst,
In the presence of Lewis acid compounds ethylene and the general formula (In the formula, R ¹ represents halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group. Or an aralkyl group.) When an ethylene copolymer is produced by copolymerizing an acrylic ester and / or an α-substituted acrylic ester represented by
From (a) a vanadium compound and (b) a metal salt of an organic carboxylic acid having 8 or more carbon atoms, a metal salt of an organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and a metal salt of an alcohol having 8 or more carbon atoms Using a reaction product with one or more selected compounds, and [B] an organoaluminum compound as an organometallic compound of Groups I to III of the periodic table, and a halogen-containing aluminum compound as a Lewis acid compound. A method for producing an ethylene copolymer, which comprises: 2. The method according to claim 1, wherein the vanadium compound (a) used for preparing the catalyst component [A] is vanadium tetrachloride or oxytriethylvanadate. 3. A catalyst containing [A] a transition metal-containing component and [B] an organometallic compound of Groups I to III of the periodic table as a catalyst,
In the presence of Lewis acid compounds ethylene and the general formula (In the formula, R ¹ represents halogen, hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ² represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group. Or an aralkyl group.) When an ethylene copolymer is produced by copolymerizing an acrylic ester and / or an α-substituted acrylic ester represented by
(A) a vanadium compound, (b) a metal salt of an organic carboxylic acid having 8 or more carbon atoms, a metal salt of an organic phosphoric acid having an aliphatic hydrocarbon group having 8 or more carbon atoms, and a metal salt of an alcohol having 8 or more carbon atoms One or more selected compounds and (c) an organometallic compound of Groups I to III of the periodic table (provided that
Limited to those containing an alkyl group. ), And [B] an organoaluminum compound as an organometallic compound of Groups I to III of the periodic table, and a halogen-containing aluminum compound as a Lewis acid compound. How to make a coalesce.