JPS61133209A - Production of ethylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer of good printability and dyeability in high conversion, by copolymerization between ethylene, acrylic ester etc., in the presence of a Lewis acid, using as a catalyst a combination of vanadium- contg. component and reaction product from organoaluminum compound and specific modifier. CONSTITUTION:The objective copolymer can be obtained by copolymerization, in the presence of a Lewis acid, between ethylene, an acrylic ester (e.g., ethyl acrylate) and/or alpha-substituted acrylic ester using as a catalyst, a combination of (A) a vanadium-contg. component (e.g., vanadium chloride) and (B) a reaction product from (i)organoaluminum compound as an aluminum-contg. component and (ii) at least one sort of modifier selected from alcohols, amines, carboxylic acids, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer comprising ethylene and an acrylic ester and/or an α-substituted acrylic ester.゛Conventionally, polyethylene has been 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.

Therefore, in order to improve these properties of polyethylene, a method of copolymerizing an unsaturated compound that is copolymerizable with ethylene has been considered. For example, Japanese Patent Publication No. 49-23317 proposes a method of copolymerizing ethylene and acrylic ester using a catalyst in the presence of a Lewis acid compound. However, this method has disadvantages in that the copolymerization activity is not sufficient and the conversion rate of acrylic ester to a copolymer is low.

The present inventors have conducted extensive research in order to develop an extremely efficient method for producing ethylene copolymers that eliminates the above-mentioned conventional problems. As a result, by using modified organoaluminum together with a vanadium-containing component as a catalyst in the copolymerization reaction of ethylene and acrylic ester, it was found that the copolymerization activity and the conversion of acrylic ester (α-substituted acrylic ester) to a copolymer were improved. The present invention was completed based on this finding.

That is, the present invention first uses a catalyst consisting of [A] a vanadium-containing component and [B] an aluminum-containing component, and ethylene and an acrylic ester and/or an α-substituted acrylic ester in the presence of a Lewis acid. By copolymerizing 1t) x In producing the tyrene copolymer, [B] a reaction product of an organoaluminum compound 'lFI as an aluminum-containing component and at least one modifier selected from alcohols, amines, and carboxylic acids; The present invention also provides a method for producing an ethylene copolymer, characterized in that it uses a ethylene copolymer.

Second, the present invention uses a catalyst consisting of [A] a vanadium-containing component and [B] an aluminum-containing component, and reacts ethylene with an acrylic ester and/or an α-substituted ester in the presence of a Lewis acid. In producing an ethylene copolymer by copolymerizing J/Iz acid esters, [B] an organoaluminum compound and a small amount selected from alcohols, amines, and carboxylic acids (all together with one type of modifier) as the aluminum-containing component. [A] a vanadium compound as the vanadium-containing component; (a) an organometallic compound of Groups 1 to 2 of the Periodic Table; (b) a carboxylic acid, an alcohol, and an organic phosphoric acid. (c) an electron-donating compound; (d) a Lewis acid compound of groups ■ to ■ of the periodic table; and (e) a metal salt of at least one compound of the periodic table.
The present invention also provides a method for producing an ethylene copolymer, which is characterized by using a reaction product with at least one compound selected from metal compounds of group (1).

The catalyst used in the method of the present invention consists of [A] a vanadium-containing component and [B] an aluminum-containing component.

Here, [A] vanadium-containing component usually has the general formula
It is a vanadium compound represented by V COR')nX'5Yrt...CI). In the general formula (1), R1 represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of R1 include a methyl group, an ethyl group, a propyl group, an n-butyl group, a hexyl group, and an octyl group.

Examples include 2-ethylhexyl group, cyclopentyl group, cyclohexyl group, phenyl group, and benzyl group. X
I is a halogen atom, that is, chlorine.

Examples include bromine and iodine, with chlorine being particularly preferred.

Y represents an oxygen atom, a cyclopentagenyl group or an acetylacetonate group. Furthermore, m and n are each real numbers from 0 to 5.

A specific example of such a vanadium compound is VCl
a, Vanadium chloride such as VCh; VOCh, voc
vanadium oxychloride such as tz; v(0·n-CJq
)a+VO(OCJs)s+VO(0・n−CJJi
vanadium alkoxides such as; cyclopentagenyl vanadium derivatives such as dicyclopentadienyl vanadium chloride; V(acac)s + VO(acac
) z and other vanadium acetylacetonate compounds. Note that here, acac represents an acetylacetonate group, that is, an acetylacetone ion.

Next, [B] is reacted with the vanadium-containing component [A].
] As the aluminum-containing component, a reaction product of an organoaluminum compound and at least one modifier selected from alcohols, amines, and carboxylic acids is used.

Here, the organoaluminum compound is represented by the general formula % (in the formula, R2 is an alkyl group having 1 to 10 carbon atoms, X2 is a halogen atom, and p is a real number of 1 to 3). Alkylaluminum or aluminoxane may be mentioned.

Here, specific examples of the alkylaluminum represented by the above general formula (ff) include trimethylaluminum,
Trialkylaluminium compounds such as triethylaluminum, triisopropylaluminium, triisobutylaluminum, trioctylaluminum, and diethylaluminium monochloride, diethylaluminum monopromide, diethylaluminium monoiodide.

Dialkylaluminum monohalides such as diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, iShunga ethylaluminum sesquipromide.

Alkylaluminum sesquihalides such as butylaluminum sesquichloride/etc. are preferred, and mixtures thereof are also preferred.

Further, as the aluminoxane, an alkyl group-containing aluminoxane produced by a reaction between an alkyl aluminum and water can also be used.

These existing aluminum compounds include trimethylaluminum and triethylaluminum.

Triisobutylaluminum, diethylaluminium monochloride and the like are preferably used.

In the present invention, [B] the above-mentioned organoaluminum compound and at least one selected from alcohol, amine, and carboxylic acid as the aluminum-containing component
A reaction organism with a seed denaturant is used.

Here, the alcohol has the general formula R'OH...CIII) (wherein R3 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group or hydroxyalkyl group having 1 to 20 carbon atoms.) It is expressed as A specific example of the alcohol represented by the above general formula (I[) is methanol.

Ethanol, normal propatool, isopropanol, normal butanol, imbutanol.

t-butanol, amyl alcohol, hexanol, cyclohexanol, cyclopentanol.

In addition to alcohols such as benzyl alcohol, phenols such as phenol and catechol can be mentioned.

In addition, as an amine, the general formula R4・R'NH... (IV) (in the formula, R
', R' is hydrogen or an alkyl group having 1 to 2 carbon atoms, an alkenyl group, or a cycloalkyl group.

Indicates an aryl group, an aralkyl group, or a hydroxyalkyl group. ), and diamines can also be used. A specific example of the amine used in the present invention is dimethylamine.

diethylamine, dipropylamine, dibutylamine,
Secondary amines and butylamine such as cyamylamine, dihexylamine, and dioctylamine.

Primary amines such as hexylamine, octylamine and hexamethylene diamine can be mentioned.

Furthermore, as a carboxylic acid, the general formula R'C0OH... (V) (wherein R6 is hydrogen or an alkyl group having 1 to 2 carbon atoms, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, or a hydroxyalkyl group) ), and dicarboxylic acids can also be used. Specific examples of carboxylic acids used in the present invention include formic acid and acetic acid.

Examples include propionic acid, butyric acid, isobutyric acid, pivalic acid, trimethylacetic acid, stearic acid, malonic acid, succinic acid, cyclohexylcarboxylic acid, benzoic acid, and the like.

Here, when preparing the aluminum-containing component [B], at least one modifier selected from alcohol, amming, and carboxylic acid is added to the organoaluminum compound in a molar ratio of 0.1 to 50, preferably 0. .2~2
It should be used in a ratio of 0 (molar ratio). For the above-mentioned reactions, conditions may be set as appropriate depending on the type of organoaluminum compound and modifier used, but usually the temperature is 0 to 100°C, preferably 5 to 50°C for 1 minute to 1 minute.
The reaction may be carried out for 5 hours, preferably 5 minutes to 1 hour.

In the first method of the present invention, [B] an aluminum-containing Ingredients, [A]
Used as a catalyst together with vanadium-containing components. This [A
There is no particular restriction on the ratio of the component [B] to the vanadium in the component [A], but the ratio of aluminum in the component [B] to vanadium in the component [A] is usually 0.1 to 5,000 (molar ratio), preferably 1. The ratio may be 200 to 200 (molar ratio).

According to the first method of the present invention, the above [A] and [B]
Using a catalyst consisting of both components, ethylene and acrylic ester and/or α-substituted acrylic ester are copolymerized in the presence of a Lewis acid.

Here, examples of the Lewis acid include Lewis acid compounds capable of forming a chain with a lone pair of electrons of a polar group, such as halogenated compounds of groups 1 to 2 or group 2 of the periodic table. Especially aluminum, boron, and zinc.

Halogenated compounds such as tin, magnesium, and antimony, such as aluminum chloride, ethylaluminum dichloride, diethylaluminium chloride, boron trichloride, zinc chloride, tin tetrachloride, alkyltin halides, magnesium chloride, antimony pentachloride, and antimony trichloride, etc. Preferred examples include aluminum chloride and ethylaluminum dichloride.

Further, 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. R in the ceremony? is hydrogen.

It represents a halogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, etc., and R1 represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl 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. In the present invention, the acrylic ester and the α-substituted acrylic ester may be one or both of the above-mentioned acrylic esters and α-substituted acrylic esters.

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.

In addition, the ratio of the Lewis acid and the acrylic ester and/or α-substituted acrylic ester to these esters is 10 or less (molar ratio) of the Lewis acid, preferably 0.2 to 1 (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, and halogenated hydrocarbons are used as the polymerization solution. Polymerization conditions include reaction temperature of -80 to 200°C1
Preferably the temperature is -50 to 100°C, and the reaction pressure is normal pressure to
100 kg/cm”G, preferably normal pressure ~30
kg/cm"G. The reaction time can be arbitrarily selected from 1 minute to 10 hours.

In the first aspect of the present invention as described above, [A] a vanadium-containing component and [B] an organoaluminum compound as an aluminum-containing component are reacted with at least one modifier selected from alcohols, amines, and carboxylic acids. By using these as catalysts, it is possible to carry out copolymerization with high activity, and the conversion rate of acrylic esters and the like can be improved.

Next, the second aspect of the present invention is that in the first aspect of the present invention described above, [
A] A vanadium compound as a vanadium-containing component, (
a) Organometallic compounds of groups I to III of the periodic table, (b)
a metal salt of at least one compound selected from the group consisting of carboxylic acids, alcohols and organic phosphoric acids; (c)
Electron donating compound.

(d) Lewis acid compounds of groups ■ to ■ of the periodic table and (e
) It is characterized in that it uses a reaction product with at least one compound selected from metal compounds of Group Ib or Group II of the Periodic Table.

The vanadium compound used in the second aspect of the present invention is as described in the first aspect of the present invention.

This vanadium compound and the above (a) and (b).

A reaction product obtained by reacting with at least one compound selected from compounds (c), (d) and (e) is used as the vanadium-containing component [A].

Here, the compound (a) is an organometallic compound belonging to Groups I to III of the periodic table, and among these compounds represented by the general formula R9, MX'□-2... (■) are preferred. R9 in this general formula (■)
represents an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms. Specific examples of R9 include a methyl group and an ethyl group.

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

Further, M represents lithium, sodium, potassium, zinc, cadmium, aluminum, boron, or gallium. Furthermore, x3 is a halogen atom, that is, chlorine, bromine,
Indicates iodine, etc. 2 is the valence of M, usually 1,2
Or 3. y is a real number with Q<y5z and indicates various values.

Specific examples of this (a) compound include methyllithium,
Alkyl lithium such as ethyl lithium, propyl lithium, butyl lithium, dialkyl zinc such as dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc, or trimethyl gallium, triethyl gallium, tripropyl gallium.

Examples include alkyl gallium compounds such as um, tributyl gallium, and the like. In addition, there are various examples of compounds in which M is aluminum, specifically trialkyl aluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and diethylaluminum monochloride. , dialkylaluminum monohalides such as diethylaluminium monopromide, diethylaluminium monoiodide, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride, or methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquipromide, Alkylaluminium sesquihalides such as 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.

Next, the 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 and calcium salts.

Manganese salts are 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. Further, in this case, it may be either saturated or unsaturated (but preferably has 1 or more carbon atoms, especially 8 or more carbon atoms). Alcohols are preferably used in the present invention, and metal salts of these alcohols, particularly magnesium salts, calcium salts, and manganese salts, are preferably used.Furthermore, the phosphoric acid constituting the metal salt of organic phosphoric acid is phosphorous acid. mono- or dialkyl esters of phosphoric acid or phosphorous acid (R'0PToO+, (R'0)ZP
H02, R'OPH! 02, etc.) and mono- or dialkyl()phosphoric acid (RSPH2O3゜R'2PH(h+
R'PHtOznato). , 1m, ::
teR' represents an alkyl group. The phosphoric acid preferably has an aliphatic hydrocarbon group, particularly one 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, nonyl group, decyl group, lauryl group, myristyl group, heptadecyl group, stearyl group,
Examples include 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 organic phosphoric acids, 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 alkylmagnesium such as dibutylmagnesium. In addition, the above-mentioned magnesium salts, 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.

The electron donating compound (c) is an organic compound or olefin containing oxygen, nitrogen, phosphorus or sulfur. Specific examples include amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, thioethers, thioesters, acid anhydrides, acid halides, aldehydes, organic acids, etc. .

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride, and 1)-)ruic anhydride; acetone; 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 naphthaldehyde
5 aldehydes; 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, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl toluate Ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, ethyl p-butoxybenzoate, ethyl 0-chlorobenzoate, ethyl naphthoate, γ-butyrolactone,
Esters having 2 to 18 carbon atoms such as δ-valerolactone, coumarin, phthalide, and ethylene carbonate; Acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzyl chloride, toluyl chloride, and anisyl chloride; methyl ether; ethyl ether, isopropyl ether, n
-C2-20 such as butyl ether, amyl ether, tetrahydrofuran, dioxane, anisole, diphenyl ether, ethylene glycol butyl ether, etc.
ethers; acid amides such as acetic acid amide, benzoic acid amide, 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.

Further, examples of the phosphorus compound include esters of phosphoric acid or phosphorous acid, and phosphines. Specifically, trimethyl phosphate and triethyl phosphate.

Phosphate esters or halides thereof such as tributyl phosphate, triphenyl phosphate, diphenyl phosphate chloride, phenyl phosphate dichloride, methyl phosphite, ethyl phosphite, butyl phosphite.

triphenyl phosphite, diphenyl phosphite chloride,
Examples include phosphorous acid esters such as phenylphosphite dichloride or halides thereof, and phosphines such as triethylphosphine, tributylphosphine, diphenylchlorophosphine, and phenyldichlorophosphine.

Among these, esters, ethers, ketones, amines, phosphines, acid anhydrides and the like are preferred.

In particular, alkyl esters of aromatic carboxylic acids, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid having 1 to 1 carbon atoms;
Alkyl esters of No. 4 are preferred, and aromatic ketones such as benzoquinone, aromatic carboxylic acid anhydrides such as benzoic anhydride, ethers such as tetrahydrofuran, dioxane, and ethylene glycol butyl ether are also preferred. In addition, olefins include ethylene and plastic.
Examples include monoolefins and diolefins having 1 to 20 carbon atoms, such as t-robilene, butene, butadiene, hexene, and octene, and styrene derivatives.

Furthermore, as the compound (d), a Lewis acid compound of group ff-V of the periodic table, aluminum, boron, zinc,
tin, magnesium, antimony, 3. ’ halogenated compounds, such as aluminum chloride.

Ethylaluminum dichloride, diethylaluminum chloride, boron trichloride, zinc chloride, tin tetrachloride, alkyltin chloride, alkyltin bromide, magnesium chloride, antimony pentachloride.

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

Further, the compound (e) is a metal compound of group RB or group Ⅰ of the periodic table. Specific examples of compounds (,3) include silver chloride (AgC1), cuprous chloride (cuC1),
), nickel chloride (NtCh) + ferrous chloride (Fe
nickel diacetylacetonate, iron diacetylacetonate, tris(triphenylphosphine)nickel (Ni (P(cJs))
3) Complex compounds such as z), nickel chloride hydrate (Ni
Ch HzO).

Complex of ferrous chloride and triphenylphosphine (FeC
Examples include coordination complexes such as 1z (P(06H5)3) z), and organic salts such as nickel acetate.

In the second aspect of the present invention, [A] a vanadium compound as a vanadium-containing component, and (a) above.

A reaction product with at least one compound selected from compounds (b), (c), (d) and (e) is suitable. For the reaction between the two, conditions may be set as appropriate depending on the type of compound used, but usually the reaction temperature is -50 to 100°C, preferably -20 to 80°C for 1 minute to 10 hours, preferably What is necessary is just to let it react for 5 minutes - 5 hours. Also, the amount of both used is the former, that is, the vanadium compound, and the latter, that is, the above-mentioned (a) and (b).
, (c).

At least one compound selected from compounds (d) and (e) should be selected in a range of 0.0001 to 50 (molar ratio), preferably 0.1 to 10 (molar ratio).

According to the second aspect of the present invention, using a catalyst consisting of both components [A] and [B], ethylene and acrylic ester and/or α- Ethylene copolymers are produced by copolymerizing substituted acrylic esters. Here Lewis acid, acrylic acid ester.

The α-substituted acrylic ester is as already described in the first aspect of the present invention. Further, the conditions for type 2 polymerization and the like are also as already described in the first aspect of the present invention.

In the second aspect of the present invention such as on the ridge, [B] an organoaluminum compound and at least one selected from alcohol, amine, and carboxylic acid as the aluminum-containing component.
[A] A vanadium compound as a vanadium-containing component, (a) an organometallic compound of Groups 1 to 2 of the periodic table, (b) a carboxylic acid, an alcohol, and an organic phosphoric acid. a metal salt of at least one compound selected from the group consisting of; (c) an electron-donating compound; (d) a Lewis acid compound of Groups ■ to ■ of the Periodic Table; and (e) Group Ib or ■ of the Periodic Table. Copolymerization can be carried out with even higher activity by using a reaction product with at least one compound selected from the group metal compounds. Furthermore, the conversion rate of acrylic esters and the like can be further improved.

Therefore, according to the present invention, staining property,
Ethylene copolymers with excellent printability, adhesive properties, etc. can be produced.

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

Example 1 (1) Preparation of aluminum-containing catalyst component Into a 25 ml flask purged with argon, 5 ml of hexane and a hexane solution of 1 mmol of triethylaluminum were added, and while stirring, a hexane solution of ethanol (1 mmol/ml) was added.
l) 0.75 ml) was added dropwise at 25°C,
The reaction resulted in an aluminum-containing catalyst component.

(2) Production of ethylene copolymer 300 ml of hexane was placed in a 500 ml reaction vessel purged with argon, and then a hexane slurry containing 8 mmol of ethyl acrylate and 8 mmol of ball-milled aluminum chloride was added.

Next, after raising the temperature to 50°C, ethylene was added at l kg/
0.02 mmol of vanadium tetrachloride as a vanadium-containing component, the total amount of the aluminum-containing catalyst component prepared in (L) above as an aluminum-containing component, and then 2 kg of ethylene
/ am "Continuously introduce 3 to maintain G.
A time copolymerization reaction was performed. After the copolymerization reaction was completed, the ethylene was depressurized, the reaction product was poured into methanol, and the copolymer was collected by filtration. The obtained copolymer was treated with a mixture of hydrochloric acid and methanol, and then extracted with acetone for 5 hours.

Next, the extracted residue was dried under reduced pressure at 80° C. for 2 hours to obtain 3.32 g of a copolymer.

The activity of this catalyst was 6.5 kg/g.vanadium. When this copolymer was subjected to infrared absorption spectrum analysis, absorption due to the carbonyl group at 1730 cm-J and absorption due to the ether bond at 1160 cm-' were observed, and the content of ethyl acrylate in the copolymer was 2.
．． It was found to be 1% by weight. Further, the conversion rate of ethyl acrylate to the copolymer was 4.4%10, Ol mmol vanadium.

□ Comparative Example 1 The same procedure as in Example 1 was conducted except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 1.6 kg/g vanadium, the content of ethyl acrylate was 0.7% by weight, and the conversion rate of ethyl acrylate to the copolymer was 0.8%, 10.01 mmol.・It was vanadium.

Example 2 In Example 1, 0.02 mmol of vanadium trisacetylacetone was used as the vanadium-containing component,
The same procedure as in Example 1 was conducted except that a reaction product of 1 mmol of diethylaluminum monochloride and 0.5 mmol of ethanol was used as the aluminum-containing component. As a result, the catalyst activity was 3.71 qr/g vanadium, the content of ethyl acrylate was 3.7% by weight, and the conversion rate of ethyl acrylate to the copolymer was 8.
．． It was 8% 10.01 mmol vanadium.

Comparative Example 2 The same procedure as in Example 2 was conducted except that diethylaluminium monochloride was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 3.7 kg/g vanadium, the content of ethyl acrylate was 1.6% by weight, and the conversion rate of ethyl acrylate to the copolymer was 3.8%10
．． 01 mmol vanadium.

Example 3 (1) Preparation of vanadium-containing catalyst component 1.50 mJ of heptane was placed in a 300 ml flask purged with argon, and 4.7 mmol of vanadium tetrachloride was added at 25°C and stirred. 50 ml of a hebutane solution containing 1.57 mmol of butyl gallium was added dropwise over 5 minutes, and the mixture was reacted for 3 hours. The yield of vanadium, the reddish-purple solid catalyst component, was 70 mol%.

(2) Preparation of aluminum-containing catalyst component Add 5 ml of hexane and 1 mmol of triethylaluminum to a flask with an internal volume of 25+1 and which has been purged with argon, and while stirring,
Add 0.75 mmol of ethanol in hexane solution to this.
The aluminum-containing catalyst component was obtained by dropwise addition and reaction at 5°C.

(3) Production of ethylene copolymer A 500 ml reaction vessel purged with argon was charged with 300 ml of hexane, and 8 mmol of ethyl acrylate and 8 mmol of ball milled aluminum chloride were added thereto. Next, the temperature was raised to 50'C and ethylene was introduced until it reached l kg/cm''G.
Add 0.02 mmol of the vanadium-containing catalyst component prepared in the above (1) as the vanadium-containing component, the total amount of the aluminum-containing catalyst component prepared in the above (2) as the aluminum catalyst component, and further add 2 kg/c of ethylene.
The copolymerization reaction was carried out for 3 hours by continuously introducing m 2 (,). After the copolymerization reaction was completed, the reaction product was poured into methanol, and the copolymer was collected by filtration.

Further, this copolymer was treated with a mixture of hydrochloric acid and methanol, and then extracted with acetone for 5 hours. The obtained extraction residue was dried under reduced pressure at 80°C for 2 hours. As a result, the yield of copolymer was 15.1 g, and the catalytic activity was 14.9 g.
kg/g・vanadium. In addition, the content of ethyl acrylate in the copolymer was 1.0% by weight, and the conversion rate of ethyl acrylate to the copolymer was 17.0%10.0
It was 1 mmol vanadium.

Comparative Example 3 The same procedure as in Example 3 was conducted except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 7.1 kg/g vanadium, the content of ethyl acrylate was 0.1% by weight, and the conversion rate of ethyl acrylate to the copolymer was 0.5%, 10.01 mmol.・It was vanadium.

Example 4 In preparing a vanadium-containing catalyst component, 16 mmol of vanadium oxytrichloride was used instead of vanadium tetrachloride, and the amount of tri-n-butyl gallium used was 2.
A gray-green vanadium-containing catalyst component was obtained in the same manner as in Example 3 (1) except that the amount was 9 mmol.

An ethylene copolymer was obtained in the same manner as in Example 3 (3) except that this vanadium-containing catalyst component was used as the vanadium-containing component. The catalyst activity in this case is 2.5k
g/g vanadium, the content of ethyl acrylate was 10.6% by weight, and the conversion rate of ethyl acrylate to the copolymer was 19.8%, 10.01 mmol vanadium.

Comparative Example 4 The same procedure as in Example 4 was conducted except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 2.1 kg/g vanadium, the content of ethyl acrylate was 1.6% by weight, and the conversion rate of ethyl acrylate to the copolymer was 2.2%, 10.01 mmol. -Vanadium- Example 5 In Example 3, 7.1 mmol of vanadium tetrachloride and 35.1 mmol of tetrahydrofuran were used as vanadium-containing components.
Example 3 except that the reaction product with 5 mmol was used.
I did the same thing. The catalyst activity in this case is 2.5 kg
/g.vanadium, the content of ethyl acrylate was 7.9% by weight, and the conversion rate of ethyl acrylate to the copolymer was 17.9%, 10.01 mmol vanadium.

Comparative Example 5 The same procedure as in Example 5 was conducted except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 2.3 kg/g vanadium, the content of ethyl acrylate was 3.3% by weight, and the conversion rate of ethyl acrylate to the copolymer was 4.9%10.01 It was millimole vanadium.

Example 6 Example 3 was carried out in the same manner as in Example 3, except that a reaction product of 7.1 mmol of vanadium tetrachloride and 35.5 mmol of dioxane was used as the vanadium-containing component. As a result, the catalyst activity was 10°0+tg/g・
It is vanadium, and the content of ethyl acrylate is 2.4
The weight percent and conversion of ethyl acrylate to copolymer was 15.4%, 10.01 mmol vanadium.

Comparative Example 6 In Example 6, triethylaluminum is reacted with ethanol as the aluminum-containing component. Example 6 was carried out in the same manner as in Example 6, except that the sample was used without any liquid. In this case, the catalyst activity was 3.4 kg/g vanadium, the content of ethyl acrylate was 3.4% by weight, and the conversion rate of ethyl acrylate to the copolymer was 4.1%10.
01 mmol vanadium.

Example 7 In Example 3, 4.7 mmol of vanadium tetrachloride and 2 mmol of triphenylphosphine were used as vanadium-containing components.
Example 3 was carried out in the same manner as in Example 3, except that the reaction product with 3.5 mmol was used. The catalyst activity in this case is 5.
The content of ethyl acrylate was 4.0% by weight, and the conversion rate of ethyl acrylate to the copolymer was 13.8%, 10.01 mmol vanadium.

Comparative Example 7 The same procedure as in Example 7 was conducted except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 5.3 kg/g° vanadium, the content of ethyl acrylate was 1.5% by weight, and the conversion rate of ethyl acrylate to the copolymer was 5.1%, 10.01 mmol.・It was vanadium.

Example 8 In Example 3, 1 mmol of vanadium tetrachloride and 1 mmol of dioctyl magnesium phosphate were used as vanadium-containing components.
The same procedure as in Example 3 was carried out except that the reaction product with mmol was used. What is the catalytic activity in this case? , 11q
r/g vanadium, the content of ethyl acrylate was 4.0% by weight, and the conversion rate of ethyl acrylate to the copolymer was 13.8%, 10.01 mmol vanadium.

Comparative Example 8 The same procedure as in Example 8 was carried out except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol. In this case, the catalyst activity was 2.1 kg/g vanadium, the content of ethyl acrylate was 1.3% by weight, and the conversion rate of ethyl acrylate to the copolymer was 1.7%, 10.01 mmol.・It was vanadium.

Example 9 (1) Preparation of vanadium-containing catalyst component Heptane Loom 12 was placed in a 300 ml flask purged with argon, 4.7 mmol of vanadium tetrachloride was added at 5°C, and then 4.7 mmol of hebutane was added to tetrahydrofuran. Solution Ion/ was added dropwise over 5 minutes, and the reaction was allowed to proceed for 1 hour with stirring. Continued at 20℃
A solution of 1.56 mmol of tri-n-butylgallium in hebutane at 10 mA was added dropwise over 5 minutes.
A time reaction was performed. After the reaction was completed, the dark green solid product was washed and collected to obtain a vanadium-containing catalyst component.

(2) Production of ethylene copolymer In Example 3, the vanadium-containing component was
Example 3 was carried out in the same manner as in Example 3, except that the vanadium-containing catalyst component prepared in ) was used.

As a result, the catalyst activity was 4.2 kg/g.vanadium, the content of ethyl acrylate was 1.4% by weight, and the conversion rate of ethyl acrylate to the copolymer was 3.7%10.
01 mmol vanadium.

Example 10 Example 9 was carried out in the same manner as in Example 9, except that a reaction product of 1 mmol of triethylaluminum and 0.75 mmol of propionic acid was used as the aluminum-containing component. As a result, the catalyst activity was 4.5 kg
/g.vanadium, the content of ethyl acrylate was 2.7% by weight, and the conversion rate of ethyl acrylate to the copolymer was 7.8%, 10.01 mmol vanadium.

Example 11 Example 9 was carried out in the same manner as in Example 9, except that a reaction product of 1 mmol of triethylaluminum and 0.75 mmol of 2-ethylhexanol was used as the aluminum-containing component. As a result, the catalytic activity was 5
．． The content of ethyl acrylate was 3.3% by weight, and the conversion rate of ethyl acrylate to the copolymer was 12.0% and 10.01 mmol vanadium.

Example 12 Example 9 was carried out in the same manner as in Example 9, except that a reaction product of 1 mmol of triethylaluminum and 0.75 mmol of di-n-butylamine was used as the aluminum-containing component.

As a result, the catalytic activity was 4.2 kg/g vanadium, the content of ethyl acrylate was 3.1% by weight,
The conversion rate of ethyl acrylate to the copolymer was 8.3% or 10.01 mmol vanadium.

Example 13 The same procedure as in Example 9 was carried out except that a reaction product of 1 mmol of triethylaluminum and 0.75 mmol of cyclohexylcarboxylic acid was used as the aluminum-containing component.

As a result, the catalyst activity was 5.5 kg/g vanadium, the content of ethyl acrylate was 4.0% by weight, and the conversion rate of ethyl acrylate to the copolymer was 13.8%10
．． 01 mmol vanadium.

Comparative Example 9 The same procedure as in Example 9 was carried out except that triethylaluminum was used as the aluminum-containing component without reacting with Etacool. As a result, the catalyst activity was 4.4 kg/g vanadium, the content of ethyl acrylate was 0.7% by weight, and the conversion rate of ethyl acrylate to the copolymer was 1.9%10.0
Example 14 (1) Preparation of vanadium-containing catalyst component Into a 300 ml flask, 100 ml of heptane was added.
1, a hexane slurry of 4.7 mmol of vanadium tetrachloride and 4.7 mmol of ball-milled aluminum chloride was added, and the mixture was reacted at 20° C. for 1 hour.

Next, 1.56 mmol of tri-n-butyl gallium was added dropwise to this and reacted for 3 hours to obtain a purple solid catalyst component.

(2) Production of ethylene copolymer In Example 3, the vanadium-containing component was
Example 3 was carried out in the same manner as in Example 3, except that the vanadium-containing catalyst component prepared in ) was used.

As a result, the catalyst activity was 22.9 kg/g vanadium, the content of ethyl acrylate was 0.6% by weight, and the conversion rate of ethyl acrylate to the copolymer was 8.7%10
．． 01 mmol vanadium.

Comparative Example 10 The same procedure as Example 14 was carried out except that triethylaluminum was used as the aluminum-containing component without reacting with Etacool. As a result, the catalyst activity was 7.3 kg/g.vanadium, the content of ethyl acrylate was 0.16% by weight, and the conversion rate of ethyl acrylate to the copolymer was 0.7%10.
01 mmol vanadium.

Example 15 (1) Preparation of vanadium-containing catalyst component Into a flask with an internal volume of 300 m2, 80 m2 of hexane was added.
Add amimoles of nickel chloride and 7 mmoles of vanadium oxytrichloride, and add 2 mmoles of nickel chloride while stirring at 50°C.
Allowed time to react. Next, 3.9 mβ of a hexane solution containing 0.66 mmol of tri-n-butyl gallium was added thereto, and the mixture was reacted at 40'C for 3 hours to obtain a dark green solid catalyst component.

(2) Production of ethylene copolymer In Example 3, the vanadium-containing component was
Example 3 was carried out in the same manner as in Example 3, except that the vanadium-containing catalyst component prepared in ) was used.

As a result, the catalyst activity was 3.8 kg/g vanadium, the content of ethyl acrylate was 8.3% by weight, and the conversion rate of ethyl acrylate to the copolymer was 17.2%.
It was 10.01 mmol vanadium.

Comparative Example 11 Example 15 was carried out in the same manner as in Example 5, except that triethylaluminum was used as the aluminum-containing component without reacting with ethanol.

As a result, the catalyst activity was 2.6 kg/g vanadium, the content of ethyl acrylate was 6.8% by weight, and the conversion rate of ethyl acrylate to the copolymer was 11.5%10
．． 01 mmol vanadium.

Claims (2)

[Claims] (1) Copolymerizing ethylene and acrylic ester and/or α-substituted acrylic ester in the presence of a Lewis acid using a catalyst consisting of [A] a vanadium-containing component and [B] an aluminum-containing component as a catalyst. In producing an ethylene copolymer, [B] an organoaluminum compound and at least one selected from alcohol, amine, and carboxylic acid as the aluminum-containing component;
A method for producing an ethylene copolymer, which comprises using a reaction product of a species with a modifier. (2) Copolymerizing ethylene and acrylic ester and/or α-substituted acrylic ester using a catalyst consisting of [A] a vanadium-containing component and [B] an aluminum-containing component and in the presence of a Lewis acid. In producing an ethylene copolymer, [B] an organoaluminum compound and at least one selected from alcohol, amine, and carboxylic acid as the aluminum-containing component;
[A] A vanadium compound as a vanadium-containing component, (a) an organometallic compound of groups I to III of the periodic table, (b) a carboxylic acid, an alcohol, and an organic phosphoric acid. a metal salt of at least one compound selected from the group consisting of (c) an electron-donating compound, (d) a Lewis acid compound of Groups II to V of the Periodic Table, and (e) a group Ib of the Periodic Table or 1. A method for producing an ethylene copolymer, comprising using a reaction product with at least one compound selected from Group VIII metal compounds.