JPH0699522B2 - Process for producing ethylene copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an ethylene copolymer, and more specifically, it has a high conversion rate of acrylic acid ester and / or α-substituted acrylic acid ester into the copolymer, and further the acrylic acid ester and / or The present invention relates to a method for efficiently producing an ethylene copolymer having a high α-substituted acrylate content.

In general, polyethylene is a resin having excellent properties, but since it is chemically inert, it 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 and 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 controlled arbitrarily. In addition, Japanese Patent Publication No. 48-37755 and Japanese Patent Laid-Open No. 59-59
The method described in JP-A-43003 has 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 determined that a vanadium compound as a transition metal compound is an electron donating compound and an organometallic compound of Group I to III of the periodic table. (However, it is limited to those containing an alkyl group.) As one component of the catalyst, a combination of this and an organoaluminum compound as an organometallic component is used as a catalyst to obtain copolymerization activity and acrylic acid. The inventors have found that the conversion rate of acid ester and / or α-substituted acrylic acid ester into a copolymer can be improved, and have completed the present invention.

That is, 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
Using a reaction product of (a) a vanadium compound, (b) an electron-donating compound, and (c) an organometallic compound of Groups I to III of the periodic table (provided that it contains an alkyl group), and [B] A method for producing an ethylene copolymer, characterized in that an organoaluminum compound is used as an organometallic compound of Groups I to III of the periodic table, and a halogen-containing aluminum compound is used as a Lewis acid compound. .

The catalyst component [A] in the present invention is a transition metal-containing component, and includes (a) a vanadium compound, (b) an electron-donating compound, and (c) an organometallic compound of Group I to III of the periodic table (provided that (Limited to those containing an alkyl group).

Here, the vanadium compound (a) is not particularly limited, but it is usually represented by the general formula M ¹ (OR ¹ ) lX ¹ mYn ………… [2] [In the formula, M ¹ represents vanadium and R ¹ 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 . ] Specifically, the above-mentioned general formula [2]
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
₄ H ₉ ) ₃ and other vanadium alkoxides; 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 an electron donating compound.

Here, the electron-donating compound (b) 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 and the like. .

More specifically, organic acids such as aromatic carboxylic acids such as benzoic acid and p-oxybenzoic acid; acid anhydrides such as succinic anhydride, benzoic anhydride and p-toluic anhydride; acetone, methyl ethyl ketone, Methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone and other ketones having 3 to 15 carbon atoms; acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde,
2 to 15 carbon atoms such as tolualdehyde and naphthaldehyde
Aldehydes of 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, methacrylic acid Methyl, ethyl crotonate, ethyl bivalate, 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 ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, p
-Ethyl butoxybenzoate, ethyl o-chlorobenzoate, ethyl naphthoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other C2-C18 esters; acetyl chloride, benzyl chloride, toluyl C2-C15 acid halides such as acid chloride and anisic acid chloride; carbon such as methyl ether, ethyl ether, isopropyl ether, n-butyl ether, amyl ether, tetrahydrofuran, dioxane, anisole, zophenyl ether, ethylene glycol butyl ether Ethers of the number 2 to 20; Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; triethylamine, tributylamine, N, N'-dimethylpiperazine, tribenzylamine, aniline, pyridine, picoline, tetrame Amines such as ethylene diamine; acetonitrile, benzonitrile, nitriles such as tolunitrile; tetramethylurea, nitrobenzene, and the like can be exemplified lithium butyrate. Of these, preferred are esters, ethers, ketones, amines, acid anhydrides and the like. Above all,
Alkyl esters of aromatic carboxylic acids, such as benzoic acid, p-methoxybenzoic acid, p-ethoxybenzoic acid, toluic acid, and other alkyl carboxylic acids having 1 to 4 carbon atoms are preferable, and aromatic esters such as benzoquinone are also preferable. Group aromatic ketones, aromatic carboxylic acid anhydrides such as benzoic anhydride,
Ethers such as tetrahydrofuran, dioxane and ethylene glycol butyl ether are also preferable. As olefins, ethylene, propylene, butene, butadiene, hexene, octene and the like have 1 to 1 carbon atoms.
Examples include 20 monoolefins, diolephins, and styrene derivatives.

Subsequently, the component (c) used for preparing the catalyst component [A] is an organometallic compound of Groups I to III of the Periodic Table (provided that it contains an alkyl group).

Here, an organometallic compound of Group I to Group III of the periodic table (provided that
Limited to those containing an alkyl group. ) Is a general formula R ² qM ² X ² pq ………… [3] [In the formula, M ² represents a metal of Group I to III of the periodic table, and R ² represents an alkyl group having 1 to 20 carbon atoms. X ² represents 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, with gallium, boron and magnesium being particularly preferred.

Here, an organometallic compound of Group I to Group III of the periodic table (provided that
Limited to those containing an alkyl group. ), Trimethylgallium, triethylgallium,
Alkylgallium compounds such as tripropylgallium and tributylgallium; Alkylmagnesium compounds such as ethylbutylmagnesium and dibutylmagnesium;
Methyl lithium, ethyl lithium, propyl lithium,
Alkyl lithium compounds such as butyl lithium; dialkyl zinc compounds such as dimethyl zinc, diethyl zinc, dipropyl zinc, dibutyl zinc and the like.

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

Next, in the present invention, an organoaluminum compound is used as the catalyst component [B]. Specific examples of the organoaluminum compound include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and diethylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoiodide, Dialkyl aluminum monohalides such as diisopropyl aluminum monochloride, diisobutyl aluminum monochloride and dioctyl aluminum monochloride or alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide and butyl aluminum sesquichloride are suitable. , Mixtures of these were also mentioned as 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, preferably 1 to 5000, of the metal atom of the catalyst component [B] to the metal atom of the transition metal compound in the catalyst component [A]. 2
The ratio may be 000 (molar 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, the Lewis acid compound is a Lewis acid compound capable of forming a complex with a lone electron pair of a polar group, and a halogen-containing aluminum compound is used. Specific examples of the halogen-containing aluminum compound include aluminum chloride, ethylaluminum dichloride, diethylaluminum chloride and the like.

In addition, the acrylic acid ester and / or α-substituted acrylic acid ester copolymerized with ethylene has 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, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, and other acrylate esters, methyl methacrylate. , Ethyl methacrylate, butyl methacrylate, methacrylic acid
Examples thereof include methacrylic acid esters such as 2-ethylhexyl and phenyl methacrylate.

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

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 solution. The polymerization conditions include a reaction temperature of 0 to 200 ° C, preferably 20 to 100 ° C,
Reaction pressure is normal pressure to 50 kg / cm ² G, preferably normal pressure to 30 kg / cm
It is ² G. The molecular weight at the time of polymerization may be adjusted by a known means such as hydrogen. The reaction time may be appropriately selected from 0.1 minutes to 20 hours, preferably 1 minute to 10 hours.

In the present invention, as a catalyst, a reaction product of a vanadium compound as a transition metal compound, an electron donating compound, and an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group). Since it is used in combination with an organoaluminum compound as an organometallic component, the copolymerization activity can be improved.

Therefore, according to the method of the present invention, the conversion rate of acrylic acid ester and / or α-substituted acrylic acid ester into a copolymer can be improved, and at the same time, acrylic acid ester and / or α-substituted acrylic acid ester can be obtained. A copolymer having a high content of is obtained.

Therefore, the present invention can be effectively utilized 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] After replacing a 300 ml four-necked flask equipped with a dropping funnel and a stirrer with argon, 100 ml of heptane was added and 0.5 ml (4.7 mmol) of vanadium tetrachloride was added at 5 ° C. Then, 10 ml of a heptane solution of ethyl benzoate (0.47 mmol / ml) as an electron-donating compound was added dropwise over 5 minutes, and the reaction was carried out for 1 hour. Then, the liquid temperature was raised to 20 ° C. and 5 ml of 10 ml of a heptane solution of tri-n-butylgallium (0.156 mmol / ml) was added.
The mixture was added dropwise over a period of 3 minutes, and the reaction was performed for 3 hours. The supernatant of the obtained dark green solid product was washed 5 times with heptane to obtain a solid catalyst component.

(2) Manufacture of copolymer 300 ml of hexane in a pressure vessel equipped with a stirrer and replaced with argon.
And 0.87 ml (8 mmol) of ethyl acrylate and aluminum chloride 8 ball-milled as Lewis acid compound
The mmol hexane slurry was added sequentially. Next, this was heated to 50 ° C., ethylene was introduced so as to be 1 kg / cm ² G, and then a hexane solution of triethylaluminum (2
1.25 ml of the catalyst component [A] obtained in (1) above was added. 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 5.86 g of a white copolymer.

The activity of this catalyst was 2.3 kg / g.vanadium. The results of the obtained copolymer analyzed by infrared absorption spectrum (IR analysis) the were line summer, absorption attributed to the ester bonds to 1730 cm ^-1 and 1160 cm ^-1 was observed, the absorbance ratio of more methylene chain and the carbonyl group The content of ethyl acrylate in the copolymer obtained from the above was 2.0% by weight. The conversion of ethyl acrylate was 14.6%.

Example 2 14.5 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 16 mmol.

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

Example 3 3.57 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 40 mmol.

The activity of this catalyst was 1.4 kg / g.vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate in the copolymer was 9.7% by weight, and the conversion 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 (1) of Example 1 except that 4.7 mmol of dioxane was used as the electron donating compound.

(2) Production of Copolymer The amounts of ethyl acrylate and aluminum chloride used in (2) of Example 1 were each 20 mmol, and the solid catalyst component [A] obtained in (2) above was used. Except for the above, copolymer 7.90 was prepared in the same manner as in (2) of Example 1.
got g. The activity of this catalyst was 3.1 kg / g.vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate in the copolymer was 6.0% by weight, and the conversion of ethyl acrylate was 23.7%.

Example 5 A copolymer (6.11 g) was obtained in the same manner as in (4) of Example 4 except that the amounts of ethyl acrylate and aluminum chloride used in (4) of Example 4 were each 40 mmol.

The activity of this catalyst was 2.4 kg / g.vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate in the copolymer was 11.0% by weight, and the conversion 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 in (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 the solid catalyst component [A] obtained in (1) above was used in (2) of Example 1
6.62 g of a copolymer was obtained in the same manner as in (2). The activity of this catalyst was 2.6 kg / g.vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate in the copolymer was 1.3% by weight, and the conversion 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 (1) of Example 1 except that 4.7 mmol of vinyl acetate was used as the electron-donating compound.

(2) Production of copolymer Example 1 except that the solid catalyst component [A] obtained in (1) above was used in (2) of Example 1
A copolymer (8.66 g) was obtained in the same manner as in (2). The activity of this catalyst is 3.4 kg / g vanadium. The results of IR analysis were the same as in Example 1. The content of ethyl acrylate in the copolymer was 1.7% by weight and the conversion of ethyl acrylate was 18.4%.

Example 8 (1) Preparation of catalyst component [A] A light purple solid catalyst component was obtained in the same manner as in (1) of Example 1 except that 4.7 mmol of tetrahydrofuran was used as the electron-donating compound.

(2) Production of copolymer Example 1 except that the solid catalyst component [A] obtained in (1) above was used in (2) of Example 1
11.21 g of a copolymer was obtained in the same manner as in (2). The activity of this catalyst was 4.4 kg / g.vanadium. The results of IR analysis were the same as in Example 1, and the content of ethyl acrylate in the copolymer was 1.2% by weight and the conversion of ethyl acrylate was 16.8%.

Example 9 (1) Preparation of catalyst component [A] A black-brown solid catalyst component was obtained in the same manner as in (1) of Example 1 except that 4.7 mmol of triethylamine was used as the electron-donating compound.

(2) Production of copolymer Example 1 except that the solid catalyst component [A] obtained in (1) above was used in (2) of Example 1
Copolymer (5.09 g) was obtained in the same manner as in (2). The activity of this catalyst was 2 kg / g.vanadium. The results of 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 of ethyl acrylate was 10.2%.

Example 10 Except that 8 mmol of methyl methacrylate was used in place of ethyl acrylate in (2) of Example 1 and the catalyst component [A] obtained in (4) of Example 4 was used. 8.5 g of a copolymer was obtained in the same manner as in (2) of Example 1. The activity of this catalyst was 3.3 kg / g.vanadium. The results of IR analysis were the same as in Example 1, and the content of methyl methacrylate in the copolymer was 5.2% by weight and the conversion of methyl methacrylate was 30.7%.

Comparative Example 1 3.82 g of copolymer 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. Got The activity of this catalyst was 1.5 kg / g.vanadium.
The results of 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 of ethyl acrylate was 4.8%, which were both low.

[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 (2)

[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
Using a reaction product of (a) a vanadium compound, (b) an electron-donating compound, and (c) an organometallic compound of Groups I to III of the periodic table (provided that it contains an alkyl group), and [B] A method for producing an ethylene copolymer, which comprises using 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. (C) An organometallic compound of Groups I to III of the Periodic Table (provided that it contains an alkyl group),
Lithium, sodium, potassium, zinc, cadmium,
The method according to claim 1, which is an organic compound of aluminum, boron or gallium.