JPH0699519B2 - 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.

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 and an acrylate ester in the presence of a Lewis acid compound. However, in this case, the copolymerization activity cannot be said to be 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-mentioned conventional methods, the present inventors have previously identified a vanadium compound as a transition metal compound with an organometallic compound of Group I to III of the periodic table (provided that an alkyl group is used). Containing one of the above) as a catalyst component, and by combining this with an organoaluminum compound as an organometallic component to use as a catalyst, the copolymerization activity and the acrylate ester They have found that the conversion rate to a polymer 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.) In producing an ethylene copolymer by copolymerizing an acrylic acid ester and / or an α-substituted acrylic acid ester represented by An organoaluminum is used as a organometallic compound of Group I to III of the periodic table, using a reaction product with an organometallic compound of Group I to III (however, those containing an alkyl group). A method for producing an ethylene copolymer, which comprises using a halogen-containing aluminum compound as a Lewis acid compound together with a compound. It

The catalyst component [A] in the present invention is a transition metal-containing component, and is a vanadium compound and an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group).
The reaction product with is used.

Here, the transition metal compound is represented by the general formula M ¹ (OR ³ ) lX ¹ mYn [I] [wherein M ¹ represents vanadium, R ³ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, or It represents 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
₄ H ₉ ) ₃ and other vanadium alkoxides; dicyclopentadienyl vanadium chloride and other cyclopentadienyl vanadium derivatives; and V (acac) ₃ , V (acac) ₂ and other vanadium acetylacetonate compounds. Here, acac is an acetylacetonate group,
That is, it represents an acetylacetone ion.

In the present invention, a reaction product of the vanadium compound as described above and an organometallic compound of Groups I to III of the periodic table (provided that it contains an alkyl group) is used as the catalyst component [A]. .

Here periodic table I~III organometallic Group of No. of the general formula R ⁴ qM ² X ² p _- in q (II) [wherein, M ² represents a periodic table I~III metals , R ⁴ represents an alkyl group having 1 to 20 carbon atoms, and 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 reaction of the above vanadium compound with an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group) is generally -50 to 100 ° C, preferably 20 to 80 ° C.
It is carried out at a temperature of ° C for 0.5 minutes to 20 hours, preferably 5 minutes to 5 hours. The charge amount of both is former / latter = 0.01 in terms of molar ratio.
-50, preferably 0.1-5.

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]. Specific examples of the organoaluminum compound include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and diethylaluminium 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 preferred. Yes Mixtures thereof may be 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 and ethylaluminum dichloride.

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 is a compound represented by). Specifically, acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate and benzyl acrylate, methyl methacrylate, Ethyl methacrylate, butyl methacrylate, methacrylic acid 2-
Methacrylic acid esters such as ethylhexyl and phenyl methacrylate can be mentioned.

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 0.2 with respect to 1 of these esters.
-1 (molar ratio).

There are no particular restrictions on the type of polymerization, slurry polymerization, solution polymerization,
Both gas phase polymerization and the like are possible, and continuous polymerization and discontinuous polymerization are also 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 250 ° C., preferably 20 to 150 ° C., and a reaction pressure of atmospheric pressure to 50 kg / cm ² G, preferably atmospheric pressure to 30 kg / cm 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 and an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group) is an organometallic compound. Since the organoaluminum compound as a component is used in combination, the copolymerization activity can be improved.

Therefore, according to the present invention, the conversion rate of acrylic acid ester and / or α-substituted acrylic acid ester into a copolymer can be improved.

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] In a 300 ml three-necked flask equipped with a stirrer, 80 ml of hexane and 0.66 ml (7 mmol) of vanadium trichloride were added, and then hexane of trinormal butyl gallium was added thereto. 3.9 ml of the solution [0.17 mmol / ml] was added dropwise over 30 minutes. Next, the reaction was carried out at 20 ° C. for 3 hours, and the produced solid catalyst component [A] was washed 5 times with 100 ml of hexane, and finally the total volume was adjusted to 200 ml. The vanadium concentration in the slurry of this catalyst component was 21 mmol /.

(2) Manufacture of copolymer To a 500 ml pressure vessel equipped with a stirrer, 300 ml of hexane under an argon atmosphere and a hexane slurry of 2.67 g (20 mmol) of aluminum chloride finely pulverized as a Lewis acid were added, and ethyl acrylate 2.17 was added thereto. ml (2 mmol) was added and stirred at 50 ° C. Then, 2 mmol of triethylaluminum as a catalyst component [B] was added thereto, and 2.38 ml of the slurry of the above catalyst component [A] (0.05 mmol as vanadium) was added thereto, and at 50 ° C., the total pressure of ethylene was adjusted to 2 kg / cm ² G. To be introduced continuously 3
Time polymerization was performed. After completion of the polymerization reaction, the product was washed and decalcified with a mixed solution of methanol and hydrochloric acid, and further extracted with acetone for 6 hours. Dry the residual product
5.35 g of copolymer was obtained.

The activity of this catalyst was 2.10 kg / g.vanadium. The obtained copolymer was analyzed by infrared absorption spectrum (IR analysis). As a result, absorptions due to ester bonds were observed at 1160 cm ^-1 and 1730 cm ^-1 and the absorption between the methylene chain and the carbonyl group was confirmed. The ethyl acrylate content determined from the density ratio was 10% by weight. The conversion of ethyl acrylate was 26.9%.

Example 2 (1) Preparation of catalyst component [A] In place of the trinormal butyl gallium used in (1) of Example 1, 0.47 ml (2.3 mmol) of triethylboron was dissolved in 20 ml of hexane, and the reaction temperature was used. To
A slurry having a vanadium concentration of 26.1 mmol / m was obtained in the same manner as in (1) of Example 1 except that the temperature was 40 ° C.

(2) Manufacture of copolymer Instead of the slurry of the catalyst component [A] in (2) of Example 1, 1.91 ml of the slurry of the catalyst component [A] obtained in the above (1) (0.05 mmol as vanadium). Except that the copolymer 7.30 was used in the same manner as in (2) of Example 1.
got g.

The activity of this catalyst was 2.90 kg / g.vanadium. The IR analysis result of the obtained copolymer was the same as that of Example 1, and the content of ethyl acrylate was 5.7% by weight. The conversion of ethyl acrylate was 20.8%.

Comparative Example 1 (2) of Example 2 except that 0.05 mmol of vanadium oxytrichloride was used as the catalyst component [A] instead of the slurry of the catalyst component [A] used in (2) of Example 2. In the same manner, 2.49 g of a copolymer was obtained.

In this case, the catalytic activity was 0.98 kg / g.vanadium and the content of ethyl acrylate was 14.3% by weight. The conversion of ethyl acrylate was 17.9%.

Example 3 (1) Preparation of catalyst component [A] 7 mmol of vanadium tetrachloride was used in place of vanadium oxytrichloride used in (1) of Example 1, and butylethylmagnesium was used in place of trinormal butyl gallium 2.3. A slurry having a vanadium concentration of 15.2 mmol / m was obtained in the same manner as in (1) of Example 1 except that millimol was used.

(2) Production of Copolymer Instead of the slurry of the catalyst component [A] in (2) of Example 1, 0.05 mmol of vanadium was used as the slurry of the catalyst component [A] obtained in (1) above. Further, 4.58 g of a copolymer was obtained in the same manner as in (2) of Example 1 except that the amount of aluminum chloride used was 8 mmol and the amount of ethyl acrylate used was 8 mmol.

The activity of this catalyst was 1.80 kg / g.vanadium. The result of IR analysis of the obtained copolymer was the same as in Example 1, and the content of ethyl acrylate was 1.5% by weight. The conversion of ethyl acrylate was 8.6%.

Comparative Example 2 Similar to (2) of Example 3 except that 0.05 mmol of vanadium tetrachloride was used as the catalyst component [A] instead of the slurry of the catalyst component [A] used in (3) of Example 3. To obtain 4.07 g of a copolymer. The catalytic activity in this case is
The content was 1.60 kg / g-vanadium, and the content of ethyl acrylate was 1.3% by weight. The conversion of ethyl acrylate was 6.8%.

Example 4 In a 500 ml pressure-resistant container equipped with a stirrer, 300 ml of hexane under an argon atmosphere and 1.07 g of aluminum chloride as a Lewis acid (8
Hexane) slurry was added, and 0.85 ml (8 mmol) of methyl acrylate was further added thereto. Subsequent operations were performed in the same manner as in Example 1 to obtain 4.85 g of a copolymer.

The catalytic activity was 1.9 kg / g.vanadium, and the content of methyl methacrylate was 1.9% by weight. The conversion of methyl methacrylate was 11.5%.

[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.) In producing an ethylene copolymer by copolymerizing an acrylic acid ester and / or an α-substituted acrylic acid ester represented by An organoaluminum is used as a organometallic compound of Group I to III of the periodic table, using a reaction product with an organometallic compound of Group I to III (however, those containing an alkyl group). A method for producing an ethylene copolymer, which comprises using a compound and a halogen-containing aluminum compound as a Lewis acid compound. 2. The method according to claim 1, wherein the vanadium compound is vanadium oxychloride or vanadium tetrachloride. 3. An organogallium compound, an organoboron compound or an organomagnesium compound which is an organometallic compound of Group I to III of the periodic table (provided that it contains an alkyl group) used for the preparation of the catalyst component [A]. A method according to claim 1 which is a compound.