JP2003048909A - Catalyst for polymerizing methacrylic ester and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a methacrylic ester polymer with a high activity. SOLUTION: A methacrylic ester is polymerized by using a catalyst for polymerizing the methacrylic ester comprising an iron complex having nitrogen ligands and an aluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel methacrylic acid ester polymerization catalyst and a method for producing a methacrylic acid ester polymer using the catalyst.

[0002]

2. Description of the Related Art Vinyl polymers having polar groups in their side chains have various functions such as solubility, chemical resistance, weather resistance, and gas barrier properties as compared with nonpolar vinyl polymers such as polyethylene and polypropylene. It is known. Although such a polymer is mainly synthesized by radical polymerization, it is generally difficult to control the primary structure of the polymer such as the three-dimensional structure and the molecular weight.

On the other hand, the polymerization with an organic transition metal catalyst is relatively easy to control, and is therefore often used for the polymerization of nonpolar vinyl monomers such as ethylene and propylene. Living polymerization is possible. However, in the polymerization of polar vinyl monomers with organic transition metal catalysts, the reported groups are limited because polar groups often become catalyst poisons. Then, Polymer Letters, VOL. 9,281-287 (1971) includes dialkylbis (bipyridyl) iron complex (R ₂ Fe
It has been reported that (dipy) ₂ ) serves as a polymerization catalyst for methyl methacrylate, but the polymerization activity is very low, and the structure of the polymer could hardly be controlled.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and it is a polymerization catalyst capable of polymerizing a methacrylic acid ester with high activity and a methacrylic acid ester polymer using the catalyst. It is intended to provide a method for producing a united body.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors have found that a methacrylic acid ester composed of an iron complex having a nitrogen ligand and an aluminum compound having a bulky substituent. It was found that the polymerization catalyst can polymerize methacrylic acid ester with high activity,
The present invention has been completed.

That is, the present invention provides a methacrylic acid ester polymerization comprising an iron complex having a nitrogen ligand represented by the general formula (1) and an aluminum compound having a bulky substituent represented by the general formula (2). And a method for producing a methacrylic acid ester polymer, which comprises polymerizing a methacrylic acid ester in the presence of a catalyst for polymerization and the above-mentioned catalyst for polymerization.

The present invention will be described in detail below. The iron complex having a nitrogen ligand represented by the general formula (1), which is a component of the methacrylic acid ester polymerization catalyst of the present invention, includes:
The following can be illustrated.

R ¹ of the iron complex having a nitrogen ligand represented by the general formula (1) used in the present invention is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or halogen, Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, norbornyl group, phenyl group, styryl group,
Biphenyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, Tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group Group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

The substituents R ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a carbon atom having 1 carbon atom.
To a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms. As an example of the hydrocarbon group having 1 to 20 carbon atoms,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, norbornyl group, phenyl group, styryl group,
Biphenyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, Tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group Group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like. Examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group,
Hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group, dibutylsilyl group, diphenylsilyl group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, Tributylsilyl group,
Triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, trimethylsilylmethyl group,
Trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl)
Examples thereof include a propyl group, a bis (trimethylsilyl) butyl group, a bis (trimethylsilyl) phenyl group, and a triphenylsilylmethyl group. Examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, phenylamino group, benzylamino group, phenylethylamino. Group, phenylpropylamino group, phenylbutylamino group, naphthylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group , Dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis ( Dimethylamino) Eniru group, phenylaminomethyl group, diphenylamino methyl group, and a diphenylamino phenyl group. Examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butylphenoxy group, biphenoxy group. Group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group Group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, phenoxyphenyl group and the like.

Specific iron complexes represented by the above general formula (1) include dimethylbis (bipyridyl) iron, diethylbis (bipyridyl) iron and dipropylbis (bipyridyl).
Iron, dibutylbis (bipyridyl) iron, dimethylbis (6
-Methylbipyridyl) iron, diethylbis (6-methylbipyridyl) iron, dipropylbis (6-methylbipyridyl) iron, dibutylbis (6-methylbipyridyl) iron, dimethylbis (4,4'-di-t-butylbipyridyl)
Iron, diethylbis (4,4'-di-t-butylbipyridyl) iron, dipropylbis (4,4'-di-t-butylbipyridyl) iron, dibutylbis (4,4'-di-t-butylbipyridyl) iron, Dimethylbis (4,4'-diphenylbipyridyl) iron, diethylbis (4,4'-diphenylbipyridyl) iron, dipropylbis (4,4'-diphenylbipyridyl) iron, dibutylbis (4,4'-diphenylbipyridyl) iron, dimethyl Bis (6,6'-dibromobipyridyl) iron, diethylbis (6,6'-dibromobipyridyl) iron, dipropylbis (6,6'-dibromobipyridyl) iron, dibutylbis (6,6'-dibromobipyridyl) iron, dimethylbis (4,4′-Dimethylbipyridyl) iron, diethylbis (4,4′-dimethylbipyridyl) iron, dipropylbis (4,4 ′) Dimethylbipyridyl) iron, dibutylbis (4,4′-dimethylbipyridyl) iron, dimethylbis (4,4′-dinonylbipyridyl) iron, diethylbis (4,4′-dinonylbipyridyl) iron, dipropylbis (4,4 ′) -Dinonylbipyridyl) iron, dibutylbis (4,4'-dinonylbipyridyl) iron, dimethylbis (biquinoline) iron, diethylbis (biquinoline) iron, dipropylbis (biquinoline) iron,
Dibutylbis (biquinoline) iron, dimethylbis (phenanthroline) iron, diethylbis (phenanthroline)
Iron, dipropylbis (phenanthroline) iron, dibutylbis (phenanthroline) iron, dimethylbis (5-chlorophenanthroline) iron, diethylbis (5-chlorophenanthroline) iron, dipropylbis (5-chlorophenanthroline) iron, dibutylbis (5-chlorophenanthroline) iron , Dimethylbis (5-methylphenanthroline) iron, diethylbis (5-methylphenanthroline) iron, dipropylbis (5-methylphenanthroline) iron, dibutylbis (5-methylphenanthroline)
Iron, dimethylbis (4,7-dimethylphenanthroline) iron, diethylbis (4,7-dimethylphenanthroline) iron, dipropylbis (4,7-dimethylphenanthroline) iron, dibutylbis (4,7-dimethylphenanthroline) iron, dimethylbis ( 4,7-Diphenylphenanthroline) iron, diethylbis (4,7-diphenylphenanthroline) iron, dipropylbis (4,7-diphenylphenanthroline) iron, dibutylbis (4,7)
-Diphenylphenanthroline) iron, dimethylbis (2,9-dimethyl-4,7-diphenylphenanthroline) iron, diethylbis (2,9-dimethyl-4,7-
Diphenylphenanthroline) iron, dipropylbis (2,9-dimethyl-4,7-diphenylphenanthroline) iron, dibutylbis (2,9-dimethyl-4,7-
Diphenylphenanthroline) iron, dimethylbis (3,3
4,7,8-Tetramethylphenanthroline) iron, diethylbis (3,4,7,8-tetramethylphenanthroline) iron, dipropylbis (3,4,7,8-tetramethylphenanthroline) iron, dibutylbis (3,4,4)
Examples include 7,8-tetramethylphenanthroline) iron and the like.

Examples of the aluminum compound having a bulky substituent represented by the general formula (2), which is a component of the catalyst for methacrylic acid ester polymerization of the present invention, include the following.

Substituents R ³ of the aluminum compound represented by the general formula (2) used in the present invention are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen, and 1 to 1 carbon atoms. Examples of 20 hydrocarbon groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, norbornyl group, phenyl group, styryl group,
Biphenyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, Tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group Group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like.

The substituents R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a carbon atom having 1 carbon atom.
To a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms. As an example of the hydrocarbon group having 1 to 20 carbon atoms,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group, norbornyl group, phenyl group, styryl group,
Biphenyl group, naphthyl group, tolyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, dipropylphenyl group, dibutylphenyl group, diphenylphenyl group, trimethylphenyl group, triethylphenyl group, Tripropylphenyl group, tributylphenyl group, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, diphenylmethyl group, diphenylethyl group, diphenylpropyl group, diphenylbutyl group, vinyl group, propenyl group, butenyl group, butadienyl group Group, pentenyl group, pentadienyl group, hexenyl group, hexadienyl group and the like. Examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include methylsilyl group, ethylsilyl group, propylsilyl group, butylsilyl group, pentylsilyl group,
Hexylsilyl group, phenylsilyl group, benzylsilyl group, dimethylsilyl group, diethylsilyl group, dipropylsilyl group, dibutylsilyl group, diphenylsilyl group, dibenzylsilyl group, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, Tributylsilyl group,
Triphenylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, trimethylsilylmethyl group,
Trimethylsilylethyl group, trimethylsilylpropyl group, trimethylsilylbutyl group, trimethylsilylphenyl group, bis (trimethylsilyl) methyl group, bis (trimethylsilyl) ethyl group, bis (trimethylsilyl)
Examples thereof include a propyl group, a bis (trimethylsilyl) butyl group, a bis (trimethylsilyl) phenyl group, and a triphenylsilylmethyl group. Examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, phenylamino group, benzylamino group and phenylethylamino. Group, phenylpropylamino group, phenylbutylamino group, naphthylamino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diphenylamino group, dibenzylamino group, dimethylaminomethyl group, dimethylaminoethyl group , Dimethylaminopropyl group, dimethylaminobutyl group, dimethylaminophenyl group, bis (dimethylamino) methyl group, bis (dimethylamino) ethyl group, bis (dimethylamino) propyl group, bis (dimethylamino) butyl group, bis ( Dimethylamino) Eniru group, phenylaminomethyl group, diphenylamino methyl group, and a diphenylamino phenyl group. Examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, naphthoxy group, methylphenoxy group, ethylphenoxy group, propylphenoxy group, butylphenoxy group, biphenoxy group. Group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, phenoxymethyl group, methoxyethyl group, ethoxyethyl group,
Propoxyethyl group, butoxyethyl group, phenoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, butoxypropyl group, phenoxypropyl group, methoxybutyl group, ethoxybutyl group, propoxybutyl group, butoxybutyl group, phenoxybutyl group Group, methoxyphenyl group, ethoxyphenyl group, propoxyphenyl group, butoxyphenyl group, phenoxyphenyl group and the like.

Specific aluminum compounds represented by the above general formula (2) include (2,6-di-t-butylphenoxy) dimethylaluminum and (2,6-di-t-).
Butylphenoxy) diethylaluminum, (2,6-
Di-t-butylphenoxy) diisobutylaluminum, bis (2,6-di-t-butylphenoxy) methylaluminum, bis (2,6-di-t-butylphenoxy) ethylaluminum, bis (2,6-di- t-Butylphenoxy) isobutylaluminum, bis (2,6)
-Di-t-butyl-4-methylphenoxy) methyl aluminum, bis (2,6-di-t-butyl-4-methylphenoxy) ethyl aluminum, bis (2,6-di-
t-Butyl-4-methylphenoxy) isobutylaluminum, bis (2,6-di-t-butyl-4-bromophenoxy) methylaluminum, bis (2,6-di-t)
-Butyl-4-bromophenoxy) ethyl aluminum, bis (2,6-di-t-butyl-4-bromophenoxy) isobutyl aluminum, bis (2,6-diphenylphenoxy) methyl aluminum, bis (2,6-
Examples thereof include diphenylphenoxy) ethylaluminum, bis (2,6-diphenylphenoxy) isobutylaluminum, and tris (2,6-diphenylphenoxy) aluminum.

The molar ratio of the iron complex having a nitrogen ligand represented by the general formula (1) to the aluminum compound having a bulky substituent represented by the general formula (2) is not particularly limited,
Al: Fe is preferably 0.01: 1 to 100: 1.

A methacrylic acid ester polymer can be produced by homopolymerizing or copolymerizing a methacrylic acid ester in the presence of the catalyst of the present invention. At this time, the order of adding the catalyst is not particularly limited, and it is preferable that the polymerization reaction is carried out without solvent or in a solvent which is inert to the polymerization reaction and which is liquid at the time of polymerization. Specifically, benzene, toluene, xylene, butane, pentane, hexane, heptane, octane, nonane, decane, tetradecane, cyclopentane, cyclohexane, chloroform,
Examples thereof include methylene chloride, 1,2-dichloroethane, chlorobenzene and the like.

The methacrylic acid ester used in the polymerization reaction of the present invention is methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate,
Examples thereof include lauryl methacrylate and stearyl methacrylate, and a mixed component of two or more of these components can be polymerized, but the present invention is not limited thereto.

The polymerization temperature is not particularly limited and is -100 to 1
00 ° C is preferred.

The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

The polymerization operation, reaction and solvent purification are
All were done under inert gas. All the solvents and the like used in the reaction were previously purified, dried and deoxygenated by known methods. Further, the compounds used in the reaction were those synthesized and identified by known methods. The molecular weight of the polymer was measured using gel permeation chromatography.

[0021]

EXAMPLES Example 1 Diethylbis (bipyridyl) iron (Et ₂ Fe (dip
y) ₂ ) Synthesis In a 300 ml Schlenk tube, iron acetylacetonate 9.0 g, bipyridyl 9.0 g, diethyl ether 50
ml was added at room temperature and cooled to -20 ° C. To this, 75.1 mmol of diethylaluminum ethoxide was added.
After reacting at 0 ° C. for 6 hours and at room temperature for 10 hours, the solution portion was filtered, washed with 50 ml of ether and 50 ml of hexane, and dried under reduced pressure at room temperature to obtain the desired product.

Polymerization of Methyl Methacrylate In a Schlenk tube of 50 ml, 20 ml of toluene, 2.5 ml of methyl methacrylate, bis (2,6-di-t-butyl-4-methylphenoxy) methylaluminum "MA
0.25 mmol of "D" (Tokyo Kasei) was added, and then 0.05 mmol of an iron complex was introduced to initiate polymerization at room temperature. After 2 hours, hydrochloric acid (1 ml) / Ekinen (50 m
After the polymer solution was charged in l), it was washed with Echinene and dried to obtain a polymer in a yield of 100%. Mw
Was 130000, Mw / Mn = 1.2, and rr determined by ¹³ C-NMR was 70% polymethylmethacrylate.

Example 2 Methyl methacrylate was polymerized in the same manner as in Example 1 except that the amount of methyl methacrylate added was 1.25 ml, and a polymer was obtained with a yield of 100%. Mw is 70
000, Mw / Mn = 1.2, rr determined by ¹³ C-NMR was confirmed to be 70% polymethylmethacrylate.

Comparative Example 1 Polymerization of methyl methacrylate was carried out in the same manner as in Example 1 except that MAD was not added, but no polymer could be obtained.

Example 3 Synthesis of bis (2,6-di-t-butyl-4-methylphenoxy) ethylaluminum "EAD" In a 300 ml Schlenk tube, 2,6-di-t-butyl-p-crezo- 4.7 g of toluene and 50 ml of toluene were added, and then 10.6 m of triethylaluminum was added at room temperature.
mol was added dropwise. The reaction was carried out at room temperature for 6 hours and further at 60 ° C. for 3 hours, and toluene was distilled off. It was washed twice with 20 ml of hexane to obtain the desired product.

Polymerization of Methyl Methacrylate Polymerization of methyl methacrylate was carried out in the same manner as in Example 1 except that EAD was used instead of MAD, and a polymer was obtained with a yield of 100%. Mw is 63000, Mw / Mn
It was confirmed that the polymethyl methacrylate was 1.1.

Example 4 Synthesis of bis (2,6-diphenylphenoxy) methylaluminum (MAPH) To a Schlenk tube of 300 ml, 5.0 g of 2,6-diphenylphenol and 50 ml of toluene were added, and thereafter,
Triethylaluminum 10.1 mmol was added dropwise at room temperature. React at room temperature for 6 hours, then at 60 ° C for 3 hours,
The toluene was distilled off. It was washed twice with 20 ml of hexane to obtain the desired product.

Polymerization of Methyl Methacrylate Methyl methacrylate was polymerized in the same manner as in Example 1 except that MAPH was used instead of MAD, and a polymer was obtained with a yield of 100%. Mw is 98000, Mw / M
It was confirmed that the polymethyl methacrylate was n = 1.2.

[0029]

According to the present invention, a novel methacrylic acid ester polymerization catalyst can be provided, and by using the polymerization catalyst of the present invention, a methacrylic acid ester polymer can be produced with high activity. it can.

Claims (2)

[Claims] 1. The following general formula (1): (In the formula, each R ¹ independently represents a hydrogen atom or a carbon number of 1 to 20.
Is a hydrocarbon group or halogen. R ² is independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, halogen,
Silicon-containing hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
It is a nitrogen-containing hydrocarbon group of 0 or an oxygen-containing hydrocarbon group of 1 to 20 carbon atoms. ) An iron complex having a nitrogen ligand represented by the following general formula (2) (In the formula, each R ³ independently represents a hydrogen atom or a carbon number of 1 to
20 hydrocarbon groups, R ⁴ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon having 1 to 20 carbon atoms A group or an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, and n is 0, 1 or 2. ) A catalyst for methacrylic acid ester polymerization, which comprises an aluminum compound represented by 2. A method for producing a methacrylic acid ester polymer, which comprises polymerizing a methacrylic acid ester in the presence of the polymerization catalyst according to claim 1.