JPH07300459A - Production of polymerizable imide compound - Google Patents

Abstract

PURPOSE:To obtain in high yield the subject compound containing in the molecule at least two C=C bonds, useful as e.g. a raw material for polyimides, by reaction between a specific tetracarboxylic dianhydride and an isocyanate in the presence of a tertiary amine catalyst in a polar organic solvent. CONSTITUTION:The objective compound is obtained by reaction between (A) a compound of formula I. (R<0> is an organic group such as a 6-30C aromatic group) and (B) a compound of formula II (R<1> is a 2-30C C=C bond-contg. organic group) (C) in the presence of a tertiary amine catalyst such as tri-n- butylamine (D) in a polar organic solvent such as DMF. Alternatively, this compound can also be obtained by reaction between the component A and a compound of formula III (R<3> is a 4-15C organic group) in the presence of the component C in the component D followed by reaction with (meth)acrylic acid, an OH-bearing (meth)acrylic ester derivative, or (meth)acrylamide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymerizable imide compound.

[0002]

2. Description of the Related Art As a method for producing a polymerizable imide compound, for example, a method of synthesizing an imide alcohol from an acid anhydride and monoethanolamine and then synthesizing it by an esterification reaction of the imide alcohol and acrylic acid or methacrylic acid is known. (Japanese Patent Laid-Open No. 3-271272).
However, since this method is a two-step synthetic method, it is not industrially preferable.

As another synthetic method, a one-step synthetic method in which an acid anhydride is reacted with diisocyanate to obtain a polyimide by decarboxylation of an isocyanate group is also known (latest heat-resistant polymer). However, when an attempt is made to synthesize a polymerizable imide compound by this method, there is a problem that the yield of the desired synthetic product is low because there is no catalyst.

[0004]

The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a method for producing a polymerizable imide compound in a high yield.

[0005]

DISCLOSURE OF THE INVENTION The first aspect of the present invention is to provide an isocyanate containing a tetracarboxylic dianhydride represented by the general formula (I) and a carbon-carbon double bond represented by the general formula (II). The present invention provides a method for producing a polymerizable imide compound having two or more carbon-carbon double bonds in one molecule, which comprises reacting a compound with a tertiary amine catalyst in a polar organic solvent.

Secondly, the present invention relates to a tetracarboxylic dianhydride represented by the general formula (I) and a diisocyanate represented by the general formula (III) in the presence of a tertiary amine catalyst.
Characterized by reacting in a polar organic solvent and then with acrylic acid, methacrylic acid, a (meth) acrylic acid ester derivative containing a hydroxyl group or (meth) acrylamide, and having two or more carbons in one molecule. −
Provided is a method for producing a polymerizable imide compound containing a carbon double bond.

[0007]

[Chemical 3]

In the formula, R ⁰ represents an organic group containing an aromatic group having 6 to 30 carbon atoms. R ¹ —NCO (II) In the formula, R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 30 carbon atoms. During ^OCN-R 3 -NCO (III) formula, ^{R 3} represents 4 to 15 amino organic group having a carbon number.

The present invention will be described in detail below. The general formula (I) which is a starting material commonly used in the method of the present invention
In the tetracarboxylic dianhydride represented in, R ⁰
Is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms. If the carbon number exceeds 30, it is difficult to obtain and it is not practical. As a specific example, for example,

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

And the like.

In the first method of the present invention, these tetracarboxylic dianhydrides and the isocyanate represented by the general formula (II) are reacted under predetermined conditions.
In the isocyanate represented by I), R ¹ is a carbon-carbon double bond-containing organic group having 2 to 30 carbon atoms.
As a specific example, an acryloyl group, a methacryloyl group,
Methacryloyloxyethyl group, vinyl group, allyl group,
Butenyl group, pentenyl group, hexenyl group, octenyl group, decenyl group, undecenyl group, isopropenyl group,
Examples thereof include o-vinylphenyl group, m-vinylphenyl group, p-vinylphenyl group, m-isopropenyl-α, α-dimethylbenzyl group.

A compound obtained by reacting a diisocyanate compound with a compound having at least one carbon-carbon double bond and at least one OH group as the isocyanate represented by the general formula (II) is also preferably used. As a specific example, for example, 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diisocyanate-3,3'-dimethylbiphenyl, 4,4'-diisocyanate-3,3'-dimethyldiphenylmethane,
Diisocyanate compounds such as 1,4-diisocyanate butane and 1,5-diisocyanate-2-methylpentane, and, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy Propyl (meta)
An isocyanate compound having a carbon-carbon double bond obtained by reacting acrylate, 2-hydroxy-1- (meth) acryloxy-3- (meth) acryloxypropane, and the like can be mentioned. In this case, a diisocyanate compound, a compound having at least one carbon-carbon double bond and at least one OH group are charged in equimolar amounts and reacted in the presence of an organic solvent capable of dissolving any compound, particularly a polar organic solvent, as a reaction solvent. The above carbon
An isocyanate compound containing a carbon double bond can be obtained. In this case, it is preferable to use N, N-dimethylformamide as a reaction solvent from the viewpoints of subsequent utilization in the synthesis of the polymerizable imide compound and solubility and reactivity. When the reaction is carried out at a reaction temperature of -5 to 10 ° C and a reaction time of 6 to 48 hours and is to be isolated after the completion of the reaction, it should be appropriately isolated using a known isolation and purification method such as a distillation method or a column fractionation method. You can

The tetracarboxylic dianhydride and the general formula (I
The molar ratio of the isocyanate represented by I) is usually 1: 2.
˜1: 10, more preferably 1: 2 to 1: 6, and particularly preferably 1: 2 to 1: 4.

The reaction is carried out in a polar organic solvent in the presence of a tertiary amine. As the polar organic solvent, for example, sulfolane, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N, N
-Dimethylethylene urea and the like. From the viewpoint of solubility and reactivity, it is preferable to use N, N-dimethylformamide.

Examples of the tertiary amine coexisting as a catalyst include triethylenediamine, tri-n-butylamine and 1,8-diazabicyclo (5,4,0) -7-.
There are many tertiary amines such as undecene,
Particularly, tri-n-butylamine is preferable. The amount of the catalyst used is 0.5 to 30 mol%, preferably 3 to 15 mol%, and particularly preferably 4 to 10 mol% based on the tetracarboxylic dianhydride represented by the general formula (I).

Further, in the above reaction, a polymerization inhibitor may be added in order to increase the stability during the heating reaction. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like.

The reaction temperature is usually 70 to 150 ° C, preferably 80 to 120 ° C, particularly preferably 90 to 110 ° C. The time required for the reaction is usually 3 to 24 hours, preferably 3 to 12 hours, particularly preferably 4 to 6 hours.

After the completion of the reaction, the reaction product can be isolated and purified by, for example, extraction with chloroform or the like, and then a known isolation and purification method such as a column preparative method, a reprecipitation method or a recrystallization method. Thereafter, for example, by performing vacuum drying, a polymerized imide compound which is a reaction product can be obtained.

In the second method of the present invention, first, the tetracarboxylic dianhydride represented by the general formula (I) is reacted with the diisocyanate represented by the general formula (III) under predetermined conditions. R ³ of the diisocyanate represented by (III) is an organic group having 4 to 15 carbon atoms, for example, an aromatic, aliphatic or alicyclic hydrocarbon group. Specific examples of the diisocyanate include, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
4,4'-diisocyanate-3,3'-dimethylbiphenyl, 4,4'-diisocyanate-3,3'-dimethyldiphenylmethane, 1,4-diisocyanate butane, 1,5-diisocyanate-2-methylpentane and the like can be mentioned. To be

Tetracarboxylic acid dianhydride and the general formula (II
The molar ratio with the diisocyanate represented by I) is preferably an excess molar amount of the latter with respect to the former, usually N: N.
It is used in a molar ratio of +1 (N is 1 to 10).

The reaction between the two is carried out in the presence of a tertiary amine in a polar organic solvent.
The type of tertiary amine and the amount thereof used are the same as in the first reaction.

The reaction temperature is generally -10 to 40 ° C, preferably -5 to 30 ° C, particularly preferably -5 to 10 ° C. The time required for the reaction is usually 3 to 48 hours, preferably 12 to 30 hours.

After completion of the above reaction, the reaction product contains acrylic acid, methacrylic acid, and a hydroxyl group (meth).
React with an acrylic ester derivative or (meth) acrylamide. In this case, both relations of the both are selected so that the latter reacts in a double molar amount of the former.

The reaction temperature is usually 70 to 150 ° C., preferably 80 to 120 ° C., particularly preferably 90 to 110 ° C.,
The reaction time is generally 3 to 24 hours, preferably 3 to 12 hours, particularly preferably 4 to 6 hours.

Further, in the above reaction, a polymerization inhibitor may be added in order to increase the stability during the heating reaction. Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine and the like.

After completion of the reaction, the reaction product can be isolated and purified by, for example, extraction with chloroform or the like, and then a known isolation and purification method such as a column preparative method, a reprecipitation method and a recrystallization method. Then, for example, by performing vacuum drying, a polymerizable imide compound as a reaction product can be obtained.

[0030]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 2-methacryloyloxyethyl isocyanate was added to a 30 ml capacity two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 2,2-bis (3,4-dicarboxyphenyl) -hexafluoropropane dianhydride (hereinafter abbreviated as 6FDA) 1.752 g (4 mmo)
l), 0.037 g of tri-n-butylamine (0.2 m
mol), 7 mg of phenothiazine and 10 ml of N, N-dimethylformamide are charged, and the mixture is stirred with a magnetic stirrer for 140 minutes while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 85%. The obtained solid matter was analyzed by elemental analysis, infrared absorption spectrum analysis, ¹ H-N
It was confirmed by MR analysis that a polymerizable imide compound represented by the formula (IV) was obtained.

[0032]

[Chemical 7]

Example 2 2-methacryloyloxyethyl isocyanate was added to a 30 ml capacity two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), 0.037 g of tri-n-butylamine
(0.2 mmol), phenothiazine 7 mg, N, N-
Charge 10 ml of dimethylformamide and set the temperature to 100.
Stir with a magnetic stirrer for 5 hours while maintaining at ℃. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 89%.

Example 3 2-methacryloyloxyethyl isocyanate was placed in a 30 ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), 0.022 g of triethylenediamine (0.
2 mmol), 7 mg of phenothiazine and 10 ml of N, N-dimethylformamide are charged, and the mixture is stirred with a magnetic stirrer for 140 minutes while maintaining the temperature at 100 ° C.
After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 67%.

Example 4 2-methacryloyloxyethyl isocyanate was placed in a 30 ml capacity two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), 1,8-diazabicyclo (5,4,0)-
0.030 g (0.2 mmol) of 7-undecene, 7 mg of phenothiazine, N, N-dimethylformamide 10
After adding ml, the mixture is stirred with a magnetic stirrer for 140 minutes while keeping the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 79%.

Example 5 2-methacryloyloxyethyl isocyanate was placed in a 30-ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 3,3′-benzophenone tetracarboxylic dianhydride 1.289 g (4 mm1),
Tri-n-butylamine 0.037 g (0.2 mmo
1), 7 mg of phenothiazine and 10 ml of N, N-dimethylformamide are charged, and the mixture is stirred with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, followed by reprecipitation with methanol to isolate and purify the desired product. Then, vacuum drying was performed to obtain a white solid. It was confirmed by the elemental analysis, the infrared absorption spectrum analysis, and the ¹ H-NMR analysis that the obtained solid was a polymerizable imide compound represented by the formula (V).

[0037]

[Chemical 8]

Example 6 2-methacryloyloxyethyl isocyanate was added to a 30-ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 4,4'-biphthalic anhydride 1.177 g (4 mmol), tri-n-butylamine 0.037 g (0.2 mmol), phenothiazine 7 m
g, 10 ml of N, N-dimethylformamide was charged,
Stir with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After the reaction was completed, the precipitate was washed with acetone and then vacuum dried to obtain a white solid. The obtained solid matter is subjected to elemental analysis, infrared absorption spectrum analysis, ¹
It was confirmed by 1 H-NMR analysis that a polymerizable imide compound represented by the formula (VI) was obtained.

[0039]

[Chemical 9]

Example 7 2-methacryloyloxyethyl isocyanate was added to a 30-neck two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 4,4'-oxydiphthalic anhydride 1.241 g (4 mmol), tri-n-butylamine 0.037 g (0.2 mmol), phenothiazine 7 mg, N, N-dimethylformamide 10 ml were charged, and the temperature was adjusted. Stir with a magnetic stirrer for 5 hours while maintaining at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, followed by reprecipitation with methanol to isolate and purify the desired product. Then, vacuum drying was performed to obtain a white solid. It was confirmed by the elemental analysis, the infrared absorption spectrum analysis, and the ¹ H-NMR analysis that the obtained solid was a polymerizable imide compound represented by the formula (VII).

[0041]

[Chemical 10]

Example 8 1.93 g (8%) of 2,4-tolylene diisocyanate was placed in a 50 ml two-necked flask equipped with a condenser and a thermometer.
mmol), 6FDA 1.752 g (4 mmol),
Tri-n-butylamine 0.037 g (0.2 mmo
1) and 10 ml of N, N-dimethylformamide are charged and stirred with a magnetic stirrer for 30 hours while keeping the temperature at 3 ° C. Thereafter, 1.041 g (8 mmol) of 2-hydroxyethyl methacrylate and 7 mg of phenothiazine are added, and the mixture is stirred with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform and reprecipitation with methanol are carried out to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. It was confirmed by the elemental analysis, the infrared absorption spectrum analysis, and the ¹ H-NMR analysis that the obtained solid was a polymerizable imide compound represented by the formula (VIII).

[0043]

[Chemical 11]

Comparative Example 1 2-methacryloyloxyethyl isocyanate was added to a 30 ml capacity two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), phenothiazine (7 mg) and N, N-dimethylformamide (10 ml) are charged, and the mixture is stirred with a magnetic stirrer for 140 minutes while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 46%.

Comparative Example 2 2-methacryloyloxyethylisocyanate was added to a 30 ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), phenothiazine (7 mg) and N, N-dimethylformamide (10 ml) are charged, and the mixture is stirred with a magnetic stirrer for 5 hours while maintaining the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 58%.

Comparative Example 3 2-methacryloyloxyethyl isocyanate was added to a 30 ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), tetra-n-butylammonium bromide 0.064 g (0.2 mmol), phenothiazine 7
Charge 10 mg of N, N-dimethylformamide, and stir for 140 minutes with a magnetic stirrer while keeping the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 42%.

Comparative Example 4 2-methacryloyloxyethyl isocyanate was added to a 30 ml two-necked flask equipped with a condenser and a thermometer.
240 g (8 mmol), 6FDA 1.752 g (4
mmol), tetra-n-butylammonium chloride 0.056 g (0.2 mmol), phenothiazine 7
Charge 10 mg of N, N-dimethylformamide, and stir for 140 minutes with a magnetic stirrer while keeping the temperature at 100 ° C. After completion of the reaction, extraction with chloroform is carried out, and then column fractionation is carried out using an ethyl acetate: n-hexane = 2: 1 developing solvent to isolate and purify the desired product. Then, vacuum drying was performed to obtain a yellow solid. The yield is 42%.

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Claims (2)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R ⁰ represents an organic group containing an aromatic group having 6 to 30 carbon atoms) and a tetracarboxylic dianhydride represented by the general formula (II) R ¹ -NCO (II) (wherein , R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 30 carbon atoms), and an isocyanate having a carbon-carbon double bond represented by the following formula, in the presence of a tertiary amine catalyst:
A method for producing a polymerizable imide compound having two or more carbon-carbon double bonds in one molecule, which comprises reacting in a polar organic solvent. 2. A compound represented by the general formula (I): (In the formula, R ⁰ represents an organic group containing an aromatic group having 6 to 30 carbon atoms) and a tetracarboxylic dianhydride represented by the general formula (III) OCN-R ³ -NCO (III) ( In the formula, R ³ represents an organic group having 4 to 15 carbon atoms) and is reacted with a diisocyanate in the presence of a tertiary amine catalyst in a polar organic solvent, and then acrylic acid,
A polymerizable imide compound having two or more carbon-carbon double bonds in one molecule, characterized by reacting with methacrylic acid, a (meth) acrylic acid ester derivative containing a hydroxyl group or (meth) acrylamide Production method.