JPH051078A - Production of reactive silicon group-containing imide compound - Google Patents

Abstract

PURPOSE:To obtain the subject compound curable at relatively low temperatures, excellent in long-term storage stability and heat resistance, useful for coating agents, etc., by reaction between each specific tetracarboxylic dianhydride and primary amine to give an imide compound followed by reaction of this imide compound with a specific hydrosilane. CONSTITUTION:Reaction is made in an organic polar solvent such as DMF between (A) a tetracarboxylic dianhydride of formula I (R<0> is 6-30C tetravalent organic group containing aromatic group) such as pyromellitic dianhydride and (B) a primary amine of formula II. (R<1> is 2-20C organic group containing C=C bond) such as allylamine to form an amic acid solution, which is then converted to an imide compound. This compound is then hydrosilylated with a hydrosilane of formula III [R<2> is 1-20C monovalent organic group or of formula IV (R<3> is 1-10C monovalent hydrocarbon); X is OH or hydrolyzable group; (a) is 1-3] such as methyldimethoxysilane in a solvent such as hexane in the presence of a hydrosilylating catalyst such as chloroplatinic acid, thus obtaining the objective compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing a reactive silicon group-containing imide compound. More specifically, an imide compound having two carbon-carbon double bond-containing organic groups in one molecule is obtained from an aromatic tetracarboxylic dianhydride and an amine containing a carbon-carbon double bond-containing organic group, The present invention further relates to a process for producing a reactive silicon group-containing imide compound, which comprises hydrosilylating the imide compound with a hydrosilane having a reactive group.

[0002]

Conventionally, various kinds of room temperature curable compositions have been developed, but they are cured at a relatively low temperature, and after curing, heat resistance, chemical resistance,
A curable composition that gives a cured product having excellent mechanical properties has hardly been developed.

For example, as a room temperature curable composition, a composition containing an alkoxysilyl group-terminated polyether has been disclosed (JP-A-52-73998). The cured product obtained from this composition is rubber-like at room temperature and has excellent mechanical properties, especially at low temperatures, but at temperatures of 100 ° C and above, the mechanical properties are greatly reduced in a short time, so it is virtually Cannot be used. Moreover, the cured product is greatly swollen by various organic solvents such as hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, ether solvents, amide solvents, halogen solvents and the like, and the mechanical properties are greatly changed. It also has the drawback.

Further, as a curable resin composition which gives a cured product excellent in surface hardness, impact resistance, chemical resistance, adhesiveness and the like after curing, Japanese Patent Publication No. 58-32163 discloses tetracarboxylic dianhydride. Having a reactive silicon group by reacting an acid anhydride such as a compound or an acid anhydride terminated polyamic acid obtained by reacting the acid anhydride with a diamine and an aminosilicon compound at -20 to + 50 ° C. A (poly) amic acid prepolymer is obtained, and this prepolymer is used as a precursor as it is without imidization, or is chemically imidized under mild conditions to form a reactive silicon group-containing (poly) imide prepolymer. Then, a curable resin composition is disclosed which is crosslinked to form a (poly) imidosiloxane. When the precursor is used as it is without imidization, it can be converted into a (poly) imidosiloxane by heating the precursor in a solution state and crosslinking the precursor as the imidization proceeds.

However, this reactive silicon group-containing (poly) amic acid prepolymer requires treatment at a high temperature for imidization, and a pre-imidized reactive silicon group-containing (poly) imide prepolymer is required. Treatment with a dehydrating agent to produce often results in gelling of the entire solution. Furthermore, the carboxyl group or amino group present in the reactive silicon group-containing (poly) amic acid prepolymer reacts with the reactive silicon group to form a crosslinked structure, which causes various problems such as poor storage stability. Have

[0006]

The present invention is a reaction which has excellent long-term storage stability and is cured at a low temperature by the action of heating and / or a catalyst to give a cured product having excellent heat resistance and chemical resistance. The purpose of the present invention is to provide a process for producing an imide compound containing a crystalline silicon group, and (a) the general formula (I):

[0007]

[Chemical 5]

(Wherein R ⁰ represents a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms) and a tetracarboxylic dianhydride represented by the general formula (II):

[0009]

[Chemical 6]

(Wherein R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 20 carbon atoms) and a primary amine containing a carbon-carbon double bond-containing organic group By reacting in a polar solvent to obtain a solution of amic acid, (b) and then imidizing this solution, two carbon atoms in one molecule can be obtained.
-An imide compound having a carbon double bond-containing organic group,
(c) In the presence of a hydrosilylation catalyst, the imide compound obtained in (b) is represented by the general formula (III):

[0011]

[Chemical 7]

(In the formula, R ² is a monovalent organic group having 1 to 20 carbon atoms or the general formula (IV):

[0013]

[Chemical 8]

(Wherein R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and 3 R ³ may be the same or different), and X is a hydroxyl group. Or represents a hydrolyzable group, a is 1, 2 or 3,
When two or more R ² and X are present, they may be the same or different and are hydrosilylated with a hydrosilane having a reactive group represented by The present invention relates to a method for producing an imide compound containing two reactive silicon groups.

[0015]

[Operations and Examples] In the production method of the present invention, the general formula (I)
:

[0016]

[Chemical 9]

The tetracarboxylic dianhydride represented by the general formula (II):

[0018]

[Chemical 10]

A primary amine containing a carbon-carbon double bond-containing organic group represented by is reacted in an organic polar solvent to obtain a solution of amic acid, which is then imidized to obtain one An imide compound having two carbon-carbon double bond-containing organic groups is prepared.

As a method for producing the imide compound having two carbon-carbon double bond-containing organic groups in one molecule (hereinafter, also referred to as carbon-carbon double bond-containing organic group-containing imide compound), aromatic tetracarbon The acid dianhydride is reacted with a primary amine containing a carbon-carbon double bond-containing organic group in an organic polar solvent to obtain a solution of amic acid, which is then thermally imidized by heating. Method, an aromatic tetracarboxylic acid dianhydride and a primary amine containing a carbon-carbon double bond-containing organic group are reacted in an organic polar solvent to obtain a solution of amic acid, and then a solution of acetic anhydride or the like is obtained. A method of chemically imidizing by acting a dehydrating agent, an aromatic tetracarboxylic dianhydride and a primary amine containing a carbon-carbon double bond-containing organic group are reacted in an organic polar solvent to form an amic acid. The solution of Then, a method may be mentioned in which this solution is brought into contact with a poor solvent for amic acid such as water or hydrocarbon to precipitate amic acid as a precipitate, and this is heated.

The carbon can be obtained by any of these methods.
-A carbon double bond-containing organic group-containing imide compound can be produced and is not particularly limited, but the production apparatus and production process are simpler or easier,
Since the raw materials used are easy to obtain,
That is, a method of reacting an aromatic tetracarboxylic dianhydride and an amine containing a carbon-carbon double bond-containing organic group in an organic polar solvent to obtain a solution of amic acid, and then heating this to perform imidization Is preferred.

In the general formula (I), R ⁰ has 6 to 6 carbon atoms.
It is a tetravalent organic group containing 30 aromatic groups. If the carbon number exceeds 30, it is difficult to obtain and not practical. Among the tetravalent organic groups, a tetravalent group having an aromatic ring having 6 to 30 carbon atoms and having an aromatic ring bonded through a divalent group has high heat resistance after curing. It is preferable because it gives an excellent cured product. Among them, particularly preferable specific examples are, for example,

[0023]

[Chemical 11]

[0024]

[Chemical 12]

And the like.

The tetracarboxylic acid dianhydride represented by the general formula (I) can be used alone or as a mixture of two or more kinds.

In the general formula (II), R ¹ has 2 carbon atoms.
-20 carbon-carbon double bond-containing organic groups having a carbon number of more than 20 are difficult to obtain and are not practical.

Specific examples of the carbon-carbon double bond-containing organic group include, for example, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, isopropenyl group. , 2-methyl-2-propenyl group, o-vinylphenyl group,
Examples thereof include m-vinylphenyl group and p-vinylphenyl group.

The organic polar solvent is not particularly limited as long as it does not react with an acid dianhydride or an amine having one carbon-carbon double bond, and specific examples thereof include dimethyl sulfoxide, diethyl sulfoxide and the like. Sulfoxide solvents; N, N-dimethylformamide, N, N-
Formamide solvents such as diethylformamide; N, N-
Acetamide solvents such as dimethylacetamide and N, N-diethylacetamide; pyrrolidone solvents such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; phenol, o-cresol, Examples thereof include phenol solvents such as m-cresol, p-cresol, xylenol, halogenated phenol, and catechol; pyridine, hexamethylphosphoamide, or a mixture of two or more thereof.

The reaction for obtaining a solution of the amic acid is carried out at a temperature of 80 ° C. or lower, preferably 50 ° C. or lower, by adding a carbon-carbon double bond-containing organic group to a solution of tetracarboxylic anhydride dissolved in an organic polar solvent. The method of adding a primary amine containing the above or a solution of the primary amine dissolved in an organic polar solvent, or conversely to a solution of a primary amine containing a carbon-carbon double bond-containing organic group dissolved in an organic polar solvent, It can be carried out by mixing the two components by a method of adding a carboxylic acid anhydride or a solution in which it is dissolved in an organic polar solvent, and then reacting the mixture at 80 ° C. or lower, preferably 50 ° C. or lower for 0.1 to 3 hours.

The ratio of the primary amine containing the carbon-carbon double bond-containing organic group to the tetracarboxylic dianhydride is (primary amine containing the carbon-carbon double bond-containing organic group) / (tetra Carboxylic dianhydride) in a molar ratio of 2/1
˜5 / 1, preferably 2/1 to 3/1, more preferably 2/1 to 2.5 / 1. (Carbon-carbon double bond-containing organic group-containing primary amine) / (tetracarboxylic dianhydride)
Is less than 2/1, of course, unreacted acid anhydride groups remain, and the yield of the target carbon-carbon double bond-containing organic group-containing imide compound decreases, which is not preferable. Also, 5 /
If it exceeds 1, the amount of unreacted acid anhydride groups remaining decreases, but it is not preferable because it becomes difficult to remove the primary amine containing the carbon-carbon double bond-containing organic group used in excess.

As the above-mentioned imidization method, the method of thermal imidization is preferable as described above. For the thermal imidization, the organic polar solvent solution containing the amic acid obtained in the above reaction is heated to 100 to 250 ° C., preferably 100 to 200 ° C., and 0.5 to 15 hours, preferably 0.5 to 10 hours. Just hold it.

In the present invention, the carbon-carbon double bond-containing organic group-containing imide compound has the general formula (V):

[0034]

[Chemical 13]

A group represented by (hereinafter referred to as a reactive silicon group) is introduced to produce an imide compound containing two reactive silicon groups in one molecule.

The introduction of the reactive silicon group to the carbon-carbon double bond-containing organic group-containing imide compound is carried out by reacting the carbon-carbon double bond-containing organic group-containing imide compound in the presence of a hydrosilylation catalyst. The method of hydrosilylation with a hydrosilane having a functional group is preferable from the viewpoint of yield, easiness of operation and the like.

The hydrosilane having a reactive group is represented by the general formula (III):

[0038]

[Chemical 14]

It is a compound represented by:

In the above general formula (III), R ² has 1 to 20 carbon atoms.
Individual monovalent organic groups or general formula (IV):

[0041]

[Chemical 15]

(In the formula, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and three R ³ may be the same or different) and is a triorganosiloxy group.

When R ² is the above-mentioned monovalent organic group, if the number of carbon atoms exceeds 20, it is difficult to obtain the raw material. Such a monovalent organic group has 1 to 20 carbon atoms, preferably 1
To 15 alkyl groups, 6 to 20 carbon atoms, preferably 6 to
15 aryl groups, 7 to 20 carbon atoms, preferably 7 to 15 carbon atoms
Aralkyl groups.

When R ² is the above triorganosiloxy group and R ³ has more than 10 carbon atoms, it is difficult to obtain the raw material.

Specific examples of R ³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group,
Examples thereof include a heptyl group, an octyl group, a nonyl group, a decyl group, an isopropyl group, an isobutyl group, a t-butyl group and a phenyl group.

Specific examples of R ² include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, isopropyl group, isobutyl group. , Alkyl groups such as isooctyl group; cycloalkyl groups such as cyclohexyl group, cyclopentyl group, methylcyclohexyl group, methylcyclopentyl group, aralkyl groups such as benzyl group, phenethyl group, cumyl group; trimethylsiloxy group, triethylsiloxy group, t- Examples thereof include a butyldimethylsiloxy group, a methyldiphenylsiloxy group, a dimethylphenylsiloxy group, and a triphenylsiloxy group.

When a plurality of R ^2's are present in the molecule, they may be the same or different.

X represents a hydroxyl group or a hydrolyzable group.
The hydrolyzable group is not particularly limited, and includes conventionally known hydrolyzable groups, specifically, for example, hydrogen atom, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide. Group, aminooxy group, mercapto group, alkenyloxy group and the like. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are preferable because the raw materials are easily available and the reactivity is high. An alkoxy group is particularly preferable from the viewpoint of mild degradability and easy handling. When two or more Xs are present in the molecule, they may be the same or different.

A represents 1, 2, or 3. That is, the group represented by X can be bonded to one silicon atom in the range of 1 to 3.

When the value of a is 2 or 3, the groups represented by X may be the same or different.

Specific examples of the hydrosilylation catalyst include, for example, a simple substance of platinum, a simple substance of alumina, silica, carbon black or the like on which solid platinum is supported, H ₂
Chloroplatinic acid such as PtCl ₆・ 6H ₂ O, complexes of chloroplatinic acid with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (eg Pt (CH ₂ = CH ₂ ) ₂ (PPh ₃ )
₂ Pt (CH ₂ = CH ₂ ) ₂ Cl ₂ ); platinum-vinyl siloxane complex (for example, Ptn (ViMe ₂ SiOSiMe ₂ Vi) _m , Pt
[(MeViSiO) ₄ ] _m ), platinum-phosphine complex (eg Pt (PPh ₃ ) ₄ , Pt (PBu) ₄ ), platinum-phosphite complex (eg Pt [(P (OPh) ₃ ] ₄ ) ( In the above formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group,
Ph represents a phenyl group, m and n represent integers), dicarbonyldichloroplatinum, and platinum-hydrocarbon complexes described in Ashby US Pat. Nos. 3159601 and 3159662. Lamorea
ux) U.S. Pat. No. 3,220,972, such as the platinum alcoholate catalysts. In addition, the platinum chloride-olefin composites described in Modic US Pat. No. 3,516,946 are also useful in the present invention. Further, examples of the catalyst other than platinum compounds, for example, _{RhCl (PPh 3) 3, RhCl} 3, Rh / Al 2 O 3, RuCl 3,
IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl ₂・ 2H ₂ O, NiCl ₂ , Ti
Cl ₄ etc. can be given. Among these, chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The ratio of the hydrosilane having a reactive group to be used is 1 to 10 with respect to 1 mol of the carbon-carbon double bond-containing organic group in the carbon-carbon double bond-containing organic group-containing imide compound.
Mol, preferably 1 to 5 mol, more preferably 1 to 3
It is in the molar range. If the proportion of hydrosilane is less than 1 mol, it is difficult to obtain the target compound in good yield, which is not preferable. On the other hand, if it exceeds 10 mols, hydrosilane is generally expensive and the production cost is high, and it is difficult to remove excess hydrosilane, which is not preferable.

The amount of the hydrosilylation catalyst used is not particularly limited, but it is 10 ^-1 to 1 mol per 1 mol of the alkenyl group.
It is preferably used in the range of 10 ^-8 mol, preferably 10 ^-3 to 10 ^-6 mol. If the amount of the catalyst is less than 10 ^-8 mol, curing tends not to proceed sufficiently, and if it exceeds 10 ^-1 mol, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas is generated. However, the cured product may foam.

The hydrosilylation reaction is generally 0 to 1
It is carried out in a temperature range of 50 ° C, and if necessary, a hydrocarbon solvent such as hexane, heptane, benzene, toluene, xylene; diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether. , Ether solvents such as anisole; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate;
Methanol, ethanol, propanol, butanol,
Alcohol solvents such as 1,4-butanediol and ethylene glycol; suitable organic solvents such as halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene, alone or as a mixture of two or more. Good.

The method and order of addition of the three components of the carbon-carbon double bond-containing organic group-containing imide compound, the reactive group-containing hydrosilane, and the hydrosilylation catalyst are within the range that does not reduce the yield of the desired reaction product. It is not particularly limited as long as it is a carbon-carbon double bond-containing organic group-containing imide compound and a mixture of a hydrosilane having a reactive group or a solution obtained by dissolving it in an organic solvent may be added with a hydrosilylation catalyst. Alternatively, a method may be used in which the hydrosilylation catalyst and the carbon-carbon double bond-containing organic group-containing imide compound or the hydrosilane having a reactive group are mixed in advance and the remaining one component is added.

Specific examples of the compound thus obtained are, for example,

[0057]

[Chemical 16]

[0058]

[Chemical 17]

[0059]

[Chemical 18]

[0060]

[Chemical 19]

[0061]

[Chemical 20]

[0062]

[Chemical 21]

And the like.

The imide compound obtained by the production method of the present invention has excellent long-term storage stability and is liquid or room temperature at room temperature.
It shows a melting point below ℃, hexane, heptane, benzene,
Hydrocarbon solvents such as toluene and xylene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and anisole; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, benzoin Ester solvents such as methyl acidate and ethyl benzoate;
Methanol, ethanol, propanol, butanol,
Alcohol solvent such as ethylene glycol; soluble in halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride, chlorobenzene, etc., and it cures at a temperature of 200 ° C or less without catalyst. When using a condensation catalyst
It cures at temperatures as low as 80 ° C. The cured products obtained by these two methods have essentially the same properties. Since the resin obtained by curing is excellent in heat resistance, chemical resistance and mechanical properties, the imide compound obtained by the method of the present invention can be used in various applications such as resin modifiers and sites that are easily exposed to high temperatures. It is preferably used as a coating agent and the like.

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

Example 1 Pyromellitic dianhydride 21.8 g (0.10 mo
l) was dissolved in 350 ml of N, N-dimethylacetamide (hereinafter abbreviated as DMAc). Allylamine 1 at room temperature
1.4 g (0.20 mol) was added slowly over about 30 minutes.
After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the obtained amic acid solution was heated to reflux, and the mixture was further heated and stirred for 3 hours for imidization. After cooling, the reaction solution was poured into a large amount of methanol to precipitate the product, which was then filtered. The obtained needle crystals were washed with methanol and dried under reduced pressure at room temperature for several hours. The melting point of the obtained imide compound was 220 to 225 ° C.

10 g of the obtained imide compound was added to chloroform.
It was dissolved in 200 ml, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was added thereto. At room temperature, 12.5 ml of methyldimethoxysilane was added with a dropping funnel and reacted at 50 ° C. for 1 hour. After the reaction, the reaction solution was poured into methanol to cause precipitation, followed by filtration, washing with methanol, and drying at room temperature for several hours to obtain a target compound of formula (VI):

[0069]

[Chemical formula 22]

Thus, 15.1 g of the imide compound (VI) having a reactive silicon group represented by the above formula was obtained.

Melting point: 120-126 ° C.

¹ H NMR (CDCl ₃ ) δ: 0.14 (s, 6H, SiCH ₃ ).
, 0.66 (t, 4H, Si CH ₂ ), 1.79 (m, 4H, CH ₂ CH ₂ CH ₂ )
, 3.50 (s, 12H, Si (OCH ₃ ) ₂ ), 3.74 (t, 4H, NCH ₂ )
, 8.25 (s, 2H, aromatic).

Example 2 An imide compound having two allyl groups in the molecule was obtained in the same manner as in Example 1. The melting point of the obtained imide compound is 2
The temperature was 20 to 225 ° C. The obtained imide compound (34.0 g) was dissolved in chloroform (700 ml), and H ₂ PtCl ₆ · 6H ₂ was added thereto.
0.85 ml of O 10% ethanol solution was added. At room temperature, add 55.8 g of dimethoxymethylsilane with a dropping funnel,
The reaction was carried out at 50 ° C for 5 hours. During the reaction, phenomena such as increase in viscosity of the reaction solution and gelation were not observed. After the reaction, the reaction solution was poured into methanol to cause precipitation, which was then filtered, washed with methanol, and dried at room temperature for several hours to obtain 48.9 g of an imide compound (VI) having the same reactive silicon group as above. The imide compound hardly gelled even after being stored in air at room temperature for 2 weeks.

Example 3 20 ml of chloroform was added to 10 g of the imide compound (VI) obtained in Example 1 to prepare a chloroform solution of the imide compound, and 0.3 g of tin octylate and 0.075 g of laurylamine were used as catalysts. Was mixed to obtain a curable composition. The composition was stored at 50 ° C. and 60% relative humidity for 4 days, and then cured at 250 ° C. for 12 hours to prepare a cured product.

Using the differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd., the obtained cured product was subjected to TGA measurement under a nitrogen stream. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 4 5 g of the imide compound (VI) obtained in Example 1 was stored for 6 hours in a perfect oven kept at 180 ° C. without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The cured product thus obtained was subjected to TGA measurement under a nitrogen stream using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. The excess 5% and 10% weight loss obtained there is shown in Table 1. Further, the cured product is N, N-dimethylformamide,
The results of appearance evaluation after immersion in 10% hydrochloric acid at room temperature for 10 days are shown in Table 2.

Example 5 32.2 g (0.10 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was dissolved in 200 ml of DMAc under a nitrogen stream. At room temperature, allylamine 11.4 g (0.20 m
ol) was gradually added over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain an imide compound. The melting point of the obtained imide compound is 153-
It was 154 ° C.

10 g of the obtained imide compound was added to chloroform.
It was dissolved in 200 ml, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was added thereto. At room temperature, 12.5 ml of methyldimethoxysilane was added with a dropping funnel and reacted at 50 ° C. for 1 hour. After the reaction, the reaction solution was poured into methanol to cause precipitation, which was filtered, washed with methanol, and dried at room temperature for several hours to obtain the target compound of formula (VII):

[0081]

[Chemical formula 23]

12.9 g of an imide compound (VII) having a reactive silicon group represented by

Melting point: 82-86 ° C.

¹ H NMR (CDCl ₃ ) δ: 0.14 (s, 6H, SiCH ₃ ).
, 0.66 (t, 4H, SiCH ₂ ), 1.77 (m, 4H, CH ₂ CH ₂ CH ₂ )
, 3.51 (s, 12H, Si (OCH 3) 2), 3.70 (t, 4H, NCH 2)
, 8.02 (d, 2H, aromatic), 8.15 (m, 4H, aromatic).

Example 6 To 10 g of the imide compound (VII) obtained in Example 5 was added 20 ml of chloroform to prepare a chloroform solution of the imide compound, and 0.3 g of tin octylate and 0.075 g of laurylamine were used as catalysts. The curable composition was obtained by blending. The composition was stored at 50 ° C. and 60% relative humidity for 4 days, and then cured at 250 ° C. for 12 hours to prepare a cured product.

The obtained cured product was subjected to TGA measurement under a nitrogen stream using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 7 5 g of the imide compound (VII) obtained in Example 5 was stored in a perfect oven kept at 150 ° C. for 6 hours without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA measurement under a nitrogen stream using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Further, the cured product is N, N-dimethylformamide,
The results of appearance evaluation after immersion in 10% hydrochloric acid at room temperature for 10 days are shown in Table 2.

Example 8 31.0 g (0.10 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was added to 400 g of DMAc under a nitrogen stream.
dissolved in l. At room temperature, allylamine 11.4 g (0.2
0 mol) was gradually added over about 30 minutes. After addition 2
Stirring was continued for 0 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain an imide compound. The melting point of the obtained imide compound is 153-1.
It was 54 ° C.

10 g of the obtained imide compound was added to chloroform.
It was dissolved in 200 ml, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was added thereto. At room temperature, 14.5 ml of triethoxysilane was added with a dropping funnel and reacted at 50 ° C. for 1 hour. After the reaction, the reaction solution was poured into methanol to cause precipitation, which was filtered, washed with methanol, and dried at room temperature for several hours to obtain the target compound of formula (VIII):

[0092]

[Chemical formula 24]

There was obtained 12.2 g of the imide compound (VIII) having a reactive silicon group represented by:

Melting point: 71-74 ° C.

¹ H NMR (CDCl ₃ ) δ: 0.66 (t, 4H, SiC
H ₂ ), 1.19 (t, 9H, SiOCH ₂ CH ₃ ), 1.77 (m, 4H, CH ₂ CH ₂ C
H ₂ ), 3.70 (t, 4H, NCH ₂ ), 3.81 (q, 6H, SiOCH ₂ C
H ₃ ), 7.38 (m, 4H, aromatic), 7.88 (d, 2H, aromatic)
.

Example 9 20 ml of chloroform was added to 10 g of the imide compound (VIII) obtained in Example 8 to prepare a chloroform solution of the imide compound, and 0.3 g of tin octylate was used as a catalyst.
And 0.075 g of laurylamine were blended to obtain a curable composition. The composition was stored at 50 ° C. and 60% relative humidity for 4 days, and then cured at 250 ° C. for 12 hours to prepare a cured product.

The obtained cured product was subjected to TGA measurement under a nitrogen stream using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 10 Under a nitrogen stream, 35.8 g (0.10 mol) of 3,3'4,4'-diphenylsulfone tetracarboxylic dianhydride was added to DMAc 200
dissolved in ml. At room temperature, 11.4 ml of allylamine (0.
20 mol) was added gradually over about 30 minutes. After the addition is complete
Stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain an imide compound. The melting point of the obtained imide compound is 201 to 2
It was 04 ° C.

10 g of the obtained imide compound was added to chloroform.
It was dissolved in 200 ml, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was added thereto. At room temperature, add 10.3 ml of methyldiacetoxysilane with a dropping funnel and add 1 at 80 ℃.
Reacted for hours. After the reaction, the reaction solution was poured into methanol to cause reprecipitation, followed by filtration and washing with methanol,
After drying at room temperature for several hours, the desired formula (IX):

[0101]

[Chemical 25]

10.5 g of an imide compound (IX) having a reactive silicon group represented by

Melting point: 97-100 ° C.

¹ H NMR (CDCl ₃ ) δ: 0.14 (s, 6H, SiCH ₃ ).
, 0.66 (t, 4H, SiCH ₂ ), 1.77 (m, 4H, CH ₂ CH ₂ CH ₂ ),
2.02 (s, 12H, Si (OCOCH ₃ ) ₂ ), 3.72 (t, 4H, NCH ₂ ),
8.03 (d, 2H, aromatic), 8.38 (m, 4H, aromatic).

Example 11 5 g of the imide compound (IX) obtained in Example 10 was stored in a perfect oven kept at 180 ° C. for 6 hours without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA measurement under a nitrogen stream using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Comparative Example 1 3 g of tin octylate and 0.75 g of laurylamine were added to 100 g of polypropylene glycol having a dimethoxymethylsilyl group at both ends (molecular weight of about 8000), and the mixture was kneaded. A rubber-like cured product was obtained by storing at 50 ° C. (60% relative humidity).

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. under a nitrogen stream. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Comparative Example 2 Instead of the polypropylene glycol having dimethoxymethylsilyl groups at both ends in Comparative Example 1, poly (γ-methyl-δ-valerolactone) having dimethoxymethylsilyl groups at both ends (molecular weight: about 8000). ) Was used, and a rubber-like cured product was obtained in exactly the same manner as in Comparative Example 1.

The obtained cured product was subjected to TGA measurement under a nitrogen gas flow using a differential balance TG-DTA manufactured by Rigaku Denki Co., Ltd. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

[0111]

[Table 1]

[0112]

[Table 2]

It can be seen from Table 1 that the resin obtained by curing the imide compound obtained by the method of the present invention has excellent heat resistance.

Example 12 Under nitrogen atmosphere, 32.2 g (0.10 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was dissolved in 200 ml of DMAc. At room temperature, allylamine 11.4 g (0.20 m
ol) was gradually added over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain 38.1 g of an imide compound having two allyl groups in the molecule. The melting point of the obtained imide compound 38.1 g is 153 to 154 ° C.
Met.

38.1 g of the obtained imide compound was dissolved in 700 ml of chloroform, and 0.95 ml of 10% H ₂ PtCl ₆ .6H ₂ O ethanol solution was added thereto. At room temperature, 32.8 g of dichloromethylsilane was added with a dropping funnel and reacted at 50 ° C. for 5 hours. During the reaction, phenomena such as increase in viscosity of the reaction solution and gelation were not observed. After the reaction, n-
Pour into hexane, precipitate, then filter, wash with n-hexane and dry at room temperature for several hours to give the desired formula (X):

[0117]

[Chemical formula 26]

49.9 g of an imide compound (X) having a reactive silicon group represented by

Example 13 31.0 g (0.10 mol) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was added to DMAc 400 under a nitrogen stream.
dissolved in ml. 23.8 g of p-aminostyrene at room temperature
(0.20 mol) was added slowly over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain 46.6 g of an imide compound.

46.6 g of the obtained imide compound was dissolved in 1000 ml of chloroform, and 1.17 ml of 10% H ₂ PtCl ₆ .6H ₂ O ethanol solution was added thereto. At room temperature, 58.3 g of tris (dimethylamino) silane was added with a dropping funnel and reacted at 50 ° C. for 5 hours. During the reaction, phenomena such as increase in viscosity of the reaction solution and gelation were not observed. After the reaction, the reaction solution was poured into n-hexane, precipitated and then filtered, washed with n-hexane and dried at room temperature for several hours to obtain a desired imide compound having a silicon group, formula (XI):

[0122]

[Chemical 27]

A compound represented by the formula (XII):

[0124]

[Chemical 28]

A compound of the formula (XIII):

[0126]

[Chemical 29]

72.6 g of a mixture of compounds of the formula

The mixture of the above-mentioned imide compounds showed almost no gelation even after being stored in air at room temperature for 2 weeks.

Example 14 Under a nitrogen stream, 35.8 g (0.10 mol) of 3,3'4,4'-diphenylsulfone tetracarboxylic dianhydride was added to DMAc 200
dissolved in ml. 23.8 g of m-aminostyrene at room temperature
(0.20 mol) was added slowly over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 1 was carried out to obtain 50.7 g of an imide compound.

50.7 g of the obtained imide compound was dissolved in 1000 ml of chloroform, and 1.17 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was added thereto. At room temperature, 56.5 g of methyldiacetoxysilane was added with a dropping funnel and reacted at 80 ° C. for 1 hour. During the reaction, phenomena such as increase in viscosity of the reaction solution and gelation were not observed. After the reaction, the reaction solution was poured into methanol to reprecipitate and then filtered,
Washed with n-hexane, dried at room temperature for several hours, the target imide compound having a silicon group of the formula (XIV):

[0132]

[Chemical 30]

A compound represented by the formula (XV):

[0134]

[Chemical 31]

A compound represented by the formula (XVI):

[0136]

[Chemical 32]

75.1 g of a mixture of compounds of the formula are obtained.

The mixture of the above imide compounds showed almost no gelation even after being stored in air at room temperature for 2 weeks.

Comparative Example 3 Under a nitrogen stream, 12.9 g (0.04 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride was suspended in 50 ml of DMAc. At 0-5 ° C, 13.1 g (0.08 mol) of (γ-aminopropyl) -dimethoxymethylsilane was gradually added over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes at room temperature to obtain an amic acid containing a reactive silicon group. A mixture of 8.5 g of acetic anhydride and 6.6 g of pyridine was added to this solution at room temperature, and stirring was continued for 16 hours. During this time, a large amount of precipitate formed. The viscosity of the reaction solution increased with the elapse of the reaction time, and after 16 hours, the reaction solution completely gelled.

[0140]

According to the production method of the present invention, first, an imide compound containing a carbon-carbon double bond-containing organic group is synthesized,
Since the method of subsequent hydrosilylation is used, the material is easily available, side reactions such as gelation do not occur during the production of the target reactive silicon group-containing imide compound, and the yield is high. An imide compound of
Moreover, since the carboxyl group and amino group do not exist in the system, the obtained imide compound has excellent long-term storage stability. Furthermore, since the curing reaction of the obtained imide compound substantially proceeds only by the condensation reaction of silanol, the curing reaction can proceed at a relatively low temperature. The obtained cured product from the imide compound has excellent heat resistance and chemical resistance.

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[Procedure amendment]

[Submission date] August 21, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction content]

The amount of the hydrosilylation catalyst used is not particularly limited, but it is 10 ^-1 to 1 mol per 1 mol of the alkenyl group.
It is preferably used in the range of 10 ^-8 mol, preferably 10 ^-3 to 10 ^-6 mol. If the amount of catalyst is less than 10 ^-8 mol, hydrosilyl
The hydrogenation reaction tends not to proceed sufficiently, and if it exceeds 10 ⁻¹ mol, the hydrosilylation catalyst is generally expensive and corrosive .
The yield of the compound may decrease .

Claims (1)

Claims (a) General formula (I): (In the formula, R ⁰ contains an aromatic group having 6 to 30 carbon atoms;
A tetracarboxylic acid dianhydride represented by the general formula (II): (Wherein R ¹ represents a carbon-carbon double bond-containing organic group having 2 to 20 carbon atoms) and a primary amine containing a carbon-carbon double bond-containing organic group in an organic polar solvent. To obtain a solution of amic acid, which is (b) and then imidized to obtain an imide compound having two carbon-carbon double bond-containing organic groups in one molecule, (c) (b) The imide compound obtained in the formula (III): embedded image was prepared in the presence of a hydrosilylation catalyst. (In the formula, R ² is a monovalent organic group having 1 to 20 carbon atoms or the general formula (IV): (In the formula, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and three R ³ may be the same or different), X is a hydroxyl group or hydrolyzed. Represents a reactive group, a is 1, 2 or 3, and when two or more R ² and X are present, they may be the same or different, and a reactive group represented by A method for producing an imide compound having two reactive silicon groups in one molecule, which comprises performing hydrosilylation with a hydrosilane.