JP3241355B2 - Imide compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel imide compound. More specifically, a liquid that is a liquid or a solid having a low melting point at room temperature, cures quickly when a catalyst is actuated, and cures quickly, and has excellent heat resistance, chemical resistance, and mechanical properties after curing. Imide compound which gives a product.

[0002]

2. Description of the Related Art Various compositions have been developed as room temperature curable compositions. However, cured compositions having excellent heat resistance, chemical resistance and mechanical properties after curing have been developed. Few curable compositions have been developed.

[0003] As an example of the room-temperature curable composition, for example, a composition containing a silyl ether group-terminated polyether is disclosed (JP-A-52-73998).
The cured product obtained from this composition is rubbery at room temperature and has excellent mechanical properties, especially at low temperatures, but at temperatures above 100 ° C., the mechanical properties are significantly reduced in a short time. Under such conditions, it is practically unusable. A room-temperature-curable resin composition having a main chain of polyester is also disclosed (Japanese Patent Publication No. Sho 49).
In the case of this composition, the heat resistance of the obtained cured product is not sufficient. In general, polyesters have better heat resistance than polyethers, but satisfactory ones have not yet been obtained.

An object of the present invention is to provide an imide compound which is condensed at a low temperature by the action of a catalyst to form a cured product having excellent heat resistance.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on such problems, and as a result, a novel imide compound having an imide skeleton and a reactive silicon group in the same molecule has been found to be liquid or low-temperature at room temperature. The present inventors have found that a solid having a melting point makes it easy to prepare a cured product and gives a cured product having excellent heat resistance after curing, and has completed the present invention.

The present invention provides a compound represented by the general formula (I):

[0007]

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(Wherein R ⁰ is a tetravalent aromatic group having 6 to 30 carbon atoms or —CO— , —O— , —SO ₂ —, —C
_{(CH 3) 2 -, -} C (CF 3) 2 -, - S -, - Si (C
H _{3) 2} - and _{-Si (CH 3) 2 -O-} Si (CH 3) 2
_{-O-Si (CH 3) 2} - 2 selected from monovalent radicals comprising an aromatic ring linked via a tetravalent radical, R ¹ is 1 to the number of carbon atoms
20 divalent aliphatic alkylene group, a phenylene group, a naphthylene group, a group selected from the anthracenylene group, R ²
Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or

[0009]

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Wherein R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and three R ³ may be the same or different, and X represents CH ₃ COO—, (CH ₃ ) ₂
N-, CH ₃ CONH- or _{(CH 3) 2 C = N} -O-
Wherein a is 1, 2 or 3, two R ¹ may be the same or different, and when two or more R ² and X are present, they may be the same ,
And may be different).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The imide compound of the present invention has the general formula (I):

[0012]

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A novel compound represented by the formula:

In the general formula (I), R ⁰ has 6 to 3 carbon atoms.
0 tetravalent aromatic groups or -CO-, -O- , -SO
_{2 -, - C (CH 3} ) 2 -, - C (CF 3) 2 -, - S-,
-Si (CH _{3) 2} - and _{-Si (CH 3) 2 -O-} Si
It is a tetravalent group composed of an aromatic ring bonded via a divalent group selected from (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — .
If the number of carbon atoms exceeds 30, it is difficult to obtain and is not practical. R
It is preferable that ⁰ is any of these groups, since a cured product having excellent heat resistance after curing is obtained.

Particularly preferred examples of the tetravalent group include, for example,

[0016]

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[0017]

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And the like. These may contain only one kind or two or more kinds may be mixed and contained.

R ¹ is a group selected from a divalent aliphatic alkylene group having 1 to 20 carbon atoms, a phenylene group, a naphthylene group and an anthracenylene group. Those having more than 20 carbon atoms are difficult to obtain and are not practical.

Specific examples of the divalent aliphatic alkylene group represented by R ¹ include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, and the like.
Examples include a decylene group, an undecylene group, a dodecylene group, an isopropylene group, an isobutylene group, and an isooctylene group.

The two R ¹ in the general formula (I) may be the same or different. R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or

[0022]

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(Wherein, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and three R ^{3 s} may be the same or different).
When R ² is an alkyl group, it is preferably an alkyl group having 1 to 15 carbon atoms, when it is an aryl group, an aryl group having 6 to 15 carbon atoms is preferable, and when it is an aralkyl group, it has 7 carbon atoms.
Up to 15 aralkyl groups are preferred. In this case, if the carbon number exceeds 20, it becomes difficult to obtain a raw material. Also, R ²
Is a triorganosiloxy group, R ³ has 10 carbon atoms
If it exceeds 300, it becomes difficult to obtain raw materials.

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

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

When two or more groups represented by R ² are present in the molecule, they may be the same or different.

X is CH ₃ COO—, (CH ₃ ) ₂ N—, C
H ₃ CONH— or (CH ₃ ) ₂ C = N—O—
A hydrolysable group). In the case where X is such, it is preferable from the viewpoint that the hydrolysis reaction occurs very quickly. Further, from the viewpoint that a large easy and reactivity to obtain raw materials.

When two or more Xs are present in a 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 groups.

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

Specific examples of the imide compound of the present invention include:
For example

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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And the like.

In the method for producing the imide compound of the present invention, first, a corresponding alkenyl group-containing imide compound is synthesized, and then,

[0039]

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(Wherein R ² and a are the same as described above;
X 'represents a hydroxyl group or a hydrolyzable group. The hydrolyzable group is not particularly limited, and includes a conventionally known hydrolyzable group. Specifically, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, an oxime group, a ketoxime group, an amino group, an amide group And an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, a hydrogen atom, an alkoxy group, an acyloxy group, an oxime group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group and an alkenyloxy group are easily available and have high reactivity. Halogen atom, acyloxy group, oxime group, amino group, and amide group are particularly preferable from the viewpoint that the hydrolysis reaction occurs very quickly, and alkoxy group is particularly preferable from the viewpoint that the hydrolytic property is mild and easy to handle. . X 'is 2 in the molecule
When there are more than one, they may be the same or different) (hereinafter referred to as a reactive silicon group), and if necessary, conversion of the hydrolyzable group (X ') is performed. This method is particularly preferable in terms of availability of materials, yield, and the like.

The method for producing the corresponding alkenyl group-containing imide compound includes the following method. That is, a method of reacting an aromatic tetracarboxylic dianhydride with an alkenyl group-containing amine in an organic polar solvent to obtain an amic acid solution, and then heating the solution to thermally imidize the solution, A carboxylic acid dianhydride and an alkenyl group-containing amine are reacted in an organic polar solvent to obtain a solution of an amic acid, and then a dehydrating agent such as acetic anhydride is applied thereto,
A method of chemically imidizing an aromatic carboxylic acid dianhydride with an alkenyl group-containing amine in an organic polar solvent to obtain a solution of an amide acid, and then the solution is converted to an amide such as water or hydrocarbon. A method in which an amide acid is precipitated as a precipitate by contacting with a poor solvent for an acid and heated, a method in which an aromatic tetracarboxylic acid component and an alkenyl group-containing isocyanate are reacted in an organic polar solvent to directly obtain an imide compound, and the like. Can be given. Although the imide compound of the present invention can be produced by any of these methods, the production apparatus and the production process are simpler or easier, and the raw materials to be used are easily available.
I.e., an aromatic tetracarboxylic dianhydride and an alkenyl group-containing amine are reacted with a sulfoxide solvent such as dimethyl sulfoxide and diethyl sulfoxide; a formamide solvent such as N, N-dimethylformamide and N, N-diethylformamide An acetamide-based solvent such as N, N-dimethylacetamide, N, N-diethylacetamide; N-methyl-2-pyrrolidone;
Pyrrolidone solvents such as N-acetyl-2-pyrrolidone and N-vinyl-2-pyrrolidone; phenol solvents such as phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol; pyridine; Hexamethylphosphamide, γ-
A method is preferred in which a solution of an amic acid is obtained by reacting at 80 ° C. or lower in a single or a mixture of two or more organic polar solvents such as butyrolactone, and then the solution is heated to 100 to 250 ° C. for imidization.

As a method for introducing a reactive silicon group into the alkenyl group-containing imide compound, there is a method in which a hydrosilane having a hydrolyzable group is allowed to act on the alkenyl group-containing imide compound to perform hydrosilylation. The hydrosilane having a hydrolyzable group is represented by the general formula (II):

[0043]

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(Wherein R ² , X ′, and a are the same as those described above). X ′ in the general formula (II),
When two or more R ² are present, they may be the same or different.

The introduction reaction of the reactive silicon group into the alkenyl group-containing imide compound, for example H ₂ PtCl ₆ · 6H
₂ O, metal platinum, RhCl (PPh ₃ ) ₃ , RhCl ₃ , R
h / Al ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , A
lCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl ₄
The reaction can be carried out by performing a hydrosilylation reaction using a compound such as a catalyst.

The hydrosilylation reaction is generally carried out at 0 to 150
Carried out in a temperature range of ℃, if necessary, hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene; diethyl ether, tetrahydrofuran, 1,
Ether solvents such as 4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and anisole; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, benzoate Ester solvents such as ethyl acid; methanol, ethanol, propanol, butanol,
The reaction is performed using an appropriate organic solvent such as an alcoholic solvent such as 1,4-butanediol and ethylene glycol; a single or a mixture of two or more halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene. be able to.

The conversion of the hydrolyzable group (X ′ → X) is
General formula (I '):

[0048]

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The imide compound represented by the general formula (II)
I): a compound represented by H-X (III) (wherein X represents a halogen atom, an acyloxy group, an oxime group, an amino group or an amide group), or a general formula (IV): MX (IV) (Wherein X is the same as above and M represents an alkali metal atom).
The reaction can be easily carried out by reacting at a temperature of 1 to 24 hours. At this time, if necessary, for example, 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 and methyl isobutyl ketone, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate and ethyl benzoate, methylene chloride, chloroform, A suitable organic solvent such as a halogenated hydrocarbon solvent such as ethylene chloride and chlorobenzene alone or a mixture of two or more thereof may be used.

The imide compound of the present invention is a liquid at room temperature or shows a melting point of 150 ° C. or less, and is a hydrocarbon solvent such as hexane, heptane, benzene, toluene and xylene; diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene Ether solvents such as glycol dimethyl ether, ethylene glycol diethyl ether and anisole; ketone solvents such as acetone, methyl ethyl ketone and ethyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate and ethyl benzoate Alcohol solvents such as methanol, ethanol, propanol, butanol, 1,4-butanediol, and ethylene glycol;
It is soluble in halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene, and cures at a temperature of 200 ° C. or less even without a catalyst. Further, when a condensation catalyst is used, the composition is cured even at a low temperature of 80 ° C. or less. The cured products obtained by these two methods have essentially the same properties. The resin obtained by curing has a high thermal decomposition temperature, is excellent in acid resistance, alkali resistance, water resistance and chemical resistance, and is also excellent in mechanical properties.

The curable composition comprising the imide compound of the present invention is a composition comprising one or more of the imide compounds represented by the above general formula (I) and one or more of the silanol condensation catalyst. is there.

Specific examples of the silanol condensation catalyst include titanates such as tetrabutyl titanate and tetrapropyl titanate; and tin carboxylic acids such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate. Salts; reaction products of dibutyltin oxide and phthalic acid esters; dibutyltin diacetylacetonate; aluminum trisacetylacetonate;
Organoaluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, mono Ethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl ) Phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimida And amine compounds such as 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) or their salts with carboxylic acids; low molecular weight polyamides obtained from excess polyamines and polybasic acids Resin; reaction product of excess polyamine and epoxy compound; silane coupling agent having an amino group such as γ-aminopropyltrimethoxysilane, N- (β
Silanol condensation catalysts such as -aminoethyl) aminopropylmethyldimethoxysilane, and also other acidic catalysts,
Known silanol condensation catalysts such as basic catalysts and the like can be mentioned. These catalysts may be used alone or in combination of two or more. Of these, a tin compound, an organoaluminum compound, and an amine compound, alone or as a mixture of two or more thereof, are particularly preferred because of excellent workability, easy handling, and uniform curing.

The amount of the silanol condensation catalyst in the composition is preferably 0.01 to 20 parts, and more preferably 0.1 to 100 parts (parts by weight, hereinafter the same) of the imide compound.
To 10 parts. If the amount of the catalyst is too small, the curing rate will be slow, and it will be difficult for the curing reaction to proceed sufficiently, and it will be difficult to obtain a good cured product. Heat generation and foaming occur, and a good cured product tends to be hardly obtained.

When the imide compound is a solid, the imide compound may be, for example, hexane, heptane,
Hydrocarbon solvents such as benzene, toluene and xylene;
Ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and anisole; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, propyl acetate, acetic acid Butyl, methyl benzoate,
Ester solvents such as ethyl benzoate; alcohol solvents such as methanol, ethanol, propanol, butanol, 1,4-butanediol, and ethylene glycol; halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride, and chlorobenzene. May be dissolved in a suitable organic solvent alone or in a mixture of two or more, and a silanol condensation catalyst may be added to form a composition.

The amount of the solvent used is not particularly limited as long as the workability is not impaired. However, it is easy to remove the solvent at the time of curing, and it is easy to obtain a homogeneous cured product with less foaming. The total concentration of the imide compound and the silanel condensation catalyst is preferably from 20% (% by weight, the same applies hereinafter) to 100%, and more preferably from 30% to 100%.
It is more preferably at most 40%, particularly preferably at least 40% and at most 100%.

The composition may further contain, if necessary, an adhesion improver, a physical property modifier, a storage stability improver, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, a metal deactivator, and ozone deterioration. Various additives such as an inhibitor, a light stabilizer, an amine-based radical chain inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added. The total amount of the additives is not particularly limited as long as the various properties of the cured product are not significantly reduced, but is more preferably 1 to 300 parts, more preferably 1 to 1 part, per 100 parts of the imide compound.
00 parts.

The imide compound of the present invention and the curable composition using the same can be cured by moisture and / or heat.

When the imide compound is cured by heat, the imide compound may be cured at a temperature not lower than its melting point and not higher than 350 ° C., preferably not higher than 300 ° C., more preferably not higher than 250 ° C. for 5 minutes to 24 hours. For example, a method of holding for 10 minutes to 12 hours. If the processing temperature is too high, local heat generation and foaming occur during curing,
It becomes difficult to obtain a good cured product.

In the case where the curable composition is cured by heat, the curing method may be selected from the melting temperature of the composition.
300 ° C., preferably 250 ° C. or less, more preferably 200 ° C. or less for 1 minute to 24 hours, preferably 10 minutes
For example, a method in which the temperature is maintained for minutes to 12 hours. If the treatment temperature is too high, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product.

When the composition is an organic solvent solution, the composition is heated to a temperature at which the organic solvent can volatilize (may be lower than the boiling point), or is depressurized at a temperature lower than the boiling point of the organic solvent. By treating below, it is possible to cure while distilling off the solvent.

When the composition is cured by moisture, the composition is heated at room temperature to 80 ° C. and a relative humidity of 60 to 95%.
A method of storing for 1 hour to 2 weeks, preferably for 1 hour to 1 week. When cured by moisture and heat, the composition is kept at room temperature to 80 ° C. and a relative humidity of 60 to 95.
% For one hour to two weeks, preferably one hour to one week.
After storing for a week, the compound is cured at a temperature of from the melting point of the compound to 350 ° C. or less, preferably 300 ° C. or less, more preferably 200 ° C. or less for 10 minutes to 12 hours.

The resin obtained by curing the composition is essentially a crosslinked product crosslinked by siloxane bonds,
It has a high thermal decomposition temperature, and is excellent in acid resistance, alkali resistance, water resistance, chemical resistance, and also excellent in mechanical properties, and is used in various applications such as resin modifiers and electric and electronic parts that are easily exposed to high temperatures. It is suitably used as a coating agent for surrounding parts and a heat-resistant adhesive.

[0063]

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

Reference Production Example 1 21.8 g of pyromellitic dianhydride in a stream of nitrogen
(0.10 mol) was dissolved in 350 ml of N, N-dimethylacetamide (hereinafter abbreviated as DMAc). At room temperature, 11.4 g (0.20 mol) of allylamine
Was slowly added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the obtained amic acid solution was heated to reflux, and further heated and stirred for 3 hours to carry out imidization. After cooling, the reaction solution was poured into a large amount of methanol to precipitate the product, followed by filtration. 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.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
And drop 12.5 ml of methyldimethoxysilane
The reaction was carried out at 50 ° C. for 1 hour. After the reaction,
After pouring the reaction solution into methanol and reprecipitating,
Filter, wash with methanol, dry at room temperature for several hours,
Equation (V):

[0067]

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15.1 g of an imide compound (V) having a reactive silicon group represented by the following formula was obtained.

Melting point: 120-126 ° C. _{^{1 H NMR (CDCl 3) δ}} : 0.14 (s, 6H, SiCH 3), 0.66 (t, 4H,
SiCH ₂ ), 1.79 (m, 4H, CH ₂ CH ₂ CH ₂ ), 3.50 (s, 12H, Si (OC
_{H 3) 2), 3.74 (} t, 4H, NCH 2), 8.25 (s, 2H, aromatic).

Reference Example 1 A chloroform solution of an imide compound was prepared by adding 20 ml of chloroform to 10 g of the imide compound (V) obtained in Reference Production Example 1, and 0.3 g of tin octylate and laurylamine were used as condensation catalysts. 0.075 g was obtained to obtain a curable composition. The composition is stored at 50 ° C. and 60% relative humidity for 4 days, after which it is further stored at 250 ° C. for 12 days.
After curing for a time, a cured product was prepared.

Using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. on the obtained cured product under a nitrogen stream, TG
A measurement was performed. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Reference Example 2 5 g of the imide compound (V) obtained in Reference Production Example 1 was stored for 6 hours in a perfect oven maintained at 180 ° C. without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

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

Reference Production Example 2 32.2 g (0.10 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride in a stream of nitrogen
Was dissolved in 200 ml of DMAc. At room temperature,
Allylamine 11.4 g (0.20 mol) was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Reference Production Example 1 was performed to obtain an imide compound. The melting point of the obtained imide compound is 1
53-154 ° C.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
And drop 12.5 ml of methyldimethoxysilane
The reaction was carried out at 50 ° C. for 1 hour. After the reaction,
After pouring the reaction solution into methanol and reprecipitating,
Filter, wash with methanol, dry at room temperature for several hours,
Equation (VI):

[0077]

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12.9 g of an imide compound (VI) having a reactive silicon group represented by the following formula was obtained.

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 (OC
H ₃ ) ₂ ), 3.70 (t, 4H, NCH ₂ ), 8.02 (d, 2H, aromatic),
8.15 (m, 4H, aromatic).

Reference Example 3 A chloroform solution of an imide compound was prepared by adding 20 ml of chloroform to 10 g of the imide compound (VI) obtained in Reference Production Example 2, and 0.3 g of tin octylate and laurylamine were used as condensation catalysts. 0.075 g was blended to obtain a curable composition. The composition was heated at 50 ° C. and a relative humidity of 6
It was stored at 0% for 4 days, and then cured at 250 ° C. for 12 hours to produce a cured product.

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

Reference Example 4 5 g of the imide compound (VI) obtained in Reference Production Example 2 was stored for 6 hours in a perfect oven maintained at 150 ° C. 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 gas flow using a differential thermal balance TG-DTA manufactured by Rigaku Corporation. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Reference Production Example 3 31.0 g (0.10 m) of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride in a nitrogen stream
ol) was dissolved in 400 ml of DMAc. At room temperature, 11.4 g (0.20 mol) of allylamine was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Reference Production Example 1 was carried out to obtain an imide compound. The melting point of the obtained imide compound is 15
3-154 ° C.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
14.5 ml of triethoxysilane is dropped in the funnel
And reacted at 50 ° C. for 1 hour. After the reaction, the reaction
Pour the solution into methanol, reprecipitate and filter
Wash with methanol, dry at room temperature for several hours,
Formula (VII):

[0087]

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12.2 g of an imide compound (VII) having a reactive silicon group represented by the following formula was obtained.

Melting point: 71-74 ° C. ¹ H NMR (CDCl ₃ ) δ: 0.66 (t, 4H, SiCH ₂ ), 1.19 (t, 9
H, SiOCH ₂ CH ₃ ), 1.77 (m, 4H, CH ₂ CH ₂ CH ₂ ), 3.70 (t, 4H,
NCH ₂ ), 3.81 (q, 6H, SiOCH ₂ CH ₃ ), 7.38 (m, 4H, aromati
c), 7.88 (d, 2H, aromatic).

Reference Example 5 A chloroform solution of an imide compound was prepared by adding 20 ml of chloroform to 10 g of the imide compound (VII) obtained in Reference Production Example 3, and 0.3 g of tin octylate and laurylamine were used as condensation catalysts. 0.075 g was blended to obtain a curable composition. The composition is stored at 50 ° C. and 60% relative humidity for 4 days, after which it is further stored at 250 ° C. for 12 days.
After curing for a time, a cured product was prepared.

The obtained cured product was subjected to TGA under nitrogen flow using a differential thermal balance TG-DTA manufactured by Rigaku Corporation.
A measurement was made. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 1 35.8 g (0.10 mol) of 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride in a stream of nitrogen
l) was dissolved in 200 ml of DMAc. At room temperature, 11.4 ml (0.20 mol) of allylamine was slowly added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Reference Production Example 1 was carried out to obtain an imide compound. The melting point of the obtained imide compound is 20
1 to 204 ° C.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
12.5 ml of methyldiacetoxysilane is dropped
The mixture was added by a funnel and reacted at 80 ° C. for 1 hour. reaction
Thereafter, the reaction solution was poured into methanol and reprecipitated.
After filtration, washing with methanol, drying at room temperature for several hours,
The desired formula (VIII):

[0095]

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10.5 g of an imide compound (VIII) having a reactive silicon group represented by the following formula was obtained.

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 (OC
OCH ₃ ) ₂ ), 3.72 (t, 4H, NCH ₂ ), 8.03 (d, 2H, aromati
c), 8.38 (m, 4H, aromatic).

Example 2 5 g of the imide compound (VIII) obtained in Example 1 was stored in a perfect oven maintained at 180 ° C. for 6 hours without adding a condensation catalyst. The solid obtained by this treatment was insoluble in chloroform.

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

[0100] Reference Production Example 4 and Reference Example _{6 H 2 PtCl 6 · 6H 2} O 10% ethanol solution of 0.2
A reactive silicon group-containing imide compound was obtained in the same manner as in Example 1 except that 3 ml was added and methyldimethoxysilane was used instead of diacetoxymethylsilane, and a cured product was produced in the same manner as in Example 2.

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

Comparative Example 1 To 100 parts of polypropylene glycol having a dimethoxymethylsilyl group at both terminals (molecular weight: about 8,000), 3 parts of tin octylate and 0.75 part of laurylamine were added and kneaded, followed by kneading at room temperature. After further storage at 50 ° C. (60% relative humidity) for 4 days, a rubber-like cured product was obtained.

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

Comparative Example 2 Poly (γ-methyl-δ-valerolactone) having a dimethoxymethylsilyl group at both ends instead of polypropylene glycol having a dimethoxymethylsilyl group at both ends in Comparative Example 1 (molecular weight: about 8,000) ) Was used, and the other conditions were the same as in Comparative Example 1 to obtain a rubber-like cured product.

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

Example 3 Nitrogen gasification, pyromellitic dianhydride 26.2 g
(0.12 mol) was dissolved in 350 ml of DMAc. At room temperature, 11.4 g of allylamine (0.20
mol) was slowly added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the obtained amic acid solution was heated until the solution was refluxed, and further heated and stirred for 3 hours. After cooling, the reaction solution was poured into a large amount of methanol to precipitate the product, followed by filtration. The obtained needle crystals were washed with methanol and dried under reduced pressure at room temperature for several hours.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
In the above, 16.4 g of diacetoxymethylsilane was added dropwise.
The reaction was carried out at 50 ° C. for 5 hours. After the reaction,
The reaction solution was poured into methanol and reprecipitated.
Filter, wash with methanol, dry at room temperature for several hours,
Equation (IX):

[0109]

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Thus, 17.3 g of the imide compound (IX) having a reactive silicon group represented by the following formula was obtained.

Example 4 2 g of the imide compound (IX) obtained in Example 3 was dissolved in 6 g of chloroform to prepare a chloroform solution of the imide compound, and 0.06 tin tin octylate was used as a condensation catalyst.
g and 0.015 g of uralylamine were blended to obtain a thermosetting composition. The composition was stored at 50 ° C. and 60% relative humidity for 2 days. Thereafter, curing was further performed at 200 ° C. for 3 hours to produce 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 Corporation. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Comparative Example 3 Under a nitrogen stream, 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 mol) was gradually added over about 30 minutes. After completion of the addition, 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 to carry out imidization. After allowing to cool, the reaction solution was poured into a large amount of methanol to precipitate the product, followed by filtration. The obtained powder was washed with methanol and dried at room temperature under reduced pressure for several hours.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
8.6 g of dichloromethylsilane in the dropping funnel
More reaction was carried out at 50 ° C. for 5 hours. After the reaction,
The solution was poured into n-hexane, precipitated, and then filtered.
And washed with n-hexane, dried at room temperature for several hours,
Equation (X):

[0116]

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13.1 g of an imide compound (X) having a reactive silicon group represented by the following formula was obtained.

Comparative Example 4 2 g of the imide compound (X) obtained in Comparative Example 3 was dissolved in 6 g of chloroform.
It was stored in a thermo-hygrostat maintained at a relative humidity of 85% for one week. The solid obtained by this treatment was insoluble in chloroform.

The obtained cured product was subjected to TGA under nitrogen flow using a differential thermal balance TG-DTA manufactured by Rigaku Corporation.
A measurement was made. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 5 31.0 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride was added with DMAc in a stream of nitrogen.
Dissolved in 400 ml. At room temperature, allylamine 1
1.4 g (0.20 mol) was gradually added over about 30 minutes. After completion of the addition, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Example 3 was carried out to obtain an imide compound.

10 g of the obtained imide compound was added to chloroform.
Dissolved in 200 ml of _TwoPtCl₆・ 6H_Two
0.25 ml of a 10% ethanol solution was added. room temperature
12.5 g of tris (dimethylamino) silane
The mixture was added through a dropping funnel and reacted at 50 ° C. for 5 hours. Anti
After the reaction, the reaction solution was poured into n-hexane to precipitate.
After filtration, washing with n-hexane and drying at room temperature for several hours
And the desired formula (XI):

[0123]

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18.6 g of an imide compound (XI) having a silicon group represented by the following formula was obtained.

Example 6 2 g of the imide compound (XI) obtained in Example 5 was dissolved in 6 g of chloroform, and the solution was added at 80 ° C. without adding a curing catalyst.
Stored in a thermo-hygrostat maintained at 85% relative humidity for one week,
Thereafter, curing was further performed at 200 ° C. for 1 hour to prepare a cured product. The solid obtained by this treatment was insoluble in chloroform.

Using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd., the cured product was subjected to TG under nitrogen flow.
A measurement was performed. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 7 10 g (0.0%) of the imide compound (X) obtained in Comparative Example 3
16 mol) was dissolved in 200 ml of chloroform. 5.6 g of acetamide was previously added to this solution at -78 ° C.
(0.096 mol) and 1.6 M n- of n-BuLi
A reaction solution obtained by reacting 60 ml (0.096 mol) of a hexane solution was added dropwise at -78 ° C over about 30 minutes. After completion of the dropwise addition, the reaction solution was kept at -78 ° C and stirred for 5 hours. After heating to room temperature, the precipitated LiCl was removed by filtration, and the filtrate was poured into n-hexane. The precipitate formed here is filtered, washed with n-hexane and dried at room temperature for several hours to obtain the desired compound of the formula (XII):

[0128]

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There was obtained 7.0 g of an imide compound (XII) having a silicon group represented by the following formula:

Example 8 2 g of the imide compound (XII) obtained in Example 7 was dissolved in 6 g of chloroform to prepare a chloroform solution of the imide compound.
6 g and 0.015 g of laurylamine were blended to obtain a thermosetting composition. The composition is cured at 50 ° C. and 60% relative humidity for 2 hours.
Saved for days. Thereafter, curing was further performed at 200 ° C. for 3 hours to produce 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 Corporation. The resulting 5% and 10% weight loss temperatures are shown in Table 1. Table 2 shows the results of appearance evaluation after immersing the cured product in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

[0132]

[Table 1]

[0133]

[Table 2]

From Table 1, it can be seen that the cured product obtained by curing the imide compound of the present invention and the curable composition using the same has excellent heat resistance.

[0135]

The imide compound of the present invention has a relatively low melting point and is excellent in solubility in an organic solvent. In addition, the curable resin composition comprising the imide compound and the silanol condensation catalyst cures rapidly even at a relatively low temperature of 100 ° C. or less, and can be easily cured into various shapes. It has extremely good heat resistance, chemical resistance and mechanical properties.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08G77 / 54 C08G77 / 54 (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumi-ku, Kobe-shi, Hyogo (56) Reference J. Prakt. Chem. , Band 313, Heft 3, S.M. 461-482 (58) Field surveyed (Int.Cl. ⁷ , DB name) C07F 7/10 C07F 7/12 C07F 7/18

Claims (1)

(57) [Claims] 1. A compound of the general formula (I): (In the formula, R ⁰ is a tetravalent aromatic group having 6 to 30 carbon atoms or —CO— , —O— , —SO ₂ —, —C (CH ₃ ) ₂ —,
—C (CF ₃ ) ₂ —, —S—, —Si (CH ₃ ) ₂ — and
_{-Si (CH 3) 2 -O-} Si (CH 3) 2 -O-Si (C
A tetravalent group comprising an aromatic ring bonded through a divalent group selected from H ₃ ) ₂ — , and R ¹ represents a divalent aliphatic alkylene group having 1 to 20 carbon atoms, a phenylene group, or a naphthylene A group selected from an anthracenylene group, and R ² has 1 to ² carbon atoms.
0 alkyl groups, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (Wherein, R ³ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the three R ³ may be the same or different), and X represents CH ₃ COO—, (CH ₃ ) ₂ N-, CH ₃ C
Represents ONH— or (CH ₃ ) ₂ C ＝ NO— , a is 1, 2 or 3, two R ¹ may be the same or different, and R ² and X are 2 And when they are present, they may be the same or different).