JPS62108862A - Imide ring-containing diamine and its preparation - Google Patents

Abstract

NEW MATERIAL:An imide ring-containing diamine of formula I (R is tetravalent group selected from the group consisting of 2C or more aliphatic, alicyclic, single ring aromatic groups, and noncondensed polycyclic aromatic group in which the aromatic groups are bonded to one another directly or through bridge groups). EXAMPLE:A reaction product between pyromellitic dianhydride and m- aminobenzylamine. USE:Monomers of heat-resistant polymers, especially starting substances for polyimides or polyamideimides. A curing agent for epoxy resins. PREPARATION:The reaction of a tetracarboxylic dianhydride of formula II with m-aminobenzylamine in an organic polar solvent gives an imide ring- containing diamine of formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel imide ring-containing diamine tI'I and a method for producing the same.

Further, in detail, general formula (II) (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, an aromatic The present invention relates to imide ring-containing diamines represented by (representing a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the groups are interconnected directly or through a bridge member) and a method for producing the same.

The novel imide ring-containing diamines represented by the general formula (II) include heat-resistant polymers, especially polyimides,
It is expected that it will be a useful substance as a raw material component for polyamideimide, etc., and as a curing agent for epoxy resins. For example, conventionally, when producing copolyimide, (+
) A mixture of polyimides with certain repeating units,
There have been methods such as (li) mixing at the stage of polyamic acid, which is a precursor of polyimide, and (iii) mixing at the stage of monomer, and polymerizing it as a reaction raw material.

In the case of (i) and (ii), the obtained polymer becomes a block copolymer, and in order to obtain a polymer with constant performance with good reproducibility, conditions such as compounding ratio and mutual solubility must be set in detail. There is a need. Moreover, the polyimide obtained by the method (iii) also has a polymer structure of a random copolymer, and has the same problems as the cases (i) and (ii).

The compounds of the present invention are diamines that already contain an imide ring in the monomer skeleton, and by using this as a monomer and selecting a tetracarboxylic dianhydride, different imide structures can be alternately formed. Copolyimides can be produced containing:

In addition, diamines, diphenols, etc. have conventionally been used as curing agents for epoxy resins, but by using the imide ring-containing diamines of the present invention as curing agents, heat-resistant properties can be added to epoxy resins. This makes it possible to introduce an excellent imide skeleton, which is expected to be of great help in improving the heat resistance of epoxy resins.

(Prior Art) No new imide ring-containing diamines represented by the general formula (II) have been known so far. Therefore, its manufacturing method is also unknown.

t Suh? ), diamine compositions containing an imide ring composed of butanetetracarboxylic dianhydride and various diamines as epoxy resin curing agents, and methods for producing them are known (JP-A-49-97900, JP-A-5O). −
51600). However, there is no example of using m-aminobenzyl as a diamine component as a reaction raw material, and no method for producing imide ring-containing diamines as a monomer is known at all.

(Problems to be Solved by the Invention) An object of the present invention is to provide novel imide ring-containing diamines represented by the general formula (II) that are useful as raw materials for heat-resistant polymers, and a method for producing the same. be.

(Means for solving the ill 1. If problem) In order to achieve the above object, the present inventors have made extensive studies and have completed the present invention.

That is, the present invention relates to the general formula (I1) (wherein R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, an aromatic Imide ring-containing diamines represented by (representing a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups in which the groups are directly or interconnected through a bridge member) and these compounds are generally referred to as A tetracarboxylic dianhydride represented by formula (I) (wherein R has the same meaning as in general formula (II)),
Contains m-aminobenzylamine! This is a method for producing imide ring-containing diamines represented by the general formula (I), characterized in that the reaction is carried out in a polar solvent.

The method for producing the novel imide ring-containing diamines of the present invention is as follows.

Examples of the tetracarboxylic dianhydride used as a raw material in this method include ethylenetetracarboxylic dianhydride, cyclopencune carboxylic dianhydride, pyromellitic dianhydride, 3,3゛4.4゛-benzophenone tetracarboxylic dianhydride 2.2"13.3°-benzophenone tetracarboxylic dianhydride, 3.3", 4,
4°-Biphenyltetracarboxylic dianhydride, 2.2'
, 3.3'-biphenyltetracarboxylic dianhydride,
2.2-bis(3,4-dicarboxyphenyl)propanihydride, 2.2-bis(2,3-dicarboxyphenyl)propanihydride, bis(314-dicarboxyphenyl)ether dianhydride, bis( 3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,
3-dicarboxyphenyl)ethane dianhydride, bis(2
,3-zylcapoxyphenyl)methanidianhydride, bis(
3,4-zylcapoxyphenyl)methane dianhydride, 2,
3,6.7-naphthalenetetracarboxylic dianhydride, 1
, 4,5.8-naphthalenetetracarboxylic dianhydride,
1,2,5.6=naphthalenetetracarboxylic dianhydride, 1.2.3゜4-benzenetetracarboxylic dianhydride, 3,4,9゜10-perylenetetracarboxylic dianhydride, 2, Examples include 3.6°7-anthracenetetracarboxylic dianhydride and 1.2,7.8-phenanthrenetetracarboxylic dianhydride.

In addition, the diamine compound used as a reaction raw material in this production method is m-aminohensylamine, and this compound is a unique compound that has an aliphatic amine group and an aromatic amino group with different basicities in the same molecule. It is a diamine compound.

The amount of these raw material compounds to be used is at least 2 times the molar amount of m-aminobenzylamine relative to the tetracarboxylic dianhydride, preferably 2 to 3 times the molar amount.

When the tetracarboxylic dianhydride represented by the general formula (I) and m-aminobenzylamine are reacted in an organic polar solvent, the following general formula (III) (wherein R is the general formula (+ ) The reaction in which an amic acid-containing diamine compound, which is an intermediate represented by
(hereinafter referred to as the first step reaction) and further, the amic acid-containing diamine compound represented by the general formula (Ill) is subjected to an intramolecular dehydration reaction to form the amic acid-containing diamine compound represented by the general formula (I+). It consists of a two-stage reaction (hereinafter referred to as the second step reaction) for producing a new imide ring-containing diamine compound.

The solvent used in this reaction, that is, the solvent used to synthesize the amic acid-containing diamine ti compound in the first step, is an organic polar solvent that does not react with the reaction raw materials diamine and acid anhydride, and the product In addition to being soluble in the amic acid-containing diamines, the solvent used in the reaction in the first step that dissolves at least one, preferably both, of the reaction raw materials may include N, N'' −
Dimethylacetamide, N,N'-dimethylformamide, N-methyl, 2-pyrrolidone, 1,3-dumenal-2-imidazolidinone, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, hexamethylphosphor Examples include amide, tetramethylene, tetramethylurea, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, and the like.

In addition, in the second step of this reaction, that is, the dehydration cyclization step by heating from amic acid to imide, the general formula (Il
The amic acid-containing diamine represented by l) does not react, and the temperature required for thermal dehydration imidization, i.e., 100-3
Any solvent can be used as long as it can be heated to 00°C, preferably 150-250°C, but the above-mentioned solvents that can dissolve the intermediate amic acid-containing diamines in terms of ease of handling and operation, etc. Organic polar solvents are preferred.

In addition, the amount of solvent used is not particularly limited, but usually
1-10ffi for raw materials! Double is enough.

When carrying out the reaction, there are no particular restrictions on the method of charging raw materials, etc., but this reaction, especially the reaction in the first step, is preferably carried out under substantially anhydrous conditions, and water contained in the solvent is preliminarily removed. It is preferable to remove the raw material by an azeotropic method using a water-immiscible solvent such as Hensen, toluene, xylene, etc., and then charge the raw material under a nitrogen atmosphere.

The reaction is usually carried out by charging doaminobenzylamine in a solvent from which water has been removed in advance under a nitrogen atmosphere, and then
This is a method of adding tetracarboxylic dianhydride. Moreover, the method of adding the tetracarboxylic dianhydride may be either by adding it as a solid or by dropping it dissolved in a solvent.

In the reaction of the first step, the reaction temperature is usually 5
The temperature is 0°C or lower, preferably 5°C or lower.

The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure.

In addition, the reaction time is based on the tetracarboxylic dianhydride used,
The reaction time varies depending on the type of solvent and the reaction temperature, and is usually allowed to react for a time sufficient to complete the production of the amic acid-containing diamine. Usually 0.5-15 hours.

Furthermore, in the second step reaction in which the amic acid-containing diamine obtained in the first step reaction is thermally dehydrated and cyclized to produce an imide ring-containing diamine, the reaction temperature is usually 100°C.
-300°C, preferably 130-250°C. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. Also,
The reaction time varies depending on the tetracarboxylic dianhydride used, the type of solvent, and the reaction temperature, and usually 1 to 15 hours is sufficient to allow the reaction to complete the production of the imide ring-containing diamine.

The end point of the reaction can be determined by infrared absorption spectroscopy, high performance liquid chromatography, etc.

After the reaction is completed, the desired product is cooled and the desired product is filtered off, or the reaction solution is directly discharged into water to obtain a crude product of the desired product.

(Functions and Effects) According to the present invention, doaminobenzylamine having an aliphatic amino group and an aromatic amino group with different basicities in the same molecule is used as a diamine compound as a reaction raw material, and various tetracarboxylic acids are used. A novel imide ring-containing diamine compound can be produced relatively easily by reacting it with a dianhydride.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 100 ml of N-methyl-2-pyrrolidone and 30 ml of xylene were charged into a container equipped with a stirrer, a reflux condenser, a Dean-Starck water tank and a nitrogen inlet tube,
After removing water in the solvent by azeotropic dehydration, it was cooled to room temperature, and in a nitrogen atmosphere, doaminobenzylamine 1
2.2 g (0.1 mol) are charged.

After that, it was cooled to -2℃, and the pyromellitic dianhydride was
10.9 g (0.05 mol) was added over about 1 hour while maintaining the solution temperature in the range of -2 to 5°C, and stirring was continued for about 30 minutes.

Thereafter, the reaction solution was heated and stirred at 150-170°C for about 2 hours. After the reaction is completed, the mixture is cooled and an imide ring-containing diamine in the form of orange needles is precipitated.

After cooling to room temperature, the needle-like crystals were separated by filtration, washed with 10 ml of N-methyl-2-pyrrolidone and 101 methanol, and dried under reduced pressure at 150°C and 3 (lsmHg) for 3 hours to obtain orange needle-like crystals. The desired product was obtained as crystals. Yield: 116.1g.
(Yield 81χ) Orange needle crystals ll1p 309 315°C (DTA analysis) Elemental analysis CIIN Calculated value (χ)"67.60 4.25 13.14 Analytical value (χ) 67.84 4.15 13.07 Cx
MS as 411+5Nt04: 426 (M”), 320.106I
R (KBr, c, -+): 3480 and 3390
(NHz M) 1775 (imide group) Example 2 100 ml of N-methyl-2-pyrrolidone and 30 ml of xylene were charged into a reaction vessel similar to that in Example 1, and after removing water in the solvent by azeotropic dehydration. , cool to room temperature,
Under a nitrogen atmosphere, m-aminobenzylamine 12
．． 2 g (0.1 mol) are charged. Thereafter, it was cooled to -2°C, and 16.1g (0.05 mol) of 3.3',4.4°-tetracarboxylic dianhydride was added to the solution at a temperature of -2-5°C.
The mixture was added over about 1 hour while maintaining the temperature within the range of 6°C, and stirring was continued for about 3°C.

Thereafter, the reaction solution was heated and stirred at 150-170°C for about 2 hours. After the reaction is completed, cool it and add 50% of water.
Drain to 0ml and filter the crystals. Add 1 part of 35z hydrochloric acid to this
0.5g and 502m1 Me9 /-) Lt/Water 5001
Add 11 and heat to dissolve, add 2g of activated carbon and filter,
The mixture was neutralized with aqueous ammonia, and the crystals were filtered, washed with water, and dried to obtain the desired product as pale yellow crystals.

Yield 115.9g (Yield 60χ) Pale yellow crystal ap 234 23B℃ Purity 99.0Z (by high performance liquid chromatography analysis) Elemental analysis value CI (N Calculated value (χ Via 0.19 4.15 10.57 Analysis value (χ) ?0.15 4.05 10.31Cs+
MS as HttNaOs; 530 (MI), 425

Claims (1)

[Claims] 1) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic represents a tetravalent group selected from the group consisting of an aromatic group, a fused polycyclic aromatic group, and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member) Imide ring-containing diamines represented. 2) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an aliphatic group with 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, or a fused A tetracarboxylic acid represented by a polycyclic aromatic group (representing a tetravalent group selected from the group consisting of a polycyclic aromatic group and a non-fused polycyclic aromatic group in which aromatic groups are interconnected directly or through a bridge member) General formula (II), characterized by reacting dianhydride and m-aminobenzylamine in an organic polar solvent ▲There are numerical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R A method for producing an imide ring-containing diamine represented by formula (I).