JPS62145063A - Novel diphenol having imide ring and production thereof - Google Patents

Abstract

NEW MATERIAL:A novel diphenol, having imide ring and expressed by formula I (R is tetrafunctional group selected from >=2C aliphatic, cycloaliphatic, monocylic aromatic, condensed polycyclic aromatic and uncondensed polycyclic aromatic groups in which aromatic groups are directly or mutually communicated through crosslinking members). EXAMPLE:A compound obtained by reacting 2-(4-hydroxyphenyl)-2-(4'- aminophenyl)propane with 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride. USE:A raw material for various resins, e.g. epoxy resins, polyimide resins, etc., having improved heat resistance. PREPARATION:A tetracarboxylic acid dianhydride expressed by formula II is reacted with 2-(4-hydroxyphenyl)-2-(4'-aminophenyl)propane in an organic plar solvent to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to novel diphenols having an imee ring and a method for producing the same.

More specifically, general formula (■) (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 group) (represents a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups connected directly or through a bridge member) and a method for producing the same. .

The new diphenols having an imide ring represented by the above general formula (II) have never been produced, so there are no known uses for them. However, they can be used in various resins such as epoxy resins and polyimide resins. It is expected that this substance will be useful as a raw material for. Furthermore, it is expected that various resins with excellent heat resistance can be produced from the structure.

(Prior Art) Conventionally, for example, benzophenone tetracarboxylic dianhydride and 7-minophenol are reacted to produce bisimidophenol, which is then reacted with diglycidyl ether of bisphenol A to produce an imide epoxy resin. Known (Japanese Unexamined Patent Publication No. 49-38119),
L-kashi, 2-(4-hythrodiphenyl'I-2
There are no examples of using -(4''-aminophenyl)propane, and no examples of producing diphenols having an imide ring as the 411M form are known.
-Hydroxyphenyl)-2-(4''-aminophenyl)propane can be easily produced industrially by reacting isopropenylphenol and its monomer with aniline (JP-A-55-64552).

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel diphenol having an imide ring that is useful as a raw material for various resins expected to have excellent heat resistance properties, and a method for producing the same. .

(Means for solving the problem) In order to achieve the above object, the inventors have made extensive studies,
The present invention has now been completed.

That is, the general formula (It) (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 group directly or A new diphenol having an imide ring represented by (representing a tetravalent group selected from the group consisting of non-fused polycyclic aromatic groups interconnected by a bridge) and this compound, the general formula (1) ) (wherein R has the same meaning as in general formula (1)) and 2-(4-hydroxyphenyl)-2-(4°-aminophenyl) ) This is a method of producing propane by reacting it in an organic polar solvent.

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°, 3,3''-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(3,4-dicarboxyphenyl)ether anhydride, Bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3
-dicarboxyphenyl)ethane dianhydride, bis(2,
3-Zylcapoxyphenyl)methanihydride, bis(3
,4-zylcapoxyphenyl)methanihydride, 2,3
．． 6.7-naphthalenetetracarboxylic dianhydride, 1,
4,5.8-naphthalenetetracarboxylic dianhydride, 1
, 2.5.6-naphthalenetetracarboxylic dianhydride,
1,2,3.4-benzenetetracarboxylic dianhydride,
Examples include 3,4.9,10-perylenetetracarboxylic dianhydride, 2,3.6,7-anthracenetetracarboxylic dianhydride, 1,2゜7.8-phenanthrenetetracarboxylic dianhydride, etc. It will be done.

In addition, the reaction raw material used in the present invention is 2-(4-hydroxyphenyl)-2-(4°-aminophenyl)propane, and the amount of these raw materials used is twice that of tetracarboxylic dianhydride. It is sufficient if the amount is at least mol, preferably 2 to 3 times the mol.

When the tetracarboxylic dianhydride represented by the general formula (1) and 2-(4-hydroxyphenyl)-2-(41-aminophenyl)propane are reacted in an organic polar solvent, the following general formula is obtained. (III) (wherein R is as described above)
A reaction for producing an amic acid-containing Schiff, enol compound which is an intermediate represented by (hereinafter referred to as the first stage reaction),
Furthermore, the amic acid-containing diphenol compound represented by the general formula (III) is subjected to an intramolecular dehydration reaction to produce a diphenol compound having an imide ring represented by the general formula (11) (hereinafter referred to as , the second stage reaction).

The solvent used in this reaction, that is, the solvent used to synthesize the amic acid-containing diphenol that is the first-stage intermediate, is an organic polar solvent whose functional group does not react with the amine or acid anhydride. It is a solvent for diphenols having an imide ring that are inert to the system and is a product, and is preferably a solvent for both reaction raw materials, and includes a solvent that dissolves at least one of the reaction raw materials. .

For example, the solvent used in the first stage reaction is:
N,N'-dimethylacetamide, N,N'-dimethylformamide 3-dimethyl-2-imidazolidinone, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, cresol, hexamethylphosphoramide, tetramethylene , tetramethylurea, dimethyl sulfoxide,
Examples include dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, and the like. These solvents can be used alone or in combination with other solvents, and further in combination with solvents such as benzene, toluene, xylene, and cyclohexane.

In addition, in the second stage reaction of the present invention, that is, the dehydration cyclization step from amic acid to imide by heating, the amic acid-containing diphenol represented by the general formula (Hl) does not react, and furthermore, the thermal dehydration Temperature required for imidization, i.e. 100-300
Any solvent can be used as long as it can be heated to 150 to 250°C, but from the viewpoint of ease of handling, the above-mentioned organic solvents that can dissolve the intermediate amic acid-containing diphenol may be used. Polar solvents are preferred.

In addition, the amount of solvent used is not particularly limited, but usually
It is sufficient to use 1 to 10 times the weight of the raw material.

When carrying out the reaction, there are no particular restrictions on the charging method of raw materials, etc., but this reaction, especially the first stage reaction, is preferably carried out under substantially anhydrous conditions, and the water contained in the solvent is removed in advance. It is preferable to remove it by a method such as azeotropy, and then charge the raw material under a nitrogen atmosphere.

The reaction is usually carried out in a solvent from which moisture has been removed in advance under a nitrogen atmosphere, and 2-(4-hydroxyphenyl) -2-(
This method involves charging 4'-aminophenyl)propane and then 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 first stage reaction, the reaction temperature is usually 50°C.
℃ or less, preferably 40℃ or less, most preferably 20℃ or less
~25°C. 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 sufficient time to complete the production of the amic acid-containing diphenol. Usually 0.5-15 hours.

Through the above reaction, an amic acid-containing diphenol represented by the following general formula (III) is obtained.

(In the formula, R is as described above.) Furthermore, in the second stage reaction of heating and cyclizing the amic acid-containing diphenol obtained in the first stage reaction to produce an imide ring-containing diphenol, The reaction temperature is usually 100-300°C, preferably 130-250°C. The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure. In addition, the reaction time varies depending on the tetracarboxylic dianhydride used, the solvent III, and the reaction temperature, and usually
The reaction is allowed to occur for a sufficient period of time to complete the production of the imide ring-containing diphenol. Usually 1 to 15 hours is sufficient.

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. This crude product can be purified by recrystallization or the like.

(Functions and Effects) According to the present invention, novel diphenols having imide rings and compounds thereof, which have not been previously known in the production examples, can be produced relatively easily and in high yields.

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

Example 1 250 ml of N,N-dimethylacetamide and 60 m+1 of xylene were charged into a container equipped with a stirrer, a reflux condenser, a Dean-Starck water separator, and a nitrogen inlet tube, and water in the solvent was removed by azeotropic dehydration. After that, it was cooled to room temperature, and in a nitrogen atmosphere, 47.7 g (0.21 mol) of 2-(4-hydroxyphenyl)-2-(4'-aminophenyl)propane and 3.3°, 4.4 '
-benzophenonetetracarboxylic dianhydride 33,8
g (0,105 mol) is charged at 0 then 15 at room temperature.
Stirring was continued for an hour. Thereafter, the reaction solution was heated to 150
Stirring was carried out at ~170°C for about 5 hours. After the reaction is completed, the reaction mixture is cooled, 25 kl of methanol is charged, and the mixture is stirred to precipitate a pale yellow imide ring-containing diphenol.

The pale yellow crystals were filtered and washed with 20 ml of a mixed solvent of N,N-dimethylacetamide and methanol.
The product was washed with ml of methanol and dried to obtain the desired product as a pale yellow powder. Purity by high performance liquid chromatography is 9
It was 9.0%.

Yield 63.7g (yield 82%) @p250-256℃
Elemental analysis CHN calculation (j! (χ)”?6.22 4.86 3.78
Analysis value (X)? 5.83 4.53 3.76suC
□l1sJt as MS (FD method), 741 (M-1) IR (Br,
ell-1): 1660 (carbonyl group), 1
720.177G (carbonyl group of imide group) 3480 (hydroxyl group) Example 2 N,N-dimethylacetamide 1001 and xylene 30- were placed in a container equipped with a stirrer, a reflux condenser, a Dean-Starck water separator, and a nitrogen inlet tube. Charge 1,
After removing water in the solvent by azeotropic dehydration, it was cooled to room temperature, and in a nitrogen atmosphere, 2-(4-hydroxyphenyl)-2-(4°-aminophenyl)propane 22
．． 7 g (0.1 mol) and 15.5 g (0.05 mol) of bis(3,4-dicarboxyphenyl)ether anhydride were charged and stirring was continued for 15 hours at room temperature. Thereafter, the reaction solution was heated and stirred at 150 to 170°C for about 5 hours. After the reaction was completed, it was cooled and discharged into 900 ml of water to obtain crude crystals of imide ring-containing diphenol. The sludge was washed and dried to obtain a white crystalline imide ring-containing diphenol. Purity by high performance liquid chromatography was 99.0%.

Yield 25.8g (yield 71%) sp206-212℃
Elemental analysis CHN Calculated value (X)”75.80 4.95 3.85 Analysis value α) 75.53 4.56 3.85 Kushi' Ca*
HshNz is M, 5 (FD method), 729 +N″111R (
KBr, ---+): 1240 (ether bond)
, 1720, 1770 (carbonyl group of imide group) 3400 (hydroxyl group) Example 3 250 ml of N,N-dimethylacetamide and After charging xylene 60+*1 and removing water in the solvent by azeotropic dehydration, it was cooled to room temperature, and in a nitrogen atmosphere, 2-(4-hydroxyphenyl)-2-(4'-aminophenyl) was extracted. 47.7 g (0.21 mol) of propane and 22.9 g (0.105 mol) of pyromellitic dianhydride were charged, and stirring was continued for 15 hours at room temperature. Thereafter, the reaction solution was heated and stirred at 150 to 170° C. for about 5 hours. After completion of the reaction, it was cooled to precipitate yellow crystals of imide ring-containing diphenol. The crystals were filtered and 201
After washing twice with 1 Il of N,-dimethylacetamide and 50 ml of methanol and drying, a yellow powder of imide ring-containing diphenol was obtained. Yield 60.1g (yield 90%) mp Elemental analysis above 300℃ C11N Calculated value (χ Via 5.50 5.03 4.40 Analysis value (
χ)? 5.20 4.86 4.49S C4゜Hl
As Jz

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) A novel diphenol having an imide ring as shown below. 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 2-(4-hydroxyphenyl)-2-(4'-aminophenyl)propane in an organic polar solvent ▲Mathematical formula, chemical formula, table, etc. ▼(II) A method for producing a novel diphenol having an imide ring represented by the formula (wherein R has the same meaning as in general formula (I)).