JPH0456851B2 - - Google Patents

Description

[Detailed description of the invention]

<<Industrial Application Field>> The present invention relates to a method for producing co-poly(imideether) containing polyether. <Prior Art> Conventionally, polyimide is produced by heating a polyamic acid precursor produced by low-temperature polycondensation of an organic dianhydride and a diamine in a polar solvent.
Synthesized by dehydration and ring closure. The polyimide resin synthesized in this way has high mechanical strength, excellent heat resistance and light resistance, and has a wide range of uses in many fields such as electrical component materials, heat-resistant films, paints, and adhesives. is well known. On the other hand, in order to use such polyimide, the synthesized polyimide has poor solubility and processability, and is difficult to mold. Therefore, a solution of a polyamic acid precursor is molded by a casting method, and then the solution is removed after the solvent is removed. It is common to obtain a resin-like molded product by heat treatment, which has the disadvantage that its uses are inevitably limited. As one method for solving these drawbacks, it is generally done to modify the polyimide by copolymerizing the above-mentioned polyimide with a third component. Depending on the type of third component used in this case, it is possible to add new functions while taking advantage of the advantages of polyimide resin, and it is also adopted as a method for improving the moldability of polyimide resin. <<Problems to be Solved by the Invention>> As a result of intensive research from this perspective, the present inventors have found that when a polyether having a certain molecular length is introduced as the third component of polyimide, the superior properties of polyimide resin can be improved. In addition to these properties, the inventors have discovered that it is possible to improve moldability and gas permeability, and in particular, the permeability of oxygen to nitrogen is extremely high, and the present invention has been achieved. Therefore, a first object of the present invention is to provide a new method for copolymerizing polyimide with polyether. A second object of the present invention is to provide a new method for producing a new resin with excellent heat resistance and light resistance and high gas permeability. Furthermore, a third object of the present invention is to provide a new method for producing a new resin that can be used as an oxygen separation membrane at high temperatures. <<Means for Solving the Problems>> The above objects are obtained by adding 60 to 95% by weight of a diamine represented by the following general formula () to an organic acid dianhydride represented by the following general formula () and the following general formula ( This was achieved by a process for the production of co-poly(imide ethers) characterized in that a mixture of diamines consisting of 5 to 40% by weight of diaminated polyethers of the formula (2) is reacted. General formula () In the general formula (), Ar is as well as , Xa is -O-,

[Formula] and -CH ₂ -. In the general formula () H ₂ N−Re−NH ₂ In the general formula (), Re is as well as represents -O-,

【formula】

【formula】

[Formula] and -SO ₂ -. General formula () (However, in the general formula, R represents a hydrogen atom or a methyl group, and m represents an integer from 3 to 300.) The co-poly(imide ether) of the present invention is an organic acid represented by the general formula (). A mixture of diamines consisting of 60 to 95% by weight of diamine represented by the following general formula () and 5 to 40% by weight of diaminated polyether represented by the following general formula () to the dianhydride in a polar solvent, It can be synthesized by reacting at room temperature to synthesize copolymerized polyamic acid, and heating this as a precursor to 200 to 350°C. These raw materials will be explained in detail below. General formula () In the general formula (), Ar is a carbonyl group directly bonded to an adjacent carbon atom, 1,2; 3,4;
5, 6; 7, 8; 9, 10; 11, 12; 13, 14 and
15, 16; preferably an aromatic group. Next, representative groups represented by Ar are listed. where =Y is =O, =N-R ₈ -N= or =N-
R ₈ -NH ₂ , preferably =O, R ₉ is alkylene, arylene, etc., R ₁₀ is an alkyl group, R ₁₁ is preferably an alkylene group, but the following divalent It may be a base.

[Formula] -S-,

【formula】

【formula】

【formula】

[Formula] In the above formula, the alkyl group can be substituted by an aryl group such as a phenyl group. _R8
is a divalent organic group, and the following are representative examples thereof. −R ₉ −, Here, Ya, R ₉ and R ₁₁ represent the same as described above. Moreover, R ₈ to R ₁₁ are halogen, NO ₂ , COOH,
COOZ (Z is alkyl, aryl, alkaryl,
(representing an aralkyl group, etc.). Examples of organic acid anhydrides that can be preferably used in the present invention include pyromellitic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, and 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 4,4'-isopropylidene diphthalic anhydride, 4,4'-sulfonyl-diphthalic anhydride 3,4,9,10-perylenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5, 8-Naphthalenetetracarboxylic dianhydride, 2,3,6,7
-naphthalenetetracarboxylic dianhydride, 3,
3'-isopropylidene diphthalic anhydride, 3,
3'-ethylidene diphthalic anhydride, 4,4'-ethylidene diphthalic anhydride, 3,3'-methylene diphthalic anhydride, 4,4'-methylene diphthalic anhydride, 2,3, 5,6-pyrazinetetracarboxylic dianhydride, 2,3,4,5-thiophenetetracarboxylic dianhydride, 4,4'-biphthalic anhydride,
3,3'-biphthalic anhydride, 2,3,4,5-pyrrolidonetetracarboxylic dianhydride, 1,4-dimethyl-7,8-diphenylbicyclo(2,2,
2) Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,4,7,8-tetrachlorobicyclo(2,2,2)oct-7-ene-
2,3,5,6-tetracarboxylic dianhydride,
7,8-diphenylbicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,8-dimethyldicyclo(2,
2,2) Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, Examples include 3,3',4,4'-benzophenonetetracarboxylic dianhydride and other acid anhydrides described in Japanese Patent Publication No. 19349/1983. In the present invention, among these, those in which Ar is represented by the following general formula are particularly preferred. as well as is preferred. However, in this case, Xa is -O-,

[Formula] and represents a -CH ₂ - group. Next, the diamine represented by the following general formula () to be reacted with the organic acid dianhydride will be explained. General formula () H ₂ N-Re-NH ₂ Re in the diamine represented by the general formula () used in the present invention represents the same group as R ₈ in the general formula (). Preferred examples of such diamines include 4,4'-diaminodiphenyl ether, 4,4'-isopropylidene-dianiline, 4,4'-methylene-dianiline, benzidine, and 3,3'-dichloro. Benzidine, 4,4'-thiodianiline, 3,3'-sulfonyl-dianiline, 4,4'-oxydianiline, 1,5-naphthalenediamine, 4,4'-(ethylphosphinylidene)dianiline, 4, 4'-(N-methylamino)
Dianiline, 4,4'-(N-phenylamino)dianiline, metaphenylenediamine, paraphenylenediamine, 2,6-diaminopyridine, 4,
4'-methylenedicyclohexylamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,4-cyclohexanediamine, and other diamines such as those described in Japanese Patent Publication No. 19349/1983. can be mentioned. Particularly preferred diamines in the present invention are those in which Re in the general formula () is the following group. as well as In the above formula, Ya is -O-,

[Formula] − CH ₂ −,

[Formula] and -SO ₂ -. General formula () (R in the general formula represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and m is 3 to
Represents 300 integers. ) The diamine represented by the general formula () that can be used in the present invention is obtained by cyanating polyethylene glycol or polypropylene glycol having -OH groups at both ends by a Michael addition reaction with acrylonitrile, and then cyanating both ends. It can be obtained by hydrogenation in contact with PtO ₂ , and hereinafter these will be referred to as PEO amine and PPG amine in this specification. The rate of amino group introduction into PEO amine and PPG amine is easily 99
% or more. In the present invention,
The degree of polymerization of the glycol moiety of PEO amine and PPG amine is preferably 3 to 200, and the degree of polymerization distribution of these diamines used in the reaction may be wide or narrow. If the degree of polymerization is 3 or less, the polyimide will not be sufficiently modified, which is not preferable. Further, if the degree of polymerization is 200 or more, the properties of polyether become strong and the excellent properties of polyimide are lost, which is not preferable. The amount of PEO amine and/or PPG amine used in the present invention is 5 of the total diamines that react with the organic acid dianhydride (i.e., the total amount of diamines represented by general formula () and general formula ()). ~40
The amount is preferably 10 to 30% by weight. If it is less than 10% by weight, the modification will not be sufficient, and if it is more than 30% by weight, the film-forming ability of the obtained polymer will decrease, which is not preferable. That is, the physical properties of the co-poly(imide ether) obtained in the present invention are based on the above PEO diamine and/or
Since it greatly depends on the amount of PPG diamine used and their molecular weight, new functions can be imparted to the co-poly(imide ether) of the present invention by adjusting these. The synthesis reaction of the co-poly(imide ether) of the present invention can be carried out in an appropriate solvent that does not interfere with the reaction and does not unduly react with the diamide-dicarboxylic acid produced during the reaction. Preferred solvents are so-called polar solvents, and specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methylcaprolactam, and dimethylsulfoxide. , N-methyl-
2-pyrrolidone, tetramethylene urea, pyridine, dimethyl sulfone, hexamethyl phosphoric acid amide, tetramethylene sulfone, formamide, N
- Methylformamide, butyrolactone, N-acetyl-2-pyrrolidone, ketones such as methyl ethyl ketone, nitroalkanes such as nitroethane, nitropropane and the like. Particularly preferred solvents among these are N, N
-dimethylformamide and N,N-dimethylacetamide. These solvents may be used alone or in combination, and may also be used in combination with poor solvents such as benzene, benzonitrile, dioxane, xylene, toluene, and cyclohexane. <<Effects of the Invention>> The copoly(imide ether) copolymer obtained by the production method of the present invention has mechanical strength similar to polyimide, although it has better moldability than polyimide resin. Furthermore, it has good acid resistance and alkali resistance, making it extremely useful. Furthermore, when the resin obtained by the production method of the present invention is made into a film, it has good gas permeability, and in particular, the permeability of oxygen to nitrogen is high, making it suitable for use at high temperatures. It is extremely useful as an oxygen separation membrane. The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited thereby. 《Example》 Example 1 While passing nitrogen into a two-necked flask equipped with a three-way cap, 0.948 g (4.74 x 10 ^-3 mol) of 4,4'-diaminodiphenyl ether and 400 g of PEO amine were added.
(Average degree of polymerization m=6.45) 0.105g (0.26×10 ^-3 mol)
Then, 20 ml of N,N-dimethylacetamide was added. While stirring this solution with a magnetic stirrer in a water bath, 1.09 g of pyromellitic anhydride (5×
10 ^-3 mol) was gradually added, and the reaction was allowed to proceed for 2 hours. The system gradually became viscous. The relative viscosity ηsp/c of the copolymerized polyamic acid thus obtained in an N,N-dimethylacetamide solution is 1.96 (concentration 0.5 g/10 ml, temperature 30°C)
It was hot. A portion of this solution was cast on a 10 cm square glass plate and heated at 50°C under reduced pressure for 1 hour.
The solvent was removed by heating at 150°C for 1 hour. after that,
Imidization was carried out by heating at 250°C for 3 hours in an electric furnace under a nitrogen stream. After cooling, it was peeled off from the glass plate to obtain a uniform yellow transparent film with a thickness of 25 μm. In the IR spectrum of this film, in addition to polyimide-based absorptions at 3150 cm ^-1 (phenyl group), 1780 and 1730 cm ^-1 (imide groups), polyether-based absorptions at 2930 and 1150 cm ^-1 were observed. Furthermore, in differential thermal analysis (DTA) of the polymer, a broad endothermic peak was observed between 200 and 300°C, which is thought to be due to glass transition, and the weight loss rate due to TGA was also 1% at 300°C.
Below, it was shown that it was 9% at 500°C. or,
When this film was bent and placed on a hot press and deformed at 250°C and 100 atm, a slight fusion phenomenon was observed and permanent deformation remained, resulting in a film thickness of less than 20 μm. It is clear that the polyimide resin of the invention has improved moldability. Example 2 In the same manner as in Example 1, 0.914 g (4.56 × 10 ^-3 mol) of 4,4'-diaminodiphenyl ether and 3.61 g (0.44 × 10 ^-3 mol) of PEO amine 8300 (m = 182) were mixed with N. , N-dimethylacetamide (50 ml).
This was stirred with a magnetic stirrer while cooling in a water bath, and 1.09 g of pyromellitic anhydride (5×
10 ^-3 mol) was gradually added, and the reaction was allowed to proceed for 2 hours. The system gradually became viscous, and the relative viscosity ηsp/c of this copolymerized polyamic acid in N,N-dimethylacetamide was 0.43 (concentration 0.5 g/10 ml, temperature 30°C). In the same manner as in Example 1, a copolymerized poly(imide-ether) film was formed from this solution. Although a yellow transparent film was obtained, it was confirmed that the strength was considerably lower than that of the film of Example 1, and that it would tear when pulled by hand. Furthermore, the thermal reduction rate due to TGA was 18% at 300°C and 79% at 500°C, and although the physical properties of the polymer in this example were not necessarily sufficient, a fusion phenomenon was observed as in Example 1. It was found that moldability was improved. Example 3 In the same manner as in Example 1, 0.94 g (4.74×10 ^-3 mol) of p,p'-methylene dianiline and 400 (m
= 6.45) 0.104 g (0.26 × 10 ^-3 mol) was dissolved in 24 ml of N,N-dimethylacetamide, and 3,3',4,
4′-Benzophenonetetracarboxylic dianhydride
1.61 g (5 x 10 ^-3 mol) was reacted. The relative viscosity of the copolymerized polyamic acid produced in N,N-dimethylacetamide was 0.69 (30°C, 0.5g/10ml)
It was hot. A copolymerized poly(imide-ether) film was also prepared in the same manner, and a uniform yellow transparent film with a thickness of 29 μm was obtained. The IR spectrum of this film includes absorptions at 1780 and 1730 cm ^-1 due to imide groups, absorptions at 1690 cm ^-1 due to carbonyl groups indicating that it is polyimide, and absorptions at 2930 and 1150 cm ^-1 due to polyether. was also confirmed. The softening point of this polymer by DTA is approximately 170°C to approximately 220°C.
℃, and a reduction in fusion was observed by pressing at approximately 250℃ and 100 atm, demonstrating that the film formability was improved. Furthermore, the weight reduction rate due to TGA was approximately 2% at 300°C and approximately 10% at 500°C, demonstrating that it has heat resistance. Example 4 3.61 g (0.44 mmol) of PEO amine 6000 (average molecular weight Mn = 8300) was placed in a 50 ml two-necked flask, and 50 ml of N,N-dimethylacetamide was added thereto, followed by heating and dissolving at 60°C. Cool this solution to room temperature and add 0.914 g of 4,4'-diaminodiphenyl ether.
(4.56 mmol) and stir well.

【table】

[Table] Meanwhile, 1.09 g (5 mmol) of pyromellitic anhydride was gradually added to react. The system became very viscous after stirring for about 2 hours at room temperature. From this polyamic acid production solution, the thickness was
A uniform yellow polyimide film of 25 μm was obtained. Example 5 The film-forming ability and gas permeability of various films with varying amounts of PEO amine were investigated using the methods of Examples 1, 2 and 4. The results are shown in Tables 1 and 4, respectively. Table 2 shows that the co-poly(imide ether) membrane of the present invention has an excellent ability to separate nitrogen gas and oxygen gas.

Claims (1)

[Claims] 1. An organic acid dianhydride represented by the following general formula (), and a diamine 60 to 95 represented by the following general formula ().
1. A method for producing a co-poly(imide ether), which comprises reacting a mixture of diamines consisting of 5 to 40% by weight of diaminated polyether represented by the following general formula (). General formula () In the general formula (), Ar is as well as , and Xa represents -O-, [Formula] and -CH ₂ -. In the general formula () H ₂ N−Re−NH ₂ In the general formula (), Re is as well as Ya represents -O-, [Formula] [Formula] [Formula] and -SO ₂ -. General formula () (However, in the general formula, R represents a hydrogen atom or a methyl group, and m represents an integer from 3 to 300.)