JPS60115629A - Production of aromatic polyether-amide-imide polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer which is freed from clouding during formation of a membrane and is excellent in adhesion to bases, heat resistance, etc., by polycondensing an aromatic dicarboxylic acid (derivative) with trimellitic acid (derivative) and a specified aromatic diamine. CONSTITUTION:(A) An aromatic dicarboxylic acid or its reactive acid derivative (e.g., terephthaloyl dichloride) with (B) trimellitic acid or its reactive acid derivative (e.g., trimellitoyl chloride) at a molar ratio, A/B, of 5/5-9/1. 90- 130mol% this mixture is subjected to interfacial or solution polycondensation with 100mol% aromatic diamine of formula I (wherein R1-4 are each H, a lower alkyl, a lower alkoxy, Cl, or Br, R5-6 are H, CH3, C2H5, C3H7, trifluoromethyl or trichloromethyl), {e.g., 2,2-bis[4-(4-aminophenoxy)-phenyl]propane} in a reaction solvent such as cyclohexanone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel aromatic polyether amitimide polymer.

Conventionally, there has been known a method for producing aromatic polyetheramide polymers with excellent heat resistance and moldability by condensation polymerization of aromatic ether diamines and aromatic dicarboxylic acids or their reactive acid derivatives. Kosho 5
4-21397).

This type of polymer can be applied as engineering plastics and heat-resistant coating materials.

Furthermore, there are many applications that require improved heat resistance.

In recent years, attempts have been made to apply this glaze polymer to control alignment films for liquid crystal display devices. but.

This polymer not only has insufficient adhesion to a substrate in some cases, but also has the disadvantage that it becomes cloudy when the polymer is dissolved in a polar organic solvent to form a film.

The present invention provides a novel polymer free of such drawbacks.

That is, 9 the present invention combines an aromatic dicarboxylic acid or its reactive acid derivative, trimellitic acid or other reactive acid derivative, and the general formula +11 (however, in formula 9, R + ,
&, R3 and R4 are hydrogen.

It represents a lower alkyl group, a lower alkoxy group, chlorine or bromine, and they may be the same or different from each other. The present invention relates to a method for producing an aromatic polyether amitimide polymer, which is characterized by subjecting aromatic diamines represented by methyl groups (which may be the same or different) to a polycondensation reaction.

In the present invention, aromatic dicarboxylic acid or its reactive acid derivative and trimellitic acid or its reactive acid derivative are preferably blended in a molar ratio of 515 to 9/1, particularly 6/1. It is preferable that the ratio is 9 to 8/2. If this ratio is too small, the solubility tends to decrease, and if this ratio is too large, the heat resistance tends to decrease.

Also, for the compound represented by the general formula +11.

It is preferred to use a total amount of aromatic dicarboxylic acid and trimellitic acid or their reactive acid derivatives from 90 to 130 moles, particularly preferably at or near 100 moles.

In the present invention, the aromatic diamine having an ether bond represented by the general formula (11) is 2,2-bis(
4-(4-aminophenoxy)phenyl]propane, 2
．． 2-bis[3-methyl-4-(4-aminophenoxy)phenyl]furopanoxy)phenyl]furopane, 2.
2-bis[3-fromo4-(4-aminophenoxy)
phenyl]propane.

2,2-bis[3-ethyl-4-(4-aminophenoxy)phenyl]propane, 212bis[3-7'rohil-4-(4-aminophenoxy)phenyl]propane,
2,2-bis[3-isopropyl-4-(4-aminophenoxy)phenyl]propane.

2.2-bis[3-butyl-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[3-5eC-
Butyl-4-(4-aminophenoxy]phenyl]propane, 2.2-bis[3-methoxy-4-(4-aminophenoxy)phenyl]propane, 2.2-bis[3-
Ethoxy-4-(4-aminophenoxy)phenyl]propane, 2I2-bis[3,5-dimethyl-4-(4-
aminophenoxy)phenyl]propane, 2,2-bis(3,5-cyclo4-(4-aminophenoxy)phenyl)propane, 2,2-bis[3,5-dibromo-
4-(4-aminophenoxy)phenyl]propane, 2
．． 2bis[3,5-dimethoxy-4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-chloro-4-(4-aminophenoxy)-5-methylphenyl]propane, 1.1 -bis(4-(4-aminophenoxy)phenyl)ethane, 1.1-bis[3-methyl-
4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis[3-chloro-4-(4-aminophenoxy)
phenyl]ethane.

1.1-bis[3-bromo-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3-ethyl-4
-(4-aminophenoxy)phenyl]ethane, 1.1
-bis[3-propyl-4-(4-aminophenoxy)
phenyl]ethane, 1,1-bis[3-isopropyl-
4-(4-aminophenoxy)phenyl]ethane, 1.
1-bis(3-butyl-4-aminophenoxy/)phenyl]ethane.

1.1-bis(3-5ec-butyl-4-(4-aminophenoxy)phenyl)ethane, 1.1-bis[3-
Methoxy-4-(4-aminoenoxy)phenyl]ethane, 1,1-bis[3-ethoxy-4-(4-aminophenoxy)phenyl]ethane.

1.1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]ethane, 1,1-bisC3゜5-
Dichloro-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3,5-dibromo-4-(4-aminoenoxy)phenyl]ethane.

1.1-bis[3,5-dimeth-4-(4-aminophenoxy)phenyl]ethane, 1.1-bis[3-
Chloro-4-(4-aminophenoxy)-5-methylphenyl]ethane, bis(4-(4-aminophenoxy)
Phenylcomethane, bis[3-methyl-4-(4-aminophenoxy)phenylcomethane, bis[3-chloro-
4-(4-aminophenoxy)phenylcomethane, bis[3-promo 4-(4-aminophenoxy)phenylcomethane, bis[3-ethyl-4-(4-aminophenoxy)phenylcomethane, bis[3 -propyl-4-(
4-aminophenoxy)phenylcomethane, bis[3-
Isopropyl-4-(4-aminophenoxy)phenylcomethane, bis[3-butyl-4-(4-aminophenoxy)phenylcomethane, bis[3-5ee-butyl-
4-(4-aminophenoxy)phenylcomethane, bis[3-methoxy-4-(4-aminophenoxy)phenylcomethane, bis[3-ethoxy-4-(4-aminophenoxy)phenylcomethane, bis[ 3,5=dimethyl-4-(4-aminophenoxy)phenylcomethane, bis[3,5-dichloro-4-(4-aminophenoxy)
Phenylcomethane, bis[3,5-dibromo-4-(4
-aminophenoquine) phenylcomethane, bis(3,5
-dimethoxy-4-(4-7S nophenoxy)phenylcomethane.

Bis[3-chloro-4-(4-aminophenoxy)-5
-methylphenyl]methane, 1.1.1.3.3.3
-hexafluoro-2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,1.1,3.3.
3-hexachloro-2,2-bis[4-(4-aminophenoxy)phenyl]furopane, 3,3-bis(4-(
4-aminophenoxy)phenyl]pentane, 1.1-
Bis[4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3.3-hegizafluoro-2,
2-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1,1°1,3.3.3-
hexachloro-2,2-bis[3,5-dimethyl-4-
(4-aminophenoxy)phenyl]propane, 3,3
-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]pentane.

1.1-bis[3,5-dimethyl-4-(4-aminophenoxy)phenyl]propane, 1.1.1.3.3
．． 3-hexafluoro-2,2-bis(3,5-dibromo-4(4-aminophenoxy)phenyl)propane,
1.1.1.3.3.3-hexachloro-λ2-bis[
3,5-dibromo-4-(4-aminophenoxy)phenyl]clopane, 3,3-bis(3,5-dibromo-4
-(4-aminophenoxy)phenyl]pentane, 1.
1-bis[3,5-dibromo-4-(4-aminophenoxy)phenyl]propane, 2,2,-his[4-(4
-aminophenoxy)phenylcobutane, 2,2-bis[3-methyl-4-(4-aminophenoquine)phenylcobutane, 2,2-bis[315-dimethyl-4-(4
-aminophenoxy)phenylcobutane, 2,2-bis[a,5-dibromo-4-(4-aminophenoxy)phenylcobutane, 1.1.1.3,3.3-hexafluoro-2,2 -bis[3-methyl-4-(4-aminophenoxy)phenyl]propane and the like. Of these.

2.2-bisC4-(4-aminophenoxy)phenyl]propane is representative. If desired, mixtures of the above diaminos can be used.

In the present invention, there are 2787 known cases of rainbow, tb 4.4
'-cyamino diphenyl ether, 4.4'-diaminodiphenylmethane, 4.4'-diaminophenyl sulfone, metaphenylene diamine, 4.4'-di(4-aminophenoxy) phenyl sulfone, paraphenylene diamine, 4.4' An aromatic polyamide polymer containing at least one of -di(3-aminophenoxy)phenylsulfone, 3,3'-diaminodiphenylsulfone, etc. can be used.

The ratio of these diamines to the total diamines is preferably 30 molti or less. If this ratio exceeds 30 molar ratio, it is not preferable because it does not adversely affect the solubility of the 9 polymer.

The aromatic dicarboxylic acid in the present invention includes:

For example, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid-4+4'+ diphenyl sulfone dicarboxylic acid-4,4', diphenyl dicarboxylic acid-4,
4' and naphthalene dicarboxylic acid-1,5, etc., but terephthalic acid and isophthalic acid are commonly produced and can be preferably used.

In particular, a mixture of terephthalic acid and isophthalic acid is desirable from the viewpoint of solubility of the resulting polymer. Note that the reactive acid derivative of aromatic dicarboxylic acid in the present invention means dichloride, dichloride, diester, etc. of the aromatic dicarboxylic acid.

In the present invention, when a mixture of terephthalic acid and isophthalic acid is used, the blending ratio of isophthalic acid having a nicalhoginyl group at the mec position of the benzene nucleus [terephthalic acid having a carboxyl group at the para position of the benzene nucleus] is 20% of the former.
-80%, the latter is preferably within the range of 80 to 20%, especially from the viewpoint of solubility.

Heat resistance can be further improved by copolymerizing trimellitic acid or its reactive acid derivative.

Examples of reactive acid derivatives of trimellitic acid include trimellitic acid chloride.

In the present invention, as the reaction method, a known method used for the reaction of an amine and an acid or a reactive acid derivative thereof can be adopted, and the various conditions are not particularly limited either. For example, this can be achieved by an interfacial polycondensation method, a solution polycondensation method, a solution polycondensation method, or the like. In the interfacial polycondensation reaction, a known water-soluble neutralizing agent described below is used. It's Kade.

In the case of solution polymerization, a neutralizing agent consisting of a known tertiary amine such as triethylamine, pyridine, tributylamine, pyridine, etc. is used. In the interfacial polycondensation method and the solution polymerization method, a reaction solvent is used, and this solvent may be at least one of aromatic diamine solution, aromatic dicarboxylic acid and trimellitic acid solution, or reactive acid derivatives thereof. If possible, one must be able to dissolve both. A representative example of a particularly effective reaction solvent for use in the present invention is cyclohexanone. Some other solvents that can be used include methylene chloride, trichlene, perchlorene, dichloroethane, nitrobenzene, chloroform, carbon tetrachloride, diisobutyl ketone, acetophenone, p-methylacetophenone,
N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacedoS, N,N-dimethylmethoxyacedoS, dimethylsulfoxide, N-methyl-2 -Pyrrolidone, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylene sulfone, dimethyltetramethylene sulfone, and the like.

Two or more reaction solvents may be used in combination, if necessary, to facilitate the dissolution operation. Also.

In order to obtain polymeric needles as much as possible, it is preferable to use highly dehydrated solvents for dissolving the aromatic dicarboxylic acid and trimellitic acid or their reactive acid derivatives. In particular, N,N-dimethylformamide, N,N-
Dimethylacetamide.

When performing solution polycondensation using a polar solvent such as N-methyl-2-pyrrolidone, adding 5 to 10 times more of lithium chloride, calcium chloride, calcium rhodan, etc. as a co-solvent will result in a marked increase in solubility. It's even more convenient. In addition to this co-solvent, all other known co-solvents as described below are effective.

The reaction can also be carried out by the following method.

That is, unlike the usual interfacial polycondensation method in which the diamine is dissolved in an alkaline aqueous solution, the diamine is dispersed in an alkaline aqueous solution, and the aromatic dicarboxylic acid and trimellitic acid tubalide are dissolved in an organic solvent. This method involves adding a solution and causing a reaction. By polymerizing in this method, the generated halogenated aqueous liquid is neutralized with a neutralizing agent and becomes water and halogenated gold paulownia, which dissolves in water.When the polymer is precipitated from the organic phase, the polymer is Since no agent remains, this gives favorable results for polymeric products. In this case, the amount of alkali used is between 1.3 and 1.3 degrees, preferably between 1.0 and 11 degrees, relative to the halide of aromatic dicarboxylic acid and trimellitic acid.
This is the current location. here.

Neutralizing agents used include water-soluble sodium hydroxide, potassium hydroxide, sodium carbonate, and hydrogen carbonate).
Examples include, but are not limited to, IJum. Further, the amount of water is sufficient as long as the above-mentioned neutralizing agent is sufficiently dissolved at room temperature. Of course, even if it is used more than that, it will not interfere with the two reactions. The reaction temperature is the state where water is liquid.

That is, it is in the range of 0 to 100°C, preferably 5 to 60°C. The above polycondensation method can be carried out, for example, by the following procedure. First, a neutralizing agent is dissolved in water at a suitable temperature of 1°, and an aromatic diamine is added thereto. Furthermore, a solution of an aromatic dicarboxylic acid and a trimellitic acid halide dissolved in an organic solvent is added to cause a reaction. At this time, it is preferable to carry out the reaction in a state where the aromatic diamine is dispersed in the alkaline aqueous solution by stirring. Next, only the organic phase is separated and placed in an organic solvent that does not dissolve the polymer and is easily compatible with the reaction solvent to precipitate the polymer. By filtering all of this, an aromatic polyetheramide resin is obtained. In the present invention, the aforementioned various aromatic diamines and aliphatic diamines can be used as neutralizing agents. In this case, the proportion of 1 equivalent or less (darkness not involved in the reaction)
You can increase the amount.

In addition, known polyamide-forming reactions between aromatic dicarboxylic acids and amide-forming derivatives other than halides of trimellitic acid and aromatic diamines represented by the general formula (11), such as high-temperature polycondensation or transesterification using phosphorus catalysts, are also available. etc. can also be adopted.

The aromatic polyether amide S dopolymer obtained according to the present invention is dissolved in, for example, a polypropylene solvent during film formation.

Here, the polar solvent is acetamide.

N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide.

Examples include N,N-diethylacetamide, N-methyl-2-hydrolidone, dimethylsulfoxide nitrobenzene, glycol carbonate, and cyclohexanone, and these may be used alone or in combination of two or more. Polar solvents may also be hygroscopic. If only polar solvents are used, the film tends to become cloudy during film formation.

It is preferable to use a solvent with low hygroscopicity.

Examples of solvents with low hygroscopicity include methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, xylene, 2-ethylhexyl acetate, N-butyl lactate, acetophenone, 2-ethylhexyl alcohol, and ethyl N-amyl ketone. Such a solvent is not particularly limited as long as it has low hygroscopicity. Note that this solvent may not be able to read the aromatic polyetheramide-imide polymer.

It was. Since the aromatic polyether amide imide polymer has excellent heat resistance and solvent resistance, it is advantageous for application to fields that require such properties.

Regarding solvent resistance, gasoline, commercial oil, and benzene.

For toluene, aliphatic alcohols, acetone, methyl ethyl ketone, various ester solvents, etc.

Insoluble.

7'f I/i'-'-Ji gbl 114)
- ZR1 and I6111fr? h MMR1'l
-) Z-A: 4-Sa is not limited by these.

For evaluation of film-forming properties, a solution of each mixed solvent was prepared and coated on a glass substrate rc using a spinner, and the state of the film was examined visually or with a liposcopic microscope.

Implementation ρIIt Resin: Set a stirring rod, thermometer, and lower funnel in a 1000 m flask, and add 17.2 g of NaCH to 80 g of water.
Dissolve in ml and put into a flask. Next, 2.2 bis C
4(4-aminophenoxy)phenyl]prohane 73.
The mixture was dissolved in 99Q cyclohexanone 34o9, poured into a flask, and cooled to -2°C. - power, prephthalic acid dichloride io, 9 g and isophthalic acid dichloride 10.99 and trimellitic anhydride chloride 15
．． 29 was dissolved in cyclohexanone 2409, and this acid chloride solution was poured into the flask from the dropping funnel.
On this occasion.

The reaction was allowed to proceed for 3 hours while ensuring that the reaction temperature did not exceed 10°C. The reaction solution was poured into methanol to isolate the polymer. After drying this, add dimethylborum 7S again.
K ifi)I+'1. An aromatic polyether amitimide polymer was purified by distilling l-O-h and extracting W. Reduced viscosity of this polymer (ηsp//c)
(Measured in a 0.2% by weight solution of dimethylformamide at 30° C.) was 1.1 del 9. 5 g of this polymer was dissolved in 959 N-methylpyrrolidone-butyl cellosolve acetate (mixing ratio 4:6) to prepare a 5 weight φ varnish. Apply the varnish with a spinner (10
00rpm-30SeC)j, 25°C-72%⇠I
(When it was left in a desiccator, it did not become cloudy even after 2 hours.

Example 2 A polymer and varnish were prepared in the same manner as in Example 1, except that raw materials having the following compositions were used.

The reduced viscosity (ηSp/c) of this polymer was 12 dg/g.

This polymer varnish was prepared in the same manner as in Example 1.

Although it was left in a 72% H desiccator at 25°C, it did not become cloudy even after 2 hours.

Comparative Example An aromatic polyetheramide polymer and varnish were prepared in the same manner as in Example 1, except that raw materials having the following compositions were used.

The reduced viscosity (η3p, /, ) of this polymer is 1.3 d
It was el 9.

A film (thickness 5
0 to 80 μm) was prepared, and the temperature at which lid reduction started was measured using a thermobalance. (Constant rate temperature increase 5°C/m1n) The results are shown in Table 1VC.

Table 1 Measurement Results As is clear from the above results, the aromatic polyether amide imide polymer obtained by the present invention does not become cloudy during film formation, and is also suitable for use in liquid crystal alignment control films, etc. It is useful as a coating material in fields that require high performance. In addition, film formation or membrane formation is possible at low temperatures and in a short time.

Note that the resulting coating film has particularly excellent heat resistance.

Claims (1)

[Scope of Claims] 1. Aromatic dicarboxylic acid or its reactive acid derivative, trimellitic acid or its reactive acid derivative, and general formula (Il (wherein formula 1, ax, R2, R3 and R4 are hydrogen. Lower Indicates an argyl group, a lower alkoxy group, chlorine or bromine, which may be the same or different from each other.
, Rls and R6 are hydrogen, methyl group, ethyl group,
An aromatic polyether amide produced by subjecting an aromatic diamine represented by a propyl group, a trifluoromethyl group, or a trichloromethyl group, which may be the same or different from each other, to a polycondensation reaction. Method for producing imide polymer.