JPS6264829A - Aromatic polyamide-imide-ether - Google Patents

Abstract

PURPOSE:To obtain a polytrimellitamide-imide of excellent processability without detriment to the inherent mechanical properties and heat resistance, by composing it so that the major part of the total repeating units may be specified structural units. CONSTITUTION:An aromatic polyamide-imide-ether comprising at least 60mol%, based on the total repeating units, structural units of the formula (wherein the left and right sides of the formula in each pair of parentheses may be reversed). Said polyamide-imide-ether can be produced without causing gelation by directly polymerizing trimellitic anhydride with 3,4'-diaminodiphenyl ether in N-methylpyrrolidone. The polymer obtained in this way can be formed into a flexible film by baking at a temperature of about 250 deg.C. Said polymer can be used in a wide variety of applications such as varnishes, adhesives, films, fibers, matrix resins for fiber-reinforced composites and resins for compression molding, extrusion molding and injection molding.

Description

[Detailed description of the invention] <a. Industrial application field> The present invention applies to varnishes, adhesives, films, and fibers.

The present invention relates to a novel polyamideimide ether with excellent processability that can be used in a wide range of applications, such as matrix resins for miscellaneous reinforced composite materials, and molding resins for compression molding, extrusion molding, injection molding, etc.

<b. Prior Art> It is well known that aromatic polytrimellidoamideimide can be obtained by reacting trimellitic acid anhydride or its functional derivative with aromatic diamine or its functional derivative. .

In particular, those having 4,4'-diaminodiphenyl ether residues as aromatic diamine residues have a good balance of heat resistance, processability, cost, etc. among heat-resistant polymers, and are used for varnishes, films, and molding. It has been put to practical use in various applications such as resins.

These polytrimelide amide imides have the following formula E, where,
represents 10- or -CH2-. ] is generally expressed as a repeating unit.

The reason why this polyamideimide has processability that can be used in a wide range as described above is thought to be because the trimellidoamideimide structure has an asymmetric structure, as understood from the above formula. First of all, it is clear that the polymer is asymmetrical with respect to the axial direction, but four types of sea fences can also be considered in the perpendicular direction depending on how the amide groups and imide groups are arranged. When the unit of trimellidoamideimide is expressed as AI, the following 4 types -AI-AI
-AI -... (A) -IA-AI-IA-...
It is expressed as a sea fence of (01 -AI-AI-1Δ-...(c) -IA-AI-AI-...(d).

Comparing this to stereoregulatory polymerization in the case of poly-α-olefins, (a) is isotaftic.

fo] corresponds to syndiotastic, and (c) and (d) correspond to heterotaffic.

Depending on the manufacturing method, the above-mentioned polyamide-imide has AI arranged in (a) type, (0) type, or (i) type.
A random thing containing a mixture of ~(d)! Although it is possible to create an IL, a random one is easiest to manufacture.

However, even if the polytrinolyl-hairamide imide comprising the repeating unit represented by the formula (If) has the above-mentioned random structure, it cannot be said that the processability thereof is sufficient.

For example, this becomes clear when attempting to obtain, for example, a flexible polyamide-imide coating by direct polymerization of trimellidic anhydride and aromatic diamine, which is the cheapest method for producing such polyamide-imide.

Generally, such polymerization is difficult to perform by melt polymerization, so a high-boiling polar solvent such as N-methylpyrrolidone is used as a plasticizer rather than a solvent and thermally polymerized at high concentration.
It is best to obtain a highly polymerized chain polymer as it is, so dilute it with -l to make a dope, and after coating it,
A method is used in which post-polymerization and curing are carried out at a temperature of about 0°C three times.
In this case, as will be explained in detail later in the comparative example, when 4,4'-diaminodiphenyl ether is used as the aromatic diamine, the polymerization solution becomes cloudy and eventually becomes cloudy and glue-like, making further polymerization difficult and requiring dilution. However, the solution will not be uniform.

On the other hand, when 4,4'-diaminodiphenylmethane is used, a highly concentrated solution during polymerization tends to cause gelation.
It is necessary to pay attention to the conditions. Therefore, when applying a polymer manufactured under conditions that do not cause gelation and attempting to perform post-polymerization at a temperature around 250°C, the diphenylmethane bond is easily oxidized and is not thermally stable enough, resulting in decomposition and polymerization. It has been found that this occurs in parallel, making it difficult to obtain a flexible coating.

<a1 Purpose of the Invention> Therefore, in order to obtain a polytrimelide amide-imide with better workability without impairing the mechanical properties and heat resistance of the polytrimelide amide-imide as described above, the present invention was made based on intensive studies. has been reached.

<d. Structure of the invention> In the present invention, 60 mol% or more of all repeating units has the following formula (
I) However, the expressions within each 0 may be independently reversed left and right.

It is an aromatic polyamideimide ether consisting of the structural unit represented by

The aromatic polyamideimide ether of the present invention dramatically increases the randomness in the main chain direction by using an asymmetric aromatic diamine as well as the trimellitic acid residue. In addition, the 3,4'-diaminodiphenyl ether residue has good linearity and no large bending when the molecular chain is stretched, so it can be incorporated into the structure of, for example, a high-strength, high-Young's-modulus aramid fiber. Moreover, the raw material, for example, 3,4'-diaminodiphenyl ether, can be produced in one or two steps from industrially produced intermediates, which is advantageous in terms of cost.

Furthermore, since the middle part of the structure is rich in asymmetrical structure, the randomly polymerized trimellitic acid component and diamine component can have 16 main types using the expressions (a) to (d) above. For example, considering only the orientation of trimellitic acid amide imide and 3,4'-diaminodiphenyl ether residue, chain structural units are included, as shown below.
There are structural units of species.

! .

The aromatic polyamideimide ether of the present invention is produced by directly polymerizing trimellitic anhydride and 3,4'-diaminodiphenyl ether in N-methylbidaylidone, as detailed in the examples. The polymer thus obtained can be produced at 250%
A flexible film can be obtained by baking at a temperature around °C. This fact is based on the 4゜4'-diaminodiphenyl ether residue or 4゜4'-
This could not be achieved with those having a diaminosifnylmethane residue, and it is understood that the object of the present invention has been fully achieved.

As a method for producing the polyamideimide ether of the present invention, any known method for producing aromatic polytrimelideamideimide can generally be applied.

These production methods will be explained below in the following order: one in which the orientation of trimellidic acid residues and diamine residues is random, and one in which the directions are thought to be regularly arranged. However, as stated in the claims, the polymer of the present invention is due to its structure and not due to its manufacturing method.

(I-1) Direct reaction method of trimellidic anhydride and 3,4'-diaminodiphenyl ether The polycondensation reaction between trimellidic anhydride and 3,4'-diaminodiphenyl ether can in principle be carried out in the bulk state. However, the high melting point makes it difficult to carry out industrially, so it is generally carried out in the coexistence of a liquid reaction medium. Methods using such liquid media are classified into two types: those using solvents that have solubility in the polymer, and those using solvents that do not have solubility in the polymer.

An example of the former is N-methylpyrrolidone.

N,N'-dimethyl cyclic ethylene urea, high boiling point non-button polar solvents such as tetramethylene sulfone, and cresol, xylenol, phenol.

Examples include phenolic solvents such as 0-phenylphenol.

The reaction proceeds uniformly in such a solvent. First, the acid anhydride group of trimellidic anhydride reacts with the amino group, then the dehydration ring closure of the adduct forms an imide group, and then the carboxyl group of trimellidic anhydride reacts with the remaining amine group to form an amide group. Proceed in order.

The reaction to form an imide group easily proceeds at around 150°C in a homogeneous state, but the direct reaction between an aromatic amino group and a carboxyl group is relatively difficult to occur and does not proceed easily unless the temperature is 200°C or higher. . Therefore, in the latter half of the reaction, the concentration of the polymer becomes quite high, and the solvent is allowed to react in such a state that it acts as a kind of plasticizer. The by-produced water needs to be azeotropically distilled off with the solvent or distilled off together with its vapor.

In such a reaction in a solvent, it is generally difficult to allow the reaction to proceed to a degree of polymerization that allows the formation of a flexible film as it is. By conducting temperature
The general direction in this case is to obtain a flexible molding.

The solid phase-containing polymer is melted again,
It can also be shaped again.

The reaction can also be carried out by adding a small amount of a catalyst for promoting the reaction between aromatic amino groups and carboxyl groups, such as polyphosphoric acid, 1- to rifhenyl phosphite, etc.

Furthermore, a condensing agent that participates in the synthesis reaction between an aromatic amino group and a carboxyl group and also changes itself to promote the amide formation reaction can also be used. Examples of such condensing agents include (]・liphenylphosphine+pyridine), diphenyl phosphine, diphenyl carbonate, and the like.

Such a condensing agent may be added in an amount sufficient to react all the 4-carboxyl groups of the trimellidic acid residue with the remaining amino groups at the stage of the imidization reaction and the distillation of the resulting water, but it is more economical. In order to carry out the reaction, it is also possible to advance the polymerization as much as possible by reaction in a solvent, and then add only the amount corresponding to the remaining terminals. In this case, the reaction temperature varies depending on the reaction activity of the condensing agent,
(triphenylphosphine pyridine) system is generally below 100°C, and in the case of diphenyl carbonate, the temperature is 15°C.
A range of 0°C to 200°C is generally used.

On the other hand, a solvent that does not have solubility for the polymer is used as a kind of heat medium in the form of dispersing the polymer in a molten state or in the same phase state. Therefore, the solvents used for this purpose have a high boiling point, good thermal stability, and are not very polar, such as diphenoxybenzene, 0-terphenyl, diphenyl ether, and other aromatic and mineral oil heating media. I can do things. The reaction temperature was finally 25
It is preferable to be able to carry out the process down to around 0°C.

(I-2) When an activated functional derivative of trimellidic anhydride is used, the cyclic acid anhydride group of trimellidic anhydride is, as described above,
Although it has sufficient reactivity towards aromatic amine groups,
Since the activity of the carboxyl group at the 4-position is low, it is necessary to use a derivative in which this is activated.

A method for activating the reactivity of a carboxyl group to a nucleophilic reagent is to increase the electronegativity of the carbonyl of a carboxyl group, such as a carboxylic acid halide, an active carboxylic acid amide, or an active carboxylic acid gx ster.

Examples of carboxylic acid halides include 4-chloro-activated amides such as trimellidic acid-4-imidazolide-1,2-anhydride and trimellidic acid-4-phenyl ester-1A.
− Can give fortune telling etc.

Regarding the reactivity of these activated forms, acid chloride has greater reactivity with amino groups than acid anhydride, imidazolide has approximately the same reactivity depending on the reaction atmosphere, and phenyl ester has less reactivity than acid anhydride. Can be categorized.

Therefore, in the case of 4-phenyl esterified derivatives, polymerization can be carried out basically by the same reaction method as in the case of using trimellidic acid anhydride. However, in the case of amide formation, the by-product is not water but phenols that are soluble in the polymer, and this acts as a plasticizer, making bulk polymerization and suspension polymerization easier and more efficient. proceed as planned.

Further, when using solution polymerization, there is an advantage that the post-polymerization can proceed efficiently even if the post-polymerization is performed by heat treatment after molding using a solution.

When using a 4-acid chloride derivative, the desired polyamide can be synthesized using the following formula (Il+) using a method via polyamic acid, such as the so-called interfacial polymerization method and low-temperature solution polymerization method used for the synthesis of wholly aromatic polyamides. You can get Imidonychill.

(Margin below) In the interfacial polymerization method, te]~rahydrofuran.

It is carried out using a moderately polar organic solvent such as methyl ethyl ketone and water. That is, a water-soluble dehydrochlorination agent such as soda carbonate or potassium carbonate is dissolved in water, and the organic solvent is divided into two parts, and the aromatic amine is added to one part and 4-chloroformylphthalic anhydride is added to the other part. This is carried out by a method in which the aqueous solution and amine solution are dissolved and then added and polymerized all at once while stirring the aqueous solution and the amine solution using a high-speed stirrer such as a household mixer. As a result, the polymer in the form of polyamic acid is recovered in powder or flake form.

This polymer powder is heated under an inert atmosphere or under reduced pressure for 2
00 to 300 ° C., hO heat, ring closure, recover as polyamide imide nityl powder, and use it for subsequent molding.Dissolve the polyamic acid powder in a solvent, mold from the solution,
Thereafter, the polyamide acid solution is heated as a solution, then an imidization ring-closing agent such as pyridine + acetic anhydride is added, heated to imidize in the solution, and used as a polyamide-imide solution. An appropriate method can be selected depending on the application and conditions of use, such as the method of shaping.

The low-temperature solution method uses a so-called aprotic polar solvent such as N-methylpyridone, N,N-dimethylacetamide, N,N'-dimethylethyleneurea, etc., and if necessary, in the presence of a deoxidizing agent, at a low temperature to around room temperature. 4-chloroformylphthalic anhydride and diamine are reacted to obtain a polymer in the form of a polyamic acid solution. The polyamic acid thus obtained can be reprecipitated and recovered from the solution, and processed and shaped in the same manner as in the interfacial polymerization method.

Furthermore, the above polyamic acid solution can be used as it is as a stock solution for molding. At this time, it is preferable to react the hydrogen chloride produced as a by-product with, for example, ethylene oxide to eliminate corrosivity as ethylene chlorohydrin. Further, the solution can be heated, polyamic acid is added to polyamideimide, and the solution can be used as it is for the next shaping.

At that time, the by-produced water is azeotroped with chlorohydrin to -1
q - It is preferable to distill it off.

In the case of imidazolide, it can be reacted and treated in the same manner as acid chloride using the above-mentioned low-temperature solution polymerization method.

In the case of imidazolide reactions, adding an acid to the system can accelerate the reaction.

(I-3) When using activated f'l derivatives of aromatic diamines A method of activating aromatic diamines without using trimellidic acid anhydride is to use the corresponding diisocyanate. I can do it.

[Formula 02) 1% Formula %] By carrying out this reaction in an aprotic polar solvent such as N-methylpyrrolidone, the desired polyamideimide solution can be obtained, and the carbon dioxide gas produced as a by-product can be obtained. can be easily removed from the system as a gas, so it is the most advantageous method when using a polymer as a solution. However, as a reaction raw material, diisocyanate must be produced from diamine by reaction with phosgene, and the corresponding 4,4'-Schiffnylmethine diisocyanate, such as 4,4'-diaminodiphenylmethane, is
It is especially advantageous if it has other uses and is mass-produced, but if a special diamine is used as in the case of the present invention, it may be disadvantageous unless you are in a position to easily make diisocyanate from it. .

Furthermore, although the amino group is not necessarily activated, it is also possible to acylate it with a lower aliphatic acid such as acetylation, and carry out the amidation reaction in the form of IIRit acid or the like. This method is particularly advantageous when the reaction is carried out at a high temperature in the final stage of the polymerization reaction, for example, when performing solid phase polymerization. That is, amino groups, especially aromatic amino groups, are susceptible to oxidation and thermal decomposition at high temperatures. Therefore, if an attempt is made to form an amide group by direct reaction between an amino group and a carboxyl group at high temperatures, decomposition of the amino group will occur. Although the degree of polymerization may not be sufficiently high, the acylated amino group becomes stable in that respect, and a polyamide-imide with a high polymer content may be easily obtained, which is advantageous.

Utilizing the difference in reactivity between the two functional groups of trimellidic anhydride or its functional derivatives, that is, the cyclic acid anhydride group and the carboxyl group or its functional derivatives, or as an intermediate in the diamine production process. By controlling the order of reactions by using the body, it may be possible to regularize the orientation. Even in that case, if the reaction conditions in the subsequent stage are severe, an exchange reaction may occur and the regularity once obtained may be disrupted, so care must be taken.

It is extremely difficult to analytically confirm the presence or absence of this regularity, and we believe that it is currently impossible.

Therefore, the rest is based on a comparison of properties, but in many cases there is not much difference, and in the end it is often only a matter of guessing from the manufacturing method. In general, the manufacturing method for obtaining regular polymers is often more complicated than that for obtaining random polymers, as described below, and considering the characteristics of the polymer of the present invention, it is also suitable for random purposes. It can be said that there are many cases in which something is preferable.

(n-1) In case of Al-Al-Al type, a typical method for producing 3,4'-diaminodiphenyl ether is represented by the following formula 0(8).

Therefore, by using the intermediate 3-amino-4'-nitrodiphenyl ether, it is possible to obtain a regular polymer according to the route shown in formula 04) below.

1 % 5 - Possible I -25- Hehe - Since the reaction conditions for each reaction can be easily carried out by a person skilled in the art based on the above explanation, the details will be omitted.

(TI-3) AI-IA-AI type Currently, it is difficult to control the direction of the diamine in this type, but the direction of AI can be controlled by the path as shown in the following formula (151). You can get things.

(Margin below) 11 11 II I1
In this case as well, the details of the reaction conditions for each reaction will be omitted since it is believed that the reaction conditions can be easily carried out by a person skilled in the art based on the above explanation and using techniques that are easily understood by those skilled in the art.

The polymer of the present invention is preferably composed only of the formula (T), but 60 mol% or more of the total repeating units is of the formula (T).
I), the characteristics are generally maintained.

Therefore, in order to impart performance that can better meet the performance requirements of each application while maintaining the original characteristics, up to 40 mol% of other repeating units can be copolymerized and introduced. As such a copolymerizable unit, the following aromatic amide unit Q61 (161'), imide unit 071, and amide-imide unit (2) are preferable.

(However, in the formula Ar + , Ar 2 , Ar 3
, Ars.

Ary, Ars are divalent aromatic groups having 6 to 20 carbon atoms, Ar4 is a tetravalent aromatic group having 6 to 20 carbon atoms, and Ars is a trivalent aromatic group having 6 to 20 carbon atoms. Examples of the aromatic group include a benzene nucleus, 2-3, and more specifically, the following examples. That is, instead of a part of the acid amide imide residue, a pyromellitic acid imide residue (Ar4-lutetracarboxylic acid diimide residue M
(Ar4- can be done.

Similarly, terephthalic acid amide residues can also be used as isophthalic acid amide residues.

Furthermore, N − (m or p −) ■ Nirentorimeri can also be formed.

As described above, when only the carboxylic acid component and the copolymerization component are introduced, Ar 2 and Ar s are 3,4', while
A part of the 3.4'-diaminodiphenyl ether component can be used in place of other aromatic diamines. Such aromatic diamines include m- or p-phenylene diamine, 4,4'-diaminodiphenyl nityl,
3.3'- or 4'-diaminodiphenylsulfone, 3.3'- or 4,4'-diaminobencyphenone, bis(IIl or p-aminophenoxy 11.3- or -1,4-benzene) etc. can be given.

Furthermore, it is also possible to replace both the carboxylic acid component and the diamine component with the above components within the scope of the claims.

Furthermore, after molding, the polyamideimide ether of the present invention can be heat-treated to improve heat resistance in use by partially maintaining the structure of formula (I) and introducing a crosslinked structure into the polyamide-imide ether. I can do it. As a method for introducing such a crosslinked structure, aromatic triamine or tetramine is added to the resulting polymer at the end of the polymerization reaction, and after molding in an uncrosslinked state, it reacts with the end groups by heat treatment to form a crosslinked structure. The easiest and most effective method is to introduce

As such triamine and tetramine, 2°4.4'
-1-riaminodiphenyl ether, 1°3.5
- or 1,2,4-triaminobenzene.

Examples include 3.3', 4.4'-tetraaminodiphenyl ether.

On the other hand, polycarboxylic acids having trifunctionality or higher functionality for aromatic amino groups, such as trimesic acid or its derivatives, can also be used.

The polyamideimide ether of the present invention must have a degree of polymerization that allows it to form a self-supporting film after being shaped and, if necessary, subjected to heat treatment.

The logarithmic viscosity of the prepolymer, including one step, in its soluble state is generally between 0.05 and 2, more preferably between 0.597 and 0.597, as measured in N-methylpyrrolidone solution.
15 to 1.2 is used.

In order to form a film without post-thermal polymerization and to have self-supporting properties, a logarithmic viscosity of 0.4 or more is generally required, but as mentioned above, a prepolymer with a logarithmic viscosity of 0.4 or more is required, for example, 0.4 or more.
Even if it is about 15, it is possible to cause a terminal reaction etc. by heat treatment after shaping, and to make a flexible polymer by post-polymerization or post-crosslinking.

Even if the polyamideimide ether of the present invention is thought to consist only of the same repeating structure of formula (I), there may be some differences in properties depending on the manufacturing method.

This may be due to the above-mentioned sequence difference, but it is also thought that the reaction conditions generally vary depending on the manufacturing method, so that slight side reactions can affect the properties.

Polyamideimide ether, which is thought to consist only of general formula (I), has a glass transition point of about 230 to 250°C (measurement method: TMA needleman method) and a softening point of about 300°C (
Measuring method: capillary one-type rheometer),
It has heat resistance that can withstand long-term use up to 240°C.

The polymer of the present invention can be used in varnishes and adhesives as described above.

It can be used in a wide range of applications such as films, Il fibers, matrix resins for mu-reinforced composites, and molding resins for compression molding, extrusion molding, injection molding, etc.

For varnishes, it is generally in the form of a solution containing N-methylpyrrolidone or cresol as the main solvent, and can be used for enamel varnishes for electric wires, aluminum fixtures, etc. Furthermore, the powdered polymer can be used for metal surface coatings by powder baking.

Films and fibers can be formed from a solution of the polymer by wet or dry molding. Both, its good heat resistance,
1. Electrical insulation using flammability.

It can be used for protective clothing, etc.

As the adhesive, it is possible to use a dry film adhesive formed into a film, or a solution adhesive in which a solution is applied to an adherend and then heat-sealed after drying. The material to be adhered to is metal, especially iron.

Used for bonding aluminum, stainless steel, copper, etc.

The matrix resin for fiber-reinforced composite materials can be applied to the surface of reinforcing fibers in the form of a solution or powder interstitial, formed into strands, unidirectional prepreg, etc., and processed by autoclave molding, press molding, filament winding, etc. Molded objects can be obtained by means. For molding resin, we create a molding resin compound with various additives,
Using it, a molded product can be obtained by compression molding, extrusion molding, injection molding, etc.

As mentioned above, the molded products described above have well-balanced performance in heat resistance, mechanical properties, and chemical resistance.
It can be widely used in advanced technology fields as functional parts for various transportation equipment such as aerospace, automobiles, and ships, as well as components for electrical, electronic, automation equipment, sporting goods, energy equipment, etc.

In actual use, various additives, other polymers, etc. can be blended and used.

The present invention will be explained in detail with reference to Examples below. The examples are illustrative and not limiting.

Example 1 [Method by direct reaction of trimellitic anhydride and 3,4'-diaminodiphenyl ether (3,4'-r)APE] 500 d three-neck flask equipped with a stirrer, thermometer and nitrogen inlet Completely dry the 3.4'-DAPE (
3,4'-diaminosyphinyl ether) 60.00
NMP (
N-Methylpyrrolidone>ioog was added and dissolved. Add TMAA (1-limellitic anhydride) to this solution.
57.58 g and 0.539 g of triphenyl phosphite were added, and the temperature was increased by heating. N containing water from the polymerization reaction system
As MP was distilled off, the viscosity of the solution gradually increased and the internal temperature of the polymerization reaction system also increased. Approximately 85g of NMP
The m degree in the system was 262°C at the time when (water content) was distilled off. In order to obtain an appropriate solution viscosity as a stock solution for film formation, NMP 209 was added to dilute the solution.

A portion of this solution was taken out and precipitated with water in a mixer in a conventional manner to obtain a polymer powder. The degree of polymerization of this polymer was measured with NMP at a concentration of 0.5 g/dl at 30° C., and η1nh was 0.26. The infrared absorption spectrum of the obtained polymer is shown in FIG. It can be seen from the characteristic absorption that the desired polyamideimide ether was obtained.

The above polymer solution was cast onto a glass plate using a doctor knife and placed in a hot air dryer to form a film at 120-180°C x 6
0 minutes, 250°C x 60 minutes), a relatively tough film was obtained.

Comparative Example 1 In exactly the same manner as in Example 1, 4.4'-DAPE30
．． When 00g and TMAA28.789 were subjected to a polymerization reaction in the presence of triphenyl phosphite in NMPloo, the inside of the system gradually became opaque during the distillation of NMP, and the polymer finally gelled and precipitated. No processable polymer was obtained.

Example 2 Polymer solution prepared using the same equipment and monomer/solvent preparation as in Example 1 (prepolymer concentration: 64% by weight)
) 22.9g of diphenyl carbonate 0.59 and N
10 g of M P was added and heated to 210 to 240°C. Since the solution viscosity of the polymerization system gradually increases, N
Diluted with MP. The finally obtained polymer solution having a polymer concentration of 25% by weight was formed into a film in the same manner as in Example 1 to obtain a relatively tough film.

The polymer obtained by precipitation from the polymer solution obtained in this example in a conventional manner had ηinh of 0.5.

Example 3 Activated functional derivatives of trimellitic anhydride and 3.4
'-Polymerization of DAPE; Part 1] 500Id equipped with a stirrer, thermometer and nitrogen inlet! Thoroughly dry the three-necked flask of 3.4'-r) A P E 17.83 g
and NMP 10 dehydrated with molecular sieves.
0g was added and dissolved. This solution was cooled to -10°C, and CPΔ (4-chloroformylphthalic anhydride) 18,839 purified by vacuum distillation was gradually added. The mixture was further stirred for 3 hours or more to prepare a polyamic acid solution. A portion of the obtained polyamic acid solution was diluted with NMP to a concentration of 0.5 g/old, and ηinh measured at 30° C. was 0.5.

In the same manner as in Example 1, a relatively tough film was obtained by casting on a glass plate using a doctor knife and forming a film under the same conditions in a hot air dryer. The infrared absorption spectrum of the obtained film is shown in FIG.

[Mechanical properties of the obtained film] Mechanical properties Example 4 [Activated functional derivative of trimellitic anhydride and 3.4
'-Polymerization of DAPF; Part 2] Completely dry a 500 d three-necked flask equipped with a stirrer, thermometer and nitrogen inlet, and add 3.4'-DA P E 17.839.
100 g of metacresol was added and dissolved. Add 23.88 g of phenyl ester of trimellitic anhydride to this solution.
Added 9. This solution was polymerized in the same manner as in Example 1 while increasing the reaction temperature while distilling off the solvent. The resulting viscous solution was diluted with metacresol while cooling to 150°C to obtain a 25% by weight polymer solution.
A relatively strong film was obtained in the same manner as above.

Example 5 [Polymerization reaction between trimellitic anhydride and activated derivative of 3.4'-DAPE] In exactly the same manner as in Example 2, 1-24.84 g of diisocyanate of 3.4'-DAPE and T M A A 2
4.089 were gradually mixed and stirred in 100 g of NMP. The reaction temperature was gradually raised and the mixture was further stirred at 100°C for 1 hour. The solution was diluted little by little with NMP as the viscosity of the solution -F increased, and the final polymer concentration was 20% by weight.

η of the polymer precipitated from a portion of the resulting polymer solution
inh is 0.5 dl/g.

Casting was carried out using a doctor knife on a glass plate in exactly the same manner as in Example 1, and the solvent was removed using a hot air dryer to obtain a relatively tough film.

Example 6 Method for producing polyamideimide ether whose E orientation seems to be regular] 3.4′-r″1APE13,369 is N M P 3
0- (solution A). Same <NMP150-
It was quickly dissolved at 15°C (solution B). After mixing solution B and solution A, 3.4'-[)APF powder 13,3
59 was added to carry out a Φ combination reaction. Part of the obtained polymer solution was precipitated, and the polymer ηinh was 0.4 dl/
It was g.

Example 7 The polymer powder obtained in Example 2 was measured using a capillary one-type rheometer (capillary: diameter 0.5M x length 0,
5. ) The flow characteristics were measured. It exhibited fluidity at temperatures above about 300°C, and at 350°C it exhibited good fluidity in a molten state. On the other hand, a similarly prepared polymer from 4°4'-DAPE exhibited fluidity only at 375°C.

The polymer powder obtained in Example 2 was placed in a hot compression mold,
A good test sample was obtained by molding at 350° C. and 500 kg/cd.

Example 8 Activated functional derivatives of trimellitic anhydride and 3.4
'-Copolymerization with DAPE and MPDA (meta-phenylenediamine)] Completely dry a 500 d three-necked flask equipped with a stirrer, thermometer and nitrogen inlet, and 3.4'-DAPE
i6,989 and 4,59 g of MPDA were added, and 150 g of NMP (N-methylpyrrolidone) dehydrated with molecular sieves was added and dissolved. Add this solution to 10
℃, and CPA (4-chloroformylphthalic anhydride) 26.87 (j) purified by vacuum distillation was gradually added. Further, the mixture was stirred for 3 hours or more to prepare a polyamic acid solution. The obtained polyamide A portion of the acid solution was diluted with NMP to a concentration of 0.59/old and measured at 30°C. A portion of the polyamic acid solution was diluted with NMP to a concentration of 0.5 g/old and ηinh was measured at 30°C. was 0.4.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum chart of a polyamideimide nityl polymer powder obtained by the same procedure as in Example 1 of the present invention. Figure 2 shows infrared absorption spectrum chart 1 of a polyamide-imide ether film obtained by the same procedure as in Example 3 of the present invention.
7-1~. FIG. 3 is an infrared absorption spectrum chart of a polyamideimide ether film thin film whose orientation appears to be regular, obtained by the same procedure as in Example 4 of the present invention. FIG. 4 is a thermal gravity analysis (TGA) chart of the polyimide obtained in Example 3 of the present invention. jJNk goill shi l5Nk notoyo 1Z (54 no JLJ
W! aM Procedural Amendment 4 1985 10 month z P day

Claims (1)

[Claims] 60 mol% or more of all repeating units are represented by the following formula (I)▲Mathematical formula, chemical formula, table, etc.▼……(I) However, each formula in parentheses is independently left and right reversed. It may be facing the same direction. Aromatic polyamideimide ether consisting of the structural unit represented by.