DE2030415A1 - Thermoplastic imide copolymers ("copolyimides") - Google Patents

Description

Dipl. Ing. Helmut Zoepke
Dipl. Ing. Carl O. Zoepke

Patent attorney · -. ₁ "

ÖMünchen5, ErhardWraße 11 ZUJUA! B

D-9256
W / Sch

International Harvester Company ^ June 1970

401, North Michigan Avenue
Chicago, Illinois 606II (V.St.A.)

Thermoplastic imid copolymers ("copolyimides")

The invention relates to aromatic Xmidmisehpolmerisate and In particular aromatic imide isohpolymers, which have the useful « lent properties of the previously known polyimides have "which are, however, thermoplastic and accordingly with the help of the Procedures such as those used for deforming other thermoplastic shear materials, deformed into objects can be «

Aromatic polyimides are because of their chemical inertness, Strength, high temperature resistance, etc. extremely valuable Materials. However, aromatic polyimides have not yet found widespread use around the world because the previously known representatives do not use the deformed material for thermoplastics could be processed. Because of this property, they can can only be deformed into objects by a limited number of methods, and these methods are all Compared to those with which thermoplastic materials can be processed / relatively expensive.

To solve this problem of poor processability, an attempt was made to produce an aromatic imide homopolymer with the aid of a wciävi - "\: - '. 0098 52 / 7.1-7P .;

BATH ORIGINAL

Implementation to produce in which an aromatic Dianhyirld and an aromatic bag at high temperature in one! Solvent and in the presence of a tertiary amine as a catalyst " are implemented (US Pat. No. 2,422,064).

In this process, a deformable one is proven Powder obtained which combines to form a homogeneous phase at a temperature below the crystalline melting point of the polyimide can be.

However, the association requires the specified USA patent deformable powder pressures obtained from 14o to 2100 kg / cm. As the currently commercially available Presses can only generate pressures of up to 140 kg / cm, be = such materials have little practical value. In addition, the process by which they are made would them because of the severance and others contained in it Make steps too expensive to be technically attractive.

Another attempt at the problem of poor workability «= The ability to solve the known polyimides consists in that one an imide polymer from an aromatic tetracarboxylic acid and two aromatic diamines, one of which also forms has an aliphatic radical (USA "Patent 3 424 718). While such copolymers the desired Thermoplasticity, they are due to the presence of the aliphatic radicals very little thermally stable and therefore lack one of the main properties, the aromatic polyimides give such great value.

The object of the invention are therefore new Imidmisöhpolymerisate which the benefits of the well-known aromatic imide homopolymers such as for example chemical invulnerability, high strength ;, Have high temperature strength, etc. and which are also heat deformable are.

009852/2120

3 - ■ ■ 2030Λ15

Another object of the invention are new imide copolymers, which are inexpensive to manufacture and from precursors with a long shelf life can be made from.

Another object of the invention is to provide new precursors by simple heating in flexible SohKume made of Xmid copolymer material can be converted, as well as new monomeric "resinous precursors for Xmidmlschpolymerisate and a process" Ren for the production of such precursors and their conversion into heat-deformable Xmidmlschpolymerisate, flexible imide copolymer foams and amic acid copolymer precursors of Imidmisohpoiymerisate.

There have now been certain new aromatic, thermoplastic imide copolymers found that the above mentioned disadvantages of the do not have previously proposed solutions to the problem of poor processability of aromatic polyimides. You wise have an exceptionally high heat resistance and can with Pressures are transferred into a homogeneous phase «which is essential are lower than the sun unite those described above deformable powder required pressures * In addition, the process is by means of which they are made are decidedly less expensive than the processes by which the above mentioned Polymers are produced.

The subject matter of the invention is a practically monomeric, resinous imide-isohpolymeric precursor which is essentially a solid solution of a 3 # 3 ^IJ " ^J " ^L -Btn "ophthalmic acid trivit and at least two aromatic disatlones, the are free of aliphatic radicals and of which at least one is n-substituted and five non-substituted ρ-substituted ones, and the ratio of the functional groups required for formation is approximately equimolar. The new aromatic Imldmitohpolymererntt are preferably made from the above all Vorauf he *

BADQfclGJNAL

The invention also relates to a method for production of a monomeric "resinous material" that is practical represents a solid solution of ingredients that lead to a precursor polymerized in the form of a polyimide or a polyamic acid which is characterized in that one a solution of a 3 * 3 * 4,4'-benzophenone tetracarboxylic acid derivative and at least two aromatic diamines in a solvent which is inert towards the acid derivative and the diamines, at least one of the diamines being m-substituted, all non-substituted diamines are ρ-substituted and the ratio of the] fActlonelles required for Xmid formation Groups is practically equimolar, and that the solution is heated to a temperature high enough to the solvent to escape, and which is kept below the temperature at that between the acid derivative and the diamines condensation reactions take place to a significant extent. In a preferred embodiment of this process, the monomeric precursors are prepared by adding 3 * 3 * 4,4'-benzo » phenontetracarboxylic acid planhydride in an excess of an esterification and solvent such as ethanol dissolves, and the solution mixed with the aromatic diamines that you find in the excess Ethanol can dissolve. (As esterifications and solvents Other alcohols can also be used, albeit ethanol because of its easy availability and low cost and other properties is preferred. A change in the alkyl group of the esterifying agent only affects the rate of hardening of the product and properties related to the resinous nature of the material, such as stickiness, drying time, etc.) The solvent is then removed, whereby an amorphous, ηioht-converted, Resin-like mass remains, which is in low-boiling Solvents easily dissolves and which has a long useful life owns what the "Oründe 1" individual in the USA

Patent drill. (Patent application 712 908/1968) of the same Applicant are set out. The invention also relates to a method for producing

. 009852/2120

Position of a particulate, thermoplastic imide polymerizate which can be shaped into consumer goods and which is characterized in that a solid solution of a ₁ ) H ¹ -benzophenone-carbonic acid derivative and at least two aromatic diamines containing no aliphatic radicals is prepared, at least one of the Diamine is in-substituted, all non-m-substituted * diamines are ρ-substituted and the ratio of the functional groups required for imide formation is practically equimolar, that the solution is foamed by heating to a temperature between about 125 and about 150 ° C, that the Foam is divided into particles and the material obtained is hardened by heating to a temperature between about 500 and about 225 * 0. The foam is preferably crushed by grinding.

Finally, the subject matter of the invention is a process for the production of a molded body from the imide copolymer produced by the above process, which is characterized in that the cured particulate polymer is processed at a pressure between about 21 and about 84 kg / cm and a temperature of at least about 330 ^° C deformed to the desired shaped body. The average deformation pressure used is about 56 kg / cm, and the deformation temperature
Settlement temperature of the polymer.

2
56 kg / cm, and the deformation temperature is far below the decomposition

An advantage of the new method of manufacture described of polyimides is that it eliminates the need to use expensive solvents. Another benefit is dad the polymerization reaction simply involves heating requires.

Waiter is advantageous that there are no ohemisms in the deformation stage Reactions occur and accordingly no solvent vapor « or develop other conversion products. This advantage allows the production of tight * void-free structures.

In addition, the production is a »*

0G ° ^e 52 '

as is the case with most of the polyimides known to date is required off because the polyimide is immediately off the monomeric resinous precursor can be prepared. The new systems disclosed in this specification also have a number of advantages due to the inherent shafts of the monomeric precursor according to the USA patent, (application 712 908/1968) by the same applicant.

In the process described above, the particulate material is in most cases, starting from the monomer, converted directly into the intermediate polymer without passing through the intermediate stage of the amic acid copolymer; however, such an intermediate can be formed, but in these cases it is not isolated. For the reasons discussed above, this process for preparing the imide copolymer is preferred for applications such as molding. However, the use of a polymeric precursor can be advantageous for other purposes, such as, for example, the coating of surfaces. In these cases, the diamines and the acid derivative are heated in a solvent, such as Ν, Ν ¹ -dimethylformamide, to a temperature of about 100% until the polymerization occurs. The polymer intermediate can then be isolated by precipitation in water and subsequent filtration.

In connection with what has been said, in another process for the preparation of the newly described Imldmisohpolymerisate the solution of the diamines and the Tetracarbon3äurederivates in a solvent such as Ν, Ν ¹ -dimethylformamide, heated to reflux temperature until polymerization occurs. The polymer is then separated off from the solvent as above. In these cases the isolated polymer is the Xmidmisohpolymerisat.

The thermoplasticity of the new misoh polymers described iut the arbitrary distribution of the recurring units in the polymer chain. More precisely, consists in

0098S2 / 2120 ^;

BATH ORIGINAL

an imide homopolymer a uniformity of the recurring » the units, since the imide homopolymers have the following structure:

- [recurring unitJ-,

where χ is the number of repetitions of the recurring unit represents. Such polymers are accordingly inflexible and crystalline, which is why their excessive temperatures are so are high, because when they are deformed, extensive oxidation occurs takes place. Accordingly, such polymers cannot be thermoformed. .

In contrast, by using me as a diamine component an element of arbitrariness introduced into the polymer chain. This means that in the new Tjnidmlsohpolymerisaten Degree of crystallization in comparison also with the previously known aromatic homopolymers !! observed noticeably decreased.

More precisely, copolymers have just as many different ones repeating units, as are combinations of such there are recurring units forming reaction participants. Mixed polymers can be represented by the following formula:

«[Recurring unit A] _— [recurring unit Bl-- etc.

χ y

If the implementation of the components is subject to chance, χ and y are different and the chain is through an arbitrary one Distribution of the recurring units involved. As mentioned above, tinea leads to a lower degree of crystallinity. It leads to a change in crystallinity to a lowering of the upper temperature of the polymer under his · decomposition door and allows »o, daö · β with Using the same procedures as with others then & oplastleehen materials are used «would be deformed can be. GItlohe «itig there is no loss to WKxrae ·

009852/2120

BATH ORIQINAL

strength as in the known systems discussed above, since im In contrast to these systems, no introduction of aliphatic Residues in the chain takes place (polymers, the aliphatisohe residues included are heat and oxidation susceptibility),

As will be shown below, it already suffices if at the production of the new Imldmleohpolymerisate of the present Invention, only two diamines can be used · However, for some applications it is preferred that three or more diamines can be used and that at least two of them are m-substituted are. If a rigid polymer is to be produced, at least one ρ-substituted diamine is used.

In addition to the above-mentioned advantages, the novel aromatic amine copolymers of the present invention are preferred over other aromatic polyimides, such as the ImId- = copolymers according to the above-mentioned USA patent application 3,424,718, since / 3 made them without forming a polymeric precursor can be. This is important because the aforementioned polymeric precursors are even at room temperature have an extremely short shelf life

Also in connection with what has been said above, it is pointed out that the polymeric precursors of previously known aromatic polyimides were prepared from tetraarbonic acid dihydrides and primary diamines in solvents such as N, N * -dlmethylaoetamide and N, N ¹ -dimethylformamide, which are quite expensive. In addition, the process of converting the polymeric intermediate products into the end product generates volatile substances (solvents and condensation products) which are trapped and lead to a polymer which contains hollow cells. This is of course undesirable. Especially in those cases in which maximum strength of the product lake is required.

In contrast to this, it is possible to use raw thermoplastic imido polymers of the present invention in cheap solvents such as

009852/2120

BAO ORiSfNAL

for example ethanol. They also run When they are deformed, they do not produce volatile substances, which means that they are deformed into dense, void-free objects is guaranteed.

Imldmisohpolymerisate, which are made from 3,> ^f 4,4 * -Benzophenontetraaarbonsäurediethy! Ester »2,6-diaminopyridine, 3,3'-Dlaminodlphenylsulfon and 4,4 ^f -diaminodiphenylsulfon, the functional amino groups and those necessary for imide formation are for many purposes The carbonic acid derivative groups are present in practically equimolar amounts, preferably. These particular polyimides form stable monomeric precursors with long shelf life, and this system therefore results in a very economical manufacturing process. For other purposes, however, systems can be used instead which contain a different, both larger and smaller, number of Dian ι inen.

In each pail it is preferred, although not absolutely necessary, that the diamines used have a base dissociation constant for the primary amino groups of less than about " ^1. (All three diamines listed above have base dissociation constants for the primary amino groups in the order of magnitude of 10). This property is important from an economic point of view, since precursors with more reactive amines do not have long lifetimes. In such systems, even at room temperature, the amino groups of the monomers react with atmospheric oxygen and the carboxyl groups of the monomers, and such reactions make the monomeric material unusable.

In systems where more reactive amines are used, the precursor must also be in an oxygen-free environment, e.g. in a solvent and / or an inert gas atmosphere, for example under argon, because the amino groups otherwise they are oxidized, contributing to chain termination

0098 52/2120

S € leads her short chain lengths. Such a polymerization process is of course expensive and therefore from economic lending Point of view inexpedient, especially since the removal of the Solvent and drying steps included. Another feature of systems that work with more reactive diamines is this is that the polymers are much darker than those according to the preferred systems.

In contrast, the preferred precursors are according to the invention essentially not susceptible to oxidative degradation even during the curing process. Accordingly own they have a long shelf life and can by simply Be polymerized by heating in air, which is relatively inexpensive *

Nevertheless, the more reactive diamines in the monomeric precursors of the present invention can be used when other considerations consider the benefits of long life and make the workability in air appear low. Examples of aromatic m- and p-substituted diamines which, instead of or together with one or more of the above listed Less reactive diamines that can be used in such circumstances are:

3.2 ^f -dlamino diphenyl ether 4,4'-diaminodiphenyl ether m-phenylenediamine
4,4'-bisoxyaniline

The resinous materials of the present invention are useful except for the above-mentioned production of diohten, void-free Structures also for the production of foams. The monomeric, resinous precursor is used to create a Sohaum Typically in an air circulation in the absence of solvents oven from room temperature to one temperature in the

009052/212 0

BATH ORIGINAL

Heated in the order of 300 to 325 ^° C. (In "foam-making" systems, all diamines must have base dissociation constants for the primary amino groups not greater than 10. Systems with more reactive diamines must be polymerized in a solvent, but heating in the absence of a solvent to produce a homogeneous foam .) The materials obtained are B & idmischpolymerlsatschaum of low density, which are very elastic and have a uniform line size. These foams are suitable as acoustic, thermal and electrical insulators at high temperatures and because of their transparency properties at radar frequencies for use in radar devices.

Foams can be made from precursors «which are merely contain two diamines. For the production of foams Two m-substituted diamines are used with maximum elasticity. If a less elastic foam is desired is «become a pn-substituted and an m-substituted diamond used. Resilient foams can because of the regularity the polymer chain is not made from imide homopolymer will. As mentioned above, "this would lead" to her would be crystalline and relatively inflexible.

The resinous substances described above are also suitable for other application ^ purposes. For example, they can be used in solution for impregnation and in the absence of solvents for production used by composite structures.

The invention is to be explained in more detail in the following on the basis of examples will.

example 1

32.22 g (0.10 mol) of I, 3 * 4,4'-benzophenonetraoarboxylic acid dianhydride were dissolved in 125 ml of ethanol to convert it into the diester. To the diester solution were added 4 _t yj g at room temperature

009852/2120

BADORIQfNAL

is- 2030A 1 5

(O, O4 mol) of 2,6-Pyridlndiamin, added 9 * 93 g (0.04 MoI) of 3,3 ^f -Dlaminodiphenylsulfon and 4.97 g (0.02 MoI) 4 ₁ 4 ^t -Diamlnodiphenylsulfön and 125 ml of ethanol . The mixture was stirred and heated (30 minutes at about 30 ^° C.) until all of the solids were dissolved. The solution was filtered and the solvent in a rotary evaporator and subsequently removed in a vacuum oven at 78 ^1C. The foam obtained was powdered and dried in vacuo at 80 ° for 1 hour, after which a monomeric resin-like powder was obtained.

The monomeric resinous product thus produced had a long shelf life. After four months of storage it was it nooh a free flowing powder. Besides, it was in ethanol and acetone remained very soluble.

Example p

The resinous substance according to Example 1 was in an air environment wMlzofen heated from room temperature to 150% within 10 minutes. A foam body was obtained which was homogeneous and was light yellow and its cells were the same size. This Foam body was powdered and 10 hours in air heated. The powder obtained was finely ground in

introduced a steel mold and under a pressure of 63 kg / cm heated to 330T. After 30 minutes the sample was cooled and taken out of shape. A transparent reddish β was obtained Cookies (pellet). The material had a Rookwell-B-HMrt of 73 and a density of 1.4 g / om ♦ This was surprising insofar as than most polyimides Rookwell B hardnesses of about 5 have.

Example 3

A monomeric, resinous substance was made according to the regulation from example 1, but using only twelfth diamonds, manufactured. To this end, 32.22 g (0.10 NoI) 3 »3 * 4,4'-bensophenone tetraoarboxylic huredlanhydride were added for conversion into the diester dissolved in 150 ml of ethanol and mixed with 100 ml of ethanol with

0098S2 / 2120

"WS ORIGINAL

5> 46 g (0.05 mol) of 2,6-pyridinediamine and 12.42 g (0.05 mol) of 4,4'-diaminodiphenylsulfone were added. The Qemisoh was stirred until homogeneous and heated (to about 4O ⁰ C) and then filtered. The solvent was removed under reduced pressure to give a resinous product similar to that obtained in Example 1.

This resinous product was made on a ceramic tile in one Oven heated to 315 ° C. in air. After 15 minutes, one obtained Foam body. This body was elastic, had a slight one Density of about 0.03 g / onr and a light yellow color. The material had an open cell structure and was found useful for use as an acoustic insulating material.

Example 4

The resinous product according to Example 3 was powdered and mixed with aluminum powder in a weight ratio of 4: 1. The whole was then heated to 315 ° C., whereupon a foam body was obtained in which the aluminum was homogeneously dispersed. ^: '■ ■ -.- ■ .- -

With similar results, lead, copper, Asbestos, silicon dioxide, boron and tin powders are used. Other materials can be added if fabrics with certain property combinations for certain application purposes should be produced.

Example 5

The resinous product of Example 1 was heard as described in Example 2. The hardened Inldmisohpolymerisatpulver was mixed with fibrous boron, placed in a mold and pressed under a pressure of 60 to 70 kg / cm ^{2 at} 33W. The material formed a tablet (pellet) that was transparent and in which the boron fibers could be seen.

ι * * - ■. - 2030A15

Example 6

4.37 g (0.04 mol) of 2,6-diaminopyridine, 9.93 g (0.04 mol) of 3,3 »-diaminodiphenylsulfone and 4.96 g (0.02 mol) of ^^ '-dlaminodiphenylsulfone were in added to 200 g of PolyphosphorsMure in a round bottom flask. The Qemisoh was stirred and heated to 60 ° C and, after it had become homogeneous, cooled to 30%. Then 52.22 g (0.10 mol) of 3,5 * 4,4'-benzophenonetetraoarboxylic acid dianhydride were added and the whole thing was ^{heated at 23O 4} C until homogeneous.

W. The reaction mixture was cooled to about 80 * C and in 3 1

entered distilled water. The solid obtained became filtered off, washed three times with distilled water and then three times with reagent ethanol. That way polymer obtained was dried and heated for five hours.

A portion of this polymer was placed in a mold, and for 10 minutes at 33O ¹ C and a pressure of 56 kg / cm verpreöt. Under these conditions the polymer proved to be flowing.

Example 7

To 200 g of PolyphosphorsKure were added the following as in Example 6 Diamines added!

n-phenylenediamine 3.24 g (0.03 mol)

2,6-diaminopyridine 3.27g (0.03 mol)

4.4 ^f -diaminodiphenyl sulfone 4.97 g (0.02 mol)

4,4'-BlSOXyaniline 4.00 g (0.02 mol)

The reaction mixture was stirred at 60 ° C. and then Chilled to 30Ϊ. It was cut at 32.22 g (0.10 mol) BenzophenontetraoarbonaMuredianhydrid added and the whole thing heated to 260% »A polymer was obtained which Regulations from Beiepitl 6 isolated and gtwasohtn and since "sioh al" under the same temperature and pressure conditions, as described in Example 6 "proved flowing."

0098S2 / 2120

BATH ORIGINAL

Example 8 The following diamines were in 250 ml of N, N'-dimethylformamide

dissolved under inert gas

m-phenylenedlamine 4.52 g (0.04 mol)

2,6-Diaminopyridln 4.57 g (0.04 mol)

4,4'-BiSOXyaniline 4.00g (0.02 mol)

NaOH homogeneously the mixture, it was cooled to 15 ¹ C and-Benzophenontetraoarbone 5'4,4' * uredianhydrid added 52.22 g (0.10 mole) of 5 '. The whole was stirred until completely dissolved, after which the mixture was allowed to cool to room temperature. The mixture was then heated to RUokflu & temperature, cooled and poured into 2 liters of water. A polymer was obtained which was isolated by vacuum filtration and washed several times with water and ethanol. It was then dried and heated to 515 * 6 in argon.

■ ρ

A sample of this polymer was at 550U and about 70 kg / cm grouted and turned out to be in the same way as that in Example 2 described material flowing.

In the present example, the polymer isolated from N, N'-dimethylformamide was a mixture of the alcoholic polymeric acid and the corresponding intermediate amine acid polymer. If it had been desired to obtain the material in the form of the intermediate product instead of in the form of a mixture of the intermediate product and the intermediate polymer, the diamine / dianhydride mixture would have been heated to a lower temperature of the order of 100 ⁸ C instead of the temperature.

As already «« rttrtertert, Zmldmlnohpolymeritate Hit three polyimides for some uses of the present invention preferred. If desired, however, swel or more mis three diamines can be used if it is appropriate at the time.

00985 & /> 120

Example 9

150 ml of reagent ethanol were mixed with 32.2? g (0.10 mol) 3.3 ^I 4.4 ^I -Benzophenontetraoarbonsguredianhydrld added. The mixture was heated to reflux until the solid had dissolved. Then 5.45 g (0.05 mol) of 2,6-diaminopyridine and 24.81 g (0.05 mol) of 3.3 ^f -diaminodiphenyl sulfone were added to the mixture at room temperature together with 100 ml of ethanol. The mixture was stirred and heated to about 40% until the solid constituents had dissolved. The solution was then filtered and the solvent was removed under reduced pressure at a temperature of up to 71%. The material obtained was powdered and dried overnight. It was then polymerized by heating to 150% under argon. The polymeric material was ground and heated to 303%, giving an Imldmisohpolymerisat, which was allowed to melt in a mold at 328% and 63 kg / cm pressure * The deformed part was transparent and quite flexible; it had a density of 1.4 g / omega.

Example 10 As in the previous example, 32.23 g (0.10 mol) of 3,3'-

4,4'-BenzophenontetracarbonsKuredianhydrid in Xthanol and in the resulting diester solution 2 g (0.01 mol) 4,4'-Bisoxyanllin, 4.37 g (0.04 mol) 2.6 ~ Diamino pyridine, 9.92 g ( 0.04 mol) 4,4'-diaminodiphenyl sulfone and 2.48 g (0.01 mol) 3.3 ¹ -

Diamlnodiphenylsulfon dissolved. The solution was filtered and

the solvent removed under reduced pressure. The received The precursor was heated under argon to polymerize, and the resulting copolymer was in a mold at 328% and Melted 63 kg / cm pressure. The obtained molded sole was a little darker, but otherwise that in the previous one Example received the same.

The present example also proves that Di «iine with a BaeendIesojsiat ion constant for the primary amino groups of over 10 in practicing the present invention as well can be used so long as the polymerization is carried out in an inert atmosphere.

009852/2120

BADORFOIN /

- ■ 17

Those obtained according to the procedures of Examples 2-9 Materials were determined by infrared spectrometry and were «· sen in each case as imide copolymers. In each Traps were imide bands and amide bands in the spectra absent. Likewise, the material obtained was allowed to melt in each case by deforming it with no evidence of a removal set.

009852/2120

Claims (1)

Claims 1. Practically monomeric! ·, Resinous imide polymer precursor, which is essentially a solid solution of a 2, j5 ^r = · 4,4 ^I -benzophenone tetracarboxylic acid derivative and at least two aromatic diamines which are free from aliphatic radicals and from which at least one is m-substituted and all non-m-substituted en ρ »are substituted, and the ratio of the functional groups required for imide formation is practically equimolar. 2. precursor according to claim 1 »characterized» that the diamines Baeendlssoziationskonstanten for the primary amino groups not exceeding 10. 2. precursor according to claim 1, characterized in that the m-substituted diamines 2,6-diaminopyridine and bi; w. or 3,3'-Dlaminodiphenylsulf on are. 4. precursor gemäfl claim 1 * characterized ', DAFL t he is the only ρ-substituted diamine 4 _# 4 ^V -Dlaninodiphenyl8ulfon contains. 5. precursor according to any one of claims 1 to 4, d a d u r ο h gekennzelahnetj that at least one of the diamines is ρ-substituted. 6. Precursors according to one of the claims 1 to 5, since it is worthwhile that it is essentially a solution to the diet of 3 # 3 ^v 4 «4 ^t -Benzophenonetraoarboxylic acid» 2 _# 6-Diaminopyridin, ^ '- Diaainodiphenylaulfon and 4,4'-Diaeinodiphenyliulfon 1st. _19th ■ 203QA15 7 · Amldsäuremlsohpolyraerisat intermediate product, consisting of at least two different recurring units «the Condensation products from a 3 * 3 * 4,4 * benzophenone tetracarbon s Kurederlvat and at least two aromatic diamines without aliphatic radicals, at least one of the diamines being substituted and all diamines »which are not m-substituted are, ρ-substituted and the different recurring Units are randomly distributed. 8. AmidsKuremiechpolymerlsat intermediate product according to claim 7 " dadur ο h characterized" that at least one of the diamines is ρ-substituted. 9. Amic acids! ischpolymerisat intermediate product according to claim 7 » Knowing it is worthwhile, that the recurring Units are condensation products of at least three diamines, at least two of the diamines being m-substituted are. 10. Amidsäuremlsohpolymerisat-Zwisohenprodukt gtnKf claim 7 »by gekennzei oh net" da0 have the diamines Basendissoziationekonetanten for prlaKren Auinogruppen of hioht about 10 ~ ^10th 11 · Amldsiuremieohpolymerisat-Zwieohenprodukt according to claim 7 » didu ro h gekennze reward »dai the TetraoarbonaMure derivative the dictum he reads from 2,3H * V-Benzophenontetraoarbonsäure and the diamines 2,6-dlaelnopyridiHj, 3,3 * - Are diaminodiphenyl sulfone and ^, ^ '- dlaminodiphenyl sulfone. 12. Ieideiisohpolynitrieat with at least Bwel venohiedenon, repeating units, which means that the repeating units are condensation products from a 3 »3H, 4 ^t -benzophenon tetraocarboneaur« - derlvate and at least two Various aromatic dianines without allphatic radicals, with at least one of the dia ".Ine being m-substituted and all non-m-substituted diamines 009B52 / 2120 BADOfUOINAt 2030 11 5 ρ »are substituted and the repeating ones that differ from one another Units are randomly distributed. 12. Imidmlechpolymerisat according to claim 12 * thereby
characterized in that at least one of the diamines is ρ-substituted. 14. Imidmisehpolymerisat according to claim 12, characterized
characterized in that the recurring preheated condensation products of at least three diamines,
wherein at least two of the diamines are m-substituted. 15. Imidmlschpolymerisat according to claim 12, characterized
characterized in that the diamines have base dissociation constants for the primary amino groups not greater than about 10. 16. Imide copolymer according to Claim 12, thereby
marked Ichnet that the tetraoarboxylic acid derivative of the diet hy Ie st he of ^, JH ^ '- Benzophenontetraoarbonsäure and the diamines are 2,6-diaminopyridine, jSS'-diaminodiphenylsulphone and 4,4 * -diaminodiphenylsulphone. 17 · Process for the production of a monomeric, resinous material, which is practically a solid solution of constituents which can be polymerized to a precursor in the form of a polyimide or a polyamic acid, thereby
characterized in that a solution of a 3 * 2'-4,4 ^I -Benzophenontetraoarbonsäurederivats and at least two aromatic diamines in one opposite the acid derivative and
produces inert solvents for the diamines, at least one of the diamines being m-substituted, all non-m-substituted diamines being ρ-substituted and the ratio of the functional groups required for imide formation being practical 009852/2120
BATH 21 - ■■■ 2030A is equimolar, and that the solution is heated to a temperature high enough for the solvent to escape let «and which is kept below the temperature at which between the acid derivative and the diamines to a significant extent Condensation reactions take place. 18. The method according to claim 17 »characterized in that the solvent for the solution of the Tetracarboxylic acid derivatives and the diamine ethanol used, 19 * A process for the preparation of a particulate thermoplastic deformable to a use Imidmischpolymerisats as lohnet by geke η η ζ E, which is a 3 '3 * ⁱ t a solid solution, ⁱ t' BenzophenontetraQarbonsäurederlvates and at least two aromatic, no aliphatic radicals containing diamines, where at least one of the diamines is m-substituted, all non-m-substituted diamines ρ »are substituted and the ratio of the functional groups required for imide formation is practically equimolar that the solution can be heated to a temperature between about 125 and about 15O ⁴ C, that the foam is broken up into particles and the material obtained is hardened by heating to a temperature between about 300 and about 25 <C. 20. The method according to claim 19 »characterized in that at least one of the diamines is used Diamine with a base association constant for the primary Amino groups of at least 10 are used and that the polymerization of the tetraoarboxylic acid derivative and the diamines in one practically oxygen-free environment. 21. The method according to claims 19 *, characterized in that all diamines are used together with all diamines twisted, the bases of which the associationekonetanttn for dlt primary 009052/2120 Amino groups do not exceed 10 and the polymerization of the tetracarboxylic acid derivative and the diamines in air carries out. 22. The method according to claim 19, characterized in that the tetracarbonic acid derivative used is the diethyl ester of 3 ">> H, 4 * -BenzophenonetraoarbonsKure and as the diamines 2,6-Dlaminopyridln, j ^ '- Dlaminodiphenylsulfon and 4,4 ^t -diaminodiphenylsulfon. 23. Process for the preparation of an amic acid) isehpolyme rlsate precursor with at least two different «randomly distributed recurring units, thereby marking refuses to use a benzophenone tetra-carboxylic acid derivative and at least two aromatic diamines » of which at least one is substituted with m »and all are not m-substituted ρ-substituted «and where the ratio of the imide-forming groups is practically equimolar »heated in a suitable solvent. 24. Process for the production of a thermoplastic ImIdmlsohpolymerisates with at least two different recurring units distributed, as a result characterized that one is a practically monomeric, resinous material that is essentially a solid solution of a 3 * 3 * 4,4'-benzophenone tetracarboxylic acid derivative and min « at least two aromatic diamines, one of which is m-substituted and all non-m-substituted ρ-substituted and wherein the ratio of the imide-forming functional groups is practically equimolar, heated. 25 * The method according to claim 24, characterized by d a d u r o h , that the fatty solution is first brought to a temperature between about 125 and about 100% and in the mill to a temperature between about 300 and "about 3 & 5 ^ 6". BAD OTOQtWAL 26. Process for the production of a shaped body «d a d u r c h characterized by being a solid solution a 3.3 * 4.4 · benzophenone tetracarboxylic acid derivative and at least two aromatic diamines which do not contain any aliphatic radicals, where at least one of the diamines is m-substituted and all non-m-substituted are p-substituted and the ratio of the olefin-forming functional groups is practically equimolar that the solution can be heated to a temperature between about 125 and about 150% foams that the foam obtained is comminuted by heating the particulate material obtained to a temperature. door hardens between about 300 and about 325% and that one that cured particulate material under a pressure between about 21 and about 84 kg / cm and a temperature of deformed at least about 330% into the desired article. 27. A process for the production of an elastic imide copolymer risat "= foams of low density, characterized in that a solid solution of a 3" 3 ^f 4,4 ^f "Benzophenontetracarbonsäurederlvat and at least two aromatic diamines, with at least one of the diamines m-substituted and all non-m-substituted p-substituted and the ratio of the imide-forming functional groups is practically equimolar, and that the solid solution is heated to a temperature between about 300 and about 325% for curing in the absence of solvents. 28. Shaped body made of imide bulk polymer with at least two ver = different repeating units, the condensation products of a 3.3 * 4.4 * benzophenone tetracarboxylic acid derivative and at least two different aromatic diamines «which are not aliphatic Residues are included, with at least one of the diamines being m-substituted and all non-m-eubstituted p-eubstituted and the different recurring units are randomly distributed; 009852/2120 BAD ORfQINAU 29 «Shaped body getnSS claim 28 / characterized in that that it also contains a filler material distributed in calibration. 0 09852/2120