DE2131705A1 - Thermosetting cyclized polydiene resins - Google Patents

Description

Description of the patent application by

TEW Inc., Redondo Beach, California, U.S.A.

Priority: 17-8.1970 - U.S.A.

"Thermosetting Cyclized Polydiene Resins"

Because of their excellent chemical stability and because of their good physical properties, they are thermoset Polydiene resins have been very interesting for several years. From US Pat. No. 2,586,594 it is known that a tough, chemically stable resin coating on a substrate through the application of liquid polybutadiene and subsequent leashes Peroxide hardening can be produced. Although this system offered good physical and chemical properties, however, that required liquid polybutadiene special and critical processing techniques this system could be improved through further development, but the processing difficulties were still there not completely eliminated. U.S. Patent 3,431,235 now offers a solution to the processing problem, indeu initially e ^ Ti elastooeres intermediate product is produced,

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which can be handled and processed without special equipment and precautionary measures. Here, in a polymer compounding machine capable of processing viscous and sticky material, a resin composition which are cured into an intermediate elastomeric stage. can. The finished product will then manufactured without a special device for handling viscous sticky polymeric materials ♦ Although brought US Pat. No. 3,431,235 solves many problems, associated with thermoset polydiene resins, but the hot-cured polydiene resins still showed shrinkage, Processing and liability problems.

With the present invention, the visualization, Machining and adhesion problems associated with peroxide curing linked by polydiene resins are largely eliminated. This is achieved by the fact that a functional closed polydiene, such as 1,2-polybutadiene diol or 3,4-polyisoprene diol, with an organic acid anhydride is reacted to produce a dicarboxylic acid capped polydiene. The carboxylic acid-capped polydiene comes with an organic chain extender and with a radical peroxide initiator mixed, whereby an elastomeric material is formed by reaction, which the peroxide homogeneously distributed in a largely unreacted state contains. When the temperature of the elastomer is raised, the peroxide in the elastomer is activated, with a hard, thermoset resin is produced. Furthermore, the production, the elastomer and its conversion into one hard state can be done at the same time by a single heating stage. That in the production of the invention thermosetting resin, polydiene polymer should be used a predominant amount of olefinic satisfaction in fona of the 1,2-configuration (pendent vinyl groups)

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have, and preferably, the olefinic unsaturation should at least be 80 $ depends from vinyl groups, or from the 1,2-configuration of 1,2-polybutadiene or ^ »^ polyisoprene. These polydienes are produced by the anionic polymerization of butadiene or isoprene using an alkyl metal catalyst dispersion in a polar solvent such as tetrahydrofuran or 1,2-bimethoxyethane. The polymer may be with a suitable inorganic oxide, such as Ithylenoadd, or with an organic sulfide, such as ethylene sulfide reacted, and subsequently i are acidified closing, to produce chemically funkfcionelle terminal hydroxyl or mercapto groups on the polydiene. US Patents 3,055,952, 3,135,7 "* 6 and 3,048,568 contain precise information on the production of these functionally closed polymers * Alternatively, the polydienes with a high vinyl group content can also be terminated by amino groups - Patent 3,109,8-1 gives details of the preparation of amine-capped polybutadiene. While the molecular weights of these materials are not critical, it is preferred that the molecular weight of the capped polydiene be between about 500 and 5,000 Process conditions also use higher molecular weights.

The functionally closed polydiene is used to produce the carboxylic acid-capped polydiene adduct moderate temperatures reacted with an organic anhydride. It is true that the polydiene and the anhydride react Room temperature, however, reduce temperatures by about 65 to 107 ° C increases the viscosity of the polydiene and makes it easier to mix and react the polydiene with the anhydride.

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Typical organic anhydrides _f which can be reacted with the difunctional polydiene _¥:

TABLE I

Trimellitic anhydride, hexahydrophthalic anhydride fTadin acid anhydride methylnadic acid anhydride Oxalic anhydride Malonic anhydride Azelaic anhydride Adipic acid anhydride Pimelic anhydride tetrahydrophthalic anhydride Chloric anhydride Maleic anhydride Succinic anhydride Succinic anhydride Sebacic anhydride glutaric anhydride phthalic anhydride

In another procedure, the bifunctionally terminated polydiene can be reacted with a certain amount of an organic dianhydride to produce a polycarboxylic acid adduct. With this reaction it is
It is desirable to use an equivalent amount of the manhydride for the preparation of the polycarboxylic acid adduct, but an amount of dianhydride can also be used in excess
equivalence can be used if adducts with reduced viscosities are desired. Typical dianhydrides that can be used for this are:

* Chloric acid «1,4,5

5-en-2,3-di car bons äur e 209809 / U41

TABLE II

1. 3,3 '»4-» 4- · -Benzophenone-tetracarboxylic acid dianhydride

2. Polyazelaic acid polyanhydride

3. Pyromellitic dianhydride

Ψ. I ^ romellitic acid dianhydride / glycol adducts 5 x 1,2,3, ^ - cyclopentanetetracarboxylic acid dianhydride

The chain-extended elastomeric intermediate is made by Implementation of the diacid adduct with an organic chain extender. The adduct and the chain 'lengthener are mixed together and reacted at temperatures in the range from 51 * 7 to 121.1 ° C. As in the previous one 2nd stage, higher temperatures reduce the viscosity of the adduct and allow better mixing After mixing is complete, the temperature is maintained for 5 minutes to several hours, depending on the presence or absence of a catalyst, the temperature of the polymer, the mass of the material to be reacted and the degree of desired chain elongation

Chain extension of the diacid adduct (to produce an elastomeric material) is achieved by reacting the adduct with an aliphatic or aromatic substituted compound, the compound being selected from diepoxides, diimines, diimides, diols, diaziridines or dimercaptans. The chain extension is accomplished by mixing the reactants under comparatively moderate conditions. A certain chain lengthening can already take place at room temperature, but the time required for this stage is significantly reduced by increasing the temperature to a range from 51 »7 to 121.1 ° G. The chain extension reaction can continue through

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the use of catalysts can be accelerated. Examples of diepoxide chain extenders are as follows:

TABLE III

1. Epoxy novolacs

2. Bis-epoxydicyelopentyl ether of ethylene glycol

3. Epiehlorohydrin / Bi sphenol-A

4 »i-epoxyethyl-3,4-epoxyeyelohexane

5. Dieyclopentadiene Dioxide

6. Lime Dioxide

7. BisCS ^ J-epoxypropoiEy) - ^ © ^^ ©! 8 vinyl cyclohexane dioxide

9 «3,4-epoxy-6-methylcyclohexylmethyl-3,4- ~ epoxy-6-methylcyclohexane carboxylate

10. Zeaxanthin diepoxide

11. ^ lO-Epoxy - ^ - hydroxyoctadecanoic acid triester of Glycerin.

Suitable biimine, diimide and triimide chain extenders are the following:

TABLE IV

1. 1,6-hexane, rr, IT ^r -diethylenimine

2. 1 _t 6-hexane _t Ν, Ν'-dipropylenimine 3. » 1,7-heptane, N, N ^f -diethylenimine

4. 1,7-heptane, Ν, Ν'-dipropyleneimine

5. 1,8-oetane, Ν, Ν'-diethylenimine

6. 1,8-octane, Ν, Ν'-dipropyleneimine

7. 1,3-Di (carboxy-N-propyleneimide) benzene

8. 1,3 »5 ~ tri (carboxy-N-propyleniinide) -benzene

9. 1,3-Di (ethylene-N-1,2-butylimine) benzene

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The radical peroxide initiator can be used in the chain-extended Elastomer can be incorporated in two different ways · In one way, the peroxide gets into the elastomer after the Eettenverlängerungsstufe incorporated, while with the other Process the peroxide is incorporated into the liquid polydiene prior to chain extension. Both procedures result the same end result, i.e. an extended chain elastomer in which a free radical peroxide initiator is homogeneous and is largely distributed unimplemented. However, the method used may vary depending on the existing processing i

depend on the device. The amount of peroxide used is generally in the range between approximately 0.5 and 10% by weight, based on the polymer _t, however, these amounts are not very critical, namely because amounts of peroxide above 10 % also work well. However, such amounts are large amounts of peroxide are undesirable from an economic point of view. Amounts of peroxide below 0.5 # also give a reaction. However, the reaction is usually very slow and sometimes the product does not have the optimal properties. Other! Factors that influence the amount of the peroxide, for example, are, when the peroxide on \ a temperature in the range of approximately 148.9 to 218 _t heat the peroxide compound used, the polydiene used, the anhydride used and the chain extender used * 3 ° C then the peroxide is activated and the elastomer is cured into a very hard thermoset resin with less than 0.7 % shrinkage and improved machinability. Radical peroxide initiators for use in these "methods are _y are the following:

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GABgLLE?

Λ «, di ° -t ~ butyl peroxide.

2. 2,5-'33iineth3rl-2,5-fois (tert-butylperoxy) -hexane

3. n-Butyl-4,4-bis (tert-butylperoxy) valerate

^. 2,5 ~ Diniethyl-2,5-bis (tert-butylperoxy) ~ hexyne-3

5. tert-butyl perbenzoate;

6. Dicumyl peroxide

7 »Methyl ethyl ketone peroxide

8. Oil hydroperoxide

9 · Di-N-methyl-t-butyl-percarbamai;

10. Lamroyl peroxide

11. Acetyl peroxide
12 * decanoyl peroxide
'i3- t-Butyl ^ peracetate

14. t-butyl peroxyisobutryrate

The idealized overall reaction for the production of the he ~ Harxe according to the invention using 1,2 * ~ polybutadiene diol, Tetrahydrophthalic anhydride and 4,4 * -isopropylidene- diphenol is as follows:

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«D CO O

HO - OH ₂ - * CHp - O -

H-C

CH ₂ - OH + O '

Dihydroxy-1,2-polybutadiene Tetrahydrophthalic anhydride

H
O - CH ₂ - CH ₂ - C - CH ₂

- OH

s-

Adduct

CH

CHCH ₂ - 0 -

H ι

σ - CH ₂ +

ττ _ä

H OH,

σ ** CH ₀ «*
ι ²

- CH ₂ - 0 - C

HO-C

* O - CH ₂ CH.

CH.

2.

Chain extension for the production of an elastomer

O ~ OHp -

HO

- O - OH

R - •

O - CHp - CH OH

CH,

CH,

p - CH ₅ - O - C 2

- 0 - CH ₀ -

Hardening to produce the hardened resin

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In-first reaction between the polybutadiene diol and the anhydride functional active terminal hydroxyl groups on the polybutadiene with the anhydride react ^ wherein a Diearbonsäureaddukt arises _a When the epichlorohydrin / bisphenol-A is reacted with the adduct, then the adduct is _chain-i wherein check a Elastomer forms »When heat is applied in the third reaction, the peroxide initiator is displaced, creating free radicals, which cause the cyclization of the pendent yinyl groups of the polydiene and cross-linking of neighboring chains. In the above equation, η typically denotes an integer which is sufficiently high that an average molecular weight results which corresponds to the polydiene used _? and moreover, χ is a sufficiently high integer number that a hard, crosslinked product is formed.

The following examples explain the invention

Approximately 89 »1 g 1 _? 2-polybutadiene diol and approximately 10.0 g of tetrahydrophthalic anhydride were combined in a 500 ml container equipped with a mechanical stirrer, thermometer, heating mantle, and nitrogen inlet tube. The container was heated to 102 ° C for 11/2 hours under nitrogen and stirred rapidly, operating under nitrogen. The finished mixture was degassed and cooled. Then 4.0 g of dicumyl peroxide were placed in the container at 60 ° C and stirred in for 5 minutes, after which approximately 1 ₅ 2 g of triethylenediamine were added and stirring was continued for a further 5 minutes * Finally, approximately 5 g of alicyclic diepoxycarboxylate (CT ~ 179, CIBA Industries) added to the mixture

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and stirred in for 30 minutes. The contents of the container have been degassed, Poured into a crystallization tray containing a mold release agent was coated and covered with an aluminum foil. The sample was then placed in an oven which was programmed as follows:

Temperature ⁰ C Time (hour) 90 16 120 6th 130 16 140 6th 170 16

The casting obtained after hardening had the following
Characteristics:

Properties of experimental data

Tensile strength (kg / cm) according to ASTM D638

Extensibility (#) according to

ASTM D638 4.1

ο Compressive strength (kg / cm) according to

ASTM D695 according to 2065 , 07 Pressure module (kg / cm) 3.8 ASTM D695 I75OO 8th Deflection (#) 18th specific weight Hardening (#) 1 Shrinkage in the Barcol hardness EXAMPLE II 3.

Approximately 100.0 grams of 1,2-polybutadiene diol and approximately 29.7 grams
Chloric anhydride (chlorendic anhydride) were made into a
1 1-capacity container introduced, which is equipped with a heating jacket, a mechanical stirrer, a nitrogen inlet tube and

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a thermometer was fitted »The mixture was under Nitrogen and heated to 130 ° C. with vigorous stirring until all the solids had gone into solution. The opaque solution was degassed, whereby a viscous, amber-colored product was obtained. »This product was cooled to 60 ° G, then approximately 16.3 g of diglycidyl ether were obtained from Bisphenol-A (D.E.R. 332, Dow Chemical) (in a liquefied state) was added to the stirred mixture and allowed to stir was continued for another 10 minutes. Then dicumyl- peroxide was added at 60 ° C and the mixture was stirred for an additional 10 minutes. The contents of the container were put into a Introduced crystallization dish, covered with an aluminum foil and placed in an oven, which as in Example I was programmed ..

The cured product had the following properties:

Properties of experimental data

Tensile strength (kg / cm ") according to

ASTM D638 584.5

Extensibility (#) according to

ASTM D638 3.5

ο
Compressive strength (kg / cm) according to

ASTM D695 2170

Pressure module (kg / cm) according to

ASTM D695 22400

Deflection (#) 20 Specific gravity 1.18

Shrinkage on curing (#) 2.1

Bareol hardness 43

Medrig shrinking molding compositions can be made from the inventive Resins are made by incorporating a filler material. While it is preferred that Filler material to be added to a mixture of the liquid adduct and the chain extender before the chain is extended.

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work, but the filler materials can also be used after the grinded lette extension into the elastomer obtained if an appropriate device is available : do. Filler materials, such as ζ · Β. Silica flour, Aluminum oxide flour, wood flour, metal particles, metal carbides and carbon particles can be in amounts up to 80 wt .- #, Drawn on the product, can be incorporated without the Properties of the finished resin product are significantly impaired. Molding compounds made from these highly filled Resins consist of a gel in their consistency mixed with a low spiral flow (suitable for pressure » cast) to a dry, tack-free, granular material are sufficient*

The following example explains the manufacture and properties a molding compound:

EXAMPLE III

Approximately 65.5 S 1,2-polybutadiene diol and approximately 34.5 g Chloric anhydride were in a 1 1 container that came with a mechanical stirrer, a thermometer, a heating jacket and a nitrogen outlet tube, a j brought. The container was heated to 130 ° C under nitrogen heated and stirred rapidly until all solids were in solution. The opaque solution was degassed, leaving a viscous, amber product was obtained. The contents of the container were cooled to 60 ° G, and the following ingredients were added in the order listed, each ingredient carefully dissolved or wetted was before the next ingredient was added.

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component <0.05 mm Weight j £ g ^ Dicumyl peroxide *,8th Silicone 2.5 Silica flour Bisphenol-A 510.0 Calcium stearate 1.3 Magnesium oxide 2.0 Diglycidyl ether of

(Epon 836, Shell Oil) 21.2

The mixture was stirred for 20 minutes and then in one up 93.3 ° C oven placed for one hour * The chain-extended elastomer was removed again and allowed to cool calmly. The chain-lengthened molding compound was then introduced into molds and cured at 176 ° C. for 5 minutes.

During curing, the molding compound had an ASTM cup flow at 176.7 ° C. of 210 kg / cm ² and a Hull spiral flow of 25.0 mm at 176.7 ° C. and 210 kg / cm. The properties of the cured product were determined as follows:

Flexural strength (23.9 ° C) 0.98 10 ⁵ kg / cm ² Flexural strength (148.9 ° C) 0.266 χ 10 ³ kg / cm ²

Retention at increased

Temperature 27 &

Flexural modulus (23.9 ° C) 0.182 χ 10 ⁶ kg / cm ²

Flexural modulus (148.9 ° C) 0.0378 χ 10 ⁶ kg / cm ²

Retention at increased

Temperature 21 %

Barcol-HSrte (23.9 ° C) 81

Mold shrinkage 0.58 %

The resin according to the invention is also suitable for the production of high quality laminates. Coated with silane Glass textiles made with the reaction product of 1,2-polybutadiene diol / pyroraellitic dianhydride adduct and one

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Epoxy chain extenders were coated to give laminates

Ti p

with a flexural strength of about 5.4-6 × 10 kg / cm · The strength retention was 74% after a heat treatment at 148.9 ° C. and 87% after a treatment in boiling water of 1,2-polybutadiene diol / trimellitic anhydride adduct and an epoxy chain extender had been coated, laminates with a flexural strength of 77 x 10 · ^ kg / cm and a flexural modulus of 0.322 χ 10 * d

2
kg / cm. The strength retention after boiling water treatment was 100 # and after treatment at 148.9 ° C was 40 #. Other reinforcing materials suitable as laminates or fillers can be selected from carbon fibers, silica fibers, and metal spun.

The new resins are thermal at temperatures of 400 ° C stable · They are tough, impact-resistant, machinable and have low shrinkage after a molding process. The thermally stable "stiff" character of the new Harsse has its reason in the condensed cyclic configuration | ration of the polydiene polymer chains between chemical crosslinks · The properties of the new resins are based on the Adduct formation and the subsequent chain extension of the polydiene back. All of these advantages result from Materials that have a relatively high hydrocarbon content.

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Claims (1)

Claim e 1. Hard thermoset resin, characterized in that it is the reaction product of the following components: (1) a polydiene with (a) several functional groups, namely hydroxyl, amino and mercapto groups, and (b) predominantly pendant vinyl groups on alternating carbon atoms of the polydiene skeleton, (2) a carboxylic acid adduct forming organic acid anhydride, which reacts with the functional groups of the polydiene is capable of (3) a polyfunctional organic chain extender that reacts with the carboxylic acid adduct capable, and (4) an organic radical peroxide initiator. 2. Resin according to claim 1, characterized in that the polydiene is selected from 1,2- polybuteae and 3,4-polyisoprene. 3. Resin according to claim 1, characterized in that the organic acid anhydride is selected from the following: trimellitic anhydride , tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, nadinic anhydride, nadic anhydride, azoic anhydride anhydride, maleic anhydride, oxalic anhydride Sebacic _{anhydride f} adipic anhydride, gluten acid anhydride, piaelic anhydride and phthalic anhydride. ". 4. Hars paeh Anaprucfa 1, characterized in that the organic chain extender is selected from the following: aliphatic substituted diepoxides, aromatic substituted diepoxides, aliphatic substituted ones 209809/1441 Diamines, aromatic substituted diimines, aliphatic substituted diimides, aromatic substituted diimides, aliphatic substituted diols, aromatic substituted Diols, aliphatic substituted diaziridines, aromatic substituted diaziridines, aliphatic substituted dimercaptans and aromatic substituted dimercaptans. 5. Resin according to claim 1, characterized in that the organic acid anhydride is selected from the following: 3,3 ', ^, ^' - benzophenone tetracarboxylic acid dianhydride, polyazelaic acid polyanhydride, pyromellitic acid dianhydride, Λ , 2,3,4 -Cyclopentane-tetracarboxylic acid dianhydride and Endocis-bicyclo (2.2.1) -5-heptene-2,3-dicarboxylic acid dianhydride. 6ο resin according to claim 1, characterized in that it as filler silicon dioxide, aluminum oxide, metals, wood, Contains metal carbides or carbon. 7. Resin according to claim 1, characterized in that it is glass fibers, foal fibers, Contains spun fibers or silicon dioxide fibers. Hot 8. / hardening elastomeric polymer, characterized in that that it contains a reaction product from (1) a polydiene with (a) several fractional groups, namely hydroxyl, amino or mercapto groups and (b) with predominantly pendent Vinyl groups on alternating carbon atoms of the polydiene skeleton, (2) forming a carboxylic acid adduct organic acid anhydride, which leads to a reaction is capable of the functional groups of the polydiene, and (3) a polyfunctional organic chain extender, which is capable of reacting with the carboxylic acid adduct; whereby the reaction product contains an organic free radical peroxide initiator distributed homogeneously in itself. 20980 9 / U A 1 9. Polymer according to claim 8, characterized in that the pelydiene is selected from 1,2-polybutadiene and 3,4-polyisoprene is. 10. The polymer according to claim 8, characterized in that the organic acid anhydride is selected from the following: trimellitic anhydride ₉ tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anitydride, tetrabromophthalic anhydride, chloric anhydride, maleic anhydride, maleic anhydride, oxic anhydride anhydride (nadic anhydride), maleic anhydride, maleic anhydride, oxenic anhydride, tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, Malonic anhydride, suberic anhydride, azelaic anhydride, sebacic anhydride, adipic anhydride, glutaric anhydride, pimelic anhydride and phthalic anhydride * 11. Polymer according to claim 8, characterized in that the organic chain extender is selected from the following is: aliphatic substituted diepoxides, aromatic substituted diepoxides, aliphatic substituted diimines, aromatic substituted diimines, aliphatic substituted diimides, aromatic substituted diimides, aliphatic substituted moles, aromatic substituted Diols, aliphatic substituted diaziridines, aromatic substituted diaziridines, aliphatic substituted dimercaptans and aromatic substituted dimercaptans. 12 * polymer according to claim 8, characterized in that the organic acid anhydride is selected from the following: 3,3 ', 4 _t 4 ^f ~ benzophenone tetracarboxylic acid dianhydride, polyazelaic acid polyanhydride, pyromellitic acid dianhydride, 1,2,, 3, ⁱ '- * - cyclopentane-tetracarboxylic acid - dianhydride and Endocis ~ bicyclö (2 "2" 1) -5-heptene-2,3-dicarboxylic acid dianhydride " 13- polymer according to claim 8, characterized in that it contains silicon dioxide, aluminum oxide, metals, wood, metal carbides or carbon as a filler. 209809 / U41 14, polymer according to claim 8, characterized in that it as reinforcement material glass fibers, carbon fibers, Contains metal webs or silicon dioxide fibers, Ί5- Method of making a hard thermoset Polydiene resin, characterized in that one (A) (1) a polydiene with (a) multiple functional Groups, namely hydroxyl, amino or mercapto groups, and with (b) predominantly ab- j hanging vinyl groups on alternating Carbon atoms of the polydiene skeleton, and (2) an organic acid anhydride which is capable of reacting with the functional groups of the polydiene, to make a carboxylic acid capped adduct; (B) the polydiene / carboxylic acid adduct with (3) an organic radical peroxide initiator and (4-) an organic chain extender that reacts with the adduct is able to mix; (C) the adduct and the chain extender react with one another to form an elastomeric polymer Produce material which largely unreacted the free radical peroxide initiator contains homogeneously distributed in itself; and (D) the elastomer cures into a hard thermoset resin. 16. The method according to claim 15, characterized in that that as polydiene 1,2-polybutadiene or 3,4-polyisoprene is used. 17. The method according to claim 15, characterized in that that the organic acid anhydride is derived from the following 209809/1441 is chosen: trimellitic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Tetrabromophthalic acid anhydride, chloric acid anhydride (ehlorendic anhydride), nadic anhydride (nadic anhydride), Maleic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride * suberic anhydride, azelaic anhydride, Sebaic anhydride, adipic anhydride, glutaric anhydride, pimelic anhydride and phthalic anhydride . 18. The method according to claim 15 ·, characterized in that the organic chain extender is selected from the following: aliphatic substituted diepoxides, aromatic substituted diepoxides, aliphatic substituted diimines, aromatic substituted diimines _? aliphatic substituted diimides, aromatic substituted diimides, aliphatic substituted moles, aromatic substituted diols _t aliphatic substituted diaziridines, aromatic substituted diaziridines, aliphatic substituted dimercaptans and aromatic substituted dimercaptans 19 · The method according to claim 15, characterized in that that the organic acid anhydride is selected from the following: 3,3 ', ^, 4'-benzophenone-tetracarboxylic acid dianhydride, Polyazelaic acid polyanhydride, pyromellitic acid dianhydride, 1,2,3,4 · -Cyclopentane-tetracarboxylic acid dianhydride and Endocis-bieyclo (2.2.1) -5 "-heptene-2,3-clicarboxylic acid dianhydride. 20, method according to claim 15 »characterized in that that incorporated as a finely divided filler silicon dioxide, metal, metal oxide, metal carbide or carbon will. 21. The method according to claim 15, characterized in that glass fibers, carbon fibers, Metal webs or silicon dioxide fibers incorporated .-IN O. 209809 / Ί4Α1