GB2045269A - Thermoplastic Polymers from Diamines and Diepoxides - Google Patents

Abstract

The invention provides a process for the preparation of high molecular weight, thermoplastic epoxide-amine polyadducts, wherein a diepoxide, preferably 2,2-bis-(4- glycidyloxypnenyl)-propane, is reacted with a diamine of the general formula:- <IMAGE> in which R is an aralkyl radical and R' is a divalent straight-chained or branched alkylene, cycloalkylene, arylene or heterocyclic radical which optionally contains hetero atoms and/or double and/or triple bonds, in a mole ratio of about 1.0:1.0 and preferably in a mole ratio of from 0.95:1.0 to 1.0:1.05, without the use of a solvent or diluent. The present invention also provides shaped bodies made from the epoxide-amine polyadducts obtained by the above process.

Description

SPECIFICATION Process for the Preparation of Thermoplastic Epoxide-amine Polyadducts The present invention is concerned with a process for the preparation of high molecular weight thermoplastic epoxide-amine polyadducts.

More particularly, the present invention is concerned with a process for the preparation of high molecular weight thermoplastic epoxideamine polyadducts which, as polyhydroxypolyamine compounds, contain the following characteristic structural element:

wherein R is an aralkyl radical, preferably a benzyl radical, R' and R", which can be the same or different, are divalent, straight-chained or branched alkylene, cycloalkylene, arylene or heterocyclic radicals or can also be mixed radicals of this class or corresponding radicals containing hetero atoms, for example, boron, oxygen, sulphur or nitrogen atoms, and/or several double and/or triple bonds.

High molecular weight polymers of this type possess, as spatially cross-linked epoxide-amine polyadducts, valuable technical properties, such as good adhesion, high mechanical strength, good electrical properties and the like, which permit a wide variety of uses for shaped articles, adhesives, lacquers, coatings, films, for the embedding and insulation of electronic constructional elements, as laminating and casting resins and the like.

On the basis of their thermoplasticity and solubility, however, the epoxide-amine polyadducts according to the present invention are even more widely useful and can be worked up by advantageous techniques as spatially crosslinked epoxide-amine polyadducts and are especially useful for the formation of films and fibres from melts and solutions thereof, as well as for injection moulding, extruding, pressing and drawing.

Whereas polymeric meshes of epoxide resins and polyamines have been extensively investigated and have also been widely used for technical purposes, the poly-addition of diepoxides with disecondary diamines to give high molecular weight but unbranched and noncross-linked, as well as uniform polyadducts of the above-given structure have hitherto only been realised in a.few exceptional cases (referred to the meanings as R, R' and R") or under specific process conditions, mostly by reaction in suitable solvents.

German Patent Specification No. 676,117 describes the preparation of addition products from crude diepoxides and various disecondary diamines in hydroxyl-containing solvents.

However, according to the description, the products in question are resin-like substances and are obviously neither high molecular weight products nor thermoplastic materials in the sense of the specific properties of macromolecular work materials. Furthermore, it is clear that the corresponding addition products can only be obtained by reaction in solvents and, therefore, cannot be obtained, in the described manner, as products suitable for use as casting resins.

In the subsequent literature, it was unanimously stated that a solvent-free formation of non-cross-linked polyadducts gives rise to extraordinary difficulties (see Houben-Weyl, Methoden der organischen Chemie, Vol. XIV/2, p.

499, pub. Georg Thieme Verlag, Stuttgart, 1971; K. Jellinek, 2nd Internationale Tagung tiber glasfaserverstärke Kunststoffe and Giessharze, Berlin, 13th to 18th March, 1967), namely, because either the tertiary amino groupings formed in the course of the reaction act catalytically on the ring-opening polymerisation of the epoxide groups, which are here to be excluded or because the hydroxyl groups formed participate in the reaction. In particular, the partial polymerisation of the epoxides, which is to be feared, would give rise not only to the disturbance of the equivalence of the components of the polyaddition system but also to cross-linking.

Therefore, in spite of much effort, because of the great tendency of the epoxide groups to undergo autopolymerisation, it has not been possible to prepare high molecular weight, hardenable, noncross-linked casting resins similar to the systems which lead to polyurethane thermoplastics, for which reason other ways had to be used for solving technical problems, for example, for making flexible and removing brittleness (toughening) of the epoxide resins. On the other hand, in cases where solubility, thermoplasticity or meltability are necessary, generally it is necessary to make use of oligomers, whereby the known disadvantages which are due to the low molecular weight, such as brittleness and low strength, have to be put up with or have to be removed by subsequent reactions.

Attempts to produce high molecular weight and thermoplastic, non-cross-linked epoxideamine polyadducts have been repeatedly carried out. In Makromolekulare Chemie, 116 158172/1968, there is described the poly-addition of N,N'-bis-(2,3-epoxypropyl)-piperazine in a manner analogous to that described in Example 2 of German Patent Specification No. 676,11 7 with primary aliphatic and aromatic amines and with aliphatic, aromatic and cycloaliphatic, heterocyclic disecondary diamines. The polyreaction is again carried out in solvents and only gives rise to products with relatively low molecular weights of from 2000 to 6900.

Piperazine and N,N'-dialkyl-substituted aliphatic diamines also react with 2,2'-bis-(4glycidyloxyphenyl)-propane in dilute solutions but instead of giving high molecular weight polymers, only give oligocyclic compounds (see S. Ore and O.G. Tjugum, Acta chim. Scand., 24, 2397/1970).

It is also known from U.S. Patent Specification No. 3,554,956 to produce thermoplastic polyhydroxypolyamine compounds by using a mixture of an epoxide compound with terminal 1 ,2-epoxide groups and a disecondary diamine in a mole ratio of 0.9 to 1.1:1 which, as essential component, contains an inert diluent. However, it is of considerable disadvantage and is also very restrictive that this reaction can only be carried out with the help of the said diluent. As stated in Example 1 of this U.S. Patent Specification, without the use of a diluent, unmeltable products are obtained which cannot be used as thermopiastics.High molecular weight, thermoplastic casting systems and the like cannot be produced according to this process and, according to the totality of the prior art, it is, in general, not possible to obtain high molecular weight, thermoplastic polyadducts with the use of di-secondary diamines.

It is also known from U.S. Patent Specification No. 3,592,946 that, in the special case of the poly-addition of N,N'-dimethylethylenediamine and resorcinol diglycidyl ether, a soluble polyadduct is obtained. However, one disadvantage of this process is the limitation to the special case, the formation of elastomeric, non-thermoplastic products, and that the reaction of the said disecondary diamines with the resorcinol diglycidyl ether takes place very rapidly, for which reason the poly-addition can only be controlled by a complicated method of carrying out the reaction. Furthermore, due to the great volatility of the amine and of its sensitivity to carbon dioxide, considerable technical difficulties arise in maintaining the stoichiometry of the polyaddition components.

Furthermore, it has been suggested to prepare optical adhesives, which give rise to low-stress cementings of optical parts which harden at ambient temperature and can be thermally separated in the temperature range of from 120 to 200 C., on the basis of unmodified, low molecular weight epoxide resins containing at least two epoxide groups per molecule and N,N' dibenzylethylenediamine (see Germany Democratic Republic Patent Application No.

C09J/202908), as well as other disecondary diamines (see German Democratic Republic Patent Specifications Nos. 122,258 and 130,580). However, in that case, it was not the object of the inventions in question to prepare high molecular weight, thermoplastic epoxide polyadducts so that the object of the present invention cannot be solved therewith. The relative molecular weights of the advantageously effective polyadducts with the described properties lie, in general, in the range below 6000 so that even the hardened optical adhesives according to the mentioned Patent Specifications cannot display the technically also valuable properties typical for high molecular weight, thermoplastic epoxide-amine polyadducts.In ~particular, some mechanical properties, such as impact strength, tear strength, toughness and the like, are, up to a limiting molecular weight range, very much dependent upon the molecular weight and, in this particular case, only achieve interesting value ranges at relative molecular weights of Mn > 8000.

Various other epoxide-amine resin systems have also been suggested which admittedly use disecondary diamines but none of which lead to thermoplastic high molecular weight epoxideamine polyadducts and thus which cannot solve the problem with which the present invention is concerned. In general, they all have the common deficiency that they harden to give insoluble, nonmeltable, cross-linked products (see Federal Republic of Germany Patent Specifications Nos.

1,019,451; 1,038,278 and 2,164,099 and British Patent Specification No. 868,733).

It is an object of the present invention to provide a generally applicable process for the preparation of high molecular weight (Mn > 8000) thermoplastic epoxide-amine polyadducts which enable the use of diluents to be omitted and in the case of which, by variations of the addition components, polyadducts can be prepared with a wide range of physical properties. In particular, it is an object of the present invention to provide a process for the preparation of thermoplastic work materials with glass transition temperatures Tg of Oto 1500C.

Surprisingly and unpredictably, we have now found that high molecular weight, thermoplastic epoxide-amine polyadducts can, according to the present invention, be prepared by a process wherein a diepoxide and preferably pure diandiglycidyl ether, i.e. 2,2'-bis-(4-glycidyloxyphenyl)-propane, is reacted with a diamine of the general formula:-

in which R and R' have the same meanings as above, in a mole ratio of 1.0:1.0, without the use of a solvent or diluent.

According to the present invention, high molecular weight polyaddition products are also obtained when the mole ratio of the polyaddition components is from 0.95:1.0 to 1.0:1.05 (diepoxide:diamine) and also when mixtures of these diamines and/or mixtures of these diepoxides are employed.

The process according to the present invention can also be employed in such a manner that, for the formation of shaped bodies, the polyaddition process is carried out in a shape-imparting vessel, for the formation of coatings it is carried out directly on the surface to be coated, in the case of adhesive joints and sealings it is carried out directly between the parts to be joined and, in the case of fibre-reinforced and filled work materials, duplex materials and laminates, it is carried out directly in the case of the incorporation of the materials to be incorporated.

Examples of diepoxides which are highly preferred for the purpose of the present invention include 2,2-bis-(4-glycidyloxyphenyl)-propane, bis(glycidyl)-alkyl and aryl ethers, bis-(glycidyl)amines and the like compounds.

The process according to the present invention can, of course, be extended to diepoxide resins which contain mixtures of several diepoxides. In this case, the difficulty consists in excluding accompanying materials which contain, per molecule, only one epoxide group or more than two epoxide groups, as well as maintaining the equivalence of the reaction components. The optimum amount of diamine can here be determined by epoxide equivalent weight determination or empiricaliy by experimentation.

The polyaddition reaction according to the present invention can be accomplished in the most simple manner by keeping in reaction, possibly by heating, the equivalent amounts of diepoxide and disecondary diamine, after thorough mixing, until the desired high molecular weight (over 8000) has been reached. Depending upon the nature of the substituents R and R', it is advantageous to maintain reaction temperatures of from 20 to 2000C. It is also preferable gradually to increase the reaction temperature to the region of the glass temperature of the polyadduct to keep it there for quite a long time and subsequently to increase it to a temperature which is about 500 C. above the glass transition temperature Tg.The thermoplastic polyadducts according to the present invention can be worked up by the conventional technical processes, for example, by injection moulding, extruding, pressing, drawing and stamping.

Instead of pure, individual components, i.e.

diepoxide and diamine, there can also be used, in the case of maintaining the equivalence according to the present invention of the functional groups, mixtures of the diamines to be used according to the present invention and/or mixtures of the various diepoxides to be used according to the present invention. Thus, for example, in order to obtain polyadducts with glass transition temperatures above 800C., it is advantageous to use mixtures with N,N'-dibenzyl derivatives of aromatic diamines. A substantial advance in comparison with the above-mentioned U.S.

Patent Specification No. 3,554,936 is to be seen in the fact that the process according to the present invention permits, without problems, without the use of diluents, the formation of the polyadduct with simultaneous shaping to give shaped bodies, such as cast bodies, seals, pressed bodies or laminates or to give planar bodies, such as lacquer films or adhesions.These epoxideamine polyadducts according to the present invention display, because of their non-crosslinked structure, mechanical properties other than those of the known cross-linked epoxide-amine casting resins: as coatings, adhesive joints, sealing masses and polymer components in in fibre-reinforced and filled work materials, duplex materials, laminates and the like, they display, in particular, a lower internal stress and comparatively low brittleness which, in comparison with the known epoxide-amine crosslinked materials, signifies a considerable improvement with regard to the reduction of stress crack formation which is a reason for mechanical, electrical and optical work material faults and for defects due to ageing. Filaments and foils can be produced from melts and solutions in the usual manner with the polyadducts.

The diepoxides employed can be prepared in known manner and purified by distillation, recrystallisation or other known methods.

Some of the disecondary diamines employed according to the present invention have been prepared for the first time by known methods of synthesis, for example, by the reaction of dichloro compounds with benzylamine or by the reaction of diprimary diamines with benzaldehyde and subsequent hydrogenation of the Schiff bases thus obtained. Some of the disecondary diamines used according to the present invention are already commercially available, for example N,N'dibenzylethylenediamine, and others can be obtained by known processes (see Makromol.

Chemie, 17, 77--130/1955). Examples of disecondary diamines which can be used according to the present invention include N,N'dibenzylethylenediamine, N,N' dibenzyltetramethylene-1 4-diamine, N,N' dibenzylhexamethylenel-6-diam ine, N,N' dibenzyi-2,2,4(2,4,4)trimethylhexamethylene- 1 ,6-diamine, N,N'-dibenzyl-3,6-dioxaoctane-1 ,8- diamine, N,N'-dibenzyl-p-xylyienediamine, N,N' dibenzyl-2,7-bis-(aminomethyl)-fluorene, N,N- - (dibenzyl-4,4'-diaminodiphenylmethane, N,N' dibenzyl-4,4'-diaminodicyclohexylmethane, N,N' dibenzylbut-2-ene-1 ,4-diamine, N,N'-dibenzyl 2,5-bis-(aminomethyl)-thiophene, N,N'diphenethylethylene-diamine and N,N'-dibenzyl1 -phenylethylenediamine.

That, according to the process of the present invention, no cross-linking of the polyadducts takes place, can be regarded as being surprising insofar as N,N-dimethylbenzylamine, which is substantially structurally analogous to the nitrogen-containing region of the polymeric chains produced according to the present invention, is known as an effective catalyst for the polymerisation of epoxides. However, according to the present invention, precisely N,N'dibenzyldiamines are highly preferred addition components for the production of non-crosslinked high molecular weight polyadducts. In the course of extensive experiments, we have found that various substituents R which do not belong to the aralkyl series, lead either to cross-linkings or only to low molecular weight polyadducts.

Furthermore, for one embodiment of the present invention, it is of considerable importance that the volume concentration in the case of the use of 2,2-bis-(4-glycidyloxyphenyl)-propane and of the disecondary diamines to be used according to the present invention is smaller than 5% and preferably 3 to 5% of the volume of the monomer mixture. By means of the use of monomer mixtures already partly reacted according to the present invention and by the incorporation of filler materials, such as silica gel or quartz powder, the effect of volume contraction, which is bound up with the poly-addition, can be still further reduced.In limiting cases, by means of injection moulding or of hot pressing of the completely reacted thermoplastic polyadducts, even the volume change in the case of the shaping can be reduced only to the thermal expansion of the polymers, which can be regarded as being extraordinarily advantageous for solving various technical problems.

The following Examples are given for the purpose of illustrating the present invention: Example 1 34.040 g. of crystalline 2,2-bis-(4-glycidyloxy phenyl)-propane (m.p. 42.5-430C.) are weighed into a flat-bottomed flask which can be closed in a gas-tight manner and melted. After cooling, 24,034 g. N,N'-dibenzyl-ethylenediamine (b.p.

1 56--1 57 OC./0.08 mm.Hg; nD =1.5652) are added thereto. The reaction components are mixed by stirring for 30 minutes under an atmosphere of an inert gas, a homogeneous, liquid mixture thereby being obtained.

Subsequently, the reaction mixture is degassed in a vacuum, again covered with an inert gas and heated to 800C. for 72 hours. There is obtained a colourless, glass-like, solid polyadduct, the Tg of which (DSC-1 Perkin-Elmer) is +51 0C.

This product is soluble in tetrahydrofuran, pyridine, toluene/cyclohexanone, and chloroform/methanol. The relative molecular weight is found, by vapour pressure osmometric measurement, to be 16,200 (chloroform/methanol 4:1 v/v). The limiting viscosity value (+250C., chloroform/methanol 4:1 v/v) is [77]=41.4 (in ml. g-1).

After dissolving the polyadduct in toluene/cyclohexanone (4:1 v/v) and precipitation with petroleum ether, as well as drying of the colourless powder at +500C., there is obtained the following elementary analysis: calc: C 76.52%; H 7.64%; N 4.82% found: C 76.28%; H 7.93%; N 4.48% Films can be cast and lacquer-like coatings can be produced in the usual manner from solutions of the polyadduct. The polyadduct softens at a temperature above +800C. to give a very viscous mass which can be shaped according to known techniques to give films, rodlets and other objects.

If the polyreaction, after mixing and degassing, is carried out in a shape-imparting vessel, for example in a hollow cylinder made of "Teflon", then a corresponding round rod is obtained which -displays good strength values.

Example 2 N,N'-Dibenzylhexamethylene-1,6-diamine (b.p.

189-1930C./0.2 mm.Hg; m.p. 30.50C.; nD =1.5452) is prepared from bis-(benzylidene)hexamethylene-1 6-diamine by reduction with sodium boranate in ethanolic solution. After repeated distillation, the diamine is obtained in the form of a colourless, oily liquid which is thin layer chromatographically pure and uniform (thin layer chromatography on "Silufol", elution agent ethanol/isobutylacetate (25% aqueous ammonia solution 10:10;3).

Analysis: C2oH2aN2 (M.W. 296.5) calc.: C 81.03%; H 9.52%; N 9.45% found: C 81.15%; H 9.82%; N 9.56% 10.700 g. of colourless, crystalline 2,2-bis-(4glycidyloxyphenyl)-propane (m.p. 42.5--43 0 C.) are reacted in the manner described in Example 1 with 9.118 g. N,N'-dibenzylhexamethylene-1,6- diamine, first for 24 hours at ambient temperature and subsequently for 120 hours at +600C. Even after 24 hours, a relative molecular weight of 8500 is achieved which, after a further 100 hours, increases to about 12,000.

There is obtained a colourless, glass-like solid body (Tg+350C.) which above +600C., begins to flow without decomposition. The polyadduct is soluble in chloroform/methanol. Readily adhering films can be cast from this solution. The polyadduct can be thermo-plastically shaped in known manner.

Example 3 N,N'-Dibenzyl-3,6-dioxaoctane-1 ,8-diamine (b.p. 2(57-2100C./0.1 mm.Hg; n2 =1.5406) is prepared from 1 ,8-dichloro-3,6-dioxaoctane by reaction with benzylamine: for this purpose, 1 mol (187.1 g.) 1 ,8-dichloro-3,6-dioxaoptane are added dropwise, with stirring, in the course of 1 hour to 10 mol (1071.5 g.) benzylamine. The reaction mixture is heated for 1 hour at 1 400C.

and for a further 3 hours at 900C. After cooling, 4 mol (224 g.) potassium hydroxide are added thereto in the form of a 25% aqueous solution.

The mixture is vigorously shaken up in a separating funnel. After separation of the phases, the upper amine phase is separated off, dried over solid potassium hydroxide and subjected to vacuum distillation. After distilling off excess benzylamine, the residue is fractionally distilled.

The diamine is obtained in the form of a colourless, oily liquid which is thin layer chromatographically uniform (thin layer chromatography on "Silufol", elution agent ethanoVisobutyl acetate/25% aqueous ammonia 10:10:3). The yield is 50% of theory.

Analysis: C20H2{N2O2 (M.W. 328.5) calc.: C 73.13%; H 8.59%; N 8.53%; found: C 73.14%; H 8.72%; N 8.40% The corresponding dihydrochloride melts at 189.5-1 900C.

Analysis: C2oH2BN202.2HCI (M.W. 401.4) calc.: C 38.52%; H 6.41%; N 37.92% found: C 38.64%; H 6.14%; N 37.67% 10.000 g. colourless crystalline 2,2-bis-(4glycidyloxyphenyl)-propane (m.p. 42.5-430C.) are reacted in the manner described in Example 1 with 9.439 g. N,N'-dibenzyl-3,6-dioxaoctane-1 8- diamine first for 24 hours at ambient temperature and subsequently for 120 hours at 600C. A pale yellow, glass-like solid body is obtained with a relative molecular weight of 10,000 (Tg+40C.) which begins to melt above +450C. without decomposition. The polyadduct is soluble in chloroform/methanol. Readily adhering films can be cast from this solution. The polyadduct can be thermoplastically shaped in known manner.

Example 4 N,N'-Dibenzyl-p-xylylenediamine (b.p.

1 300C./0.2 mm.Hg; m.p. +530C., nD =1.5800) is prepared from p-xylylene dichloride by reaction with benzylamine in the following manner: 1 mol (175.0 g.) pxylylene dichloride are introduced portionwise, with stirring, in the course of 1 hour to 10 mo1(1071.5 g.) benzylamine. The reaction mixture is heated to 1 500C. for 2 hours. After cooling, 4 mol (224 g.) potassium hydroxide are added thereto in the form of a 25% aqueous solution. Two phases are formed, the upper of which is separated in a separating funnel and dried with potassium hydroxide until a clear liquid is obtained.This is distilled in a vacuum under a protective atmosphere of nitrogen: at +680C./1 0 mm.Hg residual benzylamine is obtained and at +1 300C./0.2 mm.Hg. the desired diamine. The diamine is isolated as a pale yellow, oily liquid which, after some time, crystallises to give colourless crystals and is thin layer chromatographically uniform (thin layer chromatography on "Silufol", elution agent ethanol/isobutyl acetate/25% aqueous ammonia solution 7:10:2). The yield is 71% of theory.

Analysis: C22H24N2 (M.W. 316.4) caic.: C 83.50%; H 7.64%; N 8.85% found: C 84.12%; H 7.68%; N 8.73% 1 9.439 g. colourless crystalline 2,2'-bis-(4 glycidyloxyphenyl)-propane (m.p. 42.5--430C.) are reacted in the manner described in Example 1 with 1 7.674 g. N,N'-dibenzyl-p-xylylenediamine for 50 hours at 800C. There is obtained a polyadduct with a relative molecular weight of 10,000 in the form of a yellowish, glass-like solid body (Tg+570C.) which begins to flow above 1000C. without decomposition. Readily adhering films can be cast from solutions of this polyadduct. The product can be thermoplastically shaped in known manner.

Example 5 4,4'-Bis-(N-benzylamino)-diphenylmethane (m.p. 11 00C.) is prepared by reacting 4,4'diaminodiphenyl-methane with benzyl alcohol and potassium hydroxide at 2700C. After recrystallisation from ethanol, the product is obtained in the form of a colourless crystalline product which is thin layer chromatographically uniform (thin layer chromatography on "Silufol", elution agent ethanol/isobutyl acetate/25% aqueous ammonia solution 7/10/2 v/v/v).

Analysis: C2,H26N2 (M.W. 378.5) calc.: C C 85.67%; H 6.92%; N 7.41% found: C 85.96%; H 6.98%; N 7.40% 10.508 g. of colourless, crystalline 2,2'-bis-(4 glycidyloxyphenyl)-propane (m.p. 42.53 0 C.) are reacted as described in Example 1 with 10.695 g. 4,4'-bis-(N-benzyiamino)- diphenylmethane for 50 hours at 1 500 C. Even after 20 hours, a relative molecular weight of 5000 is achieved which, after a further 30 hours at this temperature, increases to about 10,000. A yellow-brown, glass-like solid body is obtained (Tg+870C.) which begins to flow above 1 200C.

without decomposition. The polyadduct is soluble in chloroform/methanol. Readily adhering films can be cast from this solution. The polyadduct is thermoplastically shapable in known manner.

Example 6 N,N'-Dibenzyl-2,2,4(2,4,4) trimethylhexamethylene-1 ,6-diamine (b.p.

200 C./0.15 mm.Hg) is prepared analogously to Example 2 by reacting 2,2,4-(2,4,4)-trimethyl hexamethylene-1 ,6-diamine with benzaldehyde and subsequent reduction with sodium borohydride.

Analysis: C23H34N2 (M.W. 338.5) calc.: C 81.60%; H 10.12%; N 8.28% found: C 81.72%; H 10.19%; N 8.29% In the manner described in Example 1, 10.000 g. crystalline 2,2'-bis-(4-glycidyloxyphenyl)propane are reacted with 9.898 g. N,N'-dibenzyl- 2,2,4(2,4,4-tri-methylhexamethylene-1 ;6-diamine for 72 hours at 600 C. A soluble, thermoplastically shapable polyadduct is obtained (Tg+360C.) with a relative molecular weight of 8200.

Claims (10)

Claims

1. A process for the preparation of high molecular weight, thermoplastic epoxide-amine polyadducts, wherein a diepoxide is reacted with a diamine of the general formula:-

in which R is an aralkyl radical and R' is a divalent, straight-chained or branched alkylene, cycloalkylene, arylene or heterocyclic radical which optionally contains hetero atoms and/or double and/or triple bonds, in a mole ratio of about 1.0:1.0, without the use of a solvent or diluent.

2. A process according to claim 1, wherein the mole ratio of diepoxide to diamine is from 0.95:1.0 to 1.0:1.05.

3. A process according to claim 1 or 2, wherein a mixture of two or more diamines is used.

4. A process according to any of the preceding claims, wherein a mixture of two or more diamines is used.

5. A process according to any of the preceding claims, wherein the diepoxide used is 2,2-bis-(4glycidyl-oxyphenyl)-propane.

6. A process according to any of the preceding claims, wherein the polyaddition reaction is carried out directly in a shape-imparting vessel to give a shaped body or, for the formation of coatings, is carried out directly on the surface to be coated or, for the production of adhesive joints or sealings, is carried out directly between the parts to be adhered or sealed.

7. A process according to any of claims 1 to 5, wherein in the case of fibre-reinforced work materials or of filled work materials or of duplex or laminated materials, the polyaddition reaction is carried out directly with the addition of the materials to be incorporated.

8. A process for the preparation of high molecular weight, thermoplastic, epoxide-amine polyadducts according to claim 1 substantially as hereinbefore described and exemplified.

9. High molecular weight, thermoplastic epoxide-amine polyadducts, whenever prepared by the process according to any of claims 1 to 8.

10. Shaped bodies, whenever comprising or consisting of a high molecular weight, thermoplastic epoxide-amine polyadduct according to claim 9.