DE2350496A1 - NEW, HEAT-TURNING AND STORAGE-STABLE MIXTURES - Google Patents

Description

Dr. F. Zumsfeln sen. - Dr. E. Assmann OOCn / flff

Dr.R. Koenigsberger - Phye. R. Holzbauer ZJOU H> 3

Dr. F. Zumstein jun. Patent attorneys

8 Munich 2, Bräuhoussfraße 4 / III

Case>

Germany

New, heat-curing and storage-stable mixtures

The present invention relates to new, thermosetting and storage-stable blends of polyimides of certain unsaturated dicarboxylic acids, polyamines and assomethines, and a process for the production of molded articles from these new mixtures.

In the American patent specification 2 818 405 the

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Production of elastomers from bis-maleimides and certain long-chain amines with a molecular weight between 750 and 12,000 described. However, these curable mixtures are less suitable for the production of, for example, molding compounds or laminates; also is
the heat resistance of the molded materials made from them is not particularly good.

The French patent 1 555 564 also describes the production of products from Ν, Ν'-bis-imides of certain unsaturated dicarboxylic acids and diprimary diamines. The indicated properties of these products, such as the bending strength are, however, only after 15 - reached 230 ⁰ C - 50stündiger curing at 200th These long curing times can be shortened by applying pressure, but then curing has to be done

at a pressure of up to 100 kp / cm. In contrast, the molding materials according to the invention can substantially shorter curing times and without the use of pressure. As a further advantage, they have one Significantly higher dimensional stability in the heat without becoming more brittle as a result. The mechanical properties the molding materials obtained from the mixtures according to the invention are better than those according to the French Patent specification obtained molding materials. For the broadest possible applicability of a macromolecular shape

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It is substance. It is important that this has a combination of as many beneficial and valuable properties as possible having. For example, a macromolecular molding material with very high heat resistance is often used for a technical Application not usable »because these can only be processed into technical products with difficulty can, or because of this other, disadvantageous property such as brittleness.

In "Tetrahedron" 27, page 2203 ff, the addition of 2 molecules of an N-substituted maleimide on an azomethine described. However, this reaction is not very favorable, like the gex-ingen yields of average show only 40%. In addition, this addition has the disadvantage that it takes place relatively very slowly. Geinäss the publication cited above, for example, one of N-phenyl-maleimide and Ν, Ν-dimethylbenzylidene-methylamine existing mixture after 10 hours of continuous heating to 135 ° only 32% of the theoretically expected- " get the adduct.

It has now been found that mixtures of a polyamine and excess polyimide react quickly and almost quantitatively with the azomethine. Surprisingly, will without the use of pressure or very long curing times and without any other application difficulties

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Molding materials with valuable and advantageous properties are obtained compared with those according to the French Patent No. 1,555,564 from bis-imide and diprimary Moldings made from diamines.

The present invention thus relates to new, storage-stable, heat-curable mixtures which are characterized in that they are are that they contain

a) Polyimides of certain unsaturated dicarboxylic acids of the general formula I ~

(D

in which A is an x-valent, organic radical with at least 2 and at most 30 carbon atoms, B for a remainder of the formulas

CH ₃ CH,
HC ^X C

H .. CH ₃

stands, and χ means the number 2 or 3,

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h) polyamines of the formula II or III

(ID

KH ₀

■ Ö

(HD

-Ία

wherein in formula II the radical D is a y-valent organic Is a radical having 2 to 40 carbon atoms, and y is an integer from 2 to 4, and wherein in formula III the radicals R-. one each by separation of the oxygen atom obtained divalent hydrocarbon residue of an aldehyde or ketone with 1 to 8 carbon atoms "mean, m. for. a number from 0.1 to 2 stands,

c) Azomethines of the general formulas IV, V or VI

IU

R ₂ - C = N -

R,

R ₂ -C = NEN = C -

^R 2

- N = C- R ₃ -C = N -

(IV)

(V) (VI)

in which

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R «is a hydrogen atom, a linear or branched one aliphatic hydrocarbon radical with up to 12 carbon atoms, a cycloaliphatic or cycloaliphatic-aliphatic Hydrocarbon radical with up to 12 carbon atoms, an aromatic radical with 6-12 carbon atoms, an araliphatic radical Hydrocarbon radical with up to 20 carbon atoms or a heterocyclic or heterocyclic-aliphatic Rest means

R ~ and R. with the exception of the meaning for a hydrogen atom have the same meaning as R2, where Ro together with R ^ including the two C atoms bearing substituents can also mean a cycloaliphatic ring system, and

E is a divalent organic radical with at least 2 and at most 30 carbon atoms, and optionally

-d) a curing catalyst.

The mixtures according to the invention preferably contain

a) Poly-imides of the formula I, in which A is a radical of Formulas

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CiBA-GEIGYAG _ 7 -

CH

Y \

0-C.Hc

ι ⁶ -

η = 2-8, O = P

' ^V 2

^U 6 ⁿ 5 _ _x Y "° 6 ⁿ 5

HQ

and B denotes the vinylene radical,

b) di- or tri-primary polyamines of the formula II, in which D is an organic radical having 2 to 40 carbon atoms, and

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CIBA-GEIGY AG

■ - 8 -

c) Azomethines of the formulas IV or V, in which R ^ denotes a hydrogen atom, R ₃ and L each denote a phenyl radical and E a radical of the formulas

^or

2-8

means.

The polyimides of the formula I represent a known class of compounds and can be obtained by applying the methods described in US Pat. No. 2,444,5j56 and in British Patent specification 1,137,592 methods described by reacting the corresponding diamines with the unsaturated Dicarboxylic anhydrides prepared in a polar solvent and in the presence of a catalyst will.

The symbol A in the formula I can be a linear or a

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branched alkylene radical with less than 20 carbon atoms, a phenylene radical, a CycXohexylenrest or a Remainder of the formula

in which a represents an integer from 1 to 3, mean *

The symbol A can also comprise several phenylene or cyclohexyl radicals which are directly or by a simple valence bond or by an atom or an inert group, such as oxygen or sulfur atoms, alkylene groups with 1 to 3 carbon atoms or via the following groups -CO-, -SO ₂ -, -KR- "(R = alkyl), ..- S = N-, -COM- ,. -COO-, -CONH-A-NHCO-, O = P (O- ^ ₁ S = P (O-) _{3 are} connected.

In addition, the various phenylene or cyclohexyl radicals be substituted by methyl groups. The symbol A can also be used for the grouping

—C-ö

-GoH, - N N- CH- -CH - N N- C ^ H _A -3 6 ν s 36 3 6 \ /

G C

stand. Therein R-, R ₆ , R ^ and R _{g denote} hydrogen atoms or identical or different aliphatic hydrocarbons

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Substance residues with 1-6 carbon atoms, where R ₁ - and R, - together with the carbon atom in position 5 can also form a 5- or 6-membered aliphatic ring.

Specific examples of polyimides of the formula I may be called:

NjN'-Aethylen-bis-maleinimid NjN'-Hexamethylene-bis-maleinimid t ^ i ^ -m-Phenylen-bis-maleinimid N, N ¹ -p-Phenylen-bis-maleinimid N, N'-4,4'- Diphenyimethan-bis-maleinimid N, N'-4,4'-3,3'-dichloro-dipheny! Methan-bis-maleinimid .N, N ^l * 4,4'-Diphenyläther-bis-maleinimid N, N'- 4,4'-Diphenylsulfon-bis-maleinimid N, K '". 4 _J 4 ^l -Dicyclohexylmethan-bis-maleinimid N _i N ^t * -aja ^l * -4,4'-diriethylenecyclohexane-bis-maleinimid N, N' -m-xylylene-bis-maleinimid NjN ^ p-xylylene-bis-maleinimide N, N'-4,4'-diphenylcyclohexane-bis-maleinimide N, N '-m-phenylene-bis-citraconimide Ν, Ν * -4 , 4'-Diphenj'lmethan-bis-citraconimid N, N ^l -4,4'-2,2-diphenylpropane-bis-maleimide

maleinimid

N, N'-4,4'-diphenylmethane-bis-itaconic acid imide N.N'-p-phenylene-bis-itaconic acid imide

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N, K'-4,4'-diphenylmethane-bis-dimethylmaleimide N, N '-4,4'-2,2-diphenylpropane-bis-dimethylnialeinimide N, N'-hexamethylene-bis-dimethylmaleimide N, N'-4 , 4'-Diphenylether-bis-dimethylmaleimide jj _} N'-4,4'-Diphenylsulfon-bis -dimethylmaleimide

the Ν, Η'-bis-maleinimide of 4,4'-diamino-tri "phenyl-phosphate,

the NjN'-bis-maleinimide of 4,4'-diamino-triphenyl-phosphite,

the NjN'-bis-maleimide of 4,4 ^l -diamino-triphenylthiophosphate,

the K, N ¹ , N "-trismaleinimide of tris (4-aminophenyl) phosphate,

the N, N ¹ , N ⁿ trismaleinimide of tris (4-aminophenyl) phosphite,

the N, N ¹ , N "-trismaleinimide of tris (4-aminophenyl) thiophosphate.

Mixtures of two or more of these Pol3 ^T imides can also be used.

The polyamines of the formulas II and III are known compounds.

If the polyamine of the formula II is a diprimary, then D in formula II has the same meaning as A in formula I and χ

Examples of diamines of the formula II include: 4,4'-diamino-dicyclohexylmethane, 1,4-diamino-cyclohexane, m-phenylenediamine, p-phenylenediamine, 4,4'-diamino-diphenyl-

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methane, bis (4-aminophenyl) -2,2-propane, 4,4'-diamino-diphenyl ether, 4,4'-diarainodiphenylsulfone, 1,5-diaminonaphthalene * m-xylylenediamine, p-xylylenediamine, ethylenediamine, Hexamethylenediamine, bis (; p-aminopropyl) -5,5-dimethyl-hydantoin, 4,4'-diaminotriphenyl phosphate.

The use of m-phenylenediamine, 4,4'-diaminodipheny is preferred line than, 4,4'-diamino-diphenyl ether, hexamethylenediamine , 4,4'-diamino triphenyl phosphate, 4,4'-diaminotriphenyl thiophosphate, 4,4'-diamino triphenyl phosphite.

Among the diprimary polyamines of the formula II Various polyamines of the formula II are preferably used those which have fewer than 40 carbon atoms and have 3 or 4 NHo groups per molecule. The NH2 groups can optionally through Methyl group substituted benzene ring, naphthalene ring, pyridine ring or triazine ring. You can can also be substituted on several benzene rings, which are interconnected by a simple valence bond Atom or an inert group which have already been mentioned under the diprimary polyamines of the formula II, or also by one of the following groups

O S

!) 1

-N-, -CH-, -ΟΡΟ-, -ΟΡΟ-, -ΟΡΟΙ I j ί i

0 0 0

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be connected. As examples of such polyamines, the following can be mentioned; 1,2,4-Triamin © ben: z: ol, 1,3,5-Triarainobenzol, 2,4,6-Triaminotöluo 1, 2,4,6-Triamino-13,5-trimethylbenzi> l ,, 1, 3, .7-Triarainonaphthalin, 2,, 4,4 ^r - ■■ Triaminödiphenyl ^ 3,4 _f 6-T ^ ciaminopyridin ,: 2,, 4,4'-Triamino- pheßyläther _t i ^^ '- Triaminodiptienyliiiethan ,, 2,4,4 ⁱ -Triaminodiphenylstilfon, 2,4 _f 4 ^r -TriaminoBen2iöpttenön, 2,4,4 * - Triamina-S-mettiyl-diphenyltfiethan, K, K., K-Tri (4-äffiioopheöyi) äriiift, Tr " i- (4-aittittophenyl) -methane _f tri- (4-antiriopheny 1) -phosphate »TrI- (4-aminophenyl) -phosphite, tri * (4-amiEtophenyl) -thiophosphate, 3,5 ^ 4 '-Triaminobenzäiniiicij melamine ^ 3> 5 »3 ^f , 5 ^r -teträaminöbenzöphenOri, 1,2,4, S-

3, - 3 *, 4,4 ^r -Tetraaminöphettylather, 3,3 ^f , 4,4 '-Tetraämittödiphenyimeehan, 3,3 ^r ^, A'-TetraaminodipheirtylsMlfötti 3,5-Bl S- * (3 y 4 ^r -diatnlEiöpheny 1) -pyridift.

xtita die Verwertdüng von tri- (4-ami «öphenyi> tri ^ (4-aiQinophenyl} * phosphite and tri * (4-amitio- 'phenyl) thiophosphate or a mixture of these.

The polyamines of the formula III are also known compounds and can after the in the French Pätertt sehrifteti 1,430,977 and 1,481,932 by reacting primary aromatic amines with aldehydes or ketones can be obtained.

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The aldehydes or ketones used are, for example, formaldehyde , acetaldehyde, benzaldehyde, oenanthaldehyde, acetone, methyl methyl ketone, cyclohexanone and acetophenone.

The azomethines of the formula IV and V represent a well-known one Class of compounds and are obtained by taking aldehydes or ketones of the formula

I ³

Ro - C. = O

(VII)

where R « ^unc ^ & -i ° ^ ^{e have the} same meaning as in formulas IV and V, with monoamines of the formula

(VIII)

or diamines of the formula

H ₂ N - E - NH ₂ - (IX)

wherein R, and E have the same meaning as in formula IV and V have reacted in equivalent amounts and optionally in the presence of a catalyst.

The azomethines of the formula VI are also known compounds and are prepared in an analogous manner by dialdehydes or diketones of the formula

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^R 2

.0 = C - R ₃ - C = 0 (X)

wherein R ₉ and R ~ have the same meaning as in formula VI, with monoamines of the formula X in equivalent amounts and optionally in the presence of a catalyst.

The azomethines of the formulas IV, V and VI can after a der'known processes are produced as they are for Example summarized in "Houben-Weyl", methods of Organic Chemistry, Volume 11/2 (1958), page 73 ff.

In the azomethines of the formulas IV, V and VI, the radicals R ₉ , Rn ^unc * R, insofar as they are an aliphatic or araliphatic radical, in the hydrocarbon chain can also contain the grouping -0-, -SO ₂ -, -CONH- or -COO-included. If the radicals R ₉ , R and R represent aliphatic, aromatic, araliphatic, cycloaliphatic, cycloaliphatic-aliphatic or heterocyclic radicals, these radicals can also be substituted with groups which do not adversely affect the addition mechanism when the mixture cures. Examples of such groups are: halogen atoms, alkyls, alkoxyls, -NO ₉ -, -CON (R) ₉ or -COOR (R = alkyl) and -SO ₉ . In the heterocyclic and heterocyclic-aliphatic radical, the following

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G. - 16 -

de heteroatoms or hetero groups are included: -0-, -SO ^ -, -S-, -SO-, and = N- or -NH-. Preferably means the heterocyclic radical is a Ν, Ν-heterocyclic Rest.

As carbonyl compounds of the formulas VII and VIII for the preparation of the azomethines of the formulas IV, V or VI are especially mentioned:

Acetaldehyde, propionaldehyde, isobutyraldehyde, butyraldehyde, caproaldehyde, caprylaldehyde, capric aldehyde, tetrahydrobenzaldehyde, hexahydrobenzaldehyde, furfurol, benzaldehyde, 2-methylbenzaldehyde, p-methoxybenzaldehyde, ß- naphthaldehyde, di-naphthaldehyde, acetone, methylethylketone, di-naphthaldehyde, di-naphthaldehyde, di-naphthyl ketone, di-naphthaldehyde ketone, di-naphthaldehyde ketone, di-naphthaldehyde ketone, di-naphthaldehyde ketone, di-naphthaldehyde, acetone Acetophenone, butyrophenone, benzophenone, 2-methyacetophenone, 4-methoxypropiophehone, cyclopentanone, terphthalaldehyde, isophthalaldehyde, glyoxal, glutaraldehyde and acetonylacetone.

As monoamines of the formula VIII for the preparation of the azomethines of the formula V or VII may be mentioned in particular: methylamine, butylamine, isobutylamine, hexylamine, dodecylamine, Cyclohexylamine, benzylamine, aniline, toluidine, a-naphthylamine, ß-naphthylamine.

As diamines of the formula IX, for the preparation of the azomethine of the formula V may be mentioned in particular: ethylenediamine, 1,6-hexamethylenediamine, 3,3,5-trimethyl-1,6-di-amino

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hexane, isophoronediamine, m-phenylenediamine, p-phenylenediamine, 4.4 ^l ~ diamino-diphenyl ~ methane, 3,3'-dichloro-4 _s 4 '~. diaminodiphenyl methane, 4.4 ^! Diamino diphenyl ether, 4,4'-diamino-diphenyl sulfone, 4,4'-diamino-dicyclohexyl-methane, m-XyIylendiamin, p-XyIylendiamin, 4,4 '~ diamino-l, 1-diphenyl-propan ^f , Bis - (^ - aminopropyl) -5,5-dimethyl-hydantoin.

Specific azomethines that may be mentioned are: N / N '~ bis (benzylidene) hexamethylenediamine, N, N ¹ -bis- (benzylidene) -p-phenylenediamine, N ^ H ¹ -BIs- (berLzyiidenJ-diarainodiphenylmetiian, Ben-

Benzalaniline »

The mixing ratio between the polyimide of the formula I, the polyamines of the formula II or JLII and the azoiaethines of formulas IV, V. and VI can vary within a wide range * The ratio of these 3 components is chosen so that 0.1 to 0.85 equivalents of primary amino group per 1 equivalent of imide group in the reaction mixture and 0.45 to 0.08 equivalents> .C = N group are, where the sum of the equivalents of the primary amino group and ^ C = N group is 0.33 to 1.0 equivalents, preferably 1.0 equivalent, per 1 equivalent of imide group amounts to. *. '

The hardenable mixture can also consist of several, different Poly-imides, poly-amines and azomethines consist »

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Curing of the mixtures according to the invention is effected by heating the mixtures to temperatures between 100 280 ° C, preferably 150-250 ⁰ C, with the blends without release of volatile reaction products in crosslinked, insoluble and infusible products pass.

It is also possible to produce only a prepolymer from the novel mixtures by the homogeneously mixed, if appropriate finely ground raw materials temporarily at 50 - heated 140 ⁰ C, so that a more thermally deformable, partially soluble product. This prepolymer may have to be ground again to a processable powder. The prepolymerization can also be carried out by heating a solution or suspension of the starting materials. In addition, substances come into question that do not react with the starting materials and that solve them sufficiently if desired. Examples of such liquids are: dimethylformamide, tetramethylurea, dimethyl sulfoxide, N-methylpyrrolidone, dichloroethylene, tetrachlorethylene, tetrachloroethane, tetrabromoethane, chlorobenzene, dichlorobenzene, bromobenzene, cyclohexanone, dioxane, or alkylated aromatic hydrocarbons.

It is also possible to first prepare a prepolymer from imide and amine or imide and azomethine, in which

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the homogeneously mixed starting materials are temporarily heated to 50 - 140 °, so that a still fusible, sufficient soluble product is formed, which later becomes one with the still missing third reaction component homogeneous reaction mixture or homogeneous reaction solution can be processed and hardened.

For some technical applications it is the addition of a curing catalyst advantageous. By adding, for example, a small amount of an organic peroxide or Persalzes, the hardened state is reached more quickly. Compounds such as di-tert-butyl peroxide, Dilauryl peroxide, tert-butyl cumyl peroxide or tert-butyl perbenzoate in a concentration of 0.01-5 percent, preferably 0.25-0.5 percent, based on the total, weight of the curable mixture, suitable. However, other, non-peroxidic hardening accelerators or Additives that have a beneficial effect on hardening can be used.

The curable mixtures according to the invention are used primarily in the areas of surface protection, electrical engineering, lamination processes and construction. They can be adapted in each case to the specific application Formulation, in the unfilled or filled state, if necessary in the form of solutions or dispersions, as paints, molding compounds, sintering powder, immersion resins,

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Casting resins, injection molding formulations, impregnating resins, Binders and laminating resins can be used.

The invention therefore also provides a process for the production of crosslinked, insoluble and infusible ones Plastic products, characterized in that they are polyimides certain unsaturated carboxylic acids of the formula I, polyamines of the formulas II and / or III and azomethines of Formula IV, V or VI, and optionally in the presence of a curing catalyst at temperatures of about 100 ° and 280 ° with each other.

The inventive production of the crosslinked, infusible Products are usually made with simultaneous shaping into moldings, flat structures, laminates, Bonding. The curable compositions can be those customary in the technology of curable plastics Additives such as fillers, plasticizers, pigments, dyes, mold release agents, flame retardants added will. For example, glass fibers, mica, quartz powder, kaolin, colloidal silicon dioxide can be used as fillers or metal powder can be used; calcium stearate, for example, can serve as a mold release agent. The shaping can be heated to the preferred

done 200 kp / cm - example 170-250 ⁰ C at a pressure of Figure 1. The resulting molded bodies already have sufficient mechanical strength so that they

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half of the press in an oven at 200-280 ⁰ C can be completely cured.

First, the curable mixtures become a prepolymer produced, this can be ground to a fine powder using the fluidized bed sintering process as a surface protection agent be used.

A solution or. Suspension of the prepolymer in a £ Suitable solvents can be used for the production of lamina * ..ι serve by making porous fabrics such as fabric, fa-matting or nonwovens, especially fiberglass mats or fiberglass fabrics, impregnated with solutions or suspensions and the solvent is removed by a drying process. The further hardening takes place in a press at

2 preferably 170-250 ° C and 5-200 kp / cm pressure. It

is also possible in the press only precure the laminates and the products thus obtained in an oven at 200 - 280 ⁰ C post cure to achieve optimal performance characteristics.

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CLBA-GEIGY AG example 1

71.6 g (Q, 20 moles) N, N ^! -4,4'-Diaminoxiiphenylmethan-bis-maleiniraid, (in the following examples abbreviated as "bis-imide I"), 9.9 g (0.026 mol) of tri- (4-aminophenyl) -phosphate and 23 , 5 g (0.08 mol) Ν, Ν'-BLs- (benzylidene) -hexamethylenediamine were mixed well, melted in an oil bath at 160 ° C. and degassed in vacuo at 15 torr. The clear melt was poured into a mold measuring 150 × 150 × 4 mm and cured at 160 °, 180 ° and 200 ° C. for two hours. The properties of the hardened body are shown in Tables 1 and 2.

Example 2

143.6 g (0.234 mol) of N, N ', N "-tris-maleinimide of tri - (" 4-aminophenyl) phosphate, (referred to as "bis-imide II" for short in the following examples), 9.3 g (0.047 mol) of 4,4'-diaminodiphenylmethane and 57.1 g (0.152 mol) of Ν, Ν'-bis (benzylidene) -p-phenylenediamine were mixed well, melted in an oil bath at 180 ° C and in a vacuum at 15 Torr degassed. The clear melt was in a form similar to that in Example 1 at 180 ° C. and 200 ° C. for 3 hours each hardened. The properties of the hardened body are shown in Tables 1 and 2.

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CIBA-GEIGYAG ο- *

■ - CL? -

Example 3 - 2350496.

75.0 g (0.204 mol) of "bis-imide I ^lt , 8, lg (0.04 l mol) of 4,4'-diaminodiphenylmethane and 23.9 g (0.082 mol) of Ν, Ν'-ΒΙε-φβητ-zyliden ^ hexamethylenediamine were well mixed, melted in an oil bath of l6o C and degassed in a vacuum at 15 Torr. The clear melt was transferred as in example 1 in a cured molding body, whose properties are shown in Ta ble 1 and 2..

Example 4

60.7 grams (0.169 moles) of "bis-imide Ι", 13.6 grams (0.069 moles) of 4,4'-diaminodiphenylmethane and 20.7 g (0.051 mol) of N, N'-bis (benzylidene) hexanediol-1,6-di (7-aminopropyl) ether were mixed well, melted in a round bottom flask at ΙβΟ C and degassed. The clear melt was poured and cured as in Example 1. The test data of the molded article obtained are listed in Table 1.

Example 5

63.6 g (0.178 mol) of "bis-imide I", 14.1 g (0.071 mol) 4.4 ^f -diaminodiphenylmethane and 22.3 g (0.053 mol) N, N ^! -Bis- (benzylidene) -l, 3-di- (7-aminopropyl) -5> 5-cliniethylhydantoin were mixed well in a round bottom flask, melted at 160 ° C. and degassed. The clear melt was poured and cured as in Example 1. The test data for the molded body obtained are listed in Table 1. - · "

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'70.01.335

CIBA-GEIGYAG - 24 - Example 6

65.2 g (0.20 mol) of N, N ^t -4.4 ^t -diaminophenyl ether bis-maleimide, 14.35 g (0.073 mol) of N, N ^t -4,4'-diaminodiphenylmethane and 20.45 g (0.055 mol) N, N '- bis (benzylidene-diaminodiphenymethane) were mixed well in a round bottom flask, melted and degassed at 160 ° C. The clear melt was poured and cured as in Example 1. The test data of the molded body obtained are given in Table 1.

Example 7

70.5 grams (0.197 moles) of "bis-imide I", 15.6 grams (0.079 moles) of 4,4'-diamino-diphenyl methane and 13.9 g (0.059 mol) of N, N'-bis (benzylidene) ethylenediamine were mixed well in a round bottom flask, melted at 160 ° C. and degassed. The clear melt was cast and cured as in Example 1. The test data of the test specimen obtained are given in Table 1 .

. Example 8

65.1 grams (0.182 moles) of "bis-imide i", 14.4 grams (0.073 moles) of 4,4'-diaminodiphenylmethane and 20.5 g (0.55 moles of N, N'-bis (benzylidene) -4,4'-diaminodiphenyl ether were mixed well in a round bottom flask, melted at ΙβΟ C and degassed. The clear one Melt was poured and cured as in Example 1. The test data of the molded body obtained are given in Table 1,

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CIBA-GEIGYAG _ox -

- DO -

Example 9

62.8 grams (0.175 moles) of "bis-imide i", 1. 9 grams (0.07 moles) of 4,4'-diaminodiphenyl methane and 2j5,; 5 g (0.0525 mol) of Ν, Ν'-bis (benzylidene) -4,4'-diamino-3i ^ '- dlchlorodiphenylmethane were mixed well in a round bottom flask, melted at 160 ° C and degassed. The clear melt was as in Example 1 potted and hardened. The test data of the test piece obtained are given in Table 1.

Example 10

71.4 grams (0.116 moles) of "Bis-imide II", 8.7 grams (0.023 moles) of tri (4-aminophenyl) phosphate and 19.9 S (0.070 moles) N, N'-bis (benzylidene) -p-phenylenediamine were mixed well in a round bottom flask, melted at 160 C and degassed. The clear one Melt was poured and cured as in Example 1. The test data of the molded body are given in Table 1.

Example U

75.0 grams (0.21 moles) of "bis-imide i", 16.6 grams (0.084 moles) of 4,4'-diaminodiphenymethane and 18.4 g (0.063 moles) of Ν, Κ'-bis (benzylidene ^ hexamethylenediamine were mixed, melted at 180 C, degassed and poured as in Example 1 and hardened. The test data for the molded body are given in Table 1 specified. -

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CiBA-GEIGYAG - 2 β - Example 12

215 grams (0.60 moles) of "bis-imide i", 47.0 grams (0.235 moles) of 4,4'-biaminodiphenylmethane and 67.5 g (0.18 moles) of N, N'-bis (benzylidene) diaminodiphenylmethane were mixed well in a round bottom flask, melted at 160 ° C and degassed. The clear one Melt is poured into molds with the dimensions 150x150x4 mm and 150x150x2 mm and cured as in Example 1. the Test data for the moldings are given in Table 1.

Example Ij5

69.5 grams (0.194 moles) of "bis-imide I", 18.7 grams (0.05 moles of tri (4-aminophenyl) phosphate and 21.8 g (0.075 mol) of Ν, Ν'-ΒΪΞ-cylidene) diaminodiphenylmethane were mixed, melted, degassed, potted and cured as in Example 1. the Test data for the molding are given in Table 1.

Example 14 _f

66.7 grams (0.186 moles) of "Bis-imide I", 14.7 grams (0.074 moles) 4.4 ^! - Diaminodiphenylmethane, 8.2 g (0.028 mol) Ν, Ν'-bis (benzylidene ^ hexamethylenediamine and 10.5 g (0.028 mol) Ν, Ν'-bis (benzylidene) -diaminodiphenylmethane were mixed as in Example 1, melted, degassed, potted and hardened The test data of the molded body are given in Table 1.

409817/1020

CIBA-GEIGY AG - 27 -. Example 15

66.7 β (0.186 mol) "bis-imide I", 7.35 g (0.0 ^ 7 mol) diaminqdiphenylmethane, 7.35 g (0.037 mol) 4,4'-diaminodiphenyl ether, 8.2 g (0.028 mol ) N, N'-bis (benzylidene ^ hexamethylenediamine and 10.45 g (0.028 mol) N, N ¹ -benzylidene-diaminodiphenyl methane were mixed, melted, degassed, cast and cured as in Example 1. The test data of the
Pormodies are given in Table 1.

Example l6

74.2 g (0.208 mole) of "bis-imide i", 16.4 g (0.083 mole) 4.4 ¹ -diaminodiphenylmethane and 19.4 g (0.062 mole) N, N'-bis (benzylidene) -p -xylylenediamine were mixed, melted, degassed, cast and cured as in Example 1. The test data of the "T-shaped body" are given in Table 1.

Example 17

68.6 grams (0.192 moles) of "bis-imide I", 7.6 grams (0.038 moles) of 4,4'-diaminodiphenylmethane, and 28.8 grams (0.077 moles) of N, N'-bis-Cbenzylidene) diamino diphenylme than were as in Example 1
cured to a shaped body, the test data of which are given in Tables 2 and 3.

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70.01.335

CIBA-GEIGYAG

~ ~ CLO -

Example l8

- 28 -

1 (Ii *

ti ■ * t i f

206.4 g (0.575 mol) "bis-imide 1", 42.6 g (0.116 mol) tri- (4-aminophenyl) phosphate and 75.0 g (0.20 mol) N, N ^! -Bis- (benzylidene) -diaminodiphenylmethane were cured as in Example 1 to give moldings, the test data of which are given in Table 3.

Example 19

215 grams (0.60 moles) of "bis-imide i", 47 grams (0.237 moles) of 4,4'-diaminodiphenylmethane and 67.5 g (0, S.8 mol) Ν, Ν'-ΒΙε-φεη-zylidene) -diaminodiphenylmethane were cured to moldings as in Example 1, the test data of which are given in Table 3 are.

Comparative example -

According to the French patent specification 1,555 * 564 were 72.0 g (0.20 mol) of "bis-imide I" and 19.8 g (0.10 mol) of 4.4 '· Diaminodiphenylmethane mixed, melted, degassed and potted and for 1.5 hours at Ι4θ, 1.5 hours cured at 160 °, 1.5 hours at 180 ° and 1.5 hours at 200 °. The test data are given in Table 1.

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TABLE 1'

Moldings Flexural strength according to VSM * Impact resistance according to Dimensional stability in the according to 77103 (kg / mm2) VSM 77105 (cmkg / cm ² ) Heat according to ISO / R ** 75 (oc) example 1 11.0 12.5 240 ■ ■ ^: ■ 2 10.5 ' , 7.8. 229 3 13.0 12.6 246 4th 10.3 . 14.3 168; VJi 11.7 11.7 '' 224. '; 6th 9.1 10.9 219 7th 10.1 7.9 228: 8th 9.5 9.5. 215 ■ 9 9.1 7.6 226 10 '12.3 8.6 230 11 13.1 15.7 237 12th 10.6 10.0 227 ■. 13th 12.1 9.8 231 - 14th 11.1 11.9. 220 15 ' 10.7 10.5 222 16 11.7 10.0 .233 Comparison example 9.2 6.9 209

*) VSM = standards of the Association of Swiss Machine Manufacturers · **) ISO / R = norms of the International Standard Organization / Recommendation

TABEL

O IO O

Dielectric dissipation factor
tgS XlO ² at 10 ⁶ Hz after 30 days
Storage in
H ₂ O at 23 ⁰ C Dielectric constant E
at 10 ⁶ Hz after 30 days
Storage in
H ₂ O at .23 ⁰ C Specific passage
against st and .Ω. after 30 days
Storage in
H ₂ O at 23 ⁰ C example 1 Baseline 2.85 Starting
value 4.0 Baseline 5.3.10 ¹⁵ Example 2 1.56 2.33 3.7 4.2 β, 5th IQ ¹⁶ 4.2 .. ΙΟ ¹⁵ Example 3 1.24 0.53 3.8 . 4.3 7,6,10 ^1β 4,4.10 ¹⁵ Example 17 0.27 0.32 3.6 4.0 ^{5,6.10 οβ} 1,2.10 ^1β 0.17 3.5 1.1, ΙΟ ¹⁷

Is) Ca)

TABEL

O CO OO

CD KJ O

17th Dielectric
tg δχΙΟ ² at 50 Loss factor
Hz and ⁰ C Dielectric constant £
at 50 Hz and C. 160 ° C 200 ⁰ C Specific through
input resistance SX at 18th 23 ⁰ C 160 ° C 200 28 23 ° 5 · 3.4 ". '3, 3 2 ^ ⁰ C 16O ⁰ C 200 ⁰ C 19th 0.20 0.28 0, 51 3, 4th • 3.4, 3, 4th ίο ¹⁸ ι, ο.ίο ¹⁸ ■ 10 ¹⁸ example 0.19 0.27 .0, 40 .3, 4th 3.3 3, 3 5, j5.1O 1,2.10 4.0.10 example 0.23 0.28 O, 3, 9.8.1O ¹⁵ 7.3.io ¹⁴ 9, o.io ¹⁵ example

CIBA-GEIGYAG -

Table 1 shows the valuable properties of those produced from the curable mixtures according to the invention Moldings, which compared to the moldings produced according to the French patent 1,555 * 564 are significantly better. The moldings produced from the mixtures according to the invention are particularly notable due to better impact resistance and higher dimensional stability under heat. In addition, these are beneficial Properties of the moldings according to the invention after significantly shorter curing times and without Pressure application reached.

Tables 2 and J5 contain electrical characteristics of the. Moldings produced according to the invention. ' The tables show the very good properties that are under the long permanent influence of water or increased temperature remain largely unchanged.

Example 20

6.50 g of "bis-imide I", 1.45 g of 4.4 ¹ -diaminodiphenylmethane and 2.05 g of N ^ '- bis-CbenzylidenJ-diaminodiphenylmethane were mixed well in a rectangular frame made of 1 mm thick polytetrafluoroethylene (" Teflon ") between two 1 mm thick Teflon layers in a press at 180 ° C and light

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Pressure below 5 atmospheres for 15 minutes to one 1 mm thick molded body, which was further hardened at 200 C for 24 hours. The properties of the obtained Moldings are given in Table 4.

Example 21.

As in Example 20, a mixture was prepared which However, 0.1 g of tert-butyl perbenzoate was added. As in Example 20, this mixture became a shaped body cured, the properties of which are given in Table 4 are.

Example 22

7.16 g "Bis-imide I", 2.12 g N; N ^! -Bis- (furfurylidene) -4,4'-diaminodlphenylmethane and 2.12 g 3.3 * ~ Ώχοη1θΓθ-4.4 ^! Diaminodiphenylmethane were mixed and cured as in Example 20 to give a molded body, the properties of which are given in Table 4.

Example 23

5.68 g of N, N'-m-phenylenebismaleinimide, 1.70 g of terephthaldianil and 1.5δ g of 4.4 ^I- diaminodiphenylmethane were cured in Example 20 to give a shaped body, the properties of which are given in Table 4 . . . ·

409817/1020

Tn IM MC

CIBA-GEiGY AG -, κ Example 24

I ₃ Vo g ^w bis-imide i ", 2.24 g N, N'-bis (benzylidene) -4,4'-diaminodiphenylmethane, 0.46 g 1,6-hexamethylenediamine and 0.35 g pzperazine were xtfie cured in Example 20 to a shaped body, the properties of which are given in Table 4.

Example 25 -

g of N, N'-4, V-diaminodipheny! methane-bis-citraconimide, 1.70 g of terephthal-dianil and 1.58 g of 4,4'-diaminodiphenylraethane were hardened as in Example 20 to give a shaped body , whose properties are given in Table K.

Example 26

3.58 g of "Bis-imld i", 0.99 g of tris (4-aminophenyl) phosphate and 1.12 g of N, N'-BiSt (benzylidene) -4,4'-diaminodiphenylmethane were obtained as in Example 20 Cured to a shaped body, the properties of which are given in Table 4.

The moldings produced in Examples 20-26 were subjected to a thermogravimetric test. The analysis by thermogravimetry was carried out in dry air the device "Recording Vacuum Thermoanalyzer TA-1" from the company Mettler with an initial weight of 50 mg and a heating rate of 2 ° C / minute. With the thermogravimetric

409817/1020

CIBA-GEIGY AG

Analysis will draw a curve as a function of the weight of the sample recorded from the temperature ("thermogravimetric. '. curve") and at the same time the first derivative of this thermogravimetric Curve ('differentiated' thermogravimetric Curve "). The temperature of the maximum rate of evaporation is the point of the greatest slope of the thermogravimetry Curve; at this temperature the differentiated thermogravimetric curve shows a maximum. The weight fraction that corresponds to the area between two minima corresponds to the differentiated thermogravimetric curve is called the fraction. The measurement results of this Test methods are listed in Table 4.

Table 4: Thermogravimetric analysis of the moldings

20th Maximum decomposition 1 2 3 part of the (*) 2 .3 Loss of weight I.
312 shape 21 ting speed about 100 4oo 650 Factions 25.2 73.8 338 body 22nd speed ( ⁰ C) about 110 420 624 ■ 25.7 73.2 333 according to 23 fraction approx. 50 515 600 44.1 53.5 l ° / oo per minute 324 24 about I30 396 596 1 22.8 76.2 at ⁰ C 324 25th about 80 398 610 1.0 29.7 69.1 342 example 26th about 130 427 613 1.1 29.3 70.0 326 about 120 4io 605 2.4 28.0 71.4 1.0 1.2 0.7 0.6

Table 4 shows that the moldings of Examples 20 to

409817/1020

CIBA-GEIGYAG _,

26 do not begin to decompose until above 310 C (weight loss 1 per cent per minute). The first maxima of the decomposition rate are also very high at at least 396 C, the corresponding weight fraction being relatively small at approx. 30%.

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70.01.335

Claims (1)

CfBA-GSfGYAG - 37. ■ " Claims 1. Storage-stable hot-curable mixtures, characterized in that that they contain a) Polyimides of unsaturated dicarboxylic acids of the general formula I. (I) in the A an x-valued, organic residue with ' at least 2 and at most 30 carbon atoms means B for a remainder of the formulas IiiIq Kjtliy UtIo HC \ ^ VC -! ii 'IP H CH ₃ and χ denotes the number 2 or 3, b) polyamines of the formula II or III ) (II) 409817/1020 CIBAGEIGYAG NH JL - ^ iR, - J- NH "T (III) in which in formula II the radical D is a y-valent organic radical having 2 to 40 carbon atoms, and y is an integer from 2 to 4, and in which in formula III the radicals R-, one each by separation of the oxygen atom the resulting divalent hydrocarbon radical of an aldehyde or ketone having 1 to 8 carbon atoms, m is a number from 0.1 to 2, c) Azomethines of the general formulas IV, V or VI N - R ₇ , (IV) R ₂ - C = "Ό ί ³ ί ³ R ₂ -C = NEN = C (V) R ₄ - N "R, = C - Ro - C = N - R / (VI) in which Ra is a hydrogen atom, a linear or branched one aliphatic carbon residue with 409817/1020 CLBA-GEIGY AG j9 up to 12 carbon atoms, a cycloaliphatic ^ or cyclos-lipatic-aliphatic hydrocarbon radical with up to 12 carbon atoms, an aromatic radical with 6-12 carbon atoms, an araliphatic radical Hydrocarbon radical with up to 20 carbon atoms or a heterocyclic or means heterocyclic-aliphatic radical, Ro and R, with the exception of the meaning for a hydrogen atom have the same meaning as R2, where R “together with R” including the two C-atoms bearing substituents also have a cycloaliphatic one Ring system can mean, and E denotes a divalent organic radical having at least 2 and at most 30 carbon atoms, and possibly- d) a curing catalyst. 2. Mixtures according to claim 1, characterized in that they contain a) Poly ~ imides of the formula I, in which A is a radical of the formulas - '. 0-9817 / 1020 CIBA-GEIGY AG -O y- \ _n = 2-8, I) ₁ ■ ° - ^C 6 ^H 5 O = P (ο- ^ ° - ^C 6 ^H 5 O = P S = P | 0- and B denote the vinyl radical, b) di- or tri-primary polyamines of the formula II, V7O rin D means an organic radical with 2 to 40 carbon atoms, and c) Azomethines of the formulas IV or V, in which R ^ a Hydrogen atom means, R- and R, each one 4Ö9817 / 1020 Phenyl radical and E denotes a radical of the .Forme CH, rmein or - (CH) - η = 2-8 means. · 3. Mixtures geraäss claim 1, characterized in that that in the mixture per 1 equivalent of imide group 0.1 to 0.85 equivalents of primary amino group and 0.45 to 0.08 equivalents ^ C ^ N group are included, . where the sum of the equivalents from the primary amino group and ^ C = N group 0.33 to 1.0 equivalents per 1 equivalent imide group. 4. Mixtures according to claim 1, characterized in that that the sum of the equivalents from primary amino group and ,, C = N group 1.0 equivalent per 1 equivalent Imide group. 409817/1020 CIBA-GEIGY AG - 42 - 5. Mixtures according to claim 1, characterized in that that it is a polyimide of the formula Γ NjN '- ^ V-diaminodiphenylmethane-bis-maleimide contain. 6. Mixtures according to claim 1, characterized in that they are a tris-malein- · imid of the formula D = P 0 where D is an oxygen atom or a sulfur atom., contain. 7. Mixtures according to claim 1, characterized in that
that it is a polyimide of the formula I Ν _Λ Ν'-4, V-diaminophenyl ether-bis-maleimide, N, N'-m-phenylene-bis-maleimide or N ^ N '- ^ V-diaminodiphenylmethane-bis-eitracon - imi d contain en. 8. Mixtures according to claim I ₃ characterized.,
that they contain 4,4'-diaminodiphenyl methane or tri- (4-aminophenyl) phosphate as the polyamine of the formula II, 9. Mixtures according to claim I _3, characterized in that 409817/1020 CiBA-GEIGYAG ^ that they are 4,4'-diaminodiphenyl ether as polyamine of formula II, 3,3'-Diehloro - ^, 4'-aiaminodiphenylmethane or Contain hexamethylenediamine. 10. Mixtures according to claim 1, characterized in that they contain N, N'-bis (benzylidene) -hexamethylenediamine or N, N ^f -bis (benzylidene) -p-phenylenediamine as azomethine. 11. Mixtures according to claim 1, characterized in that they contain as azomethine N, N'-bis (benzylidene) -hexanediol-1,6-di- (7-aminopropyl) -etherj N ^ N'-bis (benzylidene) -!, ^ - (Ύ-aminopropyl) -5i5-dimethylhydantoin _i N, N '-Bis- (benzylidene) -ethylenediamine, N, N'-bis- (benzylidene) -4,4'-diaminodiphenyl ether, Ν, Ν' -Bis- (benzylidene) -4,4'-diamino-3 _J 3'-di chlorodipheny! Methane, Ν, Ν '-Bis- (benzylidene) - * p-xylylenediamine, N, N'-bis (furfurylidene) - 4 _J 4'-diaminodiphenylmethane or Terephthaldianil included. 12. Mixtures according to claim 1, characterized in that that they use tert-butyl perbenzoate as a curing catalyst contain. 409817/1020 70.01.335 CIBA-GEIGY AG Process for the production of insoluble and infusible plastic products, characterized in that that he a) Poly-imide-determined unsaturated dicarboxylic acids of the general formula I. - + - N B (D in the A an x-xizertigen, organic residue with means at least 2 and at most 30 carbon atoms, B for a radical of the formulas CH, H-C H-fi. "V CH CH CLL stands, and χ means the number 2 or 3, b) polyamines of the formula II or III D- (NH,), (II) 409817/1020 CIBA-GEIGY AG NH NH (in) m wherein in formula II the radical D is a y-valent organic radical having 2 to 40 carbon atoms and y stands for an integer from 2 to 4, and in which in formula III the radicals R, one obtained by separating off the oxygen atom divalent hydrocarbon radical of a Mean aldehydes or ketones with 1 to 8 carbon atoms, m stands for a number from 0.1 to 2, c) Azomethines of the general formulas IV, V or VI R ₂ - C = N - (IV) R ₂ - C = N - E - N = w - .ν ₂ Rr Rr -N = C- R ₃ -C = N- (V) (VI) in which R _{2 is} a hydrogen atom, a linear or branched aliphatic hydrocarbon radical with up to 12 carbon atoms, a eycloaliphatic 4Ö9817 / 1020 CIBA-GEfGY AG see or cycloaliphatic-aliphatic hydrocarbon remainder with up to 12 carbon atoms, an aromatic residue with 6 - 12 carbon atoms, an araliphatic hydrocarbon radical with up to 20 carbon atoms or a heterocyclic or heterocyclic-aliphatic Rest means Ro and R, with the exception of the meaning for a hydrogen atom, have the same meaning as R2, where Ro together with R ₉ including the carbon atom bearing the two substituents can also mean a cycloaliphatic ring system and E a divalent organic radical with at least 2 and at most 30 carbon atoms, optionally in the presence of a curing catalyst at temperatures between 100 - 280 ⁰ C are reacted together. l4. Process according to claim 1jJ, characterized in that that you can mix it up a) Poly-imides of the formula I, in which A is a radical of Formulas / —Ν / "" v / \ i ³ 7 \ ^v v ptl / \\ <. · "ι— f < '· - VjCI η \ · - ·. 'Vj "'• ^ ^{J ww} CH ₃ A09817 / 1020 = J η = 2-8, 6 5 ro- ( W / 3 and B denotes the vinylene radical, b) di- or tri-primary polyamines of the formula II, wherein D is an organic radical having 2 to 40 carbon atoms, and c) Azomethines of the formulas IV or V, in which F ^ means one hydrogen atom, Ro and Ra each one Phenyl radical and E denotes a radical of the formulas 409817/1020 CIBA-GEIGYAG f y or - (CH ₂ -) - η = 2-8,
means used. 15. The method according to claim 13j, characterized in that one starts from mixtures in which 0.1 to 0.85 equivalents of primary amino group and 0.45 to 0.08 equivalents of ^ -C = N group are contained per 1 equivalent of imide group, where the sum of the equivalents of the primary amino group and ^ C = N-GrUpPe 0.33 to 1.0
Equivalents per 1 equivalent imide group. l6. Process according to claim I5, characterized in that that one starts from mixtures in which the sum of the equivalents of the primary amino group and ^ C = N - group 1.0 equivalent per 1 equivalent imide group. 409817/1020 C (BA-GEIGYAQ 2 {.g 17. The method according to claim 13, characterized in that that the polyimide of the formula I is N, N'-4,4'-diaminodiphenylmethane-bis-maleimide used. _% -l8. Process according to claim IJ, characterized in that the polyimide of the formula I is a tris-maleinimide of the formula where D is an oxygen atom or a sulfur atom, used, 19 «The method according to claim 3, characterized in that that the polyimide of the formula I is N, N'-4,4'-diaminophenyl ether-Ms-maleinimide, N, N'-m-phenylene bismaleimide or N, N'-4,4'-diaminodiphenyl methane biscitraconimide used, . 20. The method according to claim I5, characterized in that that taan as a polyamine of the formula II is 4,4'-diaminodiphenylmethane or tri- (4-aminophenyl) phosphate is used. 4 09817/1020 CIBA-GEIGYAG _ Cj ₀ 21. The method according to claim 1, characterized in that the polyamines of the formula II, 4, V-diaminodiphenyl ether, 3 * 3'-dichloro-4,4 ^! -diaminodiphenylraethane or hexamethylenediamine is used. 22. The method according to claim 13, characterized in that that the azomethine is N, N'-bis (benzylidene) hexamethylenediamine or N, N'-bis (benzylidene) -p-phenylenediamine is used. ..... .. Process according to claim 1, characterized in that the azomethine used is N, N'-bis- (1) enzylidene) -hexanediol 1,6-di- (7-aminopropy 1) -ether, N, N'-bis- (benzylidene) - ^ -13- (7-aminopropyl) -5,5-dimethylhydantoin, Ν, Ν'-bis (benzylidene) ethylenediamine, N, N-bis (benzylidene) - K ₃ 4'-diaminodiphenyl ether, N, N'-bis (benzylidene) -4,4'-diamino-5,3 ^f -dichlorodiphenylmethane, Ν, Ν'-bis (benzylidene) -p-xylylenediamine _i N, N'-bis (furfurylidene) - 4,4'-diamino dipheny! Methane or terephthaldianil is used. 24. The method according to claim 3, characterized in that that the curing catalyst used is tert-butyl perbenzoate used. • 'r PO 3.33 (Sta) Sta / vs ' 409817/1020