CA1069903A - Imidyl-benzene-dicarboxylic and-tricarboxylic acid derivatives - Google Patents

Abstract

Abstract of the Disclosure New imidyl-benzenedicarboxylic and -tricarboxylic acid de-rivatives of the formulae and wherein A denotes a radical of the formula , , , , or

Description

~6~9(:93 The present invention relates to new imidyl-benzene-dicarboxylic and ~tricarboxylic acid.derivati~es and a process for their manufacture.
The new imidyl benzene-dicarboxylic and -tricarboxylic acid derivatives correspond to the formula I
... .
. O .' rl ( I ) A . N- _z .~ \C~
; _ _ n - ~ ` Rl R2 CH2 wherein A denotes a radical of the formula -C = C-, -C - CH2-, .. . . .. .. .. ... . .
~ , ~ , ~ or ~ , R1 and R2 independently of one another denote hydrogen, chlorine or bromine, n denotes the number 1 or 2 and, when n - 1, Z denotes a radical of the for-mula ~ . ` `
: . R30 ~ 4 ., .. ,,, - :

and, when n = 2, Z denotes a radical of the formula ~ OR~
R4 denotes a hydroxyl group3 an unsubstituted or substituted _ 2 ~

. ~ 6~ ~ ~ 3 phenoxy group, an alkoxy group with 1-18 carbon atoms or a -O M+ group, or the twoR4s conjointly denote the -O- grouping and, when R4 represents an unsubstituted or substituted phenoxy group or an alkoxy group wi-th 1~18 carbon atoms, or the two R~s conjointly represent -O-, R3 denotes a chlorine atom, a hydroxyl group, an unsubstituted or substituted phenoxy group, an alkoxy group with 1-18 carbon atoms or a -O M+ group and, when R4 represents a hydroxyl group, R~ denotes a hydroxyl group, an unsubstituted or substituted phenoxy ~roup or an alkoxy group with 1-18 carbon atoms and, when R4 represents a -O-M+ group, R3 denotes a -O M+ group 5 an unsubstituted or substituted phenoxy group or an alkoxy group with 1-18 carbon atoms and M+ denotes an alkali metal cation, a trialkylammonium cation with 3-24, and especially 3-12, carbon atoms or a quaternary ammonium cation.
The new imidyl-benzene-dicarboxylicand -tricarboxylic àcid derivatives can be manu~actured, according to the in~ention, by reacting an amine of the formula II

[ H2N~Z t (II~

in at Ieast the stoichiometric amount with an anhydride of the ~ormula III
....... .. .
o ., ' f~
/ . (III) O
'''''.''' ' ,.

, ~ .

~136~ 3 to give a compound of the formula IV
[ HOOC-A-CO-NH ~ Zl (IV) wherein A and n have the meaning indicated under formula I and, .
when n = 1, Z' denotes a radlcal of the formula R3'0C y ~ C~R4 ~OR4 and9 when n = 2, Z' denotes a radical of the formula ., . ~.

~ COR4' . .. . . . ~ . . .. . .
wherein R4' denotes a hydroxyl group, an unsubstituted phenox~ .
group or a subs-tituted phenoxy group which is free from electro-negative substituents, an alkoxy group with 1-18 carbon atoms or a -O~M+ group, and, when R4' represents a phenoxy or alkoxy group according to the definition, R3' denotes a hydroxyl group, -an unsubstituted phenoxy group or a substituted phenoxy group which is free from electronegative substituents, an alkoxy group .
with 1-18 carbon atoms or a -O-M+ group and, when R4' represents a hydroxyl group, R3' denotes a hydroxyl group or a phenoxy or .
alkoxy group according -to the definition and, when R4' repre-sents a -O M+ group, R3' denotes a -O M+ group or a phenoxy or - .
alkoxy group according to the definition and M+ has the meaning indicated under formula I, subsequently cyclising the compound of the formula IV and optionally con~erting the resulting . . .

, ~6~9~33 compound of the formula I into another derivative, according to the definition, of the formula I.
- Preferably, A represents a radical of the ~ormula and especially a radical o~ the formula -CH=CH-. If R3~ R3', R4 or R4' represent substituted phenoxy groups, the latter are, in particular, phenoxy groups which are substituted by nitro groups or alkyl or alkoxy groups with 1 or 2 carbon atoms or by halogen atoms, above all chlorine or fluorlne, such as the

2-, 3- or 4-nitrophenoxy group, the 2,4- or 3,5-dinitro- ~;
phenoxy group, the 3,5-dichlorophenoxy group, the pentachloro- -phenoxy group or the 2-methyl- or 2~methoxy-phenoxy group.
According to the definition, substituted phenoxy groups R3' and R4' are free from electronegative substituents, such a~ nitro groups or halogen atoms. End products o~ the formula I, wherein R3 and/or R4 denote phenoxy groups which contain electro~egative substituents of this type, are ~appropriately manufactured as indicated further below - ~rom the corresponding anhydrides3 acid anhydrides or acid chloride-anhydrides or by trans-esterification.
Alkoxy groups R3, R3', R4 or R4' can be straight-chain or branched. Examples which may be mentioned are: the methoxy, etho~y, n-propoxy, isopropoxy, n-butoxy, tert.-butoxy, hexyloxy, octoxy,~ decyloxy, dodecyloxy, tetradecyloxy and octadecyloxy group.
If R3, R3', R4 or R4' denote a -O M+ group, M~ represents, .: :;

' .: ~ ' .:

~ 6~ ~ ~ 3 for example, the lithium, sodium, potassium, trimethyl-ammonium, triethylammonium, methyi-diethylammonium, tri-n-octylammonium, benzyltrimethylammonium or tetramethylammonium cation. M~ preferably represents the sodium cation.
Compounds of the formula I wherein A represents -the radical .. ....... . .
and above all the radical -CH=CH- and, when n = 1, Z repres-ents a radical of the formula - .... - - ................................ .

., and, when n = 2, Z represen~s a radical of the formula .

and R~ denotes a chlorine atom or an alkoxy group with 1-12 carbon atoms and especially 1-4 carbon atoms are particularly preferred.
The starting materials of the formulae II and III are known or can be manufactured in a manner which is in itself known.
Appropriately, the free acids, esters according -to -the ~6~ 3 definition or salts, especially the Na salts, are used as the amines and diamines of the ~ormula II. The use of amines or . diamines of the formula II.wherein R3' denotes -OH or an alkoxy group with 1-12, and especially 1-4, carbon atoms and the R49 s denote -OH groups is preferred.
The aminobenzene-dicarboxylic and -tricarboxylic acids o~ the ~ormula II, and their derivatives, can be employed as such or can be manufactured in situ by reducing the correspond-ing nitrobenzene-dicarboxylic or -tricarboxylic acidsg or deri~atives thereof, and used further without.intermediate isolation~ -Examples which may be mentioned of suitable anhydridesof the formula III are: maleic anhydride, itaconic anhydride, chloromaleic anhydride, 2,3-dichloromaleic anhydride 5 2,3-dibromomaleic anhydride, 4- and 2-cyclohexene-1,2-dicarboxylic acid anhydride, 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride (nadic anhydride) and 3,6-endoxo-1~2,3,6-tetrahydro-phthalic anhydride. Nadic anhydride and, above all, maleic anhydride are preferably used. ~. ~
The reaction of the amines of the formula II with the ~ .
anhydrides of the formula III can be carried out in the melt, :
by heating the reactants to temperatures of up to about 150C, or in an aqueous, a~ueous-organic or organic medium, in which case the reaction is appropriately carried out at temperatures be-tween about 0C and 50C, especially between about 15C and 25C, Appropriately, the anhydride of the formula III is - 7 - ~ .

, -~ .. . .. -.. ~ . .. ,", . , , , ; ; -~6~9~3 employed in the stoichiometric amount or in a slight excess over the ~Qine of the formula II, ~or example in an up to about 2~/o molar excess. The ~eaction is advantageously carried out in an organic medium. Organic solvents which can be used are, above all, aprotic organic solvents. Examples of suitable aprotic organic solvents are: optionally chlorinated ali-phatic or aromatic hydrocarbons, such as ben~ene, toluene, methylene chloride, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,2~dichloroethylene and chlorobenzene;
aliphatic and cycloaliphatic ketones, such as acetone, methyl i-b ethyl ketone, cyclopentanone and cyclohexanone; cyclic ethiers, such as tetrahydrofurane, tetrahydropyrane and dioxane;
cyclic amides, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-methyl-E-caprolactam; N,N-dialkylamides of aliphatic monocarboxylic acids with 1-~ carbon atoms in the acid part, such as N,N-dimethylformamide, N,N-dimethylacet-amide, N,N-diethylacetamide and NsN-dimethylmethoxyacetiamide;
alkyi esters of aliphatic monocarboxylic acids with a total o~
2-6 carbon atoms, such as formic acid methyl, ethyl or n-butyl ester or acetic acid methyl, ethyl or n-butyl ester; hexa-methylphosphoric acid triamide (hexametapol~; N,N,N',N'-tetramethylurea; tetrahydrothiophene dioxide (sulpholane);
and dialkylsulphoxides 9 such as dimethylsulphoxide and diethyl-sulphoxide. Mixtures of sol~ents of this type can also be employed. ~ioxane is the preferred solvent.
When the reaction has ended, the amide-acid deriva-tives of the formiula IV are isolated in a customary manner, by , . .

~ .................. . . ~, .; . ... - .... . ........ .
. . . . .

~6g~03 filtration or by stripping off the solvent, and optionally purified, for example by washing with water and/or suitable solvents, such as methanol, dioxane, diethyl ether, methylene chloride and chloroform, or by recrystallisation or extraction with suitable organic solvents, such as ethyl acetate.
Solvent mixtures can also be usedO
However, the amide-acids of the formula IV can also be cyclised direct, without intermedia-te isolation, to give the imidyl compounds of the formula I. The cyclisation of the amide-acids of the formula IV to compounds of the formula I can;~
be carried out, ln a manner which is in itsel~ known, chemi-cally, that is to say using catalysts which are in themselves known for forming imides and9 optionally, anhydrides, and/or using dehydrating agents, and/or by the action of heat~
The cyclisation is generally carried out at tempera-turès between about 40 and 120C, preferably at 70-90C, with the addition of suitable catalyst;s and/or dehydrating agents and optlonally in the presence of` an aprotic organic solventO
- Dehydrating agents which can be used are, above all, anhydrides of aliphatic monocarboxylic acids which have 2-5 carbon atoms and are optionally substituted by halogen atoms or alkyl groups, such as acetic anhydride, propionic anhydrlde, butyric anhydride and valeric anhydride~and trichloro-, tri-- fluoro-, trimethyl-, triethyl- and tri-n-butyl-acetic anhydride.
Acetic anhydride is the pre~erred dehydrating agent.
Catalysts which can be used are, for example, alkaline earth metal salts or alkali metal salts of aromatic mono-`J . _ 9 _ ~ 3 carboxylic acids or of aliphatic monocarboxylic acids with 1-3 -carbon atoms, such as sodium benzoate, sodium salicylate, calcium formate and sodium formate, calcium acetate, magnesium acetate, sodium acetate and potassium acetate and sodium propionate; bases, such as trimethylamine and triethylamine, or nickel salts or nickel complexes, such as nickel 2-acetate or nickel acetylacetonate.
Preferred catalysts are sodium acetate, nickel 2-acetate and triethylamine.
Depending on the nature of the amide-acid of the ~ormula IV which is to be cyclised, it c~n be advantageous additionally to use an aprotic organic solvent, above all benzene or toluene. The cyclisation to compounds of the formula I can also be carried out by the action o~ heat, by heating to temperatures o~ about 40C to 150C. The com-pounds of the formula I obtained after the cyclisation can, if ~-desired - and depending on the nature of the amines of the ~ormula II which have been used - be converted into other derivatives, according to the de~inition, of the formula I in a manner which is in itself known, for example as follows:
free aoids (R~ = -OH) by hydrolysis of compounds of the formula I wherein the twoR4sconjointly form an -O- grouping, acid chlorides (R3 = -Cl) by reaction of compounds of the ~o~mula I wherein R3 = -OH or -O M+ with suitable chlorinating agents, such as thionyl chloride, oxalyl chloride and phosgene, esters (R or R4 = unsubstituted or substituted pheno~y or alkoxy) by reaction of compounds of the ~ormula I wherein R3 =

.... .... .. .

., . . :, , , : -. :, ,.~: . ~ ; , - - , ;

., , . ~. ~ . . . . . . . . .. . . . . .

~69911 3 -Cl or -OH, or the two R4sconjointly = -O-, with corresponding alcohols or by trans-esterification of compounds of the formula I wherein R3 or R4 = unsubstituted or substituted phenoxy or ~;
alkoxy, and salts (R3 or R~ O M+) by reaction of the free acids with corresponding bases, such as NaOH.
Furthermore, it is possible to convert compounds of the formula I wherein A represents -CH=CH- into compounds of the formula I wherein A represents -the group ~ ~ ~ or .. -- -- , . . . .
by an addition reaction with 1,3-butadiene, cyclopentadiene or furane. The addition reaction is appropria-tely carried out in an inert organic solvent of the abovementioned type, for example in benzene or toluene.
The imidylbenzene-dicarboxylic and -tricarboxylic acid derivatives of the formula I are obtained in the form of colour-lçss to slightly- yellowish crystals and can be isolated9 and ``-~`
purified, in the customary manner, for example by extraction -and/or recrystallisation from sultable organic solvents, such as benzene, methanol, glacial acetic acid, ethyl acetate, cyolohexane, dioxane, diethyl ether or methylene chloride or mixtures of such solvents.
Compounds of the formula I wherein Z denotes a radical of the formula ~699~3 ~3''C~C\o o~ ~\

and R3" denotes a hydroxyl group, an unsubstituted or sub- !
stituted phenoxy group or an alkoxy group with 1-18 carbon atoms, and especially 1-12 carbon atoms, are valuable curing agents for optionally modified epoxide resins. The produc-ts or materials cured with these compounds are distinguished by good mechanical~ thermal and/or electrical properties, such as a high heat distortion point and/or a low dielectric loss factor.
The invention thus also relates to-curable mixtures which are suitable for the production of mouldings, impregnated products, coatings, adhesive bonds and the like. These mixtures are characterised in tha-t they contain (a) a poly-epoxide compound and (b) as the curing agent, at least one compound of the formula I, wherein Z has the abovementioned , meaning~and what has been stated under ~ormula I applies in respect of A and n, and (c) optionally at least one vinyl ~oompound.
Curable mixtures which contain, as the curing agent ~(b), at least one compound of the formula I wherein A denotes the radical or, in particular, the radical -CH=CH-, n denotes the number 1 ; - 12 -- ;: . , . .;:.. .. , . ~ : . , . , ;: , . .. : ,. . . . ; .

~[)69903 and Z denotes a radlcal of t~e ~ormula ,. ~0 , in which R3" represents an alkoxy group with 1-12, especially 1-4, carbon atoms are preferred.
When vinyl compounds (c) are also used it is particul-arly advantageous when these vinyl compounds are linked covalently to the epoxide resin by copolymerisation with the unsaturated curing agents (b). ~ ~
- Appropriately, 0.5 - 1.5 mols, preferably about O.9 - ` -1.0 mol, of a curing agent (b) or of a mixture of a curing agent (b) and a vinyl compound (c) are used per 1 equivalent of epoxide group in the polyepoxide compound (a).
Vinyl compounds (c) which can be used are, for example, those of the formula V

C~ (V) Z3 : ~
wherein Zl and Z3 each represent hydrogen, Z represents ~ ~ -hydrogen, chlorine or methyl and Z4 represents hydrogen, ~ ~ ;
methyl, ethyl, chlorine, -CN,~ COOH, -CONH2, phenyl, methyl-phenyl, methoxyphenyl, cyclohexyl, pyridyl, imidazolyl, pyrrolidonylj -COO alkyl wi~h 1-12 carbon atoms in the alkyl part, -COO-phenyl, -COOCH~C~ ~ H29 --COO-alkyl-OH with 1-3 `
carbon atoms in the alkyl part, -OCO-alkyl with 1-4 carbon atoms in the alkyl part, -OCO-phenyl, CO-alkyl with 1-3 carbon , ~ 3 : - .

~ ~9 9 ~ 3 atoms in the alkyl part, alkoxy with 1-6 carbon atoms, ; .
phenoxy 9 -CH=CH2 or ' _~CH=CH2 t or Zl and Z2 each represent hydrogen and Z3 ~nd Z4 conjointly form the grouping ~ ~ O /C~O .
Examples which may be mentioned of vinyl compounds o~
this type are: ethylene, propylene, l-butene, isoprene, 1,4 butadiene, vinyi chloride, vinylidene chloride, acrylic aci.d, methacrylic acid, acrylonitrile, methacry10nitrl1e, chloro~
acrylonitrile, styrene, methylstyrenes which are substitutedin the nucleus, 4-methoxystyrene, vinylcyclohexane, acrylic acid methyl, ethyl, isopropyl, 2-ethylhexyl and phenyl ester and methacrylic acid methyl, ethyl, isopropyl, 2-ethylhexyl and phenyl ester, acetic acid vinyl ester and propionic acid vinyl ~:
ester, acrylic acid 2,3-epoxypropyl ester and methacrylic acid :~
2,3-epoxypropyl ester, benzoic acid vinyl ester, 2-vinyl-pyrldine, 4-vinylpyridine, vinylimidazole, vinylpyrrolidone, methyl vinyl ketone, ethyl vinyl ketone, ethyl vinyl ether, n-butyl vinyl ether and divinylbenzene. ~ :
Mixtures of several vinyl compounds of the formula V
oan also be used.
: Vinyl compounds of the formula V wherein Zl and Z3 each denote hydrogen, Z2 denotes hydrogen or methyl and Z4 denotes -COO-:alkyl with l-lO carbon atoms in the alky~ part, or Zl' Z2 and Z3 each denote hydrogen and Z4 denotes -CN, chlorine, phienyl or -OCOCH3, are pre~erably used, .

~69~3 Polyepoxide compounds a) which can be used are all those which can be cured with anhydride curing agents.
The following may be mentioned in particular: alicyclic poly-epoxides, such as epoxyethyl-3,4~epoxycyclohexane (vinylcyclo- .
hexenediepoxide), limonene diepoxide, dicyclopentadiene diepoxide, bis-(~,4-epoxycyclohexylmethyl3 adipate, 3',4'- ~ -epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3',4'-epoxy 6'-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexane-carboxylate, 3-(3',4'-epoxycyclohexyl)-2,4-dioxaspiro-(5,5)-8,9-epoxyundecane and 3-(glycidyloxy~ethoxyethyl)-2,4-dioxa- Y ~ .
spiro(5,5)-8,9-epoxyundecane; di- or poly-glycidyl ethers of `-~ -polyhydric alcohols, such as 1,4-butanediol, or of polyalkylene glycols, such as polypropylene glycol; di- or poly-glycidyl :
ethers o~ cycloaliphatic polyols, such as 2,2-bis~(4-hydroxy- .
cyclohexyl)-propane; di- or poly-glycidyl ethers o~ poly-hydric phenols, such as resorcinol, bis-(p-hydroxyphe~yl)-methane, 2,2-bis-(p-hydroxyphenyl)-propane (diomethane), 2,2-bis-(4'-hydroxy-3',5'-dibromophenyl)-propane and 1,1,2,2-tetrakis-(p-hydroxyphenyl)-ethane,-or condensation products of phenols and ~ormaldehyde which have been obtained under acid conditions, such as phenol novolacs and cresol novolacs;
and also di- or poly-(~-methylglycidyl) ethers of the above-mentioned polyalcohols and polyphenols; polyglycidyl esters and poly-(~-methylglycidyl) esters of polybasic carboxylic acids, such as ~hthalic acid,~terephthalic acid, tetrahydrophthalic acid and hexahydrophthalic acid; N-glycidyl derivatives of amines, amides and heterocyclic ni-trogen bases, such as N,N-. 15 -~6~903 diglycidylaniline, N,N-diglycidyltoluidinb and N,N,N',N'-tetraglycidyl-bis-(p-aminophenyl)-methane; triglycidyl isocyanurate; N,N'-diglycidylethyleneurea; N,N'-diglycidyl-5,5-dimethylhydantoin, N,N'-diglycidyl-5-isopropyl-hydantoin and N,N'-diglycidyl-5,5-dimethyl-6-isopropyl-5,6-dihydrouracil.
If desired, active diluents, such as, for example, styrene oxide, butyl glycidyl ether, isooctyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and glycidyl esters of synthetic, highly branched aliphatic monocarboxylic acids, which in the main are tertiary, can be added to the -curable mixtures in order to lower the viscosity.
Curing accelerators can also be employed during curing;
such accelerators are, for example, tertiary amines, the salts thereof or quaternary ammonium compounds, for example 2,4,6-tris-(dimethylaminomethyl)-phenol, benzyldimethylamine, 1-methylimidazole, 2-ethyl-4-methyl-imidazole, 4-aminopyridine and triamylammonium phenolate; or alkali metal alcoholates5 such as, for example, sodium hexanetriolate. Curing of the mixtures, according to the invention, of a curing agent (b), ; -~according to the definition,the epoxide resin (a) and, option-ally, a vinyl compound ~c) is appropriately carried out in the temperature range from 20C - 250C, preferabl~ from 100C -220C.
Curing of mixtures which contain a polyepoxide com-pound (a), a curing agent (b) and a vi~yl compound (c) is advantageously carried out in the presence of free radical initiators which are in -themselves known, such as inorganic and ; - 16 -.

. . - - . .. . . . . .

~069~3~3 .
organic peroxides or azo compounds, for example hydrogen peroxide, potassium peroxydisulphate, tert.-butyl hydroperoxide, di-tert.-butyl peroxide, peracetic acid, benzoyl peroxide, diacyl peroxides, cumene hydroperoxide, tert.-butyl perbenzoate, tert -alkyl peroxycar~onates and a,a'-azo-isobutyronitrile.
It is also possible to use redox systems, for example mixtures of peroxides, such as hydrogen peroxide, and a reducing agent, such as divalent iron ions, in place of the initiators mentioned. The free radical initiators and redox systems are generally employed in amounts of 0.01 to 5% by weight, prefer-ably 0.01 to 1.5~o by weight, based on the total weight of the curing agent mixture.
It is also possible, in a known manner, to carry out the curing in two or more stages, the first curing stage being carried out a~ a relatively low temperature and the post-curlng being carried ou-t at a relatively high temperature.
If desired, curing can also be carried out in 2 stages in such a way that the curing reaction is ~irst discontinued prematurely or the first stage is carried out at a slightly elevated temperature, in which case a curable precondensate which is still fusible and/or soluble ~s~alled "B stage") is obtained from the epoxide component a), the curing agent b) and, optionally, the vinyl compound c). A precondensate of this type can be used, for example, to manufacture "prepregs", moulding compositions or; in particular, sintering powders.
- As used here, the expression "curing" denotes the con-version of the soluble polyepoxides, which are either liquid or ' _ 17 -;, .'., ', ~65~9~)3 fusible, into solid, insoluble and infusi~le three-dimensionally crosslinked products and materials and, in particular, this conversion is as a rule effected with simul- :
taneous shaping to give shaped articles 9 such as castings, compression mouldings and laminates, or to produce impregnated products, coatings, lacquer films or adhesive bonds.
The curable mixtures according to the invention can also contain suitable plasticisers, such as dibutyl phthalate, ~:
dioctyl phthalate or tricresyl phosphate.
- Furthermore, extenders, fillers and reinforcing agents, such as, for example, coal tar, bitumen, textile fibres, glass fibres, asbestos fibres, boron fibres, carbon fibres, mineral silicates, mica, ground quartz, titanium dioxide, hydrated aluminium oxide, bentonites, kaolin, silica aerogel or metal powders, such as aluminium powder or iron powder, and also pigments and dyestuffs, such as carbon black, coloured oxide pigments, titanium dioxide and the like~ can be added to the curable mixtures according to the invention, in any desired ::
phase prior to curing. Fur~hermore, other customary addi- ~.
tives, for example flameproofing agents, such as antimony tri-oxide, thixotropic agents or flow control agents, such as silicones, waxes or stearates (some of which are also used as mould release agents) can also be added to the curable mixtures.
The manufacture of the curable mixtures according to the invention can be carried out in the customary manner with the aid of known mixing equipment (stirrers, kneaders, roll mills and the like).

~6,~9903 The curable epoxide resin mixtures according to the invention are employed, above all, in the fields of surface protection, electrical englneering and laminating processes and in the building trade. They can be used, in the un~illed or ~illed state, in a formulation which in each case is suited to the particular application, for example as paints or lacquers, as moulding compositions, dipping resins, casting resins, injection moulding formulations, impregnating resins and adhesives and as tool resins, laminating resins, sealing compositions and surface fillers, floor covering compositions and binders for mineral aggregates.
The following epoxide resin was used for the manu-facture of curable mixtures, which is de~cribed in the application examples: `Epoxide resin A ~ ` An epoxide resin (industrial product) which is liquid at room temperature? has an epoxide content of 5.12 - 5.54 epoxide equivalents/kg and was manufactured by a condensation reaction of 2,2-bis-(p-hydroxyphenyl)-propane with a stoi- s chiometric excess of epichlorohydrin in the presence of alkali, and whiGh in the main consists of the monomeric diglycidyl ether of the formula C~2~C~-C~I2-C ~ ~- ~ 0~ 2-~H f~H2 0 CH3 ~~``
.. . .. . . . .. . . . .
Viscosity (Hoeppler) at 25C: 9,000 - 13,000 cP.

~69~6~3 In order to determine the mechanical properties of the curable mixtures described in the examples which follow, 4 mm thick sheets were man~factured. The test pieces for deter- ;
mination of the heat distortion point according to IS0/R 75 (DIN ~3,~61) and the flexural strength and the deflection according to VSM 77,103 were machined from the sheets.
Sheets 1 mm and 2 mm thick were manufac-tured in order to determine the electrical properties (dielectric loss factor according to DIN 53,483 and the di-electric constant according to DIN 53,483).
The imidyl derivatives, according to the invention, of ~he formula I are suitable for the manufacture of crosslinkable polymers and of polymers which may already be partly cross-linked, especially for the manufacture of polycondensation products, by reacting them in a manner which is in itself known with substantially stoichiometric amounts of diamines, diols or aminoalcohols, or derivatives thereof, and optionally in the presence of further di-, tri- or tetra-carboxylic acid derivatives, or functional derivatives thereof.
Crosslinkable polymers can also be obtained by homo-polymerisation of compounds of the formula I or by copolymerisa-tion of compounds of the formula I with vinyl comonomers, such as vinyl chloride, vinylidene chloride, vinyl acetate, styrene and derivatives thereof, methacrylic acid derivatives, acrylo-nitrile or divinylbenzene. - -By suitable choice of the comonomers or of the poly-condensation components it is possible to manufacture polymers _ 20 -.

~699~3 which have any desired number, and a statistical distribution, of the crosslinkable or crosslinked groups and to convert these polymers into polymers which have a degree of cross-lînking suited to the particular application. The polymers obtained are distinguished by good processability and, above all, by good solubility in the customary organic solvents and good fusibility and are suitable for the manufacture of shaped articles of very diverse types, for example fibres, films (thin or thick) and compression mouldings.
A. ~ L~
Example 1 ~, .. . .
,., ., . . , . , .. , , ,, , .; , .. . .
~OOH COOH ~~ -~3 H~03(25~ Pd~ ,, ~OOH
21~o2 . 02N NO ca~ LystH2N NH2 O
ll ~OOH
,~C . ' ' ' COO~
~ ~ ) , ~ . ,~ ~ , ; B HOOC-C~=CH-CO-~1 ~ NH-CO-C~=C,Ii-COOX

I-bo ~ acetic anhydride ~

. 0~0 O~=fO ~
- ,. .
813 g (3.59 mols) of 3,5-dinitro-o--toluic acid and 80250 ml of 25% strength nitric acid are heated to 150C for 5 hours in an autoclave. After cooling the reaction mixture to '' '' ' ' .~ " "''' '' ',',"' ' '' ' '' ' .',; ' '" '.' ,' ' ' : ' ''' ': ' ' ' '" ' ~L~6~9(~3 25C, excess 3,5-dinitro-o-toluic acid is filtered off.
The filtrate is concentrated to dryness at 50C in a rotary evaporator, the residue is dried for 12 hours at 120C/100 mm Hg and then boiled in 2,700 ml of benzene for 3 hours, whilst stirring, and, finally, the mixture is filtered hot. After drying the reaction product for 36 hours at 100C/100 mm Hg, 495 g of 3,5-dinitrophthalic acid (53.8% of theory based on the 3,5 dinitro-o toluic acid employed and 86.40/o of theory when the excess 3,5-dinitro-o~toluic acid, wh~h is recovered, -~
".
is taken into account) are obtained.
76.8 g (0.33 mol) of 3,5-dinitroph-thalic acid are hydrogenated at 30C, in 2,400 ml o~ dioxane, in the presence of 8 g of a palladium-on-charcoal catalyst containing 5% by weight of palladium. The reaction solution is ~iltered and 91.2 g (0.93 mol) o~ maleic anhydride are then added to the ~iltrate and the mixture is stirred ~or 12 hours at 20-25C
and finally is concentrated to dryness at 50C in a rotary evaporator. The residue is first extracted with twice 400 ml o~ hot ethyl acetate and then dried for 12 hours at 70C/100 mm Hg~ -74.5 g (63.50/o of theory) o~ 395-bis-maleamidyl-phthalic acid are obtained.
- ~ 23.5 g (o.06 mol)~of this 3~5-bis-maleamidyl-phthalic acid are mixed wi~h 1.14 g of anhydrous sodium acetate and 96 ml of acetic anhydride~and the mixture is heated to 80C for 35 minutes. m e resulting solution is evaporated to dryness and the residue is after-dried at 60C/0.1 mm Hg. m e resi-due is extracted with three times 200 ml o~ ethyl acetate.
-~ , .

``,', ''' ' , ' ,`": ' '" ' `'',' ` '.'.,'.,"'~, '.' ' ., , :`' ,. . , ': '.,. `' ' , , , `"-:: .
': . .' , , ,' , ~ ' ' . . . ~ : ' ~ :, -, . , ,;,, ., , .; , , , ` ',, , ' , :

~ ;99(~3 The extracts are combined and filtered through 2 g of animal charcoal, the filtrate is evaporated to half its volume and 500 ml of cyclohexane are then added. The reaction product which has crystallised out is filtered of~ and dried for 12 hours a-t 80C/O.1 mm Hg. 12 g (59~14% of theory) o~ crystal-line 3,5-bis-(maleimidyl)-phthalic anhydride are obtained;
melting point 246-247C (with decomposition).
Analysis for C16H6N207 (molecular weight 338.24):
calculated C 56.82% H 1.79% N 8.28%
found C 56.70/ H 2.00% N 8.10%
~ .
. . . .
~ CO\ HN03/H2s042~ ~ 00~ Pd/C

HOO ~ CO - HOO ~ COOH
.. . ..
O
H2N ~ OOH ~HOOC-C~--CH-COi~ff ~ COOH
1 I Y ~
HOOC~ ~~ ~OOH ~~ . ~OOC~--COOH
~, O - ' '^, o Na acetate CO N ~CO C~N~CO~
acetic a~llydride ~OOC CO ClOC ~ cof ... . . .. . . .
96 g (O.5 mol) of trimellitic anhydride in 1,360 ml of H2S04 (97% strength) and 680 ml of 100% strength HN03 are heated at 97C for 19 hours. The reaction solution is then poured onto 2,000 g of ice and the mixture is stirred for 2 hours at -5C. The 5-nitro--trimellitic acid which has crystallised out is dissolved in 125 ml of hot water and the ~ .

-" , ;' , ' ' , ' ;:.' ' ' ',:, ' '., ' ' . ,: .;' ' , '; .;; ' ';: ' . ` "' ': ' , ':`

solution is rendered basic (pH 9) wi-th 30/0 strength aqueous sodium hydroxide solution and,finally acidified to pH 1 with concentrated hydrochloric acid~ The reaction solution is then evaporated to dryness and the residue is extracted with twice 400 ml of dioxane. The extrac-ts are combined and evaporated to dryness, the residue is boiled with 120 ml of benzene, the mixture is filtered and the product is dried.
66 g (51.7% of theory) of 5-nitro-trimellitic acid are obtainedO
102 g (0.4 mol) of this 5-nitro-trimellitic acid are hydrogenated at 30C in 1,000 ml of dioxane in the presence of 10 g of a palladium-on-charcoal catalyst containing 5% by weight of palladium. The reaction solution is filtered and 46.8 g (0.48 mol) of maleic anhydride are then added to the filtrate. The reaction mixture is left to stand at room temperature (20-25C) for 12 hours and then evaporated to dryness at 60C in a rotary evaporatorr The residue is twice heated to the boil with? in each case, 400 ml of e-thyl &cetate, whilst stirring, and is then filtered of~ and dried at 80C/100 mm Hg for 24 hours. 105 g (81.3% of theory) of ~ -5-maleamidyl-trimellitic acid are obtained.
32.3 g (0.1 mol) of the 5-maleamidyl-trimellitic acid are mixed with 1.6 g of anhydrous sodium acetate and 83 ml of acetic anhydride and the mixtùre is heated to 80C for 30 minutes. The resulting solution is evaporated to dryness and the residue is after-dried at 50C/0.05 mm Hg. 200 ml of -thionyl chloride are added to the residue and the mixture is heated to 80C for 2.5 hours. The reaction mix~ure is then .
;~ - 2~ -.......... , . ~.. . , - . .... ,. , -.. ........ ~ .. ...
: : :: . .. .. . .. , . .. .. . . ,,, ; . ..

., :, ~ .. ., . . ,,. , :, . . . .

~ . . , ; . , : -.; :. .:. . :: ,.: , ~L~699~3 concentrated to dryness,. 150 ml of benzene are added to the residue, the mixture is filtered and the filtrate is evaporated and, finally~ the residue is dried at 80C/O.1 mm Hg. 50 ml of benzene are added to the residue and the mixture is stirred intensively ~or 4 hours at 20-25C. A crystal slurry forms and is filtered and the crystals are then washed with 20 ml of a 1:3 mixture by volume of cyclohexane and benzene and ~inally dried for 12 hours at 80C/O.1 mm Hg. 18.31 g (600/o of theory) of crystalline 5-maleimidyl-trimellitic anhydride-chloride are obtained; melting point 143-144C.
Analysis for C13H14N06Cl (molecular weight 305.61):
calculated C 51.09% H 1.32% N 4.58%
found C 51.09% H 1.44% N 4.57%-. ~.
Example 3 ~:
.. . .... . . . ...... .. .. .. .
Q2N~,~ ~O H~ 02N ~,~COOH /C H2N~ ~CH
ClOC CO 2 H5C2C COOH H C OOC~COOH

... .... .. .. . ... ..

~ ¢ b : HOOC_CH=CH-CONH OOOH
: . ~o~ .. . ~ ~ . acetic-anhydride - H~C2ooo~ ~` COOH Na.acetate :
..
- D~
G`~O

-- - - -- - - . ... .. . ~ . . . . . .

. . .

~L~6~9~3 102 g (0.4 mol) o~ 5-nitro-trimellitic acid are dis-solved in 150 ml of ace-tic anhydride at 130-1~0C. The resulting solution is evaporated to dryness. 280 ml o~ ¦
benzene are added to the residue, the mixture is stirred for 12 hours and filtered and the product is dried at 60C in a drying cabinet. 85.7 g (78.5% of theory) of 5-ni-tro-tri- I~`
mellitic anhydride are obtained; melting point 232Co 85. 36 g (0.36 mol) o~ 5-nitro~trimellitic anhydride are suspended in 200 ml o~ benzene and 52.4 ml (0.72 mol) of thionyl chloride and 1 ml o~ N,N-dimet~ylformamide are added.
The reaction mixture is heated until a clear solution has formed (about 60 minutes). The reaction mixture is then cooled to about 15C, whereupon 5-nitro-trimellitic anhydride-chloride crystallises out. This is filtered of~, washed with 60 ml o~ cyclohexane and dried over phosphorus pentoxide at 50C in a drylng cabinet~ 77 g (83.5/ o~ theory) of 5-nitro-trimellitic anh~dride~chloride are obtained; melting point 90-91C.
61.33 g (0.24 mol) of 5-nitro-trimellitic anhydride- ~--chloride are dissolved in 120 ml of dioxane and 13~94 ml (0.24 mol) o~ ethanol are added, whilst stirrirlg. The reac-tion mixture is stirred at 25C for 12 hours, then heated to -~ 80C for 1 hour and ~inally evaporated to dryness.
The residue is dissolved in 180 ml o~ dioxane and 100 ml of water are added dropwise and a~ter one hour the mix-ture is evaporated to dryness. The resulting residue is ~inely suspended in 100 ml of benzene, the suspension is . .
.. . : .... . , .. , .. , , . . , ".,; .. ,. . , .; , , ,; .... . ...

- -, ., ,, , : .. : ., .. :: .. : . .. - . " , .. . ,:. ~. : . . .: . . .

,. , .: :, : ` :. :. :: :, ~,:~' :`' :'~ ,';. :. ,::.:, : :; ::

~6~903 filtered and the product is dried at 80C in a drying cabinet. 60.5 g (89% of theory) of 5-nitro-trimellitic acid ethyl ester are obtained; melting point 189-191C. -- 65.13 g (0.23 mol~ of 5-nitro-trimellitic acid ethyl ester are dissolved in 150 ml of dioxane and hydrogenated at 30C in the presence of 6.5 g of a palladium-on-charcoal catalyst containing 5% by weight of Pd. The reaction solu-tion is filtered, 27 g of maleic anhydride are then added to -~
the filtrate and the mixture is left to stand for 12 hours at 20-25C. The solution is then evapora-ted at 40~60C and 250 ml of diethyl ether are added to the oily residue, whilst s-tirring. 5-Maleamidyl-trimellitic acid ethyl ester, which separates out as a fine white precipitateg is filtered off and dried at 50C in a drying cabinet. 76.7 g (95/ of theory) of the said ester are obtained; melting point 142-14l~C.
58 g (0.165 mol) of 5-maleamidyl-trimellitic acid ethyl ester are introduced slowly, in the course of 15 minutes, at 80C into a mixture of 65 ml of acetic anhydride and 14.5 g of sodiùm acetate~ The reaction mixture is stirred at this s temperature fDr 3 hours and then concentrated to dryness and the residue is extracted with three times 200 ml of toluene.
The combined toluene extracts are evaporated to dryness, finally at 50C/0.2 mm Hg. `The solid residue is dissolved in 100 ml of hot toluene and the solution is filtered. m e 5-maleimidyl-trimellitic anhydride-ethyl ester, which has crystallised out after the solution has cooled, is filtered off and dried at 70C in a drying cabinet/ 39.6 g (600/o of , , ' . .,,., ;., ! .-: ~'' , ',., ;'" !"

~06~9~3 theory) of 5-maleimidyl-trimellitic anhydride-ethyl ester with a melting point of 178-179C are ob-tained.
Analysis ~or C15HgN07 (molecular weight 315.24?:
calculated: C 5'7.14% H 2.88~/o N 4O440/o found: C 56.76% H 3.03% N 4.35%
~ ' . .
.
/'b ~/
,` O N~,CO~

CH~3 ( CH2 ) 11C .,, I
~ 1.11 g (0.2 mol) of 5-nitro-trimellitic anhydride-chloride are dissolved in 100 ml o~ dioxane. A solution o~
37.27 g (0.2 mol) of n-dodecanol in 80 ml of dioxane is then added dropwise and the reaction mixture is heated to 80C for 2~ hours. The reaction mixture is then evaporated to dry-ness, the residue is again dissolved in 150 ml of dioxane and 10 ml o~ water are added dropwise, whilst stirring. After 1 hour the reactlon solution is again e~aporated to dryness and 80 ml of benzene are added to the residue. After i-stirring for 12 hours, the resulting fine suspension is filtered and the product is dried at 70C in a drying cabinet.
76 g ~90% of theory) of 5-nitro-trimellitic acid dodecyl ester are obtained; melting point 148C.
78.06 g ~0.1843 mol) of 5-nitro-trimellitic acid dodecyl ester are dissolved in 250 ml of dioxane and hydrogenated at 25C in the presence of 8 g of a palladiu~-on-charcoal ca-talyst containing 5% by weight of Pd. Thé
.

., , , . .. ; ,. :-, .: , .:: ;: . . -: : .. : : . . ,, , : -.. ~ . , .... . , ;:: ; .. : :. ... .;.: :. ,: : . ~. ,;, : : :. . , , , . ; . . . .

~,~G99~3 :
catalyst is removed by filtration. 22 g of maleic anhydride are added to the clear reaction solution and the mixture is stirred for 12 hours at 20-25C. After distilling off the dioxane at 40-60~C, an oily residue is obtained and 200 ml of diethyl ether are added to this. The resulting white sus-pension is filtered and the product is dried at 50C in a drying cabinet. 63 g (69.5% of theory) of 5-maleamidyl- ¦, trimelli-tic acid dodecyl ester are obtained; mel~ing point 133C. `~
61.44 g (0.125 mol) of 5-maleamidyl-trimellitic acid dodecyl ester are introduced in portions, in the course of 15 ;~
minutes, whilst stirring, into a suspension, whlch has been heated to 80C, of 8.3 g of anhydrous sodium acetate in 50 ml of acetic anhydride.
The reaction mixture is subsequently stirred for a further 30 minutes at the same temperature and then evaporated to dryness~ The residue is extracted with twice 250 ml of dioxane. The combined extracts are evaporated and 200 ml of diethyl ether are added to the oily residue, ~hilst stirring.
A fine crystalline suspension is formed, this is filtered and the product is dried at 50C in a drying cabinet. 23.5 g (41% of theory) of 5-maleimidyl-trimellltic anhydride-dodecyl ester are obtained; melting point 86C.
Analysis for C25H29N7 (moleCular weig 55 5 ) calculated: C 65.920/o H 6.42% N 3.07%
found: C 65.64% H 6.560io N 3.07% .

:

, . , . ,: . .. ., ..... .. -,. . - . . ., .. : , .-~1699G13 ` .
~\

n'H9'4 In accordance with the procedure described in Example 3, 5-nitro-trimellitic anhydride-chloride is reacted with the stoichiome-tric amount o~ n-butyl alcohol. After further reaction as described in Example 3, 5-maleimidyl-trimellitic anhydride-n-butyl ester is obtained in the ~orm of a very ~ -viscous oil.
Analysis for C17H13N07 (molecular weight 343.29):
calculated: C 59.480/o H 3.82% N 4.08% .
~ound: C 59.37% H 3.71% N 3.84%.
IR ~pectrum in dioxane: 1850 cm 1, 1790 cm 1 (-C0-0-C0-) and 1730 cm 1, (-C0-N-C0-).
NMR spectrum ~ = 7~35 ppm . - - .

~ ( H X Co~N )'`~` ~
~. ; . . . .
~ Example 6 :
.
' ~ ~ CO :~> ~CO~ ~O, n.H9c4ooc CO n.H,gC400C~ ~0' .. . ~
7.33 g (0.213 mol) of the 5-maleimidyl-trimellitic .

, ! ., . , . .. ; , , ... .: .,. " ;. , ' : '; ' ::: ` .; .' : . :., . . . , ., : : , , ., : .~. , , .. t ~1~6~903~

anhydride-n-butyl ester prepared according to Example 5 are dissolved in 25 ml of toluene. 1.552 g (0.0235 mol) of freshly distilled cyclopentadiene are then added. After leaving the reaction mixture to stand for 12 hours at 25C 7 the solvent is evaporated and -the oily residue is dried for 5 hours at 80C/0.2 mm Hg.
8.72 g (quantitative yield) of 5-endomethylenetetra-hydrophthalimidyl-trimellitic 1,2-anhydride-4-n-butyl ester are obtained in the form of a very viscous oil~
Analysis for C22HlgN07 (molecular weight 409.37): -calculated: C 64.54% H 4.67~o N 3.42%
found: C 64.04% H 4.86% N ~.26%.
B) _Application Examples Example I
1.44 g of epoxide resin A (epoxide content 5.20 epoxide equivalents/kg) and 2 25 g of the 335-bis-(maleimidyl)-phthalic anhydride prepared according to Example 1 (corres-ponding to 0.9 mol of the anhydride per 1 equivalent of epoxide groups) are mixed and the mixture is warmed to 120C.
The mixture is initially stirred vigorously and then kept at 120C for 40 minutes. After cooling, the mixture is finely powdered, introduced into a compression mould for circular discs, which has been prewarmed to 185C, and moulded by the compression process at 185C for 30 minutes under 225 kg/cm2.
Well consolidated, transparent mouldings are obtained and are post-cured ~in an oven for 3 hours at 150C and for 5 hours at 220C; dielectric loss factor Tg o of the mouldings , .

.

, ~069~3~3 according to DIN 5~,483 at 180C (50 Hz) = 0~018; dielectric constant ~ according to DIN 53,483 at 180C = 3.8.
Exam~le II
7.68 g of epoxide resin A (epoxide content 5~20 epoxide equivalents/kg) and 11.35 g of the 5-maleimidyl-trimellitic 1,2-anhydride-4-ethyl ester prepared according to Example 3 (corresponding to 0.9 mol of the anhydride per 1 equivalent of epoxide groups) are mixed and the mixture is warmed to 165C for 10 minutes, whilst stirring. A clear solution is formed and, in order to produce 4 mm thick sheets, is cast into an aluminium mould, which has been prewarmed to 150C. Curing is effected in a circulating air oven, first for ~ hours at 150C and then ~or 5 hours at 220C. Transparent, bubble-free castings are obtained;
heat distortion point of the castings according to IS0/R 75 (DIN 53,461) = 194C; flexural strength according to VSM
77,103 = 48 N/mm2; deflection according to VSM 77,103 = 2 mm.
~ ' 4080 g of epoxide resin A (epoxide content 5.20 epoxide equivalents/kg) and 10.25 g of the 5-maleimidyl-trimellitic 1,2-anhydride-4-lauryl ester prepared according to Example 4 [corresponding to 0.9 mol o~ the an~ydride per 1 equivalent of epoxide groups) are mixed and -the mixture is warmed to 100C for 20 minutés, whilst stirring. A clear solution is formed and is processed according to the procedure described in Example II to give transparent, bubble-free castings; -heat distortion point of the castings according to '.

,, . .,, ., ,. ., ,, , ,- : :,: :;: ! ! : ' ' ~L~69~q33 :~

ISO/R 75 (DIN 53,461) = 132C; flexural strength according to V';M 77,103 = 57 N/mm2; deflection according to VSM 77,103 =
4 mm [ISO/R = Internationai Standards Organisation/
Recommendations; VSM = Verein Schweizerischer M~schinen-industrieller (Association of Swiss Machine Industrialists)].
Example IV
1.92 g of epoxide resin A (epoxide content 5.20 epoxide ~quivalents/kg) and 2.83 g of the 5-maleimid~
trimellitic 1,2-anhydride-4 ethyl ester prepared according to Example 3 (corresponding to 0.9 mol of the anhydride per 1 e~uivalent o~ epoxide groups) are mixed and the mixture is wa~ned to 110C. - The mixture is initially stirred vigorously and then kept at 110C for 15 minutes. After cooling, the mixture is finely powdered and sieved. The powder is intro-duced into a compression mould for circular discs, which has been prewarmed to 220C, and moul~ed by the compression process at 220C for 25 minutes under 330 kg/cm2. Well consolidated, transparent mouldings are obtained and are post-cured for 5 hours at 220C in an oven. m e ~ielectric loss P
factor Tg ~3 ~according to DIN 53,483, of these mouldings is 0.009 at 180C (50 Hz) and the dielectric constant ~ according to DIN 53,483 at 180C (50 Hz) = 306 tDIN = Deutsche Industrie Norm ~German Industrial Standard))~
Example V
7.931 g (0.040 mol) of 4,4'-diaminodiphenylmethane are -dissolved in 160 ml of anhydrous N,N-dimethylacetamide (DMA) under a nitrogen atmosphere in a sulphonation flask. This 1 '-', . , " , ". . , ~ , ,,, ., . ,; " , . . .

: ' :: , ' ' , . ,: ,: : , ' ' - ' ' '.' , .,' ' ': ~,.. ~''''. i: ',::::`'' 'i:' : . . : ; , . .

t ~6996~3 solution is cooled to -15C to -20C. A mixture of 6.738 g (0.032 mol) of trimellitic anhydride-chloride and 2.445 g (0.008 mol) of the 5-maleimidyl-trimellitic anhydride-chloride prepared according to Example 2, in the solid form, is then added in portions, whilst stirring, at such a rate that the temperature does not exceed -15C. When the addition is complete, the solution is stirred for a further 1 hour at 20 -25C- i Part of the resulting polymer solution is cast onto an aluminium foil and heated as follows: 30 minutbs each at 70C/20' mm Hg, 90C/20 mm Hg, 110C/20 mm Hg, 130C/20 mm Hg and 150C/20 mm Hg, 1 hour at 180C/10 1 mm Hg and 1 hour at 200C/10 1 mm Hg. A clear, mechanically strong coating of the crosslinked polyamide~imide is obtained. A transparent, flexible film of good mechanical strength is obtained by dis-solving off the aluminium foil with dllute hydrochloric acid.
Example VI

3.056 g (0.01 mol) of 5-maleimidyl-trimellitic anhydride-chloride are added, in portions, whilst stirring and under a nitrogen atmosphere at -15C, to a solution of 2.182 g (0.02 mol) of 3-aminophenol in 30 ml of anhydrous DMA and the mixture is stirred for a further 30 minutes. 2.03 g (0.01 mol) of isophthalic acid dichloride in the solid form are then added at the same temperature, the reaction mixture is stirred for 30 minutes and 3.033 g (0.03 mol) of triethylamine are then added dropwise. The cooling bath is removed and the reaction mixture is stirred for 2 hours at 20-25C. The ,, . . ., . , ..... , . ;, . , ; ,, . , : ~ .;.. . . . . .. ,.,. ; , :

'' ': ' ' "'' ,, :, ' , '''.': '~'','".. :: '',.. " ' " ''.' '. '';' ', ."., ,' . :`

~L069~03 triethylamine hydrochloride which has precipitated out is then filtered o~f. The resulting polymer solution is cast onto an aluminium foil and heated as described in Example V. A
transparent coating of the crosslinked polyester-amide-imide is obtained~
Example VII
7~80 g o~ epoxide resin A (epoxide content 5013 epoxide equivalents/kg) and 12.36 g of the 5-maleimidyl-trimellitic 1,2-anhydride-4-n-butyl ester prepared according to Example 5 (corresponding to O.g mol of the anhydride per 1 ~ ;
equivalent of epoxide groups) are mixed and the mixture is warmed to 100C for 15 minutes, whilst stirring. 1.15 g (0.012 mol) of styrene and 1 drop of di-tert.-butyl peroxide are added to the resulting clear solution and the mixture is poured into an aluminium mould for sheets, which has been pre-warmed to 120C. Curing is effected in a circulat-ing air oven, first ~or 3 hours at 120C and then for 13 hours at 160C. Transparent, bubble-free castings are obtained. Dielectric loss ~actor Tg ~, according to DIN
53,483, of the castings at 180 C = 0.0144; dielectric constant ~ according to DIN 53,483 at 180C = 4.4.
Example VIII
3.90 g of epoxlde resin A (epoxide content 5.13 epoxide equivalents/kg) and 7.37 g of the 6-endomethylenetetrahydro-phthalimidyl-trimellitic anhydride-4-n-butyl ester prepared ~ -according to Example 5 (corresponding to 0.9 mol of the anhydride per 1 equivalent of epoxide groups) are mixed and the -- 35 -~
, - ',' ; 1, : '' , .
, ;99~3 mixture is warmed to 120C ~or 10 minutes, whilst stirring.
In order to produce 2 mm thick sheets, the resulting clear solution is poured into an,aluminium mould, which has been warmed to 150C, and cured as described in Application ' Exam~le II. A transparentJ bubble-free casting is obtained. .~'-Dielectric loss factor Tg ~, according to DIN 53,483~ of the castin~sat 180C = 0.0188; dielectric constant ~ according to DIN 53,483 at 180C = 4.0~

, . . ' , . :::

., ' ', . I :.
!
~ - . . ...

, . . , .

~ ~ .

- .

, ~
. ~ . ~ .
., .. .

I' ' .. , ,, . ,., .,.. , ,. . ....... .... ~:
. . .. , . , .. ,., .. .. . . -, .. ., .... .. ` ; , . .. , , , .i . ; ~ ~ ; -, . . ...... .- . . ,........ . i. .; . .; . ..... .. .... .... . ........ ....... .
.. ...... ....... ... ., ..... .,. ..,.......... ..... ... , .. ,, ,.. ..~
.i, . , . . ", , " , . .. , .. ., . . , . .. .i . i ... ... , .,,,, ., , ,, ,, ,, ,, , ;,. ..
, . , ... .~ . ...... . .. . ...... ,......... ; ,.......... . ........ . i~ .. - . . .. .. ..
., .... ~. . . .. , . . . . .. .. ... . .. . . . . ..... . -. . . , , ,. ~ ...
, , .... ..... , . .. , .. ,. .. . .... , .. .... . - ~. .. .,. . , ,.. , - . . ..

Claims (11)

What we claim is:

1. An imidyl-benzene-dicarboxylic or -tricarboxylic acid derivative of formula I

(I) wherein A denotes a radical of the formula , , , , or , R1 and R2 independently of one another denote hydrogen, chlorine or bromine, n denotes the number 1 or 2 and, when n = 1, Z denotes a radical of the formula and, when n = 2, Z denotes a radical of the formula , R4 denotes a hydroxyl, phenoxy, phenoxy substituted by nitro, by alkyl of 1 to 2 carbon atoms, by alkoxy of 1 to 2 carbon atoms or by halogen, alkoxy with 1-18 carbon atoms or a group -O-M+, in which M+ denotes an alkali metal cation, a trialkylammonium cation with 3-24 carbon atoms or a qua-ternary ammonium cation, or the two R4's conjointly denote the -O- grouping; and, when R4 represents phenoxy, substi-tuted phenoxy or alkoxy as defined above, or the two R4's conjointly represent -O-, R3 denotes chlorine, hydroxyl, phenoxy, phenoxy substituted by nitro, by alkyl of 1 to 2 carbon atoms, by alkoxy of 1 to 2 carbon atoms or by ha-logen, alkoxy with 1-18 carbon atoms or a group -O-M+; and, when R4 represents hydroxyl, R3 denotes hydroxyl, phenoxy, phenoxy substituted by nitro, by alkyl of 1 to 2 carbon atoms, by alkoxy of 1 to 2 carbon atoms or by halogen, or alkoxy with 1-18 carbon atoms; and, when R4 represents a -O-M+ group, R3 denotes a -O-M+ group, phenoxy, phenoxy substituted by nitro, by alkyl of 1 to 2 carbon atoms, by alkoxy of 1 to 2 carbon atoms or by halogen, or alkoxy with 1-18 carbon atoms, and M+ is as defined above.

2. A compound of formula I according to claim 1 where-in A represents the radical .

3. A compound of the formula I according to claim 1 wherein A represents the radical -CH=CH-.

4. A compound of formula I according to claim 1 where-in n denotes the number 1 and Z denotes a radical of the formula in which R3 denotes a chlorine atom or an alkoxy group with 1-12 carbon atoms.

5. A compound of formula I according to claim 1, where-in n denotes the number 2 and Z denotes a radical of the formula .

6. A process for the manufacture of an imidyl-benzene-dicarboxylic or -tricarboxylic acid derivative of formula I according to claim 1, characterised in that an amine of formula II

(II) is reacted, in at least the stoichiometric amount, with an anhydride of formula III

(III) to give a compound of formula IV

(IV) wherein A and n have the meaning indicated in claim 1, and, when n = 1, Z' denotes a radical of the formula and, when n = 2, Z' denotes a radical of the formula wherein R4' denotes hydroxyl, phenoxy, phenoxy substituted by alkyl of 1 to 2 carbon atoms or by alkoxy of 1 to 2 car-bon atoms, alkoxy with 1-8 carbon atoms or a -O-M+ group, and, when R4' represents phenoxy, substituted phenoxy or alkoxy as defined above, R3' denotes hydroxyl,phenoxy; phen-oxy substituted by alkyl or alkoxy of 1 to 2 carbon atoms, alkoxy with 1-18 carbon atoms or a -O-M+ group and, when R4' represents hydroxyl, R3' denotes hydroxyl, phenoxy, substituted phenoxy or alkoxy as defined above, and, when R4' represents a -O-M+ group, R3' denotes a -O-M+ group, pherloxy, substituted phenoxy or alkoxy as defined above, and M+ has the meaning indicated in claim 1, and the com-pound of formula IV is subsequently cyclised.

7. A process as claimed in claim 6, characterized in that the resulting compound of formula I is converted into another derivative, according to the definition, of formula I.

8. A curable mixture which is suitable for the produc-tion of mouldings, impregnated products, coatings and ad-hesive bonds, characterised in that it contains (a) a poly-epoxide compound, (b) as the curing agent, a compound of formula I according to claim 1, wherein A and n have the indicated meaning and Z represents a radical of the formula or and R3" represents hydroxyl, phenoxy, phenoxy substituted by nitro, by alkyl of 1 to 2 carbon atoms, by alkoxy of 1 to 2 carbon atoms or by halogen, or alkoxy with 1-18 car-bon atoms.

9. A curable mixture according to claim 8, characte-rised in that it contains a vinyl compound.

10. A curable mixture according to claim 8, characte-rised in that it contains, as the curing agent (b), a com-pound of formula I wherein A denotes the radical , n denotes the number 1 and Z denotes a radical of the formula in which R3" represents an alkoxy group with 1-12 carbon atoms.

11. A curable mixture as claimed in claim 10, wherein A denotes the radical -CH=CH-.