DE2139005A1 - PREPARATION OF MODIFIED 2,4,5TRIKETOIMIDAZOLIDINE COMPOUNDS - Google Patents

Description

REICHHOLD ALEERT CHEMIE AO, HAMBURG 70. IVERSSTRA SE 57

Patent application

Production of modified ^, S-triketoimidazolidine compounds, in particular naoh patent .. (patent application P 20 30 2J5.4)

The invention relates to a method for producing modified N, N'-substituted 2,4,5-triketoimidazolidines with conversion of QxamidsKurealkylestern with isocyanates or leooyanat cleaving Links.

It has also been proposed to use allyl oxamides with isocyanates with formation of N, N'-substituted 2,4,5, -tri'ietoimidazolldynes to implement. The conversion can take place according to equation (l) of the attached form. The second mole of isoyanate serves as a Condensing agent in the formation of the imidazolidine ring.

As has also been suggested, this response is particular Interesting for the production of precondensates which still contain end groups that can be linked to one another, e.g. B. according to Oleiohung (2) of the attached formula sheet. The meaning of R, R and R is explained below.

In equations (1) and (2),

R is a mononuclear or polynuclear, mono- to hexavalent, in · den Equations (2) and (3) are only shown as a divalent remainder, aromatic or heteroaromatic radical with up to 20 carbon atoms, which is optionally substituted, where the aromatic radicals in certain cases can also be quinones, and polyvalent aromatic radicals through aliphatic radicals or can be linked to one another through heteroatoms;

3 0 9807/1288 ^{/ 2}

R ^r "has the meaning given under R or means one

aliphatic hydrocarbon radical with up to 18 carbon atoms or a cycloaliphatic hydrocarbon radical with up to to 12 carbon atoms;

Ty ν R and R are identical or different radicals, namely ali Phatieohe hydrocarbon radicals with up to 1 3, preferably up to 6 carbon atoms, cycloaliphatic hydrocarbon radicals with up to 8 carbon atoms, mononuclear aromatic Hydrocarbon radicals with 6 carbon atoms that are not substituted or with hydrocarbon radicals with up to 14 carbon atoms are substituted.

The German patent application P 20 30 233.4 contains a method for the preparation of modified N, N'-substituted 2,4,5-triketoimidazolidines by reacting alkyl oxamates with

Isocyanates or isocyanate-releasing compounds, the Oxamic acid esters have a group -NH-CO-CO-OR, in which

R is an aliphatic hydrocarbon radical with up to 18, preferably up to 6 carbon atoms, a cyoloaliphatic hydrocarbon radical with up to 8 carbon atoms, a mononuclear aromatic Hydrocarbon radical, which can optionally be substituted with hydrocarbon radicals having up to 14 carbon atoms, generally means at temperatures from -20 to + 280 C and optionally in the presence of a catalyst, with additional Polycarboxylic acids are reacted with the formation of condensation products with amide and / or imide groups, whereupon the formed, Products containing polymerizable groups, if appropriate are polymerized. This reaction is illustrated in equations (3) through (5). In these equations the symbols have the meaning given above, also means:

R ₊ _ a trivalent aliphatic, carbo- or heterocyclic, mono- or polynuclear, e.g. B. cyclo-

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aliphatic, aliphatic-aromatic or aromatic Hydrocarbon atoffreat with 2 to 20 carbon atoms.

Further explanations for the production of the Araid or. Imide groups containing polymers result from the German patent application P 20 30 233.4.

It has been found that valuable products can be prepared from the polymeric 2,4,5-triketoimidazolidine compounds. the The invention relates to a process for the production of modified N, N'-substituted 2,4,5-tri-ketoimidazolidines with conversion of OxamideHurealkyIesters with isocyanates or isoÄnate split off

Compounds, where the OxamidsKureester is a grouping

ν ν

-NH-CO-CO-OR, in which R is an aliphatic hydrocarbon radical with up to 18, preferably up to 6, carbon atoms cyoloallphatisohen hydrocarbon radical with up to 8 carbon atoms, a mononuclear aromatic hydrocarbon radical, which can optionally be substituted with hydrocarbon radicals having up to 14 carbon atoms, means - in general at temperatures of -20 to + 28o ° C and optionally in the presence of a catalyst, where appropriate - in particular according to patent .... (patent application P 20 30 233 * 4) - additional polycarboxylic acids are converted with the formation of condensation products with amide and / or imide groups and where the products containing polymerizable groups that are formed are polymerized with the Indicator that azomethines of the formula (37) (see Formula sheet) or azo compounds of the formula (38) (see formula sheet) and / or their metallohelates are reacted in which

R is a mononuclear or polynuclear aromatic radical with 6

up to 14 carbon atoms, the one in the o-position to the azomethine group contains an OH group and which is optionally substituted one or more times by alkyl, cycloalkyl, oxy, aryl, aryloxy,

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Carboxyl, acyl, ζ. B. Acety 1% nitro groups or halogen atoms

• substituted let, and where the substituted each up to to 6 and the Reat R including have up to 22 carbon atoms, and

to 6 and the radical R including all substituents

R is a monovalent or polyvalent aromatic radical with C to 14 C atoms, which contains a hydroxyl group in the o-position to the azo group and which is optionally replaced by alkyl, alkoxy, acyl, carboityalkyl, pluoroar bon groups or halogen, z. B. chlorine, is substituted. where the Sunstituenten up to 6 carbon atoms

VII and the radical R including all substituents up to

Have 22 carbon atoms, ! «.

These compounds obtained by the present invention are already known as such · brewable, z. B. due to their favorable thermostable properties as storage-stable and thermostable additives or Plastics. The good Ijiger stability is probably due to the Chelate-forming groups, through which any metal traces causing the degradation of hair, are intercepted • However, I nooh continue to implement it, e. B. with metal compounds.

In doing so, those in the conversion products can be made from

end the first stage existing chelating groups taking chelation education respond. From this round one becomes advantageous or dig polyvalent compounds of such metals that form chelates or lexes. But it is also possible that already in the first process stage instead of or together with the azomethine

respectively. or azo compounds whose metal chemicals are reacted.

The time of the chelation can be chosen arbitrarily, z. B. before, during or after the synthesis of the polymer chain. He depends on. Time of addition of the metal compounds.

The installation of the ohelate-forming azo or. Azomethine compounds or the chelate can take place by reaction, e.g. in suitable solvents, with the other components and the isocyanates. On the basis of the oliohung (6) the complicated reaction sequence is supposed to be

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be explained in a simplified manner. Therein mean:

A '= the number of moles of oxamic acid ester

B * »the number of moles of isoyanate (4l)

G ¹ = the number of moles of polycarboxylic acid (3 °)

D ^f = the number of moles of azo or azomethine compound (42)

The installation of the components, e.g. B. ohelate-forming compounds, into the polymer chain usually takes place via the carboxyl groups of the polycarbonate or amidocarboxylic acid residue by reaction with the isocyanate groups of the reactant with the formation of SSureamide groups. The o-hydroxy group can initially also with isocyanate with formation of phenolic carbamic acid esters react. However, these are cleaved again in the course of the polycondensation, especially at the higher reaction temperatures

For example, it becomes the chelating link in the polymer chain installed and then this polymer z. B. reacted with a divalent metal compound, so are crosslinked Polymers obtained, as can be seen from equation 7 (see formula sheet).

The cross-linking process is activated when a polymer solution, in which a solo chelating agent is incorporated, e.g. B. zuisoht a cobalt (II) salt and heated the Misohung to 150-2G0 ° C. To gelling occurs for a short time. After removal of the solvent, this gel gives a completely insoluble and infusible one Polymer.

For the reaction of the oxalic acid ester, the polycarboxylic acids, isocyanates and azo or azomethine compounds ^{, the equation applies if A f} to D ^f all have the same functionality

wherein aC 0.05 to 1.07, preferably 0.98 to

1.02 means.

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The isoyanate component can therefore be in a slight over or Undersole, based on the three remaining components will. Different functionalities of the components are to be considered accordingly. With different numbers of the functional groups alleviate the mutual molars Shares in a known manner.

On the other hand, the ratio of the oxamic acid esters to the ohelate-forming azo or azomethine compounds or their chelates is generally (2 to 9 ^), preferably (1 to 80): (0.1 to 50). Preferably (5 to 20) mol%. In addition, if Nooh polycarboxylic will used as Ausgangsamterial, amounts to their

Proportion 5 to 95, preferably 10 to 80 mol %, the total amount always being 100 mol % in both cases.

The chelating metal compounds can be used in a proportion are used, which is about that of the chelating groups equiraolecular.

The reaction partners are converted, if necessary in a stepwise one-pot reaction, in suitable solvents. The reaction of the azomethine or azo compounds can take place before, during or after the reaction of the oxamido esters with the isocyanates. In general, the components, consisting of oxamidescure esters, azo or azomethine compounds and, if appropriate, a polyarbone mure, are dissolved or finely divided in a solvent. The isoyanate is then added in solid, liquid or dissolved form at temperatures between minus 20 and 380 ° C., preferably between 0 and 250 ° C., in particular between 50 and 200 ° C. The condensation is then carried out at temperatures between 100 and 250 ° C. until no more CO ₂ and no alcohol are split off from the reaction mixture. It is

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but also possible to drive the condensation only so far that the Kquiraolecular amount of alcohol or C0_ has not yet been split off. Less high molecular weight is obtained, e.g. B. also monomeric or oligomers products whose further condensation to form high molecular weight Products can possibly only take place during later processing or after production.

Suitable oxamide acid esters of the formula VII. (See formula sheet), in which the formula explanation given in the application P 20 JO 225.4 applies, are, for example, bis-oxamide acid esters of the formula (50) (see formula sheet), in which R 1 has the above meaning. A ^f - an optionally substituted divalent cyclic, preferably

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wise aromatic radical has up to 12 carbon atoms in the ring system, whereby a nucleus can be substituted up to four times, means.

Suitable radicals for A ¹ are, for. B. those of the formulas (47) to (4g) (see formula sheet), in which X = ■ -CHp-, -0-, -S-, -SS-, -SO ₃ -, -N = N-, furthermore Pyridylene, quinonylene, thiophenylene, benzofurylene and N-methylcarbazolylene radicals which are present in one or more aromatic and / or heterocyclic nuclei one or more times, e.g. B. by alkyl, alkoxy, haloalkyl, ester, alkyl ketone, (C & - m) ketoalkyl, alkylsulfonyl groups each with 5 carbon atoms, where m is an integer from 1 to 3, such as - CH ,, -C ₂ H- »-OCEL, -OCpH, -CM, -COCH ,, -SO ₂ CH-, -CF-, -COOC ₂ H-, also nitro, cyano groups, halogen, especially F, chlorine , Bromine can be substituted. Further suitable bisoxaraide acid esters and polyarboxylic acid cures of the formula (44) (see formula sheet) are those mentioned in German patent application P 20 30 233.4. Here is

R is a mononuclear or polynuclear, mono- to hexavalent, in the Although equations (P) and (3) are only represented as a divalent remainder, aromatic or heteroaromatic radical with up to 20 carbon atoms, which is substituted separately by halogen, nitro, dialkylamino, dlarylamino, alkylaryamino groups, Alkyl, alkoxy. Carboxyalkyl, carboxyaryl, acyl, ζ. B. acetyl », cycloalkyl groups or halogenated Alkyl, alkoxy, carboxyalkyl, carboxyaryl, acyl, ζ, Β. Acetyl, cycloalkyl groups, sometimes with up to 18 carbon atoms, where the aromatic radicals in certain cases can also be quinones, and polyvalent aromatic radicals through aliphatic radicals or can be linked to one another through heteroatoms;

In addition, the one mentioned in the above applies to both formulas. Sign up specified formula class. The OxamidsKureester can therefore 1 have up to 6 ester groups.

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“AD

In formula (44) (see formula sheet) for the polycarboxylic acids mean

R, a di- to 6-, preferably trivalent, given poly

fall by substituted alkyl, halogen or amino groups aliphatic, 'oarbo- or heterocyclic, single or multinuclear, e.g. B. cycloaliphatic ^ aliphatisoharomatic or aromatic hydrocarbon rust with two to 20 carbon atoms, the aliphatic © radical being saturated, one or more times, e.g. B. double, olefinic can be unsaturated, and ρ is an integer from 2 to 6.

The polycarboxylic acids can therefore be up to 6-valent. It is possible, that the polycarboxylic acids as such, optionally together with amines, or in the form of polycarboxylic acids containing amide or amide groups can be used. The polycarboxylic acid (39) according to SS Equation 6 (see formula sheet) can be used before the start of the polycondensation in the reaction vessel from the components, so to speak in one One-pot-stage reaction can be produced, in the case of the component (3 °) e.g. B. from 4,4-diamino-diphenylsulfone - hzw "the corresponding Compound of 4,4-diamino-diphenylmethar. and 2 moles of trimellitic acid anhydride in the solvent suitable for the polycondensation. Then, as mentioned above, the actual policy ondensat ion carried out.

Suitable polycarboxylic acids or their anhydrides are, for example Isophthalic, bromoisophthalic, 3-aminoisophthalic, trimellitic, Pyromellite-, terephthal-, 2,5-dianilinoterephthal-, 2,5-ditoluidino-terephthal-, 4-Arainonaphthal-, 4,4-Methylenbisanthranil-, Hemimellite, Mellith, Malein, Fumar, Itacon, Hexahydroterephthal, Adipic, glutaric, amber, sebacic, cor ^ acid, ^ etrahydrofurantetrao ar bonsäure, Beazophenontetracarbonsäure, 1,4,5, -8-Naphthal intetracarbon-, Perylenetetracarbpnsic acid, benzophenonhexaoarbonskuredilacton, also condensed systems that contain at least 2 carboxyl groups in the molecule, such as. B. M, N'-terephthaloyl-bis-glycine, N.N'-isophthaloyl-bls-glycine, bis-carboxymetl-tylamino-diphenylmethane (or diphenyl ether or diphenyl sulfone). Also polycarboxylic acids

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2139003

according to formulas XXIV to XXVIIa (see formula sheet) are suitable for the implementation. Further suitable polycarboxylic acids containing amine groups, are z. B. AmidsHuren, as they are implemented by Maleic acid anhydride with diaminodiphenyl '-' ether, p-phenylenedlamine or m-phenylenediamine with amide formation and liberation of a carboxyl group of maleic cure anhydride.

The amines are di- to hexavalent, mono- or polynuclear carbo- or heteroxyclic, aliphatic or cycloaliphatic with up to suitable for 20 carbon atoms in the unsubstituted radical. The residues of the amines can optionally be replaced by halogen. Nitro, or if necessary halogenated- alkyl-, alkoxy-, carboxyalkyl-, carboxyar-yl-, Il acyl, ζ. B. acetyl, cycloalkyl groups, all with up to

18 carbon atoms, be substituted, the aromatic radicals also Quinones can be. Suitable radicals of the amines are those given above for A '.

Suitable isocyanates of the formula (VIII) (see formula sheet), in which the formula explanation given in application P 20 3C 233.4 applies, are trivalent and tetravalent, such as 2,4,6-triisocyanatotoluene, 4.4 ^t , 4 "- Triisocyanato-triphenylmethane. 2, Λ.4'-Triisoxyanatodipheny! Methane. 2.2 ^f , 5.5 ^! -Tetralsooyanato-diphenylmethane, also trivalent isocyanates of the formula XX (see formula sheet O, which can be obtained, for example, by adding trimethylolpropane to tolylene diisocyanate isocyanate of the ^ ormel XXT, which can be prepared by reacting hexamebhylene diisocyanate and water

(see formula) or isocyanates with up to four free isocyanate groups the formula XXTT (see formula sheet), as z. B.

e from the reaction of tolylene diisocyanate in hexamethylene diisocyanate can be produced. Suitable divalent isocyanates are, for. B. 4,4'-diisocyanato-diphenyl ether, 4,4'-diisooyanato-diphenylmethane, 2,4-toluylene diisocyanate, as well as those in German Registration P 20 JO 2 ^ 3.4 are described.

Also the tri- and tetrate oxyanates can be the same as those listed above Have substituents such as the diisocyanates.

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Portions of the free isocyanates can also be compounds which split off Ieocyanate, eg. B. Diphenylmethane-4,4'-bis (carfcarinic acid phenyl ester), DiphenylHthane-4,4 * -bis (carbamide-Kurebutylester), Diphenyl -4,4'bis (oarbaminsSurediethylamid), can be used.

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8AO

I. I vj JUU ""

-yf-

KX

The diisocyanates shown in equation 6 are also to be understood as those that are z. B. according to equation 9 (a formula sheet) from monomeric diisocyanates and DiecarbonsKuren in known Let build wise.

The Ieooyanate can as such or in the form of conversion products with terminal reactive isocyanate groups or groups which split off these are used, these conversion products being composed of isocyanates or their releasing agents and polycarboxylic acids have been produced.

Trifunctional or higher-functional isocyanates or isocyanates can also be used.

Use polycarboxylic acids. However, their concentration should generally be 1 to 5 mol percent, based on the particular Do not exceed the proportion of the same component type, otherwise the optimal properties of the polycondensation products will not be achieved can be obtained.

The synthesis of the isocyanates (46) can be carried out in a known manner by reacting (n + 1) moles of the diisocyanates (44) with η moles of the dicarboxylic acids (4 =) in inert solvents at temperatures from 0 to 200.degree. C., preferably from 50 to 160.degree. As for all solvents, those mentioned below are preferred. The so obtained solutions of the isocyanates (4i) can be used directly as such serve for the reaction according to the invention. But you can too by precipitation, e.g. B. with aoetone or toluene, obtained in solid form and so in the reaction to the Use.

Examples of suitable azomethine compounds are: Reaction products from 5-Aminoisoph ^ halic acid with salioylaldehyde, l-hydroxy-2-naphthaldehyde (compare formula 37 in each case), 2-hydroxy-1-napthaldehyde, 4-methylsalioylaldehyde, 4-carboxyüthyl-salicylaldehyde, 4-methoxysalicylaldehyde, 3-chloro- or 3-bromo-alkylaldehyde, 4-acetylsalicylaldehyde, 4-hydroxy-diphenyl-3-aldehyde, ^ -Hydroxydiphenyl - ^ - aldehyde, p-benzyl-salicylaldehyde.

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BATH ORIGINAL

Suitable azo compounds are those which duroh reaction of diazotized 5-aminoisophthalic acid, for. B. have been prepared with one of the following compounds (see formula 38) 1 p-cresol, 2,4-dimethylphenol, 2 Λ-di-tert-butyl phenol, p-chlorophenol, 2,4-diolphenol, p-Qxyaoetophenon, hydroquinone monoethyl ether, p-cyclohexylphenol, p-octylphenol, B-naphthol, 4-methyl- «£ -naphthol, 4-bromonaphthol; 4-Hydroxydiphenyl, ^ -hydroxy- ^ - athoxydiphenyl, 4,4 ^f dihydroxydlphenylmetban-raonomethyläther.

Compounds, for example, can be used as ohelate-forming metal compounds with metals of the 1st to 8th groups of the periodic 3 system in embossing. Preferably, however, connections of Lithium * sodium. Potassium. Zinc, magnesium, barium, aluminum, titanium, bromine, lead, chromium, Elsen, cobalt or nickel for chelating used. The oxides, hydroxides, carbonates, halides, alcoholates, z. B. Methylates, ethylates, butylates, phenates, such as those of phenol, of cresols or xylenols, acetates, formates. 3ctoate, Naphthenates u.a..A'J.oh complex compounds of metals, e.g. B. such ' of the acetylacetone or the enol'ized acetoacetic ester are suitable. In these compounds, the metals can be one, two or be superior.

Suitable solvents are e.g. B. phenol, cresol, Oemisohe teohnischer phenols, dimethylformamide. Dirnethylacetamide, dimethylsulfoxide, IJ-methylpyrrolidin. N ^f , Η ^f , K, N, -Tetramethyl-urea, N.ir ^ I ^ .- HexamethylphoBphorsauretriamld, acetonitrile, cyclohexanone, isophorone, nitrobenzene, lyridine, tar base mixtures or mixtures thereof. In addition, up to about JO% 'higher-boiling aromatics or hydroaromatics, z. B. diethylbenzene or decahydronaphthalene, or glycol ethers, 7 .. B. DLstthylenglykoldimethylMthe · - c-the butanediol diethyl ether are mixed with the aforementioned solvents. The between.

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2139OsTR

JM

Accordingly, the polymers are generally obtained in solution. By precipitation with other solvents, e.g. toluene, Water, acetone, carbon tetrachloride, ethyl acetate, they are obtained in solid form. But you can also apply to others Manner, for example by volatilizing the solvents, such as vacuum spray drying, in solid form.

The claimed reaction can in many cases by the Use of suitable catalysts can be accelerated. Such are e.g. tertiary amines, such as triethylamine, tributylamine, Ν, Ν-dimethylaniline, diazabicyclooctane, pyridine, tryphenylamine, N.N'-tetramethyl-ethylenediamine, also e.g. hexamethylphosphoric acid triamide, Dibutyloxotin, dibutyltin dilaurate, triphenyl phosphite. Alkyl titanates, e.g. tetrabutyl titanate, ferrocene, Heavy metal complex compounds, e.g. iron aoetylacetonate, but also alcoholates or phenolates of metals of the 1st, 2nd or 3rd group of the periodic table, such as lithium benzoate or Calcium carbonate.

The catalysts can be added before or during the condensation take place. Different catalysts can also be added at different points in time during the course of the reaction will. The amounts are generally between 0.001 and 5 percent by weight of the reaction mixture, but preferably between 0.05 and 1 ^.

After fulfilling its task, the catalyst, if it is a metal compound, can be used to build up the chelate system. This can be particularly important if ^e z * .B. should only be effective in the first part of the reaction sequence.

The monomers and polymers produced according to the invention, especially The low molecular weight compounds are extremely versatile, e.g. they are valuable intermediates f for organic syntheses. They serve - especially in theirs

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low molecular weight - as starting materials for the production of pesticides,

such as insecticides, hycocides, bactericides also for the synthesis of dyes and plastics and for the stabilization of high molecular weight substances, preferably polymerization and condensation resins. The products obtained according to the invention are also suitable as stabilizers for polymeric products, in particular for polymerization and / or polycondensation resins. But they can also be mixed with such polymers, including the polymerization and / or condensation resins with heterocyclic groups, at temperatures from minus 10 to plus 250 ^° C., preferably at plus 20 to 190 ^° C., in solution, melt or in the solid phase low or high molecular weight products obtained according to the invention or solutions of the polymers with chelating groups or chelate groups are generally yellow to red-brown colored, highly viscous solutions. The inherent viscosity is between 0.2 and 1.2, measured on aqueous solutions in dimethylacetamide or N-methylpyrrolidone.

The polymers as obtained according to the invention show high thermal stability and very good adhesive strength the most varied, especially on metallic and silicate surfaces.

Surprisingly, it has been found that polymers in the manufacture of which small amounts of a chelating agent - e.g. as little as 0.02 mol / mol polymer unit - were added, solutions that are much more storable than solutions without chelating agents. They practically did not change their viscosity over months, while comparative solutions in this time had doubled their initial viscosity.

In addition, it has been found that such small amounts of a built-in chelating agent are significantly lighter

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Polymer solutions compared to solutions without chelating agents were obtained. Films made from these solutions were considerably lighter in color (e.g. yellow instead of brown-orange) as films made from chelating compound-free polymers. This is due to the blocking of the engineering raw materials used traces of existing heavy metal traces. These traces are known to catalyze auto-oxidation processes and thus lead to discoloration. The extraordinary thermal stability of the Polymers in an oxygen-containing atmosphere.

The products produced by the process according to the invention are also particularly suitable for coating metals, in particular metallic molded bodies such as wires, sheets, plates, tubes, preferably electrical conductors, regardless of whether they are applied in powder form or in solution, in the same way However, they can also be applied to ceramic moldings. After thermal polycondensation or after crosslinking with chelation, very well adhering, even high-temperature-resistant, thermally stable coatings are obtained on these objects. However, the claimed compounds are also suitable, especially in powder form, after mixing with fillers, especially of an inorganic nature. eg mineral powders, glass powder, glass fibers, asbestos fibers, graphite, metal powders and chips, for the production of shaped bodies by the hot pressing process. With these fillers, the products produced according to the invention can be ^{processed into shaped bodies at high temperatures, for example at 230 to 500 °} C., and high pressure, for example / up to 5000 at. Furthermore, they can be used to form crystal-clear sheets and films as well as fibers. These products also show high thermal stability. In addition, like the coatings, they can have a very high surface hardness with constant elasticity.

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point. They also show high elasticity at low temperatures, very high softening points (54o to over 4G0 ^o C) and high thermal endurance. The products produced according to the invention also show very good adhesive strength on various types of surfaces, in particular metallic and silicate surfaces, and are therefore also suitable for the production of laminated bodies. The products can be processed into foam-like material with high temperature resistance by means of suitable measures, for example the addition of propellants - but possibly also without such, since the alcohol released and the carbonic acid formed can also act as a propellant.

Another area of application is the manufacture of high-temperature resistant materials Foams that are particularly important for insulation purposes.

Example 1

564 g (= 1 mol) of 4,4 "-bis (4-carboxyphthalimido) -diphenylsulfone, 548 g (= 1 mol) of 4,4" -bis (4-carboxyphthalimido) -diphenyl ether are put in a 10 o 1 three-necked flask in 23oo ml of N-methylpyrrolidone and 2,000 ml of dimethyl sulfoxide slurried at 60 ° C. Then 67 g (0.2 mol) of the azomethine (melting point = 300 ° C. with decomposition) from 2-oxynaphthaldehyde-1 and 5-aminoisophthalic acid are added. It is then heated to 140 ° C. At this temperature, within J> hours, 199 g (0.5 mol) of 4,4-bis (ethoxalylamino) diphenylmethane, 176.4 g (0.7 mol) of 4,4-di-isoeyanato-diphenyl ether and 500 g (2 , ο mol) 4,4 * -diisoeyanato-diphenylmethane registered. It is stirred at 150 ⁰ C until the elimination of CO ₂ finished 1st (about 6 to> hours). After addition of 2 g of tributylamine, the temperature is increased to 200 ⁰ C and held for 4 hours Finally be 4oo ml of cyclohexanone and 2oo ml Diäthy! Benzene introduced for dilution. After cooling down

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a light orange-yellow, hocliviscous polymer solution is obtained. 72oo g: the solids content is about 25 weight box ₁ ^ yield.. The inherent viscosity of the polymer is 0.44 (20 ° C.), measured in a 1 # solution.

Example 2

158 * 5 g (oj8 mol) 4,4-Diaminoöiphonylmefchan are dissolved with stirring in 128o ml of N-methylpyrrolidone at room temperature. Then 3o7.2 g (^ 1.6 mol) of trimellitic anhydride are added in portions at 80.degree. After the addition of toluene as an azeotrope agent, the temperature is increased to 180 ° C. and condensation is continued until no more water is split off. r This is the case after about 2 hours. Now 79.6 g (o, 2 moles) of 4,4 "-bis-äthoxalylaminodiphönylmethan and 11.4 g (o o4 mol) of the azomethines (mp = 237 C ^e) from 5-aminoisophthalic acid and salicylaldehyde added. After cooling to 160 ° C., 250 g (= 1 mol) of 4,4'-diisocyanate-diphenylmethane are introduced. It is condensed at 160 to 130 ° C. until the COg elimination has ended. Finally, it is increased to 205 ⁰ C and then distilled off over a Püilkörperkolonne the liberated during the condensation alcohol, that the head temperature does not exceed 125 ° C. It is then cooled and diluted with 100 ral dimethylacetamide, 100 ml hexamethylphosphoric acid triamide and 90 ral cyclohexanone.

There are 2; 5oo g of a yellowish brown, hechviskosen solution with a Pestkürpergehalt of about yi% erhalten- The Inhärenzvlskosit.it of the polymer, measured in l ^ strength solution, cheating 0.5O (20 ^e C).

Example ^

15 p. 5 g (0.8 mol) 4,4-diaminodiphenylmothane are in 000 ml N-Methylpyrrolidcm and 50 ml of dimethyl sulfoxide dissolved and at

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8AD ORIGINAL

acc changed input * "- received on 2 5 * 5 7- 1..

At 60 ° C., 3o7.2 g (^ 1.6 mol) of trimellitic anhydride were added. The temperature rises to 95 ° C during this process. After toluene has been added as an azeotrope, the ^{condensation is carried out at 185 °} C. until the elimination of water has ended. It is then cooled to 8O ^e C., and 235 g (= o, 94 mol) of 4,4 'diisocyanatodiphenylmethane dissolved in 44o ml of N-methylpyrrolidone was added dropwise over 3o minutes. After three hours of stirring, the temperature is raised to 200 * C and 39 * 8 g (= o, l mol) of 4 _J 4 '-Bisäthoxalylaminodiphenylmethanveingerührt. Finally, as in Example 2, the alcohol is distilled off. After cooling to 140 ° C., it is diluted with 300 ml of N-methylpyrrolidone and 50 ml of isophores. 2300 g of a highly viscous red-orange polymer solution with a solids content of 5 % are obtained up to room temperature.

That precipitated from the polymer solution with an aceto-alcohol mixture Polymer showed an inherent viscosity of 0.77 in a solution in N-methylpyrrolidone.

Example 4

213.4 g (= 0.4 mol) 4,4'-bis (4-carboxyphthalimido) -diphenylmethane and 3 * 55 g (= o, ol mol) 5- (4-carboxyphthalimido ^ isophthalic acid are dissolved in 400 ml of N. dissolved methylpyrrolidone and stirred at 120 ⁰ C 39.8 g (o, l mol) of 4,4 'diphenylmethane--Bisäthoxalylamino. After cooling to 100 ⁰ C, a solution of 130 g (= 0.52 mol) of 4,4 'diisocyanato-diphenylmethane in 260 ml of N-methylpyrrolidone is added dropwise within 2 hours. Then, after adding 0.5 g of dibutyltin dilaurate at 170 ⁰ C is condensed until the CO elimination ₈ is completed. after the temperature was increased to 20O ⁰ C by the addition of ^2, 85 g (= o, oil mole) of the azomethines of 5-aminoisophthalic acid and salicylaldehyde. at this temperature is in the

3 0 9807/1288

Alcohol liberated from condensation is distilled off as described in Example 2. The mixture is then heated to 2O5 ° C. and 4.9 g of cobalt octoate, dissolved in 2o g of dimethyl sulfoxide, are added and the mixture is diluted with 2oo ml of N-methylpyrrolidone. After cooling to room temperature, 150 g of a clear, highly viscous, brown-orange colored solution with a solids content of about 29 fo are obtained. Inhärenzviskosität: 0.67 solution of the solid polymer in N-methylpyrrolidone at 20 ⁰ C)

Example 5

79.2 g (= 0.4 mol) of 4,4-diamino-diphenylmethane and 153.6 g (= 0.3 mol) of trimellitic anhydride are stirred with 200 ml of N-methylpyrrolidone and 200 ml of dimethyl sulfoxide. After xylene has been added as an azeotropic agent, ^{condensation is carried out at 190 °} C. until no more I ^ .0 is split off. It is then cooled to 120 ° C. 2.5 g of triethylamine and 0.5 g of butyl titanate are mixed in. Then 39 "B g (" = o ₃ l mol) 4,4'-bis (ethoxalylamino) diphenylmethane and 6.7 g (o, o2 mol) of the azomethine from 5-aminoisophthalic acid and 2-hydroxynaphthaldehyde-l registered. At 100 ⁰ C then 1 og ^ (= 0.52 mol) of 4,4 '-Diisooyanatdiphenylmethan dissolved in 260 ml of N-Methylpyrrolldon added dropwise within an hour. After the addition is complete, the mixture is ^{heated to 202 °} C. and condensation is completed at this temperature for 6 hours. After cooling to l60 ^e C

1I60

diluted with 2oo ml of cyclohexanone. A pale yellow and clear polymer solution with a solids content of about 150 % is obtained. The viscosity of the solution is about 24ooo OP (20 ⁰ C).

Example 6

298 g (1 mol) bis-ethoxalyl-aminodlphenylmethane, 67 g (0.2 mol) Azomethine from 2-oxynaphthaldehyde-1 and 5-aminoisophthalic acid are dissolved in 600 ml of N-methylpyrrolidone at 60 ° C. Thereon

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are slowly added ^ 40 g (1.22 mol) 4,4 ⁵ -DiisooyaEato-diphenyl ether. Then the oil temperature is increased to 150 ⁹ C. The reaction mixture is kept at this temperature until there is no longer any evolution of CO ₂ . Finally, the mixture is heated to 250 ° C. for four hours until no more ethyl alcohol is split off. One rhält © * a clear light yellow-brown highly viscous solution (with the i-nhärenzvisko- "intensity of o, k (20 ^e C) The solids content is about 50 wt .- ^. Yield: 1 g ^ 05.

July 26, 1971
Dr LG / be / ma

3Ü9807 / 1 288

Claims (3)

Claims 1. A process for the preparation of modified N, N ^f -substituted 2,4,5-triketoimldazoildines with the reaction of alkyl oxamates with isocyanates or compounds which split off isocyanates, the oxamates having a grouping -NH-CO-CO-OR, in which R is an aliphatic Hydrocarbon radical with up to 18, preferably up to 6 carbon atoms, a cycloaliphatic hydrocarbon radical with up to 8 carbon atoms, a mononuclear aromatic hydrocarbon radical which can optionally be substituted with hydrocarbon radicals with up to 14 carbon atoms, generally means at temperatures from minus 20 to plus 2dO ^e C and optionally in the presence of a catalyst, with - in particular according to patent ........... (patent application P 2 ο? ο 23 $ Λ) " optionally additionally implemented polycarboxylic acids are formed with the formation of condensation products with amide and / or Imldgruppen and optionally contain the polymerizable groups formed the products are polymerized, characterized in that azomethines of the normal (37) and / or their metal chelates or azo compounds of the normal (j53) and / or their metal chelates are reacted, in which R is a mononuclear or mononuclear aromatic Remainder with 6 to Io C atoms, which is in the o-position to the azomethine group contains an OH group and which is optionally substituted one or more times by alkyl, cycloalkyl, hydroxy, aryl, aryloxy, Carboxyl, acyl, nitro groups of the halogen atoms is substituted and where the substituents are each up to 6 and the remainder R ^VI including all substituents up to 3 0 9807/1288 «AD ORIQiHAL Have 22 carbon atoms, R ^ is a mono- or polyvalent aromatic radical with 6 to 14 carbon atoms which contains a hydroxyl group in the o-position to the azo group and which is optionally substituted by alkyl, alkoxy, acyl, carboxyalkyl, fluorocarbon groups or halogen where the substituents have up to 6 carbon atoms and the radical R ^VI1, including all substituents, have up to 22 carbon atoms. 2. The method according to claim 1, characterized in that the reaction products which still contain chelating groups, be reacted with metal compounds. J5. Process according to Claims 1 or Z _1, characterized in that the ratio of the oxamide acid esters to the chelating azo or azomethine compounds or their chelates is (2 to 94) :( 0.1 to 50) Mo1 $, the sum always being 100 Mo1 $ 4. Process according to Claims 1 to 3> characterized in that d. ^: o Polycarboxylic acids are reacted in a proportion of 5 to 95 mols, the sum always being 100 mols. 5. Process according to Claims 1 to 4, characterized in that the reaction takes place in the presence of solvents from which the reaction products are deposited by adding other solvents. 6. The method according to claims 1 to 5, characterized in that that the oxamic acid esters, the chelating azo or azomethine 3 0 9807/1288 Zk compounds or their chelates and optionally the polycarboxylic acids are mixed and the isocyanate is then added. 7. The method according to claims 1 to 6, characterized in that that the chelating metal compounds are used in a proportion which is approximately that of the chelating metal compounds Groups is equimolecular. 3. Process according to Claims 1 to J, characterized in that the polycarboxylic acids are used together with amines or in the form of polycarboxylic acids containing imide or amide groups. 9. The method according to claims 1 to 'ί, characterized in that that the formation of the reaction products in the presence of Kata lysatoren takes place in the form of metal compounds, the In second stage are incorporated into the reaction products. Io. Process according to Claims 1 to 9, characterized in that that the isocyanates in the form of such reaction products with terminal reactive isocyanate or these cleavage Groups are used which have been prepared from isocyanates or their splitting offs and polycarboxylic acids. SAD ORIGINAL 3 0 9807/1288 Blank page