DE2030233C2 - Process for the preparation of modified N, N'-substituted 2,4,5-triketoimidazolidines and their use - Google Patents

Description

It has already been proposed in German Patent 1,916,932, alkyl oxamates with isocyanates to implement with formation of Ν, Ν'-substituted 2,4,5-triketoimidazolidines. The implementation can after Equation (1) on the attached formula sheet. The second mole of isocyanate serves as a condensing agent in the formation of the imidazolidine ring.

As has also already been proposed (patent application P 19 20 845.8), this reaction is particular Interesting for the production of precondensates, the end groups that can still be linked to one another included, e.g. B. according to equation (2) of the attached formula sheet.

The end groups -NH-CO-COOR ^ and -NH-CO0R ^v contained in the precondensates can be converted into poly-2,4,5-triketoimidazolidines upon thermal treatment with elimination of alcohol according to equation (3). It has already been stated in the aforementioned application P 19 20 845.8 that this reaction sequence is capable of great generalization.

In equations (2) and (3),

R is a mono- or polynuclear mono- to hexavalent aromatic or heteroaromatic radical with up to to 20 carbon atoms, optionally by halogen, nitro, dialkylamino, diarylamino, alkylarylamino groups, Alkyl, alkoxy, carboxyalkyl, carboxyaryl, acyl, e.g. B. acetyl, cycloalkyl groups or halogenated alkyl, alkoxy, carbalkoxy, carboxyaryl, acyl, ζ. B. Actyl-, Cycloalkyl groups, all substituted by up to 18 carbon atoms, the aromatic radicals can also be quinones if R is bonded to an oxamic acid ester residue or if this ester radical is zero and where polyvalent aromatic radicals replaced by aliphatic radicals or can be linked by heteroatoms,

R '"has the meaning given under R or means an aliphatic hydrocarbon residue with up to 18 carbon atoms or a cycloaliphatic Hydrocarbon radical with up to 12 carbon atoms.

The precondensates obtained after the reaction according to equation (3), which contain triketoimidazolidine rings, These compounds generally have a relatively low molecular weight have worked well, for some uses it was desirable to have connections with to use higher molecular weight in order to expand their application possibilities and improve their handling.

The French patent application 20 05 695 describes the production of poly (arylene-triketoimidazolidines) by converting bis (oxylic acid monoalkyl ester monoamides) of aromatic diamines with practically equimolar amounts of aromatic diisocyanates in polar solvents at temperatures, that between that of the beginning of an alkanol splitting off and the decomposition temperature of the particular used Bis-toxic acid-monoalkylester-monoamides), with removal of the split off alcohol. When using an excess of diisocyanate, the Polymers containing isocyanate end groups with chain

id extension agents such as water, diamines or the like, to be implemented further. The implementation of polymeric triketoimidazolidines with polycarboxylic acids is not described in this citation. The FR-PS15 75 421 deals with the production of

Γ * imide groups containing polyhydantoin plastics by reacting a polyhydric Glycinesterderivats with an excess of a polyisocyanate in a first stage at temperatures from 20 to 300 ⁰ C in a hydantoin and urethane and / or Harnstoffgrup-

w pen-containing pre-adduct and conversion of the same in a second stage at temperatures from 100 to 500 ⁰ C with a polyvalent compound with at least e ^; ner cyclic anhydride group in a plastic containing imide groups.

r> An improvement of the products according to the earlier German application P 19 20 845.8 becomes according to the invention achieved in that, in addition to the bisoxamic acid esters and the diisocyanates, up to hexavalent anhydride-forming polycarboxylic acids, preferably at most tetravalent carboxylic acids, and / or their anhydrides, insofar as they exist, are converted so that condensation products are formed form containing amide and / or imide groups. The subject of the invention is that in the > Proverbs 1 to 7 described method and the use described in claims 8 to 10.

The process according to the invention thus enables the production of monomeric to high molecular weight Condensation products that simultaneously contain 2,4,5-tri-

bueketoimidazolidines and polyamides, -imides or polyamidoimides are to draw compounds that have a combination of these different groups are characterized by particularly good processing properties.

hi Comparative tests have shown that the reaction products prepared according to the invention from bisoxamic acid esters, diisocyanates and polycarboxylic acids lead to better wire enamelling

as comparable commercial products made from high-temperature-resistant polymers based on from

a) aromatic polyamides made from an aromatic diamine and trimellitic anhydride chloride,

b) aromatic polyamides obtained by reacting trimellitic anhydride chloride with aromatic One or two-ring diamines, the two-ring diamines with one another via alkylene groups linked, won,

c) Polyhydantoins, which contain aromatic rings, which are connected to one another via alkylated hydantoin rings are connected.

It has been shown that the values with regard to the breakdown voltage, the abrasion resistance and the Film hardness, even after storage in acetone, cresol and dimethylformamide, for the products according to the invention are cheaper.

In further experiments, products according to FR-PS 1575 421 were compared with those according to the invention in compared with regard to their thermal stability, which enables a clear comparison of the quality. Included it has been shown that the weight losses during thermal degradation in air and nitrogen in the case of the invention obtained products are much lower than the products according to the FR-PS. this means in other words, that the products which can be prepared according to the invention are less decomposable and their decomposition temperature is less is considerably higher than that of the FR-PS products.

When carrying out the process according to the invention, it is not necessary to use the mixtures of the reactants to use; Rather, it is also possible to carry out the reaction in such a way that one partner begins first is presented, optionally in a mixture with only an insignificant proportion of the second and optionally third partner and that thereupon the main amount of the second and optionally third reactant is added. This embodiment can be carried out both in solution and in the melt will. A catalyst can be added to the reactant initially introduced and / or to the reactant used later be admitted. At first only two components can be connected to each other and the third in be reacted in a further stage. For example, first know the polycarboxylic acids - at least partially - are reacted with the isocyanates, e.g. with imide or amide formation, whereupon in the second stage the reaction with the oxamic acid ester - and optionally in a further one Stage the reaction with the remaining polycarboxylic acid - this reaction takes place in two stages, for example As illustrated in equations (4) and (5), the product is still reactive on both sides Contains groups, these can in general with further isocyanate groups and optionally further Oxamic acid ester groups with chain extension, e.g. B. under amide or imide formation, according to equation (6) and react with branching if necessary. In the equations (4) to (6) mean

R ₁ , a trivalent radical of the type defined in claim 1 under h) to m), and

R ^IV and R ^v aliphatic hydrocarbon radicals with up to 18 carbon atoms, cycloaliphatic hydrocarbon radicals with up to 8 carbon atoms, mononuclear aromatic hydrocarbon radicals with 6 carbon atoms which are unsubstituted or substituted by hydrocarbon radicals with up to 14 carbon atoms, ' where R ^IV and R ^{v can be} identical or different.

In compound VI, the chain linkage is after conversion of the anhydride groups of compound V. shown with the isocyanate II. So you get an imide bond. The free isocyanate group can then according to equation (5) again with oxamic acid ester to form triketcimidazoüdiriringen react. The free ester group of the compound V can with further isocyanate, for. B. with compound II, III or VI react with chain extension and formation of further triketoimidazolidine rings. The reactions according to equations (4) to (6) take place with the escape of alcohol or carbon dioxide. They make condensation and are not limited to tricarboxylic acids. Di- and other polycarboxylic acids can also be used in an analogous manner implemented.

.Vj In the products obtained according to the invention can the same radicals as in the compounds I and IV form the end groups. But it is also possible that oxamic acid ester groups on both sides or these ester groups only on one side and on the other Side each urethane or isocyanate radicals or both sides urethane or isocyanate radicals are arranged. Depending on the reaction conditions, the process according to the invention can be used to form monomers or polymeric compounds. At the inven-

Ji the implementation of the invention can also be obtained branched monomers or polymers, if one z. B. of at least trivalent carboxylic acids, optionally mixed with dibasic carboxylic acids - goes out. If the branching is to take place on the tricarboxylic acid residue, z. B. the free acid analog Equation (4) can be reacted with three moles of diisocyanate, so that an amide linkage in three directions he follows.

Monomeric compounds are e.g. B. Compounds according to the formulas XXIX (see formula sheet). In this, Q and Q 'have the meaning -NH-COOR ^ or -NH-CO-COOR ^V and R has the meaning given in claim 1.

so R "has the meaning given under R, where R

and R "can be the same or different,

R '"has the meaning given in claim 1

and is identical or different with R 'and R "',

means a bivalent or trivalent, optionally by alkyl, halogen or amino groups substituted aliphatic, carbon or heterocyclic, mononuclear or polynuclear, z. B. cycloaliphatic !!, aliphatic-aromatic or aromatic hydrocarbon radical with two to 20 carbon atoms, furthermore mean

NuIL if y = 1 or 1,

Zero or an integer from 1 to 70,

an integer of 1 or, if Q = zero, two;

/ and k can each be the same or different and

CO-

- NH-CO- or —N

CO-

g and h each 1 or 2, where the sum of (g + h)

is at most 3,
dLe, J
and j each represent the number one or zero, the sum of (d + e + f + j) being at least 1, and

where one of the radicals R and R '"is always aromatic and, when R'" is aliphatic or cycloaliphatic, the R '" adjacent radicals R, R 'or R "must always be aromatic.

As can be seen from formula XXIX and the associated definition, R _{poly is shown} here only as a divalent or trivalent radical. But it is also easily possible a more than three-valued, z. B. to use tetravalent to hexavalent carboxylic acid. In this case, Rp ^ y is a four- to six-valent radical, g and /! Each mean an integer from 1 to 5, where (g + h) is at most 6. Then R _p0 | _y a branch occurs, which can be seen, for example, from formula XXXI.

D''e molar ratios of the reactants oxamic acid ester, isocyanate and polycarboxylic acid can be used in can be varied within wide limits. They are best represented by the following equation:

{(LA + aC) = b £ ')

In it mean

α is the number of oxamic acid ester groups in moles of oxamic acid ester,

b is the number of isocyanate groups in B ' moles of isocyanate,

c is the number of carboxyl groups in C moles of polycarboxylic acid.

Here, α and b each mean 2 and c an integer from 2 to 6. d means 0.97 to 0.03 mol, C "means 0.03 to 0.97 mol, the sum of A and C" always being 1 . (bJ ¥) can be up to three times, preferably up to l, l times larger than (ttÄ + cC).

The oxamic acid esters, isocyanate and polycarboxylic acids can each be used as the sole representative of their Substance class or as mixtures.

In the reaction between the oxamic acid esters, the isocyanates and the polycarboxylic acids can be done with the molar ratios given above ' Depending on the reaction conditions, products are obtained with only a moderately high degree of polymerization. At this Reaction can, for example, one mole of bisoxamic acid ester with one mole of diisocyanate and then with one Mol of a di- or tricarboxylic acid anhydride or the free acid react, but only one isocyanate group is used for ring formation, while the other takes on the role of condensing agent, d. H. that the alcohol released during the ring closure is anchored intramolecularly in the compound formed in the form of a urethane group. This urethane group, which can also be referred to as blocked isocyanate, is now added, for example elevated temperature with or without a catalyst with elimination of alcohol and carbon dioxide with the Carboxyl group of an amide or imide group. This reaction proceeds according to equation (8) below Formation of compound XXXIII. In addition, however, multiple forms of the compound XXXIII can also arise. In this case, in this connection / is greater than 1. In these cases, the ring closure can be free alcohol that has become intramolecularly in the polymer and / or extramolecularly to unreacted isocyanate be bound. These products can e.g. B. the end groups

O O

ν Il Il

RV ₀ -CC-NH-O

- NH - C - OR ^1V - COOH

- COOR ^V

- COOR ^IV

and

-N = C =

contain. R ^lv and R ^v can be different if a mixture of oxamic acid esters with different alkyl groups is used.

As is easy to see, the new process enables the implementation of very different starting materials.

The claimed method offers further advantages. For example, while the per se known reaction frequently leads of polycarboxylic acids or anhydrides thereof with diisocyanates at temperatures above 8O ⁰ C to insoluble imido-containing polymers, the processing is extremely difficult, the reaction of the same reactants provides the concomitant use of a Oxamidsäureesters in the ratios indicated above clear Polymer solutions.

The process according to the invention can be carried out within a wide temperature range. Thus, the reaction can, in the absence or, advantageously, in the presence of solvents at temperatures of -20 to +280 ⁰ C, preferably from 0 ⁰ C to 180 ⁰ C, take place. The reaction is exothermic and in many cases takes place at room temperature or at a slightly elevated temperature, e.g. B. even at 40 to 50 ⁰ C from. To complete the reaction and when using less reactive components, e.g. B. some Isoc ^v anates or percarboxylic acids or their Anhvdriden, sometimes heating may be useful. It is also possible to convert the starting products in the melt and, if appropriate, then in - preferably phenolic - solvents.

The reaction can e.g. B. take place in solvents in which the claimed reaction products are insoluble, e.g. B. in ligroin, benzene, toluene, XyIoL chlorobenzene, nitrobenzene, cyclohexane, ethyl acetate, butyl acetate, or in those in which the reaction products are soluble, as in
Ν, Ν'-dimethylformamide,
Ν, Ν'-dimethylacetamide,
Dimethyl sulfoxide,
N-methylpyrrolidone,

Ν, Ν ', Ν'-hexamethylphosphoric acid triamide,
Phosphoric acid tris (dimethylamide),
Cyclohexanone, isophorone, acetophenone,

also in phenols with up to 10 carbon atoms, ζ. Β. Phenol, Cresol, Xyieno !. Except for those already mentioned In solvents, the products are also soluble in ketones such as acetone, methyl ethyl ketone and dibutyl ketone.

The resulting solutions of the polycondensation products can be used as such. By suitable precipitants, e.g. B. water, alcohols, aliphatic and / or aromatic hydrocarbons, The reaction products can be obtained from the solutions as mostly more or less strongly colored powders to be deposited. The latter can also be achieved by evaporating these solutions in suitable devices, z. B. in spray dryers. Win.

You can also prepare polymers in that the products prepared according to the invention which still contain polymerizable groups, eg. B. the radicals -NH-COOR ¹ *, -NH-CO-COOR "(hereinafter referred to as Q and Q '), -COOH, -C00R ^v , -C00R ^IV and -N = C = O, where R ^IV and R ^{v have} the meanings given above under R ^v and can be identical or different, according to equation (7), in which the above symbols apply and η is an integer from 1 to 70, preferably from 1 to 50, are polymerized. This may be the case when the present invention obtained monomeric reaction products, either in solution or in solvent-free form, in the molten or "solid state, to 120 to 55O ⁰ C, preferably at 260 to 48O ⁰ C, in particular 280 to 450 ⁰ C. In the process, chemical-resistant, temperature-resistant, practically insoluble film-forming polymers are formed. If the reaction temperature is selected to be so high, for example 150 to 300 ^° C., the reaction of the end groups Q and Q 'proceeds at a sufficient rate "Polymerization" is to be understood here as chain lengthening by addition and / or condensation. The polymers can be separated off by precipitation and filtration. They are light yellow to brownish powders which, surprisingly, can be readily soluble. Such a solution is made by adding For example, water, alcohol or the like are deposited practically unchanged talline, e.g. B. also microcrystalline substances.

Depending on the reaction conditions chosen, more or less polymeric products can be produced in the claimed process (cf. formula XI, in which η ζ, for example, can be an integer from 1 to 70). As a rule, products are obtained with a molecular weight that is not yet so high, so that, contrary to expectations, the products have a relatively good solubility in the usual solvents that do not contain reactive protons (= "aprotic"), (e.g. dimethylformamide, N- Methylpyrrolidone, dimethylsulfoxide, N, N ', N "-hexamethylphosphoric triamide). Even 30-70% solutions in the aforementioned aprotic solvents can be obtained without difficulty, without the viscosity of the same being very high. The solutions also remain at Stored unchanged and do not tend to crystallize. These properties allow a versatile use of the products prepared according to the invention for obtaining polymeric heterocyclic compounds with particularly good processability. As a result of the high molecular weight, the products show an improvement in the film-forming properties and high thermal stability in most of the L Solvent-insoluble polymers.

According to the invention, these insoluble polymers can, under certain conditions, also be used directly in can be produced in one step. This can e.g. B. when used to produce chemically resistant Moldings would be beneficial.

The reaction according to the invention can be carried out with or without catalysts. Suitable as catalysts basically those that are also used in other reactions of isocyanates with compounds with reactive Hydrogen atoms are used, e.g. B. tertiary bases, such as amines, ζ. B. triethylamine, tributylamine, N-isobutylmorpholine, pyridine, N-methylpiperidine, N, N-dimethylaniline, triethylenediamine, furthermore triphenylphosphine, trimorphoiinophosphine or their Mixtures. Other catalysts are e.g. lithium methylate, lithium benzoate, sodium ethylate, potassium tert-butylate as well as organic tin compounds such as dibutyltin oxide, dimethyltin stearate, dibutyltin glycolate, Dibutyltin dilaurate, diphenyltin oxide, ferrocene [= dicyclopentadienyl-iron- (II)], furthermore metal chelates, such as iron acetylacetonate, cobalt complexes, each individually or combinations of such compounds.

The method is well suited in the same manner as for the preparation of symmetrical or asymmetrical Open _t Triketoimidazolidinverbindungen built. This is

for example possible when using a polycarboxylic acid according to formula XXVlI (see formula sheet).

The theimostabililäl is particularly large in product

j <> th with a low content of hydrogen, in particular but in the absence of aliphatically or cycloaliphatically bound hydrogen in the hetero ring system. The films and foils that are obtained from the claimed preliminary products are also distinguished characterized by very good elasticity properties. Their adhesion to metal surfaces is great.

The radical R in the oxamic acid esters is more aromatic Nature, d. H. a carbocyclic or heterocyclic radical with aromatic character.

•> o Suitable bifunctional radicals R of the bis-oxamic acid esters are z. B. those according to formulas XII to XV of the formula sheet, in which X = -CH ₁ -, -O-, -S-, -SS-, -SO ₂ -, - N = N -, - NR ^v "- (- R ^v "is an aliphatic, cycloaliphatic or aromatic radical with

·>'Up to 8 carbon atoms), also diphenylene, dimethyldiphenylene, anthraquinonylene, pyridylene, quinolylene, thiophenylene, benzofurylene and N-methylcarbazolylene radicals. The radical R- can also be mono- or polysubstituted in one or more aromatic and / or heterocyclic nuclei or in the side chain, provided that the substituents do not react with the isocyanates under the conditions claimed. These substituents can be alkyl, alkoxy, haloalkyl, ester, alkylketo-. (o> -m -) - ketoalkyl, alkylsulfonyl groups each having 5 carbon atoms, where m is an integer from 1 to 3, such as -CH ₃ , -C ₂ H ₅ , -OCH ₃ , -OC ₂ H ₅₁ -CF ₃₇ -COOC ₂ H ₅ , -CN, -COCH ₃ , -SO ₂ CH ₃ , furthermore nitro, cyano groups, halogen, in particular F, Cl, Br.

R ™ and R ^v in the oxamic acid esters used are, for. B. alkyl radicals with up to 6 carbon atoms, preferably -CH ₃ , -C ₂ H ₅ , -C ₄ H ₉ , phenyl or with alkyl, ζ. B. the aforementioned groups substituted phenyl radicals.

The radical R '"in the isocyanates means a divalent, z. B. an aliphatic, cycloaliphatic ^ aromatic or mixed aromatic-aliphatic Remainder with generally up to 20, preferably

up to 15 carbon atoms, e.g. B. ethylene, propylene, butylene, also the radicals according to formulas XII and XIII, in which X is -CH ₂ - or -O-, and according to formulas XIV to Xix of the formula sheet.

These residues can be used in one or more ways, for. B. by at least one alkyl, alkoxy, haloalkyl group each with up to 5 carbon atoms, also nitro groups, halogen, especially F, Cl, Br, z. B. -CH ₃ , -C ₂ H ₅ , -OCH ,, -OC ₂ H ₅ , CF ₃ , with several aromatic rings by -CH ₂ -, -O-, '-S-, -SS-, -SO ₂ -, -CO- or N = N- can be linked. Appropriately, however, no more than 5 Η atoms are substituted by such groups in each radical R '″.

Instead of the free isocyanates, isocyanate can also be used separating compounds, e.g. B.

Diphenylmethane-4,4'-bis (phenyl carbamate),

Diphenylethane-4,4'-bis (butyl carbamate).

Diphenyl-4,4'-bis (carbamic acid diethylamide) can be used.

Suitable polycarboxylic acids or their anhydrides are, for example

Isophthalic, bromoisophthalic,

5-aminoisophthalic, trimellite, pyromellite, terephthalic,

2,5-dianilinoterephthal-,

2,5-ditoluidino-terephthal-,

4-aminonaphthalene,

4,4-methylenebisanthranil-,

Hemimellite, Mellith, Malein, Fumar, Itacon, Hexahydroterephthal, Adipic, glutaric, succinic, sebacic, suberic acid,

Tetrahydrofuran tetracarboxylic acid, benzophenone tetracarboxylic acid, 1,4,5, e-naphthalene tetracarbon, Perylenetetracarboxylic acid,

Benzophenonhexacarbonsäuredilacton, furthermore condensed systems, the at least 2 carboxyl groups contained in the molecule, such as B.

Ν, Ν'-terephthaloyl-bis-glycine, Ν, Ν'-isophthaloyl-bis-glycine, Biscarboxymethylamino-diphenylmethane,

(or diphenyl ether or diphenyl sulfone). Polycarboxylic acids of the formula XXIV bis XXVIIa (see formula sheet) are suitable for the implementation.

The yields of Ν, Ν'-disubstituted 2,4,5-triketoimidazolidines are generally high in the present process, mostly over 90% of theory.

It is also possible to increase the molecular weight of the reaction products prepared according to the invention by a thermal treatment at temperatures between 200 and 550 ^° C., preferably between 260 and 480 ^° C., and thereby achieve extraordinary thermal stability and practical insolubility in the usual solvents.

The monomeric and polymeric compounds prepared according to the invention, especially the low molecular weight compounds are extremely versatile, z. B. They are valuable intermediates for organic products Syntheses. They serve - especially in their low molecular weight form - as starting materials for the manufacture of pharmaceuticals, pesticides such as insecticides, myocids and 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 and polymers produced by the process according to the invention are also suitable in particular for the coating of metallic moldings, such as wires, sheets, plates, tubes, preferably electrical conductors, being indifferent

ο is whether the application is in powder form or in solution. In the same way, however, they can also be applied to ceramic Shaped bodies are applied. After the thermal polycondensation, these objects Well-adhering, even high-temperature-resistant, thermostable coatings are obtained. The claimed connections but are also suitable, especially in powder form, after mixing with fillers, in particular inorganic nature, e.g. B. mineral powders, glass powder, glass fibers, asbestos fibers, graphite, metal powders

■ Ti and chips, for the production of shaped bodies by the hot pressing process. With these fillers, the products according to the invention can be used at high temperatures, e.g. B. at 280 to 500 ⁰ C, and high pressure, z. B. 50 to 5000 at, to moldings

> ö be working. Furthermore, they can be used to form crystal-clear sheets and films as well as fibers. Appropriate measures, e.g. B. The addition of propellants - but possibly also without such, since the alcohol released and carbonic acid formed can also act as a propellant - the products can be processed into foam-like material with high temperature resistance. The products obtained according to the invention are also suitable as stabilizers for polymeric products, in particular for polymerization and / or polycondensation resins. But you can also with such polymers, including the polymerization and / or condensation resins with heterocyclic groups, at temperatures from -10 to +250 ⁰ C, preferably at +20 to 190 ⁰ C in solution,

4 (in the melt or in the solid phase and mixed to form moldings and / or coatings are further processed. Another area of application is manufacturing high temperature resistant foams, which are particularly important for insulation purposes.

"'Examples

1. 605 g (2.4 mol) of 4,4'-diisocyanato-diphenyl ether are in 924 g of N-methylpyrrolidone-cyclohexanone mixture (30: 70% by weight) at 100 ⁰ C

-, ο solved. After adding 16 g of triethylamine, 318.5 g (0.8 mol) of 4,4'-bis (ethoxalylamino) diphenylmethane (= formula XXXII, see formula sheet) are entered within one hour. The temperature of the mixture between 105-110 ⁰ C is maintained by cooling. The viscosity increases towards the end of the addition. Then, four hours is stirred at 105-110 ⁰ C. A solution of 76.8 g (0.4 mol) of trimellitic anhydride in 240 g is then added within one hour

ω N-methylpyrrolidone at 105 ⁰ C are added dropwise The viscosity of the clear reaction product continues to rise. Finally, it is stirred at 100 ⁰ C until the CO ₂ elimination is finished This is about two to four hours according to the case.

2154 g of a clear, red-brown, highly viscous polymer solution are obtained (solids content 46% by weight). An iron sheet coated with this solution shows

ι ο

15th

20th

burn at 350 ⁰ C a pale, orange-yellow coating.

2. 199 g of 4,4'-bis (ethoxalylamino) -diphenyunethane (0.5 mol) and 96 g (04 mol) of "irimellitic anhydride are added to 544 g of N-methylpyrrolidone after adding 1 g of lithium benzoate and 5 ml of tri-nbutylamine heated to 120 ⁰ C and within 30 minutes of 250 g (1 mol) of 4,4'-diphenylmethane-Düsocyanato added. Finally, it is stirred for four to six hours at 120 ⁰ C until completion of the elimination of CO _2. After cooling, 1065 g of a clear, highly viscous polymer solution were obtained.

3. 199 g (04 mol) of bis (ethoxalylamino) diphenylmethane, 96 g (04 mol) of trimellitic anhydride, 1 g of lithium benzoate and 5 g of triethylamine are dissolved in 670 g of N-methylpyrrolidone-dimethylformamide (weight ratio 1: 1). After the mixture has been heated to 150 ^° C., 375 g (1.5 mol) of 4,4'-diisocyanatodiphenylmethane are introduced over the course of 120 minutes. ^{After cooling to 110 °} C., the reaction mixture is stirred for four hours to end the condensation. After cooling, 1185 g of a tough, clear red-brown polymer solution are obtained.

^{4. 756 g (3 mol) of 4,4'-diisocyanatodiphenyl ether are heated to 100 °} C. in 1154 g of N-methylpyrrolidone-cyclohexanone mixture (weight ratio 30:70) and, after 20 ml of triethylamine have been added, within entered for two hours 398 g (1 mol) of bis (ethoxalylamino) diphenylmethane. After 45 minutes, 161 g (0.5 mol) of benzophenone tetracarboxylic acid dianhydride are added over the course of one hour with vigorous stirring. The viscosity increases very sharply. After three hours of stirring at 100 to 110 ⁰ C a clear, .otbraune polymer solution is obtained. Yield: 2400 g (solids content approx. 52%).

5. 398 g (1 mole) of bis (äthoxalylamino) diphenylmethane and 96 g (0.5 mol) of trimellitic anhydride are in 1000 g Ν, Ν'-dimethylformamide-cyclohexanone (weight ratio 40: 60) dissolved at 40 ⁰ C. After addition of 15 ml of triethylamine and 1 g Äthylhexyltitanat 522 g (3 mol) are added dropwise 2,4-tolylene diisocyanate so that the temperature does not exceed 50 ⁰ C. The mixture is then subsequently stirred at 50 ^° C. for two hours. 1890 g of a clear, viscous solution with a solids content of about 50% are obtained.

6. 134 g (0.5 mole) of naphthalene and 398 g (1 mole) of bis (äthoxalylamino) diphenylmethane be in 1,150 g of a mixture of N-methylpyrrolidino-dimethylsulfoxide (Ge-weight ratio 45: 55) dissolved at 100 ⁰ C and within three hours, 756 g of 4,4'-diisocyanate t> o-to-diphenyl ether (3 mol) were introduced with vigorous stirring and in a protective gas atmosphere.

Finally, the mixture is subsequently stirred at 100 ^° C. for two hours. 2390 g of a dark brown viscous polymer solution are obtained. The bs viscosity of this solution is above 100,000 cps (at 2O ⁰ C).

If you work in the same way, but instead of 756 g of the diphenyl ether mentioned, 731 g (2.9 mol) of this ether and an additional 15.4 g (0.1 mol) of m-chlorophenyl isocyanate are obtained, a polymer solution with a is obtained Viscosity of only about 30,000 cP (at 20 ^° C.).

398 g (1 mol) of bis (ethoxalyiamino) diphenylmethane and 188 g (04 mol) of 2,5-bis (toluidino) terephthalic acid are dissolved in 1336 g of dimethylsulfoxide-N, N'-dimethylacetamide (weight ratio 1: 1) , heated to 100 ⁰ C and added 5 g of diazabicyclooctane as a catalyst. 750 g (3 moles) of 4,4'-diisocyanato-diphenylmethane are then added at 100-120 ⁰ C. Under strong increase in viscosity, the reaction mixture turns a deep red-brown mixture was then for two hours at 100 to 120 ⁰ C stirred. 2630 g of a clear, highly viscous polymer solution are obtained.

398 g (1 mol) of 4,4'-bis (ethoxalylamino) diphenylmethane and 106.5 g (0.5 mol) of 4-amino-naphthalic anhydride are dissolved in 1026 g of N-methylpyrrolidone and, after the addition of 20 ml of triethylamine, are dissolved 13O ⁰ C heated. Then 522 g (3 mol) of 2,4-tolylene diisocyanate are added dropwise over the course of one hour. Then zwej hours is stirred at 100 ⁰ C. 2035 g of a clear, brown polymer solution are obtained.

161 g (0.5 mol) Benzophenontetracarbonsäuredianhyrid and 398 g (1 mol) of 4,4'-bis (äthoxalylamino) diphenylmethane is dissolved in 1,081 g of N-methylpyrrolidone at 100 ⁰ C and 10 ml of tribenzylamine added. Within three hours 522 g (3 mol) are added dropwise 2,4-tolylene diisocyanate at 120-140 ⁰ C. To complete the reaction, the mixture is subsequently stirred at 100 ^° C. for two hours. 2100 g of a highly viscous, orange-red polymer solution are obtained.

199 g (0.5 mol) of 4,4'-bis (ethoxyalylamino) diphenylmethane and 250 g (1 mol) of 4,4'-diisocyanatodiphenylmethane are dissolved in 511 g of N-methylpyrrolidone-cyclohexanone (weight ratio 30:70) at 10O ⁰ C solved. After adding 10 ml of triethylamine, the reaction mixture warms to 135.degree. The mixture is stirred for a further two hours at 100 ^° C., the viscosity of the solution increasing sharply. Then 62 g (0.25 mol) of tetrahydrofuran tetracarboxylic acid, dissolved in 186 g of N-methylpyrrolidone, are added dropwise over the course of 10 minutes. Until completion of the CO ₂ elimination is stirred at 100 ⁰ C. 1190 g of a clear polymer solution are obtained.

796 g (2 mol) of 4,4-bis (äthoxalylamino) diphenylmethane and 756 g (3 moles) of 4,4'-diisocyanato-diphenyl ether are dissolved in 1000 ml of N-methylpyrrolidone and heated to 8O ⁰ C. As a result of the exothermic reaction that sets in, the temperature rises to 143 ° C. After the reaction is at 130 ⁰ C 140 g (0.5 mol) of N, N-Terephthaloylbis-glycine dissolved in 692 g N-methylpyrrolidone added over one hour. Finally, for four hours at 13O ⁰ C is stirred. Yield: 3340 g.

12. 796 g (2 mol) 4,4'-bis- {äthoxalylainino) -diphenylmethane and 140 g (0.5 mol) Ν, Ν'-terephthaloylbis-glycine are in 1000 ml of N-methyl pyrrolidone with the addition of 2C ml of triethylamine dissolved at 100 ° C After stirring for one hour at 100 ⁰ C, a solution of 756 g (3 moles) of 4,4-diisocyanato-diphenyl ether in 692 g of N-methylpyrrolidone is added within 30 minutes. The temperature rises to 106-108 ⁰ C. The mixture is stirred at 100 ^° C. for a further four hours. Yield: 3335 g of a clear, red-brown, viscous solution which shows greenish fluorescence.

16.

13. 272 g (0.5 mol) of 4,4'-bis- (4-carboxy-phthalimido) -diphenylmethane and 199 g (0.5 mol) of 4,4-bis- (ethoxyalylamino) -diphenylmethane are in 1040 g N-methylpyrrolidone ^{heated to 120 °} C., 5 ml of tributylamine were added and 375 g (1.5 mol) of 4,4'-diisocyanatodiphenylmethane were added over the course of 90 minutes. Fine crystals separate from the originally clear solution.

Then is condensed at 190 to 198 ⁰ C until the now completely clear, viscous Reakticnsgemisch be! Room temperature gives a clear, viscous polymer solution. This is the case after about eight to ten hours. Yield: 1790 g of a clear, highly viscous polymer solution.

14. 213 g (0.5 mol) 4,4'-bis (ethoxalylamino) -3,3'-di- ω methyl-diphenylmethane (melting point 136 ° C.) and 250 g (1 mol) 4,4'-diisocyanato -diphenylmethane are dissolved in 800 g dimethyl formamide at 80 ⁰ C. After adding 1.0 g of n-butyl titanate and 5 ml of tributylamine, the temperature rises to 92-95 ° C due to an exothermic reaction. After stirring for two hours, the temperature is increased to 160 ^° C. and 57.6 g (0.3 mol) of trimellitic anhydride are introduced over the course of 30 minutes. Finally, stirring is continued for six hours at this temperature. After cooling, 1290 g of a clear, viscous polymer solution are obtained.

98.4 g (0.2 mol) of crude l, 4-bis (p-äthoxalylaminophenoxyj-benzene (melting point 165 ° C) and 19.2 g (0,1MoI) of trimellitic anhydride are dissolved in 100 ml of dimethylacetamide at 130 ⁰ C and 04 ml of tribenzylamine are added. A mixture of 47.5 g (0.15 mol) of 4,4-diisocyanatodiphenylmethane and 45.4 g (0.18 mol) of 4,4-diisocyanatodiphenyl ether is added at this temperature over the course of one hour. Finally, at 140 ° C is stirred for four hours then cooled to 70 ⁰ C and 100 g of technical cresol mixture stirred After cooling to room temperature, 402 g of clear, highly viscous polymer solution are obtained, the solids content is about 50%

A mixture of 199 g (0.5 mol) of 4,4'-bis (äthoxalylamino) diphenylmethane (melting point 148 ⁰ C), 200 g (0.5 mol) of 4,4'-bis (äthoxalylamino) -diphenyläther (Melting point 140 ^° C.) and 10.9 g of pyromellitic dianhydride (0.05 mol) are dissolved in 750 g of dimethylsulfoxide-N-methylpyrrolidone mixture (weight ratio 70:30) at 70 ^° C. After adding 5 g of triethylamine and 0.05 g of lithium benzoate, 325 g (1.3 mol) of 4,4'-diisocyanatodiphenyl ether are introduced within two hours. The temperature rises up to 90 ⁰ C. After three hours of stirring at 80-90 ⁰ C is cooled to room temperature. 1465 g of a clear, red-brown, highly viscous polymer solution are obtained, the solids content of which is about 49%.

1000 g of the polymer solution prepared according to Example 16 are added dropwise with vigorous stirring to 3000 ml 60 ⁰ C warm ethyl alcohol within three hours. The pale yellow polymer body which separates out is filtered off with suction after the precipitation has ended, washed with 1000 ml of an ethanol-toluene mixture (weight ratio 1: 1) and ^{dried at 100 °} C. in a vacuum. There are 475 g of a loose, obtained pale yellow polymer powder whose softening range is 140-150 ⁰ C.

Formula sheet

O O

(1) A-NH-CC-OR ^V + 2B-N = C = OO

Il Il

c — c ο

/ \ Il

► A - NN - B + B - NH-C --OR ^N

C. O

19th

(2) R ^V OOC-CO-NH-R-NH-CO-COOR ^V + O = C = N-R '"- N = C = O

O O

Il I! c-c

► R ^V OOC —CO — NH-R — NN - R '"- NH-COOR ^V

(D

Il ο

-) 2nR ^v OH

(3) η (Γ) »

O O

! I Il c-c

R — N N-

Il ο

(η = 1-70)

CO

(A) OR _u -COOH + O = C = NR "'- N = C =

CO (II)

CO

> OR _Ir - CO - NH - R '"- N = C = O + CO ₂ T

CO amide (III)

+ R ^IV OOC-CO-NH-R -NH-CO -COOR ^V

(5) oxamic acid ester (IV)

CO CO - CO

OR _lr —CO —NH-R '"—NN —R —NH-CO —COOR ^V + R ^1V OH

^x co

Triketoimidazolidine-imide (V)

CO

CO (6) O = C = N-R '"- N = C = O + θ' ^X R _lr -CO

(II)

(V)

CO

O = C = N- R '"- NR ₁ -CO + CO ₂ T

\ / Imide (Vl) CO

21 22

co-co co

rivq - CO - CO - NH - R - NN - R '"- NH - CO - R _1x

CO

CO

CO - CO
-R '"- n' ^X N —Κ"'- NH-CO —OR ^v -) (nR ^lv —OH + nR ^v —OH)

CO

(X)

R ^IV O - CO - CO - NH- R-

co-co co

^N N-R '"- NH-CO-R _l f

—R '"-

CO

co

co-co

Q —R —N N - R '"- Q'

CO
-X

(XIII) H ₃ CH ₃ C co-co

co

-I - R '"- NH-CO-OR ^V

(XD

(IX)

(XII)

- (CH ₂ ) ₆ -

H ₃ C

(χ ν in

CH ₂ -

(XVIII)

CH ₃
-CH-CH ₂ -CH ₂ -

(XIX)

NCO

CH ₃ -O-CO-NH

NCO

CH, - CH ₂ -C-CH ₂ -O- CO - NH- <ΤΎ> - CH ₃ (XX)

CH ₂ -O-CO-NH

NCO

23

C-NH- (CHA-NCO

OCN- (CHA-N

NCO

C_NH- (CH _{2) 6} -NCO OO

O = C

= O O = C

HOOC 0

Il

HO-C HO - C 'Il ο

NCO

CH) O

I J

OJ-NCO CH ₃

COOH

COOH 24

CH ₃

NCO

O O
M. V O OH
OH O O
U COH
Il Il
Χ — Ν
Il Jl _M
II c—
(
c— Il
—C— Il
COH
j Il
O M.
O M. Il
O O
Il Il
O Il
r
I. c— <
H Il
O

HOOC

COOH

COOH (XXII)

(XXIV)

(XXV)

(XXVI)

(XXVlI)

(CH ₂ ) _m , m = 2-8)

25th

OO

nhc-y-c-nh

(= (CH ₂ ) ,,, ρ = 2-8)

26th

(XXVIIa)

(XXVIID

(XXVIIIa)

QR (4I) _x -RpOIv- (It) ₇

ν ■

- R ¹ - (k) ,,

■ - R '- (k) _s

CO - CO

NICO CO

CO

t-N

Rpoly

CO-COCO—

CO

CO - CO

CO _ Jt J ν JZ

H ₂ C = (C ₆ H ₄ -NH-CO-COOC ₂ Hj) ₂

(8) Q-R-Q '+ R'"= 4N = C = O) ₂

CO - CO
> Q - Ri - hi / \ - R '"- Q'

-R "'—Q' (XXlX)

(XXXD

(XXXID

(XXXIID

co

Claims (10)

Patent claims: 1. Process for the preparation of modified Ν, Ν'-substituted 2,4,5-triketoimidazolidines with conversion of bisoxamic acid esters of the formula R- (NH - CO - CO - OR ^ (VI) with diisocyanates of the formula
R '"_ (N = C = O) ₂ St. (VIII) or compounds which split off these isocyanates, in which ι ■> R ^{v means} 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 is optionally substituted by hydrocarbon radicals with up to 14 carbon atoms, at temperatures from 0 to 250 ^° C. and optionally in the presence of a catalyst, characterized in that additionally dicarboxylic acids or higher, up to hexavalent anhydride-forming polycarboxylic acids and / or their anhydrides are reacted to form condensation products with amide and / or imide groups , where in the above formulas R is a remainder of the group a) an at least mononuclear divalent s; aromatic residue with up to 20 carbon atoms, b) a pyridylene, quinolylene, thiophenylene, Benzofurylene or N-methylcaroazoylene radical, c) a radical a) or b), which is replaced by halogen, nitro, cyano, dialkylamino, diarylamino, Alkyl arylamino, alkyl, alkoxy, carboxyalkyl, Carboxyaryl, acyl, cycloalkyl, haloalkyl, haloalkoxy, halocarboxyalkyl, Halocarboxyaryl or halo-acyl groups each with up to 18 carbon atoms, (<a-m -) - ketoalkyl or alkylsulfonyl groups is substituted by 5 carbon atoms in each case, d) is an anthraquinone radical, which is replaced by halogen, nitro, cyano, dialkylamino, diarylamino, Alkyl arylamino, alkyl, alkoxy, carboxyalkyl, carboxyaryl, acyl, Cycloalkyl, haloalkyl, haloalkoxy, halocarboxyalkyl, halocarboxyaryl or haloacyl groups, each with up to 18 carbon atoms or with (ω-m -) - ketoalkyl groups can be substituted with 5 carbon atoms, where in the ketoalkyl groups mentioned under c) and d) m is an integer from 1 to 3, R '"is a divalent residue, namely e) an aliphatic, aromatic or mixed aromatic-aliphatic radical with up to 20 carbon atoms, G) a cycloaliphatic hydrocarbon radical with up to 12 carbon atoms, a radical e) or f), which is replaced by at least one of the radicals halogen, nitro, alkyl, Alkoxy or haloalkyl is substituted by up to 5 carbon atoms, the di- or polycarboxylic acid residue is a residue of the group h) an unsubstituted bivalent to hexavalent carbocyclic hydrocarbon radical with 2 up to 20 carbon atoms, a remainder of the acid anhydride according to the formula O O Il Il NHC-Y-C-NH (XXVIII) Y = = (CH ₂ ), (XXVIIIa) i) a radical h) which is substituted by halogen or amino groups or a bis-toluidinterephthal- acid residue or a terephthaloylbisglycine residue, k) an aliphatic divalent alkylene residue with 2 to 8 carbon atoms, 1) a heterocyclic radical with 2 to 20 carbon atoms or a radical of the acids according to the formulas O O HOOC COOH (XXIV) (XXV) OI N-x-N TO OI> -x-n OI N-x-N TO (XXVII) HOOC X = (CH ₂ ) _m , m = 2-f COOH and formulas XXVIII and XXVIIIa (see above) m) a heterocyclic radical 1), which by Is substituted by alkyl, halogen or amino groups, and where the molar ratio of the oxamic acid esters to the polycarboxylic acids is 0.97 to 0.03: 0.03 to 0.97, the sum of the two compounds always being one mole. 2. The method according to claim 1, characterized in that the reaction with the polycarboxylic acids takes place during and / or after the reaction of the oxamic acid esters with the isocyanates. 3. The method according to claims 1 or 2, characterized in that the by heating monomeric compound obtained in the first stage- (XXVIIa) gen with at least one end group Q and Q '(-NH-COOR ¹ "' and -NH-CO-COOR *) to 200 to 55O ⁰ C in solid form or in the presence of solvents are post-polymerized, where R ^IV and R ^{v the} same or can be different and mean aliphatic hydrocarbon radicals with up to 18 carbon atoms, cycloaliphatic hydrocarbon radicals with up to 8 carbon atoms, mononuclear aromatic hydrocarbon radicals with 6 carbon atoms which are unsubstituted or substituted by hydrocarbon radicals with up to 14 carbon atoms . 4. Process according to claims] to 3, characterized in that trimellitic anhydride is used as a polycarboxylic acid. 5. Process according to claims 1 to 4, characterized in that 4,4'-diisocyanato diphenylmethane is used as the isocyanate. 6. Process according to claims 1 to 3, characterized in that the oxamic acid ester 4,4'-bis (ethoxyalylaniino) diphenylmethane is used will. 7. The method according to claims 1 to 6, characterized in that first the polycarboxylic acids with the isocyanates in the presence of at least one solvent to form a precondensate are reacted with isocyanate end groups, whereupon the precondensate in a further stage also in the presence of at least one solvent at an elevated temperature with the Oxamic acid esters further to higher molar, especially polymeric products with triketoimidazolidine rings is implemented. 8. Use of the products prepared by the process according to claims 1 to 7 for Manufacture of moldings and coatings. 9. Use according to claim 8 for the production of moldings containing mineral fillers, preferably contain glass fibers and / or graphite. 10. Use according to claims 8 or 9 for the production of moldings, the fibers and / or foils.