What is the formula of urea oxalate


The present invention also relates to processes for the preparation of the above-mentioned modified azulmic acids, their acid addition salts and complex compounds and the mixed products of these modified azulmic acids with additives, the processes consisting in that one

1) known azulmic acid almost free of defects in an aqueous medium,

a) optionally treated in the presence of additives with organic or inorganic acids, or

b) optionally treated in the presence of additives with bases or basic salts, or

c) treated with water in the neutral range, or

d) treated with vegetable ashes, catalytically active natural substances and / or fertilizers, or

e) optionally treated with metal salts in the presence of oxidizing agents and optionally in the presence of organic acids, or

f) treated with metal salt complexes stabilized azulmic acids, or

g) treated with oxidizing agents,


or that one

2) Hydrocyanic acid is polymerized with the aid of basic catalysts under hydrolyzing conditions in an aqueous medium, optionally in the presence of additives,
or that one

3) Modified azulmic acids are reacted with bases in an aqueous medium and, if necessary, the cation is then exchanged by treatment with metal salts,
or that one

4) modified azulmic acids treated in an aqueous medium with organic or inorganic acids,


and the products produced by one of the processes mentioned are then optionally treated with acid or base.

The invention also relates to the use of the products according to the invention for various purposes. For example, they are suitable as intermediate products for the production of stabilized azulmic acids, which are azulmic acids with high resistance to the elimination of hydrocyanic acid. Furthermore, the substances according to the invention can be used as catalysts and reactive fillers in isocyanate chemistry for the production of polyurethane plastics. Those substances according to the invention which have a high ionic content and thus have a polyelectrolyte character can function as ion exchangers. Products according to the invention which contain phosphoric acid, phosphorous acid, polymethylene ureas and / or polymethylene melamines or other suitable additives can be used as flame retardants, anti-aging agents and as reactive fillers for a wide variety of polyurethane plastics, vinyl polymers, polyamide plastics, rubbers and epoxy resins. In addition, the products according to the invention can either be used as agrochemicals themselves or serve as intermediates for the production of agrochemicals.

In the present case, modified azulmic acids are to be understood as meaning those hydrocyanic acid polymers which have ionic groups of the formulas

and

contain. Such groups have their origin in nitrile groups which are present in azulmic acid and which can be regarded as stopping points in the cyclizing nitrile polymerization.

In an idealized representation, the transition from a nitrile group of azulmic acid to a corresponding carboxyl group can be illustrated by a formula as follows:

or.



Of course, amide or imide groups are also formed from nitrile groups. So z. B. show the formation of amide groups by the equation below.



The inventive generation of ionic or nonionic groups of the above formulas takes place not only on nitrile groups that are already present in the polymer used, but also on those nitrile groups that are formed by catalytic decyclizations. In addition, various other hydrolysis reactions are responsible for the formation of defects. For example, a

those in the molecular association of A.Zulmic acid is to be understood as α-aminonitrile, can be converted into a carbonyl group by splitting off hydrogen cyanide and subsequent topochemical hydrolysis reaction according to the following equation:



The following are the ionic groups of the formula

as F1-Faults and the groups of the formula

as F2-Defects designated.

The F2- Defects arise from the F1- Defects in which R stands for hydrogen or another suitable ion, according to the following equation:

or in the molecular association of azulmic acid:

Defects due to the decarboxylation reaction

Increase in NH2-Group concentration, loss of acidity, increase in basicity.



As can be seen from the formula (II) given above, each F generated1- Defect in the immediate vicinity of an α-position and a ß-position amino group. Thus, at the F1-Faults in the constitution

either intramolecular zwitterionic salts of the constitution

or intermolecularly cross-linked salts between several azulmic acid molecules of the following idealized representation:



The formation of intramolecular salts, i.e. 5-membered rings, is preferred.

Since the emergence of the F1-Faults with the release of ammonia and the formation of the F2-Faults is coupled with the release of carbon dioxide, the released amount of ammonia and carbon dioxide represents a quantitative measure for the amount of the generated defects. The quotient of the released molar amount of ammonia and the released molar amount of carbon dioxide provides information about the ratio of F.1- to F2-Faults.

The defect content of the modified azulmic acids according to the invention in percent by weight is determined below in each case in such a way that the equivalent weight of the defect in question (- ionic or non-ionic group F1 or F2) relates to the corresponding weight size (100 g) which has not been converted into an ionic or non-ionic group. This is how, for example, the concentration of flaws for an F is calculated1Defect in which R stands for hydrogen, from the molar amount of ammonia formed in each case and the fact that the associated ionic group of the formula

has an equivalent weight of 73.

The F is calculated in an analogous manner2Defect content from the particular molar amount of carbon dioxide released and the fact that the grouping in question has the formula

has an equivalent weight of 29.

It is to be regarded as extremely surprising that the modified azulmic acids according to the invention and their acid addition salts, complex compounds and mixed products from the known azulmic acids are accessible in a topochemical reaction, although the polymers used as starting materials are completely insoluble and only one because of the low porosity have a relatively small surface. In contrast to the previously known hydrocyanic acid polymers, the modified azulmic acids according to the invention dissolve very easily in 0.5 to 1 normal aqueous sodium hydroxide solution or potassium hydroxide solution. It is also surprising that the targeted introduction of flaws is possible.

The substances according to the invention have a significantly higher swellability than the previously known azulmic acids. They have reactive groups and can be used in many ways. In particular, they are suitable as starting products for the production of stabilized azulmic acids, which in the present case are to be understood as meaning condensation products of azulmic acids containing defects with aldehydes or ketones. The substances according to the invention thus represent a valuable addition to technology.

The defects contained in the modified azulmic acids according to the invention are represented by the formulas (F1) and (F2) Are defined. In the formula (F1) R preferably represents hydrogen, ammonium or an equivalent of a cation of a metal from main groups I to V or from subgroups I to VIII, the cations of lithium, sodium, potassium, beryllium, magnesium, calcium , Strontium, barium, aluminum, thallium, tin, lead, bismuth, copper, silver, gold, zinc, cadmium, mercury, titanium, zircon, chromium, manganese, iron, cobalt, nickel, platinum and palladium, rhodium and rutenium are mentioned as examples be.

B. Permethylation, the aforementioned basic nitrogen compounds arise. Particularly preferred nitrogen bases in this context are methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tert-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, ethylenediamine, pyrrolidine, piperidine, morpholine, imidazole, 2,4-triazole, 1,2,3-triazole, 2-ethyl-imidazole and aminotriazole. Furthermore, R preferably represents trialkylsulfonium cations, in particular the triethylsulfonium cation.

Azulmic acid addition salts according to the invention are to be understood as meaning those salts which are formed by addition of a proton of an inorganic or organic acid to an amino group or another suitable group in a modified azulmic acid. Inorganic acids that can be used here are preferably hydrohalic acids such as hydrofluoric acid, hydrochloric acid and hydrobromic acid, furthermore acids of phosphorus such as phosphoric acid, phosphorous acid, dialkylphosphoric acid, e.g. dibutylphosphoric acid, polyphosphoric acid with molecular weights of 6,000 to 40,000 and phospholine oxy-phosphonic acids, e.g. those of the formulas

also nitric acid and acids derived from sulfur, such as sulfuric acid and sulphonic acids, ethylsulphonic acid, p-toluenesulphonic acid and naphthalene-1,5-disulphonic acid being mentioned as examples. Preferred organic acids are saturated or unsaturated carboxylic acids, such as formic acid, acetic acid, propionic acid, 2-ethylcaproic acid, acrylic acid, methacrylic acid, oleic acid and ricinoleic acid, and also halocarboxylic acids, such as chloroacetic acid
acid, dichloroacetic acid and trichloroacetic acid, also dicarboxylic acids such as maleic acid, fumaric acid and succinic acid and half esters derived therefrom, and also hydroxycarboxylic acids such as hydroxyacetic acid, tartaric acid, citric acid and salicylic acid.

Azulmic acid complex compounds according to the invention are preferably to be understood as meaning complexes of modified azulmic acids and metal compounds or ammonium salts. Particularly suitable metal compounds here are salts, acids, hydroxides or oxides of metals from main groups II to V or subgroups I to VIII. Examples include calcium chloride, acetate, nitrate and hydroxide or oxide, strontium nitrate, barium chloride and acetate, borates, aluminum acetate and formate, thallium sulfate, thallium nitrate, silicon tetrachloride, sodium or potassium silicate, Tin-II-chloride, lead-II-chloride, -II-acetate and -II-hydroxide, bismuth-III-hydroxide and bismuth-III-nitrate, copper sulfate, -nitrate and -acetate, silver nitrate, tetrachloroauric acid, zinc chloride and acetate, cadmium chloride, mercury II chloride, titanium tetrachloride and tetrabutoxide, zirconium sulphate, vanadates, chromium III chloride, molybdates, tungstates and their heteropoly acids, manganese II sulphate and II acetate, iron II sulfate, II acetate and III chloride, cobalt chloride, nickel chloride, hexachloroplatinic acid and palladium II chloride. - Particularly suitable ammonium salts are ammonium nitrate and ammonium acetate.

Organic natural substances and products obtained therefrom, inorganic natural substances and products obtained therefrom, synthetic organic products, synthetic inorganic products and / or mixed products of organic and inorganic products can be contained as additives in the products according to the invention.

Organic natural substances and products obtained therefrom are preferably wood powder, lignin powder, lignin sulfonic acids, ammoniated lignin sulfonic acids, humus, humic acids, ammoniated humic acids, peat, proteins and the degradation products, e.g. hydrolysis products of yeast, algae material (alginates), Polypeptides such as wool and gelatine, fish meal and bone meal, and also amino acids, oligopolypeptides, pectins, monosaccharides such as glucose and fructose, disaccharides such as sucrose, oligosaccharides, polysaccharides such as starch and cellulose, furthermore hemicelluloses, homogenized materials of vegetable and animal origin, activated charcoal and ashes obtained by partial oxidation, complete oxidation or combustion of organic substances formed by photosynthesis or conventional fuels, whereby fir ash, gorse ash, ashes from Serbian spruce, oak ash, birch ash, beech ash, willow ash and tobacco leaf ash specifically g be named.

Inorganic natural substances and products obtained therefrom are preferably silicates, such as aluminum silicates, calcium silicates, magnesium silicates and alkali silicates, also sea sand and other naturally occurring silicon dioxides, silicas, in particular dispersed silicas, silica gels, furthermore clay minerals, mica, carbonates such as calcium carbonate, Phosphorite and phosphates such as calcium phosphate and ammonium magnesium phosphate, sulfates such as calcium sulfate and barium sulfate, as well as oxides such as zirconium dioxide, nickel oxide, palladium oxide, barium oxide, disperse antimony oxides and aluminum oxides such as bauxite, aluminum oxide hydrate, as well as fly ash and soot types of various kinds.

As synthetic organic products are preferably aminoplast condensates, in particular those made from urea, dicyandiamide, melamine or oxamide and aldehydes, such as formaldehyde, acetaldehyde, isobutyraldehyde, hydroxypivalaldehyde, crotonaldehyde, hydroxyacetaldehyde, furfural, glucose, and specifically named be condensation products of urea and formaldehyde, urea and glyoxal, urea and acetaldehyde, urea and isobutyraldehyde, urea and crotonaldehyde, urea and hydroxypivalaldehyde and 2-oxo-4-methyl-6-ureido-hexahydropyrimidine, which is a known condensation product from 1 and 2 moles of urea is formed from intermediate crotonylidene diurea with saturation of the double bond and which has the constitution

comes to. Also suitable as synthetic organic products are preferably plastics such as polyamide powder, polyurethane powder and polycarbodiimides, also polymeric quinones, addition or condensation products of quinones, in particular benzoquinone, with amines or ammonia, and also with aldehydes, in particular formaldehyde, crosslinked gelatins, synthetic Soil improvers, such as the product known as Hygromull (= urea-formaldehyde resin flakes), in addition synthetic sugars, such as formose-sugar mixtures made from formaldehyde, and also sparingly soluble cane sugar complexes, such as the sucrose-calcium oxide complex with a composition of 1 mol sucrose 3 moles of calcium oxide, and finally organic ammonium salts such as ammonium carbaminate and other organic nitrogen compounds such as hexamethylenetetramine and hexahydrotriazines.

As synthetic inorganic products that preferablyF. Possible fertilizers, such as superphosphate, Thomas slag, rhenaniaphosphate, phosphorite, calcium cyanamide, calcium ammonium nitrate, leunas nitrate, potassium phoaphate, potassium nitrate and ammonium nitrate, and also pigments such as iron oxides and titanium dioxide, also metal oxides and metal hydroxides such as calcium oxide, Bismuth hydroxide, manganese hydroxide and magnesium hydroxide, with hydroxides produced in situ being particularly preferred, furthermore synthetic silicas, in particular silicic acid produced in situ and its salts, also water glass, salts such as cobalt molybdate, ammonium carbonate and calcium carbonate, and also catalysts, in particular heavy metal catalysts, of the most varied types .

Mixed products of inorganic and organic products are preferably neutral, basic or acidic soils, natural soil improvers, biologically active garden soil and sewage sludge.

The additives can be present in the products according to the invention in a physical and / or chemical bond in an amount from 1 to 95 percent by weight, preferably from 5 to 90 percent by weight. In some cases, there may be products in which the modified azulmic acids are encased by the additives. An example of such products are polycarbodiimides coated, e.g. microencapsulated, modified azulmic acids.

In the production of the products according to the invention by the process (1) according to the invention, variants (a) to (g), hydrocyanic acid polymers, so-called azulmic acids, which are virtually free of defects, are used as starting materials. Such azulmic acids, which are almost free of defects, are already known (cf. Houben-Weyl, Volume 8 (1952), page 261; DT-PS 662 338 and DT-PS 949 600).

According to variant (a) of process (1) according to the invention, the azulmic acids, which are virtually free from defects, are treated with inorganic or organic acids, if appropriate in the presence of additives. In this connection, all those acids which have already been preferably enumerated in connection with the description of the azulmic acid addition products according to the invention are preferably used as inorganic or organic acids. Organic natural substances and products obtained therefrom, inorganic natural substances and products obtained therefrom, synthetic organic products, synthetic inorganic products and / or mixed products of organic and inorganic products can be used as additives. These preferably include all those materials which have already been mentioned as preferred in connection with the description of the additives which may be present in the substances according to the invention.

When carrying out variant (a) of process (1) according to the invention, the process is carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as hydrogen sulfide or alcohols, methanol and ethanol being specifically mentioned.

In the case of variant (a) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 0.degree. C. and 200.degree. C., preferably between 20.degree. C. and 120.degree. C., are used.

The reaction according to variant (a) of process (1) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out variant (a) of process (1) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight 54) of almost defect-free azulmic acid a catalytic amount or 1 to 4 mol of an inorganic or organic acid and optionally such an amount of additives that their proportion in the end product is between 1 and 95 percent by weight, preferably between 5 and 90 percent by weight. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried.

When carrying out variant (a) of process (1) according to the invention, nitric acid is used to generate defects and the reaction temperature is kept relatively low, preferably between 20 and 30 ° C., traces of hydrocyanic acid split off are oxidized, while additions are extremely easy at the same time of nitric acid to the amino groups of the modified azulmic acids and modified azulmic acid types are obtained in a simple topochemical reaction, the ionic groups of the constitution on their amino groups

In this way, for every 100 parts by weight of modified azulmic acid, about 0.5 mol of nitric acid is bound. Depending on the type of process and the duration of action of the dilute nitric acid on the modified azulmic acids, about 30 to 50% of the amino groups present are amenable to salt formation. Traces of free nitric acid can advantageously be converted into ammonium nitrate by gassing the products with gaseous ammonia, the reaction advantageously being carried out in the solid phase in a fluidized bed.

When carrying out variant (a) of process (1) according to the invention, phosphoric acid or phosphorous acid is used to generate defects and the reaction temperatures are kept relatively low, preferably between 20 ° C and 55 ° C, so decarboxylation reactions and the associated ones Generation of F2-Faults largely pushed back. At the same time, the acids are bound extremely easily by the amino groups of the modified azulmic acids in a heterogeneous reaction. In this way, of 100 parts by weight of modified azulmic acid, about 0.2 mol of phosphoric acid or about 0.5 mol of phosphorous acid are bound within five minutes. The resulting salts are almost insoluble in water. Small amounts of free phosphoric acid or phosphorous acid contained in the products can advantageously be converted to the corresponding ammonium salts by treating the products with gaseous ammonia, the reaction advantageously being carried out in the solid phase in a fluidized bed.

In a particular embodiment of variant (a) of process (1) according to the invention, the azulmic acid is used in the presence of hydrolytically degradable natural substances, such as celluloses, hemicelluloses, sugar, lignin, polymeric quinones, wood powder, vegetable material, polypeptides such as gelatin and wool, also yeast proteins, algae masses and peat plants, with 0.2 to 80% phosphoric acid or phosphorous acid. The creation of defects takes place with simultaneous hydrolytic degradation of the respective natural substances used. If polypeptides are used, these are split into mixtures of amino acids. Due to its numerous amino groups, azulmic acid binds about 0.3 to 0.4 mol of phosphoric acid or phosphorous acid, while the phosphoric acid salts of the amino acids or those of the oligopolypeptides, or the other low molecular weight breakdown products of the natural substances used, even if they are water-soluble are often fixed in large quantities by the azulmic acid matrix. Excess acid, e.g. B. phosphoric acid, can be precipitated as calcium phosphate on the azulmic acid matrix by adding calcium hydroxide. If hydrolyzed sugars and oligosaccharides are present, these are absorbed in the form of their mostly poorly soluble calcium complexes on the azulmic acid. The process products obtained according to this variant of process (1) according to the invention can be stored for a long time without an unpleasant odor occurring, as is otherwise the case when natural substances such as oligopeptides, peptide-sugar mixtures, etc. are broken down by biological processes.

Another particular embodiment of variant (a) of process (1) according to the invention consists in that 1 to 4 mol of 1 molar phosphoric acid solution are used to generate the defects, and the excess phosphoric acid is then used as Calcium phosphate is precipitated as magnesium phosphate by adding magnesium chloride or as ammonium magnesium phosphate by adding ammonia and magnesium salts. Various kinds of additives can be used at the same time. Particularly preferred additives in this case are vegetable ashes, insoluble polyquinones, addition or condensation products of benzoquinone with amines, in particular with Ammoriak, ferrer lignin, ligninsulphonic acid, humic acids, various fly ashes, bauxite, aluminum oxide, cobalt molybdate, silicon dioxide, activated carbon, zirconium dioxide, nickel oxide , Palladium oxide and barium oxide. Furthermore, sugars such as cane sugar and other sugars which do not contain free aldehyde groups, or also formose sugar mixtures made from formaldehyde, are also possible as preferred additives. These different types of sugar can be fixed in the channels and pores of the rigid azulmic acid body. In addition, the various sugars can also be absorbed by the azulmic acids in the form of their mostly poorly soluble calcium complexes.

According to variant (b) of process (1) according to the invention, the azulmic acids, which are virtually free of defects, are treated with bases or basic salts, if appropriate in the presence of additives. Both organic and inorganic bases can be used as bases here. Organic bases that can preferably be used are ammonia, alkylamines with 1 to 6 carbon atoms, dialkylamines with 1 to 6 carbon atoms per alkyl group, trialkylamines with 1 to 6 carbon atoms per alkyl group, hydroxyalkylamines with 1 to 6 carbon atoms, di- (hydroxyalkyl) amines with 1 up to 6 carbon atoms per hydroxyalkyl group, tri- (hydroxyalkyl) amines with 1 to 6 carbon atoms per hydroxyalkyl group, alkyl hydroxyalkyl amines with 1 to 6 carbon atoms in the alkyl or in the hydroxyalkyl group. Cycloalkylamines with 3 to 8 carbon atoms, alkylenediamines with 2 to 6 carbon atoms, guanidine, melamine, dicyandiamide, saturated or unsaturated heterocyclic nitrogen bases with 5 to 7 ring members and 1 to 3 nitrogen atoms in the heterocyclic ring, as well as those bases that differ from the quaternization, for example permethylation, derive compounds formed from the aforementioned nitrogen compounds, and also those bases which are derived from trialkylsulfonium compounds. Particularly preferred nitrogen bases in this context are ammonia, methylamine, methylethanolamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tert-butylamine, ethanolamine, diethanolamine, triethanolamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, ethylenediamine, pyrrolidine, piperoline, imide, pyrrolidine, piperoline Pyrazole, 1,2,4-triazole, 1,2,3-triazole, 2-ethyl-imidazole, aminotriazole and triethylsulfonium hydroxide.

Inorganic bases which can preferably be used are alkali and alkaline earth metal hydroxides, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide may be mentioned in particular.

The basic salts used when carrying out variant (b) of process (1) according to the invention are preferably alkali sulfides, such as sodium sulfide, sodium hydrogen sulfide and potassium hydrogen sulfide, also sodium thiosulfate, ammonium thiosulfate, ammonium polysulfide, calcium hydrogen sulfide, calcium thiosulfate and calcium cyanamide, furthermore potassium hydrogen carbonate, potassium hydrogen carbonate and water glass (sodium or potassium water glass) to insert. Mixtures of ammonia and sodium thiosulphate, ammonium thiosulphate, sodium hydrogen sulphide, sodium sulphide and / or ammonium polysulphides are also particularly suitable for creating defects using this method.

When carrying out variant (b) of method (1) according to the invention, organic natural substances and products obtained therefrom, inorganic natural substances and products obtained therefrom, synthetic organic products, synthetic inorganic products and / or mixed products of organic and inorganic products can be used as additives be used. These preferably include all those materials which have already been mentioned as preferred in connection with the description of the additives which may be present in the substances according to the invention.

When carrying out variant (b) of process (1) according to the invention, one works in an aqueous medium or in an aqueous-alcoholic medium. A preferred reaction medium is water or a mixture of water and alcohol, such as methanol or ethanol. However, it is also possible to partially replace water with hydrogen sulfide. - If you work in the presence of hydrogen sulphide or in the presence of reagents that give off hydrogen sulphide under the reaction conditions and keep the reaction temperature between 700C and 100 ° C, small amounts of split-off hydrocyanic acid are converted into carbon oxysulphide and ammonia with simultaneous generation of defects.

In the case of variant (b) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, one works at temperatures between 00C and 200 ° C, preferably between 20 ° C and 150 ° C.

The reaction according to variant (b) of process (1) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased pressure. The latter is particularly recommended when gaseous ammonia is used to create defects.

When carrying out variant (b) of process (1) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight 54) of almost flawless azulmic acid a catalytic amount or 1 to 4 mol, preferably 1 to 2 mol of base or basic salt and optionally such an amount of additives that their proportion in the end product is between 1 and 95 percent by weight, preferably between 5 and 90 percent by weight. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried. The base still contained in the end product can advantageously also be neutralized by adding an appropriate amount of acid, such as phosphoric acid, so that the resulting products then also contain the respective salts.

If an excess of acid is used in this neutralization, acid addition salts of the respective modified azulmic acids are formed.

If, when carrying out variant (b) of process (1) according to the invention, strong bases are used to generate faulty atoms, azulmic acids with particularly high fault site contents can be prepared after relatively long reaction times. The resulting products have a polyelectrolyte character. The course of such a reaction can be illustrated idealized by the following equation for the case that potassium hydroxide is used as the base.



If, in this variant (b) of process (1) according to the invention, an excess of concentrated (25%) ammonia solution is used and the reaction is carried out at room temperature, modified azulmic acids containing high levels of defects are obtained after about 6 to 20 hours of reaction time whose carboxyl groups are partly in the form of ammonium carboxylate groups. However, it is also possible to convert modified azulmic acids in which free carboxyl groups are present into the corresponding ammonium salt-containing products by gassing with ammonia in a fluidized bed.

In a particular embodiment of variant (b) of process (1) according to the invention, the azulmic acid is used in an aqueous-alcoholic medium at temperatures between 120.degree. C. and 1400C with gaseous ammonia under pressure. This produces modified azulmic acids, which have a high content of ammonium carboxylate groups. The free amino groups contained in these products are also able to bind acids such as phosphoric acid, so that the end products contain ammonium ions and acid residues side by side.

In a further particular embodiment of variant (b) of process (1) according to the invention, the azulmic acid is reacted in a topochemical reaction with catalytic or larger amounts of water glass - about 1 to 4 mol of water glass to 100 g of azulmic acid -. This results in modified azulmic acids loaded with potassium or sodium ions, the saponifiable nitrile groups of which act as latent acids and precipitate silicas. The latter are finely distributed on the reaction products. Any excess sodium or potassium silicate present can be precipitated by simply gassing the respective dispersions with carbon dioxide or, in a particularly advantageous manner, precipitated by adding phosphoric acid or calcium chloride mixed with potassium or sodium phosphates or calcium silicates.

According to variant (c) of process (1) according to the invention, the azulmic acids, which are virtually free of defects, are treated for 4 to 60 hours with distilled water in the neutral range, preferably at pH values ​​between 6 and 6.5. The reaction temperatures can be varied within a relatively wide range. In general, temperatures between 60.degree. C. and 150.degree. C., preferably between 80.degree. C. and 120.degree. C., are used. The reaction is generally carried out under normal pressure. However, it is also possible to work under increased pressure. In this variant of the process according to the invention, too, the reaction products are isolated by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is dried.

According to variant (d) of process (1) according to the invention, the azulmic acids which are almost free of defects are treated with vegetable ashes, catalytically active natural substances and / or fertilizers.

The combustion products of the most varied of substances formed by photosynthesis come into consideration as vegetable ashes. The ashes of fir, gorse, Serbian spruce, oak, straw, birch, beech, willow, tobacco leaves, tobacco stalks, also of cereals, such as rye or barley, and of mushrooms, for example porcini mushrooms, apples, carrot roots, potato tubers and cabbage leaves, may be mentioned as preferred . The use of ash types rich in potassium is particularly advantageous. In this context, ashes are also to be understood as meaning mixtures of different vegetable ashes.

As catalytically active natural substances are preferably biologically active garden soil and basic or acidic soils of the most varied of types.

All commercially available fertilizers can be used as fertilizers in the generation of defects according to variant (d) of method (1) according to the invention. Peat types loaded with plant nutrients, superphosphate, Thomas slag, rhenaniaphosphate, phosphorite, calcium cyanamide, calcium ammonium nitrate, leunas nitrate, potassium phosphates, potassium nitrate and ammonium nitrate may be mentioned as preferred.

When carrying out variant (d) of process (1) according to the invention, the process is carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as hydrogen sulfide or alcohols, methanol and ethanol being specifically mentioned.

In the case of variant (d) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 50.degree. C. and 150.degree. C., preferably between 80.degree. C. and 120.degree. C., are used.

The reactions according to variant (d) of process (1) according to the invention are in general carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out variant (d) of process (1) according to the invention, the azulmic acid is reacted with catalytic or else with larger amounts of vegetable ashes, catalytically active natural substances and / or fertilizers. If the vegetable ashes, catalytically active natural substances and / or fertilizers are used in larger quantities, these substances not only serve to create defects, but they are also contained in the resulting products as additives. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the resultant F.est product washes and dries if necessary.

According to variant (e) of process (1) according to the invention, the azulmic acids, which are virtually free of defects, are treated with metal compounds, if appropriate in the presence of oxidizing agents and if appropriate in the presence of organic acids.

Suitable metal compounds here are preferably salts of metals from main groups II to V or from subgroups I to VIII. Examples include calcium chloride, acetate and nitrate, strontium nitrate, barium chloride and acetate, aluminum acetate and formate, thallium sulfate and nitrate, silicon tetrachloride, sodium or potassium silicate, tin (II) chloride, lead (II) chloride, II acetate and II nitrate, bismuth III nitrate, copper sulphate, nitrate and acetate, silver nitrate, tetrachloroauric acid, zinc chloride and acetate, cadmium chloride, mercury II chloride, titanium tetrachloride and tetrabutoxide, zirconium sulphate, Chromium III chloride, manganese II sulphate and acetate, iron II sulphate, II acetate and III chloride, cobalt chloride, nickel chloride, hexachloroplatinic acid and palladium II chloride. Metal compounds that can also be used with preference are the acids of vanadium, molybdenum and tungsten, and their heteropolyacids.

As oxidizing agents which can be present when carrying out variant (e) of process (1) according to the invention, all customary oxygen-releasing agents are suitable. Air, nitric acid, hypochlorous acid, perchloric acid, calcium hypochlorite and hydrogen peroxide can preferably be used.

Suitable organic acids which may be present when carrying out variant (e) of process (1) according to the invention are preferably saturated and unsaturated, optionally substituted carboxylic acids. Formic acid, acetic acid, propionic acid, 2-ethyl-caproic acid, acrylic acid, methacrylic acid, oleic acid, ricinoleic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid and hydroxyacetic acid may be mentioned in particular.

When carrying out variant (e) of process (1) according to the invention, the process is generally carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as acids or organic hydrocarbons, formic acid and xylene being specifically mentioned.

In the case of variant (e) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 0.degree. C. and 150.degree. C., preferably between 20.degree. C. and 120.degree. C., are used.

The implementation according to VAriante (e) of the invention Vexperience (1) is generally carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out variant (e) of process (1) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight of 54) azulmic acid a catalytic amount or a larger amount - about 1 to 2 mol - of metal compound and optionally a catalytic or larger amount of oxidizing agent and optionally a catalytic or larger amount of organic acid. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried.

Any excess metal compounds present in the products according to the invention can be precipitated in the form of finely divided, often sparingly soluble, precipitates, depending on the metal compound, by adding bases such as ammonia, sodium hydride or potassium hydroxide, or by adding acids such as phosphoric acid.

According to variant (f) of process (1) according to the invention, the azulmic acids which are virtually free from defects are treated with metal salt complexes of stabilized azulmic acids.

In this context, stabilized azulmic acids are to be understood as meaning those products which are obtained by reacting azulmic acids containing defects with aldehydes, preferably formaldehyde, at temperatures between 20 ° C. and 150 °0C. arise in an aqueous medium and which are very stable to the elimination of hydrogen cyanide both at room temperature and at elevated temperature. If metal salts of this type, stabilized with aldehydes, are allowed to act, the metal salt complexes of stabilized azulmic acids required as starting materials for carrying out variant (f) of process (1) according to the invention are formed. Metal salt complexes which can preferably be used are those which are derived from those metal compounds which have already been mentioned as preferred in connection with variant (e) of process (1) according to the invention.

When carrying out variant (f) of process (1) according to the invention, the process is carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as alcohols.

In the case of variant (f) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 0.degree. C. and 150.degree. C., preferably between 20.degree. C. and 120.degree. C., are used.

The reaction according to variant (f) of process (1) according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out variant (f) of process (1) according to the invention, 1 mol (based on the molecular unit NC-C-NH with the equivalent weight of 54) of almost defect-free azulmic acid is preferably 0.5 to 1 mol of metal salt A complex of stabilized azulmic acid. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product thus obtained is optionally washed and dried.

Any excess metal compounds present in the products which can be prepared according to variant (f) of process (1) according to the invention can be converted into, depending on the metal compound, by adding bases such as ammonia, sodium hydroxide or potassium hydroxide, or by adding acids such as phosphoric acid Precipitate in the form of finely divided, often poorly soluble, precipitates.

According to variant (g) of process (1) according to the invention, the azulmic acids which are virtually free from defects are treated with oxidizing agents. All conventional oxidizing reagents can be used as oxidizing agents. Air, oxygen, potassium permanganate, hydrogen peroxide, chromic acid and chlorinated lime can preferably be used.

When carrying out variant (g) of process (1) according to the invention, the process is carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents such as organic carboxylic acids, formic acid and acetic acid being specifically mentioned.

In the case of variant (g) of process (1) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 0 ° C. and 150 ° C., preferably between 20 ° C. and 120 ° C., are used0C.

The reaction according to variant (g) of process (1) according to the invention is in general carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out variant (g) of process (1) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight 54) of almost defect-free azulmic acid, a catalytic amount or a larger, optionally equimolar amount of oxidizing agent. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried.

In process (2) according to the invention, monomeric aqueous hydrocyanic acid is polymerized, if appropriate in the presence of additives, with the aid of basic catalysts under hydrolyzing conditions. This is based on dilute aqueous hydrocyanic acid solutions. In general, solutions are used whose hydrocyanic acid concentration is between 10 and 30%, preferably between 15 and 25%.

Suitable basic catalysts in process (2) according to the invention are organic and inorganic bases and basic salts of the most varied of types. Alkali metal cyanides and alkali metal cyanates, such as sodium cyanide, potassium cyanide, sodium cyanate and potassium cyanate, and also amines and ammonia, can preferably be used. Mixtures of the most varied of bases or basic salts can advantageously also be used; for example, a mixture of sodium cyanate and aqueous ammonia solution may be mentioned.

Organic natural substances and products obtained therefrom, inorganic natural substances and products obtained therefrom, synthetic organic products, synthetic inorganic products and / or mixed products of organic and inorganic products can be used as additives when carrying out method (2) according to the invention. These preferably include all those materials which have already been mentioned as preferred in connection with the description of the additives that may be present in the substances according to the invention.

When carrying out process (2) according to the invention, one works in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as hydrogen sulfide or alcohols, methanol and ethanol being specifically mentioned.

In the case of process (2) according to the invention, the reaction temperatures can be varied within a certain range, but the temperature control must be adapted to the particular reaction phase. In general, the procedure is to first polymerize for 1 to 4 hours at temperatures between 30.degree. C. and 70.degree. C., preferably between 40.degree. C. and 60.degree. C., so that about 60% conversion of the monomeric hydrocyanic acid is achieved. Polymerization is then carried out for a further 4 to 10 hours at temperatures between 70 ° C. and 95 ° C., preferably between 80 ° C. and 90 ° C., as a result of which a conversion of about 90 to 95% is achieved. The reaction can then be completed and any hydrocyanic acid still present and any volatile amines or ammonia present can be removed by heating to temperatures of around 100 ° C. for several hours.

The reaction according to process (2) according to the invention is in general carried out under normal pressure. However, it is also possible to work at temperatures between 120.degree. C. and 150.degree. C. under increased pressure. In this way, relatively large amounts of defects can be generated in the process products in a targeted manner.

When carrying out process (2) according to the invention, the basic catalyst is used in an amount such that the proportion is 1 to 15%, preferably 2 to 10%, of the monomeric hydrocyanic acid used.

The additives are optionally added to the reaction mixture in such an amount that their proportion in the end product is between 1 and 95 percent by weight, preferably between 5 and 90 percent by weight. Working up is carried out by customary methods. In general, the procedure is that after the removal of excess hydrocyanic acid and any volatile amines or ammonia present, the reaction mixture is filtered and the solid product obtained is optionally washed and dried.

In process (3) according to the invention, modified azulmic acids are first treated with bases or basic salts and then optionally reacted with metal salts in a second stage. - Modified azulmic acids are to be understood here as meaning azulmic acids which contain defects and which have been produced by one of the aforementioned processes.

Suitable bases or basic salts when carrying out process (2) according to the invention are a wide variety of inorganic or organic bases and also basic salts. Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate and potassium hydrogen carbonate, alkali metal sulphides such as sodium sulphide, potassium sulphide and potassium hydrogen sulphide, alkali metal thiosulphides such as ammonium metal thiosulphates such as ammonium metal thiosulphates, such as ammonium metal thiosulphates, and furthermore ammonium metal thiosulphates, such as sodium hydroxide, can preferably be used.

Suitable metal salts when carrying out the second stage of process (3) according to the invention are preferably all those metal salts which have already been mentioned as preferred in connection with the description of variant (e) of process (1) according to the invention. Iron (II) acetate, iron (II) sulfate, iron (III) sulfate, copper acetate, zinc acetate, manganese (II) acetate, cobalt chloride, zinc chloride and tin (II) chloride may be mentioned specifically.

When carrying out process (3) according to the invention, one works in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as hydrogen sulfide or alcohols, methanol and ethanol being specifically mentioned.

In the case of process (3) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the temperature is between 50.degree. C. and 120.degree. C., preferably between 60.degree. C. and 110.degree.

The reaction by process (3) according to the invention is in general carried out under normal pressure. However, it is also possible to work under increased pressure. The latter is particularly recommended when ammonium hydroxide or volatile amines have been used as bases.

When carrying out process (3) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight 54) of modified azulmic acid, preferably 0.5 to 4 mol of base or basic salt and optionally 1 to 2 mol of metal salt. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried. However, it is also possible to first concentrate the dispersion obtained after the reaction with bases or basic salts, then to add alcohol, such as methanol, to concentrate again under reduced pressure and, after repeating this process several times, to filter off the solid product obtained in the process and if necessary to dry.

In process (4) according to the invention, modified azulmic acids are treated with inorganic or organic acids. - Modified azulmic acids are to be understood here as meaning azulmic acids which contain defects and which have been produced by one of the aforementioned processes. Inorganic or organic acids that can be used are preferably all those acids which have already been enumerated in connection with the description of the products according to the invention.

The process (4) according to the invention is carried out in an aqueous medium, preferably in water. However, it is also possible to partially replace the water with other diluents, such as alcohols, methanol and ethanol being specifically mentioned.

In the case of process (4) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, between 0.degree. C. and 200.degree. C., preferably between 20.degree. C. and 120.degree. C., are used.

The reaction by process (4) according to the invention is in general carried out under normal pressure. However, it is also possible to work under increased pressure.

When carrying out process (4) according to the invention, 1 mol (based on the molecular unit NC-C-NH) is used2 with the equivalent weight 54) of modified azulmic acid a catalytic or a larger amount, preferably 1 to 4 mol, of inorganic or organic acid. Working up is carried out by customary methods. In general, one proceeds in such a way that, after the reaction has ended, the reaction mixture is filtered and the solid product obtained is optionally washed and dried. Any excess acid still present in the products formed in this way can be converted into the corresponding ammonium salt by gassing with ammonia, the reaction advantageously being carried out in the solid phase in a fluidized bed.

If free amino groups are still present in the products prepared by processes (1) to (4) according to the invention, these products can be converted into the corresponding acid addition salts by treatment with inorganic or organic acids. The procedure here is to stir the products in an aqueous medium, if appropriate at elevated temperature, with the respective acid. The reaction products are isolated by filtration.

If free carboxyl groups are still present in the products prepared by processes (1) to (4) according to the invention, these products can be converted into the corresponding salts by treatment with bases. The procedure here is to stir the products in an aqueous medium, if appropriate at elevated temperature, with the respective base. The reaction products are isolated by filtration.

As already mentioned, the products according to the invention are very versatile. For example, they are suitable as intermediate products for the production of stabilized azulmic acids, which are understood to mean azulmic acids with high resistance to hydrocyanic acid cleavage. Stabilized azulmic acids of this type can be prepared by adding the modified azulmic acids according to the invention in an aqueous medium at temperatures between 200C and 150OC, preferably between 50 ° C and 1200C is reacted with carbonyl compounds, preferably aldehydes, with formaldehyde, acetaldehyde, crotonaldehyde, isobutyraldehyde, glyoxal, acrolein, hydroxyacetaldehyde, hydroxypivalaldehyde, glyceraldehyde, furfural, chloral or chloral hydrate, hydroxymamethyl furfural or chloral hydrate, hydroxymamine, paramethyl furfurol or hexaldehyde, and traldehyde, paraldehyde-dehydrogenated, glucose and traldehyde, methylglyoxalioxane formaldehyde, and traldehyde, paraldehyde-dehydrogenated, and traldehyde, as are specifically mentioned. The reaction products are isolated by filtration. Stabilized azulmic acids of this type do not split off any hydrogen cyanide even after prolonged storage at room temperature or even at higher temperatures. The substances in question can be used for a wide variety of purposes. Examples include their use as fillers in polyurethanes or other plastics, and also their use as catalysts or catalyst carriers, flame retardants and agricultural chemicals.

The substances according to the invention can also be used as reactive fillers and as catalysts in isocyanate chemistry for the production of polyurethane plastics. Those substances according to the invention which contain metal salts or metal ions are particularly suitable here.

Those substances according to the invention which have a high ionic content and thus have a polyelectrolyte character can serve as ion exchangers or also as catalysts. Azulmic acid potassium salts may be mentioned as examples in this context.

Numerous substances according to the invention can be used as flame retardants or anti-aging agents in a wide variety of polyurethane plastics, polyamide plastics, vinyl polymers, rubbers and epoxy resins. Particularly suitable for this purpose are those substances according to the invention which contain phosphoric acid, phosphorous acid, polymethylene ureas, polymethylene melamines, calcium phosphates, aluminum phosphates, aluminum silicates, aluminum oxide hydrate, water glass, melamine phosphate, barium phosphates, ammonium magnesium phosphates and / or urea oxalate.

In addition, the products according to the invention can either be used as agrochemicals themselves or serve as intermediates for the production of agrochemicals. Those compounds which contain salts which are important for plant nutrition are particularly suitable for this purpose.

example 1



Comparative experiment: polymerization of monomeric hydrogen cyanide in the presence of potassium cyanate (cf. Angew. Chem. 72, (1960) page 380, example 4).

200 parts by weight of a 30% strength aqueous hydrocyanic acid solution are heated to 40 to 50 ° C. for 5 hours in the presence of 1.08 parts by weight of potassium cyanate. The product formed is filtered off, washed successively with distilled water and ethanol and then dried at 80.degree. Azulmic acid is obtained in the form of a black powder in a yield of 95% of theory.

Elemental analysis:

41.4% C; 4.0% H; 43.2% N; 11.4% 0



On the basis of the oxygen values ​​given, this azulmic acid, the constitution of which is roughly characterized by the formula (I) given on page 3 of this application, has the empirical formula C24H28O5N22 to (see. Angew. Chem. 72 (1960) p. 383).

This polymer cleaves, even after careful long-term drying at room temperature or at 80 ° C., continuously small amounts of monomeric hydrocyanic acid. Subsequent intensive washing and renewed drying, even in a high vacuum, does not stop the cyanide cleavage.

The hydrogen cyanide is determined by customary methods.

If 2000 g of azulmic acid, which was prepared by the method given above, were stored at 500C in a container with an air volume of 12 liters, a hydrogen cyanide concentration of 0.066 g hydrogen cyanide per 12 liters of air is measured after 2 hours. This results in a hydrogen cyanide MAK value (MAK = maximum workplace concentration) of 4583 ppm, i.e. a MAK value that is 416 times greater than the legally stipulated MAK value of 11 ppm. Accordingly, such an azulmic acid is completely useless for practical use.

If 10 parts by weight of the azulmic acid prepared by the above process are treated for 3 hours at 100 ° C. with 100 parts by weight of distilled water and the cyanide ion concentration is then determined in the filtrate, a cyanide ion concentration is found which has a hydrogen cyanide content of 26 to over 28 mg per liter of water. Such concentrations of cyanide ions already kill and deactivate important bacteria and their enzyme systems that occur in the soil.

Example 2



Comparative experiment: polymerization of monomeric hydrogen cyanide by the "feed process" in the presence of ammonia (cf. DT-PS 949 060).

A mixture of 5600 g of water, 1400 g of hydrocyanic acid and 88 g of ammonia is polymerized exactly according to the information contained in Example 1 of DT-PS 949 060. After a polymerization time of about five hours at 50 ° C., after the cooling has been switched off, the internal temperature rises to 90 ° C., remains at this level for about an hour and then drops. The azulmic acid formed is isolated, washed with water and dried at 80.degree. Yield 98% of theory.

Thermal stability:

Storage of 2000 g of azulmic acid for two hours at 50 ° C (see Example 1): MAK value above 5000 ppm.



Hydrolytic stability:

Treatment of 10 parts by weight of azulmic acid with 100 parts by weight of distilled water at 100 ° C. for three hours (see Example 1): hydrogen cyanide concentration of 30 to 36 mg per liter of water.


Example 3



108 g of an azulmic acid prepared according to Example 2 (apart from the end groups, this amount corresponds to an average of 2 basic moles of polymerized aminocyano carbene units of the structure

Equivalent weight = 54), after prior drying at 80.degree. C. in a closed stirring apparatus, 1000 g of distilled water and 98 g (1 mol) of phosphoric acid are added and the mixture is heated to 100.degree. M.The reaction mixture is kept at this temperature for 16 hours and during this time, in which the azulmic acid is undergoing heterogeneous hydrolysis or partial decyclization, a nitrogen stream serving as a propellant gas is passed through the reaction mixture at a rate of about 50 ml per minute. The exiting nitrogen flow is passed through two washing bottles connected one after the other, the first being filled with 200 ml of 1N aqueous hydrochloric acid to bind the ammonia contained in the nitrogen flow, and the second washing bottle being filled with 200 ml of 1N aqueous sodium hydroxide solution to bind the carbon dioxide present in the nitrogen flow . The amounts of ammonia and carbon dioxide released from the azulmic acid are determined titrimetrically at intervals of 1 to 3 hours. After a reaction time of 16 hours, the total amount of ammonia produced by the hydrolytic generation of F1-Faults in the formula

(Equivalent weight 73) was formed, 6.4 g (≈ 0.38 mol). The total amount of carbon dioxide produced by the decarboxylation of F1-Faults to F2-Faults in the formula

(Equivalent weight 29) is 4.3 g (≈ 0.1 mol) (determined titrimetrically according to the barium carbonate method). A molar NH can be calculated from these numbers3/ CO2-Quotient rounded up to around 3.8. This numerical value means that of about 4 carboxyl groups generated by decyclization and saponification of nitrile groups of azulmic acid (F.1Defects), for example, is decarboxylated and thus becomes an F2-Fault leads.

Working up is done in such a way that the solid reaction product is filtered off, washed and dried. 109 g of an F are obtained1- and F2- (Modified) azulmic acid containing defects.

On the basis of this yield information and the determined molar NH3/ CO2Quotients of 3.8 as well as the fact that the F2-Faults from the F1- Defects have arisen (0.38 mol - 0.1 mol = 0.28 mol), it can be calculated that 100 parts by weight of the process product contain about 18.6 percent by weight of F1Defects and about 2.67 percent by weight of F2-Faults included. The sum to F1- and F?Defects is 21.3 percent by weight.

As can be seen from the elemental analysis, the modified azulmic acid contains about 9.3 percent by weight of phosphoric acid. This phosphoric acid is bound to the polymeric matrix via the free amino groups (anchor groups) of the modified azulmic acid.

Example 4



108 g (2 basic mol) of an azulmic acid prepared according to Example 2 are mixed with 1000 g of distilled water and 0.5 mol of calcium sulfite dihydrate after prior drying at 80.degree. C. and heated to 100.degree. The reaction mixture is kept at this temperature for 8 hours and during this time a stream of nitrogen is passed through at a rate of about 50 ml per minute. The ammonia and carbon dioxide content in the nitrogen stream exiting is determined in the manner indicated in Example 3. A modified azulmic acid is obtained whose molar NH3/C02Quotient is 2.68.

Example 5



108 g (2 basic mol) of an azulmic acid prepared according to Example 2 are, after prior drying at 80.degree. C., mixed with 1000 g of deionized water in a closed stirring apparatus and heated to 100.degree. The reaction mixture, in which the pH value is 6.2, is kept at this temperature for 8 hours and during this time a stream of nitrogen is passed through at a rate of 50 ml per minute. The ammonia and carbon dioxide content in the nitrogen stream exiting is determined in the manner indicated in Example 3. The total amount of ammonia released is 0.059 mol.

The total amount of carbon dioxide released is 0.023 mol.

This results in a molar NH3/ C02Quotient of 2.57.

From the released amounts of ammonia and carbon dioxide it is calculated by forming the difference (0.059-0.023-0.036) that about 0.036 equivalents of F1-Faults and about 0.023 equivalents of F2- Defects have arisen.

Yield of modified azulmic acid: 107 g



From this yield, the molar NH3/ CO2Quotients and the difference between the molar amounts of ammonia and carbon dioxide released (0.059-0.023-0.036) are calculated that 100 parts by weight of the process product contain about 2.57 percent by weight of F1Defects and about 0.7 percent by weight of F2-Faults included.

Example 6



To 7 liters of 20% aqueous hydrocyanic acid (- 1400 g (52 mol) hydrogen cyanide) are added 350 g of about 25 weight percent aqueous ammonia solution (= 87.5 g (about 5.15 mol) ammonia) with vigorous stirring added containing 70 g (1.1 mol) of sodium cyanate. This mixture is heated to 40 ° C. The temperature then rises to 70 ° C due to the heat of polymerization released. The mixture is heated to 90 ° C. for a further 4 hours and then worked up by filtering off the brown-black polymer which does not form colloidal solutions in water, washing it successively with water and ethanol and then drying it at 50 ° -80 ° C. under reduced pressure.

Yield: 94.9% of theory.

Elemental analysis:

40.6% C; 4.1% H; 42.4% N; 12.8% O



In the mother liquor of the polymerization batch, the carbonate content is detected in a concentration that corresponds to an amount of released carbon dioxide of about 0.02 mol per 100 g of polymer. Accordingly, 0.56 percent by weight of F2-Faults have been introduced into the product. Furthermore, assuming a molar NH3/ C02-Quotient of about 4, as it was found in a parallel experiment in the two-hour hydrolysis of a sodium cyanate-free azulmic acid at 90 ° C, that an amount of 0.08 mol of ammonia was released per 100 g of the polymer produced, which an F.1- Corresponds to a defect content of 4 percent by weight.