Modified azulmic acids

Claim 2

Solid modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR37## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR38##

Claim 3

An acid addition salt of the modified azulmic acid of claim 1 prepared by addition of a proton of an inorganic or organic acid onto an amino group or other suitable group in said modified azulmic acid.

Claim 4

An azulmic acid complex compound of solid modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR39## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR40## and a metal compound or an ammonium salt.

Claim 5

An azulmic acid complex compound of solid modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR39## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR40## and a metal compound or an ammonium salt.

Claim 6

A mixture comprising solid modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR41## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR42## and a material selected from the group consisting of wood flour; lignin powder; lignin-sulphonic acids; ammonified lignin-sulphonic acids; humus, humic acids; ammonified humic acids; peat; proteins and their degradation products; algal material; polypeptides; fish-meal; bone-meal; aminoacids; oligopolypeptides; pectins; monosaccharides; disaccharides; aligosaccharides; polysaccharides; hemicelluloses; charcoals and ashes which are obtainable by oxidation of organic substances formed by photosynthesis or of customary fuels; metallic silicates; silicon dioxides; silicic acids and salts thereof; silica gels; clay minerals; mica; metallic and ammonium carbonates; phosphorite; metallic and ammonium phosphates; metallic and ammonium sulphates; metallic oxides; aminoplast condensates; polymeric quinones; addition products and condensation products of quinones with amines, ammonia, and aldehydes; crosslinked gelatin; urea/formaldehyde resin flakes; formose sugar mixtures prepared from formaldehyde; sparingly soluble cane sugar complexes; hexamethylene-tetramine; hexahydrotriazines; superphosphate; basic slag; Rhenania phosphate; calcium cyanamide; calcium ammonium nitrate; Leuna saltpeter; potassium nitrate; ammonium nitrate; metal hydroxides; and cobalt molybdate; and mixtures thereof.

Claim 7

A mixture comprising solid modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR41## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR42## and a material selected from the group consisting of wood flour; lignin powder; lignin-sulphonic acids; ammonified lignin-sulphonic acids; humus, humic acids; ammonified humic acids; peat; proteins and their degradation products; algal material; polypeptides; fish-meal; bone-meal; aminoacids; oligopolypeptides; pectins; monosaccharides; disaccharides; aligosaccharides; polysaccharides; hemicelluloses; charcoals and ashes which are obtainable by oxidation of organic substances formed by photosynthesis or of customary fuels; metallic silicates; silicon dioxides; silicic acids and salts thereof; silica gels; clay minerals; mica; metallic and ammonium carbonates; phosphorite; metallic and ammonium phosphates; metallic and ammonium sulphates; metallic oxides; aminoplast condensates; polymeric quinones; addition products and condensation products of quinones with amines, ammonia, and aldehydes; crosslinked gelatin; urea/formaldehyde resin flakes; formose sugar mixtures prepared from formaldehyde; sparingly soluble cane sugar complexes; hexamethylene-tetramine; hexahydrotriazines; superphosphate; basic slag; Rhenania phosphate; calcium cyanamide; calcium ammonium nitrate; Leuna saltpeter; potassium nitrate; ammonium nitrate; metal hydroxides; and cobalt molybdate; and mixtures thereof.

Claim 8

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR43## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR44## comprising treating in an aqueous medium with an organic or inorganic acid an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted between 0° C. to 200° C. and from 1 to 4 mols of organic or inorganic acid are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 9

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR43## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR44## comprising treating in an aqueous medium with an organic or inorganic acid an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted between 0° C. to 200° C. and from 1 to 4 mols of organic or inorganic acid are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 10

The process of claim 5, wherein the treating is conducted in the presence of a material selected from the group consisting of wood flour; lignin powder; lignin-sulphonic acids; ammonified lignin-sulphonic acids; humus, humic acids; ammonified humic acids; peat; proteins and their degradation products; algal material; polypeptides; fish-meal; bone-meal; aminoacids; oligopolypeptides; pectins; monosaccharides; disaccharides; aligosaccharides; polysaccharides; hemicelluloses; charcoals and ashes which are obtainable by oxidation of organic substances formed by photosynthesis or of customary fuels; metallic silicates; silicon dioxides; silicic acids and salts thereof; silica gels; clay minerals; mica; metallic and ammonium carbonates; phosphorite; metallic and ammonium phosphates; metallic and ammonium sulphates; metallic oxides; aminoplast condensates; polymeric quinones; addition products and condensation products of quinones with amines, ammonia, and aldehydes; crosslinked gelatin; urea/formaldehyde resin flakes; formose sugar mixtures prepared from formaldehyde; sparingly soluble cane sugar complexes; hexamethylene-tetramine; hexahydrotriazines; superphosphate; basic slag; Rhenania phosphate; calcium cyanamide; calcium ammonium nitrate; Leuna saltpeter; potassium nitrate; ammonium nitrate; metal hydroxides; and cobalt molybdate; and mixtures thereof.

Claim 11

The process of claim 5, further comprising treating the resultant product with an acid or base.

Claim 12

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR45## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR46## comprising treating in an aqueous medium, with bases or basic salts an azulmic acid prepared by aqueous polymerization of hydrocyanic acid wherein the treatment is conducted between 0° and 200° C. and from 1 to 4 mols of base or basic salt are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 13

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR45## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR46## comprising treating in an aqueous medium, with bases or basic salts an azulmic acid prepared by aqueous polymerization of hydrocyanic acid wherein the treatment is conducted between 0° and 200° C. and from 1 to 4 mols of base or basic salt are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 14

The process of claim 8, wherein the treating is conducted in the presence of a material selected from the group consisting of wood flour; lignin powder; lignin-sulphonic acids; ammonified lignin-sulphonic acids; humus; humic acids; ammonified humic acids; peat; proteins and their degradation products; algal material; polypeptides; fish-meal; bone-meal; aminoacids; oligopolypeptides; pectins; monosaccharides; disaccharides; aligosaccharides; polysaccharides; hemicelluloses; charcoals and ashes which are obtainable by oxidation of organic substances formed by photosynthesis or of customary fuels; metallic silicates; silicon dioxides; silicic acids and salts thereof; silica gels; clay minerals; mica; metallic and ammonium carbonates; phosphorite; metallic and ammonium phosphates; metallic and ammonium sulphates; metallic oxides; aminoplast condensates; polymeric quinones; addition products and condensation products of quinones with amines, ammonia, and aldehydes; crosslinked gelatin; urea/formaldehyde resin flakes; formose sugar mixtures prepared from formaldehyde; sparingly soluble cane sugar complexes; hexamethylene-tetramine; hexahydrotriazines; superphosphate; basic slag; Rhenania phosphate; calcium cyanamide; calcium ammonium nitrate; Leuna saltpeter; potassium nitrate; ammonium nitrate; metal hydroxides; and cobalt molybdate; and mixtures thereof.

Claim 15

The process of claim 8, further comprising treating the resultant product with an acid or base.

Claim 16

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR47## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR48## comprising treating with water for 4 to 60 hours at a pH of from 6 to 6.5 and at a temperature of from 60° to 150° C. an azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 17

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR47## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR48## comprising treating with water for 4 to 60 hours at a pH of from 6 to 6.5 and at a temperature of from 60° to 150° C. an azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 18

The process of claim 11, further comprising treating the resultant product with an acid or base.

Claim 19

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR49## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR50## comprising treating azulmic acid in an aqueous medium, with the ashes produced by the combustion of fir, broom, Serbian spruce, oak, straw, birch, beech, willow, tobacco leaves, tobacco stalks, cereals, fungi, apples, carrots, potato tubers and the leaves of white cabbage, an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted at a temperature of from 50° to 150° C.

Claim 20

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR49## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR50## comprising treating azulmic acid in an aqueous medium, with the ashes produced by the combustion of fir, broom, Serbian spruce, oak, straw, birch, beech, willow, tobacco leaves, tobacco stalks, cereals, fungi, apples, carrots, potato tubers and the leaves of white cabbage, an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted at a temperature of from 50° to 150° C.

Claim 21

The process of claim 13, further comprising treating the resultant product with an acid or base.

Claim 22

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR51## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR52## comprising treating in an aqueous medium with a metal salt an azulmic acid prepared by aqueous polymerization of hydrocyanic acid wherein the treatment is conducted at a temperature of from 0° to 150° C., and from 1 to 2 mols of metal salt are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 23

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR51## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR52## comprising treating in an aqueous medium with a metal salt an azulmic acid prepared by aqueous polymerization of hydrocyanic acid wherein the treatment is conducted at a temperature of from 0° to 150° C., and from 1 to 2 mols of metal salt are used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 24

The process of claim 15, wherein the treatment is conducted in the presence of oxidizing agents, organic acids, or mixtures thereof.

Claim 25

The process of claim 15, further comprising treating the resultant product with an acid or base.

Claim 26

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR53## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR54## comprising treating in an aqueous medium with a metal salt complex of a stabilized azulmic acid, an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted at a temperature of from 0° to 150° C. and from 0.5 to 1 mol of complex is used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 27

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR53## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR54## comprising treating in an aqueous medium with a metal salt complex of a stabilized azulmic acid, an azulmic acid prepared by aqueous polymerization of hydrocyanic acid, wherein the treatment is conducted at a temperature of from 0° to 150° C. and from 0.5 to 1 mol of complex is used per mol of azulmic acid prepared by aqueous polymerization of hydrocyanic acid.

Claim 28

The process of claim 18, further comprising treating the resultant product with an acid or base.

Claim 29

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR55## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR56## comprising polymerizing hydrocyanic acid under hydrolyzing conditions in an aqueous medium in the presence of basic catalysts wherein the polymerization is conducted between 40° and 60° C. up to a conversion of about 60% of the acid, then at between 80° to 90° C. to a conversion of about 90 to 95% of the acid and then at 100° C. for several hours until completion of the reaction.

Claim 30

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR55## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR56## comprising polymerizing hydrocyanic acid under hydrolyzing conditions in an aqueous medium in the presence of basic catalysts wherein the polymerization is conducted between 40° and 60° C. up to a conversion of about 60% of the acid, then at between 80° to 90° C. to a conversion of about 90 to 95% of the acid and then at 100° C. for several hours until completion of the reaction.

Claim 31

The process of claim 20, wherein the polymerization is conducted in the presence of a material selected from the group consisting of wood flour; lignin powder; lignin-sulphonic acids; ammonified lignin-sulphonic acids; humus, humic acids; ammonified humic acids; peat; proteins and their degradation products; algal material; polypeptides; fish-meal; bone-meal; aminoacids; oligopolypeptides; pectins; monosaccharides; disaccharides; aligosaccharides; polysaccharides; hemicelluloses; charcoals and ashes which are obtainable by oxidation of organic substances formed by photosynthesis or of customary fuels; metallic silicates; silicon dioxides; silicic acids and salts thereof; silica gels; clay minerals; mica; metallic and ammonium carbonates; phosphorite; metallic and ammonium phosphates; metallic and ammonium sulphates; metallic oxides; aminoplast condensates; polymeric quinones; addition products and condensation products of quinones with amines, ammonia, and aldehydes; crosslinked gelatin; urea/formaldehyde resin flakes; formose sugar mixtures prepared from formaldehyde; sparingly soluble cane sugar complexes; hexamethylene-tetramine; hexahydrotriazines; superphosphate; basic slag; Rhenania phosphate; calcium cyanamide; calcium ammonium nitrate; Leuna saltpeter; potassium nitrate; ammonium nitrate; metal hydroxides; and cobalt molybdate; and mixtures thereof.

Claim 32

The process of claim 20, further comprising treating the resultant product with an acid or base.

Claim 33

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR57## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR58## comprising reacting said modified azulmic acids with a base in an aqueous medium.

Claim 34

A process for the preparation of solid modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR57## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR58## comprising reacting said modified azulmic acids with a base in an aqueous medium.

Claim 35

The process of claim 23, further comprising replacing the resultant cation by treatment with metal salts.

Claim 36

The process of claim 23, further comprising treating the resultant product with an acid or base.

Claim 37

A process for the preparation of modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR59## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR60## comprising reacting said modified azulmic acids with an organic or inorganic acid in an aqueous medium.

Claim 38

A process for the preparation of modified azulmic acids containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR59## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR60## comprising reacting said modified azulmic acids with an organic or inorganic acid in an aqueous medium.

Claim 39

The process of claim 26, further comprising treating the resultant product with a base.

Claim 40

In the preparation of an isocyanate-polyaddition product by reacting an organic isocyanate with an active hydrogen containing material, the improvement wherein modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR61## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR62## are included in the reaction mixture.

Claim 41

In the preparation of an isocyanate-polyaddition product by reacting an organic isocyanate with an active hydrogen containing material, the improvement wherein modified azulmic acids, containing from 0.5 to 55 percent by weight of ionic groups of the formula ##STR61## wherein R represents hydrogen, ammonium, one equivalent of a protonated or quaternized organic nitrogen base or of a sulphonium cation or one equivalent of a metal cation, and containing from 0.5 to 15 percent by weight of groups formed by decarboxylation reactions, said groups formed by decarboxylation reactions being of the formula ##STR62## are included in the reaction mixture.