Aspartic acid copolymers and their preparation

Abstract

Aspartic acid precursors such as mono and diammonium maleate, maleamic acid, ammonium maleamate, ammonium malate and mixtures of these and other precursors are copolycondensed thermally with a variety of mono, di and multifunctional monomers containing amino, hydroxyl and carboxyl functional groups. The resulting condensation copolymers and terpolymers contain succinimide units derived from aspartic acid precursors, condensed with other functional group monomers usually . .though.!. .Iadd.through .Iaddend.amide and ester linkages. Hydrolysis of the polysuccinimide copolymers and terpolymers with alkali, alkaline earth and ammonium hydroxide produces aspartic acid copolymer and terpolymer salts.

We claim: 
     
       1. A method for producing aspartic acid copolymers and salts which comprises heating . .mixtures of.!. .Iadd.a mixture comprising (a) an .Iaddend.aspartic acid . .precursors and.!. .Iadd.precursor, a .Iaddend.substituted aspartic acid . .precursors with amino, hydroxyl, and substituted aspartic acid precursors with.!. .Iadd.precursor or combination thereof and (b) an .Iaddend.amino, hydroxyl. ., and.!. .Iadd.or .Iaddend.carboxyl functional group.Iadd.-.Iaddend.containing . .monomers.!. .Iadd.monomer .Iaddend.at a temperature of at least 120° C. .Iadd.for .Iaddend.a sufficient length of time for thermal polymerization to a polysuccinimide copolymer to occur and subsequently hydrolyzing the polysuccinimide copolymer with alkali. .,.!. .Iadd.metal hydroxide, .Iaddend.alkaline earth. .,.!. .Iadd.metal hydroxide .Iaddend.or ammonium hydroxide. .s.!., to form the aspartic acid copolymer and salts .Iadd.thereof.Iaddend., wherein . .the.!. .Iadd.component (a) of .Iaddend.said mixture . .of.!. .Iadd.comprises as said .Iaddend.aspartic acid . .precursors and.!. .Iadd.precursor or .Iaddend.substituted aspartic acid . .precursors comprise.!. .Iadd.precursor .Iaddend.at least one of the following combinations of compounds: maleic anhydride and ammonium carbonate, citraconic anhydride and ammonium carbonate, itaconic anhydride and ammonium carbonate, maleic anhydride and asparagine, citraconic anhydride and asparagine, . .iraconic.!. .Iadd.itaconic .Iaddend.anhydride and asparagine, maleic anhydride and ammonium maleamate, citraconic anhydride and ammonium maleamate, itaconic anhydride and ammonium maleamate, maleic anhydride and monoammonium aspartate, itaconic anhydride and monoammonium aspartate, maleic acid and ammonium carbonate, citraconic acid and ammonium carbonate, itaconic acid and ammonium carbonate, maleic acid and asparagine, citraconic acid and asparagine, itaconic acid and asparagine, maleic acid and ammonium maleamate, citraconic acid and ammonium maleamate, . .iraconic.!. .Iadd.itaconic .Iaddend.acid and ammonium maleamate, maleic acid and monoammonium aspartate, citraconic acid and . .monoamonium.!. .Iadd.monoammonium .Iaddend.aspartate, itaconic acid and monoammonium aspartate, malic acid and ammonium carbonate, malic acid and asparagine, malic acid and ammonium maleamate, malic acid and monoammonium aspartate, fumaric acid and ammonium carbonate, fumaric acid and asparagine, fumaric acid and ammonium maleamate, fumaric acid and monoammonium aspartate, maleic anhydride and mono . .and.!. .Iadd.or .Iaddend.diammonium maleate, citraconic anhydride and mono . .and.!. .Iadd.or .Iaddend.diammonium maleate, . .iraconic.!. .Iadd.itaconic .Iaddend.anhydride and mono . .and.!. .Iadd.or .Iaddend.diammonium maleamate, maleic acid and mono . .and.!. .Iadd.or .Iaddend.diammonium . .maleamate.!. .Iadd.maleate, fumaric acid and mono or diammonium maleate.Iaddend., malic acid and mono . .and.!. .Iadd.or .Iaddend.diammonium . .maleamate, iraconic.!. .Iadd.maleate, itaconic .Iaddend.acid and mono . .and.!. .Iadd.or .Iaddend.diammonium maleate, citraconic acid and mono . .and.!. .Iadd.or .Iaddend.diammonium maleate. 
     
     
       2. The method in accordance with claim 1 wherein . .the.!. said amino, hydroxyl . .and.!..Iadd., or .Iaddend.carboxyl functional group-containing . .monomers comprise.!. .Iadd.monomer comprises .Iaddend.at least one of the following compounds: lactic acid, citric acid, glycolic acid, malic acid, tartaric acid, succinic acid, adipic acid, butanetetracarboxylic acid, gluconic acid, . .glucluronic.!. .Iadd.glucuronic .Iaddend.acid, glucaric acid, aconitic acid, sulfosuccinic acid, phosphinicosuccinic acid, phosphonosuccinic acid, iminodiacetic acid, nitrilotriacetic acid, stearic acid, palmitic acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic . .acid.!. anhydride, terephthalic acid, phthalic acid, phthalic . .acid and.!. anhydride, crotonic acid, sorbitol, glycerol, glucose, fructose, sucrose, maltose, glycine, alanine, . .aspartic acid,.!. glutamic acid, lysine, serine, threonine, cystine, cysteine, ethylenediamine, diethylenetriamine, . .triethylenetetramine.!. .Iadd.triethylenetetraamine.Iaddend., polyamines, 1,6-diaminohexane, octadecylamine, glucosamine, alkoxylated amines, alkoxylated diamines, alkoxylated triamines, 6-aminocaproic acid, 4-aminobutyric acid, diaminocyclohexane, urea, melamine, carbohydrazide, hydrazine, ascorbic acid, isoascorbic acid, sorbic acid, maleuric acid, cyanuric acid, alkyldiamines, alkyltriamines, acrylic acid, methacrylic acid, . .alkyltriamines, acrylic acid, methacrylic acid,.!. maleic acid . .and.!..Iadd., maleic .Iaddend.anhydride, alkylmaleic acids, alkenylsuccinic acids . .and anhydrides, methlenemalonic.!..Iadd., alkenylsuccinic anhydrides and methylenemalonic .Iaddend.acid. . .3. The method in accordance with claim 1 wherein the said amino, hydroxyl, and carboxyl functional group-containing monomers comprise at least one of the following compounds: lactic acid, citric acid, glycolic acid, malic acid, tartaric acid, succinic acid adipic acid, butanetetracarboxylic acid, gluconic acid, glucuronic acid, glucaric acid, aconitic acid, sulfosuccinic acid, phosphoinicosuccinic acid, phosphonosuccinic acid, iminodiacetic acid, nitrilotriacetic acid, stearic acid, palmitic acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic acid anhydride, terephthalic acid, phthalic acid, phthalic acid anhydride, crotonic acid, sorbitol, glycerol, glucose, fructose, sucrose, maltose, glycine, alanine, glutamic acid, lysine, serine, threonine, cystine, cysteine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyamines, 1,6-diaminohexane, octadecylamine, glucosamine, alkoxylated amines, alkoxylated diamines, alkoxylated triamines, 6-aminocaproic acid, 4-aminobutyric acid, diaminocyclohexane, urea, melamine, carbohydrates, hydrazine, ascorbic acid, isoascorbic acid, sorbic acid, maleuric acid, cyanuric acid, alkyldiamines, alkyltriamines, acrylic acid, methacrylic acid, maleic acid and anhydride, alkylmaleic acids, alkenylsuccinic acids 
     
     
        and anhydrides, methylenemalonic acid..!.4. The method in accordance with claim 1 wherein . .the.!. said . .hydroxides include.!. .Iadd.hydroxide includes .Iaddend.at least one of the following compounds: sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, cobalt hydroxide, ferric hydroxide, ferrous hydroxide. .,.!. .Iadd.and .Iaddend.ammonium 
     
     
        hydroxide. 5. The method in accordance with claim 3 wherein . .the.!. said . .hydroxides include.!. .Iadd.hydroxide includes .Iaddend.at least one of the following compounds: sodium hydroxide, potassium hydroxide, magnesium hydroxide, lithium hydroxide, calcium hydroxide, zinc hydroxide, barium hydroxide, cobalt hydroxide, ferric hydroxide, ferrous hydroxide. .,.!. .Iadd.and .Iaddend.ammonium hydroxide. .Iadd.6. A method for producing aspartic acid copolymers and salts thereof which comprises heating (a) an aspartic acid precursor, a substituted aspartic acid precursor or mixture thereof with (b) at least one amino, hydroxyl or carboxyl functional group-containing monomer at a sufficient temperature and for a sufficient length of time for thermal polymerization to a polysuccinimide copolymer to occur and subsequently hydrolyzing the polysuccinimide copolymer to form the aspartic acid copolymer and salts thereof..Iaddend..Iadd.7. The method in accordance with claim 6 wherein said component (a) comprises at least one compound selected from the group consisting of monoammonium maleate, diammonium maleate, maleamic acid, ammonium maleamate, monoammonium malate, diammonium malate, monoammonium fumarate, diammonium fumarate, asparagine, monammonium aspartate, monoammonium itaconate, diammonium itaconate, monoammonium citraconate, diammonium citraconate, monoammonium mesaconate, diammonium mesaconate, monoammonium chlorosuccinate, diammonium chlorosuccinate, monoammonium bromosuccinate, diammonium bromosuccinate, monoammonium mercaptosuccinate and diammonium mercaptosuccinate..Iaddend..Iadd.8. The method in accordance with claim 6 wherein said component (a) comprises at least one of the following combinations of compounds: maleic anhydride and ammonium carbonate, citraconic anhydride and ammonium carbonate, itaconic anhydride and ammonium carbonate, maleic anhydride and asparagine, citraconic anhydride and asparagine, itaconic anhydride and asparagine, maleic anhydride and ammonium maleamate, citraconic anhydride and ammonium maleamate, itaconic anhydride and ammonium maleamate, maleic anhydride and monoammonium aspartate, itaconic anhydride and monoammonium aspartate, maleic acid and ammonium carbonate, citraconic acid and ammonium carbonate, itaconic acid and ammonium carbonate, maleic acid and asparagine, citraconic acid and asparagine, itaconic acid and asparagine, maleic acid and ammonium maleamate, citraconic acid and ammonium maleamate, itaconic acid and ammonium maleamate, maleic acid and monoammonium aspartate, citraconic acid and monoammonium aspartate, itaconic acid and monoammonium aspartate, malic acid and ammonium carbonate, malic acid and asparagine, malic acid and ammonium maleamate, malic acid and monoammonium aspartate, fumaric acid and ammonium carbonate, fumaric acid and asparagine, fumaric acid and ammonium maleamate, fumaric acid and monoammonium aspartate, maleic anhydride and monoammonium maleate, maleic anhydride and diammonium maleate, citraconic anhydride and monoammonium maleate, citraconic acid and diammonium maleate, itaconic anhydride and monoammonium maleate, itaconic anhydride and diammonium maleamate, maleic acid and monoammonium maleate, maleic acid and diammonium maleate, fumaric acid and monoammonium maleate, fumaric acid and diammonium maleate, malic acid and monoammonium maleate, malic acid and diammonium maleate, itaconic acid and monoammonium maleate, itaconic acid and diammonium maleate, citraconic acid and monoammonium maleate or citraconic acid and diammonium maleate..Iaddend..Iadd.9. The method in accordance with claim 6 wherein said functional group-containing monomer is selected from the group consisting of polybasic carboxylic acids and anhydrides thereof, fatty acids, monobasic polyhydroxycarboxylic acids, alcohols, amines, diamines, triamines, polyamines, alkoxylated alcohols, alkoxylated amines, alkoxylated diamines, alkoxylated triamines, amino sugars, carbohydrates, sugar carboxylic acids, amino acids, non-protein forming aminocarboxylic acids, lactams, lactones, diols, triols, polyols, unsaturated dicarboxylic acids, tricarboxylic acids and unsaturated monocarboxylic acids..Iaddend..Iadd.10. The method in accordance with claim 6 wherein said functional group-containing monomer comprises at least one of the following compounds: lactic acid, citric acid, glycolic acid, malic acid, tartaric acid, succinic acid, adipic acid, butanetetracarboxylic acid, gluconic acid, glucuronic acid, glucaric acid, aconitic acid, sulfosuccinic acid, phosphinicosuccinic acid, phosphonosuccinic acid, iminodiacetic acid, nitrilotriacetic acid, stearic acid, palmitic acid, cyclohexanedicarboxylic acid, cyclohexanedicarboxylic anhydride, terephthalic acid, phthalic acid, phthalic anhydride, crotonic acid, sorbitol, glycerol, glucose, fructose, sucrose, maltose, glycine, alanine, glutamic acid, lysine, serine, threonine, cystine, cysteine, ethylenediamine, diethylenetriamine, triethylenetetraamine, polyamines, 1,6-diaminohexane, octadecylamine, glucosamine, alkoxylated amines, alkoxylated diamines, alkoxylated triamines, 6-aminocaproic acid, 4-aminobutyric acid, diaminocyclohexane, urea, melamine, carbohydrazide, hydrazine, ascorbic acid, isoascorbic acid, sorbic acid, maleuric acid, cyanuric acid, alkyldiamines, alkyltriamines, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, alkylmaleic acids, alkenylsuccinic acids, alkenylsuccinic anhydrides and methylenemalonic 
     
     
        acid..Iaddend..Iadd.1.  The method in accordance with claim 6 wherein said hydrolysis is carried out with a base selected from the group consisting of alkali metal hydroxide, alkaline earth metal hydroxide and ammonium hydroxide..Iaddend..Iadd.12. The method in accordance with claim 6 wherein said temperature is in the range of from about 100° C. to about 350° C..Iaddend..Iadd.13. The method in accordance with claim 6 wherein said temperature is at least 120° C..Iaddend.