Novel reaction product of starches and aromatic acids and/or aromatic anhydrides

Abstract

This invention relates to the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein the starch is reacted in the solid state with solid state reactants comprising the aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between the anhydride and/or acid.

We claim:  
     
         1 . A reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, in the absence of a base catalyst, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group.  
     
     
         2 . The reaction product of  claim 1  wherein said starch is derived from rice, wheat, tapioca, potatoes, and/or corn.  
     
     
         3 . The reaction product of  claim 1  herein said starch is acid-modified prior to said solid state reaction.  
     
     
         4 . The reaction product of  claim 1  wherein said starch is in a granulated form.  
     
     
         5 . The reaction product of  claim 1  wherein the number average molecular weight of the starch is 10,000-300,000.  
     
     
         6 . The reaction product of  claim 1  wherein the number average molecular weight of the starch is 80,000-120,000.  
     
     
         7 . The reaction product of  claim 1  wherein said aromatic anhydride and/or aromatic acid is present in the amount of 0.05 to 6 weight % and wherein the total weight percentage of starch and anhydride or acid equals 100 weight %.  
     
     
         8 . The reaction product of  claim 7  wherein said aromatic anhydride and/or aromatic acid is present in the amount of 3.0 to 5.0 weight %.  
     
     
         9 . The reaction product of  claim 1  wherein said aromatic anhydride initially has a particle size of 2 mm or less.  
     
     
         10  The reaction product of  claim 1  wherein said aromatic anhydride is selected from the group consisting of trimellitic anhydride, pyromellitic dianhydride and phthalic anhydride.  
     
     
         11 . The reaction product of  claim 10  wherein said aromatic anhydride is phthalic anhydride.  
     
     
         12 . The reaction product of  claim 1  having a D.S. of 0.001 to 0.10.  
     
     
         13 . The reaction product of  claim 7  having a D.S. of 0.001 to 0.07.  
     
     
         14 . The reaction product of  claim 1  wherein, during the solid state reaction, said solid state reactants have a total water content of 0 to 6.0 weight % based on a total weight percentage for the solid state reactants of 100% weight %.  
     
     
         15 . The reaction product of  claim 14  wherein said solid state reactants have a total water content of 0.1 to 4.0% weight %.  
     
     
         16 . The reaction product of  claim 14  wherein said solid state reactants have a total water content of less than 1.0% weight %.  
     
     
         17 . The reaction product of  claim 1  wherein a base is added to the final reaction product to react with unreacted aromatic anhydride or aromatic acid.  
     
     
         18 . The reaction product of  claim 17  wherein said base is selected from the group consisting of ammonia, aqua ammonia, amines, polyamines, and aminoalcohols.  
     
     
         19 . The reaction product of  claim 1  wherein said at least one starch and said at least one aromatic anhydride and/or aromatic acid are mixed in a dry blender during the reaction.  
     
     
         20 . A reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group; and wherein, during said solid state reaction, said solid state reactants have a total water content of 0 to 6.0 weight % based on a total weight percentage.  
     
     
         21 . The reaction product of  claim 20  wherein said starch is derived from rice, wheat, tapioca, potatoes, and/or corn.  
     
     
         22 . The reaction product of  claim 20  wherein said starch is acid-modified prior to said solid state reaction.  
     
     
         23 . The reaction product of  claim 20  wherein said starch is in a granulated form.  
     
     
         24 . The reaction product of  claim 20  wherein the number average molecular weight of the starch is 10,000-300,000.  
     
     
         25 . The reaction product of  claim 24  wherein the number average molecular weight of the starch is 80,000-120,000.  
     
     
         26 . The reaction product of  claim 1  wherein said aromatic anhydride and/or aromatic acid is present in the amount of 0.05 to 6 weight % and wherein the total weight percentage of starch and anhydride or acid equals 100 weight %.  
     
     
         27 . The reaction product of  claim 20  wherein said aromatic anhydride and/or aromatic acid is present in the amount of 3.0 to 5.0 weight %.  
     
     
         28 . The reaction product of  claim 20  wherein said aromatic anhydride initially has a particle size of 2 mm or less.  
     
     
         29 . The reaction product of  claim 20  wherein said aromatic anhydride is selected from the group consisting of trimellitic anhydride, pyromellitic dianhydride and phthalic anhydride.  
     
     
         30 . The reaction product of  claim 20  wherein said aromatic anhydride is phthalic anhydride.  
     
     
         31 . The reaction product of  claim 20  having a D.S. of 0.001 to 0.10.  
     
     
         32 . The reaction product of  claim 20  having a D.S. of 0.001 to 0.07.  
     
     
         33 . The reaction product of  claim 20  wherein said solid state reactants have a water content of less than 5.0% by weight.  
     
     
         34 . The reaction product of  claim 20  wherein said solid state reactants have a total water content of 0.1-4.0% by weight.  
     
     
         35 . The reaction product of  claim 20  wherein said solid state reactants have a total water content of less than 1.0% by weight.  
     
     
         36 . The reaction product of  claim 20  wherein said at least one starch and said at least one aromatic anhydride and/or aromatic acid are mixed in a dry blender during the reaction.  
     
     
         37 . A textile sizing agent comprising the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, in the absence of a base catalyst, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group.  
     
     
         38 . A textile sizing agent comprising the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group; and wherein, during said solid state reaction, said solid state reactants have a total water content of 0 to 6.0 weight % based on a total weight percentage of 100 weight %.  
     
     
         39 . A textile sizing agent for polyester fibers and polyester-containing yarn comprising the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, in the absence of a base catalyst, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group.  
     
     
         40 . A textile sizing agent for polyester fibers and polyester-containing yarn comprising the reaction product of at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group; and wherein, during said solid state reaction, said solid state reactants have a total water content of 0 to 6.0 weight % based on a total weight percentage of 100 weight %.  
     
     
         41 . A textile yarn sized with the textile sizing agents of claims  37  and  38 .  
     
     
         42 . The textile yarn of  claim 41  comprising one or more polyesters.  
     
     
         43 . The textile yarn of  claim 42  wherein said one or more polyesters comprise 80 to 100 mole % terephthalic acid residues and 100 to 80 mole % ethylene glycol wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         44 . The textile yarn of  claim 43  comprising poly(ethylene terephthalate).  
     
     
         45 . The textile yarn of  claim 42  wherein said one or more polyesters comprise 80 to 100 mole % terephthalic acid residues and 100 to 80 mole % 1,4-cyclohexanedimethanol wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         46 . The textile yarn of  claim 42  wherein said one or more polyesters comprise 80 to 100 mole % terephthalic acid residues, 10 to 50 mole % 1,4-cyclohexanedimethanol residues, and 90 to 50 mole % ethylene glycol residues, wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         47 . The textile yarn of  claim 41  comprising a blend of polyester fibers and fibers selected from the group consisting of cotton, polyacrylics, polyolefins, rayons, and wool.  
     
     
         48 . A process for sizing a textile substrate material comprising applying to the textile material a composition comprising the reaction product of claims  1  and  20 .  
     
     
         49 . The process of  claim 45  wherein said textile substrate material comprises one or more polyesters.  
     
     
         50 . The process of  claim 49  wherein said one or more polyesters comprising 80 to 100 mole % terephthalic acid residues and 100 to 80 mole % ethylene glycol wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         51 . The textile yarn of  claim 49  wherein said one or more polyesters comprise 80 to 100 mole % terephthalic acid residues and 100 to 80 mole % 1,4-cyclohexanedimethanol wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         52 . The textile yarn of  claim 49  wherein said one or more polyesters comprise 80 to 100 mole % terephthalic acid residues, 10 to 50 mole % 1,4-cyclohexanedimethanol residues, and 90 to 50 mole % ethylene glycol residues, wherein the total mole percentages of the glycol component equals 100 mole % and the total mole percentages of the acid component equals 100 mole %.  
     
     
         53 . The process of  claim 49  comprising a blend of polyester fibers and fibers selected from the group consisting of cotton, polyacrylics, polyolefins, rayons, and wool.  
     
     
         54 . The process of reacting at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, in the absence of a base catalyst, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group.  
     
     
         55 . The process of reacting at least one starch with at least one aromatic anhydride and/or aromatic acid wherein said starch is reacted in the solid state with solid state reactants comprising said aromatic anhydride and/or aromatic acid, and at a time and temperature sufficient to obtain a reaction between said anhydride and/or acid and said starch(es) to form an ester substituent group; and wherein, during said solid state reaction, the solid state reactants have a total water content of 0 to 6.0 weight % based on a total weight percentage of 100 weight %.  
     
     
         56 . The process of  claim 55  wherein said starch and aromatic anhydride or aromatic acid are dried prior to the solid state reaction to a water content of 0.1 to 4.0 weight %.  
     
     
         57 . The process of  claim 56  wherein said starch and aromatic anhydride or aromatic acid are dried prior to the solid state reaction to a water content of less than 1 weight %.  
     
     
         58 . The process of  claim 56  wherein said starch and aromatic anhydride or aromatic acid are dried under vacuum where said temperature is increased to the initial reaction temperature.