Poly(aminoamideureylene) resin, its synthesis, and its use in paper and paperboard manufacture

Abstract

The invention provides a novel poly(aminoamideureylene) resin and a process for making the resin without epichlorohydrin. The resin useful for improving wet strength of paper and paperboard intermediates. The resin is formed by making a prepolymer by reacting a diaminoamine, a dicarboxylic acid, and urea, allylating the prepolymer, and then reacting with hypohalous acid to produce an allylated quaternized poly(aminoamideureylene) having halohydrin substituents with resort to using epichlorohydrin. The resin can be activated for use in a papermaking process by treatment with a caustic (alkaline) agent. Optionally, the resin can be cross-linked prior to activation by heating in the presence of a caustic agent. The invention also provides an improvement in making polymers having halohydrin substituents formed by reacting an allylated polymer with hypohalous acid wherein the reaction is conducted without control of the pH. This invention also provides a method for producing hypohalous acid by acidifying an aqueous solution of an alkali metal hypohalite.

What is claimed is: 
     
       1. A process for producing a polymer, comprising the steps of: A. reacting (i) a diaminoamine, (ii) a dicarboxylic acid or a derivative thereof, and (iii) urea to produce a poly(aminoamideurylene); and   B. reacting the poly(aminoamideureylene) produced in step A. with an allyl halide to produce a quaternized allylated poly(aminoamideureylene) in a yield of ≦99.95.   
     
     
       2. The process defined by claim 1, further comprising the step of: C. reacting the quaternized allylated poly(aminoamideureylene) produced in step B. with hypohalous acid to produce a quaterized halohydrin-substituted poly(aminoamideureylene).   
     
     
       3. The process defined by claim 2, further comprising the step of: D. reacting the quaternized halohydrin-substituted poly(aminoamideureylene) produced in step C. with a caustic material in an amount effective to convert the halohydrin substituents to epoxide substituents.   
     
     
       4. The process defined by claim 3, wherein the amount of caustic reacted in step D, is effective to initiate cross-linking of the polymer. 
     
     
       5. The process defined by claim 4, wherein the amount of caustic reacted is effective to provide a polymer having a Gardner-Holdt viscosity in the range of D to E. 
     
     
       6. The process defined by claim 5, further comprising reacting the polymer with an amount of acid sufficient to terminate said cross-linking reaction and provide a cross-linked acid-stabilized polymer. 
     
     
       7. The process defined by claim 6, further comprising reacting the cross-linked acid-stailized polymer with an amount of caustic effective to activate the polymer for use in the manufacture of paper or paperboard products. 
     
     
       8. The process of claim 1, wherein the molar ratio of dicarboxylic acid to urea is in the approximate range of between 4:1 and 1:4. 
     
     
       9. The process defined by claim 8, wherein the molar ratio of dicarboxylic acid to urea is in the approximate range of between 3:1 and 1:3. 
     
     
       10. The process defined by claim 9, wherein the molar ratio of dicarboxylic acid to urea is in the approximately range of between 2:1 and 1:2. 
     
     
       11. The process defined by claim 1, wherein the hypohalous acid is hypochlorous acid. 
     
     
       12. The process defined by claim 11, wherein the hypochlorous acid is provided by chlorine sparging an aqueous solution of the quaternized allylated poly(aminoamideurelyene). 
     
     
       13. The process defined by claim 11, wherein the hypochlorous acid is provided by acidifying an aqueous solution of an alkali metal hypochlorite. 
     
     
       14. The process defined by claim 1, wherein the diaminoamine is of the formula NR 1  (R 2  NH 2 ) 2 , wherein R 1  is an alkyl group, and the two R 2  moieties, which may be the same or different, are each independently chosen as an alkyl group. 
     
     
       15. The process defined by claim 14, wherein the diaminoamine is methylbis(3-aminopropyl)amine. 
     
     
       16. The process defined by claim 1, wherein the dicarboxylic acid is of the formula HOOC--R 3  --COOH, wherein R 3  is a C 1-3  alkyl group or is omitted. 
     
     
       17. The process defined by claim 16, wherein the dicarboxylic acid is oxalic acid. 
     
     
       18. The process defined by claim 1, wherein the allyl halide is of the formula XCH 2  --CH 2 ) z  CH═CH 2 , in which X is a halogen, z is a positive integer of 5 or less or is zero, and wherein the hydrocarbyl chain is optionally branched. 
     
     
       19. A process of using the polymer prepared by the process of claim 1 which comprises: providing a furnish suitable for the manufacture of paper or paperboard products; providing said polymer in an aqueous solution; and adding said solution to said furnish in an amount effective to increase the wet strength of the product. 
     
     
       20. The process defined by claim 19, wherein the added solution comprises 0.01% to 10% by weight of the polymer based on the dry weight of the furnish. 
     
     
       21. A process of making a paper or paperboard product, which comprises: providing a furnish suitable for making said product; providing the polymer prepared by the process of claim 1 in an aqueous solution; adding said solution to said furnish in an amount effective to increase the wet strength of the product; forming a wet-laid sheet from said furnish; and drying said wet-laid sheet to form a paper or paperboard product. 
     
     
       22. The process defined by claim 21, wherein the added solution comprises 0.01% to 10% by weight of the polymer based on the dry weight of the furnish. 
     
     
       23. The process defined by claim 21, wherein the polymer is defined by claim 11. 
     
     
       24. A process of forming a polymer, comprising the steps of: A. providing a polyamine polymer having secondary amine (--NH--) groups in its backbone;   B. reacting said polyamine with an allyl halide to produce a quaternized allylated polyamine; and   C. reacting the quaternized allylated polyamine produced in step B. with hypochlorous acid to produce a quaternized halohydrin-substituted polyamine, characterized in that said hypohalous acid is provided by the acidification of an aqueous solution of an alkali metal hypochlorite.   
     
     
       25. The process defined by claim 24, further comprising the step of: D. reacting the quaternized halohydrin-substituted polyamine with a caustic material in an amount effective to initiate cross-linking of the polymer.   
     
     
       26. The process defined by claim 25, wherein the amount of caustic material is effective to provide a polymer having a Gardner-Holdt viscosity in the range of D to E. 
     
     
       27. The process defined by claim 25, further comprising the step of terminating said cross-linking by the addition of an amount of acid effective to provide a cross-linked acid-stabilized polymer having halohydrin substituents. 
     
     
       28. The process defined by claim 27, further comprising the step of reacting the cross-linked acid-stabilized polymer with an amount of caustic material effective to activate the polymer for use in the manufacture of paper or paperboard products. 
     
     
       29. A process for producing a polymer having halohydrin substituents, comprising: providing an allylated polymer having allyl groups; and reacting the allylated polymer with hypohalous acid, wherein the pH of the reaction is not controlled. 
     
     
       30. The process defined by claim 29, wherein the allylated polymer is a polyamine having allyl groups pendant from its backbone. 
     
     
       31. A process for the production of hypohalous acid, comprising: providing an aqueous solution of an alkali metal hypohalite; and acidifying said aqueous solution with an amount of mineral acid effective to produce said hypohalous acid. 
     
     
       32. The process defined by claim 31, wherein the mineral acid is hydrochloric acid. 
     
     
       33. The process defined by claim 31, wherein the alkali metal hypohalite is sodium hypohalite. 
     
     
       34. The process defined by claim 31, wherein the amount of mineral acid is effective to produce a pH in the range of 4 to 6.