Polyamine Polyamidoamine Epihaloohydrin Compositions and Processes for Preparing and Using the Same

Abstract

Compositions of and processes for preparing a polyamine-polyamidoamine-epihalohydrin resin generally include reacting a first polyamine, a polyamidoamine, and an epihalohydrin to form the polyamine-polyamidoamine-epihalohydrin (PPAE) resin, wherein the polyamidoamine is prepared by reacting a polycarboxylic acid or a polycarboxylic acid derivative with a second polyamine to form the polyamidoamine, wherein a molar ratio of the polyamine to the polycarboxylic acid is 1.05 to 2.0. The PPAE resin can be used in an adhesive formulation for use in creping applications for forming paper products such as tissue products.

1 . A process for preparing a polyamine-polyamidoamine-epihalohydrin resin comprising:
 reacting a polyamidoamine, a first polyamine, and an epihalohydrin to form the polyamine-polyamidoamine-epihalohydrin resin, wherein the polyamidoamine is prepared by a process comprising reacting a polycarboxylic acid and/or a polycarboxylic acid derivative with a second polyamine to form the polyamidoamine, wherein a molar ratio of the second polyamine to the polycarboxylic acid and/or polycarboxylic acid derivative is 1.05 to 2.0.   
     
     
         2 . The process of  claim 1 , wherein reacting the first polyamine, the polyamidoamine, and the epihalohydrin is conducted in an aqueous media. 
     
     
         3 . The process of  claim 1 , wherein the epihalohydrin is epichlorohydrin. 
     
     
         4 . The process of  claim 1 , wherein the polycarboxylic acid and/or the polycarboxylic acid derivative is selected from the group comprising malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4 butanetetracarboxylic acid, nitrilotriacetic acid, N,N,N′,N′-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) and 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, diethyl glutarate, succinic anhydride, maleic anhydride, N,N,N′,N′-ethylenediaminetetraacetate dianhydride, phthalic anhydride, mellitic anhydride, pyromellitic anhydride, adipoyl chloride, glutaryl chloride, sebacoyl chloride, and mixtures thereof. 
     
     
         5 . The process of  claim 1 , wherein the first polyamine is selected from the group consisting of ammonium, aliphatic amines, aromatic amines, ethylene diamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP), pentaethylenehexamine (PEHA), and mixtures thereof. 
     
     
         6 . The process of  claim 1 , wherein the second polyamine is selected from the group consisting of diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP), pentaethylenehexamine (PEHA), and mixtures thereof. 
     
     
         7 . The process of  claim 1 , wherein the first and second polyamines are the same. 
     
     
         8 . The process of  claim 1 , wherein the first and second polyamines are different. 
     
     
         9 . The process of  claim 1 , wherein the ratio of EPI mass (g) over PA mass (g) is greater than about 1.499x-0.007, where N is the ratio of EPI sites (mole) over the product of RSV (dL/g) and PA mass (g). 
     
     
         10 . The process of  claim 1 , wherein the first polyamine to the polyamidoamine is at a weight ratio of 1:100 to 100:1. 
     
     
         11 . The process of  claim 1 , wherein the polyamine-polyamidoamine-epihalohydrin resin has a weight average molecular weight of 350 Daltons (Da) to 10 million Da. 
     
     
         12 . The process of  claim 1 , wherein the polyamine-polyamidoamine-epihalohydrin resin has a rewettability ratio of 5 to 100. 
     
     
         13 . The process of  claim 1 , wherein the polyamine-polyamidoamine-epihalohydrin resin has an insolubility percentage of 5 to 100%. 
     
     
         14 . A process for forming a creped paper product comprising:
 applying an adhesive formulation comprising a polyamine-polyamidoamine-epihalohydrin resin to a drying surface, wherein the polyamine-polyamidoamine-epihalohydrin resin has a rewettability ratio of 5 to 100, and an insolubility percentage of 5 to 100%, and wherein the polyamidoamine is prepared by a process comprising reacting a polycarboxylic acid and/or a polycarboxylic acid derivative with a second polyamine to form the polyamidoamine, wherein a molar ratio of the second polyamine to the polycarboxylic acid and/or polycarboxylic acid derivative is 1.05 to 2.0;   pressing a paper web against the drying surface to effect adhesion of the paper web to the surface; and   dislodging the paper web from the drying surface by contact with a doctor blade to form the creped paper product.   
     
     
         15 . The process of  claim 14 , wherein the creped paper product is an article selected from the group consisting of facial tissue, bath tissue, wipes, paper towels, paper napkins, filter papers, and coffee filters. 
     
     
         16 . The process of  claim 14 , wherein the epihalohydrin is epichlorohydrin. 
     
     
         17 . A composition comprising a polyamine-polyamidoamine-epihalohydrin resin, wherein the polyamidoamine is prepared by a process comprising reacting a polycarboxylic acid and/or a polycarboxylic acid derivative with a second polyamine to form the polyamidoamine, wherein a molar ratio of the second polyamine to the polycarboxylic acid and/or polycarboxylic acid derivative is 1.05 to 2.0. 
     
     
         18 . The composition of  claim 17 , wherein the polyamine-polyamidoamine-epihalohydrin resin has a rewettability ratio of 5 to 100. 
     
     
         19 . The composition of  claim 17 , wherein the polyamine-polyamidoamine-epihalohydrin resin has an insolubility percentage of 5 to 100%. 
     
     
         20 . The composition of  claim 17 , wherein the epihalohydrin is epichlorohydrin. 
     
     
         21 . The composition of  claim 17 , wherein the polycarboxylic acid and/or the polycarboxylic acid derivative is selected from the group comprising malonic acid, glutaric acid, adipic acid, azelaic acid, citric acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), 1,2,3,4 butanetetracarboxylic acid, nitrilotriacetic acid, N,N,N′,N′-ethylenediaminetetraacetate, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,4-benzenetricarboxylic acid (trimellitic acid) and 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid), dimethyl adipate, dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, diethyl glutarate, succinic anhydride, maleic anhydride, N,N,N′,N′-ethylenediaminetetraacetate dianhydride, phthalic anhydride, mellitic anhydride, pyromellitic anhydride, adipoyl chloride, glutaryl chloride, sebacoyl chloride, and mixtures thereof. 
     
     
         22 . The composition of  claim 17 , wherein the polyamine-polyamidoamine-epihalohydrin resin has a weight average molecular weight of 350 Daltons (Da) to 10 million Da. 
     
     
         23 . The composition of  claim 17 , wherein the polyamine of the polyamine-polyamidoamine-epihalohydrin resin and the second polyamine are selected from the group consisting of diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), dipropylenetriamine (DPTA), bis-hexamethylenetriamine (BHMT), N-methylbis(aminopropyl)amine (MBAPA), aminoethyl-piperazine (AEP), pentaethylenehexamine (PEHA), and mixtures thereof, wherein the polyamine and the second polyamine are the same or different. 
     
     
         24 . The composition of  claim 17 , wherein the polyamine of the polyamine-polyamidoamine-epihalohydrin resin is at a weight ratio to the polyamidoamine of 1:100 to 100:1. 
     
     
         25 . The composition of  claim 17 , further comprising water. 
     
     
         26 . The composition of  claim 25 , further comprising a co-adhesive, a plasticizer, a phosphate, a release aid, or mixtures thereof. 
     
     
         27 . The composition of  claim 26 , wherein the co-adhesive is selected from the group consisting of polyvinyl alcohol, polyamine epichlorohydrin, polyamidoamine, polyamidoamine epichlorohydrin, polyvinylamine, polyethyleneimine, polymethacrylamide, poly(acrylic acid), poly(methacrylic acid), poly(hydroxyethyl acrylate), poly(hydroxyethyl methacrylate), poly(n-vinyl pyrrolidinone), poly(ethylene oxide), hydroxyethyl cellulose, hydroxypropyl cellulose, guar gum, starch, agar, chitosan, alginic acid, carboxymethyl cellulose, silylated polyamidoamines polyvinylamine/N-vinylformamide, polyethyeleneimine, glyoxylated polyacrylamide, and mixtures thereof. 
     
     
         28 . The composition of  claim 26 , wherein the plasticizer is selected from the group consisting of glycerol, sorbitol and polyethylene glycol. 
     
     
         29 . The composition of  claim 26 , wherein the release aid is selected from the group consisting of mineral oil, vegetable oil, polyethylene glycol monoester, polyethylene glycol diester, ethoxylated polyethylene glycol, fatty acid imidazolinium surfactant, and mixtures thereof. 
     
     
         30 . The composition of  claim 26 , wherein the phosphate is selected from the group consisting of monoammonium phosphate and diammonium phosphate.