Blends of polymers as wet strengthening agents for paper
Resin systems and methods for making and using same are provided. The method for making a paper product can include contacting a plurality of pulp fibers with a resin system. The resin system can include a first polyamidoamine-epihalohydrin resin and a second resin that can include a second polyamidoamine-epihalohydrin resin, a urea-formaldehyde resin, or a mixture thereof to produce a paper product. The first resin and the second resin can be sequentially or simultaneously contacted with the plurality of pulp fibers. The period for sequential addition between the first resin and the second resin is about 1 second to about 1 hour.
1. A resin system, comprising:
a first resin comprising a first polyamidoamine-epihalohydrin resin having azetidinium ions and amide residues, wherein the first polyamidoamine-epihalohydrin resin has an azetidinium equivalent weight of at least 2,000 to 3,800, wherein a ratio of the azetidinium ions to the amide residues is at least 0.7 to 1.0, and wherein the first polyamidoamine-epihalohydrin resin comprises a polyamine structural unit that is partially crosslinked with a bridging moiety derived from a functionally symmetric crosslinker; and
a second resin comprising a second polyamidoamine-epihalohydrin resin, a urea-formaldehyde resin, or a mixture of both, wherein the first resin and the second resin have at least one different property with respect to one another.
2. The resin system of claim 1 , wherein the at least one different property is a molecular weight, a chemical structure, or both a molecular weight and a chemical structure.
3. The resin system of claim 1 , wherein the functionally symmetric crosslinker comprises N,N ′-methylene-bis-acrylamide, N,N ′-methylene-bis-methacrylamide, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, polyethylene glycol diacrylate, or a mixture thereof.
4. The resins system of claim 1 , wherein the functionally symmetric crosslinker comprises:
wherein R 4 is (CH 2 ) t , and wherein t is 1, 2, or 3;
wherein x is from about 1 to about 100;
wherein y is from about 1 to about 100;
wherein x′ is at least 1, y′ is at least 1, and x′+y′ is from about 2 to about 100;
wherein z is from about 1 to about 100;
wherein a q/p ratio is from about 10 to about 1,000;
a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer with an azetidinium-functionalized monomer comprising:
or a mixture thereof; or
any mixture thereof.
5. The resin system of claim 1 , wherein the functionally symmetric crosslinker comprises a di-acrylate compound, a bis(acrylamide) compound, N,N′-methylene-bis-methacrylamide, a di-epoxide compound, a polyazetidinium compound, a poly(alkylene glycol) diglycidyl ether, or a mixture thereof.
6. The resin system of claim 1 , wherein the polyamine structural unit has the chemical formula:
wherein R is an alkyl, a hydroxyalkyl, an amine, an amide, an aryl, a heteroaryl, or a cycloalkyl and w is an integer from 2 to about 10,000.
7. The resin system of claim 1 , wherein the second resin comprises the urea-formaldehyde resin.
8. The resin system of claim 1 , wherein the second resin comprises the urea-formaldehyde resin, and wherein the resin system comprises greater than 30 wt % to about 80 wt % of the urea-formaldehyde resin, based on a combined solids weight of the first resin and the second resin.
9. The resin system of claim 1 , wherein the ratio of the azetidinium ions to the amide residues is about 0.8 to 1.0.
10. The resin system of claim 1 , wherein the second resin comprises the urea-formaldehyde resin, and wherein the urea-formaldehyde resin has a molar ratio of formaldehyde to urea of about 1:1 to about 3:1 and a weight average molecular weight of about 1,000 to about 500,000.
11. The resin system of claim 1 , wherein the polyamine structural unit comprises diethylenetriamine.
12. A process for making a paper product, comprising:
contacting a plurality of pulp fibers with a resin system comprising a first resin and a second resin to produce a mixture, wherein:
the first resin comprises a first polyamidoamine-epihalohydrin resin having azetidinium ions and amide residues, wherein the first polyamidoamine-epihalohydrin resin has an azetidinium equivalent weight of at least 2,000 to 3,800, wherein a ratio of the azetidinium ions to the amide residues is at least 0.7 to 1.0, and wherein the first polyamidoamine-epihalohydrin resin comprises a polyamine structural unit that is partially crosslinked with a bridging moiety derived from a functionally symmetric crosslinker,
the second resin comprises a second polyamidoamine-epihalohydrin resin, a urea-formaldehyde resin, or a mixture of both, and
the first resin and the second resin have at least one different property with respect to one another; and
at least partially curing the resin system in the mixture to produce the paper product.
13. The process of claim 12 , wherein the second resin comprises the urea-formaldehyde resin, and wherein the resin system comprises greater than 30 wt % to about 80 wt % of the urea-formaldehyde resin, based on combined solids weight of the first resin and the second resin.
14. The process of claim 12 , wherein the functionally symmetric crosslinker comprises N,N′-methylene-bis-acrylamide, N,N′-methylene-bis-methacrylamide, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, polyethylene glycol diacrylate, or a mixture thereof.
15. The process of claim 12 , wherein the functionally symmetric crosslinker comprises:
wherein R 4 is (CH 2 ) t , and wherein t is 1, 2, or 3;
wherein x is from about 1 to about 100;
wherein y is from about 1 to about 100;
wherein x′ is at least 1, y′ is at least 1, and x′+y′ is from about 2 to about 100;
wherein z is from about 1 to about 100;
wherein a q/p ratio is from about 10 to about 1,000;
a copolymer of an acrylate monomer, a methacrylate monomer, an alkene monomer, or a diene monomer with an azetidinium-functionalized monomer comprising:
or a mixture thereof; or
any mixture thereof.
16. The process of claim 12 , wherein the functionally symmetric crosslinker comprises a di-acrylate compound, a bis(acrylamide) compound, N,N′-methylene-bis-methacrylamide, a di-epoxide compound, a polyazetidinium compound, a poly(alkylene glycol) diglycidyl ether, or a mixture thereof.
17. The process of claim 12 , wherein the polyamine structural unit has the chemical formula:
wherein R is an alkyl, a hydroxyalkyl, an amine, an amide, an aryl, a heteroaryl, or a cycloalkyl and w is an integer from 2 to about 10,000.
18. A paper product, comprising:
a plurality of pulp fibers and an at least partially cured resin system, wherein the resin system, prior to curing, comprises a first resin comprising a first polyamidoamine-epihalohydrin resin having azetidinium ions and amide residues, wherein the first polyamidoamine-epihalohydrin resin has an azetidinium equivalent weight of at least 2,000 to 3,800, wherein a ratio of the azetidinium ions to the amide residues is at least 0.7 to 1.0, and wherein the first polyamidoamine-epihalohydrin resin comprises a polyamine structural unit that is partially crosslinked with a bridging moiety derived from a functionally symmetric crosslinker, and a second resin comprising a second polyamidoamine-epihalohydrin resin, a urea-formaldehyde resin, or a mixture of both, and wherein the first resin and the second resin have at least one different property with respect to one another.
19. The paper product of claim 18 , wherein the second resin comprises the urea-formaldehyde resin, and wherein the resin system comprises greater than 30 wt % to about 80 wt % of the urea-formaldehyde resin, based on combined solids weight of the first resin and the second resin.
20. The paper product of claim 18 , wherein the paper product has a repulpability of 98 % or more.