Strengthened composite products and methods for making and using same
The disclosure provides strengthened products, including strengthened fibrous composite products and methods for making and using same and strengthened particulates, such as particulate fertilizer products, and methods for making and using same. The fibrous composite product can include a plurality of fibers and an at least partially cured strengthening resin. The fertilizer composition can include a particulate core that can include a plant nutrient, at least one coating layer of the strengthening resin, and at least one coating layer of a water insoluble material. The strengthening resin can include one or more aldehyde-based resins and one or more crosslinked resins. The crosslinked resin can include one or more polyamines at least partially crosslinked by one or more symmetric crosslinks and can include one or more azetidinium functional groups.
1. A fibrous composite product, comprising:
a plurality of fibers; and
an at least partially cured strengthening resin, wherein, prior to curing, the strengthening resin comprises an aldehyde-based resin and a polyamine,
wherein the polyamine has azetidinium ions and is partially crosslinked by a bridging moiety derived from a functionally symmetric crosslinker, and
wherein the fibrous composite product comprises about 5% to about 60% of the at least partially cured strengthening resin, based on a combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.
2. The fibrous composite product of claim 1 , wherein the functionally symmetric crosslinker comprises a diacrylate, a bis(acrylamide), a bis(methacrylamide), a diepoxide, a polyazetidinium compound, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, a dialdehyde, or a mixture thereof.
3. The fibrous composite product of claim 1 , wherein the polyamine having azetidinium ions and partially crosslinked by the bridging moiety derived from the functionally symmetric crosslinker is also at least partially crosslinked by a bridging moiety derived from an epihalohydrin.
4. The fibrous composite product of claim 3 , wherein the functionally symmetric crosslinker comprises N,N′-methylenebisacrylamide, and wherein the epihalohydrin comprises epichlorohydrin.
5. The fibrous composite product of claim 1 , wherein the polyamine comprises a reaction product of a crosslinked intermediate compound and an epihalohydrin, and wherein the crosslinked intermediate compound comprises a reaction product of a polyamidoamine and a bisacrylamide.
6. The fibrous composite product of claim 1 , wherein the fibrous composite product comprises about 10% to about 40% of the at least partially cured strengthening resin, based on the combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.
7. The fibrous composite product of claim 1 , wherein the strengthening resin comprises about 85% to about 99.5% of the aldehyde-based resin, based on a combined solids weight of the aldehyde based resin and the polyamine.
8. The fibrous composite product of claim 1 , wherein the strengthening resin comprise about 90% to about 99.5% of the aldehyde-based resin, based on the combined solids weight of the aldehyde-based resin and the polyamine.
9. The fibrous composite product of claim 1 , wherein the aldehyde-based resin comprises a urea-formaldehyde resin, a phenol-formaldehyde resin, a resorcinol-formaldehyde resin, a phenol-resorcinol-formaldehyde resin, a phenol-urea-formaldehyde resin, a melamine-formaldehyde resin, a melamine-urea-formaldehyde resin, a phenol-melamine-formaldehyde resin, or a mixture thereof.
10. The fibrous composite product of claim 1 , wherein the plurality of fibers comprises glass fibers, mineral fibers, ceramic fibers, carbon fibers, or a mixture thereof.
11. The fibrous composite product of claim 1 , wherein:
the plurality of fibers comprises glass fibers,
the strengthening resin comprises about 85% to about 99.5% of the aldehyde-based resin, based on a combined solids weight of the aldehyde based resin and the polyamine,
the aldehyde-based resin comprises a urea-formaldehyde resin,
the functionally symmetric crosslinker comprises a diacrylate, a bis(acrylamide), a bis(methacrylamide), a diepoxide, a polyazetidinium compound, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, a dialdehyde, or a mixture thereof, and
the fibrous composite product comprises about 10% to about 25% of the at least partially cured strengthening resin, based on the combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.
12. A fibrous composite product, comprising:
a fiber web; and
an at least partially cured strengthening resin, wherein prior to curing, the strengthening resin comprises a urea-formaldehyde resin and a polyamine,
wherein the polyamine has azetidinium ions and is partially crosslinked by a bridging moiety derived from a functionally symmetric crosslinker, and
wherein the fibrous composite product comprises about 10% to about 20% of the at least partially cured strengthening resin, based on a combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.
13. The fibrous composite product of claim 12 , wherein the fiber web comprises a plurality of glass fibers, and wherein the functionally symmetric crosslinker comprises a bisacrylamide.
14. The fibrous composite product of claim 12 , wherein:
the fiber web comprises a plurality of glass fibers,
the polyamine having azetidinium ions and partially crosslinked by the bridging moiety derived from the functionally symmetric crosslinker is also at least partially crosslinked by a bridging moiety derived from epichlorohydrin,
the functionally symmetric crosslinker comprises N,N′-methylenebisacrylamide, and
the strengthening resin comprises about 85% to about 99.5% of the urea-formaldehyde resin, based on a combined solids weight of the urea-formaldehyde resin and the polyamine.
15. A process for making a fibrous composite product, comprising:
contacting a plurality of fibers with a strengthening resin to produce a mixture, wherein the strengthening resin comprises an aldehyde-based resin and a polyamine, and wherein the polyamine has azetidinium ions and is at least partially crosslinked by a bridging moiety derived from a functionally symmetric crosslinker; and
at least partially curing the strengthening resin in the mixture to produce the fibrous composite product, wherein the fibrous composite product comprises about 5% to about 60% of the at least partially cured strengthening resin, based on a combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.
16. The process of claim 15 , wherein the mixture is heated to a temperature of about 100° C. to about 350° C. for about 1 second to about 5 minutes to at least partially cure the strengthening resin.
17. The process of claim 15 , wherein the functionally symmetric crosslinker comprises a diacrylate, a bis(acrylamide), a bis(methacrylamide), a diepoxide, a polyazetidinium compound, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, a dialdehyde, or a mixture thereof.
18. The process of claim 15 , wherein the strengthening resin comprises about 85% to about 99.5% of the aldehyde-based resin, based on a combined solids weight of the aldehyde based resin and the polyamine.
19. The process of claim 15 , wherein the plurality of fibers comprises glass fibers, mineral fibers, ceramic fibers, carbon fibers, or a mixture thereof.
20. The process of claim 15 , wherein:
the plurality of fibers comprises glass fibers,
the strengthening resin comprises about 85% to about 99.5% of the aldehyde-based resin, based on a combined solids weight of the aldehyde based resin and the polyamine,
the aldehyde-based resin comprises a urea-formaldehyde resin,
the functionally symmetric crosslinker comprises a diacrylate, a bis(acrylamide), a bis(methacrylamide), a diepoxide, a polyazetidinium compound, a diisocyanate, a 1,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, a dialdehyde, or a mixture thereof, and
the fibrous composite product comprises about 10% to about 25% of the at least partially cured strengthening resin, based on the combined solids weight of the plurality of fibers and the at least partially cured strengthening resin.