Compositions and preparation methods of gpam

Abstract

GPAM COMPOSITIONS AND METHODS. The present invention generally relates to glyoxylated polyacrylamide (GPAM) compositions, methods of preparation and methods of use thereof, particularly in the paper industry. Furthermore, the present invention generally pertains to cationic GPAM compositions, methods of preparation and methods of use thereof in papermaking applications and in products such as paper-based products, wherein the cationic GPAM compositions can provide greater wet and / or dry strength to paper-based products, and wherein such cationic GPAM compositions optionally require a reduced volume of an aqueous carrier for storage or transport compared to the volume of an aqueous carrier required for conventional GPAMs used in papermaking.

Description

Descriptive Report of the Invention Patent for GPAM COMPOSITIONS AND PREPARATION METHODS. FIELD OF THE INVENTION

[001] The present invention relates to glyoxylated polyacrylamide (GPAM) compositions and articles comprising them and methods of using them, particularly GPAM compositions useful in the paper industry and, more particularly, cationic GPAM compositions and their use in papermaking applications and in products such as paper-based products. The present invention also generally relates to methods of preparing said cationic GPAM compositions. BACKGROUND

[002] Glyoxylated polyacrylamide (GPAM) compositions are widely used in the paper industry, often to increase the wet and dry strength of paper. For example, glyoxylated polyacrylamide can increase the initial wet strength of many household paper products, a useful property since household paper products often come into contact with water during their use. The application of glyoxylated polyacrylamide in paper products can also increase the compressive strength and dimensional stability of many board-grade paper products.

[003] GPAM is typically prepared via a reaction between glyoxal and a polyacrylamide base polymer, such as a cationic polyacrylamide backbone. In some cases, the reaction between glyoxal and cationic polyacrylamide is carried out in slightly alkaline aqueous solution and stabilized under acidic conditions. In practice, the polyacrylamide component of GPAM compositions often contains relatively low amounts of cationic monomer, typically below about 5 mol percent thereof, thus limiting the cationic charge contribution to the GPAM composition. Petition 870240109898, dated 12 / 24 / 2024, page 14 / 182 2 / 56

[004] Furthermore, GPAMs produced by conventional methods generally cannot be dried into a solid particulate form without inducing significant and rapid crosslinking of the GPAM, which limits the usefulness of the resulting GPAM composition. As such, GPAM compositions are typically stored and transported in a bulk aqueous fluid vehicle. The volumes of GPAM composition transported in this manner can be significant, often requiring large-volume containers or tankers for transport. Shipping such large volumes of product significantly increases costs for those who transport and use GPAM compositions.

[005] As a result of the properties of the compositions of Given current GPAM (Garbled Passenger Maturity) considerations and logistical aspects of its transportation, there remains a need for GPAM compositions that incorporate properties that promote lower transportation costs and / or lower transportation quantities of GPAM compositions, while still maintaining the desired properties of the GPAM composition. BRIEF SUMMARY

[006] The present invention relates to a cationic glyoxylated polyacrylamide (GPAM) composition suitable for use as a dry and / or wet strengthening agent, wherein said cationic GPAM composition comprises: a. a first base polymer having a weighted average molecular weight of less than 30,000 Da; and b. a second base polymer having a weighted average molecular weight of at least 30,000 Da; wherein the first base polymer and the second base polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, or even optionally about 30:70 to about 70:30; wherein the first base polymer and the second base polymer are each, Petition 870240109898, dated 12 / 24 / 2024, page 15 / 182 3 / 56 glyoxalated; and wherein, optionally, the cationic GPAM composition requires a reduced volume of an aqueous carrier for storage or transport compared with a volume of an aqueous carrier required for conventional GPAMs used in papermaking.

[007] In some embodiments, the weighted average molecular weight of the first base polymer may be at most 25 kDa or less, 20 kDa or less, 15 kDa or less, 10 kDa or less or 8 kDa or less. In some embodiments, the weighted average molecular weight of the second base polymer may be at least 30 kDa or more, 40 kDa or more, 50 kDa or more, 75 kDa or more, 100 kDa or more, 125 kDa or more, 150 kDa or more, 175 kDa or more, 200 kDa or more, 225 kDa or more, 250 kDa or more, 275 kDa or more, 300 kDa or more, 325 kDa or more, 350 kDa or more, 375 kDa or more, 400 kDa or more, or 500 kDa or more.In some embodiments, the glyoxylation percentage of the cationic GPAM composition can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the glyoxylation percentage of the first base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the glyoxylation percentage of the second base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%.In some embodiments, the GPAM content of the cationic GPAM composition may be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. In some embodiments, the GPAM content... Petition 870240109898, dated 12 / 24 / 2024, p. 16 / 182 4 / 56 of the first base polymer can be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. In some embodiments, the GPAM content of the second base polymer can be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. In some embodiments, the first base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein, optionally, the first base polymer may be amphoteric.In some embodiments, the second base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the second base polymer may be amphoteric. In some embodiments, the first base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the first base polymer may be amphoteric.In some embodiments, the second base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, or at least 30% by weight. Petition 870240109898, dated 12 / 24 / 2024, page 17 / 182 5 / 56 weight, at least 35% by weight, at least 40% by weight, at least 50% by weight or at least 60% by weight, wherein optionally the second base polymer may be amphoteric. In some embodiments, the cationic GPAM composition may comprise a weight percentage of solids of about 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0% or more, 5.5% or more, 6.0% or more, 6.5% or more, 7.0% or more, 7.5% or more, 8.0% or more, 8.5% or more, 9.0% or more, 9.5% or more, 10.0% or more, 10.5% or more, 11.0% or more or 11.5% or more. In some embodiments, the composition of cationic GPAM may comprise a weight percentage of solids of about 1.0% to about 20.0%, optionally from about 3.0% to about 15.0%.In some embodiments, the cationic GPAM composition may comprise a weight ratio between glyoxal and the total base polymer of at least about 1:99, at least about 2.5:97.5, at least about 5:95, at least about 7.5:92.5, at least about 10:90, at least about 12.5:87.5, at least about 15:85, at least about 17.5:82.5, at least about 20:80, at least about 22.5:77.5, at least about 25:75, at least about 27.5:72.5, at least about 29:71, or at least about 30:70. In some embodiments, the first base polymer may comprise an acrylamide-based polymer. In some embodiments, the second base polymer may comprise an acrylamide-based polymer. In some embodiments, the first base polymer may comprise one or more cationic monomers. In some embodiments, the second base polymer may comprise one or more cationic monomers.In some embodiments, the first base polymer may comprise a weight ratio of cationic monomer to acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and still optionally from about 25:75 to about 50:50. Petition 870240109898, dated 12 / 24 / 2024, page 18 / 182 6 / 56 In some embodiments, the second base polymer may comprise a weight ratio of cationic monomer to acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and still optionally from about 25:75 to about 50:50. In some embodiments, the first base polymer may be amphoteric and may comprise more cationic monomers than anionic monomers. In some embodiments, the second base polymer may be amphoteric and may comprise more cationic monomers than anionic monomers. In some embodiments, the first base polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, the second base polymer may comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers.In some embodiments, the viscosity of the cationic GPAM composition may be about 10 cPs or more, about 15 cPs or more, about 20 cPs or more, about 25 cPs or more, about 30 cPs or more, or about 35 cPs or more, for example, as measured by a Brookfield LV viscometer at 25 °C and 600 rpm using spindle number 1. In some embodiments, the aqueous vehicle may comprise water.

[008] In some embodiments, one or more cationic monomers may each be selected from the group consisting of acryloyloxyethyltrimethylammonium chloride (AETAC), methacryloyloxyethyltrimethylammonium chloride, methacrylamidepropyltrimethylammonium chloride (MAPTAC), acrylamidepropyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, diallyldimethylammonium chloride (DADMAC); dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, Petition 870240109898, dated 12 / 24 / 2024, page 19 / 182 7 / 56 including, but not limited to, quaternary salt of dimethylaminoethyl methyl acrylate chloride (DMAEA.MCQ), quaternary salt of dimethylaminoethyl acrylate methyl sulfate (DMAEM.MCQ), quaternary salt of benzyl chloride of dimethylaminoethyl acrylate (DMAEA.BCQ), sulfuric acid salt of dimethylaminoethyl acrylate, hydrochloric acid salt of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of methyl chloride of dimethylaminoethyl methacrylate, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of benzyl chloride of dimethylaminoethyl methacrylate, sulfuric acid salt of dimethylaminoethyl methacrylate, hydrochloric acid salt of dimethylaminoethyl methacrylate, acid salt dimethylaminoethyl methacryloyl hydrochloride dialkylaminoalkylacrylamides or methacrylamides and their quaternary salts or acids, such as acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropylacrylamide, hydrochloric acid salt of dimethylaminopropylacrylamide, chloride of methacrylamidopropyltrimethylammonium, quaternary salt of dimethylaminopropyl methacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropyl methacrylamide, hydrochloric acid salt of dimethylaminopropyl methacrylamide, diethylaminoethylacrylate, diethylaminoethyl methacrylate and diallyldialkylammonium halides, such as diallyldiethylammonium chloride and diallyldimethylammonium chloride. In some embodiments, one or more cationic monomers may comprise DADMAC. In some embodiments, one or more cationic monomers may comprise acryloyloxyethyltrimethylammonium chloride (Q9). In some embodiments, one or more cationic monomers may each comprise DADMAC and / or acryloyloxyethyltrimethylammonium chloride (Q9). In some embodiments, one or Petition 870240109898, dated 12 / 24 / 2024, page 20 / 182 8 / 56 more cationic monomers can each be selected from the group consisting of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (Q9), 3-(methacrylamide)propyltrimethyltrimethylammonium chloride, 3-(acryloylamide)propyltrimethyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylammonioethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and dimethylaminopropyl acrylamide, dimethylaminopropylmethacrylamide.

[009] In some embodiments, the acrylamide-based polymer may comprise one or more primary amide-containing monomers. In some embodiments, the acrylamide-based polymer may comprise one or more monomers selected from the group consisting of acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof. In some embodiments, the acrylamide-based polymer may comprise one or more acrylamide monomers.

[0010] In exemplary embodiments, the cationic GPAM in the GPAM composition is selected from the following: a. the first base polymer and the second base polymer comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers; b. the first base polymer and / or the second base polymer comprises a copolymer of (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC) monomers; c. the first base polymer or the second base polymer comprises a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; d. the first base polymer and the second base polymer comprise a copolymer of acrylamide and other monomers Petition 870240109898, dated 12 / 24 / 2024, page 21 / 182 9 / 56 dimethyldiallylammonium chloride (DADMAC); (e.) The first base polymer and the second base polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers, and the glyoxal:base polymer ratio for the glyoxation reaction varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71; f. the first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa or 250 kDa or 246 kDa; g. the first base polymer and the second base polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; and the glyoxal:base polymer ratio for the glyoxylation reaction used to glyoxylate the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; h. The first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to Petition 870240109898, dated 12 / 24 / 2024, page 22 / 182 10 / 56 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, also optionally from about 30:70 to about 70:30, still optionally from about 40:60 to about 60:40; or i. the first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer ranges from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, also optionally from about 30:70 to about 70:30, still optionally from about 40:60 to about 60:40 and the GPAM content varies from about 5% to about 7%, or about 6%-7.5% or about 6% to 7%.

[0011] Furthermore, the present invention relates to a paper product comprising one or more cationic GPAM compositions, as discussed in this document. In some embodiments, said paper product may comprise at least one layer or sheet of paper containing the cationic GPAM composition. In some embodiments, the paper product may comprise the cationic GPAM composition on at least one surface of the paper product. In some embodiments, said paper product may comprise one or more of paper sheets, cardboard, paper fabric, and wallpaper. In some embodiments, said product Petition 870240109898, dated 12 / 24 / 2024, page 23 / 182 11 / 56 of paper may comprise one or more of the following: kraft paper, sulfite paper, semi-chemical paper and the like, including paper produced using bleached pulp, unbleached pulp or combinations thereof. In some embodiments, said paper product may comprise a fiber-based product.In some embodiments, the said paper product may comprise one or more of the following: hand sheets, cardboard-type paper products, beverage carriers, towels, milk and juice cartons, food trays, paper bags, lining board for corrugated cardboard containers, cardboard-type packaging, paper materials, paper towels, diapers, sanitary napkins, baby training pants, panty liners, incontinence underwear, tampons, pet urine mats, garbage can liners, coffee filters, air filters, floor cleaning cloths, absorbent facial tissue, absorbent bathroom tissue, napkins, wrapping paper and / or other cardboard products such as cardboard boxes and paper for shopping bags. In some embodiments, the said paper product may comprise cellulose cardboard sheets that optionally comprise predominantly cellulose fibers.In some embodiments, said paper product may comprise from about 0.02% to about 10% of cationic GPAM composition by dry weight of cellulose fibers, optionally in the range of about 0.05% by weight to 5% by weight of dry paper weight. In some embodiments, the paper product may comprise improved paper strength, for example, as determined by STFI tests, compared to a paper product that does not comprise a cationic GPAM composition. For example, in some embodiments, said paper product may comprise an STFI value improvement of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0%. Petition 870240109898, dated 12 / 24 / 2024, page 24 / 182 12 / 56 or more at 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton or 10 lbs / ton test compared to a pure sample used for the STFI test of the paper product. In some embodiments, the paper product may comprise an improved paper strength, for example, as determined by the explosion resistance test, compared to a paper product that does not comprise a cationic GPAM composition. For example, in some embodiments, the said paper product may comprise an improvement in the explosion resistance value of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more, 27.5% or more, 30.0% or more, 32.5% or more, 35.0% or more, 37.5% or more, or 40% or more in 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a pure sample used for the explosion resistance test.

[0012] In exemplary embodiments, the paper product comprising one or more cationic GPAM compositions comprises a cationic GPAM, wherein: a. the first base polymer and the second base polymer comprise a copolymer of acrylamide or methacrylamide monomers and one or more cationic monomers; b. the first base polymer and / or the second base polymer comprises a copolymer of (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC) monomers; c. the first base polymer or the second base polymer comprises a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; d. the first base polymer and the second base polymer comprise a copolymer of acrylamide and other monomers Petition 870240109898, dated 12 / 24 / 2024, page 25 / 182 13 / 56 dimethyldiallylammonium chloride (DADMAC); (e.) The first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer, and the glyoxal / base polymer ratio for the glyoxation reaction varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71 monomers; f. the first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa or 250 kDa or 246 kDa; g. the first base polymer and the second base polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; and the glyoxal / base polymer ratio for the glyoxylation reaction used to glyoxylate the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; h. The first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to Petition 870240109898, dated 12 / 24 / 2024, page 26 / 182 14 / 56 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, also optionally from about 30:70 to about 70:30, still optionally from about 40:60 to about 60:40; or i. the first base polymer and the second base polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; the molecular weight of the first base polymer is not more than 25 kDa, 20 kDa, 15 kDa, 8 kDa or 5 kDa and the molecular weight of the second base polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa or about 246 kDa; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer ranges from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40 or is about 29:71; and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, also optionally from about 30:70 to about 70:30, still optionally from about 40:60 to about 60:40 and the GPAM content varies from about 5% to about 7%, or about 6%-7.5% or about 6% to 7%.

[0013] Furthermore, the present invention generally relates to a method of papermaking, wherein said method comprises adding one or more cationic GPAM compositions, as discussed in this document, during the papermaking method in an amount effective to increase the wet and / or dry strength of the paper products produced by said method. In some embodiments, one or more cationic GPAM compositions may be added to a composition comprising fiber and / or pulp used in the method before the paper product is formed. In some embodiments, one or more cationic GPAM compositions may Petition 870240109898, dated 12 / 24 / 2024, page 27 / 182 15 / 56 to be added to one or more surfaces of the paper product after the paper product has been formed.

[0014] In addition, the present invention generally relates to a method for producing hand sheets, said method comprising: a. providing a pulp stock; b. diluting the pulp stock; c. adding one or more salts to a desired level of conductivity; d. adjusting the pH to a desired value; e. adding one or more cationic GPAM compositions as discussed in this document; f. adding the treated pulp to a dynamic sheet former; g. pressing the sheets resulting from f.; h. drying the sheets; and i. conditioning the sheets.

[0015] Furthermore, the present invention generally pertains to a method of manufacturing one or more paper products, wherein said method comprises: a. providing a composition comprising predominantly cellulose fibers; b. adding a predetermined amount of one or more cationic GPAM compositions, as discussed in this document; and c. forming the desired paper product.

[0016] In addition, the present invention generally relates to a method of manufacturing one or more paper products, optionally one or more absorbent paper products, wherein said method comprises: (a) . provide a composition comprising any softwood fiber, hardwood fiber, recycled fiber, refined fiber or a mixture of any of the foregoing in a quantity sufficient to form a general supply of approximately 1 to 100% hardwood fiber, softwood fiber, recycled fiber, refined fiber or a mixture of any of the foregoing; (b) add a predetermined quantity of one or Petition 870240109898, dated 12 / 24 / 2024, page 28 / 182 16 / 56 plus cationic GPAMs, as discussed in this document; and (c) forming a paper product by drying through one or more drying means to a desired moisture content level.

[0017] In addition, the present invention generally relates to a method for increasing paper strength, comprising contacting pulp fibers with a strengthening resin comprising at least a cationic GPAM composition, as discussed in this document, and at least partially curing the cationic GPAM in the pulp fiber and cationic GPAM mixture to produce a paper product with enhanced strength.

[0018] In some embodiments, the cationic GPAM composition can be added at the wet end of a papermaking plant to cellulose fiber suspensions. In some embodiments, the cationic GPAM composition can be added from about 0.02% by dry weight to about 10% by dry weight of the cellulose fibers, optionally in the range of about 0.05% by weight to 5% by weight of the dry paper weight. In some embodiments, the cationic GPAM composition can be added before, during, and / or after paper forming. In some embodiments, the cationic GPAM composition can be added to one or more surfaces of the paper product after the paper product has been formed. In some embodiments, the cationic GPAM composition can provide an improvement in paper strength to the paper product, for example, as determined by the STFI test.For example, in some embodiments, the paper product may comprise an improvement in STFI value of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more in 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton or 10 lbs / ton test compared to a pure sample used for STFI testing of the paper product. In some embodiments, a. Petition 870240109898, dated 12 / 24 / 2024, p. 29 / 182 17 / 56 cationic GPAM composition can provide an enhancement of paper strength to the paper product, for example, as determined by the explosion resistance test. For example, in some embodiments, the paper product may comprise an improvement in the explosion resistance value of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more, 27.5% or more, 30.0% or more, 32.5% or more, 35.0% or more, 37.5% or more, or 40% or more in 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a pure sample used for the explosion resistance test.In some embodiments, the paper product may comprise one or more of the following: hand sheets, paperboard-type products, beverage carriers, towels, milk and juice cartons, food trays, paper bags, lining board for corrugated cardboard containers, paperboard-type packaging, paper materials, paper towels, diapers, sanitary napkins, baby potty pants, panty liners, incontinence underwear, tampons, pet urine mats, garbage can liners, coffee filters, air filters, floor cleaning cloths, absorbent facial tissue, absorbent bathroom tissue, napkins, wrapping paper and / or other cardboard products such as cardboard boxes and paper for shopping bags. In some embodiments, the paper product may comprise cellulose cardboard sheets that optionally comprise predominantly cellulose fibers.In some embodiments, the cationic GPAM composition can decrease the drainage time of a treated sample compared to drainage time without the use of the cationic GPAM composition. For example, in some embodiments, cationic GPAM compositions can effect efficient drainage, such as OCC pulp drainage, demonstrating an improvement in... Petition 870240109898, dated 12 / 24 / 2024, page 30 / 182 18 / 56 Drainage time, for example, time to collect a given amount of filtrate from OCC pulp, of 25.0% or more, 30.0% or more, 35.0% or more, 40.0% or more, 45.0% or more, 50.0% or more, 55.0% or more compared to drainage without the use of a cationic GPAM composition. In some embodiments, the cationic GPAM composition can increase the drainage rate of a treated sample, resulting in an increased paper production rate compared to a drainage rate without the use of the cationic GPAM composition. In some embodiments, cationic GPAM compositions can improve the drying energy economy of the papermaking product.Furthermore, cationic GPAM compositions can affect a decrease in the total amount of solids present in a treated sample, for example, a decrease in the total solids present in a filtrate collected from OCC pulp treated with a cationic GPAM composition, for example, a decrease in the solids content of white water from the tray or silo after sheet formation, such as an improvement (decrease in solids content) of 15% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more, 27.5% or more, 30.0% or more, or 32.5% or more, compared to the total amount of solids present in a sample without the use of a cationic GPAM composition. In some embodiments, the cationic GPAM composition can improve drying energy savings.

[0019] Furthermore, the present invention generally relates to a method for preparing the cationic GPAM composition discussed in this document, particularly the cationic GPAM composition comprising a. a first base polymer with a weighted average molecular weight of less than 30,000 Da; and b. a second base polymer with a weighted average molecular weight of at least 30,000 Da; wherein the first base polymer and the second Petition 870240109898, dated 12 / 24 / 2024, page 31 / 182 19 / 56 base polymers have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, and optionally about 30:70 to about 70:30; wherein the first base polymer and the second base polymer are each glyoxalized; and wherein optionally the cationic GPAM composition requires a reduced volume of aqueous carrier for storage or transport compared with the volume of aqueous carrier required for conventional GPAMs used in papermaking. In some embodiments, the method may comprise a. glyoxalizing the first base polymer in a first glyoxalation reaction comprising glyoxal to produce a glyoxalized first base polymer; b.glyoxation of the second base polymer in a second glyoxation reaction comprising glyoxal to produce a second glyoxated base polymer, wherein optionally the first and / or second base polymer comprises or consists of acrylamide or methacrylamide and monomers charged with DADMAC or acryloyloxyethyltrimethylammonium chloride; and c. combination of the first glyoxated base polymer with the second glyoxated base polymer to produce the cationic GPAM composition; wherein steps (a) and (b) may be carried out in any order or simultaneously. In some embodiments, the method may comprise a. combination of the first base polymer with the second base polymer; and b. glyoxation of the combination of the first base polymer with the second base polymer in a glyoxation reaction comprising glyoxal to produce the cationic GPAM composition. In some embodiments, the method may comprise a.a. glyoxylation of the first base polymer in a glyoxylation reaction comprising glyoxal to produce a glyoxylated first base polymer; and b. addition of the second base polymer and, optionally, additional glyoxal to the glyoxylation reaction to produce the cationic GPAM composition. Petition 870240109898, dated 12 / 24 / 2024, page 32 / 182 20 / 56 In some embodiments, the method may comprise a. glyoxylation of the second base polymer in a glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and b. addition of the first base polymer and, optionally, additional glyoxal to the glyoxylation reaction to produce the cationic GPAM composition. In some embodiments, the method may comprise a. glyoxylation of the first base polymer in a first glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; and b. glyoxylation of the second base polymer in a second glyoxylation reaction comprising glyoxal and the first glyoxylated base polymer to produce the cationic GPAM composition. In some embodiments, the method may comprise a. glyoxylation of the second base polymer in a second glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and b.glyoxation of the first base polymer in a first glyoxation reaction comprising glyoxal and the second glyoxated base polymer to produce the cationic GPAM composition.

[0020] In addition, the present invention provides compositions of Cationic GPAMs produced by any of the methods mentioned above.

[0021] In addition, the present invention provides compositions comprising one or more cationic GPAM compositions produced by one or more of the methods mentioned above. DETAILED DESCRIPTION DEFINITIONS

[0022] As used in this document, the singular forms a / an and the / the include plural referents, unless the context clearly indicates otherwise. All technical and scientific terms used in this document have the same common meaning. Petition 870240109898, dated 12 / 24 / 2024, page 33 / 182 21 / 56 understood by a person skilled in the art to which the invention pertains, unless clearly stated otherwise.

[0023] As used in this document, unless otherwise specified, when we refer to a % in relation to a compound or composition, it means % by weight.

[0024] As used in this document, the term monomer generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers.

[0025] As used in this document, the terms polymer, polymers, polymeric and similar terms are used in their common sense as understood by those skilled in the art, and therefore may be used in this document to refer to or describe a large molecule (or group of such molecules) comprising recurring units. Polymers may be formed in various ways, including by the polymerization of monomers and / or by the chemical modification of one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer may comprise a homopolymer which may comprise substantially identical recurring units which may be formed by various methods, for example, by the polymerization of a specific monomer.Unless otherwise specified, a polymer may also comprise a copolymer comprising two or more different recurring units which may be formed, for example, by copolymerization, two or more different monomers and / or by chemical modification of one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer or copolymer may also comprise a terpolymer comprising polymers comprising three or more different recurring units. The term polymer, as used herein. Petition 870240109898, dated 12 / 24 / 2024, page 34 / 182 22 / 56 document, is intended to include both the acidic form of the polymer and its various salts. Polymers can be amphoteric in nature, that is, contain anionic and cationic substituents, although not necessarily in the same proportions.

[0026] As used in this document, the term nonionic monomer generally refers to a monomer that has a neutral charge.

[0027] As used in this document, the term anionic monomers may refer to anionic monomers that are substantially anionic in whole or (at equilibrium) in part, at a pH in the range of about 4.0 to about 9.0. Anionic monomers may be neutral at low pH (from a pH of about 2 to about 6), or they may be anionic monomers that are anionic at low pH. In some embodiments, anionic monomers, for example, vinyl monomers, may comprise, but are not limited to, those comprising a carboxylic acid functional group, a sulfonic acid functional group, a phosphonic acid functional group and their corresponding water-soluble salts and any combinations thereof.In some embodiments, anionic monomers may comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylamide methanesulfonic acid, acrylamide ethanesulfonic acid, 2-hydroxy-3-acrylamide propanesulfonic acid, styrenesulfonic acid, vinylphosphonic acid, and combinations thereof, as well as their corresponding water-soluble or water-dispersible alkali metal, alkaline earth metal, ammonium salts, and any combinations thereof. In some embodiments, the cationic GPAM composition may comprise base polymers that are optionally amphoteric, i.e., base polymers comprising cationic and anionic monomers. Petition 870240109898, dated 12 / 24 / 2024, page 35 / 182 23 / 56

[0028] As used in this document, the term cationic monomer generally refers to a monomer with a positive charge. Examples of cationic monomers may include, but are not limited to, those comprising acryloyloxyethyltrimethylammonium chloride (AETAC), methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidepropyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethylmethacrylate sulfate and / or diallyldimethylammonium chloride (DADMAC). The aforementioned cationic monomers may also comprise, but are not limited to, dialkylamino alkyl acrylates and methacrylates and their quaternary salts or acids, including, but not limited to, the quaternary salt of dimethylaminoethyl methyl acrylate chloride (DMAEA).methyl sulfate (MCQ), dimethylaminoethyl acrylate quaternary salt (DMAEM.MCQ), dimethylaminoethyl acrylate benzyl chloride quaternary salt (DMAEA.BCQ), dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate, methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate quaternary salt, methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dialkylaminoalkylaacrylamides or methacrylamides and their quaternary salts or acids, such as acrylamide propyltrimethylammonium chloride, dimethylaminopropyl quaternary salt. Petition 870240109898, dated 12 / 24 / 2024, page 36 / 182 24 / 56 acrylamide methyl sulfate, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, methacrylamide propyltrimethylammonium chloride, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethyl acrylate, diethylaminoethyl methacrylate halides and diallyldialkylammonium, such as diallyldiethylammonium chloride and diallyldimethylammonium chloride. Alkyl groups may generally comprise, but are not limited to, those comprising C1-8 alkyl groups. In some embodiments, cationic monomers may comprise quaternary ammonium or vinylamide acid salts, vinyl carboxylic acid, methacrylate and their derivatives.Cationic monomers can be combined, for example, to form a terpolymer of quaternary salt of methyl dimethylaminoethyl methacrylate chloride and diallyldimethyl ammonium chloride and acrylamide.

[0029] As used in this document, the term glyoxation percentage refers to the percentage of acrylamide-based monomers that are glyoxated into a polymer of the cationic GPAM composition, for example, the first base polymer and / or the second base polymer.

[0030] As used in this document, the term GPAM content refers to the sum of glyoxylated base polymers plus free glyoxal in the cationic GPAM composition.

[0031] As used in this document, the terms papermaking process and papermaking application generally refer to any process in which any form of paper and / or cardboard product can be produced. For example, such processes include producing paper products from pulp, such as methods comprising the formation of a papermaking supply. Petition 870240109898, dated 12 / 24 / 2024, page 37 / 182 25 / 56 aqueous cellulosic and drainage of the feedstock to form a sheet and dry the sheet. The papermaking feedstock formation, drainage, and drying steps can be performed in any conventional manner generally known in the art.

[0032] As used in this document, the terms polyacrylamide or PAM generally refer to polymers and copolymers comprising acrylamide fractions, and the terms encompass any polymers or copolymers comprising acrylamide fractions, for example, one or more acrylamide copolymers. In some cases, PAMs may comprise anionic PAMs (APAMs), cationic PAMs (CPAMs), and / or sulfonated PAMs (SPAMs). In some embodiments, a polyacrylamide may be a cationic polyacrylamide (cPAM).

[0033] As used in this document, the term glyoxalated polyacrylamide (GPAM) generally refers to a polymer obtained by the reaction of glyoxal and a polyacrylamide base polymer. Methods for producing glyoxalated polyacrylamides are known in the art (see, for example, U.S. Patent No. 3,556,932 which first disclosed the synthesis of a GPAM composition prepared by the reaction of glyoxal with a cationic polyacrylamide). In some cases, the GPAM polyacrylamide backbone may incorporate a small amount of a cationic monomer, making the polymer self-retaining in fibers. In general, GPAM comprises a reactive polymer that can covalently bind to cellulose after dehydration.

[0034] The present invention provides cationic GPAM compositions with specific properties that are well suited for use in papermaking processes, i.e., for use as additives to increase the wet and / or dry strength of paper; and which have improved storage and transport properties, for example, unlike conventional GPAMs used in papermaking processes, the cationic GPAMs in question can be Petition 870240109898, dated 12 / 24 / 2024, page 38 / 182 26 / 56 stored and transported without the need to add large volumes of aqueous vehicles, which is undesirable and expensive, as this usually requires large-volume containers or tankers for transport. In some cases, the aqueous vehicle may comprise water. In some cases, the volume of aqueous vehicle used during the transport of the cationic GPAMs discussed in this document may be less than that used to transport a conventional GPAM. For example, in some cases, conventional GPAMs may comprise a solids percentage of 4% or less, while in some embodiments the cationic GPAM compositions may comprise a solids percentage greater than 4%, i.e., from more than 4% to about 11%, for example, from about 4% to about 9%, from about 5% to about 8%, or from about 6% to about 7.5%.

[0035] As used in this document, the terms cationic GPAM or cationic GPAM composition generally refers to a GPAM composition comprising a first base polymer having a weighted average molecular weight of less than 30,000 Da and a second base polymer having a weighted average molecular weight of at least 30,000 Da, wherein the first base polymer and the second base polymer have a weight ratio of about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, optionally from about 30:70 to about 70:30, wherein the first base polymer and the second base polymer are each glyoxalated, and wherein optionally the cationic GPAM composition requires a reduced volume of an aqueous carrier for storage or transport compared with a volume of an aqueous carrier required for conventional GPAMs used in the manufacture of paper.In some embodiments, the weighted average molecular weight of the first base polymer may be a maximum of 25 kDa or less, 20 kDa or less, 15 kDa or less, 10 kDa or less, or 8 kDa. Petition 870240109898, dated 12 / 24 / 2024, p. 39 / 182 27 / 56 or less. In some embodiments, the weighted average molecular weight of the second base polymer may be at least 30 kDa or more, 40 kDa or more, 50 kDa or more, 75 kDa or more, 100 kDa or more, 125 kDa or more, 150 kDa or more, 175 kDa or more, 200 kDa or more, 225 kDa or more, 250 kDa or more, 275 kDa or more, 300 kDa or more, 325 kDa or more, 350 kDa or more, 375 kDa or more, 400 kDa or more, or 500 kDa or more. In some embodiments, the glyoxylation percentage of the cationic GPAM composition can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the glyoxylation percentage of the first base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%.In some embodiments, the glyoxylation percentage of the second base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the GPAM content of the cationic GPAM composition can be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. In some embodiments, the GPAM content of the first base polymer can be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%.In some embodiments, the GPAM content of the second base polymer may be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. Petition 870240109898, dated 12 / 24 / 2024, p. 40 / 182 28 / 56 In some embodiments, the first base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight or at least 60% by weight, wherein optionally the first base polymer is amphoteric. In some embodiments, the second base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the second base polymer is amphoteric.In some embodiments, the first base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the first base polymer may be amphoteric. In some embodiments, the second base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the second base polymer may be amphoteric.In some embodiments, the composition of cationic GPAM may comprise a weight percentage of solids of about 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0% or more, 5.5% or more, 6.0% or more, 6.5% or more, 7.0% or more, 7.5% or more, 8.0% or more, 8.5% or more, 9.0%. Petition 870240109898, dated 12 / 24 / 2024, page 41 / 182 29 / 56 or more, 9.5% or more, 10.0% or more, 10.5% or more, 11.0% or more, or 11.5% or more. In some embodiments, the composition of cationic GPAM may comprise a weight percentage of solids of about 1.0% to about 20.0%, optionally from about 3.0% to about 15%. In some embodiments, the cationic GPAM composition may comprise a weight ratio between glyoxal and the total base polymer of at least about 1:99, at least about 2.5:97.5, at least about 5:95, at least about 7.5:92.5, at least about 10:90, at least about 12.5:87.5, at least about 15:85, at least about 17.5:82.5, at least about 20:80, at least about 22.5:77.5, at least about 25:75, at least about 27.5:72.5, at least about 29:71, or at least about 30:70. In some embodiments, the first base polymer may comprise an acrylamide-based polymer.In some embodiments, the second base polymer may comprise an acrylamide-based polymer. In some embodiments, the first base polymer may comprise one or more cationic monomers. In some embodiments, the second base polymer may comprise one or more cationic monomers. In some embodiments, the first base polymer may comprise a weight ratio of cationic monomer / acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and also optionally from about 25:75 to about 50:50. In some embodiments, the second base polymer may comprise a weight ratio of cationic monomer to acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and still optionally from about 25:75 to about 50:50. In some embodiments, the first base polymer is amphoteric and comprises more cationic monomers than anionic monomers.In some embodiments, the second base polymer is amphoteric and comprises... Petition 870240109898, dated 12 / 24 / 2024, page 42 / 182 30 / 56 more cationic monomers than anionic monomers. In some embodiments, the first base polymer may comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers. In some embodiments, the second base polymer may comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers. In some embodiments, the one or more cationic monomers may comprise DADMAC and / or may comprise acryloyloxyethyltrimethylammonium chloride (also known as Q9). In some embodiments, the main structure polymer may comprise an acrylamide-based polymer, wherein the acrylamide monomer is replaced by other primary amide-containing monomers, such as methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, or N-ethyl methacrylamide, or any combination thereof. In some embodiments, the main structure polymer may comprise acrylamide monomers.In some embodiments, the viscosity of the cationic GPAM composition may be about 10 cPs or more, about 15 cPs or more, about 20 cPs or more, about 25 cPs or more, about 30 cPs or more, or about 35 cPs or more, for example, as measured by a Brookfield LV viscometer at 25 °C and 600 rpm using spindle number 1. The cationic GPAM compositions described in this document may be used in any papermaking process as described in this document. Furthermore, the cationic GPAM compositions described in this document possess properties that should reduce transportation and manufacturing costs, thus providing benefits to manufacturers and end users of the cationic GPAM compositions.

[0036] As used in this document, the term white water generally refers to process water and / or produced water that may be removed from the pulp supply during product formation. Petition 870240109898, dated 12 / 24 / 2024, page 43 / 182 31 / 56 of paper, such as a sheet, for example, a sheet of paper. COMPOSITIONS AND METHODS Cationic GPAM compositions

[0037] GPAM compositions have known use in the paper industry, typically as wet and / or dry strengthening agents. However, conventional GPAMs generally need to be stored and transported in a bulk aqueous carrier fluid in large volumes, which often requires large-volume containers or tank vessels for transport. Shipping such large volumes of product significantly increases costs for those transporting and using GPAM compositions. As such, there is a need for improved GPAM compositions, such as those comprising cationic GPAMs, which, based on their composition, are useful in papermaking processes and possess storage properties that should result in reduced transportation costs.

[0038] To this end, the present invention generally relates to improved glyoxylated polyacrylamide (GPAM) compositions suitable for use as a dry and / or wet strengthening agent, wherein said cationic GPAM compositions comprise a first base polymer having a weighted average molecular weight of less than 30,000 Da and a second base polymer having a weighted average molecular weight of at least 30,000 Da, wherein the first base polymer and the second base polymer have a weight ratio of about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, or even optionally from about 30:70 to about 70:30, wherein the first base polymer and the second base polymer are each glyoxylated, such compositions being useful in papermaking processes and possessing improved storage properties which should result in transportation costs Petition 870240109898, dated 12 / 24 / 2024, page 44 / 182 32 / 56 reduced, still optionally where the cationic GPAM composition requires a reduced volume of aqueous carrier for storage or transport compared to the volume of aqueous carrier required for conventional GPAMs used in papermaking. For example, the volume of aqueous carrier used during the transport of the cationic GPAM compositions discussed in this document may be less than that used to transport a conventional GPAM. For example, in some cases, conventional GPAMs may comprise a solids percentage of 4% or less, while in some embodiments the cationic GPAM compositions may comprise a solids percentage greater than 4%, i.e., from more than 4% to about 11%, for example, from about 5% to about 9%, for example, from about 5% to about 8% or from about 6% to about 7.5%.

[0039] In some embodiments, the cationic GPAM composition may comprise a first base polymer with a weighted average molecular weight of at most 25 kDa or less, 20 kDa or less, 15 kDa or less, 10 kDa or less or 8 kDa or less. In some embodiments, the cationic GPAM may comprise a second base polymer with a weighted average molecular weight of at least 30 kDa or more, 40 kDa or more, 50 kDa or more, 75 kDa or more, 100 kDa or more, 125 kDa or more, 150 kDa or more, 175 kDa or more, 200 kDa or more, 225 kDa or more, 250 kDa or more, 275 kDa or more, 300 kDa or more, 325 kDa or more, 350 kDa or more, 375 kDa or more, 400 kDa or more, or 500 kDa or more.

[0040] In some embodiments, the glyoxylation percentage of the cationic GPAM composition may be from about 2% to about 90%, optionally from about 3% to about 80%, still optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the percentage Petition 870240109898, dated 12 / 24 / 2024, p. 45 / 182 The glyoxylation percentage of the first base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%. In some embodiments, the glyoxylation percentage of the second base polymer can be from about 2% to about 90%, optionally from about 3% to about 80%, also optionally from about 4% to about 70%, and still optionally from about 5% to about 60%.

[0041] In some embodiments, the weighted average molecular weight of the first base polymer varies from no more than 2 to 25 kDa, 5-20 kDa or 5-15 kDa.

[0042] In some embodiments, the weighted average molecular weight of the second base polymer ranges from at least 100 kDa to 500 kDa, 150-400 kDa, 200-300 kDa, 225 kDa to 275 kDa or is about 250 kDa.

[0043] In some embodiments, the first and second base polymers comprise copolymers of a first monomer comprising acrylamide or methacrylamide and a second monomer comprising DADMAC (dimethyldiallylammonium chloride) or Q9, optionally wherein the first monomer comprises acrylamide and the second monomer comprises DADMAC, wherein the percent ratio of the first and second monomer varies from about 30:70 to about 70:30.

[0044] In some embodiments, both the first and second base polymers comprise copolymers of a first monomer comprising acrylamide or methacrylamide and a second monomer comprising DADMAC (dimethyldiallylammonium chloride) or Q9, optionally wherein the first monomer comprises acrylamide and the second monomer comprises DADMAC, wherein the percent ratio of the first and second monomer varies from about 40:60 to about Petition 870240109898, dated 12 / 24 / 2024, page 46 / 182 34 / 56 60:40 or approximately 40:60.

[0045] In some embodiments of the glyoxation reaction used to produce the first and second glyoxal base polymer, the glyoxal base polymer ratio varies from 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, or comprises about 30:70.

[0046] In some embodiments, the ratio between the first and second base polymer varies from 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0047] In some embodiments, both the first and second base polymers comprise acrylamide and DADMAC (dimethyldiallylammonium chloride) copolymers, the percentage ratio of acrylamide and DADMAC monomers in these ranging from about 40:60 to about 60:40; and the ratio between the first and second base polymer in the strengthening agent ranging from 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40.

[0048] In some embodiments, both the first and second base polymers comprise acrylamide and DADMAC copolymers, the weighted average molecular weight of the first base polymer ranging from no more than 2 to 25 kDa, 5-20 kDa or 5-15 kDa; the weighted average molecular weight of the second base polymer ranging from at least 100 kDa to 500 kDa, 150-400 kDa, 200-300 kDa, 225 kDa to 275 kDa or is about 250 kDa; and the ratio between the first and second base polymers ranging from 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40.

[0049] In some embodiments, the GPAM content of the composition of Cationic GPAM can be from about 2% to about 20%, optionally from about 3% to about 10%, also optionally from about 4% to about 8%, and still optionally from about 5% to about 7%. In some embodiments, the GPAM content of the first base polymer can be from about 2% to about 20%, optionally from about 3% to about 10%, and still optionally from about 4% to about 8%. Petition 870240109898, dated 12 / 24 / 2024, p. 47 / 182 35 / 56 optionally from about 5% to about 7%. In some embodiments, the GPAM content of the second base polymer may be from about 2% to about 20%, optionally from about 3% to about 10%, optionally from about 4% to about 8%, and optionally from about 5% to about 7%.

[0050] In some embodiments, the first base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight or at least 60% by weight, wherein optionally the first base polymer is amphoteric. In some embodiments, the second base polymer may comprise a cationic filler of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the second base polymer is amphoteric.

[0051] In some embodiments, the first base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or at least 60% by weight, wherein optionally the first base polymer may be amphoteric. In some embodiments, the second base polymer may comprise a cationic monomer percentage of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight, or Petition 870240109898, dated 12 / 24 / 2024, page 48 / 182 36 / 56 at least 60% by weight, wherein optionally the second base polymer may be amphoteric.

[0052] In some embodiments, the composition of cationic GPAM may comprise a weight percentage of solids of about 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0% or more, 5.5% or more, 6.0% or more, 6.5% or more, 7.0% or more, 7.5% or more, 8.0% or more, 8.5% or more, 9.0% or more, 9.5% or more, 10.0% or more, 10.5% or more, 11.0% or more, or 11.5% or more. In some embodiments, the composition of cationic GPAM may comprise a weight percentage of solids of about 1.0% to about 20.0%, optionally from about 3.0% to about 15%.

[0053] In some embodiments, the cationic GPAM composition may comprise a weight ratio between glyoxal and the total base polymer of at least about 1:99, at least about 2.5:97.5, at least about 5:95, at least about 7.5:92.5, at least about 10:90, at least about 12.5:87.5, at least about 15:85, at least about 17.5:82.5, at least about 20:80, at least about 22.5:77.5, at least about 25:75, at least about 27.5:72.5, at least about 29:71 or at least about 30:70.

[0054] In some embodiments, the first base polymer may comprise an acrylamide-based polymer. In some embodiments, the second base polymer may comprise an acrylamide-based polymer. In some embodiments, the first base polymer may comprise one or more cationic monomers. In some embodiments, the second base polymer may comprise one or more cationic monomers.Those skilled in the art will be able to easily determine an appropriate cationic monomer / acrylamide weight ratio for the first base polymer and / or the second base polymer. For example, in some embodiments, the first base polymer may comprise a ratio. Petition 870240109898, dated 12 / 24 / 2024, page 49 / 182 37 / 56 weight ratio between cationic monomer / acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and also optionally from about 25:75 to about 50:50. For example, in some embodiments, the second base polymer may comprise a weight ratio between cationic monomer / acrylamide of about 15:85 to about 60:40, optionally from about 20:80 to about 55:45, and also optionally from about 25:75 to about 50:50. In some embodiments, the first base polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the second base polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the first base polymer may comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers.In some embodiments, the second base polymer may comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers.

[0055] In some embodiments, the viscosity of the composition of Cationic GPAM can be around 10 cPs or more, around 15 cPs or more, around 20 cPs or more, around 25 cPs or more, around 30 cPs or more, or around 35 cPs or more, for example, as measured by an LV Brookfield viscometer at 25 °C and 600 rpm using spindle number 1.

[0056] In some embodiments, the cationic monomer of the first and second base polymers of the cationic GPAM composition may comprise any one or more of the cationic monomers described in this document. In some embodiments, one or more cationic monomers may each be selected from the group consisting of acryloyloxyethyltrimethylammonium chloride (AETAC), methacryloyloxyethyltrimethylammonium chloride, methacrylamidepropyltrimethylammonium chloride (MAPTAC), chloride of Petition 870240109898, dated 12 / 24 / 2024, page 50 / 182 38 / 56 acrylamide propyltrimethylammonium, methacryloyloxyethyldimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, diallyldimethylammonium chloride (DADMAC); dialkylaminoalkyl acrylates and methacrylates and their quaternary salts or acids, including, but not limited to, quaternary salt of dimethylaminoethyl methyl acrylate chloride (DMAEA.MCQ), quaternary salt of dimethylaminoethyl acrylate methyl sulfate (DMAEM.MCQ), quaternary salt of dimethylaminoethyl benzyl chloride acrylate (DMAEA.(BCQ), dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate, methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate quaternary salt, methyl sulfate, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt. dialkylaminoalkylacrylamides or methacrylamides and their quaternary salts or acids, such as acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropylacrylamide, hydrochloric acid salt of dimethylaminopropylacrylamide, chloride of methacrylamidopropyltrimethylammonium, quaternary salt of dimethylaminopropyl methacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropyl methacrylamide, hydrochloric acid salt of dimethylaminopropyl methacrylamide, diethylaminoethylacrylate, diethylaminoethyl methacrylate halides and diallyldialkylammonium, such as diallyldiethylammonium chloride and diallyldimethylammonium chloride. In some embodiments, one or more cationic monomers may comprise Petition 870240109898, dated 12 / 24 / 2024, page 51 / 182 39 / 56 DADMAC. In some embodiments, one or more cationic monomers may comprise acryloyloxyethyltrimethylammonium chloride (Q9). In some embodiments, one or more cationic monomers may each comprise DADMAC and / or acryloyloxyethyltrimethylammonium chloride (Q9). In some embodiments, one or more cationic monomers may each be selected from the group consisting of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (Q9), 3-(methacrylamide)propyltrimethyltrimethylammonium chloride, 3-(acryloylamide)propyltrimethyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylammonioethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl methacrylate and dimethylaminopropyl acrylamide, dimethylaminopropylmethacrylamide.

[0057] In some embodiments, the acrylamide-based polymer of the first and second base polymers may each comprise one or more primary amide-containing monomers. In some embodiments, the acrylamide-based polymer may comprise one or more monomers selected from the group consisting of acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof. In some embodiments, the acrylamide-based polymer may comprise one or more acrylamide monomers.

[0058] The properties of such cationic GPAM compositions, such as cationic charge, percentage of cationic monomer, percentage of solids, GPAM content, and / or percentage of glyoxylation, compared to conventional GPAMs, demonstrate desirable and effective end-use performance, and the properties of the cationic GPAMs disclosed and exemplified in this document should translate into enormous reductions in the volumes of products that need to be transported and handled, such as, for example, where Petition 870240109898, dated 12 / 24 / 2024, page 52 / 182 40 / 56 shipments of rail vehicles or tank trucks and the like are involved, and therefore significant savings in costs and handling can be achieved by using the cationic GPAMs in question.

[0059] In some embodiments, the cationic polyacrylamide of Cationic GPAM, that is, of the first base polymer and / or the second base polymer, may comprise a cationic acrylamide or methacrylamide copolymer (cPAM). In some embodiments, the cPAM may comprise a cationic acrylamide or methacrylamide copolymer that may be produced by copolymerizing acrylamide or methacrylamide with one or more cationic monomers. In some embodiments, said one or more cationic monomers may comprise any one or more of the cationic monomers discussed in this document.In some embodiments, the aforementioned one or more cationic monomers may include, but are not limited to, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (Q9), 3-(methacrylamide)propyltrimethylammonium chloride, 3-(acryloylamido)propyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, and similar monomers.In some embodiments, cationic GPAM may comprise a cationic monomer comprising any one or more of 2-vinylpyridine, 2-vinyl-N-methylpyridine chloride, (p-vinylphenyl)trimethylammonium chloride, diallyldimethylammonium chloride, 2-(dimethylamino)ethyl acrylate, trimethyl p-(vinylbenzyl)ammonium chloride, p-dimethylaminoethylstyrene, dimethylaminopropyl acrylamide, 2-methylacroyloxyethyltrimethylammonium methylsulfate, or 3-acrylamide-3-methylbutyl trimethylammonium chloride, or any combination thereof. In some embodiments, cPAM may comprise a copolymer of acrylamide or methacrylamide and DADMAC. In some embodiments, cPAM may comprise a... Petition 870240109898, dated 12 / 24 / 2024, page 53 / 182 41 / 56 acrylamide or methacrylamide copolymer and Q9. In some embodiments, a cPAM may comprise one or more cationic monomers, such as those discussed in this document, a net cationic filler, and an acrylamide or methacrylamide backbone. In some embodiments, a cPAM may comprise an acrylamide or methacrylamide-based polymer that is treated after polymerization to make it cationic, for example, using Hofmann or Mannich reactions. In some embodiments, a cPAM may comprise a cationic acrylamide or methacrylamide copolymer that can be prepared by conventional radical initiation polymerization methods.

[0060] In some embodiments, the main structure polymer, for example, the main structure of the first base polymer and / or the main structure of the second base polymer, may comprise an acrylamide-based polymer, wherein the acrylamide monomer is replaced by other primary amide-containing monomers, such as methacrylamide, ethyl acrylamide, crotonamide, N-methylacrylamide, N-butyl-a, or any combination thereof. In some embodiments, the main structure polymer may comprise acrylamide monomers.In some embodiments, one or more cationic monomers may be selected from the group consisting of acryloyloxyethyltrimethylammonium chloride (AETAC), methacryloyloxyethyltrimethylammonium chloride, methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropylmethacrylamide, methacryloyloxyethyltrimethylammonium chloride, dimethylaminoethylmethacrylate sulfate, diallyldimethylammonium chloride (DADMAC); dialkylaminoalkyl acrylates and methacrylates and their quaternary salts or acids, including, but not limited to, quaternary salt of methyl acrylate chloride. Petition 870240109898, dated 12 / 24 / 2024, page 54 / 182 42 / 56 dimethylaminoethyl (DMAEA.MCQ), quaternary salt of dimethylaminoethyl acrylate methyl sulfate (DMAEM.MCQ), quaternary salt of benzyl chloride of dimethylaminoethyl acrylate (DMAEA.BCQ), sulfuric acid salt of dimethylaminoethyl acrylate, hydrochloric acid salt of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of methyl chloride of dimethylaminoethyl methacrylate, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of benzyl chloride of dimethylaminoethyl methacrylate, sulfuric acid salt of dimethylaminoethyl methacrylate, hydrochloric acid salt of dimethylaminoethyl methacrylate, hydrochloric acid salt of dimethylaminoethyl methacrylate, dialkylaminoalkylacrylamides or methacrylamides and their quaternary salts or acids, such as acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropylacrylamide, hydrochloric acid salt of dimethylaminopropylacrylamide, chloride of methacrylamide propyltrimethylammonium, quaternary salt of dimethylaminopropyl methacrylamide methyl sulfate, sulfuric acid salt of dimethylaminopropyl methacrylamide, hydrochloric acid salt of dimethylaminopropyl methacrylamide, diethylaminoethyl acrylate, diethylaminoethyl methacrylate halides and diallyldialkylammonium, such as diallyldiethylammonium chloride and diallyldimethylammonium chloride. In exemplary embodiments, the first or second base polymers comprise or consist of (i) a first monomer comprising acrylamide and / or methacrylamide; and (ii) a second monomer comprising DADMAC or Q9 monomers, wherein, optionally, the percent ratio of the first and second monomers varies from about 30:70 to about 70:30 or 40:60 to about 60:40. Methods of Using Cationic GPAM Compositions Petition 870240109898, dated 12 / 24 / 2024, page 55 / 182 43 / 56

[0061] Based on the foregoing, the present invention also relates generally to a method of papermaking, wherein said method comprises adding one or more cationic GPAM compositions as previously described, which, based on their composition, are useful in papermaking processes and which, moreover, possess storage properties that should result in reduced transportation costs; wherein the method generally comprises adding one or more such cationic GPAM compositions during a papermaking method in an amount effective to increase the wet and / or dry strength of the paper. In some embodiments, one or more cationic GPAM compositions are added to a composition comprising fiber and / or pulp used in the method before the paper product is formed.In some embodiments, one or more cationic GPAM compositions are added to one or more surfaces of the paper product after the paper product has been formed. In some embodiments, the cationic GPAM composition may comprise any one or more of the cationic GPAM compositions disclosed in this document. In some embodiments, the cationic GPAM composition may comprise a first base polymer with a weighted average molecular weight of less than 30,000 Da, and a second base polymer with a weighted average molecular weight of at least 30 Da.000 Da, optionally wherein the first base polymer and the second base polymer comprise or consist of (i) a first monomer comprising acrylamide and / or methacrylamide; and (ii) a second monomer comprising DADMAC or Q9 monomers, further optionally wherein the first base polymer and the second base polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, further optionally about 30:70 to about 70:30 or about 40:60 to about . Petition 870240109898, dated 12 / 24 / 2024, page 56 / 182 44 / 56 60:40, wherein the first base polymer and the second base polymer are each glyoxated.

[0062] In some embodiments, the cationic GPAM compositions described in this document provide thermosetting resins that are particularly suitable for use as additives in papermaking methods, i.e., where the addition of said cationic GPAM compositions results in papers with desirable temporary dry and wet strength and / or increases the water removal rate of papermaking.

[0063] Furthermore, the present invention also relates to paper products comprising one or more improved GPAM compositions, as disclosed in this document. In some embodiments, the paper product may comprise at least one layer of paper or web containing the cationic GPAM composition, for example, paperboard, cardboard, thin paper and wallpaper. In some embodiments, the paper product comprises the cationic GPAM composition on at least one surface of the paper product. The cationic GPAM composition is not limited to use in any specific type of paper or papermaking method and should be applied to kraft paper, sulfite paper, semi-chemical paper and the like, including paper produced using bleached pulp, unbleached pulp or combinations thereof.

[0064] When using a cationic GPAM composition as disclosed in this document during a papermaking method, the cationic GPAM composition may be added at any time before, during, and / or after paper forming. In some cases, the cationic GPAM composition may be added at the wet end of a papermaking facility to cellulose fiber suspensions, typically at a point where moisture-resistant resins are conventionally added. In Petition 870240109898, dated 12 / 24 / 2024, page 57 / 182 45 / 56 In some embodiments, the cationic GPAM composition can be added to a previously prepared paper, for example, to one or more surfaces of a previously prepared paper, by padding, spraying, dipping and / or printing and the like. Furthermore, in some embodiments, the cationic GPAM composition can be added to the paper pulp over a wide range of pH values, such as from about 4 to about 9.

[0065] In some cases, the amount of cationic GPAM composition added during a papermaking method may vary from about 0.02% by dry weight to about 10% by dry weight of the cellulose fibers, for example, in the range of about 0.05% by weight to 5% by weight of the dry paper weight.

[0066] In addition, the present invention generally relates to a paper product, for example, a hand sheet, comprising one or more cationic GPAMs, for example, cationic GPAMs as described above, which, based on their composition, are useful in papermaking processes and which optionally possess storage properties that should result in reduced transportation costs.In some embodiments, the paper product may comprise fiber-based products, for example, hand sheets, paperboard-type products, beverage carriers, towels, milk and juice cartons, food trays, paper bags, lining board for corrugated cardboard containers, paperboard-type packaging, paper materials, paper towels, diapers, sanitary napkins, baby potty pants, panty liners, incontinence underwear, tampons, pet urine mats, garbage can liners, coffee filters, air filters, floor cleaning cloths, absorbent facial tissue, absorbent bathroom tissue, napkins, wrapping paper and / or other cardboard products such as cardboard boxes and paper for shopping bags. In some. Petition 870240109898, dated 12 / 24 / 2024, page 58 / 182 46 / 56 modalities, the paper product may comprise cellulose cardboard sheets comprising: (a) (b) predominantly cellulose fibers and one or more cationic GPAM compositions.

[0067] In some embodiments, the paper product may comprise improved paper strength, for example, as determined by STFI tests, compared with a paper product that does not comprise a cationic GPAM composition. For example, in some embodiments, the paper product may comprise a handsheet comprising one or more cationic GPAM compositions, wherein said handsheet may comprise an STFI value improvement of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more at 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton or 10 lbs / ton test compared with a pure sample used for the STFI test.

[0068] In some embodiments, the paper product may comprise improved paper strength, for example, as determined by explosion resistance testing, compared to a paper product that does not comprise a cationic GPAM composition. For example, in some embodiments, a handsheet comprising one or more cationic GPAM compositions may comprise an improvement in the burst resistance value of 6% or more, 7% or more, 8% or more, 9% or more, 10% or more, 12.5% ​​or more, 15.0% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more, 27.5% or more, 30.0% or more, 32.5% or more, 35.0% or more, 37.5% or more, or 40% or more in 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to the pure sample used for the burst resistance test.

[0069] In some modalities, the GPAM compositions Petition 870240109898, dated 12 / 24 / 2024, page 59 / 182 47 / 56 Cationic compositions can decrease the drainage time of a treated sample compared to drainage time without the use of the cationic GPAM composition. For example, in some embodiments, cationic GPAM compositions can effect efficient drainage, for example, drainage of OCC pulp, such as demonstrating an improvement in drainage time, for example, time to collect a given amount of filtrate from OCC pulp, of 25.0% or more, 30.0% or more, 35.0% or more, 40.0% or more, 45.0% or more, 50.0% or more, 55.0% or more compared to drainage without the use of a cationic GPAM composition. In some embodiments, the cationic GPAM composition increases the drainage rate of a treated sample resulting in an increased paper production rate compared to drainage rate without the use of the cationic GPAM composition. In some applications, the composition of cationic GPAM improves the energy efficiency of the papermaking drying process.Furthermore, cationic GPAM compositions can affect a decrease in the total amount of solids present in a treated sample, for example, a decrease in the total solids present in a filtrate collected from OCC pulp treated with a cationic GPAM composition, for example, a decrease in the solids content of white water from the tray or silo after sheet formation, such as an improvement (decrease in solids content) of 15% or more, 17.5% or more, 20.0% or more, 22.5% or more, 25.0% or more, 27.5% or more, 30.0% or more, or 32.5% or more, compared to the total amount of solids present in a sample without the use of a cationic GPAM composition. In some embodiments, the cationic GPAM composition can improve drying energy savings.

[0070] In addition, the present invention generally relates to a method of manufacturing a hand sheet, said method Petition 870240109898, dated 12 / 24 / 2024, page 60 / 182 48 / 56 comprising: a. providing a pulp stock; b. diluting the pulp stock; c. adding one or more salts to a desired level of conductivity; d. adjusting the pH to a desired value; e. adding one or more cationic GPAM compositions; f. adding the treated pulp to a dynamic sheet former; g. pressing the sheets resulting from f.; h. drying the sheets; and i. conditioning the sheets.

[0071] In addition, the present invention generally relates to a method of producing one or more paper products, wherein said method comprises: a. providing a composition comprising predominantly cellulose fibers; b. adding a predetermined amount of one or more cationic GPAM compositions; and c. forming the desired paper product.

[0072] In addition, the present invention generally encompasses a method of manufacturing one or more paper products, for example, one or more absorbent paper products, wherein said method comprises: (a) . provide a composition comprising any softwood fiber, hardwood fiber, recycled fiber, refined fiber or a mixture of any of the foregoing in a quantity sufficient to form a general supply of approximately 1 to 100% hardwood fiber, softwood fiber, recycled fiber, refined fiber or a mixture of any of the foregoing; (b) adding a predetermined amount of one or more cationic GPAM compositions, as discussed in this document; and (c) forming a paper product by drying through one or more drying means to a desired moisture content level.

[0073] In addition, the present invention generally relates to a method for strengthening paper, comprising (i) bringing pulp fibers into contact with a resin Petition 870240109898, dated 12 / 24 / 2024, page 61 / 182 49 / 56 strengthening resin comprising at least one cationic GPAM composition, for example, at least one of the improved cationic GPAM compositions disclosed in this document, such GPAM compositions possessing specific attributes that make them well suited for use in papermaking processes, and (ii) at least partially curing the strengthening resin comprising at least one cationic GPAM composition in the pulp fiber and cationic GPAM composition mixture to produce a paper product with increased strength. Methods for Preparing Cationic GPAM Compositions

[0074] The present invention also generally relates to a method for preparing the cationic GPAM compositions disclosed in this document, particularly the cationic GPAM composition comprising a first base polymer with a weighted average molecular weight of less than 30,000 Da, optionally from 2 to 25 kDa, or 5 to 15 kDa and a second base polymer with a weighted average molecular weight of at least 30.000 Da; optionally, a weighted average molecular weight of at least 50 kDa or a weighted average molecular weight ranging from 100 kDa to 500 kDa, 150-400 kDa, 200-300 kDa, 225 kDa to 275 kDa or about 250 kDa; also optionally wherein the first base polymer and / or the second base polymer comprise (i) acrylamide or methacrylamide monomers and (ii) DADMAC or Q9 monomers, wherein the first base polymer and the second base polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, also optionally about 30:70 to about 70:30 or about 40:60 to about 60:40; wherein the first base polymer and the second base polymer are each glyoxalated; and wherein the cationic GPAM composition optionally requires a reduced volume of aqueous carrier for storage or transport compared to. Petition 870240109898, dated 12 / 24 / 2024, page 62 / 182 50 / 56 a volume of an aqueous vehicle required for conventional GPAMs used in paper manufacturing.

[0075] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. glyoxylation of the first base polymer in a first glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; b. glyoxylation of the second base polymer in a second glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and c. combining the first glyoxylated base polymer with the second glyoxylated base polymer to produce the cationic GPAM composition; wherein steps (a) and (b) may be carried out in any order or simultaneously.

[0076] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. combining the first base polymer with the second base polymer; and b. glyoxylation of the combination of the first base polymer with the second base polymer in a glyoxation reaction comprising glyoxal to produce the cationic GPAM composition.

[0077] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. glyoxylation of the first base polymer in a glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; and b. addition of the second base polymer and, optionally, additional glyoxal to the glyoxylation reaction to produce the cationic GPAM composition.

[0078] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. glyoxylation of the second base polymer in a Petition 870240109898, dated 12 / 24 / 2024, page 63 / 182 51 / 56 glyoxation reaction comprising glyoxal to produce a second glyoxalated base polymer; and b. addition of the first base polymer and, optionally, additional glyoxal to the glyoxation reaction to produce the cationic GPAM composition.

[0079] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. glyoxylation of the first base polymer in a first glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; and b. glyoxylation of the second base polymer in a second glyoxylation reaction comprising glyoxal and the first glyoxylated base polymer to produce the cationic GPAM composition.

[0080] In some embodiments, the method for preparing a cationic GPAM composition disclosed in this document may comprise: a. glyoxylation of the second base polymer in a second glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and b. glyoxylation of the first base polymer in a first glyoxylation reaction comprising glyoxal and the second glyoxylated base polymer to produce the cationic GPAM composition.

[0081] The compositions and methods illustrated in this document may be appropriately applied in the absence of any element not specifically disclosed in this document and / or any element specifically disclosed in this document. EXAMPLES Example 1: Sample Preparation and Handsheets

[0082] The cationic GPAM compositions and hand sheets used in the following examples were prepared as follows. All GPAM samples were prepared by reacting glyoxal with the cationic polyacrylamide base polymers shown in Table 1. Petition 870240109898, dated 12 / 24 / 2024, page 64 / 182 52 / 56 TABLE 1 - BASE POLYMER COMPOSITIONS Samples Base polymer MW (kilodalton) % of base polymer filler (% by weight) Base polymer 1* 8 40% Base polymer 2 15 10% Base polymer 3 246 40% Each of the base polymers 1, 2, and 3 are copolymers consisting of acrylamide and DADMAC (dimethyldiallylammonium chloride) monomers.

[0083] Cationic copolymers comprising acrylamide and DADMAC monomers were used in the examples in this document because such copolymers are widely used as a model cationic polymer. In this sense, it is reasonably expected that the results obtained using these copolymers will be obtained with other cationic polymers, such as cationic copolymers comprising other cationic monomers that are disclosed in this document.

[0084] The compositions of the GPAM samples prepared by the reaction of glyoxal with the base polymers in Table 1 are described in Table 2. For each reaction, the glyoxal:base polymer ratio was 29:71. TABLE 2 - GPAM SAMPLE COMPOSITIONS Samples Preparation Method Solids GPAM 1 Glyoxylation of base polymer 1. 14% GPAM 2 Glyoxylation of base polymer 3. 5% GPAM 3 Glyoxylation of a 20:80 mixture of base polymer 1: base polymer 3. 6.1% GPAM 4 Glyoxylation of a 30:70 mixture of base polymer 1: base polymer 3. 7.3% GPAM 5 A 25:75 mixture of GPAM 1:GPAM 2. 6.0% GPAM 6 A 33:67 mixture of GPAM 1:GPAM 2. 6.4% GPAM 7 Base polymer 3 carried out with glyoxylation reaction in the presence of GPAM 1. Base polymer ratio 6.0% Petition 870240109898, dated 12 / 24 / 2024, page 65 / 182 53 / 56 1: Base polymer 3 was 25:75. GPAM 8 Glyoxylation of base polymer 2. 7.0% GPAM 9 Glyoxylation of a 25:75 mixture of base polymer 2: base polymer 3. 7.0% GPAM 10 Glyoxylation of a 40:60 mixture of base polymer 2: base polymer 3. 6.7% GPAM 11 Glyoxylation of a 60:40 mixture of base polymer 2: base polymer 3. 7.2%

[0085] GPAM 1, GPAM 2 and GPAM 8 are conventional GPAM compositions. GPAM 1 was prepared using the low molecular weight (8 kDa) base polymer 1 and has a high final solids content (14%) while GPAM 2 was prepared using the high molecular weight (246 kDa) base polymer 3 and has a low final solids content (5%). GPAM 8 was prepared using the low molecular weight (15 kDa) base polymer 2.

[0086] New GPAM 3 to 7 compositions were prepared with base polymers 1 and 3 by various methods. GPAM 3 and GPAM 4 were prepared by glyoxation of base polymer mixtures. GPAM 5 and GPAM 6 were simple mixtures of GPAM 1 and GPAM 2. GPAM 7 was prepared by a two-step reaction. In the first step, GPAM 1 was produced by glyoxation of base polymer 1. In the second step, base polymer 3 and more glyoxal were added to the finished GPAM 1 and an additional glyoxation reaction was carried out to produce the final GPAM 7 composition.

[0087] The new GPAMs 3-7 had considerably higher solids contents than GPAM 2 (5.0%) prepared from base polymer 3. For example, GPAM 4 had a solids content of 7.3%, 46% higher than that of GPAM 2. When GPAM products are produced with a solids content below 6%, the cost associated with production, transport and handling is often greater than the cost of the raw material. As a result, a 45% increase in the product's solids content resulted in a significant reduction in Petition 870240109898, dated 12 / 24 / 2024, p. 66 / 182 54 / 56 total product cost.

[0088] The new GPAMs 9-11 were prepared by performing the glyoxylation reaction of a mixture of base polymer 2 and base polymer 3. The ratio of base polymer 2:base polymer 3 was as indicated in Table 2. As shown in Table 2, GPAMs 9, 10 and 11 have solid contents of 7.0%, 6.7% and 7.2%, respectively, which are each significantly higher than GPAM 2 (5.0%), prepared from base polymer 3, resulting in a significant reduction in the total cost of the product.

[0089] Hand sheets were prepared using the above GPAMs as follows: OCC pulp material was obtained from a recycled paperboard mill. First, the thick material was diluted to 0.5% consistency using tap water. NaCl was added to the diluted pulp to match the conductivity of the residual white water. 1 M HCl solution was then added to the pulp to adjust the pH to 6.4. Second, the GPAM compositions were introduced into the diluted pulp under air agitation. The treated pulp was then added to the dynamic sheet former (DSF) (TECHPAP France, type - FDA) to produce a 110 g / m2 sheet. Next, the formed sheets are pressed with spray paper at 15 psi using a pneumatic roller press and then dried in a rotary dryer at 110°C.Next, the dried paper sheets were cured in an oven (conventional convection oven) at 105°C for 5 minutes and then conditioned in the standard TAPPI control room overnight. Finally, the paper strips were cut along the transverse direction. Example 2: Explosion resistance test

[0090] The explosion resistance test was performed according to the TAPPI T-403 standard method. The results are shown in Table 3. TABLE 3 - EXPLOSION RESISTANCE OF HAND-MADE SHEETS Petition 870240109898, dated 12 / 24 / 2024, page 67 / 182 55 / 56 TREATED WITH VARIOUS GPAM PRODUCTS 2.26 kg / ton (5 lb / ton) 4.53 kg / ton (10 lb / ton) Samples Explosion Improvements Explosion Improvements Blank 35.2 NA 35.2 NA GPAM 1 40.8 16.0% 44.0 25.1% GPAM 2 43.1 22.7% 48.4 37.6% GPAM 3 43.5 23.7% 48.2 37.1% GPAM 4 43.2 22.9% 48.1 36.8%

[0091] As shown in Table 3, each of the new GPAM and GPAM 4 products provided comparable dry strength performance to GPAM 2. In addition, these new GPAM products had a considerably higher solids content than GPAM 2. Example 3: STFI Test

[0092] The STFI test was performed according to the standard method. TAPPI T-826. The results are shown in Table 4 and Table 5. TABLE 4 - STFI RESISTANCE OF HAND-TREATED SHEETS WITH VARIOUS GPAM PRODUCTS 4.08 kg / ton (9 lb / ton) Samples STFI Improvements Blank 8.64 NA GPAM 1 10.01 15.9% GPAM 2 10.61 22.8% GPAM 5 10.56 22.2% GPAM 6 10.53 21.9% GPAM 7 10.65 23.3% TABLE 5 - STFI RESISTANCE OF HAND-TREATED SHEETS WITH VARIOUS GPAM PRODUCTS 2.04 kg / ton (4.5 lb / ton) STFI Samples Improvements Petition 870240109898, dated 12 / 24 / 2024, page 68 / 182 56 / 56 Blank 8.54 NA GPAM 2 9.25 8.3% GPAM 8 8.84 3.5% GPAM 9 9.29 8.8% GPAM 10 9.60 12.4% GPAM 11 9.77 14.4%

[0093] As shown in Table 4, each of the new GPAMs GPAM 5, GPAM 6, and GPAM 7 provided comparable dry strength performance to GPAM 2. Furthermore, as discussed above, these new GPAM products had a considerably higher solids content than GPAM 2.

[0094] Table 5 presents the STFI results for hand sheets treated with conventional GPAM 2 and GPAM 8 prepared from base polymer 3 and base polymer 2, respectively, as well as with novel GPAM 9-11 compositions. Conventional GPAM 2 and GPAM 8 increased STFI by 8.3% and 3.5%, respectively. In comparison, the novel GPAM 9 to 11 increased STFI by 8.8%, 12.4%, and 14.4%, respectively. This study clearly demonstrated that novel GPAM compositions prepared with a mixture of base polymer 2 and base polymer 3 can provide a comparable or considerably greater increase in paper strength compared to conventional GPAMs prepared with base polymer 2 or base polymer 3 alone.

[0095] In the previous procedures, several steps were described. It will, however, be evident that various modifications and alterations can be made, and additional procedures can be implemented, without departing from the broader scope of the procedures, as set forth in the following claims.

Claims

1. Cationic glyoxylated polyacrylamide (GPAM) composition suitable for use as a dry and / or wet strengthening agent, characterized in that said cationic GPAM composition comprises: i. a first base polymer with a weighted average molecular weight ranging from 7 kDa to less than 30 kDa before glyoxylation; and ii.a second base polymer having a weighted average molecular weight ranging from at least 100 kDa to 500 kDa, 150 to 400 kDa, 200 to 300 kDa, 225 to 275 kDa or is about 250 kDa before glyoxation; wherein the weight ratio of the first base polymer to the second base polymer ranges from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, even more optionally from about 30:70 to about 70:30, even more optionally from about 40:60 to about 60:40; wherein the first base polymer is glyoxated and the second base polymer is glyoxated; and wherein the first base polymer and the second base polymer comprise acrylamide-based polymers comprising one or more cationic monomers.

2. Cationic GPAM, according to claim 1, characterized in that: (i) the weighted average molecular weight of the first base polymer varies from no more than 7 to 25 kDa, 7-20 kDa, or 7-15 or 8-15 kDa; (ii) the weight ratio of the glyoxal polymer / base for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71; Petition 870240109898, dated 12 / 24 / 2024, p. 70 / 182 2 / 14 (iii) the cationic composition of GPAM comprises a glyoxal / total base polymer weight ratio of at least about 1:99, at least about 2.5:97.5, at least about 5:95, at least about 7.5:92.5, at least about 10:90, at least about 12.5:87.5, at least about 15:85, at least about 17.5:82.5, at least about 20:80, at least about 22.5:77.5, at least about 25:75, at least about 27.5:72.5, at least about 29:71, or at least about 30:70;(iv) the glyoxylation percentage of the GPAM cationic composition is from about 2% to about 90%, optionally from about 3% to about 80%, additionally optionally from about 4% to about 70%, additionally optionally from about 5% to about 60%; (v) the glyoxylation percentage of the first base polymer and / or the second base polymer is from about 2% to about 90%, optionally from about 3% to about 80%, additionally optionally from about 4% to about 70%, additionally optionally from about 5% to about 60%; (vi) the GPAM content of the GPAM cationic composition is from about 2% to about 20%, optionally from about 3% to about 10%, additionally optionally from about 4% to about 8%, additionally optionally from about 5% to about 7% or about 6%-7.5%, or about 6% to 7%;(vii) the GPAM content of the first base polymer is from about 2% to about 20%, optionally from about 3% to about 10%, additionally optionally from about 4% to about 8%, additionally optionally from about 5% to about 7%, or about 6%-7.5%, or about 6% to 7%; (viii) the GPAM content of the second base polymer is from about 2% to about 20%, optionally from about 3% to about 10%, optionally from about 4% to about 8%, optionally from about Petition 870240109898, dated 12 / 24 / 2024, page 71 / 182 3 / 14 from 5% to about 7%; (ix) the cationic composition of GPAM comprises a weight percentage of solids of about 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.0% or more, 5.5% or more, 6.0% or more, 6.5% or more, 7.0% or more, 7.5% or more, 8.0% or more, 8.5% or more, 9.0% or more, 9.5% or more, 10.0% or more, 10.5% or more, 11.0% or more, or 11.5% or more, or 1.0% to about 20.0%, optionally from about 3.0% to about 15%;or (x) and combination of (i)-(ix).; 3. Cationic GPAM, according to claim 1 or 2, characterized in that: (i) the first base polymer and / or the second base polymer comprise a percentage of cationic monomer of at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight, at least 50% by weight or at least 60% by weight, wherein optionally the first base polymer and / or the second base polymer is amphoteric; (ii) the first base polymer and / or the second base polymer is amphoteric and comprises more cationic monomers than anionic monomers;(iii) one or more cationic monomers comprise each selected from the group consisting of acryloyloxyethyltrimethylammonium chloride (“AETAC”), methacryloyloxyethyltrimethylammonium chloride (MAETAC), methacrylamidopropyltrimethylammonium chloride (“MAPTAC”), acrylamidopropyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium sulfate, methacryloyloxyethyltrimethylammonium chloride, diallyldimethylammonium chloride (“DADMAC”); (iv) the first base polymer and / or the second base polymer comprises an acrylamide or methacrylamide copolymer and one or more cationic monomers; (v) the first base polymer and / or the second base polymer comprises acryloyloxyethyltrimethylammonium chloride or dimethyldiallylammonium chloride (DADMAC) monomers;(vi) the first base polymer and / or the second base polymer comprises a copolymer of (a) acrylamide and / or methacrylamide monomers and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC) monomers; (vii) the first base polymer and / or the second base polymer comprises a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; (viii) the viscosity of the GPAM cationic composition is about 10 cPs or more, about 15 cPs or more, about 20 cPs or more, about 25 cPs or more, about 30 cPs or more, or about 35 cPs or more, for example, as measured by an LV Brookfield viscometer at 25°C and 60 rpm using spindle number 1; (ix) the aqueous vehicle comprises water; or (x) a combination of any two or more of (i)-(ix).; 4. Cationic GPAM, according to any one of claims 1 to 3, characterized in that: (i) the cationic GPAM composition is capable of being stored and / or transported in a reduced volume of an aqueous carrier compared to the volume of an aqueous carrier required for the storage and / or transport of conventional GPAMs used in papermaking; (ii) the first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or Petition 870240109898, dated 12 / 24 / 2024, page 73 / 182 5 / 14 is about 29:71;and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, even more optionally from about 30:70 to about 70:30, even more optionally from about 40:60 to about 60:40 and the GPAM content varies from about 5% to about 7%, or about 6%-7.5%, or about 6% to 7%; (iii) one or both, the first and second base polymers comprise copolymers of a first monomer comprising acrylamide or methacrylamide and a second monomer comprising DADMAC (dimethyldiallylammonium chloride) or acryloyloxyethyltrimethylammonium chloride, optionally wherein the first monomer comprises acrylamide and the second monomer comprises DADMAC, wherein the percent ratio of the first and second monomers varies from about 30:70 to about 70:30;(iv) one or both of the first and second base polymers comprise copolymers of a first monomer comprising acrylamide or methacrylamide and a second monomer comprising DADMAC (dimethyldiallylammonium chloride) or acryloyloxyethyltrimethylammonium chloride, optionally wherein the first monomer comprises acrylamide and the second monomer comprises DADMAC, wherein the percent ratio of the first and second monomers varies from about 40:60 to about 60:40, or is about 40:60; (v) one or both of the first and second base polymers comprise copolymers of acrylamide and DADMAC (dimethyldiallylammonium chloride), the percent ratio of the acrylamide and DADMAC monomers therein varies from about 40:60 to about 60:40; and the ratio of the first and second base polymer in the strengthening agent varies from 20:80 to 80:20, 30:70 to 70:30 or 40:60 to 60:40; or Petition 870240109898, of 12 / 24 / 2024, page 74 / 182 6 / 14 (vi) any combination of (i)-(v).; 5. Paper product, characterized in that it comprises one or more cationic GPAM compositions as defined in any one of claims 1 to 4.

6. Paper product according to claim 5, characterized in that the cationic GPAM composition comprises: a. the first base polymer and / or the second base polymer comprise a copolymer of (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC); b. the first base polymer and / or the second base polymer comprise a copolymer of acrylamide monomers and dimethyldiallylammonium chloride (DADMAC); c. The first base polymer and the second base polymer comprise a copolymer of acrylamide monomers and dimethyldiallylammonium chloride (DADMAC), and the glyoxal polymer / base ratio for the glyoxation reaction varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71; d.The first base polymer and the second base polymer comprise a copolymer of acrylamide monomers and dimethyldiallylammonium chloride (DADMAC); the molecular weight of the first base polymer is not greater than 25 kDa, 20 kDa, 15 kDa or 8 kDa and the molecular weight of the second base polymer is at least 150 kDa, 200 kDa or 250 kDa or 246 kDa; or e. the first base polymer and the second base polymer comprise a copolymer of acrylamide monomers and dimethyldiallylammonium chloride (DADMAC); the molecular weight of the first base polymer is not greater than 25 kDa, 20 kDa, 15 kDa or 8 kDa and the molecular weight of the second base polymer is at least 150 kDa, 200 kDa, Petition 870240109898, dated 12 / 24 / 2024, page.75 / 182 7 / 14 250 kDa or about 246 kDa; the glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71; and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, still optionally from about 30:70 to about 70:30, even more optionally from about 40:60 to about 60:40 and the GPAM content varies from about 5% to about 7%, or about 6%-7.5%, or about 6% to 7%.

7. Paper product according to claim 5 or 6, characterized in that said paper product: a. comprises at least one layer of paper or web containing the cationic composition of GPAM; b. comprises the cationic composition of GPAM on at least one surface of the paper product; c. comprises one or more sheets of paper, cardboard, tissue paper and wallboard; d. comprises one or more of Kraft paper, bond paper, semi-chemical paper and the like, including paper produced using bleached pulp, unbleached pulp or combinations thereof; e. comprises a fiber-based product; f.includes one or more of the following: sheets of paper, cardboard-based products, beverage carriers, towels, milk and juice cartons, food trays, paper bags, cardboard liner for corrugated cardboard containers, packaging grade cardboard and tissue and towel grade, paper materials, paper towels, diapers, sanitary napkins, training pants, panty liners, incontinence underwear, tampons, urinal pads, litter box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent facial tissues, absorbent toilet paper, napkins, wrapping paper and / or other cardboard products, such as boxes and paper for bags; g. includes cellulose cardboard fabric or sheets that optionally comprise predominantly cellulose fibers; h.comprises cellulose fibers and from about 0.02% to about 10% cationic GPAM composition by dry weight of cellulose fibers, optionally in the range of about 0.05% by weight to 5% by weight of the dry weight of cellulose fibers; i. comprises improved paper strength, e.g. as determined by the STFI test, compared to a paper product that does not comprise a cationic GPAM composition; j. comprises improved paper strength, e.g. as determined by the burst strength test, compared to a paper product that does not comprise a cationic GPAM composition; and / or k. comprises a combination of any two or more of (a)-(j).

8. Use of one or more cationic GPAM compositions according to any of claims 1 to 4 in a papermaking method to increase the wet and / or dry strength of paper products produced by said method, characterized in that said method comprises adding one or more cationic GPAM compositions during the papermaking method in an amount effective to increase the wet and / or dry strength of the paper products, wherein: a. one or more cationic GPAM compositions are added to a composition comprising fiber and / or pulp used in the method before the paper product is formed; and / or b. one or more cationic GPAM compositions are added to one or more surfaces of the paper product after the paper product is formed.

9. A method for manufacturing one or more paper products, characterized in that said method comprises: a. providing a composition comprising: (i) predominantly cellulose fibers; or (ii) any softwood fiber, hardwood fiber, recycled fiber, refined fiber, or a mixture of any of the foregoing in an amount sufficient to form an overall supply of approximately 1 to 100% hardwood fiber, softwood fiber, recycled fiber, refined fiber, or a mixture of any of the foregoing; b. adding a predetermined amount of one or more cationic GPAM compositions according to claims 1 to 4; and c. forming the desired paper product, wherein when the composition is in accordance with a. (ii), the formation is c.It is to form a paper product by drying using one or more drying methods to a desired moisture content level, optionally wherein one or more paper products are one or more adsorbent paper products.

10. Use of at least one cationic composition of GPAM according to any one of claims 1 to 4 in a method for reinforcing paper, the method characterized by comprising contacting cellulose fibers with a reinforcing resin comprising at least one cationic composition of GPAM and curing, at least partially, the reinforcing resin that comes into contact with the cellulose fibers to produce a paper product of enhanced strength.

11. Method or use according to any one of claims 8 to 10, characterized in that: a. the cationic composition of GPAM is added at the wet end of a papermaking plant to a cellulose fiber suspension; b. the cationic composition of GPAM is added in an amount of about 0.02% by dry weight to about 10% by dry weight of the cellulose fibers, optionally in the range of about 0.05% by weight to 5% by weight of the dry weight of the cellulose fibers; c. the cationic composition of GPAM is added before, during and / or after the paper product is formed; d. the cationic composition of GPAM is added to one or more surfaces of the paper product after the paper product is formed; e. The cationic composition of GPAM provides an increase in paper strength to the paper product, for example, as determined by the STFI test; f.The cationic composition of GPAM provides an increase in paper strength to the paper product, for example, as determined by the tear strength test; g. the paper product comprises one or more of the following: paper sheets, cardboard-based products, beverage carriers, towels, milk and juice cartons, food trays, paper bags, lining paper for corrugated cardboard containers, packaging paper grade and tissue and towel grade, paper materials, paper towels, diapers, sanitary napkins, training pants, panty liners, incontinence briefs, tampons, urinal pads, litter box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent facial tissues, absorbent toilet paper, napkins, wrapping paper and / or other cardboard products such as boxes and paper for bags; h.The paper product comprises cellulose board webs (Petition 870240109898, 12 / 24 / 2024, p. 79 / 182 11 / 14) that optionally comprise predominantly cellulose fibers; i. the cationic composition of GPAM decreases the drainage time of a treated sample compared to the drainage time without the use of the cationic composition of GPAM; j. the cationic composition of GPAM increases the drainage rate of a treated sample, resulting in an increased paper production rate compared to a drainage rate without the use of the cationic composition of GPAM; k. the cationic composition of GPAM improves the drying energy economy of the papermaking method; l. the cationic composition of GPAM decreases the total solids content of a treated sample, such as the total solids content of white water from the tray or silo after sheet formation, compared to the total solids content without the use of a cationic composition of GPAM; and / or m.a combination of any two or more of (a)-(l).

12. Method according to any one of claims 8 to 11, characterized in that one or more cationic GPAM compositions comprise GPAM wherein: a. the first base polymer and the second base polymer comprise an acrylamide or methacrylamide copolymer and one or more cationic monomers; b. the first base polymer and / or the second base polymer comprise a copolymer of (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC) monomers; c. the first base polymer and / or the second base polymer comprise an acrylamide copolymer and dimethyldiallylammonium chloride (DADMAC) monomers;Petition 870240109898, of 12 / 24 / 2024, page 80 / 182 12 / 14 d. the first base polymer and the second base polymer comprise a copolymer of acrylamide monomers and dimethyldiallylammonium chloride (DADMAC) comprising any combination of (i)-(iv): (i) the glyoxal / base polymer ratio for the glyoxation reaction varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71; (ii) the molecular weight of the first base polymer is not greater than 25 kDa, 20 kDa, 15 kDa, or 8 kDa and the molecular weight of the second base polymer is at least 150 kDa, 200 kDa, 250 kDa or about 246 kDa; (iii) the glyoxal / base polymer ratio for the glyoxalation reaction used to glyoxylate the first and / or second base polymer ranges from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71;(iv) the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, optionally from about 20:80 to about 80:20, further optionally from about 30:70 to about 70:30, still more optionally from about 40:60 to about 60:40; or e. the first base polymer and the second base polymer comprise an acrylamide-dimethyldiallylammonium chloride (DADMAC) copolymer; the molecular weight of the first base polymer is not greater than 25 kDa, 20 kDa, 15 kDa or 8 kDa and the molecular weight of the second base polymer is at least 50 kDa, 200 kDa, 250 kDa or about 246 kDa; The glyoxal / base polymer ratio for the glyoxation reaction of the first and / or second base polymer varies from about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or is about 29:71;and the weight ratio of the first base polymer to the second base polymer varies from about 10:90 to about 90:10, Petition 870240109898, 12 / 24 / 2024, p. 81 / 182 13 / 14 optionally from about 20:80 to about 80:20, even more optionally from about 30:70 to about 70:30, even more optionally from about 40:60 to about 60:40 and the GPAM content varies from about 5% to about 7%, or about 6%-7.5%, or about 6% to 7%.; 13. Method for preparing a GPAM cationic composition as defined in any of claims 1-4, the method being characterized by comprising: a. glyoxylating the first base polymer in a first glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; b. glyoxylating the second base polymer in a second glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and c. combining the first glyoxylated base polymer and the second glyoxylated base polymer to produce the GPAM cationic composition; wherein steps (a) and (b) may be carried out in any order or simultaneously; or the method may further comprise: a. combining the first base polymer and the second base polymer; and b.glyoxylation of the combination of the first base polymer and the second base polymer in a glyoxylation reaction comprising glyoxal to produce the cationic composition of GPAM; or the method may further comprise: a. glyoxylating the first base polymer in a glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; and b. adding the second base polymer and optionally additional glyoxal to the glyoxylation reaction to produce the cationic composition of GPAM; or the method may further comprise: a. glyoxylating the second base polymer in a glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and b. Add the first base polymer and optionally additional glyoxal to the glyoxation reaction to produce the cationic composition of GPAM; or the method may further comprise: a.a. glyoxylate the first base polymer in a first glyoxylation reaction comprising glyoxal to produce a first glyoxylated base polymer; and b. glyoxylate the second base polymer in a second glyoxylation reaction comprising glyoxal and the first glyoxylated base polymer to produce the cationic composition of GPAM; or the method may further comprise: a. glyoxylate the second base polymer in a second glyoxylation reaction comprising glyoxal to produce a second glyoxylated base polymer; and b. glyoxylate the first base polymer in a first glyoxylation reaction comprising glyoxal and the second glyoxylated base polymer to produce the cationic composition of GPAM.

14. Composition comprising one or more cationic GPAM compositions, characterized in that one or more cationic GPAM compositions are produced by any combination of the methods as defined in claim 13.