GPAM composition and method

Abstract

The present disclosure generally relates to glyoxalated polyacrylamide (GPAM) compositions, methods for preparing the same, and methods for using the same in particular in the paper industry. Additionally, the present disclosure generally relates to cationic GPAM compositions, methods for preparing the same, and methods for using the same in papermaking applications and in products such as paper-based products, wherein the cationic GPAM compositions can provide increased wet and / or dry strength to paper-based products, and optionally, such cationic GPAM compositions require a smaller volume of aqueous carrier for storage or transport compared to the volume of aqueous carrier required for conventional GPAMs used in papermaking.

Description

Technology Field

[0001] The present disclosure generally relates to glyoxalated polyacrylamide (GPAM) compositions and articles containing the same, and methods of using the same, particularly GPAM compositions useful in the paper industry, and more specifically cationic GPAM compositions and their use in papermaking applications and products such as paper-based products. The present disclosure also generally relates to methods for preparing the aforementioned cationic GPAM compositions. Background Technology

[0002] Glyoxalated polyacrylamide (GPAM) compositions are widely used in the paper industry and are often used to increase paper wet strength and dry strength. For example, glyoxalated polyacrylamide can increase the initial wet strength of many household tissues, which is a useful property since household tissues often come into contact with water during use. Applying glyoxalated polyacrylamide to paper products can also increase the compressive strength and dimensional stability of many cardboard-grade paper products.

[0003] GPAM is generally prepared through the reaction between glyoxal and a basic polyacrylamide polymer, such as a cationic polyacrylamide backbone. In some cases, the reaction between glyoxal and cationic polyacrylamide is carried out in a weakly alkaline aqueous solution and stabilized under acidic conditions. In practice, the polyacrylamide component of a GPAM composition often contains a relatively small amount of cationic monomer, typically less than about 5 mol%, thereby limiting the cationic material contribution to the GPAM composition.

[0004] Furthermore, GPAM produced by conventional methods generally cannot be dried into solid particulate form without inducing significant and rapid cross-linking of the GPAM, which limits the utility of the resulting GPAM composition. As such, GPAM compositions are typically stored and transported in bulk aqueous fluid carriers. The volume of GPAM compositions transported in this manner can be massive, often requiring large-volume containers or tanker storage tanks for transport. Transporting such large volumes of product significantly increases the cost of transporting and using the GPAM composition.

[0005] As a result of the characteristics of current GPAM compositions and logistical considerations regarding their transport, there remains a need for GPAM compositions that include characteristics that enable lower transport costs and / or smaller transport volumes of GPAM compositions while still maintaining the desired characteristics of GPAM compositions.

[0006] The present disclosure relates to a cationic glyoxalated polyacrylamide ("GPAM") composition suitable for use as a generally dry and / or wet reinforcing agent, wherein the cationic GPAM composition comprises: a. a first basic polymer having a weight average molecular weight of less than 30,000 Da; and b. a second basic polymer having a weight average molecular weight of at least 30,000 Da, wherein the first basic polymer and the second basic polymer 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; the first basic polymer and the second basic polymer are each glyoxalated; optionally, the cationic GPAM composition requires a reduced volume of aqueous carrier compared to the volume of aqueous carrier required for conventional GPAM used in papermaking for storage or transport.

[0007] In some embodiments, the weight average molecular weight of the first basic 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 weight average molecular weight of the second basic polymer may be at least 30 kDa, 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 glyoxalation percentage of the cationic GPAM composition may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the glyoxalation percentage of the first basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the glyoxalation percentage of the second basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the GPAM content of the cationic GPAM composition may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the GPAM content of the first basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%.In some embodiments, the GPAM content of the second basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the first basic polymer may contain a cationic amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein optionally the first basic polymer may be amphoteric. In some embodiments, the second basic polymer may comprise a cationic monomer content of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the second basic polymer may optionally be amphoteric. In some embodiments, the first basic polymer may comprise a cationic monomer percentage of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the first basic polymer may optionally be amphoteric. In some embodiments, the second basic polymer may comprise a percentage of cationic monomer of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the second basic polymer may optionally be amphoteric. In some embodiments, the cationic GPAM composition comprises about 1.0% or more, 2.0% or more, 3.0% or more, 4.0% or more, 5.It may include a weight percentage of solids of 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 cationic GPAM composition may include a weight percentage of solids of about 1.0% to about 20.0%, optionally about 3.0% to about 15.0%. In some embodiments, the cationic GPAM composition may comprise a glyoxal to total basic 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. In some embodiments, the first basic polymer may comprise an acrylamide-based polymer. In some embodiments, the second basic polymer may comprise an acrylamide-based polymer. In some embodiments, the first basic polymer may comprise one or more cationic monomers. In some embodiments, the second basic polymer may comprise one or more cationic monomers. In some embodiments, the first basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50. In some embodiments, the second basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50.In some embodiments, the first basic polymer may be amphoteric and may contain more cationic monomers than anionic monomers. In some embodiments, the second basic polymer may be amphoteric and may contain more cationic monomers than anionic monomers. In some embodiments, the first basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, the second basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, the viscosity of the cationic GPAM composition may be, for example, about 10 cP or more, about 15 cP or more, about 20 cP or more, about 25 cP or more, about 30 cP or more, or about 35 cP or more when measured with an LV Brookfield viscometer at 25°C and 600 rpm using spindle number 1. In some embodiments, the aqueous carrier may contain water.

[0008] In some embodiments, one or more cationic monomers are each acryloyloxyethyl trimethylammonium chloride ("AETAC"), methacryloyloxyethyl trimethylammonium chloride, methacrylamidopropyl trimethylammonium chloride ("MAPTAC"), acrylamidopropyl trimethylammonium chloride, methacryloyloxyethyl dimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, diallyldimethylammonium chloride ("DADMAC"); dialkylaminoalkyl acrylate, and methacrylate, and quaternary salt of dimethylaminoethyl acrylate methyl chloride ("DMAEA.MCQ"), quaternary salt of dimethylaminoethyl acrylate methyl sulfate ("DMAEM.MCQ"), quaternary salt of dimethylaminoethyl acrylate benzyl chloride ("DMAEA.MCQ").BCQ"), dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of dimethylaminoethyl methacrylate benzyl chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacryloyl hydrochloride, dialkylaminoalkylacrylamide or methacrylamide and their quaternary salts or salts, e.g., acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylmethacrylamide methyl sulfate, dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide It may be selected from the group consisting of hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diallyldialkylammonium halides such as diallyldiethylammonium chloride and diallyldimethylammonium chloride, but not limited thereto, quaternary salts or salts thereof. 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 more cationic monomers may each be selected from the group consisting of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (also known as Q9), 3-(methacrylamido)propyltrimethylammonium chloride, 3-(acryloylamido)propyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide.

[0009] 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, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethyl methacrylamide, and any combination thereof. In some embodiments, the acrylamide-based polymer may comprise one or more acrylamide monomers.

[0010] In an exemplary embodiment, the cationic GPAM in the GPAM composition is selected from the following:

[0011] a. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide or methacrylamide and one or more cationic monomers;

[0012] b. A first basic polymer and / or a second basic polymer comprising (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) a copolymer of dimethyldiallylammonium chloride (DADMAC) monomers;

[0013] c. A first basic polymer or a second basic polymer comprising a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers;

[0014] d. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers;

[0015] e. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallyammonium chloride (DADMAC) monomers, wherein the ratio of glyoxal to basic polymer for the glyoxalation reaction is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71;

[0016] f. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC); the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, or 250 kDa, or 246 kDa;

[0017] g. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers; the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; The ratio of glyoxal to basic polymer for the glyoxalation reaction used to glyoxylate the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71;

[0018] h. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallyammonium chloride (DADMAC); the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; and the ratio of glyoxal to basic polymer for the glyoxalation reaction of the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71; The weight ratio of the first basic polymer to the second basic polymer is in the range 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, and even also optionally about 40:60 to about 60:40; or

[0019] i. A first basic polymer and a second basic polymer comprising a copolymer of acrylamide and dimethyldiallyammonium chloride (DADMAC); the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; and the ratio of glyoxal to basic polymer for the glyoxalation reaction of the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71; The weight ratio of the first basic polymer to the second basic polymer is in the range 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, and even also optionally about 40:60 to about 60:40, and the GPAM content is in the range of about 5% to about 7%, or about 6% to 7.5%, or about 6% to 7%.

[0020] Additionally, the present disclosure relates to a paper product comprising one or more cationic GPAM compositions as generally discussed herein. In some embodiments, the paper product may comprise at least one paper layer or web 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, the paper product may comprise one or more of paper sheets, cardboard, tissue paper, and wallpaper. In some embodiments, the paper product may comprise one or more of kraft paper, sulfite paper, semi-chemical paper, etc., including paper produced using bleached pulp, unbleached pulp, or a combination thereof. In some embodiments, the paper product may comprise a fiber-based product. In some embodiments, the aforementioned paper product may comprise one or more of other paperboard products such as hand sheets, cardboard-based products, beverage containers, towels, milk and juice cartons, food trays, paper bags, corrugated container liner cartons, packaging carton grades, and tissue and towel grades, paper materials, paper towels, diapers, sanitary pads, training panties, panty liners, incontinence briefs, tampons, urine pads, potty box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent face tissues, absorbent bathroom tissues, napkins, wrapping paper, and / or carton and bag paper. In some embodiments, the aforementioned paper product may optionally comprise a cellulose paperboard web comprising mostly cellulose fibers. In some embodiments, the aforementioned paper product may comprise a cationic GPAM composition ranging from about 0.02% to about 10% based on the dry weight of the cellulose fibers, optionally from about 0.05 wt% to 5 wt% based on the dry weight of the paper.In some embodiments, the paper product may have improved paper strength compared to a paper product that does not contain a cationic GPAM composition, for example, when measured by an STFI test. For example, in some embodiments, the aforementioned paper product may have an improved 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, or 25.0% or more in a 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a blank sample used in the STFI test of the paper product. In some embodiments, the paper product may have improved paper strength compared to a paper product that does not contain a cationic GPAM composition, for example, when measured by a burst strength test. For example, in some embodiments, the paper product described above may have an improved burst strength 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 a 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a blank sample used in a burst strength test.

[0021] In an exemplary embodiment, a paper product comprising one or more cationic GPAM compositions comprises cationic GPAM, wherein

[0022] a. The first basic polymer and the second basic polymer comprise a copolymer of an acrylamide or methacrylamide monomer and one or more cationic monomers;

[0023] b. The first basic polymer and / or the second basic polymer comprises a copolymer of (a) acrylamide and / or methacrylamide and acryloyloxyethyltrimethylammonium chloride and / or (b) dimethyldiallylammonium chloride (DADMAC) monomers;

[0024] c. The first basic polymer and / or the second basic polymer comprises a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers;

[0025] d. The first basic polymer and the second basic polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers;

[0026] e. The first basic polymer and the second basic polymer comprise copolymers of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers, and the ratio of glyoxal to basic polymer for the glyoxalation reaction is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71;

[0027] f. The first basic polymer and the second basic polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC); wherein the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, or 250 kDa, or 246 kDa;

[0028] g. The first basic polymer and the second basic polymer comprise a copolymer of acrylamide and dimethyldiallylammonium chloride (DADMAC) monomers, wherein the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; The ratio of glyoxal to basic polymer for the glyoxalation reaction used to glyoxylate the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71;

[0029] h. The first basic polymer and the second basic polymer comprise a copolymer of acrylamide and dimethyldiallyammonium chloride (DADMAC); wherein the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; and the ratio of glyoxal to basic polymer for the glyoxalation reaction of the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71; The weight ratio of the first basic polymer to the second basic polymer is in the range 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, and even also optionally about 40:60 to about 60:40; or

[0030] i. The first basic polymer and the second basic polymer comprise a copolymer of acrylamide and dimethyldiallyammonium chloride (DADMAC) monomers, wherein the molecular weight of the first basic polymer is 25 kDa, 20 kDa, 15 kDa, 8 kDa, or 5 kDa or less, and the molecular weight of the second basic polymer is at least 50 kDa, 100 kDa, 150 kDa, 200 kDa, 250 kDa, or about 246 kDa; and the ratio of glyoxal to basic polymer for the glyoxalation reaction of the first and / or second basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, 40:60 to 60:40, or about 29:71; The weight ratio of the first basic polymer to the second basic polymer is in the range 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, and even also optionally about 40:60 to about 60:40, and the GPAM content is in the range of about 5% to about 7%, or about 6% to 7.5%, or about 6% to 7%.

[0031] Additionally, the present invention generally relates to a papermaking method, wherein the method comprises the step of adding one or more cationic GPAM compositions discussed herein during the papermaking method in an amount effective for increasing the wet and / or dry strength of the paper product produced by the method described above. In some embodiments, one or more cationic GPAM compositions may be added to a composition comprising fibers and / or pulp used in the method before the paper product is formed. In some embodiments, one or more cationic GPAM compositions may be added to one or more surfaces of the paper product after the paper product is formed.

[0032] Additionally, the present disclosure generally relates to a method for manufacturing a hand sheet, wherein the method comprises: 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 herein; f. adding the treated pulp to a dynamic sheet-forming agent; g. pressing the sheet produced from step f; h. drying the sheet; and i. conditioning the sheet.

[0033] Additionally, the present disclosure relates to a method for generally manufacturing one or more paper products, wherein the method comprises: a. providing a composition comprising mostly cellulose fibers; b. adding a predetermined amount of one or more cationic GPAM compositions as discussed herein; and c. forming a desired paper product.

[0034] Additionally, the present disclosure relates to a method for generally manufacturing one or more paper products, optionally one or more adsorbent paper products, wherein the method comprises: a. providing a composition comprising one of soft wood fibers, hard wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above in an amount sufficient to form a total feed of about 1 to 100% of hard wood fibers, soft wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above; (b) adding a predetermined amount of one or more cationic GPAMs as discussed herein; and (c) forming a paper product by drying to a desired moisture content level through one or more drying means.

[0035] In addition, the present invention generally relates to a method for reinforcing paper, the method comprising the steps of contacting a pulp fiber with a reinforcing resin comprising at least a cationic GPAM composition as discussed herein, and at least partially curing the cationic GPAM in a mixture of the pulp fiber and the cationic GPAM to produce a paper product of reinforced strength.

[0036] In some embodiments, the cationic GPAM composition may be added to a cellulose fiber suspension at the wet end of a papermaking facility. In some embodiments, the cationic GPAM composition may be added in a range of about 0.02% to about 10% by dry weight of the cellulose fibers, optionally about 0.05 wt% to 5 wt% by dry weight of the paper. In some embodiments, the cationic GPAM composition may be added before, during, and / or after the paper is formed. In some embodiments, the cationic GPAM composition may be added to one or more surfaces of the paper product after the paper product is formed. In some embodiments, the cationic GPAM composition may provide enhanced paper strength to the paper product, for example, when measured by an STFI test. For example, in some embodiments, the paper product may have an improved 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, or 25.0% or more in 4.5 lbs / ton, 5.0 lbs / ton, or 10 lbs / ton tests compared to the blank sample used in the STFI test of the paper product. In some embodiments, the cationic GPAM composition may provide the paper product with improved paper strength, for example, when measured by a burst strength test. For example, in some embodiments, the paper product may have an improved burst strength 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 a 4.5 lbs / ton, 5.0 lbs / ton, or 9.0 lbs / ton, or 10 lbs / ton test compared to the blank sample used in the burst strength test.In some embodiments, the paper product may include one or more of other paperboard products such as hand sheets, cardboard-based products, beverage containers, towels, milk and juice cartons, food trays, paper bags, liner cardboard for corrugated containers, packaging carton grades, and tissue and towel grades, paper materials, paper towels, diapers, sanitary pads, training panties, panty liners, incontinence briefs, tampons, urine pads, potty box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent face tissues, absorbent bathroom tissues, napkins, wrapping paper, and / or carton and bag paper. In some embodiments, the paper product may optionally include a cellulose paperboard web comprising mostly cellulose fibers. In some embodiments, the cationic GPAM composition may reduce the discharge time of the treated sample compared to the discharge time when the cationic GPAM composition is not used. For example, in some embodiments, the cationic GPAM composition may affect efficient discharge, such as showing an improvement of, for example, the discharge of OCC pulp, i.e., the time to collect a given amount of filtrate from OCC pulp by more than 25.0%, more than 30.0%, more than 35.0%, more than 40.0%, more than 45.0%, more than 50.0%, or more than 55.0% compared to discharge when the cationic GPAM composition is not used. In some embodiments, the cationic GPAM composition may increase the discharge rate of the treated sample compared to the discharge rate when the cationic GPAM composition is not used, which leads to an increase in the paper production rate. In some embodiments, the cationic GPAM composition may improve the energy savings required for drying paper products. In addition, the cationic GPAM composition is 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 32.0% compared to the total amount of solids present in the sample when the cationic GPAM composition is not used.It may affect the reduction of the total amount of solids present in the treated sample, such as a 5% improvement (reduction in solid content), for example, the reduction in the total solids present in the filtrate collected from OCC pulp treated with the cationic GPAM composition, for example, the reduction in the solid content of the white water from tray or silo pre-sheet formation. In some embodiments, the cationic GPAM composition may improve the energy savings required for drying.

[0037] Additionally, the present disclosure relates to a method for preparing a cationic GPAM composition as generally discussed herein, and in particular, the cationic GPAM composition comprises: a. a first basic polymer having a weight average molecular weight of less than 30,000 Da; and b. a second basic polymer having a weight average molecular weight of at least 30,000 Da, wherein the first basic polymer and the second basic polymer 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; the first basic polymer and the second basic polymer are each glyoxalated; optionally, the cationic GPAM composition requires a reduced volume of aqueous carrier compared to the volume of aqueous carrier required for conventional GPAM used in papermaking for storage or transport. In some embodiments, the method comprises: a. a. a step of glyoxalizing a first basic polymer in a first glyoxalization reaction containing glyoxal to produce a first glyoxalized basic polymer; b. a step of glyoxalizing a second basic polymer in a second glyoxalization reaction containing glyoxal to produce a second glyoxalized basic polymer, wherein optionally, the first and / or second basic polymer comprises or consists of acrylamide or methacrylamide, and DADMAC or acryloyloxyethyltrimethylammonium chloride packed monomer; and c. a step of combining the first glyoxalized basic polymer and the second glyoxalized basic polymer to produce a cationic GPAM composition; and steps (a) and (b) may be performed in any order or simultaneously. In some embodiments, the method comprises: a. combining the first basic polymer and the second basic polymer; and b. The method may include the step of glyoxalizing a combination of a first basic polymer and a second basic polymer in a glyoxalization reaction containing glyoxal to produce a cationic GPAM composition. In some embodiments, the method comprises: a.The method may comprise a step of producing a first glyoxalized basic polymer by glyoxalizing a first basic polymer in a glyoxalization reaction containing glyoxal; and b. a step of producing a cationic GPAM composition by adding a second basic polymer and optionally additional glyoxal to the glyoxalization reaction. In some embodiments, the method may comprise a step of producing a second glyoxalized basic polymer by glyoxalizing a second basic polymer in a glyoxalization reaction containing glyoxal; and b. a step of producing a cationic GPAM composition by adding a first basic polymer and optionally additional glyoxal to the glyoxalization reaction. In some embodiments, the method may comprise a step of producing a first glyoxalized basic polymer by glyoxalizing a first basic polymer in a first glyoxalization reaction containing glyoxal; and b. The method may include the step of producing a cationic GPAM composition by glyoxalizing a second basic polymer in a second glyoxalization reaction comprising glyoxal and a first glyoxalized basic polymer. In some embodiments, the method may include: a. the step of producing a second glyoxalized basic polymer by glyoxalizing a second basic polymer in a second glyoxalization reaction comprising glyoxal; and b. the step of producing a cationic GPAM composition by glyoxalizing a first basic polymer in a first glyoxalization reaction comprising glyoxal and a second glyoxalized basic polymer.

[0038] In addition, the present disclosure provides a cationic GPAM composition produced by any one of the methods described above.

[0039] In addition, the present disclosure provides a composition comprising one or more cationic GPAM compositions produced by one or more of the methods described above. Specific details for implementing the invention

[0040] definition

[0041] The singular forms "one," "one," and "one" as used herein include plural references unless otherwise specified in the context. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention pertains.

[0042] Unless otherwise specified, as used herein, when "%" is referred to in relation to a compound or composition, it means "weight %" or "weight basis %".

[0043] The term "monomer" as used herein generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers.

[0044] The terms “polymer,” “polymers,” “polymericity,” and similar terms as used herein are used in their ordinary meanings as understood by those skilled in the art and may thus be used herein to refer to or describe large molecules (or groups of such molecules) containing repeating units. Polymers may be formed in various ways, including the polymerization of monomers and / or the chemical modification of one or more repeating units of a precursor polymer. Unless otherwise specified, polymers may include “homogenomers” that may contain substantially identical repeating units, which may be formed by various methods, such as, for example, the polymerization of a specific monomer. Unless otherwise specified, polymers may also include “copolymers” that may contain two or more different repeating units, which may be formed, for example, by the copolymerization of two or more different monomers and / or the chemical modification of one or more repeating units of a precursor polymer. Unless otherwise specified, the polymer or copolymer may also include a “terpolymer” which may include a polymer comprising three or more different repeating units. As used herein, the term “polymer” is intended to include the acidic form of the polymer as well as its various salts. The polymer may be inherently amphoteric, that is, may contain both anionic and cationic substituents, but they do not necessarily have to be present in equal proportions.

[0045] The term "nonionic monomer" as used herein generally refers to a monomer that possesses a neutral charge.

[0046] As used herein, the term “anionic monomer” may refer to anionic monomers that are substantially anionic, either wholly or partially (at equilibrium), at a pH in the range of about 4.0 to about 9.0. “Anionic monomers” may be neutral at a low pH (about 2 to about 6) or may be anionic monomers that are anionic at a low pH. In some embodiments, anionic monomers, e.g., vinyl monomers, may include, but are not limited to, carboxylic acid functional groups, sulfonic acid functional groups, phosphonic acid functional groups, and their corresponding water-soluble salts, and any combination thereof. In some embodiments, the anionic monomer may include acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, 2-hydroxy-3-acrylamidepropanesulfonic acid, styrene sulfonic acid, vinyl phosphonic acid, and combinations thereof, as well as their corresponding water-soluble or dispersible alkali metals, alkaline earth metals, and ammonium salts, and any combination thereof. In some embodiments, the cationic GPAM composition may optionally include an amphoteric basic polymer, i.e., a basic polymer comprising both the cationic monomer and the anionic monomer.

[0047] As used herein, the term "cationic monomer" generally refers to a monomer that possesses a positive charge. Examples of cationic monomers may include, but are not limited to, acryloyloxyethyl trimethylammonium chloride ("AETAC"), methacryloyloxyethyl trimethylammonium chloride, methacrylamidopropyl trimethylammonium chloride ("MAPTAC"), acrylamidopropyl trimethylammonium chloride, methacryloyloxyethyl dimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, and / or diallyl dimethylammonium chloride ("DADMAC"). The aforementioned cationic monomers are also dialkylaminoalkyl acrylates, and methacrylates, and the quaternary salt of dimethylaminoethyl acrylate methyl chloride ("DMAEA.MCQ"), the quaternary salt of dimethylaminoethyl acrylate methyl sulfate ("DMAEM.MCQ"), and the quaternary salt of dimethylaminoethyl acrylate benzyl chloride ("DMAEA").BCQ"), dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of dimethylaminoethyl methacrylate benzyl chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacryloyl hydrochloride, dialkylaminoalkylacrylamide or methacrylamide and their quaternary salts or salts, e.g., acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylmethacrylamide methyl sulfate, dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide It may include, but is not limited to, quaternary salts or salts thereof, including but not limited to diallyldialkylammonium halides such as hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diallyldiethylammonium chloride and diallyldimethylammonium chloride. The alkyl group is generally C. 1-8 The monomers may include, but are not limited to, those containing alkyl groups. In some embodiments, the cationic monomer may include a quaternary ammonium or salt of vinyl amide, vinyl carboxylic acid, methacrylate, and derivatives thereof. The cationic monomers may be combined to form, for example, a quaternary salt of dimethylaminoethyl methacrylate methyl chloride, and a terpolymer of diallyldimethylammonium chloride and acrylamide.

[0048] The term “glyoxalation percentage” as used herein refers to the percentage of glyoxalated acrylamide monomers in the polymer of the cationic GPAM composition, for example, the first basic polymer and / or the second basic polymer.

[0049] The term "GPAM content" as used herein refers to the sum of glyoxalated basic polymer(s) + free glyoxal in a cationic GPAM composition.

[0050] As used herein, the terms “papermaking process” and “papermaking application” generally refer to any process from which any form of paper and / or paperboard product may be produced. For example, such a process may include steps for manufacturing paper products from pulp, such as a method comprising the steps of forming an aqueous cellulose paper feed, discharging the feed to form a sheet, and drying the sheet. The steps of forming the paper feed, discharging, and drying may be performed in any conventional manner generally known in the art.

[0051] As used herein, the terms “polyacrylamide” or “PAM” generally refer to polymers and copolymers comprising an acrylamide moiety, and the terms include any polymer or copolymer comprising an acrylamide moiety, e.g., one or more acrylamide (co)polymers. In some cases, PAM may include anionic PAM (APAM), cationic PAM (CPAM), and / or sulfonated PAM (SPAM). In some embodiments, polyacrylamide may be cationic polyacrylamide (cPAM).

[0052] As used herein, the term “glyoxalated polyacrylamide” (“GPAM”) generally refers to a polymer obtained by reacting glyoxal with a basic polyacrylamide polymer. Methods for producing glyoxalated polyacrylamide 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 reacting glyoxal with a cationic polyacrylamide). In some cases, the polyacrylamide backbone of GPAM may contain a small amount of cationic monomer, which causes the polymer to self-retain on the fiber. Generally, GPAM comprises a reactive polymer capable of covalently bonding with cellulose upon dehydration.

[0053] The present invention provides a cationic GPAM composition having specific properties that are highly suitable for use in papermaking processes, namely, properties that are highly suitable for use as an additive to increase paper wet strength and / or dry strength; which possesses improved storage and transport properties, unlike conventional GPAM used in papermaking processes, which are not only undesirable but also costly because, for example, they generally require large-capacity containers or tanker vessels for transport. That is, the cationic GPAM can be stored and transported without the need to add a large amount of aqueous carrier. In some cases, the aqueous carrier may contain water. In some cases, the volume of the aqueous carrier used during the transport of the cationic GPAM discussed herein may be smaller than the volume used to transport conventional GPAM. For example, in some cases, conventional GPAM may contain a solid content percentage of 4% or less, whereas in some embodiments, the cationic GPAM composition may contain a solid content percentage of more than 4%, i.e., more than 4% to about 11%, for example, more than about 4% to about 9%, more than about 5% to about 8%, or about 6% to about 7.5%.

[0054] The terms “cationic GPAM” or “cationic GPAM composition” as used herein generally refer to a GPAM composition comprising a first basic polymer having a weight average molecular weight of less than 30,000 Da and a second basic polymer having a weight average molecular weight of at least 30,000 Da, wherein the first basic polymer and the second basic polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, optionally about 30:70 to about 70:30, and the first basic polymer and the second basic polymer are each glyoxalated, wherein optionally the cationic GPAM composition requires an aqueous carrier for storage or transport with a reduced volume compared to the volume of an aqueous carrier required for conventional GPAM used in papermaking. In some embodiments, the weight average molecular weight of the first basic 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 weight average molecular weight of the second basic polymer may be at least 30 kDa, 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 glyoxalation percentage of the cationic GPAM composition may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%.In some embodiments, the glyoxalation percentage of the first basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the glyoxalation percentage of the second basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the GPAM content of the cationic GPAM composition may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the GPAM content of the first basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the GPAM content of the second basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the first basic polymer may contain a cationic amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein optionally the first basic polymer is amphoteric. In some embodiments, the second basic polymer may comprise a cationic amount of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein optionally the second basic polymer is amphoteric.In some embodiments, the first basic polymer may comprise a percentage of cationic monomers of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the first basic polymer may optionally be amphoteric. In some embodiments, the second basic polymer may comprise a percentage of cationic monomers of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the second basic polymer may optionally 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 cationic GPAM composition may comprise a weight percentage of solids of about 1.0% to about 20.0%, optionally about 3.0% to about 15%. In some embodiments, the cationic GPAM composition may comprise a glyoxal to total basic 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.In some embodiments, the first basic polymer may comprise an acrylamide-based polymer. In some embodiments, the second basic polymer may comprise an acrylamide-based polymer. In some embodiments, the first basic polymer may comprise one or more cationic monomers. In some embodiments, the second basic polymer may comprise one or more cationic monomers. In some embodiments, the first basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50. In some embodiments, the second basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50. In some embodiments, the first basic polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the second basic polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the first basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, the second basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, one or more cationic monomers may comprise DADMAC and / or acryloyloxyethyltrimethylammonium chloride (also known as Q9). In some embodiments, the backbone polymer may comprise an acrylamide-based polymer, wherein the acrylamide monomer is replaced with other primary amide-containing monomers such as methacrylamide, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethyl methacrylamide, and any combination thereof.In some embodiments, the backbone polymer may comprise an acrylamide monomer. In some embodiments, the viscosity of the cationic GPAM composition may be, for example, about 10 cP or more, about 15 cP or more, about 20 cP or more, about 25 cP or more, about 30 cP or more, or about 35 cP or more when measured by an LV Brookfield viscometer at 25°C and 600 rpm using spindle number 1. The cationic GPAM composition described herein may be used in any papermaking process as further described herein. Additionally, the cationic GPAM composition described herein has the characteristic of providing benefits to manufacturers and end users of the cationic GPAM composition by lowering shipping and manufacturing costs.

[0055] The term "white water" as used herein generally refers to process water and / or produced water that can be removed from the pulp feed during the formation of paper products, e.g., sheets, e.g., hand sheets.

[0056] Composition and method

[0057] I. Cationic GPAM composition

[0058] GPAM compositions have applications in the paper industry generally known as wet and / or dry reinforcing agents. However, conventional GPAMs generally need to be stored and transported in large bulk aqueous carrier fluids, which often requires large-capacity containers or tankers for transport. Transporting such large volumes of product significantly increases the cost of transporting and using GPAM compositions. As such, there is a need for improved GPAM compositions, such as compositions containing cationic GPAMs that are useful in papermaking processes and possess storage properties that lead to reduced transport costs.

[0059] To this end, the present disclosure relates to an improved glyoxalated polyacrylamide (GPAM) composition suitable for use as a dry and / or wet reinforcing agent, wherein the aforementioned cationic GPAM composition comprises a first basic polymer having a weight average molecular weight of less than 30,000 Da and a second basic polymer having a weight average molecular weight of at least 30,000 Da, wherein the first basic polymer and the second basic polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, and further optionally about 30:70 to about 70:30, and the first basic polymer and the second basic polymer are each glyoxalated, and the composition has improved storage characteristics useful for papermaking processes and leading to reduced transport costs, and further optionally the cationic GPAM composition has a reduced volume of storage or transport compared to the volume of aqueous carrier required for conventional GPAM used in papermaking An aqueous carrier is required for this. For example, the volume of the aqueous carrier used during transport of the cationic GPAM composition discussed herein may be smaller than the volume used to transport conventional GPAM. For example, in some cases, conventional GPAM may contain a solid content percentage of 4% or less, whereas in some embodiments, the cationic GPAM composition may contain a solid content percentage of greater than 4%, i.e., greater than 4% to about 11%, for example, greater than about 5% to about 9%, for example, greater than about 5% to about 8%, or about 6% to about 7.5%.

[0060] In some embodiments, the cationic GPAM composition may include a first basic polymer having a weight average molecular weight of up to 25 kDa, 20 kDa, 15 kDa, 10 kDa, or 8 kDa. In some embodiments, the cationic GPAM composition may comprise a second basic polymer having a weight average molecular weight of at least 30 kDa, 40 kDa, 50 kDa, 75 kDa, 100 kDa, 125 kDa, 150 kDa, 175 kDa, 200 kDa, 225 kDa, 250 kDa, 275 kDa, 300 kDa, 325 kDa, 350 kDa, 375 kDa, 400 kDa, or 500 kDa.

[0061] In some embodiments, the glyoxalation percentage of the cationic GPAM composition may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the glyoxalation percentage of the first basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%. In some embodiments, the glyoxalation percentage of the second basic polymer may be about 2% to about 90%, optionally about 3% to about 80%, additionally optionally about 4% to about 70%, and additionally optionally about 5% to about 60%.

[0062] In some embodiments, the weight average molecular weight of the first basic polymer is in the range of 2 to 25 kDa, 5 to 20 kDa, or 5 to 15 kDa.

[0063] In some embodiments, the weight average molecular weight of the second basic polymer is in the range of at least 100 kDa to 500 kDa, 150 to 400 kDa, 200 to 300 kDa, 225 kDa to 275 kDa, or about 250 kDa.

[0064] In some embodiments, either or both of the first and second basic polymers comprise a copolymer 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, and the percentage ratio of the first and second monomers is in the range of about 30:70 to about 70:30.

[0065] In some embodiments, either or both of the first and second basic polymers comprise a copolymer 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, and the percentage ratio of the first and second monomers is in the range of about 40:60 to about 60:40, or about 40:60.

[0066] In some embodiments of the glyoxalation reaction used to produce glyoxylated first and second basic polymers, the ratio of glyoxal to basic polymer is in the range of about 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, or includes about 30:70.

[0067] In some embodiments, the ratio of the first and second basic polymers is in the range of 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0068] In some embodiments, either or both of the first and second basic polymers comprise a copolymer of acrylamide and DADMAC (dimethyldiallylammonium chloride), and the percentage ratio of the acrylamide and DADMAC monomers is in the range of about 40:60 to about 60:40; and the ratio of the first and second basic polymers in the reinforcing agent is in the range of 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0069] In some embodiments, both the first and second basic polymers comprise copolymers of acrylamide and DADMAC, and the weight average molecular weight of the first basic polymer is in the range of 2 to 25 kDa, 5 to 20 kDa, or 5 to 15 kDa; the weight average molecular weight of the second basic polymer is in the range of at least 100 kDa to 500 kDa, 150 to 400 kDa, 200 to 300 kDa, 225 kDa to 275 kDa, or about 250 kDa; and the ratio of the first and second basic polymers is in the range of 20:80 to 80:20, 30:70 to 70:30, or 40:60 to 60:40.

[0070] In some embodiments, the GPAM content of the cationic GPAM composition may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the GPAM content of the first basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%. In some embodiments, the GPAM content of the second basic polymer may be about 2% to about 20%, optionally about 3% to about 10%, additionally optionally about 4% to about 8%, and additionally optionally about 5% to about 7%.

[0071] In some embodiments, the first basic polymer may comprise a cationic content of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the first basic polymer is optionally amphoteric. In some embodiments, the second basic polymer may comprise a cationic content of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the second basic polymer is optionally amphoteric.

[0072] In some embodiments, the first basic polymer may comprise a percentage of cationic monomers of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the first basic polymer may optionally be amphoteric. In some embodiments, the second basic polymer may comprise a percentage of cationic monomers of at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 50 wt%, or at least 60 wt%, wherein the second basic polymer may optionally be amphoteric.

[0073] 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 cationic GPAM composition may comprise a weight percentage of solids of about 1.0% to about 20.0%, optionally about 3.0% to about 15%.

[0074] In some embodiments, the cationic GPAM composition may comprise a glyoxal to total basic 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.

[0075] In some embodiments, the first basic polymer may comprise an acrylamide-based polymer. In some embodiments, the second basic polymer may comprise an acrylamide-based polymer. In some embodiments, the first basic polymer may comprise one or more cationic monomers. In some embodiments, the second basic polymer may comprise one or more cationic monomers. A person skilled in the art will be able to easily determine an appropriate cationic monomer:acrylamide weight ratio for the first basic polymer and / or the second basic polymer. For example, in some embodiments, the first basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50. For example, in some embodiments, the second basic polymer may comprise a cationic monomer:acrylamide weight ratio of about 15:85 to about 60:40, optionally about 20:80 to about 55:45, and further optionally about 25:75 to about 50:50. In some embodiments, the first basic polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the second basic polymer is amphoteric and comprises more cationic monomers than anionic monomers. In some embodiments, the first basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers. In some embodiments, the second basic polymer may comprise a copolymer of acrylamide or methacrylamide and one or more cationic monomers.

[0076] In some embodiments, the viscosity of the cationic GPAM composition may be about 10 cP or more, about 15 cP or more, about 20 cP or more, about 25 cP or more, about 30 cP or more, or about 35 cP or more when measured with an LV Brookfield viscometer at 25°C and 600 rpm using spindle number 1.

[0077] In some embodiments, the cationic monomers of the first and second basic polymers of the cationic GPAM composition may comprise any one or more of the cationic monomers described herein. In some embodiments, one or more cationic monomers are each acryloyloxyethyl trimethylammonium chloride ("AETAC"), methacryloyloxyethyl trimethylammonium chloride, methacrylamidopropyl trimethylammonium chloride ("MAPTAC"), acrylamidopropyl trimethylammonium chloride, methacryloyloxyethyl dimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, diallyldimethylammonium chloride ("DADMAC"); Dialkylaminoalkyl acrylate, and methacrylate, and quaternary salt of dimethylaminoethyl acrylate methyl chloride ("DMAEA.MCQ"), quaternary salt of dimethylaminoethyl acrylate methyl sulfate ("DMAEM.MCQ"), quaternary salt of dimethylaminoethyl acrylate benzyl chloride ("DMAEA."BCQ"), dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of dimethylaminoethyl methacrylate benzyl chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacryloyl hydrochloride, dialkylaminoalkylacrylamide or methacrylamide and their quaternary salts or salts, e.g., acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylmethacrylamide methyl sulfate, dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide It may be selected from the group consisting of hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diallyldialkylammonium halides such as diallyldiethylammonium chloride and diallyldimethylammonium chloride, but not limited thereto, quaternary salts or salts thereof. 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 more cationic monomers may each be selected from the group consisting of methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (also known as Q9), 3-(methacrylamido)propyltrimethylammonium chloride, 3-(acryloylamido)propyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide.

[0078] In some embodiments, the acrylamide-based polymers of the first and second basic 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, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethyl methacrylamide, and any combination thereof. In some embodiments, the acrylamide-based polymer may comprise one or more acrylamide monomers.

[0079] The characteristics of such cationic GPAM compositions, such as the amount of cations, the percentage of cationic monomers, the percentage of solids, the GPAM content, and / or the glyoxalation percentage, demonstrate desirable end-use performance when compared to conventional GPAMs, and because the characteristics of the cationic GPAM disclosed and exemplified herein provide a significant reduction in the volume of products required for transport and handling, such as those involving, for example, railway tanker cars or tanker truck transport, significant savings in cost and handling can be achieved through the use of the cationic GPAM.

[0080] In some embodiments, the cationic polyacrylamide of the cationic GPAM, i.e., the cationic polyacrylamide of the first basic polymer and / or the second basic polymer, may comprise a cationic copolymer of acrylamide or methacrylamide (cPAM). In some embodiments, the cPAM may comprise a cationic copolymer of acrylamide or methacrylamide that may be produced by copolymerizing acrylamide or methacrylamide with one or more cationic monomer(s). In some embodiments, the aforementioned one or more cationic monomers may comprise any one or more cationic monomers discussed herein. In some embodiments, the above-described one or more cationic monomers may include, but are not limited to, methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride (also known as Q9), 3-(methacrylamido)propyltrimethylammonium chloride, 3-(acryloylamido)propyltrimethylammonium chloride, diallyldimethylammonium chloride (DADMAC), dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, and similar monomers. In some embodiments, the cationic GPAM may comprise a cationic monomer comprising any one or more of 2-vinylpyridine, 2-vinyl-N-methylpyridinium 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-acrylamido-3-methylbutyltrimethylammonium chloride, or any combination thereof. In some embodiments, the cPAM may comprise a copolymer of acrylamide or methacrylamide and DADMAC. In some embodiments, the cPAM may comprise a copolymer of acrylamide or methacrylamide and Q9.In some embodiments, the cPAM may comprise one or more cationic monomers as discussed herein, a total cationic volume, and an acrylamide or methacrylamide backbone. In some embodiments, the cPAM may comprise an acrylamide or methacrylamide-based polymer that is treated after polymerization to make it cationic, for example, by using a Hofmann or Mannish reaction. In some embodiments, the cPAM may comprise a cationic copolymer of acrylamide or methacrylamide that can be prepared by conventional radical-initiated polymerization methods.

[0081] In some embodiments, the backbone polymer, e.g., the backbone of the first basic polymer and / or the backbone of the second basic polymer, may comprise an acrylamide-based polymer, wherein the acrylamide monomer is replaced with other primary amide-containing monomers such as methacrylamide, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethyl methacrylamide, and any combination thereof. In some embodiments, the backbone polymer may comprise an acrylamide monomer. In some embodiments, one or more cationic monomers are acryloyloxyethyl trimethylammonium chloride ("AETAC"), methacryloyloxyethyl trimethylammonium chloride, methacrylamidopropyl trimethylammonium chloride ("MAPTAC"), acrylamidopropyl trimethylammonium chloride, methacryloyloxyethyl dimethylammonium sulfate, dimethylaminoethyl acrylate, dimethylaminopropyl methacrylamide, methacryloyloxyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, diallyldimethylammonium chloride ("DADMAC"); dialkylaminoalkyl acrylate, and methacrylate, and quaternary salt of dimethylaminoethyl acrylate methyl chloride ("DMAEA.MCQ"), quaternary salt of dimethylaminoethyl acrylate methyl sulfate ("DMAEM.MCQ"), quaternary salt of dimethylaminoethyl acrylate benzyl chloride ("DMAEA.BCQ"), dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of dimethylaminoethyl methacrylate benzyl chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacryloyl hydrochloride, dialkylaminoalkylacrylamide or methacrylamide and their quaternary salts or salts, e.g., acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylacrylamide methyl sulfate, dimethylaminopropylacrylamide sulfate, dimethylaminopropylacrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropylmethacrylamide methyl sulfate, dimethylaminopropylmethacrylamide sulfate, dimethylaminopropylmethacrylamide It may be selected from the group consisting of hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diallyldialkylammonium halides such as diallyldiethylammonium chloride and diallyldimethylammonium chloride, but not limited thereto, quaternary salts or salts thereof. In an exemplary embodiment, the first or second basic polymer may comprise or consist of (i) a first monomer comprising acrylamide and / or methacrylamide; and (ii) a second monomer comprising DADMAC or Q9 monomer, wherein optionally the percentage ratio of the first and second monomers is in the range of about 30:70 to about 70:30 or 40:60 to about 60:40.

[0082] II. Method of using cationic GPAM composition

[0083] Based on the foregoing, the present disclosure also generally relates to a papermaking method, wherein the method comprises the step of adding one or more cationic GPAM compositions as described above, wherein, based on the composition, the method has storage characteristics that are useful for the papermaking process and lead to a reduction in transportation costs; wherein the method generally comprises the step of adding one or more of these cationic GPAM compositions during the papermaking method in an amount effective for increasing the wet strength and / or dry strength of the paper. In some embodiments, one or more cationic GPAM compositions are added to a composition comprising fibers 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 is formed. In some embodiments, the cationic GPAM composition may comprise any one or more of the cationic GPAM compositions disclosed herein. In some embodiments, the cationic GPAM composition may comprise a first basic polymer having a weight average molecular weight of less than 30,000 Da and a second basic polymer having a weight average molecular weight of at least 30,000 Da, wherein optionally, the first basic polymer and the second basic polymer comprise or consist of (i) a first monomer comprising acrylamide and / or methacrylamide; and (ii) a second monomer comprising DADMAC or Q9 monomer, additionally optionally, the first basic polymer and the second basic polymer have a weight ratio of about 10:90 to about 90:10, optionally about 20:80 to about 80:20, additionally optionally about 30:70 to about 70:30 or about 40:60 to about 60:40, wherein the first basic polymer and the second basic polymer are each glyoxalated.

[0084] In some embodiments, the cationic GPAM compositions described herein provide a thermosetting resin particularly suitable for use as an additive in a papermaking method. That is, the addition of the aforementioned cationic GPAM compositions leads to the production of paper having desirable dry and transient wet strength and / or an increase in the papermaking dehydration rate.

[0085] In addition, the present disclosure also relates to paper products comprising one or more improved GPAM compositions as disclosed herein. In some embodiments, the paper product may comprise at least one paper layer or web containing the cationic GPAM composition, e.g., paper sheet, cardboard, tissue 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 particular type of paper or papermaking method, and applications may be found in kraft paper, sulfite paper, semi-chemical paper, etc., including paper produced using bleached pulp, unbleached pulp, or a combination thereof.

[0086] When using a cationic GPAM composition as disclosed herein during a papermaking method, the cationic GPAM composition may be added at any time before, during, and / or after paper formation. In some cases, the cationic GPAM composition may be added to a cellulose fiber suspension at the wet end of the papermaking facility, generally at the time when a wet reinforcing resin is typically added. In some embodiments, the cationic GPAM composition may be added to one or more surfaces of previously manufactured paper, e.g., paper previously manufactured by padding, spraying, dipping, and / or printing. Additionally, in some embodiments, the cationic GPAM composition may be added to the paper pulp over a wide range of pH values, such as about 4 to about 9.

[0087] In some cases, the amount of cationic GPAM composition added during the papermaking method may be in the range of about 0.02% to about 10% based on the dry weight of the cellulose fibers, for example, in the range of about 0.05 wt% to 5 wt% based on the dry weight of the paper.

[0088] Additionally, the present disclosure relates to paper products, for example, hand sheets comprising one or more cationic GPAMs, for example, cationic GPAMs as described above, which are useful in papermaking processes based on their composition and optionally have storage properties leading to a reduction in transportation costs. In some embodiments, the paper products may include fiber-based products, for example, hand sheets, cardboard-based products, beverage containers, towels, milk and juice cartons, food trays, paper bags, corrugated container liner cardboard, packaging carton grades, and tissue and towel grades, paper materials, paper towels, diapers, sanitary pads, training panties, panty liners, incontinence briefs, tampons, urine pads, urinary box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent face tissues, absorbent bathroom tissues, napkins, wrapping paper, and / or other paperboard products such as carton and bag paper. In some embodiments, the paper product may comprise a cellulose paperboard web comprising (a) mostly cellulose fibers and (b) one or more cationic GPAM compositions.

[0089] In some embodiments, the paper product may have improved paper strength compared to a paper product that does not contain a cationic GPAM composition, for example, when measured by an STFI test. For example, in some embodiments, the paper product may include a hand sheet containing one or more cationic GPAM compositions, wherein the hand sheet described above may have an improved 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, or 25.0% or more in a 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a blank sample used in the STFI test.

[0090] In some embodiments, the paper product may have improved paper strength when measured, for example, by a burst strength test, compared to a paper product that does not contain a cationic GPAM composition. For example, in some embodiments, a hand sheet comprising one or more cationic GPAM compositions may have an improved burst strength 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 a 4.5 lbs / ton, 5.0 lbs / ton, 9.0 lbs / ton, or 10 lbs / ton test compared to a blank sample used in a burst strength test.

[0091] In some embodiments, the cationic GPAM composition can reduce the discharge time of the treated sample compared to the discharge time when the cationic GPAM composition is not used. For example, in some embodiments, the cationic GPAM composition can affect efficient discharge, such as showing an improvement of at least 25.0%, 30.0%, 35.0%, 40.0%, 45.0%, 50.0%, or 55.0% in the time to collect a given amount of filtrate from OCC pulp compared to the discharge when the cationic GPAM composition is not used. In some embodiments, the cationic GPAM composition increases the discharge rate of the treated sample compared to the discharge rate when the cationic GPAM composition is not used, which leads to an increase in the paper production rate. In some embodiments, the cationic GPAM composition can improve the energy savings required for the drying step of the papermaking method. Additionally, the cationic GPAM composition may affect the reduction of the total amount of solids present in the treated sample, such as an improvement (reduction in solid 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% compared to the total amount of solids present in the sample when the cationic GPAM composition is not used, for example, a reduction in the total solids present in the filtrate collected from OCC pulp treated with the cationic GPAM composition, for example, a reduction in the solid content of white water from tray or silo pre-sheet formation. In some embodiments, the cationic GPAM composition may improve the energy savings required for drying.

[0092] In addition, the present disclosure generally relates to a method for manufacturing a hand sheet, wherein the above-described method comprises: 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-forming agent; g. pressing the sheet produced from step f; h. drying the sheet; and i. conditioning the sheet.

[0093] Additionally, the present disclosure relates to a method for generally manufacturing one or more paper products, wherein the method comprises: a. providing a composition comprising mostly cellulose fibers; b. adding a predetermined amount of one or more cationic GPAM compositions; and c. forming a desired paper product.

[0094] Additionally, the present disclosure comprises a method for generally manufacturing one or more paper products, for example, one or more adsorbent paper products, wherein the method comprises: a. providing a composition comprising one of soft wood fibers, hard wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above in an amount sufficient to form a total feed of about 1 to 100% of hard wood fibers, soft wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above; (b) adding a predetermined amount of one or more cationic GPAM compositions as discussed herein; and (c) forming a paper product by drying to a desired moisture content level through one or more drying means.

[0095] Additionally, the present disclosure generally relates to a method for reinforcing paper, wherein the method comprises: (i) contacting a pulp fiber with a reinforcing resin comprising at least one cationic GPAM composition, for example, at least one of the improved cationic GPAM compositions described herein, wherein the GPAM composition has specific properties that make it highly suitable for use in a papermaking process; and (ii) at least partially curing a reinforcing resin comprising at least one cationic GPAM composition in a mixture of the pulp fiber and the cationic GPAM composition to produce a paper product having enhanced strength.

[0096] III. Method for preparing a cationic GPAM composition

[0097] The present disclosure also relates to a method for preparing a cationic GPAM composition, generally disclosed herein, comprising a first basic polymer having a weight average molecular weight of less than 30,000 Da, optionally 2 to 25 kDa, or 5 to 15 kDa, and a second basic polymer having a weight average molecular weight of at least 30,000 Da, optionally at least 50 kDa, or in the range of 100 kDa to 500 kDa, 150 to 400 kDa, 200 to 300 kDa, 225 kDa to 275 kDa, or about 250 kDa, wherein, additionally optionally, the first basic polymer and / or the second basic polymer comprises (i) an acrylamide or methacrylamide monomer, and (ii) a DADMAC or Q9 monomer, wherein the first basic polymer and the second basic The polymer has 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 60:40; the first basic polymer and the second basic polymer are each glyoxalated; optionally, the cationic GPAM composition requires a reduced volume of aqueous carrier compared to the volume of aqueous carrier required for conventional GPAM used in papermaking for storage or transport.

[0098] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. glyoxalizing a first basic polymer in a first glyoxalization reaction comprising glyoxal to produce a first glyoxalized basic polymer; b. glyoxalizing a second basic polymer in a second glyoxalization reaction comprising glyoxal to produce a second glyoxalized basic polymer; and c. combining the first glyoxalized basic polymer and the second glyoxalized basic polymer to produce a cationic GPAM composition; and steps (a) and (b) may be performed in any order or simultaneously.

[0099] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. combining a first basic polymer and a second basic polymer; and b. glyoxalizing the combination of the first basic polymer and the second basic polymer in a glyoxalization reaction comprising glyoxal to produce a cationic GPAM composition.

[0100] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. glyoxalizing a first basic polymer in a glyoxalization reaction comprising glyoxal to produce a first glyoxalized basic polymer; and b. adding a second basic polymer, and optionally additional glyoxal, to the glyoxalization reaction to produce a cationic GPAM composition.

[0101] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. glyoxalizing a second basic polymer in a glyoxalization reaction comprising glyoxal to produce a second glyoxalized basic polymer; and b. adding a first basic polymer and optionally additional glyoxal to the glyoxalization reaction to produce a cationic GPAM composition.

[0102] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. glyoxalizing a first basic polymer in a first glyoxalization reaction comprising glyoxal to produce a first glyoxalized basic polymer; and b. glyoxalizing a second basic polymer in a second glyoxalization reaction comprising glyoxal and the first glyoxalized basic polymer to produce a cationic GPAM composition.

[0103] In some embodiments, a method for preparing a cationic GPAM composition disclosed herein may comprise: a. glyoxalizing a second basic polymer in a second glyoxalization reaction comprising glyoxal to produce a second glyoxalized basic polymer; and b. glyoxalizing a first basic polymer in a first glyoxalization reaction comprising glyoxal and the second glyoxalized basic polymer to produce a cationic GPAM composition.

[0104] The compositions and methods disclosed herein by way of example may be practiced in the absence of any element not specifically disclosed herein and / or any element specifically disclosed herein.

[0105] Examples

[0106] Example 1: Preparation of Sample and Hand Sheet

[0107] The cationic GPAM composition and hand sheet used in the following examples were prepared as follows. Table 1 All GPAM samples were prepared by reacting the cationic polyacrylamide basic polymer shown in with glyoxal.

[0108] Basic polymer composition Sample Basic polymer MW (kilodalton, kD) Basic polymer volume % (wt%) Basic polymer 1* 8 40% Basic polymer 2* 15 10% Basic polymer 3 246 40%

[0109] * Basic polymers 1, 2, and 3 are each copolymers composed of acrylamide and DADMAC (dimethyldiallylammonium chloride) monomers.

[0110] In the embodiments of the present invention, cationic copolymers comprising acrylamide and DADMAC monomers were used because these copolymers are widely used as "model" cationic polymers. Therefore, the results obtained using these copolymers can reasonably be expected to be obtained using other cationic polymers, such as cationic copolymers comprising other cationic monomers disclosed herein.

[0111] Table 2 Is Table 1 The composition of GPAM samples prepared by reacting a basic polymer with glyoxal is described. For each reaction, the glyoxal:basic polymer ratio was 29:71.

[0112] GPAM sample composition Sample manufacturing method Solids GPAM 1 Glyoxalation of basic polymer 1. 14% GPAM 2 Glyoxalation of basic polymer 3. 5% GPAM 3 Glyoxalation of a 20:80 mixture of basic polymer 1 and basic polymer 3. 6.1% GPAM 4 Glyoxalation of a 30:70 mixture of basic polymer 1 and basic polymer 3. 7.3% GPAM 5 25:75 mixture of GPAM 1:GPAM 2. 6.0% GPAM 6 33:67 mixture of GPAM 1:GPAM 2. 6.4% GPAM 7 The glyoxalation reaction of basic polymer 3 was performed in the presence of GPAM 1. The ratio of basic polymer 1 to basic polymer 3 was 25:75. 6.0% GPAM 8 Glyoxalation of basic polymer 2. 7.0% GPAM 9 Glyoxalation of a 25:75 mixture of basic polymer 2 and basic polymer 3. 7.0% GPAM 10 Glyoxalation of a 40:60 mixture of basic polymer 2 and basic polymer 3. 6.7% GPAM 11 Glyoxalation of a 60:40 mixture of basic polymer 2 and basic polymer 3. 7.2%

[0113] GPAM 1, GPAM 2, and GPAM 8 are conventional GPAM compositions. GPAM 1 was prepared using a low molecular weight (8 kDa) basic polymer 1 and has a high final solid content (14%), whereas GPAM 2 was prepared using a high molecular weight (246 kDa) basic polymer 3 and has a low final solid content (5%). GPAM 8 was prepared using a low molecular weight (15 kDa) basic polymer 2.

[0114] New GPAM compositions 3 to 7 were prepared in various ways using both basic polymers 1 and 3. GPAM 3 and GPAM 4 were prepared by glyoxalation of a basic polymer blend. GPAM 5 and GPAM 6 were simple blends of GPAM 1 and GPAM 2. GPAM 7 was prepared by a two-step reaction. In the first step, GPAM 1 was produced by glyoxalation of basic polymer 1. In the second step, basic polymer 3 and more glyoxal were added to the finished GPAM 1, and an additional glyoxalation reaction was performed to produce the final GPAM 7 composition.

[0115] The new GPAMs 3 through 7 had significantly higher solid content than GPAM 2 (5.0%), which was produced from basic polymer 3. For example, GPAM 4 had a solid content of 7.3%, which was 46% higher than the content of GPAM 2. When GPAM products are produced with a solid content of less than 6%, costs associated with production, delivery, and handling are often higher than the cost of raw materials. Consequently, a 45% increase in product solid content resulted in a significant reduction in the total cost of the product.

[0116] New GPAMs 9 to 11 were prepared by performing a glyoxalation reaction of a blended mixture of basic polymer 2 and basic polymer 3. The ratio of basic polymer 2 to basic polymer 3 is graph 2 It was as shown in. graph 2 As shown in [figure], GPAM 9, 10, and 11 have solid content of 7.0%, 6.7%, and 7.2%, respectively, which is significantly higher than the solid content of GPAM 2 (5.0%) made from basic polymer 3, thus resulting in a significant reduction in the total cost of the product.

[0117] Hand sheets were prepared using the aforementioned GPAM as follows: A concentrated stock of OCC pulp was obtained from a recycled liner cardboard mill. First, the concentrated stock was diluted to a concentration of 0.5% using tap water. NaCl was added to the diluted pulp to match the conductivity of the mill white water. Then, a 1 M HCl solution was added to the pulp to adjust the pH to 6.4. Second, the GPAM composition was introduced into the diluted pulp under overhead stirring. Then, the treated pulp was added to a dynamic sheet forming agent (DSF) (TECHPAP France, Type - FDA) to produce a 110 gsm sheet. Next, the formed sheet was pressed into blotting paper using a pneumatic roll press at 15 psi and then dried on a rotary dryer at 110°C. Next, the dry paper sheet was cured in an oven (forced air convection oven) at 105°C for 5 minutes, and then conditioned overnight in a standard TAPPI control room. Finally, the paper strip was cut along the transverse direction.

[0118] Example 2: Burst strength test

[0119] A burst strength test was performed according to TAPPI standard method T-403. Table 3 represents the result.

[0120] Rupture strength of hand sheets treated with various GPAM products 5 lb / ton 10 lb / ton Sample rupture improvement rupture improvement 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%

[0121] graph 3 As shown in [figure], the new GPAM 3 and GPAM 4, respectively, provided dry strength performance similar to GPAM 2. In addition, these new GPAM products had a significantly higher solid content than GPAM 2.

[0122] Example 3: STFI Test

[0123] STFI testing was performed according to TAPPI standard method T-826. Table 4 and Table 5 represents the result.

[0124] STFI strength of hand sheets treated with various GPAM products 9 lb / ton Sample STFI improvement 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%

[0125] STFI strength of hand sheets treated with various GPAM products 4.5 lb / ton Sample STFI improvement 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%

[0126] Table 4 As shown in [figure], the new GPAM 5, GPAM 6, and GPAM 7 each provided dry strength performance similar to GPAM 2. In addition, as discussed above, these new GPAM products had a significantly higher solid content than GPAM 2.

[0127] graph 5 Figure 1 shows the STFI results for hand sheets treated with conventional GPAM 2 and GPAM 8, prepared from basic polymer 3 and basic polymer 2, respectively, and hand sheets treated with new GPAM compositions 9 to 11. Conventional GPAM 2 and GPAM 8 increased STFI by 8.3% and 3.5%, respectively. By comparison, new GPAM 9 to 11 increased STFI by 8.8%, 12.4%, and 14.4%, respectively. This study clearly demonstrated that new GPAM compositions prepared from a combination of basic polymer 2 and basic polymer 3 can provide comparable or significantly greater paper strength improvement compared to conventional GPAM prepared from only one of basic polymer 2 or basic polymer 3.

[0128] In the aforementioned procedure, various steps have been described. However, it will be apparent that various variations and modifications may be made to the exemplary procedure as set forth in the following claims, and that additional procedures may be implemented, without exceeding the broader scope of the exemplary procedure.

Claims

Claim 1 A cationic glyoxalated polyacrylamide ("GPAM") composition for use as a dry or wet reinforcing agent, wherein the cationic GPAM composition comprises: i. a first basic polymer having a weight average molecular weight in the range of 7 to 25 kDa prior to glyoxalation; ii. a second basic polymer having a weight average molecular weight in the range of 50 to 500 kDa prior to glyoxalation; and iii. a weight ratio of the first basic polymer to the second basic polymer of 10:90 to 90:10, wherein the first basic polymer is glyoxalated and the second basic polymer is glyoxalated; wherein the first basic polymer is an acrylamide-based polymer comprising one or more acrylamide-based monomers and one or more cationic monomers; and wherein the second basic polymer is an acrylamide-based polymer comprising one or more acrylamide-based monomers and one or more cationic monomers. Claim 2 The cationic GPAM composition of claim 1 comprises: i. a glyoxalization percentage of the cationic GPAM composition of 2% to 90%; ii. a glyoxalization percentage of the first basic polymer of 2% to 90%; iii. a glyoxalization percentage of the second basic polymer of 2% to 90%; iv. a GPAM content of 2% to 20% by weight; v. a viscosity of 10 to 35 cP when measured by an LV Brookfield viscometer at 25°C and 60 rpm using spindle number 1; vi. a solid content weight percentage of 1.0% to 20.0% by weight; vii. a glyoxal to basic polymer weight ratio of 1:99 to 30:70; or viii. any combination of items (i) to (vii), the cationic GPAM. Claim 3 A cationic GPAM composition according to claim 1, wherein i. the first basic polymer comprises a cationic amount; ii. the second basic polymer comprises a cationic amount; iii. the first basic polymer comprises a cationic monomer percentage of 5% to 60% by weight; iv. the second basic polymer comprises a cationic monomer percentage of 5% to 60% by weight; v. the first basic polymer is amphoteric and comprises one or more acrylamide-based monomers, one or more cationic monomers, and one or more anionic monomers; vi. the second basic polymer is amphoteric and comprises one or more acrylamide-based monomers, one or more cationic monomers, and one or more anionic monomers; vii. any combination of items (i) to (vi). Claim 4 In paragraph 3, i. one or more acrylamide monomers are selected from the group consisting of acrylamide, methacrylamide, ethylacrylamide, crotonamide, N-methylacrylamide, N-butylacrylamide, N-ethylmethacrylamide, and any combination thereof; or ii. One or more cationic monomers are acryloyloxyethyl trimethylammonium chloride ("AETAC"), methacryloyloxyethyl trimethylammonium chloride, methacrylamidopropyl trimethylammonium chloride ("MAPTAC"), acrylamidopropyl trimethylammonium chloride, methacryloyloxyethyl dimethylammonium sulfate, dimethylaminoethyl acrylate, methacryloyloxyethyl trimethylammonium chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminopropyl methacrylamide, diallyldimethylammonium chloride ("DADMAC"), dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, quaternary salt of dimethylaminoethyl acrylate methyl chloride ("DMAEA.MCQ"), quaternary salt of dimethylaminoethyl acrylate methyl sulfate ("DMAEM.MCQ"), quaternary salt of dimethylaminoethyl acrylate benzyl chloride ("DMAEA."BCQ"), dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, diethylaminoethyl acrylate, quaternary salt of methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl chloride, quaternary salt of dimethylaminoethyl methacrylate methyl sulfate, quaternary salt of dimethylaminoethyl methacrylate benzyl chloride, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dimethylaminoethyl methacryloyl hydrochloride, dialkylaminoalkylacrylamide, methacrylamide and their quaternary or acid salts, acrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropyl acrylamide methyl sulfate, dimethylaminopropyl acrylamide sulfate, dimethylaminopropyl acrylamide hydrochloride, methacrylamidopropyltrimethylammonium chloride, quaternary salt of dimethylaminopropyl methacrylamide methyl sulfate, dimethylaminopropyl methacrylamide sulfate, dimethylaminopropyl methacrylamide iii. Selected from the group consisting of hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and diallyldialkylammonium halide, diallyldiethylammonium chloride and diallyldimethylammonium chloride, and any combination thereof; iii. One or more anionic monomers selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, 2-hydroxy-3-acrylamidepropanesulfonic acid, styrene sulfonic acid, vinyl phosphonic acid, and combinations thereof, as well as their corresponding water-soluble or dispersible alkali metals, alkaline earth metals, and ammonium salts, and any combination thereof; iv. A cationic GPAM composition which is any combination of items (i) to (iii). Claim 5 A cationic GPAM according to claim 4, wherein i. the first basic polymer comprises (a) acrylamide, methacrylamide, or a combination thereof; and (b) a copolymer comprising dimethyldiallylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), or a combination thereof; and ii. the second basic polymer comprises (a) acrylamide, methacrylamide, or a combination thereof; and (b) a copolymer comprising dimethyldiallylammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium chloride (AETAC), or a combination thereof. Claim 6 A cationic GPAM composition according to claim 4, wherein i. the first basic polymer comprises a copolymer comprising acrylamide and dimethyldiallyammonium chloride (DADMAC); and ii. the second basic polymer comprises a copolymer comprising acrylamide and dimethyldiallyammonium chloride (DADMAC). Claim 7 A paper product comprising one or more cationic GPAM compositions according to any one of claims 1 to 6. Claim 8 In claim 7, the paper product comprises: i. at least one paper layer or web containing a cationic GPAM composition; ii. a cationic GPAM composition on at least one surface of the paper product; iii. one or more of paper sheets, paperboard, tissue paper, and wallpaper; iv. one or more of kraft paper, sulfite paper, and semi-chemical paper, including paper produced using bleached pulp, unbleached pulp, or a combination thereof; v. a fiber-based product; and vi. One or more of hand sheets, cardboard-based products, beverage containers, towels, milk and juice cartons, food trays, paper bags, corrugated container liner cartons, packaging carton grades, and tissue and towel grades, paper materials, paper towels, diapers, sanitary pads, training panties, panty liners, incontinence briefs, tampons, urine pads, potty box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent facial tissues, absorbent bathroom tissues, napkins, wrapping paper, other paperboard products, cartons, and bag paper; vii. comprising a cellulose paperboard web comprising cellulose fibers; viii. comprising cellulose fibers, and a cationic GPAM composition in the range of 0.02% to 10% based on the dry weight of the cellulose fibers, or a cationic GPAM composition in the range of 0.05 wt% to 5 wt% based on the dry weight of the cellulose fibers; or ix. A paper product having improved paper strength when measured by STFI testing compared to a paper product not containing a cationic GPAM composition; x; having improved paper strength when measured by burst strength testing compared to a paper product not containing a cationic GPAM composition; xi; and any two or more combinations of items (i) to (x). Claim 9 A papermaking method comprising: i. forming a paper product from a composition comprising cellulose fibers; and ii. adding at least one cationic GPAM composition according to any one of claims 1 to 6 during the papermaking method in an amount effective for increasing the wet or dry strength of the paper product, wherein (a) the cationic GPAM composition is added to the composition comprising cellulose fibers before the paper product is formed; (b) the cationic GPAM composition is added to one or more surfaces of the paper product after the paper product is formed; and (c) the cationic GPAM composition is added to the composition comprising cellulose fibers before the paper product is formed, and the cationic GPAM composition is added to one or more surfaces of the paper product after the paper product is formed. Claim 10 In claim 9, the method comprises: (i) any one of soft wood fibers, hard wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above, in an amount sufficient to form a whole feed of 1 to 100% hard wood fibers, soft wood fibers, regenerated fibers, refined fibers, or a mixture of any one of the above; (ii) the method further comprises a step of drying a paper product to a desired moisture content level; (iii) the method further comprises a step of partially curing a reinforcing resin after adding it to the cellulose fibers; or (iv) any combination of items (i) to (iii). Claim 11 In claim 9, i. the cationic GPAM composition is added to a cellulose fiber suspension at the wet end of a papermaking facility; ii. the cationic GPAM composition is added in an amount ranging from 0.02% to 10% based on the dry weight of the cellulose fibers, or from 0.05 wt% to 5 wt% based on the dry weight of the cellulose fibers; iii. the cationic GPAM composition is added before, during, or after the formation of a paper product; iv. the cationic GPAM composition is added to one or more surfaces of a paper product after the formation of a paper product; v. the cationic GPAM composition provides enhanced paper strength to the paper product as measured by an STFI test; vi. the cationic GPAM composition provides enhanced paper strength to the paper product as measured by a burst strength test; vii. The paper product comprises one or more of hand sheets, cardboard-based products, beverage containers, towels, milk and juice cartons, food trays, paper bags, liner cardboard for corrugated containers, packaging carton grades, and tissue and towel grades, paper materials, paper towels, diapers, sanitary pads, training panties, panty liners, incontinence briefs, tampons, urine pads, potty box liners, coffee filters, air filters, dryer pads, floor cleaning pads, absorbent facial tissues, absorbent bathroom tissues, napkins, wrapping paper, other paperboard products, and carton and bag paper; viii. The paper product comprises a cellulose paperboard web containing cellulose fibers; ix. The cationic GPAM composition reduces the discharge time of the treated sample compared to the discharge time when the cationic GPAM composition is not used; x. The cationic GPAM composition increases the discharge rate of the treated sample, leading to an increase in paper production rate compared to the discharge rate when the cationic GPAM composition is not used; xi. A cationic GPAM composition improves the drying energy saving of a papermaking method or; xii.A cationic GPAM composition that reduces the total solid content of a treated sample, or the total solid content of white water from tray or silo pre-sheet formation, compared to the total solid content when the cationic GPAM composition is not used; xiii. any combination of two or more of items (i) to (xii). Claim 12 A method for preparing a cationic GPAM composition according to any one of claims 1 to 6, comprising: i. contacting a first basic polymer with glyoxal; ii. contacting a second basic polymer with glyoxal; and iii. contacting the first basic polymer with the second basic polymer; wherein steps (i) to (iii) may be performed in any order or simultaneously. Claim 13 In claim 12, i. a step of combining a first basic polymer and a second basic polymer; and a step of producing a cationic GPAM composition by contacting the combination of the first basic polymer and the second basic polymer with glyoxal; or ii. a step of producing a first glyoxalized basic polymer by contacting the first basic polymer with glyoxal; a step of producing a second glyoxalized basic polymer by contacting the second basic polymer with glyoxal; and a step of producing a cationic GPAM composition by combining the first glyoxalized basic polymer and the second glyoxalized basic polymer; or iii. a step of producing a first glyoxalized basic polymer by glyoxalizing the first basic polymer in a glyoxalization reaction containing glyoxal; and a step of producing a cationic GPAM composition by adding the second basic polymer to the glyoxalization reaction; or iv. A method comprising: a step of glyoxalizing a second basic polymer in a glyoxalization reaction containing glyoxal to produce a second glyoxalized basic polymer; and a step of adding a first basic polymer to the glyoxalization reaction to produce a cationic GPAM composition. Claim 14 A composition comprising one or more cationic GPAM compositions according to any one of claims 1 to 6. Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 delete Claim 21 delete Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete