ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING HIGH MOLECULAR WEIGH GPAM COMPOSITIONS AND METHODS OF USE AS STRENGTH AND DRAINAGE AIDS RELATED APPLICATIONS [0001] The present invention relates to and claims benefit of priority to U.S. Provisional Application Number 63/655,689, filed on June 4, 2024, and Finnish Application Number FI 20245993, filed on August 8, 2024, the contents of both are which are incorporated by reference in their entirety herein. FIELD OF THE INVENTION [0002] The present invention generally relates to glyoxalated polyacrylamide (GPAM) compositions, articles comprising, and methods of use thereof, particularly high molecular weight GPAM compositions with high GPAM standard viscosities that are useful in the paper industry, and more particularly cationic GPAM compositions and use thereof in papermaking applications and in products such as paper-based products. The present disclosure also generally relates to methods of preparing said cationic GPAM compositions and use of GPAM compositions for improving tensile strength and drainage rates of paper-based products. BACKGROUND OF THE INVENTION [0003] Glyoxylated polyacrylamide (GPAM) is used in a variety of paper grades to increase papermaking drainage and dewatering rates. GPAM additives are also used to enhance the dry and temporary wet strength of paper products and to increase the tensile strength and the dimensional stability of board-grade paper products and paper or board for printing, writing, or packaging. [0004] Strength additives and drainage aids are generally added to the furnish as it approaches the headbox of the paper machine and may also comprise a coagulant/flocculant system used in conjunction with one or more shearing stages. When used as a strength additive and/or drainage aid, GPAM is typically added in the pulp suspension before paper sheet formation. Upon drying of the treated paper sheet, GPAM forms covalent bonds with paper cellulose to increase paper dry strength. [0005] GPAM is generally prepared through the reaction between glyoxal and a cationic polyacrylamide base polymer which generally contains acrylamide monomers and a cationic monomer, such as DADMAC (for example, as discussed in U.S. Pat. Nos.3,556,932, 4,605,702, and 7,828,934). The original GPAM was reported in US Pat. No.3,556,932. The cationic polyacrylamide base polymer has a molecular weight (MW) below 25,000 Da and a molar ratio of acrylamide to diallyldimethylammonium chloride of 99:1 to 75:1. [0006] There is a generally recognized need in the art to provide GPAMs with higher MW (i.e., MW higher than 1,000 kDa) and higher final viscosity (> 50 cPs). Higher MW GPAM polymers are expected to provide improved dewatering rate during the papermaking process. In addition, higher molecular weight strength resins often results in greater paper strength properties. [0007] GPAM compositions have, to date, been limited by their final MW and viscosity. The viscosity of a polymer increases with its molecular weight, often in an exponential manner. If GPAM MW and viscosity are too high, final products are not storage-stable and tend to gel in a short period of time.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING Such products may gel before being applied to a paper machine, thereby rendering them useless as strength additives and drainage aids. [0008] US patent 4954538 discloses compositions comprising microparticles of a cross-linkable, glyoxalated (meth)acrylamide containing, polymeric material, which are useful as wet and dry strength agents for paper production. Inverse micro-emulsion polymerization was used to produce polyacrylamide base polymers of high molecular weight, typically greater than one million Dalton. The glyoxalation reaction was carried out inside polyacrylamide microparticles dispersed in continuous oil phase. However, this process allows for inter-polymer glyoxal cross-linking to occur to a large extent as glyoxal reacts with acrylamide polymer, which ultimately results in gelation of the GPAM product. [0009] US. Patent No.8222343 discloses a glyoxalated polymer prepared from vinylamide base polymer having an average molecular weight of 1.36 million Dalton and use as a strength agent for a paper or board. However, the glyoxalated polymer produced lower strength properties than the ones prepared using polyacrylamide samples below one million Dalton. [0010] US patent 8703847 discloses a method for preparing a cellulose-reactive functionalized poly- vinylamide adduct comprising reacting a substantially aqueous reaction mixture comprising a vinylamide base polymer and a cellulose reactive agent, such as glyoxal, to form the adduct. The vinylamide base polymer has an average MW of up to 500,000 Daltons; however, the concentration of the vinylamide polymer is less than 4 weight percent and the final product has a viscosity of no more than 30 cPs. [0011] Commercially available GPAM based strength agents and drainage aids remain inadequate for manufacture of paper and board, especially when using a high percentage of recycled fiber content. There remains a need in the art for high MW, high viscosity GPAM additives for use in the manufacturing of paper, tissue, towel, and/or board, especially from recycled materials, which provide drainage and strength enhancements. [0012] It is an object of the present invention to provide high MW, high GPAM standard viscosity (> 2.5 cPs) GPAM compositions, methods of making such compositions, and methods of use for improving drainage rates and/or tensile strength of paper or board products produced from a high percentage of recycled fiber content. SUMMARY OF THE INVENTION [0013] The present invention generally relates to cationic GPAM compositions having high MW, high standard viscosity (≥50 cPs), and high GPAM standard viscosity (>2.5 cPs) for use as a strength agents and drainage aids for manufacture of paper or board, especially from recycled materials. Preparation of paper sheets with the inventive GPAMS provided increases in tensile strength and DDA drainage rates. [0014] In one aspect, the present invention provides a glyoxalated polyacrylamide (GPAM) composition for use as a strength and/or drainage aid for papermaking, wherein said GPAM composition comprises: (a) at least one cationic glyoxalated polyacrylamide (GPAM) comprising a mixture of glyoxalated cationic base polymers; and (b) a GPAM standard viscosity of greater than 2.5 cPs measured as 1 wt% of said GPAM composition in 0.5 M NaCl using a Brookfield LVT viscometer at a speed of 60 rpm and reduced viscosity of at least 10 dL/g at a temperature of 25° C. [0015] In some exemplary embodiments, the GPAM composition comprises:
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0016] (a) said GPAM standard viscosity of 2.6-100 cPs, 2.7-90 cPs, 2.8-80 cPs, 2.9-70 cPs, 3-60 cPs, 4-50 cPs, 5-40 cPs, 6-30 cPs, 7-20 cPs, 8-20 cPs, 9-20 cPs, 10-20 cPs, or 4-10 cPs, 5-10 cPs, 6-10 cPs, 7- 10 cPs, 8-10 cPs, or 9-10 cPs; [0017] (b) a standard viscosity (SV) of at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300-1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs measured as 0.1 wt% of said GPAM composition in 1 M NaCl using a Brookfield LVT viscometer with UL adapter at 60 rpm, pH 5, and a temperature of 25 °C; [0018] (c) a reduced viscosity of at least 10 dL/g, at least 20 dL/g, at least 40 dL/g, at least 60 dL/g, at least 80 dL/g, at least 100 dL/g, at least 125 dL/g, at least 150 dL/g; or ranging from 10-400 dL/g, 20- 380 dL/g, 40-360 dL/g, 60-340 dL/g, 80-320 dL/g, 100-300 dL/g, 120-280 dL/g, 140-260 dL/g, 140-240 dL/g, 160-240 dL/g, or 180-220 dL/g at a temperature of 25 °C; [0019] (d) a GPAM emulsion, an inverse GPAM emulsion, or an oil-in-water GPAM emulsion comprising an aqueous continuous phase; [0020] (e) a GPAM content ranging from 1-20 wt-%; 2-10 wt-%, 3-10 wt%, 4-10 wt%, 4-8 wt-%, 4-7 wt-%, or 4-6 wt-%; [0021] (f) a ratio of glyoxal to total cationic base polymers (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3; [0022] (g) a percent glyoxalation ranging from 1-100%, 5-90%, 5-80%, 10-60%, 10-40%, 15-35%, 20- 30%, or 22-28%; [0023] (h) a net cationic charge ranging from 0.1 to 5.0 mEq/g, 0.4 to 4.0 mEq/g, 0.5 to 3.0 mEq /g, or 0.6 to 2.0 mEq /g; or [0024] (i) any combination of (a)-(h). [0025] In some exemplary embodiments of the GPAM composition, the mixture of cationic base polymers comprises: (a) a first base polymer comprising a first standard viscosity (SV) of ≤ 1.4 cPs; and a second base polymer comprising a second standard viscosity (SV) of greater than 1.4 cPs, wherein said first and second standard viscosities are measured as 0.1 wt% of base polymer in 1 M NaCl using a Brookfield LVT viscometer with UL adapter at 60 rpm, pH 5, and a temperature of 25 °C; and (b) a ratio of said first base polymer to said second base polymer (wt:wt) ranging from 99:1 to 1:99, 90:10 to 10:90, 80:20 to 20:80, 80:20 to 30:70, 80:20 to 40:60, 80:20 to 50:50, or 70:30 to 60:40. [0026] In some exemplary embodiments of the GPAM composition, the first base polymer: [0027] (a) is prepared by a radical polymerization reaction comprising a solution polymerization reaction in water, an inverse emulsion polymerization, or a dispersion polymerization, and optionally comprising a chain transfer reagent; [0028] (b) comprises said first standard viscosity (SV) ranging from ≤1.4, 1.2-1.4 cPs, 1.25-1.4 cPs, 1.3-1.4 cPs, or 1.35-1.4 cPs; [0029] (c) comprises a weight average molecular weight ranging from 10-1000 kDa, 50-1000 kDa, 100-1000 kDa, 200-1000 kDa, 300-1000 kDa, 400-1000 kDa, 500-900 kDa, or 600-800 kDa;
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0030] (d) comprises one or more acrylamide-based copolymers comprising one or more neutral monomers, one or more cationic monomers, and optionally one or more anionic monomers, wherein: [0031] (i) said one or more neutral monomers are selected from the group consisting of primary amide-containing monomers, acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof; [0032] (ii) said one or more cationic monomers are selected from the group consisting of acryloyloxyethyltrimethyl ammonium chloride (Q9), methacryloyloxyethyltrimethylammonium chloride (MAETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), methacryloyloxyethyldimethylammonium sulfate, diallyldialkylammonium halides diallyldimethylammonium chloride (DADMAC), diallyldiethylammonium chloride; dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates and their quaternary or acid salts; dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides, methacrylamides and their quaternary or acid salts; acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, and diethylaminoethylmethacrylate; and any combination thereof; and [0033] (iii) optionally, said one or more anionic monomers contain functional groups selected from the group consisting of carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water soluble salts, their corresponding water dispersible salts, and any combination thereof; or said one or more anionic monomers comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, and ammonium salts, or any combination thereof; [0034] (e) comprises a neutral monomer content or an acrylamide content ranging from 1-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 40-60 wt-%, 40-50 wt-%, or 50-70 wt-%; [0035] (f) comprises a cationic monomer content ranging from 1-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 50-70 wt-%; [0036] (g) optionally comprises an anionic monomer content ranging from 0-50% by weight;
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0037] (h) comprises a net cationic charge ranging from 1-99 mol%, 5-90 mol%, 10-80 mol%, 30-80 mol%, 40-80 mol%, 40-60 mol%, 40-50 mol%, 50-70 mol%, 10-60 mol%, 10-50 mol%, 10-40 mol%, or 10-30 mol% at pH 7; [0038] (i) comprises an aqueous composition comprising a polymer, optionally a polymer which exists as a liquid at a temperature of ~ 25 °C, wherein the polymer content of the aqueous composition by weight ranges from 0.5-20 wt-%, 1-15 wt-%, 2-10 wt-%, or 4-8 wt-%; or [0039] (j) any combination of (a)-(i). [0040] In some exemplary embodiments of the GPAM composition, the second base polymer: [0041] (a) is prepared by a radical polymerization reaction comprising and inverse emulsion polymerization or a dispersion polymerization; [0042] (b) comprises said second standard viscosity (SV) ranging from greater than 1.4 cPs, greater than 1.4-3.5 cPs, 1.5-3.5 cPs, 1.6-3.5 cPs, 1.8-3.5 cPs, 2.0-3.5 cPs, 2.2-3.5 cPs, 2.4-3.5 cPs, 2.6-3.5 cPs, 2.8-3.5 cPs, or 3.0-3.5 cPs; [0043] (c) comprises one or more polymers or copolymers comprising one or more cationic monomers, optionally one or more neutral monomers, and optionally one or more anionic monomers, wherein: [0044] (i) said one or more cationic monomers are selected from the group consisting of acryloyloxyethyltrimethyl ammonium chloride (Q9), methacryloyloxyethyltrimethylammonium chloride (MAETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), methacryloyloxyethyldimethylammonium sulfate, diallyldialkylammonium halides diallyldimethylammonium chloride (DADMAC), diallyldiethylammonium chloride; dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates and their quaternary or acid salts; dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides, methacrylamides and their quaternary or acid salts; acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, and diethylaminoethylmethacrylate; and any combination thereof; [0045] (ii) optionally, said one or more neutral monomers are selected from the group consisting of primary amide-containing monomers, acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof; and
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0046] (iii) optionally, said one or more anionic monomers contain functional groups selected from the group consisting of carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water soluble salts, their corresponding water dispersible salts, and any combination thereof; or said one or more anionic monomers comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, and ammonium salts, or any combination thereof; [0047] (d) comprises a neutral monomer content or an acrylamide content ranging from 0-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 50-70 wt-%; [0048] (e) comprises a cationic monomer content ranging from 1-100 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 70-80 wt-%; [0049] (f) optionally comprises an anionic monomer content ranging from 0-50 wt-%; [0050] (g) comprises a net cationic charge ranging from 1-100 mol%, 10-90 mol%, 20-80 mol%, 30-80 mol%, 40-80 mol%, 40-60 mol%, 40-50 mol%, or 50-70 mol% at pH 7; [0051] (h) comprises a dispersion, an emulsion, an invert emulsion, or an oil-in-water emulsion comprising an aqueous continuous phase and further optionally comprising a polymer content of said second base polymer ranging from 0.5-50 wt-%, 1-45 wt-%, 2-40 wt-%, 4-35 wt-%, 0.5-20 wt-%, 1-15 wt-%, 2-10 wt-%, or 4-8 wt-%; [0052] (i) comprises any combination of (a)-(h). [0053] In some exemplary embodiments of the GPAM composition, according to any of the foregoing: [0054] (a) said first base polymer comprises (i) acrylamide and DADMAC, Q9, MAPTAC, or any combination thereof; or (ii) acrylamide and DADMAC; (b) said first base polymer comprises said acrylamide content ranging from 5-95 wt-%, 30-70 wt-% or 50-70 wt-% and said cationic monomer content ranging from 5-95 wt-%, 30-70 wt-% or 30-50 wt-%; (c) said first base polymer comprises said net cationic charge ranging from 1-95 mol%, 30-70 mol% or 30-50 mol%; (d) said first base polymer comprises said aqueous composition comprising a polymer; (e) said second base polymer comprises (i) acrylamide and DADMAC, Q9, MAPTAC, or any combination thereof; (ii) acrylamide and Q9, or (iii) Q9; (f) said second base polymer comprises said acrylamide content ranging from 0-95 wt-%, 0-70 wt-%, 0-60 wt-%, or 10-40 wt-% and said cationic monomer content ranging from 0-95 wt-%, 30-100 wt-%, 40-100 wt-%, or 60-90 wt-%; (g) said second base polymer comprises a net cationic charge ranging from 1-100 mol%, 30-100 mol%, 40-100 mol%, or 60-90 mol%; (h) said second base polymer comprises an emulsion polymer or copolymer; (i) said GPAM composition comprises said GPAM emulsion; (j) said GPAM composition is suitable for use as a dry strengthening agent, a wet strengthening agent, a drainage aid, a retention aid, or any combination thereof; (k) said GPAM composition is suitable for use in the manufacture of paper, paperboard, newsprint, tissue, wherein said paper or paperboard are optionally used for printing, writing, or packaging; or (l) any combination of (a)-(k). [0055] In some exemplary embodiments, according to any of the foregoing, the GPAM composition, when added to a papermaking furnish, a cellulosic fiber stock, or a composition comprising cellulosic fibers for the manufacture of paper or board at a dosage of 0.1-20 lb/ton, 0.5-18 lb/ton, 1-16 lb/ton,
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING 2-14 lb/ton, 2-12 lb/ton, or 3-9 lb/ton, optionally in combination with a silica and/or a flocculant, results in a paper product comprising one or more of the following properties: [0056] (i) a percent GPAM solids ranging from 0.02-15 wt-% or 0.05-10 wt-% of the paper product after drying; (ii) an increased dry tensile strength; (iii) an increased cross-directional tensile strength; (iv) a decreased drainage time determined by dynamic drainage analyzer (DDA); or (v) any combination of (i)-(iv), wherein properties (ii)-(iv) are compared to a paper product that does not contain said GPAM composition or contains an alternate GPAM composition comprising a lower GPAM standard viscosity and/or a lower standard viscosity (SV) than said GPAM composition, a GPAM standard viscosity of 2.5 cPs or less, a standard viscosity of less than 40 cPs, a lower reduced viscosity than said GPAM composition, or a reduced viscosity of less than 10 dL/g. [0057] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: (a) glyoxalating the first base polymer in a glyoxalation reaction by contacting the first base polymer with glyoxal, optionally a molar excess of glyoxal; (b) contacting the second base polymer with the glyoxalation reaction; and (c) optionally adding additional glyoxal to produce the GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0058] In some exemplary embodiments of the method: [0059] (a) step (a) comprises a ratio of glyoxal to said first base polymer (wt/wt) ranging from 0.01- 99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2- 0.4, or 0.2-0.3; [0060] (b) step (a) comprises a GPAM content ranging from 1-20 wt-%, 1-10 wt-%, 3-9 wt%, 4-8 wt%, 5-7 wt%, or 5-6 wt%; [0061] (c) step (a) comprises a first pH ranging from 6-10, 7.5-9.5, 7.5-9, 7.5-8.5, or 7.5-8; [0062] (d) the method further comprises after step (a), allowing the glyoxalation reaction to reach a first standard viscosity ranging from 10-100 cPs, 15-80 cPs, 20-60 cPs, 20-45 cPs, 25-35 cPs, or 30-35 cPs; [0063] (e) the method further comprises after reaching said first standard viscosity and prior to step (b), adding an amount of water and adjusting to a second pH ranging from 2-9, 2.5-9, 4-9, 4.5-9, 5-9, 5.2-9, 5.4-9, 5.6-9, 5.8-9, 6-9, 6.5-9, 7-9, or 7.5-8.8; [0064] (f) the method further comprises after step (b), allowing the glyoxalation reaction to reach a second standard viscosity ranging from at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300-1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs; [0065] (g) the method further comprises after reaching said second standard viscosity, adjusting to a final pH ranging from 2.5-3.5, 2.8-3.2, or 3-3.2; [0066] (h) step (c) comprises a ratio of total added glyoxal to total base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15- 0.6, 0.2-0.4, or 0.2-0.3; [0067] (i) allowing the GPAM composition to reach a GPAM standard viscosity of greater than 2.5 cPs, 2.6-100 cPs, 2.7-90 cPs, 2.8-80 cPs, 2.9-70 cPs, 3-60 cPs, 4-50 cPs, 5-40 cPs, 6-30 cPs, 7-20 cPs, 8-
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING 20 cPs, 9-20 cPs, 10-20 cPs, or 4-10 cPs, 5-10 cPs, 6-10 cPs, 7-10 cPs, 8-10 cPs, or 9-10 cPs; or (j) any combination of (a)-(i). [0068] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: [0069] (a) the steps of (i) glyoxalating the second base polymer in a glyoxalation reaction by contacting the second base polymer with glyoxal; (ii) contacting the first base polymer and optionally additional second base polymer with the glyoxalation reaction; and (iii) optionally adding additional glyoxal to produce the GPAM composition; [0070] (b) the steps of (i) glyoxalating the first base polymer in a glyoxalation reaction by contacting the first base polymer with glyoxal, to produce a first glyoxalated base polymer; (ii) contacting the first glyoxalated base polymer with the second base polymer; (iii) optionally adding additional glyoxal and/or additional first base polymer to produce the GPAM composition; or [0071] (c) the steps of (i) glyoxalating the second base polymer in a glyoxalation reaction by contacting the second base polymer with glyoxal, to produce a second glyoxalated base polymer; (ii) contacting the second glyoxalated base polymer with the first base polymer; (iii) optionally adding additional glyoxal and/or additional second base polymer to produce the GPAM composition. [0072] In some exemplary embodiments of the method: [0073] (a) step (a)(i), (b)(i), or (c)(i) comprises a ratio of glyoxal to said first or second base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05- 0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3; [0074] (b) step (a)(i), (b)(i), or (c)(i) comprises a GPAM content ranging from 1-20 wt-%, 1-10 wt-%, 3-9 wt%, 4-8 wt%, 5-7 wt%, or 5-6 wt%; [0075] (c) step (a)(i), (b)(i), or (c)(i) comprises a first pH ranging from 6-10, 7-10, 7.5-9.5, 7.5-9, 7.5- 8.5, or 7.5-8; [0076] (d) the method further comprises after step (a)(i), (b)(i), or (c)(i), allowing the glyoxalation reaction to reach a first standard viscosity ranging from 10-100 cPs, 15-80 cPs, 20-60 cPs, 20-45 cPs, 25-35 cPs, or 30-35 cPs; [0077] (e) the method further comprises, after reaching said first standard viscosity and prior to step (a)(ii), (b)(ii), or (c)(ii), adding an amount of water and adjusting to a second pH ranging from 2-9, 2.5-9, 4-9, 4.5-9, 5-9, 5.2-9, 5.4-9, 5.6-9, 5.8-9, 6-9, 6.5-9, 7-9, or 7.5-8.8; [0078] (f) the method further comprises after step (a)(ii), (b)(ii), or (c)(ii), allowing the glyoxalation reaction to reach a second standard viscosity ranging from at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300-1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs; [0079] (g) the method further comprises after reaching said second standard viscosity, adjusting to a final pH ranging from 2.5-3.5, 2.8-3.2, or 3-3.2; [0080] (h) step (a), (b), or (c) comprises a ratio of total added glyoxal to total base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1- 0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3; or
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0081] (i) any combination of (a)-(h) [0082] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: [0083] (a) the steps of (i) glyoxalating the first base polymer in a first glyoxalation reaction by contacting said first base polymer with glyoxal to produce a first glyoxalated base polymer; (ii) glyoxalating the second base polymer in a second glyoxalation reaction by contacting said second base polymer with glyoxal to produce a second glyoxalated base polymer; and (iii) combining the first glyoxalated base polymer and the second glyoxalated base polymer, and optionally adding additional glyoxal, to produce the cationic GPAM composition, wherein steps (i) and (ii) are performed in any order or simultaneously; or [0084] (b) the steps of (i) combining the first base polymer and the second base polymer; (ii) glyoxalating by contacting the first base polymer and the second base polymer with glyoxal, and (iii) optionally adding additional glyoxal and/or additional first base polymer and/or additional second base polymer to produce the cationic GPAM composition. [0085] In another aspect, the present invention provides a method of papermaking, the method comprising: [0086] (a) contacting an aqueous suspension comprising cellulosic fibers with one or more GPAM compositions according any of the foregoing GPAM compositions; [0087] (b) removing sufficient water from the aqueous suspension to form a wet fibrous web, preferably by introducing the aqueous suspension into a headbox and draining the aqueous suspension on a wire screen; and [0088] (c) pressing and drying the wet fibrous web to obtain a paper product. [0089] In some exemplary embodiments of the method: [0090] (a) the method further comprises diluting the aqueous suspension with water, brine, process water, or white water, [0091] (b) the method further comprises adjusting the aqueous suspension to a pH ranging from 5-9, 5-7.5, 6-7, 6.2-6.8, or 6.4-6.6 prior to or after addition of the one or more GPAM compositions; [0092] (c) the method further comprises optionally contacting the aqueous suspension with one or more flocculants to form a flocculated fiber suspension prior to, during, or after said addition of the one or more GPAM compositions; [0093] (d) said one or more flocculants comprise polyacrylamide flocculants, anionic polyacrylamide flocculants, cationic polyacrylamide flocculants, and/or amphoteric polyacrylamide flocculants, optionally having a standard viscosity (SV) ranging from 3-7 cPs, 4-6 cPs, or 4.5-5.5 cPs; [0094] (e) the method further comprises optionally adding one or more inorganic microparticles prior to, during, or after said addition of the one or more GPAM compositions; [0095] (f) said one or more inorganic microparticles are selected from the group of microparticles and nanoparticles consisting of silica microparticles; colloidal silica; aluminum phyllosilicate mineral particles, including but not limited to bentonite, sodium bentonite, calcium bentonite, and montmorillonite; [0096] (g) said paper product comprises paper, paperboard, newsprint, or tissue, wherein said paper or paperboard are optionally used for printing, writing, or packaging; or
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0097] (h) any combination of (a)-(g). [0098] In some exemplary embodiments of the method said aqueous suspension comprising cellulosic fibers comprises: [0099] (a) one or more cellulosic fibers optionally comprising softwood fiber, hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated broke, non-wood fibers, straw pulp, wheat pulp, or a combination of any of the foregoing; [0100] (b) a papermaking furnish comprising pulp, Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp, process water from pulp, paper, and/or board production, neutral sulfite semi chemical (NSSC) pulp, mechanical pulp, non-wood pulp, or a mixture of any of the foregoing; [0101] (c) a cellulosic fiber stock comprising a thick stock, a thick stock diluted with chemical water, synthetic water, white water, and/or process water, and a thin stock, or a mixture of any of the foregoing; or [0102] (d) any combination of (a)-(c). [0103] In some exemplary embodiments of the method: [0104] (a) said GPAM composition is added to said aqueous suspension comprising cellulosic fibers at a dosage of 0.1-20 lb/ton, 0.5-18 lb/ton, 1-16 lb/ton, 2-14 lb/ton, 2-12 lb/ton, or 3-9 lb/ton; [0105] (b) the method results in said paper product comprising one or more of the following properties: [0106] (i) a percent GPAM solids ranging from 0.02-15 wt-% or 0.05-10 wt-% of the paper product after drying; [0107] (ii) an increased dry tensile strength; [0108] (iii) an increased cross-directional tensile strength; [0109] (iv) a decreased drainage time determined by dynamic drainage analyzer (DDA); or [0110] (v) any combination of (i)-(iv), [0111] wherein properties (ii)-(iv) are compared to a paper product that does not contain said GPAM composition or contains an alternate GPAM composition comprising a lower GPAM standard viscosity and/or a lower standard viscosity than said GPAM composition, a GPAM standard viscosity of 2.5 cPs or less, a standard viscosity of less than 40 cPs, a lower reduced viscosity than said GPAM composition, or a reduced viscosity of less than 10 dL/g. [0112] In another aspect, the present invention provides a fiber stock composition comprising: (a) an aqueous suspension comprising cellulosic fibers; and (b) a GPAM composition according to any of the foregoing or obtainable by a method according to any of the foregoing methods of GPAM preparation. [0113] In another aspect, the present invention provides a paper product produced according to any of the foregoing methods of paper preparation or containing a fiber stock composition according to any of the foregoing.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING BRIEF DESCRIPTION OF THE DRAWINGS [0114] The invention will be described in more detail with reference to appended drawings, described in detail below. [0115] FIG 1 provides an exemplary graph of tensile strength (lb/in) for handsheets prepared from OCC furnish treated with GPAMs according to Example 2. [0116] FIG 2 provides an exemplary graph of GPAM reduced viscosity vs. tensile strength (data labels indicate GPAM sample) for handsheets prepared according to Example 2. [0117] FIG 3 provides an exemplary graph of drainage testing results from Dynamic Drainage Analyzer (DDA) testing of OCC furnish treated with GPAMs and silica according to Example 3. [0118] FIG 4 provides an exemplary graph of GPAM reduced viscosity vs. DDA drainage time (data labels indicate GPAM sample) from drainage testing performed according to Example 3. DETAILED DESCRIPTION OF THE INVENTION [0119] Before describing the invention, the following definitions are provided. Unless stated otherwise all terms are to be construed as they would be by a person skilled in the art. DEFINITIONS [0120] As used herein, all technical and scientific terms have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs unless clearly indicated otherwise. [0121] As used herein, the singular forms “a,” “an,” and “the” may mean “one” but also include plural referents such as “one or more” and “at least one” unless the context clearly dictates otherwise. All technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs unless clearly indicated otherwise. [0122] As used herein, the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” [0123] As used herein the term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term unless stated otherwise. PAPERMAKING [0124] As used herein, the term "paper" includes products comprising a cellulosic sheet material including paper sheet, paperboard, and the like. [0125] As used herein, the terms “papermaking”, “papermaking process”, and “papermaking application” generally refers to any process in which any form of paper and/or paperboard product may be produced. For example, such processes include making paper products from pulp, such as methods comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet, and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known in the art. [0126] As used herein, the terms “wet end of a paper machine” or “wet end” generally refer to the parts of a papermaking process between pulping (or bleaching) and wet-pressing of the paper.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0127] As used herein, the term “fiber” or “cellulosic fiber” refers to the basic structural unit of paper or board. [0128] As used herein, the terms “recycled fiber” and “recovered fiber”, refer to paper, paperboard, and fibrous wastes from retail stores, office buildings, homes, manufacturing plants, and so forth, after they have passed through their end-usage as a consumer item. Manufacturing wastes include: dry paper and paperboard waste generated after completion of the papermaking process including by way of example: envelope cuttings, bindery trimmings, and other paper and paperboard waste resulting from printing, cutting, forming, and other converting operations; bag, box, and carton manufacturing wastes; mill wrappers, and rejected unused stock; and repulped finished paper and paperboard from obsolete inventories of paper and paperboard manufacturers, merchants, wholesalers, dealers, printers, converters, or others. In particular the term “recycled fibers” includes recycled fibers derived by processing of paper and other consumer cellulosic materials, e.g., paper, old corrugated containerboard (OCC), mixed office waste (MOW), old magazine (OMG), unbleached kraft pulp, neutral sulphite semi chemical (NCCS) pulp and/or mechanical pulp. Source materials for recycled fibers may be selected from old corrugated containerboard, mixed office waste, old newsprint, old magazines, double liner kraft, and any mixtures thereof. Mixed waste (MXW) denotes recycled mixture of recycled board, such as OCC, white lined chipboard and/or folding boxboard, and recycled paper, such as old newsprint, old magazines and/or office waste papers. Mixed office waste denotes recycled fiber material mainly containing copying papers, printer papers and offset papers. Double lined kraft denotes recycled fiber material comprising clean sorted unprinted corrugated cardboard cartons, boxes, sheet or trimmings, e.g., of kraft or jute liner. White lined chipboard (WLC) denotes multiply board comprising deinked fiber material and/or un-deinked recycled fiber material originating e.g., from OCC, mixed office waste or old newspapers (ONP) in or more of the layers. Presence of any of these recycled fiber materials in the fiber suspension usually decreases drainage and paper strength and provides a substantial load of starch, hydrophobic, and colloidal substances to the process. [0129] As used herein, the term “OCC” refers to old corrugated cardboard and/or containerboard. Corrugated refers to those boxes where the materials are made from three separate layers of paper, two liners and a corrugated, or wavy, layer sandwiched between them. Brown paper bags are commonly accepted with OCC for recycling. The term OCC denotes recycled fiber material which have liners of test liner, jute or kraft, and may cover also double sorted corrugated containerboard (DS OCC). [0130] As used herein, the terms “broke” or “mill broke” refer to paper, which during the paper making process becomes suitable only for repulping e.g., trimmings or paper that is out of specification. Broke is re-used material which never left the mill is not regarded as recycled or recovered. Broke is a valuable source of fiber and is recycled internally at the mill. As used herein, the term “coated broke” refers to broke that contains coatings that are applied to the base sheet of paper as it is being manufactured. When the broke contains these coatings, it presents special problems in recycling to recover fiber values because the coatings introduce materials which would not normally be present in the original stock of fiber used to manufacture the base paper sheet. The coated broke may also contain dyes and/or other additives. In the present application coated broke includes surface-sized, dyed, and/or creped broke. [0131] As used herein, the term “recycled fiber composition” generally refers to a composition comprising recycled cellulosic fibers, typically a composition wherein most or all are recycled fibers, e.g., at least 20, 40, 50, 60, 70, 80, 90 or 100%.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0132] As used herein, the term “aqueous solution” or “solution” generally refers to a mixture of water and a water-soluble solute or solutes which are completely dissolved with little to no residual undissolved polymer gel. The solution may be homogenous. An exemplary aqueous polymer solution comprises a polymer mixed with an excess of water so that the polymer is preferably fully dissolved and the obtained polymer solution is preferably free from discrete polymer particles or granules or residual gel. [0133] As used herein, the term “aqueous suspension”, “aqueous slurry”, or “slurry” generally refer to a heterogeneous mixture of a fluid that contains insoluble or sparingly soluble solid particles sufficiently large for sedimentation. Suspensions and slurries of the present invention may also comprise some amount of solid particles, often termed colloidal particles, which do not completely settle or take a long time to settle completely. [0134] As used herein, the term “fiber suspension” is understood as an aqueous suspension, which comprises fibers, preferably recycled fibers, and optionally fillers. For example, the fiber suspension may comprise at least 5 %, preferably 10-30 %, more preferably 11 - 19 % of mineral filler. Mineral filler may be any filler conventionally used in paper and board manufacturing, such as ground calcium carbonate, precipitated calcium carbonate, clay, talc, gypsum, titanium dioxide, synthetic silicate, aluminum trihydrate, barium sulphate, magnesium oxide or their any of mixtures. [0135] As used herein, the term “slurry” generally refers to a mixture of water, dissolved paper pulp, and optionally other soluble or insoluble components produced or added during the stock preparation phase of papermaking. [0136] As used herein the term “headbox” refers a receptacle in a papermaking machine that holds suspended aqueous cellulosic solids and which regulates the flow thereof onto a wire or screen that provides for the draining of water therefrom. [0137] As used herein the term “lignocellulosic substrate” refers to a paper and/or paperboard product formed from plant dry matter from any source, virgin or recycled, which may be coated, printed, and/or formed into a packaging product. For example, such substrates include paper products made from pulp, such as by methods comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet, and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known in the art. The substrates may contain polymeric strengthening agents, such as wet strength and dry strength agents. [0138] As used herein, the terms “furnish” or “papermaking furnish” generally refers to a mixture of cellulosic fibers, pulp, optional fillers, dyes, and water from which paper or board is made. [0139] As used herein, the term “thick stock” generally refers to mixture of papermaking pulp and other materials with a consistency of about 1 to 5%. [0140] As used herein, the term “thin stock” generally refers to a mixture of papermaking pulp and other materials, after having been diluted to a consistency below 1% with whitewater or other process water at a fan pump. [0141] As used herein, the term “white water” generally refers to process water within a paper machine system, especially referring to water that is drained from paper as the sheet is being formed.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0142] As used herein, the term "produced water" generally refers to any aqueous fluids produced during any type of industrial process, e.g., an paper or board manufacturing process, e.g., a pulp, paper, or cardboard process. [0143] As used herein, the term “flocculation” generally refers to the tendency for fibers to collect together in bunches in the presence of flow, and especially in the presence of retention aids; the same word also refers to the action of high-mass polymers in forming bridges between suspended colloidal particles, causing strong, relatively irreversible agglomeration. [0144] The term “flocculant” may generally refer to a reagent that may bridge neutralized or facilitate coagulation of particles into larger agglomerates, typically resulting in more efficient settling. Flocculation process generally involves addition of a flocculant followed by mixing to facilitate collisions between particles, allowing for the destabilized particles to agglomerate into larger particles that can be removed by gravity through sedimentation or by other means, e.g., centrifugation, filtration. [0145] As used herein the term "dry strength" generally refers to the force or energy required to break a paper sample, by one of various procedures, after equilibration in a standard atmosphere. [0146] As used herein the term "wet strength" generally refers to the strength of a sheet of paper after it has been exposed to a standard solution for a standard length of time, but often expressed as a ratio vs. the dry strength. POLYMERS [0147] As used herein, the terms “polymer” or “polymeric additives” and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or describe a large molecule (or group of such molecules) that may comprise recurring units. Polymers may be formed in various ways, including by polymerizing monomers and/or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer may comprise a “homopolymer” that may comprise substantially identical recurring units that may be formed by, for example, polymerizing a particular monomer. Unless otherwise specified, a polymer may also comprise a "copolymer” that may comprise two or more different recurring units that may be formed by, for example, copolymerizing, two or more different monomers, and/or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer or copolymer may also comprise a “terpolymer” or a “tetrapolymer” which generally refer to polymers that comprise three, four, or more different recurring monomer units. The term “polymer” as used herein is intended to include both the acid form of the polymer as well as its various salts. Polymers may be amphoteric in nature, that is, containing both anionic and cationic substituents, although not necessarily in the same proportions. Polymer molecular weights may be measured by various methods known to persons of skill in the art. For example, weight average molecular weight may be measured using gel permeation chromatography (GPC). Polymer molecular weights may be measured by various methods known to persons of skill in the art. For example, weight average molecular weight may be measured using gel permeation chromatography (GPC). Additionally, polymer molecular weights may be measured by GPC/Light Scattering/Viscometry also known as Triple Detection GPC which employs Refractive Index Detector (with or without UV Detector), Dilute Solution Viscometry and Light Scattering all in series to determine molecular weights, distribution and related solution parameters. [0148] As used herein, the terms “polyacrylamide” or “PAM” generally refer to polymers and co- polymers comprising acrylamide moieties, and the terms encompass any polymers or copolymers,
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING including terpolymers, comprising acrylamide moieties, e.g., one or more acrylamide (co)polymers of acrylamide and additional monomers capable of copolymerizing with acrylamide. Furthermore, PAMs may comprise any of the polymers or copolymers discussed herein. Additionally, the PAMs described herein, e.g., one or more acrylamide (co)polymers, may be produced in one of various forms, including, for example, dry (powder ) form (e.g., DPAM), emulsion polyacrylamide (EPAM), or liquid polyacrylamide. Amphoteric polyacrylamides (AmPAM) may be formulated in dry (powder ) form (e.g., AmDPAM), or emulsion form (AmEPAM) . [0149] As used herein, the term “amphoteric polymer” refers to polymers containing both anionic and cationic groups on the macromolecular chain. These polymers exhibit both attraction and repulsion in their electrostatic intermolecular interactions (resulting in anti-polyelectrolyte association called “Amphoteric Effect”) and they exhibit excellent salt tolerance, especially in high Ca+2 aqueous compositions. [0150] As used herein, the term "emulsion polymer" generally refers to inverse emulsions (water-in- oil) in which water droplets containing the polymer are suspended in an oil phase, also termed a hydrophobic phase. [0151] As used herein, the term “inverse phase emulsion” refers to an aqueous liquid polymer composition which is dispersed into an oil phase (e.g., hydrophobic liquid) to form an oil-continuous phase, which is then mixed with an aqueous solution so that the dispersed polymer phase of the aqueous polymer becomes a substantially aqueous-continuous phase, and the hydrophobic liquid phase becomes a dispersed, discontinuous phase. The inversion point can be characterized as the point at which the viscosity of the inverted polymer solution has substantially reached its maximum under a given set of conditions. In practice, this may be determined for example by measuring viscosity of the composition periodically over time and when three consecutive measurements are within the standard of error for the measurement, then the solution is considered inverted. [0152] As used herein a “liquid polymer” refers to a polymer which exists partially or totally as a liquid at a temperature of ~25℃ when comprised in a liquid, typically an aqueous liquid. The liquid polymer in a may be thoroughly dissolved or may be a partially dissolved suspension, dispersion, or slurry. [0153] As used herein an “aqueous polymer mixture” or “hydrated polymer composition” refers to a combination of at least one polymer and an aqueous liquid. When a dry polymer is combined with an aqueous liquid, the polymer is initially partially hydrated at the polymer–water interface. Polymers do not dissolve instantaneously in aqueous or non-aqueous solvents. Dissolution is controlled by either the disentanglement of the polymer chains or by the diffusion of the chains through a boundary layer adjacent to the polymer–solvent interface. After thorough mixing, the polymer may become fully hydrated, at which point the wetting process is complete and the polymer may be either partially dissolved or fully dissolved, depending on the nature and composition of the polymer and solvent. [0154] The term “water-soluble polymer” generally refers to any polymer that may dissolve and/or disperse in water. Said polymers may modify the physical properties of aqueous systems undergoing gelation, thickening, viscosification, or emulsification/stabilization. Said polymers may perform a variety of functions, including but not limited to use as dispersing and suspending agents, stabilizers, thickeners, viscosifiers, gellants, flocculants and coagulants, film-formers, humectants, binders, and lubricants.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0155] As used herein, the term “monomer” generally refers to nonionic monomers, anionic monomers, cationic monomers, zwitterionic monomers, betaine monomers, and amphoteric ion pair monomers. [0156] As used herein “acrylamide” or “AMD” refers to a neutral monomer of molecular formula: C3H5NO and a molecular weight of 71.08 g/mol. [0157] As used here “Q9 monomer” refers to [2-(acryloyloxy)ethyl] trimethylammonium chloride (Q9) which has a molecular formula of C8H16ClNO2 and a molecular weight of 193.67 g/mol. [0158] As used herein, the term "cationic monomer" generally refers to a monomer that possesses a positive charge. Examples thereof include acryloyloxy ethyl trimethylammonium chloride (Q9) monomers. Cationic monomers may also be selected from acryloyloxyethyltrimethyl ammonium chloride (“AETAC”), methacryloyloxyethyltrimethylammonium chloride (“MAETAC”), methacrylamidopropyltrimethylammonium chloride (“MAPTAC”), acrylamidopropyltrimethylammonium chloride (“APTAC”), methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium chloride (“DADMAC”); dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates and their quaternary or acid salts, including but not limited to, dimethylaminoethyl acrylate (“DMAEA”), dimethylaminoethyl methacrylate (“DMAEA”), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides and methacrylamides and their quaternary or acid salts, including but not limited to, acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, methacrylamidopropyltrimethylammonium chloride, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate; and diallyldialkylammonium halides, including but not limited to, diallyldiethylammonium chloride and diallyldimethylammonium chloride (“DADMAC”), and any combination thereof. In exemplary embodiments of the present invention, cationic monomers comprise Q9, DADMAC, and/or MAPTAC. [0159] As used herein the term “nonionic monomer” generally refers to a monomer that possesses a neutral charge. Exemplary nonionic monomers may comprise but are not limited to comprising monomers selected from the group consisting of acrylamide (“AMD”), methacrylamido, vinyl, allyl, ethyl, and the like, all of which may be substituted with a side chain selected from, for example, an alkyl, arylalkyl, dialkyl, ethoxyl, and/or hydrophobic group. In an exemplary embodiment, a nonionic monomer may comprise AMD. In some embodiments, nonionic monomers may comprise but are not limited to comprising vinyl amide (e.g., acrylamide, methacrylamide, N-methylacrylamide, N,N- dimethylacrylamide), 4-acryloylmorpholine, maleic anhydride, N-vinylpyrrolidone, vinyl acetate, N- vinyl formamide and their derivatives, such as hydroxyethyl(methyl(acrylate CH2=CR-COO- CH2CH2OH (I) and CH2=CR-CO-N(Z1)(Z2) (2) N-substituted (methyl) acrylamide (II), R=H or Me; Z1=5- 15C alkyl; 1-3C alkyl substituted by 1-3 phenyl , phenyl or 6-12C cycloalkyl (both optionally
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING substituted) and Z2=H; or Z1 and Z2 are each 3-10C alkyl; (II) is N-tert. hexyl, tert. octyl, methylundecyl, cyclohexyl, benzyl, diphenylmethyl or triphenyl acrylamide. Nonionic monomers include N-isopropylacrylamide, N-vinyl formamide, methacrylamide; N-alkylacrylamides, including but not limited to, N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, and N- butylacrylamide; N,N-dialkylacrylamides, including, but not limited to, N,N-dimethylacrylamide and N,N-diethylacrylamide; N-alkyl methacrylamides; alkyl acrylates; hydroxyalkyl acrylates and methacrylates, including but not limited to, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 3- hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; dihydroxyalkyl acrylates and methacrylates, including but not limited to, 2,3-dihydroxypropyl acrylate, 3,4- dihydroxybutyl acrylate, 2,3-dihydroxypropyl methacrylate (DHPMA), and 3,4-dihydroxybutyl methacrylate; alkyl acrylates, including but not limited to, methyl methacrylate; acrylonitrile; N- vinylmethylacetamide, N-vinylmethylformamide; N-vinyl acetate, glyoxalated acrylamides, and vinyl pyrrolidone. Nonionic monomers can be combined for example to form copolymers with acrylamide. [0160] In some embodiments, non-ionic monomers of the present invention comprise any of the foregoing non-ionic monomers. In exemplary embodiments, non-ionic monomers are selected from the group consisting of acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N- methylacrylamide, N-butylacrylamide, N-tert-butylacrylamide, N-ethyl methacrylamide, and any combination thereof. [0161] As used herein, the term “anionic monomers” may refer to either anionic monomers that are substantially anionic in whole or (in equilibrium) in part, at a pH in the range of about 1.0 to about 10.0. The “anionic monomers” may be neutral at low pH (e.g., from a pH of about 0-1, 0-2, or 0-3) depending on the pKa values of acidic protons contained therein. Some anionic monomers are obtained in anionic form as alkali metal salts, alkaline earth metal salts, and ammonium salts. Anionic monomers may comprise acrylic acid (AA), methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, ammonium salts, and any combination thereof. [0162] As used herein, the term “cationic monomer content” refers to the percentage of a substance's total mass that is contributed by positively charged cations or cationic monomers. In certain embodiments, “cationic monomer content” may refer to the wt% of cationic monomers in a substance, wherein the substance may be a polymer, a polymer composition, a base polymer, a GPAM, or a GPAM composition. In certain embodiments, “cationic monomer content” may be calculated as 100% times the mass of cationic monomers divided by the total mass of the substance. [0163] As used herein the term “net charge” refers to the overall electric charge of a substance, determined by the balance of positive and negative charges within the substance under a given set of conditions. In certain embodiments, the substance may be a polymer, a polymer composition, a base polymer, a GPAM, or a GPAM composition. In certain embodiments, the amount of net charge of a substance may be expressed as the milliequivalents of total electric charge per mass of the substance (mEq/g). The net charge of an aqueous solution of a polymer or a GPAM composition may be pH dependent or pH independent, depending on the presence or absence of permanently charged monomers and the presence or absence of ionizable monomers. [0164] As used herein the term “net cationic charge” refers to a “net charge” of a substance that is greater than zero (i.e., positive). In certain embodiments, the substance may be a polymer, a
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING polymer composition, a base polymer, a GPAM, or a GPAM composition. In certain embodiments, the amount of net cationic charge of a substance may be expressed as the milliequivalents of total electric charge per mass of the substance (mEq/g), wherein the net electric charge is positive. “Net cationic charge” of a polymer may also be expressed in units of mol%, which refers to the net mole percentage of monomers bearing a net cationic charge in the polymer calculated as 100%*(number of cationic monomers – number of anionic monomers)/total monomers. [0165] As used herein the term “polymer content” refers to the weight percent of a polymer in a liquid composition, typically an aqueous composition. STRENGTH AND DRAINAGE AIDS [0166] As used herein, the term “cationic glyoxalated polyacrylamides (GPAMs)” or “GPAM” generally refers to a polymer obtained by reacting glyoxal and a “base polymer” to form a glyoxalated polymer backbone. In general, GPAM comprises a reactive polymer that can covalently bond with cellulose upon dehydration. Exemplary GPAMS are reactive cationic polymers containing reactive aldehydes, which react with carboxylate and -OH moieties on cellulosic and lignocellulosic fibers to form covalent bonds. Exemplary GPAMS are used as wet and/or dry strength additives and as retention and drainage aids in papermaking. [0167] As used herein, the term “glyoxylation percentage” refers to the percentage of acrylamide- based monomers which are glyoxalated in a polymer of the cationic GPAM composition, e.g., the first base polymer and/or the second base polymer. [0168] As used herein, the term “GPAM content” may refer to the combined weight percent (wt-%) of glyoxal and base polymer solids in a glyoxalation reaction mixture. “GPAM content” may also refer to the combined wt-% of GPAM, unreacted glyoxal, and unreacted base polymer in a GPAM composition, such as a GPAM emulsion. [0169] As used herein, the terms “anionic microparticles”, “anionic organic or inorganic microparticles”, or “anionic additives” generally refers to anionic materials added to papermaking furnish as part of drainage-aid programs. Exemplary anionic organic or inorganic microparticles are selected from the group of microparticles and nanoparticles consisting of silica microparticles; colloidal silica; aluminum phyllosilicate mineral particles, including but not limited to bentonite, sodium bentonite, calcium bentonite, and montmorillonite; and anionic polymer microparticles, including but not limited to highly structured anionic polyacrylamides. Preferred anionic organic or inorganic microparticles may include silica or colloidal silica. The function of the colloidal silica appears to involve (a) release of water from polyelectrolyte bridges, causing them to contract, and (b) acting as a link in bridges that involve macromolecules adsorbed on different fibers or fine particles. These effects create more streamlined paths for water to flow around the fibers. The tendency of microparticles to boost first-pass retention also will tend to have a positive effect on initial dewatering rates. It has been reported that paper produced by means of a microparticle retention and drainage program has a more open, porous structure, though the effect may become obscured by subsequent wet-pressing and calendering operations. [0170] As used herein the term “high viscosity polymer” or “high viscosity base polymer” generally refers to a polymer with a standard viscosity (SV) greater than 1.4 cPs. [0171] As used herein the term “high molecular weight polymer” or “high molecular weight base polymer” generally refers to a polymer with a weight average molecular weight greater than or equal to 1,000 kDa.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0172] As used herein the term “high viscosity GPAM” generally refers to a GPAM with a standard viscosity (SV) greater than or equal to 50 cPs, 100 cPs, or 200 cPs or a GPAM with a GPAM standard viscosity (GPAM SV) greater than 2.5 cPs. [0173] As used herein the term “high molecular weight GPAM” generally refers to a GPAM with a weight average molecular weight greater than or equal to 1,000 kDa. VISCOSITY [0174] As used herein the term “relative viscosity” refers to the ratio of polymer solution viscosity over solvent (water) viscosity. [0175] As used herein, the term “reduced viscosity” refers to the ratio of relative viscosity over polymer concentration (g/dL). [0176] As used herein, the term “specific viscosity” refers to the “relative viscosity” of a polymer solution of known concentration minus 1; usually determined at low concentration of the polymer; for example, 0.5 gram per 100 milliliters of solution, or less. [0177] As used herein the term “standard viscosity” or “SV” refers to the viscosity of a 0.1 wt% polymer or GPAM solution in 1 M NaCl. Standard viscosity (SV) is determined by adding 50 g of a 0.2 wt% aqueous polymer solution to 50 g of a 2 M NaCl solution, stirring the resulting mixture for 5 minutes, adjusting the pH to 5 and determining the standard viscosity at 25±0.1 °C using a Brookfield viscometer (LVT model) with UL adapter at 60 rpm. [0178] As used herein the term “GPAM standard viscosity” or “GPAM SV” refers to the viscosity of 1 wt% of GPAM in 0.5 M NaCl, wherein said GPAM includes both glyoxalated polyacrylamide and free glyoxal. GPAM standard viscosity (GPAM SV) is generally measured using a Brookfield LVT viscometer with a UL adapter at 60 rpm and 25 °C. If the GPAM standard viscosity (GPAM SV) is higher than 9.5 cps, the spindle rpm is lowered to 30 rpm to ensure the viscometer torque range < 95%. TERMS AND UNITS [0179] As used herein, the term “ppm” refers to parts per million on the basis of milligrams of solute per liter of aqueous solution or slurry (e.g., mg/L). [0180] As used herein, the terms “lbs/ton” denote pounds of dry mass of added material (e.g., additive, solute, and/or particle) per ton of suspended solids (e.g., weight of AKD per total dry ton of suspended solids). [0181] As used herein, the term “% by wt”, “wt-%”, or “wt%” denotes pounds of dry mass of additive per dry mass of solids in the formulation, solution, or slurry, multiplied by 100%. [0182] As used herein, the term “consistency” generally refers to percent oven dry mass in the stock, slurry, or furnish (i.e., 100% * oven dry mass/total mass). DESCRIPTION OF THE INVENTION [0183] Paper manufacturers, especially in mills with high recycled content with higher levels of calcium ions and high conductivity, require effective chemical additives that will provide on-machine retention and drainage and increased strength properties. [0184] In the production of paper or paperboard, a dilute aqueous composition known as "furnish" or "stock" is sprayed onto a moving mesh known as a "wire" or “wire screen”. Solid components of
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING this composition, such as cellulosic fibers, fines, and inorganic particulate mineral fillers are drained or filtered by the wire to form a paper sheet. [0185] Drainage relates to the rate of removal of water from the furnish as the paper sheet is formed. Drainage usually refers to only water removal which takes place in the "drainage zone" (gravity and vacuum sections) of the paper machine primarily before any pressing of the wet paper web subsequent to formation of the web. Drainage aids are used to improve the overall efficiency of dewatering in the production of paper or paperboard. Increased rates of gravity drainage and drainage under vacuum are preferred for increasing productivity. [0186] Tensile strength is a measure of the resistance of a manufactured paper or paperboard product to breaking or tearing under a force load. A strengthening agent is often added to improve tensile strength of the dry paper product. Increased tensile strengths are preferred. [0187] There is a generally recognized need in the art to provide GPAMs with higher MW (i.e., MW higher than 1,000 kDa). Higher MW GPAM polymers are expected to provide improved drainage rates and greater paper strength properties during the papermaking process. [0188] It is an object of the present invention to provide high MW, high standard viscosity (> 50 cPs) and/or high GPAM standard viscosity GPAM compositions, methods of making such compositions, and methods of use for improving drainage rates and/or tensile strength of paper or board products produced from a high percentage of recycled fiber content. I. Cationic GPAM Compositions [0189] The present invention generally relates to high MW (at least 1000 kDa) cationic glyoxalated polyacrylamide (GPAM) compositions for use as drainage and strength additives for paper or board. The GPAM compositions are preferably formulated as emulsion polymers with aqueous phase as the continuous phase, with high viscosities (at least 40 cPs), and high reduced viscosities (at least 10 dL/g) at a temperature of 25° C. [0190] The inventive high MW, high viscosity GPAMs have high molecular weights (i.e., in excess of 1000 kDa) and/or high standard viscosities in excess of 50, 100, or 200 cPs. In exemplary embodiments, the polyacrylamide backbone (base polymer) of the GPAM comprises acrylamide and one or more cationic monomers, rendering the polymer self-retaining on fibers. In some embodiments, cationic glyoxalated polyacrylamides (GPAMs) refers to aldehyde containing polymers or copolymers, preferably GPAMs suitable for use as a dry and/or wet strengthening agent and as retention and drainage aids in papermaking. [0191] GPAM compositions of the present invention comprise mixtures of base polymers which are glyoxalated. The base polymer mixtures comprise at least a first, low MW, low SV base polymer (e.g., MW less than 1000 kDa, SV ≤ 1.4 cPs) and a second, high MW, high SV base polymer (e.g., SV greater than 1.4 cPs). Because SV of a polymer generally increases with MW of the polymer, it is assumed for the present invention that the high SV base polymer (SV >1.4 cPs) is also a high MW base polymer (i.e., with MW > 1000 kDa). [0192] The inventive GPAM compositions shows unexpected performance efficiency for enhancing tensile strength and drainage rates when used in papermaking furnish containing high amounts of recycled content. Without being bound to theory, it is rationalized that intrapolymer cross-linking predominates in GPAM compositions of the present invention as evidenced by a decrease in viscosity as the glyoxal reaction proceeds. The differences in the molecular weights of the polymers employed and the types of glyoxal cross-linking of the present invention results in polymers with
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING significantly different structures than those previously reported, thereby causing greater stability at higher MW and higher viscosity formulation. This is further evidenced by the fact that, unlike previous examples of glyoxalated acrylamide polymers, which must be essentially water-soluble, the glyoxalated acrylamide polymers of the present invention provided good wet-strength to paper even when they are cross-linked to the extent that they are merely dispersible in water. [0193] GPAM compositions of the present invention comprise products of reactions between glyoxal and cationic polyacrylamide copolymers, which may also contain un-reacted glyoxal, un-reacted polyacrylamide, and additional polymers. [0194] In one aspect, the present invention provides a glyoxalated polyacrylamide (GPAM) composition for use as a strength and/or drainage aid for papermaking, wherein said GPAM composition comprises: (a) at least one cationic glyoxalated polyacrylamide (GPAM) comprising a mixture of glyoxalated cationic base polymers; and (b) a GPAM standard viscosity of greater than 2.5 cPs measured as 1 wt% of said GPAM composition in 0.5 M NaCl using a Brookfield LVT viscometer at a speed of 60 rpm and a temperature of 25° C. [0195] In some exemplary embodiments, the GPAM composition comprises a GPAM standard viscosity of greater than 2.5 to 10,000 cPs, greater than 2.5 to 8,000 cPs, greater than 2.5 to 6,000 cPs, greater than 2.5 to 4,000 cPs, greater than 2.5 to 2,000 cPs, greater than 2.5 to 1,000 cPs. In some exemplary embodiments, the GPAM composition comprises a GPAM standard viscosity of 2.6- 100 cPs, 2.7-90 cPs, 2.8-80 cPs, 2.9-70 cPs, 3-60 cPs, 4-50 cPs, 5-40 cPs, 6-30 cPs, 7-20 cPs, 8-20 cPs, 9-20 cPs, 10-20 cPs, or 4-10 cPs, 5-10 cPs, 6-10 cPs, 7-10 cPs, 8-10 cPs, or 9-10 cPs. [0196] In some exemplary embodiments, the GPAM composition comprises a standard viscosity of at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or a viscosity ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300-1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs measured as 0.1 wt% of said GPAM composition in 1 M NaCl using a Brookfield LVT viscometer at a speed of 60 rpm at a temperature of 25 °C. [0197] In some exemplary embodiments, the GPAM composition comprises a reduced viscosity of at least 10 dL/g, at least 20 dL/g, at least 40 dL/g, at least 60 dL/g, at least 80 dL/g, at least 100 dL/g, at least 125 dL/g, at least 150 dL/g; or ranging from 10-400 dL/g, 20-380 dL/g, 40-360 dL/g, 60-340 dL/g, 80-320 dL/g, 100-300 dL/g, 120-280 dL/g, 140-260 dL/g, 140-240 dL/g, 160-240 dL/g, or 180- 220 dL/g at a temperature of 25 °C. [0198] In some exemplary embodiments, the GPAM composition comprises a GPAM emulsion, an inverse GPAM emulsion, or preferably an oil-in-water GPAM emulsion comprising an aqueous continuous phase. [0199] In some exemplary embodiments, the GPAM composition comprises a GPAM content ranging from 1-20 wt-%; 2-10 wt-%, 3-10 wt%, 4-10 wt%, 4-8 wt-%, 4-7 wt-%, or 4-6 wt-%, wherein GPAM content refers to the wt-% of GPAM, glyoxal and base polymer in the composition. [0200] In some exemplary embodiments, the GPAM composition comprises a ratio of glyoxal to total cationic base polymers (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01- 4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3, or 0.40, 0.29, 0.23, 0.29, 0.22, 0.21, 0.23, 0.21, 0.23, 0.22.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0201] In some exemplary embodiments, the GPAM composition comprises a percent glyoxalation ranging from 1-100%, 5-90%, 5-80%, 10-60%, 10-40%, 15-35%, 20-30%, or 22-28%. [0202] In some exemplary embodiments, the GPAM composition comprises a net cationic charge ranging from 0.1 to 5.0 mEq /g, 0.4 to 4.0 mEq /g, 0.5 to 3.0 mEq /g, or 0.6 to 2.0 mEq /g. [0203] In some exemplary embodiments of the GPAM composition, the mixture of cationic base polymers comprises: (a) a first base polymer comprising a first standard viscosity (SV) of ≤ 1.4 cPs; and a second base polymer comprising a second standard viscosity (SV) of greater than 1.4 cPs, wherein said first and second standard viscosities are measured as 0.1 wt% of base polymer in 1 M NaCl using a Brookfield LVT viscometer with UL adapter at 60 rpm, pH 5, and a temperature of 25 °C; and (c) a ratio of said first base polymer to said second base polymer (wt:wt) ranging from 99:1 to 1:99, 90:10 to 10:90, 80:20 to 20:80, 80:20 to 30:70, 80:20 to 40:60, 80:20 to 50:50, or 70:30 to 60:40. [0204] In some exemplary embodiments of the GPAM composition, the first base polymer: (a) is prepared by a radical polymerization reaction comprising a solution polymerization reaction in water, an inverse emulsion polymerization, or a dispersion polymerization, and optionally comprising a chain transfer reagent; (b) comprises said first standard viscosity (SV) ranging from ≤ 1.4 cPs, 1.2-1.4 cPs, 1.25-1.4 cPs, 1.3-1.4 cPs, or 1.35-1.4 cPs; (c) comprises a weight average molecular weight ranging from 10-1000 kDa, 50-1000 kDa, 100-1000 kDa, 200-1000 kDa, 300-1000 kDa, 400-1000 kDa, 500-900 kDa, or 600-800 kDa. [0205] In some exemplary embodiments of the GPAM composition, the first base polymer: comprises one or more acrylamide-based copolymers comprising one or more neutral monomers, one or more cationic monomers, and optionally one or more anionic monomers, wherein: (i) said one or more neutral monomers are selected from the group consisting of primary amide-containing monomers, acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N- butyl acrylamide, N-ethyl methacrylamide, and any combination thereof; (ii) said one or more cationic monomers are selected from the group consisting of acryloyloxyethyltrimethyl ammonium chloride (Q9), methacryloyloxyethyltrimethylammonium chloride (MAETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), methacryloyloxyethyldimethylammonium sulfate, diallyldialkylammonium halides diallyldimethylammonium chloride (DADMAC), diallyldiethylammonium chloride; dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates and their quaternary or acid salts; dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides, methacrylamides and their quaternary or acid salts; acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt,
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, and diethylaminoethylmethacrylate; and any combination thereof; and (iii) optionally, said one or more anionic monomers contain functional groups selected from the group consisting of carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water soluble salts, their corresponding water dispersible salts, and any combination thereof; or said one or more anionic monomers comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, and ammonium salts, or any combination thereof. [0206] In some exemplary embodiments of the GPAM composition, the first base polymer comprises a neutral monomer content or an acrylamide content ranging from 1-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 40-60 wt-%, 40-50 wt-%, or 50-70 wt-%. [0207] In some exemplary embodiments of the GPAM composition, the first base polymer comprises a cationic monomer content ranging from 1-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 50-70 wt-%. [0208] In some exemplary embodiments of the GPAM composition, the first base polymer optionally comprises an anionic monomer content ranging from 0-50% by weight. [0209] In some exemplary embodiments of the GPAM composition, the first base polymer comprises a net cationic charge ranging from 1-99 mol%, 5-90 mol%, 10-80 mol%, 30-80 mol%, 40-80 mol%, 40- 60 mol%, 40-50 mol%, 50-70 mol%, 10-60 mol%, 10-50 mol%, 10-40 mol%, or 10-30 mol% at pH 7. [0210] In some exemplary embodiments of the GPAM composition, the first base polymer comprises a dry powder and or an aqueous composition comprising a polymer, optionally a polymer which exists as a liquid at a temperature of ~ 25 °C, wherein the polymer content of the aqueous composition by weight ranges from 0.5-20 wt-%, 1-15 wt-%, 2-10 wt-%, or 4-8 wt-%. [0211] In some exemplary embodiments of the GPAM composition, the second base polymer: (a) is prepared by a radical polymerization reaction comprising and inverse emulsion polymerization or a dispersion polymerization; (b) comprises said second standard viscosity (SV) ranging from greater than 1.4 cPs, greater than 1.4-3.5 cPs, 1.5-3.5 cPs, 1.6-3.5 cPs, 1.8-3.5 cPs, 2.0-3.5 cPs, 2.2-3.5 cPs, 2.4-3.5 cPs, 2.6-3.5 cPs, 2.8-3.5 cPs, or 3.0-3.5 cPs. [0212] In some exemplary embodiments of the GPAM composition, the second base polymer comprises one or more polymers or copolymers comprising one or more cationic monomers, optionally one or more neutral monomers, and optionally one or more anionic monomers, wherein: (i) said one or more cationic monomers are selected from the group consisting of acryloyloxyethyltrimethyl ammonium chloride (Q9), methacryloyloxyethyltrimethylammonium chloride (MAETAC), methacrylamidopropyltrimethylammonium chloride (MAPTAC), acrylamidopropyltrimethylammonium chloride (APTAC), methacryloyloxyethyldimethylammonium sulfate, diallyldialkylammonium halides diallyldimethylammonium chloride (DADMAC), diallyldiethylammonium chloride; dialkylaminoalkyl acrylates, dialkylaminoalkyl methacrylates and their quaternary or acid salts; dimethylaminoethyl acrylate (DMAEA), dimethylaminoethyl methacrylate (DMAEMA), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt,
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides, methacrylamides and their quaternary or acid salts; acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, and diethylaminoethylmethacrylate; and any combination thereof; (ii) optionally, said one or more neutral monomers are selected from the group consisting of primary amide-containing monomers, acrylamide, methacrylamide, ethyl acrylamide, crotonamide, N-methyl acrylamide, N-butyl acrylamide, N-ethyl methacrylamide, and any combination thereof; and (iii) optionally, said one or more anionic monomers contain functional groups selected from the group consisting of carboxylic acids, sulfonic acids, a phosphonic acids, their corresponding water soluble salts, their corresponding water dispersible salts, and any combination thereof; or said one or more anionic monomers comprise acrylic acid, methacrylic acid, maleic acid, itaconic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), acrylamido methanesulfonic acid, acrylamido ethanesulfonic acid, 2-hydroxy-3-acrylamide propane sulfonic acid, styrene sulfonic acid, and vinyl phosphonic acid, their corresponding alkali metal, alkaline earth metal, and ammonium salts, or any combination thereof. [0213] In some exemplary embodiments of the GPAM composition, the second base polymer comprises a neutral monomer content or an acrylamide content ranging from 0-99 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 50-70 wt-%. [0214] In some exemplary embodiments of the GPAM composition, the second base polymer comprises a cationic monomer content ranging from 1-100 wt-%, 10-90 wt-%, 20-80 wt-%, 30-80 wt-%, 40-80 wt-%, 50-80 wt-%, 60-80 wt-%, or 70-80 wt-%. [0215] In some exemplary embodiments of the GPAM composition, the second base polymer optionally comprises an anionic monomer content ranging from 0-50 wt-%. [0216] In some exemplary embodiments of the GPAM composition, the second base polymer comprises a net cationic charge ranging from 1-100 mol%, 10-90 mol%, 20-80 mol%, 30-80 mol%, 40-80 mol%, 40-60 mol%, 40-50 mol%, or 50-70 mol% at pH 7. [0217] In some exemplary embodiments of the GPAM composition, the second base polymer comprises a dispersion, an emulsion, an inverted emulsion, or an oil-in-water emulsion comprising an aqueous continuous phase and further comprising a polymer content of said second base polymer ranging from 0.5-50 wt-%, 1-45 wt-%, 2-40 wt-%, or 4-35 wt-%. [0218] In some exemplary embodiments of the GPAM composition, (a) said first base polymer comprises (i) acrylamide and DADMAC, Q9, MAPTAC, or any combination thereof; or (ii) acrylamide and DADMAC; (b) said first base polymer comprises said acrylamide content ranging from 5-95 wt-%, 30-70 wt-% or 50-70 wt-% and said cationic monomer content ranging from 5-95 wt-%, 30-70 wt-% or 30-50 wt-%; (c) said first base polymer comprises said net cationic charge ranging from 1-95 mol%, 30-70 mol% or 30-50 mol%; (d) said first base polymer comprises said aqueous composition comprising a polymer; (e) said second base polymer comprises (i) acrylamide and DADMAC, Q9,
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING MAPTAC, or any combination thereof; (ii) acrylamide and Q9, or (iii) Q9; (f) said second base polymer comprises said acrylamide content ranging from 0-95 wt-%, 0-70 wt-%, 0-60 wt-%, or 10-40 wt-% and said cationic monomer content ranging from 0-95 wt-%, 30-100 wt-%, 40-100 wt-%, or 60-90 wt-%; (g) said second base polymer comprises a net cationic charge ranging from 1-100 mol%, 30- 100 mol%, 40-100 mol%, or 60-90 mol%; (h) said second base polymer comprises an emulsion polymer or copolymer; (i) said GPAM composition comprises said GPAM emulsion; (j) said GPAM composition is suitable for use as a dry strengthening agent, a wet strengthening agent, a drainage aid, a retention aid, or any combination thereof; (k) said GPAM composition is suitable for use in the manufacture of paper, paperboard, newsprint, tissue, wherein said paper or paperboard are optionally used for printing, writing, or packaging; or (l) any combination of (a)-(k). [0219] In some exemplary embodiments, according to any of the foregoing, the GPAM composition, when added to a papermaking furnish, a cellulosic fiber stock, or a composition comprising cellulosic fibers for the manufacture of paper or board at a dosage of 0.1-20 lb/ton, 0.5-18 lb/ton, 1-16 lb/ton, 2-14 lb/ton, 2-12 lb/ton, or 3-9 lb/ton, optionally in combination with a silica and/or a flocculant, results in a paper product comprising one or more of the following properties: [0220] (i) a percent GPAM solids ranging from 0.02-15 wt-% or 0.05-10 wt-% of the paper product after drying; (ii) an increased dry tensile strength; (iii) an increased cross-directional tensile strength; (iv) a decreased drainage time determined by dynamic drainage analyzer (DDA); or (v) any combination of (i)-(iv), wherein properties (ii)-(iv) are compared to a paper product that does not contain said GPAM composition or contains an alternate GPAM composition comprising a lower GPAM standard viscosity and/or a lower standard viscosity (SV) than said GPAM composition, a GPAM standard viscosity of 2.5 cPs or less, a standard viscosity of less than 40 cPs, a lower reduced viscosity than said GPAM composition, or a reduced viscosity of less than 10 dL/g. [0221] In another aspect, the present invention provides a fiber stock composition comprising: (a) an aqueous suspension comprising cellulosic fibers; and (b) a GPAM composition according to any of the foregoing. II. Methods of Preparing Cationic GPAM Compositions [0222] This invention also discloses a method of producing the above GPAM compositions by reacting glyoxal with at least two base polymers, preferably acrylamide copolymers. The first base polymer has a standard viscosity less than or equal to 1.4 cPs while the second base polymer has a standard viscosity greater than 1.4 cPs. The inventive high MW, high viscosity GPAMs may be prepared as needed on site or may be prepared in advance on site or elsewhere, such as in a manufacturing facility. [0223] The first, low molecular weight base polymer is preferably a copolymer of acrylamide and at least one cationic monomer, such as DADMAC, Q9, or MAPTAC. The acrylamide content may be from 1 wt% to 99 wt%. The cationic monomer content may be from 1 wt% to 99%. The low molecular weight acrylamide polymer may also contain anionic monomers, non-charged monomers, and hydrophobic monomers. [0224] The first, low molecular weight acrylamide copolymers are typically prepared using solution polymerization with water being the solvent. Their weight average molecular weights are normally below one million Dalton and their standard viscosities (SV) are ≤ 1.4 cPs. Optionally, inverse emulsion polymerization or dispersion polymerization may be used. A considerable amount of chain transfer reagent may be added to lower the MW range of the first base polymer.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0225] The second, high molecular weight base polymer is preferably an acrylamide copolymer containing at least one cationic monomer, such as DADMAC, Q9, or MAPTAC. The second base polymer may also be a homopolymer of cationic monomers, such as DADMAC, Q9, or MAPTAC. The cationic monomer content may be from 1 wt% to 100 wt%. The acrylamide content may be from 0 wt% to 99 wt%. The high molecular weight acrylamide polymer may also contain anionic monomers, non-charged monomers, and hydrophobic monomers. [0226] The second, high molecular weight, high standard viscosity (SV > 1.4 cPs) base polymers are typically produced using inverse emulsion polymerization, gel polymerization, or dispersion polymerization. Inverse emulsion polymerization and dispersion polymerization may also be used. [0227] Molecular weight analysis can be carried out on low molecular weight polymers using gel permeation chromatography (GPC) and light scattering. However, both methods have certain technical challenges when used to analyze high molecular weight (> one million Dalton) polymers, especially emulsion polymers such as the second base polymer. As a result, polymer molecular weights were compared using standard viscosity (SV) analysis in this invention. SV increases with MW and may be used as an indicator of MW. [0228] In one aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: (a) glyoxalating the first base polymer in a glyoxalation reaction by contacting the first base polymer with glyoxal, optionally a molar excess of glyoxal; (b) contacting the second base polymer with the glyoxalation reaction; and (c) optionally adding additional glyoxal to produce the GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0229] In some exemplary embodiments of the method step (a) comprises (i) a ratio of glyoxal to said first base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01- 4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3; (ii) a GPAM content ranging from 1- 20 wt-%, 1-10 wt-%, 3-9 wt%, 4-8 wt%, 5-7 wt%, or 5-6 wt%; and (iii) a first pH ranging from 6-10, 7- 10, 7.5-9.5, 7.5-9, 7.5-8.5, or 7.5-8. [0230] In some exemplary embodiments the method further comprises after step (a), allowing the glyoxalation reaction to reach a first standard viscosity ranging from 10-100 cPs, 15-80 cPs, or 20-60 cPs. [0231] In some exemplary embodiments the method further comprises after reaching said first standard viscosity and prior to step (b), adding an amount of water and adjusting to a second pH ranging from 2-9, 2.5-9, 4-9, 4.5-9, 5-9, 5.2-9, 5.4-9, 5.6-9, 5.8-9, 6-9, 6.5-9, 7-9, or 7.5-8.8. [0232] In some exemplary embodiments the method further comprises after step (b), allowing the glyoxalation reaction to reach a second standard viscosity ranging from at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300- 1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs. [0233] In some exemplary embodiments the method further comprises after reaching said second standard viscosity, adjusting to a final pH ranging from 2.5-3.5, 2.8-3.2, or 3-3.2. [0234] In some exemplary embodiments the method further comprises, after step (b) and/or step (c), allowing the GPAM composition to reach a GPAM standard viscosity of greater than 2.5 cPs, 2.6-
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING 100 cPs, 2.7-90 cPs, 2.8-80 cPs, 2.9-70 cPs, 3-60 cPs, 4-50 cPs, 5-40 cPs, 6-30 cPs, 7-20 cPs, 8-20 cPs, 9-20 cPs, 10-20 cPs, or 4-10 cPs, 5-10 cPs, 6-10 cPs, 7-10 cPs, 8-10 cPs, or 9-10 cPs [0235] In some exemplary embodiments the method step (c) comprises a ratio of total added glyoxal to total base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3. [0236] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: (i) glyoxalating the second base polymer in a glyoxalation reaction by contacting the second base polymer with glyoxal, optionally a molar excess of glyoxal; (ii) contacting the first base polymer and optionally additional second base polymer with the glyoxalation reaction; and (iii) optionally adding additional glyoxal to produce the GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0237] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: (i) glyoxalating the first base polymer in a glyoxalation reaction by contacting the first base polymer with glyoxal, optionally a molar excess of glyoxal, to produce a first glyoxalated base polymer; (ii) contacting the first glyoxalated base polymer with the second base polymer; (iii) optionally adding additional glyoxal and/or additional first base polymer to produce the GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0238] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising: (i) glyoxalating the second base polymer in a glyoxalation reaction by contacting the second base polymer with glyoxal, optionally a molar excess of glyoxal, to produce a second glyoxalated base polymer; (ii) contacting the second glyoxalated base polymer with the first base polymer; (iii) optionally adding additional glyoxal and/or additional second base polymer to produce the GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0239] In some exemplary embodiments of the method: step (i) comprises a ratio of glyoxal to said first or second base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3; step (i) comprises a GPAM content ranging from 1-20 wt-%, 1-10 wt-%, 3-9 wt%, 4-8 wt%, 5-7 wt%, or 5-6 wt%; step (i) comprises a first pH ranging from 6-10, 7-10, 7.5-9.5, 7.5-9, 7.5-8.5, or 7.5-8. In some exemplary embodiments the method further comprises after step (i), allowing the glyoxalation reaction to reach a first standard viscosity ranging from 10-100 cPs, 15-80 cPs, 20-60 cPs, 20-45 cPs, 25-35 cPs, or 30-35 cPs. In some exemplary embodiments the method further comprises, after reaching said first standard viscosity and prior to step (ii), adding an amount of water and adjusting to a second pH ranging from2-9, 2.5-9, 4-9, 4.5-9, 5-9, 5.2-9, 5.4-9, 5.6-9, 5.8-9, 6-9, 6.5-9, 7-9, or 7.5-8.8. [0240] In some exemplary embodiments the method further comprises after step (ii), allowing the glyoxalation reaction to reach a second standard viscosity ranging from at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50-2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300- 1500 cPs, 400-1400 cPs, 500-1300 cPs, 500-1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs. [0241] In some exemplary embodiments the method further comprises after reaching said second standard viscosity, adjusting to a final pH ranging from 2.5-3.5, 2.8-3.2, or 3-3.2.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0242] In some exemplary embodiments the method comprises adding a ratio of total added glyoxal to total base polymer (wt/wt) ranging from 0.01-99, 0.01-50, 0.01-20, 0.01-10, 0.01-8, 0.01-6, 0.01-4, 0.01-2, 0.01-1, 0.05-0.9, 0.1-0.8, 0.15-0.6, 0.2-0.4, or 0.2-0.3. [0243] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising the steps of: (i) glyoxalating the first base polymer in a first glyoxalation reaction by contacting said first base polymer with glyoxal to produce a first glyoxalated base polymer; (ii) glyoxalating the second base polymer in a second glyoxalation reaction by contacting said second base polymer with glyoxal to produce a second glyoxalated base polymer; and (iii) combining the first glyoxalated base polymer and the second glyoxalated base polymer, and optionally adding additional glyoxal, to produce the cationic GPAM composition, wherein steps (i) and (ii) are performed in any order or simultaneously, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0244] In another aspect, the present invention provides a method for preparing the GPAM composition according any of the foregoing, the method comprising the steps of: (i) combining the first base polymer and the second base polymer; (ii) glyoxalating by contacting the first base polymer and the second base polymer with glyoxal, and (iii) optionally adding additional glyoxal and/or additional first base polymer and/or additional second base polymer to produce the cationic GPAM composition, wherein the GPAM composition comprises a reduced viscosity of at least 10dL/g at a temperature of 25° C. [0245] In some exemplary embodiments of the method, according to any of the foregoing, the cationic GPAM composition comprises: [0246] (i) a standard viscosity of at least 40 cPs, at least 50 cPs, at least 60 cPs, at least 80 cPs, at least 100 cPs, at least 125 cPs, at least 150 cPs, at least 175 cPs, at least 200 cPs, at least 2250 cPs, at least 250 cPs, at least 300 cPs, at least 400 cPs, or at least 500 cPs; or ranging from 40-2000 cPs, 50- 2000 cPs, 75-2000 cPs; 100-1800 cPs; 200-1600 cPs, 300-1500 cPs, 400-1400 cPs, 500-1300 cPs, 500- 1200 cPs; 500-1100 cPs, 500-1000 cPs, or 600-800 cPs at a temperature of 25 °C; and/or [0247] (ii) a reduced viscosity of at least 10 dL/g, at least 20 dL/g, at least 40 dL/g, at least 60 dL/g, at least 80 dL/g, at least 100 dL/g, at least 125 dL/g, at least 150 dL/g; or ranging from 10-400 dL/g, 20- 380 dL/g, 40-360 dL/g, 60-340 dL/g, 80-320 dL/g, 100-300 dL/g, 120-280 dL/g, 140-260 dL/g, 140-240 dL/g, 160-240 dL/g, or 180-220 dL/g at a temperature of 25 °C. [0248] In another aspect, the present invention provides a GPAM composition obtainable by a method according to any of the foregoing methods of GPAM preparation. [0249] In another aspect, the present invention provides a fiber stock composition comprising: (a) an aqueous suspension comprising cellulosic fibers; and (b) a GPAM composition according to any of the foregoing or obtainable by a method according to any of the foregoing methods of GPAM preparation. III. Methods of Using Cationic GPAM Compositions [0250] Methods of use of the inventive GPAM compositions for improving drainage rates and/or tensile strength of paper or board products produced from a high percentage of recycled fiber content. [0251] GPAMS of the present invention may also be used for water treatment, wastewater treatment, or for treatment of any process stream related to mining, mined ore , oil sands, oil sand
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING tailings, or textiles. GPAMS of the present invention may also be used for any industrial process for which GPAMs are useful. [0252] In one aspect, the present invention provides a method of papermaking, the method comprising: (a) contacting an aqueous suspension comprising cellulosic fibers with one or more GPAM compositions according any of the foregoing GPAM compositions; (b) removing sufficient water from the aqueous suspension to form a wet fibrous web, preferably by introducing the aqueous suspension into a headbox and draining the aqueous suspension on a wire screen; and (c) pressing and drying the wet fibrous web to obtain a paper product. [0253] In some exemplary embodiments the method further comprises diluting the aqueous suspension with water, brine, process water, or white water. [0254] In some exemplary embodiments of the method the method further comprises adjusting the aqueous suspension to a pH ranging from 5-9, 5-7.5, 6-7, 6.2-6.8, or 6.4-6.6 prior to or after addition of the one or more GPAM compositions. [0255] In some exemplary embodiments the method further comprises optionally contacting the aqueous suspension with one or more flocculants to form a flocculated fiber suspension prior to, during, or after said addition of the one or more GPAM compositions. [0256] In some exemplary embodiments said one or more flocculants comprise polyacrylamide flocculants, anionic polyacrylamide flocculants, cationic polyacrylamide flocculants, and/or amphoteric polyacrylamide flocculants, optionally having a standard viscosity (SV) ranging from 3-7 cPs, 4-6 cPs, or 4.5-5.5 cPs. [0257] In some exemplary embodiments the method further comprises optionally adding one or more inorganic microparticles prior to, during, or after said addition of the one or more GPAM compositions. [0258] In some exemplary embodiments said one or more inorganic microparticles are selected from the group of microparticles and nanoparticles consisting of silica microparticles; colloidal silica; aluminum phyllosilicate mineral particles, including but not limited to bentonite, sodium bentonite, calcium bentonite, and montmorillonite. [0259] In some exemplary embodiments said paper product comprises paper, paperboard, newsprint, or tissue, wherein said paper or paperboard are optionally used for printing, writing, or packaging. [0260] In some exemplary embodiments of the method said aqueous suspension comprising cellulosic fibers comprises: (a) one or more cellulosic fibers optionally comprising softwood fiber, hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated broke, non-wood fibers, straw pulp, wheat pulp, or a mixture of any of the foregoing; (b) a papermaking furnish comprising pulp, Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp, process water from pulp, paper, and/or board production, neutral sulfite semi chemical (NSSC) pulp, mechanical pulp, non-wood pulp, or a mixture of any of the foregoing; (c) a cellulosic fiber stock comprising a thick stock, a thick stock diluted with chemical water, synthetic water, white water, and/or process water, and a thin stock, or a mixture of any of the foregoing; or (d) any combination of (a)-(c). [0261] In some exemplary embodiments of the method said GPAM composition is added to said aqueous suspension comprising cellulosic fibers at a dosage of 0.1-20 lb/ton, 0.5-18 lb/ton, 1-16 lb/ton, 2-14 lb/ton, 2-12 lb/ton, or 3-9 lb/ton.
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0262] In some exemplary embodiments the method results in said paper product comprising one or more of the following properties: (i) a percent GPAM solids ranging from 0.02-15 wt-% or 0.05-10 wt-% of the paper product after drying; (ii) an increased dry tensile strength; (iii) an increased cross- directional tensile strength; (iv) a decreased drainage time determined by dynamic drainage analyzer (DDA); or (v) any combination of (i)-(iv), wherein properties (ii)-(iv) are compared to a paper product that does not contain said GPAM composition or contains an alternate GPAM composition comprising a lower GPAM standard viscosity and/or a lower standard viscosity (SV) than said GPAM composition, a GPAM standard viscosity of 2.5 cPs or less, a standard viscosity of less than 40 cPs, a lower reduced viscosity than said GPAM composition, or a reduced viscosity of less than 10 dL/g. [0263] In another aspect, the present invention provides a paper product produced according to any of the foregoing methods of paper preparation. [0264] The methods and compositions illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein and/or any element specifically disclosed herein. Exemplary embodiments of the invention and its advantages are further disclosed in the following examples. EXAMPLES [0265] The examples provided herein are for illustrative purposes so that the invention may be more fully understood. These examples should not be construed as limiting the invention in any way. Example 1: Polymer Preparation [0266] Base polymer preparation [0267] Acrylamide copolymers were prepared for use as base-polymers for GPAM production using polymerization techniques based on molecular weight and application requirements. [0268] Low molecular weight acrylamide base-polymers were prepared using solution polymerization in water. Inverse emulsion polymerization and dispersion polymerization are also suitable for preparing the low molecular weight acrylamide copolymers. The typical weight average molecular weight for low acrylamide base-polymers ranges from 10-1000 kDa and their standard viscosities (SV) are ≤ 1.4 cPs. [0269] High molecular weight (MW >1000 kDa or SV greater than 1.4 cPs) acrylamide polymers were produced using inverse emulsion polymerization. Gel polymerization and dispersion polymerization are also suitable methods. [0270] Molecular weight analysis was carried out on low molecular weight polymers using gel permeation chromatography (GPC) or light scattering. Both methods have technical challenges when analyzing high molecular weight polymers. As a result, polymer molecular weights were compared using standard viscosity (SV) analysis in this invention. [0271] Standard Viscosity (SV) for each base polymer was measured by adding 50 g of a 0.2% aqueous polymer solution to 50 g of 2 M NaCl solution, stirring the resulting mixture for 5 minutes, adjusting the pH to 5 and determining the viscosity at 25±0.1 °C using a Brookfield viscometer (LVT model) with UL adapter at 60 rpm. [0272] Properties of acrylamide base polymers (BP 1-7) are shown in Table 1. BP 1, a copolymer of acrylamide and dimethyldiallylammonium chloride, was prepared using solution polymerization in
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING water as described in US Patents 3556932, 8435382, and US Patent Application 20230140638. BP 2- 5, copolymers and acrylamide and acryloyloxyethyltrimethylammonium chloride (Q9) or a homopolymer of Q9, were prepared using inverse emulsion polymerization as described in US Patent 3624019, US Patent 5298555, and US Patent Application 20200087859. [0273] Table 1: Properties of acrylamide base polymers (BP1-7). *
[0274] GPAM preparation 1 [0275] A GPAM Control and GPAMs 1-9 were prepared using base polymers from Table 1. Compositions and properties of the GPAM control and GPAMs 1-9 are shown in Table 2. [0276] The GPAM Control was prepared from BP 1 using the method documented in US Patents 3556932, 8435382, and US Patent Application 20230140638. The glyoxal to base polymer weight ratio, Glyoxal/BPtotal (wt/wt), was 0.4. The finished GPAM Control had a GPAM content of 5.5 wt-%, a Brookfield viscosity of 35 cPs, and reduced viscosity of 6 dL/g. As used herein, GPAM content refers to the combined weight percent (wt-%) of glyoxal and base polymer solids in the reaction mixture. [0277] Each of GPAMs 1-9 was prepared using a mixture of two base polymers, which contained a first base polymer, BP 1 (SV=1.3 cPs), and a second base polymer selected from one of BP 2-4 (SV>1.4 cPs). BP 1 is a copolymer of acrylamide and dimethyldiallylammonium chloride prepared using solution polymerization and having a SV of 1.3 cPs. BP 2-4 are emulsion copolymers of acrylamide and/or Q9 prepared using inverse emulsion polymerization and having SV values ranging from 1.7-2.1 cPs. [0278] Preparation of GPAMs 1-9 was performed by first combining the first base polymer (e.g., BP 1) and glyoxal. The reaction was performed at GPAM content of 5.5 wt-% and a pH of 8-9.5 until a first viscosity of 30-35 cPs was reached. [0279] Water was then added to slow down the reaction and the pH was adjusted to 5.0 prior to addition of the second base polymer. [0280] A second base polymer (e.g., one of BP 2-4) was added to the reaction mixture. Once the reaction reached a desired final viscosity as shown in Table 2, the pH was lowered to 3.0 to stabilize the GPAM product. [0281] GPAM standard viscosities (GPAM SV) were determined by measuring the viscosity of 1 wt% of GPAM in 0.5 M NaCl using a Brookfield LVT viscometer with a UL adapter at 60 rpm and 25 °C. If
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING the GPAM standard viscosity (GPAM SV) was higher than 9.5 cps, the spindle rpm was lowered to 30 rpm to ensure the viscometer torque range < 95%. [0282] Table 2: Compositions and properties of GPAMS 1-9. AM
p epa a o [0284] GPAMS 10-11 were then prepared using base polymers from Table 1. Compositions and properties of GPAMs 10-11 are shown in Table 3. GPAMs 10-11 were prepared using a mixture of two base polymers, BP 1 is a copolymer of acrylamide and dimethyldiallylammonium chloride prepared using solution polymerization. BP 5 is an emulsion copolymer of acrylamide and Q9 prepared using inverse emulsion polymerization. [0285] BP 1 (SV=1.3 cPs), BP 5 (SV=1.9 cPs), glyoxal, and water were first added to the reactor and the pH value was adjusted to 8.0-9.0 range. Once the reaction mixture reached the desired final viscosity as shown in Table 3, sulfuric acid was added to lower the pH value to around 3.0. [0286] Table 3: Properties of GPAMS 10 and 11 GPAM 10 GPAM 11 1st BP* BP 1 BP 1
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING *BP - Base Polymer; BPtotal - Combined Mass of 1st BP and 2nd BP Example 2: Evaluation of high MP GPAMs as strength aids [0287] Handsheet preparation [0288] Handsheets were prepared using GPAMs produced according to Example 1. Old corrugated cardboard (OCC) pulp was obtained as a thick stock from a recycled liner board paper mill. The thick stock was initially diluted to 0.5% consistency (i.e., wt-% dry solids) using tap water. NaCl was added to the diluted stock to match mill white water conductivity. The pH of the pulp was adjusted to pH 6.4 by addition of 1 M HCl. Afterwards, GPAM compositions were introduced at 3 lb/ton, 6 lb/ton, and 9 lb/ton to the diluted pulp while agitating with an overhead stirrer. [0289] The treated pulp was then added to a dynamic sheet former (DSF) (TECHPAP France, type - FDA) to produce 110 gsm sheets. Formed sheets were pressed with blotting paper at 15 psi using a pneumatic roll press and then dried on a rotary dryer at 110 °C. Finally, dry paper sheets were oven cured at 105 °C for 5 minutes using forced air in a conventional oven and then conditioned in a standard TAPPI control room overnight. [0290] Dry tensile strength testing [0291] Handsheet tensile strengths were determined according to TAPPI Test Method T494 using a Thwing-Albert QC3A tensile tester. [0292] Cross-direction dry tensile strength was measured by applying a constant-rate-of-elongation to a handsheet sample and then recording three tensile breaking properties: (i) the force per unit width required to break a specimen (cross-direction dry tensile strength), (ii) the percentage elongation at break (stretch), and (iii) the energy absorbed per unit area of the specimen before breaking (tensile energy absorption). Only the dry tensile strength measurement is reported. [0293] Twelve measurements per condition were taken and average values were calculated. All results are normalized to 175.8 g/m2 basis weight. Cross-direction dry tensile strength results are shown in Table 4. [0294] Table 4: Cross-direction dry tensile strength Tensile Strength (lb/in) GPAM Dosage 3 lb/ton 6 lb/ton 9 lb/ton is represented as a graph of GPAM reduced viscosity
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING [0296] These results indicate that all GPAM samples provided significantly higher tensile strength than the blank. Tensile strength generally increased in a dose dependent manner as GPAM dosage was increased from 3-9 lb/ton. [0297] In addition, GPAMS 1-3 of the present invention, which have relatively high reduced viscosities of 56, 180, and 48 dL/g respectively, generated higher tensile strengths than the Control GPAM, which was a conventional GPAM product with relatively low reduced viscosity of only 6 dL/g. GPAM 2 had the highest reduced viscosity and provided the highest tensile strength across all dosages. [0298] It was surprisingly found by plotting Reduced Viscosity vs. Tensile Strength (see FIG 2) that a V-shaped curve was observed indicating that GPAM reduced viscosity is not linearly correlated with tensile strength. Tensile strength improvement over control was observed for GPAMs 1 and 3, with reduced viscosities between 40-60 dL/g, and for GPAM 2, with reduced viscosity of 180 dL/g. This is surprisingly in contrast with the linear correlation observed for reduced viscosity vs. drainage time (see FIG 4 and Example 3) [0299] These results provide proof of concept that the inventive high MW GPAMS, prepared by glyoxalating a mixture of two base polymers containing a first base polymer (BP 1; SV≤1.4 cPs) and a second base polymer (BP 2 or BP3; SV>1.4 cPs) provide paper strength enhancements over a lower MW conventional GPAM product prepared by glyoxalating a single base polymer (BP 1; SV=1.3 cPs). Example 3: Evaluation of high MP GPAMs as drainage aids [0300] DRAINAGE TESTING [0301] GPAM samples prepared according to Example 1, were subjected to drainage tests performed using a Dynamic Drainage Analyzer 5 (DDA) (PulpEye). For DDA testing, two OCC pulp suspensions (OCC Pulp 1 and 2) were obtained from two container board mills without wet end chemical addition. [0302] In the first set of experiments, 800 mL of OCC pulp 1 (0.8% consistency, 45 °C) was added to the DDA with overhead stirring at 800 rpm. GPAM product (4 lb/ton, see Tables 1-2) was then added to the pulp and the mixture was stirred for 20 sec using overhead stirring at 800 rpm. The overhead stirrer speed was then increased to 1000 rpm and a high molecular weight cationic polyacrylamide flocculant (10 mole% cationic, SV=5 cPs) was added at 0.3 lb/ton and the mixture was stirred for 5 seconds. The overhead stir speed was then lowered to 800 rpm and a micro silica product was added at various dosages according to Table 5 and the mixture was stirred for 5 seconds. [0303] The overhead stirrer was then stopped, and the treated OCC pulp was drained under 125 mBar vacuum. The time required to drain the pulp before vacuum break (i.e., a rapid increase in pressure) was recorded as the drainage time. Drainage time results are shown in Table 5. [0304] Table 5: Drainage testing results using OCC pulp 1. Consistency = 0.8%, temperature = 45 °C, pH = 6.7. Drainage time (sec) Silica Dosage 0.25 lb/ton 0.5 lb/ton 0.75 lb/ton
ATTY DOCKET NO.1149704.076013 CLIENT REF NO. US2388 – PCT FILING
[0305] Data rom Tabe 5 s potted n FIG 3 and s represented as a graph of GPAM reduced viscosity vs. drainage time in FIG 4. [0306] These results indicate that all inventive GPAM samples provided significantly faster DDA drainages rates across all dosages of silica compared to control. GPAM 6, which had the highest reduced viscosity, provided the fastest DDA drainage times. All inventive GPAM samples have relatively higher reduced viscosities (e.g., 48-132 dL/g) compared to the Control GPAM (e.g., 6 dL/g). [0307] It was surprisingly found by plotting GPAM reduced viscosity vs. drainage time (see FIG 4) that GPAM reduced viscosity is linearly correlated with drainage time. As GPAM reduced viscosity increased, the DDA drainage times decreased. This is surprisingly in contrast with the V-shaped curve observed for reduced viscosity vs. tensile strength (see FIG 2 and Example 2). [0308] In the 2nd set of drainage experiments, 700 mL of OCC pulp 2 (1.2% consistency, 21 °C) was added to the DDA with overhead stirring at 800 rpm. A GPAM product (2 lb/ton, 4 lb/ton, see Tables 3) was then added to the pulp and the mixture was stirred for 20 sec using overhead stirring at 800 rpm. The overhead stirrer speed was then increased to 1000 rpm and a high molecular weight cationic polyacrylamide flocculant (10 mole% cationic, SV=5 cPs) was added at 0.3 lb/ton and the mixture was stirred for 5 seconds. The overhead stir speed was then lowered to 800 rpm and a micro silica product was added at various dosages according to Table 6 and the mixture was stirred for 5 seconds. [0309] The overhead stirrer was then stopped, and the treated OCC pulp was drained under 125 mBar vacuum. The time required to drain the pulp before vacuum break (i.e., a rapid increase in pressure) was recorded as the drainage time. Drainage time results are shown in Table 6. [0310] Table 6. Drainage testing results using OCC pulp 2. Consistency = 1.2%, temperature = 21 °C, pH = 7.0. Drainage tine (sec) GPAM dosage 2 lb/ton 4 lb/ton t the inventive high MW GPAMS, prepared by (SV=1.3 cPs) and BP 5 (SV=1.9 cPs), provide faster
DDA drainage rates than a lower MW conventional GPAM product prepared from by glyoxalating a single base polymer (BP 1; SV=1.3 cPs).