Compositions and methods for papermaking

Abstract

Compositions and colloidal particles are provided that can be used to improve the papermaking process. The compositions and colloidal particles may include a polymer and an inorganic salt. A papermaking process carried out using the compositions and colloidal particles of the present disclosure may produce paper products with increased strength properties.

Description

[Technical Field]

[0001] The present disclosure relates generally to the field of papermaking. More specifically, the present disclosure relates to compositions and particles that can be used in papermaking processes. [Background technology]

[0002] The papermaking process may include pulping wood or some other papermaking fiber source and producing a paper material from the pulp, where a paper mat is an aqueous slurry of cellulose fibers. The slurry may then be deposited on a moving papermaking wire or fabric, and a sheet may be formed from the solid components of the slurry by draining the water. The sheet may then be pressed and dried to further remove water, and optionally the process may include passing the dried sheet through a size press to rewet the dried sheet and further drying to form a paper product.

[0003] When conducting a papermaking process, several factors must be considered to ensure the quality of the resulting paper product. For example, care should be taken to retain as many fibers as possible when draining the water from the slurry. In addition, the process should be carried out in a manner that ensures the resulting sheet has adequate strength.

[0004] The ability to form paper of excellent strength at minimal cost is important to the manufacture of paper products. Paper strength depends on several factors, including fiber selection, refining method, press load, and chemical additives used. There is an increasing use of lower quality fiber sources, and the use of such fibers often leads to the need for increased refining, greater press load, and / or chemical additives.

[0005] More beating usually results in undesirable paper properties, such as increased paper density, reduced tear, decreased porosity, and delayed production time. Increased press loads can also have mechanical limitations, such as sheet breakage, leading to inefficient paper production. Therefore, chemical additives are commonly added to the papermaking process to improve paper properties. These additives can be used to increase the strength of paper products, such as internal strength, surface strength, compressive strength, burst strength, dry strength, and tensile strength. Summary of the Invention [Problem to be solved by the invention]

[0006] The present disclosure provides compositions and methods for improving the papermaking process. [Means for solving the problem]

[0007] In some embodiments, the present disclosure provides a composition comprising a polymer and an aluminum salt and / or a ferric salt. The composition comprises the aluminum and / or ferric salt and the polymer in a weight ratio of about 0.05:1 to 100:1. In some embodiments, the composition comprises about 0.01% to about 10% by weight of the polymer.

[0008] In certain embodiments, the polymer comprises a Huggins constant of about 0.0 to about 1. In certain embodiments, the polymer comprises a conformational plot slope of about 0.05 to about 1.

[0009] In some embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, polyaluminum chloride (PAC), aluminum chlorohydrate, aluminum salts of the formula Al n Cl (3n-m) (OH) m wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n, and any combination thereof.

[0010] In some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0011] In certain embodiments, the composition comprises water.

[0012] In some embodiments, the polymer comprises monomers selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof.

[0013] In some examples, the polymer is selected from the group consisting of acrylamide, methacrylamide, 2-(dimethylamino)ethyl acrylate ("DMAEA"), 2-(dimethylamino)ethyl methacrylate ("DMAEM"), 3-(dimethylamino)propyl methacrylamide ("DMAPMA"), 3-(dimethylamino)propyl acrylamide ("DMAPA"), 3-methacrylamidopropyl-trimethyl-ammonium chloride ("MAPTAC"), 3-acrylamidopropyl-trimethyl-ammonium chloride ("APTAC"), N-vinyl pyrrolidone ("NVP"), diallyldimethylammonium chloride, and the like. chloride, "DADMAC"), diallylamine, 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride ("DMAEA.MCQ"), 2-(methacryloyloxy)-N,N,N-trimethylethanaminium chloride ("DMAEM.MCQ"), N,N-dimethylaminoethyl acrylate benzyl chloride ("DMAEA.BCQ"), N,N-dimethylaminoethyl methacrylate benzyl chloride ("DMAEM.The monomer units include a monomer selected from the group consisting of 2-acrylamido-2-methylpropane sulfonic acid ("BCQ"), 2-acrylamido-2-methylpropane sulfonic acid ("AMPS"), 2-acrylamido-2-methylbutane sulfonic acid ("AMBS"), acrylamide tertbutylsulfonate ("ATBS"), [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, salts of any of the foregoing monomer units, and any combination thereof.

[0014] In certain embodiments, the polymer comprises glyoxalated polyacrylamide (GPAM), polyvinylamine (PVAM), polyethylenimine (PEI), polyamidoamine epichlorohydrin (PAE), or any combination thereof.

[0015] In some embodiments, the polymer is a linear polymer. In some embodiments, the polymer is amphoteric.

[0016] In certain embodiments, the polymer comprises a weight average molecular weight of about 10,000 Da to about 10,000,000 Da.

[0017] In some embodiments, the polymer comprises from about 1 mol % to about 99 mol % cationic monomers and / or from about 1 mol % to about 99 mol % anionic monomers.

[0018] In some embodiments, the polymer comprises from about 0 mol % to about 80 mol % cationic monomers.

[0019] In certain embodiments, the polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

[0020] In some embodiments, the polymer comprises a carboxylic acid. In some embodiments, the polymer comprises about 1 mole % to about 8 mole % of a carboxylic acid.

[0021] In certain embodiments, the composition further comprises colloidal particles comprising a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex. In certain embodiments, the colloidal particles are water-insoluble. In certain embodiments, the colloidal particles have an average particle size ranging from about 0.01 to about 1,000 microns. In certain embodiments, the composition comprises at least about 0.01% by weight of colloidal particles.

[0022] In some embodiments, the composition excludes polysaccharides, anionic polysaccharides, and / or pulp fibers. In some embodiments, the polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines, and / or N-chloroamines.

[0023] In certain embodiments, the composition is an aqueous composition comprising a pH of about 1.0 to about 8.5.

[0024] The present disclosure also provides methods for papermaking. In some embodiments, the present disclosure provides methods for improving a papermaking process, comprising adding a composition to a papermaking machine. The composition comprises a polymer and an aluminum salt and / or a ferric salt. The composition comprises the aluminum and / or ferric salt and the polymer in a weight ratio of about 0.05:1 to 100:1.

[0025] In some embodiments, about 0.1 to about 100 lb / ton of polymer is added to the paper machine relative to solid fibers.

[0026] In some embodiments, about 0.1 to about 100 lb / ton of aluminum and / or ferric salts are added to the paper machine relative to the solid fibers.

[0027] In certain embodiments, the composition is added to the thin stock, the thick stock, the headbox, before the headbox, after the headbox, before the press section, or any combination thereof.

[0028] In some embodiments, the composition comprises from about 0.01% to about 10% by weight of the polymer.

[0029] In certain embodiments, the polymer comprises a Huggins constant of about 0.0 to about 1. In certain embodiments, the polymer comprises a conformational plot slope of about 0.05 to about 1.

[0030] In some embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, PAC, aluminum chlorohydrate, aluminum salts of the formula Al n Cl (3n-m) (OH) m wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n, and any combination thereof.

[0031] In some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0032] In certain embodiments, the composition further comprises water, hi certain embodiments, the composition is an aqueous composition comprising a pH of about 1.0 to about 8.5.

[0033] In some embodiments, the polymer comprises a monomer selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof. In some embodiments, the polymer comprises a monomer selected from the group consisting of acrylamide, methacrylamide, DMAEA, DMAEM, DMAPMA, DMAPA, MAPTAC, APTAC, NVP, DADMAC, diallylamine, DMAEA.MCQ, DMAEM.MCQ, DMAEA.BCQ, DMAEM.BCQ, AMPS, AMBS, ATBS, [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, a salt of any of the foregoing monomer units, and any combination thereof.

[0034] In certain embodiments, the polymer comprises GPAM, PVAM, PEI, PAE, or any combination thereof. In certain embodiments, the polymer is a linear polymer. In certain embodiments, the solvent is amphoteric.

[0035] In some embodiments, the polymer comprises a weight average molecular weight of about 10,000 Da to about 10,000,000 Da.

[0036] In some embodiments, the polymer comprises from about 1 mol % to about 99 mol % cationic monomers and / or from about 1 mol % to about 99 mol % anionic monomers.

[0037] In certain embodiments, the polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

[0038] In some embodiments, the polymer comprises a carboxylic acid. In some embodiments, the polymer comprises about 1 mole % to about 8 mole % of a carboxylic acid.

[0039] In certain embodiments, the paper machine includes papermaking process water and the composition is added to the papermaking process water, hi certain embodiments, the papermaking process water includes components selected from the group consisting of fibers, paper sheets, particulates, filler particles, pulp, and any combination thereof.

[0040] In some embodiments, the method further comprises forming colloidal particles in papermaking process water. In some embodiments, the colloidal particles comprise a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex. In certain embodiments, the colloidal particles are formed in the absence of paper fibers. In certain embodiments, the colloidal particles are water-insoluble. In some embodiments, the colloidal particles have an average particle size ranging from about 0.01 to about 1,000 microns. In some embodiments, the composition comprises at least about 0.01% by weight of colloidal particles.

[0041] In certain embodiments, the composition excludes polysaccharides, anionic polysaccharides, and / or pulp fibers. In certain embodiments, the polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines, and / or N-chloroamines.

[0042] The present disclosure also provides a method for preparing colloidal particles. The method includes adding a polymer to a solvent, adding an aluminum salt and / or a ferric salt to the solvent, and increasing the pH of the solvent, wherein the solvent contains the aluminum salt and / or the ferric salt and the polymer in a weight ratio of about 0.05:1 to about 100:1. In some embodiments, the pH of the solvent is about 1.0 to about 6.5 before the increasing step. In some embodiments, the pH of the solvent is about 7.0 to about 8.5 after the increasing step.

[0043] In certain embodiments, the solvent comprises from about 0.01% to about 10% by weight of the polymer.

[0044] In some embodiments, the polymer comprises a Huggins constant of about 0.0 to 1. In some embodiments, the polymer comprises a conformational plot slope of about 0.05 to about 1.

[0045] In certain embodiments, the aluminum salt is aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, PAC, aluminum chlorohydrate, aluminum salts of the formula Al n Cl (3n-m) (OH) m wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n, and any combination thereof.

[0046] In certain embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0047] In some embodiments, the solvent comprises water.

[0048] In some embodiments, the polymer comprises a monomer selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof. In certain embodiments, the polymer comprises a monomer selected from the group consisting of acrylamide, methacrylamide, DMAEA, DMAEM, DMAPMA, DMAPA, MAPTAC, APTAC, NVP, DADMAC, diallylamine, DMAEA.MCQ, DMAEM.MCQ, DMAEA.BCQ, DMAEM.BCQ, AMPS, AMBS, ATBS, [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, a salt of any of the foregoing monomer units, and any combination thereof.

[0049] In some embodiments, the polymer comprises GPAM, PVAM, PEI, PAE, or any combination thereof.

[0050] In certain embodiments, the polymer is a linear polymer. In certain embodiments, the solvent is amphoteric. In some embodiments, the polymer comprises a weight average molecular weight of about 10,000 Da to about 10,000,000 Da.

[0051] In some embodiments, the polymer comprises from about 1 mol % to about 99 mol % cationic monomers and / or from about 1 mol % to about 99 mol % anionic monomers.

[0052] In certain embodiments, the polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

[0053] In some embodiments, the polymer comprises a carboxylic acid. In certain embodiments, the polymer comprises about 1 mole % to about 8 mole % of a carboxylic acid.

[0054] In some embodiments, the colloidal particles comprise a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

[0055] In certain embodiments, the colloidal particles are formed in the absence of paper fibers. In certain embodiments, the colloidal particles are water-insoluble. In certain embodiments, the colloidal particles have an average particle size ranging from about 0.01 to about 1,000 microns.

[0056] In some embodiments, the solvent excludes polysaccharides, anionic polysaccharides, and / or pulp fibers. In some embodiments, the polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines, and / or N-chloroamines.

[0057] In certain embodiments, the method further comprises co-supplying the polymer with an aluminum salt and / or a ferric salt in a solvent.

[0058] In some embodiments, the present disclosure provides a colloidal composition comprising colloidal particles including a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex, the composition having a pH of about 2 to about 8.5.

[0059] The present disclosure also provides a method for improving a papermaking process. In some embodiments, the method includes adding a composition to a paper machine, the composition including colloidal particles, the colloidal particles including a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

[0060] Additional methods of improving a papermaking process are provided herein. In some embodiments, the methods include treating a component of the papermaking process with colloidal particles, the colloidal particles being formed from mixing a polymer with an aluminum salt and / or a ferric salt.

[0061] The foregoing has outlined broadly the features and technical advantages of the present disclosure in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the present disclosure will be described hereinafter, which form the subject of the claims of this application. It should be appreciated by those skilled in the art that the conception and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other embodiments for carrying out the same purposes of the present disclosure. It should also be realized by those skilled in the art that such equivalent embodiments do not depart from the spirit and scope of the present disclosure as set forth in the appended claims. [Brief explanation of the drawings]

[0062] A detailed description of the present invention is set forth herein below with specific reference to the following drawings:

[0063] [Figure 1] Figure 1 shows the average strength results for the cross-linked and non-cross-linked polymers. [Figure 2]Figure 2 shows the average strength results for the cross-linked and non-cross-linked polymers.

[0064] [Figure 3] Figure 3 shows the average strength data for various crosslinker ratios.

[0065] [Figure 4] FIG. 4 shows the average strength improvement data for polymers with and without carboxylic acid groups.

[0066] [Figure 5] FIG. 5 shows the average strength improvement data for polymers pre-blended with PAC as opposed to polymers co-fed or sequentially fed with PAC. DETAILED DESCRIPTION OF THE INVENTION

[0067] Various embodiments of the techniques of the present disclosure are described below. The relationship and function of the various elements of the embodiments may be better understood by reference to the detailed description below. However, the embodiments are not limited to those explicitly described below.

[0068] Unless otherwise indicated, alkyl groups described herein alone or as part of another group are optionally substituted, linear or branched, saturated monovalent hydrocarbon substituents containing, for example, from 1 to about 60 carbon atoms in the main chain, e.g., from 1 to about 30 carbon atoms. Examples of unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, s-pentyl, t-pentyl, and the like.

[0069] The terms "aryl" or "ar," as used herein alone or as part of another group (e.g., arylene), refer to an optionally substituted homocyclic aromatic group, such as a monocyclic or bicyclic group containing from about 6 to about 12 carbons in the ring portion, such as phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. The term "aryl" also includes heteroaryl functional groups. It is understood that the term "aryl" applies to cyclic substituents that are planar and contain 4n+2n electrons according to Hückel's rule.

[0070] "Cycloalkyl" refers to a cyclic alkyl substituent containing, for example, about 3 to about 8 carbon atoms, preferably about 4 to about 7 carbon atoms, and more preferably about 4 to about 6 carbon atoms. Examples of such substituents include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Cyclic alkyl groups can be unsubstituted or further substituted with alkyl groups such as methyl, ethyl, and the like.

[0071] "Heteroaryl" refers to a monocyclic or bicyclic 5- or 6-membered ring system, wherein the heteroaryl group is unsaturated and satisfies Hückel's rule. Non-limiting examples of heteroaryl groups include furanyl, thiophenyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, 1,3,4-oxadiazol-2-yl, 1,2,4-oxadiazol-2-yl, 5-methyl-1,3,4-oxadiazole, 3-methyl-1,2,4-oxadiazole, pyridinyl, pyrimidinyl, pyrazinyl, triazinyl, benzofuranyl, benzothiophenyl, indolyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolinyl, benzothiazolinyl, quinazolinyl, and the like.

[0072] The compounds of the present disclosure may be substituted with suitable substituents. As used herein, the term "suitable substituent" is intended to mean a chemically acceptable functional group, preferably a moiety that does not negate the activity of the compound. Such suitable substituents include, but are not limited to, halo groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxy groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroaralkyl groups, aralkoxy or heteroaralkoxy groups, HO-(C=O)- groups, heterocyclic groups, cycloalkyl groups, amino groups, alkyl- and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxy-carbonyl groups, alkylsulfonyl groups, and arylsulfonyl groups. In some embodiments, suitable substituents include halogen, unsubstituted C1-C 12 alkyl group, unsubstituted C4-C6 aryl group, or unsubstituted C1-C 10 Those skilled in the art will recognize that many substituents may be substituted with additional substituents.

[0073] The term "substituted," as in "substituted alkyl," means that in the group (i.e., the alkyl group), at least one hydrogen atom bonded to a carbon atom is substituted with hydroxy (-OH), alkylthio, phosphino, amido (-CON(R A )(R B )(wherein, R A and R B are independently hydrogen, alkyl, or aryl), amino (-N(R A )(R B )(wherein, R A and R B are independently hydrogen, alkyl, or aryl), halo (fluoro, chloro, bromo, or iodo), silyl, nitro (—NO2), ether (—OR A (In the formula, R Ais alkyl or aryl), esters (-OC(O)R A (In the formula, R A is alkyl or aryl), keto (-C(O)R A (In the formula, R A means substituted with one or more substituents such as alkyl or aryl), heterocyclo, etc.

[0074] Where the term "substituted" introduces a list of possible substituents, it is intended that the term apply to all members of that group, i.e., the phrase "optionally substituted alkyl or aryl" should be interpreted as "optionally substituted alkyl or optionally substituted aryl."

[0075] As used herein, the term "aluminum salts" refers to inorganic compounds containing aluminum ions, including, but not limited to, alum, aluminum chloride, aluminum sulfate, PAC, and aluminum chlorohydrate. Aluminum salts are compounds that contribute aluminum ions in aqueous solution. These can include, but are not limited to, aluminum sulfate, aluminum chloride, aluminum phosphate, aluminum nitrate, and aluminum acetate.

[0076] As used herein, the term "ferric salts" refers to inorganic compounds containing ferric ions, including, but not limited to, ferric chloride, ferric sulfate, polyferric sulfate, and polyferric chloride. Ferric salts are compounds that contribute ferric ions in aqueous solutions. These can include, but are not limited to, ferric sulfate, ferric chloride, ferric phosphate, ferric nitrate, and ferric acetate.

[0077] Terms such as "co-feed," "co-feeding," "co-fed," and the like refer to the addition of two or more components, raw materials, chemicals, etc., to a location, such as a reactor, storage vessel, and / or paper machine, separately but at essentially / substantially the same time and location. For example, two components, such as a polymer and an inorganic salt, may be fed through separate injection pipes to a location in the wet end of the paper machine, such as the furnish. Each pipe may simultaneously inject chemicals, either continuously or intermittently, into a single location within the paper machine or into two or more locations within the paper machine that are close to each other (e.g., within about 1 to about 12 inches, e.g., about 1 to about 10 inches, about 1 to about 8 inches, or about 1 to about 6 inches).

[0078] The term "degree of cross-linking" refers to the average number of linkage bonds that connect one polymer chain to another. For example, a polymer sample with an average chain length of 1000 monomer units, with 10 monomer units connected to another chain, has a degree of cross-linking of 1%.

[0079] As used herein, the term "paper" or "paper product" includes all types of fibrous webs, such as paper, paperboard, board, tissue, towels, and / or sheet materials, that contain paper fibers, such as natural and / or synthetic fibers, including, for example, cellulose fibers, wood fibers, cotton fibers, fibers from recycled paper, rayon, nylon, glass fibers, and polyolefin fibers.

[0080] The term "weight average molecular weight" refers to the average molecular weight of a polymer as determined by static light scattering measurements, specifically by Size-Exclusion Chromatography / Multi-Angle Laser Light Scattering (SEC / MALLS) techniques. The polymers of the present disclosure have a weight average molecular weight of about 10,000 to about 10,000,000 daltons.

[0081] The term "average particle size" refers to the average diameter of particles as determined by a dynamic light scattering particle size analyzer when the particles are less than 10 microns, or by a laser diffraction size analyzer when the particles are between 1 and 1,000 microns. The particles of the present disclosure have an average particle size of about 0.01 to about 1,000 microns.

[0082] The present disclosure provides compositions, particles, and methods of using the compositions and particles in papermaking processes. In some embodiments, the compositions and particles are used in methods for increasing the strength, such as the dry strength, of paper products. The compositions, which may be aqueous compositions, include colloidal particles, which may be interchangeably referred to as "particles" throughout this disclosure. The particles include a polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

[0083] Surprisingly, it has been found that the particles significantly improve the strength of paper products compared to polymer alone. In some embodiments, the particles of the present disclosure are formed by mixing trivalent ions, such as aluminum salts and / or ferric salts, with a polymer, and the resulting mixture is added to a paper machine. However, in a typical papermaking process, when trivalent ions, such as aluminum polychloride, are added to process water, they are added alone as a charge scavenger. Those skilled in the art would not attempt to combine a charge scavenger with other compounds, such as the polymer of the present disclosure, before adding it to a paper machine, because the polymer would be expected to interfere with the charge scavenger and destroy its intended function.

[0084] The polymers of the present disclosure are chemically and / or physically entangled and / or embedded in colloidal aluminum hydroxide and / or colloidal ferric hydroxide complexes. The polymers may include one or more anionic monomers, one or more cationic monomers, one or more nonionic monomers, one or more zwitterionic monomers, or any combination of these monomers.

[0085] In some embodiments, the polymer has a net negative charge, while in other embodiments, the polymer has a net positive or neutral charge. In certain embodiments, the solvent is aqueous. In some embodiments, the polymer comprises carboxylic acid groups.

[0086] For example, the polymer can contain from about 1 mol % to about 50 mol %, e.g., from about 1 mol % to about 40 mol %, from about 1 mol % to about 30 mol %, from about 1 mol % to about 20 mol %, from about 1 mol % to about 10 mol %, from about 10 mol % to about 50 mol %, from about 20 mol % to about 50 mol %, from about 30 mol % to about 50 mol %, or from about 40 mol % to about 50 mol % of a carboxylic acid.

[0087] In some embodiments, the polymer comprises from about 1 mol% to about 8 mol%, from about 1 mol% to about 7 mol%, from about 1 mol% to about 6 mol%, from about 1 mol% to about 5 mol%, from about 1 mol% to about 4 mol%, from about 1 mol% to about 3 mol%, or from about 1 mol% to about 2 mol% carboxylic acid, e.g., about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, about 5 mol%, about 6 mol%, about 7 mol%, or about 8 mol% carboxylic acid.

[0088] Illustrative, non-limiting examples of nonionic monomers that may be included in the polymer may be selected from acrylamide, methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide, N-vinylmethylacetamide, N-vinylpyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, N-tert-butylacrylamide, N-methylolacrylamide, diallylamine, allylamine, and the like.

[0089] Illustrative, non-limiting examples of anionic monomers include acrylic acid and its salts (including, but not limited to, sodium acrylate and ammonium acrylate), methacrylic acid and its salts (including, but not limited to, sodium methacrylate and ammonium methacrylate), AMPS, the sodium salt of AMPS, sodium vinyl sulfonate, styrene sulfonate, maleic acid and its salts (including, but not limited to, the sodium and ammonium salts), sulfonate itaconate, sulfopropyl acrylate or methacrylate, or other water-soluble forms of these or other polymerizable carboxylic or sulfonic acids, sulfomethylated acrylamide, allyl sulfonate, sodium vinyl sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinyl phosphonic acid, vinyl sulfonic acid, allyl phosphonic acid, sulfomethylated acrylamide, phosphonomethylated acrylamide, and the like.

[0090] Illustrative, non-limiting examples of cationic monomers include dialkylaminoalkyl acrylates and methacrylates and their quaternary or acid salts, such as dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfate, dimethylaminoethyl acrylate hydrochloride, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, dialkylaminoalkyl acrylamides or methacrylamides and their quaternary or acid salts, such as acrylamidopropyltrimethylammonium chloride, dimethylaminoethyl ...acrylate sulfate, dimethylaminoethyl methacrylate hydrochloride, Examples of the alkyl acrylates include, but are not limited to, aminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, methacrylamide propyl trimethyl ammonium chloride, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfate, dimethylaminopropyl acrylamide hydrochloride, methacrylamide propyl trimethyl ammonium chloride, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfate, dimethylaminopropyl methacrylamide hydrochloride, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, diallyl diethyl ammonium chloride, and diallyl dimethyl ammonium chloride.

[0091] Illustrative, non-limiting examples of zwitterionic monomers include N,N-dimethyl-N-acryloyloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-N-acrylamidopropyl-N-(2-carboxymethyl)-ammonium betaine, 2-(methylthio)ethylmethacryloyl-S-(sulfopropyl)-sulfonium betaine, 2-[(2-acryloylethyl)dimethylammonio]ethyl 2-methylphosphate, 2-(acryloyloxyethyl)-2'-(trimethylammonium phosphate), ... Examples of suitable amines include N-(4-sulfobutyl)-N-methyl-N,N-diallylamine ammonium betaine (MDABS), N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine, N-(4-sulfobutyl)-N-methyl-N,N-diallylamine ammonium betaine (MDABS), and N,N-diallyl-N-methyl-N-(2-sulfoethyl)ammonium betaine.

[0092] In some embodiments, the polymer comprises a monomer selected from the group consisting of acrylamide, DMAEA, DMAEM, DMAPMA, DMAPA, MAPTAC, APTAC, NVP, DADMAC, DMAEA.MCQ, DMAEM.MCQ, DMAEA.BCQ, DMAEM.BCQ, AMPS, AMBS, ATBS, [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, a salt of any of the foregoing monomer units, and any combination thereof.

[0093] In some embodiments, the polymer comprises GPAM, PVAM, PEI, PAE, or any combination thereof.

[0094] Additional examples of polymers can be found in Table 1.

[0095] [Table 1-1] [Table 1-2]

[0096] In Table 1, DAAM refers to diacetone acrylamide, AAEM refers to acetoacetoxyethyl methacrylate, and MAA refers to methacrylic acid. In some embodiments, the polymer comprises about 90 mol % acrylamide, about 8 mol % DMAEA.MCQ, and about 2 mol % itaconic acid.

[0097] The molar percentage of each monomer in the polymer is not particularly limited, hi some embodiments, the polymer comprises from about 1 mol % to about 99 mol % of cationic monomer. For example, the polymer may contain from about 1 mol % to about 90 mol %, from about 1 mol % to about 80 mol %, from about 1 mol % to about 70 mol %, from about 1 mol % to about 60 mol %, from about 1 mol % to about 50 mol %, from about 1 mol % to about 40 mol %, from about 1 mol % to about 30 mol %, from about 1 mol % to about 20 mol %, from about 1 mol % to about 10 mol %, from about 10 mol % to about 99 mol %, from about 20 mol % to about 99 mol %, from about 30 mol % to about 99 mol %, from about 40 mol % to about 99 mol %, from about 50 mol % to about 99 mol %, from about 60 mol % to about 99 mol %, from about 70 mol % to about 99 mol %, from about 80 mol % to about 99 mol %, or from about 90 mol % to about 99 mol % of the cationic monomer.

[0098] In some embodiments, the polymer comprises about 1 mol% to about 99 mol% anionic monomer. For example, the polymer can comprise about 1 mol% to about 90 mol%, about 1 mol% to about 80 mol%, about 1 mol% to about 70 mol%, about 1 mol% to about 60 mol%, about 1 mol% to about 50 mol%, about 1 mol% to about 40 mol%, about 1 mol% to about 30 mol%, about 1 mol% to about 20 mol%, about 1 mol% to about 10 mol%, about 10 mol% to about 99 mol%, about 20 mol% to about 99 mol%, about 30 mol% to about 99 mol%, about 40 mol% to about 99 mol%, about 50 mol% to about 99 mol%, about 60 mol% to about 99 mol%, about 70 mol% to about 99 mol%, about 80 mol% to about 99 mol%, or about 90 mol% to about 99 mol% anionic monomer.

[0099] In some embodiments, the polymer comprises from about 1 mol% to about 99 mol% of nonionic monomers. For example, the polymer can comprise from about 1 mol% to about 90 mol%, from about 1 mol% to about 80 mol%, from about 1 mol% to about 70 mol%, from about 1 mol% to about 60 mol%, from about 1 mol% to about 50 mol%, from about 1 mol% to about 40 mol%, from about 1 mol% to about 30 mol%, from about 1 mol% to about 20 mol%, from about 1 mol% to about 10 mol%, from about 10 mol% to about 99 mol%, from about 20 mol% to about 99 mol%, from about 30 mol% to about 99 mol%, from about 40 mol% to about 99 mol%, from about 50 mol% to about 99 mol%, from about 60 mol% to about 99 mol%, from about 70 mol% to about 99 mol%, from about 80 mol% to about 99 mol%, or from about 90 mol% to about 99 mol% of nonionic monomers.

[0100] In some embodiments, the polymer comprises from about 1 mol% to about 99 mol% zwitterionic monomer. For example, the polymer can comprise from about 1 mol% to about 90 mol%, from about 1 mol% to about 80 mol%, from about 1 mol% to about 70 mol%, from about 1 mol% to about 60 mol%, from about 1 mol% to about 50 mol%, from about 1 mol% to about 40 mol%, from about 1 mol% to about 30 mol%, from about 1 mol% to about 20 mol%, from about 1 mol% to about 10 mol%, from about 10 mol% to about 99 mol%, from about 20 mol% to about 99 mol%, from about 30 mol% to about 99 mol%, from about 40 mol% to about 99 mol%, from about 50 mol% to about 99 mol%, from about 60 mol% to about 99 mol%, from about 70 mol% to about 99 mol%, from about 80 mol% to about 99 mol%, or from about 90 mol% to about 99 mol% zwitterionic monomer.

[0101] In certain embodiments, the polymers disclosed herein comprise from about 1 mol% to about 10 mol% cationic monomers and from about 1 mol% to about 5 mol% anionic monomers. For example, the polymers can comprise from about 5 mol% to about 10 mol% cationic monomers, e.g., about 6 mol%, about 7 mol%, about 8 mol%, or about 9 mol% cationic monomers, and about 1 mol%, about 2 mol%, about 3 mol%, about 4 mol%, or about 5 mol% anionic monomers.

[0102] In some embodiments, the polymer is not a disaccharide or polysaccharide. In certain embodiments, the polymer excludes monosaccharide monomers. In certain embodiments, the compositions or particles disclosed herein exclude polysaccharides, anionic polysaccharides, and / or pulp fibers. In some embodiments, the polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines, and / or N-chloroamines. In certain embodiments, the polymer contains unmodified / unreacted amide and / or amine side chains. In some embodiments, if the polymer contains amide and / or amine side chains, less than 10% of these side chains are modified / reacted with other functional groups, such as less than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, or 0%, before the polymer is embedded in the colloidal aluminum hydroxide complex and / or colloidal ferric hydroxide complex.

[0103] In some embodiments, the polymers of the present disclosure are water-soluble amphoteric polymers containing carboxylic acid groups. In certain embodiments, the polymers of the present disclosure can be linear, branched, crosslinked, structured, synthetic, semi-synthetic, natural, and / or functionally modified. The polymers of the present disclosure can be in the form of, for example, a solution, a dry powder, a liquid, or a dispersion.

[0104] The weight-average molecular weight of the polymer is not particularly limited. In some embodiments, the polymer has a molecular weight in the range of about 10,000 Da to about 10,000,000 Da. For example, the polymer may have a molecular weight of about 10,000 Da to about 5,000,000 Da, about 10,000 Da to about 3,000,000 Da, about 10,000 Da to about 1,000,000 Da, about 10,000 Da to about 750,000 Da, about 10,000 Da to about 500,000 Da, about 10,000 Da to about 250,000 Da, about 10,000 Da to about 100,000 Da, about 10,000 Da to about 50,000 Da, or about 100,000 Da. It may have a molecular weight in the range of 0 Da to about 10,000,000 Da, about 500,000 Da to about 10,000,000 Da, about 750,000 Da to about 10,000,000 Da, about 1,000,000 Da to about 10,000,000 Da, about 3,000,000 Da to about 10,000,000 Da, about 5,000,000 Da to about 10,000,000 Da, or about 8,000,000 Da to about 10,000,000 Da.

[0105] As an additional example, the weight average molecular weight of the polymer can be from about 200,000 Da to about 1,000,000 Da, for example, from about 200,000 Da to about 800,000 Da, from about 200,000 Da to about 600,000 Da, or from about 300,000 to about 500,000 Da.

[0106] In some embodiments, the polymers of the present disclosure comprise a Huggins constant of from about 0.0 to about 1.0. For example, the Huggins constant of the polymers disclosed herein can be from about 0.1 to about 0.9, from about 0.1 to about 0.8, from about 0.1 to about 0.7, from about 0.1 to about 0.6, from about 0.1 to about 0.5, from about 0.1 to about 0.4, from about 0.1 to about 0.3, from about 0.1 to about 0.2, from about 0.2 to about 0.8, from about 0.2 to about 0.7, or from about 0.2 to about 0.6.

[0107] The Huggins equation is an empirical equation used to relate the reduced viscosity of a dilute polymer solution to the concentration of polymer in the solution. The Huggins equation is:

number

[0108] The Huggins formula is η s It is also a useful tool because it can be used to determine the intrinsic viscosity [η] or IV from experimental data by plotting / c against the concentration of the solution, c.

[0109] The Huggins constant can be calculated as follows:

number

number

[0110] For the disclosed SEC / MALLS analysis, the polymer solution was diluted to approximately 0.05% with an aqueous mobile phase (0.3 M NaCl, 0.1 M NaH2PO4, 25 ppm NaN3). Approximately 200 μL of the solution was injected into a set of TSKgel PW columns (TSKgel GMPW+GMPW+G1000PW), and the mobile phase had a flow rate of approximately 1.0 mL / min. Bovine serum albumin (BSA) was used as a standard for normalization of the multi-angle light scattering detector. The calibration constant of the RI detector was verified with sodium chloride (NaCl).

[0111] The inventors have found that linear polymers, when complexed with metal salts such as PAC, provide higher dry strength than crosslinked polymers. The linearity of a polymer can be defined using the Huggins constant, with a lower Huggins constant indicating a more linear polymer.

[0112] Certain polymers disclosed herein can have a conformation plot slope of about 0.05 to about 1.0. For example, the polymer can have a conformation plot slope of about 0.1 to about 1.0, about 0.2 to about 1.0, about 0.3 to about 1.0, about 0.4 to about 1.0, about 0.5 to about 1.0, about 0.05 to about 0.5, about 0.05 to about 0.3, or about 0.05 to about 0.1.

[0113] SEC / MALLS characterizes the LCB (long chain branching) in macromolecules through conformation plots. The conformation plots are plotted using the rms radius (radius of gyration, R g ) versus molar mass (M). Light scattering performed as SEC / MALLS can effectively and quickly characterize branching in polymers. Polymers with LCB exhibit a lower slope than corresponding linear polymers, which varies depending on the degree of LCB. Conformational plots can be constructed by SEC / MALLS analysis (see AN1005: Identifying short-chain branched polymers with conformational analysis, Wyatt Technology, Chris Deng, Ph.D., the disclosure of which is incorporated herein in its entirety).

[0114] The conformation plot is obtained by taking the average radius of gyration calculated based on the molecular weight at each point and the corresponding molecular weight on the chromatogram, and the corresponding slope is calculated from the conformation plot.

[0115] Linear polymers should have a higher conformational gradient, such as about 0.5 to 1, about 0.6 to 1, about 0.7 to 1, or about 0.8 to 1. Crosslinked polymers should have a lower conformational gradient, typically less than about 0.5, e.g., about 0 to about 0.4, about 0 to about 0.3, about 0 to about 0.2, or about 0 to about 0.1.

[0116] Illustrative, non-limiting examples of polymers of the present disclosure are listed in Table 2 along with their corresponding Huggins constants and conformational plot slopes.

[0117] [Table 2]

[0118] In some embodiments, the polymer can be crosslinked with the aluminum or iron of an aluminum hydroxide complex or a ferric hydroxide complex. In some embodiments, the polymer has a degree of crosslinking greater than 1%, greater than 2%, greater than 3%, greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, or greater than 10%. In certain embodiments, the polymer has a degree of crosslinking less than about 50%, less than about 40%, less than about 30%, or less than about 20%. For example, the polymer can have a degree of crosslinking of about 1% to about 50%, about 5% to about 50%, about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 30% to about 50%, about 2% to about 25%, about 2% to about 20%, about 2% to about 15%, about 2% to about 10%, about 3% to about 25%, about 3% to about 20%, about 3% to about 15%, about 3% to about 10%, about 4% to about 25%, about 4% to about 20%, about 4% to about 15%, or about 4% to about 10%.

[0119] In some embodiments, the crosslinks are formed from the interaction / reaction of the anionic monomer with iron and / or aluminum. For example, the polymer may include carboxylic acid groups and the crosslinks may be formed from the reaction / interaction between the carboxylic acid groups and iron and / or aluminum.

[0120] The aqueous medium can include colloidal particles (thereby forming an aqueous colloidal composition), and the aqueous medium can have a pH of, for example, about 2 to about 8.5, about 4.5 to about 8.5, about 5.5 to about 8.5, about 5.5 to about 8, about 6 to about 8, or about 7 to about 8. In some embodiments, the aqueous medium includes a pH of about 3.5 to about 8.5. In some embodiments, the colloidal particles are water-insoluble.

[0121] In certain embodiments, colloidal particles are prepared by adding a polymer disclosed herein to an aqueous solvent, such as water, and then adding an aluminum salt and / or a ferric salt to the solvent. The polymer and metal salt can be added continuously, intermittently, and in any order. In some embodiments, the polymer and metal salt are co-fed in the solvent.

[0122] In some embodiments, the solvent comprises about 0.01% to about 10% by weight of the polymer, e.g., about 0.01% to about 9%, about 0.01% to about 8%, about 0.01% to about 7%, about 0.01% to about 6%, about 0.01% to about 5%, about 0.01% to about 4%, about 0.01% to about 3%, about 0.01% to about 2%, or about 0.01% to about 1% by weight of the polymer.

[0123] In some embodiments, the solvent comprises an aluminum salt and / or ferric salt to polymer in a weight ratio of about 0.05:1 to 100:1. For example, the solvent can comprise an aluminum salt and / or ferric salt to polymer in a weight ratio of about 0.1:1, about 0.5:1, about 1:1, about 5:1, about 10:1, about 20:1, about 30:1, about 40:1, about 50:1, about 60:1, about 70:1, about 80:1, or about 90:1. In some embodiments, the solvent comprises more aluminum salt and / or ferric salt than polymer.

[0124] As an illustrative example, when the weight ratio of PAC (based on Al2O3) to polymer is about 1:1, the aluminum ions are about 159 mol % of the polymer. As a further non-limiting example, when the weight ratio of PAC to polymer is about 0.1:1, the aluminum ions are about 15.9 mol % of the polymer.

[0125] The aqueous solvent may have a pH of, for example, about 1.0 to about 6.5, and after at least a portion of the polymer and metal salt are added, the pH may be increased to about 7.0, about 7.5, about 8.0, about 8.5, or higher. In some embodiments, the pH of the composition may be increased by adding a base such as sodium hydroxide, diluting the composition with water, or the like. In certain embodiments, the pH of the composition is increased by adding a base to papermaking process water, and the pH of the papermaking process water may be, for example, about 6.5 to about 8.5. While some colloidal particles may form in the composition before the pH is increased, a substantial majority or all of the colloidal particles are formed after the pH is increased.

[0126] The colloidal particles have a weight ratio of aluminum hydroxide and / or ferric hydroxide to polymer of about 0.1:99 to about 99:0.1. For example, the weight ratio can be about 0.1:50 to about 50:0.1, about 0.1:25 to about 25:0.1, about 0.1:10 to about 10:0.1, about 0.1:5 to about 5:0.1, or about 0.1:2 to about 2:0.1. In certain embodiments, the weight ratio of aluminum hydroxide and / or ferric hydroxide to polymer is about 0.1:1 to about 2:1. In some embodiments, the weight ratio of aluminum hydroxide and / or ferric hydroxide to polymer is about 0.1:1 to about 0.9:1, or 0.1:1 to about 0.5:1.

[0127] The colloidal particles comprise from about 1% to about 99% by weight of polymer. For example, the colloidal particles may comprise from about 5% to about 99% by weight, from about 5% to about 95% by weight, from about 10% to about 99% by weight, or from about 10% to about 90% by weight of polymer.

[0128] The colloidal particles contain about 1% to about 99% by weight of aluminum hydroxide and / or ferric hydroxide. For example, the colloidal particles may contain about 5% to about 99% by weight, about 5% to about 95% by weight, about 10% to about 99% by weight, or about 10% to about 90% by weight of aluminum hydroxide and / or ferric hydroxide.

[0129] The colloidal particles have an average particle size in the range of about 0.01 to about 1,000 microns. For example, the average particle size can be about 0.05 to about 100 microns, about 0.05 to about 80 microns, about 0.05 to about 60 microns, about 0.05 to about 40 microns, about 0.05 to about 20 microns, about 0.05 to about 10 microns, about 0.1 to about 50 microns, about 0.1 to about 40 microns, about 0.1 to about 30 microns, about 0.1 to about 20 microns, or about 0.1 to about 10 microns.

[0130] As an additional example, the average particle size can be about 50 nm to about 500 nm, for example, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 100 nm to about 200 nm, about 100 nm to about 300 nm, or about 100 nm to about 400 nm.

[0131] In some embodiments, the colloidal particles have a zeta potential in the range of about -50 to about +70 mV. For example, the colloidal particles can have a zeta potential in the range of about -40 to about +60, about -30 to about +50, about -20 to about +40, about -10 to about +30, or about 0 to about +30 mV.

[0132] In some embodiments, the aqueous composition may comprise at least about 0.01 wt.% colloidal particles, based on the particle dosage in an aqueous slurry of cellulosic fibers, such as a papermaking furnish. In some embodiments, the composition comprises greater than 0.01 wt.% particles to about 10 wt.% particles, e.g., greater than about 0.02 wt.%, greater than about 0.05 wt.%, greater than about 1 wt.%, greater than about 2 wt.%, or greater than about 3 wt.% to about 5 wt.% particles. Percentages in this section refer to particle dosage relative to solid fibers dispersed in the furnish.

[0133] The compositions and / or particles disclosed herein may include additional papermaking additives, including, but not limited to, strength agents, fillers, retention aids, optical brighteners, pigments, sizing agents, starches, dewatering agents, particulates, coagulants, enzymes, and any combination thereof.

[0134] The present disclosure also provides methods of using the compositions and particles of the present disclosure in papermaking processes. For example, the compositions and / or particles can be added to a papermaking machine, such as a papermaking furnish or papermaking process water, to increase the strength of the resulting paper product.

[0135] In some embodiments, a composition including the particles is added to a paper machine. For example, a polymer can be premixed with trivalent ions, such as aluminum salts and / or ferric salts, in an aqueous medium to form particles, and the resulting mixture can be added to a paper machine.

[0136] In some embodiments, the composition includes a polymer and an inorganic salt, such as an aluminum salt and / or a ferric salt. The composition can optionally include colloidal particles, as defined herein, in an amount, such as about 0% to about 20% by weight, about 0% to about 15% by weight, about 0% to about 10% by weight, about 0% to about 5% by weight, or about 0% to about 1% by weight.

[0137] The composition can be an aqueous composition comprising a pH of about 1 to about 14, e.g., about 1 to about 10, about 1 to about 9, about 1 to about 8.5, about 3 to about 14, about 3 to about 10, about 3 to about 8.5, about 3.5 to about 8.5, about 5 to about 14, about 5 to about 10, or about 5 to about 8. In certain embodiments, the composition comprises a pH of about 1 to about 7, e.g., about 3 to about 5.

[0138] In some embodiments, the composition comprises an aluminum and / or ferric salt to polymer in a weight ratio of about 0.05:1 to 100:1. For example, the composition may comprise an aluminum and / or ferric salt to polymer in a weight ratio of about 0.1:1, about 0.5:1, about 1:1, about 5:1, about 10:1, about 20:1, about 30:1, about 40:1, about 50:1, about 60:1, about 70:1, about 80:1, or about 90:1. In some embodiments, the composition comprises more aluminum and / or ferric salt than polymer.

[0139] In certain embodiments, the composition comprises about 0.01% to about 10% by weight of polymer. For example, the composition may comprise about 0.01% to about 9%, about 0.01% to about 8%, about 0.01% to about 7%, about 0.01% to about 6%, about 0.01% to about 5%, about 0.01% to about 4%, about 0.01% to about 3%, about 0.01% to about 2%, or about 0.01% to about 1% by weight of polymer.

[0140] In some embodiments, the polymer comprises one or more anionic monomers. The pH of the aqueous composition can be adjusted to be greater than the lowest pKa value of the monomers of the polymer. The pKa of the anionic monomer is equal to the pH value, but 50% of the anionic monomers have an anionic charge. When the pH of the solution is higher than the pKa, more anionic charge sites appear on the polymer chain, which can promote interaction with trivalent ions and their derivatives. When the aqueous composition containing the polymer is added separately from the inorganic salt, for example, when the polymer and the inorganic salt are co-supplied, the pH of the aqueous composition containing the polymer can be adjusted as described in the previous section.

[0141] In some embodiments, the polymer and aluminum and / or ferric salts are co-fed to a location such as a reaction vessel, a storage tank, or a paper machine. Other ingredients, such as retention aids, drainage agents, or strength agents, may also be co-fed with the polymer and / or inorganic salt. In some embodiments, when the polymer and inorganic salt are co-fed to a location, the particles are formed in the reaction vessel, storage tank, and / or paper machine, such as in the furnish. In some embodiments, the papermaking process water receiving the polymer, inorganic salt, and / or colloidal particles has a near-neutral pH, for example, a pH of about 5.5 to about 8.5 or about 6 to about 8.

[0142] For example, an injection pipe may lead to a location in the papermaking furnish, and the pipe may inject a polymer into the furnish. There may be an adjacent pipe, which may add an additional chemical, such as an inorganic salt. The addition of each chemical may be, for example, continuous or intermittent. The injection pipes are adjacent or substantially adjacent to each other so that the chemicals are delivered to substantially the same location in the furnish at substantially the same time. The chemicals may interact in the furnish and form colloidal particles.

[0143] Thus, in some embodiments, the colloidal particles are formed in the furnish or process water, and optionally, the colloidal particles are additionally or alternatively added to the furnish or process water. In some embodiments, the colloidal particles may be formed in the composition before the composition is added to the paper furnish or process water, and optionally, the colloidal particles may be formed in the furnish or process water.

[0144] Any suitable aluminum salt may be selected and used with the innovations disclosed herein. In some embodiments, the aluminum salt may be aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, PAC, aluminum chlorohydrate, aluminum salts of the formula Al n Cl (3n-m) (OH) m wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n, and any combination thereof.

[0145] Any suitable ferric salt may be selected and used with the innovations disclosed herein, hi some embodiments, the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

[0146] The composition, particles, polymer, aluminum salt, and / or ferric salt can be added at any location or time during the papermaking process. Two or more components can be added together and / or two or more components can be co-fed to the papermaking machine. For example, the composition, particles, polymer, aluminum salt, and / or ferric salt can be added together, separately, and / or co-fed to the thin stock, thick stock, headbox, before the headbox, after the headbox, before the press section, and / or any combination of the aforementioned locations. The composition, salt, polymer, and / or particles can be added to a liquid medium of the papermaking process, such as process water or furnish.

[0147] In some embodiments, the polymer is added to the papermaking process, such as in the furnish, before, after, and / or simultaneously with the aluminum and / or ferric salt. The polymer and aluminum and / or ferric salt can be added at the same location and / or at different locations.

[0148] In some embodiments, a composition comprising any one or more of an aluminum salt, a ferric salt, a polymer, and particles is added during the papermaking process, for example, to the pulp slurry prior to the formation of a paper product. In some embodiments, one or more of the aluminum salt, the ferric salt, the polymer, and the particles may be added separately to the papermaking process, such as by co-feeding. In certain embodiments, the aluminum and / or ferric salt and the polymer are premixed prior to addition to the pulp slurry.

[0149] The amounts of polymer and aluminum and / or ferric salt added to the papermaking process are not particularly limited. In some embodiments, about 0.1 to about 100 lb / ton of aluminum and / or ferric salt is added to the papermaking process, such as pulp slurry, based on the solid fibers. For example, about 0.1 to about 75 lb / ton, about 0.1 to about 50 lb / ton, about 0.1 to about 25 lb / ton, about 1 to about 30 lb / ton, or about 1 to about 20 lb / ton of aluminum and / or ferric salt is added to the papermaking process, such as pulp slurry, based on the solid fibers.

[0150] In some embodiments, about 0.1 to about 100 lb / ton of polymer is added to a papermaking process, such as a pulp slurry, relative to the solid fibers. For example, about 0.1 to about 75 lb / ton, about 0.1 to about 50 lb / ton, about 0.1 to about 25 lb / ton, about 1 to about 30 lb / ton, or about 1 to about 20 lb / ton of polymer is added to a papermaking process, such as a pulp slurry, relative to the solid fibers.

[0151] The present disclosure also provides a method for improving a papermaking process, comprising treating a component of the papermaking process with the colloidal particles disclosed herein. As used herein, the term "treating" refers to contacting, reacting, mixing, or otherwise bringing together colloidal particles and a component. As described throughout this disclosure, the colloidal particles are formed by mixing a polymer with an aluminum salt and / or a ferric salt. In some embodiments, the colloidal particles are water-insoluble and have an average particle size ranging from about 0.01 to about 1,000 microns. In some embodiments, the colloidal particles are formed in the absence of paper fibers. For example, the colloidal particles may be formed prior to addition to the papermaking process and may contact the paper fibers only after formation and addition to the papermaking process.

[0152] In certain embodiments, components of a papermaking process are treated with colloidal particles. In certain embodiments, the components are located in papermaking process water, such as water containing thin stock, thick stock, furnish, pulp slurry, etc., and particles are added to the process water to perform the "treating" step. In certain embodiments, a polymer and an inorganic salt, such as an aluminum salt and / or a ferric salt, are added to the process water. The polymer and salt can be added together in a single composition, added separately in any order, and / or co-fed into the process water. In these embodiments, all or at least a portion of the colloidal particles are formed in the process water. When the polymer and salt are added together in a single composition, the composition can optionally include some colloidal particles.

[0153] Any component of a papermaking process can be treated with the compositions and / or particles disclosed herein. In some embodiments, the component being treated is selected from the group consisting of fibers, such as cellulose fibers, paper sheets, paper products, particulates, filler particles, pulp, and any combination thereof.

[0154] Additionally, the "treating" step may be performed at one or more locations throughout the papermaking process, such as before the headbox, in the headbox, after the headbox, before the press section, and any combination thereof.

[0155] The polymer may comprise any one or more of the polymers disclosed herein, such as a polymer comprising a monomer selected from the group consisting of anionic monomers, cationic monomers, nonionic monomers, zwitterionic monomers, and any combination thereof.

[0156] As described throughout this disclosure, the colloidal particles have an average particle size ranging from about 0.1 to about 1,000 microns.

[0157] The foregoing may be better understood by reference to the following examples, which are intended for illustrative purposes and are not intended to limit the scope of the disclosure or its application in any way. [Example]

[0158] Example

[0159] Several inorganic complexes were dosed into recycled paperboard furnish to test the dry strength performance of the paper. The samples (listed in Table 3) were added to the wet end of the papermaking system (a dilute suspension of fibers in water) at the indicated doses. Sheets were then formed in handsheets, pressed, and dried. The resulting sheets were allowed to equilibrate for about 18 hours at about 23°C and about 50% relative humidity before strength testing. Strength tests included tensile strength, short span compression strength (SCT or STFI), burst strength, and ring crush strength (RCT).

[0160] [Table 3]

[0161] In Table 3, complexes were prepared by mixing diluted polymer and PAC solutions. The polymer and PAC can be diluted with water from any source.

[0162] In one study, a polyampholyte backbone (polymer 14:8 mol% methylchloride quat (MCQ) / 4 mol% acrylic acid (AA) / 88 mol% acrylamide) was crosslinked with PAC and zirconyl chloride at active ratios of about 1:1 and about 0.06:1, respectively. The polymer backbone (control sample) and crosslinked sample were dosed into fiber stock at about 4 and about 8 lb / ton actives. Table 4 shows the polymer sample details. Figure 1 shows the average strength results, which are also summarized in Table 6. The results show that the PAC crosslinked sample provides a significant improvement in strength compared to the uncrosslinked control polymer. The zirconyl chloride sample performs similarly to the control.

[0163] As can be seen in Table 5, cationic polymers (polymer 8) or polyampholytes with an overall cationic charge (polymer 17) have no or weak interactions with PAC, whereas anionic polymers or polyampholytes with an overall anionic charge have stronger interactions with PAC. Also, much lower pH and / or lower concentrations are required to minimize gelation or high viscosity.

[0164] [Table 4]

[0165] [Table 5]

[0166] In Table 5, the complexes were prepared by adding concentrated PAC (approximately 24% Al2O3) dropwise to the dilute polymer solution with mixing. The "PAC:polymer ratio" is the ratio of PAC active (as Al2O3) to polymer active.

[0167] [Table 6]

[0168] Another study was conducted to evaluate the performance of different inorganic crosslinkers. As in the previous study, the same base polyampholyte was used (Polymer 14). PAC, alum, and ferric chloride were used as crosslinkers at an actives ratio of approximately 1:1. The polymer backbone (control sample) and crosslinked samples were dosed into recycled fiber stock at approximately 4 and 8 lb / ton actives. Figure 2 shows the average strength results, which are summarized in Table 7. Here, the results of the previous study were confirmed, with the PAC crosslinked sample providing significant strength improvement compared to the control. Both the alum and ferric chloride samples showed strength improvement compared to the control, but the measured overall strength was not at the same level as the PAC crosslinked sample.

[0169] [Table 7]

[0170] Another study was performed to evaluate the optimal PAC crosslinking ratio. Polymer 14 polyampholyte backbone was used and crosslinked with PAC at the following ratios (PAC:polyampholyte), based on polymer active: about 0.125:1, about 0.25:1, about 0.5:1, about 1:1, and about 2:1. Figure 3 shows the average strength data, which is summarized in Table 8. The average strength increases as the crosslinker ratio increases up to a ratio of about 1:1. Further increasing the PAC content to about 2:1 did not result in any further strength improvement.

[0171] [Table 8]

[0172] Additional studies were performed to examine the effect of anionic charge on strength improvement. Three polymers were tested, each with 0 mol% (Polymer 8), 1 mol% (Polymer 33), and 4 mol% (Polymer 14) acrylic acid content. These polymers were added alone (control) without PAC, sequentially with PAC added first (1:1 ratio with polymer, based on actives), and as a premixed PAC complex (1:1 ratio with polymer, based on actives). The results are summarized in Table 9. These results show that strength increases when PAC is added sequentially with each polymer. This increase is nearly equivalent to the strength provided by PAC alone. When complexed with PAC, each polymer shows further strength improvement compared to sequential PAC addition. This strength improvement is proportional to the acrylic acid content, and the effect of PAC complexation is more pronounced at higher acrylic acid contents. These results indicate that acrylic acid is not necessary to observe strength improvements via PAC complexation, but the presence of acrylic acid in the polymer backbone enhances the strength improvements achieved via PAC complexation, with higher acrylic acid content resulting in higher strength.

[0173] [Table 9]

[0174] In further studies, polymer 14 was blended with either PAC or polyferric sulfate (PFS) at low pH (below about 4.5) in the ratios shown in Table 10. The "PFS:polymer ratio" is the ratio of PFS actives (as Fe2O3) to polymer actives. The polymer / salt mixture was then dosed into paper pulp (lab-produced recycled fiber, pH about 6.5) at 8 lb / ton based on polymer actives. Sheets made with the different polymer / salt blends were then tested for strength parameters shown in Table 10. It can be seen that, in general, increasing the PFS content in the sample results in an increase in average sheet strength. Additionally, the 1:1 PFS sample performs similarly to the 1:1 PAC sample.

[0175] [Table 10]

[0176] In additional studies, samples were dosed into recycled paperboard furnish. Samples (described below) were added to the wet end of the papermaking system (a dilute suspension of fibers in water) at the indicated dose. Sheets were then formed in handsheets, pressed, and dried. The resulting sheets were allowed to equilibrate for approximately 18 hours at approximately 23°C and approximately 50% relative humidity before strength testing.

[0177] In the first trial, approximately 8 lb / ton of Polymer 41 and approximately 5 lb / ton of alum were added separately to the furnish (alum first). In the second trial, approximately 5 lb / ton of alum was added to approximately 8 lb / ton of an aqueous solution of Polymer 41, and the resulting mixture was added to the furnish. The mixture had a pH of approximately 3.5. In the third trial, approximately 5 lb / ton of alum was added to approximately 8 lb / ton of an aqueous solution of Polymer 41. The pH of the mixture was adjusted to approximately 4.5 using NaOH. The resulting mixture was added to the furnish. In the fourth trial, approximately 5 lb / ton of alum was added to approximately 8 lb / ton of an aqueous solution of Polymer 41. The pH of the mixture was adjusted to approximately 6 using NaOH. The resulting mixture was added to the furnish. In the fifth trial, approximately 5 lb / ton of alum was added to approximately 8 lb / ton of an aqueous solution of Polymer 41. The pH of the mixture was adjusted to about 8 using NaOH. The resulting mixture was added to the furnish. In a sixth trial, about 5 lb / ton of alum was added to about 8 lb / ton of Polymer 41 in water. The pH of the mixture was adjusted to about 10 using NaOH. The resulting mixture was added to the furnish. In a seventh trial, about 5 lb / ton of alum was added to about 8 lb / ton of Polymer 41 in water. The pH of the mixture was adjusted to about 12 using NaOH. The resulting mixture was added to the furnish. The strength results are shown in Table 11 as a percent improvement over baseline.

[0178] [Table 11]

[0179] The data show a beneficial effect at pHs from about 3.5 to about 8.5, however, the effect was minimal at pH 10 and almost nonexistent at pH 12.

[0180] Additional strength studies were performed that showed that a polymer containing carboxylic acid groups (Polymer 16) provided advantageous performance over a polymer containing anionic monomers without carboxylic acid functionality (Polymer 17). As can be seen in Figure 4 and Table 12, Polymer 16 outperformed Polymer 17 at all dosage levels. Data were obtained using a procedure similar to that described above to obtain the data shown in Figure 1.

[0181] [Table 12]

[0182] In additional experiments, the inventors confirmed that premixing of polymer and metal salt resulted in the formation of well-defined nanoparticles under papermaking conditions and provided the greatest improvement in dry strength compared to co-feeding and sequential feeding schemes.

[0183] To perform sequential feed trials, approximately 8 lb / ton of PAC was dosed into the furnish and allowed to mix for approximately 10 seconds. Then, approximately 8 lb / ton of polymer was dosed into the furnish and allowed to mix for approximately 10 seconds. For co-feed trials, approximately 8 lb / ton of PAC and approximately 8 lb / ton of polymer were dosed into the furnish simultaneously from different streams and allowed to mix in the furnish for approximately 20 seconds. For pre-mix trials, the polymer and PAC were dosed into an aqueous medium at a 1:1 actives ratio to form a pre-mix composition. This composition was then added to the furnish at 8 lb / ton of polymer actives and allowed to mix in the furnish for approximately 20 seconds. The polymer used in these examples was Polymer 14 in Table 1.

[0184] Sheets were then hand-formed, pressed, and dried. The resulting sheets were allowed to equilibrate at about 23°C and about 50% relative humidity for about 18 hours before strength testing. The data are shown in Figure 5 and Table 13.

[0185] [Table 13]

[0186] All of the compositions and methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. The invention may be embodied in many different forms, and certain preferred embodiments of the invention are described in detail herein. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. Additionally, unless expressly stated otherwise, the term "a" is intended to include "at least one" or "one or more." For example, "a polymer" is intended to include "at least one polymer" or "one or more polymers."

[0187] Any range given in either absolute or approximate terms is intended to encompass both, and any definitions used herein are intended to be descriptive, not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Furthermore, all ranges disclosed herein should be understood to encompass all subranges subsumed therein, including all fractional and whole values.

[0188] Any composition disclosed herein can comprise, consist of, or consist essentially of any element, component, and / or ingredient disclosed herein, or any combination of two or more of the elements, components, or ingredients disclosed herein.

[0189] Any method disclosed herein may comprise, consist of, or consist essentially of any method step(s) disclosed herein, or any combination of two or more of the method steps disclosed herein.

[0190] The transitional phrase "comprising," which is synonymous with "including," "containing," or "characterized by," is inclusive or open-ended and does not exclude additional, unrecited elements, components, ingredients, and / or method steps.

[0191] The transitional phrase "consisting of" excludes any element, component, ingredient, and / or method step not specified in the claim.

[0192] The transitional phrase "consisting essentially of" limits the scope of a claim to certain elements, components, ingredients, and / or steps, and those that do not materially affect the basic and novel characteristics of the claimed invention.

[0193] Unless otherwise specified, all molecular weights referred to herein are weight average molecular weights and all viscosities were measured at 25°C using neat (undiluted) polymer.

[0194] As used herein, the term "about" refers to a cited value that is within error resulting from the standard deviation found in their respective testing measurements; where such error cannot be determined, "about" may refer, for example, to within 5% of the cited value.

[0195] Furthermore, the present invention encompasses all possible combinations of any or all of the various embodiments described herein. It should also be understood that various changes and modifications to the preferred embodiments of the present invention described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its intended advantages. It is therefore intended that such changes and modifications be covered by the appended claims.

Claims

1. A polymer; an aluminum salt and / or a ferric salt, The composition comprises the aluminum salt and / or the ferric salt and the polymer in a weight ratio of about 0.05:1 to 100:

1.

2. The composition of claim 1, wherein the composition comprises from about 0.01% to about 10% by weight of the polymer.

3. The composition of claim 1 or 2, wherein the polymer has a Huggins constant of from about 0.0 to about 1.

4. The composition of any one of claims 1 to 3, wherein the polymer has a conformation plot slope of from about 0.05 to about 1.

5. The aluminum salt may be aluminum chloride, aluminum chloride hydrate, aluminum sulfate, alum, polyaluminum chloride (PAC), aluminum chlorohydrate, aluminum salts of the formula Al ｎ Cl （３ｎ－ｍ） (OH) ｍ wherein m is an integer from 0 to 100, n is an integer from 1 to 100, and m is less than 3n; and any combination thereof.

6. 6. The composition of any one of claims 1 to 5, wherein the ferric salt is selected from the group consisting of ferric chloride, ferric sulfate, polyferric salts, and any combination thereof.

7. The polymer may be selected from the group consisting of acrylamide, methacrylamide, 2-(dimethylamino)ethyl acrylate ("DMAEA"), 2-(dimethylamino)ethyl methacrylate ("DMAEM"), 3-(dimethylamino)propyl methacrylamide ("DMAPMA"), 3-(dimethylamino)propyl acrylamide ("DMAPA"), 3-methacrylamidopropyl-trimethyl-ammonium chloride ("MAPTAC"), 3-acrylamidopropyl-trimethyl-ammonium chloride ("APTAC"), N-vinylpyrrolidone ("NVP"), diallyldimethylammonium chloride ("DADMAC"), diallylamine, 2-(acryloyloxy)-N,N,N-trimethylethanaminium chloride ("DMAEA.MCQ"), 2-(meth ...

7. The composition of any one of claims 1 to 6, comprising a monomer selected from the group consisting of N,N-trimethylethanaminium chloride ("DMAEM.MCQ"), N,N-dimethylaminoethyl acrylate benzyl chloride ("DMAEA.BCQ"), N,N-dimethylaminoethyl methacrylate benzyl chloride ("DMAEM.BCQ"), 2-acrylamido-2-methylpropanesulfonic acid ("AMPS"), 2-acrylamido-2-methylbutanesulfonic acid ("AMBS"), acrylamido tert butyl sulfonate ("ATBS"), [2-methyl-2-[(1-oxo-2-propenyl)amino]propyl]-phosphonic acid, acrylic acid, methacrylic acid, maleic acid, itaconic acid, a salt of any of the foregoing monomer units, and any combination thereof.

8. 8. The composition of any one of claims 1 to 7, wherein the polymer comprises glyoxalated polyacrylamide (GPAM), polyvinylamine (PVAM), polyethyleneimine (PEI), polyamidoamine epichlorohydrin (PAE), or any combination thereof.

9. The composition of any one of claims 1 to 8, wherein the polymer is a linear polymer.

10. 10. The composition of any one of claims 1 to 9, wherein the polymer is cationic, anionic, zwitterionic, nonionic, amphoteric with a net positive charge, or amphoteric with a net negative charge.

11. The composition of any one of claims 1 to 10, wherein the polymer comprises from about 1 mol % to about 8 mol % of a carboxylic acid.

12. The composition of any one of claims 1 to 11, further comprising colloidal particles comprising the polymer embedded within a colloidal aluminum hydroxide complex and / or a colloidal ferric hydroxide complex.

13. The composition of any one of claims 1 to 12, wherein the composition excludes polysaccharides, anionic polysaccharides, and / or pulp fibers.

14. The composition of any one of claims 1 to 13, wherein the polymer excludes hydroxamic acid groups, isocyanate groups, N-bromoamines and / or N-chloroamines.

15. 1. A method for improving a papermaking process, said method comprising:

1. A method comprising adding a composition to a paper machine, the composition comprising a polymer and an aluminum salt and / or a ferric salt, the composition comprising the aluminum salt and / or the ferric salt to the polymer in a weight ratio of about 0.05:1 to 100:

1.

16. 16. The method of claim 15, wherein the composition is added to the thin stock, the thick stock, the headbox, before the headbox, after the headbox, before the press section, or any combination thereof.

17. 17. The method of claim 15 or 16, wherein the composition comprises colloidal particles and / or the colloidal particles are formed in the process water of the paper machine.

18. 18. The method of claim 17, wherein the colloidal particles are formed in the absence of paper fibers.

19. 1. A method for preparing colloidal particles, said method comprising: adding a polymer to a solvent; adding an aluminum salt and / or a ferric salt to the solvent; and increasing the pH of the solvent, wherein the solvent comprises the aluminum salt and / or the ferric salt and the polymer in a weight ratio of about 0.05:1 to 100:

1.

20. 20. The method of claim 19, wherein the pH of the solvent is from about 1.0 to about 6.5 before the increasing step.

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