REPULPABLE POLYMER SYNTHESIS WITH TEMPORARY MOISTURE RESISTANCE FOR TISSUE APPLICATION

Abstract

A grafted polyvinyl alcohol polymer has a balance between hydrophilicity and hydrophobicity. The grafted polyvinyl alcohol polymer has a chemical functionality that allows adsorption onto pulp fibers, formation of a polymer film upon drying, water repellency upon wetting, and expansion and rupture of the polymer film upon prolonged wetting in water. When incorporated into paper products, the polymer can provide paper with improved moisture resistance, temporary water repellency, and / or dispersibility in aqueous solutions.

Description

REPULPABLE POLYMER SYNTHESIS WITH TEMPORARY MOISTURE RESISTANCE FOR TISSUE APPLICATION This application claims the benefit of priority pursuant to 35 USC §119(e) from prior US Provisional Patent Application No. 62 / 754,598, filed on November 2, 2018, which is incorporated herein by reference in its entirety. FIELD OF INVENTION The present invention relates to a grafted polyvinyl alcohol polymer, compositions containing the grafted polyvinyl alcohol polymer, and its use for the manufacture of paper and associated products. BACKGROUND OF THE INVENTION In general, papermaking involves forming a water-based pulp composition, then laminating and drying the pulp to create a desired paper product. If the paper product is to be used in a wet application, such as paper towels or tissues, good moisture resistance is often desirable. However, if the moisture resistance is too strong, the paper may not disperse when submerged in water, potentially clogging sewer lines. The lack of water dispersion also makes paper difficult to recycle. Office paper, for example, is often recycled. When recycled, paper must be repulped, which generally involves dispersing the paper in an aqueous solution. However, to be usable with printers, office paper needs to be water-repellent; otherwise, the ink applied to the paper by the printer will run, reducing the quality of the printed document or image. Various additives have been used to improve the moisture resistance and water repellency of paper. Generally, these additives are polymers bonded to paper fibers by covalent bonds. While these polymers can improve moisture resistance or water repellency, they create problems when paper is recycled. When paper is repulped, remnants of the additives, which provide covalent bonding to the paper fibers, leave behind hydrophilic and sticky polymer residues that re-agglomerate in various parts of the paper mill. These agglomerates, known as sticky residues, can clog various components of a paper mill. nQy / rn / Lznz / q / Yi Therefore, there is a need for an additive that produces a paper that is easily dispersible in water, while improving the paper's moisture resistance, providing the paper with temporary water repellency and / or providing the paper with water absorption retarding properties. BRIEF DESCRIPTION OF THE INVENTION A feature of the present invention is to provide a novel non-reactive grafted polyvinyl alcohol polymer that has a finely tuned balance between hydrophilicity and hydrophobicity. Another feature of the present invention is to provide a resin that is water-dispersible and readily adsorbs onto cellulosic substrates, but has temporary properties of repelling water and / or retarding water adsorption. An additional feature of the present invention is to provide a disposable blotting paper and / or tissue that will temporarily adsorb much less water when treated with a polymer and / or resin containing the polymer. An additional feature of the present invention is to provide a disposable handkerchief, wherein prolonged immersion of the treated disposable handkerchief in water does not prevent the water from breaking the fiber-fiber intertwining, thus allowing complete dispersion of the disposable handkerchief in water. Another feature of the present invention is to provide a polymer that imparts dry tensile strength and / or wet tensile strength to the disposable tissue, but allows good water dispersibility in sewer lines. An additional feature of the present invention is to provide a polymer that does not prevent the re-pulping and / or recycling of the paper, since it can be slowly plasticized and then washed or redispersed with water for a few minutes from the initial dispersion. Another feature of the present invention is to provide a novel grafted polyvinyl alcohol polymer that is a reaction product of a polyvinyl alcohol having a relatively low degree of hydrolysis and vinyl cationic monomers. The additional features and advantages of the present invention will be partly set forth in the following description and partly evident from the description, or can be learned through the practice of the present invention. The objectives and other advantages of the present invention will be realized and attained by means of the elements and combinations specifically mentioned in the description and the appended claims naj / rn / Lznz / q / Yi. One or more of the foregoing features have been achieved according to the present invention by providing a grafted polyvinyl alcohol polymer of the present invention. The grafted polyvinyl alcohol polymer has or includes a polyvinyl alcohol backbone and a plurality of side chains grafted onto the polyvinyl alcohol backbone. One or more of said side chains of the plurality of side chains includes: i) one or more units selected from: an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and / or a reactive quaternary ammonium salt; and, optionally, ii) units of an aliphatic amide or a branched alkyl acrylate or any combination thereof. The present invention further relates to a polymer composition comprising the grafted polyvinyl alcohol polymer and an aqueous medium in which the grafted polyvinyl alcohol polymer is dispersed. The present invention further relates to an aqueous-based emulsion polymer that includes the grafted polyvinyl alcohol polymer. The present invention further relates to a cellulosic pulp product comprising cellulosic pulp and the grafted polyvinyl alcohol polymer. The present invention further relates to a paper product comprising a paper material and the grafted polyvinyl alcohol polymer. The present invention further relates to a product that includes at least one layer of paper containing the grafted polyvinyl alcohol polymer. The product is paper sheets, cardboard, disposable tissues, and / or cardstock. The present invention further relates to a fibrous material comprising cotton fibers and the grafted polyvinyl alcohol polymer. The present invention further relates to a papermaking process, which includes a step of absorbing or otherwise treating a quantity of polyvinyl alcohol polymer grafted onto cellulosic papermaking fibers in an aqueous suspension. The process may further include a step of forming the aqueous suspension into a mesh and drying the mesh. In the process, the quantity of grafted polyvinyl alcohol polymer is effective in increasing the paper's wet strength and / or dry strength and / or water dispersibility compared to paper made from the aqueous suspension without the grafted polyvinyl alcohol polymer. The present invention further relates to a process for manufacturing a grafted polyvinyl alcohol polymer. The process includes the steps of providing an aqueous solution of a polyvinyl alcohol polymer and adding to the aqueous solution at least one free-radical initiator and a plurality of monomers forming the side chain(s), referred to as side-chain monomers. In the process, the plurality of side-chain monomers includes: (a) an aliphatic monocarboxylic acid and / or an aliphatic dicarboxylic acid and / or a reactive quaternary ammonium salt, or any combination thereof; (b) optionally an aliphatic amide; and (c) optionally a branched alkyl acrylate. The present invention further relates to a process for repulping paper. The process includes a step of contacting a paper product with a caustic aqueous solution containing alkali metal ions. Following this contact, the carboxylic functionalities in the grafted polyvinyl alcohol polymer according to the present invention are converted into alkali metal carboxylate functionalities. In this process, the paper product comprises a paper material and the grafted polyvinyl alcohol polymer of the present invention. The present invention further relates to a polymer blend comprising a first grafted polyvinyl alcohol polymer comprising a first polyvinyl alcohol backbone and a first plurality of side chains grafted onto the first polyvinyl alcohol backbone. The side chains of the first plurality of side chains include: i) one or more units selected from: an aliphatic monocarboxylic acid and / or an aliphatic dicarboxylic acid; and, optionally, ii) an aliphatic amide or a branched alkyl acrylate or any combination thereof. The polymer blend also includes a second grafted polyvinyl alcohol polymer comprising a second polyvinyl alcohol backbone and a second plurality of side chains grafted onto the second polyvinyl alcohol backbone.The side chains of the second plurality of side chains include: i) one or more units of a reactive quaternary ammonium salt; and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof. It should be understood that both the above general description and the following detailed description are merely illustrative and explanatory and are intended to provide further explanation of the present invention, as claimed. BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows a Fourier transform infrared spectroscopy of an embodiment of the grafted polyvinyl alcohol polymer of the present invention. Figure 2 shows the particle size analysis of an embodiment of the grafted polyvinyl alcohol of the present invention by dynamic light scattering. Figure 3 shows the molecular weight distribution by gel permeation chromatography of an embodiment of the grafted polyvinyl alcohol polymer of the present invention. Figure 4 is a bar chart showing the wet and dry strengths of hand-molded paper sheets treated with some examples of the grafted polyvinyl alcohol resin preparation of the present invention. Figure 5 is a bar chart showing the paper dispersibility test of hand-molded paper sheets treated with some examples of grafted polyvinyl alcohol resin preparation of the present invention. Figure 6 is a bar chart showing a comparison of the deterioration of moisture resistance of hand-molded paper sheets treated with examples of the grafted polyvinyl alcohol polymer of the present invention and compared with paper treated with glyoxylated polyacrylamide. Figure 7 is a bar chart showing a comparison of the relative wet and dry strengths as well as the water dispersibility of handmade leaves treated with some examples of the present invention. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a grafted polyvinyl alcohol polymer that is water-dispersible and readily adsorbs onto cellulosic substrates, but which has temporary water-repellent and / or water-retardant properties. Paper products incorporating the grafted polyvinyl alcohol polymer may have temporary moisture resistance and be repulpable, thus enabling recycling and / or dispersion in sewer lines. The grafted polyvinyl alcohol polymer of the present invention comprises or includes a polyvinyl alcohol backbone having a plurality of vinyl alcohol and vinyl acetate repeating units linked together. This backbone therefore has a plurality of acetate and hydroxyl residues hanging from a carbon backbone of the polyvinyl alcohol backbone. The polyvinyl alcohol backbone structure provides acetate and hydroxyl residues when the polyvinyl alcohol backbone is in its unreacted form, and these residues can then be reacted with monomers to form the grafted polyvinyl alcohol polymer of the present invention.Alternatively, repeating alkylene units may be present in the main chain, and thus the polyvinyl alcohol main chain can be described as a polymer of poly(alkylene-co-vinyl alcohol-co-vinyl acetate). Consequently, the polyvinyl alcohol main chain may be considered, called, or referred to as a polymer, copolymer, or terpolymer. The free, unreacted polyvinyl alcohol backbone can have a degree of hydrolysis from approximately 74 mol% to approximately 99 mol%, or other amounts below or above this range. All values ​​between 74 mol% and 99 mol% are included in this range, including the endpoints, and therefore the range can be 74 mol% to 95 mol%, 74 mol% to 90 mol%, 74 mol% to 88 mol%, 76 mol% to 95 mol%, 76 mol% to 90 mol%, and 76 mol% to 88 mol%.Since all values ​​between 74 mol% and 99 wt% are included in this range, the degree of hydrolysis can be 74 mol%, 75 mol%, 76 mol%, 77 mol%, 78 mol%, 79 mol%, 80 mol%, 81 mol%, 82 mol%, 83 mol%, 84 mol%, 85 mol%, 86 mol%, 87 mol%, 88 mol%, 89 mol%, 90 mol%, 91 mol%, 92 mol%, 9 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, and 98 mol%, with decimals and fractions thereof. included. As used in the present invention, the word approximately refers to a degree of hydrolysis of ± 1 mol% of the value mentioned for the degree of hydrolysis. In a preferred aspect, the polyvinyl alcohol main chain, in its free, unreacted form, has a degree of hydrolysis of approximately 74 mol% to approximately 88 mol%, and this polyvinyl alcohol main chain, in its free, unreacted form, reacts with at least one monomer comprising the reactive quaternary ammonium salt. The degree of hydrolysis can be an indicator of how many free dangling hydroxyl groups (-OH) are present in the polyvinyl alcohol backbone. The synthesis of polyvinyl alcohol first involves the polymerization of vinyl acetate, which forms polyvinyl acetate. The acetate moieties (O-(CO)-CH3) are then replaced by alcohol moieties through a hydrolysis reaction to form the free dangling hydroxyl groups. Therefore, as used in the present invention, the degree of hydrolysis can refer to the mole percent of acetate moieties that are replaced by alcohol moieties upon transesterification of polyvinyl acetate. Thus, as an example, 74 mole percent of acetate moieties are replaced by alcohol moieties for a polyvinyl alcohol backbone characterized by a degree of hydrolysis of 74 mole percent. In one aspect of the present invention, the polyvinyl alcohol backbone, in its unreacted form, can have a number-average molecular weight of approximately 1,000 Daltons to approximately 50,000 Daltons. The weighted average molecular weight of the polyvinyl alcohol backbone, in its unreacted form, can be from 10,000 Daltons to 200,000 Daltons. The main chain of polyvinyl alcohol, in its unreacted form, can have a polydispersity, Mw / Mn, of 1.1 to 10, such as 2 to 7. The unimodal molecular weight distribution of the polyvinyl alcohol backbone, in its unreacted form, can be from 5 K to 500 K Daltons, or from 50 K to 500 K Daltons. The unimodal molecular weight distribution can have a mean of approximately 219 K Daltons ± 50,000 Daltons, or approximately 219 K Daltons ± 10,000 Daltons. The free, unreacted polyvinyl alcohol that forms the main chain of the grafted polyvinyl alcohol polymer may be referred to in the present invention as PVOH. The polyvinyl alcohol main chain, in its unreacted form, may be one or more of POVAL™ (Kuraray Co. Ltd.) 5 / 88, 3 / 80, 3 / 82, 3 / 85, 4 / 85, 4 / 88, 5 / 82, 6 / 88, 13 / 88, 3 / 88, 5 / 74, 5 / 88, 8 / 88 and RS2117, one or more of SELVOL™ (Sekisul Specialty Chemicals America, LLC) 502, 513, 518, 418, 425, 443, 203, 523, 205 and 540, and any combination thereof. Following the reaction of the polyvinyl alcohol backbone and monomers, a plurality of side chains are grafted onto one or more of the repeating units of the polyvinyl alcohol backbone in, by means of, or through the acetate and / or hydroxyl moieties thereof. The monomers may be: i) one or more monomers selected from: an aliphatic monocarboxylic acid and / or an aliphatic dicarboxylic acid and / or a reactive quaternary ammonium salt; and, optionally, ii) an aliphatic amide or a branched alkyl acrylate or any combination thereof. Without wishing to be bound to any particular theory or chemical reaction mechanism, all or part of the acetate and / or hydroxyl moieties may be replaced with monomers during the grafting reactions. The plurality of side chains comprises, essentially consists of, includes or is side chains comprising: i) one or more units selected from: an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and / or a reactive quaternary ammonium salt; and, optionally, i) units of an aliphatic amide, or a branched alkyl acrylate, or any combination thereof. nQ / yrn / Lznz / q / Yi Therefore, the monomers that react with polyvinyl alcohol are selected from an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, a reactive quaternary ammonium salt, an aliphatic amide, and / or a branched alkyl acrylate. Any combination of these monomers can be included in the reaction with polyvinyl alcohol to form the polyvinyl alcohol backbone. In the grafted polyvinyl alcohol polymer of the present invention, at least 75% of the side chains of the plurality of side chains may comprise: i) one or more units selected from: aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and / or a quaternary ammonium reactive salt; and, optionally, ii) units of aliphatic amide, or branched alkyl acrylate, or any combination thereof. Furthermore, no more than 25% of the side chains of the plurality of side chains may comprise units of aliphatic amide, or units of branched alkyl acrylate, or any combination thereof, and may not have units of aliphatic monocarboxylic acid, or aliphatic dicarboxylic acid, and / or a quaternary ammonium reactive salt. Alternatively, one or more of the side chains of the plurality of side chains may comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. In a grafted polyvinyl alcohol polymer of the present invention, the side chains of the plurality of side chains may comprise: i) units of the reactive quaternary ammonium salt; and, optionally, ii) units of the aliphatic amide, or units of the branched alkyl acrylate, or any combination thereof. In this aspect, the side chains of the grafted polyvinyl alcohol polymer do not require, or do not have, units of an aliphatic monocarboxylic acid and / or units of an aliphatic dicarboxylic acid. In one aspect of the present invention, at least 75%, by number, of the side chains of the plurality of side chains may comprise: i) units of the reactive quaternary ammonium salt; and, optionally, ii) units of the aliphatic amide, or units of the branched alkyl acrylate, or any combination thereof.Furthermore, no more than 25%, by number, of the side chains of the plurality of side chains may comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid units, aliphatic dicarboxylic acid units, and quaternary ammonium reactive salt units. In another aspect of the present invention, at least 75% of the side chains in the plurality of side chains may comprise: i) nQy / rn / Lznz / q / Yi units of the quaternary ammonium salt; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid or aliphatic dicarboxylic acid units. No more than 25% of the side chains in the plurality of side chains may comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, or quaternary ammonium reactive salt units. Another aspect of the present invention relates to a grafted polyvinyl alcohol polymer in which one or more of said side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. Another aspect of the present invention relates to a grafted polyvinyl alcohol polymer in which the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. At least 75% of the side chains of the plurality of side chains may comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.Furthermore, no more than 25%, by number, of the side chains of the plurality of side chains may comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid units, aliphatic dicarboxylic acid units, and quaternary ammonium reactive salt units. Another aspect of the present invention relates to a grafted polyvinyl alcohol polymer in which at least 75% of the side chains of the plurality of side chains may comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, ii) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have quaternary ammonium reactive salt units. No more than 25% of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid units, aliphatic dicarboxylic acid, or quaternary ammonium reactive salt units. Another aspect of the present invention relates to a grafted polyvinyl alcohol polymer in which one or more of said side chains of the plurality of side chains comprise the aliphatic amide, or the branched alkyl acrylate, or any combination thereof. When quaternary ammonium salt units are present in the side chains of the grafted polyvinyl alcohol polymer, these side chains can be called cationic side chains. These side chains can contribute to the rapid adsorption of the grafted polyvinyl alcohol polymer onto cellulose fibers and to its repulpability. Some side chains of the grafted polyvinyl alcohol polymer do not necessarily need to contain quaternary ammonium salt units. Rapid adsorption onto cellulose fibers can still occur when, for example, at least 75% of the grafted polyvinyl alcohol side chains comprise or include quaternary ammonium salt units. In another aspect of the present invention, the side chains of the grafted polyvinyl alcohol polymer may have carboxylic acid units. When a paper product comprising a grafted polyvinyl alcohol polymer having side chains comprising carboxylic acid units is washed with water, the embodiment slowly swells and then breaks down or redisperses, thereby converting a resin of the polymer from a solid state to a water-dispersible polymer, regardless of the exact metal ions within the solution and the exact carboxylate residues provided. The carboxylate residues may be anionic to negatively charged residues on the paper fibers. Carboxylic acid units in the side chains of a grafted polyvinyl alcohol polymer can contribute to its repulpability. When a paper product comprising the grafted polyvinyl alcohol polymer with side chains comprising carboxylic acid units is washed in a caustic solution, the carboxylic acid moieties can be converted into carboxylate moieties, thus converting the grafted polyvinyl alcohol polymer resin from a solid state to a water-dispersible polymer. For example, the carboxylic moieties can be converted into carboxylate moieties by contacting a paper product containing the polymer with a caustic aqueous solution containing metal ions. Furthermore, if sodium ions are included in the caustic aqueous solution containing metal ions, then a portion of the carboxylic moieties can be converted into sodium carboxylate moieties.Regardless of the exact metal ions within the solution and the exact carboxylate residues provided, the carboxylate residues can be anionic to negatively charged residues on the paper fibers. The carboxylate residues of the grafted polyvinyl alcohol polymer can become anionic with carboxylate residues on the cellulosic fibers within the paper. With the presence of negatively charged anionic residues on the paper fibers, the grafted polyvinyl alcohol polymer of the present invention and the paper fibers can repel each other, thereby increasing water dispersibility. The carboxylic acid moieties that contribute to water dispersibility in caustic and / or non-caustic solutions can be provided by carboxylic acid side chains. The carboxylic acid in these side chains can be, but is not limited to, acrylic acid, methacrylic acid, acrylates, methacrylates, itaconic acid, methylenesuccinic acid, or any combination thereof. The hydrophilic nature of hydroxyl and amide moieties within a grafted polyvinyl alcohol polymer can also increase the dispersion of paper products in non-caustic solutions. When paper comprising the grafted polyvinyl alcohol polymer is dispersed in water, the hydroxyl and amide moieties can swell, causing the paper to lose mechanical strength after a short period. The mechanical strength and the rate of strength loss can also depend on the sheet thickness. Hydroxyl groups that contribute to water dispersibility in caustic and / or non-caustic solutions can be provided by polyvinyl alcohol chains. For example, free dangling hydroxyl groups from the polyvinyl alcohol backbone, still present after reaction with the backbone and monomers, can contribute to this water dispersibility. The presence of amide units within the side chains of the grafted polyvinyl alcohol polymer can contribute to water dispersibility. When dispersed in water, these amide moieties can swell, causing the paper to lose mechanical strength. The amide units within the side chains of the grafted polyvinyl alcohol polymer can contribute to the dry and / or wet strength of paper. When the pH of an aqueous solution of the grafted polyvinyl alcohol polymer is sufficiently acidic, the amine moieties of the amide moieties can be converted into a protonated cationic form, sensitive to negatively charged moieties within the paper fibers. As such, the protonated amide moieties in the grafted polyvinyl alcohol polymer can electrostatically attract the polymer to the paper fibers, thereby increasing wet and / or dry strength. For example, the protonated amide moieties can be electrostatically attracted to carboxylic moieties within the cellulosic fibers.Regardless of the negatively charged residues within the paper fibers, a sufficient amount of protonated amide residues can be provided to link the grafted polyvinyl alcohol polymer to the paper fibers when the pH of the aqueous solution comprising the grafted polyvinyl alcohol polymer, and / or a resin incorporating the polymer, is from approximately 3 to approximately 6, preferably from approximately 4 to approximately 5. The amide units within the grafted polyvinyl alcohol polymer side chains may be provided by an aliphatic amide, such as, but not limited to, acrylamide, methacrylamide, dimethyl acrylamide, diethyl acrylamide, dipropyl acrylamide, or Nt-butyl acrylamide, or any combination thereof. Although amide, hydroxyl, and / or quaternary ammonium salt moieties within the grafted polyvinyl alcohol polymer can contribute to water dispersion, polyethylene moieties grafted onto the polyvinyl alcohol backbone can provide a temporary water barrier. This temporary water barrier provided by the alkyl moieties can decrease the paper's water absorption rate, thereby increasing its moisture resistance. Alkyl moieties with low glass transition temperature and / or surface tension can improve the temporary water barrier provided by the grafted polyvinyl alcohol polymer of the present invention. These moieties can also improve the adhesion of the grafted polyvinyl alcohol polymer to moist cellulose fibers by reducing the strong intramolecular hydrogen bonding or molecular cohesive energy of the polyvinyl alcohol, thus making the cellulose more substantial. A temporary water barrier can also be provided by grafting one or more branched alkyl acrylates, such as, but not limited to, 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate, 2-ethylbutyl acrylate, and any combination thereof, onto the polyvinyl alcohol backbone. In this aspect of the present invention, the units of one or more branched alkyl acrylates are present in the side chains of the grafted polyvinyl alcohol polymer. In one aspect of the present invention, side chains providing units of an aliphatic monocarboxylic acid, units of an aliphatic dicarboxylic acid, units of a reactive quaternary ammonium salt, units of an aliphatic amide, and / or units of a branched alkyl acrylate, or any combination thereof, can be grafted onto the acetate moieties of the vinyl acetate repeating units in the polyvinyl alcohol backbone. This grafting provides a grafted polyvinyl alcohol polymer according to structure (I): [CH2-CH(OH)]a→CH2-CH(R)]b(I). In this structure, the total weight percent of (a) units can be from 74 wt% to 84 wt% based on the total weight of the grafted polyvinyl alcohol polymer. All values ​​between 74 wt% and 84 wt% are included in this range, including endpoints, and therefore the value can be 75 wt%, 76 wt%, 77 wt%, 78 wt%, 79 wt%, 80 wt%, 81 wt%, 82 wt%, and 83 wt%. The range can be 74 wt% to 82 wt%, 77 wt% to 84 wt%, 80 wt% to 84 wt%, or 80 wt% to 82 wt%. The total weight percentage of units (b) is from 16% to 26% by weight based on the total weight of the grafted polyvinyl alcohol polymer.All values ​​between 16% by weight and 26% by weight are included in this interval, including the endpoints; therefore, the value can be 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, and 25% by weight. The interval can be from 16% by weight to 23% by weight, from 16% by weight to 20% by weight, from 20% by weight to 26% by weight, or from 20% by weight to 23% by weight. The total weight percentage of units (a) and (b) can be equal to, or is, 100% by weight. In structure (I), R is any combination of acetate and a side chain comprising units of an aliphatic monocarboxylic acid, units of an aliphatic dicarboxylic acid, units of a reactive quaternary ammonium salt, units of an aliphatic amide, units of a branched alkyl acrylate, or any combination thereof. According to structure (I), there are multiple R groups; therefore, some side chains do not have to contain any quaternary ammonium reactive salt units. The side chain at R comprising units of a quaternary ammonium reactive salt monomer may comprise diallyl dimethyl ammonium chloride units, 3-acrylamidopropyl trimethyl ammonium chloride, and / or any combination thereof. The side chain at R comprising carboxylic acid units may comprise acrylic acid units, methacrylic acid, tachonic acid, 3-yl methylenesuccinic acid, and / or any combination thereof. The side chain at R comprising aliphatic amide units may comprise acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, dipropylacrylamide, N-butylacrylamide, and / or any combination thereof.The side chain at R comprising units of a branched alkyl acrylate may comprise units of 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate, 2-ethylbutyl acrylate, and / or any combination thereof. As used in the present invention, the phrase "the side chain" is not limited to a single side chain but may refer to multiple side chains of the same or similar structure. In an alternative structure, side chains providing units of an aliphatic monocarboxylic acid, units of an aliphatic dicarboxylic acid, units of a reactive quaternary ammonium salt, units of an aliphatic amide, and / or units of a branched alkyl acrylate, or any combination thereof, can be grafted onto the acetate moieties of the vinyl acetate repeating units in the polyvinyl alcohol backbone having repeating units of vinyl alcohol units, ethylene units, and vinyl acetate units. This grafting provides a grafted polyvinyl alcohol polymer according to structure (II): [CH2-CH(OH)]a-[CH2-CH2]b-[CH2-CH(R)]c(II). In structure (II), the total weight percent of (a) units is from 90 wt% to 95 wt% based on the total weight of the grafted polyvinyl alcohol polymer. All values ​​between 90 wt% and 95 wt% are included in this range, including endpoints, and therefore the range includes, for example, 91 wt%, 92 wt%, 93 wt%, and 94 wt%. The total weight percent of (b) units is from 1 wt% to 8 wt% based on the total weight of the grafted polyvinyl alcohol polymer. All values ​​between 1 wt% and 8 wt% are included in this range, including endpoints, and therefore the range includes, for example, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, and 7 wt%. The total weight percentage of units (c) is 1% to 3% based on the total weight of the grafted polyvinyl alcohol polymer.All values ​​between 1% by weight and 3% by weight are included in this range, including 2% by weight, with endpoints included. According to structure (II), there are multiple R groups. Each R group can be an acetate unit or a side chain comprising units of an aliphatic monocarboxylic acid, units of an aliphatic dicarboxylic acid, units of a quaternary ammonium reactive salt, units of an aliphatic amide, and / or units of a branched alkyl acrylate, or any combination thereof. The side chain at R comprising units of a quaternary ammonium reactive salt monomer can comprise units of diallyl dimethyl ammonium chloride, 3-acrylamidopropyl methyl ammonium chloride, and / or any combination thereof. The side chain at R comprising carboxylic acid units can comprise units of acrylic acid, methacrylic acid, itaconic acid, methylenesuccinic acid, and / or any combination thereof.The side chain at R comprising units of an aliphatic amide may comprise units of acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, dipropylacrylamide, Nt-butylacrylamide, and / or any combination thereof. The side chain at R comprising units of a branched alkyl acrylate may comprise units of 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate, 2-ethylbutyl acrylate, and / or any combination thereof. As used in the present invention, the phrase "the side chain" is not limited to a single side chain but may refer to multiple side chains of the same or similar structure. In another alternative structure, a side chain, or side chains, providing amide, carboxylic and / or polyethylene moieties can be grafted onto acetate moieties of the polyvinyl alcohol backbone to provide a grafted polyvinyl alcohol polymer according to structure (III): [CH2-CH(OH)]a-[CH2-CH(R)]b-[X]c(III). In this structure, a ranges from 0.70 to 0.95, b ranges from 0.01 to 0.30, c ranges from 0 to 0.5, a+b+c = 1, and X is any monomer (monomer X) polymerizable with vinyl acetate. For a, all values ​​within this interval are included; therefore, a can be any of 0.71, 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, 0.80, 0.81, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, 0.89, 0.90, 0.91, 0.92, 0.93, and 0.94. Preferably, a is from 0.80 to 0.95, more preferably from 0.90 to 0.95. For b, all values ​​within this interval are included; therefore, b can be any of 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, and 0.29. Preferably, b is from 0.05 to 0.25, more preferably from 0.05 to 0.20. For c, all values ​​within this interval are included; therefore, c can be any of 0.1, 0.2, 0.3, and 0.4. Preferably, c is from 0.1 to 0.5. According to structure (III), there are multiple R groups. Each R group can be an acetate unit or a side chain comprising units of a non-acetic acid; ;rn / i znz / □ / ¥!< The R-membered side chain comprising units of an aliphatic monocarboxylic acid, units of an aliphatic dicarboxylic acid, units of a quaternary ammonium reactive salt, units of an aliphatic amide, units of a branched alkyl acrylate, or any combination thereof. The R-membered side chain comprising units of a quaternary ammonium reactive salt monomer may comprise units of diallyl dimethyl ammonium chloride, 3-acrylamidopropyl trimethyl ammonium chloride, and / or any combination thereof. The R-membered side chain comprising carboxylic acid units may comprise units of acrylic acid, methacrylic acid, itaconic acid, methylenesuccinic acid, and / or any combination thereof. The R-membered side chain comprising aliphatic amide units may comprise units of acrylamide, methacrylamide, dimethylacrylamide, diethylacrylamide, dipropylacrylamide, Nt-butylacrylamide, and / or any combination thereof.The side chain at R comprising units of a branched alkyl acrylate may comprise units of 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate, 2-ethylbutyl acrylate, and / or any combination thereof. As used in the present invention, the phrase "the side chain" is not limited to a single side chain but may refer to multiple side chains of the same or similar structure. Each of a, b, and c represents molar quantities of residues within the structure (III) described above. In structure (III), monomer X is any monomer that can polymerize with vinyl acetate under any reaction condition to form a polyvinyl alcohol. Optionally, monomer X can be ethylene, propylene, butylene, 1-pentene, and 4-methyl-1-pentene.Other options for monomer X include, but are not limited to, vinyl fluoride, vinyl chloride, vinyl bromide, styrene, vinyl ketone, (meth)acrylonitrile, acrylophenone, (meth)methyl acrylate, (meth)ethyl acrylate, (meth)propyl acrylate, (iso)butyl (meth)acrylate, butyl cyanoacrylate, glycidyl (meth)acrylate, (meth)acrylic acid, itaconic acid, ethyl cyanoacrylate, N-(2-hydroxypropyl) methacrylamide, (meth)acrolein, (meth)acrylamide, methyl 2-chloroacrylate, methyl 2-fluoroacrylate, methyl cyanoacrylate, vinyl propionate, N-vinylacetamide, 4-vinylbenzyl chloride, 2-vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, vinylsilane, vinylsulfonic acid or 4-vinyltoluenesulfonic acid, or any combination thereof. Regardless of the structure, the main polyvinyl alcohol chain in the grafted polyvinyl alcohol of the present invention may have incorporated units that provide additional functionality, such as a carboxyl functionality, an amine functionality, an amide functionality, or an imide functionality, or any combination thereof, in an amount not exceeding 3% by moles. nQy / rn / Lznz / q / Yi Regardless of the structure, and for any form of the polyvinyl alcohol backbone, side chains can be grafted from approximately 90% to approximately 100% of the available vinyl acetate repeating units within the polyvinyl alcohol backbone and / or can be grafted from approximately 90% to approximately 100% of the vinyl alcohol repeating units within the polyvinyl alcohol backbone. All values ​​within these ranges are included, and therefore the value can be 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, and 99%. As an option, regardless of how it is produced, the grafted polyvinyl alcohol polymer may have or include a structure (IV): nQy / rn / Lznz / q / Yi Structure (IV) In structure (IV), the total weight percent of a is 30% to 34% based on the total weight of the grafted polyvinyl alcohol polymer; the total weight percent of b is 6% to 10% based on the total weight of the grafted polyvinyl alcohol polymer; the total weight percent of c is 0.5% to 1.0% based on the total weight of the grafted polyvinyl alcohol polymer; and the total weight percent of d is 58% to 62% based on the total weight of the grafted polyvinyl alcohol polymer. For a, all values ​​between 30% by weight and 34% by weight are included in this interval, including the endpoints; therefore, the interval includes, for example, 31% by weight, 32% by weight, and 33% by weight. For b, all values ​​between 6% by weight and 10% by weight are included in this interval, including the endpoints; therefore, the interval includes, for example, 7% by weight, 8% by weight, and 9% by weight. For c, all values ​​between 0.5% by weight and 1.0% by weight are included in this interval, including the endpoints; therefore, the interval includes, for example, 0.6% by weight, 0.7% by weight, 0.8% by weight, and 0.9% by weight. For d, all values ​​between 58% by weight and 62% by weight are included in this interval, including the endpoints; therefore, the interval includes, for example, 59% by weight, 60% by weight, and 61% by weight. The side-chain monomers may be attached to the polyvinyl alcohol backbone in a ratio ranging from 1:2:8 to 1.5:3:6 by weight and standardized to an amount of (b) aliphatic amide. The grafted polyvinyl alcohol polymer may have several desirable properties, such as, but not limited to, a water dispersibility of at least 25% solids by weight, such as 23% to 27% solids by weight or more, and / or the ability to form a dry solid particulate. Depending on the desired properties, the grafted polyvinyl alcohol polymer of the present invention may comprise a weight percentage of polyvinyl alcohol main chain of approximately 40% to approximately 42%, preferably 40% to 50%, by weight of total solids, a weight percentage of quaternary ammonium salt side chain of approximately 5% to approximately 10%, preferably 6% to 8%, by weight of total solids, a weight percentage of aliphatic amide of approximately 4% to approximately 10%, preferably 5% to 8%, by weight of total solids, and a weight percentage of branched alkyl acrylate of approximately 35% to approximately 45%, by weight of total solids. Alternatively, regardless of how it is produced, the grafted polyvinyl alcohol polymer may have or include the structure (V): nQy / rn / Lznz / q / Yi In structure (V), the total weight percent of a is 0.05% to 0.5% based on the total weight percent, the total weight percent of b is 1.25% to 2.5% based on the total weight percent, the total weight percent of c is 0.5% to 4.0% based on the total weight percent, the total weight percent of d is 40% to 42% based on the total weight percent, and the total weight percent of g is 50% to 60%, such as 55%, based on the total weight percent. In structure (V), the side chain monomers can be attached to the polyvinyl alcohol backbone in a ratio range a:b:c from 3:1:5 to 2.5:1:4 on a weight basis and normalized to an amount of (b) aliphatic amide. To form a grafted polyvinyl alcohol of the present invention, a side chain can be grafted onto repeating units of vinyl acetate and / or vinyl alcohol of the polyvinyl alcohol backbone by various mechanisms. For example, side chains comprising a vinyl moiety, such as, but not limited to, methylenesuccinic acid, acrylates, acrylic acids, methacrylates, quaternary ammonium reactive salt monomers, and / or methacrylic acids, can be added to the polyvinyl alcohol backbone by radical-induced polymerization of the monomers in the presence of free PVOH. The radical-induced polymerization of the monomers can be achieved by grafting the side chains to the polymer in the presence of a free-radical initiator, such as an oxidant and / or a reductant.Suitable free-radical initiators include, but are not limited to, peroxides, azo compounds, potassium persulfates, ammonium persulfates, and / or any combination thereof. Suitable reducing agents include, but are not limited to, sodium bisulfite, sodium metabisulfite, sodium formaldehyde sulfoxylate, iron(II) sulfate, and / or any combination thereof. Suitable oxidizing agents include, but are not limited to, tert-butyl hydroperoxide, hydrogen peroxide, ammonium persulfate, benzyl peroxide, dicumyl peroxide, and / or any combination thereof. Accordingly, the grafted polyvinyl alcohol polymer can be prepared by providing an aqueous solution of an unreacted polyvinyl alcohol polymer and adding, to the aqueous solution, a free-radical initiator and the desired plurality of side-chain forming monomers.The side-chain monomers added to the aqueous solution may include: (a) reactive quaternary ammonium side-chain monomers comprising at least one aliphatic, allylic, vinyl, and acrylic quaternary ammonium salt; (b) an aliphatic amide; and (c) a branched alkyl akylate. Other side chains may include units of an aliphatic amide and / or units of a branched alkyl akylate without having units of the aliphatic, allylic, vinyl, and acrylic quaternary ammonium salts. To control the pH of the aqueous solution, a buffer salt can be used such as, but not limited to, sodium bicarbonate, sodium acetate, sodium dihydrogen phosphate and / or any combination thereof. After a sufficient period of time (e.g., three to four hours or more), the free residual monomers can be suppressed by adding a sufficient amount of a reduction / oxidation pair, such as, but not limited to, 0.01% sodium formaldehyde sulfoxylate / 0.08% (wt.%) tert-butyl hydroperoxide, a hydrogen peroxide / iron(II) compound, and / or any combination thereof. The sufficient amount of the reduction / oxidation pair is not particularly limited, provided that the free residual monomers are suppressed. Preferably, the amounts of the reduction / oxidation pair are 0.005 and 0.08 wt., respectively. The grafted polyvinyl alcohol polymer may have several desirable properties, such as, but not limited to, a water dispersibility of at least 16% by weight of solids, such as 16% by weight to 20% by weight of solids or more, and / or the ability to form a dry solid particulate. Depending on the desired properties, the grafted polyvinyl alcohol polymer may comprise a weight percentage of polyvinyl alcohol main chain of approximately 30% to approximately 60%, preferably 40% to 50%, by weight of total solids, a weight percentage of carboxylic acid side chain of approximately 12% to approximately 25%, preferably 15% to 21%, by weight of total solids, a weight percentage of aliphatic amide of approximately 2.5% to approximately 15%, preferably 6% to 11%, by weight of total solids, and a weight percentage of branched alkyl acrylate of approximately 20% to approximately 35%, by weight of total solids. As an additional option, the grafted polyvinyl alcohol polymer, or its polyvinyl alcohol backbone, may be or is crosslinked. Crosslinking can occur through internal ionic or covalent bonds between polyvinyl alcohol backbone residues. Alternatively, crosslinking can be achieved by reacting any suitable crosslinking agent with polyvinyl alcohol backbone residues. The present invention also relates to a polymer mixture that may comprise, essentially consist of, include, or has a first grafted polyvinyl alcohol polymer comprising a first polyvinyl alcohol main chain and a first plurality of side chains grafted to the first polyvinyl alcohol main chain, wherein the side chains of the first plurality of side chains comprise: i) one or more units selected from: an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid; and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof;and a second grafted polyvinyl alcohol polymer comprising a second polyvinyl alcohol backbone and a second plurality of side chains grafted onto the second polyvinyl alcohol backbone, wherein the side chains of the second plurality of side chains comprise: i) one or more units of a reactive quaternary ammonium salt; and, optionally, ii) an aliphatic amide or a branched alkyl acrylate or any combination thereof. The polymer blend may comprise, consist of, essentially consist of, include, or have, the first grafted polyvinyl alcohol polymer and the second grafted polyvinyl alcohol polymer in a weight ratio of the first grafted polyvinyl alcohol polymer to the second grafted polyvinyl alcohol polymer of 10:1 to 1:10, or other weight ratios outside this range. Each of the first grafted polyvinyl alcohol polymer and the second grafted polyvinyl alcohol polymer can have any structure described in the present invention. The first grafted polyvinyl alcohol polymer can function as a retention aid for the second grafted polyvinyl alcohol, or vice versa. Both the first and second grafted polyvinyl alcohols can be considered a two-component crosslinking system due to the difference in particle charge density between the two grafted polyvinyl alcohols. The polymer mixture of the present invention can be used in any process described in the present invention that is carried out with, on, or in the grafted polyvinyl alcohol polymer. A polymer composition can be produced by dispersing the grafted polyvinyl alcohol polymer of the present invention in an aqueous medium. The grafted polyvinyl alcohol polymer of the present invention can be incorporated into various products. For example, the polymer can be incorporated into paper products to increase wet strength and / or dry strength and / or provide temporary water repellency and / or provide water absorption retardation properties. The incorporation of the polymer into a paper product can be achieved by producing a fibrous pulp comprising a fibrous material suitable for papermaking, such as, but not limited to, cellulosic fibers and the grafted polyvinyl alcohol polymer. Preferably, the fibrous material includes negatively charged residues, such as, but not limited to, carboxylate residues. The fibrous pulp can be transformed into an aqueous suspension, within which the grafted polyvinyl alcohol polymer can be absorbed or adsorbed onto the fibrous material. The aqueous suspension can be provided by adding the grafted polyvinyl alcohol polymer to a pulp deposit, preferably one containing negatively charged residues. For example, the polymer can be added to a pulp deposit comprising cellulose papermaking fibers.Regardless of how it is supplied, the suspension can be formed into a mesh and dried to produce a paper product. Forming the suspension into a mesh can be achieved by draining the suspension after the grafted polyvinyl alcohol polymer has adsorbed onto the fibrous material. Preferably, the aqueous suspension comprises an amount of the grafted polyvinyl alcohol polymer effective in increasing wet strength and / or dry strength and / or water dispersibility, compared to a paper product made with the aqueous suspension without the grafted polyvinyl alcohol polymer. For example, in the case of a cellulose paper product, the aqueous suspension may comprise 4 to 10 pounds (1.81 to 4.53 kg) of the grafted polyvinyl alcohol polymer per tonne of dry cellulose papermaking fiber. Ideally, the amount of grafted polyvinyl alcohol polymer within the aqueous suspension is effective in increasing the wet strength and / or dry strength of the paper by at least 10% (e.g., from 10% to 50% or more) compared to the paper product made with the aqueous suspension without the grafted polyvinyl alcohol polymer. The moisture resistance of a paper product can be measured by subjecting a dry piece of the paper product to 100% relative humidity for five minutes at room temperature, and then measuring the tensile strength of the wet paper product. Tensile strength can be measured using the following method: 1. Cut strips of blotting paper measuring 13 x 150 mm using a cutter. 2. Condition all strips at 45°C for 12 hours. 3. Condition all strips at room temperature (RT) (e.g., 25°C) for at least 2 hours inside a desiccator. 4. Prepare a polymer solution at 0.0015% by weight or whatever polymer concentration is required. naj / rn / Lznz / q / Yi 5. Immerse each strip in the 0.0015% by weight polymer solution for one second or simply dip and remove it. 6. Place each set of strips on a sheet of blotting paper. 7. Dry the strips at 60°C for 24 hours. 8. Condition all strips in a desiccator at room temperature for at least 2 hours. 9. Use a 50 kg load cell to test tensile strength. 10. Test 5 strips from each set to measure dry tensile strength. 11. Take 5 strips from each set at a time and place them in the humidity chamber at 100% RH and room temperature for 5 min. 12. Add an open glass bottle inside the chamber to hold the strips after five minutes. 13. After 5 minutes at 100% RH, keep the strips inside the glass bottle and close it tightly to maintain the humidity level as constant as possible inside the strips. 14. Test 5 strips from each set to determine wet tensile strength using the same tensiometer software set up for dry tensile strength. Other moisture resistance testing methods may include a standard test method known as TAPPI T-465 om-15, in which a paper sample is folded and immersed in a cup of water (The Finch Cup) for a moment before being tested on a tensiometer. The dry strength of a paper product can be measured by a similar method to that used to measure tensile strength as described above, except that the hand-molded sheets are cut to a size of, for example, 13 x 127 mm and then conditioned at room temperature and 50% relative humidity for several hours before measuring the tensile strength on the tensiometer. Water dispersibility can be measured by cutting 10 x 20 mm samples of blotting and / or hand-molded paper, then conditioning the samples at 50 °C and 50% relative humidity for 4 hours. Each paper sample is then placed in a beaker containing 200 ml of DI water. The water containing the paper sample is then magnetically stirred at 300 rpm. The time for complete dispersion of the paper sample is recorded. Paper samples treated with grafted polyvinyl alcohol showed a dispersion time of less than 60 seconds; however, those treated with nQy / rn / Lznz / q / Yi G-PAM showed more than 180 seconds and / or no dispersion in some other batches of G-PAM. Water repellency can be measured by placing a drop of water on top of the blotting paper treated with the grafted polyvinyl alcohol polymer and recording the time required for this drop of water to diffuse into the treated blotting paper. Regardless of the strength, water repellency and / or dispersibility that can be provided, the amount of polyvinyl alcohol polymer grafted within the aqueous suspension can provide a ratio of paper wet strength, determined by the Finch Cup method and / or humidity chamber method, to dry strength determined by tensiometer of approximately 0.6, or 0.6 ± 0.2 or 0.6 ± 0.1. The paper product, regardless of how it is produced, may comprise a paper material and the grafted polyvinyl alcohol polymer. The paper material of the paper product may comprise a cellulosic fiber having carboxylic moieties that interact electrostatically with protonated amines and quaternary ammonium salts in a portion of the aliphatic amides grafted onto the repeating units of the polyvinyl alcohol backbone. The paper product can be incorporated into a further product comprising a paper product layer, such as, but not limited to, paper sheets, cardboard, tissues, or card stock. Accordingly, the paper layer can comprise a cellulosic fiber having carboxyl moieties that interact electrostatically with protonated amines and quaternary ammonium salts in a portion of the reactive aliphatic amides and / or quaternary ammonium salts grafted onto the repeating units of the polyvinyl alcohol backbone. The grafted polyvinyl alcohol polymer of the present invention can be used to treat fibrous materials other than paper products. For example, clothing with a fibrous material containing negatively charged residues can be treated with the polymer. For instance, a fibrous material comprising cotton fibers having carboxylic residues that interact electrostatically with protonated amines and / or quaternary ammonium salts in a portion of the reactive aliphatic amides and / or quaternary ammonium salts grafted onto the repeating units of the poly(vinyl alcohol-vinyl coacetate). Regardless of the fiber types within the material, the fibrous material can be obtained by coating and / or impregnating the fibers with the grafted polyvinyl alcohol polymer. nQy / rn / Lznz / q / Yi The variety of monomers and relative concentrations of polyvinyl alcohol polymers are relevant to achieving the desired performance of this temporary moisture resistance, imparting the necessary moisture resistance during end use or customer application and allowing complete dispersibility in a sewer line after disposal. This “intelligent” dual-function performance distinguishes this polymer from covalently crosslinked products that can only perform one function within a certain pH range. As with other additives commonly used to improve moisture resistance, conventional glyoxylated polyacrylamide is covalently bonded to paper fibers. Furthermore, it lacks hydroxyl residues along its structure. This lack of hydroxyl residues limits the ability of glyoxylated polyacrylamide-treated papers to undergo mechanical deformation due to water swelling. Even if glyoxylated polyacrylamide-treated paper were to swell with a sufficient amount of water, the covalent bond between the glyoxylated polyacrylamide and the paper fibers prevents the resulting mechanical deformation from dispersing the paper. Unlike glyoxylated polyacrylamide, the grafted polyvinyl alcohol polymers of the present invention bond to paper fibers through an electrostatic interaction between protonated amine and / or quaternary ammonium salt residues and negatively charged carboxyl residues within the paper fibers.This weaker electrostatic interaction is more susceptible to disruption when the grafted polyvinyl alcohol swells in water. As such, the weaker electrostatic interaction between protonated amine units and / or quaternary ammonium reactive salt units within the grafted polyvinyl alcohol polymer and the paper fibers contributes to improved water dispersibility. Therefore, similar results would be expected compared to other additives covalently bonded to paper fibers. The present invention will be further clarified by the following examples, which are intended to be exemplary of the present invention. EXAMPLES Examples 1-4 Synthesis and characterization of the grafted polyvinyl alcohol polymer (TWS 15) Samples of grafted polyvinyl alcohol were prepared by dissolving a 15 wt% solids content polyvinyl alcohol polymer (CAS # 25213-24-5) in water. Diallyl dimethyl ammonium chloride (CAS # 7398-69-8) as a quaternary ammonium salt side-chain monomer, acrylamide (CAS # 79-06-1) as an aliphatic amide side-chain monomer, and 2-ethylhexyl acrylate (CAS # 103-11-7) as a branched alkyl acrylate side-chain monomer were then added to the aqueous PVOH solution. Diallyl dimethyl ammonium chloride and acrylamide were added to the 15% aqueous PVOH solution at 65 °C. 2-Ethylhexyl acrylate was added dropwise over a period of 120 minutes. Then sodium bisulfate (CAS # 7631-90-5) and ammonium persulfate (CAS # 7727-54-0) were added to the emulsion as free radical forming initiators and sodium bicarbonate (CAS # 144-55-8) as a buffering salt.Next, semicontinuous polymerization was initiated by feeding a 0.8 wt% ammonium persulfate solution at 65 °C for 240 minutes. Polymerization was then propagated at 80 °C for 2 hours while ammonium persulfate was introduced into the emulsion at a constant rate. Residual free monomers were then suppressed by adding hydrogen peroxide (CAS # 7722-84-1) and tert-butyl hydroperoxide (CAS # 75-91-2) to the emulsion at 0.1 wt%. Stirring at 200–300 rpm was maintained for 1 hour at 80 °C. The batch was then cooled to room temperature before being discharged into packaging containers. The final emulsion had the following percentages by weight: nQy / rn / Lznz / q / Yi Example 1 Example 2 Example 3 Example 4 Chemical Name M5-TWS 13 wt% M7-TWS 13 wt% M8-TWS 13 wt% M9-TWS 13 wt% Water 76.5 75 75 75 Acrylamide 1.42 1.40 1.40 1.40 Methacrylic Acid 0 0 1.40 1.40 Diallyl Dimethylammonium Chloride 1.85 1.83 0.0 0.0 2-Ethylhexyl Acrylate 8.57 11.26 11.42 11.42 Polyvinyl Alcohol (CAS #25213-24-5) 10.71 Poval 5-74 10.56 Poval 3-80 9.8 Poval 3-80 10.72 Poval 5-74 Sodium bicarbonate 0.002 0.01 0.01 0.01 Ammonium persulfate 0.075 0.075 0.075 0.16 Sodium bisulfate 0.028 0.01 0.01 0.05 Hydrogen peroxide 0.015 0.08 0.08 0.08 tert-Butyl hydroperoxide 0.015 0.08 0.08 0.08 Total 100 100 100 100 The grafted polyvinyl alcohol polymer produced was then characterized by Fourner transform infrared spectroscopy, particle size analysis by dynamic light scattering, gel permeation chromatography, pH and dispersion solids content. The degree of hydrolysis (%) of the previous examples as percentages was as follows: M5-TWS13 (74%), M7-TWS13 (80%), M8-TWS13 (80%) and M9-TWS13 (74%)). Temporary moisture resistance deterioration test Hand-molded sheets were prepared by mixing hardwood and softwood pulps in a 1:1 weight ratio. The pulp was diluted to a consistency of 1% by weight. One liter of the diluted pulp was treated at a 10 lb / ton (5 g / kg) equivalent from different embodiments, such as Examples 1–4. The hand-molded sheets were cut into strips measuring 13 x 127 x 0.125 mm. Examples 3 and 4 were slightly anionic due to the methacrylic acid side chain residues. Examples 1 and 2 were slightly cationic due to the quaternary ammonium salt side chain residues. Examples 1 and 4 contained polyvinyl alcohol with a lower degree of hydrolysis than that used in Examples 3 and 4. All handmade strips were dried at 90°C for 24 hours and then conditioned at room temperature for 2 hours in a desiccator. The hand-molded strips were then subjected to TAPPI T-465 om-15, in which a paper sample is folded and immersed in a cup of water (The Finch Cup). Tensile strength and moisture resistance deterioration were measured. Dry and wet tensile strength results are shown in Figure 4. Water dispersibility of handmade sheets treated with Examples 1–4 and G-PAM is shown in Figure 5, and moisture resistance deterioration is shown in Figure 6 for all four Examples against blank and glyoxylated G-PAM. As can be seen in Figure 4, the strips treated with glyoxylated polyacrylamide and grafted polyvinyl alcohol polymer dispersions had similar dry strength, except for M7-TWS13. The strips treated with the slightly cationic resin examples, Examples 1 and 2 (M5 and M7), showed two and three times the moisture resistance of those treated with G-PAM. The wet / dry tensile strengths of M5-TWS13 and M7-TWS13 were higher than those of Blanco, G-PAM, and the slightly anionic resins. The deterioration of wet tensile strength of the strips treated with cationic resins, M5-TWS13 and M7-TWS13, exceeded that of Blanco, G-PAM and anionic resins where the initial moisture resistance drops to approximately 1 / 2 after 120 seconds, however, it remains almost the same after the same period for the rest of the samples. nQ / yrn / Lznz / q / Yi Examples 5-8 Synthesis and characterization of the grafted polyvinyl alcohol polymer (TWS 15) A grafted polyvinyl alcohol polymer was prepared by dissolving a polyethylene vinyl alcohol polymer (CAS # 26221-27-2) with a solids content of 10 wt% in water. Then, methacrylic acid (CAS # 79-41-4) as the carboxylic acid side-chain monomer, acrylamide (CAS # 79-06-1) as the aliphatic amide side-chain monomer, and 2-ethylhexyl acrylate (CAS # 103-11-7) as the branched alkyl acrylate side-chain monomer were emulsified in the 10 wt% polyethylene vinyl alcohol polymer solution for at least 30 minutes. Sodium bisulfate (CAS # 7631-90-5) and ammonium persulfate (CAS # 7727-54-0) were added to the emulsion as free-radical initiators, and sodium bicarbonate (CAS # 144-55-8) was added as a buffer salt. Batch polymerization was then initiated by feeding a 0.8 wt% ammonium persulfate solution at 60 °C.Polymerization was then propagated at 80 °C for 2 hours while ammonium persulfate was introduced into the emulsion at a constant rate. Residual free monomers were then suppressed by adding sodium formaldehyde sulfoxylate (CAS # 6035-47-8), hydrogen peroxide (CAS # 7722-84-1), and tert-butyl hydroperoxide (CAS # 75-91-2) to the emulsion. Stirring at 200 rpm was maintained for 1 hour at 80 °C. The batch was then cooled to room temperature. The final emulsion had the following percentages by weight: nQy / rn / Lznz / q / Yi Example 5 Example 6 Example 7 Example 8 Chemical Name TWS 15 TWS 16 TWS 22 TWS 18 Water 84 84 84 77 Acrylamide 1.5 1.5 1.5 6.66 Methacrylic Acid 3 3 3 3.33 2-Ethylhexyl Acrylate 4.47 4.47 4.47 8.33 Polyvinyl Alcohol [CAS #26221-27-2] 6.765 6.765 6.765 4.29 Sodium Bicarbonate 0.01 0.01 0.01 0.01 Ammonium Persulfate 0.075 0.075 0.075 0.16 Sodium Bisulfate 0.01 0.01 0.01 0.05 Formaldehyde Sulfoxylate Sodium 0.01 0.01 0.01 0.01 Hydrogen peroxide 0.08 0.08 0.08 0.08 tert-Butyl hydroperoxide 0.08 0.08 0.08 0.08 Total 100 100 100 100 The grafted polyvinyl alcohol polymer produced was then characterized by Fourier transform infrared spectroscopy, particle size analysis by dynamic light scattering, gel permeation chromatography, pH and dispersion solids content. Examples 9 and 10 Comparative tests of temporary humidity resistance and dispersibility Blotting paper was cut to 13 x 127 x 0.125 mm. Ten strips were immersed for 1 second in polymer solutions of 0.0015 wt% glyoxylated polyacrylamide, grafted polyvinyl alcohol polymer TWS-15, 16, 22, and 18. The polyvinyl alcohol polymers TWS-16 and TWS-22 were prepared by a method analogous to those detailed in Example 5, except that TWS 16 and 22 were prepared starting from a semi-continuous mode, adding methacrylic acid and acrylamide when the reaction temperature reached 62 °C and 40 °C respectively. Example 8 (TWS 18) had a different composition in which the concentration of polyalkylene vinyl alcohol was reduced and the concentrations of the two monomers, acrylamide and 2-ethylhexyl acrylate, were higher than the rest of the examples, as shown above in the chemical composition table. All dipped strips were dried at 50 °C for 24 hours. The dipped strips were then conditioned at room temperature for two hours in a desiccator. Next, the dipped strips were subjected to 100% relative humidity for 5 minutes at room temperature. Each set of dipped strips was then removed from the humidity chamber and placed in sealed glass bottles to maintain a constant humidity level for wet tensile strength and dispersibility testing. Tensile strength and dispersibility were measured as described above. The results of the wet tensile strength and dispersibility tests are shown in Figure 7. As can be seen in Figure 7, the strips dipped in glyoxylated polyacrylamide and the grafted polyvinyl alcohol polymer dispersions had similar moisture resistance, except for TWS 18, which has a different chemical formulation. The strips dipped in the grafted polyvinyl alcohol polymer solutions had significantly better water dispersibility than the strips treated with polyvinyl polymers grafted with glyoxylated polyacrylamide. nQy / rn / Lznz / q / Yi The present invention includes the following aspects / embodiments / features in any order and / or in any combination. 1. A grafted polyvinyl alcohol polymer comprising a polyvinyl alcohol main chain and a plurality of side chains grafted onto the polyvinyl alcohol main chain, wherein one or more of said side chains of the plurality of side chains comprise: i) one or more units selected from: an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and a reactive quaternary ammonium salt; and, optionally, i) units of an aliphatic amide, or a branched alkyl acrylate, or any combination thereof. 2. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein at least 75%, by number, of said side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid, aliphatic dicarboxylic acid and quaternary ammonium reactive salt; and, optionally, i) units of aliphatic amide, or branched alkyl acrylate, or any combination thereof. 3. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein not more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units. 4. The grafted polyvinyl alcohol polymer in accordance with any foregoing or following embodiment / feature / aspect, wherein one or more of said side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 5. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein the side chains of the plurality of side chains comprise: i) quaternary ammonium reactive salt units; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 6. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) quaternary ammonium reactive salt units; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 7. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein not more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units. 8. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) quaternary ammonium reactive salt units; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid or aliphatic dicarboxylic acid units. 9. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein not more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units. 10. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein one or more of said side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 11. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 12. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof. 13. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein not more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units. 14. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have quaternary ammonium reactive salt units. 15. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein not more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units. 16. The grafted polyvinyl alcohol polymer according to any above or following embodiment / feature / aspect, wherein one or more of said side chains of the plurality of side chains comprise the aliphatic amide, or the branched alkyl acrylate, or any combination thereof. 17. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein the polyvinyl alcohol main chain, in its unreacted form, has a monomodal molecular weight distribution of approximately 5 K to 20000 K Daltons. 18. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein the polyvinyl alcohol main chain, in its unreacted form, has a degree of hydrolysis of approximately 74 mol% to approximately 99 mol%. 19. The grafted polyvinyl alcohol polymer according to any above or below embodiment / feature / aspect, wherein the polyvinyl alcohol main chain, in its unreacted form, has a degree of hydrolysis of approximately 74 mol% to approximately 90 mol%. 20. The grafted polyvinyl alcohol polymer according to any above or following embodiment / feature / aspect, wherein one or more of said side chains of the plurality of side chains are grafted into the polyvinyl alcohol main chain through acetate residues of the polyvinyl alcohol main chain. 21. The grafted polyvinyl alcohol polymer according to any above or following embodiment / feature / aspect, wherein one or more of said side chains of the plurality of side chains are grafted into the polyvinyl alcohol main chain through hydroxyl residues of the polyvinyl alcohol main chain. 22. The grafted polyvinyl alcohol polymer according to any foregoing or following embodiment / feature / aspect, wherein the quaternary ammonium reactive salt comprises at least one of diallyl dimethyl ammonium chloride, 3-acrylamidopropyl trimethyl ammonium chloride or a combination thereof; wherein the aliphatic amide comprises at least one of acrylamide, methacrylamide, dimethyl acrylamide, diethyl acrylamide, dipropyl acrylamide and Nt-butyl acrylamide; and wherein the branched alkyl acrylate comprises at least one of 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate and 2-ethylbutyl acrylate. 23. The grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / aspect, including structure (I): [CH2-CH(OH)]a-[CH2-CH(R])]b(I) wherein a total weight percent of (a) units is from 74% to 84% based on the total weight of the grafted polyvinyl alcohol polymer, wherein a total weight percent of (b) units is from 16% to 26% based on the total weight of the grafted polyvinyl alcohol polymer, wherein each R is acetate or a side chain of the plurality of side chains. 24. The grafted polyvinyl alcohol polymer in accordance with any foregoing or following embodiment / feature / aspect, comprising: nQy / rn / Lznz / q / Yi a weight percentage of the polyvinyl alcohol main chain of approximately 40% to approximately 50%, by total weight of solids; a weight percentage of the quaternary ammonium reactive salt side chain of approximately 6% to approximately 10% of total solids weight; an aliphatic amide weight percentage of approximately 6% to approximately 9% by weight of total solids; and a branched alkyl acrylate weight percentage of approximately 24% to approximately 50% by weight of total solids. 25. The grafted polyvinyl alcohol polymer according to any above or following embodiment / feature / aspect, having or comprising structure (IV): nQy / rn / Lznz / q / Yi where the total weight percentage of a is 30% to 34% based on the total weight of the grafted polyvinyl alcohol polymer, the total weight percentage of b is 6% to 10% based on the total weight of the grafted polyvinyl alcohol polymer, the total weight percentage of c is 0.5% to 1.0% based on the total weight of the grafted polyvinyl alcohol polymer, and the total weight percentage of d is 58% to 62% based on the total weight of the grafted polyvinyl alcohol polymer. 26. The grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / appearance, having a solids content of at least 25% solids. 27. The grafted polyvinyl alcohol polymer in accordance with any above or below embodiment / feature / appearance in the form of dry solid particles. 28. A polymer composition comprising: the grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / aspect; and an aqueous medium in which the grafted polyvinyl alcohol polymer is dispersed. 29. The polymer composition in conformity with any above or below embodiment / feature / aspect, having a pH of approximately 3 to approximately 6. 30. An aqueous-based graft emulsion polymer, comprising the grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / aspect. 31. A cellulose pulp product comprising: cellulosic pulp; and the grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / appearance. 32. A paper product comprising: a paper material; and the polyvinyl alcohol polymer grafted in accordance with any foregoing or following embodiment / feature / appearance. 33. The paper product according to any above or following embodiment / feature / aspect, wherein the paper material comprises a cellulosic fiber comprising a carboxyl group, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein a unit of the quaternary ammonium reactive salt units comprises a cationic charge that interacts electrostatically with the carboxyl group of the cellulosic fiber. 34. A product comprising at least one layer of paper comprising the grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / aspect, wherein the product is sheets of paper, cardboard, disposable tissues or card. 35. The product in accordance with any above or following embodiment / feature / aspect, wherein the paper layer comprises a cellulosic fiber comprising a carboxyl group, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein a unit of the units of the quaternary ammonium reactive salt comprises a cationic charge that interacts electrostatically with the carboxyl group of the cellulosic fiber. 36. A fibrous material comprising: cotton fibers; and the grafted polyvinyl alcohol polymer in accordance with any above or following embodiment / feature / appearance. 37. The fibrous material in accordance with any above or following embodiment / feature / aspect, wherein the cotton fibers are coated with the grafted polyvinyl alcohol polymer. 38. The fibrous material in accordance with any above or following embodiment / feature / aspect, wherein the cotton fibers are impregnated with the grafted polyvinyl alcohol polymer. 39. The fibrous material according to any above or following embodiment / feature / aspect, wherein at least a portion of the cotton fibers comprises a cellulosic fiber comprising a carboxyl group, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein a unit of the quaternary ammonium reactive salt units comprises a cationic charge that interacts electrostatically with the carboxyl group of the cellulosic fiber. 40. A paper manufacturing process, the process comprises: absorb an amount of the grafted polyvinyl alcohol polymer in accordance with any above or below embodiment / feature / aspect onto aqueous suspension cellulose papermaking fibers; forming said suspension on a mesh; and drying said mesh, wherein the amount of the grafted polyvinyl alcohol polymer is effective in increasing at least one of the paper's wet strength, dry strength, and water dispersibility compared to a paper made from the aqueous suspension without the grafted polyvinyl alcohol polymer. 41. The process in conformity with any foregoing or following embodiment / feature / aspect, wherein the aqueous suspension comprises 4 to 10 pounds (1.81 to 4.53 kg) of grafted polyvinyl alcohol polymer per tonne of dry cellulose papermaking fiber. nQy / rn / Lznz / q / Yi 42. The process in conformity with any above or following embodiment / feature / aspect, wherein the amount of grafted polyvinyl alcohol polymer is effective in increasing at least one of the selected paper properties of paper wet strength and paper dry strength by at least 10% compared to paper made from the aqueous suspension without the grafted polyvinyl alcohol polymer. 43. The process in conformity with any prior or subsequent embodiment / feature / aspect, wherein the amount of grafted polyvinyl alcohol polymer is effective in providing a paper moisture strength to paper dry strength ratio of 0.6, wherein the moisture strength value is determined by the Finch Cup and Humidity Chamber methods and the dry strength value is determined by direct tensile strength measurement of the conditioned dry paper. 44. The process in accordance with any foregoing or following embodiment / feature / aspect, wherein absorbing the quantity of polyvinyl alcohol polymer grafted onto cellulose papermaking fibers in the aqueous suspension comprises: providing a pulp deposit comprising cellulose papermaking fibers; and adding the quantity of grafted polyvinyl alcohol polymer to the pulp deposit, and wherein forming said suspension on the mesh comprises: drain the suspension after absorbing the amount of grafted polyvinyl alcohol polymer; and form the drained suspension into one of paper and cardboard. 45. A process for manufacturing a grafted polyvinyl alcohol polymer comprising: provide an aqueous solution of a polyvinyl alcohol polymer; adding to the aqueous solution at least one free radical forming initiator and a plurality of side chain monomers, the plurality of side chain monomers comprising: (a) an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and a reactive quaternary ammonium salt, or any combination thereof; (b) optionally an aliphatic amide; and (c) optionally a branched alkyl acrylate. naj / rn / Lznz / q / Yi 46. ​​The process of conformity with any preceding or subsequent embodiment / feature / aspect, which further comprises: joining at least a portion of the plurality of side-chain monomers to a polyvinyl alcohol backbone in an a:b:c ratio range of 3:1:5 to 2.5:1:4 on a weight basis and normalized to an amount of (b) aliphatic amide. 47. A process for repulping paper, the process comprising: contacting a paper product with a caustic aqueous solution containing alkali metal ions to convert the carboxylic functionalities in the grafted polyvinyl alcohol polymer according to any prior or following embodiment / feature / aspect into alkali metal carboxylate functionalities, wherein the paper product comprises: a paper material; and the grafted polyvinyl alcohol polymer. 48. A polymer mixture, comprising: a first grafted polyvinyl alcohol polymer comprising a first polyvinyl alcohol main chain and a first plurality of side chains grafted onto the first polyvinyl alcohol main chain, wherein the side chains of the first plurality of side chains comprise: i) one or more units selected from: an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid; and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof; and a second grafted polyvinyl alcohol polymer comprising a second polyvinyl alcohol main chain and a second plurality of side chains grafted onto the second polyvinyl alcohol main chain, wherein the side chains of the second plurality of side chains comprise: i) one or more units of a reactive quaternary ammonium salt;and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof.; 49. The polymer mixture according to any above or following embodiment / feature / aspect, comprising the first grafted polyvinyl alcohol polymer and the second polyvinyl alcohol polymer in a weight ratio of the first grafted polyvinyl alcohol polymer to the second polyvinyl alcohol polymer of 10:1 to 1:10. The present invention may include any combination of these various features or prior and / or subsequent embodiments as set forth in sentences and / or paragraphs. Any combination of the features disclosed in this application is considered part of the present invention, and no limitation is intended with respect to the combinable features. The Applicants specifically incorporate the full content of all references cited in this disclosure. Furthermore, where a quantity, concentration, or other value or parameter is provided as a range, preferred range, or list of upper and lower preferred values, this is to be understood as a specific disclosure of all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether the ranges are described separately. Where a range of numerical values ​​is stated in this application, unless otherwise indicated, the range is intended to include its endpoints and all whole numbers and fractions within the range. The scope of the invention is not intended to be limited to the specific values ​​listed in defining a range. Other embodiments of the present invention will become evident to those skilled in the art from consideration of this specification and the practice of the invention described in this application. This specification and the examples are intended to be considered as examples only, the true scope and spirit of the invention being indicated by the following claims and their equivalents.

Claims

1. A grafted polyvinyl alcohol polymer comprising a polyvinyl alcohol main chain and a plurality of side chains grafted onto the polyvinyl alcohol main chain, wherein one or more of said side chains of the plurality of side chains comprise: i) one or more units selected from: an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid and a reactive quaternary ammonium salt; and, optionally, i) units of an aliphatic amide, or a branched alkyl acrylate, or any combination thereof.

2. The grafted polyvinyl alcohol polymer according to claim 1, wherein at least 75%, by number, of said side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid, aliphatic dicarboxylic acid and quaternary ammonium reactive salt; and, optionally, i) units of aliphatic amide, or branched alkyl acrylate, or any combination thereof.

3. The grafted polyvinyl alcohol polymer according to claim 2, wherein no more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units.

4. The grafted polyvinyl alcohol polymer according to claim 1, wherein one or more of said side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.

5. The grafted polyvinyl alcohol polymer according to claim 1, wherein the side chains of the plurality of side chains comprise: i) quaternary ammonium reactive salt units; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.

6. The grafted polyvinyl alcohol polymer according to claim 5, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) units of the reactive quaternary ammonium salt; and, optionally, i) units of the aliphatic amide, or units of the branched alkyl acrylate, or any combination thereof.

7. The grafted polyvinyl alcohol polymer according to claim 6, wherein no more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units.

8. The grafted polyvinyl alcohol polymer according to claim 5, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) quaternary ammonium reactive salt units; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and have no aliphatic monocarboxylic acid or aliphatic dicarboxylic acid units.

9. The grafted polyvinyl alcohol polymer according to claim 8, wherein no more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units.

10. The grafted polyvinyl alcohol polymer according to claim 5, wherein one or more of said side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.

11. The grafted polyvinyl alcohol polymer according to claim 1, wherein the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.

12. The grafted polyvinyl alcohol polymer according to claim 11, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof.

13. The grafted polyvinyl alcohol polymer according to claim 12, wherein no more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units.

14. The grafted polyvinyl alcohol polymer according to claim 1, wherein at least 75%, by number, of the side chains of the plurality of side chains comprise: i) one or more units selected from: aliphatic monocarboxylic acid and aliphatic dicarboxylic acid; and, optionally, i) aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have quaternary ammonium reactive salt units.

15. The grafted polyvinyl alcohol polymer according to claim 14, wherein no more than 25%, by number, of the side chains of the plurality of side chains comprise aliphatic amide units, or branched alkyl acrylate units, or any combination thereof, and do not have aliphatic monocarboxylic acid, aliphatic dicarboxylic acid, and quaternary ammonium reactive salt units.

16. The grafted polyvinyl alcohol polymer according to claim 15, wherein one or more of said side chains of the plurality of side chains comprise the aliphatic amide or branched alkyl acrylate or any combination thereof.

17. The grafted polyvinyl alcohol polymer according to claim 1, wherein the polyvinyl alcohol main chain, in its unreacted form, has a monomodal molecular weight distribution of approximately 5 K to 20000 K Daltons.

18. The grafted polyvinyl alcohol polymer according to claim 1, wherein the polyvinyl alcohol main chain, in its unreacted form, has a degree of hydrolysis of approximately 74 mol% to approximately 99 mol%.

19. The grafted polyvinyl alcohol polymer according to claim 1, wherein the polyvinyl alcohol main chain, in its unreacted form, has a degree of hydrolysis of approximately 74 mol% to approximately 90 mol%.

20. The grafted polyvinyl alcohol polymer according to claim 1, wherein one or more of said side chains of the plurality of side chains are grafted into the polyvinyl alcohol main chain through acetate residues of the polyvinyl alcohol main chain.

21. The grafted polyvinyl alcohol polymer according to claim 1, wherein one or more of said side chains of the plurality of side chains are grafted into the polyvinyl alcohol main chain through hydroxyl residues of the polyvinyl alcohol main chain.

22. The grafted polyvinyl alcohol polymer according to claim 1, wherein the quaternary ammonium reactive salt is present and comprises at least one of diallyl dimethyl ammonium chloride, 3-acrylamidopropyl trimethyl ammonium chloride, or a combination thereof; wherein the aliphatic amide is present and comprises at least one of acrylamide, methacrylamide, dimethyl acrylamide, diethyl acrylamide, dipropyl acrylamide, and N-t-butyl acrylamide; and wherein the branched alkyl acrylate is present and comprises at least one of 2-ethylheptyl acrylate, 2-ethylhexyl acrylate, 2-ethylpentyl acrylate, and 2-ethylbutyl acrylate.

23. The grafted polyvinyl alcohol polymer according to claim 1, which is or comprises structure (I): [CH2-CH(OH)]a-[CH2-CH(R])]b (I) wherein a total weight percent of (a) units is from 74% to 84% based on the total weight of the grafted polyvinyl alcohol polymer, wherein a total weight percent of (b) units is from 16% to 26% based on the total weight of the grafted polyvinyl alcohol polymer, wherein each R is acetate or a side chain of the plurality of side chains.

24. The grafted polyvinyl alcohol polymer according to claim 1, comprising: a weight percentage of polyvinyl alcohol main chain of approximately 40% to approximately 50% by weight of total solids; a weight percentage of quaternary ammonium reactive salt side chain of approximately 6% to approximately 10% by weight of total solids; a weight percentage of aliphatic amide of approximately 6% to approximately 9% by weight of total solids; and a weight percentage of branched alkyl acrylate of approximately 24% to approximately 50% by weight of total solids.

25. The grafted polyvinyl alcohol polymer according to claim 1, which is or comprises structure (IV): nQ / yrn / Lznz / q / Yii wherein the total weight percent of a is 30% to 34% based on the total weight of the grafted polyvinyl alcohol polymer, the total weight percent of b is 6% to 10% based on the total weight of the grafted polyvinyl alcohol polymer, the total weight percent of c is 0.5% to 1.0% based on the total weight of the grafted polyvinyl alcohol polymer, and the total weight percent of d is 58% to 62% based on the total weight of the grafted polyvinyl alcohol polymer.

26. The grafted polyvinyl alcohol polymer according to claim 1, having a solids content of at least 25% solids.

27. The grafted polyvinyl alcohol polymer according to claim 1 in the form of dry solid particles.

28. A polymeric composition comprising: the grafted polyvinyl alcohol polymer according to claim 1; and an aqueous medium in which the grafted polyvinyl alcohol polymer is dispersed.

29. The polymer composition according to claim 28, having a pH of approximately 3 to approximately 6.

30. An aqueous-based graft emulsion polymer, comprising the grafted polyvinyl alcohol polymer according to claim 1.

31. A cellulosic pulp product comprising: cellulosic pulp; and the grafted polyvinyl alcohol polymer according to claim 1.

32. A paper product comprising: a paper material; and the grafted polyvinyl alcohol polymer according to claim 1.

33. The paper product according to claim 32, wherein the paper material comprises a cellulosic fiber comprising a carboxyl group, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein a unit of the quaternary ammonium reactive salt units comprises a cationic charge that interacts electrostatically with the carboxyl group of the cellulosic fiber.

34. A product comprising at least one layer of paper comprising the grafted polyvinyl alcohol polymer according to claim 1, wherein the product is sheets of paper, cardboard, disposable tissues or cardstock.

35. The product according to claim 34, wherein the paper layer comprises a cellulosic fiber comprising a carboxyl group, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein a unit of the quaternary ammonium reactive salt units comprises a cationic charge that interacts electrostatically with the carboxyl group of the cellulosic fiber.

36. A fibrous material comprising: cotton fibers; and the grafted polyvinyl alcohol polymer according to claim 1.

37. The fibrous material according to claim 36, wherein the cotton fibers are coated with the grafted polyvinyl alcohol polymer.

38. The fibrous material according to claim 36, wherein the cotton fibers are impregnated with the grafted polyvinyl alcohol polymer.

39. The fibrous material according to claim 36, wherein at least a portion of the cotton fibers comprises a cellulosic fiber comprising a carboxyl moiety, wherein one or more of said side chains of the plurality of side chains comprise units of the quaternary ammonium reactive salt, and wherein one unit of the quaternary ammonium reactive salt units nQy / rn / Lznz / q / Yi comprises a cationic charge that interacts electrostatically with the carboxyl moiety of the cellulosic fiber.

40. A papermaking process, the process comprising: absorbing an amount of the grafted polyvinyl alcohol polymer according to claim 1 onto cellulosic papermaking fibers in aqueous suspension; forming said suspension into a mesh; and drying said mesh, wherein the amount of the grafted polyvinyl alcohol polymer is effective in increasing at least one of the paper's wet strength, dry strength, and water dispersibility compared to paper made from the aqueous suspension without the grafted polyvinyl alcohol polymer.

41. The process according to claim 40, wherein the aqueous suspension comprises 4 to 10 pounds (1.81 to 4.53 kg) of grafted polyvinyl alcohol polymer per tonne of dry cellulose papermaking fiber.

42. The process according to claim 40, wherein the amount of grafted polyvinyl alcohol polymer is effective in increasing at least one of the selected paper properties of paper wet strength and paper dry strength by at least 10% compared to paper made from the aqueous suspension without the grafted polyvinyl alcohol polymer.

43. The process according to claim 40, wherein the amount of grafted polyvinyl alcohol polymer is effective in providing a paper moisture strength to paper dry strength ratio of 0.6, wherein the moisture strength value is determined by the Finch Cup and Humidity Chamber methods and the dry strength value is determined by direct tensile strength measurement of the dry, conditioned paper.

44. The process according to claim 40, wherein absorbing the amount of polyvinyl alcohol polymer grafted onto cellulose papermaking fibers in the aqueous suspension comprises: providing a pulp reservoir comprising the cellulose papermaking fibers; and adding the amount of grafted polyvinyl alcohol polymer to the pulp reservoir, and wherein forming said suspension on the screen comprises: draining the suspension after absorbing the amount of grafted polyvinyl alcohol polymer; and forming the drained suspension into a paper and cardboard container.

45. A process for manufacturing the grafted polyvinyl alcohol polymer of claim 1, said method comprising: providing an aqueous solution of a polyvinyl alcohol polymer; adding to the aqueous solution at least one free-radical initiator and a plurality of side-chain monomers, the plurality of side-chain monomers comprising: (a) an aliphatic monocarboxylic acid, an aliphatic dicarboxylic acid, or a reactive quaternary ammonium salt, or any combination thereof; (b) optionally an aliphatic amide; and (c) optionally a branched alkyl acrylate.

46. ​​The process according to claim 45, further comprising: joining at least a portion of the plurality of side-chain monomers to a polyvinyl alcohol backbone in a ratio range a:b:c from 3:1:5 to 2.5:1:4 on a weight basis and normalized to an amount of (b) aliphatic amide.

47. A process for repulping paper, the process comprising: contacting a paper product with a caustic aqueous solution containing alkali metal ions to convert the carboxylic functionalities in the grafted polyvinyl alcohol polymer according to claim 1 into alkali metal carboxylate functionalities, wherein the paper product comprises: a paper material; and the grafted polyvinyl alcohol polymer.

48. A polymer mixture, comprising: a first grafted polyvinyl alcohol polymer comprising a first polyvinyl alcohol main chain and a first plurality of side chains grafted onto the first polyvinyl alcohol main chain, wherein the side chains of the first plurality of side chains comprise: i) one or more units selected from: an aliphatic monocarboxylic acid and an aliphatic dicarboxylic acid; and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof; and a second grafted polyvinyl alcohol polymer comprising a second polyvinyl alcohol main chain and a second plurality of side chains grafted onto the second polyvinyl alcohol main chain, wherein the side chains of the second plurality of side chains comprise: i) one or more units of a reactive quaternary ammonium salt;and, optionally, i) an aliphatic amide or a branched alkyl acrylate or any combination thereof.; 49. The polymer blend according to claim 48, comprising the first grafted polyvinyl alcohol polymer and the second polyvinyl alcohol polymer in a weight ratio of the first grafted polyvinyl alcohol polymer to the second polyvinyl alcohol polymer of 10:1 to 1:10.