CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Patent Application No. 62/939,421, filed on November 22, 2019, which is incorporated by reference herein.

BACKGROUND

Field

[0002] Embodiments described generally relate to di alkenyl succinic amide acids and processes for making and using same.

Description of the Related Art

[0003] In the papermaking industry, sizing is utilized to make paper having water resistance and hot water penetration resistance by manipulating the internal sizing and paper surface sizing of the paper product. Internal sizing processes typically involve adding a sizing agent such as an alkyl ketene dimer (AKD), an alkenyl succinic anhydride (ASA), or rosin directly to a paper furnish. In general, particles of the sizing agent are capable of forming larger agglomerates which are adsorbed onto the surfaces of the fibers and fillers of the paper furnish. The particles of the sizing agent are generally retained in the wet paper sheet and in the drying section. Influenced by drying temperature, the particles of the sizing agent generally melt and spread onto surface of the paper fibers. Reactive functional groups of the sizing agent direct inward or toward the paper fibers and hydrophobic groups of the sizing agent direct outward or away from the paper fibers. The reactive functional groups react with a hydroxyl group of the paper fibers to form a covalent bond that results in sizing of the paper product.

[0004] The alkenyl succinic anhydride has a number of advantages for the sizing of paper when compared to the alkyl ketene dimer. For example, alkenyl succinic anhydride provides rapid sizing over a wide pH range, is easily emulsified, is compatible with aluminum sulfate, is more easily synthesized, costs less, and is less of an environmental pollutant. Alkenyl succinic anhydride has been utilized in high-grade paper production worldwide and is suitable for producing high-grade cultural paper, coating paper, paperboard, and the like. Alkenyl succinic anhydride, however, hydrolyzes easily due to high reactivity. In particular, the hydrolysis of alkenyl succinic anhydride is often severe when used in processes for making paper with high moisture content. There is a need, therefore, for improved sizing agents, sizing compositions containing same, and processes for making and using same. SUMMARY

[0005] Di alkenyl succinic amide acids and processes for making and using same are provided. In some embodiments, the di alkenyl succinic amide acid can have a chemical formula of (I): where R ¹ and R ² can independently be a linear or branched C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ can independently be O or S, and X can be O, S, or N.

[0006] In some embodiments, a sizing composition can include a sizing agent, an emulsifier, and a diluent. The sizing agent can include the di alkenyl succinic amide acid that can have the chemical formula of (I).

[0007] In some embodiments a process for making a di alkenyl succinic amide acid can include mixing a polyamine, a solvent, and an alkenyl succinic anhydride that can include a linear or branched C8 to C24 alkenyl group to produce a mixture. The process can also include reacting the polyamine and the alkenyl succinic anhydride in the mixture to produce the di alkenyl succinic amide acid.

[0008] In some embodiments, a process for making a sizing composition can include mixing a sizing agent, an emulsifier, and a diluent to produce an emulsion. The sizing agent can include the di alkenyl succinic amide acid that can have the chemical formula of (I).

[0009] In some embodiments, a process for making paper can include incorporating into the paper or applying to a surface of the paper a sizing composition that can include the di alkenyl succinic amide acid that can have chemical formula of (I).

DETAILED DESCRIPTION

[0010] Di alkenyl succinic amide acids (DASA) have been synthesized. The di alkenyl succinic amide acid can have a chemical formula of (I): where R ¹ and R ² can independently be a linear or branched C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ can independently be O or S, and X can be O, S, or N. In some embodiments, each Z ¹ , Z ² , Z ³ , and Z ⁴ can be O or each Z ¹ , Z ² , Z ³ , and Z ⁴ can be S and X can be O, S, or N. In some embodiments, two of Z ¹ , Z ² , Z ³ , and Z ⁴ can be O, two of Z ¹ , Z ² , Z ³ , and Z ⁴ can be S, and X can be O, S, or N. In some embodiments, three of Z ¹ , Z ² , Z ³ , and Z ⁴ can be O, one of Z ¹ , Z ² , Z ³ , and Z ⁴ can be S, and X can be O, S, or N. In some embodiments, three of Z ¹ , Z ² , Z ³ , and Z ⁴ can be S, one of Z ¹ , Z ² , Z ³ , and Z ⁴ can be O, and X can be O, S, or N. In some embodiments, R ¹ and R ² can independently be a linear C8 to Cl 8 alkenyl group. In some embodiments, R ¹ and R ² can independently be a branched Cl 6 to C24 alkenyl group. In some embodiments, R ¹ and R ² can each be a branched Cl 8 alkenyl group, a branched C20 alkenyl group, a branched C22 alkenyl group, or a branched C24 alkenyl group.

[0011] It has been surprisingly and unexpectedly discovered that the di alkenyl succinic amide acids can be used as a sizing agent for paper products. The inventors of the present application tried for several years to modify the chemical structure of alkenyl succinic anhydride, a commonly employed sizing agent, to produce new compounds for use in sizing paper, but nothing was found that worked. Surprisingly and unexpectedly, however, it was discovered that the di alkenyl succinic amide acid having formula (I) provides sizing to paper products. The di alkenyl succinic amide acid can be used alone and/or as a component of a sizing composition that can be used to internally size paper products and/or to surface size paper products.

[0012] The di alkenyl succinic amide acid can be produced by reacting one or more polyamines and one or more alkenyl succinic anhydrides. In some embodiments, the polyamine and the alkenyl succinic anhydride can be mixed, blended, or otherwise combined with one or more solvents to produce a mixture and the polyamine and the alkenyl succinic anhydride can react in the mixture to produce the di alkenyl succinic amide acid. In some embodiments, one or more catalysts can be mixed, blended, or otherwise combined with the polyamine and the alkenyl succinic anhydride or the polyamine, the alkenyl succinic anhydride, and the solvent to produce the mixture.

[0013] In some embodiments, a molar ratio of the alkenyl succinic anhydride to the polyamine can be about 0.8:1, about 0.9:1, about 1:1, or about 1.1:1 to about 1.5:1, about 1.6:1, about 1.7:1, about 1.8:1, about 1.9:1, about 2:1. The polyamine and the alkenyl succinic anhydride can react at a temperature of about 60°C, about 70°C, about 80°C, or about 85°C to about 90°C, about 110°C, about 140°C, about 160°C, or about 180°C. The polyamine and the alkenyl succinic anhydride can be reacted for a period of time of about 30 minutes, about 60 minutes, about 180 minutes, or about 240 minutes to about 24 hours or more. In some embodiments, the reaction mixture can be stirred or otherwise agitated during reaction of the polyamine and the alkenyl succinic anhydride.

[0014] In some embodiments, once the di alkenyl succinic amide acid has been produced, at least a portion of the solvent can be separated therefrom. In some embodiments, azeotropic distillation and/or layer separation, can be used to remove at least a portion of the solvent. In other embodiments, the as prepared reaction product that includes the di alkenyl succinic amide acid can be used as prepared.

[0015] The alkenyl succinic anhydride can have a chemical formula of (II): where R can be a linear or branched C8 to C24 alkenyl group. In some specific embodiments, the alkenyl succinic anhydride can be or can include, but is not limited to, 3-[(E)-oct-l- enyl]oxolane-2,5-dione (1-octenylsuccinic anhydride); 3-non-l-enyloxolane-2,5-dione (nonenyl succinic anhydride); 3-[(£)-dodec-l-enyl]oxolane-2,5-dione (dodecenylsuccinic anhydride); 3-dodec-2-enyloxolane-2,5-dione ((2-dodecen-l-yl)succinic anhydride); 3-(16- methylheptadec-l-enyl)oxolane-2,5-dione (i-octadecenyl succinic anhydride); 3-[(£)-hexadec- l-enyl]oxolane-2,5-dione (hexadecenylsuccinic anhydride); 3-[ £)-dec-2-enyl]oxolane-2,5- dione (2-Decenylsuccinic anhydride); 3 - [(£)-4, 6, 8 -trimethylnon-2-en-2-yl] oxolane-2, 5 -dione (tetrapropenyl succinic anhydride); one or more C20-C24 alkenyl succinic anhydrides, or any mixture thereof.

[0016] The polyamine can be or can include, but is not limited to, urea, thiourea, 1- (diaminomethylene)urea, guanidine, 1,3-diaminourea, benzene- 1,3-diamine, 2,4,6- triaminopyrimidine, short chain poly(lysine) having about 4 to about 10 repeat units of the lysine amino acid, or any mixture thereof.

[0017] The solvent can be or can include one or more polar protic solvents, one or more polar aprotic solvents, or a mixture thereof. In some embodiments, the solvent can be or can include, but is not limited to, sulfolane, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, N-ethyl pyrrolidone, glacial acetic acid, or any mixture thereof.

[0018] The catalyst, if present, can be or can include, but is not limited to, acetic anhydride, acetic acid, a mixture of acetic anhydride and sodium acetate, trifluoro acetic acid, methane sulfonic acid, chloroacetic acid, sodium phenylphosphinate, phosphorous acid, bromo acetic acid, fluoro acetic acid, trifluoroacetic anhydride, para toluene sulfonic acid, or any mixture thereof. The catalyst, if present, can be present in an amount of about 0.01 mol% about 0.03 mol%, or about 0.05 mol% to about 0.7 mol%, about 0.9 mol%, about 0.1 mol%, or about 1.2 mol%, based on a combined amount of the polyamine, the solvent, the alkenyl succinic anhydride, and the catalyst.

[0019] In some embodiments, a sizing composition can include one or more sizing agents, one or more emulsifiers, and a diluent, where the sizing agent can be or can include the di alkenyl succinic amide acid. In some embodiments, the sizing composition can have a ratio of the emulsifier to the sizing agent (emulsifier : sizing agent), on a volume basis, of about 0.03:1, about 0.1:1, about 0.3:1, about 0.4:1, about 0.5:1, about 0.6:1, about 0.65:1, about 0.70:1, about 0.75:1, or about 0.8:1 to about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, about 1.3:1, about 1.4:1, or about 1.5:1.

[0020] The sizing composition can include about 1 wt%, about 3 wt%, about 5 wt%, about 7 wt%, about 10 wt%, about 13 wt%, about 15 wt%, or about 18 wt% to about 22 wt%, about 25 wt%, about 27 wt%, about 30 wt%, about 33 wt%, about 35 wt%, about 37 wt%, or about 40 wt% of the sizing agent, based on a combined weight of the sizing agent, the emulsifier, and the diluent. The sizing composition can include about 0.01 wt%, about 0.1 wt%, about 1 wt%, about 3 wt%, about 5 wt%, about 7 wt%, or about 9 wt% to about 11 wt%, about 13 wt%, about 15 wt%, about 17 wt%, or about 20 wt% of the emulsifier, based on a combined weight of the sizing agent, the emulsifier, and the diluent. The sizing composition can include about 40 wt%, about 45 wt%, about 50 wt%, about 55 wt%, about 60 wt%, or about 65 wt% to about 70 wt%, about 75 wt%, about 80 wt%, about 85 wt%, about 90 wt%, about 95 wt%, or about 99 wt% of the diluent, based on a combined weight of the sizing agent, the emulsifier, and the diluent. In some embodiments, the sizing composition can include about 1 wt% to about 40 wt% of the sizing agent, about 0.01 wt% to about 20 wt% of the emulsifier, and about 40 wt% to about 99 wt% of the diluent, based on a combined weight of the sizing agent, the emulsifier, and the diluent.

[0021] In some embodiments, the sizing composition can include one or more additional sizing agents in addition to the di alkenyl succinic amide acid. Suitable additional sizing agents can be or can include, but are not limited to, one or more alkenyl succinic anhydrides, one or more alkyl ketene dimers, one or more rosins, or any mixture thereof. In some embodiments, suitable additional sizing agents that can be used in combination with the di alkenyl succinic amide acid can include those disclosed in U.S. PatentNos.: 8,852,400; 8,709,207; and 8,840,759; and U.S. Patent Application Publication Nos.: 2015/0020988; and 2014/0336314.

[0022] In some embodiments, the diluent can be or can include, but is not limited to, water, sulfolane, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, N-ethyl pyrrolidone, glacial acetic acid, or any mixture thereof.

[0023] The emulsifier can be or can include, but is not limited to, cationic agents and/or non- cationic agents. In some embodiments, the emulsifier can be or can include, one or more cationic water soluble vinyl addition or condensation polymers having a weight average molecular weight of about 1,000,000 or less. In some embodiments, the cationic water soluble vinyl addition or condensation polymer can have a weight average molecular weight of about 10,000 to about 1,000,000. In some embodiments, about 10 wt% to about 100 wt% of a mer content of the cationic water soluble vinyl addition or condensation polymer can be a cationic vinyl monomer or a cationically modified monomer. Suitable cationic water soluble vinyl addition or condensation polymers can be or can include, but are not limited to, acrylamide- dimethylaminoethylacrylate, acrylamide-dimethylaminoethylacrylate quaternaries, acrylamide-diethylaminoethylacrylate, acrylamide-diethylaminoethylacrylate quaternaries, acrylamide-dimethylaminoethylmethacrylate, acrylamide-dimethylaminoethylmethaciylate quaternaries, acrylamide-diallyldimethyl ammonium chloride, polydiallyl-dimethyl ammonium chloride, polydimethylaminoethylmethacrylate and its quaternaries, polymethaaylamidopropyltrimethyl ammonium chloride, acrylamide- methacrylamidopropyltrimethyl ammonium chloride, or any mixture thereof. Other suitable emulsifiers can be or can include, polymers of acrylamide that have been subjected to a "Mannich" reaction with formaldehyde and a lower alkyl secondary amine. These Manniched polyacrylamide polymers may or may not be quatemized. In some embodiments, the cationic water soluble vinyl addition or condensation polymer can be in the form of a water-in-oil emulsion, dry powders, and or aqueous solutions. The cationic water soluble vinyl addition or condensation polymer can include those disclosed in U.S. Patent No. 4,657,946.

[0024] Other suitable emulsifiers can be or can include, but are not limited to, polymers derived from 2-methacryloyloxtethyl phosphorylcholine or copolymers of 2-methacryloyloxtethyl phosphorylcholine and one or more comonomers. In some embodiments, the emulsifier can be or can include polyphosphorylcholine glycol acrylate, 2-(N,N,N-Trimethylamino)ethyl 2- (2-methyl-2-propenoyloxy)ethyl phosphate inner salt, polymer with butyl 2-methyl-2- propenoate (Polyquatemium-51, CAS No. 125275-25-4), or any mixture thereof. [0025] In some embodiments, the emulsifier can be or can include, but is not limited to, alkyl and aryl primary, secondary and tertiary amines and their corresponding quaternary salts, sulfosuccinates, fatty acids, ethoxylated fatty acids, fatty alcohols, ethoxylated fatty alcohols, fatty esters, ethoxylated fatty esters, ethoxylated triglycerides, sulfonated amides, sulfonated amines, ethoxylated polymers, propoxylated polymers, ethoxylated and propoxylated copolymers, polyethylene glycols, phosphate esters, phosphonated fatty acid ethoxylates, phosphonated fatty alcohol ethoxylates, alkyl and aryl sulfonates and sulfates, or any mixture thereof. In other embodiments, the emulsifier can be or can include, but is not limited to, carboxylated alcohols; alkylphenol ethoxylates; carboxylic acids; diphenyl sulfonate derivatives; ethoxylated alcohols; ethoxylated alkylphenols; ethoxylated amines; ethoxylated amides; ethoxylated aryl phenols; ethoxylated glycol esters; polyethylene glycols; glycerol esters; glycol esters; certain lanolin-based derivatives; monoglycerides, diglycerides and derivatives; olefin sulfonates; phosphate esters; phosphorus organic derivatives; polymeric polysaccharides; propoxylated and ethoxylated fatty acids; alkyl and aryl sulfates and sulfonates; ethoxylated alkylphenols; sulfosuccinamates; sulfosuccinates. In still other embodiments, the emulsifier can be or can include, but is not limited to, starches, non-cationic starch derivatives, guar gums, dextrines, carboxymethyl cellulose, gum arabic, gelatin, polyvinyl alcohol, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitol hexaoleate, polyoxyethylene sorbitol laurate, polyoxyethylene sorbitol oleate-laurate, sodium dioctyl sulfosuccinate, polyoxyethylene alkyl phosphate, or any mixture thereof.

[0026] Still other suitable emulsifiers can be or can include, but are not limited to, glyoxalated poly(DADMAC)/AcAm polymer having a 5 mole % DADMAC monomer content; glyoxalated poly(DADMAC)/AcAm polymer having a 5 mole % DADMAC monomer content and further comprising MgS0 ₄ .7Hi0; glyoxalated poly(DADMAC)/AcAm polymer having a 12 mole % DADMAC monomer content; and glyoxalated poly(DADMAC)/AcAm polymer having a 12 mole % DADMAC monomer content and further comprising MgS0 ₄ .7H ₂ 0. As used herein, the term “DADMAC” refers to diallyldimethyl ammonium chloride. As used herein, the term “AcAm” refers to acrylamide.

[0027] Additional suitable emulsifiers can be or can include, but are not limited to, a polymer that can include at least one primary and/or at least one secondary amine containing monomer. In some embodiments, the amine-containing polymer can have a molecular weight greater than about 10,000 Daltons and below about 2,000,000 Daltons, where at least 1 mole percent and up to 99 mole percent of the mer content of the polymer is a polymerizable primary and/or secondary amine-containing monomer. In other embodiments, the amine-containing polymer can have molecular weight of about 200,000 to about 1,500,000 Daltons. In some embodiments, at least 1 mole percent and up to 99 mole percent of the mer units can be amine containing vinyl- or allyl-monomers. In some embodiments, the amine-containing polymer can be or can include diallylamine ("DAA"). In some embodiments, the amine-containing polymer can be a diallylamine-acrylamide ("DAA-AcAm" or “DAA/ACAm”) copolymer. In the DAA/AcAm copolymer, the mole percentage of DAA can be about 1%, about 10%, about 20%, about 30%, or about 40% to about 50%, about 60%, about 70%, about 80%, about 90%, or about 99%.

[0028] Commercially available emulsifiers that can be used to make the sizing composition that includes the di alkenyl succinic amide acid can be or can include, but are not limited to, NALSIZE ^® 7548 and NALSIZE ^® 7541, available from Nalco Chemical Company; LIPIDURE ^® emulsifiers such as LIPIDURE ^® -NR, NA; LIPIDURE ^® -HM, PMB; LIPIDURE ^® - C; and LIPIDURE ^® for cosmetics that are available from NOF America Corporation; and any mixture thereof. Other suitable emulsifiers can include those disclosed in U.S. Patent Nos.: 7,455,751; 8,709,207; 8,840,759; 8,852,400; 8,747,616; 9,624,623; 10,006,171; and 10,227,731 and U.S. Patent Application Publication Nos.: 2014/0336314 and 2015/0020988. [0029] The sizing composition can be prepared using well-known procedures. The general concept includes imparting energy to a mixture of hydrophobic material, e.g., sizing agent, and diluent, e.g., water, in the presence of an emulsifier that can produce small droplets of the hydrophobic material suspended in the diluent. In some embodiments, the sizing composition can be emulsified via high-speed agitators, mechanical homogenizers, turbine pumps, centrifugal pumps, static in-line mixers, peristaltic pumps, ultrasonic homogenizers, rotor- stator mixers, colloid mills, or any combination thereof. In some embodiments, the sizing composition can be emulsified as disclosed in colloid science (e.g., S. E. Friberg & S. Jones, “Emulsions” in the Encyclopedia of Chemical Technology, Vol. 9 (4 ^th edition)); and/or U.S. Patent Nos.: 4,040,900; 4,657,946; and 8,840,759.

[0030] The sizing composition can have a median droplet size of about 0.01 pm, about 0.1 pm, or about 0.1 pm to about 2 pm, about 5 pm, or about 10 pm. In some embodiments, the sizing composition can have a median droplet size or median particle size of less than 5 pm, less than 3 pm, less than 2.5 pm, less than 2 pm, less than 1.5 pm, or less than 1 pm. The median droplet size or median particle size can be measured by laser light scattering with the Malvern Mastersizer Micro from Malvern Instruments Ltd., UK.

[0031] The sizing composition can be used to size paper prepared from all types of cellulosic fibers, non-cellulosic fibers, and combinations of cellulosic and non-cellulosic fibers. The cellulosic fibers can be or can include, but are not limited to, sulfate (Kraft), sulfite, soda, neutral sulfite semi-chemical (NSSC), thermomechanical (TMP), chemi-thermomechanical (CTMP), groundwood (GWD), and any mixture thereof. The cellulosic fibers can be bleached or unbleached. These designations refer to wood pulp fibers that have been prepared by any of a variety of processes that are typically used in the pulp and paper industry. The non- cellulosic or synthetic fibers can be or can include, but are not limited to, rayon, polyethylene, polypropylene, polyester, nylon, or any mixture thereof.

[0032] The size composition that includes the di alkenyl succinic amide acid can be used in the manufacture of all grades of paper in which resistance to the penetration of liquids, e.g., dairy products, citrus juices, oils, water, and inks, is a desired property. In some embodiments, the paper product can be gypsum wall board liner, boxboard, liquid packaging board, folding carton, cup stock, sack paper, molded paper products, newspaper and printing paper, construction paper, and the like.

[0033] The sizing composition can be used for internal sizing of paper products, surface sizing of paper products, and/or internal sizing and surface sizing. Internal sizing refers to treatment of a fiber slurry with the sizing composition during manufacture of the paper product so that the paper product will resist fluids. Surface sizing refers to the addition of the sizing composition onto the surface of a dried paper product rather than to the fiber slurry.

[0034] In some embodiments, the sizing composition can be fed to the wet end of a paper machine, which can include thin stock, thick stock, or white water systems. For example, the sizing composition can be fed in the thin stock approach line to a headbox, which can also include a white water system, e.g., pre-fan pump. Although wet end addition of the sizing emulsion is the norm, any addition point that can introduce the composition to the final paper sheet can yield a sized sheet and can be used. In some embodiments, a mixing chamber can be used to introduce the sizing composition into the papermaking process. Examples of such mixing chambers can include those disclosed in U.S. Patent No. 7,550,060.

[0035] In some embodiments, the sizing composition can be applied to at least one surface of a paper product. For example, the sizing composition can be applied to the surface of the paper using a puddle or film size press or a size press by using a calender or a doctor knife blade. In another embodiment, the sizing composition can be sprayed onto the paper web or be applied by dipping the paper into the aqueous surface sizing composition. In some embodiments, the paper product containing the sizing composition on a surface thereof can be allowed to air dry and/or can be heated, e.g., in an oven, to produce the surface sized paper product. Accordingly, sized paper products that include the di alkenyl succinic amide acid can include the di alkenyl succinic amide acid as an internal sizing agent, as an external or surface sizing agent, or a combination thereof. Suitable sizing processes can include those disclosed in U.S. Patent Nos. 4,657,946; 7,455,751; 7,550,060; 8,840,759; and 10,006,171.

[0036] The amount of sizing composition that can be used to size paper can vary depending, for example, on the particular sizing composition employed, the particular pulp involved, the specific operating conditions, the contemplated end-use of the paper, and the like. Typical concentrations of the sizing composition, based on the dry weight of the pulp in the finished sheet or web, can be about 5 g, about 50 g, about 100 g, about 250 g, or about 500 g to about 2 kg, about 2.5 kg, about 5 kg, about 10 kg, or about 25 kg of the sizing composition per metric ton of dry fiber in the sized paper product.

[0037] The sizing composition can also be used in conjunction with or serially with other additives conventionally used in the production of paper and other cellulosic products. Such additional additives conventionally used can include, but are not limited to, colorants, inorganic pigments, fillers, anti-curl agents, surfactants, plasticizers, humectants, defoamers, UV absorbers, light fastness enhancers, polymeric dispersants, dye mordants, optical brighteners, leveling agents, and the like. Other additives, including, for example, alum, as well as other sizing agents, may also be used in the manufacture of paper products.

Examples

[0038] In order to provide a better understanding of the foregoing discussion, the following non-limiting examples are offered. Although the examples can be directed to specific embodiments, they are not to be viewed as limiting the invention in any specific respect. All parts, proportions, and percentages are by weight unless otherwise indicated.

[0039] Example 1 - first a di alkenyl succinic amide acid was prepared according to the following synthesis procedure. An alkenyl succinic anhydride having a branched Cl 8 alkenyl group was reacted with urea according to Scheme 1 shown below. One mole of urea was reacted with two moles of the alkenyl succinic anhydride in the presence of sulfolane and refluxed at a temperature of about 150°C to produce the first di alkenyl succinic amide acid product that contained about 50% actives. As used herein the term “actives” refers to the amount of the di alkenyl succinic amide acid present in the reaction product.

[0040] Example 2 - a second di alkenyl succinic amide acid was prepared according to the following synthesis procedure. An alkenyl succinic anhydride having a branched Cl 8 alkenyl group was reacted with thiourea according to Scheme 2 shown below. One mole of thiourea was reacted with two moles of the alkenyl succinic anhydride in the presence of sulfolane and refluxed at a temperature of about 150°C to produce the second di alkenyl succinic amide acid product that contained about 50% actives.

[0041] Example 3 - a third di alkenyl succinic amide acid was prepared according to the following synthesis procedure. An alkenyl succinic anhydride having a branched C22 alkenyl group was reacted with urea according to Scheme 3 shown below. One mole of urea was reacted with two moles of the alkenyl succinic anhydride in the presence of sulfolane and refluxed at a temperature of about 150°C to produce the third di alkenyl succinic amide acid product that contained about 50% actives.

[0042] Example 4 - a fourth di alkenyl succinic amide acid was prepared according to the following synthesis procedure. An alkenyl succinic anhydride having a branched C22 alkenyl group was reacted with thiourea according to Scheme 4 shown below. One mole of thiourea was reacted with two moles of the alkenyl succinic anhydride in the presence of sulfolane and refluxed at a temperature of about 150°C to produce the fourth di alkenyl succinic amide acid product that contained about 50% actives.

[0043] Fourier transform infrared spectrometry (FTIR) was used to confirm the presence of the characteristic amide acid functional units at 1713 cm ¹ absorption in the four di alkenyl succinic amide acids. In addition, the absence of the amine group absorption band and the characteristic anhydride absorption bands indicates the reaction of the alkenyl succinic anhydride and the urea or thiomrea.

[0044] The di alkenyl succinic amide acids made according to Schemes 1 and 2 were used to size paper handsheets. Aqueous sizing compositions that contained about 83.3 wt% of the di alkenyl succinic amide acid and about 16.7 wt% of an emulsifier, based on a combined weight of the di alkenyl succinic amide acid and the emulsifier were prepared. The aqueous sizing composition contained about 5 wt% of the di alkenyl succinic amide acid and about 1 wt% of the emulsifier, based on a combined weight of the di alkenyl succinic amide acid, the emulsifier, and water. The emulsifier was NALSIZE ^® 7548, sold by Nalco Chemical Company. A comparative sized paper handsheet was also prepared with a standard aqueous alkenyl succinic anhydride sizing composition NALSIZE ^® 7542, which is also sold by Nalco Chemical Company. The comparative aqueous sizing composition contained about 5 wt% of the alkenyl succinic anhydride and about 1 wt% of the same emulsifier as used in Examples 1 and 2, based on a combined weight of the di alkenyl succinic amide acid, the emulsifier, and water.

[0045] The sized handsheets in Examples 1 and 2 and Comparative Example 1 were prepared according to the following procedure. Hand sheets were prepared by mixing a simulated gypsum furnish at 800 RPM in a Dynamic Drainage Jar. The furnish aliquot was designed to produce an 80 gsm basis weight sheet. The hand sheets prepared with the simulated gypsum furnish were first dosed with about 10 lb/T of papermaker’s alum at the start of mixing. This was followed by the addition of about 2, about 2.5 or about 3 lb/T of the sizing agent at about 15 seconds, followed by the addition of about 1 lb/T NALCO ^® 61067 flocculant (high molecular weight cationic acrylamide copolymer) at about 30 seconds. Mixing was stopped after about 45 seconds and the furnish was transferred to a Noble & Wood handsheet mold deckle box. The hand sheet was formed by drainage through a 100 mesh forming wire that produced an 8” X 8” hand sheet. The hand sheet was couched from the sheet mold wire by placing three blotters and a metal plate on the wet hand sheet and roll pressing with six passes of a 25 lb metal roller. The forming wire and one blotter were removed and the hand sheet was placed between two new blotters and the press felt and pressed at about 50 psi using the roll press. All of the blotters were removed and the hand sheet was dried (wire side facing the dryer surface) on a rotary drum drier set at a temperature of about 220°F for about 90 seconds in a single pass. After drying, the handsheets were placed in the controlled temperature and humidity room at a temperature of about 23°C and about 50% relative humidity overnight before subsequent size testing. The sized handsheets were subjected to a dye penetration test according to TAPPI T-530. The results are shown in Table 1 below.

[0046] While the di alkenyl succinic amide acid based sizing compositions did not perform better than the standard alkenyl succinic anhydride sizing composition, some sizing performance was observed. As noted above, the observation of some sizing performance was by itself a surprising and unexpected observation.

[0047] The di alkenyl succinic amide acids made according to Schemes 3 and 4 were used to size paper handsheets (Examples 3 and 4) according to the same procedure that was used to make the handsheets in Examples 1 and 2. The comparative sized paper handsheet (CE2) was prepared according to the same procedure as in CE1. As such, the aqueous sizing compositions contained about 5 wt% of the di alkenyl succinic amide acid (Examples 3 and 4) or about 5 wt% of the alkenyl succinic anhydride (CE2) and about 1 wt% of the emulsifier, based on a combined weight of the di alkenyl succinic amide acid or the alkenyl succinic anhydride, the emulsifier, and water.

[0048] The sized handsheets in Examples 3 and 4 and Comparative Example 2 were prepared according to the same procedure as the sized handsheets in Examples 1 and 2 and Comparative Example 1. The handsheets were subjected to a dye penetration test according to TAPPI T- 530. The results are shown in Table 2 below. [0049] As can be seen from Table 2, the di alkenyl succinic amide acids produced in Examples 3 and 4 showed better performance than the standard alkenyl succinic anhydride based sizing composition. Similar to the di alkenyl succinic amide acids made in Examples 1 and 2, seeing any sizing performance at all was surprising and unexpected and outperforming the comparative examples was also surprising and unexpected.

[0050] Embodiments of the present disclosure further relate to any one or more of the following paragraphs:

[0051] 1. A di alkenyl succinic amide acid having a chemical formula of (I): wherein: R ¹ and R ² are independently a linear or branched C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ are independently O or S, and X is O,

S, or N.

[0052] 2. A sizing composition, comprising: a sizing agent; an emulsifier; and a diluent, wherein the sizing agent comprises a di alkenyl succinic amide acid having a chemical formula wherein: R ¹ and R ² are independently a linear or branched C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ are independently O or S, and X is O,

S, or N.

[0053] 3. A process for making a di alkenyl succinic amide acid, comprising: mixing a polyamine, a solvent, and an alkenyl succinic anhydride comprising a linear or branched C8 to C24 alkenyl group to produce a mixture; and reacting the polyamine and the alkenyl succinic anhydride in the mixture to produce the di alkenyl succinic amide acid.

[0054] 4. The process according to paragraph 3, wherein the di alkenyl succinic amide acid has a chemical formula of (I): wherein: R ¹ and R ² are independently a linear or branched

C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ are independently O or S, and X is O, S, or N. [0055] 5. A process for making a sizing composition, comprising: mixing a sizing agent, an emulsifier, and a diluent to produce an emulsion, wherein the sizing agent comprises a di alkenyl succinic amide acid having a chemical formula of (I): wherein: R ¹ and R ² are independently a linear or branched

C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ are independently O or S, and X is O, S, or N. [0056] 6. A process for making paper, comprising incorporating into the paper or applying to a surface of a paper a sizing composition comprising a di alkenyl succinic amide acid having a chemical formula of (I): wherein: R ¹ and R ² are independently a linear or branched

C8 to C24 alkenyl group, Z ¹ , Z ² , Z ³ , and Z ⁴ are independently O or S, and X is O, S, or N. [0057] 7. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is O and X is O.

[0058] 8. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is O and X is S.

[0059] 9. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is O and X is N.

[0060] 10. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is S and X is O.

[0061] 11. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is S and X is S. [0062] 12. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein each Zl, Z2, Z3, and Z4 is S and X is N.

[0063] 13. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein two of Zl, Z2, Z3, and Z4 are O, two of Zl, Z2, Z3, and Z4 are S, and X is O.

[0064] 14. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein two of Zl, Z2, Z3, and Z4 are O, two of Zl, Z2, Z3, and Z4 are S, and X is S.

[0065] 15. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein two of Zl, Z2, Z3, and Z4 are O, two of Zl, Z2, Z3, and Z4 are S, and X is N.

[0066] 16. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are O, one of Zl, Z2, Z3, and Z4 is S, and X is O.

[0067] 17. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are O, one of Zl, Z2, Z3, and Z4 is S, and X is S.

[0068] 18. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are O, one of Zl, Z2, Z3, and Z4 is S, and X is N.

[0069] 19. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are S, one of Zl, Z2, Z3, and Z4 is O, and X is O.

[0070] 20. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are S, one of Zl, Z2, Z3, and Z4 is O, and X is S.

[0071] 21. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 6, wherein three of Zl, Z2, Z3, and Z4 are S, one of Zl, Z2, Z3, and Z4 is O, and X is N.

[0072] 22. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 21, wherein R1 and R2 are independently a linear C8 to Cl 8 alkenyl group. [0073] 23. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 21, wherein R1 and R2 are independently a branched C16 to C24 alkenyl group.

[0074] 24. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1, 2, or 4 to 21, wherein R1 and R2 are each a branched Cl 8 alkenyl group, a branched C20 alkenyl group, a branched C22 alkenyl group, or a branched C24 alkenyl group.

[0075] 25. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1 , 2, or 4 to 6, wherein R1 and R2 are each a branched C22 alkenyl group, each Zl, Z2, Z3, and Z4 is O, and X is S.

[0076] 26. The di alkenyl succinic amide acid, the sizing composition, or the process according to any of paragraphs 1 , 2, or 4 to 6, wherein R1 and R2 are each a branched C22 alkenyl group, each Zl, Z2, Z3, and Z4 is O, and X is O.

[0077] 27. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 26, wherein the sizing composition comprises about 1 wt% to about 30 wt% of the sizing agent, based on a combined weight of the sizing agent, the emulsifier, and the diluent.

[0078] 28. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 27, wherein a ratio of the emulsifier to the sizing agent, on a volume basis, is about 0.6:1 to about 1.25:1.

[0079] 29. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 28, wherein the emulsifier comprises one or more cationic water soluble vinyl addition or condensation polymers having a weight average molecular weight of about 10,000 to about 1,000,000, where about 10 wt% to about 100 wt% of a mer content of the polymer is a cationic vinyl monomer or a cationically modified monomer.

[0080] 30. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 29, wherein the emulsifier comprises an alkyl primary amine, an alkyl secondary amine, an alkyl tertiary amine, an aryl primary amine, an aryl secondary amine, an aryl tertiary amine, or a corresponding quaternary salt thereof.

[0081] 31. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 30, wherein the diluent comprises water, sulfolane, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, N-ethyl pyrrolidone, glacial acetic acid, or a mixture thereof.

[0082] 32. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 31, wherein the sizing composition has a median droplet size of about 2.5 pm or less. [0083] 33. The sizing composition or process according to any of paragraphs 2, 5, or 7 to 32, wherein the sizing composition has a median droplet size of about 1.5 pm or less.

[0084] 34. The process according to any of paragraphs 3, 4, or 7 to 26, wherein the solvent comprises a polar aprotic solvent, a polar protic solvent, or a mixture thereof.

[0085] 35. The process according to any of paragraphs 3, 4, 7 to 26, or 34, wherein the solvent comprises sulfolane, dimethyl sulfoxide, dimethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, 1 -ethyl pyrrolidone, water, or a mixture thereof.

[0086] 36. The process according to any of paragraphs 3, 4, 7 to 26, 34, or 35, wherein the polyamine comprises urea; thiourea; 1 -(diaminomethylene)urea, guanidine; 1,3-diaminourea; benzene- 1,3-diamine; 2,4,6-triamino pyrimidine; or a mixture thereof.

[0087] 37. The process according to any of paragraphs 3, 4, 7 to 26, or 34 to 36 wherein the alkenyl succinic anhydride has a chemical formula of (II): (II), and wherein R is a linear or branched C8 to a C24 alkenyl group.

[0088] 38. The process according to any of paragraphs 3, 4, 7 to 26, or 34 to 37, wherein a molar ratio of the alkenyl succinic anhydride to the polyamine is about 0.8: 1 to about 2: 1. [0089] 39. The process according to any of paragraphs 3, 4, 7 to 26, or 34 to 38, wherein the polyamine and the alkenyl succinic anhydride are reacted at a temperature of about 60°C to about 180°C.

[0090] 40. The process according to any of paragraphs 3, 4, 7 to 26, or 34 to 39, wherein the polyamine and the alkenyl succinic anhydride are reacted at a temperature of about 80°C to about 90°C.

[0091] 41. The process according to any of paragraphs 3, 4, 7 to 26, or 34 to 40, further comprising mixing a catalyst with the polyamine, the alkenyl succinic anhydride, and the solvent to produce the mixture.

[0092] 42. The process according to paragraph 41, wherein the mixture comprises about 0.01 mol% to about 0.1 mol% of the catalyst, based on a combined amount of the polyamine, the solvent, the alkenyl succinic anhydride, and the acid catalyst.

[0093] 43. The process according to paragraphs 41 or 42, wherein the catalyst comprises acetic anhydride, acetic acid, a mixture of acetic anhydride and sodium acetate, trifluoro acetic acid, methane sulfonic acid, chloroacetic acid, sodium phenylphosphinate, phosphorous acid, or a mixture thereof.

[0094] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges including the combination of any two values, e.g., the combination of any lower value with any upper value, the combination of any two lower values, and/or the combination of any two upper values are contemplated unless otherwise indicated. Certain lower limits, upper limits and ranges appear in one or more claims below. All numerical values are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by a person having ordinary skill in the art.

[0095] Various terms have been defined above. To the extent a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term as reflected in at least one printed publication or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.

[0096] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.