Polyetheramine-based compositions

Abstract

The present disclosure is generally directed to a method for preserving a polymer emulsion in the wet state. The method may include dosing the polymer emulsion with a polyetheramine of Formula I. For instance, the polyetheramine may be present in the polymer emulsion at a concentration of from about 1000 ppm to about 10000 ppm.

Description

Attorney Docket No.: ARXP-329-PCT (LP3750PC00)POLYETHERAMINE-BASED COMPOSITIONSRELATED APPLICATIONS

[0001] The present application is based on and claims priority to U.S. Provisional Patent application Serial No. 63 / 749817, filed on January 27, 2025, which is incorporated herein by reference.BACKGROUND

[0002] Isothiazolinones and pyrithiones have been widely used as broad-spectrum biocides for the preservation of water-based products such as latex, paints and adhesives against spoilage from bacteria, yeasts and fungi. Typical examples of isothiazolinone biocides include 5-chloro-2-methyl-4-isothiazolinone (CMIT), 2-methyl-4-isothiazolinone (MIT), l,2-benzisothiazolin-3-one (BIT), n-butyl-l,2-benzisothiazolin-3-one (BBIT), 2-octyl-4-isothiazolinone (OIT), and 4,5-dichloro -2-octyl-4-isothiazolinone (DCOIT). Typical examples of pyrithiones include zinc pyrithione (ZPT), sodium pyrithione (NaPT) and copper pyrithione (CuPT). However, both isothiazolinones and pyrithiones are under regulatory scrutiny.

[0003] As such, evolving regulations require reduced levels of allowable active biocides in products. Certain countries, such as Canada, forbid the use of certain biocides in certain applications (e.g., ZPT is forbidden in textiles). As a result, the industry is now facing not only the ineffective biocidal performance at lower active level, but also the fewer choices of effective biocides.

[0004] For these reasons, there exists a strong need to develop new formulations of ingredients that enable preservation in the current regulatory landscape. Of particular interest are ingredients that enhance the activity of primary actives or can provide preservation with minimal or no use of certain unfavorable preservatives. Additional interest is driven by those ingredients that can allow for preservation meeting “label free” requirements in certain regions. Further, if the ingredient is multifunctional, there may be simultaneous savings and SKU-reduction on functions supplied by numerous other additives (e.g., dispersants, defoamers, rheology modifiers, surfactants, pH adjusters).SUMMARY

[0005] The present disclosure is generally directed to a method for preserving a polymer emulsion in the wet state. The method may include dosing the polymer emulsionAttorney Docket No.: ARXP-329-PCT (LP3750PC00)with a poly etheramine. For instance, the poly etheramine may be present in the polymer emulsion at a concentration of from about 1000 ppm to about 10000 ppm.

[0006] Additionally, example aspects of the present disclosure are directed to a method for preparing a water-based industrial material. The method may include dosing the waterbased industrial material with a polymer emulsion disclosed herein.

[0007] Other features and aspects of the present disclosure are discussed in greater detail below.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] A full and enabling disclosure of the present disclosure is set forth more particularly in the remainder of the specification, including reference to the accompanying figure, in which:

[0009] Figure 1 depicts chemical structures of polyetheramines (PEA).

[0010] Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.DETAILED DESCRIPTION

[0011] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only and is not intended as limiting the broader aspects of the present disclosure.

[0012] The present disclosure is generally directed to a method for preserving a polymer emulsion in the wet state. The method may include dosing the polymer emulsion with a poly etheramine. For instance, the poly etheramine may be present in the polymer emulsion at a concentration of from about 1000 ppm to about 10000 ppm. Paints prepared using the polyetheramine-containing polymer emulsion may require less total isothiazolinone for effective preservation due to the carryover polyetheramine, or polyetheramine-based booster composition used in the emulsion.

[0013] Beneficially, dosing polyetheramines disclosed herein into a polymer emulsion may effectively lower the amount of isothiazolinone / pyrithione-based biocides present in paints and coatings while maintaining and / or improving the wet-state preservation to meet the increasing strict regulations. In addition, the polyetheramines disclosed herein and their formulated products are multifunctional. As such, poly etheramines disclosed herein may provide additional benefits such as enhanced alkaline pH and viscosity stabilization. Also,Attorney Docket No.: ARXP-329-PCT (LP3750PC00)advantageously, polyetheramines disclosed herein may be free of volatile organic compounds (VOCs) and thus has no impact on paint VOC.

[0014] In one example embodiment, the polymer emulsion may include at least one poly etheramine. The poly etheramine may have the following formula (I):R-(R1)(R2)(R3)(R4) (I),wherein R is C*(CH2—)4 (tetrafunctional), CH CH2C*(CH2— )3 (trifunctional), CH3C*H= (difunctional), — H2C(C&HIO)*CH2— (difunctional), CH3OCH2C*H2— (monofunctional), or a combination thereof; and Ri, R2, R3, R4 are independently — H, — NH2,— (OCH2CHR’)nNH2, or a combination thereof; and wherein R’ is H or Cl-9 alkyl chain and n = 1 to 50, preferably 1 to 20. In Formula (I), R may be the junction point (*: junction carbon atom) of multiple polyetheramine chains and not limited to the exemplary structures disclosed herein.

[0015] In one example embodiment, the polyetheramine may be a primary aliphatic polyamine. For instance, the poly etheramine may be poly oxypropylenediamine or polyoxypropylenetriamine. In one embodiment, the polyetheramine of Formula I is Jeffamine® T403 polyetheramine (Huntsman Corp., Houston, Texas).

[0016] In another example embodiment, the polyetheramine may be a linear polyetheramine. The linear polyetheramine may have a molecular weight greater than about 118 Daltons (Da). For instance, the linear poly etheramine may have a molecular weight greater than about 150 Da, such as greater than about 200 Da, such as greater than about 230 Da, such as greater than about 300 Da, such as greater than about 400 Da, such as greater than about 500 Da, such as greater than about 600 Da, such as greater than about 800, such as greater than about 900 Da, such as greater than 1500 Da, such as greater than about 2000 Da, or such as greater than about 2500 Da.

[0017] The linear polyetherarmine may have the following formula:

[0018] In one example embodiment, the linear poly etheramine of Formula 1 may include, but are not limited to, JEFFAMINE® ED900, JEFFAMINE® D2000, JEFFAMINE® ED600, JEFF AMINE® D400, and JEFFAMINE® D230, JEFFAMINE® M2005, or JEFFAMINE® M600.

[0019] In another example embodiment, the polyetheramine may be a cycloaliphatic polyetheramine. For instance, the polyetheramine of Formula 1 may be JEFFAMINE®Attorney Docket No.: ARXP-329-PCT (LP3750PC00)RFD270. RFD270 is a reaction product of 1,4-cyclohexanedimethanol, propylene oxide, and ammonia.

[0020] In one example embodiment, the polyetheramine may be present in the polymer emulsion in an amount from about 0.001% by weight to about 5% by weight, such as from about 0.01% by weight to about 3% by weight, such as from about 0.1% by weight to about 1% by weight, or any range therebetween, based on the weight of the polymer emulsion. For instance, in one example embodiment, the polyetheramine may be present in the polymer emulsion in an amount from about 0.001% by weight to about 5% by weight. For instance, in another example embodiment, the polyetheramine may be present in the polymer emulsion in an amount from about 0.01% by weight to about 3% by weight. For instance, in another example embodiment, the polyetheramine may be present in the polymer emulsion in an amount from about 0.1% by weight to about 1% by weight.

[0021] In one example embodiment, the polyetheramine may be present in the polymer emulsion at a concentration of 1000 parts per million (ppm) to 10000 ppm, such as from about 1500 ppm to about 9000 ppm, such as from about 3000 ppm to about 7500 ppm, such as from about 4000 ppm to about 6000 ppm, or any range therebetween. In one example embodiment, for instance, the polyetheramine may be present in the polymer emulsion at a concentration of 1000 ppm to 10000 ppm. In another example embodiment, for instance, the polyetheramine may be present in the polymer emulsion at a concentration of 1500 ppm to 9000 ppm. In another example embodiment, for instance, the polyetheramine may be present in the polymer emulsion at a concentration of 3000 ppm to 7500 ppm. In another example embodiment, for instance, the polyetheramine may be present in the polymer emulsion at a concentration of 4000 ppm to 6000 ppm.

[0022] If desired, in one example embodiment, the polymer emulsion disclosed herein may include at least one isothiazolinone compound. For instance, the isothiazolinone compound may include an isothiazolin-3-one compound. The isothiazolin-3-one compound may include, but is not limited to, l,2-benzisothiazolin-3-one (“BIT”), N-butyl-1,2-benzisothiazolin-3-one (“BBIT”), N-methyl-l,2-benzisothiazolin-3-one (“nMBIT”), 2-methyl-2H-isothiazol-3-one (“MIT”), 5-chloro-2-methyl-2H-isothiazol-3-one (“CMIT”), 2-octyl-3(2H)-isothiazolone (“OIT”), 4,5-dichloro-2n-octyl-3(2H)-isothiazolone (“DCOIT”), 2,2-dithiobis(N-methylbenzamide) (“DTMB”), or a combination thereof. In one example embodiment, the polymer emulsion disclosed herein may include l,2-benzisothiazolin-3-one (“BIT”). In another example embodiment, the polymer emulsion disclosed herein mayAttorney Docket No.: ARXP-329-PCT (LP3750PC00)include 2-methyl-2H-isothiazol-3-one (“MIT”). In another example embodiment, the polymer emulsion disclosed herein may include CMIT / MIT.

[0023] In one example embodiment, the isothiazolinone may be present in the polymer emulsion at a concentration of 5 ppm to 750 ppm, such as from about 10 ppm to about 500 ppm, such as from about 50 ppm to about 400 ppm, such as from about 100 ppm to about 300 ppm, or any range therebetween. In one example embodiment, for instance, the isothiazolinone may be present in the polymer emulsion at a concentration of 5 ppm to 750 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the polymer emulsion at a concentration of 10 ppm to 500 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the polymer emulsion at a concentration of 50 ppm to 400 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the polymer emulsion at a concentration of 100 ppm to 300 ppm.

[0024] If desired, in one example embodiment, the polymer emulsion may include a combination of a polyetheramine and at least one isothiazolinone compound. For instance, the weight ratio of the polyetheramine and the isothiazolinone compound present in the polymer emulsion may be from about 2000: 1 to about 1:10. For instance, in one example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound present in the polymer emulsion may be from about 2000: 1 to about 1:10, such as from about 75: 1 to about 1:5, such as from about 60: 1 to about 1 :3, such as from about 50: 1 to about 2:3, or any range therebetween. In one example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound may be from about 75: 1 to about 1:5. In another example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound may be from about 60:1 to about 1:3. In another example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound may be from about 50: 1 to about 2:3. In the example ratios recited above, the isothiazolinone compound may include one or more of the isothiazolin-3-one compounds described above.

[0025] Optionally, in one example embodiment, the polymer emulsion may include a polar solvent. For instance, the polar solvent may be selected from a group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or a combination thereof.

[0026] Optionally, the polymer emulsion may further include at least one additive or booster including, but are not limited to, an inorganic metal compound, a silicate, aAttorney Docket No.: ARXP-329-PCT (LP3750PC00)pyrithione salt, an organic amine, or a combination thereof. In one embodiment, the polyetheramine to additive has a weight ratio of from about 1 :500 to about 50:1, such as from about 1 :400 to about 40: 1, such as from about 1 :250 to about 25: 1, such as from about 1 : 100 to about 20: 1, such as from about 1 :50 to about 15:1, such as from about 1 :20 to about 10: 1, or any range therebetween.

[0027] If desired, the polymer emulsion disclosed herein may include an inorganic metal compound. For instance, the inorganic metal compound may include, but is not limited to, an inorganic zinc compound, an inorganic magnesium compound, an inorganic copper compound, an inorganic lithium compound, or a combination thereof. In one embodiment, the inorganic metal compound is an inorganic zinc compound, such as one or more of zinc oxide (at times referred to herein as “ZnO”), zinc acetate, zinc sulfate, zinc chloride, and zinc carboxylate. Preferably, the zinc oxide may have a zinc oxide particle size of less than 50 microns. The inorganic zinc compound may be present in the polymer emulsion at a concentration from about 0.2% by weight to about 5% by weight, 0.5% by weight to 3.5% by weight, 1% by weight to 2.5% by weight, 1.5% by weight to 2% by weight, or any range therebetween, based on the weight of the composition.

[0028] In one example embodiment, the inorganic metal compound may be an inorganic magnesium compound, such as magnesium oxide. For instance, the magnesium compound may be present in the polymer emulsion at a concentration from about 5% by weight to about 20% by weight, such as from about 7.5% by weight to about 15% by weight, such as from about 10% by weight to about 13.5% by weight, or any range therebetween.

[0029] In one example embodiment, the inorganic metal compound may be an inorganic cuprous or cupric compound, such as copper salts. For instance, copper salt may include copper sulfate, copper nitrate, copper carbonate, basic copper carbonate, copper oxide, copper oxychloride, copper hydroxide, copper acetylacetonate, copper pyrrolidone carboxylic acid (PCA), copper PCA methylsilanol, copper acetyl tyrosinate methylsilanol, copper acetylmethionate, copper aminoacetylamidoimidazolyl propionate, copper picolinate, copper tripeptide- 1, bis (tripeptide- 1) copper acetate, copper ascorbyl phosphate succinoyl tripeptide-34, copper pyrithione, sodium calcium copper phosphate, copper pyridoxal-5-phosphate, sodium copper chlorophyllin, copper chlorophyll, disodium EDTA copper, or a combination thereof. In one embodiment, the copper salt may include one or more of copper sulfate, copper nitrate, copper carbonate, copper oxide, and copper acetylacetonate.Attorney Docket No.: ARXP-329-PCT (LP3750PC00)

[0030] In one example embodiment, the inorganic metal compound may be an inorganic lithium compound, such as lithium salts. For instance, lithium salts may include lithium carbonate, lithium acetate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, lithium metasilicate, or a combination thereof.

[0031] If desired, the polymer emulsion disclosed herein may include a silicate.Silicates may include, but are not limited to, silicas such as modified silicas and fumed silicas. In one example embodiment, the silicate may be one or both of potassium methylsiliconate and sodium metasilicate (e.g., sodium metasilicate pentahydrate).Commercial examples include Silres 168 (Wacker), Tyson WR50 (Tyson, Singapore), and Xiameter OFS0777 (Dow Chemical). The silicate may be present in the polymer emulsion in an about from about 0.5% by weight to about 15% by weight, such as from about 1% by weight to about 10% by weight, such as from about 2.5% by weight to about 7.5% by weight, or any range therebetween, based on the weight of the composition.

[0032] If desired, the polymer emulsion disclosed herein may include one or more pyrithione salts. For instance, such pyrithione salts may include zinc pyrithione, sodium pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, calcium pyrithione, magnesium pyrithione, an organic amine pyrithione, barium pyrithione, strontium pyrithione, copper pyrithione, cadmium pyrithione, or a combination thereof. The pyrithione salt may be present in the polymer emulsion in an amount from about 0.005% by weight to about 1% by weight, such as from about 0.015% by weight to about 0.5% by weight, such as from about 0.025% by weight to about 0.25% by weight, or any range therebetween, based on the weight of the composition. For instance, the pyrithione salt can be present in the polymer emulsion from about 5 ppm to about 500 ppm, such as from about 50 ppm to about 300 ppm, such as from about 100 ppm to about 250 ppm, or any range therebetween.

[0033] If desired, the polymer emulsion disclosed herein may include an organic amine, such as a pH adjusting agent. The organic amine may include, but are not limited to, 2-amino-2-methyl-l -propanol (“AMP95”), ethanolamine, l-amino-2-propanol, 3 -amino- 1-propanol, 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2(propylamino)ethanol, 2(isopropylamino)ethanol, diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, , 2-amino-2-ethyl-l,3-propanediol (also called AEPD), 2(2-aminoethoxy)ethanol (also called diglycol amine), N-methyldiethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylaminoethanol, N,NAttorney Docket No.: ARXP-329-PCT (LP3750PC00)dimethylamino-2-propanol, etc. The organic amines may be used individually or in any combination. In one embodiment, the organic amine may comprise 2-amino-2-methyl-l-propanol (“AMP95”). For instance, AMP95 may be present in the composition at a concentration from about 5% by weight to about 75% by weight, such as from about 15% by weight to about 65% by weight, such as from about 25% by weight to about 60% by weight, or any range therebetween.

[0034] If desired, the polymer emulsion disclosed herein may include an alkali compound. For instance, the alkali compound may include, but are not limited to, potassium / sodium methyl siliconate, potassium / sodium hydroxide, potassium / sodium carbonate / bicarbonate, or a combination thereof.

[0035] Optionally, the polymer emulsion disclosed herein may utilize one or more surfactants. The surfactants function as emulsifiers and help to keep the water-insoluble components of the formulation in the form of a stable dispersion (emulsion) of small particles suspended in an aqueous phase.

[0036] Suitable types of nonionic surfactants include, but are not limited to, polyoxyalkylene glycol alkyl ethers (e.g., polyoxyethylene glycol alkyl ethers, polyoxypropylene alkyl ethers, polyoxyethylene / propylene alkyl ethers), glucoside alkyl ethers, polyoxyalkylene glycol alkylphenol ethers (e.g., polyoxyethylene glycol alkylphenol ethers, polyoxypropylene glycol alkylphenol ethers, polyoxyethylene / propylene glycol alkylphenol ethers), glycerol alkyl esters, polyoxyalkylene glycol sorbitan alkyl esters (e.g., polyoxyethylene glycol sorbitan alkyl esters), sorbitan alkyl esters, cocamide MEA, cocamide DEA, block copolymers of polyethylene glycol and polypropylene glycol (poloxamers), polyalkoxylated tallow amines, alkoxylated fatty acids and the like and combinations thereof.

[0037] Particular nonionic surfactants include alkoxylated aliphatic mono-alcohols and alkoxylated aromatic mono-alcohols. Such surfactants are typically prepared by reacting one or more alkylene oxides (e.g., ethylene oxide, propylene oxide, mixtures of ethylene oxide and propylene oxide) with one or more mono-alcohols (e.g., aliphatic alcohols, which may be for example linear or branched, primary or secondary, or aromatic alcohols, such as phenols, including alkyl- and aralkyl-substituted phenols). The number of moles of alkylene oxide reacted per mole of the mono-alcohol may be varied as may be desired, but typically is from about 2 to about 50 on average. If more than one type of alkylene oxide is used, the alkylene oxides may be reacted as a mixture (to provide a polyoxyalkyleneAttorney Docket No.: ARXP-329-PCT (LP3750PC00)segment having a random copolymer structure) or sequentially (to provide a polyoxyalkylene segment having a block copolymer structure).

[0038] Another type of nonionic surfactant for use in the present disclosure is an alkoxylated aliphatic mono-alcohol which is an ethoxylated Cio-Cis aliphatic alcohol (in particular, a linear primary C12-C16 aliphatic alcohol or mixture of such alcohols) which has been reacted with about 6 to about 15 moles of ethylene oxide per mole of aliphatic alcohol to provide an alkoxylated alcohol containing an average of about 6 to about 15 oxy ethylene repeating units per molecule). For example, the alkoxylated aliphatic mono-alcohol may be an ethoxylated C12-C16 linear aliphatic alcohol containing an average of about 8 to about 12 ethylene oxide units per molecule. In particular, ethoxylated tridecanol containing an average of about 10 ethylene oxide units is suitable for use in the present disclosure.

[0039] Another type of nonionic surfactant for use in the present disclosure is an alkoxylated C2-C8 aliphatic alcohol containing both ethylene oxide and propylene oxide units. The C2-C8 aliphatic alcohol may be n-butanol, for example. The ethylene oxide and propylene units may be arranged in a block manner (e.g., the surfactant may contain a polyoxyethylene block and a polyoxypropylene block). Also suitable for use as nonionic surfactants are alkoxylated phenols, in particular ethoxylated phenols wherein the phenol may be substituted with one or more alkyl groups (in particular, long chain alkyl groups such as nonyl or dodecyl groups or aralkyl groups, such as in tristyrylphenol).

[0040] Suitable anionic surfactants include, but are not limited to, surfactants containing anionic functional groups at their head, such as sulfate groups, sulfonate groups, phosphate groups, and carboxylate groups. The cationic counterion to the anionic functional group may be, for example, an alkali metal (e.g., Na, K) or an amine (ammonium) cation such as a quaternary ammonium. Useful types of anionic surfactants in the present disclosure include, but are not limited to, alkyl sulfates, alkyl ether sulfates, sulfated alkanolamides, glyceride sulfates, alkyl aryl sulfonates (including straight-chain alkylbenzenesulfonates, branched alkylbenzenesulfonates, alkylnaphthalene-sulfonates), alpha olefin sulfonates, lignosulfonates, sulfo-carboxylic compounds (e.g., sodium lauryl sulfoacetate, sulfosuccinates (including dialkylsulfosuccinates), sulfosuccinamates, organo phosphored surfactants, sacrosides, hydroxyalkane-sulfonates, alkanesulfonates, alkylphenoxy polyoxyethylene propyl sulfonates, salts of polyoxyethylenealkyl sulfophenyl ethers, sodium N-methyl-N-oleyltaurates, monoamide di sodium N-alkyl sulfosuccinates, petroleum sulfonates, sulfated castor oil, sulfated tallow oil, salts of sulfuric esters of aliphatic alkylesters, salts of alkylsulfuric esters, salts of alkylsulfuricAttorney Docket No.: ARXP-329-PCT (LP3750PC00)esters, sulfuric esters of polyoxyethylenealkylethers, salts of sulfuric esters of aliphatic monoglycerides, sodium salt of the monosulfated monoglyceride of hydrogenated coconut oil fatty acids, salts of sulfuric esters of polyoxyethylene alkylphenylethers, salts of alkylphosphoric esters, salts of phosphoric esters of polyoxyethylenealkylethers, salts of phosphoric esters of polyoxyethylenealkylphenylethers, partially saponified compounds of styrene-maleic anhydride copolymers, partially saponified compounds of olefin-maleic anhydride copolymers, naphthalenesulfonate-formalin condensates, higher alkyl sulfoacetates, and higher fatty acid esters of 1,2-dihydroxy propane sulfonate and combinations thereof. Particular among these anionic surfactants are sulfonate surfactants, in particular salts of alkyl aryl sulfonates, especially salts of Cs-Cis alkyl benzene sulfonates such as salts of dodecylbenzene sulfonate, and combinations thereof.

[0041] A total amount of surfactant is used that is effective, in combination with the any thickeners and / or suspending agent that may be present in the composition, to provide a physically stable dispersion. The amount of surfactant needed to achieve a physically stable dispersion will depend on a number of factors, including, for instance, the types and amounts of the poly etheramine and thickeners / suspending agents present in the polymer emulsion and the types of surfactants utilized. Typically, however, an amount of surfactant is used which is sufficient to provide a weight ratio of polyetheramine to surfactant within the range of from about 5 : 1 to about 50:1 or from about 6: 1 to about 20: 1.

[0042] Further, certain surfactants and combinations of surfactants also have well-known activities disrupting membranes. This activity is general to several cationic surfactants, but is also true of certain non-ionic and ionic surfactants.

[0043] If desired, the polymer emulsions of the present disclosure may include one or more substances capable of functioning as thickener or suspending agents to render the compositions physically stable. In particular, the types and amounts of thickeners and / or suspending agents may be selected such that at twenty-five degrees Celsius (25 °C) the resulting polymer emulsion has a viscosity of at least 300 cps. In other example embodiments, the viscosity of the polymer emulsion at 25 °C is at least 400 cps or at least 500 cps. Generally, it will be desirable for the viscosity of the polymer emulsion to not be increased to the point where it becomes difficult to transfer or handle the polymer emulsion by pumping. Viscosity is measured using a Brookfield viscometer (spindle #5, 100 rpm).

[0044] Suitable thickeners / suspending agents include, without limitation, clays (including natural clays and organo-modified clays), silicates (e.g., silicas such as modifiedAttorney Docket No.: ARXP-329-PCT (LP3750PC00)silicas and fumed silicas), polysaccharides (e.g., gums such as xanthan gum, cellulosic polymers), polyacrylates, and the like and combinations thereof.

[0045] One or more other components, in addition to those mentioned above, may additionally be present in the polymer emulsions of the present disclosure. In certain example embodiments, however, the polymer emulsion consists essentially of or consists of only the aforementioned components, except that one or more defoamers may optionally be present in such example embodiments.

[0046] Additional optional components include, but are not limited to, dispersants, defoamers (antifoams, e.g., silicone-based defoamers, mineral oil-based defoamers, hydrophobic silica-based defoamers), sequestering / chelating agents, fillers, coloring agents, antifreezing agents, corrosion inhibitors (anti-corrosion additives), ultraviolet light stabilizers, antioxidants, solvents, co-solvents, scale inhibitors, and the like.

[0047] Further components may include ingredients known in the art of preparing stable isothiazolinone concentrates, most typically magnesium nitrate, sodium nitrate, potassium iodate, copper nitrate, or other salts known in the art as particularly useful as stabilizing agents. Concentrates of isothiazolinones and polyetheramines may utilize one or more of these established stabilization systems to overcome reactivity between the polyetheramine and isothiazolinone.

[0048] The polymer emulsions disclosed herein may also be pH adjusted to affect the chemical stability or solubility of the isothiazolinone or polyetheramine in the formulation. Methods well known in the art may be used for controlling the chemical stability of isothiazolinone concentrates.

[0049] The polymer emulsions disclosed herein may also contain other ingredients known to stabilize isothiazolinones.

[0050] Polymer emulsions in accordance with the present disclosure may be prepared by adaptation of any of the techniques known in the art for creating dispersions of waterinsoluble substances in water using surfactants (emulsifiers), thickeners, suspending agents, and combinations of these ingredients. For example, a suitably sized mixing vessel may be charged with water, followed by the surfactants desired to be included in the polymer emulsion. While agitating the surfactant / water mixture, the polyetheramine and a portion of the thickeners / suspending agents are added. Mixing at high speed and / or high shear may be continued until a homogeneous emulsion having the desired particle size (typically 5 to 75 microns) is obtained. The mixture may be heated to a temperature somewhat above room temperature during this step. The remaining thickeners / suspendingAttorney Docket No.: ARXP-329-PCT (LP3750PC00)agents may then be added, and the mixture agitated until homogeneous once again. The mixture may be cooled to room temperature prior to the final addition of thickeners / suspending agents. The polymer emulsion may then be transferred by pumping or other means to one or more suitable storage containers such as tanks, drums or totes.

[0051] The polymer emulsion of the present disclosure may include various formulations. The preservative may be effective in many aqueous or water-based industrial formulations, including but not limited to solutions including soluble liquids, sols, gels, partially hydrated and / or dispersed biopolymers; suspensions including suspension concentrates, mineral slurries, suspensions of various biological materials including microorganisms in viable and non-viable form; microcapsules of many forms including conventional capsule suspensions; emulsions including oil in water emulsions, water in oil emulsions and microemulsions, and mixtures of the above types of formulations. In one example aspect, the polymer emulsion of example aspects of the present disclosure may be in an aqueous industrial formulation. In another example aspect, the polymer emulsion of example aspects of the present disclosure may be in an aqueous or oil-based formulation which may be a solution, a suspension, a microcapsule, an emulsion, or a mixture thereof, as described herein. In one embodiment, the polymer emulsion may be oil soluble.

[0052] Advantageously, the polyetheramine disclosed herein may enhance performance characteristics of a polymer emulsion with or without additional biocidal agents being present. These performance enhancing characteristics may include, but are not limited to, material property enhancements to pH, defoaming efficacy, viscosity stability, scrub resistance, or other desired features of the end-use material.

[0053] The polymer emulsion disclosed herein may be employed for various applications. For instance, the polymer emulsion disclosed herein may be dosed or added to various water-based industrial materials (or end-use formulations) include, but are not limited to, metalworking fluids, polymer latex, paints, polymer emulsion, coatings, adhesives, admixtures, spackling and joint compounds, sealants, caulks, mineral and pigment slurries, printing inks, household products, personal care products, leather and hide treatment products, etc. In one embodiment, the metalworking fluid may be a coolant.

[0054] In one example embodiment, a water-based industrial material may be prepared by dosing the water-based industrial material with a polymer emulsion disclosed herein. In one example embodiment, the polymer emulsion disclosed herein may be useful in preserving a polymer emulsion in which it is dosed into. For instance, the polymer emulsion may be dosed into a water-based industrial material, such as a latex emulsion.Attorney Docket No.: ARXP-329-PCT (LP3750PC00)Alternatively, the polymer emulsion may be dosed into a water-based industrial material, such as into a paint. Beneficially, the water-based industrial material may not include added biocides.

[0055] In one example embodiment, the pH of the water-based industrial material may be about 7.5 or more, such as about 8.0 or more, such as about 8.5 or more, such as about 9,0 or more, such as about 10 or more. In one example embodiment, for instance the pH of the water-based industrial material may be about 7.5 or more. In another example embodiment, for instance the pH of the water-based industrial material may be about 8.0 or more. In another example embodiment, for instance the pH of the water-based industrial material may be about 9.0 or more. In another example embodiment, for instance the pH of the water-based industrial material may be about 10.0 or more.

[0056] In one example embodiment, the poly etheramine of Formula I may be present in the water-based industrial material in an amount from about 0.001% w / w to about 3% w / w, such as from about 0.01% w / w to about 3% w / w, such as from about 0.1% w / w to about 1% w / w, or any range therebetween. In one example embodiment, for instance, the poly etheramine of Formula I may be present in the water-based industrial material in an amount from about 0.01% w / w to about 3% w / w. In another example embodiment, for instance, the poly etheramine of Formula I may be present in the water-based industrial material in an amount from about 0.1% w / w to about 1% w / w.

[0057] In one example embodiment, the polyetheramine disclosed herein may be present in the water-based industrial material at a concentration of from about 500 ppm to about 5000 ppm, such as from about 1000 ppm to about 3000 ppm, such as from about 1500 ppm to about 2500 ppm, or any range therebetween. In one example embodiment, for instance, the polyetheramine disclosed herein may be present in the water-based industrial material at a concentration of from about 500 ppm to about 5000 ppm. In another example embodiment, for instance, the polyetheramine disclosed herein may be present in the water-based industrial material at a concentration of from about 1000 ppm to about 3000 ppm. In another example embodiment, for instance, the polyetheramine disclosed herein may be present in the water-based industrial material at a concentration of from about 1500 ppm to about 2500 ppm.

[0058] In one example embodiment, the at least one isothiazolinone may be present in the water-based industrial material at a total concentration of from about 5 parts per million (ppm) to about 750 ppm, such as from about 10 ppm to 500 ppm, such as from about 50 ppm to about 400 ppm, such as from about 100 ppm to about 300 ppm, or any rangeAttorney Docket No.: ARXP-329-PCT (LP3750PC00)therebetween. In one example embodiment, for instance, the isothiazolinone may be present in the water-based industrial material at a concentration of 5 ppm to 750 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the water-based industrial material at a concentration of 10 ppm to 500 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the water-based industrial material at a concentration of 50 ppm to 400 ppm. In another example embodiment, for instance, the isothiazolinone may be present in the water-based industrial material at a concentration of 100 ppm to 300 ppm.

[0059] If desired, in one example embodiment, the water-based industrial material may include a combination of a polyetheramine and at least one isothiazolinone compound. For instance, the weight ratio of the polyetheramine and the isothiazolinone compound present in the water-based industrial material may be from about 100: 1 to about 1:10. For instance, in one example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound present in the water-based industrial material may be from about 100:1 to about 1:10, such as from about 75:1 to about 1:5, such as from about 60:1 to about 1:3, such as from about 50:1 to about 2:3, or any range therebetween. In one example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound may be from about 75: 1 to about 1:5. In another example embodiment, the weight ratio of the polyetheramine and the isothiazolinone compound may be from about 60:1 to about 1 :3. In another example embodiment, the weight ratio of the poly etheramine and the isothiazolinone compound may be from about 50:1 to about 2:3. In the example ratios recited above, the isothiazolinone compound may include one or more of the isothiazolin-3 -one compounds described above.

[0060] The polymer emulsions disclosed herein may be added to a water-based industrial material as a concentrate. In one example implementation, the concentration of the concentrate in the water-based industrial material may be from about 0.05 wt.% to about 5 wt.%, such as from about 0.1 wt.% to about 4 wt.%, such as from about 0.5% wt.% to about 3 wt.%, such as from about 1 wt.% to about 2.5 wt.%, or any range therebetween.

[0061] The method of preserving a polymer emulsion may include dosing the polymer emulsion with an effective amount of a polytheramine disclosed herein so that the polymer emulsion imparts resistance to microorganism growth, including bacterial, fungal and algae growth in the polymer emulsion. As the polymer emulsion are typically prepared containing relatively high concentrations of active ingredients (i.e., biocides), they generally find use as concentrates which are combined, in relatively small quantities, withAttorney Docket No.: ARXP-329-PCT (LP3750PC00)one or more other ingredients in order to formulate a final product suitable for use for its intended purpose.

[0062] The polyetheramine disclosed herein may be effective against bacteria and / or fungi. Exemplary microorganisms can include one or more species from one or both of the following groups.

[0063] Bacteria: Alcaligenes such as Alcaligenes faecalis, Acinetobacter such as Acinetobacter calcoaceticus, Bacillus such as Bacillus subliHs. Citrobacter such as Citrobacter freundii. Corynebacterium such as Corynebacterium ammoniagenes, Enterobacter such as Enterobacter aerogenes or Enterobacter cloacae, Enterococcus such as Enterococcus hirae, Escherichia such as Escherichia coll, Proteus such as Proteus hauseri. Pseudomonas such as Pseudomonas aeruginosa, Pseudomonas fluorescens, or Pseudomonas stutzeri, Salmonella such as Salmonella enterica, Staphylococcus such as Staphylococcus aureus,'

[0064] Fungi: Acremonium such as Acremonium strictum, Altemaria such as Alternaria tenuis or Alternaria alternata, Aspergillus such as Aspergillus niger or Aspergillus brasiliensis, Candida such as Candida albicans, Chaetomium such as Chaetomium globosum, Fusarium such as Fusarium solani, Geotrichum such as Geotrichum candidum, Lentinus such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Penicillium funiculosum, or Penicillium pinophilum, Rhodotorula such as Rhodotorula rubra or Rhodotorula mucilaginosa, Stachybotrys such as Stachybotrys chartarum, Trichoderma such as Trichoderma virens.

[0065] The working compositions of the disclosure include a polyetheramine and at least one isothiazolinone disclosed herein.

[0066] The polymer emulsions of the present disclosure may be added to a product or locus in or on which microorganisms are to be controlled. The polyetheramine and the at least one isothiazolinone may be in the form of a concentrate including essential ingredients, i.e., the polyetheramine and the at least one isothiazolinone (“preservative concentrate”), which can then be added to said product. The concentrate may also be diluted with or suspended, dissolved or emulsified in a suitable solvent or carrier before being added to the product. The addition of the polymer emulsion to the product to be protected can be used to produce a biocidal product.

[0067] The polymer emulsion of the present disclosure may be provided in a concentrated form or in a ready to use form which has been diluted. In view of handling ability, the polymer emulsion of the present disclosure may be water based and may beAttorney Docket No.: ARXP-329-PCT (LP3750PC00)prepared as a stock solution having a high concentration so that the user dilutes the fluid as necessary with water to use the diluted fluid as desired.

[0068] The preceding description is exemplary in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure.

[0069] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related.

[0070] As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optional ingredients, components or limitations described herein or otherwise useful in polymer emulsions.

[0071] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percentages, and so forth, as used in the specification or claims are to be understood as being modified by the term “about”. Accordingly, unless otherwise indicated, implicitly or explicitly, the numerical parameters set forth are approximations that may depend on the desired properties sought and / or limits of detection under standard test conditions / methods. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[0072] As used herein, “optional” or “optionally” means that the subsequently described material, event or circumstance may or may not be present or occur, and that the description includes instances where the material, event or circumstance is present or occurs and instances in which it does not. As used herein, “w / w%” and “wt%” mean by weight as relative to another component or a percentage of the total weight in the composition.

[0073] The term “about” is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters setAttorney Docket No.: ARXP-329-PCT (LP3750PC00)forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0074] The term “substantially free of’ when used to describe the amount of substance in a material is not to be limited to entirely or completely free of and may correspond to a lack of any appreciable or detectable amount of the recited substance in the material. Thus, e.g., a material is “substantially free of’ a substance when the amount of the substance in the material is less than the precision of an industry-accepted instrument or test for measuring the amount of the substance in the material. In certain example embodiments, a material may be “substantially free of’ a substance when the amount of the substance in the material is less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.5%, or less than 0.1% by weight of the material.

[0075] The phrase “effective amount” means an amount of a compound that promotes, improves, stimulates, or encourages a response to the particular condition or disorder or the particular symptom of the condition or disorder.

[0076] The term “biocidal agent” as used herein refers to any chemical compound that is intended to inhibit or kill organisms on a surface and / or that prevents or kills the growth of organisms in an aqueous solution, such as a coolant.

[0077] As used herein, the terms “first”, “second”, and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.

[0078] Here and throughout the specification and claims, range limitations are combined and interchanged, such ranges are identified and include all the sub-ranges contained therein unless context or language indicates otherwise. For example, all ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other.

[0079] This written description uses examples to disclose the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do notAttorney Docket No.: ARXP-329-PCT (LP3750PC00)differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

[0080] Furthermore, certain aspects of the present disclosure may be better understood according to the following examples, which are intended to be non-limiting and exemplary in nature. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described.EXAMPLESExample 1:Wet-State Preservation o f BIT / PEA in Latex Emulsion and Paint

[0081] The susceptibility of latex emulsion #1 (self-crosslinking acrylic emulsion, 44% Solid) prepared with various poly etheramines (PEA), alone or in combination with 1,2-benzisothiazolin-3-one (BIT) were evaluated. Paints (58% PVC, 30% Solid Vol, 46 g / L VOC, Table 1) prepared from these PEA or PEA / IST containing polymer emulsions were also evaluated in parallel. Product susceptibility was assayed using a modified ASTM D2574 Standard Test Method of Resistance of Emulsion Paints in the Container to Attack by Microorganisms. BIT (Proxel BD20) and polyetheramines were added into the latex emulsion to achieve 360 ppm BIT and 0.8% polyetheramine. The dosed latex emulsions were speed mixed at 2000 rpm for 2 minutes for homogenous emulsions. Aliquots of the dosed latex emulsions were used for formulating the latex paints to achieve the dose level of 72 ppm BIT and 0.16% poly etheramine. Both the dosed latex emulsions and paints were equilibrated for at least overnight prior to any tests.Table 1. Composition of Latex Paint #1Attorney Docket No.: ARXP-329-PCT (LP3750PC00)

[0082] The wet-state preservation test is designed to determine the susceptibility of products to microbial growth in a liquid sample when inoculated with spoilage microbes. The following bacterial strains were utilized for the inoculations:■ Acinetobacter calcoaceticus ATCC 14987■ Enterobacter cloacae ATCC 7256■ Escherichia coli ATCC 11229■ Pseudomonas aeruginosa ATCC 10145

[0083] Bacterial cultures were obtained from a culture collection stored at -80 °C. Test bacteria were adapted to grow at pH levels of 5, 7, and 9. Test organisms were chosen from the pH that most closely matched that of the sample. Lawns of the test bacteria were harvested from tryptic soy agar (TSA) using sterile PBS. Where growth was observed in the unpreserved control after the first inoculation, a standard inoculation regimen was followed. For each of the sample ladder(s) the inoculum volume was equivalent to 10% of the paint size. The efficacy of the preservatives in controlling contamination was monitored at 7 days after each inoculation by streaking the samples on plates of Campylobacter Blood Agar (CVA) for bacterial challenge samples. CVA plates were evaluated after incubation at 33 °C for 48 hours. The degree of growth on CVA streak plates was interpreted in Table 2.Table 2. Rating Scale of Microbial Growth

[0084] The susceptibility of the latex emulsion with and without BIT / polyetheramine-dosed latex emulsions is shown in Table 3. Both BIT alone and BIT / poly etheramine combinations passed the wet-state preservation test at 360 ppm and 360 ppm / 0.80% levels while most polyetheramine alone failed at 0.80% level except for PEA D230 and RFD270 with > 6xl0'2meq / g amine level.Table 3. Summary Table of Wet-State Preservation Efficacies of BIT / PEA in Latex Emulsion #1Attorney Docket No.: ARXP-329-PCT (LP3750PC00)

[0085] The wet-state preservation efficacies of BIT / polyetheramine-dosed latex paints are given in Table 4. Only BIT / polyetheramine combinations with > l><10'2meq / g amine level passed the test at 72 ppm / 0.16% level while BIT alone, poly etheramine alone and the rest of BIT / polyetheramine combinations failed at the respective 72 ppm, 0.16% and 72 ppm / 0.16% level.Table 4. Summary Table of Wet-State Preservation Efficacies of BIT / PEA in Latex Paint #1

[0086] Overall, the above wet-state preservation results demonstrate that the paint prepared from the polymer emulsions containing both BIT and polyetheramine combinations are less susceptible to growth.Example 2pH o f BIT / PEA in Latex Emulsion and PaintAttorney Docket No.: ARXP-329-PCT (LP3750PC00)

[0087] In addition to wet-state preservation efficacies, the pHs of BIT / PEA-dosed latex emulsions and paints in Example 1 were also measured using a pH meter. Polyetheramine leads to higher alkaline either by itself or in combination with BIT (Table 5). This is particularly beneficial to latex emulsion and paint as alkaline pH is needed for storage stability provided by anionic additive package.Table 5. pHs of BIT / PEA-dosed Latex Emulsions and Paints

[0088] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims

Attorney Docket No.: ARXP-329-PCT (LP3750PC00)What Is Claimed:

1. A method of preserving a polymer emulsion in the wet state, the method comprises:dosing the polymer emulsion with a poly etheramine of Formula I,R-(R1)(R2)(R3)(R4) (I),wherein R is a junction point, preferably C*(CH2—)4 (tetrafunctional), CH3CH2C*(CH2-)3(trifunctional), CH3C*H= (difunctional), — H2C(C6HIO)*CH2— (difunctional), CH3OCH2C*H2— (monofunctional), or a combination thereof; and Ri, R2, R3, R4 are independently — H, — NH2, — (OCH2CHR’)nNH2, or a combination thereof, wherein R’ is H or Cl -9 alkyl chain and n = 1 to 50;2. The method of claim 1, wherein the poly etheramine is present in the polymer emulsion at a concentration of from about 1000 ppm to about 10000 ppm.

3. The method of claim 1, wherein the poly etheramine is present in the polymer emulsion at a concentration of from about 1500 ppm to about 9000 ppm.

4. The method of claim 1, wherein the polymer emulsion further comprises at least one isothiazolinone.

5. The method of any one of claims 1-3, wherein the at least one isothiazolinone is present in the polymer emulsion at a concentration of from about 5 ppm to about 750 ppm.

6. The method of any one of claims 1-4, wherein the at least one isothiazolinone is present in the preservative composition at a concentration of from about 10 ppm to about 500 ppm.

7. The method of any one of claims 1-5, wherein the at least one isothiazolinone is present in the preservative composition at a concentration of from about 50 ppm to about 400 ppm.

8. The method of any one of claims 1-6, wherein the at least one isothiazolinone is present in the preservative composition at a concentration of from about 100 ppm to about 300 ppm.Attorney Docket No.: ARXP-329-PCT (LP3750PC00)9. The method of any one of claims 1-7, wherein the weight ratio of the polyetheramine to the at least one isothiazolinone is from about 2000: 1 to about 1:10.

10. The method of any one of claims 1-8, wherein the weight ratio of the polyetheramine to the at least one isothiazolinone is from about 75: 1 to about 1:5.

11. The method of any one of claims 1 -9, wherein the weight ratio of the polyetheramine to the at least one isothiazolinone is from about 60: 1 to about 1 :3.

12. The method of any one of claims 1-10, wherein the at least one isothiazolinone comprises l,2-benzisothiazolin-3-one (“BIT”), N-butyl-l,2-benzisothiazolin-3-one (“BBIT”), N-methyl-l,2-benzisothiazolin-3-one (“nMBIT”), 2-methyl-2H-isothiazol-3-one (“MIT”), 5-chloro-2-methyl-2H-isothiazol-3-one (“CMIT”), 2-octyl-3(2H)-isothiazolone (“OIT”), 4,5-dichloro-2n-octyl-3(2H)-isothiazolone (“DCOIT”), 2,2-dithiobis(N-methylbenzamide) (“DTMB”), or a combination thereof.

13. The method of any one of claims 1-11, wherein the polymer emulsion further comprises a polar solvent.

14. The method of claim 13, wherein the polar solvent is selected from a group consisting of ethylene glycol, propylene glycol, glycerin, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, or a combination thereof.

15. The method of any one of claims 1-13, wherein the polymer emulsion further comprises a zinc compound.

16. The method of claim 14, wherein the zinc compound comprises zinc acetate, zinc oxide, zinc sulfate, zinc chloride, zinc carboxylate, or a combination thereof.

17. The method of any one of claims 1-15, wherein the polymer emulsion further comprises an alkali compound.Attorney Docket No.: ARXP-329-PCT (LP3750PC00)18. The method of claim 16, wherein the alkali compound comprises potassium / sodium methyl siliconate, potassium / sodium hydroxide, potassium / sodium carbonate / bicarbonate, or a combination thereof.

19. The method of any one of claims 1-17, wherein the polyetheramine is present in the polymer emulsion at a concentration of from about 0.01% to about 3% by weight of the polymer emulsion.

20. The method of claim 18, wherein the poly etheramine is present in the polymer emulsion at a concentration of from about 0.1% to about 1% by weight of the polymer emulsion.

21. The method of any one of claims 1-19, wherein the polymer emulsion is a latex emulsion.

22. The method of any one of claims 1-19, wherein the polymer emulsion is a paint.

23. A method of preparing a water-based industrial material, the method comprising:dosing a water-based industrial material with a polymer emulsion comprising at least one isothiazolinone and 0.1% - 1.0% w / w of a polyetheramine of Formula I,R-(R1)(R2)(R3)(R4) (I),wherein R is a junction point preferably C*(CH2— )4 (tetrafunctional), CH3CH2C*(CH2-)3(trifunctional), CH3C*H= (difunctional), — H2C(C6HIO)*CH2— (difunctional), CH3OCH2C*H2— (monofunctional), or a combination thereof; and Ri, R2, R3, R4 are independently — H, — NH2, — (OCH2CHR’)nNH2, or a combination thereof, wherein R’ is H or Cl -9 alkyl chain and n = 1 to 50.

24. The method of claim 23, wherein the polyetheramine is present in the water-based industrial material at a concentration of from about 500 ppm to about 5000 ppm.

25. The method of any one of claims 23-24, wherein a pH of the water-based industrial material is about 7.5 or more.Attorney Docket No.: ARXP-329-PCT (LP3750PC00)26. The method of any one of claims 23-25, wherein the water-based industrial material is essentially free of additional added biocides.

27. The method of any one of claims 23-26, wherein the polyetheramine to the at least one isothiazolinone are present in the water-based industrial material at a weight ratio of from about 100:1 to about 1:10.

28. The method of any one of claims 23-27, wherein the weight ratio of the polyetheramine to the at least one isothiazolinone is from about 75: 1 to about 1:5.

29. The method of any one of claims 23-28, wherein the weight ratio of the polyetheramine to the at least one isothiazolinone is from about 60: 1 to about 1 :3.

30. The method of any one of claims 23-29, wherein the at least one isothiazolinone is present in the water-based industrial material at a concentration of from about 5 ppm to about 750 ppm.

31. The method of any one of claims 23-30, wherein the at least one isothiazolinone is present in the water-based industrial material at a concentration of from about 10 ppm to about 500 ppm.

32. The method of any one of claims 23-31, wherein the at least one isothiazolinone is present in the water-based industrial material at a concentration of from about 50 ppm to about 400 ppm.

33. The method of any one of claims 23-32, wherein the at least one isothiazolinone is present in the water-based industrial material at a concentration of from about 100 ppm to about 300 ppm.

34. The method of any one of claims 23-33, wherein the at least one isothiazolinone comprisesl,2-benzisothiazolin-3-one (“BIT”), N-butyl-l,2-benzisothiazolin-3-one (“BBIT”), N-methyl-l,2-benzisothiazolin-3-one (“nMBIT”), 2-methyl-2H-isothiazol-3-one (“MIT”), 5-chloro-2-methyl-2H-isothiazol-3-one (“CMIT”), 2-octyl-3(2H)-isothiazoloneAttorney Docket No.: ARXP-329-PCT (LP3750PC00)(“OIT”) 4,5-dichloro-2n-octyl-3(2H)-isothiazolone (“DCOIT”), 2,2-dithiobis(N-methylbenzamide) (“DTMB”), or a combination thereof.

35. The method of any one of claims 23-34, wherein BIT is present in the water-based industrial material at a concentration of less than about 360 ppm.

36. The method of any one of claims 23-34 wherein CMIT / MIT is present in the waterbased industrial material at a concentration of less than about 15 ppm.

37. The method of any one of claims 23-34, wherein MIT is present in the water-based industrial material at a concentration of less than about 15 ppm.

Images