Polyetheramine-based preservative compositions

Abstract

The present disclosure is generally directed to a preservative composition including a cycloaliphatic polyetheramine and 1,2-benzisothiazolin-3-one ("BIT"). The preservative composition may include a cycloaliphatic polyetheramine and BIT present at a weight ratio of 100:1 to 1:10.

Description

POLYETHERAMINE-BASED PRESERVATIVE COMPOSITIONSRELATED APPLICATIONS

[0001] The present application is based on and claims priority to U.S. Provisional Patent application Serial No. 63 / 654,237, filed on May 31, 2024, which is incorporated herein by reference.BACKGROUND

[0002] Preservation of water-based materials continues to be complicated by regulations that ban or restrict the use of certain active components. For the actives that continue to be widely used, most carry labeling implications at typical use levels. Methods of improving the activity of in-can preservatives at “label-free’' levels is highly desired by the industry, but the activity of these ingredients on their own is typically insufficient.

[0003] Due to the complications surrounding preservative use, many coatings producers are now choosing to produce biocide-free paints. These biocide-free paints are produced by bringing the pH to ~11, which is believed to inhibit the growth of microorganisms. However, this approach appears to only create new microbiological and consumer safety challenges, as the high pH can be irritating, the alkalinity limits the use of many commonly used paint additives, and spoilage remains rampant.

[0004] Beyond limitations set by regulators, even in regions where active substance use levels are broader and do not carry labeling implications, producers often struggle to achieve good preservation at reasonable cost-in-use.

[0005] 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 those that can provide preservation without the use of certain unfavorable preservatives. Additional interest is driven by those ingredients that can allow7for preservation meeting “label free” requirements in certain regions. Further, if the ingredient being 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

[0006] The present disclosure is generally directed to a preservative composition including a cycloaliphatic poly etheramine and l,2-benzisothiazolin-3-one (“BIT”). The cycloaliphatic polyetheramine may have the following formula, Formula I:. The preservative composition may include the cycloaliphatic polyetheramine and BIT present at a weight ratio of 100: 1 to 1 : 10.

[0007] Additionally, example aspects of the present disclosure are directed to an aqueous industrial material including a cycloaliphatic polyetheramine of Formula I. The aqueous industrial material may include Formula I present in an amount from about 0.05% w / w to about 5% w / w. Also, the aqueous industrial material may include cycloaliphatic polyetheramine of Formula I in combination with BIT present at a weight ratio of from about 50:1 to about 2:3.

[0008] Also, example aspects of the present disclosure are directed to a method for enhancing preservative performance of an oil soluble industrial material, including adding an effective amount of the preservative composition disclosed herein to an aqueous industrial material.

[0009] Other features and aspects of the present disclosure are discussed in greater detail below.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] 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:

[0011] Figure 1 depicts the activity of Jeffamine RFD270 and BIT against the test organism Pseudomonas aeruginosa.

[0012] 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

[0013] 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.

[0014] The present disclosure is generally directed to a preservative composition including a cycloaliphatic poly etheramine having the structure of Formula I:(I); and and l,2-benzisothiazolin-3-one (“BIT"’). The cycloaliphatic polyetheramine and 1,2- benzisothiazolin-3-one (‘"BIT”) may be present in the preservative composition at a weight ratio of from about 100: 1 to about 1:10.

[0015] Advantageously, the cycloaliphatic polyetheramine may be useful in a preservative composition at a low active content compared to non-cycloaliphatic poly etheramines. Unexpectedly, formulations disclosed herein including cycloaliphatic polyetheramine alone or in combination with BIT significantly outperform formulations containing non-cycloaliphatic poly etheramines. As such, the composition disclosed herein may be useful as a preservative booster at lower levels of the cycloaliphatic polyetheramine and the isothiazolinone, with performance characteristics that exceed or match industry standards containing formaldehyde-adducts and fungicides.

[0016] The polyetheramine may be a cycloaliphatic polyetheramine. In one example embodiment, the polyetheramine of Formula 1 may be JEFF AMINE® RFD270. RFD270 is a reaction product of 1,4-cyclohexyanedimethanol, propylene oxide, and ammonia.

[0017] In one example embodiment, the cycloaliphatic polyetheramine may be present in the preservative composition in an amount from about 1% by weight to about 99% by weight, such as from about 10% by weight to about 80% by weight, such as from about 15% by weight to about 75% by weight, such as from about 20% by weight to about 65% by weight, such as from about 30% by weight to about 60% by weight, such as from about 40% by weight to about 55% by weight, or any range therebetween, based on the weight of the composition.

[0018] The preservative composition disclosed herein may include an 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, 1,2- 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. In one example embodiment, the preservative composition disclosed herein may include l,2-benzisothiazolin-3-one (“BIT”).

[0019] The preservative composition may include a combination of a cycloaliphatic polyetheramine and an isothiazolinone compound. For instance, the weight ratio of the cycloaliphatic polyetheramine and the isothiazolinone compound present in the preservative composition may be from about 150: 1 to about 1 :50.

[0020] In one example embodiment, the weight ratio of the cycloaliphatic polyetheramine and the isothiazolinone compound present in the preservative composition 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 cycloaliphatic poly etheramine and the isothiazolinone compound is from about 50:1 to about 1:50. In another example embodiment, the weight ratio of the cycloaliphatic polyetheramine and the isothiazolinone compound is 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.

[0021] Optionally, the preservative composition of the present disclosure may utilize one or more surfactants. The surfactants function as emulsifiers and help to keep the waterinsoluble components of the formulation in the form of a stable dispersion (emulsion) of small particles suspended in an aqueous phase.

[0022] Suitable ty pes of nonionic surfactants include, but are not limited to, poly oxy alkylene glycol alkyl ethers (e.g., polyoxyethylene glycol alkyl ethers, polyoxypropylene alkyl ethers, polyoxy ethylene / propylene alkyd ethers), glucoside alkyl ethers, polyoxyalkylene glycol alkylphenol ethers (e.g., polyoxyethylene glycol alkydphenol ethers, polyoxypropylene glycol alkylphenol ethers, polyoxyethylene / propylene glycol alkylphenol ethers), glycerol alky l 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.

[0023] Particular nonionic surfactants include alkoxylated aliphatic mono-alcohols and alkoxylated aromatic mono-alcohols. Such surfactants are typically prepared by reacting one or more alkydene 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 ofalkylene oxide reacted per mole of the mono-alcohol may be varied as may be desired, but ty pically is from about 2 to about 50 on average. If more than one type of alkylene oxide is used, the alkydene oxides may be reacted as a mixture (to provide a poly oxyalkylene segment having a random copolymer structure) or sequentially (to provide a polyoxyalkylene segment having a block copolymer structure).

[0024] Another ty pe of nonionic surfactant for use in the present disclosure is an alkoxy lated 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 alkoxy lated alcohol containing an average of about 6 to about 15 oxy ethylene repeating units per molecule). For example, the alkoxylated aliphatic monoalcohol 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.

[0025] 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).

[0026] 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, alkyd ether sulfates, sulfated alkanolamides, glyceride sulfates, alkyl aryl sulfonates (including straight-chain alkylbenzenesulfonates, branched alky lbenzenesulfonates, 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 polyoxyethylene alkylsulfophenyl ethers, sodium N-methyl-N-oleyltaurates, monoamide disodium N- alkylsulfosuccinates. petroleum sulfonates, sulfated castor oil, sulfated tallow oil, salts of sulfuric esters of aliphatic alkylesters, salts of alkylsulfunc esters, salts of alkylsulfuric 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 alkyd benzene sulfonates such as salts of dodecylbenzene sulfonate, and combinations thereof.

[0027] 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 cycloaliphatic poly etheramine and thickeners / suspending agents present in the preservative composition and the types of surfactants utilized. Typically, however, an amount of surfactant is used which is sufficient to provide a weight ratio of cycloaliphatic polyetheramine to surfactant within the range of from about 5: 1 to about 50: 1 or from about 6: 1 to about 20: 1.

[0028] 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.

[0029] If desired, the preservative compositions 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 preservative composition has a viscosity7of at least 300 cps. In other example embodiments, the viscosity of the preservative composition at 25 °C is at least 400 cps or at least 500 cps. Generally, it will be desirable for the viscosity of the preservativecomposition to not be increased to the point where it becomes difficult to transfer or handle the preservative composition by pumping. Viscosity is measured using a Brookfield viscometer (spindle #5, 100 rpm).

[0030] Suitable thickeners / suspending agents include, without limitation, clays (including natural clays and organo-modified clays), silicates (e.g., silicas such as modified silicas and fumed silicas), polysaccharides (e.g., gums such as xanthan gum, cellulosic polymers), polyacrylates, and the like and combinations thereof.

[0031] One or more other components, in addition to those mentioned above, may additionally be present in the preservative compositions of the present disclosure. In certain example embodiments, however, the preservative composition consists essentially of or consists of only the aforementioned components, except that one or more defoamers may optionally be present in such example embodiments.

[0032] 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.

[0033] Further components may include ingredients known in the art of preparing stable isothiazolinone concentrates, most ty pically magnesium nitrate, sodium nitrate, potassium iodate, copper nitrate, or other salts known in the art as particularly useful as stabilizing agents.

[0034] The preservative compositions may also be pH adjusted to affect the chemical stability7or solubility7of the isothiazolinone or cycloaliphatic poly etheramine in the formulation. Methods well known in the art may be used for controlling the chemical stability of isothiazolinone concentrates.

[0035] Preservative compositions disclosed herein may also be free of preservative active ingredients (e.g. isothiazolinones, pyrithiones, formaldehyde, and formaldehy dedonors) and include one or more of the aforementioned optional components. These optional components can be added to provide the cycloaliphatic polyetheramine formulations with multifunctional properties beyond preservation or preservative performance enhancement, or enhance the ability of the cycloaliphatic polyetheramine to be used in different applications.

[0036] Preservative compositions in accordance with the present disclosure may be prepared by adaptation of any of the techniques known in the art for creating dispersions ofwater-insoluble 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 preservative composition. While agitating the surfactant / water mixture, the poly etheramine 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 / suspending 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 preservative composition may then be transferred bypumping or other means to one or more suitable storage containers such as tanks, drums or totes.

[0037] The preservative composition 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 preservative composition of example aspects of the present disclosure may be in an aqueous industrial formulation. In another example aspect, the preservative composition of example aspects of the present disclosure may be in an aqueous or oilbased formulation which may be a solution, a suspension, a microcapsule, an emulsion, or a mixture thereof, as described herein. In one embodiment, the preservative composition may be oil soluble.

[0038] Advantageously, the cycloaliphatic polyetheramine disclosed in aqueous industrial materials to enhance performance characteristics of the material, with or without additional biocide. These performance enhancing characteristics may include, but are not limited to, material property enhancements to pH, defoaming efficacy, viscosity stability7, scrub resistance, or other desired features of the end-use material. In one example embodiment, the aqueous industrial material may include a cycloaliphatic poly etheramine disclosed herein. For instance, the cycloaliphatic polyetheramine of Formula I may bepresent in the aqueous industrial material in an amount from about 0.05% w / w to about 5% w / w, such as from about 0.1% w / w to about 3% w / w, such as from about 0.5% w / w to about 2.5% w / w. such as from about 0.75% w / w to about 2% w / w, or any range therebetween.

[0039] In one example embodiment, the aqueous industrial material may include a cycloaliphatic polyetheramine and an isothiazolinone compound. For instance, the cycloaliphatic poly etheramine of Formula I and BIT may be present in the aqueous industrial material at a weight ratio of from about 50: 1 to about 2:3, such as from about 30: 1 to about 1:3, or any range therebetween. In one example embodiment, the compound of Formula I and BIT are present in the aqueous industrial material at a weight ratio of about 1: 1.

[0040] In one example embodiment, the aqueous industrial material disclosed herein may include BIT present at a concentration of from about 10 parts per million (ppm) to about 100 ppm, such as from about 20 ppm to about 80 ppm, such as from about 30 ppm to about 60 ppm, or any range therebetween.

[0041] The preservative compositions disclosed herein may be added to an aqueous industrial formulation as a concentrate. In one example implementation, the concentration of Formula I in the industrial formulation 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.

[0042] The preservative compositions of the present disclosure are useful for imparting resistance to microorganism growth, including bacterial, fungal and algae grow th, in a wide variety of w orking compositions, in particular water-based products. As the preservative composition 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, with one or more other ingredients in order to formulate a final product suitable for use for its intended purpose.

[0043] The biocidal compositions of the invention are particularly effective against bacteria and / or fungi. Exemplary microorganisms can include one or more species from one or both of the following groups.

[0044] Bacteria: Alcaligenes such as Alcaligenes faecalis, Acinetobacter such as Acinetobacter calcoaceticus , Bacillus such as Bacillus subtilis, Citrobacter such as Citrobacter freundii, Corynebacterium such as Corynebaclerium ammoniagenes . Enterobacter such as Enterobacter aerogenes or Enterobacter cloacae. Enterococcus suchas Enterococcus hirae. Escherichia such as Escherichia coh, 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.'

[0045] 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.

[0046] The working compositions of the disclosure include a cycloaliphatic polyetheramine and an isothiazolinone compound disclosed herein. In one example embodiment, the preservative composition includes a cycloaliphatic polyetheramine and BIT.

[0047] The preservative compositions of the present disclosure may be added to a product or locus in or on which microorganisms are to be controlled. The cycloaliphatic polyetheramine and the isothiazolinone compound may be in the form of a concentrate including essential ingredients, i.e., the cycloaliphatic polyetheramine and isothiazolinone compound (“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 preservative composition to the product to be protected can be used to produce a biocidal product.

[0048] The preservative composition disclosed herein may be employed for various applications. For instance, the applications (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.

[0049] The preservative composition of the present disclosure may be utilized in an architectural paint. For instance, the architectural paint may include a solvent, a latex binder, and the preservative composition described herein. Optionally , the architectural paint can further include a dispersant and / or surfactant to improve distribution of the latexbinder throughout the architectural paint. In this manner, the dispersant and / or surfactant can be used to produce a more homogenous mixture that can provide a more even coating of the architectural paint. Optionally, the architectural paint can include a thickening agent to adjust the viscosity of the architectural paint to improve adhesion of the wet paint to an applicator (e.g., a brush or roller). Optionally, the architectural paint can include one or more pigments (e.g., TiO2) for providing a color to the architectural paint. Optionally, the architectural paint can include a cosolvent (e.g., ethylene glycol) that can improve solubility of components of the architectural paint.

[0050] The latex binder may include various polymers suitable for architectural paints such as an acry lates (e.g., polymethylmethacrylate), that can be formed as a homopolymer or co-polymer. For example, a co-polymer can include incorporation of another monomer (e.g.. butadiene styrene). In some implementations, the acrylate can be modified to include one or more nitrile groups. Thus, latex binders can include various acrylates, acry late butadiene styrene copolymers, and acrylonitrile butadiene styrene copolymers.Additionally, these latex binders are provided for example purposes, and additional latex binders may be used alone or in combination with implementations of the disclosure.

[0051] As an example for illustration, an implementation of the present disclosure may include an architectural paint including a latex binder with an acrylate. The acrylate can include a polymer or copolymer that includes one or more acrylate monomers. Example aspects of the acrylate polymer or copolymer can include a mass fraction of an acrylate monomer. For instance, the acrylate can include a copolymer that includes an acrylate monomer (e.g., methyl methacrylate) and a second monomer (e.g., butadiene styrene). The mass fraction of the acry late monomer to the total weight of the copolymer can define the mass fraction. In some acry lates the mass fraction of acrylate monomer to the total weight of the copolymer can be no less than about twenty (20) wt% and no greater than about one hundred (100) wt% such as no less than about thirty (30) wt% and no greater than about eighty (80) wt%, no less than about forty' (40) wt% and no greater than about seventy' (70) wt%, or no less than about forty five (45) wt% and no greater than about sixty' (60) wt% (e.g., one hundred (100) wt%, ninety five (95) wt%. ninety (90) wt%. eighty five (85) wt%, eighty (80) wt%, seventy five (75) wt%, seventy (70) wt%, sixty five (65) wt%, sixty (60) wt%, fifty five (55) wt%, or fifty' (50) wt%). In particular, certain implementations can include an acry late having a mass fraction of acry late monomer to the total weight of acrylate greater than fifty (50) wt%.

[0052] The preservative composition of the present disclosure may be utilized in a metalworking fluid. These fluids are used to reduce heat and friction and to remove metal particles during metalworking processes. For instance, the composition may be utilized to cool and / or lubricant metalworking processes such as turning, grinding, boring, drawing, tapping, gear shaping, reaming, rolling, hobbing, and band- and hack-sawing. The composition may improve the quality of the workpiece by continuously removing the fines, chips, and swarfs from the tool being used and the surface of the workpiece.

[0053] The preservative composition 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 preservative composition of the present disclosure may be water based and may be 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.

[0054] 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.

[0055] 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.

[0056] 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 preservative compositions.

[0057] 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.

[0058] 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.

[0059] 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 set 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] As used herein, the terms “first”, “second”, and “third” may7be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.

[0064] 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.

[0065] 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 not 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.

[0066] 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.EXAMPLESExperimental Methods:Minimum Inhibitory Concentration Testing

[0067] MICs were determined via microbroth dilution using the following specific test parameters:

[0068] Necessary organism dilutions via ODeoo were calculated based on ODeoo of 1.0 being equivalent to 8* 108CFU / mL. Biocide dilutions were performed in 2-fold increments for each assay.Bacterial Challenge Testing

[0069] Bacterial challenge testing organisms were Alcaligenes faecalis (ATCC #25094), Enterobacter aerogenes (ATCC #13048), Escherichia coli (ATCC #11229), and Pseudomonas aeruginosa (ATCC #10145). All bacteria were blended from separate overnight cultures grown in Tryptic Soy Broth (TSB) and mixed at equal CFU via ODsoo measurements, then diluted to ODeoo = 0.7 (~108CFU / mL) to create the final bacterial consortium. The consortium was prepared weekly and shortly before each inoculation.Inoculations were performed by adding 0.5 mL to 50 g of the indicated test sample to give ~106CFU / g per inoculation. Viability readings were performed at the indicated intervals following each challenge by applying a small amount of the test sample onto Tr ptic Soy Agar (TSA). Plates were then incubated at 32 °C for 3-5 days before being evaluated on a semi-quantitative scale. This scale estimates the approximate CFU / g by visual assessment of the colony density along the streak lines. Readings are recorded as the average of two duplicate semi-quantitative readings from '‘0” to “4.” Samples were mixed before every viability reading and after every inoculation. The pass criteria is a “0” rating seven days after the last inoculation, though any significant differentiation against the control can be interpreted as a degree of performance.Example 1:Antibacterial Activity of Jeffamine RFD270 Alone and in Combination with BIT

[0070] The comparative efficacy of Jeffamine T403 (polyoxypropylenetriamine) and Jeffamine RFD270 (a cycloalipathic polyetheramine) were evaluated for efficacy alone and in combination with BIT. The source of BIT was Proxel GXL, a ~20 w / w% BIT product in glycolic solvent. Blends were made on weight (1: 1) and tested for their activity through minimal inhibitory concentration (MIC) testing against three industrially relevant bacterial organisms: P. aeruginosa (ATCC #10145), E. coli (ATCC #8739), and S. aureus (ATCC #6538). The results are shown below in Table 1.Table 1

[0071] Jeffamine RFD270 was found to be highly synergistic with BIT against diverse bacterial species. MIC values for Proxel GXL, Jeffamine RFD270, and 1 : 1 mixtures (based on weight%) were determined against the test organism using 96-well microbroth dilution methodology. The MIC values are reported on product level. The data presented is a summary of at least 6 replicates.Example 2Effective Ratios of BIT and Jeffamine RFD270

[0072] The ratios of Jeffamine RFD270 and BIT where synergy is maintained (SI <= 0.5) against Pseudomonas was determined experimentally. For this test, Jeffamine RFD270 was diluted to 20% active in DMSO and subsequently mixed with Proxel GXL (-20% BIT) at ratios from 1:50 to 50: 1. The MIC of these mixtures was then determined against Pseudomonas aeruginosa (ATCC #10145)using 96-well microbroth dilution methodology. The MIC values are reported on the level of active. The data presented is a summary of 3 replicates.

[0073] The data for Jeffamine RFD270 (Table 2, Figure 1) show that synergy (SI < 0.5) is observed when the ratio of RFD270:BIT is between 50: 1 to 2:3.Table 2Example 3Efficacy of Jeffamine RFD270 in Paint

[0074] To determine whether the observed synergy Jeffamine RFD270 would translate into improvements for preservation applications, challenge testing was conducted using a consortium of industrially important bacterial isolates. The activity of 0. 1% - 0.4% w / w each PEA was evaluated alone and in combination with 50 ppm BIT in an unpreserved interior paint formulation (Sample U230286-07). The non-synergistic Jeffamine M600 and synergistic Jeffamine T403 were included as controls. Challenge testing revealed that Jeffamine RFD270 preserved the paint formulation at 0.2% w / w and significantly improved the activity of 50 ppm BIT at 0. 1% w / w. The non-synergistic PEA Jeffamine M600 did not improve the preservation of the paint alone or in combination with 50 ppm BIT.Table 3

[0075] 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 beinterchanged both in whole or in part. Furthermore, those of ordinary7skill 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

What Is Claimed:

1. A preservative composition, comprising: a cycloaliphatic poly etheramine of the Formula I,1.2-benzisothiazolin-3-one ("‘BIT”), wherein a weight ratio of the compound of Formula I to BIT is from about 100: 1 to about 1 : 10.

2. The composition of claim 1, wherein the weight ratio of the compound of Formula I to BIT is from about 75: 1 to about 1:5.

3. The composition of claim 1, wherein the weight ratio of the compound of Formula I to BIT is from about 60: 1 to about 1:3.

4. The composition of claim 1, wherein the weight ratio of the compound of Formula I to BIT is from about 50: 1 to about 2:3.

5. The composition of claim 1, wherein the compound of the Formula I is present in the composition at a concentration of from about 10% by weight to about 80% by weight.

6. The composition of claim 1, wherein the compound of the Formula I is present in the composition at a concentration of from about 20% by weight to about 65% by weight.

7. An aqueous industrial material, comprising: a cycloaliphatic poly etheramine of the Formula I,wherein Formula I is present in the aqueous industrial material in an amount from about 0.05% w / w to about 5% w / w.

8. The aqueous industrial material of claim 7, wherein Formula I is present in the aqueous industrial material in an amount from about 0.1% w / w to about 2% w / w.

9. The aqueous industrial material of claim 7, wherein the industrial material is a nonreactive aqueous industrial material.

10. The aqueous industrial material of claim 7, wherein the industrial material is selected from the group consisting of metalworking fluids, paints, coatings, plasters, adhesives, sealants, caulks, mineral slurries, pigment dispersions, admixtures, joint compounds and spackles, pigment slurries, concrete, polymer emulsions, polymerdispersions, inks, sizes, agricultural pesticide formulations, household cleaning products, personal care products, varnishes, sealing compositions, leather auxiliaries, paper coating agents, cosmetics, shampoos, bodywashes, conditioners, and preservatives for such industrial materials.

11. The aqueous industrial material of claim 7, wherein the aqueous industrial material is substantially free of BIT.

12. The aqueous industrial material of claim 7, wherein the aqueous industrial material is substantially free of additional biocides.

13. An aqueous industrial material, comprising: a cycloaliphatic poly etheramine of the Formula I,(1), and l,2-benzisothiazolin-3-one (‘'BIT”), wherein the compound of Formula I and BIT are present in the aqueous industrial material at a weight ratio of from about 50: 1 to about 2:3.

14. The aqueous industrial material of claim 13, wherein the compound of Formula I and BIT are present in the aqueous industrial material at a weight ratio of about 1 : 1.

15. The aqueous industrial material of claim 13, wherein Formula I is present in the aqueous industrial material in an amount from about 0.05% w / w to about 5% w / w.

16. The aqueous industrial material of claim 15, wherein Formula I is present in the aqueous industrial material in an amount from about 0.1% w / w to about 3% w / w.

17. The aqueous industrial material of claim 13, wherein BIT is present in an amount of from about 10 ppm to about 100 ppm.

18. The aqueous industrial material of claim 17, wherein BIT is present in an amount of from about 20 ppm to about 80 ppm.

19. The aqueous industrial material of claim 17, wherein BIT is present in an amount of from about 30 ppm to about 60 ppm.

20. The aqueous industrial material of claim 13, wherein the industrial material is selected from the group consisting of metalworking fluids, paints, coatings, plasters, adhesives, sealants, caulks, mineral slurries, pigment dispersions, pigment slurries, concrete, polymer emulsions, polymer dispersions, inks, sizes, agricultural pesticide formulations, household cleaning products, personal care products, varnishes, sealingcompositions, leather auxiliaries, paper coating agents, cosmetics, shampoos, bodywashes, conditioners, and preservatives for such industrial materials.

21. An oil or water-based concentrate for the aqueous industrial material of claim 7.

22. The oil or water-based concentrate of the aqueous industrial material of claim 21, wherein the Formula I is present in the concentrate from about 20% w / w to about 80% w / w.

23. An oil or water-based concentrate for the aqueous industrial material of claims 13- 20.

24. A method for enhancing in-container preservative performance of an aqueous industrial material, comprising adding an effective amount of the preservative composition according to claim 1.

25. The method of claim 24, comprising inhibiting or preventing growth of microorganisms in the industrial material.

26. The method of claim 25, wherein the microorganisms are selected from a group consisting of bacteria, fungi, yeasts, algae, slimes, and a combination thereof.

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