WO2026011100A1

WO2026011100A1 - Polyetheramine-based preservative compositions

Info

Publication number: WO2026011100A1
Application number: PCT/US2025/036389
Authority: WO
Inventors: Jake JACOBS; Ashley GIL; Weiyu YIN; Meihua Yang
Original assignee: TROY TECHNOLOGY II Inc
Current assignee: TROY TECHNOLOGY II Inc
Priority date: 2024-07-03
Filing date: 2025-07-03
Publication date: 2026-01-08
Anticipated expiration: 2027-01-03

Abstract

The present disclosure is generally directed to a preservative composition including at least one primary aliphatic polyetheramine and an isothiazolin-3-one blend with a first isothiazolin-3-one and a second isothiazolin-3-one. The primary aliphatic polyetheramine and the isothiazolin-3-one blend are present in the preservative composition at a weight ratio of from about 100:1 to 2:1.

Description

POLYETHERAMINE-BASED PRESERVATIVE COMPOSITIONS

RELATED APPLICATIONS

[0001] The present application is based on and claims priority to U.S. Provisional Patent application Serial No. 63/667,167, filed on July 03, 2024, which is incorporated herein by reference.

BACKGROUND

[0002] Metalworking fluids (MWFs) are commonly used during metal processing for the purpose of cooling and lubricating the metal while also eliminating metal chips generated by the machinery. A major challenge with MWFs is their susceptibility to bacterial and fungal contamination during their use in metalworking operations, which not only negatively impacts the performance of the MWFs but can expose workers to aerosolized pathogens.

[0003] MWFs are typically provided to metalworking operators in concentrate form, and the concentrate is subsequently diluted with water and used over a period of several weeks or months. As such, MWFs typically also contain high concentrations of bactericidal and fungicidal biocidal agents in order to prevent microorganism growth in the fluid throughout its use. In some metalworking fluid formulations, formaldehyde or compounds that give off formaldehyde have been used to provide microbial resistance and are recognized as highly effective and long-acting preservative systems. However, with increasing regulatory scrutiny on formaldehyde, non-volatile alternatives that match the performance of formaldehyde are needed.

[0004] The most common preservative used to replace formaldehyde in metalworking fluid is benzoisothiazolinone (BIT), an isothiazolinone based biocide used due to its stability at high pH, stability in the presence of amines, and regulatory advantaged position compared to other isothiazolinones. However, BIT lacks the performance of formaldehyde and formaldehy de-releasing chemistries, is not highly effective against fungal grow th, and MWF formulators are typically forced to utilize higher concentrations or accept systems with lower use lifecycles. The combined effect of these forces leads to less sustainable MWFs with potentially higher human health risks due to contamination or high biocide use rates. For this reason, solutions that aim to reduce the level of formaldehyde in MWFs without sacrifices to performance are highly desired and necessary to achieve sustainable MWF preservation. SUMMARY

[0005] The present disclosure is generally directed to a preservative composition including at least one primary aliphatic poly etheramine and an isothiazolin-3-one blend with a first isothiazolin-3-one and a second isothiazolin-3-one. The primary aliphatic polyetheramine and the isothiazolin-3-one blend may be present in the preservative composition at a weight ratio of from about 100: 1 to 2: 1.

[0006] Other features and aspects of the present disclosure are discussed in greater detail below.

BRIEF DESCRIPTION OF THE DRAWINGS

[0007] 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:

[0008] Figure 1 depicts a table showing synergy' of butylbenzisothiazolinone (BBIT) with either benzoisothiazolinone (BIT) or primary aliphatic poly etheramine (Jeffamine T403) against Pseudomonas aeruginosa.

[0009] Figure 2 depicts the efficacy of isothiazolinone blends and Jeffamine T403 compared to blends containing the industry -standard blends of bactericide (Grotan or BIT) plus fungicide (iodopropynyl buty lcarbamate (IPBC) and/or BBIT).

[0010] Figure 3 depicts the efficacy of isothiazolinone blends and Jeffamine T403 compared to single isothiazolinone (Mergal K10N), dual isothiazolinone (BIT+BBIT), boosted isothiazolinone (BBIT + Jeffamine T403), or the combination of two isothiazolinones and Jeffamine T403.

[0011] Figure 4 depicts the efficacy of blends of BIT/BBIT compared to blends containing BIT/BBIT and commercially available polyetheramines in a soluble oil (U23- 0222-01) diluted to 5% with tap water.

[0012] Figure 5 depicts the efficacy of blends of BIT/BBIT compared to blends containing BIT/BBIT and commercially available polyetheramines in a semi-synthetic formulation (U23-0432-03) diluted to 2.5% with tap water.

[0013] 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

[0014] 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.

[0015] The present disclosure is generally directed to a preservative composition including at least one primary aliphatic polyetheramine compound and an isothiazolinone blend with a first isothiazolin-3-one and a second isothiazolin-3-one. According to example aspects of the present disclosure, the weight ratio of the primary aliphatic poly etheramine to the isothiazolin-3-one blend may be from about 100: 1 to about 2: 1.

[0016] In one exemplary' embodiment, the weight ratio of the primary aliphatic polyetheramine to the isothiazolin-3-one blend is from about 100:1 to about 2: 1, such as from about 75: 1 to about 1 :50. such as from about 50: 1 to about 1 : 15. such as from about 10: 1 to about 1: 10, such as from about 5: 1 to about 1:5, such as from about 3: 1 to about 1:3, such as from about 2: 1 to about 1:2, or any range therebetween. In one example embodiment, the weight ratio of the primary aliphatic poly etheramine to the isothiazolin-3- one blend may be from about 100: 1 to about 2: 1.

[0017] The primary aliphatic polyetheramine compound may have the structure of Formula I:

(I),

[0018] wherein R1 is H or Ci to C9 alky l, each of R2, R3, and R4 is independently H or CH3, and each of x, y, and z is independently 1 to 10.

[0019] Surprisingly, ternary combinations of polyetheramine and an isothiazolin-3-one blend disclosed herein are useful for metalworking fluid preservation at a low active content. Unexpectedly, formulations disclosed herein including the blend of two isothiazolin-3-ones and poly etheramine (ternary mixtures) significantly outperform the formulations containing polyetheramine and a single isothiazolin-3-one, and formulations containing two isothiazolin-3-ones. As such, the composition disclosed herein may be useful as a preservation at lower levels of isothiazolinone, with performance characteristics that exceed or match industry' standards containing formaldehyde-adducts and fungicides. [0020] The degree of polymerization (x. y, and z) of Formula I may be independently one (1) to ten (10). The polymerization degrees x, y, and z can be the same or different in some instances. For instance, x may be one, y may be two, and z may be three. In another instance, z, y, and z may each be two. In one example embodiment, the sum of polymerization (e.g., the total of x, y, and z values) is no less than five (5), such as six (6), seven (7), eight (8), nine (9), or ten (10). In one example embodiment, the sum of x, y, and z values is no greater than ten (10).

[0021] The poly etheramine may be a primary' aliphatic poly amine. For instance, the polyetheramine may be polyoxypropylenediamine or polyoxyprolyenetriamine. In one example embodiment, the poly etheramine of Formula 1 may be Jeffamine® T403 poly etheramine (Huntsman Corp., Houston, Texas). The preservative composition of the present disclosure may include one or more poly etheramines. The polyetheramine may be present in the composition in an amount from about twenty percent (20%) by weight to about eighty percent (80%) by weight, such as from about twenty-five percent (25%) by weight to about seventy -five percent (75%) by weight, such as from about thirty-five percent (35%) by weight to about sixty' percent (60%) by weight, such as from about forty percent (40%) by weight to about fifty-five percent (55%) by weight, or any range therebetween, based on the weight of the composition.

[0022] The preservative disclosed herein may include an isothiazolinone blend, such as an isothiazolin-3-one blend. Isothiazolinones are understood to be effective against a broad range of microorganisms. Generally, the isothiazolinone blend may include at least a first isothiazolin-3-one and a second isothiazolin-3-one that provides a desired biocidal activity. As used herein, an “isothiazolin-3-one blend-’ refers to a mixture of at least two distinct isothiazolin-3-one compounds. For instance, the isothiazolin-3-one blend may include a first isothiazolinone and a second isothiazolinone. It is understood the first isothiazolin-3- one and the second isothiazolin-3-one are distinct isothiazolin-3-one compounds.

[0023] In one example embodiment, the isothiazolin-3-one may be a 2-alkyl-4- isothiazolin-3-one, l,2-benzisothiazolin-3-one, or any combination thereof. It should be understood that the aforementioned isothiazolin-3-ones may be substituted or unsubstituted.

[0024] In one example embodiment, the isothiazolin-3-one may be at least one 2-alkyl- 4-isothiazolin-3-one that can be substituted or unsubstituted. For instance, the isothiazolin- 3-one may be a 2-(C4-Cio) alkyl-4-isothiazolin-3-one. Substituted 2-(C4-CIO) alkyl-4- isothiazolin-3-ones may contain (C1-C4) alky l groups or chloro substituents at one or both of the 4- and 5-positions of the isothiazoline ring.

[0025] In the 2-alkylisothiazolin-3-one, the alkyd radical denotes an n-alkyl, i-alkyl, or c-alkyl radical. The alkyl radical may include one (1) to ten (10), in particular one (1) to eight (8), carbon atoms. Particular embodiments are 2-n-octy lisothiazolin-3-one and 4,5- dichloro-2-n-octylisothiazolin-3-one.

[0026] In one example embodiment, the isothiazolin-3-one may be at least one substituted or unsubstituted l,2-benzisothiazolin-3-one. For instance, if substituted, the substituent may be a C1-C10 alkyl, such as a Ci-Ce alky 1, such as a C2-C5 alky l, such as a C4 alky l.

[0027] For instance, in one example embodiment, the isothiazolin-3-one may include 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.

[0028] In another example embodiment, the isothiazolin-3-one may include BIT, BBIT, MIT, CMIT, OIT, DCOIT, or a combination thereof. In another example embodiment, the isothiazolin-3-one may include BIT, BBIT, CMIT, and/or MIT. In another example embodiment, the isothiazolin-3-one may include BIT and/or BBIT.

[0029] In one example embodiment, the isothiazolin-3-one may include a fused benzyl ring. For instance, in one example embodiment, the isothiazolin-3-one may include BIT, BBIT, nMBIT, or any combination thereof. In another example embodiment, the isothiazolin-3-one may include BIT. BBIT, or any combination thereof. In another particular example embodiment, the isothiazolin-3-one includes BIT. In another particular example embodiment, the isothiazolinone includes BBIT.

[0030] Also, it should be understood that the aforementioned isothiazolinones may be used individually or in any combination.

[0031] Regardless of the isothiazolin-3-ones utilized in the isothiazolin-3-one blend, the first isothiazolin-3-one and the second isothiazolin-3-one may be present in the isothiazolin-3-one blend at a ratio of from about 20: 1 to about 1 :20, such as from about 10:5 to about 1:5, such as from about 5: 1 to about 1 :2, or any range therebetween. [0032] In one example embodiment, the first isothiazolin-3-one may be BIT and the second isothiazolin-3-one may be BBIT. For instance, BIT and BBIT may be present in the isothiazolin-3-one blend at a ratio of from about 3: 1 to about 1 :3. In one example embodiment, BIT and BBIT may be present in the isothiazolin-3-one blend at a ratio of about 1 : 1.

[0033] If desired, the preservative composition according to example aspects of the present disclosure may include additional non-isothiazolinone biocidal agent. For example, the preservative composition may include one or more non-isothiazolinone biocidal agents, such as methylbenzimidazole-2-yl carbamate (“BCM”), IPBC, 3-(3,4-di chlorphenyl)- 1,1- dimethylurea (“Diuron”), and/or 2-bromo-2-nitropropane-l,3-diol (“Bronopol”). Supplemental algaecides that can be used include, but are not limited to, 2-tert- Butylamino-4-ethylamino-6-methylthio-1.3.5-triazin (“Terbutryn”) and 3-(4- isopropylphenyl)- 1,1 -dimethylurea (“Isoproturon”).

[0034] Other examples of non-isothiazolinone biocidal agents are tetraalkylphosphonium halogenides, guanidine derivatives, imidazole containing compounds such as 4-[l - (2,3-dimethylphenyl)ethyl]-l H-imidazole [medetomidine] and derivatives, macrocyclic lactones including avermectins and derivatives thereof such as ivermectin, or spinosyns and derivatives thereof such as spinosad, or enzymes such as oxidase, or proteolytically, hemicellulolytically, cellulolytically, lipolytically or amylolytically active enzymes.

[0035] In example embodiments, it may be advantageous for any biocide present in the preservative composition disclosed herein to be in the form of relatively fine particles, for example, particles having a particle size of from five (5) microns to seventy-five (75) microns. The desired particle size may be attained with conventional techniques such as grinding, milling, sieving and the like. The biocidal agent may be present in the preservative composition in an about from about 0.001 % by weight to about 1 % by weight, such as from about 0.015% by weight to about 0.85% by weight, such as from about 0.25% by weight to about 0.5% by weight, or any range therebetween, based on the weight of the composition. For instance, the biocidal agent can be present in the preservative composition from about 50 ppm to about 1500 ppm, such as about 100 ppm to about 1000 ppm, such as from about 250 ppm to about 750 ppm, such as from about 350 ppm to about 500 ppm, or any range therebetween.

[0036] Optionally, the preservative composition of the present disclosure 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.

[0037] Suitable types of nonionic surfactants include, but are not limited to, polyoxyalkylene glycol alkyl ethers (e.g., polyoxyethylene glycol alkyl ethers, polyoxypropylene alkyl ethers, polyoxy ethylene/propylene alky l ethers), glucoside alkyd ethers, polyoxyalky dene glycol alkydphenol ethers (e.g., polyoxyethylene glycol alkydphenol ethers, polyoxypropylene glycol alkylphenol ethers, polyoxy ethylene/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.

[0038] 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 alky dene 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 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).

[0039] 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 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. [0040] Another type of nonionic surfactant for use in the present disclosure is an alkoxy lated 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).

[0041] 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, alky l 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 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 alky lesters, salts of alky lsulfuric esters, salts of alkydsulfuric esters, sulfuric esters of polyoxyethylenealkydethers, 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 polyoxyethylenealkydethers, salts of phosphoric esters of polyoxyethylenealkylphenylethers, partially saponified compounds of styrene-maleic anhydride copolymers, partially saponified compounds of olefin-maleic anhydride copolymers, naphthalenesulfonate-formahn 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 ary l sulfonates, especially salts of Cs-Cis alkyd benzene sulfonates such as salts of dodecylbenzene sulfonate, and combinations thereof. [0042] 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 poly etheramines and thick eners/suspending agents present and well as the ty pes of surfactants utilized. Typically, however, an amount of surfactant is used which is sufficient to provide a weight ratio of poly etheramine: surfactant within the range of from about 5: 1 to about 50: 1 or from about 6: 1 to about 20: 1.

[0043] Further, certain surfactants and combinations of surfactants also have well- known activities disrupting membranes. This activity⁷ is general to several cationic surfactants, but is also true of certain non-ionic and ionic surfactants.

[0044] 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 viscosity of 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 preservative composition 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).

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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 of water-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 dunng 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 by pumping or other means to one or more suitable storage containers such as tanks, drums or totes.

[0049] 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 formulation. In another example aspect, the preservative composition 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 preservative composition may be oil soluble. [0050] The preservative compositions disclosed herein may be added to an aqueous industrial formulation as a concentrate. In one example implementation, the concentration of the aliphatic primary poly etheramine 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.

[0051] The preservative composition of the present disclosure are useful for imparting resistance to microorganism growth, including bacterial, fungal and algae growth, in a wide variety of working 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.

[0052] 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.

[0053] Bacteria: Alcaligenes such as Alcaligenes faecalis, Acinetobacter such as Acinetobacter calcoaceticus , Bacillus such as Bacillus subtilis, Citrobacter such as Citrobacter freundii, Corynebacterium such as Corynebacterium ammoniagene , Enterobacter such as Enterobacter aerogenes or Enterobacter cloacae, Enterococcus such as Enterococcus hirae, Escherichia such as Escherichia coli, 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,'

[0054] Fungi: Acremonium such as Acremonium strictum, Altemaria such as Altemaria tenuis or Altemaria 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, Tri choderma such as Trichoderma virens.

[0055] The working compositions of the disclosure include a poly etheramine and an isothiazolin-3-one blend disclosed herein. In one example embodiment, the preservative composition includes a poly etheramine and an isothiazolin-3-one blend.

[0056] 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 poly etheramine and an isothiazolin-3-one blend may be in the form of a concentrate including essential ingredients, i.e., the poly etheramine compound and the isothiazolin-3-one blend (“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.

[0057] 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, 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.

[0058] The preservative composition of the present disclosure may be utilized as 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.

[0059] 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 maybe 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.

[0060] The preservative composition of the present disclosure may be used to inhibit the corrosion of substrates such as metal substrates. As such, the preservative composition prevents or reduces the rate of oxidation of a metal surface, generally when the metal is exposed to water or air, or a combination of the two. Not to be limited by theory, it is believed that the preservative composition of the present disclosure migrates to the surface of the metal substrate and blocks oxygen and/or air form causing further oxidation of the metal substrate surface. As such, the preservative composition of the present disclosure may first be applied to the metal substrate and thereafter a paint may be applied to the coated metal substrate. [0061] The metal substrate may generally be a metal surface. For instance, the metals may include, but are not limited to, iron, copper, aluminum, brass, tin, zinc, and iron alloys such as steel, metal alloys, cast iron.

[0062] In one example embodiment, the preservative composition may be employed as a coolant preservative. Advantageously, the preservation quality of coolants can be maintained without formaldehyde at low levels of isothiazolinones. Combination of polyetheramine and the isothiazolin-3-one blend is key to matching the performance of traditional preservation strategies based on the long-established dogma of coolant preservation with formaldehyde-donors and fungicides like IPBC. Further, because the preservation effect can be achieved at low levels of total isothiazolinone, the preservative composition disclosed herein has clear advantages over standard preservation requiring significantly higher biocide content.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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. [0067] 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] As used herein, the terms “first”, “second”, and “third” may⁷ be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components. [0073] 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.

[0074] 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.

[0075] 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.

EXAMPLES

Experimental Methods:

Inoculum Preparation

[0076] Axenic stocks of six bacterial strains Pseudomonas aeruginosa (ATCC #10145), Pseudomonas putida (ATCC #12633), E. coli (ATCC #11229), Alcaligenes faecalis (ATCC #8750), Klebsiella pneumoniae (ATCC #4352), and Pseudomonas aeruginosa (ATCC #15442) were cultured as lawns on Tryptic Soy Agar (TSA) and incubated overnight at 32 °C. After incubation, bacterial lawns were collected into 5 mL sterile dH2O and adjusted to ODeoo = 8 using additional CIH2O. This mixture was inoculated into the test samples at 1% v/v. Separately, fungal cultures of Aspergillus brasiliensis (ATCC #16404). Fusarium solani (ATCC #26671) and Candida albicans (ATCC #10231) were grown on Malt Extract Agar (MEA) for 2-3 days at 28 °C. The fungal lawns were then flooded with 5 mL sterile dH2O and centrifuged at 5 minutes (4,500 rpm) to collect the cells. The pellets were then washed twice with 5 mL sterile dH2O before being resuspended again in 5 mL dH2O. The resulting suspensions were then counted with a hemocytometer and adjusted to l* 10⁷ spores/mL with additional dH2O. Immediately before inoculation, the concentration adjusted fungal cultures are mixed at equal volumes and inoculated into the test samples at 1% v/v.

MWF Challenge Test Procedure

[0077] Test samples were prepared by diluting the MWF concentrates to 2% - 5% w/v with tap water (Florham Park, NJ). The samples were then inoculated with either bacteria (1% v/v) and/or fungus (1% v/v), shaken at 200 rpm at 35 °C for 12 hours, then held static at 35 °C for 12 hours. This cycle was repeated daily. Seven days following inoculation, 20 pL of the sample are plated onto TSA and Potato Dextrose Agar (PDA). TSA plates are incubated at 35 °C for 2 days, and PDA plates are incubated at 28 °C for 5 days. Colonies are then counted and reported as CFU/mL when countable, or too numerous to count (TNTC) when the growth is confluent. Failure is defined as detection of bacterial concentrations >10⁵ CFU/mL or fungal counts >10³ CFU/mL.

Minimum Inhibitory Concentration Testing

[0078] MICs were determined via microbroth dilution using the following specific test parameters:

[0079] Necessary organism dilutions via ODeoo were calculated based on ODeoo of 1.0 being equivalent to 8xl0⁸ CFU/mL. Biocide dilutions were performed in 2-fold increments for each assay.

Synergy’ Index Calculations

[0080] Synergy' index (SI) scores were calculated according to the mass action equation below:

S.I = [MIC [A ]in-blend / MIC [A ]alone ] + [MIC [B]in-blend / MIC[B]alone ] [0081] Combinations of ingredients were determined to be synergistic (S.I. < 0.5), additive (S.I. > 0.5 to 1), indifferent (S.I. > 1 to < 2) or antagonistic (S.I. > 2), as defined by European Committee for Antimicrobial Susceptibility Testing (EUCAST) of the European Society of Clinical Microbiology' and Infectious Diseases (ESCMID) guidelines. Test Biocide Compositions

Preservative Descriptions

Unpreserved Matrices

[0082] Unpreserved test matrices of coolants:

Example 1.

Formulations of BIT, BBIT, and Jeffamine T403

[0083] The synergy of BIT, BBIT, and Jeffamine T403 was evaluated against Pseudomonas aeruginosa (ATCC #10145). The test stocks included Jeffamine T403 and Densil DN diluted to 20% in dipropylene glycol, and Mergal BIT20X tested as supplied. The minimum inhibitory concentration (MIC) data shows that a combination of BIT, BBIT, and T403 (10%, 10%, 45%) resulted in MIC values significantly below any single component (SI = 0.10). (Table 1).

[0084] The synergy of ratios of BBIT and Jeffamine T403 and BIT was explored at ratios ranging from 1 :3 to 3: 1. Synergy indices were independently calculated for each ratio across independent MIC measurements using Pseudomonas aeruginosa (ATCC #10145) as the test organism and reported as the fractional amount of BBIT (by weight%) in the indicated combination. Combinations of BIT and BBIT were not synergistic (SI = 1.02) indicating the synergy of the blend in Table 1 was driven by the combination with Jeffamine T403. The data shows that Jeffamine T403 is synergistic with BBIT when the level of Jeffamine T403 is present in excess BBIT concentrations (Table 2. Figure 1).

Example 3

Efficacy of BIT BBIT Jeffamine T403 Compared to Typical Preservation Packages Combinations in Soluble Oil

[0085] The efficacy of blends containing the broad-spectrum isothiazolinone blend of BIT, BBIT, and Jeffamine T403 were compared to blends containing the industry-standard blends of bactericide (Grotan or BIT) plus fungicide (IPBC or BBIT). Testing in a 3% solution of a generic soluble oil formulation showed that Grotan worked well wi th either IPBC or BBIT, but delivery' of BBIT + BIT showed substandard performance, failing on the second inoculation at 100 ppm each active or fifth inoculation at 150 ppm each active. In contrast, combinations of BIT, BBIT, and Jeffamine T403 achieved 7 inoculations of protection at 100 ppm each active or 8 inoculations of protection with 150 ppm each active. The data show that the preservation quality' of coolants can be maintained without formaldehyde at low levels of isothiazolinones using low levels of Jeffamine T403. The data is shown in Figure 2. Example 4:

Efficacy of BIT/BBIT/ Jeffamine T403 compared to other blends

[0086] The efficacy of combinations of BIT, BBTT, and Jeffamine T403 were compared with single isothiazolinone (Mergal KI ON), dual isothiazolinone (BIT+BBIT), boosted isothiazolinone (BBIT + Jeffamine T403), or the combination of two isothiazolinones and Jeffamine T403. The results in a 2% dilution of soluble oil formulation U21-0521-34 show significant improvement over all other options, showing no growth through 8 inoculations at -200 ppm total isothiazolinone. The data is shown in Figure 3.

Example 5:

Efficacy ofBIT/BBIT with other polyetheramines compared to other blends

[0087] The efficacy of blends of BIT/BBIT were compared to blends containing BIT/BBIT and several commercially available poly etheramines in a soluble oil (U23-0222- 01) diluted to 5% with tap water. Microbiological challenge of the dilutions showed that polyetheramines Jeffamine T403, D230, D400, D205, and RFD270 improved the performance of BIT and BBIT, enabling the diluted fluids to harbor undetectable (<50 CFU/mL) or low levels of microbial growth for longer compared to fluids containing only BIT and BBIT at significantly higher levels (Figure 4).

[0088] The efficacy of blends of BIT/BBIT were also compared to blends containing BIT/BBIT and several commercially available polyetheramines in a semi-synthetic formulation (U23-0432-03) diluted to 2.5% with tap water. Microbiological challenge of the dilutions showed that poly etheramines Jeffamine T403, D230, D400, and RFD270 significantly improved the performance of BIT and BBIT, enabling the diluted fluids to harbor undetectable (<50 CFU/mL) or low levels of microbial grow th for longer compared to fluids containing only BIT and BBIT at significantly higher levels (Figure 5).

[0089] 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 w ay 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: at least one primary aliphatic polyetheramine; and an isothiazolin-3-one blend comprising a first isothiazolin-3-one and a second isothiazolin-3-one, wherein the primary aliphatic poly etheramine and the isothiazolin-3-one blend are present in the preservative composition at a weight ratio of from about 100: 1 to 2: 1.

2. The composition of claim 1, wherein the isothiazolin-3-one blend comprises 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.

3. The composition of claim 1, wherein the first isothiazolin-3-one is different than the second isothiazolin-3-one.

4. The composition of claim 1, wherein the first isothiazolin-3-one comprises BIT.

5. The composition of claim 4, wherein the second isothiazolin-3-one comprises BBIT.

6. The composition of claim 1 , wherein the ratio of the first isothiazolin-3-one and the second isothiazolin-3-one is from about 5:1 to about 1:5.

7. The composition of claim 1, wherein the ratio of the first isothiazolin-3-one and the second isothiazolin-3-one is from about 3: 1 to about 1:3.

8. The composition of claim 1, further comprising at least one additive comprising an inorganic metal compound, a silicate, a pyrithione salt, or an organic amine.

9. The composition of claim 8, wherein the inorganic metal compound comprises one or both of an inorganic zinc compound, an inorganic magnesium compound, an inorganic copper compound, or an inorganic lithium compound.

10. The composition of claim 9, wherein the inorganic zinc compound comprises one or more of zinc oxide, zinc nitrate, zinc chloride, and zinc acetate.

11. The composition of claim 8, wherein the inorganic magnesium compound comprises magnesium oxide.

12. The composition of claim 8, wherein the inorganic copper compound comprises one or more of copper sulfate, copper nitrate, copper carbonate, copper oxide, and copper acetylacetonate.

13. The composition of claim 8, wherein the inorganic lithium compound comprises one or more of lithium carbonate, lithium acetate, lithium fluoride, lithium sulfate, lithium nitrate, lithium tetraborate, lithium metaborate, lithium pyrophosphate, lithium tripolyphosphate, lithium orthosilicate, and lithium metasilicate.

14. The composition of claim 8, wherein the silicate comprises one or both of potassium methyl siliconate, and sodium metasilicate.

15. The composition of claim 8, wherein the pyrithione salt comprises one or both of zinc pyrithione and sodium pyrithione.

16. The composition of claim 8, wherein the organic amine comprises a pH adjusting agent.

17. The composition of claim 1 , wherein the pH adjusting agent comprises 2-amino-2- methyl- 1 -propanol .

18. A preservative composition, comprising: at least one primary aliphatic polyetheramine; and an isothiazolin-3-one blend comprising l,2-benzisothiazolin-3-one (“BIT’), N- butyl-1 ,2-benzisothiazolin-3-one (“BBIT”), wherein primary aliphatic poly etheramine and the isothiazolin-3-one blend are present in the preservative composition at a weight ratio of from about 100: 1 to 2: 1.

19. The composition of claim 18, wherein the ratio of the first isothiazolin-3-one and the second isothiazolin-3-one is from about 5: 1 to about 1 :5.

20. The composition of claim 18, wherein the ratio of the first isothiazolin-3-one and the second isothiazolin-3-one is from about 3: 1 to about 1 :3.