Method and composition for stable resins for aqueous processing

Abstract

Methods and compositions are provided for emulsified water-based resins and / or polymer emulsions stabilized in aqueous fluids characterized by extreme chemical environments having high ionic strength and / or extreme pH. The methods include combining an organic premix including the aqueous fluid and the emulsified water-based resin / emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and a fluid having an extreme chemical environment (e.g., an acidic passivator) to obtain a composition in which the emulsified water-based resin is stabilized. Another method includes combining the emulsified water-based resin / emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and a fluid having an extreme chemical environment (e.g., an acidic passivator) to obtain a composition in which the emulsified water-based resin is stabilized.

Description

[Technical field]

[0001] The present invention relates generally to resin and / or emulsion polymer compositions, and more particularly to a method for making water-based resin and / or emulsion polymer compositions that are stable in extreme chemical environments characterized by high / low pH and / or high ionic strength. [Background technology]

[0002] A wide variety of resins may be used as additives in commercial specialty coatings and industrial fluids. For example, industrial coatings for a variety of substrates include resins that help prevent undesirable conditions such as corrosion or wear in metalworking applications.

[0003] Many of the commercially available polymers found to be most useful as additives for industrial coatings are insoluble in water, and since many industrial coatings and fluids are water-based, these polymers are manufactured as "resins" using emulsion and dispersion techniques in order to properly incorporate them into water-based industrial fluids and coatings.

[0004] Many existing resins useful for imparting advantageous physical properties (e.g., abrasion resistance, water repellency, extended pot life, anti-syneresis, high film strength, high adhesion, and self-healing / corrosion resistance), particularly those useful for metal processing, are stable in aqueous environments not characterized by high / low pH and / or high ionic strength as a result of existing emulsion and dispersion technology. However, these resins are often not stable in fluids having "extreme" chemical environments characterized by high or low pH and / or high ionic strength. These resin / emulsion polymers may be characterized as being due to a polymer synthesis that results in an unstable chemical formula in the "extreme" chemical environment.

[0005] Another way to characterize these particular resins / emulsion polymers is by their Critical Coagulation Concentration ("CCC"), which is the concentration of ions present in an aqueous fluid at which a particular resin or emulsion polymer will aggregate or destabilize. A CCC level close to 0 indicates that the resin is easily destabilized, while high CCC levels are rare among resins / emulsion polymers. Typically, "unstable" resins and / or emulsion polymers have polymer compositions that result in low CCC levels (i.e., resins that are easily destabilized in the "extreme" environments described herein). In particular, combining high / low pH and / or high ionic strength fluids with these typical "unstable" resins / emulsion polymers (i.e., those that are considered in the art not to remain stable in fluids with high / low pH and / or high ionic strength) generally does not work, resulting in either immediate emulsion destabilization and / or fluid gelation over time.

[0006] Unfortunately, many coating compositions and industrial fluids in which these "unstable" resins would be useful have "extreme" chemical environments, i.e., chemical environments characterized by high ionic strength and / or very low or very high pH. Thus, many existing resins useful for imparting desirable properties are stable in neutral or near-neutral aqueous environments as a result of surfactant-enabled emulsion and dispersion techniques, but are not stable in industrial fluids (e.g., passivation fluids) that have "extreme" chemical environments characterized by high or low pH and / or high ionic strength. Thus, while it would be beneficial to include these resins in industrial fluids and coatings, it is difficult for formulators to incorporate these resins and maintain emulsions, dispersions, and / or colloids due to the "extreme" chemical environments of such fluids and coatings.

[0007] In response to these challenges, efforts have been made to develop methods to stabilize resins in extreme chemical environments. For example, rather than attempting to stabilize existing resins known to be effective in imparting useful properties (e.g., corrosion or abrasion resistance), formulators may attempt to completely change the entire chemical makeup of commercially available polymers and resins to obtain modified synthetic resins / polymer emulsions that are inherently stable in high / low pH and / or high ionic strength fluids. These resins are understood to have undergone fundamental chemical changes (either during or after synthesis) to establish stability in extreme environments. Such attempts often involve complex polymerization processes involving numerous ingredients (including polymer stabilizers), high temperatures, and specialized reactor equipment. Notably, such processes are cost and time impractical for many formulators to implement to achieve stability in industrial fluids and coatings with resin additives. In addition, many industrial plants are not equipped with the reaction vessels required to carry out the synthesis of these modified resins. Thus, it is very difficult or impossible for many formulators to carry out such complex and costly "reformulation" or "modification" processes.

[0008] The resins and emulsion polymers may also be "reformulated" or "modified" after synthesis by adding reactive surfactants, i.e., surfactants that react with the resin and / or emulsion polymer such that the chemical formula of the surfactant changes. The "reactive" surfactants may form covalent bonds with the resins and emulsion polymers to form the "reformulated" or "modified" resins.

[0009] Additionally, these "reformulated" or "modified" resin additives, while essentially stable in the "extreme" chemical environments present in industrial fluids and coatings, are generally chemically altered such that desirable properties (e.g., corrosion or wear resistance) may be altered or less effective compared to properties typically associated with resins that are "unstable" (i.e., resins that, until the inventive systems and processes herein, were not stable in fluids having high / low pH and / or high ionic strength). That is, reformulating a resin at a fundamental chemical level often changes its properties in a way that makes it less desirable as an additive to industrial fluids and coatings.

[0010] It would therefore be useful to have a simple method for stabilizing typically "unstable" resins that are water-based and do not tolerate "extreme" environments in various industrial fluids and coatings. Furthermore, it would be useful if formulators could easily implement these methods to produce new resins that are inherently stable in "extreme" environments without the need for complex materials, polymerization processes, or "reactive" surfactants. In addition, it would be desirable to have a universal stabilization process for "extreme" chemical environments that can be implemented with readily available and commercially available materials and resins. Surprisingly, the inventors of the present system and process have been able to stabilize typically "unstable" resins with proven beneficial properties in "extreme" chemical environments without fundamentally changing the chemistry of the resin / emulsion polymer itself. Thus, the inventors have discovered and implemented the present system and process that eliminates the need to develop new synthetic resins that are inherently stable in "extreme" environments, thereby reducing both time and economic costs, as well as resulting in industrial fluids with additives that have known effective and desirable properties. Summary of the Invention

[0011] Summary of the Invention In one embodiment, there is a method for stabilizing an emulsified water-based resin in an aqueous fluid characterized by an extreme chemical environment having high ionic strength and / or high / low pH. The method includes combining an aqueous resin / emulsion polymer or an organic premix including an aqueous fluid and an aqueous resin / emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and an industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivating fluid) to obtain a composition in which the emulsified water-based resin is stabilized despite the "extreme" chemical environment of the industrial fluid or coating. The emulsified water-based resin may be or may include an emulsion polymer. The resulting composition may include about 0.5% to about 50% by weight of the aqueous resin.

[0012] In some embodiments of the method, the high ionic strength of the extreme chemical environment of the industrial fluid or coating (e.g., acidic passivation fluid) is characterized by an ionic strength that can destabilize the resin or emulsion polymer as produced, i.e., the ionic strength of the industrial fluid or coating would destabilize the selected resin or emulsion polymer without the techniques of the method disclosed herein, for example. That is, the "extreme chemical environment" is defined by the stability characteristics of the resin and / or emulsion polymer desired to be used in the formulation. In addition, the "extreme chemical environment" may also be characterized by a pH that destabilizes the selected resin / polymer emulsion system. In general, the extreme chemical environment may alternatively or additionally be characterized by a pH below about 3 or above about 11. Aqueous fluids characterized by an extreme chemical environment with high ionic strength include any class of electrolytes present in a dissolved state that destabilize the resin / emulsion polymer system. In general, strong electrolytes are useful in some industrial fluid or coating formulations, but reduce the stability of the emulsion. These electrolytes include, but are not limited to, nitrates, phosphates, sulfates, chlorates, and combinations thereof. In other embodiments, the high ionic strength of the extreme chemical environments of industrial fluids or coatings are characterized by any ionic strength that destabilizes the various resin / emulsion polymer combinations used in the formulations.

[0013] The resin / emulsion polymer referred to herein can refer to any single resin or emulsion polymer, or any combination thereof, that is typically destabilized in an "extreme" chemical environment when used in any formulation according to the methods presented herein.

[0014] In some embodiments of the method, an organic premix is ​​provided that includes the selected resin / emulsion polymer and an aqueous fluid. The aqueous fluid of the organic premix may include an industrial fluid or a coating composition. The aqueous fluid of the organic premix may include any of the resins, polymers, surfactant stabilizers, waxes, wetting aids, defoamers, fillers, rheology modifiers, film formers, and any other additives useful for the selected industrial application, either individually or in combination.

[0015] In some embodiments of the method, an organic premix comprising an aqueous fluid and an aqueous resin is combined with a high hydrophobic lipophilic balance (HLB) surfactant and an additional industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivation fluid). The high HLB surfactant comprises one or more of the nonionic class of ethoxylate surfactants with an HLB in the range of 8 or greater. The resulting composition may comprise from about 0.1% to about 15% by weight of the high HLB surfactant. The amount of high HLB surfactant may be increased as the ionic strength of the aqueous fluid increases to maintain the stability of the emulsified aqueous resin system of the organic premix.

[0016] In another embodiment of the invention, a method is provided for stabilizing an emulsified water-based resin / polymer in an aqueous fluid characterized by an extreme chemical environment having high ionic strength and / or high / low pH. The method includes combining a water-based resin and / or a water-based emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and an industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivating fluid) to obtain a composition in which the water-based resin and / or emulsion polymer is stabilized despite the "extreme" chemical environment of the aqueous fluid. The emulsified water-based resin may be or may include an emulsion polymer. The resulting composition may include about 0.5% to about 50% by weight of the water-based resin.

[0017] In some embodiments of the method, the aqueous fluid characterized by an "extreme" chemical environment is a passivating fluid. The passivating fluid, or passivate, includes one or more of a passivating species, or a combination of passivating species, that can react with or incorporate into a film on a metal surface to provide corrosion resistance benefits. The passivating species may include a Cr source, such as Cr(VI) oxide, Cr(III) nitrate, Cr(III) phosphate, combinations thereof, or any other metal used to improve corrosion resistance. Other additives may be added to the passivating agent, such as reducing agents, waxes, antifoaming agents, and any other additives useful for the selected industrial application.

[0018] These passivators may also be strongly acidic in nature, which may be useful for the selected industrial application. Strong acids include, but are not limited to, common mineral acids such as nitric acid (HNO3), phosphoric acid (H3PO4), and HEDP / etidronic acid (C2H8O7P2). Strong acids may include both organic and inorganic acids. Thus, fluids having an "extreme" chemical environment may be acidic passivators. Acidic passivators may include other additives such as reducing agents, waxes, antifoaming agents, and any other additives useful for the selected industrial application.

[0019] In some embodiments of the method, the aqueous resin / emulsion polymer is stabilized in an extreme environment, where stability can be evaluated by accelerated or environmental testing. The aqueous resin / emulsion polymer is considered "stable" in the system if it retains its properties in a flowable liquid state for at least 2 years in sealed ambient conditions, or at least 30 days in accelerated extreme temperature testing. Accelerated extreme temperature testing includes both high and low temperature protocols. High temperature accelerated testing is accomplished by exposing the resin system to a sealed oven / heating environment at 60°C for one month (30 days) and continually evaluating the resin / emulsion polymer system for changes in consistency, gelling, or degradation of properties. Low temperature accelerated testing is accomplished by exposing the resin / emulsion polymer system to a sealed refrigeration system at 5°C for one month (30 days) and continually evaluating the resin / emulsion polymer system for changes in consistency, gelling, or degradation of properties. An example of a similar, but less rigorous, type of evaluation is ASTM D1849. Loss of stability occurs when the resin / emulsion polymer system experiences any of the following: gelation, clumping, gassing, loss of liquid fluidity, phase separation, other phase changes, or performance degradation in less than two years under closed environmental conditions or less than 30 days in closed, accelerated testing (as described above).

[0020] In some embodiments of the method, an organic premix is ​​provided that includes an aqueous fluid and an aqueous resin, and a high HLB surfactant is added to the organic premix to obtain a mixture of the organic premix with an emulsified aqueous resin and the high HLB surfactant. An industrial fluid or coating that features an "extreme" chemical environment (e.g., and an acidic passivator) can then be added to the mixture of the organic premix and the high HLB surfactant to obtain a composition of an aqueous resin / emulsion polymer stabilized in an "extreme" chemical environment. In some embodiments, to prevent agglomeration, the industrial fluid or coating that features an "extreme" chemical environment (e.g., an acidic passivator) can be added to the mixture of the organic premix and the high HLB surfactant in a slow manner or in a stepwise manner where a portion of the acidic passivator is added slowly and then gradually faster.

[0021] In another embodiment, there is a stabilized resin emulsion system that includes an emulsified waterborne resin, an aqueous fluid characterized by an extreme chemical environment having high ionic strength (e.g., an acidic passivator), and a high hydrophobic lipophilic balance (HLB) surfactant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] Surprisingly, it has been found that water-based resins / emulsion polymers can be stabilized in water-based industrial or coating fluids having "extreme" chemical conditions without chemically altering the resin / emulsion polymer itself. Heretofore, organic resins such as epoxy or acrylic polymer emulsions have been difficult to stabilize in extreme chemical environments such as strongly acidic media (pH<3), strongly basic media (pH>11), and environments characterized by high concentrations of electrolytes (e.g., high concentrations of phosphates, nitrates). Surprisingly, however, it has been found that resins / emulsion polymers can be readily formulated as additives into commercial specialty coatings and industrial fluids according to the methods herein, without the need for costly and complex polymer stabilization techniques or reactive surfactants that fundamentally alter the chemistry and properties of the resin / emulsion polymer itself. Remarkably, embodiments of the process according to the invention herein provide a convenient and universal means by which chemical formulators can stabilize a wider variety of resins in a wider variety of water-based industrial fluids / coatings characterized by "extreme" chemical environments.

[0023] The process according to the embodiments of the invention herein ideally involves commercially available and universally available water insoluble (e.g., emulsified / water dispersed) resins, surfactants, industrial fluids / coatings, and other materials readily available to chemical formulators. Furthermore, the process results in stabilized resin / polymer emulsions, ideally avoiding complex polymerization processes requiring multiple components (including polymer stabilizers) and chemical changes to the resin / emulsion polymer that may impair useful industrial properties. Finally, the process provides a universal process for producing stabilized aqueous resin emulsions in aqueous environments having "extreme" chemical conditions, i.e., chemical conditions characterized by high ionic strength and / or extreme pH.

[0024] In some embodiments, the methods of the present invention are useful for producing industrial fluids or coatings with stabilized emulsified resin additives that are useful on a variety of substrates. Such industrial fluids / coatings exhibit high water repellency, extended pot life, resistance to syneresis (gelling and separation of liquids), strong film strength, significantly improved metal corrosion protection performance over comparable compositions, high adhesion, and improved self-healing capabilities (slowing corrosion spread). Substrates for which these industrial fluids / coatings may be useful include, but are not limited to, steel alloys, galvanized steel, galvalume, galvanneal, aluminized, or other metals. Substrates may also include non-metals, including wood, plastic, or textiles.

[0025] An exemplary method for stabilizing an aqueous resin / emulsion polymer in an aqueous fluid characterized by an extreme chemical environment with high ionic strength and / or extreme pH includes combining an "organic premix" containing the aqueous fluid and the aqueous resin / emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and an aqueous fluid characterized by an extreme chemical environment with high ionic strength and / or extreme pH (e.g., an acidic passivator) to obtain a composition in which the emulsified aqueous resin is stabilized despite the "extreme" environment. The high HLB surfactant may be a non-reactive surfactant, i.e., the non-reactive surfactant associates with the resin / emulsion polymer through interactions that do not cause chemical changes, e.g., do not form covalent bonds with the resin / emulsion polymer. Such a non-reactive surfactant does not alter the chemical and physical properties of the resin / emulsion polymer.

[0026] The "organic premix" includes an aqueous fluid. The aqueous fluid of the organic premix may be or include an industrial fluid or a coating composition. The aqueous fluid of the organic premix may also include an industrial passivation fluid that is already stable and can be combined with an "extreme environment" acidic passivation fluid (wherein the resin / emulsion polymer in the organic premix would be unstable without the systems and methods of the present invention) according to embodiments of the methods herein.

[0027] Additionally, the "organic premix" includes an organic water-based resin / emulsion polymer, whereby in some embodiments the organic water-based resin / emulsion polymer is separate from the aqueous fluid of the organic premix and has not yet been emulsified (such emulsification may not occur until an appropriate surfactant, such as a high HLB surfactant, is added). Suitable chemical species for the organic water-based resin include, but are not limited to, acrylic, epoxy, polyurethane, polyvinylidene chloride, or hybridized (i.e., partially acrylic and epoxy in character). Examples of suitable resins are Alberdingk AC2360, an acrylic resin, and Alberdingk M2959, an epoxy-acrylic hybrid.

[0028] In some embodiments, the addition of a high HLB surfactant to the organic premix results in emulsification of the aqueous resin. The emulsified aqueous resin may be or may include an emulsion polymer.

[0029] The "organic premix" may also contain a number of additives as desired, which may include surfactants, waxes, defoamers, film forming aids, wetting aids, fillers, plasticizers, pigments, rheological additives, or any other additives useful in the selected industrial application.

[0030] Suitable high HLB surfactants include the class of nonionic ethoxylated surfactants such as Tomadol 91-8 and Triton X-405. A "high HLB surfactant" is any surfactant having an HLB value of 8 or greater. It has been found that the range of HLB values ​​suitable for metal corrosion protection purposes is generally about 8 to 18. In addition, since different aqueous resin systems have different emulsifying properties, a "high HLB surfactant" can also refer to any surfactant having an HLB value high enough to stabilize the system in the aqueous formulation. The methods, systems, and formulations according to embodiments of the invention herein use about 0.30% to about 4.0% by weight of a high HLB surfactant.

[0031] A further exemplary method of stabilizing the waterborne resin / emulsion polymer in aqueous fluids characterized by extreme chemical environments having high ionic strength and / or extreme pH includes combining the waterborne resin / emulsion polymer with a high hydrophobic lipophilic balance (HLB) surfactant and an industrial fluid or coating characterized by an "extreme chemical environment" (e.g., an acidic passivator) to obtain a composition in which the emulsified waterborne resin is stabilized in the "extreme" environment.

[0032] Industrial fluids or coatings that are characterized by "extreme" chemical environments may be acidic passivators. Suitable acidic passivators include one or more acidic passivators in which a passivating species is used to provide increased corrosion protection to a surface (e.g., metal). This includes, but is not limited to, common and new transition metal species in the industry, such as chromium, vanadium, manganese, zinc, titanium, and combinations thereof. Suitable acidic passivators may also include non-metallic species, such as silicon, phosphorus, nitrogen, and combinations thereof.

[0033] Suitable aqueous industrial fluids, coatings, and / or industrial passivation fluids used in the claimed methods and formulations according to the aspects of the invention herein may have an "extreme" chemical environment characterized by high ionic strength, and further characterized by any ionic strength that exceeds the typical stability requirements and / or critical coagulation concentration (CCC) of the resin / emulsion polymer used in the system. The high ionic strength may come from a substantial concentration of electrolytes, particularly strong electrolyte systems that interact with the electrical double layer of the emulsion resin / polymer or emulsion system in the organic premix. Classes of electrolytes that impart high ionic strength include, but are not limited to, nitric acid, phosphate, HEDP, chromium (III), salts of other passivating metals, as well as materials that are useful in various industrial applications that fully dissociate to form ionic interactions in aqueous solution. The extreme chemical environment may alternatively or additionally be characterized by any pH that destabilizes the organic premix system, which may generally fall within the range of a pH below about 3 or above about 11. For example, many industrial passivation fluids are characterized by a low pH, e.g., a pH below about 3.

[0034] The "organic premix" portion of the composition according to the present invention embodiment herein may also be formulated as a "receiving" fluid that receives the addition of another fluid having an "extreme environment" in some cases, for example, when the resin / emulsion polymer system is not stable when the "organic premix" portion is added to a fluid characterized by an "extreme environment". For example, a suitable water-immiscible resin or resin blend is added to a portion of DI water at a loading of 0.5-50 wt / wt% solids to form the "organic premix". If desired, other additives such as defoamers and waxes are added to the "organic premix" at loadings required for the selected industrial application. The diluted resin "organic premix" is mixed with a selected stabilizing high HLB surfactant (e.g., loading of 0.1-15 wt / wt%). An acidic passivating fluid having an "extreme environment" with respect to the resin / emulsion polymer present in the "organic premix" can then be added to the high HLB surfactant stabilized "organic premix" to obtain a stable resin / emulsion polymer system according to an embodiment of the present invention.

[0035] In some embodiments of the method, the water-based resin is stabilized in an "extreme" environment for 30 days under accelerated conditions characterized by high and low temperatures. In certain embodiments, stabilized water-based resins made according to aspects of the invention remain stable at 60° C. sealed in an oven for at least 30 days, and at 5° C. sealed in a refrigerated environment for at least 30 days. In other embodiments, stabilized water-based resins made according to the invention remain stable at ambient / room temperature in a sealed container for at least 2 years. The stability of the resulting water-based resin / polymer emulsion composition can be determined by observing a phase change of the composition. A stable composition according to the invention can have a liquid consistency suitable for application to a substrate surface, for example, as a roll coating. Instability of such a composition can be observed when such a "liquid" composition begins to gel, thicken, or solidify. Other ways to determine a stable to unstable phase change include a change in the composition from translucent to opaque, or the appearance of particulate precipitation or settling in the composition.

[0036] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may comprise from about 0.5% to about 50% by weight of the aqueous resin / polymer emulsion, from 1% to about 40% by weight of the aqueous resin / polymer emulsion, or from about 2% to about 30% by weight of the aqueous resin / polymer emulsion, or from about 3% to about 20% by weight of the aqueous resin / polymer emulsion, or from about 4% to about 10% by weight of the aqueous resin / polymer emulsion, or from about 5% to about 9% by weight of the aqueous resin / polymer emulsion, or from about 6% to about 8% by weight of the aqueous resin / polymer emulsion. In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may comprise about 0.5% by weight of the aqueous resin / polymer emulsion, 1% by weight of the aqueous resin / polymer emulsion, about 2% by weight of the aqueous resin / polymer emulsion, about 3% by weight of the aqueous resin / polymer emulsion, about 4% by weight of the aqueous resin / polymer emulsion, about 5% by weight of the aqueous resin / polymer emulsion, about 6% by weight of the aqueous resin / polymer emulsion, about 7% by weight of the aqueous resin / polymer emulsion, about 8% by weight of the aqueous resin / polymer emulsion, about 9% by weight of the aqueous resin / polymer emulsion, about 10% by weight of the aqueous resin / polymer emulsion, about 20% by weight of the aqueous resin / polymer emulsion, about 30% by weight of the aqueous resin / polymer emulsion, about 40% by weight of the aqueous resin / polymer emulsion, or about 50% by weight of the aqueous resin / polymer emulsion.

[0037] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may contain about 0% to about 85% water by weight, or about 5% to about 80% water by weight, about 10% to about 75% water by weight, about 15% to about 70% water by weight, about 20% to about 65% water by weight, about 25% to about 60% water by weight, about 30% to about 55% water by weight, about 35% to about 50% water by weight, or about 40% to about 45% water by weight. In some embodiments, the water may be DI water.

[0038] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may contain from about 0.1% to about 15% by weight of the high HLB surfactant, or from about 1% to about 14% by weight of the high HLB surfactant, or from about 2% to about 13% by weight of the high HLB surfactant, or from about 3% to about 12% by weight of the high HLB surfactant, or from about 4% to about 11% by weight of the high HLB surfactant, or from about 5% to about 10% by weight of the high HLB surfactant, or from about 6% to about 9% by weight of the high HLB surfactant, or from about 7% to about 8% by weight of the high HLB surfactant. In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may contain about 0.4% by weight of high HLB surfactant, about 1% by weight of high HLB surfactant, about 2% by weight of high HLB surfactant, about 3% by weight of high HLB surfactant, about 4% by weight of high HLB surfactant, about 5% by weight of high HLB surfactant, about 6% by weight of high HLB surfactant, about 7% by weight of high HLB surfactant, about 8% by weight of high HLB surfactant, about 9% by weight of high HLB surfactant, about 10% by weight of high HLB surfactant, about 11% by weight of high HLB surfactant, about 12% by weight of high HLB surfactant, about 13% by weight of high HLB surfactant, about 14% by weight of high HLB surfactant, or about 15% by weight of high HLB surfactant. In some embodiments, the amount of high HLB surfactant may be increased as the ionic strength of the aqueous fluid increases to maintain the stability of the aqueous resin / polymer emulsion.

[0039] In some embodiments, the high HLB surfactant has an HLB value of about 8 to about 18, about 9 to 17, about 10 to 16, about 11 to 15, or about 12 to 14. In some embodiments of the invention herein, the high HLB surfactant has an HLB value of at least about 8, at least about 9, at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, or at least about 17. In some embodiments, the high HLB surfactant has an HLB value of about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, or about 18.

[0040] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may contain from about 1% to about 20% by weight of additives (e.g., waxes, defoamers, rheology modifiers, pigments, fillers), or from about 5% to about 16% by weight of additives, or from about 9% to about 12% by weight of additives.

[0041] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may comprise an industrial fluid or coating having an "extreme" chemical environment of about 1% to about 85% by weight, or an industrial fluid or coating having an "extreme" chemical environment of about 5% to about 80% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 10% to about 75% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 15% to about 70% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 20% to about 65% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 25% to about 60% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 30% to about 55% by weight, an industrial fluid or coating having an "extreme" chemical environment of about 35% to about 50% by weight, or an industrial fluid or coating having an "extreme" chemical environment of about 40% to about 45% by weight.

[0042] In some embodiments, the resulting stabilized aqueous resin / polymer emulsion composition may include an acidic passivating fluid. The acidic passivating fluid may have a pH of less than about 3. A stabilized aqueous resin / polymer emulsion composition according to the present invention may include from about 1% to about 85% by weight of the acidic passivating fluid, or from about 5% to about 80% by weight of the acidic passivating fluid, from about 10% to about 75% by weight of the acidic passivating fluid, from about 15% to about 70% by weight of the acidic passivating fluid, from about 20% to about 65% by weight of the acidic passivating fluid, from about 25% to about 60% by weight of the acidic passivating fluid, from about 30% to about 55% by weight of the acidic passivating fluid, from about 35% to about 50% by weight of the acidic passivating fluid, or from about 40% to about 45% by weight of the acidic passivating fluid.

[0043] In some embodiments, the resulting stabilized aqueous resin emulsion composition may contain about 15% by weight to about 95% by weight of the organic premix, or about 20% by weight to about 90% by weight of the organic premix, or about 25% by weight to about 85% by weight of the organic premix, or about 30% by weight to about 80% by weight of the organic premix, or about 35% by weight to about 75% by weight of the organic premix, or about 40% by weight to about 70% by weight of the organic premix.

[0044] In some embodiments of the method, an organic premix is ​​provided that includes an aqueous fluid and an aqueous resin / emulsion polymer. The organic premix may already contain a high HLB surfactant (e.g., to stabilize the resin / emulsion polymer in an aqueous environment). In some embodiments, the high HLB surfactant is present in the organic premix in an amount that is not sufficient to stabilize the resin / emulsion polymer in the "extreme" chemical environment of a typical industrial fluid and / or coating. In some embodiments, the organic premix may already be provided with a high HLB surfactant to stabilize the resin / emulsion polymer in an aqueous environment, and additional high HLB surfactant may be added to stabilize the resin / emulsion polymer in the "extreme" chemical environment of a typical industrial fluid and / or coating.

[0045] In other embodiments, the organic premix may be provided without the high HLB surfactant, and the high HLB surfactant may be added to the organic premix to obtain an organic premix containing the high HLB surfactant. An industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivator) may then be added to the organic premix containing the high HLB surfactant to obtain the composition of the present invention. The industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivator) may be added stepwise to the organic premix containing the high HLB surfactant to obtain a stabilized resin / emulsion polymer system. The industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivator) may also be added slowly at first until the mixture is stable enough to gradually add the industrial fluid or coating having an "extreme" chemical environment (e.g., an acidic passivator) to the mixture faster and faster.

[0046] In some embodiments, a stabilized resin emulsion in a fluid having an "extreme" chemical environment is provided. The stabilized resin emulsion includes an emulsified aqueous resin / emulsion polymer, an industrial fluid or coating characterized by an extreme chemical environment having high ionic strength and / or high or low pH, a high hydrophobic lipophilic balance (HLB) surfactant, and an acidic passivator.

[0047] In some embodiments, stabilized resin emulsions in fluids having "extreme" chemical environments are provided, comprising an aqueous resin / emulsion polymer, an industrial fluid or coating characterized by an extreme chemical environment having high ionic strength and / or high or low pH, and a high hydrophobic lipophilic balance (HLB) surfactant.

[0048] In some embodiments, stabilized resin emulsions in fluids having "extreme" chemical environments are provided. The stabilized resin emulsions include an "organic premix" that includes an aqueous resin / emulsion polymer and an aqueous fluid, a high hydrophobic lipophilic balance (HLB) surfactant, and an industrial fluid or coating that is characterized by an extreme chemical environment having high ionic strength and / or high or low pH. The "organic premix" may include one or more additives in the aqueous fluid, and the "organic premix" may or may not already include a high HLB surfactant. EXAMPLES

[0049]

[0050] [Table 1]

[0051] Stable formulations according to the embodiments of the invention described herein may include an organic premix including resin / emulsion polymer, water (e.g., DI water), additives (e.g., waxes, defoamers, rheology modifiers, pigments, fillers), and high HLB surfactants. The formulations further include acidic passivation fluids of extreme environments (e.g., industrial fluids having a pH of less than about 3).

[0052] [Table 2-1]

[0053] [Table 2-2]

[0054] [Table 3-1]

[0055] [Table 3-2]

[0056] [Table 3-3]

[0057] [Table 3-4]

[0058] [Table 3-5]

[0059] [Table 3-6]

[0060] [Table 4-1]

[0061] [Table 4-2]

[0062] [Table 5]

[0063] Table 5 summarizes the differential performance between two different steel manufacturers for hot dip galvanized (HDG) and galvalume (four substrates in total). The data includes performance for substrates ranging from low grades (faster failure) to high grades (slower failure). Control formulations 1, 2, and 3 are formulations lacking a stabilization system and are manufactured according to a method that does not utilize the stabilization method of the present invention herein.

[0064] It will be appreciated by those skilled in the art that modifications may be made to the exemplary embodiments shown and described above without departing from the broad concept of the present invention. It will therefore be understood that the present invention is not limited to the exemplary embodiments shown and described, but is intended to encompass modifications within the spirit and scope of the present invention as defined in the claims. For example, certain features of the exemplary embodiments may or may not be part of the claimed invention, and various features of the disclosed embodiments may be combined. Unless otherwise indicated herein, the terms "a", "an" and "the" should be read as meaning "at least one" and not limited to one element.

[0065] It will be understood that at least some of the drawings and descriptions of the present invention have been simplified to focus on elements relevant to a clear understanding of the present invention, and that other elements that are understood by those skilled in the art may form part of the present invention, although they have been omitted for purposes of clarity, and descriptions of such elements are not provided herein, however, because such elements are well known in the art and do not necessarily facilitate a better understanding of the present invention.

[0066] Furthermore, to the extent that the method of the present invention does not depend on the particular order of steps set forth herein, the particular order of steps should not be viewed as a limitation on the claims. Any claims relating to the method of the present invention should not be limited to performing their steps in the order described, and one of ordinary skill in the art can readily appreciate that the steps can be varied and still remain within the spirit and scope of the present invention.

Claims

1. 1. A method for stabilizing an emulsified aqueous resin or polymer in a fluid characterized by an extreme chemical environment having a pH and / or ionic strength that is incompatible with the stability of said emulsified aqueous resin or polymer, said method comprising: combining an organic premix comprising an aqueous fluid and the emulsified water-based resin or polymer with a high hydrophobic lipophilic balance (HLB) surfactant and the fluid characterized by the extreme chemical environment to obtain a composition in which the emulsified water-based resin or polymer is stabilized in a resin / polymer emulsion system comprising the fluid characterized by the extreme chemical environment; A method comprising:

2. 2. The method of claim 1, wherein the incompatible pH and / or ionic strength of the extreme chemical environment for stability is characterized by any ionic strength or any pH that can destabilize the emulsified aqueous resin or polymer.

3. 3. The method according to claim 1 or 2, wherein the fluid characterized by an extreme chemical environment is a coating medium or industrial fluid containing water as the main component.

4. 3. The method of claim 1 or 2, wherein the organic premix comprises industrial film-forming fluids, organic additives that are incompatible in the extreme chemical environment, and / or other coating media used in industrial applications.

5. 3. The method of claim 1 or 2, wherein the resin / polymer emulsion system is stabilized for at least 2 years in a sealed state at ambient conditions, at least 30 days in a sealed oven / heated environment at 60°C, or at least 30 days in a sealed refrigerated system at 5°C.

6. 3. The method of claim 1 or 2, wherein the fluid characterized by the extreme chemical environment includes one or more of Cr(VI) oxide, Cr(III) nitrate, Cr(III) phosphate, any other metal used to improve corrosion resistance, common mineral acids, reducing agents, waxes, antifoaming agents, and any other additives.

7. 3. The method of claim 1 or 2, wherein the extreme chemical environment is further characterized by a pH of less than about 3 or greater than about 11.

8. 3. The method of claim 1, wherein the high HLB surfactant has an HLB value of about 8 to about 18, about 9 to 17, about 10 to 16, about 11 to 15, or about 12 to 14.

9. 3. The method of claim 1 or 2, wherein the high HLB surfactant has an HLB value of at least about 8, at least about 9, at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, or at least about 17.

10. 3. The method of claim 1 or 2, wherein the high HLB surfactant has an HLB value of about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, or about 18.

11. 3. The method of claim 1, wherein the fluid characterized by the extreme chemical environment is an acidic passivator.

12. The method of claim 1 or 2, wherein the composition comprises from about 0.1% to about 15% by weight of a high HLB surfactant.

13. The method of claim 1 or 2, wherein the composition comprises from about 0.5% to about 50% by weight of a resin emulsified in the aqueous fluid.

14. 3. The method of claim 1 or 2, wherein the high HLB surfactant is added to the organic premix to obtain a mixture of the organic premix and the high HLB surfactant.

15. 3. The method of claim 1 or 2, wherein the fluid characterized by the extreme chemical environment is added to the mixture of an organic premix and a high HLB surfactant to obtain the composition.

16. 3. The method of claim 1 or 2, wherein the fluid characterized by the extreme chemical environment is added stepwise to the mixture of organic premix and high HLB surfactant.

17. 3. The method of claim 1 or 2, wherein the fluid characterized by an extreme chemical environment has a high ionic strength and contains electrolytes capable of destabilizing the emulsified aqueous resin or polymer.

18. 18. The method of claim 17, wherein the electrolyte comprises phosphates, nitrates, salts of nitric and phosphoric acids, HEDP, chromium (III), other passivating metals, and combinations thereof.

19. A stabilized resin / polymer emulsion system prepared according to the method of claims 1 or 2.

20. aqueous resin and / or polymer emulsions, a fluid characterized by an extreme chemical environment having a pH and / or ionic strength that is incompatible with the stability of said aqueous resin and / or polymer emulsion; High hydrophobic lipophilic balance (HLB) surfactants, and Acidic passivators, A stabilized resin and / or polymer emulsion comprising:

21. 21. The stabilized resin and / or polymer emulsion of claim 20, wherein the pH and / or ionic strength of the extreme chemical environment that is incompatible with the stability is characterized by any ionic strength or any pH that can destabilize the aqueous resin and / or polymer emulsion.

22. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the fluid characterized by an extreme chemical environment is a coating medium or industrial fluid comprising water as a major component.

23. 22. The stabilized resin and / or polymer emulsion of claims 20 or 21, wherein the aqueous resin and / or polymer emulsion contains industrial film-forming fluids, organic additives that are incompatible in the extreme chemical environment, and / or other coating media used in industrial applications.

24. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the resin / polymer emulsion is stabilized for at least 2 years in a sealed state at ambient conditions, at least 30 days in a sealed oven / heated environment at 60°C, or at least 30 days in a sealed refrigerated system at 5°C.

25. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the fluid characterized by the extreme chemical environment contains one or more of Cr(VI) oxide, Cr(III) nitrate, Cr(III) phosphate, any other metal used to improve corrosion resistance, common mineral acids, reducing agents, waxes, antifoaming agents, and any other additives.

26. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the extreme chemical environment is further characterized by a pH of less than about 3 or greater than about 11.

27. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the high HLB surfactant has an HLB value of about 8 to about 18, about 9 to 17, about 10 to 16, about 11 to 15, or about 12 to 14.

28. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the high HLB surfactant has an HLB value of at least about 8, at least about 9, at least about 10, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, or at least about 17.

29. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the high HLB surfactant has an HLB value of about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, or about 18.

30. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the fluid characterized by the extreme chemical environment is an acidic passivator.

31. 31. The stabilized resin and / or polymer emulsion of claim 30, wherein the acidic passivating agent has a pH of less than about 3.

32. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the composition comprises from about 0.1% to about 15% by weight of the high HLB surfactant, or from about 1% to about 14% by weight of the high HLB surfactant, or from about 2% to about 13% by weight of the high HLB surfactant, or from about 3% to about 12% by weight of the high HLB surfactant, or from about 4% to about 11% by weight of the high HLB surfactant, or from about 5% to about 10% by weight of the high HLB surfactant, or from about 6% to about 9% by weight of the high HLB surfactant, or from about 7% to about 8% by weight of the high HLB surfactant.

33. 33. The stabilized resin and / or polymer emulsion of claim 32, comprising about 0.4 wt% high HLB surfactant, about 1 wt% high HLB surfactant, about 2 wt% high HLB surfactant, about 3 wt% high HLB surfactant, about 4 wt% high HLB surfactant, about 5 wt% high HLB surfactant, about 6 wt% high HLB surfactant, about 7 wt% high HLB surfactant, about 8 wt% high HLB surfactant, about 9 wt% high HLB surfactant, about 10 wt% high HLB surfactant, about 11 wt% high HLB surfactant, about 12 wt% high HLB surfactant, about 13 wt% high HLB surfactant, about 14 wt% high HLB surfactant, or about 15 wt% high HLB surfactant.

34. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the composition comprises from about 0.5% to about 50% by weight of the aqueous resin and / or polymer emulsion, or from about 1% to about 40% by weight of the aqueous resin and / or polymer emulsion, or from about 2% to about 30% by weight of the aqueous resin and / or polymer emulsion, or from about 3% to about 20% by weight of the aqueous resin and / or polymer emulsion, or from about 4% to about 10% by weight of the aqueous resin and / or polymer emulsion, or from about 5% to about 9% by weight of the aqueous resin and / or polymer emulsion, or from about 6% to about 8% by weight of the aqueous resin and / or polymer emulsion.

35. The composition may contain about 0.5% by weight of an aqueous resin and / or polymer emulsion, about 1% by weight of an aqueous resin and / or polymer emulsion, about 2% by weight of an aqueous resin and / or polymer emulsion, about 3% by weight of an aqueous resin and / or polymer emulsion, about 4% by weight of an aqueous resin and / or polymer emulsion, about 5% by weight of an aqueous resin and / or polymer emulsion, about 6% by weight of an aqueous resin and / or polymer emulsion, about 7% by weight of an aqueous resin and / or polymer emulsion, about 8% by weight of an aqueous resin and / or polymer emulsion, 22. The stabilized resin and / or polymer emulsion of claim 20 or 21 comprising an aqueous resin and / or polymer emulsion, about 9% by weight of the aqueous resin and / or polymer emulsion, about 10% by weight of the aqueous resin and / or polymer emulsion, about 20% by weight of the aqueous resin and / or polymer emulsion, about 30% by weight of the aqueous resin and / or polymer emulsion, about 40% by weight of the aqueous resin and / or polymer emulsion, or about 50% by weight of the aqueous resin and / or polymer emulsion.

36. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, wherein the fluid characterized by an extreme chemical environment has a high ionic strength and contains electrolytes capable of destabilizing the aqueous resin and / or polymer emulsion.

37. 37. The stabilized resin and / or polymer emulsion of claim 36, wherein the electrolyte comprises phosphates, nitrates, salts of nitric and phosphoric acids, HEDP, chromium (III), other passivating metals, and combinations thereof.

38. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, comprising about 0% to about 85% water by weight, or about 5% to about 80% water by weight, about 10% to about 75% water by weight, about 15% to about 70% water by weight, about 20% to about 65% water by weight, about 25% to about 60% water by weight, about 30% to about 55% water by weight, about 35% to about 50% water by weight, or about 40% to about 45% water by weight.

39. 39. The stabilized resin and / or polymer emulsion of claim 38, wherein the water is DI water.

40. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, comprising from about 1% to about 20% by weight of the additive, or from about 5% to about 16% by weight of the additive, or from about 9% to about 12% by weight of the additive.

41. 41. The stabilized resin and / or polymer emulsion of claim 40, wherein the additives include one or more of a wax, an antifoaming agent, a rheology modifier, a pigment, and a filler.

42. 22. The stabilized resin and / or polymer emulsion of claim 20 or 21, comprising from about 1% to about 85% by weight of a fluid characterized by an extreme chemical environment, or from about 5% to about 80% by weight of a fluid characterized by an extreme chemical environment, from about 10% to about 75% by weight of a fluid characterized by an extreme chemical environment, from about 15% to about 70% by weight of a fluid characterized by an extreme chemical environment, from about 20% to about 65% by weight of a fluid characterized by an extreme chemical environment, from about 25% to about 60% by weight of a fluid characterized by an extreme chemical environment, from about 30% to about 55% by weight of a fluid characterized by an extreme chemical environment, from about 35% to about 50% by weight of a fluid characterized by an extreme chemical environment, or from about 40% to about 45% by weight of a fluid characterized by an extreme chemical environment.