WO2025216887A1 - High internal phase emulsion - Google Patents

Abstract

The present disclosure provides for a high internal phase emulsion (HIPE) for use with a polyol in forming a polyurethane. The HIPE includes a dispersed phase material; a continuous phase material, where the continuous phase material is immiscible with the dispersed phase material; and a surfactant, where the dispersed phase material has a D50 particle size of 20 nanometer to 125 micrometer 5 weeks after preparing the HIPE. The continuous phase material can comprise water, one or more polyols and combinations thereof, while the dispersed phase material can be selected from the group consisting of an oil, a rosin, a wax and combinations thereof. The surfactant can be selected from the group consisting of a non-ionic alcohol ethoxylate, and combinations thereof. The present disclosure also provides for a polyol mixture that includes the HIPE and a polyol, where the polyol mixture and an isocyanate are used to form a polyurethane.

Description

HIGH INTERNAL PHASE EMULSION Technical Field The present disclosure relates generally to emulsions and, more specifically, to high internal phase emulsions. Background High internal phase emulsions (HIPEs) are emulsions where the dispersed phase (internal phase) constitutes a large volume fraction of the overall system. In traditional emulsions, the dispersed phase is a relatively small fraction of the continuous phase. However, in HIPEs, the dispersed phase volume fraction can be as high as 75-95%, making them unique and versatile materials. Direct preparation of oil-in-polyol emulsions for use in preparing polyurethane foams is, however, difficult due to the mutual solubility of the phases and the lack of a suitable stabilizing agent or agents. Stabilization of different oils like rosins, waxes and castor oil is important in trying to generate different polyurethane foams, including memory foams. Due to their lower interfacial tensions and partial solubility in polyol, the oils in oil-in-polyol emulsions tend to produce large emulsion droplets which are prone to phase separation with time. As such, there is a need in the art for oil-in-polyol emulsions that can remain stable for extended periods of time. Summary The present disclosure provides for an oil-in-polyol high internal phase emulsion (HIPE) that can remain stable for extended periods of time. Such HIPEs of the present disclosure can provide shelf stable oil-in-polyol emulsions, as described herein, for, among other things, use in forming a polyurethane. The HIPE of the present disclosure can also be used to create formulated polyol mixtures for different polyurethane applications such as polyurethane foams as discussed herein. Broadly, the present disclosure first creates a HIPE of oil in a small volume of water/glycol, producing small oil droplets that are further diluted into at least one polyol to create the oil-in-polyol emulsion with improved stability. As discussed herein, different oil-based additives can be used to form stable HIPEs with polyols, where the HIPE can have particle sizes that are smaller than those achieved with direct emulsification. These and other advantages of the present disclosure are discussed herein. For the various embodiments there is provided a high internal phase emulsion (HIPE) for use with a polyol in forming a polyurethane. For the various embodiments, the HIPE includes: (a) 65 to 96 weight percent (wt.%) of a dispersed phase material; (b) 2 to 17.5 wt.% of a continuous phase material, where the continuous phase material is immiscible with the dispersed phase material; and (c) 2 to 17.5 wt.% of a surfactant, where the dispersed phase material has a D50 particle size of 20 nanometer to 125 micrometer and the wt.% values are based on the total weight of the HIPE. For the various embodiments, the dispersed phase material has the D50 particle size of 20 nanometer to 125 micrometer for up to 5 weeks after preparing the HIPE. For the various embodiments, the continuous phase material can comprise water, one or more polyols and combinations thereof. For the various embodiments, the one or more polyols can be selected from the group consisting of a glycerol, a propoxylated glycerine, an ethoxylated glycerine, an alkoxylated glycerine where the alkylene oxide is a mixture of ethylene oxide and propylene oxide, a polyol made from adding ethylene oxide to any of the foregoing polyols and combinations thereof. For the various embodiments, the continuous phase material can be a polyol, where the polyol has an average equivalent weight of 80 to 3000 g/mol. For the various embodiments, the dispersed phase material can be selected from the group consisting of an oil, a rosin, a wax and combinations thereof. For the various embodiments, the oil can be selected from the group consisting of castor oil, mineral oil, silicone oil and combinations thereof. For the various embodiments, the rosin can be selected from the group consisting of a polyterpene resin, a hydrogenated rosin, an esterified rosin and combinations thereof. For the various embodiments, the wax can be selected from the group consisting of a paraffin wax, a polyolefin wax, a polyether wax, a natural wax (animal or vegetable) and combinations thereof. For the various embodiments, the surfactant can be selected from the group consisting of a non-ionic alcohol ethoxylate, a silicone ethoxylate/ether, a poloxomer and combinations thereof. For the various embodiments, the surfactant is present in an amount of 2 to 5 wt.% based on the total weight of the HIPE. Embodiments of the present disclosure also provide for a polyol mixture for use in forming a polyurethane. For the various embodiments, the present disclosure provides for a polyurethane foam composition that comprises a reaction product of an isocyanate component; and an isocyanate-reactive component comprising the HIPE as provided herein. In an additional embodiment, the isocyanate-reactive component can comprise the polyol mixture, as provided herein. Embodiments of the present disclosure also provide for a method of preparing the polyurethane foam composition that comprises combining the isocyanate component and the isocyanate-reactive component to form a mixture and reacting the mixture to form the polyurethane foam composition. For the various embodiments, the polyol mixture can include the HIPE as provided herein and a diluent selected from a polyol, water or a combination thereof to form the polyol mixture. Embodiments of the present disclosure also provide for a polyurethane foam that is formed from the polyol mixture, as provided herein, and an isocyanate. The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. In several places throughout the application, guidance is provided through lists of examples, which examples can be used in various combinations. In each instance, the recited list serves only as a representative group and should not be interpreted as an exclusive list. Detailed Description The present disclosure provides for an oil-in-polyol high internal phase emulsion (HIPE) that can remain stable for extended periods of time. Such HIPEs of the present disclosure can provide shelf stable oil-in-polyol emulsions, as described herein, for, among other things, use in forming a polyurethane. The HIPE of the present disclosure can also be used to create formulated polyol mixtures for different polyurethane applications such as polyurethane foams as discussed herein. Broadly, the present disclosure first creates a HIPE of oil in a small volume of water/glycol, producing small oil droplets that are further diluted into at least one polyol to create the oil-in-polyol emulsion with improved stability. As discussed herein, different oil-based additives can be used to form stable HIPEs with polyols, where the HIPE can have particle sizes that are smaller than those achieved with direct emulsification. These and other advantages of the present disclosure are discussed herein. As used herein, a HIPE is an emulsion where the dispersed phase material occupies a high volume fraction (e.g., >50%) within the continuous phase material, where both the dispersed phase material and the continuous phase material are immiscible. To that end, for the various embodiments the HIPE of the present disclosure includes: (a) 65 to 96 weight percent (wt.%) of a dispersed phase material; (b) 2 to 17.5 wt.% of a continuous phase material, where the continuous phase material is immiscible with the dispersed phase material; and (c) 2 to 17.5 wt.% of a surfactant. Preferably, the HIPE of the present disclosure includes: (a) 75 to 96 wt.% of a dispersed phase material; (b) 2 to 14.5 wt.% of a continuous phase material; and (c) 2 to 10.5 wt.% of a surfactant. More preferably, the HIPE of the present disclosure includes: (a) 85 to 96 wt.% of a dispersed phase material; (b) 2 to 10 wt.% of a continuous phase material; and (c) 2 to 5 wt.% of a surfactant. For the various embodiments, the wt.% values of (a), (b) and (c) can total 100 wt.%. The wt. % values provided herein are based on the total weight of the HIPE. Dispersed phase material For the various embodiments, the HIPE of the present disclosure includes the dispersed phase material having a concentration in the range of (a) 65 to 96 wt.%; preferably (a) 75 to 96 wt.% and more preferably (a) 85 to 96 wt.%, where the wt. % values provided herein are based on the total weight of the HIPE. For the various embodiments, the dispersed phase material can be selected from the group consisting of an oil, a rosin, a wax and combinations thereof. Oil The kind of oil that can be used in the HIPE of the present disclosure is not particularly limited, and examples thereof may be at least one selected from the group consisting of hydrocarbon-based oils including mineral oil, castor oil, isohexadecane, isodecane, undecane, squalane, alpha olefin oligomers, hydrogenated polydecene, hydrogenated polyisobutene, squalane, and ceresin; natural oils including meadowfoam seed oil, soybean oil, canola oil, tallow oil, sunflower seed oil, macadamia seed oil, green tea seed oil, ginger oil, ginseng oil, coconut oil, olive oil, and camellia oil; dimerized unsaturated fatty acids, or “dimer acids”, made from any of the forgoing natural oils with carbon-carbon unsaturated bond(s); dimerized unsaturated fatty diols, or “dimer diols”, made from dimer acids; ester-based oils including cetyl ethylhexanoate, phytosteryl/octyldodecyllauroyl glutamate, isostearyl isostearate, methyl heptyl isostearate, dicaprylyl carbonate, and isopropyl palmitate; ether-based oils including dicaprylyl ether; and silicone oils including dimethicone, cyclopentasiloxane, cyclohexasiloxane, phenyltrimethicone, trisiloxane, and methyltrimethicone. Preferably, combinations of oil, as provided herein, are miscible. In particular, for the various embodiments, the oil can be selected from the group consisting of castor oil, mineral oil, silicone oil and combinations thereof. Rosin For the various embodiments, a “rosin” refers to the resinous constituent of oleoresin exuded by various plant species, mainly conifers such as pine, after removal of essential oils. “Rosin” includes, for example, wood rosin, gum rosin and tall oil rosin. The main components of rosin are 20-carbon, tricyclic, aliphatic carboxylic acids that have two or more carbon-carbon double bonds, including one or more of abietic acid, neoabietic acid, palustric acid, levopimaric acid, dihydroabietic acid, pimaric acid, isopimaric acid and sandaracopimaric acids. The rosin can also include terpenes, including polyterpenes. A polyterpene may be a polymer of one or more of α-pinene, β-pinene and d-limonene. For the various embodiments, the rosin can be selected from the group consisting of a polyterpene resin, a hydrogenated rosin, an esterified rosin and combinations thereof. A hydrogenated rosin is a rosin as just described in which one or more of the carbon-carbon double bonds of at least some of the constituent carboxylic acids have been hydrogenated. An esterified rosin is a rosin as described above in which some or all of the carboxylic acid groups of the constituent carboxylic acids have been converted to ester groups, typically by reaction with an alcohol compound that has one or more alcohol groups. The ester may be, for example, an alkanol ester such as a methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl or t- butyl ester. The ester may be a polyester ester of such carboxylic acids and a polyol having up to 6 carbon atoms such as glycerin, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- propane diol (i.e., propylene glycol), dipropylene glycol, 1,3-propane diol, 1,2-butane diol, 1,4- butane diol, 1,6-hexane diol, trimethylolpropane, trimethylolethane and the like. For the various embodiments, the rosin can be selected from the group consisting of a polyterpene resin, a hydrogenated rosin, an esterified rosin and combinations thereof. Wax For the various embodiments, waxes are generally defined as organic materials that are solids at room temperature, but melt or soften without decomposing at temperatures above about 40 °C. Waxes may be branched or linear, and may have low crystallinity or high crystallinity. A wax with “low” crystallinity has a crystallinity below about 20%, preferably from about 9% to about 20% crystallinity. A wax with “moderate” crystallinity has a crystallinity of from about 20% to about 40%. A wax with “high” crystallinity has a crystallinity above 40%, preferably from about 70% to about 95%. In preferred embodiments of the invention, the crystallinity of the wax is from about 20% to about 90%. Waxes also have relatively low polarity. Their weight average molecular weights may range from about 180 to about 900 and have melting points ranging from about –6 °C to about 100 °C. Preferred waxes have a weight average molecular weight of from about 220 to about 850, more preferably from about 250 to about 550, and most preferably less than 400. Useful waxes also have a preferred polydispersity (Pd) index of from about 1.0 to about 4.0, more preferably from about 1.0 to about 2.5 and most preferably from about 1.0 to about 1.5. For the various embodiments, the number of carbon atoms per molecule of the wax, as provided herein, can be from 13 to 60. The friability of a wax, its affinity to be reduced in particle size by mechanical forces, increases with higher crystallinity and decreases with increasing density and molecular weight of a wax. Oxidized waxes tend to create higher dispersion viscosities in water (e.g., about 300 centipoise (cps) to about 400 cps at room temperature (about 23 °C)) than non-oxidized waxes (about 30 cps to about 150 cps at room temperature) in an aqueous dispersion. The melt viscosity of waxes above their melting point is typically low. In preferred embodiments, the waxes have a melt viscosity at 140 °C of from about 5 cps to about 10,000 cps, more preferably from about 5 cps to about 100 cps and most preferably from about 5 cps to about 80 cps. Viscosity values are measured using techniques that are well known in the art and may be measured, for example, using capillary, rotational or moving body rheometers. A preferred measurement tool is a Brookfield rotational viscometer, commercially available from Brookfield Engineering Laboratories, Inc. of Middleboro, Mass. Suitable waxes include both natural and synthetic waxes. Suitable waxes non-exclusively include animal waxes, such as beeswax, Chinese wax, shellac wax, spermaceti, lard, and wool wax (lanolin); vegetable waxes, such as bayberry wax, carnauba wax, castor wax, esparto wax, Japan wax, Jojoba oil wax, ouricury wax, rice bran wax and soy wax; mineral waxes, such as ceresin waxes, montan wax, ozocerite wax and peat waxes; petroleum waxes, such as paraffin wax and microcrystalline waxes; and synthetic waxes, including polyolefin waxes, including polyethylene and polypropylene waxes, wax grade polytetrafluoroethylene waxes (PTFE wax- like grades), polyether waxes such as poly(ethylene glycol) wax, poly(ethylene oxide) wax, Fischer-Tropsch waxes, stearamide waxes (including ethylene bis-stearamide waxes), polymerized α-olefin waxes, substituted amide waxes (e.g. esterified or saponified substituted amide waxes) and other chemically modified waxes, such as PTFE-modified polyethylene wax as well as combinations of the above. Of these, the preferred waxes include paraffin waxes, micro-crystalline waxes, Fischer-Tropsch waxes, branched and linear polyethylene waxes, polypropylene waxes, carnauba waxes, ethylene bis-stearamide (EBS) waxes and combinations thereof. For the various embodiments, the wax can be selected from the group consisting of a paraffin wax, a polyether wax, a polyolefin wax, a natural wax (animal or vegetable) and combinations thereof. Continuous phase material For the various embodiments, the HIPE of the present disclosure includes a continuous phase material having a concentration in the range of (b) 2 to 17.5 wt.%, preferably (b) 2 to 14.5 wt.%, and more preferably (b) 2 to 10 wt.%, where the wt. % values provided herein are based on the total weight of the HIPE. For the various embodiments, the continuous phase material can comprise water, one or more polyols and combinations thereof. In one embodiment, the continuous phase material can be just water. In an additional embodiment, the continuous phase material can be just water and one or more polyols as provided herein. For the various embodiments, the one or more polyols can be selected from the group consisting of a glycerol, a propoxylated glycerine, an ethoxylated glycerine, an alkoxylated glycerine where the alkylene oxide is a mixture of ethylene oxide and propylene oxide, a polyol made from adding ethylene oxide to any of the foregoing polyols and combinations thereof. For the various embodiments, the one or more polyols can have an equivalent weight of 80 to 3000 g/mol. Preferably, the one or more polyols can have an average equivalent weight of 120 to 2000 g/mol. For the various embodiments, the one or more polyols can have an average hydroxyl functionality of 2 to 8. Examples of suitable glycols can include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, triethylene glycol and combinations thereof. Examples of suitable propoxylated glycerines can include those having a degree of propoxylation in the range of on average 2.5 to 154 propylene oxide units added to the glycerol. Examples of commercially available propoxylated glycerines suitable for the present disclosure can include VORANOL™ Polyols from The Dow Chemical Company, as well as POLY-G® 55-56 (Monument Chemical); propoxyglycerin PPG-400; Pluracol® GP-430 (BASF); Sovermol® 815 (Covestro); Jeffox® PG-56 (Huntsman Corporation); NIAX® PCP 0401 (Momentive Performance Materials); Voranol™ CP 420 (DOW); Baytec® PAG 35 (Covestro); Kosmos® 27-280 (Stepan Company); JEFFOL® PG-56P (Huntsman Corporation); Daltocast® P-210 (Nagase America Corporation); Adeka Polyol GP-350 (Adeka Corporation); DYTEK® DPG-250 (Invista); Niax® LP-204 (Momentive Performance Materials), among others. Surfactant For the various embodiments, the HIPE of the present disclosure can be stabilized by a stabilizing amount of a surfactant. The concentration of the surfactant is preferably not less than 1 wt.%, more preferably not less than 2 wt.%, and preferably not more than 20 wt.%, more preferably not more than 17.5 wt.%, based on the total weight of the HIPE. For examples, as discussed herein the HIPE of the present disclosure can include (c) 2 to 17.5 wt.% of the surfactant; preferably, (c) 2 to 10.5 wt.% of the surfactant; and more preferably (c) 2 to 5 wt.% of the surfactant, where the wt. % values are based on the total weight of the HIPE. For the various embodiments, the surfactant is non-ionic. For the various embodiments, the surfactant can be selected from the group consisting of a non-ionic alcohol ethoxylate, a silicone ethoxylate/ether, a poloxomer, and combinations thereof. Preferably, the surfactant of the present disclosure is a non-ionic alcohol ethoxylate. Examples of preferable non-ionic alcohol ethoxylates can include, but are not limited to, non-ionic secondary alcohol ethoxylates, as provided herein. Examples of non-ionic alcohol ethoxylates, including non-ionic secondary alcohol ethoxylates, can include lauryl alcohol ethoxylate, cetyl alcohol ethoxylate, stearyl alcohol ethoxylate, isotridecyl alcohol ethoxylate, behenyl alcohol ethoxylate, octylphenol Ethoxylate, tallow alcohol ethoxylate, dodecyl alcohol ethoxylate, hexadecyl alcohol ethoxylate, isodecyl alcohol ethoxylate, oleyl alcohol ethoxylate, coco alcohol ethoxylate, glyceryl laurate ethoxylate, isotetradecyl alcohol ethoxylate, and isotetrapropenyl alcohol ethoxylate, among others. Examples of non-ionic surfactants suitable for stabilizing the HIPE of the present disclosure can further include polyethylene glycol fatty acid mono- and diesters (such as PEG-8 laurate, PEG- 10 oleate, PEG-8 dioleate, and PEG-12 distearate), polyethylene glycol glycerol fatty acid esters (such as PEG-40 glyceryl laurate and PEG-20 glyceryl stearate), alcohol-oil transesterification products (such as PEG-35 castor oil, PEG-25 trioleate, and PEG-60 corn glycerides), polyglycerized fatty acids (such as polyglyceryl-2-oleate and polyglyceryl-10 trioleate), propylene glycol fatty acid esters (such as propylene glycol monolaurate), mono- and diglycerides (such as glyceryl monooleate and glyceryl laurate), sterol and sterol derivatives (such as cholesterol), sorbitan fatty acid esters and polyethylene glycol sorbitan fatty acid esters (such as sorbitan monolaurate and PEG-20 sorbitan monolaurate), polyethylene glycol alkyl ethers (such as PEG-3 oleyl ether and PEG-20 stearyl ether), sugar esters (such as sucrose monopalmitate and sucrose monolaurate), polyethylene glycol alkyl phenols (such as PEG-10- 100 nonyl phenol, and PEG-15-100 octyl phenol ether), polyoxyethylene-polyoxypropylene block copolymers and polyoxyethylene-polyoxypropylene-polyoxyethylene block copolymers (such as poloxamer 108, poloxamer 182, and Pluronic F127), and lower alcohol fatty acid esters (such as ethyl oleatea and isopropyl myristate). Examples of silicone ethoxylate/ether surfactants suitable for stabilizing the HIPE of the present disclosure can include those provided in U.S. Pat. No.5,830,907, which is incorporated herein by reference in its entirety. Specific examples of silicone ethoxylate/ether surfactants can include Forming the HIPE The HIPE emulsion can be prepared by a variety of methods, including batch and continuous methods well known in the art. In a preferred continuous method (described generally by Pate et al. in U.S. Pat. No.5,539,021, column 3, line 15 to column 6, line 27, which passage is incorporated herein by reference) a stream containing the dispersed phase material is flowed through a first conduit and merged continuously with a stream of the continuous phase material disperse emollient phase that is flowed through a second conduit. The streams are merged into a disperser in the presence of a stabilizing amount of the surfactant. The surfactant can be added to either stream, or as a separate stream, but is preferably added to the stream containing the dispersed phase material. The rates of the streams are adjusted within the HIPE emulsion region so that particle size and polydispersity of the emulsion are optimized for the particular application. Preferably, the rates of the streams are adjusted so as to produce a HIPE emulsion having a 65 wt.% to 96 wt.% of the dispersed phase material. Alternatively, the HIPE emulsion of the present disclosure can be formed under shear to disperse the dispersed phase material into the continuous phase material. The mixing step can be performed using a wide variety of mixing devices including stirrers, static mixers, pin mixers and the like. For the various embodiments, the dispersed phase material can be heated above its softening point if it is a room temperature solid. It is often advantageous to heat the dispersed phase material, even when it is a room temperature liquid, to reduce its viscosity and thus facilitate its dispersal into the continuous phase material. The dispersed phase material may be heated, for example, to a temperature of 40 to 100 °C, preferably 40 to 70 °C, prior to forming the HIPE and mixed with the other ingredients while at such a temperature. Mixing speed and duration are adjusted so that particle size and polydispersity of the emulsion are optimized for the particular application. In general, the HLB, or hydrophilic-lipophilic balance, of a surfactant is the measure of the degree of hydrophilicity or lipophilicity of that surfactant determined by calculating a percentage of molecular weights for hydrophilic and lipophilic portions of the structure specifically. An HLB conducive to the formation of an oil-in-water emulsion is preferred, where a combination of emulsifiers with HLBs ranging from 0 to 20 can be employed such that total HLB is larger than approximately 7. The surfactant can be added to either phase but is preferably added to the dispersed phase material. The median particle size (D50) of the dispersed phase of the HIPE emulsion is application dependent, where the D50 particle size can be in a range of 20 nanometer (nm) to 125 micrometer (µm), as discussed herein. For the various embodiments, the median particle size (D50) of the dispersed phase of the HIPE emulsion can be in a range of 20 nm to 125 µm 5 weeks after preparing the HIPE. Polyol Mixture of HIPE and Polyol Embodiments of the present disclosure further include a polyol mixture for use in forming a polyurethane, as discussed herein. For the various embodiments, the polyol mixture can include the HIPE as provided herein and a diluent selected from a polyol, water or a combination thereof. For the various embodiments, the polyol used with the HIPE can be any of those provided and discussed above for the formation of the HIPE. For the various embodiments, the HIPE can be diluted with the diluent to form the polyol mixture in a ratio from 1:1 to 1:6 HIPE:diluent by weight. As discussed above, the diluent can be a combination of polyol and water, where suitable ratios of such a mixture can be in the range of 0.5:10 to 10:0.5 polyol:water. Forming the polyol mixture can take place a room temperature and atmosphere pressure, where combining and mixing the diluent with the HIPE can take place in a single step or incrementally so as not to destabilize the droplet interface and induce coalescence as the diluent is introduced to the HIPE. Polyurethane Formation with HIPE Embodiments of the present disclosure also provide for a polyurethane composition, including a polyurethane foam composition, that includes the HIPE and/or the polyol mixture as provided herein. For example, the present disclosure provides for a polyurethane foam composition that comprises a reaction product of an isocyanate component and an isocyanate- reactive component comprising the HIPE and/or the polyol mixture as provided herein. Embodiments of the present disclosure also provide for a method of preparing the polyurethane foam composition that comprises combining the isocyanate component and the isocyanate- reactive component to form a mixture and reacting the mixture to form the polyurethane foam composition. For the various embodiments, the polyurethane (e.g., a polyurethane foam) can be obtained by mixing at least: the isocyanate component (“A-side”) and the isocyanate-reactive component (“B-side” or “polyol side” or “polyol blend”), where the isocyanate-reactive component includes the HIPE and/or the polyol mixture of the present disclosure. In forming the polyurethane, the isocyanate component, isocyanate-reactive components, and optional components and/or additives (if needed and as discussed herein) are mixed, creating a curing reaction mixture that is processed to form the polyurethane foam, which can be provided as a polyurethane article or composite. Where the isocyanate component and the isocyanate- reactive component are combined in the presence of blowing agents, aqueous fluids and/or blowing catalysts, the curing reaction mixture that generates a polyurethane foam that can have a density ranging from 0.05 g/mL to 2.5 g/mL measured using ASTM D792 upon cure. Other examples of forming a polyurethane foam are also possible based on the present disclosure. For the various embodiments, the isocyanate component and the isocyanate-reactive component can be used in forming a polyurethane foam. Generally, polyurethane foam compositions are prepared by combining an isocyanate component and the isocyanate-reactive component to form a mixture; and reacting the mixture to form the polyurethane composition or foam. For example, the polyurethane foam composition can be formed by combining the HIPE and/or the polyol mixture of the present disclosure, which can further include one or more of a blowing agent, a catalyst, a surfactant, among other known components useful in forming a polyurethane foam, with the isocyanate component to form a reaction mixture that reacts and cures to form the foam. Examples of useful isocyanates can include polyisocyanates that include m-phenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6- diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene-1,5-diisocyanate, 1,3- and/or 1,4-bis(isocyanatomethyl)cyclohexane (including cis- and/or trans isomers), methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4′- diisocyanate, diphenylmethane-2,4′-diisocyanate, hydrogenated diphenylmethane-4,4′- diisocyanate, hydrogenated diphenylmethane-2,4′-diisocyanate, 4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenyl diisocyanate, 3,3′-dimethyl-4-4′-biphenyl diisocyanate, 3,3′- dimethyldiphenyl methane-4,4′-diisocyanate, 4,4′,4″-triphenyl methane triisocyanate, polymethylene polyphenylisocyanate (PMDI), toluene-2,4,6-triisocyanate and 4,4′- dimethyldiphenylmethane-2,2′,5,5′-tetraisocyanate, and mixtures thereof. Preferably the polyisocyanate is diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, PMDI, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate or mixtures thereof. Diphenylmethane-4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate and mixtures thereof are generically referred to as MDI, and all can be used. “Polymeric MDI”, which is a mixture of PMDI and MDI, can be used, in particular a polymeric MDI that contains at most 70% by weight MDI, especially 50 to 70% by weight MDI. Toluene-2,4-diisocyanate, toluene-2,6- diisocyanate and mixtures thereof are generically referred to as TDI, and all can be used. Polymeric MDI is particularly preferred. The reaction mixture is preferably formed by combining the HIPE and/or the polyol mixture having any additional components with the isocyanate using a mixing vessel, inline pin- mixer with rotor/stator, or other apparatus that creates an intimate mixture of these components. The reaction mixture is then foamed and cured. The process does not necessarily require special foaming conditions; therefore, foaming conditions and equipment described in the art for making the polyurethane foam are entirely suitable. In general, the isocyanate will react spontaneously with the polyol mixture even at room temperature (22 °C), especially in the presence of catalyst that promotes the urethane reaction known in the literature, such as metal carboxylates and tertiary amines. If necessary, heat can be applied to the reaction mixture to speed the curing reaction. This can be done by heating some or all of the ingredients prior to combining them, by applying heat to the reaction mixture, or by heating the mold (typically metal mold) that the reaction mixture is dispensed into, or some combination of each. For the various embodiments, the curing reaction mixture can be mixed at a temperature of from 10 to 90 °C, preferably from 20 to 60 °C and in particular from 20 to 50 °C. Reaction temperature for the curing reaction mixture once dispensed can be from 15 to 110 °C, preferably from 25 to 70 °C and in particular from 25 to 60 °C. Curing is continued until the reaction mixture has expanded and cured sufficiently to form a stable foam. The polyurethane foam can be formed in an open (free-rise or slabstock) or closed mold process, as are known in the art, and can done under atmospheric or vacuum conditions. As is known in the art, a polyurethane foam can be formed with one or more of the above identified components included in the composition of the present disclosure with a desired stoichiometric index of the isocyanate to the composition of the present disclosure. For the various embodiments, the stoichiometric index of the isocyanate component to the isocyanate reactive groups (e.g., hydroxyl groups) in the HIPE and/or polyol mixture of the present disclosure can be 0.5 to 3.0. For the various embodiments, the isocyanate component can have an isocyanate equivalent weight 130 g/eq to 200 g/eq. All individual values and subranges from 130 g/eq to 200 g/eq are included herein; for example, the isocyanate component can have an isocyanate equivalent weight from a lower limit of 130 or 132 g/eq to an upper limit of 200, 198 or 196 g/eq. For the various embodiments, the polyurethane foam composition of the present disclosure can further include up to 25 wt.% of one or more additives selected from the group consisting of a filler (e.g., micron and/or nano sized), silica, water, a surfactant (e.g., a silicone polyether), a catalysts (e.g., an amine-based, metal-based, blocked, delayed action, and others), a plasticizer, a chemical blowing agent other than water, a physical blowing agent (e.g., a gas or low boiling point liquid such as CFC, HFC, HFO, various alkanes, acetone, other volatile chemicals) and combinations thereof. Additional additives can also include pigments, colorants, flame retardants as are known in art, crosslinkers, chain extenders, antioxidants, bioretardant agents, and combinations thereof, among others. Examples All components purchased from commercial vendors and used as received unless otherwise noted. Amounts provided for the compositions of the Examples (EX) and Comparative Examples (CE) are in weight percent (wt.%) based on the total weight of the composition, unless otherwise noted. The components used in forming the EX and CE are provided in Table 1. Test methods for the following are provided at the end of the Examples section. Table 1 - Materials/Ingredients Ingredient Type Materials Composition Material Supplier n al al al Product Formulations All high internal phase emulsions (HIPEs) formulated Examples (EX) and Comparative Examples (CE) totaled 15 gram (g). When diluted into glycol, each diluted EX or CE totaled to 5 g (1 g of HIPE and 4 g of glycol). Table 2 – EX and CE HIPEs Dispersed DP Total Surf. Surf. Surf.1: Surf.1 Surf.2 Cont. CP Phase (DP) DP Mass % mas Surf.2 mass Mass Phase Mass % [g] s [g] ratio [g] [g] (CP) [g] C^{E A} 30* Castor oil 4.50 5 0.75 50-50 0.375 0.375 water 9.75 C^{E B} 50* Castor oil 7.50 5 0.75 50-50 0.375 0.375 water 6.75 E^{X 1} 96 Castor oil 14.40 2 0.3 50-50 0.15 0.15 water 0.30 E^{X 2} 93 Castor oil 13.95 5 0.75 100-0 0.75 0 water 0.30 EX 3 93 Castor oil 13.95 5 0.75 75-25 0.56 0.19 water 0.30 EX 4 93 Castor oil 13.95 5 0.75 50-50 0.375 0.375 water 0.30 E^{X 5} 93 Castor oil 13.95 5 0.75 25-75 0.19 0.56 water 0.30 E^{X 6} 93 Castor oil 13.95 5 0.75 0-100 0 0.75 water 0.30 E^{X 7} 93 Castor oil 13.95 3.5 0.53 50-50 0.26 0.26 water 0.53 E^{X 8} 90 Castor oil 13.50 5 0.75 100-0 0.75 0 water 0.75 E^{X 9} 90 Castor oil 13.50 5 0.75 75-25 0.56 0.19 water 0.75 E^{X 10} 90 Castor oil 13.50 5 0.75 50-50 0.375 0.375 water 0.75 E^{X 11} 90 Castor oil 13.50 5 0.75 25-75 0.19 0.56 water 0.75 E^{X 12} 90 Castor oil 13.50 5 0.75 0-100 0 0.75 water 0.75 C^{E C} 90 Castor oil 13.50 1 0.15 50-50 0.075 0.075 water 1.35 E^{X 13} 90 Castor oil 13.50 3 0.45 50-50 0.225 0.225 water 1.05 EX 14 90 Castor oil 13.50 7 1.05 50-50 0.525 0.525 water 0.45 E^{X 15} 90 Castor oil 13.50 9 1.35 50-50 0.675 0.675 water 0.15 C^{E D} 90 Castor oil 13.50 5 0.75 100-0 0.75 0 glycol 0.75 E^{X 16} 90 Castor oil 13.50 5 0.75 75-25 0.56 0.19 glycol 0.75 E^{X 17} 90 Castor oil 13.50 5 0.75 50-50 0.375 0.375 glycol 0.75 E^{X 18} 90 Castor oil 13.50 5 0.75 25-75 0.19 0.56 glycol 0.75 E^{X 19} 90 Castor oil 13.50 5 0.75 0-100 0 0.75 glycol 0.75 C^{E E} 90 Castor oil 13.50 1 0.15 50-50 0.075 0.075 glycol 1.35 E^{X 20} 90 Castor oil 13.50 3 0.45 50-50 0.225 0.225 glycol 1.05 E^{X 21} 90 Castor oil 13.50 7 1.05 50-50 0.525 0.525 glycol 0.45 E^{X 22} 90 Castor oil 13.50 9 1.35 50-50 0.675 0.675 glycol 0.15 EX 23 90 Paraffin wax 13.50 5 0.75 100-0 0.75 0 glycol 0.75 EX 24 90 Paraffin wax 13.50 5 0.75 75-25 0.56 0.19 glycol 0.75 EX 25 90 Paraffin wax 13.50 5 0.75 50-50 0.375 0.375 glycol 0.75 EX 26 90 Paraffin wax 13.50 5 0.75 25-75 0.19 0.56 glycol 0.75 EX 27 90 Paraffin wax 13.50 5 0.75 0-100 0 0.75 glycol 0.75 R _{i 1 1 1 t 7} mixed at 500 rpm for 15 seconds. To not destabilize the droplet interface and induce coalescence the polyol was introduced to the HIPE in 0.5 mL increments and gently incorporated with tongue depressors. The final, diluted sample totaled 5 mL of material, containing both the HIPE and glycol. Thus, only a small amount glycol was introduced at a time. When a 1:4 HIPE:polyol dilution was achieved, sample was vortex mixed for about 30 seconds at 2500 rpm. Tested Property Results Legend for data presented in this section: Letter ‘G’ denotes droplet diameter which is less than 125 µm by Week 5 Letter ‘R’ denotes droplet diameter which is either greater than 125 µm or unstable, by Week 5 Table 3 - Control Experiments: CE G 50 Castor oil 5 50-50 water 213.3 366.8 R CE H 90 Castor oil 1 50-50 water 123.7 Not stable R CE I 90 Castor oil 1 50-50 glycol 153.6 441.1 R CE J 90 Castor oil 5 100-0 glycol Not Not stable stable R Samples are identified as comparative examples under the following conditions: • Less than a 75% Dispersed Phase Percentage (as is typical of traditional emulsions and not the HIPE approach of the present disclosure) • Samples containing small amounts of surfactant (1% surfactant loading) • Or low HLB surfactant usage (100-0) in glycol with castor oil (appropriate surfactant package not identified and initial emulsion on Day 0 is not stable) Table 4 - Data from HIPE of Present Disclosure Dispersed Dispersed Surfactant Day 0 Surfactant 1- Continuous droplet Wee Droplet Phase Phase k 5 droplet size Percentag Phase diameter Percentage material e Surfactant materia size (µm) 2 ratio l (µm) summary EX 30 96 Castor oil 2 50-50 water 3.67 5.83 G EX 31 93 Castor oil 5 100-0 water 30.08 38.81 G EX 32 93 Castor oil 5 75-25 water 9.52 10.3 G EX 33 93 Castor oil 5 50-50 water 2.38 7.76 G EX 34 93 Castor oil 5 25-75 water 8.81 7.87 G EX 35 93 Castor oil 5 0-100 water 18.71 27.03 G EX 36 93 Castor oil 3.5 50-50 water 4.63 6.31 G EX 37 90 Castor oil 5 100-0 water 138.7 122.5 G EX 38 90 Castor oil 5 75-25 water 52.81 53.17 G EX 39 90 Castor oil 5 50-50 water 5.43 4.88 G EX 40 90 Castor oil 5 25-75 water 31.14 29.29 G EX 41 90 Castor oil 5 0-100 water 116.1 99.44 G EX 42 90 Castor oil 3 50-50 water 71.58 83.11 G EX 43 90 Castor oil 7 50-50 water 7.41 8.23 G EX 44 90 Castor oil 9 50-50 water 6.68 6.17 G EX 45 90 Castor oil 5 75-25 glycol 68.12 122.2 G EX 46 90 Castor oil 5 50-50 glycol 43.95 51.95 G EX 47 90 Castor oil 5 25-75 glycol 24.29 31.14 G EX 48 90 Castor oil 5 0-100 glycol 1.23 9.29 G EX 49 90 Castor oil 3 50-50 glycol 83.72 84.19 G EX 50 90 Castor oil 7 50-50 glycol 23.44 28.08 G EX 51 90 Castor oil 9 50-50 glycol 20.9 21.54 G EX 52 90 Paraffin wax 5 100-0 glycol 70.9 102.3 G EX 53 90 Paraffin wax 5 75-25 glycol 36.21 51.66 G EX 54 90 Paraffin wax 5 50-50 glycol 29.66 43.37 G EX 55 90 Paraffin wax 5 25-75 glycol 9.36 16.2 G EX Par 56 90 affin wax 5 0-100 glycol 10.05 14.58 G Data Analysis CE F – CE J in Table 3 include samples formed as ‘traditional emulsions,’ with oil loading levels less than 75%, which is the minimum required for a HIPE. EX 30 – EX 56 in Table 4 were formed under HIPE conditions. The CE showcase changing droplet size via ripening, with sample emulsion diameter either increasing by more than 200 µm or becoming altogether unstable in all cases over the course of several weeks. All EX made via a HIPE approach do not exhibit an average droplet size greater than 125 µm by Week 5, demonstrating a comparatively greater stability than in comparison to the CEs. Measurement Information A Beckman Coulter LS 13-320 Laser Diffraction-Particle Size Analyzer using a small volume sample cell holder was used for all droplet size measurements. Samples were prepared by adding 4-5 droplets of the HIPE diluted into glycol (1:4 dilution) into the sample cell containing the same glycol and then subsequently transferring to the instrument for characterization. Droplet sizes are reported as volume mean average. A specific method was designed on the instrument using the refractive index of the glycol to give as accurate a droplet size measurement as possible. The refractive index was determined by an Atago Refractometer (model: RX-7000 alpha).

Table 3 - Control Experiments: Samples are identified as comparative examples under the following conditions:

• Less than a 75% Dispersed Phase Percentage (as is typical of traditional emulsions and not the HIPE approach of the present disclosure)

• Samples containing small amounts of surfactant (1% surfactant loading)

• Or low HLB surfactant usage (100-0) in glycol with castor oil (appropriate surfactant package not identified and initial emulsion on Day 0 is not stable)

Table 4 - Data from HIPE of Present Disclosure

Data Analysis

CE F - CE J in Table 3 include samples formed as ‘traditional emulsions,’ with oil loading levels less than 75%, which is the minimum required for a HIPE. EX 30 - EX 56 in Table 4 were formed under HIPE conditions. The CE showcase changing droplet size via ripening, with sample emulsion diameter either increasing by more than 200 pm or becoming altogether unstable in all cases over the course of several weeks. All EX made via a HIPE approach do not exhibit an average droplet size greater than 125 pm by Week 5, demonstrating a comparatively greater stability than in comparison to the CEs.

Measurement Information

A Beckman Coulter LS 13-320 Laser Diffraction-Particle Size Analyzer using a small volume sample cell holder was used for all droplet size measurements. Samples were prepared by adding 4-5 droplets of the HIPE diluted into glycol (1:4 dilution) into the sample cell containing the same glycol and then subsequently transferring to the instrument for characterization. Droplet sizes are reported as volume mean average. A specific method was designed on the instrument using the refractive index of the glycol to give as accurate a droplet size measurement as possible. The refractive index was determined by an Atago Refractometer (model: RX-7000 alpha).

Claims

What is Claimed is: 1. A high internal phase emulsion (HIPE) for use with a polyol in forming a polyurethane, the HIPE comprising: (a) 65 to 96 weight percent (wt.%) of a dispersed phase material; (b) 2 to 17.5 wt.% of a continuous phase material, wherein the continuous phase material is immiscible with the dispersed phase material; and (c) 2 to 17.5 wt.% of a surfactant, wherein the dispersed phase material has a D50 particle size of 20 nanometer to 125 micrometer and the wt.% values are based on the total weight of the HIPE.

2. The HIPE of claim 1, wherein the continuous phase material comprises water, one or more polyols and combinations thereof.

3. The HIPE of claim 2, wherein the one or more polyols is selected from the group consisting of a glycerol, a propoxylated glycerine, an ethoxylated glycerine, an alkoxylated glycerine where the alkylene oxide is a mixture of ethylene oxide and propylene oxide, a polyol made from adding ethylene oxide to any of the foregoing polyols and combinations thereof.

4. The HIPE of any one of claims 1-3, wherein the continuous phase material is a polyol, wherein the polyol has an average equivalent weight of 80 to 3000 g/mol.

5. The HIPE of any one of claims 1-4, wherein the dispersed phase material is selected from the group consisting of an oil, a rosin, a wax and combinations thereof.

6. The HIPE of claim 5, wherein the oil is selected from the group consisting of castor oil, mineral oil, silicone oil and combinations thereof.

7. The HIPE of claim 5, wherein the rosin is selected from the group consisting of a polyterpene resin, a hydrogenated rosin, an esterified rosin and combinations thereof.

8. The HIPE of claim 5, wherein the wax is selected from the group consisting of a paraffin wax, a polyolefin wax, a polyether wax, a natural wax and combinations thereof. Page 18 of 20

9. The HIPE of any one of claims 1-8, wherein the surfactant is selected from the group consisting of a non-ionic alcohol ethoxylate, a silicone ethoxylate/ether, a poloxomer, and combinations thereof.

10. The HIPE of any one of claims 1-9, wherein the surfactant is present in an amount of 2 to 5 wt.% based on the total weight of the HIPE.

11. A polyol mixture for use in forming a polyurethane, comprising: the HIPE of any one of claims 1-10: and a diluent selected from a polyol, water or a combination thereof to form the polyol mixture.

12. A polyurethane foam composition, comprising a reaction product of: an isocyanate component; and an isocyanate-reactive component comprising the HIPE of any one of claims 1-10.

13. The polyurethane foam composition of claim 12, wherein the isocyanate-reactive component comprises the polyol mixture of claim 11.

14. A method of preparing the polyurethane foam composition of any one of claims 12-13, comprising: combining the isocyanate component and the isocyanate-reactive component to form a mixture; and reacting the mixture to form the polyurethane foam composition. Page 19 of 20