Emulsifier for solubilizing polar solvents in oils and polyols

Abstract

The present disclosure is directed to compositions having lecithin, a plasticizer, and an emulsifier. The composition may be used solubilize polar solvents in non-polar liquids. Methods of producing and using the compositions disclosed herein are also disclosed.

Claims

1. A method of solubilizing a polar solvent in a non-polar liquid, the method comprising: mixing lecithin with a plasticizer and a co-surfactant, thus producing an emulsifier blend; and mixing the non-polar liquid comprising a biobased polyol and a petroleum polyol with the emulsifier blend and the polar solvent, such that the emulsifier blend stabilizes the combination of the biobased polyol with the petroleum based polyol.

2. The method of claim 1, wherein the polar solvent is glycerol.

3. The method of claim 1, wherein the polar solvent is propylene glycol.

Description

DETAILED DESCRIPTION

(1) In the present application, including the claims, other than in the operating examples or where otherwise indicated, all numbers expressing quantities or characteristics are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, any numerical parameters set forth in the following description may vary depending on the desired properties one seeks to obtain in the compositions and methods according to the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter described in the present description should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

(2) Any patent, publication, or other disclosure material, in whole or in part, that is said to be incorporated by reference herein is incorporated herein only to the extent that the incorporated material does not conflict with existing definitions, statements, or other disclosure material set forth in this disclosure. As such, and to the extent necessary, the disclosure as set forth herein supersedes any conflicting material incorporated herein by reference. Any material, or portion thereof, that is said to be incorporated by reference herein, but which conflicts with existing definitions, statements, or other disclosure material set forth herein is only incorporated to the extent that no conflict arises between that incorporated material and the existing disclosure material.

(3) The embodiments disclosed herein are directed to compositions and methods that comprise lecithin. In various embodiments, the composition is a blend of lecithin in amounts ranging from 5% to 95% by weight of the disclosed compositions, and in certain embodiments from 70% to 95%; and the plasticizer in amounts ranging from 5% to 95% by weight of the disclosed compositions, and in certain embodiments from 5% to 30%.

(4) It has been found that the combination of lecithin and one or more plasticizers results in a composition that is able to solubilize a polar solvent in an oil or polyol.

(5) Lecithins suitable for use in the disclosed compositions and methods include, but are not limited to, crude filtered lecithin, fluid lecithin, de-oiled lecithin, chemically and/or enzymatically modified lecithin, standardized lecithin, and blends of any thereof. Lecithins employed in the present disclosure generally tend to have a hydrophilic-lipophilic balance (HLB) value ranging from 1.0 to 10.0 depending on the processing conditions and additives used to obtain the lecithin and produce the lecithin product. For example, crude filtered lecithin has an HLB value of approximately 4.0 and favors the formation of water-in-oil emulsions. Standardized lecithin includes co-emulsifiers having HLB values ranging from 10.0 to 24.0, which results in lecithin compositions having HLB values of 7.0 to 12.0 and favoring oil-in-water emulsions. Any lecithin or combinations of lecithins are suitable for use in the disclosed compositions and methods regardless of the initial HLB value of the lecithin. Lecithins useful in the disclosed compositions and methods may comprise co-emulsifiers having a hydrophilic-lipophilic balance value ranging from 10.0 to 24.0, and in certain embodiments 10.0 to 18.0.

(6) The emulsifier and/or surfactant properties of an amphiphilic substance such as lecithin, for example, may be predicted at least in part by the hydrophilic-lipophilic balance (HLB) value of the substance. The HLB value may function as an index of the relative preference of an amphiphilic substance for oil or waterthe higher the HLB value, the more hydrophilic the molecule; the lower the HLB value, the more hydrophobic the molecule. A description of HLB values is provided in U.S. Pat. No. 6,677,327, which is incorporated by reference herein in its entirety. HLB is also described in Griffin, Classification of Surface-Active Agents by HLB, J. Soc. Cosmetic Chemists 1 (1949); Griffin, Calculation of HLB Values of Non-Ionic Surfactants, J. Soc. Cosmetic Chemists 5 (1954); Davies, A quantitative kinetic theory of emulsion type, I. Physical chemistry of the emulsifying agent, Gas/Liquid and Liquid/Liquid Interfaces, Proceedings of the 2d International Congress on Surface Activity (1957); and Schick, Nonionic Surfactants: Physical Chemistry, Marcel Dekker, Inc., New York, N.Y., pp. 439-47 (1987), each of which is incorporated by reference herein in its entirety.

(7) In one embodiment, the nonionic co-surfactant is selected from the group consisting of ethoxylated monoglycerides, fatty acid ethoxylates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, propylene glycol alkyl esters, polyglycerol esters, glycols, polyoxyethylene sorbitan alkyls esters, mono and di esters of polyols, derivatives of any thereof, and combinations of any thereof.

(8) In various embodiments, the plasticizer used in the disclosed compositions and methods may be selected from the group consisting of a lactate, a citrate, an adipate, an ester of a lactate, an ester of a citrate, an ester of an adipate, a pentaerythritol ester, an isosorbide ester, and combinations of any thereof. The plasticizer may also be a bio-derived plasticizer. Substances of a bio-derived origin are derived from biological materials as opposed to being derived from petrochemical sources. Bio-derived substances may be differentiated from petroleum derived substances by their carbon isotope ratios using ASTM International Radioisotope Standard Method D 6866. As used herein, the term bio-derived refers to being derived from or synthesized by a renewable biological feedstock, such as, for example, an agricultural, forestry, plant, fungal, bacterial, or animal feedstock.

(9) Various agencies have established certification requirements for determining bio-derived content. These methods require the measurement of variations in isotopic abundance between bio-derived products and petroleum derived products, for example, by liquid scintillation counting, accelerator mass spectrometry, or high precision isotope ratio mass spectrometry. Isotopic ratios of the isotopes of carbon, such as the .sup.13C/.sup.12C carbon isotopic ratio or the .sup.14C/.sup.12C carbon isotopic ratio, can be determined using isotope ratio mass spectrometry with a high degree of precision. Studies have shown that isotopic fractionation due to physiological processes, such as, for example, CO.sub.2 transport within plants during photosynthesis, leads to specific isotopic ratios in natural or bio-derived compounds. Petroleum and petroleum derived products have a different .sup.13C/.sup.12C carbon isotopic ratio due to different chemical processes and isotopic fractionation during the generation of petroleum. In addition, radioactive decay of the unstable .sup.14C carbon radioisotope leads to different isotope ratios in bio-derived products compared to petroleum products. Bio-derived content of a product may be verified by ASTM International Radioisotope Standard Method D 6866. ASTM International Radioisotope Standard Method D 6866 determines bio-derived content of a material based on the amount of bio-derived carbon in the material or product as a percent of the weight (mass) of the total organic carbon in the material or product. Bio-derived products will have a carbon isotope ratio characteristic of a biologically derived composition.

(10) Bio-derived materials offer an attractive alternative for industrial manufacturers looking to reduce or replace their reliance on petrochemicals and petroleum derived products. The replacement of petrochemicals and petroleum derived products with products and/or feed stocks derived from biological sources (i.e., bio-based products) offer many advantages. For example, products and feed stocks from biological sources are typically a renewable resource. In most instances, bio-derived chemicals and products formed therefrom are less burdensome on the environment than petrochemicals and products formed from petrochemicals. As the supply of easily extracted petrochemicals continues to be depleted, the economics of petrochemical production will likely force the cost of the petrochemicals and petroleum derived products to higher prices compared to bio-based products. In addition, companies may benefit from the marketing advantages associated with bio-derived products from renewable resources in the view of a public becoming more concerned with the supply of petrochemicals.

(11) In various embodiments, plasticizers suitable for use in the disclosed compositions and methods include, but are not limited to propylene glycol monoester (PGME), butyl benzyl phthalate (BBP), di-n-butyl maleate (DBM), di-n-butyl phthalate (DBP), diethylene glycol dibenzoate (DEGD), di(2-ethylhexyl) phthalate (DEHP), dioctyl phthalate (DOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), diisodecyl adipate (DIDA), diisodecyl phthalate (DIDP), diisoheptyl phthalate (DIHP), diisononyl adipate (DINA), diisononyl cyclohexane-1,2-dicarboxylate (DINCH), diisononyl phthalate (DINP), diisooctyl adipate (DIOA), diisooctyl phthalate (DIOP), dimenthyl phthalate (DMP), di-n-hexyl phthalate (DnHP), di-n-octyl adipate (DnOA), di-n-octyl phthalate (DnOP), dinonyl phthalate (DNP), dioctyl adipate (DOA), di-(2-ethylhexyl) adipate (DEHA), dioctyl maleate (DOM), dioctyl sebacate (DOS), dioctyl terephalate (DOTP), dioctyl azelate (DOZ), dipropylene glycol dibenzoate (DPGB), di(2-propylheptyl) phthalate (DPHP), ditridecyl adipate (DTDA), ditridecyl phthalate (DTDP), diundecyl phthalate (DUP), 2-ethylhexanol (2-EH), epoxidized linseed oil (ELO), epoxidized soybean oil (ESO), general-purpose phthalate (GPP), isodecyl alcohol (IDA), isononyl alcohol (INA), phthalic anhydride (PA), 2-propylheptanol (2-PH), polyvinyl chloride (PVC), tricresyl phosphate (TCP), triisononyl trimellitate (TINTM), triiisooctyl trimellitate (TIOTM), trimellitic anhydride (TMA), trioctyl trimellitate (TOTM), triphenyl phosphate (TPP), trixylyl phosphate (TXP), undecyl dodecyl phthalate (UDP), soybean oil, medium chain triglycerides, a polyglycerol ester, epoxidised methyl soyate, a monoester of a polyol, a diester of a polyol, hydroxymethyl furfural, isosorbide, and combinations of any thereof.

(12) As used herein, the term DEHA includes di-(2-ethylhexyl) adipate. DEHA is also referred to as dioctyl adipate or DOA in the art. As used herein, unless otherwise indicated, dioctyl adipate (DOA) refers to the ester of adipic acid and linear n-octanol.

(13) ##STR00001##
It is also important to note that both moieties may be used as plasticizersalone, together, or in combination with other plasticizersin various embodiments described herein.

(14) In various embodiments, the disclosed compositions may also comprise one or more co-surfactants. The one or more co-surfactants may comprise one or more anionic surfactants, one or more non-ionic surfactants, or combinations of one or more anionic surfactants and one or more non-ionic surfactants. In various embodiments, the co-surfactant or co-surfactant combinations may have a hydrophilic-lipophilic balance ranging from 10.0 to 24.0, and in some embodiments from 10.0 to 18.0. In various embodiments, the lecithin may comprise from 5% to 95% by weight of the disclosed composition, in some embodiments from 60% to 90%, and in other embodiments from 80% to 90%; the plasticizer may comprise from 1% to 20% by weight of the disclosed composition, in some embodiments from 5% to 15%, and in other embodiments from 5% to 10% or 10% to 15%; and the co-surfactant may comprise from 2% to 20% by weight of the composition, in some embodiments from 5% to 15%, and in other embodiments from 10% to 15%.

(15) Anionic surfactants suitable for use in the disclosed compositions and methods include, but are not limited to, sodium and potassium salts of straight-chain fatty acids, polyoxyethylenated fatty alcohol carboxylates, linear alkyl benzene sulfonates, alpha olefin sulfonates, sulfonated fatty acid methyl ester, arylalkanesulfonates, sulfosuccinate esters, alkyldiphenylether(di)sulfonates, alkylnaphthalenesulfonates, isoethionates, alkylether sulfates, sulfonated oils, fatty acid monoethanolamide sulfates, polyoxyethylene fatty acid monoethanolamide sulfates, aliphatic phosphate esters, nonylphenolphosphate esters, sarcosinates, fluorinated anionics, anionic surfactants derived from oleochemicals, and combinations of any thereof. In various embodiments, the surfactant comprises an anionic surfactant, such as, for example, a phosphate ester.

(16) Non-ionic surfactants suitable for use in the disclosed compositions and methods include, but are not limited to, sorbitan monostearate, polyoxyethylene ester of rosin, polyoxyethylene dodecyl mono ether, polyoxyethylene-polyoxypropylene block copolymer, polyoxyethylene monolaurate, polyoxyethylene monohexadecyl ether, polyoxyethylene monooleate, polyoxyethylene mono(cis-9-octadecenyl)ether, polyoxyethylene monostearate, polyoxyethylene monooctadecyl ether, polyoxyethylene dioleate, polyoxyethylene distearate, polyoxyethylene sorbitan monolaurate polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, polyglycerol ester of oleic acid, polyoxyethylene sorbitol hexastearate, polyoxyethylene monotetradecyl ether, polyoxyethylene sorbitol hexaoleate, fatty acids, tall-oil, sorbitol hexaesters, ethoxylated castor oil, ethoxylated soybean oil, rapeseed oil ethoxylate, ethoxylated fatty acids, ethoxylated fatty alcohols, ethoxylated polyoxyethylene sorbitol tetraoleate, glycerol and polyethylene glycol mixed esters, alcohols, polyglycerol esters, monoglycerides, sucrose esters, alkyl polyglycosides, polysorbates, fatty alkanolamides, polyglycol ethers, derivatives of any thereof, and combinations of any thereof.

(17) In various embodiments, the surfactant comprises a non-ionic surfactant, such as, for example, ethoxylated monoglycerides, fatty acid ethoxylates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, propylene glycol esters, glycol esters, polyoxyethylene sorbitan alkyls esters, glycerol esters, derivatives of any thereof, and combinations of any thereof.

(18) In various embodiments, the disclosed compositions and methods may comprise lecithin, a plasticizer, a first non-ionic surfactant, and a second non-ionic surfactant that is different than the first non-ionic surfactant. In various embodiments, the plasticizer may comprise di-(2-ethylhexyl) adipate and one of the non-ionic surfactants may comprise a fatty acid ethoxylate. In various embodiments, the first non-ionic surfactant and the second non-ionic surfactant may be present in the disclosed composition in a weight ratio ranging from 1:9 to 9:1. The first and the second non-ionic surfactant may comprise 1% to 10% by weight of the disclosed composition, and in some embodiments from 3% to 7%.

(19) In various embodiments, the disclosed compositions find utility in products selected from the group consisting of a paint, an ink, a coating, a magnetic fluid, concrete, a ceramic, a textile auxiliary agent, an aid in leather finishing, a plastic compounding agent, a lubricant, an oilfield drilling additive, a mold release agent, a cosmetic, and a composite used in engineered woods (wood composite).

(20) Water-based coatings may include, but are not limited to, latex paints. In various embodiments, the disclosed compositions may be used as dispersion vehicles for pigments in paint and ink formulations. In various embodiments, the disclosed compositions advantageously aid in pigment processing, including, but not limited to, grinding, milling and release aids, which may contribute to improved gloss, colorant and body in pigmented formulations. The low viscosity of the disclosed compositions provides improved coating uniformity to pigments and other particulates in dispersions. In this context, among others, the disclosed compositions provide improved dispersant, wetting agent, and/or stabilizer properties and performance.

(21) In various other embodiments, the disclosed compositions may be used in magnetic fluid applications. In one embodiment, the disclosed compositions may be used to stabilize magnetic particles in a solvent base, including, but not limited to, a mixture of a base oil and an ester compound. The improved wetting and dispersant properties of the disclosed compositions result in reduced agglomeration of the suspended particles in magnetic fluids without resulting in adverse effects on the viscosity of the fluid.

(22) The disclosed compositions may also be used in nanotechnology applications. In one embodiment, the disclosed compositions may be used as a dispersant, wetting agent, solubilizer, and/or stabilizer in nanoparticle suspensions. Additional applications for the disclosed compositions and methods include, but are not limited to, use in fiberglass, concrete, ceramics, plastics, and composites. Additional uses of the disclosed compositions include, but are not limited to, uses as textile auxiliary agents, leather finishing agents, plastic compounding agents, lubricants, oilfield drilling additives, emollients, film-formers, and mold release agents.

(23) The embodiments disclosed herein are also directed to methods of preparing the disclosed compositions. In various embodiments, lecithin is heated to a temperature above ambient temperature, a plasticizer is added to the lecithin at the elevated temperature, and the plasticizer and lecithin are mixed together to form a lecithin-plasticizer blend. The blend is cooled to ambient temperature. The resulting blend has a viscosity lower than the lecithin ingredient alone, which may be less than 3000 cP. In various embodiments, the viscosity of the lecithin-plasticizer blend may be less than 2000 cP, less than 500 cP, or less than 100 cP. In various other embodiments, one or more non-ionic emulsifiers may be added to the lecithin either before or simultaneously with one or more plasticizers. The one or more non-ionic emulsifiers may alternatively be added to the blend of the lecithin and the one or more plasticizers.

(24) The versatility of the surfactant package or system was determined by being able to solubilize 10% in soybean oil, tall fatty acids, and castor oil. Solubilization of polar components in non-polar oils typically requires very high surfactant concentrations that form a microemulsion. One characteristic of the surfactant packages disclosed herein is that polar additives are able to be solubilized in a variety of oils with a limited amount of the surfactant package.

EXAMPLES

(25) The following exemplary, non-limiting examples are provided to further describe the embodiments presented herein. Those having ordinary skill in the art will appreciate that variation of these Examples are possible within the scope of the invention.

Example 1

(26) A blend of crude filtered lecithin (Yelkin T, Archer-Daniels-Midland Company, Decatur, Ill., USA), DEHA (Plastomoll DOA, BASF, North Mount Olive, N.J., USA), a tall fatty acid ethoxylate surfactant (Ninex MT-610, Stepan Company, Northfield, Ill., USA), and a phosphate ester surfactant (Stepfac 8170, Stepan Company, Northfield, Ill., USA) was prepared. The blend was 80% lecithin, 10% DEHA, 7% fatty acid ethoxylate surfactant, and 3% phosphate ester surfactant by weight. The blend was prepared by mixing the lecithin, DEHA, and two surfactants and heating the mixture to 50 C. under constant stirring for 30 to 60 minutes. The blend was cooled to ambient temperature (approximately 25 C.). The blend was a free-flowing liquid at ambient temperature. The blend was water dispersible.

Example 2

(27) A blend of crude filtered lecithin (Yelkin T, Archer-Daniels-Midland Company, Decatur, Ill., USA), DEHA (Plastomoll DOA, BASF, North Mount Olive, N.J., USA), a tall fatty acid ethoxylate surfactant (Ninex MT-610, Stepan Company, Northfield, Ill., USA), and a phosphate ester surfactant (Surfonic PE-BP 2, Huntsman, Woodland, Tex., USA) was prepared. The blend was 80% lecithin, 10% DEHA, 7% fatty acid ethoxylate surfactant, and 3% phosphate ester surfactant by weight. The blend was prepared by mixing the lecithin, DEHA, and two surfactants and heating the mixture to 50 C. under constant stirring for 30 to 60 minutes. The blend was cooled to ambient temperature (approximately 25 C.). The blend was a free-flowing liquid at ambient temperature. The blend was water dispersible.

Example 3

(28) A lecithin based microemulsion was produced with the ingredients of Table 1.

(29) TABLE-US-00001 TABLE 1 Ingredient Amount YELKIN T 36% Polysorbate 80 10.4% Fatty acids 3.2% 88% strength lactic acid 8% Sodium lactate 18.4% Ethyl lactate 4.0% Mineral oil 20.0%

(30) To produce the microemulsion, a lecithin-cosurfactant blend was prepared by mixing: the YELKIN T brand lecithin (available from Archer-Daniels-Midland Company of, Decatur, Ill.); a co-surfactant, polysorbate 80 (available from BASF, New Jersey); and fatty acids. The components were mixed at 50 C. under constant stirring for between 30 minutes to 60 minutes, thus producing an amber, transparent lecithin concentrate. The lecithin-cosurfactant blend is miscible in mineral oil.

(31) The lecithin-cosurfactant blend was mixed with the sodium lactate (available from Archer-Daniels-Midland Company, Decatur, Ill.), followed by the 88% strength lactic acid (available from Archer-Daniels-Midland Company, Decatur, Ill.). To this blend, the ethyl lactate (available from Archer-Daniels-Midland Company, Decatur, Ill.) was added. 80 g of this blend was mixed with 20 g mineral oil to form a microemulsion that was clear and transparent. This lecithin based microemulsion is infinitely miscible in mineral oil. In addition, this lecithin based microemulsion can solubilize additional water in an amount of up to 5-40% wt/wt and still maintain its clear and transparent microemulsion phase.

Example 4

(32) A lecithin based microemulsion was produced with the ingredients of Table 2.

(33) TABLE-US-00002 TABLE 2 Ingredient Amount YELKIN T 36% Polysorbate 80 10.4% Fatty acids 3.2% 88% strength lactic acid 8% Sodium lactate 18.4% Ethyl lactate 24.0%

(34) To produce the microemulsion, a lecithin-cosurfactant blend was prepared by mixing: the YELKIN T brand lecithin (available from Archer-Daniels-Midland Company of, Decatur, Ill.); a co-surfactant, polysorbate 80 (available from BASF, New Jersey); and fatty acids. The components were mixed at 50 C. under constant stirring for between 30 minutes to 60 minutes, thus producing amber, transparent lecithin concentrate.

(35) The lecithin-cosurfactant blend was mixed with the sodium lactate (available from Archer-Daniels-Midland Company, Decatur, Ill.), followed by the 88% strength lactic acid (available from Archer-Daniels-Midland Company, Decatur, Ill.). To this blend, the ethyl lactate (available from Archer-Daniels-Midland Company, Decatur, Ill.) was added. 90 g of this blend was mixed with 10 g glycerol to form a microemulsion that was clear and transparent. In addition, this lecithin based microemulsion can solubilize additional water in an amount of up to 5-40% wt/wt and still maintain its clear and transparent microemulsion phase.

Example 5

(36) 50% by weight of the composition produced in Example 1 was mixed with 50% by weight of ethoxylated monoglycerides (Mazol 80, available from BASF) to produce an emulsifier blend using propylene glycol as a co-solvent.

(37) The ability of the emulsifier blend to stabilize of mixture of a biobased polyol (soy polyol) with a petroleum based polyol in the presence of glycerol was tested. The compounds used and percentages of each are set forth in Table 3. The compounds were weighed in a glass jar, mixed well with sweep agitation for 5 minutes at 60 C., and monitored for stability over time for any phase separation.

(38) TABLE-US-00003 TABLE 3 Soy Emulsifier Sample polyol (%) Petroleum polyol (%) Glycerol (%) blend (%) A 63 35 2 4 B 61 35 4 4 C 59 35 6 4 D 57 35 8 4 E 55 35 10 4

(39) A water soluble dye was added to the glycerol before blending in order to be able to visualize any phase separation in the blends of Table 3. This was helpful since the refractive index of glycerol and Pyrex glass are very similar (RI of about 1.47). The presence of the emulsifier blend helped reduce the amount of phase separation as compared to a control sample that did not have the emulsifier blend, where the glycerol with the water soluble dye settled at the bottom.

(40) The present invention has been described with reference to certain exemplary and illustrative embodiments, compositions and uses thereof. However, it will be recognized by persons having ordinary skill in the art that various substitutions, modifications or combinations of any of the exemplary embodiments may be made without departing from the scope of the invention. Thus, the invention is not limited by the description of the exemplary and illustrative embodiments, but rather by the appended claims.