Bio-based alkylglyceryl ethers and methods for producing and using them

Abstract

The present invention relates to bio-based alkyl, alkenyl or alkynyl glyceryl ether compounds and compositions and their uses, including formulations containing same, methods for preparing the bio-based compounds of the invention, and the use of the compounds and compositions of the invention in the formulation of products or components of products.

Description

Technical Field

[0001] [Cross - reference to Related Applications] This application claims the benefit of the filing date of U.S. Provisional Patent Application No. 63 / 029,281, filed May 22, 2020, the entire content of which is incorporated herein by reference.

[0002] The present invention relates to bio - based alkyl glyceryl ether compounds and compositions, formulations containing such compounds and compositions, methods for manufacturing and using such compounds, compositions and formulations, and their uses including, in particular, cosmetic uses.

Background Art

[0003] Alkyl glyceryl ethers are compounds that have exceptional utility across a wide range of industries, mainly due to their non - ionic amphiphilic properties. 1 Alkyl glyceryl ethers are particularly useful in the formulation of cosmetics and / or personal care products, and such compounds can function as surfactants, detergents, foaming boosters, emulsifiers, skin conditioning agents, humectants, skin softeners and deodorants. 2

[0004] Branched - chain alkyl glyceryl ethers such as 2 - ethylhexyl glycerin, isodecyl glyceryl ether and isostearyl glyceryl ether impart greater fluidity at low temperatures (e.g., many are viscous fluids at 5 °C or below) and can enhance the ease of processing of formulations and the compatibility of various excipients, and are particularly useful because of their branched - chain alkyl groups. For example, 2 - ethylhexyl glycerin (EHG, Figure 1) has a melting point of - 13 °C and is a liquid that can be poured at room temperature, while the corresponding alkyl glyceryl ether with a straight - chain alkyl group (i.e., caprylyl glyceryl ether, shown below) is a solid at room temperature and has a reported melting point of about sixty - nine (69) °C. 3 2

Chem.

[0005] A medium-chain branched alkyl group, that is, a branched alkyl glyceryl ether having 4 to 10 carbon atoms, is particularly useful. As a so-called medium-chain terminal diol, EHG is well known for its ability to impair the integrity of the membranes of microorganisms. 4 This membrane-disrupting ability is attributed to the amphiphilic nature of EHG, which is characterized by an octanol-water partition coefficient (log K ow ) value of 1.9. Due to these properties of EHG, EHG is a useful ingredient for the preservation of aqueous formulations against microbial contamination, such as cosmetics, toiletries, and pharmaceuticals, and also as an anti-odor agent in deodorants.

[0006] The main synthetic routes of EHG are shown in Schemes 1 to 3 below. As shown in Scheme 1, propylene is generally used as a feedstock for the preparation of 2-ethylhexanol. [Chemical formula]

[0007] As shown in Scheme 2, propylene is also a common feedstock for the synthesis of ECH. [Chemical formula]

[0008] Finally, Scheme 3 shows the general synthetic route of EHG, which proceeds by the etherification of 2-ethylhexanol with epichlorohydrin (ECH) followed by the immediate in situ hydrolysis of the epoxide to obtain a 1,2-diol. [Chemical formula]

[0009] However, as shown above, the well-known synthetic routes for EHG rely on propylene, a non-renewable feedstock typically obtained from petroleum or natural gas. Therefore, EHG is considered neither "natural" nor "sustainable" by consumers, and incorporating EHG into consumer products is becoming increasingly undesirable. Summary of the Invention Problems to be Solved by the Invention

[0010] There is still a need for bio-based alkyl, alkenyl, and / or alkynyl glyceryl ethers prepared from sustainable and renewable plant-derived feedstocks. Means for Solving the Problems

[0011] The present invention relates to a bio-based compound of formula (I):

Chemical formula

[0012] In some embodiments, the present invention relates to a compound of formula (I) wherein n is 1 and compositions containing the same. Such compositions may optionally contain one or more compounds of formula (I) wherein n = 2 and / or n = 3.

[0013] In some embodiments, the R1-O bond in the compound of formula (I) is at the secondary carbon of R1. In some embodiments, R1 is a branched C6-C 16 alkyl containing at least one methyl branch.

[0014] In some embodiments, R1 is a branched C6-C 12 alkyl, alkenyl or alkynyl. In some embodiments, R1 is a branched C6-C10 It is an alkyl, alkenyl, or alkynyl compound. In some embodiments, R1 is a branched C8 alkyl, alkenyl, or alkynyl compound. In some embodiments, the compound of formula (I) is 1-methylheptylglycerin.

[0015] The present invention also relates to compositions comprising one or more compounds of formula (I). In some embodiments, the compositions of the present invention include a branched C6-C compound where R1 is branched C6-C 10 The present invention comprises at least one compound of formula (I) which is alkyl, alkenyl, or alkynyl and n=1. In some embodiments, the composition of the present invention comprises a branched C6-C compound where R1 is branched C6-C 16 A compound of formula (I) first, which is alkyl, alkenyl, or alkynyl, with n=1, and R1 is branched C6~C 10 The present invention comprises a compound of formula (I) 2, which is alkyl, alkenyl, or alkynyl, and n=1, wherein the compound of formula (I) 1 and the compound of formula (I) 2 are not the same. In some embodiments, the composition of the present invention comprises a methyl branched C6-C compound where R1 is methyl branched C6-C 16 The present invention comprises a compound of formula (I) which is alkyl, alkenyl, or alkynyl, wherein the methyl-branched compound is present in a ratio of 10:1 or higher compared to the concentration of the corresponding ethyl-branched compound. In some embodiments, the composition of the present invention comprises a methyl-branched C6-C with R1 having a single methyl branch. 16 The composition contains an alkyl compound of formula (I), which accounts for 95 wt% or more of all compounds of formula (I) present in the composition. In some embodiments, the composition of the present invention contains 1-methylheptylglycerin (MHG). In some embodiments, MHG is the only compound of formula (I) present in the composition.

[0016] In some embodiments, the composition of the present invention further comprises a solvent or diluent. In some embodiments, the composition of the present invention is silicone-free.

[0017] The present invention also includes formula (I): [ka] (In the formula, R1 is branch C6~C) 16 A method for preparing a compound (which is alkyl, alkenyl, or alkynyl, where n is 1 to 3), comprising a bio-based branched C6-C6 compound. 16 The present invention relates to a method comprising contacting an alcohol, alkenol, or alquinol with a bio-based C3 epihalohydrin or oxyranyl alcohol in the presence of a catalyst, followed by hydrolysis.

[0018] In some embodiments, the process of the present invention is a bio-based branched C6-C 16 This includes utilizing compounds in which the -OH group of an alcohol, alkenol, or alquinol is not located at the terminal position. In some embodiments, the process of the present invention is branched C6~C 12 Alcohol, alkenol or alkinol, or branched C6-C 10 This includes utilizing a bio-based alcohol that is an alcohol, alkenol, or alkinol, or the bio-based alcohol is 2-octanol.

[0019] In some embodiments, the process of the present invention includes a catalyst that is boron trifluoride or tin tetrachloride. In some embodiments, the bio-based epihalohydrin is epichlorohydrin. In some embodiments, the bio-based oxyranyl alcohol is glycidol.

[0020] The present invention also includes (i) Formula (I): [ka] (In the formula, R1 is branch C6~C) 16 A bio-based compound having an alkyl, alkenyl, or alkynyl group, where n is 1 to 3, and substantially all carbon atoms present in the compound of formula (I) are bio-based, (ii) at least one other bio-based component, Regarding formulations containing the above.

[0021] In some embodiments, the formulation is a personal care product selected from cosmetics, conditioners for hair, nails, skin, or textiles, shampoos, hair styling products, oils or waxes for facial hair care, permanent wave solutions, hair coloring agents, facial cleansers and / or body soaps, makeup removers, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, sunscreen gels, lotions or creams, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliners, wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleaning products, dishwashing products, hair or fur cleaning products, or lotions or moisturizers, or a component of a personal care product.

[0022] In some embodiments, the formulation includes a compound of formula (I) which is MHG.

[0023] Suitable ingredients for use with the formulation of the present invention include, but are not limited to, water, surfactants, emollients, moisturizers, conditioning agents, chelating agents, surfactants, bleaching or whitening agents, pH adjusters, fragrances, colorants, exfoliants, antioxidants, plant components, mica, smectite, thickeners, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and their derivatives, glycerin and its derivatives, enzymes, anti-inflammatory agents and other drugs, bactericides, antifungal agents, disinfectants, antioxidants, UV absorbers, dyes and pigments, preservatives, sunscreen surfactants, antiperspirant surfactants, oxidizing agents, pH balancers, moisturizers, peptides and their derivatives, anti-aging surfactants, hair growth agents, anti-cellulite surfactants, and combinations thereof. Furthermore, in some embodiments, the ingredients are bio-based.

[0024] In some embodiments, the compound of formula (I) is present in the formulation at a concentration of about 0.05 wt% to about 10 wt% or about 0.5 wt% to about 2.5 wt%. In some embodiments, the formulation has a pH of about 2 to about 10 or about 3 to about 7.5.

[0025] In some embodiments, the formulation comprises an oil-in-water emulsion. In some embodiments, the formulation comprises a micelle solution containing water and at least one surfactant. In some embodiments, the formulation is silicone-free.

[0026] The present invention relates to (i) the formula (I) of the effective quantity: [ka] (In the formula, R1 is branch C6~C) 16 The present invention also relates to a method for mitigating microbial contamination, comprising (ii) blending a biobased compound (which is an alkyl, alkenyl, or alkynyl group, where n is 1 to 3, and substantially all carbon present in the compound of formula (I) is biobased) with at least one other component.

[0027] In some embodiments, the method of the present invention for reducing microbial contamination comprises blending an effective amount of the compound of formula (I) with at least one other component suitable for use in formulations described herein, including pharmaceuticals, food processing products, and any other consumer products that require preservation. In some embodiments, the at least one other component is bio-based.

[0028] In some embodiments, the present invention's method for reducing microbial contamination involves blending a compound of formula (I) into a composition or formulation at a concentration of about 0.05 wt% to about 10 wt%, about 0.5 wt% to about 2.5 wt%, or about 0.5 wt% to about 1.5 wt%.

[0029] In some embodiments, the compositions, formulations, and products containing the same, as well as related methods of the present invention, further include boosters. Suitable boosters for use with the compositions, formulations, products, and methods of the present invention include, but are not limited to, medium-chain diols, medium-chain polyols, chelating agents, and combinations thereof.

[0030] Suitable chelating agents for use with the compositions, formulations, products, and methods of the present invention include C6-C 10 Examples of chelating agents include, but are not limited to, alkylhydroxamic acid or its alkylhydroxamate salts, tetrasodium glutamate diacetate, phytic acid or its salts, gluconic acid or its salts, galacturonic acid or its salts, galactaric acid or its salts, and combinations thereof. In some embodiments, the chelating agent is caprylhydroxamic acid, a hydroxamate of caprylhydroxamic acid, or a combination thereof. [Brief explanation of the drawing]

[0031] [Figure 1] This figure shows a graphical representation of the "soaping score" as a function of the "number of rub-in cycles," and the details of the experiment are presented in Example 18 and Comparative Examples 8 to 10 of the present invention. [Modes for carrying out the invention]

[0032] Before describing the compounds, compositions, and methods of the present invention in particular, it should be understood that the invention is not limited to the specific processes, compositions, or methods described, as these may be modified. It should also be understood that the terms used in the description are intended solely to describe specific versions or embodiments and are not intended to limit the scope of the invention, which is limited only by the appended claims. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. Any methods and materials similar to or equivalent to those described herein may be used in carrying out or testing embodiments of the present invention, but preferred methods, devices, and materials are described herein. All publications referenced herein constitute part of this specification by literal quotation. Nothing in this specification should be construed as acknowledging that the present invention has no prior rights to such disclosure for the sake of prior art.

[0033] Furthermore, when used herein and in the appended claims, it should be noted that the singular forms "a," "an," and "the" refer to multiple objects unless otherwise clearly indicated by the context. For example, a reference to "cell" refers to one or more cells and their equivalents that are known to those skilled in the art.

[0034] Unless otherwise specified, "%" can refer to either weight percentage or volume percentage.

[0035] "Cosmetic-acceptable" means suitable for use in contact with the skin without excessive toxicity, incompatibility, instability, irritation, allergic reactions, etc.

[0036] Where applicable, chemical substances are designated by their INCI names in accordance with the International Nomenclature Guidelines for Cosmetic Ingredients. Additional information, including suppliers and trade names, can be found in the appropriate INCI monographs in the International Cosmetic Ingredient Dictionary and Handbook, 16th Edition published by the Personal Care Products Council, Washington, DC, or online at the Personal Care Products Council's Online INFOBASE (http: / / online.personalcarecouncil.org).

[0037] The branched alkyl, alkenyl, and alkynyl glyceryl ether (collectively, "BAGE") compounds of the present invention are bio-based. Therefore, the bio-based BAGE compounds of the present invention contain up to 100% renewable carbon (i.e., carbon derived from plant sources) and are prepared using bio-based (i.e., renewable) starting materials instead of conventional petrochemical-derived carbon sources. The bio-based BAGE compounds of the present invention offer all the advantages of petrochemical-derived BAGE compounds, plus additional benefits in terms of improved sustainability and consumer appeal, given the growing consumer demand for more natural and sustainable products in the market.

[0038] The biobased carbon content of a compound, composition, or formulation can be determined by radiocarbon dating, which determines the relative age of materials composed of organic (i.e., carbon-containing) substances. Radiocarbon is 14 It is an unstable isotope of carbon, known as ¹¹C. 14 C emits radiant energy in the form of beta particles at a very consistent rate, eventually becoming more stable 14It is an unstable isotope that decays into N (i.e., its half-life as radioactive carbon is 5730 years). Petroleum-based (i.e., petrochemical-derived) raw materials originate from plants and animals buried millions of years ago, so the radioactive carbon in the raw materials (i.e., 14 C) is lost through radioactive decay. The ASTM international standard sets out a test standard for determining the certainty of "bio-based compounds" using radiocarbon, which can be found in ASTM D6866-16. This standard distinguishes between newer carbon and carbon derived from fossil fuels or petroleum and petrochemical sources, i.e., "older carbon" in recent or current biomass. 14 Since the amount of C is known, the percentage of carbon derived from renewable sources can be estimated from total organic carbon analysis, which provides the data necessary to determine whether a compound truly originates from “natural” and / or “sustainable” (“renewable”) source materials, or conversely, from “old” sequestration compounds (i.e., from petrochemical or petroleum-based sources). The use of petroleum-based or often labeled fossil-based source materials is generally considered unsustainable; that is, “old carbon” derived from petroleum or other fossil fuels is unsustainable, not a renewable source material, and is not considered “natural” and / or “sustainable” among those skilled in the art.

[0039] The carbon content of a biobase can also be determined by isotopic analysis methods, such as mass spectrometry, which evaluates the ratio of carbon-12 / carbon-13 and / or hydrogen-1 / hydrogen-2. Such tests are available through several analytical service laboratories and are faster, more cost-effective, and provide more detailed information compared to radiocarbon dating. Stable isotope analysis is based on the principle of kinetic isotope effects. The latter effect is well known to those skilled in the art of chemical reaction kinetics. In a broad sense, heavier isotopes of certain elements react more slowly than lighter isotopes (e.g., carbon-12 to carbon-13). Therefore, when plants incorporate carbon dioxide into their biomass, the ratio of carbon-12 to carbon-13 varies depending on the type of chemistry the plant uses to produce biomass (e.g., whether the plant uses the C3 photosynthetic pathway or the C4 photosynthetic pathway). This is generally δ 13 C / 12 C ratio (i.e., δ 13 This is reported as C) and refers to the current carbon dioxide standard. In addition, similar isotopic kinetic effects have been observed when water is incorporated into new biomass, which is δ 2 H / 1 H ratio (i.e., δ 2 It is measured as H). Those familiar with the related technology will know δ 13 C ratio and δ 2 By using combinations of H ratios, the nature of the supply raw materials used in the preparation of the preservative product being analyzed (i.e., whether they are petrochemical in origin or derived from recently living or living algae, plants, or similar biosources) can be easily distinguished and verified.

[0040] Because the bio-based BAGE compounds of the present invention are bio-based, substantially all of their carbon originates from natural or sustainable sources. That is, the bio-based BAGE compounds of the present invention are determined to have a bio-based carbon content of 100% ± 1%, within the margin of experimental error. Similarly, the bio-based BAGE compounds of the present invention are substantially free of carbon from unsustainable and / or non-renewable sources. The bio-based BAGE compounds of the present invention are substantially free of carbon from petroleum and / or petrochemicals, natural gas, or coal.

[0041] Similarly, the method for preparing the bio-based BAGE compounds of the present invention involves using feedstocks and / or reagents containing carbon derived from renewable sources. Therefore, the method for preparing the bio-based BAGE compounds of the present invention utilizes starting materials that are substantially free of petroleum-derived carbon. For example, the bio-based BAGE compounds of the present invention can preferably be prepared from feedstocks obtained from sustainable agricultural activities using non-genetically modified organisms or biomass. Such feedstocks are referred to herein as “natural” and “renewable” (i.e., “sustainable”) and are known in the art as non-petroleum-derived feedstocks. As a further example, the bio-based BAGE compounds of the present invention can be prepared from bio-based feedstocks derived from plant, vegetable and / or algae sources, and / or by fermentation. These exemplary materials used in the preparation of the bio-based BAGE compounds of the present invention contain substantially only “new” carbon and substantially no “old” carbon fossil fuel sources. Therefore, the feedstocks and starting materials used in the preparation of the bio-based BAGE compounds of the present invention do not originate from fossil sources such as petroleum, natural gas and / or coal. Such products are referred to herein as “natural” products and are known in the art as non-petrochemical or “bio” products.

[0042] As used herein, “sustainable” refers to materials derived from renewable sources. In contrast, “unsustainable” refers to materials derived from limited natural resources such as fossil fuels (e.g., oil, natural gas, coal, etc.).

[0043] In some embodiments, the present invention relates to formula (I): [ka] (In the formula, R1 is C6~C 16 The present invention relates to bio-based BAGE compounds (which are branched alkyl, alkenyl, or alkynyl, and where n is 1 to 3). Those skilled in the art will recognize that the bio-based BAGE compound of the present invention with n=1 contains a glyceryl ether. Similarly, the bio-based BAGE compound of the present invention with n=2 or n=3 contains repeated glycerol functional groups and is therefore polyglycerol.

[0044] In some embodiments, the present invention comprises a substantially pure compound of formula (I) with optionally one or more solvents or diluents. Compositions comprising mixtures of bio-based BAGE compounds are also within the scope of the present invention. In some embodiments, a composition comprising one or more compounds of formula (I) is n=1, where R1 is a variety of C6-C 16 This includes compounds that are combinations of branched alkyl, alkenyl, and alkynyl groups.

[0045] When used in this specification, R1 is branch C6~C 16 It includes alkyl, alkenyl, and alkynyl groups. In some preferred embodiments, R1 is branched C6~C 16 It is an alkyl group.

[0046] In some embodiments, the ether bond to R1 is formed at a non-primary carbon atom, i.e., a secondary or tertiary carbon atom. Furthermore, R1 is C6~C 10 It may further contain a branched alkyl, alkenyl, or alkynyl. In some embodiments, R1 is a C7-C9 branched alkyl, alkenyl, or alkynyl. It is more preferable that R1 is a C7-C9 branched alkyl. In a particular embodiment, R1 is a branched C8 alkyl, alkenyl, or alkynyl. In a particular embodiment of the present invention, the compound of formula (I) is [ka] That is the case.

[0047] Other specific embodiments include compounds of formula (I) shown below. [ka]

[0048] The present invention also relates to compositions and formulations comprising the bio-based BAGE compounds of the present invention. In some embodiments, compositions and / or formulations comprising the bio-based BAGE compounds of the present invention substantially do not contain any components prepared using unsustainable carbon starting materials. However, without limitation, the bio-based BAGE compounds of the present invention are nevertheless interchangeable with components prepared using petroleum-based carbon.

[0049] In some embodiments, the bio-based BAGE compounds of the present invention exist in combination with solvents and / or diluents. For example, one or more solvents or diluents may be added to control viscosity and / or to facilitate handling for transport, storage and / or subsequent use of the bio-based BAGE compounds. The solvents and / or diluents may be combined with the bio-based BAGE compounds of the present invention after synthesis or purification, or may be present by retaining one or more solvents and / or diluents used in one or more synthesis and / or purification processes. In some embodiments, the composition comprises one or more bio-based BAGE compounds and solvents and / or diluents present at concentrations of about 30% to about 90% by weight, about 30% to about 80% by weight, or about 30% to about 70% by weight of the composition.

[0050] In some embodiments, the solvents and / or diluents used with the compounds, compositions, formulations and / or processes of the present invention are bio-based (i.e., substantially free of non-renewable carbon). Suitable solvents and / or diluents for use with the compounds, compositions and / or processes of the present invention include, but are not limited to, water, glycerin, propanediols (1,2-propanediol (propylene glycol), 1,3-propanediol, etc.), butanediols (1,2-butanediol, 1,3-butanediol, 2,3-butanediol, etc.), and / or pentanediols (e.g., 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, etc.).

[0051] In some embodiments, the bio-based BAGE of formula (I) of the present invention contains R1 having one or more methyl branches (i.e., R1 is "methyl-branched"), and the concentration of methyl-branched bio-based BAGE exceeds about 95 wt%. In particular, the concentration of methyl-branched bio-based BAGE in the composition is greater than about 95 wt%, and the total concentration of branched bio-based BAGE other than the methyl-branched compound is less than about 5 wt%. In certain embodiments, the concentration of methyl-branched bio-based BAGE in the composition is greater than about 95 wt%, and the concentration of ethyl-branched bio-based BAGE is less than about 5 wt%.

[0052] One particular embodiment is given by formula (I): [ka] The composition comprises a compound and at least one other component, where R1 is methyl branched C6~C 16 The compounds are alkyl, alkenyl, or alkynyl, with n ranging from 1 to 3, and the methyl branched compound is present in a ratio of 10:1 or greater compared to the concentration of the corresponding ethyl branched compound.

[0053] When used herein, the bio-based C6-C of the present invention 16The "corresponding ethyl branched compound" of a compound is one in which an ethyl group is present instead of a terminal methyl group, and is used only to illustrate embodiments in which a terminal methyl group may be preferred. Such "corresponding" compounds may have the same number or one more carbon atoms at R1.

[0054] In some embodiments, the methyl branched compound is present in the composition in a ratio of 12:1, 15:1, 20:1, 25:1, 50:1, or 100:1 compared to the concentration of the corresponding ethyl branched compound. In some embodiments, R1 is a methyl branched C6-C having a single methyl branch. 16 It is an alkyl, alkenyl, or alkynyl compound, present in the composition at a concentration of 95 wt% or more, 98 wt% or more, or 99 wt% or more.

[0055] In one particular embodiment, the bio-based compound in the composition is [ka] That is the case.

[0056] In some embodiments, the composition of the present invention comprises one or more of the following compounds, wherein the carbon in the compound is biobased, preferably derived from a plant source. [ka]

[0057] The bio-based BAGE of the present invention can be incorporated into formulations (or components of products) of any product containing surfactants, detergents, foaming agents, emulsifiers, skin conditioning agents, moisturizers, emollients, and / or deodorants. Non-limiting examples of products that may contain the compound and / or composition include personal care, home care and / or institutional care products, pharmaceuticals and / or veterinary drugs, food and / or food processing products, textile care products, and industrial products. Products or components of products containing the bio-based BAGE compound and / or composition of the present invention include, but are not limited to, liquids, solids, aerosols, gels, waxes, oils, lotions, emulsions, oil-in-water emulsions, and micelle compositions. In some embodiments, the bio-based BAGE compound or a composition containing the bio-based BAGE compound is incorporated into formulations for personal care products or components thereof. Non-exclusive examples of personal care products that may contain formulations include cosmetics, conditioners for hair, nails, skin, or textiles, shampoos, hair styling products, oils or waxes for facial hair care, permanent wave solutions, hair coloring agents, facial cleansers or body washes, makeup removers, cleansing lotions, emollient lotions or creams, bar soaps, liquid soaps, shaving creams, foams or gels, sunscreens, sunscreen gels, lotions or creams, deodorants or antiperspirants, moisturizing gels, shaving foams, face powders, foundations, lipsticks, blushes, eyeliners, wrinkle creams or anti-aging creams, eyeshadows, eyebrow pencils, mascaras, mouthwashes, toothpastes, oral care products, skin cleansing products, textile cleaning products, dishwashing products, hair or fur cleaning products, toners or moisturizers, and the like.

[0058] Embodiments include incorporating it into a formulation together with at least one other ingredient. In some embodiments, at least one other ingredient is biobased. Suitable formulations and additive ingredients include, but are not limited to, those known to those skilled in the art and are listed in the International Cosmetic Ingredient Dictionary and Handbook, 16th Edition published by the Personal Care Products Council, Washington, DC, or online at the Personal Care Products Council's Online INFOBASE (http: / / online.personalcarecouncil.org).

[0059] Examples of formulations and ingredients that are acceptable for use in formulations for human use include, but are not limited to, water, surfactants, emollients, moisturizers, conditioning agents for hair, skin, or nails, chelating agents, surfactants, bleaching or whitening agents, additional pH adjusters, fragrances, colorants, exfoliating agents, antioxidants, plant components such as plant extracts, mica, smectite, thickeners, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and their derivatives, glycerin and its derivatives, enzymes, anti-inflammatory agents and other drugs, bactericides, antifungal agents, disinfectants, antioxidants, UV absorbers, dyes and pigments, preservatives, sunscreen surfactants, antiperspirant surfactants, oxidizing agents, pH balancers, moisturizers, peptides and their derivatives, anti-aging surfactants, hair growth agents, anti-cellulite surfactants, etc.

[0060] The formulations and compositions may contain one or more biobased BAGE compounds. In preferred embodiments, the type and amount of biobased BAGE compounds used in embodiments of the formulations and / or compositions are such that they impart antimicrobial or preservative effects to the formulations and / or compositions in order to protect them from microbial contamination and / or improve their antimicrobial effect on surfaces, such as skin and hair. For this purpose, one embodiment includes a formulation and / or composition comprising at least one fully biobased branched medium-chain terminal diol and at least one other component. Further aspects of the present invention encompass methods for mitigating microbial contamination, comprising blending an effective amount of at least one fully biobased branched medium-chain terminal diol and at least one other component. Embodiments of the formulations and / or compositions include formula (I): [ka] (In the formula, R1 is C6~C 16 The bio-based branched medium-chain terminal diol is a bio-based BAGE compound (which is a branched alkyl, alkenyl, or alkynyl, where n is 1-3). In some embodiments, R1 is C6-C 10 That is the case.

[0061] In one particular embodiment, the branched mid-chain terminal diol is [ka] That is the case.

[0062] In other specific embodiments, the branched medium-chain terminal diol is the following compound: [ka]

[0063] The effective amount of the bio-based BAGE compound in the formulation is about 0.05 wt% to about 10 wt%, preferably about 0.1 wt% to about 5 wt%, more preferably about 0.25 wt% to about 4 wt%. In certain embodiments, the bio-based BAGE compound is bio-based methylheptylglycerin ("bio-MHG"), where the formulation and / or composition contains about 0.05 wt% to about 10 wt% of bio-MHG, preferably 0.2 wt% to about 5 wt% of bio-MHG, most preferably about 0.5 wt% to about 2.5 wt% of MHG.

[0064] Formulations and / or compositions and methods for preservation and mitigation of microbial contamination may have a pH value of about 2 to about 10, preferably about 3 to about 9, most preferably about 4 to about 8. Certain embodiments have a pH of less than about 7, preferably less than about 6.5, more preferably less than about 6, most preferably less than about 5.6.

[0065] In other embodiments, the antimicrobial and / or antiseptic efficacy of the bio-based BAGE compound of the present invention can be enhanced by the use of a booster, i.e., a compound known to those skilled in the art to enhance bacteriostatic and / or fungiostatic activity. 10 Diols, medium-chain polyols, and chelating agents can be added to the composition as boosters, all of which are preferably bio-based. Blends of bio-based BAGE compounds with such boosters can be prepared as concentrates to be added to formulations to protect against microbial contamination and growth. Suitable medium-chain diols include, but are not limited to, alkanediols and glyceryl esters. Suitable C4-C 10Examples of alkanediols include 1,2-alkanediols, 2,3-alkanediols, and mixtures thereof, such as 1,2-butanediol, 1,2-hexanediol, 1,2-heptanediol, caprylyl glycol, decylen glycol, 2,3-butanediol, 2,3-octanediol, etc., but are not limited to these, and are preferably bio-based. Preferred glyceryl esters are typically glycerol and one or more C6-C6 compounds. 10 These are monoesters with fatty acids, and examples of such glyceryl esters include glyceryl caproate, glyceryl heptanoate, glyceryl caprylate, glyceryl pelargonate, glyceryl caprate, and glyceryl caprylate / caprate. Bio-based polyols that can be added to such compositions include glycerin, propanediol (1,2-propanediol (propylene glycol), 1,3-propanediol, etc.), butanediol (1,2-butanediol, 1,3-butanediol, 2,3-butanediol, etc.), pentanediol (e.g., 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, etc.), sorbitol, sorbitan, etc. Bio-based chelating agents include bio-based C6~C 10 Alkylhydroxamic acid and its corresponding alkylhydroxamate salts, such as heptanohydroxamic acid, caprylohydroxamic acid (caprylhydroxamic acid), pelargohydroxamic acid, and caprohydroxamic acid. Caprylohydroxamic acid (caprylhydroxamic acid) or its corresponding hydroxamate salt, such as potassium caprylohydroxamate or sodium caprylohydroxamate, are preferred. Other bio-based chelating agents that can be used as boosters include tetrasodium glutamate diacetate, phytic acid and its salts, gluconic acid and its salts, galacturonic acid and its salts, galactaric acid and its salts, and combinations thereof.

[0066] In some embodiments, the bio-based BAGE compound of the present invention is present in a preservative blend composition by preparing a mixture of the bio-based BAGE compound and one or more of the above-described components. Such preservative blend compositions containing the bio-based BAGE compound of the present invention have further utility in the formulation(s) of the finished consumer product. In some embodiments, the preservative blend is a homogeneous mixture or solution of the bio-based BAGE compound and(s) other components(s). A preferred embodiment of such a preservative blend comprises one or more bio-based BAGE compounds, an alkylhydroxamic acid or its corresponding alkylhydroxamic acid salt, and optionally a diol or polyol. In such embodiments, the bio-based BAGE compound is present at a concentration of about 20% to about 80%, preferably about 30% to about 80%, more preferably about 50% to about 75%. In such embodiments, the alkylhydroxamic acid is present at a concentration of about 1% to about 20%, preferably about 2% to about 15%, more preferably about 4% to about 15%. In such embodiments, the diol or polyol is present in a concentration of optionally about 5% to about 70%, preferably about 10% to about 60%. In an exemplary embodiment, the present invention relates to a preservative blend comprising 60% to 80% methylheptylglycerin (MHG), 10% to 20% caprylhydroxamic acid (CHA), and 10% to 20% glycerin, propanediol, or a combination thereof. In a particularly preferred embodiment, the present invention relates to a preservative blend comprising about 65% to about 75% methylheptylglycerin, about 12.5% ​​to about 17.5% caprylhydroxamic acid, and about 12.5% ​​to about 17.5% glycerin, propanediol, or a combination thereof. In some embodiments, MHG, CHA, and glycerin or propanediol are each bio-based.

[0067] Embodiments of formulations and / or compositions and methods for preservation and mitigation of microbial contamination may further include reducing microorganisms by 90% within 1 week to 1 month. Certain embodiments include reducing microorganisms by 90% within 7 days. Other embodiments include reducing 99% of bacteria and 90% of yeasts and fungi within 7 days.

[0068] Embodiments of formulations and / or compositions may be incorporated and, for example, not limited to, solutions; conditioners for hair, nails, skin or textiles; shampoos; hairsprays; mustache / beard oils or waxes; hair styling products; permanent wave solutions; hair coloring products; glazes; lotions; facial and body washes; makeup removers; cleansing lotions; emollient lotions / creams; bar soaps; shaving creams; sunscreens; sunscreens; deodorants; moisturizing gels; moisturizing essences; and UV exposure It can take the form of: protective essence; shaving foam; face powder; foundation; lipstick, blush; eyeliner; wrinkle cream and anti-aging cream; eyeshadow; eyebrow pencil; mascara; mouthwash; toothpaste; oral care composition; skin cleansing composition; textile cleaning composition; dishwashing composition; hair or fur cleaning composition; deodorant or antiperspirant; color cosmetics or makeup; hair styling composition; skin moisturizer; skin conditioner; hair conditioner and nail conditioner.

[0069] In some embodiments, formulations of the present invention, when applied to the skin, exhibit a reduced "soaping" or foaming effect compared to compositions that do not contain the compounds of the present invention. Generally, foaming can occur when a formulation is applied to the skin, hair, or another surface. While the foaming effect may be beneficial in some applications, such as shower gels or shampoos, it may be undesirable in formulations of creams, lotions, and aqueous solutions intended for use on the skin, hair, and other surfaces.

[0070] For some formulations, such as personal care products, excipients such as silicones are commonly added to reduce the foaming behavior of the formulation when applied to skin, hair, or other surfaces. However, silicones are generally undesirable for use in personal care and / or home care products, and their use has been a subject of considerable debate. In some formulations, silicones are used instead of high-quality vegetable oils, and their use has become a cost-effective alternative for formulation manufacturers. However, it is well known that silicones do not decompose easily, persist in the natural environment, and can adversely affect fauna and / or flora. Therefore, in some embodiments, compositions and formulations containing the bio-based BAGE compounds of the present invention are "silicone-free" (i.e., do not contain silicones such as dimethicone or cyclopentasiloxane). "Silicone-free" compositions and formulations contain less than 1 wt%, preferably less than 0.5 wt%, more preferably less than 0.1 wt%, of silicone components, or most preferably do not contain silicone at a measurable concentration or amount. Typically, silicone-free compositions respond to friction (e.g., rubbing into skin) by becoming increasingly opaque or by "soaping," resulting in an undesirable whitening effect. This effect is particularly common in silicone-free formulations that are oil-in-water emulsions. Silicones are generally added to provide an "anti-soaping" benefit. In some embodiments, formulations containing the bio-based BAGE compounds of the present invention exhibit a reduced or substantially reduced soaping effect and may be referred to as "non-soaping" compositions or formulations. Accordingly, some embodiments include silicone-free non-soaping formulations containing at least one bio-based BAGE compound of the present invention. In some embodiments, the silicone-free non-soaping formulations contain the bio-based BAGE compound of the present invention at a concentration of about 0.05 wt% to about 10 wt%, preferably about 0.5 wt% to about 2.5 wt%.

[0071] In some embodiments, compositions and formulations containing the bio-based BAGE compound of the present invention are silicone-free oil-in-water emulsions comprising an aqueous phase and a non-aqueous, water-insoluble oil phase. In some embodiments, the oil-in-water emulsion comprises an emulsifier or stabilizer. Suitable solvents, emollients, and other components for use in the oil phase of the emulsion generally include hydrocarbons, esters, triglycerides, etc. Suitable emulsifiers include known anionic, cationic, nonionic, or amphoteric emulsifiers. One or more nonionic fatty alcohols may be present as co-emulsifiers. Compositions and formulations containing the bio-based BAGE compound of the present invention may also comprise a micelle solution comprising water and at least one surfactant.

[0072] The present invention also relates to a method for producing bio-based BAGE compounds. For example, formula (I): [ka] (In the formula, R1 is C6~C 16 A method for preparing a branched alkyl, alkenyl, or alkynyl compound (where n is 1-3) is a bio-based branched C6-C6 compound. 16 The method involves contacting an alcohol, alkenol, or alquinol with a bio-based C3 epihalohydrin or oxyranyl alcohol in the presence of a catalyst, followed by hydrolysis.

[0073] An example of a bio-based epihalohydrin is epichlorohydrin ("bio-ECH"). Bio-ECH can be supplied from any process that converts plant-derived glycerin to ECH. Plant-derived glycerin refers to glycerol obtained from the hydrolysis or transesterification (e.g., metanolysis) of plant-derived triglycerides, such as coconut oil, palm kernel oil, soybean oil, rapeseed oil, canola oil, cottonseed oil, castor oil, and sunflower seed oil. Plant-derived glycerin is preferably obtained by directly hydrolyzing plant-derived triglyceride oil with steam under high temperature and pressure, thereby splitting the oil into glycerin and fatty acids. The glycerin can then be converted to bio-ECH, for example, as shown in Scheme 4. [ka]

[0074] Therefore, one embodiment is a bio-based C4-C 10 The reaction involves a branched alcohol with bio-ECH. To obtain the glyceryl ether moiety, a bio-based compound such as oxyranyl alcohol, for example, bio-glycidol, can also be used. Exemplary catalysts such as boron trifluoride or tin tetrachloride may also be used.

[0075] In a preferred embodiment, bio-based C6-C 16 Branched alcohols are reacted with bio-ECH via a simultaneous etherification-hydrolysis pathway to obtain 100% bio-based bagage that has the same or improved performance as petrochemical-derived bagage, along with improved sustainability and better perceived consumer benefits. For example, the reaction of bio-2-octanol with bio-ECH yields bio-methylheptylglycerin (bio-MHG), as shown in Scheme 5 below. [ka]

[0076] In certain embodiments, bio-based C6-C16 Branched alkyl, alkenyl, alkynyl, or any combination thereof comprises an alcohol having a methyl branch and may have only one branch on its carbon skeleton. The branch may be defined with respect to any carbon or heteroatom in the molecule, or it may point to a stereocenter. For example, in a particular embodiment, the methyl branch is located at position 1, i.e., on a carbon atom having a hydroxyl group in an alcohol such as 1-methylheptyl alcohol, as shown below. [ka]

[0077] In certain embodiments, the bio-based branched alcohol is a secondary alcohol. Some exemplary bio-based branched alcohols are C6-C6. 10 Branched alcohols are one example. Preferred bio-based C6-C in some embodiments. 10 The branched alcohol is a completely bio-based 2-octanol ("1-methylheptyl alcohol").

[0078] Those skilled in the art will understand that bio-based BAGE can be synthesized via any route capable of efficiently converting a bio-based precursor to BAGE. For example, various routes, including U.S. Patent No. 6,437,196 and its cited documents, U.S. Patent No. 7,666,903 and its cited documents, and U.S. Patent No. 8,877,983 and its cited documents (all of which are collectively part of this specification), are available for the synthesis and purification of BAGE. Homogeneous or heterogeneous acid or base catalysis can be used. 5In a typical reaction pathway based on bio-ECH, a glycidyl ether is obtained as an intermediate, which can be immediately hydrolyzed in situ to the corresponding glyceryl ether using an aqueous base solution. Suitable bases include sodium hydroxide, potassium hydroxide, and calcium hydroxide. The reaction can be carried out in bulk or in a solvent, but a bulk reaction is preferred to avoid the need for solvent recovery, reuse, or disposal.

[0079] The obtained BAGE can be purified by any means known in the art, including distillation, liquid-liquid separation, liquid-phase extraction, solid-phase extraction, chromatographic separation, filtration, etc. Such processes can be used to remove any unreacted starting materials and undesirable by-products, odors, or colors from the BAGE product. [Examples]

[0080] These detailed descriptions are useful in illustrating the above general description and embodiments that form part of the present invention. These detailed descriptions are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0081] Example 1: Bio-based methylheptylglycerin ("Bio-MHG") Bio-MHG was prepared according to known methods in the art for the synthesis of petrochemical BAGEs, which can be summarized as follows: Bio-2-octanol (Oleris® 2-octanol, 99%, Arkema, Inc.) and bio-epichlorohydrin (i.e., "ECH") (Epicerol®, Advanced Biochemical Thailand Co., Ltd.) were reacted in the presence of a Lewis acid catalyst (SnCl4) to form a glycidyl ether intermediate, which was immediately hydrolyzed in situ by reaction with an aqueous sodium hydroxide solution. After pH adjustment and separation, the resulting crude bio-MHG was esterified with formic acid, purified by distillation of the formic acid ester adduct, followed by hydrolysis, separation, distillation and deodorization of the ester to obtain bio-MHG with a purity of 99+%.

[0082] ASTM Method D6866-18 Radiocarbon ( 14 C) Characterization of bio-MHG according to the decision 14 This indicated that carbon was present at 100% ± 1%. Therefore, virtually all carbon present in the bio-MHG was bio-based, and the bio-MHG composition contained virtually no petrochemical carbon.

[0083] Example 2: Natural lotion formulation containing Bio-MHG A lotion containing 100% bio-based ingredients was prepared according to the formulation in Table 1 using the following procedure. Water and glycerin were placed in a beaker of appropriate size equipped with an overhead mechanical stirrer, anchor-type blades, and a heating hot plate. Mixing was started at a low to medium speed, and xanthan gum was slowly separated into the aqueous phase and mixed until uniformly dispersed (no lumps remained). The mixture was then heated to 80°C. The oil phase components were combined in a separate beaker and heated to 80°C while mixing at a low speed until uniform. The oil phase mixture was added to the 80°C aqueous phase mixture while mixing at a medium to high speed. After reaching a uniform appearance, the mixture was cooled to approximately 75°C and then homogenized at 3500 rpm for 3 minutes. After homogenization, the mixture was cooled to approximately 45°C to 50°C while stirring at a medium speed. Methylheptylglycerin was added at 45°C to 50°C. After cooling to room temperature (23°C ± 2°C), the batch pH was adjusted to 5.1 ± 0.1 using citric acid (20% aqueous solution). After mixing until the composition was homogeneous, it was transferred to a suitable container and stored.

[0084] TIFF0007888469000022.tif123170

[0085] Example 3: Natural lotion formulation containing Bio-MHG Example 3 was prepared according to the procedure used in Example 2, except that the percentage of methylheptylglycerin added to the formulation was 1.00%.

[0086] Comparative Example 1: Natural lotion formulation without Bio-MHG Comparative Example 1 was prepared following the procedure used in Example 2, except that methylheptylglycerin was excluded from the formulation.

[0087] Microbiological challenge testing (MCT) of natural lotion formulations to determine preservative efficacy: The preservative efficacy of Bio-MHG in Example 1 was determined by conducting a challenge test in accordance with the United States Pharmacopeia (USP) and PCPC official test methods (see Personal Care Products Council Technical Guidelines, Microbiology Guidelines, 2018 Edition, published by Personal Care Products Council, Washington, DC, and the references cited therein). The results are shown in Tables 2A to 2D. The tables show the logarithmic values ​​of the viable cell count measured after the end of the period. The row titled "Inoculation Level" indicates the initial number of organisms present at the start of the test.

[0088] Comparative Example 1, which does not contain bio-MHG, fails to meet the PCPC acceptance criteria of a 99% reduction in bacteria and a 90% reduction in yeast and fungi within 7 days. Examples 2 and 3, which contain bio-MHG as a preservative to inhibit microbial growth, meet all USP 51 and PCPC acceptance criteria for all organisms and exceed the acceptance criteria for Gram-positive bacteria, Gram-negative bacteria, and yeast. Furthermore, Examples 2 and 3 were observed to meet the European Pharmacopoeia (EP) "B" criterion (EP-B) for the control of bacteria, yeast, and mold, namely a 99.9% reduction in bacteria (3-log reduction) and a 90% reduction in yeast and mold (1-log reduction) within 14 days (see European Pharmacopeia (Ph. Eur.) 10.0, 2021, Section 5.1.3, Efficacy of Antimicrobial Preservation).

[0089] TIFF0007888469000023.tif79170

[0090] TIFF0007888469000024.tif57170

[0091] TIFF0007888469000025.tif57170

[0092] TIFF0007888469000026.tif117170

[0093] Example 4: Natural lotion formulation containing Bio-MHG Example 4 was prepared following the procedure used in Example 2, except that the pH of the formulation was adjusted to a pH value of 6.5 ± 0.2.

[0094] Example 5: Natural lotion formulation containing Bio-MHG Example 5 was prepared following the procedure used in Example 4, except that the percentage of methylheptylglycerin added to the formulation was 1.00%.

[0095] Comparative Example 2: Natural lotion formulation without Bio-MHG Comparative Example 2 was prepared following the procedure used in Example 4, except that methylheptylglycerin was excluded from the formulation.

[0096] Microbiological challenge testing (MCT) of natural lotion formulations to determine preservative efficacy: The preservative efficacy of Bio-MHG in Example 1 was determined by conducting a challenge test in accordance with USP and PCPC official test methods. The results are shown in Tables 4A to 4D. The tables show the logarithmic values ​​of the number of viable cells measured after the end of the period. The row titled "Inoculation Level" indicates the initial number of organisms present at the start of the test.

[0097] Comparative Example 2, which does not contain bio-MHG, failed to meet the PCPC acceptance criteria of a 99% reduction in bacteria and a 90% reduction in yeast and fungi within 7 days. Examples 4 and 5, which contain bio-MHG as a preservative to inhibit microbial growth, met all PCPC acceptance criteria for all organisms and exceeded the acceptance criteria for Gram-positive bacteria, Gram-negative bacteria, and yeast. Furthermore, Examples 4 and 5 were observed to meet the European Pharmacopoeia (EP) "A" criterion, i.e., EP-A, for the control of bacteria, yeast, and mold (see European Pharmacopeia (Ph. Eur.) 10.0, 2021, Section 5.1.3, Efficacy of Antimicrobial Preservation).

[0098] TIFF0007888469000027.tif55170

[0099] TIFF0007888469000028.tif55170

[0100] TIFF0007888469000029.tif55170

[0101] Example 6: Micellar water formulation containing Bio-MHG Micellar water was prepared according to the formulation in Table 5 using the following procedure: Water was poured into a beaker of appropriate size equipped with an overhead mechanical stirrer and anchor-type blades. Mixing was started at a low to medium speed, and polysorbate 20, butylene glycol, and methylheptylglycerin were added to the batch and mixed until a clear, homogeneous solution was formed. Citric acid (20% aqueous solution) was added to adjust the pH to 5.1 ± 0.1. After mixing the batch until homogeneous, it was transferred to a suitable container and stored.

[0102] TIFF0007888469000030.tif88170

[0103] Example 7: Micellar water formulation containing Bio-MHG Example 7 was prepared following the procedure used in Example 4, except that the pH of the mixture was adjusted to 6.5 ± 0.2.

[0104] Comparative Example 3: Micellar water formulation without Bio-MHG Comparative Example 3 was prepared following the procedure used in Example 4, except that methylheptylglycerin was excluded from the formulation.

[0105] Comparative Example 4: Micellar water formulation without Bio-MHG Comparative Example 4 was prepared following the procedure used in Example 7, except that methylheptylglycerin was excluded from the formulation.

[0106] TIFF0007888469000031.tif57170

[0107] TIFF0007888469000032.tif57170

[0108] TIFF0007888469000033.tif57170

[0109] TIFF0007888469000034.tif57170

[0110] Microbiological challenge tests ("MCT") of micellar water formulations to determine preservative efficacy: The preservative efficacy of Bio-MHG in Example 1 was determined by conducting a challenge test in accordance with USP and PCPC official test methods. The results are shown in Tables 6A to 6D. "N / R" indicates "Not reported".

[0111] Comparative Examples 3 and 4, which do not contain Bio-MHG, fail to meet the PCPC acceptance criteria of a 99% reduction in bacteria and a 90% reduction in yeast and fungi within 7 days. Examples 6 and 7, which contain Bio-MHG as a preservative to inhibit microbial growth, exhibit remarkable preservative efficacy. Example 6 meets and exceeds all PCPC acceptance criteria for all organisms, and also meets the EP-A acceptance criteria of a 99% reduction in bacteria in 2 days (2-log reduction), a 99.9% reduction in bacteria in 7 days (3-log reduction), and a 99% reduction in yeast and mold in 14 days (2-log reduction). Example 7, which has a higher pH value, shows a significant improvement in preservative efficacy against Gram-positive bacteria, Gram-negative bacteria, and yeast compared to the unpreserved control (Comparative Example 4). However, at pH 6.5 ± 0.2, micellar water preserved with Bio-MHG failed to meet the PCPC acceptance criteria for preservative efficacy against mold.

[0112] TIFF0007888469000035.tif201170

[0113] Example 8: Sunscreen formulation containing bio-MHG A sunscreen formulation containing bio-MHG was prepared according to the formulation in Table 7 and the following procedure: Xanthan gum was dispersed in glycerin to form a premix. Water, glycerin-xanthan gum premix, butylene glycol, tetrasodium EDTA, and methylheptylglycerin were added to a beaker of appropriate size equipped with an overhead mechanical stirrer and a hot plate. This aqueous phase was heated to 80°C and mixed until homogeneous. The oil phase components were combined in a separate beaker, heated to 80°C, and mixed until homogeneous. Once both phases were homogeneous at 80°C, the oil phase was added to the aqueous phase while mixing at medium to high speed to form an emulsion. The emulsion was homogenized at 3500 rpm for 3 minutes. The batch was cooled to 45°C while mixing, and Simulgel NS and silica were added to the formulation during the cooling period and mixed until homogeneous. After cooling to room temperature (23°C ± 2°C), the batch pH was adjusted to 5.1 ± 0.1 using citric acid (20% aqueous solution). After mixing until the batch was homogenized, it was transferred to a suitable container and stored.

[0114] Example 9: Sunscreen formulation containing bio-MHG Example 9 was prepared according to the procedure of Example 8, except that the concentration of bio-MHG in the formulation was increased to 1.50%.

[0115] Comparative Example 5: Sunscreen formulation without Bio-MHG Comparative Example 5 was prepared according to the formulation in Table 7 and the procedure in Example 8, except that bio-MHG was excluded from the formulation.

[0116] Example 10: Sunscreen formulation containing bio-MHG Example 10 was prepared according to the formulation in Table 8 and the procedure in Example 8, except that the pH of the formulation was adjusted to 6.5 ± 0.2 using citric acid (20% aqueous solution).

[0117] Example 11: Sunscreen formulation containing bio-MHG Example 11 was prepared using the procedure of Example 10, according to the formulation in Table 8, except that the concentration of bio-MHG in the formulation was increased to 1.50%.

[0118] Comparative Example 6: Sunscreen formulation without Bio-MHG Comparative Example 6 was prepared according to the formulation in Table 8 and the procedure in Example 10, except that bio-MHG was excluded from the formulation.

[0119] TIFF0007888469000036.tif228170

[0120] The preservative efficacy of Bio-MHG in Example 1 of the sunscreen formulation was determined by conducting challenge tests in accordance with USP and PCPC official test methods. The results are shown in Tables 9A to 9F.

[0121] TIFF0007888469000037.tif55170

[0122] TIFF0007888469000038.tif55170

[0123] TIFF0007888469000039.tif55170

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[0125] TIFF0007888469000041.tif55170

[0126] TIFF0007888469000042.tif55170

[0127] Comparative Examples 5 and 6, which do not contain bio-MHG, fail to meet the PCPC acceptance criteria of a 99% reduction in bacteria and a 90% reduction in yeast and fungi within 7 days. Examples 8 to 11, which contain bio-MHG as a preservative to inhibit microbial growth, meet and exceed all USP, PCPC, and EP (A and B) acceptance criteria for all organisms, demonstrating remarkable preservative efficacy.

[0128] TIFF0007888469000043.tif85170

[0129] Example 12: Natural shampoo formulation containing Bio-MHG Example 12 was prepared according to the formulation in Table 10. Water, lauryl glucoside, sodium cocoyl glutamate, cocamidopropyl betaine, and methylheptylglycerin were added to a beaker of appropriate size equipped with an overhead mechanical stirrer. The batch was mixed at a low to medium speed until the contents were homogeneous, and then the pH was adjusted to 5.1 ± 0.1 using citric acid (20% aqueous solution).

[0130] Example 13: Natural shampoo formulation containing Bio-MHG Example 13 was prepared using the procedure of Example 12, according to the formulation in Table 10, except that the concentration of bio-MHG in the formulation was increased to 1.50%.

[0131] Comparative Example 7: Natural shampoo formulation without Bio-MHG Comparative Example 7 was prepared according to the formulation in Table 10 and the procedure in Example 12, except that bio-MHG was excluded from the formulation.

[0132] A challenge test was conducted in accordance with USP and PCPC official test methods to determine the preservative efficacy of Bio-MHG in Example 1 of the natural shampoo formulation. The results are shown in Tables 11A to 11C.

[0133] TIFF0007888469000044.tif55170

[0134] TIFF0007888469000045.tif55170

[0135] TIFF0007888469000046.tif55170

[0136] Examples 12 and 13 contained bio-MHG as a preservative to inhibit microbial growth and showed remarkable preservative efficacy that met and exceeded the USP, PCPC, and EP-B acceptance criteria for all organisms, while Comparative Example 7 showed significantly weaker preservative efficacy.

[0137] Examples 14-17: Lotion formulations containing a bio-MHG preservative blend Preservative blends were prepared by combining Bio-MHG with Spectrastat® CHA (caprylhydroxamic acid or CHA) and either glycerin or propanediol. Preservative blend A was a homogeneous mixture consisting of 71% Bio-MHG, 15% CHA, and 14% glycerin, while preservative blend B used Bio-based 1,3-propanediol instead of glycerin. Natural lotion formulations similar to those in Examples 4 and 5 were prepared using the procedure described above, according to the formulations in Table 12. Preservative blends A and B were incorporated in place of Bio-MHG. Comparative Example 2, which did not contain Bio-MHG or any of the preservative blends, was evaluated for comparison.

[0138] TIFF0007888469000047.tif176170

[0139] Challenge tests were conducted in accordance with USP and PCPC official test methods to determine the preservative efficacy of preservative blends A and B in the natural lotion formulation. The results are shown in Tables 12A to 12E.

[0140] TIFF0007888469000048.tif55170

[0141] TIFF0007888469000049.tif55170

[0142] TIFF0007888469000050.tif55170

[0143] TIFF0007888469000051.tif55170

[0144] TIFF0007888469000052.tif55170

[0145] Examples 14-17, containing bio-MHG-based preservative blends, demonstrated significant preservative efficacy that met and exceeded the USP, PCPC, EP-A, and EP-B acceptance criteria for all organisms. Comparative Example 2, however, showed very poor preservative efficacy and failed to meet the acceptance criteria for bacteria and yeast. Compared to the natural lotion formulations of Examples 4 and 5, which used bio-MHG alone at 1.0 wt% and 1.5 wt%, respectively, lower concentrations of bio-MHG (0.71 wt%) were used as components of preservative blends A and B, resulting in higher preservative efficacy at lower concentrations. This result is attributed to the boosting effect of CHA, which enhances the effectiveness of bio-MHG.

[0146] Example 18 and Comparative Examples 8-10: Anti-soaping effect of bio-MHG Preparation of cationic oil-in-water ("O / W") emulsions. The cationic O / W emulsions shown in Table 13 were prepared according to the following procedure. The aqueous phase components were placed in a beaker of appropriate size equipped with an overhead mechanical stirrer and a hot plate, and heated to 80°C while mixing until homogeneous. The oil phase components were placed in a separate beaker, and heated to 80°C while mixing until homogeneous. When both phases were homogeneous at 80°C, the oil phase was added to the aqueous phase and homogenized at 4000 rpm for 3 minutes. The resulting emulsion was cooled to room temperature while gently mixing at low speed, and then transferred to a suitable container for storage. The resulting emulsion had a pH value in the range of 4.0 to 4.2.

[0147] TIFF0007888469000053.tif161170

[0148] Assessment of soaping during application: A controlled amount of emulsion was applied to the clean, dry forearms of volunteers. The emulsion was rubbed into the skin in a controlled manner, and the appearance of the emulsion on the skin was evaluated as a function of the number of rubs. "Rubbing" was defined as swiping the index and middle fingers of the dominant hand once back and forth to apply the emulsion to the forearm using consistent motion and constant pressure. Images of the emulsion on the skin during rubbing were taken after 4, 8, and 12 rubs. Panelists (n=18) were asked to rate the appearance of the soaping effect in the images on a scale of 0 to 5, with 5 being the best soaping appearance. The scoring was normalized against Comparative Example 9 (silicone-free control), which was defined as having a soaping score of 5 after 4, 8, and 12 rubs. The evaluation results are presented in Table 14 and Figure 1.

[0149] TIFF0007888469000054.tif63170

[0150] Comparative Example 8, a cationic O / W emulsion containing 5% dimethicone, did not exhibit a soaping effect when applied to and rubbed into the skin, and its average soaping score as a function of the number of rubs was evaluated as substantially zero. Dimethicone in Comparative Example 8 was replaced with a silicone substitute (triglycerides, triheptanoins and hydrocarbons, C 13~15When replaced with LexFeel® WOW-A), an alkane emollient mixture, the resulting silicone-free O / W emulsion exhibits severe soaping upon rubbing. Comparative Example 9 demonstrates a conventional approach to mitigate this effect using a small amount of silicone (0.5 wt% dimethicone) and additional caprylyl glycol. Example 18 shows that by incorporating 2.0 wt% bio-MHG instead of 0.5 wt% dimethicone and 2.0 wt% caprylyl glycol from Comparative Example 10, a silicone-free O / W emulsion with similar, if not significantly, anti-soaping performance can be achieved using bio-based MHG instead of petroleum-based components.

[0151] Example 19: Anti-soaping effect of bio-MHG in anionic / nonionic O / W emulsions Oil-in-water ("O / W") emulsions were prepared using the same procedure as in Examples 4 and 5, following the formulations described in Table 15, and stabilized with glyceryl stearate SE (a self-emulsifying combination of the nonionic emulsifier glyceryl stearate and the anionic emulsifier potassium stearate), cetyl alcohol, and stearyl alcohol. A comparative O / W emulsion was prepared as Comparative Example 11, in which bio-MHG was excluded from the formulation. Details of the formulations are shown in Table 15.

[0152] TIFF0007888469000055.tif130170

[0153] During the evaluation of the soaping behavior when rubbed in, Comparative Example 11 was observed to exhibit severe soaping and a whitened appearance. However, when rubbed in, the O / W emulsion of Example 19 containing bio-MHG showed a dramatic reduction in soaping behavior and a favorable aesthetic appearance.

[0154] The present invention is not limited in scope by the specific embodiments described herein. In fact, various modifications of the present invention, in addition to those described herein, will be apparent to those skilled in the art from the above description and drawings. Such modifications are intended to be included in the appended claims. Term 1. Formula (I): [ka] (In the equation, R1 is branch C) 6 ~C 16 A biobased compound having an alkyl, alkenyl, or alkynyl group, where n is 1 to 3, and substantially all carbon atoms present in the compound of formula (I) are biobased. Item 2. A bio-based compound as described in Item 1, wherein n is 1. Item 3. A bio-based compound according to item 1 or 2, wherein the R1-O bond is located on the secondary carbon of R1. Section 4. R1 is branched at C 6 ~C 12 A bio-based compound according to any one of claims 1 to 3, which is alkyl, alkenyl, or alkynyl. Item 5. R1 is branched C 6 ~C 10 A bio-based compound according to any one of items 1 to 4, which is alkyl, alkenyl, or alkynyl. Item 6. R1 is branched C 8 A bio-based compound according to any one of claims 1 to 5, which is alkyl, alkenyl, or alkynyl. Section 7. [ka] A bio-based compound as described in any one of items 1 to 3. Section 8. Branch C containing at least one methyl branch R1 6 ~C 16 A bio-based compound as described in any one of items 1 to 6, which is alkyl. Item 9. A composition comprising one or more bio-based compounds of formula (I) as described in any one of items 1 to 8. Item 10. One or more bio-based compounds of formula (I) are such that R1 is branched C 6 ~C 10 The composition according to claim 9, comprising at least one compound that is alkyl, alkenyl, or alkynyl and n=1. Item 11. One or more bio-based compounds of formula (I) are such that R1 is branched C 6 ~C 16 A bio-based compound of formula (I) 1, which is alkyl, alkenyl, or alkynyl, with n=1, and R1 is branched C 6 ~C 10 The composition according to claim 9, comprising an alkyl, alkenyl, or alkynyl biobase compound of formula (I) having n=1, wherein the first biobase compound of formula (I) and the second biobase compound of formula (I) are not the same. Item 12. R1 is methyl branched C 6 ~C 16 The composition according to claim 9 or 10, wherein the alkyl, alkenyl, or alkynyl methyl branched compound is present in a ratio of 10:1 or higher compared to the concentration of the corresponding ethyl branched compound. Item 13. The bio-based compound of formula (I) is methyl branched C 6 ~C 16 A composition according to any one of claims 9 to 12, comprising a compound wherein R1 has a single methyl branch, and this compound accounts for 95 wt% or more of all compounds of formula (I) present in the composition. Section 14. The bio-based compound of formula (I) above,

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[0155] It should be further understood that all values ​​are approximations and are provided for illustrative purposes only. All references cited and discussed herein constitute part of this specification by citation to the same extent that each reference constitutes part of this specification by citation.

[0156] References 1. K. Urata and N. Takaishi, "Ether Lipids Based on the Glyceryl Ether Skeleton: Present State, Future Potential," J. Amer. Oil. Chem. Soc. 73(7):819-830 (1996). 2. W. Johnson, Jr. et al., "Safety Assessment of Alkyl Glyceryl Ethers as Used in Cosmetics," Int. J. Tox. 32(Suppl 3):5S-21S (2013). 3. Schuelke, http: / / www.ethylhexylglycerin.com / ethylhexylglycerin / en / Applications.php 4. Langsrud et al. PLoS One 11(10):e0165228 (2016). 5. M. Ricciardi, et al., "First Attempt of Glycidol-to-Monoalkyl Glyceryl Ethers Conversion by Acid Heterogeneous Catalysis: Synthesis and Simplified Sustainability Assessment," ChemSusChem 11:1829-1837 (2018). See also U.S. Patent Nos. 6,437,196, 7,666,903, and 8,877,983.

Claims

1. Equation (I): 【Chemistry 1】 A bio-based compound, It is 3-[(1-methylheptyl)oxy]-1,2-propanediol having a purity of at least 99% by weight, Substantially all carbon present in the compound of formula (I) is biobased. Bio-based compounds.

2. A composition comprising the bio-based compound of formula (I) as described in claim 1.

3. A compound of formula (I) in an amount of 20% to 80% by weight, and Containing 1% to 20% by weight of alkylhydroxamic acid or its alkylhydroxamic acid salt, The composition according to claim 2.

4. The composition according to claim 3, wherein the composition is silicone-free.

5. Formula (I): 【Chemistry 2】 A method for preparing a bio-based compound, The process involves contacting a bio-based 2-octanol with a bio-based epichlorohydrin in the presence of a catalyst, followed by hydrolysis. The compound of formula (I) is 3-[(1-methylheptyl)oxy]-1,2-propanediol having a purity of at least 99% by weight. method.

6. The method according to claim 5, wherein the catalyst is boron trifluoride or tin tetrachloride.

7. A bio-based compound of formula (I) as described in claim 1, At least one other ingredient, A compound containing the following ingredients.

8. An antimicrobial composition comprising the bio-based compound described in claim 1.

9. The bio-based compound according to claim 1, which is a liquid at room temperature.

10. A personal care product, home care product, textile care product, institutional care product, pharmaceutical product, veterinary pharmaceutical product, food product or industrial product, or a component thereof, The at least one other component is selected from the group consisting of water, surfactants, emollients, moisturizers, conditioning agents, chelating agents, surfactants, bleaching or whitening agents, pH adjusters, fragrances, emulsifiers, exfoliants, antioxidants, plant components, mica, smectite, thickeners, cannabinoids, oils, dyes, waxes, amino acids, nucleic acids, vitamins, hydrolyzed proteins and their derivatives, glycerin and its derivatives, enzymes, anti-inflammatory agents and other drugs, bactericides, antifungal agents, disinfectants, antioxidants, UV absorbers, dyes and pigments, preservatives, sunscreen activators, antiperspirant activators, oxidizing agents, pH balancers, moisturizers, peptides and their derivatives, anti-aging activators, hair growth activators, anti-cellulite activators, and combinations thereof. The formulation according to claim 7.

11. The composition according to claim 7, wherein the bio-based compound of formula (I) is present in the composition at a concentration of 0.05% to 10% by weight.

12. The formulation according to claim 7, which is silicone-free.

13. The formulation according to claim 7, which is a lotion, micellar water, oil-in-water emulsion, sunscreen, shampoo, or deodorant.

14. The formulation according to claim 7, which is a liquid, solid, aerosol, gel, wax, oil, emulsion, or micelle composition.

15. The composition according to claim 8, further comprising a booster selected from the group consisting of medium-chain diols, medium-chain polyols, chelating agents, and combinations thereof.

16. The medium-chain diol is selected from the group consisting of C4-C10 alkanediols, glyceryl esters of C6-C10 fatty acids, and combinations thereof. The medium-chain polyol is selected from the group consisting of glycerin, 1,2-propanediol, 1,3-propanediol, and combinations thereof. The chelating agent is selected from the group consisting of C6-C10 alkylhydroxamic acid or its alkylhydroxamic acid salt, tetrasodium glutamate diacetate, phytic acid or its salt, gluconic acid or its salt, galacturonic acid or its salt, galactaric acid or its salt, and combinations thereof. The antimicrobial composition according to claim 15.

17. The antimicrobial composition according to claim 16, wherein the chelating agent is present and is caprylhydroxamic acid, a hydroxamate of caprylhydroxamic acid, or a combination thereof.

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