polyol partial esters of poly(multihydroxyaliphatic acids)

Abstract

The present invention provides polyol partial esters of poly(multihydroxyaliphatic acids), methods for their production and uses, in particular in cosmetics.

Description

Technical Field

[0001] This invention provides polyol metaesters of poly(polyhydroxy fatty acids), their production methods and uses, particularly in cosmetics.

[0002] Existing technology Existing technology application areas Poly(ricinoleic acid) and poly(hydroxystearic acid) are homopolymers derived from the polymerization of monohydroxy fatty acids ricinoleic acid and 12-hydroxystearic acid, respectively.

[0003] Esters of poly(ricinoleic acid) and poly(hydroxystearic acid) are well known in cosmetic applications, for example, under the following INCI names: Dimeric linoleyl alcohol bis-polyricinoleate, polyethylhexyl ricinoleate, polylauryl / myristyl ricinoleate, polymethyl ricinoleate, polyglycerol-4 oleate / polyricinoleate, polyglycerol-3 polyricinoleate, polyglycerol-4 polyricinoleate, polyglycerol-5 polyricinoleate, polyglycerol-6 polyricinoleate, polyglycerol-10 polyricinoleate, propylene glycol dimeric ricinoleate Polyhydroxystearate behenate, dipentaerythritol tetrabenzene / polyhydroxystearate, dipentaerythritol tri-polyhydroxystearate, polyethylhexyl hydroxystearate, stearoyl polyethylhexyl hydroxystearate, Glyceryl polyether-18 polyhydroxystearate, polyhydroxystearate isooctyl ester, polyethylene glycol-30 dihydroxystearate, pentaerythritol behenate / polyhydroxystearate, polyglycerol-4 diisostearate / polyhydroxystearate / sebate, polyglycerol-2 dihydroxystearate, polyglycerol-6 polyhydroxystearate, polyglycerol-10 polyhydroxystearate.

[0004] In particular, esters that can be obtained by esterification of polyols with poly(ricinoleic acid) and / or poly(hydroxystearic acid) have proven to be highly versatile in terms of potential applications.

[0005] For example, polyglycerol polyricinoleate (PGPR, E476) is an emulsifier that can be used to reduce the viscosity of chocolate, cocoa butter substitute chocolate, and similar coatings, especially when used in combination with other substances such as lecithin. It can also be used as an emulsifier in salad dressings and spreads, or to improve the texture of baked goods.

[0006] EP1500427 discloses polyglycerol metaesters of polyhydroxystearic acid and polyfunctional carboxylic acids, which can be obtained by esterification with the following substances: a) Polyglycerol mixtures, with b) Polyhydroxystearic acid and c) Dicarboxylic acids, tricarboxylic acids, or mixtures thereof.

[0007] These polyglycerol metaesters allow for the formulation of highly liquid emulsions that have a pleasant feel on the skin, while also providing improved low-temperature storage resistance.

[0008] EP1683781 discloses polyglycerol metaesters of polyricinoleic acid and polyfunctional carboxylic acids, which are prepared by esterification of the following substances: a) Polyglycerol mixtures with b) At least one specific polyricinoleic acid And, optionally present, polyhydroxystearic acid, and c) At least one dicarboxylic acid and / or tricarboxylic acid and d) At least one fatty acid.

[0009] These polyglycerol metaesters allow for the formulation of low-viscosity emulsions with a light, skin-like feel, as well as formulations that are highly stable at high temperatures and also stable at low temperatures.

[0010] EP3500550 discloses polyglycerol metaesters obtained by esterification of a mixture of polyglycerol and carboxylic acids, wherein the carboxylic acid mixture comprises: a) At least one polyhydroxycarboxylic acid having 8 to 32 carbon atoms. b) At least one short-chain dicarboxylic acid having 2 to 16 carbon atoms, c) At least one long-chain dicarboxylic acid having 24 to 44 carbon atoms, and d) At least one fatty acid selected from linear unsaturated and branched saturated fatty acids having 14 to 24 carbon atoms.

[0011] These polyglycerol metaesters can be used as W / O emulsifiers.

[0012] The esters in the aforementioned examples all suffer from the drawback of being based on castor seed oil, which is a source of ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid) and 12-hydroxystearic acid (which is hydrogenated ricinoleic acid).

[0013] For sustainability reasons, it is essential to diversify the base of renewable raw materials.

[0014] Existing technologies for epoxidation and polymerization The epoxidation and dihydroxylation of unsaturated fatty acids and unsaturated vegetable oils are well known. The condensation / polymerization of (polyhydroxy) monocarboxylic acids and epoxide monocarboxylic acids are also well known.

[0015] Aguilera et al. described the lipase-catalyzed epoxidation of oleic acid in Chemical Engineering & Processing: Process Intensification 174 (2022) 108882. As a side reaction in the epoxidation process, they described the formation of an ester through a ring-opening reaction with the carboxylic acid group as the main nucleophile, which is equivalent to the homopolymerization of 9,10-epoxystearic acid to poly(9,10-dihydroxystearic acid).

[0016] Miao et al., in Journal of Polymer Science, Part A: Polymer Chemistry (2008), 46 (12), 4243-4248, described the epoxidation of oleic acid (99% C18:1) using Candida antarctica lipase B and hydrogen peroxide (H2O2) in toluene as a solvent to obtain what they called “oleic acid epoxide” (in fact, 9,10-epoxystearic acid). This intermediate epoxy fatty acid was then homopolymerized under solvent-free conditions to obtain what they called “poly(oleic acid)” (which is equivalent to poly(9,10-dihydroxystearic acid)).

[0017] In J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3159–3170, Evans et al. described the synthesis of 9,10-epoxystearic acid from oleic acid (90% C18:1) and its subsequent homopolymerization. Furthermore, illustrative and representative descriptions of the polymerization process are provided.

[0018] In Angew. Chem. Int. Ed. 2003, 42, 5623–5625, Usui et al. described the catalytic dihydroxylation of oleic acid to 9,10-dihydroxystearic acid using H2O2 and resin-supported sulfonic acid in organic solvents and metal-free systems.

[0019] DE2129994 A1 discloses the condensation of (polyhydroxy) monocarboxylic acids (examples of glyceric acid, 9,10-dihydroxystearic acid, or trihydroxystearic acid) having 2 to 6 hydroxyl groups and a total of 3 to 22 carbon atoms for use in coating compositions. Cocondensation with other (monohydroxy) monocarboxylic acids such as 12-hydroxystearic acid and ricinoleic acid, oleic acid, lauric acid, etc., is also described. The resulting polymer is monofunctional with respect to the carboxyl group. Copolyesters of various dihydroxycarboxylic acids are also described. Example 2 describes the synthesis of poly(9,10-dihydroxystearic acid) in xylene, starting from 9,10-dihydroxystearic acid. The resulting poly(9,10-dihydroxystearic acid) has an acid value of 22 mg KOH / g and a hydroxyl value of 166 mg KOH / g.

[0020] Fehling, in JAOCS 1995, 72, 355-359, describes hydroxylated fatty acids (HOFAs) prepared from various vegetable oils containing a large amount of laurylates, which are formed through intermolecular esterification of HOFAs. These laurylates mainly consist of saturated fatty acids that are esterified to threo-9,10-dihydroxyoctadecanoic acid or dihydroxytetrahydrofuranoctadecanoic acid, such as 9,12-dihydroxy-10,13-epoxyoctadecanoic acid and 10,13-dihydroxy-9,12-epoxyoctadecanoic acid.

[0021] Casali et al. described in Green Chem 2022, 24, 2082-2093 that when linoleic acid is subjected to specific epoxidation and subsequent hydrolysis conditions, a dihydroxytetrahydrofuran derivative can be formed by intramolecular dehydration of an intermediate dihydroxy derivative obtained from the partial hydrolysis of diepoxystearic acid.

[0022] DE4125031 discloses a method for producing hydroxylated fatty acid compounds by acid-catalyzed hydrolysis of epoxidized fatty acids, their esters, and amides, characterized in that the epoxidized fatty acid compounds having one or more central ethylene oxide rings are reacted with water in the presence of water under conditions where acid-activated clay and / or silicates and / or activated carbon are used as catalysts.

[0023] JAOCS 1995, 72, 349 discloses a method for the industrial production of hydroxylated fatty acids by epoxidation of vegetable oils and their derivatives, followed by catalytic ring-opening of the epoxide in the presence of water or other hydrogen donors such as alcohols, glycols and amines.

[0024] The object of this invention is to provide excellent emulsifiers, particularly for use in cosmetic formulations and food applications. Summary of the Invention

[0025] Surprisingly, it has been found that poly(polyhydroxy fatty acid) polyol esters obtainable by the method of the present invention described below can solve the problems that give rise to the present invention.

[0026] The subject of this invention is the method for producing poly(polyhydroxy fatty acid) polyol esters as described in claim 1.

[0027] Another subject of the present invention is polyol esters of poly(polyhydroxy fatty acids) obtainable by the method of the present invention, and formulations containing the same.

[0028] Another subject of the present invention is the use of poly(polyhydroxy fatty acid) polyol esters according to the present invention in various fields.

[0029] One advantage of this invention is that the poly(polyhydroxy fatty acid) polyol esters described herein can be prepared entirely from renewable raw materials.

[0030] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters described in this article can be prepared based on green chemistry principles.

[0031] Another advantage of the present invention is that it can provide formulations that do not contain polyethylene glycol ethers.

[0032] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters described herein are biodegradable.

[0033] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters described in this article have good ecotoxicological properties.

[0034] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described in this article is that they are very gentle on the skin, non-irritating, and non-toxic.

[0035] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described herein is their improved sensory properties in formulations. The stickiness of sunscreen formulations is reduced after application. The formulations are absorbed by the skin more quickly due to increased absorption during application and within 5 minutes thereafter on the skin.

[0036] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described in this article is that they enhance the "velvety smoothness" of the formulation.

[0037] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters described in this article have good skin moisturizing effects.

[0038] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters described herein are well-suited for use in sunscreen formulations with very high concentrations of UV-protective filters.

[0039] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described herein is that they impart very high water resistance to the formulation. In sunscreen formulations, this results in the formulation ensuring prolonged UV protection in water or after bathing.

[0040] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that they impart increased abrasion resistance to coloring pigments when used in cosmetic applications.

[0041] In the context of pigment-containing formulations, another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that they allow the pigments to be well dispersed in the formulation.

[0042] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described in this article is their good compatibility with formulations containing UV-protective filters or pigments.

[0043] Generally speaking, the poly(polyhydroxy fatty acid) polyol esters described in this article impart good stability to the formulation.

[0044] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is their ease of processing, as they are readily mixed with typical cosmetic oils and can be quickly incorporated into the corresponding emulsions.

[0045] Another advantage of the poly(polyhydroxy fatty acid) polyol esters described in this article is that they impart a high gloss to solid or waxy formulations such as lipsticks.

[0046] Another advantage of the polyglycerol metaesters according to the invention is that they are particularly resistant to electrolytes, which means that formulations containing, for example, large amounts of salt remain stable.

[0047] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that they have a structuring and viscosity-increasing effect in formulations with high oil content or even pure oil.

[0048] One advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that formulations based on the poly(polyhydroxy fatty acid) polyol esters described herein can be prepared by a cold process without heating.

[0049] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention are highly resistant to different oil phase contents in emulsions.

[0050] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention are highly resistant to different oil phase compositions in the emulsion.

[0051] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention have a pleasant, less "industrial" odor.

[0052] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that even high proportions of natural oils such as almond oil can be well stabilized in emulsions.

[0053] Another advantage of the poly(polyhydroxy fatty acid) polyol esters according to the present invention is that the emulsion can be stabilized over a wide viscosity range, from spray to emulsion to cream.

[0054] Another advantage of the present invention is that the emulsion based on the emulsifier according to the invention has very good compatibility with propellants such as propane, n-butane and isobutane, thereby simplifying the production of aerosol systems.

[0055] Another advantage of the poly(polyhydroxy fatty acid) polyol ester according to the present invention is that the emulsion stabilized with the poly(polyhydroxy fatty acid) polyol ester has a skin feel that is at least as good as that of prior art emulsifiers.

[0056] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention can be used as emulsifiers and lubricating additives in metalworking fluids (pure oil or water-based fluids), in which they provide excellent emulsion stability, reduce oil droplet coalescence, increase lubrication properties such as the lubricity of base oils, especially under high friction, and are even soluble in GTL oils, providing optimal additional lubricity under stress and reducing the applied torque during tapping. Furthermore, the poly(polyhydroxy fatty acid) polyol esters according to the present invention provide excellent stability for rolling oil emulsions, with reduced coalescence, good lubricity, and good surface quality.

[0057] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention can be used as friction modifiers for lubricants.

[0058] Another advantage is that the poly(polyhydroxy fatty acid) polyol ester according to the present invention can reduce the coefficient of friction.

[0059] Another advantage is that, due to the lower treatment rate and / or a better combination of oil compatibility and friction-reducing properties, the poly(polyhydroxy fatty acid) polyol esters according to the present invention can lead to more efficient friction reduction.

[0060] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention can improve flow properties, reduce Casson yield value in chocolate and cocoa butter substitutes, and provide excellent viscosity control.

[0061] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention work well when used in combination with ammonium phospholipids (AMP) and lecithin.

[0062] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention are tasteless and odorless, preventing off-flavors and unpleasant castor oil odors from developing in chocolate.

[0063] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the invention can be pumped at room temperature or easily mixed with (cosmetic) oils for convenient handling.

[0064] Another advantage is that the poly(polyhydroxy fatty acid) polyol esters according to the present invention allow for optimal molding, with excellent distribution in the mold and no bubbles.

[0065] Therefore, the present invention provides a method for producing polyol esters of poly(polyhydroxy fatty acids), comprising the following steps: A) Provide at least one poly(polyhydroxy fatty acid), B) Provide at least one polyol, preferably a mixture of more than one polyol. C) Esterify the at least one poly(polyhydroxy fatty acid) and the at least one polyol.

[0066] The term "polyhydroxy fatty acid" as used in this invention describes saturated or unsaturated, linear or branched, cyclic or acyclic carboxylic acids having 2 to 12, preferably 2 to 10, more preferably 2 to 6 hydroxyl groups, and a total of 3 to 36, preferably 6 to 28, more preferably 8 to 22 carbon atoms.

[0067] The term "epoxy fatty acid" as used in this invention describes a saturated or unsaturated, linear or branched, cyclic or acyclic carboxylic acid having at least one epoxy functional group and a total of 3 to 36, preferably 6 to 28, more preferably 8 to 22 carbon atoms.

[0068] The term "poly(polyhydroxy fatty acid)" within the meaning of this invention describes a polyester polymer that can be obtained by polymerizing at least one polyhydroxy fatty acid and / or at least one epoxy fatty acid.

[0069] Preferably, the poly(polyhydroxy fatty acid) within the meaning of this invention is monofunctional with respect to the carboxyl group.

[0070] More preferably, at least two of the 2 to 12, more preferably 2 to 10, and more preferably 2 to 6 hydroxyl groups in the polyhydroxy fatty acid structural unit form an ortho-diol, that is, at least two hydroxyl groups are attached to adjacent carbon atoms.

[0071] When averages are stated below, they are multiple averages unless otherwise stated.

[0072] Unless otherwise stated, percentages are data expressed as a weight percentage. The same applies to parts per million (ppm).

[0073] When measurements are stated below, unless otherwise stated, these values ​​were determined at a temperature of 25 °C and a pressure of 1013 mbar.

[0074] The preferred method according to the present invention is characterized in that step A) includes the following sub-steps: A1) Provides at least one unsaturated fatty acid, A2) Epoxidize at least one carbon-carbon double bond of the at least one unsaturated fatty acid to obtain an epoxidized fatty acid. A3) Ring-opening of the epoxy groups of the epoxide fatty acid, simultaneously obtaining a polyhydroxy fatty acid, and A4) Polymerize the epoxy fatty acid and / or the polyhydroxy fatty acid to obtain at least one poly(polyhydroxy fatty acid).

[0075] The preferred method according to the present invention is characterized in that the unsaturated fatty acid is selected from the group consisting of: arachidonic acid, octadecanoic acid, catalpain, dihomo-γ-linolenic acid, docosahexaenoic acid, docosapentaenoic acid, docosatraenoic acid, eicosapentaenoic acid, eicosatraenoic acid, eicosaenoic acid, 11-eicosaenoic acid, trans oleic acid, α-tungsten acid, β-tungsten acid, erucic acid, codoleic acid, linoleic acid, trans linoleic acid, linolenic acid, α-linolenic acid, γ-linolenic acid. -Linolenic acid, meadic acid, myristone acid, nervonic acid, octadecanoic acid, octadecanoic acid, oleic acid, ω-3 fatty acids, ω-6 fatty acids, ω-7 fatty acids, ω-9 fatty acids, palmitoleic acid, α-parilla oleic acid, guaranaic acid, phellandrene, terpineic acid, punicic acid, ricinoleic acid, rumen acid, sapiensic acid, stearatetraenoic acid, sulphuric acid, undecenoic acid, isoleic acid and piperidinic acid, preferably erucic acid, linoleic acid, oleic acid and palmitoleic acid.

[0076] The preferred method according to the invention is characterized in that, in sub-step A1), a mixture of at least two unsaturated fatty acids is provided, more preferably a mixture of at least two unsaturated fatty acids selected from erucic acid, linoleic acid, oleic acid and palmitic acid.

[0077] The alternative preferred method according to the invention is characterized in that, in sub-step A1), a mixture of at least one unsaturated fatty acid and at least one saturated fatty acid is used.

[0078] The saturated fatty acids are preferably selected from the group consisting of: hexanoic acid, heptanoic acid (preferably obtained by pyrolysis of ricinoleic acid), octanoic acid, nonanoic acid (e.g., obtained by ozone decomposition or oxidative cracking of oleic acid), decanoic acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, arachidic acid, behenic acid, ceramide, and ceramide.

[0079] The preferred method according to the invention is characterized in that the epoxidation in sub-step A2) is catalyzed by an enzyme in the presence of at least one peroxide, preferably hydrogen peroxide, said enzyme being preferably selected from cytochrome P450 enzymes, lipoxygenases, peroxidases, epoxide hydrolases and lipases, preferably lipases.

[0080] According to the present invention, the lipase preferably used in method step A2) is in a state of being immobilized on a solid carrier.

[0081] According to the present invention, the lipase preferably used in method step A2) is a lipase selected from the group consisting of: lipases from Thermomyces lanuginosus The lipase (accession number O59952) is from *Candida antarcticis*. Candida antarctica Lipases A and B (accession number P41365) and those from Mucor spp. ( Mucor miehei The lipase (accession number P19515) from Humicola sp. The lipase (accession number O59952) is from Rhizopus javanica ( Rhizomucor javanicus The lipase (accession number S32492) from Rhizopus oryzae ( Rhizopus oryzae The lipase (accession number P61872) from Candida albicans ( Candida rugosa Lipases (accession numbers P20261, P32946, P32947, P3294, and P32949) from *Rhizopus sylvatica* (… Rhizopus niveus The lipase (accession number P61871) from Penicillium carmenere ( Penicillium camemberti The lipase (accession number P25234) from Aspergillus niger ( Aspergillus niger Lipases (ABG73613, ABG73614 and ABG37906) and those from Penicillium circulatoryum ( Penicillium cyclopium Lipases from *Candida antarctica* (accession number P61869) are preferred, especially those derived from *Candida antarctica*. Candida antarctica Lipases A and B (accession number P41365), and their respective homologs at an amino acid level of at least 60%, preferably at least 80%, preferably at least 90%, and particularly preferably at least 95%, 98%, or 99%.

[0082] In the context of this invention, the accession number listed corresponds to an NCBI Protein Bank database entry dated January 1, 2017; the version number of this entry is typically identified by ".number" in this context, such as ".1".

[0083] Enzymes that are homologous at the amino acid level preferably exhibit at least 50%, and especially at least 90%, of the enzyme activity compared to the reference sequence defined in the context of this invention in propyl laurate units (PLU).

[0084] To determine enzyme activity in PLU (propyl laurate units), 1-propanol and lauric acid were homogenized in an equimolar ratio at 60 °C. The reaction was initiated with the addition of the enzyme, and the reaction time was measured. Samples were taken from the reaction mixture at regular intervals, and the amount of lauric acid converted was determined by titration with potassium hydroxide solution. Enzyme activity in PLU was derived from the rate at which 1 g of the relevant enzyme synthesizes 1 µmol of propyl laurate per minute at 60 °C; for this purpose, see also US20070087418, particularly

[0185] .

[0085] Commercial examples and the lipases also preferably used in the methods according to the invention are the commercial products LipozymeTL IM, Novozyme 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all commercial products from Novozymes A / S, Bagsvaerd, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercial products from Roche Molecular Biochemicals, Mannheim, Germany), CALB Immo Plus™ from Purolite, and Lipase M "Amano", Lipase F-AP 15 "Amano", Lipase AY "Amano", Lipase N "Amano", Lipase R "Amano", Lipase A "Amano", Lipase D "Amano", Lipase G "Amano" (all commercial products from Amano, Japan).

[0086] For the purposes of this invention, "homology at the amino acid level" should be understood as meaning "amino acid identity," which can be determined using known methods. Generally, a dedicated computer program with an algorithm that takes into account specific requirements is used. A preferred method for determining identity first generates the maximum alignment between the sequences to be compared. Computer programs for determining identity include, but are not limited to, the GCG package, which includes... - GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), p. 387, Genetics Computer Group University of Wisconsin, Medicine (WI), and - BLASTP, BLASTN, and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pp. 403-410). The BLAST procedure is available from the National Center for Biotechnology Information (NCBI) and other sources (BLAST Handbook, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., ibid.).

[0087] Those skilled in the art will recognize that various computer programs are available for calculating the similarity or identity between two nucleotide or amino acid sequences. For example, the percentage of identity between two amino acid sequences can be determined using an algorithm developed, for instance, by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which has been integrated into the GAP program in the GCG software package (available at http: / / www.gcg.com), using a Blossom 62 matrix or a PAM250 matrix with vacancy weights of 16, 14, 12, 10, 8, 6, or 4, and length weights of 1, 2, 3, 4, 5, or 6. Those skilled in the art will recognize that using different parameters will result in slightly different results, but the percentage of identity between the two amino acid sequences will not differ significantly overall. The Blossom 62 matrix is ​​typically used with the default settings (vacancy weight: 12, length weight: 1).

[0088] In the context of this invention, 60% identity according to the above algorithm means 60% homology. This also applies to higher levels of identity.

[0089] In step A2), according to the present invention, it is preferred to use a lipase with a concentration of 1 to 2000 PLU, more preferably 5 to 1500 PLU, and more preferably 50 to 1250 PLU per gram of unsaturated fatty acid to be converted.

[0090] Method step A2) According to the present invention, it is preferably carried out in the presence of an aqueous hydrogen peroxide solution with a concentration of 1% to 65%, preferably 5% to 60%, more preferably 15% to 55%.

[0091] Method step A2) According to the present invention, it is preferably carried out at a temperature of 20°C to 95°C, more preferably 30°C to 90°C, and more preferably 35°C to 80°C.

[0092] Preferably, during the time period of step A2), the temperature increases within the range of 10 K to 50 K. The temperature increase can be achieved gradually or through a gradual temperature change.

[0093] Method step A2) According to the present invention, it is preferably carried out at a pressure of 1 mbar to 1013 mbar, more preferably 5 mbar to 900 mbar, and even more preferably 10 mbar to 500 mbar.

[0094] Preferably, during the time period of method step A2), the pressure decreases within the range of 100 mbar to 1000 mbar. The pressure decrease can be achieved gradually or through a pressure gradient.

[0095] The preferred method according to the invention is characterized in that, in sub-step A4), at least one selected from 9,10-epoxy-18-hydroxyoctadecanoic acid and 9,10,18-trihydroxyoctadecanoic acid is copolymerized with the epoxy fatty acid and / or the polyhydroxy fatty acid.

[0096] The preferred method according to the invention is characterized in that the poly(polyhydroxy fatty acid) provided in step A) of the method of the invention has an acid value (AV) of 10 to 200 mg KOH / g, preferably 35 to 120 mg KOH / g, and particularly preferably 40 to 90 mg KOH / g.

[0097] Appropriate methods for determining acid value, especially those according to DGF CV 2, DIN EN ISO 2114, Ph.Eur. 2.5.1, ISO 3682 and ASTM D 974.

[0098] The preferred method according to the invention is characterized in that the poly(polyhydroxy fatty acid) provided in step A) of the method of the invention has an epoxy-[O] content (ethylene oxide oxygen content) of ≤10.0%, preferably ≤5.0%, more preferably ≤1.0%, wherein the percentage refers to all poly(polyhydroxy fatty acids) provided in step A).

[0099] The determination of epoxy-[O] content can be achieved as described below: The epoxy ring reacts with hydrochloric acid (HCl) in a strictly non-aqueous medium to form a C-Cl and a C-OH group through ring-opening. Excess hydrochloric acid is back-titrated with potassium hydroxide (KOH) in ethanol, while simultaneously considering parallel blank titrations. Water interferes with the ring-opening reaction with hydrochloric acid. Basic compounds neutralize some of the hydrochloric acid required for ring-opening. Due to their basicity, amines neutralize some of the hydrochloric acid required for ring-opening. Acidic compounds cause incorrect consumption of KOH during back titration.

[0100] Material: A 0.05 g solution of cresol red in tetrahydrofuran (THF; 100 mL) was used as an indicator solution. A solution of 0.1 mol / L HCl in 1,4-dioxane / THF (2:1 v / v) An ethanolic solution of KOH (0.1 mol / L) Ethanol (industrial grade) The required sample quantity (SQ) is calculated using the following formula and must be weighed accurately to ±0.1 mg: SQ (in grams) = 3.2 / X in SQ = Required sample amount, in grams X = Expected epoxy-[O] content (ethylene oxide oxygen content), in %

[0101] The maximum deviation from the target sample volume must not exceed 5%. Add 40 ml of 0.1 mol / L HCl in 1,4-dioxane / THF (2:1 v / v) to the calculated sample volume using a full-volume pipette. Seal the flask with a suitable glass stopper. Gently rotate the mixture until the sample is completely dissolved. Now allow the mixture to react at room temperature for 15 minutes. During the reaction time, the mixture should be gently rotated intermittently. Under no circumstances should the mixture be heated above 25 °C. Then, top the mixture with ethanol to a volume of 100 ml. After adding a few drops of indicator solution, titrate the mixture with 0.1 mol / L potassium hydroxide ethanol solution. When the indicator is added, the solution turns brick red and then lemon yellow shortly before the endpoint. The titration endpoint is reached when a new color change to blue-violet occurs. Collect two blank values ​​in parallel with the sample titration, in the same manner as above but without sample material. Furthermore, care must be taken to ensure that the ethanol (KOH) does not come into contact with CO2 in the air. It is recommended to use a suitable CO2 absorption tube, otherwise interference may occur. The volume of water consumed for blank titration must be between 38 and 42 ml, and in the case of duplicate titrations, the deviation between them must not exceed 0.15 ml. Otherwise, the blank titration must be repeated. Considering the consumption of 0.1 mol / L ethanol-potassium hydroxide solution for blank titration and sample titration, as well as the sample weight, the epoxy-[O] content is calculated as follows: in V 空白 = Consumption of 0.1 mol / L KOH ethanol solution (in ml) during blank value determination. V = The volume of 0.1 mol / L KOH ethanol solution consumed during sample titration (in ml). c = Concentration of the KOH ethanol solution (here, 0.1 mol / L) M = Molecular weight of oxygen (here, 16 g / mol) SQ = Sample quantity (in grams) The preferred method according to the invention is characterized in that the poly(polyhydroxy fatty acid) provided in step A) of the method of the invention has a hydroxyl value (OHV) of 10 to 400 mg KOH / g, preferably 50 to 300 mg KOH / g, and particularly preferably 70 to 200 mg KOH / g.

[0102] Suitable methods for determining hydroxyl values, especially those according to DGF CV 17a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.

[0103] The preferred method according to the invention is characterized in that the poly(polyhydroxy fatty acid) provided in step A) of the method of the invention has a saponification value (SV) of 140 to 500 mg KOH / g, preferably 150 to 250 mg KOH / g.

[0104] Suitable methods for determining saponification value, especially those according to DGF CV 3, DIN EN ISO 3681 and Ph.Eur. 2.5.6.

[0105] The preferred method according to the invention is characterized in that the poly(polyhydroxy fatty acid) provided in step A) comprises at least one dihydroxytetrahydrofuranoctadecanoic acid, which is either a free monomeric dihydroxytetrahydrofuranoctadecanoic acid or covalently bound to the poly(polyhydroxy fatty acid).

[0106] Preferably, the dihydroxytetrahydrofuranoctadecanoic acid is present in an amount of 0.0001% to 10%, wherein the percentage refers to the sum of the total poly(polyhydroxy fatty acids) provided in step A) and all dihydroxytetrahydrofuranoctadecanoic acid.

[0107] The term "dihydroxytetrahydrofuranoctadecanoic acid" within the meaning of this invention is defined according to the definitions of Fehling in JAOCS 1995, 72, 355-359 and Casali et al. in Green Chem 2022, 24, 2082-2093.

[0108] The preferred method according to the invention is characterized in that the polyol provided in step B) has three or more, preferably four or more, especially more than six carbon atoms.

[0109] When using several polyols, the mixture naturally has an average of three or more, preferably four or more, and especially more than six carbon atoms.

[0110] The preferred method according to the present invention is characterized in that the polyol provided in step B) is selected from the group consisting of: 1,10-decanediol, 1,12-dodecanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-pentanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-dimethyl-1,3-propanediol (neopentanediol), 2,4-diethyl-1,5-pentane, 2,5-dimethyl-3-hexyn-2,5-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl 1,3-Propanediol, 2-Methyl-2-propyl-1,3-Propanediol, 2-Methyl-2-propyl-1,3-Propanediol, 2-sec-butyl-2-methyl-1,3-propane, 3-hexyn-2,5-diol, bis(trimethylolpropane), isosorbide, pinacol, tricyclodecanediethanol, tripentaerythritol, 1,2-butanediol, 1,2-propanediol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,4-sorbitol, 1,5-sorbitol, diglycerides, dipentaerythritol, erythritol, glycerol, isomaltitol, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, dehydrated xylitol, xylitol and polyglycerol, preferably polyglycerol.

[0111] The term "polyglycerol" within the meaning of this invention should be understood to refer to polyglycerol that may also contain glycerol. Therefore, glycerol content may need to be considered in calculations of amount, mass, etc. Due to its polymerization properties, polyglycerol represents a statistical mixture of different compounds. Polyglycerol can have ether bonds between two primary sites, one primary site and one secondary site, and between two secondary sites of the glycerol monomer. Therefore, the polyglycerol backbone typically consists not only of linearly linked glycerol units but can also contain branched and cyclic structures. For details, see, for example, "Original synthesis of linear, branched and cyclic oligoglycerol standards", Cassel et al., J. Org. Chem. 2001, 875-896.

[0112] The preferred method according to the invention is characterized in that the polyol provided in step B) comprises polyglycerol, wherein the polyglycerol preferably accounts for at least 20% by weight of all polyols, preferably at least 40% by weight, and even more preferably at least 60% by weight, particularly preferably at least 80% by weight.

[0113] More preferably, the method according to the invention is characterized in that the polyglycerol provided in step B) has an average degree of polymerization of 2.0 to 20, preferably 2.5 to 16, and most preferably 3.0 to 12.

[0114] To calculate the average degree of polymerization of polyglycerol <n>The hydroxyl value (OHV, in mg KOH / g) of polyglycerol is determined by the formula: = (112200 – 18) OHV) / (74 OHV – 56100) is used for calculation.

[0115] More preferably, the method according to the invention is characterized in that the polyglycerol provided in step B) has a cyclic oligomer content of 1.0% to 50% by weight, preferably 2.0% to 40% by weight, particularly preferably 3.0% to 30% by weight, wherein the weight percentage refers to all the polyglycerol provided in step B).

[0116] If a polyol mixture comprising polyglycerol is provided in step B), preferably, at least one additional polyol is selected from the group consisting of: 1,10-decanediol, 1,12-dodecanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-pentanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-dimethyl-1,3-propanediol (neopentanediol), 2,4-diethyl-1,5-pentane, 2,5-dimethyl-3-hexyn-2,5-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl 1,3-Hexanediol, 2-Methyl-1,3-propanediol, 2-Methyl-2-propyl-1,3-propanediol, 2-Methyl-2-propyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propane, 3-hexyn-2,5-diol, bis(trimethylolpropane), isosorbide, pinacol, tricyclodecanediethanol, tripentaerythritol, 1,2-butanediol, 1,2-propanediol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,4-sorbitol, 1,5-sorbitol, dipentaerythritol, erythritol, isomaltitol, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, dehydrated xylitol, and xylitol. The preferred ingredients are isosorbide, 1,2-butanediol, 1,2-propanediol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,4-sorbitol, 1,5-sorbitol, dipentaerythritol, erythritol, isomaltitol, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, dehydrated xylitol, and xylitol.

[0117] The preferred method according to the present invention is characterized in that, in step C), at least one selected from monocarboxylic acids and polycarboxylic acids is co-esterified into a polyol, wherein the polycarboxylic acid is preferably a dicarboxylic acid.

[0118] However, it is preferred that the total amount of all poly(polyhydroxy fatty acids) accounts for at least 5% by weight, preferably at least 10% by weight, and more preferably at least 20% by weight of all carboxylic acids esterified into the polyol.

[0119] The monocarboxylic acid is preferably selected from the group of natural fatty acids. Natural fatty acids can be produced based on naturally occurring plant or animal oils, and preferably have 6 to 30 carbon atoms, especially 8 to 22 carbon atoms. Natural fatty acids are generally unbranched and typically consist of an even number of carbon atoms. Any double bonds have a cis configuration. The natural fatty acids present in step C) of the method of the present invention, or even more preferably, are selected from the following: octanoic acid, heptanoic acid (preferably obtained via pyrolysis of ricinoleic acid), caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, nonanoic acid (e.g., obtained by ozone decomposition or oxidative cracking of oleic acid), isostearic acid (e.g., a byproduct of dimer acids obtained during the catalytic dimerization of C18 unsaturated fatty acids), stearic acid, ricinoleic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecanoic acid (obtained by pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, phellandrene, transoleic acid, arachidic acid, behenic acid, erucic acid, codoleic acid, eicosapentaenoic acid, docosahexaenoic acid, arachidonic acid, 18-hydroxyoctadec-9-enoic acid, 20-hydroxyeicosanoic acid, and 20-hydroxyeicosanoic acid.

[0120] Polycarboxylic acids, such as aconitic acid, agaric acid, 1,2,3,4-butanetetracarboxylic acid, citric acid, ethylene-1,1,2,2-tetracarboxylic acid, isocitric acid, propane-1,2,3-tricarboxylic acid, or pyromellitic acid, can be coesterified into polyols.

[0121] Preferably, the polycarboxylic acid is a dicarboxylic acid.

[0122] Short-chain and / or long-chain dicarboxylic acids can be coesterified into polyols.

[0123] In the context of this invention, the term "short-chain dicarboxylic acid" should be understood to mean a dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 6 to 10 carbon atoms, such as itaconic acid.

[0124] In the context of this invention, the term "long-chain dicarboxylic acid" should be understood to mean a dicarboxylic acid having 24 to 44, preferably 30 to 40, more preferably 34 to 38 carbon atoms.

[0125] According to the present invention, the short-chain dicarboxylic acid co-esterified into the polyol is preferably selected from aliphatic linear dicarboxylic acids, especially succinic acid, maleic acid, tartaric acid, malic acid, fumaric acid, sorbic acid, α-ketoglutaric acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, and brassic acid, with adipic acid, pimelic acid, octanoic acid, azelaic acid, and sebacic acid being particularly preferred.

[0126] According to the present invention, the long-chain dicarboxylic acid co-esterified into the polyol is preferably selected from the group comprising dimer fatty acids, which are oligomeric forms of various unsaturated monomeric fatty acids. Dimer fatty acids are mixtures of acyclic and cyclic dicarboxylic acids obtained by catalytic dimerization of unsaturated fatty acids having 12 to 22 carbon atoms. For information on the preparation and uses of dimer acids and their physical and chemical properties, refer to the publication "The Dimer Acids: The chemical and physical properties, reactions and applications", ed. EC Leonard; HumkoSheffield Chemical, 1975, Memphis, Tenn.

[0127] The dicarboxylic acid may also contain small amounts of trifunctional and polyfunctional carboxylic acids. The functionality of the mixture should not exceed 2.4 on a molar average. Particularly suitable long-chain dicarboxylic acids for use according to the invention are dimer acids or mixtures of dimer and trimer acids obtained from vegetable oils with high content of unsaturated C18 fatty acids (oleic acid, linoleic acid, linolenic acid) (e.g., Radiacid 0977 from Oleon).

[0128] The present invention further provides polyol esters of poly(polyhydroxy fatty acids) that are obtainable by the method according to the present invention.

[0129] The polyol esters of poly(polyhydroxy fatty acids) according to the present invention preferably have an acid value of 0.005–50 mg KOH / g, more preferably 0.01–25 mg KOH / g.

[0130] Appropriate methods for determining acid value, especially those according to DGF CV 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

[0131] The polyol esters of poly(polyhydroxy fatty acids) according to the present invention preferably have a hydroxyl value of 10–900 mg KOH / g, more preferably 30–250 mg KOH / g.

[0132] Suitable detection methods for determining hydroxyl values, especially those according to DGF CV 17a (53), Ph. Eur. 2.5.3 Method A and DIN 53240.

[0133] The polyol esters of poly(polyhydroxy fatty acids) according to the present invention preferably have a saponification value of 30–300 mg KOH / g, more preferably 100–250 mg KOH / g.

[0134] Suitable testing methods for determining saponification value, especially those according to DGF CV 3, DIN EN ISO 3681 and Ph.Eur. 2.5.6.

[0135] Another subject of the invention is a mixture comprising a poly(polyhydroxy fatty acid) polyol ester obtainable by the method of the invention and at least one selected from cosmetic oils and emollients.

[0136] To facilitate the processing of poly(polyhydroxy fatty acid) polyol esters, the mixture preferably contains cosmetic oils and / or emollients, wherein the oils and / or emollients have a viscosity in the range of 1-100 mPa·s at 25 °C and a surface tension in the range of 25-34 mN / m.

[0137] A suitable method for determining viscosity is to use a Brookfield RV viscometer (using a rotor SC4-21, running at 20 RPM, displaying 53.0% of torque; torque constant = 1, rotor multiplier constant = 5, rotor shear rate constant = 0.93) and a Brookfield Thermosel.

[0138] Surface tension was determined at 20°C using the du Noüy ring method.

[0139] The cosmetic oils and emollients contained in the mixture are preferably selected from natural oils, isoamyl laurate, isoamyl cocoate, diethylhexyl carbonate, isopropyl myristate, isopropyl palmitate, decyl cocoate, ethylhexyl palmitate, phenoxyethyl octanoate, C12-15 benzoyl alcohol, ethylhexyl stearate, cetyl ethylhexanoate, lauryl oleate, caprylic / capric triglyceride, trinonanoic acid glyceride, PPG-3 myristyl ether, oleyl erucic acid, baobab seed oil, PPG-15 stearyl ether, and PPG-14 butyl ether, preferably natural oils.

[0140] Preferably, the ratio (w / w) of all poly(polyhydroxy fatty acid) polyol esters contained in the mixture to all cosmetic oils and emollients is from 30:70 to 99.5:0.5.

[0141] Preferably, the mixture contains at least 50% by weight of all poly(hydroxy fatty acid) polyol esters and at least 70% by weight of all cosmetic oils and emollients in the whole mixture, and more preferably at least 90% by weight.

[0142] Since the poly(polyhydroxy fatty acid) polyol esters according to the present invention and the mixtures according to the present invention have excellent use properties, especially in cosmetic formulations, the present invention further provides the use of the poly(polyhydroxy fatty acid) polyol esters according to the present invention in the preparation of formulations, preferably aqueous formulations.

[0143] The formulation prepared according to the invention is preferably a cosmetic or pharmaceutical formulation, and is preferably for topical application.

[0144] The formulation prepared according to the invention preferably contains at least one additional component selected from the group consisting of: Moisturizer Emulsifier, Auxiliary emulsifiers, Thickener / viscosity modifier / stabilizer Antioxidants Water-soluble substances (or polyols), Solids and fillers Pearlescent additives and opacifiers, Insect repellents Self-tanning agent preservative, Conditioner, essence, Colorant, Cosmetic active ingredients Nursing additives Fat additives, Solvent.

[0145] Substances that can be used as exemplary representatives of each group are known to those skilled in the art and may be derived, for example, from German application DE102008001788.4. This patent application is incorporated herein by reference and is therefore considered to form part of the disclosure.

[0146] For information on other optional components and their dosages, please refer to relevant manuals known to those skilled in the art, such as K. Schrader, "Grundlagen und Rezepturen der Kosmetika" [Cosmetic Fundamentals and Formulations], 2nd edition, pp. 329-341, Hüthig Buch Verlag, Heidelberg.

[0147] The amount of each additive used depends on the intended use.

[0148] Typical guide formulations for relevant applications are known prior art and are included in, for example, manuals from manufacturers of the relevant base materials and active substances. These existing formulations can generally be used as is. However, any necessary modifications for adjustment and optimization can be made directly through simple testing.

[0149] The present invention further provides formulations comprising polyol esters of poly(polyhydroxy fatty acids) according to the present invention or mixtures according to the present invention, wherein preferred formulations according to the present invention are those obtained in the above-described method according to the present invention.

[0150] The present invention further provides the use of poly(polyhydroxy fatty acid) polyol esters or mixtures thereof according to the present invention as emulsifiers in aqueous formulations, preferably as W / O emulsifiers. Attached Figure Description

[0151] Figure 1 : A schematic diagram of an exemplary synthetic route for obtaining poly(9,10-dihydroxystearic acid) as a precursor for esterification with polyols, starting from oleic acid. The structure of poly(9,10-dihydroxystearic acid) shown is only a representative structure, because the poly(polyhydroxy fatty acid) according to the invention may comprise a mixture of regioisomers and a polyester in which two ortho-hydroxyl groups of at least some monomers are esterified.

[0152] The following embodiments describe the invention by way of example and are not intended to limit the invention (the scope of which is obvious from the entire specification and claims) to the embodiments specified in the embodiments.

[0153] Example Epoxidation Example 1: Oleic acid enzymatically epoxidized to 9,10-epoxyoctadecanoic acid Oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, iodine value (IV) = 92 g I / 100 g, 523.75 g, 1.86 mol carbon-carbon double bond = 1.00 equivalent) and immobilized Candida antarctica ( Candida antarctica A mixture of lipase B (15.7 g, Purolite D5619, equivalent to 136339 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 210.56 g, 1.85 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 40 °C for 24 hours. Subsequently, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product was a pale yellow liquid that solidified upon storage to give a white solid with a waxy consistency and an epoxy-[O] content of 3.8%.

[0154] Example 2: Oleic acid enzymatically epoxidized to 9,10-epoxyoctadecanoic acid Oleic acid (DakoLub MB 6098, AV = 198 mg KOH / g, IV = 87 g I / 100 g, 173.85 g, 0.62 mol carbon-carbon double bond = 1.00 equivalent) and immobilized Candida antarctica ( Candida antarctica A mixture of lipase B (5.4 g, Purolite D5619, equivalent to 46894 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 69.8 g, 0.62 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 40 °C for 24 hours. Afterward, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product was a pale yellow liquid that solidified upon storage to give a white solid with a waxy consistency and an epoxy-[O] content of 3.8%.

[0155] Example 3: Linoleic acid was enzymatically epoxidized to 9,10:12,13-diepoxyoctadecanoic acid Linoleic acid (Caila & Pares Cypacid G-35, AV = 200 mg KOH / g, IV = 133 g I / 100g, 246.4 g, 1.29 mol carbon-carbon double bond = 1.00 equivalent) and immobilized Candida antarctica ( Candida antarctica A mixture of lipase B (7.4 g, Purolite D5619, equivalent to 64261 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 146.3 g, 1.29 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 40 °C for 24 hours. Subsequently, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product was a yellow liquid that solidified upon storage to give a pale yellow solid with a waxy consistency and an epoxy-[O] content of 3.4%.

[0156] Example 4: Enzymatic epoxidation of erucic acid to 13,14-epoxydocosalicylic acid Erucic acid (Oleon Nouracid RE07, AV = 166 mg KOH / g, IV = 72 g I / 100 g, 292.1 g, 0.875 mol carbon-carbon double bond = 1.00 equivalent) and immobilized Candida antarctica ( Candida antarctica A mixture of lipase B (8.7 g, Purolite D5619, equivalent to 75550 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 99.2 g, 0.875 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 50 °C for 24 hours. Subsequently, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product was a pale yellow liquid that solidified upon storage to give a white solid with an epoxy-[O] content of 2.8%.

[0157] Example 5: Enzymatic epoxidation of castor oil acid to 9,10-epoxy-12-hydroxyoctadecanoic acid A mixture of ricinoleic acid (Oleon Nouracid CZ 80, AV = 183 mg KOH / g, IV = 90 g I / 100 g, 253.05 g, 0.789 mol carbon-carbon double bonds = 1.00 equivalent) and immobilized Candida antarctica lipase B enzyme (7.5 g, Purolite D5619, equivalent to 64755 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 89.5 g, 0.790 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 40 °C for 24 hours. Afterward, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product is a colorless and transparent liquid with an epoxy-[O] content of 1.7%.

[0158] Example 6: Enzymatic epoxidation of undecenoic acid to 10,11-epoxyundecanoic acid Undecyl-10-enoic acid (TH. Geyer, 98%, 198.3 g, 1.076 mol carbon-carbon double bond = 1.00 equivalent) and immobilized Candida antarctica ( Candida antarctica A mixture of lipase B (6.0 g, Purolite D5619, equivalent to 52104 PLU) was heated to 40 °C with stirring and N2 introduction. After reaching 40 °C, hydrogen peroxide (30% aqueous solution, 122.0 g, 1.076 mol, 1.00 equivalent) was added dropwise over 2 hours, and the mixture was then stirred at 40 °C for 24 hours. Subsequently, the mixture was dried at 65 °C and 10 mbar for 2 hours. The mixture was filtered through a Buchner funnel with black filter paper to remove the enzyme. The resulting product was a colorless, transparent liquid that partially solidified during storage, with an epoxy-[O] content of 1.2%.

[0159] Epoxy fatty acids are converted into polyhydroxy fatty acids Example 7: Conversion of 9,10-epoxyoctadecanoic acid to 9,10-dihydroxyoctadecanoic acid A mixture of 9,10-epoxyoctadecanoic acid (90 g), water (8.23 g), and sulfuric acid (96%, 1.79 g) obtained according to Example 1 was heated to 120 °C and refluxed for 4 hours with stirring. After cooling to room temperature, the mixture was washed with water (2 × 20 mL). The resulting product was a turbid yellow liquid.

[0160] Example 8: Conversion of 9,10:12,13-diepoxyoctadecanoic acid to 9,10:12,13-tetrahydroxyoctadecanoic acid A mixture of 9,10:12,13-diepoxyoctadecanoic acid (68.81 g), water (6.24 g), and sulfuric acid (96%, 1.31 g) obtained according to Example 3 was heated to 120 °C and refluxed for 4 hours with stirring. After cooling to room temperature, the mixture was washed with water (2 × 20 mL). The resulting product was a turbid amber liquid.

[0161] Polymerization of epoxidized fatty acids or polyhydroxy fatty acids Example 9: Polymerization of 9,10-epoxyoctadecanoic acid to poly(9,10-dihydroxyoctadecanoic acid) The 9,10-epoxyoctadecanoic acid (196.0 g) obtained according to Example 1 was heated to 120 °C for 14 hours with stirring and N2 introduction. The resulting product was a viscous yellow liquid with AV of 60 mg KOH / g, SV of 202 mg KOH / g, OHV of 135 mg KOH / g, and an epoxy-[O] content of 0.3%.

[0162] Example 10: Polymerization of 9,10-dihydroxyoctadecanoic acid to poly(9,10-dihydroxyoctadecanoic acid) 155.3 g of 9,10-dihydroxyoctadecanoic acid obtained according to Example 7 was heated to 200 °C for 4.5 hours with stirring and N2 introduction. The resulting product was a viscous yellow liquid with AV of 55 mg KOH / g, SV of 202 mg KOH / g, and OHV of 122 mg KOH / g.

[0163] Example 11: Polymerization of 9,10:12,13-diepoxyoctadecanoic acid to poly(9,10,12,13-tetrahydroxyoctadecanoic acid) 178.0 g of 9,10:12,13-diepoxyoctadecanoic acid obtained according to Example 3 was heated to 120 °C for 14 hours with stirring and N2 introduction. The resulting product was a viscous yellow liquid with AV of 58 mg KOH / g, SV of 201 mg KOH / g, OHV of 163 mg KOH / g, and an epoxy-[O] content of 0.1%.

[0164] Example 12: Polymerization of 13,14-epoxydocosalicylic acid to poly(13,14-dihydroxydocosalicylic acid) The 13,14-epoxydocosalicylic acid (164.9 g) obtained according to Example 4 was heated to 120 °C for 16 hours with stirring and N2 introduction. The resulting product was a viscous yellow liquid with AV of 54 mg KOH / g, SV of 167 mg KOH / g, OHV of 110 mg KOH / g, and an epoxy-[O] content of 0.2%.

[0165] Poly(polyhydroxy fatty acid) polyol esters Example 13: Polyglycerol metaester with poly(9,10-dihydroxyoctadecanoic acid) (of the present invention) A mixture of poly(9,10-dihydroxyoctadecanoic acid) (AV = 60 mg KOH / g, 27.1 g) and oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 69.7 g, 0.247 mol) obtained according to Example 9 was heated to 200 °C for 3 hours. Then, polyglycerol (OHV = 1100 mg KOH / g, 35.2 g) was added, and the mixture was heated to 240 °C with stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 5 mg KOH / g was achieved. The resulting product was a two-phase mixture with an upper phase to lower phase ratio of approximately 9:1. The mixture was separated at 80 °C using a separatory funnel. The lower phase mainly consists of unreacted polyglycerol, while the separated upper / upper phase of the mixture is a yellow transparent liquid (AV = 1.2 mg KOH / g, OHV = 126 mg KOH / g, SV = 164 mg KOH / g).

[0166] Example 14: Polyglycerol metaester with poly(9,10,12,13-tetrahydroxyoctadecanoic acid) (of the present invention) A mixture of poly(9,10,12,13-tetrahydroxyoctadecanoic acid) (AV = 58 mg KOH / g, 29.8 g) and oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 gI / 100 g, 77.0 g, 0.273 mol) obtained according to Example 11 was heated to 200 °C for 3 hours with stirring and nitrogen purging. Then, polyglycerol (OHV = 1100 mg KOH / g, 37.2 g) was added, and the mixture was heated to 240 °C with stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 5 mg KOH / g was achieved. The resulting product was a two-phase mixture with an upper phase to lower phase ratio of approximately 9:1. The mixture was separated at 80 °C using a separatory funnel. The lower phase mainly consists of unreacted polyglycerol, and the separated upper / upper phase of the mixture is a yellow transparent liquid (AV = 2.0 mg KOH / g, OHV = 109 mg KOH / g, SV = 175 mg KOH / g).

[0167] Example 15: Polyglycerol metaester with poly(13,14-dihydroxyicosanoic acid) (of the present invention) A mixture of poly(13,14-dihydroxyicosanoic acid) (AV = 54 mg KOH / g, 28.0 g) and oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 72.2 g, 0.257 mol) obtained according to Example 12 was heated to 200 °C with stirring and nitrogen purging. Then, polyglycerol (OHV = 1100 mg KOH / g, 34.8 g) was added, and the mixture was heated to 240 °C with stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 5 mg KOH / g was achieved. The resulting product was a two-phase mixture with an upper phase to lower phase ratio of approximately 9:1. The mixture was separated at 80 °C using a separatory funnel. The lower phase mainly consists of unreacted polyglycerol, while the separated upper / upper phase of the mixture is a yellow transparent liquid (AV = 1.7 mg KOH / g, OHV = 96 mg KOH / g, SV = 170 mg KOH / g).

[0168] Example 16: Polyglycerol metaester with poly(9,10-dihydroxyoctadecanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 33.6 g), poly(9,10-dihydroxyoctadecanoic acid) obtained according to Example 9 (AV = 60 mg KOH / g, 27.0 g), oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 69.72 g, 0.247 mol), and sebacic acid (13.0 g, 0.064 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 2.0 mg KOH / g was achieved. The product was a yellow, transparent liquid (AV = 0.4 mg KOH / g, OHV = 144 mg KOH / g, SV = 192 mg KOH / g).

[0169] Example 17: Polyglycerol metaester with poly(9,10-dihydroxyoctadecanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 28.4 g), poly(9,10-dihydroxyoctadecanoic acid) obtained according to Example 9 (AV = 60 mg KOH / g, 45.6 g), oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 58.9 g, 0.209 mol), and sebacic acid (11.0 g, 0.054 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 3.0 mg KOH / g was achieved. The product was a yellow, transparent liquid (AV = 0.5 mg KOH / g, OHV = 133 mg KOH / g, SV = 196 mg KOH / g).

[0170] Example 18: Polyglycerol metaester with poly(9,10-dihydroxyoctadecanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 34.3 g), oleic acid (Palmera A1818, from KLKEmmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 68 g, 0.241 mol), and sebacic acid (13.3 g, 0.066 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 7.0 mg KOH / g was achieved. Then, a mixture of poly(9,10-dihydroxyoctadecanoic acid) (AV = 60 mg KOH / g, 26.7 g) and oleic acid (Palmera A1818, from KLKEmmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 2.8 g, 0.01 mol), obtained according to Example 9, was added. The combined mixture was heated to 240 °C under stirring and nitrogen purging, and the resulting water was continuously distilled until an acid value of 2.0 mg KOH / g was achieved. The product was a yellow, transparent liquid with AV = 0.6 mg KOH / g, OHV = 137, and SV = 196.

[0171] Example 19: Polyglycerol metaester with poly(9,10-dihydroxyoctadecanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 33.6 g), poly(9,10-dihydroxyoctadecanoic acid) obtained according to Example 10 (AV = 55 mg KOH / g, 27.0 g), oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 69.72 g, 0.247 mol), and sebacic acid (13.0 g, 0.064 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 2.0 mg KOH / g was achieved. The resulting product was a yellow, transparent liquid (AV = 0.9 mg KOH / g, OHV = 128 mg KOH / g, SV = 194 mg KOH / g).

[0172] Example 20: Polyglycerol metaester with poly(9,10,12,13-tetrahydroxyoctadecanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 33.7 g), poly(9,10,12,13-tetrahydroxyoctadecanoic acid) obtained according to Example 11 (AV = 58 mg KOH / g, 27.0 g), oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 69.7 g, 0.248 mol), and sebacic acid (11.0 g, 0.054 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 3.0 mg KOH / g was achieved. The product was a yellow, transparent liquid (AV = 0.3 mg KOH / g, OHV = 150 mg KOH / g, SV = 200 mg KOH / g).

[0173] Example 21: Polyglycerol metaester with poly(13,14-dihydroxyicosanoic acid) (of the present invention) A mixture of polyglycerol (OHV = 1100 mg KOH / g, 33.6 g), poly(13,14-dihydroxyicosanoic acid) obtained according to Example 12 (AV = 54 mg KOH / g, 27.0 g), oleic acid (Palmera A1818, from KLK Emmerich GmbH, AV = 200 mg KOH / g, IV = 92 g I / 100 g, 69.72 g, 0.247 mol), and sebacic acid (13.0 g, 0.064 mol) was heated to 240 °C under stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 3.0 mg KOH / g was achieved. The product was a yellow, transparent liquid (AV = 0.6 mg KOH / g, OHV = 145 mg KOH / g, SV = 196 mg KOH / g).

[0174] Comparative Example 22: Polyglycerol metaester of poly(12-hydroxystearic acid) (not of this invention) according to Example 13 of EP1500427 A mixture of polyglycerol (OHV = 1190 mg KOH / g, 63.0 g), isostearic acid (PRISORINE 3505-LQ-(GD), from CRODA GmbH, AV = 193 mg KOH / g, 91.1 g, 0.313 mol), and sebacic acid (20.2 g, 0.100 mol) was heated to 240 °C with stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 9.0 mg KOH / g was achieved. Then, poly(12-hydroxystearic acid) (AV = 45 mg KOH / g, 141.7 g, 0.114 mol) was added, and the combined mixture was heated to 240 °C with stirring and nitrogen purging. The resulting water was continuously distilled until an acid value of 4.3 mg KOH / g was achieved.

[0175] Application Examples The purpose of the following examples is to distinguish the emulsifying properties of the poly(polyhydroxy fatty acid) polyol esters according to the present invention from those of the prior art.

[0176] Application Example 23: A comparison was made with the polyol ester containing poly(12-hydroxystearic acid) of Comparative Example 22, which is based on Example 13 of EP1500427.

[0177] Homogenization techniques known to those skilled in the art were used to prepare the emulsions. All concentrations are given as weight percentages. Preparation was carried out using a cold / cold process. To analyze emulsion stability, the emulsions were stored at 25°C for one month and at 50°C for three days. The freeze-thaw resistance of the emulsions was studied by performing three consecutive freeze-thaw cycles (-15°C / 25°C).

[0178] According to the present invention In test formulation 1, all polyol esters of the present invention exhibited stability comparable to Comparative Example 22 after storage at 25°C for one month and at 50°C for three days. Furthermore, it was surprisingly found that all polyol esters of the present invention provided perfect stability throughout three consecutive freeze-thaw cycles, covering a wide range of different viscosities, with Example 13 showing a viscosity almost identical to Comparative Example 22.

[0179] It should be noted that, according to the document, Comparative Example 22, which represents an embodiment of EP1500427, already has excellent freeze-thaw resistance, while the poly(polyhydroxy fatty acid) polyol ester of the present invention surpasses it.

[0180] Application Example 23b: A more challenging test was conducted using formulations identical to formulations 1a-e but with only 1.5% instead of 2.0% polyol esters.

[0181] When these formulations were stored at 50°C for 48 hours, the polyol esters of the present invention were also able to perfectly stabilize these emulsions with almost the same viscosity.

[0182] Application Example 24: The emulsions were prepared similarly to the formulations shown in Application Example 23. Compared to formulations 1a-e, formulations 2a-e contain a less polar oil phase.

[0183] According to the present invention Exactly the same as Comparative Example 22 used in Formulation 2a, the emulsion produced by the poly(polyhydroxy fatty acid) polyol ester of the present invention showed no instability after storage at 50°C for 3 days. Surprisingly, it was found that Example 13 of the polyol ester of the present invention provided freeze-thaw resistance for the test formulation, and was superior to Comparative Example 22 in Formulation 2a, although the two emulsions showed no difference in viscosity. It should be noted that, according to this document, Comparative Example 22, representing an embodiment of EP1500427, already exhibited excellent freeze-thaw resistance, which the poly(polyhydroxy fatty acid) polyol ester of the present invention surpasses.

[0184] Preparation Examples The following examples of emulsions are intended to explain the subject matter of the invention in more detail, but are not intended to limit it to these examples. These examples demonstrate that the emulsifiers of the present invention can be used to stabilize a variety of cosmetic formulations as well as to disperse pigments and other solids. Furthermore, these examples demonstrate compatibility with typical co-emulsifiers, cosmetic oils, emollients, waxes, and stabilizers, as well as tolerance to unstable components of the emulsion, such as UV filters, antimicrobial agents, electrolytes, and active ingredients.

[0185] Preparation is carried out using a hot / cold or cold / cold process, employing homogenization techniques known to those skilled in the art. When using a hot / cold process, the oil phase is typically heated to 75-80°C. The aqueous phase is then added over 2 minutes with stirring. The mixture is then briefly homogenized and cooled. After reaching a temperature <30°C, the emulsion is homogenized again. In the case of a cold / cold process, the aqueous phase is added to the oil phase over 2 minutes with stirring. The emulsion is then homogenized. Compounds such as preservatives or active ingredients are preferably added below 40°C after homogenization. When an organic acid is used as a preservative, the pH is adjusted in the aqueous phase.

[0186] The sample formulations listed below were prepared using each polyol ester (hereinafter referred to as "Example X") according to Examples 13 to 21 of the present invention. Thus, for each example formulation presented below, nine different formulations were prepared.

[0187] W / O Cream

[0188] Cold-processable emulsions

[0189] Moisturizing lotion containing urea

[0190] W / O lotion with a silky and soft skin feel

[0191] Baby care products

[0192] Foot care products

[0193] Sunscreen with insect repellent SPF 30 UVA

[0194] Sunscreen SPF 30 UVA according to ecological standards

[0195] Sunscreen spray SPF 30 UVA

[0196] Sunscreen spray SPF 50 UVA

[0197] SPF 50 sunscreen lotion according to FDA standards

[0198] Foundation 1

[0199] Foundation 2:

[0200] CC (color control) liquid

[0201] AP / Deo spray or aerosol spray

[0202] Sunscreen aerosol SPF 50 UVA

[0203] Cooling body lotion < / n>

Claims

1. A method for producing poly(polyhydroxy fatty acid) polyol esters, comprising the following steps: A) Provide at least one poly(polyhydroxy fatty acid), B) Provide at least one polyol, preferably a mixture of more than one polyol. C) Esterify the at least one poly(polyhydroxy fatty acid) and the at least one polyol.

2. The method according to claim 1, characterized in that, Step A) includes the following sub-steps: A1) Provides at least one unsaturated fatty acid, A2) Epoxidize at least one carbon-carbon double bond of the at least one unsaturated fatty acid to obtain an epoxidized fatty acid. Optional A3) causes the epoxy group of the epoxide fatty acid to open the ring, thereby obtaining a polyhydroxy fatty acid, and A4) Polymerize the epoxy fatty acid and / or the polyhydroxy fatty acid to obtain at least one poly(polyhydroxy fatty acid).

3. The method according to claim 2, characterized in that, The unsaturated fatty acids are selected from the group consisting of: arachidonic acid, octadecanoic acid, catalpa acid, dihomo-γ-linolenic acid, docosahexaenoic acid, docosapentaenoic acid, docosatraenoic acid, eicosapentaenoic acid, eicosatraenoic acid, eicosaenoic acid, 11-eicosaenoic acid, trans oleic acid, α-tungsten acid, β-tungsten acid, erucic acid, codoleic acid, linoleic acid, trans linoleic acid, linolenic acid, α-linolenic acid, γ-linolenic acid, and meadic acid. Myristone acid, nervonic acid, octadecanoic acid, octadecanoic acid, oleic acid, ω-3 fatty acid, ω-6 fatty acid, ω-7 fatty acid, ω-9 fatty acid, palmitoleic acid, α-parilla oleic acid, guaranaic acid, phellandrene, terpineic acid, punicic acid, ricinoleic acid, rumen acid, sapiensic acid, stearatetraenoic acid, sulphuric acid, undecenoic acid, isoleic acid and piperidinic acid, with erucic acid, linoleic acid, oleic acid and palmitoleic acid being preferred.

4. The method according to claim 2 or 3, characterized in that, The epoxidation in sub-step A2) is catalyzed by an enzyme in the presence of at least one peroxide, preferably hydrogen peroxide, said enzyme preferably selected from cytochrome P450 enzymes, lipoxygenases, peroxidases, epoxide hydrolases and lipases, preferably lipases.

5. The method according to any one of the preceding claims, characterized in that, The poly(polyhydroxy fatty acid) provided in step A) has an acid value of 10 to 200 mg KOH / g, preferably 35 to 120 mg KOH / g, and particularly preferably 40 to 90 mg KOH / g.

6. The method according to any one of the preceding claims, characterized in that, The poly(polyhydroxy fatty acid) provided in step A) has an epoxy-[O] content of ≤10.0%, preferably ≤5.0%, and more preferably ≤1.0%.

7. The method according to any one of the preceding claims, characterized in that, The poly(polyhydroxy fatty acid) provided in step A) has a hydroxyl value of 10 to 400 mg KOH / g, preferably 50 to 300 mg KOH / g, and particularly preferably 70 to 200 mg KOH / g.

8. The method according to any one of the preceding claims, characterized in that, The polyol provided in step B) has three or more, preferably four or more, and especially more than six carbon atoms.

9. The method according to any one of the preceding claims, characterized in that, The polyol provided in step B) is selected from the group consisting of: 1,10-decanediol, 1,12-dodecanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-pentanediol, 1,4-bis(hydroxymethyl)cyclohexane, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2,2-bis(4-hydroxycyclohexyl)propane, 2,2-dimethyl-1,3-propanediol (neopentanediol), 2,4-diethyl-1,5-pentane, 2,5-dimethyl-3-hexyn-2,5-diol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, and 2-methyl-1,3-propanediol. 2-Methyl-2-propyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-sec-butyl-2-methyl-1,3-propane, 3-hexyn-2,5-diol, bis(trimethylolpropane), isosorbide, pinacol, tricyclodecanediethanol, tripentaerythritol, 1,2-butanediol, 1,2-propanediol, 1,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,4-sorbitol, 1,5-sorbitol, diglycerides, dipentaerythritol, erythritol, glycerol, isomaltitol, lactitol, maltitol, mannitol, pentaerythritol, sorbitol, trimethylolethane, trimethylolpropane, dehydrated xylitol, xylitol and polyglycerol, preferably polyglycerol.

10. The method according to claim 9, characterized in that, The polyglycerol provided in step B) has an average degree of polymerization of 2.0 to 20, preferably 2.5 to 16, and most preferably 3.0 to 12.

11. The method according to claim 9 or 10, characterized in that, The polyglycerol provided in step B) has a cyclic oligomer content of 1.0% to 50% by weight, preferably 2.0% to 40% by weight, and particularly preferably 3.0% to 30% by weight, wherein the weight percentage refers to all the polyglycerol provided in step B).

12. The method according to any one of the preceding claims, characterized in that, In step C), at least one selected from monocarboxylic acids and polycarboxylic acids is coesterified into a polyol, wherein the polycarboxylic acid is preferably a dicarboxylic acid.

13. Poly(polyhydroxy fatty acid) polyol esters, which can be obtained by the method according to any one of the preceding claims.

14. A mixture comprising a polyol ester of the poly(polyhydroxy fatty acid) of claim 13 and at least one selected from cosmetic oils and emollients.

15. Use of the poly(polyhydroxy fatty acid) polyol ester or mixture according to claim 14 for the preparation of formulations, preferably aqueous formulations, and / or as an emulsifier in aqueous formulations, preferably as a W / O emulsifier.

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