Nonanoic acid ester

Abstract

The present invention provides n-nonanoic acid esters of xylitol, sorbitol or erythritol, their preparation and their use, especially in cosmetic or household care compositions.

Description

[Technical field]

[0001] The present invention provides n-nonanoic acid esters of xylitol, sorbitol or erythritol, their preparation and their use, particularly in cosmetic compositions.

[0002] prior art Nonanoic Acid / Pelargonic Acid n-Nonanoic acid (pelargonic acid, CAS 112-05-0) can be obtained by oxidation of n-nonanal of petrochemical origin (“Carboxylic Acids, Aliphatic,”: Ullmann's Encyclopedia of Industrial Chemistry 2014). n-Nonanoic acid can also be obtained by ozonolysis of ω-9-fatty acids, such as oleic acid and erucic acid or their esters. However, ozonolysis is a process with high energy demands and specific process requirements, such as the use of ozone generators. Moreover, the ω-9-fatty acids used are often obtained from tropical vegetable oils, such as palm oil, palm kernel oil and coconut oil. Even more sustainable methods for producing n-nonanoic acid are based on hydrogen peroxide (Soutelo-Maria et al. in Catalysts 2018, 8, 464), especially when such processes, such as those described in US9272975, US8846962, US8222438, WO2007039481 and WO2011080296, proceed also from omega-9-fatty acids or their esters not obtained from tropical vegetable oils.

[0003] Esters of xylitol and n-nonanoic acid Savelli et al., International Journal of Pharmaceutics 1999, 182, 221-23, describe the regioselective synthesis of the stereoisomerically pure 1-O-nonanoyl-D,L-xylitol and its amphiphilic properties (water solubility, critical micelle concentration (CMC), surface tension, formation of lyotropic liquid crystals, HLB value). A drawback of the process described in the prior art is the three-step synthesis in the presence of organic solvents using the isopropylidene protecting group, where nonanoyl chloride is used for acylation, which is also a drawback. Similar studies, e.g. the determination of the transition temperatures, for 1-O-nonanoyl-D,L-xylitol obtained by the same synthetic route are described by Goodby et al. in Liquid Crystals 1997, 22, 367-378 and by Douillet et al. in FR-A-2 728 257. Dahlhoff et al., in Zeitschrift für Naturforschung, B: Chemical Sciences 1996, 51, 1229-1234, chose the boranediyl protecting group introduced in carcinogenic benzene as solvent for the synthesis of 1-O-nonanoyl-D,L-xylitol. Here too, the properties of the pure 1-O-nonanoyl-D,L-xylitol stereoisomers were investigated in the form of liquid crystals.

[0004] Esters of sorbitol and n-nonanoic acid EP 879872 discloses fully esterified sorbitol hexanonanoate as a component of lubricating oil compositions.

[0005] Other Prior Art Korean Patent No. 10-1939851 describes the use of anhydrous xylitol esters and carboxylic acid esters of said anhydrous xylitol as rheological additives / viscosity modifiers in emulsions.One of the disadvantages of the anhydrous xylitol carboxylates described in the prior art is reduced hydrophilicity.Another disadvantage of the anhydrous xylitol carboxylates described in the prior art is their dark color.Another disadvantage of such anhydrous xylitol carboxylates is the lack of thickening performance in aqueous surfactant systems.

[0006] DE 102009001748 A1 describes sorbitan esters obtained from the solvent-free reaction of 1 mol of sorbitol (also called glucitol) with 1.55 mol of caprylic acid, and the use of the sorbitan esters thus obtained as thickeners for aqueous surfactant systems. A drawback of this process is that under the reaction conditions described, sorbitol is substantially completely, but at least partially, dehydrated to form what is called sorbitan (product mixture). Furthermore, a discolored and odorous product is obtained, which does not meet the quality standards for cosmetic applications without additional bleaching or treatment with activated carbon.

[0007] The problem addressed by the present invention was to provide n-nonanoic acid esters which are able to overcome at least one of the drawbacks of the prior art.

[0008] Detailed Description of the Invention Surprisingly, it has been found that the n-nonanoic acid esters described below and the methods described below are capable of solving the problems addressed by the present invention.

[0009] One advantage of the present invention is that the n-nonanoic acid ester according to the present invention is an excellent thickener for aqueous surfactant systems compared to the prior art. A further advantage is that the n-nonanoic acid ester according to the present invention also has an excellent color and a very good odor compared to the prior art. One advantage of the method according to the present invention is that only very low levels of decomposition products or esters of decomposition products of the sugar or sugar alcohol used are obtained as reaction products. One advantage of the present invention is that the method according to the present invention can be carried out in the absence of a solvent. One advantage of the present invention is that the method according to the present invention can be carried out in one reaction step. One advantage of the present invention is that the method according to the present invention can be carried out without chemical reactions of protective groups. A further advantage of the present invention is that the n-nonanoic acid ester is obtained in a homogeneous reaction mixture, so that no additional process steps are necessary, such as extraction, crystallization, filtration or distillation. One advantage of the present invention is that the method can be carried out at high temperatures. This leads to an improved miscibility of the co-reactants, while the recyclability of the enzymes used is surprisingly high. A further advantage of the present invention is that the resulting n-nonanoic acid esters can be very easily incorporated into formulations, especially cosmetic and household care formulations.

[0010] The present invention therefore provides n-nonanoic acid esters of xylitol, sorbitol or erythritol, characterized in that the n-nonanoic acid esters are in the form of a mixture of at least two esters which differ with respect to at least one esterification position of at least one nonanoyl group in xylitol, sorbitol or erythritol, with the proviso that n-nonanoic acid esters of erythritol having an average degree of esterification greater than 3.2 are excluded.

[0011] Thus, the present invention provides for a mixture composition of structurally different esters.

[0012] For example, the n-nonanoic acid esters preferred according to the invention are characterized in that they comprise at least two positional isomers of mono-n-nonanoic acid esters. The expression "the n-nonanoic acid esters are in the form of a mixture, in which at least two esters differ with respect to at least one esterification position of at least one nonanoyl group in xylitol, sorbitol or erythritol" is understood to mean that at least two esters of the same sugar alcohol, respectively, differ from each other.

[0013] In the case of the n-nonanoic acid esters of xylitol, these various esters can be chosen, for example, from the following: 1-O-nonanoyl xylitol, 2-O-nonanoyl xylitol, 3-O-nonanoyl xylitol, 4-O-nonanoyl xylitol, 5-O-nonanoyl xylitol, 1,2-O-dinonanoyl xylitol, 1,3-O-dinonanoyl xylitol, 1,4-O-dinonanoyl xylitol, 1,5-O-dinonanoyl xylitol, 2,3-O-dinonanoyl xylitol, xylitol, 2,4-O-dinonanoyl xylitol, 2,5-O-dinonanoyl xylitol, 3,4-O-dinonanoyl xylitol, 3,5-O-dinonanoyl xylitol, 4,5-O-dinonanoyl xylitol, 1,2,3-O-trinonanoyl xylitol, 1,2,4-O-trinonanoyl xylitol, 1,2,5-O-trinonanoyl xylitol, 1,3,4-O-trinonanoyl xylitol, 1,3,5-O-trinonanoyl xylitol, 1,4,5-O-trinonanoyl xylitol, Linonanoyl xylitol, 2,3,4-O-trinonanoyl xylitol, 2,3,5-O-trinonanoyl xylitol, 2,4,5-O-trinonanoyl xylitol, 3,4,5-O-trinonanoyl xylitol, 1,2,3,4-O-tetranonanoyl xylitol, 1,2,3,5-O-tetranonanoyl xylitol, 1,2,4,5-O-tetranonanoyl xylitol, 1,3,4,5-O-tetranonanoyl xylitol, 2,3,4,5-O-tetranonanoyl xylitol xylitol and 1,2,3,4,5-O-pentanonanoylxylitol, particularly preferred are 1-O-nonanoylxylitol, 2-O-nonanoylxylitol, 3-O-nonanoylxylitol, 4-O-nonanoylxylitol, 5-O-nonanoylxylitol, 1,2-O-dinonanoylxylitol, 1,5-O-dinonanoylxylitol, 4,5-O-dinonanoylxylitol, 1,2,5-O-trinonanoylxylitol and 1,4,5-O-trinonanoylxylitol.

[0014] In the case of n-nonanoic acid esters of sorbitol, these various esters can be chosen, for example, from: 1-O-nonanoylsorbitol, 2-O-nonanoylsorbitol, 3-O-nonanoylsorbitol, 4-O-nonanoylsorbitol, 5-O-nonanoylsorbitol, 6-O-nonanoylsorbitol, 1,2-O-dinonanoylsorbitol, 1,3-O-dinonanoylsorbitol, 1,4-O-dinonanoylsorbitol, 1,5-O-dinonanoylsorbitol, 1,6-O-dinonanoylsorbitol , 2,3-O-dinonanoyl sorbitol, 2,4-O-dinonanoyl sorbitol, 2,5-O-dinonanoyl sorbitol, 2,6-O-dinonanoyl sorbitol, 3,4-O-dinonanoyl sorbitol, 3,5-O-dinonanoyl sorbitol, 3,6-O-dinonanoyl sorbitol, 4,5-O-dinonanoyl sorbitol, 4,6-O-dinonanoyl sorbitol, 5,6-O-dinonanoyl sorbitol, 1,2,3-O-trinonanoyl sorbitol, 1,2,4-O-trinonanoyl sorbitol, 1,2,5-O-trinonanoyl sorbitol, Nanoyl sorbitol, 1,2,6-O-trinonanoyl sorbitol, 1,3,4-O-trinonanoyl sorbitol, 1,3,5-O-trinonanoyl sorbitol, 1,3,6-O-trinonanoyl sorbitol, 1,4,5-O-trinonanoyl sorbitol, 1,4,6-O-trinonanoyl sorbitol, 1,5,6-O-trinonanoyl sorbitol, 2,3,4-O-trinonanoyl sorbitol, 2,3,5-O-trinonanoyl sorbitol, 2,3,6-O-trinonanoyl sorbitol, 2,4,5-O-trinonanoyl sorbitol, 2,4,6-O-trinonanoyl sorbitol, 2,5,6-O-trinonanoyl sorbitol, 3,4,5-O-trinonanoyl sorbitol, 3,4,6-O-trinonanoyl sorbitol, 3,5,6-O-trinonanoyl sorbitol, 4,5,6-O-trinonanoyl sorbitol, 1,2,3,4-O-tetranonanoyl sorbitol, 1,2,3,5-O-tetranonanoyl sorbitol, 1,2,3,6-O-tetranonanoyl sorbitol, 1,2,4,5-O-tetranonanoyl sorbitol,6-O-tetranonanoyl sorbitol, 1,2,5,6-O-tetranonanoyl sorbitol, 1,3,4,5-O-tetranonanoyl sorbitol, 1,3,4,6-O-tetranonanoyl sorbitol, 1,3,5,6-O-tetranonanoyl sorbitol, 1,4,5,6-O-tetranonanoyl sorbitol, 2,3,4,5-O-tetranonanoyl sorbitol, 2,3,4,6-O-tetranonanoyl sorbitol, 2,3,5,6-O-tetranonanoyl sorbitol, 2,4,5,6-O-tetranonanoyl sorbitol and 3,4,5,6-O-tetranonanoyl sorbitol are particularly preferred. sorbitol, 5-O-nonanoyl sorbitol, 6-O-nonanoyl sorbitol, 1,2-O-dinonanoyl sorbitol, 1,6-O-dinonanoyl sorbitol, 5,6-O-dinonanoyl sorbitol, 1,2,3-O-trinonanoyl sorbitol, 1,2,6-O-trinonanoyl sorbitol, 1,5,6-O-trinonanoyl sorbitol, 4,5,6-O-trinonanoyl sorbitol, 1,2,4,6-O-tetranonanoyl sorbitol, 1,2,5,6-O-tetranonanoyl sorbitol, 1,3,4,6-O-tetranonanoyl sorbitol, 1,3,5,6-O-tetranonanoyl sorbitol and 1,4,5,6-O-tetranonanoyl sorbitol.

[0015] In the case of n-nonanoic acid esters of erythritol, the various esters can be chosen, for example, from the following: 1-O-nonanoylerythritol, 2-O-nonanoylerythritol, 3-O-nonanoylerythritol, 4-O-nonanoylerythritol, 1,2-O-dinonanoylerythritol, 1,3-O-dinonanoylerythritol, 1,4-O-dinonanoylerythritol, 2,3-O-dinonanoylerythritol, 2,4-O-dinonanoylerythritol, 3,4-O-dinonanoylerythritol, 1,2,3-O-trinonanoylerythritol, 1,2,4-O-trinonanoylerythritol, 1,3,4- O-trinonanoylerythritol, 2,3,4-O-trinonanoylerythritol and 1,2,3,4-O-tetranonanoylerythritol, particularly preferred are 1-O-nonanoylerythritol, 2-O-nonanoylerythritol, 3-O-nonanoylerythritol, 4-O-nonanoylerythritol, 1,2-O-dinonanoylerythritol, 1,3-O-dinonanoylerythritol, 1,4-O-dinonanoylerythritol, 2,4-O-dinonanoylerythritol, 1,2,4-O-trinonanoylerythritol, 1,3,4-O-trinonanoylerythritol and 1,2,3,4-O-tetranonanoylerythritol.

[0016] The n-nonanoic acid esters preferred according to the invention are characterized in that they include mono-n-nonanoic acid ester and di-n-nonanoic acid ester, preferably tri-n-nonanoic acid ester.

[0017] Preferably, the mono-n-nonanoic acid esters present in this context have at least two positional isomers.

[0018] According to the invention, it is preferred that the n-nonanoic acid esters according to the invention have an average degree of esterification of 1.0 to 4.0, preferably 1.0 to 3.8, more preferably 1.1 to 2.5, particularly preferably 1.3 to 2.3, with the exception of n-nonanoic acid esters of erythritol which have an average degree of esterification of more than 3.2. Regarding the determination of the degree of esterification of the n-nonanoic acid esters according to the invention by GC, see below.

[0019] The n-nonanoic acid esters preferred according to the invention are characterized in that they are present in a mixed composition containing less than 25% by weight, preferably 0.01% to 20% by weight, particularly preferably 0.05% to 10% by weight, of free n-nonanoic acid, where the weight percentages are based on the sum of all n-nonanoic acid esters of xylitol, sorbitol and erythritol and n-nonanoic acid. The free n-nonanoic acid may be in protonated or neutralized form.

[0020] The content of free n-nonanoic acid in the mixture composition according to the invention containing nonanoic acid ester is first determined by determining the acid number, which can be used to determine the weight proportion of n-nonanoic acid by its molar mass. Suitable methods for determining the acid number are in particular those according to DGF CV 2, DIN EN ISO 2114, Ph.Eur. 2.5.1, ISO 3682 and ASTM D 974. The saponification number is determined by a person skilled in the art according to DGF CV 3 or DIN EN ISO 3681.

[0021] The n-nonanoic acid esters preferred according to the present invention are characterized in that they are present in a mixed composition comprising 0.05% by weight to 40% by weight, preferably 0.2% by weight to 25% by weight, particularly preferably 0.5% by weight to 10% by weight, most preferably 2.0% by weight to 8.0% by weight of free xylitol, sorbitol and / or erythritol, where the weight percentages are based on the sum of all n-nonanoic acid esters of xylitol, sorbitol and erythritol and all xylitol, sorbitol and erythritol.

[0022] A preferred mixed composition according to the present invention comprises the n-nonanoic acid ester according to the present invention in an amount of 40.0% by weight to 99.5% by weight, preferably 50.0% by weight to 98.0% by weight, particularly preferably 40.0% by weight to 95.0% by weight, most preferably 60.0% by weight to 80.0% by weight, where the weight percentages are based on the total mixed composition.

[0023] The n-nonanoic acid esters according to the invention have good processability in liquid form, for example for the production of formulations, in particular for cosmetic applications.

[0024] Thus, the mixed compositions which are preferred according to the invention and which contain an n-nonanoic acid ester according to the invention are characterized in that they contain from 0.1% to 60% by weight, preferably from 1.0% to 50% by weight, even more preferably from 5.0% to 40% by weight, particularly preferably from 10% to 35% by weight of at least one solvent. Preferably, according to the invention, these solvents are from the following group: a) 1,2-diols, 1,3-diols, 1,4-diols and α,ω-diols, with the aforesaid preferably having 2 to 8 carbon atoms; b) polyols, in particular glycerol, oligoglycerols, such as diglycerol and polyglycerol; c) glycerol fatty acid partial esters, oligoglycerol fatty acid partial esters, such as diglycerol fatty acid partial esters and polyglycerol fatty acid partial esters, and d) water Particularly preferred solvents are selected from propane-1,3-diol, propylene glycol, glycerin and water.

[0025] According to the invention, n-nonanoic acid esters are preferred which are characterized in that the complete diester component of the n-nonanoic acid ester comprises 10% by weight to 50% by weight, preferably 15% by weight to 45% by weight, particularly preferably 20% by weight to 35% by weight of a positional isomer in which at least one secondary hydroxyl group has been esterified.

[0026] The determination of the degree of esterification, the content of the various positional isomers, for example in the complete monoester and diester components of the n-nonanoic acid esters according to the invention and the content of triester species relative to the sum of all the n-nonanoic acid esters according to the invention present, and the content of the positional isomers in the complete diester components of the n-nonanoic acid esters according to the invention in which at least one secondary hydroxyl group has been esterified, can be carried out by gas chromatography, optionally in combination with mass spectrometry (GC-FID and GC-MS): First, a 100 mg sample of the appropriate n-nonanoic acid ester is dissolved in 5 ml of pyridine / dichloromethane (4:1). Then, 0.5 ml of N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) and 0.5 ml of a mixture of pyridine and trimethylsilylimidazole (39:11) are added. Derivatization is carried out at 80° C. for 30 minutes. A sample of the clear solution thus obtained is analyzed by GC-FID and GC-MS. The analytical parameters are as follows: Gas chromatograph: Agilent MSD 7890 Column: Agilent SimDist (10m, 0.32mm, 0.1μm) Flow rate: constant hydrogen at 3 ml / min (GC-MS: helium) Temperature 65°C, 10°C / min; 365°C, 15 min, injector 0.1 μl, on-column Detector: FID, 370℃ / GC-MS Scan 35-650 d

[0027] In GC-FID analysis, the esters present in the sample are separated according to their total chain length. The proportion of the individual ester species relative to one another is determined by the respective area proportions of the GC-FID peaks. The peaks are identified / assigned to the individual ester species by GC-MS and, if necessary, also by comparison with the retention times of separately prepared and separated standards, for example of mono- and diesters in which only the primary hydroxyl groups are esterified. In this way, the content of free protonated carboxylic acids and also the content of free neutralized carboxylic acids can be determined as well, since these are also derivatized.

[0028] The degree of esterification is determined by the sum of the peak areas of all mono-, di-, tri-, tetra-, penta- and hexa-esters respectively:

number

number

number

[0029] The n-nonanoic acid ester of xylitol, sorbitol or erythritol according to the present invention can be produced by any process known to those skilled in the art.When the n-nonanoic acid ester of xylitol or sorbitol according to the present invention is produced at relatively high temperature in the presence of chemical catalyst, at least partial dehydration of xylitol and / or sorbitol may occur.Three decomposition products of xylitol frequently occur under such conditions are anhydropentitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol (J. Carbohydr. Chem. 2004, 23, 4, 169-177 and Adv. Carbohydr. Chem. Biochem., 1983, 41, 27-66). Four decomposition products of sorbitol frequently occurring under such conditions are anhydrohexitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol (Advances in Carbohydrate Chemistry and Biochemistry, 1983, 41, 27-66) and isosorbide (1,4:3,6-dianhydrosorbitol; ChemSusChem. 5 (1): 167-176). During the esterification reaction to produce n-nonanoic acid esters of xylitol or sorbitol according to the invention, the aforementioned decomposition products of xylitol and sorbitol typically also give rise to mono-, di- and triesters of the decomposition products, respectively, in the form of mixtures of various positional isomers. Mixture compositions preferred according to the invention and comprising n-nonanoic acid esters according to the invention preferably contain only trace amounts of such esters of decomposition products of xylitol and sorbitol.Thus, all n-nonanoic acid esters of xylitol, sorbitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol present in the mixed composition preferred according to the invention are 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol. and 1,4-anhydroribitol residues in total of less than 20% by weight, preferably less than 15% by weight, particularly preferably less than 10% by weight, particularly preferably less than 5% by weight, where the weight percentages are based on all residues of xylitol, sorbitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol present in said n-nonanoic acid esters.

[0030] Alternatively preferred, the n-nonanoic acid esters of decomposition products of xylitol and sorbitol are contained in the mixed composition according to the invention in large amounts.These alternatively preferred mixed compositions according to the invention have outstanding properties in dishwashing applications, for example, they help to reduce the adhesion of undesirable substances to dishware, especially metal cutlery.Thus, all n-nonanoic acid esters of xylitol, sorbitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol present in the alternatively preferred mixed composition according to the invention are 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol, 1,4-anhydroribitol, ... The n-nonanoic acid esters preferably contain a total of 50% to 95% by weight, preferably 60% to 90% by weight, particularly preferably 70% to 85% by weight of xylitol, sorbitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol residues, where the weight percentages are based on all residues of xylitol, sorbitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol present in said n-nonanoic acid esters.

[0031] The content of xylitol, its degradation products (1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol), sorbitol and its degradation products (1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide) is determined using high performance liquid chromatography (HPLC). The method involves alkaline hydrolysis of the n-nonanoic acid esters to be analyzed, removal of the carboxylic acids and analysis of the sugar and sugar alcohol fractions. For this purpose, 150 mg of the analytes in 2.00 ml of 1 M aqueous KOH solution are n-NonanosateThe initial charge of is hydrolyzed at 95 °C for 30 min with stirring. The reaction solution is then cooled to room temperature and adjusted to pH 2-3 with 2 M aqueous HCl. The resulting precipitated carboxylic acid is then extracted with diethyl ether (3 × 3.00 ml), removing the organic supernatant after each extraction with a pipette. After extraction, the aqueous solution is heated to 50 °C with stirring for 20 min to remove the remaining ether (boiling point of diethyl ether: 34.6 °C). The resulting aqueous solution is made up to 10.0 ml with redistilled H2O, then diluted 1:10 and an aliquot of the solution is analyzed by HPLC. The analysis is carried out under the following conditions: Column: Aminex HPX-87C column 300 x 7.8 mm Eluent: H2O Injection volume: 10.0μl Flow rate: 0.60ml / min Column temperature: 50℃ Detector: G1362A / 1260 RID (Agilent), 35°C Runtime: 30.0 minutes

[0032] Xylitol and its decomposition products, and sorbitol and its decomposition products are separated by ion exchange process. For evaluation, the sum of the peak areas of xylitol and sorbitol is expressed in relation to the sum of the peak areas of 1,4-anhydroxylitol, 1,4-anhydroarabinitol and 1,4-anhydroribitol, 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide. Reference substances of the decomposition products of xylitol and sorbitol are commercially available or alternatively can be obtained by heating xylitol and / or sorbitol in the presence of an acidic catalyst (>140°C) or a basic catalyst (>180°C or higher).

[0033] The invention therefore further provides a formulation, in particular a cosmetic formulation or a household care formulation, comprising an n-nonanoic acid ester of xylitol, sorbitol or erythritol according to the invention and / or a mixed composition according to the invention.

[0034] The present invention further provides a method for the enzymatic preparation of n-nonanoic acid esters of xylitol, sorbitol or erythritol according to the invention, comprising the steps of: A) providing xylitol, sorbitol or erythritol and at least one n-nonanoyl group donor, in particular selected from n-nonanoic acid esters and n-nonanoic acid, more preferably n-nonanoic acid, B) reacting xylitol, sorbitol or erythritol with at least one n-nonanoyl group donor in the presence of a lipase at a temperature between 75° C. and 110° C., preferably between 77° C. and 100° C., even more preferably between 80° C. and 95° C., to obtain n-nonanoic acid esters of xylitol, sorbitol or erythritol, and optionally C) purifying n-nonanoic acid esters of xylitol, sorbitol or erythritol; The present invention provides a method comprising:

[0035] The n-nonanoic acid esters advantageously used according to the invention as acyl group donors are selected from esters based on alkanols and polyols having up to 6 carbon atoms, particularly preferably esters based on alkanols and polyols having up to 3 carbon atoms, very particularly preferably glycerol esters.

[0036] The n-nonanoic acid advantageously used according to the invention as acyl group donor can be used in particular in the form of technical grade n-nonanoic acid, where such technical grade n-nonanoic acid is understood to mean a material that is not ultra-pure but contains a proportion of impurities, for example in the form of further fatty acids. Particularly preferred is the use of technical grade n-nonanoic acid with a purity of more than 85% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight, in particular more than 98% by weight, based on the total fatty acids present, which is preferably obtained by proceeding in a hydrogen peroxide-based process from ω-9-fatty acids, preferably oleic acid and / or erucic acid, in particular from non-tropical vegetable oils, such as rapeseed oil, sunflower oil and / or safflower oil. Thus, in the method according to the invention, the provision of n-nonanoic acid in process step A) preferably comprises the additional step of providing ω-9-fatty acids, preferably oleic acid and / or erucic acid, which are reacted with hydrogen peroxide in the presence of a catalyst, in particular a tungsten-based catalyst, such as tungstic acid and its salts, pertungstic acid and its salts, tungstophosphoric acid and its salts, niobium oxide, cobalt salts, such as cobalt acetate and cobalt naphthenate, to obtain n-nonanoic acid. The ω-9-fatty acids provided, preferably oleic acid and / or erucic acid, are preferably obtained from non-tropical vegetable oils, such as rapeseed oil, sunflower oil and / or safflower oil.

[0037] A process preferred according to the invention is characterized in that xylitol, sorbitol or erythritol and the at least one n-nonanoyl group donor make up at least 80% by weight, preferably at least 90% by weight, particularly preferably at least 95% by weight, of the overall reaction mixture at the start of process step B).

[0038] When the reaction mixture includes two or more selected from xylitol, sorbitol and erythritol, these are added together.

[0039] In this context, only little, if any, solvent may be present in the entire reaction mixture, since it consists mostly of the reactants, i.e. xylitol, sorbitol and / or erythritol, and the n-nonanoyl group donor. From the above, it is clear that in the process according to the invention, the n-nonanoyl group donor is not encompassed by the term "solvent". Possible solvents would be, for example, ketones, such as methyl isobutyl ketone or cyclohexanone, sterically hindered secondary alcohols, such as 2-butyl-1-octanol, methylcyclohexanol, 1-methoxy-2-propanol, butane-2,3-diol, 2-octanol, diacetone alcohol, 2-methyl-2-butanol, and ethers, such as 1,4-dioxane, tetrahydrofuran and Varonic® APM. Based on the entire reaction mixture, the solvent is present in a maximum total amount of less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight. The phrase "present in a maximum amount of less than X% by weight" can be considered equivalent to "containing less than X% by weight."

[0040] Particular preference is given to carrying out the process according to the invention solvent-free.

[0041] A preferred method according to the present invention is characterized in that the molar ratio of all hydroxyl groups provided by the xylitol, sorbitol or erythritol provided to n-nonanoyl groups present in all n-nonanoyl group donors provided is within the range of 1.00:0.05 to 1.00:0.90, preferably 1.00:0.07 to 1.00:0.75, particularly preferably 1.00:0.10 to 1.00:0.50, or particularly preferably 1.00:0.15 to 1.00:0.35.

[0042] If the reaction mixture also contains two or more selected from xylitol, sorbitol and erythritol, and optionally further sugars or sugar alcohols (see below), the hydroxyl groups provided by these are added.

[0043] A method step preferred according to the present invention is characterized in that process step A) comprises blending xylitol, sorbitol or erythritol with at least one n-nonanoyl group donor for at least 10 minutes, preferably 30 minutes, even more preferably 60 minutes, wherein blending is preferably carried out within a temperature range of 80°C-120°C, preferably 90°C-120°C, even more preferably 95°C-120°C, even more preferably 100°C-120°C.

[0044] The lipase advantageously used according to the invention in process step B) is present immobilized on a solid support.

[0045] Lipases which are advantageously used according to the invention in process step B) are lipase from Thermomyces lanuginosus (accession number O59952), lipases A and B from Candida antarctica (accession number P41365) and lipase from Mucor miehei (accession number P19515), lipase from Humicola sp. (accession number O59952), lipase from Rhizomucor javanicus (accession number S32492), lipase from Rhizopus oryzae (accession number P61872), lipase from Candida rugosa ... Lipases from Rhizopus niveus (accession number P61871), Penicillium camemberti (accession number P25234), Aspergillus niger (ABG73613, ABG73614 and ABG37906) and Penicillium cyclopium (accession number P61869), particularly preferably Candida antarctica (accession number P20261, P32946, P32947, P3294 and P32949), Rhizopus niveus (accession number P61871), Penicillium camemberti (accession number P25234), Aspergillus niger (ABG73613, ABG73614 and ABG37906) and Penicillium cyclopium (accession number P61869). and lipases A and B from (Arabia antarctica) (Accession No. P41365) and their respective homologues at the amino acid level of at least 60%, suitably at least 80%, preferably at least 90%, particularly preferably at least 95%, 98% or 99%.

[0046] The accession numbers cited in the context of the present invention correspond to the NCBI Protein Bank database entries dated January 1, 2017; generally, in the context of the present invention, version numbers of entries are identified by ".number", e.g., ".1".

[0047] By comparison with the reference sequence, the enzymes that are homologous at the amino acid level preferably have an enzymatic activity of at least 50%, in particular at least 90%, in the propyl laurate unit, as defined in the context of the present invention. To measure the enzymatic activity in PLU (propyl laurate unit), 1-propanol and lauric acid are mixed homogeneously in an equimolar ratio at 60°C. The reaction is started by adding the enzyme, and the reaction time is stopped. Samples are taken from the reaction mixture at regular intervals, and the content of converted lauric acid is measured by titration with potassium hydroxide solution. The enzymatic activity in PLU is obtained from the rate at which 1 g of the enzyme synthesizes 1 μmol of propyl laurate per minute at 60°C, and in this regard, see also US Patent Publication No. 20070087418, in particular

[0185] .

[0048] Examples of commercially available lipases, and which can likewise be used advantageously in the method according to the invention, are the commercial products Lipozyme TL IM, Novozym 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523 (all commercially available from Novozymes A / S, Bagsberg, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercially available from Roche Molecular Biochemicals, Mannheim, Germany), CALB Immo Plus® from Purolite, and also 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" (both are commercially available products manufactured by Amano Enzyme Co., Ltd. (Japan)), Evoxx Lipase 4.3.040 191G immobilized, Evoxx Addzyme CALB 165G immobilized, Evoxx Addzyme TL 165G immobilized, Evoxx Addzyme RD 165G immobilized, Evoxx Addzyme CALB 10P, Evoxx Addzyme CALB 5L, Evoxx Addzyme TL 100P, Evoxx Addzyme TL 100L, Evoxx Addzyme RD 50P, Evoxx Addzyme RD 10L (all commercial products manufactured by Evoxx (Germany)), Fermenta Biocatalyst CAL B 1L-10L, Fermenta Biocatalyst CAL B 1L-10L, Fermenta Biocatalyst CAL B TA 10000 immobilized, Fermenta Biocatalyst CAL B 1000-5000 immobilized (all commercially available from Fermenta Biotech (India)), Purolite CALB Immo 8285 immobilized, Purolite CALB Immo 8806 immobilized, Purolite CALB Immo Kit immobilized, Purolite CALB Immo Plus immobilized (all commercially available from Purolite (USA)), Vland L Lipase Kingpase, Vland Kingzyme IM-100, Vland L Lipase Coated Lipase (all commercially available from Vland (China)), Clea B1, Eucodis CALB, Eucodis EL001, Eucodis EL012, Eucodis EL013, Eucodis EL016, Eucodis EL056, Eucodis EL070 (all commercially available from Eucodis (Austria)).

[0049] "Homology at the amino acid level" in the context of the present invention is understood to mean "amino acid identity" that can be determined using known methods. In general, special computer programs are used with algorithms that take into account certain requirements. A preferred method for determining identity first produces a maximum alignment between the sequences to be compared. Computer programs for determining identity include: - GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), page 387, Genetics Computer Group University of Wisconsin, Medicine (WI) and - BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pages 403-410 BLAST programs include, but are not limited to, the GCG program package from 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., supra). Those skilled in the art will recognize that a variety of 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, for example, by the algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which is integrated into the GAP program of the GCG software package (available at http: / / www.gcg.com), using either a Blossom 62 matrix or a PAM250 matrix, a gap weight of 16, 14, 12, 10, 8, 6 or 4, and a length weight of 1, 2, 3, 4, 5 or 6. Those skilled in the art will recognize that using different parameters will give slightly different results, but overall the percentage of identity between two amino acid sequences will not be significantly different. The Blossom 62 matrix is ​​usually used with the default settings (gap weight: 12, length weight: 1). In the context of the present invention, 60% identity according to the above algorithm means 60% homology. The same applies for identities greater than this.

[0050] In process step B), it is advantageous according to the invention to use 25 PLU to 2000 PLU, preferably 200 PLU to 1500 PLU, particularly preferably 500 PLU to 1250 PLU of lipase per g of xylitol, sorbitol or erythritol to be converted.

[0051] If the reaction mixture contains two or more selected from xylitol, sorbitol and erythritol, and optionally further sugars or sugar alcohols (see below), their weights are added.

[0052] Preferably, according to the invention, process step B) is carried out at a pressure of less than 1 bar, preferably less than 0.5 bar, particularly preferably less than 0.1 bar.

[0053] Alternatively, and more preferably according to the invention, process step B) is carried out in a bubble column reactor and at least one inert gas is passed through the reaction mixture, which gas is preferably selected from the group comprising, and preferably consisting of, nitrogen and argon. In this context, it is preferred according to the invention that the gas flow is between 1 and 60 kg / h, preferably between 5 and 25 kg / h, even more preferably between 10 and 14 kg / h.

[0054] Preferably according to the invention, process step B) is characterized in that it is finished at the latest 180 hours, preferably 120 hours, particularly preferably 100 hours after the lipase has been added.

[0055] A method step preferred according to the invention is characterized in that by-products formed in process step B), such as water if the n-nonanoyl group donor used is n-nonanoic acid or the corresponding alcohol if the n-nonanoyl group donor used is an n-nonanoic acid ester, are removed. This is possible, for example, by distillation.

[0056] Process step C) of the method according to the invention comprises the purification of the n-nonanoic acid esters of xylitol, sorbitol or erythritol. For this purpose, the methodologies usable make it possible to obtain higher concentrations of n-nonanoic acid esters of xylitol, sorbitol or erythritol.

[0057] Preferably according to the invention, the process according to the invention comprises in process step C) removing the lipase used in the process according to the invention.

[0058] When the lipase is immobilized on a carrier, according to the present invention, it is preferred that the lipase is removed by filtration through a filter, particularly a bag filter, having a mesh size of 0.1 μm to 1250 μm, preferably 0.5 μm to 200 μm, and particularly preferably 50 μm to 100 μm.

[0059] According to the invention, the method of the invention preferably comprises, in process step A), in addition to xylitol, sorbitol or erythritol, the addition of sugars from the following group: agarose, allitol, allulose, altritol, amylopectin, amylose, arabinitol, arabinose, cellobiose, cellulose, chitin, cyclodextrin, deoxyribose, dextran, erythritol, fructan, fructose, fucose, galactitol, galactose, glucitol, glucose, glycogen, hyaluronic acid, iditol, inulin , isomalt, isomaltulose, isomelisitose, lactitol, lactose, lactulose, maltitol, maltohexose, maltopentose, maltose, maltotetrose, maltotriose, maltulose, mannitol, mannose, melizitose, pectin, raffinose, rhamnose, ribitol, ribose, sucrose, sorbitol, sorbose, stachyose, starch, starch hydrolysates, threitol, trehalulose, umbelliferose, xylitol and xylose, more preferably aliquots of maltose, ... is selected from the group consisting of tallow, allulose, altritol, arabinitol, arabinose, cellobiose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucitol, glucose, iditol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, sucrose, sorbitol, sorbose, threitol, trehalulose, xylitol and xylose. Characterized in that at least one other sugar or sugar alcohol is provided, very preferably the sugar or sugar alcohol is selected from erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose, maltulose, mannitol, sucrose, sorbitol, sorbose, xylitol and xylose, particularly preferably erythritol, fructose, glucose, sorbitol, xylitol and xylose, which also pass through further process steps.

[0060] In the context of the present invention, the expression "one other sugar or sugar alcohol" means a sugar or sugar alcohol other than xylitol, for example when xylitol is present, and similarly for sorbitol and erythritol.

[0061] The present invention further provides n-nonanoic acid esters of xylitol, sorbitol or erythritol obtainable by the process according to the invention.

[0062] The present invention further provides the use of the n-nonanoic acid esters of xylitol, sorbitol or erythritol according to the invention and / or the n-nonanoic acid esters of xylitol, sorbitol or erythritol obtainable by the process according to the invention, as well as the mixed compositions according to the invention, as viscosity modifiers, care actives, foam boosters or solubilizers, antibacterial agents, antistatic agents, binders, corrosion inhibitors, dispersants, emulsifiers, film-forming agents, water retention agents, opacifying agents, oral care agents, preservatives, skin care agents, hydrophilic emollients, foam stabilizers and / or non-ionic surfactants, preferably as viscosity modifiers, emulsifiers, antibacterial agents and / or hydrophilic emollients, particularly preferably as viscosity modifiers, in particular as thickeners and / or antibacterial agents, in particular in cleaning or care formulations.

[0063] The following examples are provided to illustratively explain the present invention, and are not intended to limit the scope of the present invention, the scope of which is clear from the entire specification and claims, to the embodiments specified in the examples.

[0064] The following figures are an integral part of the embodiment. [Brief description of the drawings]

[0065] [Figure 1] FIG. 1 shows gas chromatography of Example 1. [Diagram 2] FIG. 1 shows the gas chromatography of Example 4. [Diagram 3] FIG. 1 shows the gas chromatography of Example 6.

[0066] Working Example: Example 1: Enzymatic esterification of xylitol with 1.50 equivalents of n-nonanoic acid (according to the invention) A mixture of xylitol (176.3 g, 1.16 mol, 1.00 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 275.0 g, 1.74 mol, 1.50 equiv.) was heated to 90 °C with stirring and N2 flow, and after 1 h immobilized Candida antarctica lipase B enzyme (13.5 g; Purolite D5619, equivalent to 117234 PLU) was added. The mixture was stirred at 85 °C and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product was homogenous in the molten state, light yellow in color, and had an acid value of 1.5 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, and triesters, each consisting of multiple positional isomers, as evident in Figure 1, where, for example, the signals at 11.55 and 11.93 min correspond to the monoester positional isomers, and the signals at 15.51, 15.57, and 16.06 min correspond to the diester positional isomers.

[0067] Example 2: Enzymatic esterification of a mixture of 0.90 equivalents of xylitol, 0.10 equivalents of xylose and 1.50 equivalents of n-nonanoic acid (according to the invention) A mixture of xylitol (77.0 g, 0.506 mol, 0.90 equiv.), xylose (8.56 g, 0.057 mol, 0.10 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 129.1 g, 0.816 mol, 1.45 equiv.) was heated to 90 °C with stirring and N2 flow, and after 1 h immobilized Candida antarctica lipase B enzyme (6.44 g; Purolite D5619, equivalent to 55925 PLU) was added. The mixture was stirred at 85 °C and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product was slightly hazy in the molten state, pale yellow in color, and had an acid value of 5.6 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, and triesters, each consisting of multiple positional isomers.

[0068] Example 3: Enzymatic esterification of a mixture of 0.90 equivalents of xylitol, 0.10 equivalents of xylose and 1.27 equivalents of n-nonanoic acid (according to the invention) A mixture of xylitol (82.9 g, 0.545 mol, 0.90 equiv.), xylose (9.21 g, 0.061 mol, 0.10 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 121.75 g, 0.769 mol, 1.27 equiv.) was heated to 90 °C with stirring and N2 flow, and after 1 h immobilized Candida antarctica lipase B enzyme (6.42 g; Purolite D5619, equivalent to 55751 PLU) was added. The mixture was stirred at 85 °C and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product was homogeneous in the molten state, light yellow in color, and had an acid value of 5.0 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, and triesters, each consisting of multiple positional isomers.

[0069] Example 4: Enzymatic esterification of erythritol with 1.5 equivalents of n-nonanoic acid (according to the invention) A mixture of erythritol (125.0 g, 1.02 mol, 1.00 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 226.31 g, 1.54 mol, 1.50 equiv.) was heated to 85 °C with stirring and N2 flow. After 1 h, immobilized Candida antarctica lipase B enzyme (10.5 g; Purolite D5619, equivalent to 91258 PLU) was added and the mixture was stirred at 85 °C and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 5.6 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, tri-, and tetraesters, each of which consisted of multiple positional isomers. This is evident in Figure 2, where the signals at 11.09 and 11.34 min correspond to the monoester positional isomers, and the signals at 15.56 and 15.89 min correspond to the diester positional isomers.

[0070] Example 5: Enzymatic esterification of sorbitol with 1.55 equivalents of n-nonanoic acid (according to the invention) A mixture of sorbitol (96.5 g, 0.530 mol, 1.00 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 129.9 g, 0.821 mol, 1.55 equiv.) was heated to 100 °C under stirring and N2 flow. After 1 h, the mixture was cooled to 85 °C and immobilized Candida antarctica lipase B enzyme (6.79 g; equivalent to Purolite D5619, 58807PLU) was added and the mixture was further stirred at 85 °C and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 3.2 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, tri-, and tetraesters, each consisting of multiple positional isomers.

[0071] Example 5a: Enzymatic esterification of sorbitol with 2.90 equivalents of n-nonanoic acid (according to the invention) A mixture of sorbitol (96.5 g, 0.530 mol, 1.00 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 243.2 g, 1.54 mol, 2.90 equiv.) was heated to 100 °C under stirring and N2 flow. After 1 h, the mixture was cooled to 85 °C and immobilized Candida antarctica lipase B enzyme (10.2 g; equivalent to Purolite D5619, 88236PLU) was added and the mixture was further stirred at 85 °C and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 3.9 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, tri-, and tetraesters, each consisting of multiple positional isomers.

[0072] Example 6: Enzymatic esterification of a mixture of 0.74 equivalents of xylitol, 0.26 equivalents of sorbitol and 1.30 equivalents of n-nonanoic acid (according to the invention) A mixture of xylitol (65.5 g, 0.430 mol, 0.74 equiv.), sorbitol (28.1 g, 0.154 mol, 0.26 equiv.) and n-nonanoic acid (acid value = 355 mg KOH / g, 99%, 120.2 g, 0.759 mol, 1.30 equiv.) was heated to 90 °C with stirring and N2 flow, and after 1 h immobilized Candida antarctica lipase B enzyme (6.41 g; Purolite D5619, equivalent to 55500 PLU) was added. The mixture was stirred at 85 °C and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 1.5 mg KOH / g. Analysis by GC-FID showed a mixture of mono-, di-, tri-, and tetraesters, each consisting of multiple positional isomers. This is evident in Figure 3, where the signals at 12.32 and 12.73 min correspond to the positional isomers of the xylityl monoester, the signals at 13.85 and 14.52 min correspond to the positional isomers of the sorbityl monoester, the signals at 16.08, 16.45, and 16.97 min correspond to the positional isomers of the xylityl diester, and the signals at 17.63 and 18.41 min correspond to the positional isomers of the sorbityl diester.

[0073] Example 7: Enzymatic esterification of xylitol with 1.50 equivalents of caprylic / capric acid (not according to the invention) A mixture of xylitol (75.7 g, 0.497 mol, 1.00 equiv.) and a mixture of caprylic and capric acids (acid value = 362 mg KOH / g, 60:40 ratio of caprylic and capric acids, 115.7 g, 0.746 mol, 1.50 equiv.) was heated to 90 °C with stirring and N2 for 1 h, cooled to 85 °C, and then immobilized Candida antarctica lipase B enzyme (5.74 g; Purolite D5619, equivalent to 49710 PLU) was added. The mixture was stirred at 85 °C and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 1.5 mg KOH / g.

[0074] Example 8: Enzymatic esterification of a mixture of 0.74 equivalents of xylitol, 0.26 equivalents of sorbitol and 1.30 equivalents of caprylic / capric acid (not according to the invention) A mixture of xylitol (131.5 g, 0.864 mol, 0.74 equiv.), sorbitol (56.4 g, 0.309 mol, 0.26 equiv.), and a mixture of caprylic and capric acids (acid value = 362 mg KOH / g, 60:40 ratio of caprylic and capric acids, 239.6 g, 1.53 mol, 1.30 equiv.) was heated to 90 °C under stirring and N2 flow, and after 30 min immobilized Candida antarctica lipase B enzyme (12.8 g; Purolite D5619, equivalent to 110827 PLU) was added. The mixture was then stirred at 80 °C and 20 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered at 80 °C through a Büchner funnel with a black band filter to remove the enzyme. The resulting product had an acid value of 3.0 mg KOH / g.

[0075] Examples 9a to 9f: Chemical esterification of xylitol and sorbitol (according to the invention) Xylitol or sorbitol (or an aqueous solution thereof) was initially charged together with n-nonanoic acid, and after adding the catalyst, the reaction mixture was heated to the reaction temperature under stirring at a given pressure within 1 hour, and the water formed was continuously removed until the given acid value was reached. Finally, the mixture was filtered through a filter press.

[0076] [Table 1]

[0077] Example 9g: Preparation of xylitol caprylate (=xylitol octanoate) similar to Example 3 of WO 94 / 12651 (not according to the invention): A mixture of xylitol (0.5 g, 3.3 mmol) and octanoic acid (99%, 3.35 g, 23.2 mmol) was heated to 50 °C under mechanical stirring. Sodium octanoate (0.85 g, 5.1 mmol) and Candida antarctica lipase B enzyme (0.5 mL of an aqueous solution containing 5000 PLU / mL) were then added, and the mixture was then stirred at 50 °C for 20 hours. The mixture was then filtered through a Buchner funnel with a black band filter at 50 °C.

[0078] Example 10: Thickening performance in relatively low concentration cosmetic formulations The thickening effect of Examples 1 and 4 according to the invention was evaluated in comparison with a thickening agent not according to the invention. For this purpose, cosmetic formulations were prepared in water consisting of 4.8% cocoamphoacetate, 4.8% cocamidopropyl betaine, 3.6% sodium lauroyl sarcosinate. The pH of the formulations was adjusted to 5.2 with citric acid. 0.6% of the above-mentioned exemplary substance was incorporated into each of these formulations by stirring at 60° C. for 30 minutes, and the viscosity was measured at 22° C. using a Brookfield viscometer (spindle 62, 30 rpm). The results of the viscosity measurements are shown in Table 2.

[0079] [Table 2]

[0080] Example 11: Thickening performance in relatively high concentration cosmetic formulations The thickening effect of Examples 3, 4, 5 and 6 according to the invention was evaluated in comparison with thickeners not according to the invention. For this purpose, cosmetic formulations were prepared in water consisting of 4.8% cocoamphoacetate, 4.8% cocamidopropyl betaine, 3.6% sodium lauroyl sarcosinate. The pH of the formulations was adjusted to 5.2 with citric acid. 0.8% of the above-mentioned exemplary substance was incorporated into each of these formulations by stirring at 60° C. for 30 minutes, and the viscosity was measured at 22° C. using a Brookfield viscometer (spindle 62, 30 rpm). The results of the viscosity measurements are shown in Table 3.

[0081] [Table 3]

[0082] Example 12: Thickening performance in cosmetic formulations The thickening effect of Examples 1, 4, 5 and 6 according to the invention was evaluated in comparison with thickeners not according to the invention. For this purpose, cosmetic formulations were prepared in water consisting of 9% SLES, 3% cocamidopropyl betaine and 0.7% NaCl. The pH of the formulations was adjusted to 5.2 with citric acid. 1.1% of the above-mentioned exemplary substances were incorporated into each of these formulations by stirring at 60° C. for 30 minutes, and the viscosity was measured at 22° C. using a Brookfield viscometer (spindle 62, 30 rpm). The viscosity measurements are shown in Table 4. [Table 4]

[0083] Example 13: Hand washing test To evaluate the skin feel during washing, a test was carried out by a trained sensory panel. The formulation of Example 10 was used for a sensory hand washing test. For this purpose, a group of at least 10 trained testers washed their hands according to a clearly defined procedure. Before application, the hands had to be cleansed with 2 g of a standard surfactant solution for 10 seconds before testing in a standardized manner, and the formulation was rinsed off for 10 seconds. After this pre-washing step, 2 g of the formulation containing the given composition was applied to wet palms. A lather was generated between the hands and the skin feel during washing was judged on a rating scale from 1 (very poor) to 5 (very good). The formulation was rinsed off for 15 seconds. Afterwards, two separate judgments were made on the skin smoothness and skin softness on a rating scale from 1 (very poor) to 5 (very good). This judgment was made immediately after drying and after 3 minutes.

[0084] [Table 5]

[0085] As can be seen from the measurements in Table 5, washing the hands with the formulation according to the invention using the composition according to the invention gives the highest score for skin feel after application.

[0086] Example formulation [Table 6-1] [Table 6-2] [Table 6-3] [Table 6-4] [Table 6-5] [Table 6-6] [Table 6-7]

Table 6-8

Table 6-9

Table 6-10

Table 6-11

Table 6-12

Table 6-13

Table 6-14

Table 6-15

Table 6-16

Table 6-17

Table 6-18

Table 6-19

Claims

1. 1. An n-nonanoic acid ester of xylitol, sorbitol or erythritol, characterized in that said n-nonanoic acid ester is in the form of a mixture in which at least two esters differ with respect to at least one esterification position of at least one nonanoyl group in xylitol, sorbitol or erythritol, with the proviso that n-nonanoic acid ester of erythritol having an average degree of esterification greater than 3.2 is excluded.

2. 2. The n-nonanoic acid ester of claim 1, wherein the n-nonanoic acid ester comprises at least two positional isomers of mono-n-nonanoic acid ester.

3. The n-nonanoic acid ester according to claim 1 or 2, characterized in that the n-nonanoic acid ester includes a mono-n-nonanoic acid ester and a di-n-nonanoic acid ester.

4. 3. The n-nonanoic acid ester according to claim 1, characterized in that the n-nonanoic acid ester has an average degree of esterification of 1.0 to 4.

0.

5. 3. A mixed composition comprising the n-nonanoic acid esters according to claim 1 or 2, characterized in that the composition contains less than 25% by weight of free n-nonanoic acid, where the weight percentage is based on the sum of all n-nonanoic acid esters of xylitol, sorbitol and erythritol and n-nonanoic acid.

6. The mixed composition according to claim 5, characterized in that the composition contains 0.05% to 40% by weight of free xylitol, sorbitol and / or erythritol, where the weight percentages are based on the sum of all n-nonanoic acid esters of xylitol, sorbitol and erythritol and all xylitol, sorbitol and erythritol.

7. 6. The mixture composition of claim 5, wherein the composition comprises 0.1% to 60% by weight of at least one solvent.

8. A method for enzymatically producing n-nonanoic acid esters of xylitol, sorbitol or erythritol according to claim 1 or 2, comprising the steps of: A) providing xylitol, sorbitol or erythritol and at least one n-nonanoyl group donor; B) reacting xylitol, sorbitol or erythritol with said at least one n-nonanoyl group donor in the presence of a lipase at a temperature between 75° C. and 110° C. to obtain n-nonanoic acid esters of xylitol, sorbitol or erythritol; and optionally C) purifying the n-nonanoic acid esters of xylitol, sorbitol or erythritol; A method comprising:

9. 9. The method of claim 8, characterized in that process step A) comprises blending said xylitol, sorbitol or erythritol with said at least one n-nonanoyl group donor for at least 10 minutes.

10. 9. The process according to claim 8, characterized in that the xylitol, sorbitol or erythritol and the at least one n-nonanoyl group donor represent at least 80% by weight of the total reaction mixture at the start of process step B).

11. The lipase may be selected from the group consisting of lipases derived from Thermomyces lanuginosus (Accession No. O59952), lipase A and B derived from Candida antarctica (Accession No. P41365), and lipase derived from Mucor miehei (Accession No. P19515), lipase derived from Humicola sp. (Accession No. O59952), lipase derived from Rhizomucor javanicus (Accession No. S32492), lipase derived from Rhizopus oryzae (Accession No. S32493), and lipase derived from Rhizopus oryzae (Accession No. S32494). oryzae (accession number P61872), Candida rugosa (accession numbers P20261, P32946, P32947, P3294 and P32949), Rhizopus niveus (accession number P61871), Penicillium camemberti (accession number P25234), Aspergillus niger (ABG73613, ABG73614 and ABG37906) and Penicillium cyclopium (ABG73616).

9. The method according to claim 8, characterized in that the lipase is selected from the group comprising the lipase from Bacillus subtilis (Accession No. P61869), Bacillus cyclopium (Accession No. P61869), and their respective homologues of at least 60% at the amino acid level.

12. 9. The method according to claim 8, characterized in that process step B) is carried out at a pressure of less than 1 bar.

13. In process step A, in addition to the xylitol, sorbitol or erythritol, the following group of sugars may be used: agarose, allitol, allulose, altritol, amylopectin, amylose, arabinitol, arabinose, cellobiose, cellulose, chitin, cyclodextrin, deoxyribose, dextran, erythritol, fructan, fructose, fucose, galactitol, galactose, glucitol, glucose, glycogen, hyaluronic acid, iditol, inulin, isomalt, isomaltulose, isomelisitose, lactitol, lactose, la.

9. The method according to claim 8, characterized in that at least one other sugar or sugar alcohol selected from the group consisting of cutulose, maltitol, maltohexose, maltopentose, maltose, maltotetrose, maltotriose, maltulose, mannitol, mannose, melizitose, pectin, raffinose, rhamnose, ribitol, ribose, sucrose, sorbitol, sorbose, stachyose, starch, starch hydrolysis products, threitol, trehalulose, umbelliferose, xylitol and xylose is provided, which also passes through further process steps.

14. 9. An n-nonanoic acid ester of xylitol, sorbitol or erythritol obtainable by the process according to claim 8.

15. Use of the n-nonanoic acid ester according to claim 1 or 2 as a viscosity modifier, a care active ingredient, a foam booster or solubiliser, an antibacterial agent, an antistatic agent, a binder, a corrosion inhibitor, a dispersant, an emulsifier, a film former, a water retention agent, an opacifying agent, an oral care agent, a preservative, a skin care agent, a hydrophilic emollient, a foam stabilizer and / or a non-ionic surfactant.

Images