Method for enzymatically preparing sugar esters and / or sugar alcohol esters

Abstract

The subject matter of the present invention is a process for the enzymatic preparation of sugar esters and / or sugar alcohol esters, and a mixed composition comprising sugar esters and / or sugar alcohol esters.

Description

Field of the Invention

[0001] The subject matter of the present invention is a process for the enzymatic preparation of sugar esters and / or sugar alcohol esters, and a mixed composition comprising sugar esters and / or sugar alcohol esters. Prior art

[0002] Fatty acid esters of sugars and sugar alcohols have surfactant properties and, due to their natural raw material basis and sustainability, are particularly suitable for applications in the food sector and the cosmetics industry.

[0003] The conventional synthesis of fatty acid esters of sugars or sugar alcohols is carried out by reacting sugars or sugar alcohols with fatty acid chlorides in the presence of pyridine (Surfactants, K. Kosswig in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2000, https: / / doi.org / 10.1002 / 14356007.a25_747).

[0004] However, a disadvantage of the process described in the prior art is that the use of such solvents in applications in the food or cosmetics sector is unacceptable and, moreover, the corresponding separation of the solvent requires additional process steps such as crystallization, filtration or distillation. Another disadvantage of the process described in the prior art is the quantitative release of HCl when fatty acid chlorides are used, since HCl can lead to corrosion of the metal surfaces of the reactor.

[0005] An alternative prior art process used, in particular on an industrial scale, reacts sugars or sugar alcohols with free fatty acids or fatty acid alkyl esters in the absence of solvent at a temperature of 200-250° C. in the presence of a basic catalyst such as sodium hydroxide ( GeorgThieme VerlagKG, 2019 Regarding the keywords "Sorbitane" and Surfactants, K. Kosswig in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2000, https: / / doi.org / 10.1002 / 14356007.a25_747). However, the disadvantage of the method described in the prior art is that, during the reaction of sorbitol, for example, under the above conditions, dehydration of the sugar or sugar alcohol occurs as a side reaction. This side reaction occurs even at temperatures of about 140° C. in the presence of an acidic catalyst. For example, sorbitol first dehydrates to anhydrosorbitan (by losing one molecule of water) and further becomes isosorbide (by losing another molecule of water). The sugar or sugar alcohol used therefore loses its hydrophilicity and is therefore less and less suitable as a hydrophilic head group for a surfactant. A further disadvantage of the processes described in the prior art is that the side reactions that occur lead to a dark colour of the resulting products, which optionally require further treatment, for example with bleaching agents such as hydrogen peroxide or activated carbon, in order to be able to use the resulting products, for example, in cosmetic formulations. A further disadvantage of the processes described in the prior art is that the side reactions that occur lead to a bad odour in the resulting products, which can interact undesirably with the perfumes used in cosmetic formulations.

[0006] The enzymatic preparation of fatty acid esters of sugars or sugar alcohols in dilute solutions in organic solvents such as 2-methyl-2-butanol, pyridine, dimethylformamide or 2-pyrrolidone has been described (A. Ducret, A. Giroux, M. Trani, and R. Lortie, Characterization of enzymatically prepared biosurfactants, J. Am. Oil Chem. Soc. 1996, 73, 109-113, doi: 10.1007 / BF02523456; M. Therisod, AMKlibanov, Facile enzymatic preparation of monoacylated sugars in pyridine, J. Am. Chem. Soc., 1986, 108 (18), pp 5638-5640; J. Chem. Soc., Perkin Trans. 1, 1989, 0, 1057-1061, 10.1039 / P19890001057; AEM Janssen, C. Klabbers, MCR Franssen, K. van't Riet, Enzymatic synthesis of carbohydrate esters in 2-pyrrolidone, Enzyme and Microbial Technology, 1991, 13 (7), 565-572). However, the disadvantages of the processes described in the prior art are that the use of such solvents in applications in the food or cosmetics sector is unacceptable and that, in addition, the corresponding separation of the solvent requires additional process steps such as crystallization, filtration or distillation which consume a lot of energy.

[0007] The enzymatic synthesis of fatty acid esters of sugars or sugar alcohols using dilute aqueous solutions of enzymes is described in AEM Janssen, AG Lefferts, K. van 't Riet, Enzymatic synthesis of carbohydrate esters in aqueous media, Biotechnology Letters 1990, 12 (10), 711-716, DOI https: / / doi.org / 10.1007 / BF01024726; H. Seino, T. Uchibori, T. Nishitani et al., Enzymatic synthesis of carbohydrate esters of fatty acid (I) esterification of sucrose, glucose, fructose and sorbitol, J. Am. Oil Chem. Soc. 1984, 61 1761-1765, https: / / doi.org / 10.1007 / BF02582144 and WO9412651. A disadvantage of the methods described in the prior art is that the separation of the product from the aqueous system requires additional energy-intensive process steps, such as crystallization, filtration or distillation, and in the case of buffered aqueous systems, it is also necessary to remove the salt load. A further disadvantage here is that when fatty acids are used as acyl donors, the presence of water hinders the shift of the equilibrium position towards the product. Another disadvantage is that enzymes generally exhibit maximum performance at a specific water activity.

[0008] T.Itoh, Ionic Liquids as Tool to Improve Enzymatic Organic Synthesis, Chemical Reviews 2017, 117, 10567-10607 discloses the fatty acid ester of sugar or sugar alcohol prepared by enzyme catalysis in ionic liquid as solvent. However, the disadvantage of the method described in the prior art is that at least one additional energy-intensive method step such as crystallization, filtration or distillation is required to separate the ionic liquid, because the ionic liquid cannot be retained in the product for downstream applications in the food field or the cosmetics industry. Another disadvantage of the method described in the prior art is that ionic liquids are produced from petrochemical raw materials, so their use is undesirable for natural and sustainable applications in the food field or the cosmetics industry. Another disadvantage of the method described in the prior art is the use of fatty acid vinyl esters as acyl donors, because they release toxicologically harmful acetaldehyde during the reaction, which makes industrial-scale operation difficult, and is also undesirable for applications in the food field or the cosmetics industry. In addition, fatty acid vinyl esters are prepared from petrochemical raw materials such as acetylene or ethylene in the presence of toxicologically harmful metal catalysts such as mercury, cadmium, palladium or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27_419), which excludes the natural and sustainable use of these raw materials in the food sector or the cosmetics industry.

[0009] The enzymatic preparation of fatty acid esters of sugars or sugar alcohols in the presence of choline chloride (or other ammonium or phosphonium salts) to form eutectic mixtures has also been described (S. Siebenhaller, C. Muhle-Goll, B. Luy, F. G. Brenner-Weiss, E. Hiller et al., Sustainable enzymatic synthesis of glycolipids in a deepeutectic solvent system, J. Mol. Catal. B Enzym. 2016, 133, 281–287, doi: 10.1016 / j.molcatb.2017.01.015). However, the disadvantage of the method described in the prior art is that, if left in the product, choline chloride or other ammonium salts or phosphonium salts will negatively affect the application of fatty acid esters of sugar or sugar alcohol due to their salt properties. Another disadvantage of the method described in the prior art is that choline chloride of industrially available quality is a petrochemical raw material, so its presence in the product is undesirable for natural and sustainable applications in the food field or the cosmetics industry. Therefore, another disadvantage of the method described in the prior art is that in order to separate choline chloride or other ammonium salts or phosphonium salts, at least one additional method step, such as crystallization, filtration or distillation, is required.

[0010] The enzymatic esterification of individual sugars contained in honey or agave syrup with fatty acid vinyl esters as acyl donors is described in S. Siebenhaller, J. Gentes, A. Infantes, C. Muhle-Goll, F. G. Brenner-Weiβ, K. Ochsenreither, C. Syldatk, Lipase-Catalyzed Synthesis of SugarEsters in Honey and Agave Syrup, Front. Chem. 2018, 6, Article 24, 1–9, doi: 10.3389 / fchem.2018.00024). A disadvantage of the process described in the prior art is the use of fatty acid vinyl esters as acyl donors, since they release toxicologically harmful acetaldehyde during the reaction, which makes industrial-scale operation difficult and is also undesirable for use in the food sector or the cosmetics industry. In addition, fatty acid vinyl esters are prepared from petrochemical raw materials such as acetylene or ethylene in the presence of toxicologically harmful metal catalysts such as mercury, cadmium, palladium or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27_419), which excludes the natural and sustainable application of these raw materials in the food field or the cosmetics industry. Another disadvantage of the method described in the prior art is that only 0.066 equivalents of acyl donors are used based on the total amount of sugars and sugar alcohols. Another disadvantage of the method described in the prior art is that the large amount of excess sugars and sugar alcohols used leads to the need for at least one additional additional method step such as extraction, crystallization, filtration or distillation to separate the fatty acid esters of sugars and sugar alcohols. Another disadvantage of the method described in the prior art is that the large amount of excess sugars and sugar alcohols used is uneconomical on an industrial scale, and in addition, the sugars and sugar alcohols used need to be recycled in a complex manner. A further disadvantage of the methods described in the prior art is that in the case of honey as substrate only glucose esters are detected and in the case of agave syrup as substrate only fructose esters are detected, i.e. in each case only one of the sugar components contained in the honey or agave syrup is actually esterified.

[0011] JPS58116688 discloses the enzymatic esterification of a mixture of polysaccharides and / or monosaccharides and oligosaccharides; thus always containing oligosaccharides and / or polysaccharides. The reaction is carried out in water or hexane as solvent; comparative examples show that in the absence of solvent or only in small amounts of solvent, almost no conversion can be achieved.

[0012] KR20180007129 discloses a method for preparing a mixture of sucrose esters, fructose esters and glucose esters by enzymatic esterification of sucrose. The method operates in a solution that has been diluted so strongly with water that the lauric acid used is present in a dissolved form. Due to the aqueous acidic conditions, sucrose is cleaved into corresponding monosaccharides and esterified during the reaction. Acyl groups are always used in insufficient amounts relative to the esterified sugar obtained so that the product always contains unreacted sugar. Sucrose esters always account for the majority of the esters obtained. Another disadvantage of this prior art method is that the ratio of the different sugar esters obtained cannot be predicted or controlled.

[0013] The object of the present invention is to provide a process for preparing sugar esters and / or sugar alcohol esters containing in particular 4 to 12, preferably 4 to 6 carbon atoms in the sugar part and the sugar alcohol part, respectively, which process can overcome at least one disadvantage of the prior art processes. In particular, the sugar esters and / or sugar alcohol esters should be prepared from readily available sugars or sugar alcohols having 4 to 12, preferably 4 to 6 carbon atoms.

[0014] Description of the invention

[0015] Surprisingly, it has been found that the process described below enables the objects of the present invention to be achieved.

[0016] The subject of the present invention is a method for the enzymatic preparation of a mixed composition comprising at least two components selected from the group consisting of sugar esters and / or sugar alcohol esters, said sugar esters and / or sugar alcohol esters containing in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar part and the sugar alcohol part, respectively, comprising the following method steps:

[0017] B) reacting a mixture comprising at least two members selected from sugars and sugar alcohols, wherein the sugars and sugar alcohols contain in particular 4 to 12, preferably 4 to 6, carbon atoms, with at least one acyl donor, preferably a fatty acid acyl donor, in particular selected from fatty acid esters and fatty acids, particularly preferably fatty acids, in the presence of a lipase.

[0018] Another subject of the present invention is a mixed composition containing specific sugar esters and / or sugar alcohol esters containing in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar part and the sugar alcohol part, respectively.

[0019] An advantage of the present invention is that the process according to the invention can be carried out in the absence of solvents.

[0020] Another advantage of the present invention is that the process according to the invention can be carried out using natural and sustainable synthetic components.

[0021] Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters according to the invention are obtained in a homogeneous reaction mixture and that these properties can be achieved even at a low degree of esterification.

[0022] Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters according to the present invention have excellent color properties.

[0023] A further advantage of the present invention is that the sugar esters and / or sugar alcohol esters according to the invention have little odor, in particular the typical odor of caramel is barely perceptible.

[0024] An advantage of the present invention is that substrates in a mixture can be successfully converted whereas their individual conversion in the absence of a solvent is unsuccessful.

[0025] A further advantage of the present invention is that no undesired by-products are formed from the sugars / sugar alcohols used, such as sorbitol, upon elimination of water, such as the formation of anhydrosorbitan from sorbitol.

[0026] A further advantage of the present invention is that the sugar esters and / or sugar alcohol esters obtained can be incorporated very easily into formulations, in particular into cosmetic formulations.

[0027] Another advantage of the present invention is that the obtained sugar esters and / or sugar alcohol esters can be used to prepare mild formulations.

[0028] A further advantage of the present invention is that formulations having a particularly good skin feel can be prepared by means of the sugar esters and / or sugar alcohol esters obtained.

[0029] Another advantage of the present invention is that sustainable formulations free of petrochemical components can be prepared by means of the obtained sugar esters and / or sugar alcohol esters.

[0030] Another advantage of the present invention is that the resulting sugar esters and / or sugar alcohol esters can be prepared without quantitative release of HCl or acetaldehyde.

[0031] Another advantage of the present invention is that, due to the good miscibility of the reaction mixture, the reaction can be carried out in a bubble column, thus achieving a longer catalyst life.

[0032] Another advantage of the present invention is that a large amount of acyl donors can be used, based on the total molar amount of sugar and / or sugar alcohol.

[0033] A further advantage of the present invention is that the esters of sugars and sugar alcohols used are obtained in a homogeneous reaction mixture, so that no additional process steps such as extraction, crystallization, filtration or distillation are necessary.

[0034] Another advantage of the present invention is that more than just one of the sugar and sugar alcohol components used is esterified during the reaction.

[0035] Another advantage of the present invention is that a homogeneous melt is obtained when reacting at a relatively low degree of esterification.

[0036] The subject of the present invention is a process for the enzymatic preparation of a mixed composition comprising at least two components selected from the group consisting of sugar esters and / or sugar alcohol esters, which contain in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar part and the sugar alcohol part, respectively, comprising the following process steps:

[0037] B) a mixture containing at least two selected from sugars and sugar alcohols

[0038] The reaction is carried out in the presence of a lipase with at least one acyl donor, preferably a fatty acid acyl donor, in particular selected from fatty acid esters and fatty acids, particularly preferably fatty acids.

[0039] The term "two selected from sugar esters and / or sugar alcohol esters" in the context of the present invention is understood to mean that the two esters are different in terms of their sugar and / or their sugar alcohol. Therefore, esters with two different residues in terms of sugar and / or sugar alcohol residues must be included. Unless otherwise indicated, the percentages (%) shown are mass percentages.

[0040] According to the present invention, all sugars and sugar alcohols can be used, such as agarose, pullulan, amylose, cellulose, chitin, cyclodextrin, dextran, fructan, glycogen, hyaluronic acid, inulin, isomelizitose, maltohexaose, maltopentaose, maltotetraose, maltotriose, melezitose, pectin, raffinose, stachyose, starch, starch hydrolyzate, umbelliferyl, cellobiose, isomalt, isomaltulose, Lactitol, lactose, lactulose, maltitol, maltose, maltulose, sucrose, trehalose, trehalulose, allitol, allulose, altritol, arabitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose.

[0041] Preferably according to the present invention, the sugars and sugar alcohols are selected from sugars and sugar alcohols containing 4 to 12, preferably 4 to 6 carbon atoms.

[0042] According to the present invention, preferably, the sugar and sugar alcohol selected from the group consisting of sugars and sugar alcohols containing 4 to 12 carbon atoms are selected from the group consisting of cellobiose, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, sucrose, trehalose, trehalulose, allitol, psicose, altritol, arabitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose, wherein allitol, psicose, altritol, arabitol, arabinose, deoxyribose, erythritol, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose. Arabinose, cellobiose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, trehalulose, xylitol and xylose are particularly preferred, and erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose, maltulose, mannitol, sorbitol, sorbose, xylitol and xylose are very particularly preferred.

[0043] According to the present invention, preferably, the sugars and sugar alcohols selected from sugars and sugar alcohols containing 4 to 6 carbon atoms are selected from allitol, psicose, altritol, arabitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose, among which erythritol, fructose, glucose, sorbitol, xylitol and xylose are particularly preferred.

[0044] Particularly preferably according to the invention, the sugars and sugar alcohols are selected from the group mentioned.

[0045] A preferred method according to the invention is characterized in that in method step B), as a mixture comprising at least two substances selected from sugars and sugar alcohols, a mixture comprising:

[0046] Glucose, fructose and maltose, with a glucose content of 40 to 50% by weight and a fructose content of 47 to 57% by weight, based in each case on all sugars and sugar alcohols contained in the mixture, and glucose, fructose and sucrose, with a glucose content of 5 to 24% by weight and a fructose content of 75 to 94% by weight, based in each case on all sugars and sugar alcohols contained in the mixture.

[0047] According to the invention, all acyl donors can be used. These are, for example, carboxylic acid esters or carboxylic acids themselves and mixtures thereof. Carboxylic acid esters preferably used as acyl donors according to the invention are selected from esters based on alkanols and polyols having up to 6 carbon atoms, particularly preferably having up to 3 carbon atoms, very preferably glycerol esters.

[0048] The carboxylic acid esters particularly preferably used as acyl donors according to the invention are selected from triglycerides, in particular natural fats and oils, particularly preferably from the group comprising, preferably consisting of, coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algae oil, sesame oil, soybean oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuaçu oil and oils with a high proportion of polyunsaturated fatty acids (PUFA). Sorbitan esters, mono- and diglycerides, in particular those containing the acyl groups described below, can likewise be preferably used.

[0049] Preferably according to the present invention, the acyl donor is selected from fatty acid acyl donors, which particularly provide the acyl group of the acyl group selected from natural fatty acids. Natural fatty acids can be produced based on naturally occurring vegetable oils or animal oils, and preferably have 6-30 carbon atoms, especially 8-22 carbon atoms. Natural fatty acids are usually unbranched, mostly composed of an even number of carbon atoms. Possible double bonds all have cis configurations. Examples are: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, nonanoic acid (can be obtained from the ozonolysis of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (can be obtained from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0050] Preferred for use according to the invention as acyl donors are carboxylic acids, in particular fatty acids, with particular preference being given to using the fatty acids specifically mentioned above.

[0051] According to the invention, vinyl esters are preferably excluded as acyl donors, since they release toxicologically harmful acetaldehyde during the reaction, which makes industrial-scale operation difficult and is also undesirable for use in the food industry or the cosmetics industry. In addition, fatty acid vinyl esters are prepared from petrochemical raw materials such as acetylene or ethylene in the presence of toxicologically harmful metal catalysts such as mercury, cadmium, palladium or silver salts (G. Roscher, Vinyl Esters in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2012, DOI: 10.1002 / 14356007.a27-419), which excludes the natural and sustainable use of these raw materials in the food industry or the cosmetics industry.

[0052] According to the present invention, it is particularly preferred that the sugars and sugar alcohols are selected from erythritol, fructose, glucose, sorbitol, xylitol and xylose, and the acyl donor is selected from at least one of the following groups: caproic acid, caprylic acid, nonanoic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0053] The preferred method according to the invention is characterized in that the mixture containing at least two substances selected from sugars and sugar alcohols used in method step B) contains substances selected from the group consisting of choline salts, ammonium salts and phosphonium salts in an amount of less than 2% by weight, preferably less than 1% by weight, particularly preferably less than 0.1% by weight, and in particular contains no such substances, wherein the weight percentages are based on all sugars and sugar alcohols in the mixture containing at least two substances selected from sugars and sugar alcohols in method step B).

[0054] A preferred process according to the invention is characterized in that in process step B), the molar ratio of all sugars and sugar alcohols to the acyl groups contained in all acyl donors is 1.00:0.08 to 1.00:10.00, preferably 1.00:0.50 to 1.00:7.00, particularly preferably 1.00:1.25 to 1.00:2.25 or particularly preferably 1.00:2.00 to 1.00:4.50.

[0055] A preferred process according to the invention is characterized in that in process step B), the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols to the acyl groups contained in all acyl donors is from 1.00:0.10 to 1.00:3.00, particularly preferably from 1.00:1.25 to 1.00:2.25.

[0056] A preferred process according to the invention is characterized in that in process step B) a mixture comprising sugars and / or sugar alcohols having 4 to 6 carbon atoms is used and the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols having 4 to 6 carbon atoms to the acyl groups contained in all acyl donors is from 1.00:0.20 to 1.00:1.5.

[0057] The lipase used preferably according to the invention is present in the form of an immobilized solid support.

[0058] The lipase preferably used according to the invention in process step B) is a lipase selected from the group consisting of the lipase from Thermomyces lanuginosus (Accession No. 059952), the lipase A and B from Candida antarctica (Accession No. P41365) and the lipase from Mucor miehei (Accession No. P19515), the lipase from Humicola sp. (Accession No. 059952), the lipase from Rhizomucor javanicus (Accession No. S32492), the lipase from Rhizopus oryzae (Accession No. P61872), the lipase from Candida rugosa (Accession No. rugosa (Accession Nos. P20261, P32946, P32947, P3294 and P32949), a lipase from Rhizopus niveus (Accession No. P61871), a lipase from Penicillium camemberti (Accession No. P25234), a lipase from Aspergillus niger (ABG73613, ABG73614 and ABG37906) and a lipase from Penicillium cyclopium (Accession No. P61869), and at least 60%, preferably at least 80%, preferably at least 90%, particularly preferably at least 95%, 98% or 99% homologues thereof at the amino acid level.

[0059] Compared to the reference sequence, an enzyme which is homologous at the amino acid level preferably has at least 50%, in particular at least 90% of the enzyme activity expressed in propyl laurate units as defined in the context of the present invention.

[0060] Commercial examples and carboxyl ester hydrolases which are likewise preferably used in the process according to the invention are the commercial products Lipozyme TLIM, Novozym 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 TM 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).

[0061] "Homology at the amino acid level" is understood in the context of the present invention to mean "amino acid identity", which can be determined by known methods. Usually, special computer programs are used, in which the algorithms take into account specific requirements. A preferred method for determining identity first produces the greatest possible correspondence between the sequences to be compared. Computer programs for determining identity include, but are not limited to, the GCG program package, including

[0062] -GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), p. 387, Genetics Computer Group University of Wisconsin, Medicine (WI), and

[0063] - BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pp. 403-410. The BLAST programs are available from the National Center for Biotechnology Information (NCBI) and other sources (BLAST Manual, Altschul S. et al., NCBINLM NIH Bethesda ND 22894; Altschul S. et al., supra).

[0064] Those skilled in the art will appreciate that various computer programs can be used to calculate the similarity or identity between two nucleotide or amino acid sequences. For example, the percent identity between two amino acid sequences can be determined, for example, by an algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which is incorporated into the GAP program of the GCG software package (available from http: / / www.gcg.com), using a Blossom 62 matrix or a PAM250 matrix with 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 result in slightly different results, but the percent identity between two amino acid sequences will not be significantly different overall. The Blossom 62 matrix is ​​typically used with the default settings (gap weight: 12, length weight: 1).

[0065] In the context of the present invention, 60% identity means 60% homology according to the above algorithm. The same applies to higher identities.

[0066] According to the invention, process step B) is preferably carried out at a reaction temperature of 20 to 160°C, preferably 35 to 130°C, in particular 50 to 110°C.

[0067] According to the invention, process step B) is preferably carried out at a pressure of less than 1 bar, preferably less than 0.5 bar, particularly preferably less than 0.05 bar.

[0068] According to the invention, process step B) is alternatively carried out in a bubble column reactor, wherein at least one inert gas is passed through the reaction mixture; the inert gas is preferably selected from the group comprising, preferably consisting of, nitrogen and argon. In this respect, according to the invention, it is preferred that the gas flow rate is from 1 to 60 kg / h, preferably from 5 to 25 kg / h, even more preferably from 10 to 14 kg / h.

[0069] A preferred process according to the invention is characterized in that in process step B), the mixture comprising at least two substances selected from the group consisting of sugars and sugar alcohols and the acyl donor constitutes in total at least 10% by weight, preferably at least 86% by weight, particularly preferably at least 90% by weight of the entire reaction mixture. Such a high weight proportion of reactants accordingly leaves little room for solvents such as water or hexane.

[0070] A preferred process according to the invention is characterized in that in the process, solvent, in particular water or hexane, is added in an amount of not more than 5% by weight, preferably not more than 2% by weight, particularly preferably not at all, the weight percentages being based on the entire reaction mixture.

[0071] A preferred process according to the invention is characterized in that by-products formed in process step B), such as water when the acyl donor used is an acid and the corresponding alcohol when the acyl donor used is an ester, are removed. This can be done, for example, by distillation.

[0072] According to the invention, the method according to the invention preferably comprises method step A): providing at least two substances selected from the group consisting of sugars and sugar alcohols in solid form or dissolved in water spatially separated from one another and mixing them to obtain a mixture comprising at least two substances selected from the group consisting of sugars and sugar alcohols used in method step B). It is particularly preferred here to concentrate the mixture comprising at least two substances selected from the group consisting of sugars and sugar alcohols and the acyl donor by removing water so that the above components together account for at least 10%, preferably at least 86% by weight, particularly preferably at least 90% by weight of the entire reaction mixture.

[0073] In this context, it is particularly preferred that method step A) comprises reducing the water content of the mixture comprising at least two substances selected from sugars and sugar alcohols used in method step B) to less than 17% by weight, preferably less than 14% by weight, particularly preferably less than 10% by weight, wherein the weight percentages are based on the entire mixture comprising at least two substances selected from sugars and sugar alcohols used in method step B).

[0074] According to the invention, preferably, the process according to the invention comprises process step C) isolating the lipase.

[0075] Also preferably according to the present invention, the method according to the present invention comprises a method step D): filtering the mixed composition comprising at least two selected from sugar esters and / or sugar alcohol esters through a filter, especially a bag filter, with a fineness of 0.1 μ to 1250 μ, preferably 0.5 μ to 100 μ. Preferably according to the present invention, method step D) is carried out in a temperature range of 20° C. to 150° C., especially 40° C. to 120° C. Preferably according to the present invention, method step D) is carried out in a pressure range of 1 bar to 25 bar, especially 1.5 bar to 10 bar.

[0076] Preferably according to the invention, the process according to the invention comprises no further purification steps apart from the optional process steps C) and D).

[0077] Another subject of the present invention is a mixed composition comprising at least two selected from sugar esters and sugar alcohol esters, containing in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar part and the sugar alcohol part, respectively, obtainable by the process according to the invention.

[0078] Another subject of the present invention is also a mixed composition comprising sugar esters and / or sugar alcohol esters, characterized in that the sugar residues and / or sugar alcohol residues of the sugar esters and / or sugar alcohol esters are selected from at least two sugar residues and / or sugar alcohol residues, and the sugar residues and / or sugar alcohol residues are selected from the group consisting of allitol, psicose, altritol, arabitol, arabinose, cellobiose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, iditol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, sucrose, sorbitol, sorbose, threitol, trehalose, trehalulose, xylitol and xylose,

[0079] Preferably selected from erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose, maltulose, mannitol, sucrose, sorbitol, sorbose, xylitol and xylose, particularly preferably selected from erythritol, fructose, glucose, sorbitol, xylitol and xylose,

[0080] and

[0081] The ester residue is at least one acyl group selected from the acid residues of fatty acids,

[0082] The fatty acids are preferably caproic acid, caprylic acid, nonanoic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

[0083] Preferred mixed compositions according to the present invention preferably contain 4 to 6 carbon atoms in the sugar part and the sugar alcohol part, respectively.

[0084] Mixture compositions preferred according to the invention contain sugar esters and / or sugar alcohol esters in an amount of at least 50% by weight, preferably at least 80% by weight, particularly preferably at least 95% by weight, the weight percentages being based on the entire mixture composition.

[0085] Preferred mixed compositions according to the invention are characterized in that the sugar esters and / or sugar alcohol esters contained have a degree of esterification of 1.00 and more, in particular 1.00 to 7.00, particularly preferably 1.25 to 2.25, or particularly preferably 2.00 to 4.50.

[0086] The following examples illustrate the invention by way of example without intending to restrict the invention to the embodiments mentioned in the examples, the scope of application of the invention being derived from the entire description and the claims. Example

[0087] Method for determining acid value

[0088] Suitable methods for determining the acid number are, in particular, those in accordance with DGF CV 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

[0089] Method for determining the specific activity in PLU of the enzyme used

[0090] To determine the enzyme activity expressed in PLU (propyl laurate units), 1-propanol and lauric acid are homogeneously mixed in an equimolar ratio at 60° C. The reaction is started by adding the enzyme and the reaction time is measured. Samples are taken from the reaction mixture at regular intervals and the content of converted lauric acid is determined by titration with potassium hydroxide solution. The enzyme activity expressed in PLU is derived from the rate at which 1 μmol of propyl laurate is synthesized per minute by 1 g of the relevant enzyme at 60° C.; see US20070087418, in particular

[0185] .

[0091] Methods for determining color values

[0092] An aliquot (approximately 10 g, so that the cuvette is completely filled) was measured at 90° C. in a Lico 690 spectrocolorimeter in an 11 mm round cuvette, and the color value indicated in each case was recorded.

[0093] Example 1: Enzymatic esterification of xylitol with 2.00 equivalents of octanoic acid (not according to the present invention)

[0094] A mixture of xylitol (60.0 g, 0.394 mol, 1.00 equiv) and octanoic acid (acid value = 389 mg KOH / g, >98%, 113.70 g, 0.788 mol, 2.00 equiv) was heated to 80° C. under stirring and N2, and after 1 hour, immobilized Candida antarctica lipase B enzyme (5.21 g; Purolite D5619, corresponding to 45110 PLU) was added. The mixture was stirred at 80° C. and 15 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, colorless in the melt and had an acid value of 1.8 mg KOH / g.

[0095] Example 2: Enzymatic esterification of fructose with 2.00 equivalents of octanoic acid (not according to the invention)

[0096] A mixture of fructose (83.31 g, 0.462 mol, 1.00 equiv) and octanoic acid (acid value = 389 mg KOH / g, >98%, 133.36 g, 0.925 mol, 2.00 equiv) was heated to 80° C. under stirring and N2, and after 30 minutes, immobilized antarctic Candida antarctica lipase B enzyme (6.50 g; Fermenta BIOCATALYST CALB TA 10000 NLT 95%, corresponding to 63788 PLU). The mixture was stirred at 80° C. and 20 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was inhomogeneous, reddish in the melt, with an acid number of about 140.5 mg KOH / g (due to the inhomogeneity, the acid number could not be determined unambiguously).

[0097] Example 3: Physical mixture of Examples 1 and 2 (not according to the invention)

[0098] A mixture of the ester obtained as described in Example 1 (42.00 g) and the ester obtained as described in Example 2 (18.00 g) was heated to 80° C. for 1 hour with stirring and N2. The resulting product was inhomogeneous, turbid, orange in the melt, with an acid number of about 40 mg KOH / g (the acid number could not be determined unambiguously due to the inhomogeneity).

[0099] Example 4: Enzymatic esterification of a mixture of xylitol and fructose (70:30) with 2.00 equivalents of octanoic acid (according to the invention) A mixture of xylitol (42.00 g, 0.276 mol), D-(-)-fructose (18.00 g, 1.00 equivalent) and octanoic acid (acid value = 389 mg KOH / g, >98%, 108.40 g, 0.752 mol, 2.00 equivalent, based on the total weight of xylitol and fructose) was heated to 80° C. under stirring and N2, and after 1 hour, immobilized Candida antarctica lipase B enzyme (5.05 g; Purolite D5619, corresponding to 43724 PLU) was added. The mixture was stirred at 80° C. and 15 mbar for 27 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black band filter to remove the enzyme. The resulting product was homogeneous, transparent, pale yellow in the melt and had an acid value of 2.4 mg KOH / g.

[0100] Example 5: Enzymatic esterification of xylitol with 1.50 equivalents of octanoic acid (not according to the invention)

[0101] A mixture of xylitol (89.14 g, 0.586 mol, 1.00 equiv) and octanoic acid (acid value = 389 mg KOH / g, >98%, 126.7 g, 0.879 mol, 1.50 equiv) was heated to 80° C. under stirring and N2 flow, and after 30 minutes, immobilized antarctic Candida antarctica lipase B enzyme (6.47 g; Fermenta BIOCATALYST CALB TA 10000 NLT 95%, corresponding to 63493 PLU). The mixture was stirred at 80° C. and 20 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, colorless in the melt and had an acid number of 1.3 mg KOH / g.

[0102] Example 6: Enzymatic esterification of sorbitol with 1.50 equivalents of octanoic acid (not according to the invention)

[0103] A mixture of sorbitol (98.09 g, 0.538 mol, 1.00 eq.) and octanoic acid (acid number = 389 mg KOH / g, >98%, 116.47 g, 0.808 mol, 1.50 eq.) was heated to 100° C. under stirring and N2 flow, and after 30 minutes, immobilized Candida antarctica lipase B enzyme (6.44 g; Purolite D5619, corresponding to 55759 PLU) was added. The mixture was then stirred at 90° C. and 50 mbar for 24 hours, during which the water formed was continuously distilled off. The resulting product mixture was inhomogeneous, pale yellow after 24 hours, with an acid number of about 10-11 mg KOH / g (due to the inhomogeneity, the acid number could not be determined unambiguously).

[0104] Example 7: Physical mixture of Example 5 and Example 6

[0105] A mixture of the ester obtained as described in Example 5 (42.00 g) and the ester obtained as described in Example 6 (18.00 g) was heated to 80° C. for 1 hour with stirring and N 2. The product obtained was heterogeneous in the melt and had an acid value of 3.7 mg KOH / g.

[0106] Example 8: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 1.50 equivalents of octanoic acid (according to the invention) A mixture of xylitol (64.15 g, 0.421 mol), sorbitol (27.49 g, 0.151 mol) and octanoic acid (acid value = 389 mg KOH / g, >98%, 123.81 g, 0.859 mol, 1.50 equivalents, based on the total weight of xylitol and sorbitol) was heated to 80° C. under stirring and N2. After 30 minutes, immobilized Candida antarctica lipase B enzyme (6.02 g; Fermenta BIOCATALYST CALB TA 10000 NLT 95%, corresponding to 59077 PLU). The mixture was then stirred at 80° C. and 20 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, colorless in the melt and had an acid number of 1.6 mg KOH / g.

[0107] Example 9: Enzymatic esterification of a mixture of xylitol and sorbitol (66:34) with 2.00 equivalents of technical grade oleic acid (according to the present invention)

[0108] A mixture of xylitol (11.72 g, 0.077 mol), sorbitol (6.01 g, 0.033 mol) and oleic acid (acid value = 200 mg KOH / g, iodine value = 92.3 g I2 / 100 g, 61.7 g, 0.22 mol, 2.00 equivalents, based on the total weight of xylitol and sorbitol) was heated to 90° C. under stirring and N2 flow. After 30 minutes, immobilized Candida antarctica lipase B (2.3 g; Fermenta BIOCATALYST CALB TA 10000 NLT 95%, corresponding to 59077 PLU). The mixture was then stirred at 80° C. and 10 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous in the melt, slightly turbid, light yellow and had an acid number of 2.0 mg KOH / g.

[0109] Example 10: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 2.00 equivalents of technical grade oleic acid (according to the present invention)

[0110] A mixture of xylitol (28.0 g, 0.184 mol), sorbitol (12.0 g, 0.066 mol) and oleic acid (acid value = 200 mg KOH / g, iodine value = 92.3 g I2 / 100 g, 140.2 g, 0.50 mol, 2.00 equivalents, based on the total weight of xylitol and sorbitol) was heated to 80° C. under stirring and N2, and after 1 hour, immobilized Candida antarctica lipase B enzyme (5.40 g; Purolite D5619, corresponding to 46754 PLU) was added. The mixture was then stirred at 80° C. and 25 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, slightly turbid, pale yellow in the melt and had an acid value of 1.9 mg KOH / g.

[0111] Example 11: Enzymatic esterification of xylitol with 2.00 equivalents of stearic acid (not according to the invention)

[0112] A mixture of xylitol (40.00 g, 0.263 mol, 1.00 equiv) and stearic acid (acid value = 198 mg KOH / g, >92%, 148.18 g, 0.526 mol, 2.00 equiv) was heated to 90° C. under stirring and N2, and after 1 hour, immobilized Candida antarctica lipase B enzyme (5.65 g; Purolite D5619, corresponding to 48919 PLU) was added. The mixture was then stirred at 90° C. and 15 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, light yellow in the melt and had an acid value of 1.3 mg KOH / g.

[0113] Example 12: Enzymatic esterification of fructose with 2.00 equivalents of stearic acid (not according to the invention)

[0114] A mixture of fructose (42.00 g, 0.233 mol, 1.00 equiv) and stearic acid (acid value = 198 mg KOH / g, >92%, 132.42 g, 0.482 mol, 2.00 equiv) was heated to 90° C. under stirring and N2 flow, and immobilized antarctic Candida antarctica lipase B enzyme (5.18 g; Fermenta BIOCATALYST CALB TA10000 NLT 95%, corresponding to 50834 PLU). The mixture was subsequently stirred at 90° C. and 15 mbar for 51 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 90° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, orange-red in the melt and had an acid number of 14.7 mg KOH / g.

[0115] Example 13: Physical mixture of Example 11 and Example 12

[0116] A mixture of the ester obtained as described in Example 11 (42.00 g) and the ester obtained as described in Example 12 (18.00 g) was heated to 80° C. for 1 hour with stirring and N2. The product was homogeneous, clear, orange in the melt and had an acid number of 5.1 mg KOH / g.

[0117] Example 14: Enzymatic esterification of a mixture of xylitol and fructose (70:30) with 2.00 equivalents of stearic acid (according to the invention) A mixture of xylitol (28.0 g, 0.184 mol) and fructose (12.0 g, 0.067 mol) was heated to 130° C. with stirring and N2 and cooled to 90° C. after 2 hours. Subsequently, stearic acid (acid value = 198 mg KOH / g, about 95%, 142.14 g, 0.501 mol, 2.00 equivalents) was added with stirring and N2. After stirring at 90° C. for 30 minutes, an immobilized Candida antarctica lipase B enzyme (Purolite D5619, 5.46 g, corresponding to 47274 PLU) was added. The mixture was then stirred at 90° C. and 10 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 80° C. and 2 bar N2 pressure through a filter press with a Seitz T-750 depth filter to remove the enzyme. The resulting product was homogeneous, clear in the melt and had an acid number of 3.2 mg KOH / g.

[0118] Example 15: Enzymatic esterification of a mixture of xylitol, sorbitol and fructose (50:25:25) with 1.91 equivalents of octanoic acid (according to the present invention)

[0119] A mixture of xylitol (39.59 g, 0.260 mol), sorbitol (19.80 g, 0.109 mol), fructose (19.80 g, 0.110 mol) and octanoic acid (acid value = 389 mg KOH / g, >98%, 138.05 g, 0.957 mol, 1.91 equivalents, based on the total weight of xylitol, sorbitol and fructose) was heated to 100° C. and stirred for 1 hour under stirring and N2. Subsequently, the mixture was cooled to 80° C., immobilized antarctic Candida antarctica lipase B enzyme (5.92 g; Purolite D5619, corresponding to 51257 PLU) was added, and further stirred at 80° C. and 20 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 90° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, yellow in the melt and had an acid number of 3.1 mg KOH / g.

[0120] Example 16: Enzymatic esterification of a mixture of xylitol, sorbitol and glucose (65:25:10) with 1.91 equivalents of octanoic acid (according to the present invention)

[0121] A mixture of xylitol (52.12 g, 0.342 mol), sorbitol (20.05 g, 0.110 mol), glucose (8.02 g, 0.045 mol) and octanoic acid (acid value = 389 mg KOH / g, >98%, 136.91 g, 0.949 mol, 1.91 equivalents, based on the total weight of xylitol, sorbitol and glucose) was heated to 100° C. and stirred for 1 hour under stirring and N2. Subsequently, the mixture was cooled to 80° C., immobilized antarctic Candida antarctica lipase B enzyme (5.91 g; Purolite D5619, corresponding to 51170 PLU) was added, and further stirred at 80° C. and 20 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 90° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, clear, light yellow in the melt and had an acid value of 10.0 mg KOH / g.

[0122] Example 17: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 1.50 equivalents of lauric acid (according to the invention)

[0123] A mixture of xylitol (51.7 g, 0.340 mol), sorbitol (22.16 g, 0.122 mol) and lauric acid (acid value = 280 mg KOH / g, >99%, 138.60 g, 0.692 mol, 1.50 equivalents, based on the total weight of xylitol and sorbitol) was heated to 100° C. under stirring and N2, and after 60 minutes, immobilized Candida antarctica lipase B enzyme (6.02 g; Purolite D5619, corresponding to 52122 PLU) was added. The mixture was then stirred at 95° C. and 50 mbar for 24 hours, during which the water formed was continuously distilled off. The mixture was then filtered at 90° C. through a Buchner funnel with a black belt filter to remove the enzyme. The resulting product was homogeneous, slightly turbid and pale yellow to almost colorless in the melt and had an acid value of 0.8 mg KOH / g.

[0124] Embodiment 18: Differences between the embodiments of the present invention and the prior art

[0125] The following examples are intended to describe the subject matter of the present invention in detail without limiting the subject matter to these examples. These examples are intended to show that the method according to the present invention has advantages over the prior art. In this case, the representative of the selected prior art is an example not according to the present invention.

[0126] Technical effects: uniformity and smell

[0127] Table 1 compares Example 4 according to the invention with Examples 1, 2 and 3 not according to the invention in terms of reaction course, uniformity and odor.

[0128] Table 1:

[0129]

[0130] As can be seen from Table 1, Example 2 according to the present invention is not uniform after 24 hours of reaction time, still has a high residual acid value of about 140.5 mg KOH / g, and still has a distinct fatty acid smell in addition, which is considered to be unpleasant in the case of short-chain fatty acids such as tamarind. On the contrary, although Example 1 according to the present invention is uniform and has a residual acid value of only <1.3 mg KOH / g after 24 hours of reaction time, a distinct fatty acid smell can also be detected for this embodiment. This also applies to the physical mixture of Example 1 and Example 2 (Example 3). Only in Example 4 according to the present invention, low residual acid value (i.e. high conversion rate of fatty acid), uniform product and pleasant smell (like popcorn) are achieved after 24 hours of reaction time.

[0131] Technical effect: Homogeneous even at low esterification degrees

[0132] Table 2 compares Example 8 according to the invention with Examples 5 and 6 not according to the invention in terms of reaction course and uniformity.

[0133] Table 2:

[0134]

[0135] As can be seen from Table 2, Example 5 not according to the invention exhibited phase separation in the form of sediment in the melt at 80° C. This phenomenon was even more pronounced in Example 6 not according to the invention and also occurred in the physical mixture of Example 5 and Example 6 (Example 7). Only Example 8 according to the invention was homogeneous in the melt at 80° C. and did not exhibit phase separation despite the relatively low degree of esterification of 1:1.5 (sugar / fatty acid molar ratio).

[0136] Technical effects: color and reactivity (i.e. conversion of fatty acids)

[0137] Table 3 compares Example 14 according to the invention with Example 13 not according to the invention in terms of reaction course and color.

[0138] Table 3:

[0139]

[0140] As can be seen from Table 3, the physical mixture (Example 13) exhibits a significantly worse color than the process product according to the invention (Example 14).

[0141] Formulation Examples

[0142] The examples which follow are intended to show that the compositions according to the invention can be used in various cosmetic formulations.

[0143] Formulations 1a, 1b and 1c: Antiperspirant / deodorant formulations containing aluminum salts

[0144]

[0145] Formulations 2a, 2b and 2c: Aluminium-free deodorant formulations without antiperspirant active ingredients

[0146]

[0147]

[0148] Formulations 3a, 3b and 3c: O / W deodorant emulsions containing potassium alum

[0149]

[0150] Formulations 4a and 4b: Antiperspirant / deodorant lotion

[0151]

[0152]

[0153] Formulations 5a, 5b and 5c: Antiperspirant / deodorant cream

[0154]

[0155] Formulations 6a and 6b: Sunscreen Spray SPF 30

[0156]

[0157]

[0158] Formulations 7a, 7b and 7c: Sunscreen spray

[0159]

[0160] Formulations 8a, 8b and 8c: Sunscreen lotion, SPF 30

[0161]

[0162]

[0163] Formulations 9a, 9b and 9c: Sunscreen lotion SPF 30, high UVA protection

[0164]

[0165] Formulations 10a, 10b and 10c: Sunscreen lotion SPF 30

[0166]

[0167]

[0168] Formulations 11a, 11b and 11c: Sunscreen lotion SPF 50, high UVA protection

[0169]

[0170]

[0171] Formulations 12a, 12b and 12c: Sunscreen lotion SPF 50

[0172]

[0173] Formulations 13a, 13b and 13c: Sunscreen lotion SPF 50+

[0174]

[0175]

[0176] Formulations 14a and 14b: Body Lotion

[0177]

[0178] Formulations 15a and 15b: Natural Care Cream

[0179]

[0180] Formulations 16a and 16b: Anti-aging cream

[0181]

[0182]

[0183] Formulations 17a and 17b: O / W foundation

[0184]

[0185] Formulations 18a, 18b, 18c and 18d: Body lotion containing cosmetic active ingredients

[0186]

[0187]

[0188] Formulations 19a, 19b and 19c: Body lotions with low oil content

[0189]

[0190] Formulations 20a, 20b, 20c and 20d: O / W Serum 1

[0191]

[0192]

[0193] Formulations 20e, 20f, 20g and 20h: O / W Serum 2

[0194]

[0195]

[0196] Formulations 21a, 21b and 21c: O / W concealer body lotion

[0197]

[0198] Formulations 22a, 22b, 22c and 22d: Body lotion for sensitive skin

[0199]

[0200] Formulations 23a, 23b, 23c and 23d: Dry Skin Lotion 1

[0201]

[0202]

[0203] Formulations 23e, 23f, 23g and 23h: Dry Skin Lotion 2

[0204]

[0205] Formulations 24a, 24b and 24c: Preservative-free Body Lotion 1

[0206]

[0207] Formulations 24d, 24e and 24f: Preservative-free Body Lotion 2

[0208]

[0209] Formulations 25a and 25b: W / O Body Lotion

[0210]

[0211] Formulations 26a and 26b: W / O cream

[0212]

[0213]

[0214] Formulations 27a and 27b: Instant Cream

[0215]

[0216] Formulations 28a, 28b and 28c: Cooling Body Lotion

[0217]

[0218]

[0219] Formulations 29a, 29b and 29c: W / O creams based on natural ingredients

[0220]

[0221] Formulations 30a, 30b and 30c: Cold Toning Body Lotion

[0222]

[0223] Formulations 31a, 31b and 31c: Moisturizing lotion containing urea

[0224]

[0225]

[0226] Formulations 32a, 32b, 32c and 32d: W / O body lotion with a silky light feel

[0227]

[0228] Formulations 33a, 33b and 33c: Baby care products

[0229]

[0230] Formulations 34a, 34b and 34c: Foot care products

[0231]

[0232]

[0233] Formulations 35a and 35b: Sunscreen lotion SPF 30UVA with insect repellent protection

[0234]

[0235] Formulations 36a and 36b: Sunscreen lotion SPF 30 UVA according to Ecocert standard

[0236]

[0237] Formulations 37a, 37b, 37c and 37d: Sunscreen spray SPF 30 UVA

[0238]

[0239]

[0240] Formulations 38a, 38b, 38c and 38d: Sunscreen lotion SPF 50 UVA

[0241]

[0242]

[0243] Formulations 39a, 39b and 39c: Sunscreen lotion SPF 50 according to FDA standards

[0244]

[0245] Formulations 40a, 40b, 40c, 40d, 40e and 40f: Foundation

[0246]

[0247]

[0248] Formulations 41a, 41b, 41c, 41d, 41e, 41f and 41g: CC (color control) fluids

[0249]

[0250]

[0251]

[0252] Formulations 42a, 42b, 42c, 42d and 42e: Antiperspirant / deodorant spray or aerosol spray

[0253] Formulations 43a, 43b, 43c and 43d: Sunscreen Aerosol SPF 50 UVA

[0254]

[0255] Formulation 44: Shower Gel

[0256]

[0257]

[0258] Formulation 45: Shower Gel

[0259] Formulation 46: Shampoo

[0260] Formulations 47a and 47b: Shampoo

[0261]

[0262]

[0263] Preparation 48: Hand sanitizer

[0264] water to 100% Glycerin (Glycerin EP, Vegetable, Spiga Nord) 4.0％ alcohol 4.0％ Sodium Cocoyl Sulfate (Texapon HC G, BASF) 3.0％ Lauryl glucoside (Plantacare 1200 UP, BASF, 50%) 6.0％ The composition of embodiment 4, 8, 15 or 16 2.0％ Composition of Example 17 1.0％ Xanthan gum (Keltrol CG-SFT, CPKelco) 1.5％ Mangifera indica (Mango) fruit extract (Mango Extract, Draco Natural Products) 0.5％ Limonene (Dipentene 122, Hercules Inc.) 0.1％ Linalool (Lipofresh, Lipo Chemicals, Inc.) 0.1％ Citric acid To pH 4.9 preservative Moderate dye Moderate .

[0265] Formulation 49: Soap paste

[0266]

[0267] Formulation 50: Oil bath

[0268]

[0269]

[0270] Formulation 51: Micellar water for makeup removal

[0271]

[0272] Formulations 52a and 52b: Solutions for Wet Wipes

[0273]

[0274] Formulation 53: Antiperspirant deodorant

[0275]

[0276] Formulation 54: Mouthwash

[0277] The composition of embodiment 4, 8, 15 or 16 0.4％ Glycolipid (Rheance One, Evonik) 0.2％ Flavoring 0.2％ water to 100.0% Sorbitol (Karion FP Liquid, Merck) 3.0％ preservative Moderate dye Moderate .

[0278] Preparation 55: Toothpaste

[0279]

Claims

1. A method for enzymatically preparing a mixed composition comprising at least two selected from sugar esters and / or sugar alcohol esters, comprising the following method steps: B) mixing a mixture containing at least two selected from sugars and sugar alcohols with at least one acyl donor is reacted in the presence of a lipase, The acyl donor is selected from fatty acids, wherein in process step B), the mixture comprising at least two species selected from the group consisting of sugars and sugar alcohols and the acyl donor constitutes in total at least 86% by weight of the entire reaction mixture, and wherein the water formed in process step B) is removed, wherein the sugar and sugar alcohol are selected from the group consisting of fructose, glucose, sorbitol, xylitol, and The lipase is selected from lipase B from Candida antarctica.

2. The method according to claim 1, characterized in that In process step B), the mixture comprising at least two species selected from the group consisting of sugars and sugar alcohols and the acyl donor constitutes in total at least 90% by weight of the entire reaction mixture.

3. The method according to any one of claims 1 to 2, characterized in that: The acyl donor is selected from hexanoic acid, caprylic acid, nonanoic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

4. The method according to any one of claims 1 to 2, characterized in that: The mixture containing at least two substances selected from sugars and sugar alcohols used in process step B) contains substances selected from the group consisting of choline salts, ammonium salts and phosphonium salts in an amount of less than 2% by weight, wherein the weight % data are based on all sugars and sugar alcohols in the mixture containing at least two substances selected from sugars and sugar alcohols in process step B).

5. The method according to claim 4, characterized in that: The mixture comprising at least two substances selected from sugars and sugar alcohols used in process step B) does not comprise substances selected from the group consisting of choline salts, ammonium salts and phosphonium salts.

6. The method according to any one of claims 1 to 2, characterized in that: In process step B), the molar ratio of all sugars and sugar alcohols to the acyl groups contained in all acyl donors is from 1.00:0.08 to 1.00:10.

00.

7. The method according to claim 6, characterized in that: In process step B), the molar ratio of all sugars and sugar alcohols to the acyl groups contained in all acyl donors is from 1.00:2.00 to 1.00:4.

50.

8. The method according to any one of the preceding claims 1 to 2, characterized in that: In process step B), the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols to acyl groups contained in all acyl donors is from 1.00:0.10 to 1.00:3.

00.

9. The method according to claim 8, characterized in that: In process step B), the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols to acyl groups contained in all acyl donors is from 1.00:1.25 to 1.00:2.

25.

10. The method according to any one of claims 1 to 2, characterized in that: Process step B) is carried out at a reaction temperature of 20°C to 160°C.

11. The method according to claim 10, characterized in that: Process step B) is carried out at a reaction temperature of 50°C to 110°C.

12. The method according to any one of claims 1 to 2, characterized in that: Process step B) is carried out at a pressure of less than 1 bar.

13. The method according to claim 12, characterized in that: Process step B) is carried out at a pressure of less than 0.05 bar.

14. The method according to any one of claims 1 to 2, characterized in that: It comprises the following method steps A) providing at least two substances selected from sugars and sugar alcohols in solid form or dissolved in water spatially separated from one another and mixing them to obtain a mixture containing at least two substances selected from sugars and sugar alcohols used in method step B).

15. The method according to claim 14, characterized in that: Process step A) comprises reducing the water content of the mixture comprising at least two substances selected from sugars and sugar alcohols used in process step B) to less than 17% by weight, wherein the weight % data are based on the entire mixture comprising at least two substances selected from sugars and sugar alcohols used in process step B).

16. The method according to claim 15, characterized in that: Process step A) comprises reducing the water content of the mixture comprising at least two substances selected from sugars and sugar alcohols used in process step B) to less than 10% by weight, wherein the weight % data are based on the entire mixture comprising at least two substances selected from sugars and sugar alcohols used in process step B).

Images