EP4077696A1

EP4077696A1 - Process for enzymatically preparing sugar esters and/or sugar alcohol esters

Info

Publication number: EP4077696A1
Application number: EP20833824.4A
Authority: EP
Inventors: Jan Marian Von Hof; Stefan Julian LIEBIG; Hans Henning Wenk; Marrit Friederike Eckstein; Sunay Karacocuk; Maxim YAVORSKY
Original assignee: Evonik Operations GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2019-12-20
Filing date: 2020-12-17
Publication date: 2022-10-26
Also published as: BR112022011453A2; JP2023507448A; US20230023141A1; WO2021122973A1; JP2023507450A; BR112022011457A2; CN114787368A; CN114829617A; EP4077698A1; EP4077697A1; CN114787118A; JP2023507446A; US20230033620A1; US20230055814A1; WO2021122972A1; EP3839052A1; WO2021122971A1; BR112022011988A2

Abstract

The invention relates to a process for enzymatically preparing sugar esters and/or sugar alcohol esters and to mixture compositions containing sugar esters and/or sugar alcohol esters.

Description

Process for the enzymatic production of sugar esters and / or sugar alcohol esters

Field of invention

The invention relates to a process for the enzymatic production of sugar esters and / or sugar alcohol esters and mixed compositions containing sugar esters and / or sugar alcohol esters.

State of the art

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 in the cosmetics industry.

The classic synthesis of fatty acid esters of sugars or sugar alcohols takes place by reacting the 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).

A disadvantage of this process described in the prior art, however, is that the use of such solvents for applications in the food or cosmetics sector is unacceptable and, moreover, a corresponding separation of the solvents requires additional process steps such as crystallization, filtration or distillation. Another disadvantage of this process described in the prior art is the quantitative release of HCl when using fatty acid chlorides, since HCl can lead to corrosion on the metallic surfaces of the reactors.

An alternative method of the prior art, which is used in particular on an industrial scale, converts the sugars or sugar alcohols with the free fatty acids or the fatty acid alkyl esters in the absence of a solvent at temperatures of 200-250 ° C in the presence of basic catalysts such as sodium hydroxide ( Römpp, Georg Thieme Verlag KG, 2019 on the keyword "Sorbitans" and Surfactants, K. Kosswig in Ullmann's Encyclopedia of Industrial Chemistry, Online, Wiley-VCH, Weinheim, 2000, https://doi.org/10.1002/14356007.a25_747) . A disadvantage of this process described in the prior art, however, is that when, for example, sorbitol is converted under the conditions mentioned, dehydration of the sugars or sugar alcohols occurs as a side reaction. In the presence of acidic catalysts, this side reaction occurs even from around 140 ° C. For example, sorbitol is first dehydrated to sorbitan (by losing one molecule of water) and then to isosorbide (by losing another molecule of water).

The sugars or sugar alcohols used lose their hydrophilicity and are therefore always less suitable as hydrophilic head groups for surfactants. Another disadvantage of this process described in the prior art is that the side reactions that occur lead to a dark coloration of the products obtained, which may require further treatment, for example with bleaching agents such as hydrogen peroxide or activated carbon, in order to convert the products obtained into cosmetic formulations, for example to be able to use. Another disadvantage of this process described in the prior art is that the side reactions that occur lead to a bad odor in the products obtained, which can have an undesirable interaction with the perfumes used in cosmetic formulations.

The enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols is described in dilute solutions in organic solvents such as 2-methyl-2-butanol, pyridine, dimethylformamide or 2-pyrrolidone (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, AM Klibanov, 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 / PI 9890001057; AEM Janssen, C. Klabbers, MCR Franssen, K. van't Riet, Enzymatic synthesis of carbohydrate rate esters in 2-pyrrolidone, Enzyme and Microbial Technology, 1991, 13 (7), 565-572). A disadvantage of these methods described in the prior art, however, is that the use of such solvents for applications in the food or cosmetics sector is not acceptable and, moreover, a corresponding separation of the solvents requires additional high amounts of energy-consuming process steps such as crystallization, filtration or distillation. An enzymatic synthesis of fatty acid esters of sugars or sugar alcohols using dilute aqueous solutions of the enzymes is described in A. E. M. Janssen, A. G. 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 in W09412651. Disadvantages of this method described in the prior art are the energy-consuming process steps such as crystallization, filtration or distillation that are additionally required to isolate the products from the aqueous systems, and in the case of a buffered aqueous system, the removal of the salt load. Another disadvantage here is that the presence of water when using fatty acids as acyl donor makes it more difficult to shift the equilibrium position towards the products. Another disadvantage is that enzymes usually have a maximum performance at a certain water activity. T. Itoh, lonic Liquids as Tool to Improve Enzymatic Organic Synthesis, Chemical Reviews 2017, 117, 10567-10607 discloses the enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols in ionic liquids as solvents. A disadvantage of these methods described in the prior art, however, is that at least one additional, energy-intensive process step such as crystallization, filtration or distillation is required to separate the ionic liquids, since the ionic liquids for subsequent applications in the food sector or in the cosmetic industry are not in the product can remain. Another disadvantage of these methods described in the prior art is that the ionic liquids are produced from petrochemical raw materials, and their use is therefore not desirable for natural and sustainable applications in the food sector or in the cosmetic industry. Another disadvantage of the processes described in the prior art is the use of fatty acid vinyl esters as acyl donor, since these release toxicologically harmful acetaldehyde during the reaction, which makes handling on an industrial scale difficult and is also undesirable for applications in the food sector or in the cosmetics industry. In addition, the fatty acid vinyl esters are produced in the presence of toxicologically questionable metal catalysts such as mercury, cadmium, palladium or silver salts from petrochemical raw materials such as acetylene or ethylene (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 use of these raw materials for natural and sustainable applications in the food sector or in the cosmetics industry.

The enzyme-catalyzed production of fatty acid esters of sugars or sugar alcohols is also described in the presence of choline chloride (or other ammonium or phosphonium salts) to form deep-eutectic mixtures (S. Siebenhaller, C. Muhle-Goll, B. Luy, F. Kirschhöfer , G. Brenner-Weiss, E. Hiller, et al., Sustainable enzymatic synthesis of glycolipids in a deep eutectic solvent system, J. Mol. Catal. B Enzym. 2016, 133, 281-287, doi: 10.1016 / j. molcatb.2017.01.015). A disadvantage of this method described in the prior art is, however, that choline chloride or other ammonium or phosphonium salts, due to their salt character, can negatively influence the application profiles of fatty acid esters of sugars or sugar alcohols, provided they remain in the product. Another disadvantage of this process described in the prior art is that the industrially available quality of the choline chloride is a petrochemical raw material, the presence of which in the product is therefore undesirable for natural and sustainable applications in the food sector or in the cosmetics industry. Therefore, a further disadvantage of this process described in the prior art is that at least one additional process step such as crystallization, filtration or distillation is required to separate off the choline chloride or other ammonium or phosphonium salts. The enzyme-catalyzed esterification of a single sugar contained in honey or agave syrup with fatty acid vinyl esters as acyl donor is described in S. Siebenhaller, J. Gentes, A. Infantes, C. Muhle-Goll, F. Kirschhöfer, G. Brenner-Weiß, K. Ochsenreither, C. Syldatk, Lipase- Catalyzed Synthesis of Sugar Esters in Honey and Agave Syrup, front. Chem. 2018, 6, Article 24, 1-9, doi: 10.3389 / fchem.2018.00024). A disadvantage of this process described in the prior art is the use of fatty acid vinyl esters as acyl donor, since they release toxicologically harmful acetaldehyde during the reaction, which makes handling on an industrial scale difficult and is also undesirable for applications in the food sector or in the cosmetics industry. In addition, the fatty acid vinyl esters are produced in the presence of toxicologically questionable metal catalysts such as mercury, cadmium, palladium or silver salts from petrochemical raw materials such as acetylene or ethylene (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 use of these raw materials for natural and sustainable applications in the food sector or in the cosmetics industry. Another disadvantage of this process described in the prior art is the use of a maximum of only 0.066 equivalents of the acyl donor, based on the total amount of sugars and sugar alcohols. Another disadvantage of this method described in the prior art is that the large excess of the sugars and sugar alcohols used means that at least one additional process step such as extraction, crystallization, filtration or distillation is required to isolate the fatty acid esters of the sugars and sugar alcohols is. A further disadvantage of this process described in the prior art is that the large excess of the sugars and sugar alcohols used is uneconomical on an industrial scale and, moreover, necessitates laborious recycling of the sugars and sugar alcohols used. Another disadvantage of this method described in the prior art is that only glucose esters are detected in the case of honey as substrate and only fructose esters in the case of agave syrup as substrate, i.e. only one of the sugar components contained in honey or agave syrup is actually esterified.

JPS58116688 discloses the enzymatically catalyzed esterification of mixtures of polysaccharides and / or mono- and oligosaccharides; so it always contains oligo- or polysaccharides. The reactions are carried out in water or hexane as the solvent; the comparative examples show that hardly any conversion can be achieved with no or only small amounts of solvent

KR20180007129 discloses a method for the production of mixtures of sucrose, fructose and glucose esters by enzymatic esterification of sucrose.

The work is carried out in solutions that are so strongly diluted with water that the lauric acid used is present in dissolved form. Due to the aqueous, acidic conditions, sucrose is split into the corresponding monosaccharides and esterified in the course of the reaction. The acyl groups are always used in deficit based on the esterified saccharides obtained, so that the product always contains unreacted saccharides. The sucrose esters always make up the largest part of the esters obtained.

A further disadvantage of this prior art method is that the ratio of the different saccharide esters obtained cannot be foreseen and controlled.

The object of the invention was to provide a process for producing sugar esters and / or sugar alcohol esters which contain in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol part, which at least one disadvantage of the prior art processes technology can overcome. In particular, it should be possible to represent the sugar esters and / or sugar alcohol esters from the readily available sugars or sugar alcohols having 4 to 12, preferably 4 to 6, carbon atoms.

Description of the invention

It has surprisingly been found that the method described below is able to achieve the object of the invention.

The present invention relates to a process for the enzymatic production of a mixture composition comprising at least two selected from sugar esters and / or sugar alcohol esters which contain in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol part, comprising the process step

B) Reacting a mixture containing at least two selected from sugars and sugar alcohols, the sugars and sugar alcohols in particular containing 4 to 12, preferably 4 to 6, carbon atoms, with at least one acyl group donor, preferably fatty acid acyl group donor, in particular selected from fatty acid esters and fatty acids, especially preferably fatty acids, in the presence of a lipase.

The invention also relates to mixture compositions containing certain sugar esters and / or sugar alcohol esters which contain, in particular, 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol part.

An advantage of the present invention is that the process according to the invention can be carried out in the absence of a solvent.

Another advantage of the present invention is that the method according to the invention can be carried out using natural and sustainable synthetic building blocks. Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters according to the invention are obtained in homogeneous reaction mixtures, and this property can be achieved even at low degrees of esterification.

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

Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters according to the invention have a low odor; in particular, a typical caramel smell is barely perceptible.

An advantage of the present invention is that substrates can be converted successfully in a mixture, whereas their sole conversion is not successful in the absence of a solvent.

Another advantage of the present invention is that no undesired by-products with elimination of water, such as sorbitans from sorbitol, are formed from the sugars / sugar alcohols used.

Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters obtained can be incorporated very easily into formulations, especially into cosmetic formulations.

Another advantage of the present invention is that mild formulations can be produced with the sugar esters and / or sugar alcohol esters obtained.

Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters obtained can be used to produce formulations with a particularly good skin feel. Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters obtained can be used to produce sustainable formulations without petrochemical components.

Another advantage of the present invention is that the sugar esters and / or sugar alcohol esters obtained can be produced without the quantitative release of HCl or acetaldehyde. A further advantage of the present invention is that the reaction can take place in a bubble column due to the good miscibility of the reaction mixture, as a result of which longer catalyst service lives can be achieved.

Another advantage of the present invention is that a large amount of acyl donors based on the total amount of substance of sugars and / or sugar alcohols can be used.

Another advantage of the present invention is that the esters of the 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 required.

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.

Another advantage of the present invention is that homogeneous melts are obtained in the reaction at lower degrees of esterification. The present invention relates to a process for the enzymatic production of a mixture composition comprising at least two selected from sugar esters and / or sugar alcohol esters which contain in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol part, comprising the process step

B) Reacting a mixture containing at least two selected from sugars and sugar alcohols with at least one acyl group donor, preferably fatty acid acyl group donor, in particular selected from fatty acid esters and fatty acids, particularly preferably fatty acids, in the presence of a lipase.

The term “two selected from sugar esters and / or sugar alcohol esters” in connection with the present invention is to be understood as meaning that the two esters differ with regard to their sugars or with regard to their sugar alcohols. It must therefore contain esters which have two different residues with regard to sugar and / or sugar alcohol residues.

Unless otherwise stated, all percentages (%) given are percentages by mass. According to the invention, all sugars and sugar alcohols, such as agarose, amylopectin, amylose, cellulose, chitin, cyclodextrins, dextrans, fructans, glycogen, hyaluronic acid, inulin, isomelicose, maltohexose, maltopentose, maltotetrose, maltotriose, melicitose, starch, maltotriose, melicitose, can be used , Starch hydrolysates, umbelliferose,

Cellobiose, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, sucrose, trehalose, trehalulose,

Allitol, allulose, altritol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose are used. According to the invention, the sugars and sugar alcohols are selected from the group of sugars and sugar alcohols containing 4 to 12, preferably 4 to 6, carbon atoms.

According to the invention, the sugars and sugar alcohols of the group of sugars and sugar alcohols containing 4 to 12 carbon atoms selected from cellobiose, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, sucrose, trehalose, trehalulose,

Allitol, allulose, altritol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose, whereby allitol, allulose, altritol, arabinitol, 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 especially and

Erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, maltose, maltulose, mannitol, sorbitol, sorbose, xylitol and xylose are very particularly preferred.

According to the invention, the sugars and sugar alcohols from the group of sugars and are preferred

Sugar alcohols containing 4 to 6 carbon atoms selected from

Allitol, allulose, altritol, arabinitol, arabinose, deoxyribose, erythritol, fructose, fucose,

Galactitol, galactose, glucose, iditol, mannitol, mannose, rhamnose, ribitol, ribose, sorbitol, sorbose, threitol, xylitol and xylose, with erythritol, fructose, glucose, sorbitol, xylitol and xylose being particularly preferred.

According to the invention, the sugars and sugar alcohols selected from the group are particularly preferred.

A method preferred according to the invention is characterized in that, in method step B), as a mixture containing at least two selected from sugars and sugar alcohols containing mixtures

Glucose, fructose and maltose, each with a glucose content of 40% by weight to 50% by weight and a fructose content of 47% by weight to 57% by weight, based on all the sugars and sugar alcohols contained in the mixture, and

Glucose, fructose and sucrose, each with a glucose content of 5% by weight to 24% by weight and a fructose content of 75% by weight to 94% by weight, based on all sugars and sugar alcohols contained in the mixture, are excluded.

All acyl group donors can be used according to the invention. Such are, for example, carboxylic acid esters or carboxylic acids themselves and mixtures thereof. Carboxylic acid esters preferably used as acyl group donors according to the invention are selected from esters based on alkanols and polyols with up to 6 carbon atoms, particularly preferably with up to 3 carbon atoms, very particularly preferably glycerol esters.

Carboxylic acid esters preferably used as acyl group donors according to the invention are selected from triglycerides, in particular natural fats and oils, particularly preferably selected 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 oils Sesame oil, soybean oil, avocado oil, jojoba oil, diestel oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuaccu butter and oils with a high proportion of polyunsaturated fatty acids (PUFAS) used. Sorbitan esters, monoglycerides and diglycerides, in particular with the acyl groups described below, can also be used with preference.

According to the invention, the acyl group donor is selected from fatty acid acyl group donors which, in particular, provide an acyl group selected from the group of acyl groups of natural fatty acids. Natural fatty acids can be prepared on the basis of naturally occurring vegetable or animal oils and preferably have 6-30 carbon atoms, in particular 8-22 carbon atoms. Natural fatty acids are usually unbranched and usually consist of an even number of carbon atoms. Any double bonds have a cis configuration. Examples are: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable from the ozonolysis of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, oleic acid, linoleic acid (obtainable from the pyrolysis of oleic acid) , Linolenic acid, petroleic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

According to the invention, carboxylic acids, in particular fatty acids, are preferably used as acyl group donors, the specifically aforementioned fatty acids being used with particular preference.

According to the invention, it is preferred that vinyl esters are excluded as acyl group donors because they release toxicologically questionable acetaldehyde during the reaction, which makes handling on an industrial scale difficult and is also undesirable for applications in the food sector or in the cosmetics industry. In addition, the fatty acid vinyl esters are produced in the presence of toxicologically questionable metal catalysts such as mercury, cadmium, palladium or silver salts from petrochemical raw materials such as acetylene or ethylene (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 use of these raw materials for natural and sustainable applications in the food sector or in the cosmetic industry.

In particular, it is preferred according to the invention that the sugars and sugar alcohols are selected from erythritol, fructose, glucose, sorbitol, xylitol and xylose and the acyl group donor is selected from at least one from the group caproic acid, caprylic acid, pelargonic 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, petroleic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid. A method preferred according to the invention is characterized in that the mixture used in method step B) contains at least two substances selected from sugars and sugar alcohols selected from the group consisting of choline, ammonium 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, in particular none of the substances, the weight percent being based on all sugars and sugar alcohols in process step B) in the mixture containing at least two selected from sugars and sugar alcohols.

A method preferred according to the invention is characterized in that in method step B) the molar ratio of all sugars and sugar alcohols to acyl groups contained in all acyl group donors is in a range from 1.00 to 0.08 to 1.00 to 10.00, preferably from 1.00 00 to 0.50 to 1.00 to 7.00, particularly preferably from 1.00 to 1.25 to 1.00 to 2.25, alternatively particularly preferably from 1.00 to 2.00 to 1.00 to 4 , 50, lies. A method preferred according to the invention is characterized in that in method step B) the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols to acyl groups contained in all acyl group donors is in a range from 1.00 to 0.10 to 1.00 to 3.00 , particularly preferably from 1.00 to 1.25 to 1.00 to 2.25. A method preferred according to the invention is characterized in that in method step B) a mixture containing sugars and / or sugar alcohols with 4 to 6 carbon atoms is used and the molar ratio of all primary hydroxyl groups in all sugars and sugar alcohols with 4 to 6 carbon atoms to in all acyl group donors contained acyl groups in a range from 1.00 to 0.20 to 1.00 to 1.5.

Lipases preferably used according to the invention are immobilized on a solid support. Lipases preferably used according to the invention in process step B) are lipases selected from the group comprising the lipase from Thermomyces lanuginosus (accession number 059952), the lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei (accession number P19515), the Lipase from Humicola sp. (accessionnumber 059952), the lipase from Rhizomucor javanicus (accessionnumber S32492), the lipase from Rhizopus oryzae (accessionnumber P61872), the lipases from Candida rugosa (accessionnumber P20261, P32946, P32947, P3294 and P32949), the lipase from Rhizopus number P61871), the lipase from PenicilHum camemberti (accessionnumber P25234), the lipases from Aspergillus niger (ABG73613, ABG73614 and ABG37906) and the lipase from PenicilHum cyclopium (accessionnumber P61869), as well as each of them at the amino acid level, preferably at least 60%, preferably at least 80% at least 90%, particularly preferably at least 95%, 98% or 99% homologous. The enzymes homologous at the amino acid level preferably have, compared to the reference sequence, at least 50%, in particular at least 90%, enzyme activity in propyl laurate units defined in connection with the present invention.

Commercial examples and also preferably used carboxyl ester hydrolases in the process according to the invention are the commercial products Lipozyme TL IM, 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, as well as 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),

“Homology at the amino acid level” in the context of the present invention means the “amino acid identity” which can be determined with the aid of known methods. In general, special computer programs with algorithms are used, taking special requirements into account. Preferred methods for determining the identity initially produce the greatest correspondence between the sequences to be compared. Computer programs used to determine identity include, but are not limited to, the GCG program package, including

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

BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of Molecular Biology 215 (1990), pages 403-410. The BLAST program can be obtained from the National Center For Biotechnology Information (NCBI) and from other sources (BLAST Handbuch, Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S. et al., Supra) Those skilled in the art are aware that various computer programs can be used to calculate the similarity or identity between two nucleotide or amino acid groups. The percent identity between two amino acid sequences can be determined, for example, by the Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)) algorithm which is included in the GAP program in the GCG Software package (available from 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. The person skilled in the art is recognized suggest that the use of different parameters will lead to slightly different results, but that the percent identity between two amino acid sequences will not be significantly different overall. The Blossom 62 matrix is usually used with the default settings (gap weight: 12, length weight: 1).

An identity of 60% according to the above algorithm means 60% homology in connection with the present invention. The same goes for higher identities. According to the invention, process step B) is preferably carried out at reaction temperatures in the range between 20 ° C. and 160 ° C., preferably 35 ° C. and 130 ° C., in particular between 50 ° C. and 110 ° C.

Process step B) is preferably carried out according to the invention at a pressure of less than 1 bar, preferably less than 0.5 bar and particularly preferably less than 0.05 bar.

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

A method preferred according to the invention is characterized in that in method step B) the mixture containing at least two selected from sugars and sugar alcohols and the acyl group donor in total at least 10% by weight, preferably at least 86% by weight, particularly preferably at least 90% by weight. %, make up of the total reaction mixture.

The aforementioned high proportions by weight of the starting materials accordingly leave little room for the presence of solvents, such as, for example, water or hexane.

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

A method preferred according to the invention is characterized in that by-products formed in method step B), for example in the case that the acyl group donor used is an acid, water, in the case that the acyl group donor used is an ester, the corresponding alcohol, are removed.

This is possible, for example, by distillation.

According to the invention, the process according to the invention preferably comprises process step A) spatially separated provision of the at least two selected from sugars and sugar alcohols in solid or water-dissolved form and mixing them into the mixture used in process step B) containing at least two selected from sugars and sugar alcohols. Here it can be particularly preferred to concentrate the mixture containing at least two selected from sugars and sugar alcohols as well as the acyl group donor by removing water in order to increase the aforementioned total of at least 10% by weight, preferably at least 86% by weight, particularly preferably at least 90% by weight. -% to achieve the total reaction mixture. In this context, it is particularly preferred that process step A) a reduction in the water content of the mixture used in process step B) containing at least two selected from sugars and sugar alcohols to less than 17% by weight, preferably less than 14% by weight, particularly preferred less than 10% by weight, the percentages by weight being based on the total mixture used in method step B) containing at least two selected from sugars and sugar alcohols.

According to the invention, the process according to the invention preferably comprises process step C) separating off the lipase.

Also preferably according to the invention, the process according to the invention comprises process step D) Filtration of the mixture composition comprising at least two selected from sugar esters and / or sugar alcohol esters through a filter, in particular a bag filter, with a fineness of 0.1 m to 1250 m, preferably of 0.5 m to 100 m. Process step D) is preferably carried out in a temperature range from 20 ° C. to 150 ° C., in particular from 40 ° C. to 120 ° C., according to the invention.

According to the invention, process step D) is preferably carried out in a pressure range from 1 bar to 25 bar, in particular from 1.5 bar to 10 bar.

According to the invention, the process according to the invention preferably comprises no further purification step in addition to process steps C) and D).

Another object of the present invention is a mixture composition comprising at least two selected from sugar esters and sugar alcohol esters obtainable by the process according to the invention, which contain in particular 4 to 12, preferably 4 to 6, carbon atoms in the sugar or sugar alcohol part.

Another object of the present invention is a mixture composition containing sugar esters and / or sugar alcohol esters, characterized in that the sugar and / or sugar alcohol residue of the sugar ester and / or the sugar alcohol ester is selected from at least two sugar and / or sugar alcohol residues selected from the group of residues of allitol, allulose, altritol, arabinitol, 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, preferably of erythritol, fructose, glucose, isomalt, isomaltulose, lactitol, lactose, maltitol, Maltose, maltulose, mannitol, sucrose, sorbitol, sorbose, xylitol and xylose, particularly preferably of erythritol, fructose, glucose, sorbitol, xylitol and xylose , and the ester residue is selected from at least one acyl group from the group of acid residues of fatty acids, preferably caproic acid, caprylic acid, pelargonic acid, capric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, linoleum acid, dihydroxystearic acid , Petroleic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

Mixture compositions preferred according to the invention preferably contain 4 to 6 carbon atoms in the sugar or sugar alcohol part.

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

Mixture compositions preferred 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 greater, in particular from 1.00 to 7.00, particularly preferably from 1.25 to 2.25, alternatively particularly preferably from 2.00 to 4.50.

In the examples listed below, the present invention is described by way of example without the invention, the scope of which is evident from the entire description and the claims, being restricted to the embodiments mentioned in the examples.

Examples:

Method for determining the acid number

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

Method for determining the specific activity of the enzyme used in PLU: To determine the enzyme 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 with the addition of enzyme and the reaction time is stopped. Samples are taken from the reaction mixture at intervals and the content of converted lauric acid is determined by means of titration with potassium hydroxide solution. The enzyme activity in PLU results from the rate at which 1 g of the enzyme under consideration synthesizes 1 pmol propyl laurate per min at 60 ° C., cf. also US20070087418, in particular [0185]

Method for determining the color numbers

An aliquot (approx. 10 g; so that the cuvette is sufficiently filled) was measured at 90 ° C. in an 11 mm round cuvette in a Lico 690 spectral colorimeter, and the respective color numbers indicated were recorded.

Example 1: Enzymatic esterification of xylitol with 2.00 eq. Caprylic acid (not according to the invention)

A mixture of xylitol (60.0 g, 0.394 mol, 1.00 eq.) And caprylic acid (acid number = 389 mg KOH / g,> 98%, 113.70 g, 0.788 mol, 2.00 eq.) Was dissolved with stirring and passage of ISL 80 ° C and after 1 h immobilized enzyme Candida antarctica lipase B (5.21 g; Purolite D5619, corresponds to 45110 PLU) was added. The mixture was stirred at 80 ° C. and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous in the melt, colorless and had an acid number of 1.8 mg KOH / g.

Example 2: Enzymatic esterification of fructose with 2.00 eq. Caprylic acid (not according to the invention)

A mixture of fructose (83.31 g, 0.462 mol, 1.00 eq.) And caprylic acid (acid number = 389 mg KOH / g,> 98%, 133.36 g, 0.925 mol, 2.00 eq.) Was heated to 80 ° with stirring and ISL passage C, and after 30 min immobilized enzyme Candida antarctica lipase B (6.50 g; Fermenta BIOCATALYST CALBT _A 10000 NLT 95%, corresponds to 63788 PLU) was added. The mixture was stirred at 80 ° C. and 20 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was inhomogeneous in the melt, reddish in color and had an acid number of approx. 140.5 mg KOH / g (due to the inhomogeneity, the acid number could not be clearly determined). Example 3: Physical mixture of Example 1 and Example 2 (not according to the invention)

A mixture of an ester obtained as described in Example 1 (42.00 g) and an ester obtained as described in Example 2 (18.00 g) was heated to 80 ° C. for 1 h while stirring and passing through ISL. The product obtained was inhomogeneous, cloudy, orange in the melt and had an acid number of about 40 mg KOH / g (because of the inhomogeneity, the acid number could not be clearly determined).

Example 4: Enzymatic esterification of a mixture of xylitol and fructose (70:30) with 2.00 eq. Caprylic acid (according to the invention)

A mixture of xylitol (42.00 g, 0.276 mol), D - (-) - fructose (18.00 g, 0.100 mol) and caprylic acid (acid number = 389 mg KOH / g,> 98%, 108.40 g, 0.752 mol, 2.00 eq. based on the total weight of xylitol and fructose), the mixture was heated to 80 ° C. with stirring and passing through ISL, and after 1 h the immobilized enzyme Candida antarctica lipase B (5.05 g; Purolite D5619, corresponds to 43724 PLU) was added. The mixture was stirred at 80 ° C. and 15 mbar for 27 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear and yellowish in the melt and had an acid number of 2.4 mg KOH / g.

Example 5: Enzymatic esterification of xylitol with 1.50 eq. Caprylic acid (not according to the invention)

A mixture of xylitol (89.14 g, 0.586 mol, 1 .00 eq.) And caprylic acid (acid number = 389 mg KOH / g,> 98%, 126.7 g, 0.879 mol, 1.50 eq.) Was obtained with stirring and IS flow-through 80 ° C, and after 30 min immobilized enzyme Candida antarctica lipase B (6.47 g; Fermenta BIOCATALYST CALB _TA 10000 NLT 95%, corresponds to 63493 PLU) was added. The mixture was stirred at 80 ° C. and 20 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear and colorless in the melt and had an acid number of 1.3 mg KOH / g. Example 6: Enzymatic esterification of sorbitol with 1.50 eq. Caprylic acid (not according to the invention)

A mixture of sorbitol (98.09 g, 0.538 mol, 1.00 eq.) And caprylic acid (acid number = 389 mg KOH / g,> 98%, 116.47 g, 0.808 mol, 1.50 eq.) Was heated to 100 ° while stirring and passing through IS C. and after 30 min immobilized enzyme Candida antarctica lipase B (6.44 g; Purolite D5619, corresponds to 55759 PLU) was added. The mixture was then stirred at 90 ° C. and 50 mbar for 24 h and the water formed was continuously distilled off during this time. The reaction mixture obtained was inhomogeneous, pale yellow after 24 h and had an acid number of approx. 10-11 mg KOH / g (the acid number could not be clearly determined due to the inhomogeneity).

Example 7: Physical mixture of Example 5 and Example 6

A mixture of an ester obtained as described in Example 5 (42.00 g) and an ester obtained as described in Example 6 (18.00 g) was heated to 80 ° C. for 1 h while stirring and passing through ISL. The product obtained was inhomogeneous in the melt and had an acid number of 3.7 mg KOH / g.

Example 8: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 1.50 eq. Caprylic acid (according to the invention)

A mixture of xylitol (64.15 g, 0.421 mol), sorbitol (27.49 g, 0.151 mol) and caprylic acid (acid number = 389 mg KOH / g,> 98%, 123.81 g, 0.859 mol, 1.50 eq. Based on the total weight of xylitol and sorbitol) was heated to 80 ° C with stirring and ISL passage and after 30 min immobilized enzyme Candida antarctica lipase B (6.02 g; Fermenta BIOCATALYST CALB _TA 10000 NLT 95%; corresponds to 59077 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 through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear and colorless in the melt and had an acid number of 1.6 mg KOH / g.

Example 9: Enzymatic esterification of a mixture of xylitol and sorbitol (66:34) with 2.00 eq. technical oleic acid (according to the invention)

A mixture of xylitol (11.72 g, 0.077 mol), sorbitol (6.01 g, 0.033 mol) and oleic acid (acid number = 200 mg KOH / g, iodine number = 92.3 g I2 / 100 g, 61.7 g, 0.22 mol, 2.00 eq on the Total weight of xylitol and sorbitol) was heated to 90 ° C with stirring and ISL passage and after 30 min immobilized enzyme Candida antarctica lipase B (2.3 g; Fermenta BIOCATALYST CALB _TA 10000 NLT 95%; corresponds to 59077 PLU) was added. The mixture was then stirred at 80 ° C. and 10 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous in the melt, slightly cloudy and light yellow and had an acid number of 2.0 mg KOH / g.

Example 10: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 2.00 eq. technical oleic acid (according to the invention)

A mixture of xylitol (28.0 g, 0.184 mol), sorbitol (12.0 g, 0.066 mol) and oleic acid (acid number = 200 mg KOH / g, iodine number = 92.3 g I2 / 100 g, 140.2 g, 0.50 mol, 2.00 eq on the

Total weight of xylitol and sorbitol) was heated to 80 ° C. while stirring and passing through ISL and after 1 h immobilized enzyme Candida antarctica lipase B (5.40 g; Purolite D5619, corresponds to 46754 PLU) was added. The mixture was then stirred at 80 ° C. and 25 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous in the melt, slightly cloudy and light yellow and had an acid number of 1.9 mg KOH / g. Example 11: Enzymatic esterification of xylitol with 2.00 eq. Stearic acid (not according to the invention)

A mixture of xylitol (40.00 g, 0.263 mol, 1.00 eq.) And stearic acid (acid number = 198 mg KOH / g,> 92%, 148.18 g, 0.526 mol, 2.00 eq.) Was heated to 90 ° while stirring and passing through ISL C. and after 1 h immobilized enzyme Candida antarctica lipase B (5.65 g; Purolite D5619, corresponds to 48919 PLU) was added. The mixture was then stirred at 90 ° C. and 15 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 80 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear, light yellow in the melt and had an acid number of 1.3 mg KOH / g.

Example 12: Enzymatic esterification of fructose with 2.00 eq. Stearic acid (not according to the invention) A mixture of fructose (42.00 g, 0.233 mol, 1.00 eq.) And stearic acid (acid number = 198 mg KOH / g,> 92%, 132.42 g, 0.482 mol, 2.00 eq.) Was heated to 90 ° while stirring and passing through IS C. and after 1 h immobilized enzyme Candida antarctica lipase B (5.18 g; Fermenta BIOCATALYST CALB _TA 10000 NLT 95%, corresponds to 50834 PLU) was added. The mixture was then stirred at 90 ° C. and 15 mbar for 51 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 90 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear, orange-red in the melt and had an acid number of 14.7 mg KOH / g.

Example 13: Physical mixture of Example 11 and Example 12

A mixture of an ester obtained as described in Example 11 (42.00 g) and an ester obtained as described in Example 12 (18.00 g) was heated to 80 ° C. for 1 h while stirring and passing through ISL. The product obtained was homogeneous, clear, orange in the melt and had an acid number of 5.1 mg KOH / g.

Example 14: Enzymatic esterification of a mixture of xylitol and fructose (70:30) with 2.00 eq. 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 cooled to 90 ° C. after 2 h. Stearic acid (acid number = 198 mg KOH / g, approx. 95%, 142.14 g, 0.501 mol, 2.00 eq) was then added while stirring and passing through N2. After stirring for 30 min at 90 ° C., immobilized enzyme Candida antarctica lipase B (Purolite D5619, 5.46 g, corresponds to 47274 PLU) was added. The mixture was then stirred at 90 ° C. and 10 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered through a filter press with a Seitz T-750 depth filter at 80 ° C. and 2 bar N2 pressure in order to remove the enzyme. The product obtained was homogeneous, clear in the melt and had an acid number of 3.2 mg KOH / g.

Example 15: Enzymatic esterification of a mixture of xylitol, sorbitol and fructose (50:25:25) with 1.91 eq. Caprylic acid (according to the invention)

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 caprylic acid (acid number = 389 mg KOH / g,> 98%, 138.05 g, 0.957 mol, 1.91 eq. Based on the total weight of xylitol, sorbitol and fructose) was heated to 100 ° C. with stirring and passing through N2 and stirred for 1 h. The mixture was then heated to 80 ° C cooled, immobilized enzyme Candida antarctica lipase B (5.92 g; Purolite D5619, corresponds to 51257 PLU) was added, the mixture was further stirred at 80 ° C. and 20 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 90 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear and yellow in the melt and had an acid number of 3.1 mg KOH / g.

Example 16: Enzymatic esterification of a mixture of xylitol, sorbitol and glucose (65:25:10) with 1.91 eq. Caprylic acid (according to the invention)

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 caprylic acid (acid number = 389 mg KOH / g,> 98%, 136.91 g, 0.949 mol, 1.91 eq. Based on the total weight of xylitol, sorbitol and glucose) were heated to 100 ° C. while stirring and passing through N2 and stirred for 1 h. The mixture was then cooled to 80 ° C., immobilized enzyme Candida antarctica lipase B (5.91 g; Purolite D5619, corresponds to 51170 PLU) was added, the mixture was further stirred at 80 ° C. and 20 mbar for 24 h and the water formed was continuously distilled off during this time. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 90 ° C. in order to remove the enzyme. The product obtained was homogeneous, clear and pale yellow in the melt and had an acid number of 10.0 mg KOH / g.

Example 17: Enzymatic esterification of a mixture of xylitol and sorbitol (70:30) with 1.50 eq. Lauric acid (according to the invention)

A mixture of xylitol (51.7 g, 0.340 mol), sorbitol (22.16 g, 0.122 mol) and lauric acid (acid number = 280 mg KOH / g,> 99%, 138.60 g, 0.692 mol, 1.50 eq. Based on the total weight of xylitol and sorbitol) was heated to 100 ° C. with stirring and passing through ISL and after 60 min the immobilized enzyme Candida antarctica lipase B (6.02 g;

Purolite D5619, corresponds to 52122 PLU) added. The mixture was then stirred at 95 ° C. and 50 mbar for 24 h, during which the water formed was continuously distilled off. The mixture was then filtered through a Buchner funnel with a Schwarzband filter at 90 ° C. in order to remove the enzyme. The product obtained was homogeneous in the melt, slightly cloudy and light yellow to almost colorless and had an acid number of 0.8 mg KOH / g.

Example 18 Differentiation of the Examples According to the Invention from the Prior Art The following examples are intended to explain the subject matter of the invention in more detail without restricting it to these examples. These examples are intended to show that the method according to the invention Has advantages over the prior art. The examples not according to the invention were chosen as representatives of the prior art. Technical effect: homogeneity & smell

In Table 1, example 4 according to the invention is compared with examples 1, 2 and 3 not according to the invention with regard to the course of the reaction, homogeneity and odor. Table 1 :

As can be seen from Table 1, Example 2, which is not according to the invention, is inhomogeneous after a reaction time of 24 hours, still has a high residual acid number of approx. 140.5 mg KOH / g and, in addition, a pronounced fatty acid odor, which is the case with the short-chain fatty acids Caprylic acid is perceived as unpleasant. In contrast, Example 1, which is not according to the invention, is homogeneous after a reaction time of 24 hours and has a residual acid number of only <1.3 mg KOH / g, but a pronounced fatty acid odor can also be detected in this example. The same applies to the physical mixture of Example 1 and Example 2 (example 3). Only in example 4 according to the invention is a low residual acid number (ie a high conversion of the fatty acid), a homogeneous product and a pleasant odor (popcorn-like) achieved after a reaction time of 24 hours.

Technical effect: Homogeneous even with lower degrees of esterification

In Table 2, Example 8 according to the invention is compared with Examples 5 and 6 not according to the invention with regard to the course of the reaction and homogeneity. Table 2:

As can be seen from Table 2, Example 5, not according to the invention, shows a phase separation in the melt at 80 ° C. in the form of a sediment. This phenomenon is even more pronounced in example 6, which is not according to the invention, and also occurs in the physical mixture from example 5 and example 6 (example 7). Only example 8 according to the invention is homogeneous in the melt at 80 ° C. and shows no phase separation, despite the comparatively low degree of esterification of 1: 1.5 (molar ratio of sugar /

Fatty acid). Technical effect: color and reactivity (i.e. conversion rate of the fatty acid)

In Table 3, example 14 according to the invention is compared with example 13 not according to the invention with regard to the course of the reaction and color. Table 3:

As can be seen from Table 3, the physical mixture (Example 13) has a significantly poorer color than a process product according to the invention (Example 14). Formulation examples

The following examples are intended to show that the compositions according to the invention can be used in a large number of cosmetic formulations.

Recipes 1a, 1b and 1c: AP / deodorant formulations containing aluminum salts

Formulations 2a, 2b and 2c: Aluminum-free deodorant formulation without AP active ingredients

Formulations 3a, 3b and 3c: ON deodorant emulsion containing potassium alum

Recipe 4a and 4b: AP / Deodorant Lotion

Recipes 5a, 5b and 5c: AP / deodorant creams

Recipe 6a and 6b: Sun Care Spray SPF 30

Recipes 7a, 7b and 7c: sun protection spray

Recipes 8a, 8b and 8c: Sun protection lotion SPF 30

Recipes 9a, 9b and 9c: Sun protection lotion SPF 30, high UVA protection

Recipes 10a, 10b and 10c: Sun protection lotion SPF 30

Formulations 11a, 11b and 11c: Sun protection lotion SPF 50, high UVA protection

Recipes 12a, 12b and 12c: Sun protection lotion SPF 50

Recipes 13a, 13b and 13c: Sun protection lotion SPF 50+

Recipe 14a and 14b: body lotion

Recipes 15a and 15b: Natural care cream

Recipe 16a and 16b: Anti-aging cream

Formulation 17a and 17b: 0 / W Foundation

Formulations 18a, 18b, 18c and 18d: Lotions with cosmetic active ingredients

Formulations 19a, 19b and 19c: Lotion with low oil phase content

Recipes 20a, 20b, 20c and 20d: OLL / sera 1

Recipes 20e, 20f, 20g and 20h: OAV serums 2

Formulations 21a, 21b and 21c: O / W Blemish Balm Lotion

Formulations 22a, 22b, 22c and 22d: Lotion for sensitive skin

Recipes 23a, 23b, 23c and 23d: Nourishing lotion for dry skin 1

Recipes 23e, 23f, 23g and 23h: Nourishing lotion for dry skin 2

Formulations 24a, 24b and 24c: Preservative-Free Lotions 1

Formulations 24d, 24e and 24f: preservative-free lotions 2

Formulations 25a and 25b: W / O lotion

Recipes 26a and 26b: W / O cream

Recipes 27a and 27b: Quick-breaking cream Formulations 28a, 28b and 28c: Cooling Body Lotion

Formulations 29a, 29b and 29c: W / O cream based on natural ingredients

Formulations 30a, 30b, and 30c: Cold Manufacture Lotion

Formulations 31a, 31b and 31c: Moisturizing lotion with urea

Formulations 32a, 32b, 32c and 32d: W / 0 lotion with a silky, light skin feel

Recipes 33a, 33b and 33c: Baby Care

Recipes 34a, 34b and 34c: Foot Care

Formulations 35a and 35b: Sun protection lotion SPF 30 UVA with insect repellent

Recipes 36a and 36b: Sun protection lotion SPF 30 UVA according to Ecocert criteria

Formulations 37a, 37b, 37c and 37d: Sun protection spray SPF 30 UVA

Formulations 38a, 38b, 38c and 38d: Sun protection lotion SPF 50 UVA

Recipes 39a, 39b and 39c: Sun protection lotion SPF 50 according to FDA criteria

Recipes 40a, 40b, 40c, 40d, 40e and 40f: Foundation

Recipes 41a, 41b, 41c, 41 d, 41 e, 41 f and 41g: CC (Color Control) Fluid

Recipes 42a, 42b, 42c, 42d and 42e: AP / deodorant spray or aerosol spray Recipes 43a, 43b, 43c and 43d: Sunscreen aerosol SPF 50 UVA

Recipe 44: cream shower

Recipe 45: body shampoo

Recipe 46: shampoo

Formulation 47a and 47b: Shampoo

Recipe 48: Liquid Soap

Recipe 49: Cream Soap

Recipe 50: Oil Bath

Recipe 51: Micellar Water formake-up removal

Recipes 52a and 52b: Solution for wet wipes

Recipe 53: Anti-perspirant deodorant

Recipe 54: mouthwash

Recipe 55: toothpaste

Claims

Expectations

Process for the enzymatic production of a mixture composition comprising at least two selected from sugar esters and / or sugar alcohol esters comprising the process step

Process according to claim 1, characterized in that the sugars and sugar alcohols are selected from the group agarose, allitol, allulose, altritol, amylopectin, amylose, arabinitol, arabinose, cellobiose, cellulose, chitin, cyclodextrins, deoxyribose, dextrans, erythritol, fructans, Fructose, fucose, galactitol, galactose, glucose, glycogen, hyaluronic acid, iditol, inulin, isomalt, isomaltulose, isomelicitose,

Lactitol, lactose, lactulose, maltitol, maltohexose, maltopentose, maltose, maltotetrose, maltotriose, maltulose, mannitol, mannose, melicitose, pectins, raffinose, rhamnose,

Ribitol, ribose, sucrose, sorbitol, sorbose, stachyose, starch, starch hydrolysates, threitol, trehalulose, umbelliferose, xylitol and xylose.

Process according to claim 1 or 2, characterized in that the acyl group donor is selected from fatty acid acyl group donors, in particular an acyl group selected from the group of acyl groups of caproic acid, caprylic acid, pelargonic 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, petroleic acid, elaidic acid, arachidic acid, behenic acid, erucic acid, gadoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

Process according to at least one of the preceding claims, characterized in that the mixture used in process step B) contains at least two substances selected from sugars and sugar alcohols selected from the group consisting of choline, ammonium and phosphonium salts in an amount less than 2 wt. -%, preferably less than 1% by weight, particularly preferably less than 0.1% by weight, in particular none of the substances, the weight percent being based on all sugars and sugar alcohols in process step B) in the mixture containing at least two selected from sugars and sugar alcohols.

5. The method according to at least one of the preceding claims, characterized in that in method step B) the molar ratio of all sugars and sugar alcohols to acyl groups contained in all acyl group donors is in a range from 1.00 to 0.08 to 1.00 to 10, 00 preferably from 1.00 to 0.500 to 1.00 to 7.00, particularly preferably from 1.00 to 1.25 to 1.00 to 2.25, alternatively particularly preferably from 1.00 to 2.00 to 1, 00 to

4.50.

6. The method according to at least one of claims 1 to 5, 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 group donors in a range from 1.00 to 0.10 to 1.00 to 3.00, particularly preferably from 1.00 to 1.25 to 1.00 to 2.25.

7. The method according to at least one of the preceding claims, characterized in that the lipase selected from the group comprising the lipase from Thermomyces lanuginosus (accession number 059952), the lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei ('accession number P19515), the lipase from Humicola sp. (accession number 059952), the lipase from Rhizomucor javanicus (accession number S32492), the lipase from Rhizopus oryzae (accession number P61872), the lipases from Candida rugosa (accession number P20261, P32946, P32947, P3294 and

P32949), the lipase from Rhizopus niveus (accessionnumber P61871), the lipase from PenicilHum camemberti (accessionnumber P25234), the lipases from Aspergillus niger (ABG73613, ABG73614 and ABG37906) and the lipase from PenicilHum 69number, as well as their cyclopium (accessionnumber P61869number) Amino acid level at least 60%, homologous.

8. Process according to at least one of the preceding claims, characterized in that process step B) is carried out at reaction temperatures in the range between 20 ° C and 160 ° C, preferably 35 ° C and 130 ° C, in particular between 50 ° C and 110 ° C becomes.

9. The method according to at least one of the preceding claims, characterized in that method step B) is carried out at a pressure of less than 1 bar, preferably less than 0.5 bar and particularly preferably less than 0.05 bar.

10. The method according to at least one of the preceding claims, characterized in that in method step B) the mixture containing at least two selected from sugars and sugar alcohols and the acyl group donor in total at least 10% by weight, preferably at least 86% by weight, particularly preferably at least 90 % By weight of the total reaction mixture. 11. Process according to at least one of the preceding claims, characterized in that by-products formed in process step B), for example in the case that the acyl group donor used is an acid, water, in the case that the acyl group donor used is an ester, the corresponding alcohol is removed .

12. The method according to at least one of the preceding claims, characterized in that it includes the method step

A) providing spatially separate provision of the at least two selected from sugars and sugar alcohols in solid or water-dissolved form and mixing them into the mixture used in process step B) containing at least two selected from sugars and sugar alcohols. 13. The method according to claim 12, characterized in that process step A) a

Reduction of the water content of the mixture used in process step B) containing at least two selected from sugars and sugar alcohols to less than 17 wt.%, Preferably less than 14 wt.%, Particularly preferably less than 10 wt the weight percent on the total mixture used in process step B) containing at least two selected from sugars and

Obtain sugar alcohols.

14. Mixture composition comprising at least two selected from sugar esters and sugar alcohol esters obtainable by a process according to at least one of the preceding claims.

15. Mixture composition containing sugar esters and / or sugar alcohol esters, characterized in that the sugar and / or sugar alcohol residue of the sugar ester and / or the sugar alcohol ester is selected from at least two sugar and / or sugar alcohol residues selected from Group of residues of allitol, allulose, altritol,

Arabinitol, arabinose, cellobiose, deoxyribose, erythritol, fructose, fucose, galactitol, galactose, glucose, iditol, isomalt, isomaltulose, lactitol, lactose, lactulose, maltitol, maltose, maltulose, mannitol, mannose, rhamnose, ribitol, ribose, sucrose, Sorbitol, sorbose, threitol, trehalulose, xylitol and xylose and the ester residue is selected from at least one acyl group from the group of acid residues of fatty acids.