EP-4734915-A1 - POLYGLYCEROL PARTIAL ESTER COMPRISING OLEIC ACID

EP4734915A1EP 4734915 A1EP4734915 A1EP 4734915A1EP-4734915-A1

Abstract

The invention relates to a polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid.

Inventors

VON HOF, JAN MARIAN
Maier, Renate
BECKERS, Sebastian Johannes
FRIEDRICH, ACHIM
MEYER, JUERGEN
ZIMMERMANN, SEBASTIAN

Assignees

Evonik Operations GmbH

Dates

Publication Date: 20260506
Application Date: 20240627

Claims (1)

202300092 Foreign Filing 35 Claims 1. Polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid. 2. Polyglycerol partial ester according to Claim 1, characterized in that the polyglycerol esterified into the polyglycerol partial ester has a glycerin content of 0.05% by weight to 25.0% by weight, preferably of 0.1% by weight to 15.0% by weight, more preferably of 0.1% by weight to 10.0% by weight. 3. Polyglycerol partial ester according to Claim 1 or 2, characterized in that the polyglycerol esterified into the polyglycerol partial ester has an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0. 4. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the polyglycerol esterified into the polyglycerol partial ester has a content of cyclic isomers of 1% by weight to 50% by weight, preferably of 2% by weight to 40% by weight, more preferably of 3% by weight to 30% by weight. 5. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial ester has an average degree of condensation P of 1.5 to 9.0, preferably of 2.0 to 7.0, more preferably 3.0 to 5.0. 6. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial ester has an acid value of between 188 mg KOH/g and 20 mg KOH/g, preferably between 97 mg KOH/g and 33 mg KOH/g, more preferably between 65 mg KOH/g and 40 mg KOH/g. 7. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the dicarboxylic acid is selected from azelaic acid and sebacic acid. 8. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that the molar ratio of the poly(hydroxycarboxylic) acid esterified into the polyglycerol partial 202300092 Foreign Filing 36 ester, the at least one dicarboxylic acid esterified into the polyglycerol partial ester and the oleic acid esterified into the polyglycerol partial ester is in the range of 0.50 : 1.00 : 2.90 to 4.00 : 1.00 : 6.50, preferably 0.60 : 1.00 : 2.80 to 3.50 : 1.00 : 5.80, more preferably 0.70 : 1.00 : 2.75 to 2.50 : 1.00 : 5.20, and most preferably 0.75 : 1.00 : 2.70 to 1.50 : 1.00 : 4.50. 9. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has a HLB value of from 1.0 to 9.0, preferably from 1.5 to 7.5 and more preferably from 2.5 to 6.0. 10. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has an iodine value of 28.0 g I/100 g to 52.0 g I/100 g, preferably 31.0 g I/100 g to 49.0 g I/100 g, more preferably of 34.0 to 46.0 g I/100 g. 11. Polyglycerol partial ester according to at least one of the preceding claims, characterized in that it has a viscosity at 25 °C of 100 mPas to 10000 mPas, preferably 500 mPas to 8000 mPas, more preferably 1000 mPas to 6000 mPas. 12. Method for preparing a polyglycerol partial ester, comprising the method steps of A) providing a polyglycerol, preferably having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0, B) providing a carboxylic acid mixture comprising: poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, at least one dicarboxylic having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and oleic acid, C) esterifying the polyglycerol with the carboxylic acid mixture. 13. Formulation, especially a cosmetic formulation, comprising 1) polyglycerol partial esters according to at least one of Claims 1 to 11 or obtainable according to the method of Claim 12, and, each of the following optionally 2) at least one antioxidant, 2A) at least one preservative, preferably selected from the group comprising anisic acid, levulinic acid, benzoic acid, sorbic acid, salicylic acid, pentylene glycol, glyceryl caprylate, glyceryl caprate, phenyl propanol, phenethyl alcohol and triethylcitrate, and 2B) at least one selected from ester emollients and triglycerides. 202300092 Foreign Filing 37 14. Use of a polyglycerol partial ester according to at least one of Claims 1 to 11 or obtainable according to the method of Claim 12 as ingredient, especially as emulsifier and/or lubricity additive, in metalworking fluids.

Description

202300092 Foreign Filing 1 Polyglycerol partial ester comprising oleic Field of the invention The invention relates to a polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid. Prior art EP1500427 discloses polyglycerol partial ester of poly(hydroxystearic) acid and polyfunctional carboxylic acids, obtainable by esterification of a a) polyglycerol mixture with b) poly(hydroxystearic) acid and c) di- and/or tricarboxylic acids and optionally/or with d) dimer fatty acids, and e) fatty acids having 6 to 22 C atoms. These polyglycerol partial esters allow formulation of highly liquid emulsions which have a pleasant sensation on the skin and at the same time an improved resistance to freezing-thawing. These polyglycerol partial ester, however, are not capable of stabilizing high amount of oil in water- in-oil-emulsions. EP3500550 discloses polyglycerol partial esters obtainable by esterification of a polyglycerol with a carboxylic acid mixture comprising: a) at least one polyhydroxycarboxylic acid of a hydroxycarboxylic acid having 8 to 32 carbon atoms, b) at least one short-chain dicarboxylic acid having 2 to 16 carbon atoms, c) at least one long-chain dicarboxylic acid having 24 to 44 carbon atoms, and d) at least one fatty acid selected from linear, unsaturated and branched, saturated fatty acids having 14 to 24 carbon atoms. EP3325582 discloses lubricating oil compositions comprising (a) 0.2 to 5% by weight of polyglycerol partial esters, based on the total weight of the lubricating oil composition, characterized in that the polyglycerol partial esters are obtainable by esterification of a polyglycerol mixture with 202300092 Foreign Filing 2 (i) polyfunctional carboxylic acids and (ii) saturated or unsaturated, linear or branched fatty acids and/or (ii) poly(hydroxystearic acid), wherein the degree of esterification of the polyglycerol mixture is between 30 and 75% of the OH groups; (b) 85 to 99.8% by weight of an apolar base stock selected from the group consisting of API Group II, III and IV and/or mixtures thereof, based on the total weight of the lubricating oil composition; and (c) 0 to 10% by weight of a polar ester oil of Group V according to the definition of the American Petroleum Institute (API), based on the total weight of the lubricating oil composition. It is an objective of the invention to improve the skin sensation of formulations even further and to reduce the whitening of formulations when applied to the skin. Description of the invention that, surprisingly, polyglycerol partial esters as described in claim 1 solve the problem underlying the instant invention. The present invention therefore provides a polyglycerol partial ester obtainable by esterification of a) a polyglycerol mixture, b) poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, c) at least one dicarboxylic acid having 6 to 12, preferably 9 to 10, carbon atoms, more preferably selected from azelaic acid and sebacic acid, and d) oleic acid. The invention further provides a method for preparing a polyglycerol partial ester comprising the method steps of A) providing a polyglycerol, preferably having an average degree of condensation N of 2.4 to 15.0, preferably 2.6 to 10.0, especially 2.8 to 8.0, B) providing a carboxylic acid mixture comprising: poly(hydroxycarboxylic) acid, preferably selected from poly(hydroxystearic) acid and poly(ricinoleic) acid, wherein poly(hydroxystearic) acid is particularly preferred, at least one dicarboxylic acid having 4 to 18, preferably 4 to 14, more preferably 8 to 12, carbon atoms, and oleic acid, C) esterifying the polyglycerol with the carboxylic acid mixture. 202300092 Foreign Filing 3 An advantage of the present invention is that the polyglycerol partial esters described herein may be prepared from exclusively renewable raw materials. A further advantage is that the polyglycerol partial esters described herein can be prepared on the basis of principles of green chemistry. Another advantage of the present invention is that formulations can be provided that are polyglycol ether-free. A further advantage is that the polyglycerol partial esters described herein are biodegradable. A further advantage is that the polyglycerol partial esters described herein have a good ecotoxicological profile. A further advantage of the polyglycerol partial esters described herein is that they are very mild on the skin, not irritating and non-toxic. Another advantage of the polyglycerol partial esters described herein is that they have improved sensory properties in formulations. The tackiness of sun protection formulations is reduced after application. The formulations u