Polyol ester of branched C18 fatty acid

Abstract

The present invention relates to a mixture of polyol esters of branched C18 fatty acids, a process for preparing such a mixture, and its use in various industrial fields, such as the lubricant and cosmetic fields.

Description

[Technical Field]

[0001] The present invention relates to mixtures of polyol esters of branched C18 fatty acids, methods for preparing such mixtures, and their use in various industrial sectors such as lubricants and cosmetics. [Background technology]

[0002] Commercially available branched fatty acid compositions, such as "isostearic acid" (ISA), are obtained as by-products of catalytic and thermal dimerization of unsaturated linear fatty acid(s). In fact, instead of oligomerization, a portion of the fatty acid(s) is rearranged to produce branched monomeric fatty acids that can be isolated from the oligomerized fatty acids. This branched fatty acid composition, commercially known as "isostearic acid," is a mixture of various linear and primarily branched (both mono- and poly-branched) saturated monocarboxylic fatty acids.

[0003] Esters derived from these "isostearic acids" are known and are used in lubricant compositions and cosmetics.

[0004] In lubricant compositions, some esters of branched fatty acids are used as base oils or additives.

[0005] In cosmetics, some esters of branched fatty acids are used as emollients.

[0006] In particular, WO 2013 / 093411 describes compounds of formula I, R 1 -COOR 2 [In the formula, R 1 and R 2 is a hydrocarbon chain; and at least 60% by weight of the molecules of formula I are monoalkyl branched R 1 and wherein less than 25% by weight of the molecules of formula I are polyalkyl branched R 1 The use of monoesters of the formula [including the formula:] as emollients is described. Summary of the Invention [Problem to be solved by the invention]

[0007] The applicant has surprisingly found that polyol esters obtained from particular branched fatty acid compositions exhibit lower viscosity, better water resistance, better film-forming properties and / or higher hardness than corresponding esters obtained from commercially available branched fatty acid compositions having different characteristics.

[0008] These properties are of particular interest for some lubricant compositions and cosmetic products. [Means for solving the problem]

[0009] The present invention therefore relates to a mixture of polyol esters of branched C18 fatty acids, said mixture being obtainable by esterification of a branched C18 fatty acid composition with a polyol, said composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio of mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids, - at most 10% by weight of cyclic compounds, Including, Weight percentages refer to mixtures based on the weight of the composition.

[0010] This particular mixture of polyol esters of branched C18 fatty acids exhibits a lower viscosity than other mixtures of polyol esters of branched C18 fatty acids obtained from branched C18 fatty acid compositions having characteristics different from those claimed. In particular, the kinematic viscosity at 40°C of the mixture of polyol esters according to the invention is at least 15% lower than the kinematic viscosity at 40°C of the corresponding polyol ester obtained from a branched C18 fatty acid composition having characteristics different from those claimed. DETAILED DESCRIPTION OF THE INVENTION

[0011] A "branched" fatty acid is intended to mean that the hydrocarbon chain of the fatty acid has one or more alkyl side groups that are generally short chains.

[0012] "Short alkyl side group" is intended to mean a group containing fewer than 5 carbon atoms. More particularly, each short alkyl side group is linear and, even more particularly, is selected from the group formed by methyl, ethyl and propyl. Preferably, each short alkyl side group is methyl and / or ethyl, more preferably methyl.

[0013] A "singly branched" fatty acid is intended to mean that the straight hydrocarbon chain of the fatty acid has only one alkyl side group, which is generally short chain.

[0014] "Multiple-branched" fatty acid is intended to mean that the linear hydrocarbon chain of the fatty acid has two or more alkyl side groups that are generally short chains.

[0015] In the term "CX", X indicates the number of carbon atoms in the fatty acid, that is, the number of carbon atoms in the hydrocarbon chain and the optional alkyl side group. Thus, "branched C18 fatty acid" refers to all branched fatty acids having 18 carbon atoms. In particular, these branched fatty acids are positional isomers.

[0016] "CX-CY fatty acids" means that the number of carbon atoms in each fatty acid falls independently within the range of X to Y.

[0017] In this application, all numerical ranges used should be understood to include the endpoints, unless otherwise stated.

[0018] Preferably, the amount of mono-branched C18 fatty acids and multi-branched fatty acids in the branched C18 fatty acid composition is at least 82% by weight, more preferably at least 84% by weight, based on the weight of the composition.

[0019] Preferably, the amount of mono-branched C18 fatty acids and poly-branched C18 fatty acids in the branched C18 fatty acid composition is at most 98% by weight based on the weight of the composition.

[0020] Polyols are straight or branched hydrocarbon chains containing two or more hydroxyl groups.

[0021] The polyol preferably consists only of carbon, oxygen and hydrogen atoms.

[0022] Preferably, the polyol is saturated.

[0023] Suitable polyols for the present invention include, but are not limited to, trimethylolpropane, pentaerythritol, neopentyl glycol, glycerol, ethylene glycol, propylene glycol, and 1,3-propanediol.

[0024] Preferably, the polyol is selected from the group consisting of neopentyl glycol, pentaerythritol and trimethylolpropane.

[0025] More preferably, the polyol is pentaerythritol or trimethylolpropane.

[0026] Preferably, in the mixture of polyol esters of branched C18 fatty acids according to the invention, the average degree of esterification is higher than 1.

[0027] More preferably, in the mixture of polyol esters of branched C18 fatty acids according to the invention, all hydroxyl groups of the polyol are esterified.

[0028] The straight chain fatty acids preferably contain from 6 to 24 carbon atoms.

[0029] Preferably, the straight chain fatty acids are saturated.

[0030] Preferably, no unsaturated fatty acids are present in the mixture of polyol esters according to the invention.

[0031] Preferably, no unsaturated compounds are present in the mixture of polyol esters according to the invention.

[0032] Advantageously, in the mixture of polyol esters according to the invention, the amount of linear fatty acids is at most 10% by weight, based on the weight of the composition.

[0033] Preferably, the amount of straight chain fatty acids is at most 8% by weight, more preferably at most 7% by weight, even more preferably at most 6% by weight, based on the weight of the composition.

[0034] Preferably, the amount of straight chain fatty acid is in the range of 1% to 10% by weight, more preferably 1% to 8% by weight, even more preferably 1% to 7% by weight, for example 1% to 6% by weight, based on the weight of the composition.

[0035] Cyclic compounds include, but are not limited to, alicyclic carboxylic acids or esters thereof, aromatic compounds, alkylcyclopentanones, lactones, and mixtures thereof.

[0036] Preferably, the cyclic compound contains 14 to 22 carbon atoms, more preferably 16 to 18 carbon atoms.

[0037] Advantageously, in the mixture of polyol esters according to the invention, the amount of cyclic compounds is at most 8% by weight, based on the weight of the composition.

[0038] Preferably, the amount of cyclic compound is at most 7% by weight, more preferably at most 6% by weight, based on the weight of the composition.

[0039] Preferably, the amount of cyclic compound ranges from 1% to 8% by weight, more preferably from 1% to 7% by weight, even more preferably from 1% to 6% by weight, for example from 1% to 5% by weight, based on the total weight of the composition.

[0040] Advantageously, in the mixture of polyol esters according to the invention, the amount of mono-branched C18 fatty acids is at least 45% by weight, based on the weight of the composition.

[0041] Preferably, the amount of mono-branched C18 fatty acid is at least 50% by weight based on the weight of the composition.

[0042] Preferably, the mixture according to the invention does not comprise a polyol ester of an oligomerized fatty acid. More particularly, the branched C18 fatty acid composition does not comprise an oligomerized fatty acid.

[0043] Oligomerized fatty acids are in particular dimeric, trimeric or tetrameric fatty acids.

[0044] In one preferred embodiment, the branched C18 fatty acid composition comprises: - 80 to 98% by mass of mono-branched C18 fatty acids and poly-branched C18 fatty acids; - 1 to 8% by mass of straight-chain fatty acids; - 1 to 8% by mass of a cyclic compound; Including, The mass ratio of mono-branched C18 fatty acids to multi-branched C18 fatty acids is greater than 1, Weight percentages are based on the weight of the composition.

[0045] In a particularly preferred embodiment, the branched C18 fatty acid composition comprises: - 84 to 98% by mass of mono-branched C18 fatty acids and poly-branched C18 fatty acids, wherein the amount of mono-branched C18 fatty acids is at least 50% by mass; - 1 to 6% by mass of straight-chain fatty acids; - 1 to 6% by mass of a cyclic compound; Including, The mass ratio of mono-branched C18 fatty acids to multi-branched C18 fatty acids is greater than 1, Weight percentages are based on the weight of the composition.

[0046] The present invention also provides a method for preparing a mixture of polyol esters of branched C18 fatty acids, comprising esterifying a branched C18 fatty acid composition with a polyol, Also disclosed are methods wherein the branched C18 fatty acid composition comprises: - at least 80% by weight of mono- and poly-branched C18 fatty acids, with a mono-branched C18 fatty acid / poly-branched C18 fatty acid mass ratio of more than 1; - maximum 15% by weight of straight-chain fatty acids; and - maximum 10% by weight of cyclic compounds; Here, the weight percentages are based on the weight of the branched C18 fatty acid composition.

[0047] The branched C18 fatty acids, polyols, straight chain fatty acids and cyclic compounds are as described above, including preferred and advantageous positions.

[0048] The esterification reaction can be carried out according to well-known conventional reaction conditions.

[0049] The esterification reaction is preferably carried out under stirring and heating at a temperature of at least 100° C., more preferably at least 120° C. In particular, the esterification reaction can be carried out at a temperature of 100 to 250° C., preferably 120 to 240° C.

[0050] An esterification catalyst such as methanesulfonic acid can be used.

[0051] Advantageously, water is removed as it is formed from the reaction mixture.

[0052] Preferably, the esterification reaction is carried out with at least one molar equivalent of a branched C18 fatty acid.

[0053] More preferably, the molar ratio of branched C18 fatty acid to polyol is at least 1.

[0054] Preferably, the esterification reaction is carried out until the acid number is less than 20 mg KOH / g, preferably less than 15 mg KOH / g, the acid number being measured according to standard AOCS Cd 3D-63.

[0055] In this application, unless otherwise specified, all acid numbers are measured according to standard AOCS Cd 3D-63.

[0056] Preferably, the esterification reaction is carried out until the hydroxyl number is less than 100 mg KOH / g, preferably less than 25 mg KOH / g, the hydroxyl number being measured according to standard ASTM D1957.

[0057] In this application, unless otherwise specified, all hydroxyl numbers are measured according to standard ASTM D1957.

[0058] Advantageously, the method according to the invention further comprises the preparation of a branched C18 fatty acid composition from a starting material comprising at least 80% by weight of linear monoethylenically unsaturated C18 fatty acids based on the total weight of the starting material, said preparation comprising: i) isomerizing linear unsaturated C18 fatty acids by heating in the presence of a zeolite catalyst having an orthorhombic framework structure with one-dimensional straight channels of 10-membered rings or with a two-dimensional channel system of 10-membered rings intersected by 8-membered rings; ii) separating the monomer fraction from the oligomeric fraction formed during step i); iii) purifying the monomer fraction to obtain a branched C18 fatty acid composition; Includes:

[0059] Straight-chain unsaturated C18 fatty acids consist of monoethylenically and polyethylenically unsaturated C18 fatty acids.

[0060] Preferably, the straight-chain unsaturated C18 fatty acids are oleic acid and / or elaidic acid, and linoleic acid and / or linolenic acid.

[0061] The linear monoethylenically unsaturated C18 fatty acid can be oleic acid and / or elaidic acid. Preferably, the linear monoethylenically unsaturated C18 fatty acid is oleic acid.

[0062] The starting materials are advantageously fatty acids of renewable oils, which are preferably vegetable or animal oils.

[0063] Some renewable oils naturally contain at least 80% by weight of oleic acid, based on the weight of the renewable oil. This fatty acid can be recovered from one of these oils by any method known in the art. Preferably, the starting material is fatty acid obtained from high oleic sunflower oil.

[0064] Some renewable oils that are monoethylenically unsaturated and polyethylenically unsaturated but contain less than 80% by weight of oleic acid groups, based on the weight of the renewable oil, can be partially hydrogenated to optimize their content of the corresponding fatty acids before recovery. Suitable renewable oils for partial hydrogenation are rapeseed oil, corn oil, soybean oil, sunflower oil, safflower oil and tall oil.

[0065] Fatty acids obtained from any renewable oil may be fractionated to isolate oleic acid and obtain a suitable starting material.

[0066] Preferably, the starting material comprises no more than 95% by weight, more preferably no more than 90% by weight, of linear monoethylenically unsaturated C18 fatty acids, based on the total weight of the starting material.

[0067] Preferably, the starting material further comprises at least 5% by weight of linear polyethylenically unsaturated C18 fatty acids.

[0068] Preferably, the linear polyethylenically unsaturated C18 fatty acid is a linear diethylenically unsaturated C18 fatty acid, in particular linoleic acid.

[0069] Step i) is carried out at a temperature sufficient to achieve the isomerization reaction. The isomerization step is carried out at a temperature in the range of 150°C to 300°C, preferably 180°C to 260°C, more preferably 230°C to 250°C, and at a temperature of 2 x 10 5 Pa~11×10 5 Pa, preferably 3 x 10 5 Pa~9×10 5 It can be carried out at pressures in the range of Pa.

[0070] The isomerization step can be carried out for 2 to 16 hours, preferably 6 to 12 hours.

[0071] The isomerization step may be carried out in the presence of water, the water content preferably being in the range of 0.1 to 5% by mass based on the total mass of the starting materials.

[0072] The isomerization step may be followed by an additional step of separating the zeolite catalyst from the reaction product of step i), preferably by filtration.

[0073] Step ii) is preferably achieved by distillation, in particular molecular distillation, at a temperature in the range of 200-300° C. and a pressure in the range of 1-4 mbar.

[0074] Step iii) may involve hydrogenation, crystallization, fractionation and / or distillation.

[0075] Hydrogenation can be carried out by methods known in the art, for example, using palladium-on-carbon or supported nickel as catalyst. Preferably, the temperature during hydrogenation is in the range of 180-250 °C and the pressure is 16 × 10 5 Pa~26×10 5 The range is Pa.

[0076] To separate the resulting solidified straight-chain fatty acids from the liquid branched fatty acids, crystallization can be carried out using sulfates or urea (clathration) or alternatively, crystallization can be carried out at low temperatures, for example at temperatures below 10°C (cold crystallization).

[0077] The distillation is preferably carried out at a temperature in the range of 200 to 300° C. and a pressure in the range of 1 to 4 mbar.

[0078] Preferably, step iii) comprises hydrogenation, crystallization, fractionation and distillation.

[0079] After step iii), a branched C18 fatty acid composition is obtained, which comprises at least 80% by weight of branched C18 fatty acids, less than 15% by weight of straight-chain fatty acids, and less than 10% by weight of cyclic compounds, with a mass ratio of mono-branched C18 fatty acids / multi-branched C18 fatty acids greater than 1, wherein the mass percentages are based on the mass of the branched C18 fatty acid composition.

[0080] In one preferred embodiment, the method for preparing a mixture of polyol esters of branched C18 fatty acids comprises: - preparing a branched C18 fatty acid composition comprising the steps of: i) isomerizing a starting material of linear unsaturated C18 fatty acids, which contains at least 80% by weight of linear monoethylenically unsaturated C18 fatty acids based on the total weight of the starting material, by heating in the presence of a zeolite catalyst having an orthorhombic framework structure with one-dimensional straight channels of 10-membered rings or a two-dimensional channel system of 10-membered rings intersecting with 8-membered rings; ii) separating the monomer fraction from the oligomeric fraction formed during step i); and iii) purifying the monomer fraction to obtain a branched C18 fatty acid composition; - esterification of branched C18 fatty acid compositions with polyols; Includes:

[0081] The process according to the invention makes it possible to obtain the mixture according to the invention. Thus, the mixture of polyol esters according to the invention can be obtained by the process according to the invention, which is an economically viable process.

[0082] In a zeolite catalyst having an orthorhombic framework structure with a two-dimensional channel system of 10-membered rings intersecting with 8-membered rings, preferably both the 10-membered rings and the 8-membered rings are elliptical and have dimensions of 4.2 x 5.4 angstroms and 3.5 x 4.8 angstroms, respectively.

[0083] The zeolite catalyst is preferably a zeolite catalyst of MTT, TON or FER framework type, in particular ZSM-22, ZSM-23 or ferrierite (FER).

[0084] Preferably, the zeolite catalyst is calcined prior to use in the isomerization step.

[0085] More specifically, the zeolite catalyst is H-ZSM-22, H-ZSM-23 or H-FER.

[0086] Preferably, the amount of zeolite catalyst is at least 0.1 wt %, more preferably at least 0.5 wt %, even more preferably at least 1 wt %, based on the weight of the starting material.

[0087] Preferably, the amount of zeolite catalyst is at most 10% by weight, more preferably at most 7% by weight, even more preferably at most 5% by weight, based on the weight of the starting material.

[0088] The present invention also relates to the use of a mixture of polyol esters according to the invention in a lubricant composition.

[0089] As illustrated in Example 3, mixtures of polyol esters of branched C18 fatty acids according to the present invention exhibit lower viscosities than corresponding polyol esters of branched C18 fatty acids with different characteristics.

[0090] However, regardless of the branched C18 fatty acid composition, the flash points of different mixtures of polyol esters of branched C18 fatty acids remain similar.

[0091] Two temperatures are similar if one temperature is equal to ±10% of the other temperature.

[0092] The same applies to the pour point of the mixture of polyol esters of branched C18 fatty acids according to the invention, which is not lower than the pour point of mixtures of polyol esters of other branched C18 fatty acid compositions.

[0093] Therefore, the mixture of polyol esters according to the present invention is preferred in applications requiring low viscosity lubricants.

[0094] The present invention therefore also relates to a lubricant composition comprising a mixture of polyol esters according to the invention and a base oil.

[0095] Preferably, the base oil content is at least 50 mass %, more preferably at least 75 mass %, based on the mass of the lubricant composition.

[0096] Preferably, the amount of the mixture of polyol esters according to the invention is at least 2% by weight, more preferably at least 5% by weight, based on the weight of the lubricant composition.

[0097] Preferably, the amount of the mixture of polyol esters according to the invention is at most 50% by weight, more preferably at most 45% by weight, based on the weight of the lubricant composition.

[0098] The base oil may comprise one or more oils selected from mineral oils, renewable oils and / or synthetic oils. Preferably, the base oil is selected from the group consisting of mineral oils and / or synthetic oils.

[0099] Mineral oils are oils obtained from petroleum refining, such as paraffinic oils, hydrorefined oils, hydrocracked oils, and hydroisomerized oils, which consist essentially of carbon and hydrogen atoms.

[0100] Mineral oils are divided into three groups. Group I oils: These oils have a saturated hydrocarbon content of less than 90% by weight, an aromatic hydrocarbon content of more than 1.7% by weight, a sulfur content of more than 0.03% by weight and a viscosity index of 80 to 120. Group II oils: These oils have a saturated hydrocarbon content of more than 90% by weight, an aromatic hydrocarbon content of less than 1.7% by weight, a sulfur content of less than 0.03% by weight and a viscosity index of 80 to 120. Group III oils: these oils have a saturated hydrocarbon content of more than 90% by weight, an aromatic hydrocarbon content of less than 1.7% by weight, a sulfur content of less than 0.03% by weight and a viscosity index of more than 120. Here, the weight percent is based on the weight of the oil.

[0101] Synthetic oils are obtained by chemical reactions between molecules of petrochemical and / or renewable origin, excluding the usual chemical reactions used to obtain mineral oils (e.g., hydrorefining, hydrocracking, hydrotreating, hydroisomerization, etc.). Examples of synthetic oils are esters, polyalkylene glycols (PAGs), and polyalphaolefins (PAOs). Preferably, the synthetic oil is a polyalkylene glycol (PAG), a polyalphaolefin (PAO), or a mixture thereof.

[0102] The lubricant compositions of the present invention find advantageous use in industrial and automotive applications.

[0103] Examples of industrial lubricant compositions are textile oils, industrial transmission oils, compressor oils, turbine oils, gear oils and hydraulic oils.

[0104] Examples of lubricant compositions for the automotive sector are hydraulic oils, transmission fluids, coolants, engine oils, axle oils, gearbox fluids, brake fluids, shock absorber oils and damper oils.

[0105] In this patent application, the terms "oil" and "liquid" are used interchangeably in specifying the application / use of the compositions according to the invention.

[0106] Preferably, the mixture of polyol esters according to the invention can be used for the preparation of lubricant compositions for the automotive and / or industrial sector.

[0107] In fact, due to their lower viscosity compared to mixtures of polyol esters with similar flash points, the mixtures of polyol esters according to the invention are suitable for any lubricant composition requiring a low viscosity.

[0108] For example, the polyol ester mixtures according to the invention are particularly suitable for use as hydraulic fluids. Indeed, due to their lower viscosity compared to mixtures of polyol esters with similar flash points, the hydraulic fluids are easier to handle and require less energy to pump, which allows for reduced energy consumption.

[0109] Thus, the present invention also relates to a method for reducing the viscosity of a mixture of polyol esters of branched C18 fatty acids by esterifying the branched C18 fatty acid composition with a polyol, the composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio of mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids; and - maximum 10% by weight of cyclic compounds; Here, weight percent is based on the weight of the composition.

[0110] The mixture of polyol esters, branched C18 fatty acids, polyols, straight chain fatty acids and cyclic compounds are as described above, including preferred and advantageous positions.

[0111] The present invention also relates to the use of the mixture of polyol esters according to the invention in cosmetic products.

[0112] The polyol ester mixtures of the present invention are also useful in cosmetics, particularly personal care products, because they exhibit good film-forming, water resistance, and hardness properties, as exemplified in Example 4.

[0113] These properties are particularly valuable for cosmetics: film-forming properties actually prevent the skin from drying out; water-resistance allows the cosmetic to remain on the skin longer by resisting washing and / or perspiration; and hardness properties allow the cosmetic to be formed into a solid form.

[0114] The present invention also relates to cosmetic products, in particular personal care products, comprising a mixture of polyol esters according to the invention and active ingredients and / or preservatives.

[0115] Preferably, the active ingredient is a UV filter, an anti-aging agent and / or a moisturizer.

[0116] More specifically, the active ingredient is selected from the group consisting of allantoin, tocopherol, ascorbic acid, ascorbyl palmitate, vitamin D, polyphenols, flavonoids, and mixtures thereof.

[0117] More specifically, the preservative is selected from the group consisting of phenoxyethanol, glycol ethers, benzoic acid, sorbic acid, salicylic acid, glycols, parabens, thiazolinones, ethylhexylglycerin, aldehydes, and mixtures thereof.

[0118] Preferably, the personal care product is a lipstick, lip gloss, moisturizer, sunscreen or mascara.

[0119] The present invention therefore relates to a method for improving the film-forming properties of a cosmetic product by adding to the cosmetic product a mixture of polyol esters of branched C18 fatty acids obtainable by esterifying a branched C18 fatty acid composition with a polyol, the composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio of mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids; and - maximum 10% by weight of cyclic compounds; Here, weight percent is based on the weight of the composition.

[0120] As exemplified in Example 4.2, improved film formability is measured by a reduction in water loss from the substrate onto which the film is formed, preferably by at least 25%, more preferably by at least 30%.

[0121] The present invention also relates to a method for improving the water resistance of a cosmetic product by adding to the cosmetic product a mixture of polyol esters of branched C18 fatty acids obtainable by esterifying a branched C18 fatty acid composition with a polyol, said composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio of mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids; and - maximum 10% by weight of cyclic compounds; Here, weight percent is based on the weight of the composition.

[0122] As illustrated in Example 4.3, the improvement in water resistance corresponds to a reduction in the cosmetic's solubility in water, preferably by at least 10%.

[0123] The present invention relates to a method for improving the hardness of a cosmetic product by adding to the cosmetic product a mixture of polyol esters of branched C18 fatty acids obtainable by esterifying a branched C18 fatty acid composition with a polyol, the composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio of mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids; and - maximum 10% by weight of cyclic compounds; Here, weight percent is based on the weight of the composition.

[0124] As exemplified in Example 4.4, the improvement in hardness is preferably at least 30%, more preferably at least 40%, and even more preferably at least 50%.

[0125] In the method according to the invention, the mixture of polyol esters, branched C18 fatty acids, polyols, linear fatty acids, cyclic compounds and cosmetic agents are as described above, including their preferred and advantageous positions. [Example]

[0126] The present invention is further illustrated by the following examples, it being understood that the invention as claimed is not intended to be limited in any way by these examples.

[0127] Example 1: Method for preparing a mixture of polyol esters of branched C18 fatty acids according to the present invention 1.1 Preparation of branched C18 fatty acid compositions ISA1 to ISA3 1.1.1 Isomerization of linear unsaturated fatty acids using zeolite catalysts Three compositions of branched C18 fatty acids ISA1 to ISA3 were prepared using different zeolite catalysts H-ZSM22, H-ZSM23, and ferrierite, respectively.

[0128] For each composition, 1200 g of fatty acids obtained from high oleic sunflower oil (containing 83% by weight of oleic acid and 7.3% by weight of linoleic acid) and 30 g of zeolite catalyst were placed together in an autoclave. The air in the autoclave was purged with nitrogen. The mixture was heated to 240°C with stirring. This reaction temperature was maintained for 7 hours, and the pressure was increased to 11 x 10 5 It rose to Pa.

[0129] The reaction mixture was then cooled to 80° C. and simultaneously the gaseous components were removed by flushing with nitrogen.

[0130] The zeolite catalyst was subsequently removed from the reaction product by vacuum filtration.

[0131] 1.1.2 Collection of the monomer fraction More than 90% by weight of the monomer fraction was separated from the oligomer fraction by distillation up to 260° C. under 2 mbar.

[0132] 1.1.3 Purification of the monomer fraction A hydrogenation step was performed on the monomer fraction using 0.20% palladium-on-carbon catalyst. The product was hydrogenated at 200 °C until hydrogen consumption ceased.

[0133] The product was then further purified by crystallization to isolate the branched fatty acids. To this end, an aqueous solution containing 1.2% by weight of sodium decyl sulfate and magnesium sulfate was added to the monomer fraction, and the mixture was cooled to 10°C. The aqueous phase, together with the crystals of mainly linear fatty acids, was removed from the branched fatty acids by centrifugation. The branched fatty acid composition was washed three times with water.

[0134] The same aqueous solution was then added to the branched fatty acids and the mixture was cooled to 4° C. The aqueous solution was then removed as before and the new composition of branched C18 fatty acids was washed three times with water.

[0135] In the final purification step, low molecular weight compounds were removed by fractional distillation.

[0136] 1.1.4 Analysis of Branched C18 Fatty Acid Composition To characterize the branched C18 fatty acid compositions obtained after the purification process, the latter carboxylic acids were esterified with methanol. Samples of each composition were then analyzed by gas chromatography according to standard ISO 12966-1:2014. The contents of each of the obtained branched C16 to C18 fatty acid compositions are shown in Table 1 below.

[0137] [Table 1] 1.2 Preparation of the Polyol Ester Mixture According to the Invention Branched C18 fatty acid compositions ISA1 and ISA3 were esterified with trimethylolpropane (trimethylolpropane flakes from Perstorp) to form triesters and pentaerythritol (Voxtar M40 from Perstorp) to form tetraesters, respectively.

[0138] The esterification reaction was carried out until the acid number was constant and the hydroxyl number was less than 5 mg KOH / g. The acid number was measured according to standard AOCS Cd 3D-63 and the hydroxyl number according to standard D1957.

[0139] After filtration over dicalite (0.5% by weight), excess isostearic acid was removed by distillation.

[0140] Example 2: Comparative mixtures of polyol esters of branched C18 fatty acids 2.1 Preparation of Comparative Mixtures of Polyol Esters of Branched C18 Fatty Acid Compositions The esterification of three branched C18 fatty acid compositions C1 (Radiacid 5909 from Oleon), C2 (Radiacid 0909 from Oleon) and C3 (prepared from high oleic sunflower oil and fatty acids obtained from a bentonite clay catalyst as described in Example 1 of WO 2019 / 215054), which are not suitable for the present invention, was carried out according to the method described in Example 1.2 using trimethylolpropane and pentaerythritol as polyols.

[0141] [Table 2] Example 3: Viscosity, flash point and pour point of blends of polyol esters 3.1 Measurement of kinematic viscosity The kinematic viscosity at 40° C. was measured according to standard ASTM D445. The results obtained for each mixture of polyol esters of branched C18 fatty acid composition are summarized in Table 3 below. [Table 3] As described above, a polyol ester mixture containing at least 80 mass% of a polyol ester of a branched C18 fatty acid having a higher content of mono-branched fatty acids than poly-branched fatty acids and a low content of cyclic compounds has a low kinematic viscosity.

[0142] 3.2 Measurement of dynamic viscosity The dynamic viscosity was measured according to the ISO 2884-2 standard. The results obtained for each mixture of polyol esters of branched C18 fatty acids are summarized in Table 4 below. [Table 4] As described above, a polyol ester mixture containing at least 80% by mass of polyol esters of branched C18 fatty acids, which has a higher content of mono-branched than poly-branched fatty acids and a low content of cyclic compounds (2.7% by mass for ISA1 and 19.5% by mass for C2), has a low dynamic viscosity.

[0143] 3.2 Flash point and pour point measurements The flash point was measured according to standard ASTM D92.

[0144] The pour point was measured according to the standard ASTM D97 standard.

[0145] The results obtained for each mixture of polyol esters of branched C18 fatty acids are summarized in Table 5 below. [Table 5] It can be seen that the flash points of the polyol esters of branched C18 fatty acids are similar (eg, less than 10% difference) regardless of the content of the branched C18 fatty acid composition.

[0146] The pour points of the polyol esters of branched C18 fatty acids are also similar, except for the C3 pour point, which is lower than the others due to the specific branched C18 fatty acid composition as taught in WO 2019 / 215054.

[0147] Example 4: Cosmetics containing polyol isostearate 4.1 Lipstick The chemicals and their amounts are listed in Table 6 below.

[0148] To prepare the lipstick, Phase A was prepared by adding all ingredients to a main beaker and heating at 80° C. until a clear solution was obtained.

[0149] Phase B was prepared in a separate beaker by stirring the pigment and pearlizing agent with the emollient until a uniform paste was obtained.

[0150] Phase B was added to Phase A and the heat was turned off.

[0151] After the temperature had decreased to 50°C, the ingredients of Phase C were added to the mixture of Phase A+B.

[0152] The resulting mixture was poured into specific molds and then left at 4°C for 15 minutes.

[0153] After reaching room temperature, the lipstick was demolded.

[0154] [Table 6] To compare the effect of the lipstick according to the invention (L1), three comparative lipsticks were prepared: CL1 is a lipstick in which the mixture of polyol esters according to the invention has been replaced by natural film-forming and water-resistant polymers (Polyester-7 (and) neopentyl glycol diheptanoate, Lexfilm SUN from Inolex). - CL2 is a lipstick control that does not contain a mixture or polymer of polyol esters of branched C18 fatty acids, but contains more glyceryl triethylhexanoate (20% by weight). CL3 is a lipstick prepared using a comparative mixture of polyol esters of branched C18 fatty acids (trimethylolpropane triisostearate from C2) instead of the mixture of polyol esters according to the invention. CL4 is a lipstick prepared using a comparative mixture of polyol esters of branched C18 fatty acids (pentaerythritol tetraisostearate of C2 origin) instead of the mixture of polyol esters according to the invention.

[0155] 4.2 Film formation To evaluate the film-forming properties of the different lipsticks prepared in Example 4.1, a film of the lipstick was applied to a cup covered with Kraft paper and the evaporation of water therefrom was measured.

[0156] The covered cup was kept in a 40°C oven for 48 hours.

[0157] The moisture content was measured, and the difference in the moisture content before and after 2 days in the oven is shown in Table 7 as a loss rate (%).

[0158] [Table 7] It can be observed that lipsticks L1 and L2 according to the invention have the lowest water loss of 11.89% and 12.02%, respectively. It can be concluded that lipsticks containing these mixtures of branched C18 fatty acids and polyol esters show better film-forming properties than the other lipsticks, even better than the lipstick obtained using a polymer known to form a film (CL1, water loss 16.62%).

[0159] 4.3 Water resistance To evaluate the water resistance of the lipstick prepared in Example 4.1, the solubility of the lipstick in water was measured.

[0160] Each lipstick was applied to a pre-weighed (WO) sheet of white cotton fabric, which was then immersed in a beaker of water and stirred for 30 minutes.

[0161] Each cotton sheet was then kept at 80°C for 24 hours.

[0162] The cotton sheet was then weighed (W24) and the percentage of lipstick remaining on the cloth is shown in Table 8 below.

[0163] [Table 8] It can be seen that lipsticks L1 and L2 according to the invention remain on the cotton fabric in a higher percentage, which means that these lipsticks exhibit better water resistance than the other lipsticks.

[0164] 4.4 Hardness A needle probe penetration test was performed to measure the hardness of the lipsticks. The method for testing the hardness of lipsticks is adapted from standard ASTM D1321-10, using a 2 mm needle probe (TA39). Before testing, each lipstick was centered under the needle probe to facilitate their penetration. The measurements were performed under the following conditions: - Test type: Compression - Preload test speed: 1.0mm / s - Test speed: 10mm / s - Post-test speed: 10.0 mm / s - Target value: 5mm - Trigger Force: 5g (0.049N)

[0165] Hardness measurements were repeated three times for each lipstick, and the average hardness values ​​obtained are summarized in Table 9 below.

[0166] [Table 9] The lipstick according to the present invention exhibits a higher hardness than other lipsticks. By comparing the hardness of L1 (1.437) with that of CL3 (0.671) and that of L2 (1.235) with that of CL4 (0.731), an increase in hardness of at least 30% can be observed. The use of a mixture of polyol esters of branched C18 fatty acids in cosmetics can improve the hardness of the product.

Claims

1. 1. A mixture of polyol esters of branched C18 fatty acids, said mixture being obtainable by esterifying a branched C18 fatty acid composition with a polyol, said composition comprising: - at least 80% by weight of mono-branched and poly-branched C18 fatty acids, wherein the mass ratio mono-branched C18 fatty acids / poly-branched C18 fatty acids is greater than 1; - maximum 15% by weight of straight-chain fatty acids; and - at most 10% by weight of cyclic compounds; Here, weight percent is based on the weight of the composition.

2. 2. The mixture of polyol esters of claim 1, wherein the amount of the straight chain fatty acid is up to 10% by weight based on the weight of the composition.

3. 3. The mixture of polyol esters according to claim 1 or 2, wherein the amount of the cyclic compounds is up to 8% by weight based on the weight of the composition.

4. 4. The mixture of polyol esters according to claim 1, wherein the amount of mono-branched C18 fatty acids is at least 45% by weight, preferably at least 50% by weight, based on the weight of the composition.

5. 1. A method for preparing a mixture of polyol esters of branched C18 fatty acids, comprising esterifying a branched C18 fatty acid composition with a polyol; The method wherein the branched C18 fatty acid composition comprises: - at least 80% by weight of mono- and poly-branched C18 fatty acids, with a mono-branched C18 fatty acid / poly-branched C18 fatty acid weight ratio of more than 1; - maximum 15% by weight of straight-chain fatty acids; and - at most 10% by weight of cyclic compounds; wherein the weight percentages are based on the weight of the branched C18 fatty acid composition.

6. 6. The method of claim 5, further comprising preparing the branched C18 fatty acid composition from a starting material, wherein the starting material comprises at least 80% linear monoethylenically unsaturated C18 fatty acids based on the total weight of the starting material, and wherein the preparation comprises the steps of: i) isomerizing the linear unsaturated C18 fatty acid by heating in the presence of a zeolite catalyst having an orthorhombic framework structure with one-dimensional linear channels of 10-membered rings or with a two-dimensional channel system of 10-membered rings intersected by 8-membered rings; ii) separating the monomer fraction from the oligomeric fraction formed in step i); iii) purifying the monomer fraction to obtain the branched C18 fatty acid composition.

7. Use of a mixture of polyol esters according to any one of claims 1 to 4 in a lubricant composition.

8. Use of the mixture of polyol esters according to any one of claims 1 to 4 in cosmetic products.

Images