Method for synthesising bio-based solid fats

Abstract

The invention relates to a method for preparing a mixture of linear alkanes of natural origin, preferably of plant origin, comprising the steps of: i) metathesis of at least one terminal linear olefin having from 5 to 24 carbon atoms, derived from at least one fatty acid or fatty acid ester of natural origin, preferably of plant origin, in the presence of a non-isomerising olefin metathesis catalyst, whereby a first mixture of internal olefins (I) is obtained; ii) isomerising metathesis of the mixture of internal olefins (I) obtained in step i) in the presence of a catalyst or a mixture of catalysts, whereby a second mixture of internal olefins (II) is obtained; and iii) hydrogenation of the mixture of internal olefins (II) in the presence of a catalyst, whereby a mixture (III) of linear alkanes of natural origin is obtained.

Description

[0001] Description

[0002] Title: Process for the synthesis of bio-sourced solid fatty substances

[0003] Technical field

[0004] The present description relates to a process for preparing a mixture of linear alkanes of natural origin, in particular of plant origin, in the form of a solid fatty substance, in particular a wax or a pasty mixture. It also relates to the mixtures of linear alkanes capable of being obtained by this process and their use in the fields of cosmetics, pharmaceuticals, coatings, inks, varnishes, paper, adhesives, candles, plastics, rubbers and / or food products.

[0005] Prior art

[0006] Paraffins, also known as mineral waxes, are hydrocarbon compounds derived from petroleum refining. Consisting of various alkanes with a wide range of chain lengths between 18 and 60 carbon atoms, paraffins are substances with a solid to semi-solid consistency at room temperature. They are generally characterized by a melting point between 40 and 90°C, excellent oxidation and temperature stability, odor neutrality, and clarity.

[0007] Synthetic waxes are synthetic products obtained from petroleum derivatives. These include polymers or silicone waxes, which generally have a high melting point. These properties make them highly sought-after products for many applications such as the manufacture of matches, candles, paper, adhesives, paints, pharmaceuticals, and cosmetics.

[0008] However, the mineral and synthetic waxes or paraffins currently available on the market pose problems in terms of environmental friendliness and safety.

[0009] Indeed, mineral paraffins, including MOSH (mineral oil saturated hydrocarbons) and / or MOAH (mineral oil aromatic hydrocarbons) are suspected of toxicity, particularly carcinogenic effects, so that regulations now require their concentration in food products to be limited.

[0010] Furthermore, due to their origin, mineral paraffins contribute negatively to the increase in anthropogenic carbon dioxide. In addition, they are not biodegradable and induce bioaccumulation in the environment.

[0011] This is why many sectors are looking for eco-friendly, biodegradable, and sustainable alternatives to mineral and synthetic paraffins. So-called natural waxes, of plant or animal origin, such as beeswax, candelilla wax, or carnauba wax, offer a renewable alternative to mineral paraffins.

[0012] However, in many applications, natural waxes cannot completely replace mineral or synthetic paraffins.

[0013] Scientific work has recently investigated the possibility of substituting mineral paraffins in lipstick formulations with mixtures of lipids of natural origin, in this case a mixture of linear C35-C38 alkenones, derived from algal resources. However, low stabilities were observed (Huynh, A. et al. Evaluation of alkenones, a renewably sourced, plant-derived wax as a structuring agent for lipsticks. Int. J. Cosmet. Sci. 42, 146-155 (2020)).

[0014] Other scientific work has recently shown that in the field of lipsticks, the substitution of synthetic waxes of petroleum origin by waxes of plant origin poses problems of product stability, strength of the lipstick, exudation, incompatibilities and / or oxidation, with which increasingly demanding consumers are not ready to deal (de Clermont-Gallerande et al. Substitution of synthetic waxes by plant-based waxes in lipsticks, OCL, 2022, 29, 19).

[0015] Thus, this study shows that when the composition obtained with vegetable waxes is solid, it has hardness values ​​that are too low, which results in breakages during application that are too frequent in the case of sticks.

[0016] Furthermore, stability over time is not satisfactory. This can result in the appearance of exudation, polymorphism, a change in the appearance of the product surface: appearance of inhomogeneities in appearance, with the presence of matt surface area(s), or film-coated area(s), or even a change in sensoriality upon application over time (reduction in melting, slipperiness).

[0017] Furthermore, natural vegetable waxes with a high melting point, i.e. around 80°C, do not allow for sufficiently sensory textures to be obtained: they are very rigid, lack flexibility and the sensation when applied to the skin or lips is unpleasant. Finally, vegetable waxes with a melting point below 80°C do not allow for sufficient structure in the composition to be used to mold lipsticks into sticks.

[0018] There is therefore a real need to find substitute products of natural origin, particularly plant-based, ecological and sustainable to replace mineral paraffins.

[0019] Abstract A process has now been developed for preparing a mixture of linear alkanes of natural origin, particularly plant-based, in the form of a solid fatty substance, whose physicochemical characteristics, particularly hardness, texture, and / or melting point, are very close to those of existing mineral paraffins.

[0020] Thus, according to a first aspect, the invention relates to a process for preparing a mixture of linear alkanes of natural origin, preferably of plant origin, comprising the steps of: i) Metathesis of at least one terminal linear olefin, comprising between 5 and 24 carbon atoms, derived from at least one fatty acid or fatty acid ester of natural origin, preferably of plant origin, in the presence of a non-isomerizing olefin metathesis catalyst, whereby a first mixture of internal olefins (I) is obtained; ii) Isomerizing metathesis of the mixture of internal olefins (I) obtained in step i) in the presence of a catalyst or a mixture of catalysts, whereby a second mixture of internal olefins (II) is obtained, and iii) Hydrogenation of the mixture of internal olefins (II) in the presence of a catalyst, whereby a mixture (III) of linear alkanes of natural origin is obtained.

[0021] Surprisingly, the inventors were able to observe that the process made it possible to obtain, in a very reproducible manner and with good yields, mixtures of linear alkanes characterized by a very controlled distribution of chain lengths.

[0022] Then, very advantageously, the inventors were able to show that by varying the composition of the starting mixture of terminal olefins, in particular the chain length of these olefins, and / or their relative proportion within the mixture, the process made it possible to control this distribution and therefore the physicochemical characteristics of the mixture obtained, in particular the melting point of the mixture obtained. Thus, starting from an equimolar mixture of terminal olefins, the process makes it possible to obtain an alkane mixture having a symmetrical chain length distribution, i.e. a Gaussian distribution. Furthermore, the inventors were able to observe that the greater the proportion of short chain within the starting mixture of terminal olefins, the more the Gaussian distribution will shift towards smaller alkane chains (positive asymmetric distribution).Conversely, the greater the proportion of long chains in the mixture, the more the Gaussian distribution will shift towards larger alkane chains (negative asymmetric distribution).

[0023] Very advantageously, the process thus makes it possible to access mixtures of linear alkanes of natural origin having a melting point which can vary to a large extent, in particular from 32°C to 90°C measured by differential scanning calorimetry (DSC). These mixtures can in particular be in the form of a wax or a pasty compound.

[0024] According to another aspect, the invention relates to a mixture of linear alkanes of natural origin, in particular of plant origin, said mixture being capable of being obtained according to the process of the invention.

[0025] According to another aspect, the invention relates to a mixture of linear alkanes of natural origin, in particular of plant origin, in particular in the form of a solid fatty substance, in which: each linear alkane constituting the mixture comprises between C8 and C90 carbon atoms, in particular between C10 and C85 carbon atoms, better still between 10 and 75 carbon atoms, preferably between 10 and 70 carbon atoms, even more preferably between 24 and 60 carbon atoms, and the distribution of the numbers of each linear alkane, arranged by increasing number of carbon atoms, is: o increasing between the linear alkane having the smallest number of carbon atoms up to the mode of the distribution; and o decreasing between the mode of the distribution and the linear alkane having the largest number of carbon atoms, the numbers being calculated as a percentage by weight relative to the total weight of the mixture of linear alkanes of natural origin.

[0026] The said distribution of numbers can in particular be characterized by its extent, defined as the difference between the maximum value and the minimum value of the distribution. It has a value that is always positive and all the greater as the values ​​of the series are spread out.

[0027] For the purposes of this application, the extent is defined as the difference between the number of carbon atoms of the linear alkane having the largest number of carbon atoms and the number of carbon atoms of the linear alkane having the smallest number of carbon atoms.

[0028] The range thus defined can be measured by gas chromatography (GC), which makes it possible to determine the length of the linear alkanes in the distribution, including the length of the smallest alkane and the largest alkane. A person skilled in the art is able to adapt parameters such as the column dimension, the nature of the stationary phase, the measurement temperature, etc., in order to determine the nature of the alkanes present in the reaction mixture. In particular, a person skilled in the art is able to adapt the experimental conditions of gas chromatography in order to determine the smaller and larger alkanes present in the mixture. The larger the range, the broader the distribution that characterizes the mixture of linear alkanes. Vice versa, the smaller the range, the narrower the distribution that characterizes the mixture of linear alkanes.

[0029] According to a preferred embodiment, the mixture of linear alkanes according to the invention is characterized by a range greater than 15, preferably greater than 20. The range may, in addition, preferably be less than 60, more preferably less than 55.

[0030] The extent of the distribution which characterizes the mixture of linear alkanes according to the present invention is linked to the extent of the melting range of said mixture.

[0031] The term "melting range" is used because the mixture of alkanes obtained by means of the claimed method is a set of several alkanes having a different chain length and, consequently, different melting points. In the case of a mixture of alkanes, the endothermic melting peak observed with a differential scanning calorimetry (DSC) analysis is characterized by an "onset point" and an "endset point" corresponding, respectively, to the temperature at which melting begins to be observed and to the temperature at which melting of the mixture is complete.

[0032] The inventors were able to demonstrate that a narrower distribution of chain lengths in the mixture of alkane, as for example described in the prior art, results in a narrower melting range and that, conversely, the wider distribution of chain lengths in the mixture of alkane described in the present application results in a wider melting range.

[0033] The Examples of the present application demonstrate that, thanks to the process according to the invention, it is possible to obtain waxes having a significant melting range, measured as the difference between the "endset point" and the "onset point", which reflects the extent of the distribution of the alkane.

[0034] In a preferred embodiment, the wax is characterized by a melting point of 79.6°C, and the melting range by an “onset point” of 55.2°C and an “endset point” of 90.7°C.

[0035] According to another preferred embodiment, the wax is characterized by a melting point of 48.9°C, and the melting range by an “onset point” of 36.3°C and an “endset point” of 56.8°C.

[0036] According to another preferred embodiment, the wax is characterized by a melting point of 75.2°C, and the melting range an “onset point” of 66.9°C and an “endset point” of 79.2°C.

[0037] According to another preferred embodiment, the wax is characterized by a melting point of 68.5°C, and the melting range by an “onset point” of 56.8°C and an “endset point” of 75.1°C. According to another preferred embodiment, the wax is characterized by a melting point of 74°C, and the melting range by an “onset point” of 32°C and an “endset point” of 86.4°C.

[0038] The present invention differs from the processes known in the prior art which do not make it possible to obtain mixtures of linear alkanes characterized by a Gaussian distribution. For example, patent application WO 2021 / 183330 A1 discloses a two-step process based on an isomerizing metathesis step followed by a step of hydrogenation of the internal olefins obtained by metathesis. The mixture of linear alkanes obtained at the end of these two steps is not characterized by a Gaussian distribution (see in particular Comparative Example 16 reproducing Example 4 of WO 2021 / 183330 A1 and the associated [Fig. 21]). Furthermore, the distributions that characterize the mixtures described in application WO 2021 / 183330 A1 have a span of 8 carbon atoms between the larger linear alkane and the smaller linear alkane.Such a range is therefore significantly narrower than that of the distributions of linear alkanes obtained by the implementation of the present invention.

[0039] The inventors were able to show that obtaining a mixture of linear alkanes characterized by a Gaussian distribution, in particular having a significant range of at least 15 carbon atoms, makes it possible to faithfully reproduce the characteristics of synthetic waxes available on the market, and thus allow the substitution of synthetic waxes with biosourced waxes. Indeed, the use of mixtures of linear alkanes not having Gaussian distributions, and in particular having a narrow range, as a substitute for synthetic waxes in cosmetic compositions does not make it possible to reproduce all of the properties of synthetic waxes, and can lead to various problems during their formulation such as gelation of the composition and / or inhomogeneous crystallization on the surface.

[0040] The specificity of the process according to the present invention lies in the combination of a first non-isomerizing metathesis step, followed by an isomerizing metathesis step before the hydrogenation step. As demonstrated by the inventors in Comparative Example 16, it is thanks to the addition of an intermediate isomerizing metathesis step that the process according to the invention makes it possible to achieve a Gaussian distribution, in particular one with a significant extent.

[0041] This effect is all the more unexpected since it is known in the state of the art to seek to avoid or reduce any isomerization reaction during metathesis in order to maximize the yield of the product of interest. Several documents in the state of the art describe technical solutions for avoiding or reducing any isomerization reaction. This is the case, for example, of the publication by Butilkov D. et al. entitled "Jojoba oil olefin metathesis: a valuable source for bio-renewable materials" (Green Chemistry, vol. 16, no. 11, 2014, pp. 4728-4733). This publication describes strategies to avoid or minimize the isomerizing metathesis reaction which takes place, for example, when the catalyst degrades under the extreme conditions of the reaction.It is therefore to the credit of the inventors to have implemented a second step of isomerizing metathesis, whereas the prior art teaches to avoid any isomerization during the metathesis, in order to obtain a Gaussian distribution of linear alkanes, and in particular presenting a significant extent, rich in linear alkanes having different chain lengths.

[0042] Particularly advantageously, and unlike the prior art, the inventors were able in particular to develop a mixture of linear C24 to C60 alkanes, of natural origin, in the form of a wax, having physicochemical characteristics very close to those of a synthetic mineral wax, commonly used in the field of lipsticks. In particular, the inventors were able to show that the wax obtained according to the process is compatible with the oils commonly used in the field of cosmetics and that it makes it possible to obtain lipsticks having a texture, hardness and stability comparable to those obtained for a lipstick including mineral paraffins used in the field.

[0043] More generally, these mixtures of linear alkanes make it possible in particular to obtain compositions, in particular anhydrous and solid compositions, and more particularly in stick form, whose physicochemical properties are similar to those obtained with analogous compositions prepared from mineral wax(es) in terms of hardness, sensoriality and stability over time while being free of mineral and / or synthetic waxes. They also make it possible to obtain mascara compositions (emulsions of waxes in water) which provide volume to the eyelashes similar to that obtained with analogous compositions prepared from mineral wax(es) while being free of mineral and / or synthetic waxes.

[0044] Particularly advantageously, by the sequence of two successive selective metathesis steps, one non-isomerizing and the other isomerizing, the process according to the present invention makes it possible to obtain mixtures of linear alkanes having sufficiently high melting points (very close to the melting points of synthetic waxes), using as reactant terminal olefins having shorter chains (i.e. having a number of carbon atoms equal to or less than 20) compared to the olefins used in the processes known from the state of the art. The shorter terminal olefins have the advantage of being less expensive compared to longer olefins. The process according to the present application makes it possible, for example, to obtain C24 to C60 alkanes from terminal olefins having a number of carbon atoms between 16 and 20 (Example 1, [Fig.8]), thus reproducing in particular the melting points of the synthetic waxes of interest at a lower cost.

[0045] According to yet another aspect, the invention relates to a composition comprising a mixture of linear alkanes according to the invention.

[0046] According to yet another aspect, the invention relates to the use of a mixture of linear alkanes according to the invention, in the field of cosmetics, pharmaceuticals, coatings, inks, varnishes, paper, adhesives, candles, plastics, rubbers and / or food products.

[0047] The features set out in the following paragraphs may, optionally, be implemented independently of each other or in combination with each other.

[0048] The process according to the invention may comprise the following additional characteristics: the non-isomerizing olefin metathesis catalyst in step i) is chosen from transition metal complexes, in particular transition metal alkylidenes, in particular ruthenium; the non-isomerizing olefin metathesis catalyst is chosen from Ru-1 a, Ru-1 b or a mixture thereof;

[0049] [Chem 1]

[0050] Ru-1b the catalyst or mixture of catalysts used in step ii) is a transition metal complex, in particular ruthenium; the olefin isomerizing metathesis catalyst is a mixture of Ru-2 and Ru-3

[0051] [Chem 3]

[0052] Ru-3 the terminal olefins used in step i) are prepared from fatty acid esters derived from jojoba oil; said at least one terminal linear olefin used in step i) is a mixture of at least two distinct terminal linear olefins each comprising between 5 and 24 carbon atoms, in particular between 16 and 24 carbon atoms, preferably between 16 and 20 carbon atoms; said at least two terminal linear olefins differ from each other by a number of carbon atoms of at least two; said at least one terminal linear olefin used in step i) is a mixture of three terminal linear olefins, preferably C6 / C7 / C8, C8 / C9 / C10, C10 / C12 / C14, or C16 / C18 / C20, this mixture being able in particular to comprise: o 0.5 to 10%, preferably 1 to 10%, even more preferably 1 to 5% of C16 terminal olefins;o 45 to 55%, preferably 45 to 52.5%, even more preferably 45 to 49.5% of C18 terminal olefins; and o 45 to 55%, preferably 45 to 52.5%, even more preferably 45 to 49.5% of C20 terminal olefins; the percentages being expressed in moles relative to the total molar weight of the mixture of terminal olefins.;

[0053] Generally speaking, the higher the proportion of short chain length (C16) terminal linear olefins in the mixture, the lower the melting point of the alkane mixture obtained at the end of the two metathesis steps and the hydrogenation step will be. Thus, the person skilled in the art will choose the composition of the terminal linear olefin mixture so as to obtain the desired melting point for the final alkane mixture.

[0054] The mixture of linear alkanes of natural origin according to the invention which can be obtained according to the process of the invention may comprise at least two distinct linear alkanes, said at least two distinct linear alkanes each comprising between 8 and 90 carbon atoms, in particular between 10 and 85 carbon atoms, preferably between 10 and 75 carbon atoms, better still between 10 and 70 carbon atoms and even more preferably between 24 and 60 carbon atoms. The mixture of linear alkanes of natural origin, in particular of plant origin, in particular in the form of a solid fatty substance, according to the invention may further comprise one or more of the following additional characteristics: each linear alkane in the distribution differs by a number of carbon atoms equal to one from the consecutive linear alkane in the distribution; each linear alkane constituting the mixture comprises between 24 and 60 carbon atoms;the mode of the distribution is between 40 and 45 carbon atoms; the median of the distribution is between 40 and 45 carbon atoms; the mixture has a melting point between 75 and 85°C; the mixture is characterized in that: o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 15 and 19 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 42 and 46; or o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 20 and 24 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56; or where the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 10 and 14 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 45 and 49;or where the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 48 and 52;or o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56, or o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 16 and 20 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 63 and 67, or o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 13 and 17 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 66 and 70, or o the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 19 and 23 and the linear alkane with the highest carbon number has a number of carbon atoms between 49 and 53.;

[0055] The composition comprising a mixture of linear alkanes according to the invention may further comprise and / or be characterized by one or more of the following additional characteristics: comprising less than 3% by weight, in particular less than 1% by weight, preferably free of solid fatty substances of mineral and / or synthetic origin, the percentages by weight being expressed relative to the total weight of the composition; characterized in that it is a cosmetic or pharmaceutical composition, the cosmetic composition being able to be in particular a perfuming, care or makeup product for the skin, mucous membranes or superficial body growths; characterized in that it is an anhydrous composition; characterized in that it is a solid composition; characterized in that it is a solid composition in stick form; characterized in that it is a mascara composition.

[0056] Brief description of the drawings

[0057] Other characteristics, details and advantages will appear on reading the detailed description below, and on analyzing the attached drawings, in which:

[0058] Fig. 1

[0059] [Fig. 1] schematically represents the process according to the invention, which corresponds to a targeted sequential catalytic process leading to a mixture of alkanes from terminal olefins. The reaction conditions are as follows: (i) metathesis: Ru-1 a / Ru-1 b 3 / 7 (0.3 mol%), THF (9M), 75°C, 2 days; (ii) isomerization / metathesis: Ru-2 (0.5 mol%), Ru-3 (1 mol%), MeOH (100eq / cat), THF (1.3M), 75°C, 2h; (iii) hydrogenation: H2 (1 bar), Pd / C (0.4% wt Pd / substrate), cyclohexane (0.2g / mL), 50°C, 16h.

[0060] Fig. 2

[0061] [Fig. 2] schematically represents a process for obtaining a mixture of terminal olefins from esters of saturated and unsaturated fatty acids.

[0062] Fig. 3

[0063] [Fig. 3] schematically represents an example of a process for obtaining C16, C18 and C20 terminal olefins, respectively. The reaction conditions are as follows: preparation of the Grignard reagent: Alkyl bromide (1.5 eq), Mg (3 eq), I2 (0.1 mol%), THF (1.3M), 0°C to 20°C, 1 h; cross-coupling: CuCh (2 mol%), 1-phenylpropyne (10 mol%), THF (0.9M), 0°C to 20°C, 1.5 h; Yields: C16 (1.7g; 77%); C18 (2.3g, 90%; 63.5g, 91%); C20 (9.9g, 99%; 69.5g, 99%). Fig. 4

[0064] [Fig. 4] represents the cross metathesis step according to step i) of the process of the invention, from a specific mixture of C16, C18 and C20 terminal linear olefins, according to example 1. The reaction conditions are as follows: starting terminal olefins: C16 (0.01 eq), C18 (0.495 eq), C20 (0.495 eq); metathesis: Ru-1 a / Ru-1 b 3 / 7 (0.3 mol%), THF (9M), 75°C, 2 days.

[0065] Fig. 5

[0066] [Fig. 5] represents the isomerizing metathesis step according to step ii) of the process of the invention, from a specific mixture of terminal linear olefins in C16, C18 and C20, used in step i). The reaction conditions are as follows: Ru-2 (0.5 mol%), Ru-3 (1 mol%), MeOH (100eq / cat), THF (2.4M), 75°C, 15h.

[0067] Fig. 6

[0068] [Fig. 6] represents the GC analysis of the internal olefin mixture obtained in step ii) of Example 1 from a specific mixture of C16, C18 and C20 terminal linear olefins, implemented in step i), according to Example 1.

[0069] Fig. 7

[0070] [Fig. 7] represents the hydrogenation step according to step iii) of the process according to the invention. The reaction conditions are as follows: H2 (1 bar), Pd / C (0.4% wt Pd / substrate), cyclohexane (0.2g / mL), 50°C, 16h.

[0071] Fig. 8

[0072] [Fig. 8] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a specific mixture of terminal linear olefins in C16, C18 and C20 (C16 (0.01 eq), C18 (0.495 eq), C20 (0.495 eq)), used in step i), according to example 1.

[0073] Fig. 9

[0074] [Fig. 9] schematically represents the ethenolysis reaction of jojoba oil leading to dec-1-ene, according to example 2. The reaction conditions are as follows: ethenolysis: ethylene (10 bar), Ru-4 (100 ppm), 40°C, 6h.

[0075] Fig. 10

[0076] [Fig. 10] represents the process of the invention from dec-1-ene according to example 2: (i) metathesis: Ru-1 a / Ru-1 b 3 / 7 (0.3 mol%), THF (1 M), 75°C, 4 days; (ii) isomerization / metathesis: Ru-2 (0.5 mol%), Ru-3 (1 mol%), MeOH (100eq / cat), THF (0.7M), 75°C, 2h; (iii) hydrogenation: H2 (1 bar), Pd / C (0.4% wt Pd / substrate), cyclohexane (0.2g / mL), 50°C, 6h. [Fig. 11] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from dec-1-ene carried out in step i), according to example 2.

[0077] Fig. 12

[0078] [Fig. 12] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a specific mixture of terminal linear olefins in C16, C18 and C20 (Ci6 (0.01 eq), Cia (0.495 eq), C20 (0.495 eq)) used in step i), according to example 3.

[0079] Fig. 13

[0080] [Fig. 13] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a specific mixture of terminal linear olefins in C6, C7 and C8 (Ce (0.33 eq), C7 (0.33 eq), Ce (0.33 eq)) according to example 4.

[0081] Fig. 14

[0082] [Fig. 14] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a specific mixture of terminal linear olefins in C8, C9 and C10 (Ce (0.33 eq), C9 (0.33 eq), C10 (0.33 eq)) according to example 5.

[0083] Fig. 15

[0084] [Fig. 15] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a specific mixture of terminal linear olefins in C10, C12 and C14 (C10 (0.33 eq), C12 (0.33 eq), C14 (0.33 eq)) according to example 6.

[0085] Fig. 16

[0086] [Fig. 16] schematically represents a process for obtaining a mixture of terminal olefins from jojoba oil. The reaction conditions are as follows: isomerization: Fe(CO)5 (50 mol%), hexane (0.1 M), UV lamps (2 x λ = 365nm), 24 h, 50°C, pyridine (20eq / cat); ethenolysis: ethylene (20 bar), Ru-4 (0.5 mol%), 40°C, 16 h.

[0087] Fig. 17

[0088] [Fig. 17] schematically represents a process for obtaining a mixture of terminal olefins from erucic acid ester (methyl erucate). The reaction conditions are as follows: isomerization: Fe(CO)5 (10 mol%), hexane (0.04 M), UV lamps (2 x λ = 365nm), 7 h, 50°C, pyridine (20eq / cat); ethenolysis: ethylene (20 bar), Ru-4 (0.3 mol%), 40°C, 16 h.

[0089] Fig. 18

[0090] [Fig. 18] represents the CPG analysis of the mixture of linear alkanes obtained in step iii) from a mixture of terminal linear olefins obtained by isomerization then ethenolysis of jojoba oil used in step i), according to example 14. Fig. 19

[0091] [Fig. 19] represents the GC analysis of the mixture of linear alkanes obtained in step iii) from a mixture of terminal linear olefins obtained by isomerization then ethenolysis of methyl erucate used in step i), according to example 15.

[0092] Fig. 20

[0093] [Fig. 20] schematically represents the process of Example 4 of application WO 2021 / 183330 A1.

[0094] Fig. 21

[0095] [Fig. 21] represents the CPG analysis of the mixture of linear alkanes obtained using the method according to Example 4 of application WO 2021 / 183330 A1 and the general diagram of which is specified in [Fig. 20],

[0096] Detailed description

[0097] The invention is now described in more detail and in a non-limiting manner in the following description. Unless otherwise indicated, all percentages relating to quantities are percentages by mass.

[0098] For the purposes of this description, the term "mineral wax" means a refined or semi-refined product obtained from the processing and refining of crude oil, consisting mainly of saturated hydrocarbons. This includes a paraffin or a microcrystalline wax.

[0099] For the purposes of this description, the term "synthetic wax" means a wax synthesized from hydrocarbons derived from petroleum refining. These are mainly polymers of fossil (petrochemical) origin. Examples include polyolefin waxes synthesized from the polymerization of ethylene (polyethylene wax), propylene (propylene wax) and other monomers of fossil origin.

[0100] For the purposes of this description, the term "terminal linear olefin" means a linear hydrocarbon chain comprising in particular from 5 to 24 carbon atoms and one or two double bonds at the end of the hydrocarbon chain ((-CH=CH2)). Thus, the terminal linear olefin is an alpha-olefin having the formula (C n iH2ni+i)CH=CH2 or CH2=CH(Cn2H2n2)CH=CH2 where n1 is an integer between 4 and 22 and n2 is an integer between 1 and 5.

[0101] For the purposes of this description, the term "linear alkanes of natural origin" means alkanes that have been obtained from biomass, and in particular from plants, and which therefore comprise carbon of renewable origin. Unlike ingredients derived from fossil materials, ingredients derived from renewable raw materials contain 14 C. All carbon samples taken from living organisms (animals or plants) are in fact a mixture of 3 isotopes: 12 C (representing ~ 98.892%), 13 C (~ 1.108%) and 14 C (traces: 1,2.10 12 %). The report 14 C / 12 C of living tissues is identical to that of the atmosphere. In the environment, the 14 C exists in two main forms: in mineral form, i.e. as carbon dioxide (CO2), and in organic form, i.e. as carbon integrated into organic molecules.

[0102] In a living organism, the ratio 14 C / 12 C is kept constant by metabolism because carbon is continually exchanged with the environment. The proportion of 14 C being constant in the atmosphere, it is the same in the organism, as long as it is alive, since it absorbs this 14 C as it absorbs the 12 C. The average ratio of 14 C / 12 It is equal to 1.2x10 -12 .

[0103] THE 12 It is stable, that is, the number of atoms of 12 C in a given sample is constant over time. The 14 C, itself, is radioactive (each gram of carbon in a living being contains enough isotope 14 C to give 13.6 disintegrations per minute) and the number of such atoms in a sample decreases over time (t) according to the law: n = no exp(-at) in which:

[0104] - no is the number of 14C at the origin (at the death of the creature, animal or plant),

[0105] - n is the number of 14C atoms remaining after time t,

[0106] - a is the decay constant (or radioactive constant); it is related to the half-life.

[0107] The half-life (or period) is the time at the end of which any number of radioactive nuclei or unstable particles of a given species is reduced by half by disintegration; the half-life T1 / 2 is related to the decay constant a by the formula aTi / 2= In 2. The half-life of the 14 C is worth 5730 years.

[0108] Considering the half-life (T1 / 2) of the 14 C, it is considered that the content of 14 It is constant from the extraction of animal or plant raw materials to the manufacture of the formulation, and even until the end of its use.

[0109] The applicant considers that the mixture of linear alkanes is of natural origin, i.e. derived from renewable raw materials if it contains at least 20% by mass of C of renewable origin on the total mass of carbon, preferably at least 50% by mass of C of renewable origin on the total mass of carbon, more preferably at least 80% by mass of C of renewable origin on the total mass of carbon, even more preferably at least 90% by mass of C of renewable origin on the total mass of carbon, this percentage being preferably measured according to the ASTM D 6866 standard. In other words, an alkane is derived from renewable raw materials if it contains at least 0.2.10' 10 % by mass of 14 C, preferably 0.6.10' 1 °% by mass of 14 C.

[0110] Currently, there are at least two different techniques for measuring the content of 14 C of a sample:

[0111] - By liquid scintillation spectrometry: This method consists of counting 'Beta' particles resulting from the disintegration of the 14 C: We measure the Beta radiation from a sample of known mass (number of atoms 12 C known) for a certain time. This 'radioactivity' is proportional to the number of atoms of 14 C, which can thus be determined. The 14 C present in the sample emits B- radiation, which on contact with the scintillating liquid (scintillator) give rise to photons. These photons have different energies (between 0 and 156 Kev) and form what is called a spectrum of 14 C. According to two variants of this method, the analysis is carried out either on the CO2 previously produced by the carbon sample in a suitable absorbent solution, or on the benzene after prior conversion of the carbon sample into benzene.

[0112] - By mass spectrometry: The sample is reduced to graphite or CO2 gas, analyzed in a mass spectrometer. This technique uses an accelerator and a mass spectrometer to separate the ions 14 C of 12 C and therefore determine the ratio of the two isotopes.

[0113] All these methods of measuring the content of 14 C of materials are described precisely in ASTM D 6866 standards (especially D6866-06) and in ASTMD 7026 standards (especially 7026-04). These methods measure the ratio 14 C / 12 C of a sample and compare it with the ratio 14 C / 12 C of a reference sample of 100% renewable origin, to give a relative percentage of C of renewable origin in the sample.

[0114] The measurement method preferably used in the case of the mixture of linear alkanes of the invention is mass spectrometry described in standard ASTM D6866-06 (“accelerator mass spectroscopy”).

[0115] For the purposes of the present invention, the term "fatty substance" means any oily organic substance, comprising at least one carbon chain comprising at least 11 carbon atoms, and whose solubility in water at 25°C (1 atm) is less than 0.1% by weight.

[0116] The “solid fatty substances” preferably have a melting point greater than or equal to 35°C and / or have a viscosity at a temperature of 40°C and under a shear rate of 1 S' 1, greater than or equal to 1 Pa.s., in particular ranging from 1 Pa.s to 1,000,000 Pa.s and preferably from 10 to 1,000 Pa.s. The viscosity measurements can be carried out at a temperature of approximately 40°C, on a Carri-Med CSL2-500. The solid fatty substances according to the invention can be crystallized, amorphous or pasty. The melting point preferably ranges from 35 to 250°C and more particularly from 40 to 150°C. The melting points can be measured by differential scanning calorimetry (DSC), in particular with a temperature rise rate of 10°C / min. The melting point is then the temperature corresponding to the peak of the endothermic melting peak obtained during the measurement.

[0117] The prior art describes mixtures of linear alkanes having the same melting points as commercially available synthetic waxes.

[0118] However, measuring the melting point is not sufficient to characterize all the physicochemical properties of waxes.

[0119] This is because, as stated above, mixtures of linear alkanes are complex mixtures, in which each alkane has different physicochemical properties.

[0120] It is to the credit of the inventors to have developed a process making it possible to obtain mixtures of linear alkanes reproducing not only the melting point but all the physicochemical properties of synthetic waxes available on the market such as their melting range, hardness, exudation, stability, etc.

[0121] The solid fatty substance according to the invention may in particular be a wax or a pasty fatty substance.

[0122] A "wax", within the meaning of the present invention, is a lipophilic compound, solid at room temperature (approximately 25°C), with a reversible solid / liquid state change, having a melting point above approximately 40°C and up to 200°C, and having an anisotropic crystalline organization in the solid state. Generally speaking, the size of the wax crystals is such that the crystals diffract and / or scatter light, giving the composition comprising them a more or less opaque cloudy appearance. By bringing the wax to its melting temperature, it is possible to make it miscible with oils and to form a microscopically homogeneous mixture, but by bringing the temperature of the mixture back to room temperature, a recrystallization of the wax is obtained in the oils of the mixture, detectable microscopically and macroscopically (opalescence). In the definition of waxes, we can cite for example PDDorgan, Drug and Cosmetic Industry, December 1983, pp. 30-33.

[0123] For the purposes of the present invention, the term "pasty fatty body" means a lipophilic fatty compound with a reversible solid / liquid state change having an anisotropic crystalline organization in the solid state, and comprising at a temperature of 23°C a liquid fraction and a solid fraction.

[0124] In other words, the starting melting temperature of the pasty fatty substance may be less than 23°C. The liquid fraction of the pasty fatty substance measured at 23°C may represent 9 to 97% by weight of the pasty fatty substance. This liquid fraction at 23°C preferably represents between 15 and 85%, more preferably between 40 and 85% by weight.

[0125] For the purposes of the invention, the melting temperature corresponds to the temperature of the most endothermic peak observed in thermal analysis (DSC) as described in standard ISO 1 1357-3; 1999. The melting point of a pasty fatty substance can be measured using a differential scanning calorimeter (DSC), for example the calorimeter sold under the name “MDSC 2920” by the company TA Instruments.

[0126] The measurement protocol is as follows:

[0127] A 5 mg sample of pasty fatty substance placed in a crucible is subjected to a first temperature rise from -20°C to 100°C, at a heating rate of 10°C / minute, then is cooled from 100°C to -20°C at a cooling rate of 10°C / minute and finally subjected to a second temperature rise from -20°C to 100°C at a heating rate of 5°C / minute. During the second temperature rise, the variation in the difference in power absorbed by the empty crucible and by the crucible containing the sample of pasty fatty substance as a function of temperature is measured. The melting point of the pasty fatty substance is the temperature value corresponding to the top of the peak of the curve representing the variation in the difference in power absorbed as a function of temperature.

[0128] The liquid fraction by weight of the pasty fat at 23°C is equal to the ratio of the enthalpy of fusion consumed at 23°C to the enthalpy of fusion of the pasty fat. The enthalpy of fusion of the pasty fat is the enthalpy consumed by the latter to pass from the solid state to the liquid state. The pasty fat is said to be in the solid state when its entire mass is in crystalline solid form. The pasty fat is said to be in the liquid state when its entire mass is in liquid form.

[0129] The enthalpy of fusion of the pasty fatty substance is equal to the area under the curve of the thermogram obtained using a differential scanning calorimeter (DS C), such as the calorimeter sold under the name MDSC 2920 by the company TA instrument, with a temperature rise of 5 or 10 °C per minute, according to the ISO 11357-3:1999 standard.

[0130] The enthalpy of fusion of the pasty fat is the amount of energy required to transform the pasty fat from the solid state to the liquid state. It is expressed in J / g.

[0131] The enthalpy of fusion consumed at 23°C is the amount of energy absorbed by the sample to pass from the solid state to the state it presents at 23°C consisting of a liquid fraction and a solid fraction.

[0132] The liquid fraction of the pasty fatty substance measured at 32°C preferably represents from 30 to 100% by weight of the pasty fatty substance, preferably from 50 to 100%, more preferably from 60 to 100% by weight of the pasty fatty substance. When the liquid fraction of the pasty fatty substance measured at 32°C is equal to 100%, the temperature at the end of the melting range of the pasty fatty substance is less than or equal to 32°C.

[0133] The liquid fraction of the pasty fat measured at 32°C is equal to the ratio of the enthalpy of fusion consumed at 32°C to the enthalpy of fusion of the pasty fat. The enthalpy of fusion consumed at 32°C is calculated in the same way as the enthalpy of fusion consumed at 23°C.

[0134] The olefin metathesis reaction is a well-known reaction in organic chemistry. This reaction, which takes place in the presence of a suitable catalytic system, consists of the exchange of alkylidene groups between two olefins according to the following equations:

[0135] 1. First case, called "self metathesis" or "homometathesis" (i.e. metathesis of an olefin molecule on a molecule of the same olefin):

[0136] [Chem 5]

[0137] 2. Second case, called "cross-metathesis" (i.e. metathesis between two different olefins):

[0138] [Chem 6]

[0139] The olefin metathesis reaction is a balanced reaction. It can occur in the presence of a wide variety of catalysts, most commonly based on transition metals from groups IVA to VIII, including tungsten, molybdenum, rhenium, and ruthenium, either in a homogeneous or heterogeneous phase.

[0140] By "isomerizing metathesis" is meant an olefin metathesis reaction which is carried out in the presence of metal hydrides resulting either a) from the intrinsic decomposition of the metathesis catalyst or b) from a metal hydride catalyst added to the reaction medium; the action of which is to isomerize the double bond(s) present in the starting compound and / or in the product resulting from the metathesis reaction. A "distribution" is generally a function which associates a frequency of occurrence with a class of values. In this case, as used in the present description, this term refers to the distribution of the chain lengths of the linear alkanes constituting the mixture obtained by the process, or in other words, to the distribution of the number of carbon atoms of the linear alkanes constituting this mixture. Thus, each linear alkane of the mixture is associated with its number, in particular with its percentage by weight relative to the total weight of the mixture.The analysis of this distribution can be carried out in particular by means of gas chromatography (GC), possibly coupled with mass spectrometry (GC-MS).

[0141] This distribution is characterized in particular by the central values, namely the mode, the median and the mean.

[0142] The mode or dominant value corresponds to the most frequent value in the distribution. In this case, it corresponds to the linear alkane most represented in the mixture, and therefore for which the weight content in the mixture is maximum.

[0143] With chain lengths listed in ascending order, the median is the chain length that divides the sample into two equal subsets: 50% of the alkanes have chain lengths greater than the median, and 50% have values ​​lower than the median.

[0144] The average is the sum of the values ​​divided by the number of elements.

[0145] When these three central values ​​are combined (mode = mean = median), the distribution is called normal or Gaussian. The graphical representation of this distribution forms a bell-shaped curve, symmetrical with respect to the mean.

[0146] This distribution can also present an asymmetry, positive or negative.

[0147] When the distribution is positively skewed, the tail of the distribution extends further towards the upper side of the mean than towards the mean. In other words, there are more extreme values ​​on the upper side of the mean. The tail on the lower side is shorter.

[0148] Conversely, when the distribution is negatively skewed, the tail of the distribution is longer on the lower side of the distribution than the mean. There are more extreme values ​​on the lower side, and the tail on the upper side is shorter.

[0149] These types of asymmetric distributions are characterized by a measure called skewness, which quantifies the degree of asymmetry. A zero skew corresponds to a perfectly symmetric distribution, while a positive or negative skew indicates skewness on the respective side. Process for the preparation of a mixture of naturally occurring linear alkanes

[0150] According to a first aspect, the invention relates to a process for preparing a mixture of linear alkanes of natural origin, preferably of plant origin, comprising the steps of: i) Metathesis of at least one terminal linear olefin comprising between 5 and 24 carbon atoms, derived from at least one fatty acid or fatty acid ester of natural origin, preferably of plant origin, in the presence of a non-isomerizing olefin metathesis catalyst, whereby a first mixture of internal olefins (I) is obtained; ii) Isomerizing metathesis of the mixture of internal olefins (I) obtained in step i) in the presence of a catalyst or a mixture of catalysts, whereby a second mixture of internal olefins (II) is obtained, and iii) Hydrogenation of the mixture of internal olefins (II) in the presence of a hydrogenation catalyst, whereby a mixture (III) of linear alkanes of natural origin is obtained.

[0151] Step i) of metathesis

[0152] The non-isomerizing olefin metathesis catalyst in step i) may consist of a single catalyst or a mixture of non-isomerizing olefin metathesis catalysts. It may in particular be chosen from transition metal complexes, in particular transition metal alkylidenes, in particular ruthenium, or mixtures thereof.

[0153] According to a particular embodiment, the non-isomerizing metathesis catalysts of step i) described above are selective non-isomerizing catalysts in that they prevent the isomerization of terminal olefins.

[0154] As a result, the process according to the present invention is further distinguished from certain processes of the prior art such as the process described in patent application WO 2021 / 183330 A1 which, on the contrary, is based on the use of metathesis catalysts which are non-selective because they are isomerizing. Isomerizing catalysts such as those described in patent application WO 2021 / 183330 A1 are well known in the prior art.

[0155] Preferably, the ruthenium catalyst is chosen from [Ru-1 a], [Ru-1 b] or a mixture thereof. The catalyst may in particular be used in the form of a mixture of Ru-1 a and Ru-1 b, in particular in a Ru-1 a / Ru-1 b weight ratio of between 1 and 2, in particular 3 / 7. [Chem 1]

[0156] Ru-1a

[0157] Ru-1 aa for chemical formula: C51H59CI2N4RU and for molecular mass: 900.03 g. mol -1 .

[0158] [Chem 2]

[0159] Ru-1 b

[0160] Ru-1 ba for chemical formula: C51H67CI2N2PRU and for molecular mass: 911.05 g. mol -1 .

[0161] The quantity of catalyst can vary between 0.01 and 1.0 mol%, in particular between 0.1 and 0.5 mol% relative to the mixture of terminal linear olefins used in step i).

[0162] Step i) is carried out in particular at a temperature between 70°C and 90°C, under an inert atmosphere. It is carried out in particular in a polar and aprotic solvent, for example THF.

[0163] The mixture may be stirred until the at least one terminal olefin is completely converted, which may be monitored by proton NMR. The mixture may thus be stirred until the terminal olefin protons have completely disappeared, for example for 1 to 3 days, in particular for two days.

[0164] At the end of step i), the catalyst can be neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture.

[0165] Preferably, the metathesis catalyst is removed, for example by silica gel chromatography and / or filtration.

[0166] The non-isomerizing selective catalysts make it possible in particular to control the mixture of internal olefins which is obtained at the end of step i) and, in particular, to obtain internal olefins at the end of step i) having longer chains, which makes it possible to avoid additional distillation steps to remove the internal olefins having shorter chains. Step ii) of isomerizing metathesis of olefins

[0167] Step ii) is carried out from the selective and controlled mixture of internal olefins obtained in step i) described above.

[0168] The isomerizing metathesis step can be carried out in the presence of a single catalyst or a mixture of at least two catalysts.

[0169] When a single catalyst is used, it is chosen from catalysts capable of carrying out both an olefin isomerization and an olefin metathesis reaction. These include transition metal alkylidenes, in particular ruthenium, tungsten or molybdenum. As an example, the Ru-2 catalyst described below may be mentioned.

[0170] When a mixture of catalysts is used, said mixture may comprise a first catalyst for carrying out olefin metathesis and a second catalyst for carrying out only olefin isomerization. The catalyst for carrying out olefin isomerization may be chosen from transition metal-based catalysts, in particular palladium, ruthenium, copper, or iron. For example, the isomerization catalysts may be chosen from a palladium catalyst (CAS: 185812-86-6) and a ruthenium catalyst [RuH(CI)(CO)(PCy3)3] or [CpRu(PN)(MeCN)]BArF4. Alternatively, the mixture may comprise two catalysts, both capable of carrying out both olefin isomerization and an olefin metathesis reaction. Such catalysts may be chosen from transition metal alkylidenes, in particular ruthenium, tungsten or molybdenum.Examples include the Ru-2 and Ru-3 catalysts described below.

[0171] This type of catalyst or mixture of catalysts is notably described in the article: LJ Goopen et al. Chem. Eur. J. 2019, 25, 7416 - 7425.

[0172] Preferably, the catalyst or mixture of catalysts used in step ii) is or comprises a transition metal complex, in particular ruthenium.

[0173] Preferably, the isomerizing metathesis catalyst is a mixture of Ru-2 and Ru-3 catalysts. Preferably the Ru-2 / Ru-3 molar ratio varies from 0.1 to 1 and is in particular 0.5.

[0174] [Chem 3]

[0175] Ru-2 Ru-2 has the chemical formula: C52H77CI2N2PRU, for molar mass: 933.15 g. mol -1 , and for CAS reference: 373640-75-6.

[0176] [Chem 4]

[0177] Ru-3

[0178] Ru-3 has the chemical formula: C39H50CI2F3N3O2RU, for molar mass: 821.81 g. mol -1 and for CAS reference: 1212008-99-5.

[0179] The amount of catalyst can vary between 0.01 and 2 mol%, in particular between 0.1 and 1 mol% relative to the mixture of internal olefins used in step ii).

[0180] Step ii) is carried out in particular at a temperature between 70°C and 90°C, under an inert atmosphere. It is carried out in particular in a polar and aprotic solvent, for example THF.

[0181] The reaction mixture in step ii) may be stirred until the internal olefin mixture from step i) is completely converted, which may be monitored by proton NMR. The mixture may thus be stirred for 1 to 3 hours, in particular for 2 hours.

[0182] At the end of step i), the catalyst can be neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture of step ii).

[0183] Preferably, the metathesis catalyst is removed, for example by silica gel chromatography and / or filtration.

[0184] Step iii) hydrogenation

[0185] The hydrogenation step can be carried out in the presence of a palladium-on-carbon catalyst, in particular at a temperature between 40°C and 60°C, in an apolar aprotic solvent, such as cyclohexane.

[0186] It is carried out in the presence of dihydrogen, for example under a pressure of 1 bar.

[0187] The reaction mixture from step iii) can be stirred until the complete conversion of the mixture of internal olefins from step ii), which can be monitored by proton NMR. The reaction mixture in step iii) can thus be stirred for several hours, in particular for 10 to 20 hours. It can include a filtration step to remove the catalyst at the end of the reaction.

[0188] Naturally occurring linear terminal olefins

[0189] The origin of the terminal olefins used in step i) can be varied. Indeed, the terminal olefins can be synthesized from unsaturated fatty acid esters derived from vegetable oils or fatty esters derived from jojoba oil, according to methods known to those skilled in the art. In this regard, reference may be made in particular to the following publications: JE Moore et al. / Journal of Colloid and Interface Science 547 (2019) 275-290; J. Terao et al. Angew. Chem. Int. Ed. 2007, 46, 2086-2089, Y. Fujimoto et al., Org. Biomol. Chem. 2016, 14, 6672; Angelici et al. J. Org. Chem. 1996, 61, 7784-7792).

[0190] For example, these terminal olefins can be obtained by an ethenolysis reaction involving esters of unsaturated fatty acids derived from vegetable oils, preferably unsaturated fatty esters derived from jojoba oil [Fig. 9]. An ethenolysis catalyst is used. These include transition metal alkylidenes, especially ruthenium. For example, the Ru-4 catalyst described below can be mentioned.

[0191] [Chem 7]

[0192] Ru-4

[0193] Ru-4 has the chemical formula C33H42CI2NORU, with a molar mass of 639.67 g / mol.

[0194] Ru-4 is notably described in the article: Sytniczuk et al., Chem Catalysis 3, 100713.

[0195] The amount of catalyst can vary between 0.001 and 1 mol%, especially between 0.01 and 0.5 mol% relative to jojoba oil.

[0196] The ethenolysis reaction is carried out at a temperature between 35°C and 45°C, particularly at 40°C.

[0197] The ethenolysis reaction is carried out in an autoclave in the presence of ethylene (99.95% purity), for example under a pressure of 10 bar.

[0198] The mixture can then be stirred for 4 to 8 hours, in particular for 6 hours. At the end of the ethenolysis reaction, the catalyst is neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture.

[0199] The conversion of the ethenolysis reaction can be quantified by GC using an internal standard, trimethoxybenzene.

[0200] Advantageously, the terminal olefins used in step i) are obtained according to a process comprising at least the following two steps: a) Isomerization of a carboxylic acid and / or a mixture of carboxylic acids and / or a carboxylic acid ester and / or a mixture of carboxylic acid esters in the presence of an acid catalyst or a metal complex, preferably iron carbonyl complexes, preferably iron pentacarbonyl; b) Ethenolysis of the reaction product from step a) in the presence of a ruthenium catalyst in order to obtain a mixture of terminal olefins.

[0201] This process makes it possible to synthesize the terminal olefins used in step i) with a reduced number of steps compared to the process known in the art and as described in [Fig. 2], based on the following steps: a) Reduction of a carboxylic acid in order to obtain a primary alcohol, b) Bromination of the primary alcohol from step a) in order to obtain a bromoalkane, c) Reaction of the bromoalkane from step b) with magnesium in order to obtain an organomagnesium halide, d) Cross-coupling between the organomagnesium halide from step c) and a terminal bromoalkene in order to obtain a mixture of terminal olefins.

[0202] In embodiments, said at least one terminal linear olefin used in step i) is a mixture of at least two distinct terminal linear olefins, in particular three distinct terminal olefins, each comprising between 5 and 24 carbon atoms, in particular between 16 and 24 carbon atoms, preferably between 16 and 20 carbon atoms.

[0203] The distinct terminal linear olefins necessarily differ from each other by a carbon number of at least one. Step i) is then a cross metathesis step.

[0204] In embodiments, said at least two terminal linear olefins differ from each other by a carbon number of at least one, in particular at least two.

[0205] According to a preferred embodiment, said at least one terminal linear olefin used in step i) is a mixture of three terminal linear olefins, preferably C16 / C18 / C20.

[0206] In particular, a mixture of terminal linear olefins comprising or consisting of: From 0.5 to 10%, preferably from 1 to 10%, even more preferably from 1 to 5% of C16 terminal olefins will be used;

[0207] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C18 terminal olefins; and

[0208] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C20 terminal olefins;

[0209] The percentages are expressed in moles relative to the total molar weight of the terminal olefin mixture.

[0210] Mixture of naturally occurring linear alkanes

[0211] According to another aspect, the invention relates to a mixture of linear alkanes of natural origin, in particular of plant origin, said mixture being capable of being obtained according to the process of the invention.

[0212] According to embodiments, the mixture comprises at least two distinct linear alkanes, said at least two distinct linear alkanes each comprising between 8 and 90 carbon atoms, in particular between 10 and 85 carbon atoms, preferably between 10 and 75 carbon atoms, even better between 17 and 70 carbon atoms, even more preferably between 24 and 60 carbon atoms.

[0213] According to yet another aspect, the invention relates to a mixture of linear alkanes of natural origin, in particular of plant origin, in the form of a solid fatty body, in which: each linear alkane constituting the mixture comprises between 8 and 90 carbon atoms, in particular between 10 and 85 carbon atoms, preferably between 10 and 75 carbon atoms, better still between 10 and 70 carbon atoms, even better still between 17 and 70 carbon atoms, even more preferably between C24 and C60, and the distribution of the numbers of each linear alkane, arranged by increasing number of carbon atoms, is: o increasing between the linear alkane having the smallest number of carbon atoms up to the mode of the distribution; and decreasing between the mode of distribution and the linear alkane having the highest carbon number, the numbers being calculated as a percentage by weight relative to the total weight of the mixture of linear alkanes of natural origin.

[0214] According to embodiments, each linear alkane in the distribution differs from the consecutive linear alkane in the distribution by a carbon number equal to one. For example, in the case of a distribution where the smallest number of carbon atoms is C16, and where the largest number of atoms is C20, then the distribution includes the following alkanes: C16, C17, C18, C19 and C20. According to embodiments, the number of distinct linear alkanes constituting the mixture is at least 10, in particular at least 20, in particular at least 30, in particular at least 40. According to embodiments, the mixture has a melting point between 32°C and 90°C. The melting point is in particular determined by DSC thermogravimetric analysis.

[0215] The alkane having the smallest or largest number of atoms is in particular an alkane whose weight percentage represents at least 1% by weight relative to the total weight of the mixture of linear alkanes. Below this threshold, any linear alkanes present will be considered to be present in trace amounts and will not be considered to be part of the distribution. For example, a mixture of alkanes according to the present application in the form of a C16-C20 distribution, that is to say where the smallest number of carbon atoms is C16, and where the largest number of atoms is C20, may possibly contain C14, C15, C21, or C22 alkanes but their respective concentration by weight will be less than 1% by weight of the total mixture.

[0216] This threshold value of 1% by weight is set in particular in relation to a sample whose concentration is at least 100pg / mL, analyzed by Gas Chromatography (GC), with a Shimadzu GC-2014 device with an Agilent VF-5ht column having the following characteristics: 30m X 0.25mm X 0.1 Opm, maximum temperature: 430°C, or in particular with a Shimadzu GC-2030 device with a Restek MXT-1 HT SimDist column having the following characteristics: 5m X 0.53mm X 0.1 Opm, maximum temperature: 450°C.

[0217] According to embodiments, each linear alkane constituting the mixture comprises between 20 and 65 carbon atoms. In the context of the present description, this means in other words that the linear alkane having the smallest number of carbon atoms within the distribution is a C20 alkane and / or the alkane having the largest number of atoms is a C65 alkane.

[0218] According to embodiments, each linear alkane constituting the mixture comprises between 24 and 60 carbon atoms.

[0219] According to embodiments, the distribution mode is between 40 and 45 carbon atoms, and is in particular 41 carbon atoms.

[0220] According to embodiments, the median of the distribution is between 40 and 45 carbon atoms, and is notably between 41 and 43 carbon atoms.

[0221] According to embodiments, the average of the distribution is between 40 and 45 carbon atoms, and is notably between 41 and 42 carbon atoms.

[0222] According to embodiments, the distribution of linear alkanes is asymmetric. According to embodiments, the mixture has a melting point between 75 and 85°C, of ​​about 80°C.

[0223] Preferably, the mixture of linear alkanes is characterized in that it contains from 3% to 6% by weight of linear C30 to C54 alkanes, relative to the total weight of the mixture.

[0224] According to embodiments, the mixture of linear alkanes is a mixture in which: the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 15 and 19 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 42 and 46; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 20 and 24 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 10 and 14 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 45 and 49;or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 48 and 52; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 16 and 20 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 63 and 67; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 13 and 17 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 66 and 70;or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 19 and 23 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 49 and 53.;

[0225] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 15 and 19 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 42 and 46, and has a melting point of about 49°C.

[0226] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 20 and 24 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 52 and 56, and has a melting point of about 75°C.

[0227] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 19 and 23 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 49 and 53, and has a melting point of about 68.5°C.

[0228] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 10 and 14 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 45 and 49, and has a melting point of about 32°C.

[0229] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 48 and 52, and has a melting point of about 37°C.

[0230] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 52 and 56, and has a melting point of about 58°C.

[0231] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 16 and 20 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 63 and 67, and has a melting point of about 74°C.

[0232] In embodiments, the mixture of linear alkanes constituting the mixture is a mixture in which the linear alkane having the lowest number of carbon atoms has a number of carbon atoms between 13 and 17 and the linear alkane having the highest number of carbon atoms has a number of carbon atoms between 66 and 70, and has a melting point of about 74°C.

[0233] By "about x" we mean the values ​​in the interval from x - 0.1x to x + 0.1x.

[0234] Compositions

[0235] According to yet another aspect, the invention relates to a composition comprising a mixture of linear alkanes according to the invention, in particular a cosmetic and / or pharmaceutical composition. According to embodiments, the compositions according to the invention comprise less than 3% of additional solid fatty substances of mineral and / or synthetic origin, in particular less than 1%. Preferably, the cosmetic compositions are free of additional solid fatty substances of mineral and / or synthetic origin, the percentages being expressed by weight relative to the total weight of the composition.

[0236] Cosmetic composition

[0237] According to yet another aspect, the invention relates to a cosmetic composition comprising a mixture of linear alkanes according to the invention.

[0238] According to embodiments, the cosmetic compositions comprise from 0.1% to 25% by weight of a mixture of linear alkanes according to the invention, relative to the total weight of the composition.

[0239] In particular, when the cosmetic composition is in the form of a cream, in particular a relatively compact one, it may comprise from 0.1% to 5% by weight of a mixture of linear alkane according to the invention, relative to the total weight of the composition.

[0240] When the cosmetic composition is in the form of a product cast in a cup, it may comprise from 0.1% to 12% by weight of a mixture of linear alkanes according to the invention, relative to the total weight of the composition.

[0241] When the cosmetic composition is in the form of a stick, it may comprise from 0.1% to 25% by weight of a mixture of linear alkanes according to the invention, relative to the total weight of the composition.

[0242] When the cosmetic composition is in the form of a mascara, it may comprise from 0.1% to 15% by weight of a mixture of linear alkanes according to the invention, relative to the total weight of the composition.

[0243] The cosmetic composition may be characterized in particular in that it is a care product, a makeup product, or a perfuming product. This product may be intended for the skin (face, eyelids), mucous membranes (in particular the lips) or appendages (eyelashes, eyebrows, hair, nails). Among these products, mention may in particular be made of anhydrous products or products in emulsion form, such as wax-in-water emulsions, water-in-oil emulsions, oil-in-water emulsions or multiple emulsions. It may in particular be a cosmetic composition, preferably anhydrous, in solid form for the care and / or makeup of keratin materials, in particular the skin, eyelids, eyebrows or lips, comprising, in a physiologically acceptable medium, a mixture of linear alkanes according to the invention.By "anhydrous composition" is meant in particular that water is preferably not deliberately added to the composition of the invention but may be present in trace amounts in the various compounds used in the composition. In particular, the composition according to the invention comprises less than 4% by weight of water, preferably less than 3%, preferably less than 2%, more preferably less than 1%, even more preferably less than 0.5% by weight of water, relative to the total weight of said composition, or even is completely free of water. According to a particular embodiment, the composition is free of water. By "composition in solid form" is meant according to the invention a composition having, at a temperature of 20°C and at atmospheric pressure (760 mm Hg), a hardness greater than 30 Nm. -1 , preferably greater than 40 Nm -1. Hardness can be measured at 20°C by the so-called "butter cutter" method, which consists of evaluating the firmness of a lipstick by measuring, in particular, the resistance to cutting the stick product. This measurement is carried out 24 hours after formulation, using a texturometer (TAXTPIus, MicroStable Systems, United Kingdom) equipped with a 5 kg force cell and its Butter Cutter A / BC probe (Swantech, MicroStable Systems, United Kingdom). It allows the maximum resistance force of the stick to be measured when the butter cutter penetrates to a depth of 9 mm at a speed of 1.6 mm / s. To ensure the reproducibility of the measurements, the analysis is repeated on 6 sticks and the relative deviation between the measurements must not be greater than 10%, ideally 5%. For each type of product, a reference (target) range is established to guarantee the mechanical properties of the stick.The solid composition according to the invention will generally have a hardness greater than or equal to 70g, in particular greater than or equal to 90g, for example ranging from 100g to 400g, and preferably ranging from 140g to 300g and even more preferably ranging from 175g to 250g. Such compositions (corresponding in particular to cast sticks in a standard format of approximately 12.7mm), have adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application and is thus compatible with packaging in a stick or in another solid form and with application by friction on the surface to be treated and / or made up; they are also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture. The composition may in particular be in the form of a stick or a composition packaged in a cup.These can also be fluid products such as lip gloss or mascara (wax emulsions in water). They can also be products in the form of loose or compact powders.

[0244] The cosmetic compositions according to the invention may further comprise other ingredients, in particular additional solid fatty substances, in particular polar and / or apolar waxes, or pasty fatty substances.

[0245] By "additional solid fatty substances" is meant here fatty substances distinct from the mixtures of linear alkanes according to the invention. These additional solid fatty substances may in particular be of mineral and / or synthetic origin. According to embodiments, the cosmetic compositions according to the invention comprise less than 3% by weight of additional solid fatty substances of mineral and / or synthetic origin, in particular less than 1% by weight. Preferably, the cosmetic compositions are free of additional solid fatty substances of mineral and / or synthetic origin, the percentages being expressed by weight relative to the total weight of the composition.

[0246] Polar wax means a wax comprising at least one heteroatom such as oxygen, nitrogen, silicon or phosphorus.

[0247] In particular, the polar wax may be chosen from the group comprising beeswax, carnauba wax, candelilla wax, cotton wax, rice bran wax, bay wax, Chinese insect wax, lanolin and its alcohol derivatives, acetylated, esterified, polyethoxylated, kapok wax, sugar cane wax, hexyl laurate, jojoba wax, shellac wax, polyethoxylated cholesterol ether, synthetic beeswaxes marketed by Koster Keunen under the trade name Kester Wax K82H, or a mixture thereof.

[0248] Mention may also be made of plant ester waxes chosen from the group comprising the mixture of jojoba esters, polyglycerin-3, Acacia decurrens flower wax and sunflower seed wax, said mixture being marketed by Gattefosse under the trade name Acticire®, jojoba esters marketed by Floratech under the trade name Floraesters 60 or Floraesters 70, alkyl esters or hydrogenated alkyl esters marketed by Sophim under the trade name Phytowax, such as for example hydrogenated lauroyl oleate esters marketed under the name Phytowax Olive 12L44.

[0249] By "apolar wax" we mean a hydrocarbon wax and / or a silicone wax.

[0250] “Non-polar hydrocarbon wax” means a wax comprising only carbon and hydrogen atoms and not comprising heteroatoms such as oxygen, nitrogen, silicon or phosphorus.

[0251] Examples of apolar hydrocarbon waxes suitable for use in the compositions of the invention include polyethylene wax, such as that marketed by New Phase Technologies under the name Performalene 400 (P400) or by Jeen International Corporation under the name Jeenate 3H, a blend of high molecular weight linear polyethylene and ethylene / propylene copolymer, marketed by Safi-Alcan under the trade name Lipwax® PZ80-20, a synthetic wax such as that marketed by Sasol under the name Sasol Wax C80, blends of synthetic waxes and vegetable waxes, such as, for example, a blend of synthetic wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smart wax 202, a blend of synthetic wax, Candelilla wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smartwax 7743S,Fischer Tropsch waxes such as those marketed by Cirebelle under the name Cirebelle 303, or one of their mixtures, montan wax, ceresins, ozokerites, microcrystalline waxes, mineral paraffins.,

[0252] The term “non-polar silicone wax” means a wax comprising a silicon heteroatom.

[0253] An example of a suitable silicone apolar wax in the compositions of the invention is C24-28 alkyl dimethicone, marketed by Evonik Industries AG under the name Abil Wax.

[0254] The cosmetic compositions according to the invention may comprise an additional pasty fatty substance. A compound of this type is in particular a mixture of sterol esters, such as the mixture of cholesterol and lanosterol ester available from the manufacturer CRODA under the trade name Super Sterol Ester®.

[0255] The compositions according to the invention may further comprise a pasty fatty substance which may advantageously be chosen from: vaselines also called petrolatum, lanolin and its derivatives, polymeric or non-polymeric silicone compounds, polymeric or non-polymeric fluorinated compounds, vinyl polymers, in particular homopolymers and copolymers of olefins, homopolymers and copolymers of hydrogenated dienes, linear or branched oligomers, homo or copolymers of alkyl (meth)acrylates preferably having a C8-C30 alkyl group, homo and copolymeric oligomers of vinyl esters having C8-C30 alkyl groups, homo and copolymeric oligomers of vinyl ethers having C8-C30 alkyl groups, liposoluble polyethers resulting from the polyetherification between one or more C2-C100 diols, preferably C2-C50,mixtures of beeswax and octyldodecanol such as that marketed under the name Zenibee Cream by the company Zenitech, esters, vegetable butters such as mango butter, shea butter, cocoa butter, cotton butter, avocado butter, etc. or a mixture thereof.

[0256] Among the esters, it is possible to use in particular: esters of an oligomeric glycerol, in particular diglycerol esters, in particular condensates of adipic acid and glycerol, for which a part of the hydroxyl groups of the glycerols have reacted with a mixture of fatty acids such as stearic acid, capric acid, stearic acid and isostearic acid and 12-hydroxystearic acid, such as those marketed under the brand name Softisan 649 by the company Sasol, arachidyl propionate marketed under the brand name Waxenol 801 by Alzo, phytosterol esters such as the product corresponding to the INCI name "bis-behenyl / isostearyl / phytosteryl dimer dilinoleyl dimer dilinoleate" marketed under the name Plandool-G by the company Nippon Fine Chemical Co, the " Phytosteryl / behenyl / octyldodecyl / isostearyl lauroyl glutamate » marketed under the name Eldew-PS308 by the company Ajinomoto, fatty acid triglycerides and their derivatives,for example the mixture of stearyl heptanoate and stearyl caprylate marketed under the name DUB solid by the company Stéarinerie Dubois, pentaerythritol esters, non-crosslinked polyesters resulting from the polycondensation between a linear or branched C4-C50 dicarboxylic acid or polycarboxylic acid and a C2-C50 diol or polyol, aliphatic esters of ester resulting from the esterification of an aliphatic hydroxycarboxylic acid ester by an aliphatic carboxylic acid such as cetyl lactate marketed under the name ceraphyl 28 by the company ISP (International Speciality Products), polyesters resulting from the esterification, by a polycarboxylic acid, of an aliphatic hydroxycarboxylic acid ester, said ester comprising at least two hydroxyl groups such as the products Risocast DA-H ®, and Risocast DA-L ®, or a mixture thereof.,

[0257] Among the additional pasty fatty substances, phytosterol esters will preferably be chosen, such as the product with the INCI name "bis-behenyl / isostearyl / phytosteryl dimer dilinoleyl dimer dilinoleate" marketed under the name Plandool-G by the company Nippon Fine Chemical Co, "Phytosteryl / behenyl / octyldodecyl / isostearyl lauroyl glutamate" marketed under the name Eldew-PS308 by the company Ajinomoto, or a mixture of these.

[0258] The compositions may comprise additional fatty substances having a melting point between 25°C and 55°C. The fatty substance having a melting point between 25°C and 55°C is chosen from hydrogenated oils solid at 25°C or fatty esters solid at 25°C and mixtures thereof.

[0259] Among the hydrogenated oils solid at 25°C, we can cite hydrogenated castor oil, hydrogenated palm oil, hydrogenated tallow, hydrogenated coconut oil such as for example that available under the trade name hydrobase 32-34 by the company Prod'Hyg.

[0260] Fatty esters that are solid at 25°C include propylene glycol myristate, myristyl myristate, and cetyl alcohol. The fatty component with a melting point between 25°C and 55°C is preferably hydrogenated coconut oil.

[0261] The cosmetic compositions according to the invention may further comprise a lipophilic gelling agent, or a film-forming polymer.

[0262] Lipophilic gelling agent

[0263] The term “lipophilic gelling agent” designates, in the context of the present application, a substance capable of solidifying or gelatinizing the oil present in the composition of the invention.

[0264] Among the lipophilic gelling agents used, we can cite in particular organic or mineral polymeric or molecular lipophilic gelling agents.

[0265] As an example of a polymeric organic lipophilic gelling agent, mention may be made of esters of sucrose and fatty acids, and preferably esters of sucrose, stearic acid and acetic acid, such as sucrose tetrastearate triacetate (corresponding to the INCI name sucrose tetrastearate triacetate) available under the trade name Sisterna® A10E-C from the company Sisterna.

[0266] Another type of polymeric organic lipophilic gelling agent other than sucrose polyester is dextrin esters. Examples include dextrin fatty acid esters, such as dextrin palmitate.

[0267] Another type of polymeric organic lipophilic gelling agent is glyceryl esters. Examples include the diester of eicosadioic acid and glycerol esterified with behenic acid. It is available under the trade name NOMCORT® HK-G from NISSHIN OILLIO.

[0268] As a mineral lipophilic gelling agent, we can cite fumed silica, possibly hydrophobically treated on the surface, whose particle size is less than 1 μm. It is indeed possible to chemically modify the surface of the silica, by chemical reaction generating a reduction in the number of silanol groups present on the surface of the silica. In particular, silanol groups can be substituted by hydrophobic groups: we then obtain a hydrophobic silica. The hydrophobic groups can be: trimethylsiloxyl groups, which are notably obtained by treating fumed silica in the presence of hexamethyldisilazane. Silicas thus treated are called "Silica silylate" according to the CTFA (8th edition, 2000).They are, for example, marketed under the references Aerosil R812® by the company DEGUSSA, CAB-O-SIL TS-530® by the company CABOT, dimethylsilyloxyl or polydimethylsiloxane groups, which are obtained in particular by treatment of fumed silica in the presence of polydimethylsiloxane or dimethyldichlorosilane. Silicas thus treated are called "Silica dimethyl silylate" according to the CTFA (8th edition, 2000). They are, for example, marketed under the references Aerosil R972®, and Aerosil R974® by the company DEGUSSA, CAB-O-SIL TS-610® and CAB-O-SIL TS-720® by the company CABOT.

[0269] Hydrophobic fumed silica in particular has a particle size that can be nanometric to micrometric, for example ranging from approximately 5 to 200 nm.

[0270] Polymeric organic lipophilic gelling agents are, for example, partially or totally crosslinked elastomeric organopolysiloxanes with a three-dimensional structure, such as those sold under the names KSG6®, KSG16® and KSG18® by the company SHIN-ETSU, Trefil E-505C® and Trefil E-506C® by the company DOW-CORNING, Gransil SR-CYC®, SR DMF10®, SR-DC556®, SR 5CYC gel®, SR DMF 10 gel® and SR DC 556 gel® by the company GRANT INDUSTRIES, SF 1204® and JK 113® by the company GENERAL ELECTRIC; ethylcellulose such as that sold under the name Ethocel® by the company DOW CHEMICAL; galactommanans comprising from one to six, and in particular from two to four, hydroxyl groups per ose, substituted by a saturated or unsaturated alkyl chain, such as guar gum alkylated by C1 to C6, and in particular C1 to C3, alkyl chains or a mixture thereof.Block copolymers of the "diblock", "triblock" or "radial" type of the polystyrene / polyisoprene, polystyrene / polybutadiene type such as those marketed under the name Luvitol HSB® by the company BASF, of the polystyrene / copoly(ethylene-propylene) type such as those marketed under the name Kraton® by the company SHELL CHEMICAL CO or of the polystyrene / copoly(ethylene-butylene) type, mixtures of triblock and radial (star) copolymers in isododecane such as those marketed by the company PENRECO under the name Versagel® such as for example the mixture of butylene / ethylene / styrene triblock copolymer and ethylene / propylene / styrene star copolymer in isododecane (Versagel M 5960) or in hydrogenated polyisobutene (Versagel ME 2000).

[0271] Another type of polymeric organic lipophilic gelling agent is polyamide resins or poly(ester-amide) resins, such as ester-terminated polyamides (ETPA), ester-terminated poly(ester-amides) (ETPEA), tertiary amide-terminated polyamides (ATPA), polyalkyleneoxy-terminated polyamides (PAOPA) or polyether polyamides (PEPA).

[0272] Examples of ester-terminated polyamides (ETPAs) are those identified by the INCI name "Ethylenediamine / Stearyl Dimer Dilinoleate Copolymer" and available, for example, under the trade name Uniclear® 100VG from Arizona Chemical.

[0273] Examples of ester-terminated poly(ester-amides) (ETPEAs) are those identified by the INCI name polyamide-8 which are "Ethylenediamine bis-stearyl ethylenediamine / neopentyl glycol / stearyl dibenzoate dimer copolymers" and available, for example, under the trade name Oloecraft® LP-20-PA-MV from Croda. Examples of tertiary amide terminated polyamides (ATPA) are those identified by the INCI name "Ethylenediamine / Hydrogenated Dimer Diilinoate Copolymer Bis-Di-C14-18 Alkyl Amide" and available, for example, under the trade name Sylvaclear® A200V or Sylvaclear® A2614V from Arizona Chemical or those identified by the INCI name "Diisostearyl malate and bis-dioctadecylamide dimer dilinoleic acid / ethylenediamine" and available, for example, under the trade name Haimalate PAM from Kokyu Alcohol Kogyo.

[0274] Examples of polyalkyleneoxy terminated polyamides (PAOPAs) are those identified by the INCI name Polyamide-3 and available, for example, as Sylvaclear® AF1900V, Sylvaclear® PE1800V and Sylvaclear® PA1200V from Arizona Chemical.

[0275] Examples of polyether polyamides (PEPAs) are those identified by the INCI name Polyamide-6 and available, for example, as Sylvaclear® PE400V from Arizona Chemical. Another type of polymeric organic lipophilic gelling agent is N-acyl glutamic acid diamides. Examples include N-acyl glutamic acid diamide having a straight-chain alkyl group such as dibutyl lauroyl glutamide and N-acyl glutamic acid diamide having a branched-chain alkyl group, such as dibutyl ethylhexanoyl glutamide. Dibutyl lauroyl glutamide is commercially available as GP-1 and dibutyl ethylhexanoyl glutamide is commercially available as EB-21, both marketed by Ajinomoto.

[0276] Among the lipophilic gelling agents, sucrose and fatty acid esters, dextrin esters and glyceryl esters are preferred.

[0277] Filmoqène

[0278] The composition according to the invention may also comprise at least one film-forming polymer.

[0279] Among the film-forming polymers that can be used in the compositions of the present invention, mention may be made of synthetic polymers, of radical type or of polycondensate type, polymers of natural origin, and their mixtures.

[0280] By radical film-forming polymer is meant a polymer obtained by polymerization of monomers with unsaturation, in particular ethylenic unsaturation, each monomer being capable of homopolymerizing (unlike polycondensates).

[0281] The radical-type film-forming polymers may in particular be vinyl polymers or copolymers, in particular acrylic polymers. The vinyl film-forming polymers may result from the polymerization of ethylenically unsaturated monomers having at least one acid group and / or esters of these acid monomers and / or amides of these acid monomers.

[0282] As monomer carrying an acid group, it is possible to use α,β-ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid. Preferably, (meth)acrylic acid, itaconic acid and crotonic acid are used, and more preferably itaconic acid (for example a metal salt of poly(itaconic acid) such as that sold under the commercial reference REVCARE NE 100S by the company Itaconix).

[0283] The acid monomer esters are advantageously chosen from (meth)acrylic acid esters (also called (meth)acrylates), in particular alkyl (meth)acrylates, in particular C1-C30 alkyl, preferably C1-C20 alkyl, aryl (meth)acrylates, in particular C6-C10 aryl, hydroxyalkyl (meth)acrylates, in particular C2-C6 hydroxyalkyl.

[0284] Among the alkyl (meth)acrylates, mention may be made of methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate.

[0285] Among the hydroxyalkyl (meth)acrylates, mention may be made of hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate.

[0286] Among the aryl (meth)acrylates, we can cite benzyl acrylate and phenyl acrylate.

[0287] Particularly preferred esters of (meth)acrylic acid are alkyl (meth)acrylates.

[0288] According to the present invention, the alkyl group of the esters may be either fluorinated or perfluorinated, i.e. some or all of the hydrogen atoms of the alkyl group are substituted by fluorine atoms.

[0289] Examples of amides of acid monomers that may be mentioned include (meth)acrylamides, and in particular N-alkyl (meth)acrylamides, in particular C2-C12 alkyl. Among the N-alkyl (meth)acrylamides, mention may be made of N-ethyl acrylamide, Nt-butyl acrylamide, Nt-octyl acrylamide and N-undecylacrylamide.

[0290] Vinyl film-forming polymers may also result from the homopolymerization or copolymerization of monomers selected from vinyl esters and styrene monomers. In particular, these monomers may be polymerized with acid monomers and / or their esters and / or their amides, such as those mentioned above. Examples of vinyl esters include vinyl acetate, vinyl neodecanoate, vinyl pivalate, vinyl benzoate, and vinyl t-butyl benzoate.

[0291] Examples of styrenic monomers include styrene and alpha-methyl styrene.

[0292] We can also mention styrene / butadiene block copolymers such as products from Kraton, or OLEOFLEX EG 200 from APPLECHEM.

[0293] Among the film-forming polycondensates, we can cite polyurethanes, polyesters, polyester amides, polyamides, and epoxy ester resins, polyureas.

[0294] The polyurethanes may be chosen from anionic, cationic, non-ionic or amphoteric polyurethanes, polyurethane-acrylics, polyurethane-polyvinylpyrrolidones, polyester-polyurethanes, polyether-polyurethanes, polyureas, polyurea-polyurethanes, and mixtures thereof.

[0295] Polyesters can be obtained, in a known manner, by polycondensation of dicarboxylic acids with polyols, in particular diols.

[0296] The dicarboxylic acid can be aliphatic, alicyclic, or aromatic. Examples of such acids include: oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, 2,2-dimethylglutaric acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,5-norbornane dicarboxylic acid, diglycolic acid, thiodipropionic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid. These dicarboxylic acid monomers can be used alone or in combination of at least two dicarboxylic acid monomers. Among these monomers, phthalic acid, isophthalic acid and terephthalic acid are preferably chosen.

[0297] The diol may be chosen from aliphatic, alicyclic, aromatic diols. Preferably, a diol chosen from: ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, cyclohexane dimethanol, 4-butanediol is used. As other polyols, glycerol, pentaerythritol, sorbitol, trimethylol propane may be used.

[0298] Polyester amides can be obtained in a similar way to polyesters, by polycondensation of diacids with diamines or amine alcohols. As diamine, ethylenediamine, hexamethylenediamine, meta- or para-phenylenediamine can be used. As amino alcohol, monoethanolamine can be used. As polyamide resins, mention may also be made of that corresponding to the INCI name DIISOSTEARYL MALATE & BIS DIOCTADECYLAMIDE DIMER DILINOLEIC ACID / ETHYLENE DIAMINE COPOLYMER marketed under the name Haimalate PAM by the company Kokyu alcohol Kogyo.

[0299] The polyester may further comprise at least one monomer carrying at least one -SO3M group, with M representing a hydrogen atom, an ammonium ion NHT or a metal ion, such as for example an Na ion + , Li + , K + , Mg 2+ , That 2+ , Cu 2+ , Fe 2+ , Fe 3+ . In particular, a bifunctional aromatic monomer comprising such a -SO3M group can be used.

[0300] The aromatic nucleus of the bifunctional aromatic monomer further bearing a -SO3M group as described above may be chosen, for example, from benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyldiphenyl, methylenediphenyl nuclei. Examples of bifunctional aromatic monomer further bearing a -SO3M group include: sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid.

[0301] It is possible to use copolymers based on isophthalate / sulfoisophthalate, and more particularly copolymers obtained by condensation of diethylene glycol, cyclohexane dimethanol, isophthalic acid, sulfoisophthalic acid.

[0302] The polymers of natural origin, optionally modified, may be chosen from shellac resin, sandarac gum, gum arabic (ACACIA SENEGAL GUM), dammars, elemis, copals, cellulose polymers, polymers extracted from the fruit of Caesalpinia spinosa and / or the algae Kappaphycus alvarezii (such as the product Filmexel® marketed by the company Silab), and mixtures thereof. A natural polymer such as Filmexel® makes it possible in particular to improve the strength of the film obtained from the composition according to the invention. Mention may also be made of the film-forming polymers corresponding to the INCI name SHOERA ROBUSTA RESIN + BEESWAX, SHOERA ROBUSTA RESIN + SUNFLOWER OIL, ARAUCARIA + SUNFLOWER OIL, ARAUCARIA + CASTOR OIL, SHOERA ROBUSTA + OCTYLDODECANOL. Rosin esters such as glyceryl rosinate available under the trade name NatPure GR from the company Gattefossé can also be mentioned.

[0303] According to one embodiment, the film-forming polymer may be a polymer solubilized in a liquid fatty phase comprising oils or organic solvents (the film-forming polymer is then said to be a liposoluble polymer).

[0304] Examples of liposoluble polymers include copolymers of vinyl ester (the vinyl group being directly linked to the oxygen atom of the ester group and the vinyl ester having a saturated, linear or branched hydrocarbon radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group) and at least one other monomer which may be a vinyl ester (different from the vinyl ester already present), an α-olefin (having from 8 to 28 carbon atoms), an alkyl vinyl ether (the alkyl group of which has from 2 to 18 carbon atoms), or an allylic or methallyl ester (having a saturated, linear or branched hydrocarbon radical of 1 to 19 carbon atoms, linked to the carbonyl of the ester group).

[0305] These copolymers can be crosslinked using crosslinkers which can be either of the vinyl type, or of the allylic or methallyl type, such as tetraallyloxyethane, divinylbenzene, divinyl octanedioate, divinyl dodecanedioate, and divinyl octadecanedioate.

[0306] Examples of such copolymers include vinyl acetate / allyl stearate, vinyl acetate / vinyl laurate, vinyl acetate / vinyl stearate, vinyl acetate / octadecene, vinyl acetate / octadecyl vinyl ether, vinyl propionate / allyl laurate, vinyl propionate / vinyl laurate, vinyl stearate / octadecene-1, vinyl acetate / dodecene-1, vinyl stearate / ethyl vinyl ether, vinyl propionate / cetyl vinyl ether, vinyl stearate / allyl acetate, 2,2-dimethyl vinyl octanoate / vinyl laurate, 2,2-dimethyl allyl pentanoate / vinyl laurate, vinyl dimethyl propionate / vinyl stearate, allyl dimethyl propionate / vinyl stearate, vinyl propionate / vinyl stearate, crosslinked with 0.2% divinyl benzene, vinyl dimethyl propionate / vinyl laurate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecyl vinyl ether, crosslinked with 0.2% tetraallyloxyethane,vinyl acetate / allyl stearate, crosslinked with 0.2% divinyl benzene, vinyl acetate / octadecene-1 crosslinked with 0.2% divinyl benzene and allyl propionate / allyl stearate crosslinked with 0.2% divinyl benzene.,

[0307] Liposoluble film-forming polymers may also include liposoluble copolymers, and in particular those resulting from the copolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the allyl radicals having from 10 to 20 carbon atoms.

[0308] Such liposoluble copolymers may be chosen from copolymers of polyvinyl stearate, polyvinyl stearate crosslinked using divinylbenzene, diallyl ether or diallyl phthalate, copolymers of poly(meth)acrylate of stearyl, polyvinyl laurate, poly(meth)acrylate of lauryl, these poly(meth)acrylates being able to be crosslinked using methylene glycol dimethacrylate or tetraethylene glycol.

[0309] The liposoluble copolymers defined above are known and in particular described in application FR-A-2232303; they can have a weight-average molecular weight ranging from 2,000 to 500,000 and preferably from 4,000 to 200,000. Mention may also be made of liposoluble homopolymers, and in particular those resulting from the homopolymerization of vinyl esters having from 9 to 22 carbon atoms or of alkyl acrylates or methacrylates, the alkyl radicals having from 2 to 24 carbon atoms.

[0310] Examples of liposoluble homopolymers include: polyvinyl laurate and lauryl poly(meth)acrylates, these poly(meth)acrylates being able to be crosslinked using ethylene glycol dimethacrylate or tetraethylene glycol.

[0311] As liposoluble film-forming polymers which can be used in the invention, mention may also be made of polyalkylenes and in particular copolymers of C2-C20 alkenes, such as polybutene, alkylcelluloses with a linear or branched alkyl radical, saturated or not in C1 to C8 such as ethylcellulose and propylcellulose, copolymers of vinylpyrrolidone (VP) and in particular copolymers of vinylpyrrolidone and alkene in C2 to C40 and better in C3 to C20. As an example of a VP copolymer that can be used in the invention, mention may be made of the VP / vinyl acetate copolymer, VP / ethyl methacrylate, butylated polyvinylpyrrolidone (PVP), VP / ethyl methacrylate / methacrylic acid, VP / eicosene (ANTARON V220 marketed by the company Ashland), VP / hexadecene (ANTARON V216 marketed by the company Ashland), VP / triacontene, VP / styrene, VP / acrylic acid / lauryl methacrylate.

[0312] We can also mention dextrin esters and in particular: - dextrin isostearate & isostearic acid marketed under the name UNIFILMA HVY by the company Chiba Flour Milling - dextrin palmitate / ethylhexanoate marketed under the name RHEOPEARL TT by the company Chiba Flour Milling - Dextrin Myristate marketed under the name RHEOPEARL MKL2 by the company Chiba Flour Milling

[0313] We can also mention sugar esters and in particular sucrose acetate isobutyrate marketed under the name EASTMAN SUSTANE SAIB by the company EASTMAN.

[0314] Silicone resins, generally soluble or swellable in silicone oils, which are crosslinked polyorganosiloxane polymers, may also be mentioned. The nomenclature for silicone resins is known as "MDTQ", the resin being described according to the different siloxane monomeric units it comprises, each of the letters "MDTQ" characterizing a type of unit.

[0315] Examples of commercially available polymethylsilsesquioxane resins include those marketed by Wacker under the reference Resin MK, such as Belsil PMS MK, and by SHIN-ETSU under the references KR-220L, or silform flexible resin.

[0316] Examples of siloxysilicate resins include trimethylsiloxysilicate (TMS) resins such as those marketed under the reference SR1000 by General Electric or under the reference TMS 803 by Wacker. Mention may also be made of trimethylsiloxysilicate resins marketed in a solvent such as cyclomethicone, sold under the name “KF-7312J” by Shin-Etsu, “DOWSIL™ RSN-0749”, “DOWSIL™ 593 Fluid” by Dow Corning.

[0317] Mention may also be made of copolymers of silicone resins such as those mentioned above with polydimethylsiloxanes, such as the pressure-sensitive adhesive copolymers marketed by the company Dow Corning under the reference BIO-PSA and described in document US 5,162,410 or even silicone copolymers resulting from the reaction of a silicone resin, such as those described above, and a diorganosiloxane such as described in document WO 2004 / 073626.

[0318] It is also possible to use copolymers with a non-silicone organic skeleton grafted with monomers containing a polysiloxane unit, such as for example butyl acrylate / hydroxypropyl dimethicone acrylate copolymer marketed under the name GRANACRYSIL BAS by the company GRANT.

[0319] Finally, we can mention the acrylate / polytrimethylsiloxymethacrylate copolymers comprising a carbosiloxane dendrimer structure grafted onto a vinyl skeleton commercially available under the references DOWSIL FA 4002 ID or DOWSIL FA 4001 CM.

[0320] It is also possible to use silicone polyamides of the polyorganosiloxane type such as those described in documents US-A-5,874,069, US-A-5,919,441, US-A-6,051,216 and US-A-5,981,680.

[0321] As film formers, natural resins, dextrin esters and rosin esters are preferred.

[0322] In a preferred embodiment, the composition according to the invention comprises from 1 to 15% by weight of a film-forming polymer, preferably 5 to 12% by weight of at least one film-forming polymer.

[0323] Oil

[0324] For the purposes of the present invention, the term "oil" means a compound which is liquid at room temperature (25°C), and which, when introduced at a rate of at least 1% by weight into water at 25°C, is not at all soluble in water, or soluble to a level of less than 10% by weight, relative to the weight of oil introduced into the water.

[0325] Non-volatile oil

[0326] "Non-volatile oil" means an oil which has a boiling point generally above 300°C at 760 mm Hg (101325 Pa) and which has little or no vapor pressure.

[0327] The non-volatile oils may in particular be chosen from non-volatile silicone oils, non-volatile hydrocarbon oils and mixtures thereof. The term “silicone oil” means an oil comprising at least one silicon atom, and in particular at least one Si-O group.

[0328] Examples of non-volatile silicone oils include polydimethylsiloxanes containing at least 8 silicon atoms, polyalkylmethylsiloxanes whose alkyl chain contains 8 to 20 carbon atoms, and oils identified by the INCI name phenyl trimethicone.

[0329] "Hydrocarbon oil" means an oil containing hydrogen and carbon atoms.

[0330] Examples that may be mentioned are hydrocarbons such as squalane, phytosqualane, polybutene, hydrogenated polyisobutene, hydrogenated polydecene, synthetic (poly)esters also called "ester oils" and (poly)ethers, in particular (poly)esters of C6-C20 acids and C6-C20 alcohols, advantageously branched such as isononyl isononanoate; vegetable oils; branched and / or unsaturated fatty acids; branched and / or unsaturated fatty alcohols such as octyldodecanol; or a mixture thereof.

[0331] The term "ester oil" means a mono-, di-, tri- or tetra-ester oil. Ester oils are obtained by reacting a mono-, di-, tri- and more generally a polyol with a mono-, di-, tri- and more generally a polycarboxylic acid, said reactants being able to be linear or branched, saturated or unsaturated, aliphatic or aromatic, and possibly comprising alkoxylated groups. Ester oils can in particular be hydroxylated.

[0332] In particular, the non-volatile ester oil may comprise from 18 to 70 carbon atoms.

[0333] The non-volatile ester oil may in particular be chosen from: monoesters comprising 18 to 40 carbon atoms, in particular monoesters of formula R1 COOR2 in which R1 represents the residue of a linear or branched fatty acid comprising from 6 to 20 carbon atoms and R2 represents a hydrocarbon chain, in particular a branched chain, containing from 6 to 20 carbon atoms, such as, for example, Purcellin oil (cetostearyl octanoate), isononyl isononanoate, isodecyl neopentanoate, C12 to C15 alkyl benzoates, 2-ethylhexyl palmitate, octyldodecyl neopentanoate, 2-octyldodecyl stearate, 2-octyldodecyl erucate, isostearyl isostearate, benzoate 2-octyldodecyl, alkyl octanoates, decanoates or ricinoleates, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, 2-ethylhexyl palmitate, 2-hexyldecyl laurate, 2-octyldecyl palmitate,2-octyldodecyl myristate, 2-diethylhexyl succinate; diesters comprising 18 to 60 carbon atoms, in particular 18 to 50 carbon atoms, such as diesters of dicarboxylic acids and monoalcohols, such as diisostearyl malate; diesters of glycol and monocarboxylic acids, such as neopentyl glycol diheptanoate or polyglyceryl-2 diisostearate; triesters comprising 35 to 70 carbon atoms, such as triesters of tricarboxylic acids, such as triisostearyl citrate or tridecyl trimellitate; or triesters of glycol and monocarboxylic acids such as polyglyceryl-2 triisostearate such as, for example, that available under the trade name Cithrol-PG-32-IS by the company Croda; tetraesters comprising 35 to 70 carbon atoms, such as tetraesters of penthaerythritol or polyglycerol and a monocarboxylic acid, for example pentaerythrityl tetrapelargonate,pentaerythrityl tetraisostearate, pentaerythrityl tetraisononanoate, glyceryl tridecyl-2 tetradecanoate, polyglyceryl tetraisostearate-2 or pentaerythrityl tetradecyl-2 tetradecanoate; polyesters obtained by condensation of dimer and / or trimer of unsaturated fatty acid and diol such as those described in patent application FR 0 853 634, such as the polyester of dilinoleic acid and 1,4-butanediol; esters and polyesters of dimer diol and mono- or dicarboxylic acid, such as esters of dimer diol and fatty acid such as polyglyceryl-2 isostearate / dimer dilinoleate copolymer available under the trade name Hailuscent ISDA-MB by the company Kogyo Alcohol and esters of dimer diols and dimer dicarboxylic acid, in particular those obtained from a dimer of an unsaturated fatty acid in C8 to C34, in particular in C12 to C22, in particular in C16 to C20, and more particularly in C18,such as esters of dilinoleic diacids and dilinoleic diol dimers, for example those marketed by the company NIPPON FINE CHEMICAL under the trade name LUSPLAN DD-DA5® and DD-DA7®; fatty acid triglycerides (liquid at room temperature), in particular fatty acids having 7 to 40 carbon atoms, such as triglycerides of heptanoic or octanoic acids or jojoba oil; saturated triglycerides such as caprylic / capric triglyceride, glyceryl triheptanoate, glycerin trioctanoate; C18-36 acid triglycerides such as those marketed under the reference DUB TGI 24 marketed by Stéarineries Dubois); and unsaturated triglycerides such as castor oil, olive oil, ximenia oil, pracaxi oil; or a mixture thereof.,

[0334] The non-volatile oil used in the present invention may be a glossy oil.

[0335] A "bright oil" is an oil whose refractive index is greater than 1.43, preferably greater than 1.45, even more preferably greater than 1.50.

[0336] The refractive index is measured using an ABBE paralux refractometer ref 60-6400-9. An additional non-volatile oil can also be used to provide additional properties to the composition of the invention.

[0337] For example, diisostearyl malate, or Polyglyceryl-3 diisostearate available under the trade name Cithrol PG32IS by Croda or pentaerythrityl Adipate / Caprate / Caprylate / Heptanoate available under the trade name LEXFEEL 700 EX-LO MB by Inolex can be added because they allow for good dispersion of the pigments. Other additional oils can be added to improve the sensory properties of the formula.According to one embodiment, the non-volatile oil is selected from squalane, octyldodecanol, polyglyceryl-2 tri isostearate, polyglyceryl-10 decaisostearate, pentaerythrityl adipate / caprate / caprylate / heptanoate, dicaprylyl carbonate, octyldodecyl myristate, dimer dilinoleyl dimer dilinoleate, polyglyceryl-2 isostearate / dimer dilinoleate, sorbitan sesquioleate isostearate, polyglyceryl-3 diisostearate, isononyl isononanoate, meadowfoam seed oil, caprylic / capric triglyceride, sunflower oil, dipentaerythrityl tetrahydroxystearate / isostearate, diisostearyl malate, jojoba oil.

[0338] Volatile oil

[0339] According to an advantageous embodiment of the invention, the composition does not contain (0%) or very little (maximum 5% by weight relative to the total weight of the composition) volatile oil.

[0340] By "volatile oil" we mean an oil that is likely to evaporate on contact with the skin in less than one hour, at room temperature and atmospheric pressure.

[0341] The volatile oil is a volatile cosmetic oil, liquid at room temperature, having in particular a non-zero vapor pressure at room temperature and atmospheric pressure, in particular having a vapor pressure of between 0.13 Pa and 40,000 Pa (0.001 to 300 mm Hg), preferably of between 1.3 Pa and 13,000 Pa (0.01 to 100 mm Hg), and more preferably still of between 1.3 Pa and 1,300 Pa (0.01 to 1,000 mm Hg).

[0342] Volatile oils include volatile silicone oils and / or volatile hydrocarbon oils.

[0343] The volatile silicone oils optionally used in the compositions of the invention are linear or cyclic, have in particular from 2 to 7 silicon atoms, optionally alkyl or alkoxy groups having from 1 to 10 carbon atoms, and have a viscosity, at room temperature, of less than 5 cSt.

[0344] Examples of volatile silicone oil that may be mentioned more particularly are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, cyclotetradimethylsiloxane, cyclopentadimethylsiloxane, cyclohexadimethylsiloxane, hexamethyldisiloxane, octamethyltrisiloxane, rhexylheptamethyltrisiloxane, roctylheptamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, heptamethylhexyl trisiloxane, heptamethyloctyl trisiloxane or a mixture thereof.

[0345] Concerning the volatile hydrocarbon oil, we can more particularly cite a short-chain hydrocarbon oil, volatile linear alkanes such as for example described in document FR2933865 incorporated by reference.

[0346] Examples of short-chain hydrocarbon oil(s) include those chosen from the group comprising isododecane, isodecane, isohexadecane, dodecane or one of their mixtures.

[0347] Examples of volatile linear alkanes include those with hydrocarbon chains in:

[0348] C9-C17, C10-C14, such as a mixture of undecane and tridecane, marketed by BASF Care Creations under the name Cetiol® Ultimate,

[0349] C15-19, such as those marketed by Seppic under the name Emogreen L15, C12-14, such as those marketed by Biosynthis under the name Vegelight 1214LC, C9-12 alkane, such as those marketed by Daito under the name Makigreen D10.

[0350] Coloring agent

[0351] The coloring agent may in particular be chosen from water-soluble or fat-soluble dyes, pigments, pearlescent agents, lakes or mixtures thereof.

[0352] These coloring agents may optionally be surface-treated with a hydrophobic agent such as silanes, silicones, fatty acid soaps, C9-15 fluoroalcohol phosphates, acrylate / dimethicone copolymers, mixed C9-15 fluoroalcohol phosphate / silicone copolymers, lecithins, carnauba wax, polyethylene, chitosan, and optionally acylated amino acids such as lauroyl lysine, disodium stearoyl glutamate, and aluminum acyl glutamate. The pigments may be mineral or organic, natural or synthetic.

[0353] Examples of mineral pigments include titanium dioxide, zinc oxide, iron, zinc or chromium oxides, manganese violets, ultramarines, ferric ferrocyanide known as Prussian Blue, as well as composite pigments and goniochromatic, pearlescent, Is interference, photochromic or thermochromic pigments, without this list being limiting. Examples of organic pigments that can be used in the invention include carbon black, D&C type pigments, lakes based on cochineal carmine, barium, strontium, calcium or aluminum or even diketopyrrolopyrrole (DPP) described in documents EP-A-542669, EP-A-787730, EP-A-787731 and WO-A-96 / 08537.

[0354] The pearlescent agents can be chosen from those conventionally present in makeup products, such as mica / titanium dioxide. Alternatively, they can be pearlescent agents based on mica / silica / titanium dioxide, based on synthetic fluorphlogopite / titanium dioxide (SUNSHINE® from MAPRECOS), calcium sodium borosilicate / titanium dioxide (REFLECKS® from ENGELHARD) or calcium aluminum borosilicate / silica / titanium dioxide (RONASTAR® from MERCK). Bismuth oxychloride can also be mentioned.

[0355] Advantageously, when it contains one or more pigments, the composition according to the invention also contains at least one dispersant such as diisostearyl malate.

[0356] The coloring agents are present in the composition in a content of between 0.1% and 15%, the percentages being percentages by weight relative to the total weight of the composition.

[0357] Charges

[0358] These fillers are preferably colorless or white.

[0359] The particles that constitute it can be porous or not, and come in various forms, notably platelet, spherical or oblong, whatever the crystallographic form (for example sheet, cubic, hexagonal, orthorhombic, etc.).

[0360] In particular, the filler may be chosen from cellulose, lauroyl lysine, boron nitride, silicone microbeads such as those marketed under the name Tospearl by Toshiba for example, precipitated calcium carbonate, hydroxyapatite, elastomeric polyorganosiloxane particles, glass or ceramic microcapsules, zinc myristate, magnesium myristate, magnesium stearate, magnesium and aluminum silicate such as that marketed under the trade name Neusilin ULF2 by the company Fuji Chemical Industry, starch, a clay or a mixture thereof.

[0361] Among the fillers we can cite starch, clay or a mixture of them.

[0362] The starch can be chosen, for example, from rice, tapioca, potato or corn starch. Rice starch is preferred, particularly that with the INCI name distarch phosphate marketed under the name "Rice PO4 Natural" by the company Agrana Starch.

[0363] The clay can be natural or synthetic. It is made lipophilic by treatment with an alkyl ammonium salt such as a C10 to C22 ammonium chloride, for example distearyl dimethyl ammonium chloride. It can be chosen from bentonites, in particular hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, and vermiculites. Preferably, the clay is chosen from hectorites. Examples of hectorite include the product sold under the name Bentone 38V CG by the company ELEMENTIS SPECIALTIES (INCI name disteardimonium hectorite) or the product sold under the name Bentone Gel EUG V by the company ELEMENTIS SPECIALTIES.

[0364] Additional Additives

[0365] Apart from the aforementioned constituents, the composition according to the invention may contain various ingredients, such as a UV filter, a vegetable or synthetic butter, a sweetening agent, an antioxidant, a sequestrant, a pH adjuster, a preservative, perfumes, vitamins, moisturizing agents, or a mixture thereof.

[0366] UV filters may in particular be chosen from organic and inorganic filters or a mixture thereof. As organic filters, mention may in particular be made of dibenzoylmethane derivatives (including butyl methoxydibenzoylmethane), cinnamic acid derivatives (including ethylhexyl methoxycinnamate), salicylates, para-aminobenzoic acids, p,p'-diphenylacrylates, benzophenones, benzylidene camphor derivatives, phenylbenzimidazoles, triazines, phenylbenzotriazoles and anthranilic derivatives. As inorganic filters, mention may in particular be made of filters based on mineral oxides in the form of pigments or nanopigments, coated or not, and in particular based on titanium dioxide or zinc oxide.

[0367] The composition according to the invention may also contain one or more sweetening agents such as sorbitol, sucrose, xylitol, acesulfame K and sodium saccharin; antioxidants such as alkylated or phosphorylated esters of ascorbic acid, or tocopherol and its esters; sequestering agents such as EDTA salts; pH adjusters; preservatives; fragrances; vitamins; moisturizing agents; or a mixture thereof.

[0368] Examples of such adjuvants are cited in particular in the CTFA Dictionary (International Cosmetic Ingredient Dictionary and Handbook published by The Cosmetic, Toiletry and Fragrance Association, 11th Edition, 2006).

[0369] Preferably, the cosmetic compositions according to the invention comprise less than 3% by weight of additional solid fatty substances of mineral and / or synthetic origin, in particular less than 1% by weight, and better still absent from the composition are: the solid fatty substances chosen from synthetic beeswaxes marketed by Koster Keunen under the trade name Kester Wax K82H, or a mixture thereof; polyethylene wax, such as that marketed by New Phase Technologies under the name Performalène 400 (P400) or by Jeen International Corporation under the name Jeenate 3H, a mixture of high molecular weight linear polyethylene and ethylene / propylene copolymer, marketed by Safi-Alcan under the trade name Lipwax® PZ80-20, a synthetic wax such as that marketed by Sasol under the name Sasol Wax C80, mixtures of synthetic waxes and vegetable waxes,such as for example a mixture of synthetic wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smart wax 202, a mixture of synthetic wax, Candelilla wax and carnauba wax (Copernica cerifera) marketed by Strahl & Pitsch under the name Smartwax 7743S, Fischer Tropsch waxes such as those marketed by Cirebelle under the name Cirebelle 303, or one of their mixtures, montan wax, ceresins, ozokerites, microcrystalline waxes, mineral paraffins; and Pasty fatty substances chosen from vaselines also called petrolatum.,

[0370] Pharmaceutical composition

[0371] According to yet another aspect, the invention relates to a pharmaceutical composition comprising a mixture of linear alkanes according to the invention.

[0372] Use of a mixture of linear alkanes

[0373] According to yet another aspect, the invention relates to the use of a mixture of linear alkanes according to the invention in the field of cosmetics, pharmaceuticals, coatings, inks, varnishes, paper, adhesives, candles, plastics, rubbers and / or food products.

[0374] Specific mixture of terminal olefins

[0375] According to yet another aspect, the invention relates to a mixture of terminal olefins which consists of:

[0376] From 0.5 to 10%, preferably from 1 to 10%, even more preferably from 1 to 5% of C16 terminal olefins;

[0377] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C18 terminal olefins; and

[0378] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C20 terminal olefins; the percentages being expressed in moles relative to the total molar weight of the mixture of terminal olefins.

[0379] This mixture is particularly useful for preparing, according to the process of the invention, a wax of natural origin having physicochemical properties comparable to those of mineral paraffins, notably used in the field of lipsticks.

[0380] Mixture of internal olefins obtained in step ii) According to yet another aspect, the invention relates to a mixture of internal olefins of natural origin, in particular of plant origin, capable of being obtained according to steps i) and ii) of the process according to the invention.

[0381] In embodiments, said at least one terminal linear olefin used in step i) of the process is a mixture of C16, C18 and C20 terminal linear olefins.

[0382] In embodiments, the mixture of C16, C18 and C20 terminal linear olefins consists of:

[0383] From 0.5 to 10%, preferably from 1 to 10%, even more preferably from 1 to 5% of C16 terminal olefins;

[0384] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C18 terminal olefins; and

[0385] From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C20 terminal olefins; the percentages being expressed in moles relative to the total molar weight of the mixture of terminal olefins.

[0386] This mixture is particularly useful as a synthesis intermediate for preparing the mixture of linear alkanes according to the process of the invention.

[0387] Examples

[0388] Materials and methods

[0389] Materials

[0390] Mixtures of linear alkanes were prepared from commercial products, such as:

[0391] Ru-2 CAS: 373640-75-6 (M206)

[0392] Ru-3 CAS: 1212008-99-5 (M711)

[0393] The Ru1 a / Ru1 b catalyst was prepared according to the publication Dalton Trans., 2014, 43, 7044.

[0394] Methods

[0395] Gas chromatography (GC) analysis:

[0396] Gas chromatography allows the determination of the different components of a mixture that diffuse at different speeds depending on their affinity with the mobile phase and the stationary phase. The products are thus separated from each other to form a chromatogram. Thanks to calibration lines previously carried out on each of the isolated compounds, these can be quantified. The samples were prepared at a known concentration in vials and analyzed by gas chromatography (GC) according to: “method 1”: with a Shimadzu GC-2014 device with an Agilent VF-5ht column with the following characteristics: 30 m X 0.25 mm X 0.10 pm, maximum temperature: 430°C. A temperature gradient is used during the analysis: [Table 1]

[0397] Analysis time: 68 min or according to “method 2” (for the widest distributions): with a Restek MXT-1 HT SimDist column with the following characteristics: 5 m X 0.53 mm X 0.10 pm, maximum temperature: 450°C. Samples were prepared at a known concentration (0.1 mg / mL). A temperature gradient is used during the analysis:

[0398] [Table 2]

[0399] Analysis time: 23 min

[0400] Analysis by gas chromatography coupled with mass spectrometry (GC / MS):

[0401] This technique combines gas chromatography (explained previously) and mass spectrometry which allows the determination of the molecular masses of the analyzed compounds according to their mass / charge ratio. The samples were prepared in vials and analyzed on a Shimadzu GC-2010 Plus device with a Shimadzu SH-Rxi-5ms column with the following characteristics: 30m X 0.25mm X 0.25pm, maximum temperature: 330°C. A temperature gradient is used during the analysis:

[0402] [Table 3]

[0403] Analysis time: 32 min

[0404] Nuclear Magnetic Resonance (NMR) Analysis:

[0405] The synthesized molecules are characterized by Nuclear Magnetic Resonance (NMR) spectrometry. The NMR spectra were recorded on a Bruker ARX400 device ( 1 H: 400 MHz, 13 C: 101 MHz, 31P: 162MHz). Solvent: CDCb. Analysis by DSC (Differential Scanning Calorimetry):

[0406] Synthesized waxes, formulated solid compositions including lipsticks are analyzed by a DSC 25 device from the TA Instruments brand in order to know precisely their fusion profile.

[0407] Polymorphism protocol 100°C (temperature gradient):

[0408] DSC is a thermal analysis technique that measures the differences in heat exchange between a reference and a sample to be analyzed. It allows us to know: the melting point of the samples, the melting start temperature, which is desired to be as high as possible to limit the risks of exudation and thermal instability, the 100% melt temperature, to establish the industrial process temperature by ensuring complete melting of the crystals, the enthalpy, which corresponds to the energy required to melt the wax crystals. The highest possible enthalpy is desirable to maximize the quantity of crystals and allow for a harder stick.

[0409] Solid fats and crystals more generally can sometimes exhibit what is called polymorphism. Polymorphism corresponds to the possibility of forming different types of crystals depending on external conditions (cooling rate or storage time for example). Thus, these different types of crystals, which can coexist, are characterized by different melting points, densities, plasticities, etc. For some waxes, the cooling rate impacts the crystals formed. It is essential to avoid waxes exhibiting this type of polymorphism for the sake of stability and repeatability of industrial batches. Polymorphism can be anticipated from the DSC profile by subjecting the sample to successive coolings at different rates.

[0410] All these parameters are evaluated using a differential scanning calorimeter (DSC 25, Discovery DSC Series, TA Instruments, France) connected to a computer with Trios software (TA Instruments, France) allowing measurements to be launched and the spectra obtained to be analyzed. For each candidate, 11 + / - 0.5 mg of wax are taken and introduced into a standard crucible, sealed using a crimper (Tzero Sample Press, TA Instruments, France). The program follows the following protocol: first heating to erase the thermal past of the raw material (5°C / min from 15°C to 120°C), followed by slow cooling (2°C / min from 120°C to -5°C), a second heating (5°C / min from -5°C to 120°C), rapid cooling (25°C / min from 120°C to -5°C), then a final heating (5°C / min from -5°C to 120°C). Comparison of the profiles of the second and third heatings allows conclusions to be drawn as to the polymorphism or not of each raw material.For all syntheses, two samples are prepared to ensure repeatability of measurements. Texturometer:.

[0411] Study of the hardness of red lipsticks:

[0412] The butter cutter test allows a rapid assessment of the firmness of a lipstick by measuring in particular the resistance to cutting the stick product. This measurement is carried out 24 hours after formulation, using a texturometer (TAXTPIus, MicroStable Systems, United Kingdom) equipped with a 5 kg force cell and its Butter Cutter A / BC probe (Swantech, MicroStable Systems, United Kingdom). It allows the measurement of the maximum resistance force of the stick when the butter cutter penetrates to a depth of 9 mm at a speed of 1.6 mm / s. To ensure the reproducibility of the measurements, the analysis is repeated on 6 sticks and the relative deviation between the measurements should not be greater than 10%, ideally 5%.

[0413] Example 1: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins (melting temperature = 80°C)

[0414] The process according to the invention comprises three stages: olefin metathesis - isomerizing olefin metathesis - hydrogenation ([Fig 1]). It makes it possible to obtain a mixture of alkanes from a mixture of terminal olefins.

[0415] Terminal olefins can be prepared according to known synthetic methods (see [Fig. 2], [Fig. 3]).

[0416] Step 1: Olefin metathesis involving a mixture of terminal olefins

[0417] A cross metathesis reaction carried out on 3 terminal olefins composed respectively of 16, 18 and 20 carbons of plant origin in the presence of Ruthenium catalysts allows the production of a mixture of internal olefins ranging from C30 to C38 [Fig. 4],

[0418] Protocol

[0419] In a two-necked flask equipped with a magnetic bar and a condenser, the mixture of terminal olefins Ci6 (0.01 eg, 786 mg), Cis (0.495 eg, 43.74 g) and C20 (0.495 eg, 48.6 g) is charged and heated under vacuum to 80 ° C. After 1 hour the catalyst (Ru-1 a / Ru-1 b 3 / 7, 0.3 mol%, 953 mg) is added under argon as well as the distilled solvent (THF, 40 mL). The mixture is then stirred at 75 ° C for two days. The reaction is hydrolyzed with ethyl vinyl ether and the reaction mixture is purified by chromatography on silica gel with hot cyclohexane to remove the remaining catalyst. Cold filtration to remove the last traces of catalyst is carried out with acetone to give the desired product in the form of a white powder.

[0420] NMR

[0421] NMR analysis 1H (solvent CDCh) shows the appearance of olefinic protons from the terminal olefin as well as the complete disappearance of the terminal olefinic protons. Analysis of the final product by gas chromatography shows a mixture of olefins composed of 30 to 38 carbons. Step 2: Isomerizing olefin metathesis

[0422] The isomerizing olefin metathesis reaction in the presence of a duo of ruthenium catalysts [Fig. 5] gives access to a mixture of internal olefins. A gas chromatographic analysis made it possible to determine the composition of this mixture, obtaining a distribution of internal olefins comprising from 24 to 60 carbons (according to “method 1”, [Fig. 6]).

[0423] Protocol

[0424] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (50g) is introduced and heated under vacuum at 80°C for 1 hour. The catalysts (Ru-2, 0.5mol%, 464mg and Ru-3, 1mol%, 817mg) are then added under argon along with the distilled solvent (THF, 41 mL) and methanol (4.1 mL). The mixture is stirred at 75°C for 15 hours. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. Cold filtration to remove the last traces of catalyst is carried out with acetone to give the desired product in the form of a white powder.

[0425] The hydrogenation of the previously obtained mixture of internal olefins in the presence of palladium on carbon was then studied according to “method 1” ([Fig. 7]) and allowed the production of a mixture of alkanes comprising 24 to 60 carbons.

[0426] Protocol

[0427] In a flask under argon equipped with a magnetic bar, the mixture of internal olefins (48.1g), the catalyst (Pd / C, 1.9g; 0.4% wt Pd / substrate) and the solvent (cyclohexane, 240mL) are introduced. The reaction is heated to 50°C and purged 3 times under H2. The mixture is left stirring at 50°C for 16 hours under 1 bar of hydrogen. The reaction medium is filtered through a frit with hot cyclohexane and then concentrated using a rotary evaporator. Cold filtration with acetone to remove the last traces of catalyst is carried out to give the desired product (45g) in the form of a white powder with a mass yield of 93%.

[0428] NMR

[0429] NMR analysis 1 H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0430] CPG

[0431] Analysis of the reaction mixture by GC (according to “method 1”, ([Fig. 8]) confirms the presence of the mixture of alkanes and made it possible to determine the exact composition of the mixture in the form of a distribution containing from 24 to 60 carbons. This mixture is designated “Wax A”.

[0432] DSC Thermogravimetric analysis shows that the melting temperature and enthalpy are very close to those of Lipwax® PZ80-20 with respective values ​​of 79.6 vs 80.6°C and 226 vs 212 J / g. In addition, the "onset point", which determines the initial melting point of the wax, is lower than that of Lipwax® PZ80-20 (55.2 vs 63.5°C) and the melting temperature of the last alkane in the mixture ("endset point") is higher for Wax A (90.7 vs 89.9°C), which implies that the alkane range of Wax A is greater than that of Lipwax® PZ80-20.

[0433] Example 2: Synthesis of a mixture of linear alkanes of natural origin from a terminal linear olefin (melting temperature = 49°C)

[0434] From jojoba oil (Flora esters® marketed by Floratech), it is possible to carry out ethenolysis without going through isomerization ([Fig. 9]). The product of this synthesis, dec-1-ene, can then be engaged in a sequential process of metathesis / isomerizing metathesis / hydrogenation [Fig. 10] to obtain a mixture composed of alkanes ranging from C17 to C44.

[0435] Protocol

[0436] Decolorized jojoba oil (1g) is loaded into a vial fitted with a magnetic stir bar and a septum. The oil is heated at 180°C for 2h under vacuum. Vacuum-argon purges are performed. The catalyst is added as a solution (Ru-4, 1 mg / mL in dichloromethane, 120pL, 0.01 mol%) under argon. The septum is quickly removed and the vial is placed in an autoclave. Ethylene purges (purity = 99.95%) are performed and the mixture is stirred at 10 bar of ethylene for 6h at 40°C. The reaction is hydrolyzed with ethyl vinyl ether and the product is analyzed by GC with trimethoxybenzene as an internal standard. The conversion is 98% and the product obtained is predominantly dec-1-ene.

[0437] Decene (1g; 7.13mmol) is loaded into a Schlenk flask equipped with a magnetic stir bar. Rapid vacuum-argon purges are performed and the catalyst (Ru-1 a / Ru-1 b 3 / 7, 0.3mol%, 19.4mg) is added under argon as well as the distilled solvent (THF, 7mL). The mixture is then stirred at 75°C for four days. The reaction is hydrolyzed with ethyl vinyl ether and the solvent is removed under reduced pressure. The product is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The product obtained (554mg) is a light yellow liquid with a mass yield of 62% and is analyzed by GC and GC-MS.

[0438] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (500mg) is introduced and heated under vacuum at 80°C for 1 hour. The catalysts Ru-2 (9.2mg; 0.5mol%) and Ru-3 (16.3mg; 1mol%) are then added under argon along with the distilled solvent (THF, 2.8mL) and methanol (82pL). The mixture is stirred at 75°C for 2 hours. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst to give the desired product (476mg) as a light yellow paste with a mass yield of 95%.

[0439] The internal olefin mixture (350 mg) and the catalyst (Pd / C, 14 mg; 0.4% wt Pd / substrate) are introduced into a microwave tube equipped with a magnetic stir bar and heated under vacuum at 50 ° C. The solvent (cyclohexane, 1.75 mL) is added under argon. Vacuum-hydrogen purges are carried out (3 times). The mixture is left to bubble under hydrogen at 1 atm for 30 seconds and the mixture is then stirred at 50 ° C for 6 hours at 1 atmosphere of hydrogen. The crude mixture is purified by silica gel chromatography with hot cyclohexane. After removal of the solvent under vacuum, cold filtration with acetone to remove the last traces of catalyst is carried out to give the desired product in the form of a white powder with a mass yield of 59%. The product is analyzed by GC and NMR 1 H.

[0440] NMR

[0441] NMR analysis 1H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0442] CPG

[0443] Analysis of the reaction mixture by GC (according to “method 1”) [Fig. 11] confirms the presence of a mixture in the form of a Gaussian composed of alkanes containing 17 to 44 carbons.

[0444] DSC

[0445] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 48.9°C and 134.2 J / g respectively. The onset point is obtained at 36.3°C and the endset point at 56.8°C.

[0446] Example 3: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins (Tfusion = 75°C)

[0447] From a mixture of terminal olefins, it is possible to obtain a mixture of alkanes ranging from C22 to C54 using a sequential process of metathesis / isomerizing metathesis / hydrogenation. The final product has the particularity of having a melting point equal to 75°C.

[0448] Protocol

[0449] In a Schlenk equipped with a magnetic bar, the mixture of terminal olefins Ci6 (0.01 eq, 11 mg), Cis (0.495 eq, 625 mg), C20 (0.495 eq, 694 mg) and the catalyst (Ru-1 a, 32 mg) are loaded. Under argon, the mixture is heated to 80 °C. Hydrochloric acid in ethyl acetate (3 mL) is added. The mixture is then stirred at 80 °C for 2 hours. A few milligrams of catalyst (30 mg) and hydrochloric acid in ethyl acetate (5 mL) are added and the mixture is stirred at 80 °C for 2 hours. Again, a few milligrams of catalyst (30 mg) and hydrochloric acid in ethyl acetate (2 mL) are added and the mixture is stirred at 80 ° C for 2 hours. The catalyst is neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture. The product is purified by chromatography on silica gel with hot cyclohexane to remove the remaining catalyst.The product obtained (811 mg) is a white solid with a mass yield of 61% and is analyzed by GC and NMR. 1 H.

[0450] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (300mg) and the catalyst (Ru-2, 0.5mol%, 3mg) are introduced and heated under vacuum at 80°C for 20 minutes. The distilled solvent (THF, 0.6mL) and methanol (100pL) are then added under argon. The mixture is stirred at 80°C overnight. The catalyst is neutralized with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (300mg) is obtained as a white solid with a mass yield of 99% and is analyzed by GC.

[0451] The internal olefin mixture (260mg) and the catalyst (1.2mL; 50% wt Raney Nickel) are introduced into an autoclave equipped with a magnetic stir bar and heated to 110°C. Hydrogen purges are carried out (3 times). The autoclave is filled with 25 bar of hydrogen. The mixture is stirred at 110°C overnight at 25 bar of hydrogen. The crude mixture is purified by silica gel chromatography with hot cyclohexane. After removal of the solvent under vacuum, the desired product (260mg) is obtained in the form of a white powder with a mass yield of 99%. The product is analyzed by NMR 1 H, CPG and DSC.

[0452] NMR

[0453] NMR analysis 1 H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0454] CPG

[0455] Analysis of the reaction mixture by GC [Fig. 12] confirms the presence of a mixture composed of alkanes containing from 22 to 54 carbons.

[0456] DSC

[0457] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 75.2°C and 214 J / g respectively. The onset point is obtained at 66.9°C and the endset point at 79.2°C.

[0458] Example 4: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins in C6, C7 and C8 (melting temperature = 32°C)

[0459] From a mixture of terminal olefins, it is possible to obtain a mixture of alkanes ranging from C12 to C47 using a sequential process of metathesis / isomerizing metathesis / hydrogenation. The final product has a melting point of 32°C. [Fig. 13], Protocol

[0460] The catalyst (Ru-1a, 27mg) is loaded into a two-necked flask equipped with a magnetic stir bar and a condenser. Under argon, the terminal olefins Ce (0.33 eq, 737|JL), C7 (0.33 eq, 836|JL) and Ce (0.33 eq, 933|JL) are added. The mixture is heated to 75°C. Hydrochloric acid in ethyl acetate (2mL) is added. The mixture is then stirred at 75°C for 24 hours. A few milligrams of catalyst (14mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 20 hours. Again, a few milligrams of catalyst (14 mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 6 hours. The catalyst is neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture. The product is purified by chromatography on silica gel with pentane to remove the remaining catalyst.The product obtained (1.1 g) is a light yellow liquid with a mass yield of 63% and is analyzed by GC and NMR. 1 H.

[0461] In a two-necked flask, equipped with a magnetic stir bar and a condenser, the internal olefin mixture (550 mg) is introduced and heated under vacuum at 75 °C for 10 minutes. The catalysts Ru-2 (42 mg; 0.5 mol%) and Ru-3 (73 mg; 1 mol%) are then added under argon as well as the distilled solvent (THF, 9 mL) and methanol (200 μL). The mixture is stirred at 75 °C for 2 hours. The catalyst is neutralized with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (404 mg) is obtained as a light yellow paste with a mass yield of 74% and is analyzed by GC.

[0462] The internal olefin mixture (300mg) and the catalyst (Pd / C, 12mg; 0.4% wt Pd / substrate) are introduced into a microwave tube equipped with a magnetic stir bar and heated under vacuum at 50°C. The solvent (cyclohexane, 1.5mL) is added under argon. Vacuum-hydrogen purges are carried out (3 times). The mixture is left to bubble under hydrogen at 1 atm for 30 seconds and the mixture is then stirred at 50°C for 16h at 1 atmosphere of hydrogen. The crude mixture is purified by chromatography on silica gel with hot cyclohexane. The product (278mg) is obtained in the form of a white paste with a mass yield of 93%. The product is analyzed by NMR 1 H, CPG and DSC.

[0463] NMR

[0464] NMR analysis 1 H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0465] CPG

[0466] Analysis of the reaction mixture by GC (according to “method 1”) [Fig. 13] confirms the presence of a mixture composed of alkanes containing 12 to 47 carbons.

[0467] DSC Thermogravimetric analysis shows a melting temperature and enthalpy equal to 32°C and 195.9 J / g respectively. The endset point is obtained at 56.3°C.

[0468] Example 5 - Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins in C8, C9 and C10 (melting point = 37.2°C)

[0469] From a mixture of terminal olefins, it is possible to obtain a mixture of alkanes ranging from C11 to C50 by a sequential process of metathesis / isomerizing metathesis / hydrogenation. The final product obtains a melting point equal to 37.2°C. [Fig. 14]

[0470] Protocol

[0471] The catalyst (Ru-1a, 20mg) is loaded into a two-necked flask equipped with a magnetic stir bar and a condenser. Under argon, the terminal olefins Ce (0.33 eq, 700pL), C9 (0.33 eq, 771 pL) and C10 (0.33 eq, 844pL) are added. The mixture is heated to 75°C. Hydrochloric acid in ethyl acetate (1 mL) is added. The mixture is then stirred at 75°C for 15 hours. A few milligrams of catalyst (10mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 10 hours. Again, a few milligrams of catalyst (10 mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 15 hours. The catalyst is neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture. The product is purified by chromatography on silica gel with pentane to remove the remaining catalyst.The product obtained (1.36g) is a light yellow liquid with a mass yield of 81% and is analyzed by GC and NMR. 1 H.

[0472] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (679 mg) is introduced and heated under vacuum at 75 °C for 10 minutes. The catalysts Ru-2 (31 mg; 0.5 mol%) and Ru-3 (55 mg; 1 mol%) are then added under argon as well as the distilled solvent (THF, 7 mL) and methanol (200 μL). The mixture is stirred at 75 °C for 2 hours. The catalyst is neutralized with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (600 mg) is obtained as a light yellow paste with a mass yield of 88% and is analyzed by GC.

[0473] The internal olefin mixture (450 mg) and the catalyst (Pd / C, 18 mg; 0.4% wt Pd / substrate) are introduced into a microwave tube equipped with a magnetic stir bar and heated under vacuum at 50 ° C. The solvent (cyclohexane, 2.25 mL) is added under argon. Vacuum-hydrogen purges are carried out (3 times). The mixture is left to bubble under hydrogen at 1 atm for 30 seconds and the mixture is then stirred at 50 ° C for 16 h at 1 atmosphere of hydrogen. The crude mixture is purified by chromatography on silica gel with hot cyclohexane. The product (438 mg) is obtained as a white paste with a mass yield of 97%. The product is analyzed by NMR 1 H, CPG and DSC.

[0474] NMR Analysis by NMR 1 H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0475] CPG

[0476] Analysis of the reaction mixture by GC (according to “method 1”) [Fig. 14] confirms the presence of a mixture composed of alkanes containing 11 to 50 carbons.

[0477] DSC

[0478] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 37.2°C and 217 J / g respectively. The endset point is obtained at 63.6°C.

[0479] Example 6: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins in C10, C12 and C14 (melting point = 58.3°C)

[0480] From a mixture of terminal olefins, it is possible to obtain a mixture of alkanes ranging from C11 to C54 by a sequential process of metathesis / isomerizing metathesis / hydrogenation. The final product obtains a melting point equal to 57°C. [Fig. 15]

[0481] Protocol

[0482] The catalyst (Ru-1a, 19mg) is loaded into a two-necked flask equipped with a magnetic stir bar and a condenser. Under argon, the terminal olefins Cio (0.33 eq, 810pL), C12 (0.33 eq, 950pL) and C14 (0.33 eq, 1085pL) are added. The mixture is heated to 75°C. Hydrochloric acid in ethyl acetate (1 mL) is added. The mixture is then stirred at 75°C for 15 hours. A few milligrams of catalyst (10mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 10 hours. Again, a few milligrams of catalyst (10 mg) and hydrochloric acid in ethyl acetate (1 mL) are added and the mixture is stirred at 75°C for 15 hours. The catalyst is neutralized, in particular by adding an alkyl vinyl ether to the reaction mixture. The product is purified by chromatography on silica gel with pentane to remove the remaining catalyst.The product obtained (2.03g) is a light yellow liquid with a mass yield of 94% and is analyzed by GC and NMR. 1 H.

[0483] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (1.01g) is introduced and heated under vacuum at 75°C for 10 minutes. The catalysts Ru-2 (30mg; 0.5mol%) and Ru-3 (53mg; 1mol%) are then added under argon as well as the distilled solvent (THF, 6.5mL) and methanol (200pL). The mixture is stirred at 75°C for 2 hours. The catalyst is neutralized with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (963mg) is obtained as a light yellow paste with a mass yield of 95% and is analyzed by GC.

[0484] The mixture of internal olefins (430mg) and the catalyst (Pd / C, 17mg; 0.4% wt Pd / substrate) are introduced into a microwave tube equipped with a magnetic stir bar and heated under vacuum at 50°C. The solvent (cyclohexane, 2.15ml) is added under argon. Vacuum-hydrogen purges are carried out (3 times). The mixture is left to bubble under hydrogen at 1 atm for 30 seconds and the mixture is then stirred at 50°C for 16h at 1 atmosphere of hydrogen. The crude mixture is purified by chromatography on silica gel with hot cyclohexane. The product (410mg) is obtained in the form of a white paste with a mass yield of 95%. The product is analyzed by NMR 1 H, CPG and DSC.

[0485] NMR

[0486] NMR analysis 1 H (CDCh) of the final mixture shows the absence of olefinic protons around 5=5.4 ppm which confirms that we have a mixture of alkanes.

[0487] CPG

[0488] Analysis of the reaction mixture by GC (according to “method 1”) [Fig. 15] confirms the presence of a mixture composed of alkanes containing 11 to 54 carbons.

[0489] DSC

[0490] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 58.3°C and 201.7 J / g respectively. The endset point is obtained at 72°C.

[0491] Example 7: Lipstick formulation

[0492] Protocol

[0493] The lipstick formulation in Table 4 was prepared as follows: All the raw materials making up the white body, including the wax with a melting point of 80°C obtained according to Example 1, are melted at 90°C while stirring at approximately 250 rpm. When the mixture is homogeneous and clear, the previously ground pigments are incorporated into the Lexfeel 700. Stirring is increased to 350 rpm for 10 minutes and then increased to 250 rpm for 5 minutes. The pearlescent particles are incorporated. Mixing is continued for 5 minutes. The antioxidant and perfume - if present - are added and stirring is maintained for 5 minutes. The mixture is poured into molds at 85°C.

[0494] Place the molds at -20°C for 10 minutes then unmold.

[0495] Stability tests were carried out on the lipsticks. Different lipstick sticks were incubated at different temperatures (4°C, 20°C, 40°C and 45°C). The lipsticks were then observed at D+1, D+15, D+30 and D+60. The lipsticks formulated with the wax obtained according to the process described in Example 1 retained their good hold, their sliding effect and their shine throughout the incubation.

[0496] The formulations of Lipwax® PZ80-20 lipsticks and the wax obtained according to the process described in Example 1 were subjected to hardness tests (butter wire test). The results of these rheological tests are excellent since the measured hardness of the lipsticks formulated with the wax obtained according to the process described in Example 1 are similar to those of the lipsticks formulated with Lipwax® PZ80-20 (160g vs 150g respectively).

[0497] Exudation tests were also carried out. Exudation is a seepage phenomenon resulting in the appearance of oily rises to the surface of the anhydrous product in the form of micro-pitting, droplets, oily areas, etc. For this test, 4 lipsticks are positioned at different temperatures (27°C, 30°C, 35°C and 45°C) and are examined after 1 hour, 4 hours and 24 hours of waiting to see if seepage is visible. No exudation phenomenon was observed with the lipsticks formulated with the wax obtained according to the process described in Example 1, just like those formulated with Lipwax® PZ80-20.

[0498] Finally, a DSC analysis was used to compare lipsticks containing Lipwax® PZ80-20 or the wax obtained according to the process described in Example 1. According to the thermograms, the melting point of these lipsticks is very close (73°C with Wax A vs 73.7°C with Lipwax® PZ80-20). The "onset point" (33.5 vs 33°C), the "endset point" (92.5 vs 91.2°C) as well as the enthalpy

[0499] (25.25 vs 25.19 J / g) are equivalent.

[0500] [Table 4]

[0501] A lipstick stick is obtained which has adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application and is therefore compatible with packaging in stick form or in another solid form and with application by friction on the surface to be made up; the stick is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.

[0502] Example 8: Scented formula

[0503] The formulation according to Table 5 is prepared as follows: Weigh all the raw materials except the cellulose powder, the sorbitan sesquiisostearate and the perfume. Heat the raw materials to 70°C while stirring. When the mixture is completely melted, clear and homogeneous, add the cellulose and then the Sorbitan Sesquiisostearate, still stirring. Lower the temperature to 65°C while continuing to stir. At 65°C, add the perfume. Homogenize and pour into cups at 65°C.

[0504] [Table 5]

[0505] A solid perfumed formula is obtained which has adequate stability and hardness: the composition is sufficiently rigid and solid, it does not exude over time and does not present heterogeneities on the surface and is therefore compatible with packaging in solid form cast in a cup and with application by friction on the surface to be perfumed; the composition is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.

[0506] Example 9: Lip Gloss Formula

[0507] The formula in Table 6 was prepared as follows: The white body composed of the wax with a melting point of 80°C obtained according to Example 1, Cithrol PG 32 IS, isononyl isononanoate, dextrin palmitate and sucrose acetate isobutyrate is weighed and heated to 98°C while stirring at 150 rpm. When everything is melted, the temperature is lowered to 95°C. The mother-of-pearl is weighed and added and incorporated while stirring at 250 rpm. Stirring is reduced to 150 rpm to de-bubbles. The antioxidant is weighed and added. The temperature is lowered to 90°C (plus or minus 2°C). It is drained and poured into cups at 90°C. After 10 minutes at room temperature, the cups are placed at -19°C for 10 minutes.

[0508] [Table 6]

[0509] A solid lip gloss cast in a pot is obtained which has adequate stability and hardness: the composition is sufficiently rigid and solid, it does not exude over time and does not present heterogeneities on the surface and is thus compatible with packaging in solid form in a pot and with application by friction on the surface to be made up; the composition is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.

[0510] Example 10: Lip balm formula

[0511] The formula in Table 7 was prepared as follows: Weigh all the raw materials in the formula: S-Face, Eutanol G, Super Sterol Esters, Bentone gel, wax with a melting point of 80°C obtained according to Example 1, paste with a melting point of 37°C obtained according to Example 5, squalane, Salacos 43V and Shea butter. Do not include the pearlescent agents, pigments and their dispersing oil, active ingredients, perfume and antioxidant. Heat to 90°C while stirring at 250 rpm. When everything is melted, weigh and add the previously ground pigments in their dispersing oil. Mix for 10 minutes while stirring at 250 rpm. Incorporate the pearlescent agents while stirring at 250 rpm. Reduce stirring to 150 rpm to de-bubble. Weigh and add the antioxidant, active ingredients, and fragrance. Mix for 5 minutes at 150 rpm. Pour into molds at 90°C. Wait 10 minutes at room temperature, level off, and then place the molds at -19°C for 10 minutes.Wait 2 minutes at room temperature and unmold.

[0512] [Table 7]

[0513] A lip balm stick is obtained which has adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application, does not exude over time, does not have surface heterogeneities and is thus compatible with packaging in stick form and with application by friction on the surface to be made up or protected; the stability tests carried out are the same as those described in example 7. The stick is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.

[0514] Example 11: Lipstick formula The formula according to Table 8 was prepared as follows: All the raw materials making up the white body, including the wax with a melting point of 80°C obtained according to Example 1 and the paste with a melting point of 32°C obtained in Example 4, are melted at 90°C with stirring at approximately 250 rpm. When the mixture is homogeneous and clear, the previously ground pigments are incorporated into the Cithrol PG32IS. Stirring is increased to 350 rpm for 10 minutes and then increased to 250 rpm for 5 minutes. The pearlescent and active ingredients are incorporated. Mixing is continued for 5 minutes. The antioxidant and perfume are added and stirring is maintained for 5 minutes. The mixture is poured into molds at 85°C.

[0515] [Table 8]

[0516] A lipstick stick is obtained which has adequate stability and hardness: the stick is sufficiently rigid and solid, does not break during application, does not exude over time, does not have surface heterogeneities and is therefore compatible with packaging in stick form and with application by friction on the surface to be made up; the stability tests carried out are the same as those described in example 7. The stick is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture. Example 12: Formulation of a skin care product: Nutrition balm

[0517] The formula according to Table 9 was prepared as follows: the fatty phase is weighed: salacos 168EV, salacos 222, Indopol H-100, Meadowfoam seed oil, jojoba oil, Floraester, shea butter, Nomcort HK-G, wax with a melting point of 49°C (wax according to Example 2) according to the invention described above, camellia oil, rice wax, Span 120 and starch, stirred at 250 rpm and heated to 90°C, approximately 30 min. The cellulose powder and Lipex omega are added to the fatty phase once it is homogeneous and the stirring is increased to 350 rpm for 5 min and then switched to 250 rpm for 5 min. Add the glycerin and camellia extract and then lower the stirring speed to 150 rpm to avoid bubbling for 10 minutes. Add the antioxidant and perfume and continue stirring for 5 minutes. Drain at 90°C or pour into the jars at 80°C - 7 minutes at room temperature (RT) and 10 minutes at -19°C.

[0518] [Table 9]

[0519] A care balm is obtained in a cast pot which has adequate stability and hardness: the cast care balm is sufficiently rigid and solid, does not exude over time, does not present surface heterogeneities and is therefore compatible with packaging in solid form in a pot and with application by friction on the surface to be nourished; the balm is also characterized by ease of application such as good glide, good deposit from the first application and a comfortable texture.

[0520] Example 13: Formulation of a mascara

[0521] The formula according to Table 10 was prepared as follows: All the raw materials of the fatty phase are melted at 90°C with stirring: palmitostearic acid, wax according to the invention with a melting point of 58°C (wax according to Example 6), beeswax, carnauba wax, PVP Hexadecene copolymer. When the mixture is melted and homogeneous, the iron oxides are added and ground for 30 minutes in a deflocculator. The water, polyols, preservatives, triethanolamine and AMPD are heated to 85°C. The gels are dispersed. The emulsion is made by pouring the colored fatty phase into the aqueous phase. Homogenize for 20 minutes. The cellulose beads are added. Cool to 50°C, add the antioxidant. Drain at 30°C.

[0522] [Table 10]

[0523] A mascara is obtained which has adequate stability and rheology: the mascara composition is compatible with packaging in a bottle and with application by a brush on eyelashes or eyebrows; the composition is also characterized by ease of application such as good grip, good deposit and a texture which provides volume to the eyelashes similar to that obtained with a mascara of formula in all respects equal to this one with the exception of the wax of example 6 substituted by paraffin wax.

[0524] Example 14: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins from jojoba oil ("Tfusion = 68.5°C)

[0525] From jojoba oil, it is possible to obtain a mixture of alkanes ranging from C21 to C51 using a sequential process of isomerization / ethenolysis / metathesis / isomerizing metathesis / hydrogenation. The final product has the particularity of having a melting point equal to 68.5°C.

[0526] Protocol

[0527] In a flask equipped with a magnetic bar, decolorized jojoba oil (4.7g) previously treated at 150°C under vacuum for 2 hours, iron pentacarbonyl Fe(CO)5 (600pL, 50mol%) and the solvent (hexane, 89mL) are introduced. Under an argon flow, the mixture is stirred at 50°C for 24 hours under UV radiation (2 lamps λ = 365nm). After returning to room temperature, pyridine (7.2mL, 20eq / Fe(CO)5) is added and the mixture is stirred for 10 minutes. The solvent is removed using a rotary evaporator and the reaction mixture is purified by chromatography on silica gel with hot ethyl acetate. The desired product (4.2g) is obtained in the form of an orange paste.

[0528] In a vial fitted with a magnetic stir bar, the isomerized jojoba oil (4.2g) is dried at 40°C under vacuum for 1 hour. The catalyst (Ru-4, 0.5mol%, 25.3mg) in a minimum of solvent (dichloromethane, 1.5mL) is then added under argon. The vial is placed in an autoclave and purged with ethylene. The mixture is stirred at 40°C for 16 hours under 20 bar of ethylene. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. After vacuum distillation at 120°C, the desired product (1.4g) is obtained as a clear yellow liquid.

[0529] In a two-necked flask equipped with a magnetic bar and a condenser, the terminal olefin mixture (1.4 g) is charged and heated under vacuum to 80 ° C. After 1 hour, the catalyst (Ru-1 a / Ru-1 b 3 / 7, 5.1 mg) is added under argon as well as the distilled solvent (THF, 500 μL). The mixture is then stirred at 75 ° C for 3 hours. A few milligrams of catalyst (5.1 mg) diluted in solvent (500 μL) are added and the mixture is stirred at 75 ° C for 3 hours. A few milligrams of catalyst (15.4 mg) diluted in solvent (1 mL) are added and the mixture is stirred at 75 ° C for 16 hours. Again, a few milligrams of catalyst (25 mg) diluted in solvent (1.3 mL) are added and the mixture is stirred at 75°C for 8 hours. The reaction is hydrolyzed with ethyl vinyl ether and the reaction mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst.The product is then recrystallized from acetone and dried under vacuum at 200°C. The desired product (425 mg) is obtained in the form of a colorless paste.

[0530] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (425 mg) is introduced and heated under vacuum at 75 ° C for 1 hour. The catalysts (Ru-2, 0.5 mol%, 4.3 mg and Ru-3, 1 mol%, 7.6 mg) are then added under argon as well as the distilled solvent (THF, 926 μL) and methanol (38 μL). The mixture is stirred at 75 ° C for 2 hours. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (400 mg) is obtained as a colorless paste.

[0531] In a flask under argon equipped with a magnetic bar, the mixture of internal olefins (390 mg), the catalyst (Pd / C, 15.6 mg; 0.4% wt Pd / substrate) and the solvent (cyclohexane, 2 mL) are introduced. The reaction is heated to 60 ° C and purged 4 times under H2. The mixture is left stirring at 65 ° C for 16 hours under 1 bar of hydrogen. The catalyst (Pd / C, 7.8 mg; 0.4% wt Pd / substrate) and the solvent (cyclohexane, 2 mL) are added and the mixture is stirred at 75 ° C for 16 hours to have complete conversion. The crude mixture is purified by chromatography on silica gel with hot cyclohexane. Filtration at room temperature with acetone to remove the last traces of catalyst is carried out to give the desired product (313 mg) in the form of a white powder with a mass yield of 80%.

[0532] CPG

[0533] Analysis of the reaction mixture by GC (“method 2”) [Fig. 18] confirms the presence of a mixture in the form of a Gaussian composed of alkanes containing 21 to 51 carbons.

[0534] DSC

[0535] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 68.5°C and 232 J / g respectively. The onset point is obtained at 56.8°C and the endset point at 75.1°C.

[0536] Example 15: Synthesis of a mixture of linear alkanes of natural origin from a mixture of linear terminal olefins from methyl erucate (melting point = 74°C)

[0537] From methyl erucate, it is possible to obtain a mixture of alkanes ranging from C15 to C68 using a sequential process of isomerization / ethenolysis / metathesis / isomerizing metathesis / hydrogenation. The final product has the particularity of having a melting point equal to 74°C. Protocol

[0538] In a flask equipped with a magnetic bar, methyl erucate (5.2g), iron pentacarbonyl Fe(CO)5 (200|JL, 10mol%) and the solvent (hexane, 400mL) are introduced. Under an argon flow, the mixture is stirred at 50°C for 1 hour under UV radiation (2 lamps λ = 365nm). After returning to room temperature, pyridine (2.38mL, 20eq / Fe(CO)5) is added and the mixture is stirred for 10 minutes. The solvent is removed using a rotary evaporator and the reaction mixture is purified by chromatography on silica gel with hot ethyl acetate. The product (5.17g) is re-engaged in a flask equipped with a magnetic bar with iron pentacarbonyl Fe(CO)5 (198pL, 10mol%) and the solvent (hexane, 396mL). Under an argon flow, the mixture is stirred at 50°C for 6 hours under UV radiation (2 lamps λ = 365nm). After returning to room temperature, pyridine (2.37mL, 20eq / Fe(CO)5) is added and the mixture is stirred for 10 minutes.The solvent is removed using a rotary evaporator and the reaction mixture is purified by chromatography on silica gel with hot ethyl acetate. The desired product (5.17 g) is obtained in the form of an orange paste.

[0539] In a vial fitted with a magnetic stir bar, the isomerized methyl erucate (5.17g) is treated at 40°C under vacuum for 1 hour. The catalyst (Ru-4, 0.3mol%, 28.2mg) in a minimum of solvent (dichloromethane, 1.5mL) is then added under argon. The vial is placed in an autoclave and purged with ethylene. The mixture is stirred at 40°C for 16 hours under 20 bar of ethylene. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. The desired product (1.1g) is obtained as a clear yellow liquid.

[0540] In a two-necked flask equipped with a magnetic bar and a condenser, the terminal olefin mixture (1g) is charged and heated under vacuum to 75°C. After 1 hour, the catalyst (Ru-1a / Ru-1b 3 / 7, 12.6mg) is added under argon as well as the distilled solvent (THF, 1.2mL). The mixture is then stirred at 75°C for 40 hours. The reaction is hydrolyzed with ethyl vinyl ether and the reaction mixture is purified by silica gel chromatography with hot cyclohexane to remove the remaining catalyst. A few milligrams of catalyst (8.4mg) diluted in solvent (1.2mL) are added and the mixture is stirred at 75°C for 16 hours. The reaction is hydrolyzed with ethyl vinyl ether and the reaction mixture is purified by chromatography on silica gel with hot cyclohexane. The desired product (800 mg) is obtained as a light yellow paste.

[0541] In a two-necked flask, equipped with a magnetic bar and a condenser, the internal olefin mixture (800 mg) is introduced and heated under vacuum at 75 ° C for 1 hour. The catalysts (Ru-2, 0.5 mol%, 10 mg and Ru-3, 1 mol%, 17.5 mg) are then added under argon as well as the distilled solvent (THF, 2.1 mL) and methanol (86 μL). The mixture is stirred at 75 ° C for 2 hours. The reaction is hydrolyzed with ethyl vinyl ether and the crude mixture is purified by silica gel chromatography with hot cyclohexane. The desired product (700 mg) is obtained as a colorless paste. In a flask under argon equipped with a magnetic bar, the mixture of internal olefins (670 mg), the catalyst (Pd / C, 27 mg; 0.4% wt Pd / substrate) and the solvent (cyclohexane, 3.4 mL) are introduced. The reaction is heated to 60 ° C and purged 4 times under H2. The mixture is left stirring at 60 ° C for 16 hours under 1 bar of hydrogen.The crude mixture is purified by silica gel chromatography with hot cyclohexane. Cold filtration with acetone to remove the last traces of catalyst is carried out to give the desired product (543 mg) in the form of a white powder with a mass yield of 81%.

[0542] CPG

[0543] Analysis of the reaction mixture by GC (“method 2”) [Fig. 19] confirms the presence of a mixture in the form of a Gaussian composed of alkanes containing 15 to 68 carbons.

[0544] DSC

[0545] DSC thermogravimetry analysis shows a melting temperature and enthalpy equal to 74°C and 228.6 J / g respectively. The onset point is obtained at 32°C and the endset point at 86.4°C.

[0546] Table 11 summarizes the results of the DSC profiles according to Examples 1 to 3, 14 and 15 above:

[0547] [Table 11]

[0548] Example 16: Comparative example

[0549] The method described in Example 4 of patent application WO 2021 / 183330 A1, and shown schematically in [Fig. 20], has been reproduced.

[0550] CPG

[0551] Analysis of the reaction mixture by GC ([Fig. 21]) shows that the distribution of linear alkanes thus obtained is not characterized by a Gaussian distribution.

[0552] Furthermore, it is observed that the smallest alkane has 28 carbon atoms and the largest alkane has 34 carbon atoms. Therefore, the distribution has a very narrow range of 6 carbon atoms.

[0553] Binary formulations

[0554] In order to determine whether the mixtures of linear alkanes described in patent application WO 2021 / 183330 A1 make it possible to obtain waxes reproducing all the properties of synthetic waxes, the following test was carried out. A mixture of linear alkanes with a very narrow range as described in patent application WO 2021 / 183330 A1 was formulated into cosmetic compositions.

[0555] This mixture contains the linear alkanes C36H74, C38H78 and C40H82 in a ratio of 1:1:1.

[0556] The C36 / C38 / C40 mixture thus prepared was used in the preparation of a binary formulation containing 30% waxes and 70% oils.

[0557] The results of the visual analysis of the binary formulations thus prepared are summarized in Table 12 below:

[0558] [Table 12]

[0559] Binary formulations using the C36 / C38 / C40 mixture present problems of poor gelation and / or inhomogeneous crystallization on the surface, unlike the binary formulation using the commercial synthetic wax Lipwax® PZ80-20 sold by Safic Alcan.

[0560] The same mixture of C36 / C38 / C40 alkanes thus prepared was used in the preparation of lipsticks containing 12% waxes. It is observed that it is impossible to demould the lipstick sticks thus prepared, unlike the lipsticks using Lipwax® PZ80-20, which demonstrates that the mixture of alkane of the prior art does not make it possible to obtain lipsticks having the desired properties.

Claims

Claims

1. A process for preparing a mixture of linear alkanes of natural origin, preferably of plant origin, comprising the steps of: i. Metathesis of at least one terminal linear olefin, comprising between 5 and 24 carbon atoms, derived from at least one fatty acid or fatty acid ester of natural origin, preferably of plant origin, in the presence of a non-isomerizing olefin metathesis catalyst, whereby a first mixture of internal olefins (I) is obtained; ii. Isomerizing metathesis of the mixture of internal olefins (I) obtained in step i) in the presence of a catalyst or a mixture of catalysts, whereby a second mixture of internal olefins (II) is obtained, and iii. Hydrogenation of the mixture of internal olefins (II) in the presence of a catalyst, whereby a mixture (III) of linear alkanes of natural origin is obtained.

2. Process according to claim 1, in which the non-isomerizing olefin metathesis catalyst in step i) is chosen from transition metal complexes, in particular transition metal alkylidenes, in particular ruthenium.

3. The process of claim 2, wherein the non-isomerizing olefin metathesis catalyst is selected from Ru-1a, Ru-1b or a mixture thereof. [Chem 1]

4. Process according to any one of the preceding claims, in which the catalyst or mixture of catalysts used in step ii) is a transition metal complex, in particular ruthenium.

5. The process of claim 4, wherein the olefin isomerizing metathesis catalyst is a mixture of Ru-2 and Ru-3 [Chem 3] Ru-3

6. Process according to any one of the preceding claims, in which the terminal olefins used in step i) are prepared from fatty acid esters derived from jojoba oil.

7. Process according to any one of the preceding claims, in which the terminal olefins used in step i) are prepared according to the following process: a) Reduction of a carboxylic acid in order to obtain a primary alcohol, b) Bromination of the primary alcohol resulting from step a) in order to obtain a bromoalkane, c) Reaction of the bromoalkane resulting from step b) with magnesium in order to obtain an organomagnesium halide, d) Cross-coupling between the organomagnesium halide resulting from step c) and a terminal bromoalkene in order to obtain a mixture of terminal olefins.

8. A process according to any one of the preceding claims, wherein the terminal olefins used in step i) are prepared according to the following process: a) Isomerization of a carboxylic acid and / or a mixture of carboxylic acids and / or a carboxylic acid ester and / or a mixture of carboxylic acid esters in the presence of an acid catalyst or a metal complex, preferably iron carbonyl complexes, preferably iron pentacarbonyl; b) Ethenolysis of the reaction product from step a) in the presence of a ruthenium catalyst in order to obtain a mixture of terminal olefins.

9. Process according to any one of the preceding claims, in which said at least one terminal linear olefin used in step i) is a mixture of at least two distinct terminal linear olefins each comprising between 5 and 24 carbon atoms, in particular between 16 and 24 carbon atoms, preferably between 16 and 20 carbon atoms.

10. A method according to claim 9, wherein said at least two terminal linear olefins differ from each other by a number of carbon atoms of at least two.

11. Process according to any one of the preceding claims, wherein said at least one terminal linear olefin used in step i) is a mixture of three terminal linear olefins, preferably C6 / C7 / C8, C8 / C9 / C10, C10 / C12 / C14, or C16 / C18 / C20.

12. A method according to claim 11, wherein the mixture comprises: From 0.5 to 10%, preferably from 1 to 10%, even more preferably from 1 to 5% of C16 terminal olefins; From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C18 terminal olefins; and From 45 to 55%, preferably from 45 to 52.5%, even more preferably from 45 to 49.5% of C20 terminal olefins; The percentages are expressed in moles relative to the total molar weight of the terminal olefin mixture.

13. Process according to any one of the preceding claims, in which the terminal olefin used in step i) is biosourced.

14. Mixture of linear alkanes of natural origin, in particular of plant origin, said mixture being capable of being obtained according to the process as defined in the claims

15. Mixture of linear alkanes of natural origin, in particular of plant origin, in particular in the form of a solid fatty substance, in which: each linear alkane constituting the mixture comprises between 8 and 90 carbon atoms, in particular between 10 and 85 carbon atoms, better still between 10 and 75, preferably between 10 and 70 carbon atoms, even more preferably between 24 and 60, and the distribution of the numbers of each linear alkane, arranged by increasing number of carbon atoms, is: o increasing between the linear alkane having the smallest number of carbon atoms up to the mode of the distribution; and o decreasing between the mode of the distribution and the linear alkane having the largest number of carbon atoms, the numbers being calculated as a percentage by weight relative to the total weight of the mixture of linear alkanes of natural origin.

16. A mixture of linear alkanes according to claim 15, characterized by a range greater than 15, preferably greater than 20, and less than 60, preferably less than 55, said range being defined as the difference between the number of carbon atoms of the linear alkane having the largest number of carbon atoms and the number of carbon atoms of the linear alkane having the smallest number of carbon atoms.

17. A mixture of linear alkanes according to claim 15 or 16, wherein each linear alkane in the distribution differs by a number of carbon atoms equal to one from the consecutive and / or preceding linear alkane in the distribution.

18. A mixture of linear alkanes according to claims 15 to 17, wherein the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 8 and 26 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 55 and 90.

19. A mixture of linear alkanes according to claims 15 to 18, wherein the mode of distribution is between 40 and 45 carbon atoms.

20. A mixture of linear alkanes according to any one of claims 15 to 19, wherein the median of the distribution is between 40 and 45 carbon atoms.

21. A mixture of linear alkanes according to any one of claims 15 to 20, wherein the mixture has a melting point of between 75 and 85°C.

22. A mixture of linear alkanes according to any one of claims 15 to 17, wherein:the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 15 and 19 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 42 and 46; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 20 and 24 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 10 and 14 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 45 and 49; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 48 and 52;or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 9 and 13 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 52 and 56; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 16 and 20 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 63 and 67; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 13 and 17 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 66 and 70; or the linear alkane having the smallest number of carbon atoms has a number of carbon atoms between 19 and 23 and the linear alkane having the largest number of carbon atoms has a number of carbon atoms between 49 and 53.;

23. A composition comprising a mixture of linear alkanes according to any one of claims 14 to 22.

24. Composition according to claim 23, comprising less than 3% by weight, in particular less than 1% by weight, preferably free of solid fatty substances of mineral and / or synthetic origin, the percentages by weight being expressed relative to the total weight of the composition.

25. Composition according to claim 23 or 24, characterized in that it is a cosmetic or pharmaceutical composition, preferably a cosmetic composition in the form of a perfuming, care or makeup product for the skin, mucous membranes or appendages.

26. Composition according to one of claims 23 to 25, characterized in that it is a solid composition, preferably in stick form.

27. ​​Use of a mixture of linear alkanes according to any one of claims 14 to 22 to substitute synthetic waxes of petroleum origin.

Images