FR3108608A1 - Functionalized branched olefins and their preparation process - Google Patents

Abstract

Functionalized branched olefins and their preparation process The present application relates to branched olefins comprising n carbon atoms, n representing an integer between 9 and 50 and comprising at least one pendant group chosen from COOR, CH (COOR) (COOR), CH (COOR) CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 atoms of carbon, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms. Figure for the abstract: None

Description

Functionalized branched olefins and process for their preparation

The present invention relates to functionalized branched olefins or mixture of branched olefin isomers comprising n carbon atoms, n representing an integer between 9 and 50.

Olefins, which allow access to many functionalized or non-functionalized alkanes, said alkanes then being able to be used in particular as ingredients in cosmetic formulations, in agrochemical formulations, as plasticizer additives, lubricants, etc., are generally derived from fossil resources, in particular oil. The use of such resources is harmful to the environment.

Furthermore, in order to provide products having varied properties, it is essential to be able to provide olefins having a high carbon number, asymmetric olefins, olefins comprising functional groups, etc.

One objective of the present invention is therefore to provide higher functionalized branched olefins, in particular comprising from 9 to 50 carbon atoms.

Another objective of the present invention is to provide such olefins having a lower level of impurities.

Another object of the present invention is also to provide a process for the preparation of such olefins.

Still other objectives will appear on reading the description of the invention which follows.

The present application relates to branched olefins comprising n carbon atoms, n representing an integer between 9 and 50, preferably between 9 and 35, and comprising at least one pendant group chosen from COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms.

Preferably, the branched olefins include a functional group. When the functional group is a COOH group then the olefin according to the invention can comprise two COOH functional groups.

In the context of the present invention, the heterocycles can be aromatic or not, partially or totally saturated, monocyclic or polycyclic.

In the context of the present invention, the aryls can be monocyclic or polycyclic.

Preferably, the olefins according to the invention correspond to the following formula (I):

(I)

R ¹ , R ² , R ³ and R ⁴ , which are identical or different, are chosen from H, linear or branched alkyls, at least one of these alkyls being branched, comprising from 1 to 48 carbon atoms and the number number of carbon atoms of formula (I) is equal to n;

provided that :

• at least two of R ¹ , R ² , R ³ and R ⁴ is different from H; And
• R ¹ and R ² cannot be simultaneously H; And
• R ³ and R ⁴ cannot be simultaneously H; And
• One of R ¹ , R ² , R ³ or R ⁴ comprises a group chosen from COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, from preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 atoms of carbon.

Preferably, at most one of R ¹ , R ² , R ³ and R ⁴ is H.

Preferably, in the compounds of formula (I), R ¹ is H or linear or branched alkyl comprising from 1 to 15 carbon atoms, and R ² , R ³ and R ⁴ , which are identical or different, are chosen from alkyls, linear or branched, comprising from 1 to 15 carbon atoms.

Preferably, in the compounds of formula (I), R¹is H,R² is an alkyl, linear comprising from 1 to 15 carbon atoms, R³and R⁴, identical or different, are chosen from alkyls, linear or branched, comprising from 1 to 15 carbon atoms.

According to the invention, an alkyl group designates a hydrocarbon-based, saturated, linear or branched aliphatic group comprising, unless otherwise stated, from 1 to 48 carbon atoms. By way of examples, mention may be made of the methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, undecenyl, lauryl, palmyl, oleyl, terpenyl, linoleyl, erucyl or ricinoleyl groups.

The invention also relates to a composition comprising a mixture of these functionalized branched olefins.

The functionalized branched olefins according to the invention can be obtained by co-dimerization of lower olefins or by metathesis of lower olefins.

In the context of the present invention, by lower olefins is meant olefins comprising less than n carbon atoms.

The co-dimerization process is implemented between an olefin comprising m carbon atoms and an olefin comprising p carbon atoms, m and p being integers chosen so that m+p=n.

The lower olefins used in the co-dimerization process can for example be of formula (II) and (III):

R ⁵ R ⁶ C=CR ⁷ R ⁸ (II) R ⁹ R ¹⁰ C=CR ¹¹ R ¹² (III)

the olefin (II) being an exo (terminal double bond) or endo (non-terminal double bond) olefin comprising 4t carbon atoms, t being an integer between 1 and 6

thus, in formulas (II) and (III)

R ⁷ and R ⁸ represent H and R ⁵ and R ⁶ , which are identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms; Or

R ⁵ , R ⁶ , R ⁷ and R ⁸ , which are identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms; Or

R ⁵ represents H and R ⁶ , R ⁷ and R ⁸ , identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms;

R ⁹ , R ¹⁰ , R ¹¹ and R ¹² , which are identical or different, represent an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms; Or

R ⁹ , R ¹¹ and R ¹² represent H and R ¹⁰ represents an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms;

the number of total carbon atoms of formula (II) being m and the number of total carbon atoms of formula (III) being p,

at least one of the olefins used in the preparation process comprises at least one pendent group COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms carbon, that is to say that at least one of the alkyls R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ or R ¹² comprises at least one pendant group COOR, CH(COOR )(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms.

The metathesis process is implemented between an olefin comprising q carbon atoms and an olefin comprising r carbon atoms, q and r being integers chosen so that q+r is greater than n. Indeed, the metathesis reaction is at the origin of the loss of carbon atoms in the final compound (loss of at least two carbon atoms), the number of carbon atoms lost being a function of the olefins put in game and in particular the nature of the substituents of the two carbon atoms of the double bond.

The lower olefins used in the metathesis process can for example be of formula (IV) and (V):

R ¹³ R ¹⁴ C=CR ¹⁵ R ¹⁶ (IV) R ¹⁷ R ¹⁸ C=CR ¹⁹ R ²⁰ (V)

the olefin (IV) being an exo (terminal double bond) or endo (non-terminal double bond) olefin comprising 4t carbon atoms, t being an integer between 1 and 6

thus, in formulas (IV) and (V)

R ¹⁵ and R ¹⁶ represent H and R ¹³ and R ¹⁴ , which are identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms; Or

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , which are identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms; Or

R ¹³ represents H and R ¹⁴ , R ¹⁵ and R ¹⁶ , identical or different, represent a linear or branched alkyl group comprising from 1 to 12 carbon atoms;

R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ , which are identical or different, represent an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms; Or

R ¹⁷ , R ¹⁹ and R ²⁰ represent H and R ¹⁸ represents an alkyl group, linear or branched, comprising from 1 to 12 carbon atoms;

the number of total carbon atoms of formula (IV) being q and the number of total carbon atoms of formula (V) being r

at least one of the olefins used in the preparation process comprises at least one pendent group COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms carbon, that is to say that at least one of ^the alkyls R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ or R ²⁰ comprises at least one pendant group COOR, CH( COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms.

The co-dimerization stage can be carried out in the presence of a catalyst chosen from Brönsted acids in solution, for example H2SO4, H3PO4, HF, methanesulfonic acid, triflic acid (CF ₃ SO ₃ H); solid Brönsted acids, for example organic resins, clays, zeolites, H3PO4 on silica; Lewis acids, for example ZnCl2, AlCl3; organometallic compounds, for example Ni complexes, mixtures of Ni and Al complexes; ionic liquids, for example [BMIm][N(CF3SO2)2]/HN(CF3SO2)2; clays with lamellar structures such as Montmorillonite; organic resins such as amberlysts, sulphonic resins; organometallic compounds such as for example [LNiCH ₂ R ²¹ ][AlCl4] in which L=PR ²² , R ²¹ represents an alkyl, linear or branched, comprising 9 carbon atoms and R ²² represents a –CH ₂ -R ²¹ group.

Preferably, the amount of catalyst used in the co-dimerization is between 1000 ppm and 10% by weight, preferably between 1000 ppm and 5% by weight, relative to the weight of olefin.

The co-dimerization step is preferably carried out at a temperature between 30 and 250°C, preferably between 100 and 200°C.

Particularly advantageously, the olefins can be obtained from isobutene. Preferably, said isobutene is obtained from bioresources, in particular as described in application WO2012052427, for example from polysaccharides (sugars, starches, celluloses, etc.).

The metathesis step is carried out by reacting the two olefins in the presence of a metathesis catalyst, in particular a catalyst chosen from catalysts known to those skilled in the art for metathesis, in particular ruthenium catalysts, in particular Grubbs catalysts ^2nd generation, for example Benzylidene 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene dichloro(tricyclohexyl-phosphine)ruthenium or (1,3-dimesitylimidazolidine-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride.

The amount of catalyst is preferably between 50 ppm and 5% by weight of Ru element, preferably between 200 ppm and 1%, relative to the weight of olefin. The reaction is preferably carried out at a temperature between 0 and 150°C, for example 20 and 100°C. The medium then undergoes a purification step, for example the reaction medium is dissolved in a solvent, for example toluene, then the mixture obtained is filtered, for example through neutral alumina.

The olefins according to the invention can be used for the formulation of cosmetic compositions, plasticizer compositions or even lubricant compositions.

The olefins of the invention can also be hydrogenated to corresponding alkanes, said alkanes being able to be used in the formulation of cosmetic compositions, plasticizer compositions or even lubricant compositions.

The present application will now be described using the examples below.

Example 1: Metathesis

The following are charged into a stirred, closed autoclave placed under an inert atmosphere:

- 100 g of isooctene (rich in methyl -2 dimethyl -4,4 pentene -1)

- 100 g of methyl pent -1 en -5 oate

- 200 g toluene

Then

- 5 g of catalyst called "Grubbs' ^2nd generation catalyst"

The mixture is heated at 50° C. for 24 hours.

The reaction mixture is cooled to room temperature.

The liquid phase is diluted in the solvent toluene for the needs of the analysis.

The conversion of the compounds involved is between 90 and 95%. The yields of isolated co-dimerization product between isooctene and pent -1 en -5 methyl oate are between 85 and 95%.

An identical process can be implemented for the following reactions:

Example 2: Co-dimerization

The following are charged into a stirred, closed autoclave placed under an inert atmosphere:

- 100 g of isooctene

- 100 g of methyl pent -1 en -5 oate

. - 10g of Montmorillonite

- 5g of Isooctane

The mixture is gradually heated and co-dimerization begins at around 150°C.

Continue to increase the temperature to 200°C.

The mixture is kept under stirring and at this temperature level for 3 hours.

Cool the reaction mixture to room temperature

The Montmorillonite catalyst is separated from the liquid phase by filtration.

The liquid phase is diluted in a cyclohexane solvent for the needs of the analysis.

The conversion of the compounds involved is between 70 and 95%. The yields of co-dimerization products between isooctene and pent -1 en -5 methyl oate are between 50 and 90%.

An identical process can be implemented for the following reactions:

Claims (7)

Branched olefin comprising n carbon atoms, n representing an integer between 9 and 50 and comprising at least one pendant group chosen from COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear alkyl group or branched comprising from 1 to 10 carbon atoms. Olefin according to claim 1 corresponding to the following formula (I):

(I)
R¹, R², R³and R⁴, identical or different, are chosen from H, alkyls, linear or branched, at least one of these alkyls being branched, comprising from 1 to 48 carbon atoms and the total number of carbon atoms of the formula (I ) is equal to n;
provided that :

• at least two of R ¹ , R ² , R ³ and R ⁴ is different from H; And
• R ¹ and R ² cannot be simultaneously H; And
• R ³ and R ⁴ cannot be simultaneously H; And
• One of R ¹ , R ² , R ³ or R ⁴ comprises a group chosen from COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR, a heterocycle comprising from 5 to 10 heteroatoms, from preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 atoms of carbon.

Olefin according to Claim 2, in which R ¹ is H or linear or branched alkyl comprising from 1 to 15 carbon atoms, and R ² , R ³ and R ⁴ , which are identical or different, are chosen from the alkyls, linear or branched, comprising from 1 to 15 carbon atoms. Olefin according to claim 2, wherein R¹is H, R² is an alkyl, linear comprising from 1 to 15 carbon atoms, R³and R⁴, identical or different, are chosen alkyls, linear or branched, comprising from 1 to 15 carbon atoms. Process for preparing an olefin according to any one of Claims 1 to 4, in which the olefin is obtained by co-dimerization between an olefin comprising m carbon atoms and an olefin comprising p carbon atoms, m and p being integers chosen so that m+p=n; at least one of the olefins comprising at least one COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR group, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms. Process for preparing an olefin according to any one of Claims 1 to 4, in which the olefin is obtained by metathesis between an olefin comprising m carbon atoms and an olefin comprising p carbon atoms, m and p being integers chosen so that m+p is greater than n; at least one of the olefins comprising at least one COOR, CH(COOR)(COOR), CH(COOR)CN, CHO, OR group, a heterocycle comprising from 5 to 10 heteroatoms, preferably the heteroatoms are chosen from O, N or S, including at least one nitrogen atom, an aryl comprising from 6 to 10 carbon atoms, in which R represents H, a linear or branched alkyl group comprising from 1 to 10 carbon atoms. Use of olefins according to any one of Claims 1 to 4, for the formulation of cosmetic compositions, plasticizer compositions or even lubricant compositions.