Synthesis of a branched unsaturated compound by means of cross metathesis

• US 9,382,189 B2
• Filed: 02/10/2014
• Issued: 07/05/2016
• Est. Priority Date: 02/08/2013
• Status: Active Grant

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Dubois, Jean-Luc, Couturier, Jean-Luc
• Primary Examiner(s): Cutliff, Yate K
• Application Number:
  US14/766,588
• Publication Number:
  US 20150376108A1
• Time in Patent Office: 876 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 253/00 Preparation of carboxylic acid nitriles of cyanogen or compounds thereof C01C3/00
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/06 of an acyclic and unsaturated carbon skeleton
• CPC Class Codes: C07C 51/353 by isomerisation; by change of size of the carbon skeleton
• CPC Class Codes: C07C 57/03 Monocarboxylic acids
• CPC Class Codes: C07C 67/343 by increase in the number of carbon atoms
• CPC Class Codes: C07C 67/347 by addition to unsaturated carbon-to-carbon bonds
• CPC Class Codes: C07C 69/533 Monocarboxylic acid esters having only one carbon-to-carbon double bond
• CPC Class Codes: C07D 301/02 Synthesis of the oxirane ring

Abstract

The invention relates to a method for the synthesis of a branched unsaturated fatty compound, said method comprising the metathesis, in the presence of a metathesis catalyst, of a linear unsaturated fatty compound and a branched olefin. The branched unsaturated fatty compound is used in particular for the production of at least one of the following products: dielectric fluids, specialty surfactants, emulsifiers, frictions agents, antistatic additives, antifogging additives, mould release agents, pigment dispersants, high-performance lubricants, waxes and wax emulsifiers, polymer conversion additives, PVC stabilizing agents, inks, resins, paints, varnishes, solvents, lipsticks, creams for the skin, deodorants, particularly stick deodorants, hair dyes, shampoos and other liquid soaps, shaving foam, laundry detergents, cleaning agents, fabric softeners, and mixtures of same.

Claims

1. A process for synthesizing a branched unsaturated fatty compound of formula III:

A-CH═

CB′

—

B wherein;

A is a radical consisting of an linear alkyl chain, comprising from 1 to 20 carbon atoms and comprising an acid, ester of a monoalcohol or of a polyol or nitrile end function;

B′

is H or an alkyl chain comprising from 1 to 10 carbon atoms; and

B is;

if B′

is an alkyl chain, B is an alkyl chain comprising from 1 to 11 carbon atoms; and

if B′

is H, B is an alkyl chain comprising from 3 to 11 carbon atoms bearing at least one branched alkyl radical of formula C_nH_2n+1 with n in the range from 1 to 5, said process comprising;

performing metathesis in the presence of a metathesis catalyst between;

(a) a linear unsaturated fatty compound of formula I R—

(CH₂)_a-[(CH═

CH)—

(CH₂)]_b—

(CH₂)_c—

R′

is wherein R′

is a radical —

COOH, COOR₁ or —

CN, R₁ being a monoalcohol or a polyol residue R is H or an acid, monoalcohol ester or nitrile function, and a, b, c are integers such that 0≦

a≦

11;

1≦

b≦

6;

2≦

c≦

12, the sum a+3*b+c+1 being in the range from 8 to 36; and

(b) a branched olefin II comprising from 4 to 23 carbon atoms, wherein the main chain comprises at least one branching of formula C_nH_2n+1 with n in the range from 1 to 5 when B′

is H.

2. The process as claimed in claim 1, wherein the linear unsaturated fatty compound I is chosen from:

monounsaturated or polyunsaturated fatty acids or fatty acid esters, Including mono-, di- and triglycerides, and nitrile derivatives, of the following fatty acids;

oleic, petroselinic, linoleic, ricinoleic, gadoleic, gondoic, vaccenic, linolenic, palmitoleic, erucic, nervonic, and mixtures thereof.

3. The process of claim 1, wherein compound I is chosen from:

nitrile derivatives obtained by nitridation of an ester or acid function of a fatty ester or fatty acid;

difunctional molecules bearing acid, ester or nitrile functions at each end of the molecule;

triglycerides; and

functional molecules comprising from 8 to 12 carbon atoms.

4. The process of claim 1, wherein the branched olefin II used for the metathesis reaction contains at least 5 carbon atoms in total.

5. The process of claim 1, wherein the branched olefin II is of formula II:

R₀R₀′

C≡

CBB′

wherein;

B′

is H or an alkyl chain comprising from 1 to 10 carbon atoms, and

if B′

Is an alkyl chain, B is an alkyl chain comprising from 1 to 11 carbon atoms, and

if B′

is H, B is an alkyl chain comprising from 3 to 11 carbon atoms including at least one carbon atom bearing an alkyl radical of formula C_nH_2n+1 with n in the range from 1 to 5, and

R′

₀ is H or an alkyl chain comprising from 1 to 10 carbon atoms, and

if R′

₀ is H, R₀ is H, CH₃, C₂H or an alkyl chain comprising from 3 to 11 carbon atoms Including at least one carbon atom bearing an alkyl radical of formula CH_2n+1 with n in the range from 1 to 5, and

if R′

₀ is an alkyl chain, R₀ s H or an alkyl chain comprising from 1 to 11 carbon atoms.

6. The process as claimed in claim 5, wherein, in formula II of the olefin, B′

is H and B is of formula —

(CR₂R)_m—

CH₃ wherein R₂ and R₃, which may be identical or different, are either H or a saturated alkyl radical comprising from 1 to 5 carbon atoms, the radicals R₂, on the one hand, and the radicals R₃, on the other hand, linked to the carbon atoms of the chain being identical to or different from each other, and at least one of the radicals R₂ and R₃ being a saturated alkyl radical.

7. The process of claim 1, wherein said at least one branching of the olefin is located closer to the double bond C≡

C than the end of the chain which bears said branching.

8. The process of claim 7, wherein each carbon atom of the double bond of formula II:

R₀R₀′

C≡

CBB′

bears only one alkyl chain.

9. The process of claim 1, wherein the carbon atoms of said at least one double bond of the olefin are linked on one side of the double bond to a chain of not more than 2 other carbon atoms.

10. The process of claim 1, wherein the metathesis catalyst comprises at least one ruthenium-carbene catalyst chosen from the charged or uncharged catalysts of general formula:

(X₁)_a(X₂)_bRu(carbene C)(L₁)_c(L₂)_d(L₃)_e

wherein;

a, b, c, d and e are Integers, which may be Identical or different, with a and b equal to 0, 1 or 2;

c, d and e equal to 0, 1, 2, 3 or 4;

X₁ and X₂, which may be identical or different, each represent a charged or uncharged and monochelating or polychelating ligand; and

L₁, L₂ and L₃, which may be identical or different, are electron-donating ligands.

11. The process as claimed in claim 10, wherein the catalyst comprises a saturated NHC ligand substituted with phenyls substituted with mesityl (Mes) or Isopropyl (iPr) groups.

12. The process of claim 1, wherein the process is performed in liquid medium at a temperature in the range from 20 to 160°

C. and at a pressure in the range from 1 to 30 bar.

13. The process as claimed in claim 8, wherein the process is performed at a temperature in the range from 20 to 120°

C. and at a pressure in the range from 1 to 10 bar.

14. The process of claim 1, wherein the reaction Is performed in the presence of a solvent.

15. The process of claim 1, further comprising:

after the production of compound III bearing at least one double bond C≡

C, at least one of the following reactions

hydrogenation of said at least one double bond C≡

C, which leads, depending on the type of hydrogenation, for the esters, to saturated esters, saturated alcohols, or even branched paraffins, and, for the nitriles, to branched amines;

hydrolysis of ester, which leads to an acid;

nitration of acid or ester, depending on whether or not there Is an Intermediate hydrolysis;

epoxidation of said at least one double bond C≡

C, with or without opening of the epoxy ring to form diols, carbonates or esters, leading to the epoxy of a branched chain; and

/or

new step of metatheses.

16. The process of claim 1, further comprising:

a step of hydrogenation for the synthesis of saturated branched fatty compounds.

17. The process of claim 1, further comprising an epoxidation of compound III, compound I being chosen from triglycerides and esters derived from oils rich in polyunsaturated fatty acids.

18. The process of claim 1, wherein the linear alkyl chain of A is unsaturated.

19. The process of claim 1, wherein the alkyl chain of B is branched, when B′

is an alkyl chain.

20. The process of claim 4, wherein said branch olefin II used for the metathesis reaction comprises from 7 to 12 carbon atoms in total.

21. The process of claim 5, wherein the alkyl chain of B is branched, when B′

is an alkyl chain.

22. The process of claim 5, wherein the alkyl chain of R₀ is branched, when R′

₀ is an alkyl chain.

23. The process of claim 5, wherein each carbon atom of the double bond of formula II:

R₀R′

₀C≡

CBB′

bears only one alkyl chain.

24. The process of claim 9, wherein said carbon atoms are of the 1-alkene, 2-alkene, or 3-alene type.

25. The process of claim 11, wherein said catalyst Is of formula: