Method for the controlled hydroformylation and isomerization of a nitrile/ester/omega unsaturated fatty acid

Patent metadata

Field	Value
Publication number	US-2016115120-A1
Application number	US-201414896247-A
Country	US
Kind code	A1
Filing date	Jun 6, 2014
Priority date	Jun 6, 2013
Publication date	Apr 28, 2016
Grant date	—

Abstract

A method to synthesize a fatty nitrile/ester aldehyde comprising the following steps:
1) hydroformylation of a ω-unsaturated fatty nitrile/ester/acid substrate under particular conditions of partial pressure, temperature, reaction time, conversion rate of the ω-unsaturated fatty nitrile/ester/acid reactant, catalyst, [substrate]/[metal] molar ratio and [ligand]/[metal] molar ratio so as after the reaction to obtain:
a hydroformylation product comprising at least one fatty nitrile/ester/acid aldehyde of formula: OHC—(CH 2 ) r+2 —R, and an isomerate comprising at least one fatty nitrile/ester/acid isomer with internal unsaturation in which at least 80% of the internal isomer(s) of the isomerate are formed of the ω-1 unsaturated isomer of formula CH 3 —CH═CH—(CH 2 ) r−1 —R; followed by:
2) separation and recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.

First claim

1 . A method to prepare a fatty nitrile/ester/acid aldehyde comprising the following steps:
1) hydroformylation of a ω-unsaturated fatty nitrite/ester/acid substrate selected from among the compounds of formula CH 2 ═CH—(CH 2 ) r —R, where R is CN or COOR 1 , R 1 being H or an alkyl radical having 1 to 4 carbon atoms, r is an integer index such that 1≦r≦13, advantageously 2≦r≦13 and preferably 4≦r≦13, wherein said substrate is reacted with carbon monoxide and dihydrogen under the following conditions: CO partial pressure of 40 bar or lower, H 2 partial pressure of 40 bar or lower, and the P i CO/P i H 2 ratio between the respective CO and H 2 partial pressures is in the range of 0.5:1 to 3:1, temperature in the range of 70 to 150° C. reaction time of 24 h or less, in the presence of a catalyst comprising at least one Group VIII metal and at least one bidentate or monodentate ligand, [substrate]/[metal] molar ratio in the range of 5 000 to 100 000 [ligand]/[metal] molar ratio in the range of 10:1 to 100:1,
so as after the reaction to obtain:
a hydroformylation product comprising at least one fatty nitrile/ester/acid aldehyde of formula: OHC—(CH 2 ) r+2 —R, and
an isomerate comprising at least one fatty nitrile/ester/acid isomer with internal unsaturation of which at least 80% of the internal isomer(s) of the isomerate are formed of the ω-1-unsaturated isomer of formula CH 3 —CH═CH—(CH 2 ) r−1 —R; followed by:
2) separation and recovery of the fatty nitrile/ester/acid aldehyde and of the isomerate.

2 . The method according to claim 1 wherein the ω-unsaturated fatty nitrile/ester/acid substrate meets formula CH 2 ═CH—(CH 2 ) r —R, with R═COOR 1 , R 1 being H or an alkyl radical having 1 to 4 carbon atoms.

3 . The method according to claim 1 , wherein hydroformylation is conducted under CO partial pressure in the range of 10 to 40 bar, under H 2 partial pressure in the range of 5 to 20 bar, and/or with a P i CO/P i H 2 ratio between the respective CO and H 2 partial pressures in the range of 1:1 to 3:1.

4 . The method according to claim 1 , wherein hydroformylation is conducted at a temperature within the range of 100 to 130° C., preferably 100 to 120° C., preferably at a temperature of substantially 120° C.

5 . The method according to claim 1 , wherein hydroformylation is conducted for a time in the range of 1 to 12 h, preferably in the range of 2 to 6 h, preferably in the range of 3 to 5 h, preferably in the order of 4 h.

6 . The method according to claim 1 , wherein the ligand of the catalyst is a bidentate ligand, advantageously a chelating diphosphine selected from among Dppm, Dppe, Dppb, Xantphos and/or BiPhePhos, preferably selected from among Xantphos and/or BiPhePhos, and is further preferably BiPhePhos.

7 . The method according to claim 1 , wherein the metal of the catalyst is provided in the form of a precursor comprising said metal and at least one compound selected from among acetylacetonates, carbonyl compounds, cyclooctadienes, chlorine, and mixtures thereof.

8 . The method according to claim 7 wherein the hydroformylation catalyst comprises rhodium, preferably provided by a precursor such as Rh(acac)(CO) 2 , ruthenium, preferably provided by a precursor such as Ru 3 (CO) 12 , where acac is an acetylacetonate ligand and CO is a carbonyl ligand, and/or iridium, preferably provided by a precursor such as Ir(COD)Cl where COD is a 1,5-cyclooctadiene ligand and Cl is a chlorine ligand, preferably it comprises iridium.

9 . The method according to claim 6 , wherein hydroformylation is catalyzed by a system selected from among: Rh-Xantphos, Rh-BiPhePhos, Ir-Xantphos, Ir-BiPhePhos and the mixtures thereof.

10 . The method according to claim 1 , wherein the [substrate]/[metal] molar ratio is in the range of 5000 to 50 000.

11 . The method according to claim 7 , wherein the [ligand]/[metal] molar ratio is in the range of 20:1 to 100:1, preferably 40:1 to 100:1.

12 . The method according to claim 1 , wherein hydroformylation is performed using a sufficient amount of solvent to solubilize at least part of the catalyst, preferably in an amount of less than 1%, preferably less than 1/1000 relative to the ω-unsaturated fatty nitrile/ester/acid reactant.

13 . The method according to claim 1 , wherein the hydroformylation step comprises recycling of the hydroformylation catalyst, optionally completed by the providing of new catalyst and/or ligand at a subsequent hydroformylation cycle.

14 . The method according to claim 1 , further comprising, prior to the hydroformylation step, a step to pre-treat the substrate, this pre-treatment being performed for example by distillation of the substrate followed by purification via adsorption of the substrate using alumina.

15 . The method according to claim 1 , further comprising a step:
to separate and recover the isomers from the isomerate, and/or to convert at least one isomer of the isomerate to isomer derivative(s), in particular by conversion of one or more isomer functions to an acid, aldehyde, alcohol and/or amine function, and/or by reaction(s) of the internal double bond of isomer(s), in particular hydrogenation, epoxidation and/or polymerization.

16 . The method according to claim 1 further comprising:
2′) oxidation step in the presence of dioxygen during which the nitrile/ester/acid-aldehyde obtained at step 1) is converted to fatty nitrile/ester/acid acid of formula HOOC—(CH 2 ) r+2 —R, or
2″) a reduction step during which the nitrile/ester/acid aldehyde obtained at step 1) is converted to fatty nitrile/ester/acid alcohol of formula HOC—(CH 2 ) r+2 —R, or to an amino alcohol of formula HOC—(CH 2 ) r+3 —NH 2 for nitrile.

17 . The method according to claim 16 wherein the oxidation step is implemented by dispersing &oxygen or a gaseous mixture containing dioxygen in the product resulting from hydroformylation.

18 . The method according to claim 16 , wherein the oxidation step is implemented without the addition of solvent and/or without the addition of dioxygen-activating catalyst.

19 . The method according to claim 16 , wherein the oxidation step is implemented under dioxygen partial pressure ranging from 0.2 bar to 50 bar, in particular 1 bar to 20 bar, preferably 1 to 5 bar.

20 . The method according to claim 16 , wherein the dioxygen is continuously injected into the reaction medium, preferably in the form of a stream of air or oxygen, preferably injected in excess relative to the stoichiometry of the oxidation reaction.

21 . The method according to claim 16 , wherein the molar ratio of dioxygen relative to the product derived from the hydroformylation step is in he range of 3:2 to 100:2.

22 . The method according to claim 16 , wherein oxidation is conducted at a temperature in the range of 0° C. to 100° C., preferably 20° C. to 100° C., more preferably 30° C. to 90° C., further preferably 40° C. to 80° C., optionally with two consecutive temperature holds at increasing temperature.

23 . The method according to claim 16 also comprising:
3′) a reduction step during which the nitrile acid obtained at step 2′) is converted to ω-amino acid of formula HOOC—(CH 2 ) r+3 —NH 2 with regard to a nitrile acid; or
3″) a hydrolysis step during which the ester acid obtained at step 2′) is converted to diacid of formula HOOC—(CH 2 ) r+2 —COOH with regard to an ester acid.

24 . The method according to claim 1 , further comprising a polymer

Assignees

• Arkema France
• Univ Rennes
• Centre Nat Rech Scient

Inventors

• Dubois Jean-Luc
• Couturier Jean-Luc
• Ternel Jeremy
• Carpentier Jean-Francois

Classifications

• C07C253/30 Primary

  by reactions not involving the formation of cyano groups · CPC title

• C07C227/04

  Formation of amino groups in compounds containing carboxyl groups · CPC title

• C07C51/373

  by introduction of functional groups containing oxygen only in doubly bound form · CPC title

• C07C253/34

  Separation; Purification · CPC title

• C07C67/347

  by addition to unsaturated carbon-to-carbon bonds · CPC title