US 2014O155647A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2014/0155647 A1 Dubois (43) Pub. Date: Jun. 5, 2014 (54) METHOD FOR THE SYNTHESIS OF DIACIDS Publication Classification OR DESTERS FROMINATURAL FATTY ACDS AND/ORESTERS (51) Int. Cl. C07C 67/303 (2006.01) (71) Applicant: Arkema France, Colombes (FR) CD7C5L/36 (2006.01) (52) U.S. Cl. (72) Inventor: Jean-Luc Dubois, Millery (FR) CPC ............... C07C 67/303 (2013.01); C07C 51/36 (2013.01) (21) Appl. No.: 13/946,292 USPC ........................................... 560/190; 562/592 (57) ABSTRACT (22) Filed: Jul.19, 2013 Disclosed herein a process for the synthesis of diacids or diesters of general formula ROOC (CH)x-COOR, in O O which in represents an integer between 5 and 14 and R is either Related U.S. Application Data H or an alkyl radical of 1 to 4 carbon atoms, starting from (63) Continuation of application No. 12/664,182, filed on long-chain natural monounsaturated fatty acids or esters Apr. 21, 2010, now abandoned, filed as application No. comprising at least 10 adjacent carbonatoms per molecule, of PCT/FR2008/051038 on Jun. 11, 2008. formula CH (CH)n-CHR—CH2—CH=CH-(CH2)p- COOR, in which R represents Horan alkyl radical compris (30) Foreign Application Priority Data ing from 1 to 4 carbon atoms, R is either H or OH, and n and p, which are identical or different, are indices between 2 and Jun. 13, 2007 (FR) ....................................... O755733 11. US 2014/O 155647 A1 Jun. 5, 2014 METHOD FOR THE SYNTHESIS OF DACDS -continued OR DESTERS FROMINATURAL FATTY ACDS AND/ORESTERS 0001. The invention is targeted at a process for the synthe OH sis by metathesis of Saturated long-chain diacids or diesters OH starting from a monounsaturated fatty acid or fatty ester which is either natural or originates from the direct conver sion of a natural oil. 0002 Diacids are obtained industrially by various meth Adipic acid ods, all of which, however, exhibit some disadvantages. A great variety of these methods is enlarged upon in the Kirk Othmer Encyclopedia, Vol. A8, pages 523-539. 0003. It is possible to distinguish therein methods by deg radation, such as oZonolysis or oxidation, of vegetable fatty 0004. The ozonolysis of oleic acid, of petroselinic acid and acids. of erucic acid makes it possible to respectively produce the diacids comprising 9, 6 and 13 carbonatoms according to the OH above reaction process for petroselinic acid. 0005. Another example is the cleavage of ricinoleic acid -n-n-n-n-n-N---so by the action of sodium hydroxide at a temperature of greater Petroselinic acid than 180°C. This method, used industrially, makes it possible to obtain the diacid comprising 10 carbon atoms. The same method, as illustrated in the scheme below, can be OH applied to lesquerolic acid and results in the formation of a diacid comprising 12 carbon atoms. This method exhibits the advantage of using renewable start Lauric acid ing materials but is restricted essentially to the Co diacid, -- lesquerolic acid being still not very widespread, and thus this method is relatively little used. OH OH CH Ricinoleic acid OR OH OH N CH Lesquerolic acid NaOH, 180-250° / Not 2500 C. US 2014/O 155647 A1 Jun. 5, 2014 -continued O OH ~~~~~ O OH O OR OH O OR ~~~~. OH OH -- O O ~~~~ OH CH3 OH --~~~ CH 0006 Mention may also be made of the oxidative degra acids oleic (cis-9-octadecenoic) acid, elaidic (trans-9-octade dation of monocarboxylic acids by the action of NO. The cenoic) acid, petroselinic (cis-6-octadecenoic) acid, vaccenic oxidation of stearic acid makes it possible to obtain a mixture (cis-11-octadecenoic) acid and ricinoleic (12-hydroxy-cis-9- of sebacic acid and of caprylic acid; Suberic acid can be octadecenoic) acid, the Co acids gadoleic (cis-9-eicosenoic) obtained from palmitic acid. acid, gondoic (cis-11-eicosenoic) acid, cis-5-eicosenoic acid 0007. It is also possible to obtain diacids from smaller and lesquerolic (14-hydroxy-cis-11-eicosenoic) acid, and the molecules by using variant techniques of carbonylation. C. acids cetoleic (cis-11-docosenoic) acid and erucic (cis 0008 Finally, mention may be made of the bacterial fer 13-docosenoic) acid. mentation of paraffins, a well known method which makes it 0014. These various acids result from the vegetable oils possible to obtain numerous diacids of variable chain length. extracted from various plants, such as Sunflower, rape, castor However, this method does not make it possible to obtain oil plant, bladderpod, olive, soya, palm tree, coriander, celery, diacids with a length of greater than 16 carbon atoms as the dill, carrot, fennel or Limnanthes alba (meadowfoam). paraffins then have a melting point which is far too high for 0015 They also result from the terrestrial or marine ani conversion to be possible. Another major disadvantage is that mal world and, in the latter case, both in the form of fish or the bacteria consume a portion of the paraffins in order to mammals, on the one hand, and of algae, on the other hand. provide for their growth, resulting in low yields and in the They are in general fats originating from ruminants, from fish, need to purify the products. Such as the cod, or from marine mammals, such as whales or 0009. In the polymer industry, in particular for the produc dolphins. tion of polyamides of diacids/diamines type or of industrial polymers, it is necessary to have available a whole range of 0016. The invention is targeted at a process for the synthe diacids as starting materials, which diacids can in addition be sis of diacids or diesters of general formula ROOC (CH) converted to diamines of the same chain length by a simple COOR, in which X represents an integer between 5 and 24 chemical reaction. and R is either H or an alkyl radical of 1 to 4 carbon atoms, starting from long-chain natural monounsaturated fatty acids 0010. It is therefore necessary to find a type of process or esters comprising at least 10 adjacent carbon atoms per which makes it possible to obtain a virtually complete range molecule, of formula CH (CH), CHR CH of diacids and which, in addition, uses renewable materials of CH=CH-(CH2). COOR, in which R represents Horan natural origin. alkyl radical comprising from 1 to 4 carbonatoms, R is either 0011. The object of the invention is a process for the pro H or OH, and n and p, which are identical or different, are duction of a whole range of Saturated diacids or diesters of indices between 2 and 11, preferably between 3 and 11, which general formula ROOC (CH), COOR starting from fatty consists, in a first stage, in converting said natural fatty acid or acids of natural origin. ester, either by pyrolysis or by ethenolysis (ethylene cross 0012. The solution provided consists in carrying out the metathesis), into an W-monounsaturated fatty acid or ester of operation starting from long-chain natural monounsaturated general formula CH2=CH-(CH2), COOR, in which mis fatty acids. Long-chain natural fatty acid is understood to equal to p or p--1, depending on the nature of the fatty acid/ mean an acid resulting from plant or animal sources, includ ester treated and the conversion used, ethenolysis or pyroly ing algae, more generally from the plant kingdom, which are sis, then, in a second stage, in Subjecting the product thus thus renewable, comprising at least 10 and preferably at least obtained to a metathesis reaction, either homometathesis, in 14 carbon atoms per molecule. order to obtain a compound of formula ROOC (CH), 0013 Mention may be made, as examples of such acids, of CH=CH-(CH), COOR, or cross-metathesis with a the Co acids obtusilic (cis-4-decenoic) acid and caproleic compound of formula ROOC (CH), CH=CH-R, in (cis-9-decenoic) acid, the C acids lauroleic (cis-5-dode which R is either Horan alkyl radical comprising from 1 to cenoic) acid and linderic (cis-4-dodecenoic) acid, the Ca 4 carbon atoms, r is either 0 or 1 or 2 and R is H, CH or acids myristoleic (cis-9-tetradecenoic) acid, physeteric (cis COOR, in the last case forming a cyclic or noncyclic mol 5-tetradecenoic) acid and tsuZuic (cis-4-tetradecenoic) acid, ecule, in order to obtain an unsaturated compound of formula the C acid palmitoleic (cis-9-hexadecenoic) acid, the Cs ROOC (CH), CH=CH-(CH), COOR, and then, US 2014/O 155647 A1 Jun. 5, 2014 in a third stage, in finally converting, by hydrogenation of the acid, both oleic acid and linoleic acid; and rapeseed oil com double bond, the unsaturated compound to give a saturated prises, in addition to oleic acid, simultaneously linoleic acid, compound. linolenic acid and gadoleic acid. The presence of these diun 0017. The natural monounsaturated fatty acid or ester of saturated or polyunsaturated acids is not of major conse general formula CH (CH), CHOH-CH CH=CH-(CH2). COOR can be subjected to a pyrolysis quence with regard to the progression of the process insofar reaction. as, during the first stage, in the case of ethenolysis, linoleic 0018. The acid or the ester of formula CH=CH-(CH) acid will also form the w-monounsaturated fatty acid of gen —COOR resulting from the first stage can be subjected to eral formula CH2=CH (CH), COOR, with minor a homometathesis, the product of which, ROOC (CH.) amounts of short dienes and of C-olefins. In the case of 1 CH=CH-(CH2).