EP2867196A1 - Verfahren zur synthese von biobasierten ungesättigten säuren - Google Patents

Verfahren zur synthese von biobasierten ungesättigten säuren

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Publication number
EP2867196A1
EP2867196A1 EP13744649.8A EP13744649A EP2867196A1 EP 2867196 A1 EP2867196 A1 EP 2867196A1 EP 13744649 A EP13744649 A EP 13744649A EP 2867196 A1 EP2867196 A1 EP 2867196A1
Authority
EP
European Patent Office
Prior art keywords
compound
formula
process according
reaction
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13744649.8A
Other languages
English (en)
French (fr)
Inventor
Jessica ALLARD
Frédéric CAIJO
Aurélie MOREL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Omega Cat System
Novance SA
Original Assignee
Omega Cat System
Novance SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Omega Cat System, Novance SA filed Critical Omega Cat System
Publication of EP2867196A1 publication Critical patent/EP2867196A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones

Definitions

  • the invention relates to a process for preparing a diacid, preferably a long-chain diacid, by alkenolysis from a long chain fatty acid having at least one unsaturation or from a mixture of such acids.
  • fat preferably bio-based.
  • Long-chain diacids are used in more and more varied fields and are the subject of an industrial demand which is constantly increasing.
  • the demand is particularly strong especially in the field of polymers, such as polyesters, lubricants and cosmetics.
  • the diacids can be produced from vegetable oils via various synthetic routes such as fermentation, oligomerization, oxidative cleavage, hydroformylation followed by an oxidation step and finally the metathesis of olefins.
  • the metathesis of olefins is a chemical reaction that induces a redistribution of the alkylidene moieties by cleavage of the carbon-carbon double bond in the alkenes.
  • the reaction is catalyzed by transition metals such as nickel, tungsten, rhenium, ruthenium and molybdenum.
  • transition metals such as nickel, tungsten, rhenium, ruthenium and molybdenum.
  • the invention relates to a process for preparing a compound of formula (I),
  • n is an integer from 1 to 21.
  • the process comprises reacting a light olefin fraction in the presence of a metathesis catalyst with a compound having 10 to 24 carbon atoms of the following formula (II): in which,
  • n is an integer from 1 to 21,
  • R is a hydrogen atom or an alkyl or alkenyl chain of 1 to 20 carbon atoms optionally substituted with at least one hydroxyl group
  • the process according to the invention allows the preparation of diacids of formula (I) from a single compound of formula (II), that is to say, from a previously purified product.
  • the compound of formula (II) may be used in a mixture comprising at least one other compound of formula (II).
  • the process allows the preparation of a diacid of formula (I) from a hydrolysed vegetable oil, comprising for the most part a compound of formula (II) and other compounds, especially saturated chain fatty acids, or other compounds of formula (II), such as monounsaturated and polyunsaturated chain fatty acids.
  • major compound is meant a compound (II) present at least 50% by weight of the mixture.
  • This particular embodiment makes it possible to obtain diacid compounds from vegetable oils or hydrolysed triglycerides, without it being necessary to purify and / or separate the starting compound (II) in order to use it. in the reaction.
  • the preparation of a diacid of formula (I) is made from a purified hydrolysed oil, comprising a compound of formula (II) present at more than 80% of the mixture.
  • the compound of formula (II) is preferably a long chain natural fatty acid.
  • Long-chain natural fatty acid is understood to mean an acid derived from a plant or animal medium, including algae, and more particularly from the plant kingdom and therefore easily renewable.
  • the compound of formula (II) has at least 12 carbon atoms and more preferably at least 14 carbon atoms.
  • C 10 acids such as obtusilic acid (cis-4-decenoic acid) and caproleic acid
  • C 12 acids lauroleic acid (cis-5-dodecenoic acid) and linderic acid (cis-4-dodecenoic acid)
  • C14 acids such as myristoleic acid (cis-9-tetradecenoic acid), physetric acid (cis-5-tetradecenoic acid) and tsuzuic acid (cis-4 -tetradecémoique)
  • C16 acids such as palmitoleic acid (cis-9-hexadecenoic)
  • C18 acids such as oleic acid (cis-9-octadecenoic), elaidic acid (trans-9) -octadecenoic), petroselinic (cis-6-octadecenoic), vaccenic acid (cis-11-octadecenoi
  • the fatty acids used are oleic acid (cis-9-octadecenoic acid), myristoleic acid (cis-9-tetradecenoic acid), palmitoleic acid (cis-9-hexadecenoic acid), elaidic acid (trans - 9-octadecenoic acid), ricinoleic acid (12 ⁇ hydroxy-9-cis octadécéno 'AICS), gadoleic acid (cis-9-eicosenoic) or erucic acid.
  • the acid of formula (II) is oleic acid.
  • the polyunsaturated chain fatty acid is chosen from linoleic acid and linolenic acid.
  • a saturated chain fatty acid may be palmitic acid (C16) or stearic acid (C18).
  • the fatty acids that can be used as substrates in the process of the invention are advantageously biobased and may for example be derived from rapeseed, sunflower, soybean, oleic sunflower, castor oil, safflower or coconut oil. palm, tallow, olive, cotton, flax, corn, Chinese wood, peanut, calendula, grape seed.
  • the catalyst used is chosen from the group consisting of ruthenium based metathesis reaction catalysts, based on tungsten or on the basis of molybdenum, optionally based on osmium, chromium and / or of rhenium and / or other metals selected from groups 6, 7 and 8 of the periodic table of elements.
  • the catalysts that can be used for cross-fat metathesis reactions are known to those skilled in the art and a list of acceptable catalysts is for example given in document WO2009 / 020667 (pages 18 to 46) as well as WO2008 / 065187 ( pages 29 to 36) which are incorporated by reference.
  • the catalysts particularly suitable for the practice of the process according to the invention are for example the first and second generation Grubbs catalysts based on ruthenium.
  • a catalyst particularly suitable for producing the desired yields is the catalyst of formula D:
  • M71 a-2F (M71). This catalyst is available from Umicore (Belgium) under the name M71-SiPr.
  • This catalyst is available from Materia Inc. (United-States) under the name HG-SIPr (Hoveyda-Grubbs SIPr).
  • the catalyst used in this reaction may be supported or unsupported.
  • the supports that can be used during this reaction are of a varied nature and may be chosen from the group consisting of resins, polymers, PEGs or silica gels having an amino, hydroxy, alkylthio, haloalkyl or carboxylic surface or terminal group. Carbon nanotubes and biopolymers are also possible supports.
  • Catalysis can be carried out in the presence or absence of solvent and / or ionic liquid.
  • the ionic liquids possibly used during this reaction are chosen from the group consisting of liquid salts of general formula Q + A " in which Q + represents a quaternary phosphonium, a quaternary ammonium, a quaternary guanidinium or a quaternary sulphonium and A " represents an anion that is capable of forming a liquid salt below 90 ° C.
  • the catalyst may be added either in dissolved form in an organic solvent (eg dichloromethane), or in powder form in the initial reaction mixture. Furthermore, the catalyst may be added either sequentially to the reaction medium, for example in two portions, or continuously in the reaction mixture.
  • organic solvent eg dichloromethane
  • olefin light fraction is meant at least one compound selected from a range of unsaturated hydrocarbons comprising at least one double bond and consisting of a number of carbon atoms ranging from 2 to 10, preferably from 2 to 5.
  • this compound is chosen from the group consisting of ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, 2-pentene and 2-pentene. 1-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, cyclopentene and a mixture of these compounds.
  • Ethylene is particularly suitable for the process according to the invention.
  • the process according to the invention makes it possible to obtain high yields (for example at least 60% by weight of the compound (I)), in a short reaction time, for example less than or equal to 10 hours and preferably less than 10 hours. 6 hours.
  • a short reaction time for example less than or equal to 10 hours and preferably less than 10 hours. 6 hours.
  • at least 60% by weight of the compound (I) is obtained, in a reaction time of less than or equal to 4 hours, preferably less than 2 hours.
  • at least 70% by weight of the compound (I) is obtained in 2 hours, more preferably 72% by weight of compound (I).
  • the reaction is conducted at a temperature ranging from 44 ° C to 120 q C.
  • the temperature is selected within the range of 45 ⁇ 80 ° C, preferably 45 ⁇ to 65 ° C and more preferably in the range of 48 ° C to 55 ° C.
  • the reaction is carried out at a temperature of approximately 50 ° C., that is to say 50 ⁇ 1 ° C.
  • the reaction temperature is advantageously chosen to be equal to or lower than the temperature at which the diacid, or compound of formula (I), precipitates.
  • this temperature is also advantageous to choose this temperature so that it is greater than or equal to the melting point of the compound of formula (II) in the majority of the starting mixture and / or by-products of the reaction. This temperature range thus makes it possible to precipitate the diacid selectively and rapidly, while keeping the other compounds of the reaction mixture in soluble form. This makes it possible to promote equilibrium displacements in the desired direction.
  • the reaction should proceed at a temperature above the melting temperature of elaidic acid (42-44 ⁇ C).
  • Elaidic acid is a monoacid of configuration E which is a by-product of the metathesis reaction between 1-decene and dec-9-enoic acid which are themselves the alkylidene moieties obtained by the split of the carbon double bond carbon of oleic acid (see Figure 1).
  • the reaction must It can also be carried out at a temperature advantageously chosen lower than the melting temperature of octadec-9-enedioic acid (E), ie at a temperature of less than 98% in order to maintain the desired diacid in solid form.
  • These temperatures correspond to the limiting temperatures related to the physicochemical characteristics of the compounds involved.
  • a reaction temperature of about 50.degree. C. is therefore particularly suitable for the synthesis of octadec-9-enedioic acid (E).
  • the reaction should preferably take place at a temperature above the melting temperature of the acidic acid, the isomer (E) of erucic acid, which is around 58 ° C and below the melting temperature of the diacid (E) (1, 26-hexacos-13-enedioic acid) at about 95-1 10 ° C.
  • a temperature ranging from 65 to 85 ° C. is therefore adapted to this particular aspect of the invention.
  • the light olefin fraction is reacted in gaseous form and / or at a pressure of between atmospheric pressure and 100 bar.
  • the light olefin fraction is at a pressure ranging from 2 to 30 bar, and more preferably from 5 to 20 bar, for example 10 bar.
  • the light olefin fraction is reacted at a pressure of 1 bar to 3 bar.
  • it is from 1.5 bar to 2.5 bar, more preferably from 1.7 bar to 2.3 bar, typically the pressure is 2 bar +/- 1 bar.
  • the process makes it possible to obtain predominantly the compound in the Trans configuration.
  • the compound of formula (I) obtained by the process according to the invention is octadec-9-enedioic acid, which is obtained by reacting oleic acid with ethylene, in the presence of a metathesis catalyst preferably with ruthenium, at a temperature preferably chosen in the range from 45 to 65 ° C, and more particularly 49 to 52 ⁇ C (for example 50 ° C), and under an ethylene pressure preferably chosen in the range ranging from 5 to 20 bar or from 1 to 3 bar (for example 2 bar).
  • the synthesis is completed in less than 10 hours, and preferably in about 2 hours.
  • the process according to the invention can be used in an integrated diacid synthesis process or compound of formula (I).
  • This process comprises at least one preliminary step of converting a triglyceride, such as a vegetable oil, into an acid of formula (II) by reacting hydrolyzing and / or pretreating the product of a hydrolysis reaction carried out on triglycerides, for example, to remove or reduce certain impurities.
  • the process according to the invention may comprise a purification step of the diacid obtained.
  • the hydrolysis of triglycerides to obtain fatty acids is a known reaction which is carried out by subjecting the triglycerides to a sodium-based treatment.
  • the pretreatment of the hydrolysis product is an advantageous step which makes it possible to improve the efficiency of the metathesis reaction.
  • the fatty acids obtained by hydrolysis of vegetable oils contain impurities, in particular peroxides, which can act as poisons for ruthenium-based olefin metathesis catalysts.
  • the presence of these impurities in fatty acids depends on several factors including the plant from which the oil is extracted, the geographical origin, the date of harvest, the extraction method and the hydrolysis method.
  • Selective pretreatments can therefore be applied in order to reduce the content of impurities, and particularly peroxide, to less than 1 mEq / kg, preferably less than 0.5 mEq / kg.
  • the solid particles can be removed by decantation and / or by filtration on filters of 60 ⁇ at 5 ⁇ , preferably from 10 ⁇ to 5 ⁇ .
  • Vacuum degassing or nitrogen bubbling can be performed to remove traces of oxygen.
  • the fatty acids may be treated thermally and / or chemically to remove impurities that may reduce the effectiveness of the catalysts used, for example, there may be mentioned in particular: peroxides, glycerol, water, aldehydes, alcohols, by-products related to oxidative degradation of fatty acids, terminal conjugated polyolefins, nitriles and other colored impurities such as indane, naphthalene, phenanthrene, pyrene and alkylbenzenes.
  • the heat treatment is generally carried out at a temperature ranging from 30 ° C. to 200 ° C., preferably from ⁇ ' ⁇ to ⁇ ⁇ ' ⁇ and according to a time appropriate to the impurity content which must be eliminated.
  • This heat treatment can be carried out under reduced pressure to increase its effectiveness.
  • the chemical treatment of the product of the hydrolysis of triglycerides can be carried out with sodium bisulfite and / or sodium borohydride.
  • Sodium bisulphite is known to reduce peroxides to aldehydes and form with them water-soluble complexes.
  • Sodium bisulfite in aqueous solution may be added to the composition at 5% to 0.1% by weight, preferably 0.5% to 0.1% by weight.
  • Sodium bisulfite is then removed from the medium by aqueous treatment.
  • Sodium borohydride is known to reduce peroxides to aldehydes and then to alcohols. Its use in the pretreatment of the fatty acid compositions also makes it possible to remove colored impurities or the glycerol resulting from the hydrolysis of the oil.
  • Sodium borohydride may be added to the vegetable oil in a proportion of from 5% to 0.1% by weight and preferably from 0.5% to 0.1% by weight. The sodium borohydride is then removed from the medium by aqueous treatment.
  • the aqueous phase is then removed by decantation or by centrifugal force or by any other liquid-liquid separation means.
  • Traces of residual water can be removed by flash distillation, which consists in vaporizing residual traces of water and obtaining two phases in liquid-vapor equilibrium at the temperature and flash pressure.
  • the invention also relates to the diacids directly produced by the process as described above as well as to their industrial and cosmetic uses.
  • FIG. 1 represents the reaction scheme of the reaction carried out in the example
  • Fig. 2 shows a non-exhaustive list of catalyst structures that can be used to practice the invention (Fig. 2A, Fig. 2B, Fig. 2C, Fig. 2D, Fig. 2E, Fig. 2F, Fig. 2G, Fig. 2H), and
  • FIG. 3 represents the diagram of an integrated diacid synthesis process described above.
  • the catalyst is destroyed by adding 1 mL of ethylvinyl ether.
  • the solid thus obtained undergoes filtering and washing steps with two successive additions of 20 ml of cyclohexane. Then it is heated to 60 ° C in suspension in 20 mL hexane, filtered hot and washed with 20 mL hot hexane.
  • the catalyst is destroyed by adding 1 mL of ethylvinyl ether.
  • the solid thus obtained undergoes filtering and washing steps with two successive additions of 20 ml of cyclohexane. Then it is heated to 60 ° C in suspension in 20 mL hexane, filtered hot and washed with 20 mL hot hexane.
  • the mass percentages of the constituent compounds of the solid obtained are as follows:
  • Example 2 The protocol of Example 2 is repeated identically with the HG-SIPr catalyst.
  • the mass percentages of the constituent compounds of the solid obtained are as follows:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP13744649.8A 2012-06-29 2013-06-27 Verfahren zur synthese von biobasierten ungesättigten säuren Withdrawn EP2867196A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1256280A FR2992642B1 (fr) 2012-06-29 2012-06-29 Procede de synthese d’acides insatures biosources
PCT/FR2013/051506 WO2014001725A1 (fr) 2012-06-29 2013-06-27 Procédé de synthèse d'acides insaturés biosourcés

Publications (1)

Publication Number Publication Date
EP2867196A1 true EP2867196A1 (de) 2015-05-06

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EP13744649.8A Withdrawn EP2867196A1 (de) 2012-06-29 2013-06-27 Verfahren zur synthese von biobasierten ungesättigten säuren

Country Status (5)

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US (1) US9376366B2 (de)
EP (1) EP2867196A1 (de)
CN (1) CN104411672A (de)
FR (1) FR2992642B1 (de)
WO (1) WO2014001725A1 (de)

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GB201413216D0 (en) * 2014-07-25 2014-09-10 Croda Internat Plc And Sederma Sas Anti-Dandruff Composition
FR3024037B1 (fr) 2014-07-25 2018-03-02 Sederma Ingredient actif cosmetique ou dermatologique comprenant un melange d'acides dicarboxyliques gras insatures, compositions le comprenant et utilisations cosmetiques ou dermatologiques
US9469394B2 (en) 2015-03-10 2016-10-18 Qualcomm Incorporated Adjustable weight distribution for drone
US11267555B2 (en) * 2018-01-08 2022-03-08 GEOSAT Aerospace & Technology Methods and unmanned aerial vehicles for longer duration flights
CN115073281B (zh) * 2022-07-28 2024-01-23 安徽农业大学 木本油基不饱和二酸的制备方法、在制备聚酰胺中的应用及制成的聚酰胺

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Publication number Priority date Publication date Assignee Title
WO1996004289A1 (en) * 1992-04-03 1996-02-15 California Institute Of Technology High activity ruthenium or osmium metal carbene complexes for olefin metathesis reactions and synthesis thereof
CA2442636A1 (en) * 2001-03-30 2002-10-10 California Institute Of Technology Selective ring-opening cross-metathesis of cycloolefins
FR2896500B1 (fr) * 2006-01-24 2010-08-13 Inst Francais Du Petrole Procede de co-production d'olefines et de diesters ou de diacides par homometathese de corps gras insatures dans des liquides ioniques non-aqueux.
FR2896498B1 (fr) * 2006-01-24 2008-08-29 Inst Francais Du Petrole Procede de co-production d'olefines et de diesters ou de diacides a partir de corps gras insatures.
FR2909382B1 (fr) 2006-11-30 2009-01-23 Enscr Complexes catalytiques a base de ruthenium et utilisation de tels complexes pour la metathese d'olefines
FR2917406B1 (fr) * 2007-06-13 2012-08-03 Arkema France Procede de synthese de diacides ou diesters a partir d'acides et/ou d'esters gras naturels
EP2183205A4 (de) * 2007-08-09 2013-10-02 Elevance Renewable Sciences Chemische verfahren zur behandlung eines metathese-einsatzmaterials
FR2921363B1 (fr) 2007-09-20 2009-11-06 Arkema France Procedes de synthese de diacides gras par metathese de diacides insatures obtenus par fermentation d'acides gras naturels
FR2933695B1 (fr) * 2008-07-10 2010-08-20 Arkema France Procede de synthese de l'acide amino-9-nonanoique ou de ses esters a partir d'acides gras naturels insatures.

Non-Patent Citations (1)

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Title
See references of WO2014001725A1 *

Also Published As

Publication number Publication date
FR2992642A1 (fr) 2014-01-03
US9376366B2 (en) 2016-06-28
FR2992642B1 (fr) 2015-06-19
CN104411672A (zh) 2015-03-11
US20150336871A1 (en) 2015-11-26
WO2014001725A1 (fr) 2014-01-03

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