Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
• • 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
  • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
  • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats

Definitions

• the subject of the present invention is a process for the preparation of monocarboxylated fatty acids, carrying at least two vicinal hydroxyl groups, and / or at least one epoxy function, from unsaturated fatty acids and / or their derivatives.
• One of these methods consists in oxidizing an unsaturated fatty acid in the form of an acid and / or of an ester with hydrogen peroxide, in the presence of a metal oxide based on tungsten or molybdenum. As a reminder, the resulting products are subsequently brought into contact with oxygen and a cobalt catalyst to obtain saturated fatty acids or their esters.
• reaction times are always long.
• one of the objects of the present invention is to provide a reaction which does not have a lag time.
• Another object of the present invention is to provide a method for controlling the exothermicity of this reaction, therefore helping to increase safety during the implementation thereof.
• the present invention makes an additional contribution to the safety conditions of the process, by proposing to carry out the reaction with an outstanding amount of hydrogen peroxide for the entire duration thereof.
• the process according to the invention makes it possible to achieve these objectives, not only without harming the yields of the reaction but on the contrary by improving them.
• the present invention which therefore relates to a process for the preparation of derivatives of monocarboxylic fatty acids, comprising at least two vicinal hydroxyl functions and / or at least one epoxy function, from unsaturated fatty acids and / or their derivatives, consisting in bringing into contact at least one reagent chosen from unsaturated fatty acids in the form of an acid and / or of an ester with hydrogen peroxide, in the presence of a tungsten compound and / or molybdenum.
• the process is characterized in that the reaction is carried out: 1) in the presence of at least one co-catalyst of formulas (I) and / or (II) below:
• R1, R 2 identical or different, represent a hydrogen atom; a C-1-C30 hydrocarbon radical, optionally carrying at least one group
• R 4 representing a hydrogen atom or a C-1-C4 hydrocarbon radical, and / or optionally bearing at least one double bond, and / or optionally bearing at least one hydroxyl group; a radical derived from an oil of vegetable origin or from an oil or fat of animal origin, the latter possibly being obtained from an alcoholysis reaction;
• R 3 represents a C-1-C30 hydrocarbon radical, optionally carrying at least one group -COOR 4 with R 4 representing a hydrogen atom or a C1-C4 hydrocarbon radical, and / or optionally carrying at least one double bond, and / or optionally bearing at least one hydroxyl group; a radical derived from an oil of vegetable origin or from an oil or fat of animal origin, the latter possibly being obtained from an alcoholysis reaction;
• the present invention likewise relates to the use of the compounds resulting from the abovementioned process, in which said products are reacted with nitric acid in the presence of a vanadium-based catalyst, optionally in the presence of a co- catalyst, followed by recovery of the resulting mono- and di-carboxylic acids. It has been found that implementing the production of these dihydroxylated compounds under the conditions claimed, makes it possible to have immediate oxidation with very good productivity.
• the drawbacks of the processes of the prior art such as the thickening of the reaction mixture or the uncontrollable nature of the temperature causing the appearance of undesirable products, unexpectedly, are avoided.
• the method according to the invention can be used on an industrial scale, with good guarantees of safety during implementation. Indeed, it is not necessary to provide a step of preliminary treatment of the catalyst.
• the risks of being in uncontrollable reaction conditions are very low.
• the reagent, as well as the oxidizing agents, used in the process will first be described.
• the method of the invention applies to any reagent chosen from unsaturated fatty acids, having at least one double bond.
• unsaturated fatty acid will be used generically and it will denote both the unsaturated fatty acids per se, alone or as a mixture, as well as their derivatives, that is to say -to say their ester or triglyceride form.
• the method according to the invention can be implemented using at least one reagent corresponding to an unsaturated fatty acid, of formula (III): [R5 - C (O) - O] n - 6 (III) formula in which:
• - n is a number equal to 1, 2 or 3
• R5 represents a C4-C40 alkenyl or alkadienyl radical, linear or branched,
• unsaturated fatty acids there may be mentioned unsaturated fatty acids having a single double bond such as linderic, myristoleic, palmitoleic, oleic, petroselenic, doeglic, gadoleic, erucic acids; unsaturated fatty acids having two double bonds such as linoleic acid; unsaturated fatty acids having 3 double bonds such as linolenic acid; unsaturated fatty acids having more than 4 double bonds such as isanic, stearodonic, arachidonic, chypanodonic acids; unsaturated fatty acids carrying a hydroxyl group such as ricinoleic acid.
• fatty acids chosen from palmitoleic, oleic, petroselenic, erucic, linoleic, linolenic and ricinoleic acids are used more particularly.
• oils and fats which it is quite possible to use as a reagent, in the process according to the invention.
• oils of animal origin mention may be made, among others, of sperm whale, dolphin, whale, seal, sardine, herring, shark, cod liver oils; beef feet as well as beef, pork, horse and mutton fats (tallow).
• sources of vegetable origin mention may be made, among others, of rapeseed, sunflower, peanut, olive, walnut, corn, soybean, flax, hemp, grape seed, copra, palm, seeds cotton, babassu, jojoba, sesame, castor, coriander.
• oils mentioned below are preferably used in the process of the invention are rapeseed, sunflower, soybean, flax, castor, coriander oils. It is also possible to start from the esters corresponding to the said acids, in particular the methyl, ethyl and propyl esters, and there may be mentioned more particularly the alcoholysis products, more specifically methanolysis, oils in particular, and more preferably oils. rapeseed.
• the reactant is oxidized by hydrogen peroxide.
• the hydrogen peroxide used according to the invention can be in the form of an aqueous solution.
• aqueous solutions have a hydrogen peroxide concentration less than or equal to 70%.
• the hydrogen peroxide in the context of a first variant, consisting in introducing hydrogen peroxide gradually into the reaction medium, the hydrogen peroxide can be implemented in a concentrated form, as soon as the rate of introduction hydrogen peroxide remains such that the total concentration of this compound in the reaction medium, during the reaction, is less than or equal to 20%.
• the reaction according to the invention is carried out in the presence of an amount of hydrogen peroxide equal to the stoichiometry or corresponding to an excess ranging from 1 to 300 mol% relative to the number of double bonds to be reacted (in other words, to be oxidized), present in the reagent. More particularly, an excess corresponding to 1 - 200 mol% is used. According to an advantageous embodiment of the invention, the reaction is carried out in the presence of hydrogen peroxide with an excess of 1 - 100 mol%.
• the first step of the process according to the invention is carried out in the presence of at least one tungsten and / or molybdenum compound, as a catalyst.
• the catalyst is preferably chosen from: tungstic acid, phosphotungstic acid, molybdic acid, phosphomolybdic acid, or their precursors. It is therefore preferably in acid form. It is possible to start directly from the abovementioned compounds or else to form them in situ from their oxides or salts.
• molybdenum-based catalysts there may be mentioned: - molybdenum halides, for example, molybdenum hexafluoride, molybdenum tri-tetra- or pentachloride, molybdenum di- tri- or tetrabromide,
• molybdenum oxides such as dioxide, trioxide, pentaoxide or molybdenum sesquioxide
• molybdenum oxyhalides such as molybdenum oxifluoride or oxytetrafluoure, oxidichloride, oxytrichloride, oxytetrachloride, molybdenum oxypentachloride, molybdenum acid oxychloride, molybdenum oxidibromide,
• tungsten halides for example, tungsten hexafluoride, tungsten di-tetra-penta- or hexachloride, tungsten di-penta- or hexabromide, - tungsten oxides such as dioxide, trioxide, pentaoxide or tungsten sesquioxide,
• tungsten oxyhalides such as tungsten oxytetrafluoure, oxydichloride, tungsten oxytetrachloride, oxydibromide, tungsten oxytetrabromide, - tungsten metaphosphate,
• the amount of catalyst based on tungsten and / or molybdenum used, expressed by the weight ratio between the hydrogen peroxide and said catalyst, can advantageously be between 1 and 35%, preferably between 3 and 20%.
• the process according to the invention is therefore characterized in that the reaction is carried out in the presence of at least one cocatalyst which is chosen from the compounds of formulas (I) or (II) below:
• ° R 1 , R 2 identical or different, represent a hydrogen atom; a C1-C30 hydrocarbon radical, optionally carrying at least one group
• R 4 represents a hydrogen atom or a C1-C4 hydrocarbon radical, and / or optionally bearing at least one double bond, and / or optionally bearing at least one hydroxyl group
• a derivative radical an oil of vegetable origin or an oil or fat of animal origin possibly being obtained from an alcoholysis reaction
• R 3 represents a C1-C30 hydrocarbon radical, optionally carrying at least one -COOR 4 group with R 4 representing a hydrogen atom or a C1-C4 hydrocarbon radical, and / or optionally carrying at least one double bond, and / or optionally bearing at least one hydroxyl group
• a radical derived from an oil of vegetable origin or from an oil or fat of animal origin the latter possibly being obtained from an alcoholysis reaction
• the compounds of formulas (I) and (II) further comprising at least 7 carbon atoms;
• the reaction according to the invention is carried out in the presence of at least one co-catalyst of formula (I) or (II) chosen from the compounds for which at least one of the radicals R 1 , R2, or l 'one of the radicals R3, comprises at least 7 carbon atoms.
• at least one of the radicals R 1 , R 2 , or one of the radicals R 3 may contain one or more hydroxyl groups. In the case where there are several hydroxyl groups, these can be vicinal or not, for all or only some of them.
• the reaction is carried out in the presence of a co-catalyst chosen from fatty acid derivatives or fatty acid esters, saturated or not, comprising at least 7 , and preferably at least 9 carbon atoms in their longest chain, and further carrying at least two vicinal hydroxyl functions or at least one epoxy function.
• a co-catalyst chosen from fatty acid derivatives or fatty acid esters, saturated or not, comprising at least 7 , and preferably at least 9 carbon atoms in their longest chain, and further carrying at least two vicinal hydroxyl functions or at least one epoxy function.
• dihydroxylated fatty acids / esters (vicinal OH) or epoxidized which may be used, reference may be made to the derivatives of those mentioned in the list of reagents which can be used in the process according to the invention .
• the process according to the invention can be implemented in the presence of dihydroxylated (vicinal OH) or epoxidized derivatives of those whose list has been indicated previously; list relating to the reagents likely to be used in the process, as a reagent.
• a co-catalyst of this type there may be mentioned, without intending to be limited thereto, the acid 9,10 - stearic dihydroxy, the acid 6,7 - stearic dihydroxy, acid 4, 5 - dihydroxy dodecanoic acid 12,13 - dihydroxy oleic, acid 9,10 - dihydroxy linoleic, acid 9,10,12,13 - tetrahydroxy stearic, acid 15,16 - dihydroxy linoleic, l 9,10,12,13,15,16 - stearic hexahydroxy
• the co-catalyst is chosen so that it corresponds to the final product obtained by the process according to the invention.
• the proportion of cocatalyst relative to that of the catalyst based on molybdenum and / or tungsten is greater than 0.2, preferably greater than 1.
• the oxidation reaction is carried out by gradually introducing the hydrogen peroxide so that the concentration of this compound in the reaction mixture does not exceed 20% by weight of said mixture.
• the concentration of hydrogen peroxide in the reaction mixture, during the reaction is between 3 and 15% by weight of the reaction mixture.
• Another characteristic of the invention consists in carrying out the reaction at a temperature between 80 ° C and 100 ° C.
• the reaction is carried out at a temperature in the region of 100 ° C.
• the reaction is carried out at the reflux temperature of water.
• the reaction according to the present invention can also be carried out in the presence of a solvent.
• the latter is more particularly chosen from the compounds inert with respect to the reactants and oxidizing agents used, namely hydrogen peroxide and the tungsten / molybdenum-based compound, in the reaction conditions.
• the solvent chosen is preferably insoluble in water.
• linear, branched or cyclic alkanes comprising at least six carbon atoms, optionally halogenated; aromatic compounds, optionally halogenated; saturated acids comprising from two to 12 carbon atoms.
• Saturated oils are also suitable.
• suitable compounds there may be mentioned very particularly hexane, cyclohexane, heptane, ethyl acetate, benzene, chlorobenzene, dichlorobenzene, trifluoromethylbenzene, toluene, xylene, acid acetic, pelargonic acid, lauric acid, etc.
• the solvent can either be stored in the reaction mixture, or separated from the latter by using any suitable method, such as the distillation of the solvent, or the crystallization of the product resulting from the reaction. It should be noted that it is particularly advantageous to use, as solvent, the reagent used during the reaction according to the invention. And in the case where the product resulting from the reaction according to the invention is subsequently used in a subsequent reaction, such as an oxidative cleavage reaction in the presence of nitric acid, the solvent can advantageously correspond to the product resulting from this reaction with nitric acid.
• the process of the invention is generally carried out under atmospheric pressure but it can also be carried out under pressures higher or lower than atmospheric pressure.
• the process according to the invention can be carried out continuously or not.
• the contacting of the reactants, co-catalyst and oxidizing agents can be carried out in all possible ways insofar as the process conditions mentioned previously, such as in particular the concentration in hydrogen peroxide, are checked.
• the reactant, the co-catalyst and, optionally, the compound based on molybdenum and / or tungsten are brought into contact first.
• the hydrogen peroxide is gradually introduced, possibly in the presence of the tungsten and / or molybdenum-based compound, if the latter has not been introduced beforehand.
• a sufficient part of the dihydroxy or epoxide compound produced during this step is returned to the reactor in which the reaction is carried out. If necessary, additions of hydrogen peroxide are made to this reactor.
• the products resulting from the reaction according to the invention can then be separated from the reaction mixture by implementing known methods of separation. For example, separation by decantation can be carried out, in the case where a solvent is present. We can also consider implementing a crystallization step.
• the products resulting from the reaction according to the invention can, and this represents a second object of the invention, be used in a process for the preparation of saturated fatty acids.
• the products resulting from the reaction according to the invention are reacted with nitric acid in the presence of a vanadium-based catalyst, optionally in the presence of a cocatalyst, followed by recovery of the mono- acids. and resulting dicarboxylics.
• the products resulting from the reaction according to the invention, prior to contacting with nitric acid can be used after or without prior purification. But according to a preferred embodiment of the invention, the latter are used without purification. It should be noted that according to a variant of the invention, and in the case where the products obtained after the reaction according to the invention are not purified, the reaction mixture is separated from the water produced during the reaction according to the invention.
• reaction mixture thus obtained does not undergo any other separation treatment, before being engaged in the reaction with nitric acid; operation during which an oxidative hydrolysis and cutting is carried out.
• an aqueous solution of nitric acid having a concentration which can vary between 30% and 100% is used.
• Nitric acid is involved in large excess.
• the amount of nitric acid represents from 2 to 50 times and preferably from 4 to 10 times the weight of the starting reagent.
• NO + generator it is preferable, in order to initiate nitric oxidation, to add a NO + generator.
• a NO + generator one can start from nitrogen dioxide, nitrogen anhydride, nitrogen peroxide, or even nitrogen oxide.
• said agent is gaseous under the reaction conditions, it is bubbled into the medium.
• the amount of this agent can vary widely. It is advantageously between 0 and 5% of the weight of nitric acid and preferably between 0 and 1%.
• nitric acid is used in the presence of a vanadium-based catalyst.
• vanadium halides such as vanadium tri-tetra- or pentafluoride, vanadium di- or tetrachloride, vanadium tribromide,
• vanadium oxides such as vanadium oxide, vanadium dioxide, vanadium sesquioxide, vanadium pentaoxide,
• the vanadium oxyhalides in particular the vanadium di- or trifluoride oxides, the vanadium monodi- or trichloride, the oxy monodi- or vanadium tribromide,
• ammonium vanadates are preferably chosen as catalyst.
• the amount of vanadium-based catalyst used, expressed by the weight ratio between the catalyst expressed as HVO3 and nitric acid is preferably between 0.001 and 1%.
• a co-catalyst based on a metal from group Vlla and VIII of the periodic table is used, and there may be mentioned, preferably, catalysts based on: manganese, iron, nickel, ruthenium and cobalt.
• the preferred salts are the following: iron nitrate II, iron nitrate III, nickel nitrate II, cobalt nitrate, cobalt III nitrate, cobalt II acetate, manganese carbonate II, ruthenium III chloride.
• the amount of cocatalyst expressed by the weight ratio between the cocatalyst and nitric acid is preferably between 0.001 and 1%.
• a preferred embodiment of the invention consists in carrying out this nitric oxidation step, in the presence of oxygen or a gas containing it.
• the quantity of oxygen to be used is not critical insofar as it is such that neither the feed gases, nor any gas phase capable of appearing in the reaction zone is in the range of the explosive compositions , taking into account the other parameters or reaction conditions chosen.
• the quantity of oxygen can be in excess or in defect with respect to the stoichiometry of the reaction, with respect to the substrate to be oxidized.
• the oxygen or air pressure of the reaction varies between 1 and 10 bar.
• the temperature is preferably chosen between 40 ° C and 100 ° C, and more preferably between 60 and 90 ° C.
• reaction with nitric acid is carried out at atmospheric pressure.
• the aqueous and organic phases are separated, preferably by hot decantation.
• One or more washes of the organic phase are preferably carried out with water in order to recover any saturated dicarboxylic fatty acids remaining in the organic phase.
• the carboxylic acids obtained are then recovered by crystallization, by simply cooling the aqueous phase and they are recovered according to conventional techniques of solid / liquid separation, preferably by filtration.
• the separation can optionally be followed by one or more washes with water. Furthermore, the organic phase is treated in order to remove the organic solvent by distillation.
• the monocarboxylic acids are separated from the organic phase according to conventional liquid / liquid separation techniques, preferably distillation.
• the reaction of the compounds comprising vicinal hydroxyl or epoxy functions is described in patent application EP 701 989, to which reference may be made for more details.
• the mixture is heated to 80 ° C. with stirring, then 1.05 g of hydrogen peroxide (30% solution) are introduced and the mixture is left to react for 15 minutes (test 1) and for 45 minutes (test 2).
• the aqueous phase is removed and the organic mass is dried by vacuum distillation.
• the assays are carried out by NMR analysis.
• the assembly is composed of three glass reactors mounted in cascade, comprising a double envelope for circulation of thermostatically controlled water and mechanical stirring means.
• Thermal monitoring is carried out and recorded on the heating flows, and in the masses.
• - Reactor 2 aqueous solution of hydrogen peroxide (15%) heated to 87 ° C and comprising tungstic acid.
• the temperature of the mass is then controlled by the water brought to the boil.
• the end of the reaction is observed by the end of the exotherm.
• reaction mass is then drained into reactor 3 (decanter 70 ° C), with gentle stirring and then decanted after stirring has stopped.
• composition used is as follows:

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• 1999
  • 1999-01-28 FR FR9900960A patent/FR2789073B1/fr not_active Expired - Fee Related
• 2000
  • 2000-01-28 EP EP00901668A patent/EP1147073A1/de not_active Withdrawn
  • 2000-01-28 WO PCT/FR2000/000201 patent/WO2000044704A1/fr not_active Ceased
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