Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/32—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids

Definitions

• the invention relates to a process for the synthesis of long-chain ⁇ , ⁇ -aminoalkanoic acids or esters from a monounsaturated fatty acid or ester comprising at least one metathesis step.
• nylon 6 methylene chain length (-CH 2 ) n separating two amide functions -CO-NH-, which is why nylon 6, nylon 6-6, nylon 6 are known. 10, Nylon 7, Nylon 8, Nylon 9, Nylon 1 1, Nylon 13, etc.
• These monomers are generally manufactured by chemical synthesis using C2-C4 olefins, cycloalkanes or benzene, hydrocarbons derived from fossil sources, but also in certain cases from castor oil (Nylon, for example as raw materials). 1 1) or erucic oil (Nylon 13/13) or lesquerolic (Nylon 13).
• the first consists of a methanolysis of castor oil in a basic medium producing methyl ricinoleate which is then subjected to pyrolysis to obtain on the one hand heptanaldehyde and, on the other hand, methyl undecylenate.
• the latter has gone into acid form by hydrolysis.
• the formed acid is subjected to hydrobromination to give the ⁇ -bromo acid from which ammonia is passed to 1-amino-1-undecanoic acid.
• an adsorbent is a solution that requires the use of a large amount of adsorbent and is expensive in the process since it requires the investment of an adsorption column and a regeneration step of the adsorbent. It also leads to a loss of raw material that remains trapped in porosity on solid.
• the subject of the invention is a process for the synthesis of a long chain saturated ⁇ , ⁇ -amino ester (acid) comprising from 6 to 17 carbon atoms, said process comprising a first step of cross metathesis between a first acrylic compound chosen from acrylonitrile, acrylic acid or an acrylic ester and a second monounsaturated compound having at least one trivalent, nitrile, acid or ester function, one of these compounds having a nitrile function and the other an acid or ester function, in the presence of a ruthenium carbene type metathesis catalyst, and a second step of hydrogenation of the mono-unsaturated nitrile-ester (acid) obtained, said monounsaturated compound comprising at least one trivalent nitrile, acid or ester function having previously been subjected to purification by thermal and / or chemical treatment.
• R 1 H or (CH 2 ) m -R 4,
• R 2 COOR 5 or CN
• R 3 COOR 5 or CN
• R 4 H or R 2>
• R 5 alkyl radical of 1 to 4 carbon atoms, or H
• R 2 identical or different from R3.
• the purification by chemical or thermal treatment mentioned above is applicable to a process for preparing diacids, diesters, and / or dinitriles.
• the final ⁇ , ⁇ -aminoester (acid) formula synthesized essentially depends on that of the compound reacting with the acrylic compound.
• R 1 is either H, an alkyl radical or an alkyl functional radical having a trivalent function (CN, COOH or COOR).
• Ri will be H when the natural fatty ester will for example be subjected to ethenolysis or in some cases to pyrolysis.
• the ⁇ ' ⁇ , ⁇ -aminoester / acid formula obtained is then directly linked to the radical - (CH 2 ) n - of the fatty ester.
• n will be equal to 7 with oleic acid, 4 with petroselenic acid, 8 from ricinoleic acid subjected to pyrolysis, 10 from lesquerolic acid subjected to pyrolysis, etc. as described in the French patent application published under the number FR 2 912 741.
• R 1 will be an alkyl radical when in (CH 2 ) m -R 4 , R 4 is H. This corresponds to the use in the process of a monounsaturated natural fatty acid such as, for example, oleic, palmitoleic and petroselenic acids. , lauroleic etc.
• R 1 will be an alkyl radical functional when in (CH 2 ) m -R, R is a radical representing a trivalent function CN, COOH or COOR which will be identical to R 2 .
• the compound will then be in the diacid, diester or dinitrile form. It will then be particularly advantageous if the formula of the compound has a symmetry making it possible to optimize the yields of ⁇ , ⁇ -aminoester / final acid. Obtaining this type of compounds, particularly by metathesis, is described in the applications FR 2912741, FR0857780 and FR0950704 cited above.
• the choice of the trivalent function R3 may be related to the nature of the trivalent function of the other compound, R3 being able to be nitrile when R2 is ester acid and reciprocally ester / acid when R2 is nitrile.
• the cross-metathesis reaction with acrylonitrile is carried out with a compound chosen from 9-decenoic acid or 9-decenoate of methyl, resulting from the ethenolysis of oleic acid or methyl oleate.
• a triglyceride containing oleic acid, 10-undecenoic acid or 10-undecenoate of methyl derived from the cracking of ricinoleic acid or methyl ricinoleate, oleic acid or oleate of methyl, 9-octadecenedioic acid or methyl 9-octadecenedioate, derived from the homometathesis or fermentation of oleic acid, erucic acid and methyl erucate, 12-tridecenoic acid or Methyl 12-tridecenoate from the thermal cracking of desquerolic acid, 13-tetradecenoic acid or methyl 13-tetradecenoate derived from the ethenolysis of erucic acid, lesquerolic acid and methyl laquerolate, Gondoic acid or methyl gondoate , 1 1 -dodecenoic acid or 1 1-methyl dodecenoate derived from the
• the cross-metathesis reaction of the (acid) acrylic ester is carried out with a compound chosen from 9-decenenitrile derived from 9-decenoic acid, 10-undecenenitrile derived from 10-undecenoic acid, 9-octadecenenitrile or oleonitrile, derived from oleic acid, 9-octadecenedinitrile, derived from 9-octadecenedioic acid or the homometathesis of 9-decenenitrile, eruconitrile, 13-tetradecenonitrile derived from erucic acid, 12 -tridecenenitrile derived from lesquerolic acid after a thermal cracking step, 1 1 -dodecenenitrile from lesquerolic or gondoic acid after an ethenolysis step.
• the process for purifying the monounsaturated compounds derived from fatty acids comprising a nitrile, acid or ester function, prior to the metathesis step consists in destroying the hydroperoxide and / or peroxide type compounds by a heat treatment and / or chemical.
• the heat treatment is carried out at a temperature between 80 ° C and 250 ° C, preferably between 80 ° C and 180 ° C, in an inert atmosphere for a time sufficient to decompose the hydroperoxide and / or peroxide compounds.
• the temperature is between 100 and 200 ° C, more preferably between 100 and 150 ° C.
• the heat treatment is carried out without a solvent under a nitrogen atmosphere.
• the chemical treatment comprises a step of adding a compound selected from inorganic acids, bases, reducing agents, metals, metal salts, organic or inorganic compounds comprising ruthenium and mixtures thereof, for decomposing the compounds of type hydroperoxide and / or peroxide by reaction.
• the chemical treatment is carried out without a solvent or in a solvent subsequently used for the metathesis step.
• the reaction is carried out under conditions close to the stoichiometry between the peroxide and the reagent in question.
• the inorganic acids used are preferably chosen from sulfuric acid, perchloric acid and hydrochloric acid, and mixtures thereof, and used at a temperature of preferably between 20 and 50 ° C.
• the bases used are preferably amines chosen from triethylamine, diethylamine, isobutylamine, triethanolamine, dimethylaniline, diethylaniline, dimethylparatoluidine, and mixtures thereof and used at a temperature of preferably between 20 and 120.degree. vs.
• the reducing agents used are preferably chosen from trialkyl and triaryl phosphines, in particular triphenylphosphine, trialkyl or triaryl phosphites, especially triphenylphosphite, inorganic or organic sulphides, such as sodium hydrogen sulphide or thioxane, hydrazine, or the like.
• alkyl or aryl hydrazines such as diphenylhydrazine, hydroxylamine, formic acid, oxalic acid and mixtures thereof and carried out at a temperature of between 20 and 50 ° C.
• the metals used are preferably selected from alkali, alkaline earth and rare earth metals, aluminum, titanium, zirconium, zinc, tin, lead, bismuth, iron, nickel, cobalt, copper, silver and mixtures thereof, and in particular the iron, nickel, cobalt, copper, silver and their mixtures, and implemented at a temperature between 20 and 150 ° C, and most preferably between 20 ° C and 50 ° C.
• the most reactive compounds will be the alkali metals, then the alkaline earth metals, then the rare earths and finally the transition metals, silver being a less reactive compound.
• the metal salts used are preferably selected from iron derivatives and preferably iron (II) acetate, iron (III) acetate, iron (II) acetylacetonate, iron (III) acetylacetonate, ), cobalt derivatives and preferably cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) 2-ethylhexanoate, copper derivatives and preferably copper (1) acetate, copper (II) acetate, copper (1) acetylacetonate, copper (II) 2-ethylhexanoate, manganese derivatives and preferably acetate of manganese (II), manganese acetate (III), manganese acetylacetonate (II), manganese acetylacetonate (III), nickel derivatives and preferably nickel acetate (II), nickel (II)
• Ru (NH 3 ) 6 2+ As an example of a ruthenium-based compound, mention may be made of Ru (NH 3 ) 6 2+ .
• the cross-metathesis reaction with an acrylic-type compound is carried out under perfectly known conditions.
• the metathesis reaction is preferably carried out at a reaction temperature between 20 and 120 ° C and the pressure is between 1 and 30 bar in the presence of a ruthenium catalyst. It will preferably be conducted at low pressure of between 1 and 10 bar and more preferably at atmospheric pressure when the cross metathesis leads to the formation of a light compound, for example ethylene to allow easy release.
• the reaction can be conducted without solvent or in the presence of a solvent such as toluene, xylenes or dichloromethane. benzene, chlorobenzene or dimethylcarbonate.
• Grubbs catalysts (Grubbs et al., Angew Chem., Ed., Engl., 34 (1995) 2039 and Organic Letters 1 (1999) 953) have appeared which are ruthenium-benzylidene complexes operating in homogeneous catalysis.
• a, b, c, d and e are integers, identical or different, with a and b equal to 0, 1 or 2; c, d and e are 0, 1, 2, 3 or 4;
• X1 and X2 identical or different, each represent a mono- or multi-chelating ligand, charged or not; by way of examples, mention may be made of halides, sulphate, carbonate, carboxylates, alcoholates, phenolates, amides, tosylate, hexafluorophosphate, tetrafluoroborate, bis-triflylamidide, alkyl, tetraphenylborate and derivatives.
• X1 or X2 may be bonded to (L1 or L2) or (carbene C) to form a bidentate ligand or chelate on ruthenium; and • L1, L2 and L3 identical or different, are electron donor ligands such as phosphine, phosphite, phosphonite, phosphinite, arsine, stilbine, an olefin or an aromatic, a carbonyl compound, an ether, an alcohol, an amine, a pyridine or derivative, an imine, a thioether, or a heterocyclic carbene
• electron donor ligands such as phosphine, phosphite, phosphonite, phosphinite, arsine, stilbine, an olefin or an aromatic, a carbonyl compound, an ether, an alcohol, an amine, a pyridine or derivative, an imine, a thioether, or a heterocyclic carbene
• (carbene C) being represented by the general formula: C_ (R1) _ (R2) for which R1 and R2 are identical or different groups such as hydrogen or any other hydrocarbon group saturated or unsaturated, cyclic, branched or linear, or aromatic.
• R1 and R2 are identical or different groups such as hydrogen or any other hydrocarbon group saturated or unsaturated, cyclic, branched or linear, or aromatic.
• a functional group for improving the retention of the ruthenium complex in an ionic liquid may be grafted onto at least one of the ligands X1, X2, L1, L2, or carbene C.
• This functional group may or may not be charged. charged, such as, preferably, an ester, an ether, a thiol, an acid, an alcohol, an amine, a nitrogen heterocycle, a sulphonate, a carboxylate, a quaternary ammonium, a guanidinium, a quaternary phosphonium, a pyridinium, an imidazolium, a morpholinium or a sulfonium.
• the metathesis catalyst may optionally be heterogenized on a support in order to facilitate its recovery / recycling.
• the cross-metathesis catalysts of the process of the invention are preferably ruthenium carbenes described for example in Aldrichimica Acta, Vol 40, No. 2, 2007, p.45-52.
• the preferred catalysts are the Umicore® M51 catalyst (marketed by Umicore®) of formula (A) below, and the Umicore® M71 SIPr catalyst (marketed by Umicore®) of formula (B) below, or the catalysts marketed by Materia®.
• the reaction time is chosen according to the reagents and the operating conditions used and to reach the end of the reaction.
• the other way to shift the equilibrium is to use an excess of reagent, typically here an excess of acrylonitrile or alkyl acrylate (usually methyl).
• the first step would be completed with the exhaustion of the metathesis catalyst, the excess acrylate or acrylonitrile would be distilled for recycling, then in the second step the ⁇ - ⁇ nitrile compound - ester / unsaturated acid content in the reaction medium is hydrogenated in the presence of the metal of the 1 st stage catalyst in the hydrogenation function.
• the amount of ruthenium metathesis catalyst introduced during the first step is chosen such that it ensures all possible transformation of the non-acrylic reagent contained in the feedstock.
• said catalyst under the operating conditions of the metathesis stage, is at the end of the transformed reaction; it is depleted or deactivated and loses its catalytic activity in terms of metathesis - it will be designated later by the qualifier "degraded" for said reaction.
• the amount of catalyst can easily be adjusted to give the desired conversion to complete degradation of the catalyst.
• the reaction medium is subjected to hydrogenation.
• the hydrogenation reaction can be carried out directly on the reaction mixture resulting from the metathesis step and in the presence of the residual metathesis catalyst with ruthenium acting as hydrogenation catalyst. It can also be carried out with a conventional hydrogenation catalyst.
• the metals conventionally used for hydrogenation mention may be made of nickel, palladium, platinum, rhodium or iridium.
• the catalyst used will be Raney nickel or palladium on carbon.
• the reaction is carried out under hydrogen pressure and in the presence of a base.
• the pressure is between 5 and 100 bar, preferably between 20 and 30 bar.
• the temperature is between 50 and 150 ° C, preferably between 80 and 100 ° C.
• the base may be, for example, sodium hydroxide, potassium hydroxide, potassium tert-butoxide or ammonia.
• the base is generally used at a content of 10 to 80 mol% relative to the nitrile-unsaturated ester substrate.
• the hydrogenation reaction can be carried out with or without a solvent.
• the preferred solvents used for the metathesis and hydrogenation steps are aromatic solvents such as toluene or xylenes or a chlorinated solvent such as dichloromethane, chlorobenzene or dimethylcarbonate.
• amino acids or amino-esters obtained according to the process of the invention can be used as monomers for the synthesis of polyamides.
• the invention also relates to polymers obtained by polymerization of ⁇ , ⁇ -aminoesters (acids) synthesized according to the methods defined above.
• the process of the invention is illustrated by the following examples.
• 10-undecenenitrile was prepared by reaction of 10-undecenoic acid with ammonia in the presence of zinc oxide.
• the initial peroxide level determined by the potassium iodide and sodium thiosulfate method is 10 meq / kg.
• the peroxide level after treatment is less than 1 meq / kg.
• the product is used as for the metathesis reaction.
• the metathesis reactor is a 250ml double-jacketed glass reactor equipped with mechanical agitation, a condenser, a temperature probe, a nitrogen inlet and a syringe pump to add the metathesis catalyst continuously.
• the nitrogen-purged reactor 5 g of 10-undecenenitrile purified previously (30 mmol), 5.2 g of methyl acrylate (60 mmol) and 50 g of dried toluene on molecular sieve are charged.
• Example 2 (Comparative) The example was carried out under the same conditions as Example 1 without purification of 10-undecenenitrile and using 0.0075 mol% of Umicore® M71 SIPr catalyst.
• the conversion of 10-undecenenitrile is 5%.
• the turnover number of the catalyst is 666.
• the impurities present in a form combined with Ruthenium give alcohols, alcohols-esters, or even amino-alcohols-esters.
• these impurities act as chain growth inhibitors, resulting in the (difficult) production of a poor quality polymer.
• the heat and / or chemical treatment of the process of the invention makes it possible to target the impurities, and remove them as soon as possible, while limiting the loss of raw material, which improves the selectivity of the step of metathesis, but also surprisingly, all the steps downstream of the metathesis step, in particular hydrogenation, and possible polymerization of the monomer obtained according to the method of the invention.

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