Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
  • C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups

Definitions

• the present invention relates to a process for synthesizing diamines and / or primary triamines from dimeric and / or trimeric nitriles, which nitriles may themselves be derived from dimeric and / or trimeric fatty acids.
• amines find many applications as anticorrosive agents, in the detergency, as additives for bitumen, flotation agents, anti-caking agent, anti-dust, crosslinking agents, petroleum additives, lubricating agents, additives in the treatment of water, additives for concrete.
• Dimeric and trimeric acids are obtained by high temperature and pressure polymerization of unsaturated fatty acids.
• unsaturated fatty acids mainly oleic (C: 18-1) or linoleic (C: 18-2) acids
• These unsaturated fatty acids come mainly from tall oil, which is itself derived from pulp processes of the Kraft type. This source of acid is preferred for cost reasons (85% of the acids consumed in this field), but it is quite possible to use unsaturated fatty acids from other vegetable sources.
• a mixture is obtained containing on average 30-35% of monocarboxylic acids often isomerized relative to the starting acids, 60-65% of dicarboxylic acids (dimer acids) with twice the number of carbon per molecule.
• trimeric acids having the triple carbon number with respect to the starting acids. Purification of this mixture gives the different commercial grades of dimer and / or trimeric acids which may exist in hydrogenated or non-hydrogenated form.
• diacids and triacids lie in the fact that these compounds remain liquid at room temperature while having a low viscosity despite their average carbon number of 36 or 54. This is due to the mixture of the many isomers that constitute the product as well. than cycloaliphatic rings and the presence of unsaturations. In addition, most diacids and triacids are derived from vegetable raw materials and therefore renewable.
• No. 3,231,545 discloses (column 2, line 61) that dimeric fatty acids can be converted to the corresponding nitriles and then hydrogenated to diamines. In addition, it is specified that purification is necessary at each step in order to obtain diamines of good purity for use in the field of polymers.
• the present invention firstly proposes a method of synthesis, by hydrogenation of di- and / or tri-amines of high purity from di- or tri-nitriles (also hereinafter referred to as "nitriles").
• the di- and / or tri-nitriles used may be in particular mixtures of dimerization and / or trimerization products of mono-nitriles comprising generally 8 to 30 carbon atoms, and one or more unsaturations, mainly in the form of double bond (s), which allow said dimerization and / or trimerization.
• This step of hydrogenation of the nitriles to primary amines takes place in a reactor under pressure, for example in an autoclave, in the presence of a hydrogenation catalyst, ammonia and optionally at least one strong base.
• a hydrogenation catalyst such as, for example, Raney nickel, Raney cobalt, palladium or rhodium supported on carbon or alumina are charged into the reactor which is then purged with nitrogen.
• the ammonia is then introduced at room temperature so as to create a partial pressure of ammonia and the reaction medium is stirred at a temperature between 100 0 C and 130 0 C before introducing hydrogen.
• the temperature of the reaction is generally comprised, in the broad sense, between 110 ° C. and 170 ° C., and preferably from 130 ° C. to 150 ° C.
• the amount of hydrogenation catalyst used represents from 0.1% to 15%, preferably from 3% to 10% by weight of the nitrile feedstock and more preferably from 4% to 8%. - AT -
• the total pressure of the reactor during this step is generally between 2 MPa and 4 MPa, but one could operate at higher pressure (15 MPa) without inconvenience and without departing from the scope of the invention.
• the reaction can be carried out in a solvent medium, the solvent being chosen from the conventional solvents used for this type of reaction.
• the reaction is conducted in the absence of a solvent, especially in the case where the starting polynitriles are in liquid form.
• the reaction is continued in this way until the hydrogen consumption stops and the measurement of the alkalinity index no longer varies.
• the molar ratio ammonia / nitrile functions is between 0.2 and 3.
• molar ratio ammonia / nitrile functions is meant the ratio between the number of moles of ammonia introduced and the number of functions. nitriles present in the reaction medium.
• the number of nitrile functions present in the reaction medium can be determined by any quantitative analysis method known to those skilled in the art and for example by quantitative analysis by infrared spectrometry.
• the polynitrile involved in the hydrogenation reaction comes from a mixture of fatty acids as indicated above, it may be envisaged to determine the number of acid functions according to techniques known to those skilled in the art. The number of nitrile functions generated during the ammoniation reaction described below can then be understood as being equal to the number of transformed acid functions.
• the base which may be added to the reaction medium may be of any type, and in particular a strong base, organic or inorganic, preferably mineral, in particular chosen from alkali metal or alkaline earth metal hydroxides, for example hydroxide hydroxide. sodium or potassium hydroxide. It is particularly preferred to use sodium hydroxide.
• a mixture of two or more bases may also be used.
• the molar ratio ammonia / nitrile functions is between 0.2 and 1, 3, and preferably between 0.5 and 1
• at least one strong base such as sodium hydroxide and / or hydroxide potassium is added to the reaction mixture in a proportion of 0.07% to 1% by mole, and preferably from 0.35% to 0.75% by mole, relative to the number of nitrile functions present in the reaction medium and such that defined it above.
• the at least one strong base is preferably added in aqueous form. It should be understood that when the molar ratio ammonia / nitrile functions is between 1, 3 and 3, and preferably between 1, 5 and 2.6, one can overcome the presence of strong base.
• the hydrogenation step of the process according to the invention makes it possible to convert the nitrile functions to 100% primary amine functions with a selectivity greater than 97% of primary amines, which makes it possible to use diamines and triamines directly and without purification. in applications where the required purity is very important.
• the polynitriles in particular di- and tri-nitriles used in the process for the preparation of primary amines, principally in the form of diamines and triamines, can advantageously be obtained from di- and / or tri-fatty acids. mothers, according to conventional ammoniation techniques known to those skilled in the art.
• the ammoniation reaction may for example be carried out in the conventional manner in the presence of an ammoniation catalyst preferably chosen from metal oxides, and preferably zinc oxide, in a weight ratio of catalyst / diacids and / or triacids. between 0.01% and 0.15% and preferably 0.03% and 0.1%.
• the reaction medium is stirred and heated to a temperature generally ranging from 150 ° C. to 170 ° C., followed by ammonia. gaseous is introduced into the reactor, for example by means of a diving rod, and the temperature is increased, preferably in steps, at a temperature generally ranging from 250 ° C. to 320 ° C., preferably from 290 ° C. to 310 ° C. 0 C.
• the pressure is generally between 0.05 MPa and 0.4 MPa, to atmospheric pressure (0.1 MPa) being preferred.
• the water formed and the excess ammonia may be collected in a trap via a dephlegmator maintained at 130 0 C.
• the reaction is continued until the acid value of the reaction medium is less than or equal to 0.1 mg KOH / g, for a duration of 12 to 17 hours. Infrared and mass spectroscopy analyzes show that the acid functions are almost quantitatively transformed into nitriles.
• the ammoniation reaction can be carried out in a solvent medium. However, it is preferred to carry out the conversion of the acid functions to nitrile functions in the absence of a solvent, especially when the compounds carrying the acid functions are used in the liquid state.
• nitriles thus obtained can be used as such, that is to say without intermediate purification, for the hydrogenation reaction described above to form the di- and tri-amines.
• the present invention provides a process for synthesizing high purity di- and / or tri-amines from di- and / or trimer fatty acids in two steps which does not require any purification step, comprising the following steps: N in a reactor under stirring, conversion of the acid functional groups of the dimer and / or trimeric acids to nitriles to give di- and tri-nitriles in the presence of an ammoniation catalyst preferably chosen from oxides metal, and preferably zinc oxide, in a catalyst / diacid and / or triacid weight ratio of between 0.01% and 0.15%, then introduction of gaseous ammonia into the reactor,
• reaction temperature from 110 0 C to 170 0 C and preferably from 130 ° C. to 150 ° C.
• the amount of hydrogenation catalyst used represents from 0.1% to 15% by weight of the nitrile feedstock, and the molar ratio of ammonia to nitrile functions is between 0.2 and 3.
• step A In the 1st step (step A), converting the acid functions of dimer acids and / or trimers of nitrile function to obtain di- and tri-nitriles
• step B the nitrile functions are converted to primary amino function by hydrogenation, as indicated above.
• the process of the invention can be advantageously used for the preparation of primary amines, in the form of di- and / or tri-amines of high purity, with a high selectivity.
• high selectivity it is meant that the nitrile functions are converted into primary amine functions, in particular more than 95% transformed into primary amine functions, with respect to the total number of amine functions formed, more specifically to more than 97% in functions.
• the other amine functions formed may be predominantly secondary amines, for example in proportions of less than 5%, preferably less than 3%, relative to the total number of amine functions formed.
• tertiary amines if they are formed, they are generally only in trace amounts.
• the process of the present invention finds a particularly advantageous application in the selective synthesis of primary di- and / or tri-amines, with high selectivity, from unsaturated fatty acids from tall oil or other vegetable sources. and which are mainly in the form of di- and / or trimers. Of such acidic forms are well known and described for example in US Pat. No. 3,475,406 or patent application WO 2003/054092.
• a, b, c and d represent independently of each other the number of methylene links (-CH 2 -) on each of the chains.
• a, b, c and d are each between 1 and 24, more generally between 2 and 20, more particularly between 4 and 16.
• the primary amines obtained according to the process of the present invention find applications in very many fields.
• AT Examples of use of these amines include their use as anti-corrosion agents, in the detergency, as additives for bitumen, flotation agents, anti-mottants, anti-dust, crosslinking agents, petroleum additives, lubricating agents, water treatment additives, concrete additives, and others.
• the introduction of ammonia is continued until the acid number of the reaction medium is less than 0.1 mg of KOH / g.
• the reaction time is about 12 to 14 hours.
• the reaction medium is cooled to 40 ° C. and the reactor is emptied.
• the yield is close to 100% and the selectivity is almost complete in dinitrile.
• Monitoring is provided by measuring the alkalinity as the reaction progresses. This lasts around 10 am.
• the reaction medium is cooled to ambient temperature, the hydrogen and ammonia are purged with nitrogen, and the crude reaction product is drained.
• the catalyst is recovered by filtration under nitrogen and the latter can be recycled.
• the conversion of the nitrile is 100% and the content of secondary amines is less than 3% (limit of quantification by NMR).
• the reaction medium is cooled to ambient temperature, the hydrogen and ammonia are purged with nitrogen, and the crude reaction product is drained.
• the catalyst is recovered by filtration under nitrogen and the latter can be recycled.
• the conversion of the nitrile is 100% and the content of secondary amines is less than 3% (limit of quantification by NMR).

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

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• 2007
  • 2007-04-05 FR FR0754304A patent/FR2907781B1/fr not_active Expired - Fee Related
  • 2007-10-26 JP JP2009533921A patent/JP5389657B2/ja not_active Expired - Fee Related
  • 2007-10-26 IN IN2522DEN2009 patent/IN2009DN02522A/en unknown
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  • 2007-10-26 MX MX2009004502A patent/MX2009004502A/es active IP Right Grant
  • 2007-10-26 EP EP07866497A patent/EP2086920A1/fr not_active Withdrawn
  • 2007-10-26 US US12/446,323 patent/US20110190541A1/en not_active Abandoned
  • 2007-10-26 WO PCT/FR2007/052253 patent/WO2008053113A1/fr active Application Filing
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