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
  • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • 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
  • C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
  • C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/42—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

• This patent application relates to a process for the continuous production of ⁇ -bromoalkanoic acids and esters by hydrobromination. It also relates to a process for the production of aminocarboxylic acid and esters and of polyamide or copolyamide from said ⁇ -bromoalkanoic acids or esters.
• Br-(CH 2 ) n+ 2-COOR (II) are interesting precursors in the polymer industry. In particular, they constitute intermediates for the amino acids and amino esters necessary for the manufacture of polyamides. Thus, 11-bromoundecanoic acid is the precursor of 11-aminoundecanoic acid used on an industrial scale for the manufacture of polyamide 11.
• CH 2 CH-(CH 2 ) n -COOR (I) in which n is an integer between 7 and 9, R is chosen from H or an alkyl radical containing from 1 to 10 linear or branched carbon atoms.
• the hydrobromination is carried out by addition of anti-Markovnikov type of HBr to the compound of formula (I) in the presence of a radical initiator and of one or more solvents.
• Patent CN 103804209 B describes the hydrobromination of 10-undecenoic acid continuously in a system of two reactors stirred in series.
• a mixture of 10-undecenoic acid in toluene and benzene, 1 to 5% by weight of azobisisobutyronitrile or benzoyl peroxide as radical initiator and HBr are injected into the first stirred reactor, maintained at a temperature of 10 - 30°C with a residence time of 30 to 90 minutes.
• the reaction medium from the first reactor is withdrawn continuously and injected into separation equipment heated to 65-80°C.
• the residual HBr released in the form of gas is returned to the first reactor.
• the maximum efficiency indicated is 92.1%. This process requires a long residence time for moderate yield. Furthermore, the large amount of radical initiator can be the source of troublesome residues in the product.
• All of these continuous processes operate with benzene, a carcinogenic and mutagenic solvent, and/or toluene, a solvent capable of producing benzyl bromide, a tear gas compound.
• Patent EP 3030543 B1 proposes a process for the continuous hydrobromination of 10-undecenoic acid which makes it possible to at least partially replace the benzene with cyclohexane and/or methylcyclohexane.
• 10-undecenoic acid is reacted with HBr in liquid form.
• the document teaches that the implementation of the process in a counter-current column with modification of solvent leads to a loss of yield, which can be compensated for when two successive reactors are used, the first with a turbulent flow and the second a laminar flow.
• This method has the disadvantage of requiring an HBr in liquid form, which has the consequence of constraints in terms of HBr purity and considerable energy expenditure and investment to cool the HBr or an HBr solution to temperatures significantly below 0°C so that the solubility of HBr is sufficient.
• the object of the invention is therefore to provide a process for the continuous synthesis of w-bromoalkanoic acids and esters by hydrobromination not using benzene and/or toluene, which has a satisfactory yield of the product of formula (II). , preferably at least 92% and in particular at least 94%.
• the aim of the invention is to propose a continuous synthesis process which saves energy, in particular requiring neither high pressure nor a temperature below 5°C.
• the aim of the invention is to provide a continuous synthesis process allowing the use of HBr contaminated with hydrogen, HCl or water.
• the aim of the invention is to propose a continuous synthesis process making it possible to reduce the quantity of HBr supplied to the process, this compound being expensive to produce and to dispose of.
• the object of the invention is to provide a continuous synthesis process with a reduced residence time, in particular less than 30 minutes, and very particularly less than 15 minutes.
• the aim of the invention is to propose a continuous synthesis process making it possible to produce a compound of formula (II) comprising few or no impurities.
• the object of the invention is to provide a continuous synthesis process that does not require solid radical initiators, which are reagents at risk of violent decomposition.
• the aim of the invention is a process for producing an aminocarboxylic acid or ester from a compound of formula (II).
• the object of the invention is a process for producing a polyamide or copolyamide from a compound of formula (II).
• the present invention is based on the observation that it is possible to replace benzene and toluene, in the continuous production of w-bromoalkanoic acids and esters by hydrobromination with aliphatic solvents while maintaining a high yield under the condition of ensure a sufficient molar excess of HBr during the reaction.
• the subject of the invention is a process for the continuous synthesis of a compound of formula (II) Br-(CH2) n+ 2-COOR, comprising a step consisting of:
• the ratio between the molar flow rate of HBr injected in step (a) and the molar flow rate of the compound of formula (I) injected in step (a) is from 1.2 to 3, preferably from 1.3 to 2.2 , more preferably from 1.4 to 2, and in particular from 1.5 to 1.9.
• the reactor outlet flow of the liquid reaction mixture at the end of step (a) comprises at least 2%, preferably at least 3%, and more preferably at least 3.5% and in particular at least 4% by weight of HBr.
• the method of the invention further comprises the subsequent steps consisting of:
• step (b) separating excess HBr from the liquid reaction mixture from step (a);
• step (b1) optionally, separation of the excess HBr from the gaseous reaction mixture resulting from step (a);
• step (c) recycling the HBr separated in step (b) and (bl) if necessary to step (a).
• the method of the invention comprises the steps consisting of:
• step (c) recycling of the separated HBr to step (al).
• Step (a) can be carried out in a reaction medium saturated with HBr. It can be carried out at a temperature of between 5 and 50°C, preferably between 10 and 40°C and very particularly at 20 to 30°C.
• the radical initiator can be molecular oxygen used as it is or mixed with inert gases, for example air or oxygen-enriched air.
• the first reactor may in particular be a stirred tank with a self-aspirating turbine or a jet loop reactor comprising a venturi.
• the separation equipment can in particular be a stirred tank or a column.
• the process according to the invention is carried out in the absence of aromatic solvent.
• the product of formula (I) can be chosen from 11-bromoundecanoic acid, 10-bromodecanoic acid and 9-bromononanoic acid.
• the solvent can be chosen from cyclohexane, methylcyclohexane, methylcyclopentane, n-hexane, 2-methylhexane, 3-methylhexane, n-heptane, isooctane, petroleum ether, tetralin, 1,1,1-trichloroethane, dibromoethane, chloroform, tetrachloride carbon, tetrachlorethylene, 1-bromopropane, dimethyl carbonate, tetrahydrofuran, 1,4 dioxane, 2-methyltetrahydrofuran, tetrahydropyran, 1-propoxypropane, 1-ethoxybutane, 2-isopropoxypropane, acetonitrile and mixtures thereof.
• the invention relates to a process for the synthesis of a compound of formula (III) NH 2 - (CH 2 ) n+ 2-COOR, comprising a step consisting of: (i) ammonolysis on the compound of formula (II) obtained by the above process; and
• the invention relates to a process for synthesizing a polyamide or copolyamide comprising the step of polycondensation of the compound of formula (III) obtained by the process above, alone or as a mixture with other monomers.
• Fig. 1 an installation diagram for implementing a method according to one embodiment of the invention
• Fig 2 an installation diagram for the implementation of a method according to one embodiment of the invention comprising a venturi and an external heat exchanger
• Fig. 3 an installation diagram for the implementation of a method according to an embodiment of the invention comprising a venturi.
• the term “stoichiometric excess” is understood to mean, in the context of a continuous process, a molar flow rate of reactant greater than that required for the reaction envisaged. For example, one mole/hour of HBr is required to carry out the hydrobromination of one mole/hour of compound of formula (I). Also, a ratio of the molar flow rate of HBr/molar flow rate of the compound of formula (I) > 1 constitutes a stoichiometric excess of HBr.
• the term “residence time” is understood to mean the ratio between the volume occupied by the liquid reaction mixture and the sum of the volume flow rates of compound of formula (I) and of solvents supplied to the process.
• ⁇ -bromoalkanoic acids or esters is understood to denote alkanoic acids or esters bearing at least one bromine atom on the terminal carbon atom. Preferred are straight chain ⁇ -alkanoic acids or esters.
• the process of the invention aims to produce in particular w-bromoalkanoic acids or esters of formula (II) below:
• n is an integer between 7 and 9
• R is chosen from H or an alkyl radical containing from 1 to 10 linear or branched carbon atoms, in particular methyl, ethyl, isopropyl or propyl.
• the process is particularly interesting for the manufacture of 12-bromododecanoic acid, 11-bromoundecanoic acid and 10-bromodecanoic acid.
• the w-bromoalkanoic acids or esters of formula (II) can be obtained by hydrobromination of a terminally unsaturated carboxylic acid or ester of formula (I):
• CH 2 CH-(CH 2 ) n -COOR (I) in which n is an integer between 7 and 9, and R is chosen from H or an alkyl radical containing from 1 to 10 linear or branched carbon atoms, in particular methyl, ethyl, isopropyl or propyl.
• the compound of formula (I) is advantageously 10-decenoic acid, 11-undecenoic acid or 12-dodecenoic acid or one of their esters, in particular their methyl, ethyl, isopropyl or propyl ester.
• 11-undecenoic acid is advantageously from castor oil, as described in particular in FR 952985.
• the compounds of formula (I) are preferably used in liquid form, either in molten form or in solution in a suitable solvent.
• the compound of formula (I) is used at a temperature of 10 to 70°C, and in particular of 20 to 50°C.
• HBr is commercially available or can be produced by reaction of bromine with hydrogen or be the coproduct of another reaction, for example the bromination of an aromatic compound.
• HBr can be obtained advantageously by:
• HBr can be used pure but one of the advantages of the process of the invention is that it also allows its use in a mixture with other gases such as hydrogen, G HCl, carbon dioxide or water. .
• the total content of HBr in other gases is nevertheless less than 30% molar, advantageously less than 20% molar and very particularly less than 10% molar with respect to HBr.
• the water content of the HBr is advantageously less than 3%, advantageously 1% molar with respect to the HBr.
• the HBr is introduced into the reaction mixture in step (a) in gaseous form. Nevertheless, the HBr can dissolve partially or totally in the reaction medium comprising the compound of formula (I), the solvent, as well as the product of formula (II), the reaction medium which is most often in liquid form.
• the flow rate of HBr injected into the reaction mixture in step (a) is the sum of the HBr supplied to the process and, where appropriate, of the recycled HBr.
• the inventors have found that the selectivity and therefore the yield of the hydrobromination reaction is favored in the presence of a high quantity of HBr dissolved in the reaction medium, which is obtained by injecting a large stoichiometric excess of HBr in the reaction medium.
• the ratio of the molar flow rates between the HBr injected into the reaction mixture in step (a) and the compound of formula (I) injected in step (a) will most often be 1.2 to 3, preferably from 1.3 to 2.2, more preferably from 1.4 to 2, and in particular from 1.5 to 1.9.
• the HBr can dissolve in the reaction mixture and be available for the intended reaction.
• HBr in excess of its solubility in the reaction mixture or which does not manage to dissolve in the reaction medium can be evacuated from the reactor in gas form, in particular to regulate the pressure.
• the part of the other gases supplied with the HBr which is not solubilized in the reaction medium can likewise be evacuated from the reactor.
• the HBr not consumed by the reaction remains in the reaction mixture as residual HBr and can then be evacuated in this form.
• the reactor outlet stream of the liquid reaction mixture comprises at least 2%, preferably at least 3%, and more preferably at least 3.5% and in particular at least 4% by weight of HBr, relative to the weight of the liquid outlet stream from the reactor.
• the amount of recycled HBr can vary, depending on the molar ratio of total HBr injected into the reaction medium, the gas-to-liquid transfer, but also, where appropriate, the conditions for separating the reaction mixture.
• the recycled HBr has a molar ratio with the compound of formula (I) greater than 0.2 and less than 1.5. Most often this molar ratio will be from 0.3 to 1, preferably from 0.4 to 0.9, more preferably from 0.5 to 0.8.
• the HBr supplied to the process is preferably injected in stoichiometric excess, and therefore has a molar ratio with the compound of formula (I) greater than 1. Most often this molar ratio will be from 1.01 to 1.5, preferably from 1.02 to 1.4, more preferably from 1.03 to 1.3, and in particular from 1.03 to 1.2.
• the inventors have discovered that the use of HBr recycling makes it possible to increase the selectivity and the yield while minimizing the consumption of HBr and the discharges into the environment of the excess HBr.
• the flow rate can be determined by the usual means of analysis of HBr, in particular by argentimetry, acid-base titration or ion chromatography.
• the flow rate of HBr supplied to the process may be increased.
• the flow rate of recycled HBr can be increased by improving the conditions separation of the residual HBr during the separation step HBr, for example by increasing the temperature of the HBr separation step as indicated below.
• a stoichiometric excess of HBr is ensured in the reaction medium of step (a) by controlling the flow rate of HBr evacuated from the reactor in gas form.
• This control can be carried out for example by measuring the total gas flow evacuated from the reactor and the HBr concentration of this gas.
• the ratio between the gaseous molar flow rate of HBr evacuated from the reactor and that of the HBr supplied to the reactor is preferably between 0.01 and 0.5, more preferably between 0.02 and 0.4, more preferably between 0.03 and 0.3 and in particular between between 0.03 and 0.2.
• the process does not use benzene or toluene.
• the solvents suitable for the process of the invention are inert organic solvents which solubilize the compound of formula (I) and the reaction product of formula (II) as well as HBr at the reaction temperature. .
• Suitable solvents can be chosen from aliphatic or cycloaliphatic compounds, in particular linear or branched alkanes containing 1 to 10 carbon atoms, where appropriate substituted by one or more halogen atoms, in particular bromine or chlorine, alkoxy groups or nitrile groups; cycloaliphatic compounds, in particular cycloalkanes comprising a cycle of 4 to 8 carbon atoms optionally substituted and/or interrupted, in particular by one or more oxygen atoms.
• Certain solvents can be esters, in particular carbonate esters.
• cyclohexane methylcyclohexane, methylcyclopentane, n-hexane, 2-methylhexane, 3-methylhexane, n-heptane, isooctane, petroleum ether, tetraline, 1,1,1-trichloroethane, dibromoethane, chloroform, carbon tetrachloride, tetrachloroethylene, 1-bromopropane, dimethyl carbonate, tetrahydrofuran, 1,4 dioxane, 2- methyltetrahydrofuran, tetrahydropyran, 1-propoxypropane, 1-ethoxybutane, 2-isopropoxypropane, acetonitrile, fluorobenzene, chlorobenzene, trifluorotoluene, ethylbenzene , o-xylene, m-xy
• the method does not use solvents posing HSE problems and/or aromatic solvents.
• the solvent used is chosen from cyclohexane, methylcyclohexane, methylcyclopentane, 2-methylhexane, 3-methylhexane, n-heptane, isooctane, petroleum ether, and mixtures thereof. Particularly preferred are cyclohexane and methylcyclohexane.
• the ratio of the mass flow rates between the compound of formula (I) and the solvent entering the process can vary widely and it can be determined according to the conditions of the process by routine tests. In principle, a mass flow rate ratio between the compound of formula (I) and the solvent entering the process of 1:1 to 1:20 and preferably 1:2 to 1:10 and most particularly 1:3 to 1: 6 is suitable. It is generally preferable to work under concentrated conditions in order to optimize productivity. Nevertheless, it is preferable that the quantity of solvent be sufficient so as to prevent the compound of formula (I) or (II) from crystallizing in particular in the reaction stage.
• the solvent used in the process can be injected into the reaction medium separately or else mixed with the compound (I).
• the solvent injected into the reaction medium contains recycled HBr as described below.
• the hydrobromination reaction generally requires the presence of a radical initiator.
• the radical initiator can be chosen for example from oxygen, a gas containing oxygen such as air, a peroxide such as benzoyl peroxide, a diazo compound such as azobisisobutyronitrile or any other radical generator such as UV.
• oxygen or a gas containing oxygen such as air or oxygen-depleted air, are preferred radical initiators because they are readily available, inexpensive and produce little or no residue in the product. and do not present any storage stability problem.
• the amount of radical initiator is that used conventionally.
• oxygen or a gas containing oxygen when used as a radical initiator, its quantity, expressed as a molar ratio of oxygen with the quantity of HBr supplied to the process (excluding HBr possibly recycled, therefore), may vary in particular between 1:5000 and 1:50 and preferably between 1:1000 and 1:200.
• Equipment and process conditions when oxygen or a gas containing oxygen is used as a radical initiator, its quantity, expressed as a molar ratio of oxygen with the quantity of HBr supplied to the process (excluding HBr possibly recycled, therefore), may vary in particular between 1:5000 and 1:50 and preferably between 1:1000 and 1:200.
• Step (a) of hydrobromination of the process of the invention can be carried out very simply by continuously bringing the compound of formula (I) into contact with HBr in the presence of the radical initiator and one or more several solvents.
• the step is advantageously carried out in a reactor promoting gas/liquid material transfer.
• reactors can for example be based on a column, such as a spray column, a falling film column, a bubble column, an ejector column, a mechanically stirred column, a counter-packed column current or co-current or even a column with perforated plates.
• it can also be a reactor based on a stirred tank, for example equipped with a turbine mixer or a venturi ejector.
• This type of reactor comprises a tank in which a pump continuously withdraws the liquid reaction medium optionally comprising a gaseous fraction in the form of bubbles to return it to an ejector connected to the gaseous flow of HBr injected into the reaction medium.
• the liquid reaction mixture is ejected at high speed and the gas stream of HBr is dispersed in the reaction medium in the form of fine bubbles.
• the output of the ejector is sent to the tank.
• a pipe connects the gas phase of the tank with the gas inlet of the ejector.
• the hydrobromination step is carried out in a stirred tank with a turbine or in a jet loop reactor, in particular a jet loop reactor with a venturi ejector.
• the reactor temperature during the hydrobromination step is preferably set above the crystallization temperature of the reactant and products. Furthermore, it is preferable to choose a temperature that is not too low in order to limit energy expenditure. It is preferred to choose a temperature that is not too high so as to ensure good selectivity. Generally, the temperature during the reaction step will preferably be 5 to 50°C, preferably 10 to 40°C and especially 20 to 30°C.
• the hydrobromination reaction of the compound of formula (I) is strongly exothermic.
• a heat exchange device Such devices are known to those skilled in the art, it can be for example a double jacket around the reactor, or a device located on an outer loop, or even inside the reactor.
• the heat exchange device is located on an outer loop, outside the reactor.
• liquid reaction medium is withdrawn continuously in the reactor, sent to the external exchanger and then returned to the reactor.
• Any type of heat exchanger can be envisaged, such as for example tubular or plate exchangers.
• a packed column in which the solvent and the reagent (I) are injected at the top and at the bottom the HBr and the radical initiator and in which part of the reaction medium liquid is taken from the bottom of the column and sent using a pump to a heat exchanger and reinjected into the top of the column.
• the reactor used will be a jet loop reactor comprising a heat exchanger between the pump and the ejector.
• the compound of formula (I) is added in liquid form.
• a compound of formula (I) with a melting point of 10°C or lower may be added at a temperature close to room temperature, i.e. 15 to 35°C.
• a compound of formula (I) with a melting point above 10° C. is preferably heated before introduction into the reactor, for example at a temperature 25° C. above its melting point.
• the solvent is preferably introduced into the reactor with a temperature of 5 to 35°C, and preferably close to ambient temperature, that is to say from 15 to 35°C.
• the pressure in the reactor during stage (a) of hydrobromination is generally between 0.5 and 5, preferably between 0.9 and 3 and in particular from 1 to 1.5 bar absolute.
• the reactor is at an absolute pressure between 1.05 and 1.25 bar absolute.
• the installation provided for the implementation of the method comprises at least one gas vent, in order to control the pressure. It is thus possible to keep the pressure constant by eliminating the excess gas, in particular the non-reactive gaseous compounds brought by the HBr, as well as the HBr which has not dissolved in the reaction medium.
• step (a) of hydrobromination of the process of the invention makes it possible to achieve almost total conversion of the compound of formula (I) with a reduced residence time.
• the residence time in the reactor is generally between 1 and 60 minutes and preferably between 2 and 45 minutes and preferably between 5 and 30 minutes.
• Step (b) of separating the residual HBr from the reaction mixture can be carried out in suitable separation equipment, for example a stirred tank, an exchanger and flash drum device, or even, preferably, a column fitted with a packing or trays and comprising a reboiler at the bottom.
• suitable separation equipment for example a stirred tank, an exchanger and flash drum device, or even, preferably, a column fitted with a packing or trays and comprising a reboiler at the bottom.
• Recycling of HBr can be accomplished by withdrawing the reaction mixture from the hydrobromination reactor and returning it to separation equipment, where HBr can be separated from the reaction mixture by simple heating.
• the liquid mixture is heated to a temperature close to the boiling point of the solvent, so as to evaporate more than 70%, preferably more than 80% and preferably more than 90% and in particular more than 99% residual HBr present in the reaction stream.
• the gaseous HBr thus recovered can then be returned to the first reactor by conventional means. It would remain within the scope of this invention if the gaseous stream resulting from the separation step were cooled, thus inducing at least partial condensation of the solvent entrained in this gaseous stream, the gaseous and liquid streams being returned to step (a ).
• a liquid stream of product of formula (II) and of solvent is also recovered.
• This liquid stream can be subjected to a washing step followed by decantation, for example with water or a dilute aqueous sodium hydroxide solution in order to eliminate traces of residual HBr.
• the solvent can be eliminated for example by evaporation then if necessary be recycled in the reaction.
• the crude product of formula (II) recovered can then be purified by conventional means, in particular by crystallization in the molten state or by recrystallization, in particular from the reaction solvent, or else used as it is without a purification step.
• step (a) it is proposed to at least partially recycle the HBr present in the gaseous stream leaving step (a) by separating at least partially the HBr contained in the stream gas from the reaction mixture of step (a) and returning the separated HBr to step (a).
• Said gas flow leaving step (a) is advantageously brought into contact with optionally recycled solvent to absorb part of the HBr. This bringing into contact can be carried out by means known to those skilled in the art, such as for example a packed column.
• the stream of solvent enriched in HBr thus obtained can then be sent to step (a).
• the product of formula (II) may undergo an ammonolysis reaction by reaction with ammonia to form the corresponding w-aminocarboxylic acid or ester of formula (III).
• the compound of formula (III) after optionally having undergone purification steps, can be polymerized, for example by polycondensation, into the corresponding polyamide. Alternatively, it can also be used with other monomers such as, for example, diamines and dicarboxylic acids, one or more lactams or polyethers for the manufacture of corresponding copolymers.
• the process according to the invention makes it possible to obtain a product of formula (II) comprising fewer impurities, which simplifies the purification steps before the reaction with ammonia or, if it is used without purification, after the reaction with ammonia.
• a hydrobromination reactor (1) comprises a continuous feed (2) of compound of formula (I), a continuous feed (3) of solvent, a continuous supply (4) of initiator, a continuous supply (5) of gaseous HBr supplied to the process and a continuous supply (6) of recycled HBr in gaseous form.
• the reactor also comprises a gaseous vent (7) making it possible to eliminate the excess gas arriving at the reactor. It comprises a liquid withdrawal (8) of reaction mixture sent to an HBr separation equipment (9) which comprises a withdrawal of HBr (6) and a withdrawal (10) of liquid phase containing the compound of formula (II) and the solvent.
• a hydrobromination reactor (1) comprises a tank (11) provided with a recirculation loop (12) with a pump (13) whose The suction is connected to the tank (11) and the discharge to a heat exchanger (14), which is connected to a venturi (15) connected to the reactor.
• a continuous supply (5) of HBr supplied to the process and a continuous supply (6) of recycled HBr and an equilibration loop (16) of the gas overhead of the reactor are connected to the gas suction of the venturi.
• the continuous supplies (2) of solvent, (3) of compound of formula (I) and (4) of initiator are connected on the line between the heat exchanger and the venturi.
• a liquid withdrawal line (8) of the reaction mixture is connected to an HBr separation tank (9) which comprises a continuous withdrawal (6) of recycled HBr in gaseous form and a continuous withdrawal (10) of liquid phase containing the compound of formula (II) and the solvent.
• a hydrobromination reactor (1) comprises a jacketed vessel (11) cooled by a continuous supply (14) of heat transfer fluid, a recirculation loop (12) with a pump (13) whose suction is connected to the tank (11) and the discharge to a venturi (15) connected to the reactor.
• a continuous supply (5) of gaseous HBr supplied to the process and (6) of recycled HBr in gaseous form and an equilibration loop (16) of the gaseous headspace of the reactor are connected to the gas suction of the venturi.
• the continuous supply (2) of a mixture of compound of formula (I), solvent and initiator is connected to the line between the heat exchanger and the venturi.
• a line (8) for liquid withdrawal of reaction mixture is connected to a second jacketed vessel (9) for separating HBr which comprises a continuous withdrawal of HBr (6) in gaseous form and a continuous withdrawal of liquid phase containing the compound of formula (II) and the solvent by a pump (10).
• the venturi (15) is a glass water pump (water jet pump reference 181-9205 from VWR International) the liquid outlet of which is connected to the cylindrical jacketed vessel (11).
• the recirculation pump (13) has a flow rate of 100 l/h.
• a flow rate of 2361 g/h of a solution of 10-undecenoic acid in cyclohexane at 15% by mass at room temperature and a flow of air are injected via the supply (2).
• the gaseous HBr supplied to the process is continuously injected at a flow rate such that the ratio of the gaseous HBr flow rate in mol/h to the 10-undecenoic acid flow rate in mol/h is 1.15.
• the ratio of HBr volume flow to air volume flow is 35:1.
• the vessel (11) is maintained at a pressure 0.1 bar above atmospheric pressure by the vent (7) on the gas phase of the reactor connected to the atmosphere by a vent treatment system. Throughout the duration of the experiment, the temperature in the tank (11) is kept constant at 24° C. thanks to the circulation in the double envelope of a heat transfer fluid.
• the volume of reaction medium in tank (11) and loop (12) is kept constant at 0.3 liters by continuous export (8) to a separation tank (9).
• the residence time in the first reactor is of the order of 6 minutes.
• the separation tank (9) is agitated by a magnetic bar and heated by the circulation of heat transfer fluid in the jacket so as to maintain the temperature of the reaction liquid at 80°C.
• the liquid level in the tank (9) is maintained at 0.15 liter by continuously exporting the reaction mixture using the pump (10).
• tank (11) and the loop contain cyclohexane saturated with HBr, and tank (9) is empty.
• an aliquot of liquid reaction mixture is taken from line (8) and subjected to analysis. by argentimetry and by gas chromatography. Argentimetric analysis makes it possible to determine the mass concentration of HBr in the aliquot.
• the analysis by gas chromatography is carried out by derivatization of 0.1ml of liquid reaction mixture with 1 ml of N,0-Bis(trimethylsilyl)trifluoroacetamide with 1% trimethylchlorosilane for 30 minutes at 80°C then injection on an apolar column and detection by flame ionization. From the chromatogram, the ratio of the area corresponding to 10-undecenoic acid relative to the sum of the areas corresponding to the compounds with 11 carbon atoms is determined. The conversion of 10-undecenoic acid can then be calculated by subtracting this ratio from 1, according to the following formula:
• the ratio of the molar flow rate of gaseous HBr injected into the reaction mixture (equal to the sum of the molar flow rate of HBr supplied to the process (5) and the molar flow rate of recycled HBr (6)), relative to the molar flow rate of 10-undecenoic acid, is estimated at 1.85.
• Example 1 is reproduced with the same apparatus but in which the second tank (9) and the vent recycling line (6) have been removed.
• the ratio of the flow rate of gaseous HBr injected into the reaction mixture in mol/h to the flow rate of 10-undecenoic acid in mol/h is adjusted to 1.5.
• Example 2 is reproduced but adjusting the ratio of the flow rate of gaseous HBr injected into the reaction mixture in mol/h to the flow rate of 10-undecenoic acid in mol/h at a value of 1.4.
• Example 2 is reproduced with a ratio of the flow rate of gaseous HBr injected into the reaction mixture in mol/h to the flow rate of 10-undecenoic acid in mol/h adjusted to 1.3. The results are reported in Table 2.
• Example 1 is reproduced by replacing the HBr injected in (5) with an HBr / hydrogen / HCl mixture in the volume ratio 90/4/1 and ensuring a ratio of the flow rate of HBr supplied to the process in (5) in mol/h (not counting hydrogen or HCl) on the flow rate of 10-undecenoic acid in mol/h of 1.05. The results are reported in Table 2.
• the tank (9) is replaced by a column comprising a packing and a reboiler at the bottom, regulated at 100°C, in which the liquid flow coming from the tank is injected at the top, the reaction liquid is withdrawn at the bottom by the pump (10) to maintain a constant level in the reboiler, with a liquid volume of 0.06 liters, and the gaseous vent at the top of the column is returned to the gas suction of the venturi.
• Example 2 is reproduced, replacing the tank (11) and the venturi and the liquid loop with the pump by a double-envelope stirred tank with a self-priming turbine.
• the HBr stream (5) is fed under the stirrer wheel.
• the ratio of the flow rate of gaseous HBr injected into the reaction mixture in mol/h to the flow rate of 10-undecenoic acid in mol/h is adjusted to 1.85 and the temperature in the tank (11) is maintained at 20° vs.

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