EP1381584A2 - Method for preparing a halogenated olefin - Google Patents

Method for preparing a halogenated olefin

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Publication number
EP1381584A2
EP1381584A2 EP02737895A EP02737895A EP1381584A2 EP 1381584 A2 EP1381584 A2 EP 1381584A2 EP 02737895 A EP02737895 A EP 02737895A EP 02737895 A EP02737895 A EP 02737895A EP 1381584 A2 EP1381584 A2 EP 1381584A2
Authority
EP
European Patent Office
Prior art keywords
palladium
methylacetylene
propadiene
compound
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02737895A
Other languages
German (de)
French (fr)
Inventor
Véronique Mathieu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay SA
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Filing date
Publication date
Application filed by Solvay SA filed Critical Solvay SA
Publication of EP1381584A2 publication Critical patent/EP1381584A2/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons

Definitions

  • the present invention relates to a process for the preparation of a halogenated olefin, in particular 2-chloroprop-1-ene.
  • 2-Chloroprop-1-ene is an intermediate in the synthesis of halogen precursors of 1, 1, 1,3,3-pentafluorobutane (HFC-365mfc) used as a solvent and as a swelling agent in the preparation of polymeric cellular foams.
  • 2-chloroprop-1-ene is particularly useful for the synthesis of the precursor 1,1,1,3,3-pentachlorobutane.
  • Patent application EP-A-905 113 in the name of the Applicant teaches a process for the preparation of 2-chloroprop-1-ene by reaction of methylacetylene and / or propadiene with hydrogen chloride in a liquid medium containing at least
  • a hydrochlorination catalyst which comprises at least one compound chosen from compounds of the metals of the Villa group and of lanthanides; and (b) an organic solvent capable of solubilizing the catalyst.
  • the invention therefore relates to a process for the preparation of a halogenated olefin by reacting an alkyne and / or an allenic compound with a hydrogen halide in a liquid medium comprising at least
  • R 1 denotes a hydrogen, alkyl, aryl or carboxyl group. ester or halogen.
  • R 1 is chosen from a carboxyl group, an alkyl group comprising from 1 to 10 carbon atoms, a phenyl group optionally substituted by 1,2 or 3 alkyl substituents comprising from 1 to 4 carbon atoms, an alkyl ester carrying an alkyl radical comprising from 1 to 10 carbon atoms or an aryl ester.
  • R 2 and R 3 are independently chosen from a hydrogen group, a carboxyl group, an alkyl group comprising from 1 to 10 carbon atoms, a phenyl group optionally substituted by 1,2 or 3 alkyl substituents comprising from 1 to 4 carbon atoms , an alkylester carrying an alkyl radical comprising from 1 to 10 carbon atoms or an aryl ester.
  • R 2 R 3 C XC-CH 3 (TV) in which R 1 , R 2 and R 3 have the same meaning as described above and X denotes a halogen preferably chosen from bromine and chlorine in particular chlorine.
  • a hydrogen halide chosen from hydrogen bromide and hydrogen chloride. Hydrogen chloride is particularly preferred.
  • the invention relates in particular to a process for preparing 2-chloroprop-1-ene by reaction of methylacetylene and / or propadiene with hydrogen chloride in a liquid medium comprising at least
  • the process according to the invention makes it possible to obtain 2-chloroprop-1-ene with improved selectivity by compared to the known process.
  • the process according to the invention also makes it possible to improve the conversion of methylacetylene while retaining a high selectivity for 2-chloroprop-1-ene. This makes it possible to increase the efficiency of the manufacture of 2-chloroprop-1-ene, in particular when a starting product comprising methylacetylene is used.
  • an organic nitrile is used as the solvent capable of dissolving the catalyst.
  • the organic nitrile comprises 1, 2, 3 or 4 nitrile functionalities.
  • the aliphatic nitriles of general formula CH3- (CH2) n -CN with n an integer from 3 to 7 are especially usable; aliphatic dinitriles of general formula NC- (CH2) m -CN with m an integer from 3 to 10; and aromatic nitriles such as benzonitrile and toluonitrile.
  • Aliphatic dinitriles of general formula NC- (CH2) m -CN with m an integer from 3 to 10, preferably with m an integer from 4 to 6 are preferred.
  • Adiponitrile is very particularly preferred.
  • the catalyst used in the process of the present invention comprises at least one palladium compound.
  • the palladium compound is often chosen from complexes and salts containing palladium in the oxidation stage 0 or 2.
  • a palladium compound containing palladium in the oxidation stage 2 is used.
  • the palladium compounds used are chosen from halides. A preference is shown for chlorides or bromides but any other compound which can transform into halide in the presence of hydrogen halide can also be used.
  • palladium compounds complexed by electron-rich systems such as amines, oxygenated compounds such as carbonyl compounds or ethers, cyclic or acyclic, sulfur compounds, aromatic compounds or compounds carrying aromatic nuclei.
  • the salts formed between palladium and an acidic organic compound are advantageously considered as palladium compounds which can be used, not only with carboxylic acids but also with other compounds, such as acetylacetone.
  • We can also implement as catalyst for palladium (0) complexes such as complexes formed with triphenylphosphine or triphenylphosphine oxide.
  • palladium (H) complexes as catalyst, such as ⁇ -al yl complexes such as, for example, bis- ( ⁇ 3 -allyl- ⁇ -chloropalladium (LI)).
  • Suitable palladium salts are, for example, F palladium acetate (H), palladium nitrate (LT) palladium bromide (II) and palladium chloride (II). Palladium (II) chloride and palladium bromide (LT) are particularly preferred. Palladium chloride (TJ) is very particularly preferred.
  • the nature and / or the amount of catalyst used is such that all of the catalyst is in dissolved form.
  • a catalyst in quantity or in nature such that at least one action thereof is present in the liquid medium in dispersed solid form, without prejudice to the invention.
  • the quantity of catalyst used is generally greater than or equal to 0.1 millimole per liter of liquid medium.
  • the liquid medium consists essentially of an organic nitrile as described above.
  • the invention also relates to a catalytic system comprising any one of the above-mentioned palladium compounds and any one of the above-mentioned organic nitriles, preferably in the amounts of catalyst mentioned in the above-mentioned organic nitrile.
  • a cocatalyst which comprises at least one compound of at least one metal from groups Ib or TVb such as copper, silver, tin or lead .
  • metals such as copper and tin, in particular copper.
  • the metal compound of groups Ib or TVb used as cocatalyst in this embodiment is a chloride. Particular preference is shown for copper chloride (TJ).
  • the cocatalyst is used in a molar ratio relative to the catalyst greater than 0.1. Preferably, this molar ratio is greater than or equal to 1.
  • this molar ratio is greater than or equal to 2. However, this molar ratio is usually less than 20.
  • this molar ratio is less than or equal to 15.
  • this molar ratio is less than or equal to 10.
  • the cocatalyst can be introduced at the start of the reaction, at the same time as the catalyst, or it can be introduced during the reaction.
  • the liquid medium comprises at least one organic co-solvent.
  • the choice of the nature of the organic co-solvent used is conditioned in particular by the need for it to be inert with respect to the reactants under the reaction conditions and for it to be miscible with the solvent at the reaction temperature. and that it is capable of dissolving it, in particular when the latter is solid at room temperature.
  • organic co-solvents are chosen from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, for example C7 to C ⁇ paraffins and alkylbenzenes, in particular xylenes, propylbenzenes, butylbenzenes, methylethylbenzenes.
  • the co-solvent used is preferably chosen from commercial products consisting of mixtures of aliphatic hydrocarbons such as the product ISOPAR from ESSO or
  • Suitable co-solvents are for example aliphatic co-solvents
  • ® saturated such as the product SHELLSOL D70, consisting of petroleum fractions having a boiling point greater than or equal to approximately 190 ° C and less than or equal to approximately 250 ° C.
  • co-solvents that can be envisaged on the basis of the various criteria given above are certain heavy halogenated compounds, such as haloalkanes, halobenzenes and other halogenated derivatives of aromatic compounds.
  • the weight ratio between the organic nitrile and the co-solvent is generally at least 0.1. More often this ratio is at least 0.2. Preferably it is at least 0.3. Where appropriate, when the process according to the invention is carried out in the presence of a co-solvent, the weight ratio between the organic nitrile and the co-solvent is generally at most 10. More often this ratio is at most 5. Preferably it is at most 3.
  • the method according to the invention is carried out in the absence of co-solvent.
  • a particularly liquid medium in the process according to the invention, a particularly liquid medium
  • preferred contains palladium chloride (TJ) as the catalyst and adiponitrile as the solvent. More particularly preferred is a liquid medium consisting essentially of palladium chloride (TJ) as catalyst and adiponitrile as solvent.
  • TJ palladium chloride
  • the process for manufacturing 2-chloroprop-1-ene according to the invention is carried out by bringing methylacetylene and / or propadiene into contact with hydrogen chloride in any suitable reactor containing the liquid medium. This contacting is generally carried out by introducing a gaseous fraction comprising methylacetylene and / or propadiene into the liquid medium.
  • the introduction of the gaseous fraction into the liquid medium is preferably carried out so as to maximize the gas / liquid exchange surface.
  • means of introduction and / or stirring will be chosen ensuring good dispersion of the gas in the form of bubbles in the liquid medium.
  • means of introduction are inter alia porous plates or porous frits having an adequate porosity and distribution pipes having multiple holes allowing the passage of the gaseous fraction.
  • the flow rate of the gases introduced into the reactor is advantageously adjusted so as to maximize the gas / liquid exchange surface.
  • the process according to the invention can be carried out, discontinuously or continuously, conventionally in any apparatus promoting gas-liquid exchange such as a column with trays, a column with stackings, in particular an embedded column with stackings, a saturator type reactor or a bubble column.
  • saturator type reactor is understood to mean in particular a tabular reactor containing during the reaction alternating segments of liquid medium and of gas which are propelled towards the outlet of the tube by the pressure of the gas.
  • the apparatuses used in the process according to the invention are generally made of a material which has sufficient resistance to corrosion in the presence of hydrogen chloride and of the liquid medium, in especially in the presence of the catalytic system.
  • Useful materials are selected for example from graphite impregnated polymer and steel, for example of HASTELLOY ® etlNCONEL ®, optionally coated with polymer.
  • the polymer with which the graphite is impregnated or the steel is coated is preferably chosen from a fluorinated polymer, in particular polytetrafluoroethylene (PTFE) and a phenolic polymer.
  • PTFE polytetrafluoroethylene
  • graphite-impregnated polymer available are those marketed under the names GRAPHELOR ® which is a graphite impregnated PTFE and DIABON ® NS-1 which is a graphite impregnated with a phenolic polymer.
  • GRAPHELOR ® which is a graphite impregnated PTFE
  • DIABON ® NS-1 which is a graphite impregnated with a phenolic polymer.
  • steel coated with polymer is that marketed under the name ARMTLOR, which is a steel coated with PTFE.
  • the graphite impregnated with polymer or the coated steel is advantageously used to produce the parts of the reactor or other components of the equipment of the process which are regularly in contact with the liquid medium such as pumps or introduction means. as described above.
  • HASTELLOY ® B and C steels are well suited.
  • HASTELLOY ® C type steel is preferred.
  • HASTELLOY ® C type steel is advantageously used to make the parts of the reactor which are, if necessary, substantially exclusively in contact with the gas phase present in the reactor.
  • the materials mentioned above are well suited for implementing the method according to the invention. They can also be used with other catalytic systems as described for example in application EP-A-905113.
  • the invention relates in a particular aspect therefore also to the use of reactors as described above comprising the materials as described above for carrying out a hydrochlorination reaction with hydrogen chloride in a liquid medium containing at least one hydrochlorination catalyst which preferably comprises at least one compound chosen from compounds of the metals of the group VTJIa and lanthanides, and an organic solvent capable of solubilizing the catalyst.
  • the gas / liquid contact time which is the period during which the gas is in contact with the liquid medium, for example in the form of a bubble which passes through a given quantity of liquid medium, is generally greater than or equal to 0.5 seconds.
  • the contact time is greater than or equal to 1 second.
  • the time to gas / liquid contact does not exceed 5 minutes. It is most often less than or equal to 2 minutes.
  • it is less than or equal to 1 minute. It has been found that particularly good selectivities and yields of 2-chloroprop-1-ene are obtained by implementing the method according to the invention under the contact time conditions mentioned above.
  • the molar ratio between hydrogen chloride and methylacetylene and / or propadiene introduced into the reactor is generally greater than or equal to about 0.5. Preferably, this ratio is greater than or equal to 1. In general, this molar ratio is less than or equal to about 10. Preferably, this ratio is less than or equal to 5. Good results have been obtained with a molar ratio between the hydrogen chloride and methylacetylene and / or propadiene introduced into the reactor less than or equal to about 2.5.
  • the methylacetylene and / or propadiene and hydrogen chloride can be brought into contact in the reactor or mixed before their introduction into the reactor.
  • the process of the invention can be carried out from ambient temperature to approximately 200 ° C. At higher temperatures, the catalyst tends to degrade.
  • the preferred reaction temperature that is to say that offering the best compromise between productivity, yield and stability of the catalyst, is greater than or equal to 80 ° C. The best results are obtained at temperatures greater than or equal to about 100 ° C. Preferably, the reaction temperature does not exceed about 180 ° C. A reaction temperature less than or equal to about 160 ° C is particularly preferred.
  • the pressure is generally greater than or equal to atmospheric pressure and equal to or less than 15 bars. Preferably, the pressure is less than or equal to 10 bars. A particular preference is shown for a pressure less than or equal to 5 bars.
  • the process of the invention often takes place at a pressure close to or greater than 1 bar.
  • a pressure greater than or equal to 2 bars gives good results.
  • a pressure of around 3 bars is particularly suitable.
  • the flow rate of reagents, generally gaseous, is generally sufficient to allow efficient mixing of the liquid medium. It is also possible to use known stirring means for the liquid medium, such as mechanical stirrers.
  • the residence time which is the ratio between the volume of liquid medium in the reactor and the volume flow rate of the reactants, is generally greater than or equal to 0.5 seconds.
  • the time to stay is greater than or equal to 1 second.
  • the residence time does not exceed 5 minutes. It is most often less than or equal to 2 minutes.
  • it is less than or equal to 1 minute.
  • TETRENE Air Liquide under the name of TETRENE. Its molar composition is approximately 25% methylacetylene, 13% propadiene, 46% propylene, 4% propane and 12% C4 hydrocarbons.
  • the liquid medium is saturated with hydrogen chloride before introducing the methyl acetylene and / or the propadiene into the reactor. This makes it possible to maintain a particularly good activity of the catalytic system during the reaction.
  • the invention therefore also relates to a method for preparing 2-chloroprop-1-ene by reacting a methylacetylene / propadiene mixture with hydrogen chloride in a liquid medium comprising at least one hydrochlorination catalyst and at least one organic solvent capable of solubilizing the catalyst, method in which
  • step (c) the fraction comprising unreacted methylacetylene and propadiene is recycled to step (a).
  • the molar ratio between methylacetylene and propadiene in the fraction comprising unreacted methylacetylene and propadiene is substantially identical to the initial molar ratio between these same constituents.
  • the variation in the molar ratio between methylacetylene and propadiene in the fraction comprising unreacted methylacetylene and propadiene relative to the initial molar ratio is generally less than or equal to 10%. Preferably this variation is less than or equal to 5%. A variation less than or equal to 1% is more particularly preferred. A variation less than or equal to 0.5% is very particularly preferred. We can even arrive at a variation of 0%.
  • the variation can be adjusted, if necessary by operations intended to modify the molar ratio between methylacetylene and propadiene such as for example an addition of one of these compounds or a selective separation operation such as an adsorption.
  • operations intended to modify the molar ratio between methylacetylene and propadiene such as for example an addition of one of these compounds or a selective separation operation such as an adsorption.
  • the process according to the invention described above makes it possible to obtain, at the end of the reaction, a fraction comprising unreacted methylacetylene and propadiene with a molar ratio between methylacetylene and propadiene substantially identical to the molar ratio initial.
  • the method according to the invention allows very efficient use of the raw materials while avoiding an accumulation of one of the starting materials in the reactor.
  • the invention also relates to a process for manufacturing a fluorinated compound, in particular a hydrofluoroalkane comprising
  • the manufacture of the halogen precursor can be, for example, a telomerization reaction in which 2-chloroprop-1-ene is reacted with a haloalkane in the presence of a catalyst and optionally a cocatalyst.
  • This type of reaction is particularly suitable for obtaining 1,1,1,3,3-pentachlorobutane, which is a halogen precursor of 1, 1, 1,3,3-pentafluorobutane.
  • 2-chloroprop-1-ene is therefore reacted with tetrachloromethane in the presence of a catalyst comprising a copper compound and a cocatalyst chosen from amines to form 1, 1, 1, 3,3-peritachlorobutane.
  • the preferred fluorinated reagent is anhydrous hydrogen fluoride.
  • the fluorination can be carried out in the presence or absence of a fluorination catalyst.
  • the fluorination is advantageously chosen from the metal halides of group 4, 5, 14 and 15, in particular the derivatives of tin, antimony, titanium, niobium and tantalum.
  • the preferred hydrofluoroalkane is 1,1,1,3,3-pentafluorobutane.
  • the reaction was carried out in a reactor of saturator type provided with a double jacket in which circulates oil thermostatically controlled at the test temperature and surmounted by a cooled condenser to condense the solvent and co-solvent vapors .
  • a reactor of saturator type provided with a double jacket in which circulates oil thermostatically controlled at the test temperature and surmounted by a cooled condenser to condense the solvent and co-solvent vapors .
  • 0.15 mmol of PdCTj was dissolved by slightly heating in 80 ml of adiponitrile. After complete dissolution of the palladium chloride, the liquid phase was poured into the reactor previously heated to 140 ° C. Hydrogen chloride was then injected at a rate of
  • the process according to the invention makes it possible to obtain 2-chloroprop-1-ene with better selectivity compared to the process catalyzed by PtCl 2 / adiponitrile.
  • the conversion of methylacetylene is greatly improved.
  • the process according to the invention therefore provides unexpected and superior results compared to the process catalyzed by PtCVadiponitrile.
  • the conversion rates of propadiene and methylacetylene are identical. Therefore the mixture of propadiene and methylacetylene unconverted is, after separation of 2-chloroprop-1-ene, suitable for recycling to the manufacturing reaction.

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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)

Abstract

The invention relates to a method for preparing a halogenated olefin by reacting an alkyne and/or an allenic compound with a hydrogen halide in a liquid medium comprising at least one hydrohalogenation catalyst containing at least one palladium compound.

Description

Procédé dé préparation d'une oléfine halogénée Process for the preparation of a halogenated olefin
La présente invention concerne un procédé de préparation d'une oléfine halogénée, en particulier du 2-chloroprop-l-ène.The present invention relates to a process for the preparation of a halogenated olefin, in particular 2-chloroprop-1-ene.
Le 2-chloroprop-l-ène est un intermédiaire dans la synthèse de précurseurs halogènes du 1, 1, 1,3,3-pentafluorobutane (HFC-365mfc) utilisé comme solvant et comme agent gonflant dans la préparation de mousses cellulaires polymériques. Le 2-chloroprop-l-ène est particulièrement utile pour la synthèse du précurseur 1,1,1,3,3-pentachlorobutane.2-Chloroprop-1-ene is an intermediate in the synthesis of halogen precursors of 1, 1, 1,3,3-pentafluorobutane (HFC-365mfc) used as a solvent and as a swelling agent in the preparation of polymeric cellular foams. 2-chloroprop-1-ene is particularly useful for the synthesis of the precursor 1,1,1,3,3-pentachlorobutane.
La demande de brevet EP-A-905113 au nom de la Demanderesse enseigne un procédé de préparation du 2-chloroprop- 1 -ène par réaction de méthylaçétylène et/ou de propadiène avec du chlorure d'hydrogène dans un milieu liquide renfermant au moinsPatent application EP-A-905 113 in the name of the Applicant teaches a process for the preparation of 2-chloroprop-1-ene by reaction of methylacetylene and / or propadiene with hydrogen chloride in a liquid medium containing at least
(a) un catalyseur d'hydrochloration qui comprend au moins un composé choisi parmi les composés des métaux du groupe Villa et des lanthanides ; et (b) un solvant organique capable de solubiliser le catalyseur.(a) a hydrochlorination catalyst which comprises at least one compound chosen from compounds of the metals of the Villa group and of lanthanides; and (b) an organic solvent capable of solubilizing the catalyst.
Ce procédé connu donne globalement des résultats très satisfaisants. Toutefois, il était désirable de trouver un procédé de préparation du 2- chloroprop-1-ène par réaction de méthylaçétylène et/ou de propadiène permettant d'obtenir une sélectivité améliorée en 2-chloroprop-l-ène. Il était également souhaitable de trouver un tel procédé permettant une conversion efficace de méthylaçétylène et de propadiène, assurant une utilisation encore plus efficace de ces matières premières.This known method gives overall very satisfactory results. However, it was desirable to find a process for the preparation of 2-chloroprop-1-ene by reaction of methylacetylene and / or propadiene making it possible to obtain improved selectivity for 2-chloroprop-1-ene. It was also desirable to find such a process allowing an efficient conversion of methylacetylene and propadiene, ensuring an even more efficient use of these raw materials.
L'invention concerne dès lors un procédé de préparation d'une oléfine halogénée par réaction d'un alkyne et/ou d'un composé allénique avec un halogénure d'hydrogène dans un milieu liquide comprenant au moinsThe invention therefore relates to a process for the preparation of a halogenated olefin by reacting an alkyne and / or an allenic compound with a hydrogen halide in a liquid medium comprising at least
(a) un catalyseur d'hydrohalogénation comprenant au moins un composé de palladium; et(a) a hydrohalogenation catalyst comprising at least one palladium compound; and
(b) au moins un solvant organique capable de solubiliser le catalyseur, choisi parmi les nitriles organiques. Conviennent bien à titre d' alkyne, les alkynes de formule générale (I)(b) at least one organic solvent capable of dissolving the catalyst, chosen from organic nitriles. Suitable as an alkyne, the alkynes of general formula (I)
P C≡C-H dans laquelle R1 désigne un groupement hydrogène, alkyle, aryle, carboxyle, . ester ou halogène. De préférence R1 est choisi parmi un groupement carboxyle, un groupement alkyl comprenant de 1 à 10 atomes de carbone, un groupement phényle éventuellement substitué par 1,2 ou 3 substituants alkyl comprenant de 1 à 4 atomes de carbone, un alkylester porteur d'un radical alkyl comprenant de 1 à 10 atomes de carbone ou un aryl ester.PC≡CH in which R 1 denotes a hydrogen, alkyl, aryl or carboxyl group. ester or halogen. Preferably R 1 is chosen from a carboxyl group, an alkyl group comprising from 1 to 10 carbon atoms, a phenyl group optionally substituted by 1,2 or 3 alkyl substituents comprising from 1 to 4 carbon atoms, an alkyl ester carrying an alkyl radical comprising from 1 to 10 carbon atoms or an aryl ester.
Conviennent bien à titre de composé allénique, les composés de formule générale (TJ)Suitable as an allenic compound, the compounds of general formula (TJ)
R2R3C=C=CH2 (H) dans laquelle R2 et R3 désignent indépendamment un groupement hydrogène alkyl, aryl, carboxyle, ester ou halogène. De préférence 2 est R3 sont choisis indépendamment parmi un groupement hydrogène, un groupement carboxyle un groupement alkyl comprenant de 1 à 10 atomes de carbone, un groupement phényle éventuellement substitué par 1,2 ou 3 substituants alkyl comprenant de 1 à 4 atomes de carbone, un alkylester porteur d'un radical alkyl comprenant de 1 à 10 atomes de carbone ou un aryl ester.R 2 R 3 C = C = CH 2 (H) in which R 2 and R 3 independently denote a hydrogen group alkyl, aryl, carboxyl, ester or halogen. Preferably 2 and R 3 are independently chosen from a hydrogen group, a carboxyl group, an alkyl group comprising from 1 to 10 carbon atoms, a phenyl group optionally substituted by 1,2 or 3 alkyl substituents comprising from 1 to 4 carbon atoms , an alkylester carrying an alkyl radical comprising from 1 to 10 carbon atoms or an aryl ester.
On a en effet observé que le procédé selon l'invention permet de manière particulièrement sélective d'accéder à des halooléfines de formule générale (ni) et (TV) I^-XC≈CEk (m)It has in fact been observed that the process according to the invention makes it possible, in a particularly selective manner, to access haloolefins of general formula (ni) and (TV) I ^ -XC≈CEk (m)
R2R3C=XC-CH3 (TV) dans lesquelles R1, R2 et R3 ont la même signification que décrite plus haut et X désigne un halogène choisi de préférence parmi le brome et le chlore en particulier le chlore. Dans le procédé selon l'invention on préfère mettre en œuvre un halogénure d'hydrogène choisi parmi le bromure d'hydrogène et le chlorure d'hydrogène. Le chlorure d'hydrogène est particulièrement préféré.R 2 R 3 C = XC-CH 3 (TV) in which R 1 , R 2 and R 3 have the same meaning as described above and X denotes a halogen preferably chosen from bromine and chlorine in particular chlorine. In the method according to the invention it is preferred to use a hydrogen halide chosen from hydrogen bromide and hydrogen chloride. Hydrogen chloride is particularly preferred.
L'invention concerne en particulier un procédé de préparation du 2- chloroprop-1-ène par réaction de méthylaçétylène et/ou de propadiène avec du chlorure d'hydrogène dans un milieu liquide comprenant au moinsThe invention relates in particular to a process for preparing 2-chloroprop-1-ene by reaction of methylacetylene and / or propadiene with hydrogen chloride in a liquid medium comprising at least
(a) un catalyseur d'hydrochloration comprenant au moins un composé choisi parmi les composés de palladium; et(a) a hydrochlorination catalyst comprising at least one compound chosen from palladium compounds; and
(b) au moins un solvant organique capable de solubiliser le catalyseur, choisi parmi les nitriles organiques. II a été trouvé, de manière surprenante, que le procédé selon l'invention permet d'obtenir du 2-chloroprop-l-ène avec une sélectivité améliorée par rapport au procédé connu. Le procédé selon l'invention permet de plus d'améliorer la conversion du méthylaçétylène tout eh conservant une sélectivité élevée en 2-chloroprop-l-ène. Ceci permet d'augmenter l'efficacité de la fabrication du 2- chloroprop-1-ène en particulier lorsqu'on met en œuvre un produit de départ comprenant du méthylaçétylène.(b) at least one organic solvent capable of dissolving the catalyst, chosen from organic nitriles. It has been found, surprisingly, that the process according to the invention makes it possible to obtain 2-chloroprop-1-ene with improved selectivity by compared to the known process. The process according to the invention also makes it possible to improve the conversion of methylacetylene while retaining a high selectivity for 2-chloroprop-1-ene. This makes it possible to increase the efficiency of the manufacture of 2-chloroprop-1-ene, in particular when a starting product comprising methylacetylene is used.
La suite de la description se rapportera en particulier au procédé de synthèse de 2-chloroprop-l-ène. Il est cependant entendu que les variantes et préférences décrites s'appliquent le cas échéant également au procédé selon l'invention de fabrication d'une halooléfine de formule générale (III) ou (IV). De manière avantageuse, le procédé selon l'invention se déroule en absence substantielle d'eau.The following description will relate in particular to the process for the synthesis of 2-chloroprop-1-ene. It is however understood that the variants and preferences described also apply, where appropriate, to the process according to the invention for the manufacture of a haloolefin of general formula (III) or (IV). Advantageously, the process according to the invention takes place in the substantial absence of water.
Comme solvant capable de solubiliser le catalyseur, on utilise un nitrile organique. Généralement, le nitrile organique comprend 1, 2, 3 ou 4 fonctionnalités nitrile. Sont notamment utilisables les nitriles aliphatiques de formule générale CH3-(CH2)n-CN avec n un entier de 3 à 7 ; les dinitriles aliphatiques de formule générale NC-(CH2)m-CN avec m un entier de 3 à 10 ; et les nitriles aromatiques tels que le benzonitrile et le toluonitrile. Les dinitriles aliphatiques de formule générale NC-(CH2)m-CN avec m un entier de 3 à 10, de préférence avec m un entier de 4 à 6 sont préférés. L'adiponitrile est tout particulièrement préféré.As the solvent capable of dissolving the catalyst, an organic nitrile is used. Generally, the organic nitrile comprises 1, 2, 3 or 4 nitrile functionalities. The aliphatic nitriles of general formula CH3- (CH2) n -CN with n an integer from 3 to 7 are especially usable; aliphatic dinitriles of general formula NC- (CH2) m -CN with m an integer from 3 to 10; and aromatic nitriles such as benzonitrile and toluonitrile. Aliphatic dinitriles of general formula NC- (CH2) m -CN with m an integer from 3 to 10, preferably with m an integer from 4 to 6 are preferred. Adiponitrile is very particularly preferred.
Le catalyseur utilisé dans le procédé de la présente invention comprend au moins un composé de palladium. Le composé de palladium est souvent choisi parmi les complexes et les sels contenant le palladium à l'étage d'oxydation 0 ou 2. De préférence on met en œuvre un composé de palladium contenant le palladium à l'étage d'oxydation 2. Avantageusement, les composés de palladium mis en œuvre sont choisis parmi les halogénures. Une préférence est montrée pour les chlorures ou les bromures mais tout autre composé pouvant se transformer en halogénure en présence d'halogénure d'hydrogène peut aussi être utilisé. Peuvent également être mis en œuvre, les composés de palladium complexés par des systèmes riches en électrons tels que les aminés, les composés oxygénés comme les composés carbonylés ou les éthers, cycliques ou acycliques, les composés soufrés, les composés aromatiques ou les composés porteurs de noyaux aromatiques. Sont avantageusement considérés comme composés dé palladium utilisables, les sels formés entre le palladium et un composé organique acide, non seulement avec les acides carboxyliques mais aussi avec d'autres composés, tels que l'acétylacétone. On peut également mettre en œuvre comme catalyseur des complexes de palladium (0) tels que les complexes formés avec la triphénylphosphine ou l'oxyde de triphénylphosphine. On peut également mettre en œuvre comme catalyseur des complexes de palladium (H) tels que des complexes π-al yl comme par exemple le bis-(η3-allyl-μ-chloropalladium(LI)). A titre de sels de palladium conviennent, par exemple, F acétate de palladium (H), le nitrate de palladium (LT) le bromure de palladium (II) et le chlorure de palladium (II). Le chlorure de palladium (II) et le bromure de palladium (LT) sont particulièrement préférés. Le chlorure de palladium (TJ) est tout particulièrement préféré. Avantageusement, la nature et/ou la quantité de catalyseur mise en œuvre est telle que, tout le catalyseur se trouve sous forme dissoute. On peut cependant aussi mettre en œuvre un catalyseur en quantité ou de nature telle qu'une f action au moins de celui-ci soit présente dans le milieu liquide sous forme solide dispersé, sans porter préjudice à l'invention. La quantité de catalyseur engagé est généralement supérieure ou égale à 0,1 millimole par litre de milieu liquide. De préférence, elle est supérieure ou égale à 0,5 millimole par litre de milieu liquide. Avantageusement, elle est supérieure ou égale à 1 millimole par litre de milieu liquide. La quantité de catalyseur est habituellement inférieure ou égale à 50 millimoles par litre de milieu liquide. De préférence, elle est inférieure ou égale à 20 millimoles par litre de milieu liquide. Avantageusement, elle est inférieure ou égale à 10 millimoles par litre de milieu liquide. De préférence, le milieu liquide est constitué essentiellement d'un nitrile organique tel que décrit plus haut.The catalyst used in the process of the present invention comprises at least one palladium compound. The palladium compound is often chosen from complexes and salts containing palladium in the oxidation stage 0 or 2. Preferably, a palladium compound containing palladium in the oxidation stage 2 is used. Advantageously , the palladium compounds used are chosen from halides. A preference is shown for chlorides or bromides but any other compound which can transform into halide in the presence of hydrogen halide can also be used. Can also be used, palladium compounds complexed by electron-rich systems such as amines, oxygenated compounds such as carbonyl compounds or ethers, cyclic or acyclic, sulfur compounds, aromatic compounds or compounds carrying aromatic nuclei. The salts formed between palladium and an acidic organic compound are advantageously considered as palladium compounds which can be used, not only with carboxylic acids but also with other compounds, such as acetylacetone. We can also implement as catalyst for palladium (0) complexes such as complexes formed with triphenylphosphine or triphenylphosphine oxide. It is also possible to use palladium (H) complexes as catalyst, such as π-al yl complexes such as, for example, bis- (η 3 -allyl-μ-chloropalladium (LI)). Suitable palladium salts are, for example, F palladium acetate (H), palladium nitrate (LT) palladium bromide (II) and palladium chloride (II). Palladium (II) chloride and palladium bromide (LT) are particularly preferred. Palladium chloride (TJ) is very particularly preferred. Advantageously, the nature and / or the amount of catalyst used is such that all of the catalyst is in dissolved form. However, it is also possible to use a catalyst in quantity or in nature such that at least one action thereof is present in the liquid medium in dispersed solid form, without prejudice to the invention. The quantity of catalyst used is generally greater than or equal to 0.1 millimole per liter of liquid medium. Preferably, it is greater than or equal to 0.5 millimole per liter of liquid medium. Advantageously, it is greater than or equal to 1 millimole per liter of liquid medium. The amount of catalyst is usually less than or equal to 50 millimoles per liter of liquid medium. Preferably, it is less than or equal to 20 millimoles per liter of liquid medium. Advantageously, it is less than or equal to 10 millimoles per liter of liquid medium. Preferably, the liquid medium consists essentially of an organic nitrile as described above.
L'invention concerne aussi un système catalytique comprenant l'un quelconque des composés de palladium précités et l'un quelconque des nitriles organiques précités, de préférence dans les quantités de catalyseur dans le nitrile organique précitées.The invention also relates to a catalytic system comprising any one of the above-mentioned palladium compounds and any one of the above-mentioned organic nitriles, preferably in the amounts of catalyst mentioned in the above-mentioned organic nitrile.
Dans une variante du procédé selon l'invention, on met aussi en œuvre un cocatalyseur, lequel comprend au moins un composé d'au moins un métal des groupes Ib ou TVb tel que le cuivre, l'argent, l'étain ou le plomb. Une préférence est marquée pour des métaux tels que le cuivre et l'étain, en particulier le cuivre. De préférence, le composé de métal des groupes Ib ou TVb mis en œuvre comme cocatalyseur dans ce mode de réalisation est un chlorure. Une préférence particulière est montrée pour le chlorure de cuivre (TJ). Généralement, le cocatalyseur est mis en œuvre dans un rapport molaire par rapport au catalyseur supérieur à 0,1. De préférence, ce rapport molaire est supérieur ou égal à 1. Avantageusement, ce rapport molaire est supérieur ou égal à 2. Toutefois, ce rapport molaire est habituellement inférieur à 20. De préférence, ce rapport molaire est inférieur ou égal à 15. Avantageusement, ce rapport molaire est inférieur ou égal à 10. Le cocatalyseur peut être introduit au début de la réaction, en même temps que le catalyseur, ou il peut être introduit en cours de réaction. Dans une autre variante, outre le composé de palladium et le nitrile organique, le milieu liquide comprend au moins un co-solvant organique. Le choix de la nature du co-solvant organique mis en œuvre est conditionné notamment par la nécessité qu'il soit inerte vis-à-vis des réactifs dans les conditions de réaction, qu'il soit miscible avec le solvant à la température de réaction et qu'il soit capable de le solubiliser, en particulier lorsque ce dernier est solide à température ambiante. Par ailleurs, pour des raisons de sécurité et de facilité d'emploi, on donne la préférence aux co-solvants organiques peu volatils. Le choix du co-solvant organique est aussi influencé par sa capacité de dissolution du méthylaçétylène et/ou du propadiène. Des co-solvants satisfaisant aux différents critères exposés ci-dessus sont choisis parmi les hydrocarbures aliphatiques, cycloaliphatiques et aromatiques et leurs mélanges, par exemple les paraffines en C7 à C\ζ et les alkylbenzènes, notamment les xylènes, les propylbenzènes, les butylbenzènes, les méthyléthylbenzènes. Le co-solvant mis en œuvre est de préférence choisi parmi les produits commerciaux constitués de mélanges d'hydrocarbures aliphatiques tels que le produit ISOPAR de ESSO ouIn a variant of the process according to the invention, a cocatalyst is also used, which comprises at least one compound of at least one metal from groups Ib or TVb such as copper, silver, tin or lead . A preference is marked for metals such as copper and tin, in particular copper. Preferably, the metal compound of groups Ib or TVb used as cocatalyst in this embodiment is a chloride. Particular preference is shown for copper chloride (TJ). Generally, the cocatalyst is used in a molar ratio relative to the catalyst greater than 0.1. Preferably, this molar ratio is greater than or equal to 1. Advantageously, this molar ratio is greater than or equal to 2. However, this molar ratio is usually less than 20. Preferably, this molar ratio is less than or equal to 15. Advantageously, this molar ratio is less than or equal to 10. The cocatalyst can be introduced at the start of the reaction, at the same time as the catalyst, or it can be introduced during the reaction. In another variant, in addition to the palladium compound and the organic nitrile, the liquid medium comprises at least one organic co-solvent. The choice of the nature of the organic co-solvent used is conditioned in particular by the need for it to be inert with respect to the reactants under the reaction conditions and for it to be miscible with the solvent at the reaction temperature. and that it is capable of dissolving it, in particular when the latter is solid at room temperature. Furthermore, for reasons of safety and ease of use, preference is given to low-volatile organic co-solvents. The choice of organic co-solvent is also influenced by its ability to dissolve methylacetylene and / or propadiene. Co-solvents satisfying the various criteria set out above are chosen from aliphatic, cycloaliphatic and aromatic hydrocarbons and their mixtures, for example C7 to C \ paraffins and alkylbenzenes, in particular xylenes, propylbenzenes, butylbenzenes, methylethylbenzenes. The co-solvent used is preferably chosen from commercial products consisting of mixtures of aliphatic hydrocarbons such as the product ISOPAR from ESSO or
® le produit SHELLSOL D70 de SHELL ou de mélanges de composés® SHELLSOL D70 from SHELL or mixtures of compounds
® aromatiques tels que le produit SOLVESSO de ESSO ou le produit® aromatics such as the SOLVESSO product from ESSO or the product
SHELLSOL® AB de SHELL. Des co-solvants appropriés sont par exemple les co-solyants aliphatiquesSHELLSOL ® AB from SHELL. Suitable co-solvents are for example aliphatic co-solvents
® saturés tels que le produit SHELLSOL D70, constitué de coupes pétrolières ayant un point d'ébullition supérieur ou égal à environ 190 °C et inférieur ou égal à environ 250 °C.® saturated such as the product SHELLSOL D70, consisting of petroleum fractions having a boiling point greater than or equal to approximately 190 ° C and less than or equal to approximately 250 ° C.
D'autres co-solvants envisageables sur base des divers critères donnés ci- dessus sont certains composés halogènes lourds, tels que des halogénoalcanes, halogénobenzènes et autres dérivés halogènes de composés aromatiques.Other co-solvents that can be envisaged on the basis of the various criteria given above are certain heavy halogenated compounds, such as haloalkanes, halobenzenes and other halogenated derivatives of aromatic compounds.
Lorsque le procédé selon l'invention est effectué en présence d'un co- solvant, le rapport pondéral entre le nitrile organique et le co-solvant est généralement d'au moins 0,1. Plus souvent ce rapport est d'au moins 0,2. De préférence il est d'au moins 0,3. Le cas échéant, lorsque le procédé selon l'invention est effectué en présence d'un co-solvant le rapport pondéral entre le nitrile organique et le co-solvant est généralement d'au plus 10. Plus souvent ce rapport est d'au plus 5. De préférence il est d'au plus 3.When the process according to the invention is carried out in the presence of a co-solvent, the weight ratio between the organic nitrile and the co-solvent is generally at least 0.1. More often this ratio is at least 0.2. Preferably it is at least 0.3. Where appropriate, when the process according to the invention is carried out in the presence of a co-solvent, the weight ratio between the organic nitrile and the co-solvent is generally at most 10. More often this ratio is at most 5. Preferably it is at most 3.
Dans une variante qui est préférée, le procédé selon l'invention est effectué en l'absence de co-solvant. Dans le procédé selon l'invention, un milieu liquide particulièrementIn a variant which is preferred, the method according to the invention is carried out in the absence of co-solvent. In the process according to the invention, a particularly liquid medium
, préféré contient du chlorure de palladium (TJ) comme catalyseur et de l' adiponitrile comme solvant. Est plus particulièrement préféré un milieu liquide constitué essentiellement de chlorure de palladium (TJ) comme catalyseur et d' adiponitrile comme solvant. Le procédé de fabrication du 2-chloroprop-l-ène selon l'invention est réalisé par mise en contact de méthylaçétylène et/ou de propadiène avec du chlorure d'hydrogène dans tout réacteur approprié renfermant le milieu liquide. Cette mise en contact est généralement réalisée par introduction d'une fraction gazeuse comprenant du méthylaçétylène et/ou de propadiène dans le milieu liquide., preferred contains palladium chloride (TJ) as the catalyst and adiponitrile as the solvent. More particularly preferred is a liquid medium consisting essentially of palladium chloride (TJ) as catalyst and adiponitrile as solvent. The process for manufacturing 2-chloroprop-1-ene according to the invention is carried out by bringing methylacetylene and / or propadiene into contact with hydrogen chloride in any suitable reactor containing the liquid medium. This contacting is generally carried out by introducing a gaseous fraction comprising methylacetylene and / or propadiene into the liquid medium.
L'introduction de la fraction gazeuse dans le milieu liquide est réalisée de préférence de manière à maximaliser la surface d'échange gaz/liquide. On choisira de préférence des moyens d'introduction et/ou d'agitation assurant une bonne dispersion du gaz sous forme de bulles dans le milieu liquide. Des exemples de moyens d'introduction sont entre autres des plaques poreuses ou frittes poreux présentant une porosité adéquate et des tuyaux de distribution présentant des multiples trous permettant le passage de la fraction gazeuse.The introduction of the gaseous fraction into the liquid medium is preferably carried out so as to maximize the gas / liquid exchange surface. Preferably, means of introduction and / or stirring will be chosen ensuring good dispersion of the gas in the form of bubbles in the liquid medium. Examples of means of introduction are inter alia porous plates or porous frits having an adequate porosity and distribution pipes having multiple holes allowing the passage of the gaseous fraction.
Dans le procédé selon l'invention, on ajuste avantageusement le débit des gaz introduits au réacteur de manière à maximaliser la surface d'échange gaz/liquide.In the process according to the invention, the flow rate of the gases introduced into the reactor is advantageously adjusted so as to maximize the gas / liquid exchange surface.
Le procédé selon l'invention peut être réalisé, de façon discontinue ou de façon continue, classiquement dans tout appareillage favorisant l'échange gaz- liquide telle qu'une colonne à plateaux, une colonne à empilages, en particulier une colonne noyée à empilages, un réacteur de type saturateur ou une colonne à bulles. Par réacteur de type saturateur, on entend en particulier un réacteur tabulaire contenant au cours de la réaction des segments alternants de milieu liquide et de gaz qui sont propulsés en direction de la sortie du tube par la pression du gaz.The process according to the invention can be carried out, discontinuously or continuously, conventionally in any apparatus promoting gas-liquid exchange such as a column with trays, a column with stackings, in particular an embedded column with stackings, a saturator type reactor or a bubble column. The term “saturator type reactor” is understood to mean in particular a tabular reactor containing during the reaction alternating segments of liquid medium and of gas which are propelled towards the outlet of the tube by the pressure of the gas.
Les appareillages mis en oeuvre dans le procédé selon l'invention sont généralement réalisés en un matériau qui présente une résistance suffisante à la corrosion en présence de chlorure d'hydrogène et du milieu liquide, en particulier en présence du système catalytique. Des matériaux utilisables sont choisis par exemple parmi le graphite imprégné de polymère et les aciers, par exemple de type HASTELLOY® etlNCONEL®, éventuellement revêtus de polymère. Le polymère avec lequel le graphite est imprégné ou l'acier est revêtu est de préférence choisi parmi un polymère fluoré, en particulier le polytétrafluoroéthylène (PTFE) et un polymère phénolique. Des exemples de graphite imprégné de polymère disponibles sont ceux commercialisés sous les dénominations GRAPHELOR® qui est un graphite imprégné de PTFE et DIABON® NS-1 qui est un graphite imprégné de polymère phénolique. Un exemple d'acier revêtu de polymère est celui commercialisé sous la dénomination ARMTLOR, qui est un acier revêtu de PTFE. Le graphite imprégné de polymère ou l'acier revêtu est avantageusement utilisé pour réaliser les parties du réacteur ou d'autres composantes de l'équipement du procédé qui se trouvent régulièrement en contact avec le milieu liquide telles que des pompes ou des moyens d'introduction tels que décrits plus haut.The apparatuses used in the process according to the invention are generally made of a material which has sufficient resistance to corrosion in the presence of hydrogen chloride and of the liquid medium, in especially in the presence of the catalytic system. Useful materials are selected for example from graphite impregnated polymer and steel, for example of HASTELLOY ® etlNCONEL ®, optionally coated with polymer. The polymer with which the graphite is impregnated or the steel is coated is preferably chosen from a fluorinated polymer, in particular polytetrafluoroethylene (PTFE) and a phenolic polymer. Examples of graphite-impregnated polymer available are those marketed under the names GRAPHELOR ® which is a graphite impregnated PTFE and DIABON ® NS-1 which is a graphite impregnated with a phenolic polymer. An example of steel coated with polymer is that marketed under the name ARMTLOR, which is a steel coated with PTFE. The graphite impregnated with polymer or the coated steel is advantageously used to produce the parts of the reactor or other components of the equipment of the process which are regularly in contact with the liquid medium such as pumps or introduction means. as described above.
Parmi les aciers, les aciers de type HASTELLOY® B et C conviennent bien. L'acier de type HASTELLOY® C est préféré. L'acier de type HASTELLOY® C est avantageusement utilisé pour réaliser les parties du réacteur qui se trouvent, le cas échéant, substantiellement exclusivement en contact avec la phase gazeuse présente dans le réacteur.Among the steels, HASTELLOY ® B and C steels are well suited. HASTELLOY ® C type steel is preferred. HASTELLOY ® C type steel is advantageously used to make the parts of the reactor which are, if necessary, substantially exclusively in contact with the gas phase present in the reactor.
Les matériaux mentionnés ci-avant conviennent bien pour la mise en oeuvre du procédé selon l'invention. Ils peuvent également être mis en oeuvre avec d'autres systèmes catalytiques tels que décrits par exemple dans la demande EP-A-905113. L'invention concerne dans un aspect particulier dès lors aussi la mise en oeuvre de réacteurs tels que décrits plus haut comprenant les matériaux tels que décrits ci-avant pour effectuer une réaction d'hydrochloration avec du chlorure d'hydrogène dans un milieu liquide renfermant au moins un catalyseur d'hydrochloration qui comprend de préférence au moins un composé choisi parmi les composés des métaux du groupe VTJIa et des lanthanides, et un solvant organique capable de solubiliser le catalyseur.The materials mentioned above are well suited for implementing the method according to the invention. They can also be used with other catalytic systems as described for example in application EP-A-905113. The invention relates in a particular aspect therefore also to the use of reactors as described above comprising the materials as described above for carrying out a hydrochlorination reaction with hydrogen chloride in a liquid medium containing at least one hydrochlorination catalyst which preferably comprises at least one compound chosen from compounds of the metals of the group VTJIa and lanthanides, and an organic solvent capable of solubilizing the catalyst.
Dans le procédé selon l'invention, le temps de contact gaz/liquide, qui est la durée pendant laquelle le gaz est en contact avec le milieu liquide, par exemple sous forme d'une bulle qui traverse une quantité donnée de milieu liquide, est généralement supérieur ou égal à 0,5 secondes. Avantageusement, le temps de contact est supérieur ou égal à 1 seconde. En général, le temps de contact gaz/liquide ne dépasse pas 5 minutes. Il est le plus souvent inférieur ou égal à 2 minutes. Avantageusement, il est inférieur ou égal à 1 minute. Il a été trouvé que de particulièrement bonnes sélectivités et rendements en 2- chloroprop-1-ène sont obtenus grâce à la mise en oeuvre du procédé selon l'invention dans les conditions de temps de contact mentionnées ci-avant. Dans le procédé selon l'invention, le rapport molaire entre le chlorure d'hydrogène et le méthylaçétylène et/ou le propadiène introduits dans le réacteur est en général supérieur ou égal à environ 0,5. De préférence, ce rapport est supérieur ou égal à 1. En général, ce rapport molaire est inférieur ou égal à environ 10. De préférence, ce rapport est inférieur ou égal à 5. De bons résultats ont été obtenus avec un rapport molaire entre le chlorure d'hydrogène et le méthylaçétylène et/ou le propadiène introduits dans le réacteur inférieur ou égal à environ 2,5. Le méthylaçétylène et/ou le propadiène et le chlorure d'hydrogène peuvent être mis en contact dans le réacteur ou mélangés préalablement à leur introduction dans le réacteur.In the method according to the invention, the gas / liquid contact time, which is the period during which the gas is in contact with the liquid medium, for example in the form of a bubble which passes through a given quantity of liquid medium, is generally greater than or equal to 0.5 seconds. Advantageously, the contact time is greater than or equal to 1 second. In general, the time to gas / liquid contact does not exceed 5 minutes. It is most often less than or equal to 2 minutes. Advantageously, it is less than or equal to 1 minute. It has been found that particularly good selectivities and yields of 2-chloroprop-1-ene are obtained by implementing the method according to the invention under the contact time conditions mentioned above. In the process according to the invention, the molar ratio between hydrogen chloride and methylacetylene and / or propadiene introduced into the reactor is generally greater than or equal to about 0.5. Preferably, this ratio is greater than or equal to 1. In general, this molar ratio is less than or equal to about 10. Preferably, this ratio is less than or equal to 5. Good results have been obtained with a molar ratio between the hydrogen chloride and methylacetylene and / or propadiene introduced into the reactor less than or equal to about 2.5. The methylacetylene and / or propadiene and hydrogen chloride can be brought into contact in the reactor or mixed before their introduction into the reactor.
Le procédé de l'invention est réalisable de la température ambiante jusqu'à environ 200 °C. A plus haute température, le catalyseur a tendance à se dégrader. La température de réaction préférée, c'est-à-dire celle offrant le meilleur compromis entre productivité, rendement et stabilité du catalyseur est supérieure ou égale à 80 °C. Les meilleurs résultats sont obtenus à des températures supérieures ou égales à environ 100 °C. De préférence, la température de réaction ne dépasse pas environ 180 °C. Une température de réaction inférieure ou égale à environ 160 °C est particulièrement préférée. La pression est généralement supérieure ou égale à la pression atmosphérique et égale ou inférieure à 15 bars. De préférence, la pression est inférieure ou égale à 10 bars. Une préférence particulière est montrée pour une pression inférieure ou égale à 5 bars. Le procédé de l'invention se déroule souvent à une pression proche supérieure ou égale à 1 bar. Une pression supérieure ou égale à 2 bars donne de bons résultats. Une pression d'environ 3 bars convient particulièrement bien. Le débit des réactifs, généralement gazeux, est généralement suffisant pour permettre un brassage efficace du milieu liquide. On peut également mettre en œuvre des moyens d'agitation connus du milieu liquide, tels que des agitateurs mécaniques.The process of the invention can be carried out from ambient temperature to approximately 200 ° C. At higher temperatures, the catalyst tends to degrade. The preferred reaction temperature, that is to say that offering the best compromise between productivity, yield and stability of the catalyst, is greater than or equal to 80 ° C. The best results are obtained at temperatures greater than or equal to about 100 ° C. Preferably, the reaction temperature does not exceed about 180 ° C. A reaction temperature less than or equal to about 160 ° C is particularly preferred. The pressure is generally greater than or equal to atmospheric pressure and equal to or less than 15 bars. Preferably, the pressure is less than or equal to 10 bars. A particular preference is shown for a pressure less than or equal to 5 bars. The process of the invention often takes place at a pressure close to or greater than 1 bar. A pressure greater than or equal to 2 bars gives good results. A pressure of around 3 bars is particularly suitable. The flow rate of reagents, generally gaseous, is generally sufficient to allow efficient mixing of the liquid medium. It is also possible to use known stirring means for the liquid medium, such as mechanical stirrers.
Dans un procédé en continu, le temps de séjour, qui est le rapport entre le volume de milieu liquide dans le réacteur et le débit volumique des réactifs, est généralement supérieur ou égal à 0,5 secondes. Avantageusement, le temps de séjour est supérieur ou égal à 1 seconde. En général, le temps de séjour ne dépasse pas 5 minutes. Il est le plus souvent inférieur ou égal à 2 minutes.In a continuous process, the residence time, which is the ratio between the volume of liquid medium in the reactor and the volume flow rate of the reactants, is generally greater than or equal to 0.5 seconds. Advantageously, the time to stay is greater than or equal to 1 second. In general, the residence time does not exceed 5 minutes. It is most often less than or equal to 2 minutes.
Avantageusement, il est inférieur ou égal à 1 minute.Advantageously, it is less than or equal to 1 minute.
Dans le procédé selon l'invention, on préfère utiliser comme réactif un mélange d'hydrocarbures contenant du méthylaçétylène et du propadiène, parIn the process according to the invention, it is preferred to use as a reactant a mixture of hydrocarbons containing methylacetylene and propadiene, for example
® exemple celui commercialisé par Air Liquide sous le nom de TETRENE . Sa composition molaire est environ de 25 % de méthylaçétylène, 13 % de propadiène, 46 % de propylène, 4 % de propane et 12 % d'hydrocarbures en C4.® example that marketed by Air Liquide under the name of TETRENE. Its molar composition is approximately 25% methylacetylene, 13% propadiene, 46% propylene, 4% propane and 12% C4 hydrocarbons.
De préférence, le milieu liquide est saturé en chlorure d'hydrogène avant d'introduire le métylacétylène et/ou le propadiène dans le réacteur. Ceci permet de maintenir une particulièrement bonne activité du système catalytique au cours de la réaction.Preferably, the liquid medium is saturated with hydrogen chloride before introducing the methyl acetylene and / or the propadiene into the reactor. This makes it possible to maintain a particularly good activity of the catalytic system during the reaction.
Lorsqu'on met en œuvre un mélange d'hydrocarbures contenant du méthylaçétylène et du propadiène, il est particulièrement souhaitable d'atteindre une conversion efficace du méthylaçétylène et du propadiène.When using a mixture of hydrocarbons containing methylacetylene and propadiene, it is particularly desirable to achieve efficient conversion of methylacetylene and propadiene.
L'invention concerne dès lors aussi une méthode de préparation du 2-chloroprop-l-ène par réaction d'un mélange méthylacétylène/propadiène avec du chlorure d'hydrogène dans un milieu liquide comprenant au moins un catalyseur d'hydrochloration et au moins un solvant organique capable de solubiliser le catalyseur, méthode dans laquelleThe invention therefore also relates to a method for preparing 2-chloroprop-1-ene by reacting a methylacetylene / propadiene mixture with hydrogen chloride in a liquid medium comprising at least one hydrochlorination catalyst and at least one organic solvent capable of solubilizing the catalyst, method in which
(a) on introduit un mélange méthylacétylène/propadiène dans le milieu liquide et(a) a methylacetylene / propadiene mixture is introduced into the liquid medium and
(b) on récupère à l'issue de la réaction d'une part du 2-chloropropène et d'autre part une fraction comprenant du méthylaçétylène et du propadiène non réagis et(b) on the one hand, 2-chloropropene and, on the other hand, a fraction comprising unreacted methylacetylene and propadiene, are recovered at the end of the reaction, and
(c) on recycle la fraction comprenant du méthylaçétylène et du propadiène non réagis vers l'étape (a).(c) the fraction comprising unreacted methylacetylene and propadiene is recycled to step (a).
De préférence le rapport molaire entre le méthylaçétylène et le propadiène dans la fraction comprenant du méthylaçétylène et du propadiène non réagis est substantiellement identique au rapport molaire initial entre ces mêmes constituants. La variation du rapport molaire entre le méthylaçétylène et le propadiène dans la fraction comprenant du méthylaçétylène et du propadiène non réagis par rapport au rapport molaire initial est généralement inférieure ou égale à 10%. De préférence cette variation est inférieure ou égale à 5%. Une variation inférieure ou égale à 1% est plus particulièrement préférée. Une variation inférieure ou égale à 0,5 % est tout particulièrement préférée. On peut même arriver à une variation de 0%.Preferably, the molar ratio between methylacetylene and propadiene in the fraction comprising unreacted methylacetylene and propadiene is substantially identical to the initial molar ratio between these same constituents. The variation in the molar ratio between methylacetylene and propadiene in the fraction comprising unreacted methylacetylene and propadiene relative to the initial molar ratio is generally less than or equal to 10%. Preferably this variation is less than or equal to 5%. A variation less than or equal to 1% is more particularly preferred. A variation less than or equal to 0.5% is very particularly preferred. We can even arrive at a variation of 0%.
La variation peut être ajustée, si nécessaire par des opérations destinées à modifier le rapport molaire entre le méthylaçétylène et le propadiène telles que par exemple un appoint en l'un de ces composés ou une opération sélective de séparation telle qu'une adsorption. Toutefois, le procédé selon l'invention décrit plus haut, permet d'obtenir à l'iss,ue de la réaction une fraction comprenant du méthylaçétylène et du propadiène non réagis avec un rapport molaire entre le méthylaçétylène et le propadiène substantiellement identique au rapport molaire initial.The variation can be adjusted, if necessary by operations intended to modify the molar ratio between methylacetylene and propadiene such as for example an addition of one of these compounds or a selective separation operation such as an adsorption. However, the process according to the invention described above makes it possible to obtain, at the end of the reaction, a fraction comprising unreacted methylacetylene and propadiene with a molar ratio between methylacetylene and propadiene substantially identical to the molar ratio initial.
La méthode selon l'invention permet une utilisation très efficace des matières premières tout en évitant une accumulation de l'un des produits de départ dans le réacteur.The method according to the invention allows very efficient use of the raw materials while avoiding an accumulation of one of the starting materials in the reactor.
L'invention concerne aussi un procédé de fabrication d'un composé fluoré, en particulier un hydrofluoroalcane comprenantThe invention also relates to a process for manufacturing a fluorinated compound, in particular a hydrofluoroalkane comprising
(a) l'utilisation d'une oléfine halogénée, en particulier le 2-chloroprop-l-ène, obtenue selon le procédé selon l'invention ou selon la méthode selon l'invention, pour la fabrication d'un précurseur halogène du composé fluoré(a) the use of a halogenated olefin, in particular 2-chloroprop-1-ene, obtained according to the method according to the invention or according to the method according to the invention, for the manufacture of a halogen precursor of the compound fluorinated
(b) la fluoration du précurseur obtenu avec un réactif fluoré, de préférence le fluorure d'hydrogène, pour former le composé fluoré.(b) fluorination of the precursor obtained with a fluorinated reagent, preferably hydrogen fluoride, to form the fluorinated compound.
La fabrication du précurseur halogène peut être, par exemple, une réaction de télomérisation dans laquelle on fait réagir du 2-chloroprop-l-ène avec un haloalcane en présence d'un catalyseur et éventuellement d'un cocatalyseur. Ce type de réaction convient particulièrement bien pour l'obtention de 1,1,1,3,3- pentachlorobutane, qui est un précurseur halogène du 1, 1, 1,3,3- pentafluorobutane. Dans une réaction de télomérisation préférée, on fait dès lors réagir du 2-chloroprop-l-ène avec du tétrachlorométhane en présence d'un catalyseur comprenant un composé de cuivre et un cocatalyseur choisi parmi les aminés pour former du 1, 1, 1,3,3-peritachlorobutane. Dans la fluoration du précurseur obtenu, le réactif fluoré préféré est le fluorure d'hydrogène anhydre. La fluoration peut être effectuée en la présence ou en l'absence de catalyseur de fluoration. Lorsque la fluoration est effectuée en la présence de catalyseur, ce dernier est avantageusement choisi parmi les halogénures de métaux de groupe 4, 5, 14 et 15, en particulier les dérivés d'étain, d' antimoine, de titane, de niobium et de tantale. L'hydroflùoroalcane préféré est le 1,1,1,3,3-pentafluorobutane. L'invention est illustrée de manière non limitative dans les exemples suivants. Exemple 1The manufacture of the halogen precursor can be, for example, a telomerization reaction in which 2-chloroprop-1-ene is reacted with a haloalkane in the presence of a catalyst and optionally a cocatalyst. This type of reaction is particularly suitable for obtaining 1,1,1,3,3-pentachlorobutane, which is a halogen precursor of 1, 1, 1,3,3-pentafluorobutane. In a preferred telomerization reaction, 2-chloroprop-1-ene is therefore reacted with tetrachloromethane in the presence of a catalyst comprising a copper compound and a cocatalyst chosen from amines to form 1, 1, 1, 3,3-peritachlorobutane. In the fluorination of the precursor obtained, the preferred fluorinated reagent is anhydrous hydrogen fluoride. The fluorination can be carried out in the presence or absence of a fluorination catalyst. When the fluorination is carried out in the presence of catalyst, the latter is advantageously chosen from the metal halides of group 4, 5, 14 and 15, in particular the derivatives of tin, antimony, titanium, niobium and tantalum. The preferred hydrofluoroalkane is 1,1,1,3,3-pentafluorobutane. The invention is illustrated in a nonlimiting manner in the following examples. Example 1
La réaction a été conduite dans un réacteur de type saturateur muni d'une double enveloppe dans laquelle circule de l'huile thermostatisée à la température de l'essai et surmonté d'un réfrigérant refroidi pour condenser les vapeurs de solvant et de co-solvant. Dans un bêcher, on a dissout en chauffant légèrement 0,15 mmol de PdCTj dans 80 ml d' adiponitrile. Après dissolution totale du chlorure de palladium, on a versé la phase liquide dans le réacteur préalablement chauffé à 140 °C. On a alors injecté du chlorure d'hydrogène à un débit deThe reaction was carried out in a reactor of saturator type provided with a double jacket in which circulates oil thermostatically controlled at the test temperature and surmounted by a cooled condenser to condense the solvent and co-solvent vapors . In a beaker, 0.15 mmol of PdCTj was dissolved by slightly heating in 80 ml of adiponitrile. After complete dissolution of the palladium chloride, the liquid phase was poured into the reactor previously heated to 140 ° C. Hydrogen chloride was then injected at a rate of
1,3 1/h pendant 30 minutes. Ensuite, conjointement au chlorure d'hydrogène, on a injecté un mélange constitué, sur une base molaire, de 25 % de . méthylaçétylène, de 13 % de propadiène, de 46 % de propylène, de 4 % de propane et de 12 % d'hydrocarbures en C4 dans le réacteur à un débit de 2,41/h. Le temps de séjour dans le réacteur était de 23 s.1.3 l / h for 30 minutes. Then, together with hydrogen chloride, a mixture consisting of 25% of a molar base was injected. methylacetylene, 13% propadiene, 46% propylene, 4% propane and 12% C4 hydrocarbons in the reactor at a rate of 2.41 / h. The residence time in the reactor was 23 s.
Les produits de la réaction obtenus au cours du temps ont été analysés par une analyse chromatographique en phase gazeuse en ligne. Les résultats sont présentés dans le tableau I ci-après. Dans ce tableau, le tau de conversion est le rapport entre la concentration initiale en méthylaçétylène et en propadiène diminuée de sa concentration finale divisée par la concentration initiale, multiplié par 100 ; la sélectivité en 2-chloroprop-l-ène est le rapport entre la concentration finale en 2-chloroprop-l-ène divisée par la concentration initiale en méthylaçétylène et en propadiène diminuée de sa concentration finale, multiplié par 100. Exemple 2 (comparaison)The reaction products obtained over time were analyzed by on-line gas chromatographic analysis. The results are presented in Table I below. In this table, the conversion tau is the ratio between the initial concentration of methylacetylene and propadiene minus its final concentration divided by the initial concentration, multiplied by 100; the selectivity for 2-chloroprop-1-ene is the ratio between the final concentration of 2-chloroprop-1-ene divided by the initial concentration of methylacetylene and of propadiene minus its final concentration, multiplied by 100. Example 2 (comparison)
On a mis en œuvre un milieu liquide contenant 0, 15 mmόl de PtCl2 dans 80 ml d'adiponitrile. La réaction a été effectuée dans le même appareillage et dans les mêmes conditions qu'à l'exemple 1, à l'exception du temps de séjour qui a été porté à 46s. Le résultat obtenu est indiqué dans le tableau 1. Tableau 1A liquid medium containing 0.15 mmόl of PtCl 2 in 80 ml of adiponitrile was used. The reaction was carried out in the same apparatus and under the same conditions as in Example 1, with the exception of the residence time which was brought to 46 s. The result obtained is shown in Table 1. Table 1
Il apparaît que le procédé selon l'invention permet d'obtenir du 2-chloroprop-l-ène avec une meilleure sélectivité par rapport au procédé catalysé par PtCl2/adiponitrile. La conversion de méthylaçétylène est fortement améliorée. Le procédé selon l'invention fournit donc des résultats inattendus et supérieurs par rapport au procédé catalysé par PtCVadiponitrile. Les taux de conversion de propadiène et de méthylaçétylène sont identiques. Des lors le mélange de propadiène et de méthylaçétylène non convertis est, après séparation du 2-chloroprop-l-ène, approprié au recyclage vers la réaction de fabrication. It appears that the process according to the invention makes it possible to obtain 2-chloroprop-1-ene with better selectivity compared to the process catalyzed by PtCl 2 / adiponitrile. The conversion of methylacetylene is greatly improved. The process according to the invention therefore provides unexpected and superior results compared to the process catalyzed by PtCVadiponitrile. The conversion rates of propadiene and methylacetylene are identical. Therefore the mixture of propadiene and methylacetylene unconverted is, after separation of 2-chloroprop-1-ene, suitable for recycling to the manufacturing reaction.

Claims

REVENDI C AT I ON SREVENDI C AT I ON S
1 - Procédé de préparation d'une oléfine halogénée par réaction d'un alkyne et/ou d'un composé allénique avec un halogénure d'hydrogène dans un milieu liquide comprenant au moins1 - Process for the preparation of a halogenated olefin by reaction of an alkyne and / or of an allenic compound with a hydrogen halide in a liquid medium comprising at least
(a) un catalyseur d'hydrohalogénation comprenant au moins un composé de palladium; et(a) a hydrohalogenation catalyst comprising at least one palladium compound; and
(b) au moins un solvant organique capable de solubiliser le catalyseur, choisi parmi les nitriles organiques.(b) at least one organic solvent capable of dissolving the catalyst, chosen from organic nitriles.
2 - Procédé selon la revendication 1 dans lequel l' alkyne répond à la formule générale (I)2 - Process according to claim 1 in which the alkyne corresponds to the general formula (I)
Ri-C≡C-HR i -C≡CH
dans laquelle R1 désigne un groupement alkyl, aryl, carboxyle, esterou halogène et/ou le composé allénique répond à la formule générale (TJ)in which R 1 denotes an alkyl, aryl, carboxyl, ester or halogen group and / or the allenic compound corresponds to the general formula (TJ)
R2R3C=C=CH2 (II)R 2 R 3 C = C = CH 2 (II)
dans laquelle R2 et R3 désignent indépendamment un groupement hydrogène alkyl, aryl, carboxyle, ester ou halogène.in which R 2 and R 3 independently denote an alkyl, aryl, carboxyl, ester or halogen hydrogen group.
3 - Procédé selon la revendication 1 ou 2 dans lequel on prépare du 2- chloroprop-1-ène par réaction de méthylaçétylène et/ou de propadiène avec du chlorure d'hydrogène.3 - Process according to claim 1 or 2 wherein 2-chloroprop-1-ene is prepared by reaction of methylacetylene and / or propadiene with hydrogen chloride.
4 - Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le composé de palladium est choisi parmi les complexes et les sels contenant le palladium à l' étage d' oxydation 0 ou 2.4 - Process according to any one of claims 1 to 3, in which the palladium compound is chosen from complexes and salts containing palladium on the oxidation stage 0 or 2.
5. - Procédé selon la revendication 4, dans lequel le composé de palladium contient le palladium à l' étage d' oxydation 2. 5. - Method according to claim 4, wherein the palladium compound contains palladium in the oxidation stage 2.
6. - Procédé selon la revendication 5, dans lequel le composé de palladium est un sel, choisi parmi l'acétate de palladiumHl), le nitrate de palladium (II), le bromure de palladium (TJ) et le chlorure de palladium (TT).6. - Method according to claim 5, wherein the palladium compound is a salt, chosen from palladium acetate (Hl), palladium nitrate (II), palladium bromide (TJ) and palladium chloride (TT ).
7. - Procédé selon la revendication 6, dans lequel le composé de palladium est le chlorure de palladium (U).7. - Method according to claim 6, wherein the palladium compound is palladium chloride (U).
8. - Procédé selon l'une quelconque des revendications 1 à 7 dans lequel le nitrile organique comprend 1, 2, 3 ou 4 fonctionnalités nitrile.8. - Method according to any one of claims 1 to 7 wherein the organic nitrile comprises 1, 2, 3 or 4 nitrile functionalities.
9 - Procédé selon la revendication 8 dans lequel le nitrile organique est l' adiponitrile.9 - Process according to claim 8 wherein the organic nitrile is adiponitrile.
10 - Procédé selon l'une quelconque des revendications 1 à 9 dans lequel la pression à laquelle on effectue la réaction est de 1 à 5 bars et la température à laquelle on effectue la réaction est de 100 à 160°C.10 - Process according to any one of claims 1 to 9 wherein the pressure at which the reaction is carried out is from 1 to 5 bars and the temperature at which the reaction is carried out is from 100 to 160 ° C.
11. - Méthode de préparation du 2-chloroprop-l-ène par réaction d'un mélange méthylacétylène/propadiène avec du chlorure d'hydrogène dans un milieu liquide comprenant au moins un catalyseur d'hydrochloration et au moins un solvant organique capable de solubiliser le catalyseur, méthode dans laquelle11. - Method for preparing 2-chloroprop-1-ene by reaction of a methylacetylene / propadiene mixture with hydrogen chloride in a liquid medium comprising at least one hydrochlorination catalyst and at least one organic solvent capable of solubilizing the catalyst, method in which
(a) on introduit un mélange méthylacétylène/propadiène dans le milieu liquide et(a) a methylacetylene / propadiene mixture is introduced into the liquid medium and
(b) on récupère à l'issue de la réaction d'une part du 2-chloropropène et d'autre part une fraction comprenant du méthylaçétylène et du propadiène non réagis et(b) on the one hand, 2-chloropropene and, on the other hand, a fraction comprising unreacted methylacetylene and propadiene, are recovered at the end of the reaction, and
(c) on recycle la fraction comprenant du méthylaçétylène et du propadiène non réagis vers l'étape (a).(c) the fraction comprising unreacted methylacetylene and propadiene is recycled to step (a).
12. - Méthode selon la revendication 11, dans lequel le rapport molaire entre le méthylaçétylène et le propadiène dans la fraction comprenant du méthylaçétylène et du propadiène non réagis est. substantiellement identique au rapport molaire initial entre ces mêmes constituants.12. - Method according to claim 11, wherein the molar ratio between methylacetylene and propadiene in the fraction comprising unreacted methylacetylene and propadiene is . substantially identical to the initial molar ratio between these same constituents.
13. Procédé de fabrication d'un composé fluoré, en particulier un hydrofluoroalcane comprenant (a) l'utilisation d'une oléfine halogénée, en particulier le 2-chloroprop-l-ène, obtenue selon le procédé selon l'une quelconque des revendications 1 à 10 ou selon la méthode selon la revendication 11 ou 12, pour la fabrication d'un précurseur halogène du composé fluoré;13. Process for manufacturing a fluorinated compound, in particular a hydrofluoroalkane comprising (a) the use of a halogenated olefin, in particular 2-chloroprop-1-ene, obtained according to the method according to any one of claims 1 to 10 or according to the method according to claim 11 or 12, for the manufacture of a halogen precursor of the fluorinated compound;
(b) la' fluoration du précurseur obtenu avec un réactif fluoré, de préférence le fluorure d'hydrogène pour former le composé fluoré.(b) fluorinating the precursor obtained with a fluoride reagent, preferably hydrogen fluoride to form the fluorine compound.
14. - Procédé de fabrication selon la revendication 13, dans lequel le composé fluoré est le 1,1,1,3 ,3-pentafluorobutane.14. - The manufacturing method according to claim 13, wherein the fluorinated compound is 1,1,1,3,3-pentafluorobutane.
15. Système catalytique comprenant un composé de palladium et un nitrile organique. 15. Catalytic system comprising a palladium compound and an organic nitrile.
EP02737895A 2001-03-22 2002-03-20 Method for preparing a halogenated olefin Withdrawn EP1381584A2 (en)

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CN1531517A (en) 2004-09-22
AU2002312773A1 (en) 2002-10-08
US20040116754A1 (en) 2004-06-17
FR2822459B1 (en) 2004-07-09
US7109386B2 (en) 2006-09-19
FR2822459A1 (en) 2002-09-27
WO2002076913A3 (en) 2003-07-31
WO2002076913A2 (en) 2002-10-03
JP2004525933A (en) 2004-08-26

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