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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• 2001
  • 2001-03-22 FR FR0103908A patent/FR2822459B1/fr not_active Expired - Fee Related
• 2002
  • 2002-03-20 WO PCT/EP2002/003238 patent/WO2002076913A2/fr active Application Filing
  • 2002-03-20 CN CNA028102657A patent/CN1531517A/zh active Pending
  • 2002-03-20 US US10/472,784 patent/US7109386B2/en not_active Expired - Fee Related
  • 2002-03-20 AU AU2002312773A patent/AU2002312773A1/en not_active Abandoned
  • 2002-03-20 JP JP2002576176A patent/JP2004525933A/ja active Pending
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