Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
  • C07C41/01—Preparation of ethers
  • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups

Definitions

• the present invention relates to a process for the synthesis of hydrogenated and / or fluorinated compounds of the polyoxyethylene-alkyl ether type. It also relates to compounds of this type and their application as nonionic surfactants.
• the processes used up to now for the synthesis of nonionic fluorinated surfactants of general formula R F (CH 2 ) ⁇ (OC 2 H 4 ) n OH in which R F is a fluorinated chain, are based on the condensation of ethylene oxide on the fluorinated alcohol of formula R F (CH 2 ) ⁇ OH.
• the product of the condensation reaction is a mixture of surfactants having a more or less wide distribution of the number n of ether units.
• the pure products that is to say the fluorinated compounds having a number n of well-defined ether units, can then be obtained by distillation.
• the yields are only around 20 to 30% approximately [R. TATEMATSU et al. Yakagaku (1976), 25 p. 287 and Yakagaku (1980) 29, p. 23].
• Patent application JP 73.36.514 published under the number 123.184 / 74 relates to obtaining aqueous emulsions containing a fluorocarbon derivative as main substituent, a nonionic surfactant and water.
• the surfactants used to obtain these emulsions are obtained by adding ethylene oxide to alcohols. They are in the form of mixtures having a distribution conforming to a Gaussian curve and not in the form of pure products.
• the hydrogenated homologs of these fluorinated compounds can be obtained by ethoxylation according to a process analogous to that defined above. above or by Williamson type addition of a polyalcohol to an alcohol or by etherification of a tosilate. These methods make it possible to obtain a number of well-defined ether units with yields of the order of 20 to 50%. To this end, reference may be made to the article by SHICK "Non ionic surfactants" M. Dekker NY 1966. However, none of these Williamson type addition processes or etherification of a tosilate has been, to the knowledge of the applicant, used to obtain nonionic fluorinated surfactants.
• R z is a partially hydrogenated hydrocarbon, fluorocarbon or fluorocarbon chain and n is an integer at least equal to 1, consists of:
• fluorocarbon chain is meant, in the present description, the alkyl chains li nea i re s or branched completely fluorinated.
• partially hydrogenated fluorocarbon chains mention may in particular be made of hydrogenated fluorocarbon chains at the end of the chain.
• the first step of the process of the invention consists in the formation of the monosalt chloride of oxyphosphonium by reaction of the trisdimethylaminophosphine on a polyethylene glycol. It is important to operate in an environment which makes it possible to dissolve the glycol and in which the monosel precipitates immediately after its formation.
• the choice of reaction medium therefore depends on the glycol used and the monosal formed. It will be indicated by way of example that tetrahydrofuran is suitable as a reaction medium for polyethylene glycols having 1 to 5 ether units. For a number of ether units greater than 5, a tetrahydrofuran / ether mixture is advantageously used.
• the operation is advantageously carried out at a temperature between -20 and -40 ° C. and under an inert atmosphere, for example under a nitrogen atmosphere. At a higher temperature, monosel also forms, but this is then not stable and breaks down immediately. In general, approximately one molar equivalent of alcohol of the formula is advantageously used
• An aqueous solution of an excess of potassium hexafluorophosphate is preferably used, containing for example 2 molar equivalents of this salt.
• the oxyphosphonium salt thus formed is then extracted from the reaction mixture using an organic solvent, for example methylene chloride and is then dried.
• the patent FR 73.17.883 also relates to obtaining functional d - alkyloxytrisdialkylaminophosphonium salts.
• the third step of the process of the invention consists of a nucleophilic substitution on the oxyphosphonium salt of polyoxyethylene glycol thus obtained with a fluorinated alcoholate of formula R z (CH 2 ) 0M, in which M is a cation, for example sodium.
• the fluorinated alcoholate in solution in an aprotic organic solvent is reacted by heating with the oxyphosphonium salt of polyoxyethyleneglycol.
• the operation is advantageously carried out at a temperature between 50 and 100 ° C., for example at 60 ° C. for 8 and 48 hours, in particular for 24 hours, under an inert atmosphere and stirring.
• Solvents of the ether, mono- or polyether type with high boiling point are particularly suitable, such as for example dimethoxyethane, dioxane, the latter being particularly preferred. Mixtures of such solvents can also be used. In general, about 1 molar equivalent of fluorinated alcoholate is used for 1 molar equivalent of oxyphosphonium salt of polyoxyethyleneglycol.
• the reaction mixture thus obtained is evaporated and the residue is extracted with, for example, ether.
• the resulting organic phase is then washed and dried, then the products formed are prepared by chromatography.
• the chromatographic eluent can be, for example, ethyl acetate or a mixture of ethyl acetate / methanol.
• the starting compounds used in the process of the invention namely the polyoxyethyleneglycol of formula H (OC 2 H 4 ) n OH and the alcoholate fluorinated R z CH 2 0M feels obtained by conventional means.
• polyoxyethyleneglycol H (OC 2 H 4 ) n OH is obtained by condensation of ethylene oxide with a glycol or by a similar process
• the fluorinated alcoholate can be obtained by reaction of a methylate, for example sodium methylate in methanolic solution with the fluorinated alcohol of formula R z CH 2 OH and evaporation under vacuum of the solvent, for example methanol.
• the present invention also relates to the compounds obtained by the above process. It thus relates, as new products, to fluorinated compounds of formula R F CH 2 (OC 2 H 4 ) n OH in which n is greater than or equal to 6 and R. is a fluorocarbon or fluorocarbon chain partially hydrogenated.
• the compounds according to the invention have the characteristic properties of nonionic surfactants and are therefore suitable as nonionic surfactants.
• the present invention therefore also relates to the application of the fluorinated compounds defined above as surfactants.
• the entire reaction system was placed under a nitrogen atmosphere before being cooled to around -40 ° C.
• TDAP was then added slowly. The addition lasted 3 hours and after the addition was allowed to react for a maximum of 30 minutes.
• reaction mixture was then thrown onto 100 ml of water and the reactor was washed twice more.
• the aqueous phase was washed with ether before mixing with an aqueous solution of 2 equivalents (18.4 g) of potassium hexafluorophosphate.
• the extraction of the oxyphosphinium salt was then carried out by washing with methylene chloride.
• This organic phase was dried over Na 2 S0 4 . before evaporation on a rotary evaporator.
• the fluorinated alcoholate of formula C 7 F 15 CH 2 O Na was prepared; 0.25 g of sodium was added to 50 ml of methanol. To this methanolic solution of 1.1 equivalents of sodium methylate, 1.2 equivalents (4.8 g) of fluorinated alcohol C 7 F 15 CH 2 OH were added. Evaporation in vacuo of the solvent made it possible to obtain the fluoroalcoholate, which was subsequently dissolved in 50 ml of dioxane in the presence of an equivalent of the oxyphosphonium salt of tetraoxyethylene glycol obtained according to the above procedure.
• the solution thus obtained was heated for 24 hours at 60 ° C. under a nitrogen atmosphere and magnetic stirring.
• reaction mixture was evaporated and the residue was extracted with ether. This organic phase was washed with an HCL2N acid solution (3 x 100 ml) and dried over MgSO .. The reaction products were separated chromatographically using ethyl acetate as eluent. Chromatography was carried out on silica (120 g).
• the nucleophilic substitution reaction was carried out for 24 hours at 62 ° C. After extraction, washing, drying and chromatography on silica (120 g; eluent; ethyl acetate / methanol 95/5), 2.6 g of a yellowish liquid were obtained, the elementary analysis of which was as follows:
• the nucleophilic substitution reaction was carried out for 24 hours at 60 ° C; after treatment of the residue and chromatography (120 g of silica; eluent: ethyl acetate / methanol 95/5), 2.20 g of a yellowish liquid were obtained, the elementary analysis of which made it possible to identify the compound of formula
• This compound had the following physicochemical characteristics: cloud point ⁇ 0 ° C

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• 1980
  • 1980-10-24 FR FR8022874A patent/FR2492814A1/fr active Granted
• 1981
  • 1981-10-23 WO PCT/FR1981/000137 patent/WO1982001546A1/fr not_active Ceased
  • 1981-10-23 EP EP81401691A patent/EP0051527A1/fr not_active Withdrawn
  • 1981-10-23 EP EP81902971A patent/EP0063148A1/fr not_active Withdrawn

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