WO2005121290A1 - Procede de fabrication de fluoropolymere - Google Patents

Procede de fabrication de fluoropolymere Download PDF

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Publication number
WO2005121290A1
WO2005121290A1 PCT/EP2005/007061 EP2005007061W WO2005121290A1 WO 2005121290 A1 WO2005121290 A1 WO 2005121290A1 EP 2005007061 W EP2005007061 W EP 2005007061W WO 2005121290 A1 WO2005121290 A1 WO 2005121290A1
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Prior art keywords
polymerization
fluoropolymer
surfactant
reactor
optionally
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PCT/EP2005/007061
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English (en)
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Patrick Kappler
Marie-José Lina
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Arkema
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Publication of WO2005121290A1 publication Critical patent/WO2005121290A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine

Definitions

  • the present invention relates to a process for the preparation of a fluoropolymer by polymerization of an aqueous dispersion of fluoromonomers.
  • such aqueous dispersions of fluoromonomers comprise a fluorosurfactant, a radical initiator, optionally a chain-transfer agent and optionally a paraffin wax.
  • the surfactants used to date could be biopersistent and bioaccumulable.
  • the process of the present invention uses surfactants which do not exhibit these disadvantages.
  • perfluorocarboxylic acids under the generic names of PFOA (perfluorooctyl acid C 7 F 15 COOH in the form of ammonium or lithium salts) or of APFO (ammonium perfluorooctanoate) are by far the most widely used industrially, all the more so since, because of the absence of terminations by hydrogen transfer, they are until now the only ones which allow PTFE elastomers of very high molar masses to be obtained.
  • PFOA perfluorooctyl acid C 7 F 15 COOH in the form of ammonium or lithium salts
  • APFO ammonium perfluorooctanoate
  • Patents US 5 998 521 and US 6 013 795 disclose the synthesis and the use of ⁇ -branched surfactants for emulsion polymerization.
  • These surfactants exhibit the advantage of not being bioaccumulable.
  • These surfactants have a branching in the position ⁇ to the acid functional group which weakens the molecule and improves its biodegradability.
  • these surfactants can be decomposed by heat treatment.
  • One of these surfactants is C 7 F 15 CF(CF 3 )-COONH 4 . It is applicable to the polymerization of TFE or VDF and the copolymerization of HFP and VDF.
  • the prior art has already described the use of partially fluorinated surfactants to prepare fluoropolymers.
  • Patent WO 97/08214 discloses the use of sulphonic derivatives of the C 6 Fi 3 C 2 H SO 3 M type, M being a cation with a valency of 1 , for the polymerization in an aqueous medium of fluoromonomers.
  • TFE tetrafluoroethylene
  • VDF perfluoroolefins or perfluoro(vinyl ether)s.
  • VDF perfluoroolefins or perfluoro(vinyl ether)s.
  • Cs homologue C 8 F 17 C 2 H 4 S ⁇ 3 M, is more bioaccumulable than the Ce homologue.
  • the distinguishing feature of these compounds is the presence of an alkylene group (CH 2 )m positioned between two perfluorinated groups (R f and R't).
  • the transfer of hydrogen with this type of surfactant is less significant than with a conventional surfactant, such as perfluoroethylsulphonat.es (RfC 2 H SO3M).
  • RfC 2 H SO3M perfluoroethylsulphonat.es
  • These compounds prove to be of use in the emulsion polymerization of fluoromonomers (TFE, VDF or HFP).
  • TFE, VDF or HFP fluoromonomers
  • the polymers obtained (PTFE or others) exhibit a high molecular weight despite the presence of hydrogen in the surfactant.
  • These surfactants exhibit bioaccumulation characteristics which are enhanced with the length of the perfluorinated chains but those having short perfluorinated chains are not very effective in the stabilization of PVDF latexes.
  • Patent Application EP A1 -0816397 discloses a process for the microemulsion polymerization of VDF in the optional presence of 0.1 to 10 mol% of one or more other fluorocomonomers.
  • the microemulsion comprises a (per)fluoropolyether having neutral end groups or fluoropolyoxyalkylenes and a surfactant based on (per)fluoropolyethers having carboxylate end groups, preferably sodium carboxylate end groups.
  • the fluoropolymers have an improved whiteness index and their level of residual surfactant is lowered and can reach 70 p. p.m. This type of perfluoropolyether- based surfactant, in particular those of low mass, are the most effective.
  • the present invention relates to a process for the preparation of a fluoropolymer by polymerization of an aqueous dispersion of at least one fluoromonomer, this dispersion additionally comprising a fluorosurfactant, a radical initiator, optionally a transfer agent and optionally a paraffin wax, in which process the fluorosurfactant is chosen from one or more of the following products:
  • lower alkyl is understood to mean a number of carbon atoms of at most 4 and generally having the value 2 or 3.
  • Ammonium salts are advantageously used. They have the advantage of resulting in polymers of high purity. In the general case, the choice will be made of a counterion which prevents yellowing of the polymer during heat treatments.
  • m 3, 4 or 5.
  • the process of the invention exhibits the following advantages: • lower biopersistence related to a number of CF 2 units in the surfactant of at most 5 and advantageously of 4, • reduced ability to become concentrated in the cells; this ability can be modelled by calculation of log of Kow as defined later in the text, • good thermal stability, in particular of PVDF comprising surfactant residues in the ammonium form which can range up to 1000 ppm. This result is unexpected, in view of the very poor thermal stability of PVDFs comprising between 300 and 1000 ppm of C 7 F 15 COONH 4 or C 8 F 17 COONH 4 .
  • TFE tetrafluoroethylene C 2 F 4
  • radical initiators from the family of organic peroxides, peresters, such as percarbonates or perpivalates, or in
  • the radical initiator employed represents from 0.05 to 1 % by weight with respect to the total weight of the fluoromonomer(s) employed.
  • the polymerization is generally carried out at pressures of 40 to 120 bar and between 40 and 130°C, preferably between 50 and 90°C.
  • the amount of surfactant necessary depends on the concentration of monomer in the dispersion. It also depends on the size of the polymer particles required.
  • the fluorosurfactant employed represents from 0.05 to 0.5% by weight with respect to the total weight of the fluoromonomer(s) employed.
  • the polymerization in aqueous dispersion can be carried out in the presence of a paraffin wax with a melting point ranging from 40 to 70°C and representing from 0.005 to 0.1 % by weight with respect to the total weight of the fluoromonomer(s).
  • the molar masses can be adjusted by addition of a chain- transfer agent.
  • the polymer can be isolated by conventional methods, such as precipitation, by addition of an electrolyte or of a solvent, by conversion to a dry powder by spray-drying or by freeze drying.
  • the latex can also be stabilized for applications by coating or impregnation.
  • the process is said to be an "emulsion” process or any other process derived from the emulsion (microsuspension, miniemulsion, and the like) which are fully known to a person skilled in the art.
  • the fluoropolymer is separated from the water and from the possible residues of the reactants used.
  • the polymer is present in the form of a latex composed of very fine particles, the mean diameter of which is generally less than 1 micron. This latex can be coagulated and optionally concentrated by removing a portion of the water, for example by centrifuging.
  • the invention is of particular use for the preparation of PVDF homopolymer or copolymer.
  • the invention relates to these products.
  • this term is used to denote any polymer having, in its chain, at least one monomer chosen from compounds comprising a vinyl group capable of opening in order to polymerize and which comprises, directly attached to this vinyl group, at least one fluorine atom, one fluoroalkyl group or one fluoroalkoxy group.
  • ком ⁇ онент Mention may be made, as examples of monomer, of vinyl fluoride; vinylidene fluoride (VDF); trifluoroethylene (VF3); chlorotrifluoroethylene (CTFE); 1 ,2-difluoroethylene; tetrafluoroethylene (TFE); hexafluoropropylene (HFP); or perfluoro(alkyl vinyl) ethers, such as perfluoro(methyl vinyl) ether (PMVE), perfluoro(ethyl vinyl) ether (PEVE) and perfluoro(propyl vinyl) ether (PPVE).
  • the fluoropolymer can be a homopolymer or a copolymer; it can also comprise nonfluorinated monomers, such as ethylene.
  • the fluoropolymer is chosen from:
  • VDF vinylidene fluoride
  • CTFE chlorotrifluoroethylene
  • HFP hexafluoropropylene
  • VF3 trifluoroethylene
  • TFE tetrafluoroethylene
  • VF3 trifluoroethylene
  • CTFE chlorotrifluoroethylene
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • the fluoropolymer is poly(vinylidene fluoride) (PVDF) homopolymer or copolymer.
  • PVDF poly(vinylidene fluoride)
  • the PVDF comprises, by weight, at least 50% of VDF, more preferably at least 75% and better still at least 85%.
  • the comonomer is advantageously HFP.
  • radical initiator this term is used to denote any generator of radicals which is capable of bringing about the polymerization of the fluoromonomers in the process described above.
  • the radical initiator employed represents from 0.05 to 1% by weight with respect to the total weight of the fluoromonomer(s) employed.
  • the initiator can be organosoluble.
  • hydrocarbonaceous peroxides such as di(tert-butyl) peroxide, dicumyl peroxide or benzoyl peroxide, dialkyl peroxydicarbonates, such as diethyl or diisopropyl peroxydicarbonate or di(n-propyl) peroxydicarbonate, peracids or peresters, such as t-butyl perpivalate, t-amyl perpivalate or t-butyl peroxybenzoate.
  • the initiator can be a persulphate, advantageously an alkali metal persulphate and preferably a potassium persulphate or an ammonium persulphate.
  • this term is used to denote any product which makes it possible to limit the molar mass of the polymer while propagating the polymerization reaction. It generally exhibits a hydrogen bond sensitive to a radical attack. Mention may be made, by way of example, of ethane, propane, acetone, isopropanol, methyl acetate, ethyl acetate, diethyl ether, methyl tert-butyl ether, n-butyl acetate, diethyl malonate, diethyl carbonate, HFA161 (CH 3 -CH 2 F) and various chlorofluorocarbon compounds.
  • the amount of transfer agent depends essentially on its nature and on the average molar mass desired for the polymer fraction obtained in its presence, which conditions the mean viscosity of the final product.
  • the transfer agent employed represents from 0.05 to 5% by weight with respect to the PVDF manufactured.
  • ethyl acetate is used.
  • a paraffin wax is also added.
  • the paraffin wax employed has a melting point ranging from 40 to 70°C and represents from 0.005 to 0.1 % by weight with respect to the total weight of the fluoromonomers.
  • the invention is a batchwise or semicontinuous process for the manufacture of fluoropolymer, in which: • water, the surfactant and optionally a paraffin wax are charged to the polymerization reactor, • the reactor is deaerated to remove the oxygen, • the reactor is brought to the chosen temperature and the fluoromonomer and optionally one (or more) optional comonomer(s) are charged until the desired pressure is reached, • the optional transfer agent is introduced into the reactor, either in its entirety or partly at the start and partly during the polymerization, • the initiator is added, in all or in part, to initiate the polymerization, and the fall in pressure which results therefrom is compensated for by the addition of fluoromonomer and optional comonomer, • the possible remainder of the initiator is added during the polymerization, • after introduction of the planned amount of fluoromonomer and optional comonomer, the reactor is degassed and the fluoropolymer is separated by any
  • the temperature chosen is the temperature which is sufficient to polymerize the monomers and is of the order of 45 to 130°C.
  • the desired pressure is of the order of 40 to 120 bar.
  • the volume of water in which the monomers are dispersed and the amounts of surfactant, initiator and transfer agent can be easily determined by a person skilled in the art.
  • the polymerization is carried out in a stirred reactor and then the fluoropolymer (it is in the form of solid particles) and the water are separated by any means.
  • the reactor After charging the polymerization reactor with water, surfactant, optionally paraffin wax, transfer agent, in all or in part, and radical initiator, in all or in part, the reactor is pressurized, after having removed the oxygen, by adding thereto a fluoromonomer, alone or as a mixture with another unsaturated fluoromonomer, and the mixture is brought to the chosen temperature.
  • the fluoromonomer(s) is/are added to maintain the pressure, along with initiator, incrementally or by continuous addition.
  • the transfer agent can be added at the start or during the polymerization. After introduction of the planned amount of fluoromonomer(s), the reactor is degassed and the fluoropolymer dispersion emptied.
  • This dispersion is denoted by latex in emulsion processes.
  • the latex is diluted and then introduced into a coagulator, where it is subjected to shearing in the presence of air. Under the combined effect of these two actions, the latex is converted into an aerated slurry where the density is lower than that of water.
  • This slurry can be washed countercurrentwise with deionized water according to the process disclosed in EP 0 460 284.
  • the washing stage makes it possible to remove water-soluble entities incorporated before the polymerization or generated during the polymerization.
  • the aerated slurry is conveyed to a storage container before being directed, by pumping, to an spray-dryer, where it is converted to a dry powder.
  • atomize the slurry without preliminary washing.
  • This stage of drying in an spray-dryer can also be applied to the initial latex, optionally diluted, to the coagulated latex, for example coagulated by mechanical shearing, with or without preliminary dilution, or alternatively to the aerated cream.
  • An aqueous dispersion of the organosoluble radical initiator, stabilized by a surfactant which can be that used to carry out the polymerization is prepared.
  • the water, the radical initiator and the surfactant are mixed in a disperser. It is this dispersion which is added at the beginning of and then optionally during the polymerization.
  • the optional transfer agent is added, the reactor is pressurized, after having removed the oxygen, by adding thereto the fluoromonomer, alone or as a mixture with the comonomer, and the mixture is brought to the chosen temperature.
  • the aqueous emulsion is polymerized at a temperature of 45 to 130°C.
  • the polymerization is carried out at an absolute pressure of 40 to 120 bar.
  • the reaction is initiated by addition of the radical initiator dispersion.
  • the fluoromonomer, alone or as a mixture with a comonomer is optionally added to maintain the pressure or to obtain a controlled pressure variation.
  • the radical initiator is optionally added, incrementally or continuously. After introduction of the planned amount of fluoromonomer(s), the reactor is degassed and the fluoropolymer dispersion emptied. The fluoropolymer can be recovered as described in the preceding process.
  • M is advantageously ammonium.
  • R f comprises from 2 to 4 carbon atoms.
  • m has the value of 3, 4 or 5.
  • n has the value of 0 or 1.
  • Use may be made of a mixture of surfactants, for example a mixture of products of formula [1] or of a product of any one of the formulae with at least one other product of another formula or of the other two formulae or any combination of these possibilities.
  • the surfactant is preferably chosen from one or more of the following products: C 2 F 5 (CH 2 CF 2 ) 3 -CH 2 CO2NH 4 C 2 F 5 (CH 2 CF 2 ) 2 -CH 2 CO2NH 4 C 2 F 5 (CH 2 CF 2 ) 3 -CO 2 NH 4 C 3 F 7 (CH 2 CF 2 ) 2 -CH 2 CO2NH 4 C 4 F9(CH2CF2)2-CH2CO 2 NH4 C 2 F 5 (CH2CF 2 ) 3 CH 2 CH 2 SO 3 K C 3 F 7 (CH2CF 2 ) 2 CH 2 CH 2 SO 3 K C 4 F 9 (CH 2 CF 2 ) 3 CH 2 CH 2 SO 3 K C 4 F 9 (CH2CF 2 ) 2 CH 2 CH 2 SO 3 K
  • the surfactant represents from 0.05 to 0.5% by weight, preferably 0.01 to 0.025%, with respect to the total weight of the fluoromonomers.
  • This novel characteristic makes possible simplified finishing, such as drying by spray-drying or on a rotary drier without a preliminary washing stage. It is also possible, in the case of an emulsion process, to use a method for finishing the latex by coagulation and washing, as described in Patent US 4 128 517, which makes it possible to prepare a fluoropolymer possessing good thermal stability.
  • the initiator is advantageously potassium persulphate, n-propyl peroxydicarbonate, isopropyl peroxydicarbonate, di(tert-butyl) peroxide, tert- butyl peroxypivalate or tert-amyl peroxypivalate.
  • the transfer agent is advantageously ethyl acetate, ethane, propane, diethyl malonate or diethyl carbonate.
  • the surfactant is advantageously:
  • the iodinated precursors R f (CH 2 CF 2 ) m -l are obtained, in a well known way, by telomerization of perfluoroalkyl iodide C n F 2 n+ ⁇ l with vinylidene fluoride, for example in the liquid phase in the presence of a radical initiator of peroxide type.
  • the olefins can be oxidized using conventional reagents, such as potassium permanganate or dichromate. However, it does not result in a single carboxylic acid as the attack of the oxidizing agent takes place both on the fluorinated carbon ⁇ to the olefin and, to a lesser extent, on the protonated carbon in the ⁇ position.
  • Another method for the synthesis of the carboxylic acids of formula [1] consists in starting from the corresponding sulphinates R f (CH 2 CF 2 )m-SO 2 Na of formula [2].
  • the sulphinates can be prepared by analogy with known techniques described in the perfluorinated series, for example by Chang-Ming Hu in J. Org. Chem., Vol.
  • the conversion of the sulphinates can be carried out by analogy with the method described by Chinese researchers of the Shanghai Institute of Organic Chemistry, who, starting from perhalofluoroalkylated sulphinates and from an oxidizing or redox system 2+ (NH 4 ) 2 S 2 O 8 , Ce(SO4) 2 or H 2 O 2 /Fe - have obtained perhalofluorocarboxylic acids (Journal of Fluorine Chemistry, 49, 1990, pp 433-437) and, by photooxidation under UV irradiation in methanol with a high-pressure mercury lamp at ambient temperature and in the presence of oxygen, have identified the corresponding methyl esters ⁇ Tetrahedron Letters, 30, No. 48, pp 6717-6720). It has now been shown that it is possible to obtain the carboxylic acids
  • R f (CH 2 CF 2 )m-rCH 2 COOH by dissolution of the sulphinates R f (CH 2 CF 2 ) m -SO 2 Na in water and generation of radicals using water-soluble radical initiators, such as certain azo compounds.
  • the amount of radical initiator can vary, for example, from 0.01 to 0.2 by molar ratio with respect to the sulphinate. It will preferably be added in solution and slowly, so as to generate the radicals little by little in order to avoid radical secondary reactions.
  • the reaction will preferably be carried out in a homogeneous medium in an organic solvent or in water at a concentration which can vary, depending on the solubility of the precursor sulphinates, from a few per cent to 70-80% by weight, preferably between 10 and 30%.
  • the reaction temperature will depend on the radical initiator used. By way of example, it is between 45 and 70°C.
  • the reaction medium can be one or more polar organic solvents in which the sulphinates are soluble, such as, for example, alcohols, esters and ketones.
  • the choice will preferably be made of the ester which was used beforehand to extract the intermediate sulphinate from the aqueous solution, such as ethyl or isopropyl acetate.
  • a radical initiator from the family of the commonest azo compounds, such as 2,2'-azobisisobutyronitrile (AZDN ® from Atofina) or 2,2'-azobis(2-methylbutanenitrile) (Vazo ® 67 from DuPont). It can be advantageous to carry out the reaction in an aqueous medium.
  • AZDN ® 2,2'-azobisisobutyronitrile
  • Vazo ® 67 2,2'-azobis(2-methylbutanenitrile)
  • a water-soluble azo radical initiator will be chosen, such as the following commercial products: 4,4'-azobis(4-cyanopentanoic acid) (Azocarboxy ® from Atofina), 2,2'-azobis(2-amidinopropane) hydrochloride (V50 from Wako) or 2,2'-azobis[2- (2-imidazolin-2-yl)propane] hydrochloride (Vazo ® 44WSP from DuPont).
  • the conversion of the sulphinates to carboxylic acids can advantageously be carried out in the reaction medium for the synthesis of the sulphinate precursors without isolation of the latter and without removing the byproducts and inorganic salts before addition of the radical initiator.
  • the carboxylic acids formed can be isolated either by separation by settling or filtration or by extraction with an organic solvent and then evaporation of the latter.
  • the surfactant of formula [2] by reaction of sodium hydrosulphite (dithionite) with the iodinated derivative in a water/acetonitrile or water/ethanol medium in the presence of an alkaline earth metal neutralizing agent, preferably sodium hydrogenocarbonate.
  • an alkaline earth metal neutralizing agent preferably sodium hydrogenocarbonate.
  • a sheet with dimensions of 260 x 20 x 4 mm is formed by compressive moulding, under 30 bar and at 205°C for 6 minutes, from 40 g of powder, which sheet is subjected to steeping in water at 20°C.
  • the sheet is subsequently reheated in a Metrastat® PSD 260 oven at 265°C for 1 hour in the presence of air. After this heat treatment, the sheet can be more or less coloured.
  • the colour is determined by a measurement of yellowing index.
  • the sheet is placed on a calibrated white ceramic plate and the yellowing index is measured by a Minolta® CR 210 colorimeter using the ASTM D 1925 standard for the calculation of the yellowing index. To reduce the standard deviation of this measurement, the latter is repeated a further time and the value shown is a mean yellowing index with a standard deviation of 1.5.
  • This melt flow index is determined using a melt flow tester according to the ISO 1133 standard at a temperature of 230°C and a weight of 5 kg. The index is expressed according to the standard in g/10 min.
  • Example 1 Preparation of a mixture of C 2 F 5 (CH2CF2) 3 -CO 2 NH4 and C 2 F5(CH2CF 2 ) 2 -CH 2 CO2NH4 in the molar proportions 70/30.
  • b) Preparation of the olefin C 2 F 5 (CH 2 CF 2 )m- ⁇ -CH CF 2
  • iodinated telomer C 2 F 5 (CH 2 CF 2 ) 4 -I and 33 g of water are introduced into a jacketed reactor heated using a thermostatically-controlled bath which is equipped with a mechanical stirrer, an upright reflux condenser, a dropping funnel and a temperature probe.
  • the mixture is heated beforehand to 40°C and 23.2 g of triethylamine are run thereon without exceeding 45°C; after 4 hours at 40°C, the reaction mixture is separated by settling, washed with water and then distilled at 68°C under 4 mbar.
  • a 15% aqueous solution is prepared by addition of aqueous ammonia to a pH of 6.9.
  • the sulphinate is obtained in the form of a white solid with a melting point of 86°C, with a yield of 95%.
  • the sulphinate can be converted to carboxylic acid by four different processes, b1 to b4.
  • b1 Treatment of the sulphinate with water: 45.9 g of sulphinate are dissolved in 600 g of demineralized water and are kept stirred for several hours. The pH changes from 6 to 1.
  • the white precipitate formed is filtered off on a sintered glass funnel and then a further precipitate is formed in the filtrate. After a few weeks, the precipitates, which are of the same nature (characteristic band in the IR spectrum of the -COOH groups at 1706 cm "1 ), are combined.
  • the temperature of the air introduced into the spray-dryer is 140°C; the water is removed at a flow rate of 7 kg/h. A portion of the surfactant is removed during the drying.
  • the melt flow index is 3.5 g/10 min.
  • Example 3 The following are successively introduced at 20°C into a stirred reactor described in Example 3: 17.9 I of deionized water, 141 g of a 15% aqueous solution of a surfactant of formula C 2 F 5 (CH 2 CF2)3CH 2 CO2NH4 prepared in Example 2, 1.4 g of paraffin wax with a melting point of approximately 60°C.
  • the reactor is closed, the air is driven off using a vacuum pump and the medium is placed under stirring and brought to 83°C.
  • Vinylidene fluoride is then introduced up to an absolute pressure of 45 bar and then 54 ml of ethyl acetate and 20 g of a 30% by weight solution of n-propyl peroxydicarbonate in methyl pivalate are added.
  • the polymerization begins and the medium is maintained at 83°C and the VDF pressure is maintained at 45 bar by a continuous addition of monomer, while the solution of n-propyl peroxydicarbonate in methyl pivalate is introduced at a constant flow rate of 13 g/hour. After having introduced a total of 7 kg of VDF monomer, the introductions of monomer and of initiator are halted and the gas pressure in the reactor falls to 15 bar. The unreacted VDF monomer is degassed. 24.4 kg of latex having a solids content of 26% are obtained. The amount of coagulate formed during the polymerization is 1.5% as dry weight of PVDF formed.
  • the latex is diluted, so as to bring its solids content to 20%, and is then spray-dried in a 1 m 3 spray-dryer.
  • the temperature of the air introduced into the spray-dryer is 140°C; the water is removed at a flow rate of 7 kg/h.
  • the 19 F NMR analysis gives a residual level of surfactant of 700 ppm.
  • the melt flow index is 1.3 g/10 min.
  • Example 4 The surfactant used in Example 4 is replaced by 141 g of a 15% solution of a mixture of ammonium perfluoroalkylate corresponding to the overall formula C 8 . 4 Fi7.8COONH .
  • the polymerization and the treatment for recovery of the polymer take place as in Example 4. After a heat treatment at 265°C for 1 hour, the PVDF formed in the comparative example is more coloured than the PVDF produced in Example 4.
  • the yellowing index is 45.

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Abstract

L'invention concerne un procédé de préparation de fluoropolymère par polymérisation d'une dispersion aqueuse d'au moins un fluoropolymère, cette dispersion comprenant en outre un tensioactif fluoré, un initiateur radicalaire, éventuellement un agent de transfert et éventuellement une paraffine. Dans ce procédé le tensioactif fluoré est choisi parmi un ou plusieurs des produits suivants: Rf(CH2CF2)m-1- (CH2)nCO2M [1] Rf(CH2CF2)mSO2M [2] Rf (CH2 CF2)m(CH2)n'SO3M [3] dans lesquels: Rf représente un groupe perfluoroalkyle linéaire ou ramifié comprenant entre 1 et 5 atomes de carbone, de préférence entre 2 et 4, m représente un entier compris entre 2 et 6, n représente un entier compris entre 0 et 2, n' prend la valeur de 0 ou 2, M représente un atome d'hydrogène ou un atome de métal alcalin ou un groupe d'ammonium ou un groupe d'ammonium comprenant au moins un substituant d'alkyle inférieur. A titre d'exemple, le procédé de l'invention est utilisé dans la polymérisation (homo ou copolymérisation) de monomères fluorovinyle, tels que, par exemple, du tétrafluoroéthylène C2F4 (TFE), de fluorure de vinylidène H2C=CF2 (VDF), d'hexafluoropropène CF2=CF-CF3 (HFP).
PCT/EP2005/007061 2004-06-10 2005-06-01 Procede de fabrication de fluoropolymere WO2005121290A1 (fr)

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FR0406264 2004-06-10
FR0406264A FR2871469A1 (fr) 2004-06-10 2004-06-10 Procede de fabrication de polymere fluore

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Cited By (26)

* Cited by examiner, † Cited by third party
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WO2006135825A1 (fr) * 2005-06-10 2006-12-21 3M Innovative Properties Company Polymerisation sous emulsion aqueuse de monomeres fluores en presence d'oligomere partiellement fluore comme emulsifiant
WO2007011633A1 (fr) * 2005-07-15 2007-01-25 3M Innovative Properties Company Polymerisation en emulsion aqueuse de monomeres fluores utilisant un tensioactif fluore
WO2009062006A1 (fr) * 2007-11-09 2009-05-14 Dupont Performance Elastomers L.L.C. Procédé de production de polymères fluorés
WO2009062002A1 (fr) * 2007-11-09 2009-05-14 Dupont Performance Elastomers L.L.C. Procédé de production de polymères fluorés
WO2009137734A1 (fr) * 2008-05-09 2009-11-12 E. I. Du Pont De Nemours And Company Réduction d’acides fluoroéther carboxyliques ou de sels utilisés dans la fabrication de résine de fluoropolymère
US7659333B2 (en) 2005-11-24 2010-02-09 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
WO2010056688A1 (fr) * 2008-11-13 2010-05-20 E. I. Du Pont De Nemours And Company Fluorosulfonates
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
US20100160584A1 (en) * 2008-12-23 2010-06-24 E. I. Du Pont De Nemours And Company Ethylene-Tetrafluoroethylene Carboxylic Acids and Salts
WO2010075362A1 (fr) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Polymérisation aqueuse de monomère fluoré à l'aide d'un tensio-actif éther fluoré ramifié à base d'hydrogène
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
WO2010129842A1 (fr) * 2009-05-08 2010-11-11 E. I. Du Pont De Nemours And Company Réduction thermique d'acides carboxyliques fluoroéthérés ou de sels de ceux-ci provenant de dispersions de fluoropolymères
US7838608B2 (en) 2005-12-21 2010-11-23 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US20110124782A1 (en) * 2008-07-18 2011-05-26 Dams Rudolf J Fluorinated ether compounds and methods of using the same
US8119750B2 (en) 2006-07-13 2012-02-21 3M Innovative Properties Company Explosion taming surfactants for the production of perfluoropolymers
JP2012153707A (ja) * 2006-08-29 2012-08-16 Unimatec Co Ltd ポリフルオロアルカンカルボン酸フルオライドおよびその製造法
US8268186B2 (en) 2009-10-15 2012-09-18 E. I. Du Pont De Nemours And Company Fluorinated amphoteric surfactants
US8404790B2 (en) 2005-07-15 2013-03-26 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
US9212693B2 (en) 2007-04-27 2015-12-15 3M Innovative Properties Company Fluoropolymer coated articles
JP2016534211A (ja) * 2013-09-04 2016-11-04 ハネウェル・インターナショナル・インコーポレーテッド 改良された生分解性を有するフッ素系界面活性剤
WO2017153663A1 (fr) 2016-03-08 2017-09-14 Arkema France Films poreux obtenus a partir de latex de polymeres
EP3604349A4 (fr) * 2017-03-31 2020-12-30 Daikin Industries, Ltd. Procédé de fabrication de fluoropolymère, et tensio-actif pour polymérisation ainsi que mise en uvre de ce dernier
CN115651184A (zh) * 2022-09-28 2023-01-31 四川弘氟新材料有限公司 一种含氟聚醚羧酸型表面活性剂及其制备方法
US11767379B2 (en) 2018-03-01 2023-09-26 Daikin Industries, Ltd. Method for manufacturing fluoropolymer
WO2023182229A1 (fr) * 2022-03-23 2023-09-28 ダイキン工業株式会社 Procédé de production de polymère fluoré, et composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524197A (en) * 1984-08-28 1985-06-18 E. I. Du Pont De Nemours And Company Process for making vinylidene fluoride containing fluoroelastomers
EP0822175A2 (fr) * 1996-07-26 1998-02-04 E.I. Du Pont De Nemours And Company Fluorosurfactante contenant de l' hydrogène et son utilisation dans la polymérisation
JP2002308914A (ja) * 2001-04-17 2002-10-23 Daikin Ind Ltd 含フッ素重合体ラテックスの製造方法
EP1334996A2 (fr) * 2002-02-12 2003-08-13 Solvay Solexis S.p.A. Dispersion aqueuse de fluorpolymère

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3954817A (en) * 1973-03-05 1976-05-04 Ciba-Geigy Corporation Process for the manufacture of perfluoroalkylmethylene-carboxylic acids
US3857827A (en) * 1974-01-25 1974-12-31 Pennwalt Corp Method of preparing high-quality vinylidene fluoride polymer in aqueous emulsion
FR2277102A1 (fr) * 1974-07-03 1976-01-30 Kureha Chemical Ind Co Ltd Procede de polymerisation de resines de fluorure de vinylidene
WO1984001894A1 (fr) * 1982-11-12 1984-05-24 American Hospital Supply Corp Sterilisation chimique de tissu biologique implantable
US5285002A (en) * 1993-03-23 1994-02-08 Minnesota Mining And Manufacturing Company Fluorine-containing polymers and preparation and use thereof
IT1265033B1 (it) * 1993-05-28 1996-10-28 Ausimont Spa Polivinilidenfluoruro ad elevate prestazioni meccaniche ed elevata stabilita' termochimica, e relativo processo di preparazione
JPH08333408A (ja) * 1995-06-07 1996-12-17 Asahi Glass Co Ltd 含フッ素共重合体の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4524197A (en) * 1984-08-28 1985-06-18 E. I. Du Pont De Nemours And Company Process for making vinylidene fluoride containing fluoroelastomers
EP0822175A2 (fr) * 1996-07-26 1998-02-04 E.I. Du Pont De Nemours And Company Fluorosurfactante contenant de l' hydrogène et son utilisation dans la polymérisation
JP2002308914A (ja) * 2001-04-17 2002-10-23 Daikin Ind Ltd 含フッ素重合体ラテックスの製造方法
EP1334996A2 (fr) * 2002-02-12 2003-08-13 Solvay Solexis S.p.A. Dispersion aqueuse de fluorpolymère

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 2003, no. 02 5 February 2003 (2003-02-05) *

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WO2006135825A1 (fr) * 2005-06-10 2006-12-21 3M Innovative Properties Company Polymerisation sous emulsion aqueuse de monomeres fluores en presence d'oligomere partiellement fluore comme emulsifiant
WO2007011633A1 (fr) * 2005-07-15 2007-01-25 3M Innovative Properties Company Polymerisation en emulsion aqueuse de monomeres fluores utilisant un tensioactif fluore
US7776946B2 (en) 2005-07-15 2010-08-17 3M Innovative Properties Company Aqueous emulsion polymerization of fluorinated monomers using a fluorinated surfactant
US7671112B2 (en) 2005-07-15 2010-03-02 3M Innovative Properties Company Method of making fluoropolymer dispersion
US8404790B2 (en) 2005-07-15 2013-03-26 3M Innovative Properties Company Aqueous emulsion polymerization process for producing fluoropolymers
US7659333B2 (en) 2005-11-24 2010-02-09 3M Innovative Properties Company Fluorinated surfactants for use in making a fluoropolymer
US7838608B2 (en) 2005-12-21 2010-11-23 3M Innovative Properties Company Fluorinated surfactants for making fluoropolymers
US7728087B2 (en) 2005-12-23 2010-06-01 3M Innovative Properties Company Fluoropolymer dispersion and method for making the same
US7754795B2 (en) 2006-05-25 2010-07-13 3M Innovative Properties Company Coating composition
US8119750B2 (en) 2006-07-13 2012-02-21 3M Innovative Properties Company Explosion taming surfactants for the production of perfluoropolymers
JP2012153707A (ja) * 2006-08-29 2012-08-16 Unimatec Co Ltd ポリフルオロアルカンカルボン酸フルオライドおよびその製造法
US9212693B2 (en) 2007-04-27 2015-12-15 3M Innovative Properties Company Fluoropolymer coated articles
US7754810B2 (en) 2007-11-09 2010-07-13 Dupont Performance Elastomers Process for producing fluoropolymers
CN101903421B (zh) * 2007-11-09 2012-06-20 纳幕尔杜邦公司 制备含氟聚合物的方法
WO2009062002A1 (fr) * 2007-11-09 2009-05-14 Dupont Performance Elastomers L.L.C. Procédé de production de polymères fluorés
WO2009062006A1 (fr) * 2007-11-09 2009-05-14 Dupont Performance Elastomers L.L.C. Procédé de production de polymères fluorés
WO2009137734A1 (fr) * 2008-05-09 2009-11-12 E. I. Du Pont De Nemours And Company Réduction d’acides fluoroéther carboxyliques ou de sels utilisés dans la fabrication de résine de fluoropolymère
US8633288B2 (en) * 2008-07-18 2014-01-21 3M Innovative Properties Company Fluorinated ether compounds and methods of using the same
US20110124782A1 (en) * 2008-07-18 2011-05-26 Dams Rudolf J Fluorinated ether compounds and methods of using the same
CN102216345A (zh) * 2008-11-13 2011-10-12 纳幕尔杜邦公司 氟磺酸盐
US7989568B2 (en) 2008-11-13 2011-08-02 E.I. Du Pont De Nemours And Company Fluorosulfonates
JP2012508810A (ja) * 2008-11-13 2012-04-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー フルオロスルホネート
WO2010056688A1 (fr) * 2008-11-13 2010-05-20 E. I. Du Pont De Nemours And Company Fluorosulfonates
US20110245135A1 (en) * 2008-11-13 2011-10-06 E. I. Du Pont De Nemours And Company Fluorosulfonates
US8703998B2 (en) 2008-11-13 2014-04-22 E I Du Pont De Nemours And Company Fluorosulfonates
WO2010075362A1 (fr) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Polymérisation aqueuse de monomère fluoré à l'aide d'un tensio-actif éther fluoré ramifié à base d'hydrogène
CN102264684A (zh) * 2008-12-23 2011-11-30 杜邦公司 乙烯-四氟乙烯羧酸和盐
WO2010075354A1 (fr) * 2008-12-23 2010-07-01 E. I. Du Pont De Nemours And Company Acides éthylène-tétrafluoroéthylène carboxyliques et sels correspondants
US20100160584A1 (en) * 2008-12-23 2010-06-24 E. I. Du Pont De Nemours And Company Ethylene-Tetrafluoroethylene Carboxylic Acids and Salts
WO2010129842A1 (fr) * 2009-05-08 2010-11-11 E. I. Du Pont De Nemours And Company Réduction thermique d'acides carboxyliques fluoroéthérés ou de sels de ceux-ci provenant de dispersions de fluoropolymères
US8329813B2 (en) 2009-05-08 2012-12-11 E I Du Pont De Nemours And Company Thermal reduction of fluoroether carboxylic acids or salts from fluoropolymer dispersions
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US8268186B2 (en) 2009-10-15 2012-09-18 E. I. Du Pont De Nemours And Company Fluorinated amphoteric surfactants
JP2016534211A (ja) * 2013-09-04 2016-11-04 ハネウェル・インターナショナル・インコーポレーテッド 改良された生分解性を有するフッ素系界面活性剤
WO2017153663A1 (fr) 2016-03-08 2017-09-14 Arkema France Films poreux obtenus a partir de latex de polymeres
EP3604349A4 (fr) * 2017-03-31 2020-12-30 Daikin Industries, Ltd. Procédé de fabrication de fluoropolymère, et tensio-actif pour polymérisation ainsi que mise en uvre de ce dernier
EP4257638A3 (fr) * 2017-03-31 2023-12-13 Daikin Industries, Ltd. Procédé de production de fluoropolymère, tensioactif pour polymérisation et utilisation de tensioactif
US11767379B2 (en) 2018-03-01 2023-09-26 Daikin Industries, Ltd. Method for manufacturing fluoropolymer
WO2023182229A1 (fr) * 2022-03-23 2023-09-28 ダイキン工業株式会社 Procédé de production de polymère fluoré, et composition
CN115651184A (zh) * 2022-09-28 2023-01-31 四川弘氟新材料有限公司 一种含氟聚醚羧酸型表面活性剂及其制备方法

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