Classifications

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  • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
• • C—CHEMISTRY; METALLURGY
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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  • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
  • C08F214/22—Vinylidene fluoride
• • 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
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/20—Manufacture of shaped structures of ion-exchange resins
  • C08J5/22—Films, membranes or diaphragms
  • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
  • C08J5/2218—Synthetic macromolecular compounds
  • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
  • C08J5/2237—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or 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; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N15/00—Thermoelectric devices without a junction of dissimilar materials; Thermomagnetic devices, e.g. using the Nernst-Ettingshausen effect
  • H10N15/10—Thermoelectric devices using thermal change of the dielectric constant, e.g. working above and below the Curie point
  • H10N15/15—Thermoelectric active materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10N30/00—Piezoelectric or electrostrictive devices
  • H10N30/80—Constructional details
  • H10N30/85—Piezoelectric or electrostrictive active materials
  • H10N30/857—Macromolecular compositions
• • 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
  • C08F2438/00—Living radical polymerisation
• • 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
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

• the present invention relates to a radical copolymerization process of fluorinated monomers and particularly trifluoroethylene and additional monomers different from trifluoroethylene, controlled by a compound xanthate or trithiocarbonate or monoiodé.
• the invention also makes it possible to prepare thermoplastic block copolymers by this process.
• the invention also provides the thermoplastic block copolymers obtainable thereby.
• Fluoropolymers are a class of compounds with outstanding properties for a variety of applications, from paint and specialty coatings to seals, optics, microelectronics and membrane technology.
• the copolymers are particularly interesting because of their diversity, their morphology, their exceptional properties and their versatility.
• controlled radical copolymerization techniques that is to say, to obtain a control of the molecular weight and the polymolecularity index of polymers, as well as a synthesis of copolymers to controlled architectures (block, grafted, alternating, gradient, hyperbranched ).
• copolymers could be prepared by controlled radical copolymerization methods using xanthate compounds as chain transfer agents, under the name MADIX, for "Macromolecular Design via Interchange of Xanthates"; or alternatively by means of iodinated compounds as chain transfer agents.
• MADIX Macromolecular Design via Interchange of Xanthates
• WO 01/60869 describes the synthesis of fluorinated elastomers by copolymerization in aqueous medium of VDF with HFP, TFE, CTFE or PAVE (perfluoroalkoxy alkyl vinyl ethers) and a third comonomer considered as a monomer at site brominated or iodinated crosslinking providing a subsequent crosslinking.
• US 2008/0081 195 discloses terpolymers, such as terpolymers of vinylidene fluoride, trifluoroethylene and chlorotrifluoroethylene, having two functional terminations and prepared by controlled polymerization with borane or di-iodinated transfer agents.
• thermoplastic fluorinated copolymers particularly by means of controlled radical copolymerization methods.
• the invention relates first of all to a process for the preparation of a thermoplastic copolymer, comprising a step of controlled radical copolymerization of a trifluoroethylene monomer with at least one additional monomer, other than trifluoroethylene, in the presence of a chain transfer agent.
• said chain transfer agent being a xanthate compound, a trithiocarbonate compound or a monoiodinated compound.
• - consist of vinylidene fluoride and trifluoroethylene; or - include vinylidene fluoride, trifluoroethylene, and at least one additional monomer.
• the additional monomer or monomers are chosen from fluorinated monomers, and preferably from 2,3,3,3-tetrafluoropropene, vinyl fluoride, 2-chloro-1,1-difluoroethylene, 2-bromo-1,1-difluoroethylene, hexafluoropropene, 3,3,3-trifluoropropene, 3,3,3-trifluoro-2-chloropropene, 1,1,1,3-tetrafluoropropene, 3, 3,3-trifluoro-2-bromoropropene, 1H-pentafluoropropene, 2H-pentafluoropropene, perfluoromethylvinylether, perfluoroethylvinylether, perfluoropropylvinylether, ⁇ -trifluoromethacrylic acid and its derivatives; or are chosen from hydrogenated monomers, and preferably from vinyl acetate, N-vinyl pyrrolidone,
• the copolymer prepared is a thermoplastic block copolymer. This means that the copolymers according to the invention are fusible semi-crystalline polymers.
• the controlled radical copolymerization process employed is of the RAFT / MADIX type (by reversible addition-fragmentation chain transfer).
• the xanthate or trithiocarbonate compound is O-ethyl-S- (1-methyloxycarbonyl) ethylxanthate.
• the chain transfer agent is a mono-iodinated compound which is a 1-iodofluoroalkane, and which is preferably a compound of formula RF- (CH 2 CF 2 ) nl, in which n is a whole number ranging from 1 to 500, and R F represents a perfluorocarbon group, more particularly preferably selected from the groups CF 3 , C 2 F 5 , C 3 F 7 and C m F 2m + 1, m being an even integer ranging from 4 to 20.
• the invention also relates to a copolymer having trifluoroethylene units and having a xanthate or trithiocarbonate or monoiodinated termination.
• the copolymer has:
• the additional units are chosen from fluorinated units, and preferably from 2,3,3,3-tetrafluoropropene, vinyl fluoride, 2-chloro-1,1-difluoroethylene, 2-bromo- 1,1-Difluoroethylene, hexafluoropropene, 3,3,3-trifluoropropene, 3,3,3-trifluoro-2-chloropropene, 1,1,1,3-tetrafluoropropene, 3,3,3-trifluoro-2-bromopropene, 1H-pentafluoropropene, 2H-pentafluoropropene, perfluoromethylvinylether, perfluoroethylvinylether, perfluoropropylvinylether, alpha-trifluoromethacrylic acid and its derivatives; or chosen from hydrogenated units, and preferably from vinyl acetate units, N-vinyl pyrrolidone, methacrylates,
• the copolymer is a block copolymer of which at least one block comprises trifluoroethylene units, or is a homo-poly (trifluoroethylene) block.
• At least one block comprises vinylidene fluoride units.
• At least one block comprises vinylidene fluoride and trifluoroethylene units.
• At least one block comprises units chosen from fluorinated units, and preferably from 2,3,3,3-tetrafluoropropene, vinyl fluoride, 2-chloro-1, 1-difluoroethylene, 2 units. bromo-1,1-difluoroethylene, hexafluoropropene, 3,3,3-trifluoropropene, 3,3,3-trifluoro- 2-chloropropene, 1,1,1,3-tetrafluoropropene, 3,3,3-trifluoro-2-bronnoropropene, 1H-pentafluoropropene, 2H-pentafluoropropene, perfluoromethylvinylether, perfluoroethylvinylether, perfluoropropylvinylether, acid a- trifluoromethacrylic acid and its derivatives; or chosen from hydrogenated units, and preferably from vinyl acetate units, N-vinyl pyrrolidone, me
• the block copolymer comprises:
• copolymer block comprising vinylidene fluoride and trifluoroethylene units and a copolymer block comprising vinylidene fluoride and trifluoroethylene units and additional units.
• the block copolymer comprises:
• copolymer block comprising vinylidene fluoride and trifluoroethylene units and a copolymer block comprising vinylidene fluoride, trifluoroethylene and 2,3,3,3-tetrafluoropropene units;
• the invention also relates to a method for preparing a copolymer (c), comprising a reaction step of a copolymer (a) which as described above, with at least one comonomer (b).
• the copolymer (c) is a block copolymer described above.
• the comonomer (b) is chosen from fluorinated monomers, and preferably from vinylidene fluoride, 2,3,3,3-tetrafluoropropene, vinyl fluoride, 2-chloro-1, 1-Difluoroethylene, 2-bromo-1,1-difluoroethylene, hexafluoropropene, 3,3,3-trifluoropropene, 3,3,3-trifluoro-2-chloropropene, 1, 1, 1, 3 tetrafluoropropene, 3,3,3-trifluoro-2- bromoropropene, 1H-pentafluoropropene, 2H-pentafluoropropene, perfluoromethylvinylether, perfluoroethylvinylether, perfluoropropylvinylether, alpha-trifluoromethacrylic acid and its derivatives; or is selected from hydrogenated monomers, and preferably from vinyl acetate, N-vin
• the process comprises a preliminary step of preparing the copolymer (a) according to the method described above.
• the invention also relates to a film or a membrane comprising at least one copolymer as described above.
• the invention also relates to a piezoelectric device comprising a film as described above.
• the invention also relates to a ferroelectric device comprising a film as described above.
• the invention also relates to a pyroelectric device comprising a film as described above.
• the invention also relates to a coating comprising a film as described above.
• the present invention makes it possible to meet the existing needs in the state of the art. It provides more particularly a controlled radical copolymerization process of trifluoroethylene-based copolymers (and especially based on vinylidene fluoride and trifluoroethylene, or based on vinylidene fluoride and trifluoroethylene and a third comonomer) simpler and more sure that known methods based on the use of boranes.
• the invention also provides thermoplastic block copolymers based on trifluoroethylene.
• the invention also has one or preferably more of the advantageous features listed below.
• the invention makes it possible to obtain a wide variety of block copolymers from polymers or copolymers having a terminating xanthate or trithiocarbonate or monoiodea, and additional comonomers.
• copolymers according to the invention can be functionalized in a wide variety of ways. For example, these copolymers may be used for subsequent crosslinking or grafting steps.
• the invention is particularly useful for the manufacture of piezoelectric, ferroelectric or pyroelectric compounds.
• Figure 1 shows a 1 H NMR spectrum in deuterated acetone of a PVDF- ⁇ -polyblock copolymer (VDF-ter-TrFE-ter-1234yf) (see Example 1).
• Figure 2 shows a 19 F NMR spectrum in deuterated acetone of the same block copolymer.
• Figure 3 shows a 1 H NMR spectrum in deuterated acetone of a xanthate-terminated poly (VDF-co-TrFE) copolymer (see Example 2).
• Figure 4 shows a 19 F NMR spectrum in deuterated acetone of the same copolymer.
• FIG. 5 represents a 1 H NMR spectrum in deuterated acetone of a xanthate-terminated poly (VDF-co-TrFE) -i-poly (VDF-ter-TrFE-ter-1234yf) block copolymer (see FIG. Example 3).
• Figure 6 shows a 19 F NMR spectrum in deuterated acetone of the same block copolymer.
• Figure 7 shows a 1 H NMR spectrum in deuterated acetone of a xanthate-terminated poly (VDF-co-TrFE) -i-PVDF block copolymer (see Example 4).
• Figure 8 shows a 19 F NMR spectrum in deuterated acetone of the same block copolymer.
• FIG. 9 represents a steric exclusion chromatogram (SEC or GPC) of a poly (VDF-co-TrFE) copolymer (see Example 2) with xanthate termination, and a polyblock copolymer (VDF-co -VDF (VDF-ter-TrFE-ter-1234yf) terminally xanthate-terminated (see Example 3).
• SEC steric exclusion chromatogram
• FIG. 10 represents a steric exclusion chromatogram (SEC or GPC) of a poly (VDF-co-TrFE) copolymer (see example 2) at termination xanthate, and a xanthate-terminated poly (VDF-co-TrFE) -i -PVDF block copolymer (see Example 4).
• SEC steric exclusion chromatogram
• the retention time in minutes is plotted on the abscissa, and the intensity in mV is on the ordinate.
• the highest molar masses correspond to the lowest retention times.
• FIG. 11 represents a thermogravimetric thermogram made in air of poly (VDF-ter-TrFE-ter-1234yf) polycarbonyl-terminated copolymers (see example 1), poly (VDF-co-TrFE ) xanthate-terminated (see Example 2), xanthate-terminated poly (VDF-co-TrFE) -i-poly (VDF-ter-TrFE-ter-1234yf) (see Example 3) and poly (VDF- Xanthate-terminated co-TrFE) -i -PVDF (see Example 4).
• the numbers shown in the figure correspond to the numbers of the examples.
• the temperature in ° C is indicated on the abscissa, and the residual mass in% is indicated on the ordinate.
• TrFE or VF 3 denote trifluoroethylene
• VDF denotes vinylidene fluoride
• PVDF denotes polyvinylidene fluoride
• 1234yf denotes 2,3,3,3-tetrafluoropropene.
• the invention provides for preparing a thermoplastic block copolymer by means of a copolymerization reaction between TrFE and at least one additional monomer, possibly several, in the presence of a xanthate or trithiocarbonate compound or a monoiodinated compound as a chain transfer agent for controlling the copolymerization reaction.
• a copolymer having TrFE units and units corresponding to the additional monomer X is obtained.
• the copolymer obtained is denoted poly (TrFE-co-X) or poly (X-co-TrFE). ).
• VDF VDF-co-TrFE
• TrFE-co-VDF poly (TrFE-co-VDF).
• another additional monomer for example selected from fluorinated monomers, and preferably from 2,3,3,3-tetrafluoropropene (1234yf), vinyl fluoride, 2-chloro-1, difluoroethylene, 2-bromo-1,1-difluoroethylene, hexafluoropropene, 3,3,3- trifluoropropene, 3,3,3-trifluoro-2-chloropropene, 1,1,1,3-tetrafluoropropene, 1H-pentafluoropropene, 2H-pentafluoropropene, 3,3,3-trifluoro-2-bromoropropene, perfluoromethylvinyl ether, perfluoroethylvinyl ether, perfluoropropylvinyl ether, alpha-trifluoromethacrylic acid and its derivatives; or chosen from hydrogenated monomers, and preferably from vinyl acetate, N-vinylpyrrol
• the invention makes it possible to obtain the poly (VDF ter-TrFE-ter-1234yf) copolymer.
• the xanthate or trithiocarbonate compound is a compound of formula (I):
• R 1 represents an aliphatic (preferably alkyl) group having from 1 to 20 carbon atoms
• -Z represents a group -O-R2 in which R 2 represents an alkyl or aryl group containing from 1 to 10 carbon atoms (in this case in which case it is a xanthate compound) or
• -Z represents a group -S-R3, in which R3 represents an aliphatic (preferably alkyl) group having from 1 to 20 carbon atoms (in this case it is of a trithiocarbonate compound).
• R 1, R 2 and R 3 may be substituted or unsubstituted, preferably unsubstituted.
• R 1, R 2 and R 3 are linear or branched groups, and preferably they are saturated groups.
• thermostability can be achieved with copolymers prepared from a xanthate or trithiocarbonate compound, as compared to copolymers made from a mono-ion compound (see Figure 11 in this regard).
• the mono-iodinated compound is a compound having a single iodine atom. It may in particular be a 1-iodofluoroalkane, and in particular a compound of formula RF- (CH 2 CF 2 ) nl, in which n is an integer ranging from 1 to 500, and R F represents a perfluorocarbon group, preferably chosen from the groups CF 3 , C 2 F 5 , C 3 F 7 and C m F 2m + 1, m being an even integer ranging from 4 to 20.
• the copolymers obtained according to the process of the invention then have a monoiodinated (single) terminal, that is to say a single terminal iodine atom.
• the copolymerization reaction is carried out in the presence of an initiator.
• an initiator may be, for example, tert-butyl peroxypivalate, ter-amyl peroxypivalate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, sodium, ammonium or potassium persulfates, benzoyl peroxide, terf-butyl hydroxy peroxide, terf-butyl peroxide or 2,5-bis (tert-butylperoxy) -2,5-dimethylhexane.
• the reaction is carried out in a solvent, which is for example chosen from 1, 1, 1, 3,3-pentafluorobutane, acetonitrile, methyl ethyl ketone, 2,2,2-trifluoroethanol, hexafluoroisopropanol, acetate methyl, ethyl acetate, cyclohexanone, water and mixtures thereof.
• a solvent which is for example chosen from 1, 1, 1, 3,3-pentafluorobutane, acetonitrile, methyl ethyl ketone, 2,2,2-trifluoroethanol, hexafluoroisopropanol, acetate methyl, ethyl acetate, cyclohexanone, water and mixtures thereof.
• the reaction is preferably carried out at a temperature of 10 to 200 ° C, preferably 35 to 170 ° C, and a pressure of 10 to 120 bar, preferably 20 to 80 bar.
• the choice of the optimum temperature depends on the initiator that is used. Generally, the reaction is carried out for at least 6 hours, at a temperature at which the half-life of the initiator is about 1 hour.
• the molar ratio of the amount of chain transfer agent to the amount of monomers makes it possible to control the molar mass of the copolymer.
• this ratio is from 0.001 to 0.020, more preferably from 0.005 to 0.010.
• the initial molar ratio of the amount of the monomer TrFE to the amount of the comonomers can be, for example, from 10% to 90%, preferably from at 50%.
• a copolymer containing about 65% VDF and 35% TrFE (in molar proportions) is particularly advantageous.
• the molar mass of the copolymer obtained is preferably from 10,000 to 400,000 g / mol, more preferably from 40,000 to 300,000 g / mol. The higher the molar mass, the better the properties of the materials obtained.
• the polymolecularity index of the copolymer obtained is preferably from 1.2 to 1.9, more preferably from 1.4 to 1.7.
• copolymer obtained by this synthetic technique because of its xanthate or trithiocarbonate termination or monoiodinated termination, may in turn be reacted with one (or more) comonomer for the preparation of another block copolymer.
• the comonomer (s) may be chosen in particular from those listed above.
• the block copolymer thus obtained may comprise (or consist of) a first block and a second block.
• the first block can in particular be a block copolymer of vinylidene fluoride and trifluoroethylene or a terpolymer based on vinylidene fluoride, trifluoroethylene and 2,3,3,3-tetrafluoropropene (1234 yf).
• the second block may be a homopolymer, copolymer or terpolymer block.
• the second block may be a polyvinylidene fluoride block, a terpolymer based on vinylidene fluoride, trifluoroethylene and 2,3,3,3-tetrafluoropropene, a terpolymer based on vinylidene fluoride, trifluoroethylene and vinyl fluoride, a terpolymer based on vinylidene fluoride, trifluoroethylene and 2-chloro-1,1-difluoroethylene, a terpolymer based on vinylidene fluoride, trifluoroethylene and 2-bromo-1,1-difluoroethylene, a terpolymer based on vinylidene fluoride, trifluoroethylene and hexafluoropropene, a terpolymer based on vinylidene fluoride, trifluoroethylene and 3,3,3-trifluoropropene, a terpolymer based on vinylidene fluoride, tri
• the molar ratio of the amount of comonomer to the amount of xanthate or trithiocarbonate or monoiodinated terminated copolymer is preferably from 1 to 200, more preferably from 5 to 100.
• copolymers obtained according to the invention are particularly useful for the manufacture of electrolytes or for the manufacture of membranes. They are also useful for the manufacture of piezoelectric, ferroelectric or pyroelectric devices as well as coatings.
• PVDF-ter-TrFE-ter-1234yf The synthesis of the PVDF- ⁇ -poly block polymer (VDF-ter-TrFE-ter-1234yf) was carried out in two steps, as follows:
• the radical copolymerization is carried out in a 100 ml autoclave Parr Hastelloy equipped with a pressure gauge, a bursting disc, and gas introduction and release valves.
• a regulated electronic device controls both agitation and heating of the autoclave.
• the reactor is placed under vacuum for 40 minutes, then f-butyl peroxypivalate TBPPI (0.60 g, 3.47 mmol) and 60 ml of 1,1,1,3,3-pentafluorobutane. are introduced.
• the reactor is then cooled to -60 ° C. (acetone / liquid nitrogen mixture), followed by 1,1,2-trifluoroethylene or TrFE (7.47 g, 0.091 mol), 2,3,3,3-tetrafluorocarbon.
• 2-propene or 1234yf (1.49 g, 0.013 mol
• the vinylidene fluoride or VDF (10 g, 0.156 mmol
• the reactor is progressively heated to 74 ° C, and changes in pressure and temperature are recorded.
• an increase in the pressure inside the reactor is observed, due to the exothermicity of the reaction, and then a decrease thereof, caused by the conversion of the gaseous fluorinated monomers into the desired polymer.
• the pressure is around 35 bar (a rapid increase in temperature to 78 ° C is observed, which shows that the reaction is exothermic).
• the pressure goes from 35 bars to 12 bars with a temperature maintained at 74 ° C.
• the reactor is left in ice for 30 min and then degassed (release of the unreacted fluorinated monomers).
• the reference A designates the CFH group of TrFE;
• the reference B denotes the group CF 2 CH 2 -I;
• C denotes the normal diads - CH 2 CF 2 -CH 2 CF 2 - of VDF and CH 2 of 1234yf;
• the reference D denotes the inverse diads -CF2CH2-CH2CF2- of VDF.
• the calculated proportion of TrFE is 20 mol%.
• reference E denotes 1234yf.
• the ATG thermogram (made under air) of the copolymer is visible in FIG. 11 (curve No. 1).
• This copolymerization is carried out as previously in a 100 mL HC-276 reactor by introducing respectively i-butyl peroxypivalate (0.904 g, 5.2 mmol), 2-mercaptopropionic acid methyl ester O-ethyl dithiocarbonate (Rhodixan; 0.81 g, 3.9 mmol) and 50 mL of 1,1,1,3,3-pentafluorobutane.
• the reactor is then cooled to -60 ° C. (acetone / liquid nitrogen mixture), then TrFE (12.81 g, 0.156 mol) followed by VDF (15 g, 0.234 mmol) are then successively introduced therein.
• the reactor is progressively heated to 74 ° C, and changes in pressure and temperature are recorded. During the polymerization, an increase in the pressure inside the reactor is observed, due to the exothermicity of the reaction, and then a decrease thereof, caused by the consumption of the fluorinated monomers gas in the desired polymer. At 74 ° C, the pressure is around 22 bar (related to the exotherm up to 76 ° C).
• the reference A designates the group CHF; reference B denotes the group -CF 2 CH 2 SC (S) OEt; C is -CH 2 CF 2 -CH 2 CF 2 -; and the reference D denotes the group tBu-VDF.
• the references a, b, c and d correspond to the positions indicated on the illustrated formula of the copolymer.
• the reference E designates -CH 2 CF 2 -CH 2 .
• the GPC chromatogram of the copolymer is visible in FIGS. 9 and 10.
• the molar mass of this copolymer is 40,000 g / mol (PMMA equivalent) and its DPI polymolecularity index is 1.61.
• This copolymerization is carried out by introducing the copolymers based on VDF and TrFE of Example 2 (6.2 g, 0.026 mol, 2%) into the autoclave.
• the reactor is placed under vacuum for 40 minutes, then t-butyl peroxypivalate (0.60 g, 3.47 mmol) and 60 ml of 1,1,1,3,3-pentafluorobutane are introduced therein.
• the reactor is then cooled to -60 ° C., TrFE (7.47 g, 0.091 mol), 1234yf (1.49 g, 0.013 mol) and finally VDF (10 g, 0.156 mmol) are then respectively introduced.
• the reactor is progressively heated to 74 ° C, and changes in pressure and temperature are recorded.
• the GPC chromatogram of the copolymer is visible in FIG. 9.
• the molar mass of the block copolymer is 55,000 g / mol (PMMA equivalent) and the DPI is 1.71).
• the ATG thermogram of the copolymer is visible in FIG. 11 (curve No. 3).
• the copolymerization is carried out by introducing the xanthous-terminated VDF and TrFE copolymer synthesized in Example 2 (6.2 g, 0.026 mol, 2%) into the autoclave.
• the reactor is placed under vacuum for 40 minutes, then f-butyl peroxypivalate (0.43 g, 1.87 mmol) and 60 ml of 1,1,1,3,3-pentafluorobutane are introduced therein.
• the reactor is then cooled to -60 ° C (acetone / liquid nitrogen mixture), and then the VDF (12 g, 0.187 mmol) is introduced.
• the reactor is progressively heated to 74 ° C, and changes in pressure and temperature are recorded.
• the desired copolymer in the form of a white powder, is characterized by 1 H NMR spectroscopy (FIG. 7) and 19 F (FIG. 8). The calculated yield is 79%.
• the GPC chromatogram of the copolymer is visible in FIG. 10.
• the molar mass of this block copolymer is 43,000 g / mol (PMMA equivalent) and the DPI is 1.72.
• the ATG thermogram of the copolymer is visible in FIG. 11 (curve No. 4).

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