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  • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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  • 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
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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
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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
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  • C08F214/22—Vinylidene fluoride
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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
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  • C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
  • C08L27/22—Compositions of 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; Compositions of derivatives of such polymers modified by chemical after-treatment
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  • 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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  • C08F214/18—Monomers containing fluorine
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  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
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  • C08F2810/00—Chemical modification of a polymer
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  • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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  • C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
  • C08J2327/22—Characterised by the use of 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; Derivatives of such polymers modified by chemical after-treatment
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  • C08L2203/20—Applications use in electrical or conductive gadgets
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  • C08L2205/00—Polymer mixtures characterised by other features
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  • C08L2312/00—Crosslinking

Definitions

• the present invention relates to crosslinkable electroactive fluoropolymers, a process for preparing them, and films made therefrom.
• Electroactive fluorinated polymers or PFEAs are mainly derivatives of polyvinylidene fluoride (PVDF). See in this regard the article Vinylidene fluoride and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties? of Soulestin et al. "in Prog. Polym. Sci. 2017 (DOI: 10.1016 / j.progpolymsci.2017.04.004). These polymers have particularly interesting dielectric and electromechanical properties. Fluorinated copolymers formed from monomers of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) are particularly interesting because of their piezoelectric, pyroelectric and ferroelectric properties. In particular, they make it possible to convert mechanical or thermal energy into electrical energy or vice versa.
• VDF polyvinylidene fluoride
• TrFE trifluoroethylene
• fluorinated copolymers also comprise units derived from another monomer having a substituent chlorine, bromine or iodine, and in particular chlorotrifluoroethylene (CTFE) or chlorofluoroethylene (CFE).
• CTFE chlorotrifluoroethylene
• CFE chlorofluoroethylene
• Such copolymers have a set of useful properties, namely a ferroelectric relaxor character (characterized by a maximum of dielectric constant, as a function of temperature, broad and dependent on the frequency of the electric field), a high dielectric constant, a high saturation polarization, semi-crystalline morphology.
• the electroactive fluorinated polymers are shaped as films, generally by depositing from a formulation called "ink".
• in the manufacture of electroactive devices it may be necessary to render some or all of the film insoluble in a predefined pattern. Indeed, it is often necessary to deposit other layers above the film of polymer, in order to manufacture the desired device. This deposition of other layers often involves the use of a solvent. If the electroactive fluoropolymer is not crosslinked, it can be damaged by this solvent during the deposition of the other layers.
• crosslinking requires the presence of a crosslinking agent in addition to the polymer.
• This agent complicates the preparation of the polymer film and may lead to the degradation of the electroactive properties. It is generally desirable to reduce the number of components used in the formulation for the preparation of the polymeric film.
• WO 2013/087500 discloses a fluoropolymer manufactured by polymerization of VDF, TrFE, and a third monomer containing an azide group. This fluorinated polymer may then be crosslinked, preferably in the presence of a crosslinking agent.
• WO 2013/087501 relates to a composition comprising a fluoropolymer comprising units derived from VDF and TrFE and a crosslinking agent comprising azide groups.
• WO 2015/128337 discloses a fluoropolymer manufactured by polymerization of VDF, TrFE, and a third monomer of (meth) acrylic type. This fluorinated polymer may then be crosslinked, preferably in the presence of a crosslinking agent.
• WO 2010/021962 discloses fluorinated polymers comprising azide groups, which can be obtained either by reaction of a fluorinated polymer with an azide compound, or by polymerization of monomers in the presence of an azide compound.
• fluoropolymers provided in the document are copolymers based on VDF and HFP (hexafluoropropylene), or iodinated terminated polymers (PVDF-I and 1-iodo-perfluorooctane) reacting with sodium azide.
• the invention firstly relates to a copolymer comprising units derived from monomers of vinylidene fluoride and / or trifluoroethylene and fluorinated monomers X comprising a double bond and a leaving group chosen from chlorine, bromine and carbon atoms. iodine, the leaving groups being partially replaced by azide groups in the copolymer.
• the fluorinated monomers X are chosen from chlorotrifluoroethylene and chlorofluoroethylene.
• the copolymer comprises both units derived from vinylidene fluoride monomers and units derived from trifluoroethylene monomers, the proportion of units originating from trifluoroethylene monomers being preferably from 15 to 55 mol%. relative to the sum of units derived from monomers of vinylidene fluoride and trifluoroethylene.
• the copolymer comprises a total content of units derived from fluorinated monomers X of 1 to 20 mol%, preferably 2 to 15 mol%.
• the molar proportion of leaving groups in the copolymer replaced by groups The azides are 5 to 90%, preferably 10 to 75%, and more preferably 15 to 40%.
• the composition is a solution or dispersion of the copolymer in a liquid vehicle.
• the invention also relates to a process for the preparation of a copolymer as described above, comprising:
• the compound comprising an azide group is sodium azide.
• the contacting is carried out in a solvent, preferably chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate.
• a solvent preferably chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate,
• the invention also relates to a composition
• a composition comprising:
• a first copolymer comprising units originating from vinylidene fluoride and / or trifluoroethylene fluoride monomers as well as fluorinated monomers X 'comprising a double bond and a leaving group chosen from chlorine, bromine and iodine atoms;
• a second copolymer comprising units derived from monomers of vinylidene fluoride and / or trifluoroethylene and also fluorinated monomers X comprising a double bond and a leaving group chosen from chlorine, bromine and iodine atoms, all or part of leaving groups being replaced by azide groups in the copolymer.
• the fluorinated monomers X are chosen from chlorotrifluoroethylene and chlorofluoroethylene; and / or the fluorinated monomers X 'are chosen from chlorotrifluoroethylene and chlorofluoroethylene; and preferably the fluorinated monomers X and X 'are identical.
• the first copolymer comprises both units derived from vinylidene fluoride monomers and units derived from trifluoroethylene monomers, the proportion of units derived from trifluoroethylene monomers being preferably from 15 to 55 mol.
• the second copolymer comprises both units derived from vinylidene fluoride monomers and units derived from trifluoroethylene monomers, the proportion of units originating from trifluoroethylene monomers being preferably from 15 to 55 mol% relative to to the sum of units derived from monomers of vinylidene fluoride and trifluoroethylene.
• the first copolymer comprises a total content of units derived from fluorinated monomers X of from 1 to 20 mol%, preferably from 2 to 15 mol%; and / or the second copolymer comprises a total content of units derived from fluorinated monomers X 'of from 1 to 20 mol%, preferably from 2 to 15 mol%.
• the composition comprises from 5 to 95% by weight of the first copolymer and from 5 to 95% by weight of the second copolymer; preferably 30 to 70% by weight of the first copolymer and 30 to 70% by weight of the second copolymer; the contents being expressed relative to the sum of the first copolymer and the second copolymer.
• the composition is a solution or dispersion of the first copolymer and the second copolymer in a liquid vehicle.
• the invention also relates to a method for manufacturing a composition as described above, comprising:
• the supply of the second copolymer comprises the preparation of this second copolymer, comprising:
• the compound comprising an azide group is sodium azide.
• the contacting is carried out in a solvent, preferably chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate.
• a solvent preferably chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate,
• the invention also relates to a method for manufacturing a film, comprising:
• the crosslinking is performed in a predefined pattern, the method then comprising removing portions of copolymer or non-crosslinked composition (e) by contacting a solvent.
• the invention also relates to a film obtained by the method described above.
• the invention also relates to an electronic device comprising a film as described above, the electronic device being preferably chosen from field effect transistors, memory devices, capacitors, sensors, actuators, electromechanical microsystems. , electro-caloric devices and haptic devices.
• the present invention overcomes the disadvantages of the state of the art. More particularly, it provides crosslinkable electroactive polymers and compositions containing crosslinkable electroactive polymers. After crosslinking, the invention makes it possible to obtain insoluble polymer films having predefined patterns and having one or more of the following properties (and preferably all): a semi-crystalline morphology, a high dielectric constant, a saturation polarization high, and a Curie transition.
• the invention makes it possible to carry out the crosslinking without resorting to excessive energy irradiation, and without the addition of a crosslinking agent.
• the invention is based on the use of copolymers comprising units (here also called structural units, or units) derived from VDF and / or TrFE monomers as well as monomers comprising a leaving group (Br, Cl or I). Part of the leaving groups are replaced by azide groups, which allow crosslinking. This replacement can be carried out simply by reacting the polymer with an azide compound such as sodium azide. Another part of the leaving groups are retained, so that the polymer film has the advantageous properties mentioned above.
• Another advantage of the invention is that it makes it possible to obtain crosslinkable polymers from existing polymer ranges, the synthesis of which is perfectly controlled, without therefore having to develop new polymerization processes.
• Figure 1 is a graph showing the infrared absorbance spectra of polymers according to the invention and a control polymer (according to Example 1). The wavelength is indicated on the abscissa axis.
• FIG. 2 is a photograph obtained by optical microscopy of a polymer film according to the invention (according to example 2).
• the scale bar corresponds to 500 ⁇ .
• FIG. 3 represents the dielectric constant of a film according to the invention before crosslinking, after crosslinking and after development (according to Example 2).
• the frequency is indicated on the abscissa axis and the dielectric constant on the ordinate axis.
• FIG. 4 is a graph showing the polarization curves of a film according to the invention before crosslinking, after crosslinking and after development (as in Example 2). The electric field is indicated on the abscissa axis and the polarization on the ordinate axis.
• FIG. 5 is a graph showing the infrared absorbance spectra of a polymer according to the invention before and after crosslinking (according to Example 3). The wavelength is indicated on the abscissa axis.
• PF polymers fluoropolymers
• PF polymers may be used as starting polymers and modified to graft them with azide groups (-N3); the fluoropolymers thus modified are hereinafter referred to as PFM polymers.
• a polymer PF comprises units derived from VDF and / or TrFE monomers and from at least one other fluorinated monomer X comprising a double bond and a leaving group chosen from Cl, Br and I.
• the polymer PF is a P (VDF-X) copolymer. In certain variations, the polymer PF is a P (TrFE-X) copolymer.
• the polymer PF is a terpolymer
• units from several different fluorinated monomers X may be present in the polymer PF.
• units derived from one or more additional monomers in addition to those mentioned above may be present in the PF polymer.
• the PF polymer include units derived from both VDF and TrFE.
• the proportion of units derived from TrFE is preferably 5 to 95 mol% relative to the sum of the units resulting from VDF and TrFE, and in particular: from 5 to 10 mol%; or from 10 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 35 mol%; or 35 to 40 mol%; or from 40 to 45 mol%; or 45 to 50 mol%; or from 50 to 55 mol%; or from 55 to 60 mol%; or from 60 to 65 mol%; or from 65 to 70 mol%; or from 70 to 75 mol%; or from 75 to 80 mol%; or from 80 to 85 mol%; or from 85 to 90 mol%; or from 90 to 95 mol%.
• a range of 15 to 55 mol% is particularly preferred.
• the fluorinated monomer X comprises at least one fluorine atom.
• the fluorinated monomer X preferably comprises at most 5 carbon atoms, more preferably at most 4 carbon atoms, more preferably at most 3 carbon atoms, and more preferably it has 2 carbon atoms.
• the fluorinated monomer X preferably has a formula
• each X 1, X 2, X 3, X 4 group independently represents an H, F, Cl, I or Br atom, or a C 1 -C 3 (preferably C 1 -C 2) alkyl group optionally comprising one or more substituents chosen from F , Cl, I and Br.
• each X1, X2, X3, X4 group independently represents an H, F, Cl, I or Br atom, or a methyl group optionally having one or more substituents selected from F, Cl, I and Br.
• each X1, X2, X3, X4 group independently represents an H, F, Cl, I or Br atom.
• only one of the groups X1, X2, X3 and X4 represents a Cl or I or Br atom
• the other groups X1, X2, X3 and X4 independently represent: an H or F atom or an alkyl group C1-C3 optionally comprising one or more fluorine substituents; preferably, an H or F atom or a C 1 -C 2 alkyl group optionally comprising one or more fluorine substituents; and more preferably, an H or F atom or a methyl group optionally comprising one or more fluorine substituents.
• the fluorinated monomer X is chosen from bromotrifluoroethylene, chlorofluoroethylene, chlorotrifluoroethylene and chlorotrifluoropropene.
• Chlorofluoroethylene may refer to either 1-chloro-1-fluoroethylene or 1-chloro-2-fluoroethylene.
• the 1-chloro-1-fluoroethylene isomer is preferred.
• the chlorotrifluoropropene is preferably 1-chloro-3,3,3-trifluoropropene or 2-chloro-3,3,3-trifluoropropene.
• the most preferred fluorinated monomers X are chlorotrifluoroethylene (CTFE) and chlorofluoroethylene, especially 1-chloro-1-fluoroethylene (CFE).
• CTFE chlorotrifluoroethylene
• CFE 1-chloro-1-fluoroethylene
• the proportion of units derived from fluorinated monomers X in the polymer PF can vary for example from 0.5 to 1 mol%; or from 1 to 2 mol%; or from 2 to 3 mol%; or from 3 to 4 mol%; or from 4 to 5 mol%; or from 5 to 6 mol%; or from 6 to 7 mol%; or from 7 to 8 mol%; or from 8 to 9 mol%; or from 9 to 10 mol%; or from 10 to 12 mol%; or from 12 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 40 mol%; or from 40 to 50 mol%. Ranges of
• the molar composition of the units in the PF polymers can be determined by various means such as infrared spectroscopy or RAMAN spectroscopy. Conventional methods for elemental analysis in carbon, fluorine and chlorine or bromine or iodine elements, such as X-ray fluorescence spectroscopy, make it possible to calculate without ambiguity the mass composition of the polymers, from which the molar composition is deduced.
• Multi-core NMR techniques can also be performed by analyzing a solution of the polymer in a suitable deuterated solvent.
• the NMR spectrum is recorded on an FT-NMR spectrometer equipped with a multi-nuclear probe.
• the specific signals given by the various monomers are then identified in the spectra produced according to one or the other nucleus.
• the unit resulting from TrFE gives in proton NMR a specific signal characteristic of the CFH group (at about 5 ppm). It is the same for the VDF Ch groups (massive centered at 3 ppm).
• the relative integration of the two signals gives the relative abundance of the two monomers, i.e. the VDF / TrFE molar ratio.
• the -CFH- group of TrFE for example gives characteristic and well isolated signals in fluorine NMR.
• the combination of the relative integrations of the different signals obtained by proton NMR and by fluorine NMR leads to a system of equations whose resolution leads to obtaining the molar concentrations of the units resulting from the different monomers.
• the polymer PF is preferably random and linear.
• the polymer PF may be homogeneous or heterogeneous.
• a homogeneous polymer has a uniform chain structure, the statistical distribution of the units from different monomers does not vary substantially between the chains.
• the chains have a distribution in units resulting from the different monomers of multinnodal or spreading type.
• a heterogeneous polymer therefore comprises richer chains in a given unit and poorer chains in this unit.
• An example of a heterogeneous polymer is disclosed in WO 2007/080338.
• the polymer PF is an electroactive polymer.
• this maximum is called “Curie temperature” and corresponds to the transition from a ferroelectric phase to a paraelectric phase.
• This maximum temperature, or transition temperature can be measured by differential scanning calorimetry or by dielectric spectroscopy.
• the melting temperature has a melting temperature of 90 to 180 ° C, more preferably 100 to 170 ° C.
• the melting temperature can be measured by differential scanning calorimetry according to ASTM D3418.
• the polymer PF can be produced using any known method, such as emulsion polymerization, suspension polymerization and solution polymerization, it is preferable to use the method described in WO 2010/1 16105. This method makes it possible to obtain polymers of high molecular weight and suitable structuring.
• the preferred method comprises the following steps:
• the radical polymerization initiator may in particular be an organic peroxide of the peroxydicarbonate type. It is generally used in an amount of 0.1 to 10 grams per kilogram of the total monomer charge. Preferably, the amount used is 0.5 to 5 g / kg.
• the initial mixture advantageously comprises only VDF and / or TrFE in a proportion equal to that of the desired final polymer.
• the second mixture preferably has a composition which is adjusted so that the total monomer composition introduced into the autoclave, including the initial mixture and the second mixture, is equal to or approximately equal to the desired final polymer composition.
• the weight ratio of the second mixture to the initial mixture is preferably 0.5 to 2, more preferably 0.8 to 1.6.
• the pressure in the autoclave reactor is preferably from 80 to 10 bar, and the temperature is maintained preferably from 40 ° C to 60 ° C.
• the second mixture can be injected continuously into the autoclave. It can be compressed before being injected into the autoclave, for example by using a compressor or two successive compressors, generally at a pressure higher than the pressure in the autoclave.
• the polymer can be washed and dried.
• the weight average molecular weight Mw of the polymer is preferably at least 100,000 g. mol "1 , preferably at least 200000 g, mol " 1 and more preferably at least 300000 g. mol "1 or at least 400000 g mol " 1 . It can be adjusted by modifying certain process parameters, such as the temperature in the reactor, or by adding a transfer agent.
• the molecular weight distribution can be estimated by SEC (Size Exclusion Chromatography) in dimethylformamide (DMF) as an eluent, with a set of 3 columns of increasing porosity.
• the stationary phase is a styrene-DVB gel.
• the detection method is based on a measurement of the refractive index, and the calibration is performed with polystyrene standards.
• the sample is dissolved in 0.5 g / l in DMF and filtered through a 0.45 ⁇ m nylon filter.
• the PFM polymer can be made from a PF polymer by reaction with an azide compound.
• the PFM polymer comprises azide groups embedded in the polymer chain in the form of -CC (X) N3-C- units, where X represents a hydrogen or halogen atom or an alkyl group, substituted or unsubstituted. no, and preferably X is H or F.
• Possible azide compounds for the reaction include compounds of the formula M ( N 3 ) n wherein M represents a monovalent or multivalent cation or H or halogen (I, Br or Cl) or a pseudohalogen (especially CN), and n represents an integer.
• M represents a monovalent or multivalent cation or H or halogen (I, Br or Cl) or a pseudohalogen (especially CN), and n represents an integer.
• M is a cation and n is the valency of the cation.
• M may especially be a metal cation or an ammonium cation (or a derivative, such as a tetraalkylammonium cation).
• Monovalent metal cations potassium or sodium, for example
• divalent calcium or magnesium for example
• the azide compound is preferably selected from sodium azide NaN 3 and potassium azide KN 3. Sodium azide is particularly preferred.
• the conversion of the polymer PF into a PFM polymer can be carried out by bringing the polymer PF and the azide compound in the presence of a solvent in which the polymer PF is dissolved.
• dimethylformamide As a solvent, it is especially possible to use dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone (or butan-2-one), methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate. Mixtures of these compounds can also be used.
• the concentration of polymer PF introduced into the reaction medium may be, for example, from 1 to 200 g / l, preferably from 5 to 100 g / l, more preferably from 10 to 50 g / l.
• the amount of azide compound introduced into the reaction medium can be adjusted according to the degree of replacement of the leaving groups by the azide groups which is desired. Thus, this amount may be from 0.1 to 0.2 molar equivalents (of azide groups introduced into the reaction medium, relative to the leaving groups present in the polymer PF); or from 0.2 to 0.3 molar equivalents; or from 0.3 to 0.4 molar equivalents; or from 0.4 to 0.5 molar equivalents; or from 0.5 to 0.6 molar equivalents; or from 0.6 to 0.7 molar equivalents; or from 0.7 to 0.8 molar equivalents; or from 0.8 to 0.9 molar equivalents; or from 0.9 to 1.0 molar equivalents; or from 1.0 to 1.5 molar equivalents; or from 1.5 to 2 molar equivalents; or from 2 to 5 molar equivalents; or from 5 to 10 molar equivalents; or from 10 to 50 molar equivalents.
• the reaction is preferably carried out with stirring.
• the reaction is preferably carried out at a temperature of 20 to 80 ° C, more preferably 30 to 70 ° C, and more preferably 40 to 65 ° C.
• the reaction time may be, for example, 15 minutes to 48 hours, preferably 1 hour to 36 hours, more preferably 2 to 24 hours.
• the PFM polymer can be precipitated in a non-solvent, for example deionized water. It can then be filtered and dried.
• a non-solvent for example deionized water.
• the composition of the PFM polymer can be characterized by elemental analysis and NMR, as described above, as well as by infrared spectrometry. In particular, a valence vibration band characteristic of the azide function is observed around 2150 cm -1 .
• the composition of the PFM polymer in azide groups can be characterized by differential scanning calorimetry, preferably modulated, by correlating the enthalpy of the exothermic reaction of the azide groups with the results of the elemental analysis and / or the NMR, during the first rise in temperature.
• all of the leaving groups of the starting polymer PF have been replaced by -N3 azide groups in the PFM polymer.
• the leaving groups of the starting polymer PF have only been partially replaced by azide groups in the PFM polymer.
• the molar proportion of leaving groups (for example of Cl groups, in the case of using CTFE or CFE) replaced by azide groups may be from 5 to 10 mol%; or from 10 to 20 mol%; or from 20 to 30 mol%; or from 30 to 40 mol%; or from 40 to 50 mol%; or from 50 to 60 mol%; or from 60 to 70 mol%; or from 70 to 80 mol%; or from 80 to 90 mol%; or from 90 to 95 mol%; or more than 95 mol%.
• the proportion of residual structural units comprising a leaving group can be, for example, from 0.1 to 0.5 mol%; or from 0.5 to 1 mol%; or from 1 to 2 mol%; or from 2 to 3 mol%; or from 3 to 4 mol%; or from 4 to 5 mol%; or from 5 to 6 mol%; or from 6 to 7 mol%; or from 7 to 8 mol%; or from 8 to 9 mol%; or from 9 to 10 mol%; or from 10 to 12 mol%; or from 12 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 40 mol%; or from 40 to 50 mol%. Ranges of 1 to 15 mol%, and preferably 2 to 10 mol%, are particularly preferred.
• the proportion of structural units comprising an azide group can be, for example, from 0.1 to 0.5 mol%; or from 0.5 to 1 mol%; or from 1 to 2 mol%; or from 2 to 3 mol%; or from 3 to 4 mol%; or from 4 to 5 mol%; or from 5 to 6 mol%; or from 6 to 7 mol%; or from 7 to 8 mol%; or from 8 to 9 mol%; or from 9 to 10 mol%; or from 10 to 12 mol%; or from 12 to 15 mol%; or from 15 to 20 mol%; or from 20 to 25 mol%; or from 25 to 30 mol%; or from 30 to 40 mol%; or from 40 to 50 mol%. Ranges of 1 to 15 mol%, and preferably 2 to 10 mol%, are particularly preferred.
• a fluoropolymer film according to the invention may be prepared by depositing on a substrate: one or more PFM polymers only; at least one PF polymer and at least one PFM polymer.
• the monomers containing leaving groups used for the manufacture of the polymer PF are the same as those used for the manufacture of the PFM polymer.
• the mass proportion of polymer (s) PF relative to all of the PF and PFM polymers may be in particular 5 to 10%; or 10 to 20%; or from 20 to 30%; or from 30 to 40%; or 40 to 50%; or 50 to 60%; or 60 to 70%; or 70 to 80%; or 80 to 90%; or 90 to 95%.
• the manufacture of the film may comprise a step of depositing PFM polymers (or PFM and PF) on a substrate, followed by a crosslinking step.
• the PFM (or PFM and PF) polymers may also be combined with one or more other polymers, especially fluorinated polymers, such as, in particular, a P (VDF-TrFE) copolymer.
• the substrate may in particular be a surface of glass, or of silicon, or of polymeric material, or of metal.
• a preferred method is to dissolve or suspend the polymer (s) in a liquid vehicle, to form a so-called ink composition before depositing it on the substrate.
• the liquid vehicle is a solvent.
• this solvent is chosen from: dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate. Mixtures of these compounds can also be used.
• the total mass concentration of polymers in the liquid carrier may be in particular from 0.1 to 30%, preferably from 0.5 to 20%.
• the ink may optionally comprise one or more additives, especially chosen from modifying agents for surface tension, modifying agents for rheology, modifying agents for holding the aging, adhesion modifiers, pigments or dyes, fillers (including nanofillers).
• Preferred additives include co-solvents modifying the surface tension of the ink. In particular, it may be, in the case of solutions, organic compounds miscible with the solvents used.
• the ink composition may also contain one or more additives used for the synthesis of the polymer (s).
• the ink comprises at least one crosslinking aid additive, preferably a photoinitiator and / or a crosslinking agent.
• the photoinitiator may for example be chosen from 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2,4,6-trimethylbenzoyl-diphenylphosphineoxide, diphenylphosphine oxide, 2 , 4,6-trimethylbenzoylphenyltrimethylbenzoylphenyl phosphinate, 1-hydroxy-cyclohexyl-phenylphenylketone, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 1- [4- (2- hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propanepropan-1-one, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1 [4- (methylthio) ) phenylphenyl] -2-morpholinopropan-1-one, 2,4-diethylthioxanthonediethylthioxanthone, their
• the crosslinking agent may for example be chosen from molecules, oligomers, and polymers bearing at least two reactive double bonds, such as triallylisocyanurate (TAlC), bi- or poly (meth) acrylic compounds, polybutadiene ; compounds bearing at least two reactive triple bonds of carbon-carbon or carbon-nitrogen type such as tripropargyl amine; their derivatives, and mixtures thereof.
• TlC triallylisocyanurate
• bi- or poly (meth) acrylic compounds such as polybutadiene
• compounds bearing at least two reactive triple bonds of carbon-carbon or carbon-nitrogen type such as tripropargyl amine
• no crosslinking aid additive such as a photoinitiator or a crosslinking agent, is present in the ink deposited on the substrate.
• the deposition may be carried out in particular by coating by centrifugation ("spin-coating”), by spraying or atomizing (“spray coating”), by coating, in particular with a bar or a film-dragger (“bar coating”), by immersion ( Dip coating), by roll-to-roll printing, by screen printing or by lithographic printing or by ink jet printing.
• the liquid vehicle is evaporated after the deposit.
• the fluoropolymer layer thus formed may have in particular a thickness of 50 nm to 50 ⁇ m, preferably 100 nm to 5 ⁇ m, more preferably 150 nm to 1 ⁇ m, more preferably 200 nm to 500 nm.
• the crosslinking step may be carried out in particular by heat treatment and / or by UV irradiation.
• UV irradiation is particularly advantageous in the case where only a part of the polymer film must be crosslinked, in a predetermined pattern, since a mask can then be used to protect the portions of the film that are not intended to be crosslinked.
• the heat treatment can be carried out by subjecting the film for example to a temperature of 50 to 150 ° C, preferably 60 to 130 ° C, for example in a ventilated oven or on a hot plate.
• the duration of the heat treatment may especially be from 1 minute to 1 hour, preferably from 2 to 15 minutes.
• UV irradiation means irradiation with electromagnetic radiation at a wavelength of 200 to 650 nm, and preferably 220 to 500 nm. Wavelengths of 250 to 450 nm are particularly preferred.
• the radiation can be monochromatic or polychromatic.
• the total dose of the UV irradiation is preferably less than or equal to 40 J / cm 2 , more preferably less than or equal to 20 J / cm 2 , more preferably less than or equal to 10 J / cm 2 , more preferably less than or equal to 5 J / cm 2 , more preferably less than or equal to 3 J / cm 2 .
• a low dose is advantageous to avoid degrading the surface of the film.
• the treatment is carried out essentially in the absence of oxygen, always in order to avoid any degradation of the film.
• the treatment can be carried out under vacuum, or in an inert atmosphere, or by protecting the film from ambient air with a physical barrier impermeable to oxygen (glass plate or polymer film for example).
• a thermal pre-treatment and / or a thermal post-treatment, before and / or after the UV irradiation, can be carried out.
• the heat pretreatment and the heat post-treatment can in particular be carried out at a temperature of 40 to 80.degree. 50 to 70 ° C, and for example about 60 ° C for a period of less than 30 minutes, preferably less than 15 minutes.
• a development step can then be performed, so as to remove the uncrosslinked portions of the film and to reveal the desired geometric pattern for the film.
• the development can be carried out by contacting the film with a solvent, preferably by immersion in a solvent bath.
• the solvent may preferably be chosen from dimethylformamide; dimethylacetamide; dimethylsulfoxide; ketones, especially acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclopentanone; furans, especially tetrahydrofuran; esters, especially methyl acetate, ethyl acetate, propyl acetate, butyl acetate and propylene glycol methyl ether; carbonates, especially dimethyl carbonate; phosphates, especially triethylphosphate. Mixtures of these compounds can also be used.
• non-solvent liquid may in particular be any solvent which is different from the following solvents: dimethylformamide; dimethylacetamide; dimethyl sulfoxide; ketones; furans; esters; carbonates; phosphates.
• a protic solvent that is to say a solvent comprising at least one H atom bonded to an O atom or to an N atom.
• an alcohol such as ethanol or isopropanol
• Non-solvent mixtures may also be used.
• the presence of a non-solvent in combination with the solvent can make it possible to further improve the sharpness of the patterns obtained, compared with the assumption that the non-solvent is used only during rinsing.
• the development may preferably be carried out at a temperature of 10 to 100 ° C, preferably 15 to 80 ° C, and more preferably 20 to 60 ° C.
• the development time is preferably less than 15 minutes, more preferably less than 10 minutes.
• the film may be rinsed with a non-solvent liquid for the fluoropolymer.
• a non-solvent liquid for the fluoropolymer may be in particular a protic solvent, that is to say a solvent comprising at least one H atom linked to a O atom or N atom.
• a protic solvent that is to say a solvent comprising at least one H atom linked to a O atom or N atom.
• an alcohol such as ethanol or isopropanol
• deionized water can be used.
• Non-solvent mixtures may also be used. This rinsing step improves the sharpness of the film patterns.
• the rinsing may be carried out in particular by spraying the non-solvent on the crosslinked PFM film. Rinsing can also be performed by immersion in a non-solvent bath.
• the temperature during rinsing may be from 5 to 80 ° C, more preferably from 10 to 70 ° C and particularly at room temperature from 15 to 35 ° C.
• the duration of the rinsing step is less than 10 minutes, more preferably less than 5 minutes and particularly less than 1 minute.
• the film may be dried under air, and optionally undergo a post-crosslinking heat treatment, by exposing it to a temperature ranging for example from 30 to 150 ° C, preferably from 50 to 140 ° C.
• the film according to the invention is preferably characterized by a dielectric constant (or relative permittivity) at 1 kHz and at 25 ° C. which is greater than or equal to 10, more preferably greater than or equal to 15, more preferably greater than or equal to at 20, more preferably greater than or equal to 25.
• the measurement of the dielectric constant can be carried out using an impedance meter able to measure the capacity of the material knowing the geometric dimensions (thickness and facing surfaces). Said material is disposed between two conductive electrodes.
• the film according to the invention can be used as a layer in an electronic device.
• one or more additional layers may be deposited on the substrate provided with the film of the invention, for example one or more layers of polymers, semiconductor materials, or metals, in a manner known per se.
• the term electronic device is either a single electronic component or a set of electronic components, capable (s) to perform one or more functions in an electronic circuit.
• the electronic device is more particularly an optoelectronic device, that is to say capable of emitting, detecting or controlling electromagnetic radiation.
• electronic devices, or possibly optoelectronic devices, concerned by the present invention are transistors (in particular field effect), chips, batteries, photovoltaic cells, light-emitting diodes (LEDs), organic light-emitting diodes ( OLED), sensors, actuators, transformers, haptic devices, electromechanical microsystems, electro-caloric devices and detectors.
• the film according to the invention can be used in a field effect transistor, in particular an organic field effect transistor, as a layer or part of the dielectric layer.
• Electronic and optoelectronic devices are used and integrated in many electronic devices, equipment or subassemblies and in many objects and applications such as televisions, mobile phones, rigid or flexible screens, thin-film photovoltaic modules, lighting sources, energy sensors and converters, etc.
• Example 1 manufacture of a modified polymer according to the invention
• VDF-TrFE-CTFE A P terpolymer (VDF-TrFE-CTFE) is used as the starting material.
• This terpolymer contains 61.8 mole% of units derived from VDF, 30.4 mole% of units derived from TrFE and 7.8 mole% of units derived from CTFE.
• terpolymer powder 1.2 g are dissolved in 50 ml of dimethylformamide. 39 mg (0.5 molar equivalents, based on the number of moles of CTFE) of NaN 3 are then added to the reaction medium. The reaction is maintained at 55 ° C for 12 h. The product is recovered after precipitation in deionized water. It is then filtered and dried at 40 ° C. under vacuum for 24 hours.
• the infrared spectrum of the various polymers is obtained with a Fourier transform infrared spectrometer (IRTF) in ATR mode (reflection) directly on the polymer film:
• IRTF Fourier transform infrared spectrometer
• a 7% by weight formulation in butan-2-one is made by mixing 50/50 by weight of an unmodified P (VDF-TrFE-CTFE) terpolymer containing 7.8 mol. % of units from CTFE with another terpolymer P (VDF-TrFE-CTFE) initially containing 12.7 mol. % of units from the CTFE and modified in the same way as in Example 1 with
• a 250 nm film is made on a spin-silicon substrate from the previously prepared formulation. It is then dried at 60 ° C for 5 min.
• crosslinking of the film according to a predefined pattern is carried out by irradiation
• UV (with mainly wavelengths of 300 to 400 nm), the dose administered being 20 J / cm 2 .
• the film is then developed by rinsing in cyclopentanone at room temperature for 1 minute.
• the pattern obtained is visible in the photograph of Figure 2.
• the dark areas are those where the polymer is present.
• the pattern has good resolution.
• the results are visible in the graphs of FIGS. 3 and 4.
• the graph of FIG. 3 illustrates the stability of the dielectric properties of the film during the process.
• the graph in FIG. 4 describes the evolution of the polarization curves during the different stages of manufacture of the film. A high saturation polarization is observed for the film C, crosslinked and developed.
• Example 3 Production of a Film According to the Invention by Heat Treatment
• the modified polymer of Example 1 obtained with 0.5 molar equivalent of NaNs
• a film is produced from this polymer.
• the film has a thickness of 2 ⁇ . It is made on a spin and dried at 60 ° C for 5 min.
• the infrared spectrum of the film is measured before and after crosslinking.
• the crosslinking is carried out thermally at 125 ° C for 20 minutes.

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