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    • 专利摘要:
    The present invention relates to the use of a fluorinated copolymer in the manufacture of a solid polymeric film, to impart to said film adhesion properties on a metal surface or on glass. It also relates to a method for improving the adhesion to a metal or vitreous substrate of a fluorinated polymer, as well as a composite part comprising a solid polymer film in direct contact with at least one metallic or vitreous element.
    公开号:FR3047008A1
    申请号:FR1650548
    申请日:2016-01-25
    公开日:2017-07-28
    发明作者:Thierry Lannuzel；Dos Santos Fabrice Domingues；Thibaut Soulestin；Vincent Ladmiral；Bruno Ameduri
    申请人:Centre National de la Recherche Scientifique CNRS；Universite de Montpellier I；Arkema France SA；Ecole Nationale Superieure de Chimie de Montpellier ENSCM；Universite de Montpellier；
    IPC主号:
    专利说明:

    USE OF A VINYLIDENE FLUORIDE COPOLYMER FOR CONFINING A FILM OF PROPERTIES
    MEMBERSHIP
    FIELD OF THE INVENTION
    The present invention relates to the use of a fluorinated copolymer in the manufacture of a solid polymeric film, to impart to said film adhesion properties on a metal surface or on glass. It also relates to a method for improving the adhesion to a metal or vitreous substrate of a fluorinated polymer, as well as a composite part comprising a solid polymer film in direct contact with at least one metallic or vitreous element.
    TECHNICAL BACKGROUND
    Metallized polymer films have many applications, especially in the manufacture of electrically conductive devices. Among the polymers that can be used, fluorinated polymers based in particular on vinylidene fluoride (VDF) represent a class of compounds having remarkable properties for a large number of applications. P VDF and copolymers comprising VDF and trifluoroethylene (TrFE) are particularly interesting because of their piezoelectric properties. They can thus be used for the manufacture of various electroactive equipment, such as actuators or sensors, generally comprising a film of the polymer sandwiched between two electrodes.
    Conversely, it is known to apply a polymer film to a metal substrate, in particular for the purpose of giving it corrosion resistance. It has also been suggested to use VDF-based polymers for this purpose as long as they have good barrier and weather-resistant properties.
    It is understood that in these different applications, an essential condition for obtaining the desired result is the good adhesion of the polymer to the metal.
    However, it has been observed that PVDF and copolymers of VDF have, due to their hydrophobic character, insufficient adhesion to metals.
    To remedy this problem, it has been proposed to mix PVDF with copolymers improving its compatibility with metals, especially methyl methacrylate copolymerized with monomers bearing phosphonic acid functions (C. Bressy-Brondino et al., J. Appl Polym Sci., 2002, 8, 2277-2287). These additives, however, modify the properties of PVDF and in particular its dielectric activity. Alternatively, it has been suggested to interpose a layer of these copolymers between the metal substrate and the PVDF film (US 2010/0057189). This approach is also not suitable for the formation of electroactive devices, in which the electroactive fluoropolymers must be in direct contact with the metal surface to limit the dielectric losses.
    Another solution consisted in grafting acidic monomers onto PVDF previously oxidized by ozonation (Brondino et al., J. Appl Polym Sci., 1999, 72, 611-620). This technique is, however, likely to cause degradation of the polymer chains during the ozonation step. Similarly, it has been proposed to copolymerize vinylidene fluoride with perfluorinated vinyl ethers (Yamabe et al., Euro Polym J., 2000, 36, 1035-1041) or with vinyl esters such as acetate vinyl (WO 2014/149911) or with a glycidyl ether type epoxy monomer combined with a maleic acid monoester used as crosslinking agent (EP 0 751 157). If this approach improves the adhesion of the polymer, it has the disadvantage of modifying its properties and in particular its electroactivity properties.
    VDF copolymers are also known with monomers bearing phosphonic acid functional groups, such as vinylphosphonic acid (WO 2012/030784, US2012 / 0184653 and WO 2014/162080). However, it has never been suggested, to the knowledge of the Applicant, that such copolymers have a remarkable adhesion to metals and / or glass.
    SUMMARY OF THE INVENTION
    There remains the need for a simple, economically advantageous and effective means for imparting good adhesion of VDF-based polymers to polar hydrophilic surfaces such as metal surfaces and glass, without significantly modifying the properties of these polymers and especially their thermal properties and their electroactivity.
    It has been found that this need could be met by copolymerizing the VDF with an adhesion promoter monomer which consists of a non-perfluorinated vinyl or vinylenic monomer carrying at least one weak acidic function or weak acid precursor. It is thus possible to envisage the use of these copolymers in the manufacture of polymer films intended to be assembled with metal parts in order to obtain various composite parts. The invention thus relates to the use of a fluorinated copolymer in the manufacture of a solid polymer film, for imparting to said film adhesion properties on a metal surface or on glass, characterized in that said copolymer is obtained by (a) radical copolymerization of monomers comprising, and preferably consisting of: (i) at least one fluorinated monomer chosen from vinylidene fluoride (VDF) and trifluoroethylene (TrFE), (ii) optionally at least one other monomer fluorine and (iii) an adhesion promoter monomer which is a non-perfluorinated vinyl or vinylenic monomer bearing at least one weak acid function or a weak acid precursor, with the exception of the carboxyvinyl, carboxyvinylene, 1-alkyl- carboxyvinyl, 1-alkylcarboxyvinylene and their precursors, and (b) when present, conversion of the weak acid precursor functions to weak acid functions . The subject of the invention is also a process for improving the adhesion to a metal or vitreous substrate of a fluorinated polymer obtained from at least one fluorinated monomer chosen from vinylidene fluoride (VDF) and trifluoroethylene (TrFE). and optionally at least one other fluorinated monomer, characterized in that it comprises introducing into said fluoropolymer units resulting from the radical copolymerization of a non-perfluorinated vinyl or vinylenic monomer carrying at least one weak acid function or weak acid precursor, except carboxyvinyl, carboxyvinylene, 1-alkyl-carboxyvinyl, 1-alkylcarboxyvinylene monomers and their precursors, and the conversion of the weak acid to weak acid precursor function when it is present.
    It also relates to a composite part comprising a solid polymer film in direct contact with at least one metallic or vitreous element, characterized in that said film is made from a copolymer obtained by: (a) radical copolymerization of monomers comprising and preferably consisting of: (i) at least one fluorinated monomer selected from vinylidene fluoride (VDF) and trifluoroethylene (TrFE), (ii) optionally at least one other fluorinated monomer and (iii) a monomer promoting adhesion which is a non-perfluorinated vinyl or vinylenic monomer carrying at least one weak acidic function or weak acid precursor, with the exception of carboxyvinyl, carboxyvinylene, 1-alkylcarboxyvinyl, 1-alkylcarboxyvinylene monomers and their precursors, and (b) when present, conversion of the weak acid precursor functions to weak acid functions.
    It has been observed that the introduction of the above-mentioned adhesion promoter monomer into fluorinated polymers, including in amounts as small as 1 mol% or less, makes it possible to considerably increase the adhesion of these polymers to metal surfaces without modifying substantially their thermal stability, in particular their degradation temperature at 5% mass loss, determined by thermogravimetric analysis, their dielectric properties, and in particular their Curie temperature, measured by differential scanning calorimetry, as well as their semi-crystalline character, determined by their melting temperature and their enthalpy of fusion. In addition, these copolymers have a polarization curve similar to that of polymers lacking adhesion promoting monomer, namely the same remanent polarization, the same coercive field and the same hysteresis. As a result, the range of uses of the fluoropolymers, modified according to the invention by the introduction of an adhesion promoter monomer, is not limited by the introduction of this monomer.
    BRIEF DESCRIPTION OF THE FIGURES
    Figure 1 illustrates the radical terpolymerization of VDF with TrFE and DMVP and the hydrolysis of the obtained terpolymer.
    FIG. 2 is a 1H NMR spectrum (recorded at 20 ° C. in acetone-d6) making it possible to observe the different types of protons present in the poly (VDF-ter-TrFE-Zer-DM VP) terpolymers prepared according to US Pat. Example 1 (bottom) and poly (VDF-ter-TrFE-iron-VPA) prepared according to Example 2 (top).
    FIG. 3 is a 19F NMR spectrum (recorded at 20 ° C. in acetone-d6) making it possible to observe the different types of fluorine atoms present in the poly (VDF-iron-TrFE-iron-DMVP) terpolymer prepared according to Example 1.
    FIG. 4 represents an ATG thermogram at 10 ° C./min, in air, of the poly (VDF-ter-TrFE-ter-DMVP) terpolymer prepared according to Example 1.
    FIG. 5 represents superimposed ATG thermograms, at 10 ° C./min, in air, of the poly (VDF-ter-TrFE-iron-DMVP) terpolymer prepared according to Example 1 and of a comparative copolymer devoid of DMVP units.
    Figure 6 shows a DSC thermogram of the poly (VDF- / tr-TrFE-ter-DMVP) terpolymer prepared according to Example 1.
    FIG. 7 shows the superimposed DSC thermograms of a poly (VDF-iron-TrFE-ter-VPA) terpolymer prepared according to Example 2 (bottom curve) of a poly (VDF-ter-TrFE-terpolymer terpolymer). DMVP) prepared according to Example 1 (middle curve) and a comparative copolymer devoid of DMVP patterns (top curve). FIG. 8 is a RM NMR spectrum (recorded at 20 ° C. in acetone-de) for observing the different types of protons present in the poly (VDF-iron-TrFE-ter-MAF) terpolymer prepared according to US Pat. Example 3
    FIG. 9 is a 19F NMR spectrum (recorded at 20 ° C. in acetone-de) for observing the different types of fluorine atoms present in the poly (VDF-ter-TrFE-ter-MAF) terpolymer prepared according to Example 3.
    Figure 10 illustrates the appearance of films prepared with Poly copolymer (VDF-co-TrFE) (left), Poly terpolymer (VDF-ter-TrFE-ter-DMVP) (center) and Poly terpolymer (VDF). -ter-TrFE-ter-VPA) (right), respectively, when applied to an aluminum foil.
    DESCRIPTION OF EMBODIMENTS OF THE INVENTION The invention will now be described in more detail and in a nonlimiting manner in the description which follows. The invention relates to the use of a fluorinated copolymer in the manufacture of a solid polymer film, to impart to said film adhesion properties on a metal surface or on glass.
    The fluorinated copolymer used in this invention comprises at least one unit derived from a fluorinated monomer chosen from vinylidene fluoride (VDF) and trifluoroethylene (TrFE), preferably a mixture of these units. H also optionally contains at least one other fluorinated monomer, which may be chosen in particular from: tetrafluoroethylene (TFE), chlorofluoroethylene (CFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoropropene, tetrafluoropropene, chloro-trifluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, perfluoroethers such as PMVE and PPVE, and mixtures thereof. It is understood that all the geometric isomers of the aforementioned fluorinated compounds are included in the above terminologies, such as 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene (or 1234yf), 3 chloro-2,3,3-trifluoropropene (or 1233yf) and 3-chloro-3,3,3-trifluoropropene. Preferably, when present, said other fluorinated monomer is selected from CFE and CTFE.
    This fluoro homopolymer or copolymer does not in itself exhibit good adhesion properties on polar hydrophilic surfaces such as metal surfaces or glass. To give this polymer the desired adhesion properties, patterns derived from an adhesion promoter monomer are introduced into this polymer. To do this, the aforementioned monomers are copolymerized, by radical copolymerization, with an adhesion promoter monomer which is a non-perfluorinated vinyl or vinylenic monomer carrying at least one weak acidic function or weak acid precursor. In the case where the adhesion promoter monomer carries a weak acid precursor function, the copolymerization step is followed by a step of converting the weak acid precursor functions into weak acid functions.
    The weak acid function of the adhesion promoter monomer is advantageously chosen from a carboxylic acid function and a phosphonic acid function. When this monomer carries several (usually two or three) weak acid functions, these may be the same or different. In a preferred embodiment of the invention, the adhesion promoter monomer carries a single weak acid function.
    It should be noted that this monomer is distinct from a carboxyvinyl, carboxyvinylene, 1-alkyl-carboxyvinyl, 1-alkylcarboxyvinylene monomer and their precursors. Thus, acrylic acid, methacrylic acid and their esters are not included among the adhesion promoter monomers useful in the present invention. In the case where the adhesion promoter monomer carries a carboxylic acid function, it is preferred that this carboxylic acid function be carried on a vinyl monomer bearing an electron withdrawing group such as a trifluoromethyl group.
    According to a particular embodiment of the invention, the adhesion promoter monomer carries at least one weak acid precursor function, in particular a carboxylic acid precursor or, more preferably, a phosphonic acid precursor. Such precursors are, in particular, carboxylic acid salts and alkyl esters and phosphonic acid salts and alkyl esters. In the present invention, it is preferred to use phosphonic acid alkyl esters. Examples of such functions are the monoalkyl ester and dialkyl ester functions and preferably phosphonic acid dialkyl esters, such as methyl, ethyl or isopropyl phosphonic acid esters, more particularly the phosphonic acid methyl esters. A vinyl monomer carrying such functions is in particular vinylphosphonic acid dimethyl ester (DMVP).
    It is understood that the adhesion promoter monomer can carry both a weak acidic function and a weak acid precursor function, chosen from those described above.
    The preferred adhesion promoter monomers according to this invention are chosen from a dialkyl ester of vinylphosphonic acid, in particular vinylphosphonic acid dimethyl ester, vinylphosphonic acid and (2-trifluoromethyl) acrylic acid.
    The molar mass of the adhesion promoter monomer is for example between 100 and 250 g / mol, preferably between 100 and 200 g / mol.
    The adhesion promoting monomer may be introduced into the fluoropolymer in any molar amount so long as it does not substantially affect the thermal, mechanical or electrical properties of the copolymer. For obvious economic reasons, however, the molar percentage of the unit derived from this monomer within the copolymer will generally not exceed an amount sufficient to achieve the desired adhesion properties. Thus, it is preferred according to this invention that the molar proportion of the units derived from the adhesion promoter monomer represents less than 1% of the copolymer, preferably from 0.5 to 0.8% of the copolymer.
    According to one embodiment, the copolymer according to the invention has the following composition (in moles): a proportion of units derived from vinylidene fluoride of 40 to 95%, preferably from 50 to 85%; a proportion of units derived from an additional fluorinated monomer of 0 to 15%, a proportion of trifluoroethylene units of from 5 to 60%, preferably from 15 to 50%; and a proportion of units derived from the adhesion promoter monomer of from 0.1 to 5%, preferably from 0.5 to 2% and more preferably from 0.5 to 0.8%.
    The copolymers used according to the invention are advantageously statistical and linear.
    The copolymerization reaction is generally carried out in the presence of a radical initiator. This may for example be a t-alkyl peroxyester such as tert-butyl peroxypivalate (or TBPPI), tert-amyl peroxypivalate, a peroxydicarbonate such as bis (4-tert-butylcyclohexyl) peroxydicarbonate, sodium, ammonium or potassium persulfates, benzoyl peroxide and its derivatives, a t-alkyl hydroperoxide such as tert-butyl hydroxyperoxide, a t-alkyl peroxide such as tert-butyl peroxide or a t-alkyl-peroxyalkane such as 2,5-bis (tert-butylperoxy) -2,5-dimethylhexane. Alternatively or additionally, azo initiator or redox system can be used as the radical initiator.
    According to one embodiment, the copolymerization can be carried out in the presence of a dispersing agent. This may be for example a water-soluble cellulose derivative, such as alkyl celluloses or alkyl hydroxyalkyl celluloses, a paraffin, polyvinyl alcohols and mixtures thereof.
    According to one embodiment, the copolymerization can be carried out in the presence of a chain transfer agent for regulating the molar mass of the copolymer, in particular with a view to facilitating its implementation. The molar mass regulating agents may be, for example, alkyl acetates such as ethyl acetate, bisalkyl carbonates such as diethyl carbonate, ketones such as butan-2-one, thiols, thiols and the like. alkyl halides, saturated alcohols such as isopropanol and alkanes such as propane.
    Finally, the reaction medium may comprise one or more pH adjusting agents.
    According to a first embodiment, the copolymer used according to the invention is prepared by a solution radical polymerization process, comprising a step of copolymerizing a reaction mixture of fluorinated monomer (s) and of a monomer promoter of adhesion in the presence of a radical initiator in a solvent.
    According to a particular embodiment: the molar proportion of VDF in the reaction mixture is 40 to 95%, preferably 50 to 85%; The molar proportion of TrFE in the reaction mixture is from 5 to 60%, preferably from 15 to 50%; The molar proportion of additional fluorinated monomer in the reaction mixture is from 0 to 15%, and the molar proportion of adhesion promoter monomer in the reaction mixture is from 0.1 to 5%, preferably from 0.5 to 2% and more preferably from 0.5 to 0.8%, the molar proportions being based on the sum of the moles of the monomers.
    According to one embodiment, the reaction mixture consists essentially of, and preferably consists of, a mixture of vinylidene fluoride and / or trifluoroethylene with the adhesion promoter monomer and optionally at least one other fluorinated monomer, of radical initiator , and solvent. By "essentially consists" is meant that it contains at least 70 mol%, more preferably at least 80 mol%, for example at least 90 mol%, or even at least 95 mol%, of these constituents.
    The reaction is carried out in a solvent, which is for example selected from a halogenated organic solvent such as 1,1,1,3,3-pentafluorobutane, 2,2,2-trifluoroethanol, hexafluoroisopropanol; acetonitrile; a ketone such as methyl ethyl ketone or cyclohexanone; a carbonate such as dimethyl carbonate; an ester such as methyl acetate, ethyl acetate; water and mixtures thereof.
    According to one embodiment, the reaction mixture is heated to a reaction start temperature of between 20 and 100 ° C and preferably between 25 and 80 ° C. The initial pressure inside the autoclave varies depending on the solvent, the temperature of the reaction and the amount of monomers. It is generally between 0 and 80 bars, for example between 20 and 40 bars. The choice of the optimum temperature depends on the initiator that is used. Generally, the reaction is carried out for a duration equal to two to four times the half-life of the initiator used, for example from 6 hours to 25 hours, at a temperature at which the half-life time of the initiator is between 1 and 10 hours.
    The molar mass of the copolymer obtained by solution polymerization is preferably from 5,000 to 200,000 g / mol, more preferably from 10,000 to 150,000 g / mol.
    According to another embodiment, said terpolymer is prepared by a radical polymerization in suspension process, comprising a step of copolymerizing a reaction mixture of the monomers in the presence of water, a radical initiator, optionally a surfactant, dispersion and, optionally, a chain transfer agent.
    The suspension process makes it possible to avoid the use of toxic solvents and fluorinated surfactants (PFOA or PFOS type bioaccumulative, toxic and persistent) during the synthesis and purification of the copolymer.
    In the slurry process, the monomers are charged to a stirred reactor containing deionized water, optionally a dispersing agent and, optionally, a chain transfer agent.
    The reactor is then brought to the desired initiation temperature, this temperature being maintained during the polymerization at a value between 40 and 60 ° C. The initiator is then injected into the reactor to start the polymerization. The pressure is generally maintained in the range of 80 to 110 bar by injection of deionized water or a mixture of monomers. The consumption of the monomers leads to a decrease in pressure which is compensated by a continuous supply of water. The pressure is thus maintained in a range from 80 to 110 bar. The reactor is then cooled and degassed. The product is unloaded and recovered as a slurry. This suspension is filtered and the wet powder is washed and then dried.
    The suspension polymerization process is simplified because it allows continuous injection of only water to maintain the pressure in the reactor.
    According to yet another embodiment, the terpolymer used according to the invention is prepared according to a radical emulsion polymerization process.
    To do this, an aqueous dispersion of the initiator stabilized with the surfactant used to carry out the polymerization is advantageously prepared. To achieve this dispersion, the water, the initiator and a small fraction of the totality of the surfactant are mixed in a disperser. It is this dispersion which is added at the beginning and then possibly during the polymerization. After loading the polymerization reactor with water, surfactant and possibly paraffin, the reactor is pressurized after having removed the oxygen, by adding vinylidene fluoride alone or as a mixture with the comonomers, and the reaction mixture is heated. the chosen temperature. Advantageously, the aqueous emulsion is polymerized at a temperature of 50 to 130 ° C. Preferably, the polymerization is carried out at an absolute pressure of 40 to 120 bar. The start of the reaction is obtained by adding the initiator dispersion. During the polymerization, VDF is optionally added alone or in mixture with the comonomers to maintain the pressure or to obtain a controlled pressure variation. The initiator is optionally added in increments or continuously. A chain transfer agent (CTA) may optionally be added at the beginning or during the polymerization. In the latter case, it can be introduced incrementally or continuously. After introducing the expected amount of VDF or monomer mixture, the reactor is degassed and cooled and the latex is drained.
    Recovery of the polymer from the latex is the finishing operation. This essentially consists of coagulating the latex and then drying the coagulai to obtain a dry powder. The finish may also include a washing step. This washing may, for example, be carried out by introducing the latex, optionally diluted, into a coagulator where it is subjected to shear in the presence of air. Under the cumulative effect of these two actions, the latex is transformed into aerated cream with a density lower than that of water. This cream is optionally backwashed with deionized water, for example according to the process described in US Pat. No. 4,128,517 and EP 0 460 284. The drying can be carried out according to any industrial means known to the man of the invention. art. In particular, the coagulated latex or cream can be advantageously dried in an atomizer. Thus, at the exit of the washing column or immediately after coagulation, the aerated cream is sent into a storage container before being pumped into an atomizer which transforms it into a dry powder. This drying step in an atomizer can also be applied to the initial latex, optionally diluted, to the coagulated latex, for example by mechanical shearing with or without prior dilution or with the aerated cream.
    Another emulsion polymerization process that can be used to prepare the terpolymer is that described in US Pat. No. 7,122,608. At the end of the copolymerization reaction, the copolymers obtained must be hydrolysed in the case where the adhesion promoter monomer used contains a weak acid precursor function, in order to transform it into a weak acid function. This hydrolysis reaction can be carried out using conventional reagents and hydrolysis (dealkylation) conditions, especially with the aid of strong acids or bases, such as hydrochloric acid, which are used hot (by example at 80-100 ° C) or, in the case in particular phosphonic acid alkyl esters, by treatment with sodium bromide followed by an acidification step or more preferably by reaction with a halogenated silane, such as bromotrimethylsilane, in an organic solvent such as THF, at a temperature of 20 to 40 ° C, for example, followed by a step of hydrolysis with methanol.
    The copolymer used according to the invention has sufficient mechanical properties to enable it to be shaped into a film. This film shaping can be done for example: by extrusion; casting a copolymer solution in an organic solvent; by centrifugation deposition of a copolymer solution in an organic solvent; or by printing a solution of copolymers in an organic solvent. The films thus obtained, after a drying step and then an annealing step, have good mechanical properties and can be stretched.
    Prior to this film-forming step, it is possible to add various additives to the copolymer, such as reinforcing fillers, conductive fillers such as carbon nanotubes, conductive salts, piezoelectric particles such as BaTiCL nanoparticles, plasticizers, crosslinking agents, crosslinking initiators, triethoxysilanes and mixtures thereof. The copolymer may also be mixed with another polymer such as PVDF.
    The copolymers used according to the invention preferably additionally satisfy at least one criterion which qualifies them as electroactive polymers, in particular they have a Curie temperature of less than 11 CFC, preferably less than 100 ° C., and a maximum of dielectric constant greater than 30.
    Their melting temperature is generally between 110 and 160 ° C., more particularly between 115 and 155 ° C.
    Because of their good adhesion to polar hydrophilic surfaces such as glass and more particularly metal surfaces, these copolymers can be used as coatings for these surfaces or, on the contrary, as substrates for metallic coatings. "Metal surfaces" means surfaces formed or coated with metals, metal oxides or metal alloys. The metals considered can be selected from steel, copper, gold, silver, nickel or aluminum, without this list being limiting. These films are useful for the manufacture of composite parts comprising a solid polymer film of the copolymer in direct contact with at least one metallic or vitreous element. This composite part may constitute an electroactive device, such as an actuator, a sensor or an artificial muscle; a membrane; a capacitor; a binder for lithium-ion batteries; or a component of a power generation device such as a fuel cell.
    EXAMPLES
    The following examples illustrate the invention without limiting it.
    Techniques and instruments for measuring Nuclear Magnetic Resonance (NMR). The NMR spectra are recorded on a Bruker AC 400 apparatus, deuterated acetone is used as a solvent. Coupling constants and chemical shifts are respectively given in Hertz (Hz) and in parts per million (ppm). The acquisition parameters for the NMR * H [or 19F] are: rotation angle 90 ° [30 °], acquisition time 4.5 s [0.7 s], pulse sequence 2 s, number of scans 8 [128] and pulse duration of 5 ps for 19 F NMR.
    Thermogravimetric analyzes (ATG). ATG assays are performed on 10-15 mg samples on TA Instruments TGA Q50 instrument in aluminum cups. The rise in temperature is carried out at 10 ° C./min, under air between 25 and 590 ° C.
    Differential Scanning Colorimetry (DSC). The DSC measurements are obtained on 10-15 mg samples on a Netzsch DSC 200 F3 instrument using the following analysis cycle: cooling of the ambient temperature to -50 ° C to 20 ° C / min, isothermal to -50 ° C for 5 min, first rise from -50 to 200 ° C at 10 ° C / min, cooling from 200 to -50 ° C to 10 ° C / min, isothermal at -50 ° C for 3 min, second rise to temperature of -50 to 200 ° C at 10 ° C / min and last cooling of 200 ° C at room temperature. Calibration was performed with noble metals and verified with an indium sample prior to analysis. The Curie transition and melting temperatures are determined at the maximum endothermic peaks.
    EXAMPLE 1 Radical Terpolymerization of VDF with TrFE and DMVP
    A poly (VDF-ter-TrFE-ter-DMVP) terpolymer was prepared according to the reaction scheme illustrated in FIG. 1 (1st step).
    To achieve this, a 100 mL Hastelloy autoclave is equipped with inlet and outlet valves, a rupture disk, a pressure gauge and a pressure sensor connected to a computer to record the pressure evolution as a function of time. The autoclave is pressurized with 30 bar of nitrogen to check for leaks. It then undergoes three vacuum-nitrogen cycles to eliminate any trace of oxygen. After inerting the reactor, 60 mL of a degassed solution containing di (tert-butylcyclohexyl) peroxydicarbonate (617 mg, 1.6 mmol) and dimethylvinyl phosphonate (DMVP, 683 mg, 5.0 mmol) in dimethylcarbonate (DMC) were introduced into the reactor. The reactor is then cooled to -80 ° C to introduce the gaseous monomers. Trifluoroethylene (TrFE, 17.0 g, 207 mmol) and then vinylidene fluoride (VDF, 20.0 g, 313 mmol) are transferred to the reactor and the amount of each monomer is measured by double weighing. After loading all reagents, the autoclave is warmed to room temperature and then heated to 48 ° C. The reaction lasts 17 hours and a pressure drop of 22 bar is observed compared to 30 bars at the start of polymerization. After the reaction, the reactor is placed in an ice bath and degassed. The crude solution, viscous and colorless, is transferred into a beaker and diluted in 200 mL of acetone. This solution is precipitated in 4 L of cold pentane. The product obtained, a white solid, is dried at 80 ° C. under vacuum for 14 hours. The polymer obtained (34.5 g, yield = 91%) is characterized by 1H NMR spectroscopy (FIG. 2), 19F (FIG. 3) and 31P, CES, ATG (FIG. 4) and DSC (FIG. 6).
    As illustrated in FIG. 5, the curve obtained by ATG for this terpolymer is superimposable to that obtained for the corresponding copolymer, devoid of units derived from the DMVP monomer. It can thus be concluded that the introduction of this monomer does not modify the thermal properties of the fluoropolymer which remains stable up to 300 ° C. with a degradation temperature corresponding to 5% mass loss which is equal to 390 ° C. .
    Likewise, as shown in Figure 7, the DSC curve of the terpolymer of Example 1 is substantially the same as that of the comparative copolymer, with a melting temperature of 150 ° C and a melting enthalpy of 21 J / g. The semicrystalline structure of the copolymer is thus not impaired by the introduction of the adhesion promoter monomer. In addition, the terpolymer has the same electroactivity properties as the comparative copolymer, with a Curie transition temperature of 66 ° C., characteristic of the transition from a ferroelectric phase to a para-electric phase.
    Example 2: Preparation of a terpolymer poly (VDF-ter-TrFE-ter-VPA).
    The poly (VDF-ter-TrFE-ter-DMVP) terpolymer obtained according to Example 1 was hydrolysed according to the reaction scheme illustrated in FIG. 1 (2nd step) to obtain a poly (VDF-iron-TrFE-terpolymer terpolymer). VPA) in which the phosphonic ester functions are converted into phosphonic acid functions.
    To do this, a 250 ml tri-neck flask equipped with a 50 ml dropping funnel, a water cooler and a thermometer is dried and purged with nitrogen for 15 minutes. It contains 10.0 g of the terpolymer prepared in Example 1. A low nitrogen pressure in the assembly prevents any entry of moisture. 60 mL of dry tetrahydrofuran (THF) are introduced through the dropping funnel. The reaction medium is placed in an ice bath and cooled to 4 ° C. 675 mg of bromo trimethylsilane (TMSBr) are added dropwise over 15 minutes. Then, the reaction medium is gradually warmed to room temperature. After 15 hours of reaction, 100 ml of methanol (MeOH) are introduced through the dropping funnel. The solution is stirred vigorously for 2 hours. After the reaction, the solvents are evaporated using a rotary evaporator. The solid thus obtained is dissolved in acetone and then precipitated twice in 2 L of cold pentane. The white powder obtained (8.2 g, yield = 82%) is dried under vacuum for 14 hours and then characterized by NMR * spectroscopy (Figure 2), 19F and 31P, ATG and DSC.
    In FIG. 2, the comparison of the spectrum obtained for the terpolymer of Example 2 with that of the terpolymer of Example 1 shows a disappearance of the solid mass between 3.7 and 3.9 ppm, which is characteristic of the protons of the methyl groups of DMVP. and thus confirms the total hydrolysis of DMVP units (vinylphosphonic acid dimethyl ester) to VPA (vinylphosphonic acid).
    Example 3: Radical terpolymerization of VDF with TrFE and MAF
    A 100 mL Hastelloy autoclave is equipped with inlet and outlet valves, rupture disc, pressure gauge and a pressure sensor connected to a computer to record the evolution of the pressure as a function of time (Figure 9 ). The autoclave is pressurized with 30 bar of nitrogen to check for leaks. It then undergoes three vacuum-nitrogen cycles to eliminate any trace of oxygen. After inerting the reactor, 60 mL of a degassed solution containing di (tert-butylcyclohexyl) peroxydicarbonate (180 mg) and 2-trifluoromethylacrylic acid (MAF, 0.7 g, 5 mmol) in dimethylcarbonate (DMC ) were introduced into the reactor. The reactor is then cooled to -80 ° C to introduce the gaseous monomers. Trifluoroethylene (TrFE, 14.0 g, 169 mmol) and then vinylidene fluoride (VDF, 21.0 g, 328 mmol) are transferred to the reactor and the amount of each monomer is measured by double weighing. After loading all reagents, the autoclave is warmed to room temperature and then heated to 48 ° C. The reaction lasts 18 hours and a pressure drop of 22 bar is observed compared to 23 bars at the start of polymerization. After the reaction, the reactor is placed in an ice bath and degassed. The crude solution, viscous and colorless, is transferred into a beaker and diluted in 200 mL of acetone. This solution is precipitated in 4 L of cold water. The product obtained, a white solid, is dried at 80 ° C. under vacuum for 14 hours. The polymer obtained (30.1 g, yield = 84%, VDF / TrFE / MAF molar composition = 68/31/1) is characterized by 1 H NMR spectroscopy (FIG. 8) and 19 F (FIG. 9), ATG and DSC.
    In FIG. 8, the proton signal of the MAF units is included in the characteristic proton mass of the VDF units, ie between 2.2 and 3.4 ppm. The mass between 5.1 and 6.0 ppm is characteristic of the protons of the TrFE units. In Figure 9, the signals between -63 and -71 ppm are characteristic of the CF3 moieties of the MAF units. The signals between -90 and -135 ppm are characteristic of the CF2 groups of the TrFE and VDF units. The signals between -193 and -221 ppm are characteristic of the CFH groups of the TrFE units. The combination of FIGS. 8 and 9 makes it possible to calculate the composition of the terpolymer obtained.
    The following Table 1 summarizes the conditions of radical terpolymerizations of VDF with TrFE and DMVP or MAF and the properties of the polymers obtained according to Examples 1 to 3.
    Table 1
    In this table, "monomers" indicates the percentage of each of the monomers relative to the initial mixture of monomers and "polymer" indicates the weight percent of units resulting from these monomers in the polymer, as measured by 19F NMR spectroscopy. In addition, "MPA" refers to the adhesion promoter monomer used (DMVP in Example 1, VPA in Example 2, MAF in Example 3).
    Yield means the yield of the reaction.
    Mn is the number average molecular weight of the polymer.
    Td5% refers to the degradation temperature of the polymer leading to 5% mass loss.
    Te represents the Curie temperature as determined by maximum differential scanning calorimetry (DSC) of the endotherm during the second temperature rise at 20 ° C / min.
    Tf represents the melting temperature of the terpolymer, as determined by differential scanning calorimetry (DSC) at the maximum of the endotherm during the second temperature rise. ΔΗγ represents the melting enthalpy measured by differential scanning calorimetry (DSC) during the second temperature rise.
    As can be seen from this table, the semicrystalline and electroactive nature of the fluorinated polymer, as well as its thermal stability, are not substantially altered by the introduction of MAF groups, as has been observed for the groups DMVP and VPA.
    Example 4: Preparation of films and adhesion tests
    In order to characterize the improvement of the adhesion properties, thin films have been prepared on aluminum substrates. To this end, 1.00 g of the poly (VDF-ter-TrFE-ter-DMVP) terpolymer (Example 1) and 1.00 g of the poly (VDF-iron-TrFE-iron-VPA) terpolymer (Example 2) are dissolved separately in 5.00 g of methyl ethyl ketone (MEK) at room temperature. The viscous solutions are deposited on the substrates and the solvent evaporates at room temperature for 8 hours. The films thus obtained are dried for 14 hours at 80 ° C. under vacuum and then annealed at 110 ° C. for 4 hours. A comparative film is prepared under the same conditions, from a poly (VDF-co-TrFE) copolymer.
    It is observed that the film prepared from the comparative copolymer (FIG. 10, left) peels off the aluminum foil without cracking. The film obtained using the terpolymer of Example 1 (FIG. 10, center) does not adhere to the aluminum substrate; it peels off and creaks because of its contraction during drying. On the contrary, the film prepared from the terpolymer of Example 2 (FIG. 10, right) adheres perfectly to the aluminum foil even when the latter is deliberately deformed (folded, rolled, etc.). The film obtained from this terpolymer therefore has good adhesion properties.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    1. Use of a fluorinated copolymer in the manufacture of a solid polymeric film, for imparting to the film adhesion properties on a metal surface or on glass, characterized in that the said copolymer is obtained by: (a) copolymerization radical of monomers comprising, and preferably consisting of: (i) at least one fluorinated monomer selected from vinylidene fluoride (VDF) and trifluoroethylene (TrFE), (ii) optionally at least one other fluorinated monomer and (iii) a adhesion promoter monomer which is a non-perfluorinated vinyl or vinylenic monomer bearing at least one weak acidic function or weak acid precursor, with the exception of carboxyvinyl, carboxyvinylene, 1-alkylcarboxyvinyl, 1-alkylcarboxyvinylene and of their precursors, and (b) when present, conversion of the weak acid precursor functions to weak acid functions.
    [2" id="c-fr-0002]
    2. Use according to claim 1, characterized in that the molar proportion of the units derived from said adhesion promoter monomer represents less than 1% of the copolymer, preferably from 0.5 to 0.8% of the copolymer.
    [3" id="c-fr-0003]
    3. Use according to claim 1 or 2, characterized in that said other fluorinated monomer is selected from: tetrafluoroethylene (TFE), chlorofluoroethylene (CFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP), trifluoropropene, tetrafluoropropene, chloro-trifluoropropene, hexafluoroisobutylene, perfluorobutylethylene, pentafluoropropene, perfluoroethers such as PMVE and PPVE, and mixtures thereof, preferably CFE or CTFE.
    [4" id="c-fr-0004]
    4. Use according to any one of claims 1 to 3, characterized in that the weak acidic function is selected from a carboxylic acid function and a phosphonic acid function.
    [5" id="c-fr-0005]
    5. Use according to any one of claims 1 to 4, characterized in that the precursor weak acid function is selected from the salts and alkyl esters of carboxylic acid and phosphonic acid salts and alkyl esters, preferably alkyl esters of phosphonic acid. phosphonic acid.
    [6" id="c-fr-0006]
    6. Use according to claim 5, characterized in that the precursor of weak acid function is a phosphonic acid alkyl ester and in that step (b) is carried out by reaction with a halogenated silane, in an organic solvent followed by a hydrolysis step using methanol.
    [7" id="c-fr-0007]
    7. Use according to any one of claims 1 to 4, characterized in that the adhesion promoter monomer is selected from a dialkyl ester of vinylphosphonic acid, vinylphosphonic acid and (2-trifluoromethyl) acrylic acid.
    [8" id="c-fr-0008]
    8. Process for improving the adhesion to a metal or vitreous substrate of a fluorinated polymer obtained from at least one fluorinated monomer chosen from vinylidene fluoride (VDF) and trifluoroethylene (TrFE) and optionally at least one another fluorinated monomer, characterized in that it comprises introducing into said fluoropolymer units resulting from the radical copolymerization of a non-perfluorinated vinyl or vinylenic monomer bearing at least one weak acidic function or weak acid precursor, with the exception of the carboxyvinyl, carboxyvinylene, 1-alkylcarboxyvinyl, 1-alkylcarboxyvinylene monomers and their precursors, and the conversion of the weak acid to weak acid precursor function, when present.
    [9" id="c-fr-0009]
    9. Composite part comprising a solid polymer film in direct contact with at least one metallic or vitreous element, characterized in that said film is made from a copolymer obtained by: (a) radical copolymerization of monomers comprising, and preferably consisting of: (i) at least one fluorinated monomer selected from vinylidene fluoride (VDF) and trifluoroethylene (TrFE), (ii) optionally at least one other fluorinated monomer and (iii) an adhesion promoting monomer which is a non-perfluorinated vinyl or vinylenic monomer bearing at least one weak acidic function or weak acid precursor, with the exception of carboxyvinyl, carboxyvinylene, 1-alkylcarboxyvinyl, 1-alkylcarboxyvinylene monomers and their precursors, and (b) when present, transformation of the weak acid precursor functions into weak acid functions.
    [10" id="c-fr-0010]
    10. Composite part according to claim 9, characterized in that it constitutes an electroactive device, such as an actuator, a sensor or an artificial muscle; a membrane; a capacitor; a binder for lithium-ion batteries; or a component of a power generation device such as a fuel cell.
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    同族专利:
    公开号 | 公开日
    JP6847119B2|2021-03-24|
    KR20180127323A|2018-11-28|
    US20190062476A1|2019-02-28|
    EP3408088A1|2018-12-05|
    CN108883608B|2021-03-19|
    WO2017129881A1|2017-08-03|
    JP2019509365A|2019-04-04|
    FR3047008B1|2019-10-25|
    CN108883608A|2018-11-23|
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    WO2014162080A1|2013-04-03|2014-10-09|Arkema France|Copolymers containing vinylidene fluoride and trifluoroethylene|CN111065681A|2017-08-09|2020-04-24|阿克马法国公司|Electroactive fluoropolymer-based formulation for actuator|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1650548A|FR3047008B1|2016-01-25|2016-01-25|USE OF A VINYLIDENE FLUORIDE COPOLYMER FOR CONFINING A FILM OF ADHESION PROPERTIES|
    FR1650548|2016-01-25|FR1650548A| FR3047008B1|2016-01-25|2016-01-25|USE OF A VINYLIDENE FLUORIDE COPOLYMER FOR CONFINING A FILM OF ADHESION PROPERTIES|
    CN201780008105.3A| CN108883608B|2016-01-25|2017-01-17|Use of vinylidene fluoride copolymers for providing adhesion properties to films|
    EP17706539.8A| EP3408088A1|2016-01-25|2017-01-17|Use of a vinylidene fluoride copolymer for providing a film with properties of adhesion|
    PCT/FR2017/050101| WO2017129881A1|2016-01-25|2017-01-17|Use of a vinylidene fluoride copolymer for providing a film with properties of adhesion|
    KR1020187024499A| KR20180127323A|2016-01-25|2017-01-17|Use of a vinylidene fluoride copolymer for providing a film having adhesive properties|
    US16/072,225| US11279782B2|2016-01-25|2017-01-17|Use of a vinylidene fluoride copolymer for providing a film with properties of adhesion|
    JP2018538763A| JP6847119B2|2016-01-25|2017-01-17|Use of vinylidene fluoride copolymer to impart adhesiveness to film|
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