REVERSIBLE OR DYNAMIC POLYMER ENCAPSULANT FOR PHOTOVOLTAIC PANELS ALLOWING IMPROVED DISMANTLING TO FACILITATE THE SEPARATION OF PANEL COMPONENTS

Abstract

The present invention relates to a photovoltaic module encapsulant, characterized in that it comprises, - a polyolefin of formula (I), and - a disiloxane group, in particular a dialkylsiloxane group chosen from dimethylsiloxane and diethylsiloxane, and / or the polydialkylsiloxane of formula (II) as crosslinker; the polyolefin representing from 78 to 99.75% by mass, the crosslinker from 0.25 to 22% by mass relative to the total mass of the composition of the encapsulant. The invention relates to the use of such an encapsulant in a photovoltaic module. Figure for abstract: None

Description

Title of the invention: REVERSIBLE OR DYNAMIC POLYMER ENCAPSULANT FOR PHOTOVOLTAIC PANEL ALLOWING IMPROVED DISMANTLING TO FACILITATE THE SEPARATION OF THE PANEL COMPONENTS Technical field of the invention

[0001] The invention relates to the field of polymers used as encapsulants of photovoltaic modules for photovoltaic panels. In particular, the invention relates to the use of a polymer crosslinked via covalent dynamic chemistry as an encapsulant in photovoltaic modules for easier dismantling and recycling of the various components of the panel. Technical background

[0002] As global warming linked to anthropogenic greenhouse gas emissions accelerates, current societies require a drastic change in their ways of producing energy, and so-called renewable energies are emerging as a viable solution for the production of decarbonized energy. Among these renewable energies, solar energy is produced via the conversion of solar radiation into electricity by photovoltaic panels. If the method of energy production is indeed more renewable than the combustion of fossil resources, it is nevertheless appropriate, in order to limit the environmental impact of solar energy production, to limit as much as possible the impact, on the environment and the availability of resources, of the production and end-of-life phases of photovoltaic panels.

[0003] Currently, the majority of photovoltaic panels are made up of an assembly of several layers, which constitute a module, and include, from the layer facing the sun to the support layer: - a transparent substrate, generally optical quality glass; - a layer of encapsulant; - photovoltaic cells; - another layer of encapsulant; - a protective layer supporting everything (also called backsheet in English).

[0004] The composition of a standard photovoltaic module is illustrated in [Fig.l].

[0005] Silicon is the main element used for the manufacture of photovoltaic panels. Silicon tends to react when it comes into contact with other molecules, particularly oxygen. If the encapsulant is not of good quality and does not effectively play its role of protecting the modules from the environment and external elements (rain, wind, etc.), the silicon cells will come into contact with water and / or air and the panel will begin to oxidize. The panel will then lose efficiency and be damaged.

[0006] The primary role of the encapsulant is therefore to protect and isolate the modules from the environment and external elements (rain, wind, etc.) and thus ensure their operation over long periods (today around 25 years). A module is manufactured via a process called lamination, which allows all the layers shown in [Fig.l] to be combined into a single block. This process consists of making a sandwich with the different components and then applying hot pressure to allow fusion / crosslinking of the encapsulant layer. The photovoltaic cells are thus coated with the encapsulant, allowing them to be isolated from the external environment.

[0007] The second role of the encapsulant is to act as an adhesive between the different components of the module and to ensure the dimensional stability of the solar panel. The front protective layer, which is a solar glass, or the back protective layer (backsheet), which is often a multilayer of polymers with effective barrier properties (water vapor transmission rate value of around 0.1 g / m2 / day), must not delaminate over time and detach from the assembly. Currently, crosslinkable resins, such as ethylene-vinyl acetate or EVA (ethylene-vinyl acetate in English), are used to fulfill the role of encapsulant. They allow fusion at the start of the process, then crosslink during heating to set the system and obtain their final properties: adhesion, thermal, chemical and mechanical stability.While this method has proven its worth for the qualities of the modules formed in terms of ease and cost of production and efficiency during the energy production phase, it remains limited when addressing the issue of the end of life of the modules. Indeed, the crosslinked nature of the encapsulant prevents it from being melted and allowing easy delamination of the different layers of the modules to then process them in separate streams. The panel recycling stage therefore often involves grinding followed by pyrolysis allowing degradation of the organic fraction (panel polymers). This method is costly in terms of CO2-emitting energy. Alternative separation processes are being developed with precise cutting of the encapsulant layer to separate the different elements.However, this type of process is difficult to implement because the thickness of the encapsulant is low (less than 500 pm) and must be . adjusted to each panel technology. The recycling of photovoltaic panels is nevertheless essential from an ecological and economic point of view due to the rare metals present in the panels (silver, copper and to a lesser extent silicon). In addition, regarding the backsheet, separate treatment is necessary because this layer often contains fluorinated polymers, aluminum, etc. After mechanical crushing / incineration or separation, recovery of the rare metals included in the photovoltaic cells by hydrometallurgical or pyrometallurgical processes is possible. These recycling routes are expensive because the different compounds must be extracted and purified before they can be further recovered.

[0008] In order to overcome this problem, thermoplastic encapsulants have recently been developed. Since these encapsulants are not crosslinked, a thermal or chemical process makes it possible to easily consider delamination of the panels at the end of their life. Heating the panels above the melting temperature of these polymers allows the polymer to pass into the molten state and thus allow the separation of the different layers of the modules. Another solution is to use a solvent route to dissolve the encapsulant and separate the different layers of the panel. These separation processes can be carried out at moderate temperatures (60-120°C) and if recycling of the solvent is planned for solvent-based processes, lower energy consumption and environmental impact are expected.However, this type of system deviates from cross-linked EVA systems with ideal properties and has lower technical properties (thermal, mechanical and chemical stability).

[0009] More complex encapsulant systems can be considered. For example, adding a layer of thermoplastic between two crosslinked EVA films or a layer of thermoplastic on either side of a crosslinked EVA layer in contact with the silicon cell and the glass or the silicon cell and the backsheet. This type of technology makes it possible to obtain more effective encapsulants while ensuring better separation of the different components of the panel at the end of its life. However, after this separation, a residual layer of EVA is present on the different components, a layer as complex to treat as in the case of conventional EVA systems. The production of this type of encapsulant is also more complex because two distinct polymers are inherently incompatible. The production of this multilayer requires complex plastics processing equipment and produces a new type of material on the market that will not be able to be recycled.Indeed, the mixture of two polymers leads to a drastic drop in properties during recycling due to the induced phase separation. All of these points slow down. the marketing of these encapsulants, despite the significant advantage offered at the end of their life compared to crosslinkable resins.

[0010] There is therefore a real need to have a photovoltaic module encapsulant having the quality, performance and final properties of a thermoplastic crosslinkable resin layer such as EVA, particularly in terms of adhesion, thermal, chemical and mechanical stability, while also allowing easy dismantling and recycling of the various components of the module and the photovoltaic panel, such as thermoplastic resins.

[0011] In particular, there is still a need for a photovoltaic module encapsulant having all of the aforementioned properties, and in addition ease of implementation during the lamination step of the photovoltaic module, good optical properties (transparency, low level of Haze and refractive index), perfect adhesion to different supports, good resistance to finishing for a temperature above 80°C, low water permeability, good resistance to UV (Ultra-Violet), good electrical insulation. Summary of the invention

[0012] The present invention aims precisely to meet this need, by providing a photovoltaic module encapsulant, characterized in that it comprises,

[0013] - a polyolefin formula (I)

[0014] in which

[0015] n = 1 to 100%,

[0016] m = (100-n)%,

[0017] R1 and R2, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 24 carbon atoms, a cycloalkyl group comprising 3 to 24 carbon atoms, the alkyl and cycloalkyl groups being optionally substituted,

[0018] said polyolefin having • a melt flow index (also called IFC) greater than 0.1 g / 10 min and less than 50 g / 10 min (ISO 1133-1 (2011) standard), 190°C, 2.16 kg), and • a mass crystallinity rate of less than 30%;

[0019] - a disiloxane group, in particular a dialkylsiloxane group chosen from dimethylsiloxane and diethylsiloxane, and / or polydialkylsiloxane of formula (II):

[0020] in which • a = 1 to 100%, • b = (100 - a)%, and • the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, • R3 represents a methyl group, an ethyl group or which is the point attachment of R3 to the polyolefin by a covalent bond, R4, R5, R6, R7, and R8, identical or different, represent a group methyl or an ethyl group, „ -X represents the point of attachment of the polydialkylsiloxane to polyolefin A by a covalent bond,

[0021] as a crosslinker;

[0022] the polyolefin representing from 78 to 99.75% by mass, the crosslinker from 0.25 to 22% by mass relative to the total mass of the encapsulant composition.

[0023] The invention consists in using, as encapsulant, a crosslinked polymer having dynamic and / or reversible covalent bonds in its structure, allowing easy separation of the encapsulant and all of the constituents of the photovoltaic panels, or a new lamination to reassemble a material which has undergone degradation.

[0024] Indeed, current systems based on EVA are crosslinked covalently and irreversibly using thermally activated crosslinking agents (peroxides in particular), or by exposure to UV rays implementing radical crosslinking. Consequently, on current panels, delamination is an irreversible phenomenon and leads to the scrapping of degraded panels.

[0025] Recently, the use of dynamic covalent chemistry and reversible covalent chemistry has made it possible to develop crosslinked polymer systems that can be reshaped under temperature stimuli (from a threshold temperature) via the dynamics or reversibility of chemical bonds. Dynamic systems make it possible to maintain a constant crosslinking rate, while allowing the systems to be reshaped under heat via exchange reactions.

[0026] Reversible systems allow a break in covalent bonds from a certain threshold temperature and therefore involve a reduction in the crosslinking rate. past this temperature. The major difference between associative and dissociative systems is the change in viscosity as a function of temperature. The viscosity of associative systems follows an Arrhenius law as a function of the inverse of the temperature, a behavior similar to that of glass, unlike the dissociative system whose viscosity drops sharply past the dissociation temperature.

[0027] In the context of the present invention, a chemistry involving an associative or dissociative system or an associative / dissociative mixture can be used to develop a dynamically reversibly crosslinked polymer in order to obtain a polymer network having properties equivalent to current EVA systems, while ensuring separability of all the constituents or offering the possibility of reshaping the material at the end of the life of the panels.

[0028] Thus, an encapsulant according to the invention can have a dual objective: - extend the lifespan of solar panels by allowing relamination of panels that have undergone delamination; and - facilitate the separation of the different constituents by relying on the reversibility of the chemical bonds used.

[0029] The principle of a crosslinked network with dynamic or reversible chemistries and the mechanistic differences that this implies are represented in [Fig.2].

[0030] Different routes exist to obtain crosslinked networks in a reversible or dynamic manner. Some of these routes are presented in [Fig.3]. As can be seen, crosslinking relies on the functionalization of polymer materials (either during polymerization or during a post-polymerization step). In the case of polyolefins of formula (I), this functionalization is often carried out in bulk by radical grafting chemistry. The dark gray and black chemical functions in the diagram denote dynamic or reversible covalent chemistries and classical covalent chemistry respectively. A characteristic temperature of the polymer network is associated with the presence of dynamic or reversible chemistry from which the dynamic or reversible chemistry will be activated, and the material will be malleable.In the case of reversible chemistry, exceeding the dissociation temperature Td allows the network to be decrosslinked and a non-crosslinked thermoplastic to be obtained.

[0031] While reversible dynamic crosslinked systems have a Td which will be similar to a fusion in the viscoelastic behavior of the polymer (breaking of bonds and fusion), associative dynamic systems do not have a change in behavior such as decrosslinking or the like, which induces a sudden change in viscoelastic behavior.

[0032] In the case of dynamic chemistry, the bonds are exchanged in an associative manner and therefore without a decrease in the crosslinking rate, which makes the decrease in viscosity less abrupt (the viscosity then evolving linearly with the inverse of the temperature). There is no temperature beyond which the behaviors abruptly change properties. In these cases, the process temperature used is defined arbitrarily according to the desired characteristics in terms of viscosity and reprocessability. Reprocessability means rapid reshaping without degradation of the polymer.

[0033] For dynamic chemistries, we can cite the chemistry of siloxane exchanges, as shown in [Fig.4]. [Fig.4] shows that the dynamic exchange of siloxane groups occurs without breaking bonds. The initial polymer has a melt flow index (also called IFC) greater than 0.1 g / 10 min and less than 50 g / 10 min (ISO 1133-1 (2011) standard, 190°C, 2.16 Kg) in order to have low-viscosity systems at the start, to which a crosslinking compound carrying reversible or dynamic covalent chemical bonds is covalently grafted. This crosslinking compound has a functionality of 2 or more in order to allow the formation of a network between the polymer chains.

[0034] The grafting of the crosslinking compound to the polymer chains can be done by several routes which diverge in the synthesis conditions.

[0035] The synthesis of the dynamic or reversible polymer network is carried out in one step or in two steps.

[0036] One-step synthesis is generally carried out in bulk (in a reactive extrusion process) and consists of crosslinking polyolefins which do not initially have reactive functions. Crosslinking occurs by reacting a molecule having a functionality greater than or equal to 2 by radical means using a radical generator (peroxide for example) and having a dynamic or reversible bond in its chemical structure.

[0037] The two-step synthesis consists of functionalizing the polyolefin-type polymer by introducing reactive functions along the polymer chain in a first step, before proceeding to the crosslinking step during which the reactive functions react with a molecule having a functionality greater than or equal to 2 in a second step. The first step can be carried out directly during the synthesis of the polymer by carrying out a copolymerization (for example ethylene and another monomer of interest having a vinyl function) or by post-functionalization of a non-functional polymer by radical route. Once this functionalized polymer has been synthesized, the introduction of a crosslinking compound leads to obtaining the polymer network. The crosslinking compound is a molecule having a functionality greater than or equal to 2 and capable of reacting with the reactive functions of the polymer.The dynamics or reversibility of the polymer network thus obtained comes from the chemical structure of the crosslinking compound. Indeed, it must present in its structure the dynamic or reversible bond of interest. This route of . Crosslinking can be done directly by extrusion (and therefore in bulk) or by solvent route. These synthesis routes and conditions are well known to those skilled in the art and described, for example, in “The synthesis of polyolefin graft copolymers by reactive extrusion” (Prog. Polym. Sci., 1999, 24, 81-142).

[0038] The grafting chemistries for grafting functionalities to polyolefins by radical routes are diverse: maleic anhydride, maleimides, vinyls, (meth)acrylates, etc.

[0039] The exchange chemistries possibly applicable to the polymers of the invention are also very numerous (reversible or dynamic): siloxane, imine, disulfide bridge, ester, boronic ester, metathesis, etc.

[0040] The invention also relates to the use of an encapsulant of the invention in a photovoltaic module.

[0041] Another object of the invention is a photovoltaic module comprising - a transparent substrate, often corresponding to a solar glass having the following characteristics: low reflection, high transmissivity and high resistance.

[0042] The glasses used are either crystalline glasses (mono or polycrystalline), or thin-film glasses. The glasses are sometimes coated to reduce their reflection and with a low Fe content, in order to obtain high transparency values known as low iron glass or ultra-white glass, - an encapsulant layer according to the invention, - a photovoltaic cell, in particular based on silicon, copper indium selenide (CuIn(Se)2, or CIS), copper indium gallium selenide (CuInGa(Se)2, also called CIGS), or cadmium telluride (CdTe), - another encapsulant layer according to the invention, - a protective layer supporting the whole (backsheet), in particular made of polyvinylidene fluoride (PVDF), poly(p-phenylene oxide) (PPG) or poly(p-phenylene ether) (PPE), poly(ethylene terephthalate) (PET), polyvinyl chloride (PVC), or elastomer thermoplastic (TPE) or glass. Brief description of the figures

[0043] Other characteristics and advantages of the invention will appear during the reading of the detailed description which follows for the understanding of which reference will be made to the appended drawings in which:

[0044] [Fig. 1] represents the composition of a standard photovoltaic module.

[0045] [Fig.2] is a representative diagram of a polymer system carrying reversible and dynamic chemical bonds.

[0046] [Fig.3] represents the synthesis routes of polymer networks with dynamic or reversible covalent bonds.

[0047] [Fig.4] represents the dynamic exchange (without breaking of bonds) of disiloxane groups.

[0048] [Fig.5] schematically represents the grafting reaction of an allyl group onto a polyethylene (PE) chain by radical means.

[0049] [Fig.6] schematically represents the grafting reaction of maleic anhydride onto a polyethylene (PE) chain by radical route followed by a reaction with a primary amine.

[0050] [Fig.7] represents the ADM curves at the top and the results of the swelling tests (swelling rate and insoluble fraction) after 48h at 110°C in xylene of the encapsulant of example 1 without catalyst and with 0.08% by mass of catalyst at the bottom.

[0051] [Fig.8] shows the result of the finishing recovery of the material of example 1 without catalyst and with 0.08% by mass of catalyst.

[0052] [Fig.9] represents all the stages of the lamination / delamination / relamination test carried out to demonstrate the potential of an encapsulant according to the invention to extend the life of solar panels or facilitate their disassembly at the end of their life. The different stages are grouped together in the form of photographs. Detailed description of the invention

[0053] The present invention relates to a photovoltaic module encapsulant, characterized in that it comprises,

[0054] characterized in that it comprises,

[0055] - a polyolefin formula (I)

[0056] in which

[0057] n = 1 to 100%,

[0058] m = (100-n)%,

[0059] R1 and R2, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 24 carbon atoms, a cycloalkyl group comprising 3 to 24 carbon atoms, the alkyl and cycloalkyl groups being optionally substituted,

[0060] said polyolefin having • a melt flow index (also called IFC) greater than 0.1 g / 10 min and less than 50 g / 10 min (ISO 1133-1 (2011) standard), 190°C, 2.16 kg), and • a mass crystallinity rate of less than 30%;

[0061] - a disiloxane group, in particular a dialkylsiloxane group chosen from dimethylsiloxane and diethylsiloxane, and / or polydialkylsiloxane of formula (II):

[0062] in which • a = 1 to 100%, b = (100 - a)%, and the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, R3 represents a methyl group, an ethyl group or \which is the point attachment of R3 to the polyolefin by a covalent bond, • R4, R5, R6, R7, and R8, identical or different, represent a group methyl or an ethyl group, * represents the point of attachment of the polydialkylsiloxane to the polyolefin rx by a covalent bond,

[0063] as a crosslinker;

[0064] the polyolefin representing from 78 to 99.75% by mass, the crosslinker from 0.25 to 22% by mass relative to the total mass of the encapsulant composition.

[0065] The encapsulant of the invention therefore comprises a linear polymer of polyolefin type (polyethylene, PE, or polypropylene, PP) of formula (I). Rj

[0066] R1 and R2, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 24 carbon atoms, a cycloalkyl group comprising 3 to 24 carbon atoms, the alkyl and cycloalkyl groups being optionally substituted,

[0067] is crosslinked by disiloxane groups.

[0068] Unless otherwise indicated, in the present description, the indices m, n, a, and b are positive real numbers which are not necessarily integers but representative of the average molecular structure in percentage (statistical values).

[0069] For the purposes of the present invention, the term "alkyl" means a linear, branched, saturated, optionally substituted carbon radical comprising 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. Examples of saturated, linear or branched alkyl that may be mentioned are methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecanyl radicals and their branched isomers.

[0070] The term "cycloalkyl" means a mono- or polycyclic, saturated, optionally substituted carbon radical comprising 3 to 24 carbon atoms, preferably 3 to 12 carbon atoms. As saturated cyclic alkyl radicals, mention may be made of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco[2,1,1]hexyl, bicyclo[2,2,1]heptyl, bicyclo[3,3,1]nonane radicals.

[0071] The alkyl and cycloalkyl radicals may optionally be substituted by one or more halogen atoms chosen from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more alkyl groups, with alkyl as defined in the context of the present invention.

[0072] In the context of the present invention, the term “disiloxane” group is understood to mean in particular a dialkylsiloxane group chosen from a dimethylsiloxane and diethylsiloxane group, and / or polyalkylsiloxane of formula (II):

[0073] in which • a = 1 to 100%, • b = (100 - a)%, and • the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, • R3 represents a methyl group, an ethyl group or \ jJ> which is the point attachment of R3 to the polyolefin by a covalent bond, • R4, R5, R6, R7, and R8, identical or different, represent a group methyl or an ethyl group, • \represents the point of attachment of the polydialkylsiloxane to the polyolefin HAS by a covalent bond.

[0074] According to a preferred embodiment, the polyolefin is chosen from

[0075] - linear low-density polyethylene (LLDPE or Linear low-density polyethylene in English). Its density is 0.92 g / cm3.

[0076] - low density polyethylene (LDPE or LDPE) English). LDPE is the one with the most branching, resulting in a less compact molecular structure and therefore a lower density. It has a density of 0.910 to 0.925 g / cm3.

[0077] - polypropylene (PP). It has a density between 0.895 g / cm3 and 0.92 g / cm3.

[0078] The density of polyolefins is determined according to ASTM D 1505.

[0079] The polyolefin is chosen with a low viscosity for the dismantling step. Ideally, the Hot Melt Index (HMI) at 190°C of the polyolefin is greater than 0.1 g / 10 min.

[0080] In one embodiment of the invention, the Hot Melt Flow Index (MFI) at 190°C of the polyolefin of formula (I) may be greater than 0.1 and less than 50 g / 10 min (ISO standard 1133-1 (2011)), 190°C, 2.16 kg.

[0081] In another embodiment of the invention, the Hot Melt Index (HMI) of the polyolefin of formula (I) may be 14 g / 10 min.

[0082] The polyolefin of formula (I) has a mass crystallinity rate of less than 30%, in particular less than 20%.

[0083] The mass crystallinity rate of a crystallized polymer sample is defined by the ratio of the mass of the crystalline phases to the mass of the sample studied expressed in %. X-ray diffractometry, differential scanning calorimetry (measurement of enthalpies of fusion), densimetry (density measurement by means of a pycnometer, or with gradient columns, the latter method is often used for measuring the density of polyolefins), broadband nuclear magnetic resonance (NMR) and infrared spectroscopy (IR) are the main physical techniques for measuring the crystallinity rate of a polymer. In the present invention, the mass crystallinity rate of the polyolefin was determined by differential scanning calorimetry (DSC).

[0084] The polyolefin of formula (I) is functionalized with groups having a dynamic or reversible chemistry. The dynamic or reversible chemistries used can be varied. In the context of the present invention, the chemistry of siloxane exchanges is preferentially chosen. This chemistry, illustrated in [Fig. 4], can be used to facilitate the formulation of the encapsulants of the invention by playing in particular the role of adhesion promoter. For this, a disiloxane group, in particular a dialkylsiloxane group chosen from dimethylsiloxane and diethylsiloxane, and / or polyalkylsiloxane, must be integrated into the initial polymer. disiloxane group can be integrated and grafted to the polyolefin via several precursors. These precursors can be chosen from 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,3-bis(chloropropyl)tetramethyldisiloxane, 1,3-bis(hydroxypropyl)tetramethyldisiloxane, the grafting of which results in a polyalkylsiloxane of formula (II) ^5 R3 Rg R?

[0085] in which • a = 1 to 100%, • b = (100 - a)%, and • the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, • R3 represents a methyl group, an ethyl group or "XjS which is the point V x attachment of R3 to the polyolefin by a covalent bond, • R4, R5, R6, R7, and R8, identical or different, represent a methyl group or an ethyl group, • represents the point of attachment of the polydialkylsiloxane to the polyolefin by a covalent bond.

[0086] All of these precursors have one or more central disiloxane group(s), as well as two reactive functions at the end of the chain, which can be used to be grafted to the polyolefin. Depending on the two reactive functions at the end of the molecule, the grafting routes to the polyolefin can vary.

[0087] For example, if the reactive functions are allyl groups, 1,3-diallyltetramethyldisiloxane for example, the grafting can be done without an intermediate by radical route, in the presence of a radical initiator. According to one embodiment of the invention, the polyolefin is LLDPE. [Fig.5] shows the grafting reaction of an allyl group onto a polyethylene chain by radical route.

[0088] An initiator is a compound that decomposes to initiate and propagate chemical reactions by generating radicals which will then transfer to the polyolefin chains and thus allow the grafting of molecules by radical reaction with the reactive functions, for example with the vinyls of vinyl-functionalized polydimethylsiloxanes for the crosslinking of the polyolefin. grafted. The person skilled in the art is familiar with the initiators and is able to manufacture them.

[0089] In the context of the present invention, the initiator may be chosen from

[0090] - a peroxide chosen from diisopropyl peroxide, dicumyl peroxide (DCP) (also called bis(l-phenyl-l-methylethyl) peroxide);

[0091] - a nitrogen compound chosen from 2,2'azo-bis(2-methylpropionitrile), azobisisobutyronitrile (AIBN).

[0092] If the functions are NH2 or OH, for example in the case of 1,3-bis(hydroxypropyl)tetramethyldisiloxane and 1,3-bis(3-aminopropyl)tetramethyldisiloxane), it may be necessary to carry out an intermediate step, preferably consisting of incorporating a reactive group within the polyolefin, for example LLDPE, in particular via a reaction with maleic anhydride, widely described in the literature. The polymer thus obtained will be reactive with respect to NH2 or OH functions. [Fig.6] shows a grafting reaction of maleic anhydride onto a polyethylene chain by radical means followed by a reaction with a secondary amine.

[0093] According to one embodiment, the crosslinking agent may represent from 0.25 to 10% by mass relative to the total mass of the encapsulant composition.

[0094] According to another embodiment, the crosslinking agent may represent from 1 to 10% by mass relative to the total mass of the encapsulant composition.

[0095] In the case of siloxane exchange chemistry and in the case of other covalent dynamic chemistries, it may be necessary to have a compound serving as a catalyst within the polymer. By "catalyst within the polymer" is meant a chemically active free molecule (here the catalyst) which is found within the polymer or grafted onto the polymer (here the polymer being the polyolefin of formula (I)). In the present case, it is possible to use in particular organic bases based on ternary amines, chosen from the group consisting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, and 1,1,3,3-tetramethylguanidine. It is also possible to use a quaternary ammonium chosen from the group consisting of tetramethylammonium hydroxide and tetramethylammonium silanolates.In order to reduce the toxicity of the material and its environmental hazard, other bases selected from the group consisting of KOH, and potassium trimethylsilalonate, etc. can be incorporated to act as catalysts. Other catalysts exist such as Brpnsted acids but these compromise the durability of solar panels as they can cause long-term acid corrosion in the modules. Lewis acids are also promoters of the siloxane exchange reaction. Lewis acids. may be chosen from metal salts such as zinc trifluoromethanesulfonate (also called zinc triflate) or scandium trifluoromethanesulfonate (also called scandium triflate).

[0096] The catalyst loading can be up to 10% by mass of the polyolefin. According to one embodiment of the invention, the catalyst loading is between 0.01 and 10% by mass of the polyolefin. According to another embodiment, the catalyst loading is less than 1% by mass of the polyolefin.

[0097] The encapsulant of the invention may further comprise additives chosen from the group consisting of adhesion promoters, antioxidants, UV absorbers.

[0098] The adhesion promoter may be vinyltrimethylsilane. The concentration of the adhesion promoter in the mixture may be from 0.1 to 10% by mass, more particularly between 0.5 and 3.5% by mass relative to the mass of polyolefin.

[0099] The antioxidant may be a HALS (called Hindered Amine Light Stabilizer). These antioxidants are scavengers of free radicals created by reactions with UV light.

[0100] In this respect, we can cite, for example, Tinuvin® 770. The concentration of the antioxidant in the mixture can be less than 5% by mass relative to the mass of polyolefin.

[0101] In addition to the antioxidant, in the first phase, the mixture may comprise a UV absorber such as for example Cyasorb® UV 531, with a concentration of less than 5% by mass relative to the mass of polyolefin.

[0102] The dynamic covalent chemistries cited are not exhaustive and a multitude of other chemistries are possible.

[0103] Other dynamic covalent chemistries that can be used include: disulfide bond exchange chemistry, boronic ester exchange, transesterification chemistry, or acetal exchange chemistry.

[0104] The crosslinked polyolefin of the invention can be prepared by conventional production processes for polymers in a molten medium and continuously such as extrusion to then be laminated into a film of the desired thickness at the extrusion outlet or in a dedicated step, then used as an encapsulant in photovoltaic panels. For example, the polyolefin used in the composition of the encapsulant of the invention can be manufactured by a reactive extrusion process. This reactive mixing can be carried out in a twin-screw extruder, preferably co rotating or alternatively counter-rotating, or preferably in a single-screw extruder. It is thus possible to co-extrude the polyolefin of formula (I), the disiloxane precursor and optionally a reaction initiator well known to those skilled in the art at a temperature between 70 and 140°C to mix them, then trigger the reaction of the crosslinker using the optional reaction initiator with the polyolefin at a temperature between 150 and 200°C, optionally supplemented by a catalyst, an adhesion promoter, an antioxidant, a UV absorber, in order to correlate the crosslinking kinetics of the polyolefin to the screw profile of the extruder and the residence time of the mixture in this extruder.

[0105] The optimum mixing temperature can range from 70°C to 140°C.

[0106] The optimum reaction temperature corresponding to crosslinking can be between 150°C and 200°C.

[0107] It is favorable to carry out a mixing step at low temperature so as not to trigger the functionalization and crosslinking reaction, to achieve a homogeneous molten medium, and then in a second step to trigger the functionalization and crosslinking reaction at high temperature. Ideally, the mixing and the crosslinking reaction take place in the same extruder.

[0108] In this process, there is at least one phase with a residence time which can be between 30 seconds and 30 minutes and a reaction temperature between 165°C and 185°C. More particularly, the optimal residence time is 10 seconds to 10 minutes for a reaction temperature between 165°C and 180°C.

[0109] These methods are described in the state of the art and well known to those skilled in the art.

[0110] The adhesion promoter, the antioxidant and the UV absorber are as previously described within the scope of this disclosure.

[0111] The shaping into a photovoltaic panel of an encapsulant according to the invention is carried out at a temperature at least higher than that of melting of the base polymer. At the end of the life of the solar panels, the dynamically crosslinked polyolefin can be melted again by bringing it to a high temperature (higher than the melting temperature of the base polyolefin), activating the dynamics of the chains.

[0112] The encapsulant according to the invention has the following properties: - a storage modulus (E') greater than the loss modulus (E”) at all temperatures (excluding polymer degradation), i.e. E'>E” at all T (excluding degradation), which can be measured in ADM or rheology, - hot reprocessability, or the ability of the polymer to flow at a temperature higher than the melting temperature of the initial polyolefin, - delaminability / relaminability, - water permeability less than 15 g / m2 / day but preferably less than 10 g / m2 / day and even more preferably less than 5 g / m2 / day, - optical transmission greater than 85% in the 280-1200 nm range, preferably greater than 90% in the 280-1200 nm range, - cut-off point or cut-off in English less than 375nm,

[0113] The encapsulant of the invention must first of all be compared to the thermoplastic resins known and used as encapsulants, which are developed to allow the recyclability of photovoltaic panels. Several defects of thermoplastic resins of the state of the art have been noted: - The use of polymer systems other than EVA, which are often less efficient (mechanical, optical, UV stability). The recyclability of the system compensates for this overall loss of performance, but the ideal case would be to have the properties of crosslinked EVA, with the disassembly of a thermoplastic. - The hot viscosity of the thermoplastic resins used remains high and is likely to require chemical treatments (solvents) to effectively remove the polymer from all the elements of the recycled panels (glass substrate, photovoltaic modules). - The need in some cases, to compensate for the lack of properties of the thermoplastic layers, to add a layer of cross-linked EVA between the layers to allow separation, which complicates the assembly and makes recycling and cleaning of each component of the assembly complex. Disassembly is made easier but EVA residues remain on the various components of the panel.

[0114] The encapsulant of the invention has the advantage of allowing easy separation of the constituents of the photovoltaic panels while retaining the use of low-cost resins, but without compromising on the properties in use compared to EVA.

[0115] A process for relaminating the panels may also be considered in the event of delamination between the glass and the encapsulant or structural impacts of the glass. For example, if panels are impacted by a hailstorm and the protective glass is cracked, replacement of the glass may be considered while keeping the rest of the panel structure intact.

[0116] It also allows energy savings during the lamination of the assembly, the formation of the polymer network having already been carried out beforehand. It is possible to envisage an optimization of the lamination process with a reduction in lamination temperatures compared to traditional recipes used for EVA.

[0117] Photovoltaic modules with EVA encapsulants are generally laminated at a temperature of 160°C to allow in situ crosslinking by peroxides. The lower temperature lamination conditions with the encapsulants of the invention could be an advantage for the encapsulation of more fragile and temperature-degrading photovoltaic cells (e.g., tandem cell with perovskite layer).

[0118] In addition, the formation of the polyolefin network is done beforehand by decomposition of peroxide. Controlling the decomposition of these radical initiators (peroxides) is easier. In addition, for the final formulation, the incorporation of UV absorbers, radical inhibitors, adhesion promoters, etc. can be done after the formation of the polyolefin network. These therefore do not interfere with the network formation reaction and therefore will not block the radical reactions.

[0119] The invention also relates to the use of an encapsulant of the invention in a photovoltaic module.

[0120] The use of a polyolefin of formula (I) crosslinked via covalent dynamic chemistry in the composition of the encapsulant in the photovoltaic modules facilitates the dismantling and recycling of the various components of the panel.

[0121] Another object of the invention is a photovoltaic module comprising - a transparent substrate, often corresponding to a solar glass having the following characteristics: low reflection, high transmissivity and high resistance.

[0122] The glasses used are either crystalline glasses (mono or polycrystalline), or thin-film glasses. The glasses are sometimes covered with a coating in order to reduce their reflection and with a low iron (Fe) content, in order to obtain high transparency values known as low iron glass or ultra-white glass, - an encapsulant layer according to the invention, - a photovoltaic cell, in particular based on silicon, copper indium selenide (CuIn(Se)2, or CIS), copper indium gallium selenide (CuInGa(Se)2, also called CIGS), or cadmium telluride (CdTe), - another encapsulant layer according to the invention, - a protective layer supporting the whole (backsheet), in particular made of polyvinylidene fluoride (PVDF), poly(p-phenylene oxide) (PPG) or poly(p-phenylene ether) (PPE), poly(ethylene terephthalate) (PET), polyvinyl chloride (PVC), or elastomer thermoplastic (TPE) or glass.

[0123] Thermoplastic elastomers can be chosen from TPA, TPC, TPO, TPS, TPU and TPV. An overview of thermoplastic elastomers can be found in “Thermoplastic Elastomers” (Biron, M. (2000). Thermoplastic Elastomers (TPE). Ed. Techniques Ingénieur). EXAMPLES

[0124] Two examples of embodiment are given below.

[0125] Polyethylene was purchased from DOW® (part number PV Engage 8669). Dicumyl peroxide, maleic anhydride, and potassium trimethylsilanolate were purchased from Sigma-Aldrich®. Vinyl-terminated polydimethylsiloxane was purchased from Gelest® (part number DMS-V03). 1,3-Bis(3-aminopropyl)tetramethyldisiloxane was purchased from ABCR. Xylene was purchased from Carlo Erba. Example 1#:

[0126] 45 g polyethylene having an IFC (Hot Melt Flow Index) or MFI (Melt Flow English index) =14g / 10min (190°C, 2.16kg, ASTM D1238) are placed in the chamber of a HAAKE™ Rheomix QC50 internal mixer placed on a HAAKE™ PolyLab QC (Thermo Scientific™) platform with an internal volume of 70 cm3 and mixed at 90°C, with stirring at 30 rpm until a stable torque is obtained. The grafting step of the vinyl-terminated polydimethylsiloxane also called divinyl PDMS (SOOg.mol1) is then carried out by adding to the mixture 1.5g of this compound and 95mg of dicumyl peroxide also called DCP. If a catalyst is added to the mixture, the addition is also carried out at this time. A mixing step is carried out at 90°C for 10 to 15min in order to obtain a homogeneous mixture. Then the set temperature of the internal mixer is brought to 165°C (in order to obtain a maximum temperature in the mixer of 175°C, heating due to friction and the radical decomposition reaction of the peroxide).Mixing is continued for 10 minutes when the set temperature is reached in the mixer to allow time for the reaction to take place (decomposition of the peroxides for the generation of radicals). The mixer is then stopped and the polymer can be recovered.

[0127] The material is then shaped into a plate approximately 1 mm thick using a CAR VER 3850CE press heated to 150°C, the pressure applied is 3 tonnes over a surface area of 22 cm by 22 cm. The plate obtained can be used as an encapsulant for small photovoltaic modules (cells and glass plate of 20 x 20 cm) by placing them in compression in the order glass, polymer, cells, polymer, backsheet at 160°C for 16 minutes. The module thus obtained can be dismantled by heating the system to 150°C and peeling the glass off the encapsulated module. Example 2

[0128] In a second example, the grafting reaction of divinyl PDMS is replaced by a grafting reaction of maleic anhydride. The functionalized polymer is then crosslinked with 1,3-bis(3-aminopropyl)tetramethyldisiloxane. The first step consists of placing 45 g of polyethylene (also called PE) having an IFC=14 g / 10 min (190°C, 2.16 kg, ASTM D1238) in the chamber of a HAAKE™ Rheomix QC50 internal mixer placed on a HAAKE™ PolyLab QC (Thermo Scientific™) platform with an internal volume of 70 cm3 and mixed at 130°C, with stirring at 30 rpm until a stable torque is obtained. 0.6 g of maleic anhydride is then placed in the internal mixer and then 23 mg of a radical activator, presently dicumyl peroxide, is added and left to stir for 10 min. The set temperature is then brought to 175°C and the medium is left to react for 10 min once the set temperature is reached.The crosslinking step is carried out using a solvent. The functionalized polymer is solubilized in hot xylene (110°C) at a level of 10% by mass of polymer. 1,3-bis(3-aminopropyl)tetramethyldisiloxane is then added (quantity calculated from the functionalization rate of the PE to be 1 molar equivalent in terms of functions) to the reaction medium. Gelation of the medium occurs in a few minutes. The xylene is then evaporated. Drying is carried out in a vacuum oven in order to completely shift the reaction equilibrium between the maleic anhydride functions and the amine functions. Following this drying step, the polymer is reshaped into a film so that it can then be used as an encapsulant in photovoltaic panels. Tests and measurements.

[0129] Dynamic mechanical analysis (DMA) and measurement of the swelling rate of the polymer obtained in Example 1

[0130] The measurement method Dynamic Mechanical Analysis (DMA) is a measurement of viscoelasticity which shows the formation of a polymer network. The device used is a DMA Q800 from TA Instrument®.

[0131] [Fig.7] shows the ADM curves (left) and the results of the swelling tests (swelling rate and insoluble fraction) (right) after 48 hours at 110°C in xylene of the polymer obtained in Example 1 without catalyst and with 0.1 mol% of catalyst (relative to the Si-O functions).

[0132] The insoluble rate (mass of polymer not dissolved after treatment in xylene at 110°C, 48 hours, divided by the total mass of sample expressed as a percentage) is close to 50%. The elastic modulus is greater than the loss modulus at the rubber plateau.

[0133] These two results confirm the obtaining of a polymer network in the encapsulants according to the invention. Creep test with the encapsulant of example 1

[0134] The device used for the creep test is a DMA Q800 from TA Instrument®.

[0135] The creep test was conducted at 140°C by imposing a constant stress of 1000 Pa for 30 minutes and releasing the stresses for a period of 30 minutes and at the same time measuring the deformation of the material over time. The test described corresponds to one cycle and the material underwent 6 successive cycles.

[0136] [Fig.8] shows the creep recovery result of the material of example 1 (with or without catalyst) (creep condition: o=1000 Pa, creep time: 30 min, recovery time: 30 min, number of cycles: 6). The material does not fully recover its percentage of deformation, it has therefore crept.

[0137] The creep test as well as the reprocessability of the materials when hot despite the presence of a network confirms the dynamics of the crosslinking points.

[0138] Optical property measurements by transmittance with the encapsulant of Example 1

[0139] Optical measurements of the encapsulants were carried out using the following equipment: BYK Haze Gard i.

[0140] This equipment makes it possible to give values of total transmission T, haze (turbidity) H, and clarity C.

[0141] The results are grouped in Table 2:

[0142] - with catalyst (0.1mol% relative to Si-O function): BA61 samples

[0143] - without catalyst: BA29 samples

[0144] The measurements were carried out 5 times on the same film but changing the measurement area.

[0145] Table 2: THC BA29 88.6 25.4 57.2 89 26.2 57.3 89 27.6 58.4 88.9 26.6 56 88.6 31.5 54.7 BA61 90.4 28.2 20.2 90.2 23.9 39.1 89.9 25.5 40.5 89.9 24.5 42.8 89.3 31.5 35.5

[0146] The given values of transmission T, haze H and clarity C are given in %.

[0147] The total transmission T is defined by the ratio between the total transmitted light intensity ITT and the incident light intensity Ib

[0148] T=100%xItt / I1

[0149] This value makes it possible to evaluate the proportion of light reflected or absorbed by the sample.

[0150] The haze value H measures the portion of transmitted light that deviates from the incident beam by more than 2.5° on average. It is defined by the ratio between the intensity scattered at an angle greater than 2.5° IDiff and the total transmitted intensity.

[0151] Haze = 100%x IDiff / ITT

[0152] The brightness value C allows the amount of narrow-angle scattering to be assessed. This is a more complex calculation that allows the amount of light intensity scattered at an angle less than 2.5° IR to be assessed compared to the unscattered light intensity and therefore transmitted parallel to the incident ray Ic.

[0153] C= 100% x (Ic-IR) / (Ic+Ir)

[0154] A value of 100% corresponds to a case where there is no scattered light.

[0155] A value of 0% corresponds to a case where the intensity of the scattered light I Rest is equal to the intensity of the incident light Ic.

[0156] Lamination / delamination / relamination of the glass / encapsulant / protective layer assemblies supporting the whole or backsheet

[0157] A lamination / delamination / relamination test was carried out to demonstrate the potential of this type of encapsulant to extend the lifespan of solar panels or facilitate their disassembly at the end of their life. Step 1#:

[0158] A glass (8cm x 8cm square) / encapsulant / backsheet assembly was prepared by lamination under a hydraulic press for 20 min at 150°C under a pressure of approximately 400 kg. The adhesion of the backsheet to the glass due to the presence of the encapsulant was demonstrated by having the assembly support a weight of 7 kg. Step 2#:

[0159] This assembly is then placed at 150°C for 10 minutes without applying pressure. The “backsheet + encapsulant” bilayer could be easily removed by hand from the solar glass. The solar glass shows very few traces of residual polymers. Step 3#:

[0160] The assembly was reformed by hot lamination (20 min at 150°C under 400 kg) of the two previously delaminated parts (solar glass and “backsheet + encapsulant "). The adhesion was again demonstrated by having the assembly support a weight of 7 kg.

[0161] All of these steps are described in [Fig.9] grouping the different steps in the form of photographs.

Claims

1. Claims Photovoltaic module encapsulant, characterized in that it comprises, - a polyolefin formula (I) [Chem.l] in which n = 1 to 100%, m = (100 - n)%, R1 and R2, identical or different, represent a hydrogen atom, an alkyl group comprising 1 to 24 carbon atoms, a cycloalkyl group comprising 3 to 24 carbon atoms, the alkyl and cycloalkyl groups being optionally substituted, said polyolefin having • a melt flow index (also called IFC) greater than 0.1g / 10min and less than 50g / 10min (ISO 1133-1 (2011) standard), 190°C, 2.16 kg), and • a mass crystallinity rate of less than 30%; - a disiloxane group, in particular a dialkylsiloxane group chosen from dimethylsiloxane and diethylsiloxane, and / or polydialkylsiloxane of formula (II): [Chem.2] in which • a = 1 to 100%, • b = (100 - a)%, and • the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, • R3 represents a methyl group, an ethyl group or \ which is the point of attachment of R3 to the polyolefin by a covalent bond, • R4, R5, R6, R7, and R8, identical or different, represent a methyl group or an ethyl group, • \ represents the point of attachment of the polydialkylsiloxane r to the polyolefin by a covalent bond, as crosslinker; the polyolefin representing from 78 to 99.75% by mass, the crosslinker from 0.25 to 22% by mass relative to the total mass of the composition of the encapsulant.

2. Encapsulant according to claim 1, characterized in that the polyolefin of formula (I) is chosen from linear low-density polyethylene (LLDPE or linear low-density polyethylene in English), low-density polyethylene (LDPE or low-density polyethylene in English), - polypropylene (PP).

3. Encapsulant according to one of claims 1 or 2, characterized in that the precursor of the disiloxane group is chosen from 1,3-bis(3-glycidyloxypropyl)tetramethyldisiloxane, 1,3-divinyl tetramethyldisiloxane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,3-bis(chloropropyl)tetramethyldisiloxane, 1,3-bis(hydroxypropyl)tetramethyldisiloxane, the grafting of which results in a polyalkylsiloxane of formula (II) [Chem. 3] s / 1 \ / VMJ < [MM i 5¾ 'b Rs in which • a = 1 to 100%, • b = (100 - a)%, and • the number of Si-O-Si repeat units is between 1 (dialkylsiloxane) and 5000, • R3 represents a methyl group, an ethyl group or \ which is the point of attachment of R3 to the polyolefin by a covalent bond, • R4, R5, R6, R7, and R8, identical or different, represent a methyl group or an ethyl group, * \ represents the point of attachment of the polydialkylsiloxane to the polyolefin by a covalent bond.

4. Encapsulant according to any one of claims 1 to 3, characterized in that the crosslinker represents from 0.25 to 10% by mass, relative to the total mass of the composition of the encapsulant.

5. Encapsulant according to any one of claims 1 to 4, characterized in that the crosslinker represents from 1 to 10% by mass relative to the total mass of the composition of the encapsulant.

6. Encapsulant according to any one of claims 1 to 5, characterized in that it comprises within the polyolefin or grafted onto the polyolefin, a catalyst chosen from - an organic base based on a ternary amine chosen from the group consisting of 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,5-diazabicyclo[4.3.0]non-5-en-silanolate,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane, and 1,1,3,3-tetramethylguanidine; - a quaternary ammonium chosen from the group consisting of tetramethylammonium hydroxide and tetramethylammonium silanolates; - a base chosen from the group consisting of KOH, potassium trimethylsilalonate; - a Lewis acid chosen from metal salts such as zinc trifluoromethanesulfonate (also called zinc triflate) or scandium trifluoromethanesulfonate (also called scandium triflate).

7. Encapsulant according to claim 6, characterized in that the catalyst loading is up to 10% by mass of the polyolefin of formula (I).

8. Encapsulant according to any one of claims 1 to 7, characterized in that the encapsulant further comprises additives selected from the group consisting of adhesion promoters, antioxidants, UV absorbers.

9. Use of an encapsulant according to any one of claims 1 to 8 in a photovoltaic module.

10. Photovoltaic module comprising - a transparent substrate, corresponding to solar glass, crystalline glass (mono or polycrystalline), thin-film glass, or ultra-white glass, - a layer of encapsulant according to the invention, - a photovoltaic cell, in particular based on silicon, copper-indium selenide (CuIn(Se)2, or CIS), copper, indium and gallium selenide (CuInGa(Se)2, also called CIGS), or cadmium telluride (CdTe), - another encapsulant layer according to the invention, - a protective layer supporting the whole (backsheet), made of polyvinylidene fluoride (PVDF), poly(p-phenylene oxide) (PPG) or poly(p-phenylene ether) (PPE), poly(ethylene terephthalate) (PET), polyvinyl chloride (PVC), or thermoplastic elastomer (TPE) or glass.

Images