Polymer and application thereof, packaging adhesive film and preparation method thereof, and photovoltaic module

Abstract

The invention relates to the field of solar cells, in particular to a polymer and application thereof, a packaging adhesive film and a preparation method thereof, and a photovoltaic module. The polymer provided by the invention has a structure as shown in the following formula 1: the polymer with the formula 1 is used for an ultraviolet light conversion agent, can effectively absorb ultraviolet light, can convert the absorbed ultraviolet light into visible light, and can remarkably improve the weather resistance of an ultraviolet light conversion packaging adhesive film; and the photoelectric conversion efficiency and the light transmittance of a photovoltaic module assembled by the ultraviolet light conversion packaging adhesive film containing the organic matter are obviously improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of solar cells, in particular to a polymer and application thereof, an encapsulation adhesive film and a preparation method thereof, and a photovoltaic module. BACKGROUND

[0002] The photoelectric conversion efficiency of a photovoltaic cell is one of the focuses in photovoltaic technology. According to theoretical calculation, the power generation efficiency of a solar cell can reach 26.8% to 30%. These losses are partly derived from the natural limitations of photoelectric conversion, the inherent band gap of a semiconductor material and the inherent spectrum of sunlight, which determines that light waves with a wavelength less than the minimum absorption limit and a photon energy greater than the part of the band gap are generally released through thermal vibration, i.e. ultraviolet light cannot be utilized. At the same time, some cell pieces are severely aged after being irradiated by ultraviolet light, especially heterojunction modules, which have a very high photoelectric conversion efficiency to a great extent due to the excellent surface passivation ability of intrinsic amorphous silicon to crystalline silicon. The disadvantage is that the transparent conductive oxide (TCO) film layer and the amorphous silicon film layer will absorb ultraviolet light, resulting in a lower current of the cell than ordinary cells and leading to a power attenuation of the module. Therefore, the requirement of heterojunction modules for resisting ultraviolet light is very high, not only to prevent the radiation aging of solar cell modules by ultraviolet light, but also to have a film layer with high light transmittance in the visible light region, while improving the photoelectric conversion efficiency of the cell module.

[0003] A light conversion agent is a product that can absorb negative gain light for a product and convert it into positive gain light, which is added to the adhesive film as an additive or an aid to form a light conversion film. The light conversion agent not only can absorb ultraviolet light, but also can convert the absorbed ultraviolet light into visible light. The functional principle of the light conversion agent is that after the material absorbs energy of a certain wavelength, the electron is excited to an excited state and is in a high-energy state. This energy can be transferred to the central ion, so that the electron jumps from the unstable high-energy state to the stable ground state. At the same time, in the return process, the energy is released in the form of light, thereby realizing light conversion.

[0004] The ultraviolet light conversion agent in the prior art is difficult to balance high light transmittance, high ultraviolet light absorption conversion rate, high weather resistance and low brightness decay ratio. SUMMARY

[0005] Therefore, the technical problem to be solved by the present application is to overcome the defects of the ultraviolet light conversion agent in the prior art, which is difficult to balance high light transmittance, high ultraviolet light absorption conversion rate and light stability, so as to provide a polymer and application thereof, an encapsulation adhesive film and a preparation method thereof, and a photovoltaic module.

[0006] As used in the present application, for example, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0007] As used in the present application, for example, the term "C3-C30 cycloalkyl" refers to a monocyclic or polycyclic hydrocarbon having 1 to 30 ring backbone carbon atoms, which can include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0008] In the present application, aryl and arylene include monocyclic, polycyclic or fused ring aryl, which can be interrupted by short non-aromatic units between the rings, and can contain a spiro structure, aryl includes but is not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, and the like, arylene includes but is not limited to phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, and the like.

[0009] As used in the present application, the term "substituted" means that a hydrogen atom in the compound is replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by the substituent. When two or more substituents are present, the two or more substituents can be the same or different.

[0010] In the present application, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range, for example, C6-C30 aryl, which represents the number of carbon atoms of the aryl group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25, or 30, and the like.

[0011] The scheme employed in the present application is as follows:

[0012] The present application provides a polymer having the structure shown in the following formula 1:

[0013]

[0014] wherein R1, R1' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 straight chain alkyl, substituted or unsubstituted C6-C60 aryl;

[0015] R3, R4 are each independently selected from substituted or unsubstituted C1-C30 straight chain alkyl, or substituted or unsubstituted C3-C30 cycloalkyl;

[0016] R2 is selected from one of the following structures:

[0017]

[0018] wherein T1, T2 are each independently selected from hydrogen or methyl; and at least one of T1, T2 is methyl;

[0019] T3, T4 are each independently selected from C1-C30 linear alkyl or T3, T4 are linked to form a ring A selected from a substituted or unsubstituted C3-C30 cycloalkane ring, a substituted or unsubstituted C3-C30 cycloalkene ring, or a substituted or unsubstituted C6-C60 aryl ring;

[0020] wherein T5 is a methyl group;

[0021] T6 is selected from C1-C30 linear alkyl;

[0022] n is a natural number greater than or equal to 1 and less than or equal to 100;

[0023] wherein the substituents of the substituted C1-C30 linear alkyl, the substituted C6-C60 aryl, the substituted C3-C30 cycloalkyl, the substituted C3-C30 cycloalkenyl, the substituted C3-C30 cycloalkane ring, the substituted C3-C30 cycloalkene ring, the substituted C6-C60 aryl ring are each independently selected from a hydroxyl group, a C1-C30 linear alkyl, a C1-C30 branched alkyl, a C2-C30 alkenyl, a C1-C16 alkoxy, a C1-C3 aldehyde group, a C2-C30 alkenyl-substituted carboxyl group, a C1-C16 alkoxysiloxy group, a C1-C16 alkoxysiloxy amine group, a C1-C16 ester group, a C1-C10 epoxyalkyl group, a C1-C10 ketone group, or a C1-C16 ester group.

[0024] Preferably, R1, R1' are each independently selected from a hydrogen, a deuterium, a substituted or unsubstituted C1-C15 linear alkyl, or a substituted or unsubstituted C6-C30 aryl;

[0025] and / or, R3, R4 are each independently selected from a substituted or unsubstituted C1-C15 linear alkyl, a substituted or unsubstituted C3-C15 cycloalkyl;

[0026] wherein the substituents of the substituted C1-C15 linear alkyl, the substituted C6-C30 aryl, the substituted C3-C15 cycloalkyl, the substituted C3-C15 cycloalkenyl are each independently selected from a hydroxyl group, a C1-C30 linear alkyl, a C1-C30 branched alkyl, a C2-C30 alkenyl, a C1-C16 alkoxy, a C1-C3 aldehyde group, a C2-C30 alkenyl-substituted carboxyl group, a C1-C16 alkoxysiloxy group, a C1-C16 alkoxysiloxy amine group, a C1-C16 ester group, a C1-C10 epoxyalkyl group, a C1-C10 ketone group, a C1-C16 ester group.

[0027] Preferably, T3, T4, T6 are each independently selected from a methyl group, an ethyl group, a propyl group, a butyl group, a n-pentane group, a n-hexane group, a n-heptane group, a n-octane group.

[0028] Preferably, ring A is selected from a substituted or unsubstituted cyclopentane ring, a substituted or unsubstituted cyclohexane ring.

[0029] wherein the substituents of the substituted cyclopentane ring, the substituted cyclohexane ring are methyl.

[0030] Preferably, R1, R1' are each independently selected from substituted or unsubstituted group B, group B is selected from the group consisting of methyl, phenyl;

[0031] wherein the substituents of the substituted group B are selected from the group consisting of hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl substituted carboxyl, C1-C16 alkoxy siloxy, C1-C16 alkoxy siloxy amine, C1-C16 ester, C1-C10 epoxy alkyl, C1-C10 ketone, C1-C16 ester;

[0032] Preferably, the substituents of the substituted group B are selected from the group consisting of methyl, hydroxyl, aldehyde, methoxy, trifluoromethyl, vinyl, or a group having the following structure:

[0033]

[0034] Preferably, R2 is selected from substituted or unsubstituted group C, group C is selected from the group consisting of methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, phenyl, cyclopentadienyl;

[0035] wherein the substituents of the substituted group C are selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl substituted carboxyl, C1-C16 alkoxy siloxy, C1-C16 alkoxy siloxy amine, C1-C16 ester, C1-C10 epoxy alkyl, C1-C10 ketone, C1-C16 ester;

[0036] Preferably, R3, R4 are each independently selected from substituted or unsubstituted group D, group D is selected from the group consisting of methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl;

[0037] wherein the substituents of the substituted group D are selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl substituted carboxyl, C1-C16 alkoxy siloxy, C1-C16 alkoxy siloxy amine, C1-C16 ester, C1-C10 epoxy alkyl, C1-C10 ketone, C1-C16 ester;

[0038] Preferably, n is a natural number from 2 to 60;

[0039] Further preferably, n is a natural number from 2 to 30;

[0040] Still further preferably, n is a natural number from 4 to 8.

[0041] Preferably, the polymer is selected from one of the following compounds:

[0042]

[0043]

[0044]

[0045] The present application also provides an ultraviolet light conversion agent, which is one or more of the above-mentioned polymers.

[0046] The present application also provides an adhesive film, which comprises one or more of the above-mentioned polymers.

[0047] Preferably, the adhesive film is a light conversion encapsulation adhesive film.

[0048] Further preferably, the adhesive film is an ultraviolet light conversion encapsulation adhesive film.

[0049] Preferably, the adhesive film further comprises a base material and an auxiliary agent selected from at least one of a photoinitiator, a light stabilizer, a crosslinking agent, a co-crosslinking agent, an antioxidant and a silane coupling agent.

[0050] Preferably, the adhesive film comprises a base material, an ultraviolet light conversion agent, a photoinitiator, a light stabilizer, a crosslinking agent, a co-crosslinking agent, an antioxidant and a silane coupling agent.

[0051] wherein the ultraviolet light conversion agent is one or more of the above-mentioned polymers.

[0052] Preferably, the adhesive film, in terms of weight parts, comprises: 100 parts of a base material, 0.005-2 parts of an ultraviolet light conversion agent, 0-2 parts of a photoinitiator, 0.1-1 parts of a light stabilizer, 0-3 parts of a crosslinking agent, 0-2 parts of a co-crosslinking agent, 0.05-1 parts of an antioxidant and 0.2-1 parts of a silane coupling agent.

[0053] Further preferably, the adhesive film, in terms of weight parts, comprises: 100 parts of a base material, 0.01-1 parts of an ultraviolet light conversion agent, 0.1-2 parts of a photoinitiator, 0.1-1 parts of a light stabilizer, 0.1-3 parts of a crosslinking agent, 0.1-2 parts of a co-crosslinking agent, 0.05-1 parts of an antioxidant and 0.2-1 parts of a silane coupling agent.

[0054] Preferably, the base material is an ethylene copolymer.

[0055] Preferably, the base material is at least one of ethylene-vinyl acetate copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate multi-copolymer, ethylene-methyl acrylate multi-copolymer, ethylene-ethyl acrylate multi-copolymer, ethylene-methyl methacrylate multi-copolymer, ethylene-ethyl methacrylate multi-copolymer, or ethylene-α-olefin copolymer.

[0056] Preferably, the base material is ethylene-vinyl acetate copolymer.

[0057] Preferably, the base material is ethylene-vinyl acetate copolymer, and the content of vinyl acetate structural unit in the ethylene-vinyl acetate copolymer is 25-35wt%, the melt index of the ethylene-vinyl acetate copolymer is 0.1-40g / min, the melting point is 40-90℃, and the light transmittance is ≥90%.

[0058] Preferably, the photoinitiator is selected from any one of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, benzophenone, (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, 2-hydroxy-2-methyl-1-phenylpropanone (2-hydroxy-1-(4-(2-hydroxy-2-methylpropanoyl) phenyl) benzyl)-2-methyl-1-propanone, titanium metallocene photoinitiator, thioxanthone / iodonium salt system, organic peroxide system, borate / dye system, hexaarylbiimidazole / dye system, coumarin ketone / dye system, benzil ketone photoinitiator, acetophenone photoinitiator, anthraquinone photoinitiator and its derivatives, benzoate photoinitiator, bicyclic diketone compound, camphorquinone, or a mixture of at least two thereof.

[0059] Preferably, the light stabilizer is selected from one or a mixture of at least two of bis(2,2,6,6-tetramethyl-4-piperidinol) sebacate, bis-2,2,6,6-tetramethylpiperidinol sebacate, 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, [[3,5-di-tert-butyl-4-hydroxyphenyl] methyl] butyl malonic acid di(1,2,2,6,6-pentamethyl-4-piperidyl) ester, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.

[0060] Preferably, the co-crosslinking agent is selected from one or a mixture of at least two of triallyl isocyanurate, ethylene glycol dimethacrylate, N,N'-m-phenyl bismaleimide, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, and ethoxylated pentaerythritol tetraacrylate.

[0061] Preferably, the antioxidant is selected from one or a mixture of at least two of 2,6-di-tert-butyl-p-cresol, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, beta-(3,5-di-tert-butyl-4-hydroxybenzyl) propionic acid isooctyl ester, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tetra(beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid) pentaerythritol ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), tetrakis(2,4-di-tert-butylphenyl-4,4'-biphenyl) bisphosphite, tris(2,4-di-tert-butylphenyl) phosphite.

[0062] Preferably, the silane coupling agent is selected from one or a mixture of at least two of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-triethoxysilyl-1-propylamine, (triethoxysilyl) ethylene, gamma-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane, gamma-methacryloyloxypropyltrimethoxysilane, gamma-methacryloyloxypropyltriisopropoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane.

[0063] The present application also provides a preparation method of the adhesive film, comprising the following steps: uniformly mixing, kneading and casting the base material, the ultraviolet light converter, the photoinitiator, the light stabilizer, the crosslinking agent, the co-crosslinking agent, the antioxidant and the silane coupling agent to obtain the adhesive film.

[0064] Preferably, the kneading temperature is 70-120℃; the kneading time is 10-40min; the rotation speed during the kneading process is 100-300r / min; and / or,

[0065] The thickness of the adhesive film after the casting is 0.3-0.8mm.

[0066] Preferably, the thickness of the adhesive film after the casting is 0.5mm.

[0067] Optionally, the flow casting process is carried out in a casting machine, and the ultraviolet light conversion packaging adhesive film is obtained through plasticizing extrusion, stretching, traction and winding.

[0068] The application further provides a photovoltaic module comprising the adhesive film prepared by the preparation method.

[0069] The application further provides a preparation method of the photovoltaic module, comprising the following steps: sequentially stacking a photovoltaic glass, the adhesive film prepared by the preparation method, a cell sheet, the adhesive film prepared by the preparation method, a photovoltaic back plate, and then performing heating and pressing to obtain the photovoltaic module.

[0070] Preferably, in the heating and pressing process, the heating temperature is 80-170 DEG C, the pressing pressure is 40 KPa-70 KPa, and the pressing time is 15-30 min.

[0071] Optionally, the flow casting process is carried out in a casting machine, and the ultraviolet light conversion packaging adhesive film is obtained through plasticizing extrusion, stretching, traction and winding.

[0072] The technical scheme of the application has the following advantages:

[0073] The polymer of the application has the structure of formula 1 as an ultraviolet light conversion agent. The ultraviolet light conversion packaging adhesive film prepared by using the structure of formula 1 can absorb ultraviolet light and convert it into visible light, thereby reducing the transmittance of ultraviolet light, and the ultraviolet light conversion packaging adhesive film has high permeability and can increase the transmittance of visible light. The polymer of the application comprises a structure molecule of triazole, and the 1-position and / or 3-position nitrogen atom in the triazole can form a weak interaction with H on the adjacent methyl group to form an intramolecular chelate ring, thereby increasing the conjugated area of the molecule. The polymer as an ultraviolet light conversion agent can increase the absorption of ultraviolet light. After absorbing the ultraviolet light, the energy is transferred to the light-emitting unit through intramolecular charge transfer, thereby converting it into visible light radiation, promoting the absorption of visible light by the solar cell, and improving the photoelectric conversion efficiency of the photovoltaic module. In addition, the polymer of the application can increase the stability of the ultraviolet light conversion packaging adhesive film, thereby reducing the brightness decay rate of the ultraviolet light conversion packaging adhesive film comprising the polymer, and thereby improving the weather resistance of the photovoltaic module. DETAILED DESCRIPTION

[0074] The following examples are provided to better further understand the application and are not limited to the best mode, and do not limit the content and protection scope of the application. Any person under the inspiration of the application or the combination of the application with other prior art features can obtain any product same or similar to the application, which falls within the protection scope of the application.

[0075] When specific experimental procedures or conditions are not mentioned in the examples, they are performed according to the conventional experimental procedures described in the literature. When the manufacturer of the reagent or instrument is not mentioned, it is a conventional reagent product that can be obtained commercially.

[0076] Unless otherwise specified, the room temperature described below means 25 ± 1℃.

[0077] The ethylene-vinyl acetate copolymer used in the present application has a vinyl acetate content of 28%, a melt index of 20 g / 10 min (under test conditions of 190℃ / 2.16 kg), and a melting point of 75℃.

[0078] Example 1

[0079] This example provides a method for preparing Polymer 2, which is prepared according to the following reaction formula, and specifically includes the following steps:

[0080]

[0081] Synthesis of Intermediate 2-1: In a flame-dried Schlenk tube, 0.1 mol of 4,7-dibromo-2-isobutyl-2H-benzo[d][1,2,3]triazole, 0.1 mol of 2,2'-(9,9-diethyl-9H-fluorene-2,7-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane), 0.005 mol of methanesulfonic acid(tris-tert-butylphosphine)(2'-methylamino-1,1'-biphenyl-2-yl)palladium(II)(Pd-P(-Bu)-G4), 0.22 mol of potassium trimethylsilanolate (TMSOK), and 5 ml of dry toluene (0.05 M) were added under a nitrogen atmosphere, and then the reaction mixture was stirred at 25℃ for 24 hours to obtain Intermediate 2-1 (yield: 56%).

[0082] Synthesis of Intermediate 2-2: 0.06 mol of Intermediate 2-1 was dissolved in 140 ml of toluene solvent, and stirred while being bubbled with nitrogen. 0.06 mol of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 0.3 mol of potassium carbonate, and 0.36 mmol of tetrakis(triphenylphosphine)palladium were sequentially added, and the temperature was raised to reflux. After 6 hours, HPLC detection showed that the raw material was substantially completely reacted, the reaction was stopped, and after cooling, the crude product was filtered to obtain a toluene solution. The filtrate was rotary evaporated under reduced pressure, and the residue was subjected to column chromatography to obtain Intermediate 2-2 (yield: 61%).

[0083] Synthesis of Intermediate 2-3: The synthesis method is the same as that of Intermediate 2-2, and Intermediate 2-3 is obtained (yield: 64%).

[0084] Synthesis of polymer 2: 0.01 mol of intermediate 2-3 was dissolved in 20 ml of dichloromethane, cooled to 0°C, and 0.013 mol of boron tribromide was added. The mixture was stirred at 0°C for 24 h. After the reaction was completed, an aqueous solution of sodium bicarbonate was added to quench the reaction, and then the mixture was extracted with dichloromethane three times. After drying over anhydrous magnesium sulfate, the reaction solution was rotary evaporated under reduced pressure. Polymer 2 was obtained by column chromatography (yield: 67%, n=4-6).

[0085] Example 2

[0086] This example provides a method for preparing polymer 5, which is as follows:

[0087]

[0088] Synthesis of intermediate 5-1: The synthesis method was the same as that of intermediate 2-1, except that intermediate 5-1” was used instead of intermediate 2-1”, to obtain intermediate 5-1 (yield: 56%).

[0089] Synthesis of intermediate 5-2: The synthesis method was the same as that of intermediate 2-2, except that intermediate 5-1 was used instead of intermediate 2-1, and 1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborinanyl-2-yl)phenyl)ethanone was used instead of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, to obtain intermediate 5-2 (yield: 69%).

[0090] Synthesis of polymer 5: The synthesis method was the same as that of intermediate 5-2, except that intermediate 5-2 was used instead of intermediate 5-1, and 1-(4-bromophenyl)ethanone was used instead of 1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborinanyl-2-yl)phenyl)ethanone, to obtain polymer 5 (yield: 63%, n=5-7).

[0091] Example 3

[0092] This example provides a method for preparing polymer 12, which is as follows:

[0093]

[0094] Synthesis of intermediate 12-1: 0.1 mol of 2,4-dimethyl-3-pentanol was dissolved in 110 ml of dichloromethane, and trifluoromethanesulfonic anhydride was added dropwise. The mixture was stirred at room temperature for 5 h. The organic phase was rotary evaporated under reduced pressure, and the residue was subjected to column chromatography to obtain intermediate 2-1 (yield: 67%).

[0095] Synthesis of intermediate 12-2: 0.05 mol of 4,7-dibromo-2H- benzo[d][l,2,3]triazole was dissolved in 140 ml of toluene, 0.05 mol of intermediate 12-1, 0.125 mol of sodium tert-butoxide, 0.15 mmol of tris(dibenzylideneacetone)dipalladium, 0.15 mmol of tri-tert-butylphosphine were added, stirred under nitrogen, and warmed to reflux. After 4 h, the reaction was determined to be complete, the reaction solution was rotary evaporated under reduced pressure, and intermediate 12-2 was obtained by column chromatography (yield: 63%).

[0096] Synthesis of intermediate 12-3: The same as the synthesis of intermediate 2-1, except that intermediate 12-3' was used instead of intermediate 2-1", and intermediate 12-2 was used instead of intermediate 2-1', to obtain intermediate 12-3 (yield: 51%).

[0097] Synthesis of intermediate 12-4: The same as the synthesis of intermediate 2-2, except that intermediate 12-3 was used instead of intermediate 2-1, to obtain intermediate 12-4 (yield: 66%).

[0098] Synthesis of polymer 12: The same as the synthesis of intermediate 12-4, except that intermediate 12-4 was used instead of intermediate 12-3, and p-bromoacetophenone was used instead of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-l,3,2-dioxaborolane, to obtain polymer 12 (yield: 63%, n = 6-8).

[0099] Example 4

[0100] This example provides a preparation method of polymer 25, which is as follows:

[0101]

[0102] Synthesis of intermediate 25-1: 0.06 mol of (4-bromophenyl)trimethoxysilane was dissolved in 160 ml of 1,4-dioxane solvent, stirred under nitrogen, and 0.06 mol of pinacol diboronic acid, 0.15 mol of potassium acetate, and 0.18 mmol of ferrocene dichloropalladium were sequentially added. The reaction was warmed to reflux, and after 4 h, HPLC detection showed that the raw material was substantially reacted. The reaction was stopped, the reaction solution was rotary evaporated under reduced pressure, and the residue was obtained by column chromatography to obtain intermediate 25-1 (yield: 61%).

[0103] Synthesis of intermediate 25-2: The same as the synthesis of intermediate 2-1, except that intermediate 25-2" was used instead of intermediate 2-1", to obtain intermediate 25-2 (yield: 51%).

[0104] Synthesis of intermediate 25-3: The synthesis was performed according to the synthetic procedure of intermediate 2-2, except that intermediate 25-2 was used in place of intermediate 2-1, and 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was replaced by intermediate 25-1 to give intermediate 25-3 (yield: 68%).

[0105] Synthesis of polymer 25: The synthesis was performed according to the synthetic procedure of intermediate 25-3, except that intermediate 25-3 was used in place of intermediate 25-2, and 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was replaced by 4-bromophenyltrimethoxysilane to give polymer 25 (yield: 62%, n = 4-6).

[0106] Example 5

[0107] This example provides a preparation method of polymer 26, which is prepared according to the following reaction formula, and specifically comprises the following steps:

[0108]

[0109] Synthesis of intermediate 26-1 : The synthesis was performed according to the synthetic procedure of intermediate 2-1, except that compound 26-1 " was used in place of intermediate 2-1 " to give intermediate 26-1 (yield: 53%).

[0110] Synthesis of intermediate 26-2: The synthesis was performed according to the synthetic procedure of intermediate 2-2, except that intermediate 26-1 was used in place of intermediate 2-1, and 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was replaced by 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane to give intermediate 26-2 (yield: 62%).

[0111] Synthesis of polymer 26: The synthesis was performed according to the synthetic procedure of intermediate 26-2, except that intermediate 26-2 was used in place of intermediate 26-1, and 4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)phenyl)-1,3,2-dioxaborolane was replaced by 1 -bromo-4-(trifluoromethyl)benzene to give polymer 26 (yield: 65%, n = 6-8).

[0112] Example 6

[0113] This example provides a preparation method of polymer 30, which is prepared according to the following reaction formula, and specifically comprises the following steps:

[0114]

[0115] Synthesis of intermediate 30-1 : The synthesis method is the same as that of synthesis of intermediate 2-2, except that intermediate 26-1 is used instead of intermediate 2-1, 4,4,5,5-tetramethyl-2-(p-tolyl)-1,3,2-dioxaborinane is used instead of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, to obtain intermediate 30-1 (yield: 67%).

[0116] Synthesis of polymer 30: The synthesis method is the same as that of synthesis of intermediate 30-1, except that intermediate 30-1 is used instead of intermediate 26-1, p-bromotoluene is used instead of 4,4,5,5-tetramethyl-2-(p-tolyl)-1,3,2-dioxaborinane, to obtain polymer 30 (yield: 62%, n = 5-7).

[0117] Example 7

[0118] This example provides a preparation method of polymer 40, which is prepared according to the following reaction formula, and specifically comprises the following steps:

[0119]

[0120] Synthesis of intermediate 40-1 : The synthesis method is the same as that of synthesis of intermediate 2-2, except that intermediate 25-2 is used instead of intermediate 2-1, to obtain intermediate 40-1 (yield: 66%).

[0121] Synthesis of polymer 40: The synthesis method is the same as that of synthesis of intermediate 40-1, except that 1-bromo-4-methoxybenzene is used instead of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, to obtain polymer (yield: 64%, n = 4-6).

[0122] Example 8

[0123] This example provides a preparation method of polymer 52, which is prepared according to the following reaction, and specifically comprises the following steps:

[0124]

[0125] Synthesis of intermediate 52-1 : The synthesis method is the same as that of synthesis of intermediate 2-2, except that intermediate 26-1 is used instead of intermediate 2-1, 4-isopropoxyphenylboronic acid pinacol ester is used instead of 2-(4-methoxyphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, to obtain intermediate 52-1 (yield: 61%).

[0126] Synthesis of polymer 52: the synthesis method is the same as that of the synthesis of intermediate 52-1, except that intermediate 40-1 is used instead of intermediate 26-1, and 1-bromo-4-isopropoxybenzene is used instead of 4,4,5,5-tetramethyl-2-(p-tolyl)-1,3,2-dioxaborinane, to obtain polymer 52 (yield: 65%, n = 6-8).

[0127] Packaging adhesive film embodiment:

[0128] The packaging adhesive film embodiment is a light conversion packaging adhesive film, and the preparation method of the packaging adhesive film comprises the following steps:

[0129] The base material, the ultraviolet light conversion agent, the photoinitiator, the light stabilizer, the crosslinking agent, the co-crosslinking agent, the antioxidant, and the silane coupling agent are uniformly mixed in a mixing kettle, and then are put into a double-screw extruder, and are mixed at a speed of 200 r / min at 90°C, and then are extruded, stretched, pulled, and wound in a casting machine to obtain a light conversion packaging adhesive film with a thickness of 0.5 mm;

[0130] Packaging adhesive film embodiment 1:

[0131] The packaging adhesive film is prepared by the above preparation method, wherein the base material is 100 g of ethylene-vinyl acetate copolymer, the ultraviolet light conversion agent is 0.1 g of polymer 2, the photoinitiator is 1 g of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) butanone, the light stabilizer is 0.1 g of bis-2,2,6,6-tetramethylpiperidinyl octadecanedioate, the crosslinking agent is 0.5 g of tert-butyl 2-ethylhexyl peroxide carbonate, the co-crosslinking agent is 0.5 g of N,N'-m-phenyl bismaleimide, the antioxidant is 0.05 g of tris(nonylphenyl) phosphite, and the silane coupling agent is 0.2 g of 3-mercapto propyl triethoxysilane.

[0132] Packaging adhesive film embodiment 2:

[0133] The embodiment is similar to the packaging adhesive film embodiment 1, except that the ultraviolet light conversion agent is 0.05 g of polymer 2.

[0134] Packaging adhesive film embodiment 3:

[0135] The embodiment is similar to the packaging adhesive film embodiment 1, except that the ultraviolet light conversion agent is 0.3 g of polymer 2.

[0136] Packaging adhesive film embodiments 4-15:

[0137] The preparation method of the packaging adhesive film embodiments 4-15 is referred to the packaging adhesive film embodiment 1, except that other polymers in the application are used to replace polymer 2, and the specific polymers are shown in Table 1.

[0138] Table 1 UV light conversion agent in encapsulation adhesive film examples 4-11

[0139]

[0140]

[0141] Encapsulation adhesive film comparative example 1:

[0142] The preparation method of encapsulation adhesive film comparative example 1 refers to that of encapsulation adhesive film example 1, except that Ref1 (synthesis method refers to that of polymer 2, n = 4-6) is used to replace polymer 2.

[0143]

[0144] Encapsulation adhesive film comparative example 2:

[0145] The preparation method of encapsulation adhesive film comparative example 2 refers to that of encapsulation adhesive film example 1, except that Ref2 (synthesis method refers to that of polymer 2, n = 4-6) is used to replace polymer 2.

[0146]

[0147] Encapsulation adhesive film comparative example 3:

[0148] The preparation method of encapsulation adhesive film comparative example 3 refers to that of encapsulation adhesive film example 1, except that Ref3 is used to replace polymer 2.

[0149]

[0150] Test example

[0151] The performance of the UV light conversion encapsulation adhesive films obtained from encapsulation adhesive film examples 1-15 and encapsulation adhesive film comparative examples 1-3 was tested.

[0152] The test standard of transmittance refers to GB / T29848-2018, and the light transmittance test is performed by using a specific UV-visible spectrophotometer (PerkinElmer LAMBDA 950); the waveband of 280-380 nm and the waveband of 380-1100 nm are tested respectively.

[0153] UV aging resistance test: tested according to IEC61215 standard. Test conditions: sample area 12 cm*6 cm, irradiance 120 W / m 2 Under the conditions of 85℃ and 85% humidity for 1440h, the decay rate of the test relative to the initial brightness was tested.

[0154] Photovoltaic modules comprising encapsulant film Example 1 11 and encapsulant film Comparative Example 1-2 were tested for photoelectric conversion efficiency, wherein the photovoltaic modules were prepared by stacking photovoltaic glass, light conversion encapsulant film, cell sheet, light conversion encapsulant film and photovoltaic back sheet in order, and placing them in a laminator for lamination, laminating at 100°C for 20 min, laminating pressure 60 KPa, taking out and cooling to obtain the photovoltaic module. (The two light conversion encapsulant films in the same photovoltaic module are of the same type).

[0155] Photoelectric conversion efficiency test: a standard sunlight was emitted by a solar simulator for testing (spectrum AM1.5G, incident power 100 mW / cm 2 , temperature 25°C).

[0156] Photoelectric conversion efficiency test: a standard sunlight was emitted by a solar simulator for testing (spectrum AM1.5G, incident power 100 mW / cm 2, temperature 25°C).

[0157] The calculation method of the photoelectric conversion improvement rate in Table 2 is as follows: the photoelectric conversion efficiency of encapsulant film Comparative Example 1 is taken as the comparison standard 100%, and the photoelectric conversion efficiency of the other encapsulant films is compared respectively to calculate the improvement rate.

[0158] Photoelectric conversion improvement rate % = (photoelectric conversion efficiency of the current instance of encapsulant film - photoelectric conversion efficiency of encapsulant film Comparative Example 1) / photoelectric conversion efficiency of encapsulant film Comparative Example 1 x 100%

[0159] The test results are shown in Table 2.

[0160] Table 2

[0161]

[0162] It is obvious that the above embodiments are only examples for the purpose of clarity, and are not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. All embodiments do not need to be exhausted, and obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A polymer, characterized in that, The polymer has a structure shown in Formula 1 below: wherein R1, R1' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 linear alkyl, substituted or unsubstituted C6-C60 aryl; R3, R4 are each independently selected from substituted or unsubstituted C1-C30 linear alkyl, or substituted or unsubstituted C3-C30 cyclic alkyl; R2 is selected from one of the following structures: wherein T1, T2 are each independently selected from hydrogen or methyl; and at least one of T1, T2 is methyl; T3, T4 are each independently selected from C1-C30 linear alkyl, or T3, T4 are linked to form a ring A, and the ring A is selected from substituted or unsubstituted C3-C30 cyclic alkane ring, substituted or unsubstituted C3-C30 cyclic alkene ring, or substituted or unsubstituted C6-C60 aryl ring; wherein T5 is methyl; T6 is selected from C1-C30 linear alkyl; n is a natural number greater than or equal to 1 and less than or equal to 100; wherein the substituents in the substituted C1-C30 linear alkyl, substituted C6-C60 aryl, substituted C3-C30 cyclic alkyl, substituted C3-C30 cyclic alkene, substituted C3-C30 cyclic alkane ring, substituted C3-C30 cyclic alkene ring, substituted C6-C60 aryl ring are each independently selected from hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl-substituted carboxyl, C1-C16 alkoxy siloxy, C1-C16 alkoxy siloxy amine, C1-C16 ester, C1-C10 epoxy alkyl, C1-C10 ketone, or C1-C16 ester.

2. The polymer of claim 1, wherein R1, R1' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 linear alkyl, or substituted or unsubstituted C6-C30 aryl; and / or, R3, R4 are each independently selected from substituted or unsubstituted C1-C15 linear alkyl, substituted or unsubstituted C3-C15 cyclic alkyl; wherein the substituents in the substituted C1-C15 linear alkyl, substituted C6-C30 aryl, substituted C3-C15 cyclic alkyl, substituted C3-C15 cyclic alkene are each independently selected from hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl-substituted carboxyl, C1-C16 alkoxy siloxy, C1-C16 alkoxy siloxy amine, C1-C16 ester, C1-C10 epoxy alkyl, C1-C10 ketone, C1-C16 ester.

3. The polymer according to claim 1 or 2, characterized in that, T3, T4, T6 are each independently selected from methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl.

4. The polymer according to any one of claims 1 to 3, characterized in that, Ring A is selected from substituted or unsubstituted cyclopentane ring, substituted or unsubstituted cyclohexane ring; wherein the substituents in the substituted cyclopentane ring, substituted cyclohexane ring are methyl.

5. The polymer according to any one of claims 1 to 4, characterized in that, R1, R1' are each independently selected from substituted or unsubstituted group B, and group B is selected from the following groups: methyl, phenyl; wherein the substituents of the substituted group B are selected from the group consisting of hydroxyl, C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl-substituted carboxyl, C1-C16 alkoxysiloxy, C1-C16 alkoxysiloxyamino, C1-C16 ester, C1-C10 epoxyalkyl, C1-C10 ketone, C1-C16 ester; Preferably, the substituents of the substituted group B are selected from the group consisting of methyl, hydroxyl, aldehyde, methoxy, trifluoromethyl, vinyl, or a group having the following structure: Preferably, R2 is selected from a substituted or unsubstituted group C, and the group C is selected from the group consisting of methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl, phenyl, cyclopentadienyl; wherein the substituents of the substituted group C are selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl-substituted carboxyl, C1-C16 alkoxysiloxy, C1-C16 alkoxysiloxyamino, C1-C16 ester, C1-C10 epoxyalkyl, C1-C10 ketone, C1-C16 ester; Preferably, R3 and R4 are each independently selected from a substituted or unsubstituted group D, and the group D is selected from the group consisting of methyl, ethyl, propyl, butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, cyclopentyl, cyclohexyl; wherein the substituents of the substituted group D are selected from the group consisting of C1-C30 linear alkyl, C1-C30 branched alkyl, C2-C30 alkenyl, C1-C16 alkoxy, C1-C3 aldehyde, C2-C30 alkenyl-substituted carboxyl, C1-C16 alkoxysiloxy, C1-C16 alkoxysiloxyamino, C1-C16 ester, C1-C10 epoxyalkyl, C1-C10 ketone, C1-C16 ester; Preferably, n is a natural number from 2 to 60; Further preferably, n is a natural number from 2 to 30; More preferably, n is a natural number from 4 to 8.

6. The polymer according to any one of claims 1 to 5, characterized in that, The polymer is selected from one of the following compounds:

7. An ultraviolet light converter, characterized by, The ultraviolet light conversion agent is one or more of the polymers of any one of claims 1-6.

8. An adhesive film, characterized by The adhesive film comprises one or more of the polymers of any one of claims 1-6; Preferably, the adhesive film is a light conversion encapsulation adhesive film; Further preferably, the adhesive film is an ultraviolet light conversion encapsulation adhesive film; Preferably, the adhesive film further comprises a base material and an auxiliary agent, and the auxiliary agent is selected from at least one of a photoinitiator, a light stabilizer, a crosslinking agent, a co-crosslinking agent, an antioxidant, and a silane coupling agent; Preferably, the adhesive film comprises a base material, an ultraviolet light conversion agent, a photoinitiator, a light stabilizer, a crosslinking agent, a co-crosslinking agent, an antioxidant, and a silane coupling agent; wherein the ultraviolet light conversion agent is one or more of the polymers of any one of claims 1-6. Preferably, the raw materials of the adhesive film include: 100 parts of the base material, 0.005-2 parts of the ultraviolet light conversion agent, 0-2 parts of the photoinitiator, 0.1-1 parts of the light stabilizer, 0-3 parts of the crosslinking agent, 0-2 parts of the co-crosslinking agent, 0.05-1 parts of the antioxidant and 0.2-1 parts of the silane coupling agent. Further preferably, the raw materials of the adhesive film include: 100 parts of the base material, 0.01-1 parts of the ultraviolet light conversion agent, 0.1-2 parts of the photoinitiator, 0.1-1 parts of the light stabilizer, 0.1-3 parts of the crosslinking agent, 0.1-2 parts of the co-crosslinking agent, 0.05-1 parts of the antioxidant and 0.2-1 parts of the silane coupling agent.

9. A method of producing the adhesive film according to claim 8, characterized by, The preparation method of the adhesive film includes the following steps: uniformly mixing, kneading and flow casting the base material, the ultraviolet light conversion agent, the photoinitiator, the light stabilizer, the crosslinking agent, the co-crosslinking agent, the antioxidant and the silane coupling agent to obtain the adhesive film. Preferably, the kneading temperature is 70-120℃, the kneading time is 10-40min, the rotation speed during the kneading process is 100-300r / min, and / or the thickness of the adhesive film after the flow casting is 0.3-0.8mm. Preferably, the thickness of the adhesive film after the flow casting is 0.5mm. The adhesive film prepared by the preparation method of the adhesive film in claim 9.

10. A photovoltaic module, characterized by, Preferably, the preparation method of the photovoltaic module includes the following steps: sequentially stacking the photovoltaic glass, the adhesive film prepared by the preparation method of the adhesive film in claim 9, the cell sheet, the adhesive film prepared by the preparation method of the adhesive film in claim 9 and the photovoltaic backboard, and then performing heating and pressing to obtain the photovoltaic module. ​

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