A graftable fused ring material, grafted adhesive film and its application

Abstract

This invention discloses a graftable fused-ring material, a grafted adhesive film, and their applications. The graftable fused-ring material includes compounds having the structure shown in the following formula: the raw materials for preparing the grafted adhesive film include the graftable fused-ring material. The graftable fused-ring material of this invention has vinyl terminals and can be grafted with various resins through simple reactions (such as graft copolymerization with POE / EVA, forming C-C linkages through free radical initiation and coupling with the resin-based film to form a grafted adhesive film, thereby greatly improving the anti-migration and anti-aggregation properties of the graftable fused-ring material in the resin adhesive film), thus crosslinking onto the resin and fundamentally avoiding the migration problem between small molecules, thereby improving the service life of the color conversion adhesive film.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic materials technology, specifically to a graftable fused ring material, a grafted adhesive film, and their applications (specifically, photovoltaic modules). More particularly, it relates to a graftable fused ring material, a grafted adhesive film with high anti-migration and strong anti-aggregation properties prepared using the aforementioned graftable fused ring material, and a photovoltaic module using the aforementioned grafted adhesive film. Background Technology

[0002] Solar power generation systems have long been a focus of attention as a clean energy option with lower environmental impact. Although they typically exhibit high reliability and low failure / degradation rates during long-term field operation, their core component—the solar cell—still faces the adverse effects of solar ultraviolet radiation. Current solutions each have their limitations: while using UV-blocking encapsulating films can shield ultraviolet light, this directly results in the loss of this light energy; and while using films doped with wavelength-converting luminescent materials (light conversion agents) aims to convert harmful ultraviolet light into usable visible light (redshift), theoretically improving efficiency, the film's performance often deteriorates due to phenomena such as additive aggregation and precipitation (phase separation). The key to overcoming these technical bottlenecks lies in developing light conversion materials with excellent dispersion stability or functional encapsulating films composed of them.

[0003] Therefore, developing a light conversion material with excellent dispersion stability is of great practical significance. Summary of the Invention

[0004] Due to the aforementioned deficiencies in the existing technology, the present invention provides a light conversion material with excellent dispersion stability, specifically a graftable fused ring material, a grafted adhesive film, and its application. This type of material can crosslink with most adhesive films to form a stable color light conversion film, thereby having a longer service life and further extending the service life of the equipment.

[0005] To achieve the above objectives, the present invention provides the following technical solution:

[0006] A graftable fused ring material comprising a compound having the structure shown in (Ⅰ):

[0007]

[0008] (I)

[0009] Wherein, R1 to R6 are each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted amino, substituted or unsubstituted amide, substituted or unsubstituted cyclic imino, substituted or unsubstituted alkoxy, substituted or unsubstituted carboxyl, substituted or unsubstituted ester, and substituted or unsubstituted carbonyl, and R1 to R6 are not simultaneously H; the substituted substituents include C1 to C1. 28 Hydroxyl group, C1~C 28 Ester group, C1~C 28 Carboxyl group, C1~C 28 Amino, C1~C 28 thiol group, C1~C 28 amide group, C1~C 28 carbonyl group, C1~C 28 Alkoxy, C6~C 28 Aryl, C4~C 28 heteroaryl, C1~C 28 Alkyl, C1~C 28 Heteroalkyl, C1~C 28 alkenyl and C1~C 28 Any one of the imino groups;

[0010] L1 and L2 are each independently derived from C1~C 28 Alkylene, C1~C 28 Etheryl group, C1~C 28 Ester group, C1~C 28 Imino, C1~C 28 imide group, C1~C 28 carbonyl group, C1~C 28 aryl, C1~C 28 alkenyl, C1~C 28 Any one of the ynylene groups;

[0011] The Ar is selected from ungrouped, substituted alkylene, optionally substituted alkenyl, optionally substituted aryl, and optionally substituted heteroaryl.

[0012] This invention provides a fundamental solution using grafting crosslinking technology: this technology, through a free radical-initiated reaction, directly and stably anchors small-molecule light-converting agents to the polymer chains of the film (matrix resin) in the form of C-C covalent bonds. This in-situ chemical bonding strategy completely severs the migration and diffusion pathways of small molecules from a mechanistic perspective, thereby significantly improving the physical stability and service life of the light-converting film.

[0013] The graftable fused ring material of the present invention has vinyl ends and can be grafted with various resins through simple reactions (such as graft copolymerization of POE and EVA, forming CC linkage through free radical initiation and coupling with the resin-based film to form a grafted film, thereby greatly improving the anti-migration and anti-aggregation properties of the graftable fused ring material in the resin film), thus crosslinking onto the resin, fundamentally avoiding the migration problem between small molecules, thereby improving the service life of the color conversion film.

[0014] As a preferred technical solution:

[0015] In the graftable fused ring material described above, the substituents in the optionally substituted aryl or optionally substituted heteroaryl groups are each independently selected from one or more groups of C1 to C2. 20 Alkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C3-C7 cycloalkyl, gem-linked cycloalkyl, C1-C6 heteroalkyl, C3-C 10 Heterocyclic alkyl, aryl, aralkyl, heteroaryl, halogenated, cyano, hydroxyl, optionally substituted cyclic imino, amino, imino, amide, C1-C 10 Alkyloxy, aryloxy, acyloxy, mercapto, halogenated C1-C 10 Alkyl, C1-C 10 Alkylthio, arylthio, mono-C1 to C1-C2 10 Alkylamino, diC1-C 10 Alkylamino, quaternary ammonium salt, amino C1-C 10 Alkoxy, hydroxyl C1-C 10 Alkylamino, amino C1-C 10 Alkylthio, cyanoamino, nitro, carbamoyl, oxy, carbonyl, carboxyl, hydroxyacetyl, glycyl, hydrazine, amidoyl, aminesulfonyl, sulfonyl, sulfinyl, thiocarbonyl, thiocarboxyl, sulfonamide, ester, C-amide, N-amide, N-carbamate, O-carbamate, urea, and combinations thereof.

[0016] As described above, in a graftable fused ring material, R1 and R2 are each independently selected from H, substituted or unsubstituted C1 to C2. 20 Alkyl, substituted or unsubstituted C1-C 20 Any one of the alkenyl groups;

[0017] L1 and L2 are each independently derived from substituted or unsubstituted C1 to C2. 10 Any one of the alkyl groups.

[0018] The graftable fused-ring material described above comprises any one or a combination of at least two of the following compounds:

[0019] .

[0020] The present invention also provides a grafted adhesive film, wherein the raw materials for preparing the grafted adhesive film include the graftable fused ring material as described above.

[0021] As a preferred technical solution:

[0022] The grafted adhesive film described above is prepared from the following raw materials: resin particles, graftable fused ring material as described above, crosslinking agent, modified silane, acrylate, light stabilizer, and anti-stabilizer.

[0023] As described above, the grafted adhesive film, based on the weight parts of the raw materials for preparing the grafted adhesive film, comprises the following components:

[0024] 50-95 parts of resin particles;

[0025] 1-30 parts of graftable fused ring material;

[0026] Crosslinking agent 0.5-3 parts;

[0027] 0.3-2 parts of modified silane;

[0028] Acrylic ester 0.5~1.5 parts;

[0029] Light stabilizer 0.1~0.5 parts;

[0030] Antioxidant 0.1~0.5 parts.

[0031] By controlling the content of each component within the above range, the prepared grafted film can have better overall performance, such as higher resistance to migration and exudation, as well as better bonding strength.

[0032] Preferably, the raw materials for preparing the grafted adhesive film can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, or 95 parts by weight of resin particles.

[0033] Preferably, the raw materials for preparing the grafted film, by weight, can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, or 30 parts, etc.

[0034] As described above, the grafted adhesive film includes any one or a combination of at least two of the following crosslinking agents: tert-butyl peroxide-2-ethylhexyl carbonate, tert-amyl peroxy-2-ethylhexyl carbonate, triallyl isocyanurate, triallyl cyanurate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, or dicumyl peroxide.

[0035] The modified silane includes any one or a combination of at least two of the following: propyltrioxyethyl isocyanate, vinyltriacetoxysilane, methacryloyloxypropyltrimethoxysilane derivatives, alkylaminosilane oligomers, alkylvinylsilane oligomers, epoxysilane oligomers, aminosilane oligomers, small molecule polysiloxanes, mercaptosilane derivatives, or hybrid functional silanes.

[0036] The acrylates include any one or a combination of at least two of the following: ethoxytrimethylolpropane triacrylate, propoxytrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyethylene glycol diacrylate, tricyclodecanedimethylol diacrylate, or ditrimethylolpropane tetraacrylate.

[0037] The light stabilizer includes any one or a combination of at least two of the following: succinic acid, (a polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), bis-2,2,6,6-tetramethylpiperidinol sebacate or hindered amine light stabilizer, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(2,4-di-tert-butylphenyl) phosphite or 2,2,6,6-tetramethyl-4-piperidinol ester;

[0038] The antioxidant includes any one or a combination of at least two of the following: octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or tris[2,4-di-tert-butylphenyl]phosphite.

[0039] The grafted adhesive film as described above, wherein the resin comprises any one or a combination of at least two of polyvinyl acetate, polyethylene-octene copolymer, polyvinyl butyral, hot-melt polyolefin particles, or thermoplastic polyurethane.

[0040] It should be noted that the present invention does not impose specific limitations on the preparation method of the grafted POE film, which can be prepared according to conventional methods. For example, the preparation method of the grafted POE film includes the following steps:

[0041] POE particles, graftable fused ring materials, crosslinking agents, modified silanes, acrylates, light stabilizers, and antioxidants are mixed and then co-extruded and cast through a screw extruder to obtain a grafted POE film.

[0042] In addition, the present invention also provides a photovoltaic module comprising the grafted adhesive film and the battery as described above.

[0043] As a preferred technical solution:

[0044] The photovoltaic module described above includes any one or a combination of at least two of the following: indium gallium arsenide solar cells, organic solar cells, perovskite solar cells, cadmium sulfide / cadmium telluride solar cells, amorphous silicon solar cells, microcrystalline silicon solar cells, and crystalline silicon solar cells.

[0045] The above technical solution is only one feasible technical solution of the present invention. The scope of protection of the present invention is not limited thereto. Those skilled in the art can reasonably adjust the specific design according to actual needs.

[0046] The above invention has the following advantages or beneficial effects:

[0047] (1) The graftable fused ring material of the present invention can be grafted with various resins through a simple reaction, thereby crosslinking onto the resin, fundamentally avoiding the migration problem between small molecules, thereby improving the service life of the color conversion film.

[0048] (2) In the grafted film of the present invention, the color conversion agent that can be grafted and connected to the film through chemical bonds can exist more stably in the film, avoiding the aggregation and precipitation of the conversion agent, which can significantly improve the service life of the film, thereby improving production efficiency and having good application prospects. Detailed Implementation

[0049] The present invention will be further described below with reference to specific embodiments, but these are not intended to limit the invention.

[0050] Example 1

[0051] A graftable fused ring material Xa, with the following specific structural formula:

[0052] .

[0053] Its preparation method includes the following steps:

[0054] (1) Mix 4-hexenylphenol (98g), nitric acid (30ml) and acetic acid (300ml), then stir overnight at room temperature under nitrogen protection. After the reaction is complete, pour the reaction solution into water, extract with dichloromethane, and then distill the extract under reduced pressure (<-0.08Mpa). Separate the extract by silica gel column to obtain 4-hexenyl-2-nitrophenol (yield 88%).

[0055]

[0056] (2) 4-Hexenyl-2-nitrophenol (50g), Pd / C (0.5g), hydrazine hydrate (30ml) and ethanol (100ml) were poured into a reaction flask and reacted at 78°C for 6h under N2 atmosphere. After the reaction was completed, the mixture was filtered and concentrated under reduced pressure to obtain 4-hexenyl-2-aminophenol (yield 91%).

[0057]

[0058] (3) The intermediate product (30g), thiophene 1,4-dicarboxylate (10g), and polyphosphoric acid (200ml) obtained in step (2) were added to the reactor and deoxygenated by nitrogen. Then, the reaction was carried out at 180℃ for 5h under a nitrogen atmosphere. After the reaction was completed, the reaction solution was poured into water, extracted with ethyl acetate, concentrated by vacuum distillation, and separated by silica gel column chromatography to obtain the ultraviolet absorber Xa (yield 67%). UV-vis spectrum (chloroform): λ max =358nm.

[0059] Those skilled in the art should understand that variations can be implemented by combining existing technology with the above embodiments, which will not be elaborated here. Such variations do not affect the essence of the present invention, and will not be elaborated here either.

[0060] The preferred embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and the devices and structures not described in detail should be understood as being implemented in a conventional manner in the art. Any person skilled in the art can make many possible variations and modifications to the technical solutions of the present invention using the methods and techniques disclosed above, or modify them into equivalent embodiments with equivalent changes, without departing from the scope of the present invention. This does not affect the essential content of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the present invention's technical solutions still fall within the protection scope of the present invention.

Claims

1. A graftable fused ring material, characterized in that: Including compounds having the structure shown in (Ⅰ): (Ⅰ) Wherein, R1 to R6 are each independently selected from H, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted heteroalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted amino, substituted or unsubstituted amide, substituted or unsubstituted cyclic imino, substituted or unsubstituted alkoxy, substituted or unsubstituted carboxyl, substituted or unsubstituted ester, and substituted or unsubstituted carbonyl, and R1 to R6 are not simultaneously H; the substituted substituents include C1 to C1. 28 Hydroxyl group, C1~C 28 Ester group, C1~C 28 Carboxyl group, C1~C 28 Amino, C1~C 28 thiol group, C1~C 28 amide group, C1~C 28 carbonyl group, C1~C 28 Alkoxy, C6~C 28 Aryl, C4~C 28 heteroaryl, C1~C 28 Alkyl, C1~C 28 Heteroalkyl, C1~C 28 alkenyl and C1~C 28 Any one of the imino groups; L1 and L2 are each independently derived from C1~C 28 Alkylene, C1~C 28 Etheryl group, C1~C 28 Ester group, C1~C 28 Imino, C1~C 28 imide group, C1~C 28 carbonyl group, C1~C 28 aryl, C1~C 28 alkenyl, C1~C 28 Any one of the ynylene groups; The Ar is selected from ungrouped, substituted alkylene, optionally substituted alkenyl, optionally substituted aryl, and optionally substituted heteroaryl.

2. The graftable fused ring material according to claim 1, characterized in that, The substituents in the optionally substituted aryl group or the optionally substituted heteroaryl group are each independently selected from one or more groups of C1 to C2. 20 Alkyl, C1-C 10 alkenyl, C1-C 10 alkynyl, C3-C7 cycloalkyl, gem-linked cycloalkyl, C1-C6 heteroalkyl, C3-C 10 Heterocyclic alkyl, aryl, aralkyl, heteroaryl, halogenated, cyano, hydroxyl, optionally substituted cyclic imino, amino, imino, amide, C1-C 10 Alkyloxy, aryloxy, acyloxy, mercapto, halogenated C1-C 10 Alkyl, C1-C 10 Alkylthio, arylthio, mono-C1 to C1-C2 10 Alkylamino, diC1-C 10 Alkylamino, quaternary ammonium salt, amino C1-C 10 Alkoxy and hydroxyl groups (C1-C5) 10 Alkylamino, amino C1-C 10 Alkylthio, cyanoamino, nitro, carbamoyl, oxy, carbonyl, carboxyl, hydroxyacetyl, glycyl, hydrazine, amidoyl, aminesulfonyl, sulfonyl, sulfinyl, thiocarbonyl, thiocarboxyl, sulfonamide, ester, C-amide, N-amide, N-carbamate, O-carbamate, urea, and combinations thereof.

3. The graftable fused ring material according to claim 1, characterized in that, The graftable fused ring material includes any one or a combination of at least two of the following compounds: 。 4. A grafted adhesive film, characterized in that, The raw materials for preparing the grafted film include the graftable fused ring material as described in any one of claims 1 to 3.

5. The grafted adhesive film according to claim 4, characterized in that, The raw materials for preparing the grafted film include the following components: resin particles, graftable fused ring material as described in any one of claims 1 to 3, crosslinking agent, modified silane, acrylate, light stabilizer, and anti-stabilizer.

6. The grafted adhesive film according to claim 4, characterized in that, The raw materials for preparing the grafted adhesive film, by weight, include the following components: 50-95 parts of resin particles; 1-30 parts of graftable fused ring material; Crosslinking agent 0.5-3 parts; 0.3-2 parts of modified silane; Acrylic ester 0.5~1.5 parts; Light stabilizer 0.1~0.5 parts; Antioxidant 0.1~0.5 parts.

7. A grafted adhesive film according to claim 5 or 6, characterized in that, The crosslinking agent includes any one or a combination of at least two of the following: 2-ethylhexyl tert-butyl peroxide, 2-ethylhexyl tert-amyl peroxide, triallyl isocyanurate, triallyl cyanurate, dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide, or dicumyl peroxide. The modified silane includes any one or a combination of at least two of the following: propyltrioxyethyl isocyanate, vinyltriacetoxysilane, methacryloyloxypropyltrimethoxysilane derivatives, alkylaminosilane oligomers, alkylvinylsilane oligomers, epoxysilane oligomers, aminosilane oligomers, small molecule polysiloxanes, mercaptosilane derivatives, or hybrid functional silanes. The acrylates include any one or a combination of at least two of the following: ethoxytrimethylolpropane triacrylate, propoxytrimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, polyethylene glycol diacrylate, tricyclodecanedimethylol diacrylate, or ditrimethylolpropane tetraacrylate. The light stabilizer includes any one or a combination of at least two of the following: succinic acid, (a polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol), bis-2,2,6,6-tetramethylpiperidinol sebacate or hindered amine light stabilizer, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(2,4-di-tert-butylphenyl) phosphite or 2,2,6,6-tetramethyl-4-piperidinol ester; The antioxidant includes any one or a combination of at least two of the following: octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or tris[2,4-di-tert-butylphenyl]phosphite.

8. A grafted adhesive film according to claim 5 or 6, characterized in that, The resin includes any one or a combination of at least two of polyvinyl acetate, polyethylene-octene copolymer, polyvinyl butyral, hot-melt polyolefin particles, or thermoplastic polyurethane.

9. A photovoltaic module, characterized in that, The photovoltaic module includes the grafted adhesive film and the battery as described in any one of claims 4 to 8.

10. The photovoltaic module according to claim 9, characterized in that, The battery includes any one or a combination of at least two of the following: indium gallium arsenide solar cells, organic solar cells, perovskite solar cells, cadmium sulfide / cadmium telluride solar cells, amorphous silicon solar cells, microcrystalline silicon solar cells, and crystalline silicon solar cells.

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