Epoxy resin for photovoltaic module reinforcement layer and preparation method and application thereof

Abstract

The present invention belongs to the field of lightweight photovoltaic modules, and particularly relates to an epoxy resin for a photovoltaic module reinforcement layer, and a preparation method and application thereof, comprising epoxy resin A, epoxy resin B, active diluent, curing agent A, curing agent B, accelerator A, accelerator B, UV absorber, light stabilizer, antioxidant, and nano-coated silica. The present invention uses unique nano-coated silica as a filler, reduces voids that may be generated during epoxy resin pre-impregnation without affecting light transmittance, improves the water-blocking performance of the composite material, and has good market application prospects.

Description

Technical Field

[0001] The invention belongs to the field of lightweight photovoltaic modules, and particularly relates to an epoxy resin for a photovoltaic module reinforcement layer, and a preparation method and application thereof. Background Art

[0002] Lightweight flexible photovoltaic modules are widely used in industrial buildings, residential buildings and other roofs with limited weight due to their low weight, easy installation, and low requirements for weighing and environment. In order to strengthen lightweight flexible photovoltaic modules, glass fiber reinforced composite materials are usually added to the front and back. Common matrixes are epoxy resin and acrylic resin matrix. Most of the materials on the market are bisphenol A epoxy resin and acrylate. The advantage of bisphenol A epoxy resin is high heat resistance, but after long-term light aging, it turns yellow severely, affecting the appearance. The advantage of acrylate is good UV resistance, but its molecular weight is low, the free volume between molecular chains is large, the water barrier performance is poor, and the performance is seriously reduced after long-term aging.

[0003] US20180374974A1 prepared super-weather-resistant acrylic ester by preparing acrylic resin, but pure acrylic ester itself has poor water resistance, and long-term outdoor aging will cause plasticization. In addition, the rigidity of acrylic ester molecular chain is relatively low, and the glass transition temperature T g Below 83℃, the water permeability of the material is >4g / m 2 *d.

[0004] CN117304655B uses acrylic acid derivatives to prepare vinyl resins and prepare composite materials for photovoltaic module packaging. Compared with pure epoxy resin, the epoxy resin modified with acrylic acid has greatly improved UV resistance and hydrolysis resistance, and the rigidity of the molecular chain is guaranteed. However, the introduction of some acrylic acid esters will deteriorate the water barrier performance of the material.

[0005] CN115466565B uses polyurethane acrylic to prepare composite materials for packaging components through a two-step method. The first step is to make a pre-cured sheet by pre-impregnating diluted resin and light curing; the second step is to put the pre-cured sheet into the photovoltaic module for lamination to prepare a lightweight photovoltaic module. The patent uses diluents and coupling agents to overcome poor wettability and possible gap problems, but although the main chain has sufficient cohesive energy, its water resistance is still very poor, and its system voltage is difficult to exceed 1000V, which does not meet future trends. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide an epoxy resin for a photovoltaic module reinforcement layer, a preparation method and an application thereof, using a unique nano-coated silica as a filler to reduce the voids that may be generated during the epoxy resin pre-impregnation process without affecting the light transmittance, thereby improving the water-blocking properties of the composite material.

[0007] The present invention provides an epoxy resin for a photovoltaic module reinforcement layer, which comprises the following components in parts by weight:

[0008] Epoxy resin A 30-60 parts;

[0009] Epoxy resin B 10-30 parts;

[0010] Active diluent 10-20 parts;

[0011] Curing agent A 8-12 parts;

[0012] Curing agent B 8-12 parts;

[0013] Accelerator A 1-2 parts;

[0014] Accelerator B 0.1-0.5 part;

[0015] UV absorber 0.5-1 part;

[0016] Light stabilizer 0.5-1 part;

[0017] Antioxidant 0.2-0.5 parts;

[0018] 1-2.5 parts of nano-coated silicon dioxide;

[0019] Wherein, the nano-coated silicon dioxide is obtained by reacting the following components in parts by weight:

[0020] 20-30 parts of nano silicon dioxide;

[0021] Coating monomer A 20-30 parts;

[0022] Coating monomer B 10-20 parts;

[0023] 1-5 parts of interface treatment agent;

[0024] Initiator 0.1-0.5 parts.

[0025] Preferably, the epoxy resin A is a hydrogenated epoxy resin. The hydrogenated epoxy resin includes one or more of the high Tg hydrogenated bisphenol A (Tg=120° C.) and low Tg hydrogenated bisphenol A (Tg=73-83° C.).

[0026] Preferably, the epoxy resin B is one or more of triglycidyl p-aminophenol, N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane, and 4-(diglycidylamino)phenyl glycidyl ether. More preferably, the epoxy resin B is triglycidyl p-aminophenol.

[0027] Preferably, the active diluent is one or more of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and cyclohexanedimethanol diglycidyl ether. More preferably, the active diluent is cyclohexane-1,2-dicarboxylic acid diglycidyl ester.

[0028] Preferably, the curing agent A is one or more of isophoronediamine, 1,3-bis(aminomethyl)cyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, N-(2-aminoethyl)-1,2,3,6-tetrahydropyridine, and 4,4'-diaminodicyclohexylmethane.

[0029] Preferably, the curing agent B is one or more of 4,4'-diaminodiphenylmethane and diaminodiphenyl sulfone.

[0030] Preferably, the accelerator A is one or more of triethylenediamine, imidazole accelerators, and benzyltrimethylammonium chloride. More preferably, the accelerator A is triethylenediamine.

[0031] Preferably, the accelerator B is a boron amine complex accelerator. The ligand of boron trifluoride in the boron amine complex is one or more of n-hexylamine accelerator, monoethylamine accelerator, aniline, diethylamine, piperidine, triethylamine, and aniline, and more preferably is a boron trifluoride monoethylamine salt accelerator.

[0032] Preferably, the UV absorber is a triazine UV absorber. More preferably, the triazine UV absorber is one or more of UV1164, UV1577, and UV400.

[0033] Preferably, the light stabilizer is a benzotriazole light stabilizer. More preferably, the benzotriazole light stabilizer is one or more of UV1130 and UV928.

[0034] Preferably, the antioxidant is a hindered phenol antioxidant. More preferably, the hindered phenol antioxidant is one or more of Antioxidant 1076, Antioxidant 1098, and Antioxidant 1010.

[0035] Preferably, the coating monomer A is one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate.

[0036] Preferably, the coating monomer B is one or more of methyl methacrylate, butyl methacrylate, and isobornyl methacrylate.

[0037] Preferably, the interface treatment agent is one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltriethoxysilane.

[0038] Preferably, the initiator is one or more of benzoyl peroxide, azobisisobutyronitrile, diisopropylbenzene peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate.

[0039] The nano-silicon dioxide used in the present invention is preferably nano-silicon dioxide treated with a silane coupling agent in advance; more preferably, it is treated with a silane coupling agent KH550. The coating monomer A, the coating monomer B, and the interface treatment agent all contain double bonds, and under the condition of above 70°C and the presence of an initiator, the double bonds react with the amino groups in the silane coupling agent covered on the surface of the nano-silicon dioxide to form CN bonds, which is similar to a polymerization reaction initiated by free radicals or a Michael addition reaction, thereby obtaining the nano-coated silica.

[0040] The present invention also provides a method for preparing an epoxy resin for a photovoltaic module reinforcement layer, comprising the following steps:

[0041] (1) dissolving nano-silica particles in a solvent and ultrasonically dispersing them, adding coating monomer A, coating monomer B and an interface treatment agent according to a ratio, adding an initiator after heating, and evaporating the solvent after the reaction to obtain nano-coated silica;

[0042] (2) According to the proportion, epoxy resin A, epoxy resin B, active diluent, UV absorber, light stabilizer, antioxidant, and nano-coated silica are added to a stirring kettle and heated and stirred. After cooling, curing agent A, curing agent B, accelerator A, and accelerator B are added, stirred, and vacuumed to obtain epoxy resin for the photovoltaic module reinforcement layer.

[0043] The present invention also provides an application of epoxy resin for a photovoltaic module reinforcement layer in a lightweight flexible photovoltaic module.

[0044] Beneficial Effects

[0045] (1) The present invention uses unique nano-coated silica as filler to reduce the voids that may be generated during the epoxy resin pre-impregnation process without affecting the light transmittance, thereby improving the water barrier properties of the composite material;

[0046] (2) The present invention uses epoxy resin A and epoxy resin B in combination, which not only improves the light transmittance of the composite material, enhances the UV yellowing resistance of the composite material, but also enhances the molecular chain rigidity of the composite material, reduces the free volume of the chain segment, and increases the glass transition temperature;

[0047] (3) The present invention is divided into two stages of curing. In the first stage, curing agent A is used for partial thermal curing when producing prepreg. In the second stage, curing agent B is used to increase the crosslinking degree of the composite material and increase the glass transition temperature and molecular weight rigidity of the entire material. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 SEM image of SiO2-3 prepared in the example (right) and SEM image of uncoated nano-silicon dioxide (left). DETAILED DESCRIPTION

[0049] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0050] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0051] Table 1 Formula of nano-coated silica (parts by weight)

[0052]

[0053] The preparation method of the nano-coated silicon dioxide comprises the following steps:

[0054] 1. Ultrasonic dispersion of nano-silica particles in ethanol for 1 h to ensure uniform dispersion of the particles;

[0055] 2. Add coating monomer A, coating monomer B and interface treatment agent into a three-hole flask according to the proportion, and raise the temperature to 70°C under nitrogen atmosphere for 10 minutes;

[0056] 3. The initiator was dripped into the reactants within 20 minutes, and a viscous paste polymer was generated after 20 minutes;

[0057] 4. Then, the solvent is evaporated off by rotary evaporation, and the product is dried and crushed to obtain nano-coated silica.

[0058] Table 2 Formula of epoxy resin for photovoltaic module reinforcement layer (parts by weight, example)

[0059]

[0060] Table 3 Formula of epoxy resin for photovoltaic module reinforcement layer (weight parts, comparative example)

[0061]

[0062] The method for preparing the epoxy resin for the photovoltaic module reinforcement layer comprises the following steps:

[0063] According to the proportion, epoxy resin A, epoxy resin B, active diluent, UV absorber, light stabilizer, antioxidant and nano-coated silica are added into a stirring kettle, heated to 120°C, stirred for 20 minutes, then cooled to 80°C and curing agent A, curing agent B, accelerator A and accelerator B are added, stirred and vacuumed to obtain epoxy resin for photovoltaic module reinforcement layer.

[0064] The epoxy resin is used to prepare prepreg and composite materials, comprising the following steps:

[0065] 1. Gluing: Put the above epoxy resin into the glue coating machine and prepare a 50~60g / m 2 Adhesive film, coating temperature 80℃;

[0066] 2. Composite: 160g / m 2 The glass fiber woven cloth is unrolled and the prepreg is prepared by 2 coatings and 1 dipping. The rolling temperature is 100°C, 4 groups of rollers are used, and the rolling line speed is less than 3m / min to make the prepreg;

[0067] 3. Preparation of composite material samples: The prepreg was packaged under the conditions of 0.9atm vacuum and 143℃ / 15min curing, and the composite material performance was tested.

[0068] Table 4 Performance of composite materials in the examples

[0069]

[0070] Table 5 Comparative Example Composite Material Properties

[0071]

Claims

1. An epoxy resin for a photovoltaic module reinforcement layer, characterized in that: In parts by weight, it comprises the following components: 1-2.5 parts of nano-coated silicon dioxide; the epoxy resin A is a hydrogenated epoxy resin; the epoxy resin B is one or more of triglycidyl p-aminophenol, N,N,N,N-tetraglycidyl-4,4-diaminodiphenylmethane, and 4-(diglycidylamino)phenyl glycidyl ether; the curing agent A is one or more of isophorone diamine, 1,3-bis(aminomethyl)cyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, N-(2-aminoethyl)-1,2,3,6-tetrahydropyridine, and 4,4'-diaminodicyclohexylmethane; the curing agent B is one or more of 4,4'-diaminodiphenylmethane and diaminodiphenyl sulfone; Wherein, the nano-coated silicon dioxide is obtained by reacting the following components in parts by weight: The coating monomer A is one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate; the coating monomer B is one or more of methyl methacrylate, butyl methacrylate, and isobornyl methacrylate.

2. The epoxy resin according to claim 1, characterized in that: The active diluent is one or more of cyclohexane-1,2-dicarboxylic acid diglycidyl ester, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and cyclohexanedimethanol diglycidyl ether.

3. The epoxy resin according to claim 1, characterized in that: The accelerator A is one or more of triethylenediamine, imidazole accelerators, and benzyltrimethylammonium chloride; and the accelerator B is a boron amine complex accelerator.

4. The epoxy resin according to claim 1, characterized in that: The UV absorber is a triazine UV absorber; the light stabilizer is a benzotriazole light stabilizer; and the antioxidant is a hindered phenol antioxidant.

5. The epoxy resin according to claim 1, characterized in that: The interface treatment agent is one or more of 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltriethoxysilane; the initiator is one or more of benzoyl peroxide, azobisisobutyronitrile, diisopropylbenzene peroxide, tert-butyl hydroperoxide, and tert-butyl perbenzoate.

6. A method for preparing the epoxy resin for the photovoltaic module reinforcement layer according to any one of claims 1 to 5, comprising the following steps: (1) dissolving nano-silica particles in a solvent and ultrasonically dispersing them, adding a coating monomer A, a coating monomer B and an interface treatment agent according to a ratio, adding an initiator after heating, and evaporating the solvent after the reaction to obtain nano-coated silica; (2) According to the proportion, epoxy resin A, epoxy resin B, active diluent, UV absorber, light stabilizer, antioxidant, and nano-coated silica are added to a stirring kettle and heated and stirred. After cooling, curing agent A, curing agent B, accelerator A, and accelerator B are added, stirred, and vacuumed to obtain epoxy resin for the photovoltaic module reinforcement layer.

7. Use of the epoxy resin for photovoltaic module reinforcement layer as claimed in any one of claims 1 to 5 in a lightweight flexible photovoltaic module.

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