A transparent composite material prepreg reinforced resin and its preparation method and application

Abstract

The present invention relates to a transparent composite material prepreg reinforced resin and a preparation method and application thereof, wherein the reinforced resin comprises silicon-containing acrylate, curing agent B, rheological additive, antioxidant and ultraviolet absorber. The present invention, by introducing a specially prepared silicon-containing acrylate, is applied to a lightweight photovoltaic module, which is beneficial to further improve the weather resistance and light transmittance of the lightweight photovoltaic composite material, thereby improving the service life and power generation efficiency of the photovoltaic module, and has good market application prospects.

Description

Technical Field

[0001] The invention belongs to the field of polymer composite materials, and particularly relates to a transparent composite material prepreg reinforced resin and a preparation method and application thereof. Background Art

[0002] In lightweight flexible components, in order to increase component rigidity and reduce hidden cracks during transportation and installation, glass fiber reinforced composite materials are generally added to the front and back. For example, epoxy resin pre-impregnated composite materials are used for the front film backplane, and PP reinforced composite materials are used for the backplane. However, epoxy composite materials tend to turn yellow during light aging and long-term heat aging, resulting in a significant reduction in component efficiency. Acrylate resin has excellent weather resistance and light transmittance, but acrylate has high cohesive energy and a large molecular weight during free radical synthesis, making it difficult to disperse and unable to be directly pre-impregnated.

[0003] CN105637653B uses epoxy end-group-containing acrylate as a substrate and fiber fabric as a reinforcement layer. After lamination, the optical refractive index is increased to prepare a transparent composite material. Glycidyl methacrylate is used as an epoxy end-group-containing acrylate as a packaging material to replace glass. Its light transmittance will be higher, but during the curing process of the acrylate, as the viscosity increases, even if the curing time is extended, the degree of cross-linking is difficult to continue to increase. Therefore, after long-term use at 80°C, the surface material will undergo thermal oxidation aging, resulting in reduced material performance. Once the interface is degraded, it will further affect the performance of the component. In order to prevent this from happening, a polyester resin with good fluidity is generally added to the curing system for blending.

[0004] CN110832138B prepares a super weather-resistant polyester resin substrate by mixing polyester resin with acrylic resin for panel packaging. Although acrylic acid improves the light aging and yellowing problem of polyester, polyester and acrylic acid themselves will absorb moisture after long-term outdoor use, causing the material to further degrade and powderize. Therefore, ETFE with good UV and water resistance is used in the component. The addition of ETFE can greatly improve the overall weather resistance of the material, but ETFE has a high cost and poor water resistance, which greatly increases the cost of lightweight flexible components. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a transparent composite material prepreg reinforced resin and its preparation method and application. By introducing a special silicon-containing acrylate, its application in lightweight photovoltaic modules is beneficial to further improve the weather resistance and light transmittance of lightweight photovoltaic composite materials, thereby improving the service life and power generation efficiency of photovoltaic modules, and has good market application prospects.

[0006] The present invention provides a transparent composite material prepreg reinforced resin, wherein the reinforced resin comprises the following components in parts by weight:

[0007] 80-90 parts of silicone acrylate;

[0008] Curing agent B 5-10 parts;

[0009] Rheological additive 0.5-2 parts;

[0010] 0.5-2 parts of antioxidant;

[0011] 0.5-2 parts of UV absorber;

[0012] Wherein, the silicon-containing acrylate is obtained by reacting the following components:

[0013] 5-30 parts of organosilicon modifier;

[0014] Bisphenol A acrylate 10-15 parts;

[0015] 5-10 parts of high temperature resistant modifier;

[0016] Acrylate 5-30 parts;

[0017] Hydroxyacrylate 20-30 parts;

[0018] Curing agent A 10-20 parts.

[0019] Preferably, the organosilicon modifier is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, and trimethoxy(7-octen-1-yl)silane.

[0020] Preferably, the bisphenol A acrylate is one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate oligomers.

[0021] Preferably, the high temperature resistant modifier is bisphenol A epoxy resin diacrylate.

[0022] Preferably, the acrylate is one or more of methyl methacrylate, butyl methacrylate, ethyl methacrylate, ethoxylated trimethylolpropane triacrylate, and tripropylene glycol triacrylate.

[0023] Preferably, the hydroxy acrylate is one or more of 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate.

[0024] Preferably, the curing agent A is an isocyanate blocked by methyl ethyl ketone oxime or caprolactam.

[0025] Preferably, the curing agent B is isocyanate blocked by diethyl malonate or other aliphatic groups.

[0026] Preferably, the rheological additive is fumed silica.

[0027] Preferably, the antioxidant is one or more of a hindered phenol antioxidant and a hindered amine antioxidant.

[0028] Preferably, the ultraviolet absorber is one or more of a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber.

[0029] The present invention also provides a method for preparing a transparent composite material prepreg reinforced resin, comprising the following steps:

[0030] (1) Adding an organosilicon modifier and bisphenol A acrylate to a solvent according to the ratio and reacting at 50-60°C for 3-4 hours, then adding a high temperature resistant modifier, acrylate, and hydroxy acrylate, controlling the reaction temperature at 80-90°C and introducing nitrogen, dropping an initiator, and adding a curing agent A to obtain a silicon-containing acrylate;

[0031] (2) The silicon-containing acrylate of step (1) is extruded and pressed into sheets with a twin-screw extruder with a curing agent B, a rheological additive, an antioxidant, and a UV absorber to obtain a polymer sheet, which is then crushed and filtered to obtain a transparent composite material prepreg reinforced resin.

[0032] Preferably, the solvent in step (1) is a mixed solvent of propylene glycol monopropyl ether and xylene, and the ratio of the added amount to the total mass of the components is 1:1; the initiator is one or more of azobisisobutyronitrile, diisopropylbenzene peroxide, and benzoyl peroxide, and the added amount is 0.1-1% of the total mass of the components.

[0033] The present invention also provides an application of a transparent composite material prepreg reinforced resin in a lightweight photovoltaic module.

[0034] Beneficial Effects

[0035] (1) The present invention introduces a specially prepared silicon-containing acrylate and applies it to lightweight photovoltaic modules, which is beneficial to further improve the weather resistance and light transmittance of lightweight photovoltaic composite materials, thereby improving the service life and power generation efficiency of lightweight photovoltaic modules, and has good market application prospects.

[0036] (2) The present invention uses bisphenol A acrylate as a copolymer monomer and reacts with an organic modifier to improve the material's weather resistance and water resistance while improving wettability, reducing the porosity between the resin and the fiber, and improving light transmittance. At the same time, due to the conjugated properties of the benzene ring, the activity of the allyl radical is increased, and free radical reactions can still occur after the reaction, increasing the molecular weight, thereby improving the weather resistance and light transmittance of the lightweight flexible photovoltaic module.

[0037] (3) In order to improve the heat resistance of silicon-containing acrylates and increase the strength and cross-linking degree of the material, a high-temperature resistant modifier is added to the formula. The Tg point is above 130°C and the epoxy equivalent is above 200g / eq. It can undergo secondary curing at high temperature with the subsequent hydroxy acrylate to increase the cross-linking degree.

[0038] (4) Improve the cross-linking degree of the product through a two-component curing system. First, add curing agent A in the presence of a solvent to improve the uniformity of the curing agent. Use curing agent A to perform a preliminary cross-linking reaction, gradually increase the molecular weight, and reduce the viscosity of the system. Then, during packaging, use curing agent B to increase the cross-linking degree and increase the hydrolysis resistance of the material.

[0039] (5) The present invention is applied to lightweight photovoltaic modules, which are easy to process and can achieve continuous production, thus significantly reducing the cost of the prepreg process. DETAILED DESCRIPTION

[0040] 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.

[0041] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0042] Table 1 Silicone-containing acrylate formula

[0043]

[0044] The preparation method of silicon-containing acrylate comprises the following steps:

[0045] According to the ratio, an organosilicon modifier and bisphenol A acrylate are added to a solvent and reacted at 60°C for 3 hours, and then a high temperature resistant modifier, acrylate, and hydroxy acrylate are added. The reaction temperature is controlled at 80°C and nitrogen is introduced. An initiator is added dropwise, and a curing agent A is added. According to the ratio, an organosilicon modifier and bisphenol A acrylate are added to a solvent and reacted at 50-60°C for 3-4 hours. The reaction product is subjected to reduced pressure distillation and filtered to separate to obtain a silicon-containing acrylate. The tested molecular weight is between Mw=5000 and 10000, and the Si content in the reactant is between 1wt% and 3wt%.

[0046] Table 2 Transparent composite prepreg reinforced resin formula

[0047]

[0048] A method for preparing a transparent composite material prepreg reinforced resin comprises the following steps:

[0049] According to the proportion, the silicon-containing acrylate, the curing agent B, the rheological additive, the antioxidant and the ultraviolet absorber are extruded and pressed into sheets using a twin-screw extruder to obtain a polymer sheet, which is then crushed and filtered using an 80-mesh filter to obtain a transparent composite material prepreg reinforced resin.

[0050] Table 3 Test results of transparent composite prepreg reinforced resin application

[0051]

[0052] The application steps include:

[0053] 1. Sprinkle the reinforcing resin evenly on 160g / m 2 On the glass fiber twill fabric, the unit area mass of the resin is controlled to 100~120g / m 2 between;

[0054] 2. The powdered glass fiber cloth is baked at a temperature of 100°C to 120°C for 5 minutes to prepare a semi-preg;

[0055] 3. Place the semi-preg in a vacuum bag and refer to the packaging conditions: first draw a vacuum for 5 minutes, control the vacuum degree below 0.01MPa, raise the temperature to 145°C within 5 minutes, and maintain the temperature and pressure for 20 minutes to obtain a cured composite material.

Claims

1. A transparent composite material prepreg reinforced resin, characterized in that: The reinforcing resin comprises the following components in parts by weight: Wherein, the silicon-containing acrylate is obtained by reacting the following components: The preparation method of the silicon-containing acrylate comprises: adding an organosilicon modifier and bisphenol A acrylate to a solvent according to a ratio, reacting at 50-60° C. for 3-4 hours, then adding a high-temperature resistant modifier, acrylate, and hydroxy acrylate, controlling the reaction temperature at 80-90° C. and introducing nitrogen, dripping an initiator, and adding a curing agent A to obtain the silicon-containing acrylate.

2. The reinforced resin according to claim 1, characterized in that: The organosilicon modifier is one or more of 3-(methacryloyloxy)propyltrimethoxysilane, vinyltri(2-methoxyethoxy)silane, vinyltrimethoxysilane, and trimethoxy(7-octen-1-yl)silane.

3. The reinforced resin according to claim 1, characterized in that: The bisphenol A acrylate is one or more of 2,2'-diallyl bisphenol A, 2,2'-diallyl bisphenol S, and epoxy acrylate oligomer.

4. The reinforced resin according to claim 1, characterized in that: The high temperature resistant modifier is bisphenol A epoxy resin diacrylate.

5. The reinforced resin according to claim 1, characterized in that: The acrylic acid ester is one or more of methyl methacrylate, butyl methacrylate, ethyl methacrylate, ethoxylated trimethylolpropane triacrylate, and tripropylene glycol triacrylate; the hydroxy acrylic acid ester is one or more of 2-hydroxyethyl acrylate, hydroxypropyl methacrylate, and pentaerythritol triacrylate.

6. The reinforced resin according to claim 1, characterized in that: The curing agent A is an isocyanate blocked by methyl ethyl ketone oxime or caprolactam; the curing agent B is an isocyanate blocked by diethyl malonate or other aliphatic groups.

7. The reinforced resin according to claim 1, characterized in that: The rheological additive is fumed silica; the antioxidant is one or more of a hindered phenol antioxidant and a hindered amine antioxidant; the ultraviolet absorber is one or more of a benzotriazole ultraviolet absorber and a benzophenone ultraviolet absorber.

8. A method for preparing a transparent composite material prepreg reinforced resin according to any one of claims 1 to 7, comprising the following steps: (1) adding an organosilicon modifier and bisphenol A acrylate to a solvent according to a ratio, reacting at 50-60° C. for 3-4 hours, then adding a high temperature resistant modifier, acrylate, and hydroxy acrylate, controlling the reaction temperature at 80-90° C. and introducing nitrogen, dropping an initiator, and adding a curing agent A to obtain a silicon-containing acrylate; (2) The silicon-containing acrylate of step (1) is extruded and pressed into sheets with a twin-screw extruder with a curing agent B, a rheological additive, an antioxidant, and a UV absorber to obtain a polymer sheet, which is then crushed and filtered to obtain a transparent composite material prepreg reinforced resin.

9. The preparation method according to claim 8, characterized in that: The solvent in step (1) is a mixed solvent of propylene glycol monopropyl ether and xylene; the initiator is one or more of azobisisobutyronitrile, diisopropylbenzene peroxide, and benzoyl peroxide.

10. Use of the transparent composite material prepreg reinforced resin according to any one of claims 1 to 7 in a lightweight photovoltaic module.

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