Glass fiber reinforced material for photovoltaic module and preparation method of glass fiber reinforced material

Abstract

The invention relates to the field of photovoltaic modules, provides a glass fiber reinforced material for a photovoltaic module and a preparation method of the glass fiber reinforced material, and solves the problems that an existing glass fiber reinforced material for the photovoltaic module is low in transparency and relatively weak in tensile strength, bending strength and impact strength and does not have a recycling function. Comprising a first matrix layer, a second matrix layer, a first glass fiber layer, a third matrix layer, a second glass fiber layer, a fourth matrix layer and a fifth matrix layer which are sequentially laminated from top to bottom, the first base body layer, the second base body layer, the third base body layer, the fourth base body layer and the fifth base body layer are all renewable polymers, and the first glass fiber layer and the second glass fiber layer are composed of a plurality of broadened glass fiber tows.

Description

Technical Field

[0001] The present invention relates to the field of photovoltaic modules, and in particular to a glass fiber reinforced material for photovoltaic modules and a preparation method thereof. Background Art

[0002] Glass fiber reinforced material is a composite material made of glass fiber as reinforcement and polymer resin as matrix through a specific forming process. It combines the advantages of glass fiber and resin matrix, and can overcome the defects of a single material. In addition, glass fiber reinforced materials also have the characteristics of ultra-high specific strength and specific stiffness, excellent fatigue resistance, and corrosion resistance. Therefore, in the fields of aerospace, automobiles, and photovoltaics, glass fiber reinforced materials are widely used to replace metal components to achieve the goal of lightweighting.

[0003] Chinese patent application No. 202410364495.X discloses a lightweight flame-retardant photovoltaic backplane and its preparation method, wherein the core layer is a modified flame-retardant foamed polystyrene board, the upper surface layer is a thermosetting or thermoplastic composite material with thermal conductivity and fireproof properties, and the lower surface layer is a thermosetting or thermoplastic composite material. The upper and lower surface layers are bonded to the core layer with an adhesive. The photovoltaic backplane of this invention can achieve building Class B fire protection; compared with fireproof aluminum panels, etc., it has good insulation and a local discharge voltage of up to 2000V; it also has the characteristics of high strength and flame retardancy and stability. However, the transparency of the lightweight flame-retardant photovoltaic backplane is not high, which affects the efficiency of converting light energy into electrical energy, and the low transparency of photovoltaic modules may cause hot spot effects, which is not conducive to heat dissipation.

[0004] Chinese patent application No. 202411064844.2 discloses a composite photovoltaic front panel and its preparation method and application. The composite photovoltaic front panel includes a transparent substrate (transparent polyester film material), a resin adhesive material layer and a reinforced resin material layer coated with glass fiber cloth; the resin adhesive material includes a polyhydroxy polyester resin, a curing agent, a UV absorber, an antioxidant, a leveling agent and other additives; the molar ratio of the hydroxyl group of the polyester resin to the isocyanate group of its curing agent is 1:1-1.2; the reinforced resin material includes an epoxy resin, a curing agent, a UV absorber, an antioxidant and other additives; the molar ratio of the epoxy group of the epoxy resin to the anhydride of the curing agent is 1:0.80-0.9. The composite photovoltaic front panel has excellent light transmittance, mechanical strength and bending strength, and can also prevent the interlayer delamination phenomenon of the initial and long-term aging. The light transmittance and interlayer peeling strength after PCT48h aging are good, and it is suitable for application in flexible photovoltaic modules. However, the transparent substrate does not have the function of being recyclable. Summary of the invention

[0005] Therefore, in response to the above problems, the present invention provides a glass fiber reinforced material for photovoltaic modules and a preparation method thereof, so as to solve the problems that the existing glass fiber reinforced materials for photovoltaic modules have low transparency, relatively weak tensile strength, bending strength and impact strength, and lack of recyclability.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A glass fiber reinforced material for a photovoltaic module comprises a first substrate layer, a second substrate layer, a first glass fiber layer, a third substrate layer, a second glass fiber layer, a fourth substrate layer and a fifth substrate layer which are stacked in sequence from top to bottom, wherein the first substrate layer, the second substrate layer, the third substrate layer, the fourth substrate layer and the fifth substrate layer are all renewable polymers, and the first glass fiber layer and the second glass fiber layer are composed of a plurality of widened glass fiber bundles; the preparation process of the renewable polymer is as follows:

[0008] I. Raise the temperature to 70-90°C, melt 10-30 parts by weight of 1,4-cyclohexanedimethanol, and mix the melted 1,4-cyclohexanedimethanol, 60-100 parts by weight of terephthalic acid, 70-100 parts by weight of ethylene glycol, and 220-250 parts by weight of Sb 2 O 3 Add to polymerization reactor;

[0009] II. In N 2 Continue stirring under the environment, raise the temperature to 200-230℃ and stop heating, start the esterification reaction, and when the temperature drops to 100-110℃, the esterification reaction ends;

[0010] III. Raise the temperature to 80-90° C. at room temperature to evaporate excess ethylene glycol and 1,4-cyclohexanedimethanol, then adjust the vacuum degree of the polymerization kettle to 45-50 Pa, raise the temperature to 260-290° C., react for 1-1.5 hours, and cast into a film after the reaction is completed to obtain the renewable polymer.

[0011] Furthermore, the width of a single strand of the widened glass fiber bundle is 10-13 mm, and the thickness is 0.08-0.10 mm.

[0012] Furthermore, the thickness of the renewable polymer is 0.05-0.15 mm.

[0013] Furthermore, the preparation method of the widened glass fiber bundle is: subjecting the glass fiber roving to a tension roller treatment to obtain the widened glass fiber bundle; the roller diameter of the tension roller is 1300-1500 mm.

[0014] Further, in step II, N 2 The pressure of the environment is 0.1-0.3MPa.

[0015] A method for preparing a glass fiber reinforced material for a photovoltaic module comprises the following steps:

[0016] S1, laying out the first base layer, the second base layer, the first glass fiber layer, the third base layer, the second glass fiber layer, the fourth base layer and the fifth base layer in the order from top to bottom, and then placing them into a mold;

[0017] S2. Raise the temperature of the mold to 240-260°C at a heating rate of 10°C / min, with a pressure of 3-5MPa, and keep warm for 15-20min;

[0018] S3, cooling the mold to 150-170°C at a cooling rate of 5°C / min, and then subjecting it to a water-cooled rapid annealing treatment, lowering the temperature to room temperature, and performing a drying treatment after demoulding to obtain the glass fiber reinforced material for the photovoltaic module.

[0019] Furthermore, the drying process is carried out at a temperature of 35-40° C. and for a time of 1.5-2 h.

[0020] By adopting the above technical solution, the beneficial effects of the present invention are:

[0021] 1. The glass fiber roving is processed by a tension roller to obtain a wide glass fiber bundle, which can make the fiber bundle thinner, thereby reducing the refraction and scattering of visible light and improving the optical properties of glass fiber reinforced materials.

[0022] 2. When the refractive index difference is greater, the light refraction and scattering at the interface of the glass fiber and the matrix layer will be more serious, resulting in a serious decrease in the optical properties of the transparent glass fiber reinforced material. The renewable polymer prepared by the technical solution of this application has excellent optical properties, and its refractive index is 1.56, which is close to the refractive index of glass fiber (1.563-1.566). After being compounded with glass fiber, a high-transparency composite material can be prepared.

[0023] 3. The tensile strength, flexural strength and impact strength of renewable polymers are also excellent, and they have good processability; renewable polymers can be depolymerized into monomers or polymers, and then repolymerized to form new polyester materials for recycling and reuse.

[0024] 4. Water is produced during the synthesis of renewable polymers, but no dangerous substances such as methanol are produced, so the production and recycling process is relatively safe. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a schematic diagram of the structure of the glass fiber reinforced material in Examples 1 to 3 of the present invention;

[0026] Figure 2Schematic diagram of the synthesis of renewable polymers;

[0027] Explanation of the numbers in the figure: 1-first substrate layer, 2-second substrate layer, 3-first glass fiber layer, 4-third substrate layer, 5-second glass fiber layer, 6-fourth substrate layer, 7-fifth substrate layer. DETAILED DESCRIPTION

[0028] Example 1

[0029] A glass fiber reinforced material for a photovoltaic module, comprising a first substrate layer 1, a second substrate layer 2, a first glass fiber layer 3, a third substrate layer 4, a second glass fiber layer 5, a fourth substrate layer 6 and a fifth substrate layer 7 which are stacked in sequence from top to bottom, wherein the first substrate layer 1, the second substrate layer 2, the third substrate layer 4, the fourth substrate layer 6 and the fifth substrate layer 7 are all renewable polymers, the thickness of the renewable polymer is 0.05 mm, the first glass fiber layer 3 and the second glass fiber layer 5 are composed of a plurality of wide-spread glass fiber bundles; the preparation method of the wide-spread glass fiber bundles is as follows: a glass fiber roving is subjected to a tension roller treatment, the roller diameter of the tension roller is 1300 mm, and the wide-spread glass fiber bundles are obtained; the width of a single strand of the wide-spread glass fiber bundle is 10 mm, and the thickness is 0.08 mm;

[0030] Among them, reference Figure 2 , the preparation process of the renewable polymer is:

[0031] I. Raise the temperature to 70°C, melt 10 parts by weight of 1,4-cyclohexanedimethanol, and mix the melted 1,4-cyclohexanedimethanol, 60 parts by weight of terephthalic acid, 70 parts by weight of ethylene glycol, and 220 parts by weight of Sb 2 O 3 Add to polymerization reactor;

[0032] II. In N 2 Stir continuously under the environment, the N 2 The pressure of the environment is 0.1 MPa. The temperature is raised to 200°C and then stopped, and the esterification reaction begins. When the temperature drops to 100°C, the esterification reaction ends.

[0033] III. Raising the temperature to 80° C. at room temperature to evaporate excess ethylene glycol and 1,4-cyclohexanedimethanol, then adjusting the vacuum degree of the polymerization kettle to 45 Pa, raising the temperature to 260° C., reacting for 1 hour, and casting a film after the reaction is completed to obtain the renewable polymer.

[0034] The above-mentioned method for preparing a glass fiber reinforced material for photovoltaic modules comprises the following steps:

[0035] S1, laying out the first base layer, the second base layer, the first glass fiber layer, the third base layer, the second glass fiber layer, the fourth base layer and the fifth base layer in the order from top to bottom, and then placing them into a mold;

[0036] S2. Raise the temperature of the mold to 240°C at a heating rate of 10°C / min, with a pressure of 3MPa, and keep warm for 15min;

[0037] S3, cooling the mold to 170°C at a cooling rate of 5°C / min, and then subjecting it to a water-cooled rapid annealing treatment to reduce the temperature to room temperature, and performing a drying treatment after demoulding, wherein the drying temperature is 35°C and the time is 1.5 hours, to obtain the glass fiber reinforced material for the photovoltaic module.

[0038] Example 2

[0039] A glass fiber reinforced material for a photovoltaic module, comprising a first substrate layer 1, a second substrate layer 2, a first glass fiber layer 3, a third substrate layer 4, a second glass fiber layer 5, a fourth substrate layer 6 and a fifth substrate layer 7 which are stacked in sequence from top to bottom, wherein the first substrate layer 1, the second substrate layer 2, the third substrate layer 4, the fourth substrate layer 6 and the fifth substrate layer 7 are all renewable polymers, the thickness of the renewable polymer is 0.10 mm, the first glass fiber layer 3 and the second glass fiber layer 5 are composed of a plurality of wide-spread glass fiber bundles; the preparation method of the wide-spread glass fiber bundles is as follows: a glass fiber roving is subjected to a tension roller treatment, the roller diameter of the tension roller is 1400 mm, to obtain the wide-spread glass fiber bundles; the width of a single strand of the wide-spread glass fiber bundles is 11 mm, and the thickness is 0.09 mm;

[0040] Wherein, the preparation process of the renewable polymer is:

[0041] I. Raise the temperature to 80°C, melt 20 parts by weight of 1,4-cyclohexanedimethanol, and mix the melted 1,4-cyclohexanedimethanol, 80 parts by weight of terephthalic acid, 80 parts by weight of ethylene glycol, and 230 parts by weight of Sb 2 O 3 Add to polymerization reactor;

[0042] II. In N 2 Stir continuously under the environment, the N 2 The pressure of the environment is 0.2MPa. The temperature is raised to 220℃ and then stopped to start the esterification reaction. When the temperature drops to 105℃, the esterification reaction ends.

[0043] III. Raising the temperature to 85° C. at room temperature to evaporate excess ethylene glycol and 1,4-cyclohexanedimethanol, then adjusting the vacuum degree of the polymerization kettle to 48 Pa, raising the temperature to 280° C., reacting for 1.2 hours, and casting a film after the reaction to obtain the renewable polymer.

[0044] The above-mentioned method for preparing a glass fiber reinforced material for photovoltaic modules comprises the following steps:

[0045] S1, laying out the first base layer, the second base layer, the first glass fiber layer, the third base layer, the second glass fiber layer, the fourth base layer and the fifth base layer in the order from top to bottom, and then placing them into a mold;

[0046] S2. Raise the temperature of the mold to 250°C at a heating rate of 10°C / min, with a pressure of 4 MPa, and keep warm for 18 minutes;

[0047] S3, cooling the mold to 160°C at a cooling rate of 5°C / min, and then subjecting it to a water-cooled rapid annealing treatment to reduce the temperature to room temperature, and performing a drying treatment after demoulding. The drying treatment temperature is 38°C and the time is 1.8h to obtain the glass fiber reinforced material for the photovoltaic module.

[0048] Example 3

[0049] A glass fiber reinforced material for a photovoltaic module, comprising a first substrate layer 1, a second substrate layer 2, a first glass fiber layer 3, a third substrate layer 4, a second glass fiber layer 5, a fourth substrate layer 6 and a fifth substrate layer 7 which are stacked in sequence from top to bottom, wherein the first substrate layer 1, the second substrate layer 2, the third substrate layer 4, the fourth substrate layer 6 and the fifth substrate layer 7 are all renewable polymers, the thickness of the renewable polymer is 0.15 mm, the first glass fiber layer 3 and the second glass fiber layer 5 are composed of a plurality of wide-spread glass fiber bundles; the preparation method of the wide-spread glass fiber bundles is as follows: a glass fiber roving is subjected to a tension roller treatment, the roller diameter of the tension roller is 1500 mm, and the wide-spread glass fiber bundles are obtained; the width of a single strand of the wide-spread glass fiber bundle is 13 mm, and the thickness is 0.10 mm;

[0050] Wherein, the preparation process of the renewable polymer is:

[0051] I. Raise the temperature to 90°C, melt 30 parts by weight of 1,4-cyclohexanedimethanol, and mix the melted 1,4-cyclohexanedimethanol, 100 parts by weight of terephthalic acid, 100 parts by weight of ethylene glycol, and 250 parts by weight of Sb 2 O 3 Add to polymerization reactor;

[0052] II. In N 2 Stir continuously under the environment, the N2 The pressure of the environment is 0.3MPa. The temperature is raised to 230℃ and then stopped, and the esterification reaction begins. When the temperature drops to 110℃, the esterification reaction ends.

[0053] III. Raising the temperature to 90° C. at room temperature to evaporate excess ethylene glycol and 1,4-cyclohexanedimethanol, then adjusting the vacuum degree of the polymerization kettle to 50 Pa, raising the temperature to 290° C., reacting for 1.5 hours, and casting a film after the reaction is completed to obtain the renewable polymer.

[0054] The above-mentioned method for preparing a glass fiber reinforced material for photovoltaic modules comprises the following steps:

[0055] S1, laying out the first base layer, the second base layer, the first glass fiber layer, the third base layer, the second glass fiber layer, the fourth base layer and the fifth base layer in the order from top to bottom, and then placing them into a mold;

[0056] S2. Raise the temperature of the mold to 260°C at a heating rate of 10°C / min, with a pressure of 5 MPa, and keep warm for 20 minutes;

[0057] S3, cooling the mold to 150°C at a cooling rate of 5°C / min, and then subjecting it to a water-cooled rapid annealing treatment to reduce the temperature to room temperature, and performing a drying treatment after demoulding, wherein the drying temperature is 40°C and the time is 2h, to obtain the glass fiber reinforced material for the photovoltaic module.

[0058] Comparative Example 1

[0059] The difference from Example 1 is that the first base layer 1, the second base layer 2, the third base layer 4, the fourth base layer 6 and the fifth base layer 7 are all made of polyurethane resin, and the first glass fiber layer 3 and the second glass fiber layer 5 are composed of a plurality of commercially available known glass fiber bundles, which are not processed by tension rollers. Other technical solutions are the same as those of Example 1.

[0060] Table 1 is the experimental test data of Example 1, Example 2, Example 3 and Comparative Example 1.

[0061] Table 1

[0062]

[0063] Optical performance test: The transmittance and haze were measured according to ASTM-D103 standard.

[0064] Mechanical properties test: The tensile strength was measured according to ASTM-D3039; the flexural strength was measured according to ASTM-D7264; the impact strength was measured using a pendulum impact tester.

[0065] Although the present invention has been specifically shown and described in conjunction with the preferred embodiments, it should be understood by those skilled in the art that various changes may be made to the present invention in form and details without departing from the spirit and scope of the present invention as defined by the appended claims, all of which are within the scope of protection of the present invention.

Claims

1. A glass fiber reinforced material for photovoltaic modules, characterized in that: The invention comprises a first substrate layer, a second substrate layer, a first glass fiber layer, a third substrate layer, a second glass fiber layer, a fourth substrate layer and a fifth substrate layer which are stacked in sequence from top to bottom, wherein the first substrate layer, the second substrate layer, the third substrate layer, the fourth substrate layer and the fifth substrate layer are all renewable polymers, and the first glass fiber layer and the second glass fiber layer are composed of a plurality of widened glass fiber bundles; the preparation process of the renewable polymer is as follows: I. Raise the temperature to 70-90° C., melt 10-30 parts by weight of 1,4-cyclohexanedimethanol, and add the melted 1,4-cyclohexanedimethanol, 60-100 parts by weight of terephthalic acid, 70-100 parts by weight of ethylene glycol and 220-250 parts by weight of Sb2O3 into a polymerization kettle; II. Continue stirring under N2 environment, raise the temperature to 200-230°C and stop heating, start esterification reaction, and end esterification reaction when the temperature drops to 100-110°C; III. Raise the temperature to 80-90° C. at room temperature to evaporate excess ethylene glycol and 1,4-cyclohexanedimethanol, then adjust the vacuum degree of the polymerization kettle to 45-50 Pa, raise the temperature to 260-290° C., react for 1-1.5 hours, and cast into a film after the reaction is completed to obtain the renewable polymer.

2. A glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The width of the single-strand widened glass fiber bundle is 10-13 mm, and the thickness is 0.08-0.10 mm.

3. The glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The renewable polymer has a thickness of 0.05-0.15 mm.

4. The glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The preparation method of the widened glass fiber bundle is as follows: glass fiber roving is processed by a tension roller to obtain the widened glass fiber bundle; the roller diameter of the tension roller is 1300-1500mm.

5. The glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The pressure of the N2 environment in step II is 0.1-0.3 MPa.

6. The method for preparing a glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The following steps are involved: S1, laying out the first base layer, the second base layer, the first glass fiber layer, the third base layer, the second glass fiber layer, the fourth base layer and the fifth base layer in the order from top to bottom, and then placing them into a mold; S2. Raise the temperature of the mold to 240-260°C at a heating rate of 10°C / min, with a pressure of 3-5MPa, and keep warm for 15-20min; S3, cooling the mold to 150-170°C at a cooling rate of 5°C / min, and then subjecting it to a water-cooled rapid annealing treatment, lowering the temperature to room temperature, and performing a drying treatment after demoulding to obtain the glass fiber reinforced material for the photovoltaic module.

7. The method for preparing a glass fiber reinforced material for photovoltaic modules according to claim 1, characterized in that: The drying process is carried out at a temperature of 35-40° C. and for a time of 1.5-2 hours.

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