A method for preparing basalt fiber reinforced polymer material for photovoltaics

Abstract

The invention provides a preparation method of a basalt fiber reinforced polymer material for photovoltaic applications. The method comprises the following steps: uniformly mixing epoxy resin, (R)-N-epoxypropylphthalimide, a solvent, molten metaphenylenediamine and trifluoromethyl-containing multi-walled carbon nanotubes to obtain a glue solution; fixing basalt fibers on a steel frame, and brushing the glue solution on the basalt fibers to obtain a prepreg; compacting the prepreg with a mold to solidify the prepreg; laying the solidified prepreg in 4 layers according to a 90-degree laying mode, placing the prepreg between flat molds, laminating, solidifying, and cooling to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications; combining basalt fibers with nano-carbon fibers to enhance the interlaminar shear strength of the composite material; and improving the impact toughness of the material through the synergistic effect of the anisole, borane, trifluoromethyl and other functional groups introduced by chemical modification and the basalt fibers and the nano-carbon fibers.

Description

Technical Field

[0001] The invention relates to the technical field of polymer composite materials, in particular to a method for preparing a basalt fiber reinforced polymer material for photovoltaics. Background Art

[0002] Basalt is a natural material that comes from volcanic rocks that are frozen lava. Basalt rocks melt at about 1500-1700℃. Basalt fiber is a glass fiber drawn from natural basalt. It is composed of natural fibers, minerals, plagioclase, pyroxene and olivine. Basalt fiber can greatly improve the mechanical properties of reinforced polymer composites, and is therefore widely used in the photovoltaic field.

[0003] Chinese patent CN109422960B: discloses a carbon fiber reinforced polymer composite material and a preparation method thereof. The carbon fiber reinforced polymer composite material can improve the interface bonding strength by modifying the surface of the carbon fiber with an amphiphilic block copolymer and then forming a composite material of the surface modified carbon fiber and the polymer.

[0004] Chinese patent CN110922616B: relates to composite materials and preparation methods thereof, specifically discloses fiber-reinforced polymer composite materials and preparation methods thereof. The fiber-reinforced polymer composite material is prepared by heating and curing on a pultrusion winding machine, and the fiber-reinforced polymer composite material is made of the following components by weight: 85-112 parts of polymer resin matrix, 15-45 parts of modified reinforcing fiber, 3-8 parts of silane coupling agent, 4-7 parts of curing agent, 0.5-1 part of antioxidant and 0.5-1 part of ultraviolet absorber.

[0005] Chinese patent CN106938548A: relates to a fiber-reinforced polymer composite material and a preparation method thereof, wherein the fiber-reinforced polymer composite material comprises a polymer resin matrix in a continuous phase and chemical fiber fabrics and reinforcing fibers dispersed in the polymer resin matrix, wherein the chemical fiber fabrics cover the reinforcing fibers to prevent the reinforcing fibers from being exposed to the surface of the composite material.

[0006] The polymer composite materials prepared by the above patents and prior art have poor interlaminar shear strength and post-impact compression strength, resulting in poor overall anti-destruction ability and poor anti-deformation performance of the composite materials. Summary of the invention

[0007] In view of this, the purpose of the present invention is to provide a method for preparing a basalt fiber reinforced polymer material for photovoltaics, which enhances the interlaminar shear strength of the composite material and improves the impact toughness of the material.

[0008] To achieve the above-mentioned purpose, the preparation method of basalt fiber reinforced polymer material provided by the present invention adopts the following technical scheme:

[0009] A method for preparing a basalt fiber reinforced polymer material for photovoltaics, the operating steps of which are:

[0010] S1: Weigh 30-40 parts of epoxy resin, 3-6 parts of (R)-N-epoxypropylphthalimide, add 200-300 parts of solvent, stir and mix evenly, then add 4-7 parts of molten m-phenylenediamine and 2-5 parts of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly, and obtain a glue solution;

[0011] S2: Fix 50-60 parts of basalt fibers on a steel frame, and apply glue on the basalt fibers to obtain a prepreg;

[0012] S3: compacting and curing the prepreg using a mold;

[0013] S4: The cured prepreg is laid in 4 layers at 90°, placed between flat molds, laminated, cured, and cooled to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications.

[0014] Preferably, the epoxy resin is one of E55, E54, E44, E42, and E51.

[0015] Preferably, the solvent is one of toluene, xylene, butanone and acetone.

[0016] Preferably, the curing operation steps of S3 are: heating to 120-130°C and keeping warm for 90-120 minutes; continuing to heating to 150-170°C and keeping warm for 90-120 minutes; continuing to heating to 180-200°C and keeping warm for 90-120 minutes.

[0017] Preferably, the lamination pressure of S4 is 4-7Mpa.

[0018] Preferably, the curing operation steps of S4 are heating to 120-130° C. and keeping the temperature for 90-120 min; and further heating to 160-180° C. and keeping the temperature for 90-120 min.

[0019] Preferably, the preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is:

[0020] H1: In a stirred reactor, nitrogen is used to replace air, 0.3-0.8 parts of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether CAS: 344-48-9, 10-15 parts of propylene boric acid o-di-tert-alcohol ester, 2-5 parts of potassium tert-butoxide, and 1200-1400 parts of DMF are added by weight, and the reaction is carried out at 60-70°C and normal pressure; the reaction mixture is stirred for 30-60 minutes;

[0021] H2: Add 100-150 parts of amino multi-walled carbon nanotubes CAS#: 83602-37-3, react at 60-70° C. and normal pressure for 50-100 minutes, filter, and dry to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

[0022] The technical mechanism of the present invention is:

[0023] 1. Interaction between anisole and borane: The oxygen atom in anisole has a lone pair of electrons and can react with borane as a Lewis base; borane, as an electron-deficient compound, easily forms a complex with anisole to enhance the interaction between molecules; this interaction may increase the stability and rigidity of the material structure by forming borane-anisole adducts, thereby indirectly improving the impact toughness of the material.

[0024] 2. Introduction of trifluoromethyl group: trifluoromethyl group has a strong electron-withdrawing effect, which can significantly affect the electron distribution and reactivity of the molecule. In the modification process of carbon nanotubes, the introduction of trifluoromethyl group may lead to the redistribution of electron density between adjacent molecular chains and increase the interfacial interaction between carbon nanotubes and other substances. The enhanced interfacial interaction can effectively transfer stress and improve the overall mechanical properties of the composite material, including impact toughness.

[0025] The beneficial effects of the present invention are:

[0026] 1. Enhanced interlaminar shear strength: The combination of basalt fiber and nano-carbon fiber, using the synergistic effect of their physical properties, can form a more complex network structure in the composite material; the existence of this structure hinders the mutual sliding between layers, thereby increasing the interlaminar shear strength, which is crucial to improving the overall mechanical properties of the material.

[0027] 2. Improve impact resistance: The functional groups such as anisole, borane and trifluoromethyl introduced through chemical modification, as well as the synergistic effect of basalt fiber and nano-carbon fiber, not only enhance the bearing capacity of the material, but also improve the stress distribution of the material when it is impacted; more optimized stress distribution helps the material to perform better in absorbing and dispersing impact energy, significantly improves the impact toughness of the material, and prolongs its service life. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution of the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention.

[0029] Obviously, the described embodiments are only some embodiments of the present invention, but not all embodiments. Based on the described embodiments of the present invention, all other embodiments obtained by those skilled in the art are within the protection scope of the present invention.

[0030] Example 1

[0031] A method for preparing a basalt fiber reinforced polymer material for photovoltaics, the operating steps of which are:

[0032] S1: Weigh 30g of epoxy resin and 3g of (R)-N-epoxypropylphthalimide, add 200g of solvent and stir to mix evenly, then add 4g of molten m-phenylenediamine and 2g of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly to obtain a glue solution;

[0033] S2: Fix 50g of basalt fiber on a steel frame and apply glue on the basalt fiber to obtain a prepreg;

[0034] S3: compacting and curing the prepreg using a mold;

[0035] S4: The cured prepreg is laid in 4 layers at 90°, placed between flat molds, laminated, cured, and cooled to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications.

[0036] The epoxy resin is E55.

[0037] The solvent is toluene.

[0038] The curing operation steps of S3 are as follows: heating to 120°C and keeping warm for 90 minutes; further heating to 150°C and keeping warm for 90 minutes; further heating to 180°C and keeping warm for 90 minutes.

[0039] The lamination pressure of S4 is 4Mpa.

[0040] The curing operation steps of S4 are to heat up to 120° C. and keep the temperature for 90 minutes; then continue to heat up to 160° C. and keep the temperature for 90 minutes.

[0041] The preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is as follows:

[0042] H1: In a stirred reactor, nitrogen was used to replace air, 0.3 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether CAS: 344-48-9, 10 g of propylene boric acid o-di-tert-alcohol ester, 2 g of potassium tert-butoxide, and 1200 g of DMF were added, and the reaction was carried out at 60° C. and normal pressure; the reaction mixture was stirred for 30 minutes;

[0043] H2: 100 g of amino-modified multi-walled carbon nanotubes CAS#: 83602-37-3 were added, and the mixture was reacted at 60° C. and normal pressure for 50 minutes. The mixture was filtered and dried to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

[0044] Example 2

[0045] A method for preparing a basalt fiber reinforced polymer material for photovoltaics, the operating steps of which are:

[0046] S1: Weigh 33g of epoxy resin and 4g of (R)-N-epoxypropylphthalimide, add 240g of solvent and stir to mix evenly, then add 5g of molten m-phenylenediamine and 3g of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly to obtain a glue solution;

[0047] S2: 53 g of basalt fiber is fixed on a steel frame, and glue is applied on the basalt fiber to obtain a prepreg;

[0048] S3: compacting and curing the prepreg using a mold;

[0049] S4: The cured prepreg is laid in 4 layers at 90°, placed between flat molds, laminated, cured, and cooled to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications.

[0050] The epoxy resin is E54.

[0051] The solvent is xylene.

[0052] The curing operation steps of S3 are as follows: heating to 125°C and keeping warm for 100 minutes; further heating to 155°C and keeping warm for 100 minutes; further heating to 185°C and keeping warm for 100 minutes.

[0053] The lamination pressure of S4 is 5Mpa.

[0054] The curing operation steps of S4 are to heat up to 125°C and keep it warm for 100 minutes; then continue to heat up to 165°C and keep it warm for 100 minutes.

[0055] The preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is as follows:

[0056] H1: In a stirred reactor, nitrogen was used to replace air, 0.4 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether CAS: 344-48-9, 12 g of propylene boric acid o-di-tert-alcohol ester, 3 g of potassium tert-butoxide, and 1250 g of DMF were added, and the reaction was carried out at 65° C. and normal pressure; the reaction mixture was stirred for 40 minutes;

[0057] H2: 110 g of amino-modified multi-walled carbon nanotubes CAS#: 83602-37-3 were added, and the mixture was reacted at 65° C. and normal pressure for 70 minutes. The mixture was filtered and dried to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

[0058] Example 3

[0059] A method for preparing a basalt fiber reinforced polymer material for photovoltaics, the operating steps of which are:

[0060] S1: Weigh 38g of epoxy resin and 5g of (R)-N-epoxypropylphthalimide, add 280g of solvent and stir to mix evenly, then add 6g of molten m-phenylenediamine and 4g of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly to obtain a glue solution;

[0061] S2: Fix 58g of basalt fiber on a steel frame and apply glue on the basalt fiber to obtain a prepreg;

[0062] S3: compacting and curing the prepreg using a mold;

[0063] S4: The cured prepreg is laid in 4 layers at 90°, placed between flat molds, laminated, cured, and cooled to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications.

[0064] The epoxy resin is E44.

[0065] The solvent is butanone.

[0066] The curing operation steps of S3 are as follows: heating to 125°C and keeping warm for 110 minutes; further heating to 165°C and keeping warm for 110 minutes; further heating to 195°C and keeping warm for 110 minutes.

[0067] The lamination pressure of S4 is 6Mpa.

[0068] The curing operation steps of S4 are to heat up to 125°C and keep warm for 110 minutes; then continue to heat up to 175°C and keep warm for 110 minutes.

[0069] The preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is as follows:

[0070] H1: In a stirred reactor, the air was replaced with nitrogen, 0.7 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether CAS: 344-48-9, 14 g of propenyl boric acid o-di-tert-alcohol ester, 4 g of potassium tert-butoxide, and 1350 g of DMF were added, and the reaction was carried out at 65° C. and normal pressure; the reaction mixture was stirred for 50 minutes;

[0071] H2: 140 g of amino-modified multi-walled carbon nanotubes CAS#: 83602-37-3 were added, and the mixture was reacted at 65° C. and normal pressure for 90 minutes. The mixture was filtered and dried to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

[0072] Example 4

[0073] A method for preparing a basalt fiber reinforced polymer material for photovoltaics, the operating steps of which are:

[0074] S1: Weigh 40g of epoxy resin and 6g of (R)-N-epoxypropylphthalimide, add 300g of solvent, stir and mix evenly, then add 7g of molten m-phenylenediamine and 5g of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly, and obtain a glue solution;

[0075] S2: Fix 60g of basalt fiber on a steel frame and apply glue on the basalt fiber to obtain a prepreg;

[0076] S3: compacting and curing the prepreg using a mold;

[0077] S4: The cured prepreg is laid in 4 layers at 90°, placed between flat molds, laminated, cured, and cooled to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications.

[0078] The epoxy resin is E51.

[0079] The solvent is acetone.

[0080] The curing operation steps of S3 are: heating to 130°C and keeping warm for 120 minutes; further heating to 170°C and keeping warm for 120 minutes; further heating to 200°C and keeping warm for 120 minutes.

[0081] The lamination pressure of S4 is 7Mpa.

[0082] The curing operation steps of S4 are to heat up to 130° C. and keep the temperature for 120 minutes; then continue to heat up to 180° C. and keep the temperature for 120 minutes.

[0083] The preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is as follows:

[0084] H1: In a stirred reactor, nitrogen was used to replace air, 0.8 g of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether CAS: 344-48-9, 15 g of propylene boric acid o-di-tert-alcohol ester, 5 g of potassium tert-butoxide, and 1400 g of DMF were added, and the reaction was carried out at 70° C. and normal pressure; the reaction mixture was stirred for 60 minutes;

[0085] H2: 150 g of amino-modified multi-walled carbon nanotubes CAS#: 83602-37-3 were added, and the mixture was reacted at 70° C. and normal pressure for 100 minutes. The mixture was filtered and dried to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

[0086] Comparative Example 1

[0087] This example is a comparative example of Example 1, except that no trifluoromethyl-containing multi-walled carbon nanotubes are added.

[0088] Comparative Example 2

[0089] This example is a comparative example of Example 1, except that 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether is not added, and the other conditions are the same as those of Example 1.

[0090] Comparative Example 3

[0091] This example is a comparative example of Example 1, except that no propylene boric acid 1-di-tert-ol ester is added, and the rest is the same as Example 1.

[0092] Evaluation of the embodiment:

[0093] The composite material was mounted on a universal tensile testing machine and the impact load performance was tested: the size of the composite material was 250 mm × 25 mm × 2 mm, and the loading rate was 5 mm / min.

[0094] Interlaminar shear strength: tested in accordance with ASTM D2344, with a specimen size of 39 mm × 13 mm × 6.5 mm, a bending span and material thickness ratio of 4:1, and a test rate of 1 mm / min.

[0095] Table 4 Test results of examples and comparative examples

[0096] Interlaminar shear strength / Mpa Compression strength after impact / Mpa Example 1 59.8 264 Example 2 61.3 269 Example 3 62.5 275 Example 4 63.7 281 Comparative Example 1 40.8 175 Comparative Example 2 46.3 183 Comparative Example 3 48.1 195

[0097] Through the data analysis of the above embodiments and comparative examples, the basalt fiber reinforced polymer composite material prepared by the present invention has high interlaminar shear strength, post-impact compression strength and excellent mechanical properties.

[0098] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a basalt fiber reinforced polymer material for photovoltaic use, the operating steps of which are: S1: Weigh 30-40 parts of epoxy resin and 3-6 parts of (R)-N-epoxypropylphthalimide by weight, add 200-300 parts of solvent, stir and mix evenly, then add 4-7 parts of molten m-phenylenediamine and 2-5 parts of trifluoromethyl-containing multi-walled carbon nanotubes, mix evenly, and obtain a glue solution; S2: Fix 50-60 parts of basalt fibers on a steel frame, and apply glue on the basalt fibers to obtain a prepreg; S3: compacting and curing the prepreg using a mold; S4: laying the cured prepreg in 4 layers at 90°, placing them between flat molds, laminating, curing, and cooling to room temperature to obtain a basalt fiber reinforced polymer composite material for photovoltaic applications; The preparation method of the trifluoromethyl-containing multi-walled carbon nanotubes is as follows: H1: In a stirred reactor, 0.3-0.8 parts of 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether, 10-15 parts of propenyl boric acid o-di-tert-alcohol ester, 2-5 parts of potassium tert-butoxide, and 1200-1400 parts of DMF are added by weight, and the mixture is reacted at 60-70° C. and normal pressure; the reaction mixture is stirred for 30-60 minutes; H2: Add 100-150 parts of amino multi-walled carbon nanotubes, react at 60-70° C. and normal pressure for 50-100 minutes, filter, and dry to obtain trifluoromethyl-containing multi-walled carbon nanotubes.

2. The method for preparing a photovoltaic basalt fiber reinforced polymer material according to claim 1, characterized in that: The epoxy resin is one of E55, E54, E44, E42 and E51.

3. The method for preparing a photovoltaic basalt fiber reinforced polymer material according to claim 1, characterized in that: The solvent is one of toluene, xylene, butanone and acetone.

4. The method for preparing a photovoltaic basalt fiber reinforced polymer material according to claim 1, characterized in that: The curing operation steps of S3 are as follows: heating to 120-130°C and keeping warm for 90-120 minutes; further heating to 150-170°C and keeping warm for 90-120 minutes; further heating to 180-200°C and keeping warm for 90-120 minutes.

5. The method for preparing a photovoltaic basalt fiber reinforced polymer material according to claim 1, characterized in that: The lamination pressure of S4 is 4-7Mpa.

6. The method for preparing a photovoltaic basalt fiber reinforced polymer material according to claim 1, characterized in that: The curing operation steps of S4 are as follows: heating to 120-130° C., keeping the temperature for 90-120 minutes; and continuing to heating to 160-180° C., keeping the temperature for 90-120 minutes.