Photovoltaic sealant anti-aging nano calcium carbonate surface treatment method and photovoltaic sealant

Abstract

The application relates to a surface treatment method of anti-aging nano calcium carbonate for photovoltaic sealant. The nano calcium carbonate is treated on the surface by using monostearin and 2,4,6-tri(4-carboxyl phenyl)-1,3,5-triazine and sodium phosphite, the nano calcium carbonate treated by the method has high activity and good dispersibility, has good resistance to humid heat aging and ultraviolet aging in photovoltaic glue application, and thus improves the aging and yellowing problems existing in the current photovoltaic glue.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of nanoscale calcium carbonate preparation and relates to a surface treatment method of anti-aging nanoscale calcium carbonate for photovoltaic sealant. BACKGROUND

[0002] As a room temperature curable neutral one-component silicone sealant, silicone photovoltaic sealant is widely used in the bonding operation of the external frame and junction box of solar photovoltaic modules due to its fast deep curing, excellent bonding performance, non-corrosion to metal and environmental protection characteristics. Photovoltaic modules need to be stably operated in harsh outdoor environments for a long time, which puts strict requirements on the weather resistance of the sealant used. The aging yellowing problem is one of the main challenges in the application of silicone in the photovoltaic industry.

[0003] Chinese invention patent CN116282115A discloses a preparation method of nanoscale calcium carbonate for photovoltaic sealant. The invention obtains nanoscale calcium carbonate slurry by adding a dispersing agent and grinding and dispersing after calcination, digestion, refinement and sieving of limestone, and then adding a crystal form control and kiln gas. The modified nanoscale calcium carbonate slurry is obtained by adding a compound surface treatment agent to the nanoscale calcium carbonate slurry. The photovoltaic sealant special nanoscale calcium carbonate product is obtained by filtering, drying, crushing, grading and packaging the modified nanoscale calcium carbonate slurry. The beneficial technical effects are that the nanoscale calcium carbonate is easy to process, has low viscosity and good dispersibility when used for processing and filling of organic silicon sealant. The raw materials used in the method are cheap and easy to obtain, the cost is low, the process is simple and feasible, and the method is suitable for industrial production and has good economic and social benefits, but lacks anti-aging related properties.

[0004] Chinese invention patent CN10886473A discloses a surface treatment method of nanoscale calcium carbonate for silicone sealant of photovoltaic modules. The invention is modified for the first time with beef tallow and ammonium polyphosphate, and for the second time with a terminal carboxyl group polyester and a phosphite. The modified nanoscale calcium carbonate also has moisture resistance, high temperature resistance and oxidation resistance. When applied to photovoltaic sealant filling, it can improve the mechanical properties of the photovoltaic sealant and enhance the moisture resistance and high temperature resistance of the photovoltaic sealant, but still has deficiencies in terms of ultraviolet resistance.

[0005] Chinese invention patent CN105778568A discloses a surface treatment method of nanoscale calcium carbonate special for photovoltaic sealant. The invention is modified by using a compound surface treatment agent to obtain modified nanoscale calcium carbonate. The nanoscale calcium carbonate of the invention applied to filling photovoltaic sealant not only ensures excellent processing and mechanical properties of the sealant, but also has good viscosity, thixotropy, high tensile strength and moisture resistance and aging resistance, but still has deficiencies in terms of ultraviolet resistance.

[0006] In summary, it is necessary to seek a kind of nano calcium carbonate that can not only endow photovoltaic glue with good resistance to humid heat aging, but also provide better anti-ultraviolet effect to solve the yellowing problem. SUMMARY

[0007] The application aims to provide a preparation method of anti-aging nano calcium carbonate for photovoltaic sealant.

[0008] The application uses monostearin, 2, 4, 6-tri (4-carboxyl phenyl) -1, 3, 5-triazine and sodium phosphite to treat the surface of nano calcium carbonate, and the nano calcium carbonate treated by the method has high activity and good dispersibility, and has good resistance to humid heat aging and ultraviolet aging in photovoltaic glue application.

[0009] The application specifically implements the following steps:

[0010] A surface treatment method of anti-aging nano calcium carbonate for photovoltaic sealant glue comprises the following steps:

[0011] (1) add nano calcium carbonate slurry into a reaction kettle and heat to 60-90℃;

[0012] (2) add the prepared surface treatment agent into the slurry of step (1) to perform surface treatment, and stir to obtain modified nano calcium carbonate slurry;

[0013] (3) dehydrate, dry and crush the obtained modified nano calcium carbonate slurry to obtain nano calcium carbonate product.

[0014] The specific surface area of the nano calcium carbonate is 15-35 m2 / g, and the concentration of the nano calcium carbonate slurry is 14%-17%.

[0015] The surface treatment agent is a mixture of monostearin, 2, 4, 6-tri (4-carboxyl phenyl) -1, 3, 5-triazine and sodium phosphite.

[0016] The mass ratio of monostearin, 2, 4, 6-tri (4-carboxyl phenyl) -1, 3, 5-triazine and sodium phosphite is 15-35:1:2-5.

[0017] The addition amount of the surface treatment agent is 0.1%-0.5% of the mass of the nano calcium carbonate.

[0018] After adding the surface treatment agent, the modified nano calcium carbonate slurry is stirred at 1200-1800 r / min.

[0019] The drying temperature in step (3) is 105℃-125℃.

[0020] The key technical features of the present application are that a surface treatment agent is prepared by using monostearin, 2, 4, 6-tri (4-carboxyphenyl) -1, 3, 5-triazine and sodium phosphite in a corresponding proportion, and then high-speed stirring is used to perform surface treatment on high-concentration nano calcium carbonate slurry. Compared with the existing nano calcium carbonate surface-modified by stearic acid, the product of the present application has better dispersibility, higher specific surface area and lower oil absorption value; in photovoltaic adhesive applications, it can provide good ultraviolet resistance on the basis of existing performance. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The electron microscope images of the nano calcium carbonate obtained in Example 2 and Comparative Example 1 are shown in a) for Comparative Example 1 and b) for Example 2.

[0022] Figure 2 The ultraviolet-visible absorption spectrum of 2, 4, 6-tri (4-carboxyphenyl) -1, 3, 5-triazine is shown. It can be seen that the compound has good ultraviolet resistance.

[0023] Figure 3 The moisture and heat resistance test graphs of Example 2 and Comparative Example 1 are shown on the left for Example 2 and on the right for Comparative Example 1.

[0024] Figure 4 The ultraviolet aging test graphs of Example 2 and Comparative Example 1 are shown on the left for Example 2 and on the right for Comparative Example 1. DETAILED DESCRIPTION

[0025] The present application will be further described below through specific implementation:

[0026] Example 1

[0027] A surface treatment method of an anti-aging nano calcium carbonate for photovoltaic adhesive sealant, comprising the following steps:

[0028] (1) The nano calcium carbonate slurry with a concentration of 15.1% and a BET of 27.5 m2 / g is added to a reaction kettle, stirred, and heated to 80℃;

[0029] (2) The slurry of step (1) is surface treated with the surface treatment agent of the present application (monostearin: 2, 4, 6-tri (4-carboxyphenyl) -1, 3, 5-triazine: sodium phosphite = 15:1:2), wherein the addition amount of the compounded surface treatment agent is 0.2% of the mass of nano calcium carbonate in the slurry, and stirring is carried out at 1500 r / min for 35 min to obtain modified nano calcium carbonate;

[0030] (3) The modified nano calcium carbonate is filtered and dewatered, and dried at a drying temperature of 110℃ to obtain dried material;

[0031] (4) again the dry material is crushed, graded and packaged according to the conventional method to obtain the nano calcium carbonate product.

[0032] Example 2

[0033] A surface treatment method of anti-aging nano calcium carbonate for photovoltaic glue sealant, comprising the following steps:

[0034] (1) adding nano calcium carbonate slurry with a concentration of 15.1% and a BET of 27.5 m2 / g into a reaction kettle, stirring, and heating to 80℃;

[0035] (2) adding the surface treatment agent of the application to the slurry of step (1) for surface treatment (monostearin: 2,4, 6-tris (4-carboxyphenyl) -1, 3, 5-triazine: sodium phosphite = 20:1:3), wherein the addition amount of the compounded surface treatment agent is 0.3% of the mass of nano calcium carbonate in the slurry, stirring at 1500 r / min for 35 min to obtain modified nano calcium carbonate;

[0036] (3) filtering and dewatering the modified nano calcium carbonate, drying, and the drying temperature is 110℃ to obtain dry material;

[0037] (4) again the dry material is crushed, graded and packaged according to the conventional method to obtain the nano calcium carbonate product.

[0038] As can be seen from Figure 1 , the electron microscope shooting of the application is more uniform, and the dispersibility is stronger than that of the existing stearic acid surface treatment agent modification.

[0039] As can be seen from Figure 3 , under the same conditions, the application has no obvious difference with comparative example 1, and there is no obvious difference in anti-humidity and heat aging.

[0040] As can be seen from Figure 4 , the redness of comparative example 1 is obviously higher than that of the application, so the application has obvious advantages in anti-ultraviolet performance.

[0041] Example 3

[0042] A surface treatment method of anti-aging nano calcium carbonate for photovoltaic glue sealant, comprising the following steps:

[0043] (1) adding nano calcium carbonate slurry with a concentration of 15.6% and a BET of 28.2 m2 / g into a reaction kettle, stirring, and heating to 80℃;

[0044] (2) to the slurry of step (1), add the surface treatment agent of the present application for surface treatment (monostearin: 2, 4, 6-tri (4-carboxyphenyl) -1, 3, 5-triazine: sodium phosphite = 20: 1: 4), wherein the adding amount of the compounded surface treatment agent is 0.3% of the mass of nano calcium carbonate in the slurry, stirring at 1500r / min for 35min, obtaining modified nano calcium carbonate;

[0045] (3) filter pressing and dewatering the modified nano calcium carbonate, drying, the drying temperature is 110℃, obtaining dried material;

[0046] (4) further crushing, grading and packaging the dried material according to the conventional method to obtain nano calcium carbonate product.

[0047] Example 4

[0048] A surface treatment method of anti-aging nano calcium carbonate for photovoltaic adhesive sealant, comprising the following steps:

[0049] (1) adding nano calcium carbonate slurry with a concentration of 15.6% and a BET of 28.2m2 / g into a reaction kettle, stirring, and heating to 80℃;

[0050] (2) to the slurry of step (1), add the surface treatment agent of the present application for surface treatment (monostearin: 2, 4, 6-tri (4-carboxyphenyl) -1, 3, 5-triazine: sodium phosphite = 20: 1: 4), wherein the adding amount of the compounded surface treatment agent is 0.3% of the mass of nano calcium carbonate in the slurry, stirring at 1500r / min for 35min, obtaining modified nano calcium carbonate;

[0051] (3) filter pressing and dewatering the modified nano calcium carbonate, drying, the drying temperature is 110℃, obtaining dried material;

[0052] (4) further crushing, grading and packaging the dried material according to the conventional method to obtain nano calcium carbonate product.

[0053] Example 5

[0054] A surface treatment method of anti-aging nano calcium carbonate for photovoltaic adhesive sealant, comprising the following steps:

[0055] (1) adding nano calcium carbonate slurry with a concentration of 15.6% and a BET of 28.2m2 / g into a reaction kettle, stirring, and heating to 80℃;

[0056] (2) to the slurry of step (1), surface treatment is carried out by adding the surface treatment agent of the present application (monostearin: 2, 4, 6-tris (4-carboxyphenyl) -1, 3, 5-triazine: sodium phosphite = 28: 1: 3.5), wherein the surface treatment agent is added in an amount of 0.5% of the mass of the nano calcium carbonate in the slurry, and stirring is carried out at 1500 r / min for 35 min, to obtain modified nano calcium carbonate;

[0057] (3) the modified nano calcium carbonate is dewatered by pressure filtration, dried, and the drying temperature is 110°C, to obtain dried material;

[0058] (4) the dried material is crushed, classified and packaged according to a conventional method, to obtain nano calcium carbonate product.

[0059] Comparative Example 1

[0060] A surface treatment method for existing nano calcium carbonate includes the following steps:

[0061] (1) nano calcium carbonate slurry with a concentration of 15.1% and a BET of 27.5 m2 / g is added to a reaction kettle, stirred, and heated to 80°C;

[0062] (2) surface treatment is carried out by adding a stearic acid surface treatment agent to the slurry of step (1), wherein the stearic acid surface treatment agent is added in an amount of 0.3% of the mass of the nano calcium carbonate in the slurry, and stirring is carried out at 1500 r / min for 35 min, to obtain modified nano calcium carbonate;

[0063] (3) the modified nano calcium carbonate is dewatered by pressure filtration, dried, and the drying temperature is 110°C, to obtain dried material;

[0064] (4) the dried material is crushed, classified and packaged according to a conventional method, to obtain nano calcium carbonate product.

[0065] Comparative Example 2

[0066] A surface treatment method for existing nano calcium carbonate includes the following steps:

[0067] (1) nano calcium carbonate slurry with a concentration of 15.6% and a BET of 28.2 m2 / g is added to a reaction kettle, stirred, and heated to 80°C;

[0068] (2) surface treatment is carried out by adding a stearic acid surface treatment agent to the slurry of step (1), wherein the stearic acid surface treatment agent is added in an amount of 0.5% of the mass of the nano calcium carbonate in the slurry, and stirring is carried out at 1500 r / min for 35 min, to obtain modified nano calcium carbonate;

[0069] (3) the modified nano calcium carbonate is dewatered by pressure filtration, dried, and the drying temperature is 110°C, to obtain dried material;

[0070] (4) The dried material is crushed, classified and packaged to obtain the nano calcium carbonate product according to a conventional method.

[0071] The nano calcium carbonate obtained by the embodiments and the comparative examples is detected to obtain Table 1. The photovoltaic glue is prepared according to the following formula, and the formula of the photovoltaic glue is shown in Table 2.

[0072] Table 1: Nano calcium detection

[0073]

[0074] Table 2: Preparation of photovoltaic glue formula

[0075]

[0076] The plasticizer in the above formula is dioctyl phthalate (DOP), the crosslinking agent is dicumyl peroxide (DCP): 2,5-dimethyl-2,5-di-tert-butylperoxyhexane (double 25) = 1:3, the coupling agent is γ-aminopropyltrimethoxysilane (KH-550), and the catalyst is dibutyltin dilaurate.

[0077] The preparation method of the photovoltaic glue is as follows:

[0078] The raw materials are weighed according to the above mass fraction, the weighed hydroxyl-terminated polydimethylsiloxane, nano calcium carbonate and plasticizer are put into a planetary stirrer, and the material is mixed uniformly under the condition of a vacuum degree of-0.08 MPa or more and a temperature of 110-130℃ for 3h; cooled to below 40℃, the crosslinking agent, coupling agent and catalyst are added to the system in turn, and the system is continuously mixed uniformly under vacuum for 30min, then discharged and packaged, to obtain the finished photovoltaic glue.

[0079] The test results of the photovoltaic glue obtained by the embodiments and the comparative examples are shown in Table 3.

[0080] Table 3: Product performance test results of the photovoltaic glue prepared by the embodiments and the comparative examples

[0081]

[0082] From the above results and Figure 3 , Figure 4 It can be seen that the nano calcium carbonate modified by the embodiments of the present application has differences in conventional detection compared with the comparative examples, including a decrease in oil absorption value, an increase in BET, and a slight increase in moisture and whiteness. After the above nano calcium is made into photovoltaic glue, compared with the conventional nano calcium carbonate modification method, the effect on mechanical properties and moisture and heat aging resistance is similar, and the effect on ultraviolet resistance is significantly enhanced.

Claims

1. A surface treatment method of anti-aging nano calcium carbonate for photovoltaic glue sealant, characterized in that, It comprises the following steps: (1) adding nano calcium carbonate slurry into a reactor and heating to 60-90℃; (2) adding a prepared surface treatment agent into the slurry of step (1) for surface treatment, and stirring to obtain modified nano calcium carbonate slurry, The surface treatment agent is a mixture of glycerol monostearate, 2,4, 6-tris (4-carboxyphenyl) -1, 3, 5-triazine and sodium phosphite, and the mass ratio of glycerol monostearate, 2,4, 6-tris (4-carboxyphenyl) -1, 3, 5-triazine and sodium phosphite is 15-35:1:2-5, and the addition amount of the surface treatment agent is 0.1%-0.5% of the mass of nano calcium carbonate; (3) dehydrating, drying and crushing the obtained modified nano calcium carbonate slurry to obtain nano calcium carbonate product.

2. The surface treatment method of the anti-aging nano calcium carbonate for photovoltaic glue sealant according to claim 1, characterized in that, The specific surface area of the nano calcium carbonate is 15-35 m 2 / g, and the concentration of the nano calcium carbonate slurry is 14%-17%.

3. The surface treatment method of anti-aging nano calcium carbonate for photovoltaic glue sealant according to claim 1, characterized in that, After adding the surface treatment agent, stirring at 1200-1800r / min to obtain modified nano calcium carbonate slurry.

4. The surface treatment method of anti-aging nano calcium carbonate for photovoltaic glue sealant according to claim 1, characterized in that, The drying temperature in step (3) is 105℃-125℃.

5. A photovoltaic paste, characterized in that, The photovoltaic glue comprises the anti-aging nano calcium carbonate prepared by the method of any one of claims 1-4.

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