CN105505297A - Anti-yellowing well-stored single-component dealcoholization solar photovoltaic assembly sealant and preparation method thereof - Google Patents

Abstract

The invention relates to a one-component dealcoholized solar photovoltaic module sealant with anti-yellowing and good storage. The sealant is composed of the following raw materials in parts by weight: α,ω-dihydroxy polydimethylsiloxane 30～ 70 parts, 30-70 parts of filler, 2-10 parts of alkoxysilane crosslinking agent, 0.5-5 parts of silane coupling agent, 0.1-3 parts of titanium catalyst, 0.5-5 parts of anti-yellowing agent, 0.5 parts of hydroxyl scavenger ~5 servings. The sealant prepared by the invention is resistant to yellowing and has no corrosion effect on copper, lead, zinc, polycarbonate and other materials and has good storage stability. It is suitable for sealing the aluminum frame of the solar photovoltaic module and filling the back plate and the frame Sealing and bonding of junction boxes.

Description

Anti-yellowing, good storage one-component dealcoholized solar photovoltaic module sealant and preparation method thereof

technical field

The invention relates to a one-component dealcoholized solar photovoltaic module sealant with anti-yellowing and good storage and a preparation method thereof, belonging to the technical field of silicone sealants.

Background technique

76% of my country's land is full of sunlight, and the distribution of light energy resources is relatively uniform; compared with hydropower, wind power, nuclear power, etc., solar power generation has no emissions and noise, and the application technology is mature, safe and reliable; solar energy is the cleanest, safest and most reliable in the future In terms of energy, developed countries are taking the development and utilization of solar energy as the main content of the long-term planning of the energy revolution. The best way to use solar energy is photovoltaic conversion, which is to use the photovoltaic effect to make sunlight shine on silicon materials to generate electricity and generate electricity directly. The photoelectric conversion industry chain formed by the application and development of silicon materials is called "photovoltaic industry", including the production of high-purity polysilicon raw materials, solar cell production, solar cell module production, and related production equipment manufacturing. In order to exploit and use solar energy more effectively, countries all over the world are constantly developing solar photovoltaic module technology and making use of this "never exhausted" energy as much as possible. Photovoltaic industry is increasingly becoming another explosive development industry after IT and microelectronics industry in the world.

Photovoltaic module sealant is an indispensable and important auxiliary material in solar photovoltaic modules. It is used to bond frames and junction boxes to effectively protect silicon wafers from contamination and oxidation. Solar photovoltaic modules are directly exposed to the outside world, so there are high requirements for photovoltaic module sealants: high strength and good adhesion; ability to withstand high and low temperature environments; moisture-proof and environmental corrosion resistance; Mechanical shock and shock resistance; good resistance to yellowing and heat and humidity; good storage performance, etc.

Silicone sealant has excellent UV resistance and atmospheric aging resistance, and can keep at least 25 years without cracking, brittleness, and chalking in harsh environments such as sunlight, rain, snow, and seasonal climate changes, and has excellent high-temperature resistance. It has low temperature performance and a displacement capacity of more than 25% in a wide temperature range, and also has good electrical insulation performance, waterproof and dustproof, so it is very suitable for sealing solar photovoltaic modules.

There are many patent documents related to solar photovoltaic module sealants and one-component dealcoholized sealants. The patent application publication number CN101353563A provides a single-component silicone sealant for solar cell modules and its manufacturing method. The obtained sealant has excellent weather resistance, anti-yellowing performance, and low water vapor transmission. efficiency and good storage stability. However, its products belong to the deketoxime type sealant, which has a corrosive effect on copper, zinc, lead and polycarbonate (PC), which limits its application range.

The patent application publication number CN101717582A mentions a two-component room temperature vulcanized silicone rubber for photovoltaic modules, which includes two components, A component and B component. The glue machine evenly coats the workpiece, which has the characteristics of good bonding performance and fast curing speed. But in actual use, special equipment must be used to mix components A and B in proportion, which is inconvenient to operate.

The patent application publication number CN103146339A discloses a dealcoholized fast-curing silicone sealant and its preparation method. The prepared sealant has excellent curing speed, extreme mechanical properties, yellowing resistance and ideal storage stability It can be used for the sealing of solar photovoltaic modules, but its embodiment only involves the test of the storage period, and does not test the resistance to yellowing and other properties applied to solar photovoltaic modules.

The patent with the application publication number CN101760172A discloses a one-component dealcoholized silicone sealant, and proposes an adhesive for photovoltaic modules resistant to "Double 85", but does not mention the test method of the storage period and whether it is resistant to ultraviolet rays.

Contents of the invention

The purpose of the present invention is to overcome the existing one-component deketoxime type photovoltaic module sealant which is not resistant to yellowing and has a corrosive effect on certain materials (such as copper, lead, zinc, polycarbonate, etc.) and the existing single-component sealant. In order to solve the problem of poor storage stability of one-component dealcoholized photovoltaic module sealant, we provide a one-component dealcoholized solar photovoltaic module sealant with excellent adhesion performance, high strength and good elongation. 85” and water-resistant to yellowing under ultraviolet radiation, long storage period, suitable for sealing the aluminum frame of solar photovoltaic modules, filling and sealing the back plate and the frame, and bonding the junction box.

In view of this, a kind of anti-yellowing and good storage one-component dealcoholized solar photovoltaic module sealant provided by the present invention is composed of the following raw materials in weight ratio:

The silane coupling agent is mixed with γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane in a molar mass ratio of 1:1 to 1:3 It is prepared by mixing γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane in a molar mass ratio of 1:1 to 1:3, Put it into a heatable vacuum reactor, and react for 8-72 hours at 80-150°C and a vacuum of -0.07-0.09 MPa. After the reaction is completed, fill it with nitrogen and cool to room temperature.

Under the condition that the molar mass ratio of γ-aminopropyltriethoxysilane to γ-(2,3-glycidoxy)propyltrimethoxysilane is 1:1～1:3, γ-aminopropyl The _-NH2 in triethoxysilane is all converted to -NH-- or , On the one hand, the anti-yellowing performance is greatly improved, on the other hand, the generated product has a larger cross-linked network structure, which can greatly improve the adhesiveness of the sealant.

The viscosity of the α,ω-dihydroxypolydimethylsiloxane at 25°C is 20000-80000mpa·s.

The filler is a mixture of light calcium carbonate and heavy calcium carbonate, and the weight ratio of the mixture is light calcium carbonate: heavy calcium carbonate=1:9～9:1, wherein light calcium carbonate is modified nano Active light calcium carbonate, the particle size is 20-100nm, and the crystal form is cubic.

The alkoxysilane crosslinking agent is methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, orthosilane Any one or a mixture of two or more of ethyl orthosilicate.

The titanium catalyst is isopropyl titanate, n-butyl titanate, bis(isopropoxy)bis(acetylacetonate)titanium, bis(isopropoxy)bis(ethyl acetoacetate)titanium, 1, Any one or a mixture of two or more of 3-propanedioxybis(ethyl acetoacetate)titanium.

The anti-yellowing agent in the sealant is a combination of inorganic metal oxide filler and organic antioxidant, and the weight ratio of the combination is inorganic metal oxide:organic antioxidant=5:1˜1:5. The inorganic metal oxide filler is any one or a mixture of two or more of aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, and the organic antioxidant is butyl hydroxyanisole (BHA), dibutyl Any one or a mixture of two or more of hydroxytoluene (BHT) and tert-butylhydroquinone (TBHQ).

Hydroxyl scavenger is toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hexamethyldisilazane Any one or a mixture of two or more.

In addition, the present invention also provides a method for one-component dealcoholization-type solar photovoltaic module sealant with good yellowing resistance and good storage, which is characterized in that it comprises the following steps:

1) Mix γ-aminopropyltriethoxysilane and γ-(2,3-glycidoxy)propyltrimethoxysilane in a molar mass ratio of 1:1 to 1:3, and put it in a heating In a vacuum reactor, react for 8 to 72 hours at 80 to 150 ° C and a vacuum of -0.07 to -0.09 MPa. After the reaction is completed, fill it with nitrogen and cool to room temperature;

2): Add 30 to 70 parts of α, ω-dihydroxy polydimethylsiloxane, 30 to 70 parts of filler, and 0.5 to 5 parts of anti-yellowing agent into the vacuum kneader. Dehydration and blending under the condition of -0.06～-0.09MPa for 0.5～5hr, then cooling to room temperature to obtain the base material, set aside;

3) At room temperature, move the base material obtained in step 2) into a planetary stirring tank, then add 2 to 10 parts of alkoxysilane crosslinking agent, 0.5 to 5 parts of silane coupling agent obtained in step 1), and 0.1 parts of titanium catalyst ～3 parts, 0.5～5 parts of hydroxyl scavenger are added into the stirred tank, stirred and mixed, and reacted for 0.3～2hr at a vacuum degree of -0.08～-0.10MPa and a rotational speed of 300～900rpm, and the target product is obtained by discharging and filling.

The advantages of the present invention are as follows:

1. The silane coupling agent uses the reaction product of γ-aminopropyltriethoxysilane and γ-(2,3-epoxypropoxy)propyltrimethoxysilane under specific conditions, so that the sealant has excellent Adhesive performance, while avoiding the yellowing caused by using amino silane coupling agent alone.

2. The anti-yellowing agent uses a combination of inorganic metal oxide fillers and organic antioxidants. The synergistic effect improves the anti-yellowing effect. The sealant will not yellow after "double 85" aging and water-ultraviolet aging. The mechanical properties remain good.

3. The storage performance is good. After accelerated storage at 100°C for 24 hours and storage at room temperature for one year, the mechanical properties remain basically unchanged compared with the initial stage.

4. Dealcohol-type curing system, no corrosion to various materials.

detailed description

The present aspect is specifically described below through the examples, it is necessary to point out that the following examples are only used to further illustrate the present invention, and can not be interpreted as limiting the protection scope of the present invention, those skilled in the art can according to the present invention Make non-essential improvements and adjustments.

Example 1

Mix 22.1 parts of γ-aminopropyltriethoxysilane and 23.6 parts of γ-(2,3-glycidoxy)propyltrimethoxysilane (molar mass ratio 1:1) into a vacuum reactor , heating temperature 100°C, vacuum degree -0.08MPa, react for 16hr, fill with nitrogen and cool to room temperature to obtain silane coupling agent.

40 parts of α, ω-dihydroxypolydimethylsiloxane with a viscosity of 20000mPa·s at 25°C, 30 parts of light calcium carbonate, 30 parts of heavy calcium carbonate, 2 parts of alumina, 0.5 parts of butyl hydroxy Add anisole (BHA) into the vacuum kneader, heat at 130°C, vacuum degree -0.09MPa, dehydrate and blend for 240 minutes, cool to room temperature to obtain the base material.

At room temperature, move the base material into a planetary stirring tank, then add 1 part of vinyltriethoxysilane, 4 parts of methyltrimethoxysilane, 1 part of silane coupling agent, 2 parts of bis(isopropoxy) Bis(ethyl acetoacetate)titanium and 0.5 parts of hexamethyldisilazane were stirred and mixed, and the chemical reaction was carried out at a vacuum degree of -0.08 MPa and a rotation speed of 600 RPM for 90 minutes, and the material was sealed and stored after discharge.

The properties of the sealant are shown in Table 1.

Example 2

Mix 22.1 parts of γ-aminopropyltriethoxysilane and 47.2 parts of γ-(2,3-glycidoxy)propyltrimethoxysilane (molar mass ratio 1:2) into a vacuum reactor , heating temperature 120°C, vacuum degree -0.07MPa, react for 30 hours, fill with nitrogen and cool to room temperature to obtain silane coupling agent.

Mix 50 parts of α, ω-dihydroxypolydimethylsiloxane with a viscosity of 50000mPa·s at 25°C, 40 parts of light calcium carbonate, 20 parts of heavy calcium carbonate, 3 parts of zinc oxide, and 1 part of tert-butyl Add hydroquinone (TBHQ) into the vacuum kneader, heat at 110°C, vacuum degree -0.08MPa, dehydrate and blend for 180 minutes, cool to room temperature to obtain the base material.

At room temperature, move the base material into a planetary stirring tank, then add 3 parts of vinyltrimethoxysilane, 2 parts of phenyltrimethoxysilane, 2 parts of silane coupling agent, 0.9 parts of bis(isopropoxy)bis (Acetylacetonate)titanium, 0.5 parts of titanium n-butyl titanate, and 1.5 parts of hexamethylene diisocyanate (HDI) were stirred and mixed, and the chemical reaction was carried out at a vacuum degree of -0.09MPa and a speed of 500RPM for 70 minutes, and sealed after discharge.

The properties of the sealant are shown in Table 1.

Example 3

Mix 22.1 parts of γ-aminopropyltriethoxysilane and 70.8 parts of γ-(2,3-glycidoxy)propyltrimethoxysilane (molar mass ratio 1:3) into a vacuum reactor , heating temperature 140°C, vacuum degree -0.09MPa, reacted for 48hrs, filled with nitrogen and cooled to room temperature to obtain a silane coupling agent.

Mix 60 parts of α, ω-dihydroxypolydimethylsiloxane with a viscosity of 80000mPa·s at 25°C, 50 parts of light calcium carbonate, 10 parts of heavy calcium carbonate, 1 part of titanium dioxide, 3 parts of dibutyl Hydroxytoluene (BHT)) was added into the vacuum kneader, the heating temperature was 125°C, the vacuum degree was -0.07MPa, dehydration and blending was carried out for 120 minutes, and the base was obtained by cooling to room temperature.

At room temperature, move the base material into a planetary stirring tank, then add 3 parts of ethyl orthosilicate, 4 parts of propyl orthosilicate, 3 parts of silane coupling agent, 2.5 parts of 1,3-propanedioxybis( Ethyl acetoacetate) titanium, 1 part of diphenylmethane diisocyanate (MDI), 2 parts of isophorone diisocyanate (IPDI) were stirred and mixed, and the chemical reaction was carried out at a vacuum degree of -0.09MPa and a speed of 700RPM for 50 minutes, and the material was discharged Sealed for storage.

Comparative example 1

Mix 60 parts of α, ω-dihydroxypolydimethylsiloxane with a viscosity of 80000mPa·s at 25°C, 50 parts of light calcium carbonate, 10 parts of heavy calcium carbonate, 1 part of titanium dioxide, 3 parts of dibutyl Hydroxytoluene (BHT)) was added into the vacuum kneader, the heating temperature was 125°C, the vacuum degree was -0.07MPa, dehydration and blending was carried out for 120 minutes, and the base was obtained by cooling to room temperature.

At room temperature, move the base material into a planetary stirring tank, then add 3 parts of ethyl orthosilicate, 4 parts of propyl orthosilicate, 3 parts of silane coupling agent [γ-aminopropyltriethoxysilane and γ - (2,3-glycidoxy) propyltrimethoxysilane molar mass ratio = 1:3 direct mixture], 2.5 parts of 1,3-propanedioxy bis (ethyl acetoacetate) titanium, 1 1 part of diphenylmethane diisocyanate (MDI) and 2 parts of isophorone diisocyanate (IPDI) were stirred and mixed, and the chemical reaction was carried out at a vacuum degree of -0.09MPa and a speed of 700RPM for 50 minutes, and the material was sealed and stored after discharge.

Table 1 Performance test of one-component dealcoholized solar photovoltaic module sealant with yellowing resistance and good storage

It can be seen from Table 1 that the one-component dealcoholized solar photovoltaic module sealant prepared by the present invention has yellowing resistance, excellent physical properties and storage stability.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the scope of the present invention. within the scope of protection.

Claims (11)

1. color inhibition, store a good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, be made up of the raw material of following weight ratio:

Described silane coupling agent to be mixed with by mole mass ratio 1: 1 ~ 1: 3 by γ-aminopropyl triethoxysilane and γ-(2,3-glycidoxy) propyl trimethoxy silicane and to form.

2. color inhibition as claimed in claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described α, the viscosity of alpha, omega-dihydroxy polydimethyl siloxane 25 DEG C time is 20000 ~ 80000mPas.

3. color inhibition as claimed in claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described filler is the mixture of light calcium carbonate and water-ground limestone, and the part by weight of its mixture is light calcium carbonate: water-ground limestone=1: 9 ~ 9: 1.

4. color inhibition as claimed in claim 3, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described light calcium carbonate is modified Nano calcene, particle diameter 20 ~ 100nm, and crystal formation is cubes crystal formation.

5. color inhibition as claimed in claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described alkoxy silane cross linked dose is the mixture of any one or more in methyltrimethoxy silane, vinyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, vinyltriethoxysilane, tetraethoxy or positive silicic acid propyl ester.

6. silane coupling agent as claimed in claim 1, it is characterized in that, preparation process is as follows: by γ-aminopropyl triethoxysilane and γ-(2,3-glycidoxy) propyl trimethoxy silicane by mole mass ratio 1: 1 ~ 1: 3 mix, put into heatable vacuum reaction still, at 80 ~ 150 DEG C, vacuum tightness is react 8 ~ 72hr under the condition of-0.07 ~-0.09MPa, after completion of the reaction, inflated with nitrogen is cooled to room temperature.

7. color inhibition as claimed in claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described titanium catalyst is any one or the two or more mixtures of isopropyl titanate, tetrabutyl titanate, two (isopropoxies) two (methyl ethyl diketone) titanium, two (isopropoxies) two (methyl aceto acetate) titanium, two (methyl aceto acetate) titanium of 1,3-third dioxy base.

8. color inhibition as claimed in claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, the combination that described anti-yellowing change agent is inorganic, metal oxide filler and organic oxidation-resistant agent, wherein inorganic, metal oxide: the weight ratio of organic oxidation-resistant agent is 5: 1 ~ 1: 5.

9. color inhibition as claimed in claim 8, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described inorganic, metal oxide filler is the mixture of any one or more in aluminum oxide, magnesium oxide, zinc oxide, titanium dioxide, and described organic oxidation-resistant agent is the mixture of any one or more in butylated hydroxy anisole (BHA), butylated hydroxytoluene (BHT), Tert. Butyl Hydroquinone (TBHQ).

10. color inhibition according to claim 1, store good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, described hydroxyl scavenging agent is the mixture of any one or more in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hexamethyldisilazane.

Prepare color inhibition described in any one of claim 1-10, store the method for good single-component dealcoholization-type solar energy photovoltaic component seal gum, it is characterized in that, comprise following steps for 11. 1 kinds:

1) by γ-aminopropyl triethoxysilane and γ-(2,3-glycidoxy) propyl trimethoxy silicane by mole mass ratio 1: 1 ~ 1: 3 mix, put into heatable vacuum reaction still, at 80 ~ 150 DEG C, vacuum tightness is react 8 ~ 72hr under the condition of-0.07 ~-0.09MPa, after completion of the reaction, inflated with nitrogen is cooled to room temperature;

2) by α, alpha, omega-dihydroxy polydimethyl siloxane 30 ~ 70 parts, filler 30 ~ 70 parts, anti-yellowing change agent 0.5 ~ 5 part adds in vacuum kneader, in temperature 80 ~ 140 DEG C, vacuum tightness is the blended 0.5 ~ 5hr that dewaters under the condition of-0.06 ~-0.09MPa, is then cooled to room temperature and obtains base-material, for subsequent use;

3) at room temperature, by step 2) gained base-material moves in planet stirring still, then by alkoxy silane cross linked dose 2 ~ 10 parts, step 1) silane coupling agent 0.5 ~ 5 part of gained, titanium catalyst 0.1 ~ 3 part, hydroxyl scavenging agent 0.5 ~ 5 part adds in stirring tank and is uniformly mixed, in vacuum tightness-0.08 ~-0.10MPa, rotating speed is that 300 ~ 900rpm reacts 0.3 ~ 2hr, and namely discharging is filling obtains object product.