CN116041662A - Outer transparent self-repairing coating for elastomer polymer and photovoltaic transparent backboard - Google Patents
Outer transparent self-repairing coating for elastomer polymer and photovoltaic transparent backboard Download PDFInfo
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- CN116041662A CN116041662A CN202310069040.0A CN202310069040A CN116041662A CN 116041662 A CN116041662 A CN 116041662A CN 202310069040 A CN202310069040 A CN 202310069040A CN 116041662 A CN116041662 A CN 116041662A
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- 239000011248 coating agent Substances 0.000 title claims abstract description 63
- 229920000642 polymer Polymers 0.000 title claims abstract description 42
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- 239000000806 elastomer Substances 0.000 title claims abstract description 28
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 32
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- 239000000600 sorbitol Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
- C08G18/6208—Hydrogenated polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
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- Medicinal Chemistry (AREA)
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Abstract
The invention belongs to the technical field of photovoltaic backboard, and particularly relates to an outer transparent self-repairing coating for a photovoltaic transparent backboard and a preparation method thereof. The self-healing coating for the photovoltaic backboard comprises the following components: elastomeric polymer: 45-150 parts; fluororesin: 10-50 parts; leveling agent: 0.3 to 0.5 part; powder material: 2-8 parts; dispersing agent: 0.02-0.10 part; an antioxidant: 0.18 to 0.70 portion; UV auxiliary agent: 4-10 parts; polyisocyanate curing agent: 25-50 parts; solvent: 20-60 parts; wherein the elastomer polymer takes hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene as a main chain, hexamethylene diisocyanate as a middle section, and both ends of a molecular chain are terminated by sorbitol polyglycidyl ether. According to the self-repairing coating for the photovoltaic backboard, the coating has self-repairing characteristics through the synthetic application and the formula design of the self-repairing material, and the abrasion resistance of the outer coating of the transparent backboard is improved on the premise of not reducing the weather resistance of the transparent backboard.
Description
The application is a divisional application of application number 202111529514.2, application day 2021, 12 months and 14 days, and the invention name is an outer transparent self-repairing coating for a photovoltaic transparent back plate and a preparation method thereof.
Technical Field
The invention belongs to the technical field of photovoltaic backboard, and particularly relates to an outer transparent self-repairing coating for a photovoltaic transparent backboard and a preparation method thereof.
Background
In recent years, with the gradual popularization of solar photovoltaic, the application of the double-sided battery assembly is also wider and wider.
The double-sided battery assembly is a component with both the front side and the back side capable of generating electricity. When the sun irradiates to the double-sided component, part of light is reflected to the back surface of the double-sided component by surrounding environment, and the part of light can be absorbed by the back surface of the battery, so that the utilization efficiency of the battery to the light is improved, and the power generation of the component can be improved by 20-40%.
The conventional double-sided double-glass battery assembly is formed by laminating two glass, EVA or POE adhesive films and solar battery silicon wafers at high temperature through a laminating machine to form a composite layer, and welding strips and bus bars are used between battery pieces to collect electrons to lead terminals.
The use of transparent back sheets on a two-sided battery assembly has irreplaceable advantages over a dual-sided glass assembly, such as lighter weight, lower shipping costs, lower assembly yield, reworkability, etc.
Disclosure of Invention
The invention provides an outer transparent self-repairing coating for a photovoltaic transparent backboard and a preparation method thereof.
In order to solve the technical problems, the invention provides a self-repairing coating for a photovoltaic backboard, which comprises the following components in parts by mass: elastomeric polymer: 45-150 parts; fluororesin: 10-50 parts; leveling agent: 0.3 to 0.5 part; powder material: 2-8 parts; dispersing agent: 0.02-0.10 part; an antioxidant: 0.18 to 0.70 portion; UV auxiliary agent: 4-10 parts; polyisocyanate curing agent: 25-50 parts; solvent: 20-60 parts; wherein the elastomer polymer takes hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene as a main chain, hexamethylene diisocyanate as a middle section, and both ends of a molecular chain are terminated by sorbitol polyglycidyl ether.
In still another aspect, the present invention also provides a method for preparing a self-healing coating for a photovoltaic backsheet, comprising the steps of: firstly, mixing a solvent and a dispersing agent, then sequentially adding powder and an inorganic UV auxiliary agent, stirring and dispersing to ensure that the powder is stably suspended and does not precipitate, and preparing dispersion slurry; mixing an elastomer polymer, a fluororesin, a leveling agent, an antioxidant and an organic UV auxiliary agent, adding the dispersion slurry, and stirring and dispersing to obtain a coating semi-finished product; adding a polyisocyanate curing agent into the paint semi-finished product, and stirring and dispersing to obtain a paint finished product; and (3) coating the coating finished product on the surface of the PET sheet Tu Pin subjected to corona treatment, baking, curing to form a film, and performing corona treatment and curing to obtain the self-repairing transparent backboard outer layer coating.
The self-repairing coating for the photovoltaic backboard has the beneficial effects that the coating has self-repairing characteristics through the synthetic application and the formula design of the self-repairing material, and the abrasion resistance of the outer coating of the transparent backboard is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
In order to make the above objects, features and advantages of the present invention more comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of the preparation of the self-healing coating for a photovoltaic backsheet of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Because the double-glass assembly is formed by taking glass as the outermost layer of the assembly, when the glass is damaged, the repairing cannot be performed, so that the cost is high, and the recycling property is poor. The invention provides an outer transparent coating for a transparent backboard, which can realize the self-repairing function of the outer transparent coating of the transparent backboard so as to improve the service life and the light utilization rate of a double-sided battery assembly.
The invention provides a self-repairing coating for a photovoltaic backboard, which comprises the following components in parts by mass: elastomeric polymer: 45-150 parts; fluororesin: 10-50 parts; leveling agent: 0.3 to 0.5 part; powder material: 2-8 parts; dispersing agent: 0.02-0.10 part; an antioxidant: 0.18 to 0.70 portion; UV auxiliary agent: 4-10 parts; polyisocyanate curing agent: 25-50 parts; solvent: 20-60 parts; wherein the elastomer polymer takes hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene as a main chain, hexamethylene diisocyanate as a middle section, and both ends of a molecular chain are terminated by sorbitol polyglycidyl ether.
Specifically, the elastomer polymer is a main film forming material of the coating, the compatibility of hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene in a system can be improved through synthesis modification, the adhesive force of the coating and a PET substrate can be improved, and the self-repairing property and the wear resistance of the coating can be greatly improved.
Wherein, optionally, the elastomer polymer comprises the following components in parts by mass: hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene: 80-106 parts; hexamethylene diisocyanate: 23-45 parts; sorbitol polyglycidyl ether: 18-39 parts; organobismuth catalyst: 0.1 to 0.4 part; propylene glycol methyl ether acetate: 88-120 parts.
The elastomer polymer provided by the invention is a polymer formed by polyurethane reaction of hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene, hexamethylene diisocyanate, sorbitol polyglycidyl ether, an organic bismuth catalyst and propylene glycol methyl ether acetate under certain conditions.
Alternatively, the molecular weight Mn of the hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene is 1000 to 4500.
Optionally, the fluororesin is one or more of tetrafluoroethylene-vinyl ether resin, tetrafluoroethylene-vinyl ester resin, chlorotrifluoroethylene-vinyl ether, chlorotrifluoroethylene-vinyl ester resin; the hydroxyl value of the fluororesin is 50-80 mgKOH/g, and the fluororesin is specifically such as east fluorine chemical ZHM-2 or HLR-6 fluororesin, changxing 41011 fluororesin, dajinGK-570 fluororesin and the like; the addition of the fluororesin can cross-link with the elastomer polymer under the action of the curing agent to form a compact network structure, so that the weather resistance of the coating is further improved, and the self-repairing property of the coating can be kept for a long time.
Optionally, the powder is one or more of PTFE micropowder, PVDF micropowder and silicon micropowder. The powder is added into the coating, so that the problem of anti-sticking after the finished product is wound can be avoided.
Optionally, the solvent is one or more of butyl acetate, xylene, ethyl acetate and propylene glycol methyl ether acetate. The solvent is capable of dissolving the organic reactants to form a homogeneous system, so that the components in the coating are fully and uniformly reacted and crosslinked. Solvents of different boiling points are chosen according to the baking temperature to ensure that the coating is not tacky and has sufficient cross-linking cure time.
Optionally, the leveling agent is one or more of an acrylic leveling agent, an organosilicon leveling agent, a fluorosilicone leveling agent and a high boiling point solvent, such as BYK-300; the leveling agent migrates to the surface of the wet film through limited compatibility, influences the surface tension of a paint film, promotes the paint to form a smooth and uniform coating in the drying process, improves the permeability of the paint to a substrate, and reduces appearance flaws such as spots, marks and the like generated during brushing.
Optionally, the dispersing agent is one or more of anionic wetting dispersing agent, cationic wetting dispersing agent, nonionic wetting dispersing agent, amphoteric wetting dispersing agent, polymer hyperdispersing agent and controlled free radical hyperdispersing agent, such as Efka PU 4010; the addition of the dispersing agent can improve the surface property of powder particles and adjust the mobility of the powder particles, thereby improving the stability of the powder and avoiding flocculation sedimentation.
Optionally, the antioxidant is one or more of hindered amine, hindered phenol, phosphite ester, thiodipropionate and thiols, in particular 1010 or 168 antioxidants, and the addition of the antioxidant can delay or inhibit the thermal oxidative decomposition of the elastomer polymer, delay the aging of the polymer and prolong the service life of the polymer because the photovoltaic backboard is used under outdoor high-temperature conditions for a long time.
Optionally, the UV auxiliary agent is divided into two types, namely organic and inorganic, wherein the organic is one or more of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles and triazines; the organic UV auxiliary agent can absorb ultraviolet rays and stably generate free radicals, so that organic components in the coating are prevented from being damaged and degraded by the ultraviolet rays; the inorganic UV auxiliary agent is one or more of nano zinc oxide and nano titanium dioxide; the inorganic UV auxiliary agent can shield ultraviolet rays, the size between nano particles is equal to or smaller than that of light waves, and the light absorption is remarkably enhanced due to the increase of the interval between a conduction band and a valence band caused by the size effect. The addition of the UV auxiliary agent can effectively protect the molecular chains of the elastomer polymer and other components in the coating, so that the molecular chains are not easy to break, the problems of yellowing, cracking, stickiness and the like of the coating are avoided, and the self-repairing property of the coating is further improved.
Optionally, the polyisocyanate curing agent is one or more of an HDI trimer, an H6XDI adduct and an XDI adduct; the polyisocyanate curing agent has more than two-NCO active groups per molecule, can react with-OH functional groups carried by elastomer polymers, fluororesin and the like in the coating component to form a reticular cross-linking structure, and meanwhile, part of-NCO can also form chemical bonds with polar functional groups on a substrate to improve the adhesive force of the coating, and the self-repairing property of the coating can be stably maintained for a long time due to the reaction cross-linking characteristic of the curing agent.
In yet another aspect, as shown in fig. 1, the present invention provides a method for preparing a self-healing coating for a photovoltaic back sheet, comprising the steps of: firstly, mixing a solvent and a dispersing agent, then sequentially adding powder and an inorganic UV auxiliary agent, stirring and dispersing to ensure that the powder is stably suspended and does not precipitate, and preparing dispersion slurry; mixing an elastomer polymer, a fluororesin, a leveling agent, an antioxidant and an organic UV auxiliary agent, adding the dispersion slurry, and stirring and dispersing to obtain a coating semi-finished product; adding a polyisocyanate curing agent into the paint semi-finished product, and stirring and dispersing to obtain a paint finished product; and (3) coating the coating finished product on the surface of the PET sheet Tu Pin subjected to corona treatment, baking, curing to form a film, and performing corona treatment and curing to obtain the self-repairing transparent backboard outer layer coating.
Wherein, the preparation method of the elastomer polymer comprises the following steps: adding propylene glycol methyl ether acetate into a reaction vessel, heating to 90-100 ℃, sequentially adding hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene and an organobismuth catalyst, stirring and dispersing to prepare a pre-dispersion liquid; adding hexamethylene diisocyanate into the pre-dispersion liquid, and carrying out heat preservation reaction to obtain a pre-reaction liquid; and heating the pre-reaction liquid to 105-110 ℃, adding sorbitol polyglycidyl ether, and stirring for reaction to obtain the elastomer polymer.
Specifically, the reaction mechanism for preparing the elastomeric polymer is as follows:
example 1
Continuously introducing nitrogen into a reaction kettle, removing air and water vapor, adding 93 parts of propylene glycol methyl ether acetate into the reaction kettle, heating to 95 ℃, sequentially adding 89 parts of hydroxyl-terminated polybutadiene and 0.3 part of organic bismuth catalyst, and stirring for 0.5h at 300r/min to uniformly disperse the materials; after the temperature of the reaction kettle is stable, 31 parts of hexamethylene diisocyanate is added into the reaction kettle at one time, and the reaction is carried out for 1.5 hours at the stirring speed and the reaction temperature to fully react; continuously heating to 110 ℃, adding 21 parts of sorbitol polyglycidyl ether into a reaction kettle at one time, and keeping the stirring speed and the reaction temperature for 2.5 hours; sampling, testing NCO content by titration (di-n-butylamine), taking the NCO content as a reaction end point when the NCO content is less than or equal to 0.1%, naturally cooling, and discharging and packaging for later use.
Example 2
Continuously introducing nitrogen into a reaction kettle, removing air and water vapor, adding 88 parts of propylene glycol methyl ether acetate into the reaction kettle, heating to 90 ℃, sequentially adding 89 parts of hydrogenated hydroxyl-terminated polybutadiene and 0.2 part of organic bismuth catalyst, and stirring for 0.5h at 400r/min to uniformly disperse the mixture; after the temperature of the reaction kettle is stable, adding 35 parts of hexamethylene diisocyanate into the reaction kettle at one time, and keeping the stirring speed and the reaction temperature for reaction for 1 hour to fully react; continuously heating to 103 ℃, adding 18 parts of sorbitol polyglycidyl ether into a reaction kettle at one time, and keeping the stirring speed and the reaction temperature for 2 hours; sampling, testing NCO content by titration (di-n-butylamine), taking the NCO content as a reaction end point when the NCO content is less than or equal to 0.1%, naturally cooling, and discharging and packaging for later use.
Example 3
Continuously introducing nitrogen into a reaction kettle, removing air and water vapor, adding 120 parts of propylene glycol methyl ether acetate into the reaction kettle, heating to 100 ℃, sequentially adding 89 parts of hydrogenated hydroxyl-terminated polybutadiene and 0.4 part of organic bismuth catalyst, and stirring for 0.5h at 200r/min to uniformly disperse the mixture; after the temperature of the reaction kettle is stable, 45 parts of hexamethylene diisocyanate is added into the reaction kettle at one time, and the reaction is carried out for 2 hours at the stirring speed and the reaction temperature to fully react; continuously heating to 108 ℃, adding 39 parts of sorbitol polyglycidyl ether into a reaction kettle at one time, and keeping the stirring speed and the reaction temperature for 3 hours; sampling, testing NCO content by titration (di-n-butylamine), taking the NCO content as a reaction end point when the NCO content is less than or equal to 0.1%, naturally cooling, and discharging and packaging for later use.
Example 4
Continuously introducing nitrogen into a reaction kettle, removing air and water vapor, adding 115 parts of propylene glycol methyl ether acetate into the reaction kettle, heating to 93 ℃, sequentially adding 89 parts of hydroxyl-terminated polybutadiene and 0.1 part of organic bismuth catalyst, and stirring for 0.5h at 500r/min to uniformly disperse the components; after the temperature of the reaction kettle is stable, 23 parts of hexamethylene diisocyanate is added into the reaction kettle at one time, and the reaction is carried out for 1.8 hours at the stirring speed and the reaction temperature to fully react; continuously heating to 105 ℃, adding 27 parts of sorbitol polyglycidyl ether into a reaction kettle at one time, and keeping the stirring speed and the reaction temperature for 2.7 hours; sampling, testing NCO content by titration (di-n-butylamine), taking the NCO content as a reaction end point when the NCO content is less than or equal to 0.1%, naturally cooling, and discharging and packaging for later use.
Example 5
45 parts of butyl acetate solvent and 0.05 part of polymer type hyperdispersant are mixed and stirred uniformly, and 2.25 parts of PVDF micro powder and 2.25 parts of silicon micro powder and 0.15 part of nano zinc oxide are sequentially added; in the feeding process, the rotating speed of the stirrer is gradually increased to 2000 rpm and maintained for 20min, so that the powder is uniformly dispersed, and the powder is stably suspended without precipitation, thus the preparation of the dispersion slurry is completed.
140 parts of the elastomer polymer prepared in the example 1, 36 parts of fluororesin, 0.45 part of acrylic leveling agent, 0.3 part of hindered phenol antioxidant, 3.375 parts of triazine and 1.125 parts of benzotriazole organic UV auxiliary agent are mixed and dispersed at a high speed of 1000 rpm for 10min, and then the dispersion slurry is added, and the high speed of 2000 rpm is carried out for 45min, thus obtaining the paint semi-finished product.
Adding 38 parts of polyisocyanate curing agent into the semi-finished paint, stirring for 10min at 1000 rpm, and regulating viscosity to obtain the finished paint; the finished paint is coated on the surface of a PET sheet Tu Pin subjected to corona treatment, baked in an oven at 150 ℃ for 2min and cured at 60 ℃ for 48h after corona treatment under the corona intensity of 4.5 kW.
Example 6
24 parts of butyl acetate and 24 parts of PMA are taken as solvents, 0.1 part of polymer type hyperdispersant is added, mixed and stirred uniformly, and 1.875 parts of PVDF micro powder, 1.875 parts of PTFE micro powder and 3.75 parts of silicon micro powder are sequentially added, and 0.12 part of nano zinc oxide is added; in the feeding process, the rotation speed of the stirrer is gradually increased to 2000 rpm and maintained for 10min, so that the powder is uniformly dispersed, and the powder is stably suspended without precipitation, thus completing the preparation of the dispersion slurry.
122 parts of the elastomer polymer prepared in the example 2, 29 parts of fluororesin, 0.5 part of acrylic leveling agent, 0.45 part of hindered phenol antioxidant and 6 parts of triazine organic UV auxiliary agent are mixed and dispersed at a high speed of 1000 revolutions per minute for 30 minutes, and then the dispersion slurry is added, and the mixture is dispersed at a high speed of 2000 revolutions per minute for 60 minutes, so that a coating semi-finished product is obtained.
Adding 42 parts of polyisocyanate curing agent into the semi-finished paint, stirring for 10min at 1000 rpm, and regulating viscosity to obtain the finished paint; the finished paint is coated on the surface of a PET sheet Tu Pin subjected to corona treatment, baked in an oven at 160 ℃ for 2min and cured at 60 ℃ for 48h after corona treatment under the corona intensity of 4.5 kW.
Example 7
Mixing 32 parts of PMA solvent and 0.07 part of polymer type hyperdispersant, uniformly stirring, and sequentially adding 2.17 parts of PTFE micro powder and 4.33 parts of silicon micro powder and 0.1 part of nano titanium dioxide; in the feeding process, the rotation speed of the stirrer is gradually increased to 2000 rpm and maintained for 30min, so that the powder is uniformly dispersed, and the powder is stably suspended without precipitation, thus completing the preparation of the dispersion slurry.
132 parts of the elastomer polymer prepared in the example 3, 25 parts of fluororesin, 0.4 part of organosilicon leveling agent, 0.36 part of hindered phenol antioxidant, 4.58 parts of triazine and 0.92 part of salicylate organic UV auxiliary agent are mixed and dispersed at a high speed of 1000 rpm for 30min, and then the dispersion slurry is added, and the mixture is dispersed at a high speed of 2000 rpm for 30min, so that the coating semi-finished product is obtained.
Adding 38 parts of polyisocyanate curing agent into the semi-finished paint, stirring for 10min at 1000 rpm, and regulating viscosity to obtain the finished paint; the finished paint is coated on the surface of a PET sheet Tu Pin subjected to corona treatment, baked in an oven at 160 ℃ for 2min and cured at 60 ℃ for 48h after corona treatment under the corona intensity of 4.5 kW.
Example 8
Mixing 20 parts of butyl acetate solvent and 0.03 part of polymer type hyperdispersant, uniformly stirring, and sequentially adding 1 part of PVDF micro powder and 1 part of silicon micro powder and 0.6 part of nano zinc oxide; in the feeding process, the rotating speed of the stirrer is gradually increased to 2000 rpm and maintained for 20min, so that the powder is uniformly dispersed, and the powder is stably suspended without precipitation, thus the preparation of the dispersion slurry is completed.
45 parts of the elastomer polymer prepared in the example 4, 10 parts of fluororesin, 0.3 part of acrylic leveling agent, 0.2 part of hindered phenol antioxidant, 2.1 parts of triazine and 1.3 parts of benzotriazole organic UV auxiliary agent are mixed and dispersed at a high speed of 1000 rpm for 10min, and then the dispersion slurry is added, and the mixture is dispersed at a high speed of 2000 rpm for 45min, so that the coating semi-finished product is obtained.
Adding 25 parts of polyisocyanate curing agent into the semi-finished paint, stirring for 10min at 1000 rpm, and regulating viscosity to obtain the finished paint; the finished paint is coated on the surface of a PET sheet Tu Pin subjected to corona treatment, baked in an oven at 150 ℃ for 2min and cured at 60 ℃ for 48h after corona treatment under the corona intensity of 4.5 kW.
The coatings prepared in the examples above were subjected to relevant performance tests and the data are summarized in table 1.
Table 1 summary of the performance data for the coatings prepared in the examples
As can be seen from the data in table 1, the transparent back sheet produced in each example has a light transmittance substantially identical to that of glass and slightly higher than that of the coated and composite back sheet; in the aspect of self-repairing, the transparent backboard manufactured in each embodiment has the characteristic of thermal repairing, while the common backboard does not have the characteristic of self-repairing, and the transparent backboard can be used for thermally repairing scratches caused by outdoor use and workers during installation operation.
In summary, according to the self-repairing coating for the photovoltaic backboard, the coating has the self-repairing characteristic through the synthetic application and the formula design of the self-repairing material, so that the abrasion resistance of the outer coating of the transparent backboard is improved.
With the above-described preferred embodiments according to the present invention as an illustration, the above-described descriptions can be used by persons skilled in the relevant art to make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the description, but must be determined according to the scope of claims.
Claims (10)
1. The elastomer polymer for the self-repairing coating of the photovoltaic backboard is characterized by comprising the following components in parts by mass:
hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene: 80-106 parts;
hexamethylene diisocyanate: 23-45 parts;
sorbitol polyglycidyl ether: 18-39 parts;
organobismuth catalyst: 0.1 to 0.4 part;
propylene glycol methyl ether acetate: 88-120 parts.
2. A method for preparing an elastomeric polymer for a photovoltaic backsheet self-healing coating, comprising:
adding propylene glycol methyl ether acetate into a reaction vessel, heating to 90-100 ℃, sequentially adding hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene and an organobismuth catalyst, stirring and dispersing to prepare a pre-dispersion liquid;
adding hexamethylene diisocyanate into the pre-dispersion liquid, and carrying out heat preservation reaction to obtain a pre-reaction liquid;
and heating the pre-reaction liquid to 105-110 ℃, adding sorbitol polyglycidyl ether, and stirring for reaction to obtain the elastomer polymer.
3. The self-repairing coating for the photovoltaic backboard is characterized by comprising the following components in parts by mass:
elastomeric polymer: 45-150 parts;
the elastomer polymer takes hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene as a main chain, hexamethylene diisocyanate as a middle section, and two ends of a molecular chain are blocked by sorbitol polyglycidyl ether;
the preparation method of the elastomer polymer comprises the following steps:
adding propylene glycol methyl ether acetate into a reaction vessel, heating, sequentially adding hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene and an organic bismuth catalyst, stirring and dispersing to prepare pre-dispersion liquid;
adding hexamethylene diisocyanate into the pre-dispersion liquid, and carrying out heat preservation reaction to obtain a pre-reaction liquid;
and heating the pre-reaction liquid to 105-110 ℃, adding sorbitol polyglycidyl ether, and stirring for reaction to obtain the elastomer polymer.
4. A self-healing coating according to claim 3, wherein,
the elastomer polymer comprises the following components in parts by mass:
hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene: 80-106 parts;
hexamethylene diisocyanate: 23-45 parts;
sorbitol polyglycidyl ether: 18-39 parts;
organobismuth catalyst: 0.1 to 0.4 part;
propylene glycol methyl ether acetate: 88-120 parts.
5. The self-healing coating according to claim 4, wherein,
the molecular weight Mn of the hydroxyl-terminated polybutadiene or the hydrogenated hydroxyl-terminated polybutadiene is 1000-4500.
6. The self-healing coating of claim 3, further comprising:
a fluororesin which is one or more of tetrafluoroethylene-vinyl ether resin, tetrafluoroethylene-vinyl ester resin, chlorotrifluoroethylene-vinyl ether, chlorotrifluoroethylene-vinyl ester resin; and
the hydroxyl value of the fluororesin is 50-80 mgKOH/g.
7. The self-healing coating of claim 3, further comprising
The powder material is one or more of PTFE micropowder, PVDF micropowder and silicon micropowder.
8. The self-healing coating of claim 3, further comprising:
and the solvent is one or more of butyl acetate, xylene, ethyl acetate and propylene glycol methyl ether acetate.
9. The preparation method of the self-repairing coating for the photovoltaic backboard is characterized by comprising the following steps of:
firstly, mixing a solvent and a dispersing agent, then sequentially adding powder and an inorganic UV auxiliary agent, stirring and dispersing to ensure that the powder is stably suspended and does not precipitate, and preparing dispersion slurry;
mixing an elastomer polymer, a fluororesin, a leveling agent, an antioxidant and an organic UV auxiliary agent, adding the dispersion slurry, and stirring and dispersing to obtain a coating semi-finished product;
adding a polyisocyanate curing agent into the paint semi-finished product, and stirring and dispersing to obtain a paint finished product;
and (3) coating the coating finished product on the surface of the PET sheet Tu Pin subjected to corona treatment, baking, curing to form a film, and performing corona treatment and curing to obtain the self-repairing transparent backboard outer layer coating.
10. The method of claim 9, wherein,
the elastomer polymer comprises the following components in parts by mass:
hydroxyl-terminated polybutadiene or hydrogenated hydroxyl-terminated polybutadiene: 80-106 parts;
hexamethylene diisocyanate: 23-45 parts;
sorbitol polyglycidyl ether: 18-39 parts;
organobismuth catalyst: 0.1 to 0.4 part;
propylene glycol methyl ether acetate: 88-120 parts.
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