CN111205433B - Preparation method of organic fluorine modified polyurethane elastomer resin, coating and back plate - Google Patents

Preparation method of organic fluorine modified polyurethane elastomer resin, coating and back plate Download PDF

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CN111205433B
CN111205433B CN202010012113.9A CN202010012113A CN111205433B CN 111205433 B CN111205433 B CN 111205433B CN 202010012113 A CN202010012113 A CN 202010012113A CN 111205433 B CN111205433 B CN 111205433B
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polyurethane elastomer
isocyanate
coating
hydroxyl
micromolecule
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CN111205433A (en
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林建伟
张付特
唐邓
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JOLYWOOD (SUZHOU) SUNWATT CO Ltd
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JOLYWOOD (SUZHOU) SUNWATT CO Ltd
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    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/30—Low-molecular-weight compounds
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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    • C08G18/67—Unsaturated compounds having active hydrogen
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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    • 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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    • 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
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    • C09D7/60—Additives non-macromolecular
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • 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
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    • H01L31/042—PV modules or arrays of single PV cells
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract

The invention relates to a preparation method of organic fluorine modified polyurethane elastomer resin, a coating and a back plate. The method comprises the following steps: (1) mixing small molecular polyol containing fluorine or a mixture of the small molecular polyol containing the fluorine with small molecular polyester polyol, a small molecular chain extender containing at least two hydroxyl groups and a solvent; dropwise adding micromolecule isocyanate or a mixture containing micromolecule isocyanate, heating, stirring, and reacting for 1-6h at the temperature of 40-120 ℃ to form hydroxyl-terminated polyurethane elastomer prepolymer; (2) continuously dropwise adding micromolecule isocyanate or a mixture containing isocyanate into the hydroxyl-terminated polyurethane elastomer prepolymer at the temperature of 40-120 ℃, reacting for 2-4h, and carrying out chain extension reaction; (3) and (2) at the temperature of 40-120 ℃, dropwise adding a catalyst into the hydroxyl-terminated polyurethane elastomer prepolymer, and reacting for 2-6h to form the organic fluorine modified polyurethane elastomer resin with good weather resistance and sand resistance.

Description

Preparation method of organic fluorine modified polyurethane elastomer resin, coating and back plate
Technical Field
The invention relates to the technical field of solar cells, in particular to a preparation method of organic fluorine modified polyurethane elastomer resin, a coating and a back plate.
Background
With the increasing awareness of people on environmental protection, the use of clean energy to replace traditional petrochemical energy is a development trend. Among these clean and renewable energy sources, solar energy is one of the most important energy sources. The structure of the current mainstream solar cell module is glass, a packaging adhesive film, a cell piece, a packaging adhesive film and a solar cell backboard, wherein the solar cell backboard is used as an auxiliary material of the photovoltaic module and mainly plays a role in supporting and protecting the cell piece. The main concerns regarding the properties of the backsheet are in terms of mechanical properties (fracture productivity, tensile strength), weathering resistance, electrical properties, water vapour barrier properties, thermodynamic properties, based on the use of the backsheet material, wherein the weathering resistance is of different importance in different climatic environments.
Currently, the commonly used back sheets have various structures, and can be classified into a double-sided fluorine film back sheet (such as TPT/KPK, which has a low market rate due to high cost), a single-sided fluorine film back sheet (such as TPC/KPC type), a double-sided fluorine-containing coating type back sheet (CPC type), and a fluorine-free back sheet (such as PPE or co-extrusion type back sheet). The double-sided fluorine-containing coating type back plate is gradually accepted by the market and becomes a mainstream back plate product due to high reliability and moderate cost.
However, due to the limitations of the existing coating technology, the sandstorm impact resistance is also a great disadvantage compared to traditional fluorine film products, and the weather conditions of the sandstorm limit the application of this type of backsheet product.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of organic fluorine modified polyurethane elastomer resin, a coating and a back plate.
The preparation method of the organic fluorine modified polyurethane elastomer resin has the technical scheme that:
the method comprises the following steps:
(1) mixing small molecular polyol containing fluorine or a mixture of the small molecular polyol containing the fluorine with small molecular polyester polyol, a small molecular chain extender containing at least two hydroxyl groups and a solvent; dropwise adding micromolecule isocyanate or a mixture containing micromolecule isocyanate, heating, stirring, and reacting for 1-6h at the temperature of 40-120 ℃ to form hydroxyl-terminated polyurethane elastomer prepolymer;
(2) continuously dropwise adding micromolecule isocyanate or a mixture containing isocyanate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (1) at the temperature of 40-120 ℃, reacting for 2-4h, and carrying out chain extension reaction;
(3) and (3) at the temperature of 40-120 ℃, dropwise adding a catalyst into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (2), and reacting for 2-6h to form the organic fluorine modified polyurethane elastomer resin.
The preparation method of the organic fluorine modified polyurethane elastomer resin provided by the invention also comprises the following subsidiary technical scheme:
wherein, the fluorine-containing small molecular polyol is one or a mixture of any one of fluorine-containing polyether polyol, perfluorinated polyether polyol, fluorine-containing polyester glycol, fluoroalkyl vinyl glycol and fluorine-containing alkyl glycol; wherein, the fluorine-containing polyester diol is polycarbonate diol or polycaprolactone diol, and the average molecular weight of the fluorine-containing polyester diol is 500-2000.
Wherein, the dihydric alcohol in the polycarbonate dihydric alcohol or the polycaprolactone dihydric alcohol comprises one or the combination of any more of 1, 4 butanediol, 1, 2 propanediol, diethylene glycol, neopentyl glycol, 1, 6 hexanediol, 1, 4 dihydroxycyclohexane and hydroxyl-terminated polybutadiene.
In the step (1), dropwise adding a micromolecule isocyanate monomer into a mixture of fluorine-containing dihydric alcohol, polyester dihydric alcohol, micromolecule dihydric alcohol and a solvent within 1h, and reacting for 1-6h at the temperature of 40-120 ℃ to form a hydroxyl-terminated polyurethane elastomer prepolymer; wherein the molar ratio of OH groups to NCO groups is from 0.3 to 0.6.
Wherein, in the step (2), the micromolecule isocyanate monomer is dripped into the hydroxyl-terminated prepolymer within 1h, and reacts for 1-6h at the temperature of 40-120 ℃; wherein the molar ratio of OH to NCO is 0.6-0.9.
Wherein, in the step (1), the small molecular isocyanate is aliphatic or alicyclic diisocyanate.
Wherein, in the step (3), the catalyst is tetrabutyl titanate or organic tin, and the addition amount is 100-1000 ppm.
The invention also provides a coating which is formed by taking the organic fluorine modified polyurethane elastomer resin prepared by the preparation method as a base material and adding an inorganic filler, a leveling agent, a dispersing agent, an antioxidant, a light stabilizer and an ultraviolet absorber.
Wherein the inorganic filler comprises one or more of rutile titanium dioxide, fibrous filler, ceramic microsphere filler and whisker filler; wherein the particle size of the rutile type titanium dioxide is less than 0.3 mu m; the fibrous filler comprises one or more of polycrystalline mullite fiber powder, glass fiber powder and graphene fiber powder, and the particle size of the fibrous filler is 1000-2000 meshes; the ceramic microsphere filler comprises one or a mixture of any one of silicon oxide alloy ceramic microspheres, aluminum oxide alloy ceramic microspheres or zirconium oxide ceramic microspheres, and the particle size of the ceramic microsphere filler is less than 10 mu m; the whisker is one or a mixture of any one of calcium carbonate whisker, calcium sulfate whisker, potassium titanate whisker and aluminum borate whisker, and the length of the whisker is less than 10 mu m.
The invention also provides a backboard, which comprises a substrate layer, wherein one side of the substrate layer is provided with the high weather-resistant fluorocarbon coating layer, and the other side of the substrate layer is provided with the wind-resistant sand layer; the wind-resistant sand layer is made of the paint.
The base material layer is a film prepared by blending one or more of PET, PEN, PBT and PCT and stretching the mixture through coextrusion.
Wherein the thickness of the high weather-resistant fluorocarbon coating layer is 3-50 μm, and the thickness of the substrate layer is 100-500 μm.
The implementation of the invention comprises the following technical effects:
the organic fluorine modified polyurethane elastomer resin has good weather resistance and sand falling resistance, and can be used for preparing a coating and applying to a solar cell back plate in a wind and sand climate environment by taking the resin as a base material.
Detailed Description
The present invention will be described in detail with reference to examples.
The present invention is not limited to the above-described embodiments, and those skilled in the art can make modifications to the embodiments without any inventive contribution as required after reading the present specification, but only protected within the scope of the appended claims.
The preparation method of the organic fluorine modified polyurethane elastomer resin provided by the invention comprises the following steps:
(1) mixing small molecular polyol containing fluorine or a mixture of the small molecular polyol containing the fluorine with small molecular polyester polyol, a small molecular chain extender containing at least two hydroxyl groups and a solvent; dropwise adding micromolecule isocyanate or a mixture containing micromolecule isocyanate, heating, stirring, and reacting for 1-6h at the temperature of 40-120 ℃ to form hydroxyl-terminated polyurethane elastomer prepolymer;
(2) continuously dropwise adding micromolecule isocyanate or a mixture containing isocyanate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (1) at the temperature of 40-120 ℃, reacting for 2-4h, and carrying out chain extension reaction;
(3) and (3) at the temperature of 40-120 ℃, dropwise adding a catalyst into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (2), and reacting for 2-6h to form the organic fluorine modified polyurethane elastomer resin.
Preferably, the fluorine-containing small molecular polyol is one or a mixture of any of fluorine-containing polyether polyol, perfluorinated polyether polyol, fluorine-containing polyester glycol, fluoroalkyl vinyl glycol and fluorine-containing alkyl glycol; wherein, the fluorine-containing polyester diol is polycarbonate diol or polycaprolactone diol, and the average molecular weight of the fluorine-containing polyester diol is 500-2000.
Preferably, the dihydric alcohol in the polycarbonate dihydric alcohol or the polycaprolactone dihydric alcohol comprises one or a combination of any of 1, 4 butanediol, 1, 2 propanediol, diethylene glycol, neopentyl glycol, 1, 6 hexanediol, 1, 4 dihydroxycyclohexane and hydroxyl-terminated polybutadiene.
Preferably, in the step (1), the small molecule isocyanate monomer is dripped into the mixture of the fluorine-containing diol, the polyester diol, the small molecule diol and the solvent within 1h, and reacts for 1-6h at the temperature of 40-120 ℃ to form hydroxyl-terminated polyurethane elastomer prepolymer; wherein the molar ratio of OH groups to NCO groups is from 0.3 to 0.6.
Preferably, in the step (2), the small molecule isocyanate monomer is dripped into the hydroxyl-terminated prepolymer within 1h, and the reaction lasts for 1-6h at the temperature of 40-120 ℃; wherein the molar ratio of OH to NCO is 0.6-0.9.
Preferably, in step (1), the small molecule isocyanate is an aliphatic or alicyclic diisocyanate.
Specifically, the small molecular isocyanate is one or a mixture of any of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexanedimethylene diisocyanate (hydrogenated XDI), 1, 4 Cyclohexanediisocyanate (CHDI) and uretdione.
Preferably, in step (3), the catalyst is tetrabutyl titanate or organotin, and the addition amount thereof is 100-1000 ppm.
The invention also provides a coating which is formed by taking the organic fluorine modified polyurethane elastomer resin prepared by the preparation method as a base material and adding an inorganic filler, a leveling agent, a dispersing agent, an antioxidant, a light stabilizer and an ultraviolet absorber.
Preferably, the inorganic filler comprises one or more of rutile type titanium dioxide, fibrous filler, ceramic microsphere filler and whisker filler; wherein the particle size of the rutile type titanium dioxide is less than 0.3 mu m; the fibrous filler comprises one or more of polycrystalline mullite fiber powder, glass fiber powder and graphene fiber powder, and the particle size of the fibrous filler is 1000-2000 meshes; the ceramic microsphere filler comprises one or a mixture of any one of silicon oxide alloy ceramic microspheres, aluminum oxide alloy ceramic microspheres or zirconium oxide ceramic microspheres, and the particle size of the ceramic microsphere filler is less than 10 mu m; the whisker is one or a mixture of any one of calcium carbonate whisker, calcium sulfate whisker, potassium titanate whisker and aluminum borate whisker, and the length of the whisker is less than 10 mu m.
The rutile titanium dioxide in the embodiment plays a role in absorbing and reflecting ultraviolet rays in the coating, the ceramic microsphere filler has higher hardness, so that the cutting abrasion of sharp corners on the surface of the sandstone to the coating can be reduced, and the fiber and whisker filler can enable the coating to form a net-shaped composite structure and disperse the impact force of the sandstone to the coating.
The invention also provides a backboard, which comprises a substrate layer, wherein one side of the substrate layer is provided with the high weather-resistant fluorocarbon coating layer, and the other side of the substrate layer is provided with the wind-resistant sand layer; the wind sand resistant layer is made by adopting the organic fluorine modified polyurethane elastomer resin as a base material.
The base material layer is a film prepared by blending one or more of PET, PEN, PBT and PCT and stretching the mixture through coextrusion.
Preferably, the thickness of the high weather-resistant fluorocarbon coating layer is 3-50 μm, and the thickness of the substrate layer is 100-500 μm.
The method for producing the organofluorine-modified polyurethane elastomer resin of the present invention will be described in detail in example 1.
Example 1
(1) Removing water from propylene glycol methyl ether acetate with 4A molecular sieve to make its water content less than 50PPM, introducing N into a reaction kettle equipped with a condensing reflux device2Protecting, adding 100 parts of fluoropolyether diol ZDOL 100 parts, hydroxyl-terminated polybutadiene 25 parts, neopentyl glycol 1.5 parts, dimethylolpropionic acid 1.3 parts and propylene glycol monomethyl ether acetate 45 parts, and starting a stirrer; dripping 5.75 parts of isophorone diisocyanate (IPDI) within 30min, heating to 80 ℃ after dripping, and carrying out heat preservation reaction for 2h to form the hydroxyl-terminated polyurethane elastomer prepolymer.
(2) And (2) dropwise adding 2.88 parts of isophorone diisocyanate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (1), and carrying out heat preservation reaction for 2 hours at the temperature of 80 ℃.
(3) Dropwise adding 2.87 parts of isophorone diisocyanate, 0.01 part of dibutyltin dilaurate and 45 parts of propylene glycol methyl ether acetate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (2), carrying out heat preservation reaction at 80 ℃ for 4 hours, cooling to room temperature, and discharging to obtain the organic fluorine-modified polyurethane elastomer resin.
The coating material having a wind-and-sand resistant function according to the present invention will be described in detail in example 2.
Example 2
100 parts of the organic fluorine-modified polyurethane elastomer resin prepared in example 1 is taken, and then 20 parts of rutile titanium dioxide, 8 parts of polycrystalline mullite fiber, 8 parts of ceramic microspheres, 0.3 part of a leveling agent, 1 part of a dispersing agent, 1 part of an antioxidant, 0.3 part of a light stabilizer and 1.3 parts of an ultraviolet absorber are added to the organic fluorine-modified polyurethane elastomer resin, so that the coating with the wind and sand resistant function is formed.
The solar cell back sheet of the present invention will be described in detail in example 3.
Example 3
Adding a curing agent N3300 into the coating with the wind-sand resistant function prepared in the example 2, blade-coating the coating on the surface of a PET base material, wherein the thickness of the coating is 20-30 mu m, and baking the coating in an oven at 140 ℃ for 10Min for curing to prepare the back plate for the solar cell. The main properties were tested as follows:
resistance to falling sand test
Sample name Film thickness/. mu.m Amount of fallen sand/L
Example 1 26 110
TPC backboard 25 120
KPC backboard 22 107
CPC back plate 23 42
Long term aging Performance test
Figure BDA0002357517870000071
From the above tests of the sand-falling resistance, it can be seen that the backsheet in example 3 of the present invention has excellent sand-falling resistance and long-term aging resistance.
The method for producing the organofluorine-modified polyurethane elastomer resin of the present invention will be described in detail in example 4.
Example 4
(1) Removing water from propylene glycol methyl ether acetate with 4A molecular sieve to make its water content less than 50PPM, introducing N into a reaction kettle equipped with a condensing reflux device2And (3) protecting, adding 120 parts of side chain fluoropolyether diol, 30 parts of hydroxyl-terminated polybutadiene, 2 parts of diethylene glycol, 1.5 parts of dimethylolpropionic acid and 45 parts of propylene glycol methyl ether acetate, and starting a stirrer. Dripping 7 parts of hydrogenated MDI within 30min, heating to 80 ℃ after dripping, and carrying out heat preservation reaction for 2h to form the hydroxyl-terminated polyurethane elastomerA body prepolymer.
(2) And (2) dropwise adding 3.5 parts of hydrogenated MDI into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (1), and carrying out heat preservation reaction for 2h at the temperature of 80 ℃.
(3) And (3.5) dropwise adding hydrogenated MDI, 0.01 part of dibutyltin dilaurate and 50 parts of propylene glycol methyl ether acetate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (2), carrying out heat preservation reaction at the temperature of 80 ℃ for 4 hours, cooling to room temperature, and discharging to prepare the organic fluorine modified polyurethane elastomer resin.
The coating material having a wind-and-sand resistant function of the present invention will be described in detail in example 5.
Example 5
120 parts of the organic fluorine-modified polyurethane elastomer resin prepared in example 4 was taken, and then 25 parts of rutile titanium dioxide, 13 parts of potassium titanate whiskers, 7 parts of ceramic microspheres, 0.3 part of a leveling agent, 1 part of a dispersant, 1 part of an antioxidant, 0.3 part of a light stabilizer, and 1.3 parts of an ultraviolet absorber were added to the organic fluorine-modified polyurethane elastomer resin, to form a coating having a wind-blown sand resistance function.
The solar cell back sheet of the present invention will be described in detail in example 6.
Example 6
The coating with the wind-sand resistant function prepared in the example 5 is added with a curing agent N3300, blade-coated on the surface of a PET substrate, the thickness of the coating is 20-30 μm, and the coating is baked in an oven at 140 ℃ for 10Min for curing to prepare the back plate for the solar cell in the invention. The main properties were tested as follows:
resistance to falling sand test
Figure BDA0002357517870000081
Figure BDA0002357517870000091
Long term aging Performance test
Figure BDA0002357517870000092
From the above tests of the sand drop resistance, it can be seen that the backsheet in example 6 of the present invention has excellent sand drop resistance and long-term aging resistance.
It should be noted that, the parts or% are all by weight, the falling sand abrasion resistance test is carried out according to the GB/T23988-2009 standard, and the long-term aging test is carried out according to the IEC61215-2016 standard.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (7)

1. A preparation method of organic fluorine modified polyurethane elastomer resin is characterized by comprising the following steps:
(1) mixing fluorine-containing polyether glycol, hydroxyl-terminated polybutadiene, a micromolecule chain extender containing at least two hydroxyl groups and a solvent; dropwise adding micromolecule isocyanate or a mixture containing micromolecule isocyanate, heating, stirring, and reacting for 1-6h at the temperature of 40-120 ℃ to form hydroxyl-terminated polyurethane elastomer prepolymer;
(2) continuously dropwise adding micromolecule isocyanate or a mixture containing isocyanate into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (1) at the temperature of 40-120 ℃, reacting for 2-4h, and carrying out chain extension reaction;
(3) and (3) at the temperature of 40-120 ℃, dropwise adding micromolecule isocyanate or a mixture containing micromolecule isocyanate, a catalyst and a solvent into the hydroxyl-terminated polyurethane elastomer prepolymer treated in the step (2), and reacting for 2-6h to form the organic fluorine modified polyurethane elastomer resin.
2. The method according to claim 1, wherein in step (1), the small molecule isocyanate is an aliphatic or alicyclic diisocyanate.
3. The production method as claimed in claim 1, wherein in the step (3), the catalyst is tetrabutyl titanate or organotin in an amount of 100-1000 ppm.
4. A coating is characterized in that the coating is formed by taking the organic fluorine modified polyurethane elastomer resin prepared by the preparation method of any one of claims 1 to 3 as a base material and adding an inorganic filler, a leveling agent, a dispersing agent, an antioxidant, a light stabilizer and an ultraviolet absorber.
5. The coating of claim 4, wherein the inorganic filler comprises one or more of rutile titanium dioxide, fibrous filler, ceramic microsphere filler, and whisker filler; wherein the particle size of the rutile type titanium dioxide is less than 0.3 μm; the fibrous filler comprises one or more of polycrystalline mullite fiber powder, glass fiber powder and graphene fiber powder, and the particle size of the fibrous filler is 1000-2000 meshes; the ceramic microsphere filler comprises one or a mixture of any one of silicon oxide alloy ceramic microspheres, aluminum oxide alloy ceramic microspheres or zirconium oxide ceramic microspheres, and the particle size of the ceramic microsphere filler is less than 10 mu m; the whisker is one or a mixture of any one of calcium carbonate whisker, calcium sulfate whisker, potassium titanate whisker and aluminum borate whisker, and the length of the whisker is less than 10 mu m.
6. A backboard comprises a substrate layer, wherein one side of the substrate layer is provided with a high weather-resistant fluorocarbon coating layer, and the other side of the substrate layer is provided with a wind-resistant sand layer; characterized in that the wind sand resistant layer is made of the coating of claim 4 or 5.
7. The backsheet according to claim 6, wherein the thickness of the highly weatherable fluorocarbon coating layer is 3-50 μm, and the thickness of the substrate layer is 100-500 μm; the base material layer is a film prepared by blending one or more of PET, PEN, PBT and PCT and stretching the mixture through coextrusion.
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