CN110791247A - Solar cell backboard adhesive resin and preparation method thereof - Google Patents

Solar cell backboard adhesive resin and preparation method thereof Download PDF

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Publication number
CN110791247A
CN110791247A CN201911189695.1A CN201911189695A CN110791247A CN 110791247 A CN110791247 A CN 110791247A CN 201911189695 A CN201911189695 A CN 201911189695A CN 110791247 A CN110791247 A CN 110791247A
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solar cell
adhesive resin
polyester
acid
component
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付洪娥
王新
王玉灿
魏田
鲁琴
刘博�
李致轩
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SHENYANG CHEMICAL RESEARCH INSTITUTE Co Ltd
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SHENYANG CHEMICAL RESEARCH INSTITUTE Co Ltd
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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
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • 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
    • 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

Abstract

The invention belongs to the field of organic synthesis, relates to a high-molecular polymerization technology, and particularly relates to a solar cell backboard adhesive resin and a preparation method thereof. The solar cell backboard adhesive resin is solvent type bi-component adhesive resin, which takes epoxy chain-extended high molecular weight polyester with hydroxyl as a component A and takes polyisocyanate as a component B; wherein the component A and the component B are mixed according to the mass ratio of 3:4-20: 1. The adhesive prepared by the invention has good initial peeling strength and good weather resistance for PET films, PVF films and EVA films, and the peeling strength is still more than 6N/cm (180-degree peeling) after 3000 hours under the condition of double 85. Can completely meet the application performance requirement of the solar back panel glue.

Description

Solar cell backboard adhesive resin and preparation method thereof
Technical Field
The invention belongs to the field of organic synthesis, relates to a high-molecular polymerization technology, and particularly relates to a solar cell backboard adhesive resin and a preparation method thereof.
Background
The solar cell back plate is of a three-layer thin film structure, all layers are bonded by adhesives, and the adhesives are directly related to the performance and the service life of the back plate.
At present, the solar cell is mainly made of TPT and TPE materials, the outer-layer film has higher fluorine content and better weather resistance, but the bonding property is poor, so that the problem of low interlayer peeling force is caused. The main production enterprises of the back plate adhesive are foreign enterprises, a few domestic enterprises have low-end adhesive production lines, the production technology is backward, and the product quality is obviously different from foreign products, so that the enterprises change the coating method to produce the back plates. Because the raw materials used by the coating type backboard are imported from foreign countries, the price is high, the supply is unstable, and the coating type backboard is seriously restricted by foreign fluorine chemical enterprises. The photovoltaic industry in China mainly focuses on areas such as long, bead triangle and the like. Enterprises related to the photovoltaic industry are few in province, the existing adhesive for the solar cell panel back plate is weak in production technology base, and the difference between the existing adhesive and the technical level of the photovoltaic industry province is large. In order to change the unfavorable situations of weak application performance, low market share and the like of the domestic solar cell back panel adhesive, the project is necessary to carry out research. By the development of the adhesive with a new structure and composition, the application performance and the service life of the product are improved, and the localization of the preparation process of the high-quality backboard adhesive is realized.
CN102250577A discloses a two-component polyurethane adhesive for solar back panels, wherein a main agent is obtained by polycondensation of terephthalic acid, phthalic acid, 1, 6-hexanediol, cyclohexanedimethanol and ethylene glycol, and a curing agent is one or more of HDI tripolymer, IPDI tripolymer, TDI-HDI mixed tripolymer, hydrogenated TDI and hydrogenated MDI. The adhesive obtained by compounding has higher Tg and can be compounded with a solar backboard made of fluorine-containing materials.
CN104017531A discloses a hydrolysis-resistant photovoltaic back plate adhesive and a preparation method thereof. The component A is novel polyester polyol, added light stabilizer and the like, the component B is a diisocyanate curing agent, on the premise of keeping good mechanical property, the hydrolysis resistance of the polyurethane adhesive prepared by using the traditional polyester polyol is improved, meanwhile, the light stabilizer with a certain proportion is added into the adhesive, and the hydrolysis resistance and the aging resistance of the polyurethane adhesive used in the photovoltaic back plate are improved to a certain degree.
CN106244081A discloses an adhesive composition for solar cell back plates and a preparation method thereof, wherein the composition is composed of a prepolymer component and a curing agent component, wherein the prepolymer component comprises fluorine modified resin, polyester resin, an antioxidant, an ultraviolet light absorber, an anti-hydrolysis agent and ethyl acetate; the curing agent component is hexamethylene diisocyanate trimer. The components are physically mixed according to a certain proportion, and the obtained adhesive is used as a solar backboard adhesive, so that the double 85 test lasts for more than 3000 hours.
It can be seen from the above documents that the conventional solar back panel adhesive is a two-component polyurethane adhesive, i.e. polyester resin and polyisocyanate. The polyester resin is mostly linear long-chain polymer, and the terminal hydroxyl group of the polyester after sizing reacts with isocyanate group in trimer of HDI, TDI and MDI to be solidified so as to bond the backboard material. The linear long-chain polyester only has terminal hydroxyl, so that the anchoring points of the linear long-chain polyester, a polyisocyanate curing agent and a back plate material are few, and ester bonds of the polyester can undergo hydrolysis reaction in a long-term atmospheric environment, so that the weather resistance of the adhesive is poor. Furthermore, adhesives with new structures of different components need to be obtained, so that the application performance of the product is improved and the service life of the product is prolonged.
Disclosure of Invention
The invention aims to provide a solar cell backboard adhesive resin and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a solar cell backboard adhesive resin is a solvent type bi-component adhesive resin, which takes epoxy chain-extended high molecular weight polyester with hydroxyl as a component A and polyisocyanate as a component B; wherein the component A and the component B are mixed according to the mass ratio of 3:4-20: 1.
The epoxy chain-extended high-molecular polyester with hydroxyl is carboxyl-terminated polyester with Mn of 5000-20000 and epoxy chain extender, and the epoxy chain-extended high-molecular polyester with hydroxyl and the molecular weight of which reaches Mn of 40000-120000 is obtained through chain extension and tackifying; wherein, the addition amount of the epoxy chain extender is 1 to 20 percent of the mass of the carboxyl terminated polyester.
The epoxy chain extender is one or two of 1, 4-cyclohexanedimethanol glycidyl ether, 1, 4-butanediol diglycidyl ether, bisphenol A-diglycidyl ether, glycidyl ether, triglycidyl isocyanurate, N, N, N ', N ' -tetraglycidyl ester-4, 4 ' -diaminodiphenylmethane, bisphenol A polyglycidyl ether, bisphenol A epoxy resin and bisphenol F epoxy resin.
The epoxy chain-extended high-molecular polyester with hydroxyl is prepared by mixing aromatic dibasic acid, long-chain fatty dibasic acid, dihydric alcohol and trihydric alcohol, and then performing esterification reaction at the temperature of 270 ℃ under normal pressure; then, the esterification product is polycondensed by a polycondensation catalyst under the conditions of high temperature and high vacuum to obtain carboxyl terminated polyester with Mn of 5000-; and (3) carrying out chain extension and tackifying on the polyester and the epoxy chain extender to obtain the high-molecular polyester with the molecular weight of Mn 40000-120000.
The carboxyl-terminated polyester is prepared by mixing aliphatic diol, aliphatic dibasic acid and aromatic dibasic acid, stirring under the protection of nitrogen, heating to the temperature of 240-plus-one (270 ℃) within 1 hour for esterification reaction, carrying out heat preservation reaction for 2-3 hours until no water is distilled out of a condenser, adding a polycondensation catalyst, continuously heating to the temperature of 260-plus-one (280 ℃) and carrying out polycondensation reaction for 1-4 hours under the absolute pressure of 100-40Pa, and obtaining the carboxyl-terminated polyester with the target molecular weight of 5000-20000; adding the polyester and an epoxy chain extender into an extruder, and extending and tackifying until the molecular weight reaches 40000-120000. Wherein the molar ratio of the aromatic dibasic acid to the aliphatic dibasic alcohol to the aliphatic dibasic acid is 1-6: 1-6: 1.
the aliphatic dihydric alcohol is C2-C12Two or three of the linear or branched diols of (a); specifically, the diol may be one, two or three of ethylene glycol, 1.2-propanediol, 1.3-propanediol, butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1.6-hexanediol, 1.2-heptanediol, 1.7-heptanediol, 1.2-octanediol, 1.8-octanediol, 1.2-nonanediol, 1.9-nonanediol, 1.2-decanediol, 1.10-decanediol, 1, 11-undecanediol and 1, 12-dodecanediol. One or two of ethylene glycol, 1, 2-propylene glycol, butanediol, neopentyl glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 10-decanediol, and 1, 12-dodecanediol are preferable.
The aliphatic dibasic acid is C3-C18The fatty dibasic acid of (1); the aromatic dibasic acid is two or three of phthalic acid, terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-1, 4-dicarboxylic acid. Specifically, the acid may be one, two or three of malonic acid, succinic acid, adipic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and octadecanedioic acid. One or two of glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and dodecanedioic acid are preferred.
The aliphatic polyol used for preparing the carboxyl-terminated polyester is one or two of glycerol, trimethylolpropane and pentaerythritol.
The aromatic dibasic acid used for preparing the carboxyl-terminated polyester is benzene diacid or naphthalene diacid. Specifically, two or three of phthalic acid, terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, and naphthalene-1, 4-dicarboxylic acid may be used.
The polyisocyanate is an addition product of TDI, pentaerythritol and trimethylolpropane.
The application of the adhesive resin for the solar cell back panel as an adhesive resin in a solar back panel adhesive.
The prepared epoxy chain-extended high-molecular polyester with hydroxyl is dissolved in a solvent, wherein the solvent can be ethyl acetate, butanone and toluene. The solution with the solid content of 30 percent is the component A.
In the case of a solvent-based two-component adhesive resin for solar back sheets, the polyisocyanate is an adduct of TDI with pentaerythritol and trimethylolpropane. The obtained adduct is dissolved in ethyl acetate or butanone to obtain component B with solid content of 70-75%.
The solvent-based bi-component adhesive resin for the solar cell back panel is applied by uniformly mixing the adhesive resin components A and B according to a proportion, sequentially adding the catalyst, the ultraviolet absorbent, the light stabilizer and the antioxidant, and uniformly mixing to obtain the solar cell back panel adhesive.
And uniformly mixing the adhesive resin, a catalyst, an ultraviolet absorber, a light stabilizer and an antioxidant to obtain the solar cell backboard adhesive.
A solar cell back plate is characterized in that a solar back plate adhesive of adhesive resin is coated on a back plate supporting layer PET layer, the drying is carried out for 3 minutes at 70-100 ℃, the obtained adhesive film and a back plate supporting layer PVF layer are subjected to hot-pressing compounding at 70-90 ℃ under the pressure of 0.5MPa, and the curing is carried out for 72 hours at 60 ℃ to obtain the solar cell back plate.
The invention has the advantages that:
the solar cell backboard adhesive resin is obtained by compounding epoxy chain-extended polyester polyol and a polyisocyanate curing agent according to a certain proportion. The aromatic dibasic acid is used for improving the bonding performance, the long carbon chain aliphatic dibasic acid is used for improving the flexibility of the adhesive, the ratio of monomers is adjusted, and the prepared polyester can improve the toughening, hydrolysis resistance, high temperature resistance and high bonding strength performance of the adhesive; after the polyester epoxy chain is extended, the obtained component A has the characteristics of large molecular weight, high hydroxyl content and the like, and after the component A and the component B are compounded into a gluing agent, the advantage that the polyester adhesive material has more bonding anchoring points is realized; and branched chain dihydric alcohol is added in the molecular synthesis process. The combination of the two materials endows the adhesive with excellent double 85 resistance and still has high glass strength after 3000 hours.
Detailed Description
The present invention is further illustrated in detail by the following examples. The invention is in no way limited thereto.
The solar cell backboard adhesive resin comprises a component A, a component B and a component C, wherein the component A is epoxy chain-extended polyester, and the component B is polyisocyanate. The adhesive is used as an adhesive resin for PVF and PET and is used for an adhesive material between films of a solar back plate. The component A contains polyhydroxy active groups in molecules, and the molecular weight is 40000-120000. Component B contains TDI polymer or adduct with 3-5 isocyanate groups. The preparation method of the adhesive composition comprises the following steps: carrying out esterification reaction on aliphatic dibasic alcohol, long-chain aliphatic dibasic acid and aromatic dibasic acid in inert gas under normal pressure; then adding a catalyst for polycondensation reaction under the conditions of high temperature and high vacuum, and adding a solvent to dissolve the polymer obtained after chain extension of the obtained carboxyl-terminated polyester diol by using an epoxy compound, thereby obtaining the component A. The component B is TDI polymer or additive product of TDI and trimethylolpropane. The adhesive prepared by the invention has good initial peeling strength and good weather resistance for PET films, PVF films and EVA films, and the peeling strength is still more than 6N/cm (180-degree peeling) after 3000 hours under the condition of double 85. Can completely meet the application performance requirement of the solar back panel glue.
Example 1
580.5 g of terephthalic acid, 720.6 g of isophthalic acid, 317.0 g of sebacic acid, 496 g of ethylene glycol, 128.1 g of 1, 6-hexanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony acetate are added into a 3L polymerization reaction kettle, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the kettle is kept between 0.25 and 0.3MPa, the temperature at the top of the water distillation kettle is kept lower than 120 ℃ until the distilled water amount reaches 170 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight Mn of 19800, an acid value of 5.36mgKOH/g, and a hydroxyl value of 0.45 mgKOH/g.
1250 g of the carboxyl-terminated polyester obtained above, 183.1 g of bisphenol A epoxy resin E20 and 0.5 g of antimony trioxide are added into an extruder, the temperature is raised to 240 ℃, the extrusion speed is controlled at 10g/min, and a granulated product is obtained. The acid value was measured to be 0.89mgKOH/g, the hydroxyl value was measured to be 65.2mgKOH/g, and the molecular weight was measured by GPC as Mn 78000. Refluxing the polyester in ethyl acetate to prepare the polyester containing 30 percent of solid hydroxyl epoxy chain extension.
Example 2
824.0 g of isophthalic acid, 317.0 g of adipic acid, 378.2 g of ethylene glycol, 98.4 g of 3-methyl-1, 5-pentanediol, 4.5 g of trimethylolpropane and 1.0 g of antimony trioxide are added into a 3L polymerization reactor, the temperature is raised to 250 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, and the temperature at the top of the distillation tower is lower than 120 ℃ until the amount of distilled water reaches 90 g, so that the esterification reaction is completed. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 60Pa for about half an hour, simultaneously raising the temperature to 280 ℃, starting polycondensation reaction, reacting for 3 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 8600, an acid value of 12.80mgKOH/g and a hydroxyl value of 0.28 mgKOH/g.
1200 g of carboxyl terminated polyester, 338 g of 1, 4-butanediol diglycidyl ether and 0.5 g of antimony trioxide are added into an extruder, the temperature is increased to 240 ℃, and the extrusion speed is controlled to be 10g/min, so that a granulated product is obtained. The acid value was measured to be 0.52mgKOH/g, the hydroxyl value was measured to be 61.1mgKOH/g, and the molecular weight was measured by GPC as Mn 105000. Refluxing the polyester in ethyl acetate to prepare the polyester containing 30 percent of solid hydroxyl epoxy chain extension.
Example 3
580.5 g of phthalic acid, 720.6 g of isophthalic acid, 217.0 g of adipic acid, 612.4 g of 1, 2-propanediol, 128.1 g of 1, 4-butanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony acetate are added into a 3L polymerization reaction kettle, the temperature is raised to 260 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the kettle is kept between 0.25 and 0.3MPa, and the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 165 g, so that the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 45Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 15200, an acid value of 6.00mgKOH/g and a hydroxyl value of 0.38 mgKOH/g.
1200 g of carboxyl terminated polyester, 84 g of bisphenol A polyglycidyl ether and 0.5 g of antimony trioxide are added into an extruder, the temperature is increased to 240 ℃, the extrusion speed is controlled to be 10g/min, and a granulated product is obtained. The acid value was measured to be 0.47mgKOH/g, the hydroxyl value was measured to be 18.2mgKOH/g, and the molecular weight was measured by GPC as Mn 64000. Refluxing the polyester in ethyl acetate to prepare the polyester containing 30 percent of solid hydroxyl epoxy chain extension.
Example 4
880.0 g of terephthalic acid, 217.0 g of azelaic acid, 280.4 g of ethylene glycol, 160.5 g of neopentyl glycol and 0.8 g of antimony acetate are added into a 3L polymerization reaction kettle, the temperature is raised to 260 ℃ within about one hour, the distillation speed of generated water is adjusted, the pressure in the kettle is kept between 0.25 and 0.3MPa, the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 160 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 45Pa for about half an hour, simultaneously raising the temperature to 270 ℃, starting polycondensation reaction for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
The polyester obtained above was subjected to GPC measurement to find that it had a molecular weight of Mn 13800, an acid value of 7.50mgKOH/g and a hydroxyl value of 0.63 mgKOH/g.
1200 g of carboxyl terminated polyester, 302.3 g of bisphenol A epoxy resin E44 and 0.6 g of antimony trioxide are added into an extruder, the temperature is raised to 240 ℃, the extrusion speed is controlled to be 10g/min, and a granulated product is obtained. The acid value was measured to be 1.89mgKOH/g, the hydroxyl value was measured to be 54.0mgKOH/g, and the molecular weight was measured by GPC as Mn 105000. Refluxing the polyester in ethyl acetate to prepare the polyester containing 30 percent of solid hydroxyl epoxy chain extension.
Comparative example 1
580.5 g of terephthalic acid, 720.6 g of isophthalic acid, 317.0 g of sebacic acid, 746 g of ethylene glycol, 128.1 g of 1, 6-hexanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony acetate are added into a 3L polymerization reactor, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, the temperature at the top of the distillation tower is lower than 120 ℃ until the distilled water amount reaches 170 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 4-5 hours under the condition, slowly increasing the power, and discharging 256 g of polycondensation distillate to obtain the hydroxyl-terminated polyester.
GPC measured the molecular weight Mn 34000, hydroxyl value 2.61mgKOH/g, acid value 0.5 mgKOH/g.
Comparative example 2
320.6 g of isophthalic acid, 617.0 g of adipic acid, 296.0 g of ethylene glycol, 160.5 g of 3-methylpentanediol, 6.5 g of trimethylolpropane and 1.0 g of antimony trioxide are added into a 3L polymerization reactor, the temperature is raised to 240 ℃ within about one hour, the distillation rate of generated water is adjusted, the pressure in the reactor is kept between 0.25 and 0.3MPa, and the temperature at the top of the distillation tower is kept lower than 120 ℃ until the amount of distilled water reaches 110 g, and the esterification reaction is finished. And opening a vacuum system, adjusting the vacuum degree in the kettle to about 80Pa for about half an hour, simultaneously raising the temperature to 275 ℃, starting the polycondensation reaction, reacting for 2.5 hours under the condition, and discharging to obtain the carboxyl-terminated polyester.
GPC measured molecular weight Mn 14000, acid value 7.38mgKOH/g, hydroxyl value 0.60 mgKOH/g.
1200 g of carboxyl terminated polyester, 111.3 g of bisphenol A epoxy resin E44 and 0.6 g of antimony trioxide are added into an extruder, the temperature is raised to 240 ℃, the extrusion speed is controlled to be 10g/min, and a granulated product is obtained. The acid value was measured to be 1.49mgKOH/g, the hydroxyl value was measured to be 22.1mgKOH/g, and the molecular weight was measured by GPC as Mn 45000. Refluxing the polyester in ethyl acetate to prepare the polyester containing 30 percent of solid hydroxyl epoxy chain extension.
Application test:
preparing glue:
the products of the examples and the comparative examples are mixed with TDI pentaerythritol addition product (obtained by reacting TDI and pentaerythritol in a molar ratio of 1:4 in toluene solvent at 90 ℃ for 4 hours) according to the molar ratio of hydroxyl value of solute to NCO of 1:1.15, and then 0.3% of antioxidant, 06% of ultraviolet absorbent and 1% of hydrolysis stabilizer are added and uniformly mixed for later use.
Sample preparation:
coating the prepared adhesive on a PET sheet, wherein the adhesive application amount is 10g/m2(folding), drying at 80 ℃ for 10 minutes, placing the pretreated PVD film on the adhesive coated on the surface of the PET sheet, compounding on a plane press with the pressure of 1.0MPa, and pressing at 50 ℃ for 40 minutes. The composite sheet was cured at 40 ℃ for 48 hours.
Evaluation method:
1. and (3) testing the peel strength: the composite sheet was cut into 15mm wide sample pieces and subjected to a 180 ° peel test at a speed of 50mm/min in a universal testing machine. Reference standard: the national standard GB/T2790 adhesive 180 DEG peeling strength test method flexible materials to rigid materials.
2. Constant resistance to wet heat aging: at 85 deg.C, relative humidity 85%, 3000 h. Before and after the test, the peel strength of the sample specimens (15 × 200mm) was measured according to the national standard. Reference standard: the national standard GB/T2790 adhesive 180 DEG peeling strength test method flexible materials to rigid materials.
3. PCT aging resistance
The strips (15 x 200mm) before and after the test were subjected to the peel strength test according to the standard method in an autoclave at 121 ℃ under atmospheric pressure for 72 hours. Reference standard: the national standard GB/T2790 adhesive 180 DEG peeling strength test method flexible materials to rigid materials.
4. Weather resistance
The specimens (50 × 150mm) were placed in a xenon weather resistance tester to perform an accelerated aging test, and the appearance after light irradiation was observed. Reference is made to the standard ASTM G155.
The test data are shown in the following table:
TABLE 1 evaluation table of sample application properties
Figure BDA0002293253430000071
According to test results, after the adhesive prepared from the polyester adhesive resin prepared by the method is applied to multi-layer bonding of solar cell back plates, the weather resistance, the initial peel strength and the peel strength after 3000 hours of double-85' peeling strength of the adhesive have higher values, and the application performance requirements of the solar cell back plate adhesive can be met.

Claims (10)

1. The solar cell backboard adhesive resin is characterized in that: the solar cell backboard adhesive resin is solvent type bi-component adhesive resin, which takes epoxy chain-extended high molecular weight polyester with hydroxyl as a component A and takes polyisocyanate as a component B; wherein the component A and the component B are mixed according to the mass ratio of 3:4-20: 1.
2. The solar cell back sheet adhesive resin according to claim 1, wherein: the epoxy chain-extended high-molecular polyester with hydroxyl is carboxyl-terminated polyester with Mn of 5000-20000 and epoxy chain extender, and the epoxy chain-extended high-molecular polyester with hydroxyl and the molecular weight of which reaches Mn of 40000-120000 is obtained through chain extension and tackifying; wherein the addition amount of the epoxy chain extender is 1-20% of the mass of the carboxyl-terminated polyester.
3. The solar cell back sheet adhesive resin according to claim 2, wherein: the epoxy chain extender is one or two of 1, 4-cyclohexanedimethanol glycidyl ether, 1, 4-butanediol diglycidyl ether, bisphenol A-diglycidyl ether, glycidyl ether, triglycidyl isocyanurate, N, N, N ', N ' -tetraglycidyl ester-4, 4 ' -diaminodiphenylmethane, bisphenol A polyglycidyl ether, bisphenol A epoxy resin and bisphenol F epoxy resin.
4. The solar cell back sheet adhesive resin according to claim 2 or 3, wherein: the epoxy chain-extended high-molecular polyester with hydroxyl is prepared by mixing aromatic dibasic acid, long-chain fatty dibasic acid, dihydric alcohol and trihydric alcohol, and then performing esterification reaction at the temperature of 270 ℃ under normal pressure; then, the esterification product is polycondensed by a polycondensation catalyst under the conditions of high temperature and high vacuum to obtain carboxyl terminated polyester with Mn of 5000-; and (3) carrying out chain extension and tackifying on the polyester and the epoxy chain extender to obtain the high-molecular polyester with the molecular weight of Mn 40000-120000.
5. The solar cell back sheet adhesive resin according to claim 4, wherein: the polyester with the carboxyl end capping is prepared by mixing aliphatic diol, aliphatic dibasic acid and aromatic dibasic acid, stirring under the protection of nitrogen, heating to the temperature of 240-plus-270 ℃ within 1 hour for esterification reaction, carrying out heat preservation reaction for 2-3 hours until no water is distilled out of a condenser, adding a polycondensation catalyst, continuously heating to the temperature of 260-plus-280 ℃ and carrying out polycondensation reaction for 1-4 hours under the absolute pressure of 100-40Pa, and obtaining a polymer with the target molecular weight of 5000-plus-20000; wherein the molar ratio of the aromatic dibasic acid to the aliphatic dibasic alcohol to the aliphatic dibasic acid is 1-6: 1-6: 1.
6. the solar cell back sheet adhesive resin according to claim 5, wherein: the aliphatic dihydric alcohol is C2-C12Two or three of the linear or branched diols of (a); the aliphatic dibasic acid is C3-C18The fatty dibasic acid of (1); the aromatic dibasic acid is two or three of phthalic acid, terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid or naphthalene-1, 4-dicarboxylic acid.
7. The solar cell back sheet adhesive resin according to claim 1, wherein: the polyisocyanate is an addition product of TDI, pentaerythritol and trimethylolpropane.
8. The application of the solar cell backboard adhesive resin in claim 1 is characterized in that: the application of the adhesive resin in serving as the adhesive of the solar back panel.
9. The use of the solar cell backsheet adhesive resin of claim 1 as defined in claim 8, wherein: the adhesive resin of claim 1 is uniformly mixed with a catalyst, an ultraviolet absorber, a light stabilizer and an antioxidant to obtain the adhesive for the back plate of the solar cell.
10. A solar cell backsheet, characterized in that: the solar back panel adhesive containing the adhesive resin of claim 1 is coated on a back panel support layer PET layer, dried at 70-100 ℃ for 3 minutes, subjected to hot-pressing compounding at 70-90 ℃ and 0.5MPa with a back panel support layer PVF layer, and cured at 60 ℃ for 72 hours to obtain the solar cell back panel.
CN201911189695.1A 2019-11-28 2019-11-28 Solar cell backboard adhesive resin and preparation method thereof Pending CN110791247A (en)

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