CN116333275A - Polyester material for solar backboard and preparation method thereof - Google Patents
Polyester material for solar backboard and preparation method thereof Download PDFInfo
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- 229920000728 polyester Polymers 0.000 title claims abstract description 56
- 239000000463 material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 80
- 238000006243 chemical reaction Methods 0.000 claims description 47
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 36
- 238000006068 polycondensation reaction Methods 0.000 claims description 34
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 3
- 230000032683 aging Effects 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 206010051246 Photodermatosis Diseases 0.000 description 5
- 230000008845 photoaging Effects 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- PFZWDJVEHNQTJI-UHFFFAOYSA-N antimony titanium Chemical compound [Ti].[Sb] PFZWDJVEHNQTJI-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- 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
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The application provides a polyester material for a solar backboard and a preparation method thereof, belonging to the technical field of plastic processing. The intrinsic viscosity of the polyester material is 0.72-0.78dl/g, the terminal carboxyl content is 6-10mol/t, the DEG content is 0.7-1.4%, the b value is 4+/-3, the L value is 82+/-4, and the a value is-2.0+/-1. When the material is used for the solar back plate, the solar back plate is endowed with good mechanical property, the material has good water resistance, and the solar back plate is endowed with light aging resistance and humidity aging resistance.
Description
Technical Field
The application relates to a polyester material for a solar backboard and a preparation method thereof, belonging to the technical field of plastic processing.
Background
The solar cell is produced by components such as toughened glass, a cell piece, a back plate, EVA, aluminum alloy, a junction box, silica gel and the like through a lamination technology. The back plate has good water vapor barrier property, insulating property, photo-aging resistance and wet heat aging resistance, and has the functions of maintaining and supporting the cell plate so as to prolong the service life of the solar cell.
In the current market, the solar cell backboard adopts two types of gluing compound type and coating type, wherein the gluing compound type backboard film is of a three-layer structure formed by compounding fluorine films or EVA adhesive films on two sides of a PET polyester film; the back plate coating film is formed by coating fluorine resin on two sides of a PET polyester film and drying and curing the fluorine resin. The PET polyester film used in both forms plays a very key role in the service performance of the back plate, but the common PET polyester film often has the problems of lack of water vapor barrier, poor moisture and heat resistance and the like.
Based on the above problems, in the preparation of solar back sheets, the industry has mainly focused on the following four ways of improvement of PET polyesters:
firstly, the hydrolysis resistance agent and the ultraviolet absorber are added to prepare master batch PET polyester chips, and then the master batch PET polyester chips are blended with PET polyester chips and PET polyester chips containing silicon dioxide to prepare the PET polyester film, but the hydrolysis resistance agent and the ultraviolet absorber not only can cause threat to natural environment and human body, but also can influence the mechanical property and the optical property of the material.
Secondly, modifying with various dihydric alcohols, dibasic acids, small batches of high branched chain polyalcohols and small batches of polyene higher fatty acids or alcohols to prepare PET polyester chips, and blending with PET polyester chips containing barium sulfate, titanium dioxide or silicon dioxide to prepare the PET polyester film, wherein the preparation process involves the addition of various substances, which directly leads to the increase of the cost for producing the PET polyester chips and is not beneficial to industrial production and sale.
And thirdly, directly adopting the production process of PET polyester chips, and sequentially carrying out esterification, polycondensation and solid-phase polymerization to generate PET polyester chips, compared with the former two methods, the method reduces the process of blending master batch PET resin chips, avoids the problems of uneven dispersion and product-to-product difference caused by blending, but has the problems of strict solid-phase polymerization reaction condition and overlong reaction time, and the existence of the problems can weaken the light aging resistance and the humidity and heat aging resistance of the PET resin film. Meanwhile, the production of the polyester chips by the method needs two steps, and the chips are thickened.
Fourthly, additives such as silicon dioxide, calcium carbonate, barium sulfate, titanium dioxide and the like are added into ethylene glycol in advance, and after uniform mixing, esterification reaction, pre-polycondensation and final polycondensation are carried out to prepare PET resin slices, and the production cost is increased due to too much additive introduction.
Disclosure of Invention
In view of the above, the present application provides a polyester material for solar back sheets, which has good aging resistance and ductility, and mechanical properties far superior to those of conventional solar back sheets.
Specifically, the application is realized through the following scheme:
the polyester material for solar back plate has intrinsic viscosity of 0.72-0.78dl/g, terminal carboxyl content of 6-10mol/t, DEG content of 0.7-1.4%, b value of 4+ -3, L value of 82+ -4, and a value of-2.0+ -1.
The setting of the intrinsic viscosity value of the scheme endows the material with good mechanical properties; the arrangement of the terminal carboxyl content value endows the material with good ageing resistance and ductility; setting DEG content value, endowing the material with good fluidity; the arrangement of the values L, a and b gives the material a good appearance. When the polyester material is used for the solar back plate, the back plate can be endowed with good water vapor barrier property, insulating property, photo-aging resistance and wet heat aging resistance on the premise of meeting the mechanical property, the action effect of the solar cell panel is effectively maintained and supported, and the service life of the solar cell is prolonged.
Meanwhile, the applicant also provides a preparation method of the polyester material for the solar backboard, which comprises the steps of adding ethylene glycol, terephthalic acid and a titanium catalyst into a slurry kettle together, wherein the molar ratio of the ethylene glycol to the terephthalic acid is 2.6:1, the addition amount of the titanium catalyst in slurry formed by the ethylene glycol and the terephthalic acid is 300ppm, and uniformly mixing and stirring to obtain slurry containing the terephthalic acid and the ethylene glycol; the slurry is subjected to esterification reaction and polycondensation reaction to prepare polyester chips; the intrinsic viscosity of the polyester chip is 0.74-0.78dl/g, the terminal carboxyl content is 6-10mol/t, and the b value is 4+/-3.
The preparation method controls the glycol, the terephthalic acid and the titanium catalyst to obtain the polyester chip through esterification and polycondensation under a specific adding ratio, has simple reaction conditions and less process links, is beneficial to industrial production, is environment-friendly, and can realize one-step direct production.
Further, as preferable:
the esterification reaction comprises two steps: esterification reaction I and esterification reaction II, wherein in the esterification reaction I, the reaction time is 4 hours, the reaction temperature is 250 ℃, the reaction pressure is 70kPa, and the reaction liquid level is 70%; in the esterification reaction II, the reaction time is 1.5h, the reaction temperature is 265 ℃, the reaction pressure is 5kPa, and the reaction liquid level is 68%.
The polycondensation reaction comprises a polycondensation reaction I and a final polycondensation reaction, wherein a reaction kettle of the polycondensation reaction I is divided into an upper chamber and a lower chamber, the reaction time of slurry in the upper chamber is 0.6h, the reaction temperature is 276 ℃, the reaction pressure is 9kPa, and the reaction liquid level is 33%; the reaction time of the slurry in the lower chamber was 1h, the reaction temperature was 278℃and the reaction pressure was 0.6kPa, the reaction liquid level was 30%. The final polycondensation reaction is carried out for 1.5 hours, the reaction temperature is 282 ℃, the reaction pressure is 0.1kPa, and the reaction liquid level is 15%.
The reaction realizes the preparation of the solar backboard polyester material with special performance by controlling the esterification and polycondensation reaction flow and parameters and matching with raw materials (ethylene glycol, terephthalic acid and titanium catalyst), and endows the solar backboard with good mechanical performance, water vapor barrier performance, insulating performance, photo-aging resistance and wet heat aging resistance. Besides the catalyst, no more preparation is introduced in the reaction process, so that the melt property in the reaction process is easier to control, and the process links are less, thereby being beneficial to industrial production.
Drawings
FIG. 1 is a schematic structural diagram of a reaction vessel for polycondensation reaction I in the present application;
reference numerals in the drawings: 1. a first scraped condenser; 2. a polycondensation reaction I reaction tank; 21. an upper chamber; 22. a lower chamber; 3. a second scraped condenser; 4. a final polycondensation reaction tank; 5. a melt pump; 6. a melt filter; 7. and (5) a granulator.
Fig. 2 is a melting curve (DSC) of the polyester material for solar back sheets prepared in example 1.
Detailed Description
Example 1
The preparation of the polyester material for the solar cell backboard film comprises the following steps:
(1) Preparing materials: ethylene glycol (commercially available) and terephthalic acid (commercially available) were added to the polyester titanium catalyst C in a ratio of 2.6:1 16 H 36 O 4 Ti is added into a slurry kettle together, and evenly mixed and stirred to obtain slurry containing terephthalic acid and ethylene glycol, polyester titanium catalyst C 16 H 36 O 4 The Ti content in the slurry was 300ppm;
(2) Preparation: the slurry containing terephthalic acid and ethylene glycol obtained in the step (1) firstly enters an esterification reaction kettle through a pipeline, the reaction temperature is controlled to 250 ℃, the reaction pressure is controlled to be 70kPa, after 4 hours of reaction, the product with the acid value of 92% is sent into a reaction tank of an esterification reaction II, the reaction temperature is controlled to be 265 ℃, the reaction pressure is controlled to be 5kPa, after 1.5 hours of reaction, the product with the acid value of 98% is sent into an upper chamber 21 of a polycondensation reaction I reaction tank 2, the reaction pressure is controlled to be 9kPa after 0.6 hour of reaction, the product is sent into a lower chamber 22 of the polycondensation reaction I reaction tank 2, the reaction temperature in the lower chamber 22 is controlled to be 278 ℃, the reaction pressure in the reaction chamber is controlled to be 0.6kPa, the reaction time in the final polycondensation reaction tank 3 is controlled to be 1 hour, the reaction temperature in the final polycondensation reaction tank 3 is 282 ℃, the reaction pressure in the reaction tank is controlled to be 0.1kPa, and after 1.5 hours of reaction, the obtained product is cooled and pelletized, the polyester material is obtained.
Comparative example 1
The embodiment is a preparation method of a conventional solar backboard polyester material, and the specific process is as follows:
(1) And (3) performing ultrasonic dispersion on the aqueous solution of the silicon dioxide with the particle size of 50nm, adding the aqueous solution into the ethylene glycol solution, heating to 105 ℃ for solvent displacement and water removal to obtain the ethylene glycol suspension containing the nanoscale silicon dioxide.
(2) Mixing titanium dioxide with the particle size of 0.5 mu m, a silane coupling agent and ethylene glycol, and sequentially carrying out colloid mill and ball mill dispersion to obtain an ethylene glycol suspension containing micron-sized titanium dioxide.
(3) Adding the ethylene glycol suspension containing the nano-scale silicon dioxide obtained in the step (1), the ethylene glycol suspension containing the micro-scale titanium dioxide obtained in the step (2), terephthalic acid and ethylene glycol into a slurry kettle, and mixing and stirring to obtain slurry containing terephthalic acid and ethylene glycol; wherein the mol ratio of terephthalic acid to ethylene glycol is 1.15.
(4) Firstly, adding the slurry containing terephthalic acid and ethylene glycol obtained in the step (3), a catalyst solution and a heat stabilizer solution into an esterification kettle, heating to 240 ℃ for esterification reaction for 4 hours, and obtaining the esterified product with the terminal carboxyl content less than or equal to 600 mol/t. The catalyst solution is obtained by mixing a titanium-antimony composite catalyst with ethylene glycol, wherein the antimony content is 100ppm, the titanium content is 15ppm, and the heat stabilizer solution is obtained by mixing trimethyl phosphate with ethylene glycol.
Then the obtained esterified substance is firstly added into an up-flow pre-polycondensation reactor for reaction for 1h, then is added into a pre-polycondensation reactor for pre-polycondensation reaction for 1h at the temperature of 260 ℃ and the pressure of 400Pa, and the pre-polycondensation product is obtained.
And then adding the obtained pre-polycondensation product into a final polymerization kettle, carrying out final polycondensation reaction at the temperature of 285 ℃ and the pressure of 100Pa, discharging when the intrinsic viscosity of the material reaches 0.63dl/g, cooling, and slicing to obtain a semi-finished product of the polyester chip.
The carboxyl end group content of the semi-finished product of the polyester chip is 23mol/t.
(5) Adding the semi-finished polyester chip obtained in the step (4) into a solid-phase tackifying device, pre-crystallizing at 150 ℃, and then performing solid-phase polycondensation at 225 ℃ and 160Pa for 8 hours to obtain the polyester chip for the solar cell back film with the intrinsic viscosity of 0.80dl/g and the terminal carboxyl content of 15mo 1/t.
The polyester materials of comparative example 1 and example 1 were separately prepared into solar back sheets, and the properties thereof were tested, and the results are shown in table 1.
Table 1: performance control Table for polyester materials
In Table 1, the tensile strength, the ageing resistance, the oxygen transmission and the water vapor transmission are all tested by taking a solar backboard as a test object, the film forming property is observed on line, the tensile strength and the elongation at break are tested according to an ASTMD882 standard, the water vapor transmission is tested according to an ISO15106-3 standard, and the ageing resistance is tested according to a GB/T31899-2015 standard.
As can be seen from table 1 and fig. 2:
as for the slicing parameters corresponding to the polyester material: the intrinsic viscosity is not much different from that of comparative example 1 even without solid phase polycondensation, but the terminal carboxyl group content is far lower than the corresponding parameters of the conventional solar back sheet of comparative example 1; the values of L in this case were substantially above that of comparative example 1, and the values of b and a were lower than that of comparative example 1; the above parameters provide the basis for the enhancement of their performance.
In terms of properties of the finished polyester material/solar backsheet: the tensile strength, the elongation at break and other parameters of the polyester material are superior to those of comparative example 1, which shows that the polyester material is superior to the polyester material of the conventional solar back panel in performance stability and mechanical performance; the hydrolytic aging resistance is higher than that of the comparative example 1, and the water vapor transmittance is far lower than that of the comparative document 1 under the same condition, so that the polyester material has good water resistance, and can endow the solar backboard with photo aging resistance and wet aging resistance.
The comparison is shown in table 2 in terms of cost and use.
Table 2: comparison table of using effect of polyester material
Comparison of table 2 shows that:
(1) Time cost aspect: the polyester material prepared in the scheme can be prepared in less than 10 hours, and the comparative example 1 can obtain a finished polyester chip in about 20 hours, and the time cost of one production period can be two production periods;
(2) The preparation cost is as follows: ethylene glycol (commercially available), terephthalic acid (commercially available) and polyester titanium catalyst C 16 H 36 O 4 Ti is used as a raw material, the cost of the raw material is about 6700 yuan/ton of slice, and the product obtained by final polycondensation can be cut into slices meeting the performance requirement of a backboard, so that the solid-phase tackifying and other procedures are not needed, the viscosity of the final polycondensation product of the comparison document 1 is lower, and the higher viscosity can be obtained only by solid-phase tackifying, adding auxiliary preparations such as a silane coupling agent, a heat stabilizer and the like, and the cost is far higher than that of the scheme.
(3) The aspect of using cost: the polyester material prepared by the scheme has good photo-aging resistance and moisture-aging resistance, and good mechanical properties, so that the polyester material supports a solar back plate, and under the same use condition, the service life of the polyester material can reach about 30 years, and the service life of the polyester material is about 25 years in comparative example 1.
Claims (5)
1. The polyester material for the solar backboard is characterized in that: the intrinsic viscosity of the polyester material is 0.72-0.78dl/g, the terminal carboxyl content is 6-10mol/t, the DEG content is 0.7-1.4%, the b value is 4+/-3, the L value is 82+/-4, and the a value is-2.0+/-1.
2. A preparation method of a polyester material for a solar backboard is characterized by comprising the following steps: adding ethylene glycol, terephthalic acid and a titanium catalyst into a slurry kettle together, wherein the molar ratio of the ethylene glycol to the terephthalic acid is 2.6:1, the adding amount of the titanium catalyst in the slurry formed by the ethylene glycol and the terephthalic acid is 300ppm, and uniformly mixing and stirring to obtain the slurry containing the terephthalic acid and the ethylene glycol; the slurry is subjected to esterification reaction and polycondensation reaction to prepare the polyester chip.
3. The method for preparing the polyester material for the solar back panel according to claim 2, wherein the method comprises the following steps: the esterification reaction comprises two steps: esterification reaction I and esterification reaction II, wherein in the esterification reaction I, the reaction time is 4 and h, the reaction temperature is 250 ℃, the reaction pressure is 70kPa, and the reaction liquid level is 70%; in the esterification reaction II, the reaction time is 1.5. 1.5h, the reaction temperature is 265 ℃, the reaction pressure is 5kPa, and the reaction liquid level is 68%.
4. The method for preparing the polyester material for the solar back panel according to claim 2, wherein the method comprises the following steps: the polycondensation reaction comprises a polycondensation reaction
And a final polycondensation reaction, said polycondensation reaction->
The reaction kettle of (2) is divided into an upper chamber and a lower chamber, the reaction time of the slurry in the upper chamber is 0.6 and h, the reaction temperature is 276 ℃, the reaction pressure is 9kPa, and the reaction liquid level is 33%; the reaction time of the slurry in the lower chamber was 1h, the reaction temperature was 278 ℃, the reaction pressure was 0.6kPa, and the reaction liquid level was 30%.
5. The final polycondensation reaction is carried out for a reaction time of 1.5. 1.5h, a reaction temperature of 282 ℃, a reaction pressure of 0.1kPa and a reaction liquid level of 15%.
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