CN117164838A - Melt straight-pull semitransparent solar backboard base film and production process thereof - Google Patents
Melt straight-pull semitransparent solar backboard base film and production process thereof Download PDFInfo
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- CN117164838A CN117164838A CN202311099458.2A CN202311099458A CN117164838A CN 117164838 A CN117164838 A CN 117164838A CN 202311099458 A CN202311099458 A CN 202311099458A CN 117164838 A CN117164838 A CN 117164838A
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- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000010954 inorganic particle Substances 0.000 claims abstract description 90
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 239000006185 dispersion Substances 0.000 claims abstract description 42
- 239000000155 melt Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 70
- 239000004408 titanium dioxide Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000006068 polycondensation reaction Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical group O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000032050 esterification Effects 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 13
- 238000005273 aeration Methods 0.000 claims description 12
- 239000000454 talc Substances 0.000 claims description 10
- 229910052623 talc Inorganic materials 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 19
- 230000000694 effects Effects 0.000 description 13
- 238000001514 detection method Methods 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 10
- 235000012222 talc Nutrition 0.000 description 9
- 230000006750 UV protection Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 208000005156 Dehydration Diseases 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- 238000005276 aerator Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000048 melt cooling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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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Abstract
The application relates to the field of polyester production, and particularly discloses a melt straight-pull semitransparent solar backboard base film and a production process thereof. The semitransparent solar backboard base film is prepared from the following raw materials in parts by weight: ethylene glycol a, terephthalic acid, catalyst, and inorganic particles; the mol ratio of the terephthalic acid to the ethylene glycol A is 1 (1.2-1.7), the addition amount of the catalyst accounts for 0.03-0.04wt% of the total mass of the ethylene glycol A and the terephthalic acid, and the addition amount of the inorganic particles accounts for 0.2-1wt% of the total mass of the ethylene glycol A and the terephthalic acid; the inorganic particles are pretreated before being added, and the specific process is as follows: firstly mixing inorganic particles with glycol B, stirring, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10-50 wt%. The application has the advantage that inorganic particles are uniformly dispersed in polyester melt, so as to ensure that the quality of the solar backboard base film reaches the standard.
Description
Technical Field
The application relates to the field of polyester production, in particular to a melt straight-pull semitransparent solar backboard base film and a production process thereof.
Background
The backboard is an important component of the solar cell and plays roles of insulation, protection and support. The service life of the back plate directly determines the service life of the solar cell because the back plate is in direct contact with the external environment, so that the solar cell has strict technical requirements on the thickness, tensile strength, elongation at break, weather resistance and other performance indexes of the back plate.
The biaxially oriented polyester film is used as a base film of the solar backboard, has the advantages of high strength and good rigidity, and is formed by polymerizing ethylene glycol and terephthalic acid. According to the application requirements of different solar cells, different requirements are made on the light transmittance of the base film, and if a semitransparent base film is to be obtained, inorganic particles are required to be added, so that the light transmittance is properly reduced.
In the past, the melt obtained by polymerization of ethylene glycol and terephthalic acid is directly doped into inorganic particles in an external addition mode, but the dispersibility of the inorganic particles in the melt is poor, so that the light transmittance can not meet the requirement, and the mechanical strength is reduced.
Disclosure of Invention
In order to improve the dispersibility of inorganic particles, the application provides a melt straight-pull semitransparent solar back plate base film and a production process thereof.
In a first aspect, the application provides a melt straight-pull semitransparent solar back plate base film, which adopts the following technical scheme: a melt straight-pull semitransparent solar backboard base film is prepared from the following raw materials in parts by weight: ethylene glycol a, terephthalic acid, catalyst, and inorganic particles;
the mol ratio of the terephthalic acid to the ethylene glycol A is 1 (1.2-1.7), the addition amount of the catalyst accounts for 0.03-0.04wt% of the total mass of the ethylene glycol A and the terephthalic acid, and the addition amount of the inorganic particles accounts for 0.2-1wt% of the total mass of the ethylene glycol A and the terephthalic acid;
the inorganic particles are pretreated before being added, and the specific process is as follows: firstly mixing inorganic particles with glycol B, stirring, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10-50 wt%.
By adopting the technical scheme, terephthalic acid and ethylene glycol can undergo polycondensation reaction with the help of a catalyst to obtain a polyester macromolecule for forming the back plate base film. The addition of the inorganic particles can adjust the light transmittance of the base film to reach the translucency degree, and can improve the ultraviolet resistance and the water vapor barrier property of the base film.
The inorganic particles are prepared into dispersion liquid by using glycol as a dispersing agent, and then participate in the reaction, so that the inorganic particles have the following advantages: firstly, the dispersant glycol B and the polyester reaction raw material glycol A are the same substance, so that the normal synthetic process of the polyester is not influenced; secondly, the compatibility of the dispersing agent and the polyester reaction raw material is good, inorganic particles are easy to uniformly disperse in the reaction liquid, so that the inorganic particles are ensured to be uniformly dispersed in the polyester melt synthesized later, the prepared base film has uniform light transmission everywhere, and the use requirement is met; thirdly, compared with the rest of dispersion solvents, the method is convenient for removing the superfluous glycol.
Optionally, the inorganic particles include one or more of mica, barium sulfate, kaolin, titanium dioxide, calcium carbonate, silica, talc, and montmorillonite.
Optionally, the pretreatment process of the inorganic particles further comprises an aeration step and a dehydration step, wherein the aeration step and the stirring step are performed simultaneously, the dehydration step is arranged after the centrifugation step, and the aeration step is to introduce water vapor in an aeration mode.
By adopting the technical scheme, a large amount of water vapor is introduced into the dispersion liquid, so that a large amount of bubbles are formed in the dispersion liquid, on one hand, part of bubbles gradually expand in the floating process, and the dispersion liquid has a scattering effect on agglomerated inorganic particles, and is beneficial to uniformly dispersing the inorganic particles in ethylene glycol; on the other hand, part of bubbles are dissolved in glycol in the floating process, so that the temperature of the dispersion liquid is increased, the dispersion effect of inorganic particles is better, no additional heating means is needed, and the energy is saved. After the aeration step is completed, the dispersion liquid contains moisture, so that dehydration treatment is performed without influencing the polymerization reaction.
Optionally, the inorganic particle is titanium dioxide.
By adopting the technical scheme, compared with other types of inorganic particles, the base film prepared by the method has more excellent ultraviolet resistance and water vapor barrier property; on the other hand, titanium dioxide is stable in chemical property and has good effect of scattering bubbles during the aeration step.
Alternatively, the inorganic particles have a particle size of 0.1 to 0.5 μm.
By adopting the technical scheme, the ultraviolet resistance of the titanium dioxide is related to the particle size of the titanium dioxide, and the titanium dioxide with the particle size has good shielding effect on ultraviolet rays with the wavelength of 275-400 nm. The particle size of the titanium dioxide is directly related to the dispersing effect, and the titanium dioxide with the particle size of less than 0.1 mu m has better ultraviolet resistance, but the agglomeration phenomenon is too obvious, the bonding force among particles is strong, the scattering effect of water vapor on the titanium dioxide is not obvious, and the surface modification of the particles by using a surfactant is needed, so that the cost is high, and the titanium dioxide with the particle size of 0.1-0.5 mu m is preferable.
Optionally, the catalyst is antimony trioxide.
In a second aspect, the application provides a production process of a melt straight-pull semitransparent solar backboard base film, which adopts the following technical scheme:
a production process of a melt straight-pull semitransparent solar backboard base film comprises the following steps:
s1, preparing:
preparing slurry: mixing ethylene glycol A and terephthalic acid to prepare slurry;
preparing inorganic particle dispersion liquid: mixing inorganic particles with ethylene glycol B, stirring, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10-50 wt%;
preparing a catalyst liquid: mixing a catalyst and ethylene glycol C according to the mass ratio of 1 (20-100) to prepare a catalyst liquid;
s2 esterification: mixing the slurry with the catalyst liquid, heating to 260-265 ℃, reacting at 150-200kPa for 4-5 hours, and adding the inorganic particle dispersion liquid after the reaction is completed to obtain a first material;
s3, pre-condensing: heating the first material to 270-283 ℃, wherein the reaction pressure is 10-30kPa, the reaction time is 1.5-2h, and discharging excessive glycol in the reaction process to obtain a second material;
s4, final polycondensation: heating the second material to 280-285 ℃, wherein the reaction pressure is 100-200Pa, and the reaction time is 2-3h, so as to obtain a melt;
s5, film preparation: and (3) carrying out casting, longitudinal drawing, transverse drawing, heat setting, cooling forming and corona on the melt to obtain the melt straight-drawing semitransparent solar backboard base film.
By adopting the technical scheme, firstly, inorganic particles are directly participated in the reaction process by adopting an internal adding mode, and are not added after the reaction is finished, so that the inorganic particles have good dispersibility in polyester melt; secondly, the polyester melt can directly meet the raw material requirements required by the film drawing process, and granulation and film reproduction are not needed, so that the problems of production efficiency reduction, high equipment cost, large energy loss, quality reduction and the like caused by the processes of melt cooling and granulating, drying and crystallizing, and melt extrusion can be avoided on the premise of ensuring the quality of the base film; the process parameters of S2 esterification, S3 pre-polycondensation and S4 final polycondensation are optimized, the prepared polyester melt has good yield and good comprehensive performance, for example, the reaction temperature in the S2 esterification is properly increased, the reaction time is prolonged, the esterification conversion rate can be improved by more than 95%, for example, in the S3 pre-polycondensation, the reaction temperature is properly increased, the vacuum degree range is adjusted, and the viscosity characteristic of the second material can be adjusted, so that inorganic particles are uniformly dispersed in the second material.
Optionally, the inorganic particle is titanium dioxide.
Optionally, in the S3 pre-polycondensation, the reaction temperature is 278-283 ℃.
By adopting the technical scheme, the dispersing effect of the titanium dioxide in the second material is best when the reaction temperature is 278-283 ℃.
Alternatively, in the S4 final polycondensation, the melt has an intrinsic viscosity of 0.7 to 0.8dL/g.
By adopting the technical scheme, the high-viscosity polyester melt can be obtained without an additional tackifying step through optimization of technological parameters, so that the polyester base film meeting the quality requirement can be conveniently prepared.
In summary, the application has the following beneficial effects:
1. according to the application, the inorganic particles are pretreated and doped into the polyester in an internal adding way, so that the inorganic particles are uniformly dispersed in the polyester melt synthesized later, and the prepared base film has uniform light transmission at all positions, thereby meeting the use requirement.
2. In the application, titanium dioxide with the particle size of 0.1-0.5 μm is preferably used as inorganic particles, so that the titanium dioxide is more suitable for the dispersion means of the application, the dispersion effect in a melt is good, and the ultraviolet resistance, the water vapor barrier property and the mechanical strength of the base film are improved;
3. the application optimizes the technological parameters of S2 esterification, S3 pre-polycondensation and S4 final polycondensation, and the prepared polyester melt has good yield and good comprehensive performance.
Detailed Description
The application is further described in detail below with reference to the following examples, which are specifically described: the following examples, in which no specific conditions are noted, are conducted under conventional conditions or conditions recommended by the manufacturer, and the raw materials used in the following examples are commercially available from ordinary sources except for the specific descriptions.
In the embodiment of the application, the ethylene glycol A, the ethylene glycol B and the ethylene glycol C are all ethylene glycol, and the differences only lie in different purposes, so that the differences are distinguished by different names. Ethylene glycol A is mainly used for synthesizing polyester, ethylene glycol B is mainly used for dispersing inorganic particles, and ethylene glycol C is mainly used for dispersing catalyst.
In an embodiment of the present application, the inorganic particles comprise one or more of mica, barium sulfate, kaolin, titanium dioxide, calcium carbonate, silica, talc, and montmorillonite.
Example 1:
a production process of a melt straight-pull semitransparent solar backboard base film comprises the following steps:
s1, preparing:
preparing slurry: mixing ethylene glycol A and terephthalic acid, and uniformly stirring to prepare slurry, wherein the mol ratio of the terephthalic acid to the ethylene glycol A is 1:1.2;
preparing inorganic particle dispersion liquid: mixing mica powder with the particle size of 0.5 mu m with ethylene glycol B, stirring for 20min at the rotating speed of 400r/min, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10wt%, wherein the addition amount of inorganic particles accounts for 0.2wt% of the mass of the slurry;
preparing a catalyst liquid: mixing antimony trioxide and ethylene glycol C according to a mass ratio of 1:20 to prepare a catalyst liquid, wherein the addition amount of the antimony trioxide accounts for 0.03 weight percent of the mass of the slurry;
s2 esterification: adding the slurry and the catalyst liquid into an esterification kettle, mixing, heating to 260 ℃, reacting at 150kPa for 5 hours, and adding the inorganic particle dispersion liquid after the reaction is completed to obtain a first material;
s3, pre-condensing: introducing the first material into a pre-polycondensation kettle, heating to 270 ℃, wherein the reaction pressure is 10kPa, the reaction time is 2 hours, and discharging excessive glycol in the reaction process to obtain a second material;
s4, final polycondensation: introducing the second material into a final polycondensation kettle, heating to 280 ℃, wherein the reaction pressure is 100Pa, the reaction time is 3h, and obtaining a melt, wherein the intrinsic viscosity of the melt is 0.7dL/g, the carboxyl end group content is 18.9mmol/kg, the melting point is 257 ℃, and the ash content is 0.4%; s5, film preparation:
casting sheet: delivering the melt to a die head in a film drawing process, casting to obtain a cast sheet, rapidly cooling the cast sheet by a cooling roller at 15 ℃, and simultaneously adopting a leeward device to air-cool the other surface of the cast sheet, wherein the temperature is 10 ℃ and the air speed is 10m/s;
and (3) longitudinal pulling: the cast sheet after cooling molding enters a longitudinal stretching machine, is preheated at 80 ℃, is heated to 100 ℃ through infrared rays, is stretched longitudinally for 3.5 times, and is cooled and shaped through a cooling roller at 15 ℃ to obtain a longitudinal pulling sheet;
transverse drawing, heat setting, cooling forming and corona: preheating a longitudinal pulling piece to 100 ℃, then heating to 120 ℃, transversely stretching by 3.5 times, then carrying out high-temperature shaping treatment at 210 ℃, then cooling and trimming at 60 ℃, and finally carrying out corona treatment and rolling to obtain the melt straight-pulling semitransparent solar backboard base film.
Example 2:
a production process of a melt straight-pull semitransparent solar backboard base film comprises the following steps:
s1, preparing:
preparing slurry: mixing ethylene glycol A and terephthalic acid, and uniformly stirring to prepare slurry, wherein the mol ratio of the terephthalic acid to the ethylene glycol A is 1:1.7;
preparing inorganic particle dispersion liquid: mixing silicon dioxide with the particle size of 0.5 mu m with ethylene glycol B, stirring for 20min at the rotating speed of 400r/min, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 50wt%, wherein the addition amount of inorganic particles accounts for 1wt% of the mass of the slurry;
preparing a catalyst liquid: mixing antimony trioxide and ethylene glycol C according to a mass ratio of 1:100 to prepare a catalyst liquid, wherein the addition amount of the antimony trioxide accounts for 0.04wt% of the mass of the slurry;
s2 esterification: adding the slurry and the catalyst liquid into an esterification kettle, mixing, heating to 265 ℃, reacting at 200kPa for 4 hours, and adding the inorganic particle dispersion liquid after the reaction is completed to obtain a first material;
s3, pre-condensing: introducing the first material into a pre-polycondensation kettle, heating to 275 ℃, reacting at 30kPa for 1.5 hours, and discharging excessive glycol in the reaction process to obtain a second material;
s4, final polycondensation: introducing the second material into a final polycondensation kettle, heating to 285 ℃, wherein the reaction pressure is 200Pa, the reaction time is 2h, and obtaining a melt, wherein the intrinsic viscosity of the melt is 0.77dL/g, the carboxyl end group content is 19.6mmol/kg, the melting point is 261 ℃, and the ash content is 0.6%; s5, film preparation:
casting sheet: delivering the melt to a die head in a film drawing process, casting to obtain a cast sheet, rapidly cooling the cast sheet by a cooling roller at 15 ℃, and simultaneously adopting a leeward device to air-cool the other surface of the cast sheet, wherein the temperature is 10 ℃ and the air speed is 10m/s;
and (3) longitudinal pulling: the cast sheet after cooling molding enters a longitudinal stretching machine, is preheated at 80 ℃, is heated to 100 ℃ through infrared rays, is stretched longitudinally for 3.5 times, and is cooled and shaped through a cooling roller at 15 ℃ to obtain a longitudinal pulling sheet;
transverse drawing, heat setting, cooling forming and corona: preheating a longitudinal pulling piece to 100 ℃, then heating to 120 ℃, transversely stretching by 3.5 times, then carrying out high-temperature shaping treatment at 210 ℃, then cooling and trimming at 60 ℃, and finally carrying out corona treatment and rolling to obtain the melt straight-pulling semitransparent solar backboard base film.
Example 3:
a production process of a melt straight-pull semitransparent solar backboard base film comprises the following steps:
s1, preparing:
preparing slurry: mixing ethylene glycol A and terephthalic acid, and uniformly stirring to prepare slurry, wherein the mol ratio of the terephthalic acid to the ethylene glycol A is 1:1.5;
preparing inorganic particle dispersion liquid: mixing talcum powder with the particle size of 0.5 mu m with glycol B, stirring for 20min at the rotating speed of 400r/min, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 30wt%, wherein the addition amount of inorganic particles accounts for 0.5wt% of the mass of the slurry;
preparing a catalyst liquid: mixing antimony trioxide and ethylene glycol C according to a mass ratio of 1:50 to prepare a catalyst liquid, wherein the addition amount of the antimony trioxide accounts for 0.035wt% of the mass of the slurry;
s2 esterification: adding the slurry and the catalyst liquid into an esterification kettle, mixing, heating to 262 ℃, reacting at 180kPa for 4.5 hours, and adding the inorganic particle dispersion liquid after the reaction is completed to obtain a first material;
s3, pre-condensing: introducing the first material into a pre-polycondensation kettle, heating to 272 ℃, reacting at 20kPa for 1.75 hours, and discharging excessive glycol in the reaction process to obtain a second material;
s4, final polycondensation: introducing the second material into a final polycondensation kettle, heating to 282 ℃, wherein the reaction pressure is 150Pa, the reaction time is 2.5h, and obtaining a melt, wherein the intrinsic viscosity of the melt is 0.8dL/g, the carboxyl end group content is 18.1mmol/kg, the melting point is 255 ℃, and the ash content is 0.3%; s5, film preparation:
casting sheet: delivering the melt to a die head in a film drawing process, casting to obtain a cast sheet, rapidly cooling the cast sheet by a cooling roller at 15 ℃, and simultaneously adopting a leeward device to air-cool the other surface of the cast sheet, wherein the temperature is 10 ℃ and the air speed is 10m/s;
and (3) longitudinal pulling: the cast sheet after cooling molding enters a longitudinal stretching machine, is preheated at 80 ℃, is heated to 100 ℃ through infrared rays, is stretched longitudinally for 3.5 times, and is cooled and shaped through a cooling roller at 15 ℃ to obtain a longitudinal pulling sheet;
transverse drawing, heat setting, cooling forming and corona: preheating a longitudinal pulling piece to 100 ℃, then heating to 120 ℃, transversely stretching by 3.5 times, then carrying out high-temperature shaping treatment at 210 ℃, then cooling and trimming at 60 ℃, and finally carrying out corona treatment and rolling to obtain the melt straight-pulling semitransparent solar backboard base film.
Example 4:
the difference from example 3 is that the inorganic particle dispersion was prepared by a different process.
Preparing inorganic particle dispersion liquid: mixing talcum powder with the particle size of 0.5 mu m with glycol B, stirring at the rotating speed of 400r/min for 20min, arranging an aerator at the bottom of the stirrer, introducing 100 ℃ water vapor while stirring, forming a large number of bubbles through the aerator, grinding and centrifuging, and finally heating and dehydrating to obtain inorganic particle dispersion liquid with the mass fraction of 30wt%, wherein the addition amount of inorganic particles is 0.5wt% of the mass of the slurry.
Example 5:
the difference from example 3 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.5. Mu.m.
Example 6:
the difference from example 3 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.1. Mu.m.
Example 7:
the difference from example 4 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.5. Mu.m.
Example 8:
the difference from example 4 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.1. Mu.m.
Example 9:
the difference from example 4 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.3. Mu.m.
Example 10:
the difference from example 4 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.05. Mu.m.
Example 11:
the difference from example 4 is that in the S3 precondensation, the reaction temperature is 278 ℃.
Example 12:
the difference from example 4 is that in the S3 precondensation, the reaction temperature is 283 ℃.
Example 13:
the difference from example 4 is that in the S3 precondensation, the reaction temperature is 280 ℃.
Examples 14 to 16:
the difference from examples 11 to 13 is that talc having a particle size of 0.5 μm is replaced with titanium dioxide having a particle size of 0.5. Mu.m.
Comparative example 1:
the difference from example 3 is that the preparation of the inorganic particle dispersion is not carried out, and the inorganic particles are added after the end of the esterification.
Comparative example 2:
the difference from example 3 is that the inorganic particles are added directly to the polyester melt without preparing the inorganic particle dispersion.
And (3) basic performance detection:
the translucent solar back sheet base films of examples 1 to 3 were subjected to thickness, tensile strength, elongation at break, heat shrinkage, light transmittance and water vapor transmittance measurements to determine whether or not they meet GB/T36289.1-2018 "insulating film for crystalline silicon solar cell module part 1: polyester film.
Thickness detection reference GB/T13542.2 part 2 of film for electrical insulation: the method described in test method, namely, the micrometer was used for measurement, and the obtained results are shown in Table 1.
Tensile Strength and elongation at break detection reference GB/T13542.2 part 2 of Electrical insulation film: the results obtained by the method described in test methods are shown in Table 1.
Thermal shrinkage test reference GB/T13542.2 part 2 of film for electrical insulation: the test conditions of the method described in test method are as follows: the heating temperature was 150℃and the heating time was 30 minutes, and the results are shown in Table 1.
The light transmittance was measured by a light transmittance tester, and the obtained results are shown in Table 1.
The method described in GB/T26253 method for measuring the water vapor transmittance of plastic films and sheets by infrared detector is used for detecting the water vapor transmittance, and the test conditions are as follows: the temperature was 38℃and the humidity was 90%, and the results are shown in Table 1.
Table 1 table for recording results of performance test of base film of semitransparent solar backboard
As can be seen from table 1: all performance detection results of the solar backboard base films prepared in the embodiments 1-3 accord with GB/T36289.1-2018 insulating film part 1 for crystalline silicon solar cell module: the standard recorded in the polyester film, and the tensile strength, the elongation at break and the thermal shrinkage rate are all obviously higher than the performance requirements, which indicates that the solar back plate base film has excellent comprehensive performance.
The solar back plate base film has excellent mechanical properties, and is mainly due to the reinforcing effect of inorganic particles, and the inorganic particles are uniformly dispersed in a melt.
And (3) dispersity comparison detection:
reference is made to GB/T13542.2 part 2 of film for electrical insulation: the tensile strength of the solar back sheet base films prepared in examples 3 to 16 and comparative examples 1 and 2 was measured by the method described in test methods to determine the degree of dispersion of inorganic particles in the production process, and the obtained results are shown in Table 2.
The mechanism is as follows: the dispersion distribution state of the inorganic particles in the polymer matrix has obvious influence on the mechanical property of the base film, and if the dispersion of the inorganic particles is poor and the dispersion is uneven in the melt, the mechanical property of the base film is reduced; in contrast, if the dispersibility of the inorganic particles is good, the mechanical properties of the base film are improved.
Table 2 table for recording results of tensile strength measurements of base film of translucent solar backboard
As can be seen from table 2:
1. as can be seen from the analysis of the detection results of examples 3 and 4, the tensile strength of the base film is slightly improved after the water vapor is introduced into the dispersion liquid, and the main reason is that the mechanical scattering effect of the water vapor on the inorganic particles makes the inorganic particles more uniformly distributed in the glycol solution, so that the inorganic particle dispersion liquid can be uniformly dispersed in the melt after the esterified substance is added into the inorganic particle dispersion liquid;
2. as can be seen from the analysis of the detection results of the combination of the example 3 and the example 5, the reinforcing effect of the titanium dioxide and the talcum powder in the polyester is close, so that the tensile strength results of the titanium dioxide and the talcum powder are close;
3. as can be seen from the analysis of the detection results of the combination of the embodiment 5 and the embodiment 6, the agglomeration phenomenon is more obvious after the particle size of the titanium dioxide is reduced to 100nm, and the titanium dioxide cannot be well dispersed by the glycol alone through mixing and stirring, so that the tensile strength is reduced;
4. as is clear from the analysis of the test results of example 4 and examples 5 and 7, the tensile strength of example 7 is slightly higher than that of example 4, because the effect of the titanium dioxide by the scattering of water vapor is good;
5. as is clear from the analysis of the test results of examples 4 and examples 7 to 9, the aeration step has good dispersing effect on titanium dioxide of 0.1 to 0.5 μm, and the particle size of the titanium dioxide is reduced between 0.1 and 0.5 μm, so that the reinforcing effect is improved, and the tensile strength of examples 8, 9 and 7 is improved in sequence, and the tensile strength of example 8 is obviously higher than that of example 4;
6. as is clear from the analysis of the detection results of example 4 and example 10, since the agglomeration phenomenon of nano-sized titanium dioxide is too serious, the dispersion effect of the aeration step on titanium dioxide smaller than 0.1 μm is not good, and thus the tensile strength of example 10 is rather lowered compared with example 4;
7. as is clear from the analysis of the detection results of examples 4 and examples 11 to 16, the effect of dispersing inorganic particles in the second material, particularly titanium dioxide as inorganic particles, can be further improved by appropriately increasing the reaction temperature of the pre-polycondensation;
8. analysis of the detection results in combination with example 3 and comparative examples 1 and 2 shows that the pretreatment process of the inorganic particles can effectively improve the dispersibility of the inorganic particles, and the internal addition mode is more beneficial to the dispersion of the inorganic particles in the melt.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (10)
1. The melt straight-pull semitransparent solar backboard base film is characterized by being prepared from the following raw materials in parts by weight: ethylene glycol a, terephthalic acid, catalyst, and inorganic particles;
the mol ratio of the terephthalic acid to the ethylene glycol A is 1 (1.2-1.7), the addition amount of the catalyst accounts for 0.03-0.04wt% of the total mass of the ethylene glycol A and the terephthalic acid, and the addition amount of the inorganic particles accounts for 0.2-1wt% of the total mass of the ethylene glycol A and the terephthalic acid;
the inorganic particles are pretreated before being added, and the specific process is as follows: firstly mixing inorganic particles with glycol B, stirring, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10-50 wt%.
2. The melt-blown translucent solar back sheet base film of claim 1, wherein: the inorganic particles include one or more of mica, barium sulfate, kaolin, titanium dioxide, calcium carbonate, silica, talc, and montmorillonite.
3. The melt-blown translucent solar back sheet base film of claim 1, wherein: the pretreatment process of the inorganic particles further comprises an aeration step and a dehydration step, wherein the aeration step and the stirring step are carried out simultaneously, the dehydration step is arranged after the centrifugation step, and the aeration step is used for introducing water vapor in an aeration mode.
4. A melt-down translucent solar back sheet base film according to claim 3, characterized in that: the inorganic particles are titanium dioxide.
5. The melt-blown translucent solar back sheet base film of claim 4, wherein: the particle size of the inorganic particles is 0.1-0.5 μm.
6. The melt-blown translucent solar back sheet base film of claim 1, wherein: the catalyst is antimony trioxide.
7. A process for producing a melt-blown translucent solar back sheet base film according to claim 1, comprising the steps of:
s1, preparing:
preparing slurry: mixing ethylene glycol A and terephthalic acid to prepare slurry;
preparing inorganic particle dispersion liquid: mixing inorganic particles with ethylene glycol B, stirring, grinding and centrifuging to obtain inorganic particle dispersion liquid with the mass fraction of 10-50 wt%;
preparing a catalyst liquid: mixing a catalyst and ethylene glycol C according to the mass ratio of 1 (20-100) to prepare a catalyst liquid;
s2 esterification: mixing the slurry with the catalyst liquid, heating to 260-265 ℃, reacting at 150-200kPa for 4-5 hours, and adding the inorganic particle dispersion liquid after the reaction is completed to obtain a first material;
s3, pre-condensing: heating the first material to 270-283 ℃, wherein the reaction pressure is 10-30kPa, the reaction time is 1.5-2h, and discharging excessive glycol in the reaction process to obtain a second material;
s4, final polycondensation: heating the second material to 280-285 ℃, wherein the reaction pressure is 100-200Pa, and the reaction time is 2-3h, so as to obtain a melt;
s5, film preparation: and (3) carrying out casting, longitudinal drawing, transverse drawing, heat setting, cooling forming and corona on the melt to obtain the melt straight-drawing semitransparent solar backboard base film.
8. The process for producing a melt-drawn semitransparent solar backsheet base film according to claim 7, wherein: the inorganic particles are titanium dioxide.
9. The process for producing a melt-drawn semitransparent solar backsheet base film according to claim 8, wherein: in the S3 pre-polycondensation, the reaction temperature is 278-283 ℃.
10. The process for producing a melt-drawn semitransparent solar backsheet base film according to claim 7, wherein: in the S4 final polycondensation, the intrinsic viscosity of the melt is 0.7-0.8dL/g.
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