CN117070115A - Moisture-heat aging resistant photovoltaic backboard base film and preparation method and preparation device thereof - Google Patents
Moisture-heat aging resistant photovoltaic backboard base film and preparation method and preparation device thereof Download PDFInfo
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- CN117070115A CN117070115A CN202311043028.9A CN202311043028A CN117070115A CN 117070115 A CN117070115 A CN 117070115A CN 202311043028 A CN202311043028 A CN 202311043028A CN 117070115 A CN117070115 A CN 117070115A
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- 230000032683 aging Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 142
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007788 liquid Substances 0.000 claims abstract description 73
- 230000007246 mechanism Effects 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000003756 stirring Methods 0.000 claims abstract description 48
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000002834 transmittance Methods 0.000 claims abstract description 34
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- 239000003999 initiator Substances 0.000 claims abstract description 19
- -1 vinyl modified silica sol Chemical class 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 11
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical group C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- 238000009434 installation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000010345 tape casting Methods 0.000 claims description 3
- 230000001680 brushing effect Effects 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 abstract description 11
- 239000004925 Acrylic resin Substances 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 64
- 230000007423 decrease Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000005341 toughened glass Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 238000005191 phase separation Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Abstract
The application discloses a wet heat aging resistant photovoltaic backboard base film, a preparation method and a preparation device thereof; the raw materials of the photovoltaic backboard base film comprise, by mol, 14-22 parts of tetraethoxysilane, 2-4 parts of vinyl triethoxysilane, 16-26 parts of deionized water, 96-156 parts of ethanol, 100-200 parts of acrylic acid, 0.4-0.8 part of initiator and 0.05-0.1 part of cross-linking agent. The preparation method comprises a first step for preparing vinyl modified silica sol, a second step for preparing monomer prepolymer liquid of acrylic acid and a third step for preparing acrylic resin. The preparation device comprises a first reaction kettle, a second reaction kettle, a heating mechanism, a liquid dropping mechanism and two stirring mechanisms. The photovoltaic backboard base film has excellent light transmittance and water resistance, and simultaneously has better weather resistance, better mechanical properties such as wear resistance, impact strength, flexibility and the like.
Description
Technical Field
The application relates to the technical field of photovoltaic backboard base film materials, in particular to a photovoltaic backboard base film resistant to wet heat aging, a preparation method and a preparation device thereof.
Background
Currently, solar photovoltaic power generation is one of the important points of new energy development. Solar photovoltaic power generation relies on solar cells to directly convert light energy into electrical energy. Solar cells, also known as "photovoltaic cells" or "solar chips", are a type of semiconductor thin film. The packaging material of traditional photovoltaic module adopts toughened glass to encapsulate mostly, but toughened glass's weight is big, and is higher to bearing structure's requirement to the degree of difficulty and the installation cost of engineering construction have been increased.
In the prior art, in order to solve the problem of light weight of a photovoltaic module, a thermosetting powder coating is generally used for coating the photovoltaic module, so as to form a photovoltaic back plate base film for replacing toughened glass. However, the conventional photovoltaic back sheet base film has poor weather resistance and insufficient mechanical properties, so that the service life of the photovoltaic module is shortened.
Disclosure of Invention
The application aims to provide a photovoltaic back plate base film resistant to wet heat aging, and a preparation method and a preparation device thereof.
In order to achieve the above purpose, the application adopts the following technical scheme: the raw materials of the wet heat aging resistant photovoltaic back plate base film comprise, by mol, 14-22 parts of ethyl orthosilicate, 2-4 parts of vinyl triethoxysilane, 16-26 parts of deionized water, 96-156 parts of ethanol, 100-200 parts of acrylic acid and 0.4-0.8 part of an initiator
0.05-0.1 part of cross-linking agent.
Preferably, the molar mass part of the tetraethoxysilane is 18 parts, and the molar mass part of the vinyltriethoxysilane is 3 parts.
Preferably, the molar mass part of the ethanol is 126 parts, and the molar mass part of the deionized water is 21 parts.
Preferably, the molar mass part of the acrylic acid is 150 parts.
Preferably, the initiator is azobisisobutyronitrile, and the molar mass part of the initiator is 0.6 part.
Preferably, the cross-linking agent is diallyl phthalate, and the molar mass parts of the cross-linking agent is 0.075 parts.
The application also provides a preparation method of the wet heat aging resistant photovoltaic backboard base film, which comprises a first step, a second step, a third step and a fourth step.
The first step: firstly, adding the tetraethoxysilane, the vinyl triethoxysilane, the deionized water and the ethanol into a first reaction kettle, and stirring and mixing uniformly through a stirring mechanism; then, adding an acidic catalyst into the first reaction kettle to adjust the pH to 3.2-3.6; and then starting a heating mechanism in the first reaction kettle to heat, wherein the heating temperature is 45-55 ℃, stirring by the stirring mechanism during heating until the mixed solution is completely changed to a homogeneous transparent sol, and preparing the vinyl modified silica sol when the light transmittance of a sol system is not obviously changed.
The second step: and fully dissolving the acrylic acid, the initiator and the cross-linking agent in a mixed solvent of ethyl acetate and absolute ethyl alcohol, wherein the mass ratio of the ethyl acetate to the absolute ethyl alcohol is 1:4, so that a monomer pre-polymerization liquid is formed, and the mass fraction of the acrylic acid in the monomer pre-polymerization liquid is 20%.
The third step: firstly, filling nitrogen into the first reaction kettle to discharge air in the first reaction kettle, and then heating the vinyl modified silica sol to 74-76 ℃ through the heating mechanism; and then, dropwise adding the monomer prepolymerization liquid into the reaction kettle through a dropping mechanism, and reacting at constant temperature for 3-4 hours to obtain the raw material of the photovoltaic backboard base film.
The fourth step: and coating the raw materials of the photovoltaic back plate base film on the photovoltaic module through a brushing method, a spraying method, a dipping method or a knife coating method to obtain the photovoltaic back plate base film.
The application also provides a preparation device of the wet heat aging resistant photovoltaic backboard base film, which comprises a first reaction kettle, a second reaction kettle, a heating mechanism, a liquid dropping mechanism and two stirring mechanisms; the first reaction kettle is provided with a first feed inlet, a first discharge outlet, an air inlet and an air outlet, and the second reaction kettle is provided with a second feed inlet and a second discharge outlet; the heating mechanism is arranged in the first reaction kettle, and the two stirring mechanisms are respectively arranged in the first reaction kettle and the second reaction kettle; the liquid dropping mechanism is arranged at the inner top of the first reaction kettle and is communicated with the second discharge hole, so that the liquid dropping mechanism is used for dropping the monomer prepolymer in the second reaction kettle into the first reaction kettle.
Preferably, the upper ends of the first reaction kettle and the second reaction kettle are respectively provided with a mounting hole for mounting the stirring mechanism in a penetrating way up and down; the stirring mechanism comprises an installation box, a fixed shaft, a rotating shaft, a shaft sleeve, an upper blade, a lower blade, a middle blade, a driving assembly and a linkage assembly; the fixed shaft coaxially penetrates through the mounting hole, and is fixed to the first reaction kettle or the second reaction kettle; the upper end of the shaft sleeve is arranged on the mounting box, and the shaft sleeve and the mounting box are coaxially and rotatably arranged outside the lower end of the fixed shaft; the upper blade and the lower blade are arranged on the shaft sleeve at intervals up and down, the stirring surface of the upper blade is inclined downwards, and the stirring surface of the lower blade is inclined upwards; the upper end of the rotating shaft is rotatably arranged in the mounting box, the rotating shaft is suitable for being rotatably connected with the upper blade and/or the lower blade, and the rotating shaft is parallel to the shaft sleeve; the middle blade is arranged on the rotating shaft and is positioned between the upper blade and the lower blade; the driving component is arranged on the first reaction kettle or the second reaction kettle and is used for driving the corresponding installation box to rotate; the linkage assembly is arranged in the installation box, when the installation box rotates, the fixed shaft forces the rotating shaft to rotate through the linkage assembly, and the rotating direction of the rotating shaft is suitable for being opposite to the rotating direction of the shaft sleeve.
Preferably, a seal is formed between the shaft sleeve and the fixed shaft, the fixed shaft is of a hollow structure, and the first feed inlet and the second feed inlet are respectively formed in the corresponding fixed shaft; the upper end of the fixed shaft is communicated with a liquid mixing tank, a plurality of pipe connectors are arranged on the outer side wall of the liquid mixing tank along the circumferential direction at intervals, and each pipe connector is tangent to the inner side wall of the liquid mixing tank.
Preferably, the dropping mechanism comprises a dropping box, a buffer tank, a first connecting pipe, a second connecting pipe, a pump body and a valve body; the liquid drop box is arranged at the inner top of the first reaction kettle, a liquid storage cavity is arranged in the liquid drop box, and a plurality of liquid drop heads communicated with the liquid storage cavity are arranged at equal intervals on the lower end surface of the liquid drop box; the buffer tank is arranged above the first reaction kettle, and is provided with a liquid inlet and a liquid outlet; the two ends of the first connecting pipe are respectively communicated with the second discharging port and the liquid inlet, and the pump body is arranged on the first connecting pipe, so that the monomer prepolymer is pumped into the buffer tank through the pump body; the two ends of the second connecting pipe are respectively communicated with the liquid outlet and the liquid storage cavity, and the valve body is arranged in the second connecting pipe, so that the valve body is opened and closed at intervals, and then the monomer prepolymer is dripped into the first reaction kettle through the dripper.
Compared with the prior art, the application has the beneficial effects that: the photovoltaic backboard base film has excellent light transmittance and water resistance, better weather resistance, better mechanical properties such as wear resistance, impact strength and flexibility, and the like, thereby being beneficial to prolonging the service life of the photovoltaic module.
Drawings
Fig. 1 is a schematic diagram of a device for preparing a photovoltaic back sheet base film according to the present application.
Fig. 2 is an enlarged view of the first reaction vessel in fig. 1 provided by the present application.
Fig. 3 is an enlarged view of the stirring mechanism of fig. 1 provided by the present application.
Fig. 4 is an exploded view of the stirring mechanism of fig. 3 provided by the present application.
Fig. 5 is an enlarged view of the linkage assembly of fig. 4 at another view angle provided by the present application.
Fig. 6 is a left side view of the stirring mechanism of fig. 3 provided by the present application.
Fig. 7 is a cross-sectional view taken along line A-A in fig. 6, provided by the present application.
Fig. 8 is an enlarged view of a portion of the fig. 7 article at I provided by the present application.
Fig. 9 is an enlarged view of part II in fig. 7 provided by the present application.
Fig. 10 is a cross-sectional view taken along line B-B of fig. 7 provided by the present application.
Fig. 11 is an enlarged view of the mixing tank of fig. 1 provided by the application.
Fig. 12 is a cross-sectional view of the mixing tank of fig. 11 provided by the application.
Fig. 13 is an enlarged view of the drip mechanism of fig. 1 provided by the present application.
Fig. 14 is an enlarged view of the drip chamber of fig. 13 at another viewing angle provided by the present application.
In the figure: 1. a first reaction kettle; 11. a first feed port; 12. a first discharge port; 13. an air inlet; 14. an air outlet; 15. a mounting hole; 16. a window; 2. a second reaction kettle; 21. a second feed inlet; 22. a second discharge port; 3. a heating mechanism; 4. a dropping mechanism; 41. a drip box; 411. a drip head; 42. a buffer tank; 43. a first connection pipe; 44. a second connection pipe; 45. a pump body; 46. a valve body; 5. a stirring mechanism; 51. a mounting box; 52. a fixed shaft; 521. a shaft fixing frame; 53. a rotating shaft; 54. a shaft sleeve; 55. an upper blade; 56. a lower blade; 57. an intermediate vane; 58. a drive assembly; 581. a motor; 582. a transmission gear; 583. a drive sleeve; 59. a linkage assembly; 591. a first gear; 592. a second gear; 593. a third gear; 594. a mounting shaft; 6. a liquid mixing tank; 61. a tube interface; 100. a ball bearing; 200. a thrust bearing.
Detailed Description
The present application will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
In the description of the present application, it should be noted that, for the azimuth words such as terms "center", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc., the azimuth and positional relationships are based on the azimuth or positional relationships shown in the drawings, it is merely for convenience of describing the present application and simplifying the description, and it is not to be construed as limiting the specific scope of protection of the present application that the device or element referred to must have a specific azimuth configuration and operation. The terms first, second and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. The terms "comprises" and "comprising," along with any variations thereof, in the description and claims, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The embodiment of the application provides a wet heat aging resistant photovoltaic back sheet base film, which comprises, by mol, 14-22 parts of ethyl orthosilicate, 2-4 parts of vinyl triethoxysilane, 16-26 parts of deionized water, 96-156 parts of ethanol, 100-200 parts of acrylic acid, 0.4-0.8 part of an initiator and 0.05-0.1 part of a cross-linking agent.
The application also provides a preparation method of the wet heat aging resistant photovoltaic backboard base film, which comprises a first step, a second step, a third step and a fourth step.
A first step of: firstly, adding tetraethoxysilane, vinyl triethoxysilane, deionized water and ethanol into a first reaction kettle 1, and uniformly stirring and mixing by a stirring mechanism 5; then, an acidic catalyst is added into the first reaction kettle 1 to adjust the pH to 3.2-3.6; and then starting a heating mechanism 3 in the first reaction kettle 1 to heat, wherein the heating temperature is 45-55 ℃, and stirring by a stirring mechanism 5 during heating until the mixed solution is completely changed to a homogeneous transparent sol, and preparing the vinyl modified silica sol when the light transmittance of the sol system is not obviously changed.
And a second step of: and fully dissolving the acrylic acid, the initiator and the cross-linking agent in a mixed solvent of ethyl acetate and absolute ethyl alcohol, wherein the mass ratio of the ethyl acetate to the absolute ethyl alcohol is 1:4, so that a monomer pre-polymerization liquid is formed, and the mass fraction of the acrylic acid in the monomer pre-polymerization liquid is 20%.
And a third step of: firstly, filling nitrogen into a first reaction kettle 1 to discharge air in the first reaction kettle 1, and heating vinyl modified silica sol to 74-76 ℃ through a heating mechanism 3; and then, dripping the monomer prepolymer into a reaction kettle through a dripping mechanism 4, and reacting for 3-4 hours at constant temperature to obtain the raw material of the photovoltaic backboard base film.
Fourth step: and (3) coating the raw materials of the photovoltaic back plate base film on the photovoltaic module through a brush coating method or a spray coating method or a dip coating method or a knife coating method to obtain the photovoltaic back plate base film.
Referring to fig. 1, the application also provides a preparation device of the photovoltaic backboard base film resistant to damp-heat aging, which comprises a first reaction kettle 1, a second reaction kettle 2, a heating mechanism 3, a dropping mechanism 4 and two stirring mechanisms 5; the first reaction kettle 1 is provided with a first feed inlet 11, a first discharge outlet 12, an air inlet 13 and an air outlet 14, and the second reaction kettle 2 is provided with a second feed inlet 21 and a second discharge outlet 22; the heating mechanism 3 is arranged on the first reaction kettle 1, and the two stirring mechanisms 5 are respectively arranged on the first reaction kettle 1 and the second reaction kettle 2; the dropping mechanism 4 is arranged at the inner top of the first reaction kettle 1, and the dropping mechanism 4 is communicated with the second discharge hole 22, so that the monomer prepolymer in the second reaction kettle 2 is dripped into the first reaction kettle 1.
The working principle of the preparation device is as follows: (1) On the premise of closing a first feed port on the first reaction kettle 1, various raw materials (namely ethyl orthosilicate, vinyl triethoxysilane, deionized water, ethanol and the like) are conveniently added into the first reaction kettle 1 through a first feed port 11 on the first reaction kettle 1, the various raw materials are uniformly stirred through a stirring mechanism 5 in the first reaction kettle 1, and the mixed liquid in the first reaction kettle 1 is heated through a heating mechanism 3, so that the vinyl modified silica sol can be prepared.
(2) On the premise of closing the second discharge port 22 on the second reaction kettle 2, various raw materials (namely acrylic acid, an initiator, a cross-linking agent, ethyl acetate, absolute ethyl alcohol and the like) are conveniently added into the second reaction kettle 2 through the second feed port 21 on the second reaction kettle 2, and various raw materials are uniformly stirred through the stirring mechanism 5 in the second reaction kettle 2, so that the monomer prepolymer can be prepared.
(3) The nitrogen is filled into the first reaction kettle 1 through the air inlet 13, and the air in the first reaction kettle 1 is discharged through the air outlet 14, so that the vinyl modified silica sol in the first reaction kettle 1 is subjected to the next reaction under the protection of the nitrogen. Then, the stirring mechanism 5 in the first reaction kettle 1 is continuously started to stir, and the vinyl modified silica sol reaches a preset temperature (namely 74-76 ℃) through the heating mechanism 3; then, the monomer prepolymer in the second reaction kettle 2 is dripped into the first reaction kettle 1 through a dripping mechanism 4, and the constant temperature reaction is continued for 3-4 hours after dripping, so that the photovoltaic backboard base film can be prepared, and the acrylic resin can be discharged through opening the first discharge hole 12 on the first reaction kettle 1.
Referring to fig. 2 to 4 and fig. 6 to 7, in some embodiments of the present application, mounting holes 15 (as shown in fig. 2) for mounting the stirring mechanism 5 are vertically formed at the upper ends of the first reaction kettle 1 and the second reaction kettle 2; as shown in fig. 3 and 4, the stirring mechanism 5 includes a mounting box 51, a fixed shaft 52, a rotating shaft 53, a sleeve 54, an upper blade 55, a lower blade 56, an intermediate blade 57, a driving assembly 58, and a linkage assembly 59; the fixed shaft 52 coaxially penetrates through the mounting hole 15, and the fixed shaft 52 is fixed on the first reaction kettle 1 or the second reaction kettle 2; the upper end of the shaft sleeve 54 is arranged on the mounting box 51, and the shaft sleeve 54 and the mounting box 51 are coaxially and rotatably arranged outside the lower end of the fixed shaft 52; the upper blade 55 and the lower blade 56 are provided at an upper-lower interval in the boss 54, the stirring surface of the upper blade 55 is inclined downward, and the stirring surface of the lower blade 56 is inclined upward (as shown in fig. 6); the upper end of the rotating shaft 53 is rotatably provided to the mounting box 51, the rotating shaft 53 is adapted to be rotatably connected to the upper blade 55 and/or the lower blade 56, and the rotating shaft 53 is parallel to the boss 54; the intermediate vane 57 is provided to the rotation shaft 53, and the intermediate vane 57 is located between the upper vane 55 and the lower vane 56; the driving component 58 is arranged on the first reaction kettle 1 or the second reaction kettle 2, and the driving component 58 is used for driving the corresponding installation box 51 to rotate; the linkage assembly 59 is disposed inside the mounting box 51, and when the mounting box 51 rotates, the fixed shaft 52 forces the rotation shaft 53 to rotate through the linkage assembly 59, and the rotation direction of the rotation shaft 53 is adapted to be opposite to the rotation direction of the shaft sleeve 54.
The working principle of the stirring mechanism 5 is as follows: (1) As shown in fig. 3 and 4, when the driving unit 58 drives the mounting box 51 to rotate, the boss 54, the upper blade 55, the lower blade 56, the rotation shaft 53, and the intermediate blade 57 revolve around the fixed shaft 52; at the same time, the fixed shaft 52 forces the rotation shaft 53 to rotate through the linkage assembly 59, so as to drive the intermediate blade 57 to synchronously rotate along with the rotation shaft 53.
(2) Further, as shown in fig. 6, the stirring surface of the upper blade 55 is inclined downward, and the stirring surface of the lower blade 56 is inclined upward; therefore, when the upper blade 55 and the lower blade 56 revolve around the fixed shaft 52, the upper blade 55 pushes the mixed solution to move downward while pushing the mixed solution to perform a circular motion, so that the upper liquid in the first reaction tank 1 or the second reaction tank 2 moves downward, i.e., in a direction approaching the middle blade 57; similarly, the lower blade 56 pushes the mixed solution to move upwards while pushing the mixed solution to perform circular motion, so that the lower liquid in the first reaction kettle 1 or the second reaction kettle 2 moves upwards, that is, moves towards the direction close to the middle blade 57, so that the upper, middle and lower liquid in the first reaction kettle 1 or the second reaction kettle 2 is uniformly stirred by the middle blade 57. Therefore, through the mutual cooperation among the upper blade 55, the middle blade 57 and the lower blade 56, the solution in the first reaction kettle 1 or the second reaction kettle 2 can be stirred uniformly, the stirring efficiency is higher, the reaction time is shortened, and the production efficiency is improved.
(3) Further, since the upper blade 55 and the lower blade 56 push the mixed solution to perform a circular motion in the same direction when revolving, that is, the rotation direction of the mixed solution is the same as that of the shaft housing 54. Therefore, when the rotation direction of the rotation shaft 53 (i.e., the intermediate blade 57) is opposite to the rotation direction of the shaft housing 54, the intermediate blade 57 forces the mixed solution to reversely rotate, so that the mixing speed of the mixed solution can be increased, and the stirring efficiency can be further improved.
The rotatable mounting manner between the rotation shaft 53 and the mounting box 51 is not limited in the present application, and for example, as shown in fig. 8, the rotation shaft 53 is rotatably mounted inside the mounting box 51 by two ball bearings 100; meanwhile, the rotation shaft 53 is rotatably mounted to the mounting box 51 through two thrust bearings 200, thereby restricting displacement of the mounting shaft 594 in the axial direction.
The application is not limited to the rotatable mounting manner among the mounting box 51, the sleeve 54 and the fixed shaft 52, and for example, as shown in fig. 9, the mounting box 51 is rotatably mounted on the fixed shaft 52 by two ball bearings 100; meanwhile, the sleeve 54 is rotatably mounted to the fixed shaft 52 through two thrust bearings 200, thereby restricting axial displacement between the sleeve 54 (i.e., the mounting case 51) and the fixed shaft 52.
The rotatable manner between the rotating shaft 53 and the upper blade 55 and/or the lower blade 56 is not limited in the present application, for example, as shown in fig. 4, a circular hole for adapting to the rotating shaft 53 is provided on the upper blade 55 and/or the lower blade 56, and rotation of the rotating shaft 53 is adapted through the circular hole, thereby improving shafting stability of rotation of the rotating shaft 53.
The specific structure of the linkage assembly 59 is not limited by the present application, and only one specific structure is provided below for reference: as shown in fig. 5, the linkage assembly 59 includes a first gear 591, a second gear 592, a third gear 593, and a mounting shaft 594; the first gear 591 is coaxially fixed to the fixed shaft 52, and the third gear 593 is coaxially fixed to the rotating shaft 53; the second gear 592 is rotatably disposed on the mounting box 51 by a mounting shaft 594, and the second gear 592 is engaged with the first gear 591 and the third gear 593, respectively. As shown in fig. 10, when the drive mounting box 51 rotates clockwise, the upper blade 55, the lower blade 56, the rotation shaft 53, the second gear 592, and the third gear 593 revolve around the fixed shaft 52; since the fixed shaft 52 is fixed to the first gear 591 so as to be stationary, the second gear 592 rolls clockwise along the first gear 591 while revolving, i.e., the second gear 592 rotates clockwise, thereby forcing the third gear 593 (i.e., the rotation shaft 53) to rotate counterclockwise, and further causing the rotation direction of the rotation shaft 53 (i.e., the intermediate blade 57) to be opposite to the rotation direction of the boss 54 (i.e., the upper blade 55 and the lower blade 56).
The specific structure of the drive assembly 58 is not limited by the present application, and only one specific structure is provided below for reference: as shown in fig. 3 and 4, the drive assembly 58 includes a motor 581, a transfer gear 582, and a drive sleeve 583; the driving sleeve 583 is rotatably arranged between the mounting hole 15 and the fixed shaft 52, and the lower end of the driving sleeve 583 is fixed at the upper end of the mounting box 51; the motor 581 is arranged at the outer top of the reaction kettle, and an output shaft of the motor 581 is connected with a driving sleeve 583 through a transmission gear 582.
The fixing manner of the fixing shaft 52 is not limited in the present application, and the following only provides a specific structure for reference: as shown in fig. 3 and 4, the upper end of the fixed shaft 52 is fixed to a shaft fixing frame 521, and the shaft fixing frame 521 is mounted (e.g., welded) to the outer top of the first reaction tank 1 or the second reaction tank 2.
Referring to fig. 7, in some embodiments of the present application, a seal is formed between the sleeve 54 and the fixed shaft 52, the fixed shaft 52 has a hollow structure, and the first and second feed ports 11 and 21 are respectively formed inside the corresponding fixed shaft 52. That is, the first feed port 11 on the first reaction vessel 1 may be formed through the hollow structure of the fixed shaft 52 on the first reaction vessel 1, so that various corresponding raw materials may be added through the first feed port 11, and further, the raw materials may directly reach the inner bottom of the first reaction vessel 1 through the lower end of the shaft sleeve 54, so as to avoid splashing of the liquid in the first reaction vessel 1 when the raw materials are added. Similarly, the second feeding hole 21 on the second reaction kettle 2 can be formed through the hollow structure of the fixing shaft 52 on the second reaction kettle 2, so that various corresponding raw materials can be added through the second feeding hole 21, and further the raw materials can directly reach the inner bottom of the second reaction kettle 2 through the lower end of the shaft sleeve 54, so that the splashing phenomenon of liquid in the second reaction kettle 2 during the raw material adding process can be avoided.
Referring to fig. 1, 11 and 12, since more than one raw material is added, the upper end of the first fixed shaft 52 is communicated with the mixed liquid tank 6, and the outer side wall of the mixed liquid tank 6 is provided with a plurality of pipe interfaces 61 at intervals along the circumferential direction, and each pipe interface 61 is tangent to the inner side wall of the mixed liquid tank 6. The outer ends of the pipe connectors 61 are respectively communicated with the input pipelines of the corresponding raw materials, and after the valves of the corresponding raw material pipelines are opened, the raw materials can enter the liquid mixing tank 6 along the tangential direction of the inner side wall of the liquid mixing tank 6, so that the raw materials do circular motion in the liquid mixing tank 6, various raw materials can be primarily mixed in the liquid mixing tank 6, and the efficiency of subsequent stirring uniformity is improved. Of course, generally, the upper ends of the first reaction vessel 1 and the second reaction vessel 2 are provided with openable and closable windows 16 (as shown in fig. 1 and 2), and the reaction conditions in the first reaction vessel 1 and the second reaction vessel 2 can be easily observed through the windows 16, and various raw materials can be added by opening the windows 16.
Referring to fig. 1, 13 and 14, in some embodiments of the present application, the drip mechanism 4 includes a drip box 41, a buffer tank 42, a first connection tube 43, a second connection tube 44, a pump body 45 and a valve body 46; the drip box 41 is arranged at the inner top of the first reaction kettle 1, a liquid storage cavity is arranged in the drip box 41, and a plurality of drip heads 411 (shown in fig. 14) communicated with the liquid storage cavity are arranged at equal intervals on the lower end surface of the drip box 41; the buffer tank 42 is arranged above the first reaction kettle 1, and a liquid inlet and a liquid outlet are arranged on the buffer tank 42; the two ends of the first connecting pipe 43 are respectively communicated with the second discharge port 22 and the liquid inlet, and the pump body 45 is arranged on the first connecting pipe 43, so that the monomer prepolymer is pumped into the buffer tank 42 through the pump body 45; both ends of the second connection pipe 44 are respectively connected to the liquid outlet and the liquid storage cavity, and the valve body 46 is arranged in the second connection pipe 44, so that the monomer prepolymer is dripped into the first reaction kettle 1 through the interval opening and closing valve body 46 and the dripper 411.
The working principle of the dropping mechanism 4 is as follows: when the pump body 45 is opened, the monomer prepolymer in the second reaction kettle 2 can be pumped into the buffer tank 42 through the first connecting pipe 43 by the pump body 45; with the pump body 45 closed, the monomer prepolymer liquid in the buffer tank 42 cannot flow back into the second reaction tank 2. Since the buffer tank 42 is located above the first reaction vessel 1 (i.e., the drip box 41), when the valve body 46 is opened, the monomer prepolymer in the buffer tank 42 is fed into the liquid storage chamber through the second connecting pipe 44, so as to be dripped into the first reaction vessel 1 through each drip head 411; when the valve body 46 is closed, the monomer pre-polymer liquid in the liquid storage chamber cannot drip from the drip head 411. That is, the monomer pre-polymerization liquid may be dropped into the first reaction tank 1 by opening and closing the valve body 46 at intervals by the liquid dropping head 411; wherein the rate of drip can be controlled by controlling the frequency of the spaced closure bodies 46. The valve body 46 is preferably an automatically controlled valve, such as a solenoid valve, for automatically opening and closing.
Example 1
(1) Adding 12 parts of tetraethoxysilane, 3 parts of vinyl triethoxysilane, 21 parts of deionized water and 126 parts of ethanol into the first reaction kettle 1 according to the molar mass parts, and uniformly stirring through a stirring mechanism 5 in the first reaction kettle 1; next, an acid washing catalyst (hydrochloric acid) was added to the first reaction tank 1 to adjust the pH to 3.6; and then starting a heating mechanism 3 in the first reaction kettle 1 to heat, controlling the heating temperature to be in a range of 45-55 ℃ relatively constant, and preparing the vinyl modified silica sol when the sol is stirred to be homogeneous transparent sol and the light transmittance of the sol system is not changed obviously.
(2) Firstly, adding a mixed solvent of ethyl acetate and absolute ethyl alcohol in a mass ratio of 1:4 into a second reaction kettle 2; then, 150 parts of acrylic acid, 0.6 part of initiator (azobisisobutyronitrile) and 0.075 part of crosslinking agent (diallyl phthalate) were added to the second reaction vessel 2 by massaging mass parts, and stirred by a stirring mechanism 5 in the second reaction vessel 2, so that they were sufficiently dissolved to form a monomer prepolymer solution, and the mass fraction of acrylic acid in the monomer prepolymer solution was ensured to be 20%.
(3) Firstly, fully nitrogen is introduced into a first reaction kettle 1 through an air inlet 13, and air in the first reaction kettle 1 is discharged through an air outlet, so that the vinyl modified silica sol in the first reaction kettle 1 is heated to 74-76 ℃ through a heating mechanism 3 under the protection of nitrogen; and then, dripping the monomer prepolymerization liquid in the second reaction kettle 2 into the first reaction kettle 1 through a dripping mechanism 4, and reacting at constant temperature for 3-4 hours to obtain the raw material of the photovoltaic backboard base film.
(4) Spraying the raw materials of the photovoltaic backboard base film on an experimental glass plate, and detecting after drying.
Examples 2 to 7
Examples 2 to 7 differ from example one in that the molar mass parts of ethyl orthosilicate are 14 parts, 16 parts, 18 parts, 20 parts, 22 parts and 24 parts, respectively.
The properties of the photovoltaic backsheet base films produced in examples 1 to 7 are shown in table 1 below.
As is clear from examples 1 to 7, as the amount of ethyl orthosilicate increases, the light transmittance of the coating film of the acrylic resin gradually becomes better, while the water resistance gradually becomes worse (i.e., the water solubility of the coating film gradually increases).
Example 8
Example 8 is different from example 1 in that the molar mass part of tetraethyl orthosilicate is 18 parts and the molar mass part of vinyltriethoxysilane is 1.5 parts.
Examples 9 to 14
Examples 9 to 14 differ from example 8 in that the molar mass parts of vinyltriethoxysilane are 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts and 4.5 parts, respectively.
The properties of the photovoltaic backsheet base films produced in examples 8 to 14 are shown in table 2 below.
| Transmittance/% | Water solubility/% | |
| Example 8 | 98.8 | 35.1 |
| Example 9 | 98.3 | 24.5 |
| Example 10 | 97.9 | 18.3 |
| Example 11 | 97.2 | 6.3 |
| Example 12 | 96.4 | 5.4 |
| Example 13 | 95.2 | 5.0 |
| Example 14 | 94.7 | 4.7 |
As is clear from examples 8 to 14, as the amount of vinyltriethoxysilane increases, the film light transmittance of the acrylic resin gradually becomes worse, and the water resistance gradually becomes better (i.e., the film water solubility gradually decreases).
Thus, examples 1 to 14 show that as the fraction of tetraethoxysilane is gradually reduced or the fraction of vinyltriethoxysilane is gradually increased, that is, the higher the relative content of vinyltriethoxysilane, vinyltriethoxysilane and its hydrolysis products tend to condense on themselves, resulting in the final formation of more microcrystalline phases, thereby reducing the light transmittance of the coating film. In addition, since vinyl groups in the vinyl-modified silica sol are introduced through vinyltriethoxysilane, as the relative amount of vinyltriethoxysilane increases, the compatibility between the inorganic component and the organic component gradually increases, not only the water resistance of the coating film is improved, but also the microscopic roughness of the surface of the coating film becomes large, thereby leading to an increase in the hydrophilicity of the coating film.
Since the light transmittance is usually required to be more than 95% and the water solubility is less than 25% when used in a photovoltaic back sheet base film, it is preferable that the molar mass part of tetraethyl orthosilicate is 14 to 22 parts and the molar mass part of vinyltriethoxysilane is 2 to 4 parts. Considering together, the molar mass part of ethyl orthosilicate is preferably 18 parts, and the molar mass part of vinyltriethoxysilane is preferably 3 parts, i.e. the ratio of the molar mass parts of ethyl orthosilicate to vinyltriethoxysilane is 6:1.
Example 15
Example 15 is different from example 1 in that the molar mass part of tetraethyl orthosilicate is 18 parts, the molar mass part of vinyltriethoxysilane is 3 parts, and the molar mass part of deionized water is 11 parts.
Examples 16 to 19
Examples 16 to 22 differ from example 15 in that the molar mass parts of deionized water are 16 parts, 21 parts, 26 parts, and 31 parts, respectively.
The properties of the photovoltaic back sheet base films produced in examples 15 to 19 are shown in Table 3 below.
| Transmittance/% | Water solubility/% | |
| Example 15 | 97.9 | 29.7 |
| Example 16 | 97.5 | 18.1 |
| Example 17 | 97.2 | 6.3 |
| Example 18 | 95.3 | 6.0 |
| Example 19 | 91.4 | 5.9 |
As is clear from examples 15 to 19, as the amount of deionized water increases, the transmittance of the acrylic resin coating film gradually becomes worse, while the water resistance gradually becomes better (i.e., the water solubility of the coating film gradually decreases).
Example 20
Example 20 differs from example 1 in that: the composition was composed of, by mole, 18 parts of ethyl orthosilicate, 3 parts of vinyltriethoxysilane, 21 parts of deionized water, and 66 parts of ethanol.
Examples 21 to 24
Examples 21 to 24 differ from example 20 in that the molar mass parts of ethanol were 96 parts, 126 parts, 156 parts and 186 parts, respectively.
The properties of the photovoltaic back sheet base films produced in examples 20 to 24 are shown in Table 4 below.
| Transmittance/% | Water solubility/% | |
| Example 20 | 97.8 | 36.3 |
| Example 21 | 97.5 | 26.1 |
| Example 22 | 97.2 | 6.3 |
| Example 23 | 95.2 | 6.3 |
| Example 24 | 89.9 | 6.1 |
As is clear from examples 20 to 24, the light transmittance of the acrylic resin coating film gradually becomes worse and the water resistance gradually becomes better (i.e., the water solubility of the coating film gradually decreases) as the amount of ethanol increases.
From examples 15 to 24, it is understood that the hydrolysis reaction rate of tetraethyl orthosilicate and vinyltriethoxysilane increases with the increase of deionized water; as the amount of ethanol increases, the microcrystalline phase produced by polycondensation of tetraethyl orthosilicate and its hydrolysis products increases, and thus the light transmittance of the acrylic resin coating film gradually becomes poor, while the water resistance gradually becomes good.
Since the transmittance is generally required to be more than 95% and the water solubility is less than 25% when used in a photovoltaic back sheet base film, the molar mass part of deionized water is 16 to 26 parts, and the molar mass part of ethanol is preferably 96 to 156 parts. Considering the total, the molar mass part of deionized water is preferably 21 parts, and the molar mass part of ethanol is preferably 126 parts, namely the ratio of the sum of the molar mass parts of tetraethoxysilane and vinyltriethoxysilane to the molar mass of deionized water and ethanol is 1:1:6.
Example 25
Example 25 differs from example 1 in that: the composition was prepared from 18 parts by molar mass of ethyl orthosilicate, 3 parts by mass of vinyltriethoxysilane, 21 parts by mass of deionized water, 126 parts by mass of ethanol and 50 parts by mass of acrylic acid.
Examples 26 to 29
Examples 26 to 29 differ from example 25 in that the molar mass parts of acrylic acid are 100 parts, 150 parts, 200 parts and 250 parts, respectively.
The properties of the photovoltaic back sheet base films produced in examples 25 to 29 are shown in Table 5 below.
As is clear from examples 25 to 29, as the amount of acrylic acid increases, the light transmittance of the coating film of the acrylic resin gradually increases, while the water resistance gradually decreases (i.e., the water solubility of the coating film gradually increases).
Since the light transmittance is usually required to be more than 95% and the water solubility is less than 25% when used in a photovoltaic back sheet base film, it is preferable that the molar mass part of acrylic acid is 100 to 200 parts. In consideration of the above, the molar mass part of acrylic acid is preferably 150 parts.
Example 30
Embodiment 30 differs from embodiment 1 in that: the composition was prepared from 18 parts by molar mass of ethyl orthosilicate, 3 parts by mass of vinyltriethoxysilane, 21 parts by mass of deionized water, 126 parts by mass of ethanol, 150 parts by mass of acrylic acid, and 0.2 part by mass of an initiator (azobisisobutyronitrile).
Examples 31 to 34
Examples 31 to 34 differ from example 30 in that the molar mass parts of the initiator (azobisisobutyronitrile) are 0.4 part, 0.6 part, 0.8 part and 1.0 part, respectively.
The properties of the photovoltaic back sheet base films produced in examples 30 to 34 are shown in Table 6 below.
| Transmittance/% | Water solubility/% | |
| Example 30 | 93.2 | 39.4 |
| Example 31 | 95.7 | 24.7 |
| Example 32 | 97.2 | 6.3 |
| Example 33 | 96.1 | 6.2 |
| Example 34 | 93.7 | 6.2 |
As is clear from examples 30 to 34, the light transmittance of the coating film of the acrylic resin was gradually increased and then gradually decreased, and the water resistance was gradually improved and then tended to be unchanged (i.e., the water solubility of the coating film was gradually decreased and then tended to be unchanged).
Since it is generally desirable to have a light transmittance of greater than 95% and a water solubility of less than 25% when used in a photovoltaic backsheet base film; therefore, considering in combination, the molar part of the initiator (azobisisobutyronitrile) is preferably 0.4 to 0.8 part, and more preferably 0.6 part.
Example 35
Example 35 differs from example 1 in that: the composition was prepared from 18 parts by molar mass of ethyl orthosilicate, 3 parts by mass of vinyltriethoxysilane, 21 parts by mass of deionized water, 126 parts by mass of ethanol, 150 parts by mass of acrylic acid, 0.6 part by mass of an initiator (azobisisobutyronitrile), and 0.025 part by mass of a crosslinking agent (diallyl phthalate).
Examples 36 to 39
Examples 36 to 39 differ from example 35 in that the molar mass parts of the crosslinking agent (diallyl phthalate) were 0.05 part, 0.075 part, 0.1 part and 0.125 part, respectively.
The properties of the photovoltaic back sheet base films produced in examples 35 to 39 are shown in Table 7 below.
| Transmittance/% | Water solubility/% | |
| Example 35 | 93.3 | 27.5 |
| Example 36 | 95.1 | 15.4 |
| Example 37 | 97.2 | 6.3 |
| Example 38 | 97.3 | 6.3 |
| Example 39 | 97.3 | 6.3 |
As is clear from examples 35 to 39, as the amount of the crosslinking agent (diallyl phthalate) increases, the film light transmittance of the acrylic resin gradually increases and then tends to be unchanged, while the water resistance gradually increases and then tends to be unchanged.
Since it is generally desirable to have a light transmittance of greater than 95% and a water solubility of less than 25% when used in a photovoltaic backsheet base film; and since the light transmittance and the water solubility do not change, i.e., no benefit is generated, when the amount of the crosslinking agent (diallyl phthalate) is 0.1 part. Therefore, it is preferable that the molar mass part of the crosslinking agent (diallyl phthalate) is 0.05 to 0.075 part. In consideration of the above, the molar mass part of the crosslinking agent (diallyl phthalate) is preferably 0.05 part.
Example 40
Embodiment 40 differs from embodiment 1 in that: based on the molar mass parts, 18 parts of tetraethoxysilane, 3 parts of vinyl triethoxysilane, 21 parts of deionized water, 126 parts of ethanol, 150 parts of acrylic acid, 0.6 part of an initiator (azodiisobutyronitrile), 0.075 part of a crosslinking agent (diallyl phthalate) and 2.4 parts of a pH of the vinyl modified silica sol system.
Examples 41 to 44
Examples 41 to 44 differ from example 40 in that the pH of the vinyl modified silica sol system was 2.8, 3.2, 3.6 and 4.0, respectively.
The properties of the photovoltaic backsheet base films produced in examples 40 to 44 are shown in Table 8 below.
| Transmittance/% | Water solubility/% | |
| Example 40 | 50.4 | 61.8 |
| Example 41 | 95.3 | 24.4 |
| Example 42 | 97.2 | 6.3 |
| Example 43 | 97.5 | 6.2 |
| Example 44 | 60.5 | 50.7 |
It is understood from examples 40 to 44 that when the pH of the vinyl-modified silica sol system is 2.4 (i.e., the acidity is strong), the transmittance and the water resistance of the acrylic resin are poor, because the ethyl orthosilicate, the vinyltriethoxysilane, the ethanol and the deionized water are not mutually soluble at this time, so that the sol-gel reaction therebetween is difficult to occur, and the phase separation between them and the polyacrylic acid occurs after the coating film. When the pH of the vinyl modified silica sol system is 4.0 (weak acidity), although the ethyl orthosilicate, the vinyl triethoxysilane, the ethanol and the deionized water can be mutually dissolved to generate sol-gel reaction, the vinyl triethoxysilane is more difficult to be dissolved in the deionized water, so that the vinyl triethoxysilane is more difficult to participate in the sol-gel reaction and the free radical copolymerization reaction, no effective linkage occurs between the organic component polyacrylic acid and the inorganic component silica, and therefore, various performance indexes are poor.
When the pH of the vinyl modified silica sol system is in the range of 2.8-3.6, the hydrolysis reaction rates of tetraethoxysilane and vinyltriethoxysilane are low along with the increase of the pH, and a long Si-O long chain and a network structure with high crosslinking degree are easy to form, so that the water resistance of a coating film is improved, and the light transmittance is gradually increased. Thus, the pH of the vinyl modified silica sol system is in the range of 2.8 to 3.6, and preferably 3.6.
Example 45
Example 45 differs from example 1 in that: based on the molar mass parts, 18 parts of tetraethoxysilane, 3 parts of vinyl triethoxysilane, 21 parts of deionized water, 126 parts of ethanol, 150 parts of acrylic acid, 0.6 part of an initiator (azodiisobutyronitrile), 0.075 part of a crosslinking agent (diallyl phthalate) and 3.6 parts of a pH of the vinyl modified silica sol system.
The properties of the photovoltaic backsheet base film produced in example 45 are shown in table 9 below.
As is clear from example 45, the photovoltaic backsheet base film was excellent in light transmittance, water resistance, weather resistance (water resistance and weather resistance may also be expressed as resistance to wet heat aging), and mechanical properties such as abrasion resistance, impact resistance and flexibility.
The transmittance of the coated glass sheet was calibrated to 100% by manual calibration, and the transmittance of the coated glass sheet was measured using a DR-81 transmittance tester, and the reading was the transmittance of the coated film. The water resistance (water solubility) of the coating film was measured according to GB/T1733-1993 paint film Water resistance measurement method. The weather resistance of the coating film was carried out in accordance with GB/T1765-1979 (1989) including artificial accelerated aging for 240 hours, neutral salt spray resistance for 120 hours and wet heat resistance test for 120 hours. The impact resistance of the coating film was measured in accordance with GB/T1732-1993. The flexibility of the coating film was determined in accordance with GB/T1731-1993.
The foregoing has outlined the basic principles, features, and advantages of the present application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made therein without departing from the spirit and scope of the application, which is defined by the appended claims. The scope of the application is defined by the appended claims and equivalents thereof.
Claims (10)
1. The wet heat aging resistant photovoltaic back sheet base film is characterized by comprising, by molar mass, 14-22 parts of ethyl orthosilicate, 2-4 parts of vinyl triethoxysilane, 16-26 parts of deionized water, 96-156 parts of ethanol, 100-200 parts of acrylic acid, 0.4-0.8 part of an initiator and 0.05-0.1 part of a crosslinking agent.
2. The wet heat aging resistant photovoltaic backsheet base film according to claim 1, wherein the molar mass part of the tetraethyl orthosilicate is 18 parts and the molar mass part of the vinyltriethoxysilane is 3 parts.
3. The wet heat aging resistant photovoltaic backsheet base film according to claim 2, wherein the molar mass part of ethanol is 126 parts and the molar mass part of deionized water is 21 parts.
4. The wet heat aging resistant photovoltaic backsheet base film of claim 3 wherein the acrylic molar mass is 150 parts.
5. The wet heat aging resistant photovoltaic backsheet base film of claim 4 wherein the initiator is azobisisobutyronitrile and the molar mass parts of the initiator is 0.6 parts;
the cross-linking agent is diallyl phthalate, and the molar mass parts of the cross-linking agent are 0.075 parts.
6. The method for producing a heat aging resistant photovoltaic backsheet base film according to any one of claims 1 to 5, comprising a first step, a second step, a third step, and a fourth step;
the first step: firstly, adding the tetraethoxysilane, the vinyl triethoxysilane, the deionized water and the ethanol into a first reaction kettle, and stirring and mixing uniformly through a stirring mechanism; then, adding an acidic catalyst into the first reaction kettle to adjust the pH to 3.2-3.6; then, starting a heating mechanism in the first reaction kettle to heat, wherein the heating temperature is 45-55 ℃, and stirring by the stirring mechanism during heating until the mixed solution is completely changed to a homogeneous transparent sol, and preparing vinyl modified silica sol when the light transmittance of a sol system is not obviously changed;
The second step: fully dissolving the acrylic acid, the initiator and the cross-linking agent in a mixed solvent of ethyl acetate and absolute ethyl alcohol, wherein the mass ratio of the ethyl acetate to the absolute ethyl alcohol is 1:4, so that a monomer pre-polymerization liquid is formed, and the mass fraction of the acrylic acid in the monomer pre-polymerization liquid is 20%;
the third step: firstly, filling nitrogen into the first reaction kettle to discharge air in the first reaction kettle, and then heating the vinyl modified silica sol to 74-76 ℃ through the heating mechanism; then, dropwise adding the monomer prepolymerization liquid into the reaction kettle through a dropping mechanism, and reacting at constant temperature for 3-4 hours to obtain the raw material of the photovoltaic backboard base film;
the fourth step: and coating the raw materials of the photovoltaic back plate base film on the photovoltaic module through a brushing method, a spraying method, a dipping method or a knife coating method to obtain the photovoltaic back plate base film.
7. The device for preparing a photovoltaic backsheet base film resistant to wet heat aging according to any one of claims 1 to 5, comprising a first reaction kettle, a second reaction kettle, a heating mechanism, a dropping mechanism, and two stirring mechanisms; the first reaction kettle is provided with a first feed inlet, a first discharge outlet, an air inlet and an air outlet, and the second reaction kettle is provided with a second feed inlet and a second discharge outlet; the heating mechanism is arranged in the first reaction kettle, and the two stirring mechanisms are respectively arranged in the first reaction kettle and the second reaction kettle; the liquid dropping mechanism is arranged at the inner top of the first reaction kettle, and is communicated with the second discharge port, and the liquid dropping mechanism is used for dripping the monomer prepolymer in the second reaction kettle into the first reaction kettle.
8. The device for preparing the wet heat aging resistant photovoltaic back plate base film according to claim 7, wherein the upper ends of the first reaction kettle and the second reaction kettle are respectively provided with a mounting hole for mounting the stirring mechanism in a penetrating manner;
the stirring mechanism comprises an installation box, a fixed shaft, a rotating shaft, a shaft sleeve, an upper blade, a lower blade, a middle blade, a driving assembly and a linkage assembly; the fixed shaft coaxially penetrates through the mounting hole, and is fixed to the first reaction kettle or the second reaction kettle; the upper end of the shaft sleeve is arranged on the mounting box, and the shaft sleeve and the mounting box are coaxially and rotatably arranged outside the lower end of the fixed shaft; the upper blade and the lower blade are arranged on the shaft sleeve at intervals up and down, the stirring surface of the upper blade is inclined downwards, and the stirring surface of the lower blade is inclined upwards; the upper end of the rotating shaft is rotatably arranged in the mounting box, the rotating shaft is suitable for being rotatably connected with the upper blade and/or the lower blade, and the rotating shaft is parallel to the shaft sleeve; the middle blade is arranged on the rotating shaft and is positioned between the upper blade and the lower blade; the driving component is arranged on the first reaction kettle or the second reaction kettle and is used for driving the corresponding installation box to rotate; the linkage assembly is arranged in the installation box, when the installation box rotates, the fixed shaft forces the rotating shaft to rotate through the linkage assembly, and the rotating direction of the rotating shaft is suitable for being opposite to the rotating direction of the shaft sleeve.
9. The device for preparing a photovoltaic back sheet base film resistant to wet heat aging according to claim 8, wherein a seal is formed between the shaft sleeve and the fixed shaft, the fixed shaft is of a hollow structure, and the first feed inlet and the second feed inlet are respectively formed in the corresponding fixed shaft;
the upper end of the fixed shaft is communicated with a liquid mixing tank, a plurality of pipe connectors are arranged on the outer side wall of the liquid mixing tank along the circumferential direction at intervals, and each pipe connector is tangent to the inner side wall of the liquid mixing tank.
10. The device for preparing the photovoltaic back sheet base film resistant to wet heat aging according to claim 7, wherein the liquid dropping mechanism comprises a liquid dropping box, a buffer tank, a first connecting pipe, a second connecting pipe, a pump body and a valve body; the liquid drop box is arranged at the inner top of the first reaction kettle, a liquid storage cavity is arranged in the liquid drop box, and a plurality of liquid drop heads communicated with the liquid storage cavity are arranged at equal intervals on the lower end surface of the liquid drop box; the buffer tank is arranged above the first reaction kettle, and is provided with a liquid inlet and a liquid outlet; the two ends of the first connecting pipe are respectively communicated with the second discharging port and the liquid inlet, and the pump body is arranged on the first connecting pipe, so that the monomer prepolymer is pumped into the buffer tank through the pump body; the two ends of the second connecting pipe are respectively communicated with the liquid outlet and the liquid storage cavity, and the valve body is arranged in the second connecting pipe, so that the valve body is opened and closed at intervals, and then the monomer prepolymer is dripped into the first reaction kettle through the dripper.
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| CN202311043028.9A CN117070115A (en) | 2023-08-17 | 2023-08-17 | Moisture-heat aging resistant photovoltaic backboard base film and preparation method and preparation device thereof |
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