High weatherable light converting canopy film and method of making same

Abstract

This invention belongs to the field of greenhouse film preparation technology, specifically relating to a high weather-resistant light-converting greenhouse film and its preparation method. The high weather-resistant light-converting greenhouse film of this invention comprises an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts ETFE resin and 16-18 parts weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts ETFE resin, 15-17 parts light-converting masterbatch, and 8-10 parts weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts ETFE resin and 11-13 parts anti-drip masterbatch. The high weather-resistant light-converting greenhouse film of this invention has an outer layer that primarily provides weather protection and surface hydrophobicity, a middle layer that combines light conversion and auxiliary reinforcement, and an inner layer that primarily serves as an anti-drip function. The three layers work synergistically to give the greenhouse film excellent weather resistance, light conversion properties, and mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of greenhouse film preparation technology, specifically relating to a high weather-resistant light-converting greenhouse film and its preparation method. Background Technology

[0002] Sunlight is one of the important factors affecting plant growth. In sunlight, blue-violet light is beneficial to root and stem growth and can promote the branching and leafing of plants; red-orange light is beneficial to raising the temperature of the environment, which can stimulate the accumulation of starch and sugars, and improve the coloring rate and sweetness of fruits; while ultraviolet radiation can damage plant tissues and induce plant diseases.

[0003] Agricultural light-converting films enhance light conversion by adding light-energy conversion groups, converting sunlight that is useless for plant growth into red or blue light that is beneficial to plant growth, thereby improving the light quality transmitted through the film and promoting photosynthesis of greenhouse crops.

[0004] Currently, although the photochromic effect of rare earth organic complexes can be adjusted by selecting different rare earth ions, these rare earth organic complex light-converting agents suffer from problems such as unstable complex structure, easy photobleaching and aging when used in agricultural films for a long time, resulting in shortened fluorescence lifetime and limited service life. Furthermore, due to their limited high-temperature resistance, rare earth organic complexes cannot be used in the preparation of ETFE greenhouse films.

[0005] Furthermore, traditional light-converting agents have drawbacks such as a single spectrum, poor matching with the absorption spectrum of plants, large particle size, and easy decomposition, which greatly limit the application of light-converting films. Therefore, it is necessary to explore a new type of highly weather-resistant light-converting greenhouse film. Summary of the Invention

[0006] The purpose of this invention is to provide a high weather-resistant light-converting greenhouse film, which has excellent weather resistance, light conversion properties and mechanical properties. In addition, this invention also provides its preparation method.

[0007] The high weather-resistant light-conversion greenhouse film of the present invention is composed of an outer layer, a middle layer and an inner layer. The outer layer is composed of 100 parts by weight of ETFE resin and 16-18 parts by weight of weather-resistant reinforcing masterbatch. The middle layer is composed of 100 parts by weight of ETFE resin, 15-17 parts by weight of light-conversion masterbatch and 8-10 parts by weight of weather-resistant reinforcing masterbatch. The inner layer is composed of 100 parts by weight of ETFE resin and 11-13 parts by weight of anti-drip masterbatch.

[0008] Among them, the thickness of the high weather-resistant light-converting greenhouse film is 200 micrometers, and the thickness ratio of the outer layer, middle layer and inner layer is 1.5:2:1.

[0009] The preparation method of the weather-resistant reinforced masterbatch consists of the following steps: adding ETFE resin, weather-resistant reinforced filler, hindered amine light stabilizer and UV absorber into a mixer and mixing them, then adding the mixture into a twin-screw extruder for melt extrusion, and then filtering, underwater pelletizing, centrifugal dehydration, drying and sieving to obtain the weather-resistant reinforced masterbatch.

[0010] The weather-resistant reinforced masterbatch is composed of the following raw materials by weight: 100 parts ETFE resin, 1.6 parts weather-resistant reinforced filler, 0.2 parts hindered amine light stabilizer, and 0.1 parts UV absorber. The hindered amine light stabilizer is light stabilizer XT-8, manufactured by Beijing Tiangang Additives Co., Ltd., and the UV absorber is UV-5411.

[0011] In the preparation method of weather-resistant reinforced masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 287℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve.

[0012] The weather-resistant reinforced filler in the weather-resistant reinforced masterbatch is prepared as follows: nano-calcium fluoride, boron fiber and organosilicon microspheres are added to anhydrous ethanol-water mixed solution and ultrasonically dispersed to obtain a suspension. Acetic acid is added dropwise to the suspension to adjust the pH of the system to 4.5. Perfluorodecylethyltriethoxysilane is added under stirring. The temperature is raised to 60℃ and reacted at a constant temperature for 4.5 h. After the reaction is completed, the mixture is centrifuged, washed three times with anhydrous ethanol, and vacuum dried to obtain the weather-resistant reinforced filler.

[0013] In the preparation method of weather-resistant reinforcing filler, the mass ratio of nano-calcium fluoride, boron fiber, and organosilicon microspheres is 1:3:2. The manufacturer of organosilicon resin microspheres is Dongguan Kemai New Materials Co., Ltd., and the model number is KM-9016.

[0014] In the preparation method of weather-resistant reinforced filler, the mass ratio of nano-calcium fluoride, boron fiber and organosilicon microspheres and the volume ratio of the mixed solution of anhydrous ethanol-water is 1.0:10, with units of g / mL.

[0015] In the preparation method of weather-resistant reinforced filler, the mass ratio of anhydrous ethanol to water in the anhydrous ethanol-water mixed solution is 8:1, the ultrasonic dispersion power is 300W, and the ultrasonic dispersion time is 20min.

[0016] In the preparation method of weather-resistant reinforced filler, the mass of perfluorodecylethyltriethoxysilane accounts for 2.5% of the total mass of nano-calcium fluoride, boron fiber and organosilicon microspheres.

[0017] In the preparation method of weather-resistant reinforced filler, the vacuum drying temperature is 80℃, the drying time is 10h, and the vacuum drying pressure is -0.08MPa.

[0018] The aforementioned weather-resistant reinforced masterbatch is prepared by extruding and granulating ETFE resin, weather-resistant reinforced filler, hindered amine light stabilizer, and UV absorber as raw materials using a twin-screw extruder. The weather-resistant reinforced filler incorporates nano-calcium fluoride, boron fiber, and organosilicon microspheres. Nano-calcium fluoride, with its layered crystal structure, acts as a solid lubricant during masterbatch processing and subsequent product molding, reducing frictional resistance between materials and improving processing fluidity. Boron fiber, with its one-dimensional structure, constructs a continuous mechanical support network within the ETFE matrix, significantly enhancing the tensile strength of the masterbatch. The micron-sized spherical morphology of the organosilicon microspheres forms a micro-nano rough structure on the material surface, providing a core structural basis for the hydrophobic properties of subsequent products.

[0019] The preparation method of the light conversion masterbatch consists of the following steps: ① The light conversion powder, 3-aminopropyltriethoxysilane and anhydrous ethanol are mixed and stirred to react. After the reaction is completed, the mixture is filtered, dried and sieved to prepare silanized light conversion powder; ② ETFE resin and silanized light conversion powder are added to a mixer and mixed. Then the mixture is added to a twin-screw extruder for melt extrusion. After filtration, underwater pelletizing, centrifugal dehydration, drying and sieving, the light conversion masterbatch is prepared.

[0020] In the preparation method of the light conversion masterbatch, step ①, the mass ratio of light conversion powder, 3-aminopropyltriethoxysilane, and anhydrous ethanol is 1:0.04:40.

[0021] In step ① of the preparation method of the light conversion masterbatch, the stirring reaction temperature is 60℃, the stirring reaction time is 2h, and the stirring speed is 300r / min.

[0022] In step ① of the preparation method of the optical conversion masterbatch, the drying temperature is 80℃, the drying time is 4h, the vacuum degree is -0.08MPa, and it is passed through an 80-mesh sieve.

[0023] In step ② of the preparation method of the masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 285℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve.

[0024] The light-converting masterbatch described in step ② of the preparation method consists of the following raw materials in parts by weight: 100 parts of ETFE resin and 1.5-1.7 parts of silanized light-converting powder.

[0025] The preparation method of the light-converting powder described in step ① of the preparation method of the light-converting masterbatch consists of the following steps: ① CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3 and MgO are mixed evenly and wet ball milled. After drying and sieving, a mixture is prepared. The mixture is placed in a corundum crucible for melting. The melt is then poured into circulating water at 25°C and quenched into glass sheets. The glass sheets are removed and dried to obtain dry glass sheets; ② The dry glass sheets are coarsely crushed by a jaw crusher, then wet ball milled and spray dried to obtain glass powder; ③ The glass powder is placed in a crucible in a tube furnace and air microcrystallized in an air atmosphere. Then, it is cooled to room temperature with the furnace, pulverized by an air jet mill and dried to obtain rare earth powder.

[0026] In the preparation method of the light-converting powder, step ① of the mixture contains the following raw material composition by mass percentage: CaO 27%, SiO2 30%, Al2O3 19%, B2O3 4.6%, P2O5 3.7%, Na2O 6.0%, SrO 2.0%, Gd2O3 2%, Pr2O3 2%, Eu2O3 1.5%, Cr2O3 0.2%, MgO 2%.

[0027] In step ① of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3, and MgO, zirconia balls, and anhydrous ethanol is 50:250:59.

[0028] In the preparation method of the brightening powder, step ① involves a wet ball milling time of 2 hours and a wet ball milling speed of 200 r / min; a drying temperature of 80℃ and a drying time of 12 hours; and a drying pressure of atmospheric pressure; the powder is then passed through an 80-mesh sieve.

[0029] The melting process described in step ① of the preparation method of the optical powder involves heating to 1450℃ at a rate of 5℃ / min in air and holding at that temperature for 45min. The glass slide drying temperature is 110℃ and the glass slide drying time is 2h.

[0030] In step ② of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of glass plate, zirconia balls and anhydrous ethanol is 5:20:6. The wet ball milling time is 4 hours and the wet ball milling speed is 250 r / min.

[0031] In step ② of the preparation method of the glass powder, the inlet temperature of the spray drying is 180℃ and the outlet temperature is 90℃; the particle size D of the glass powder is...50 =0.85μm.

[0032] The air microcrystallization described in step ③ of the preparation method of the light-converting powder involves first heating to 650℃ at a heating rate of 5℃ / min and holding for 30min, and then heating to 810℃ at a heating rate of 5℃ / min and holding for 90min.

[0033] In step ③, the pressure of the air jet mill is 0.6 MPa, and the atmosphere is nitrogen; the drying treatment is carried out under vacuum at 110°C for 4 hours to prepare rare earth powder D. 50 =0.8μm.

[0034] The photoconverting powder described in this invention undergoes a two-step phase transition—nucleation and crystallization—during air microcrystallization. During the nucleation stage, Mg… 2+ With Al 3+ Formation of MgAl2O4 ion clusters, rare earth ions (Gd) 3+ Pr 3+ Eu 2+ The formation of "heterogeneous nucleation sites" occurs during the crystallization stage, where MgAl2O4 ion clusters form the MgAl2O4 main crystalline phase, and Cr... 3+ Due to the ionic radius and Al 3+ Highly matched, preferentially replacing Al in the spinel lattice during crystallization. 3+ Octahedral coordination sites, forming Cr 3+ Doped magnesium-aluminum spinel microcrystals. In the molten state at 1450℃, SiO2 in the raw material dissociates into [SiO4] tetrahedra, B2O3 forms [BO3] trigonometric bodies and [BO4] tetrahedra, and P2O5 forms [PO4] tetrahedra. These three structures cross-link to form a continuous three-dimensional network structure. Ca... 2+ Na + 、Sr 2+ Mg 2+ When cations fill the gaps in the network, Al 3+ Partially replaces Si 4+ Entering the network further stabilizes the structure. Rare earth ions (Gd) 3+ Pr 3+ Eu 2+ The ions are uniformly dispersed in the glass network in the form of dopants. During rapid quenching, the migration of ions is suppressed, and an ordered crystalline phase cannot be formed, ultimately resulting in an amorphous glass matrix.

[0035] Magnesium aluminum spinel microcrystals are Cr 3+ Providing a strong octahedral crystal field environment enables Cr 3+ The electronic transition changes from green light transition in the glass phase to red light transition in the spinel lattice, realizing the conversion from green light to red light; at the same time, the ordered lattice reduces Cr 3+The absence of radiation-free transition loss improves red light emission efficiency.

[0036] In the aforementioned photoconverter, ultraviolet light is converted by Gd 3+ The 4f electron absorbs ultraviolet photons, transitioning from the ground state to an excited state, and Cr 3+ The 3d electrons absorb ultraviolet-blue light photons and undergo dd transitions; the excited state of Gd 3+ and Cr 3+ Unstable, it transfers energy to Eu through non-radiative energy transfer. 2+ and Pr 3+ This causes the latter's electrons to transition to an excited state; the excited state Eu 2+ and Pr 3+ Electrons return to their ground state, releasing photons and converting ultraviolet light into visible light; Eu 2+ Electrons from 4f 6 5d 1 Excited state transition to 4f 7 Ground state, emits blue-green light; Pr 3+ The electron undergoes a 4f inner-shell transition and emits red-orange light.

[0037] The method for preparing the dripping masterbatch consists of the following steps: premixing hydrophilic fumed silica with PEG-4000, then adding ETFE resin and antioxidant 1010 and mixing evenly, and finally adding the mixture to a twin-screw extruder for melt extrusion under a nitrogen atmosphere, followed by filtration, underwater pelletizing, drying, and sieving to obtain the dripping masterbatch.

[0038] In the preparation method of the drip masterbatch, the mixing speed is 400 r / min, the mixing temperature is room temperature, the premixing time is 2 min, the mixing time for adding ETFE resin and antioxidant 1010 is 3 min, and the melt extrusion temperature is 285℃.

[0039] In the preparation method of the drip masterbatch, the underwater pelleting temperature is 25℃, and particles with a diameter of 2.5mm are obtained; the drying temperature is 80℃, the drying time is 15min, and the particles are passed through an 8-mesh sieve.

[0040] The droplet masterbatch is composed of the following raw materials in parts by mass: 100 parts ETFE resin, 8 parts hydrophilic fumed silica, 2 parts PEG-4000, and 0.2 parts antioxidant 1010. The hydrophilic fumed silica is Evonik Degussa fumed silica A200.

[0041] When the drip-reducing masterbatch is blended with ETFE matrix resin for blown film production, PEG-4000 (polyethylene glycol with a molecular weight of 4000) acts as a compatibilizer in the molten state, promoting the uniform dispersion of hydrophilic fumed silica in the ETFE film. During the cooling and film formation process, the hydroxyl groups on the surface of the fumed silica, being highly polar, spontaneously migrate to the air contact surface of the film, forming a continuous hydrophilic film. On the surface of the ETFE film modified by the drip-reducing masterbatch, the hydrophilic hydroxyl groups form hydrogen bonds with water molecules, causing water vapor to condense into a uniform water film (rather than water droplets). This water film slowly flows along the film surface to the edge of the greenhouse, thus eliminating dripping.

[0042] The preparation method of the high weather-resistant light-converting film of the present invention consists of the following steps:

[0043] (1) Add the outer layer raw material, the middle layer raw material and the inner layer raw material into a high-speed mixer for mixing. After mixing evenly, the outer layer mixture, the middle layer mixture and the inner layer mixture are discharged.

[0044] (2) The outer layer mixture, the middle layer mixture and the inner layer mixture are respectively added to a three-layer co-extrusion blown film machine for blown film forming, and then cooled, shaped, pulled and wound to prepare a high weather-resistant light-converting greenhouse film.

[0045] In step (1), the parameters for mixing the outer layer, the middle layer and the inner layer are the same, the temperature during mixing is room temperature, the speed during mixing is 500 r / min and the mixing time is 3 min.

[0046] Step (2) The temperature of the feeding section of the three-layer co-extrusion blown film machine is 248-250℃, the temperature of the compression section is 272-274℃, the temperature of the melting section is 286-288℃, the temperature of the homogenization section is 282-283℃, and the temperature of the die head is 284-285℃.

[0047] In step (2), the three-layer melt is extruded through a three-layer co-extrusion die, and the blow-up ratio is controlled to be 3.0 and the traction ratio is 1.7.

[0048] In step (2), the temperature of the air ring during cooling and shaping is controlled at 20℃, and the traction speed is 10m / min.

[0049] Compared with the prior art, the present invention has the following advantages:

[0050] (1) The high weather resistance and light conversion greenhouse film of the present invention has an outer layer that mainly provides weather protection and surface hydrophobicity, a middle layer that has both light conversion and auxiliary enhancement functions, and an inner layer that mainly plays the role of anti-drip function. The three-layer structure works together to make the greenhouse film have excellent weather resistance, light conversion and mechanical properties.

[0051] (2) The high weather-resistant light-converting greenhouse film of the present invention has a high proportion of weather-resistant reinforcing masterbatch added to the outer layer. On the one hand, the hydrophobic properties can reduce the adhesion of rainwater and dew on the film surface and reduce the accelerated aging of the film material caused by ultraviolet rays focusing through the water film. On the other hand, the mechanical reinforcing components can improve the tear resistance and puncture resistance of the film and resist damage from external forces such as hail and strong winds. In addition, the protective function of the outer layer can isolate the degradation of the light-converting masterbatch in the middle layer by ultraviolet rays. The middle layer has a high proportion of light-converting masterbatch added, and is combined with weather-resistant reinforcing masterbatch to form a combination of "light-converting function + auxiliary reinforcement". The light-converting masterbatch can convert the ultraviolet and green light in sunlight that are ineffective for crops into red and orange light required for plant photosynthesis, thereby improving the effective radiation of photosynthesis in the greenhouse. A small amount of reinforcing masterbatch can compensate for the decrease in mechanical properties caused by the addition of light-converting masterbatch, and at the same time form a gradient mechanical support with the outer reinforcing masterbatch, so that the tensile strength of the film material is evenly distributed and local stress concentration fracture is avoided. Adding drip-proof masterbatch to the inner layer allows its hydrophilic groups to migrate directionally to the inner surface of the membrane, forming a hydrophilic film layer. This causes water vapor inside the greenhouse to condense into a uniform water film and flow along the wall, preventing water droplets from dripping and causing frost damage or disease to crops.

[0052] (3) The high weather-resistant light-conversion greenhouse film of the present invention has an outer layer of weather-resistant protection function that reduces the degradation rate of the intermediate light-conversion masterbatch, thereby maintaining the long-lasting light-conversion function. At the same time, the intermediate light-conversion masterbatch can convert ultraviolet light into visible light, reducing the aging effect of ultraviolet light on the ETFE substrate, which in turn improves the overall weather resistance life of the film. The high content of weather-resistant reinforcing masterbatch in the outer layer provides the main mechanical strength of the film, while the small amount of weather-resistant reinforcing masterbatch in the intermediate layer provides auxiliary reinforcement. The homogeneous structure of the three substrates ensures the uniform transfer of mechanical properties, ultimately resulting in a good elongation at break of the greenhouse film, and the mechanical properties do not decay during long-term use. The inner layer's anti-drip function eliminates the harm of water droplets, and the intermediate layer's light-conversion function improves photosynthetic efficiency. The two work together to create a high-quality growth environment of "no dripping and high photosynthesis".

[0053] (4) The preparation method of the high weather-resistant light-converting greenhouse film of the present invention uses ETFE resin as the base material for all three layers, which fundamentally solves the interfacial compatibility problem when different materials are co-extruded. The process is simple, the parameters are reasonable, the greenhouse film prepared has stable performance, and the functions of each layer are coordinated and the mechanical properties are uniform. Detailed Implementation

[0054] The weather-resistant reinforced masterbatch, light conversion masterbatch, and droplet-reducing masterbatch used in Examples 1-3 below are the same, and the specific preparation process is as follows:

[0055] The preparation method of the weather-resistant reinforced masterbatch consists of the following steps: adding ETFE resin, weather-resistant reinforced filler, hindered amine light stabilizer and UV absorber into a mixer and mixing them, then adding the mixture into a twin-screw extruder for melt extrusion, and then filtering, underwater pelletizing, centrifugal dehydration, drying and sieving to obtain the weather-resistant reinforced masterbatch.

[0056] The weather-resistant reinforced masterbatch is composed of the following raw materials by weight: 100 parts ETFE resin, 1.6 parts weather-resistant reinforced filler, 0.2 parts hindered amine light stabilizer, and 0.1 parts UV absorber. The hindered amine light stabilizer is light stabilizer XT-8, manufactured by Beijing Tiangang Additives Co., Ltd., and the UV absorber is UV-5411.

[0057] In the preparation method of weather-resistant reinforced masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 287℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve.

[0058] The weather-resistant reinforced filler in the weather-resistant reinforced masterbatch is prepared as follows: nano-calcium fluoride, boron fiber and organosilicon microspheres are added to anhydrous ethanol-water mixed solution and ultrasonically dispersed to obtain a suspension. Acetic acid is added dropwise to the suspension to adjust the pH of the system to 4.5. Perfluorodecylethyltriethoxysilane is added under stirring. The temperature is raised to 60℃ and reacted at a constant temperature for 4.5 h. After the reaction is completed, the mixture is centrifuged, washed three times with anhydrous ethanol, and vacuum dried to obtain the weather-resistant reinforced filler.

[0059] In the preparation method of weather-resistant reinforcing filler, the mass ratio of nano-calcium fluoride, boron fiber, and organosilicon microspheres is 1:3:2. The manufacturer of organosilicon resin microspheres is Dongguan Kemai New Materials Co., Ltd., and the model number is KM-9016.

[0060] In the preparation method of weather-resistant reinforced filler, the mass ratio of nano-calcium fluoride, boron fiber and organosilicon microspheres and the volume ratio of the mixed solution of anhydrous ethanol-water is 1.0:10, with units of g / mL.

[0061] In the preparation method of weather-resistant reinforced filler, the mass ratio of anhydrous ethanol to water in the anhydrous ethanol-water mixed solution is 8:1, the ultrasonic dispersion power is 300W, and the ultrasonic dispersion time is 20min.

[0062] In the preparation method of weather-resistant reinforced filler, the mass of perfluorodecylethyltriethoxysilane accounts for 2.5% of the total mass of nano-calcium fluoride, boron fiber and organosilicon microspheres.

[0063] In the preparation method of weather-resistant reinforced filler, the vacuum drying temperature is 80℃, the drying time is 10h, and the vacuum drying pressure is -0.08MPa.

[0064] The preparation method of the light conversion masterbatch consists of the following steps: ① The light conversion powder, 3-aminopropyltriethoxysilane and anhydrous ethanol are mixed and stirred to react. After the reaction is completed, the mixture is filtered, dried and sieved to prepare silanized light conversion powder; ② ETFE resin and silanized light conversion powder are added to a mixer and mixed. Then the mixture is added to a twin-screw extruder for melt extrusion. After filtration, underwater pelletizing, centrifugal dehydration, drying and sieving, the light conversion masterbatch is prepared.

[0065] In the preparation method of the light conversion masterbatch, step ①, the mass ratio of light conversion powder, 3-aminopropyltriethoxysilane, and anhydrous ethanol is 1:0.04:40.

[0066] In step ① of the preparation method of the light conversion masterbatch, the stirring reaction temperature is 60℃, the stirring reaction time is 2h, and the stirring speed is 300r / min.

[0067] In step ① of the preparation method of the optical conversion masterbatch, the drying temperature is 80℃, the drying time is 4h, the vacuum degree is -0.08MPa, and it is passed through an 80-mesh sieve.

[0068] In step ② of the preparation method of the masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 285℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve.

[0069] The light-converting masterbatch described in step ② of the preparation method consists of the following raw materials in parts by weight: 100 parts of ETFE resin and 1.5-1.7 parts of silanized light-converting powder.

[0070] The preparation method of the light-converting powder described in step ① of the preparation method of the light-converting masterbatch consists of the following steps: ① CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3 and MgO are mixed evenly and wet ball milled. After drying and sieving, a mixture is prepared. The mixture is placed in a corundum crucible for melting. The melt is then poured into circulating water at 25°C and quenched into glass sheets. The glass sheets are removed and dried to obtain dry glass sheets; ② The dry glass sheets are coarsely crushed by a jaw crusher, then wet ball milled and spray dried to obtain glass powder; ③ The glass powder is placed in a crucible in a tube furnace and air microcrystallized in an air atmosphere. Then, it is cooled to room temperature with the furnace, pulverized by an air jet mill and dried to obtain rare earth powder.

[0071] In the preparation method of the light-converting powder, step ① of the mixture contains the following raw material composition by mass percentage: CaO 27%, SiO2 30%, Al2O3 19%, B2O3 4.6%, P2O5 3.7%, Na2O 6.0%, SrO 2.0%, Gd2O3 2%, Pr2O3 2%, Eu2O3 1.5%, Cr2O3 0.2%, MgO 2%.

[0072] In step ① of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3, and MgO, zirconia balls, and anhydrous ethanol is 50:250:59.

[0073] In the preparation method of the brightening powder, step ① involves a wet ball milling time of 2 hours and a wet ball milling speed of 200 r / min; a drying temperature of 80℃ and a drying time of 12 hours; and a drying pressure of atmospheric pressure; the powder is then passed through an 80-mesh sieve.

[0074] The melting process described in step ① of the preparation method of the optical powder involves heating to 1450℃ at a rate of 5℃ / min in air and holding at that temperature for 45min. The glass slide drying temperature is 110℃ and the glass slide drying time is 2h.

[0075] In step ② of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of glass plate, zirconia balls and anhydrous ethanol is 5:20:6. The wet ball milling time is 4 hours and the wet ball milling speed is 250 r / min.

[0076] In step ② of the preparation method of the glass powder, the inlet temperature of the spray drying is 180℃ and the outlet temperature is 90℃; the particle size D of the glass powder is... 50=0.85μm.

[0077] The air microcrystallization described in step ③ of the preparation method of the light-converting powder involves first heating to 650℃ at a heating rate of 5℃ / min and holding for 30min, and then heating to 810℃ at a heating rate of 5℃ / min and holding for 90min.

[0078] In step ③, the pressure of the air jet mill is 0.6 MPa, and the atmosphere is nitrogen; the drying treatment is carried out under vacuum at 110°C for 4 hours to prepare rare earth powder D. 50 =0.8μm.

[0079] The method for preparing the dripping masterbatch consists of the following steps: premixing hydrophilic fumed silica with PEG-4000, then adding ETFE resin and antioxidant 1010 and mixing evenly, and finally adding the mixture to a twin-screw extruder for melt extrusion under a nitrogen atmosphere, followed by filtration, underwater pelletizing, drying, and sieving to obtain the dripping masterbatch.

[0080] In the preparation method of the drip masterbatch, the mixing speed is 400 r / min, the mixing temperature is room temperature, the premixing time is 2 min, the mixing time for adding ETFE resin and antioxidant 1010 is 3 min, and the melt extrusion temperature is 285℃.

[0081] In the preparation method of the drip masterbatch, the underwater pelleting temperature is 25℃, and particles with a diameter of 2.5mm are obtained; the drying temperature is 80℃, the drying time is 15min, and the particles are passed through an 8-mesh sieve.

[0082] The droplet masterbatch is composed of the following raw materials in parts by mass: 100 parts ETFE resin, 8 parts hydrophilic fumed silica, 2 parts PEG-4000, and 0.2 parts antioxidant 1010. The hydrophilic fumed silica is Evonik Degussa fumed silica A200.

[0083] Example 1

[0084] The high weather-resistant light-conversion greenhouse film described in Example 1 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 17 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin, 16 parts of light-conversion masterbatch, and 9 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 12 parts of anti-drip masterbatch.

[0085] Among them, the thickness of the high weather-resistant light-converting greenhouse film is 200 micrometers, and the thickness ratio of the outer layer, middle layer and inner layer is 1.5:2:1.

[0086] The preparation method of the high weather-resistant light-converting film described in Example 1 consists of the following steps:

[0087] (1) Add the outer layer raw material, the middle layer raw material and the inner layer raw material into a high-speed mixer for mixing. After mixing evenly, the outer layer mixture, the middle layer mixture and the inner layer mixture are discharged.

[0088] (2) The outer layer mixture, the middle layer mixture and the inner layer mixture are respectively added to a three-layer co-extrusion blown film machine for blown film forming, and then cooled, shaped, pulled and wound to prepare a high weather-resistant light-converting greenhouse film.

[0089] In step (1), the parameters for mixing the outer layer, the middle layer and the inner layer are the same, the temperature during mixing is room temperature, the speed during mixing is 500 r / min and the mixing time is 3 min.

[0090] Step (2) The temperature of the feeding section of the three-layer co-extrusion blown film machine is 249℃, the temperature of the compression section is 273℃, the temperature of the melting section is 287℃, the temperature of the homogenization section is 283℃, and the temperature of the die head is 285℃.

[0091] In step (2), the three-layer melt is extruded through a three-layer co-extrusion die, and the blow-up ratio is controlled to be 3.0 and the traction ratio is 1.7.

[0092] In step (2), the temperature of the air ring during cooling and shaping is controlled at 20℃, and the traction speed is 10m / min.

[0093] Example 2

[0094] The high weather-resistant light-conversion greenhouse film described in Example 2 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 16 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin, 15 parts of light-conversion masterbatch, and 10 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 11 parts of anti-drip masterbatch.

[0095] Among them, the thickness of the high weather-resistant light-converting greenhouse film is 200 micrometers, and the thickness ratio of the outer layer, middle layer and inner layer is 1.5:2:1.

[0096] The preparation method of the high weather-resistant light-converting film described in Example 2 consists of the following steps:

[0097] (1) Add the outer layer raw material, the middle layer raw material and the inner layer raw material into a high-speed mixer for mixing. After mixing evenly, the outer layer mixture, the middle layer mixture and the inner layer mixture are discharged.

[0098] (2) The outer layer mixture, the middle layer mixture and the inner layer mixture are respectively added to a three-layer co-extrusion blown film machine for blown film forming, and then cooled, shaped, pulled and wound to prepare a high weather-resistant light-converting greenhouse film.

[0099] In step (1), the parameters for mixing the outer layer, middle layer and inner layer are the same, the mixing temperature is room temperature, the mixing speed is 500 r / min and the mixing time is 3 min.

[0100] Step (2) The temperature of the feeding section of the three-layer co-extrusion blown film machine is 248℃, the temperature of the compression section is 272℃, the temperature of the melting section is 286℃, the temperature of the homogenization section is 282℃, and the temperature of the die head is 284℃.

[0101] In step (2), the three-layer melt is extruded through a three-layer co-extrusion die, and the blow-up ratio is controlled to be 3.0 and the traction ratio is 1.7.

[0102] In step (2), the temperature of the air ring during cooling and shaping is controlled at 20℃, and the traction speed is 10m / min.

[0103] Example 3

[0104] The high weather-resistant light-conversion greenhouse film described in Example 3 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 18 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin, 17 parts of light-conversion masterbatch, and 8 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 13 parts of anti-drip masterbatch.

[0105] Among them, the thickness of the high weather-resistant light-converting greenhouse film is 200 micrometers, and the thickness ratio of the outer layer, middle layer and inner layer is 1.5:2:1.

[0106] The preparation method of the high weather-resistant light-converting film described in Example 3 consists of the following steps:

[0107] (1) Add the outer layer raw material, the middle layer raw material and the inner layer raw material into a high-speed mixer for mixing. After mixing evenly, the outer layer mixture, the middle layer mixture and the inner layer mixture are discharged.

[0108] (2) The outer layer mixture, the middle layer mixture and the inner layer mixture are respectively added to a three-layer co-extrusion blown film machine for blown film forming, and then cooled, shaped, pulled and wound to prepare a high weather-resistant light-converting greenhouse film.

[0109] In step (1), the parameters for mixing the outer layer, middle layer and inner layer are the same, the mixing temperature is room temperature, the mixing speed is 500 r / min and the mixing time is 3 min.

[0110] Step (2) The temperature of the feeding section of the three-layer co-extrusion blown film machine is 250℃, the temperature of the compression section is 274℃, the temperature of the melting section is 288℃, the temperature of the homogenization section is 283℃, and the temperature of the die head is 285℃.

[0111] In step (2), the three-layer melt is extruded through a three-layer co-extrusion die, and the blow-up ratio is controlled to be 3.0 and the traction ratio is 1.7.

[0112] In step (2), the temperature of the air ring during cooling and shaping is controlled at 20℃, and the traction speed is 10m / min.

[0113] Comparative Example 1

[0114] The preparation method of the high weather-resistant light-conversion greenhouse film described in Comparative Example 1 is the same as that in Example 1, except that the raw material composition is different. The high weather-resistant light-conversion greenhouse film described in Comparative Example 1 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin. The middle layer, by weight, consists of 100 parts of ETFE resin, 16 parts of light-conversion masterbatch, and 9 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 12 parts of anti-drip masterbatch.

[0115] Comparative Example 2

[0116] The preparation method of the high weather-resistant light-converting greenhouse film described in Comparative Example 2 is the same as that in Example 1, except that the raw material composition is different. The high weather-resistant light-converting greenhouse film described in Comparative Example 2 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 17 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin and 9 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 12 parts of anti-drip masterbatch.

[0117] Comparative Example 3

[0118] The preparation method of the high weather-resistant light-converting greenhouse film described in Comparative Example 3 is the same as that in Example 1, except that the raw material composition is different. The high weather-resistant light-converting greenhouse film described in Comparative Example 3 consists of an outer layer, a middle layer, and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 17 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin and 16 parts of light-converting masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 12 parts of anti-drip masterbatch.

[0119] The performance of the high weather-resistant light-converting greenhouse films prepared in Examples 1-3 and Comparative Examples 1-3 was tested, and the results are shown in Table 1 below. Tensile strength and elongation at break were tested according to GB / T 1040.3; the outer and inner contact angles of the ETFE film were tested according to GB / T 30693 for static contact angle; light transmittance was tested according to GB / T 2410; weather resistance was tested according to GB / T 16422.2; anti-drip performance was tested according to NY / T 1452-2007; the test method for the targeted light conversion efficiency η is as follows: ① Sample preparation: The ETFE greenhouse film to be tested was cut into 50mm × 50mm samples. Before testing, the samples were conditioned for 48 hours at 25℃ and 50% relative humidity, according to GB / T 2918-2018 "Standard Environment for Conditioning and Testing of Plastic Samples". ② Incident spectrum acquisition: The xenon lamp light source was turned on and vertically irradiated the inlet of the integrating sphere. The spectral distribution of incident light was collected and recorded within the wavelength range of 300-800 nm. The integral value of light intensity I in the 300-400 nm band was calculated and recorded. UV，in ③ Outgoing spectrum acquisition: After conditioning, the sample is tightly attached to the inlet of the integrating sphere, and the same xenon lamp source is used to illuminate the sample perpendicularly. Scan again, acquiring and recording the spectral distribution of the outgoing light transmitted through the sample. Calculate and record the integral value I of the light intensity in the 600-700nm band. RO，out ④ Parallel testing: Each group of samples was tested in parallel three times, and the results were taken as the arithmetic mean. The targeted light conversion efficiency η was calculated using the following formula: η(%) = (I RO，out - I RO，in ) / I UV，in ×100%, where I RO，in This represents the integral value of the background light intensity in the 600-700 nm band measured in step ②. The results are shown in Table 1 below:

[0120] Table 1. Test results of high weather-resistant light-converting greenhouse film performance

[0121]

[0122] As shown in Table 1, the mechanical strength of the high weather-resistant light-converting greenhouse films prepared in Examples 1-3 is greater than that of Comparative Examples 1-3. The retention rates of tensile strength and elongation at break of the high weather-resistant light-converting greenhouse films prepared in Examples 1-3 are much better than those of Comparative Examples 1-3, indicating that the weather resistance of the high weather-resistant light-converting greenhouse films prepared in Examples 1-3 is better than that of Comparative Examples 1-3. As can be seen from the targeted light conversion efficiency, the light conversion efficiency of the high weather-resistant light-converting greenhouse film in Comparative Example 2 is extremely low due to the lack of light conversion masterbatch, and the greenhouse film prepared in Comparative Example 2 basically does not have light conversion performance. In summary, the overall performance of the greenhouse films prepared in Examples 1-3 is better than that of Comparative Examples 1-3.

[0123] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A high weather-resistant light-converting greenhouse film, characterized in that: It consists of an outer layer, a middle layer and an inner layer. The outer layer, by weight, consists of 100 parts of ETFE resin and 16-18 parts of weather-resistant reinforcing masterbatch. The middle layer, by weight, consists of 100 parts of ETFE resin, 15-17 parts of light-converting masterbatch and 8-10 parts of weather-resistant reinforcing masterbatch. The inner layer, by weight, consists of 100 parts of ETFE resin and 11-13 parts of drip-proof masterbatch. The preparation method of the weather-resistant reinforced masterbatch consists of the following steps: adding ETFE resin, weather-resistant reinforced filler, hindered amine light stabilizer and UV absorber into a mixer and mixing them; then adding the mixture into a twin-screw extruder for melt extrusion; and finally filtering, underwater pelletizing, centrifugal dehydration, drying and sieving to obtain the weather-resistant reinforced masterbatch. The preparation method of the weather-resistant reinforced filler in the weather-resistant reinforced masterbatch is as follows: nano-calcium fluoride, boron fiber and organosilicon microspheres are added to anhydrous ethanol-water mixed solution and ultrasonically dispersed to obtain a suspension. Acetic acid is added dropwise to the suspension to adjust the pH of the system to 4.

5. Perfluorodecylethyltriethoxysilane is added under stirring. The temperature is raised to 60℃ and reacted at a constant temperature for 4.5h. After the reaction is completed, the mixture is centrifuged, washed 3 times with anhydrous ethanol, and vacuum dried to prepare the weather-resistant reinforced filler. The preparation method of the light conversion masterbatch consists of the following steps: ① The light conversion powder, 3-aminopropyltriethoxysilane and anhydrous ethanol are mixed and stirred to react. After the reaction is completed, the mixture is filtered, dried and sieved to obtain silanized light conversion powder; ② ETFE resin and silanized light conversion powder are added to a mixer and mixed. Then the mixture is added to a twin-screw extruder for melt extrusion. After filtration, underwater pelletizing, centrifugal dehydration, drying and sieving, the light conversion masterbatch is obtained. The preparation method of the light-converting powder described in step ① of the preparation method of the light-converting masterbatch consists of the following steps: ① CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3 and MgO are mixed evenly and wet ball milled. After drying and sieving, a mixture is prepared. The mixture is placed in a corundum crucible for melting. The melt is then poured into circulating water at 25°C and quenched into glass sheets. The glass sheets are removed and dried to obtain dry glass sheets; ② The dry glass sheets are coarsely crushed by a jaw crusher, then wet ball milled and spray dried to obtain glass powder; ③ The glass powder is placed in a crucible in a tube furnace and air microcrystallized in an air atmosphere. Then, it is cooled to room temperature with the furnace, pulverized by an air jet mill and dried to obtain rare earth powder.

2. The high weather-resistant light-converting greenhouse film according to claim 1, characterized in that: The weather-resistant reinforced masterbatch is composed of the following raw materials in parts by weight: 100 parts ETFE resin, 1.6 parts weather-resistant reinforced filler, 0.2 parts hindered amine light stabilizer, and 0.1 parts UV absorber, wherein the hindered amine light stabilizer is light stabilizer XT-8 and the UV absorber is UV-5411. In the preparation method of weather-resistant reinforced masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 287℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve.

3. The high weather-resistant light-converting greenhouse film according to claim 1, characterized in that: In the preparation method of weather-resistant reinforcing filler, the mass ratio of nano-calcium fluoride, boron fiber, and organosilicon microspheres is 1:3:

2. In the preparation method of weather-resistant reinforced filler, the mass ratio of nano-calcium fluoride, boron fiber and organosilicon microspheres and the volume ratio of the mixed solution of anhydrous ethanol-water is 1.0:10, with units of g / mL; In the preparation method of weather-resistant reinforced filler, the mass ratio of anhydrous ethanol to water in the anhydrous ethanol-water mixed solution is 8:1, the ultrasonic dispersion power is 300W, and the ultrasonic dispersion time is 20min. In the preparation method of weather-resistant reinforced filler, the mass of perfluorodecylethyltriethoxysilane accounts for 2.5% of the total mass of nano-calcium fluoride, boron fiber, and organosilicon microspheres; In the preparation method of weather-resistant reinforced filler, the vacuum drying temperature is 80℃, the drying time is 10h, and the vacuum drying pressure is -0.08MPa.

4. The high weather-resistant light-converting greenhouse film according to claim 1, characterized in that: The preparation method of the light conversion masterbatch involves step ① where the mass ratio of the light conversion powder, 3-aminopropyltriethoxysilane, and anhydrous ethanol is 1:0.04:40; In step ① of the preparation method of the optical conversion masterbatch, the stirring reaction temperature is 60℃, the stirring reaction time is 2h, and the stirring speed is 300r / min; In step ① of the preparation method of the optical conversion masterbatch, the drying temperature is 80℃, the drying time is 4h, the vacuum degree is -0.08MPa, and it is passed through an 80-mesh sieve. In step ② of the preparation method of the masterbatch, the mixing speed is 500 r / min, the mixing temperature is room temperature, and the mixing time is 3 min; the melt extrusion temperature is 285℃, the screw speed is 200 r / min; the underwater pelletizing temperature is 25℃, and particles with a particle size of 2 mm are obtained; centrifugation dehydration is performed for 2 min, the drying temperature is 80℃, the drying time is 15 min, and the particles are passed through an 8-mesh sieve. The light-converting masterbatch described in step ② of the preparation method consists of the following raw materials in parts by weight: 100 parts of ETFE resin and 1.5-1.7 parts of silanized light-converting powder.

5. The high weather-resistant light-converting greenhouse film according to claim 1, characterized in that: The preparation method of the photoconverting powder, step ①, the raw material composition of the mixture, by mass percentage, is as follows: CaO 27%, SiO2 30%, Al2O3 19%, B2O3 4.6%, P2O5 3.7%, Na2O 6.0%, SrO 2.0%, Gd2O3 2%, Pr2O3 2%, Eu2O3 1.5%, Cr2O3 0.2%, MgO 2%; In step ① of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of CaO, SiO2, Al2O3, B2O3, P2O5, Na2O, SrO, Gd2O3, Pr2O3, Eu2O3, Cr2O3, and MgO, zirconia balls, and anhydrous ethanol is 50:250:

59. In the preparation method of the optical brightener, step ① involves a wet ball milling time of 2 hours and a wet ball milling speed of 200 r / min; a drying temperature of 80℃ and a drying time of 12 hours; and a drying pressure of atmospheric pressure; the powder is then passed through an 80-mesh sieve. The melting process described in step ① of the preparation method of the optical powder involves heating to 1450℃ at a rate of 5℃ / min and holding at that temperature for 45min in an air atmosphere. The glass slide drying temperature is 110℃ and the glass slide drying time is 2h. In step ② of the preparation method of the light-converting powder, zirconia balls are used as the grinding medium and anhydrous ethanol is used as the solvent during wet ball milling. The mass ratio of glass plate, zirconia balls and anhydrous ethanol is 5:20:

6. The wet ball milling time is 4 hours and the wet ball milling speed is 250 r / min. In step ② of the preparation method of the glass powder, the inlet temperature of the spray drying is 180℃ and the outlet temperature is 90℃; the particle size of the glass powder is D50=0.85μm. The air microcrystallization described in step ③ of the preparation method of the light-converting powder is to first heat the powder to 650℃ at a heating rate of 5℃ / min and hold it for 30min, and then heat it to 810℃ at a heating rate of 5℃ / min and hold it for 90min. In step ③, the pressure of the air jet mill is 0.6 MPa and the atmosphere is nitrogen; the drying treatment is carried out under vacuum at 110°C for 4 hours to obtain rare earth powder with D50=0.8 μm.

6. The high weather-resistant light-converting greenhouse film according to claim 1, characterized in that: The method for preparing the dripping masterbatch consists of the following steps: premixing hydrophilic fumed silica with PEG-4000, then adding ETFE resin and antioxidant 1010 and mixing evenly, and finally adding the mixture to a twin-screw extruder for melt extrusion under a nitrogen atmosphere, followed by filtration, underwater pelletizing, drying, and sieving to obtain the dripping masterbatch.

7. The high weather-resistant light-transfer greenhouse film according to claim 6, characterized in that: In the preparation method of the drip masterbatch, the mixing speed is 400 r / min, the mixing temperature is room temperature, the premixing time is 2 min, the mixing time for adding ETFE resin and antioxidant 1010 is 3 min, and the melt extrusion temperature is 285℃. In the preparation method of drip masterbatch, the underwater pelleting temperature is 25℃, and particles with a diameter of 2.5mm are obtained; the drying temperature is 80℃, the drying time is 15min, and the particles are passed through an 8-mesh sieve. The droplet masterbatch is composed of the following raw materials in parts by mass: 100 parts ETFE resin, 8 parts hydrophilic fumed silica, 2 parts PEG-4000, and 0.2 parts antioxidant 1010.

8. A method for preparing the high weather-resistant light-converting film according to claim 1, characterized in that: It consists of the following steps: (1) Add the outer layer raw material, the middle layer raw material and the inner layer raw material into a high-speed mixer for mixing. After mixing evenly, the outer layer mixture, the middle layer mixture and the inner layer mixture are discharged. (2) The outer layer mixture, the middle layer mixture and the inner layer mixture are respectively added to a three-layer co-extrusion blown film machine for blown film forming, and then cooled, shaped, pulled and wound to prepare a high weather-resistant light-converting greenhouse film.

9. The method for preparing the high weather-resistant light-converting film according to claim 8, characterized in that: In step (1), the parameters for mixing the outer layer, middle layer and inner layer are the same, the mixing temperature is room temperature, the mixing speed is 500 r / min and the mixing time is 3 min; Step (2) The temperature of the feeding section of the three-layer co-extrusion blown film machine is 248-250℃, the temperature of the compression section is 272-274℃, the temperature of the melting section is 286-288℃, the temperature of the homogenization section is 282-283℃, and the temperature of the die head is 284-285℃.

10. The method for preparing the high weather-resistant light-converting film according to claim 8, characterized in that: In step (2), the three-layer melt is extruded through a three-layer co-extrusion die, and the blow-up ratio is controlled to be 3.0 and the traction ratio to be 1.

7. In step (2), the temperature of the air ring during cooling and shaping is controlled at 20℃, and the traction speed is 10m / min.

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