CN115071026A - Infrared high-barrier film and preparation method thereof - Google Patents
Infrared high-barrier film and preparation method thereof Download PDFInfo
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- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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- C08L27/00—Compositions of 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 a halogen; Compositions of derivatives of such polymers
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Abstract
The invention discloses an infrared high-barrier film and a preparation method thereof. The preparation method of the infrared high-barrier film comprises the following steps: step 1: respectively placing the raw materials of the PVC supporting layer, the PMMA heat-insulation master batch and the PVDF weather-resistant master batch into a high-speed mixer, and mixing and stirring for 20-40 minutes at 30-50 ℃ to obtain a PVC mixture, a PMMA mixture and a PVDF mixture; and 2, step: putting the PVC mixture into a three-roll calender, and calendering at 100-105 ℃ to obtain a PVC supporting layer; and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the two into a single screw extruder, extruding and immersing the two into a die cavity of a die for molding and drawing a film; obtaining a PVDF/PMMA co-extruded film; and 4, step 4: compounding a PVDF/PMMA co-extruded film and a PVC supporting layer, passing through a casting roller at 105-110 ℃, passing through a cooling roller at 40-60 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Description
Technical Field
The invention relates to the technical field of infrared barrier films, in particular to an infrared high-barrier film and a preparation method thereof.
Background
In recent years, the successful establishment of Olympic games accelerates the progress of the sports industry; the development of sports of the masses can be promoted by the construction of sports stadiums, the fitness public service level of the whole people is improved, and the sports stadium is also one of the products for accelerating the progress of the sports industry.
At present, sports venues such as stadiums, tennis courts and the like with a traditional structure are high in cost and long in period; meanwhile, the temperature and humidity in the traditional closed venue cannot be adjusted and the lighting effect cannot be provided without utilizing external facilities such as air conditioners and lamplight; and if the outdoor stadium is the traditional outdoor stadium, the influence of weather conditions is great, and the utilization rate of the stadium is seriously reduced. And an intelligent inflatable venue containing the fluorine infrared barrier film is produced. It contains infrared blocking agent under having the light transmissivity, can fall the shielding of half near-infrared energy in the solar energy, guarantees the indoor thermal comfort level of building, reduces a large amount of cooling arrangement's use, reduces the waste of energy resource.
In the prior art, the infrared reflectivity of the infrared barrier film is low; and the use of the inorganic particles may lower the light transmittance of the barrier film due to its own light transmittance. Cesium tungstate is a new transparent heat-insulating material with excellent visible light transmittance and near-infrared shielding property; the material not only has strong absorption characteristic in the near-infrared region with the wavelength of 800-1100nm, but also has strong transmission characteristic in the visible light region with the wavelength of 380-780nm, and also has strong shielding characteristic in the ultraviolet light region with the wavelength of 200-380 nm. But the latent heat is poor, and in summer with high temperature, the latent heat absorbs near infrared heat and has a certain heat load on a building; in cold winter, the absorbed near infrared heat can be quickly dissipated in the environment; is not favorable for reasonable application of heat. Meanwhile, cesium tungstate is an inorganic particle, and when the cesium tungstate is mixed with an organic polymer, the problems of dispersibility and compatibility among substances exist, and the light transmittance of the infrared barrier film is reduced. In addition, the state of the nano cesium tungstate, such as particle size and other properties, determines the infrared barrier property of the infrared barrier film; the infrared barrier property in the prior art is lower.
In conclusion, the preparation of the infrared high-barrier film is of great significance in solving the problems.
Disclosure of Invention
The invention aims to provide an infrared high-barrier film and a preparation method thereof, which aim to solve the problems in the background art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of an infrared high-barrier film comprises the following steps:
step 1: respectively placing the raw materials of the PVC supporting layer, the PMMA heat-insulating master batch and the PVDF weather-resistant master batch in a high-speed mixer, and mixing and stirring for 20-40 minutes at 30-50 ℃ to obtain a PVC mixture, a PMMA mixture and a PVDF mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 100-105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity of a die to form a drawn film according to the mass ratio of 1 (1-4); obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extrusion film with a PVC supporting layer, passing through a casting roller at 105-110 ℃, passing through a cooling roller at 40-60 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Preferably, the PVC supporting layer comprises the following raw materials: 95-105 parts of polyvinyl chloride, 26-30 parts of dioctyl phthalate (DOP), 20-24 parts of dibutyl phthalate (DBP), 0.5-1.5 parts of barium stearate (BaSt), 0.5-1 part of cadmium stearate (CdSt) and 0.1-0.3 part of paraffin wax (P-Cl).
Preferably, the PVDF weather-resistant master batch comprises the following raw materials: 95-105 parts of polyvinylidene fluoride (PVDF), 0.05-0.15 part of antioxidant 1010 and 0.2-0.5 part of UV-234 by weight; the PMMA heat insulation master batch comprises the following raw materials: 75-80 parts of polymethyl methacrylate (PMMA), 20-24 parts of infrared blocking agent and 1-4 parts of UV-234 by weight.
Preferably, the raw materials of the infrared blocking agent comprise the following components: 90-92 parts of polymethyl methacrylate, 6-7 parts of nano cesium tungstate and 3-4 parts of UV-234.
Preferably, the preparation method of the infrared blocking agent comprises the following steps: mixing polymethyl methacrylate, nano cesium tungstate and UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
Preferably, the preparation method of the infrared blocking agent comprises the following steps: placing nano cesium tungstate into a sodium dodecyl benzene sulfonate DMF-water mixed solution with the concentration of 0.1mol/L, and uniformly stirring and dispersing, wherein the solid-to-liquid ratio of the nano cesium tungstate to the sodium dodecyl benzene sulfonate solution is 0.01g:10 mL; under the nitrogen atmosphere, adding titanium dioxide as a catalyst, and refluxing for 2-3 hours at the temperature of 120-130 ℃; cooling to 100 ℃, and adding methacrylic acid; adding p-toluenesulfonic acid as a catalyst, stirring for 10-12 hours, and heating to 110 ℃ for reaction for 2 hours; heating to 120 ℃, continuing to react for 2 hours, cooling, washing and drying to obtain a cesium tungstate mixture; mixing the infrared blocking agent with polymethyl methacrylate, UV-234 and sodium acetate at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
Optimally, the adding amount of the methacrylic acid is 3-5 times of the mass of the nano cesium tungstate; the addition amount of the sodium acetate is 1-2 wt% of the methacrylic acid; the volume ratio of DMF to water in the sodium dodecyl benzene sulfonate DMF-water mixed solution is 1: 1. DMF is N, N-dimethylformamide.
Preferably, the preparation method of the nano cesium tungstate comprises the following steps: dispersing cesium salt and alanine in a citric acid solution to obtain a cesium solution; dissolving a tungsten salt in a methanol-water solvent to obtain a tungsten solution; mixing the two solutions in a nitrogen atmosphere, and stirring for 2-3 hours at the temperature of 190-200 ℃; cooling to 80-90 ℃, adding urea to adjust the pH value to 3-5, stirring for reaction for 4-5 hours, naturally cooling, aging, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2-3 hours at the temperature of 500-550 ℃ to obtain cesium tungstate powder B; placing the cesium tungstate into sodium dodecyl benzene sulfonate solution, wet grinding, washing and drying to obtain the nano cesium tungstate.
Preferably, the concentration of the citric acid is 2-3 mol/L; the addition amount of the alanine is 3-5 wt% of the mass of the cesium salt; the volume ratio of the methanol to the water is 5: 1; the mass ratio of the cesium tungstate powder A to the solid citric acid is (6-7) to (3-4).
Preferably, the infrared high-barrier film is prepared by the preparation method of the infrared high-barrier film.
In the technical scheme, the PVC film is used as a supporting layer and is thermally compounded with the PVDF/PMMA co-extruded film to obtain the infrared high-barrier film which is used for the outer surfaces of the stock buildings and the like with the requirements of cooling, energy conservation, environmental protection, improvement of human body comfort level and the like; providing natural glare-free lighting needs for venues.
In the scheme, a hot bonding process is adopted, the technology is mature, no adhesive is used, the process is environment-friendly, and the operation is simple; meanwhile, the nano cesium tungstate is optimally proportioned, so that the film has excellent performance, the light transmittance can reach over 85 percent, and the heat insulation rate can reach 80 percent. When the environment temperature is higher (above 25 ℃), the thermal radiance is very high (90%), and the PVDF/PMMA co-extrusion film is contained in the film, so that the heat dissipation is promoted; when the weather turns cold, the emissivity of the film switches to 20%, which helps to maintain the absorption of solar energy and the heat of indoor heating.
In the scheme, the infrared blocking performance is further improved by improving the preparation method of the cesium tungstate nanoparticles. During the preparation process, alanine is added into the cesium salt as a coating agent of the nano particles to inhibit the aggregation of the nano particles and the increase of the particle size, because the reaction is not carried out under the ultrasonic wave in the scheme, so that the coating agent needs to be added to enhance the uniformity of the formation of the nano particles to form the nano particles with smaller particle size and uniform dispersion. On the other hand, the coating of the substance can form reductive ammonia gas in the nitrogen pyrolysis process, increase the defect sites of cesium tungstate and increase the content of pentavalent tungsten ions, thereby enhancing the infrared barrier property of the cesium tungstate.
In addition, in the pyrolysis process, in order to promote the increase of defect sites, citric acid is further added for assisting heat treatment, and reducing carbon monoxide gas can be generated; meanwhile, the particle size is increased due to the secondary growth of cesium tungstate in the pyrolysis process, and the light transmittance and infrared barrier property are affected when the particle size is increased and used in the film; however, the presence of citric acid and alanine pyrolyzes to produce carbon coating on the nanoparticles, inhibiting particle size growth. And then wet milling is used for removing carbon to obtain the nano cesium tungstate. With the above-described modification steps, the performance of the infrared barrier film is enhanced.
In the scheme, the light transmittance and the latent heat of the infrared barrier film are improved by pretreating the cesium tungstate nanoparticles. Because of the dispersibility of the cesium tungstate nanoparticles in the polymer, the cesium tungstate nanoparticles are uniformly dispersed in a DMF-water mixed solution containing sodium dodecyl benzene sulfonate; then heating to reflux and degrade sodium dodecyl benzene sulfonate to generate dodecanol and oxidize to generate alkanoic acid; dodecanol can be esterified with methacrylic acid to generate an acrylate compound; so that it has similar compatibility with PMMA and facilitates dispersion. In another aspect, dodecanol and lauric acid form a eutectic mixture in the presence of sodium acetate; the co-feeding mixture and the acrylate compound with the dodecyl chain generated by the method have better latent heat property, and can enhance the heat absorbed by the sodium tungstate, thereby enhancing the reasonable application of the absorbed heat; the heat insulation performance of the film is increased, and the comfort level in a building venue is enhanced.
And then, improving the dispersity of the cesium tungstate nanoparticles and enhancing the performance of the infrared barrier film by utilizing the compatibility between the pretreated cesium tungstate nanoparticles and PMMA and the good compatibility between PMMA and PVDF.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 3 hours at the temperature of 190 ℃; cooling to 85 ℃, adding urea to adjust the pH value to 4, stirring to react for 4.5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) And mixing 91 parts of polymethyl methacrylate, 7 parts of nano cesium tungstate and 3 parts of UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Placing 100 parts of polyvinyl chloride, 28 parts of dioctyl phthalate, 22 parts of dibutyl phthalate, 1 part of barium stearate, 0.7 part of cadmium stearate and 0.2 part of paraffin into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVC mixture; placing 100 parts of polyvinylidene fluoride, 0.1 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 1; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 50 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Example 2:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 3 hours at the temperature of 190 ℃; cooling to 85 ℃, adding urea to adjust the pH value to 4, stirring to react for 4.5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) And mixing 91 parts of polymethyl methacrylate, 7 parts of nano cesium tungstate and 3 parts of UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Placing 100 parts of polyvinyl chloride, 28 parts of dioctyl phthalate, 22 parts of dibutyl phthalate, 1 part of barium stearate, 0.7 part of cadmium stearate and 0.2 part of paraffin into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVC mixture; placing 100 parts of polyvinylidene fluoride, 0.1 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 2; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 50 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Example 3:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 3 hours at the temperature of 190 ℃; cooling to 85 ℃, adding urea to adjust the pH value to 4, stirring to react for 4.5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) And mixing 91 parts of polymethyl methacrylate, 7 parts of nano cesium tungstate and 3 parts of UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Placing 100 parts of polyvinyl chloride, 28 parts of dioctyl phthalate, 22 parts of dibutyl phthalate, 1 part of barium stearate, 0.7 part of cadmium stearate and 0.2 part of paraffin into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVC mixture; placing 100 parts of polyvinylidene fluoride, 0.1 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and 3, step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 3; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 50 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Example 4:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 3 hours at the temperature of 190 ℃; cooling to 85 ℃, adding urea to adjust the pH value to 4, stirring to react for 4.5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) And mixing 91 parts of polymethyl methacrylate, 7 parts of nano cesium tungstate and 3 parts of UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Placing 100 parts of polyvinyl chloride, 28 parts of dioctyl phthalate, 22 parts of dibutyl phthalate, 1 part of barium stearate, 0.7 part of cadmium stearate and 0.2 part of paraffin into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVC mixture; placing 100 parts of polyvinylidene fluoride, 0.1 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 4; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 50 ℃, and fully stretching; and carrying out surface corona, edge cutting and rolling to obtain the infrared high-barrier film.
Example 5:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 3 hours at the temperature of 190 ℃; cooling to 85 ℃, adding urea to adjust the pH value to 4, stirring to react for 4.5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) Placing 7 parts of nano cesium tungstate into a 0.1mol/L sodium dodecyl benzene sulfonate DMF-water (volume ratio is 1:1) mixed solution, and uniformly stirring and dispersing, wherein the solid-to-liquid ratio of the nano cesium tungstate to the sodium dodecyl benzene sulfonate solution is 0.01g:10 mL; under the nitrogen atmosphere, 0.5 part of titanium dioxide is added as a catalyst, and the mixture is refluxed for 2 hours at the temperature of 120 ℃; cooling to 100 ℃, and adding methacrylic acid, wherein the adding amount of the methacrylic acid is 4 times of the mass of the nano cesium tungstate; adding p-toluenesulfonic acid as a catalyst, stirring for 12 hours, and heating to 110 ℃ for reaction for 2 hours; heating to 120 ℃, continuing to react for 2 hours, cooling, washing and drying to obtain a cesium tungstate mixture; mixing the mixture with 91 parts of polymethyl methacrylate, 3 parts of UV-234 and sodium acetate, wherein the addition amount of the sodium acetate is 1.5 wt% of the methacrylic acid, mixing at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Placing 100 parts of polyvinyl chloride, 28 parts of dioctyl phthalate, 22 parts of dibutyl phthalate, 1 part of barium stearate, 0.7 part of cadmium stearate and 0.2 part of paraffin into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVC mixture; placing 100 parts of polyvinylidene fluoride, 0.1 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 30 minutes at 40 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and 3, step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 3; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 50 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Example 6:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 2mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under the nitrogen atmosphere, and stirring for 2 hours at the temperature of 190 ℃; cooling to 80 ℃, adding urea to adjust the pH value to 3, stirring to react for 4 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 3 hours at the set temperature of 500 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) Putting 6 parts of nano cesium tungstate into a 0.1mol/L sodium dodecyl benzene sulfonate DMF-water (volume ratio is 1:1) mixed solution, and uniformly stirring and dispersing, wherein the solid-to-liquid ratio of the nano cesium tungstate to the sodium dodecyl benzene sulfonate solution is 0.01g:10 mL; under the nitrogen atmosphere, 0.5 part of titanium dioxide is added as a catalyst, and the mixture is refluxed for 3 hours at the temperature of 120 ℃; cooling to 100 ℃, and adding methacrylic acid, wherein the adding amount of the methacrylic acid is 3 times of the mass of the nano cesium tungstate; adding p-toluenesulfonic acid as a catalyst, stirring for 10 hours, and heating to 110 ℃ for reaction for 2 hours; heating to 120 ℃, continuing to react for 2 hours, cooling, washing and drying to obtain a cesium tungstate mixture; mixing the mixture with 90 parts of polymethyl methacrylate, 3 parts of UV-234 and sodium acetate, wherein the addition amount of the sodium acetate is 1 wt% of the methacrylic acid, mixing at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Putting 95 parts of polyvinyl chloride, 26 parts of dioctyl phthalate, 20 parts of dibutyl phthalate, 0.5 part of barium stearate, 0.5 part of cadmium stearate and 0.1 part of paraffin into a high-speed mixer, and mixing and stirring for 40 minutes at 30 ℃ to obtain a PVC mixture; placing 95 parts of polyvinylidene fluoride, 0.05 part of antioxidant 1010 and 0.2 part of UV-234 into a high-speed mixer, and mixing and stirring for 20 minutes at 30 ℃ to obtain a PVDF mixture; placing 75 parts of polymethyl methacrylate, 20 parts of infrared blocking agent and 1 part of UV-234 into a high-speed mixer, and mixing and stirring for 20 minutes at 30 ℃ to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 100 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 3; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 105 ℃, passing through a cooling roller at 40 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Example 7:
step 1: (1) the mass ratio of the cesium carbonate to the sodium tungstate is 1.5: 1; dispersing cesium carbonate and alanine in a citric acid solution with the concentration of 3mol/L to obtain a cesium solution with the concentration of 0.25 mol/L; dissolving sodium tungstate in a methanol-water solvent to obtain a tungsten solution of 0.25 mol/L; mixing the two solutions under nitrogen atmosphere, and stirring at 200 ℃ for 3 hours; cooling to 90 ℃, adding urea to adjust the pH value to 5, stirring to react for 5 hours, naturally cooling, aging for 24 hours, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2 hours at the set temperature of 550 ℃ to obtain cesium tungstate powder B; placing the mixture into a sodium dodecyl benzene sulfonate solution with the concentration of 0.1mol/L, carrying out wet milling on the mixture in a ball milling tank, wherein the ball milling medium is 3.0mm zirconium oxide grinding balls, and grinding for 60min at the rotating speed of 300 rpm; washing and drying to obtain the nano cesium tungstate.
(2) Placing 7 parts of nano cesium tungstate into a 0.1mol/L sodium dodecyl benzene sulfonate DMF-water (volume ratio is 1:1) mixed solution, and uniformly stirring and dispersing, wherein the solid-to-liquid ratio of the nano cesium tungstate to the sodium dodecyl benzene sulfonate solution is 0.01g:10 mL; under the nitrogen atmosphere, 0.5 part of titanium dioxide is added as a catalyst, and the mixture is refluxed for 2 hours at the temperature of 130 ℃; cooling to 100 ℃, and adding methacrylic acid, wherein the adding amount of the methacrylic acid is 5 times of the mass of the nano cesium tungstate; adding p-toluenesulfonic acid as a catalyst, stirring for 12 hours, and heating to 110 ℃ for reaction for 2 hours; heating to 120 ℃, continuing to react for 2 hours, cooling, washing and drying to obtain a cesium tungstate mixture; mixing the mixture with 92 parts of polymethyl methacrylate, 4 parts of UV-234 and sodium acetate, wherein the addition amount of the sodium acetate is 2 wt% of the methacrylic acid, mixing at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
(3) Putting 105 parts of polyvinyl chloride, 30 parts of dioctyl phthalate, 24 parts of dibutyl phthalate, 1.5 parts of barium stearate, 1 part of cadmium stearate and 0.3 part of paraffin into a high-speed mixer, and mixing and stirring for 40 minutes at 50 ℃ to obtain a PVC mixture; putting 105 parts of polyvinylidene fluoride, 0.15 part of antioxidant 1010 and 0.5 part of UV-234 into a high-speed mixer, and mixing and stirring for 40 minutes at 50 ℃ to obtain a PVDF mixture; placing 80 parts of polymethyl methacrylate, 24 parts of infrared blocking agent and 4 parts of UV-234 into a high-speed mixer, and mixing and stirring at 50 ℃ for 40 minutes to obtain a PMMA mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a die cavity for forming and drawing a film according to the mass ratio of 1: 3; obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film with a PVC supporting layer, passing through a casting roller at 110 ℃, passing through a cooling roller at 60 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
Comparative example 1: PVDF film 50 μm thick.
Comparative example 2: 50 μm thick neat PMMA film.
Comparative example 3: the preparation method of CN201510323309.9 in example 1 is referred to obtain nano cesium tungstate, which is used for replacing nano cesium tungstate in example 5, and the rest is the same as example 5.
Comparative example 4: the procedure was as in example 5 except that no glycine was added.
Comparative example 5: pyrolysis was assisted without the addition of solid citric acid and was otherwise the same as in example 5.
Comparative example 6: the concentration of 0.1mol/L sodium dodecylbenzenesulfonate DMF-water was changed to 0.5mol/L, and the procedure was otherwise the same as in example 5.
Comparative example 7: the procedure is as in example 5 except that no sodium acetate is added.
Experiment 1: the infrared high-barrier film prepared in the examples and the comparative examples is taken for carrying out related performance detection, and the specific data are shown in the following table:
| examples | Light transmittance% | Haze%) | Infrared shielding rate% |
| Example 1 | 92 | 1.5 | 35 |
| Example 2 | 92 | 1.7 | 52 |
| Example 3 | 86 | 2.5 | 80 |
| Example 4 | 71 | 3.3 | 88 |
| Example 5 | 89 | 2.6 | 87 |
| Example 6 | 87 | 2.5 | 84 |
| Example 7 | 86 | 2.7 | 89 |
| Comparative example 1 | 90 | 6.1 | 12 |
| Comparative example 2 | 93 | 0.5 | 12 |
| Comparative example 3 | 81 | 2.6 | 80 |
| Comparative example 4 | 84 | 2.8 | 84 |
| Comparative example 5 | 80 | 3.0 | 83 |
| Comparative example 6 | 79 | 3.1 | 85 |
| Comparative example 7 | 88 | 2.5 | 85 |
Conclusion 1: as shown by the data in the table above: comparison of examples 1-4 with comparative examples 1-2 shows that: with the increase of PMMA master batch, the infrared blocking rate gradually rises, and the light transmittance gradually falls; the reason is that: the addition of the infrared blocking agent containing nano cesium tungstate causes the problems of dispersibility and compatibility, and the light reflection is increased, so that the light transmittance is reduced; but because of the infrared shielding property of the nano cesium tungstate, the content of the nano cesium tungstate is increased, and the infrared blocking property is enhanced. The preferred embodiment is example 3: the mass ratio of the PVDF weather-resistant master batch to the PMMA heat-insulating master batch is 1: 3.
Comparison of examples 5-6 with example 3 shows that: the further treatment of the nano cesium tungstate can improve the light transmittance to a small extent, because: the pretreatment process enhances the dispersibility and substance compatibility thereof, reduces the internal reflection of light, and thus increases the light transmittance. It should be noted that: due to the addition of the long alkyl chain segment, the roughness of the film is not increased under a certain amount of conditions, and the haze influence is small; however, when the equivalent is further increased, there is an effect that the transmittance is decreased and the haze is increased as shown in the data of comparative example 6.
The comparative examples of example 5 and comparative examples 3-5 show that: the performance of the infrared barrier film can be enhanced by adjusting the preparation method of the nano cesium tungstate and controlling the performance of the nano cesium tungstate. Compared with the nano cesium tungstate which is not improved in the comparative example 3, the performance is reduced most obviously; secondly, no solid citric acid is added in comparative example 5 to assist pyrolysis and no glycine is added in comparative example 4; the reason is that: glycine is a coating agent of the nano particles, can inhibit aggregation and generation of large particles, and enhances the formation of dispersed and uniform particles of the nano particles; meanwhile, the gas with reducibility is generated in the pyrolysis process with citric acid, so that the defect sites of the nano ions are enhanced, and the performance is enhanced.
Experiment 2: the infrared high-barrier film prepared in the examples 3 and 5 and the comparative examples 6 to 7 is applied to the surface of a transparent glass container; infrared lamps (philips R125) were used as simulated solar light sources; detecting the temperature in the container by using a thermocouple; the temperatures were measured at 0 and 10 minutes and the results are shown in the following table:
| examples | Temperature of 0min | Temperature for 10min |
| Example 3 | 23.7 | 31.3 |
| Example 5 | 22.4 | 27.2 |
| Comparative example 6 | 23.1 | 26.8 |
| Comparative example 7 | 23.5 | 29.4 |
| Glass container without film | 22.3 | 41.8 |
Conclusion 2: as shown in the data above: comparison of the data of example 3 with that of an uncoated glass container shows that nano cesium tungstate has heat absorptivity and heat insulation property; comparing example 3 with example 5, it is shown that by pretreatment of nano particles, latent heat substance can be generated, and heat insulation property is enhanced; in comparative example 6, the heat insulation property was increased due to the increase of the amount of sodium dodecylbenzenesulfonate, but the increase thereof decreased the light transmittance. In comparative example 7, the addition of sodium acetate increased the thermal insulation by adding dodecanol and lauric acid to the sodium acetate eutectic mixture, thus resulting in a slight decrease in performance.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of an infrared high-barrier film is characterized by comprising the following steps: the method comprises the following steps:
step 1: respectively placing the raw materials of the PVC supporting layer, the PMMA heat-insulating master batch and the PVDF weather-resistant master batch in a high-speed mixer, and mixing and stirring for 20-40 minutes at 30-50 ℃ to obtain a PVC mixture, a PMMA mixture and a PVDF mixture;
step 2: putting the PVC mixture into a three-roll calender, and calendering at 100-105 ℃ to obtain a PVC supporting layer;
and step 3: respectively putting the PMMA mixture and the PVDF mixture into a double-screw extruder for mixing, extruding and granulating; standing and drying to obtain PMMA heat-insulating master batches and PVDF weather-resistant master batches; putting the PVDF weather-resistant master batch and the PMMA heat-insulating master batch into a single-screw extruder, and extruding and immersing into a die cavity of a die to form a drawing film according to the mass ratio of the PVDF weather-resistant master batch to the PMMA heat-insulating master batch of 1 (1-4); obtaining a PVDF/PMMA co-extruded film;
and 4, step 4: compounding a PVDF/PMMA co-extruded film and a PVC supporting layer, passing through a casting roller at 105-110 ℃, passing through a cooling roller at 40-60 ℃, and fully stretching; and performing surface corona, trimming and rolling to obtain the infrared high-barrier film.
2. The method for preparing the infrared high-barrier film according to claim 1, wherein the method comprises the following steps: the PVC supporting layer comprises the following raw materials: 95-105 parts of polyvinyl chloride, 26-30 parts of dioctyl phthalate, 20-24 parts of dibutyl phthalate, 0.5-1.5 parts of barium stearate, 0.5-1 part of cadmium stearate and 0.1-0.3 part of paraffin.
3. The method for preparing the infrared high-barrier film according to claim 1, wherein the method comprises the following steps: the PVDF weather-resistant master batch comprises the following raw materials: 95-105 parts of polyvinylidene fluoride, 0.05-0.15 part of antioxidant 1010 and 0.2-0.5 part of UV-234 by weight; the PMMA heat insulation master batch comprises the following raw materials: 75-80 parts of polymethyl methacrylate, 20-24 parts of infrared blocking agent and 1-4 parts of UV-234 by weight.
4. The method for preparing the infrared high-barrier film according to claim 3, wherein the method comprises the following steps: the raw materials of the infrared blocking agent comprise the following components: 90-92 parts of polymethyl methacrylate, 6-7 parts of nano cesium tungstate and 3-4 parts of UV-234.
5. The method for preparing the infrared high-barrier film according to claim 4, wherein the method comprises the following steps: the preparation method of the infrared blocking agent comprises the following steps: mixing polymethyl methacrylate, nano cesium tungstate and UV-234 at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
6. The method for preparing the infrared high-barrier film according to claim 4, wherein the method comprises the following steps: the preparation method of the infrared blocking agent comprises the following steps: placing nano cesium tungstate in a sodium dodecyl benzene sulfonate DMF-water mixed solution, and uniformly stirring and dispersing; under the nitrogen atmosphere, adding titanium dioxide as a catalyst, and refluxing for 2-3 hours at the temperature of 120-130 ℃; cooling to 100 ℃, and adding methacrylic acid; adding p-toluenesulfonic acid as a catalyst, stirring for 10-12 hours, and heating to 110 ℃ for reaction for 2 hours; heating to 120 ℃, continuing to react for 2 hours, cooling, washing and drying to obtain a cesium tungstate mixture; mixing the infrared blocking agent with polymethyl methacrylate, UV-234 and sodium acetate at low temperature, and placing the mixture in a double-screw extruder for mixing, extruding and granulating to obtain the infrared blocking agent.
7. The method for preparing the infrared high-barrier film according to claim 6, wherein the method comprises the following steps: the addition amount of the methacrylic acid is 3-5 times of the mass of the nano cesium tungstate; the addition amount of the sodium acetate is 1-2 wt% of the methacrylic acid; the volume ratio of DMF to water in the sodium dodecyl benzene sulfonate DMF-water mixed solution is 1: 1.
8. The method for preparing the infrared high-barrier film according to claim 4, wherein the method comprises the following steps: the preparation method of the nano cesium tungstate comprises the following steps: dispersing cesium salt and alanine in a citric acid solution to obtain a cesium solution; dissolving a tungsten salt in a methanol-water solvent to obtain a tungsten solution; mixing the two solutions in a nitrogen atmosphere, and stirring for 2-3 hours at the temperature of 190-200 ℃; cooling to 80-90 ℃, adding urea to adjust the pH value to 3-5, stirring for reaction for 4-5 hours, naturally cooling, aging, washing and freeze-drying to obtain cesium tungstate powder A; uniformly mixing the cesium tungstate powder A with solid citric acid, placing the mixture in a high-temperature furnace of inert gas, and reacting for 2-3 hours at the temperature of 500-550 ℃ to obtain cesium tungstate powder B; placing the cesium tungstate into sodium dodecyl benzene sulfonate solution, wet grinding, washing and drying to obtain the nano cesium tungstate.
9. The method for preparing an infrared high-barrier film according to claim 8, wherein the method comprises the following steps: the concentration of the citric acid is 2-3 mol/L; the addition amount of the alanine is 3-5 wt% of the mass of the cesium salt; the volume ratio of the methanol to the water is 5: 1; the mass ratio of the cesium tungstate powder A to the solid citric acid is (6-7) to (3-4).
10. The infrared high-barrier film prepared by the preparation method of the infrared high-barrier film according to any one of claims 1 to 9.
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