CN114644773B - Preparation method of anti-freezing self-cleaning agricultural anti-fog greenhouse film - Google Patents
Preparation method of anti-freezing self-cleaning agricultural anti-fog greenhouse film Download PDFInfo
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Abstract
The invention discloses a preparation method of an anti-freezing self-cleaning agricultural anti-fog greenhouse film, which is characterized by adding N, N-dimethylformamide, acetic acid and N-octyltriethoxysilane into tetrabutyl titanate to prepare a reaction liquid A, adding zein and sodium dodecyl sulfate into deionized water, sequentially adding gelatin, glucose, polyethylene glycol and silicon dioxide to prepare a reaction liquid B, and then sequentially spin-coating the reaction liquid A, B on a blown polyethylene greenhouse and drying to obtain the polyethylene greenhouse film with lasting anti-fog performance. The invention adopts the continuous spin-coating method for preparation, the process is simple, the condition is controllable, the obtained film material is environment-friendly, has lasting and stable self-cleaning and anti-freezing properties, is resistant to physical impact and chemical corrosion, and can be applied to the fog prevention of greenhouse films.
Description
Technical Field
The invention particularly relates to a preparation method for constructing an agricultural anti-fog greenhouse film with anti-freezing and self-cleaning performances on the surface of a blown polyethylene film.
Background
The film prepared by polyethylene is used as a preferred material for preparing greenhouse films due to the advantages of good light transmission, light weight, dust prevention and the like, but the greenhouse needs to be irrigated in the application process, and the transpiration of crop and soil moisture is carried out, so that the temperature and humidity in the greenhouse are very high, when the moisture in the greenhouse evaporates and meets the cold surface of the greenhouse film, the moisture condenses into water drops to generate a large amount of fog, and the polyethylene film cannot effectively prevent fog due to the characteristics of hydrophobicity, non-polarity and the like. On one hand, the generation of fog causes the light transmittance of the fog to be rapidly reduced, influences the photosynthesis of plants and causes low crop yield, and on the other hand, the fog easily causes the rot of plant fruits or root leaves, the breeding of bacteria and the generation of plant diseases and insect pests. Therefore, solving the problem of fogging of the surface of the greenhouse film is the central importance of the current development of greenhouse cultivation technology.
Functional additives such as dripping agent and the like are added into the polyethylene greenhouse film and then blown into the film, so that the antifogging property of the greenhouse film can be improved, but the strength of the film is reduced, the thermal stability and the transparency of the film are reduced, the nonpolar polyethylene resin and the polar dripping agent have poor compatibility, and the dripping agent is easy to migrate to the surface of the film and form a hydrophilic layer to be washed away by water. The external coating method is to coat the prepared antifogging dripping coating liquid on the surface of a greenhouse film to enable the greenhouse film to have an antifogging dripping function, is simple to operate and is suitable for industrial production, but needs to consider the problems of the magnitude of acting force between the antifogging agent and a polyethylene film and the uniformity of coating application.
Patent CN 112029321A discloses a long-acting antifogging dripping agent for agricultural films prepared by using silicate, modified latex and surfactant and a preparation method thereof, wherein the long-acting antifogging dripping agent has an excellent antifogging and antidrip function, but the preparation process is too complex, and the wear resistance of a coating of the agent is not supported by clear data. According to the invention, the antifogging coating with a hydrophobic titanium dioxide layer and hydrogel layer double-layer structure is constructed by a simple spin-coating method, on one hand, the constructed hydrophobic titanium dioxide layer can absorb ultraviolet light, the aging resistance of the greenhouse film is improved, and the service life of the greenhouse film is prolonged; on the other hand, the hydrogel double-network structure constructed by the zein and the gelatin improves the binding force between the coating and the polyethylene film, enhances the wear resistance of the polyethylene film, and in addition, the frost resistance of the obtained coating enables the polyethylene film to have certain weather resistance, and the self-cleaning prolongs the service life of the greenhouse film.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-freezing self-cleaning agricultural anti-fog greenhouse film, which adopts a spin-coating method to uniformly spread a solution on a blown polyethylene film and dry the film for preparation, solves the problems of complex operation process, poor mechanical property, low light transmittance and easy aging of the hydrophilic anti-fog surface preparation, and the prepared anti-fog greenhouse film has no pollution and no toxicity to the environment.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an anti-freezing self-cleaning agricultural anti-fog greenhouse film comprises the following steps:
(1) Adding N, N-dimethylformamide, acetic acid and N-octyltriethoxysilane into tetrabutyl titanate, and stirring to obtain a reaction solution A;
(2) Pouring a certain amount of zein and sodium dodecyl sulfate into deionized water, uniformly stirring, heating in a water bath, sequentially adding a proper amount of gelatin, glucose, polyethylene glycol and silicon dioxide, and stirring to react to obtain a reaction solution B;
(3) And spin-coating the reaction liquid A on a blown polyethylene film, taking out after drying, spin-coating the reaction liquid B on the reaction liquid A, and then performing secondary drying, thereby obtaining the anti-freezing self-cleaning agricultural anti-fog greenhouse film.
Further, the volume fraction of N, N-dimethylformamide used in the step (1) is 10 to 90% (preferably 50 to 90%), the volume fraction of acetic acid used is 0.001 to 10% (preferably 0.01 to 1%), the volume fraction of N-octyltriethoxysilane used is 0.001 to 10% (preferably 0.01 to 1%), and the volume fraction of tetrabutyl titanate used is 0.001 to 10% (preferably 0.01 to 1%), in terms of the sum of the volume fractions being 100%.
Further, in the step (2), 0.2-80% of zein (preferably 2-40%), 0.5-40% of sodium dodecyl sulfate (preferably 2-20%), 0.2-80% of gelatin (preferably 2-40%), 0.02-20% of glucose (preferably 0.2-2%), 0.02-20% of polyethylene glycol (preferably 0.2-2%) and 0.002-2% of silicon dioxide (preferably 0.02-2%) are added into each 50g of deionized water by mass;
wherein, the mass ratio of the gelatin to the zein is 1/10-3/1 (preferably 1/5-2/1), and the mass ratio of the glucose to the total mass of the zein and the gelatin is 1/50-2/1 (preferably 1/20-1/1). The silicon dioxide is nano silicon dioxide, and the particle size of the silicon dioxide is 1-100 nm.
Further, the reaction temperature of the step (2) is 40-150 ℃, and the reaction time is 0.5-3 h.
Further, the blown polyethylene film used in the step (3) needs to be subjected to oxygen plasma pretreatment or corona treatment before use; wherein the processing time of the oxygen plasma is 10-240 s; the output power of the corona is 2-50 kW, and the processing time is 20 s.
Further, the rotating speed of the spin coating in the step (3) is 500-3000 r/min, and the time is 5-25 s.
Further, the drying temperature in the step (3) is 5-120 ℃, the time for the first drying is 1min, and the time for the second drying is 5-60 s (preferably 10-30 s).
The invention has the advantages that:
(1) The coating prepared by the invention has excellent and lasting antifogging property, low temperature resistance and self-cleaning property, can effectively remove attached oil stains and the like, has high light transmittance and ageing resistance, does not lose the antifogging property after being irradiated by ultraviolet light for one month, can be stored for a long time, and has great potential for industrial application and production.
(2) The coating prepared by the invention has good binding force with a greenhouse film substrate, and shows excellent antifogging performance no matter the coating is physically damaged, such as sand impact with different masses, sand paper friction with 300 circles or adhesive tape adhesion with 70 circles, or is chemically damaged, such as being soaked in different solvents.
(3) The agricultural antifogging shed film is prepared by uniformly spreading and drying the solution on the polyethylene film by adopting the spin-coating method, the operation is simple, the preparation process is simple and convenient, the problems of complex preparation process, long time consumption, poor mechanical property and the like in the traditional method are solved, and the used raw materials are environment-friendly, pollution-free and low in price.
Drawings
FIG. 1 is a picture (a) and an ultraviolet spectrum (b) showing the antifogging effect of the agricultural antifogging shed film and the blank PE film prepared in the third example;
FIG. 2 is the ultraviolet-visible transmission spectrogram (a) of the agricultural antifogging shed film and the blank PE film prepared in example III after being frozen at-23 ℃ for 24 h and the optical image (b) of the agricultural antifogging shed film and the blank PE film after being frozen and exposed to the laboratory environment condition for 3 s;
FIG. 3 is an optical image (b) of the comparison of the freezing delay times of the agricultural antifogging shed film prepared in the third example and the blank PE film at different temperatures (a) and the freezing process of water drops (4 μ L) on the surface thereof at-20 ℃;
FIG. 4 is a comparison of self-cleaning conditions of the agricultural anti-fog greenhouse film prepared in example III and a blank PE film;
FIG. 5 is a graph showing the relationship between the number of times of rubbing with sandpaper and the change of contact angle of the agricultural anti-fog greenhouse film prepared in the third example, wherein the inset is an optical anti-fog picture of the coating after 300 cycles;
fig. 6 is a graph showing the relationship between the antifogging grades of the agricultural antifogging greenhouse film prepared in the third embodiment after being washed by sands with different qualities, wherein the inset is an optical antifogging picture of the coating after being impacted by the sands with different qualities;
FIG. 7 is an optical image of a shed film of comparative example one exposed to laboratory ambient conditions of 3 s after freezing at-23 ℃ for 24 h;
FIG. 8 is an optical image of the greenhouse film from comparative example two after freezing 24 h at-23 ℃ and exposure to laboratory ambient conditions of 3 s;
FIG. 9 is a comparison of the freezing delay times of the third example and the first and second comparative examples at three temperatures of-15 deg.C, -20 deg.C and-25 deg.C.
Detailed Description
A preparation method of an anti-freezing self-cleaning agricultural anti-fog greenhouse film comprises the following steps:
(1) Adding N, N-dimethylformamide, acetic acid and N-octyltriethoxysilane into tetrabutyl titanate, and stirring to obtain a reaction solution A;
(2) Pouring a certain amount of zein and sodium dodecyl sulfate into deionized water, uniformly stirring, heating in a water bath, sequentially adding a proper amount of gelatin, glucose, polyethylene glycol and silicon dioxide, and stirring to react to obtain a reaction solution B;
(3) Placing the blown polyethylene film in a beaker, sequentially performing ultrasonic treatment on the polyethylene film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the polyethylene film in an oven at 60 ℃ for drying, and cooling for later use; after the cleaned polyethylene film is subjected to oxygen plasma treatment 10-240 s or corona treatment 20 s (the output power is 2-50 kW), the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is placed in an oven at the temperature of 5-120 ℃ for drying for 1min and then taken out, the reaction liquid B is spin-coated on the polyethylene film, and the polyethylene film is continuously placed in the oven at the temperature of 5-120 ℃ for drying for 5-60 s, so that the anti-freezing self-cleaning agricultural anti-fog shed film is obtained.
Further, the volume fraction of N, N-dimethylformamide used in the step (1) is 10 to 90% (preferably 50 to 90%), the volume fraction of acetic acid used is 0.001 to 10% (preferably 0.01 to 1%), the volume fraction of N-octyltriethoxysilane used is 0.001 to 10% (preferably 0.01 to 1%), and the volume fraction of tetrabutyl titanate used is 0.001 to 10% (preferably 0.01 to 1%), in terms of the sum of the volume fractions being 100%.
Further, in the step (2), 0.2-80% of zein (preferably 2-40%), 0.5-40% of sodium dodecyl sulfate (preferably 2-20%), 0.2-80% of gelatin (preferably 2-40%), 0.02-20% of glucose (preferably 0.2-2%), 0.02-20% of polyethylene glycol (preferably 0.2-2%) and 0.002-2% of silicon dioxide (preferably 0.02-2%) are added into each 50g of deionized water by mass;
wherein, the mass ratio of the gelatin to the zein is 1/10-3/1 (preferably 1/5-2/1), and the mass ratio of the glucose to the total mass of the zein and the gelatin is 1/50-2/1 (preferably 1/20-1/1). The silicon dioxide is nano silicon dioxide, and the particle size of the silicon dioxide is 1-100 nm.
Further, the reaction temperature of the step (2) is 40-150 ℃, and the reaction time is 0.5-3 h.
Further, the rotating speed of the spin coating in the step (3) is 500-3000 r/min, and the time is 5-25 s.
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
Example one
The embodiment prepares the agricultural anti-fog greenhouse film with anti-freezing and self-cleaning functions according to the following steps:
step one, preparing a reaction solution A
Weighing 88% of N, N-dimethylformamide, 10% of acetic acid and 1% of N-octyltriethoxysilane, adding into 1% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding 1% of zein and 2% of sodium dodecyl sulfate, uniformly stirring, then carrying out water bath at 50 ℃ for 1 h, and sequentially adding 1% of gelatin, 1.6% of glucose, 0.3% of polyethylene glycol and 0.02% of silicon dioxide in the process of stirring, wherein the weight of the deionized water is recorded as reaction liquid B;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film is treated by oxygen plasma 10 s or corona 20 s (output power is 10 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is dried in an oven at 40 ℃ for 1min and then taken out, the reaction liquid B is spin-coated on the polyethylene film (the spin-coating speeds are all 500 r/min, the time is 10 s), and the polyethylene film is continuously dried in the oven at 40 ℃ for 10 s.
Example two
The embodiment prepares the agricultural anti-fog greenhouse film with anti-freezing and self-cleaning functions according to the following steps:
step one, preparing a reaction solution A
Weighing 88% of N, N-dimethylformamide, 1% of acetic acid and 5% of N-octyltriethoxysilane, adding into 6% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding zein accounting for 2.5 percent of the weight of the deionized water and sodium dodecyl sulfate accounting for 8 percent of the weight of the deionized water, uniformly stirring, then carrying out water bath at 70 ℃ for 0.5 h, and sequentially adding gelatin accounting for 2 percent of the weight of the deionized water, 1 percent of glucose, 0.5 percent of polyethylene glycol and 0.14 percent of silicon dioxide in the water bath, wherein the mixture is marked as reaction liquid B;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially performing ultrasonic treatment on the film for 15 min by using acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling the film for later use; the cleaned polyethylene film is treated by oxygen plasma for 18s or corona treatment for 20 s (the output power is 14 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is dried in an oven at 65 ℃ for 1min and then taken out, the reaction liquid B is spin-coated on the polyethylene film (the spin-coating speed is 700 r/min, the time is 12 s), and the polyethylene film is continuously dried in the oven at 65 ℃ for 13 s.
EXAMPLE III
The embodiment prepares the agricultural anti-fog greenhouse film with anti-freezing and self-cleaning functions according to the following steps:
step one, preparing a reaction solution A
Weighing 85% of N, N-dimethylformamide, 1% of acetic acid and 8% of N-octyltriethoxysilane, adding into 6% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding zein accounting for 5% of the weight of the deionized water and sodium dodecyl sulfate accounting for 6% of the weight of the deionized water, uniformly stirring, then carrying out water bath at 65 ℃ for 1.5 h, and sequentially adding gelatin accounting for 5% of the weight of the deionized water, glucose accounting for 1%, polyethylene glycol accounting for 1% of the weight of the deionized water and silicon dioxide accounting for 0.05% of the weight of the deionized water as reaction liquid B;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film is treated by oxygen plasma 15 s or corona 20 s (output power is 35 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is dried in an oven at 70 ℃ for 1min and then taken out, the reaction liquid B is spin-coated on the polyethylene film (the spin-coating speeds are 2000 r/min and the time is 15 s), and the polyethylene film is continuously dried in the oven at 70 ℃ for 40 s.
Example four
The embodiment prepares the agricultural anti-fog greenhouse film with anti-freezing and self-cleaning functions according to the following steps:
step one, preparing a reaction solution A
Weighing 73% of N, N-dimethylformamide, 7% of acetic acid and 10% of N-octyltriethoxysilane, adding into 10% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding 6% of zein and 4% of sodium dodecyl sulfate, uniformly stirring, and then adding gelatin with the weight of 8% of the deionized water, 1.7% of glucose, 10% of polyethylene glycol and 0.1% of silicon dioxide in a water bath of 3 h at 120 ℃ in turn, and marking as a reaction solution B;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film is treated by oxygen plasma 32 s or corona 20 s (output power is 43 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is dried in an oven at 110 ℃ for 1min and then taken out, the reaction liquid B is spin-coated on the polyethylene film (the spin-coating speed is 2500 r/min, the time is 25 s), and the polyethylene film is continuously dried in the oven at 110 ℃ for 25s.
EXAMPLE five
The embodiment prepares the agricultural anti-fog greenhouse film with anti-freezing and self-cleaning functions according to the following steps:
step one, preparing a reaction solution A
Weighing 77% of N, N-dimethylformamide, 8% of acetic acid and 10% of N-octyltriethoxysilane, adding into 5% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding 24% of zein and 4% of sodium dodecyl sulfate, uniformly stirring, then carrying out water bath at 140 ℃ for 1 h, and sequentially adding gelatin, 2.6% of glucose, 1.4% of polyethylene glycol and 0.6% of silicon dioxide in the deionized water, wherein the gelatin, the glucose, the polyethylene glycol and the silicon dioxide are respectively weighed as reaction liquid B;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film is subjected to oxygen plasma treatment 100 s or corona treatment 20 s (the output power is 33 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is placed in an oven at 85 ℃ for drying for 1min and then taken out, the polyethylene film is spin-coated with the reaction liquid B (the spin-coating speed is 2700 r/min and the time is 13 s), and the polyethylene film is placed in the oven at 85 ℃ for continuous drying for 17s.
FIG. 1 is a diagram (a) showing the antifogging effect and UV spectrum (b) of the agricultural antifogging shed film and blank PE film prepared in example III. As shown in fig. 1 (a), after the prepared agricultural anti-fog greenhouse film with the coating and the blank PE film are respectively placed at 2-3 cm above the same beaker with 85 ℃ for 1min, the surface of the blank PE film can be observed to be fogged (left), while the surface of the agricultural anti-fog greenhouse film with the coating is not fogged (right), characters at the bottom of the beaker can be clearly observed, and the coating is proved to have excellent anti-fog performance; as shown in fig. 1 (b), the agricultural antifogging shed film with the coating layer prepared has high light transmittance.
FIG. 2 is the UV-VISIBLE transmitted spectrum of the agricultural antifogging shed film and blank PE film prepared in example III after being frozen at-23 deg.C for 24 h (a) and the optical image of the agricultural antifogging shed film and blank PE film after being frozen and exposed to laboratory environment for 3 s (b). It can be seen from the figure that the agricultural antifogging shed film after freezing treatment maintains the original light transmittance, and has no water/frost condensation and good frost resistance.
FIG. 3 is an optical image of the freezing delay time comparison (a) between the agricultural anti-fog greenhouse film prepared in example III and the blank PE film at-15 deg.C, -20 deg.C, -25 deg.C and the freezing process of water drops (4 μ L) on the surface of the agricultural anti-fog greenhouse film and the blank PE film at-20 deg.C. The agricultural antifogging shed film with the coating can delay the freezing of water at different temperatures.
FIG. 4 is a comparison graph of the self-cleaning conditions of the agricultural anti-fog greenhouse film prepared in the third example and the blank PE film. It can be seen from the figure that the oil stain quickly slides off the surface of the agricultural antifogging shed film with the coating, and the good antifouling performance is proved.
Fig. 5 is a graph showing the relationship between the number of times of rubbing with sandpaper and the change of contact angle of the agricultural anti-fog greenhouse film prepared in the third example, wherein the inset is an optical anti-fog picture of the coating after 300 cycles. As shown in the figure, the coating is pressed on a weight of 200 g to circulate back and forth on 2000# abrasive paper, after 300 times of abrasive paper friction, the coating still has an antifogging effect, the antifogging grade is grade 1, which can be mainly attributed to two aspects, one is that the mechanical strength of the coating is improved due to the space structure of the constructed protein network, and the other is that the mechanical strength of the coating is improved due to the introduction of the SiO inorganic nano-particles 2 And the wear resistance of the coating is endowed.
Fig. 6 is a graph showing the relationship between the antifogging grades of the agricultural antifogging greenhouse film prepared in the third embodiment after being washed by sands with different qualities, wherein the inset is an optical antifogging picture of the coating after being impacted by sands with different qualities. As shown in the figure, the agricultural anti-fog greenhouse film still keeps 1-level anti-fog performance through the scouring of sand with different mass, which is mainly due to the fact that gelatin and zein can construct a solid three-dimensional reticular space structure under the condition that glucose is used as a cross-linking agent, and the gelatin and zein have good binding force with a substrate, can play a buffering role in the impact of gravel, improves the impact resistance of the agricultural anti-fog greenhouse film, and increases the wear resistance of the agricultural anti-fog greenhouse film.
Comparative example 1 (reaction solution B was not added)
Step one, preparing a reaction solution A
Weighing 85% of N, N-dimethylformamide, 1% of acetic acid and 8% of N-octyltriethoxysilane, adding into 6% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film was subjected to oxygen plasma treatment 15 s or corona treatment 20 s (output power 35 kW), and then reaction solution a was spin-coated on the polyethylene film (spin-coating speed 2000 r/min, time 15 s), and placed in an oven at 70 ℃ to dry 40 s continuously.
Comparative example 2 (zein and gelatin were not added to the reaction solution 2)
Step one, preparing a reaction solution A
Weighing 85% of N, N-dimethylformamide, 1% of acetic acid and 8% of N-octyltriethoxysilane, adding into 6% of tetrabutyl titanate, and uniformly stirring to obtain a reaction solution A;
step two, preparing a reaction solution B
Weighing 50g of deionized water, adding sodium dodecyl sulfate accounting for 6% of the weight of the deionized water into the deionized water, uniformly stirring the mixture, and then adding glucose accounting for 1% of the weight of the deionized water, polyethylene glycol accounting for 1% of the weight of the deionized water and silicon dioxide accounting for 0.05% of the weight of the deionized water into a water bath at 65 ℃ for 1.5 h;
step three, spin coating and drying
Firstly, placing a blown polyethylene film in a beaker, sequentially carrying out ultrasonic treatment on the film for 15 min by acetone, absolute ethyl alcohol and deionized water, then placing the film in a 60 ℃ drying oven for drying, and cooling for later use; the cleaned polyethylene film is treated by oxygen plasma 15 s or corona 20 s (output power is 35 kW), then the reaction liquid A is spin-coated on the polyethylene film, the polyethylene film is placed in an oven at 70 ℃ for drying for 1min and then taken out, then the polyethylene film is spin-coated with the reaction liquid B (the spin-coating speed is 2000 r/min, the time is 15 s), and the polyethylene film is placed in the oven at 70 ℃ for continuously drying 40 s.
FIGS. 7-8 are optical images of the shed films from comparative examples one and two, respectively, frozen at-23 deg.C for 24 h and exposed to laboratory ambient conditions for 3 s. As can be seen from the comparison of FIGS. 7 and 8 with FIG. 2, only the coating surface of example three has no steam accumulation, because the condensed water drops can be quickly and uniformly spread on the film surface and slowly absorbed by the coating, thereby achieving excellent anti-freezing effect; and the coating exhibited high light transmittance, the lower graphic representation being clearly visible. The water vapor on the coating of the comparative example is rapidly condensed to form tiny liquid drops, the light transmittance is sharply reduced, and the lower graph is blurred.
FIG. 9 is a graph showing the freezing retardation time of the greenhouse films obtained in the third example and the first and second comparative examples at-15 deg.C, -20 deg.C and-25 deg.C. As can be seen from the figure, the agricultural anti-fog greenhouse film obtained in example three has the best anti-freezing performance, which proves that the protein coating can delay the freezing of water to some extent, and the freezing delay effect of the protein coating can be attributed to the following reasons: (1) Water diffuses into the hydration membrane through forming a hydrogen bond with a hydrophilic zwitterion chain segment of the protein, so that better freezing resistance is obtained; (2) Free water can be absorbed into the protein film and converted into bound water; (3) The hydrophilic material is capable of forming a water-lubricating layer between the coating and the ice, which plays an important role in preventing ice crystal formation.
Table 1 shows the specific properties of the films obtained in the examples and comparative examples. The judgment of the antifogging grade is divided into 1-5 grades according to national standard GB/T31726-2015, wherein the 1 grade is the most excellent antifogging performance, and the higher the grade number is, the worse the antifogging performance is.
TABLE 1 comparative data of different properties of examples and comparative examples
From table 1, it can be seen that the third example has the best performance, the antifogging grade is 1 grade, the rolling angle is the smallest, the freezing delay time is the longest, and the freezing resistance is the most excellent. The comparative example had poor performance because no protein component was added.
In conclusion, the invention provides a preparation method of an agricultural anti-fog greenhouse film with freezing resistance and self-cleaning functions, which adopts a spin-coating method to rapidly spread liquid drops on the surface of a blown polyethylene film and obtains a hydrophilic anti-fog coating after drying. The method has mild reaction conditions, simple and convenient process and easy operation, the obtained coating has excellent rolling angle (only 4.8 degrees), oil stains can quickly roll off from the surface of the coating, meanwhile, the coating has good frost resistance, can be placed for several months at room temperature, is environment-friendly and pollution-free, and has high light transmittance, excellent binding force and wide application prospect.
It should be noted that the above-mentioned embodiments illustrate rather than limit the technical solution of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art will understand that modifications and equivalent substitutions can be made on the technical solution of the present invention, which should be covered by the scope of the claims of the present invention.
Claims (6)
1. A preparation method of an anti-freezing self-cleaning agricultural anti-fog greenhouse film is characterized by comprising the following steps: the method comprises the following steps:
(1) Adding N, N-dimethylformamide, acetic acid and N-octyltriethoxysilane into tetrabutyl titanate, and stirring to obtain a reaction solution A;
(2) Pouring a certain amount of zein and sodium dodecyl sulfate into deionized water, uniformly stirring, heating in a water bath, sequentially adding a proper amount of gelatin, glucose, polyethylene glycol and silicon dioxide, and stirring to react to obtain a reaction solution B;
(3) Spin-coating the reaction liquid A on a blown polyethylene film, taking out after drying, spin-coating the reaction liquid B on the polyethylene film, and then performing secondary drying to obtain the agricultural antifogging shed film;
adding 0.2-80% of zein, 0.5-40% of sodium dodecyl sulfate, 0.2-80% of gelatin, 0.02-20% of glucose, 0.02-20% of polyethylene glycol and 0.002-2% of silicon dioxide into 50g of deionized water;
wherein, the mass ratio of the gelatin to the zein is 1/10-3/1, and the mass ratio of the glucose to the total mass of the zein and the gelatin is 1/50-2/1.
2. The preparation method of the anti-freezing self-cleaning agricultural anti-fog greenhouse film as claimed in claim 1, wherein the method comprises the following steps: the volume fraction of the N, N-dimethylformamide used in the step (1) is 10-90%, the volume fraction of the acetic acid used is 0.001-10%, the volume fraction of the N-octyltriethoxysilane used is 0.001-10%, and the volume fraction of the tetrabutyl titanate used is 0.001-10%, based on the sum of the volume fractions being 100%.
3. The preparation method of the anti-freezing self-cleaning agricultural anti-fog greenhouse film as claimed in claim 1, wherein the method comprises the following steps: the silicon dioxide is nano silicon dioxide, and the particle size of the silicon dioxide is 1-100 nm.
4. The preparation method of the anti-freezing self-cleaning agricultural anti-fog greenhouse film as claimed in claim 1, wherein the method comprises the following steps: the reaction temperature of the step (2) is 40-150 ℃, and the reaction time is 0.5-3 h.
5. The preparation method of the anti-freezing self-cleaning agricultural anti-fog greenhouse film as claimed in claim 1, wherein the method comprises the following steps: the blown polyethylene film used in the step (3) needs to be subjected to oxygen plasma pretreatment or corona pretreatment before use;
wherein the processing time of the oxygen plasma is 10-240 s; the output power of the corona is 2-50 kW, and the treatment time is 20 s.
6. The preparation method of the anti-freezing self-cleaning agricultural anti-fog greenhouse film as claimed in claim 1, wherein the method comprises the following steps: the rotating speed of the spin coating in the step (3) is 500-3000 r/min, and the time is 5-25 s.
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