阅读说明：本技术 一种遮阳网的耐辐射防辐射改性方法 (Radiation-resistant and radiation-proof modification method of sunshade net ) 是由 郭坤 于 2020-12-03 设计创作，主要内容包括：本发明公开了一种遮阳网的耐辐射防辐射改性方法,将聚天冬氨酸溶于缓冲溶液中,加入硬脂酸钠湿法改性水滑石超声分散、磁力搅拌,离心、水洗后分散于六水合硝酸铈水溶液中,超声分散、磁力搅拌,离心、水洗得负载铈离子-聚天冬氨酸的硬脂酸钠湿法改性水滑石；将氧化石墨烯粉体加入N-甲基吡咯烷酮与苯乙烯单体混合溶液中,超声分散,与表面有机改性的氧化钐浆料混合均匀,通氮气密封,置于辐照室内常温辐照后,真空抽滤,用四氢呋喃洗涤得功能化石墨烯-氧化钐；将功能化石墨烯-氧化钐分散液与负载铈离子-聚天冬氨酸的硬脂酸钠湿法改性水滑石加入水性环氧树脂中搅拌,加入水性环氧固化剂搅匀,将所得涂层液均匀涂覆在遮阳网表面,自然干燥。(The invention discloses a radiation-resistant radiation-proof modification method of a sunshade net, which comprises the steps of dissolving polyaspartic acid in a buffer solution, adding sodium stearate wet-method modified hydrotalcite, carrying out ultrasonic dispersion and magnetic stirring, centrifuging, washing, dispersing in a cerous nitrate hexahydrate aqueous solution, carrying out ultrasonic dispersion and magnetic stirring, centrifuging, and washing to obtain cerium ion-polyaspartic acid-loaded sodium stearate wet-method modified hydrotalcite; adding graphene oxide powder into a mixed solution of N-methyl pyrrolidone and a styrene monomer, performing ultrasonic dispersion, uniformly mixing with surface organic modified samarium oxide slurry, introducing nitrogen gas for sealing, placing in an irradiation chamber for irradiation at normal temperature, performing vacuum filtration, and washing with tetrahydrofuran to obtain functionalized graphene-samarium oxide; adding the functionalized graphene-samarium oxide dispersion liquid and the sodium stearate wet-modified hydrotalcite loaded with cerium ions-polyaspartic acid into the aqueous epoxy resin, stirring, adding the aqueous epoxy curing agent, stirring uniformly, uniformly coating the obtained coating liquid on the surface of the sunshade screen, and naturally drying.)

1. A radiation-resistant radiation-proof modification method of a sunshade net is characterized by comprising the following steps of:

(1) carrying modification of hydrotalcite:

dissolving 0.2-0.4 part of polyaspartic acid in 400 parts of 200-one buffer solution, adding 2-4 parts of sodium stearate wet modified hydrotalcite to perform ultrasonic dispersion for 5-10min, magnetically stirring for 30-40min, centrifuging and washing for 3-5 times, dispersing the obtained polyaspartic acid-loaded sodium stearate wet modified hydrotalcite in 80-160 parts of cerous nitrate hexahydrate aqueous solution, performing ultrasonic dispersion for 5-10min, magnetically stirring for 1-2h, centrifuging and washing for 3-5 times to obtain cerium ion-polyaspartic acid-loaded sodium stearate wet modified hydrotalcite;

(2) preparing functionalized graphene-samarium oxide by irradiation modification:

adding 0.75-1.5 parts of graphene oxide powder into a mixed solution of 750-1500 parts of N-methyl pyrrolidone and styrene monomer, performing ultrasonic dispersion for 30-40min, uniformly mixing with 20-40 parts of samarium oxide slurry with organically modified surface, introducing nitrogen gas for sealing, placing in an irradiation chamber for normal-temperature irradiation, performing vacuum filtration, and washing with tetrahydrofuran for 3-5 times to obtain functionalized graphene-samarium oxide;

(3) coating modification of the sunshade net:

adding the functionalized graphene-samarium oxide 1:10-20 obtained in the step (2) into an N-methylpyrrolidone solution, strongly mechanically stirring for 30-40min, and performing ultrasonic treatment for 5-10min to obtain a functionalized graphene-samarium oxide dispersion liquid; adding the cerium ion-polyaspartic acid-loaded sodium stearate wet modified hydrotalcite obtained in the step (1) into 200 parts of aqueous epoxy resin 100-200 parts, stirring for 10-20min, adding 25-50 parts of aqueous epoxy curing agent, stirring uniformly, uniformly coating the obtained coating liquid on the surface of a sunshade net, and naturally drying.

2. The method for modifying radiation resistance and radiation protection of a sunshade screen according to claim 1, wherein the wet modification method of hydrotalcite in the step (1) comprises the following steps: adding 2-4 parts of hydrotalcite into 30-60 parts of deionized water, adding 0.12-0.24 part of sodium stearate, heating in a water bath at 80-85 ℃, shearing, stirring for 1-2h, carrying out suction filtration, washing to neutrality, and drying at 80-85 ℃ to constant weight to obtain sodium stearate wet-process modified hydrotalcite;

the buffer solution consists of 0.05-0.1mol/L Tris-HCl and 0.1-0.2mol/L NaCl, and the pH value is 8-9;

the concentration of the aqueous solution of the cerous nitrate hexahydrate is 0.1-0.2 mol/L.

3. The method for modifying a sunshade screen against radiation and radiation according to claim 1, wherein in the step (2), N-methyl pyrrolidone is mixed with styrene monomer 1: 1;

the samarium oxide surface organic modification method comprises the following steps: adding 10-20 parts of deionized water and 0.2-0.4 part of surface modifier stearic acid into 10-20 parts of samarium oxide, and performing ball milling at the ball milling rotation speed of 400-500rpm for 3-4h to obtain the surface organic modified samarium oxide slurry.

4. The method for modifying a sunshade screen against radiation and radiation as recited in claim 1, wherein in step (2), the irradiation dose rate is 5-10kGy/h, and the total dose is 150-250 kGy.

Technical Field

The invention belongs to the field of sunshade nets, and particularly relates to a radiation-resistant and radiation-proof modification method of a sunshade net.

Background

The sun-shading net covered in summer mainly plays a role in preventing radiation of burning sun, impact of rainstorm, high-temperature damage and spread of plant diseases and insect pests, and especially plays a good role in preventing insect pests from migrating; the effects of light blocking, rain shielding, moisture preservation and temperature reduction are achieved after the covering in summer; moisture preservation principle: after the sunshade net is covered, the communication speed between the air in the covering area and the outside is reduced due to the cooling and windproof effects, so that the relative humidity of the air is obviously increased, the humidity increase value is maximum at noon, generally reaches 13-17%, the humidity is high, the soil evaporation capacity is reduced, and the soil humidity is increased.

The sunshade net is made of polyethylene, high-density polyethylene, PE, PB, PVC, reclaimed materials, virgin materials, and polyethylene propylene, and is treated with ultraviolet stabilizer and anti-oxidation treatment, and has the characteristics of strong tensile resistance, portability and the like; the method is mainly used for the protective cultivation of vegetables, shiitake, flowers, edible fungi, nursery stocks, medicinal materials, ginseng, lucid ganoderma and other crops, the aquaculture of poultry and the like, and has obvious effects of improving the yield and the like.

However, most of commercial sunshade nets have insufficient radiation resistance and aging corrosion resistance, the application prepares the cerium ion-polyaspartic acid-loaded sodium stearate wet-process modified hydrotalcite through the loaded modified hydrotalcite, prepares the functionalized graphene-samarium oxide through irradiation modification, then mixes the functionalized graphene-samarium oxide dispersion liquid and the loaded modified hydrotalcite into the aqueous epoxy resin, and finally, the obtained sunshade net has excellent radiation resistance, radiation protection performance, aging corrosion resistance and wear resistance through coating modification.

Disclosure of Invention

The invention aims to solve the existing problems and provides a radiation-resistant radiation-proof modification method of a sunshade net, and the sunshade net coated and modified according to the method has excellent radiation-resistant radiation-proof performance, ageing-resistant corrosion performance and wear-resistant performance.

The invention is realized by the following technical scheme:

a radiation-resistant radiation-proof modification method of a sunshade net comprises the following steps of:

(1) carrying modification of hydrotalcite:

dissolving 0.2-0.4 part of polyaspartic acid in 400 parts of 200-one buffer solution, adding 2-4 parts of sodium stearate wet modified hydrotalcite to perform ultrasonic dispersion for 5-10min, magnetically stirring for 30-40min, centrifuging and washing for 3-5 times, dispersing the obtained polyaspartic acid-loaded sodium stearate wet modified hydrotalcite in 80-160 parts of cerous nitrate hexahydrate aqueous solution, performing ultrasonic dispersion for 5-10min, magnetically stirring for 1-2h, centrifuging and washing for 3-5 times to obtain cerium ion-polyaspartic acid-loaded sodium stearate wet modified hydrotalcite;

the surface of the hydrotalcite is organically modified by sodium stearate, and the sodium stearate is adsorbed on the surface of the hydrotalcite, so that free hydroxyl on the surface of the hydrotalcite is basically eliminated, and the surface modification of the hydrotalcite is successfully realized; the crystal structure of hydrotalcite is not damaged by the modified sodium stearate, the free edge of the sodium stearate modified hydrotalcite is increased, the particle roughness and the adjacent particle distance are increased, and the reflectivity to ultraviolet light is high; the method comprises the following steps of depositing polyaspartic acid on the surface of sodium stearate wet-process modified hydrotalcite by utilizing electrostatic action, and complexing with trivalent cerium ions as a corrosion inhibitor by using the polyaspartic acid as a cross-linking agent to complete modification of the surface of the hydrotalcite; the modified hydrotalcite is dispersed in the water-based epoxy resin, and the hydrotalcite with the modified surface load can play an obvious self-repairing effect when being applied to an epoxy coating, and can improve the aging and corrosion resistance of the coating;

(2) preparing functionalized graphene-samarium oxide by irradiation modification:

adding 0.75-1.5 parts of graphene oxide powder into a mixed solution of 750-1500 parts of N-methyl pyrrolidone and styrene monomer, performing ultrasonic dispersion for 30-40min, uniformly mixing with 20-40 parts of samarium oxide slurry with organically modified surface, introducing nitrogen gas for sealing, placing in an irradiation chamber for normal-temperature irradiation, performing vacuum filtration, and washing with tetrahydrofuran for 3-5 times to obtain functionalized graphene-samarium oxide;

the modified samarium oxide slurry is prepared by adopting a wet ball milling surface modification process and taking stearic acid as a surface modifier, and the surface organic modification performance ensures that the surface of samarium oxide particles has both hydrophilicity and lipophilicity, so that the samarium oxide particles can be uniformly dispersed in N-methyl pyrrolidone firstly and then can form stronger binding force with aqueous epoxy resin;

the method is characterized in that a gamma-ray irradiation method is adopted for modification to prepare functionalized graphene-samarium oxide, and graphene and surface organic modified samarium oxide are irradiated in an N-methyl pyrrolidone/styrene monomer mixed solution, so that partial reduction and intercalation modification can be realized, and the dispersion stability of the graphene-samarium oxide can be greatly improved; the functionalized graphene-samarium oxide can enhance the corrosion resistance of the coating, and the radiation resistance and radiation protection performance of the coating are good;

(3) coating modification of the sunshade net:

adding the functionalized graphene-samarium oxide 1:10-20 obtained in the step (2) into an N-methylpyrrolidone solution, strongly mechanically stirring for 30-40min, and performing ultrasonic treatment for 5-10min to obtain a functionalized graphene-samarium oxide dispersion liquid; adding the cerium ion-polyaspartic acid-loaded sodium stearate wet modified hydrotalcite obtained in the step (1) and 200 parts of aqueous epoxy resin into the mixture, stirring the mixture for 10 to 20 minutes, adding 25 to 50 parts of aqueous epoxy curing agent into the mixture, stirring the mixture uniformly, coating the obtained coating liquid on the surface of a sunshade net uniformly, and naturally drying the sunshade net;

the coating liquid is prepared by adding functional graphene-samarium oxide and sodium stearate wet-modified hydrotalcite loaded with cerium ions-polyaspartic acid, the addition of graphene is favorable for improving the wear resistance and corrosion resistance of the coating, and the functional graphene-samarium oxide modified coating liquid has excellent radiation resistance and radiation protection performance.

Further, the wet modification method of the hydrotalcite in the step (1) comprises the following steps: adding 2-4 parts of hydrotalcite into 30-60 parts of deionized water, adding 0.12-0.24 part of sodium stearate, heating in a water bath at 80-85 ℃, shearing, stirring for 1-2h, carrying out suction filtration, washing to neutrality, and drying at 80-85 ℃ to constant weight to obtain sodium stearate wet-process modified hydrotalcite;

the buffer solution consists of 0.05-0.1mol/L Tris-HCl and 0.1-0.2mol/L NaCl, and the pH value is 8-9;

the concentration of the aqueous solution of the cerous nitrate hexahydrate is 0.1-0.2 mol/L.

Further, in the step (2), N-methyl pyrrolidone is mixed with styrene monomer 1: 1;

the samarium oxide surface organic modification method comprises the following steps: adding 10-20 parts of deionized water and 0.2-0.4 part of surface modifier stearic acid into 10-20 parts of samarium oxide, and performing ball milling at the ball milling rotation speed of 400-500rpm for 3-4h to obtain the surface organic modified samarium oxide slurry.

Further, the irradiation dose rate in the step (2) is 5-10kGy/h, and the total dose is 150-250 kGy.

Compared with the prior art, the invention has the following advantages:

(1) the surface of the hydrotalcite is organically modified by sodium stearate, and the sodium stearate is adsorbed on the surface of the hydrotalcite, so that free hydroxyl on the surface of the hydrotalcite is basically eliminated, and the surface modification of the hydrotalcite is successfully realized; the crystal structure of hydrotalcite is not damaged by the modified sodium stearate, the free edge of the sodium stearate modified hydrotalcite is increased, the particle roughness and the adjacent particle distance are increased, and the reflectivity to ultraviolet light is high;

the method comprises the following steps of depositing polyaspartic acid on the surface of sodium stearate wet-process modified hydrotalcite by utilizing electrostatic action, and complexing with trivalent cerium ions as a corrosion inhibitor by using the polyaspartic acid as a cross-linking agent to complete modification of the surface of the hydrotalcite; the modified hydrotalcite is dispersed in the water-based epoxy resin, and the hydrotalcite with the surface loaded and modified can play an obvious self-repairing effect when being applied to an epoxy coating, and can improve the aging and corrosion resistance of the coating.

(1) The modified samarium oxide slurry is prepared by adopting a wet ball milling surface modification process and taking stearic acid as a surface modifier, and the surface organic modification performance ensures that the surface of samarium oxide particles has both hydrophilicity and lipophilicity, so that the samarium oxide particles can be uniformly dispersed in N-methyl pyrrolidone firstly and then can form stronger binding force with aqueous epoxy resin;

the method is characterized in that a gamma-ray irradiation method is adopted for modification to prepare functionalized graphene-samarium oxide, and graphene and surface organic modified samarium oxide are irradiated in an N-methyl pyrrolidone/styrene monomer mixed solution, so that partial reduction and intercalation modification can be realized, and the dispersion stability of the graphene-samarium oxide can be greatly improved; the functionalized graphene-samarium oxide can enhance the corrosion resistance of the coating, and the radiation resistance and radiation protection performance of the coating are good.

(3) The coating liquid is prepared by adding functional graphene-samarium oxide and sodium stearate wet-modified hydrotalcite loaded with cerium ions-polyaspartic acid, the addition of graphene is favorable for improving the wear resistance and corrosion resistance of the coating, and the functional graphene-samarium oxide modified coating liquid has excellent radiation resistance and radiation protection performance.

Detailed Description

Example 1

A radiation-resistant radiation-proof modification method of a sunshade net is characterized by comprising the following steps of:

(1) carrying modification of hydrotalcite:

dissolving 0.2 part of polyaspartic acid in 200 parts of buffer solution, adding 2 parts of sodium stearate wet-process modified hydrotalcite, ultrasonically dispersing for 5min, magnetically stirring for 30min, centrifuging, washing with water for 3 times, dispersing the obtained polyaspartic acid-loaded sodium stearate wet-process modified hydrotalcite in 80 parts of cerium nitrate hexahydrate aqueous solution, ultrasonically dispersing for 5min, magnetically stirring for 1h, centrifuging, and washing with water for 3 times to obtain cerium ion-polyaspartic acid-loaded sodium stearate wet-process modified hydrotalcite;

the wet modification method of the hydrotalcite comprises the following steps: adding 2 parts of hydrotalcite into 30 parts of deionized water, adding 0.12 part of sodium stearate, heating, shearing and stirring for 2 hours in a water bath at 80 ℃, filtering, washing to be neutral, and drying to constant weight at 80 ℃ to obtain sodium stearate wet-process modified hydrotalcite;

the buffer solution is composed of 0.05mol/L Tris-HCl and 0.1mol/L NaCl, and the pH value is 8; hexahydrate

The concentration of the cerous nitrate aqueous solution is 0.1 mol/L;

(2) preparing functionalized graphene-samarium oxide by irradiation modification:

adding 0.75 part of graphene oxide powder into 750 parts of mixed solution of N-methyl pyrrolidone and styrene monomer, performing ultrasonic dispersion for 30min, uniformly mixing with 20 parts of samarium oxide slurry with organically modified surface, introducing nitrogen and sealing, placing in an irradiation chamber for normal-temperature irradiation, performing vacuum filtration, and washing with tetrahydrofuran for 3 times to obtain functionalized graphene-samarium oxide;

wherein, N-methyl pyrrolidone is mixed with styrene monomer 1: 1;

the samarium oxide surface organic modification method comprises the following steps: adding 10 parts of deionized water and 0.2 part of surface modifier stearic acid into 10 parts of samarium oxide, and ball-milling at the ball-milling rotating speed of 400rpm for 4 hours to obtain surface organic modified samarium oxide slurry;

the irradiation dose rate is 5kGy/h, and the total dose is 150 kGy;

(3) coating modification of the sunshade net:

adding the functionalized graphene-samarium oxide 1:10 obtained in the step (2) into an N-methylpyrrolidone solution, strongly mechanically stirring for 30min, and performing ultrasonic treatment for 5min to obtain a functionalized graphene-samarium oxide dispersion liquid; adding the cerium ion-polyaspartic acid-loaded sodium stearate wet-modified hydrotalcite obtained in the step (1) and 100 parts of aqueous epoxy resin, stirring for 10min, adding 25 parts of aqueous epoxy curing agent, stirring uniformly, uniformly coating the obtained coating liquid on the surface of a sun-shading net, and naturally drying.

Example 2

A radiation-resistant radiation-proof modification method of a sunshade net is characterized by comprising the following steps of:

(1) carrying modification of hydrotalcite:

dissolving 0.4 part of polyaspartic acid in 400 parts of buffer solution, adding 4 parts of sodium stearate wet-process modified hydrotalcite, ultrasonically dispersing for 10min, magnetically stirring for 40min, centrifuging and washing for 5 times, dispersing the obtained polyaspartic acid-loaded sodium stearate wet-process modified hydrotalcite in 160 parts of cerium nitrate hexahydrate aqueous solution, ultrasonically dispersing for 10min, magnetically stirring for 2h, centrifuging and washing for 5 times to obtain cerium ion-polyaspartic acid-loaded sodium stearate wet-process modified hydrotalcite;

the wet modification method of the hydrotalcite comprises the following steps: adding 4 parts of hydrotalcite into 60 parts of deionized water, adding 0.24 part of sodium stearate, heating, shearing and stirring for 1 hour in a water bath at 85 ℃, filtering, washing to be neutral, and drying at 85 ℃ to constant weight to obtain sodium stearate wet-process modified hydrotalcite;

the buffer solution is composed of 0.1mol/L Tris-HCl and 0.2mol/L NaCl, and the pH value is 9; hexahydrate

The concentration of the cerous nitrate aqueous solution is 0.2 mol/L;

(2) preparing functionalized graphene-samarium oxide by irradiation modification:

adding 1.5 parts of graphene oxide powder into 1500 parts of a mixed solution of N-methyl pyrrolidone and styrene monomer, performing ultrasonic dispersion for 40min, uniformly mixing with 40 parts of samarium oxide slurry with organically modified surface, introducing nitrogen and sealing, placing in an irradiation chamber for normal-temperature irradiation, performing vacuum filtration, and washing with tetrahydrofuran for 5 times to obtain functionalized graphene-samarium oxide;

wherein N-methyl pyrrolidone is mixed with styrene monomer 1: 1;

the samarium oxide surface organic modification method comprises the following steps: adding 20 parts of deionized water and 0.4 part of surface modifier stearic acid into 20 parts of samarium oxide, and performing ball milling at the ball milling rotation speed of 500rpm for 3 hours to obtain surface organic modified samarium oxide slurry;

the irradiation dose rate is 10kGy/h, and the total dose is 250 kGy;

(3) coating modification of the sunshade net:

adding the functionalized graphene-samarium oxide 1:20 obtained in the step (2) into an N-methylpyrrolidone solution, strongly mechanically stirring for 40min, and performing ultrasonic treatment for 10min to obtain a functionalized graphene-samarium oxide dispersion liquid; adding the cerium ion-polyaspartic acid-loaded sodium stearate wet-modified hydrotalcite obtained in the step (1) and 200 parts of aqueous epoxy resin, stirring for 20min, adding 50 parts of aqueous epoxy curing agent, stirring uniformly, uniformly coating the obtained coating liquid on the surface of a sun-shading net, and naturally drying.

Comparative example 1

This comparative example 1 compared to example 1, the hydrotalcite was not wet modified with sodium stearate in step (1), except that the process steps were the same.

Comparative example 2

Compared with the example 2, in the comparative example 2, the samarium oxide slurry whose surface is not organically modified is not subjected to irradiation modification in the step (2), except that the steps of the method are the same.

Blank sunshade net without any modification treatment in control group

In order to compare the performances of the modified sunshade nets prepared by the present invention, the performance tests were performed according to the industry standards on the modified sunshade nets prepared by the methods of the above examples 1 and 2, comparative examples 1 and 2, and on the blank sunshade nets corresponding to the control group without any modification treatment, and the specific comparison data are shown in the following table 1:

wear resistance: referring to ASTM D4060-14 standard, the test conditions are set to 750g/1000r, the rotating speed of a turntable is 72r/min, and the mass of the coated modified sunshade net is weighed to be m by an analytical balance₁Then placing the grinding wheel on a fixed disk, setting the rotation speed and the number of turns, putting down the rocker arm to ensure that the grinding wheel is in good contact with the coating, and weighing the sunshade net again to obtain a mass m after the operation of the instrument is finished₂，m₁And m₂The difference represents the abrasion loss of the sunshade net;

aging and corrosion resistance: thermal oxygen aging test: the mass of a sunshade net sample is 50g, the diameter of a sample plate is 140mm, the thickness of a sunshade net coating film is about 2.2mm, the test temperature is 160 ℃, and the aging time is 24 hours;

testing the shielding performance of the X-ray: measuring the voltage of an X-ray tube at 120kV according to the conditions suggested in GBZ/T147-2002, and calculating the lead equivalent under the conditions that the film pressing condition is 100 ℃, the time is 10min, and the sample size is 10cm multiplied by 0.5 cm;

the sunshade net used in the embodiment of the application is produced by south China plastic products, Inc.;

TABLE 1

Item	Aging corrosion resistance grade	Lead equivalent mmPb
			Example 1	No corrosion	0.52
Example 2	No corrosion	0.53
			Comparative example 1	Weak corrosion	0.52
Comparative example 2	No corrosion	0.16
			Control group	Moderate corrosion	0.03

The sunshade net coated and modified according to the method disclosed by the embodiment of the invention has excellent aging corrosion resistance and radiation-resistant radiation-proof performance, the sunshade net has high lead equivalent, excellent X-ray shielding performance and average quality difference of abrasion loss of 0.012g, and the coated and modified sunshade net has excellent wear-resistant performance;

in comparative example 1, the hydrotalcite is not modified by the sodium stearate in a wet method, so that the ageing-resistant corrosion performance of the sunshade net is poor, but is still better than that of a blank sunshade net of a control group which is not modified; in comparative example 2, the surface organic modified samarium oxide slurry is not subjected to irradiation modification, so that the lead equivalent of the sunshade net coating is reduced, but the radiation resistance and radiation protection performance of the blank sunshade net of a control group without any modification treatment are still better.