Greenhouse asparagus beet armyworm control spraying agent and preparation process thereof

Abstract

The invention relates to the technical field of pesticides, in particular to a spraying agent for preventing and treating asparagus caterpillar of greenhouse asparagus and a preparation process of the spraying agent. Comprising the following steps: preparing a fiber wetting enhancer; compounding a photo-thermal response elastic membrane material and preparing a suspension; and preparing the spodoptera exigua prevention and control spraying agent. A hindered urea bond monomer is prepared, the hindered urea bond monomer reacts with 1, 4-bis-[4-(6-acryloyloxy hexyloxy) benzoyloxy]-2-methyl benzene, sulfhydrylation carbon nanotubes are added, stretching and fixing are performed to obtain a photo-thermal response elastic membrane material, the photo-thermal response elastic membrane material is added into the slow-release hydrogel, insect killing can be performed according to the characteristic that noctuids stay in the daytime and come out at night, and the slow-release hydrogel has the advantages that the slow-release effect is good; ineffective release of the composite insecticide in the daytime is avoided, the utilization rate of the composite insecticide is greatly increased, the effective insecticidal period is prolonged, the prevention and control efficiency of beet armyworms is improved, the spraying frequency and spraying amount of the insecticide can be reduced, and ecological and economic double benefits are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides and insecticides, and in particular to a greenhouse asparagus beet armyworm control spray and a preparation process thereof. Background Art

[0002] In recent years, with the rapid development of facility agriculture, greenhouse asparagus has become an important economic crop due to its off-season and high-yield advantages. However, the closed, high-humidity and significant temperature difference between day and night in the greenhouse (the temperature can reach 25-30℃ during the day and often drops to 15-20℃ at night) provide a breeding ground for Lepidoptera noctuid pests. Among them, the representative beet armyworm has the typical habit of hiding during the day and coming out at night. It often migrates to the tender stems of asparagus to feed at night, and it is often necessary to spray pesticides to kill its larvae and adults.

[0003] After spraying, traditional pesticides are affected by environmental factors such as temperature and light, and tend to become ineffective quickly in the environment, resulting in low pesticide utilization, frequent application of pesticides, and increased risks of pest resistance and soil residues. To address this, existing technologies often use a slow-release method to slow down the release rate of the agent, avoid its ineffective release in the environment, and thus increase the utilization rate of the agent.

[0004] In addition to conventional sustained release, current pesticide sustained release technologies also include thermosensitive sustained release and pH-responsive sustained release. Conventional sustained release can often only fix the release rate of the agent within a small range, and cannot further achieve precise and efficient prevention and control. Thermosensitive sustained release usually utilizes a PNIPAM hydrogel sustained release system, which accelerates its release rate at high temperatures and slows down its release rate at low temperatures. The habit of noctuid pests that hide during the day and come out at night is not taken into account. The pH-responsive sustained release is uncontrollable in the prevention and control of pests, and its sustained release effect is easily changed by environmental factors such as humidity, and it is also impossible to achieve precise and efficient prevention and control of pests. Summary of the invention

[0005] In order to solve the above technical defects, the present invention has developed a greenhouse asparagus beet armyworm control spray and its preparation process. By adding high-temperature shrinkage and low-temperature recovery materials into the slow-release hydrogel, it can match the habits of the armyworm hiding during the day and coming out at night to carry out targeted insecticide control, achieve the purpose of accurate and efficient control, reduce the amount of pesticides used, and better protect the ecological environment.

[0006] A preparation process of a greenhouse asparagus beet armyworm control spray, comprising the following steps: Preparation of S1 fiber wetting enhancer: grind the merbau wood into powder, perform enzymolysis and alcohol extraction to obtain merbau extract powder, dissolve the merbau extract powder and epigallocatechin gallate in anhydrous ethanol, add potassium dihydrogen phosphate aqueous solution containing laccase and mix well, then add cellulose nanofibers to react in a water bath, centrifuge and dry the precipitate to obtain the fiber wetting enhancer; S2 Preparation of composite photothermal responsive elastic film and suspension: isocyanoethyl methacrylate and N, N'-di-tert-butylethylenediamine are reacted in anhydrous dichloromethane to obtain a hindered urea bond monomer, which is then reacted with 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene and thiolated carbon nanotubes are added to obtain a photothermal liquid crystal polymer film, which is stretched and cured and then sheared in deionized water to obtain a photothermal responsive elastic film suspension; S3 preparation of beet armyworm control spray: chlorantraniliprole, patchouli ketone and graphene oxide solution are mixed and stirred in a water bath, and a composite insecticide carrier is obtained after centrifugal washing. Acrylic acid and acrylamide are pre-polymerized and added into a photothermal responsive elastic membrane suspension, a fiber wetting enhancer and the composite insecticide carrier, and stirred evenly. After heating and polymerization, the mixture is evenly mixed with deionized water to obtain a beet armyworm control spray.

[0007] Furthermore, step S1 of preparing the fiber wetting enhancer comprises the following steps: S1.1: Dry the merbau wood and grind it into powder to obtain merbau powder, then mix 30-40 parts by weight of the merbau powder, 150-200 parts by weight of citric acid aqueous solution and 3-5 parts by weight of cellulase, and place in a constant temperature water bath at 50-55° C. for 24-30 hours, filter to obtain filtrate I and filter residue I, and set aside; S1.2: The residue I of step S1.1 and an ethanol aqueous solution with a volume fraction of 75-80% are mixed in a mass ratio of 1: (40-50), and then reflux extraction is performed at 80-85°C for 8-10 hours, and filtrate II and residue II are obtained by filtration. The filtrate I and filtrate II of step S1.1 are combined and placed in a rotary evaporator, and the temperature is adjusted to 35-40°C and the vacuum degree is 0.08-0.09MPa for rotary evaporation until a paste is formed. The paste is vacuum dried at 65-70°C and the vacuum degree is 0.075-0.08MPa to constant weight, and crushed through a 60-70 mesh sieve to obtain a merbau extract powder; S1.3: Dissolve the merbau extract powder and epigallocatechin gallate in anhydrous ethanol, and then add a potassium dihydrogen phosphate aqueous solution containing laccase to obtain a composite solution, wherein the concentration of the merbau extract powder in the composite solution is 60-80 g / L, the concentration of epigallocatechin gallate is 15-20 g / L, and the volume fraction of anhydrous ethanol is 20-25%. Add 1-2 wt% of cellulose nanofibers to the composite solution, introduce oxygen at a flow rate of 0.2-0.3 L / min, and then shake at 180-200 rpm for 10-12 hours in a water bath at 35-40°C, then centrifuge to obtain the precipitate, and vacuum dry to obtain a fiber wetting enhancer.

[0008] Furthermore, step S2 is the preparation of the composite of the photothermal responsive elastic film and the suspension. S2.1: 3.8-3.85 parts by weight of isocyanoethyl methacrylate and 48-50 parts by weight of anhydrous dichloromethane are placed in a three-necked flask, nitrogen is introduced for protection, and then 2.1-2.15 parts by weight of N, N'-di-tert-butylethylenediamine and 8-10 parts by weight of anhydrous dichloromethane are slowly added dropwise to the three-necked flask, and the reaction is maintained at room temperature for 1-1.2 hours. The anhydrous dichloromethane is dried by a rotary evaporator and then cooled to obtain a hindered urea bond monomer; S2.2: 14-14.5 parts by weight of hindered urea bond monomer and 75.4-75.6 parts by weight of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene are added to 200-250 parts by weight of toluene, heated at 80-85°C until completely dissolved, cooled to room temperature, and then 1-1.2wt% of thiolated carbon nanotubes, 13-13.2 parts by weight of 3,6-dioxo-1,8-octanedithiol and 8.5-9 parts by weight of 1,5-diaminopentane are added in sequence, placed in an ultrasonic oscillator for mixing and degassing for 4-5 minutes, and then poured into a polytetrafluoroethylene mold, reacted at room temperature for 24-25 hours, and then reacted at 90-92°C for 1-1.2 hours to obtain a photothermal liquid crystal polymer film; S2.3: Control the tensile strength to 2-3MPa, stretch the photothermal liquid crystal polymer film to 140-142% of the original length and then fix it, then heat treat it at 138-140℃ for 1-1.5 hours, and naturally cool it to room temperature to obtain a photothermal responsive elastic film material. Mix the photothermal responsive elastic film material and deionized water at a solid-liquid ratio of 1: (10-15) g / mL, and then perform high-speed shear at a shear rate of 3000-4000rpm to obtain a photothermal responsive elastic film suspension, which is stored in a dark place.

[0009] Furthermore, step S3 prepares a beet armyworm control spray, comprising the following steps: S3.1: 3-4 parts by weight of chlorantraniliprole and 5-6 parts by weight of patchouli ketone are dissolved in 160-180 parts by weight of acetone, 0.2-0.3 parts by weight of polysorbate-20 are added, and then 3-3.5 parts by weight of a graphene oxide solution having a concentration of 1-1.5 g / L are added, and after being evenly stirred by magnetic stirring, the mixture is placed in a dark environment, and continuously stirred for 20-24 hours in a water bath at 24-26°C and 200-250 rpm, and then centrifuged at a centrifugal speed of 10000-12000 rpm for 10-15 minutes, and the precipitate is collected and washed 2-3 times with sterile water to obtain a composite insecticide drug carrier; S3.2: Add acrylic acid and acrylamide to deionized water at a mass ratio of 1: (5-6), stir magnetically until acrylic acid and acrylamide are completely dissolved to obtain a mixed solution with a concentration of 40-50wt%, then add 0.1-0.2% dimethylformamide, 0.8-1% ammonium persulfate and 0.4-0.6% tetramethyldiethylamine in order based on the mass percentage of acrylic acid and acrylamide, stir for 4-5 minutes after each addition, then add 1-1.5 times the mass of the photothermal response elastic film suspension, 8-10% of the fiber wetting enhancer and 30-40% of the composite insecticide drug carrier based on the mass of the reaction system, stir evenly, heat to 40-45°C for reaction for 3-4 hours, and obtain a photothermal response sustained-release hydrogel loaded with the drug; S3.3: Mix the photothermal responsive sustained-release hydrogel loaded with the drug and sterile water at a solid-liquid ratio of 1: (80-100) g / mL to obtain a beet armyworm control spray.

[0010] Furthermore, the pH of the citric acid aqueous solution in step S1.1 is 4.5-5.

[0011] Furthermore, in the potassium dihydrogen phosphate aqueous solution containing laccase in step S1.3, the concentration of potassium dihydrogen phosphate is 0.1-0.15 mol / L, and the concentration of laccase is 0.8-1 g / L.

[0012] Furthermore, in step S2.2, the inner diameter of the thiolated carbon nanotubes is 5-12 nm, and the outer diameter is 30-50 nm.

[0013] Furthermore, in step S2.2, the thickness of the photothermal liquid crystal polymer film is 80-100 μm.

[0014] A greenhouse asparagus beet armyworm control spray is prepared by the preparation process of the greenhouse asparagus beet armyworm control spray.

[0015] The beneficial effects are as follows: 1. The present invention prepares a hindered urea bond monomer, and the hindered urea bond monomer reacts with 1,4-bis-[4-(6-acryloxyhexyloxy)benzoyloxy]-2-methylbenzene and adds thiolated carbon nanotubes to obtain a photothermal liquid crystal polymer film, and the photothermal response elastic film is obtained after stretching, curing and orientation. When the temperature of the oriented photothermal liquid crystal polymer film rises, the liquid crystal molecules tend to be disordered, causing the liquid crystal elastomer to shrink along the orientation direction. By adjusting the content of the hindered urea bond monomer, the activation energy of the photothermal response elastic film can be greatly reduced, thereby controlling the phase transition temperature of the photothermal response elastic film to about 30°C. When the greenhouse temperature is controlled at about 10°C during the day, the photothermal response elastic film can be greatly reduced. When the optimal growth temperature of bamboo shoots is 20-30℃, under the photothermal effect of carbon nanotubes, the temperature of the photothermal responsive elastic film exceeds 30℃, the film keeps shrinking, and the release of the composite insecticide is reduced. When the temperature in the greenhouse drops at night and the carbon nanotubes lose their photothermal effect, the film returns to its original state. The photothermal responsive slow-release hydrogel has a good release effect on the composite insecticide, which can well match the characteristics of noctuid armyworms and their larvae that are dormant during the day and come out at night. It can avoid the ineffective release of the composite insecticide during the day, greatly improve the utilization rate of the composite insecticide, extend the effective insecticidal period, and improve the control efficiency of beet armyworms. It can reduce the number and amount of pesticide spraying, and has both ecological and economic benefits.

[0016] 2. The present invention, under the action of laccase, catalytically grafts the merbau extract powder and epigallocatechin gallate onto the surface of cellulose nanofibers, so that the catechol group of epigallocatechin gallate is oxidized to a quinone structure, which forms a strong adhesion with the insect cuticle chitin and can fix the cellulose nanofibers and the asparagus cuticle through the merbau extract, thereby enhancing the wettability and contact area of ​​the control spray on the asparagus and the insect body surface, and further improving the utilization rate of the composite insecticide. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The present invention is a flow chart of the preparation process of the greenhouse asparagus beet armyworm control spray used in the embodiments of the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1: A greenhouse asparagus beet armyworm control spray and its preparation process, such as Figure 1 As shown, the following steps are included: S1: Preparation of fiber wetting enhancer S1.1: Dry the merbau wood and grind it into powder to obtain merbau powder, then mix 30 parts by weight of the merbau powder, 150 parts by weight of a citric acid aqueous solution with a pH of 4.5 and 3 parts by weight of cellulase, and place in a constant temperature water bath at 50° C. for 24 hours, filter to obtain a filtrate I and a filter residue I, and set aside; S1.2: The residue I of step S1.1 and an ethanol aqueous solution with a volume fraction of 75% are mixed in a mass ratio of 1:40, and then reflux extraction is performed at 80°C for 8 hours, and filtrate II and residue II are obtained by filtration. The filtrate I and filtrate II of step S1.1 are combined and placed in a rotary evaporator, and the temperature is adjusted to 35°C and the vacuum degree is 0.08MPa for rotary evaporation until a paste is formed. The paste is vacuum dried at 65°C and the vacuum degree is 0.075MPa to constant weight, and crushed to pass through a 60-mesh sieve to obtain a merbau extract powder; S1.3: Dissolve the merva extract powder and epigallocatechin gallate in anhydrous ethanol, and then add a potassium dihydrogen phosphate aqueous solution containing laccase, the potassium dihydrogen phosphate concentration of the potassium dihydrogen phosphate aqueous solution containing laccase is 0.1 mol / L, and the laccase concentration is 0.8 g / L, to obtain a composite solution, the concentration of the merva extract powder in the composite solution is 60 g / L, the concentration of epigallocatechin gallate is 15 g / L, and the volume fraction of anhydrous ethanol is 20%. Add 1 wt% of cellulose nanofibers to the composite solution, introduce oxygen at a flow rate of 0.2 L / min, and then shake at 180 rpm for 10 hours in a water bath at 35°C, then centrifuge to obtain the precipitate, and vacuum dry to obtain the fiber wetting enhancer.

[0020] S2: Composite of photothermal responsive elastic membrane and preparation of suspension S2.1: 3.8 parts by weight of isocyanoethyl methacrylate and 48 parts by weight of anhydrous dichloromethane are placed in a three-necked flask, and nitrogen is introduced for protection. Then, 2.1 parts by weight of N,N'-di-tert-butylethylenediamine and 8 parts by weight of anhydrous dichloromethane are slowly added dropwise to the three-necked flask, and the reaction is maintained at room temperature for 1 hour. The anhydrous dichloromethane is dried by a rotary evaporator and then cooled to obtain a hindered urea bond monomer; S2.2: 14 parts by weight of hindered urea bond monomer and 75.4 parts by weight of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene are added to 200 parts by weight of toluene, heated at 80°C until completely dissolved, cooled to room temperature, 1wt% of thiolated carbon nanotubes, thiolated carbon nanotubes having an inner diameter of 5nm and an outer diameter of 30nm, 13 parts by weight of 3,6-dioxo-1,8-octanedithiol and 8.5 parts by weight of 1,5-diaminopentane are added in sequence, the mixture is placed in an ultrasonic oscillator for mixing and degassing for 4 minutes, and then poured into a polytetrafluoroethylene mold, reacted at room temperature for 24 hours, and then reacted at 90°C for 1 hour to obtain a photothermal liquid crystal polymer film having a thickness of 80μm; S2.3: Control the tensile strength to 2MPa, stretch the photothermal liquid crystal polymer film to 140% of the original length and then fix it, then heat treat it at 138°C for 1 hour, and naturally cool it to room temperature to obtain a photothermal responsive elastic film material. Mix the photothermal responsive elastic film material and deionized water at a solid-liquid ratio of 1:10g / mL, and then perform high-speed shear at a shear rate of 3000rpm to obtain a photothermal responsive elastic film suspension, which is stored in a dark place.

[0021] S3: Preparation of beet armyworm control spray S3.1: 3 parts by weight of chlorantraniliprole and 5 parts by weight of patchouli ketone are dissolved in 160 parts by weight of acetone, 0.2 parts by weight of polysorbate-20 is added, and then 3 parts by weight of a graphene oxide solution having a concentration of 1 g / L is added, the mixture is evenly stirred by magnetic stirring, and then placed in a dark environment, and stirred continuously for 20 hours in a water bath at 24°C and 200 rpm, and then centrifuged at a centrifugal speed of 10,000 rpm for 10 minutes, and the precipitate is collected and washed twice with sterile water to obtain a composite insecticide drug carrier; S3.2: Add acrylic acid and acrylamide to deionized water at a mass ratio of 1:5, and stir magnetically until acrylic acid and acrylamide are completely dissolved to obtain a mixed solution with a concentration of 40wt%, and then add 0.1% dimethylformamide, 0.8% ammonium persulfate and 0.4% tetramethyldiethylamine in order based on the mass percentage of acrylic acid and acrylamide, and stir for 4 minutes after each addition. Then, add 1 times the mass of the photothermal response elastic film suspension, 8% of the fiber wetting enhancer and 30% of the composite insecticide drug carrier based on the mass of the reaction system, stir evenly, heat to 40°C for reaction for 3 hours, and obtain a photothermal response sustained-release hydrogel loaded with the drug; S3.3: Mix the photothermal responsive sustained-release hydrogel loaded with the drug and sterile water at a solid-liquid ratio of 1:80 g / mL to obtain a beet armyworm control spray.

[0022] Example 2: A greenhouse asparagus beet armyworm control spray and its preparation process, such as Figure 1As shown, the following steps are included: S1: Preparation of fiber wetting enhancer S1.1: Dry the merbau wood and grind it into powder to obtain merbau powder, then mix 40 parts by weight of the merbau powder, 200 parts by weight of a citric acid aqueous solution with a pH of 4.5 and 5 parts by weight of cellulase, place in a constant temperature water bath at 50° C. for 24 hours, filter to obtain a filtrate I and a filter residue I, and set aside; S1.2: The residue I of step S1.1 and an ethanol aqueous solution with a volume fraction of 75% are mixed in a mass ratio of 1:50, and then reflux extraction is performed at 80°C for 8 hours, and filtrate II and residue II are obtained by filtration. The filtrate I and filtrate II of step S1.1 are combined and placed in a rotary evaporator, and the temperature is adjusted to 35°C and the vacuum degree is 0.08MPa for rotary evaporation until a paste is formed. The paste is vacuum dried at 65°C and the vacuum degree is 0.075MPa to constant weight, and crushed to pass through a 60-mesh sieve to obtain a merbau extract powder; S1.3: The mervatica extract powder and epigallocatechin gallate were dissolved in anhydrous ethanol, and then a potassium dihydrogen phosphate aqueous solution containing laccase was added, the potassium dihydrogen phosphate concentration of the potassium dihydrogen phosphate aqueous solution containing laccase was 0.15 mol / L, and the laccase concentration was 1 g / L, to obtain a composite solution, the concentration of the mervatica extract powder in the composite solution was 80 g / L, the concentration of epigallocatechin gallate was 20 g / L, and the volume fraction of anhydrous ethanol was 25%, 2 wt% of cellulose nanofibers were added to the composite solution, oxygen was introduced at a flow rate of 0.2 L / min, and then the solution was shaken at 180 rpm for 10 hours in a water bath at 35°C, and then the precipitate was centrifuged and vacuum dried to obtain a fiber wetting enhancer.

[0023] S2: Composite of photothermal responsive elastic membrane and preparation of suspension S2.1: 3.85 parts by weight of isocyanoethyl methacrylate and 50 parts by weight of anhydrous dichloromethane are placed in a three-necked flask, and nitrogen is introduced for protection. Then, 2.15 parts by weight of N,N'-di-tert-butylethylenediamine and 10 parts by weight of anhydrous dichloromethane are slowly added dropwise to the three-necked flask, and the reaction is maintained at room temperature for 1 hour. The anhydrous dichloromethane is dried by a rotary evaporator and then cooled to obtain a hindered urea bond monomer; S2.2: 14.5 parts by weight of hindered urea bond monomer and 75.6 parts by weight of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene are added to 250 parts by weight of toluene, heated at 80°C until completely dissolved, cooled to room temperature, 1.2wt% of thiolated carbon nanotubes, thiolated carbon nanotubes having an inner diameter of 5nm and an outer diameter of 30nm, 13.2 parts by weight of 3,6-dioxo-1,8-octanedithiol and 9 parts by weight of 1,5-diaminopentane are added in sequence, the mixture is placed in an ultrasonic oscillator for mixing and degassing for 4 minutes, and then poured into a polytetrafluoroethylene mold, reacted at room temperature for 24 hours, and then reacted at 90°C for 1 hour to obtain a photothermal liquid crystal polymer film having a thickness of 80μm; S2.3: Control the tensile strength to 2MPa, stretch the photothermal liquid crystal polymer film to 140% of the original length and then fix it, then heat treat it at 138°C for 1 hour, and naturally cool it to room temperature to obtain a photothermal responsive elastic film material. Mix the photothermal responsive elastic film material and deionized water at a solid-liquid ratio of 1:15g / mL, and then perform high-speed shear at a shear rate of 3000rpm to obtain a photothermal responsive elastic film suspension, which is stored in a dark place.

[0024] S3: Preparation of beet armyworm control spray S3.1: 4 parts by weight of chlorantraniliprole and 6 parts by weight of patchouli ketone are dissolved in 180 parts by weight of acetone, 0.3 parts by weight of polysorbate-20 is added, and then 3.5 parts by weight of a graphene oxide solution having a concentration of 1 g / L is added, and after being evenly stirred by magnetic stirring, the mixture is placed in a dark environment, and stirred continuously for 20 hours in a water bath at 24°C and 200 rpm, and then centrifuged at a centrifugal speed of 10,000 rpm for 10 minutes, and the precipitate is collected and washed twice with sterile water to obtain a composite insecticide drug carrier; S3.2: Add acrylic acid and acrylamide to deionized water at a mass ratio of 1:6, and stir magnetically until acrylic acid and acrylamide are completely dissolved to obtain a mixed solution with a concentration of 40wt%, and then add 0.2% dimethylformamide, 1% ammonium persulfate and 0.6% tetramethyldiethylamine in order based on the mass percentage of acrylic acid and acrylamide, and stir for 4 minutes after each addition. Then, add 1.5 times the mass of the photothermal response elastic film suspension, 10% of the fiber wetting enhancer and 30% of the composite insecticide drug carrier based on the mass of the reaction system, stir evenly, heat to 40°C for reaction for 3 hours, and obtain a photothermal response sustained-release hydrogel loaded with the drug; S3.3: Mix the photothermal responsive sustained-release hydrogel loaded with the drug and sterile water at a solid-liquid ratio of 1:80 g / mL to obtain a beet armyworm control spray.

[0025] Example 3: A greenhouse asparagus beet armyworm control spray and its preparation process, such as Figure 1As shown, the following steps are included: S1: Preparation of fiber wetting enhancer S1.1: Dry the merbau wood and grind it into powder to obtain merbau powder, then mix 30 parts by weight of the merbau powder, 150 parts by weight of a citric acid aqueous solution with a pH of 4.5 and 3 parts by weight of cellulase, and place in a constant temperature water bath at 55° C. for 30 hours, filter to obtain a filtrate I and a filter residue I, and set aside; S1.2: The residue I of step S1.1 and an ethanol aqueous solution with a volume fraction of 80% are mixed in a mass ratio of 1:40, and then reflux extraction is performed at 85°C for 10 hours, and filtrate II and residue II are obtained by filtration. The filtrate I and filtrate II of step S1.1 are combined and placed in a rotary evaporator, and the temperature is adjusted to 40°C and the vacuum degree is 0.09 MPa for rotary evaporation until a paste is formed. The paste is vacuum dried at 70°C and the vacuum degree is 0.08 MPa to constant weight, and crushed to pass through a 70-mesh sieve to obtain a merbau extract powder; S1.3: The mervatica extract powder and epigallocatechin gallate were dissolved in anhydrous ethanol, and then a potassium dihydrogen phosphate aqueous solution containing laccase was added, the potassium dihydrogen phosphate concentration of the potassium dihydrogen phosphate aqueous solution containing laccase was 0.1 mol / L, and the laccase concentration was 0.8 g / L, to obtain a composite solution, the concentration of the mervatica extract powder in the composite solution was 60 g / L, the concentration of epigallocatechin gallate was 15 g / L, and the volume fraction of anhydrous ethanol was 20%, 1 wt% of cellulose nanofibers was added to the composite solution, oxygen was introduced at a flow rate of 0.3 L / min, and then the solution was shaken at 180 rpm for 12 hours in a water bath at 40°C, and then the precipitate was centrifuged and vacuum dried to obtain a fiber wetting enhancer.

[0026] S2: Composite of photothermal responsive elastic membrane and preparation of suspension S2.1: 3.8 parts by weight of isocyanoethyl methacrylate and 48 parts by weight of anhydrous dichloromethane are placed in a three-necked flask, and nitrogen is introduced for protection. Then, 2.1 parts by weight of N,N'-di-tert-butylethylenediamine and 8 parts by weight of anhydrous dichloromethane are slowly added dropwise to the three-necked flask, and the reaction is maintained at room temperature for 1.2 hours. The anhydrous dichloromethane is dried by a rotary evaporator and then cooled to obtain a hindered urea bond monomer; S2.2: 14 parts by weight of hindered urea bond monomer and 75.4 parts by weight of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene are added to 200 parts by weight of toluene, heated at 85°C until completely dissolved, cooled to room temperature, 1 wt% of thiolated carbon nanotubes, thiolated carbon nanotubes having an inner diameter of 12 nm and an outer diameter of 50 nm, 13 parts by weight of 3,6-dioxo-1,8-octanedithiol and 8.5 parts by weight of 1,5-diaminopentane are added in sequence, the mixture is placed in an ultrasonic oscillator for mixing and degassing for 5 minutes, and then poured into a polytetrafluoroethylene mold, reacted at room temperature for 25 hours, and then reacted at 92°C for 1.2 hours to obtain a photothermal liquid crystal polymer film having a thickness of 100 μm; S2.3: Control the tensile strength to 3MPa, stretch the photothermal liquid crystal polymer film to 142% of the original length and then fix it, then heat treat it at 140°C for 1.5 hours, and naturally cool it to room temperature to obtain a photothermal responsive elastic film material. Mix the photothermal responsive elastic film material and deionized water at a solid-liquid ratio of 1:10g / mL, and then perform high-speed shear at a shear rate of 4000rpm to obtain a photothermal responsive elastic film suspension, which is stored in a dark place.

[0027] S3: Preparation of beet armyworm control spray S3.1: 3 parts by weight of chlorantraniliprole and 5 parts by weight of patchouli ketone are dissolved in 160 parts by weight of acetone, 0.2 parts by weight of polysorbate-20 is added, and then 3 parts by weight of a 1.5 g / L graphene oxide solution is added, and after being evenly stirred by magnetic stirring, the mixture is placed in a dark environment, and stirred continuously for 24 hours in a water bath at 26°C and 250 rpm, and then centrifuged at a centrifugal speed of 12,000 rpm for 15 minutes, and the precipitate is collected and washed three times with sterile water to obtain a composite insecticide drug carrier; S3.2: Add acrylic acid and acrylamide to deionized water at a mass ratio of 1:5, and stir magnetically until acrylic acid and acrylamide are completely dissolved to obtain a mixed solution with a concentration of 50wt%, and then add 0.1% dimethylformamide, 0.8% ammonium persulfate and 0.4% tetramethyldiethylamine in order based on the mass percentage of acrylic acid and acrylamide, and stir for 5 minutes after each addition. Then, add 1 times the mass of the photothermal response elastic membrane suspension, 8% of the fiber wetting enhancer and 30% of the composite insecticide drug carrier based on the mass of the reaction system, stir evenly, heat to 45°C for 4 hours, and obtain a photothermal response sustained-release hydrogel loaded with the drug; S3.3: Mix the photothermal responsive sustained-release hydrogel loaded with the drug and sterile water at a solid-liquid ratio of 1:100 g / mL to obtain a beet armyworm control spray.

[0028] Comparative Example 1: A greenhouse asparagus beet armyworm control spray and its preparation process. Compared with the implementation method of Example 1, the difference is that Comparative Example 1 removes step S2 and does not add a photothermal responsive elastic film suspension in step S3.2 to prepare a beet armyworm control spray, which is recorded as Comparative Example 1.

[0029] Comparative Example 2: A greenhouse asparagus beet armyworm control spray and its preparation process. Compared with the implementation method of Example 1, the difference is that Comparative Example 2 removes step S1 and does not add a fiber wetting enhancer in step S3.2 to obtain a beet armyworm control spray, which is recorded as Comparative Example 2.

[0030] Sustained-release performance test: The beet armyworm control spray prepared in Example 1 and the beet armyworm control spray prepared in Comparative Example 1 were taken as samples, and the samples were divided into multiple sample groups of equal amount, and the samples were respectively sprayed under simulated sunlight-incandescent lamp (13000 W / m 2 ) and placed in a glass container in a dark environment, the temperature of the glass container was adjusted to 15, 30 and 40°C, respectively, and the same amount of samples were taken out every 12 hours, and the concentrations of chlorantraniliprole and patchouli ketone in the samples were measured by high performance liquid chromatography, and the total release of chlorantraniliprole and patchouli ketone composite insecticide at each time point was calculated, and the parallel test was repeated 3 times, and the values ​​at each temperature and each time point were averaged. The test data are shown in Tables 1 and 2.

[0031] Table 1: Drug release at various temperatures and time points in light and dark environments in Example 1

[0032] Table 2: Comparative Example 1: Release of the drug at each temperature and time point in the light and dark environment

[0033] It can be seen from the data of the embodiment in Table 1 that the rate of releasing the composite insecticide from the beet armyworm control spray prepared in Example 1 significantly decreases with increasing temperature, and in a light environment, the magnitude of the decrease is greater than that in a dark environment, which proves that the spray prepared in Example 1 can reduce the release of the composite insecticide during the day and have a good release effect at night. It can be seen from the data of Comparative Example 1 in Table 2 that when the photothermal responsive elastic film is not added to the hydrogel, the release rate of the composite insecticide at each time point is not much different, whether it is day or night, whether it is high temperature or low temperature, and there are data to prove that the addition of the photothermal responsive elastic film to the hydrogel achieves the control effect of reducing the release rate of the composite insecticide under high temperature conditions during the day and maintaining a high release rate of the composite insecticide under low temperature conditions at night, effectively targeting the characteristics of the armyworm that hides during the day and comes out at night, and improving the utilization rate of the composite insecticide.

[0034] Contact angle test: The contact angles of water, the beet armyworm control spray prepared in Examples 1-3, and the beet armyworm control spray prepared in Comparative Example 2 with asparagus and insect body surface (3rd instar beet armyworm larvae) were measured using a contact angle meter at 25°C. The contact angles were measured within 3 seconds after the sample to be tested was dropped on the tobacco leaf and the insect body surface. The test was repeated three times and the average value was taken. The test results are shown in Table 3.

[0035] Table 3: Contact angles with asparagus and insect surfaces

[0036] It can be seen from the data in Table 3 that the contact angles between the beet armyworm control spray prepared in Examples 1-3 and asparagus and the insect surface are much smaller than the contact angles between water and asparagus and the insect surface, indicating that the beet armyworm control spray has much stronger wettability on asparagus and the insect surface than water, and can better adhere to the asparagus and the insect surface, thereby increasing the effective contact area of ​​the agent and improving the utilization rate. It can be seen from the data in Comparative Example 2 that the preparation of a fiber wetting enhancer can enhance the wettability of the spray and further improve the utilization rate of the composite insecticide.

[0037] The above embodiments are merely illustrative of the principles and effects of the present invention, and are not intended to limit the present invention. Anyone familiar with the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by a person of ordinary skill in the art without departing from the spirit and technical concept disclosed by the present invention shall still be covered by the claims of the present invention.

Claims

1. A preparation process for a greenhouse asparagus beet armyworm control spray, characterized in that: The following steps are involved: Preparation of S1 fiber wetting enhancer: grind the merbau wood into powder, perform enzymolysis and alcohol extraction to obtain merbau extract powder, dissolve the merbau extract powder and epigallocatechin gallate in anhydrous ethanol, add potassium dihydrogen phosphate aqueous solution containing laccase and mix well, then add cellulose nanofibers to react in a water bath, centrifuge and dry the precipitate to obtain the fiber wetting enhancer; S2 Preparation of composite photothermal responsive elastic film and suspension: isocyanoethyl methacrylate and N, N'-di-tert-butylethylenediamine are reacted in anhydrous dichloromethane to obtain a hindered urea bond monomer, which is then reacted with 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene and thiolated carbon nanotubes are added to obtain a photothermal liquid crystal polymer film, which is stretched and cured and then sheared in deionized water to obtain a photothermal responsive elastic film suspension; S3 preparation of beet armyworm control spray: chlorantraniliprole, patchouli ketone and graphene oxide solution are mixed and stirred in a water bath, and a composite insecticide carrier is obtained after centrifugal washing. Acrylic acid and acrylamide are pre-polymerized and added into a photothermal responsive elastic membrane suspension, a fiber wetting enhancer and the composite insecticide carrier, and stirred evenly. After heating and polymerization, the mixture is evenly mixed with deionized water to obtain a beet armyworm control spray.

2. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 1, characterized in that: Step S1: Preparation of fiber wetting enhancer, comprising the following steps: S1.1: Dry the merbau wood and grind it into powder to obtain merbau powder, then mix 30-40 parts by weight of the merbau powder, 150-200 parts by weight of citric acid aqueous solution and 3-5 parts by weight of cellulase, and place in a constant temperature water bath at 50-55° C. for 24-30 hours, filter to obtain filtrate I and filter residue I, and set aside; S1.2: The residue I of step S1.1 and an ethanol aqueous solution with a volume fraction of 75-80% are mixed in a mass ratio of 1: (40-50), and then reflux extraction is performed at 80-85°C for 8-10 hours, and filtrate II and residue II are obtained by filtration. The filtrate I and filtrate II of step S1.1 are combined and placed in a rotary evaporator, and the temperature is adjusted to 35-40°C and the vacuum degree is 0.08-0.09MPa for rotary evaporation until a paste is formed. The paste is vacuum dried at 65-70°C and the vacuum degree is 0.075-0.08MPa to constant weight, and crushed through a 60-70 mesh sieve to obtain a merbau extract powder; S1.3: Dissolve the merbau extract powder and epigallocatechin gallate in anhydrous ethanol, and then add a potassium dihydrogen phosphate aqueous solution containing laccase to obtain a composite solution, wherein the concentration of the merbau extract powder in the composite solution is 60-80 g / L, the concentration of epigallocatechin gallate is 15-20 g / L, and the volume fraction of anhydrous ethanol is 20-25%. Add 1-2 wt% of cellulose nanofibers to the composite solution, introduce oxygen at a flow rate of 0.2-0.3 L / min, and then shake at 180-200 rpm for 10-12 hours in a water bath at 35-40°C, then centrifuge to obtain the precipitate, and vacuum dry to obtain a fiber wetting enhancer.

3. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 2, characterized in that: Step S2: compounding of the photothermal responsive elastic film material and preparation of the suspension, including the following steps: S2.1: 3.8-3.85 parts by weight of isocyanoethyl methacrylate and 48-50 parts by weight of anhydrous dichloromethane are placed in a three-necked flask, nitrogen is introduced for protection, and then 2.1-2.15 parts by weight of N, N'-di-tert-butylethylenediamine and 8-10 parts by weight of anhydrous dichloromethane are slowly added dropwise to the three-necked flask, and the reaction is maintained at room temperature for 1-1.2 hours. The anhydrous dichloromethane is dried by a rotary evaporator and then cooled to obtain a hindered urea bond monomer; S2.2: 14-14.5 parts by weight of hindered urea bond monomer and 75.4-75.6 parts by weight of 1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene are added to 200-250 parts by weight of toluene, heated at 80-85°C until completely dissolved, cooled to room temperature, and then 1-1.2wt% of thiolated carbon nanotubes, 13-13.2 parts by weight of 3,6-dioxo-1,8-octanedithiol and 8.5-9 parts by weight of 1,5-diaminopentane are added in sequence, placed in an ultrasonic oscillator for mixing and degassing for 4-5 minutes, and then poured into a polytetrafluoroethylene mold, reacted at room temperature for 24-25 hours, and then reacted at 90-92°C for 1-1.2 hours to obtain a photothermal liquid crystal polymer film; S2.3: Control the tensile strength to 2-3MPa, stretch the photothermal liquid crystal polymer film to 140-142% of the original length and then fix it, then heat treat it at 138-140℃ for 1-1.5 hours, and naturally cool it to room temperature to obtain a photothermal responsive elastic film material. Mix the photothermal responsive elastic film material and deionized water at a solid-liquid ratio of 1: (10-15) g / mL, and then perform high-speed shear at a shear rate of 3000-4000rpm to obtain a photothermal responsive elastic film suspension, which is stored in a dark place.

4. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 3, characterized in that: Step S3 prepares a beet armyworm control spray, comprising the following steps: S3.1: 3-4 parts by weight of chlorantraniliprole and 5-6 parts by weight of patchouli ketone are dissolved in 160-180 parts by weight of acetone, 0.2-0.3 parts by weight of polysorbate-20 are added, and then 3-3.5 parts by weight of a graphene oxide solution having a concentration of 1-1.5 g / L are added, and after being evenly stirred by magnetic stirring, the mixture is placed in a dark environment, and continuously stirred for 20-24 hours in a water bath at 24-26°C and 200-250 rpm, and then centrifuged at a centrifugal speed of 10000-12000 rpm for 10-15 minutes, and the precipitate is collected and washed 2-3 times with sterile water to obtain a composite insecticide drug carrier; S3.2: Add acrylic acid and acrylamide to deionized water at a mass ratio of 1: (5-6), stir magnetically until acrylic acid and acrylamide are completely dissolved to obtain a mixed solution with a concentration of 40-50wt%, then add 0.1-0.2% dimethylformamide, 0.8-1% ammonium persulfate and 0.4-0.6% tetramethyldiethylamine in order based on the mass percentage of acrylic acid and acrylamide, stir for 4-5 minutes after each addition, then add 1-1.5 times the mass of the photothermal response elastic film suspension, 8-10% of the fiber wetting enhancer and 30-40% of the composite insecticide drug carrier based on the mass of the reaction system, stir evenly, heat to 40-45°C for reaction for 3-4 hours, and obtain a photothermal response sustained-release hydrogel loaded with the drug; S3.3: Mix the photothermal responsive sustained-release hydrogel loaded with the drug and sterile water at a solid-liquid ratio of 1: (80-100) g / mL to obtain a beet armyworm control spray.

5. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 2, characterized in that: The pH of the citric acid aqueous solution in step S1.1 is 4.5-5.

6. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 2, characterized in that: In step S1.3, in the potassium dihydrogen phosphate aqueous solution containing laccase, the concentration of potassium dihydrogen phosphate is 0.1-0.15 mol / L, and the concentration of laccase is 0.8-1 g / L.

7. The preparation process of a greenhouse asparagus beet armyworm control spray according to claim 3, characterized in that: In step S2.2, the inner diameter of the thiolated carbon nanotubes is 5-12 nm, and the outer diameter is 30-50 nm.

8. The preparation process of the greenhouse asparagus beet armyworm control spray according to claim 3, characterized in that: The thickness of the photothermal liquid crystal polymer film in step S2.2 is 80-100 μm.

9. A spray for controlling beet armyworm in greenhouse asparagus, characterized in that: The spray is prepared by the preparation process of the greenhouse asparagus beet armyworm control spray according to any one of claims 1 to 9.

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