CN114027298A

CN114027298A - Preparation method and application of environment-responsive controlled-release pesticide preparation

Info

Publication number: CN114027298A
Application number: CN202111517020.2A
Authority: CN
Inventors: 林宝凤; 樊超然; 刘岩; 冯蒲; 黄国焕; 姚远; 党民飞; 江凤琼
Original assignee: Guangxi University
Current assignee: Guangxi University
Priority date: 2021-12-13
Filing date: 2021-12-13
Publication date: 2022-02-11
Anticipated expiration: 2041-12-13
Also published as: CN114027298B

Abstract

The invention discloses a preparation method and application of an environment response controlled release pesticide preparation, wherein the preparation method comprises the following steps: the method comprises the following steps: adding the required pesticide and functional agent into water, and stirring to form suspension A. Step two: adding natural polymer into the suspension A, and stirring to form a mixture B. Step three: and preparing a mixture C by using the required pesticide, the functional agent, water and the cross-linking agent. Step four: and adding the mixture B into the mixture C in a dropwise manner to obtain spherical hydrogel. Step five: filtering to collect spherical hydrogel, washing and drying. The invention has the following advantages: (1) the base material is made of natural polymer, and is green, environment-friendly and renewable; (2) the preparation process is simple, and simultaneously has the advantage of high drug loading capacity; (3) the carrier improves the stability of the pesticide, promotes the absorption of the pesticide by crops or realizes the stimulated release by the functional agent, and endows the carrier with the function of responding to the controlled release pesticide by the environment by utilizing natural macromolecules.

Description

Preparation method and application of environment-responsive controlled-release pesticide preparation

Technical Field

The invention relates to the technical field of controlled-release pesticides, in particular to a preparation method and application of an environment-responsive controlled-release pesticide preparation.

Background

The pesticide refers to a general name of a pesticide which is applied to protect and promote the growth of plants and crops and is used for killing pests, bacteria and harmful animals (or weeds) in agricultural production. Due to the increase in the world population, there is an urgent need to develop high-value crops, increasing the production using pesticides and fertilizers. Worldwide producers use approximately 60 billion pounds of insecticides per year. The pesticide is a double-edged sword, on one hand, the pesticide has good effect of preventing and controlling diseases, pests and weeds, and is a chemical prevention and control means commonly adopted in plant protection; on the other hand, the pesticide has the defects of toxic residue, drug resistance of diseases and pests, damage to an ecological system and the like, and brings serious harm to the environment and human beings. The unplanned use of pesticides not only harms human health, but also causes target pests to have drug resistance to the pesticides, weakens the nitrogen fixation capacity and destroys the biological diversity of soil.

Therefore, the research of novel pesticides is a very urgent task in the field of pesticides at present. Currently, pesticide delivery systems are receiving much attention for their sustained and stable pesticide release characteristics to reduce pesticide use. Natural polymers (alginic acid, cellulose, chitosan, lignin) have excellent biocompatibility, good safety characteristics, biodegradability, abundant natural sources, low cost and easy chemical modification, and have been increasingly used for slow-release carriers. The function realized by simply using natural polymer as a pesticide carrier is limited, and the further application can be realized only by adding a functional agent to deliver active ingredients in a controllable, adjustable and personalized manner under a specific microenvironment condition.

The current research is mainly to endow the pesticide carrier with the stimulation reaction capability under indoor simulation conditions of pH, temperature, magnetism, electric charge and the like, and realize the controlled release of the pesticide. Metal-organic frameworks (MOFs) are formed by linking together inorganic units and organic units by coordination bonds (network synthesis). It has high specific surface area, and can well load and protect pesticide. The structure of the medicine can be destroyed by stimulation of water, phosphate and the like, so that the medicine can be controllably released. However, MOFs have poor processability and high cost. The use of cyclodextrins as agrochemical delivery systems to enhance biological activity is reported in patent WO2019215645, but said content does not include effects on novel nicotine drugs. And the cyclodextrin has low drug-loading rate and is released quickly as a carrier. Patent CN202011140970.3 utilizes alginic acid and attapulgite to construct an electrically-driven controlled release and migration gel-based pesticide system, so that the system has a precise release function, but the regulation is complex, and the system is driven by electricity, so that certain risks are generated in practical application.

Research and research show that although many controlled-release pesticides with excellent controlled-release performance in laboratories have been developed at present, the problems are that the preparation process is complex, the production cost is high, and the performance of the controlled-release pesticides used in fields is far lower than that expected in the laboratories, and the expected effect cannot be achieved. Compared with a laboratory, the field uncontrollable variables are more, and it is particularly important to verify whether the pesticide carrier is effective in practical application. Meanwhile, many pesticides generally have the problems of poor solubility, short pesticide effect time and low utilization rate. Therefore, if the water dispersibility of the pesticide could be improved, the precise release of the pesticide could be achieved through environmental changes, which would greatly reduce the waste of the pesticide and overcome the undesirable side effects.

Disclosure of Invention

The invention aims to provide a preparation method of an environment response controlled-release pesticide preparation, which has the advantages of low cost, high efficiency and simple process.

In order to realize the purpose of the invention, the technical scheme is as follows:

a preparation method of an environment response controlled release pesticide preparation is to mix a functional agent and a pesticide, then add a natural macromolecule, and use a cross-linking agent to enable the natural macromolecule to form a three-dimensional polymer network to embed the functional agent and the pesticide, wherein the preparation process comprises the following steps:

the method comprises the following steps: adding the required pesticide and functional agent into water, and fully stirring and mixing for 10-48 hours in a water bath at 20-60 ℃ to form a suspension A, wherein the added parts by weight are as follows: 0.5-2 parts of functional agent, 1-4 parts of pesticide and 30-60 parts of water.

Step two: adding 0.3-1.5 parts by weight of natural polymer into the suspension A, and fully stirring and dissolving for 3-24 hours in a water bath at the temperature of 20-60 ℃ to form a mixture B.

Step three: adding the required pesticide and the functional agent into water, and fully stirring at room temperature to form a mixed solution, wherein the weight ratio of the functional agent to the pesticide to the water in the mixed solution is as follows: (0.5-2): (1-4): (30-60), adding cross-linking agent into the mixed solution, and stirring uniformly to form a mixture C, wherein the mass concentration of the cross-linking agent in the solution is 0.1-5%.

Step four: and adding the mixture B into the mixture C in a dropwise manner, wherein the dropwise adding speed is 0.5-3 mL/h, and the crosslinking time is controlled to be 10-90 min, so as to obtain the spherical hydrogel.

Step five: filtering and collecting the spherical hydrogel, washing to remove pesticide residues on the surface, and drying in a dryer at 20-80 ℃ for 12-24h to obtain the environment-responsive controlled-release pesticide preparation. Washing is performed with ethanol or deionized water.

Further preferred is: the functional agent is one or more of cyclodextrin, MOFs and biomass carbon. The functional agent can load pesticide, improve the bioavailability of the pesticide and realize the controlled release capability of the pesticide under specific conditions.

Further preferred is: the pesticide is neonicotinoid pesticide including thiamethoxam, clothianidin, dinotefuran and thiacloprid.

Further preferred is: the natural polymer is one or more of sodium alginate, chitosan, carboxymethyl chitosan, lignin, sodium lignosulfonate, cellulose and carboxymethyl cellulose.

Further preferred is: the cross-linking agent is one or more of copper nitrate, zinc nitrate, calcium chloride, ferric chloride, zinc chloride, vanillin and glutaraldehyde.

The environment-responsive controlled-release pesticide preparation prepared by the preparation method of the environment-responsive controlled-release pesticide preparation can be applied to rice planting.

The present inventors used functional agents such as cyclodextrin and UiO-66 and studied their properties. When the concentration range of the beta-CD is 0-15 mmol/L, the solubility of TMX is linearly increased along with the increase of the concentration of the beta-CD, which shows that the cyclodextrin serving as a functional agent improves the solubility of the pesticide. With the increase of the phosphate concentration, the rate of releasing CTD by UiO-66@ Alg-CTD is remarkably increased, when the release time reaches 24h, the release amount of CTD reaches 31.56% when the sustained-release solution is deionized water, and when the concentrations of the sustained-release solution are respectively 0.005 and 0.02 mol/L PBS solutions, the release amounts reach 84.43% and 87.76%, and the results show that the carrier shows better response performance to the change of the phosphate concentration after the functional agent UI0-66 is added.

The present inventors have systematically studied the main factors affecting the release and stability of pesticides in field soil, such as temperature, pH, salt concentration and light, in combination with the problems existing in practical applications. According to the local temperature characteristics, TMX release curves of the controlled-release pesticide TMX-loaded Alg/beta-CD at different temperatures (27, 37 and 45 ℃) are researched. The release rate of TMX increased with increasing temperature, and the release time decreased from 60h to 24h as the temperature increased from 27 ℃ to 45 ℃. This indicates that the controlled release pesticide has a significant response to temperature changes. The release rate of TMX is relatively low at low temperatures and increases significantly as the temperature increases. This is due to the slow flow of alginate chains at low temperatures, while at high temperatures, the swelling degree of the gel network of the composite material, where water molecules can penetrate more rapidly into the carrier network, increases, thereby increasing the release of the controlled release pesticide TMX. The release curves of TMX-loaded Alg/beta-CD in PBS buffer solution simulating different soil pH values (6.1, 7.0 and 8.3) are measured, and the results of the slow release curves at three groups of different pH values are basically consistent. As the pH value is increased, the potential absolute value of the TMX-loaded Alg/beta-CD material is reduced, the swelling degree is increased, the TMX-loaded Alg has similar properties, but the slow release performance of the material is not greatly influenced, which shows that the drug carrier can control the release of the TMX under wider pH conditions, has salt concentration response and is more suitable for practical application in agricultural production. Because TMX has poor photostability, it is easily decomposed under uv light irradiation. Therefore, it is necessary to improve the utility of agricultural chemicals by improving the uv resistance of agricultural chemicals. The degradation rate of TMX-loaded Alg/beta-CD under UV irradiation was investigated. After 72h, the degradation rate of TMX reaches 94.8%, and the degradation rate of TMX-loaded Alg/beta-CD is 86%. This indicates that the photostability of TMX-loaded Alg/β -CD is higher than that of free TMX. The pesticide is slowly released from Alg/beta-CD to the environment, and the pesticide exposure to uv light is relatively low compared to free TMX. The Alg/beta-CD serves as a protective shell to prevent TMX from being directly irradiated by ultraviolet light, and can prevent TMX from being decomposed. Meanwhile, the degradation rate of UiO-66@ Alg-CTD under the irradiation of ultraviolet rays is considered, and pure CTD is used as a comparison under the same experimental conditions. With the increase of time, the degradation rate of pure CTD reaches 86.85% after 24h, while the degradation rate of CTD coated by UiO-66@ Alg is only 24.57% after 24h of ultraviolet irradiation.

The main pest rice planthopper of the rice is selected as a model pest, and compared with a blank control group and a pure TMX preparation, the pest control effect of the TMX-loaded Alg/beta-CD is evaluated. The blank control group has no control effect, and after 66 days, part of rice seedlings in the CK group withers and dies, and leaves are quite sparse. The plant height of the pure medicine group is also shorter. The slow release agent group has better growth condition than the contrast group and good leaf growth. The rice planthopper damages rice seedlings and has great influence on the plant height of the rice seedlings: the blank control group and pure TMX showed obvious reduction of plant height and withered yellow after inoculation of rice planthopper on day 22, which is caused by rice planthopper invasion. On day 66, the average plant height of the dust was 23.14 cm, which was the highest among all experimental groups, and the plant heights of CK and pure drug were much lower. The TMX Loaded Alg/beta-CD granule treatment group keeps the insecticidal rate of more than 75% in 66d, and further shows that the TMX Loaded Alg/beta-CD granule treatment group has excellent and long-acting pest control effect. In contrast, the TMX Loaded Alg/beta-CD powder can keep more than 50 percent of insecticidal rate in 66 days. The mortality rate of the shown insects is from low to high in the order: CK < pure TMX < TMX-loaded Alg/beta-CD powder < TMX-loaded Alg/beta-CD granules, which is consistent with the length and sequence of the slow release time of the medicines, shows that the slow release time of the medicines is prolonged, and is beneficial to realizing long-acting pest control. It is noteworthy that as air temperature decreased, rice seedlings grew slowly and mortality of pests increased at 66 days and rice planthopper death occurred in CK group. In conclusion, the TMX Loaded Alg/beta-CD powder has the optimal effect on long-term prevention and control of rice pests.

Compared with the prior art, the invention has the following benefits and effects:

1. compared with the traditional pesticide which uses a large amount of organic solvent harmful to the environment, most of the pesticides are difficult to be compatible with water, and the invention improves the water dispersibility of the hydrophobic pesticide by utilizing the hydrophobic characteristic in the cavity of the functional agent such as cyclodextrin and the like, thereby reducing the use of the organic solvent.

2. The natural polymer hydrogel is sensitive to temperature, pH, salt concentration, humidity and the like, and the pesticide is accurately released through environmental change, so that compared with the traditional pesticide preparation, the quick release of the pesticide in the early stage is overcome, the pesticide protection time is prolonged, the pesticide waste is reduced under the same pesticide effect, and adverse side effects are overcome.

3. The functional agent used in the method can load pesticide, improve the bioavailability of the pesticide, endow the carrier with stimulating and releasing capability, and realize intelligent controlled release of the pesticide under specific conditions.

4. The method adds the cross-linking agent into the saturated pesticide solution, and then adds the functional agent/natural polymer/pesticide mixture dropwise, so that the drug-loading rate is greatly improved compared with the existing polysaccharide pesticide.

5. The raw materials used in the method are environment-friendly and have good biocompatibility, the functional agent is combined with the natural high polymer material, the defects of the existing functional agent are overcome, such as the defects of low drug loading and quick release of cyclodextrin, the defect that MOFs materials are not easy to process is overcome, the preparation process is simple, and the method is beneficial to industrialization.

Drawings

FIG. 1 is a phase solubility curve for beta-CD;

FIG. 2 is a graph of the cumulative release rate of a pesticide from UiO-66@ Alg in phosphate solutions of various concentrations (0, 0.005, 0.02 mol/L);

FIG. 3 is a behavioral graph of the present environment responsive controlled release pesticide;

in fig. 3, (a) shows the drug loading of different materials, the drug loading of the Alg/beta-CD gel particles is up to 41%; (b) shows the release behavior of different materials and shows the release curve of TMX in Alg/beta-CD gel particles; (c) indicating the release behavior at different temperatures; (d) represents the swelling ratio of different pH values; (e) controlled release behavior and zeta potential at different pH values; (f) indicates the release behaviour of different dosage forms (error bars indicate standard deviation (n = 2)); compared with free TMX and beta-CD/TMX inclusion compound, the release time of 80 percent is prolonged from 8 hours to 60 hours, and the slow release characteristic is excellent; the beta-CD enhances the solubility of TMX and promotes the absorption of the drug by crops, and the Alg cross-linked network fixes the TMX/beta-CD; with the gradual dissolution and degradation of Alg, TMX/beta-CD is gradually released from the gel particles; due to the solubilization of β -CD, the released TMX is rapidly solubilized and absorbed by the plant;

FIG. 4 is a graph showing the degradation rate of TMX-loaded Alg/β -CD gel under UV irradiation;

FIG. 4 (a) is a photograph showing the swelling ratio and numerical values of TMX-loaded Alg at various salt concentrations; (b) swelling ratios representing different salt concentrations; (c) controlled release behavior and zeta potential for different salt concentrations; (d) shows the uv radiation resistance behavior, (error bars indicate standard deviation (n = 2));

FIG. 5 is a graph of the degradation rates of CTD and UiO-66@ Alg-CTD under UV irradiation;

FIG. 6 is a diagram of a potting experiment;

FIG. 6 (a) is a digital photograph showing a rice pot culture and a rice planthopper; (b) photographs of rice showing different times (day 22 with rice planthopper added); (c) showing the plant height statistics of potted rice; (d) indicating mortality of the pests; (i) denotes ck (ii) TMX (iii) TMX-loaded Alg/β -CD powder (iv) TMX-loaded Alg/β -CD particles, (error bars denote standard deviation (n = 2));

FIG. 7 is a recorded graph of plant height of rice;

in fig. 7, the growth state of the plants is recorded and tracked 20 days, 40 days, 60 days and 80 days after sowing, and the plant height of the plants is measured by taking five points in each cell by adopting a five-point sampling method, wherein (a) is 20 days; (b) for 40 days; (c) is 60 days; (d) for 80 days;

FIG. 8 is a graph showing the comparison of growth vigor of 60-day rice samples;

FIG. 9 is a diagram of field meteorological data for 80-day rice planting;

fig. 9 (a) shows the outdoor temperature; (b) represents outdoor relative humidity; (c) representing rainfall and transpiration; (d) indicating plant height variation; the weather condition of the rice planted for 80 days is generally displayed, a small amount of rainfall exists at the early stage of rice planting, the influence on the experiment is not large, and the transpiration amount is approximately negatively related to the rainfall. The early temperature floats between 19 and 29 ℃, and no supercooling weather occurs; obvious temperature reduction occurs after 56 days, the temperature is maintained below 20 ℃, and the temperature is reduced to about 8 ℃ in a few days before sampling; the relative humidity fluctuates around 70 RH;

FIG. 10 is a graph showing the variation of plant height of rice.

Detailed Description

In order to make the technical solutions and advantages of the present application clearer, the following describes the technical solutions clearly and completely with reference to the embodiments.

Example 1

The environment response controlled release pesticide preparation can be prepared by the following steps:

Step five: filtering and collecting the spherical hydrogel, washing to remove pesticide residues on the surface, and drying in a dryer at 20-80 ℃ for 12-24h to obtain the environment-responsive controlled-release pesticide carrier.

The functional agent is one or more of cyclodextrin, MOFs and biomass carbon.

The pesticide is neonicotinoid pesticide including thiamethoxam, clothianidin, dinotefuran and thiacloprid.

The natural polymer is one or more of sodium alginate, chitosan, carboxymethyl chitosan, lignin, sodium lignosulfonate, cellulose and carboxymethyl cellulose.

The cross-linking agent is one or more of copper nitrate, zinc nitrate, calcium chloride, ferric chloride, zinc chloride, vanillin and glutaraldehyde.

Example 2

Dissolving 1g of beta-cyclodextrin (beta-CD) in 50mL of water, adding 2g of Thiamethoxam (TMX) and stirring for more than 12h to prepare a TMX/beta-CD inclusion compound (suspension A), adding 0.3g of sodium alginate and stirring for 12h to uniformly mix the sodium alginate, the TMX/beta-CD inclusion compound and free TMX to form a mixture B. Adding 1.4g of TMX and 2g of beta-CD into 100mL of water at room temperature, uniformly stirring, adding 1.5g of calcium chloride, and uniformly stirring to form a mixture C; 50mL of mixture B was withdrawn with a syringe pump and added to mixture C at a rate of 1.35mL/min using a 0.5mm Teflon tube; and (3) forming white spherical particles after injection, stirring and crosslinking for half an hour, performing suction filtration by using a Buchner funnel, washing off the thiamethoxam on the surface by using deionized water, and drying for 24 hours at 40 ℃ to obtain a product TMX-loaded Alg/beta-CD. The environment response controlled release pesticide preparation prepared by the method is used for seed dressing, and then rice seeds are uniformly sown in soil, so that the purpose of preventing and controlling pests in rice planting is achieved.

Example 3

Dispersing 0.5g of UiO-66 in 50mL of water, adding 1.5g of Clothianidin (CTD), stirring for more than 12h to prepare the clothianidin-loaded UiO-66 (suspension A), and then adding 0.5g of sodium alginate, and magnetically stirring for 12h at room temperature to form a mixture B; adding 1.5g of UiO-66 and 3.5g of CTD into 100mL of water at room temperature, uniformly stirring, adding 1.5g of calcium chloride, and stirring to form a mixture C; 50mL of mixture B was added dropwise to mixture C using a syringe pump at a rate of 1 mL/h. And after sodium alginate and calcium chloride are crosslinked for 20 min, collecting the drug-loaded gel spheres, washing the microspheres for 3 times by using deionized water, removing the CTD attached to the surfaces of the microspheres, and finally drying the microspheres in a vacuum drier for 24h at 45 ℃ to obtain a product UiO-66@ Alg-CTD. The environment response controlled release pesticide preparation prepared by the method is used for seed dressing, and then rice seeds are uniformly sown in soil, so that the purpose of preventing and controlling pests in rice planting is achieved.

Field experiment

1. Reduction of the treatment agent in the body of rice

The reduction dynamics of each treatment agent in the rice body is regularly determined by adopting a rice residue method, rice leaves of about 100 g/cell are collected 20 days, 40 days and 60 days after sowing to perform the residue determination of the agent, and the pesticide residue detection results of the rice are recorded in the following table. In field experiments, TMX-loaded UIO-66-NH2/SL, TMX-loaded SA/beta-CD and CTD-loaded UIO-66/SA are all environment-responsive controlled-release pesticide preparations.

The data show that the sustained-release agent group has longer retention time on plants compared with pure medicines under the same conditions, the pure medicines have about 20 days, the sustained-release agent group basically reaches 40 days, and the CTD loaded UIO-66/SA granules last for 60 days. The retained drug concentration for each group generally decreased over time.

The data show that the drug concentration of the sustained-release agent group is larger than that of the pure drug group, the residue of the pure drug group can be detected in the first sampling, only the CTD1 group has a small amount of residue in the second sampling, and the drug can not be detected in the third pure drug group.

The drug concentration of the first group of TMX-loaded SA/beta-CD granules obtained by the first sampling is the highest and reaches 0.15mg/kg, the drug concentration of the first group of CTD loaded UIO-66/SA granules obtained by the second sampling is the highest and reaches 0.0097mg/kg, and the drug concentration of the third group of the TMX-loaded SA/beta-CD granules obtained by the second sampling is 0.014 mg/kg. Therefore, the TMX-loaded SA/beta-CD granules have better early-stage drug effect, and the CTD-loaded UIO-66/SA granules have slower early-stage release and better later-stage release effect.

2. Rice plant height record

The growth state of the seedlings is tracked 20 days, 40 days, 60 days and 80 days after sowing, and the plant height of the seedlings is measured by taking five points in each cell by adopting a five-point sampling method. The plant height (cm) is counted in the following table.

As shown in the table, the plant height of the sustained-release agent group is obviously higher than that of the pure drug group, and the best growth condition is TMX-loaded SA/beta-CD granules in 80 days.

3. Comparison of rice plants

In contrast to the CK group plants in the 60-day-old rice samples, the TMX-loaded SA/beta-CD granules showed no insect damage and showed good growth.

The above description is not intended to limit the present application, and the present application is not limited to the above examples, and those skilled in the art should understand that they can make various changes, modifications, additions or substitutions within the spirit and scope of the present application.

Claims

1. A preparation method of an environment response controlled release pesticide preparation is characterized in that: the preparation process comprises the following steps:

the method comprises the following steps: adding the required pesticide and functional agent into water, and fully stirring and mixing for 10-48 hours in a water bath at 20-60 ℃ to form a suspension A, wherein the added parts by weight are as follows: 0.5-2 parts of functional agent, 1-4 parts of pesticide and 30-60 parts of water;

step two: adding 0.3-1.5 parts by weight of natural polymer into the suspension A, and fully stirring and dissolving for 3-24 hours in a water bath at 20-60 ℃ to form a mixture B;

step three: adding the required pesticide and the functional agent into water, and fully stirring at room temperature to form a mixed solution, wherein the weight ratio of the functional agent to the pesticide to the water in the mixed solution is as follows: (0.5-2): (1-4): (30-60), adding a cross-linking agent into the mixed solution, and uniformly stirring to form a mixture C, wherein the mass concentration of the cross-linking agent in the solution is 0.1-5%;

step four: adding the mixture B into the mixture C in a dropwise manner, wherein the dropwise adding speed is 0.5-3 mL/h, and the crosslinking time is controlled to be 10-90 min, so as to obtain spherical hydrogel;

2. The method for preparing an environmentally-responsive controlled-release pesticidal formulation according to claim 1, wherein: the functional agent is one or more of cyclodextrin, MOFs and biomass carbon.

3. The method for preparing an environmentally-responsive controlled-release pesticidal formulation according to claim 1, wherein: the pesticide is neonicotinoid pesticide including thiamethoxam, clothianidin, dinotefuran and thiacloprid.

4. The method for preparing an environmentally-responsive controlled-release pesticidal formulation according to claim 1, wherein: the natural polymer is one or more of sodium alginate, chitosan, carboxymethyl chitosan, lignin, sodium lignosulfonate, cellulose and carboxymethyl cellulose.

5. The method for preparing an environmentally-responsive controlled-release pesticidal formulation according to claim 1, wherein: the cross-linking agent is one or more of copper nitrate, zinc nitrate, calcium chloride, ferric chloride, zinc chloride, vanillin and glutaraldehyde.

6. The use of the environment-responsive controlled-release pesticide preparation prepared by the preparation method of the environment-responsive controlled-release pesticide preparation according to claim 1 in rice planting.