CN116897940A - Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof - Google Patents

Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof Download PDF

Info

Publication number
CN116897940A
CN116897940A CN202310873339.1A CN202310873339A CN116897940A CN 116897940 A CN116897940 A CN 116897940A CN 202310873339 A CN202310873339 A CN 202310873339A CN 116897940 A CN116897940 A CN 116897940A
Authority
CN
China
Prior art keywords
release
slow
quick
abamectin
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310873339.1A
Other languages
Chinese (zh)
Inventor
曾章华
崔博
高飞
丁希权
杜谦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Environment and Sustainable Development in Agriculturem of CAAS
Original Assignee
Institute of Environment and Sustainable Development in Agriculturem of CAAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Environment and Sustainable Development in Agriculturem of CAAS filed Critical Institute of Environment and Sustainable Development in Agriculturem of CAAS
Priority to CN202310873339.1A priority Critical patent/CN116897940A/en
Publication of CN116897940A publication Critical patent/CN116897940A/en
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Toxicology (AREA)
  • Insects & Arthropods (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The application discloses an abamectin quick-release and slow-release double-effect solid pesticide and a preparation method thereof. The composition is as follows: 1% -20% of avermectin active ingredient, 1% -30% of surfactant, 0.5% -10% of slow release carrier and 40% -90% of quick release carrier. The quick-release and slow-release double-effect solid pesticide can not only combine systems with different release characteristics together in one-step preparation to play a synergistic effect, but also combine micron and nanometer double-size characteristics, so that the system has richer properties, the solid preparation form can also remarkably improve the stability of the preparation, the convenience and the safety of storage and transportation, the problems of agglomeration, flocculation, sedimentation and the like caused by interaction of electrostatic attraction, van der Waals force and the like in the water-dispersing process are overcome, and the ideal application effect is maintained.

Description

Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof
Technical Field
The application belongs to the technical field of pesticides, and in particular relates to an abamectin quick-release and slow-release double-effect solid pesticide and a preparation method thereof.
Background
The pesticide is an important material foundation for preventing and controlling agricultural diseases, insect pests and weeds and promoting stable and high-yield grains. At present, the traditional dosage forms such as emulsifiable concentrate, wettable powder and the like are still mainly used in China. The traditional dosage forms have the problems of large amount of organic solvents and auxiliary agents, dust drift, poor water dispersibility and the like, so that the loss of active ingredients in the pesticide use process is up to 70% -90%, for example, the effective utilization rate is generally less than 30% by taking protected crops as actual targets; the utilization rate is even less than 0.1% as calculated by the actual received amount of the pests. In addition, the traditional preparation has a low lasting period, and the effective concentration is difficult to maintain above the effective dosage for preventing and controlling pests for a long time, so that the traditional preparation needs to be applied for multiple times. Not only causes resource waste, but also causes serious pollution to soil, water and atmosphere. Therefore, the performance of the traditional preparation is improved, and the development of the double-effect preparation with excellent water dispersibility and stability and quick release property and slow release property is an important way for improving the effective utilization rate of the traditional preparation.
In recent years, carrier-coated slow-release pesticide systems such as microspheres, microcapsules, gels and the like have attracted more and more attention in the field of pesticide formulation processing. The slow release system can effectively inhibit pesticide decomposition and loss caused by light, heat, rainwater, soil, microorganisms and other environmental factors and other chemical substances, improve the stability of the preparation, inhibit pesticide volatilization, shield pesticide odor, reduce contact toxicity, inhalation toxicity and phytotoxicity, and reduce human and animal irritation. On the other hand, the method can effectively prolong the duration of the pesticide preparation, reduce the application dosage and times and reduce the toxicity of the pesticide to users and non-target organisms. Along with the rapid increase of agricultural labor cost and the improvement of environmental protection consciousness, the slow-release pesticide preparation gradually becomes one of the development directions of future pesticide dosage forms.
At present, a system with quick release and slow release functions in the agricultural field is a microcapsule suspension-suspension agent. The main disadvantages of the pesticide system are the stability of the liquid preparation, the quick release and slow release parts of the preparation are independent, the size of the drug carrying particles is large, sedimentation is easy to generate, more stabilizing agents and suspending agents are usually needed to be added to maintain the stability of the system, the liquid preparation is easy to be damaged by the interference of external environment, the storage and the transportation are inconvenient, and the quick-acting and slow release effects in practical application are difficult to coordinate.
The nano particles have small size effect, interface effect and high permeability effect, can improve the stability and water dispersibility of the insoluble pesticide, promote target deposition and dosage transfer, reduce loss, and further improve the pesticide utilization rate. Therefore, the pesticide quick-release nano particles are constructed by adopting nano materials and technology, so that the pesticide quick-release nano particles can not only enable the preparation to exert pesticide effect in a short time and rapidly control the spreading trend of diseases and insect pests, but also can obviously improve the dispersibility, effectiveness and safety of the pesticide. The research shows that the smaller the particle diameter of the nano particle is, the higher the dispersion rate and suspension rate of the nano particle after the nano particle is added into water, and the higher the leaf surface adhesion rate and deposition performance of the nano particle are along with the increase of the specific surface area of the particle, namely the nano-scale dispersion drug-carrying system is beneficial to the exertion of quick release property of pesticides and the improvement of biological activity. For a slow release system, according to the current literature report and the previous research results of a team, the larger the particle size of the drug-carrying particles and the thicker the shell material, the more beneficial to prolonging the release time of the drug and improving the protection performance of the pesticide. Therefore, how to combine the nano-and micro-drug delivery systems together has been a difficulty in the field of pesticide formulation processing, in terms of how to make the system have quick-acting, slow-release, stability and high-efficiency.
Disclosure of Invention
The application aims to provide an abamectin quick-release and slow-release double-effect solid pesticide and a preparation method thereof.
The abamectin quick-release and slow-release double-effect solid pesticide disclosed by the application is dispersed in water and exists in two sizes, wherein the effective components in the quick-release medicine carrying part are dispersed in water and are in nano-size of 1-100nm, and the effective components in the slow-release medicine carrying part are dispersed in water and are in micro-size of 1-5 mu m.
The abamectin quick-release-slow-release double-effect solid pesticide provided by the application comprises the following components in parts by weight:
in the abamectin quick-release and slow-release double-effect solid pesticide, the abamectin active ingredients comprise one or more of B1 abamectin, B2 abamectin and emamectin benzoate.
In the abamectin quick-release and slow-release double-effect solid pesticide, the surfactant is understood to be a substance capable of obviously changing the interface state of a solution system.
The molecule of the surfactant contains both hydrophilic groups and hydrophobic groups.
The hydrophilic group is a polar group such as carboxylic acid, sulfonic acid, sulfuric acid, amino, hydroxyl, amide, etc.; whereas hydrophobic groups are often nonpolar hydrocarbon chains.
The surfactant may be: anionic surfactant, nonionic surfactant, or a combination thereof.
The anionic surfactant may be selected from: maleic rosin polyoxyethylene-oxypropylene ether sulfonate, alkylphenol polyoxyethylene ether phosphate, monododecyl ether phosphate, didodecyl ether phosphate, octyl ether phosphate, fatty alcohol polyoxyethylene ether carboxylate, polycarboxylate and lignin sulfonate;
the nonionic surfactant may be selected from: phenolic resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, isopropyl phenol polyoxyethylene ether formaldehyde condensate, polyvinyl alcohol, castor oil polyoxyethylene ether, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, sorbitan oleic acid ester and polyoxyethylene polyoxypropylene block copolymer.
The slow release carrier is polylactic acid compound, and can be at least one of polylactic acid and polylactic acid-glycolic acid copolymer.
Laboratory researches find that the polylactic acid compound can form a good micron-sized drug carrying system in the oil-water two-phase film forming and solvent volatilizing processes of the process, a part of avermectin compounds are wrapped or adsorbed, slow release of drugs is realized, and meanwhile, the separation effect of quick release carriers and the dispersion effect of surfactants are utilized to avoid massive coalescence of the micron-sized system.
The quick-release carrier is at least one of sodium n-butyrate, sodium benzoate, sodium dodecyl sulfate, urea and lactose.
The quick-release carrier not only plays a role of supporting carrier in the composition of the preparation, so that the pesticide compound is dispersed among the carriers in the form of particles, but also accelerates the water-in dispersion and dissolution of the pesticide-carrying particles by virtue of the higher solubility and the quicker dispersibility of the pesticide-carrying compound in water. Part of avermectin compounds can be adsorbed on the surface of the quick-release carrier, and when the avermectin compounds are dispersed by adding water, medicine carrying particles can be prevented from agglomerating, flocculating and precipitating by electrostatic action or steric hindrance, so that the quick-release medicine carrying particles are ensured to suspend in water in the form of nano particles along with the dissolution of the carrier.
The abamectin quick-release and slow-release double-effect solid pesticide preparation is prepared by a method comprising the following steps according to the process flow shown in figure 1:
(1) Dissolving a slow release carrier into an organic solvent to obtain a transparent oil phase A;
(2) The avermectin active ingredient and the surfactant are added into the oil phase A, and the transparent oil phase B which is uniformly dispersed is obtained after complete dissolution;
(3) Slowly dripping the oil phase B into water, and shearing and emulsifying to obtain a mixed phase C;
(4) Adding a quick-release carrier into the mixed phase C under stirring to obtain a mixture D;
(5) And (3) removing the solvent and the water in the step D to obtain the abamectin quick-release and slow-release double-effect solid pesticide.
In the step (1) of the method, the organic solvent is a low-boiling-point organic solvent which can simultaneously dissolve the slow-release carrier and the avermectin active ingredients and is insoluble with water,
on one hand, the method is used for ensuring that the avermectin pesticide is dissolved into a molecular state, facilitating the assembly process of a micron and nanometer system, and on the other hand, the method is used for facilitating the removal of the solvent during the subsequent removal of the solvent. The water-insoluble solvent can promote the slow release carrier to gather at the oil-water two-phase interface, and then the slow release carrier can be separated out or self-assembled at the interface along with the removal of the organic solvent, so that pesticide compounds are adsorbed or wrapped, and the construction of a slow release system is realized.
The organic solvent can be dichloromethane and/or chloroform.
At present, the construction of nano pesticide particles generally needs the assistance of external crushing means such as grinding, shearing and the like, so that not only is the energy consumption high, but also the obtained particle size distribution is uneven, and a system is polluted due to the problems of corrosion, falling-off and the like of grinding beads, so that the final quality of a product is influenced. The preparation method of the application does not need high-energy consumption equipment such as a grinder, has simple preparation process, easy control, stable product quality and good reproducibility, improves the production efficiency and the pesticide utilization rate, and saves the production cost.
The amount of the slow release carrier in the application is not more than 10%, and the amount of the quick release carrier is not less than 40%, otherwise, the water dispersibility of the solid pesticide is affected, and the quick release and the slow release effects are further affected.
The application creatively fuses the micro-scale and nano-scale pesticide carrying systems through long-time research and study, and adopts a one-step preparation method to construct the abamectin quick-release and slow-release double-effect solid pesticide. When the preparation is applied, the nano-scale drug-carrying particles rapidly disperse and release the drug, thereby playing a role in quick release, and simultaneously, the small-size effect, the large specific surface effect, the interface effect and the high permeability of the nano-particles are beneficial to increasing the adhesiveness and the permeability of the drug on the leaf surfaces of crops, so that the bioavailability of the drug is improved. In contrast, the pesticide active ingredient in the micron-sized slow-release carrier slowly releases pesticide due to the wrapping/adsorbing effect of the slow-release carrier, so that the release time of the pesticide can be prolonged, the pesticide active concentration can be maintained above the effective dosage for a long time, the effectiveness and the lasting effect of the medicament are ensured, the operation cost is reduced, and the ecological and environmental benefits are improved. The nanometer and micrometer drug carrying systems are mutually fused on the composition of the preparation, thereby ensuring the uniformity of the systems and avoiding the agglomeration and aggregation among single systems. In addition, the preparation is in a solid preparation form, is less influenced by external environment compared with a liquid preparation, has obviously improved stability and shelf life, and is convenient for packaging, storage and transportation.
The quick-release and slow-release double-effect solid pesticide can not only combine systems with different release characteristics together in one-step preparation to play a synergistic effect, but also combine micron and nanometer double-size characteristics, so that the system has richer properties, the solid preparation form can also remarkably improve the stability of the preparation, the convenience and the safety of storage and transportation, the problems of agglomeration, flocculation, sedimentation and the like caused by interaction of electrostatic attraction, van der Waals force and the like in the water-dispersing process are overcome, and the ideal application effect is maintained.
Drawings
Figure 1 is a process flow chart of the application for preparing abamectin quick-release and slow-release double-effect solid pesticide.
Fig. 2 is a particle size distribution diagram of the B1 type abamectin quick-release and slow-release double-effect powder prepared in the embodiment 1 of the application after being added into water.
FIG. 3 is a graph showing the comparative sustained release performance of the immediate release-sustained release dual-effect formulation, ethylcellulose pure sustained release formulation, and dual-effect formulation with ethylcellulose as sustained release carrier in example 8 of the present application.
FIG. 4 is a graph showing the comparison of the retention performance of the immediate release-sustained release preparation in example 9 of the present application with the retention performance of the ethylcellulose pure sustained release preparation.
FIG. 5 is a sustained release profile of the formulation prepared in comparative example 1.
Detailed Description
The following detailed description of the application is provided in connection with the accompanying drawings that are presented to illustrate the application and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the application in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of B1-type Avermectin immediate Release-sustained Release Dual-effect powder with 1% mass concentration
The implementation steps of this embodiment are as follows:
(1) Weighing 0.7g of polylactic acid (Shandong national academy of pharmacy) and dissolving into 8mL of dichloromethane (Beijing Limited of national medicine group chemical reagent), and obtaining transparent oil phase A after complete dissolution;
(2) Adding 0.1g of a stock avermectin (Qilu pharmaceutical (inner Mongolia) Co., ltd.), 0.8g of agricultural emulsion 600 (styrylphenol polyoxyethylene ether, cantonese Ind.) and 0.8g of agricultural emulsion 700 (alkylphenol formaldehyde resin polyoxyethylene ether, cantonese Ind.) into A, and completely dissolving to obtain a transparent oil phase B;
(3) Slowly dripping the oil phase B into 15mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 7.6g of sodium benzoate was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 45 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, crushing the mixture again uniformly to obtain the B1 abamectin quick-release and slow-release double-effect pesticide powder.
The B1 type abamectin quick-release and slow-release double-effect powder prepared in the embodiment is dispersed by standard hard water, the wetting time is 15s, the average particle diameter of nano-scale drug-carrying particles in a drug-carrying system is measured to be 25nm by using a Markov particle sizer, and the average particle diameter of micro-scale drug-carrying particles is 2.0 microns.
Example 2 preparation of emamectin benzoate quick-Release-sustained double-effect tablet with 20% Mass concentration
The implementation steps of this embodiment are as follows:
(1) Weighing 0.3g of polylactic acid, dissolving the polylactic acid into 5mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) 2g of emamectin benzoate (Qilu pharmaceutical Co., ltd.) and 1.5g of agricultural emulsion 600 are added into A, and transparent oil phase B is obtained after complete dissolution;
(3) Slowly dripping the oil phase B into 10mL of water, shearing at 8000rpm, and obtaining a mixed phase C;
(4) 6.2g of sodium n-butyrate (carbofuran technologies Co., ltd.) was added to the mixed phase C with stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 45 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, uniformly crushing again to obtain the emamectin benzoate quick-release and slow-release double-effect powder;
(6) And (3) putting the double-effect powder into a tablet press for tabletting to prepare the emamectin benzoate quick-release and slow-release double-effect tablet.
The emamectin benzoate immediate-release and slow-release double-effect tablet prepared in the embodiment is dispersed by standard hard water, the wetting time is 42s, the average particle size of nano-scale drug-carrying particles in a drug-carrying system is 52nm, and the average particle size of micro-scale drug-carrying particles is 2.8 microns.
Example 3 preparation of B1-type Avermectin immediate Release-sustained Release Dual-effect granule with mass concentration of 5%
The implementation steps of this embodiment are as follows:
(1) Weighing 0.5g of polylactic acid, dissolving the polylactic acid into 4mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) 0.5g of B1 type avermectin raw material and 2g of polyvinyl alcohol (Shanghai source leaf biotechnology Co., ltd.) are added into A, and transparent oil phase B is obtained after complete dissolution;
(3) Slowly dripping the oil phase B into 13mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 7g of lactose (Shanghai Yuan Yes Biotechnology Co., ltd.) was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 50 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, uniformly crushing again to obtain the B1 abamectin quick-release and slow-release double-effect powder.
(6) Adding a proper amount of binder (1% PVA aqueous solution, the amount of which is 2%) into the double-effect powder, putting into an extrusion granulator for extrusion granulation, and drying the water to obtain the B1 type abamectin quick-release and slow-release double-effect granule.
The B1 type abamectin quick-release and slow-release double-effect granule prepared in the embodiment is dispersed by standard hard water, the wetting time is 32s, the average particle size of nano-scale medicine carrying particles in a medicine carrying system is 45nm, and the average particle size of micro-scale medicine carrying particles is 3.1 microns.
Example 4 preparation of B2-type Avermectin immediate Release-sustained Release Dual-effect powder with a mass concentration of 4%
The implementation steps of this embodiment are as follows:
(1) Weighing 0.5g of polylactic acid, dissolving the polylactic acid into 4mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) Adding 0.4g of B2 abamectin raw material (Hebei Xingbai agricultural science and technology Co., ltd.), 0.05g of agricultural emulsion 600 and 0.05g of maleated rosin polyoxyethylene-oxypropylene ether sulfonate (Jiangsu qingyu chemical industry Co., ltd.) into A, and completely dissolving to obtain a transparent oil phase B;
(3) Slowly dripping the oil phase B into 12mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 9.0g of sodium benzoate was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 45 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, crushing the mixture again uniformly to obtain the B2 abamectin quick-release and slow-release double-effect powder.
The B2 type abamectin quick-release and slow-release double-effect powder prepared in the embodiment is dispersed by standard hard water, the wetting time is 15s, the average particle size of nano-scale medicine carrying particles in a medicine carrying system is 67nm, and the average particle size of micro-scale medicine carrying particles is 3.3 microns.
Example 5 preparation of emamectin benzoate quick-Release-sustained double-effect tablet with a Mass concentration of 10%
The implementation steps of this embodiment are as follows:
(1) Weighing 0.05g of polylactic acid-glycolic acid copolymer (Shandong national academy of sciences of pharmacy) and dissolving the copolymer into 3mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) 1g of emamectin benzoate technical and 3g of lignosulfonate (Shanghai source leaf biotechnology Co., ltd.) are added into A, and after complete dissolution, a transparent oil phase B is obtained;
(3) Slowly dripping the oil phase B into 8mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 5.95g of sodium benzoate was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) And (3) freeze-drying the mixture D to remove dichloromethane and water, and crushing the mixture again uniformly to obtain the emamectin benzoate quick-release and slow-release double-effect powder.
(6) And (3) putting the double-effect powder into a tablet press for tabletting to prepare the emamectin benzoate quick-release and slow-release double-effect tablet.
The emamectin benzoate immediate-release and slow-release double-effect tablet prepared in the embodiment is dispersed by standard hard water, the wetting time is 41s, the average particle size of nano-scale drug-carrying particles in a drug-carrying system is 76nm, and the average particle size of micro-scale drug-carrying particles is 2.6 microns.
Example 6 preparation of B2-type Avermectin immediate Release-sustained Release Dual-effect powder with 15% mass concentration
The implementation steps of this embodiment are as follows:
(1) Weighing 1g of polylactic acid, dissolving the polylactic acid into 8mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) Adding 1.5g of B2 abamectin raw material, 0.5g of agricultural emulsion 600 and 0.5g of agricultural emulsion 700 into A, and completely dissolving to obtain a transparent oil phase B;
(3) Slowly dripping the oil phase B into 15mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 6.5g of sodium dodecyl sulfate (Shanghai Michlin Biochemical technologies Co., ltd.) was added to the mixed phase C with stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 45 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, uniformly crushing again to obtain the B2 abamectin quick-release and slow-release double-effect powder.
The B2 type abamectin quick-release and slow-release double-effect powder prepared in the embodiment is dispersed by standard hard water, the wetting time is 33s, the average particle size of nano-scale medicine carrying particles in a medicine carrying system is 72nm, and the average particle size of micro-scale medicine carrying particles is 4.3 microns.
Example 7 preparation of double-carried immediate Release-sustained Release double-effect powder of B1 Avermectin and 2.5% emamectin benzoate with a Mass concentration of 2.5%
The implementation steps of this embodiment are as follows:
(1) Weighing 0.5g of polylactic acid, dissolving the polylactic acid into 4mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) Adding 0.25g of B1-type avermectin raw material, 0.25g of emamectin benzoate raw material and 2g of polyvinyl alcohol into the solution A, and completely dissolving to obtain a transparent oil phase B;
(3) Slowly dripping the oil phase B into 10mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 7g of lactose was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 50 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, crushing the mixture again uniformly to obtain the double-load quick-release and slow-release double-effect powder of B1 abamectin and emamectin benzoate.
The B1 type avermectin and emamectin benzoate dual-carrier quick-release and slow-release double-effect powder prepared in the embodiment is dispersed by standard hard water, the wetting time is 16s, the average particle size of nano-level medicine carrying particles in a medicine carrying system is 65nm, and the average particle size of micro-level medicine carrying particles is 3.7 microns.
Example 8, sustained release performance test:
the B1 type avermectin pure sustained-release preparation taking the ethyl cellulose as a single carrier is prepared by adopting the following method. The specific preparation process comprises the following steps: (1) Weighing 0.1g of B1 type avermectin raw material and 2g of ethyl cellulose, dissolving in 5mL of dichloromethane, and stirring to completely dissolve the raw material and the ethyl cellulose to obtain an oil phase A; (2) Preparing a polyvinyl alcohol aqueous solution with the mass concentration of 5%, adding 5.9g of sodium dodecyl sulfate into 40mL of the polyvinyl alcohol aqueous solution, and stirring until the sodium dodecyl sulfate is completely dissolved to obtain a water phase B; (3) And adding the oil phase A into the water phase B at a stirring speed of 1500rpm, continuously stirring until dichloromethane is completely volatilized, filtering, washing and drying to obtain the B1 type avermectin-ethylcellulose pure sustained-release preparation.
The sustained release carrier polylactic acid in the example 1 is changed into ethyl cellulose, other components and contents are kept unchanged, and the double-effect preparation with the ethyl cellulose as the sustained release carrier is prepared.
A certain amount of the B1 type abamectin quick-release and slow-release double-effect powder, the double-effect preparation taking ethyl cellulose as a slow-release carrier and the pure ethyl cellulose slow-release preparation prepared in the example 1 are filled into a dialysis bag, and a 15% ethanol solution is used as a slow-release medium, so that the slow-release performance test is carried out in a constant-temperature shaking table at 25 ℃. And taking out 1mL of slow-release liquid after slow release for 5h, 10h, 24h, 48h, 72h, 96h and 120h respectively, measuring the content of pesticide in the slow-release liquid by adopting high performance liquid chromatography, and calculating the slow-release rate. 1mL of 15% ethanol solution was added again after each sampling to the slow release medium.
In the experiment, the sustained release performance of the medicament prepared by the application is compared with that of a preparation taking ethylcellulose as a single carrier, and the result is shown in figure 3. Test results show that the double-effect solid pesticide preparation prepared by the preparation method of the application, which takes polylactic acid as a slow release carrier and sodium benzoate as a quick release carrier, has burst release characteristics at the early stage of release, has a faster release rate, shows quick release performance, and then shows a gentle release process along with slow release of the drug in the slow release carrier, and the release rate is obviously lower than that of a control slow release preparation, so that the duration of the preparation can be effectively prolonged, and the production cost is saved.
In contrast, the release rate of pesticides in the double-effect preparation prepared by adopting ethylcellulose as a slow-release carrier is faster, and most of the drugs are released in a short time, because: in the preparation method, the ethylcellulose cannot realize good coating on the avermectin, most of pesticide active ingredients are only adsorbed on the carrier in a free way, and the pesticide active ingredients are quickly dissolved out after entering the solution so as to be released, so that the ideal controlled release effect is difficult to achieve.
Example 9 foliar adhesion retention Performance test
Leaf retention was measured by dipping. Fresh and clean cucumber and cabbage leaves are taken, the surface areas of the fresh and clean cucumber and cabbage leaves are measured by a leaf area meter, the leaves are respectively immersed in the B1 type abamectin quick-release and slow-release double-effect powder prepared in the example 1 and the aqueous dispersion of the ethylcellulose slow-release preparation, the leaves are taken out after being immersed for 15 seconds, and the leaves are vertically placed until liquid drops stop dripping. The mass of each leaf before and after soaking was recorded. Retention (Rm, mg/cm) 2 ) The calculation formula of (2) is as follows: rm= (W1-W0)/S. Wherein: w0 and W1 are mass (mg) of the blade before and after impregnation in the dispersion, and S is blade area (cm) 2 )。
As shown in the test result in figure 4, the retention of the quick-release and slow-release double-effect solid pesticide prepared by the preparation method of the application on the surfaces of hydrophilic cucumbers and hydrophobic cabbages is larger than that of the pure slow-release ethylcellulose preparation, which shows that the quick-release and slow-release double-effect solid pesticide has better surface adhesion retention performance mainly due to the small-size effect, the large specific surface effect, the interface effect and the high permeability of the nano particles. The improvement of the adhesion retention performance of the leaf surfaces can improve the effective utilization rate of pesticides, reduce the pesticide loss, reduce the dosage and improve the environmental and ecological effects of the preparation.
Example 10 biological Activity assay
The green test procedure was as follows: the B1 type abamectin quick-release and slow-release double-effect powder prepared in the example 1 and the ethyl cellulose pure slow-release preparation are diluted into a series of concentration liquid medicine by 0.05% of triton X-100 aqueous solution. Selecting proper-sized cabbage leaves, respectively immersing the cabbage leaves in liquid medicines with different concentrations, taking out the cabbage leaves after 10 seconds, airing the cabbage leaves at room temperature, placing the cabbage leaves in a disposable culture dish paved with filter paper, picking up 10 heads of 2-year primary larvae of plutella xylostella in each dish, and repeating each treatment for 4 times. A0.05% aqueous solution of triton was used as a blank. And (5) placing the treated test insects under normal feeding conditions for feeding. The death rate was calculated by checking the number of dead insects and the number of live insects after 24 hours and 72 hours, respectively. Calculating virulence regression equation and LC by DPS software 50 And a correlation coefficient.
TABLE 1 toxicity measurement results of different formulations on Plutella xylostella (24 h)
TABLE 2 toxicity measurement results of different formulations on Plutella xylostella (72 h)
The test results are shown in tables 1 and 2, and the data show that compared with the conventional slow release agent, the quick release-slow release double effect powder of the application has the LC of the plutella xylostella for 24 hours or 72 hours 50 The pesticide is lower than the ethylcellulose sustained release agent, namely, the pesticide has better insecticidal effect on quick action and long-acting performance, and has better double-effect function. The improvement of the insecticidal activity can reduce the use amount of pesticides and improve the ecological safety and economic benefit of the preparation.
Comparative example 1
(1) Weighing 2.0g of polylactic acid, dissolving the polylactic acid into 15mL of dichloromethane, and obtaining a transparent oil phase A after complete dissolution;
(2) 1.3g of B1-type avermectin raw material, 1.5g of agricultural emulsion 600 and 1.5g of agricultural emulsion 700 are added into A, and transparent oil phase B is obtained after complete dissolution;
(3) Slowly dripping the oil phase B into 25mL of water, shearing at 5000rpm, and obtaining a mixed phase C;
(4) 3.7g of sodium benzoate was added to the mixed phase C under stirring at 500rpm to obtain a mixture D;
(5) Heating the mixture D at 45 ℃ by adopting an oven, and after the dichloromethane and the water are completely volatilized, crushing the mixture again uniformly to obtain the B1 abamectin quick-release and slow-release double-effect pesticide powder.
The prepared solid preparation is dispersed by standard hard water, the wetting time is 87s, the average particle diameter of nano-scale drug-carrying particles in a drug-carrying system is 335nm, and the average particle diameter of micro-scale drug-carrying particles is 5.1 microns. Both the dispersibility and uniformity of the formulation are significantly reduced.
The slow release graph 5 shows that a 15% ethanol solution is used as a slow release medium. Because the content of the quick-release carrier which plays a role in blocking and rapid dispersion in the composition is reduced, agglomeration and adhesion are easy to occur among prepared solid particles, most of pesticide active ingredients are wrapped in the slow-release carrier, so that the dispersibility and quick-release property of the preparation are obviously reduced, meanwhile, due to the existence of particle aggregates, the particles in the slow-release medium are easy to collapse and settle, the rate of releasing the pesticide is very slow, the active ingredients in the liquid medicine are very low, and the requirements in practical application are difficult to meet.
The present application is described in detail above. It will be apparent to those skilled in the art that the present application can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the application and without undue experimentation. While the application has been described with respect to specific embodiments, it will be appreciated that the application may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains.

Claims (9)

1. The abamectin quick-release and slow-release double-effect solid pesticide comprises the following components in parts by weight:
2. the abamectin quick release-slow release double effect solid pesticide according to claim 1, characterized in that: the avermectin active ingredient comprises one or more of B1 type avermectin, B2 type avermectin and emamectin benzoate.
3. The abamectin quick release-slow release double effect solid pesticide according to claim 1 or 2, characterized in that: the surfactant is as follows: an anionic surfactant, a nonionic surfactant, or a combination thereof;
wherein the anionic surfactant is selected from the group consisting of: maleic rosin polyoxyethylene-oxypropylene ether sulfonate, alkylphenol polyoxyethylene ether phosphate, monododecyl ether phosphate, didodecyl ether phosphate, octyl ether phosphate, fatty alcohol polyoxyethylene ether carboxylate, polycarboxylate and lignin sulfonate;
the nonionic surfactant is selected from the group consisting of: phenolic resin polyoxyethylene ether, styrylphenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, isopropyl phenol polyoxyethylene ether formaldehyde condensate, polyvinyl alcohol, castor oil polyoxyethylene ether, polyvinylpyrrolidone, polyoxyethylene sorbitan monooleate, sorbitan oleic acid ester and polyoxyethylene polyoxypropylene block copolymer.
4. An abamectin quick release-slow release double effect solid pesticide according to any one of claims 1 to 3, characterised in that: the slow release carrier is polylactic acid compound.
5. The abamectin quick release-slow release double effect solid pesticide according to claim 4, characterized in that: the slow release carrier is at least one of polylactic acid and polylactic acid-glycolic acid copolymer.
6. The abamectin quick release-slow release double effect solid pesticide according to any one of claims 1 to 5, characterized in that: the quick-release carrier is at least one of sodium n-butyrate, sodium benzoate, sodium dodecyl sulfate, urea and lactose.
7. A method for preparing the abamectin quick release-slow release double effect solid pesticide preparation according to any one of claims 1 to 6, comprising the following steps:
(1) Dissolving a slow release carrier into an organic solvent to obtain a transparent oil phase A;
(2) Adding the avermectin active ingredient and the surfactant into the A, and obtaining a transparent oil phase B which is uniformly dispersed after complete dissolution;
(3) Slowly dripping the oil phase B into water, and shearing and emulsifying to obtain a mixed phase C;
(4) Adding a quick-release carrier into the C under stirring to obtain a mixture D;
(5) And (3) removing the solvent and the water in the step D to obtain the abamectin quick-release and slow-release double-effect solid pesticide.
8. The method according to claim 7, wherein: in the step (1), the organic solvent is a low-boiling-point organic solvent which is used for simultaneously dissolving the slow-release carrier and the avermectin active ingredients and is insoluble with water.
9. The method according to claim 8, wherein: the organic solvent is dichloromethane and/or chloroform.
CN202310873339.1A 2023-07-17 2023-07-17 Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof Pending CN116897940A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310873339.1A CN116897940A (en) 2023-07-17 2023-07-17 Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310873339.1A CN116897940A (en) 2023-07-17 2023-07-17 Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116897940A true CN116897940A (en) 2023-10-20

Family

ID=88356024

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310873339.1A Pending CN116897940A (en) 2023-07-17 2023-07-17 Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116897940A (en)

Similar Documents

Publication Publication Date Title
JP5883388B2 (en) Anthraquinone-containing derivatives as biochemical agricultural products
CN102823585B (en) Sustained-release preparation for water-soluble pesticide and preparation method of sustained-release preparation
JP2007509870A (en) Solid active ingredient formulation
CN102939961B (en) Pesticide microparticle preparation having core-shell structure and preparation method thereof
CN101692808A (en) Emamectin benzoate solid lipid nanoparticle and preparation method and application thereof in pesticide formulation
CN102885060A (en) Avermectin nanometer microemulsion and preparation method thereof
CN111616156A (en) Abamectin and spinosad nano suspending agent and preparation method thereof
Kök et al. Controlled release of aldicarb from carboxymethyl cellulose microspheres: in vitro and field applications
Cortesi et al. Natural antimicrobials in spray-dried microparticles based on cellulose derivatives as potential eco-compatible agrochemicals
Zhang et al. In-situ coordination assembly of polyphenol with cage-like Prussian blue as an ecofriendly nanocarrier for site-specific pesticide delivery and sustained pest control
CN113367130A (en) Pesticide compound drug-loaded microsphere for honeysuckle and preparation method thereof
CN116897940A (en) Avermectins quick-release and slow-release double-effect solid pesticide and preparation method thereof
CN110786335B (en) Novel nano pesticide preparation and preparation method thereof
JPS5920209A (en) Improved germicidal composition
CN101700008A (en) Solid lipid nano-avermectin and preparation method and application thereof
WO2009086739A1 (en) Water soluble granule of chlorfenapyr and its preparation
CN1663378A (en) Pesticide formulation of nimbin and emamectin benzoate and preparing method thereof
CN109792996B (en) Avermectin nano-powder and preparation and use method thereof
CN101218922A (en) High-efficiency and low-toxin seed-treating agent
CN114885953A (en) Emamectin benzoate-sodium alginate nanoparticle slow-release pesticide and preparation method thereof
CN1781372A (en) Water dispersion particle agent of abamectin and its producing method
CN105010384B (en) A kind of doractin and pyrethroid insecticides composition
CN116327756B (en) Nanometer preparation and preparation method and application thereof
Pengiran et al. RESEARCH ARTICLE Larvicidal efficacy of temephos impregnated onto kenaf cellulose nanofibre to control Aedes aegypti (Diptera: Culicidae) larvae
CN115735924B (en) Seed treating agent and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination