CN117426400B - Synergistic auxiliary agent of acaricide, preparation method and application thereof - Google Patents
Synergistic auxiliary agent of acaricide, preparation method and application thereof Download PDFInfo
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- CN117426400B CN117426400B CN202311757526.XA CN202311757526A CN117426400B CN 117426400 B CN117426400 B CN 117426400B CN 202311757526 A CN202311757526 A CN 202311757526A CN 117426400 B CN117426400 B CN 117426400B
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- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
-
- 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
- A01N25/22—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 ingredients stabilising the active ingredients
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- 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
- A01N25/24—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 ingredients to enhance the sticking of the active ingredients
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- 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
- A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
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- 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
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- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
- A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
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- 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
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- 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
- A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
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- 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
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Abstract
The invention provides a synergistic auxiliary agent of an acaricide, a preparation method and application thereof. The synergistic agent disclosed by the invention comprises the following components: cottonseed phenol, rosin phenol, ricinoleate, linalool, succinate, longifolene, notoginsenoside R1, camellia seed extract and auxiliary materials; the auxiliary materials comprise sodium dioctyl sulfosuccinate, sodium diisooctyl sulfosuccinate, methyl salicylate and auxiliary agents. Compared with the prior art, the synergistic auxiliary agent prepared by the invention can protect the acaricide from being irradiated and degraded by ultraviolet rays, thereby prolonging the effective life of the acaricide, having a slow release effect, prolonging the action time of the pesticide effect in the field and enhancing the action effect of the acaricide.
Description
Technical Field
The invention relates to the technical field of pesticides, in particular to a synergistic auxiliary agent of an acaricide, a preparation method and application thereof.
Background
The synergistic assistant of the acaricide is an auxiliary ingredient added in the acaricide and is used for enhancing the effect and performance of the acaricide. The synergistic agents can act through different mechanisms to improve the effect of killing mites, increase durability, improve stability and the like. The following are some common descriptions of acaricide synergists: surfactants have the ability to reduce the surface tension of liquids and to increase the wetting properties of liquids. The surfactant is added into the acaricide to enhance the adhesion and penetration capability of the acaricide to the mite surface and improve the killing effect. The solvent can dissolve and uniformly disperse the active ingredients in the acaricide to enhance the stability and bioavailability thereof. Common solvents include water, organic solvents (e.g., ethanol, acetone, etc.), and mixed solvents. The antioxidant can prevent the acaricide from being influenced by oxidation reaction during storage and use, thereby improving stability and durability. Common antioxidants include vitamin C, vitamin E, benzoic acid, and the like. The emulsifier can uniformly disperse the water phase and the oil phase in the acaricide to form stable emulsion. The emulsifier can improve suspension and dispersibility of the acaricide, and make it easier to use and spray. The pH regulator can change the ionic state and chemical activity of the acaricide by regulating the pH value of the acaricide. Some mites are sensitive to environments of different pH values, so adjusting pH can affect the effect and stability of the acaricide. The penetration enhancer can enhance the penetration of acaricide to mites, and promote the active ingredients to enter mites. These synergists increase the penetration of the acaricide, making it easier to penetrate the mite coat. The adhesive can increase the adhesive force of the acaricide on the target surface and prolong the durability and effect of the acaricide. These synergists enable the acaricide to adhere better to the surface where mites inhabit, increasing contact time and effectiveness. The preservative can prevent the acaricide from being polluted and degraded by bacteria, fungi and other microorganisms during storage and use. The synergists can maintain the purity and activity of the acaricide and prolong the effective period of the acaricide.
The prior art also has some defects in the field of acaricide synergistic assistants, and some synergistic assistants are possibly incompatible with acaricides or have poor stability, so that the mixed preparation has the problems of interaction, layering, precipitation or degradation and the like. This may affect the uniformity, performance and durability of the acaricide. Therefore, the compatibility and stability of the co-adjuvants with the acaricides need to be considered in the selection and formulation of the co-adjuvants. The existing acaricide synergistic agent is generally broad-spectrum and has a certain effect on various mites. However, different species of mites may have different sensitivities and resistances to different co-agents and acaricide combinations. Therefore, there is a need for more development of specific synergists for specific mite species to improve the selectivity and efficacy of acaricides.
These drawbacks and challenges need to be overcome by further research and development to improve the efficacy of the acaricide co-formulation.
The Chinese patent No. 105850998B discloses a preparation method and application of a plant-derived pesticide synergist, wherein the preparation method comprises the steps of adding ethanol into rosin or rosin, stirring and dissolving, and filtering to obtain rosin or rosin solution; adding alkali liquor into rosin or rosin solution to react, adding emulsifier, and filtering to obtain the synergist. The invention has the advantages of low-cost and easily-obtained raw materials, simple preparation route, no need of special reaction equipment, energy conservation, environmental protection, low cost and high yield, and is very suitable for large-scale production. The obtained synergist can reduce the surface tension of the liquid medicine, and after being compounded with various pesticides such as insecticide, acaricide, herbicide and the like, the synergist not only can improve the control effect of the pesticide and reduce the pesticide dosage, but also has the advantages of broad spectrum, high efficiency, low cost and the like, and has good popularization and application prospects and remarkable economic, social and environmental benefits. However, the ultraviolet resistance and the field efficacy of the synergistic agent prepared by the invention are still insufficient, and the compatibility with acaricides is a problem.
Disclosure of Invention
In view of the defects of poor ultraviolet resistance and poor field efficacy of the synergists in the prior art, the invention aims to provide a synergism auxiliary agent of an acaricide with good ultraviolet resistance and good field efficacy, a preparation method and application thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
a synergistic auxiliary agent of acaricide comprises the following components: cottonseed phenol, rosin phenol, ricinoleate, linalool, succinate, longifolene, notoginsenoside R1, camellia seed extract and auxiliary materials.
Preferably, the auxiliary materials comprise dioctyl sodium sulfosuccinate, diisooctyl sodium sulfosuccinate, methyl salicylate and auxiliary agents.
Preferably, the auxiliary agent is polyglycerol-3 diisostearate and a modified additive according to the mass ratio of 1: 2-4.
The method for preparing the synergistic auxiliary agent of the acaricide comprises the following steps of:
step 1, adding 0.1-0.3 part of cottonseed phenol, 0.2-0.4 part of rosin phenol, 0.05-0.2 part of ricinoleic acid ester, 1-3 parts of linalool, 0.05-0.2 part of succinic acid ester, 0.1-0.3 part of longifolene, 0.3-0.5 part of notoginsenoside R1, 0.05-0.2 part of camellia seed extract and 0.4-1 part of auxiliary materials into a reaction kettle, heating, stirring and mixing, wherein the auxiliary materials comprise 0.04-0.06 part of dioctyl sodium sulfosuccinate, 0.1-0.3 part of diisooctyl sulfosuccinate sodium salt, 0.1-0.2 part of methyl salicylate and 0.3-0.5 part of auxiliary agent, the auxiliary agent comprises 0.05-0.15 part of polyglycerol-3 diisostearate and 0.2-0.4 part of modifying additive, and the stirring speed is 500-1000 rpm, and the heating temperature is 50-70 ℃ to obtain a mixture;
and step 2, carrying out high-pressure homogenization on the mixture prepared in the step 1, wherein the high-pressure homogenization pressure is 10-20 MPa, and obtaining the synergistic additive.
The preparation method of the modified additive comprises the following steps of:
s1, adding 0.2-0.4 part of formaldehyde and 0.1-0.3 part of resorcinol into 80-120 parts of mixed solvent, stirring for 4-8 hours at 100-300 rpm at room temperature, then dropwise adding 0.7-0.9 part of tetraethyl orthosilicate, stirring for 5-10 minutes at 100-300 rpm, adding 0.5-1 part of formaldehyde and 0.5-0.7 part of resorcinol, stirring for 1-3 hours at 100-300 rpm again, centrifuging for 3-8 minutes at 5000-10000 rpm, washing completely, airing, and calcining for 3-8 hours at 500-600 ℃ to obtain a nano carrier;
s2, adding 0.5-2 parts of zinc acetate dihydrate and 1-3 parts of L-phenylalanine into 80-120 parts of water, stirring for 20-40 min at normal temperature at 100-300 rpm, then adjusting the pH to 12-13.5 by using 0.5-2 mol/L sodium hydroxide aqueous solution, stirring for 1-3 h at 100-300 rpm, centrifuging the dispersion at 8000-12000 rpm for 3-8 min, collecting the solid, respectively washing for 1-3 times by using water and absolute ethyl alcohol, and drying overnight at 40-60 ℃ to obtain a functional agent;
and S3, adding 0.02-0.04 part of nano-carrier and 0.01-0.03 part of the functional agent prepared in the step S2 into 40-60 parts of ethanol containing 0.4-0.6 part of 20-26wt% ammonia water, then adding 0.04-0.06 part of methacryloxypropyl trimethoxysilane under the stirring condition of 100-300 rpm, stirring for 5-20 hours at the temperature of 25-35 ℃ at the speed of 100-300 rpm, centrifuging for 3-8 minutes at the speed of 6000-10000 rpm, washing for 1-3 times by using absolute ethanol, and freeze-drying to obtain the modified additive.
Preferably, the mixed solvent is composed of 10-20 parts by weight of water, 5-8 parts by weight of 20-26% ammonia water and 70-90 parts by weight of absolute ethyl alcohol.
The application of the synergistic auxiliary agent is to mix the synergistic auxiliary agent prepared by the invention with the acaricide in a barrel for synergy.
The acaricide is one of 1.8% avermectin emulsifiable concentrate, 10% avermectin microcapsule suspending agent, 20% pyridaben+25% spirodiclofen suspending agent, 4% etoxazole+8% spirodiclofen suspending agent, 34% spirodiclofen suspending agent, 20% bifenazate+20% spirodiclofen suspending agent, 2% avermectin+10% etoxazole suspending agent, 3.2% avermectin emulsifiable concentrate, 57% propargite emulsifiable concentrate and 2% avermectin+18% spirodiclofen suspending agent.
The synergistic assistant of the acaricide is obtained by heating, stirring and mixing the mixture and homogenizing the mixture under high pressure. These components may act synergistically in the mixture to enhance the effect of the acaricide. The following are possible synergies:
cottonseed phenol, rosin phenol: these components may have antibacterial and insecticidal effects, and synergistic effects may increase the killing effect of the acaricide on mites.
Linalool and longifolene: these components may have insecticidal and antibacterial effects, and synergistic effects may enhance the killing effect of the acaricide.
Pseudo-ginseng saponin R1 and camellia seed extract: these components may have insecticidal effects and synergistic effects may enhance the killing effect of the acaricide on mites.
The auxiliary materials comprise dioctyl sodium sulfosuccinate, diisooctyl sodium sulfosuccinate and methyl salicylate: these ingredients may have the effect of adjusting pH, enhancing antibacterial and preservative properties, and the synergistic effect may improve the stability and preservative effect of the acaricide.
Polyglycerol-3 diisostearate and modifying additives in the auxiliary agent: these components may act synergistically in a manner that increases adhesion and stability, improving the adhesion and persistence of the acaricide.
The nano-carrier prepared by the invention has a hollow structure, is favorable for carrying medicines, and can realize effective leaf surface retention on the strawberry leaf thorn surface through the hat topological effect. The wettability of the blade and the wettability and retention of the pesticide formulation directly affect the deposition of the pesticide on the blade. The small contact angle shows that the surface of the blade has good wettability, and the rich polyphenol groups on the nano-carrier form hydrogen bonds with the wax layer, so that the wettability of the acaricide on the blade is improved. Possibly due to the increased contact area of the acaricide with the blade surface and the formation of topological effects. The acaricide added with the nano carrier has better blade adhesion. The main reasons for the high leaf retention rate may be the strong hydrogen bonding between the nano-carrier groups and the leaf wax layer (fatty alcohols, acids and aldehydes) and the topological effect between the acaricide and the leaf. Moreover, the nano-carrier has stronger ultraviolet shielding capability.
The functional agent synthesized by the invention can obtain stable and uniform emulsion because the functional agent and the polyglycerol-3 diisostearate can reduce the oil-water interfacial tension. The added functional agent forms a single-layer or multi-layer interface barrier through irreversible adsorption at the oil-water interface, and delays or prevents coalescence among emulsion droplets. The functional agent is adsorbed on the interface, dispersed in the water phase, and forms a three-dimensional network around the liquid drops to prevent the liquid drops from coalescing, thereby improving the stability of the emulsion. Individual particles may be simultaneously adsorbed on the interface of different droplets. Capillary forces are created when the functional agent particles overlap with the disturbance caused by the interfacial contact. The greater the perturbation of the functional agent particles, the stronger the capillary interaction between them. Meanwhile, the functional agent particles have higher desorption energy and are more stable. The functional agent and the polyglycerol-3 diisostearate at the interface have synergistic effect, so that the interfacial tension is greatly reduced, and the functional agent has good adhesiveness and dispersibility in emulsion formation and stabilization.
Compared with the prior art, the invention has the beneficial effects that:
1) The synergistic agent prepared by the invention contains a plurality of components, wherein the components comprise gossypol, pinoresinol, ricinoleate, linalool, succinate, longifolene, notoginsenoside R1, camellia seed extract, auxiliary materials, auxiliary agents and the like, and the synergistic agent can protect the acaricide from being irradiated and degraded by ultraviolet rays, so that the effective life of the acaricide is prolonged.
2) The nano carrier and the functional agent in the synergistic agent prepared by the invention can improve the dispersibility, stability and adsorption capacity of the synergistic agent, have a slow release effect, can prolong the action time of the field efficacy, enhance the action effect of the synergistic agent in acaricides and have a better killing effect on the tetranychus urticae.
Detailed Description
The main material sources are as follows:
cottonseed phenol: chengdu Pure technology development Co., ltd., product number: BP0687.
Rosin phenol: nanjing Shangshu Biotech Co., ltd., CAS number: 487-36-5.
Ricinoleate: nanjing Baimuda Biotechnology Inc., CAS:9004-97-1.
Linalool: guangzhou Kangyuan Biotech Co., ltd., model: FZ-542.
Succinic acid esters: merck company, cat: C6512-5G, CAS number: 1510-21-0.
Notoginsenoside R1: chengDude Biotechnology Co., ltd., CAS:80418-24-2.
Tea seed extract: shaanxi Lv Lai Biotech Co., ltd., product number: LL00329.
Example 1
A preparation method of the synergistic auxiliary agent of the acaricide comprises the following steps:
step 1, adding 0.2g of cottonseed phenol, 0.3g of rosin phenol, 0.1g of ricinoleate, 2g of linalool, 0.1g of succinate, 0.2g of longifolene, 0.4g of notoginsenoside R1, 0.1g of camellia seed extract and 0.8g of auxiliary materials into a reaction kettle, heating and stirring for mixing at a stirring speed of 800rpm, wherein the heating temperature is 60 ℃ to obtain a mixture, the auxiliary materials comprise 0.05g of dioctyl sodium sulfosuccinate, 0.2g of diisooctyl sodium sulfosuccinate, 0.15g of methyl salicylate and 0.4g of auxiliary materials, and the auxiliary materials comprise 0.1g of polyglycerol-3 diisostearate and 0.3g of modified additive;
and step 2, homogenizing the mixture prepared in the step 1 at a high pressure, wherein the high pressure homogenizing pressure is 15MPa, and thus the synergistic additive is obtained.
The preparation method of the modified additive comprises the following steps:
s1, adding 0.3g of formaldehyde and 0.2g of resorcinol into 100g of mixed solvent, stirring at 200rpm for 6 hours at room temperature, then dropwise adding 0.8g of tetraethyl orthosilicate, stirring at 200rpm for 8 minutes, adding 0.8g of formaldehyde and 0.6g of resorcinol, stirring at 200rpm for 2 hours again, centrifuging at 8000rpm for 5 minutes, washing with water, drying, and calcining at 550 ℃ for 5 hours to obtain a nano-carrier, wherein the mixed solvent consists of 14g of water, 6g of 25wt% ammonia water and 80g of absolute ethyl alcohol;
s2, adding 1g of zinc acetate dihydrate and 2g L-phenylalanine into 100g of water, stirring for 30min at normal temperature at 200rpm, then adjusting the pH to 13 by using 1mol/L sodium hydroxide aqueous solution, stirring for 2h at room temperature at 200rpm, centrifuging the dispersion at 10000rpm for 5min, collecting solids, respectively washing 3 times by using water and absolute ethyl alcohol, and drying overnight at 50 ℃ to obtain a functional agent;
s3, adding 0.03g of the nano-carrier prepared in the step S1 and 0.02g of the functional agent prepared in the step S2 into 50g of ethanol containing 0.5g of 25wt% ammonia water, then adding 0.05g of methacryloxypropyl trimethoxysilane under the stirring condition of 200rpm, centrifuging at 8000rpm for 5min after stirring at 30 ℃ for 12h at 200rpm, washing with absolute ethanol for 3 times, and freeze-drying to obtain the modified additive.
Comparative example 1
The preparation method of the synergistic assistant of the acaricide is basically the same as that of the example 1, and the only difference is that: the preparation methods of the modified additive are different.
The preparation method of the modified additive comprises the following steps:
s1, adding 1g of zinc acetate dihydrate and 2g L-phenylalanine into 100g of water, stirring for 30min at normal temperature at 200rpm, then adjusting the pH to 13 by using 1mol/L sodium hydroxide aqueous solution, stirring for 2h at room temperature at 200rpm, centrifuging the dispersion at 10000rpm for 5min, collecting solids, respectively washing 3 times by using water and absolute ethyl alcohol, and drying overnight at 50 ℃ to obtain a functional agent;
s2, adding 0.02g of the functional agent prepared in the step S1 into 50g of ethanol containing 0.5g of 25wt% ammonia water, then adding 0.05g of methacryloxypropyl trimethoxy silane under the stirring condition of 200rpm, centrifuging at 8000rpm for 5min after stirring at 30 ℃ for 12h at 200rpm, washing with absolute ethanol for 3 times, and freeze-drying to obtain the modified additive.
Comparative example 2
The preparation method of the synergistic assistant of the acaricide is basically the same as that of the example 1, and the only difference is that: the preparation methods of the modified additive are different.
The preparation method of the modified additive comprises the following steps:
s1, adding 0.3g of formaldehyde and 0.2g of resorcinol into 100g of mixed solvent, stirring at 200rpm for 6 hours at room temperature, then dropwise adding 0.8g of tetraethyl orthosilicate, stirring at 200rpm for 8 minutes, adding 0.8g of formaldehyde and 0.6g of resorcinol, stirring at 200rpm for 2 hours again, centrifuging at 8000rpm for 5 minutes, washing with water, drying, and calcining at 550 ℃ for 5 hours to obtain a nano-carrier, wherein the mixed solvent consists of 14g of water, 6g of 25wt% ammonia water and 80g of absolute ethyl alcohol;
s2, adding 0.03g of the nano-carrier prepared in the step S1 into 50g of ethanol containing 0.5g of 25wt% ammonia water, then adding 0.05g of methacryloxypropyl trimethoxy silane under the stirring condition of 200rpm, centrifuging at 8000rpm for 5min after stirring at 30 ℃ and 200rpm for 12h, washing with absolute ethanol for 3 times, and freeze-drying to obtain the modified additive.
Comparative example 3
A preparation method of the synergistic auxiliary agent of the acaricide comprises the following steps:
step 1, adding 0.2g of cottonseed phenol, 0.3g of rosin phenol, 0.1g of ricinoleate, 2g of linalool, 0.1g of succinate, 0.2g of longifolene, 0.4g of notoginsenoside R1, 0.1g of camellia seed extract and 0.7g of auxiliary materials into a reaction kettle, heating and stirring for mixing, wherein the stirring speed is 800rpm, the heating temperature is 60 ℃, and a mixture is obtained, wherein the auxiliary materials consist of 0.05g of dioctyl sodium sulfosuccinate, 0.2g of diisooctyl sodium sulfosuccinate, 0.15g of methyl salicylate and 0.3g of auxiliary materials, and the auxiliary materials are 0.3g of modified additives;
and step 2, homogenizing the mixture prepared in the step 1 at a high pressure, wherein the high pressure homogenizing pressure is 15MPa, and thus the synergistic additive is obtained.
The preparation method of the modified additive is the same as in example 1.
Comparative example 4
A preparation method of the synergistic auxiliary agent of the acaricide comprises the following steps:
step 1, adding 0.2g of cottonseed phenol, 0.3g of rosin phenol, 0.1g of ricinoleate, 2g of linalool, 0.1g of succinate, 0.2g of longifolene, 0.4g of notoginsenoside R1, 0.1g of camellia seed extract and 0.4g of auxiliary materials into a reaction kettle, heating, stirring and mixing at a stirring speed of 800rpm and a heating temperature of 60 ℃ to obtain a mixture, wherein the auxiliary materials consist of 0.05g of dioctyl sodium sulfosuccinate, 0.2g of diisooctyl sodium sulfosuccinate and 0.15g of methyl salicylate;
and step 2, homogenizing the mixture prepared in the step 1 at a high pressure, wherein the high pressure homogenizing pressure is 15MPa, and thus the synergistic additive is obtained.
Test example 1
Field efficacy test
The preparation method of the acaricide comprises the following steps: 1.8g of abamectin and 4g of the synergistic agent prepared by the invention are added into 94.2g of ethylene glycol butyl ether, heated to 40 ℃, and stirred and mixed for 5 hours at 200rpm to obtain the acaricide.
The test land is arranged in a strawberry greenhouse in Huanggang city of Hubei province, and the strawberry variety is red. Transplanting in 9 months and 5 days of 2020, wherein the plant row spacing is 30cm multiplied by 30cm, the planting density is 6000 plants/mu, and the strawberries are in the later harvest period during the test. The application rate of the acaricide is 75ga.i./hm, and clear water is used for blank control. Each test zone was 20m 2 Repeat 4 times, randomization block arrangement. Adopts a 3WBD-16B backpack electric sprayer (two plastic products factory in spiced river in Taizhou city) to uniformly spray,the spraying amount is 50 kg/mu. The administration time is 2021, 3 months and 5 days. In the test, the Tetranychus urticae is in the initial stage of the initial stage.
And 5 blades are fixed at each point by adopting random five-point sampling according to the pesticide effect test criterion in the field of the agricultural department, and 25 blades are total. The number of mites was checked before administration, and the number of mites was investigated on days 1, 7 and 14 after administration. Each group was tested three times and averaged. The test results are shown in Table 1.
Table 1 results of field efficacy test
Test example 2
Anti-ultraviolet performance test
10g of acaricide prepared in test example 1 of the invention is respectively placed in a beaker containing 300g of 75wt% ethanol aqueous solution, under the same test conditions, the acaricide is irradiated by an ultraviolet lamp, the power of the ultraviolet lamp is 300W, the concentration of avermectin in the beaker is measured at intervals of 90 min, and the degradation rate of the avermectin is calculated. The test results are shown in Table 2.
TABLE 2 ultraviolet resistance test results
From the test data in tables 1 and 2, it can be seen that the synergistic agent prepared in example 1 of the present invention has excellent anti-ultraviolet performance and field efficacy. Example 1 is probably because the nano-carrier prepared by the invention has a hollow structure, which is favorable for carrying medicine, and can realize effective leaf surface retention on the strawberry leaf thorn surface through the 'hat' topological effect. The wettability of the blade and the wettability and retention of the pesticide formulation directly affect the deposition of the pesticide on the blade. The small contact angle shows that the surface of the blade has good wettability, and the rich polyphenol groups on the nano-carrier form hydrogen bonds with the wax layer, so that the wettability of the acaricide on the blade is improved. Possibly due to the increased contact area of the acaricide with the blade surface and the formation of topological effects. The acaricide added with the nano carrier has better blade adhesion. The main reasons for the high leaf retention rate may be the strong hydrogen bonding between the nano-carrier groups and the leaf wax layer (fatty alcohols, acids and aldehydes) and the topological effect between the acaricide and the leaf. Moreover, the nano-carrier has stronger ultraviolet shielding capability.
Example 1 is probably because the functional agent synthesized in the present invention can give a stable and uniform emulsion compared with comparative examples 2 to 3 because the functional agent and polyglyceryl-3 diisostearate can lower the oil-water interfacial tension. The added functional agent forms a single-layer or multi-layer interface barrier through irreversible adsorption at the oil-water interface, and delays or prevents coalescence among emulsion droplets. The functional agent is adsorbed on the interface, dispersed in the water phase, and forms a three-dimensional network around the liquid drops to prevent the liquid drops from coalescing, thereby improving the stability of the emulsion. Individual particles may be simultaneously adsorbed on the interface of different droplets. Capillary forces are created when the functional agent particles overlap with the disturbance caused by the interfacial contact. The greater the perturbation of the functional agent particles, the stronger the capillary interaction between them. Meanwhile, the functional agent particles have higher desorption energy and are more stable. The functional agent and the polyglycerol-3 diisostearate at the interface have synergistic effect, so that the interfacial tension is greatly reduced, and the functional agent has good adhesiveness and dispersibility in emulsion formation and stabilization.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (7)
1. The synergistic assistant of the acaricide is characterized by comprising the following components: 0.1-0.3 part of cottonseed phenol, 0.2-0.4 part of rosin phenol, 0.05-0.2 part of ricinoleate, 1-3 parts of linalool, 0.05-0.2 part of cholesterol succinic monoester, 0.1-0.3 part of longifolene, 0.3-0.5 part of notoginsenoside R1, 0.05-0.2 part of camellia seed extract and 0.4-1 part of auxiliary material;
the auxiliary materials comprise 0.04-0.06 part of dioctyl sodium sulfosuccinate, 0.1-0.3 part of diisooctyl sodium sulfosuccinate, 0.1-0.2 part of methyl salicylate and 0.3-0.5 part of auxiliary agent;
the auxiliary agent is prepared by mixing 0.05-0.15 part of polyglycerol-3 diisostearate and 0.2-0.4 part of modifying additive;
the preparation method of the modified additive comprises the following steps:
s1, adding 0.2-0.4 part of formaldehyde and 0.1-0.3 part of resorcinol into 80-120 parts of mixed solvent, stirring for 4-8 hours at 100-300 rpm at room temperature, then dropwise adding 0.7-0.9 part of tetraethyl orthosilicate, stirring for 5-10 minutes at 100-300 rpm, adding 0.5-1 part of formaldehyde and 0.5-0.7 part of resorcinol, stirring for 1-3 hours at 100-300 rpm again, centrifuging for 3-8 minutes at 5000-10000 rpm, washing cleanly, drying, and calcining for 3-8 hours at 500-600 ℃ to obtain a nano carrier;
s2, adding 0.5-2 parts of zinc acetate dihydrate and 1-3 parts of L-phenylalanine into 80-120 parts of water, stirring for 20-40 min at normal temperature at 100-300 rpm, then adjusting the pH to 12-13.5 by using 0.5-2 mol/L sodium hydroxide aqueous solution, stirring for 1-3 h at 100-300 rpm, centrifuging the dispersion at 8000-12000 rpm for 3-8 min, collecting the solid, respectively washing for 1-3 times by using water and absolute ethyl alcohol, and drying overnight at 40-60 ℃ to obtain a functional agent;
s3, adding 0.02-0.04 part of nano-carrier and 0.01-0.03 part of the functional agent prepared in the step S2 into 40-60 parts of ethanol containing 0.4-0.6 part of 20-26wt% ammonia water, then adding 0.04-0.06 part of methacryloxypropyl trimethoxysilane under the stirring condition of 100-300 rpm, stirring for 5-20 hours at the temperature of 25-35 ℃ at the speed of 100-300 rpm, centrifuging for 3-8 minutes at the speed of 6000-10000 rpm, washing for 1-3 times by using absolute ethanol, and freeze-drying to obtain a modified additive;
tea seed extract: shaanxi Lv Lai Biotech Co., ltd., product number: LL00329;
the above parts refer to parts by weight.
2. The synergistic adjuvant for acaricide according to claim 1, wherein the mixed solvent comprises 10 to 20 parts by weight of water, 5 to 8 parts by weight of 20 to 26% ammonia water and 70 to 90 parts by weight of absolute ethyl alcohol.
3. A process for preparing a co-agent for an acaricide according to claim 1 or 2, which comprises the steps of:
step 1, adding gossypol, pinoresinol, ricinoleate, linalool, cholesterol succinic acid monoester, longifolene, notoginsenoside R1, camellia seed extract and auxiliary materials into a reaction kettle, heating, stirring and mixing at a stirring speed of 500-1000 rpm and a heating temperature of 50-70 ℃ to obtain a mixture;
and step 2, homogenizing the mixture prepared in the step 1 at high pressure to obtain the synergistic auxiliary agent.
4. The method of claim 3, wherein the high pressure homogenization pressure is 10-20 mpa.
5. Use of the synergistic adjuvant according to claim 1 or 2 in acaricides.
6. The use according to claim 5, wherein the co-agent and the acaricide are tank-mixed.
7. The use according to claim 5, wherein the acaricide is one of 1.8% avermectin emulsifiable concentrate, 10% avermectin microcapsule suspension, 2% avermectin +10% etoxazole suspension, 3.2% avermectin emulsifiable concentrate, 2% avermectin +18% spirodiclofen suspension.
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