CN112335673A - Organic solvent-free flying waterproof nano microemulsion and preparation method thereof - Google Patents

Organic solvent-free flying waterproof nano microemulsion and preparation method thereof Download PDF

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CN112335673A
CN112335673A CN202011254167.2A CN202011254167A CN112335673A CN 112335673 A CN112335673 A CN 112335673A CN 202011254167 A CN202011254167 A CN 202011254167A CN 112335673 A CN112335673 A CN 112335673A
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flying
water
microemulsion
spray
thiamethoxam
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沈国清
宋睿
刘永兴
唐飞龙
余洲
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Shanghai Jiaotong University
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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
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • 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
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a flying waterproof nano microemulsion without organic solvent and a preparation method thereof; the water-based nano-microemulsion comprises: thiamethoxam, acetamiprid, compound surfactant, anti-drift agent, defoaming agent, light stabilizer and water. The water-based nano microemulsion is mixed with water in proportion to form an aqueous solution, and then the flying spray preventing liquid is obtained and can be directly applied to spraying of the plant protection unmanned aerial vehicle. The invention thoroughly eliminates the organic solvent added in the traditional pesticide preparation, is safe to human and livestock and has strong environmental friendliness; the particle size of the active ingredients is in nanometer level, so that the drug effect of the preparation can be improved; the wettability and the evaporation time of the spraying liquid medicine can be obviously improved; the method can greatly increase the deposition coverage rate of the fog drops in actual spraying application and enhance the drift resistance. The preparation process is simple and easy, and the stability is high; available water dilutes with the small scale when using, and the not problem such as sediment, layering can not block up the shower nozzle, is favorable to plant protection unmanned aerial vehicle's spraying.

Description

Organic solvent-free flying waterproof nano microemulsion and preparation method thereof
Technical Field
The invention belongs to the field of pesticide preparations, and relates to a flying waterproof base type nano microemulsion without organic solvent and a preparation method thereof; in particular to a water-based nano microemulsion which is suitable for spraying of a plant protection unmanned aerial vehicle and does not contain an organic solvent and a preparation method thereof.
Background
The unmanned aerial vehicle plant protection flying prevention technology is popularized and applied to various crops in China due to the advantages of labor saving, time saving, water saving, high safety degree and the like. However, the flying defense agent is generally high-concentration spray, and the dosage per mu is 1.0-2.0L, so that many common pesticide formulations are not suitable for being directly applied to unmanned aerial vehicle spraying, for example, a petroleum solvent is contained in a missible oil formula, and potential explosion hazard exists in the spraying process; the pesticide effective component particle size in wettable powder is great, easily causes wearing and tearing etc. to the unmanned aerial vehicle shower nozzle. And the evaporation and drift problems of the droplets in the spraying operation process of the unmanned aerial vehicle cannot be ignored.
The flying prevention preparation is a special preparation suitable for spraying of a plant protection unmanned aerial vehicle, and has the following requirements in the development process: the preparation has high content of effective components, and can be diluted at low times for use; the preparation formulation is reasonable, layering, precipitation and the like can not occur in a short time after dilution, and an organic solvent with high volatility and large toxicity can not be added; the safety is high, the toxicity of the preparation to animals and the environmental safety are fully considered, and the application risk is confirmed; has good effects of sedimentation and adhesion, evaporation prevention and drift resistance. Therefore, the pesticide preparation with high pesticide effect and safety to crops is generally selected and used as a main preparation form, such as water-based water aqua, microemulsion and the like.
Thiamethoxam (Thiamethoxam) with the chemical name of 3- (2-chloro-1, 3-thiazole-5-ylmethyl) -5-methyl-1, 3, 5-oxadiazin-4-ylidene (nitro) amine is a second-generation neonicotinoid insecticide, has the advantages of wide insecticidal spectrum, high activity, long lasting period, high safety and the like, and the high activity of the Thiamethoxam is expressed by the modes of contact killing, stomach toxicity, systemic absorption and the like. Has high activity to coleoptera, diptera, lepidoptera, especially homoptera pests, and can effectively prevent and control various pests such as aphids, leafhoppers, plant hoppers, whiteflies and the like and pests generating resistance to various types of chemical pesticides. Suitable crops are rice crops, beet, rape, potatoes, cotton and the like.
Acetamiprid (Acetamiprid) with the chemical name of N- (N-cyano-ethylimino) -N-methyl-2-chloropyridine-5-methylamine is a chloronicotinyl compound. By acting on nicotinic acetylcholine receptors at synaptic sites of insect nervous system, the stimulation conduction of insect nervous system is interfered, the nervous system is caused to block, and the accumulation of neurotransmitter acetylcholine at synaptic sites is caused, thereby causing paralysis and death of insects. The pesticide effect of the acetamiprid is realized by means of contact poisoning, stomach poisoning and the like, and the acetamiprid has no cross resistance with the conventional pesticide, so the acetamiprid is widely used for preventing and controlling aphids, plant hoppers, thrips, partial lepidoptera pests and the like of rice, vegetables, fruit trees and tea leaves.
Researches show that the thiamethoxam and the acetamiprid both have high activity and safety, have no cross resistance during compound use, have obvious synergistic effect, and can reduce the field dosage of the pesticide and save the cost. However, the existing single-dose preparation of the thiamethoxam and the acetamiprid does not completely meet the requirements of safety, environmental protection, accurate pesticide application and the like advocated at present, so the invention selects the compounding of the thiamethoxam and the acetamiprid as the raw pesticide for preparing the flying waterproof base type nano microemulsion without the organic solvent, and develops a novel preparation without the organic solvent, which has excellent pesticide effect, is environment-friendly, is easy to wet and spread, prevents evaporation and drift, and is suitable for being sprayed by a plant protection unmanned aerial vehicle.
Disclosure of Invention
The invention aims to provide a flying waterproof base type nano microemulsion which is suitable for a plant protection unmanned aerial vehicle and does not contain an organic solvent and a preparation method thereof. The preparation does not use organic solvent, and is environment-friendly; the grain diameter of the effective component is in nanometer level, the excellent drug effect is shown, and the utilization rate of the pesticide is obviously improved; in the spraying process of the plant protection unmanned aerial vehicle, the liquid medicine has excellent wetting effect and light stability on the blade, the evaporation rate is low, and the drift loss can be obviously reduced. And the invention solves the problems of easy layering and precipitation and need of large-rate dilution for use in the preservation process of the water-based microemulsion through the optimization of the composition classification and the proportion.
The purpose of the invention is realized by the following technical scheme:
the invention provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1-5% of thiamethoxam, 2-10% of acetamiprid, 10-30% of compound surfactant, 1-5% of anti-drift agent, 1-3% of defoaming agent, 1-3% of light stabilizer and 44-84% of water;
the compound surfactant is a composition of an anionic surfactant and a nonionic surfactant.
Preferably, the anionic surfactant is a composition of one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium tetradecyl benzene sulfonate, sodium hexadecyl sulfate, fatty acid methyl ester sulfonate, alpha-alkenyl sodium sulfonate and potassium oleate; the nonionic surfactant is one or a combination of more of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene, alkylolamide polyoxyethylene ether and sucrose fatty acid ester.
Preferably, the mass ratio of the anionic surfactant to the nonionic surfactant is 7-20: 3-10. Most preferably 2: 1.
More preferably, the anionic surfactant is one or more of sodium fatty alcohol polyoxyethylene ether sulfate, sodium tetradecyl benzene sulfonate and sodium hexadecyl sulfate, and the nonionic surfactant is one or more of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester and alkylphenol polyoxyethylene ether.
Preferably, the anti-drift agent is one or more of guar gum, guar gum derivatives, xanthan gum, polyacrylamide and hydroxyl acrylic acid polymer.
More preferably, the anti-drift agent is one or more of guar gum, xanthan gum and polyacrylamide.
Preferably, the defoaming agent is one or more of water-based silicone solid, polydimethylsiloxane, higher alcohol fatty acid ester complex, polyoxyethylene pentaerythritol ether, polyoxypropylene amine ether and polyoxypropylene glycerol ether.
More preferably, the defoaming agent is one or more of water-based silicone solid, polydimethylsiloxane and polyoxypropylene glycerol ether.
Preferably, the light stabilizer is one or a combination of more of an ultraviolet absorber, a hindered amine light stabilizer, 2,6, 6-tetramethyl-4-piperidyl stearate and bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate.
More preferably, the light stabilizer is a combination of one or more of a hindered amine light stabilizer and bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate.
The invention also provides a preparation method of the flying waterproof nano microemulsion without organic solvent, which comprises the following steps: dissolving thiamethoxam and acetamiprid in a small amount of water, uniformly mixing, adding a compound surfactant, an anti-drift agent, a defoaming agent and a light stabilizer, and supplementing with water. Stirring and emulsifying at room temperature by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion.
Preferably, the small amount of water is 10 to 25%.
Preferably, the stirring speed of the high-speed shearing emulsification of the high-speed emulsifying machine is 5000-.
The invention also provides a flying spray-preventing liquid which comprises the flying waterproof nano microemulsion.
The invention also provides a preparation method of the flying spray preventing liquid, which comprises the following steps:
the flying water-based nano microemulsion is mixed with water according to a required proportion to form an aqueous solution, and the flying spray preventing liquid is prepared and can be directly applied to spraying of a plant protection unmanned aerial vehicle.
Preferably, the mixing mass ratio of the flying waterproof nano microemulsion to the water is 1: 10-20.
The invention utilizes the solubilization mechanism of the surfactant to adjust the compounding category and proportion of the surfactant, so that the surfactant can be used as a solvent and an emulsifier in a microemulsion system and is positioned between a water phase and an oil phase, the dispersion of the original pesticide is facilitated, and the addition of an organic solvent is avoided. Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by adjusting the category and the proportion of the compound surfactant and utilizing the solubilization of the compound surfactant on the original pesticide, the addition of an organic solvent is avoided, and the aim of environmental protection is achieved; the flying waterproof nano microemulsion has safe components, does not contain organic solvent, has high safety degree to people, livestock and environment in the spraying process of the plant protection unmanned aerial vehicle, and reduces additional pollution;
(2) the invention adopts a high-speed shearing emulsification method, and the particle size of the active ingredients of the water-based microemulsion can reach the nanometer level through proper shearing speed and emulsification time, thereby further improving the drug effect;
(3) the surfactant in the formula of the flying waterproof nano microemulsion can also play a role of an auxiliary agent, so that the wettability, the evaporation resistance and the drift resistance of the nano microemulsion are improved when the nano microemulsion is applied;
(4) the defoaming effect and the light stability of the preparation are obviously improved compared with those of a common preparation by adding a proper defoaming agent and a proper light stabilizer;
(5) the flying waterproof nano microemulsion has high content of effective components, nano-grade particle size and excellent control effect, can improve the utilization rate of pesticide in the application process, and meets the requirement of synergy and decrement;
(6) the flying waterproof nano microemulsion has simple preparation process, low requirement on storage condition and stability under both low temperature and high temperature conditions; and the method is easy to operate in the field, and the problems of precipitation, layering, nozzle blockage and the like do not occur in the small-magnification dilution use process.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a water-free microemulsions prepared in accordance with example 1 of the present invention;
fig. 2 is a result of particle size distribution of effective components obtained by testing the flying water-based nano-microemulsion of example 2 of the present invention using a laser nano-particle size analyzer and a transmission electron microscope, wherein fig. 2(a) is a microstructure of effective component particles of the flying water-based nano-microemulsion, and fig. 2(b) is a distribution graph of particle size distribution thereof;
FIG. 3 is a graph of the contact angle measurements of the spray liquids of the pesticide 2.5% thiamethoxam Microemulsion (ME) and 20% acetamiprid Wettable Powder (WP) in examples 1-4 of the present invention and the commercially available pesticide DSA100, wherein FIGS. 3(a-d) are the contact angle measurement graphs of the spray liquids of the water-proof type nano-microemulsion in examples 1-4 in sequence, and FIGS. 3(e-f) are the contact angle measurement graphs of the commercially available pesticide spray liquids;
fig. 4 is a graph comparing the deposition distribution of the sprays of the pesticide 2.5% thiamethoxam Microemulsion (ME) and 20% acetamiprid Wettable Powder (WP) of examples 1-4 according to the present invention on the droplet detection card, wherein fig. 4(a-d) are the deposition distribution of the sprays of the water-based nano-microemulsion of examples 1-4 on the droplet detection card, and fig. 4(e-f) are the deposition distribution of the sprays of the pesticide of the present invention on the droplet detection card.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
The following example provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1-5% of thiamethoxam, 2-10% of acetamiprid, 10-30% of compound surfactant, 1-5% of anti-drift agent, 1-3% of defoaming agent, 1-3% of light stabilizer and 44-84% of water.
The compound surfactant is a composition of an anionic surfactant and a nonionic surfactant.
The anionic surfactant is one or a composition of more of fatty alcohol-polyoxyethylene ether sodium sulfate, sodium tetradecyl benzene sulfonate, sodium hexadecyl sulfate, fatty acid methyl ester sulfonate, alpha-alkenyl sodium sulfonate and potassium oleate; the nonionic surfactant is one or a composition of more of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene, alkylolamide polyoxyethylene ether and sucrose fatty acid ester; the mass ratio of the anionic surfactant to the nonionic surfactant is 7-20: 3-10.
The anti-drift agent is one or a composition of guar gum, guar gum derivatives, xanthan gum, polyacrylamide and hydroxyl acrylic acid polymer.
The defoaming agent is one or a combination of more of water-based organic silicon solid, polydimethylsiloxane, higher alcohol fatty acid ester compound, polyoxyethylene pentaerythritol ether, polyoxypropylene amine ether and polyoxypropylene glycerol ether.
The light stabilizer is one or a composition of more of ultraviolet absorbent, hindered amine light stabilizer, 2,6, 6-tetramethyl-4-piperidyl stearate and bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate.
The preparation method comprises the following steps: dissolving thiamethoxam and acetamiprid in a small amount of water, uniformly mixing, adding a compound surfactant, an anti-drift agent, a defoaming agent and a light stabilizer, and supplementing with water. Stirring and emulsifying at room temperature by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion without organic solvent.
The prepared flying waterproof nano microemulsion is directly packaged by using a light-tight plastic bottle, and each bottle has the mass of 100-200g or multiple thereof and can be directly added into 1L of liquid medicine with the volume of the multiple thereof for use.
When the plant protection spraying prevention liquid is used, the flying waterproof base type nano microemulsion is mixed with water according to the mass ratio of 1:10-20 to form an aqueous solution, and then the flying spraying prevention liquid can be prepared and can be directly applied to spraying of a plant protection unmanned aerial vehicle.
The commercially available pesticide products selected for comparison in the embodiment of the invention are respectively as follows: 2.5% thiamethoxam Microemulsion (ME), according to the mass ratio of 1: 12.5 mixing with water to form an aqueous solution as a pesticide spray solution; 20% acetamiprid Wettable Powder (WP), which is prepared from the following components in percentage by mass of 1: 80 are mixed with water to form an aqueous solution as a pesticide spray solution.
Example 1
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 12% of sodium tetradecyl benzene sulfonate, 3% of fatty acid polyoxyethylene ester, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formulation 1.
Dissolving thiamethoxam and acetamiprid in 25% water, mixing uniformly, adding compound surfactant, anti-drift agent, defoaming agent and light stabilizer, and supplementing with 49% water. Stirring and emulsifying at room temperature at 5000r/min for 5min by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion without organic solvent. Fig. 1 shows a flying waterproof nano-microemulsion prepared in example 1 of the present invention.
The flying waterproof type nano microemulsion is prepared by mixing the components in a mass ratio of 1:10 and water to form an aqueous solution, and then the flying spray preventing liquid can be prepared.
Example 2
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 2% of thiamethoxam, 4% of acetamiprid, 16% of sodium hexadecylsulfate, 5% of alkylphenol polyoxyethylene, 1% of guar gum, 2% of polyacrylamide, 2% of a water-based organosilicon solid, 2% of a hindered amine light stabilizer and 66% of water; denoted as formulation 2.
Dissolving thiamethoxam and acetamiprid in 16% water, mixing uniformly, adding compound surfactant, anti-drift agent, defoaming agent and light stabilizer, and supplementing with 50% water. Stirring and emulsifying at room temperature at 6000r/min for 15min by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion without organic solvent.
The flying waterproof type nano microemulsion is prepared by mixing the components in a mass ratio of 1: 12.5 mixing with water to form aqueous solution to obtain the spray-proof liquid.
Example 3
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 3% of thiamethoxam, 6% of acetamiprid, 5% of fatty alcohol-polyoxyethylene ether sodium sulfate, 5% of alpha-sodium olefin sulfonate, 8% of potassium oleate, 8% of alkylolamide polyoxyethylene ether, 2% of xanthan gum, 2% of polyacrylamide, 2% of aqueous organosilicon solid, 2% of hindered amine light stabilizer and 57% of water; is recorded as formula 3.
Dissolving thiamethoxam and acetamiprid in 17% water, mixing uniformly, adding compound surfactant, anti-drift agent, defoaming agent and light stabilizer, and supplementing with 40% water. Stirring and emulsifying at 7000r/min for 15min at room temperature by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion without organic solvent.
The flying waterproof type nano microemulsion is prepared by mixing the components in a mass ratio of 1: 15 and water to form an aqueous solution, and then the flying spray preventing liquid can be prepared.
Example 4
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 5% of thiamethoxam, 10% of acetamiprid, 5% of sodium fatty alcohol-polyoxyethylene ether sulfate, 15% of sodium hexadecyl sulfate, 10% of castor oil polyoxyethylene ether, 2% of guar gum, 3% of xanthan gum, 3% of polyoxyproplamine ether, 3% of bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate and 44% of water; denoted as formulation 4.
Dissolving thiamethoxam and acetamiprid in 14% water, mixing uniformly, adding compound surfactant, anti-drift agent, defoaming agent and light stabilizer, and supplementing with 30% water. Stirring and emulsifying at room temperature at 8000r/min for 20min by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion without organic solvent.
The flying waterproof type nano microemulsion is prepared by mixing the components in a mass ratio of 1: 20 and water to form an aqueous solution, and then the flying spray preventing liquid is prepared.
Comparative example 1
The comparative example provides a flying waterproof nano microemulsion without organic solvent, which adopts the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 15% of sodium tetradecyl benzene sulfonate, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formulation 1'.
The preparation methods of the nano microemulsion and the flying spray prevention liquid in the comparative example 1 are the same as those in the example 1.
Comparative example 2
The comparative example provides a flying waterproof nano microemulsion without organic solvent, which adopts the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 15% of fatty acid polyoxyethylene ester, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formula 2'.
The preparation methods of the nano microemulsion and the flying spray prevention liquid of the comparative example 2 are the same as those of the example 1.
Comparative example 3
The comparative example provides a flying waterproof nano microemulsion without organic solvent, which adopts the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 12% of dodecylbenzene sulfonic acid (LABSA), 3% of propylene glycol block polyether (L62), 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; is recorded as formula 3'.
The preparation methods of the nano microemulsion and the flying spray prevention liquid of the comparative example 3 are the same as those of the example 1.
The water-repellent type nano microemulsion spray solutions prepared in the above examples 1 to 4 and comparative examples 1 to 3 were subjected to various performance tests, and compared with commercially available 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder spray solutions:
first, stability analysis
The flying waterproof type nano-micro-emulsion prepared in the invention of examples 1 to 4 and the comparative examples 1 to 3 is subjected to appearance observation and recording. The observation results are shown in table 1.
TABLE 1 stability observations of different nanomicroemulsions
Figure BDA0002772574000000071
Figure BDA0002772574000000081
The results show that examples 1-4 all give uniform and stable nanomicroemulsions and are clear and transparent fluid liquids in appearance. The nano microemulsions obtained in comparative examples 1-3 all have precipitation delamination, and the original pesticide cannot be completely dissolved, which indicates that the three comparative example systems are not stable and do not meet the application requirements, so the follow-up property is not researched. The comparative examples herein also show that the effect of the present invention cannot be achieved by adding a surfactant of a separate type or neither an anionic surfactant nor a nonionic surfactant within the range not defined by the present invention.
Secondly, analysis of particle size of active ingredient
The particle sizes of the effective components of the examples 1 to 4 of the invention and the commercial pesticide 2.5% thiamethoxam microemulsion spray solution are measured by using a laser nanometer particle size analyzer and a transmission electron microscope, and the particle size of 20% acetamiprid wettable powder is micron-level, so that the particle sizes are not separately measured. The measurement results are shown in table 2.
TABLE 2 results of particle size measurement of active ingredients of different pesticide preparations
Figure BDA0002772574000000082
As shown in Table 2, the particle size of the active ingredient of the commercial pesticide 2.5% thiamethoxam microemulsion spray is 103.6 nm. The particle sizes of the effective components in the embodiments 1 to 4 are all in a nanometer level, which is reduced by 97.5 to 98.2 percent compared with the commercial pesticides, and the effective components can better enter the body of pests by methods such as contact, organ infiltration and the like, so as to improve the pesticide effect, and the PDI values of the effective components are all lower than 0.2, which indicates that the particle size distribution is uniform.
Fig. 2 is a result of the particle size of the active ingredient of the flying waterproof nano-microemulsion according to example 2 of the present invention, wherein fig. 2(a) shows the microstructure of the active ingredient particles of the flying waterproof nano-microemulsion, and the black particles in the red circle are the active ingredient particles of the microemulsion, and it can be seen that the distribution is relatively uniform; the particle size distribution in FIG. 2(b) further illustrates the good uniformity of the particle size of the active ingredient.
Third, spray liquid drop wetting performance analysis
A static contact angle measuring mode in a DSA100 contact angle measuring instrument is used, rice leaves are used as a measuring substrate, flying spray-proof liquid is injected into a liquid drop device, after the instrument is stabilized, software is operated to control liquid drops to drop, and the corresponding contact angle size is recorded. The results of the contact angles of the examples 1 to 4 with the 2.5% thiamethoxam microemulsion and the 20% acetamiprid wettable powder spray solution are shown in Table 3.
TABLE 3 contact angle measurement results for different spray solutions
Figure BDA0002772574000000091
FIG. 3 shows the contact angles of the spray solutions of examples 1 to 4 and the commercial pesticide of 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder on rice leaves. As shown in fig. 3(a-d), the contact angles of the spray liquids of the water-proof base type nano micro-emulsions in examples 1-4 of the invention are all lower than 49.4 °, which is 9.0-19.1% lower than that of the spray liquid of the thiamethoxam micro-emulsion with the concentration of 2.5%, and 11.2-21.1% lower than that of the spray liquid of 20% acetamiprid wettable powder. The flying water-based nano microemulsion has excellent wettability, can quickly infiltrate into leaf surfaces and effectively permeate, and is greatly helpful for improving pesticide effect.
Fourthly, analysis of evaporation prevention performance of spray liquid
Sucking 1.0 μ L of spray liquid, vertically hanging, dropping on rice leaf without initial speed, starting timing when the liquid drops, stopping timing when the liquid drops are completely evaporated, and recording the time required by the complete evaporation of the spray liquid drops. The evaporation time results of examples 1-4 and 2.5% thiamethoxam microemulsion, 20% acetamiprid wettable powder spray are shown in table 4.
Table 4 evaporation time measurement results for different spray solutions
Figure BDA0002772574000000092
As can be seen from table 4, the flying anti-spraying liquid prepared by mixing the flying water-based nano-microemulsion provided in examples 1 to 4 with water and spraying the flying anti-spraying liquid, the anti-evaporation performance of the flying anti-spraying liquid of formulas 1 to 4 of the examples of the present invention is significantly better than that of the pesticide spraying liquid on the market. Wherein, compared with the flying spray-proof liquid of the thiamethoxam microemulsion of 2.5 percent, the evaporation time is prolonged by 17.5 to 26.2 percent; compared with the flying anti-evaporation liquid of 20% acetamiprid wettable powder, the evaporation time is prolonged by 25.6-34.9%, which shows that the flying waterproof nano-microemulsion provided by the embodiments 1-4 of the invention can effectively improve the anti-evaporation property of pesticide liquid.
Fifthly, analysis of anti-drift performance of spray liquid
Indoor simulated spraying operation is carried out by using a high-pressure spray head of the plant protection unmanned aerial vehicle and a water pump, and the deposition coverage rate of the fog drops is determined by using a water-sensitive paper image analysis method. The results of coverage of the droplets deposited in the spray solutions of examples 1-4 and 2.5% thiamethoxam microemulsion, 20% acetamiprid wettable powder are shown in table 5.
Table 4 deposition coverage measurements for different spray solutions
Figure BDA0002772574000000101
Further observing the experimental results of indoor simulated spraying of the flying spray-proof solutions of different pesticide preparations, fig. 4 shows the comparison of the fog drop deposition distribution of the spray solutions of examples 1 to 4 of the present invention and the spray solutions of the commercially available pesticides, namely, the 2.5% thiamethoxam microemulsion and the 20% acetamiprid wettable powder, during the spraying process. As shown in fig. 4(e) and 4(f), the flying spray-preventing liquid of the commercially available pesticide, namely the thiamethoxam microemulsion with 2.5 percent and the acetamiprid wettable powder with 20 percent, has relatively small coverage area in the spraying process, and the deposition coverage rates are respectively 11.5 percent and 10.3 percent; fig. 4(a-d) shows that in the spraying conditions of the flying spray-proof liquid in embodiments 1-4 of the present invention, the droplet particle size is small, the distribution is very dense, it can be clearly seen that the droplet deposition coverage is greatly improved, both exceeding 15%, which is improved by 33.9-57.4% compared with 2.5% thiamethoxam microemulsion, and improved by 49.5-75.7% compared with 20% acetamiprid wettable powder, which indicates that the flying water-proof nano-microemulsion of the present invention can significantly enhance the drift resistance of the spraying liquid.
Sixth, indoor toxicity determination
The rice seedling spraying method is adopted in the test. Fresh rice seedlings are placed in culture dishes, 20 heads of 3-year-old rice planthopper larvae are inoculated on each dish, 2mL of the spray-preventing liquid of the embodiment 1-4 and the commercially available pesticide of 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder are respectively sprayed, 5 concentration gradients (calculated according to active ingredients) are designed for each agent, and meanwhile, clear water control is set. Sealing with gauze, placing in a constant temperature incubator with temperature of 25 + -1 deg.C, illumination period of 16L/8D and relative humidity of 60% -80%, investigating death condition of rice planthopper larva after 24h, touching with tweezers, and making it be dead standard.
Counting the number of dead insects of each treatment, calculating mortality and corrected mortality, converting the corrected mortality of the pests into a probability value (y), converting the treatment concentration (mg/L) into a logarithm value (x), obtaining a toxicity regression equation by a least square method, and calculating LC of each medicament50Value sum LC90The values and test results are shown in Table 6.
TABLE 6 indoor toxicity test results of different spray solutions to rice planthopper
Figure BDA0002772574000000111
As can be seen from Table 6, the flying spray prevention solutions of examples 1 to 4 of the present invention all exhibited excellent control effects on rice planthoppers, and LC505.23-10.86mg/L of LC9042.32-50.20mg/L, which is obviously lower than 2.5 percent thiamethoxam microemulsion and 20 percent acetamiprid wettable powder spray solution, which shows that the pesticide effect of the embodiment of the invention is obviously improved compared with the pesticide sold in the market.
In order to further improve the practical application effect of the flying waterproof nano microemulsion, the addition ratio of the anionic surfactant to the nonionic surfactant in the compound surfactant is optimized. Examples 5-7 were set up for comparative investigation with example 1, the four examples differing only in the ratio of anionic surfactant to nonionic surfactant.
Example 5
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 11.25% of sodium tetradecyl benzene sulfonate, 3.75% of fatty acid polyoxyethylene ester, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formulation 5. It differs from example 1 only in that: the adding proportion of the anionic surfactant to the nonionic surfactant is 3: 1.
the preparation methods of the nano microemulsion and the flying spray prevention liquid in the embodiment 5 are the same as the embodiment 1.
Example 6
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 10% of sodium tetradecyl benzene sulfonate, 5% of fatty acid polyoxyethylene ester, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formulation 6. It differs from example 1 only in that: the adding proportion of the anionic surfactant to the nonionic surfactant is 2: 1.
the preparation methods of the nano microemulsion and the flying spray prevention liquid in the embodiment 6 are the same as the embodiment 1.
Example 7
The embodiment provides a flying waterproof nano microemulsion without organic solvent, which comprises the following components in percentage by mass: 1% of thiamethoxam, 2% of acetamiprid, 7.5% of sodium tetradecyl benzene sulfonate, 7.5% of fatty acid polyoxyethylene ester, 3% of guar gum, 2% of polydimethylsiloxane, 3% of ultraviolet absorbent and 74% of water; denoted as formulation 7. It differs from example 1 only in that: the adding proportion of the anionic surfactant to the nonionic surfactant is 1: 1.
the preparation methods of the nano microemulsion and the flying spray prevention liquid in the embodiment 7 are the same as the embodiment 1.
The spray liquid of the flying waterproof-base type nano microemulsion prepared in the above examples 1, 5 to 7 was subjected to various performance tests, and compared with the spray liquid of a commercially available pesticide, namely 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder:
first, stability analysis
The observation results show that the uniform and stable nano microemulsion can be obtained in the examples 1 and 5-7, the appearance of the nano microemulsion is clear and transparent flowing liquid, and the usable pesticide preparation can be obtained in four compounding ratios.
Secondly, analysis of particle size of active ingredient
The particle sizes of the effective components of the examples 1, 5 to 7 of the invention and the commercial pesticide 2.5% thiamethoxam microemulsion spray solution are measured by using a laser nanometer particle size analyzer and a transmission electron microscope, and the particle size of the 20% acetamiprid wettable powder is larger and is in a micron level, so that the particle sizes are not separately measured. The measurement results are shown in Table 7.
TABLE 7 measurement results of particle diameters of active ingredients of different pesticidal formulations
Figure BDA0002772574000000121
As is clear from Table 7, the particle diameters of the active ingredients of examples 5 to 7 were all around 2nm, and the particle diameter distribution was uniform when PDI was less than 0.2, wherein the ratio of the anionic surfactant to the nonionic surfactant was 3: 1 and 2: the effect is better when 1 is used.
Third, spray liquid drop wetting performance analysis
The results of the contact angles of the examples 1, 5-7 with the 2.5% thiamethoxam microemulsion and the 20% acetamiprid wettable powder spray solution are shown in Table 8.
TABLE 8 contact angle measurement results for different spray solutions
Figure BDA0002772574000000131
The results show that the contact angles of the spray liquids of the 5-7 flying waterproof base type nano micro-emulsions in the embodiments 1 and 5-7 flying waterproof base type nano micro-emulsions are lower than 50.1 degrees, 7.7-19.2 percent lower than that of the spray liquid of the 2.5 percent thiamethoxam micro-emulsions and 9.9-21.0 percent lower than that of the spray liquid of 20 percent acetamiprid wettable powder. The four examples show that the water-based nano microemulsion has excellent wettability, and the ratio of the anionic surfactant to the nonionic surfactant is 2: the wetting effect of the nano microemulsion is better when the emulsion is 1.
Fourthly, analysis of evaporation prevention performance of spray liquid
The evaporation time results of examples 1, 5-7 and 2.5% thiamethoxam microemulsion, 20% acetamiprid wettable powder spray are shown in Table 9.
TABLE 9 measurement of evaporation time of different spray solutions
Figure BDA0002772574000000132
As can be seen from table 9, the spray jet protection fluids of examples 1, 5 to 7 are significantly superior in evaporation resistance to commercially available pesticide spray fluids. Wherein, formula 6, i.e. the ratio of anionic surfactant to nonionic surfactant, is 2: the wetting effect of the nano microemulsion is better when the emulsion is 1.
Fifthly, analysis of anti-drift performance of spray liquid
The results of coverage of the droplets deposited by the spray solutions of examples 1, 5-7 and 2.5% thiamethoxam microemulsion, 20% acetamiprid wettable powder are shown in table 10.
TABLE 10 results of determination of deposition coverage for different spray solutions
Figure BDA0002772574000000141
The deposition coverage rate of the flying spray-proof liquid in the embodiments 1 and 5 to 7 of the invention is improved by 33.9 to 41.7 percent compared with the 2.5 percent thiamethoxam microemulsion and is improved by 49.5 to 58.3 percent compared with 20 percent acetamiprid wettable powder, which shows that the flying water-proof base type nano microemulsion of the invention can obviously enhance the drift resistance of the spraying liquid. Wherein the ratio of formula 6 to formula 7, i.e. anionic surfactant to nonionic surfactant, is 2:1 and 1: the effect is better when 1 is used.
Sixth, indoor toxicity determination
The test uses a rice seedling spraying method to perform indoor toxicity measurement on the spray-spraying prevention liquid of the examples 1, 5 to 7 and the commercial pesticide of 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder, and the test results are shown in table 11.
TABLE 11 indoor toxicity test results of different spray solutions to rice planthopper
Figure BDA0002772574000000142
As is clear from Table 11, the flying spray-preventing solutions of examples 1 and 5 to 7 of the present invention exhibited excellent control effects on rice planthoppers, and LC507.97-19.21mg/L, LC9042.26-119.83mg/L, which is obviously lower than 2.5% thiamethoxam microemulsion and 20% acetamiprid wettable powder spray solution, and the pesticide effect of the embodiment of the invention is obviously improved compared with that of the commercially available pesticide. Wherein the ratio of the anionic surfactant to the nonionic surfactant is 2: the indoor toxicity effect is better when 1 hour.
Combining the comparative performance results of examples 1 and 5 to 7, it can be seen that the ratio of the anionic surfactant to the nonionic surfactant is in the range of 2:1, the properties of the flying waterproof nano microemulsion are improved, and the flying waterproof nano microemulsion can be used as the most preferable addition proportion in the scheme of the invention.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.

Claims (10)

1. The flying waterproof nano microemulsion without organic solvent comprises the following components in percentage by mass: 1-5% of thiamethoxam, 2-10% of acetamiprid, 10-30% of compound surfactant, 1-5% of anti-drift agent, 1-3% of defoaming agent, 1-3% of light stabilizer and 44-84% of water;
the compound surfactant is a composition of an anionic surfactant and a nonionic surfactant.
2. The femto-microemulsion of claim 1 wherein the anionic surfactant is a combination of one or more of sodium fatty alcohol-polyoxyethylene ether sulfate, sodium tetradecyl benzene sulfonate, sodium hexadecyl sulfate, fatty acid methyl ester sulfonate, sodium alpha-olefin sulfonate, potassium oleate; the nonionic surfactant is one or a combination of more of castor oil polyoxyethylene ether, fatty acid polyoxyethylene ester, alkylphenol polyoxyethylene, alkylolamide polyoxyethylene ether and sucrose fatty acid ester.
3. The flying water-based nanomicroemulsion according to claim 1 or 2, wherein the mass ratio of the anionic surfactant to the nonionic surfactant is 7-20: 3-10.
4. The femto-microemulsion of claim 1 wherein the drift prevention agent is a combination of one or more of guar gum, guar derivatives, xanthan gum, polyacrylamide, and hydroxyacrylic acid polymers.
5. The flying water-based nanomicroemulsion of claim 1 wherein the antifoaming agent is a combination of one or more of aqueous silicone solids, polydimethylsiloxanes, higher alcohol fatty acid ester complexes, polyoxyethylene pentaerythritol ethers, polyoxypropylene amine ethers, and polyoxypropylene glycerol ethers.
6. The flying water-based nanomicroemulsion of claim 1 wherein the light stabilizer is a combination of one or more of uv absorbers, hindered amine light stabilizers, 2,6, 6-tetramethyl-4-piperidyl stearate, bis (1-octyloxy-2, 2,6, 6-tetramethyl-4-piperidyl) sebacate.
7. The method of preparing the flying water-based nanomicroemulsion of claim 1, comprising the steps of: dissolving thiamethoxam and acetamiprid in a small amount of water, uniformly mixing, adding a compound surfactant, an anti-drift agent, a defoaming agent and a light stabilizer, and supplementing with water; stirring and emulsifying at room temperature by using a high-speed emulsifying machine to obtain the flying waterproof nano microemulsion.
8. The method for preparing flying waterproof nano microemulsion according to claim 7, wherein the stirring speed of the high-speed shearing emulsification of the high-speed emulsifying machine is 5000-8000r/min, and the stirring time is 5-20 min.
9. A flying spray formulation comprising the flying water-based nano-microemulsion of claim 1.
10. A method of preparing the flying spray preventing fluid of claim 9, comprising the steps of:
mixing the flying waterproof nano microemulsion with water according to a required proportion to form an aqueous solution, thus preparing the flying spray-proof liquid which can be directly applied to spraying of a plant protection unmanned aerial vehicle;
the mixing mass ratio of the flying waterproof nano microemulsion to water is 1: 10-20.
CN202011254167.2A 2020-11-11 2020-11-11 Organic solvent-free flying waterproof nano microemulsion and preparation method thereof Pending CN112335673A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103583545A (en) * 2013-11-29 2014-02-19 苏州佳辉化工有限公司 Insecticidal composition containing thiamethoxam and acetamiprid
CN109699661A (en) * 2019-02-13 2019-05-03 中化化工科学技术研究总院有限公司 A kind of aviation low volume insecticidal suspending agent and its preparation and application
CN110999903A (en) * 2019-12-16 2020-04-14 上海交通大学 Flying anti-spray solid auxiliary agent and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103583545A (en) * 2013-11-29 2014-02-19 苏州佳辉化工有限公司 Insecticidal composition containing thiamethoxam and acetamiprid
CN109699661A (en) * 2019-02-13 2019-05-03 中化化工科学技术研究总院有限公司 A kind of aviation low volume insecticidal suspending agent and its preparation and application
CN110999903A (en) * 2019-12-16 2020-04-14 上海交通大学 Flying anti-spray solid auxiliary agent and preparation method thereof

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