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WO2024153171A1 - Émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation et son utilisation - Google Patents

Émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation et son utilisation Download PDF

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Publication number
WO2024153171A1
WO2024153171A1 PCT/CN2024/072966 CN2024072966W WO2024153171A1 WO 2024153171 A1 WO2024153171 A1 WO 2024153171A1 CN 2024072966 W CN2024072966 W CN 2024072966W WO 2024153171 A1 WO2024153171 A1 WO 2024153171A1
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Prior art keywords
pesticide
oil
emulsion
liquid crystal
phase
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English (en)
Chinese (zh)
Inventor
贾鑫
李萌
张倩
尚亚卓
许世武
高波
孟凡成
闫博
李丹亚
熊有鹏
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Voda Agricultural Technology Co Ltd
East China University of Science and Technology
Shihezi University
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Voda Agricultural Technology Co Ltd
East China University of Science and Technology
Shihezi University
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Publication of WO2024153171A1 publication Critical patent/WO2024153171A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P21/00—Plant growth regulators

Definitions

  • the invention belongs to the field of pesticide formulations, and in particular relates to a pesticide emulsion with a liquid crystal structure and a preparation method and application thereof.
  • pesticides As an important agricultural production material, pesticides have made great contributions to reducing crop losses and ensuring food security.
  • their unscientific and unsafe use has brought many negative impacts on agricultural sustainable development, agricultural modernization, and even human health, such as water pollution, ecological damage, and food safety issues, which have become prominent issues restricting the sustainable and stable development of my country's agriculture.
  • the long-term use of pesticides presents the problem of high quantity and low efficiency, which not only leads to enhanced resistance of pests and diseases, but also destroys the ecological structure of the soil, thus affecting the yield of crops. Therefore, it is imperative to continuously improve the level of scientific and technological innovation, promote the integrated development of technical and preparation, and achieve the "reduction in application and increase in efficiency" of pesticides, and study safe and environmentally friendly pesticide formulations.
  • WP wettable powder
  • WG water-dispersible granules
  • SC suspension concentrates
  • EW emulsions in water
  • emulsions are dust-free, with less organic solvent added, and can reduce instability phenomena such as Ostwald ripening, agglomeration, flocculation, and stratification by adding emulsifiers. It is a formulation with better performance. However, emulsions only account for 5%. The reason for this is that in addition to the problem of process scale-up, the most critical problem is the lack of high-performance emulsifiers.
  • commercial pesticide emulsifiers are mainly anionic and non-ionic surfactants, such as calcium alkylbenzene sulfonate (500#), castor oil/alkylphenol polyoxyethylene ether (EL, BY, NP series), which improve the wetting and spreading properties of fat-soluble pesticides to improve the efficacy, but still cannot meet the actual use needs of pesticides in complex environments.
  • anionic and non-ionic surfactants such as calcium alkylbenzene sulfonate (500#), castor oil/alkylphenol polyoxyethylene ether (EL, BY, NP series), which improve the wetting and spreading properties of fat-soluble pesticides to improve the efficacy, but still cannot meet the actual use needs of pesticides in complex environments.
  • the problems of this type of pesticide dispersant are as follows: the pesticide components are easily ineffective due to interaction with surfactants and adjuvants; they are very easy to break the emulsion and aggregate and precipitate under conditions of dilution, acid and alkali, high salt concentration, etc.; the adhesion and sustained release properties on the leaves are poor, and the utilization rate of pesticides is low due to environmental factors such as leaching, bouncing, and light decomposition; and the waste of resources and environmental pollution caused by the large-scale use of pesticides, surfactants and adjuvants has become a serious social problem that threatens human health. Therefore, it is urgent to develop new pesticide emulsions that do not require adjuvants, are environmentally friendly, and have high stability in complex environments.
  • the purpose of the present invention is to provide a pesticide emulsion with a liquid crystal structure and a preparation method and application thereof.
  • a liquid crystal structured pesticide emulsion contains a fat-soluble pesticide and a liquid crystal emulsifier.
  • the pesticide emulsion contains a fat-soluble pesticide, a liquid crystal emulsifier, oil, a thickener, an organic solvent and water.
  • the fat-soluble pesticide can be a fat-soluble pesticide technical or a pesticide formulation, and the formulation is, for example, a suspension, a wettable powder, a dust, a granule, an emulsifiable concentrate, an aqueous solution, and the like.
  • the fat-soluble pesticide is, for example, one or more of thiadipyridamole, thiadipyridamole, diuron, ostiamycin, abscisic acid, ethephon, indolebutyric acid, cypermethrin, thiamethoxam, etc.
  • the fat-soluble pesticide is thiadipyridamole, thiadipyridamole, and diuron.
  • the mass fraction of the fat-soluble pesticide in the pesticide emulsion can be 0.5%-20%, for example, 1%-15% or 1%-10%, and specifically 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%.
  • the liquid crystal emulsifier may be selected from one or more of alkyl glycosides, phosphates, lecithins, sucrose esters, stearoyls, and olive esters.
  • it is a lecithin emulsifier, such as a lecithin liquid crystal emulsifier; the mass fraction of the emulsifier may be 1%-10%, 2%-9%, and specifically 3%, 4%, 5%, 6%, 7%, and 8%.
  • the thickener can be selected from one or more of pectin, xanthan gum, carboxymethyl cellulose, starch, agar, alginic acid and sodium lignin sulfonate; for example, carboxymethyl cellulose; the mass fraction of the thickener can be 0.1%-5%, 0.5%-4%, specifically 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.5%, 3% and the like.
  • the oil is preferably a liquid oil.
  • the liquid oil can be a vegetable oil, an animal oil, or a synthetic oil.
  • the vegetable oil is selected from one or more of peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, avocado oil, and coconut oil.
  • the animal oil is selected from one or more of squalane and squalene.
  • Synthetic oil is selected from one or more of caprylic capric triglyceride, isooctyl palmitate, isopropyl myristate, isooctyl stearate, isononyl isononanoate, dioctyl carbonate, and diisostearyl malate.
  • the mass fraction of the liquid oil in the present invention can be 1%-20%, 2%-15% or 3%-12%, specifically 4%, 5%, 6%, 7%, 8%, 9%, 10%, and 11%.
  • the organic solvent can be a polar or non-polar solvent, such as one or more of n-butanol, methanol, chloroform, anhydrous ethanol, cyclohexane, n-hexane, ether, dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide; for example, dimethyl sulfoxide; the mass fraction of the organic solvent can be 0.5%-40%, 1%-35%, 2%-30%, or 3%-20%, specifically 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%.
  • a polar or non-polar solvent such as one or more of n-butanol, methanol, chloroform, anhydrous ethanol, cyclohexane, n-hexane, ether, dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide; for example, dimethyl sulfoxide;
  • the mass fraction of water may be 50%-90%, for example, 60%, 65%, 70%, 75%, 80%, 85%.
  • the pesticide emulsion may further contain a pH regulator; for example, one or more of sodium hydroxide, potassium hydroxide, hydrochloric acid, phosphoric acid or citric acid may be selected.
  • the pH regulator may be sodium hydroxide and citric acid.
  • the pesticide emulsion contains: 0.5%-20% fat-soluble pesticide technical, 1%-10% liquid crystal emulsifier, 1%-20% oil, 0.1%-5% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the pesticide emulsion contains: 0.5%-20% fat-soluble pesticide suspending agent, 1%-10% liquid crystal emulsifier, 1%-20% oil, 0.1%-5% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the pesticide emulsion contains: 0.5%-20% uniconazole, 1%-10% lecithin liquid crystal emulsifier, 1%-20% oil, 0.1%-5% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the pesticide emulsion contains: 1%-10% uniconazole, 1%-10% lecithin liquid crystal emulsifier, 1%-15% oil, 0.1%-4% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the pesticide emulsion contains: 0.5%-20% thidiazuron-diuron, 1%-10% lecithin liquid crystal emulsifier, 1%-20% oil, 0.1%-5% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the pesticide emulsion contains: 1%-10% thidiazuron-diuron, 1%-10% lecithin liquid crystal emulsifier, 1%-15% oil, 0.1%-4% thickener, 1%-40% organic solvent, and 50%-90% water.
  • the liquid crystal pesticide emulsion has a layered structure of oil/liquid crystal/water (O/LC/W).
  • the present invention also provides a method for preparing the above liquid crystal structure pesticide emulsion, comprising the following steps:
  • the heating temperature is 60-90°C, preferably 70-80°C.
  • the obtained aqueous phase is heated to 60-90°C, preferably 70-80°C.
  • the obtained dispersed solvent phase is heated to 60-90°C, preferably 70-80°C.
  • the oil phase and the dispersed solvent phase are sequentially poured into the water phase at a temperature of 60-90° C., and high shear homogenization is performed (for example, the rotation speed is 4000-10000 r/min) to obtain an emulsion.
  • high shear homogenization the mixture is stirred at a low speed at 25-35° C. to cool, for example, at a rotation speed of 300-1000 r/min for 10-20 minutes to cool.
  • the preparation method comprises the following steps:
  • Homogenization and emulsification pour the oil phase and the dispersion solvent phase into the water phase in sequence at a water bath temperature of 70-80°C, and perform homogenization and dispersion at a speed in the range of 5000-8000 r/min, for example, for 3-15 minutes;
  • the present invention also provides a method for preparing the above liquid crystal structure pesticide emulsion, comprising the following steps:
  • Pesticide emulsion The fat-soluble pesticide is mixed with a blank liquid crystal emulsion to obtain a pesticide emulsion.
  • the heating temperature is 60-90°C, preferably 70-80°C.
  • the obtained aqueous phase is heated to 60-90°C, preferably 70-80°C.
  • the oil phase is poured into the water phase at a temperature of 60-90°C, and high shear homogenization is performed (for example, the rotation speed is 4000-10000 r/min) to obtain an emulsion.
  • high shear homogenization the mixture is stirred at a low speed at 25-35°C to cool down, for example, stirred at a rotation speed of 300-800 r/min for 10-20 minutes to cool down.
  • the pesticide in the above step 4'), is in the form of a pesticide formulation, such as a suspension, a wettable powder, etc.
  • the preparation method comprises the following steps:
  • the present invention also provides the application of the liquid crystal pesticide emulsion in crops, for example, in promoting the growth and yield of crops.
  • the application method can be selected from drip irrigation, foliar spraying, wound application and other methods to be applied to crop planting.
  • the present invention adopts an "onion-like" layered liquid crystal emulsion system of oil layer/liquid crystal layer/water layer (O/LC/W) to encapsulate one or more pesticides between the oil core and the oil/water layer separated by liquid crystals, with an encapsulation rate of nearly 100%.
  • the liquid crystal pesticide emulsion system of the present invention can be applied to different pesticide application environments, such as foliar spraying, drip irrigation and wound spraying.
  • the liquid crystal pesticide emulsion of the present invention does not require the addition of excipients, disintegrants, stabilizers and other adjuvants in the preparation process, is environmentally friendly and widely compatible with a variety of pesticides; in actual complex environments (such as high dilution, pH changes, ion concentration changes, storage and transportation temperature changes, mechanical vibrations), it has excellent thermodynamic stability and is not prone to demulsification such as pesticide precipitation and sedimentation; it has better wetting and spreading properties on the target, promoting its effective deposition; and it has excellent sustained release properties and good diffusivity in the drip irrigation system, significantly improving the utilization rate of pesticides. It is superior to traditional pesticide water dispersants in terms of performance and utilization rate.
  • the liquid crystal pesticide emulsion described in the present invention has an excellent "pruning and shaping" effect on crops (such as cotton, corn, etc.), and is effective in shortening internodes, dwarfing plants, promoting lateral bud growth and flower bud formation, increasing chlorophyll accumulation, etc., and can also increase crop yields.
  • the pesticide preparation method adopted by the present invention has a simple operation process, is less time-consuming, has a small energy loss, and can be prepared on a large scale, which is conducive to the batch production of pesticide emulsions.
  • Figure 1 shows the microscopic morphology and macroscopic photographs of blank liquid crystal emulsion (Blank-LCE), 1% uniconazole liquid crystal emulsion (UZ-LCE), 1% uniconazole Tween-20 emulsion (UZ-TW20), 1% uniconazole ethanol solution (UZ-EtOH) and the corresponding 10-fold dilutions.
  • FIG. 2 is a microscopic morphology of uniconazole liquid crystal emulsions (UZ-LCE) with mass fractions of 1%, 3%, and 5%, respectively.
  • FIG3 is a microscopic morphology of a 1% uniconazole liquid crystal emulsion and samples thereof diluted 10 3 , 10 4 , and 10 5 times, respectively.
  • FIG. 5 shows the microscopic morphology and Zeta potential of 1% pheniconazole liquid crystal emulsion when the mass fraction of diammonium phosphate is 3%, 5%, and 10%.
  • Figure 6 shows the microscopic morphology of the 1% linconazole liquid crystal emulsion before and after centrifugal shaking (3000r/min, 30min) (a, b); and the microscopic morphology of the emulsion after a low-temperature cycle (c) or a high-temperature cycle (d) treatment, wherein the low-temperature cycle treatment transfers the UZ-LCE from a 25°C constant temperature box to a -18°C refrigerator for 24 hours, and then takes it out and places it in a 25°C constant temperature box for storage for 24 hours; the high-temperature cycle treatment transfers the UZ-LCE from a 25°C constant temperature box to a 60°C oven for 24 hours, and then takes it out and places it in a 25°C constant temperature box for storage for 24 hours.
  • the low-temperature cycle treatment transfers the UZ-LCE from a 25°C constant temperature box to a -18°C refrigerator for 24 hours, and then takes it out and places it in a 25°
  • FIG7 shows the bouncing behaviors of deionized water, 1% tert-butyl ether ethanol solution, 1% tert-butyl ether Tween-20 emulsion, blank liquid crystal emulsion and 1000-fold dilution of 1% tert-butyl ether liquid crystal emulsion on cotton leaves.
  • Figure 9 shows the diffusion efficiency (C t /C 0 ) of 5% UZ-LCE and 5% UZ-EtOH in a simulated drip irrigation device (Figure A) over time ( Figure B), where C t and C 0 represent the concentration of UZ in the outflow liquid and the initial concentration of the liquid flowing into the pipe at time t, respectively.
  • FIG. 10 shows the drug release curves (left) and fitted kinetic curves (right) of 5% chloranil liquid crystal emulsion and 5% chloranil ethanol solution.
  • FIG 11 shows the evaluation of the efficacy of different uniconazole formulations after application during the flowering period of cotton.
  • uniconazole liquid crystal emulsion UZ-LCE
  • uniconazole ethanol solution UZ-EtOH
  • uniconazole Tween-20 emulsion UZ-TW 20
  • deionized water CK
  • Figure 12 shows the defoliation effect comparison of deionized water (CK), conventional defoliant (540g/L thiadiazole ⁇ diuron suspension), conventional defoliant and Anrongle compound preparation, and conventional defoliant liquid crystal emulsion in cotton field experiments, and the change diagram of defoliation rate and number of cotton bolls before and after application.
  • CK deionized water
  • conventional defoliant 540g/L thiadiazole ⁇ diuron suspension
  • Anrongle compound preparation conventional defoliant and Anrongle compound preparation
  • conventional defoliant liquid crystal emulsion in cotton field experiments
  • the percentages (%) in the present invention are all weight percentages (wt %).
  • the first step 4 g of lecithin liquid crystal emulsifier is added to 6 g of rapeseed oil, and heated in a water bath at 70° C.-75° C. to dissolve the emulsifier in the rapeseed oil to obtain an oil phase.
  • the fourth step is to quickly pour the oil phase into the water phase at a water bath temperature of 70°C-75°C, and then quickly add the solvent phase, and homogenize at a speed of 5000-8000 r/min for 3-8 minutes to make it homogenous and uniform. Finally, under the condition of an external water bath temperature of 25-32°C, stir at a speed of 300-800 r/min for 10-20 minutes to cool it down to obtain 100g of uniconazole liquid crystal emulsion (UZ-LCE), that is, obtain 5% uniconazole liquid crystal emulsion.
  • UZ-LCE uniconazole liquid crystal emulsion
  • the preparation method is basically the same as that of Example 1, except that the composite liquid crystal emulsifier in the first step is replaced with an equal amount of Tween-20 emulsifier to obtain emulsion UZ-TW20, which is recorded as Control 1-2.
  • the preparation method is basically the same as that of Example 1, except that in the third step, no uniconazole original drug is added to obtain a blank liquid crystal emulsion Blank-LCE, which is recorded as Control 1-3.
  • control CK An equal amount of 100 g of deionized water was used as blank control CK, recorded as control 1-4.
  • the first step 4 g of lecithin liquid crystal emulsifier is added to 6 g of rapeseed oil, and heated in a water bath at 70° C.-75° C. to dissolve the emulsifier in the rapeseed oil to obtain an oil phase.
  • the fourth step is to quickly pour the oil phase into the water phase at a water bath temperature of 70°C-75°C, and then quickly add the solvent phase, and homogenize at a speed of 5000-8000 r/min for 3-8 minutes to make it homogenous and uniform. Finally, under the condition of an external water bath temperature of 25-32°C, stir at a speed of 300-800 r/min for 10-20 minutes to cool down to obtain 100g of uniconazole liquid crystal emulsion (UZ-LCE), that is, obtain 1% uniconazole liquid crystal emulsion.
  • UZ-LCE uniconazole liquid crystal emulsion
  • the preparation method is basically the same as that of Example 2, except that the composite liquid crystal emulsifier in the first step is replaced with an equal amount of Tween-20 emulsifier to obtain emulsion UZ-TW20, which is recorded as control 2-2.
  • the preparation method is basically the same as that of Example 2, except that in the third step, no original drug of uniconazole is added to obtain a blank liquid crystal emulsion Blank-LCE, which is recorded as Control 2-3.
  • control CK An equal amount of 100 g of deionized water was used as blank control CK, recorded as control 2-4.
  • Example 2 and Comparative Examples 1-3 were observed under a polarizing microscope, and their original concentrations and microscopic images after ten-fold dilution are shown in Figure 1.
  • (a 1 ) and (a 2 ) are microscopic images of the original concentration and ten-fold dilution of Blank-LCE obtained in Comparative Example 3
  • (b 1 ) and (b 2 ) are microscopic images of the original concentration and ten-fold dilution of the pesticide emulsion obtained in Example 2
  • (c 1 ) and (c 2 ) are microscopic images of the original concentration and ten-fold dilution of the UZ-TW20 emulsion obtained in Comparative Example 2
  • (d 1 ) and (d 2 ) are microscopic images of the original concentration and ten-fold dilution of the ethyl oxadiazole solution obtained in Comparative Example 1.
  • the "cross-shaped" liquid crystal structure of the blank liquid crystal (Blank-LCE) obtained in Comparative Example 3 ( Figures (a 1 ), (a 2 )) and the uniconazole liquid crystal emulsion UZ-LCE ( Figures (b 1 ), (b 2 )) obtained in Example 2 is obvious, which is highly consistent with the structural characteristics of lamellar liquid crystals.
  • the UZ-EtOH obtained in Comparative Example 1 is a 1% oxadiazole ethanol solution ( Figure d 1 ), but after diluting it 10 times, oxadiazole rapidly precipitates and aggregates and precipitates at the bottom of the bottle ( Figure d 2 ).
  • the difference between this embodiment and embodiment 2 is that the content of clofosazole is changed to 3g and 5g, and the contents of each part are shown in Table 1, and 3% clofosazole liquid crystal emulsion and 5% clofosazole liquid crystal emulsion are obtained respectively.
  • the emulsions of embodiments 2 and 3 are observed under a polarizing microscope, and their microscopic morphology is shown in Figure 2. It can be seen from the figure that with the increase of drug loading, the size of the emulsion droplets increases significantly, and the amount of pesticide encapsulated in the emulsion droplets increases significantly. When the concentration of clofosazole is 5%, the emulsion droplets are filled fully, and no clofosazole crystals are precipitated.
  • the 1% chloranil liquid crystal pesticide emulsion prepared in Example 2 was diluted 10 3 , 10 4 , and 10 5 times with deionized water to obtain a diluted dispersion.
  • the 1% chloranil liquid crystal original emulsion and the diluted dispersions after dilution by 10 3 , 10 4 , and 10 5 were observed under a polarizing microscope, and the microscopic morphology thereof is shown in FIG3 .
  • the UZ-LCE was further diluted multiple times. As the dilution multiple increased from 10 3 to 10 5 times, the liquid crystal texture at the outer edge of the emulsion droplet was intact, and no UZ crystal leakage and precipitation were observed. It can be seen that UZ-LCE has significant dilution stability and can overcome the technical problems of dilution demulsification, precipitation, aggregation, and sedimentation commonly found in traditional pesticide water dispersants.
  • Figure 4 shows the microscopic morphology and Zeta potential of Example 2 and the 5% chloramphenicol liquid crystal emulsion prepared above when the aqueous phase has a pH of 3, 7, and 11, observed under a polarizing microscope.
  • the droplets in UZ-LCE are evenly distributed, and the outer edge liquid crystal texture is intact; when the pH is 11, a small amount of droplets are broken at the outer edge due to the hydrolysis of the emulsifier.
  • UZ-LCE has good stability at different pH values, and its stability under acidic and neutral conditions is better than that under alkaline conditions.
  • this example investigates the effect of the concentration of diammonium phosphate (NH 4 H 2 PO 4 ), a commonly used nitrogen/phosphate fertilizer in the field, on the stability of the emulsion.
  • diammonium phosphate NH 4 H 2 PO 4
  • the preparation was basically carried out according to the method of Example 2, except that 3%, 5% and 10% NH 4 H 2 PO 4 were added to the aqueous phase of the emulsion prepared in the second step, respectively, and the other conditions remained unchanged, and three different pesticide emulsions were obtained.
  • the microscopic morphology and Zeta potential of the 1% uniconazole liquid crystal emulsion observed under a polarizing microscope when the mass fraction of NH 4 H 2 PO 4 was 3%, 5% and 10% are shown in Figure 5.
  • the uniconazole liquid crystal emulsion obtained in Example 2 was first centrifuged at 3000r/min for 0.5h, and then subjected to low temperature cycle and high temperature cycle respectively.
  • the low temperature cycle was that the liquid crystal emulsion at 25°C in the constant temperature box was placed in a -18°C refrigerator for 24h, and then taken out and placed in a constant temperature box at 25°C for 24h;
  • the high temperature cycle was that the liquid crystal emulsion at 25°C in the constant temperature box was placed in a 65°C oven for 24h, and then taken out and placed in a constant temperature box at 25°C for 24h.
  • the microscope micrograph after each of the above steps is shown in Figure 6.
  • lecithin liquid crystal emulsifier is added to 10 g of mixed oil (4 g of rapeseed oil, 3 g of coconut oil, and 3 g of castor oil), and heated in a water bath at 70° C.-75° C. to dissolve the emulsifier in the mixed oil to obtain an oil phase.
  • mixed oil 4 g of rapeseed oil, 3 g of coconut oil, and 3 g of castor oil
  • the third step is to quickly pour the oil phase into the water phase at a water bath temperature of 70°C-75°C, homogenize at a speed of 5000-8000 r/min for 3-8 minutes to mix them evenly, and finally stir at a speed of 300-800 r/min for 10-20 minutes to cool it down under the condition of an external water bath temperature of 25-32°C to obtain 100g of blank liquid crystal emulsion (LCE).
  • LCE blank liquid crystal emulsion
  • the fourth step is to add 20 mL of defoliant (540 g/L thiadiazole ⁇ diuron suspension), 80 mL of alkyl sulfonate additive, and 70 mL of ethephon water-soluble agent to 40 mL of blank liquid crystal emulsion, add a small amount of deionized water and shake to disperse it, mix well, add deionized water to make up to 2 L, and obtain a defoliant liquid crystal emulsion.
  • defoliant 540 g/L thiadiazole ⁇ diuron suspension
  • 80 mL of alkyl sulfonate additive 80 mL
  • 70 mL of ethephon water-soluble agent ethephon water-soluble agent
  • Test method Take pictures with a high-speed camera.
  • Example 2 After the samples in Example 2 and Comparative Examples 2-1 to 2-4 were diluted 1000 times, the bouncing behavior and wettability of the above dilutions on the clean cotton leaf surface were studied by a high-speed camera. The spreadability changes of uniconazole in different systems over time are shown in FIG7 .
  • the deionized water control 2-4 and the ethylenediaminetetracycline ethanol dispersion control 2-1 will bounce and splash to varying degrees when contacting the cotton leaf surface, causing the loss of pesticides;
  • the ethylenediaminetetracycline Tween emulsion control 2-2 has a large amount of UZ precipitated crystals, and carries a large amount of ethylenediaminetetracycline crystals when colliding with the interface, and has a very poor dispersion; while the ethylenediaminetetracycline blank liquid crystal emulsion control 2-3 and the ethylenediaminetetracycline liquid crystal emulsion Example 2 have good dispersion and stability and low interfacial free energy of the emulsification system, and show significantly better wetting and spreading properties than the control.
  • the rheological properties of pesticide formulations are closely related to their stability and leaf deposition efficiency.
  • the rheological barrier effect can reduce the migration and diffusion of emulsion droplets; the semi-solid liquid crystal network extending throughout the continuous phase can significantly enhance the stability of the emulsion by slowing down the movement of droplets. Therefore, the rheological properties of the liquid crystal pesticide emulsion were evaluated.
  • the following uniconazole liquid crystal emulsions (UZ-LCE) with different drug loadings, different pH values and different salt concentrations were prepared according to the method of Example 1:
  • Liquid crystal emulsions of 0.5% uniconazole, 10% uniconazole, and 20% uniconazole were prepared by a method similar to that in Example 1, with the amount of uniconazole added adjusted.
  • Emulsions of different salt concentrations of 5% 5% 5% 6% 7% 10% NH 4 H 2 PO 4 were added to the aqueous phase of the emulsion prepared in the second step, and other conditions remained unchanged, to obtain 5% 5% 5% 5% 6% 10% NH 4 H 2 PO 4 liquid crystal emulsions.
  • the rheological stability of the prepared unicyclic azole liquid crystal emulsion was evaluated by rheometer, as shown in Figure 8.
  • (ac), (df), and (gi) are the steady-state rheological curves, thixotropic curves, and dynamic viscoelastic curves of UZ-LCE under different UZ mass fractions, different pH values, and different NH 4 H 2 PO 4 mass fractions, respectively.
  • the steady-state rheological results (a, d, g) show that the drug loading and salt concentration significantly promote the increase in the initial viscosity ( ⁇ 0.01 ) of UZ-LCE. Since pH has no significant effect on the droplet size, it has little effect on its initial viscosity.
  • the storage modulus (G') is higher than the loss modulus (G") in the low-frequency region, and UZ-LCE mainly exhibits the elastic properties of a solid, which is beneficial to the storage and transportation of the pesticide liquid crystal emulsion; in the high-frequency region, the storage modulus (G') is less than the loss modulus (G"), and UZ-LCE mainly exhibits the viscous properties of a liquid, which is beneficial to the spraying and atomization of the pesticide liquid crystal emulsion when used.
  • Test process The 5% uniconazole liquid crystal emulsion (UZ-LCE) prepared in Example 1 and the 5% uniconazole ethanol solution (UZ-EtOH) prepared in Comparative Example 1-1 were subjected to a simulated drip irrigation diffusion experiment (the device diagram is shown in Figure 9 (left)). 1g of UZ-LCE and 1g of UZ-EtOH were taken respectively and diluted to 1L with deionized water. 1 mL was taken from each of the samples, 4 mL of anhydrous ethanol was added to each sample, and the initial concentration C 0 was determined by a UV-Vis spectrophotometer.
  • Samples were taken from the other side of the tube at regular intervals, 1 mL of the effluent was added to 4 mL of anhydrous ethanol to promote the dissolution of clofosinate, and the concentration C t at the corresponding time was determined by a UV-Vis spectrophotometer. The results were repeated three times and the average value was taken.
  • the release of pesticides in the tube is mainly divided into two stages: first, it is adsorbed on the surface of the pores of the filler (perlite) in the tube; after adsorption saturation, the adsorption and desorption of the pesticide reach a dynamic equilibrium, so the concentration of thiazolinone in the outflowing liquid remains constant.
  • the concentration of clofosazole in the release liquid flowing out of the tube is 0.
  • the sustained release performance of the uniconazole liquid crystal emulsion prepared in Example 1 and the uniconazole ethanol solution prepared in Comparative Example 1-1 was evaluated.
  • Test process: a 5% uniconazole solution was prepared in ethanol/water (v/v 3:7), and the corresponding absorbance A was measured by UV-Vis spectrophotometer. A standard curve of uniconazole concentration-absorbance A was made.
  • In vitro sustained release experiments were performed on the 5% UZ-LCE obtained in Example 1 and the 5% UZ-EtOH obtained in Comparative Example 1-1.
  • the release curves of UZ-EtOH and UZ-LCE were fitted with the first-order kinetics (the functional relationship curve of ln(C 0 /C t )-t), and the linear correlation coefficient (R 2 ) of UZ-LCE after fitting was 0.9922, indicating that the sustained-release kinetic mechanism of the liquid crystal emulsion conforms to the first-order release kinetic model, and the pesticide release process is controlled by concentration diffusion.
  • R 2 0.8711 ⁇ 0.99, which may be related to the different existence states of clofosconazole in UZ-EtOH.
  • Test method The cotton field experiment was carried out in the Woda Agroscience cotton experimental field, and the average plant height of cotton was >40cm (flowering period).
  • UZ-LCE was applied by drip irrigation and foliar spraying.
  • a blank control group (CK) control 1-4 in comparative example 1-4
  • UZ-EtOH control 1-1 in comparative example 1-1
  • UZ-TW20 control 1-2 in comparative example 1-2
  • Blank-LCE control 1-3 in comparative example 1-3
  • the total amount of ethylenediaminetetracycline (98%) was 6.84g/mu, which was drip-irrigated/sprayed three times with an interval of 7 days.
  • the first dosage is 1.9g/mu, and 38g of each product of Example 1 and Control 1-1 to 1-4 is taken, and diluted about 950,000 times in the fertilizer tank for use.
  • the second dosage is 2.28g/mu, and 45.6g of each product of Example 1 and Control 1-1 to 1-4 is taken, and diluted about 950,000 times in the fertilizer tank with water for use.
  • the third dosage is 2.66g/mu, and 53.2g of each product of Example 1 and Control 1-1 to 1-4 is taken, and diluted about 950,000 times in the fertilizer tank for use.
  • the spraying group is diluted to about 500 times with water in the sprayer for use. After the start of application, the growth of cotton is measured and recorded every three days.
  • the parameters investigated include cotton plant height, upper three internode height, number of flowering, number of fruit branches, total number of nodes, and SPAD value related to chlorophyll content. Statistics and analysis of changes in various physiological parameters of cotton to evaluate the efficacy. Specific as shown in Figure 11.
  • Figure (c) shows the height of the three-stage inverted pedestal in different experimental groups, which can directly reflect the effect on the growth of cotton apical buds.
  • the height of the top three nodes of UZ-LCE (drip irrigation) is lower than that of the control group, while the effect of UZ-LCE (spraying) is the most significant, which once again proves the significant advantages of UZ-LCE in inhibiting cell elongation, shortening internodes, and dwarfing plants, and the effect of spraying is better than drip irrigation.
  • Figure 11 (d) counts the maximum number of flowering of the top three nodes of different experimental groups (controlled by the growth law of cotton, the number of flowering of all experimental groups reached a peak on the 17th-20th day of drug application).
  • UZ-LCE spike irrigation
  • UZ-LCE drip irrigation
  • Chlorophyll content determines the efficiency of cotton photosynthesis.
  • Test method A cotton defoliant field experiment was conducted in the test field during the cotton boll opening period.
  • Four samples were applied by foliar spraying, and a blank control group (CK) (Control 8-1 in Comparative Example 8-1), a conventional defoliant group (Control 8-2 in Comparative Example 8-2) and a conventional defoliant + Anrongle group (Control 8-3 in Comparative Example 8-3) were set up respectively, which was a control experiment of the defoliant liquid crystal emulsion prepared in Example 8 (recorded as: conventional defoliant + LCE).
  • Five plants were continuously measured in each group, and two rows were randomly selected, with a total of 10 plants as samples.
  • the leaves of all the experimental groups and the control group using defoliants are more yellow, more dehydrated, more wilted, and have fewer leaves, and the leaves of the blank control (CK) group are the greenest.
  • the defoliation rates of the experimental groups and the control group with defoliants increased significantly, among which the defoliation rate of the defoliant liquid crystal emulsion (conventional defoliant + LCE) prepared in Example 8 is the highest.

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  • Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

La présente invention concerne une émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation, ainsi que son utilisation. L'émulsion comprend un principe actif pesticide et un émulsifiant à cristaux liquides. Selon la présente invention, en construisant une structure en couches "de type oignon" comprenant une couche d'huile, une couche de cristaux liquides et une couche d'eau (O/LC/W), le pesticide est limité et solubilisé entre la couche d'eau et la couche d'huile, et le rapport de charge de médicament est d'environ 100%. L'émulsion pesticide à cristaux liquides de la présente invention implique un procédé de préparation simple et écologique, peut être préparée à grande échelle, et est adaptée à divers pesticides ; l'émulsion pesticide est supérieure à des formulations pesticides dispersibles dans l'eau classiques similaires en termes de stabilité de dispersion, d'efficacité de dépôt cible et analogues, et est particulièrement appropriée pour une utilisation dans l'environnement complexe actuel.
PCT/CN2024/072966 2023-01-19 2024-01-18 Émulsion de pesticide ayant une structure de cristaux liquides, son procédé de préparation et son utilisation Ceased WO2024153171A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120036309A (zh) * 2025-04-15 2025-05-27 江西省农业科学院蔬菜花卉研究所 一种大棚芦笋甜菜夜蛾防治喷施剂及其制备工艺

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6171600B1 (en) * 1993-12-02 2001-01-09 Ifac Gmbh Stable multiple X/O/Y-emulsion
JP2003212716A (ja) * 2002-01-23 2003-07-30 Hifu Rinsho Yakuri Kenkyusho Kk 液晶型乳化組成物
WO2007140510A1 (fr) * 2006-06-02 2007-12-13 Monash University Composition agrochimique comprenant des particules de cristaux liquides
CN101232804A (zh) * 2005-07-28 2008-07-30 美国陶氏益农公司 包含仅基于覆盖有层状液晶覆盖层的油珠的水包油乳状液的农业组合物
WO2015046648A1 (fr) * 2013-09-26 2015-04-02 코스맥스 주식회사 Procédé de préparation d'une émulsion multicouche lamellaire de cristaux liquides contenant un lipide intercellulaire
EP3610728A1 (fr) * 2018-08-14 2020-02-19 EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt Revêtements antimicrobiens
CN112972381A (zh) * 2021-03-29 2021-06-18 华东理工大学 一种液晶包覆晶型药物的载药乳液及其制备方法
CN115381723A (zh) * 2022-08-15 2022-11-25 华东理工大学 一种水包油包多元醇的多重液晶乳液及其制备方法、应用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6171600B1 (en) * 1993-12-02 2001-01-09 Ifac Gmbh Stable multiple X/O/Y-emulsion
JP2003212716A (ja) * 2002-01-23 2003-07-30 Hifu Rinsho Yakuri Kenkyusho Kk 液晶型乳化組成物
CN101232804A (zh) * 2005-07-28 2008-07-30 美国陶氏益农公司 包含仅基于覆盖有层状液晶覆盖层的油珠的水包油乳状液的农业组合物
WO2007140510A1 (fr) * 2006-06-02 2007-12-13 Monash University Composition agrochimique comprenant des particules de cristaux liquides
WO2015046648A1 (fr) * 2013-09-26 2015-04-02 코스맥스 주식회사 Procédé de préparation d'une émulsion multicouche lamellaire de cristaux liquides contenant un lipide intercellulaire
EP3610728A1 (fr) * 2018-08-14 2020-02-19 EMPA Eidgenössische Materialprüfungs- und Forschungsanstalt Revêtements antimicrobiens
CN112972381A (zh) * 2021-03-29 2021-06-18 华东理工大学 一种液晶包覆晶型药物的载药乳液及其制备方法
CN115381723A (zh) * 2022-08-15 2022-11-25 华东理工大学 一种水包油包多元醇的多重液晶乳液及其制备方法、应用

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120036309A (zh) * 2025-04-15 2025-05-27 江西省农业科学院蔬菜花卉研究所 一种大棚芦笋甜菜夜蛾防治喷施剂及其制备工艺

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