Use of a choline ionic liquid, chlorantraniliprole microcapsule and preparation method and use thereof

Abstract

This invention provides an application of choline ionic liquid, chlorantraniliprole microcapsules, their preparation method, and applications, belonging to the field of microcapsules. In this invention, the choline ionic liquid with the structure shown in Formula I has a wide liquid range, and its cationic choline structure has a high affinity for chlorantraniliprole, so it can replace organic solvents to dissolve chlorantraniliprole. In addition, the choline ionic liquid has low toxicity to organisms, ensuring human health and reducing industrial waste gas and wastewater treatment.

Description

Technical Field

[0001] This invention relates to the field of microcapsules, and more particularly to the application of a choline ionic liquid, chlorantraniliprole microcapsules, their preparation methods, and applications. Background Technology

[0002] Chemical pesticides are widely used worldwide to increase farm yields. However, long-term or high-dose use of chemical pesticides not only causes phytotoxicity but also consumes significant human and material resources, increasing production costs. Therefore, improving their utilization rate and reducing pesticide dosage has become a current research hotspot. Chlorantraniliprole, developed by DuPont in 2000, is a novel o-aminobenzoamide insecticide that acts on ryanodine receptors. It has good control effects on lepidopteran insects, good environmental compatibility, and minimal harm to non-target organisms. However, chlorantraniliprole is photolabile in the environment and easily photodegrades after application. Therefore, to achieve the target control effect, it is often applied multiple times in actual production, resulting in low utilization of the pesticide.

[0003] Slow-release pesticide technology not only achieves high pesticide utilization rates but also reduces environmental pollution. Controlled-release pesticide formulations typically use polymers as carriers, adsorbing (or encapsulating) the active compound through a series of processing steps. This new formulation allows for the slow and continuous release of pesticides in the field after application, and can even achieve targeted release through polymer functionalization, thus preventing and controlling pests. Simultaneously, it effectively improves pesticide utilization, reduces pesticide usage, and ensures crop yield. Microcapsules are a typical controlled-release formulation, consisting of an active compound core and a polymer shell. Their dispersed particle size ranges from 1 to 5000 μm, and their external morphology can manifest as smooth spheres, grape-like clusters, or irregularly shaped vesicles with smooth or folded surfaces. This core-shell structure isolates easily degradable compounds from environmental factors such as ultraviolet radiation, microorganisms, and temperature, thereby protecting the active compound and prolonging its duration of action.

[0004] However, the synthesis of pesticide microcapsules has some limitations. Most pesticide active ingredients are solids, and before being processed into microcapsules, they need to be dissolved using organic solvents (dichloromethane, trichloromethane, acetone, etc.) and surface tension reduced using surfactants. However, these toxic and volatile organic solvents not only threaten the health of the personnel involved in the preparation, but also increase problems such as industrial waste gas and wastewater treatment; surfactants increase the variety of raw materials and the number of synthesis steps. Summary of the Invention

[0005] The purpose of this invention is to provide an application of choline ionic liquid, chlorantraniliprole microcapsules, their preparation method and application. The choline ionic liquid used in this invention replaces organic solvents and surfactants in the preparation of microcapsules, ensuring human health, reducing industrial waste gas and wastewater treatment, and the synthesis steps are simple.

[0006] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0007] This invention provides a choline ionic liquid having the structure shown in Formula I:

[0008]

[0009] The n is 10 to 14, and m = 2n + 1.

[0010] The present invention also provides a method for preparing the choline ionic liquid described above, comprising the following steps:

[0011] Triethanolamine, a polar organic solvent, and a compound with the structural formula C n H m A nucleophilic substitution reaction was carried out on a mixture of compounds X to give the compound shown in Formula II; wherein X is a halogen atom.

[0012]

[0013] The compound shown in Formula II is mixed with water and salicylate to undergo an ion exchange reaction to obtain the choline ionic liquid.

[0014] Preferably, the triethanolamine has the structural formula C n H m The molar ratio of compound X is 1:0.5 to 1.5.

[0015] Preferably, the polar organic solvent includes one or more of ethanol, methanol, and acetonitrile.

[0016] Preferably, the nucleophilic substitution reaction is carried out under reflux conditions, and the reaction time is 24–96 h.

[0017] The present invention also provides the application of the choline ionic liquid described in the above scheme or the choline ionic liquid prepared by the preparation method described in the above scheme in the preparation of microcapsules.

[0018] This invention also provides a method for preparing chlorantraniliprole microcapsules, comprising the following steps:

[0019] Chlorantraniliprole was dissolved in a choline ion liquid to obtain a chlorantraniliprole solution;

[0020] The chlorantraniliprole solution was mixed with a liquid silicon source, an alkaline source, and water to carry out a hydrolysis reaction, thereby obtaining the chlorantraniliprole microcapsules.

[0021] The choline ionic liquid is the choline ionic liquid described in the above scheme or the choline ionic liquid prepared by the preparation method described in the above scheme.

[0022] Preferably, the liquid silicon source includes TEOS, and the alkali source includes ammonia and / or sodium hydroxide solution.

[0023] The present invention also provides chlorantraniliprole microcapsules prepared by the preparation method described above, having a core-shell structure, wherein the core comprises choline ionic liquid and chlorantraniliprole, and the shell comprises silica.

[0024] The present invention also provides the application of the chlorantraniliprole microcapsules described above in the preparation of insecticides.

[0025] This invention provides a choline ionic liquid having the structure shown in Formula I:

[0026]

[0027] The n is 10 to 14, and m = 2n + 1.

[0028] In this invention, the choline ionic liquid with the structure shown in Formula I has a wide liquid range, and its cationic choline structure has a high affinity for chlorantraniliprole, so it can replace organic solvents to dissolve chlorantraniliprole; in addition, the choline ionic liquid has low toxicity to organisms, ensuring human health and reducing industrial waste gas and wastewater treatment.

[0029] Furthermore, compared to the traditional microcapsule synthesis process, the choline ionic liquid used in this invention can replace the surfactant CTAB / CTAC, reducing the types of inputs and significantly simplifying the synthesis steps.

[0030] The chlorantraniliprole microcapsules prepared by this invention have higher efficacy, lower dosage, and significant sustained-release effect compared to traditional emulsifiable concentrate formulations, thus exhibiting high safety for non-target organisms. Attached Figure Description

[0031] Figure 1 This is a diagram illustrating the reaction process during the preparation of the ionic liquid in this example.

[0032] Figure 2 The image shows the XRD pattern of the chlorantraniliprole microcapsules from Example 1.

[0033] Figure 3 Here is a scanning electron microscope image of the chlorantraniliprole microcapsules from Example 1;

[0034] Figure 4 This is a transmission electron microscope image of the chlorantraniliprole microcapsules from Example 1.

[0035] Figure 5 The image shown is a TGA image of the chlorantraniliprole microcapsules from Example 1.

[0036] Figure 6 The DTG diagram of chlorantraniliprole microcapsules in Example 1 is shown.

[0037] Figure 7 The nitrogen adsorption-desorption isotherm of chlorantraniliprole microcapsules in Example 1;

[0038] Figure 8 This is a pore size distribution diagram of the chlorantraniliprole microcapsules in Example 1;

[0039] Figure 9 Concentration curves of chlorantraniliprole and chlorantraniliprole microcapsules from Example 1 over time;

[0040] Figure 10 Here is a SEM image of the chlorantraniliprole microcapsules from Example 2;

[0041] Figure 11 Here is a SEM image of the chlorantraniliprole microcapsules from Example 3;

[0042] Figure 12 This is a transmission electron microscope image of comparative example 1CHO-CHL-MSH-4. Detailed Implementation

[0043] This invention provides a choline ionic liquid having the structure shown in Formula I:

[0044]

[0045] The n is 10 to 14, and m = 2n + 1.

[0046] The present invention also provides a method for preparing the choline ionic liquid described above, comprising the following steps:

[0047] Triethanolamine, a polar organic solvent, and a compound with the structural formula CnHmX were mixed and subjected to a nucleophilic substitution reaction to obtain the compound shown in Formula II; wherein X is a halogen atom.

[0048]

[0049] The compound shown in Formula II is mixed with water and salicylate to carry out an ion exchange reaction, thereby obtaining the choline ionic liquid.

[0050] This invention utilizes triethanolamine, a polar organic solvent, and a compound with the structural formula C n H mThe compounds of X were mixed and subjected to a nucleophilic substitution reaction to give the compound shown in Formula II.

[0051] In this invention, the mixing preferably includes dissolving triethanolamine in a polar organic solvent and then mixing it with a compound having the structural formula CnHmX.

[0052] In this invention, the preferred molar ratio of triethanolamine to the volume ratio of the polar organic solvent is 4 mmol: 5 mL; the polar organic solvent preferably includes one or more of acetonitrile, methanol, and ethanol.

[0053] In this invention, the triethanolamine has the structural formula C n H m The molar ratio of compound X is preferably 1:0.5 to 1.5, more preferably 1:0.8 to 1.2; X is a halogen atom; the halogen atom includes one of Cl, Br and I.

[0054] In this invention, the nucleophilic substitution reaction is preferably carried out under reflux conditions, and the reaction time is preferably 24 to 96 hours, more preferably 48 to 72 hours.

[0055] In this invention, the structural formula is C n H m Taking 1-bromododecane as an example, the equation for the nucleophilic substitution reaction is as follows:

[0056]

[0057] After the nucleophilic substitution reaction is completed, the present invention preferably removes the polar organic solvent from the product obtained by the nucleophilic substitution reaction, and then mixes the obtained residue with ethyl acetate and ultrapure water to obtain an aqueous phase; after removing the water from the aqueous phase, the compound shown in Formula II is obtained.

[0058] In this invention, the preferred method for removing polar organic solvents is rotary evaporation; the rotary evaporation is preferably carried out under vacuum conditions, the preferred temperature for rotary evaporation is 50°C, the preferred time is 30 min, and the preferred speed is 35 r / min.

[0059] In this invention, the method of removing water from the aqueous phase preferably includes rotary evaporation followed by drying.

[0060] After obtaining the compound shown in Formula II, the present invention mixes the compound shown in Formula II with water and salicylate to carry out an ion exchange reaction to obtain the choline ionic liquid.

[0061] In this invention, the mixing preferably includes dissolving the compound of Formula II in water and then mixing it with salicylate.

[0062] In this invention, the volume ratio of the compound represented by Formula II to water is preferably 1:10;

[0063] The volume ratio of the ionic liquid to the mass ratio of the salicylate is preferably 5 mL: 1 g; the salicylate preferably includes sodium salicylate.

[0064] The ion exchange reaction is preferably carried out at room temperature for a time of 10 minutes; the ion exchange reaction is preferably carried out under stirring conditions.

[0065] In this invention, taking the compound with structural formula CnHmX as a compound of formula II prepared from 1-bromododecane and sodium salicylate as a salicylate as an example, the equation for the ion exchange reaction is as follows:

[0066]

[0067] After the ion exchange reaction is completed, the present invention preferably separates the products obtained from the ion exchange reaction into layers, and performs rotary evaporation and purification on the obtained oil phase to obtain the choline ionic liquid.

[0068] The present invention also provides the application of the choline ionic liquid described in the above scheme or the choline ionic liquid prepared by the preparation method described in the above scheme in the preparation of microcapsules.

[0069] This invention also provides a method for preparing chlorantraniliprole microcapsules, comprising the following steps:

[0070] Chlorantraniliprole was dissolved in a choline ion liquid to obtain a chlorantraniliprole solution;

[0071] The chlorantraniliprole solution was mixed with a liquid silicon source, an alkaline source, and water to carry out a hydrolysis reaction, thereby obtaining the chlorantraniliprole microcapsules.

[0072] The choline ionic liquid is the choline ionic liquid described in the above scheme or the choline ionic liquid prepared by the preparation method described in the above scheme.

[0073] In this invention, the mass ratio of chlorantraniliprole to the volume ratio of choline ionic liquid is preferably 50 mg: 1 mL; the dissolution preferably includes sequential ultrasonic treatment, heating and shaking; the ultrasonic treatment power is preferably 120 W, the frequency is preferably 40 kHz, and the time is preferably 2 min; the heating temperature is preferably 50 °C, and the time is preferably 5 min.

[0074] In this invention, the mixing preferably includes: first mixing the chlorantraniliprole solution, liquid silicon source and water, and then second mixing with the alkali source.

[0075] In this invention, the volume ratio of the chlorantraniliprole solution to the liquid silicon source is preferably 1:1; the volume ratio of the chlorantraniliprole solution to water is preferably 1:49.

[0076] In this invention, the mass ratio of the liquid silicon source to the alkali source is preferably 100:5; the liquid silicon source includes TEOS, and the alkali source includes ammonia and / or sodium hydroxide solution; the mass concentration of the ammonia is preferably 25-28%; and the mass concentration of the sodium hydroxide solution is preferably 10%.

[0077] In this invention, the first mixing is preferably performed under ultrasound, wherein the power of the ultrasound is preferably 120W, the frequency is preferably 40kHz, and the time is preferably 2min.

[0078] In this invention, when the alkali source is ammonia, the second mixing preferably includes adding ammonia dropwise to the solution obtained from the first mixing.

[0079] In this invention, the hydrolysis reaction is preferably carried out under ultrasonic conditions, wherein the ultrasonic power is preferably 120W, the frequency is preferably 40kHz, and the time is preferably 5min. When the alkali source is ammonia, the dripping time is preferably less than 5min.

[0080] After the hydrolysis reaction, the present invention preferably ages, centrifuges, washes and dries the mixture obtained from the hydrolysis reaction; the aging temperature is preferably room temperature and the time is preferably 12 hours; the centrifugation speed is preferably 5000 rpm and the time is preferably 5 minutes; the washing agent is preferably deionized water; the drying temperature is preferably 50°C and the time is preferably 5 hours.

[0081] The present invention also provides chlorantraniliprole microcapsules prepared by the preparation method described above, having a core-shell structure, wherein the core comprises an ionic liquid and chlorantraniliprole, and the shell comprises silica.

[0082] The present invention also provides the application of the chlorantraniliprole microcapsules described above in the preparation of insecticides.

[0083] The following examples illustrate the application of the choline ionic liquid, chlorantraniliprole microcapsules, their preparation methods, and applications provided by this invention. However, these examples should not be construed as limiting the scope of protection of this invention.

[0084] The reaction process for preparing the ionic liquid in this invention is as follows: Figure 1 As shown.

[0085] Example 1

[0086] Preparation process of ionic liquids:

[0087] Ionic liquid CHO-12: Weigh 40 mmol of triethanolamine and dissolve it in 50 mL of ethanol. Then add 50 mmol of 1-bromododecane. Heat under reflux for 48 h. Vacuum evaporate using a rotary evaporator for 30 min (35 r / min, 50 °C). Purify with ethyl acetate and ultrapure water to remove excess raw materials. Take the aqueous phase, concentrate by rotary evaporation, and dry in an oven for 5 h to remove excess water, thus obtaining ionic liquid CHO-12.

[0088] Ionic liquid CHO-12-SA: Dissolve 5 mL of ionic liquid CHO-12 in 50 mL of deionized water, add 1 g of sodium salicylate, stir at room temperature for 10 min, the reaction solution will separate into oil and water phases, after cooling to room temperature, take the oil phase, rotary evaporate and purify for later use.

[0089] Microcapsule preparation process:

[0090] Take 1 mL of CHO-12-SA ionic liquid and 0.05 g of CHL (chlorantraniliprole) and place them in a 2 mL storage tube. Sonicate for 2 min (40 kHz, 120 W), then heat in a 50 °C water bath for 5 min and shake well. Add 1 mL of the above mixture and 1 mL of TEOS to 49 mL of deionized water, sonicate for 2 min (40 kHz, 120 W), and continue sonicating for 5 min to form a milky white suspension. Simultaneously, add 50 μL of 25% ammonia solution. After the sonication reaction stops, age the reaction solution at room temperature. After 12 h, centrifuge the reaction solution (5000 rpm, 5 min), wash the white solid product once with deionized water, and dry at 50 °C for 5 h to obtain chlorantraniliprole microcapsules (denoted as CHL@IL-PHS).

[0091] XRD analysis was performed on the chlorantraniliprole microcapsules of Example 1, and the results are as follows: Figure 2 As shown. By Figure 2 It can be seen that there is a relatively broad characteristic peak at 2θ = 15°-40°, which corresponds to the amorphous structure of silicon dioxide. Therefore, the crystal structure of chlorantraniliprole microcapsules is amorphous silicon dioxide.

[0092] Scanning electron microscopy and transmission electron microscopy were performed on the chlorantraniliprole microcapsules of Example 1. The results are as follows: Figures 3-4 As shown. By Figures 3-4 It can be seen that the microcapsules are spherical in appearance, have good morphology, good dispersibility, a small number of microcapsules agglomerate, and have a large particle size, with an average particle size of about 2 μm.

[0093] TGA and DTG analyses were performed on chlorantraniliprole, ionic liquid CHO-12-SA (denoted as IL in the figure), and the chlorantraniliprole microcapsules of Example 1. The results are as follows: Figures 5-6As shown. By Figures 5-6 It can be seen that the mass loss below 100℃ is due to the evaporation of water in the microcapsules, the mass loss between 180 and 260℃ is the mass loss of 2% of the chlorantraniliprole technical, and the mass loss between 260 and 430℃ is 55%, which may be related to the evaporation and decomposition of the ionic liquid. Between 22 and 800℃, the weight loss rate of chlorantraniliprole microcapsules is 70%, therefore the surface of the microcapsules contains 13% silica.

[0094] The nitrogen adsorption-desorption isotherm and pore size distribution of chlorantraniliprole microcapsules were measured, and the results are as follows: Figures 7-8 As shown. By Figure 7 It can be seen that the nitrogen adsorption-desorption isotherm of the microcapsules belongs to Type IV, proving that the microcapsules are mesoporous materials. When the relative pressure approaches 0.8, the adsorption curve rises rapidly, and there is a hysteresis loop between the adsorption and desorption curves, which is related to the capillary condensation phenomenon of mesoporous materials. The curve is an H2 type hysteresis loop, indicating that its mesoporous structure is an ink bottle-shaped pore.

[0095] Depend on Figure 8 It can be seen that its pore size is mainly around 3nm and 9nm, indicating that it is between micropores and mesopores.

[0096] The specific surface area, pore volume, and average pore size of the chlorantraniliprole microcapsules in Example 1 are shown in Table 1, and are 961.3960 m², respectively. 2 ·g -1 2.6416 cm3·g -1 And 10.9909nm.

[0097] Table 1. Specific surface area, pore volume, and average pore size of chlorantraniliprole microcapsules in Example 1 (BET method).

[0098]

[0099] The zeta potential of the chlorantraniliprole microcapsules in Example 1 was measured, and the results are shown in Table 2.

[0100] The mass of chlorantraniliprole in chlorantraniliprole microcapsules was quantitatively analyzed by high performance liquid chromatography (HPLC). The HPLC conditions were: Eclipse Plus C18 column (250 mm × 4.6 mm, 5 μm); mobile phase: V(acetonitrile):V(water) = 80:20; flow rate: 1.0 mL / min; detection wavelength: 230 nm; injection volume: 5 μL; column temperature: 35 °C; and then the mass was determined according to formula D. L The content of chlorantraniliprole in the microcapsules was calculated to be 47.17% using the formula: W1 / W2 × 100%. Where D... LW1 represents the drug loading percentage; W2 represents the mass of the drug in the carrier (mg); W3 represents the total mass of the drug-carrying carrier (mg).

[0101] Chlorantraniliprole and the chlorantraniliprole microcapsules of Example 1 were dispersed in 50 mL of methanol-water solution (3:7, v / v) and placed in quartz tubes. The concentration curves of chlorantraniliprole and the chlorantraniliprole microcapsules of Example 1 over time were studied under ultraviolet irradiation conditions (light wavelength 254 nm, irradiation distance 20 cm). The results are as follows: Figure 9 As shown. By Figure 9 It can be seen that the degradation kinetics data of chlorantraniliprole under ultraviolet light fit the first-order model very well (R2>0.99), and the degradation parameters DT50, DT90 and k are 2.07h, 3.68h and 0.252, respectively. In Example 1, the CHL in the chlorantraniliprole microcapsules was not completely released due to the protection of the silica shell, but the curve shows that CHO-CHL-MSH can effectively protect CHL from the influence of ultraviolet light and prolong the degradation time of CHL in the soil.

[0102] Table 2. Zeta potential of chlorantraniliprole microcapsules in Example 1

[0103]

[0104] As shown in Table 2, the average Zeta potential of the chlorantraniliprole microcapsules in Example 1 is +34.1.

[0105] Example 2

[0106] Preparation process of ionic liquids:

[0107] Ionic liquid CHO-10: Weigh 40 mmol of triethanolamine and dissolve it in 50 mL of ethanol. Then add 50 mmol of 1-bromohexane and heat under reflux for 48 h. After vacuum evaporation using a rotary evaporator for 30 min (35 r / min, 50 °C), purify the solution with ethyl acetate and ultrapure water to remove excess raw materials. Take the aqueous phase, concentrate it by rotary evaporation, and dry it in an oven for 5 h to remove excess water, thus obtaining ionic liquid CHO-10.

[0108] Ionic liquid CHO-10-SA: Dissolve 5 mL of ionic liquid CHO-10 in 50 mL of deionized water, add 1 g of sodium salicylate, stir at room temperature for 10 min, the reaction solution will separate into oil and water phases, after cooling to room temperature, take the oil phase, rotary evaporate and purify for later use.

[0109] Microcapsule preparation process:

[0110] Preparation of CHO-CHL-MSH-10 microcapsules: 1 mL of CHO-10-SA ionic liquid and 0.05 g of CHL were placed in a 2 mL storage tube. The mixture was sonicated for 2 min (40 kHz, 120 W), then heated in a 50 °C water bath for 5 min and shaken well. 1 mL of the above mixture and 1 mL of TEOS were added to 49 mL of deionized water. The mixture was sonicated for 2 min (40 kHz, 120 W) to form a milky white suspension. Sonication was continued for another 5 min, while simultaneously adding 50 μL of 25% ammonia solution. After the sonication reaction stopped, the reaction solution was aged at room temperature. After 12 h, the reaction solution was centrifuged (5000 rpm, 5 min). The white solid product was washed once with deionized water and dried at 50 °C for 5 h to obtain white CHO-CHL-MSH-10 microcapsule powder.

[0111] SEM analysis was performed on the chlorantraniliprole microcapsules of Example 2, and the results are as follows: Figure 10 As shown. By Figure 10 It can be seen that the microcapsules are spherical in appearance, have a good appearance, smooth surface, less adsorbed drug, good dispersibility, and large particle size, with an average particle size of about 2 μm.

[0112] Example 3

[0113] Preparation process of ionic liquids:

[0114] Ionic liquid CHO-14: Weigh 40 mmol of triethanolamine and dissolve it in 50 mL of ethanol. Then add 50 mmol of 1-bromononane and heat under reflux for 48 h. After vacuum evaporation using a rotary evaporator for 30 min (35 r / min, 50 °C), purify it with ethyl acetate and ultrapure water to remove excess raw materials. Take the aqueous phase, concentrate it by rotary evaporation, and dry it in an oven for 5 h to remove excess water, thus obtaining ionic liquid CHO-8.

[0115] Ionic liquid CHO-14-SA: Dissolve 5 mL of ionic liquid CHO-14 in 50 mL of deionized water, add 1 g of sodium salicylate, stir at room temperature for 10 min, the reaction solution will separate into oil and water phases, after cooling to room temperature, take the oil phase, rotary evaporate and purify for later use.

[0116] Microcapsule preparation process:

[0117] Preparation of CHO-CHL-MSH-14 microcapsules: 1 mL of CHO-14-SA ionic liquid and 0.05 g of CHL were placed in a 2 mL storage tube. The mixture was sonicated for 2 min (40 kHz, 120 W), then heated in a 50 °C water bath for 5 min, and shaken well. 1 mL of the above mixture and 1 mL of TEOS were added to 49 mL of deionized water. The mixture was sonicated for 2 min (40 kHz, 120 W) to form a milky white suspension. Sonication was continued for another 5 min, while simultaneously adding 50 μL of 25% ammonia solution. After the sonication reaction stopped, the reaction solution was aged at room temperature. After 12 h, the reaction solution was centrifuged (5000 rpm, 5 min). The white solid product was washed once with deionized water and dried at 50 °C for 5 h to obtain white CHO-CHL-MSH-14 microcapsule powder.

[0118] SEM analysis was performed on the chlorantraniliprole microcapsules of Example 3, and the results are as follows: Figure 11 As shown. By Figure 11 It can be seen that the microcapsules are spherical in appearance, have good morphology, good dispersibility, a small number of microcapsules agglomerate, and have a large particle size, with an average particle size of about 2 μm.

[0119] Comparative Example 1

[0120] Preparation process of ionic liquids:

[0121] Ionic liquid CHO: Weigh 40 mmol of triethanolamine and dissolve it in 50 mL of ethanol. Then add 50 mmol of 1-bromobutane. Heat under reflux for 48 h, then evaporate under vacuum for 30 min using a rotary evaporator (35 r / min, 50 °C). Purify by liquid chromatography with ethyl acetate and ultrapure water to remove excess raw materials. Take the aqueous phase, concentrate by rotary evaporation, and dry in an oven for 5 h to remove excess water, thus obtaining ionic liquid CHO-4.

[0122] Ionic liquid CHO-4-SA: Dissolve 5 mL of ionic liquid CHO in 50 mL of deionized water, add 1 g of sodium salicylate, stir at room temperature for 10 min, the reaction solution will separate into oil and water phases, after cooling to room temperature, take the oil phase, rotary evaporate and purify for later use, the structural formula is shown in the figure below, n=4, m=9.

[0123]

[0124] Microcapsule preparation process:

[0125] Preparation of CHO-CHL-MSH-4 microcapsules: 1 mL of CHO-SA ionic liquid was placed in a 2 mL storage tube and sonicated for 2 min (40 kHz, 120 W). The mixture was then heated in a 50 °C water bath for 5 min and shaken well. 1 mL of the above ionic liquid and 1 mL of TEOS were added to 49 mL of deionized water and sonicated for 2 min (40 kHz, 120 W) to form a milky white suspension. Sonication continued for another 5 min, while simultaneously adding 50 μL of 25% ammonia solution. After the sonication reaction stopped, the reaction solution was aged at room temperature. After 12 h, the reaction solution was centrifuged (5000 rpm, 5 min), washed once with deionized water, and dried at 50 °C for 5 h. The dried white powder was dispersed in 50 mL of ethanol, heated under reflux for 6 h, filtered, and then dried at 50 °C for 5 h to obtain white CHO-CHL-MSH-4 microcapsules.

[0126] Transmission electron microscopy analysis was performed on CHO-CHL-MSH-4 prepared in Comparative Example 1, and the results are as follows: Figure 12 As shown. By Figure 12 It can be seen that the formed material is prone to agglomeration, has an excessively large size, and does not generate independent microcapsule particles.

[0127] Bioassay Comparison: Field trial effects of the microcapsules prepared in Example 1 compared with those of chlorantraniliprole technical;

[0128] The toxicity of chlorantraniliprole and chlorantraniliprole microcapsules to 5th instar Asian grasshopper larvae was determined using the micro-droplet method, and the results are shown in Table 3. Table 3 shows that the contact toxicity of both agents was significantly higher with chlorantraniliprole microcapsules than with chlorantraniliprole technical.

[0129] Table 3. Field trial results of the microcapsules prepared in Example 1 and chlorantraniliprole technical.

[0130]

[0131] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A choline ionic liquid, characterized in that, It has the structure shown in Equation I: The n is 10 to 14, and m = 2n + 1.

2. The method for preparing the choline ionic liquid according to claim 1, characterized in that, Includes the following steps: Triethanolamine, a polar organic solvent, and a compound with the structural formula C n H m A nucleophilic substitution reaction was carried out on a mixture of compounds X to give the compound shown in Formula II; wherein X is a halogen atom. The compound shown in Formula II is mixed with water and salicylate to undergo an ion exchange reaction to obtain the choline ionic liquid.

3. The preparation method according to claim 2, characterized in that, The triethanolamine and the structural formula C n H m The molar ratio of compound X is 1:0.5 to 1.

5.

4. The preparation method according to claim 2, characterized in that, The polar organic solvent includes one or more of ethanol, methanol, and acetonitrile.

5. The preparation method according to claim 2 or 3, characterized in that, The nucleophilic substitution reaction is carried out under reflux conditions for 24–96 hours.

6. The application of the choline ionic liquid according to claim 1 or the choline ionic liquid prepared by the preparation method according to any one of claims 2 to 5 in the preparation of microcapsules.

7. A method for preparing chlorantraniliprole microcapsules, characterized in that, Includes the following steps: Chlorantraniliprole was dissolved in a choline ion liquid to obtain a chlorantraniliprole solution; The chlorantraniliprole solution was mixed with a liquid silicon source, an alkaline source, and water to carry out a hydrolysis reaction, thereby obtaining the chlorantraniliprole microcapsules. The choline ionic liquid is the choline ionic liquid according to claim 1 or the choline ionic liquid prepared by the preparation method according to any one of claims 2 to 5.

8. The preparation method according to claim 7, characterized in that, The liquid silicon source includes TEOS, and the alkali source includes ammonia and / or sodium hydroxide solution.

9. The chlorantraniliprole microcapsules prepared by the method according to claim 7 or 8, characterized in that, It has a core-shell structure, with the core consisting of choline ionic liquid and chlorantraniliprole, and the shell consisting of silica.

10. The use of the chlorantraniliprole microcapsules according to claim 9 in the preparation of insecticides.

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