A pesticide microcapsule suspension-suspension concentrate and its preparation method and application

Abstract

The embodiment of the present invention relates to a pesticide microcapsule suspension-suspension agent and a preparation method and application thereof, and relates to the field of pesticides, including cyprofen benzoate and microencapsulated emamectin benzoate suspended in an aqueous phase, and a dispersant acceptable to suspension pesticides; the microcapsule suspension-suspension agent comprises the following raw materials for forming microencapsulated emamectin benzoate suspended in an aqueous phase: urea-formaldehyde resin prepolymer aqueous solution, emamectin benzoate emulsifiable concentrate, buffer solution and acidic solution, wherein the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate is (0.1-5.5): 1, the pH value of the buffer solution is 3.5-5.5, and the pH value of the acidic solution is 2.5-5. Compared with other dosage forms of emamectin benzoate·cyprofen benzoate, the microcapsule suspension-suspension agent containing emamectin benzoate and cyprofen benzoate of the present invention has the characteristics of a long lasting period, thereby reducing the number of medications and the dosage, saving costs, less organic solvents, and reducing pollution to the environment.

Description

Technical Field

[0001] The invention relates to the field of pesticides, and in particular to a pesticide microcapsule suspension-suspending agent and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Cyproflanilide, English common name cyproflanilide, test code CAC-I-785. IUPAC name: 3′-[({2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl}amino)carbonyl]-N-(cyclopropanemethyl)-2′,4-difluorobenzanilide; CAS name: N-[3-[[[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-N-(cyclopropylmethyl)-4-fluorobenzamide. CAS registration number: 2375110-88-4; molecular formula: C 28 H 17 F 12 N2O2. The structural formula is shown in Formula 1:

[0004]

[0005] Cyprodinil is a diamide insecticide independently developed by Taihe International, classified as IRAC classification group 30, with the characteristics of high efficiency, low toxicity, and a wide insecticide spectrum. It has now entered the registration trial stage and is used to control Lepidoptera, Coleoptera and Thysanoptera pests, etc. The dosage is 1-2g / mu, and it has excellent control effects on the stem borer, rice leaf roller, beet armyworm, Spodoptera litura, diamondback moth, fall armyworm, apple leaf roller, pear borer, flea beetle, leaf beetle, and some thrips.

[0006] Emamectin Benzoate, full name is Emamectin Benzoate, English trade name is Emamectin Benzoate, molecular formula is C 49 H 75 NO 13 C7H6O2, the structural formula is shown in Formula 2:

[0007]

[0008] Emamectin benzoate is a new type of highly effective semi-synthetic antibiotic insecticide synthesized from the fermentation product avermectin B1. It has the characteristics of ultra-high efficiency, low toxicity, no residue, and no pollution. Compared with avermectin, its insecticidal activity is improved by 1-3 orders of magnitude. It has extremely high activity against lepidopteran larvae and many other pests and mites. It has both stomach poisoning and contact killing effects. It has a very good effect at a very low dose (0.084-2g / ha). In the process of pest control, it does not harm beneficial insects, which is conducive to the comprehensive control of pests. In addition, it expands the insecticidal spectrum, reduces toxicity to humans and animals, and has no cross-resistance with other types of pesticides. Common preparations of emamectin benzoate on the market are mainly emulsifiable concentrates and water-dispersible granules. The former contains a large amount of organic solvents and pollutes the environment. The latter is added with fillers and then crushed and squeezed into granules. The preparation has a high content and is easy to produce harmful dust. In addition, it has poor dispersibility and low efficacy when applied, and requires multiple applications. In addition to increasing pest resistance, it also increases the cost of farmers' application.

[0009] Microcapsule suspension uses natural or synthetic polymer materials to form core-shell structured microspheres, which can encapsulate the active ingredients of pesticides and suspend them in water. It is a new type of pesticide formulation with a long lasting effect, a small amount of organic solvents, little harm to operators, and safety to the environment.

[0010] In agricultural production, the use of a single pesticide is prone to causing pests to develop resistance, and the insecticide spectrum is limited. Different types of insect pests often need to be controlled by different pesticide varieties, which has a poor control effect, a long control cycle, and high costs. It also causes serious environmental pollution and cannot solve the actual pest damage in agricultural production. Mixed pesticides generally have advantages such as a wide control spectrum, good control effect, and can delay the resistance of insect pests. Therefore, it is urgent to develop a method for preparing a microcapsule suspension-suspension concentrate of emamectin benzoate and cyproflumizone, so as to obtain a method for preparing a microcapsule suspension-suspension concentrate of emamectin benzoate and cyproflumizone that is stable in storage and can effectively control crop pests, so as to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone that is stable in storage and can effectively control crop pests. Especially for insecticides with synergistic effects, the interaction between the active ingredients of the insecticides makes the effect of the combination better than the theoretical synthesis of the effect of using them alone, so that it can achieve twice the result with half the effort in actual use, which is more popular with users. Summary of the invention

[0011] Purpose of the Invention

[0012] The object of the present invention is to provide a pesticide microcapsule suspension-suspension concentrate and a preparation method and application thereof. The dosage form of the present invention has a high suspension rate, good storage stability, good sustained-release effect, and can kill insects in a long-term manner, and has a better control effect on diseases of various crops.

[0013] Solution

[0014] To achieve the purpose of the present invention, an embodiment of the present invention provides a pesticide composition containing cyflumizone and emamectin benzoate, wherein the pesticide composition is in the form of a microcapsule suspension-suspension concentrate, wherein the microcapsule suspension-suspension concentrate comprises cyflumizone and microencapsulated emamectin benzoate suspended in an aqueous phase, and a dispersant acceptable to pesticides for the microcapsule suspension-suspension concentrate;

[0015] The microcapsule suspension-suspending agent comprises the following raw materials for forming microencapsulated emamectin benzoate suspended in an aqueous phase: a urea-formaldehyde resin prepolymer aqueous solution, emamectin benzoate emulsifiable concentrate, a buffer solution and an acidic solution, wherein the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is (0.1-5.5):1, the pH value of the buffer solution is 3.5-5.5, and the pH value of the acidic solution is 2.5-5.

[0016] Furthermore, the urea-formaldehyde resin prepolymer aqueous solution is polymerized from raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, crosslinking agent and water is 1:(0.5-3):(0.7-2):(0.5-5), optionally 1:(0.58-2.5):(0.7-1.5):(0.5-5), optionally 1:(0.58-2):(1-1.5):(1-4.5), optionally 1:1.2:1:3, optionally 1:(0.58-1.8):(1-1.2):(1.5-4); optionally, the crosslinking agent is selected from one of sodium sulfate and sodium chloride.

[0017] Further, the pH value of the prepolymer aqueous solution is 8-10; optionally, the prepolymer is obtained by polymerization at a temperature of 65-80° C. and a reaction time of 1-2.5 hours;

[0018] Optionally, the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is (1-5.5):(1-2), optionally (1-5.5):(1-1.2), optionally (1-5.5):1, optionally (2.5-3.5):1, optionally 3.5:1.

[0019] The emamectin benzoate emulsifiable concentrate can be prepared by a method well known to those skilled in the art, for example, the emamectin benzoate, an emulsifier and an organic solvent are mixed to obtain the emamectin benzoate emulsifiable concentrate. The emamectin benzoate emulsifiable concentrate may contain raw materials in the following weight ratio: emamectin benzoate, an organic solvent and an emulsifier in a weight ratio of 1:(0.1-7):(0.01-0.5), optionally in a weight ratio of 1:(1.4-7):(0.02-0.5), optionally in a weight ratio of 1:(2-4):(0.07-0.15), optionally in a weight ratio of 1:(1.4-4.5):(0.07-0.15), optionally in a weight ratio of 1:2:0.07.

[0020] Furthermore, the emulsifier is selected from one or more of 600# phosphate (phenylphenol polyoxyethylene ether phosphate), Nongru 500# (calcium alkylbenzene sulfonate), Nongru 400# (benzyl dimethylphenol polyoxyethyl ether), styrene polyoxyethylene ether ammonium sulfate, Nongru BY series (castor oil polyoxyethylene ether), alkyl diphenyl ether disulfonic acid magnesium salt, triethanolamine salt, Nongru 700# (alkylphenol formaldehyde resin polyoxyethyl ether), Ningru 36# (phenylethylphenol formaldehyde resin polyoxyethyl ether), Nongru 1600# (phenylethylphenol polyoxyethyl polypropylene ether), ethylene oxide-propylene oxide block copolymer, OP series (nonylphenol polyoxyethylene ether), Nongru 33# (alkylaryl polyoxyethylene polyoxypropylene ether), Span series (sorbitan monostearate), Tween series (sorbitan fatty acid ester polyoxyethylene ether) or AEO series (fatty alcohol polyoxyethylene ether).

[0021] Furthermore, the organic solvent is selected from one or more of N,N-dimethylformamide, cyclohexanone, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, ethanol, trimethylcyclohexanone, N-octylpyrrolidone, ethanolamine, triethanolamine, isopropylamine, methanol, propanol, butanol, ethylene glycol, methyl oleate, ethyl acetate, vegetable oil, acetonitrile, solvent oil 150# and alkane solvent oil 200#.

[0022] Furthermore, the total concentration of the buffer pair in the buffer solution is 1-5% by weight; the buffer pair in the buffer solution includes at least one of barbital-sodium chloride buffer, citric acid-sodium citrate, phosphoric acid-triethylamine buffer, acetic acid-sodium acetate, potassium dihydrogen phosphate-dipotassium hydrogen phosphate buffer, acetic acid-sodium acetate buffer, ethanol-ammonium acetate buffer, barbital buffer, sodium formate buffer, acetate-lithium salt buffer, and acetic acid-ammonium acetate buffer; and is used to adjust the pH of a mixture of a urea-formaldehyde resin prepolymer aqueous solution and emamectin benzoate emulsifiable concentrate (the first material) to 5.5-7.

[0023] Furthermore, the concentration of the acidic solution is 1-10% by weight; the acidic solution includes at least one of hydrochloric acid, sulfuric acid solution, phosphoric acid solution, acetic acid solution and ammonium chloride solution, which is used to adjust the pH from 5.5-7 to 3.5-5.

[0024] Further, the weight ratio of emamectin benzoate to cyfluthrin is 1:(0.5-10), optionally 1:(4-7), optionally 1:(4.5-6), optionally 1:5.

[0025] Optionally, the average particle size of the ciprofloxacin is 1-5 μm.

[0026] Further, the dispersant is selected from at least one of styrylphenyl polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium methylene bisnaphthalene sulfonate, sodium 1-methylnaphthalene sulfonate formaldehyde condensate, benzylnaphthalene sulfonic acid formaldehyde condensate, sodium dodecylbenzene sulfonate, sodium lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed sodium lignin sulfonate, carboxylate structure polymer dispersant, sodium succinate sulfonate, pull-opening powder, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, polycarboxylate and polyoxyethylene polyoxypropylene block copolymer; optionally, the weight ratio of the dispersant to emamectin benzoate is (0.1-20):1;

[0027] Furthermore, the pesticide microcapsule suspension-suspension concentrate also includes one or more of a thickener and an antifreeze agent.

[0028] On the other hand, the present invention also provides a method for preparing the pesticide microcapsule suspension-suspension concentrate, comprising the following steps:

[0029] S1, mixing the urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate uniformly in a weight ratio of (0.1-5.5):1 to obtain a first material;

[0030] S2, mixing the first material obtained in step S1 with a buffer solution to obtain a second material, wherein the pH value of the second material is 5.5-7;

[0031] S3, mixing the second material obtained in step S2 with an acidic solution to obtain a third material, wherein the pH value of the third material is 3.5-5;

[0032] S4, stirring the third material obtained in step S3 at a temperature of 45-60° C. for 3-4.5 hours to obtain a fourth material;

[0033] S5, mixing the fourth material obtained in step S4 with the first dispersant, the first thickener and the first antifreeze agent to obtain emamectin benzoate microcapsule suspension;

[0034] S6, mixing the obtained emamectin benzoate microcapsule suspension, cyflumizone suspension and a second dispersant to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone.

[0035] Further, in step S1, the urea-formaldehyde resin prepolymer aqueous solution is polymerized from raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, cross-linking agent and water is 1: (0.5-3): (0.7-2): (0.5-5), optionally 1: (0.58-2.5): (0.7-1.5): (0.5-5), optionally 1: (0.58-2): (1-1.5): (1-4.5), optionally 1: (0.58-1.8): (1-1.2): (1.5-4); optionally, the cross-linking agent is selected from one of sodium sulfate and sodium chloride; optionally, the polymerization conditions include: pH value of 8-10, temperature of 65-80° C., and reaction time of 1-2.5 hours;

[0036] According to the present invention, appropriate reaction conditions can increase the thickness of the capsule shell, improve the particle size distribution of the capsule spheres, improve the coverage rate of the microcapsules, and thus improve the storage stability of the microcapsule suspension. Preferably, the mixing in step S1 is carried out under stirring conditions, and the stirring speed is 1500-2800 rpm; and / or, in step S2, the mixing is carried out under stirring conditions, and the stirring speed is 1000-1300 rpm; and / or, in step S3, the mixing is carried out under stirring conditions, and the stirring speed is 1800-2200 rpm.

[0037] Further, in step S6, the weight ratio of the emamectin benzoate microcapsule suspension, cyfluthrin suspension and the second dispersant obtained in step S5 is 1:(0.02-4):(0.02-2.5), optionally 1:(0.5-1.3):(0.02-0.2), optionally 1:(0.65-1.15):(0.03-0.15), optionally 1:(0.67-1.1):(0.03-0.14), optionally 1:0.74:0.03.

[0038] According to the present invention, the average particle size of the cycloflumizone microparticles in the cycloflumizone suspension in step S6 can be 1-5 microns. The preparation method of the cycloflumizone suspension in step S6 can be a preparation method well known to those skilled in the art, and the present invention has no particular limitation thereto. For example, the preparation method of the cycloflumizone suspension comprises: mixing, dispersing and grinding the cycloflumizone technical, the third dispersant, the second thickener, the second antifreeze agent and water; the cycloflumizone suspension is a suspended microparticle with an average particle size of 1-5 μm.

[0039] Furthermore, the first dispersant, the second dispersant and the third dispersant are each independently selected from at least one of styrylphenyl polyoxyethylene ether nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium methylene bisnaphthalene sulfonate, sodium 1-methylnaphthalene sulfonate formaldehyde condensate, benzylnaphthalene sulfonic acid formaldehyde condensate, sodium dodecylbenzene sulfonate, sodium lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed sodium lignin sulfonate, carboxylate structure polymer dispersant, sodium succinate sulfonate, opening powder, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, polycarboxylate and polyoxyethylene polyoxypropylene block copolymer.

[0040] Furthermore, the first thickener and the second thickener are each independently selected from at least one of organic bentonite, white carbon black, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, xanthan gum, guar gum and sodium carboxymethyl cellulose.

[0041] Further, the first antifreeze agent and the second antifreeze agent are each independently selected from at least one of ethylene glycol, glycerol, 1,2-propylene glycol, sorbitol and urea;

[0042] Furthermore, in step S5, the weight ratio of the fourth material to the first dispersant, the first thickener and the first antifreeze agent is 1: (0.01-0.3): (0.001-0.03): (0.01-0.2), optionally 1: (0.02-0.25): (0.02-0.25): (0.05-0.5), optionally 1: (0.02-0.2): (0.02-0.05): (0.15-0.5), optionally 1: 0.02: 0.05: 0.5.

[0043] Furthermore, the weight ratio of the cyfluthrin to the third dispersant, the second thickener, the second antifreeze agent and water is 1:(0.02-1):(0.01-0.3):(0.1-0.5):(0.5-30), optionally 1:(0.2-0.5):(0.01-0.3):(0.1-0.5):(1-20), optionally 1:0.5:0.01:(1-3).

[0044] In the composition of the present invention, the original drug of emamectin benzoate is acidic and stable, and is easily decomposed under alkaline conditions. The present invention can also include adjusting the acidity and alkalinity of the fourth material obtained in step S4 to acidity before step S5, and then performing step S5 to adjust the acidity and alkalinity of the fourth material to acidity with the first dispersant, the first thickener and the first antifreeze to obtain an emamectin benzoate microcapsule suspension. By mixing the fourth material with the first dispersant, the first thickener and the first antifreeze, the phenomenon of microcapsule aggregation, precipitation, and hardening can be avoided. The method for adjusting the acidity and alkalinity of the fourth material to acidity can adopt conventional methods in the art. For example, it can be adjusted by a buffer solution, an acid solution, etc.

[0045] In another aspect, there is provided an application of the pesticide microcapsule suspension-suspension concentrate or the pesticide microcapsule suspension-suspension concentrate prepared by the method in controlling plant pests; optionally, the plant pests include at least one of Lepidoptera pests and Coleoptera pests; optionally, the plant pests include at least one of Rice stem borer and Rice leaf folder.

[0046] On the other hand, a method for using the pesticide microcapsule suspension-suspension concentrate or the pesticide microcapsule suspension-suspension concentrate prepared by the method is provided, characterized in that the application amount of the pesticide microcapsule suspension-suspension concentrate is 0.5-20 g / mu of active ingredient, optionally 1-5 g / mu.

[0047] Beneficial Effects

[0048] (1) In the dosage form of the present invention, emamectin benzoate and cyfluthrin have a high suspension rate, good storage stability, good sustained-release effect and long-term insecticidal effect, and have a better control effect on diseases of various crops.

[0049] (2) The microcapsule suspension-suspending agent of the present invention has good heat storage stability and low temperature storage stability, and the measured suspension rate is above 95%.

[0050] (3) The effects of the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone prepared by the present invention are much better than those of a single dose of emamectin benzoate water emulsion and a single dose of cyproflumizone suspension concentrate. Compared with other dosage forms of emamectin benzoate and cyproflumizone, the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone of the present invention has the characteristics of a long lasting effect, thereby reducing the number of times and dosage of medication, saving costs, using less organic solvents, and reducing pollution to the environment. DETAILED DESCRIPTION

[0051] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "including" or its variations such as "comprising" or "including" will be understood to include the stated elements or components, without excluding other elements or other components.

[0052] In addition, in order to better illustrate the present invention, numerous specific details are provided in the specific embodiments below. It should be understood by those skilled in the art that the present invention can also be implemented without certain specific details. In some embodiments, raw materials, elements, methods, means, etc. well known to those skilled in the art are not described in detail, so as to highlight the main purpose of the present invention.

[0053] In the following examples, all raw materials are commercially available products.

[0054] Among them, cyprodinil flubendiamide was purchased from Nantong Taihe Chemical Co., Ltd.; emamectin benzoate was purchased from Jingmen Jinxianda Biotechnology Co., Ltd.; urea, formaldehyde, ethylene glycol, glycerol and 1,2-propylene glycol were purchased from Beijing Chemical Plant; styrylphenyl polyoxyethylene ether, sodium dodecyl sulfate, sodium lignin sulfonate, sodium dodecylbenzene sulfonate, styrylphenyl polyoxyethylene ether, and fatty alcohol polyoxyethylene ether were all purchased from Shanghai Jieshi Chemical Co., Ltd.; magnesium aluminum silicate was purchased from Hunan Pengtai High-tech Materials Co., Ltd.; bentonite was purchased from Zhejiang Anji Tianlong Organic Bentonite Co., Ltd.; silicone defoamer was purchased from Shanghai Maitu High-tech Materials Group; xanthan gum was purchased from Shandong Zhongxuan Co., Ltd.; sodium benzoate was purchased from Beijing Huamei Zhibo Technology Co., Ltd.; solvent oil 200# was purchased from Jiangsu Hualun Chemical Co., Ltd.; petroleum ether was purchased from Xilong Chemical Co., Ltd.; ethyl acetate was purchased from Xilong Chemical Co., Ltd.; the rest were commercially purchased reagents.

[0055] Example 1

[0056] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:1.2:1:3.

[0057] The emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate is 1:2:0.07.

[0058] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed uniformly at a weight ratio of 3.5:1 at a stirring speed of 2500 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total buffer concentration of 1.5% by weight and a pH value of 3.5 was uniformly added to the first material within 1 hour, and the mixture was mixed uniformly at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 7.0; at room temperature, a phosphoric acid solution with a concentration of 5% by weight was added to the first material within 1.5 hours. uniformly adding it to the above-mentioned second material, mixing at a stirring speed of 2000 rpm to obtain a third material whose pH value is adjusted to 4.8; stirring the third material at 56°C for 3.5 hours to obtain a fourth material; adding fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol to the fourth material and mixing them evenly to obtain a emamectin benzoate microcapsule suspension, wherein the weight ratio of the fourth material to fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol is 1:0.02:0.05:0.5, and a 4.45% emamectin benzoate microcapsule suspension is obtained.

[0059] 30% ciprofloxacin suspension concentrate: 30% by weight of ciprofloxacin (content is 95%), 1% by weight of sodium dodecylbenzene sulfonate, 5% by weight of fatty alcohol polyoxyethylene ether, 0.3% by weight of xanthan gum, 4% by weight of ethylene glycol, and 59.7% by weight of water; fully mixed and dispersed, and after uniform dispersion, passed into a sand mill for sand grinding, and sand grinding to a suspension with an average particle size of less than 5 microns, to obtain a 30% ciprofloxacin suspension concentrate.

[0060] Finally, the emamectin benzoate microcapsule suspension and the cyproflumizone suspension are mixed, and then styrylphenyl polyoxyethylene ether is added and stirred evenly to obtain the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone of the present embodiment. The weight ratio of the emamectin benzoate microcapsule suspension, the cyproflumizone suspension, and the styrylphenyl polyoxyethylene ether is 1:0.74:0.03, and the weight ratio of the emamectin benzoate to the cyproflumizone is 1:5.

[0061] Example 2

[0062] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:0.58:1:1.5.

[0063] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate (the same as the emamectin benzoate emulsifiable concentrate in Example 1) were mixed uniformly at a weight ratio of 2.5:1 at a stirring speed of 2200 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total buffer concentration of 1.5% by weight and a pH value of 3.5 was uniformly added to the first material within 1 hour, and mixed uniformly at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 6.8; at room temperature, a phosphorus solution with a concentration of 5% by weight was added to the first material; The acid solution is uniformly added to the second material within 1 hour, and the mixture is mixed at a stirring speed of 1900 rpm to obtain a third material whose pH value is adjusted to 4.5; the third material is stirred at 50°C for 4 hours to obtain a fourth material; fatty alcohol polyoxyethylene ether, xanthan gum and glycerol are added to the fourth material, and the mixture is mixed uniformly to obtain a emamectin benzoate microcapsule suspension, wherein the weight ratio of the fourth material to the fatty alcohol polyoxyethylene ether, xanthan gum and glycerol is 1:0.03:0.02:0.2 to obtain a 7.3% emamectin benzoate microcapsule suspension. The preparation method of the cyproflumizone suspension is the same as that of Example 1.

[0064] Finally, the emamectin benzoate microcapsule suspension and the cyflumizone suspension are mixed, and then benzylnaphthalenesulfonic acid formaldehyde condensate and water are added, and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone. The weight ratio of the emamectin benzoate microcapsule suspension, the cyflumizone suspension, and the benzylnaphthalenesulfonic acid formaldehyde condensate is 1:1.1:0.14, and the weight ratio of the emamectin benzoate to the cyflumizone is 1:4.5.

[0065] Example 3

[0066] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:1.8:1.2:4.

[0067] The emamectin benzoate (content of 95%), alkane solvent oil 200# and polyoxyethylene styrylphenyl ether are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate (content of 95%), alkane solvent oil 200# and polyoxyethylene styrylphenyl ether is 1:4:0.15.

[0068] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed uniformly at a weight ratio of 3:1 at a stirring speed of 2700 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total buffer concentration of 1.5% by weight and a pH value of 3.5 was uniformly added to the first material within 1.5 hours, and mixed uniformly at a stirring speed of 1300 rpm to obtain a second material with a pH value adjusted to 6.5; at room temperature, a phosphoric acid solution with a concentration of 5% by weight was added to the first material for 1 hour. The invention discloses a novel nanostructured carbonyl phosphate (N-butyl ester) ...

[0069] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0070] Finally, the emamectin benzoate microcapsule suspension and the cycloflumizone suspension are mixed, and then the polyoxyethylene polyoxypropylene block copolymer and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cycloflumizone. The weight ratio of the emamectin benzoate microcapsule suspension to the cycloflumizone suspension and the polyoxyethylene polyoxypropylene block copolymer is 1:0.67:0.03, and the weight ratio of the emamectin benzoate to the cycloflumizone is 1:6.

[0071] Example 4

[0072] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:2:1.5:4.5.

[0073] The emamectin benzoate (content of 95%), mineral oil and castor oil polyoxyethylene ether are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate (content of 95%), mineral oil and castor oil polyoxyethylene ether is 1:3.5:0.5.

[0074] The urea formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed at a weight ratio of 5.5:1 at a stirring speed of 2100 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total concentration of 1.5% by weight of a buffer pair with a pH value of 3.5 was uniformly added to the first material within 1 hour, and mixed at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 6.3; at room temperature, a phosphoric acid solution with a concentration of 5% by weight was added to the first material for 1.5 hours. The invention discloses a novel nanostructured carbonyl chloride (N-butyl acetate) ...

[0075] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0076] Finally, the emamectin benzoate microcapsule suspension and the cycloflumizone suspension are mixed, and then the polyoxyethylene polyoxypropylene block copolymer and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cycloflumizone. The weight ratio of the emamectin benzoate microcapsule suspension to the cycloflumizone suspension and the polyoxyethylene polyoxypropylene block copolymer is 1:0.25:0.5, and the weight ratio of the emamectin benzoate to the cycloflumizone is 1:3.5.

[0077] Example 5

[0078] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:0.58:1:1.

[0079] The emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate is 1:2.15:0.02.

[0080] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed uniformly at a weight ratio of 1:1.2 at a stirring speed of 2400 rpm to obtain a first material; then, at room temperature, an acetic acid-ammonium acetate buffer solution with a total concentration of 1.5% by weight of a buffer pair with a pH value of 3.5 was uniformly added to the first material within 1 hour, and mixed uniformly at a stirring speed of 1300 rpm to obtain a second material with a pH value adjusted to 6.8; at room temperature, a 5% by weight phosphoric acid solution was uniformly added to the first material within 1.5 hours. The invention discloses a method for preparing a diatomaceous earth salt microcapsule suspension comprising: adding the diatomaceous earth salt to the second material at a speed of 1800 rpm, mixing evenly at a stirring speed of 1800 rpm to obtain a third material whose pH value is adjusted to 4.6; stirring the third material at 60°C for 2 hours to obtain a fourth material; adding fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol to the fourth material and mixing evenly to obtain a diatomaceous earth salt microcapsule suspension, wherein the weight ratio of the fourth material to fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol is 1:0.02:0.02:0.17 to obtain a 11.5% diatomaceous earth salt microcapsule suspension.

[0081] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0082] Finally, the emamectin benzoate microcapsule suspension and the cyproflumizone suspension are mixed, and then styrylphenyl polyoxyethylene ether and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone. The weight ratio of the emamectin benzoate microcapsule suspension, the cyproflumizone suspension, and the styrylphenyl polyoxyethylene ether is 1:2.68:0.45, and the weight ratio of the emamectin benzoate to the cyproflumizone is 1:7.

[0083] Example 6

[0084] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:1:0.7:0.5.

[0085] The emamectin benzoate, mineral oil and ethylene oxide-propylene oxide block copolymer are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate, mineral oil and ethylene oxide-propylene oxide block copolymer is 1:1.4:0.04.

[0086] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed at a weight ratio of 4.5:1 at a stirring speed of 2100 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total concentration of 1.5% by weight of a buffer pair with a pH value of 3.5 was uniformly added to the first material within 0.5 hours, and mixed at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 6.6; at room temperature, a 5% by weight phosphoric acid solution was uniformly added to the first material within 1.5 hours; The second material is mixed evenly at a stirring speed of 2000 rpm to obtain a third material whose pH value is adjusted to 4.9; the third material is stirred for 2 hours at 60°C to obtain a fourth material and the pH value of the fourth material is adjusted to 7; fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol are added to the fourth material and mixed evenly to obtain a emamectin benzoate microcapsule suspension, wherein the weight ratio of the fourth material to fatty alcohol polyoxyethylene ether, magnesium aluminum silicate and ethylene glycol is 1:0.2:0.05:0.25 to obtain a 4.95% emamectin benzoate microcapsule suspension.

[0087] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0088] Finally, the emamectin benzoate microcapsule suspension and the cycloflumizone suspension are mixed, and then the polyoxyethylene polyoxypropylene block copolymer and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cycloflumizone. The weight ratio of the emamectin benzoate microcapsule suspension to the cycloflumizone suspension and the polyoxyethylene polyoxypropylene block copolymer is 1:0.17:0.02, and the weight ratio of the emamectin benzoate to the cycloflumizone is 1:1.

[0089] Example 7

[0090] Urea, formaldehyde, sodium chloride and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium chloride and water was 1:2.2:1.5:5.

[0091] The emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate, alkane solvent oil 200# and calcium dodecylbenzene sulfonate is 1:2:0.06.

[0092] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed at a weight ratio of 4.7:1 at a stirring speed of 2500 rpm to obtain a first material; then, at room temperature, a citric acid-sodium citrate buffer solution with a total concentration of 1.5% by weight of a buffer pair with a pH value of 3.5 was uniformly added to the first material within 1.5 hours, and mixed at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 6.5; at room temperature, a 5% by weight phosphoric acid solution was added to the first material for 1.5 hours. The invention discloses a novel nanostructured carbonyl phosphate (N-butyl ester) ...

[0093] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0094] Finally, the emamectin benzoate microcapsule suspension and the cyflumizone suspension are mixed, and then benzylnaphthalenesulfonic acid formaldehyde condensate and water are added, and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone. The weight ratio of the emamectin benzoate microcapsule suspension, the cyflumizone suspension, and the benzylnaphthalenesulfonic acid formaldehyde condensate is 1:1.33:0.2, and the weight ratio of the emamectin benzoate to the cyflumizone is 1:8.5.

[0095] Example 8

[0096] Urea, formaldehyde, sodium chloride and water were mixed and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium chloride and water was 1:2.8:1:5.

[0097] The emamectin benzoate, alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate, alkane solvent oil 200# and calcium dodecylbenzene sulfonate is 1:2.4:0.05.

[0098] The urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed at a weight ratio of 3.5:1 at a stirring speed of 2500 rpm to obtain a first material; then, at room temperature, a potassium dihydrogen phosphate-dipotassium hydrogen phosphate buffer solution with a total concentration of 3% by weight of a buffer pair with a pH value of 3.5 was uniformly added to the first material within 0.5 hours, and mixed at a stirring speed of 1200 rpm to obtain a second material with a pH value adjusted to 6.3; at room temperature, a 5% by weight phosphoric acid solution was stirred for 1.5 hours. The invention discloses a novel nanostructured carbonyl phosphate (N-butyl ester) ...

[0099] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0100] Finally, the emamectin benzoate microcapsule suspension and the cyflumizone suspension are mixed, and then the desugared condensed sodium lignin sulfonate and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone. The weight ratio of the emamectin benzoate microcapsule suspension, the cyflumizone suspension, and the desugared condensed sodium lignin sulfonate is 1:1.87:0.5, and the weight ratio of the emamectin benzoate to the cyflumizone is 1:10.

[0101] Example 9

[0102] Urea, formaldehyde, sodium sulfate and water were mixed, and reacted at a pH of 8.5 and a temperature of 72° C. for 1.5 hours to obtain a urea-formaldehyde resin prepolymer aqueous solution, wherein the weight ratio of formaldehyde, urea, sodium sulfate and water was 1:0.5:0.3:5.

[0103] The emamectin benzoate, alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate, alkane solvent oil 200# and calcium dodecylbenzene sulfonate is 1:4.5:0.04.

[0104] The polyisocyanate-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate were mixed uniformly at a weight ratio of 1:2 at a stirring speed of 2200 rpm to obtain a first material; then, at room temperature, a 3% by weight potassium dihydrogen phosphate-dipotassium hydrogen phosphate buffer solution was uniformly added to the first material within 1 hour, and mixed uniformly at a stirring speed of 1100 rpm to obtain a second material whose pH value was adjusted to 6.4; at room temperature, a 5% by weight phosphoric acid solution was uniformly added to the first material within 1.5 hours. The second material is mixed evenly at a stirring speed of 2000 rpm to obtain a third material whose pH value is adjusted to 4.2; the third material is stirred at 60°C for 2 hours to obtain a fourth material; fatty alcohol polyoxyethylene ether, xanthan gum and ethylene glycol are added to the fourth material and mixed evenly to obtain a emamectin benzoate microcapsule suspension, wherein the weight ratio of the fourth material to the fatty alcohol polyoxyethylene ether, xanthan gum and ethylene glycol is 1:0.03:0.25:0.05 to obtain a 4.53% emamectin benzoate microcapsule suspension.

[0105] The preparation method of the ciprofloxacin suspension concentrate is the same as that in Example 1.

[0106] Finally, the emamectin benzoate microcapsule suspension and the cyflumizone suspension are mixed, and then polycarboxylate and water are added and stirred evenly to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone. The weight ratio of the emamectin benzoate microcapsule suspension, the cyflumizone suspension and the polycarboxylate is 1:0.08:2.5, and the weight ratio of the emamectin benzoate to the cyflumizone is 1:0.5.

[0107] Comparative Example 1

[0108] The difference from Example 1 is that when preparing the urea-formaldehyde resin prepolymer aqueous solution, no sodium sulfate is added, and formaldehyde, urea and water are directly reacted and polymerized, wherein the weight ratio of formaldehyde, urea and water is 1:1.2:3.

[0109] Comparative Example 2

[0110] The difference from Example 4 is that when preparing the urea-formaldehyde resin prepolymer aqueous solution, the weight ratio of formaldehyde, urea, sodium sulfate and water is 1:2:2.5:4.5.

[0111] Comparative Example 3

[0112] The difference from Example 5 is that when preparing the urea-formaldehyde resin prepolymer aqueous solution, the weight ratio of formaldehyde, urea, sodium sulfate and water is 1:0.58:0.3:1.

[0113] Comparative Example 4

[0114] The difference from Example 1 is that after obtaining the first material, the pH value of the material is adjusted to 4.5 directly using a 5% by weight phosphoric acid solution without adjusting the pH value using a citric acid-sodium citrate buffer solution or an acetic acid-sodium acetate buffer solution.

[0115] Comparative Example 5

[0116] The difference from Example 1 is that after obtaining the first material, the pH value of the material is adjusted to 7.0 using a citric acid-sodium citrate buffer solution with a total concentration of 1.5% by weight of a buffer pair with a pH value of 3.5, and the second pH adjustment step is not performed.

[0117] Comparative Example 6

[0118] The difference from Example 1 is that the pH value of the third material is adjusted to 3.3 by using hydrochloric acid with a concentration of 5% by weight.

[0119] Comparative Example 7

[0120] The emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate were uniformly mixed to obtain emamectin benzoate emulsifiable concentrate, wherein the weight ratio of the emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate was 1:2:0.07. The cyproflumizone suspension was prepared in the same manner as in Example 1, and the emamectin benzoate emulsifiable concentrate and the cyproflumizone suspension were mixed in a weight ratio of 1:0.3 to obtain an emamectin benzoate·cyproflumizone suspoemulsion.

[0121] Comparative Example 8

[0122] The emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate are uniformly mixed to obtain an emamectin benzoate oil phase, water is slowly dripped into the emamectin benzoate oil phase, and ethylene glycol and xanthan gum are added while dripping to obtain an emamectin benzoate salt emulsion. The weight ratio of the emamectin benzoate (content of 95%), alkane solvent oil 200# and calcium dodecylbenzene sulfonate, water, ethylene glycol and xanthan gum is 1:2:0.07:1.2:0.005:0.001.

[0123] Comparative Example 9

[0124] Preparation of Emamectin Benzoate Microcapsule Suspension

[0125] The raw materials and preparation method of Example 1 were used, except that the ciprofloxacin suspension concentrate was not added.

[0126] Comparative Example 10

[0127] Preparation of ciprofloxacin suspension concentrate

[0128] The raw materials and preparation method of Example 1 are used, except that the emamectin benzoate microcapsule suspension is not added.

[0129] Test Example 1

[0130] This test example is used to test the microcapsule encapsulation efficiency of the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyfluthrin obtained in Examples 1-9 and Comparative Examples 1-6, the flowability, particle size change, hot storage stability and low temperature stability of the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyfluthrin obtained in Examples 1-9 and Comparative Examples 1-6, and the emamectin benzoate·cyfluthrin suspoemulsion obtained in Comparative Example 7.

[0131] 1. Determination of the particle size of the suspension: The particle size of the preparations of each embodiment and comparative example was measured using a laser particle size analyzer.

[0132] 2. Thermal storage stability determination: The preparations of the examples and comparative examples were placed in containers, sealed, and placed in a constant temperature oven at (54±2)°C. After standing for 14 days, the containers were taken out, and the fluidity was observed and the suspension rate was determined.

[0133] 3. Low-temperature stability determination: The preparations of the examples and comparative examples were placed in a container, sealed, and placed in a (0±2)°C refrigerator for 1 hour. Stirring was performed every 15 minutes for 15 seconds each time, and the appearance was observed for changes. The preparations were placed at (0±2)°C for 7 days, and then taken out and placed at room temperature for recovery. The fluidity was observed and the suspension rate was determined.

[0134] 4. Determination of suspension rate: Determined according to GB / T 14825-2006 method for determination of suspension rate of pesticides. The results are shown in Table 1.

[0135] 5. Determination of microcapsule encapsulation efficiency: The content of free emamectin benzoate in the preparations of each embodiment and comparative example was determined by high performance liquid chromatography, and the encapsulation efficiency was calculated:

[0136] Encapsulation rate (%) = (amount of original drug added - amount of free original drug) / amount of original drug added * 100%.

[0137] Table 1 Performance of each embodiment and comparative example

[0138]

[0139]

[0140] From Table 1, it can be seen that the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone obtained by the preparation method provided by the present invention (Examples 1-9) has a substantially unchanged particle size after hot storage, and has good hot storage stability and low-temperature storage stability, and the measured suspension rate is above 95%, which is higher than the physical properties of the suspoemulsion. Changing the preparation method (Comparative Examples 1-6) makes it difficult to obtain a qualified, stable microcapsule suspension-suspension concentrate product containing emamectin benzoate and cyflumizone with an encapsulation rate of more than 90%.

[0141] Test Example 2

[0142] In this test example, the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone obtained in Examples 1-9, and each group of preparations obtained in Comparative Examples 1-5 and Comparative Examples 7-10 were tested for insecticidal performance in paddy fields. Before the test, a certain amount of distilled water was added and stirred evenly, and the concentration of active ingredients in the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone obtained in Examples 1-9, and each group of preparations obtained in Comparative Examples 1-5 and Comparative Examples 7-10 were respectively adjusted to 10% by weight for standby use.

[0143] Test location: A farmer's contracted field in Jingzhou, Hubei, with medium to high soil fertility. The planting area of ​​each sample tested was 1 mu, and the rice variety was Yixiang No. 10. After planting, the rice in each treatment area was managed according to conventional production. No other pesticides were used for other pests and diseases control before the test.

[0144] The specific steps include using a WL-ASBC motorized sprayer, spraying 30kg / mu of pesticide, applying 4g of active ingredient per mu, and spraying the prepared groups of pesticide solutions on the rice in each planting area. The blank control group uses an equal amount of clean water to spray the rice plants in the planting area. When applying the pesticide, use plastic film to cover adjacent plots to prevent mutual interference between the pesticides.

[0145] The control effect was investigated 10, 20, 30 and 50 days after application. The specific test method was carried out in accordance with the "Guidelines for Field Efficacy Tests of Pesticides". Five points were sampled on the diagonal of each plot, and 5 connected clumps were investigated at each point, totaling 25 clumps. The control effect of rice stem borer and rice leaf roller in each treatment area was investigated. The mortality rate was calculated according to formula (1) and the corrected mortality rate was calculated according to formula (2). The results are shown in Table 2.

[0146]

[0147]

[0148] Table 2 Pest control effects of various embodiments and comparative examples

[0149]

[0150] As can be seen from Table 2, the preparation method provided by the present invention enhances the stability and strength of the microcapsule shell by adding a cross-linking agent, adjusts the pH value, and the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone prepared under specific reaction temperature, specific stirring speed, emulsifying dispersant, solvent and other reaction conditions has a good effect of preventing and controlling crop pests after spraying. And the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone prepared by this method has a much better effect than a single dose of emamectin benzoate salt emulsion and a single dose of cyproflumizone suspension concentrate. Compared with other dosage forms of emamectin benzoate and cyproflumizone, the microcapsule suspension-suspension concentrate containing emamectin benzoate and cyproflumizone of the present invention has the characteristics of a long lasting effect, thereby reducing the number of medications and the amount of medication, saving costs, less organic solvents, and reducing pollution to the environment.

[0151] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a pesticide microcapsule suspension-suspension concentrate, It is characterized in that The steps include: S1, mixing the urea-formaldehyde resin prepolymer aqueous solution and the emamectin benzoate emulsifiable concentrate uniformly in a weight ratio of (0.1-5.5):1 to obtain a first material; The weight ratio of urea-formaldehyde resin prepolymer aqueous solution and emamectin benzoate emulsifiable concentrate is (1-5.5):(1-2); the urea-formaldehyde resin prepolymer aqueous solution is polymerized from raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, crosslinking agent and water is 1:(0.5-3):(0.7-2):(0.5-5); the prepolymer aqueous solution is polymerized under the conditions of a temperature of 65-80°C and a reaction time of 1-2.5 hours; the crosslinking agent is selected from one of sodium sulfate and sodium chloride; the pH value of the prepolymer aqueous solution is 8-10; The emamectin benzoate emulsifiable concentrate contains the following raw materials in a weight ratio: emamectin benzoate, an organic solvent and an emulsifier in a weight ratio of 1: (0.1-7): (0.01-0.5); in the emamectin benzoate emulsifiable concentrate, the emulsifier is selected from one or more of 600# phosphate ester, Nongru 500#, Nongru 400#, styrene polyoxyethylene ether ammonium sulfate, Nongru BY series, alkyl diphenyl ether disulfonic acid magnesium salt, triethanolamine salt, Nongru 700#, Ningru 36#, Nongru 1600#, ethylene oxide-propylene oxide block copolymer, Nongru OP series, Nongru 33#, Span series, Tween series or AEO series; S2, mixing the first material obtained in step S1 with a buffer solution to obtain a second material, wherein the pH value of the second material is 5.5-7; the total concentration of the buffer pair in the buffer solution is 1-5% by weight; the buffer pair in the buffer solution includes at least one of barbital-sodium chloride buffer, citric acid-sodium citrate, phosphate-triethylamine buffer, acetic acid-sodium acetate, potassium dihydrogen phosphate-dipotassium hydrogen phosphate buffer, acetic acid-sodium acetate buffer, ethanol-ammonium acetate buffer, barbital buffer, sodium formate buffer, acetate-lithium salt buffer, and acetic acid-ammonium acetate buffer; the pH value of the buffer solution is 3.5-5.5; S3, mixing the second material obtained in step S2 with an acidic solution to obtain a third material, wherein the pH value of the third material is 3.5-5; the concentration of the acidic solution is 1-10% by weight; the acidic solution includes at least one of hydrochloric acid, sulfuric acid solution, phosphoric acid solution, acetic acid solution and ammonium chloride solution; the pH value of the acidic solution is 2.5-5; S4, stirring the third material obtained in step S3 at a temperature of 45-60° C. for 3-4.5 hours to obtain a fourth material; S5, mixing the fourth material obtained in step S4 with the first dispersant, the first thickener and the first antifreeze agent to obtain an emamectin benzoate microcapsule suspension; the weight ratio of the fourth material to the first dispersant, the first thickener and the first antifreeze agent is 1: (0.01-0.3): (0.001-0.03): (0.01-0.2); S6, mixing the obtained emamectin benzoate microcapsule suspension with cyflumizone suspension and a second dispersant to obtain a microcapsule suspension-suspension concentrate containing emamectin benzoate and cyflumizone; the weight ratio of the emamectin benzoate microcapsule suspension, cyflumizone suspension and the second dispersant obtained in step S5 is 1:(0.02-4):(0.02-2.5); the weight ratio of emamectin benzoate to cyflumizone is 1:(0.5-10); The preparation method of the ciprofloxacin suspension comprises: mixing, dispersing and grinding ciprofloxacin technical, a third dispersant, a second thickener, a second antifreeze agent and water; the weight ratio of the ciprofloxacin to the third dispersant, the second thickener, the second antifreeze agent and water is 1: (0.02-1): (0.01-0.3): (0.1-0.5): (0.5-30); the ciprofloxacin suspension is a suspended particle with an average particle size of 1-5 μm; The first dispersant, the second dispersant and the third dispersant are each independently selected from at least one of styrylphenyl polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium methylene bisnaphthalene sulfonate, sodium 1-methylnaphthalene sulfonate formaldehyde condensate, benzylnaphthalene sulfonic acid formaldehyde condensate, sodium dodecylbenzene sulfonate, sodium lignin sulfonate, desugared sodium lignin sulfonate, desugared condensed sodium lignin sulfonate, carboxylate structure polymer dispersant, sodium succinate sulfonate, pull-open powder, calcium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether, polycarboxylate and polyoxyethylene polyoxypropylene block copolymer; The first thickener and the second thickener are each independently selected from at least one of organic bentonite, white carbon, magnesium aluminum silicate, polyvinyl alcohol, polyethylene glycol, xanthan gum, guar gum and sodium carboxymethyl cellulose.

2. The preparation method according to claim 1, It is characterized in that In step S1, the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is (1-5.5):(1-1.2).

3. The preparation method according to claim 1, It is characterized in that In step S1, the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is (1-5.5):

1.

4. The preparation method according to claim 1, It is characterized in that In step S1, the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is (2.5-3.5):

1.

5. The preparation method according to claim 1, It is characterized in that In step S1, the weight ratio of the urea-formaldehyde resin prepolymer aqueous solution to the emamectin benzoate emulsifiable concentrate is 3.5:

1.

6. The preparation method according to claim 1, It is characterized in that In step S1, the urea-formaldehyde resin prepolymer aqueous solution is polymerized by raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, cross-linking agent and water is 1:(0.58-2.5):(0.7-1.5):(0.5-5).

7. The preparation method according to claim 1, It is characterized in that In step S1, the urea-formaldehyde resin prepolymer aqueous solution is polymerized by raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, cross-linking agent and water is 1:(0.58-2):(1-1.5):(1-4.5).

8. The preparation method according to claim 1, It is characterized in that In step S1, the urea-formaldehyde resin prepolymer aqueous solution is polymerized by raw materials in the following weight ratio: the weight ratio of formaldehyde, urea, cross-linking agent and water is 1:(0.58-1.8):(1-1.2):(1.5-4).

9. The preparation method according to claim 1, It is characterized in that In step S1, the urea-formaldehyde resin prepolymer aqueous solution is polymerized from raw materials in the following weight ratio: formaldehyde, urea, cross-linking agent and water in a weight ratio of 1:1.2:1:

3.

10. The preparation method according to claim 1, It is characterized in that In step S1, the polymerization conditions include: pH value of 8-10, temperature of 65-80° C., and reaction time of 1-2.5 hours.

11. The preparation method according to claim 1, It is characterized in that The mixing in step S1 is performed under stirring, and the stirring speed is 1500-2800 rpm.

12. The preparation method according to claim 1, It is characterized in that In step S1, in the emamectin benzoate emulsifiable concentrate, the weight ratio of emamectin benzoate, organic solvent and emulsifier is 1:(1.4-7):(0.02-0.5).

13. The preparation method according to claim 1, It is characterized in that In step S1, in the emamectin benzoate emulsifiable concentrate, the weight ratio of emamectin benzoate, organic solvent and emulsifier is 1:(1.4-4.5):(0.07-0.15).

14. The preparation method according to claim 1, It is characterized in that In step S1, in the emamectin benzoate emulsifiable concentrate, the weight ratio of emamectin benzoate, organic solvent and emulsifier is 1:(2-4):(0.07-0.15).

15. The preparation method according to claim 1, It is characterized in that In step S1, in the emamectin benzoate emulsifiable concentrate, the weight ratio of emamectin benzoate, organic solvent and emulsifier is 1:2:0.

07.

16. The preparation method according to claim 1, It is characterized in that In step S1, in the emamectin benzoate emulsifiable concentrate, the organic solvent is selected from one or more of N,N-dimethylformamide, cyclohexanone, toluene, xylene, dimethyl sulfoxide, N-methylpyrrolidone, ethanol, trimethylcyclohexanone, N-octylpyrrolidone, ethanolamine, triethanolamine, isopropylamine, methanol, propanol, butanol, ethylene glycol, methyl oleate, ethyl acetate, vegetable oil, acetonitrile, solvent oil 150# and alkane solvent oil 200#.

17. The preparation method according to claim 1, It is characterized in that In step S2, mixing is performed under stirring conditions, and the stirring speed is 1000-1300 rpm.

18. The preparation method according to claim 1, It is characterized in that In step S3, mixing is performed under stirring conditions, and the stirring speed is 1800-2200 rpm.

19. The preparation method according to claim 1, It is characterized in that The weight ratio of emamectin benzoate to cyfluthrin is 1:(4-7).

20. The preparation method according to claim 1, It is characterized in that The weight ratio of emamectin benzoate to cyfluthrin is 1:(4.5-6).

21. The preparation method according to claim 1, It is characterized in that The weight ratio of emamectin benzoate to cyfluthrin is 1:

5.

22. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S6, the weight ratio of the emamectin benzoate microcapsule suspension concentrate, cyfluthrin suspension concentrate and the second dispersant obtained in step S5 is 1:(0.5-1.3):(0.02-0.2).

23. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S6, the weight ratio of the emamectin benzoate microcapsule suspension concentrate, cyfluthrin suspension concentrate and the second dispersant obtained in step S5 is 1:(0.65-1.15):(0.03-0.15).

24. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S6, the weight ratio of the emamectin benzoate microcapsule suspension concentrate, cyfluthrin suspension concentrate and the second dispersant obtained in step S5 is 1:(0.67-1.1):(0.03-0.14).

25. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S6, the weight ratio of the emamectin benzoate microcapsule suspension concentrate, cyfluthrin suspension concentrate and the second dispersant obtained in step S5 is 1:0.74:0.

03.

26. The preparation method according to any one of claims 1 to 21, It is characterized in that The first antifreeze agent and the second antifreeze agent are each independently selected from at least one of ethylene glycol, glycerol, 1,2-propylene glycol, sorbitol and urea.

27. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S5, the weight ratio of the fourth material to the first dispersant, the first thickener and the first antifreeze agent is 1: (0.02-0.25): (0.02-0.25): (0.05-0.5).

28. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S5, the weight ratio of the fourth material to the first dispersant, the first thickener and the first antifreeze agent is 1: (0.02-0.2): (0.02-0.05): (0.15-0.5).

29. The preparation method according to any one of claims 1 to 21, It is characterized in that In step S5, the weight ratio of the fourth material to the first dispersant, the first thickener and the first antifreeze agent is 1:0.02:0.05:0.

5.

30. The preparation method according to any one of claims 1 to 21, It is characterized in that The weight ratio of the cyprodinil to the third dispersant, the second thickener, the second antifreeze agent and water is 1:(0.2-0.5):(0.01-0.3):(0.1-0.5):(1-20).

31. The preparation method according to any one of claims 1 to 21, It is characterized in that The weight ratio of the cyprodinil to the third dispersant, the second thickener, the second antifreeze agent and water is 1:0.5:0.01:(1-3).

32. Use of the pesticide microcapsule suspension-suspension concentrate prepared by the method according to any one of claims 1 to 31 in controlling plant pests.

33. The use according to claim 32, It is characterized in that The plant pests include at least one of Lepidoptera pests and Coleoptera pests.

34. The use according to claim 32, It is characterized in that The plant pests include at least one of the rice stem borer and the rice leaf folder.

35. A method for using the pesticide microcapsule suspension-suspension concentrate prepared by the method according to any one of claims 1 to 31, It is characterized in that The application amount of pesticide microcapsule suspension-suspension concentrate is 0.5-20g / mu of active ingredient.

36. The method of use according to claim 35, It is characterized in that The application amount of the pesticide microcapsule suspension-suspension concentrate is 1-5g / mu of active ingredient.

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