Synergistic suspending agent of chlorantraniliprole

Abstract

The invention relates to the technical field of pesticides, in particular to a chlorantraniliprole synergistic suspending agent. According to the synergistic suspending agent, a chlorantraniliprole active compound, a chlorantraniliprole active compound, a four-arm star-shaped ethyl methacrylate polymer and organic silicon graft modified acrylic acid cardanol polyoxyethylene ether which are loaded by a porous carbon material serving as a carrier are taken as main raw materials; the porous carbon material provided by the invention has relatively high adsorbability and adsorption capacity on chlorantraniliprole raw medicine, can effectively prolong the lasting time of the chlorantraniliprole synergistic suspending agent, and is compounded with the four-arm star-shaped ethyl methacrylate polymer and the organic silicon grafted and modified acrylic cardanol polyoxyethylene ether, so that the synergistic effect of the suspending agent is improved. The chlorantraniliprole active compound released in the porous carbon material and the particle size of the chlorantraniliprole active compound can be remarkably nanocrystallized, so that the systemic property of the chlorantraniliprole active compound is improved, the chlorantraniliprole active compound can be absorbed by crops to the maximum extent, the insecticidal effect is finally improved, and the application prospect is wide.

Description

Technical Field

[0001] The invention relates to the technical field of pesticides, and in particular to a synergistic suspending agent of chlorantraniliprole. Background Art

[0002] Chlorantraniliprole is a broad-spectrum, highly effective, low-toxic and highly conductive insecticide with the chemical formula CHBrCl2N5O2. It has a melting point of 208-210°C and a boiling point of 526.6°C. Chlorantraniliprole has high stability and heat resistance. The reason why it can effectively kill pests is due to its unique insecticidal principle. Chlorantraniliprole can act on the nicotinic acid-sensitive calcium ion release channel (CRC), making the calcium ion channel of the insect nicotinic acid receptor in an open state, prompting the release of calcium ions from the endoplasmic reticulum membrane. This regulatory effect on the internal calcium store is the basic reason for the activity of sandworms. Under the action of chlorantraniliprole, the nicotinic acid receptor is in an open state, prompting a large amount of calcium ions to be released from the internal calcium store, resulting in an increase in the calcium ion concentration in the cytoplasm, causing the muscle cells to complete a contraction, and the continuous release of calcium ions causes the insect body to continuously contract, vomit, and defecate, which in turn leads to cessation of feeding and ultimately death of the insect body. This mechanism of action makes chlorantraniliprole highly active against the larvae of Lepidoptera pests, with a broad insecticidal spectrum and good long-lasting effectiveness. The wide application of chlorantraniliprole has proved its remarkable effect in agricultural production. Whether it is for major rice pests, such as rice leaf folder and striped stem borer, or for pests on vegetables and fruit trees, such as beet armyworm, diamondback moth and golden moth, chlorantraniliprole has demonstrated high efficiency in killing.

[0003] However, although chlorantraniliprole has a good insecticidal effect, in order to prolong the duration of action of chlorantraniliprole in the prior art, chlorantraniliprole is generally loaded and packaged using a carrier material. However, since the general carrier requires a specific environment or specific conditions to release the active ingredient, this will inevitably lead to a delay in the efficacy of the drug due to the insensitive release of the carrier, resulting in a decrease in the insecticidal effect.

[0004] Therefore, according to the above-mentioned related technologies, it is urgent to develop a synergistic suspending agent of chlorantraniliprole. Summary of the invention

[0005] In view of this, the purpose of the present invention is to provide a synergistic suspending agent of chlorantraniliprole to solve the problem that the synergistic suspending agent of chlorantraniliprole in the prior art is difficult to achieve both high efficiency and timely synergistic effect and high lasting effect.

[0006] Based on the above purpose, the present invention provides a synergistic suspending agent of chlorantraniliprole.

[0007] A chlorantraniliprole synergistic suspension concentrate comprises the following raw materials in parts by weight: 13-13.5 parts of a chlorantraniliprole complex, 40-50 parts of chlorantraniliprole technical, 4-6 parts of a surfactant, 8-12 parts of a wetting and dispersing agent, 4-4.5 parts of a thickener, 0.5-5 parts of a synergist, 6-10 parts of an antifreeze agent, 1.5-3 parts of a defoamer, 1.5-2 parts of a preservative, 1.2-1.6 parts of a synergistic aid, and 25-30 parts of water;

[0008] The chlorantraniliprole complex is a chlorantraniliprole original drug with a porous carbon material as a carrier;

[0009] The surfactant is acrylic cardanol polyoxyethylene ether modified by organosilicon grafting;

[0010] The synergist is a four-arm star-shaped ethyl methacrylate polymer.

[0011] Preferably, the preparation method of the chlorantraniliprole complex is as follows:

[0012] The chlorantraniliprole original drug, biochar powder and sodium carboxymethyl cellulose are mixed and added into a seed pellet machine to prepare a chlorantraniliprole complex;

[0013] The mass ratio of the chlorantraniliprole original drug, the biochar powder and the sodium carboxymethyl cellulose is 10-12:100-105:0.55-0.585;

[0014] The biochar powder is powdered corncob biochar.

[0015] Preferably, the preparation method of the surfactant is as follows:

[0016] Step A1. The inhibitor, catalyst and cardanol polyoxyethylene ether are mixed evenly, nitrogen is passed for 30 minutes, and the temperature is raised to 65-70 ° C under mechanical stirring at 430-450r / min, acrylic acid is added, stirred for 2-4 minutes, and the temperature is continued to rise to 120-130 ° C. The reaction is refluxed for 5-6 hours, and the resulting product is cooled to room temperature and dissolved in dichloromethane. The system is adjusted to neutral with sodium hydroxide solution, the solution is allowed to stand and stratify, the upper layer of liquid is removed, and the lower layer of liquid is rinsed with saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A;

[0017] Step A2. Mix material A and chloroplatinic acid-ethanol solution, add heptamethyltrisiloxane dropwise after passing nitrogen for 30 minutes, condense and reflux, stir at 85-95°C for 10-12 hours, and cool to room temperature to obtain an organosilicon surfactant.

[0018] Preferably, the usage ratio of the cardanol polyoxyethylene ether, acrylic acid and dichloromethane in step A1 is 18-22 g: 1-1.2 g: 75-85 mL;

[0019] The amount of the polymerization inhibitor in step A1 is 0.6%-0.8% of the total mass of cardanol polyoxyethylene ether and acrylic acid; the polymerization inhibitor is hydroquinone;

[0020] The amount of the catalyst used in step A1 is 4%-5% of the total mass of cardanol polyoxyethylene ether and acrylic acid; the catalyst is p-toluenesulfonic acid;

[0021] The concentration of sodium hydroxide in step A1 is 0.04-0.06 mol / L;

[0022] In step A2, the amount ratio of material A to chloroplatinic acid-ethanol solution is 8-12 g: 60-80 mL; the amount ratio of material A to heptamethyltrisiloxane is 1-1.2: 1.2-1.5; and the concentration of chloroplatinic acid-ethanol solution is 0.04-0.06 mol / L.

[0023] Preferably, the preparation method of the synergist is as follows:

[0024] Step B1. Tetrahydrofuran and triethylamine were dissolved in pentaerythritol at 0°C, 2-bromo-2-methylacryloyl bromide was added dropwise thereto, and the reaction was quenched with methanol after stirring at room temperature for 22-24 hours. The solvent was removed under reduced pressure and the resulting product was recrystallized to obtain material B;

[0025] Step B2. Under a nitrogen atmosphere, material B and ethyl 2-(dimethylamino)methacrylate are dissolved in tetrahydrofuran, and cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine are added. The mixture is sealed and reacted in an oil bath at 58-60°C for 7 hours. After the reaction, the mixture is cooled to remove tetrahydrofuran and purified to obtain a synergistic aid.

[0026] Preferably, the usage ratio of tetrahydrofuran, triethylamine, pentaerythritol and 2-bromo-2-methylacryloyl bromide in step B1 is 18-22 mL: 110-112 mg: 24-26 mg: 250-255 mg.

[0027] Preferably, the usage ratio of material B, 2-(dimethylamino)ethyl methacrylate, tetrahydrofuran, cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine in step B2 is 38-42 mg: 2-2.5 g: 6-10 mL: 43-49 mg: 105-115 mg.

[0028] Preferably, the wetting and dispersing agent is any one of sodium methylene dinaphthalene disulfonate and sodium lignin sulfonate;

[0029] The thickener is any one of xanthan gum, carboxymethyl cellulose, bentonite and magnesium aluminum silicate.

[0030] Preferably, the synergist is any one of pentadecanol and heptadecanol;

[0031] The antifreeze agent is any one of ethylene glycol, glycerol and propylene glycol.

[0032] Preferably, the defoaming agent is silicone oil;

[0033] The preservatives are benzoic acid, formaldehyde and isothiazolinone.

[0034] Beneficial effects of the present invention:

[0035] The invention provides a synergistic suspending agent of chlorantraniliprole. The invention introduces chlorantraniliprole original drug loaded by a porous carbon material, wherein the porous carbon material has high adsorption property and adsorption amount for the chlorantraniliprole original drug, and can effectively increase the action time of chlorantraniliprole. Meanwhile, a four-arm star-shaped ethyl methacrylate polymer and acrylic cardanol polyoxyethylene ether modified by organosilicon grafting are compounded, so that the chlorantraniliprole original drug in the system and the chlorantraniliprole original drug released from the porous carbon material can be nano-sized, thereby increasing the systemicity of the chlorantraniliprole original drug, and further enabling the synergistic suspending agent to have the effects of reducing dosage and continuously increasing synergy. DETAILED DESCRIPTION

[0036] In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0037] The sources and properties of some of the raw materials used in the present invention are as follows:

[0038] The concentration of chlorantraniliprole technical drug was 95.3%, which was purchased from Shandong Youdao Chemical Co., Ltd.;

[0039] The degree of polymerization of the polyoxyethylene ether in the cardanol polyoxyethylene ether is 6-14, and it was purchased from Shanghai Bangao Chemical Co., Ltd.;

[0040] Powdered corncob biochar is produced by Henan Luoyang Straw Charcoal Industry Co., Ltd.

[0041] Embodiment 1: A method for preparing a synergistic suspension concentrate of chlorantraniliprole, comprising the following steps:

[0042] S1. The hydroquinone, p-toluenesulfonic acid and 18g of cardanol polyoxyethylene ether were mixed uniformly, nitrogen was passed through for 30min, and the temperature was raised to 65°C under mechanical stirring at 430r / min, 1g of acrylic acid was added, stirred for 2min, and the temperature was continued to rise to 120°C, refluxed for 5h, and the resulting product was cooled to room temperature and dissolved in 75mL of dichloromethane, and the system was adjusted to neutral with a sodium hydroxide solution having a concentration of 0.04mol / L, and the solution was allowed to stand for stratification, the upper liquid was removed, and the lower liquid was rinsed with a saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A, wherein the amount of hydroquinone was 0.6% of the total mass of cardanol polyoxyethylene ether and acrylic acid, and the amount of p-toluenesulfonic acid was 4% of the total mass of cardanol polyoxyethylene rice and acrylic acid;

[0043] S2. 8 g of material A and 60 mL of 0.04 mol / L chloroplatinic acid-ethanol solution were mixed, nitrogen was passed through for 30 min, heptamethyltrisiloxane was added dropwise, condensed and refluxed, stirred at 85 ° C for 10 h, and cooled to room temperature to obtain an organosilicon surfactant, wherein the molar ratio of material A to heptamethyltrisiloxane was 1:1.2;

[0044] S3. 18 mL of tetrahydrofuran and 110 mg of triethylamine were dissolved in 24 mg of pentaerythritol at 0°C, 250 mg of 2-bromo-2-methylacryloyl bromide was added dropwise thereto, the reaction was stirred at room temperature for 22 h, and then methanol was used to quench the reaction. After the solvent was removed under reduced pressure, the resulting product was recrystallized to obtain material B;

[0045] S4. Under a nitrogen atmosphere, 38 mg of material B and 2 g of ethyl 2-(dimethylamino)methacrylate were dissolved in 6 mL of tetrahydrofuran, and 43 mg of cuprous bromide and 105 mg of N,N,N,N,N-pentamethyldiethylenetriamine were added. The mixture was sealed and reacted in an oil bath at 58 ° C for 7 h. After the reaction was completed, the tetrahydrofuran was removed by cooling and purified to obtain a synergist;

[0046] S5. 10 g of chlorantraniliprole original drug, 100 g of powdered corncob biochar and 0.55 g of sodium carboxymethyl cellulose were mixed and added to a seed pelletizer to prepare a chlorantraniliprole complex;

[0047] S6. Evenly mix 13g of chlorantraniliprole complex, 40.5g of chlorantraniliprole original drug, 4g of surfactant, 8g of sodium methylene dinaphthalene disulfonate, 4g of xanthan gum, 0.5g of pentadecanol, 6g of ethylene glycol, 1.5g of silicone oil, 1.5g of benzoic acid, 1.2g of synergistic aid and 25g of water, and grind with a colloid mill to obtain a synergistic suspension of chlorantraniliprole.

[0048] Embodiment 2: A method for preparing a synergistic suspension concentrate of chlorantraniliprole, comprising the following steps:

[0049] S1. The hydroquinone, p-toluenesulfonic acid and 19g of cardanol polyoxyethylene ether were mixed uniformly, nitrogen was passed through for 30min, and the temperature was raised to 67°C under mechanical stirring at 435r / min, 1.1g of acrylic acid was added, stirred for 3min, and the temperature was continued to rise to 122°C, refluxed for 5.5h, the resulting product was cooled to room temperature and dissolved in 80mL of dichloromethane, and the system was adjusted to neutral with a sodium hydroxide solution having a concentration of 0.05mol / L, and the solution was allowed to stand for stratification, the upper liquid was removed, and the lower liquid was rinsed with a saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A, wherein the amount of hydroquinone was 0.7% of the total mass of cardanol polyoxyethylene ether and acrylic acid, and the amount of p-toluenesulfonic acid was 4.5% of the total mass of cardanol polyoxyethylene rice and acrylic acid;

[0050] S2. 9 g of material A and 70 mL of 0.05 mol / L chloroplatinic acid-ethanol solution were mixed, nitrogen was passed through for 30 min, heptamethyltrisiloxane was added dropwise, condensed and refluxed, stirred at 90 ° C for 11 h, and cooled to room temperature to obtain an organosilicon surfactant, wherein the molar ratio of material A to heptamethyltrisiloxane was 1.1:1.3;

[0051] S3. 19 mL of tetrahydrofuran and 111 mg of triethylamine were dissolved in 25 mg of pentaerythritol at 0°C, 251 mg of 2-bromo-2-methylacryloyl bromide was added dropwise thereto, the reaction was stirred at room temperature for 23 h, and then methanol was used to quench the reaction. After the solvent was removed under reduced pressure, the resulting product was recrystallized to obtain material B;

[0052] S4. Under a nitrogen atmosphere, 39 mg of material B and 2.1 g of ethyl 2-(dimethylamino)methacrylate were dissolved in 7 mL of tetrahydrofuran, and 44 mg of cuprous bromide and 110 mg of N,N,N,N,N-pentamethyldiethylenetriamine were added. The mixture was sealed and reacted in an oil bath at 59 ° C for 7 h. After the reaction was completed, the tetrahydrofuran was removed by cooling and purified to obtain a synergist;

[0053] S5. 11 g of chlorantraniliprole original drug, 101 g of powdered corncob biochar and 0.56 g of sodium carboxymethyl cellulose were mixed and added to a seed pelletizer to prepare a chlorantraniliprole complex;

[0054] S6. Evenly mix 13.2 g of chlorantraniliprole complex, 41.5 g of chlorantraniliprole original drug, 5 g of surfactant, 9 g of sodium lignin sulfonate, 4.1 g of carboxymethyl cellulose, 1.5 g of pentadecanol, 7 g of glycerol, 2 g of silicone oil, 1.6 g of formaldehyde, 1.3 g of synergistic aid and 26 g of water, and grind with a colloid mill to obtain a synergistic suspension of chlorantraniliprole.

[0055] Embodiment 3: A method for preparing a synergistic suspension concentrate of chlorantraniliprole, comprising the following steps:

[0056] S1. The hydroquinone, p-toluenesulfonic acid and 20g of cardanol polyoxyethylene ether were mixed uniformly, nitrogen was passed through for 30min, and the temperature was raised to 68°C under mechanical stirring at 440r / min, 1.2g of acrylic acid was added, stirred for 4min, and the temperature was continued to rise to 124°C, refluxed for 6h, the resulting product was cooled to room temperature and dissolved in 85mL of dichloromethane, and the system was adjusted to neutral with a sodium hydroxide solution having a concentration of 0.06mol / L, and the solution was allowed to stand for stratification, the upper liquid was removed, and the lower liquid was rinsed with a saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A, wherein the amount of hydroquinone was 0.8% of the total mass of cardanol polyoxyethylene ether and acrylic acid, and the amount of p-toluenesulfonic acid was 5% of the total mass of cardanol polyoxyethylene rice and acrylic acid;

[0057] S2. 10 g of material A and 80 mL of 0.06 mol / L chloroplatinic acid-ethanol solution were mixed, nitrogen was passed through for 30 min, heptamethyltrisiloxane was added dropwise, condensed and refluxed, stirred at 95 ° C for 12 h, and cooled to room temperature to obtain an organosilicon surfactant, wherein the molar ratio of material A to heptamethyltrisiloxane was 1.2:1.4;

[0058] S3. 20 mL of tetrahydrofuran and 112 mg of triethylamine were dissolved in 26 mg of pentaerythritol at 0°C, 252 mg of 2-bromo-2-methylacryloyl bromide was added dropwise thereto, the reaction was stirred at room temperature for 24 h, and then methanol was used to quench the reaction. After the solvent was removed under reduced pressure, the obtained product was recrystallized to obtain material B;

[0059] S4. Under a nitrogen atmosphere, 40 mg of material B and 2.3 g of ethyl 2-(dimethylamino)methacrylate were dissolved in 8 mL of tetrahydrofuran, and 45 mg of cuprous bromide and 112 mg of N,N,N,N,N-pentamethyldiethylenetriamine were added. The mixture was sealed and reacted in an oil bath at 60 ° C for 7 h. After the reaction was completed, the tetrahydrofuran was removed by cooling and purified to obtain a synergist;

[0060] S5. 12 g of chlorantraniliprole original drug, 103 g of powdered corncob biochar and 0.57 g of sodium carboxymethyl cellulose were mixed and added to a seed pelletizer to prepare a chlorantraniliprole complex;

[0061] S6. Evenly mix 13.3 g of chlorantraniliprole complex, 42.5 g of chlorantraniliprole original drug, 6 g of surfactant, 10 g of sodium methylene dinaphthalene disulfonate, 4.2 g of bentonite, 2.5 g of heptadecanol, 8 g of propylene glycol, 2.5 g of silicone oil, 1.7 g of isothiazolinone, 1.4 g of synergistic aid and 27 g of water, and grind with a colloid mill to obtain a synergistic suspending agent of chlorantraniliprole.

[0062] Embodiment 4: A method for preparing a synergistic suspension concentrate of chlorantraniliprole, comprising the following steps:

[0063] S1. The hydroquinone, p-toluenesulfonic acid and 21g of cardanol polyoxyethylene ether were mixed uniformly, nitrogen was passed through for 30min, and the temperature was raised to 69°C under mechanical stirring at 445r / min, 1.1g of acrylic acid was added, stirred for 3min, and the temperature was continued to rise to 128°C, refluxed for 5.5h, and the resulting product was cooled to room temperature and dissolved in 80mL of dichloromethane, and the system was adjusted to neutral with a sodium hydroxide solution having a concentration of 0.05mol / L, and the solution was allowed to stand for stratification, the upper liquid was removed, and the lower liquid was rinsed with a saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A, wherein the amount of hydroquinone was 0.7% of the total mass of cardanol polyoxyethylene ether and acrylic acid, and the amount of p-toluenesulfonic acid was 4.5% of the total mass of cardanol polyoxyethylene rice and acrylic acid;

[0064] S2. 11 g of material A and 70 mL of 0.05 mol / L chloroplatinic acid-ethanol solution were mixed, nitrogen was passed through for 30 min, heptamethyltrisiloxane was added dropwise, condensed and refluxed, stirred at 90 ° C for 11 h, and cooled to room temperature to obtain an organosilicon surfactant, wherein the molar ratio of material A to heptamethyltrisiloxane was 1.1:1.5;

[0065] S3. 21 mL of tetrahydrofuran and 111 mg of triethylamine were dissolved in 25 mg of pentaerythritol at 0°C, 254 mg of 2-bromo-2-methylacryloyl bromide was added dropwise thereto, the reaction was stirred at room temperature for 23 h, and then methanol was used to quench the reaction. After the solvent was removed under reduced pressure, the obtained product was recrystallized to obtain material B;

[0066] S4. Under a nitrogen atmosphere, 41 mg of material B and 2.4 g of ethyl 2-(dimethylamino)methacrylate were dissolved in 9 mL of tetrahydrofuran, and 48 mg of cuprous bromide and 114 mg of N,N,N,N,N-pentamethyldiethylenetriamine were added. The mixture was sealed and reacted in an oil bath at 59 ° C for 7 h. After the reaction was completed, the tetrahydrofuran was removed by cooling and purified to obtain a synergist;

[0067] S5. 11 g of chlorantraniliprole original drug, 104 g of powdered corncob biochar and 0.58 g of sodium carboxymethyl cellulose were mixed and added to a seed pelletizer to prepare a chlorantraniliprole complex;

[0068] S6. Evenly mix 13.4 g of chlorantraniliprole complex, 44.5 g of chlorantraniliprole original drug, 5 g of surfactant, 11 g of sodium lignin sulfonate, 4.4 g of magnesium aluminum silicate, 4.5 g of heptadecanol, 9 g of ethylene glycol, 2.8 g of silicone oil, 1.9 g of benzoic acid, 1.5 g of synergistic aid and 29 g of water, and grind with a colloid mill to obtain a synergistic suspending agent of chlorantraniliprole.

[0069] Embodiment 5: A method for preparing a synergistic suspension concentrate of chlorantraniliprole, comprising the following steps:

[0070] S1. The hydroquinone, p-toluenesulfonic acid and 22g of cardanol polyoxyethylene ether were mixed uniformly, nitrogen was passed through for 30min, and the temperature was raised to 70°C under mechanical stirring at 450r / min, 1g of acrylic acid was added, stirred for 2min, and the temperature was continued to rise to 130°C, refluxed for 5h, and the resulting product was cooled to room temperature and dissolved in 75mL of dichloromethane, and the system was adjusted to neutral with a sodium hydroxide solution having a concentration of 0.04mol / L, and the solution was allowed to stand for stratification, the upper liquid was removed, and the lower liquid was rinsed with a saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A, wherein the amount of hydroquinone was 0.6% of the total mass of cardanol polyoxyethylene ether and acrylic acid, and the amount of p-toluenesulfonic acid was 4% of the total mass of cardanol polyoxyethylene rice and acrylic acid;

[0071] S2. 12 g of material A and 60 mL of 0.04 mol / L chloroplatinic acid-ethanol solution were mixed, nitrogen was passed through for 30 min, heptamethyltrisiloxane was added dropwise, condensed and refluxed, stirred at 85 ° C for 10 h, cooled to room temperature, and an organosilicon surfactant was obtained, wherein the molar ratio of material A to heptamethyltrisiloxane was 1:1.5;

[0072] S3. 22 mL of tetrahydrofuran and 112 mg of triethylamine were dissolved in 26 mg of pentaerythritol at 0°C, 255 mg of 2-bromo-2-methylacryloyl bromide was added dropwise thereto, the reaction was stirred at room temperature for 24 h, and then methanol was used to quench the reaction. After the solvent was removed under reduced pressure, the obtained product was recrystallized to obtain material B;

[0073] S4. Under a nitrogen atmosphere, 42 mg of material B and 2.5 g of ethyl 2-(dimethylamino)methacrylate were dissolved in 10 mL of tetrahydrofuran, and 49 mg of cuprous bromide and 115 mg of N,N,N,N,N-pentamethyldiethylenetriamine were added. The mixture was sealed and reacted in an oil bath at 60 ° C for 7 h. After the reaction was completed, the tetrahydrofuran was removed by cooling and purified to obtain a synergist;

[0074] S5. 12 g of chlorantraniliprole original drug, 105 g of powdered corncob biochar and 0.585 g of sodium carboxymethyl cellulose were mixed and added to a seed pelletizer to prepare a chlorantraniliprole complex;

[0075] S6. Evenly mix 13.5 g of chlorantraniliprole complex, 50 g of chlorantraniliprole original drug, 6 g of surfactant, 12 g of sodium methylene dinaphthalene disulfonate, 4.5 g of magnesium aluminum silicate, 5 g of heptadecanol, 10 g of propylene glycol, 3 g of silicone oil, 2 g of isothiazolinone, 1.6 g of synergistic auxiliary agent and 30 g of water, and then grind with a colloid mill to obtain a synergistic suspension of chlorantraniliprole.

[0076] Comparative Example 1:

[0077] Compared with Example 1, the chlorantraniliprole complex was not added during the preparation of the synergistic suspending concentrate of chlorantraniliprole in this comparative example, and the remaining steps and parameters were the same, which will not be repeated in this comparative example. Finally, the synergistic suspending concentrate of chlorantraniliprole was obtained.

[0078] Comparative Example 2:

[0079] Compared with Example 1, no surfactant was added during the preparation of the synergistic suspending agent of chlorantraniliprole in this comparative example, and the remaining steps and parameters were the same, which will not be repeated in this comparative example. Finally, a synergistic suspending agent of chlorantraniliprole was obtained.

[0080] Comparative Example 3:

[0081] Compared with Example 1, no synergistic auxiliary agent was added during the preparation of the synergistic suspension concentrate of chlorantraniliprole in this comparative example, and the remaining steps and parameters were the same, which will not be repeated in this comparative example. Finally, a synergistic suspension concentrate of chlorantraniliprole was obtained.

[0082] Comparative Example 4:

[0083] Compared with Example 1, this comparative example only replaces the "chlorantraniliprole complex" with the "chlorantraniliprole original drug", and the remaining steps and parameters are the same, which will not be repeated in this comparative example. Finally, a synergistic suspending agent of chlorantraniliprole is obtained.

[0084] Comparative Example 5:

[0085] Compared with Example 1, this comparative example only replaces the "surfactant" with "acrylic acid cardanol polyoxyethylene ether", and the remaining steps and parameters are the same, which will not be repeated in this comparative example, and finally a synergistic suspending agent of chlorantraniliprole is obtained.

[0086] Comparative Example 6:

[0087] Compared with Example 1, this comparative example only replaces the "synergistic aid" with "ethyl methacrylate polymer", and the remaining steps and parameters are the same, which will not be repeated in this comparative example. Finally, a synergistic suspending agent of chlorantraniliprole is obtained.

[0088] Comparative Example 7:

[0089] Compared with Example 1, this comparative example only adjusts the dosage of the synergistic auxiliary agent from 1.2 g to 12 g, and the remaining steps and parameters are the same, which will not be repeated in this comparative example. Finally, a synergistic suspending agent of chlorantraniliprole is obtained.

[0090] Performance Test:

[0091] Contact angle test:

[0092] The contact angle of each group of samples prepared in Examples 1 to 5 and Comparative Examples 1 to 6 on corn flakes was measured using a contact angle meter JC2000D (Shanghai Zhongchen Digital Technology Equipment Co., Ltd.). The corn leaves used were taken from corn plants of the Zhengda 999 variety. The contact angle value was measured using the angle measurement method. Each sample was measured 10 times, and the results were averaged.

[0093] Maximum retention test:

[0094] Take clean corn leaves and cut them into 2×2cm 2 The size of the leaves was weighed using an analytical balance (W0), and then clamped with tweezers and placed vertically in each group of samples prepared in Example 1-Example 5 and Comparative Example 1-Comparative Example 6 for 20 seconds. The leaves were quickly pulled out of the water and suspended vertically. When no more liquid drops fell, they were weighed (W1). This was repeated 3 times. The maximum retention of the sample on the corn leaf Rm (mg / cm 2 ):

[0095]

[0096] Rainwater erosion resistance:

[0097] Cut the corn leaves into 2×2cm 2Size, the upper surface of the leaf is fixed upward in the middle of the slide, 1.0μL of each group of samples is dropped on the center of the corn leaf using a pipette, and after adding the medicine, it is placed in a 25℃ room to dry naturally for 30 minutes, and the leaves are rinsed with deionized water in an acid burette. The inclination angle of the bracket is about 45°, and each leaf is rinsed 6 times, 1.0mL of water is used each time, and the water drop rate is 3d / s. The vertical distance between the burette outlet and the leaf is 2cm, and the leaf eye membrane is crushed, rinsed with 10mL of anhydrous methanol and transferred to a centrifuge tube, vortexed for 1min, and then ultrasonicated for 5min, and then 0.5g of anhydrous Na2SO4 and 0.5g of NaCl are added, shaken and ultrasonicated for 3min, centrifuged at 4000r / min for 5min, and then filtered to remove the filtrate, and then 2mL of anhydrous methanol is added to dissolve it back, and it is placed in a sample bottle after passing through the organic phase filter membrane, and the residual amount of the drug on the leaf is determined by high performance liquid chromatography and recorded;

[0098] Synergistic effect determination:

[0099] The leaf dipping method was used, with the third-instar larvae of Plutella xylostella as the test insects. The synergistic suspension was added with 0.1% Triton-100 and emulsified to a certain concentration of dilution. Fresh cabbage leaves were collected, the surface dust was washed with clean water and dried naturally, and the leaves were cut into leaf butterflies of appropriate size with scissors. The leaf butterflies were immersed in the diluted solution for 10 seconds, the surface moisture was dried naturally, and the leaf butterflies were placed in an 80cm 2 In the insect box, 20 larvae with the same development were placed in each box, and each 20 larvae were repeated for 3 times. The results were checked 72 hours after the treatment, and the number of dead and alive insects was recorded. The synergistic multiple of the synergistic suspension concentrate on the pesticide was calculated, and the synergistic ratio was recorded. The synergistic ratio refers to the degree of improvement of the pesticide's pest control effect after the synergist is added. Specifically, it is the ratio of the median lethal dose (LD50) or median lethal concentration (LC50) of the pesticide when the test insect is treated alone to the median lethal dose (LD50) or median lethal concentration (LC50) after the synergist is added. The larger this ratio is, the more significant the synergistic effect is. The results are shown in Table 1 below:

[0100] Table 1 Summary of experimental results of Examples 1-5 and Comparative Examples 1-6

[0101] project Contact angle / ° <![CDATA[Maximum retention amount / mg / cm 2 > Residue / mg / kg Efficiency ratio Example 1 32 26.3 31.5 12.9 Example 2 31 26.9 33.7 12.5 Example 3 29 25.1 32.8 13.1 Example 4 30 24.8 32.1 12.6 Example 5 33 23.9 32.6 13.7 Comparative Example 1 38 22.8 30.8 11.8 Comparative Example 2 42 21.3 29.5 12.1 Comparative Example 3 37 23.1 31.1 10.9 Comparative Example 4 39 22.4 30.5 11.5 Comparative Example 5 41 21.6 29.9 12.3 Comparative Example 6 35 23.5 31.3 11.0 Comparative Example 7 40 22.2 30.2 11.2

[0102] Data Analysis:

[0103] From Table 1 we can see that:

[0104] The synergistic suspending agent of chlorantraniliprole prepared by the present invention has a smaller contact angle, a higher maximum retention amount, and still has a higher residual amount after being washed by rainwater. This is because the synergistic suspending agent of chlorantraniliprole provided by the present invention introduces silicone-grafted modified acrylic cardanol polyoxyethylene ether, which has better wettability with crop leaves, so that the synergistic suspending agent finally prepared has lower surface tension and better ductility, so that the efficient synergistic effect can be maintained while reducing the amount of insecticides and pesticides used;

[0105] The synergistic suspending agent of chlorantraniliprole prepared by the present invention has a higher synergistic ratio. This is because the porous biocarbon material has a high porosity. The chlorantraniliprole original drug is loaded on the porous biocarbon material, which can increase the action time of the chlorantraniliprole original drug, thereby playing a role of sustained release and controlled release. In addition, a small amount of star-shaped ethyl methacrylate polymer present in the system can reduce the particle size of the chlorantraniliprole original drug released from the porous biocarbon material and the chlorantraniliprole original drug in the system, thereby nano-izing the chlorantraniliprole original drug and the systemicity and efficacy of the nano-sized chlorantraniliprole original drug and the chlorantraniliprole original drug in the system are improved. That is, the synergistic suspending agent of chlorantraniliprole prepared by the present invention has a higher synergistic ratio. This is because the porous biocarbon material has a high porosity. The chlorantraniliprole original drug is loaded on the porous biocarbon material, which can increase the action time of the chlorantraniliprole original drug, thereby playing a role of sustained release and controlled release. In addition, a small amount of star-shaped ethyl methacrylate polymer present in the system can reduce the particle size of the chlorantraniliprole original drug released from the porous biocarbon material and the chlorantraniliprole original drug in the system, thereby nano-izing the chlorantraniliprole original drug and the systemicity and efficacy of the chlorantraniliprole original drug are improved. It is easier to be absorbed by the leaves of crops, etc., so that pests will be killed when they swallow the leaves of crops, and the specific surface area increases due to the smaller particle size, so the efficacy is increased. In addition, the remaining chlorantraniliprole original drug that is not absorbed by the crop leaves can directly kill pests by contact and feeding. At the same time, the star-shaped ethyl methacrylate material itself has a certain insecticidal effect. Therefore, in summary, the synergistic suspension concentrate of chlorantraniliprole prepared by the present invention can kill insects through multiple mechanisms, so the synergistic effect of the insecticide is relatively high, and the lasting effect time can be taken into account at the same time, truly realizing the timely synergistic effect of the insecticide and the continuous and efficient synergistic effect of reducing the amount.

[0106] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

[0107] The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A synergistic suspending agent of chlorantraniliprole, characterized in that: The invention comprises the following raw materials in parts by weight: 13-13.5 parts of chlorantraniliprole complex, 40-50 parts of chlorantraniliprole technical, 4-6 parts of surfactant, 8-12 parts of wetting and dispersing agent, 4-4.5 parts of thickener, 0.5-5 parts of synergist, 6-10 parts of antifreeze agent, 1.5-3 parts of defoamer, 1.5-2 parts of preservative, 1.2-1.6 parts of synergist and 25-30 parts of water; The chlorantraniliprole complex is a chlorantraniliprole original drug with a porous carbon material as a carrier; The surfactant is acrylic cardanol polyoxyethylene ether modified by organosilicon grafting; The synergist is a four-arm star-shaped ethyl methacrylate polymer.

2. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that The preparation method of the chlorantraniliprole complex is as follows: The chlorantraniliprole original drug, biochar powder and sodium carboxymethyl cellulose are mixed and added into a seed pellet machine to prepare a chlorantraniliprole complex; The mass ratio of the chlorantraniliprole original drug, the biochar powder and the sodium carboxymethyl cellulose is 10-12:100-105:0.55-0.585; The biochar powder is powdered corncob biochar.

3. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that, The preparation method of the surfactant is as follows: Step A1. The inhibitor, catalyst and cardanol polyoxyethylene ether are mixed evenly, nitrogen is passed for 30 minutes, and the temperature is raised to 65-70 ° C under mechanical stirring at 430-450r / min, acrylic acid is added, stirred for 2-4 minutes, and the temperature is continued to rise to 120-130 ° C. The reaction is refluxed for 5-6 hours, and the resulting product is cooled to room temperature and dissolved in dichloromethane. The system is adjusted to neutral with sodium hydroxide solution, the solution is allowed to stand and stratify, the upper layer of liquid is removed, and the lower layer of liquid is rinsed with saturated sodium chloride solution, and then washed and separated 3 times, and finally distilled under reduced pressure to obtain material A; Step A2. Mix material A and chloroplatinic acid-ethanol solution, add heptamethyltrisiloxane dropwise after nitrogen flow for 30 minutes, condense and reflux, stir at 85-95°C for 10-12 hours, and cool to room temperature to obtain an organosilicon surfactant.

4. The synergistic suspending agent of chlorantraniliprole according to claim 3, characterized in that, The usage ratio of cardanol polyoxyethylene ether, acrylic acid and dichloromethane in step A1 is 18-22 g: 1-1.2 g: 75-85 mL; The amount of the polymerization inhibitor in step A1 is 0.6%-0.8% of the total mass of cardanol polyoxyethylene ether and acrylic acid; the polymerization inhibitor is hydroquinone; The amount of the catalyst used in step A1 is 4%-5% of the total mass of cardanol polyoxyethylene ether and acrylic acid; the catalyst is p-toluenesulfonic acid; The concentration of sodium hydroxide in step A1 is 0.04-0.06 mol / L; In step A2, the amount ratio of material A to chloroplatinic acid-ethanol solution is 8-12 g: 60-80 mL; the amount ratio of material A to heptamethyltrisiloxane is 1-1.2: 1.2-1.5; and the concentration of chloroplatinic acid-ethanol solution is 0.04-0.06 mol / L.

5. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that, The preparation method of the synergistic aid is as follows: Step B1. Tetrahydrofuran and triethylamine were dissolved in pentaerythritol at 0°C, 2-bromo-2-methylacryloyl bromide was added dropwise thereto, and the reaction was quenched with methanol after stirring at room temperature for 22-24 hours. The solvent was removed under reduced pressure and the resulting product was recrystallized to obtain material B; Step B2. Under a nitrogen atmosphere, material B and ethyl 2-(dimethylamino)methacrylate are dissolved in tetrahydrofuran, and cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine are added. The mixture is sealed and reacted in an oil bath at 58-60°C for 7 hours. After the reaction, the mixture is cooled to remove tetrahydrofuran and purified to obtain a synergistic aid.

6. The synergistic suspending agent of chlorantraniliprole according to claim 5, characterized in that, The usage ratio of tetrahydrofuran, triethylamine, pentaerythritol and 2-bromo-2-methylacryloyl bromide in step B1 is 18-22 mL: 110-112 mg: 24-26 mg: 250-255 mg.

7. The synergistic suspending agent of chlorantraniliprole according to claim 5, characterized in that, The usage ratio of material B, 2-(dimethylamino)ethyl methacrylate, tetrahydrofuran, cuprous bromide and N,N,N,N,N-pentamethyldiethylenetriamine in step B2 is 38-42 mg: 2-2.5 g: 6-10 mL: 43-49 mg: 105-115 mg.

8. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that, The wetting and dispersing agent is any one of sodium methylene dinaphthalene disulfonate and sodium lignin sulfonate; The thickener is any one of xanthan gum, carboxymethyl cellulose, bentonite and magnesium aluminum silicate.

9. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that, The synergist is any one of pentadecanol and heptadecanol; The antifreeze agent is any one of ethylene glycol, glycerol and propylene glycol.

10. The synergistic suspending agent of chlorantraniliprole according to claim 1, characterized in that: The defoaming agent is silicone oil; The preservatives are benzoic acid, formaldehyde and isothiazolinone.

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