Preparation method of dinotefuran suspending agent

Abstract

The invention discloses a preparation method of a dinotefuran suspending agent, and relates to the technical field of pesticide preparation processing. Comprising the following steps: grinding raw materials of the dinotefuran suspending agent in a grinding medium for 2-3 hours, and detecting various indexes to obtain the dinotefuran suspending agent, the dinotefuran suspending agent is prepared from the following raw material components in percentage by mass: 20 percent of dinotefuran raw medicine, 12 to 15 percent of an auxiliary agent, 0.18 to 0.2 percent of xanthan gum, 1 to 1.2 percent of magnesium aluminum silicate, 0.3 percent of benzoic acid, 0.5 percent of a de-foaming agent and the balance of de-ionized water. The dinotefuran suspending agent has the beneficial effects that the auxiliary agent and the modified white carbon black in the prepared dinotefuran suspending agent play a synergistic role, so that the dinotefuran can be well prevented from being separated out in the preparation, the stability of the dinotefuran in the preparation is improved, and the suspending agent can better play a role in removing and treating ptera pests by the dinotefuran.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide formulation processing, and specifically to a preparation method of dinotefuran suspension concentrate. Background Art

[0002] Dinotefuran is a third-generation nicotinic insecticide discovered by Mitsui Chemicals, Inc. of Japan and launched in Japan in 2002. It is a highly efficient and broad-spectrum insecticide with contact and stomach toxicity effects, and at the same time has excellent systemic penetration effect. The dinotefuran suspension concentrate uses water as the dispersion medium, and the solid technical material that is insoluble or slightly soluble in water is ground and pulverized, and with the action of surfactants and other auxiliaries, it is uniformly dispersed to form a stable liquid-solid system with fine particles, high suspension, and fluidity. Compared with traditional emulsifiable concentrates and wettable powders, the suspension concentrate avoids the use of a large amount of organic solvents, reduces dust scattering, reduces the toxicity and irritation to humans and livestock, reduces the phytotoxicity to crops, and improves safety.

[0003] The dinotefuran suspension concentrate also has excellent dispersibility, high suspension rate, and strong spreading and adhesion forces on the surface of plants, is resistant to rain erosion, has significant and long-lasting efficacy. Compared with traditional nicotinic insecticides, dinotefuran does not contain halogen elements, has stronger water solubility, is more easily absorbed by plants, and has less impact on the environment and non-target organisms. The dinotefuran suspension concentrate has contact and stomach toxicity effects, and has excellent control effects on piercing-sucking mouthpart pests. It shows high insecticidal activity at very low doses, is applicable to a variety of crops such as rice, cotton, vegetables, fruit trees, etc., and the control targets include aphids, leafhoppers, planthoppers, thrips, whiteflies, etc.

[0004] Currently, in the preparation of dinotefuran suspension concentrate, surfactants are usually added. Conventional surfactants are prone to pasting phenomenon during the grinding preparation stage, and the fluidity of the formulation is insufficient, the thixotropy problem is serious, and more importantly, the stability is very poor. After standing at room temperature for a long time, it is prone to solidification and bottom settlement phenomenon. And it is easy to precipitate crystals under low-temperature conditions and does not recover at room temperature.

[0005] Therefore, in order to solve the above problems, the present invention provides a preparation method of dinotefuran suspension concentrate. Summary of the Invention

[0006] The purpose of the present invention is to provide a preparation method of dinotefuran suspension concentrate to solve the problems raised in the prior art.

[0007] To achieve the above purpose, the present invention provides the following technical solutions:

[0008] A preparation method of dinotefuran suspension concentrate includes the following process: grinding the raw materials of dinotefuran suspension concentrate under a grinding medium for 2 - 3 h, detecting various indexes, and obtaining the dinotefuran suspension concentrate; the particle size D90 in the dinotefuran suspension concentrate after grinding is below 5 μm.

[0009] More optimally, the raw materials of the dinotefuran suspension include the following components: by mass percentage, 20% of dinotefuran technical, 12 - 15% of auxiliary agent, 0.18 - 0.2% of xanthan gum, 1 - 1.2% of magnesium aluminum silicate, 0.3% of benzoic acid, 0.5% of defoaming agent, and the balance is deionized water.

[0010] More optimally, the auxiliary agent includes the following components: by mass percentage, 60 - 75% of sodium polystyrene phenol ethoxysulfonate and 25 - 40% of triamine salt of alkyl benzene sulfonic acid.

[0011] More optimally, the dinotefuran suspension further includes modified silica white, and the mass percentage of the modified silica white in the dinotefuran suspension is: 3 - 5%.

[0012] More optimally, the preparation process of the modified silica white is as follows:

[0013] S1: Add silica white and γ - aminopropyltriethoxysilane to ethanol, heat up to 40 - 50 °C, and stir for 30 - 40 min to obtain aminated silica white;

[0014] S2: Add aminated silica white and 3 - hydroxypentanoic acid to N,N - dimethylformamide, stir for 20 - 30 min, then add dicyclohexylcarbodiimide and N - hydroxysuccinimide, heat up to 90 - 100 °C, and react for 4 - 5 h to obtain intermediate A;

[0015] S3: Add intermediate A and maleic anhydride to chloroform, stir for 40 - 50 min, add p - toluenesulfonic acid as a catalyst, then heat up to 80 - 90 °C, react for 4 - 5 h, and cool to room temperature to obtain intermediate B;

[0016] S4: Under a protective atmosphere, mix intermediate B with sodium sulfite solution, heat up to 85 - 90 °C, stir for 3 - 4 h, cool to room temperature, filter, wash, and dry to obtain modified silica white.

[0017] More optimally, the aminated silica white includes the following components: by weight parts, 20 - 30 parts of silica white, 25 - 30 parts of γ - aminopropyltriethoxysilane, and 200 - 250 parts of ethanol;

[0018] The intermediate A includes the following components: by weight parts, 20 - 30 parts of aminated silica white, 10 - 12 parts of 3 - hydroxypentanoic acid, 80 - 100 parts of N,N - dimethylformamide, 0.5 - 1 part of dicyclohexylcarbodiimide, and 0.8 - 1 part of N - hydroxysuccinimide;

[0019] The intermediate B comprises the following components: by weight, 10-12 parts of intermediate A, 6-8 parts of maleic anhydride, 100-150 parts of chloroform, and 0.1-0.2 parts of p-toluenesulfonic acid;

[0020] The modified silica white comprises the following components: by weight, 10-12 parts of intermediate B and 15-20 parts of sodium sulfite solution.

[0021] More preferably: the mass concentration of the sodium sulfite solution is 20-30%.

[0022] More preferably: the dinotefuran suspending agent is mainly used for controlling aphids, leafhoppers, planthoppers, thrips, whiteflies and their resistant strains on various crops such as wheat, rice, cotton, vegetables, fruit trees, tobacco leaves, etc., and has high insecticidal activity against pests of Coleoptera, Diptera, Lepidoptera and Homoptera, and also has high insecticidal activity against sanitary pests such as cockroaches, termites, houseflies, etc.

[0023] The auxiliaries in the dinotefuran suspending agent prepared by the present invention and the modified silica white act synergistically, which can well ensure that dinotefuran does not precipitate in the preparation and improve the stability of dinotefuran in the preparation, so that the suspending agent can better exert the control effect of dinotefuran on pests of Lepidoptera. Specifically as follows:

[0024] First: Polystyrene phenol ethoxy ether sodium sulfite in the auxiliaries introduces metal ions on the basis of polystyrene phenol ethoxy ether, and can form a complexation with dinotefuran crystals, increasing the solubility of dinotefuran in water to ensure that the solubility of dinotefuran does not change greatly with temperature change and does not precipitate at low temperature;

[0025] Second: Polystyrene phenol ethoxy ether sodium sulfite in the auxiliaries and alkyl benzene sulfonic acid triamine salt act together. They form a network distribution in water, strengthening the spatial distribution hindrance, making the molecules of dinotefuran remain stable in the network, reducing the influence of gravitational force, and making the dinotefuran suspending agent relatively stable;

[0026] Third: Polystyrene phenol ethoxy ether sodium sulfite in the auxiliaries will generate charges in water due to the action of metal ions, and can adsorb on the surface of dinotefuran molecules to form a charge layer, further strengthening the repulsive force between molecules. It can prevent dinotefuran molecules from aggregating.

[0027] The dispersibility is enhanced;

[0028] Fourthly, the white carbon black in the dinotefuran suspension concentrate can be adsorbed on the surface of dinotefuran due to its huge specific surface area and surface activity to form a stable adsorption layer to prevent the aggregation and sedimentation of dinotefuran; at the same time, the present invention chemically modifies the surface of the white carbon black, and the introduced molecular structure contains two hydrophilic groups, sodium carboxylate and sodium sulfonate, which further improves the surface activity of the white carbon black, so that it can better cooperate with other components in the auxiliary agent to play a role, and the longer molecular chain also improves the dispersibility of dinotefuran to a certain extent; and the introduced group can act as an anionic surfactant, and in the interaction with metal ions, it can improve the stability and compatibility of the dinotefuran suspension concentrate in complex environments, and can still maintain its performance under extreme conditions. DETAILED DESCRIPTION

[0029] Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in the field without making any creative work shall fall within the scope of protection of the present invention.

[0030] It should be noted that the following parts are parts by weight, and the purchase manufacturers of all raw materials involved in the present invention are exemplified without any special restrictions: In the following embodiments, xanthan gum was purchased from Suzhou Sinoma Materials Co., Ltd. with a brand name of XG204; magnesium aluminum silicate was purchased from Suzhou Sinoma Materials Co., Ltd. with a brand name of SF-04; benzoic acid was purchased from Wuhan Youji Industrial Co., Ltd. with a brand name of BENZOIC; and defoaming agent was purchased from Nanjing Qunxing Co., Ltd. with a brand name of 2040-X. The CAS number of γ-aminopropyltriethoxysilane is 919-30-2, and the manufacturer purchased is Shanghai Aladdin Biochemical Technology Co., Ltd.; the CAS number of 3-hydroxyvaleric acid is 10237-77-1, and the manufacturer purchased is Beijing Bailingwei Technology Co., Ltd.; the CAS number of dicyclohexylcarbodiimide is 538-75-0, and the manufacturer purchased is Jiangsu Pules Biotechnology Co., Ltd.; the CAS number of N-hydroxysuccinimide is 6066-82-6, and the manufacturer purchased is Shanghai Changming Pharmaceutical Technology Co., Ltd.; the CAS number of maleic acid glycoside is 108-31-6, and the manufacturer purchased is Jinan Jinhao Chemical Co., Ltd.

[0031] Embodiment 1: A method for preparing a dinotefuran suspension concentrate, comprising the following steps:

[0032] The raw materials of the dinotefuran suspension concentrate include the following components: by mass percentage, 20% of dinotefuran technical, 12% of auxiliary agent, 0.18% of xanthan gum, 1% of magnesium aluminum silicate, 0.3% of benzoic acid, 0.5% of defoamer, and the balance is deionized water.

[0033] Pre-preparation: The preparation process of modified silica is:

[0034] S1: Add 20 parts of silica white and 25 parts of γ-aminopropyltriethoxysilane to 200 parts of ethanol, heat up to 40 °C, and stir for 30 min to obtain amino-functionalized silica white;

[0035] S2: Add 20 parts of amino-functionalized silica white and 10 parts of 3-hydroxyvaleric acid to 80 parts of N,N-dimethylformamide, stir for 20 min, then add 0.5 part of dicyclohexylcarbodiimide and 0.8 part of N-hydroxysuccinimide, heat up to 90 °C, and react for 4 h to obtain intermediate A;

[0036] S3: Add 10 parts of intermediate A and 6 parts of maleic anhydride to 100 parts of chloroform, stir for 40 min, add 0.1 part of catalyst p-toluenesulfonic acid, then heat up to 80 °C, react for 4 h, and cool to room temperature to obtain intermediate B;

[0037] S4: Under nitrogen, mix 10 parts of intermediate B with 15 parts of sodium sulfite solution, heat up to 85 °C, stir for 3 h, cool to room temperature, filter, wash, and dry to obtain modified silica white;

[0038] Step 1: Mix an auxiliary agent (70% polystyrene phenol ethoxysulfonate, 30% triamine salt of alkylbenzene sulfonic acid), dinotefuran technical, and deionized water to obtain a mixed solution;

[0039] Step 2: Add xanthan gum, magnesium aluminum silicate, benzoic acid, defoamer, and modified silica white to the mixed solution, stir evenly, and then perform high-speed shear predispersion to obtain a mixed raw material;

[0040] Step 3: Grind the mixed raw material under a grinding medium for 2 h, detect various indexes, and obtain a dinotefuran suspension concentrate.

[0041] Example 2: A preparation method of a dinotefuran suspension concentrate, comprising the following steps:

[0042] The raw materials of the dinotefuran suspension concentrate include the following components: by mass percentage, 20% dinotefuran technical, 15% auxiliary agent, 0.2% xanthan gum, 1.2% magnesium aluminum silicate, 0.3% benzoic acid, 0.5% defoamer, and the balance is deionized water.

[0043] The preparation process of the modified silica white is as follows:

[0044] S1: Add 30 parts of silica white and 30 parts of γ-aminopropyltriethoxysilane to 250 parts of ethanol, heat up to 50 °C, and stir for 40 min to obtain amino-functionalized silica white;

[0045] S2: Add 30 parts of aminated silica white, 12 parts of 3-hydroxyvaleric acid to 100 parts of N,N-dimethylformamide, stir for 30 min, then add 1 part of dicyclohexylcarbodiimide and 1 part of N-hydroxysuccinimide, heat up to 100 °C, react for 5 h to obtain intermediate A;

[0046] S3: Add 12 parts of intermediate A, 8 parts of maleic anhydride to 150 parts of chloroform, stir for 50 min, add 0.2 part of catalyst p-toluenesulfonic acid, then heat up to 90 °C, react for 5 h, cool to room temperature to obtain intermediate B;

[0047] S4: Under nitrogen, mix 12 parts of intermediate B with 20 parts of sodium sulfite solution, heat up to 90 °C, stir for 4 h, cool to room temperature, filter, wash, dry to obtain modified silica white;

[0048] Step 1: Mix an auxiliary agent (60% polystyrene phenol ethoxysulfonate, 40% triamine alkylbenzene sulfonate), dinotefuran technical, and deionized water to obtain a mixed solution;

[0049] Step 2: Add xanthan gum, magnesium aluminum silicate, benzoic acid, defoamer, modified silica white to the mixed solution, stir evenly and then conduct high-speed shear pre-dispersion to obtain a mixed raw material;

[0050] Step 3: Grind the mixed raw material under a grinding medium for 3 h, detect various indicators to obtain a dinotefuran suspension concentrate.

[0051] Example 3: A preparation method of a dinotefuran suspension concentrate, comprising the following steps:

[0052] The raw materials of the dinotefuran suspension concentrate include the following components: by mass percentage, 20% dinotefuran technical, 13% auxiliary agent, 0.19% xanthan gum, 1.2% magnesium aluminum silicate, 0.3% benzoic acid, 0.5% defoamer, and the balance is deionized water.

[0053] The preparation process of the modified silica white is as follows:

[0054] S1: Add 25 parts of silica white, 28 parts of γ-aminopropyltriethoxysilane to 220 parts of ethanol, heat up to 45 °C, stir for 35 min to obtain aminated silica white;

[0055] S2: Add 25 parts of aminated silica white, 11 parts of 3-hydroxyvaleric acid to 90 parts of N,N-dimethylformamide, stir for 25 min, then add 0.8 part of dicyclohexylcarbodiimide and 0.9 part of N-hydroxysuccinimide, heat up to 95 °C, react for 4.5 h to obtain intermediate A;

[0056] S3: Add 11 parts of intermediate A and 7 parts of maleic acid glycoside to 120 parts of chloroform, stir for 45 min, add 0.15 part of the catalyst p-toluenesulfonic acid, then heat to 85 °C, react for 4.5 h, and cool to room temperature to obtain intermediate B;

[0057] S4: Under nitrogen, mix 11 parts of intermediate B with 18 parts of sodium sulfite solution, heat to 88 °C, stir for 3.5 h, cool to room temperature, filter, wash, and dry to obtain modified silica white;

[0058] Step 1: Mix an auxiliary agent (70% polystyrene phenol ethoxysulfonate, 30% alkylbenzene sulfonic acid triamine salt), dinotefuran technical, and deionized water to obtain a mixed solution;

[0059] Step 2: Add xanthan gum, magnesium aluminum silicate, benzoic acid, an antifoaming agent, and modified silica white to the mixed solution, stir evenly, and then perform high-speed shearing and pre-dispersion to obtain a mixed raw material;

[0060] Step 3: Grind the mixed raw material under a grinding medium for 2.5 h, detect various indexes, and obtain a dinotefuran suspension concentrate.

[0061] Example 4: A preparation method of a dinotefuran suspension concentrate, comprising the following steps:

[0062] The raw materials of the dinotefuran suspension concentrate include the following components: by mass percentage, 20% dinotefuran technical, 13% auxiliary agent, 0.19% xanthan gum, 1.2% magnesium aluminum silicate, 0.3% benzoic acid, 0.5% antifoaming agent, and the balance is deionized water.

[0063] The preparation process of the modified silica white is as follows:

[0064] S1: Add 20 parts of silica white and 25 parts of γ-aminopropyltriethoxysilane to 200 parts of ethanol, heat to 40 °C, and stir for 30 min to obtain amino-functionalized silica white;

[0065] S2: Add 20 parts of amino-functionalized silica white and 10 parts of 3-hydroxypentanoic acid to 80 parts of N,N-dimethylformamide, stir for 20 min, then add 0.5 part of dicyclohexylcarbodiimide and 0.8 part of N-hydroxysuccinimide, heat to 90 °C, and react for 4 h to obtain intermediate A;

[0066] S3: Add 12 parts of intermediate A and 8 parts of maleic acid glycoside to 150 parts of chloroform, stir for 50 min, add 0.2 part of the catalyst p-toluenesulfonic acid, then heat to 90 °C, react for 5 h, and cool to room temperature to obtain intermediate B;

[0067] S4: Under nitrogen, mix 12 parts of Intermediate B with 20 parts of sodium sulfite solution, heat to 90 °C, stir for 4 h, cool to room temperature, filter, wash, and dry to obtain modified silica white;

[0068] Step 1: Mix an auxiliary agent (70% polystyrene phenol ethoxysulfonate sodium salt, 30% alkylbenzene sulfonic acid triamine salt), dinotefuran technical, and deionized water to obtain a mixed solution;

[0069] Step 2: Add xanthan gum, magnesium aluminum silicate, benzoic acid, defoamer, and modified silica white to the mixed solution, stir evenly, and then perform high-speed shear predispersion to obtain a mixed raw material;

[0070] Step 3: Grind the mixed raw material under a grinding medium for 2.5 h, detect various indicators, and obtain a dinotefuran suspension concentrate.

[0071] Comparative Example 1: A commercially available dinotefuran suspension concentrate.

[0072] Detection experiment: (1) Under normal temperature conditions, detect the water separation amount, solidification condition, and thixotropy of the dinotefuran suspension concentrates obtained in Example 4 and the comparative example. The results are shown in the following table:

[0073]

[0074] Table 1

[0075] (2) After placing the dinotefuran suspension concentrates obtained in Example 4 and Comparative Example 1 at 54 °C for heat storage, detect the water separation amount, solidification condition, and thixotropy. The results are shown in the following table:

[0076]

[0077]

[0078] Table 2

[0079] (3) Under low temperature of zero degree, detect the water separation amount, precipitated crystals, and restorability of the dinotefuran suspension concentrates obtained in Example 4 and Comparative Example 1. The results are shown in the following table:

[0080]

[0081]

[0082] Table 3

[0083] Conclusion: The adjuvants in the dinotefuran suspension concentrate prepared by the present invention work synergistically with the modified silica white to ensure that dinotefuran does not precipitate in the formulation and improve the stability of dinotefuran in the formulation, enabling the suspension concentrate to better exert the control effect of dinotefuran on Lepidoptera pests. Moreover, it is not prone to solidification and bottom settlement after being placed at room temperature for a long time, and it is not easy to precipitate crystals under low-temperature conditions and can recover, meeting the actual use requirements.

[0084] Finally, it should be noted that the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a dinotefuran suspension concentrate, characterized in that: The raw materials of the dinotefuran suspension concentrate include the following components: by mass percentage, 20% of dinotefuran technical, 12-15% of auxiliary agent, 0.18-0.2% of xanthan gum, 1-1.2% of magnesium aluminum silicate, 0.3% of benzoic acid, 0.5% of defoamer, and the balance is deionized water.

2. The method for preparing a dinotefuran suspension concentrate according to claim 1, characterized in that: The auxiliary agent comprises the following components: by mass percentage, 60-75% of polystyrene phenol ethoxy sulfonic acid sodium salt and 25-40% of alkylbenzene sulfonic acid triamine salt.

3. The method for preparing a dinotefuran suspension concentrate according to claim 2, characterized in that: The dinotefuran suspension concentrate also includes modified white carbon black, wherein the mass percentage of the modified white carbon black in the dinotefuran suspension concentrate is 3-5%.

4. The method for preparing a dinotefuran suspension concentrate according to claim 3, characterized in that: The preparation process of the modified white carbon black is: S1: Add silica and γ-aminopropyltriethoxysilane to ethanol, heat to 40-50°C, and stir for 30-40 minutes to obtain amination silica; S2: Add amination silica and 3-hydroxyvaleric acid to N,N-dimethylformamide, stir for 20-30 min, then add dicyclohexylcarbodiimide and N-hydroxysuccinimide, heat to 90-100°C, react for 4-5h, and obtain intermediate A; S3: Add intermediate A and maleic acid glycoside to chloroform, stir for 40-50 min, add catalyst p-toluenesulfonic acid, then heat to 80-90°C, react for 4-5 h, and cool to room temperature to obtain intermediate B; S4: Under a protective atmosphere, the intermediate B is mixed with a sodium sulfite solution, heated to 85-90° C., stirred for 3-4 hours, cooled to room temperature, filtered, washed, and dried to obtain modified silica.

5. The method for preparing a dinotefuran suspension concentrate according to claim 4, characterized in that: The amination silica comprises the following components: by weight, 20-30 parts of silica, 25-30 parts of γ-aminopropyltriethoxysilane, and 200-250 parts of ethanol; The intermediate A comprises the following components: by weight, 20-30 parts of aminated white carbon black, 10-12 parts of 3-hydroxyvaleric acid, 80-100 parts of N,N-dimethylformamide, 0.5-1 parts of dicyclohexylcarbodiimide, and 0.8-1 parts of N-hydroxysuccinimide; The intermediate B comprises the following components: by weight, 10-12 parts of intermediate A, 6-8 parts of maleic acid glycoside, 100-150 parts of chloroform, and 0.1-0.2 parts of p-toluenesulfonic acid; The modified white carbon black comprises the following components: by weight, 10-12 parts of intermediate B and 15-20 parts of sodium sulfite solution.

6. The method for preparing a dinotefuran suspension concentrate according to claim 4, characterized in that: The mass concentration of the sodium sulfite solution is 20-30%.

7. A method for preparing a dinotefuran suspension concentrate according to any one of claims 1 to 6, characterized in that: The method comprises the following processes: grinding the raw material of dinotefuran suspension concentrate under a grinding medium for 2-3 hours, detecting various indicators, and obtaining the dinotefuran suspension concentrate.

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