阅读说明：本技术 一种克菌丹和氰霜唑农药组合物及其制备方法 (Captan and cyazofamid pesticide composition and preparation method thereof ) 是由 彭成洲 戴权 周学强 于 2021-10-27 设计创作，主要内容包括：本发明公开了一种克菌丹和氰霜唑农药组合物及其制备方法,由抗菌组合物和包衣液,包衣制得,所述的抗菌组合物包括如下重量百分比原料：克菌丹1-90％、氰霜唑1-90％、余量为辅助成分；通过将柠檬酸和中间体6反应,形成柠檬酸盐,再将柠檬酸盐、壳聚糖、液态石蜡、司盘80混合,制得包衣液,再将包衣液与抗菌组合物共混后,用戊二醛交联,制得农药组合物,该农药组合物具有很好的缓释作用,表面的包衣被植物吸收后,能够促进细胞伸长以及加速下包分裂,进而促进植物生长。(The invention discloses a captan and cyazofamid pesticide composition and a preparation method thereof, wherein the captan and cyazofamid pesticide composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 1-90% of captan, 1-90% of cyazofamid and the balance of auxiliary components; citric acid reacts with the intermediate 6 to form citrate, the citrate, chitosan, liquid paraffin and span 80 are mixed to prepare coating liquid, the coating liquid and the antibacterial composition are blended and then are crosslinked by glutaraldehyde to prepare the pesticide composition, the pesticide composition has a good slow release effect, and after being absorbed by plants, the coating on the surface can promote cell elongation and accelerate package division, so that the growth of the plants is promoted.)

1. A captan and cyazofamid pesticide composition is characterized in that: the antibacterial composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 1-90% of captan, 1-90% of cyazofamid and the balance of auxiliary components;

the coating liquid is prepared by the following steps:

step A1: uniformly mixing 4, 5-dimethyl phthalic anhydride, deionized water and sodium hydroxide, performing reflux reaction, adding N, N-diethylaminoethanol and titanyl sulfate, continuously reacting to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride, and reacting to obtain an intermediate 2;

step A2: uniformly mixing the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide, carrying out reflux reaction to obtain an intermediate 3, uniformly mixing dichloromethane, N-nitro-2, 4, 6-trinitroaniline and triethylamine, stirring, introducing phosgene, reacting, and heating to react to obtain an intermediate 4;

step A3: dissolving the intermediate 4 in xylene, stirring and dropwise adding p-methylaniline, after the dropwise adding is finished, heating for reaction, adding potassium permanganate for reaction to prepare an intermediate 5, and after the intermediate 3, the intermediate 5, N-dimethylformamide and copper sulfate are uniformly mixed, reacting to prepare an intermediate 6;

step A4: heating citric acid to melt, adding the intermediate 6, stirring to obtain citrate, mixing citrate, glacial acetic acid and chitosan, stirring, adding liquid paraffin and span 80, and stirring to obtain coating solution.

2. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the auxiliary component is one or a mixture of more of a dispersing agent, a disintegrating agent, a water-soluble organic solvent and a filler in any ratio, and can be selected according to the prepared pesticide formulation.

3. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the formulation of the captan and cyazofamid pesticide composition is suspending agent, seed coating agent, wettable powder, water dispersible granules, microcapsule suspending agent, coated granules, extruded granules and effervescent tablets.

4. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the dosage ratio of the 4, 5-dimethylphthalic anhydride, the deionized water, the sodium hydroxide, the N, N-diethylaminoethanol and the titanyl sulfate described in the step A1 is 0.1mol:0.2mol:50mL:0.25mol:0.6g, and the dosage ratio of the intermediate 1, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.01mol:0.01mol:0.02g:20 mL.

5. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the using amount ratio of the intermediate 2, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step A2 is 5.8g to 11g to 100mL to 2.5g, and the using amount ratio of the dichloromethane, the N-nitro-2, 4, 6-trinitroaniline, the triethylamine and the phosgene is 20mL to 8mol to 16mol to 3 mol.

6. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the dosage ratio of the intermediate 4, the p-methylaniline and the potassium permanganate in the step A3 is 0.03mol:0.03mol:5.2g, and the dosage ratio of the intermediate 3, the intermediate 5 and the copper sulfate is 0.1mol:0.2mol:0.35 g.

7. The captan and cyazofamid pesticide composition as claimed in claim 1, wherein: the molar ratio of the intermediate 6 to the citric acid in the step A4 is 1:2, and the molar ratio of the glacial acetic acid, the chitosan and the citrate is 50mL:2g:0.5g:1.2g:1 g.

8. The preparation method of the captan and cyazofamid pesticide composition as claimed in claim 1, characterized in that: the method specifically comprises the following steps:

step S1: mixing the antibacterial composition and the coating solution, and performing ultrasonic treatment for 1-1.5h under the condition of frequency of 50-80kHz to obtain a mixed solution;

step S2: adding glutaraldehyde into the mixed solution, stirring for 3-5h at the rotation speed of 300-500r/min and the temperature of 30-35 ℃, standing for layering, removing supernatant, washing a substrate with petroleum ether, and drying to obtain the pesticide composition.

Technical Field

The invention relates to the technical field of pesticide preparation, and particularly relates to a captan and cyazofamid pesticide composition and a preparation method thereof.

Background

Captan belongs to a traditional organic sulfur bactericide, has a main protection effect and a certain treatment effect, and has an action mechanism of mainly destroying a thiamine pyrophosphate structure and influencing pyruvic acid oxidation decarboxylation and tricarboxylic acid circulation so as to influence the normal metabolism of cell energy and finally inhibit the normal growth of pathogenic hypha and spores. The pesticide composition has good control effect on various diseases on crops, such as pear scab, grape downy mildew, tomato early blight, pepper anthracnose and the like, and soil-borne diseases, such as root rot, damping off, blight and the like. The captan has been used for years on seed dressing, shows good control effect on soil-borne diseases, but has short duration.

Cyazofamid is a novel low-toxicity bactericide, has good protective activity and certain systemic therapeutic activity, has long lasting period, is rain-wash resistant, and is safe and convenient to use. The medicine belongs to a mitochondrial respiration inhibitor, the sterilization mechanism of the medicine is to lead the death of germs by inhibiting Qi in cytochrome bcl in the metabolism process of the germs, and the medicine is different from methoxy acrylate medicines (which are QO inhibitors in the cytochrome bcl). Has effects on all growth stages of oomycetes, and has activity on resistant or sensitive pathogenic bacteria of metalaxyl.

The existing pesticide bactericide has a common bactericidal effect, part of crops are infected with diseases after the bactericide is used, and the fertilizer is required to be used for multiple times to promote the growth of the crops while the bactericide is used, so that the planting cost is greatly improved.

Disclosure of Invention

The invention aims to provide a captan and cyazofamid pesticide composition and a preparation method thereof, wherein the captan and cyazofamid are compounded, so that the problem that the pesticide has a common sterilization effect at the present stage is solved, and the problems that the fertilizer needs to be used for many times to promote the growth of crops and the planting cost is high at the present stage are solved through a coating solution.

The purpose of the invention can be realized by the following technical scheme:

the captan and cyazofamid pesticide composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 1-90% of captan, 1-90% of cyazofamid and the balance of auxiliary components;

the pesticide composition is prepared by the following steps:

step S1: mixing the antibacterial composition and the coating solution, and performing ultrasonic treatment for 1-1.5h under the condition of frequency of 50-80kHz to obtain a mixed solution;

step S2: adding glutaraldehyde into the mixed solution, stirring for 3-5h at the rotation speed of 300-500r/min and the temperature of 30-35 ℃, standing for layering, removing supernatant, washing a substrate with petroleum ether, and drying to obtain the pesticide composition.

Furthermore, the volume ratio of the mixed solution to the glutaraldehyde is 5: 1.

Furthermore, the auxiliary component is one or a mixture of several of a dispersing agent, a disintegrating agent, a water-soluble organic solvent and a filler in any ratio, and can be selected according to the prepared pesticide formulation.

Furthermore, the formulation of the captan and cyazofamid pesticide composition is suspending agent, seed coating agent, wettable powder, water dispersible granule, microcapsule suspending agent, coated granule, extruded granule and effervescent tablet.

Further, the coating liquid is prepared by the following steps:

step A1: uniformly mixing 4, 5-dimethyl phthalic anhydride, deionized water and sodium hydroxide, performing reflux reaction for 3-5h at the rotation speed of 150-120 ℃ at the temperature of 110-120 ℃, adding N, N-diethylaminoethanol and titanyl sulfate, continuing the reaction for 10-15h to prepare an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride, and performing the reaction for 8-10h at the temperature of 80-90 ℃ to prepare an intermediate 2;

the reaction process is as follows:

step A2: uniformly mixing the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide, carrying out reflux reaction for 2-3h to obtain an intermediate 3, uniformly mixing dichloromethane, N-nitro-2, 4, 6-trinitroaniline and triethylamine, stirring and introducing phosgene at the rotation speed of 150-;

the reaction process is as follows:

step A3: dissolving the intermediate 4 in xylene, stirring and dropwise adding p-methylaniline under the conditions that the rotation speed is 200-plus-one at 300r/min and the temperature is 20-25 ℃, heating to the temperature of 60-70 ℃ after dropwise adding, reacting for 2-4h, adding potassium permanganate, reacting for 6-8h under the condition that the temperature is 120-plus-one at 130 ℃ to prepare an intermediate 5, uniformly mixing the intermediate 3, the intermediate 5, N-dimethylformamide and copper sulfate, and reacting for 5-7h under the conditions that the rotation speed is 200-plus-one at 300r/min and the temperature is 120-plus-one at 130 ℃ to prepare an intermediate 6;

the reaction process is as follows:

step A4: heating citric acid to be molten at the temperature of 120-130 ℃, adding the intermediate 6, stirring at the rotation speed of 150-200r/min for 3-5h to prepare citrate, mixing the citrate, glacial acetic acid and chitosan, stirring at the rotation speed of 1500-1800r/min for 30-40min, adding liquid paraffin and span 80, and stirring at the rotation speed of 800-1000r/min for 1-1.5h to prepare coating liquid.

Further, the dosage ratio of the 4, 5-dimethylphthalic anhydride, the deionized water, the sodium hydroxide, the N, N-diethylaminoethanol and the titanyl sulfate described in the step A1 is 0.1mol:0.2mol:50mL:0.25mol:0.6g, and the dosage ratio of the intermediate 1, the N-bromosuccinimide, the benzoyl peroxide and the carbon tetrachloride is 0.01mol:0.01mol:0.02g:20 mL.

Further, the using amount ratio of the intermediate 2, the potassium carbonate, the deionized water and the tetraethylammonium bromide in the step A2 is 5.8g:11g:100mL:2.5g, and the using amount ratio of the dichloromethane, the N-nitro-2, 4, 6-trinitroaniline, the triethylamine and the phosgene is 20mL:8mol:16mol:3 mol.

Further, the dosage ratio of the intermediate 4, the p-methylaniline and the potassium permanganate in the step A3 is 0.03mol:0.03mol:5.2g, and the dosage ratio of the intermediate 3, the intermediate 5 and the copper sulfate is 0.1mol:0.2mol:0.35 g.

Further, the molar ratio of the intermediate 6 and the citric acid in the step A4 is 1:2, and the molar ratio of the glacial acetic acid, the chitosan and the citrate is 50mL:2g:0.5g:1.2g:1 g.

The invention has the beneficial effects that: the invention provides a pesticide composition, which takes captan and cyazofamid as raw materials, the pesticide composition has good sterilization effect through the compounding of the captan and the cyazofamid, and coating liquid is prepared, the coating liquid takes 4, 5-dimethyl phthalic anhydride and N, N-diethylaminoethanol as raw materials to react to prepare an intermediate 1, the intermediate 1 is treated with N-bromosuccinimide to prepare an intermediate 2, the intermediate 2 is treated to prepare an intermediate 3, N-nitro-2, 4, 6-trinitroaniline is reacted with phosgene to prepare an intermediate 4, the intermediate 4 is reacted with p-methylaniline to prepare an intermediate 5, the intermediate 3 and the intermediate 5 are esterified to prepare an intermediate 6, citric acid is reacted with the intermediate 6 to form citrate, and mixing the citrate, the chitosan, the liquid paraffin and the span 80 to prepare a coating solution, blending the coating solution and the antibacterial composition, and crosslinking the mixture by glutaraldehyde to prepare the pesticide composition.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The captan and cyazofamid pesticide composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 1% of captan, 90% of cyazofamid and the balance of auxiliary components;

the pesticide composition is prepared by the following steps:

step S1: mixing the antibacterial composition and the coating solution, and performing ultrasonic treatment for 1h under the condition of 50kHz frequency to obtain a mixed solution;

step S2: adding glutaraldehyde into the mixed solution, stirring for 3h at the rotation speed of 300r/min and the temperature of 30 ℃, standing for layering, removing supernatant, washing a substrate with petroleum ether, drying to obtain a pesticide composition, and preparing the pesticide composition into a suspending agent.

The coating liquid is prepared by the following steps:

step A1: uniformly mixing 4, 5-dimethyl phthalic anhydride, deionized water and sodium hydroxide, performing reflux reaction for 3 hours at the rotation speed of 150r/min and the temperature of 110 ℃, adding N, N-diethylaminoethanol and titanyl sulfate, continuously reacting for 10 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride, and reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 2;

step A2: uniformly mixing the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide, carrying out reflux reaction for 2 hours to obtain an intermediate 3, uniformly mixing dichloromethane, N-nitro-2, 4, 6-trinitroaniline and triethylamine, stirring and introducing phosgene at the rotation speed of 150r/min and the temperature of 0 ℃, reacting for 1 hour, heating to 40 ℃, and continuing to react for 4 hours to obtain an intermediate 4;

step A3: dissolving the intermediate 4 in xylene, stirring and dropwise adding p-methylaniline under the conditions of the rotation speed of 200r/min and the temperature of 20 ℃, heating to the temperature of 60 ℃ after dropwise adding, reacting for 2 hours, adding potassium permanganate, reacting for 6 hours under the temperature of 120 ℃ to obtain an intermediate 5, uniformly mixing the intermediate 3, the intermediate 5, N-dimethylformamide and copper sulfate, and reacting for 5 hours under the conditions of the rotation speed of 200r/min and the temperature of 120 ℃ to obtain an intermediate 6;

step A4: heating citric acid to be molten at 120 ℃, adding the intermediate 6, stirring for 3 hours at the rotation speed of 150r/min to prepare citrate, mixing the citrate, glacial acetic acid and chitosan, stirring for 30 minutes at the rotation speed of 1500r/min, adding liquid paraffin and span 80, and stirring for 1 hour at the rotation speed of 800r/min to prepare the coating liquid.

Example 2

The captan and cyazofamid pesticide composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 45% of captan, 45% of cyazofamid and the balance of auxiliary components;

the pesticide composition is prepared by the following steps:

step S1: mixing the antibacterial composition and the coating solution, and performing ultrasonic treatment for 1.3h under the condition of the frequency of 60kHz to obtain a mixed solution;

step S2: adding glutaraldehyde into the mixed solution, stirring for 4h at the rotation speed of 400r/min and the temperature of 33 ℃, standing for layering, removing supernatant, washing a substrate with petroleum ether, drying to obtain a pesticide composition, and preparing the pesticide composition into water dispersible granules.

The coating liquid is prepared by the following steps:

step A1: uniformly mixing 4, 5-dimethyl phthalic anhydride, deionized water and sodium hydroxide, performing reflux reaction for 4 hours at the rotation speed of 180r/min and the temperature of 115 ℃, adding N, N-diethylaminoethanol and titanyl sulfate, continuously reacting for 13 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride, and reacting for 9 hours at the temperature of 85 ℃ to obtain an intermediate 2;

step A2: uniformly mixing the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide, carrying out reflux reaction for 2.5 hours to obtain an intermediate 3, uniformly mixing dichloromethane, N-nitro-2, 4, 6-trinitroaniline and triethylamine, stirring and introducing phosgene under the conditions that the rotating speed is 180r/min and the temperature is 3 ℃, reacting for 1.5 hours, heating to 45 ℃, and continuing to react for 5 hours to obtain an intermediate 4;

step A3: dissolving the intermediate 4 in xylene, stirring and dropwise adding p-methylaniline under the conditions that the rotation speed is 300r/min and the temperature is 23 ℃, heating to 65 ℃ after dropwise adding, reacting for 3 hours, adding potassium permanganate, reacting for 7 hours under the condition that the temperature is 125 ℃ to prepare an intermediate 5, uniformly mixing the intermediate 3, the intermediate 5, N-dimethylformamide and copper sulfate, and reacting for 6 hours under the conditions that the rotation speed is 200r/min and the temperature is 125 ℃ to prepare an intermediate 6;

step A4: heating citric acid to melt at 125 ℃, adding the intermediate 6, stirring at the rotation speed of 180r/min for 4 hours to prepare citrate, mixing the citrate, glacial acetic acid and chitosan, stirring at the rotation speed of 1800r/min for 35 minutes, adding liquid paraffin and span 80, and stirring at the rotation speed of 1000r/min for 1.3 hours to prepare the coating liquid.

Example 3

The captan and cyazofamid pesticide composition is prepared by coating an antibacterial composition and a coating solution, wherein the antibacterial composition comprises the following raw materials in percentage by weight: 90% of captan, 1% of cyazofamid and the balance of auxiliary components;

the pesticide composition is prepared by the following steps:

step S1: mixing the antibacterial composition and the coating solution, and performing ultrasonic treatment for 1.5h under the condition of frequency of 80kHz to obtain a mixed solution;

step S2: adding glutaraldehyde into the mixed solution, stirring for 5h at the rotation speed of 500r/min and the temperature of 35 ℃, standing for layering, removing supernatant, washing a substrate with petroleum ether, drying to obtain a pesticide composition, and preparing the pesticide composition into wettable powder.

The coating liquid is prepared by the following steps:

step A1: uniformly mixing 4, 5-dimethyl phthalic anhydride, deionized water and sodium hydroxide, performing reflux reaction for 5 hours at the rotation speed of 200r/min and the temperature of 120 ℃, adding N, N-diethylaminoethanol and titanyl sulfate, continuously reacting for 15 hours to obtain an intermediate 1, uniformly mixing the intermediate 1, N-bromosuccinimide, benzoyl peroxide and carbon tetrachloride, and reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 2;

step A2: uniformly mixing the intermediate 2, potassium carbonate, deionized water and tetraethylammonium bromide, carrying out reflux reaction for 3 hours to obtain an intermediate 3, uniformly mixing dichloromethane, N-nitro-2, 4, 6-trinitroaniline and triethylamine, stirring and introducing phosgene under the conditions that the rotating speed is 200r/min and the temperature is 5 ℃, reacting for 2 hours, heating to 50 ℃, and continuing to react for 6 hours to obtain an intermediate 4;

step A3: dissolving the intermediate 4 in xylene, stirring and dropwise adding p-methylaniline under the conditions that the rotation speed is 300r/min and the temperature is 25 ℃, heating to 70 ℃ after dropwise adding, reacting for 4 hours, adding potassium permanganate, reacting for 8 hours under the condition that the temperature is 130 ℃ to prepare an intermediate 5, uniformly mixing the intermediate 3, the intermediate 5, N-dimethylformamide and copper sulfate, and reacting for 7 hours under the conditions that the rotation speed is 300r/min and the temperature is 130 ℃ to prepare an intermediate 6;

step A4: heating citric acid to be molten at 130 ℃, adding the intermediate 6, stirring for 5 hours at the rotation speed of 200r/min to prepare citrate, mixing the citrate, glacial acetic acid and chitosan, stirring for 40 minutes at the rotation speed of 1800r/min, adding liquid paraffin and span 80, and stirring for 1.5 hours at the rotation speed of 1000r/min to prepare the coating liquid.

Comparative example 1

In this comparative example, compared to example 1, no citrate was added during the preparation of the coating solution, and the rest of the procedure was the same.

Comparative example 2

The comparative example is a pesticide composition disclosed in Chinese patent CN 109699665A.

The pesticide compositions prepared in examples 1-3 and comparative examples 1-2 were used for treating watermelon seeds, 30 mu of test field was divided into 5 parts for sowing, and the control effect, emergence rate and plant height of wilt disease in each treatment were investigated after 45 days, with the results shown in the following table;

	example 1	Example 2	Example 3	Comparative example 1	Comparative example 2
						Control rate (%)	95.20	94.85	94.90	94.83	90.35
Rate of emergence (%)	93.80	94.15	93.95	83.27	88.85
						Plant height (cm)	19.3	20.1	19.8	10.7	15.6

As can be seen from the above table, the control rate of the pesticide composition prepared in the examples 1 to 3 on the wilt disease is 94.85 to 95.20 percent, the emergence rate is 93.80 to 94.15, and the plant height is 19.3 to 20.1cm, which shows that the pesticide composition prepared by the invention has good disease-resistant effect and can enhance the growth of plants.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.