阅读说明：本技术 一种含有克菌丹和霜脲氰的杀菌组合物及其制备方法 (Bactericidal composition containing captan and cymoxanil 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：本发明公开了一种含有克菌丹和霜脲氰的杀菌组合物及其制备方法,该杀菌组合物包括如下重量份原料：克菌丹1-90份、氰霜唑1-90份、杀菌增强剂20-25份、余量为辅助成分；该杀菌增效剂上的壳聚糖能够增加细菌对杀菌组合物中杀菌成分的吸收效率,同时该增效剂能够通过在细胞色素b和C1间电子转移抑制线粒体的呼吸,进而抑制孢子的萌发和菌丝的生长,达到杀死细菌的效果,使得杀菌组合物的抗菌效果进一步的提升,且该杀菌增效剂含有异硫氰酸酯基,异硫氰酸酯基进一步的抑制了孢子的萌发和菌丝的生长,使得制备的杀菌组合物具有很好的抗菌效果。(The invention discloses a bactericidal composition containing captan and cymoxanil and a preparation method thereof, wherein the bactericidal composition comprises the following raw materials in parts by weight: 1-90 parts of captan, 1-90 parts of cyazofamid, 20-25 parts of bactericidal enhancer and the balance of auxiliary components; chitosan on the sterilization synergist can increase the absorption efficiency of bacteria to sterilization components in the sterilization composition, meanwhile, the synergist can inhibit the respiration of mitochondria through electron transfer between cytochrome b and C1, further inhibit the germination of spores and the growth of hyphae, the effect of killing bacteria is achieved, the antibacterial effect of the sterilization composition is further improved, the sterilization synergist contains isothiocyanate, the isothiocyanate further inhibits the germination of the spores and the growth of the hyphae, and the prepared sterilization composition has a good antibacterial effect.)

1. The bactericidal composition containing captan and cymoxanil is characterized in that: the bactericidal composition comprises the following raw materials in parts by weight: 1-90 parts of captan, 1-90 parts of cyazofamid, 20-25 parts of bactericidal enhancer and the balance of auxiliary components;

the sterilization enhancer is prepared by the following steps:

step A1: uniformly mixing 2-chloro-4-nitrophenylacetic acid, copper chloride and sodium hydroxide aqueous solution, stirring and refluxing to prepare an intermediate 1, uniformly mixing the intermediate 1, toluene and p-toluenesulfonic acid, performing reflux reaction, adding aluminum trichloride and trimethyl orthoformate, reacting to prepare an intermediate 2, and mixing the intermediate 2 with the solution

2. Uniformly mixing sodium methoxide and methanol, and reacting to obtain an intermediate 3;

step A2: uniformly mixing the intermediate 3, tin powder and concentrated hydrochloric acid, reacting, adjusting the pH value of a reaction solution to obtain an intermediate 4, uniformly mixing ammonia water and carbon disulfide, stirring, adding the intermediate 4, stirring, adding a copper sulfate solution, and continuously stirring to obtain an intermediate 5;

step A3: uniformly mixing 4, 6-dichloro-2-methylpyrimidine, manganese bromide, cobalt bromide, glacial acetic acid and hepatitis B, stirring, introducing oxygen, reacting to obtain an intermediate 6, dissolving the intermediate 6 in N, N-dimethylformamide, adding the intermediate 5, reacting, adding methanesulfonic acid, reacting to obtain an intermediate 7, uniformly mixing the intermediate 7, sodium carbonate, salicylanitrile and N, N-dimethylformamide, and reacting to obtain an intermediate 8;

step A4: dissolving chitosan in acetic acid solution, dissolving glyoxylic acid in deionized water, adding sodium hydroxide solution, adding chitosan solution, reacting, adjusting the pH value of the reaction solution, adding sodium borohydride solution, reacting to obtain carboxymethyl chitosan, uniformly mixing the intermediate 8, glycol, copper sulfate and N, N-dimethylformamide, reacting, adding carboxymethyl chitosan, and continuing to react to obtain the sterilization enhancer.

2. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the auxiliary components are one or a mixture of a plurality of dispersing agents, disintegrating agents, water-soluble organic solvents and fillers in any ratio, and are selected according to the dosage form of the prepared bactericidal composition.

3. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the formulation of the captan and cymoxanil bactericidal composition is one or more of a suspending agent, a seed coating agent, wettable powder, a water dispersible granule, a microcapsule suspending agent, a coated granule, an extruded granule and an effervescent tablet.

4. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the dosage ratio of the 2-chloro-4-nitrophenylacetic acid, the copper chloride and the sodium hydroxide aqueous solution in the step A1 is 0.1mol:0.002mol:100mL, the mass fraction of the sodium hydroxide aqueous solution is 15%, the dosage ratio of the intermediate 1, the toluene, the p-toluenesulfonic acid, the aluminum trichloride and the trimethyl orthoformate is 0.1mol:200mL:0.75mol:0.15mol:0.25mol, and the dosage ratio of the intermediate 2, the sodium methoxide and the methanol is 0.01mol:0.012mol:20 mL.

5. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the dosage ratio of the intermediate 3, the tin powder and the concentrated hydrochloric acid in the step A2 is 3.5g to 6.8g to 20mL, the mass fraction of the concentrated hydrochloric acid is 36%, the dosage ratio of the ammonia water, the carbon disulfide, the intermediate 4 and the copper sulfate solution is 45mL to 0.36g to 0.3g to 200mL, the mass fraction of the ammonia water is 25%, and the mass fraction of the copper sulfate solution is 20%.

6. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the dosage ratio of the 4, 6-dichloro-2-methylpyrimidine, the manganese bromide, the cobalt bromide, the glacial acetic acid and the hepatitis B in the step A3 is 0.25mol:0.2g:0.2g:100mL:40mL, the dosage molar ratio of the intermediate 6, the intermediate 5 and the methanesulfonic acid is 1.25:1:0.25, and the dosage ratio of the intermediate 7, the sodium carbonate, the salicylonitrile and the N, N-dimethylformamide is 0.01mol:0.008mol:0.0125mol:25 mL.

7. The bactericidal composition containing captan and cymoxanil according to claim 1, wherein: the dosage mass ratio of the chitosan to the glyoxylic acid in the step A4 is 1:4.12, the mass fraction of the sodium hydroxide solution is 4%, and the dosage ratio of the intermediate 8, the glycol, the copper sulfate and the carboxymethyl chitosan is 0.01mol:0.01mol:0.03g:2 g.

8. The method for preparing the bactericidal composition containing captan and cymoxanil according to claim 1, wherein the bactericidal composition comprises the following components in percentage by weight: the method specifically comprises the following steps:

weighing captan, cyazofamid, a sterilization enhancer and auxiliary components, uniformly mixing the raw materials, and preparing the sterilization composition according to the dosage form.

Technical Field

The invention relates to the technical field of bactericide preparation, and particularly relates to a bactericidal composition containing captan and cymoxanil and a preparation method thereof.

Background

Cymoxanil is a high-efficiency and low-toxicity fungicide, is used for cruciferous vegetables such as cucumbers, grapes, tomatoes, litchi, jucai and the like, tobacco and other crops, and is used for preventing and controlling crop diseases caused by oomycete pathogens, wherein the oomycete pathogens causing the crop diseases mainly comprise important groups such as pythium, phytophthora, peronophythora, peronospora, plasmopara, peronospora and the like;

captan, chemical name: n-trichloromethylthio-1, 2, 3, 6-tetrahydrophthalimide and captan are broad-spectrum low-toxicity bactericides, have a protective effect as a main part and a certain treatment effect, can prevent and treat various crop diseases such as pear scab, grape downy mildew, tomato early blight, pepper anthracnose and the like on fruit trees and vegetable crops, and have been used for many years, so that the resistance problem is very prominent;

the sterilization composition at the present stage has too many times of use, so that bacteria generate certain resistance, the sterilization effect of the sterilization composition is reduced, and meanwhile, the effect taking time is too long, so that the crop harvest is easily influenced;

in view of the above technical drawbacks, a solution is proposed.

Disclosure of Invention

The invention aims to provide a bactericidal composition containing captan and cymoxanil and a preparation method thereof, and solves the problems that the current bactericidal composition has a common bactericidal effect and long effect taking time, so that crop harvest is influenced through a bactericidal reinforcing agent.

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

the bactericidal composition containing captan and cymoxanil comprises the following raw materials in parts by weight: 1-90 parts of captan, 1-90 parts of cyazofamid, 20-25 parts of bactericidal enhancer and the balance of auxiliary components;

the preparation method of the pesticide composition specifically comprises the following steps:

weighing the raw materials, uniformly mixing the raw materials, and preparing the bactericidal composition according to dosage forms.

Furthermore, the auxiliary components are one or a mixture of a plurality of dispersing agents, disintegrating agents, water-soluble organic solvents and fillers in any ratio, and are selected according to the dosage form of the prepared bactericidal composition.

Furthermore, the formulation of the captan and cymoxanil bactericidal composition is one or more of a suspending agent, a seed coating agent, wettable powder, a water dispersible granule, a microcapsule suspending agent, a coated granule, an extruded granule and an effervescent tablet.

Further, the sterilization enhancer is prepared by the following steps:

step A1: uniformly mixing 2-chloro-4-nitrophenylacetic acid, copper chloride and sodium hydroxide aqueous solution, stirring and refluxing for 5-7h under the conditions of the rotation speed of 150-;

the reaction process is as follows:

step A2: uniformly mixing the intermediate 3, tin powder and concentrated hydrochloric acid, reacting for 30-40min at the rotation speed of 150-200r/min and the temperature of 95-105 ℃, adjusting the pH value of a reaction solution to 9-10 to prepare an intermediate 4, uniformly mixing ammonia water and carbon disulfide, stirring and adding the intermediate 4 at the rotation speed of 200-300r/min and the temperature of 0 ℃, stirring for 30-40min, adding a copper sulfate solution, and continuously stirring for 15-30min to prepare an intermediate 5;

the reaction process is as follows:

step A3: uniformly mixing 4, 6-dichloro-2-methylpyrimidine, manganese bromide, cobalt bromide, glacial acetic acid and hepatitis B, stirring and introducing oxygen under the conditions of the rotation speed of 150-130 ℃ and the temperature of 120-130 ℃ to react for 3-5h to prepare an intermediate 6, dissolving the intermediate 6 in N, N-dimethylformamide, adding the intermediate 5 under the temperature of 70-75 ℃, reacting for 2-3h, adding methylsulfonic acid, reacting for 3-5h under the temperature of 90-95 ℃ to prepare an intermediate 7, uniformly mixing the intermediate 7, sodium carbonate, salicylonitrile and N, N-dimethylformamide, reacting for 2-4h under the conditions of the rotation speed of 200-300r/min and the temperature of 100-105 ℃, to prepare an intermediate 8;

the reaction process is as follows:

step A4: dissolving chitosan in an acetic acid solution, dissolving glyoxylic acid in deionized water, adding a sodium hydroxide solution until the pH value is 4.5, adding a chitosan solution, reacting for 2-4h at the rotation speed of 150-200r/min and the temperature of 20-25 ℃, adjusting the pH value of the reaction solution to 10, adding a sodium borohydride solution, reacting for 4-6h to obtain carboxymethyl chitosan, uniformly mixing the intermediate 8, ethylene glycol, copper sulfate and N, N-dimethylformamide, reacting for 1-3h at the rotation speed of 200-300r/min and the temperature of 120-130 ℃, adding carboxymethyl chitosan, and continuing to react for 6-8h to obtain the bactericidal reinforcing agent.

Further, in the step A1, the use amount ratio of the 2-chloro-4-nitrophenylacetic acid, the copper chloride and the aqueous solution of sodium hydroxide is 0.1mol:0.002mol:100mL, the mass fraction of the aqueous solution of sodium hydroxide is 15%, the use amount ratio of the intermediate 1, the toluene, the p-toluenesulfonic acid, the aluminum trichloride and the trimethyl orthoformate is 0.1mol:200mL:0.75mol:0.15mol:0.25mol, and the use amount ratio of the intermediate 2, the sodium methoxide and the methanol is 0.01mol:0.012mol:20 mL.

Further, the using amount ratio of the intermediate 3, the tin powder and the concentrated hydrochloric acid in the step A2 is 3.5g:6.8g:20mL, the mass fraction of the concentrated hydrochloric acid is 36%, the using amount ratio of the ammonia water, the carbon disulfide, the intermediate 4 and the copper sulfate solution is 45mL:0.36g:0.3g:200mL, the mass fraction of the ammonia water is 25%, and the mass fraction of the copper sulfate solution is 20%.

Further, the dosage ratio of the 4, 6-dichloro-2-methylpyrimidine, the manganese bromide, the cobalt bromide, the glacial acetic acid and the hepatitis B in the step A3 is 0.25mol:0.2g:0.2g:100mL:40mL, the dosage molar ratio of the intermediate 6, the intermediate 5 and the methanesulfonic acid is 1.25:1:0.25, and the dosage ratio of the intermediate 7, the sodium carbonate, the salicylaldehyde and the N, N-dimethylformamide is 0.01mol:0.008mol:0.0125mol:25 mL.

Further, the dosage mass ratio of the chitosan and the glyoxylic acid in the step A4 is 1:4.12, the mass fraction of the sodium hydroxide solution is 4%, and the dosage ratio of the intermediate 8, the glycol, the copper sulfate and the carboxymethyl chitosan is 0.01mol:0.01mol:0.03g:2 g.

The invention has the following beneficial effects:

in the invention, captan and cymoxanil are added in the process of preparing a sterilization composition, the captan is a protective bactericide, is safe to crops and has no phytotoxicity, and also has the function of stimulating plant growth, the cymoxanil has low toxicity to people and livestock, after being mixed with other bactericides for use, the sterilization effect can be improved, a sterilization enhancer is prepared in the process of preparing the sterilization composition, the sterilization enhancer takes 2-chloro-4-nitrophenylacetic acid as a raw material for processing to prepare an intermediate 1, the intermediate 1 undergoes intramolecular dehydration and ring closure under the action of p-toluenesulfonic acid and then reacts with trimethyl orthoformate to prepare an intermediate 2, the intermediate 2 reacts with sodium methoxide to prepare an intermediate 3, the intermediate 3 is reduced to prepare an intermediate 4, the intermediate 4 is further processed to prepare an intermediate 5, oxidizing 4, 6-dichloro-2-methylpyrimidine to convert methyl into carboxyl to prepare an intermediate 6, reacting the intermediate 5 with the intermediate 6 to prepare an intermediate 7, reacting the intermediate 7 with salicylanitrile to prepare an intermediate 8, treating chitosan to prepare carboxymethyl chitosan, esterifying the intermediate 8 with ethylene glycol to react the carboxyl on the intermediate 8 with one alcoholic hydroxyl on the ethylene glycol, esterifying the residual alcoholic hydroxyl on the ethylene glycol with the carboxyl on the carboxymethyl chitosan to crosslink the intermediate 8 with the chitosan to prepare the bactericidal synergist, wherein the chitosan on the bactericidal synergist can increase the absorption efficiency of bacteria on bactericidal components in the bactericidal composition, and can inhibit the respiration of mitochondria by electron transfer between cytochrome b and C1, and further, the germination of spores and the growth of hyphae are inhibited, the effect of killing bacteria is achieved, the antibacterial effect of the sterilization composition is further improved, the sterilization synergist contains isothiocyanate groups, the germination of the spores and the growth of the hyphae are further inhibited by the isothiocyanate groups, and the prepared sterilization composition has a good antibacterial effect.

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 bactericidal composition containing captan and cymoxanil comprises the following raw materials in parts by weight: 1 part of captan, 90 parts of cyazofamid, 20 parts of sterilization enhancer and the balance of auxiliary components;

the preparation method of the pesticide composition specifically comprises the following steps:

weighing the raw materials, uniformly mixing the raw materials, and preparing the sterilizing composition suspending agent according to the dosage form.

The bactericidal enhancer is prepared by the following steps:

step A1: uniformly mixing 2-chloro-4-nitrophenylacetic acid, copper chloride and a sodium hydroxide aqueous solution, stirring and refluxing for 5 hours at the rotation speed of 150r/min and the temperature of 160 ℃ to prepare an intermediate 1, uniformly mixing the intermediate 1, toluene and p-toluenesulfonic acid, performing reflux reaction for 3 hours at the temperature of 120 ℃, adding aluminum trichloride and trimethyl orthoformate, performing reaction for 3 hours at the temperature of 100 ℃ to prepare an intermediate 2, uniformly mixing the intermediate 2, sodium methoxide and methanol, and performing reaction for 8 hours at the rotation speed of 200r/min and the temperature of-5 ℃ to prepare an intermediate 3;

step A2: uniformly mixing the intermediate 3, tin powder and concentrated hydrochloric acid, reacting for 30min at the rotation speed of 150r/min and the temperature of 95 ℃, adjusting the pH value of a reaction solution to 9 to prepare an intermediate 4, uniformly mixing ammonia water and carbon disulfide, stirring and adding the intermediate 4 at the rotation speed of 200r/min and the temperature of 0 ℃, stirring for 30min, adding a copper sulfate solution, and continuously stirring for 15min to prepare an intermediate 5;

step A3: uniformly mixing 4, 6-dichloro-2-methylpyrimidine, manganese bromide, cobalt bromide, glacial acetic acid and hepatitis B, stirring and introducing oxygen at the rotation speed of 150r/min and the temperature of 120 ℃ to react for 3h to obtain an intermediate 6, dissolving the intermediate 6 in N, N-dimethylformamide, adding the intermediate 5 at the temperature of 70 ℃, reacting for 2h, adding methanesulfonic acid, reacting for 3h at the temperature of 90 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 7, sodium carbonate, salicylalonitrile and N, N-dimethylformamide, and reacting for 2h at the rotation speed of 200r/min and the temperature of 100 ℃ to obtain an intermediate 8;

step A4: dissolving chitosan in an acetic acid solution, dissolving glyoxylic acid in deionized water, adding a sodium hydroxide solution until the pH value is 4.5, adding a chitosan solution, reacting for 2 hours at the rotation speed of 150r/min and the temperature of 20 ℃, adjusting the pH value of a reaction solution to 10, adding a sodium borohydride solution, reacting for 4 hours to obtain carboxymethyl chitosan, uniformly mixing the intermediate 8, ethylene glycol, copper sulfate and N, N-dimethylformamide, reacting for 1 hour at the rotation speed of 200r/min and the temperature of 120 ℃, adding carboxymethyl chitosan, and continuing to react for 6 hours to obtain the bactericidal reinforcing agent.

Example 2

The bactericidal composition containing captan and cymoxanil comprises the following raw materials in parts by weight: 45 parts of captan, 45 parts of cyazofamid, 23 parts of a sterilization enhancer and the balance of auxiliary components;

the preparation method of the pesticide composition specifically comprises the following steps:

weighing the raw materials, uniformly mixing the raw materials, and preparing the bactericidal composition water dispersible granule according to the dosage form.

The bactericidal enhancer is prepared by the following steps:

step A1: uniformly mixing 2-chloro-4-nitrophenylacetic acid, copper chloride and a sodium hydroxide aqueous solution, stirring and refluxing for 6 hours at the rotation speed of 180r/min and the temperature of 170 ℃ to prepare an intermediate 1, uniformly mixing the intermediate 1, toluene and p-toluenesulfonic acid, performing reflux reaction for 4 hours at the temperature of 125 ℃, adding aluminum trichloride and trimethyl orthoformate, performing reaction for 4 hours at the temperature of 103 ℃ to prepare an intermediate 2, uniformly mixing the intermediate 2, sodium methoxide and methanol, and performing reaction for 9 hours at the rotation speed of 300r/min and the temperature of-3 ℃ to prepare an intermediate 3;

step A2: uniformly mixing the intermediate 3, tin powder and concentrated hydrochloric acid, reacting for 35min at the rotation speed of 180r/min and the temperature of 100 ℃, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 4, uniformly mixing ammonia water and carbon disulfide, stirring and adding the intermediate 4 at the rotation speed of 300r/min and the temperature of 0 ℃, stirring for 35min, adding a copper sulfate solution, and continuously stirring for 20min to prepare an intermediate 5;

step A3: uniformly mixing 4, 6-dichloro-2-methylpyrimidine, manganese bromide, cobalt bromide, glacial acetic acid and hepatitis B, stirring and introducing oxygen at the rotation speed of 180r/min and the temperature of 125 ℃ to react for 4h to obtain an intermediate 6, dissolving the intermediate 6 in N, N-dimethylformamide, adding the intermediate 5 at the temperature of 73 ℃, reacting for 2-3h, adding methanesulfonic acid, reacting for 4h at the temperature of 93 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 7, sodium carbonate, salicylanitrile and N, N-dimethylformamide, and reacting for 3h at the rotation speed of 300r/min and the temperature of 103 ℃ to obtain an intermediate 8;

step A4: dissolving chitosan in an acetic acid solution, dissolving glyoxylic acid in deionized water, adding a sodium hydroxide solution until the pH value is 4.5, adding a chitosan solution, reacting for 3 hours at the rotation speed of 180r/min and the temperature of 23 ℃, adjusting the pH value of a reaction solution to 10, adding a sodium borohydride solution, reacting for 5 hours to obtain carboxymethyl chitosan, uniformly mixing the intermediate 8, ethylene glycol, copper sulfate and N, N-dimethylformamide, reacting for 2 hours at the rotation speed of 300r/min and the temperature of 125 ℃, adding carboxymethyl chitosan, and continuing to react for 7 hours to obtain the bactericidal reinforcing agent.

Example 3

The bactericidal composition containing captan and cymoxanil comprises the following raw materials in parts by weight: 90 parts of captan, 1 part of cyazofamid, 25 parts of a sterilization enhancer and the balance of auxiliary components;

the preparation method of the pesticide composition specifically comprises the following steps:

weighing the raw materials, uniformly mixing the raw materials, and preparing the wettable powder of the bactericidal composition according to the dosage form.

The bactericidal enhancer is prepared by the following steps:

step A1: uniformly mixing 2-chloro-4-nitrophenylacetic acid, copper chloride and an aqueous solution of sodium hydroxide, stirring and refluxing for 7 hours at the rotation speed of 200r/min and the temperature of 180 ℃ to prepare an intermediate 1, uniformly mixing the intermediate 1, toluene and p-toluenesulfonic acid, performing reflux reaction for 5 hours at the temperature of 130 ℃, adding aluminum trichloride and trimethyl orthoformate, performing reaction for 5 hours at the temperature of 105 ℃ to prepare an intermediate 2, uniformly mixing the intermediate 2, sodium methoxide and methanol, and performing reaction for 10 hours at the rotation speed of 300r/min and the temperature of 0 ℃ to prepare an intermediate 3;

step A2: uniformly mixing the intermediate 3, tin powder and concentrated hydrochloric acid, reacting for 40min at the rotation speed of 200r/min and the temperature of 105 ℃, adjusting the pH value of a reaction solution to 10 to prepare an intermediate 4, uniformly mixing ammonia water and carbon disulfide, stirring and adding the intermediate 4 at the rotation speed of 300r/min and the temperature of 0 ℃, stirring for 40min, adding a copper sulfate solution, and continuously stirring for 30min to prepare an intermediate 5;

step A3: uniformly mixing 4, 6-dichloro-2-methylpyrimidine, manganese bromide, cobalt bromide, glacial acetic acid and hepatitis B, stirring and introducing oxygen at the rotation speed of 200r/min and the temperature of 130 ℃, reacting for 5h to obtain an intermediate 6, dissolving the intermediate 6 in N, N-dimethylformamide, adding the intermediate 5 at the temperature of 75 ℃, reacting for 3h, adding methanesulfonic acid, reacting for 5h at the temperature of 95 ℃ to obtain an intermediate 7, uniformly mixing the intermediate 7, sodium carbonate, salicylalonitrile and N, N-dimethylformamide, and reacting for 2-4h at the rotation speed of 300r/min and the temperature of 105 ℃ to obtain an intermediate 8;

step A4: dissolving chitosan in an acetic acid solution, dissolving glyoxylic acid in deionized water, adding a sodium hydroxide solution until the pH value is 4.5, adding a chitosan solution, reacting for 4 hours at the rotation speed of 200r/min and the temperature of 25 ℃, adjusting the pH value of a reaction solution to 10, adding a sodium borohydride solution, reacting for 6 hours to obtain carboxymethyl chitosan, uniformly mixing the intermediate 8, ethylene glycol, copper sulfate and N, N-dimethylformamide, reacting for 3 hours at the rotation speed of 300r/min and the temperature of 130 ℃, adding carboxymethyl chitosan, and continuing to react for 8 hours to obtain the bactericidal reinforcing agent.

Comparative example 1

The comparative example compares to example 1 without the germicidal enhancer and the rest of the procedure is the same.

Comparative example 2

The comparative example is the bactericidal composition disclosed in Chinese patent CN 102696646A.

Comparative example 3

The comparative example is the bactericidal composition disclosed in Chinese patent CN 104904734A.

The test crop is wheat, the control object is wheat powdery mildew, the test field is flat, the soil is loam, the fertility is medium and high, the pH value is 6.9, the fertilization pipe is well managed during the test, the test medicament and the dosage are additionally provided with a blank control, the blank control is watering only, the treatment is repeated for 4 times, 33 square meters are arranged in each small area, 56 small areas are arranged in random blocks, the sterilization composition of the examples 1-3 and the comparative examples 1-3 is respectively used for controlling 1 time and 2 times are applied in the wheat booting period and the flower raising initial period;

the investigation and statistical method comprises the steps of investigating on the 5 th day, the 10 th day and the 15 th day after the 2 nd application, adopting a random five-point sampling method, taking 20 plants at each point, investigating the upper 3 leaves (including flag leaves if flag leaves exist) of each plant, recording the total leaf number, the diseased leaf number and the diseased leaf rate, recording the diseased leaf number of each level according to the 6-level standard of wheat powdery mildew, and calculating the disease index and the prevention effect, wherein the results are shown in the following table.

Level 0: no disease spots;

level 1: the lesion area accounts for less than 5% of the whole leaf area;

and 2, stage: the lesion area accounts for 6 to 15 percent of the whole leaf area;

and 3, level: the lesion area accounts for 16-25% of the whole leaf area;

4, level: the lesion area accounts for 26-50% of the whole leaf area;

and 5, stage: the lesion area accounts for more than 51 percent of the whole leaf area;

disease index (%) [ Σ (number of diseased leaves at each stage × number of relative stage)/(total number of examined leaves × 9) ] × 100%;

the control effect (%) [ (control disease index-treatment disease index)/control disease index ] × 100%.

As shown in the table, the bactericidal compositions prepared in the examples 1 to 3 have good bactericidal effect and quick response time.

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.