Disclosure of Invention
The application provides a nano-scale bactericide containing epoxiconazole and a preparation method thereof in order to improve the field control effect of the nano-scale bactericide.
In a first aspect, the application provides a nano-scale bactericide containing epoxiconazole, which adopts the following technical scheme:
The nano-grade bactericide containing epoxiconazole is mainly prepared from, by weight, 10-15% of epoxiconazole raw material, 1-3% of tripeptide-1 derivative, 0.3-0.7% of 1, 3-dimethyl-2-imidazolidinone, 1-3% of sodium laureth sulfate, 2-4% of sodium polyphosphate, 0.5-0.9% of thickener, 0.001-0.003% of preservative, 3-5% of antifreezing agent, 0.1-0.5% of organic silicon defoamer and the balance of water, wherein the tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate.
The nano-scale bactericide containing the epoxiconazole has the advantages that the epoxiconazole suspension rate is more than 96%, the residue content after pouring is less than 3%, the residue content after washing is less than 0.2%, the low-temperature stability is qualified, the heat storage stability is qualified, the epoxiconazole suspension rate is high, the epoxiconazole is easy to pour and clean, and the storage stability is good through the mutual coordination of the raw materials. The nano-scale bactericide is applied to rice for preventing and treating false smut, the field preventing and treating effect of spray application is more than 73% in 7d and the field preventing and treating effect of spray application is more than 90% in 14d, and the nano-scale bactericide has the advantages of good preventing and treating effect and high pesticide effect, and meets market demands.
The nano-scale bactericide disclosed by the application takes the epoxiconazole as an active ingredient, and the epoxiconazole is suspended in a system in a particle form, so that the epoxiconazole can inhibit the biosynthesis of ergosterol in germ cell membranes and block germ cell wall formation, and the epoxiconazole can also induce the enhancement of chitinase activity, so that chitinase can directly decompose chitin on germ cell walls, thereby leading to cell wall defect and cell membrane exposure, finally leading to germ death, and realizing the drug effect. On this basis, tripeptide-1 derivatives and 1, 3-dimethyl-2-imidazolidinone were added. The tripeptide-1 derivative is obtained by treating tripeptide-1 with ethyl oleate. The synergistic effect between the tripeptide-1 derivative and the 1, 3-dimethyl-2-imidazolidinone is utilized, so that the dispersion of the active ingredients is facilitated, the surface tension can be reduced, the wetting capacity is improved, the affinity between the active ingredients and the leaves can be enhanced, the surfaces of the leaves can be acted, the waxy layers or the horny layers are damaged, a transmission channel is formed, the permeation of the active ingredients is quickened, the active ingredients are fully absorbed, the efficacy is exerted, and the field control effect is improved.
Optionally, the tripeptide-1 derivative is prepared by mixing an organic solvent and tripeptide-1, adding ethyl oleate, stirring for 18-22h, and distilling under reduced pressure to obtain the tripeptide-1 derivative.
Optionally, the weight ratio of the tripeptide-1 to the ethyl oleate is 10 (3-4).
By adopting the technical scheme, the tripeptide-1 contains amino, the ethyl oleate contains ester groups, the ethyl oleate is grafted onto the tripeptide-1 by utilizing the reaction of the amino groups and the ester groups, and the tripeptide-1 derivative is obtained, so that the stability of the tripeptide-1 derivative preparation is ensured, and the quality and the use effect of the tripeptide-1 derivative are ensured.
Optionally, the weight ratio of the tripeptide-1 to the organic solvent is 1 (8-12).
In various embodiments, the weight ratio of tripeptide-1 to organic solvent is 1:10, and the weight ratio can be set to 1:8, 1:9, 1:11 and 1:12 according to the requirement, but the invention is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Optionally, the organic solvent is one or more of ethanol, ethylene glycol, propanol, propylene glycol and glycerol.
By adopting the technical scheme, the organic solvent is limited, so that the selection of the organic solvent is facilitated. In addition, the organic solvent can fully contact and react the tripeptide-1 and the ethyl oleate, so that the preparation stability and the use effect of the tripeptide-1 derivative are ensured.
In the preparation method of the tripeptide-1 derivative, in various embodiments, the stirring treatment is performed for 20 hours, and the stirring treatment may be performed for 18 hours, 19 hours, 21 hours, and 22 hours as needed, but the method is not limited to the listed values, and other non-listed values within the range of the values are equally applicable.
Optionally, the thickener is selected from two kinds of organic thickener and inorganic thickener, and the weight ratio of the organic thickener to the inorganic thickener is 1 (1-3).
By adopting the technical scheme, the thickener is selected from organic thickeners and inorganic thickeners. By utilizing the synergistic effect of the organic thickener and the inorganic thickener, the viscosity is increased, the fluidity is improved, the active ingredients can be stabilized, the agglomeration of the active ingredients is prevented, the sedimentation is reduced, and the stability of the nano-scale bactericide is ensured.
In various embodiments, the weight ratio of the organic thickener and the inorganic thickener is 1:2, and the weight ratio can be set to be 1:1, 1:1.5, 1:2.5 and 1:3 according to the requirement, but the invention is not limited to the listed values, and other non-listed values in the range of the values are equally applicable.
Optionally, the organic thickener is selected from one or more of xanthan gum, guar gum and sodium carboxymethyl cellulose;
the inorganic thickener is one or more selected from magnesium aluminum silicate, bentonite and white carbon black.
By adopting the technical scheme, the organic thickener and the inorganic thickener are optimized, so that the selection of the organic thickener and the inorganic thickener is facilitated. Moreover, the synergistic effect of the organic thickener and the inorganic thickener is utilized, so that the nano-scale bactericide has good stability and dispersibility, and the use effect of the nano-scale bactericide is improved.
Optionally, the preservative is selected from one or more of methylisothiazolinone, chloromethyl isothiazolinone, sodium benzoate and potassium sorbate;
The antifreezing agent is one or more selected from ethylene glycol, propylene glycol, glycerol and sorbitol.
By adopting the technical scheme, the preservative and the antifreezing agent are optimized, so that the selection of the preservative and the antifreezing agent is facilitated. Moreover, the preservative can prevent the nano-scale bactericide from deteriorating, and the shelf life is prolonged. The antifreezing agent can prevent the nano-scale bactericide from freezing in a low-temperature environment, and ensure that the nano-scale bactericide has good performance in the low-temperature environment.
Optionally, the organic silicon defoamer is selected from one or more of organic silicon defoamer AFE-1410, organic silicon defoamer AFE-7610, organic silicon defoamer BYK-022 and organic silicon defoamer BYK-093.
By adopting the technical scheme, the organic silicon defoamer is limited, so that the organic silicon defoamer is convenient to select. And the organosilicon defoamer can reduce the surface tension of foam, quickly break the foam, eliminate the foam generated in the preparation and use processes, and is beneficial to improving the stability and quality of the nano-scale bactericide.
Optionally, the mass concentration of the epoxiconazole in the epoxiconazole raw medicine is more than or equal to 95 percent, and the mass concentration of the acetone is less than or equal to 0.5 percent.
By adopting the technical scheme, the content of the epoxiconazole in the epoxiconazole raw medicine is limited, the source stability of the epoxiconazole raw medicine is ensured, the stability of the content of the active ingredient in the nano-scale bactericide is also ensured, and the efficacy and the use effect of the nano-scale bactericide are ensured.
In a second aspect, the application provides a preparation method of the nano-scale bactericide containing epoxiconazole, which adopts the following technical scheme:
the preparation method of the nano-scale bactericide containing epoxiconazole comprises the following steps:
Mixing water, epoxiconazole technical, sodium laureth sulfate, sodium polyphosphate, antifreezing agent, thickener and preservative, grinding, adding tripeptide-1 derivative, 1, 3-dimethyl-2-imidazolidinone and organosilicon defoamer, mixing, and obtaining the nano-level bactericide.
By adopting the technical scheme, the preparation of the nano-scale bactericide is convenient, the raw materials are fully mixed, and the stability and quality of the nano-scale bactericide are ensured.
In summary, the application has at least the following advantages:
1. The nano-scale bactericide containing the epoxiconazole has the advantages that the epoxiconazole suspension rate is more than 96%, the residue content after pouring is less than 3%, the residue content after washing is less than 0.2%, the low-temperature stability is qualified, the heat storage stability is qualified, the epoxiconazole suspension rate is high, the epoxiconazole is easy to pour and clean, and the storage stability is good through the mutual coordination of the raw materials.
2. The nano-grade bactericide containing the epoxiconazole takes the epoxiconazole as an active ingredient, and utilizes the synergy between the tripeptide-1 derivative and the 1, 3-dimethyl-2-imidazolidinone, thereby not only being beneficial to the dispersion of the active ingredient, but also increasing the wetting capacity, increasing the affinity with the blade, acting on the surface of the blade to form a transmission channel, accelerating the permeation of the active ingredient, leading the epoxiconazole to be fully absorbed and exert the efficacy, and improving the field control effect. And the field control effect of spray application 14d is more than 90%, so that the spray has the advantages of good control effect and high pesticide effect, and meets the market demand.
Detailed Description
The present application will be described in further detail with reference to examples.
Preparation example
Preparation example 1
A tripeptide-1 derivative prepared by the following method:
100g of tripeptide-1 was added to 1000g of ethanol at a rotation speed of 500r/min and stirred for 5min. Then, 38g of ethyl oleate was added and stirred for 20 hours. Then, the tripeptide-1 derivative is obtained by reduced pressure distillation.
Preparation example 2
A tripeptide-1 derivative is different from preparation example 1 in that ethyl oleate is added in an amount of 30g.
Preparation example 3
A tripeptide-1 derivative is different from preparation example 1 in that ethyl oleate is added in an amount of 40g.
Examples
TABLE 1 amounts of raw materials for nano-sized bactericides (unit:. Times.10 g)
。
Example 1
The nano-scale bactericide containing epoxiconazole has the raw materials and the raw material proportions shown in table 1.
Wherein the mass concentration of the epoxiconazole in the epoxiconazole raw medicine is 97 percent, the mass concentration of the acetone is 0.2 percent, the sodium laureth sulfate is selected from Jinan century chemical industry Co, the sodium polyphosphate is selected from polycarboxylic acid sodium salt HT-5040, the preservative is selected from methylisothiazolinone, the antifreezing agent is selected from ethylene glycol, the organic silicon defoamer is selected from organic silicon defoamer AFE-7610, and the tripeptide-1 derivative is prepared by adopting the method of preparation example 1.
The thickener is selected from two kinds of organic thickener and inorganic thickener, the weight ratio of the organic thickener to the inorganic thickener is 1:2, the organic thickener is selected from xanthan gum, the xanthan gum is instant xanthan gum, the inorganic thickener is selected from magnesium aluminum silicate.
A preparation method of a nano-scale bactericide containing epoxiconazole comprises the following steps:
Adding epoxiconazole technical, sodium laureth sulfate, sodium polyphosphate, antifreeze, thickener and preservative into water, and stirring for 10min. Then grinding for 8 hours at the rotation speed of 2500r/min and the temperature of 15 ℃. Then adding tripeptide-1 derivative, 1, 3-dimethyl-2-imidazolone and organic defoamer, stirring for 30min to obtain the nano-level bactericide.
Example 2
The difference between the nano-scale bactericide containing epoxiconazole and the example 1 is that the raw material ratio of the nano-scale bactericide is different, and the raw material ratio of the nano-scale bactericide is shown in table 1.
Example 3
The difference between the nano-scale bactericide containing epoxiconazole and the example 1 is that the raw material ratio of the nano-scale bactericide is different, and the raw material ratio of the nano-scale bactericide is shown in table 1.
Example 4
The difference between the nano-scale bactericide containing epoxiconazole and the example 1 is that the raw material ratio of the nano-scale bactericide is different, and the raw material ratio of the nano-scale bactericide is shown in table 1.
Example 5
The difference between the nano-scale bactericide containing epoxiconazole and the example 1 is that the raw material ratio of the nano-scale bactericide is different, and the raw material ratio of the nano-scale bactericide is shown in table 1.
Example 6
The difference between the nano-scale bactericide containing epoxiconazole and the example 3 is that the source of the tripeptide-1 derivative is different in the raw materials of the nano-scale bactericide, and the tripeptide-1 derivative is prepared by adopting the method of preparation example 2.
Example 7
The difference between the nano-scale bactericide containing epoxiconazole and the example 3 is that the source of the tripeptide-1 derivative in the raw material of the nano-scale bactericide is different, and the tripeptide-1 derivative is prepared by adopting the method of the preparation example 3.
Comparative example
Comparative example 1
A nano-class bactericide containing epoxiconazole is prepared from epoxiconazole suspension (12.5%) and is chosen from Jiangsu cultivation chemical Co.
Comparative example 2
A nano-scale bactericide containing epoxiconazole, which is different from example 3 in that tripeptide-1 derivative and 1, 3-dimethyl-2-imidazolidinone are replaced with equal amount of water in the raw material of the nano-scale bactericide.
Comparative example 3
A epoxiconazole-containing nano-scale bactericide which is different from example 3 in that the tripeptide-1 derivative is replaced with an equivalent amount of 1, 3-dimethyl-2-imidazolidinone in the raw material of the nano-scale bactericide.
Comparative example 4
A epoxiconazole-containing nano-scale bactericide which is different from example 3 in that 1, 3-dimethyl-2-imidazolidinone is replaced with the same amount of tripeptide-1 derivative in the raw material of the nano-scale bactericide.
Comparative example 5
A epoxiconazole-containing nano-scale bactericide is distinguished from example 3 in that tripeptide-1 derivatives are replaced with an equivalent amount of tripeptide-1 in the raw material of the nano-scale bactericide.
Comparative example 6
A epoxiconazole-containing nano-scale bactericide is distinguished from example 3 in that the tripeptide-1 derivative is replaced with an equivalent amount of ethyl oleate in the raw material of the nano-scale bactericide.
Performance detection
(1) The nano-sized bactericides obtained in examples 1 to 7 and comparative examples 1 to 6 were taken as test samples, respectively, and the following performance tests were carried out on the nano-sized bactericides, and the test results are shown in table 2.
Wherein, according to GB/T14825-2006 method for measuring suspension rate of pesticides, the suspension rate of epoxiconazole of the nano-scale bactericide is detected.
The residual content after pouring and the residual content after washing of the nano-scale bactericide are detected according to GB/T31737-2015 method for measuring the pourability of pesticides.
The low temperature stability is achieved by standing the nano-level bactericide for 14 days at the temperature of 2 ℃, observing that no crystallization is separated out, and no layering phenomenon is qualified, otherwise, the nano-level bactericide is unqualified.
The heat storage stability is obtained by standing the nano-level bactericide for 14 days at 54 ℃ to observe that no crystallization is separated out and no layering phenomenon is qualified, otherwise, the nano-level bactericide is unqualified.
The field control effect is realized by the following method that the rice is planted in advance on a test field, and the rice variety is 19-aroma rice. The test field control object is false smut. The nano-level bactericide is applied to paddy fields to prevent and treat false smut. The application amount of the nano-scale bactericide is 45 mL/mu, and the nano-scale bactericide is sprayed after being diluted by 1000 times by water. And the spraying and the application are carried out once 7 days before the rice false smut occurs, and the spraying and the application are carried out once again at intervals of 10 days, namely the co-spraying and the application are carried out twice in the growth period of the rice. Fixed point sampling is carried out 7 days and 14 days after the end of the two spraying application, and the field control effect is calculated. At the same time, a blank group was prepared. Water was used in place of the nanoscale germicides in the blank.
The false smut of rice is classified into 5 grades, and the grading standard is:
Grade 0, no disease spots, complete health;
stage 1, the area of the disease spots accounts for less than or equal to 5% of the total area of the blade;
stage 2, the area of the disease spots accounts for 6-25% of the total area of the blade;
Stage 3, the area of the disease spots accounts for 26-50% of the total area of the blade;
and 4, the area of the disease spots accounts for more than 50% of the total area of the blade.
Disease index/(%) = (Σ number of leaves of each stage x number of corresponding stages)/(total number of leaves investigated x number of highest stages) ×100%.
Field control effect/(%) = (disease index of blank control area-disease index of spray application area)/disease index of blank control area x 100%.
TABLE 2 detection results
As can be seen from Table 2, the nano-scale bactericide of the application has the advantages of high epoxiconazole suspension ratio, easy dumping, easy cleaning and good storage stability, and has the advantages of >96% epoxiconazole suspension ratio, <3% residual content after dumping, <0.2% residual content after washing, lasting bubbling volume <20mL, qualified low-temperature stability and qualified heat storage stability. And the pesticide is applied to the rice for preventing and treating false smut, the field preventing and treating effect of spray pesticide application 7d is more than 73 percent, the field preventing and treating effect of spray pesticide application 14d is more than 90 percent, and the pesticide has the advantages of good preventing and treating effect and high pesticide effect, and meets market demands.
Example 3 and comparative example 1 were compared. Comparative example 1 used a commercially available 12.5% epoxiconazole suspension and example 3 used a nano-sized biocide of the present application. From the results, the effect of the commercially available 12.5% epoxiconazole suspending agent on preventing and treating false smut is inferior to that of the nano-scale bactericide of the application. This is probably because the nano-scale bactericide of the present application has high epoxiconazole suspension ratio and good stability, and can make epoxiconazole fully exert the drug effect.
Comparative examples 2 to 4 and example 3 were compared. Comparative example 3 was obtained by adding 1, 3-dimethyl-2-imidazolidinone to a material of a nano-scale bactericide as compared with comparative example 2, comparative example 4 was obtained by adding a tripeptide-1 derivative to a material of a nano-scale bactericide as compared with comparative example 2, and example 3 was obtained by adding 1, 3-dimethyl-2-imidazolidinone and a tripeptide-1 derivative to a material of a nano-scale bactericide as compared with comparative example 2. From the above, it can be seen that 1, 3-dimethyl-2-imidazolidinone and tripeptide-1 derivatives are added into the raw materials simultaneously, and the synergistic effect between the two is utilized to obviously improve the field control effect and the drug effect and the use effect of the nano-scale bactericide.
Comparative examples 5 to 6 and example 3 were compared. Tripeptide-1 was added to the material of the nano-scale bactericide of comparative example 5, ethyl oleate was added to the material of the nano-scale bactericide of comparative example 6, and tripeptide-1 derivative was added to the material of the nano-scale bactericide of example 3. From this, it can be seen that by using the reaction of tripeptide-1 and ethyl oleate, grafting ethyl oleate onto tripeptide-1 can effectively increase the compatibility between ethyl oleate and raw materials, improve the heat storage stability, and also significantly improve the field control effect of the nano-scale bactericide.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.