Topramezone nano oil suspending agent aid and preparation method thereof
By using chitosaccharide polyether and its derivatives as additives, the poor emulsification effect and stability of the benzozolene oil suspension agent were solved, and a nano-oil suspension agent with an average particle size of less than 200 nanometers was prepared, which improved the deposition amount and rapid effect of the drug solution, and achieved the effect of reducing and increasing efficiency.
Patent Information
- Application Number
- CN202510580703.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-07
- Publication Date
- 2025-07-29
AI Technical Summary
The suspension agents containing oxalone oil on the market have problems such as poor emulsification effect, increased viscosity during processing, and easy to layer and bottom at room temperature storage. It is urgent to improve the emulsification effect and stability of oxalone nano-oil suspension agent.
Chitooligosaccharide polyether and its derivatives are used as additives to prepare nano-oil suspension agents with an average particle size of less than 200 nanometers through their specific functional groups and spatial structures. The emulsification performance is improved by using the hydroxyl, amino and benzene ring structures on the main chain, and the electrostatic repulsion and steric resistance are increased by the introduction of sulfate to reduce viscosity.
The stability of nano-oil suspension agent and the improvement of the deposition amount of the drug liquid are achieved, the rapid effect and effectiveness are enhanced, and the effect of reducing and increasing efficiency is achieved.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of pesticide adjuvants, and particularly to an adjuvant for pyraoxystrobin nano oil suspension concentrate and a preparation method thereof. Background Art
[0002] With the technological reform, oil suspension concentrate has become an important direction in the development of pesticide formulations. Through nano-preparation technology, the average particle size of the active ingredient of pesticides in the preparation or dispersion system can be stably present in a nano-scale dispersion state, achieving the effect of reducing dosage and increasing efficiency.
[0003] Pyraoxystrobin is a benzoyl pyrazolone herbicide developed by BASF. This drug inhibits 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) in the biosynthesis of plastoquinone, indirectly affects the synthesis of carotenoids, thus interfering with the synthesis and function of chloroplasts, and ultimately leading to severe albinism and usually death after 14 days. Sensitive weeds usually show whitening symptoms within 2 - 5 days after treatment, and the poisoning symptoms are most obvious in the above-ground growth areas (growing points, internodes, leaves, and leaf veins), and the growth of weeds is inhibited. Pyraoxystrobin has good control effects on weeds resistant to glyphosate, triazines, acetolactate synthase inhibitors, and acetyl-CoA carboxylase inhibitors, and can effectively control the main gramineous weeds and broad-leaved weeds on corn crops worldwide. Pyraoxystrobin has the advantages of a broad herbicide spectrum, high activity, strong miscibility, and safety for corn and subsequent crops.
[0004] However, the existing pyraoxystrobin oil suspension concentrates on the market have problems such as poor emulsification effect, increased viscosity during the processing process, easy stratification and bottom settling at room temperature storage, and pasting. Therefore, a new type of surfactant is urgently needed to solve the above problems. Summary of the Invention
[0005] The technical problem to be solved by the present invention is to provide an adjuvant for pyraoxystrobin nano oil suspension concentrate and a preparation method thereof, which can improve the emulsification effect and stability of pyraoxystrobin nano oil suspension concentrate.
[0006] To solve the above technical problem, the technical solution adopted by the present invention is: an adjuvant for pyraoxystrobin nano oil suspension concentrate, and the adjuvant for pyraoxystrobin nano oil suspension concentrate includes compound A or compound B; Compound A includes: (i) the structure of formula 1 when R is salicylic acid and / or the structure of formula 1 when R is ammonium salicylate sulfate, and (ii) at least one of the structure of formula 1 when R is hydrogen, the structure of formula 1 when R is jasmonic acid, and the structure of formula 1 when R is ammonium sulfate; Compound B includes: the structure of formula 1 when R is salicylic acid and the structure of formula 1 when R is ammonium salicylate sulfate; Formula 1; Among them, n is an integer from 1 to 60, m is an integer from 1 to 30, EO is ethylene oxide, PO is propylene oxide, and X is from 2 to 20.
[0007] Another technical solution adopted by the present invention is as follows: The preparation method of the above-mentioned auxiliary agent for pyraoxystrobin nano oil suspension includes the following steps: Mix chitosan oligosaccharide with potassium hydroxide, heat up to 60-80 °C and then carry out vacuum treatment, heat up to 80-120 °C again, add ethylene oxide, add propylene oxide after the reaction, continue the reaction, cool and adjust the pH value to 6-7 after the reaction is completed to obtain the structure of formula 1 when R is hydrogen.
[0008] The beneficial effects of the present invention are as follows: The auxiliary agent for pyraoxystrobin nano oil suspension of the present invention is chitosan oligosaccharide polyether and its derivatives. Through its specific functional groups and spatial structure, it has extremely strong emulsifying properties, hygroscopicity and moisturizing properties, and can firmly "anchor" on pesticide particles, which helps to prepare a pyraoxystrobin nano oil suspension with an average particle size of less than 200 nanometers, achieving the effect of reducing dosage and increasing efficiency. Specific embodiments
[0009] To illustrate the technical content, the achieved purpose and the effects of the present invention in detail, the following is described in conjunction with the embodiments.
[0010] An auxiliary agent for pyraoxystrobin nano oil suspension, the auxiliary agent for pyraoxystrobin nano oil suspension includes compound A or compound B; The compound A includes: (i) the structure of formula 1 when R is salicylic acid and / or the structure of formula 1 when R is ammonium salicylate sulfate, and (ii) at least one of the structure of formula 1 when R is hydrogen, the structure of formula 1 when R is jasmonic acid, and the structure of formula 1 when R is ammonium sulfate; The compound B includes: the structure of formula 1 when R is salicylic acid and the structure of formula 1 when R is ammonium salicylate sulfate; Formula 1; Among them, R is any one of hydrogen, salicylic acid, jasmonic acid, ammonium sulfate and ammonium salicylate sulfate, n is an integer from 1 to 60, m is an integer from 1 to 30, EO is ethylene oxide, PO is propylene oxide, and X is from 2 to 20.
[0011] As can be seen from the above description, the beneficial effects of the present invention are as follows: The chitosan oligosaccharide polyether and its derivatives are used as adjuvants for the pyrazolynate nano oil suspension. The hydroxyl groups, amino groups and benzene ring structures (salicylic acid or ammonium salicylate sulfate) on the main chain have extremely strong emulsifying properties and can firmly "anchor" on the pesticide particles. The specific macromolecular structure of the chitosan oligosaccharide polyether and its derivatives and the steric hindrance of the block polyether to the nanoparticles are strong, which helps to prepare a pyrazolynate nano oil suspension with an average particle size of less than 200 nanometers and maintain the stable state of the nano small particles. It not only has good long-term storage stability, but also can increase the deposition amount of the liquid medicine. At the same time, the structure with multiple hydroxyl groups of the adjuvant has the characteristics of good hygroscopicity and moisturizing property, so it can improve the quick-acting property and long-lasting effect, achieving the effect of reducing dosage and increasing efficiency.
[0012] Salicylic acid and jasmonic acid are functional acids with the functions of plant growth regulation and stress resistance. Introducing sulfate groups into the molecule increases its ionic property and enhances the intermolecular electrostatic repulsion force, thereby increasing the stability of the system. At the same time, sulfates can reduce the viscosity of the preparation, which is more conducive to the dispersion of the technical material.
[0013] n and m are the numbers of ethylene oxide and propylene oxide. The adjuvant for the oil suspension requires an appropriate HLB value (hydrophilic-lipophilic balance value). Too large or too small is not appropriate. The chitosan oligosaccharide polyether with different numbers of ethylene oxide and propylene oxide can be included in the adjuvant for the pyrazolynate nano oil suspension, and different chitosan oligosaccharide polyethers have different HLB values.
[0014] Furthermore, in compound A, the ratio of the mass of the formula 1 structure when R is salicylic acid and / or the formula 1 structure when R is ammonium salicylate sulfate to the total mass of the adjuvant for the pyrazolynate nano oil suspension is 10 - 39:60.
[0015] Furthermore, in compound B, the mass ratio of the formula 1 structure when R is salicylic acid to the formula 1 structure when R is ammonium salicylate sulfate is 5 - 15:3.
[0016] Furthermore, the adjuvant for the pyrazolynate nano oil suspension includes chitosan oligosaccharide polyether salicylate, and chitosan oligosaccharide polyether sulfate and / or chitosan oligosaccharide polyether ester sulfate.
[0017] As can be seen from the above description, the adjuvant for the oil suspension of the present invention preferably includes non-ionic polyether and anionic sulfate, which not only provides electrostatic repulsion, but also can provide steric hindrance to keep the preparation stable.
[0018] Further, another technical solution adopted by the present invention is as follows: The preparation method of the above-mentioned auxiliary agent for pyraoxystrobin nano oil suspension includes the following steps: Mix chitosan oligosaccharide with potassium hydroxide, heat up to 60-80 °C and then conduct vacuum treatment, heat up to 80-120 °C again, add ethylene oxide, and after the reaction, add propylene oxide and continue the reaction. After the reaction is completed, cool and adjust the pH value to 6-7 to obtain the structure of formula 1 when R is hydrogen.
[0019] Further, the weight ratio of potassium hydroxide to chitosan oligosaccharide is 3‰.
[0020] Further, the molar ratio of ethylene oxide to chitosan oligosaccharide is 1-60:1.
[0021] Further, the molar ratio of propylene oxide to chitosan oligosaccharide is 1-30:1.
[0022] Further, it also includes the following steps: Add salicylic acid and p-toluenesulfonic acid to the structure of formula 1 when R is hydrogen, introduce nitrogen, adjust the temperature to 120-135 °C for reaction to obtain the structure of formula 1 when R is salicylic acid.
[0023] Further, it also includes the following steps: Add salicylic acid and p-toluenesulfonic acid to the structure of formula 1 when R is hydrogen, introduce nitrogen, adjust the temperature to 120-135 °C and react for 60-90 min to obtain the structure of formula 1 when R is salicylic acid.
[0024] Further, the weight ratio of p-toluenesulfonic acid to salicylic acid is 5‰.
[0025] Further, it also includes the following steps: Add urea and aminosulfonic acid to the structure of formula 1 when R is salicylic acid, react at 85-95 °C for 0.3-0.7 h, and then heat up to 120-135 °C for reaction to obtain the structure of formula 1 when R is ammonium salicylate sulfate.
[0026] Further, it also includes the following steps: Add urea and aminosulfonic acid to the structure of formula 1 when R is salicylic acid, react at 85-95 °C for 0.3-0.7 h, and then heat up to 120-135 °C and react for 2-3 h to obtain the structure of formula 1 when R is ammonium salicylate sulfate.
[0027] Further, the weight ratio of urea to the total of aminosulfonic acid and chitosan oligosaccharide polyether is 6%.
[0028] As can be seen from the above description, the temperature changes during the reaction of the present invention, making the reaction more complete.
[0029] Further, the molar ratio of aminosulfonic acid to the structure of formula 1 when R is salicylic acid is greater than 1:1.
[0030] Preferably, the molar ratio of sulfamic acid to the structure of Formula 1 when R is salicylic acid is 1:1.02 to 1.07.
[0031] Further, the following steps are further included: adding jasmonic acid and p-toluenesulfonic acid to the structure of Formula 1 when R is hydrogen, introducing nitrogen, adjusting the temperature to 120-135 °C for reaction, and obtaining the structure of Formula 1 when R is jasmonic acid.
[0032] Further, the following steps are further included: adding jasmonic acid and p-toluenesulfonic acid to the structure of Formula 1 when R is hydrogen, introducing nitrogen, adjusting the temperature to 120-135 °C and reacting for 60-90 min, and obtaining the structure of Formula 1 when R is jasmonic acid.
[0033] Further, the weight ratio of p-toluenesulfonic acid to jasmonic acid is 5‰.
[0034] Further, the following steps are further included: adding urea and sulfamic acid to the structure of Formula 1 when R is hydrogen, reacting at 85-95 °C for 0.3-0.7 h, and then raising the temperature to 120-135 °C for reaction, and obtaining the structure of Formula 1 when R is ammonium sulfate.
[0035] Further, the following steps are further included: adding urea and sulfamic acid to the structure of Formula 1 when R is hydrogen, reacting at 85-95 °C for 0.3-0.7 h, and then raising the temperature to 120-135 °C and reacting for 2-3 h, and obtaining the structure of Formula 1 when R is ammonium sulfate.
[0036] Further, the weight ratio of urea to the total of sulfamic acid and chitosan polyether is 6%.
[0037] Further, the molar ratio of sulfamic acid to the structure of Formula 1 when R is hydrogen is greater than 1:1.
[0038] Preferably, the molar ratio of sulfamic acid to the structure of Formula 1 when R is hydrogen is 1:1.02 to 1.07.
[0039] Example 1 of the present invention is: Preparation method of chitosan polyether-1: adding 1 mol of the starting agent chitosan to the reaction kettle, simultaneously adding potassium hydroxide with a weight ratio of 3‰ as a catalyst, stirring, raising the temperature to 70 °C and evacuating to remove moisture, then raising the temperature to 100 °C, slowly adding 20 mol of ethylene oxide in batches, after adding, keeping warm and curing for 30 min, then adding 10 mol of propylene oxide in batches, after the reaction is completed, keeping warm and curing for 30 min, and adjusting the pH value to 6.5 after cooling to obtain chitosan polyether-1.
[0040] Example 2 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether ester-1: Chitosan oligosaccharide polyether-1 prepared in Example 1 and salicylic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p-toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 80 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 127 °C to obtain chitosan oligosaccharide polyether ester-1; The solvent toluene reflux method is: Condensing water is installed outside the sleeve, and the evaporated toluene is installed inside the sleeve, and the toluene is condensed and refluxed by the condensing water.
[0041] Example 3 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether ester-2: Chitosan oligosaccharide polyether-1 prepared in Example 1 and jasmonic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p-toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 80 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 127 °C to obtain chitosan oligosaccharide polyether ester-2.
[0042] Example 4 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether sulfate-1: Chitosan oligosaccharide polyether-1 prepared in Example 1 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 90 °C and the reaction is carried out for 0.5 h, then the temperature is adjusted to 125 °C and the reaction is carried out for 2.5 h to obtain chitosan oligosaccharide polyether sulfate-1.
[0043] Example 5 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether ester sulfate-1: Chitosan oligosaccharide polyether ester-1 prepared in Example 2 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 90 °C and the reaction is carried out for 0.5 h, then the temperature is adjusted to 125 °C and the reaction is carried out for 2.5 h to obtain chitosan oligosaccharide polyether ester sulfate-1.
[0044] Example 6 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether-2: 1 mol of starting agent chitosan oligosaccharide is added to a reaction kettle, and at the same time, potassium hydroxide with a weight ratio of 3‰ is added as a catalyst, stirred, heated to 60 °C and evacuated to remove moisture, then heated to 80 °C, and 60 mol of ethylene oxide is slowly added in batches. After adding, it is kept warm and cured for 30 min, then 25 mol of propylene oxide is added in batches. After the reaction is completed, it is kept warm and cured for 30 min, and the pH value is adjusted to 6 after cooling to obtain chitosan oligosaccharide polyether-2.
[0045] Example 7 of the present invention is: Preparation method of chitosan oligosaccharide polyether ester - 3: Chitosan oligosaccharide polyether - 2 prepared in Example 6 and salicylic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p - toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 60 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 125 °C to obtain chitosan oligosaccharide polyether ester - 3.
[0046] Example 8 of the present invention is: Preparation method of chitosan oligosaccharide polyether ester - 4: Chitosan oligosaccharide polyether - 2 prepared in Example 6 and jasmonic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p - toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 60 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 125 °C to obtain chitosan oligosaccharide polyether ester - 4.
[0047] Example 9 of the present invention is: Preparation method of chitosan oligosaccharide polyether sulfate - 2: Chitosan oligosaccharide polyether - 2 prepared in Example 6 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 85 °C and the reaction is carried out for 0.3 h, then the temperature is adjusted to 120 °C and the reaction is carried out for 2 h to obtain chitosan oligosaccharide polyether sulfate - 2.
[0048] Example 10 of the present invention is: Preparation method of chitosan oligosaccharide polyether ester sulfate - 2: Chitosan oligosaccharide polyether ester - 3 prepared in Example 7 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 85 °C and the reaction is carried out for 0.3 h, then the temperature is adjusted to 120 °C and the reaction is carried out for 2 h to obtain chitosan oligosaccharide polyether ester sulfate - 2.
[0049] Example 11 of the present invention is: Preparation method of chitosan oligosaccharide polyether - 3: 1 mol of starting agent chitosan oligosaccharide is added to a reaction kettle, and at the same time, potassium hydroxide with a weight ratio of 3‰ is added as a catalyst, stirred, heated to 60 °C and evacuated to remove moisture, then heated to 80 °C, 1 mol of ethylene oxide is slowly added in batches. After adding, it is kept warm and cured for 30 min, then 1 mol of propylene oxide is added in batches. After the reaction is completed, it is kept warm and cured for 30 min, and the pH value is adjusted to 7 after cooling to obtain chitosan oligosaccharide polyether - 3.
[0050] Example 12 of the present invention is: Preparation method of chitosan oligosaccharide polyether ester - 5: Chitosan oligosaccharide polyether - 3 prepared in Example 11 and salicylic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p - toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 90 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 130 °C to obtain chitosan oligosaccharide polyether ester - 5.
[0051] Example 13 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether ester - 6: Chitosan oligosaccharide polyether - 3 prepared in Example 11 and jasmonic acid are fed into a reaction kettle at a molar ratio of 1:1. In the case of p - toluenesulfonic acid with a weight ratio of 5‰ as a catalyst, esterification reaction is carried out for 60 min by solvent toluene reflux method, nitrogen is introduced for protection, and the esterification temperature is controlled at 125 °C to obtain chitosan oligosaccharide polyether ester - 6.
[0052] Example 14 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether sulfate - 3: Chitosan oligosaccharide polyether - 3 prepared in Example 11 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 85 °C and the reaction is carried out for 0.3 h, then the temperature is adjusted to 120 °C and the reaction is carried out for 2 h to obtain chitosan oligosaccharide polyether sulfate - 3.
[0053] Example 15 of the present invention is as follows: Preparation method of chitosan oligosaccharide polyether ester sulfate - 3: Chitosan oligosaccharide polyether ester - 5 prepared in Example 12 and sulfamic acid are put into a reaction kettle at a molar ratio of 1.05:1. In the case of urea with a weight ratio of 6% as a catalyst, the temperature is adjusted to 85 °C and the reaction is carried out for 0.3 h, then the temperature is adjusted to 120 °C and the reaction is carried out for 2 h to obtain chitosan oligosaccharide polyether ester sulfate - 3.
[0054] Example 16 of the present invention is as follows: An adjuvant for pyrazogeton nano - oil suspension concentrate, which includes the structural formula 1 when R is salicylic acid and the structural formula 1 when R is ammonium salicylate sulfate.
[0055] Formula 1; Wherein, n is an integer of 60, m is an integer of 30, EO is ethylene oxide, PO is propylene oxide, and X is 20.
[0056] Example 17 of the present invention: A preparation method of an adjuvant for pyrazogeton nano - oil suspension concentrate, the steps are as follows: S1: Add 1 mol of starting agent chitosan oligosaccharide into a reaction kettle, and at the same time add potassium hydroxide with a weight ratio of 3‰ as a catalyst, stir, heat up to 70 °C and evacuate to remove moisture, then heat up to 100 °C, slowly add 20 mol of ethylene oxide in batches. After adding, keep warm and cure for 30 min, then add 10 mol of propylene oxide in batches. After the reaction is completed, keep warm and cure for 30 min, and adjust the pH value to 6.5 after cooling to obtain chitosan oligosaccharide polyether - 1; Add 1 mol of the starting agent chitosan oligosaccharide to the reaction kettle, and at the same time add potassium hydroxide at a weight ratio of 3‰ as a catalyst, stir, heat up to 60 °C and evacuate to remove moisture, then heat up to 80 °C, slowly add 60 mol of ethylene oxide in batches. After adding, keep warm and cure for 30 min, then add 25 mol of propylene oxide in batches. After the reaction is completed, keep warm and cure for 30 min, and adjust the pH value to 6 after cooling to obtain chitosan oligosaccharide polyether-2.
[0057] S2: Charge chitosan oligosaccharide polyether-1 and salicylic acid into the reaction kettle at a molar ratio of 1:1. Under the condition of p-toluenesulfonic acid at a weight ratio of 5‰ as a catalyst, carry out an esterification reaction for 80 min by the solvent toluene reflux method, introduce nitrogen for protection, and control the esterification temperature at 127 °C to obtain chitosan oligosaccharide polyether ester-1; Charge chitosan oligosaccharide polyether-2 and jasmonic acid into the reaction kettle at a molar ratio of 1:1. Under the condition of p-toluenesulfonic acid at a weight ratio of 5‰ as a catalyst, carry out an esterification reaction for 60 min by the solvent toluene reflux method, introduce nitrogen for protection, and control the esterification temperature at 125 °C to obtain chitosan oligosaccharide polyether ester-4.
[0058] S3: Charge chitosan oligosaccharide polyether ester-1 and sulfamic acid into the reaction kettle at a molar ratio of 1.05:1. Under the condition of urea at a weight ratio of 6% as a catalyst, adjust the temperature to 90 °C and react for 0.5 h, then adjust the temperature to 125 °C and react for 2.5 h to obtain chitosan oligosaccharide polyether ester sulfate-1.
[0059] S4: Mix chitosan oligosaccharide polyether ester-1, chitosan oligosaccharide polyether ester-4 and chitosan oligosaccharide polyether ester sulfate-1 in a mass ratio of 2:2:1 to obtain an adjuvant for pyrazoxyfen nano oil suspension concentrate.
[0060] Application example 1 of the present invention is: 4% pyrazoxyfen nano oil suspension concentrate, the formula is shown in Table 1, and the physical and chemical property indexes in the formula are shown in Table 2.
[0061] Table 1
[0062] Table 2
[0063] Application example 2 of the present invention is: 8% pyrazoxyfen - nicosulfuron oil nano oil suspension concentrate, the formula is shown in Table 3, and the physical and chemical property indexes in the formula are shown in Table 4.
[0064] Table 3
[0065] Table 4
[0066] Application Example 3 of the present invention is: 30% topramezone-nicosulfuron nano-oil suspension concentrate. The formula is shown in Table 5, and the physical and chemical property indexes of each item in the formula are shown in Table 6.
[0067] Table 5
[0068] Table 6
[0069] Select the 4% topramezone nano-oil suspension concentrate in Application Example 1 and conduct a field experiment with a commercially available 4% topramezone oil suspension concentrate (Nantong Nanshen Plant Protection Technology Development Co., Ltd., Jiangsu Province, registration number PD20230538) to compare the control effects on barnyard grass and green foxtail in corn fields. The corn seedlings are at the 3-5 leaf stage, and the barnyard grass and green foxtail are at the 2-6 leaf stage. The experimental data are shown in Tables 7 and 8.
[0070] Table 7
[0071] Table 8
[0072] Note: The data in the table are the average values of 3 replicates. Different capital letters after the data indicate significant differences (P < 0.01), and different lowercase letters after the data indicate significant differences (P < 0.05).
[0073] It can be seen from the above experimental data that the 4% topramezone nano-oil suspension concentrate of the present invention has better control effects on barnyard grass and green foxtail than the commercially available 4% topramezone oil suspension concentrate, can increase the drug efficacy by 15-25%, and has the function of reducing dosage and increasing efficiency.
[0074] In summary, the topramezone nano-oil suspension concentrate adjuvant and its preparation method provided by the present invention have the following advantages: (1) The hydroxyl groups, amino groups and benzene ring structures on the main chain of the adjuvant have extremely strong emulsifying properties, enabling it to firmly "anchor" on the pesticide particles.
[0075] (2) The adjuvant is chitosan oligosaccharide polyether and its derivatives, and its specific spatial structure helps to increase the deposition amount of the liquid medicine and prepare a topramezone nano-oil suspension concentrate with an average particle size of less than 200 nanometers.
[0076] (3) The adjuvant has a structure with multiple hydroxyl groups, good hygroscopicity and moisturizing properties, and can improve the quick-acting property and long-lasting property of the topramezone nano-oil suspension concentrate.
[0077] (4) Sulfate groups are introduced into the structure of the adjuvant, increasing the stability of the system and reducing the viscosity of the preparation.
[0078] The above are only embodiments of the present invention, and do not limit the patent scope of the present invention. Any equivalent transformation made using the specification of the present invention, directly or indirectly applied in related technical fields, shall be included in the patent protection scope of the present invention by the same token.
Claims
1. An adjuvant for pyraoxystrobin nano oil suspension concentrate, characterized in that, Comprising compound A or compound B; Said compound A includes: (i) the structure of formula 1 when R is salicylic acid and / or the structure of formula 1 when R is ammonium salicylate sulfate, and (ii) at least one of the structure of formula 1 when R is hydrogen, the structure of formula 1 when R is jasmonic acid, and the structure of formula 1 when R is ammonium sulfate; Said compound B includes: the structure of formula 1 when R is salicylic acid and the structure of formula 1 when R is ammonium salicylate sulfate; Formula 1; Wherein, n is an integer from 1 to 60, m is an integer from 1 to 30, EO is ethylene oxide, PO is propylene oxide, and X is from 2 to 20.
2. The adjuvant for the pyrazoxyfen nano oil suspension agent according to claim 1, wherein The adjuvant of the pyrazolynate nano oil suspension includes chitosan oligosaccharide polyether salicylate, and chitosan oligosaccharide polyether sulfate and / or chitosan oligosaccharide polyether ester sulfate.
3. The preparation method of the adjuvant for the pyraoxystrobin nano oil suspension agent according to claim 1 or 2, characterized in that, Including the following steps: Mix chitosan oligosaccharide with potassium hydroxide, heat up to 60 - 80 °C and then carry out vacuum treatment, heat up again to 80 - 120 °C, add ethylene oxide, react and then add propylene oxide, continue to react, after the reaction is completed, cool and adjust the pH value to 6 - 7 to obtain the structure of formula 1 when R is hydrogen.
4. The preparation method of the adjuvant for the pyraoxystrobin nano oil suspension agent according to claim 3, characterized in that, The molar ratio of ethylene oxide to chitosan oligosaccharide is 1 - 60:
1.
5. The preparation method of the adjuvant for pyraoxystrobin nano oil suspension agent according to claim 3, characterized in that, The molar ratio of propylene oxide to chitosan oligosaccharide is 1 - 30:
1.
6. The preparation method of the adjuvant for pyraoxystrobin nano oil suspension agent according to claim 3, characterized in that, It also includes the following steps: Add salicylic acid and p-toluenesulfonic acid to the structure of formula 1 when R is hydrogen, introduce nitrogen, adjust the temperature to 120 - 135 °C for reaction to obtain the structure of formula 1 when R is salicylic acid.
7. The preparation method of the adjuvant for the pyraoxystrobin nano oil suspension agent according to claim 6, characterized in that, It also includes the following steps: Add urea and aminosulfonic acid to the structure of formula 1 when R is salicylic acid, react at 85 - 95 °C for 0.3 - 0.7 h, and then heat up to 120 - 135 °C for reaction to obtain the structure of formula 1 when R is ammonium salicylate sulfate.
8. The preparation method of the adjuvant for the pyraoxystrobin nano oil suspension agent according to claim 3, characterized in that, It also includes the following steps: Add jasmonic acid and p-toluenesulfonic acid to the structure of formula 1 when R is hydrogen, introduce nitrogen, adjust the temperature to 120 - 135 °C for reaction to obtain the structure of formula 1 when R is jasmonic acid.
9. The preparation method of the adjuvant for the pyrazolynate nano-oil suspension agent according to claim 3, characterized in that, It also includes the following steps: Add urea and aminosulfonic acid to the structure of formula 1 when R is hydrogen, react at 85 - 95 °C for 0.3 - 0.7 h, and then heat up to 120 - 135 °C for reaction to obtain the structure of formula 1 when R is ammonium sulfate.
10. The preparation method of the adjuvant for the pyraoxystrobin nano oil suspension agent according to claim 9, characterized in that, The molar ratio of aminosulfonic acid to the structure of formula 1 when R is hydrogen is greater than 1:1.