A soluble solution of ethephon and oligosaccharin and its preparation process

Abstract

This invention relates to the field of pesticide technology, specifically to a soluble agent of ethephon and oligosaccharide and its preparation process. By mass percentage, the raw materials for preparation include at least 20-30% ethephon, 1-10% oligosaccharide, 10-20% nonionic surfactant, 5-10% anionic surfactant, 5-15% solvent, 2-5% antifreeze agent, 1-3% silane adjuvant, 0.5-1% pH adjuster, and deionized water to make up the balance. The agent is a compound of ethephon and oligosaccharide, especially when the mass ratio of ethephon to oligosaccharide is controlled at (4-9):1. This effectively inhibits crop height and increases crop yield, achieving a regulatory effect on crop growth while improving crop disease resistance, thus achieving the purpose of disease prevention and control and increased product yield.

Description

Technical Field

[0001] This invention relates to the field of pesticide technology, specifically to a soluble agent of ethephon and oligosaccharides and its preparation process. Background Technology

[0002] Ethephon, a plant growth regulator, has physiological effects such as increasing latex secretion, accelerating ripening, abscission, and senescence, and promoting flowering. Oligosaccharides are plant-induced disease resistance agents extracted from sugar-rich fruit plants using bioengineering methods. When oligosaccharides are sprayed onto the leaves and enter the plant, they regulate plant growth and development, induce the synthesis and accumulation of phytoalexins and other disease-resistant substances, inhibiting and hindering the growth and reproduction of pathogens, thereby improving plant disease resistance and achieving the goals of disease control and increased yield.

[0003] Currently, the effects of single oligosaccharide aqueous solutions on the market are not significant, resulting in low pesticide utilization and easy decomposition and inactivation of oligosaccharides, which greatly limits their application. Existing technologies improve pesticide efficacy through the combination of active ingredients. Chinese patent application (publication number CN111869668A) discloses a compound fungicide containing fluopyram and oligosaccharides and its preparation method. Fluopyram and oligosaccharides are combined as active ingredients to prepare a soluble powder or suspension, which has a high inhibition rate, good antibacterial effect, and high control efficacy against potato late blight. Chinese patent application (publication number CN112715551A) provides a crop growth regulator composed of 28-homobrassinolide and ethephon and its application, specifically applying the mixed formulation to increase crop yield. However, currently, there is no technology that uses ethephon and oligosaccharides together as active ingredients to simultaneously regulate crop growth and improve crop disease resistance, thereby achieving the goals of disease control and increased yield. Summary of the Invention

[0004] One aspect of the present invention provides a soluble agent for ethephon and oligosaccharide, comprising at least ethephon, oligosaccharide, and deionized water.

[0005] Preferably, by mass percentage, the raw materials for preparing the soluble agent include at least 20-30% ethephon, 1-10% oligosaccharide, 10-20% nonionic surfactant, 5-10% anionic surfactant, 5-15% solvent, 2-5% antifreeze, 1-3% silane additive, 0.5-1% pH adjuster, and deionized water to make up the balance.

[0006] As a preferred technical solution, the mass ratio of ethephon to oligosaccharide is (4-9):1, preferably 9:1.

[0007] This invention uses ethephon and oligosaccharide in combination, especially controlling the mass ratio of ethephon to oligosaccharide to be (4-9):1, which can effectively inhibit crop plant height and increase crop yield, thereby regulating crop growth and improving crop disease resistance, achieving the purpose of disease prevention and control and increasing product yield.

[0008] As a preferred technical solution, the nonionic surfactant is at least one of alkylphenol polyoxyethylene ether, alcohol-based polyoxyethylene ether, alkylamine polyoxyethylene ether, and block polyether. Preferably, the nonionic surfactant is selected from one or a combination of several of castor oil polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, sorbitol polyoxyethylene ether, tallow amine polyoxyethylene ether, triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether, isomeric decaol polyoxyethylene ether, and isomeric tridecaol polyoxyethylene ether; preferably, the nonionic surfactant is a combination of triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isomeric tridecaol polyoxyethylene ether; the mass ratio of the triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether to the isomeric tridecaol polyoxyethylene ether is 1:(2-5).

[0009] As a preferred technical solution, the anionic surfactant is at least one of sulfates and sulfonates. Preferably, the anionic surfactant is selected from one or a combination of several of calcium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl ether sulfate, and sodium octyl succinate; preferably, the anionic surfactant is a combination of sodium lauryl ether sulfate and sodium octyl succinate; the mass ratio of sodium lauryl ether sulfate to sodium octyl succinate is 1:(0.2-0.5).

[0010] As a preferred technical solution, the silane additive is at least one of polyether-modified heptamethyltrisiloxane, methylallyl polyether-modified trisiloxane, and acetylenic diol ether-modified trisiloxane; preferably, the silane additive is polyether-modified heptamethyltrisiloxane (CAS No. 27306-78-1, model MY 2000), which is sourced from Anhui Mingyi Silicon Industry Co., Ltd.

[0011] In the development of soluble pesticide formulations, the miscibility between the liquid formulation and water, i.e., the dilution stability of the liquid formulation, is a technical challenge. Especially with the maturity of agricultural automation technology in recent years, the stability of soluble formulations at high concentrations directly affects the effectiveness and efficacy of subsequent pesticide applications. During their research, the inventors discovered that by constructing a stable anionic-nonionic surfactant system based on ethephon and oligosaccharides in the system, and controlling the mass ratio of nonionic to anionic surfactants to be 1:(1-2), the ethephon and oligosaccharides in the system are uniformly dispersed. This ensures that the provided soluble formulation remains clear and transparent under both low-temperature and hot storage conditions, allowing for long-term stable efficacy. In particular, the anionic-nonionic surfactant system constructed by compounding triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isotridecyl alcohol polyoxyethylene ether with sodium lauryl ether sulfate and sodium octyl succinate produces a soluble formulation that remains clear and transparent even under high-concentration dilution conditions, ensuring its stability in subsequent use. The inventors analyzed that the possible reason is that under high concentration dilution conditions, the active ingredient ethephon in the dispersible agent will instantly detach from the surfactant, resulting in crystallization and precipitation. This prevents effective synergistic effects with oligosaccharides. By using anionic and nonionic surfactants with specific HLB values ​​in the system to construct an anionic-nonionic anti-crystallization system, the probability of ethephon instantly detaching from the surfactant in the dispersible agent is significantly reduced, preventing crystallization at high concentration dilutions. Furthermore, in practical application, the inventors found that introducing 1-3 wt% of a silane adjuvant into the constructed anionic-nonionic surfactant system, especially when the silane adjuvant is polyether-modified heptamethyltrisiloxane, gives the provided dispersible agent excellent spreading, wetting, and penetrating properties, greatly promoting the spread of the solution on the crop surface and significantly improving the utilization rate and yield-increasing efficacy of the dispersible agent. The inventors analyzed that the reason might be that the introduction of polyether-modified heptamethyltrisiloxane into the system, together with the anionic nonionic surfactant system in the system, reduces the surface tension of the soluble agent, reduces the contact angle between the droplet and the leaf surface, and enhances the wetting, adhesion and spreading ability of the liquid on the plant surface, thereby improving the efficacy and reducing the dosage.

[0012] As a preferred technical solution, the solvent is at least one or a combination of methanol, ethanol, isopropanol, acetone, and ethyl acetate. Preferably, the solvent is a combination of ethanol and isopropanol; the mass ratio of ethanol to isopropanol is 1:(0.5-2). Based on the system of the present invention, by using a combination of ethanol and isopropanol as a solvent, ethephon is fully dissolved while also facilitating the dissolution of nonionic surfactants, anionic surfactants, and silane auxiliaries in the system. This ensures good compatibility between ethephon and oligosaccharides, avoids crystal precipitation in the soluble solvent system at low temperatures, and maintains a homogeneous, clear, and transparent state.

[0013] As a preferred technical solution, the antifreeze agent is at least one of ethylene glycol, propylene glycol, and urea; preferably, the antifreeze agent is ethylene glycol.

[0014] Another aspect of the present invention provides a process for preparing a soluble agent of ethephon and oligosaccharide: ethephon and silane additive are dissolved in a solvent to obtain an ethephon solution; oligosaccharide, nonionic surfactant and anionic surfactant are added to deionized water to obtain an oligosaccharide solution; the ethephon solution and oligosaccharide solution are mixed and then an antifreeze agent and a pH adjuster are added to adjust the pH to 5.0-7.0 to obtain the final product.

[0015] Beneficial effects

[0016] 1. This invention provides a soluble agent of ethephon and oligosaccharide, which is compounded with ethephon and oligosaccharide, especially by controlling the mass ratio of ethephon and oligosaccharide to (4-9):1. This can effectively inhibit crop plant height and increase crop yield, thereby regulating crop growth and improving crop disease resistance, achieving the purpose of disease prevention and control and increasing product yield.

[0017] 2. Based on the ethephon and oligosaccharide in the system, the present invention constructs a stable anionic-nonionic surfactant system, and controls the mass ratio of nonionic surfactant to anionic surfactant in the system to be 1:(1-2), so that the ethephon and oligosaccharide in the system are uniformly dispersed, and the provided soluble agent presents a clear and transparent state under low temperature and heat storage conditions, and can exert its efficacy stably for a long time.

[0018] 3. This invention constructs an anionic nonionic surfactant system by compounding triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isomeric tridecyl alcohol polyoxyethylene ether with sodium lauryl ether sulfate and sodium octyl succinate. The provided soluble agent remains clear and transparent even under high concentration dilution conditions, ensuring its stability in subsequent use.

[0019] 4. In the anionic-nonionic surfactant system, 1-3 wt% of silane adjuvant is introduced. In particular, when the silane adjuvant is polyether-modified heptamethyltrisiloxane, the provided soluble agent has excellent spreading, wetting and penetrating properties, which greatly promotes the spread of the liquid on the crop surface and fully improves the utilization rate of the soluble agent and the yield-increasing and control effects.

[0020] 5. Based on the system of the present invention, by using a combination of ethanol and isopropanol as solvents, ethephon is fully dissolved, which is beneficial to the dissolution of nonionic surfactants, anionic surfactants and silane auxiliaries in the system. This enables ethephon to achieve good compatibility with oligosaccharides, avoids crystal precipitation in the soluble solvent system under low temperature conditions, and maintains a homogeneous, clear and transparent state. Detailed Implementation

[0021] Example 1

[0022] Example 1 of the present invention provides a soluble agent of ethephon and oligosaccharide, the raw materials for which, by mass percentage, are 27% ethephon, 3% oligosaccharide, 15% nonionic surfactant, 8% anionic surfactant, 12% solvent, 3% antifreeze agent, 2% silane additive, 1% pH adjuster, and deionized water to make up the balance.

[0023] The nonionic surfactant is a combination of triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isotridecyl alcohol polyoxyethylene ether; the mass ratio of the triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and the isotridecyl alcohol polyoxyethylene ether is 1:4.

[0024] The anionic surfactant is a combination of sodium lauryl ether sulfate and sodium succinate sulfonate; the mass ratio of sodium lauryl ether sulfate to sodium succinate sulfonate is 1:0.3.

[0025] The silane additive is polyether-modified heptamethyltrisiloxane (CAS No. 27306-78-1, model MY 2000), which is sourced from Anhui Mingyi Silicon Industry Co., Ltd.

[0026] The solvent is a combination of ethanol and isopropanol; the mass ratio of ethanol to isopropanol is 1:1.

[0027] The antifreeze agent is ethylene glycol.

[0028] The pH adjuster is acetic acid.

[0029] Example 1 of the present invention provides a process for preparing a soluble agent of ethephon and oligosaccharide: ethephon and silane additive are dissolved in a solvent to obtain an ethephon solution; oligosaccharide, nonionic surfactant and anionic surfactant are added to deionized water to obtain an oligosaccharide solution; the ethephon solution and oligosaccharide solution are mixed and then an antifreeze agent and a pH adjuster are added to adjust the pH to 5.5 to obtain the final product.

[0030] Example 2

[0031] Example 2 of the present invention provides a soluble agent of ethephon and oligosaccharide, the raw materials for which, by mass percentage, are 24% ethephon, 6% oligosaccharide, 18% nonionic surfactant, 5% anionic surfactant, 10% solvent, 3% antifreeze agent, 2% silane additive, 1% pH adjuster, and deionized water to make up the balance.

[0032] The nonionic surfactant is a combination of triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isotridecyl alcohol polyoxyethylene ether; the mass ratio of the triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and the isotridecyl alcohol polyoxyethylene ether is 1:5.

[0033] The anionic surfactant is a combination of sodium lauryl ether sulfate and sodium succinate sulfonate; the mass ratio of sodium lauryl ether sulfate to sodium succinate sulfonate is 1:0.3.

[0034] The silane additive is polyether-modified heptamethyltrisiloxane (CAS No. 27306-78-1, model MY 2000), which is sourced from Anhui Mingyi Silicon Industry Co., Ltd.

[0035] The solvent is a combination of ethanol and isopropanol; the mass ratio of ethanol to isopropanol is 1:1.

[0036] The antifreeze agent is ethylene glycol.

[0037] The pH adjuster is acetic acid.

[0038] Example 2 of the present invention provides a process for preparing a soluble agent of ethephon and oligosaccharide: ethephon and silane additive are dissolved in a solvent to obtain an ethephon solution; oligosaccharide, nonionic surfactant and anionic surfactant are added to deionized water to obtain an oligosaccharide solution; the ethephon solution and oligosaccharide solution are mixed and then an antifreeze agent and a pH adjuster are added to adjust the pH to 5.5 to obtain the final product.

[0039] Example 3

[0040] Example 3 of the present invention provides a soluble agent of ethephon and oligosaccharide, the raw materials for which, by mass percentage, are 25% ethephon, 5% oligosaccharide, 15% nonionic surfactant, 8% anionic surfactant, 12% solvent, 3% antifreeze agent, 2% silane additive, 1% pH adjuster, and deionized water to make up the balance.

[0041] The nonionic surfactant is a combination of triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and isotridecyl alcohol polyoxyethylene ether; the mass ratio of the triphenylethylphenol polyoxyethylene / polyoxypropylene block polyether and the isotridecyl alcohol polyoxyethylene ether is 1:4.

[0042] The anionic surfactant is a combination of sodium lauryl ether sulfate and sodium succinate sulfonate; the mass ratio of sodium lauryl ether sulfate to sodium succinate sulfonate is 1:0.3.

[0043] The silane additive is polyether-modified heptamethyltrisiloxane (CAS No. 27306-78-1, model MY 2000), which is sourced from Anhui Mingyi Silicon Industry Co., Ltd.

[0044] The solvent is a combination of ethanol and isopropanol; the mass ratio of ethanol to isopropanol is 1:1.

[0045] The antifreeze agent is ethylene glycol.

[0046] The pH adjuster is acetic acid.

[0047] Example 3 of the present invention provides a process for preparing a soluble agent of ethephon and oligosaccharide: ethephon and silane additive are dissolved in a solvent to obtain an ethephon solution; oligosaccharide, nonionic surfactant and anionic surfactant are added to deionized water to obtain an oligosaccharide solution; the ethephon solution and oligosaccharide solution are mixed and then an antifreeze agent and a pH adjuster are added to adjust the pH to 5.5 to obtain the final product.

[0048] Comparative Example 1

[0049] Comparative Example 1 of the present invention provides a soluble agent of ethephon and oligosaccharides and its preparation process. The specific implementation method is the same as that of Example 1, except that the nonionic surfactant is isomeric tridecyl alcohol polyoxyethylene ether.

[0050] Comparative Example 2

[0051] Comparative Example 2 of the present invention provides a soluble agent of ethephon and oligosaccharides and its preparation process. The specific implementation method is the same as that of Example 1, except that the anionic surfactant is calcium dodecylbenzenesulfonate.

[0052] Comparative Example 3

[0053] Comparative Example 3 of the present invention provides a soluble agent of ethephon and oligosaccharide and its preparation method. The specific implementation method is the same as that of Example 1, except that, by mass percentage, the raw materials for preparing the soluble agent include 27% ethephon, 3% oligosaccharide, 5% nonionic surfactant, 5% anionic surfactant, 12% solvent, 3% antifreeze agent, 2% silane additive, 1% pH adjuster, and deionized water to make up the remainder.

[0054] Comparative Example 4

[0055] Comparative Example 4 of the present invention provides a soluble agent of ethephon and oligosaccharide and its preparation method. The specific implementation method is the same as that of Example 1, except that, by mass percentage, the raw materials for preparing the soluble agent include 27% ethephon, 3% oligosaccharide, 5% nonionic surfactant, 15% anionic surfactant, 12% solvent, 3% antifreeze agent, 2% silane auxiliary agent, 1% pH adjuster, and deionized water to make up the remainder.

[0056] Comparative Example 5

[0057] Comparative Example 5 of the present invention provides a soluble agent of ethephon and oligosaccharide and its preparation method. The specific implementation method is the same as that of Example 1, except that, by mass percentage, the raw materials for preparing the soluble agent include 27% ethephon, 3% oligosaccharide, 15% nonionic surfactant, 8% anionic surfactant, 12% solvent, 3% antifreeze, 1% pH adjuster, and deionized water to make up the balance.

[0058] Comparative Example 6

[0059] Comparative Example 6 of the present invention provides a soluble agent of ethephon and oligosaccharide and its preparation method, the specific implementation of which is the same as that of Example 1, except that the solvent is ethanol.

[0060] Performance testing methods

[0061] (1) Referring to GB / T19137-2003 "Determination of Low Temperature Stability of Pesticides", the low temperature stability of the soluble ethephon and oligosaccharide obtained in the examples and comparative examples of this invention was determined. If crystal precipitation occurred during 7 days of cold storage at 0°C, the low temperature stability was recorded as "poor". If crystal precipitation occurred during 7-30 days of cold storage at 0°C, the low temperature stability was recorded as "good". If the composition remained homogeneous, clear and transparent after 30 days of storage at 0°C without crystal precipitation, the low temperature stability was recorded as "excellent". The results are shown in Table 1.

[0062] (2) Referring to GB / T 19136-2003, the method for determining the thermal storage stability of pesticides, the high-temperature stability of the ethephon and oligosaccharide solubles obtained in the examples and comparative examples of this invention was determined. If the solubles became turbid after being stored at 54°C for 14 days, the high-temperature stability was recorded as "unqualified". If the solubles remained homogeneous, clear and transparent after being stored at 54°C for 14 days, the high-temperature stability was recorded as "qualified". The results are shown in Table 1.

[0063] (3) The soluble solvents of ethephon and oligosaccharides obtained in the embodiments and comparative examples of the present invention were dissolved in standard hard water (ρ(Ca)). 2+ +Mg 2+ =342mg / L, prepared according to GBT14825) After diluting 50 times, place in a constant temperature water bath at 30℃ and let stand for 24 hours. If the soluble diluent is homogeneous and there is no precipitation, the high concentration dilution stability is recorded as "qualified"; if the soluble diluent shows precipitation, the high concentration dilution stability is recorded as "unqualified". See Table 1 for the results.

[0064] (4) The soluble ethephon and oligosaccharide obtained in the embodiments and comparative examples of the present invention were diluted 20 times with deionized water to obtain a diluted solution. The surface tension and spreading area of ​​the diluted solution were measured, and the results are shown in Table 1.

[0065] (5) The soluble agents provided in Examples 1-3 of this invention were used to conduct field efficacy tests on the growth regulation of maize (variety Zhenghong 505). Our company's 30% amino acid ester and ethephon aqueous solution were used as comparisons, and water was used as a blank. The application method and water volume were whole-plant spraying, and the water volume per mu was 30 kg. The test results are shown in Table 2.

[0066] Table 1

[0067]

[0068] Table 2

[0069]

[0070]

Claims

1. A soluble liquid of ethephon and oligosaccharins, characterized in that, The preparation raw material comprises at least ethylene 20-30%, oligosaccharin 1-10%, non-ionic surfactant 10-20%, anionic surfactant 5-10%, solvent 5-15%, anti-freezing agent 2-5%, silane auxiliary 1-3%, pH regulator 0.5-1% and deionized water in percentage by mass; the mass ratio of the ethylene and the oligosaccharin is (4-9):1; the non-ionic surfactant is a combination of triphenylethyl phenol polyoxyethylene polyoxypropylene block polyether and isomeric tridecanol polyoxyethylene ether; the mass ratio of the triphenylethyl phenol polyoxyethylene polyoxypropylene block polyether and the isomeric tridecanol polyoxyethylene ether is 1:(2-5); the anionic surfactant is a combination of sodium lauryl ether sulfate and sodium succinyl propionate sulfonate; the mass ratio of the sodium lauryl ether sulfate and the sodium succinyl propionate sulfonate is 1:(0.2-0.5); the silane auxiliary is polyether modified heptamethyltrisiloxane; the solvent is a combination of ethanol and isopropyl alcohol; the mass ratio of the ethanol and the isopropyl alcohol is 1:(0.5-2).

2. The soluble liquid of ethephon and oligosaccharin according to claim 1, characterized by, The anti-freezing agent is at least one of ethylene glycol, propylene glycol and urea.

3. A process for the preparation of a soluble liquid of ethephon and oligosaccharins according to any one of claims 1-2, characterized in that, The ethylene is dissolved in the solvent to obtain an ethylene solution, the oligosaccharin, the non-ionic surfactant and the anionic surfactant are added to deionized water to obtain an oligosaccharin solution, the ethylene solution and the oligosaccharin solution are mixed, the anti-freezing agent is added, and the pH is adjusted to 5.0-7.0 by the pH regulator to obtain the product.

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