Diethylaminoethyl hexanoate-stabilized emulsifiable powder and preparation method thereof

Abstract

The invention relates to stable diethyl aminoethyl hexanoate emulsifiable powder and a preparation method thereof, and belongs to the technical field of plant growth regulators. The emulsifiable powder is prepared from diethyl aminoethyl hexanoate crude oil as a raw material for the first time and is a solid preparation, and compared with liquid preparations such as missible oil and soluble liquid, no organic solvent is used in the formula, so that a large amount of organic solvent can be saved, and harm of the organic solvent to people in the production and use process is avoided; the harm of an organic solvent to the ecological environment and the atmosphere is reduced or avoided, and the pesticide is an environment-friendly pesticide formulation. According to the diethylaminoethyl hexanoate-stabilized emulsifiable powder disclosed by the invention, by screening the adsorption capacity and chemical stability of different types of carriers to diethylaminoethyl hexanoate crude oil and compounding corresponding auxiliaries, the water dispersibility of the emulsifiable powder is improved, and the practical application effect of diethylaminoethyl hexanoate can be improved; meanwhile, the heat storage decomposition rate of the diethyl aminoethyl hexanoate is reduced, and the shelf life of the product is prolonged.

Description

Technical Field

[0001] This invention relates to an amine ester-stabilized emulsifiable powder and its preparation method, belonging to the technical field of plant growth regulators. Background Technology

[0002] Diethyl aminoethyl hexanoate (DA-6) is a plant growth regulator with broad-spectrum and breakthrough effects. The crude DA-6 is a colorless to pale yellow oily liquid with a boiling point of 87–88°C. It is sparingly soluble in water but readily soluble in organic solvents such as ethanol, acetone, and chloroform. Due to the presence of amino groups in its chemical structure, the crude solution is strongly alkaline, significantly disrupting the ester bonds and resulting in poor stability. It decomposes easily even under room temperature storage, and the decomposition is exacerbated under heat storage conditions. Currently, in actual production, manufacturers primarily coordinate it with citric acid to form a salt, preparing DA-6 citrate, thus addressing the water solubility issue.

[0003] Amino ester citrate is a white to off-white solid crystalline or powder with a light ester aroma and oily feel. It is readily soluble in water and soluble in polar organic solvents such as ethanol, methanol, and acetone. Liquid formulations of amino ester citrate, due to their presence in aqueous, alcoholic, or polar solvent systems, readily undergo hydrolysis, alcoholysis, and ammonolysis at room temperature, especially at higher temperatures where decomposition accelerates. Therefore, the shelf life of amino ester citrate formulations is generally very short. Experimental studies have found that amino ester citrate exhibits a high thermal decomposition rate when compounded with most fillers and solvents, affecting the product's efficacy and shelf life.

[0004] Chinese invention patent CN113575578B, published on December 20, 2022, discloses a soluble agent for preventing the decomposition of amino esters, specifically disclosing the preparation of an amino ester soluble agent using various organic solvents as carriers. This amino ester soluble agent, after being stored at 54℃ for 14 days, showed a decomposition rate of <5% compared to samples stored at room temperature, and met the quality standards for amino ester soluble agents. However, this amino ester soluble agent has the following problems: a) The use of large amounts of organic solvents poses potential toxicity to operators (e.g., skin contact, inhalation) and the environment (soil, water sources); organic solvents are volatile, leading to air pollution and potentially exacerbating the greenhouse effect or ozone layer depletion; and many are flammable substances, requiring strict fire prevention during storage and transportation, increasing safety hazards. b) The large-scale use of organic solvents may also be toxic to bees and aquatic organisms (e.g., fish, algae), disrupting the ecological balance; long-term use may also alter the soil microbial community structure and reduce soil activity. c. The formulation has a low content of active ingredient (amino ester) and uses a large amount of organic solvent, which increases the production cost of the formulation.

[0005] Chinese invention patent CN112889823A, published on June 4, 2021, discloses a liquid formulation for improving the stability of amino ester preparations and its preparation method. Specifically, it discloses the preparation of an amino ester liquid formulation with acceptable decomposition rate using propylene glycol methyl ether acetate, triethyl citrate, and glyceryl triacetate as dispersion media, dimethyl sulfoxide, dimethylacetamide, lactic acid, and pyruvic acid as co-solvents, and related alcohol ether adjuvants. This liquid formulation can effectively prevent the decomposition of amino esters and improve the application effect. However, this liquid formulation has the following problems: a) The selected solvents and co-solvents are expensive, making production costs difficult to control. b) The production process uses a large amount of ester and acid solvents, requiring skilled operators; careless operation can easily lead to skin contact and inhalation. c) Long-term use of acidic co-solvents can more easily corrode production equipment and plastic packaging, leading to leakage.

[0006] Chinese invention patent CN114190378A, published on March 18, 2022, discloses a pesticide solid formulation for reducing the decomposition rate of amino esters. Specifically, it discloses the preparation of a formulation using amino ester citrate as a raw material and sugar alcohols and soluble sugars as excipients, in the form of soluble powder, soluble granules, and soluble tablets. This pesticide solid formulation not only effectively reduces the decomposition of amino esters but also facilitates storage and transportation, exhibiting good thermal stability. However, this pesticide solid formulation has the following problems: a) The use of sugar alcohols and soluble sugars as excipients results in higher production costs compared to commonly used fillers. b) Sugar alcohols are highly susceptible to moisture absorption and stickiness during storage and production. Furthermore, the soluble powder formulation employs a pre-mixing, pulverizing, and re-mixing process, which can easily lead to heat accumulation during material pulverization and mixing in actual large-scale production. This increases the material's temperature, and the sugar alcohols and soluble sugars, which are prone to absorbing water and clumping, further exacerbate the stickiness, making actual production and processing difficult. Summary of the Invention

[0007] The first objective of this invention is to provide an emulsifiable powder stabilized by amino esters, and to provide a solid formulation of amino esters made from amino ester crude oil without the use of organic solvents and with good thermal storage stability.

[0008] The second objective of this invention is to provide a method for preparing an amino ester-stabilized emulsifiable powder, and to provide a simple method for preparing an amino ester-stabilized emulsifiable powder.

[0009] To achieve the above objectives, the technical solution of the present invention for an amine ester-stabilized emulsifiable powder is as follows:

[0010] An emulsifiable powder stabilized with amino esters, comprising, by mass percentage, the following main components: 8%–10% amino ester crude oil, 10%–15% emulsifier, and the remainder being a carrier; wherein the emulsifier is two or three of the following: octylphenol polyoxyethylene ether, calcium dodecylbenzenesulfonate, styrene-phenol polyoxyethylene ether, triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, and castor oil polyoxyethylene ether; wherein the carrier is two of the following: water-soluble starch, hydroxyethyl cellulose, polyacrylamide, organobentonite, silica, and diatomaceous earth.

[0011] The beneficial effects of the above technical solution are as follows: This invention, a stabilized emulsifiable powder for amino esters, is a pioneering invention. This invention is the first to prepare an emulsifiable powder using amino ester crude oil as a raw material. It is a solid formulation, and compared with liquid formulations such as emulsifiable concentrates and soluble concentrates, it does not use organic solvents in the formulation, thus saving a significant amount of organic solvents, avoiding the harm to humans caused by organic solvents during production and use, and reducing or avoiding the harm of organic solvents to the ecological environment and atmosphere. It is an environmentally friendly pesticide formulation. This invention's stabilized emulsifiable powder for amino esters improves the water dispersibility of the emulsifiable powder by screening the adsorption capacity and chemical stability of different types of carriers for amino ester crude oil, and by compounding appropriate adjuvants, thereby improving the actual application effect of amino esters; at the same time, it reduces the thermal decomposition rate of amino esters, extending the product's shelf life.

[0012] Furthermore, the amine ester-stabilized emulsifiable powder of the present invention has good flowability and no clumping, avoiding the phenomenon of material stickiness caused by heat accumulation during the production process, which is more conducive to production and packaging; the carriers used are divided into two categories: water-soluble and non-water-soluble, and many of the available carriers are cheaper than the organic solvents commonly used in emulsifiable oils and soluble concentrates, resulting in lower product costs.

[0013] Preferably, the fineness of the carrier is ≤45μm.

[0014] As a further improvement, it is composed of the following components by weight percentage: 8%–10% crude amino ester, 6%–8% octylphenol polyoxyethylene ether, 2%–4% calcium dodecylbenzenesulfonate, 30%–35% hydroxyethyl cellulose, and 40%–50% water-soluble starch.

[0015] As a further improvement, by weight percentage, it consists of the following components: 8%–10% amine ester crude oil, 6%–8% styrene-phenol polyoxyethylene ether, 6%–8% triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, 25%–30% polyacrylamide, 45%–50% organobentonite, and 5%–6% dispersant.

[0016] As a further improvement, it is composed of the following components by weight percentage: 8%–10% crude amine ester, 2%–3% calcium dodecylbenzenesulfonate, 1%–2% triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, 8%–10% castor oil polyoxyethylene ether, 20%–25% silica, 50%–55% diatomaceous earth, and 5%–6% dispersant.

[0017] As a further improvement, the dispersant is one of three selected from SP-2836, calcium lignosulfonate, sodium methylene bisnaphthalene sulfonate, and sodium alkyl naphthalene sulfonate condensate.

[0018] As a further improvement, the dispersant is SP-2836, calcium lignosulfonate, and sodium methylene bisnaphthalene sulfonate; the mass ratio of SP-2836, calcium lignosulfonate, and sodium methylene bisnaphthalene sulfonate is 2:1:2.

[0019] As a further improvement, the dispersant is sodium alkyl naphthalene sulfonate condensate, sodium methylene bisnaphthalene sulfonate, and calcium lignosulfonate; the mass ratio of sodium alkyl naphthalene sulfonate condensate, sodium methylene bisnaphthalene sulfonate, and calcium lignosulfonate is 2:3:1.

[0020] To achieve the above objectives, the technical solution of the preparation method of an amine ester-stabilized emulsifiable powder in this invention is as follows:

[0021] A method for preparing an emulsifiable powder stabilized by amino esters involves mixing crude amino esters and an emulsifier to form an oil phase, then adding a carrier and mixing until the carrier is fully adsorbed.

[0022] The beneficial effects of the above technical solution are as follows: the preparation method of the amine ester stabilized emulsifiable powder of the present invention is simple to operate, does not require complicated instruments and equipment, and is suitable for large-scale industrial production. Attached Figure Description

[0023] Figure 1 This is the chromatogram of the amino ester standard sample in Experimental Example 4 of the present invention;

[0024] Figure 2 This is a chromatogram of the emulsifiable powder sample stabilized by amino esters in Example 1 of Experimental Example 4 of the present invention at room temperature.

[0025] Figure 3 This is a chromatogram of the amine ester-stabilized emulsifiable powder thermal storage sample from Example 1 of Experimental Example 4 of the present invention.

[0026] Figure 4 This is a chromatogram of the emulsifiable powder sample stabilized by amino esters in Example 2 of Experimental Example 4 of the present invention at room temperature.

[0027] Figure 5This is a chromatogram of the amine ester-stabilized emulsifiable powder thermal storage sample from Example 2 of Experimental Example 4 of the present invention.

[0028] Figure 6 This is the chromatogram of the emulsifiable powder stabilized by amino esters in Example 3 of Experimental Example 4 of the present invention at room temperature.

[0029] Figure 7 This is a chromatogram of the amine ester-stabilized emulsifiable powder thermal storage sample from Example 3 of Experimental Example 4 of the present invention.

[0030] Figure 8 This is a chromatogram of the amine ester-stabilized emulsifiable powder sample at room temperature from Example 4 of Experimental Example 4 of the present invention.

[0031] Figure 9 This is a chromatogram of the amine ester-stabilized emulsifiable powder thermal storage sample from Example 4 of Experimental Example 4 of the present invention. Detailed Implementation

[0032] Currently, the existing technologies for aminoethyl ester formulations have the following problems: For dosage forms that can reduce the decomposition rate of aminoethyl esters, liquid formulations are limited to soluble solutions, and solid formulations are limited to soluble powders, soluble granules, and soluble tablets, all of which are water-soluble. There are currently no reports on emulsifiable powders of aminoethyl esters. Soluble solutions use large amounts of solvent, posing potential toxicity to operators (e.g., skin contact, inhalation) and the environment (soil, water sources), and many are flammable substances, requiring strict fire prevention during storage and transportation, increasing safety hazards. For solid formulations, only formulation studies using aminoethyl ester citrate as a raw material and sugar alcohols and soluble sugars as excipients have been conducted, all using water-soluble fillers. Currently, there are no reports on the impact of water-insoluble fillers on the stability of aminoethyl ester formulations. Furthermore, in solid dosage forms, sugar alcohols and soluble sugars, used as excipients, have higher production costs compared to other water-insoluble fillers. In actual large-scale production, the crushing and mixing processes easily generate heat, raising the material's temperature. Sugar alcohols and soluble sugars are prone to absorbing water and clumping, making the material more sticky and causing difficulties in actual production and processing. Meanwhile, in solid dosage forms, the only effective active ingredient is found in formulations using amino ester citrate as a raw material. Currently, there are no reports on emulsifiable powder formulations using amino ester crude oil as a raw material.

[0033] Based on this, the present invention provides an emulsifiable powder stabilized with amino esters. Emulsifiable powders are a novel formulation of pesticides or functional preparations, combining the advantages of powders and emulsions, and are characterized by environmental friendliness, high efficiency, and strong stability. They consist of three basic components: active ingredient, emulsifier, and carrier. The present invention first screens carriers based on the properties of amino esters, finding that water-soluble starch, hydroxyethyl cellulose, polyacrylamide, organobentonite, diatomaceous earth, and silica are suitable carriers for amino ester crude oil. These carriers maintain a dry powder form with a certain degree of fluidity while ensuring that the thermal decomposition rate of the amino ester crude oil is less than 5%.

[0034] Then, based on the aforementioned carriers, emulsifiers were screened, revealing that different carriers are suitable for different emulsifiers. Water-soluble carriers are suitable for use with OP-10 and agricultural emulsion 500#, while water-insoluble carriers are suitable for EL-20, agricultural emulsion 1601, agricultural emulsion 500#, and agricultural emulsion 600#. However, the addition of water-insoluble carriers resulted in precipitation in the system. Therefore, dispersants and wetting agents were added to the water-insoluble carrier system, and appropriate screening was conducted to ultimately determine the appropriate formulation composition.

[0035] The present invention will be further described below with reference to specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. The equipment and raw materials used are all commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0036] The raw materials used in the following embodiments and experimental examples of this invention are as follows:

[0037] Technical grade: aminoethyl ester crude oil, Guangdong Plant Dragon Biotechnology Co., Ltd.

[0038] Dispersants: SP-2836 (Jiangsu Qingyu Chemical Technology Co., Ltd.), calcium lignosulfonate, sodium methylene bisnaphthalene sulfonate (NNO), sodium alkyl naphthalene sulfonate condensate (D-425).

[0039] Wetting agent: Sodium dodecyl sulfate, alkyl naphthalene sulfonate and anionic wetting agent mixture (EFW).

[0040] Emulsifiers: OP-10 (octylphenol polyoxyethylene ether), Agricultural Emulsion 500# (calcium dodecylbenzene sulfonate), Agricultural Emulsion 600# (styrene-phenol polyoxyethylene ether), Agricultural Emulsion 1601 (triphenylethylphenol polyoxypropylene polyoxyethylene block polymer), EL-20 (castor oil polyoxyethylene ether).

[0041] Carriers: water-soluble starch, maltitol, glucose, polyethylene glycol 6000, hydroxyethyl cellulose, polyacrylamide (weight average molecular weight of 2000-3000), anhydrous magnesium sulfate, anhydrous sodium sulfate, ammonium sulfate, organobentonite, kaolin, diatomaceous earth, silica, and light calcium carbonate.

[0042] I. Specific embodiments of the present invention of an amine ester-stabilized emulsifiable powder and its preparation method:

[0043] Example 1

[0044] The amine ester-stabilized emulsifiable powder of this embodiment is composed of the following components by mass percentage: 10% amine ester crude oil, 10% emulsifier, and the remainder is carrier; the emulsifier is OP-10 and agricultural emulsion 500#; the carrier is water-soluble starch and hydroxyethyl cellulose.

[0045] The specific formula is as follows: 10% 98% amino acid ester crude oil, 8% OP-10, 2% agricultural emulsion 500#, 30% hydroxyethyl cellulose, and 50% water-soluble starch.

[0046] The preparation method of the amino ester-stabilized emulsifiable powder of this embodiment is as follows:

[0047] According to the formula ratio, add the amino ester crude oil and emulsifier to prepare the oil phase for later use. While stirring the weighed carrier, add the prepared oil phase and mix continuously until complete adsorption and uniform mixing. After pulverization, the product is obtained and subjected to analysis and testing of various indicators. (Since the amino ester crude oil itself is an oily liquid, it does not need to be dissolved with a solvent and can be directly mixed with the emulsifier to prepare the oil phase.)

[0048] Example 2

[0049] The amine ester-stabilized emulsifiable powder of this embodiment is composed of the following components by mass percentage: 10% amine ester crude oil, 10% emulsifier, and the remainder is carrier; the emulsifier is OP-10 and agricultural emulsion 500#; the carrier is water-soluble starch and hydroxyethyl cellulose.

[0050] The specific formula is as follows: 10% 98% amino acid ester crude oil, 6% OP-10, 4% agricultural emulsion 500#, 30% hydroxyethyl cellulose, and 50% water-soluble starch.

[0051] The preparation method of the amino ester-stabilized emulsifiable powder is as described in Example 1.

[0052] Example 3

[0053] The emulsifiable powder stabilized by amino esters in this embodiment is composed of the following components by mass percentage: 8% amino ester crude oil, 15% emulsifier, 5% dispersant, and the remainder is carrier; the emulsifier is agricultural emulsion 600# and agricultural emulsion 1601; the dispersant is SP-2836, calcium lignosulfonate and NNO; the carrier is polyacrylamide and organobentonite.

[0054] The specific formula is as follows: 8% crude oil with 98% amino acid ester, 8% agricultural emulsion 600#, 7% agricultural emulsion 1601, 2% SP-2836, 1% calcium lignosulfonate, 2% NNO, 25% polyacrylamide, and 47% organic bentonite.

[0055] The preparation method of the amino ester-stabilized emulsifiable powder is as described in Example 1.

[0056] Example 4

[0057] The emulsifiable powder stabilized by amino esters in this embodiment is composed of the following components by mass percentage: 8% amino ester crude oil, 12% emulsifier, 6% dispersant, and the remainder is carrier; the emulsifiers are EL-20, agricultural emulsion 500# and agricultural emulsion 1601; the dispersants are D-425, calcium lignosulfonate and NNO; and the carriers are silica and diatomaceous earth.

[0058] The specific formula is as follows: 8% crude oil with 98% amino acid ester, 8% EL-20, 2% agricultural emulsion 500#, 2% agricultural emulsion 1601, 2% D-425, 1% calcium lignosulfonate, 3% NNO, 20% silica, and 54% diatomaceous earth.

[0059] The preparation method of the amino ester-stabilized emulsifiable powder is as described in Example 1.

[0060] II. Experimental Examples

[0061] This invention involves extensive screening and efficacy verification of raw materials for amine ester-stabilized emulsifiable powders, resulting in a specific formulation for the amine ester-stabilized emulsifiable powder of this invention. The screening process is described in detail below:

[0062] Experiment Example 1: Selection of Carrier

[0063] When screening carriers, the primary consideration is their adsorption capacity for the active ingredient or the solution formed after dissolving in organic solvents, emulsifiers, etc. Other considerations include flowability and the impact on the chemical stability of the active ingredient. Since the oil phase needs to be uniformly dispersed on the carrier filler, the carrier's adsorption capacity directly affects the quality of the emulsifiable powder. This experimental example uses amino ester crude oil to conduct adsorption capacity tests on several carriers that have been pulverized to a certain fineness (carrier fineness ≤45μm).

[0064] Adsorption capacity test procedure: The carrier was put into a solid mixing and stirring device and the mixing and stirring were turned on. While stirring, the crude oil of amino acid ester was evenly atomized and sprayed onto the carrier with a sprayer. The state of the material after adsorption was observed. The observation results are shown in Table 1.

[0065] Table 1

[0066]

[0067]

[0068] Note: Liquidity differences: Good > Average > Poor.

[0069] As shown in Table 1, when crude oil containing amino esters is adsorbed by the carrier at a ratio of 20%, water-soluble starch, organic bentonite, kaolin, diatomaceous earth, silica, and light calcium carbonate exhibit the strongest adsorption capacity, resulting in a dry powder with good flowability after adsorption. Polyethylene glycol 6000, hydroxyethyl cellulose, polyacrylamide, anhydrous magnesium sulfate, and anhydrous sodium sulfate show the second strongest adsorption capacity, resulting in a dry powder with moderate flowability after adsorption. Maltitol, glucose, and ammonium sulfate show the weakest adsorption capacity, resulting in a powder that is not completely dry and has poor flowability after adsorption.

[0070] Therefore, water-soluble starch, organic bentonite, kaolin, diatomaceous earth, silica, light calcium carbonate, polyethylene glycol 6000, hydroxyethyl cellulose, polyacrylamide, anhydrous magnesium sulfate, and anhydrous sodium sulfate were selected as carriers for evaluating the chemical stability of the active ingredients. The chemical stability test of the active ingredients was conducted according to GB / T 19136-2021, "Determination of Thermal Storage Stability of Pesticides". The content of amino esters was detected by gas chromatography, referring to the gas chromatography method in NY / T 4116-2022, "Amino Ester (Amino Ester Citrate) Technical Grade". Specific results are shown in Table 2.

[0071] Table 2

[0072]

[0073]

[0074] As shown in Table 2, using water-soluble starch, hydroxyethyl cellulose, polyacrylamide, organic bentonite, diatomaceous earth, and fumed silica as carriers for amine ester crude oil can keep the material dry and powdery with a certain degree of fluidity; at the same time, the thermal decomposition rate of the amine ester crude oil is less than 5%.

[0075] Experimental Example 2: Screening of Emulsifiers

[0076] Emulsifiers are the core surfactants used in emulsifiable powder formulations. They are usually surfactants with both hydrophilic and lipophilic groups. The addition of a suitable emulsifier can prevent particle aggregation after the emulsifiable powder is diluted with water, thereby allowing it to be well dispersed, suspended, and emulsified in water for spray application.

[0077] 1. Water-soluble carrier

[0078] Formulations were prepared, and different emulsifiers were screened. The specific formulations and results are shown in Table 3.

[0079] Table 3

[0080]

[0081]

[0082] Note: (1) Formula 2 in the table is the formula of the amino ester stabilized emulsifiable powder of Example 1, and Formula 3 is the formula of the amino ester stabilized emulsifiable powder of Example 2.

[0083] (2) In this experimental example, the volume of the precipitate was determined according to GB / T 1603-2001, the method for determining the stability of pesticide emulsions. 0.5 g of sample was weighed and poured into a 100 mL stoppered conical graduated cylinder containing 100 mL of standard hard water at 30℃. The glass stopper was tightened, and the cylinder was inverted 30 times (180°) around the mouth of the cylinder, with each inversion and resetting taking approximately 2 seconds. After completion, the glass stopper was opened, and the graduated cylinder was placed in a 30℃ constant-temperature glass water bath. Timing was started, and the stability of the emulsion was observed after 1 hour.

[0084] When all carriers used are water-soluble substances, the emulsion is considered acceptable if it remains homogeneous and free of precipitation. If the carrier contains a large amount of non-water-soluble substances, the volume of sediment should not exceed 1 mL. However, if oil droplets or cream are observed to precipitate at the bottom or top, or cream is observed to precipitate at the top, the emulsion is considered unacceptable.

[0085] As shown in Table 3, using hydroxyethyl cellulose and water-soluble starch as adsorbent carriers and fillers, and using emulsifier OP-10 and agricultural emulsion 500# for emulsion stability adjustment, the emulsion stability of formulations 2 and 3 is qualified, with no oil droplets or oil paste precipitation, and the precipitate volume is 0 mL.

[0086] 2. Water-insoluble carrier

[0087] Formulations were prepared, and different emulsifiers were screened. The specific formulations and results are shown in Tables 4 and 5.

[0088] Table 4

[0089]

[0090]

[0091] As shown in Table 4, using polyacrylamide and organic bentonite as adsorbent carriers and fillers, and using emulsifiers Nongru 600# and Nongru 1601 to adjust the emulsion stability, the emulsion stability of Formula 6 is qualified, with no oil droplets or oil paste precipitation; however, the volume of precipitate is 2 mL.

[0092] Table 5

[0093] Formula composition Formula 7 Formula 8 Formula 9 98% amino ester crude oil 10 (Discounted 100%) 10 (Discounted 100%) 10 (Discounted 100%) EL-20 8 8 8 Agricultural Dairy 1601 4 2 - Agricultural Milk 500# - 2 4 precipitate 20 20 20 diatomite Supplement to 100 Supplement to 100 Supplement to 100 Emulsion stability (200-fold dilution with standard hard water) There are oil droplets at the bottom No oil droplets, no oil paste separation There is grease on top Precipitate volume <1mL 1.5mL 1.5mL 1.5mL

[0094] As shown in Table 5, using silica and diatomaceous earth as adsorption carriers and fillers, and emulsifiers EL-20, agricultural emulsion 1601, and agricultural emulsion 500# for emulsion stability adjustment, the emulsion stability of Formula 8 is qualified, with no oil droplets or oil paste precipitation; however, the volume of precipitate is 1.5 mL.

[0095] Experiment 3: Screening of dispersants and wetting agents

[0096] Emulsifiable powders sometimes use non-water-soluble carriers. When diluting with water, it's necessary to add wetting agents and dispersants to the formulation to ensure these carriers remain well suspended in the water. Dispersants in emulsifiable powders primarily prevent the aggregation of fine particles and maintain uniform dispersion in the solid-liquid dispersion system formed with water for a longer period. Wetting agents are substances that reduce the interfacial tension between liquid and solid, increasing the contact between the drug-containing liquid and the solid surface of the target object (plants, pests, and others), thus wetting it or accelerating the wetting process.

[0097] Based on the screening results of the emulsifier in Experiment Example 2, the emulsion stability of formulations 2 and 3 is satisfactory, with no oil droplets or oily residue precipitation; and the precipitate volume is 0 mL. This is because the selected hydroxyethyl cellulose and water-soluble starch are both water-soluble carriers. The emulsion stability of formulations 6 and 8 is satisfactory, with no oil droplets or oily residue precipitation, but because the formulations use water-insoluble carriers and have not yet added suitable dispersants and wetting agents, precipitates are produced in both. The formulations 6 and 8 will be optimized below.

[0098] 1. Optimization of Formula 6

[0099] Formulations were prepared, and different dispersants and wetting agents were screened. The specific formulations and results are shown in Table 6.

[0100] Table 6

[0101]

[0102] Note: Formulation 13 in the table is the formulation of the amino ester-stabilized emulsifiable powder of Example 3.

[0103] Based on the wetting time and suspension rate test results of formulation 6, formulation design was carried out. Different types and ratios of dispersants and wetting agents were added to formulations 10, 11, 12, and 13, respectively. By measuring their wetting time and suspension rate, it was found that formulation 13 had the best performance in all aspects.

[0104] 2. Optimization of Formula 8

[0105] Formulations were prepared, and different dispersants and wetting agents were screened. The specific formulations and results are shown in Table 7.

[0106] Table 7

[0107]

[0108]

[0109] Note: Formulation 16 in the table is the formulation of the amino ester-stabilized emulsifiable powder of Example 4.

[0110] Based on the wetting time and suspension rate test results of formulation 8, formulation design was carried out. Different types and ratios of dispersants and wetting agents were added to formulations 14, 15, 16, and 17, respectively. Through the determination of their wetting time and suspension rate, it was found that formulation 16 had the best performance in all aspects.

[0111] Experimental Example 4: Determination of Quality Indicators of Amine-Stabilized Emulsifiable Powder

[0112] This experimental example measures the quality indicators of the amino ester-stabilized emulsifiable powders from Examples 1-4. The specific procedures are as follows:

[0113] For specific quality control indicators of 10% amino ester emulsifiable powder, please refer to "New Advances in Pesticide Formulation Processing" by Chen Fuliang, Chemical Industry Press, 2018. The specific testing indicators are shown in Table 8.

[0114] Table 8

[0115]

[0116] The determination of the mass fraction of the active ingredient aminoethyl ester was carried out by gas chromatography according to the standard NY / T 4116-2022 aminoethyl ester (aminoethyl ester citrate) technical grade.

[0117] pH value determination: NY / T 1860.1-2016 Guidelines for the determination of physicochemical properties of pesticides, Part 1: pH value.

[0118] Determination of moisture content: GB / T 1600-2001 Method for determination of moisture content in pesticides.

[0119] Determination of wetting time: GB / T 5451-2001 Determination method for wettability of wettable powder of pesticides.

[0120] Determination of emulsification time: Refer to the test method for disintegration time of water dispersible granules, and use the manual rotation method to test the time required for the sample to be completely emulsified to form an emulsion. Pour 0.5 g of the sample into a stoppered conical measuring cylinder containing 100 mL of standard hard water at 30 °C (the water surface is about 4 cm from the bottom of the glass stopper), tighten the stopper, and rotate at a speed of 7-8 r / min with the middle of the measuring cylinder as the center until the sample is completely emulsified, and record the required time.

[0121] Determination of emulsion stability: GB / T 1603-2001 Determination method for emulsion stability of pesticides. When all the carriers used are water-soluble substances, it is qualified if the emulsion remains homogeneous and there is no precipitate; when there are more non-water-soluble substances in the carriers used, the volume of the sediment object can be specified not to exceed a certain number of milliliters, but if oil droplets are observed to precipitate at the bottom or top, or cream is precipitated at the top, it should be judged as unqualified.

[0122] Determination of persistent foaming property: GB / T 28137-2011 Determination method for persistent foaming property of pesticides.

[0123] Determination of fineness: GB / T 16150-1995 Determination method for fineness of pesticide powder and wettable powder.

[0124] Determination of thermal storage stability: GB / T 19136-2021 Determination method for thermal storage stability of pesticides.

[0125] The quality indexes of the emulsifiable powder stabilized by diethyl aminoethyl hexanoate in Examples 1-4 were determined according to the above detection methods of quality control item indexes, and the results are as follows:

[0126] The test results of the emulsifiable powder stabilized by diethyl aminoethyl hexanoate in Example 1 (the above formula 2) are shown in Table 9 and Figures 1-3 as shown.

[0127] Table 9

[0128]

[0129]

[0130] The test results of the emulsifiable powder stabilized by diethyl aminoethyl hexanoate in Example 2 (the above formula 3) are shown in Table 10, Figure 1 and Figures 4-5 as shown.

[0131] Table 10

[0132]

[0133] The test results of the amino ester-stabilized emulsifiable powder of Example 3 (formulation 13 above) are shown in Table 11. Figure 1 and Figures 6-7 As shown.

[0134] Table 11

[0135]

[0136]

[0137] The test results of the amino ester-stabilized emulsifiable powder (formulation 16 above) in Example 4 are shown in Table 12. Figure 1 and Figures 8-9 As shown.

[0138] Table 12

[0139]

[0140]

[0141] As can be seen from the above data, the emulsifiable powders stabilized by amino esters in Examples 1-4 of this invention meet the quality standard requirements for all indicators in both room temperature and heat storage samples.

[0142] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. The scope of patent protection of the present invention shall be determined by the claims. Similarly, any equivalent structural changes made based on the description and drawings of the present invention shall also be included within the scope of protection of the present invention.

Claims

1. An emulsifiable powder stabilized by amino esters, characterized in that: By mass percentage, it mainly consists of the following components: 8%–10% amino ester crude oil, 10%–15% emulsifier, and the remainder is a carrier; the emulsifier is two or three of the following: octylphenol polyoxyethylene ether, calcium dodecylbenzenesulfonate, styrene-phenol polyoxyethylene ether, triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, and castor oil polyoxyethylene ether; the carrier is two of the following: water-soluble starch, hydroxyethyl cellulose, polyacrylamide, organobentonite, fumed silica, and diatomaceous earth.

2. The amine ester-stabilized emulsifiable powder according to claim 1, characterized in that: By weight percentage, it consists of the following components: 8%–10% crude amine ester, 6%–8% octylphenol polyoxyethylene ether, 2%–4% calcium dodecylbenzenesulfonate, 30%–35% hydroxyethyl cellulose, and 40%–50% water-soluble starch.

3. The amine ester-stabilized emulsifiable powder according to claim 1, characterized in that: By weight percentage, it consists of the following components: 8%–10% amine ester crude oil, 6%–8% styrene-phenol polyoxyethylene ether, 6%–8% triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, 25%–30% polyacrylamide, 45%–50% organobentonite, and 5%–6% dispersant.

4. The amine ester-stabilized emulsifiable powder according to claim 1, characterized in that: By weight percentage, it consists of the following components: 8%–10% crude amine ester, 2%–3% calcium dodecylbenzenesulfonate, 1%–2% triphenylethylphenol polyoxypropylene polyoxyethylene block polymer, 8%–10% castor oil polyoxyethylene ether, 20%–25% silica, 50%–55% diatomaceous earth, and 5%–6% dispersant.

5. The amine ester-stabilized emulsifiable powder according to claim 3 or 4, characterized in that: The dispersant is one of three of the following: SP-2836, calcium lignosulfonate, sodium methylene bisnaphthalene sulfonate, and sodium salt of alkyl naphthalene sulfonate condensate.

6. The amine ester-stabilized emulsifiable powder according to claim 3, characterized in that: The dispersant is SP-2836, calcium lignosulfonate, and sodium methylene bisnaphthalene sulfonate; the mass ratio of SP-2836, calcium lignosulfonate, and sodium methylene bisnaphthalene sulfonate is 2:1:

2.

7. The amine ester-stabilized emulsifiable powder according to claim 4, characterized in that: The dispersant is sodium alkyl naphthalene sulfonate condensate, sodium methylene bisnaphthalene sulfonate, and calcium lignin sulfonate; the mass ratio of sodium alkyl naphthalene sulfonate condensate, sodium methylene bisnaphthalene sulfonate, and calcium lignin sulfonate is 2:3:

1.

8. A method for preparing an amine ester-stabilized emulsifiable powder according to any one of claims 1 to 7, characterized in that: The oil phase is prepared by mixing crude oil containing amino esters and emulsifiers, and then adding a carrier for further mixing. The mixture is obtained after the carrier has fully adsorbed the emulsion.

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