Ternary compound herbicide suspension emulsion and preparation method thereof
By using a ternary compound herbicide suspension emulsion, combined with high-speed shearing and ball milling processes, the problems of poor weed control and instability in existing technologies have been solved, achieving effective weed coverage and improved suspension stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANJING TAIHUA CHEM CO LTD
- Filing Date
- 2026-02-11
- Publication Date
- 2026-05-19
AI Technical Summary
In existing technologies, 2,4-D isooctyl ester, cyanazine, and sulfopyrazine are not effective in weed control when used alone. Suspension emulsions are prone to curdling, have insufficient fluidity, and poor stability. They are also prone to solidification and hardening at the bottom after being left at room temperature.
A ternary compound herbicide suspension emulsion is adopted, which combines 2,4-D isooctyl ester, cyanazine and sulfopyrazine with magnesium aluminum silicate, adjuvants polystyrene phenol ethoxysulfonate, alkylbenzene sulfonamide salt and cashew phenol polyoxyethylene ether, and high-speed shearing and ball milling processes to form a stable suspension emulsion, which enhances systemic conductivity and suspension stability.
It covers both monocot and dicot weeds, prolongs the herbicidal residual period, reduces the frequency of application, lowers the risk of soil and water pollution, improves the thixotropy and stability of the suspension, and reduces toxicity to non-target organisms.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of herbicide technology, specifically to a ternary compound herbicide suspension emulsion and its preparation method. Background Technology
[0002] Suspension emulsions are compound formulations that combine the characteristics of suspensions and emulsions. Their core is to uniformly disperse water-insoluble solid active ingredients and liquid or low-melting-point oily active ingredients in water in the form of micron-sized particles or droplets through physical dispersion and chemical stabilization technologies, forming a stable multiphase dispersion system.
[0003] 2,4-D isooctyl ester technical grade is mostly prepared as an emulsion for use, cypermethrin is mostly prepared as a suspension concentrate, and sulfonylpyrazole is mostly prepared as a suspension concentrate. 2,4-D isooctyl ester can control broadleaf weeds, while cypermethrin and sulfonylpyrazole mainly control gramineous weeds. Using any one of them alone does not provide good herbicidal effects. Currently, there are no suspension emulsions combining these three technical grade herbs on the market. Furthermore, suspension emulsions are prone to paste formation, have insufficient fluidity, and suffer from severe thixotropy. More importantly, the formulations have poor long-term stability and tend to solidify and harden after prolonged storage at room temperature. Therefore, this invention proposes a ternary compound herbicide suspension emulsion and its preparation method to solve the above-mentioned technical problems. Summary of the Invention
[0004] The purpose of this invention is to provide a ternary compound herbicide suspension emulsion and its preparation method, so as to solve the problems raised in the prior art.
[0005] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a ternary compound herbicide suspension emulsion includes the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir, then add deionized water, stir, and obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, stir, and obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir, disperse, and grind to obtain a ternary compound herbicide suspension emulsion.
[0006] In the above technical solution, 2,4-D isooctyl ester is a hormone-based herbicide primarily effective against broadleaf weeds; cypermethrin is a photosynthesis-inhibiting herbicide primarily effective against grasses and some broadleaf weeds; and sulfonylpyrazole exerts its herbicidal effect by inhibiting cell division. The combination of these three active ingredients covers both monocot and dicot weeds. 2,4-D isooctyl ester alone has limited effectiveness against grasses, while the addition of cypermethrin and sulfonylpyrazole enhances systemic conductivity, solving the problem of insufficient control of grasses by traditional formulations. Sulfonylpyrazole has a long-lasting inhibitory effect, and combined with the soil-sealing effect of cypermethrin, it can extend the herbicidal residual period and reduce the frequency of application. The combination of 2,4-D isooctyl ester and sulfonylpyrazole can reduce the risk of phytotoxicity to crops. Magnesium aluminum silicate enhances the thixotropic properties of the suspension, and combined with the grinding process, inhibits sedimentation. The suspension emulsion formulation design reduces the use of organic solvents, lowering the risk of secondary pollution to soil and water.
[0007] Furthermore, the ternary compound herbicide suspension emulsion comprises the following components by mass percentage: 30-35% cyanazine, 15-20% sulfonylpyrazine, 8-10% 2,4-D isooctyl ester, 12-15% adjuvants, 0.5-1.0% magnesium aluminum silicate, 0.2-0.5% defoamer, with the balance being deionized water.
[0008] Furthermore, in steps S2, S3, and S4, the stirring process conditions are as follows: stirring at a speed of 400-500 rpm for 30-40 minutes.
[0009] Furthermore, in step S4, the dispersion process conditions are as follows: using a high-speed shearing machine at a rotation speed of 2400~3000 rpm and a power of 5~7.5kW, the dispersion is carried out rapidly for 20~30 minutes.
[0010] Furthermore, in step S4, the grinding process conditions are as follows: a ball mill is used, the grinding speed is 1000~1500 rpm, the time is 20~30 min, and the grinding is repeated 1~2 times.
[0011] Furthermore, in step S4, the suspended particle size D90 < 5 μm.
[0012] Furthermore, the additive comprises the following components, by weight percentage: 20-35% polystyrene phenol ethoxysulfonate, 40-50% alkylbenzene sulfonamide salt, and 15-40% cashew phenol polyoxyethylene ether.
[0013] In the above technical solution, polystyrene phenol ethoxysulfonate, as an emulsion stabilizer, contains both hydrophobic polystyrene phenol chains and hydrophilic ethoxysulfonate groups in its molecule. It can be adsorbed at the oil-water interface, reducing the interfacial tension between oil and water, forming a stable emulsion, and preventing stratification. The hydrophobic alkyl chains of alkylbenzene sulfonate amide salt are adsorbed on the surface of oil droplets, reducing particle aggregation. The amide groups can disrupt the structure of the waxy layer of plant epidermis, promoting the penetration of the drug solution. Cashew phenol polyoxyethylene ether has wetting and thickening effects, assisting the emulsifier in reducing toxicity to non-target organisms.
[0014] Furthermore, the magnesium aluminum silicate undergoes surface modification, and the modification process is as follows: Step 1: Add magnesium aluminum silicate to hydrochloric acid solution, stir, centrifuge, and dry to obtain pretreated magnesium aluminum silicate; Step 2: Disperse the pretreated magnesium aluminum silicate in deionized water, add the initiator, stir, then add acrylic acid, heat to react, after the reaction is complete, filter, centrifuge, and dry to obtain polyacrylic acid magnesium aluminum silicate; Step 3: Add magnesium aluminum silicate polyacrylate to deionized water, disperse, add 2,3-epoxypropyltrimethylammonium chloride (GTA), adjust the pH, heat to react, centrifuge, and dry to obtain modified magnesium aluminum silicate.
[0015] In the above technical solution, magnesium aluminum silicate is treated with hydrochloric acid solution to remove a small amount of metal oxide covering its surface, exposing the hydroxyl groups (-OH) inside the magnesium aluminum silicate. Hydrogen in the hydrochloric acid reacts with the hydroxyl groups on the magnesium aluminum silicate surface via a protonation reaction, forming silanol cations, which enhance the surface grafting active sites. These silanol cations, acting as Lewis acids, can adsorb acrylic acid monomers and fix them through hydrogen bonds. Ammonium persulfate, acting as the oxidant in the redox initiation system, decomposes upon heating in aqueous solution, generating sulfate radicals. The OH bonds in the hydroxyl groups can be attacked by sulfate radicals, generating surface siloxane radicals (Si-O). The acrylic acid monomers undergo homolytic cleavage under the action of sulfate radicals, generating acrylic acid radicals. These surface siloxane radicals react with the acrylic acid monomers to form a siloxane-acrylic acid covalent bond. The acrylic acid radicals then form a polyacrylic acid chain through a chain growth reaction, yielding polyacrylic acid magnesium aluminum silicate. The surface of polyacrylic acid magnesium aluminum silicate is rich in hydroxyl groups, which directly attack the carbon atoms of the epoxy ring under alkaline conditions, forming magnesium aluminum silicate -O-CH2-CH(O) after ring opening. - )-CH2N + (CH3)3, which is then protonated to form a quaternary ammonium salt.
[0016] Magnesium aluminum silicate has a layered crystalline structure and a negatively charged surface. When added to a suspension, magnesium aluminum silicate particles can be adsorbed onto the surface of the suspended particles through electrostatic interactions, forming a protective film that inhibits sedimentation and aggregation, thus improving suspension stability. However, cyanazine molecules contain two amino groups, which protonate in solution, thereby imparting a positive charge to the molecules, which is detrimental to the stability of the suspension emulsion. This invention addresses this by acid-treating magnesium aluminum silicate to enhance the active sites of acrylic acid monomer grafting on its surface. Acrylic acid grafting increases the molecular weight and steric hindrance of magnesium aluminum silicate, improving the rheological properties of the suspension emulsion, inhibiting flocculation, and simultaneously enhancing the hydrophilicity and adsorption capacity of magnesium aluminum silicate. Furthermore, grafting quaternary ammonium salt structures onto the surface of polyacrylic acid magnesium aluminum silicate makes the surface positively charged, increases the surface charge density, optimizes intermolecular electrostatic interactions, and thus enhances the stability of the suspension emulsion.
[0017] Furthermore, in step 1, the stirring conditions are: stirring at a speed of 100~200 rpm for 10~15 min.
[0018] Furthermore, in step 1, the centrifugation process conditions are: centrifugation at a speed of 2400~3000 rpm for 30~40 min.
[0019] Furthermore, in step 1, the drying process conditions are: drying at a temperature of 60~70℃ for 1~2 hours.
[0020] Furthermore, the mass ratio of magnesium aluminum silicate to hydrochloric acid solution is 1:(8~10).
[0021] Furthermore, the concentration of the hydrochloric acid solution is 0.05~0.2 mol / L.
[0022] Furthermore, the mass ratio of pretreated magnesium aluminum silicate, deionized water, initiator, and acrylic acid is 10:(50~80):(0.05~0.15):(2~3).
[0023] Furthermore, in step 2, the stirring process conditions are as follows: stirring at a speed of 200~300 rpm for 20~30 minutes.
[0024] Furthermore, in step 2, the process conditions for the heating reaction are: at a temperature of 40~50℃, the reaction is carried out for 2~3 hours.
[0025] Furthermore, in step 2, the centrifugation process conditions are: centrifugation at a speed of 2100~2500 rpm for 30~40 min.
[0026] Furthermore, in step 2, the drying process conditions are: drying at a temperature of 60~70℃ for 1~2 hours.
[0027] Furthermore, the initiator is ammonium persulfate (APS).
[0028] Furthermore, the mass ratio of magnesium aluminum silicate polyacrylate, deionized water, and GTA is (3~5):(30~40):1.
[0029] Furthermore, in step 3, the dispersion process conditions are: dispersion at a speed of 1000~1500 rpm for 10~15 min.
[0030] Furthermore, in step 3, the process conditions for the heating reaction are: reacting at a temperature of 60~80℃ for 1~2 hours.
[0031] Furthermore, in step 3, the centrifugation process conditions are: centrifugation at a speed of 2400~3000 rpm for 30~40 min.
[0032] Furthermore, in step 3, the drying process conditions are: drying at a temperature of 60~70℃ for 1~2 hours.
[0033] Furthermore, the process conditions for adjusting pH are as follows: adjust the pH to 8-10 using 5-10 wt% NaOH solution.
[0034] Furthermore, the cashew phenol polyoxyethylene ether undergoes glycosylation, the specific process of which is as follows: Step (1): Mix cashew phenol polyoxyethylene ether with glucose, add deionized water, stir, and obtain a sugar solution; Step (2): Heat the sugar solution to 100~120℃, add the catalyst, react under vacuum of 4~6KPa for 4~6h, then adjust to atmospheric pressure and pH to obtain glycosylated mixture; Step (3): Extract and separate the glycosylated mixture to obtain glycosylated cashew phenol polyoxyethylene ether.
[0035] Furthermore, the catalyst is p-toluenesulfonic acid.
[0036] In the above technical solution, p-toluenesulfonic acid provides protons to protonate the terminal hydroxyl group (-OH) of cashew phenol polyoxyethylene ether, converting it into more easily leaving water molecules (H2O); the C6-OH (primary hydroxyl group) of glucose acts as a nucleophile, attacking the carbon atom (C-OH) at the terminal of the polyoxyethylene chain in cashew phenol polyoxyethylene ether; the OO bond breaks, releasing water, and at the same time, the primary hydroxyl group of glucose forms a new glycosidic bond (COC) with the oxygen atom of cashew phenol polyoxyethylene ether.
[0037] By introducing glycosidic bonds onto the surface of cashew phenol polyoxyethylene ether, the adsorption capacity of the molecules at the interface is enhanced, resulting in glycosylated products with lower surface and interfacial tensions than the original cashew phenol polyoxyethylene ether. Increased molecular polarity optimizes the hydrophilic-lipophilic balance, giving it excellent wetting and emulsifying capabilities in suspension systems. Glycosidic bonds are a naturally occurring linkage, making it easier for microorganisms to recognize and degrade the glycosylated products. Compared to traditional nonionic surfactants, it is more environmentally friendly and gentler, improving its biodegradability, reducing environmental pollution, and minimizing irritation to the skin and eyes. The long-chain structure of glycosylated cashew phenol polyoxyethylene ether, synergistically with glucose groups, enhances the thickening effect of suspensions, while the flexible movement of its molecular chains reduces particle aggregation and improves fluidity. The hydroxyl groups of glycosylated cashew phenol form a hydrogen bond network with the plant surface cuticle, and together with the charge repulsion effect of adjuvants, form a hydrophobic layer on the leaf surface, enhancing the herbicide's environmental resistance to rain washout.
[0038] Furthermore, the mass ratio of cashew phenol polyoxyethylene ether, glucose, deionized water and catalyst is 1:(1~3):50:(0.01~0.1).
[0039] Furthermore, in step (1), the stirring process conditions are: stirring at a speed of 200~300 rpm for 20~30 min.
[0040] Furthermore, in step (2), the process conditions for adjusting pH are as follows: use a NaOH solution of a certain concentration to adjust pH to 8~10.
[0041] Furthermore, in step (3), the extraction and separation process is as follows: a supercritical CO2 extraction vessel is used, the pressure of the extraction vessel is 25~50MPa, the separation pressure is 5~10MPa, and the temperature of both the extraction vessel and the separation vessel is 50~60℃.
[0042] Compared with the prior art, the beneficial effects of the present invention are: 1. The ternary compound herbicide suspension emulsion of the present invention covers both monocot and dicot weeds by combining three active ingredients, enhances the systemic conductivity of the herbicide, prolongs the weeding effect, and reduces the frequency of application; by adding magnesium aluminum silicate, the thixotropic properties of the suspension are enhanced, and the grinding process inhibits sedimentation. The suspension emulsion formulation design reduces the use of organic solvents and lowers the risk of secondary pollution to soil and water.
[0043] 2. The ternary compound herbicide suspension emulsion of the present invention, by adding polystyrene phenol ethoxysulfonate, alkylbenzene sulfonamide salt and cashew phenol polyoxyethylene ether as adjuvants, reduces the oil-water interfacial tension, forms a stable emulsion, prevents stratification, reduces particle aggregation, promotes the penetration of the herbicide solution, and reduces toxicity to non-target organisms.
[0044] 3. The ternary compound herbicide suspension emulsion of the present invention enhances the active sites of acrylic acid monomer grafted onto the surface of magnesium aluminum silicate by acid treatment. Grafting acrylic acid increases the molecular weight and steric hindrance of magnesium aluminum silicate, improves the rheological properties of the suspension emulsion, inhibits flocculation, and enhances the hydrophilicity and adsorption capacity of magnesium aluminum silicate. Grafting quaternary ammonium salt structures onto the surface of polyacrylic acid magnesium aluminum silicate makes the surface of magnesium aluminum silicate positively charged, enhances the surface charge density, optimizes the intermolecular electrostatic interaction, and enhances the stability of the suspension emulsion.
[0045] 4. The ternary compound herbicide suspension emulsion of the present invention enhances the adsorption capacity of molecules at the interface by introducing glycosidic bonds on the surface of cashew phenol polyoxyethylene ether. This results in the glycosylated product having lower surface tension and interfacial tension than the original cashew phenol polyoxyethylene ether, enhanced molecular polarity, optimized hydrophilic-lipophilic balance, improved biodegradability, reduced environmental pollution, and reduced irritation to the skin and eyes. Combined with the charge repulsion effect of adjuvants, it enhances the environmental resistance of the herbicide to rainwater runoff. Detailed Implementation
[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0047] In the following specific implementation, The ternary compound herbicide suspension emulsion comprises the following components by weight percentage: 30% cyanazine, 15% sulfonylpyrazole, 8% 2,4-D isooctyl ester, 12% adjuvants, 0.5% magnesium aluminum silicate, 0.2% defoamer, and the balance being deionized water. Magnesium aluminum silicate, grade SF-04, is sourced from Suzhou Sinoma Materials Co., Ltd. The defoamer, brand name 2024-X, is from Nanjing Qunxing Co., Ltd. Suspended particle size, D90 < 5 μm; The concentration of the hydrochloric acid solution is 0.05~0.2 mol / L; The initiator is ammonium persulfate; The catalyst is p-toluenesulfonic acid; Example 1: A method for preparing a ternary compound herbicide suspension emulsion, comprising the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir at 400 rpm, then add deionized water and stir for 30 min to obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, and stir at 400 rpm for 30 min to obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir at 400 rpm for 30 min, then use a high-speed shear mill at 2400 rpm and 5 kW power to quickly disperse for 20 min, then use a ball mill at 1000 rpm for 20 min, grind twice to obtain a ternary compound herbicide suspension emulsion.
[0048] The additives include the following components, by weight percentage: 20% polystyrene phenol ethoxysulfonate, 40% alkylbenzene sulfonamide salt, and 40% cashew phenol polyoxyethylene ether.
[0049] Example 2: A method for preparing a ternary compound herbicide suspension emulsion, comprising the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir at 450 rpm, then add deionized water and stir for 35 min to obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, and stir at 450 rpm for 35 min to obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir at 450 rpm for 35 min, then use a high-speed shear mill at 2500 rpm and 6 kW power to quickly disperse for 25 min, then use a ball mill at 1200 rpm for 25 min, grind twice to obtain a ternary compound herbicide suspension emulsion.
[0050] The additives include the following components, by weight percentage: 35% polystyrene phenol ethoxysulfonate, 50% alkylbenzene sulfonamide salt, and 15% cashew phenol polyoxyethylene ether.
[0051] Example 3: A method for preparing a ternary compound herbicide suspension emulsion, comprising the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir at 500 rpm, then add deionized water and stir for 40 min to obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, and stir at 500 rpm for 40 min to obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir at 500 rpm for 40 min, then use a high-speed shear mill at 3000 rpm and 7.5 kW power to quickly disperse for 30 min, then use a ball mill at 1500 rpm for 30 min, grind twice to obtain a ternary compound herbicide suspension emulsion.
[0052] The additives include the following components, by weight percentage: 25% polystyrene phenol ethoxysulfonate, 40% alkylbenzene sulfonamide salt, and 35% cashew phenol polyoxyethylene ether.
[0053] Example 4: A method for preparing a ternary compound herbicide suspension emulsion, comprising the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir at 490 rpm, then add deionized water and stir for 38 min to obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, and stir at 490 rpm for 38 min to obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir at 490 rpm for 38 min, then use a high-speed shear mill at 2800 rpm and 7 kW power to quickly disperse for 28 min, then use a ball mill at 1400 rpm for 28 min, grind twice to obtain a ternary compound herbicide suspension emulsion.
[0054] The magnesium aluminum silicate undergoes surface modification, and the modification process is as follows: Step 1: Add magnesium aluminum silicate to hydrochloric acid solution, stir at 100 rpm for 10 min, centrifuge at 2400 rpm for 30 min, and dry at 60℃ for 1 h to obtain pretreated magnesium aluminum silicate; the mass ratio of magnesium aluminum silicate to hydrochloric acid solution is 1:8. Step 2: Disperse the pretreated magnesium aluminum silicate in deionized water, add the initiator, stir at 200 rpm for 20 min, then add acrylic acid, react at 40℃ for 2 h, filter after the reaction, centrifuge at 2100 rpm for 30 min, and dry at 60℃ for 1 h to obtain polyacrylic acid magnesium aluminum silicate; the mass ratio of pretreated magnesium aluminum silicate, deionized water, initiator and acrylic acid is 10:50:0.05:2; Step 3: Add magnesium aluminum silicate polyacrylate to deionized water and disperse at 1000 rpm for 10 min. Add 2,3-epoxypropyltrimethylammonium chloride (GTA), adjust the pH to 8.5 with 5 wt% NaOH solution, react at 60℃ for 1 h, centrifuge at 2400 rpm for 30 min, and dry at 60℃ for 1 h to obtain modified magnesium aluminum silicate. The mass ratio of magnesium aluminum silicate polyacrylate, deionized water, and GTA is 3:30:1.
[0055] The cashew phenol polyoxyethylene ether undergoes glycosylation, and the specific process is as follows: Step (1): Mix cashew phenol polyoxyethylene ether with glucose, add deionized water, and stir at 200 rpm for 20 min to obtain a sugar solution; Step (2): Heat the sugar solution to 100℃, add the catalyst, react for 4 hours under a vacuum of 4KPa, then adjust to atmospheric pressure, and adjust the pH to 8 using a NaOH solution of a certain concentration to obtain a glycosylated mixture; Step (3): The glycosylated mixture was extracted using a supercritical CO2 extraction vessel with an extraction vessel pressure of 25 MPa and a separation pressure of 5 MPa. The temperature of both the extraction vessel and the separation vessel was 50°C to obtain glycosylated cashew phenol polyoxyethylene ether.
[0056] The mass ratio of cashew phenol polyoxyethylene ether, glucose, deionized water and catalyst is 1:1:50:0.01.
[0057] Example 5: A method for preparing a ternary compound herbicide suspension emulsion, comprising the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir at 500 rpm, then add deionized water and stir for 40 min to obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, and stir at 500 rpm for 40 min to obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir at 500 rpm for 40 min, then use a high-speed shear mill at 3000 rpm and 7.5 kW power to quickly disperse for 30 min, then use a ball mill at 1500 rpm for 30 min, grind twice to obtain a ternary compound herbicide suspension emulsion.
[0058] The magnesium aluminum silicate undergoes surface modification, and the modification process is as follows: Step 1: Add magnesium aluminum silicate to hydrochloric acid solution, stir at 200 rpm for 15 min, centrifuge at 3000 rpm for 40 min, and dry at 70℃ for 2 h to obtain pretreated magnesium aluminum silicate; the mass ratio of magnesium aluminum silicate to hydrochloric acid solution is 1:9. Step 2: Disperse the pretreated magnesium aluminum silicate in deionized water, add the initiator, stir at 300 rpm for 30 min, then add acrylic acid, react at 50℃ for 3 h, filter after the reaction, centrifuge at 2500 rpm for 40 min, and dry at 70℃ for 2 h to obtain polyacrylic acid magnesium aluminum silicate; the mass ratio of pretreated magnesium aluminum silicate, deionized water, initiator and acrylic acid is 10:80:0.15:3; Step 3: Add magnesium aluminum silicate polyacrylate to deionized water and disperse at 1500 rpm for 15 min. Add GTA and adjust the pH to 8.5 with 5 wt% NaOH solution. React at 80℃ for 2 h, centrifuge at 3000 rpm for 40 min, and dry at 70℃ for 2 h to obtain modified magnesium aluminum silicate. The mass ratio of magnesium aluminum silicate polyacrylate, deionized water, and GTA is 5:40:1.
[0059] The cashew phenol polyoxyethylene ether undergoes glycosylation, and the specific process is as follows: Step (1): Mix cashew phenol polyoxyethylene ether with glucose, add deionized water, and stir at 300 rpm for 30 min to obtain a sugar solution; Step (2): Heat the sugar solution to 120°C, add the catalyst, react for 6 hours under a vacuum of 6 kPa, then adjust to atmospheric pressure, and adjust the pH to 9.5 using a NaOH solution of a certain concentration to obtain a glycosylated mixture; Step (3): The glycosylated mixture was extracted using a supercritical CO2 extraction vessel with an extraction vessel pressure of 50 MPa and a separation pressure of 10 MPa. The temperature of both the extraction vessel and the separation vessel was 60°C to obtain glycosylated cashew phenol polyoxyethylene ether.
[0060] The mass ratio of cashew phenol polyoxyethylene ether, glucose, deionized water and catalyst is 1:3:50:0.1.
[0061] Comparative Example 1: This comparative example provides a herbicide suspension emulsion comprising the following components by mass percentage: 30% cyanazine, 15% sulfonylpyrazine, 8% 2,4-D isooctyl ester, 12% alkyl aryl polyoxyethylene polyoxypropylene ether (34#), 0.5% magnesium aluminum silicate, 0.2% defoamer, and the balance being deionized water.
[0062] In this comparative example, the herbicide suspension emulsion used 34# instead of the adjuvant, and the rest of the methods were the same as in Example 1.
[0063] Comparative Example 2: This comparative example provides a herbicide suspension emulsion comprising the following components by mass percentage: 30% cyanazine, 23% sulfonylpyrazine, 12% adjuvant, 0.5% magnesium aluminum silicate, 0.2% defoamer, and the balance being deionized water.
[0064] The herbicide suspension emulsion in this comparative example uses a combination of cyanazine and sulfopyrazine technical grade pesticides, and the remaining methods are the same as in Example 1.
[0065] Comparative Example 3: This comparative example provides a herbicide suspension emulsion in which magnesium aluminum polyacrylate is not treated with GTA, and the remaining methods are the same as in Example 4.
[0066] Comparative Example 4: This comparative example provides a herbicide suspension emulsion in which cashew phenol polyoxyethylene ether is amination-treated. The specific process is as follows: cashew phenol polyoxyethylene ether is mixed with isopropanolamine, the pH is adjusted, and the mixture is reacted at 60-80°C for 4-6 hours to obtain amination-treated cashew phenol polyoxyethylene ether.
[0067] The remaining methods are the same as in Example 4.
[0068] experiment: Samples were prepared from the herbicide suspension emulsions obtained in Examples 1-5 and Comparative Examples 1-4. Their performance was tested and the results were recorded under both ambient temperature and 54°C heat storage conditions. Water separation test: Using GB / T 14825-2006 as the reference standard, the sample is placed in a transparent container and left to stand for a period of time. The height of the water separation layer is visually recorded, and then the water separation volume is calculated from the total height.
[0069] Curing test: Using GB / T 14825-2006 as the reference standard, the sample was placed in a transparent container and left to stand for a period of time, and the curing condition of the sample was observed.
[0070] Thixotropic test: Using GB / T 17783-1999 as the reference standard, a rheometer was used. The viscosity was first increased from a low shear rate to a high shear rate and then decreased back to a low shear rate. The viscosity recovery was observed.
[0071] Germination rate test: Using GB / T 17980 as the reference standard, a 20wt% concentration of herbicide suspension emulsion was prepared to treat weed seeds (tribulus, alfalfa, crabgrass, dandelion, purslane). After one week, the germination status was observed and the germination rate was recorded.
[0072] Degradation rate test: Using GB / T19277 as a reference standard, soil sprayed with herbicide was inoculated with degrading microorganisms (Streptomyces and Pseudomonas) for composting treatment. After 45 days, the herbicide content was measured and the degradation rate was recorded.
[0073] Comparison table of water separation volume
[0074] Comparison table of curing conditions
[0075] Thixotropic Comparison Table
[0076] Performance Comparison Table
[0077] Based on the data in the table above, the following conclusions can be clearly drawn: Compared with the comparative examples, the ternary compound herbicide suspension emulsions obtained in Examples 1-5 have low water separation, no solidification, and good thixotropy.
[0078] Comparing Example 1 with Comparative Examples 1-2, it can be seen that the herbicide suspension emulsion prepared by combining the three technical materials 2,4-D isooctyl ester, cyanazine, and sulfopyrazine has a low germination rate and good weed control effect. When the three adjuvants polystyrene phenol ethoxysulfonate, alkylbenzene sulfonamide salt, and cashew phenol polyoxyethylene ether are used in combination, the herbicide suspension emulsion does not solidify, indicating that the adjuvants can effectively improve the stability of the herbicide suspension emulsion.
[0079] Comparing Example 4 with Comparative Example 3, the herbicide suspension emulsion prepared without GTA treatment had high water separation, solidification, and poor thixotropy. It can be seen that surface modification of magnesium aluminum silicate, followed by polyacrylic acid coating and then grafting with GTA, can effectively prevent sedimentation and improve the stability of the suspension emulsion.
[0080] Comparing Example 4 with Comparative Example 4, the herbicide suspension emulsion prepared after amination of cashew phenol polyoxyethylene ether had high water separation, solidification, poor thixotropy, and low degradation rate. It can be seen that glycosylation treatment of cashew phenol polyoxyethylene ether can improve the biodegradability of the herbicide suspension emulsion, and at the same time, it has a good anti-flocculation effect.
[0081] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.
Claims
1. A method for preparing a ternary compound herbicide suspension emulsion, characterized in that: Includes the following steps: S1: Mix the additive with deionized water to obtain mixture A; S2: Slowly add 2,4-D isooctyl ester technical grade to mixture A, stir, then add deionized water, stir, and obtain mixture A1; S3: Add cyanazine and sulfopyrazine technical grade to mixture A1, stir, and obtain mixture B; S4: Add magnesium aluminum silicate and defoamer to mixture B, stir, disperse, and grind to obtain a ternary compound herbicide suspension emulsion.
2. The method for preparing a ternary compound herbicide suspension emulsion according to claim 1, characterized in that: The ternary compound herbicide suspension emulsion comprises the following components by mass percentage: 30-35% cyanazine, 15-20% sulfonylpyrazine, 8-10% 2,4-D isooctyl ester, 12-15% adjuvants, 0.5-1.0% magnesium aluminum silicate, 0.2-0.5% defoamer, and the balance being deionized water.
3. The method for preparing a ternary compound herbicide suspension emulsion according to claim 1, characterized in that: The additive comprises the following components, by mass percentage: 20-35% polystyrene phenol ethoxysulfonate, 40-50% alkylbenzene sulfonamide salt, and 15-40% cashew phenol polyoxyethylene ether.
4. The method for preparing a ternary compound herbicide suspension emulsion according to claim 1, characterized in that: The magnesium aluminum silicate undergoes surface modification, and the modification process is as follows: Step 1: Add magnesium aluminum silicate to hydrochloric acid solution, stir, centrifuge, and dry to obtain pretreated magnesium aluminum silicate; Step 2: Disperse the pretreated magnesium aluminum silicate in deionized water, add the initiator, stir, then add acrylic acid, heat to react, after the reaction is complete, filter, centrifuge, and dry to obtain polyacrylic acid magnesium aluminum silicate; Step 3: Add magnesium aluminum silicate polyacrylate to deionized water, disperse, add 2,3-epoxypropyltrimethylammonium chloride, adjust the pH, heat to react, centrifuge and dry to obtain modified magnesium aluminum silicate.
5. The method for preparing a ternary compound herbicide suspension emulsion according to claim 4, characterized in that: The mass ratio of magnesium aluminum silicate to hydrochloric acid solution is 1:(8~10).
6. The method for preparing a ternary compound herbicide suspension emulsion according to claim 4, characterized in that: The mass ratio of pretreated magnesium aluminum silicate, deionized water, initiator, and acrylic acid is 10:(50~80):(0.05~0.15):(2~3).
7. The method for preparing a ternary compound herbicide suspension emulsion according to claim 4, characterized in that: The mass ratio of magnesium aluminum silicate polyacrylate, deionized water, and 2,3-epoxypropyltrimethylammonium chloride is (3~5):(30~40):
1.
8. The method for preparing a ternary compound herbicide suspension emulsion according to claim 3, characterized in that: The cashew phenol polyoxyethylene ether undergoes glycosylation, and the specific process is as follows: Step (1): Mix cashew phenol polyoxyethylene ether with glucose, add deionized water, stir, and obtain a sugar solution; Step (2): Heat the sugar solution to 100~120℃, add the catalyst, react under vacuum of 4~6KPa for 4~6h, then adjust to atmospheric pressure and pH to obtain glycosylated mixture; Step (3): Extract and separate the glycosylated mixture to obtain glycosylated cashew phenol polyoxyethylene ether.
9. The method for preparing a ternary compound herbicide suspension emulsion according to claim 8, characterized in that: The mass ratio of cashew phenol polyoxyethylene ether, glucose, deionized water and catalyst is 1:(1~3):50:(0.01~0.1).
10. A ternary compound herbicide suspension emulsion, characterized in that: Prepared by the preparation method according to any one of claims 1-9.