Preparation method of modified polycarboxylate surfactant and its application in pesticide preparation

Abstract

The present invention relates to the technical field of surfactants, and discloses a preparation method of a modified polycarboxylate surfactant and its application in pesticide preparations. The present invention uses 3-hexene-1,6-diamine and epichlorohydrin as raw materials, and obtains 1,6-tetraglycidylamine-3-hexene through ring opening and ring closing reactions. 1,6-tetraglycidylamine-3-hexene is used twice to react with sodium bisulfite and phosphoric acid in sequence to obtain tetrasulfonate-based hexene and tetraphosphate-based hexene, and then the two are copolymerized with acrylic acid and methacrylate to obtain a modified polycarboxylate surfactant. The modified polycarboxylate surfactant prepared by the present invention has excellent dispersibility, heat storage stability and high suspension rate.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, in particular to a preparation method of a modified polycarboxylate surfactant and application of the modified polycarboxylate surfactant in pesticide preparations. Background Art

[0002] Surfactants are surface-active compounds that can dissolve in liquids and can be directionally adsorbed on the surface of liquids or gases or other interfaces at low concentrations to reduce surface tension or interfacial tension. Surfactants used in pesticides mainly play the roles of wetting, dispersing, emulsifying, and defoaming. They play an indispensable and important role in the pesticide industry and are an indispensable component in the processing of pesticide formulations. They are known as "industrial MSG". They can maximize the effectiveness of the active ingredients of pesticides in the prevention and control of pests and diseases, improve the effectiveness of pesticide use, reduce the amount of pesticides used, and reduce the impact of pesticides on the environment.

[0003] As far as the current use of surfactants in agriculture is concerned, the surfactants used in pesticides are mostly anionic and nonionic. Since each type of surfactant has its own advantages and disadvantages, it is often difficult to meet the needs of various pesticide processing when using a single surfactant. Therefore, the development of high-performance pesticide functional surfactants has become the main direction of research and development of pesticide surfactants. Summary of the invention

[0004] The purpose of the present invention is to overcome the defects of the prior art and provide a method for preparing a modified polycarboxylate surfactant and its application in pesticide preparations. The prepared surfactant can improve the suspension performance and dispersibility of the pesticide preparation.

[0005] The object of the present invention can be achieved by the following technical scheme: a method for preparing a modified polycarboxylate surfactant, the preparation method comprising:

[0006] (1) under nitrogen protection, ethanol and 3-hexene-1,6-diamine were added to a flask, stirred and dispersed at room temperature, epichlorohydrin was added thereto, the temperature was raised to 70-75° C., the reaction was carried out for 3-6 hours, after the reaction was completed, the temperature was lowered to 40-50° C., a 30% by mass sodium hydroxide aqueous solution was added thereto, the reaction was stirred for 1-3 hours, after the reaction was completed, suction filtered, and dried to obtain 1,6-tetraglycidylamine-3-hexene;

[0007] (2) adding sodium bisulfite and deionized water to a flask, stirring to dissolve, heating to 60-75° C., adding 1,6-tetraglycidylamine-3-hexene thereto, stirring to react for 1-2.5 hours, and after the reaction is completed, cooling to room temperature, filtering with suction, and drying to obtain tetrasulfonate hexene;

[0008] (3) adding phosphoric acid and ether to a flask, stirring to dissolve, then adding 1,6-tetraglycidylamine-3-hexene, stirring to react at 40-45° C. for 4-8 hours, after the reaction is completed, removing the ether by vacuum distillation, adding ethanol, stirring to dissolve, then adding 20% ​​by mass potassium hydroxide ethanol solution, stirring to disperse, controlling the pH to 7-8, suction filtering, and drying to obtain tetraphosphate ester salt-based hexene;

[0009] (4) Add acrylic acid, methacrylate, maleic anhydride and deionized water into a flask, stir to dissolve, then add tetrasulfonate hexene, tetraphosphate hexene and ammonium persulfate, react at 70-80° C. for 2-5 hours. After the reaction is completed, adjust the pH to 7-8 with a 30% by mass sodium hydroxide solution, dry, and obtain a modified polycarboxylate surfactant.

[0010] In a preferred embodiment of the present invention, in (1), the usage ratio of 3-hexene-1,6-diamine to epichlorohydrin is 1 mol:(4-5) mol.

[0011] In a preferred embodiment of the present invention, in (2), the usage ratio of sodium bisulfite to 1,6-tetraglycidylamine-3-hexene is (3.8-4.5) mol:1 mol.

[0012] In a preferred embodiment of the present invention, in (3), the usage ratio of phosphoric acid to 1,6-tetraglycidylamine-3-hexene is (4-5) mol:1 mol.

[0013] In a preferred embodiment of the present invention, in (4), the usage ratio of acrylic acid, methacrylate, maleic anhydride, tetrasulfonate hexene and tetraphosphate hexene is 1 mol:(0.4-0.6) mol:(0.2-0.4) mol:(0.05-0.2) mol:(0.05-0.2) mol.

[0014] In a preferred embodiment of the present invention, in said (4), the amount of ammonium persulfate used is 1-2% of the total molar amount of acrylic acid, methacrylate, maleic anhydride, tetrasulfonate hexene and tetraphosphate hexene.

[0015] Another object of the present invention is to provide the use of the modified polycarboxylate surfactant of the present invention in pesticide formulations.

[0016] Beneficial effects of the present invention:

[0017] 1. The present invention uses 3-hexene-1,6-diamine and epichlorohydrin as raw materials, and obtains 1,6-tetraglycidylamine-3-hexene through ring opening and ring closing reactions. 1,6-tetraglycidylamine-3-hexene is used twice to react with sodium bisulfite and phosphoric acid in sequence to obtain tetrasulfonate-based hexene and tetraphosphate-based hexene, and then the two are copolymerized with acrylic acid and methacrylate to obtain a modified polycarboxylate surfactant. The present invention uses 1,6-tetraglycidylamine-3-hexene twice to prepare tetrasulfonate-based hexene and tetraphosphate-based hexene, and has a novel structure and a simple preparation method.

[0018] 2. The modified polycarboxylate surfactant prepared by the present invention contains strong polar groups such as carboxyl, sulfonic acid and phosphate groups on the main chain and side chain of the molecule. These strong polar groups can be adsorbed on the surface of pesticide particles through hydrogen bonding, overcome the agglomeration of pesticide particles, and keep the particles dispersed. At the same time, the hydrophobic chains of the molecules facing outward and other hydrophobic chains in the solution will also attract each other due to the hydrophobic effect, forming a double-layer adsorption. This double-layer adsorption structure enhances the dispersing effect of the surfactant on the pesticide particles, and further improves the dispersibility and suspension rate of the pesticide preparation. In addition, these strong polar groups can cooperate with each other to make up for the defects in the performance of a single group, enhance surface performance, reduce the amount of surfactant used, reduce costs, and increase efficiency. The surfactant prepared by the present invention has good suspension and dispersibility for pesticide preparations. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 It is the reaction route of 1,6-tetraglycidylamine-3-hexene;

[0020] Figure 2 It is the reaction route of tetraphosphate-based hexene;

[0021] Figure 3 This is the reaction route for tetrasulfonate hexene. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Example 1

[0024] (1) Under nitrogen protection, 100 mL of ethanol and 0.05 mol of 3-hexene-1,6-diamine were added to a flask, and the mixture was stirred and dispersed at room temperature. Then, 0.2 mol of epichlorohydrin was added thereto, and the temperature was raised to 70° C. and the reaction was carried out for 5 h. After the reaction was completed, the temperature was lowered to 45° C., and a 30% by mass sodium hydroxide aqueous solution was added thereto. The mixture was stirred and reacted for 1 h. After the reaction was completed, the mixture was filtered and dried to obtain 1,6-tetraglycidylamine-3-hexene.

[0025] (2) Add 0.22 mol of sodium bisulfite and 100 mL of deionized water into a flask, stir to dissolve, heat to 65° C., add 0.05 mol of 1,6-tetraglycidylamine-3-hexene, stir to react for 1-2.5 hours, and after the reaction is completed, cool to room temperature, filter, and dry to obtain tetrasulfonate hexene.

[0026] (3) Add 0.4 mol of phosphoric acid and 150 mL of ether to a flask, stir to dissolve, then add 0.1 mol of 1,6-tetraglycidylamine-3-hexene, stir to react at 45° C. for 6 h, and after the reaction is completed, remove the ether by vacuum distillation, add 200 mL of ethanol, stir to dissolve, then add 20% by mass potassium hydroxide ethanol solution, stir to disperse, control the pH to 8, filter, and dry to obtain tetraphosphate ester salt-based hexene.

[0027] (4) 0.2 mol of acrylic acid, 0.1 mol of methacrylate, 0.05 mol of maleic anhydride and 150 mL of deionized water were added to a flask and stirred to dissolve. Then, 0.01 mol of tetrasulfonate hexene, 0.01 mol of tetraphosphate hexene and 7.4 mmol of ammonium persulfate were added thereto. The mixture was reacted at 75° C. for 4 h. After the reaction was completed, the pH was adjusted to 8 using a 30% sodium hydroxide solution and dried to obtain a modified polycarboxylate surfactant.

[0028] Example 2

[0029] (1) Under nitrogen protection, 100 mL of ethanol and 0.05 mol of 3-hexene-1,6-diamine were added to a flask, and the mixture was stirred and dispersed at room temperature. Then, 0.25 mol of epichlorohydrin was added thereto, and the temperature was raised to 75° C. and the mixture was reacted for 3 h. After the reaction was completed, the temperature was lowered to 50° C., and a 30% by mass sodium hydroxide aqueous solution was added thereto. The mixture was stirred and reacted for 3 h. After the reaction was completed, the mixture was filtered and dried to obtain 1,6-tetraglycidylamine-3-hexene.

[0030] (2) Add 0.2 mol of sodium bisulfite and 100 mL of deionized water into a flask, stir to dissolve, heat to 75° C., add 0.05 mol of 1,6-tetraglycidylamine-3-hexene, stir to react for 1 h, and after the reaction is completed, cool to room temperature, filter, and dry to obtain tetrasulfonate hexene.

[0031] (3) Add 0.45 mol of phosphoric acid and 150 mL of ether to a flask, stir to dissolve, then add 0.1 mol of 1,6-tetraglycidylamine-3-hexene, stir to react at 40° C. for 8 h, and after the reaction is completed, remove the ether by vacuum distillation, add 200 mL of ethanol, stir to dissolve, then add 20% by mass potassium hydroxide ethanol solution, stir to disperse, control the pH to 7, filter, and dry to obtain tetraphosphate ester salt-based hexene.

[0032] (4) 0.2 mol of acrylic acid, 0.12 mol of methacrylate, 0.06 mol of maleic anhydride and 150 mL of deionized water were added to a flask and stirred to dissolve. Then, 0.02 mol of tetrasulfonate hexene, 0.02 mol of tetraphosphate hexene and 4.2 mmol of ammonium persulfate were added thereto. The mixture was reacted at 80° C. for 2 h. After the reaction was completed, the pH was adjusted to 7 using a 30% sodium hydroxide solution and dried to obtain a modified polycarboxylate surfactant.

[0033] Example 3

[0034] (1) Under nitrogen protection, 100 mL of ethanol and 0.05 mol of 3-hexene-1,6-diamine were added to a flask, and the mixture was stirred and dispersed at room temperature. Then, 0.24 mol of epichlorohydrin was added thereto, and the temperature was raised to 70° C. and the mixture was reacted for 6 h. After the reaction was completed, the temperature was lowered to 40° C., and a 30% by mass sodium hydroxide aqueous solution was added thereto. The mixture was stirred and reacted for 2 h. After the reaction was completed, the mixture was filtered and dried to obtain 1,6-tetraglycidylamine-3-hexene.

[0035] (2) Add 0.19 mol of sodium bisulfite and 100 mL of deionized water into a flask, stir to dissolve, heat to 65° C., add 0.05 mol of 1,6-tetraglycidylamine-3-hexene, stir to react for 2 h, and after the reaction is completed, cool to room temperature, filter, and dry to obtain tetrasulfonate hexene.

[0036] (3) Add 0.5 mol of phosphoric acid and 150 mL of ether to a flask, stir to dissolve, then add 0.1 mol of 1,6-tetraglycidylamine-3-hexene, stir to react at 40° C. for 4 h, and after the reaction is completed, remove the ether by vacuum distillation, add 200 mL of ethanol, stir to dissolve, then add 20% by mass potassium hydroxide ethanol solution, stir to disperse, control the pH to 8, filter, and dry to obtain tetraphosphate ester salt-based hexene.

[0037] (4) 0.2 mol of acrylic acid, 0.1 mol of methacrylate, 0.04 mol of maleic anhydride and 150 mL of deionized water were added to a flask and stirred to dissolve. Then, 0.03 mol of tetrasulfonate hexene, 0.03 mol of tetraphosphate hexene and 5 mmol of ammonium persulfate were added thereto. The mixture was reacted at 70° C. for 5 h. After the reaction was completed, the pH was adjusted to 7 using a 30% sodium hydroxide solution and dried to obtain a modified polycarboxylate surfactant.

[0038] Example 4

[0039] (1) Under nitrogen protection, 100 mL of ethanol and 0.05 mol of 3-hexene-1,6-diamine were added to a flask, and the mixture was stirred and dispersed at room temperature. Then, 0.24 mol of epichlorohydrin was added thereto, and the temperature was raised to 70° C. and the reaction was carried out for 5 h. After the reaction was completed, the temperature was lowered to 45° C., and a 30% by mass sodium hydroxide aqueous solution was added thereto. The mixture was stirred and reacted for 3 h. After the reaction was completed, the mixture was filtered and dried to obtain 1,6-tetraglycidylamine-3-hexene.

[0040] (2) Add 0.225 mol of sodium bisulfite and 100 mL of deionized water into a flask, stir to dissolve, heat to 60° C., add 0.05 mol of 1,6-tetraglycidylamine-3-hexene, stir to react for 2.5 h, and after the reaction is completed, cool to room temperature, filter, and dry to obtain tetrasulfonate hexene.

[0041] (3) Add 0.45 mol of phosphoric acid and 150 mL of ether to a flask, stir to dissolve, then add 0.1 mol of 1,6-tetraglycidylamine-3-hexene, stir to react at 45° C. for 6 h, and after the reaction is completed, remove the ether by vacuum distillation, add 200 mL of ethanol, stir to dissolve, then add 20% by mass potassium hydroxide ethanol solution, stir to disperse, control the pH to 7, filter, and dry to obtain tetraphosphate ester salt-based hexene.

[0042] (4) 0.2 mol of acrylic acid, 0.08 mol of methacrylate, 0.08 mol of maleic anhydride and 150 mL of deionized water were added to a flask and stirred to dissolve. Then, 0.04 mol of tetrasulfonate hexene, 0.04 mol of tetraphosphate hexene and 6 mmol of ammonium persulfate were added thereto. The mixture was reacted at 75° C. for 4 h. After the reaction was completed, the pH was adjusted to 8 using 30% sodium hydroxide solution and dried to obtain a modified polycarboxylate surfactant.

[0043] Comparative Example 1

[0044] The difference between this comparative example and Example 1 is that in step (4), tetrasulfonate hexene is not contained.

[0045] Comparative Example 2

[0046] The difference between this comparative example and Example 1 is that in step (4), tetraphosphate-based hexene is not contained.

[0047] 81.6 g of 97% ametryn technical, 4 g of modified polycarboxylate surfactant, 2 g of wetting agent SR-02, and 12.4 g of kaolin were mixed evenly, initially mixed using a solid sample grinder, stirred evenly, and then crushed using an ultrafine air flow grinder, and then 20 g of deionized water was added for kneading, granulation, drying, and sieving to obtain a water dispersible agent particle sample.

[0048] 5 g of water dispersant sample was added into an ampoule, sealed with an alcohol burner and placed in an electric thermostat at 55°C. After 14 days of hot storage, the sample was taken out and the suspension rate and dispersion performance were tested to determine the hot storage stability.

[0049] Refer to GB / T14825-2006 to test the suspension rate.

[0050] Table 1:

[0051]

[0052]

[0053] Dispersion performance test: add 2g of water dispersant particles into 98mL of deionized water, shake upside down 10 times for 2s each time, record the amount of sediment at 60min, shake upside down again 10 times after 60min, place in a constant temperature water bath at 25℃ for 24h, shake upside down again, and record the number of times the sediment is inverted again to disperse. The lower the number of inversions, the better the dispersion performance. If the number is less than 10 times, the sample is considered qualified.

[0054] Table 2:

[0055]

[0056] It can be seen from Table 1 and Table 2 that the modified polycarboxylate surfactant prepared by the present invention has good dispersibility, heat storage stability and high suspension rate, and the performance test results of Examples 1-4 are better than those of Comparative Examples 1-2. This is because, although two polar groups are also involved in Comparative Examples 1-2, their synergistic effect is not as good as that of three polar groups. Therefore, the modified polycarboxylate surfactant prepared by the present invention has excellent dispersibility, heat storage stability and high suspension rate.

[0057] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit the same. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a modified polycarboxylate surfactant, characterized in that: The preparation method is: (1) under nitrogen protection, ethanol and 3-hexene-1,6-diamine were added to a flask, stirred and dispersed at room temperature, epichlorohydrin was added thereto, the temperature was raised to 70-75° C., the reaction was carried out for 3-6 hours, after the reaction was completed, the temperature was lowered to 40-50° C., a 30% by mass sodium hydroxide aqueous solution was added thereto, the reaction was stirred for 1-3 hours, after the reaction was completed, suction filtered, and dried to obtain 1,6-tetraglycidylamine-3-hexene; (2) adding sodium bisulfite and deionized water to a flask, stirring to dissolve, heating to 60-75° C., adding 1,6-tetraglycidylamine-3-hexene thereto, stirring to react for 1-2.5 hours, and after the reaction is completed, cooling to room temperature, filtering with suction, and drying to obtain tetrasulfonate hexene; (3) adding phosphoric acid and ether to a flask, stirring to dissolve, then adding 1,6-tetraglycidylamine-3-hexene, stirring to react at 40-45° C. for 4-8 hours, after the reaction is completed, removing the ether by vacuum distillation, adding ethanol, stirring to dissolve, then adding 20% ​​by mass potassium hydroxide ethanol solution, stirring to disperse, controlling the pH to 7-8, suction filtering, and drying to obtain tetraphosphate ester salt-based hexene; (4) Add acrylic acid, methacrylate, maleic anhydride and deionized water into a flask, stir and dissolve, then add tetrasulfonate hexene, tetraphosphate hexene and ammonium persulfate, wherein the amount ratio of acrylic acid, methacrylate, maleic anhydride, tetrasulfonate hexene and tetraphosphate hexene is 1 mol: (0.4-0.6) mol: (0.2-0.4) mol: (0.05-0.2) mol: (0.05-0.2) mol, react at 70-80° C. for 2-5 hours, after the reaction is completed, adjust the pH to 7-8 with 30% by mass sodium hydroxide solution, dry and obtain a modified polycarboxylate surfactant.

2. The method for preparing the modified polycarboxylate surfactant according to claim 1, characterized in that: In the above (1), the usage ratio of 3-hexene-1,6-diamine and epichlorohydrin is 1 mol:(4-5) mol.

3. The method for preparing the modified polycarboxylate surfactant according to claim 1, characterized in that: In the method (2), the usage ratio of sodium bisulfite to 1,6-tetraglycidylamine-3-hexene is (3.8-4.5) mol:1 mol.

4. The method for preparing the modified polycarboxylate surfactant according to claim 1, characterized in that: In the above (3), the usage ratio of phosphoric acid and 1,6-tetraglycidylamine-3-hexene is (4-5) mol:1 mol.

5. The method for preparing the modified polycarboxylate surfactant according to claim 1, characterized in that: In the above (4), the amount of ammonium persulfate used is 1-2% of the total molar amount of acrylic acid, methacrylate, maleic anhydride, tetrasulfonate hexene and tetraphosphate hexene.

6. Use of the modified polycarboxylate surfactant prepared according to the preparation method according to claims 1-5 in pesticide preparations.

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