Preparation method of modified sulfonate surfactant and application of modified sulfonate surfactant in pesticide

Abstract

The invention relates to the technical field of surfactants, and discloses a preparation method of a modified sulfonate surfactant and application of the modified sulfonate surfactant in pesticides, diethylenetriamine and beta-(3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride are used as raw materials, and an amidation reaction is performed to obtain an intermediate product 1. The method comprises the following steps: carrying out substitution reaction on iminodipropionic acid and 1, 3-dichloro-5-vinyl benzene under the catalysis of sodium hydroxide to obtain an intermediate product 2, carrying out reaction on the intermediate product 2 and the intermediate product 1 to obtain an intermediate product 3, carrying out ring-opening reaction on the intermediate product 3 and 1, 3-propane sultone to obtain an intermediate product 4, and carrying out ring-opening reaction on the intermediate product 3 and 1, 3-propane sultone by using ammonium persulfate as an initiator to obtain the high-molecular polymer. And copolymerizing sodium p-styrenesulfonate with the intermediate product 3 and the intermediate product 4 by using sodium p-styrenesulfonate as an initiator, sodium hydrogen sulfite as a co-initiator and sodium dodecyl sulfate as an emulsifier to obtain the modified sulfonate surfactant. The modified sulfonate surfactant prepared by the preparation method disclosed by the invention has a relatively good dispersion effect and a relatively good anti-photolysis effect.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and specifically to a preparation method of a modified sulfonate surfactant and its application in pesticides. Background Art

[0002] Avermectin is a sixteen-membered macrolide compound with excellent insecticidal activity and is widely used in the control of crop pests such as rice, cotton, and vegetables. However, avermectin is prone to photolysis, and its activity and utilization rate are limited. Studying the stability of avermectin under sunlight is of great significance for the retention time of avermectin on the plant surface and improving the insecticidal effect of avermectin in the field.

[0003] Pesticide surfactants are essential auxiliaries in pesticide formulations. Sulfonate surfactants have a strongly hydrophilic sulfonic acid group, can stably exist in acidic or alkaline media, and are easily compounded with other surfactants to improve the dispersion effect.

[0004] The present invention creatively uses simple raw materials to synthesize a modified sulfonate surfactant, which not only has a good dispersion effect but also can improve the photodegradation stability of easily photolyzed pesticides, and has certain application prospects in the pesticide field. Summary of the Invention

[0005] The object of the present invention is to overcome one or more deficiencies in the prior art and provide a preparation method of a modified sulfonate surfactant and its application in pesticides. The surfactant prepared by this method not only has a good dispersion effect but also has photodegradation resistance performance. When applied to avermectin, it can improve the photodegradation resistance effect of avermectin.

[0006] To achieve the above object, a technical solution adopted by the present invention is:

[0007] A preparation method of a modified sulfonate surfactant, and the preparation method is as follows:

[0008] (1) Add diethylenetriamine and potassium carbonate to deionized water, stir and mix evenly. At 0 - 5 °C, add a benzene solution of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride thereto, stir and disperse, heat up to 20 - 30 °C, and react for 22 - 26 h. After the reaction is completed, perform negative pressure filtration, wash with deionized water, and dry to obtain intermediate 1. Using potassium carbonate as a catalyst, an amidation reaction is carried out between diethylenetriamine and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride to obtain intermediate 1, and its reaction route is:

[0009]

[0010] (2) Add iminodipropionic acid and sodium hydroxide to deionized water, stir and mix evenly, then add 1,3-dichloro-5-vinylbenzene thereto, control the reaction temperature at 60 - 80 °C, react for 1 - 3 h, perform vacuum distillation, and dry to obtain intermediate 2. Using iminodipropionic acid and 1,3-dichloro-5-vinylbenzene as raw materials, intermediate 2 is obtained through a substitution reaction. The reaction route is as follows:

[0011]

[0012] (3) Add intermediate 1 and sodium hydroxide to deionized water, stir and disperse, then add intermediate 2 thereto, react at 70 - 80 °C for 2 - 4 h. After the reaction, perform vacuum distillation and dry to obtain intermediate 3. Utilize the secondary amine group of intermediate 1 and the chlorine atom of intermediate 2 to undergo a substitution reaction to obtain intermediate 3. The reaction route is as follows:

[0013] Wherein

[0014] (4) Add sodium bisulfite and sodium dodecylsulfonate to deionized water, stir and mix evenly, then add sodium styrenesulfonate, intermediate 3, intermediate 4 and ammonium persulfate initiator, heat up to 60 - 80 °C, react for 1 - 3 h. After the reaction, use 30% sodium hydroxide aqueous solution to adjust the pH to 7 - 8, stir and mix evenly, and dry to obtain the modified sulfonate surfactant.

[0015] Preferably, in (1), the molar ratio of diethylenetriamine, potassium carbonate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1:1 - 1.2:1 - 1.2.

[0016] Preferably, in (2), the molar ratio of iminodipropionic acid, sodium hydroxide, and 1,3-dichloro-5-vinylbenzene is 0.8 - 1:0.8 - 1:1.

[0017] Preferably, in (3), the molar ratio of intermediate 1, sodium hydroxide, and intermediate 2 is 1:1 - 1.2:1 - 1.2.

[0018] Preferably, in (4), the molar ratio of sodium styrenesulfonate, intermediate 3, and intermediate 4 is 1:0.5 - 1:0.5 - 1.

[0019] Preferably, in (4), the dosage of sodium dodecylsulfonate is 2 - 3.5% of the total mass of sodium vinylsulfonate, intermediate 3, and intermediate 4; the dosage of sodium bisulfite is 3 - 7.5% of the total mass of sodium vinylsulfonate, intermediate 3, and intermediate 4; the dosage of ammonium persulfate is 5 - 8% of the total mass of sodium vinylsulfonate, intermediate 3, and intermediate 4.

[0020] Preferably, in said (4), the preparation method of intermediate product 4 is: adding intermediate product 3 to N,N-dimethylacetamide solvent, heating to 110-130° C., adding 1,3-propane sultone thereto, reacting for 3-6 hours, after completion, distilling under reduced pressure, washing with acetone, and drying to obtain intermediate product 4, and using intermediate product 3 and 1,3-propane sultone to perform ring-opening sulfonation to obtain intermediate product 4, and the reaction route is:

[0021] 1, where

[0022] Further preferably, the molar ratio of the intermediate product 3 to 1,3-propane sultone is 1:2-2.2.

[0023] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0024] (1) The present invention prepares intermediate 3 through a series of reactions, and further prepares intermediate 4 through a ring-opening reaction. The intermediate 4 has a novel structure and a relatively simple preparation method. The intermediate 4 is then copolymerized with sodium styrene sulfonate to obtain a modified sulfonate surfactant, which contains a sulfonic acid group, a carboxyl group, and a phenolic hydroxyl group. The hydrophilicity of the modified sulfonate surfactant is used to prepare a polymer molecular chain of varying lengths, which is tightly adsorbed on the surface of the pesticide particles to form an adsorption film to prevent the particles from aggregating. The synergistic effect enhances the spatial stability, improves the dispersion effect, and increases the suspension rate.

[0025] (2) In addition, the modified sulfonate surfactant prepared by the present invention contains a large amount of phenolic hydroxyl groups, which can remove active free radicals generated in photo-oxidative decomposition. Therefore, when ultraviolet rays are irradiated on the surface of pesticide particles, the surfactant adsorbed on the surface of the particles can inhibit the photo-oxidative decomposition of avermectin, thereby improving the anti-photolysis effect of avermectin. The modified sulfonate surfactant prepared by the present invention has been confirmed by experiments to have excellent dispersing effect and anti-photolysis effect. DETAILED DESCRIPTION

[0026] 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.

[0027] Preparation method of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride: Add 11.12 g of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid into chloroform, stir to dissolve, then add 16 mL of thionyl chloride thereto, heat up to 50 °C, react for 6 h. After the reaction is completed, perform reduced pressure distillation and drying to obtain β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride.

[0028] Example 1

[0029] (1) Add 20 mmol of diethylenetriamine and 24 mmol of potassium carbonate into 20 mL of deionized water, stir and mix evenly. At 0 °C, add 50 mL of a benzene solution containing 24 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride thereto, stir and disperse, heat up to 30 °C, react for 22 h. After the reaction is completed, perform negative pressure filtration, wash with deionized water, and dry to obtain Intermediate 1.

[0030] (2) Add 18 mmol of iminodipropionic acid and 18 mmol of sodium hydroxide into 100 mL of deionized water, stir and mix evenly, then add 20 mmol of 1,3-dichloro-5-vinylbenzene thereto, control the reaction temperature at 70 °C, react for 2 h, perform reduced pressure distillation, and dry to obtain Intermediate 2.

[0031] (3) Add 10 mmol of Intermediate 1 and 12 mmol of sodium hydroxide into 150 mL of deionized water, stir and disperse, then add 10 mmol of Intermediate 2 thereto, react at 75 °C for 3 h. After the reaction is completed, perform reduced pressure distillation and dry to obtain Intermediate 3.

[0032] (4) Add 10 mmol of Intermediate 3 into 100 mL of N,N-dimethylacetamide solvent, heat up to 115 °C, add 22 mmol of 1,3-propane sultone thereto, react for 5 h. After completion, perform reduced pressure distillation, wash with acetone, and dry to obtain Intermediate 4.

[0033] (5) Add 0.4 g of sodium bisulfite and 0.27 g of sodium dodecyl sulfonate into 80 mL of deionized water, stir and mix evenly, then add 8 mmol of sodium styrene sulfonate, 4 mmol of Intermediate 3, 4 mmol of Intermediate 4, and 0.67 g of ammonium persulfate initiator thereto, heat up to 70 °C, react for 2 h. After the reaction is completed, adjust the pH to 8 with 30% sodium hydroxide aqueous solution, stir and mix evenly, and dry to obtain the modified sulfonate surfactant.

[0034] Example 2

[0035] (1) 20 mmol of diethylenetriamine and 24 mmol of potassium carbonate were added to 20 mL of deionized water, stirred and mixed evenly. At 5 °C, 50 mL of a benzene solution containing 20 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride was added thereto, stirred and dispersed, then the temperature was raised to 25 °C, and the reaction was carried out for 24 h. After the reaction, vacuum filtration was carried out, washed with deionized water, and dried to obtain Intermediate 1.

[0036] (2) 20 mmol of iminodipropionic acid and 20 mmol of sodium hydroxide were added to 100 mL of deionized water, stirred and mixed evenly. Then 20 mmol of 1,3-dichloro-5-vinylbenzene was added thereto, and the reaction temperature was controlled at 60 °C. The reaction was carried out for 3 h, followed by distillation under reduced pressure and drying to obtain Intermediate 2.

[0037] (3) 10 mmol of Intermediate 1 and 10 mmol of sodium hydroxide were added to 150 mL of deionized water, stirred and dispersed. Then 12 mmol of Intermediate 2 was added thereto. At 80 °C, the reaction was carried out for 2 h. After the reaction, distillation under reduced pressure was carried out, and drying was carried out to obtain Intermediate 3.

[0038] (4) 10 mmol of Intermediate 3 was added to 100 mL of N,N-dimethylacetamide solvent, and the temperature was raised to 130 °C. 20 mmol of 1,3-propane sultone was added thereto, and the reaction was carried out for 3 h. After the reaction, distillation under reduced pressure was carried out, washed with acetone, and dried to obtain Intermediate 4.

[0039] (5) 1.5 g of sodium bisulfite and 0.6 g of sodium dodecyl sulfonate were added to 80 mL of deionized water, stirred and mixed evenly. Then 8 mmol of sodium styrene sulfonate, 7 mmol of Intermediate 3, 5 mmol of Intermediate 4 and 1 g of ammonium persulfate initiator were added thereto. The temperature was raised to 70 °C, and the reaction was carried out for 2 h. After the reaction, the pH was adjusted to 8 with 30% aqueous sodium hydroxide solution, stirred and mixed evenly, and dried to obtain the modified sulfonate surfactant.

[0040] Example 3

[0041] (1) 20 mmol of diethylenetriamine and 24 mmol of potassium carbonate were added to 20 mL of deionized water, stirred and mixed evenly. At 0 °C, 50 mL of a benzene solution containing 24 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride was added thereto, stirred and dispersed, then the temperature was raised to 20 °C, and the reaction was carried out for 26 h. After the reaction, vacuum filtration was carried out, washed with deionized water, and dried to obtain Intermediate 1.

[0042] (2) Add 16 mmol of iminodipropionic acid and 16 mmol of sodium hydroxide to 100 mL of deionized water, stir and mix evenly, then add 20 mmol of 1,3-dichloro-5-vinylbenzene thereto, control the reaction temperature at 70 °C, react for 2 h, carry out vacuum distillation, and dry to obtain intermediate 2.

[0043] (3) Add 10 mmol of intermediate 1 and 12 mmol of sodium hydroxide to 150 mL of deionized water, stir and disperse, then add 12 mmol of intermediate 2 thereto, react at 70 °C for 4 h, after the reaction is completed, carry out vacuum distillation, and dry to obtain intermediate 3.

[0044] (4) Add 10 mmol of intermediate 3 to 100 mL of N,N-dimethylacetamide solvent, heat up to 110 °C, add 22 mmol of 1,3-propane sultone thereto, react for 6 h, after completion, carry out vacuum distillation, wash with acetone, and dry to obtain intermediate 4.

[0045] (5) Add 1.9 g of sodium bisulfite and 0.89 g of sodium dodecyl sulfonate to 80 mL of deionized water, stir and mix evenly, then add 8 mmol of sodium styrene sulfonate, 7 mmol of intermediate 3, 8 mmol of intermediate 4 and 2 g of ammonium persulfate initiator thereto, heat up to 60 °C, react for 3 h, after the reaction is completed, adjust the pH to 7 with 30% aqueous sodium hydroxide solution, stir and mix evenly, and dry to obtain the modified sulfonate surfactant.

[0046] Example 4

[0047] (1) Add 20 mmol of diethylenetriamine and 24 mmol of potassium carbonate to 20 mL of deionized water, stir and mix evenly, at 5 °C, add 50 mL of a benzene solution containing 22 mmol of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride thereto, stir and disperse, heat up to 25 °C, react for 25 h, after the reaction is completed, carry out negative pressure filtration, wash with deionized water, and dry to obtain intermediate 1.

[0048] (2) Add 16 mmol of iminodipropionic acid and 18 mmol of sodium hydroxide to 100 mL of deionized water, stir and mix evenly, then add 20 mmol of 1,3-dichloro-5-vinylbenzene thereto, control the reaction temperature at 80 °C, react for 1 h, carry out vacuum distillation, and dry to obtain intermediate 2.

[0049] (3) Add 10 mmol of intermediate 1 and 11 mmol of sodium hydroxide to 150 mL of deionized water, stir and disperse, then add 10 mmol of intermediate 2 thereto, react at 80 °C for 4 h, after the reaction is completed, carry out vacuum distillation, and dry to obtain intermediate 3.

[0050] (4) Add 10 mmol of intermediate 3 to 100 mL of N,N-dimethylacetamide solvent, heat up to 120 °C, add 20 mmol of 1,3-propanesultone thereto, react for 5 h, after completion, distill under reduced pressure, wash with acetone, and dry to obtain intermediate 4.

[0051] (5) Add 1 g of sodium bisulfite and 0.5 g of sodium dodecylsulfonate to 80 mL of deionized water, stir and mix evenly, then add 8 mmol of sodium styrenesulfonate, 8 mmol of intermediate 3, 8 mmol of intermediate 4 and 1.5 g of ammonium persulfate initiator thereto, heat up to 75 °C, react for 2 h, after completion of the reaction, adjust the pH to 8 with 30% aqueous sodium hydroxide solution, stir and mix evenly, and dry to obtain the modified sulfonate surfactant.

[0052] Comparative Example 1

[0053] The difference between this comparative example and Example 1 is that in step (5), intermediate 3 is not contained.

[0054] Comparative Example 2

[0055] The difference between this comparative example and Example 1 is that in step (5), intermediate 4 is not contained.

[0056] Add 3 g of sulfonate surfactant, 45 g of 2.5% xanthan gum stabilizer, and 0.5 g of silicone defoamer to deionized water, dissolve ultrasonically, adjust the pH to 7 with dilute hydrochloric acid and dilute sodium hydroxide, then add 5.26 g of 95% abamectin technical thereto, and make up to 100 g with deionized water, and perform sanding with a sanding machine to obtain 5% abamectin aqueous suspension concentrate.

[0057] Refer to GB / T14825-2006 to test the suspension rate.

[0058] Table 1:

[0059] Suspension rate (%) Example 1 89.4 Example 2 93.5 Example 3 98.1 Example 4 99.9 Comparative Example 1 80.3 Comparative Example 2 82.4

[0060] As can be seen from the table, the suspension and dispersion effects in Comparative Example 1 and Comparative Example 2 are inferior to those in Examples 1-5. Among Examples 1-5, as the dosages of intermediate 3 and intermediate 4 increase, the suspension and dispersion effects increase. From the data of Comparative Example 1 and Comparative Example 2, it can be seen that the suspension and dispersion effect of the synergistic action of carboxylate and sulfonate is better.

[0061] Disperse 1 g of abamectin aqueous suspension concentrate into a 100 mL volumetric flask. Take out 400 μL of the dilution and spread it in a glass petri dish with a diameter of 4 cm. Keep it away from light and dry to form a film. Under ultraviolet light with a power of 30 W and a wavelength of 310 nm, irradiate for 0 h, 24 h, and 48 h respectively. Then dissolve the sample with 10 mL of methanol and use HPLC to detect the content of the technical material. The effective ingredient percentage of abamectin = the effective integral area of abamectin component in HPLC / (13088×100)×100%, and the decomposition rate (%) = (1 - the effective ingredient of abamectin at 24 h / the effective ingredient of abamectin at 0 h)×100%.

[0062] Table 2:

[0063] Decomposition rate (%) Example 1 6.4 Example 2 5.4 Example 3 4.8 Example 4 4.5 Comparative Example 1 10.5 Comparative Example 2 10.8

[0064] As can be seen from the table, the suspension concentrate prepared with the surfactant of the present invention has a good anti-photolysis effect. This is because the surfactant adsorbs on the surface of abamectin, can fully scavenge the free radicals generated in the photo-oxidative degradation of abamectin, has a good inhibitory effect on the decomposition of abamectin, improves the utilization rate of abamectin, and can be widely applied to pesticides that are prone to photolysis. The modified sulfonate surfactant prepared in the present invention not only has a good dispersion effect, but also can improve the utilization rate of pesticides that are prone to photolysis.

[0065] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements on some of the technical features; and these modifications or replacements will not make the essence of the corresponding technical solutions 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 sulfonate surfactant, characterized in that, The preparation method is as follows: (1) Add diethylenetriamine and potassium carbonate to deionized water, stir and mix evenly. At 0 - 5 °C, add a benzene solution of β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride thereto, stir and disperse, then raise the temperature to 20 - 30 °C, and react for 22 - 26 h. After the reaction is completed, perform vacuum filtration, wash with deionized water, and dry to obtain Intermediate 1; (2) Add iminodipropionic acid and sodium hydroxide to deionized water, stir and mix evenly. Then add 1,3-dichloro-5-vinylbenzene thereto, control the reaction temperature at 60 - 80 °C, react for 1 - 3 h, perform reduced pressure distillation, and dry to obtain Intermediate 2; (3) Add Intermediate 1 and sodium hydroxide to deionized water, stir and disperse. Then add Intermediate 2 thereto, and react at 70 - 80 °C for 2 - 4 h. After the reaction is completed, perform reduced pressure distillation, and dry to obtain Intermediate 3; (4) Add sodium bisulfite and sodium dodecylsulfonate to deionized water, stir and mix evenly. Then add sodium styrenesulfonate, Intermediate 3, Intermediate 4, and an ammonium persulfate initiator thereto, raise the temperature to 60 - 80 °C, react for 1 - 3 h. After the reaction is completed, adjust the pH to 7 - 8 with a 30% aqueous sodium hydroxide solution, stir and mix evenly, and dry to obtain the modified sulfonate surfactant.

2. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (1), the molar ratio of diethylenetriamine, potassium carbonate, and β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyl chloride is 1:1 - 1.2:1 - 1.

2.

3. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (2), the molar ratio of iminodipropionic acid, sodium hydroxide, and 1,3-dichloro-5-vinylbenzene is 0.8 - 1:0.8 - 1:

1.

4. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (3), the molar ratio of Intermediate 1, sodium hydroxide, and Intermediate 2 is 1:1 - 1.2:1 - 1.

2.

5. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (4), the molar ratio of sodium styrenesulfonate, Intermediate 3, and Intermediate 4 is 1:0.5 - 1:0.5 - 1.

6. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (4), the dosage of sodium dodecylsulfonate is 2 - 3.5% of the total mass of sodium vinylsulfonate, Intermediate 3, and Intermediate 4; the dosage of sodium bisulfite is 3 - 7.5% of the total mass of sodium vinylsulfonate, Intermediate 3, and Intermediate 4; the dosage of ammonium persulfate is 5 - 8% of the total mass of sodium vinylsulfonate, Intermediate 3, and Intermediate 4.

7. The method for preparing a modified sulfonate surfactant according to claim 1, characterized in that, In the above (4), the preparation method of Intermediate 4 is: Add Intermediate 3 to an N,N-dimethylacetamide solvent, raise the temperature to 110 - 130 °C, add 1,3-propane sultone thereto, react for 3 - 6 h. After completion, perform reduced pressure distillation, wash with acetone, and dry to obtain Intermediate 4.

8. The method for preparing a modified sulfonate surfactant according to claim 7, characterized in that, The molar ratio of Intermediate 3 and 1,3-propane sultone is 1:2 - 2.2.

Images