A tocopherol-containing polycarboxylate surfactant and its use in pesticides

Abstract

The present application relates to the technical field of tocopherol-containing polycarboxylate surfactant, and discloses a tocopherol-containing polycarboxylate surfactant and application thereof in pesticides, wherein the tocopherol-containing polycarboxylate surfactant is prepared from trans-1,4-dichloro-2-butene, diethanolamine, phosphorus pentoxide and the like as raw materials through substitution reaction and esterification reaction to obtain an olefin-containing tetraphosphoric acid intermediate; DL-alpha-tocopherol, maleic anhydride, polyethylene glycol and the like are used as raw materials to obtain tocopherol-modified polyethylene glycol through two-step reaction; and the olefin group contained in the tocopherol-modified polyethylene glycol is used to copolymerize with acrylic acid, the olefin-containing tetraphosphoric acid intermediate and the like to obtain the tocopherol-containing polycarboxylate surfactant. The tocopherol-containing polycarboxylate surfactant prepared by the present application can be applied to pesticides to improve the suspension effect and heat storage stability of the pesticide water suspension agent.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tocopherol-containing polycarboxylate surfactants, in particular to a tocopherol-containing polycarboxylate surfactant and its application in pesticides. BACKGROUND

[0002] Pesticide water suspending agent is a pesticide preparation with water as the base. During its storage process, flocculation and aggregation are prone to occur between particles due to Ostwald ripening, which is a thermodynamically unstable system. Therefore, a substance capable of reducing the interfacial tension between pesticide particles and liquid medium needs to be added to prevent the occurrence of Ostwald ripening, and a surfactant is incubated.

[0003] A surfactant is a substance that can play a dispersing role in a system, stabilize particles, and inhibit flocculation between particles. In a system, a surfactant has three main action modes: (1) forming a double electric layer around particles to enhance the electrostatic repulsion between particles; (2) reducing the interfacial energy of particles to inhibit the aggregation behavior between particles; and (3) adsorbing on the surface of particles to increase steric hindrance. Polycarboxylate surfactant is a homopolymer or copolymer containing carboxylic acid group monomers, and is a highly efficient anionic surfactant. However, it has been found that the effect of a single surfactant is not as good as that of a compounded system surfactant. SUMMARY

[0004] (I) Technical problems solved

[0005] In view of the deficiencies of the prior art, the present application provides a tocopherol-containing polycarboxylate surfactant and its application in pesticides. When applied to pesticide preparations, the tocopherol-containing polycarboxylate surfactant can improve the suspending effect and thermal storage stability of pesticide water suspending agent.

[0006] (II) Technical solutions

[0007] A preparation method of a tocopherol-containing polycarboxylate surfactant, the preparation method comprising:

[0008] Under a nitrogen atmosphere, tocopherol-modified polyethylene glycol, acrylic acid, methyl methacrylate, tetraphosphonic acid-containing olefin intermediate, and ammonium persulfate are added to deionized water, the temperature is controlled at 80-85°C, and the reaction is carried out for 2-5 hours. After the reaction is completed, a tocopherol-containing polycarboxylate surfactant is obtained.

[0009] In one embodiment, preferably, the mass ratio of the tocopherol-modified polyethylene glycol, acrylic acid, methyl methacrylate, tetraphosphonic acid-containing olefin intermediate, and ammonium persulfate is 0.5-1:1:0.2-0.5:0.5-1:0.1-0.3.

[0010] In one embodiment, preferably, the preparation method of the tetraphosphoric acid containing olefin intermediate is as follows:

[0011] A1, trans-1, 4-dichloro-2-butene is added to deionized water, sodium hydroxide is added thereto, the mixture is stirred and mixed uniformly, diethanolamine is added thereto, and the reaction is carried out at 40-50℃ for 10-14h, after the reaction is completed, filtration is performed, rotary evaporation is carried out, and intermediate 1 is obtained;

[0012] A2, intermediate 1 is added to deionized water, stirring and dispersion are performed, and phosphorus pentoxide is added thereto, and the reaction is carried out at 75-85℃ for 2-5h, after the reaction is completed, filtration is performed, rotary evaporation is carried out, and drying is performed, and the tetraphosphoric acid containing olefin intermediate is obtained.

[0013] In one embodiment, further preferably, in A1, the molar ratio of trans-1, 4-dichloro-2-butene, sodium hydroxide, diethanolamine is 1:1.2-1.4:2-2.4.

[0014] In one embodiment, further preferably, in A2, the molar ratio of intermediate 1, phosphorus pentoxide is 1:4.5-5.

[0015] In one embodiment, preferably, the preparation method of the tocopherol modified polyethylene glycol is as follows:

[0016] S1, DL-α-tocopherol, maleic anhydride, and triethylamine are added to cyclohexane solvent, and the reaction is carried out at reflux for 10-14h, after the reaction is completed, deionized water is added thereto, dichloromethane is extracted, hydrochloric acid and deionized water are sequentially used for washing, drying is performed, rotary evaporation is carried out, and the carboxylated tocopherol is obtained.

[0017] S2, the carboxylated tocopherol, polyethylene glycol, and p-toluenesulfonic acid are added to cyclohexane solvent, and the reaction is carried out at reflux for 6-10h, after the reaction is completed, saturated sodium bicarbonate solution is added thereto, ethyl acetate is extracted, saturated sodium bicarbonate solution is washed, drying is performed, and rotary evaporation is carried out, and the tocopherol modified polyethylene glycol is obtained.

[0018] In one embodiment, further preferably, the molar ratio of DL-α-tocopherol, maleic anhydride, and triethylamine is 1:1.5-2:1.6-2.2.

[0019] In one embodiment, further preferably, the molar ratio of the carboxylated tocopherol, polyethylene glycol, and p-toluenesulfonic acid is 1:1:1.2-1.5.

[0020] In addition to the above technical solutions, the tocopherol containing polycarboxylate surfactant prepared above can also be applied in pesticides.

[0021] (Three) beneficial technical effects

[0022] The present application utilizes trans-1,4-dichloro-2-butene and diethanolamine under alkaline conditions to obtain intermediate 1 through substitution reaction, utilizes the hydroxyl structure contained in intermediate 1 to perform esterification with phosphorus pentoxide to obtain an olefin-containing tetraphosphoric acid intermediate. DL-α-tocopherol and maleic anhydride are used to obtain carboxylated tocopherol under the catalysis of triethylamine, and then the carboxylated tocopherol is used to obtain tocopherol-modified polyethylene glycol under the catalysis of p-toluenesulfonic acid through esterification reaction, and finally the olefin structure contained in the tocopherol-modified polyethylene glycol is used to perform copolymerization with acrylic acid, the olefin-containing tetraphosphoric acid intermediate and the like under the initiation of ammonium persulfate to obtain a tocopherol-containing polycarboxylate surfactant.

[0023] The tocopherol-containing polycarboxylate surfactant prepared by the present application has a main chain structure and a tocopherol structure as a lipophilic end of the surfactant, which has many sites that can anchor pesticide particles to form multi-point adsorption on the surface of the pesticide particles, thereby playing a good anchoring role and making the surfactant less likely to transfer and desorb. The polyethylene glycol structure not only provides a large steric hindrance barrier to prevent the aggregation of pesticide particles, but also serves as a hydrophilic end of the surfactant together with the carboxyl structure and the phosphoric acid structure to extend into the aqueous phase and form a large number of negative charges around the surface of the pesticide particles, thereby providing a large electrostatic repulsion to break the aggregation of the pesticide particles, maintain the stability of the system and improve the suspension effect of the pesticide water suspending agent. In addition, the olefin-containing tetraphosphoric acid intermediate prepared by the present application contains a tetraphosphoric acid structure, and the intermolecular electrostatic repulsion of the tetraphosphoric acid structure is larger than that of a monophosphoric acid structure. The tetraphosphoric acid structure, together with the carboxylic acid structure and the polyethylene glycol structure, produces greater steric hindrance and electrostatic repulsion, thereby further improving the suspension effect of the pesticide water suspending agent. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a reaction process route of the olefin-containing tetraphosphoric acid intermediate;

[0025] Figure 2 is a reaction process route of the tocopherol-modified polyethylene glycol. DETAILED DESCRIPTION

[0026] In order to facilitate the understanding of the present application, the present application will be described more fully below, and preferred embodiments of the present application will be given. However, the present application can be realized in many different forms, and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0027] Example 1

[0028] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, 0.65 mol of sodium hydroxide was added thereto, the mixture was stirred and mixed, 1 mol of diethanolamine was added thereto, and the mixture was reacted at 45°C for 12 h. After the reaction was completed, the mixture was suction-filtered and rotary-evaporated to obtain intermediate 1.

[0029] (2) 0.2 mol of intermediate 1 was added to 50 mL of deionized water, the mixture was stirred and dispersed, 0.9 mol of phosphorus pentoxide was added thereto, and the mixture was reacted at 85°C for 4 h. After the reaction was completed, the mixture was filtered, rotary-evaporated, and dried to obtain an olefin-containing tetraphosphoric acid intermediate.

[0030] (3) 0.1 mol of DL-α-tocopherol, 0.18 mol of maleic anhydride, and 0.22 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and the mixture was refluxed for 12 h. After the reaction was completed, deionized water was added to the mixture, the mixture was extracted with dichloromethane, washed with hydrochloric acid and deionized water in this order, dried, and rotary-evaporated to obtain a carboxylated tocopherol.

[0031] (4) 0.1 mol of the carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.15 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and the mixture was refluxed for 6 h. After the reaction was completed, saturated sodium bicarbonate solution was added to the mixture, the mixture was extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried, and rotary-evaporated to obtain a tocopherol-modified polyethylene glycol.

[0032] (5) 10 g of the tocopherol-modified polyethylene glycol, 20 g of acrylic acid, 4 g of methyl methacrylate, 10 g of the olefin-containing tetraphosphoric acid intermediate, and 5 g of ammonium persulfate were added to 200 mL of deionized water under a nitrogen atmosphere, and the temperature of the mixture was controlled at 85°C. The mixture was reacted for 4 h. After the reaction was completed, a tocopherol-containing polycarboxylate surfactant was obtained.

[0033] Example 2

[0034] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, 0.7 mol of sodium hydroxide was added thereto, the mixture was stirred and mixed, 1.2 mol of diethanolamine was added thereto, and the mixture was reacted at 50°C for 10 h. After the reaction was completed, the mixture was suction-filtered and rotary-evaporated to obtain intermediate 1.

[0035] (2) 0.2 mol of intermediate 1 was added to 50 mL of deionized water, the mixture was stirred and dispersed, 0.9 mol of phosphorus pentoxide was added thereto, and the mixture was reacted at 75°C for 4 h. After the reaction was completed, the mixture was filtered, rotary-evaporated, and dried to obtain an olefin-containing tetraphosphoric acid intermediate.

[0036] (3) 0.1 mol of DL-α-tocopherol, 0.16 mol of maleic anhydride, and 0.18 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and refluxed for 12 hours. After the reaction was completed, deionized water was added thereto, and dichloromethane was extracted. The extracted product was washed with hydrochloric acid and deionized water, dried, and distilled under reduced pressure to obtain carboxylated tocopherol.

[0037] (4) 0.1 mol of carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.14 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and refluxed for 10 hours. After the reaction was completed, saturated sodium bicarbonate solution was added thereto, and ethyl acetate was extracted. The extracted product was washed with saturated sodium bicarbonate solution, dried, and distilled under reduced pressure to obtain tocopherol-modified polyethylene glycol.

[0038] (5) 14 g of tocopherol-modified polyethylene glycol, 20 g of acrylic acid, 10 g of methyl methacrylate, 14 g of tetraphosphoric acid-containing olefin intermediate, and 6 g of ammonium persulfate were added to 200 mL of deionized water under a nitrogen atmosphere, and the temperature was controlled at 80°C to react for 5 hours. After the reaction was completed, a tocopherol-containing polycarboxylate surfactant was obtained.

[0039] Example 3

[0040] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, and 0.6 mol of sodium hydroxide was added thereto. After the mixture was stirred and uniformly mixed, 1 mol of diethanolamine was added thereto, and the mixture was reacted at 40°C for 14 hours. After the reaction was completed, the mixture was filtered and distilled under reduced pressure to obtain intermediate 1.

[0041] (2) 0.2 mol of intermediate 1 was added to 50 mL of deionized water, and the mixture was stirred and dispersed. Then, 0.9 mol of phosphorus pentoxide was added thereto, and the mixture was reacted at 85°C for 4 hours. After the reaction was completed, the mixture was filtered, distilled under reduced pressure, and dried to obtain a tetraphosphoric acid-containing olefin intermediate.

[0042] (3) 0.1 mol of DL-α-tocopherol, 0.2 mol of maleic anhydride, and 0.16 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and refluxed for 10 hours. After the reaction was completed, deionized water was added thereto, and dichloromethane was extracted. The extracted product was washed with hydrochloric acid and deionized water, dried, and distilled under reduced pressure to obtain carboxylated tocopherol.

[0043] (4) 0.1 mol of carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.12 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and refluxed for 8 hours. After the reaction was completed, saturated sodium bicarbonate solution was added thereto, and ethyl acetate was extracted. The extracted product was washed with saturated sodium bicarbonate solution, dried, and distilled under reduced pressure to obtain tocopherol-modified polyethylene glycol.

[0044] (5) Under a nitrogen atmosphere, 16 g of the tocopheryl-modified polyethylene glycol, 20 g of acrylic acid, 8 g of methyl methacrylate, 16 g of the tetraphosphonic acid-containing olefin intermediate, and 2 g of ammonium persulfate were added to 200 mL of deionized water, and the temperature was controlled at 80°C, and the reaction was performed for 2 h. After the reaction was completed, a tocopheryl-containing polycarboxylate surfactant was obtained.

[0045] Example 4

[0046] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, 0.62 mol of sodium hydroxide was added thereto, and the mixture was stirred and mixed, 1 mol of diethanolamine was added thereto, and the reaction was performed at 45°C for 14 h. After the reaction was completed, filtration and rotary evaporation were performed, and an intermediate 1 was obtained.

[0047] (2) 0.2 mol of the intermediate 1 was added to 50 mL of deionized water, and the mixture was stirred and dispersed, 1 mol of phosphorus pentoxide was added thereto, and the reaction was performed at 75°C for 5 h. After the reaction was completed, filtration, rotary evaporation, and drying were performed, and a tetraphosphonic acid-containing olefin intermediate was obtained.

[0048] (3) 0.1 mol of DL-α-tocopherol, 0.18 mol of maleic anhydride, and 0.2 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and the reaction was performed at reflux for 14 h. After the reaction was completed, deionized water was added thereto, dichloromethane extraction was performed, and washing with hydrochloric acid and deionized water was sequentially performed, and drying and rotary evaporation were performed, and carboxylated tocopherol was obtained.

[0049] (4) 0.1 mol of the carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.14 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and the reaction was performed at reflux for 8 h. After the reaction was completed, saturated sodium bicarbonate solution was added thereto, extraction was performed using ethyl acetate, washing was performed using saturated sodium bicarbonate solution, drying was performed, and rotary evaporation was performed, and tocopheryl-modified polyethylene glycol was obtained.

[0050] (5) Under a nitrogen atmosphere, 16 g of the tocopheryl-modified polyethylene glycol, 20 g of acrylic acid, 8 g of methyl methacrylate, 16 g of the tetraphosphonic acid-containing olefin intermediate, and 2 g of ammonium persulfate were added to 200 mL of deionized water, and the temperature was controlled at 80°C, and the reaction was performed for 2 h. After the reaction was completed, a tocopheryl-containing polycarboxylate surfactant was obtained.

[0051] Example 5

[0052] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, 0.65 mol of sodium hydroxide was added thereto, the mixture was stirred and mixed, 1.2 mol of diethanolamine was added thereto, and the mixture was reacted at 45°C for 12 h. After the reaction was completed, the mixture was filtered and evaporated to obtain intermediate 1.

[0053] (2) 0.2 mol of intermediate 1 was added to 50 mL of deionized water, the mixture was stirred and dispersed, and 0.9 mol of phosphorus pentoxide was added thereto. The mixture was reacted at 80°C for 2 h. After the reaction was completed, the mixture was filtered, evaporated, and dried to obtain an olefin-containing tetraphosphoric acid intermediate.

[0054] (3) 0.1 mol of DL-α-tocopherol, 0.15 mol of maleic anhydride, and 0.22 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and the mixture was refluxed for 12 h. After the reaction was completed, deionized water was added to the mixture, dichloromethane was extracted, and the extracted product was washed with hydrochloric acid and deionized water, dried, and evaporated to obtain carboxylated tocopherol.

[0055] (4) 0.1 mol of carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.14 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and the mixture was refluxed for 9 h. After the reaction was completed, saturated sodium bicarbonate solution was added to the mixture, the mixture was extracted with ethyl acetate, and the extracted product was washed with saturated sodium bicarbonate solution, dried, and evaporated to obtain tocopherol-modified polyethylene glycol.

[0056] (5) 20 g of tocopherol-modified polyethylene glycol, 20 g of acrylic acid, 8 g of methyl methacrylate, 20 g of the olefin-containing tetraphosphoric acid intermediate, and 5 g of ammonium persulfate were added to 200 mL of deionized water under a nitrogen atmosphere, and the temperature of the mixture was controlled at 80°C. The mixture was reacted for 5 h. After the reaction was completed, a tocopherol-containing polycarboxylate surfactant was obtained.

[0057] Comparative Example 1

[0058] (1) 0.1 mol of DL-α-tocopherol, 0.18 mol of maleic anhydride, and 0.22 mol of triethylamine were added to 200 mL of a cyclohexane solvent, and the mixture was refluxed for 12 h. After the reaction was completed, deionized water was added to the mixture, dichloromethane was extracted, and the extracted product was washed with hydrochloric acid and deionized water, dried, and evaporated to obtain carboxylated tocopherol.

[0059] (2) 0.1 mol of carboxylated tocopherol, 0.1 mol of polyethylene glycol 200, and 0.15 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and refluxed for 6 h. After the reaction was completed, saturated sodium bicarbonate solution was added thereto, extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried, and rotary evaporated to obtain a tocopherol-modified polyethylene glycol.

[0060] (3) 10 g of the tocopherol-modified polyethylene glycol, 20 g of acrylic acid, 4 g of methyl methacrylate, and 5 g of ammonium persulfate were added to 200 mL of deionized water under a nitrogen atmosphere, and the temperature was controlled at 85°C, and reacted for 4 h. After the reaction was completed, a polycarboxylate surfactant was obtained.

[0061] Comparative Example 2

[0062] (1) 0.5 mol of trans-1,4-dichloro-2-butene was added to 50 mL of deionized water, 0.65 mol of sodium hydroxide was added thereto, and the mixture was stirred and mixed uniformly, and then 1 mol of diethanolamine was added thereto, and reacted at 45°C for 12 h. After the reaction was completed, suction filtration was performed, and rotary evaporation was performed to obtain an intermediate 1.

[0063] (2) 0.2 mol of the intermediate 1 was added to 50 mL of deionized water, and stirred and dispersed, and then 0.9 mol of phosphorus pentoxide was added thereto, and reacted at 85°C for 4 h. After the reaction was completed, filtration was performed, and rotary evaporation and drying were performed to obtain an olefin-containing tetraphosphoric acid intermediate.

[0064] (3) 0.1 mol of maleic anhydride, 0.1 mol of polyethylene glycol 200, and 0.15 mol of p-toluenesulfonic acid were added to 200 mL of a cyclohexane solvent, and refluxed for 6 h. After the reaction was completed, saturated sodium bicarbonate solution was added thereto, extracted with ethyl acetate, washed with saturated sodium bicarbonate solution, dried, and rotary evaporated to obtain a modified polyethylene glycol.

[0065] (4) 10 g of the modified polyethylene glycol, 20 g of acrylic acid, 4 g of methyl methacrylate, 10 g of the olefin-containing tetraphosphoric acid intermediate, and 5 g of ammonium persulfate were added to 200 mL of deionized water under a nitrogen atmosphere, and the temperature was controlled at 85°C, and reacted for 4 h. After the reaction was completed, a polycarboxylate surfactant was obtained.

[0066] 93% of the tebuconazole technical material 83.88 g, 8 g of the polycarboxylate surfactant, 6 g of ethylene glycol, 10 g of xanthan gum, 0.4 g of AFE-3168 silicone antifoaming agent, and 91.72 g of deionized water were added to a sanding bottle, and stirred and dissolved. 200 g of zirconium beads having a diameter of 1.2 mm were added thereto, and milled for 4 h to obtain a tebuconazole aqueous suspension.

[0067] The suspension rate of the preparation was determined according to GB / T 14825-2006, and the preparation was placed in an electric thermostatic oven at 55 DEG C for heat storage for two weeks, and then the suspension rate was determined again.

[0068] Table 1: Suspension rate before and after heat storage of each example and comparative example

[0069]

[0070] As shown in the table, in examples 1-5, with the increase of the amount of tocopherol modified polyethylene glycol and tetraphosphoric acid containing olefinic intermediate, the suspension effect increases, and the suspension rate can reach 99.9%; as shown in example 1 and comparative examples 1-2, the suspension effect of any one of the tocopherol modified polyethylene glycol and tetraphosphoric acid containing olefinic intermediate is poorer than that of example 1, and the suspension rate before and after heat storage is poorer than that of comparative example 1, which indicates that the combination of the tocopherol modified polyethylene glycol and tetraphosphoric acid containing olefinic intermediate can effectively improve the storage stability and suspension rate of the water suspension agent.

[0071] At room temperature, 0.1 g of the preparation was added into 100 mL of deionized water, shaken and mixed uniformly, and then balanced in a Zeta potential determination special dish for 5 min, and the Zeta potential on the surface of the pesticide was determined.

[0072] Table 2: Zeta potential of each example and comparative example

[0073]

[0074] The greater the absolute value of the Zeta potential, the more stable the system and the better the dispersion effect, and as shown in the table, the tocopherol-containing polycarboxylate surfactant prepared by the application has good dispersion effect when applied to pesticides.

Claims

1. A tocopherol-containing polycarboxylate surfactant characterized in that, The preparation method of the polycarboxylate surfactant is: Under a nitrogen atmosphere, the tocopherol modified polyethylene glycol, acrylic acid, methyl methacrylate, tetraphosphonic acid containing olefin intermediate, and ammonium persulfate are added to deionized water, the temperature is controlled at 80-85°C, and the reaction is carried out for 2-5 hours, wherein the mass ratio of the tocopherol modified polyethylene glycol, acrylic acid, methyl methacrylate, tetraphosphonic acid containing olefin intermediate, and ammonium persulfate is 0.5-1:1:0.2-0.5:0.5-1:0.1-0.3, after the reaction is completed, the polycarboxylate surfactant containing tocopherol is obtained; The preparation method of the tetraphosphonic acid containing olefin intermediate is: A1, trans-1, 4-dichloro-2-butene is added to deionized water, sodium hydroxide is added thereto, the mixture is stirred and uniformly mixed, diethanolamine is then added thereto, the reaction is carried out at 40-50°C for 10-14 hours, after the reaction is completed, filtration is performed, rotary evaporation is carried out, and the intermediate 1 is obtained; A2, the intermediate 1 is added to deionized water, stirring and dispersion are performed, phosphorus pentoxide is then added thereto, the reaction is carried out at 75-85°C for 2-5 hours, after the reaction is completed, filtration is performed, rotary evaporation is carried out, and drying is performed, and the tetraphosphonic acid containing olefin intermediate is obtained; The preparation method of the tocopherol modified polyethylene glycol is: S1, DL-α-tocopherol, maleic anhydride, and triethylamine are added to a cyclohexane solvent, reflux reaction is carried out for 10-14 hours, after the reaction is completed, deionized water is added thereto, dichloromethane extraction is carried out, hydrochloric acid and deionized water are sequentially used for washing, drying is performed, rotary evaporation is carried out, and the carboxylated tocopherol is obtained; S2, the carboxylated tocopherol, polyethylene glycol, and p-toluenesulfonic acid are added to a cyclohexane solvent, reflux reaction is carried out for 6-10 hours, after the reaction is completed, saturated sodium bicarbonate solution is added thereto, ethyl acetate extraction is carried out, saturated sodium bicarbonate solution washing is carried out, drying is performed, and rotary evaporation is carried out, and the tocopherol modified polyethylene glycol is obtained.

2. The tocopheryl-containing polycarboxylate surfactant of claim 1, wherein, In the A1, the molar ratio of trans-1, 4-dichloro-2-butene, sodium hydroxide, and diethanolamine is 1:1.2-1.4:2-2.

4.

3. The tocopheryl-containing polycarboxylate surfactant of claim 1, wherein, In the A2, the molar ratio of the intermediate 1 and phosphorus pentoxide is 1:4.5-5.

4. The tocopheryl-containing polycarboxylate surfactant of claim 1, wherein, The molar ratio of the DL-α-tocopherol, maleic anhydride, and triethylamine is 1:1.5-2:1.6-2.

2.

5. The tocopheryl-containing polycarboxylate surfactant of claim 1, wherein, The molar ratio of the carboxylated tocopherol, polyethylene glycol, and p-toluenesulfonic acid is 1:1:1.2-1.

5.

6. The polycarboxylate surfactant containing tocopherol prepared by the preparation method of any one of claims 1-5 is applied to pesticides.

Images