High-adhesion polymer surfactant, preparation method thereof and pesticide preparation

Abstract

The invention relates to the field of high-molecular surfactants, in particular to a high-adhesion high-molecular surfactant as well as a preparation method and a pesticide preparation thereof. The polymer surfactant is a polymer, the polymer comprises a structural unit provided by a compound shown in a formula (1), a structural unit provided by a compound shown in a formula (2) and a structural unit provided by a compound shown in a formula (3), and each compound has specific group selection. The high-molecular surfactant has high adhesion, can effectively improve the utilization rate of a pesticide by adding a small amount of the high-molecular surfactant into the pesticide, and is wide in applicable pesticide range. Formula (1) # imgabs 0 # formula (2) # imgabs 1 # formula (3) # imgabs 2 #

Description

Technical Field

[0001] The present invention relates to the field of polymer surfactants, and particularly to a polymer surfactant with high adhesiveness, a preparation method thereof, and a pesticide formulation. Background Art

[0002] Pesticides play an indispensable role in crop production and have made great contributions to the improvement of agricultural yield and quality. However, during the application process of pesticides, droplet evaporation and drift inevitably occur, thereby reducing their effective utilization rate during the spatial transfer process.

[0003] When pesticides reach the target plants, due to the presence of structures such as a waxy layer, villi, papillae, stomata, and epidermal cells on the surface of most plant leaves, the leaves have a certain degree of hydrophobicity. During the interfacial transfer process of pesticide droplets, different degrees of bouncing, splashing, and fragmentation occur, making it difficult to achieve deposition. Most pesticides enter natural environments such as soil and rivers, posing a threat to the ecological environment and human health. Therefore, it is very important to improve the deposition of pesticides on the target, thereby effectively enhancing the utilization rate of pesticides.

[0004] Currently, scientific researchers have made many efforts in increasing the retention and deposition of pesticides on the leaf surface. Surfactants can rapidly diffuse from the bulk solution to the newly formed interface, effectively inhibiting the rebound of droplets on the solid surface and increasing the final effective deposition. Based on the characteristics of surfactants, adding surfactants to pesticide formulations has become one of the most effective ways to improve the performance of pesticides and increase their utilization rate.

[0005] In order to more effectively improve the utilization rate of pesticides, considering that the surface of plant leaves is mainly composed of higher fatty compounds such as alcohols, acids, and aldehydes, it is very urgent and crucial to develop a surfactant with an adhesion function for its characteristics. Summary of the Invention

[0006] The purpose of the present invention is to overcome the problems existing in the above-mentioned prior art, and provide a polymer surfactant with high adhesiveness, a preparation method thereof, and a pesticide formulation. This polymer surfactant has high adhesiveness. When a small amount is added to pesticides, it can effectively improve the utilization rate of pesticides, and it has a wide range of applicable pesticides.

[0007] To achieve the above purpose, on the one hand, the present invention provides a polymer surfactant. This polymer surfactant is a polymer, and the polymer includes structural units provided by the compound shown in formula (1), structural units provided by the compound shown in formula (2), and structural units provided by the compound shown in formula (3).

[0008] Formula (1) Formula (2) Formula (3)

[0009] Among them, R 1 is selected from one or more of carboxyl groups of C1-C12 and one or more of those in, Y is selected from one or more of H and alkyl groups of C1-C6, and q is an integer from 1 to 120; R 2 is selected from one or more of those in, R 4 is selected from one or more of a linking bond and alkylene groups of C1-C12, each R 5 is independently selected from one or more of H, alkyl groups of C1-C6, and hydroxyl groups, and at least two R 5 are hydroxyl groups; R 3 is selected from substituted or unsubstituted alkyl groups of C1-C20, wherein the substituents of the substituted alkyl groups of C1-C20 are selected from one or more of halogens; X is selected from --O-- or --NH--; D, E, and G are each independently selected from one or more of H and alkyl groups of C1-C6.

[0010] The second aspect of the present invention provides a method for preparing the above-mentioned polymer surfactant, which is characterized in that the method includes: polymerizing the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) to obtain a polymer surfactant.

[0011] The third aspect of the present invention provides a pesticide formulation containing the above-mentioned polymer surfactant.

[0012] In the present invention, by using the compounds shown in formula (1), formula (2), and formula (3) with specific structures as monomers for polymerization reaction, a polymer surfactant with high adhesiveness is obtained. The preparation of this polymer surfactant adopts one-step synthesis, its molecular weight can be precisely controlled, and the operation is simple, the yield is high, the cost is low, the reaction conditions are easy to control, and it is suitable for industrial development. The prepared polymer surfactant has excellent surface properties and adhesion properties, can effectively reduce surface activity, can effectively improve the retention rate of pesticides at the target interface by adding a small amount to pesticides, improve the utilization rate of pesticides, and has a wide range of applicable pesticides. Specific Embodiments

[0013] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values, they can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0014] In the present invention, the alkyl group in the expressions such as "C1-C20 alkyl", "C1-C12 carboxyl group", "C1-C12 alkylene group", etc. can be a straight-chain alkyl group or a branched-chain alkyl group. The same or similar expressions are the same.

[0015] In the present invention, the dashed line in the structures such as --O--, etc. represents a connecting bond.

[0016] On the one hand, the present invention provides a polymeric surfactant, which is a polymer. The polymer comprises structural units provided by the compound shown in formula (1), structural units provided by the compound shown in formula (2), and structural units provided by the compound shown in formula (3).

[0017] Formula (1) Formula (2) Formula (3)

[0018] Wherein, R 1 is selected from one or more of C1-C12 carboxyl groups and , Y is selected from one or more of H and C1-C6 alkyl groups, and q is an integer from 1 to 120; R 2 is selected from , R 4 is selected from one or more of a connecting bond and C1-C12 alkylene groups, each R 5 is independently selected from one or more of H, C1-C6 alkyl groups and hydroxyl groups, and at least two R 5 are hydroxyl groups; R 3 is selected from substituted or unsubstituted C1-C20 alkyl groups, wherein the substituents of the substituted C1-C20 alkyl groups are selected from one or more of halogens; X is selected from --O-- or --NH--; D, E, and G are each independently selected from one or more of H and C1-C6 alkyl groups.

[0019] According to the present invention, in order to obtain a polymeric surfactant with better surface properties and adhesion properties, the structures of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) can be further selected. Preferably, R 1 is selected from one or more of C1-C6 carboxyl groups and , Y is selected from one or more of H and C1-C3 alkyl groups, and q is an integer from 2 to 90; R 2 is selected from , R 4 is selected from one or more of a connecting bond and C1-C6 alkylene groups, each R 5Each independently selected from one or more of H, C1-C3 alkyl, and hydroxyl, and at least two Rs 5 are hydroxyl; R 3 is selected from substituted or unsubstituted C1-C12 alkyl, wherein the substituents of the substituted C1-C12 alkyl are selected from one or more of F, Cl, and Br; X is selected from --O-- or --NH--; D, E, and G each independently selected from one or more of H and C1-C3 alkyl.

[0020] More preferably, R 1 is selected from one or more of acetyl, n-propionyl, n-butyryl, and ; Y is selected from one or more of H, methyl, ethyl, and n-propyl; q is an integer from 2 to 90; R 2 is selected from ; R 4 is selected from one or more of a linking bond, methylene, ethylene, n-propylene, n-butylene, n-pentylene, and n-hexylene; each R 5 is independently selected from one or more of H, methyl, ethyl, n-propyl, isopropyl, and hydroxyl, and at least two Rs 5 are hydroxyl; R 3 is selected from one or more of methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, -CH2CH2CF2CF2CF2CF3, -CH2CF2CF2CF2CF2CF2CF3, -CH2CF2CF2CF2CF2CF2CHF2, -CH2CF2CHF2, -CH2CH2CF2CF2CF2CF2CF2CF3, -CH2CF2CF2CF2CHF2, -CH2CH2CF2CF3, -CH2CH2CCl2CF3, and -CH2CF2CF2CF2CF2CF2CHCl2; X is selected from --O-- or --NH--; D, E, and G each independently selected from one or more of H, methyl, ethyl, n-propyl, and isopropyl.

[0021] According to a preferred embodiment of the present invention, the compound represented by formula (1) is selected from one or more of the compounds represented by the following formulas:

[0022]

[0023]

[0024] According to a particularly preferred embodiment of the present invention, among them, the compound shown in formula (1) is selected from one or more of the compounds shown in formula (1-1), the compound shown in formula (1-2), the compound shown in formula (1-3), and the compound shown in formula (1-4).

[0025] According to a preferred embodiment of the present invention, among them, the compound shown in formula (2) is selected from one or more of the compounds shown in the following formula:

[0026]

[0027]

[0028] According to a particularly preferred embodiment of the present invention, among them, the compound shown in formula (2) is selected from one or more of the compounds shown in formula (2-1), the compound shown in formula (2-2), the compound shown in formula (2-3), the compound shown in formula (2-4), the compound shown in formula (2-7), the compound shown in formula (2-8), the compound shown in formula (2-9), and the compound shown in formula (2-10).

[0029] According to a preferred embodiment of the present invention, among them, the compound shown in formula (3) is selected from one or more of the compounds shown in the following formula:

[0030]

[0031] According to the present invention, in order to obtain a better polymer surfactant, the molar ratio of the structural units provided by each monomer can be adjusted. Preferably, the molar ratio of the structural units provided by the compound shown in formula (1), the structural units provided by the compound shown in formula (2), and the structural units provided by the compound shown in formula (3) is 1-25:1-25:1-25, preferably 1-20:1-20:1-20. For example, it can be numerical values such as 12:9:7, 8:6:10, 20:1:20, 1:20:1, and 15:10:1, and the ranges between any numerical values.

[0032] According to the present invention, in order to improve the performance of the polymer surfactant, preferably, the number-average molecular weight of the polymer surfactant is 1×10 3 -1.5×10 5 (g / mol), preferably 5×10 3 -1×10 5 (g / mol). For example, it can be 5×10 3 (g / mol), 6.5×10 3 (g / mol), 2.2×10 4 (g / mol), 5.2×10 4 (g / mol), 8.7×104 (g / mol) and 1×10 5 (g / mol).

[0033] According to the present invention, the polymeric surfactant of the present invention has good surface properties and can well reduce surface activity. Preferably, the critical micelle concentration of the polymeric surfactant is not more than 0.85 g / L, preferably 0.2 - 0.7 g / L, and for example, it can be values such as 0.2 g / L, 0.4 g / L, 0.5 g / L, 0.65 g / L, and 0.7 g / L and the ranges between any of these values.

[0034] Preferably, the surface tension of the polymeric surfactant is 10 - 50 mN / m, preferably 20 - 40 mN / m, and for example, it can be values such as 20 mN / m, 28 mN / m, 32 mN / m, and 40 mN / m and the ranges between any of these values.

[0035] The second aspect of the present invention provides a method for preparing the above polymeric surfactant, which is characterized in that the method includes: carrying out a polymerization reaction on the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) to obtain a polymeric surfactant.

[0036] According to the present invention, in order to obtain a polymeric surfactant with better surface properties and adhesion properties, the amounts of each monomer can be adjusted. Preferably, the molar ratio of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) is 1 - 25:1 - 25:1 - 25, preferably 1 - 20:1 - 20:1 - 20, and for example, it can be values such as 12:9:7, 8:6:10, 20:1:20, 1:20:1, and 15:10:1 and the ranges between any of these values.

[0037] According to the present invention, the solvent for the polymerization reaction and its amount can be selected within a relatively wide range. In order to provide a suitable and good reaction environment, preferably, the solvent for the polymerization reaction is selected from one or more of N,N - dimethylformamide, N,N - dimethylacetamide, tetrahydrofuran, 1,4 - dioxane, dimethyl sulfoxide, acetonitrile, 1,2 - dichloroethane, and N - methylpyrrolidone.

[0038] Preferably, relative to the total weight of 1 g of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3), the amount of the solvent for the polymerization reaction is 1 - 5 g, preferably 1.5 - 3 g, and for example, it can be values such as 1.5 g, 1.8 g, 2.2 g, 2.6 g, and 3 g and the ranges between any of these values.

[0039] According to the present invention, in order to enable the polymerization reaction to proceed smoothly, preferably, the polymerization reaction is carried out in the presence of an initiator. Among them, the initiator and its dosage can be selected within a relatively wide range. In order to improve the effect of the polymerization reaction, preferably, the initiator is selected from one or more of azo initiators and peroxide initiators, and preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl benzoyl peroxide, and methyl ethyl ketone peroxide.

[0040] Preferably, the dosage of the initiator is 0.05 - 15 wt% of the total amount of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3), preferably 1 - 10 wt%, for example, it can be values such as 1 wt%, 3 wt%, 5 wt%, 8 wt%, and 10 wt% and the ranges between any of these values.

[0041] According to the present invention, in order to enable the polymerization reaction to proceed better and obtain a polymer surfactant with more excellent performance, preferably, the conditions of the polymerization reaction include: the temperature is 40 - 120 °C, and the time is 5 - 60 h. More preferably, the conditions of the polymerization reaction include: the temperature is 50 - 100 °C (for example, it can be values such as 50 °C, 65 °C, 80 °C, 90 °C, and 100 °C and the ranges between any of these values), and the time is 12 - 48 h (for example, it can be values such as 12 h, 16 h, 24 h, 32 h, and 48 h and the ranges between any of these values).

[0042] According to the present invention, in order to avoid the generation of impurities and by-products, preferably, the polymerization reaction is carried out in an inert gas atmosphere. Among them, the inert gas can be, for example, nitrogen and / or argon.

[0043] According to the present invention, after the polymerization reaction is completed, the polymer surfactant can be obtained by removing the solvent.

[0044] The third aspect of the present invention provides a pesticide formulation containing the above polymer surfactant.

[0045] According to the present invention, the pesticides of the polymer surfactant of the present invention have a relatively wide range of applications. In order to achieve better effects, preferably, the pesticides in the pesticide formulation include one or more of kasugamycin, thiodiazole copper, diuron·thidiazuron, zhongshengmycin, mesotrione, bifenazate, thiabendazole, and prothioconazole.

[0046] According to the present invention, only a small amount of the polymeric surfactant of the present invention needs to be added to the pesticide to achieve very good effects. Preferably, the content of the polymeric surfactant in the pesticide formulation is 0.05-1.2 wt%, preferably 0.1-1 wt%, and for example, it can be values such as 0.1 wt%, 0.4 wt%, 0.7 wt%, and 1 wt% and the ranges between any of these values.

[0047] In the present invention, a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3) having specific structures are used as monomers for a polymerization reaction to obtain a highly adhesive polymeric surfactant. The preparation of this polymeric surfactant adopts a one-step synthesis, its molecular weight can be precisely controlled, the operation is simple, the yield is high, the cost is low, the reaction conditions are easy to control, and it is suitable for industrial development. The obtained polymeric surfactant has excellent surface properties and adhesion properties, its critical micelle concentration is not greater than 0.85 g / L, and the surface tension is 20-40 mN / m. Adding a small amount of the polymeric surfactant of the present invention to the pesticide can greatly improve the adhesion of the pesticide on the leaf surface (compared with the blank control group, it can be increased by 10-60%), thereby effectively increasing the retention rate of the pesticide at the target interface (up to 20-70%), improving the utilization rate of the pesticide, and it has a wide range of applicable pesticides.

[0048] The present invention will be described in detail below through examples.

[0049] In the following examples, the devices used are all conventional devices in the art, the operations adopted are all operations in the art, and the raw materials, reagents, etc. used can all be obtained through commercial purchase.

[0050] The method for measuring the number-average molecular weight of the polymeric surfactant is as follows: The sample is dissolved in chromatographic grade tetrahydrofuran, and measured by a gel permeation chromatograph (GPC) (Waters). The flow rate of the mobile phase (chromatographic grade tetrahydrofuran) is 1 mL / min, and polystyrene samples are used as the standard for molar mass calibration.

[0051] The method for measuring the critical micelle concentration of the polymeric surfactant is as follows: Referring to GB / T38722-2020, a full-automatic tensiometer is used to measure the static surface tension. Using the platinum ring method, the test is carried out at (25±1) °C. Each sample is tested at least 3 times, and the average value is calculated. Taking lgC as the abscissa and the static surface tension value γ as the ordinate, a lgC-γ curve is plotted. The CMC value is determined by linear fitting.

[0052] The method for measuring the surface tension of the polymeric surfactant is as follows: A series of polymeric surfactants with different concentrations are prepared, and the platinum ring method is used for surface tension measurement (outer diameter 20.30 mm, platinum wire 0.30 mm, perimeter 61.89 mm, density 0.998 g / cm 3 , temperature 25 ± 1 °C). The instrument is calibrated with pure water before and after the measurement.

[0053] Example 1

[0054] The compounds shown in formula (1-1) (q is 90), the compounds shown in formula (2-1), and the compounds shown in formula (3-1) are added in a molar ratio of 1:20:1 to N,N-dimethylformamide (the amount of N,N-dimethylformamide is 2 g relative to the total weight of 1 g of the compounds shown in formula (1-1), the compounds shown in formula (2-1), and the compounds shown in formula (3-1)). The temperature is raised to 80 °C, and dimethyl 2,2'-azobis(2-methylpropionate) (the amount used is 8 wt% of the total amount of the compounds shown in formula (1-1), the compounds shown in formula (2-1), and the compounds shown in formula (3-1)) is added, and the reaction is carried out for 20 h. After the reaction is completed, the solvent is removed to obtain the polymeric surfactant A1.

[0055] The number-average molecular weight of the polymeric surfactant A1 is 2.5×10 4 (g / mol), the critical micelle concentration is 0.37 g / L, and the corresponding surface tension is 31.1 mN / m.

[0056] Example 2

[0057] The compounds shown in formula (1-2) (q is 2), the compounds shown in formula (2-2), and the compounds shown in formula (3-2) are added in a molar ratio of 15:10:1 to tetrahydrofuran (the amount of tetrahydrofuran is 1.8 g relative to the total weight of 1 g of the compounds shown in formula (1-2), the compounds shown in formula (2-2), and the compounds shown in formula (3-2)). The temperature is raised to 65 °C, and azobisisobutyronitrile (the amount used is 5 wt% of the total amount of the compounds shown in formula (1-2), the compounds shown in formula (2-2), and the compounds shown in formula (3-2)) is added, and the reaction is carried out for 12 h. After the reaction is completed, the solvent is removed to obtain the polymeric surfactant A2.

[0058] The number-average molecular weight of the polymeric surfactant A2 is 1.5×10 4 (g / mol), the critical micelle concentration is 0.34 g / L, and the corresponding surface tension is 31.7 mN / m.

[0059] Example 3

[0060] The compound shown in formula (1-2) (q is 21), the compound shown in formula (2-3), and the compound shown in formula (3-6) were added in a molar ratio of 1:1:20 to 1,4-dioxane (the amount of 1,4-dioxane used was 2.2 g relative to the total weight of 1 g of the compound shown in formula (1-2), the compound shown in formula (2-3), and the compound shown in formula (3-6)). The temperature was raised to 90 °C, and azobisisobutyronitrile (the amount used was 2 wt% of the total amount of the compound shown in formula (1-2), the compound shown in formula (2-3), and the compound shown in formula (3-6)) was added, and the reaction was carried out for 24 h. After the reaction was completed, the solvent was removed to obtain the polymeric surfactant A3.

[0061] The number-average molecular weight of the polymeric surfactant A3 was 1.8×10 4 (g / mol), the critical micelle concentration was 0.36 g / L, and the corresponding surface tension was 32.5 mN / m.

[0062] Example 4

[0063] The compound shown in formula (1-3) (q is 2), the compound shown in formula (2-4), and the compound shown in formula (3-3) were added in a molar ratio of 1:12:15 to dimethyl sulfoxide (the amount of dimethyl sulfoxide used was 2.6 g relative to the total weight of 1 g of the compound shown in formula (1-3), the compound shown in formula (2-4), and the compound shown in formula (3-3)). The temperature was raised to 100 °C, and tert-butyl peroxybenzoate (the amount used was 10 wt% of the total amount of the compound shown in formula (1-3), the compound shown in formula (2-4), and the compound shown in formula (3-3)) was added, and the reaction was carried out for 36 h. After the reaction was completed, the solvent was removed to obtain the polymeric surfactant A4.

[0064] The number-average molecular weight of the polymeric surfactant A4 was 2.3×10 4 (g / mol), the critical micelle concentration was 0.35 g / L, and the corresponding surface tension was 32.1 mN / m.

[0065] Example 5

[0066] The compound shown in formula (1-4) (q is 9), the compound shown in formula (2-8), and the compound shown in formula (3-4) were added in a molar ratio of 20:20:1 to acetonitrile (the amount of acetonitrile used was 2.2 g relative to the total weight of 1 g of the compound shown in formula (1-4), the compound shown in formula (2-8), and the compound shown in formula (3-4)). The temperature was raised to 60 °C, and benzoyl peroxide (the amount used was 3 wt% of the total amount of the compound shown in formula (1-4), the compound shown in formula (2-8), and the compound shown in formula (3-4)) was added, and the reaction was carried out for 48 h. After the reaction was completed, the solvent was removed to obtain the polymeric surfactant A5.

[0067] The number-average molecular weight of the polymeric surfactant A5 is 2.2×10 4 (g / mol), the critical micelle concentration is 0.58 g / L, and the corresponding surface tension is 36.8 mN / m.

[0068] Example 6

[0069] The compound shown in formula (1-1) (q is 6), the compound shown in formula (2-7), and the compound shown in formula (3-5) were added in a molar ratio of 6:10:8 to N,N-dimethylacetamide (the amount of N,N-dimethylacetamide used was 1.6 g relative to the total weight of 1 g of the compound shown in formula (1-1), the compound shown in formula (2-7), and the compound shown in formula (3-5)). The temperature was raised to 85 °C, and methyl ethyl ketone peroxide (the amount used was 1 wt% of the total amount of the compound shown in formula (1-1), the compound shown in formula (2-7), and the compound shown in formula (3-5)) was added, and the reaction was carried out for 30 h. After the reaction was completed, the solvent was removed to obtain the polymeric surfactant A6.

[0070] The number-average molecular weight of the polymeric surfactant A6 is 2×10 4 (g / mol), the critical micelle concentration is 0.35 g / L, and the corresponding surface tension is 31.5 mN / m.

[0071] Example 7

[0072] According to the method of Example 1, except that the molar ratio of the compound shown in formula (1-1) (q is 6), the compound shown in formula (2-1), and the compound shown in formula (3-1) was 1:18:1, the reaction temperature was 60 °C, and the reaction time was 5 h, and finally the polymeric surfactant A7 was obtained.

[0073] The number-average molecular weight of the polymeric surfactant A7 is 4.2×10 3 (g / mol), the critical micelle concentration is 0.62 g / L, and the corresponding surface tension is 34.2 mN / m.

[0074] Example 8

[0075] According to the method of Example 1, except that the molar ratio of the compound shown in formula (1-1) (q is 90), the compound shown in formula (2-1), and the compound shown in formula (3-1) was 1:16:2, the reaction temperature was 110 °C, and the reaction time was 50 h, and finally the polymeric surfactant A8 was obtained.

[0076] The number-average molecular weight of the polymeric surfactant A8 is 1.4×10 5 (g / mol), the critical micelle concentration is 0.65 g / L, and the corresponding surface tension is 35.3 mN / m.

[0077] Example 9

[0078] According to the method of Example 1, the difference is that the molar ratio of the compound represented by formula (1-1) (q is 90), the compound represented by formula (2-1) and the compound represented by formula (3-1) is 1:24:1, and finally the polymer surfactant A9 is obtained.

[0079] The number average molecular weight of polymer surfactant A9 is 1.3×10 4 (g / mol), the critical micelle concentration is 0.54 g / L, and the corresponding surface tension is 39.1 mN / m.

[0080] Example 10

[0081] According to the method of Example 1, the difference is that the molar ratio of the compound represented by formula (1-1) (q is 90), the compound represented by formula (2-1) and the compound represented by formula (3-1) is 1:1:25, and finally the polymer surfactant A10 is obtained.

[0082] The number average molecular weight of polymer surfactant A10 is 1.7×10 4 (g / mol), the critical micelle concentration is 0.59 g / L, and the corresponding surface tension is 32.8 mN / m.

[0083] Comparative Example 1

[0084] The compound represented by formula (1-2) (q is 45), and the compound represented by formula (3-4) were added to acetonitrile (relative to 1g of the compound represented by formula (1-2), and the total weight of the compound represented by formula (3-4), the amount of acetonitrile is 5g), the temperature is raised to 60°C, and benzoyl peroxide (the amount is the compound represented by formula (1-2), and 3 wt% of the total amount of the compound represented by formula (3-4)), and react for 30 hours. After the reaction, the solvent is removed to obtain a polymer surfactant B1.

[0085] The number average molecular weight of polymer surfactant B1 is 7.7×10 4 (g / mol), the critical micelle concentration is 0.68g / L, and the corresponding surface tension is 40mN / m.

[0086] Comparative Example 2

[0087] According to the method of Example 1, the difference is that the compound represented by formula (2-1) is replaced by Finally, the high molecular surfactant B2 is obtained.

[0088] The number average molecular weight of polymer surfactant B2 is 1.3×104 (g / mol), the critical micelle concentration is 0.47 g / L, and the corresponding surface tension is 36 mN / m.

[0089] Test Example

[0090] The polymeric surfactants A1 - A10 prepared in Examples 1 - 10 and the polymeric surfactants B1, B2 prepared in Comparative Examples 1 - 2 were added to the pesticide formulation at different addition amounts, and the retention amount of the pesticide formulation on the target leaf surface was measured by high performance liquid chromatography. Additionally, a pesticide formulation without the addition of a polymeric surfactant was set as the blank control group. The calculation formula is: retention rate (%) = retention amount of the rinsed sample / retention amount of the unrinsed sample * 100%, and the retention amount increase rate (%) = retention rate of the sample with the added surfactant - retention rate of the sample without the added surfactant. The test results are shown in Table 1.

[0091] Table 1

[0092]

[0093]

[0094]

[0095]

[0096] It can be seen from Table 1 that in the test examples adopting the technical solution of the present invention, the retention of the pesticide on the target leaf surface is relatively high, which is superior to the test examples involving Comparative Examples 1 and 2.

[0097] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A polymeric surfactant, characterized in that, The polymeric surfactant is a polymer, and the polymer comprises structural units provided by the compound shown in formula (1), structural units provided by the compound shown in formula (2), and structural units provided by the compound shown in formula (3). Among them, R 1 is selected from one or more of carboxyl groups having 1 to 12 carbon atoms and ; Y is selected from one or more of H and alkyl groups having 1 to 6 carbon atoms; q is an integer from 1 to 120; R 2 is selected from ; R 4 is selected from one or more of a linking bond and alkylene groups having 1 to 12 carbon atoms; each R 5 is independently selected from one or more of H, alkyl groups having 1 to 6 carbon atoms, and hydroxyl groups, and at least two R 5 are hydroxyl groups; R 3 is selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, wherein the substituents of the substituted alkyl groups having 1 to 20 carbon atoms are selected from one or more of halogens; X is selected from --O-- or --NH--; D, E, and G are each independently selected from one or more of H and alkyl groups having 1 to 6 carbon atoms.

2. The polymeric surfactant according to claim 1, wherein, R 1 one or more selected from carboxyl groups having 1 to 6 carbon atoms and one or more of those in, Y is selected from one or more of H and alkyl groups having 1 to 3 carbon atoms, and q is an integer from 2 to 90; R 2 selected from one or more of those in, R 4 selected from one or more of a linking bond and alkylene groups having 1 to 6 carbon atoms, each R 5 is independently selected from one or more of H, alkyl groups having 1 to 3 carbon atoms, and hydroxyl groups, and at least two R 5 are hydroxyl groups; R 3 is selected from substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, wherein the substituents of the substituted alkyl groups having 1 to 12 carbon atoms are selected from one or more of F, Cl, and Br; X is selected from --O-- or --NH--; D, E, and G are each independently selected from one or more of H and alkyl groups having 1 to 3 carbon atoms; Preferably, R 1 is selected from one or more of an acetyl group, a n-propionyl group, a n-butyryl group, and ; Y is selected from one or more of H, a methyl group, an ethyl group, and a n-propyl group; q is an integer from 2 to 90; R 2 is selected from ; R 4 is selected from one or more of a linking bond, a methylene group, an ethylene group, a n-propylene group, a n-butylene group, a n-pentylene group, and a n-hexylene group; each R 5 is independently selected from one or more of H, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a hydroxyl group, and at least two R 5 are hydroxyl groups; R 3 is selected from one or more of a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, a n-dodecyl group, -CH2CH2CF2CF2CF2CF3, -CH2CF2CF2CF2CF2CF2CF3, -CH2CF2CF2CF2CF2CF2CHF2, -CH2CF2CHF2, -CH2CH2CF2CF2CF2CF2CF2CF3, -CH2CF2CF2CF2CHF2, -CH2CH2CF2CF3, -CH2CH2CCl2CF3, and -CH2CF2CF2CF2CF2CF2CHCl2; X is selected from --O-- or --NH--; D, E, and G are each independently selected from one or more of H, a methyl group, an ethyl group, a n-propyl group, and an isopropyl group.

3. The polymeric surfactant according to claim 1 or 2, wherein, The compound shown in formula (1) is selected from one or more of the compounds shown by the following formula: And / or, the compound shown in formula (2) is selected from one or more of the compounds shown by the following formula: And / or, the compound shown in formula (3) is selected from one or more of the compounds shown by the following formula:

4. The polymeric surfactant according to any one of claims 1 to 3, wherein, The molar ratio of the structural units provided by the compound shown in formula (1), the structural units provided by the compound shown in formula (2), and the structural units provided by the compound shown in formula (3) is 1 - 25:1 - 25:1 - 25, preferably 1 - 20:1 - 20:1 - 20; And / or, the number-average molecular weight of the polymeric surfactant is 1×10 3 -1.5×10 5 , preferably 5×10 3 -1×10 5 ; And / or, the critical micelle concentration of the polymeric surfactant is not greater than 0.85 g / L, preferably 0.2 - 0.7 g / L; And / or, the surface tension of the polymeric surfactant is 10 - 50 mN / m, preferably 20 - 40 mN / m.

5. The preparation method of the polymeric surfactant according to any one of claims 1-4, characterized in that, This method includes: polymerizing the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) to obtain a polymeric surfactant.

6. The method according to claim 5, wherein The molar ratio of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3) is 1 - 25:1 - 25:1 - 25, preferably 1 - 20:1 - 20:1 - 20; And / or, the solvent for the polymerization reaction is selected from one or more of N,N - dimethylformamide, N,N - dimethylacetamide, tetrahydrofuran, 1,4 - dioxane, dimethyl sulfoxide, acetonitrile, 1,2 - dichloroethane, and N - methylpyrrolidone; And / or, relative to the total weight of 1 g of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3), the amount of the solvent for the polymerization reaction is 1 - 5 g, preferably 1.5 - 3 g.

7. The method according to claim 5 or 6, wherein, The polymerization reaction is carried out in the presence of an initiator, and the initiator is selected from one or more of azo initiators and peroxide initiators, preferably one or more of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert - butyl benzoyl peroxide, and methyl ethyl ketone peroxide; Preferably, the amount of the initiator is 0.05 - 15 wt% of the total amount of the compound shown in formula (1), the compound shown in formula (2), and the compound shown in formula (3), preferably 1 - 10 wt%.

8. The method according to any one of claims 5-7, wherein The conditions for the polymerization reaction include: the temperature is 40 - 120 °C, and the time is 5 - 60 h; More preferably, the conditions for the polymerization reaction include: the temperature is 50 - 100 °C, and the time is 12 - 48 h.

9. A pesticide formulation comprising the polymeric surfactant according to any one of claims 1 - 4.

10. The pesticide formulation according to claim 9, wherein The pesticides in the pesticide formulation include one or more of kasugamycin, thiodiazole copper, diuron·thidiazuron, zhongshengmycin, mesotrione, bifenazate, thiabendazole, and prothioconazole; Preferably, the content of the polymeric surfactant in the pesticide formulation is 0.05 - 1.2 wt%, preferably 0.1 - 1 wt%.

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