A high molecular nonionic surfactant, its preparation method and application

Abstract

The present application relates to the technical field of surfactants, and provides a high-molecular nonionic surfactant, a preparation method and application thereof, wherein the high-molecular nonionic surfactant has a catechol group, shows strong adhesion, and the surface activity and adhesion can be regulated by adjusting the types and proportions of raw materials; the preparation method of the high-molecular nonionic surfactant is simple in operation, mild in conditions, high in yield, low in cost, easy to be industrialized, and can be applied to the preparation of herbicides, fungicides, acaricides and insecticides.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, and in particular to a polymeric nonionic surfactant, its preparation method, and its application. Background Technology

[0002] With rapid population growth, pesticides play an increasingly indispensable role in agricultural production. However, during spraying, pesticide droplets inevitably undergo evaporation and drift, reducing their utilization rate during spatial transport. When pesticides reach the target plants, the presence of polar groups on the surface of most plant leaves makes them somewhat hydrophobic. This causes pesticide droplets to bounce, splash, and break apart during interfacial transport, making deposition difficult. Much of the pesticide ends up in the soil and rivers, posing a threat to the ecological environment and human health. Therefore, improving pesticide deposition on the target plant, thereby effectively increasing pesticide utilization, is crucial.

[0003] Currently, researchers have made numerous efforts to increase pesticide retention and deposition on leaves. Because surfactants can rapidly diffuse from the bulk solution to newly formed interfaces, effectively inhibiting droplet bounce on solid surfaces and increasing the final effective deposition of droplets, adding surfactants to pesticide formulations is one of the most effective ways to improve pesticide performance and increase its utilization rate.

[0004] However, existing surfactants mainly focus on their surface activity, with limited research on their adhesion properties, especially the adhesion properties of nonionic surfactants. Therefore, there is an urgent need to develop nonionic surfactants with adhesion functions. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in related technologies. To this end, the present invention provides a polymeric nonionic surfactant with the following structural formula:

[0006]

[0007] Among them, R 1 Including H, Na or At least one of them, where q is an integer, 1 <q≤90;

[0008] R 2 include One of them;

[0009] R 3 for

[0010] D is either H or CH3;

[0011] E is either H or CH3;

[0012] G is either H or CH3;

[0013] Y is either H or CH3;

[0014] s is 1 or 2;

[0015] s′ is 1 or 2;

[0016] m, n, p, and p′ are integers greater than or equal to 1, and at least one of m, n, p, and p′ has a value of 1.

[0017] According to the present invention, a polymeric nonionic surfactant is provided, wherein... In this context, r is an integer, 2≤r≤6, L includes at least one of H or F; Z includes at least one of H or F.

[0018] According to the present invention, a polymeric nonionic surfactant has a number-average molecular weight of 1,000 to 100,000 g / mol, a critical micelle concentration of 0.001 to 1 g / L, and a surface tension of 20 to 40 mN / m.

[0019] The present invention also provides a synergist, comprising the polymeric nonionic surfactant as described above, wherein the synergist is used in the preparation of herbicides, fungicides, acaricides or insecticides.

[0020] This invention also provides a method for preparing a polymeric nonionic surfactant, comprising the following steps by weight:

[0021] 1 to 20 portions 1 to 20 servings 1 to 20 servings The mixture is placed in a solvent and stirred at 50–100°C to obtain a first mixed solution. An initiator is added dropwise to the first mixed solution, and the reaction is carried out under heat preservation to obtain a high molecular weight nonionic surfactant.

[0022] The solvent includes one of 1,2-dichloroethane, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane, or acetonitrile.

[0023] According to the present invention, a method for preparing a polymeric nonionic surfactant is provided, wherein the initiator includes one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, or methyl ethyl ketone peroxide.

[0024] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0025] 1. The present invention provides a polymeric nonionic surfactant that is based on... It is prepared by initiation with an initiator using raw materials, exhibiting strong adhesion ability. Furthermore, the surface activity and adhesion properties of the polymeric nonionic surfactant can be controlled by adjusting the type and ratio of raw materials.

[0026] 2. The catechol group in the structure of the high molecular weight nonionic surfactant provided by this invention forms hydrogen bonds with the polar groups on the surface of plant leaves, and interacts with each other, thereby reducing the varying degrees of bouncing, splashing and breaking of 15% nicosulfuron suspension on plant leaves. This increases the retention of 15% nicosulfuron suspension with the addition of high molecular weight nonionic surfactant on plant leaves, further enabling better absorption of pesticides by plant leaves. It also further prevents pesticides from entering the soil and rivers and other natural environments, thus avoiding threats to the ecological environment and human health. Moreover, the prepared high-adhesion high molecular weight nonionic surfactant is an environmentally friendly surfactant that will not damage plant leaves and is safe to use.

[0027] 3. The present invention provides a method for preparing a polymeric nonionic surfactant, which is a one-step synthesis method, simple to operate, with high yield, low cost, easy to control reaction conditions, and easy to develop for industrial application.

[0028] 4. The molecular weight of the polymeric nonionic surfactant provided by this invention can be precisely controlled, with a number average molecular weight of 1000-100000 g / mol, further regulating the performance of the polymeric nonionic surfactant and reducing the influence of molecular weight on the adhesion of the polymeric nonionic surfactant.

[0029] 5. The polymeric nonionic surfactant provided by this invention has excellent surface activity and a critical micelle concentration of 0.001 to 1 g / L.

[0030] 6. The polymeric nonionic surfactant provided by this invention has excellent ability to reduce plant surface activity, good wettability, and a minimum surface tension of 20-40 mN / m.

[0031] 7. The polymeric nonionic surfactant provided by this invention can be used to prepare herbicides, fungicides, acaricides, or insecticides. The prepared herbicides, fungicides, acaricides, or insecticides have better rain erosion resistance than the commercial adjuvant SK-44 and have good application prospects.

[0032] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention are described clearly and completely below. Obviously, the described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention. The following embodiments are used to illustrate this invention but cannot be used to limit the scope of this invention.

[0034] Furthermore, the terms “first,” “second,” and “third” are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0035] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0036] This invention provides a polymeric nonionic surfactant with the following structural formula:

[0037]

[0038] Among them, R 1 Including H, Na or At least one of them, where q is an integer, 1 <q≤90;

[0039] R 2 include One of them;

[0040] R 3 for

[0041] D is either H or CH3;

[0042] E is either H or CH3;

[0043] G is either H or CH3;

[0044] Y is either H or CH3;

[0045] s and s′ are 1 or 2;

[0046] m, n, p, and p′ are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0047] According to the present invention, a polymeric nonionic surfactant is provided, wherein... In this context, r is an integer, 2≤r≤6, L includes at least one of H or F; Z includes at least one of H or F.

[0048] According to the present invention, a polymeric nonionic surfactant has a number-average molecular weight of 1,000 to 100,000 g / mol, a critical micelle concentration of 0.001 to 1 g / L, and a minimum surface tension of 20 to 40 mN / m.

[0049] The present invention also provides a synergist, comprising the polymeric nonionic surfactant as described above, wherein the synergist is used in the preparation of herbicides, fungicides, acaricides or insecticides.

[0050] This invention also provides a method for preparing a polymeric nonionic surfactant, comprising the following steps by weight:

[0051] 1 to 20 portions 1 to 20 servings 1 to 20 servings The mixture is placed in a solvent and stirred at 50–100°C to obtain a first mixed solution. An initiator is added dropwise to the first mixed solution, and the reaction is carried out under heat preservation to obtain a high molecular weight nonionic surfactant.

[0052] The solvent includes one of 1,2-dichloroethane, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane, or acetonitrile.

[0053] The mass of the initiator is 1-10% of the total mass; furthermore, the heat treatment time is 6-48 hours.

[0054] The synthesis equation is shown below:

[0055]

[0056] According to the present invention, a method for preparing a polymeric nonionic surfactant is provided, wherein the initiator includes one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, or methyl ethyl ketone peroxide.

[0057] The following describes a polymeric nonionic surfactant, its preparation method, and its application according to Examples 1-22:

[0058] It needs to be explained that the method for determining the molecular weight of high molecular weight nonionic surfactants is as follows: the sample is dissolved in chromatographic grade tetrahydrofuran and measured by gel permeation chromatography (GPC) (Waters). The flow rate of the mobile phase (chromatographic grade tetrahydrofuran) is 1 mL / min, and the polystyrene sample is used as the standard for molar mass calibration.

[0059] Furthermore, the method for determining the surface tension of polymeric nonionic surfactants is as follows: A series of polymeric nonionic surfactants of different concentrations are prepared, and the surface tension is tested using a JK99M fully automatic static surface tension meter (outer diameter 20.30 mm, platinum wire 0.30 mm, circumference 61.89 mm, density 0.998 g / cm³) using the ring method. 3 (Temperature 25±1℃). The instrument was calibrated with pure water before and after the test.

[0060] The prepared polymeric nonionic surfactant was added as a synergist to herbicides, fungicides, acaricides, or insecticides, and then a simulated rain washout experiment was conducted. The specific operation steps are as follows: the target leaf was fixed on a glass slide with double-sided tape, and the prepared polymeric nonionic surfactant was dripped onto the target leaf. After the leaf surface dried, the leaf tilt angle was fixed at 30°, and the leaf surface was repeatedly washed with deionized water. After washing, the leaf surface was dried, and the leaf was removed and immersed in the test solvent. After simulating rain washout, the content of herbicide, fungicide, acaricide, or insecticide deposited on the target leaf surface was measured by high performance liquid chromatography.

[0061] Pesticide retention test method: Weigh 0.05 g (accurate to 0.0001 g) of the following standard samples into a 50 mL volumetric flask: 15% nicosulfuron suspension (herbicide), 30% glyphosate isopropylamine salt solution (herbicide), 41% glyphosate isopropylamine salt solution (herbicide), 200 g / L glufosinate-ammonium aqueous solution (herbicide), 50% butachlor EC (herbicide), 6% kasugamycin aqueous solution (fungicide), 25% pyraclostrobin suspension (fungicide), 20% thiamethoxam suspension (fungicide), 20% etoxazole suspension (acaricide), 34% spirodiclofen suspension (acaricide), 15% pyridaben EC (acaricide), and 5% abamectin EC (insecticide). Then, use ultrasonic vibration for 5 min to completely dissolve the standard sample, cool to room temperature, shake well, and filter to obtain a stock solution with a concentration of 1000 mg / L. The mother liquor was diluted to prepare standard solutions with concentrations of 50 mg / L, 100 mg / L, 200 mg / L, 300 mg / L, and 500 mg / L, respectively. The solutions were sonicated for 5 min to ensure homogeneity. The sample was dissolved in solvent, with an injection volume of 20 μL and a flow rate of 1.0 mL / min. The formulation in the sample was separated by high-performance liquid chromatography (HPLC), and quantified using the external standard method. The mass concentration of the sample was calculated using the following formula:

[0062]

[0063] In the formula, w1 is the mass fraction of the preparation in the standard solution; w2 is the mass fraction of the preparation in the sample solution; A1 is the peak area of ​​the standard solution; A2 is the peak area of ​​the sample solution; m1 is the mass of the standard; and m2 is the mass of the sample.

[0064] In Examples 1-11, the blank control experiment involved spraying barnyard grass with 15% nicosulfuron suspension without the addition of a high molecular weight nonionic surfactant, and the retention amount of nicosulfuron suspension on the barnyard grass leaves was used as the blank control.

[0065] The blank control experiments in Examples 12-22 involve adding the commercially available surfactant SK-44 as a synergist to herbicides, fungicides, acaricides, or insecticides to simulate rainwater runoff. The operation steps are exactly the same as those in the above experiments. The content of herbicides, fungicides, acaricides, or insecticides deposited on the target leaf surface is measured by high performance liquid chromatography.

[0066] Example 1

[0067] Will and The solvent N,N-dimethylformamide was dissolved in the solution at a mass ratio of 1:20:1, stirred and heated to 80°C, and 8% dimethyl azobisisobutyrate was added dropwise. After reacting at this temperature for 20 hours, the solvent N,N-dimethylformamide was removed to obtain the high molecular weight nonionic surfactant, designated C1. The synthesis equation is shown below:

[0068]

[0069] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0070] Tests showed that C1 has a number-average molecular weight of 50996 g / mol, a critical micelle concentration of 0.466 g / L, and a corresponding minimum surface tension of 32 mN / m. When C1 is added to 15% nicosulfuron suspension at a dosage of 2 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 25%.

[0071] Example 2

[0072] Will and The azobisisobutyronitrile (AIOBR) was dissolved in tetrahydrofuran at a mass ratio of 15:10:1, stirred and heated to 70°C, and 5% AIOBR was added dropwise. After reacting at this temperature for 6 hours, the solvent tetrahydrofuran was removed to obtain the high molecular weight nonionic surfactant, designated C2. The synthesis equation is shown below:

[0073]

[0074] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0075] Tests showed that C2 has a number-average molecular weight of 12800 g / mol, a critical micelle concentration of 0.01 g / L, and a corresponding minimum surface tension of 25 mN / m. When C2 is added to 15% nicosulfuron suspension at a dosage of 2 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 28%.

[0076] Example 3

[0077] Will and The solvent 1,4-dioxane was dissolved in 1,4-dioxane at a mass ratio of 1:1:20, stirred and heated to 50°C, and 2% azobisisobutyronitrile was added dropwise. After reacting at this temperature for 30 hours, the solvent 1,4-dioxane was removed to obtain the high molecular weight nonionic surfactant, designated C3. The synthesis equation is shown below:

[0078]

[0079] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0080] Tests showed that C3 has a number-average molecular weight of 100,000 g / mol, a critical micelle concentration of 0.001 g / L, and a corresponding minimum surface tension of 20 mN / m. When C3 is added to 15% nicosulfuron suspension at a dosage of 4 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 47%.

[0081] Example 4

[0082] Will and The solvent was dissolved in dimethyl sulfoxide at a mass ratio of 1:12:15, stirred and heated to 80°C, and 10% benzoyl tert-butyl peroxide was added dropwise. After reacting at this temperature for 48 hours, the solvent dimethyl sulfoxide was removed to obtain the high molecular weight nonionic surfactant, designated C4. The synthesis equation is shown below:

[0083]

[0084] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0085] Tests showed that C4 has a number-average molecular weight of 52670 g / mol, a critical micelle concentration of 0.139 g / L, and a corresponding minimum surface tension of 37 mN / m. When C4 is added to 15% nicosulfuron suspension at a dosage of 2 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 30%.

[0086] Example 5

[0087] Will and The benzoyl peroxide was dissolved in acetonitrile at a mass ratio of 20:20:1, stirred and heated to 60°C, and 3% benzoyl peroxide was added dropwise. After reacting at this temperature for 30 hours, the solvent acetonitrile was removed to obtain the high molecular weight nonionic surfactant, designated C5. The synthesis equation is shown below:

[0088]

[0089] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0090] Tests showed that C5 has a number-average molecular weight of 76,800 g / mol, a critical micelle concentration of 0.68 g / L, and a corresponding minimum surface tension of 40 mN / m. When C5 is added to 15% nicosulfuron suspension at a dosage of 3 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 40%.

[0091] Example 6

[0092] Will and The solvent N,N-dimethylformamide was dissolved in the solution at a mass ratio of 6:10:8, stirred and heated to 100°C, and 1% benzoyl tert-butyl peroxide was added dropwise. After reacting at this temperature for 15 hours, the solvent N,N-dimethylformamide was removed to obtain the high molecular weight nonionic surfactant, designated C6. The synthesis equation is shown below:

[0093]

[0094] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0095] Tests showed that C6 has a number-average molecular weight of 31590 g / mol, a critical micelle concentration of 0.092 g / L, and a corresponding minimum surface tension of 27 mN / m. When C6 is added to 15% nicosulfuron suspension at a dosage of 4 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 37%.

[0096] Example 7

[0097] Will and The azobisisobutyronitrile (AIOBR) was dissolved in dimethyl sulfoxide at a mass ratio of 20:1:20, stirred and heated to 75°C, and 7% AIOBR was added dropwise. After reacting at this temperature for 36 hours, the solvent dimethyl sulfoxide was removed to obtain the high molecular weight nonionic surfactant, designated C7. The synthesis equation is shown below:

[0098]

[0099] In the formula, m, n, and p are integers greater than or equal to 1, and at least one of m, n, and p has a value of 1.

[0100] Tests showed that C7 has a number-average molecular weight of 86,000 g / mol, a critical micelle concentration of 0.052 g / L, and a corresponding minimum surface tension of 23 mN / m. When C7 is added to 15% nicosulfuron suspension at a dosage of 1 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 5%.

[0101] Example 8

[0102] Will and A mixture of (mass ratio 2:1) was dissolved in tetrahydrofuran at a mass ratio of 8:6:10. The mixture was stirred and heated to 55°C, and 4% azobisisobutyronitrile was added dropwise. After reacting at this temperature for 10 hours, the solvent tetrahydrofuran was removed to obtain the high molecular weight nonionic surfactant, designated C8. The synthesis equation is shown below:

[0103]

[0104] In the formula, m, n, p, and p' are integers greater than or equal to 1, and at least one of m, n, p, and p' has a value of 1.

[0105] Tests showed that C8 has a number-average molecular weight of 57200 g / mol, a critical micelle concentration of 0.662 g / L, and a corresponding minimum surface tension of 24 mN / m. When C8 is added to 15% nicosulfuron suspension at a dosage of 2 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 33%.

[0106] Example 9

[0107] Will and (W:W ()=5:3), dissolved in N,N-dimethylformamide at a mass ratio of 12:9:7, stirred and heated to 90°C, 9% methyl ethyl ketone peroxide was added dropwise, and the reaction was maintained at this temperature for 17 hours. After removing the solvent N,N-dimethylformamide, the high molecular weight nonionic surfactant was obtained, designated C9. The synthesis equation is shown below:

[0108]

[0109] In the formula, m, n, p, and p' are integers greater than or equal to 1, and at least one of m, n, p, and p' has a value of 1.

[0110] Tests showed that C9 has a number-average molecular weight of 7500 g / mol, a critical micelle concentration of 0.834 g / L, and a corresponding minimum surface tension of 38 mN / m. When C9 is added to 15% nicosulfuron suspension at a dosage of 3 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 38%.

[0111] Example 10

[0112] Will and A mixture of W:W = 2:5 was dissolved in dimethyl sulfoxide at a mass ratio of 10:8:17. The mixture was stirred and heated to 85°C, and 3% benzoyl peroxide was added dropwise. After reacting at this temperature for 27 hours, the solvent dimethyl sulfoxide was removed to obtain a high molecular weight nonionic surfactant, designated C10. The synthesis equation is shown below:

[0113]

[0114] In the formula, m, n, p, and p' are integers greater than or equal to 1, and at least one of m, n, p, and p' has a value of 1.

[0115] Tests showed that C10 has a number-average molecular weight of 26,800 g / mol, a critical micelle concentration of 0.715 g / L, and a corresponding minimum surface tension of 38 mN / m. When C10 is added to 15% nicosulfuron suspension at a dosage of 3 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 29%.

[0116] Example 11

[0117] Will and A mixture of W:W = 3:2 was dissolved in 1,4-dioxane at a mass ratio of 7:16:11. The mixture was stirred and heated to 70°C, and 5% azobisisobutyronitrile was added dropwise. After reacting at this temperature for 20 hours, the solvent 1,4-dioxane was removed to obtain the high molecular weight nonionic surfactant, designated C11. The synthesis equation is shown below:

[0118]

[0119] In the formula, q≈11, m, n, p, and p' are integers greater than or equal to 1, and at least one of m, n, p, and p' takes the value 1.

[0120] Tests showed that C11 has a number-average molecular weight of 71520 g / mol, a critical micelle concentration of 1 g / L, and a corresponding minimum surface tension of 36 mN / m. When C11 is added to 15% nicosulfuron suspension at a dosage of 4 wt%, the retention of nicosulfuron suspension on barnyard grass leaves can be increased by 31%.

[0121] The performance of the polymeric nonionic surfactants prepared in Examples 1-11 is compared below according to Table 1:

[0122] Table 1 Comparison of the performance of polymer surface-active catalysts

[0123]

[0124] As shown in Table 1, the number-average molecular weights of the C1-C11 polymeric nonionic surfactants are in the range of 1000 to 100000 g / mol, indicating that the molecular weight of the polymeric nonionic surfactants prepared by the method of this invention can be precisely controlled. This allows for the preparation of polymeric nonionic surfactants with different molecular weights by controlling the reaction raw materials and reaction conditions according to actual needs, thereby regulating the performance of the polymeric nonionic surfactants and reducing the influence of molecular weight on the adhesiveness of the polymeric nonionic surfactants.

[0125] Furthermore, as shown in Table 1, the lower the critical micelle concentration, the better the activity of the surfactant. The critical micelle concentrations of the polymeric nonionic surfactants C1-C11 are 0.001-1 g / L, indicating that the prepared polymeric nonionic surfactants C1-C11 all have good activity.

[0126] Furthermore, as shown in Table 1, the lower the minimum surface tension, the better the wettability of the surfactant. The minimum surface tension of the polymeric nonionic surfactants C1-C11 is 20-40 mN / m, indicating that the prepared polymeric nonionic surfactants C1-C11 all have good wettability.

[0127] Furthermore, as shown in Table 1, the addition of high molecular weight nonionic surfactants C1-C11 to the 15% nicotinamide suspension increased the retention of nicotinamide suspension on barnyard grass leaves, indicating that the high molecular weight nonionic surfactants C1-C11 all exhibited strong adhesion. This is because the high adhesion is mainly due to the formation of hydrogen bonds between the catechol groups in the structure of the high molecular weight nonionic surfactants C1-C11 and the polar groups on the plant leaf surface, which reduces the varying degrees of bouncing, splashing, and breaking of the 15% nicotinamide suspension on the plant leaves. This allows the 15% nicotinamide suspension with added high molecular weight nonionic surfactants C1-C11 to have a greater retention on the plant leaves, further enabling better absorption of pesticides by the plant leaves and further preventing pesticides from entering the soil and rivers and other natural environments, thus avoiding threats to the ecological environment and human health. Moreover, the prepared high-adhesion high molecular weight nonionic surfactants C1-C11 are all environmentally friendly surfactants that will not damage plant leaves and are safe to use.

[0128] Furthermore, as shown in Table 1, the retention of 15% nicosulfuron suspension of polymeric nonionic surfactants C1-C11 on plant leaves varies depending on the amount added, indicating that the adhesion performance can be controlled according to the reaction raw materials, reaction conditions and the amount of polymeric nonionic surfactant added.

[0129] Example 12

[0130] The dosage of the tested herbicide, 41% glyphosate isopropylamine salt solution, was 350 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C1 was selected as a synergist. After simulating rainwater washing, the retention rate of glyphosate isopropylamine salt deposited on the target leaf surface was measured to be 20.15%.

[0131] Control experiment: The dosage of the tested herbicide 41% glyphosate isopropylamine salt solution was 350 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of glyphosate isopropylamine salt deposited on the target leaf surface after simulating rainwater washing was measured to be 15.45%.

[0132] Example 13

[0133] The dosage of the tested herbicide, 30% glyphosate isopropylamine salt solution, was 350 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C2 was selected as a synergist. After simulating rainwater washing, the retention rate of glyphosate isopropylamine salt deposited on the target leaf surface was measured to be 35.62%.

[0134] Control experiment: The dosage of the tested herbicide 30% glyphosate isopropylamine salt solution was 350 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist. After simulating rainwater runoff, the retention rate of glyphosate isopropylamine salt deposited on the target leaf surface was measured to be 16.78%.

[0135] Example 14

[0136] The dosage of the tested herbicide, 200 g / L glufosinate aqueous solution, was 200 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C3 was selected as a synergist, and the retention rate of glufosinate content deposited on the target leaf surface after simulating rainwater washing was 30.56%.

[0137] Control experiment: The dosage of the tested herbicide 200 g / L glufosinate aqueous solution was 200 g a.i / hm. 2 The dosage of 50% butachlor EC is 500 g a.i / hm. 2 Using commercially available SK-44 as a synergist, the retention rate of glufosinate deposited on the target leaf surface after simulated rainwater runoff was measured to be 10.22%.

[0138] Example 15

[0139] The application rate of the tested herbicide, 50% butachlor EC, was 500 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C4 was selected as a synergist, and the retention rate of butachlor content deposited on the target leaf surface after simulating rainwater washing was measured to be 36.78%.

[0140] Control experiment: The application rate of the tested herbicide 50% butachlor EC was 500 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of butachlor content deposited on the target leaf surface after simulated rainwater washing was 28.93%.

[0141] Example 16

[0142] The dosage of the tested fungicide, 6% kasugamycin aqueous solution, was 750 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C5 was selected as a synergist, and the retention rate of kasugamycin content deposited on the target leaf surface after simulating rainwater washing was 52.69%.

[0143] Control experiment: The dosage of the tested fungicide, 6% kasugamycin aqueous solution, was 750 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of kasugamycin deposited on the target leaf surface after simulating rainwater washing was 41.39%.

[0144] Example 17

[0145] The dosage of the tested fungicide, 25% pyraclostrobin suspension, was 100 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C6 was selected as a synergist. After simulating rainwater washing, the retention rate of pyraclostrobin content deposited on the target leaf surface was measured to be 43.51%.

[0146] Control experiment: The dosage of the tested fungicide, 25% pyraclostrobin suspension, was 100 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of pyraclostrobin content deposited on the target leaf surface after simulating rainwater washing was measured to be 26.71%.

[0147] Example 18

[0148] The dosage of the tested fungicide, 20% thiazole zinc suspension, was 300 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C7 was selected as a synergist, and the retention rate of thiazolium zinc content deposited on the target leaf surface after simulating rainwater washing was 69.15%.

[0149] Control experiment: The dosage of the tested fungicide 20% thiamethoxam zinc suspension was 300 g a.i / hm2, and commercial SK-44 was selected as a synergist. After simulating rain washing, the retention rate of thiamethoxam zinc content deposited on the target leaf surface was measured to be 52.14%.

[0150] Example 19

[0151] The dosage of the tested acaricide, 20% etoxazole suspension, was 400 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C8 was selected as a synergist, and the retention rate of etoxazole content deposited on the target leaf surface after simulating rainwater washing was 65.22%.

[0152] Control experiment: The dosage of the tested fungicide 20% etoxazole suspension was 50 g a.i / hm2, and commercial SK-44 was selected as a synergist. After simulating rain washing, the retention rate of etoxazole content deposited on the target leaf surface was measured to be 57.91%.

[0153] Example 20

[0154] The dosage of the tested acaricide, 34% spirodiclofen suspension, was 30 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C9 was selected as a synergist, and the retention rate of spirodiclofen deposited on the target leaf surface after simulating rainwater washing was 65.31%.

[0155] Control experiment: The dosage of the tested acaricide, 34% spirodiclofen suspension, was 30 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of spirodiclofen deposited on the target leaf surface after simulating rainwater washing was 50.73%.

[0156] Example 21

[0157] The dosage of the tested acaricide, 15% pyridaben emulsifiable concentrate, was 80 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C10 was selected as a synergist. After simulating rainwater washing, the retention rate of pyridaben content deposited on the target leaf surface was measured to be 64.83%.

[0158] Control experiment: The dosage of the tested acaricide, 15% pyridaben emulsifiable concentrate, was 80 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of pyridaben deposited on the target leaf surface after simulated rain washing was 51.45%.

[0159] Example 22

[0160] The dosage of the tested insecticide, 5% abamectin EC, was 40 g a.i / hm. 2 The high-adhesion polymeric nonionic surfactant C11 was selected as a synergist, and the retention rate of abamectin content deposited on the target leaf surface after simulating rainwater washing was measured to be 75.23%.

[0161] Control experiment: The dosage of the tested insecticide, 5% abamectin EC, was 40 g a.i / hm. 2 Commercially available SK-44 was selected as an synergist, and the retention rate of abamectin deposited on the target leaf surface after simulating rainwater washing was measured to be 61.41%.

[0162] As shown in Examples 12-22, the polymeric nonionic surfactant provided by the present invention is used to prepare herbicides, fungicides, acaricides, or insecticides. The comparison of its rain erosion resistance with that of the existing commercial SK-44 synergist is shown in Table 2.

[0163] Table 2 Comparison of Rainwater Erosion Resistance

[0164]

[0165] As shown in Table 2, the prepared polymeric nonionic surfactants C1-C11 were applied to the preparation of herbicides, fungicides, acaricides, or insecticides, and simulated rainwater flushing experiments were conducted. The retention rates of the surfactants deposited on the target leaf surfaces were all higher than those of the existing commercial SK-44 synergist. This indicates that the prepared polymeric nonionic surfactants have excellent capabilities, good wetting and adhesion abilities, and have great application prospects.

[0166] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A synergist, characterized in that, The following are methods for preparing polymeric nonionic surfactants: The preparation method of polymeric nonionic surfactants, by mass parts, includes the following steps: 1-20 portions 1 to 20 servings 1 to 20 servings The mixture is placed in a solvent and stirred at 50~100℃ to obtain a first mixed solution. An initiator is added dropwise to the first mixed solution, and the reaction is carried out under heat preservation to obtain a high molecular weight nonionic surfactant. Choose one of the following structural formulas: 、 、 、 、 、 、 、 、 、 、 ； Choose one of the following structural formulas: 、 、 ； Choose one of the following structural formulas: 、 、 、 、 、 ； or Selected from one of the following mixtures: and A mixture, and A mixture, and A mixture, and A mixture; The solvent includes one of 1,2-dichloroethane, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane, or acetonitrile; The synergist is used in the preparation of herbicides, fungicides, acaricides, or insecticides.

2. The synergist according to claim 1, characterized in that, The number-average molecular weight of the high molecular weight nonionic surfactant is 1000~100000 g / mol; Its critical micelle concentration is 0.001~1 g / L; Its surface tension is 20 ~ 40 mN / m.

3. The synergist according to claim 1, characterized in that, The initiator includes one of azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, benzoyl peroxide, tert-butyl peroxide, or methyl ethyl ketone peroxide.

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