Fluorine-containing nonionic triarm surfactant and method for preparing the same

Abstract

This invention relates to the field of fluorinated surfactant technology, and provides a fluorinated nonionic three-armed surfactant and its preparation method. The fluorinated nonionic three-armed surfactant has the following structural formula and is prepared using an intermediate composed of polyethylene glycol and fluorinated alcohol as raw materials. It has a high degradation rate in the environment, low toxicity, and is environmentally friendly. Moreover, the synthesis route is short, the reaction conditions are easy to control, which is conducive to industrial development. The preparation cost is low, and it can also effectively reduce surface activity. It has good spreadability and wettability and can be used as an additive in pesticide formulations for large-scale promotion and application.

Description

Technical Field

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

[0002] Fluorinated surfactants are hydrocarbon surfactants in which all or part of the hydrogen atoms in the hydrocarbon chain are replaced by fluorine atoms, forming a class of surfactants with a hydrophobic group consisting of a fluorocarbon chain. They are an important class of specialty surfactants. Based on the polarity of the hydrophilic group, they can be divided into ionic and nonionic fluorinated surfactants. Compared to ionic fluorinated surfactants, nonionic fluorinated surfactants have unique properties, such as not ionizing in water, being insensitive to changes in pH and the presence of electrolytes, and being soluble in acidic and alkaline solutions.

[0003] Thanks to the unique structure of fluorocarbon bonds, fluorinated surfactants possess properties unmatched by conventional surfactants: high surface activity, high chemical stability, high thermal stability, and the hydrophobic and oleophobic nature of fluorocarbon chains. However, fluorinated compounds with long fluorocarbon chains (8 or more carbon atoms bonded to fluorine) are difficult to degrade in the environment and exhibit bioaccumulation, accumulating in organisms along the food chain and posing a threat to human health. For example, perfluorooctane sulfonate (PFOS) has a "half-expelled time" of up to 8.7 years in the human body, causing not only respiratory damage but also potentially neonatal death. Therefore, the development of high-performance and environmentally friendly fluorinated nonionic surfactants is of paramount importance.

[0004] Three-armed surfactants consist of three hydrophobic chains and three hydrophilic groups, covalently linked by connecting bridges. Compared to traditional surfactants (whose minimum surface tension is only around 30 mN / m), three-armed surfactants exhibit lower critical micelle concentrations (CMC), lower Krafft concentrations, unique rheological properties, and good wettability. Currently, only the synthesis of ionic three-armed surfactants has been reported, but ionic surfactants are significantly affected by pH. Research on nonionic three-armed surfactants is relatively limited, especially fluorinated short-chain nonionic three-armed surfactants, which have not yet been reported.

[0005] Therefore, the development of environmentally friendly fluorinated nonionic three-arm surfactants is of great significance. Summary of the Invention

[0006] The present invention aims to at least solve one of the technical problems existing in the related art. To this end, the present invention provides a fluorinated nonionic three-arm surfactant, the structure of which is shown in Formula 1:

[0007]

[0008] Formula 1

[0009] Wherein, R includes , or One of them;

[0010] m, n and p are all integers, 1≤m≤90, 1≤n≤90, 1≤p≤90;

[0011] R1 f R2 f and R3 f For a chain segment, the structural formula is: .

[0012] According to the present invention, a fluorinated nonionic three-arm surfactant has the following structural formula: In this context, q is an integer, 2≤q≤6; Z represents H or F.

[0013] According to the present invention, a fluorinated nonionic three-armed surfactant has a critical micelle concentration of 0.1 g / L to 2.3 g / L and a surface tension of 18 mN / m to 26 mN / m.

[0014] This invention also provides a method for preparing a fluorinated nonionic three-arm surfactant, comprising the following steps:

[0015] S1: Will , and The mixture is placed in a solvent and stirred to obtain a first mixed solution, wherein the solvent is selected from one of tetrahydrofuran, dioxane, dichloroethane, toluene, or dichloromethane;

[0016] S2: Add a first organic compound to the first mixed solution and stir at 20~110°C to obtain a fluorinated nonionic three-arm surfactant; wherein the first organic compound is selected from one of triphenylmethane triisocyanate, L-lysine triisocyanate, or a mixture of N,N'-carbonyldiimidazole and tri(2-aminoethyl)amine.

[0017] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with triphenylmethane triisocyanate is 1:0.3 to 1:0.9; The molar ratio with triphenylmethane triisocyanate is 1:0.3 to 1:0.9; The molar ratio of the triphenylmethane triisocyanate to triphenylmethane triisocyanate is 1:0.3 to 1:0.9.

[0018] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9.

[0019] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio of N,N'-carbonyldiimidazole is 1:1 to 1:1.5.

[0020] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9.

[0021] The above-described one or more technical solutions in the embodiments of the present invention have at least one of the following technical effects:

[0022] 1. This invention provides a fluorinated nonionic three-arm surfactant, prepared from an intermediate composed of polyethylene glycol and fluoroalcohol, which has a high degradation rate in the environment, with a degradation rate of 80% to 99% after 28 days, and is environmentally friendly.

[0023] 2. This invention provides a fluorinated nonionic three-armed surfactant with low toxicity, showing low toxicity in acute toxicity tests on zebrafish, and with a short synthetic route and simple operation.

[0024] 3. This invention provides a fluorinated nonionic three-arm surfactant with a critical micelle concentration of 0.1 g / L to 2.3 g / L, which can effectively reduce surface tension by 18 mN / m to 26 mN / m, and further effectively reduce surface activity. Therefore, it exhibits excellent performance when used on superhydrophobic surfaces, with good spreadability and wettability, and can significantly inhibit the evaporation of water on superhydrophobic surfaces. It can also significantly inhibit the bouncing and splashing of droplets on superhydrophobic surfaces. It can be used as an additive in pesticide formulations, not only enhancing the efficacy of pesticides, but also being environmentally friendly and easily degradable, and can be widely promoted and used in agricultural applications.

[0025] 4. This invention provides a method for preparing a fluorinated nonionic three-arm surfactant. The surface activity performance can be controlled by adjusting the types and proportions of raw materials. The reaction conditions are easy to control, which is conducive to industrial development and has low preparation cost.

[0026] 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. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in this invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0028] Figure 1 This is an experimental diagram showing the spreading of a fluorinated nonionic three-armed surfactant C2, C6 and C7 on the surface of cabbage leaves, provided by the present invention.

[0029] Figure 2 This is an experimental diagram showing the spreading of a fluorinated nonionic three-armed surfactant C1 and C2 on a paraffin film surface, provided by the present invention. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below with reference to the accompanying drawings. 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 should not be used to limit the scope of this invention.

[0031] Furthermore, the terms “first,” “second,” and “third” are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0032] 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.

[0033] This invention provides a fluorinated nonionic three-arm surfactant, the structure of which is shown in Formula 1:

[0034]

[0035] Formula 1

[0036] Wherein, R includes , or One of them;

[0037] m, n and p are all integers, 1≤m≤90, 1≤n≤90, 1≤p≤90;

[0038] R1 f R2 f and R3 f For a chain segment, the structural formula is: .

[0039] According to the present invention, a fluorinated nonionic three-arm surfactant has the following structural formula: In this context, q is an integer, 2≤q≤6; Z represents H or F.

[0040] According to the present invention, a fluorinated nonionic three-armed surfactant has a critical micelle concentration of 0.1 g / L to 2.3 g / L and a surface tension of 18 mN / m to 26 mN / m.

[0041] This invention also provides a method for preparing a fluorinated nonionic three-arm surfactant, comprising the following steps:

[0042] S1: Will , and The mixture is placed in a solvent and stirred to obtain a first mixed solution, wherein the solvent is selected from one of tetrahydrofuran, dioxane, dichloroethane, toluene, or dichloromethane;

[0043] S2: Add a first organic compound to the first mixed solution and stir at 20~110°C to obtain a fluorinated nonionic three-arm surfactant; wherein the first organic compound is selected from one of triphenylmethane triisocyanate, L-lysine triisocyanate, or a mixture of N,N'-carbonyldiimidazole and tri(2-aminoethyl)amine.

[0044] In this process, a first organic compound is added to the first mixed solution, and the mixture is stirred at 20~110 °C for 3~24 h to obtain a fluorinated nonionic three-armed surfactant.

[0045] What needs to be explained is that , and The preparation method is referenced in Chinese Patent CN114276537A. , and It is an intermediate composed of polyethylene glycol and fluoroalcohol. Both polyethylene glycol and fluoroalcohol are environmentally friendly organic compounds that are easily degraded.

[0046] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with triphenylmethane triisocyanate is 1:0.3 to 1:0.9; The molar ratio with triphenylmethane triisocyanate is 1:0.3 to 1:0.9; The molar ratio of the triphenylmethane triisocyanate to triphenylmethane triisocyanate is 1:0.3 to 1:0.9.

[0047] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9.

[0048] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio of N,N'-carbonyldiimidazole is 1:1 to 1:1.5.

[0049] According to the present invention, a method for preparing a fluorinated nonionic three-arm surfactant is provided. The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9.

[0050] The following describes a fluorinated nonionic three-arm surfactant and its preparation method provided by the present invention with reference to Examples 1-20:

[0051] It should be further explained that in Examples 1-20, the surface tension of the fluorinated nonionic three-arm surfactant provided by the present invention was tested using a JK99M fully automatic static surface tension meter via the ring method (outer diameter 20.30 mm, platinum wire 0.30 mm, circumference 61.89 mm, density 0.998 g / cm³). 3 (Temperature 25±1 ℃). The instrument was calibrated with pure water before and after the test.

[0052] Furthermore, the present invention provides a method for determining the degradation rate of a fluorinated nonionic three-armed surfactant, as specified in the standard "Chemicals: Rapid Biodegradability Test by Respirometric Method (GB / T 21801-2008)". Using the respirometric method, an appropriate amount of the fluorinated nonionic three-armed surfactant provided by the present invention is added as the sole organic carbon source to a certain volume of inoculated inorganic culture medium. The sealed bottle is continuously stirred at a constant temperature for 28 days, and the oxygen consumption is measured to determine the degradation rate of the sample.

[0053] Furthermore, the present invention provides a method for determining the toxicity of a fluorinated nonionic three-armed surfactant to aquatic organisms: 《Method for Determination of Acute Toxicity of Aquatic Substances to Freshwater Fish (Zebrafish) (GB / T 13267-1991)》. Under defined experimental conditions, zebrafish were used as the test organisms to determine the concentration of the fluorinated nonionic three-armed surfactant that caused 50% mortality in the tested zebrafish population after 96 hours of application. Based on the LC50 value at the lethal concentration, the toxicity level of the samples to fish was classified into four levels, as shown in Table 1:

[0054] Table 1. Classification of the toxicity level of samples to fish

[0055]

[0056] Example 1:

[0057] Let n=1, q=2, and Z be intermediates of H. p=1, q=2, Z is an intermediate of H. m=1, q=3, Z is an intermediate of H. The solution was dissolved in dichloroethane to obtain a mixed solution, which was then dried to remove moisture. Triphenylmethane triisocyanate was then added to the mixed solution at a molar ratio of 1:0.3 (three intermediates to triphenylmethane triisocyanate). The mixture was stirred and reacted at 80°C for 18 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C1.

[0058] The critical micelle concentration of C1, as tested using the above method, was 2.3 g / L, corresponding to a surface tension of 26 mN / m. The degradation rate after 28 days was 99%, and the acute toxicity test results for zebrafish were all low.

[0059] Example 2:

[0060] With n=22, q=4, and Z as an intermediate of H. p=44, q=2, Z is an intermediate of F. m=90, q=3, Z is an intermediate of H. The solution was dissolved in tetrahydrofuran to obtain a mixed solution, which was then dried to remove moisture. Triphenylmethane triisocyanate was then added to the mixed solution at a molar ratio of 1:0.4 (three intermediates to triphenylmethane triisocyanate). The mixture was stirred and reacted at 65°C for 19 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C2.

[0061] The critical micelle concentration of C2, as tested using the above method, was 1.98 g / L, corresponding to a surface tension of 25.2 mN / m. The degradation rate after 28 days was 92%, and the acute toxicity test results for zebrafish were all low toxicity.

[0062] Example 3:

[0063] With n=90, q=6, and Z as an intermediate of F. p=22, q=5, Z is an intermediate of H. m=44, q=3, Z is an intermediate of F. Dissolved in dioxane, a mixed solution was obtained. The solution was dried to remove moisture. Then, triphenylmethane triisocyanate was added to the mixed solution at a molar ratio of 1:0.9 (three intermediates to triphenylmethane triisocyanate). The mixture was stirred and reacted at 95°C for 20 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C3.

[0064] The critical micelle concentration of C3, as tested using the above method, was 0.65 g / L, corresponding to a surface tension of 20.2 mN / m. The degradation rate after 28 days was 91%, and the acute toxicity test results for zebrafish were all low toxicity.

[0065] Example 4:

[0066] With n=44, q=5, and Z as an intermediate of H. p=90, q=3, Z is an intermediate of H. m=66, q=2, Z is an intermediate of H. Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, triphenylmethane triisocyanate was added to the mixed solution at a molar ratio of 1:0.3 (three intermediates to triphenylmethane triisocyanate), and the mixture was stirred and reacted at 80°C for 24 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C4.

[0067] The critical micelle concentration of C4, as determined by the above methods, was 0.21 g / L, corresponding to a surface tension of 18.6 mN / m. The degradation rate after 28 days was 80%, and the acute toxicity test results for zebrafish showed low toxicity.

[0068] Example 5:

[0069] With n=11, q=2, and Z as an intermediate of F. p=11, q=2, Z is an intermediate of F. m=11, q=2, Z is an intermediate of F. The solution was dissolved in dichloromethane to obtain a mixed solution, which was then dried to remove moisture. Triphenylmethane triisocyanate was then added to the mixed solution at a molar ratio of 1:0.8 (three intermediates to triphenylmethane triisocyanate). The mixture was stirred and reacted at 39°C for 22 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C5.

[0070] The critical micelle concentration of C5, as determined by the above methods, was 0.76 g / L, corresponding to a surface tension of 23 mN / m. The degradation rate after 28 days was 94%, and the acute toxicity test results for zebrafish were all low.

[0071] Example 6:

[0072] With n=11, q=3, and Z as an intermediate of F. p=11, q=3, Z is an intermediate of F. m=11, q=3, Z is an intermediate of F Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, triphenylmethane triisocyanate was added to the mixed solution at a molar ratio of 1:0.7 (three intermediates to triphenylmethane triisocyanate), and the mixture was stirred and reacted at 110°C for 20 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C6.

[0073] The critical micelle concentration of C6, as determined by the above methods, was 0.21 g / L, corresponding to a surface tension of 26 mN / m. The degradation rate after 28 days was 94%, and the acute toxicity test results for zebrafish were all low.

[0074] Example 7:

[0075] Let n=1, q=2, and Z be intermediates of H. p=1, q=2, Z is an intermediate of H. m=1, q=3, Z is an intermediate of H. The solution was dissolved in dichloroethane to obtain a mixed solution, which was then dried to remove moisture. L-lysine triisocyanate was then added to the mixed solution at a molar ratio of 1:0.3 (three intermediates to L-lysine triisocyanate). The mixture was stirred and reacted at 80°C for 18 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C7.

[0076] The critical micelle concentration of C7, as determined by the above methods, was 2.11 g / L, corresponding to a surface tension of 25.9 mN / m. The degradation rate after 28 days was 95%, and the acute toxicity test results for zebrafish were all low.

[0077] Example 8:

[0078] With n=22, q=4, and Z as an intermediate of H. p=44, q=2, Z is an intermediate of F. m=90, q=3, Z is an intermediate of H. The intermediate was dissolved in tetrahydrofuran to obtain a mixed solution, which was then dried to remove moisture. L-lysine triisocyanate was then added to the mixed solution at a molar ratio of 1:0.44 (intermediate to L-lysine triisocyanate). The mixture was stirred and reacted at 70°C for 16 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C8.

[0079] The critical micelle concentration of C8, as determined by the above methods, was 1.76 g / L, corresponding to a surface tension of 24.6 mN / m. The degradation rate after 28 days was 89%, and the acute toxicity test results for zebrafish were all low.

[0080] Example 9:

[0081] With n=90, q=6, and Z as an intermediate of F. p=22, q=5, Z is an intermediate of H. m=44, q=3, Z is an intermediate of F. Dissolved in dioxane to obtain a mixed solution, the solution was dried to remove moisture. Then, L-lysine triisocyanate was added to the mixed solution at a molar ratio of 1:0.8 (three intermediates to L-lysine triisocyanate). The mixture was stirred and reacted at 100°C for 18 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C9.

[0082] The critical micelle concentration of C9, as determined by the above methods, was 0.78 g / L, corresponding to a surface tension of 19.8 mN / m. The degradation rate after 28 days was 88%, and the acute toxicity test results for zebrafish were all low.

[0083] Example 10:

[0084] With n=44, q=5, and Z as an intermediate of H. p=90, q=3, Z is an intermediate of H. m=66, q=2, Z is an intermediate of H. Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, L-lysine triisocyanate was added to the mixed solution at a molar ratio of 1:0.9 (three intermediates to L-lysine triisocyanate). The mixture was stirred and reacted at 105°C for 21 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C10.

[0085] The critical micelle concentration of C10, as tested using the above method, was 0.43 g / L, corresponding to a surface tension of 19.7 mN / m. The degradation rate after 28 days was 95%, and the acute toxicity test results for zebrafish were all low.

[0086] Example 11:

[0087] With n=11, q=2, and Z as an intermediate of F. p=11, q=2, Z is an intermediate of F. m=11, q=2, Z is an intermediate of F. Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, L-lysine triisocyanate was added to the mixed solution at a molar ratio of 1:0.6 (three intermediates to L-lysine triisocyanate). The mixture was stirred and reacted at 110°C for 22 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C11.

[0088] The critical micelle concentration of C11, as tested using the above method, was 0.47 g / L, corresponding to a surface tension of 19.7 mN / m. The degradation rate after 28 days was 97%, and the acute toxicity test results for zebrafish were all low.

[0089] Example 12:

[0090] With n=11, q=3, and Z as an intermediate of F. p=11, q=3, Z is an intermediate of F. m=11, q=3, Z is an intermediate of F Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, L-lysine triisocyanate was added to the mixed solution at a molar ratio of 1:0.5 (three intermediates to L-lysine triisocyanate). The mixture was stirred and reacted at 109°C for 18 h to obtain a fluorinated nonionic three-armed surfactant. It is labeled C12.

[0091] The critical micelle concentration of C12, as tested using the above method, was 0.12 g / L, corresponding to a surface tension of 18 mN / m. The degradation rate after 28 days was 99%, and the acute toxicity test results for zebrafish were all low.

[0092] Example 13:

[0093] Let n=1, q=2, and Z be intermediates of H. p=1, q=2, Z is an intermediate of H. m=1, q=3, Z is an intermediate of H. Dissolve the intermediates in dichloroethane to obtain a mixed solution, dry to remove moisture, and then add a mixture of N,N'-carbonyldiimidazole and tris(2-aminoethyl)amine in a molar ratio of 1:1.3 and 1:0.3, respectively. Stir and react at 25°C for 3 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C13.

[0094] The critical micelle concentration of C13, as tested using the above method, was 1.48 g / L, corresponding to a surface tension of 24.7 mN / m. The degradation rate after 28 days was 98%, and the acute toxicity test results for zebrafish were all low.

[0095] Example 14:

[0096] With n=22, q=4, and Z as an intermediate of H. p=44, q=2, Z is an intermediate of F. m=90, q=3, Z is an intermediate of H. Dissolve the intermediates in tetrahydrofuran to obtain a mixed solution, dry to remove moisture, and then add a mixture of N,N'-carbonyldiimidazole and tris(2-aminoethyl)amine in a molar ratio of 1:1 and 1:0.9, respectively. Stir and react at 25°C for 5 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C14.

[0097] The critical micelle concentration of C14, as tested using the above method, was 1.39 g / L, corresponding to a surface tension of 22.8 mN / m. The degradation rate after 28 days was 96%, and the acute toxicity test results for zebrafish were all low toxicity.

[0098] Example 15:

[0099] With n=90, q=6, and Z as an intermediate of F. p=22, q=5, Z is an intermediate of H. m=44, q=3, Z is an intermediate of F. Dissolved in dioxane, a mixed solution was obtained. The solution was dried to remove moisture. Then, a mixture of the three intermediates and N,N'-carbonyldiimidazole in molar ratio of 1:1.5, and the three intermediates and tris(2-aminoethyl)amine in molar ratio of 1:0.7, was added to the above mixed solution. The mixture was stirred and reacted at 25°C for 8 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C15.

[0100] The critical micelle concentration of C15, as tested using the above method, was 0.55 g / L, corresponding to a surface tension of 19.4 mN / m. The degradation rate after 28 days was 90%, and the acute toxicity test results for zebrafish were all low toxicity.

[0101] Example 16:

[0102] With n=44, q=5, and Z as an intermediate of H. p=90, q=3, Z is an intermediate of H. m=66, q=2, Z is an intermediate of H. Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, a mixture of the three intermediates and N,N'-carbonyldiimidazole in molar ratio of 1:1.2, and the three intermediates and tris(2-aminoethyl)amine in molar ratio of 1:0.6, was added to the above mixed solution. The mixture was stirred and reacted at 25°C for 8 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C16.

[0103] The critical micelle concentration of C16, as determined by the above methods, was 0.10 g / L, corresponding to a surface tension of 18 mN / m. The degradation rate after 28 days was 92%, and the acute toxicity test results for zebrafish were all low.

[0104] Example 17:

[0105] With n=4, q=2, and Z as an intermediate of F. p=4, q=2, Z is an intermediate of F. m=4, q=2, Z is an intermediate of F Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, a mixture of the three intermediates and N,N'-carbonyldiimidazole in molar ratio of 1:1.4, and the three intermediates and tris(2-aminoethyl)amine in molar ratio of 1:0.4, was added to the above mixed solution. The mixture was stirred and reacted at 20°C for 4 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C17.

[0106] The critical micelle concentration of C17, as tested using the above method, was 1.38 g / L, corresponding to a surface tension of 21.4 mN / m. The degradation rate after 28 days was 97%, and the acute toxicity test results for zebrafish were all low toxicity.

[0107] Example 18:

[0108] With n=4, q=3, and Z as an intermediate of F. p=4, q=3, Z is an intermediate of F. m=4, q=3, Z is an intermediate of F Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, a mixture of the three intermediates and N,N'-carbonyldiimidazole in molar ratio of 1:1.1, and the three intermediates and tris(2-aminoethyl)amine in molar ratio of 1:0.8, was added to the above mixed solution. The mixture was stirred and reacted at 23°C for 3 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C18.

[0109] The critical micelle concentration of C18, as tested using the above method, was 0.19 g / L, corresponding to a surface tension of 19.9 mN / m. The degradation rate after 28 days was 93%, and the acute toxicity test results for zebrafish were all low.

[0110] Example 19:

[0111] With n=11, q=2, and Z as an intermediate of F. p=11, q=2, Z is an intermediate of F. m=11, q=2, Z is an intermediate of F. Dissolved in toluene to obtain a mixed solution, the solution was dried to remove moisture. Then, a mixture of the three intermediates and N,N'-carbonyldiimidazole in molar ratio of 1:1.3, and the three intermediates and tris(2-aminoethyl)amine in molar ratio of 1:0.5, was added to the above mixed solution. The mixture was stirred and reacted at 23°C for 4 hours to obtain a fluorinated nonionic three-armed surfactant. It is labeled C19.

[0112] The critical micelle concentration of C19, as determined by the above methods, was 0.73 g / L, corresponding to a surface tension of 23.0 mN / m. The degradation rate after 28 days was 96%, and the acute toxicity test results for zebrafish were all low.

[0113] Example 20:

[0114] With n=11, q=3, and Z as an intermediate of F. p=11, q=3, Z is an intermediate of F. m=11, q=3, Z is an intermediate of F Dissolve in toluene to obtain a mixed solution, dry to remove moisture, and then add a mixture of the three intermediates and N,N'-carbonyldiimidazole in a molar ratio of 1:1.5 and the three intermediates and tris(2-aminoethyl)amine in a molar ratio of 1:0.9 to the above mixed solution. Stir and react at 23°C for 4 hours to obtain a fluorinated nonionic three-arm surfactant S, labeled C20.

[0115] The critical micelle concentration of C20, as tested using the above method, was 0.48 g / L, corresponding to a surface tension of 23.0 mN / m. The degradation rate after 28 days was 92%, and the acute toxicity test results for zebrafish were all low toxicity.

[0116] In summary, the performance comparison of the fluorinated nonionic three-arm surfactants C1-C20 prepared in Examples 1-20 is shown in Table 2:

[0117] Table 2 Performance Summary of C1-C20

[0118]

[0119] As shown in Table 2, the fluorinated nonionic three-arm surfactants C1-C20 prepared in Examples 1-20 all have excellent degradation rates. This is because the prepared C1-C20 contains hydrophilic PEG segments and fluorocarbon chains. The hydrophilic PEG segments are environmentally friendly molecules that are easily degraded, while the fluorocarbon chains contain less than or equal to 6 carbon atoms with fluorine attached, which can be degraded in the environment and do not have bioaccumulation.

[0120] In the fluorinated nonionic three-arm surfactants C1-C20 prepared in Examples 1-20, the CF bond energy is very high. Therefore, the stability of the prepared fluorinated nonionic three-arm surfactants C1-C20 is much higher than that of hydrocarbon surfactants. In addition, the fluorine atom is slightly larger than the hydrogen atom, which can provide more coverage of the carbon atom, thereby creating a shielding effect on the C-C bond and further improving the thermal and chemical stability of the fluorinated nonionic three-arm surfactants. Fluorine atoms have strong electronegativity but low polarizability. Due to the low polarizability, the interaction between fluorinated chains is weak, resulting in a low cohesive energy of carbon and fluorine. Therefore, the fluorinated nonionic three-arm surfactants have low surface tension and low critical micelle concentration (CMC).

[0121] Furthermore, as can be seen from Table 2, the surface activity properties can be controlled by adjusting the types and proportions of raw materials in Examples 1-20.

[0122] The application of a fluorinated nonionic three-armed surfactant provided by the present invention in pesticides is described below through Examples 21-28:

[0123] Example 21:

[0124] The main factor affecting the synergistic effect of pesticides is the magnitude of their surface tension. The greater the surface tension, the worse the effect. Therefore, the fluorinated nonionic three-armed surfactant C1 prepared in Example 1, which has a relatively high surface tension, was selected as the additive.

[0125] The dosage of the tested insecticide glyphosate was 200 g ai / hm. 2The fluorinated nonionic three-armed surfactant C1 prepared in Example 1 was selected as an additive, and the addition amount was 0.03% (w / w) of the glyphosate spray solution. An indoor potted method was used, with a certain number of barnyard grass plants (20 plants) placed in each pot. The pesticide was added, taking care to keep the barnyard grass plants as uniform in size and color as possible, and maintaining their integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were kept according to the grading standards. The pesticide effect was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated using the following formulas:

[0126] Fresh weight inhibition rate = (control fresh weight - treatment fresh weight) / control fresh weight × 100%;

[0127] Mortality rate = (Number of dead plants / Total number of plants) × 100%.

[0128] Example 22:

[0129] The dosage of the tested insecticide glyphosate was 500 g ai / hm. 2 The fluorinated nonionic three-armed surfactant C1 prepared in Example 1 was selected as an additive, and the addition amount was 0.03% (w / w) of the glyphosate spray solution content. An indoor potted method was used, with a certain number of morning glories (6 plants) placed in each pot, the agent added, taking care to keep the barnyard grass as uniform in size and color as possible, and maintaining its integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were made according to the grading standards. The effectiveness of the agent was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated.

[0130] Example 23:

[0131] This example is a blank control experiment, in which ultrapure water was directly sprayed. An indoor potted method was used, with a certain number of barnyard grass plants (20 plants) placed in each pot, and ultrapure water added. Care was taken to keep the barnyard grass plants as uniform in size and color as possible, and to maintain their integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were kept according to grading standards. The effect of ultrapure water was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated.

[0132] Example 24:

[0133] This example is a blank control experiment, in which ultrapure water was directly sprayed. An indoor potted method was used, with a certain number of morning glories (6 plants) placed in each pot, and ultrapure water added. Care was taken to keep the barnyard grass as uniform in size and color as possible, and to maintain its integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were kept according to grading standards. The effect of ultrapure water was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated.

[0134] Example 25:

[0135] This example is a blank control experiment, and the dosage of the tested insecticide glyphosate is 200 g ai / hm. 2 The pesticide solution was sprayed directly without adding any fluorinated nonionic three-armed surfactant. An indoor potted plant method was used, with a certain number of barnyard grass plants (20 plants) placed in each pot. The pesticide was added, ensuring the barnyard grass plants were as uniform in size and color as possible, and maintaining their integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were kept according to grading standards. The effectiveness of the pesticide was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated.

[0136] Example 26:

[0137] This example is a blank control experiment, and the dosage of the tested insecticide glyphosate is 500 g ai / hm. 2 The pesticide solution was sprayed directly without adding any fluorinated nonionic three-armed surfactant. An indoor potted method was used, with a certain number of morning glories (6 plants) placed in each pot. The pesticide was added, taking care to keep the barnyard grass as uniform in size and color as possible, and maintaining its integrity. The plants were cultivated and observed in a greenhouse (25℃), and records were kept according to grading standards. The effectiveness of the pesticide was evaluated based on the damage to the barnyard grass, and the fresh weight inhibition rate and plant mortality rate were calculated.

[0138] Table 3 shows the synergistic effect of fluorinated nonionic three-armed surfactant C1 on glyphosate-induced barnyardgrass control, as demonstrated in Examples 21, 23, and 25.

[0139] Table 3. Synergistic effect of fluorinated nonionic three-armed surfactant C1 on glyphosate's effect on barnyardgrass control.

[0140]

[0141] As shown in Table 3, it can be seen that the fluorinated nonionic three-armed surfactant C1 can significantly increase the control effect of glyphosate on barnyard grass. Among them, Example 21 showed the highest fresh weight inhibition rate and plant mortality rate of barnyard grass, reaching 99.3% and 86.2%, respectively.

[0142] Furthermore, since the surface tension of C2-C20 is less than or equal to that of C1, it can be expected that the fluorinated nonionic three-armed surfactants C2-C20 can also significantly increase the control effect of glyphosate on barnyard grass.

[0143] Table 4 shows the synergistic effect of fluorinated nonionic three-armed surfactant C1 on glyphosate's effect on morning glory, as demonstrated in Examples 22, 24, and 26.

[0144] Table 4. Synergistic effect of fluorinated nonionic three-armed surfactant C1 on glyphosate's effect on morning glory.

[0145]

[0146] As shown in Table 4, it can be seen that the fluorinated nonionic three-armed surfactant C1 has a significant synergistic effect on the glyphosate-induced killing of morning glory. In Example 22, the fresh weight inhibition rate of morning glory reached as high as 97.8%, and the mortality rate of plants reached 65.1%.

[0147] Furthermore, since the surface tension of C2-C20 is less than or equal to that of C1, it can be expected that the fluorinated nonionic three-armed surfactants C2-C20 can also significantly increase the synergistic effect of glyphosate on morning glory.

[0148] Example 27:

[0149] 50 μL of a 1.6 mmol / L fluorinated nonionic three-arm surfactant (C2, C6, and C7) was dropped onto a 24 mm diameter cabbage leaf. A blank experiment was performed by dropping 50 μL of ultrapure water onto the same 24 mm diameter cabbage leaf. The spreading of the droplets on the leaf surface was observed to confirm the excellent spreading performance of the droplets. Results are as follows: Figure 1 As shown, from left to right, water, C2, C6, and C7 were added to the cabbage leaf. In the case of water, the water droplets were spherical with a small contact area with the cabbage leaf, indicating poor spreading performance of water. Furthermore, when C2, C6, and C7 were added to the cabbage leaf, the contact area between the droplets and the cabbage leaf was significantly larger than in the blank experiment, indicating that C2, C6, and C7 have excellent spreading performance.

[0150] Among them, C2, C6 and C7 have relatively large surface tension compared to the fluorinated nonionic three-armed surfactants prepared in other embodiments. The larger surface tension corresponds to poorer spreading performance. Based on the experimental results of this embodiment, it can be expected that the fluorinated nonionic three-armed surfactants prepared in other embodiments have smaller surface tension and therefore have better spreading performance.

[0151] Example 28:

[0152] Five microliters of a 1.6 mmol / L nonionic three-armed surfactant (Examples 1 and 2) were dropped onto a superhydrophobic paraffin film at a rate of 2.0 m / s. A blank experiment was conducted by dropping five microliters of ultrapure water onto the superhydrophobic paraffin film at a rate of 2.0 m / s. The bouncing, splashing, and eventual spreading of the droplets on the paraffin film were recorded using a high-speed camera. The results are as follows: Figure 2As shown in the figure, the first figure shows that at 50 ms, ultrapure water is finally deposited on the paraffin film surface with a larger contact angle. The second figure shows that at 50 ms, C1 spreads on the paraffin film surface with a smaller contact angle. The third figure shows that at 50 ms, C2 spreads on the paraffin film surface with a smaller contact angle. This indicates that fluorinated nonionic three-arm surfactants such as C1 and C2 can significantly increase the wetting and spreading of water on superhydrophobic surfaces and reduce liquid bouncing and splashing.

[0153] The surface tensions of C1 and C2 are greater than or equal to the surface tensions of C3-C20. The greater the surface tension, the larger the corresponding contact angle. Based on the experimental results in this embodiment, it can be expected that the fluorinated nonionic three-arm surfactants C3-C20 prepared in other embodiments have smaller contact angles, which can also significantly increase the wetting and spreading of water on the superhydrophobic surface and reduce the bouncing and splashing of the liquid.

[0154] 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 fluorinated nonionic three-arm surfactant, characterized in that, The structure is shown in Equation 1: Formula 1 Where R is selected from or One of them; m, n and p are all integers and 1≤m≤90, 1≤n≤90, 1≤p≤90; R1 f R2 f and R3 f For chain segments, the structural formulas are all... q is an integer, 2≤q≤6, and Z is H or F.

2. The fluorinated nonionic three-arm surfactant according to claim 1, characterized in that, The critical micelle concentration of the fluorinated nonionic three-arm surfactant is 0.1 g / L to 2.3 g / L, and the surface tension is 18 mN / m to 26 mN / m.

3. A method for preparing a fluorinated nonionic three-arm surfactant as described in any one of claims 1-2, characterized in that, Includes the following steps: S1: Will , and The mixture is placed in a solvent and stirred to obtain a first mixed solution, wherein the solvent is selected from one of tetrahydrofuran, dioxane, dichloroethane, toluene, or dichloromethane; S2: Add a first organic compound to the first mixed solution and stir at 20~110°C to obtain a fluorinated nonionic three-arm surfactant; wherein the first organic compound is selected from L-lysine triisocyanate or a mixture of N,N'-carbonyldiimidazole and tris(2-aminoethyl)amine.

4. The method for preparing a fluorinated nonionic three-arm surfactant according to claim 3, characterized in that, The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.9; The molar ratio with L-lysine triisocyanate is 1:0.3 to 1:0.

9.

5. The method for preparing a fluorinated nonionic three-arm surfactant according to claim 3, characterized in that, The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio with N,N'-carbonyldiimidazole is 1:1 to 1:1.5; The molar ratio of N,N'-carbonyldiimidazole is 1:1 to 1:1.

5.

6. The method for preparing a fluorinated nonionic three-arm surfactant according to claim 3, characterized in that, The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9; The molar ratio with tris(2-aminoethyl)amine is 1:0.3 to 1:0.9.

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