Environment-friendly surfactant and preparation process thereof

Abstract

The application relates to the technical field of surfactants, and discloses an environment-friendly surfactant and a preparation process thereof, wherein the raw material of alkyl polyglycoside is derived from carbohydrates and natural fatty alcohols, has low biological toxicity and a fast biological degradation rate, and has the characteristics of common non-ion and anion surfactants; the organic silicon surfactant has strong wetting capacity and extremely strong adhesion, can be firmly adhered on a surface, and can rapidly spread to make a liquid film extremely thin, the liquid film can overflow into stomata of plant leaves or insects along the stomata edge, and meanwhile, effective components of the pesticide are brought in, so the environment-friendly surfactant is widely applied in insecticides, fungicides and herbicides; the quaternary ammonium salt additive has good sterilization and disinfection effects, and has high bacteriostatic activity on plant pathogenic fungi; the environment-friendly surfactant prepared by the application has the advantages of the three, has a fast biological degradation speed, and is safe and non-toxic.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, specifically to an environmentally friendly surfactant and its preparation process. Background Technology

[0002] Surfactants play an increasingly important role in production, daily life, and are figuratively called "industrial MSG." They are widely used in cosmetics, detergents, pesticide adjuvants, and other fields. Among them, pesticide adjuvants are a general term for auxiliary substances other than the active ingredients of pesticides used in pesticide processing and application. As emulsifiers and dispersants, pesticide surfactants are widely used in various pesticide formulations such as microemulsions and water-in-oil emulsions. They play an important role in fully exerting the efficacy of pesticides and achieving the purpose of insecticidal and herbicidal effects safely and economically. However, at the same time, the environmental pollution caused by the large-scale use of surfactants cannot be ignored. Therefore, the research and development of a green and environmentally friendly surfactant is of great significance for expanding its application in pesticide formulations.

[0003] The addition of surfactants significantly reduces the surface tension of pesticide formulations, decreases the contact angle, and enhances their wetting and adhesion capabilities on plant or insect surfaces, thereby improving dispersibility and efficacy. However, a problem with existing technologies is that the extensive use of traditional surfactants poses potential environmental hazards. Traditional emulsifying dispersants are mostly nonionic surfactants from the alkylphenol polyoxyethylene ether series. Alkylphenol polyoxyethylene ethers are highly toxic to aquatic organisms, exhibit estrogenic effects that negatively impact biological development, and produce byproducts that are difficult to degrade, causing significant environmental harm. Organosilicon surfactants typically possess good wetting properties. With its strong adhesion, excellent extensibility, good resistance to rain erosion, and high porosity, quaternary ammonium salt has been rapidly developed and applied in pesticide adjuvants. It has good water solubility and the ability to reduce surface tension, thus maintaining good bactericidal effects. Patent No. CN104788487B discloses a hydrolysis-resistant Si-C-Si type cationic organosilicon surfactant. A highly surface-active hydrolysis-resistant Si-C-Si type cationic organosilicon surfactant is prepared by reacting synthesized chloropropyl silane with a tertiary amine through Grignard reaction. It has certain hydrolysis resistance, but its degradability is limited and the reagent cost is high, making it unsuitable for industrial production.

[0004] This invention introduces a fully degradable alkyl glycoside structure onto an organosilicon surfactant, utilizing the synergistic effect of organosilicon, quaternary ammonium salt, and alkyl glycoside. When applied as a pesticide surfactant, it exhibits good dispersibility and stability, reducing the amount of pesticide active ingredient required and bringing significant benefits to agricultural production. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the existing technology and provide an environmentally friendly surfactant and its preparation process. This environmentally friendly surfactant has the characteristics of good dispersibility and good biodegradability.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A process for preparing an environmentally friendly surfactant, wherein the structure of the environmentally friendly surfactant is as follows: The preparation process includes the following steps:

[0008] (1) Add decyl BD-glucopyranoside and dichloromethane to a reaction flask, stir at 0-5℃ for 5-15 min, add thionyl chloride, react at 20-35℃ for 2-6 h, concentrate, add ethyl acetate and n-hexane, precipitate, filter, and obtain chloroalkyl glycoside. The preparation process is as follows:

[0009]

[0010] (2) Add the tetratert-amine organosilicon intermediate and solvent to the reaction flask, stir until homogeneous, add the chloroalkyl glycoside, stir to react, and after the reaction is complete, filter, recrystallize from ethyl acetate to obtain the environmentally friendly surfactant. The preparation process is as follows:

[0011]

[0012] Furthermore, in step (1), the mass of thionyl chloride is 40-50% of the mass of decyl BD-glucopyranoside.

[0013] Furthermore, the solvent in step (2) is any one of acetonitrile, ethanol, and N,N-dimethylformamide.

[0014] Furthermore, in step (2), the mass of the chloroalkyl glycoside is 220-300% of the mass of the tetratert-amine organosilicon intermediate.

[0015] Furthermore, in step (2), the reaction temperature is 80-100℃ and the reaction time is 8-16h.

[0016] Furthermore, the preparation process of the tetratert-amine organosilicon intermediate in step (2) includes the following steps:

[0017] S1. Add 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and thionyl chloride to a reaction flask, stir the reaction, and after the reaction is complete, concentrate the solution to remove excess thionyl chloride, yielding the tetramethyldisiloxane dibutyryl chloride intermediate. The preparation process is as follows:

[0018]

[0019] S2. Add tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to a reaction flask, then add N,N,N′,N′-tetraethyldiethylenetriamine. Stir the reaction mixture. After the reaction is complete, extract with dichloromethane and deionized water. Concentrate the organic phase and purify by column chromatography to obtain the tetratert-amine organosilicon intermediate. The preparation process is as follows:

[0020]

[0021] Furthermore, in step S1, the mass of thionyl chloride is 150-230% of the mass of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid.

[0022] Furthermore, in step S1, the reaction temperature is 75-90℃ and the reaction time is 2-5h.

[0023] Furthermore, in step S2, the mass of N,N,N′,N′-tetraethyldiethylenetriamine is 125-190% of the mass of the tetramethyldisiloxane dibutyryl chloride intermediate.

[0024] Furthermore, in step S2, the reaction temperature is 20-35℃ and the reaction time is 1-3h.

[0025] By adopting the above technical solution, the beneficial effects of the present invention are as follows:

[0026] This invention first involves chlorinating 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid with thionyl chloride to obtain a tetramethyldisiloxane dibutyryl chloride intermediate, which is then condensed with N,N,N′,N′-tetraethyldiethylenetriamine to obtain a tetratert-amine organosilicon intermediate. Next, decyl BD-glucopyranoside undergoes a chlorination reaction under the action of thionyl chloride to obtain a chloroalkyl glycoside. Finally, the chloroalkyl glycoside undergoes a quaternization reaction with the tetratert-amine organosilicon intermediate to obtain an environmentally friendly surfactant.

[0027] Alkyl glycosides are mostly made from carbohydrates and natural fatty alcohols. They have low biotoxicity, good environmental compatibility, and a fast biodegradation rate. They also possess the characteristics of both common nonionic and anionic surfactants, exhibiting strong emulsifying ability, good wetting properties, and strong detergency. Organosilicon surfactants have strong wetting ability and extremely strong adhesion to hydrophobic surfaces. When an aqueous solution containing such surfactants is dropped onto a strongly hydrophobic surface, the droplet does not bounce but adheres firmly to the surface and spreads rapidly to form an extremely thin liquid film. This liquid film can "overflow" into the stomata of plant leaves or insects along the stomatal edges, while simultaneously carrying the active ingredient of the pesticide. They are widely used in insecticides, fungicides, and herbicides. Quaternary ammonium salt adjuvants have good bactericidal and disinfecting effects and also have high antibacterial activity against plant pathogenic fungi.

[0028] The environmentally friendly surfactant prepared by this invention combines the advantages of all three: it contains multiple alkyl glycoside structures, exhibits good biodegradability, and during pesticide processing, it adsorbs onto the surface of pesticide particles to form different dispersion systems, playing a role in emulsification, wetting, and stabilization. This improves the distribution, adhesion, and penetration of the pesticide solution on the surface of the target organism, enhancing the effective transfer of pesticide dosage and directly or indirectly increasing the effective utilization rate of pesticides. With consistent efficacy, it requires a small dosage and low cost, and can be used alone to meet the needs of various pesticide processing, avoiding the need for compounding processes. Furthermore, this type of surfactant is non-irritating to the skin and eyes, biodegrades rapidly, and is safe and non-toxic, making it universally applicable in the cosmetics, detergent, and pharmaceutical industries. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] Example 1

[0031] (1) Add 100g of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and 180g of thionyl chloride to a reaction flask, react at 85°C for 3h, concentrate, remove excess thionyl chloride, and obtain tetramethyldisiloxane dibutyryl chloride intermediate.

[0032] (2) Add 100g of tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to the reaction flask, add 170g of N,N,N′,N′-tetraethyldiethylenetriamine, stir and react at 25℃ for 2h, add dichloromethane and deionized water for extraction, concentrate the organic phase, and purify by column chromatography to obtain tetratert-amine organosilicon intermediate.

[0033] (3) Add 100g of decyl BD-glucopyranoside and dichloromethane to the reaction flask, stir at 2℃ for 10min, add 45g of thionyl chloride, react at 30℃ for 5h, concentrate, add ethyl acetate and n-hexane, precipitate out, filter, and obtain chloroalkyl glycoside.

[0034] (4) Add 100g of tetratert-amine organosilicon intermediate and acetonitrile to the reaction flask, stir well, add 285g of chloroalkyl glycoside, react at 85℃ for 12h, filter, recrystallize from ethyl acetate to obtain environmentally friendly surfactant.

[0035] Example 2

[0036] (1) Add 100g of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and 150g of thionyl chloride to a reaction flask, react at 90°C for 5 hours, concentrate, remove excess thionyl chloride, and obtain tetramethyldisiloxane dibutyryl chloride intermediate.

[0037] (2) Add 100g of tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to the reaction flask, add 125g of N,N,N′,N′-tetraethyldiethylenetriamine, stir and react at 35℃ for 3h, add dichloromethane and deionized water for extraction, concentrate the organic phase, and purify by column chromatography to obtain tetratert-amine organosilicon intermediate.

[0038] (3) Add 100g of decyl BD-glucopyranoside and dichloromethane to the reaction flask, stir at 0℃ for 15min, add 40g of thionyl chloride, react at 35℃ for 6h, concentrate, add ethyl acetate and n-hexane, precipitate out, filter, and obtain chloroalkyl glycoside.

[0039] (4) Add 100g of tetratert-amine organosilicon intermediate and N,N-dimethylformamide to the reaction flask, stir well, add 220g of chloroalkyl glycoside, react at 100℃ for 8h, filter, recrystallize from ethyl acetate to obtain environmentally friendly surfactant.

[0040] Example 3

[0041] (1) Add 100g of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and 230g of thionyl chloride to a reaction flask, react at 75°C for 2 hours, concentrate, remove excess thionyl chloride, and obtain tetramethyldisiloxane dibutyryl chloride intermediate.

[0042] (2) Add 100g of tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to the reaction flask, add 190g of N,N,N′,N′-tetraethyldiethylenetriamine, stir and react at 20℃ for 1h, add dichloromethane and deionized water for extraction, concentrate the organic phase, and purify by column chromatography to obtain tetratert-amine organosilicon intermediate.

[0043] (3) Add 100g of decyl BD-glucopyranoside and dichloromethane to the reaction flask, stir at 5℃ for 5min, add 50g of thionyl chloride, react at 20℃ for 2h, concentrate, add ethyl acetate and n-hexane, precipitate out, filter, and obtain chloroalkyl glycoside.

[0044] (4) Add 100g of tetratert-amine organosilicon intermediate and ethanol to the reaction flask, stir well, add 300g of chloroalkyl glycoside, react at 80℃ for 16h, filter, recrystallize from ethyl acetate to obtain environmentally friendly surfactant.

[0045] Surface tension test: The surface tension of the surfactant solution was determined according to the method of GB5549-90. Different concentrations of surfactant solutions were prepared with deionized water. The surface tension of the surfactant was determined by the ring method of a surface / interface tension meter. The experimental temperature was 25℃. The surface tension experiment was repeated 3 times. The surface tension difference was less than 0.1mN / m.

[0046] Table 1 Surface Tension Test

[0047]

[0048] The test results in the table above show that as the concentration of environmentally friendly surfactants increases, their surface tension gradually decreases. When the concentration of environmentally friendly surfactants is 100 mg / L, the surface tension decreases by about 19 mN / m. This means that even with a low concentration of environmentally friendly surfactants, the reduction in surface tension is more significant, indicating strong surface activity. Because organosilicon molecules remove water molecules during surface adsorption and undergo structural rearrangement to reduce surface energy, they promote adsorption on the solution surface. When the solution is relatively dilute, the surfactant almost completely concentrates on the surface to form a monolayer. The surfactant concentration on the surface layer is higher than that in the solution, exhibiting lower surface tension. This makes it easier to reach the critical surface tension of different crop leaves, allowing the pesticide solution to completely wet the leaves and enhancing the pesticide's effect. Simultaneously, alkyl glycosides have high surface activity and significantly reduce surface tension, which is of great significance in the practical application of pesticides.

[0049] Comparative Example 1

[0050] (1) Add 100g of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and 180g of thionyl chloride to a reaction flask, react at 85°C for 3h, concentrate, remove excess thionyl chloride, and obtain tetramethyldisiloxane dibutyryl chloride intermediate.

[0051] (2) Add 100g of tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to the reaction flask, add 170g of N,N,N′,N′-tetraethyldiethylenetriamine, stir and react at 25℃ for 2h, add dichloromethane and deionized water for extraction, concentrate the organic phase, and purify by column chromatography to obtain tetratert-amine organosilicon intermediate.

[0052] Comparative Example 2

[0053] 100g of decyl BD-glucopyranoside and dichloromethane were added to a reaction flask and stirred at 2°C for 10 min. Then, 45g of thionyl chloride was added and the mixture was reacted at 30°C for 5 h. The mixture was then concentrated, and ethyl acetate and n-hexane were added to precipitate the precipitate. The precipitate was filtered to obtain chloroalkyl glycoside.

[0054] Preparation of indoxacarb pesticide solution: Add 1g of the surfactants prepared in Examples 1-3 and the intermediates prepared in Comparative Examples 1 and 2, 84g of deionized water, and 15g of indoxacarb technical to 5 beakers respectively. After stirring evenly, add the mixture to a sand mill and add zirconium silicate beads (0.8mm in diameter). Grind at 1500r / min for 2 hours at room temperature. After filtering out the zirconium beads, indoxacarb pesticide solutions containing different surfactants are obtained.

[0055] Preparation of nicosulfuron pesticide solution: Add 1g of the surfactants prepared in Examples 1-3 and the intermediates prepared in Comparative Examples 1 and 2, 84g of deionized water, and 25g of nicosulfuron technical to 5 beakers respectively. After stirring evenly, add the mixture to a sand mill, add zirconium silicate beads (0.8mm in diameter), and grind at 1500r / min for 2 hours at room temperature. After filtering out the zirconium beads, nicosulfuron pesticide solutions containing different surfactants are obtained.

[0056] Suspension rate test: The test was conducted in accordance with the national standard GB / T 14825-2006.

[0057] Dispersibility test: Add 100 mL of standard hard water (25℃) to a 100 mL stoppered graduated cylinder. Use a dropper to take 1 mL of the prepared pesticide solution and drop it into the water from a certain height above the surface. Observe its dispersibility, capture the state of the solution upon entering the water, and gently shake it to allow it to slowly and completely disperse. Using the middle of the graduated cylinder as the axis, invert the cylinder 30 times. After shaking well, let it stand for 1 hour and observe the dispersion state again. The dispersion state is classified into the following grades:

[0058] Excellent: It disperses automatically in standard hard water in a cloud-like manner, with no visible particles, and no sediment or stratification after standing. Good: It can disperse automatically in standard hard water, but some particles sink. It can slowly disperse after gentle shaking, and there is no or only slight sedimentation or stratification after standing. Poor: It cannot disperse automatically in standard hard water, and sinks in a flocculent or granular manner. It can only be completely dispersed after vigorous shaking, and there is obvious sedimentation or stratification after standing.

[0059] Thermal stability test: The thermal storage stability was determined according to the method of GB / T 19136-2003. 20g of the prepared pesticide solution was sealed into an ampoule and placed in a constant temperature incubator at 54℃. After standing for 14 days, the pesticide solution was taken out and tested according to the national standard test method for various performance indicators, such as appearance, particle size, suspension rate, active ingredients, rheology, etc. If all indicators meet the relevant standards, the thermal storage stability is good.

[0060] Low-temperature stability test: The low-temperature stability was determined according to the method of GB / T 19137-2003. 20g of the prepared pesticide solution was placed in an ampoule and refrigerated in a refrigerator at 0℃. After standing for 14 days, the pesticide solution was taken out and tested according to the national standard test method. If all indicators meet the relevant standards, the low-temperature stability is good.

[0061] Table 2. Suspension and stability tests of indoxacarb pesticide solution.

[0062]

[0063] Indoxacarb is a broad-spectrum insecticide with good control effects on almost all lepidopteran pests, including beet armyworm, small armyworm, cabbage armyworm, cotton bollworm, and tobacco worm, as well as larvae of all ages. The surfactant can act as a dispersant, adsorbing onto the surface of the active ingredient particles, effectively wetting the particles and eliminating air between them, thus reducing interfacial tension, reducing particle aggregation in the dispersion system, and improving dispersibility.

[0064] Formulations with high suspension rates maintain a consistent concentration of pesticide solution before and after spraying, depositing evenly on the target organism and maximizing efficacy. Conversely, low suspension rates indicate a low concentration in the upper layer and a high concentration in the middle and lower layers, sometimes even with pesticide sedimentation at the bottom. This inconsistency in concentration before and after spraying makes it difficult to guarantee efficacy and may even cause phytotoxicity. The test data in the table above shows that when surfactants are added to pesticide raw materials and form a solution system with other adjuvants, the suspension rate is around 98%, indicating good dispersibility and ensuring consistent pesticide concentration during spraying. Comparative Example 1, which only added a tetratert-amine organosilicon intermediate, had a suspension rate of only 12.1%, showing poor dispersibility. Comparative Example 2, which only added chloroalkyl glycosides, had a suspension rate of 80.43%, lower than the example. This demonstrates that the prepared environmentally friendly surfactant provides excellent dispersion in pesticide dilutions, resulting in good compatibility among the various pesticide adjuvants.

[0065] Because pesticide formulations require a certain period from production to final use by the user, maintaining product stability during this time is crucial. As shown in the test results above, the indoxacarb pesticide solution exhibits a decomposition rate of less than 1% after 14 days of storage at 54℃, demonstrating good thermal stability. After 14 days of storage at 0℃, it shows no turbidity, crystallization, or stratification, indicating excellent low-temperature stability. This suggests that the addition of the surfactant in the preparation process enables the pesticide solution to meet relevant standards, thereby expanding its application range.

[0066] Table 3. Tests on the suspension and stability properties of nisosulfuron pesticide solution.

[0067]

[0068] Mesotrione is a broad-spectrum herbicide that can effectively control major broadleaf weeds and some grassy weeds. As shown in the test data in the table above, the environmentally friendly surfactants added in Examples 1-3, after being formulated into a solution, have a suspension rate of approximately 99%, good dispersibility, and their thermal storage stability and low-temperature stability also meet relevant standards, indicating a wide range of applications.

[0069] The above embodiments of the present invention are merely illustrative examples and are not intended to limit the implementation of the invention. Those skilled in the art can make other variations and modifications based on the above description. It is impossible to exhaustively list all possible implementations here. All obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A preparation process for an environmentally friendly surfactant, characterized in that, The structure of the environmentally friendly surfactant is as follows: The preparation process includes the following steps: (1) Add decyl BD-glucopyranoside and dichloromethane to the reaction flask, stir at 0-5℃ for 5-15 min, add thionyl chloride, react at 20-35℃ for 2-6 h, concentrate, add ethyl acetate and n-hexane, precipitate out, filter, and obtain chloroalkyl glycoside. (2) Add the tetratert-amine organosilicon intermediate and solvent to the reaction flask, stir evenly, add chloroalkyl glycoside, stir to react, filter after the reaction is complete, recrystallize with ethyl acetate to obtain environmentally friendly surfactant. The preparation process of the tetratert-amine organosilicon intermediate in step (2) includes the following steps: S1. Add 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid and thionyl chloride to a reaction flask, stir the reaction, and after the reaction is completed, concentrate the mixture to remove excess thionyl chloride to obtain tetramethyldisiloxane dibutyryl chloride intermediate. S2. Add tetramethyldisiloxane dibutyryl chloride intermediate and tetrahydrofuran to the reaction flask, then add N,N,N′,N′-tetraethyldiethylenetriamine, stir the reaction, and after the reaction is complete, add dichloromethane and deionized water for extraction, concentrate the organic phase, and purify by column chromatography to obtain the tetratert-amine organosilicon intermediate.

2. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step (1), the mass of thionyl chloride is 40-50% of the mass of decyl BD-glucopyranoside.

3. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, The solvent in step (2) is any one of acetonitrile, ethanol, and N,N-dimethylformamide.

4. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step (2), the mass of the chloroalkyl glycoside is 220-300% of the mass of the tetratert-amine organosilicon intermediate.

5. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, The reaction temperature in step (2) is 80-100℃ and the reaction time is 8-16h.

6. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step S1, the mass of thionyl chloride is 150-230% of the mass of 4,4'-(1,1,3,3-tetramethyldisiloxane-1,3-diyl)dibutyric acid.

7. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step S1, the reaction temperature is 75-90℃ and the reaction time is 2-5h.

8. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step S2, the mass of N,N,N′,N′-tetraethyldiethylenetriamine is 125-190% of the mass of the tetramethyldisiloxane dibutyryl chloride intermediate.

9. The preparation process of the environmentally friendly surfactant according to claim 1, characterized in that, In step S2, the reaction temperature is 20-35℃ and the reaction time is 1-3h.

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