N-alkyl furanmethylamine sulfonate and its preparation method and application

Abstract

The present application relates to a kind of N-alkyl furan methylamine sulfonate and its preparation method and application, the N-alkyl furan methylamine sulfonate is furan group surfactant, the surfactant has good surface activity, emulsifying property, calcium resistance, has greater application potential in civil washing and industrial cleaning industry.The specific steps of the preparation method of the N-alkyl furan methylamine sulfonate are as follows: first, furfural, fatty amine, magnesium sulfate are mixed and carbamated reaction is carried out;Second, sodium borohydride is used to carry out reduction reaction;Finally, target product is prepared by using chlorosulfonic acid for sulfonation reaction, the preparation method has short reaction time, mild reaction condition.The N-alkyl furan methylamine sulfonate is applied in civil washing and industrial cleaning.Compared with prior art, the surfactant provided in the present application has good surface activity, emulsifying property, calcium resistance, and has greater application potential in civil washing and industrial cleaning industry.

Description

[0001] This invention patent application is a divisional application of Chinese patent application CN2024102532942, filed on March 6, 2024, entitled "An N-alkylfuran methylamine sulfonate and its preparation method and application". Technical Field

[0002] This invention relates to the field of surfactant technology, and in particular to an N-alkylfuran methylamine sulfonate, its preparation method, and its application. Background Technology

[0003] Surfactants, often referred to as "industrial MSG," are chemical substances that reduce interfacial tension between liquid-liquid, liquid-solid, and liquid-gas interfaces. They play a crucial role in our daily lives and are widely used in various fields such as detergents, food processing, and petrochemicals. The most commonly used surfactants in the detergent industry are linear alkylbenzene sulfonates (LAS), α-olefin sulfonates (AOS), alcohol sulfates (AS), and alcohol ether sulfates (AES). Currently, these are mainly derived from petroleum product feedstocks, such as alkylbenzenes, ethylene oxide, olefins, alkanes, and benzene, which are not renewable resources. With the over-exploitation of petroleum resources and the increasing scarcity of fossil resources, the utilization of biomass resources has become a hot research and development area to alleviate the dual pressure on petroleum resources and the human environment.

[0004] In recent years, a new generation of surfactant molecules prepared from renewable raw materials has become increasingly popular. These raw materials are derived from plant and animal sources and mainly include fatty acids, fatty alcohols, fatty amines, sugars, and amino acids. These raw materials undergo further biological or chemical transformation to produce renewable surfactants, which can then be degraded by microorganisms in the natural environment, thus continuously recycling and regenerating. Surfactants derived from biomass are often referred to as "green surfactants" and "renewable surfactants" due to their excellent properties, such as biodegradability, biocompatibility, and non-toxicity, which have made them popular with consumers.

[0005] Surfactants are key components in detergent formulations. They interact with dirt and at the dirt-solid interface through a series of physical reactions (such as wetting, penetration, emulsification, solubilization, dispersion, and foaming), achieving a cleaning effect through mechanical agitation. However, their use in water containing alkaline earth metals (i.e., hard water) impairs surfactant function and necessitates the addition of expensive and environmentally harmful chelating agents. Studies have shown that furan-based surfactants, which use benzene as a linker between polar end groups (e.g., sulfonates) and nonpolar carbon chains instead of LAS (alcohol-based surfactants), exhibit lower critical micelle concentrations (CMC) and Kraft points than LAS, and demonstrate 100 times greater stability in hard water than commercial surfactants. These properties eliminate the need for additional chelating agents in detergent formulations. Therefore, furan-based surfactants are a green alternative to traditional anionic surfactants.

[0006] Chinese patent CN201010582000.9 discloses a furfural surfactant and its preparation method. This method uses furfural as the initial reactant and sequentially employs aldehyde-amine condensation, palladium-on-carbon catalyst hydrogenation reduction, and sulfonation reaction of pyridine with a sulfur trioxide addition compound. The patent also discloses applications of this furfural surfactant in optoelectronic materials and electrolytes. However, this patent has the following drawbacks: 1) The aldehyde-amine condensation reaction of furfural and aliphatic amines does not use a catalyst, resulting in low conversion and yield. 2) Although palladium-on-carbon catalysts have advantages such as good selectivity, stable performance, small feed ratio, and reusability, they are expensive, and current palladium-on-carbon catalyst recovery technology is not yet perfect, leading to resource waste, environmental pollution, and energy consumption. 3) While the sulfonation reaction of pyridine with a sulfur trioxide addition compound has the advantages of mild reaction and stable properties, it requires a large amount and has a low conversion rate. Summary of the Invention

[0007] The purpose of this invention is to provide an N-alkylfuran methylamine sulfonate, its preparation method, and its applications. The N-alkylfuran methylamine sulfonate is a furan-based surfactant with good surface activity, emulsifying properties, and calcium resistance, showing great application potential in both domestic and industrial cleaning industries. The specific steps of the preparation method for the N-alkylfuran methylamine sulfonate are as follows: first, furfural, aliphatic amine, and magnesium sulfate are mixed and subjected to a carbonylation reaction; second, a reduction reaction is carried out using sodium borohydride; finally, a sulfonation reaction is performed using chlorosulfonic acid to obtain the target product. The preparation method using chlorosulfonic acid as the sulfonating agent has advantages such as short reaction time, mild reaction conditions, and high conversion rate. The N-alkylfuran methylamine sulfonate is also discussed for applications in domestic and industrial cleaning.

[0008] The objective of this invention can be achieved through the following technical solutions: A method for preparing N-alkylfuran methylamine sulfonate, the specific steps of which are as follows: S1. Furfural is reacted with aliphatic amines under the action of MgSO4 to obtain the first intermediate product, which is then separated from MgSO4. S2. Dissolve the first intermediate product obtained in step S1 in an anhydrous organic solvent, and add NaBH4 dropwise to carry out a reduction reaction to obtain the second intermediate product. S3. Dissolve the second intermediate product obtained in step S2 in an anhydrous organic solvent, and add chlorosulfonic acid dropwise to carry out a sulfonation reaction to obtain N-alkylfuran methylamine sulfonate.

[0009] Furthermore, in step S1, the fatty amine is selected from any one of dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.

[0010] Further, in step S1, the molar ratio between furfural, fatty amine, and MgSO4 is (1-1.25):1:(0.2-0.5).

[0011] Furthermore, in step S1, the addition of furfural, fatty amine, and MgSO4 is not required in any particular order. MgSO4 is a solid and insoluble in the reaction system, so it can be recovered by means of filtration after the reaction for reuse, thereby reducing the cost of raw materials.

[0012] Furthermore, in step S1, the carbonylation reaction is carried out at a temperature of 30-60 °C, preferably 60 °C, and for a reaction time of 4-6 h, preferably 6 h.

[0013] Furthermore, in step S2, the anhydrous organic solvent is selected from either anhydrous methanol or anhydrous ethanol, preferably anhydrous ethanol.

[0014] Furthermore, in step S2, the molar ratio of NaBH4 to the first intermediate product is (1-1.5):1.

[0015] Further, in step S2, the ratio of the first intermediate product to anhydrous organic solvent is (0.01-0.02) mol to 10 mL.

[0016] Furthermore, in step S2, the reduction reaction is carried out at a temperature of 0-15 °C, preferably 15 °C, and for a reaction time of 4-10 h, preferably 10 h.

[0017] Further, in step S3, the anhydrous organic solvent is selected from either chloroform or dichloroform, preferably chloroform.

[0018] Furthermore, in step S3, the molar ratio of chlorosulfonic acid to the second intermediate is (1-1.5):1.

[0019] Further, in step S3, the second intermediate product: anhydrous organic solvent = (0.015-0.025) mol: 10 mL.

[0020] Furthermore, in step S3, the sulfonation reaction is carried out at a temperature of 30-60 °C, preferably 30 °C, and for a reaction time of 1-2 h, preferably 2 h.

[0021] The present invention also provides an N-alkylfuran methylamine sulfonate, which is prepared by the above method, and the structural formula of the N-alkylfuran methylamine sulfonate is shown in formula (I): ; (I); Where n = 10, 12, 14 or 16.

[0022] Furthermore, the present invention also provides an application of N-alkylfuran methylamine sulfonate, which is used in the fields of domestic washing and industrial cleaning.

[0023] Furthermore, the N-alkylfuran methylamine sulfonate is used in the preparation of detergents or emulsifiers.

[0024] The principle of this invention is as follows: For the separation and purification of the reaction products, after the carbonyl amination reaction, since MgSO4 is added as a catalyst and is an insoluble solid in the reaction system, it can be recovered by filtration or other methods for reuse, reducing raw material costs. After the sulfonation reaction, the pH is neutralized to 7.0 with sodium carbonate solution. The solvent and water are removed by rotary evaporation, followed by extraction of the product with ethanol. Except for the extraction solvent ethanol, N-alkylfuran methylamine sulfonate is obtained.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: 1) This invention uses furfural and fatty amines, renewable resources, as raw materials to prepare N-alkylfuran methylamine sulfonate through reactions such as carbonylation, hydrogenation, and sulfonation. The prepared N-alkylfuran methylamine sulfonate exhibits excellent surface activity, with a minimum surface tension of 29.11 mN / m, a maximum detergency of 91%, and a hard water resistance rating of level 5. It has significant application potential in the fields of domestic detergents and industrial cleaning.

[0026] 2) This invention has the advantages of mild raw materials and reaction conditions, low energy consumption, few side reactions, high yield, stable product properties, low toxicity, and good degradability, which are in line with the development concept of green chemistry.

[0027] 3) The N-alkylfuran methylamine sulfonate prepared by this invention exhibits excellent calcium resistance. Surfactants widely used in the detergent industry require the addition of additional chelating agents to achieve calcium resistance in practical applications, which increases cost and complexity and has adverse environmental impacts. The N-alkylfuran methylamine sulfonate prepared by this invention can independently suppress the effects of hard water without the addition of chelating agents, exhibiting stable detergency and simplifying the formulation of surfactant systems for detergent applications. Attached Figure Description

[0028] Figure 1 The GC-MS total ion chromatogram of N-dodecylfuranimide, the first intermediate product in Example 1; Figure 2 The mass spectrum of N-dodecylfuranimide, the first intermediate product in Example 1; Figure 3 The GC-MS total ion chromatogram of N-dodecylfuranmethylamine, the second intermediate product in Example 1; Figure 4 The mass spectrum of N-dodecylfuranmethylamine, the second intermediate product in Example 1; Figure 5 This is the LC-MS UV detection image of the final product N-dodecylfuran methylamine sulfonate in Example 1; Figure 6 The mass spectrum of the final product N-dodecylfuran methylamine sulfonate in Example 1; Figure 7 The GC-MS total ion chromatogram of the first intermediate product N-tetradecylfuranimide in Example 3 is shown below. Figure 8 The mass spectrum of N-tetradecylfuranimide, the first intermediate product in Example 3; Figure 9 The GC-MS total ion chromatogram of N-tetradecylfuranmethylamine, the second intermediate product in Example 3; Figure 10 The mass spectrum of N-tetradecylfuran methylamine, the second intermediate product in Example 3; Figure 11 This is the LC-MS UV detection image of the final product N-tetradecylfuran methylamine sulfonate in Example 3; Figure 12 The mass spectrum of the final product N-tetradecylfuran methylamine sulfonate in Example 3; Figure 13 The GC-MS total ion chromatogram of the first intermediate product N-hexadecylfuranimide in Example 5; Figure 14 The mass spectrum of N-hexadecylfuranimide, the first intermediate product in Example 5; Figure 15 The GC-MS total ion chromatogram of N-hexadecylfuranmethylamine, the second intermediate product in Example 5; Figure 16 The mass spectrum of N-hexadecylfuran methylamine, the second intermediate product in Example 5; Figure 17 This is the LC-MS UV detection image of the final product N-hexadecylfuran methylamine sulfonate in Example 5; Figure 18 The mass spectrum of the final product N-hexadecylfuran methylamine sulfonate in Example 5; Figure 19 The GC-MS total ion chromatogram of the first intermediate product N-octadecylfuranimide in Example 7 is shown below. Figure 20 The mass spectrum of the first intermediate product N-octadecylfuranimide in Example 7; Figure 21 The GC-MS total ion chromatogram of N-octadecylfuranmethylamine, the second intermediate product in Example 7; Figure 22 The mass spectrum of N-octadecylfuran methylamine, the second intermediate product in Example 7; Figure 23 This is the LC-MS UV detection image of the final product N-octadecylfuran methylamine sulfonate in Example 7; Figure 24 The mass spectrum of the final product N-octadecylfuran methylamine sulfonate in Example 7; Figure 25 This is a graph showing the data on the removal effect of N-dodecylfuran methylamine sulfonate on different stains in Example 1; Figure 26 This is a graph showing the data on the removal effect of N-tetradecylfuran methylamine sulfonate on different stains in Example 3; Figure 27 This is a graph showing the data on the removal effect of N-hexadecylfuran methylamine sulfonate on different stains in Example 5; Figure 28 This is a graph showing the data on the removal effect of N-octadecylfuran methylamine sulfonate on different stains in Example 7; Figure 29 This is a graph showing the data on the removal effect of N-dodecylfuran methylamine sulfonate on different stains in water with different hardness in Example 1; Figure 30 This is a graph showing the emulsifying properties of N-dodecylfuran methylamine sulfonate in Example 1. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0030] A method for preparing N-alkylfuran methylamine sulfonate, the specific steps of which are as follows: S1. Furfural is reacted with aliphatic amines under the action of MgSO4 to obtain the first intermediate product, which is then separated from MgSO4. S2. Dissolve the first intermediate product obtained in step S1 in an anhydrous organic solvent, and add NaBH4 dropwise to carry out a reduction reaction to obtain the second intermediate product. S3. Dissolve the second intermediate product obtained in step S2 in an anhydrous organic solvent, and add chlorosulfonic acid dropwise to carry out a sulfonation reaction to obtain N-alkylfuran methylamine sulfonate.

[0031] In some specific embodiments of the present invention, in step S1, the fatty amine is selected from any one of dodecylamine, tetradecylamine, hexadecylamine or octadecylamine.

[0032] In some specific embodiments of the present invention, in step S1, the molar ratio between furfural, fatty amine and MgSO4 is (1-1.25):1:(0.2-0.5).

[0033] In some specific embodiments of the present invention, in step S1, the addition of furfural, fatty amine and MgSO4 is not required in any particular order. MgSO4 is a solid and insoluble in the reaction system, so it can be recovered by means of filtration after the reaction for reuse, thereby reducing the cost of raw materials.

[0034] In some specific embodiments of the present invention, in step S1, the carbonyl amination reaction is carried out at a temperature of 30-60 °C, preferably 60 °C, and for a reaction time of 4-6 h, preferably 6 h.

[0035] In some specific embodiments of the present invention, in step S2, the anhydrous organic solvent is selected from either anhydrous methanol or anhydrous ethanol, preferably anhydrous ethanol.

[0036] In some specific embodiments of the present invention, in step S2, the molar ratio of NaBH4 to the first intermediate product is (1-1.5):1.

[0037] In some specific embodiments of the present invention, in step S2, the first intermediate product: anhydrous organic solvent = (0.01-0.02) mol: 10 mL.

[0038] In some specific embodiments of the present invention, in step S2, the reduction reaction is carried out at a temperature of 0-15 °C, preferably 15 °C, and for a reaction time of 4-10 h, preferably 10 h.

[0039] In some specific embodiments of the present invention, in step S3, the anhydrous organic solvent is selected from either chloroform or dichloroform, preferably chloroform.

[0040] In some specific embodiments of the present invention, in step S3, the molar ratio of chlorosulfonic acid to the second intermediate product is (1-1.5):1.

[0041] In some specific embodiments of the present invention, in step S3, the second intermediate product: anhydrous organic solvent = (0.015-0.025) mol: 10 mL.

[0042] In some specific embodiments of the present invention, in step S3, the sulfonation reaction is carried out at a temperature of 30-60°C, preferably 30°C, and for a reaction time of 1-2 h, preferably 2 h.

[0043] The present invention also provides an N-alkylfuran methylamine sulfonate, which is prepared by the above method, and the structural formula of the N-alkylfuran methylamine sulfonate is shown in formula (I): ; (I); Where n = 10, 12, 14 or 16.

[0044] Furthermore, the present invention also provides an application of N-alkylfuran methylamine sulfonate, which is used in the fields of domestic washing and industrial cleaning.

[0045] In some specific embodiments of the present invention, the N-alkylfuran methylamine sulfonate is used in the preparation of detergents or emulsifiers.

[0046] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0047] Example 1

[0048] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.020 mol dodecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol furfural and 0.010 mol MgSO4 catalyst were added. The mixture was stirred and heated to 60 °C for 6 h. After the reaction was complete, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-dodecylfuranimine product with a yield of 98.4%. The structure of the N-dodecylfuranimine is shown below: .

[0049] The GC-MS total ion chromatogram of the product N-dodecylfuranimine is shown below. Figure 1 As shown, the mass spectrum is as follows Figure 2 As shown. The detection conditions included: injection volume: 0.20 μL; initial temperature: 180 ℃; heating rate: 5 ℃ / min; target temperature: 280 ℃; holding time: 10 min; split ratio: 50:1.

[0050] 2) Dissolve 0.010 mol of N-dodecylfuranimide product in 10.0 mL of anhydrous ethanol, start stirring and control the system temperature at 15 °C, slowly add 0.015 mol of NaBH4, and react for 10 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-dodecylfuranmamide product with a yield of 98.1%. The structure of the N-dodecylfuranmamide is shown below: .

[0051] The GC-MS total ion chromatogram of the product N-dodecylfuranmethylamine is shown below. Figure 3 As shown, the mass spectrum is as follows Figure 4 As shown.

[0052] 3) Add 0.020 mol of N-dodecylfuran methylamine product to 10 mL of dry chloroform and mix at room temperature until completely dissolved. Slowly add 0.030 mol of chlorosulfonic acid. React at 30 °C for 2 hours until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. Remove the ethanol from the supernatant by rotary evaporation to obtain N-dodecylfuran methylamine sulfonate product with a yield of 96.5%. The structure of the N-dodecylfuran methylamine sulfonate is shown below: .

[0053] The LC-MS UV spectra of the product N-dodecylfuran methylamine sulfonate are shown below. Figure 5 As shown, the mass spectrum is as follows Figure 6 As shown. The detection conditions included: injection volume: 10 μL; detection wavelength: scanning in the wavelength range of 200-600 nm; flow rate: 0.40 mL / min; gradient conditions: 0-8 min, 80% methanol, 8-28 min, 80-100% methanol, 28-80 min, 100% methanol.

[0054] Example 2

[0055] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.016 mol of dodecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol of furfural and 0.005 mol of catalyst MgSO4 were added. The mixture was stirred and heated to 30 °C for 4 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-dodecylfuranimine product with a yield of 82.1%. The structure of the N-dodecylfuranimine is shown below: .

[0056] 2) Dissolve 0.010 mol of N-dodecylfuranimide product in 10.0 mL of anhydrous methanol, start stirring and control the system temperature at 10 °C, slowly add 0.010 mol of NaBH4, and react for 4 h. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-dodecylfuranmamide product with a yield of 95.3%. The structure of the N-dodecylfuranmamide is shown below: .

[0057] 3) Add 0.020 mol of N-dodecylfuran methylamine product to 10 mL of dry dichloromethane and mix at room temperature until completely dissolved. Slowly add 0.020 mol of chlorosulfonic acid. React at 60 °C for 1 hour until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. After removing the ethanol from the supernatant by rotary evaporation, the N-dodecylfuran methylamine sulfonate product is obtained with a yield of 90.1%. The structure of the N-dodecylfuran methylamine sulfonate is shown below: .

[0058] Example 3

[0059] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.020 mol tetradecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol furfural and 0.010 mol MgSO4 catalyst were added. The mixture was stirred and heated to 60 °C for 6 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-tetradecylfuranimine product with a yield of 97.1%. The structure of the N-tetradecylfuranimine is shown below: .

[0060] The GC-MS total ion chromatogram of the product N-tetradecylfuranimide is shown below. Figure 7 As shown, the mass spectrum is as follows Figure 8 As shown.

[0061] 2) Dissolve 0.010 mol of N-tetradecylfuranimide product in 10.0 mL of anhydrous ethanol, start stirring and control the system temperature at 15 °C, slowly add 0.015 mol of NaBH4, and react for 10 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-tetradecylfuranimide product with a yield of 95.1%. The structure of the N-tetradecylfuranimide is shown below: .

[0062] The GC-MS total ion chromatogram of the product N-tetradecylfuranmethylamine is shown below. Figure 9 As shown, the mass spectrum is as follows Figure 10 As shown.

[0063] 3) Add 0.020 mol of N-tetradecylfuran methylamine product to 10 mL of dry chloroform and mix at room temperature until completely dissolved. Slowly add 0.030 mol of chlorosulfonic acid. React at 30 °C for 2 hours until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. Remove the ethanol by rotary evaporation to obtain N-tetradecylfuran methylamine sulfonate product with a yield of 93.7%. The structure of the N-tetradecylfuran methylamine sulfonate is shown below: .

[0064] The LC-MS UV spectra of the product N-tetradecylfuran methylamine sulfonate are shown below. Figure 11 As shown, the mass spectrum is as follows Figure 12 As shown.

[0065] Example 4

[0066] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.016 mol of tetradecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol of furfural and 0.0050 mol of catalyst MgSO4 were added. The mixture was stirred and heated to 30 °C for 4 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-tetradecylfuranimine product with a yield of 86.1%. The structure of the N-tetradecylfuranimine is shown below: .

[0067] 2) Dissolve 0.010 mol of N-tetradecylfuranimide product in 10.0 mL of anhydrous methanol, start stirring and control the system temperature at 10 °C, slowly add 0.010 mol of NaBH4, and react for 4 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-tetradecylfuranmamide product, with a yield of 84.1%. The structure of the N-tetradecylfuranmamide is shown below: .

[0068] 3) Add 0.020 mol of N-tetradecylfuran methylamine product to 10 mL of dry dichloromethane and mix at room temperature until completely dissolved. Slowly add 0.020 mol of chlorosulfonic acid. React at 60 °C for 1 hour until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. Remove the ethanol by rotary evaporation to obtain N-tetradecylfuran methylamine sulfonate product with a yield of 78.7%. The structure of the N-tetradecylfuran methylamine sulfonate is shown below: .

[0069] Example 5

[0070] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.020 mol hexadecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol furfural and 0.010 mol MgSO4 catalyst were added. The mixture was stirred and heated to 60 °C for 6 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-hexadecylfuranimine product with a yield of 98.9%. The structure of the N-hexadecylfuranimine is shown below: .

[0071] The GC-MS total ion chromatogram of the product N-hexadecylfuranimine is shown below. Figure 13 As shown, the mass spectrum is as follows Figure 14 As shown.

[0072] 2) Dissolve 0.010 mol of N-hexadecylfuranimide product in 10.0 mL of anhydrous ethanol, start stirring and control the system temperature at 15 °C, slowly add 0.015 mol of NaBH4, and react for 10 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-hexadecylfuranmamide product with a yield of 97.6%. The structure of the N-hexadecylfuranmamide is shown below: .

[0073] The GC-MS total ion chromatogram of the product N-hexadecylfuranmethylamine is shown below. Figure 15 As shown, the mass spectrum is as follows Figure 16 As shown.

[0074] 3) Add 0.020 mol of N-hexadecylfuran methylamine product to 10 mL of dry chloroform and mix at room temperature until completely dissolved. Slowly add 0.030 mol of chlorosulfonic acid. React at 30 °C for 2 hours until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. After removing the ethanol from the supernatant by rotary evaporation, the N-hexadecylfuran methylamine sulfonate product is obtained with a yield of 94.1%. The structure of the N-hexadecylfuran methylamine sulfonate is shown below: .

[0075] The LC-MS UV chromatogram of the product N-hexadecylfuran methylamine sulfonate is shown below. Figure 17 As shown, the mass spectrum is as follows Figure 18 As shown.

[0076] Example 6

[0077] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.016 mol of hexadecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol of furfural and 0.0050 mol of catalyst MgSO4 were added. The mixture was stirred and heated to 30 °C for 4 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-hexadecylfuranimine product with a yield of 85.6%. The structure of the N-hexadecylfuranimine is shown below: .

[0078] 2) Dissolve 0.010 mol of N-hexadecylfuranimide product in 10.0 mL of anhydrous methanol, start stirring and control the system temperature at 10 °C, slowly add 0.010 mol of NaBH4, and react for 4 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-hexadecylfuranmamide product, with a yield of 97.6%. The structure of the N-hexadecylfuranmamide is shown below: .

[0079] 3) Add 0.020 mol of N-hexadecylfuran methylamine product to 10 mL of dry dichloromethane and mix at room temperature until completely dissolved. Slowly add 0.020 mol of chlorosulfonic acid. React at 60 °C for 1 hour until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. After removing the ethanol from the supernatant by rotary evaporation, N-hexadecylfuran methylamine sulfonate product is obtained with a yield of 86.2%. The structure of the N-hexadecylfuran methylamine sulfonate is shown below: .

[0080] Example 7

[0081] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.020 mol of octadecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol of furfural and 0.010 mol of catalyst MgSO4 were added. The mixture was stirred and heated to 60 °C for 6 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-octadecylfuranimine product with a yield of 98.2%. The structure of the N-octadecylfuranimine is shown below: .

[0082] The GC-MS total ion chromatogram of the product N-octadecylfuranimide is shown below. Figure 19 As shown, the mass spectrum is as follows Figure 20 As shown.

[0083] 2) Dissolve 0.010 mol of N-octadecylfuranimide product in 10.0 mL of anhydrous ethanol, start stirring and control the system temperature at 15 °C, slowly add 0.015 mol of NaBH4, and react for 10 h until no more bubbles are generated. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-octadecylfuranimide product with a yield of 96.4%. The structure of the N-octadecylfuranimide is shown below: .

[0084] The GC-MS total ion chromatogram of the product N-octadecylfuranmethylamine is shown below. Figure 21 As shown, the mass spectrum is as follows Figure 22 As shown.

[0085] 3) Add 0.020 mol of N-octadecylfuran methylamine product to 10 mL of dry chloroform and mix at room temperature until completely dissolved. Slowly add 0.030 mol of chlorosulfonic acid. React at 30 °C for 2 hours until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. After removing the ethanol from the supernatant by rotary evaporation, the N-octadecylfuran methylamine sulfonate product is obtained with a yield of 89.5%. The structure of the N-octadecylfuran methylamine sulfonate is shown below: .

[0086] The LC-MS UV chromatogram of the product N-octadecylfuran methylamine sulfonate is shown below. Figure 23 As shown, the mass spectrum is as follows Figure 24 As shown.

[0087] Example 8

[0088] This embodiment provides an N-alkylfuran sulfonate surfactant, the preparation method of which includes the following steps: 1) 0.016 mol of octadecylamine was added to 10 mL of n-hexane and mixed thoroughly. Then, 0.020 mol of furfural and 0.0050 mol of catalyst MgSO4 were added. The mixture was stirred and heated to 30 °C for 4 h. After the reaction was completed, MgSO4 was removed by centrifugation, and the solvent and residual furfural were removed by vacuum distillation to obtain N-octadecylfuranimine product with a yield of 85.4%. The structure of the N-octadecylfuranimine is shown below: .

[0089] 2) Dissolve 0.010 mol of N-octadecylfuranimide product in 10.0 mL of anhydrous methanol, start stirring and control the system temperature at 10 °C, slowly add 0.010 mol of NaBH4, and react for 4 h. Centrifuge to remove insoluble salts, and remove solvent by vacuum distillation. Dissolve the remaining solid in methanol, centrifuge to collect the supernatant, and remove methanol by rotary evaporation to obtain N-octadecylfuranmamide product, with a yield of 89.1%. The structure of the N-octadecylfuranmamide is shown below: .

[0090] 3) Add 0.020 mol of N-octadecylfuran methylamine product to 10 mL of dry dichloromethane and mix at room temperature until completely dissolved. Slowly add 0.020 mol of chlorosulfonic acid. React at 60 °C for 1 hour until no bubbles are generated. Remove the solvent under vacuum, and neutralize the solution to pH 7.0 with sodium carbonate solution. Remove water by rotary evaporation, then extract the product with ethanol. Centrifuge and collect the supernatant. After removing the ethanol from the supernatant by rotary evaporation, the N-octadecylfuran methylamine sulfonate product is obtained with a yield of 84.5%. The structure of the N-octadecylfuran methylamine sulfonate is shown below: .

[0091] Example 9

[0092] This example is used to test and characterize the detergency of the N-dodecylfuran methylamine sulfonate surfactant prepared in Example 1, the N-tetradecylfuran methylamine sulfonate surfactant prepared in Example 3, the N-hexadecylfuran methylamine sulfonate surfactant prepared in Example 5, and the N-octadecylfuran methylamine sulfonate surfactant prepared in Example 7. The test methods are as follows: A constant-temperature stirring device was used to simulate the washing process. Clean, dried white cotton cloth was cut into 6 cm × 6 cm cubes, and its initial mass was accurately recorded (A). Soybean oil, tomato sauce, ink, and machine oil were used to create soiled cloths. The selected staining materials were evenly applied to the cotton cloths, dried until constant weight, and the mass of the soiled cloths was accurately measured (B). For the test, a 1 g / L surfactant solution was prepared, and the soiled cloth was placed in 200 mL of the test solution and reacted on a constant-temperature stirring device for 30 min. The washing temperature was 30 ℃, and the stirring speed was 200 rpm. After the test, the test cloth was carefully removed, rinsed with tap water for 1 min, and dried in an oven until constant weight. The mass of the cotton cloth after the experiment was accurately measured (C). All recorded masses in this experiment were accurate to 0.0001 g. Each experiment was repeated three times, and the stain removal efficiency was calculated using a formula.

[0093]

[0094] Test results are as follows Figure 25 , Figure 26 , Figure 27 as well as Figure 28 As shown in the figure, N-dodecylfuran methylamine sulfonate has a cleaning rate of 79.87% for soybean oil, 90.79% for tomato sauce, 91.29% for ink, and 72.36% for machine oil.

[0095] N-Tetradecylfuran methylamine sulfonate achieved a cleaning efficiency of 78.32% for soybean oil, 82.13% for tomato sauce, 88.36% for ink, and 70.65% for machine oil.

[0096] N-Hexadecylfuran methylamine sulfonate achieved a cleaning efficiency of 57.15% for soybean oil, 84.68% for tomato sauce, 91.63% for ink, and 64.5% for machine oil.

[0097] N-Octadecylfuran methylamine sulfonate achieved a cleaning efficiency of 54.65% for soybean oil, 83.65% for tomato sauce, 87.6% for ink, and 58.95% for machine oil.

[0098] Example 10

[0099] This embodiment is used to test and characterize the detergency of the N-dodecylfuran methylamine sulfonate surfactant prepared in Example 1 in hard water. The test method is the same as in Example 9.

[0100] Test results are as follows Figure 29 As shown in the figure, N-dodecylfuran methylamine sulfonate has a cleaning rate of 79.87% for soybean oil in tap water, 77.45% in 250 mg / kg hard water, and 75.83% in 500 mg / kg hard water. N-Dodecylfuran methylamine sulfonate achieved a tomato sauce removal rate of 90.79% in tap water, 87.45% in 250 mg / kg hard water, and 85.67% in 500 mg / kg hard water. N-Dodecylfuran methylamine sulfonate achieved an ink removal rate of 91.29% in tap water, 87.05% in 250 mg / kg hard water, and 84.66% in 500 mg / kg hard water. The oil-removing efficiency of N-dodecylfuran methylamine sulfonate in tap water was 71.6%, in 250 mg / kg hard water it was 80.1%, and in 500 mg / kg hard water it was 81.60%. The oil-removing properties of N-dodecylfuran methylamine sulfonate increased with increasing Ca content. 2+ Mg 2+ The concentration increases, indicating that N-dodecylfuran methylamine sulfonate exhibits good and stable detergency in tap water and water of varying hardness.

[0101] Example 11

[0102] This embodiment is used to evaluate the emulsifying performance of N-dodecylfuran methylamine sulfonate prepared in Example 1 by testing its emulsification index. The test method is as follows: Soybean oil, corn oil, rapeseed oil, and machine oil were selected as the oil phases for testing. 10 mL of the oil phase and 10 mL of different surfactant solutions (1 g / L) were added to a 30 mL glass bottle. The emulsifier was sheared at 13000 rpm for two minutes to form a homogeneous emulsion. The height of the emulsion layer was recorded after standing at 25 °C for 24 h.

[0103] Test results are as follows Figure 30 As shown in the figure, N-dodecylfuran methylamine sulfonate has good emulsifying properties, with an emulsification index of over 60% for both vegetable oil and engine oil, indicating significant application potential in the domestic and industrial cleaning industries.

[0104]

[0105] Surface tension test of the product of this invention

[0106] Instrument: Dataphysics surface tension meter

[0107] Methods: A series of surfactant solutions of different concentrations were prepared, and the surface tension of N-alkylfuran methylamine sulfonate was determined by the dip plate method at 25 °C.

[0108] Stability test of the product in hard water of this invention

[0109] Methods: Hard aqueous solutions with S1 = 3 mmol / L Ca were prepared according to the evaluation methods and standards in GB / T 7381-2010. 2+ S2 = 4.5 mol / LCa 2+ S3 = 6 mmol / L Ca 2+Add 5.0 mL, 2.5 mL, 1.2 mL, 0.6 mL, and 0.3 mL of the test solution to solutions S1, S2, and S3, respectively, and bring the volume to 50 mL. Shake well and let stand at 25°C for 1 h, then observe the appearance of the test system. Strictly follow the description of the appearance of the test system to score the hard water resistance of the test substance. The higher the average stability grade of the test sample, the stronger its hard water resistance.

[0110] Table 1 Properties of products from different embodiments

[0111] The N-alkylfuran methylamine sulfonate prepared by this invention exhibits excellent surface activity, with a minimum surface tension of 29.11 mN / m, a maximum detergency of 91%, and a hard water resistance rating of 5. It can independently suppress the effects of hard water without the addition of chelating agents, simplifying the formulation of surfactant systems for washing applications. It has significant application potential in both domestic and industrial cleaning industries.

[0112] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. An application of an N-alkylfuran methylamine sulfonate, characterized in that, The N-alkylfuran methylamine sulfonate is used in the preparation of detergents or emulsifiers; the structural formula of the N-alkylfuran methylamine sulfonate is shown in formula (I): ； (I)； Where n = 10, 12, 14 or 16.

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