Calcium and magnesium tolerant mono-aryl linked gemini surfactant preparation and applications

Abstract

The application belongs to the technical field of washing and decontamination, and relates to preparation and application of a calcium and magnesium resistant mono-aryl connected gemini surfactant. The preparation method comprises the following steps: mixing methyl undecylenate, benzene and methanesulfonic acid, and performing heating reaction; mixing the obtained product, methyl undecylenate and methanesulfonic acid, and performing heating reaction; mixing the obtained product, N,N-dimethyl-1,3-propanediamine, and performing heating reaction; mixing the obtained product, a halide salt and sodium carbonate, and performing heating reaction to obtain phenyl bis-undecanoic acid amide hydroxyl sulfonate, namely the mono-aryl connected gemini surfactant. Compared with the prior art, the application can achieve good decontamination effect in a higher hard water concentration solution without additional addition of a chelating agent.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of washing and decontamination, and relates to a preparation and application of a calcium-magnesium-resistant single-aryl-linked gemini surfactant. BACKGROUND

[0002] Detergents are one of the necessities of production and life, and are widely used in fields such as household cleaning and industrial cleaning. During the washing process, the surfactants in the detergent formula need to meet the functional requirements under different environmental conditions such as low temperature, high temperature and different water hardness. At present, the commonly used surfactants in detergents on the market include linear alkyl benzene sulfonate (SDBS), lauryl alcohol ether sulfate (AES) and fatty alcohol polyoxyethylene ether (AEO). Among them, AEO has limited solubility at room temperature and slow dissolution speed, SDBS and AEO have low cloud points and are prone to precipitate in the form of gel at low temperature, and the formula is unstable. The general method is to add a solvent or to use special non-ionic surfactants such as isomeric alcohols, but the solvent itself has no decontamination power, and some isomeric alcohols cannot reach the same decontamination power as AEO. In addition, most of the washing water in China is hard water, SDBS forms a complex with calcium and magnesium ions in water, resulting in a decrease in the decontamination power of the formula, which needs to be used in combination with a chelating agent. However, the chelating agent is not conducive to the stability of the formula, and the post-processing is complex, which increases the cost and causes environmental pollution.

[0003] The purpose of the present application is to overcome the defects of the prior art, and to provide a preparation method of an amphoteric surfactant with excellent decontamination power under low temperature and high hard water concentration conditions. Chinese patent application CN115894282A discloses a high-temperature-resistant bio-based zwitterionic surfactant and a preparation method thereof. The surfactant is prepared from oleic acid or its methyl ester as a raw material, and is sequentially subjected to alkylation reaction, amidation reaction and quaternization reaction. Compared with the prior art, the present application optimizes the alkylation technical route of double substitution of phenyl and fatty acid chain, and obtains a double alkyl benzene intermediate with a higher yield. The surfactant of the present application has good low-temperature solubility and hard water resistance when used alone, and exhibits better decontamination capacity than SDBS under high salinity hard water, and has the application potential of effective decontamination under harsh conditions such as low temperature and high concentration hard water. SUMMARY

[0004] The purpose of the present application is to provide a preparation and application of a calcium-magnesium-resistant single-aryl-linked gemini surfactant, which can exhibit good decontamination and hard water resistance without additional addition of a chelating agent, and can be used for washing and decontamination under high hard water concentration.

[0005] The purpose of the present application can be achieved by the following technical solutions:

[0006] The first aspect of the present application provides a preparation method of a mono-aryl linked gemini surfactant, comprising: mixing a phenyl-bis-undecanoic acid amide tertiary amine, a halogenated salt and sodium carbonate, and performing a quaternary ammonium reaction to obtain a phenyl-bis-undecanoic acid amide hydroxyl sulfonate (PH-2UHSB), i.e., a mono-aryl linked gemini surfactant.

[0007] Further, the molar ratio of the phenyl-bis-undecanoic acid amide tertiary amine, the halogenated salt and the sodium carbonate is 1:(1.05-5):(0.25-1.25); the halogenated salt is 3-chloro-2-hydroxypropanesulfonic acid sodium.

[0008] Further, in the quaternary ammonium reaction, the reaction temperature is 65-95 DEG C, the pH is 8-10, and the reaction time is 6-18 h.

[0009] Further, the preparation method of the phenyl-bis-undecanoic acid amide tertiary amine comprises: mixing phenyl-bis-undecanoic acid methyl ester and N,N-dimethyl-1,3-propanediamine, and performing an amidation reaction to obtain.

[0010] Further, the molar ratio of the phenyl-bis-undecanoic acid methyl ester and the N,N-dimethyl-1,3-propanediamine is 1:(1.2-6); in the amidation reaction, the reaction temperature is 100-160 DEG C, and the reaction time is 4-8 h.

[0011] Further, the preparation method of the phenyl-bis-undecanoic acid methyl ester comprises: mixing phenyl-undecanoic acid methyl ester, methyl undecenoate and methanesulfonic acid, and performing an alkylation reaction to obtain.

[0012] Further, the molar ratio of the phenyl-undecanoic acid methyl ester, the methyl undecenoate and the methanesulfonic acid is 1:(1-3):(3-12); in the alkylation reaction, the reaction temperature is 65-125 DEG C, and the reaction time is 4-10 h.

[0013] Further, the preparation method of the phenyl-undecanoic acid methyl ester comprises: mixing methyl undecenoate, benzene and methanesulfonic acid, and performing an alkylation reaction to obtain.

[0014] Further, the molar ratio of the methyl undecenoate, the benzene and the methanesulfonic acid is 1:(1-5):(2-8); in the alkylation reaction, the reaction temperature is 55-95 DEG C, and the reaction time is 4-8 h.

[0015] The second aspect of the present application provides an application of a mono-aryl linked gemini surfactant, comprising: using the mono-aryl linked gemini surfactant for hard water washing and stain removal.

[0016] Compared with the prior art, the present application has the following characteristics:

[0017] Compared with the prior art, the present application has the following characteristics:1) This invention uses methyl undecenoate, a renewable resource, as raw material to prepare phenyl bis-undecanamide salt through alkylation, amidation, quaternization and other reactions. Compared with the one-step reaction used in the traditional phenyl disubstituted alkylation, this invention adopts a two-step alkylation reaction route. The intermediate product methyl undecenoate is obtained by improving the activation at the para position, which can improve the conversion rate of phenyl disubstituted products.

[0018] 2) During surfactant washing, calcium and magnesium ions in the aqueous solution can combine with acid radicals in the surfactant molecules to form precipitates, reducing the surface activity of the surfactant solution. This necessitates the addition of chelating agents to bind the calcium and magnesium ions in the solution, achieving a good washing effect. However, excessive use of chelating agents is detrimental to environmental protection and product cost reduction. This invention uses a rigid benzene group as a spacer group, increasing the steric hindrance of the surfactant through π-π stacking, and introduces two sulfonic acid groups, improving the surfactant's water solubility and hard water resistance, making it more suitable for aqueous solutions with high calcium and magnesium ion concentrations. Compared to traditional washing with anionic surfactants like sodium dodecylbenzenesulfonate, this invention achieves good detergency even in solutions with high hard water concentrations without the need for additional chelating agents. Attached Figure Description

[0019] Figure 1 The EI mass spectrum (C10) of methyl phenyl undecanoate prepared in Example 1 is shown below. 18 H 28 O2, MW = 276.4126).

[0020] Figure 2 The EI mass spectrum (C10) of methyl phenyl diundecanedate prepared in Example 1 is shown below. 30 H 50 O4, MW = 474.3696).

[0021] Figure 3 The EI mass spectrum (C10) of the tertiary amine phenyldiundecanoic acid amide prepared in Example 1 is shown below. 38 H 70 N4O2 + Na + The m / z value is 637.5380; C 38 H70N4O2+2H + The m / z value is 308.2819.

[0022] Figure 4 The ESI mass spectrum (C1) of the phenyldiundecanoic acid amide hydroxysulfonate prepared in Example 1 is shown below. 44 H 82 N2O4(N + SO3)2+Na + m / z = 913.5350; C44 H 82 N2O4(N + SO3 - )2+2Na + of m / z = 468.2675).

[0023] Figure 5 Surface tension of phenyl bis-undecanoic amide hydroxyl sulfonate prepared in Example 1.

[0024] Figure 6 Stain removal power of phenyl bis-undecanoic amide hydroxyl sulfonate on different stains in deionized water.

[0025] Figure 7 Stain removal power of phenyl bis-undecanoic amide hydroxyl sulfonate on different stains in different concentrations of hard water. DETAILED DESCRIPTION

[0026] The application will be described in detail below with reference to the accompanying drawings and specific examples.

[0027] A phenyl bis-undecanoic amide hydroxyl sulfonate, whose synthetic route is shown as follows:

[0028]

[0029] First, a multi-substituted alkyl benzene mixture is prepared by alkylation using methyl undecenoate, methanesulfonic acid and benzene as reactants, and then phenyl bis-undecanoic methyl ester is obtained by column chromatography separation; then the phenyl bis-undecanoic methyl ester is mixed with N,N-dimethyl-1,3-propanediamine and subjected to amidation reaction to obtain phenyl bis-undecanoic amide tertiary amine; finally, the amidation reaction product is subjected to halogenation reaction with halide salt in solution to obtain phenyl bis-undecanoic amide hydroxyl sulfonate.

[0030] The specific preparation method steps are as follows:

[0031] S1: mono-substituted alkylation to prepare phenyl undecanoic methyl ester:

[0032] Methyl undecenoate, benzene and methanesulfonic acid are mixed and stirred at 55-95℃ for 4-8h, and then phenyl undecanoic methyl ester is obtained after separation and purification; wherein the molar ratio of methyl undecenoate, benzene and methanesulfonic acid is 1:(1-5):(2-8).

[0033] S2: di-substituted alkylation to prepare phenyl bis-undecanoic methyl ester:

[0034] Phenyl undecanoic methyl ester, methyl undecenoate and methanesulfonic acid are mixed and stirred at 65-125℃ for 4-10h, and then the di-substituted alkylation product is obtained after separation and purification; wherein the molar ratio of phenyl undecanoic methyl ester, methyl undecenoate and methanesulfonic acid is 1:(1-3):(3-12).

[0035] S3: Preparation of tertiary phenyldiundecanoic acid amide tertiary amine by amidation reaction:

[0036] Methyl phenyl undecanoate and N,N-dimethyl-1,3-propanediamine were mixed and heated to 100-160℃ and stirred for 4-8 hours. After separation and purification, phenyl didecanoate amide tertiary amine was obtained; wherein the molar ratio of methyl phenyl undecanoate and N,N-dimethyl-1,3-propanediamine was 1:(1.2-6).

[0037] S4: Quaternization reaction to prepare phenyldiundecanoic acid amide hydroxysulfonate:

[0038] A tertiary amine phenyldiundecanoic acid amide, a halide salt, and sodium carbonate are mixed in a solution and stirred at 65-95℃ and pH 8-10 for 6-18 hours. After separation and purification, phenyldiundecanoic acid amide hydroxysulfonate is obtained. The molar ratio of tertiary amine phenyldiundecanoic acid amide, halide salt, and sodium carbonate is 1:(1.05-5.0):(0.25-1.25). The halide salt is sodium 3-chloro-2-hydroxypropanesulfonate. The solution is a mixture of ethanol and water.

[0039] This embodiment is implemented based on the technical solution of the present invention, and provides detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiment.

[0040] The yield calculation formulas for each reaction in the following examples are as follows:

[0041]

[0042] In the formula, A 十一烯酸甲酯 A represents the total ion chromatography peak area of ​​monosubstituted alkylated methyl undecenoate by GC-MS; 苯基十一烯酸甲酯 The value represents the total ion chromatographic peak area of ​​monoalkylbenzenes after monosubstituted alkylation.

[0043]

[0044] In the formula, A 十一烯酸甲酯 A represents the LC-MS total ion chromatography peak area of ​​alkylated methyl undecanoate; 单取代产物 A represents the total ion chromatography peak area of ​​monoalkylbenzene after alkylation reaction; 双取代产物 A represents the total ion chromatographic peak area of ​​the disubstituted alkylbenzene after alkylation; 三取代产物 The value represents the total ion chromatographic peak area of ​​the trisubstituted alkylbenzene after alkylation.

[0045]

[0046] In the formula, A苯基双十一烯酸甲酯 Total ion chromatogram peak area of the bis-alkyl benzene after amidation reaction; A 苯基双十一烷基酰胺叔胺 Total ion chromatogram peak area of the bis-substituted amidation product after amidation reaction.

[0047]

[0048] wherein A 酰胺产物 Peak area of the amide product in the LC chromatogram after reaction; A 季铵产物 Peak area of the product in the LC chromatogram after reaction.

[0049] Example 1:

[0050] A phenyl bis-undecanoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0051] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 0.40 g (5.06 mmol) of benzene, and 1.46 g (15.18 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:1:3), and stir the mixture at 55°C under reflux for 4 h to perform an alkylation reaction. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecanoate, with a yield of 61.46%.

[0052] The EI mass spectrum of the methyl phenyl undecanoate is shown in Figure 1 .

[0053] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 1.01 g (5.06 mmol) of methyl undecylenate, and 1.46 g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) into a round-bottom flask, and stir the mixture at 65°C under reflux for 4 h to perform an alkylation reaction. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then separate and purify to obtain methyl phenyl bis-undecanoate with a content of 70.32%.

[0054] The EI mass spectrum of the methyl phenyl bis-undecanoate is shown in Figure 2 .

[0055] S3: Take 1.00 g (2.10 mmol) of methyl phenyl bis-undecanoate and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:1.2) into a round-bottom flask, and heat the mixture to 100°C for 4 h. After the reaction is completed, control the temperature to be 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform a reduced-pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, and obtain the product phenyl bis-undecanoic acid amide tertiary amine, with a yield of 73.76%.

[0056] The EI mass spectrum of the phenyl undecanoic acid amide tertiary amine is shown in Figure 4. Figure 3

[0057] S4: 0.43 g (2.20 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl undecanoic acid amide tertiary amine (molar ratio 1.05:0.25:1) and 30 mL of an ethanol / water solution (V 乙醇 水 =7:3) were added to a 50 mL HT-50FC flange reactor, stirring was started (1000 rpm) and the reaction was carried out at 65°C for 6 h. After the reaction was completed, ethanol and water were removed by evaporation, then the product was washed with 10 mL of ethyl acetate three times to remove the unreacted amide product, and then extracted with ethanol and centrifuged to obtain the supernatant. Ethanol was removed by rotary evaporation to obtain the final product, phenyl undecanoic acid amide hydroxyl sulfonate, with a content of 68.76%.

[0058] The EI mass spectrum of the phenyl undecanoic acid amide hydroxyl sulfonate is shown in Figure 4.

[0059] Example 2:

[0060] A phenyl undecanoic acid amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0061] S1: 1.00 g (5.06 mmol) of methyl undecylenate, 1.18 g (15.18 mmol) of benzene and 2.94 g (20.36 mmol) of methanesulfonic acid were added to a round-bottom flask (molar ratio 1:3:6), and the alkylating reaction was carried out by refluxing and stirring at 55°C for 6 h. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then the excess reaction benzene was evaporated to obtain the product, methyl phenyl undecanoate, with a yield of 75.53%.

[0062] S2: 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 3.01 g (15.18 mmol) of methyl undecylenate and 2.91 g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) were added to a round-bottom flask, and the alkylating reaction was carried out by refluxing and stirring at 65°C for 8 h. After the reaction was completed, ethyl acetate was added, the organic phase was washed with deionized water to a pH of about 6 to remove the methanesulfonic acid, and the double-substituted alkylated product was obtained after separation, with a content of 82.64%.

[0063] ​​S3: Take 1.00 g (2.10 mmol) of phenyl doundecanoic acid methyl ester and 0.65 g (6.30 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:3) into a round-bottom flask, and heat to 100°C for 6 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl doundecanoic acid amide tertiary amine with a yield of 86.63%.

[0064] S4: Take 1.24 g (6.30 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl doundecanoic acid amide tertiary amine (molar ratio 3:1:1), and 30 mL of an ethanol / water solution (V 乙醇 水 = 7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm), and react at 65°C for 10 h. After the reaction is completed, evaporate ethanol and water, then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove ethanol by rotary evaporation to obtain the final product phenyl doundecanoic acid amide hydroxyl sulfonate with a content of 80.34%.

[0065] Example 3:

[0066] A phenyl doundecanoic acid amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0067] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 1.97 g (25.3 mmol) of benzene, and 3.89 g (40.48 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:5:8), and perform an alkylation reaction by refluxing and stirring at 55°C for 8 h. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove methanesulfonic acid, and then evaporate excess benzene to obtain the product methyl phenyl undecanoate with a yield of 79.24%.

[0068] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 3.05 g (15.18 mmol) of methyl undecylenate, and 5.89 g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 65°C for 8 h. After the reaction is completed, add ethyl acetate, wash the organic phase with deionized water to a pH of about 6 to remove methanesulfonic acid, and obtain the double-substituted alkylation product with a content of 91.31% after separation.

[0069] ​S3: Take 1.00 g (2.10 mmol) of phenyl dodecanoic acid methyl ester and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:6) into a round bottom flask, and heat to 100°C for 8 hours. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl dodecanoic acid amide tertiary amine with a yield of 90.86%.

[0070] S4: Take 2.06 g (10.5 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.278 g (2.6 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl dodecanoic acid amide tertiary amine (molar ratio 5:1.25:1), and 30 mL of an ethanol / water solution (V 乙醇 水 =7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm), and react at 65°C for 18 hours. After the reaction is completed, evaporate the ethanol and water, then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl dodecanoic acid amide hydroxyl sulfonate with a content of 88.98%.

[0071] Example 4:

[0072] A phenyl dodecanoic acid amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0073] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 0.40 g (5.06 mmol) of benzene, and 1.46 g (15.18 mmol) of methanesulfonic acid into a round bottom flask (molar ratio 1:1:3), and perform an alkylation reaction by stirring at 75°C for 4 hours. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecanoate with a yield of 70.75%.

[0074] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 1.01 g (5.06 mmol) of methyl undecylenate, and 1.46 g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) into a round bottom flask, and perform an alkylation reaction by stirring at 95°C for 4 hours. After the reaction is completed, add ethyl acetate, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and obtain the disubstituted alkylation product with a content of 69.98% after separation.

[0075] ​S3: Take 1.00 g (2.10 mmol) of phenyl didecenoic acid methyl ester and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:1.2) into a round-bottom flask, and warm to 145°C for 4 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl didecenoic acid amide tertiary amine with a yield of 87.95%.

[0076] S4: Take 0.43 g (2.20 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl didecenoic acid amide tertiary amine (molar ratio 1.05:0.25:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, and start stirring (1000 rpm) and react at 85°C for 6 h. After the reaction is completed, evaporate the ethanol and water, and then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl didecenoic acid amide hydroxyl sulfonate with a content of 85.85%.

[0077] Example 5:

[0078] A phenyl didecenoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0079] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 1.18 g (15.18 mmol) of benzene, and 2.94 g (20.36 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:3:6), and perform an alkylation reaction by stirring at 75°C for 6 h. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecylenate with a yield of 78.34%.

[0080] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecylenate, 3.01 g (15.18 mmol) of methyl undecylenate, and 2.91 g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) into a round-bottom flask, and perform an alkylation reaction by stirring at 95°C for 8 h. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid to obtain a double-substituted alkylation product with a content of 86.87% after separation.

[0081] S3: Take 1.00 g (2.10 mmol) of phenyl didecenoic acid methyl ester and 0.65 g (6.30 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:3) into a round-bottom flask, and heat to 145°C for 6 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl didecanoic acid amide tertiary amine with a yield of 92.53%.

[0082] S4: Take 1.24 g (6.30 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl didecanoic acid amide tertiary amine (molar ratio 3:1:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, and start stirring (1000 rpm) and react at 85°C for 10 h. After the reaction is completed, evaporate the ethanol and water, and then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl didecanoic acid amide hydroxyl sulfonate with a content of 90.65%.

[0083] Example 6:

[0084] A phenyl didecanoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0085] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 1.97 g (25.3 mmol) of benzene, and 3.89 g (40.48 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:5:8), and perform an alkylation reaction by refluxing and stirring at 75°C for 8 h. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecanoate with a yield of 96.75%.

[0086] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 3.05 g (15.18 mmol) of methyl undecylenate, and 5.89 g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 95°C for 8 h. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid to obtain a double-substituted alkylation product with a content of 97.31% after separation.

[0087] S3: Take 1.00 g (2.10 mmol) of phenyl didecenoic acid methyl ester and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:6) into a round bottom flask, and heat to 145°C for 8 hours. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl didecanoic acid amide tertiary amine with a yield of 91.23%.

[0088] S4: Take 2.06 g (10.5 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.278 g (2.6 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl didecanoic acid amide tertiary amine (molar ratio 5:1.25:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, and start stirring (1000 rpm) and react at 65°C for 18 hours. After the reaction is completed, evaporate the ethanol and water, and then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl didecanoic acid amide hydroxyl sulfonate with a content of 92.88%.

[0089] Example 7:

[0090] A phenyl didecanoic acid amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0091] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 0.40 g (5.06 mmol) of benzene, and 1.46 g (15.18 mmol) of methanesulfonic acid into a round bottom flask (molar ratio 1:1:3), and perform an alkylation reaction by refluxing and stirring at 95°C for 4 hours. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecanoate with a yield of 95.35%.

[0092] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecanoate, 1.01 g (5.06 mmol) of methyl undecylenate, and 1.46 g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) into a round bottom flask, and perform an alkylation reaction by refluxing and stirring at 125°C for 4 hours. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid to obtain a double-substituted alkylation product with a content of 77.57% after separation.

[0093] S3: Take 1.00 g (2.10 mmol) of phenyl didecenoic acid methyl ester and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:1.2) into a round-bottom flask, and heat to 160°C for 4 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl didecenoic acid amide tertiary amine with a yield of 93.64%.

[0094] S4: Take 0.43 g (2.20 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl didecenoic acid amide tertiary amine (molar ratio 1.05:0.25:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm), and react at 95°C for 6 h. After the reaction is completed, evaporate ethanol and water, then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove ethanol by rotary evaporation to obtain the final product phenyl didecenoic acid amide hydroxyl sulfonate with a content of 87.97%.

[0095] Example 8:

[0096] A phenyl didecenoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0097] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 0.39 g (5.06 mmol) of benzene, and 1.45 g (15.18 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:1:3), and perform an alkylation reaction by stirring at 95°C for 6 h. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove methanesulfonic acid, and then evaporate excess benzene to obtain the product methyl phenyl undecylenate with a yield of 97.01%.

[0098] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecylenate, 3.01 g (15.18 mmol) of methyl undecylenate, and 2.91 g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) into a round-bottom flask, and perform an alkylation reaction by stirring at 125°C for 8 h. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove methanesulfonic acid to obtain a double-substituted alkylation product with a content of 87.86% after separation.

[0099] S3: Take 1.00 g (2.10 mmol) of phenyl didecenoic acid methyl ester and 0.65 g (6.30 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:3) into a round-bottom flask, and heat to 160°C for 6 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove unreacted N,N-dimethyl-1,3-propanediamine to obtain the product phenyl didecenoic acid amide tertiary amine with a yield of 94.88%.

[0100] S4: Take 1.24 g (6.30 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl didecenoic acid amide tertiary amine (molar ratio 3:1:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, and start stirring (1000 rpm) and react at 95°C for 10 h. After the reaction is completed, evaporate the ethanol and water, and then wash the product with 10 mL of ethyl acetate three times to remove unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl didecenoic acid amide hydroxyl sulfonate with a content of 83.67%.

[0101] Example 9:

[0102] A phenyl didecenoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0103] S1: Take 1.00 g (5.06 mmol) of methyl undecylenate, 1.97 g (25.3 mmol) of benzene, and 3.89 g (40.48 mmol) of methanesulfonic acid into a round-bottom flask (molar ratio 1:5:8), and perform an alkylation reaction by stirring at 95°C for 8 h. After the reaction is completed, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reaction benzene to obtain the product methyl phenyl undecylenate with a yield of 98.79%.

[0104] S2: Take 1.00 g (5.06 mmol) of methyl phenyl undecylenate, 3.05 g (15.18 mmol) of methyl undecylenate, and 5.89 g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) into a round-bottom flask, and perform an alkylation reaction by stirring at 125°C for 8 h. After the reaction is completed, add ethyl acetate, and wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid to obtain the double-substituted alkylation product with a content of 97.45% after separation.

[0105] S3: Take 1.00 g (2.10 mmol) of phenyl-bis-undecanoic acid methyl ester and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:6) into a round bottom flask, and heat to 160°C for 8 h. After the reaction is completed, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to remove the unreacted N,N-dimethyl-1,3-propanediamine by vacuum distillation to obtain the product phenyl-bis-undecanoic acid amide tertiary amine with a yield of 96.86%.

[0106] S4: Take 2.06 g (10.5 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.278 g (2.6 mmol) of sodium carbonate, 1.29 g (2.10 mmol) of phenyl-bis-undecanoic acid amide tertiary amine (molar ratio 5:1.25:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm), and react at 95°C for 18 h. After the reaction is completed, evaporate the ethanol and water, then wash the product with 10 mL of ethyl acetate three times to remove the unreacted amide product, and then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product phenyl-bis-undecanoic acid amide hydroxyl sulfonate with a content of 84.96%.

[0107] Example 10:

[0108] This experiment aims to evaluate the surface tension of PH-2UHSB prepared by Example 6 and its anti-stability to hard water in solution. The surface tension of PH-2UHSB is measured according to the pendant drop method, and the results are shown in Table 1, Figure 5 The anti-calcium and magnesium ion resistance of the surfactant is evaluated according to the standard GB.T7381-2010 "Determination of the stability of surfactants in hard water", and the results are shown in Table 2.

[0109] Table 1 Anti-hard water stability of surfactants

[0110]

[0111] Table 2 Anti-hard water stability of surfactants

[0112]

[0113] From Table 1, it can be seen that the CMC of PH-2UHSB prepared by Example 6 can reach 10 -5 mN / m, which is one order of magnitude lower than that of SDBS, and PH-2UHSB has a strong ability to form micelles in solution, with a surface tension of 34.45 mN / m, which is lower than that of SDBS. PH-2UHSB has good surface activity and can effectively reduce the surface tension. In addition, the Γmax less than SDBS, A min greater than SDBS, because the spacer group of Ph-2UHSB contains a rigid structure of benzene ring, the molecule is less curved at the interface, the single Ph-2UHSB molecule occupies a larger area at the interface, and the arrangement is looser. As can be seen from Table 1, the critical micelle concentration of the surfactant is and all less than zero, indicating that PH-2UHSB has a strong surface adsorption and micellization trend, and the micellization process and adsorption process of the surfactant molecule in the aqueous solution are spontaneous.

[0114] As can be seen from Table 2, the hard water stability of the synthesized zwitterionic surfactant is higher than that of the commonly used anionic surfactant sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), and the hard water stability of Ph-2UHSB is 5. Compared with anionic surfactants, zwitterionic surfactants have better hard water resistance. In addition, the surfactant molecules in the solution exist in the form of micellar structure, and the counterions are adsorbed on the surface of the micelles. The tighter the micelles formed, the less the water solubility of the surfactant is affected by the counterions. The introduction of phenyl group into the hydrophobic end of Ph-2UHSB molecule enhances the ability of the surfactant to form micelles, and has good stability in hard water. In addition, the gemini surfactant has two hydrophilic groups, which can form complex with Ca 2+ and Mg 2+ to make its hard water solubility significantly better than traditional single-chain surfactants.

[0115] Example 11:

[0116] This example is used to test the detergency of PH-2UHSB prepared in Example 6. A constant temperature stirring device is used to simulate the washing process to evaluate the detergency of the surfactant on different stains and the detergency on stains under different hard water concentrations. The experimental steps are as follows: a 6 cm x 6 cm standard white cloth is placed in a 37°C oven until the weight is constant, and the mass is recorded as B. Selecting motor oil, soybean oil, corn oil, ink, ketchup and yogurt (the motor oil used in this example is purchased from Speedmax (Shanghai) Petroleum Chemical Co., Ltd., and the soybean oil (Jinlongyu), corn oil (Jinlongyu), ink (Hero), ketchup (Hennessy) and yogurt (Junlebao) are all commercially available products) as stains, which are evenly applied on the cotton cloth, and then placed in a 37°C oven to dry until the weight is constant, to obtain the stained cloth, and the mass is recorded as A. Take the prepared stained cloth into 200 mL test solution, stir at 30°C and 200 rpm for 30 min, rinse the washed cotton sheet with tap water for 1 min, then place it in a 37°C oven to dry until the weight is constant, and record the mass as C. The final detergency of the surfactant is calculated by the following formula, and each group of experiments is repeated three times to take the average value:

[0117]

[0118] In order to study the hard water resistance of the synthesized surfactant as a cleaning agent in more detail, the oil removal rates of the surfactants in tap water, 250 mg / kg, 500 mg / kg hard water of different concentrations were further tested.

[0119] The results of the test are shown in Figure 6 , Figure 7 It can be seen from Figure 6 that the oil removal rate of PH-2UHSB is equivalent to that of SDBS without the addition of calcium and magnesium ions, and it has a better oil removal effect on soybean oil and motor oil than pure water washing. Figure 7 It can be seen that as the hard water concentration of the prepared solution increases to 500 mg / L, the oil removal rate of SDBS decreases significantly, from 90.18% to 67.83%, a decrease of 22.35%. PH-2UHSB has good hard water resistance, and as the hard water concentration increases, the oil removal rate does not decrease significantly, and the oil removal rate is more than 80%. Compared with SDBS, PH-2UHSB has good hard water resistance, and has good oil removal effect in high salinity water solution without the need for additional chelating agent.

[0120] The above description of the embodiments is for the convenience of those skilled in the art to understand and use the invention. Those skilled in the art can easily make various modifications to these embodiments, and apply the general principles described herein to other embodiments without creative labor. Therefore, the present application is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art according to the disclosure of the present application without departing from the scope of the present application should be within the scope of protection of the present application.

Claims

1. A method for preparing a monoaryl-linked gemini surfactant, characterized in that, The method includes: Methyl undecanoate, benzene, and methanesulfonic acid are mixed and alkylated to give methyl phenyl undecanoate, which has the following structural formula: ； Methyl phenyl undecanoate, methyl undecenoate, and methanesulfonic acid are mixed and alkylated to give methyl phenyl diundecanoate, which has the following structural formula: ； Methyl phenyldiseudecanoate and N,N-dimethyl-1,3-propanediamine were mixed and subjected to an amidation reaction to give tertiary phenyldiseudecanoate amide, which has the following structural formula: ； A mixture of phenyldiundecanoic acid amide tertiary amine, a halide salt, and sodium carbonate is subjected to a quaternization reaction to yield phenyldiundecanoic acid amide hydroxysulfonate, a monoaryl-linked gemini surfactant, which has the following structural formula: ； or ； The halosalt is sodium 3-chloro-2-hydroxypropanesulfonate, and the methyl undecenoate is methyl 10-undecenoate.

2. The method for preparing a monoaryl-linked gemini surfactant according to claim 1, characterized in that, The molar ratio of the phenyldiundecanoic acid amide tertiary amine, halosalt, and sodium carbonate is 1:(1.05-5):(0.25-1.25).

3. The method for preparing a monoaryl-linked gemini surfactant according to claim 1, characterized in that, In the quaternization reaction, the reaction temperature is 65-95℃, the pH is 8-10, and the reaction time is 6-18 h.

4. The method for preparing a monoaryl-linked gemini surfactant according to claim 1, characterized in that, The molar ratio of methyl phenyl diundecanedioate to N,N-dimethyl-1,3-propanediamine is 1:(1.2-6); in the amidation reaction, the reaction temperature is 100-160℃ and the reaction time is 4-8 h.

5. The method for preparing a monoaryl-linked gemini surfactant according to claim 1, characterized in that, The molar ratio of methyl phenyl undecanoate, methyl undecenoate, and methanesulfonic acid is 1:(1-3):(3-12); in the alkylation reaction, the reaction temperature is 65-125℃ and the reaction time is 4-10 h.

6. The method for preparing a monoaryl-linked gemini surfactant according to claim 1, characterized in that, The molar ratio of undecenoic acid methyl ester, benzene, and methanesulfonic acid is 1:(1-5):(2-8); in the alkylation reaction, the reaction temperature is 55-95℃ and the reaction time is 4-8 h.

7. The application of a monoaryl-linked gemini surfactant prepared by the method according to any one of claims 1 to 6, characterized in that, The monoaryl-linked gemini surfactant is used for hard water washing and stain removal.

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