Diphenylmethane-based undecanoic acid amide hydroxysulfonate salts, their preparation and use

Abstract

The application belongs to the technical field of washing and decontamination, and relates to a diphenylmethane-based diundecanoic amide hydroxyl sulfonate (DiPH-2UHSB) and a preparation method and application thereof. The preparation method comprises the following steps: mixing diphenylmethane-based diundecanoic amide tertiary amine, a halide salt and sodium carbonate in a solution, and performing quaternary ammonium reaction to obtain the product. Compared with the prior art, the DiPH-2UHSB prepared by the application has excellent decontamination and hard water resistance, and can still maintain such performance under high hard water concentration 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 diphenylmethane-based bisundecanoic acid amide hydroxyl sulfonate as well as a preparation method and application thereof. BACKGROUND

[0002] In the washing industry, surfactants are one of the main components of detergents, because surfactants have high surface activity, good wetting, emulsifying and dispersing, foaming and defoaming, and solubilizing properties. This makes them exhibit high dissolution capacity on water-insoluble substances. According to the composition and structure, surfactants can be divided into cationic, anionic, zwitterionic and non-ionic surfactants. At present, the most widely used in the washing field is anionic surfactants, such as sodium dodecyl benzene sulfonate (SDBS), alkyl naphthalene sulfonate, succinate sulfonate and the like, but the anionic surfactants are easily affected by counterions in the solution, when the water hardness increases, SDBS combines with calcium and magnesium ions in water to precipitate, and the solution decontamination capacity greatly decreases, and the general solution method is to add a chelating agent for compounding. The second is the non-ionic surfactant, such as fatty alcohol polyoxyethylene ether (AEO), etc., the cloud point of AEO is high, and the solubility in the aqueous solution is limited, and it is often compounded with a solubilizing agent or with other surfactants, the cationic surfactant has a sterilization and disinfection effect, and is generally less than the detergent. The zwitterionic surfactant is relatively less in the surfactant washing field.

[0003] In order to cope with the problems of high salinity water, low or high temperature, strong acid, strong base, strong oxidant and other extreme environmental problems in washing, some chemically stable surfactants such as secondary alkyl sulfonate, alkyl diphenyl ether sulfonate and fluorosilicon are synthesized. Among them, the alkyl diphenyl ether sulfonate has two sulfonic acid hydrophilic groups, good water solubility at low temperature, strong resistance to hard water, and can reduce the use of chelating agents and solubilizing agents, but the raw material in the synthesis process of the alkyl diphenyl ether sulfonate is alpha-olefin, which is mostly from non-renewable petrochemical products, and the two hydrophilic head groups are obtained by sulfonation reaction of sulfur trioxide, the reaction is violent and difficult to control, and there is a safety risk, and unreacted sulfur trioxide also easily pollutes the environment. SUMMARY

[0004] The purpose of the present application is to provide a diphenylmethane-based bisundecanoic acid amide hydroxyl sulfonate as well as a preparation method and application thereof, the product has excellent decontamination and hard water resistance, and can still maintain this performance under high hard water concentration without additional addition of a chelating agent.

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

[0006] The application uses methyl undecylenate obtained by castor oil cracking as a reaction raw material instead of alpha-olefin, and the reaction raw material is green and renewable. A halogenated salt is used instead of sulfur trioxide to introduce a sulfonate group, and the reaction is stable and controllable, avoiding the generation of acidic waste; the synthetic surfactant has two hydrophilic head groups, has good water solubility, and has a diphenylmethane introduced in the spacer group, and there is a pi-pi conjugation between the aromatic groups, so that the surfactant micelle is stable, has good hard water resistance, and has application potential in low-temperature and high-hard water concentration conditions.

[0007] The first aspect of the application provides a preparation method of diphenylmethane-based diundecanoic amide hydroxyl sulfonate, characterized in that the method comprises: mixing diphenylmethane-based diundecanoic amide tertiary amine, a halogenated salt and sodium carbonate in a solution, and performing quaternary ammonium reaction to obtain diphenylmethane-based diundecanoic amide hydroxyl sulfonate (DiPh-2UHSB).

[0008] Further, the molar ratio of the diphenylmethane-based diundecanoic amide tertiary amine, the halogenated salt and the sodium carbonate is 1:(1.05-5.0):(0.25-1.25).

[0009] Further, the halogenated salt is 3-chloro-2-hydroxypropanesulfonic acid sodium.

[0010] Further, in the quaternary ammonium reaction, the reaction temperature is 65-115 DEG C, the reaction time is 6-18 h, and pH=8-10.

[0011] Further, the preparation method of the diphenylmethane-based diundecanoic amide tertiary amine comprises: mixing diphenylmethane-based diundecanoic methyl ester and N,N-dimethyl-1,3-propanediamine, and performing amide reaction to obtain.

[0012] Further, the molar ratio of the diphenylmethane-based diundecanoic methyl ester and the N,N-dimethyl-1,3-propanediamine is 1:(1.2-6); in the amide reaction, the reaction temperature is 100-160 DEG C, and the reaction time is 4-8 h.

[0013] Further, the preparation method of the diphenylmethane-based diundecanoic methyl ester comprises: mixing diphenylmethane, methyl undecylenate and methanesulfonic acid, and performing double-substituted alkyl reaction to obtain.

[0014] Further, the molar ratio of the diphenylmethane, the methyl undecylenate and the methanesulfonic acid is 1:(1-6):(3-12); in the double-substituted alkyl reaction, the reaction temperature is 55-125 DEG C, and the reaction time is 5-10 h.

[0015] The second aspect of the application provides a diphenylmethane-based diundecanoic amide hydroxyl sulfonate prepared by the method described above.

[0016] The third aspect of the present application provides an application of a diphenylmethane-based bisundecanoic amide hydroxysulfate, including washing a diphenylmethane-based bisundecanoic amide hydroxysulfate hard water to remove dirt.

[0017] Compared with the prior art, the present application has the following characteristics:

[0018] 1) The present application uses renewable resource methyl undecylenate as raw material, and diphenylmethane-based bisundecanoic amide salt is prepared through alkylation, amidation, and quaternary ammonium reaction, a new route for developing biological-based raw material methyl undecylenate is developed, and the development and application of environmental protection and biological-based raw material are promoted.

[0019] 2) In the surfactant washing process, the calcium and magnesium ions in the aqueous solution can combine with the acid radical ions in the surfactant molecules to form a precipitate, which reduces the surface activity of the surfactant solution, and an additional chelating agent is needed to combine with the calcium and magnesium ions in the solution to make the surfactant solution washing achieve good results, and the overuse of the chelating agent is not conducive to environmental protection and reducing product cost. The present application uses a rigid group diphenylmethane as a spacer group, the ππ stacking increases the steric hindrance of the surfactant, and two sulfonic acid groups are introduced, which improves the water solubility and hardness resistance of the surfactant, and is more suitable for aqueous solutions with high calcium and magnesium ions. Compared with the traditional anionic surfactant SDBS, the product of the present application can achieve good dirt removal effect in a solution with high hard water concentration without additional addition of a chelating agent. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The EI mass spectrum of the diphenylmethane-based bisundecanoic amide hydroxysulfate prepared in Example 1 (C 51 H 89 N2O4(N + SO3)2+Na + The m / z of C 51 H 89 N2O4(N + SO3)2+2Na+ is 513.2909);

[0021] Figure 2 The EI mass spectrum of the diphenylmethane-based bisundecanoic amide hydroxysulfate prepared in Example 1 (C 45 H 76 N4O2+H + The m / z of C 45 H 76 N4O2+2H + The m / z of C

[0022] Figure 3ESI mass spectrum of the diphenylmethane-based bis-undecanoic acid amide hydroxyl sulfonate prepared in Example 1 (C 37 H 56 O4+H + m / z of 565.4242; C 37 H 56 O4+Na + m / z of 587.4062);

[0023] Figure 4 a graph showing the change of surface tension of the diphenylmethane-based bis-undecanoic acid amide hydroxyl sulfonate with concentration;

[0024] Figure 5 a stain removal power of the diphenylmethane-based bis-undecanoic acid amide hydroxyl sulfonate on different stains in deionized water;

[0025] Figure 6 a stain removal power of the diphenylmethane-based bis-undecanoic acid amide hydroxyl sulfonate on stains in different hard water concentrations. DETAILED DESCRIPTION

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

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

[0028]

[0029] First, the diphenylmethane-based bis-undecanoic acid methyl ester is obtained by alkylation with methyl undecylenate, methanesulfonic acid and diphenylmethane as reactants; then, the diphenylmethane-based bis-undecanoic acid amide tertiary amine is prepared by mixing the diphenylmethane-based bis-undecanoic acid methyl ester with N,N-dimethyl-1,3-propanediamine and performing an amidation reaction; finally, the diphenylmethane-based bis-undecanoic acid amide hydroxyl sulfonate (DiPH-2UHSB) is obtained by reacting the amidation reaction product with a halide salt in a solution.

[0030] The specific preparation method includes the following steps:

[0031] S1: bisubstituted alkylation to prepare diphenylmethane-based bis-undecanoic acid methyl ester:

[0032] The diphenylmethane, methyl undecylenate and methanesulfonic acid are mixed and heated to 55-125°C for reaction and stirring for 5-10h, and the bisubstituted alkylation product, diphenylmethane-based bis-undecanoic acid methyl ester, is obtained after separation and purification; wherein the molar ratio of diphenylmethane, methyl undecylenate and methanesulfonic acid is 1:(1-6):(3-12).

[0033] S2: amidation reaction to prepare diphenylmethane-based bis-undecanoic acid amide tertiary amine:

[0034] Mixing methyldiphenylmethane undecylenate and N,N-dimethyl-1,3-propanediamine, and stirring at 100-160℃ for 4-8h to obtain diphenylmethane bisundecanoic acid amide tertiary amine after separation and purification; wherein the molar ratio of methyldiphenylmethane undecylenate and N,N-dimethyl-1,3-propanediamine is 1:(1.2-6).

[0035] S3: preparing diphenylmethane bisundecanoic acid amide hydroxysulfate by quaternary ammonium reaction:

[0036] Mixing diphenylmethane bisundecanoic acid amide tertiary amine, halide salt and sodium carbonate in a solution, and stirring at 65-115℃ for 6-18h to obtain diphenylmethane bisundecanoic acid amide hydroxysulfate after separation and purification; wherein the molar ratio of diphenylmethane bisundecanoic acid amide tertiary amine, halide salt and sodium carbonate is 1:(1.05-5.0):(0.25-1.25); the halide salt is 3-chloro-2-hydroxypropanesulfonic acid sodium; the solution is a mixed solution of ethanol and water.

[0037] This embodiment is implemented on the premise of the technical scheme of the present application, and gives detailed implementation modes and specific operation processes, but the protection scope of the present application is not limited to the following examples.

[0038] The yield calculation formula of each reaction in the following examples is as follows:

[0039]

[0040] In the formula, A 十一烯酸甲酯 is the LC-MS total ion chromatographic peak area of methyl undecylenate after alkylation; A 单取代产物 is the LC-MS total ion chromatographic peak area of monoalkyl diphenylmethane after alkylation reaction; A 双取代产物 is the LC-MS total ion chromatographic peak area of disubstituted alkyl diphenylmethane after alkylation reaction; A 三取代产物 is the LC-MS total ion chromatographic peak area of trisubstituted alkyl diphenylmethane after alkylation reaction.

[0041]

[0042] In the formula, A 二苯甲烷基双十一烯酸甲酯 is the LC-MS total ion chromatographic peak area of bisalkyl diphenylmethane after amidation reaction; A 二苯甲烷基双十一烷基酰胺叔胺 is the LC-MS total ion chromatographic peak area of disubstituted amidation product after amidation reaction.

[0043]

[0044] In the formula, A 酰胺产物 is the peak area of the amide product in the LC chromatogram after the reaction; A 季铵产物Peak area of product in post-reaction LC chromatogram.

[0045] Example 1:

[0046] A diphenylmethane-based bisundecanoic acid amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0047] S1: Take 1.97 g (25.3 mmol) of methyl undecylenate, 4.24 g (25.3 mmol) of diphenylmethane, and 3.67 g (38.1 mmol) of methanesulfonic acid (molar ratio of 1:1:12), and carry out reflux stirring at 55°C to carry out alkylation reaction, and the reaction time is 6 hours. After the reaction is completed, the methanesulfonic acid is removed by washing the organic phase with deionized water to about pH 6, and then the excess reactants are evaporated to obtain a disubstituted alkylation product with a yield of 58.64%.

[0048] The EI mass spectrum of the diphenylmethane-based bisundecanoic acid methyl ester is as shown in Figure 1 .

[0049] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based bisundecanoic acid methyl ester and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio of 1:1.2), and add them to a round-bottom flask, and heat to 100°C for 4 hours. Subsequently, control the temperature at 155°C, and slowly reduce the pressure to -0.10 MPa using a vacuum pump to carry out reduced pressure distillation to remove unreacted N,N-dimethyl-1,3-propanediamine, and finally obtain the product diphenylmethane-based bisundecanoic acid amide tertiary amine with a yield of 94.99%.

[0050] The EI mass spectrum of the diphenylmethane-based bisundecanoic acid amide tertiary amine is as shown in Figure 2 .

[0051] S3: Take 0.43 g (2.2 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based bisundecanoic acid amide tertiary amine (molar ratio of 1.05:0.25:1), and add them to a 50-mL HT-50FC flange reaction kettle, and add 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3). Stir at 65°C for 6 hours (stirring speed of 1000 rpm). 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 then centrifuge and take the supernatant. Remove the ethanol by rotary evaporation, and finally obtain the product, i.e., diphenylmethane-based bisundecanoic acid amide hydroxyl sulfonate, with a content of 69.73%.

[0052] The ESI mass spectrum of the diphenylmethane-based bisundecanoic amide hydroxyl sulfonate is shown in FIG. 3.

[0053] Example 2

[0054] A diphenylmethane-based bisundecanoic amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0055] S1: Take 7.54 g (38.10 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 73.15 g (76.20 mmol) of methanesulfonic acid (molar ratio 3:1:6) into a round-bottom flask, and stir the reaction at 55°C for 8 h to perform the 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 reactants to obtain a double-substituted alkylation product, which has a content of 78.89% after separation and purification.

[0056] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based bisundecanoic methyl ester and 0.86 g (8.4 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1:4) into a round-bottom flask, and heat to 100°C for 6 h. After the reaction is completed, control the temperature to 155°C, and slowly reduce the pressure to -0.10 MPa with a vacuum pump to perform vacuum distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, thereby obtaining the product diphenylmethane-based bisundecanoic amide tertiary amine, which has a yield of 80.09%.

[0057] S3: Take 1.24 g (6.20 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based bisundecanoic 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 65°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 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 diphenylmethane-based bisundecanoic amide hydroxyl sulfonate, which has a content of 71.63%.

[0058] Example 3

[0059] A diphenylmethane-based bisundecanoic amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0060] S1 : Take 15.125 g (76.20 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane and 14.63 g (152.4 mmol) of methanesulfonic acid (molar ratio 6:1 :12) into a round bottom flask, stir the reaction at 55°C for 10 h to carry out the alkylation reaction. After the reaction is completed, wash the organic phase with deionized water to pH around 6 to remove methanesulfonic acid, then evaporate the excess reactants to obtain the disubstituted alkylation product, which has a content of 78.89% after separation.

[0061] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based methyl undecylenate and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio 1 :6) into a round bottom flask, heat to 100°C for 8 h. After the reaction is completed, control the temperature at 155°C, slowly reduce the pressure to -0.10 MPa with a vacuum pump to carry out the reduced pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine to obtain the product diphenylmethane-based undecylenic acid amide tertiary amine with a yield of 94.99%.

[0062] S3: Take 1.23 g (6.25 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.28 g (2.63 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecylenic acid amide tertiary amine (molar ratio 5:1.25:1) and 30 mL of ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm) and react at 65°C for 18 h. After the reaction is completed, evaporate to remove ethanol and water, then wash the product with 10 mL of ethyl acetate for three times to remove the unreacted amide product, then extract with ethanol and centrifuge to obtain the supernatant. Remove ethanol by rotary evaporation to obtain the final product diphenylmethane-based undecylenic acid amide hydroxyl sulfonate with a content of 75.62%.

[0063] Example 4

[0064] A diphenylmethane-based undecylenic acid amide hydroxyl sulfonate, the preparation method comprising the following steps:

[0065] S1 : Take 15.125 g (76.20 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane and 14.63 g (152.4 mmol) of methanesulfonic acid (molar ratio 6:1 :12) into a round bottom flask, stir the reaction at 55°C for 10 h to carry out the alkylation reaction. After the reaction is completed, wash the organic phase with deionized water to pH around 6 to remove methanesulfonic acid, then evaporate the excess reactants to obtain the disubstituted alkylation product, which has a content of 78.89% after separation.

[0066] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based methyl 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 to 145°C for 4 h. After the reaction is completed, control the temperature to 155°C, slowly reduce the pressure to -0.10 MPa with a vacuum pump, and perform vacuum distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine to obtain the product diphenylmethane-based undecanoic amide tertiary amine with a yield of 94.99%.

[0067] S3: Take 0.43 g (2.2 mmol) of 3-chloro-2-hydroxypropanesulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic 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 85°C for 6 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, centrifuge, and take the supernatant. Remove the ethanol by rotary evaporation to obtain the final product diphenylmethane-based undecanoic amide hydroxyl sulfonate with a content of 78.21%.

[0068] Example 5

[0069] A diphenylmethane-based undecanoic amide hydroxyl sulfonate, a preparation method thereof comprising the following steps:

[0070] S1: Take 7.54 g (38.10 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 73.15 g (76.20 mmol) of methanesulfonic acid (molar ratio 3:1:6) 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, wash the organic phase with deionized water to a pH of about 6 to remove the methanesulfonic acid, and then evaporate the excess reactants to obtain a disubstituted alkylation product with a content of 78.98% after separation.

[0071] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based methyl 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 to 145°C for 4 h. After the reaction is completed, control the temperature to 155°C, slowly reduce the pressure to -0.10 MPa with a vacuum pump, and perform vacuum distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine to obtain the product diphenylmethane-based undecanoic amide tertiary amine with a yield of 88.64%.

[0072] S3: Take 1.24 g (6.20 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic acid amide tertiary amine (molar ratio of 3:1:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reactor, start stirring (1000 rpm), and react at a temperature of 85°C for 10 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 diphenylmethane-based undecanoic acid amide hydroxyl sulfonate with a content of 78.64%.

[0073] Example 6

[0074] A diphenylmethane-based undecanoic acid amide hydroxyl sulfonate, the preparation method thereof comprising the following steps:

[0075] S1: Take 15.125 g (76.20 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 14.63 g (152.4 mmol) of methanesulfonic acid (molar ratio of 6:1:12) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 95°C for 10 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 reactants to obtain a disubstituted alkylation product with a content of 86.89% after separation.

[0076] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based undecanoic acid methyl ester and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio of 1:6) into a round-bottom flask, and react at a temperature of 145°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 perform a reduced-pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, thereby obtaining the product diphenylmethane-based undecanoic acid amide tertiary amine with a yield of 93.98%.

[0077] S3: Take 1.23 g (6.25 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium salt, 0.28 g (2.63 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic acid amide tertiary amine (molar ratio of 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 a temperature of 85°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 diphenylmethane-based undecanoic acid amide hydroxyl sulfonate with a content of 71.67%.

[0078] Example 7

[0079] A diphenylmethane-based undecanoic acid amide hydroxyl sulfonate, the preparation method thereof comprising the following steps:

[0080] S1: Take 1.97 g (25.3 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 7.315 g (76.20 mmol) of methanesulfonic acid (molar ratio of 2:1:6) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 125°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 reactants to obtain a disubstituted alkylation product with a content of 80.21% after separation.

[0081] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based undecanoic acid methyl ester and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio of 1:1.2) into a round-bottom flask, and react at a temperature of 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 a reduced-pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, thereby obtaining the product diphenylmethane-based undecanoic acid amide tertiary amine with a yield of 95.65%.

[0082] S3: Take 0.43 g (2.2 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium salt, 0.056 g (0.53 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic acid amide tertiary amine (molar ratio of 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 a temperature of 115°C for 6 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 diphenylmethane-based undecanoic acid amide hydroxyl sulfonate with a content of 71.24%.

[0083] Example 8

[0084] A diphenylmethane-based undecanoic acid amide hydroxyl sulfonate, the preparation method thereof comprising the following steps:

[0085] S1: Take 7.54 g (38.10 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 73.15 g (76.20 mmol) of methanesulfonic acid (molar ratio of 3:1:6) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 125°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 reactants to obtain a disubstituted alkylation product with a content of 82.89% after separation.

[0086] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based undecanoic acid methyl ester and 0.26 g (2.52 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio of 1:1.2) into a round-bottom flask, and react at a temperature of 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 a reduced-pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, thereby obtaining the product diphenylmethane-based undecanoic acid amide tertiary amine with a yield of 93.21%.

[0087] S3: Take 1.24 g (6.20 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium salt, 0.222 g (2.1 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic acid amide tertiary amine (molar ratio of 3:1:1), and 30 mL of an ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reactor, start stirring (1000 rpm), and react at a temperature of 115°C for 10 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 diphenylmethane-based undecanoic acid amide hydroxyl sulfonate with a content of 76.64%.

[0088] Example 9

[0089] A diphenylmethane-based undecanoic acid amide hydroxyl sulfonate, the preparation method thereof comprising the following steps:

[0090] S1: Take 15.125 g (76.20 mmol) of methyl undecylenate, 2.12 g (12.70 mmol) of diphenylmethane, and 14.63 g (152.4 mmol) of methanesulfonic acid (molar ratio of 6:1:12) into a round-bottom flask, and perform an alkylation reaction by refluxing and stirring at 125°C for 10 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 reactants to obtain a disubstituted alkylation product with a content of 85.90% after separation.

[0091] S2: Take 1.20 g (2.10 mmol) of diphenylmethane-based undecanoic acid methyl ester and 1.29 g (12.6 mmol) of N,N-dimethyl-1,3-propanediamine (molar ratio of 1:6) into a round-bottom flask, and react at a temperature of 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 perform a reduced-pressure distillation to remove the unreacted N,N-dimethyl-1,3-propanediamine, thereby obtaining the product diphenylmethane-based undecanoic acid amide tertiary amine with a yield of 94.99%.

[0092] S3: Take 1.23 g (6.25 mmol) of 3-chloro-2-hydroxypropane sulfonic acid sodium, 0.28 g (2.63 mmol) of sodium carbonate, 1.45 g (2.10 mmol) of diphenylmethane-based undecanoic acid amide tertiary amine (molar ratio of 5:1.25:1) and 30 mL of ethanol / water solution (Vethanol / Vwater=7:3) into a 50 mL HT-50FC flange reaction kettle, start stirring (1000 rpm) and react at a temperature of 115°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, then extract with ethanol and centrifuge to obtain the supernatant. Remove the ethanol by rotary evaporation to obtain the final product diphenylmethane-based undecanoic acid amide hydroxyl sulfonate with a content of 88.81%.

[0093] Example 10

[0094] This experiment aims to evaluate the surface tension of DiPH-2UHSB prepared by Example 5 and its anti-stability in solution to hard water. The surface tension of DiPH-2UHSB was evaluated by the hanging piece method, and the results are shown in Table 1, Figure 4 The evaluation of its hard water stability follows the standard GB.T7381-2010 "Determination of the stability of surfactants in hard water", and the specific calcium and magnesium ion resistance evaluation is shown in Table 2.

[0095] Table 1 Anti-hard water stability of surfactants

[0096]

[0097] Table 2 Anti-hard water stability of surfactants

[0098]

[0099] From Table 1, it can be seen that the CMC of DiPH-2UHSB prepared by Example 5 can reach 10-5, and the critical micelle concentration of DiPh-2UHSB is one order of magnitude lower than that of SDBS. The spacer of DiPh-2UHSB is composed of two long alkyl chains and an aromatic ring, and the intermolecular hydrophobic interaction is stronger, so it is easier to aggregate into micelles. Since the hydrophilic group is located at both ends of the molecule, it shows an inverted U-shaped arrangement when it is arranged at the gas-liquid interface, and the interaction between the exposed surface hydrophobic parts is strong, which increases the tightness of the liquid surface and reduces the surface tension. In addition, the Γmax of DiPH-2UHSB is greater than that of SDBS, and the Amin is less than that of SDBS, indicating that the surfactant molecules are arranged more closely on the interface. In addition, the both are less than zero, and more negative compared to SDBS, indicating that the surfactant molecules DiPH-2UHSB have a strong surface adsorption tendency, and the micellization process and surface adsorption are spontaneous.

[0100] As can be seen from Table 2, the DiPH-2UHSB prepared from Example 5 has a significantly higher grade in terms of hard water resistance than the traditional anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS), and has stronger hard water resistance. Compared with SDS and SDBS, the DiPH-2UHSB molecule has stronger micelle-forming ability in solution and forms more compact micelles, so it is less affected by calcium and magnesium ions. In addition, it can form complexes with calcium and magnesium ions, showing significantly better performance than traditional single-chain surfactants in terms of hard water resistance. This surfactant has great potential for application in higher salinity water solutions.

[0101] Example 11

[0102] This example uses a constant temperature stirring device to simulate the washing process. It aims to evaluate the stain removal effect of DiPH-2UHSB prepared from Example 5 on different stains at different hard water concentrations. The specific operation steps are as follows: First, place a standard white cloth with a size of 6 cm x 6 cm in a 37°C oven and wait for its mass to be constant, then record it as B. Choose 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 (Heinz) and yogurt (Junlebao) used are all commercially available products) as stains, evenly apply them on the cotton cloth, then put it in a 37°C oven to dry until constant, record it as A. Put the prepared contaminated cloth into a container containing 200 mL of test solution, stir at 30°C and 200 rpm for 30 minutes. Then, rinse the washed cotton sheet with tap water for 1 minute, and put it in a 37°C oven to dry until constant again, record it as C. Finally, calculate the stain removal rate of the surfactant by the following formula, and take the average of three experiments:

[0103]

[0104] In order to further study the hard water resistance of the synthetic surfactant as a cleaning agent, this example further tests the stain removal rate of the surfactant on motor oil at tap water, 250 mg / kg and 500 mg / kg different hard water concentrations.

[0105] The test results are shown in Figure 5 , Figure 6 As can be seen from Figure 5 , under the condition of pure water washing without adding calcium and magnesium ions, the DiPH-2UHSB has a slightly lower stain removal rate than SDBS, and compared with other stains, this surfactant shows better effect in removing soybean oil and motor oil stains. From Figure 6As can be seen from the above, with the increasing concentration of hard water in the prepared washing solution, the soil removal rate of SDBS decreased significantly. When the concentration of hard water increased from pure water to 500 mg / kg, the soil removal rate decreased from 90.18% to 67.83%, a decrease of 22.35%. In contrast, the soil removal rate of DiPH-2UHSB remained stable and could maintain more than 75% under different mineralization degrees. Compared with SDBS, DiPH-2UHSB showed better hard water resistance with the increase of hard water concentration, and was expected to be used in soil removal formulations under higher hard water conditions without additional addition of chelating agents.

[0106] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art within the scope of the present invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a diphenylmethane diundecaylamide hydroxysulfonate, characterized in that, Diphenylmethane diundecaylamide hydroxysulfonate has the following structural formula: ， or ， Preparation methods include: Diphenylmethane, methyl undecenoate, and methanesulfonic acid were mixed and subjected to a disubstituted alkylation reaction to obtain diphenylmethane alkyl diundecenoate methyl ester. Methyl diphenylmethane diundecanoate and N,N-dimethyl-1,3-propanediamine were mixed and subjected to amidation to obtain diphenylmethane diundecanoate tertiary amine. The product is obtained by mixing diphenylmethane diundecanoic acid tertiary amine, sodium 3-chloro-2-hydroxypropanesulfonate, and sodium carbonate in solution and then quaternizing them.

2. The method for preparing diphenylmethane diundecaylamide hydroxysulfonate according to claim 1, characterized in that, The molar ratio of diphenylmethane diundecylamide tertiary amine, sodium 3-chloro-2-hydroxypropanesulfonate, and sodium carbonate is 1:(1.05-5.0):(0.25-1.25).

3. The method for preparing diphenylmethane diundecaylamide hydroxysulfonate according to claim 1, characterized in that, In the quaternization reaction, the reaction temperature is 65℃-115℃, the reaction time is 6-18 h, and the pH is 8-10.

4. The method for preparing diphenylmethane diundecayl amide hydroxysulfonate according to claim 1, characterized in that, The molar ratio of diphenylmethane 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 4-8h.

5. The method for preparing diphenylmethane diundecaylamide hydroxysulfonate according to claim 1, characterized in that, The molar ratio of diphenylmethane, methyl undecenoate, and methanesulfonic acid is 1:(1-6):(3-12); in the disubstituted alkylation reaction, the reaction temperature is 55-125℃ and the reaction time is 5-10 h.

6. A diphenylmethane diundecanoic acid amide hydroxysulfonate, characterized in that, It is prepared by the method described in any one of claims 1 to 5.

7. An application of the diphenylmethane diundecaylamide hydroxysulfonate as described in claim 6, characterized in that, The diphenylmethane diundecaamide hydroxysulfonate is used for hard water washing and stain removal.

Images