CN118255697A

CN118255697A - Preparation and application of calcium-magnesium-resistant monoaryl-linked gemini surfactant

Info

Publication number: CN118255697A
Application number: CN202410224950.6A
Authority: CN
Inventors: 贾梦娇; 杨世忠; 牟伯中; 刚洪泽
Original assignee: East China University of Science and Technology
Current assignee: East China University of Science and Technology
Filing date: 2024-02-29
Publication date: 2024-06-28

Abstract

The invention belongs to the technical field of washing decontamination, and relates to preparation and application of a calcium-magnesium-resistant monoaryl-linked gemini surfactant, wherein the preparation method comprises the following steps: mixing methyl undecanoate, benzene and methanesulfonic acid, and heating for reaction; mixing the obtained product with methyl undecylenate and methanesulfonic acid, and heating for reaction; mixing the obtained product with N, N-dimethyl-1, 3-propylene diamine, and heating for reaction; mixing the obtained product with halogenated salt and sodium carbonate, and heating to react to obtain phenyl bisundecyl amide hydroxyl sulfonate, namely the monoaryl-connected gemini surfactant. Compared with the prior art, the invention can achieve good decontamination effect in the solution with higher hard water concentration without adding chelating agent.

Description

Preparation and application of calcium-magnesium-resistant monoaryl-linked gemini surfactant

Technical Field

The invention belongs to the technical field of washing and decontamination, and relates to preparation and application of a calcium-magnesium-resistant monoaryl-linked gemini surfactant.

Background

The detergent is one of the necessities for production and living, is widely applied to the fields of household cleaning, industrial cleaning and the like, and in the washing process, the detergent needs to face the environmental conditions of low temperature, high temperature, different hardness of water and the like, and has functional requirements on the surfactant in the detergent formula, and the conventional surfactants in the detergent on the market at present are linear alkylbenzenesulfonate (SDBS), lauryl ether sulfate (AES), fatty alcohol polyoxyethylene ether (AEO) and the like. The AEO has limited solubility at normal temperature, low dissolution speed, low SDBS and AEO cloud point, easy precipitation at low temperature to form gel, unstable formula, and general adoption of a method is to add a solvent or apply a special nonionic surfactant such as isomeric alcohol ether, but the solvent has no detergency per se, and part of isomeric alcohol ether cannot reach the same detergency as AEO. In addition, most of washing water in China is hard water, and the complex of SDBS and calcium and magnesium ions in water causes the decrease of detergency of the formula, and the complex use of the chelating agent is needed, however, the chelating agent is unfavorable for the stability of the formula, and the post-treatment is complex, thereby increasing the cost and simultaneously polluting the environment.

The invention aims to overcome the defects of the prior art, and provides a preparation method of an amphoteric surfactant with excellent detergency under the conditions of low temperature and high hard water concentration, wherein the Chinese patent application CN115894282A discloses a high-temperature resistant bio-based amphoteric ion surfactant and a preparation method thereof, and the amphoteric surfactant is prepared from oleic acid or methyl ester thereof serving as a raw material through alkylation reaction, amidation reaction and quaternization reaction in sequence. Compared with the prior art, the invention realizes the optimization of the technical route of the phenyl and fatty acid chain disubstituted alkylation, and obtains the dialkyl benzene intermediate with higher yield; the surfactant disclosed by the invention can be used alone, has good low-temperature solubility and hard water resistance stability, shows better detergency than SDBS (sodium dodecyl benzene sulfonate) under high-mineralization hard water, and has application potential of effective decontamination under harsh environments such as low-temperature and high-concentration hard water.

Disclosure of Invention

The invention aims to provide a preparation and application of a calcium-magnesium-resistant monoaryl-linked gemini surfactant, which can show good detergency and hard water resistance under the condition of not adding a chelating agent additionally, and can be used for washing and decontamination under high hard water concentration.

The aim of the invention can be achieved by the following technical scheme:

In a first aspect, the present invention provides a method for preparing a monoaryl linked gemini surfactant, comprising: mixing phenyl bisundecylamide tertiary amine, halogenated salt and sodium carbonate, and carrying out quaternization reaction to obtain phenyl bisundecylamide hydroxysulfonate (PH-2 UHSB), namely the monoaryl-linked gemini surfactant.

Further, the molar ratio of the phenyl bis-undecylamide tertiary amine, the halogenated salt and the sodium carbonate is 1 (1.05-5): 0.25-1.25; the halogenated salt is 3-chlorine-2 hydroxy propane sodium sulfonate.

Further, in the quaternization reaction, the reaction temperature is 65-95 ℃, the pH=8-10, and the reaction time is 6-18h.

Further, the preparation method of the phenyl bis-undecylamide tertiary amine comprises the following steps: mixing phenyl methyl bis undecylenate and N, N-dimethyl-1, 3-propanediamine, and carrying out amidation reaction.

Further, the molar ratio of the phenyl bisundecylenate methyl ester to the N, N-dimethyl-1, 3-propylene diamine is 1 (1.2-6); in the amidation reaction, the reaction temperature is 100-160 ℃ and the reaction time is 4-8h.

Further, the preparation method of the phenyl bisundecylenate methyl ester comprises the following steps: mixing phenyl methyl undecylenate, methyl undecylenate and methanesulfonic acid, and carrying out alkylation reaction.

Further, the molar ratio of the phenyl methyl undecylenate to the methanesulfonic acid is 1 (1-3) (3-12); in the alkylation reaction, the reaction temperature is 65-125 ℃ and the reaction time is 4-10h.

Further, the preparation method of the phenyl methyl undecylenate comprises the following steps: mixing methyl undecanoate, benzene and methanesulfonic acid, and carrying out alkylation reaction.

Further, the molar ratio of the methyl undecanoate to the benzene to the methanesulfonic acid is 1 (1-5): 2-8; in the alkylation reaction, the reaction temperature is 55-95 ℃ and the reaction time is 4-8h.

In a second aspect the present invention provides the use of a monoaryl linked gemini surfactant comprising the use of the monoaryl linked gemini surfactant for hard water wash soil release.

Compared with the prior art, the invention has the following characteristics:

1) According to the invention, renewable resources methyl undecylenate is used as a raw material, and the phenyl bis-undecylenate is prepared through alkylation, amidation, quaternization and other reactions;

2) In the process of washing the surfactant, calcium and magnesium ions in the aqueous solution can be combined with acid radical ions in surfactant molecules to form a precipitate, so that the surface activity of the surfactant solution is reduced, and a chelating agent is required to be additionally added to combine with the calcium and magnesium ions in the solution, so that the surfactant solution is washed to achieve a good effect. Compared with the traditional washing anionic surfactant sodium dodecyl benzene sulfonate, the invention can achieve good decontamination effect in a solution with higher hard water concentration without adding an additional chelating agent.

Drawings

Fig. 1 is an EI mass spectrum (C ₁₈H₂₈O₂, mw= 276.4126) of methyl phenylundecanoate prepared in example 1.

Fig. 2 is an EI mass spectrum (C ₃₀H₅₀O₄, mw= 474.3696) of phenyl bis-undecylenate methyl ester prepared in example 1.

FIG. 3 is an EI mass spectrum of phenyl bis-undecylamide tertiary amine prepared in example 1 (m/z of C ₃₈H₇₀N₄O₂+Na⁺ is 637.5380; m/z of C ₃₈H₇0N₄O₂+2H⁺ is 308.2819).

Fig. 4 is an ESI mass spectrum of phenyl bis-undecylamide hydroxysulfonate prepared in example 1 (m/z= 468.2675 of m/z＝913.5350;C₄₄H₈₂ N₂O₄(N⁺SO₃ ^-)₂+2Na⁺ of C ₄₄H₈₂N₂O₄(N⁺SO₃)₂+Na⁺).

FIG. 5 is the surface tension of phenyl bis undecylamide hydroxysulfonate prepared in example 1.

FIG. 6 is the detergency of phenyl bis-undecylamide hydroxysulfonate on various stains with deionized water.

FIG. 7 is a graph of the detergency of phenylbisundecylamide hydroxysulfonate on stains at different hard water concentrations.

Detailed Description

The invention will now be described in detail with reference to the drawings and specific examples.

A phenyl bis-undecylamide hydroxysulfonate is synthesized according to the following scheme:

Firstly, using methyl undecylenate, methanesulfonic acid and benzene as reactants, preparing a polysubstituted alkylbenzene mixture by alkylation, and then separating by column chromatography to obtain phenyl bis-methyl undecylenate; mixing the mixture with N, N-dimethyl-1, 3-propylene diamine, and carrying out amidation reaction to obtain phenyl bis undecylamide tertiary amine; and finally, carrying out a chemical reaction on the amidation reaction product and halogenated salt in a solution to obtain the phenyl bisundecyl amide hydroxyl sulfonate.

The specific preparation method comprises the following steps:

s1: preparation of methyl phenyl undecylenate by monosubstituted alkylation:

mixing methyl undecanoate, benzene and methanesulfonic acid, heating to 55-95 ℃ and stirring for reaction for 4-8h, and separating and purifying to obtain phenyl methyl undecanoate; wherein, the molar ratio of the methyl undecanoate to the benzene to the methanesulfonic acid is1 (1-5) to 2-8.

S2: preparation of phenyl methyl bis undecylenate by disubstituted alkylation:

Mixing phenyl methyl undecylenate, methyl undecylenate and methanesulfonic acid, heating to 65-125 ℃, reacting and stirring for 4-10h, and separating and purifying to obtain a disubstituted alkylation product; wherein the molar ratio of the phenyl methyl undecylenate to the methanesulfonic acid is 1 (1-3) to 3-12.

S3: amidation reaction to prepare phenyl bis undecylamide tertiary amine:

Mixing phenyl methyl undecylenate and N, N-dimethyl-1, 3-propanediamine, heating to 100-160 ℃, stirring and reacting for 4-8h, and separating and purifying to obtain phenyl bis-undecylamide tertiary amine; wherein, the mole ratio of the phenyl methyl undecylenate and the N, N-dimethyl-1, 3-propylene diamine is 1 (1.2-6).

S4: quaternization reaction to prepare phenyl bisundecyl amide hydroxy sulfonate:

Mixing phenyl bis-undecyl amide tertiary amine, halogenated salt and sodium carbonate in a solution, stirring and reacting for 6-18h at 65-95 ℃ and pH 8-10, and separating and purifying to obtain phenyl bis-undecyl amide hydroxyl sulfonate; wherein, the molar ratio of the phenyl bis-undecanamide tertiary amine, the halogenated salt and the sodium carbonate is 1: (1.05-5.0): (0.25-1.25); the halogenated salt is 3-chlorine-2 hydroxy sodium propane sulfonate; the solution is a mixed solution of ethanol and water.

The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.

The yield of each reaction in the following examples was calculated as follows:

Wherein A _{Undecylenic acid methyl ester} is the GC-MS total ion chromatographic peak area of the methyl undecylenate after the single-substituted alkylation; a _{phenyl undecylenic acid methyl ester} is the GC-MS total ion chromatographic peak area of the monoalkylbenzene after the monosubstituted alkylation reaction.

Wherein A _{Undecylenic acid methyl ester} is the LC-MS total ion chromatographic peak area of alkylated methyl undecylenate; a _{Monosubstituted products} is the area of the LC-MS total ion chromatography peak of the monoalkylbenzene after alkylation reaction; a _{disubstituted products} is the LC-MS total ion chromatographic peak area of the disubstituted alkylbenzene after alkylation reaction; a _{Trisubstituted products} is the LC-MS total ion chromatographic peak area of the trisubstituted alkylbenzene after alkylation.

Wherein A _{Phenyl bis (undecylenic) acid methyl ester} is the LC-MS total ion chromatographic peak area of dialkylbenzene after amidation reaction; a _{Phenyl bis-undecylamides tertiary amines} is the LC-MS total ion chromatographic peak area of the disubstituted amidation product of the amidation reaction.

Wherein, the peak area of the amide product in the LC chromatogram after the reaction of A _{Amide products}; peak area of product in LC chromatogram after a _{quaternary ammonium products} reaction.

Example 1:

A phenyl bis-undecylamide hydroxysulfonate, the method of preparation comprising the steps of:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 0.40g (5.06 mmol) of benzene and 1.46g (15.18 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:1:3) and the reaction was stirred at 55℃under reflux for 4h to carry out the alkylation reaction. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to obtain methyl phenylundecanoate as a product in a yield of 61.46%.

Wherein, EI mass spectrum of phenyl methyl undecylenate is shown in figure 1.

S2: 1.00g (5.06 mmol) of methyl phenyl undecylenate, 1.01g (5.06 mmol) of methyl undecylenate and 1.46g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) were added to a round-bottomed flask and the reaction was carried out at 65℃with stirring under reflux for 4 h. After the reaction, ethyl acetate was added, and the organic phase was washed with deionized water until the pH was about 6 to remove methanesulfonic acid, and after separation and purification, the content of phenyl bis-undecylenate methyl ester was 70.32%.

Wherein, EI mass spectrum of phenyl methyl bisundecylenate is shown in figure 2.

S3: 1.00g (2.10 mmol) of methyl phenyl-bis-undecylenate and 0.26g (2.52 mmol) of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:1.2) were added into a round bottom flask, the temperature was raised to 100 ℃ for reaction for 4 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and distillation under reduced pressure was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine as a product in 73.76% yield.

Wherein the EI mass spectrum of the phenyl bis-undecylamide tertiary amine is shown in figure 3.

S4: 0.43g (2.20 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.056g (0.53 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 1.05:0.25:1) and 30mL of ethanol/water solution (V _Ethanol/V_{Water and its preparation method} =7:3) are taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) is started and reacted for 6h at 65 ℃. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 68.76 percent is obtained.

Wherein, the EI mass spectrum of the phenyl bisundecylamide hydroxysulfonate is shown as 4.

Example 2:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 1.18g (15.18 mmol) of benzene and 2.94g (20.36 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:3:6) and the reaction was stirred at 55℃under reflux for 6h to effect alkylation. After the reaction, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to give methyl phenylundecanoate as a product in a yield of 75.53%.

S2:1.00g (5.06 mmol of methyl phenyl undecylenate, 3.01g (15.18 mmol) of methyl undecylenate and 2.91g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) were added to a round-bottomed flask and the alkylation reaction was carried out for 8h with reflux stirring at 65 ℃, after the reaction was completed ethyl acetate was added and the organic phase was washed with deionized water to a pH around 6 to remove methanesulfonic acid to give a disubstituted alkylation product having a content of 82.64% after separation.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 0.65g (6.30 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:3) were added into a round bottom flask, the temperature was raised to 100 ℃ for reaction for 6 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine as a product in 86.63% yield.

S4: 1.24g (6.30 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.222g (2.1 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 3:1:1) and 30mL of ethanol/water solution (V _Ethanol/V_{Water and its preparation method} =7:3) were taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) was started and reacted at 65℃for 10h. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 80.34 percent is obtained.

Example 3:

S1 alkylation was carried out by taking 1.00g (5.06 mmol) of methyl undecanoate, 1.97g (25.3 mmol) of benzene and 3.89g (40.48 mmol) of methanesulfonic acid into a round-bottomed flask (molar ratio 1:5:8), and stirring under reflux at 55℃for 8 h. After the reaction, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to give methyl phenylundecanoate as a product in a yield of 79.24%.

S2: 1.00g (5.06 mmol of methyl phenyl undecanoate, 3.05g (15.18 mmol) of methyl undecanoate and 5.89g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) were added to a round-bottomed flask and the reaction was carried out for 8h under reflux stirring at 65℃to carry out the alkylation reaction.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 1.29g (12.6 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:6) were added into a round bottom flask, the temperature was raised to 100 ℃ for reaction for 8 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine with a yield of 90.86%.

S4: 2.06g (10.5 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.278g (2.6 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 5:1.25:1) and 30mL of ethanol/water solution (V _Ethanol/V_{Water and its preparation method} =7:3) were taken into a 50mL HT-50FC flange reactor, stirring was started (1000 revolutions per minute) and reacted at 65℃for 18h. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 88.98 percent is obtained.

Example 4:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 0.40g (5.06 mmol) of benzene and 1.46g (15.18 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:1:3) and the reaction was stirred at 75℃under reflux for 4h to carry out the alkylation reaction. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to obtain methyl phenylundecanoate as a product in a yield of 70.75%.

S2:1.00g (5.06 mmol) of methyl phenyl undecylenate, 1.01g (5.06 mmol) of methyl undecylenate and 1.46g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) were added to a round-bottomed flask and the reaction was carried out for 4h with reflux stirring at 95℃to carry out the alkylation reaction.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 0.26g (2.52 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:1.2) were added into a round bottom flask, the temperature was raised to 145 ℃ for reaction for 4 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine with a yield of 87.95%.

S4: 0.43g (2.20 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.056g (0.53 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 1.05:0.25:1) and 30mL of ethanol/water solution (Vethanol/Vwater=7:3) are taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) is started and reacted for 6h at 85 ℃. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 85.85 percent is obtained.

Example 5:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 1.18g (15.18 mmol) of benzene and 2.94g (20.36 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:3:6) and the reaction was stirred at 75℃under reflux for 6h to effect alkylation. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to obtain methyl phenylundecanoate as a product in a yield of 78.34%.

S2:1.00g (5.06 mmol of methyl phenyl undecylenate, 3.01g (15.18 mmol) of methyl undecylenate and 2.91g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) were added to a round-bottomed flask and the alkylation reaction was carried out for 8h with reflux stirring at 95℃after the reaction was completed, ethyl acetate was added and the organic phase was washed with deionized water to a pH of around 6 to remove methanesulfonic acid to give a disubstituted alkylated product which was 86.87% in content after separation.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 0.65g (6.30 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:3) were added into a round bottom flask, the temperature was raised to 145 ℃ for reaction for 6 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine as a product in a yield of 92.53%.

S4: 1.24g (6.30 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.222g (2.1 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 3:1:1) and 30mL of ethanol/water solution (Vol. V. Water=7:3) were taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) was started and reacted at 85℃for 10h. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. The ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxysulfonate is obtained, and the content is 90.65%.

Example 6:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 1.97g (25.3 mmol) of benzene and 3.89g (40.48 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:5:8) and the reaction was stirred at 75℃under reflux for 8h to effect alkylation. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to obtain methyl phenylundecanoate as a product in a yield of 96.75%.

S2: 1.00g (5.06 mmol of methyl phenyl undecylenate, 3.05g (15.18 mmol) of methyl undecylenate and 5.89g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) were added to a round-bottomed flask and the alkylation reaction was carried out by stirring at 95℃for 8h, after the reaction was completed ethyl acetate was added and the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, giving a disubstituted alkylated product having a content of 97.31% after separation.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 1.29g (12.6 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:6) were added into a round bottom flask, the temperature was raised to 145 ℃ for reaction for 8 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine with a yield of 91.23%.

S4: 2.06g (10.5 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.278g (2.6 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 5:1.25:1) and 30mL of ethanol/water solution (vethanol/vwater=7:3) were taken into a 50mL HT-50FC flange reactor, stirring was started (1000 revolutions per minute) and reacted at 65℃for 18h. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. The ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxysulfonate is obtained with the content of 92.88 percent.

Example 7:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 0.40g (5.06 mmol) of benzene and 1.46g (15.18 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:1:3) and the reaction was stirred at 95℃under reflux for 4h to carry out the alkylation reaction. After the reaction, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to give methyl phenylundecanoate as a product in a yield of 95.35%.

S2: 1.00g (5.06 mmol) of methyl phenyl undecanoate, 1.01g (5.06 mmol) of methyl undecanoate and 1.46g (15.18 mmol) of methanesulfonic acid (molar ratio 1:1:3) were added to a round-bottomed flask and the reaction was carried out for 4 hours with reflux stirring at 125℃to carry out the alkylation reaction.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 0.26g (2.52 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:1.2) were added into a round bottom flask, the temperature was raised to 160 ℃ for reaction for 4 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and distillation under reduced pressure was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine with a yield of 93.64%.

S4: 0.43g (2.20 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.056g (0.53 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 1.05:0.25:1) and 30mL of ethanol/water solution (Vethanol/Vwater=7:3) are taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) is started and reacted for 6h at 95 ℃. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 87.97 percent is obtained.

Example 8:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 0.39g (5.06 mmol) of benzene and 1.45g (15.18 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:1:3) and the reaction was stirred at 95℃under reflux for 6h to carry out the alkylation reaction. After the reaction, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to give methyl phenylundecanoate as a product in a yield of 97.01%.

S2:1.00g (5.06 mmol of methyl phenyl undecylenate, 3.01g (15.18 mmol) of methyl undecylenate and 2.91g (30.3 mmol) of methanesulfonic acid (molar ratio 1:3:6) were added to a round-bottomed flask and the alkylation reaction was carried out for 8h with reflux stirring at 125 ℃, after the reaction was completed ethyl acetate was added and the organic phase was washed with deionized water to a pH around 6 to remove methanesulfonic acid to give a disubstituted alkylation product having a content of 87.86% after separation.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 0.65g (6.30 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:3) were added into a round bottom flask, the temperature was raised to 160 ℃ for reaction for 6 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine with a yield of 94.88%.

S4: 1.24g (6.30 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.222g (2.1 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 3:1:1) and 30mL of ethanol/water solution (Vol. V. Water=7:3) were taken into a 50mL HT-50FC flange reactor, stirring (1000 revolutions per minute) was started and reacted at 95℃for 10 hours. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. Ethanol is removed by rotary evaporation, and the final product phenyl bisundecyl amide hydroxyl sulfonate with the content of 83.67 percent is obtained.

Example 9:

S1: 1.00g (5.06 mmol) of methyl undecanoate, 1.97g (25.3 mmol) of benzene and 3.89g (40.48 mmol) of methanesulfonic acid were added to a round-bottomed flask (molar ratio 1:5:8) and the reaction was stirred at 95℃under reflux for 8h to carry out the alkylation reaction. After the reaction was completed, the organic phase was washed with deionized water to a pH of about 6 to remove methanesulfonic acid, and then excess reactant benzene was evaporated to obtain methyl phenylundecanoate as a product in a yield of 98.79%.

S2: 1.00g (5.06 mmol) of methyl phenyl undecylenate, 3.05g (15.18 mmol) of methyl undecylenate and 5.89g (60.72 mmol) of methanesulfonic acid (molar ratio 1:3:12) were added to a round-bottomed flask and the alkylation reaction was carried out by stirring at 125℃under reflux for 8 h.

S3: 1.00g (2.10 mmol) of phenyl-bis-undecylenate methyl ester and 1.29g (12.6 mmol of N, N-dimethyl-1, 3-propanediamine (molar ratio 1:6) were added into a round bottom flask, the temperature was raised to 160 ℃ for reaction for 8 hours, after the reaction was completed, the temperature was controlled to 155 ℃, the pressure was slowly reduced to-0.10 MPa by a vacuum pump, and reduced pressure distillation was performed to remove unreacted N, N-dimethyl-1, 3-propanediamine, to obtain phenyl-bis-undecylamide tertiary amine as a product in 96.86% yield.

S4: 2.06g (10.5 mmol) of sodium 3-chloro-2-hydroxypropanesulfonate, 0.278g (2.6 mmol) of sodium carbonate, 1.29g (2.10 mmol) of phenyl bis-undecylamide tertiary amine (molar ratio 5:1.25:1) and 30mL of ethanol/water solution (vethanol/vwater=7:3) were taken into a 50mL HT-50FC flange reactor, stirring was started (1000 revolutions per minute) and reacted at 95℃for 18h. After the reaction was completed, ethanol and water were removed by evaporation, and then the product was washed three times with 10mL of ethyl acetate to remove unreacted amidated product, and the supernatant was extracted by centrifugation with ethanol. The ethanol was removed by rotary evaporation to give the final product phenylbisundecylamide hydroxysulfonate with a content of 84.96%.

Example 10:

this experiment was conducted to evaluate the surface tension of PH-2UHSB prepared in example 6 and its stability to hard water in solution. The surface tension of PH-2UHSB was measured by the hanging-plate method, and the results are shown in Table 1 and FIG. 5. The calcium and magnesium ion resistance of the surfactant was evaluated according to the standard GB. T7381-2010 determination of stability of surfactant in hard Water, and the results are shown in Table 2.

Table 1 hard water resistance stability of surfactants

Table 2 hard water resistance stability of surfactants

As can be seen from Table 1, the CMC of PH-2UHSB prepared from solid 6 can reach 10 ^-5, which is an order of magnitude lower than that of SDBS, PH-2UHSB has stronger micelle forming ability in solution, the surface tension is 34.45mN/m lower than that of SDBS, PH-2UHSB has better surface activity, and the surface tension can be effectively reduced. In addition, Γ _max of PH-2UHSB is smaller than SDBS, A _min is larger than SDBS, because the spacer of Ph-2UHSB contains a rigid structure benzene ring, the flexibility of the molecule at the interface is smaller, and the single Ph-2UHSB molecule occupies larger area at the interface and is more loosely arranged. As can be seen from Table 1, the surfactantAnd are smaller than zero, which means that PH-2UHSB has strong surface adsorption and micelle formation trend, and the micelle formation process and adsorption process of the surfactant molecules in the aqueous solution are carried out spontaneously.

It can be seen from Table 2 that the synthesized zwitterionic surfactant has higher hard water resistance level than the commonly used anionic surfactants Sodium Dodecyl Sulfate (SDS), sodium Dodecyl Benzene Sulfonate (SDBS), wherein Ph-2UHSB has better hard water resistance than the anionic surfactant. In addition, surfactant molecules exist in a form of micelle structures in a solution, counter ions are adsorbed on the surfaces of the micelles, the formed micelles are tighter, the water solubility of the surfactant is less influenced by the counter ions, phenyl groups are introduced into the hydrophobic end of Ph-2UHSB molecules, pi-pi mutual conjugation among the molecules is beneficial to enhancing the micelle forming capacity of the surfactant, and the surfactant has good stability in hard water, and in addition, the gemini surfactant has two hydrophilic groups and can form a complex with Ca ²⁺ and Mg ²⁺, so that the hard water solubility resistance of the gemini surfactant is obviously better than that of the conventional single-chain surfactant.

Example 11:

This example was used to test the detergency of the PH-2UHSB prepared in characterization example 6, and the washing process was simulated by means of a constant temperature stirring device to evaluate the detergency of the surfactant on different stains and on stains at different hard water concentrations. The experimental procedure was as follows: a standard white cloth of 6cm by 6cm was placed in an oven at 37℃until the weight was constant, and the mass was recorded as B. The oil, soybean oil, corn oil, ink, tomato sauce and yogurt (the oil used in this example was purchased from fast horsepower (Shanghai) petrochemical company, and the soybean oil (Goldfish), corn oil (Goldfish), ink (hero's brand), tomato sauce (Henlebao) and yogurt (Junlebao) were all commercial products) were selected as stains, which were uniformly applied to cotton cloth, and then dried in an oven at 37 ℃ until constant weight, respectively to obtain a stained cloth, with a recording quality of a. Taking the prepared stained cloth, stirring the stained cloth in 200mL of test solution at 30 ℃ and 200rpm for 30min, washing the washed cotton piece with tap water for 1min, then drying the cotton piece in a 37 ℃ oven until the constant weight recording quality is C, calculating the decontamination rate of the final surfactant according to the following formula, and repeating each group of experiments for three times to obtain an average value:

To investigate the hard water resistance of synthetic surfactants as detergents in more detail, the detergency of the surfactants towards engine oils at different hard water concentrations of tap water, 250mg/kg, 500mg/kg were further tested.

The results of the test are shown in fig. 6 and 7. As can be seen from FIG. 6, the decontamination rate of PH-2UHSB is equivalent to that of SDBS without adding calcium and magnesium ions, compared with pure water washing, the decontamination rate of the pH-2UHSB has better decontamination effect on soybean oil and engine oil, and as the concentration of hard water in the prepared solution is increased to 500mg/L, the decontamination rate of the SDBS is obviously reduced from 90.18% to 67.83%, the decontamination rate is correspondingly reduced by 22.35%, the hard water resistance of PH-2UHSB is better, the reduction amplitude of the decontamination rate is not obvious along with the increase of the concentration of hard water, and the decontamination rate is over 80%. Compared with SDBS, PH-2UHSB has better hard water resistance and has better decontamination effect under the aqueous solution with higher mineralization degree without adding chelating agent.

The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.

Claims

1. A method of preparing a monoaryl-linked gemini surfactant, comprising: mixing phenyl bisundecyl amide tertiary amine, halogenated salt and sodium carbonate, and carrying out quaternization reaction to obtain phenyl bisundecyl amide hydroxyl sulfonate, namely the monoaryl-connected gemini surfactant.

2. The method for preparing the monoaryl-linked gemini surfactant according to claim 1, wherein the molar ratio of the phenyl bisundecylamide tertiary amine, the halogenated salt and the sodium carbonate is 1 (1.05-5): 0.25-1.25; the halogenated salt is 3-chlorine-2 hydroxy propane sodium sulfonate.

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

4. The method for preparing a monoaryl linked gemini surfactant according to claim 2, wherein the method for preparing phenyl bis undecylamide tertiary amine comprises: mixing phenyl methyl bis undecylenate and N, N-dimethyl-1, 3-propanediamine, and carrying out amidation reaction.

5. The method for preparing a monoaryl-linked gemini surfactant according to claim 4, wherein the molar ratio of phenyl bisundecylenate 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.

6. The method for preparing a monoaryl linked gemini surfactant according to claim 4, wherein the method for preparing phenyl bisundecylenate comprises: mixing phenyl methyl undecylenate, methyl undecylenate and methanesulfonic acid, and carrying out alkylation reaction.

7. The method for preparing the monoaryl-linked gemini surfactant according to claim 7, wherein the molar ratio of phenyl methyl undecylenate, methyl undecylenate and methanesulfonic acid is 1 (1-3): 3-12; in the alkylation reaction, the reaction temperature is 65-125 ℃ and the reaction time is 4-10h.

8. The method for preparing a monoaryl linked gemini surfactant according to claim 4, wherein the method for preparing phenyl methyl undecenoate comprises: mixing methyl undecanoate, benzene and methanesulfonic acid, and carrying out alkylation reaction.

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

10. Use of a monoaryl linked gemini surfactant prepared according to any one of claims 1 to 9, wherein the monoaryl linked gemini surfactant is for hard water wash soil release.