Carboxylic acid quaternary ammonium salt sodium sulfonate type surfactant, and preparation method and application thereof

Abstract

The application belongs to the technical field of surfactants, and relates to a carboxylic acid quaternary ammonium salt sodium sulfonate type surfactant as well as a preparation method and application thereof. A general formula of a molecular structure of the carboxylic acid quaternary ammonium salt sodium sulfonate type surfactant is as follows: The carboxylic acid quaternary ammonium salt sodium sulfonate type surfactant is synthesized from raw materials in the following molar proportions: a fatty primary amine, an alcohol solvent, acrylic acid, and 2-chloroethyl sodium sulfonate monohydrate, and the molar ratio is 1:(10.6-19.6):(2.00-2.22):(1.00-1.11). The carboxylic acid quaternary ammonium salt sodium sulfonate type surfactant can be applied as a foam inhibitor, a low-foam type surfactant or an emulsifier.

Description

Technical Field

[0001] This invention relates to the field of surfactant technology, specifically to a sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant, its preparation method, and its application. Background Technology

[0002] Surfactants, often referred to as "industrial MSG," are substances with hydrophilic and lipophilic groups that can orient themselves on the surface of a solution and significantly reduce its surface tension. Surfactants are classified into ionic and nonionic types and have significant practical value. Low-foaming surfactants are products exhibiting low-foaming properties in industrial applications and can be used in industrial cleaning and other fields.

[0003] In the prior art, there is a method for synthesizing a symmetrical imidazoline Gemini surfactant (CN109912506A), which discloses: using fatty acids and diethylenetriamine as raw materials, xylene as solvent, zinc powder as catalyst, heating to 190-210℃ for 6-10h, and distilling under reduced pressure at 130-150℃ to obtain an intermediate; adding dimethyl carbonate to the intermediate at 85℃, reacting for 4-6h, heating to 90℃, adding 1,3-dibromopropane, and reacting for 6-8h. Another study disclosed a sulfonyl and phosphate ester-based anionic surfactant and its synthesis method (CN109173920B): Sodium bisulfite was added to a reactor, water was added, (E)-oct-4-en-1,8-diacid was added, nitrogen gas was introduced, and the mixture was stirred and heated to 80-100℃ for 4-6 h to obtain intermediate A; intermediate A, N-alkylethanolamine and catalyst were added to a reactor, nitrogen gas was introduced, and the mixture was stirred and heated to 100-140℃ for 3-5 h to obtain a transparent solution intermediate B; intermediate B and phosphoric acid were added to a reaction vessel, and the mixture was stirred and heated to 50-70℃ for 2-4 h.

[0004] To date, there are not many types of sulfonate surfactants, and their synthesis cost is relatively high, which restricts their widespread use. At the same time, the inventors also noted that existing surfactants also have shortcomings in antifoaming, low-foaming, and emulsifying properties, as well as relatively complex preparation processes. Summary of the Invention

[0005] To address the shortcomings of current production methods for sulfonate-type surfactants, such as limited variety, need for performance improvement, and cumbersome preparation processes, the present invention aims to provide a sodium sulfonate quaternary ammonium carboxylate surfactant that exhibits antifoaming and low-foaming properties, etc.

[0006] The second objective of this invention is to provide a method for preparing sodium carboxylic acid quaternary ammonium salt sulfonate type surfactants. This preparation method is relatively simple, the raw materials are readily available, and the production cost is low.

[0007] The third objective of this invention is to provide an application of sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant as a defoaming agent, a low-foaming surfactant, or an emulsifier.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows:

[0009] In a first aspect of the present invention, a sodium quaternary ammonium sulfonate type surfactant is provided, the general molecular formula (QH) of which is:

[0010]

[0011] Where n = 12, 14, 16, 18;

[0012] C n H 2n+1 It is a straight-chain alkyl group;

[0013] Specifically, the sodium sulfonate-type surfactant derived from the following structure:

[0014] Formula QH-12:

[0015] Formula QH-14:

[0016] Formula QH-16:

[0017] Formula QH-18:

[0018] Studies have shown that introducing sodium sulfonate, carboxyl, and quaternary ammonium salt groups into the molecular structure of surfactants creates novel carboxylic acid quaternary ammonium salt sodium sulfonate surfactants, which exhibit good antifoaming properties, surface activity, emulsifying properties, and low-foaming performance.

[0019] In a second aspect, the present invention provides a method for preparing the sodium sulfonate quaternary ammonium carboxylate surfactant described in the first aspect, comprising the following steps:

[0020] S1: A reaction intermediate (ZT) can be obtained by mixing and reacting aliphatic primary amine, an alcohol solvent, and acrylic acid. The general structural formula of the reaction intermediate (ZT) is as follows:

[0021] C n H2 n +]N(CH2CH2COOH)2;

[0022] Where n = 12, 14, 16, 18;

[0023] C n H 2n+1 It is a straight-chain alkyl group;

[0024] S2: Sodium 2-chloroethylsulfonate monohydrate is added to reaction intermediate ZT and mixed to react, yielding sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant product QH; the solvent of product QH is evaporated under normal pressure, and then purified by recrystallization with organic solvent to obtain pure sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant QH (QH-12, QH-14, QH-16 or QH-18).

[0025] The reaction formula is:

[0026]

[0027] In one or more embodiments, the molar ratio of the fatty primary amine, alcohol solvent, acrylic acid, and sodium 2-chloroethylsulfonate monohydrate is 1:(10.6-19.6):(2.00-2.22):(1.00-1.11).

[0028] In one or more embodiments, in step S1, the aliphatic primary amine is dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.

[0029] In one or more embodiments, in step S1, the alcohol solvent is any one or more of ethanol and isopropanol.

[0030] In one or more embodiments, in step S1, the reaction temperature is 60-80℃ and the reaction time is 3-5h.

[0031] In one or more embodiments, in step S2, the organic solvent used for recrystallization separation and purification is petroleum ether, methanol, ethyl acetate, etc.

[0032] In one or more embodiments, in step S2, the reaction temperature is 60-80℃ and the reaction time is 3-5h.

[0033] In a preferred embodiment, the preparation method of the sodium sulfonate quaternary ammonium carboxylate surfactant QH specifically includes the following steps:

[0034] (1) Add the fatty primary amine to the reaction vessel, add an alcohol solvent, heat and stir at 60-80℃ to dissolve, then add acrylic acid in batches. After the addition is complete, stir and react at 60-80℃ for 3-5 hours to obtain the reaction intermediate (ZT).

[0035] (2) Sodium 2-chloroethyl sulfonate monohydrate was added to the reaction intermediate ZT in batches. After the addition was complete, the mixture was stirred at 60-80℃ for 3-5 hours to obtain sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant product QH. The solvent of product QH was evaporated under normal pressure, and then it was purified by recrystallization with organic solvent 2-3 times to obtain pure sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant QH (QH-12, QH-14, QH-16 or QH-18).

[0036] During the feeding process, acrylic acid is added in 3 to 5 batches, and sodium 2-chloroethylsulfonate monohydrate is added in 3 to 5 batches.

[0037] A third aspect of the present invention provides a sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant obtained by the above method.

[0038] A fourth aspect of the present invention provides an application of the above-mentioned sodium sulfonate quaternary ammonium carboxylate surfactant as an antifoaming agent, a low-foaming surfactant, and an emulsifier. For example, its application in industrial cleaning and cleaning of metal workpieces.

[0039] This invention uses fatty primary amines as the main raw material for sodium sulfonate quaternary ammonium salt surfactants. In the synthesis of sodium sulfonate quaternary ammonium salt surfactants, acrylic acid and sodium 2-chloroethyl sulfonate monohydrate are added sequentially to introduce sodium sulfonate groups, carboxyl groups and quaternary ammonium salt groups into the surfactant molecule structure, and the product has surface activity.

[0040] The specific embodiments of the present invention have the following beneficial effects:

[0041] (i) This invention combines sodium sulfonate, carboxyl, and quaternary ammonium salt hydrophilic groups with lipophilic groups of different carbon chain lengths to form a novel carboxylic acid quaternary ammonium salt sodium sulfonate surfactant, which has good surface activity.

[0042] (ii) The main raw material of the sodium sulfonate quaternary ammonium carboxylate surfactant of the present invention is aliphatic primary amine, which is inexpensive and has a low production raw material cost.

[0043] (iii) Existing sulfonate surfactants are mainly synthesized by sulfonation reactions using chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, and sulfur trioxide as sulfonating agents. These sulfonation reactions involve high temperatures, complex processes, and are highly hazardous and corrosive. The synthesis method of the sodium sulfonate quaternary ammonium carboxylate surfactant of this invention is simple and can be carried out at a lower temperature. Attached Figure Description

[0044] Figure 1 The infrared spectrum of product QH-12 from Example 1 is shown.

[0045] Figure 2 The NMR spectrum of product QH-12 from Example 1 is shown.

[0046] Figure 3 This is the mass spectrum of product QH-12 from Example 1.

[0047] Figure 4 The infrared spectrum of product QH-14 from Example 2 is shown.

[0048] Figure 5 The NMR spectrum of product QH-14 from Example 2 is shown.

[0049] Figure 6 This is the mass spectrum of product QH-14 from Example 2.

[0050] Figure 7 The infrared spectrum of product QH-16 from Example 3 is shown.

[0051] Figure 8 The NMR spectrum of product QH-16 from Example 3 is shown.

[0052] Figure 9 This is the mass spectrum of product QH-16 from Example 3.

[0053] Figure 10 The infrared spectrum of product QH-18 from Example 4 is shown.

[0054] Figure 11 The NMR spectrum of product QH-18 from Example 4 is shown.

[0055] Figure 12 This is the mass spectrum of product QH-18 from Example 4.

[0056] Figure 13 The graph shows the relationship between the surface tension and the concentration of product QH-12 from Example 1.

[0057] Figure 14 The graph shows the relationship between the surface tension and the concentration of product QH-14 from Example 2.

[0058] Figure 15 The graph shows the relationship between the surface tension and the concentration of product QH-16 from Example 3.

[0059] Figure 16 The graph shows the relationship between the surface tension and the concentration of product QH-18 from Example 4. Detailed Implementation

[0060] The following detailed description is illustrative. In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention is described in detail below with reference to specific embodiments and experimental examples.

[0061] Example 1

[0062] (1) Preparation of sodium sulfonate quaternary ammonium carboxylate surfactant (product QH-12):

[0063] 1) Add 185.35g dodecylamine and 800g isopropanol to the reaction vessel, heat and stir at 75°C to dissolve, add 154.9g acrylic acid in 5 batches, stir and react at 75°C for 4 hours to obtain reaction intermediate ZT-12.

[0064] 2) 197.8g of sodium 2-chloroethyl sulfonate monohydrate was added to reaction intermediate ZT-12 in 5 batches. After the addition was completed, the mixture was stirred at 75℃ for 4h to obtain sodium sulfonate sulfonate surfactant product QH-12. The solvent of product QH-12 was evaporated under normal pressure, and then it was purified by recrystallization with ethyl acetate twice to obtain pure sodium sulfonate sulfonate surfactant product QH-12.

[0065] Infrared analysis of pure QH-12 ( Figure 1 3610cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2923 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2854 cm⁻¹. -1 Peak 3 is the peak of the symmetric stretching vibration of the methylene group, at 1732 cm⁻¹. -1 Peak 4 is the absorption peak of the C=O stretching vibration in the carboxyl group, at 1398 cm⁻¹. -1 (peak 5) represents the symmetrical bending vibration of the methylene group, 1203 cm⁻¹. -1 Peak 6 is the stretching vibration absorption peak of CN, at 1056 cm⁻¹. -1 Peak 7 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 (peak 8) represents the in-plane rocking vibration of the methylene group, 599 cm⁻¹. -1 (peak 9) is the absorption peak of SO's stretching vibration.

[0066] Pure QH-12 was analyzed by NMR (nuclear magnetic resonance). Figure 2 ): 1 H NMR (400MHz, CD3OD), δ: 0.8820-0.9163 (3H, t, J = 6.86Hz, -C H 3), 1.2954(18H,s,CH3(C H 2)9CH2CH2N-),1.7458-1.7829(2H,t,J=7.42Hz,CH3(CH2)9C H 2CH2N-),2.6323-2.6645(4H,t,J=6.44Hz,2×-NCH2CH 2COOH),3.1837-3.2244(6H,t,J=8.14Hz,-NC H 2C H 2SO3Na and CH3(CH2) 10 C H 2N-),3.8046-3.8454(4H,t,J=8.16Hz,2×-C H 2CH2COOH)ppm.

[0067] Mass spectrometry analysis of pure QH-12 ( Figure 3 ): HRMS(ESI)(negative)m / z:[M-Na + ] - Calcd forC 20 H 39 O7NSCl,472.2136; Found 472.2721.

[0068] The reaction formula is:

[0069]

[0070] Example 2

[0071] (1) Preparation of sodium sulfonate quaternary ammonium carboxylate surfactant (product QH-14):

[0072] 1) Add 213.4g tetradecylamine and 800g isopropanol to the reaction vessel, heat and stir at 75°C to dissolve, add 154.9g acrylic acid in 5 batches, stir and react at 75°C for 4 hours to obtain reaction intermediate ZT-14.

[0073] 2) 197.8g of sodium 2-chloroethyl sulfonate monohydrate was added to reaction intermediate ZT-14 in 5 batches. After the addition was completed, the mixture was stirred at 75℃ for 4h to obtain sodium sulfonate sulfonate surfactant product QH-14. The solvent of product QH-14 was evaporated under normal pressure, and then it was purified by recrystallization with ethyl acetate twice to obtain pure sodium sulfonate sulfonate surfactant product QH-14.

[0074] Infrared analysis of pure QH-14 ( Figure 4 3610cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2923 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2854 cm⁻¹. -1 Peak 3 is the peak of the symmetric stretching vibration of the methylene group, at 1730 cm⁻¹. -1Peak 4 is the absorption peak of the C=O stretching vibration in the carboxyl group, at 1467 cm⁻¹. -1 (peak 5) represents the asymmetric bending vibration of the methylene group, at 1396 cm⁻¹. -1 (peak 6) represents the symmetrical bending vibration of the methylene group, 1203 cm⁻¹. -1 Peak 7 is the stretching vibration absorption peak of CN, at 1056 cm⁻¹. -1 Peak 8 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 (peak9) represents the in-plane rocking vibration of the methylene group, 594 cm⁻¹ -1 (peak 10) is the absorption peak of SO's stretching vibration.

[0075] Pure QH-14 was analyzed by NMR (nuclear magnetic resonance). Figure 5 ): 1 H NMR (400MHz, CD3OD), δ: 0.8816-0.9159 (3H, t, J = 6.86Hz, -C H 3), 1.2896(22H,s,CH3(C) H 2) 11 CH2CH2N-),1.7455-1.7821(2H,t,J=7.32Hz,CH3(CH2) 11 C H 2CH2N-),2.6302-2.6624(4H,t,J=6.44Hz,2×-NCH2C H 2COOH),3.1834-3.2241(6H,t,J=8.14Hz,-NC H 2C H 2SO3Na and CH3(CH2) 12 C H 2N-)3.8041-3.8449(4H,t,J=8.16Hz,2×-NC H 2CH2COOH)ppm.

[0076] Mass spectrometry analysis of pure QH-14 ( Figure 6 ): HRMS(ESI)(negative)m / z:[MH + ] - Calcd forC 22 H 42 O7NSClNa,522.2268; Found 522.3053.[M-Na + ] - Calcd for C 22 H 43O7NSCl,500.2449; Found 500.3057.[M-Na + -Cl - -H + ] - Calcd for C 22 H 42 O7NS,464.2682; Found 464.3166.

[0077] The reaction formula is:

[0078]

[0079] Example 3

[0080] (1) Preparation of sodium sulfonate quaternary ammonium carboxylate surfactant (product QH-16):

[0081] 1) Add 241.46g hexadecylamine and 800g isopropanol to the reaction vessel, heat and stir at 75°C to dissolve, add 154.9g acrylic acid in 5 batches, stir and react at 75°C for 4 hours to obtain reaction intermediate ZT-16.

[0082] 2) 197.8g of sodium 2-chloroethyl sulfonate monohydrate was added to reaction intermediate ZT-16 in 5 batches. After the addition was completed, the mixture was stirred at 75℃ for 4h to obtain sodium sulfonate sulfonate surfactant product QH-16. The solvent of product QH-16 was evaporated under normal pressure, and then it was purified by recrystallization with ethyl acetate twice to obtain pure sodium sulfonate sulfonate surfactant product QH-16.

[0083] Infrared analysis of pure QH-16 ( Figure 7 ): 3612cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2922 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2852 cm⁻¹. -1 Peak 3 is the peak of the symmetric stretching vibration of the methylene group, at 1732 cm⁻¹. -1 Peak 4 is the absorption peak of the C=O stretching vibration in the carboxyl group, at 1467 cm⁻¹. -1 (peak 5) represents the asymmetric bending vibration of the methylene group, 1398 cm⁻¹. -1 (peak 6) represents the symmetrical bending vibration of the methylene group, 1205 cm⁻¹. -1 Peak 7 is the stretching vibration absorption peak of CN, at 1056 cm⁻¹. -1 Peak 8 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1(peak9) represents the in-plane rocking vibration of the methylene group, 599 cm⁻¹ -1 (peak 10) is the absorption peak of SO's stretching vibration.

[0084] Pure QH-16 was subjected to NMR analysis ( Figure 8 ): 1 H NMR (400MHz, CD3OD), δ: 0.8830-0.9171 (3H, t, J = 6.82Hz, -C H 3), 1.2885(26H,s,CH3(C H 2) 13 CH2CH2N-),1.7467-1.7828(2H,t,J=7.22Hz,CH3(CH2) 13 C H 2CH2N-),2.6372-2.6693(4H,t,J=6.42Hz,2×-NCH2C H 2COOH),3.1839-3.2247(6H,t,J=8.16Hz,-NC H 2C H 2SO3Na and CH3(CH2) 14 C H 2N-),3.8047-3.8455(4H,t,J=8.16Hz,2×-NC H 2CH2COOH)ppm.

[0085] Mass spectrometry analysis of pure QH-16 ( Figure 9 ): HRMS(ESI)(negative)m / z:[MH + ] - Calcd forC 24 H 46 O7NSClNa,550.2581; Found 550.3295.[M-Na + ] - Calcd for C 24 H 47 O7NSCl,528.2762; Found 528.3354.[M-Na + -Cl - -H + ] - Calcd for C 24 H 46 O7NS,492.2995; Found 492.3395.

[0086] The reaction formula is:

[0087]

[0088] Example 4

[0089] (1) Preparation of sodium sulfonate quaternary ammonium carboxylate surfactant (product QH-18):

[0090] 1) Add 269.51g of octadecylamine and 800g of isopropanol to the reaction vessel, heat and stir at 75°C to dissolve, add 154.9g of acrylic acid in 5 batches, stir and react at 75°C for 4 hours to obtain reaction intermediate ZT-18.

[0091] 2) 197.8g of sodium 2-chloroethyl sulfonate monohydrate was added to reaction intermediate ZT-18 in 5 batches. After the addition was completed, the mixture was stirred at 75℃ for 4 hours to obtain sodium sulfonate sulfonate surfactant product QH-18. The solvent of product QH-18 was evaporated under normal pressure, and then it was purified by recrystallization with methanol three times to obtain pure sodium sulfonate sulfonate surfactant product QH-18.

[0092] Infrared analysis of pure QH-18 ( Figure 10 ): 3462cm -1 Peak 1 is the stretching vibration peak of OH, at 2918 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2850 cm⁻¹. -1 Peak 3 is the peak of the symmetric stretching vibration of the methylene group, at 1716 cm⁻¹. -1 Peak 4 is the absorption peak of the C=O stretching vibration, at 1560 cm⁻¹. -1 Peak 5 is the absorption peak of the asymmetric stretching vibration of CO, at 1471 cm⁻¹. -1 (peak 6) represents the asymmetric bending vibration of the methylene group, at 1396 cm⁻¹. -1 (peak 7) represents the symmetrical bending vibration of the methylene group, 1205 cm⁻¹. -1 Peak 8 is the stretching vibration absorption peak of CN, at 1172 cm⁻¹. -1 Peak 9 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1062 cm⁻¹. -1 Peak 10 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 (peak 11) represents the in-plane rocking vibration of the methylene group, 594 cm⁻¹ -1 Peak 12 is the absorption peak of SO stretching vibration, at 516 cm⁻¹. -1 (peak13) is the absorption peak of the bending vibration of OH.

[0093] Pure QH-18 was subjected to NMR analysis ( Figure 11 ): 1 H NMR (400MHz, CD3OD), δ: 0.8835-0.9178 (3H, t, J = 6.86Hz, -C H 3), 1.2884(30H,s,CH3(C) H 2) 15 CH2CH2N-),1.7499-1.7852(2H,t,J=7.06Hz,CH3(CH2) 15 C H 2CH2N-),2.6520-2.6841(4H,t,J=6.42Hz,2×-NCH2C H 2COOH),3.1810-3.2218(6H,t,J=8.16Hz,-NC H 2C H 2SO3Na and CH3(CH2) 16 C H 2N-),3.8030-3.8438(4H,t,J=8.16Hz,2×-NC H 2CH2COOH)ppm.

[0094] Mass spectrometry analysis of pure QH-18 ( Figure 12 ): HRMS(ESI)(Negative)m / z:[M-Na + ] - Calcd forC 26 H 51 O7NSCl,556.3075; Found556.3919.

[0095] The reaction formula is:

[0096]

[0097] Experimental Example 1

[0098] The foam suppression performance of the pure sodium carboxylic acid quaternary ammonium salt sulfonate surfactants QH (QH-12, QH-14, QH-16, or QH-18) synthesized in Examples 1-4 was tested: At room temperature, 10 mL of 0.5% (mass fraction) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain mass of sample were poured into a 100 mL stoppered graduated cylinder, and the cylinder was stopped and shaken vigorously up and down 20 times. The volume of foam produced was recorded (mL). The foam suppression value (E) can measure the foam suppression ability of the sample.

[0099] E = (V0 - V1) / V0

[0100] In the formula, V0 represents the foam volume (mL) during the blank test; V1 represents the foam volume (mL) when the sample is added.

[0101] The antifoaming properties of pure sodium carboxylic acid quaternary ammonium salt sulfonate surfactants QH (QH-12, QH-14, QH-16, or QH-18) and OP-10 (commercial product) were compared, and are shown in Table 1. It can be seen that the sodium carboxylic acid quaternary ammonium salt sulfonate surfactants QH (QH-12, QH-14, QH-16, or QH-18) prepared in Examples 1-4 have a certain antifoaming ability.

[0102] Table 1. Defoaming performance of the samples

[0103]

[0104]

[0105] Experimental Example 2

[0106] Emulsifying ability: At room temperature, take 20 mL of 0.1% (mass fraction) sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant pure product QH (QH-12, QH-14, QH-16 or QH-18) or OP-10 (commercial product) aqueous solution and 20 mL of liquid paraffin, pour into a 100 mL stoppered graduated cylinder, stopper it, shake vigorously 5 times, let stand for 1 min, repeat 5 times, and measure the time it takes for 10 mL of water to separate.

[0107] The experimental data are shown in Table 2. It can be seen that the sodium carboxylic acid quaternary ammonium salt sulfonate type surfactants QH (QH-12, QH-14, QH-16 or QH-18) synthesized in Examples 1-4 have good emulsifying ability.

[0108] Table 2 Emulsifying ability of samples

[0109] Product QH-12 251 Product QH-14 196 Product QH-16 180 Product QH-18 153 OP-10 684

[0110] Experimental Example 3

[0111] Foaming and foam stability: Prepare 80 mL of an aqueous solution of product QH (QH-12, QH-14, QH-16, or QH-18) with a molar concentration of 0.001 mol / L at room temperature. Transfer 20 mL of the solution to a 100 mL stoppered graduated cylinder and incubate at 25°C for 10 minutes. Vigorously shake 20 times, then allow it to stand in the water bath. Record the initial foam volume (H0), the foam volume after 5 minutes (H5), and the time required for the foam volume to become half of its initial volume (t). 1 / 2 (defined as half-life).

[0112] Experimental data are shown in Table 3. Compared with sodium dodecylbenzene sulfonate, the products QH (QH-12, QH-14, QH-16, or QH-18) exhibited lower foaming properties but better foam stability. This indicates that the carboxylic acid quaternary ammonium salt sulfonate type surfactants QH (QH-12, QH-14, QH-16, or QH-18) are low-foaming surfactants.

[0113] Table 3. Foaming properties and foam stability of the samples

[0114]

[0115] Experiment Example 4

[0116] Surface tension testing: The surface tension was determined using the platinum ring method, and the surface tension (γ)-logc curve was obtained (see...). Figures 13 to 16 This leads to the determination of the critical micelle concentration (CMC) and the surface tension (γ) at the CMC. CMC C 20 pC 20 and CMC / C 20 (See Table 4). It can be seen that the surface properties of products QH (QH-12, QH-14, QH-16 or QH-18) are better.

[0117] Table 4 Surface property parameters

[0118] Product QH-12 <![CDATA[3.73×10 -4 ]]> 34.1 <![CDATA[4.69×10 -5 ]]> 4.33 7.95 Product QH-14 <![CDATA[1.73×10 -4 ]]> 28.0 <![CDATA[2.34×10 -5 ]]> 4.63 7.39 Product QH-16 <![CDATA[2.56×10 -4 ]]> 33.4 <![CDATA[6.29×10 -5 ]]> 4.20 4.07 Product QH-18 <![CDATA[1.99×10 -4 ]]> 34.6 <![CDATA[2.19×10 -5 ]]> 4.11 9.09

[0119] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A sodium sulfonate-type surfactant, characterized in that, Its general molecular formula QH is: Formula QH; Where n = 12, 14, 16, 18; C n H 2n+1 It is a straight-chain alkyl group; The sodium sulfonate quaternary ammonium carboxylate surfactant is used as an antifoaming agent, a low-foaming surfactant, or an emulsifier.

2. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt according to claim 1, characterized in that, Includes the following steps: S1: By reacting aliphatic primary amines, alcohol solvents, and acrylic acid, reaction intermediate ZT can be obtained. The general structural formula of reaction intermediate ZT is: ； Where n = 12, 14, 16, 18; C n H 2n+1 It is a straight-chain alkyl group; S2: Sodium 2-chloroethylsulfonate monohydrate is added to the reaction intermediate ZT and mixed to react, yielding sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant product QH; the solvent of product QH is evaporated under normal pressure, and then it is purified by recrystallization with an organic solvent to obtain pure sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant QH.

3. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, The molar ratio of the aliphatic primary amine, alcohol solvent, acrylic acid, and sodium 2-chloroethylsulfonate monohydrate is 1: 10.6–19.6: 2.00–2.22: 1.00–1.

11.

4. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, In step S1, the fatty primary amine is dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.

5. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, In step S1, the alcohol solvent is any one or more of ethanol and isopropanol.

6. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, In step S1, the reaction temperature is 60-80℃ and the reaction time is 3-5h.

7. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, In step S2, the organic solvent used for recrystallization separation and purification is petroleum ether, methanol, or ethyl acetate.

8. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, In step S2, the reaction temperature is 60-80℃ and the reaction time is 3-5h.

9. The method for preparing the sodium sulfonate-type surfactant of carboxylic acid quaternary ammonium salt as described in claim 2, characterized in that, Specifically, the steps include the following: (1) Add the aliphatic primary amine to the reaction vessel, add an alcohol solvent, heat and stir at 60-80℃ to dissolve, then add acrylic acid in batches. After the addition is complete, stir the reaction at 60-80℃ for 3-5 hours to obtain the reaction intermediate ZT. (2) Sodium 2-chloroethyl sulfonate monohydrate is added in batches to the reaction intermediate ZT. After the addition is complete, the mixture is stirred at 60-80℃ for 3-5 hours to obtain sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant product QH. The solvent of product QH is evaporated under normal pressure, and then it is purified by recrystallization with organic solvent 2-3 times to obtain pure sodium carboxylic acid quaternary ammonium salt sulfonate type surfactant QH.

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