A quaternary ammonium salt heterocyclic surfactant, its preparation method and application

Abstract

The present invention belongs to the technical field of surfactants, and relates to a quaternary ammonium salt heterocyclic surfactant and a preparation method thereof. The general molecular structure formula of the quaternary ammonium salt heterocyclic surfactant is: wherein, n = 12, 14, 16, 18. The quaternary ammonium salt heterocyclic surfactant is prepared from raw materials with the following molar ratios: the molar ratio of fatty amine, organic solvent I, itaconic acid, 2-chloroethylsulfonate monohydrate, and water is 1:(7-15):(1.00-1.07):(1.00-1.07):(15-30). The organic solvent I is one or two of ethanol and isopropanol. The quaternary ammonium salt heterocyclic surfactant of the present invention can be used as an antifoaming agent, a low-foaming surfactant, and an emulsifier.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and particularly to a quaternary ammonium salt heterocyclic surfactant, a preparation method thereof and an application thereof. Background Art

[0002] Disclosing the information of this background art section is only intended to enhance the overall understanding of the present invention, and is not necessarily regarded as an admission or any form of implication that this information constitutes prior art already known to those of ordinary skill in the art.

[0003] Under the current situation, low-foaming surfactants need to solve: (a) Most low-foaming surfactant products are compound chemical products, and there are few reports on products with a single composition. For example, a low-foaming and low-dose glufosinate and glyphosate surfactant disclosed in Chinese Patent Application No. 201910765713.X. (b) The preparation method of low-foaming surfactants is cumbersome, the product price is high, and the use is limited. Summary of the Invention

[0004] Aiming at the disadvantages of the existing technology, such as few product types, the need to improve the use performance, and the cumbersome product preparation method, the first object of the present invention is to provide a quaternary ammonium salt heterocyclic surfactant, which exhibits foam suppression and low-foaming properties, as well as good surface properties.

[0005] The second object of the present invention is to provide a preparation and synthesis method of the above quaternary ammonium salt heterocyclic surfactant, which has a simple process, is easy to operate, and has a low production cost.

[0006] The third object of the present invention is to provide an application of the above quaternary ammonium salt heterocyclic surfactant as an antifoaming agent, a low-foaming surfactant and an emulsifier.

[0007] In order to achieve the above invention objects, the technical solution of the present invention is as follows:

[0008] In the first aspect of the present invention, a quaternary ammonium salt heterocyclic surfactant is provided, and its molecular structure general formula (XC-n) is:

[0009]

[0010] In the general formula XC-n, n = 12, 14, 16, 18.

[0011] In the general formula XC-n, is selected from:

[0012]

[0013] In the process of experimental research, it was found that if a heterocycle is designed into the structure of a surfactant molecule, and quaternary ammonium groups, carboxylic acid groups, and sodium sulfonate hydrophilic groups are introduced, and a quaternary ammonium heterocyclic surfactant (XC-n) with a novel molecular structure composed of a lipophilic group with a certain length of carbon chain is formed, the surface performance of this surfactant is better.

[0014] In the second aspect of the present invention, a preparation method of the quaternary ammonium heterocyclic surfactant (XC-n) is provided, including the following steps:

[0015] 1) Mix and react fatty amine, organic solvent I, and itaconic acid to obtain intermediate BM-n, and the structural general formula of the intermediate BM-n is:

[0016]

[0017] Among them, n = 12, 14, 16, 18;

[0018] 2) Add an aqueous solution of sodium 2-chloroethyl sulfonate monohydrate to the intermediate BM-n, mix and react to obtain the quaternary ammonium heterocyclic surfactant product XC-n; the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with organic solvent II to obtain the pure product XC-n.

[0019] The reaction is as follows:

[0020]

[0021]

[0022] In one or more embodiments, the molar ratio of the fatty amine, organic solvent I, itaconic acid, sodium 2-chloroethyl sulfonate monohydrate, and water is 1:(7 - 15):(1.00 - 1.07):(1.00 - 1.07):(15 - 30).

[0023] In one or more embodiments, the fatty amine is octadecylamine, hexadecylamine, tetradecylamine, or dodecylamine.

[0024] In one or more embodiments, in step 1), in the process of preparing the intermediate BM-n, the organic solvent I is one or two of ethanol and isopropanol.

[0025] In one or more embodiments, in step 1), in the process of preparing the intermediate BM-n, the reaction temperature is 65 - 82 °C, and the reaction time is 3 - 5 h.

[0026] In one or more embodiments, in step 2), in the process of preparing the product XC-n, the reaction temperature is 65 - 82 °C, and the reaction time is 8 - 10 h.

[0027] In one or more embodiments, in step 2), the purification process of the product XC-n is as follows: the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with the organic solvent II to obtain the pure product XC-n; preferably, the organic solvent II for recrystallization separation and purification is one or more of petroleum ether, methanol, and ethyl acetate.

[0028] In a preferred embodiment, the preparation method of the above quaternary ammonium salt heterocyclic surfactant (XC-n) specifically includes the following steps:

[0029] (1) Add the fatty amine to the reactor, then add the organic solvent I, heat and stir to dissolve, add itaconic acid in 5-9 batches, and after the addition is completed, stir and react at 65-82 °C for 3-5 h to obtain the intermediate BM-n;

[0030] (2) Dissolve sodium 2-chloroethyl sulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethyl sulfonate; add the aqueous solution of sodium 2-chloroethyl sulfonate to the intermediate BM-n in 5-9 batches, and after the addition is completed, stir and react at 65-82 °C for 8-10 h to obtain the quaternary ammonium salt heterocyclic surfactant product XC-n; the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with the organic solvent II 3-5 times to obtain the pure product XC-n.

[0031] In the third aspect of the present invention, there is provided an application of the quaternary ammonium salt heterocyclic surfactant (XC-n) described in the first aspect as an antifoaming agent, low-foaming surfactant, and / or emulsifier. For example, its application in industrial cleaning can avoid the overflow of materials during the industrial cleaning process, thereby avoiding environmental pollution caused by the overflow of materials.

[0032] The present invention uses fatty amine as the main reaction raw material for the quaternary ammonium salt heterocyclic surfactant (XC-n), and introduces a variety of hydrophilic groups into the molecular structure by adding itaconic acid and sodium 2-chloroethyl sulfonate monohydrate in the preparation process of the quaternary ammonium salt heterocyclic surfactant (XC-n), thereby improving the antifoaming property, low-foaming property, and surface activity.

[0033] The specific embodiments of the present invention have the following beneficial effects:

[0034] (1) The present invention provides several quaternary ammonium salt heterocyclic surfactants (XC-n), which form a quaternary ammonium salt heterocyclic surfactant (XC-n) with a novel molecular structure composed of a quaternary ammonium group, a carboxyl group, a sodium sulfonate hydrophilic group, and a carbon chain lipophilic group with a certain length, and has better antifoaming property, low-foaming property, and surface activity.

[0035] (2) The production cost of the quaternary ammonium salt heterocyclic surfactant (XC-n) of the present invention is low, does not require high-temperature reaction, and is easy to operate and control. Description of the Drawings

[0036] The accompanying drawings of the specification, which form a part of the present invention, are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.

[0037] Figure 1 It is the infrared spectrum of the pure product XC-12 in Example 1.

[0038] Figure 2 It is the nuclear magnetic spectrum of the pure product XC-12 in Example 1.

[0039] Figure 3 It is the mass spectrum of the pure product XC-12 in Example 1.

[0040] Figure 4 It is the infrared spectrum of the pure product XC-14 in Example 2.

[0041] Figure 5 It is the nuclear magnetic spectrum of the pure product XC-14 in Example 2.

[0042] Figure 6 It is the mass spectrum of the pure product XC-14 in Example 2.

[0043] Figure 7 It is the infrared spectrum of the pure product XC-16 in Example 3.

[0044] Figure 8 It is the mass spectrum of the pure product XC-16 in Example 3.

[0045] Figure 9 It is the infrared spectrum of the pure product XC-18 in Example 4.

[0046] Figure 10 It is the nuclear magnetic spectrum of the pure product XC-18 in Example 4.

[0047] Figure 11 It is the mass spectrum of the pure product XC-18 in Example 4.

[0048] Figure 12 It is the surface tension vs. concentration graph of the pure product XC-12 in Example 1.

[0049] Figure 13 It is the surface tension vs. concentration graph of the pure product XC-14 in Example 2.

[0050] Figure 14 It is the surface tension vs. concentration graph of the pure product XC-16 in Example 3.

[0051] Figure 15 It is the surface tension vs. concentration graph of the pure product XC-18 in Example 4. Detailed implementation manners

[0052] 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 will be described in detail below in combination with specific embodiments and experimental examples.

[0053] Example 1

[0054] (1) Preparation of quaternary ammonium salt heterocyclic surfactant (product XC-12):

[0055] 1) Add 185.35 g of dodecylamine and 500 g of isopropanol into a reaction vessel, heat and dissolve; then add 134.0 g of itaconic acid in 7 batches, and stir and react at 80 °C for 4 h to obtain intermediate BM-12.

[0056] 2) Dissolve 197.8 g of 2-chloroethylsulfonate monohydrate (purity 98%) in 395.6 g of water to obtain an aqueous solution of 2-chloroethylsulfonate; add the aqueous solution of 2-chloroethylsulfonate to intermediate BM-12 in 7 batches. After the addition, stir and react at 80 °C for 9 h to obtain the quaternary ammonium salt heterocyclic surfactant product XC-12; the isopropanol in the product XC-12 is distilled off under normal pressure, and then recrystallized and purified 3 times with ethyl acetate to obtain the pure product XC-12.

[0057] The pure product XC-12 is subjected to FTIR, NMR and MS analyses.

[0058] FTIR analysis ( Figure 1 ): 3614 cm -1 (peak 1) is the stretching vibration absorption peak of O-H, 2952 cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methyl, 2920 cm -1 (peak 3) is the asymmetric stretching vibration absorption peak of methylene, 2850 cm -1 (peak 4) is the symmetric stretching vibration absorption peak of methylene, 1718 cm -1 (peak 5) is the stretching vibration absorption peak of C=O in carboxyl, 1203 cm -1 (peak 6) is the stretching vibration absorption peak of C-N, 1062 cm -1 (peak 7) is the asymmetric stretching vibration absorption peak of S=O in sulfonic acid group, 721 cm -1 (peak 8) is the in-plane rocking vibration of methylene, 601 cm -1 (peak 9) is the stretching vibration absorption peak of S-O.

[0059] 1 H-NMR analysis ( Figure 2 ):1 1H NMR (400 MHz, CD 3 OD), δ: 0.8833 - 0.9175 (3H, t, J = 6.84 Hz, -CH 3 ), 1.2903 (18H, s, CH 3 (CH 2 ) 9 CH 2 CH 2 -), 1.6116 - 1.6864 (2H, m, -CH 3 (CH 2 ) 9 CH 2 CH 2 -), 2.6352 - 2.6571 (2H, d, -COCH 2 CH-), 2.8923 - 2.9306 (2H, t, J = 7.66 Hz, CH 3 (CH 2 ) 9 CH 2 CH 2 -), 3.1935 - 3.2157 (1H, m, -CHCOOH), 3.2841 - 3.2860 (2H, d, -NCH 2 CHCOOH), 3.6251 - 3.6465 (2H, t, J = 4.28 Hz, -NCH 2 CH 2 SO 3 Na), 3.8136 - 3.8358 (2H, t, J = 4.44 Hz, -NCH 2 CH 2 SO 3 Na) ppm. The peak at 3.3103 ppm is the solvent peak of deuterated methanol; the peak at 4.8938 ppm is the water peak of deuterated methanol.

[0060] Mass spectrometry ( Figure 3 ) : HRMS (ESI) (negative) m / z: [M - H + - Calcd for C 19 H 34 O 6 NSNaCl, 462.1693; Found 462.2260; [M - Na + - Calcd for C 19 H 35 O 6 NSCl, 440.1874; Found 440.2336; [M - Na​​+ -Cl - -H + - Calculated for C 19 H 34 O 6 NS, 404.2107; Found 404.2588.

[0061] Reaction formula:

[0062]

[0063] Example 2

[0064] (1) Preparation of quaternary ammonium salt heterocyclic surfactant (product XC-14):

[0065] 1) Add 213.4 g of tetradecylamine and 500 g of isopropanol into the reaction vessel, heat to dissolve; then add 134.0 g of itaconic acid in 7 batches, stir and react at 80 °C for 4 h to obtain intermediate BM-14.

[0066] 2) Dissolve 197.8 g of sodium 2-chloroethylsulfonate monohydrate (purity 98%) in 395.6 g of water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate BM-14 in 7 batches. After addition, stir and react at 80 °C for 9 h to obtain the quaternary ammonium salt heterocyclic surfactant product XC-14; evaporate isopropanol from product XC-14 under normal pressure, and then recrystallize and purify it 3 times with ethyl acetate to obtain the pure product XC-14.

[0067] The pure product XC-14 was analyzed by FTIR, NMR and MS.

[0068] FTIR analysis ( Figure 4 ): 3610 cm -1 (peak 1) is the stretching vibration absorption peak of O-H, 2952 cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methyl, 2922 cm -1 (peak 3) is the asymmetric stretching vibration absorption peak of methylene, 2852 cm -1 (peak 4) is the symmetric stretching vibration absorption peak of methylene, 1716 cm -1 (peak 5) is the stretching vibration absorption peak of C=O in carboxyl group, 1204 cm -1 (peak 6) is the stretching vibration absorption peak of C-N, 1060 cm -1 (peak 7) is the asymmetric stretching vibration absorption peak of sulfonic group S=O, 721 cm -1 ​(peak 8) is the in-plane rocking vibration of methylene, 601 cm -1 (peak 9) is the stretching vibration absorption peak of S-O.

[0069] 1 H-NMR analysis ( Figure 5 ): 1 H NMR (400 MHz, CD 3 OD), δ: 0.8837 - 0.9197 (3H, t, J = 7.2 Hz, -C H 3 ), 1.2896 (22H, s, CH 3 (C H 2 ) 11 CH 2 CH 2 -), 1.6096 - 1.6837 (2H, m, -CH 3 (CH 2 ) 11 C H 2 CH 2 -), 2.6357 - 2.6575 (2H, d, -COC H 2 CH-), 2.8906 - 2.9289 (2H, t, J = 7.66 Hz, CH 3 (CH 2 ) 11 CH 2 C H 2 -), 3.1995 - 3.2155 (1H, m, -C H COOH), 3.2847 - 3.2863 (2H, d, -NC H 2 CHCOOH), 3.5982 - 3.6334 (2H, t, J = 7.04 Hz, -NCH 2 C H 2 SO 3 Na), 3.8135 - 3.8357 (2H, t, J = 4.44 Hz, -NC H 2 CH 2 SO 3 Na) ppm. 3.3103 ppm is the deuterated methanol solvent peak; 4.8921 ppm is the deuterated methanol water peak.

[0070] Mass spectrometry analysis ( Figure 6 ): HRMS (ESI) (negative) m / z: [M - H+ - Calculated for C 21 H 38 O 6 NSNaCl, 490.2006; Found 490.2623; [M - Na + - Calculated for C 21 H 39 O 6 NSCl, 468.2187; Found 468.2693; [M - Na + -Cl - -H + - Calculated for C 21 H 38 O 6 NS, 432.2420; Found 432.2830.

[0071] Reaction formula:

[0072]

[0073] Example 3

[0074] (1) Preparation of quaternary ammonium salt heterocyclic surfactant (product XC - 16):

[0075] 1) Add 241.46 g of hexadecylamine and 500 g of isopropanol into a reaction vessel, heat to dissolve; then add 134.0 g of itaconic acid in 7 batches, stir and react at 80 °C for 4 h to obtain intermediate BM - 16.

[0076] 2) Dissolve 197.8 g of sodium 2 - chloroethylsulfonate monohydrate (purity 98%) in 395.6 g of water to obtain an aqueous solution of sodium 2 - chloroethylsulfonate; add the aqueous solution of sodium 2 - chloroethylsulfonate to intermediate BM - 16 in 7 batches. After adding, stir and react at 80 °C for 9 h to obtain quaternary ammonium salt heterocyclic surfactant product XC - 16; evaporate isopropanol from product XC - 16 under normal pressure, and then recrystallize and purify it 3 times with a mixed solvent of ethyl acetate and methanol to obtain pure product XC - 16.

[0077] The pure product XC - 16 is subjected to FTIR and MS analysis.

[0078] FTIR analysis (see Figure 7 ): 3610 cm -1 (peak 1) is the stretching vibration absorption peak of O - H, 2952 cm -1 ​​​(Peak 2) is the absorption peak of asymmetric stretching vibration of methyl, 2916 cm -1 (Peak 3) is the absorption peak of asymmetric stretching vibration of methylene, 2850 cm -1 (Peak 4) is the absorption peak of symmetric stretching vibration of methylene, 1718 cm -1 (Peak 5) is the absorption peak of C=O stretching vibration in carboxyl group, 1660 cm -1 (Peak 6) is the absorption peak of C=O stretching vibration of amide on the ring, 1203 cm -1 (Peak 7) is the absorption peak of C-N stretching vibration, 1060 cm -1 (Peak 8) is the absorption peak of asymmetric stretching vibration of S=O in sulfonic acid group, 721 cm -1 (Peak 9) is the in-plane rocking vibration of methylene, 601 cm -1 (Peak 10) is the absorption peak of S-O stretching vibration.

[0079] Mass spectrometry analysis (see Figure 8 ): HRMS (ESI) (negative) m / z: [M-Na + - Calcd for C 23 H 43 O 6 NSCl, 496.2500; Found 496.3032.

[0080] Reaction formula:

[0081]

[0082] Example 4

[0083] (1) Preparation of quaternary ammonium salt heterocyclic surfactant (product XC-18):

[0084] 1) Add 269.51 g of octadecylamine and 500 g of isopropanol into the reaction vessel, heat and dissolve; then add 134.0 g of itaconic acid in 7 batches, and stir and react at 80 °C for 4 h to obtain intermediate BM-18.

[0085] 2) Dissolve 197.8 g of sodium 2-chloroethylsulfonate monohydrate (purity 98%) in 395.6 g of water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate into intermediate BM-18 in 7 batches. After adding, stir and react at 80 °C for 9 h to obtain the quaternary ammonium salt heterocyclic surfactant product XC-18; evaporate isopropanol under normal pressure from product XC-18, and then recrystallize and purify it 3 times with a mixed solvent of ethyl acetate and methanol to obtain the pure product XC-18.​

[0086] The pure product XC-18 was analyzed by FTIR, NMR and MS.

[0087] FTIR analysis (see Figure 9 ): 3610 cm -1 (peak 1) is the absorption peak of O-H stretching vibration, 2920 cm -1 (peak 2) is the absorption peak of asymmetric stretching vibration of methylene, 2850 cm -1 (peak 3) is the absorption peak of symmetric stretching vibration of methylene, 1718 cm -1 (peak 4) is the absorption peak of C=O stretching vibration in carboxyl group, 1205 cm -1 (peak 5) is the absorption peak of C-N stretching vibration, 1062 cm -1 (peak 6) is the absorption peak of asymmetric stretching vibration of S=O in sulfonic group, 721 cm -1 (peak 7) is the in-plane rocking vibration of methylene, 607 cm -1 (peak 8) is the absorption peak of S-O stretching vibration.

[0088] 1 1H-NMR analysis (see Figure 10 ): 1 1H NMR (400 MHz, CD 3 OD), δ: 0.8843 - 0.9186 (3H, t, J = 6.86 Hz, -CH 3 ), 1.2888 (30H, s, CH 3 (CH 2 ) 15 CH 2 CH 2 -), 1.5061 - 1.5766 (2H, m, -CH 3 (CH 2 ) 15 CH 2 CH 2 -), 2.6467 - 2.6540 (2H, d, -COCH 2 CH-), 2.8903 - 2.9286 (2H, t, J = 7.66 Hz, CH 3 (CH 2 ) 15 CH 2 CH 2 -), 3.1919 - 3.2141 (2H, t, J = 4.44 Hz, -CH 2 CH 2 SO 3Na), 3.4744 - 3.4908 (1H, m, -CHCOOH), 3.6464 - 3.6531 (2H, d, -NCH 2 CHCOOH), 3.8130 - 3.8352 (2H, t, J=4.44 Hz, -NCH 2 CH 2 SO 3 Na) ppm. 3.3104 ppm is the deuterated methanol solvent peak; 4.8743 ppm is the deuterated methanol water peak.

[0089] Mass spectrometry analysis (see Figure 11 ): HRMS (ESI) (negative) m / z: [M - Na + - Calcd for C 25 H 47 O 6 NSCl, 524.2813; Found 524.3248.

[0090] Reaction formula:

[0091]

[0092] Experimental Example 1

[0093] The foam suppression performance of the quaternary ammonium salt heterocyclic surfactants (XC - n) prepared in Examples 1 - 4 was measured: 10 mL of a 0.5% (mass fraction) aqueous solution of sodium dodecylbenzenesulfonate (LBS) and a certain amount of the sample were added to a 100 mL stoppered graduated cylinder, the stopper was plugged, and it was shaken vigorously 20 times. The total foam volume (V 1 ) was recorded, and the foam suppression value (E) was calculated.

[0094] E = (V 0 - V 1 ) / V 0

[0095] In the formula, V 0 is the foam volume in the blank test, mL; V 1 is the foam volume when the sample (product XC - n) is added, mL.

[0096] The foam suppression performance of each sample before and after purification and OP - 10 (industrial product) is shown in Tables 1 - 2. Note: The quaternary ammonium salt heterocyclic surfactants (products XC - n) prepared in Examples 1 - 4 have good foam suppression ability.

[0097] Table 1 Foam suppression properties of each sample (product XC - n) and OP - 10 before purification

[0098] ​

[0099] Table 2 Foam suppression properties of each purified sample (product XC-n) and OP-10

[0100]

[0101] Experimental Example 2

[0102] The emulsifying ability of the quaternary ammonium salt heterocyclic surfactants (product XC-n) prepared in Examples 1 to 4 was measured as follows: 20 mL of an aqueous sample solution with a mass fraction of 0.1% and 20 mL of liquid paraffin were placed in a 100 mL stoppered graduated cylinder, shaken vigorously 5 times and allowed to stand for 1 minute, and this was repeated 5 times. The time required to separate 10 mL of water was measured.

[0103] The emulsifying ability of each sample (product XC-n) is shown in Table 3. The quaternary ammonium salt heterocyclic surfactants (product XC-n) prepared in Examples 1 to 4 all have good emulsifying ability.

[0104] Table 3 Emulsifying ability (after purification)

[0105] Product Water separation time (s) Example 1 (XC-12) 130 Example 2 (XC-14) 105 Example 3 (XC-16) 185 Example 4 (XC-18) 201 OP-10 684

[0106] Experimental Example 3

[0107] The foaming and foam stability properties of the quaternary ammonium salt heterocyclic surfactants (product XC-n) prepared in Examples 1 to 4 were measured as follows: 100 mL of an aqueous sample solution with a molar concentration of 0.001 mol / L was prepared. 20 mL was taken and placed in a 100 mL stoppered graduated cylinder, and kept at a constant temperature in a water bath at 25 °C for 15 minutes. It was shaken vigorously 20 times, and the initial volume of the foam (H 0 ) was recorded. The volume of the foam (H 5 ) was recorded after 5 minutes, and the time (t 1 / 2 , half-life) when the foam volume decayed to 1 / 2 of the initial volume was recorded.

[0108] The experimental data are shown in Table 4. The quaternary ammonium salt heterocyclic surfactants (product XC-n) prepared in Examples 1 to 4 have low foaming ability and good foam stability. It shows that the product (XC-n) belongs to a low-foaming surfactant.

[0109] Table 4 Foaming and foam stability properties of each surfactant (product XC-n) (after purification)

[0110]

[0111]

[0112] Experimental Example 4

[0113] The surface tension (γ) and critical micelle concentration (CMC) of the pure product (XC-n) of the quaternary ammonium salt heterocyclic surfactant were tested: measured by the platinum ring method, and the γ-log c curve was obtained (see Figures 12 to 15 ), and the CMC, the surface tension (γ CMC ) at CMC, C 20 , pC 20 and CMC / C 20 (Table 5) were calculated. It can be seen that the pure product (XC-n) has good surface properties.

[0114] Table 5 Surface properties of the pure product (XC-n)

[0115]

[0116] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A quaternary ammonium salt heterocyclic surfactant, characterized in that its general molecular structure formula is: ， General formula XC-n, C n H 2n+1 - is dodecyl, tetradecyl, hexadecyl, octadecyl.

2. The preparation method of the quaternary ammonium salt heterocyclic surfactant according to claim 1, characterized in that it includes the following steps: 1) Mix and react fatty amine, organic solvent I and itaconic acid to obtain intermediate BM-n, and the general structure formula of the intermediate BM-n is: ， Among them, C n H 2n+1 - is dodecyl, tetradecyl, hexadecyl, octadecyl; 2) Add an aqueous solution of sodium 2-chloroethylsulfonate monohydrate to the intermediate BM-n, mix and react to obtain a quaternary ammonium salt heterocyclic surfactant product XC-n; the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with organic solvent II to obtain a pure product XC-n; In step 1), the fatty amine is octadecylamine, hexadecylamine, tetradecylamine or dodecylamine.

3. The preparation method according to claim 2, characterized in that in step 1), the molar ratio of the fatty amine, organic solvent I, itaconic acid, sodium 2-chloroethylsulfonate monohydrate, and water is 1:7-15:1.00-1.07:1.00-1.07:15-30.

4. The preparation method according to claim 2, characterized in that in step 1), in the process of preparing the intermediate BM-n, the organic solvent I is one or two of ethanol and isopropanol.

5. The preparation method according to claim 2, characterized in that in step 1), in the process of preparing the intermediate BM-n, the reaction temperature is 65-82 °C and the reaction time is 3-5 h.

6. The preparation method according to claim 2, characterized in that in step 2), in the process of preparing the product XC-n, the reaction temperature is 65-82 °C and the reaction time is 8-10 h.

7. The preparation method according to claim 2, characterized in that in step 2), the purification process of the product XC-n is: the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with organic solvent II to obtain a pure product XC-n.

8. The preparation method according to claim 7, characterized in that in step 2), the organic solvent II for recrystallization separation and purification is one or more of petroleum ether, methanol, and ethyl acetate.

9. The preparation method according to claim 2, characterized in that specifically includes the following steps: (1) Add the fatty amine to the reactor, then add the organic solvent I, heat and stir to dissolve, add itaconic acid in 5-9 batches, and after the addition is completed, stir and react at 65-82 °C for 3-5 h to obtain the intermediate BM-n; (2) Dissolve sodium 2-chloroethylsulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to the intermediate BM-n in 5-9 batches, and after the addition is completed, stir and react at 65-82 °C for 8-10 h to obtain a quaternary ammonium salt heterocyclic surfactant product XC-n; the organic solvent I is distilled off from the product XC-n under normal pressure, and then recrystallized and purified with organic solvent II 3-5 times to obtain a pure product XC-n.

10. The application of the quaternary ammonium salt heterocyclic surfactant according to claim 1 as an antifoaming agent, low-foaming surfactant and / or emulsifier.

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