A nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, its preparation method and application

Abstract

The application belongs to the technical field of surfactants, and relates to a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant and a preparation method and application thereof. The molecular structure general formula of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is as follows: the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is prepared from the following raw materials in a molar ratio: N-alkyl-1,3-propylene diamine, an alcohol solvent, itaconic acid, acrylamide and 3-chloro-2-hydroxypropyl sodium sulfonate, and the molar ratio is 1:(11.5-25.0):(1.00-1.05):(1.00-1.07):(1.00-1.07). The alcohol solvent is any one or both of ethanol and isopropanol. The nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant can be applied as a foam inhibitor, a low-foaming surfactant, a medium-foaming surfactant and / or an emulsifier.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of surfactant technology, in particular to a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant and its preparation method and application. BACKGROUND

[0002] The information disclosed in this Background section is only for the purpose of increasing the understanding of the general background of the application and does not necessarily constitute an admission or a recognition that the information forms part of the prior art that is already known in any country in the world.

[0003] At present, the research of low-foaming or medium-foaming surfactants focuses on the formula composition of surfactants, and there are few reports on single chemical composition, and there are also disadvantages of complex synthesis method. SUMMARY

[0004] In view of the few low-foaming or medium-foaming surfactants, poor performance and complex synthesis method in the current technical method, the present application aims to provide a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, which has foam inhibition, low or medium foaming and good surface activity.

[0005] The second object of the present application is to provide a preparation method of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, which is simple, easy to obtain raw materials and low in preparation cost.

[0006] The third object of the present application is to provide the application of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant as a foam inhibitor, a low or medium foaming surfactant and an emulsifier.

[0007] In order to achieve the above technical purposes, the technical scheme of the present application is as follows:

[0008] In the first aspect of the present application, a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant is provided, and the molecular structure general formula (G) can be represented as:

[0009]

[0010] Wherein, n = 12, 14, 16 or 18; C n H 2n+1 is a straight-chain alkyl group.

[0011] In the design route of the present application, if the sodium sulfonate group, the quaternary ammonium salt, the amide group, the carboxyl group and the nitrogen-containing five-membered heterocyclic structure are designed and introduced into the molecule of the surfactant, and combined with a long carbon chain lipophilic group of a certain length, a new type of nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant with a new structure is formed. The surfactant has foam inhibition, low or medium foaming and surface activity.

[0012] In a second aspect, the application provides a preparation method of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant of the first aspect, comprising the following steps:

[0013] 1) mixing N-alkyl-1,3-propanediamine, an alcohol solvent, and itaconic acid to obtain a reaction intermediate M-1, wherein the structural general formula of the reaction intermediate M-1 is:

[0014]

[0015] wherein n = 12, 14, 16, or 18; C n H 2n+1 is a linear alkyl group;

[0016] 2) adding acrylamide to the reaction intermediate M-1 and mixing to obtain a reaction intermediate M-2, wherein the structural general formula of the reaction intermediate M-2 is:

[0017]

[0018] wherein n = 12, 14, 16, or 18; C n H 2n+1 is a linear alkyl group;

[0019] 3) adding 3-chloro-2-hydroxypropyl sulfonic acid sodium salt aqueous solution to the reaction intermediate M-2 and mixing to obtain the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G.

[0020] The reaction is as follows:

[0021]

[0022] In one or more embodiments, the molar ratio of the N-alkyl-1,3-propanediamine, the alcohol solvent, the itaconic acid, the acrylamide, and the 3-chloro-2-hydroxypropyl sulfonic acid sodium salt is 1:(11.5-25.0):(1.00-1.05):(1.00-1.07):(1.00-1.07).

[0023] Experiments have shown that the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant prepared from the above-mentioned molar ratio of raw materials has good performance, and an unsuitable molar ratio cannot prepare the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant.

[0024] In one or more embodiments, in step 1), the N-alkyl-1,3-propanediamine is N-octadecyl-1,3-propanediamine, N-hexadecyl-1,3-propanediamine, N-tetradecyl-1,3-propanediamine, N-dodecyl-1,3-propanediamine, or N-hydrogenated tallow-1,3-propanediamine.

[0025] In one or more embodiments, in step 1), the alcohol solvent is any one or both of ethanol and isopropanol.

[0026] In one or more embodiments, in step 1), during the synthesis of intermediate M-1, the reaction temperature is 65-81℃, and the reaction time is 3-5h.

[0027] In one or more embodiments, in step 2), during the synthesis of intermediate M-2, the reaction temperature is 65-81℃, and the reaction time is 3-5h.

[0028] In one or more embodiments, in step 3), during the synthesis of product G, the reaction temperature is 65-81℃, and the reaction time is 4-6h.

[0029] In one or more embodiments, in step 3), the mass fraction of the aqueous 3-chloro-2-hydroxypropyl sulfonic acid sodium salt solution is 40-60%.

[0030] In one or more embodiments, the purification method of product G is as follows: the solvent of product G is evaporated under normal pressure, and the product is separated and purified by recrystallization with an organic solvent, to obtain the product. More specifically, the organic solvent for recrystallization is methanol, petroleum ether or ethyl acetate.

[0031] In a preferred embodiment, the preparation method of the above-mentioned nitrogen-containing five-membered heterocyclic sulfonic acid sodium salt surfactant G specifically comprises the following steps:

[0032] (1) N-alkyl-1,3-propanediamine is added to a reaction container, an alcohol solvent is added, heated and stirred to dissolve, itaconic acid is added in batches, after the addition is completed, the reaction is stirred at 65-81℃ for 3-5h to obtain reaction intermediate M-1;

[0033] (2) Acrylamide is added to reaction intermediate M-1 in batches, and the reaction is stirred at 65-81℃ for 3-5h to obtain reaction intermediate M-2;

[0034] (3) 3-chloro-2-hydroxypropyl sulfonic acid sodium salt aqueous solution with a mass fraction of 40-60% is added to reaction intermediate M-2 in batches, and the reaction is stirred at 65-81℃ for 4-6h to obtain nitrogen-containing five-membered heterocyclic sulfonic acid sodium salt surfactant product G. The solvent of product G is evaporated under normal pressure, and the product is separated and purified by recrystallization with an organic solvent for 3-5 times to obtain pure product G.

[0035] In the third aspect of the present application, the nitrogen-containing five-membered heterocyclic sulfonic acid sodium salt surfactant of the first aspect is used as a foam inhibitor, a low-foaming surfactant, a medium-foaming surfactant and / or an emulsifier. For example, in industrial cleaning, the generation of a large amount of foam will cause production control to be difficult to carry out, and cause material overflow and environmental pollution.

[0036] The present application takes N-alkyl-1,3-propylene diamine as the main raw material for preparing the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, and introduces sodium sulfonate group, carboxylic acid, quaternary ammonium salt group and amide group into the emulsifier molecular structure by adding itaconic acid, acrylamide and 3-chloro-2-hydroxypropyl sulfonate sodium in the preparation process of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant, so as to improve the foam inhibition, low or medium foam and surface activity.

[0037] The specific embodiment of the present application has the following beneficial effects:

[0038] (a) The present application effectively combines the sodium sulfonate group, carboxylic acid, quaternary ammonium salt group and amide group in a certain form, and combines with a carbon chain structure lipophilic group of a certain length, so as to form a new structure of nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant G. The nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant G has more hydrophilic groups and better surface performance.

[0039] (b) The main raw material for preparing the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant in the present application is diamine compound, which is easy to obtain and low in cost.

[0040] (c) The preparation process of the present application is simple, does not require high temperature reaction, and is low in energy consumption.

[0041] (d) The production operation of the present application is not complex, has strong practicability, and has remarkable benefits. BRIEF DESCRIPTION OF DRAWINGS

[0042] The drawings accompanying the specification of the present application serve to provide a further understanding of the present application, and the schematic embodiments of the present application and the description thereof serve to explain the present application, and do not constitute an improper limitation on the present application.

[0043] Figure 1 The infrared spectrum of the pure product G of Example 1 of the present application.

[0044] Figure 2 The nuclear magnetic resonance spectrum of the pure product G of Example 1 of the present application.

[0045] Figure 3 The mass spectrum of the pure product G of Example 1 of the present application.

[0046] Figure 4 The surface tension-concentration logarithm relationship diagram of the pure product G of Example 1 of the present application. DETAILED DESCRIPTION

[0047] In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in combination with specific examples and experimental examples.

[0048] Example 1

[0049] (1) Preparation of nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G (n = 18):

[0050] 1) In a reaction vessel, 326 g of N-hydrogenated tallow-1,3-propylenediamine, 900 g of isopropyl alcohol, and 75°C heating and stirring to dissolve, then 134.0 g of itaconic acid was added in 6 batches, and stirred at 75°C for 4 h to obtain reaction intermediate M-1.

[0051] 2) To reaction intermediate M-1, 74.6 g of acrylamide was added in 6 batches, and heated and stirred at 75°C for 4 h to obtain reaction intermediate M-2.

[0052] 3) To reaction intermediate M-2, 411.2 g of 50% 3-chloro-2-hydroxypropyl sulfonic acid sodium solution (purity 98.5%) was added in 6 batches, and heated and stirred at 75°C for 5 h to obtain nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G. The product G was evaporated under normal pressure to remove the solvent, and purified by recrystallization with methanol for 3 times to obtain pure product G.

[0053] The pure product G was subjected to FTIR, NMR, and MS structure characterization.

[0054] FTIR analysis ( Figure 1 ): 3357 cm -1 (peak 1) is the O-H stretching vibration absorption peak, 3202 cm -1 (peak 2) is the N-H stretching vibration peak, 2920 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, 1681 cm -1 (peak 5) is the C=O stretching vibration peak of amide, 1575 cm -1 (peak 6) is the asymmetric stretching vibration absorption peak of C-O, 1465 cm -1 (peak 7) is the asymmetric bending vibration of methylene, 1396 cm -1 (peak 8) is the symmetric bending vibration of methylene, 1197 cm -1 (peak 9) is the symmetric stretching vibration absorption peak of sulfonic acid group S=O, 1050 cm -1 (peak 10) is the asymmetric stretching vibration absorption peak of sulfonic acid group S=O, 721 cm -1 (peak 11) is the in-plane rocking vibration absorption peak of methylene, 619 cm -1 (peak 12) is the stretching vibration absorption peak of S-O.

[0055] 1 H-NMR analysis Figure 2 ): 1 H NMR (400 MHz, CD3OD), δ: 0.8841-0.9184 (3H, t, J = 6.86 Hz, -C H 3), 1.2893 (30H, s, CH3(C H 2) 15 CH2CH2-), 1.3758 (2H, s, CH3(CH2) 15 C H 2CH2-), 1.6508-1.7339 (2H, m, -NCH2C H 2CH2N-), 2.3871-2.4128 (2H, t, J = 5.14 Hz, -CH3(CH2) 15 CH2C H 2-), 2.6426-2.6745 (2H, t, J = 6.38 Hz, -CH2CH2NC H 2CH2CH2N-), 2.9694-3.0042 (2H, t, J = 6.96 Hz, -CH2C H 2CONH2), 3.0589-3.0783 (2H, t, J = 3.88 Hz, -NC H 2CH2CONH2), 3.0964-3.1110 (4H, d, J = 2.92 Hz, -NC H 2CH(OH)CH2SO3Na and -COC H 2CHCOOH), 3.4743-3.4907 (1H, m, -C H COOH), 3.6601-3.7025 (2H, t, J = 8.48 Hz, -NCH2CH2C H 2NCO-), 3.7766-3.7866 (2H, d, J = 2 Hz, -C H 2SO3Na), 3.8048-3.8149 (2H, d, J = 2.02 Hz, -NC H 2CHCOOH), 4.2593-4.2937 (1H, m, -CH2C H (OH)CH2SO3Na), 5.5310 (1H, s, -CH2CH(O H )CH2SO3Na), 6.0453 (2H, s, -CH2CH2CON H 2) ppm. 3.3103 ppm is the deuterated methanol solvent peak; 4.8566 ppm is the deuterated methanol water peak.

[0056] Mass spectrometry analysis ( Figure 3 ): HRMS(ESI)(negative)m / z:[M-Na + ] - Calcd for C 32 H 61 O8N3SCl,682.3868; Found 682.4372.

[0057] The reactions involved:

[0058]

[0059] Experimental Example 1

[0060] The antifoaming performance of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in Example 1 was determined: 10 mL of a 0.5% (w / w) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain amount of sample were placed in a 100 mL stoppered graduated cylinder, the cylinder was stopped, and then the mixture was vigorously shaken 20 times. The volume of foam generated was immediately recorded (mL). The antifoaming value (Q) was calculated, which indicates the level of antifoaming ability of the sample.

[0061] Q = (V0 - V1) / V0

[0062] Where V0 is the foam volume during the blank test, in mL; and V1 is the foam volume when the sample is added, in mL.

[0063] The defoaming properties of pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant and OP-10 (commercial product) were compared and are shown in Table 1. It can be seen that the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant prepared in Example 1 has excellent defoaming ability.

[0064] Table 1 Foam Suppression Performance

[0065]

[0066] Experimental Example 2

[0067] The emulsifying properties of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in Example 1 were determined: 20 mL of an aqueous solution of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant with a mass fraction of 0.1% or an aqueous solution of OP-10 (commercial product) and 20 mL of liquid paraffin were taken and transferred into a 100 mL stoppered graduated cylinder. The stopper was then sealed, and the mixture was shaken vigorously 5 times, allowed to stand for 1 minute, and repeated 5 times. The time required to separate 10 mL of water was recorded immediately.

[0068] The measurement data are shown in Table 2. It can be seen that the pure product G of the nitrogen-containing five-membered heterocyclic sulfonate type surfactant prepared in Example 1 has excellent emulsifying ability.

[0069] Table 2 Emulsifying Ability

[0070]

[0071]

[0072] Experimental Example 3

[0073] The foaming and foam stability of the pure product G, a nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in Example 1, were determined as follows: 80 mL of an aqueous solution with a concentration of 0.001 mol / L was prepared. 20 mL of the solution was transferred to a 100 mL stoppered graduated cylinder and placed in a 25°C water bath for 10 minutes. The heated solution was then vigorously shaken 20 times and placed on the water bath. The initial volume of the foam (H0) was recorded immediately. Subsequently, the volume of the foam (H5) was recorded after 5 minutes. The time required for the foam volume to decay to half of its original initial volume (t) was also recorded. 1 / 2 ,half life).

[0074] The foaming and foam stability test data are shown in Table 3. It can be seen that, compared with sodium dodecylbenzenesulfonate, the pure product G prepared in Example 1 has moderate foaming properties and good foam stability, indicating that the pure product G prepared in Example 1 is a medium-foaming surfactant.

[0075] Table 3 Foaming and Foam Stability

[0076]

[0077] Experiment Example 4

[0078] The surface tension and critical micelle concentration (CMC) of the pure product G of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant synthesized in Example 1 were determined using a JHZL fully automatic interfacial tensiometer (manufactured by Yangzhou Junhao Electric Co., Ltd.). The surface tension (γ) was measured using the platinum ring method, and the γ-logc variation curve was obtained (see...). Figure 4 The CMC and the surface tension (γ) under the CMC were calculated. CMC C 20 pC 20 and CMC / C 20 (See Table 4). It can be seen that the pure product G of Example 1 has better surface properties.

[0079] Table 4 Surface performance parameters of product G

[0080] Product CMC (mol L -1 ) gamma CMC (mN·m -1 )]]> C 20 (mol·L -1 )]]> pC 20 ]]> CMC / C 20 ]]> Pure product G 1.92 x 10 -4 ]]> 39.4 5.77 x 10 -6 ]]> 5.24 33.28

[0081] The above description is only the preferred embodiment of the present application, and is not intended to limit the present application. The present application can have various changes and modifications for those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A nitrogen-containing five-membered heterocyclic sulfonate sodium surfactant, characterized in that, Its general molecular formula (G) is: Formula G; Where n = 12, 14, 16, or 18; C n H 2n+1 It is a straight-chain alkyl group.

2. The method for preparing the nitrogen-containing five-membered heterocyclic sulfonate sodium surfactant according to claim 1, characterized in that, Includes the following steps: 1) An N-alkyl-1,3-propanediamine, an alcohol solvent, and itaconic acid are mixed and reacted to obtain reaction intermediate M-1. The general structural formula of reaction intermediate M-1 is: ； Where n = 12, 14, 16, or 18; C n H 2n+1 It is a straight-chain alkyl group; The N-alkyl-1,3-propanediamine is N-hexadecyl-1,3-propanediamine, N-tetradecyl-1,3-propanediamine, N-dodecyl-1,3-propanediamine, or N-hydrogenated tallow-1,3-propanediamine; 2) Acrylamide is added to reaction intermediate M-1, and the mixture is reacted to obtain reaction intermediate M-2. The general structural formula of reaction intermediate M-2 is: ； Where n = 12, 14, 16, or 18; C n H 2n+1 It is a straight-chain alkyl group; 3) Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to reaction intermediate M-2, mix and react to obtain nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G.

3. The preparation method according to claim 2, characterized in that, The molar ratio of N-alkyl-1,3-propanediamine, alcohol solvent, itaconic acid, acrylamide, and sodium 3-chloro-2-hydroxypropylsulfonate is 1:11.5-25.0:1.00-1.05:1.00-1.07:1.00-1.

07.

4. The preparation method according to claim 2, characterized in that, In step 1), the alcohol solvent is any one or both of ethanol and isopropanol.

5. The preparation method according to claim 2, characterized in that, In step 1), during the synthesis of intermediate M-1, the reaction temperature is 65-81℃ and the reaction time is 3-5h.

6. The preparation method according to claim 2, characterized in that, In step 2), during the synthesis of intermediate M-2, the reaction temperature is 65-81℃ and the reaction time is 3-5h.

7. The preparation method according to claim 2, characterized in that, In step 3), during the synthesis of product G, the reaction temperature is 65-81℃ and the reaction time is 4-6h. Alternatively, the mass fraction of the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is 40-60%.

8. The preparation method according to claim 2, characterized in that, The purification method for product G is as follows: the solvent is evaporated off under normal pressure, and the product is purified by recrystallization with an organic solvent.

9. The preparation method according to claim 8, characterized in that, The organic solvents used for recrystallization separation and purification are methanol, petroleum ether, or ethyl acetate.

10. The preparation method according to claim 2, characterized in that, Specifically, the steps include the following: (1) Add N-alkyl-1,3-propanediamine to the reaction vessel, add alcohol solvent, heat and stir to dissolve, add itaconic acid in batches, and after the addition is complete, stir the reaction at 65-81℃ for 3-5h to obtain reaction intermediate M-1; (2) Acrylamide was added to reaction intermediate M-1 in batches and stirred at 65-81℃ for 3-5 h to obtain reaction intermediate M-2; (3) Add 40-60% sodium 3-chloro-2-hydroxypropyl sulfonate aqueous solution to reaction intermediate M-2 in batches, stir and react at 65-81℃ for 4-6h to obtain nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant product G. Evaporate the solvent from product G under normal pressure, and then recrystallize and purify it 3-5 times with organic solvent to obtain pure product G.

11. The use of the nitrogen-containing five-membered heterocyclic sodium sulfonate surfactant of claim 1 as a defoaming agent, a low-foaming surfactant, a medium-foaming surfactant, and / or an emulsifier.

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