Amide quaternary ammonium salt sodium sulfonate type surfactant and its preparation method and application

Abstract

This invention discloses a sodium amide quaternary ammonium salt sulfonate type surfactant, its preparation method, and its application, belonging to the field of fine chemical technology. The molecular structure of the sodium amide quaternary ammonium salt sulfonate type surfactant is as follows: The sodium amide quaternary ammonium salt sulfonate type surfactant is prepared from the following molar ratio of raw materials: cocoylpropyl dimethyl tertiary amine, water, and sodium 2-chloroethyl sulfonate monohydrate in a molar ratio of 1:(35-60):(1.00-1.09). The sodium amide quaternary ammonium salt sulfonate type surfactant of this invention has abundant hydrophilic groups, good antifoaming ability, emulsifying ability, and good surface activity, and can be used as an antifoaming agent, a low-foaming surfactant, or an emulsifier.

Description

Technical Field

[0001] This invention belongs to the field of fine chemical technology, specifically relating to a sodium amide quaternary ammonium salt sulfonate surfactant, its preparation method, and its application. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] Low-foaming surfactants are surfactants that do not produce foam or produce a low amount of foam under certain usage conditions. The inventors have found that currently, commercially available low-foaming surfactants are mainly compound products, with relatively little research on surfactants with independent chemical compositions. At the same time, they also suffer from drawbacks such as complex preparation techniques and high product prices. Summary of the Invention

[0004] In view of the shortcomings of current technology, such as the limited number of commercially available low-foaming surfactants, poor performance, and complicated preparation techniques, one of the objectives of this invention is to provide a sodium amide quaternary ammonium salt sulfonate type surfactant, which has certain anti-foaming properties, low foaming properties, and good surface properties.

[0005] The second objective of this invention is to provide a method for preparing the above-mentioned sodium amide quaternary ammonium salt sulfonate type surfactant. This method is simple to operate, involves a one-step reaction, has a wide range of raw material sources, and has low raw material costs.

[0006] A third objective of this invention is to provide the above-mentioned sodium amide quaternary ammonium sulfonate surfactant as an antifoaming agent, a low-foaming surfactant, or an emulsifier.

[0007] To achieve the above objectives, the technical solution of the present invention is as follows:

[0008] In a first aspect of the present invention, a sodium amide quaternary ammonium sulfonate type surfactant TU is provided, the molecular structural formula (Formula TU) of which is:

[0009]

[0010] The amide quaternary ammonium salt sodium sulfonate type surfactant TU disclosed in this invention contains hydrophilic groups such as amide groups, quaternary ammonium salts, and sodium sulfonate groups, and has good surface activity.

[0011] In a second aspect of the present invention, a method for preparing the above-mentioned sodium amide quaternary ammonium sulfonate type surfactant TU is provided, comprising the following steps:

[0012] Cocoylpropyl dimethyl tertiary amine, water, and sodium 2-chloroethyl sulfonate monohydrate were added to a reactor and reacted to obtain the surfactant product TU, which is an amide quaternary ammonium salt sulfonate.

[0013] The reaction process for preparing the sodium amide quaternary ammonium sulfonate type surfactant TU disclosed in this invention is as follows:

[0014]

[0015] In one or more embodiments, the molar ratio of the cocoylpropyl dimethyl tertiary amine, water, and sodium 2-chloroethylsulfonate monohydrate is 1:35-60:1.00-1.09.

[0016] In one or more embodiments, water is used as the reaction solvent in the preparation of product TU, and isopropanol cannot be selected; if isopropanol is selected, it has been verified experimentally that product TU cannot be synthesized.

[0017] In one or more embodiments, the mixed reaction is carried out at a temperature of 65-85°C for a time of 4-6 hours.

[0018] In one or more embodiments, the preparation method further includes: purifying the product TU, specifically: evaporating the solvent water from the product TU under normal pressure, and then recrystallizing and purifying it with an organic solvent to obtain pure product TU; preferably, the organic solvent is methanol, petroleum ether, or ethyl acetate.

[0019] In one or more embodiments, the mixing specifically involves: adding cocoylpropyl dimethyl tertiary amine and water to a reactor, heating and stirring to dissolve, and then adding sodium 2-chloroethylsulfonate monohydrate in batches.

[0020] In a third aspect of the invention, the above-described sodium amide quaternary ammonium sulfonate surfactant TU is provided for use in defoamers, low-foaming surfactants, or emulsifiers.

[0021] In one or more embodiments, the application is: the application of sodium amide quaternary ammonium salt sulfonate type surfactant in emulsified asphalt.

[0022] In one or more embodiments, the application is: the application of sodium amide quaternary ammonium salt sulfonate type surfactants in industrial cleaning agents.

[0023] The beneficial effects of this invention are as follows:

[0024] (1) In this invention, hydrophilic groups such as amide groups, quaternary ammonium salts, and sodium sulfonate groups are connected in a certain way to form a novel amide quaternary ammonium salt sodium sulfonate type surfactant TU. The amide quaternary ammonium salt sodium sulfonate type surfactant TU is a low foaming surfactant with abundant hydrophilic groups and good performance (good antifoaming ability, emulsifying ability, and good surface activity).

[0025] (2) The main raw material for preparing sodium amide quaternary ammonium salt sulfonate surfactant TU in this invention is cocoylpropyl dimethyl tertiary amine, which is easy to obtain and inexpensive.

[0026] (3) In the preparation of sodium amide quaternary ammonium salt sulfonate surfactant TU in this invention, the preparation process is simple and can be obtained in one step, which is suitable for widespread use. Attached Figure Description

[0027] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0028] Figure 1 The infrared spectrum of the pure product TU in Example 1 of this invention;

[0029] Figure 2 This is the NMR spectrum I of the pure product TU from Example 1 of the present invention;

[0030] Figure 3 This is NMR spectrum II of the pure product TU from Example 1 of the present invention;

[0031] Figure 4 This is the mass spectrum of the pure product TU from Example 1 of the present invention;

[0032] Figure 5 This is a graph showing the relationship between the surface tension and the concentration of the pure product TU in Example 1 of the present invention. Detailed Implementation

[0033] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0034] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of exemplary embodiments according to the invention. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0035] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0036] Example 1

[0037] (1) Preparation of TU, ​​a surfactant product of sodium amide quaternary ammonium sulfonate type:

[0038] 284.5 g of cocoylpropyl dimethyl tertiary amine and 900 g of water were added to a three-necked flask reactor and heated and stirred to dissolve. Then, 197.8 g of sodium 2-chloroethyl sulfonate monohydrate (98% purity) was added in seven batches, and the reaction was carried out at 80 °C with stirring for 5 h to obtain the amide quaternary ammonium salt sulfonate type surfactant product TU. The solvent water of product TU was evaporated under normal pressure, and the product was purified three times by recrystallization from ethyl acetate to obtain pure product TU.

[0039] The pure product TU was characterized by FTIR, NMR and MS.

[0040] FTIR analysis ( Figure 1 3610cm -1 Peak 1 is the absorption peak of the NH stretching vibration, at 3537 cm⁻¹. -1 Peak 2 is the peak of the NH asymmetric stretching vibration, at 2923 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2854 cm⁻¹. -1 Peak 4 is the absorption peak of the symmetric stretching vibration of the methylene group, at 1652 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of amide, at 1465 cm⁻¹. -1 (peak 6) represents the asymmetric bending vibration of the methylene group, 1205 cm⁻¹. -1 Peak 7 is the stretching vibration absorption peak of CN, at 1178 cm⁻¹. -1 Peak 8 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1060 cm⁻¹. -1 Peak 9 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 Peak 10 is the in-plane rocking vibration peak of the methylene group, at 603 cm⁻¹.-1 (peak11) is the absorption peak of SO's stretching vibration.

[0041] 1 H-NMR analysis ( Figure 2 and Figure 3 ): 1 H NMR (400MHz, CD3OD), δ: 0.8822-0.9164 (3H, t, J = 6.84Hz, -C H 3), 1.2893(16H,s,CH3(C H 2)8CH2CH2-),1.5772-1.6400(2H,m,CH3(CH2)8C H 2CH2-),1.7421-1.8147(2H,m,-CONHCH2C H 2CH2N-),2.1686-2.2059(2H,t,J=7.46Hz,-C H 2CONHCH2CH2CH2N-),2.5173(6H,s,2×-NC H 3),2.6545-2.6915(2H,t,J=7.4Hz,-CONHCH2CH2C H 2N-),3.1915-3.2136(4H,t,J=4.42Hz,-N(C H 2)2SO3Na),3.8130-3.8351(2H,t,J=4.42Hz,-CONHC H 2CH2CH2N-),6.5782-6.6201(1H,t,J=8.38Hz,-CON H CH2CH2CH2N-)ppm. 3.3103 is the solvent peak of deuterated methanol; 4.8383 is the water peak of deuterated methanol.

[0042] Mass spectrometry analysis ( Figure 4 ): HRMS(ESI)(Positive)m / z:[M-Cl - ] + Calcd for C 19 H 40 O4N2NaS,415.2607; Found 415.2587.[M-Na + -Cl - +H + ] + Calcd for C 19 H 41 O4N2S,393.2787; Found393.2769.

[0043] Comparative Example 1

[0044] (1) Preparation of TU, ​​a surfactant product of sodium amide quaternary ammonium sulfonate type:

[0045] Replacing 900g of water in Example 1 with 900g of isopropanol, with the rest remaining the same, the product TU, a sodium amide quaternary ammonium sulfonate surfactant, was not obtained.

[0046] Experimental Example 1

[0047] The antifoaming properties of the sodium dodecylbenzene sulfonate surfactant product TU synthesized in Example 1 and the pure product TU were determined: 10 mL of a 0.5% (w / w) sodium dodecylbenzene sulfonate (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 to characterize the antifoaming ability of the sample.

[0048] Q = (V0 - V1) / V0

[0049] In the formula, V0 is the foam volume (mL) during the blank test; V1 is the foam volume (mL) when product TU is added.

[0050] Tables 1 and 2 list the defoaming performance Q values ​​of sodium amide quaternary ammonium sulfonate surfactant product TU, pure product TU, and OP-10 (commercial product). It can be seen that the sodium amide quaternary ammonium sulfonate surfactant product TU and pure product TU prepared in Example 1 have good defoaming ability.

[0051] Table 1. Foam suppression performance (sample before purification)

[0052]

[0053] Table 2. Foam suppression performance (after purification)

[0054]

[0055] Experiment Example 2

[0056] The emulsifying properties of the pure product TU of sodium amide quaternary ammonium sulfonate surfactant synthesized in Example 1 were determined: 20 mL of 0.1% aqueous solution of sodium amide quaternary ammonium sulfonate surfactant product TU or 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 sealed, the cylinder was shaken vigorously 5 times, allowed to stand for 1 minute, and the process was repeated 5 times. The time taken to separate 10 mL of water was recorded.

[0057] The data are shown in Table 3. The pure product TU, a sodium amide quaternary ammonium sulfonate surfactant prepared in Example 1, has excellent emulsifying ability.

[0058] Table 3 Emulsifying Ability

[0059] product Water separation time (s) Pure product TU 171 OP-10 684

[0060] Experimental Example 3

[0061] The foaming properties of the pure product TU, a sodium sulfonate amide surfactant synthesized in Example 1, were tested: 100 mL of an aqueous solution with a molar concentration of 0.001 mol / L was prepared. 20 mL of the solution was transferred to a 100 mL stoppered graduated cylinder and kept at 25°C for 10 minutes. The mixture was then vigorously shaken 20 times, allowed to stand, and the initial foam volume (H0), the foam volume at 5 minutes (H5), and the time (t) required for the foam volume to decay to half of its initial volume were recorded. 1 / 2 (i.e., half-life).

[0062] Table 4 lists the experimental data. Compared with sodium dodecylbenzenesulfonate, the H0 of the pure product TU of the sodium amide quaternary ammonium sulfonate surfactant prepared in Example 1 is 11 mL, which indicates that it has lower foaming properties and better foam stability, indicating that the pure product TU of the sodium amide quaternary ammonium sulfonate surfactant prepared in Example 1 is a low-foaming surfactant.

[0063] Table 4 Foam Performance

[0064]

[0065] Experiment Example 4

[0066] The surface tension and critical micelle concentration (CMC) of the pure product TU, a sodium sulfonate amide surfactant synthesized in Example 1, were tested using a JHZL fully automatic interfacial tensiometer (Yangzhou Junhao Electric Co., Ltd.). Surface tension (γ) was measured to obtain the γ-log c change curve (see...). Figure 5 As shown), and the CMC and the surface tension (γ) at CMC were calculated. CMC C 20 pC 20 and CMC / C 20 The parameters are shown in Table 5. It is evident that the pure product TU, a sodium amide quaternary ammonium sulfonate surfactant from Example 1, exhibits superior surface properties.

[0067] Table 5 Surface property parameters of pure product TU

[0068] product <![CDATA[CMC(mol·L -1 )]]> <![CDATA[γ CMC (mN·m -1 )]]> <![CDATA[C 20 (mol·L -1 )]]> <![CDATA[pC 20 ]]> <![CDATA[CMC / C 20 ]]> Pure product TU <![CDATA[3.41×10 -4 ]]> 31.6 <![CDATA[3.01×10 -5 ]]> 4.52 11.33

[0069] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. The application of a sodium amide quaternary ammonium salt sulfonate type surfactant as a defoaming agent and a low-foaming surfactant, characterized in that, The molecular structure of the surfactant is as follows: ； The sodium amide quaternary ammonium sulfonate surfactant has a concentration of 3.41 × 10⁻⁶. -4 mol·L -1 The surface tension at the critical micelle concentration is 31.6 mN·m. -1 .

2. The application as described in claim 1, characterized in that, The application is: the application of sodium amide quaternary ammonium salt sulfonate surfactant in emulsified asphalt.

3. The application as described in claim 1, characterized in that, The application is: the use of sodium amide quaternary ammonium salt sulfonate surfactants in industrial cleaning agents.

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