Sodium pyrrolidone sulfonate type surfactant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of surfactants, and particularly relates to a pyrrolidone sodium sulfonate type surfactant as well as a preparation method and application thereof. In order to overcome the defects that in the prior art, the variety of low-foam surfactants is few, and the difficulty of a synthesis method is large, the molecular structural formula of the sodium pyrrolidone sulfonate type surfactant is # imgabs0. N-hydrogenated tallow group-1, 3-propylene diamine is used as a starting material for preparing the sodium pyrrolidone sulfonate type surfactant XP, and the sodium pyrrolidone sulfonate type surfactant XP is prepared by using N-hydrogenated tallow group-1, 3-propylene diamine as an auxiliary material. In the preparation process of the sodium pyrrolidone sulfonate type surfactant XP, itaconic acid, 1, 3-propane sultone and 3-chloro-2-hydroxy propyl sodium sulfonate are sequentially added, hydroxyl, carboxylic acid groups, quaternary ammonium salt groups, sulfonic acid (sodium) groups and ring acylamino hydrophilic groups are introduced into the molecular structure of the surfactant XP, and the surface performance of the surfactant XP is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of surfactants, and specifically relates to a sodium pyrrolidone sulfonate surfactant and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention, and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Surfactants are amphiphilic molecules composed of a hydrophilic head group and a hydrophobic tail chain. They can self-assemble in aqueous solution to form a variety of aggregate structures, showing unique physical and chemical properties. They are widely used in many fields such as washing, food, medicine, coatings, textiles, construction, and oil production. When surfactants are mixed with water, the hydrophilic end will dissolve in the water, while the hydrophobic end will leave the water and gather on the water surface. For surfactants on the water surface, the hydrophobic end will leave the water surface and enter the air, while the hydrophilic end will dissolve in the water and be arranged on the water surface. When the water is stirred, air will enter the water, and the hydrophobic end will envelop the air and form bubbles.

[0004] Low-foaming surfactants are surfactants that exhibit low-foaming properties in spray cleaning or other fields of use. The purpose of low foaming is to meet the requirements of the production environment. In the production process of some products, the generation of foam brings adverse effects, so low-foaming or non-foaming surfactants are needed. For example, non-foaming or low-foaming industrial detergents can be used as metal cleaning agents, metal degreasing agents, plastic cleaning agents, etc.

[0005] At present, low-foaming surfactants are mainly composite products, and products with independent chemical compositions are rarely reported, and most of them are non-ionic surfactants. A preparation method and application of a low-foaming non-ionic surfactant (CN112898559A) discloses: it is obtained by reacting alkyl polyoxypropylene ether and methyl chloride under the action of an alkaline catalyst. It has excellent high-temperature stability and can be used for fuel leakage treatment at high temperatures to avoid fire and explosion hazards.

[0006] In the prior art, there is relatively little development of sulfonate-type low-foaming surfactants, which results in high prices, complicated preparation methods, and certain defects in anti-foaming performance, surface performance, and emulsification performance. Summary of the invention

[0007] In order to solve the drawbacks of the existing low-foaming surfactants in the prior art, which are few in variety and difficult in synthesis, the present invention aims to provide a sodium pyrrolidone sulfonate surfactant and its preparation method and application. The sodium pyrrolidone sulfonate surfactant provided by the present invention has anti-foaming properties, low foaming and good surface activity, and the preparation method is relatively simple.

[0008] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0009] In a first aspect, the present invention provides a sodium pyrrolidone sulfonate surfactant, characterized in that its molecular structure is as shown in Formula XP:

[0010]

[0011] In a second aspect, the present invention provides a method for preparing the sodium pyrrolidone sulfonate surfactant as described in the first aspect, comprising the following steps:

[0012] S1. Dissolve N-hydrogenated tallow-1,3-propylene diamine in an organic solvent I, add itaconic acid, mix and heat to react, and obtain an intermediate VB-1. The structural formula of the intermediate VB-1 is:

[0013]

[0014] S2. Add 1,3-propane sultone to the intermediate VB-1, mix and heat to react, and obtain the intermediate VB-2. The structural formula of the intermediate VB-2 is:

[0015]

[0016] S3. Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate VB-2, mixing and heating the mixture to react, thereby obtaining a sodium pyrrolidone sulfonate type surfactant; distilling off the organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then purifying the mixture by recrystallization with an organic solvent II to obtain a pure sodium pyrrolidone sulfonate type surfactant.

[0017] In a third aspect, the present invention provides a use of the sodium pyrrolidone sulfonate type surfactant as described in the first aspect in a foam suppressor and / or a low-foaming surfactant and / or an emulsifier.

[0018] The beneficial effects achieved by one or more technical solutions of the present invention are as follows:

[0019] (i) The present invention connects the hydroxyl group, carboxylic acid group, quaternary ammonium salt group, sulfonic acid (sodium) group, and the hydrophilic group of the amide group on the ring in a certain manner, and coordinates C 18 H 37The lipophilic group constitutes a new type of sodium pyrrolidone sulfonate surfactant. The sodium pyrrolidone sulfonate surfactant has more hydrophilic groups and better surface properties.

[0020] (ii) The raw material sources of the sodium pyrrolidone sulfonate surfactant of the present invention are wide and the production cost is low.

[0021] (iii) The preparation process is simple, using a common reactor and does not require reaction under high temperature and high pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings in the specification, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0023] Figure 1 FTIR image of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1;

[0024] Figure 2 is the mass spectrum of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1;

[0025] Figure 3 This is a graph showing the surface tension and concentration logarithm of the pure sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1. DETAILED DESCRIPTION

[0026] The first typical embodiment of the present invention is a sodium pyrrolidone sulfonate surfactant, whose molecular structure is shown in Formula XP:

[0027]

[0028] A second typical embodiment of the present invention is a method for preparing a sodium pyrrolidone sulfonate surfactant as described in the first typical embodiment, comprising the following steps:

[0029] S1. Dissolve N-hydrogenated tallow-1,3-propylene diamine in an organic solvent I, add itaconic acid, mix and heat to react, and obtain an intermediate VB-1. The structural formula of the intermediate VB-1 is:

[0030]

[0031] S2. Add 1,3-propane sultone to the intermediate VB-1, mix and heat to react, and obtain the intermediate VB-2. The structural formula of the intermediate VB-2 is:

[0032]

[0033] S3. Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate VB-2, mixing and heating the mixture to react, thereby obtaining a sodium pyrrolidone sulfonate type surfactant; distilling off the organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then purifying the mixture by recrystallization with an organic solvent II to obtain a pure sodium pyrrolidone sulfonate type surfactant.

[0034] In one or more examples of this embodiment, the molar ratio of N-hydrogenated tallow-1,3-propylene diamine, organic solvent I, itaconic acid, 1,3-propane sultone, and sodium 3-chloro-2-hydroxypropyl sulfonate is 1: (7-21): (1.00-1.07): (1.00-1.10): (1.00-1.10).

[0035] In one or more examples of this embodiment, the organic solvent I includes one of ethanol, propanol or isopropanol.

[0036] In one or more examples of this implementation mode, the mass fraction of sodium 3-chloro-2-hydroxypropyl sulfonate in the sodium 3-chloro-2-hydroxypropyl sulfonate aqueous solution is 27-37%.

[0037] In one or more examples of this embodiment, the organic solvent II includes one of petroleum ether, methanol or ethyl acetate.

[0038] In one or more examples of this embodiment, in step S1, itaconic acid is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 3 to 5 hours.

[0039] In one or more examples of this embodiment, in step S2, 1,3-propane sultone is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 3 to 5 hours.

[0040] In one or more examples of this embodiment, in step S3, the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 6.5 to 9.5 hours.

[0041] The third typical embodiment of the present invention is the use of a sodium pyrrolidone sulfonate type surfactant as described in the first typical embodiment in a foam suppressor and / or a low-foaming surfactant and / or an emulsifier.

[0042] The invention uses N-hydrogenated tallow-1,3-propylene diamine as a starting material for preparing a sodium pyrrolidone sulfonate type surfactant XP, and sequentially adds itaconic acid, 1,3-propane sultone and sodium 3-chloro-2-hydroxypropyl sulfonate during the preparation of the sodium pyrrolidone sulfonate type surfactant XP, thereby introducing a hydroxyl group, a carboxylic acid group, a quaternary ammonium salt group, a sulfonic acid (sodium) group and a ring amide hydrophilic group into the molecular structure of the surfactant XP, thereby improving the surface performance of the surfactant XP.

[0043] 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 comparative examples.

[0044] Example 1

[0045] Preparation of Sodium Pyrrolidone Sulfonate Surfactant (XP)

[0046] 1) Add 326 g of N-hydrogenated tallow-1,3-propylene diamine and 700 g of isopropanol into a three-necked flask, heat and stir at 75° C., then add 134.0 g of itaconic acid in 8 batches, stir and react at 75° C. for 4 h to obtain intermediate VB-1.

[0047] 2) 128.2 g of 1,3-propane sultone was added to the intermediate VB-1 in 8 batches, and the mixture was stirred at 75° C. for 4 h to obtain the intermediate VB-2.

[0048] 3) 207.6 g of 3-chloro-2-hydroxypropyl sodium sulfonate with a purity of 98.5% was dissolved in 415.2 g of water to prepare an aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate. The aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate was added to the intermediate VB-2 in 8 batches, and the mixture was stirred at 75° C. for 8 h to obtain a sodium pyrrolidone sulfonate surfactant (XP). XP was evaporated under normal pressure to remove isopropanol and water, and was recrystallized and purified 3 times using methanol as a solvent to obtain pure XP.

[0049] The reaction formula is:

[0050]

[0051] XP) structural analysis:

[0052] FTIR analysis Figure 1 Shown: 3361cm -1 (1) is the OH stretching vibration absorption peak, 2920 cm -1 (2) is the asymmetric stretching vibration absorption peak of methylene, 2850 cm -1 (3) is the peak of the symmetrical stretching vibration of methylene, 1720 cm -1 (4) is the C=O stretching vibration absorption peak in the carboxyl group, 1201 cm-1 (5) is the stretching vibration absorption peak of CN, 1051 cm -1 (6) is the asymmetric stretching vibration absorption peak of the sulfonic acid group S=O, 729 cm -1 (7) is the in-plane rocking vibration of methylene, 621 cm -1 (8) is the stretching vibration absorption peak of SO.

[0053] Mass spectrometry analysis Figure 2 Shown: HRMS (ESI) (negative) m / z: [M-Na + ] - Calcd for C 32 H 62 O 10 N2S2Cl,733.3534; Found 733.4607.

[0054] Example 2

[0055] Preparation of Sodium Pyrrolidone Sulfonate Surfactant (XP)

[0056] 1) Add 326 g of N-hydrogenated tallow-1,3-propylene diamine and 500 g of ethanol into a three-necked flask, heat and stir at 62° C., then add 130.1 g of itaconic acid in 5 batches, stir and react at 62° C. for 5 h to obtain intermediate VB-1.

[0057] 2) 122.2 g of 1,3-propane sultone was added to the intermediate VB-1 in 5 batches, and the mixture was stirred at 62° C. for 5 h to obtain the intermediate VB-2.

[0058] 3) 201.6 g of 3-chloro-2-hydroxypropyl sodium sulfonate with a purity of 98.5% was dissolved in 404.0 g of water to prepare an aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate. The aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate was added to the intermediate (VB-2) in 5 batches, and the reaction was stirred at 62° C. for 9.5 hours to obtain a sodium pyrrolidone sulfonate surfactant (XP). XP was evaporated under normal pressure to remove ethanol and water, and recrystallized and purified three times using methanol as a solvent to obtain pure XP.

[0059] Example 3

[0060] Preparation of Sodium Pyrrolidone Sulfonate Surfactant (XP)

[0061] 1) Add 326 g of N-hydrogenated tallow-1,3-propylene diamine and 900 g of propanol into a three-necked flask, heat and stir at 82° C., then add 139.2 g of itaconic acid in 12 batches, stir and react at 82° C. for 3 h to obtain intermediate VB-1.

[0062] 2) 134.3 g of 1,3-propane sultone was added to the intermediate VB-1 in 12 batches, and the mixture was stirred at 82° C. for 3 h to obtain the intermediate VB-2.

[0063] 3) 219.4 g of 3-chloro-2-hydroxypropyl sodium sulfonate with a purity of 98.5% was dissolved in 438.8 g of water to prepare an aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate. The aqueous solution of 3-chloro-2-hydroxypropyl sodium sulfonate was added to the intermediate VB-2 in 12 batches, and the reaction was stirred at 82° C. for 6.5 hours to obtain a sodium pyrrolidone sulfonate surfactant (XP). XP was evaporated under normal pressure to remove propanol and water, and recrystallized and purified three times using methanol as a solvent to obtain pure XP.

[0064] Experimental Example 1

[0065] The foam suppression performance of the sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 was measured: 10 mL of 0.5% sodium dodecylbenzene sulfonate (LBS) aqueous solution and a certain mass of sample were placed in a 100 mL stoppered measuring cylinder, shaken vigorously 20 times, the foam volume was measured, and the foam suppression value (U) was calculated.

[0066] U=(V0-V1) / V0

[0067] Wherein: V0 is the foam volume (mL) in the blank experiment, and V1 is the foam volume (mL) when the sample is added.

[0068] The foam suppression performance test data are shown in Table 1 and Table 2. By comparing with OP-10, the U of XP is 0.93. It can be seen that the sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 has a good foam suppression ability.

[0069] Table 1 Antifoaming performance before purification

[0070]

[0071]

[0072] Table 2 Antifoaming performance after purification

[0073]

[0074] Experimental Example 2

[0075] Take 20mL of 0.1% (mass fraction) aqueous solution of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 (using NaOH to adjust pH = 12) and 20mL of liquid paraffin in a 100mL stoppered measuring cylinder, plug the stopper, shake vigorously 5 times, let stand for 1 minute, repeat five times, and measure the time to separate 10mL of water to be 50s, which has good emulsification ability.

[0076] Experimental Example 3

[0077] Prepare 120 mL of a 0.001 mol / L aqueous solution of the pure product (XP) of sodium pyrrolidone sulfonate surfactant prepared in Example 1. Take 20 mL of the solution in a 100 mL stoppered measuring cylinder and shake it vigorously 20 times. Measure the initial volume of the foam (L0), the volume of the foam after 5 minutes (L5), and the time required for the foam volume to become half of the original initial volume (t 1 / 2 ).

[0078] The results are shown in Table 3. Compared with sodium dodecylbenzene sulfonate, the pure product of the sodium pyrrolidone sulfonate type surfactant (XP) prepared in Example 1 has a L0 of 4 mL, indicating that the pure product of the sodium pyrrolidone sulfonate type surfactant (XP) prepared in Example 1 is a low-foaming surfactant.

[0079] Table 3 Foamability and foam stability

[0080]

[0081] Experimental Example 4

[0082] The surface tension (γ) of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 was measured to obtain a surface tension-log c diagram (eg Figure 3 The surface performance parameters were calculated (see Table 4). The surface performance of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 was good.

[0083] Table 4 Surface performance parameters of pure product (XP)

[0084]

[0085] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A sodium pyrrolidone sulfonate surfactant, characterized in that: Its molecular structure is shown in Formula XP:

2. A method for preparing the sodium pyrrolidone sulfonate surfactant according to claim 1, characterized in that: The following steps are involved: S1. Dissolve N-hydrogenated tallow-1,3-propylene diamine in an organic solvent I, add itaconic acid, mix and heat to react, and obtain an intermediate VB-1. The structural formula of the intermediate VB-1 is: S2. Add 1,3-propane sultone to the intermediate VB-1, mix and heat to react, and obtain the intermediate VB-2. The structural formula of the intermediate VB-2 is: S3. Adding an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the intermediate VB-2, mixing and heating the mixture to react, thereby obtaining a sodium pyrrolidone sulfonate type surfactant; distilling off the organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then purifying the mixture by recrystallization with an organic solvent II to obtain a pure sodium pyrrolidone sulfonate type surfactant.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the N-hydrogenated tallow-1,3-propylene diamine, the organic solvent I, itaconic acid, 1,3-propane sultone, and 3-chloro-2-hydroxypropyl sodium sulfonate is 1:7-21:1.00-1.07:1.00-1.10:1.00-1.

10.

4. The preparation method according to claim 2, characterized in that: The organic solvent I comprises one of ethanol, propanol or isopropanol.

5. The preparation method according to claim 2, characterized in that: The mass fraction of sodium 3-chloro-2-hydroxypropyl sulfonate in the sodium 3-chloro-2-hydroxypropyl sulfonate aqueous solution is 27-37%.

6. The preparation method according to claim 2, characterized in that: The organic solvent II includes one of petroleum ether, methanol or ethyl acetate.

7. The preparation method according to claim 2, characterized in that: In step S1, itaconic acid is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 3 to 5 hours.

8. The preparation method according to claim 2, characterized in that: In step S2, 1,3-propane sultone is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 3 to 5 hours.

9. The preparation method according to claim 2, characterized in that: In step S3, the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is added in 5 to 12 batches, and the reaction temperature of the mixed heating reaction is 62 to 82° C., and the reaction time is 6.5 to 9.5 h.

10. Use of the sodium pyrrolidone sulfonate surfactant according to claim 1 in a foam suppressor and / or a low foaming surfactant and / or an emulsifier.

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