A sodium pyrrolidone sulfonate surfactant, its preparation method and application

Abstract

This invention belongs to the field of surfactant technology, specifically relating to a sodium pyrrolidone sulfonate type surfactant, its preparation method, and its application. To address the shortcomings of existing low-foaming surfactants, such as limited variety and complex synthesis methods, the present invention provides a sodium pyrrolidone sulfonate type surfactant with the following molecular structure: The present invention uses N-hydrogenated tallow-1,3-propylene diamine as the starting material for preparing the sodium pyrrolidone sulfonate type surfactant XP. During the preparation of the sodium pyrrolidone sulfonate type surfactant XP, itaconic acid, 1,3-propanesulfonate lactone, and 3-chloro-2-hydroxypropyl sulfonate are added sequentially, introducing hydroxyl, carboxylic acid, quaternary ammonium salt, sulfonic acid (sodium) groups, and hydrophilic amide groups on the ring into its molecular structure, thereby improving its surface properties.

Description

Technical Field

[0001] This invention belongs to the field of surfactant technology, specifically relating to a sodium pyrrolidone 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] Surfactants are amphiphilic molecules composed of a hydrophilic head group and a hydrophobic tail chain. In aqueous solutions, they can self-assemble into various aggregate structures, exhibiting unique physicochemical properties and finding wide application in detergents, food, pharmaceuticals, coatings, textiles, construction, oil extraction, and many other fields. When a surfactant is mixed with water, the hydrophilic end dissolves in the water, while the hydrophobic end detaches and aggregates at the water surface. At the surface, the hydrophobic group leaves the water and enters the air, while the hydrophilic group dissolves and remains on the surface. When the water is agitated, air is introduced, and the hydrophobic group traps the air, forming bubbles.

[0004] Low-foaming surfactants are surfactants that exhibit low-foaming properties in spray cleaning or other applications. The purpose of low foaming is to meet the requirements of the production environment. In the manufacturing processes of certain products, foam generation has adverse effects; therefore, low-foaming or non-foaming surfactants are needed. For example, non-foaming or low-foaming industrial detergents can be used as metal cleaners, metal degreasers, and plastic cleaners.

[0005] Currently, low-foaming surfactants are mainly commercially available as composites, with few reports on products with independent chemical compositions, and most of these are nonionic surfactants. A method for preparing and applying a low-foaming nonionic surfactant (CN112898559A) discloses that it is obtained by reacting alkyl glycoside polyoxypropylene ether and chloromethane under an alkaline catalyst. It exhibits excellent high-temperature stability and can be used for fuel leak treatment at high temperatures, preventing fire and explosion hazards.

[0006] There are relatively few existing technologies for developing sulfonate-type low-foaming surfactants, which results in high prices, complex preparation methods, and certain defects in their antifoaming, surface, and emulsifying properties. Summary of the Invention

[0007] To address the shortcomings of existing low-foaming surfactants, such as a limited variety and complex synthesis methods, this invention aims to provide a sodium pyrrolidone sulfonate surfactant, its preparation method, and its applications. The sodium pyrrolidone sulfonate surfactant provided by this invention possesses antifoaming properties, low foaming characteristics, and good surface activity, and its preparation method is relatively simple.

[0008] To achieve the above objectives, the present invention is implemented through the following technical solution:

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

[0010]

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

[0012] S1. N-hydrogenated tallow-1,3-propylene diamine is dissolved in organic solvent I, and itaconic acid is added and heated to react, yielding intermediate VB-1. The structural formula of intermediate VB-1 is as follows:

[0013]

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

[0015]

[0016] S3. Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate VB-2, mix and heat to react, and obtain sodium pyrrolidone sulfonate type surfactant; evaporate organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then recrystallize and purify it with organic solvent II to obtain pure sodium pyrrolidone sulfonate type surfactant.

[0017] Thirdly, the present invention provides the use of sodium pyrrolidone sulfonate type surfactants as described in the first aspect in defoamers and / or low-foaming surfactants and / or emulsifiers.

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

[0019] (i) In this invention, hydroxyl groups, carboxylic acid groups, quaternary ammonium salt groups, sulfonic acid (sodium) groups, and hydrophilic amide groups on the ring are linked in a certain manner, and combined with C 18 H 37The lipophilic group constitutes a novel structure of sodium pyrrolidone sulfonate surfactant. This sodium pyrrolidone sulfonate surfactant has more hydrophilic groups and therefore better surface properties.

[0020] (ii) The raw materials for the sodium pyrrolidone sulfonate surfactant of the present invention are widely available and have low production costs.

[0021] (iii) The preparation process is simple, using a common reactor, and does not require reaction under high temperature and high pressure. Attached Figure Description

[0022] 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.

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

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

[0025] Figure 3 The graph shows the surface tension versus concentration logarithm of the pure sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1. Detailed Implementation

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

[0027]

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

[0029] S1. N-hydrogenated tallow-1,3-propylene diamine is dissolved in organic solvent I, and itaconic acid is added and heated to react, yielding intermediate VB-1. The structural formula of intermediate VB-1 is as follows:

[0030]

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

[0032]

[0033] S3. Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate VB-2, mix and heat to react, and obtain sodium pyrrolidone sulfonate type surfactant; evaporate organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then recrystallize and purify it with organic solvent II to obtain pure sodium pyrrolidone sulfonate type surfactant.

[0034] In one or more embodiments of this implementation, the molar ratio of N-hydrogenated tallow-1,3-propanediamine, organic solvent I, itaconic acid, 1,3-propanesulfonate lactone, and sodium 3-chloro-2-hydroxypropylsulfonate is 1:(7-21):(1.00-1.07):(1.00-1.10):(1.00-1.10).

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

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

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

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

[0039] In one or more embodiments of this implementation, in step S2, 1,3-propanesulfonate lactone is added in 5 to 12 batches, and the reaction temperature for mixing and heating is 62 to 82°C, and the reaction time is 3 to 5 hours.

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

[0041] A 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 defoamers and / or low-foaming surfactants and / or emulsifiers.

[0042] This invention uses N-hydrogenated tallow-1,3-propanediamine as the starting material for preparing sodium pyrrolidone sulfonate type surfactant XP. In the preparation process of sodium pyrrolidone sulfonate type surfactant XP, itaconic acid, 1,3-propanesulfonate lactone and 3-chloro-2-hydroxypropyl sulfonate are added sequentially to introduce hydroxyl, carboxylic acid, quaternary ammonium salt, sulfonic acid (sodium) group and hydrophilic amide group on the ring into its molecular structure, thereby improving its surface properties.

[0043] 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 and comparative examples.

[0044] Example 1

[0045] Preparation of sodium pyrrolidone sulfonate type surfactant (XP)

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

[0047] 2) Add 128.2 g of 1,3-propanesulfonate lactone to intermediate VB-1 in 8 batches, stir at 75 °C for 4 h to obtain intermediate VB-2.

[0048] 3) Dissolve 207.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (98.5% purity) in 415.2 g of water to prepare an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate. Add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate VB-2 in eight batches, and stir at 75°C for 8 hours to obtain a sodium pyrrolidone sulfonate surfactant (XP). Evaporate isopropanol and water from XP under normal pressure, and then recrystallize three times using methanol as a solvent to obtain pure XP.

[0049] The reaction formula is:

[0050]

[0051] Structural analysis of XP:

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

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

[0054] Example 2

[0055] Preparation of sodium pyrrolidone sulfonate type surfactant (XP)

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

[0057] 2) Add 122.2g of 1,3-propanesulfonate lactone to intermediate VB-1 in 5 batches, stir at 62℃ for 5h to obtain intermediate VB-2.

[0058] 3) Dissolve 201.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (98.5% purity) in 404.0 g of water to prepare an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate. Add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate (VB-2) in five batches, and stir at 62°C for 9.5 h to obtain a sodium pyrrolidone sulfonate surfactant (XP). Ethanol and water are evaporated from XP under normal pressure, and the product is purified by recrystallization three times using methanol as a solvent to obtain pure XP.

[0059] Example 3

[0060] Preparation of sodium pyrrolidone sulfonate type surfactant (XP)

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

[0062] 2) Add 134.3g of 1,3-propanesulfonate lactone to intermediate VB-1 in 12 batches, stir at 82℃ for 3h to obtain intermediate VB-2.

[0063] 3) Dissolve 219.4 g of sodium 3-chloro-2-hydroxypropyl sulfonate (98.5% purity) in 438.8 g of water to prepare an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate. Add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate VB-2 in 12 batches, and stir at 82 °C for 6.5 h to obtain a sodium pyrrolidone sulfonate surfactant (XP). Evaporate propanol and water from XP under normal pressure, and then recrystallize three times using methanol as 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 determined: 10 mL of 0.5% sodium dodecylbenzene sulfonate (LBS) aqueous solution and a certain mass of sample were placed in a 100 mL stoppered graduated cylinder, shaken vigorously 20 times, the foam volume was measured, and the foam suppression value (U) was calculated.

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

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

[0068] The data for the antifoaming performance test are shown in Tables 1 and 2. Compared with OP-10, XP's U value is 0.93. It can be seen that the sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 has better antifoaming ability.

[0069] Table 1. Antifoaming performance before purification

[0070]

[0071]

[0072] Table 2. Antifoaming properties after purification

[0073]

[0074] Experiment Example 2

[0075] Take 20 mL of 0.1% (mass fraction) sodium pyrrolidone sulfonate surfactant (XP) pure product aqueous solution prepared in Example 1 (adjusted pH=12 with NaOH) and 20 mL of liquid paraffin into a 100 mL stoppered graduated cylinder, stopper it, shake vigorously 5 times, let stand for 1 minute, repeat five times, and measure the time to separate 10 mL of water. It is 50 s, which shows that it has good emulsifying ability.

[0076] Experimental Example 3

[0077] Prepare 120 mL of a 0.001 mol / L aqueous solution of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1. Take 20 mL of this solution and place it in a 100 mL stoppered graduated cylinder. Shake 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 its initial volume (t). 1 / 2 ).

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

[0079] Table 3 Foaming and Foam Stability

[0080]

[0081] Experiment Example 4

[0082] The surface tension (γ) of the pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 was measured, and the surface tension-log c plot was obtained (as shown in the figure). Figure 3 (As shown). Surface performance parameters were calculated (see Table 4). The pure product of sodium pyrrolidone sulfonate surfactant (XP) prepared in Example 1 showed good surface performance.

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

[0084]

[0085] 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. A sodium pyrrolidone sulfonate type surfactant, characterized in that, Its molecular structure is shown in formula XP: XP; The surfactant is prepared from the following raw materials: N-hydrogenated tallow-1,3-propanediamine, organic solvent I, itaconic acid, 1,3-propanesulfonate lactone, and sodium 3-chloro-2-hydroxypropylsulfonate in a molar ratio of 1:7~21:1.00~1.07:1.00~1.10:1.00~1.

10.

2. A method for preparing a sodium pyrrolidone sulfonate type surfactant as described in claim 1, characterized in that, The following steps are involved: S1. N-hydrogenated tallow-1,3-propylene diamine is dissolved in organic solvent I, and itaconic acid is added and heated to react, yielding intermediate VB-1. The structural formula of intermediate VB-1 is as follows: ； S2. Add 1,3-propanesulfonate lactone to intermediate VB-1, mix and heat to react, and obtain intermediate VB-2. The structural formula of intermediate VB-2 is: ； S3. Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to intermediate VB-2, mix and heat to react, and obtain sodium pyrrolidone sulfonate type surfactant; evaporate organic solvent I and water from the sodium pyrrolidone sulfonate type surfactant under normal pressure, and then recrystallize and purify it with organic solvent II to obtain pure sodium pyrrolidone sulfonate type surfactant.

3. The preparation method according to claim 2, characterized in that, The organic solvent I is selected from ethanol, propanol, or isopropanol.

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

5. The preparation method according to claim 2, characterized in that, The organic solvent II is selected from petroleum ether, methanol, or ethyl acetate.

6. 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 for mixing and heating is 62 to 82°C, and the reaction time is 3 to 5 hours.

7. The preparation method according to claim 2, characterized in that, In step S2, 1,3-propanesulfonate lactone is added in 5 to 12 batches, and the reaction temperature for mixing and heating 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 S3, the aqueous solution of sodium 3-chloro-2-hydroxypropylsulfonate is added in 5 to 12 batches, and the reaction temperature of the mixture and heating reaction is 62 to 82°C, and the reaction time is 6.5 to 9.5 h.

9. The use of a sodium pyrrolidone sulfonate surfactant as described in claim 1 in defoamers and / or low-foaming surfactants and / or emulsifiers.

Images