A pyrrolidone surfactant and its preparation method and application

Abstract

The present invention belongs to the field of fine chemical technology and relates to a pyrrolidone surfactant and its preparation method and application. The molecular structural formula of the pyrrolidone surfactant is: #imgabs0# The molar ratio of the pyrrolidone surfactant preparation is: N-hydrogenated tallow-1,3-propylene diamine, organic solvent S1, itaconic acid, and 1,3-propane sultone is 1: (8.5-20.5): (1.00-1.06): (1.00-1.08). The pyrrolidone surfactant is a double-headed hydrophilic group, i.e., a propanesulfonic acid group in the molecular structure and a carboxyl group on the pyrrolidone ring. It occupies a large spatial volume, has a relatively wide spatial action range, and has a relatively good effect. It can be used as a foam suppressant, a low-foam (or medium-foam) surfactant, and an emulsifier.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and in particular to a pyrrolidone surfactant and a preparation method and application thereof. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance 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 those skilled in the art.

[0003] Low-foaming (or medium-foaming) surfactants are surfactants that exhibit low or medium foaming properties in applications such as industrial cleaning or process vessel cleaning. For example, a low-foaming organosilicon surfactant, its preparation method, and application (CN113317315A) address the problem of excessive foaming in the prior art.

[0004] Currently, the development of low-foaming (or medium-foaming) surfactants primarily focuses on the combination of multiple surfactants. Reports of substances with a single chemical structure are relatively rare, and their synthesis methods are difficult and costly. Summary of the Invention

[0005] To address the current shortage of low-foaming (or medium-foaming) surfactants, the present invention provides a pyrrolidone surfactant having anti-foaming properties, low-foaming (or medium-foaming) properties, and good surface activity. Also provided is a method for preparing the pyrrolidone surfactant.

[0006] The technical solution of the present invention is:

[0007] In a first aspect of the present invention, a pyrrolidone surfactant is provided, which is a compound represented by formula T:

[0008]

[0009] The pyrrolidone surfactant is a double-headed hydrophilic group, namely the propanesulfonic acid group in the molecular structure and the carboxyl group on the pyrrolidone ring. It occupies a large spatial volume, has a wide spatial action range, and has a good effect.

[0010] In the design process of the present invention, a variety of hydrophilic groups are designed, such as carboxylic acid groups, sulfonic acid groups, pyrrolidone structures, and tertiary amine groups. And a lipophilic group (C 18 H 37 ), forming a new type of pyrrolidone surfactant. This substance exhibits anti-foaming properties, low foaming (or medium foaming) properties and good surface activity.

[0011] The second aspect of the present invention provides a method for preparing the pyrrolidone surfactant, comprising the following steps:

[0012] 1) N-hydrogenated tallow-1,3-propylene diamine, organic solvent S1 and itaconic acid are mixed and reacted to obtain a reaction intermediate LM, the structural formula of the reaction intermediate LM is:

[0013]

[0014] 2) adding 1,3-propane sultone to the reaction intermediate LM, mixing and reacting to obtain a pyrrolidone surfactant product T; evaporating the organic solvent S1 from the product T under normal pressure, and then purifying by recrystallization from an organic solvent S2 to obtain a pure product T.

[0015] The reaction is as follows:

[0016]

[0017]

[0018] In one or more embodiments, the molar ratio of N-hydrogenated tallow-1,3-propylene diamine, organic solvent S1, itaconic acid, and 1,3-propane sultone is 1: (8.5-20.5): (1.00-1.06): (1.00-1.08).

[0019] In one or more embodiments, in step 1), the organic solvent S1 is ethanol, propanol or isopropanol.

[0020] In one or more embodiments, in step 1), during the synthesis of the reaction intermediate LM, the reaction temperature is 65-82° C., and the reaction time is 2.5-5.5 h.

[0021] In one or more embodiments, in step 2), during the synthesis of product T, the reaction temperature is 65-82° C., and the reaction time is 2.5-5.5 h.

[0022] In one or more embodiments, in step 2), the organic solvent S2 for separation and purification by recrystallization is methanol, petroleum ether or ethyl acetate, preferably ethyl acetate.

[0023] In one or more embodiments, the preparation method of the pyrrolidone surfactant T specifically comprises the following steps:

[0024] (1) Add N-hydrogenated tallow-1,3-propylene diamine to a reactor, add an organic solvent S1, heat and stir to dissolve, then add itaconic acid in 4 to 9 batches. After the addition is complete, stir and react at 65 to 82° C. for 2.5 to 5.5 hours to obtain a reaction intermediate LM;

[0025] (2) 1,3-propane sultone is added to the reaction intermediate LM in 4 to 9 batches. After the addition is completed, the mixture is stirred and reacted at 65 to 82° C. for 2.5 to 5.5 hours to obtain a pyrrolidone surfactant product T. The organic solvent S1 is evaporated from the product T under normal pressure, and the product T is then recrystallized and purified three times using an organic solvent S2 to obtain a pure product T.

[0026] In a third aspect of the present invention, there is provided a use of the pyrrolidone surfactant described in the first aspect as a foam suppressant, a low-foaming (or medium-foaming) surfactant, and an emulsifier. For example, the use in industrial cleaning can avoid the generation of large amounts of foam during the production process.

[0027] The specific embodiments of the present invention have the following beneficial effects:

[0028] (a) In the design process of the present invention, a variety of hydrophilic groups are designed, such as carboxylic acid groups, sulfonic acid groups, pyrrolidone structures, and tertiary amine groups. And a lipophilic group (C 18 H 37 ), forming a new type of pyrrolidone surfactant. This substance exhibits anti-foaming properties, low foaming (or medium foaming) properties and good surface activity.

[0029] (b) The chemical raw materials used in the present invention are easy to purchase, and the production and raw material costs are low.

[0030] (c) The preparation reaction temperature is relatively low, and a common reactor is used and the operation is carried out at normal pressure. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The accompanying drawings, 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.

[0032] Figure 1 This is the infrared spectrum of the pure product T of Example 1 of the present invention;

[0033] Figure 2 This is the NMR spectrum of the pure product T of Example 1 of the present invention (I);

[0034] Figure 3 This is the NMR spectrum of the pure product T of Example 1 of the present invention (II);

[0035] Figure 4 This is the mass spectrum of the pure product T of Example 1 of the present invention (positive);

[0036] Figure 5 This is the mass spectrum of the pure product T of Example 1 of the present invention (negative);

[0037] Figure 6 This is a graph showing the relationship between the surface tension and the logarithm of the concentration of the pure product T of Example 1 of the present invention. DETAILED DESCRIPTION

[0038] 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 with reference to specific embodiments and experimental examples.

[0039] Example 1

[0040] (1) Preparation of pyrrolidone surfactant (product T):

[0041] 1) Add 163.0 g of N-hydrogenated tallow-1,3-propylene diamine and 350.0 g of isopropyl alcohol to a reactor, heat and stir at 75° C. to dissolve, then add 67.0 g of itaconic acid in 6 batches, and stir at 75° C. for 4 hours to obtain an intermediate (LM).

[0042] 2) 64.1 g of 1,3-propane sultone was added to the intermediate (LM) in 6 batches, and the mixture was stirred at 75° C. for 4 hours to obtain a pyrrolidone surfactant product T.

[0043] The product T was evaporated to remove isopropyl alcohol under normal pressure, and then purified by recrystallization from ethyl acetate three times to obtain pure product T.

[0044] Infrared analysis ( Figure 1 ): 3431cm -1 (peak 1) is the OH stretching vibration absorption peak, 2918 cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2850 cm -1 (peak 3) is the symmetrical stretching vibration peak of methylene, 1728 cm -1 (peak 4) is the C=O stretching vibration absorption peak in the carboxyl group, 1201 cm -1 (peak 5) is the stretching vibration absorption peak of CN, 1040 cm -1 (peak 6) is the asymmetric stretching vibration absorption peak of sulfonic acid group S=O, 723 cm -1 (peak 7) is the in-plane rocking vibration of the methylene group, 609 cm -1 (peak 8) is the stretching vibration absorption peak of SO.

[0045] 1 H-NMR analysis ( Figure 2 and Figure 3 ): 1H NMR (400MHz, CD3OD), δ: 0.8846-0.9183 (3H, t, J = 6.74Hz, -C H 3),1.2887(30H,s,CH3(C H 2) 15 CH2CH2-),1.6652-1.7384(2H,m,-CH3(CH2) 15 C H 2CH2-),1.9058-1.9480(2H,m,-NCH2C H 2CH2N-),2.0944-2.1632(2H,m,-NCH2C H 2CH2SO3H),2.6779-2.7101(2H,t,J=6.44Hz,CH3(CH2) 15 CH2CH2NC H 2CH2CH2N-),2.8655-2.9043(2H,t,J=7.76Hz,-NC H 2CH2CH2SO3H),2.9871-2.9966(2H,d,-NCOC H 2CH-),3.1042-3.1377(2H,t,J=6.7Hz,CH3(CH2) 15 CH2C H 2N-),3.6404-3.6720(2H,t,J=6.32Hz,-C H 2SO3H),4.2094-4.2426(2H,t,J=6.64Hz,CH3(CH2) 15 CH2CH2NCH2CH2C H 2N-),4.2851-4.3259(1H,m,-NCOCH2C H -),4.4363-4.4637(2H,d,-NC H 2CHCOOH) ppm. 3.3103 ppm is the deuterated methanol solvent peak; 4.8929 ppm is the deuterated methanol water peak.

[0046] MS analysis ( Figure 4 ):HRMS(ESI)(Positive)m / z:[M+H + ] + Calcd for C 29 H 57 O6N2S,561.3937; Found 561.3922.

[0047] MS analysis ( Figure 5): HRMS(ESI)(negative)m / z:[MH + ] - Calcd for C 29 H 55 O6N2S,559.3781; Found 559.4324.

[0048] Experimental Example 1

[0049] The foam suppression performance of the pyrrolidone surfactant T prepared in Example 1 was measured: 10 mL of a 0.5% (mass fraction) aqueous solution of sodium dodecylbenzenesulfonate (LBS) and a predetermined amount of sample T were poured into a 100 mL stoppered graduated cylinder. The cylinder was stoppered and vigorously shaken 20 times. The foam volume was recorded. The foam suppression value (Y) represents the foam suppression ability of sample T.

[0050] Y=(V0-V1) / V0

[0051] Where V0 is the foam volume (mL) during the blank test; V1 is the foam volume (mL) when sample T is added.

[0052] The foam suppression performance of pyrrolidone surfactant T and emulsifier OP-10 is compared in Tables 1 and 2. It can be seen that the pyrrolidone surfactant T prepared in Example 1 has better foam suppression ability.

[0053] Table 1 Antifoaming ability (before purification)

[0054]

[0055] Table 2 Antifoaming ability (after purification)

[0056]

[0057]

[0058] Experimental Example 2

[0059] Take 20 ml of 0.1% (mass fraction) aqueous solution of pure pyrrolidone surfactant product T and 20 ml of liquid paraffin, pour them into a 100 ml stoppered measuring cylinder, plug the stopper, shake it up and down vigorously 5 times, then let it stand for 1 minute, repeat 5 times, and the time it takes to separate 10 ml of water is 368 seconds. The sample has a strong emulsifying ability.

[0060] Experimental Example 3

[0061] Prepare 120 ml of a 0.001 mol / L aqueous solution of pure pyrrolidone surfactant product T. Divide the solution into two equal portions, and adjust the pH of one portion to 11 by adding NaOH. Place 20 ml of the solution in a 100 ml stoppered graduated cylinder and hold at 25°C for 10 minutes. Shake the solution up and down 20 times and allow it to stand. Record the initial foam volume (H0), the foam volume after 5 minutes (H5), and the time it takes for the foam volume to decay to half its initial volume (t 1 / 2 ).

[0062] The results are shown in Table 3. Compared with sodium dodecylbenzenesulfonate, the H0 of the pure pyrrolidone surfactant product T (after alkali adjustment) prepared in Example 1 was 5 mL, which is a smaller value, indicating that the pure pyrrolidone surfactant product T (after alkali adjustment) prepared in Example 1 is a low-foaming surfactant. The H0 of product T (before alkali adjustment) was 24 mL, which is a medium value, indicating that the pure pyrrolidone surfactant product T (before alkali adjustment) prepared in Example 1 is a medium-foaming surfactant.

[0063] Table 3 Foamability and Foam Stability (After Purification)

[0064]

[0065]

[0066] Experimental Example 4

[0067] The surface tension was measured using an interfacial tension meter to obtain the surface tension-log c curve (see Figure 6 ), calculate the critical micelle concentration (CMC) of the pure product T of pyrrolidone surfactant, the surface tension (γ CMC ), C 20 、pC 20 and CMC / C 20 (See Table 4.) It can be seen that the surface properties of the pure pyrrolidone surfactant product T are better.

[0068] Table 4 Surface performance parameters

[0069]

[0070] Comparative Example 1

[0071] The following product structure was prepared:

[0072]

[0073] Its foam suppression performance is (pure product): when 0.1g is added, the foam volume is 72mL, and the foam suppression value Y is 0.14. When 0.05g is added, the foam volume is 81mL, and the foam suppression value Y is 0.04. Its foam suppression performance is poor.

[0074] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A pyrrolidone surfactant, characterized in that It is a substance represented by formula T, and the molecular structure of the substance represented by formula T is: ， Formula T; C 18 H 37 It is a straight chain structure.

2. The method for preparing a pyrrolidone surfactant according to claim 1, wherein The method includes the following steps: 1) N-hydrogenated tallow-1,3-propylene diamine, organic solvent S1 and itaconic acid are mixed and reacted to obtain a reaction intermediate LM, the structural formula of the reaction intermediate LM is: ； 2) Add 1,3-propane sultone to the reaction intermediate LM, mix and react to obtain a pyrrolidone surfactant product T; evaporate the organic solvent S1 from product T under normal pressure, and then purify it by recrystallization from organic solvent S2 to obtain pure product T.

3. The preparation method according to claim 2, wherein The molar ratio of the N-hydrogenated tallow-1,3-propylene diamine, the organic solvent S1, itaconic acid, and 1,3-propane sultone is 1:8.5-20.5:1.00-1.06:1.00-1.

08.

4. The preparation method according to claim 2, wherein In step 1), the organic solvent S1 is ethanol, propanol or isopropanol.

5. The preparation method according to claim 2, wherein In step 1), during the synthesis of the reaction intermediate LM, the reaction temperature is 65-82° C. and the reaction time is 2.5-5.5 h.

6. The preparation method according to claim 2, wherein In step 2), during the synthesis of product T, the reaction temperature is 65-82° C. and the reaction time is 2.5-5.5 h.

7. The preparation method according to claim 2, wherein In step 2), the organic solvent S2 for separation and purification by recrystallization is methanol, petroleum ether or ethyl acetate.

8. The preparation method according to claim 7, wherein In step 2), the organic solvent S2 separated and purified by recrystallization is ethyl acetate.

9. The preparation method according to claim 2, wherein The specific steps include: (1) Add N-hydrogenated tallow-1,3-propylene diamine to a reactor, add organic solvent S1, heat and stir to dissolve, then add itaconic acid in 4 to 9 batches. After the addition is complete, stir and react at 65 to 82°C for 2.5 to 5.5 hours to obtain the reaction intermediate LM; (2) 1,3-Propane sultone was added to the reaction intermediate LM in 4 to 9 batches. After the addition was completed, the reaction was stirred at 65 to 82 °C for 2.5 to 5.5 h to obtain a pyrrolidone surfactant product T. The organic solvent S1 was evaporated from the product T under normal pressure, and then the product T was recrystallized and purified three times with an organic solvent S2 to obtain a pure product T.

10. Use of the pyrrolidone surfactant according to claim 1 or the pyrrolidone surfactant prepared by the preparation method according to any one of claims 2 to 9 as a foam suppressant, a low-foaming or medium-foaming surfactant, or an emulsifier.

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