A pyrrolidone amphoteric surfactant and its preparation method and application

Abstract

This invention belongs to the technical field of amphoteric surfactants, and relates to a pyrrolidone amphoteric surfactant, its preparation method, and its application. Its molecular structural formula is: where X is Cl or Br; n = 12, 14, 16, or 18. The synthesis ratio of this pyrrolidone amphoteric surfactant is: N-alkyl-1,3-propylenediamine, alcohol solvent, itaconic acid, 1,3-propanesulfonate lactone, sodium 2-haloethylsulfonate, and water, in a molar ratio of 1:(9-20):(1.01-1.06):(1.01-1.09):(1.00-1.09):(17-28). This pyrrolidone amphoteric surfactant can be used as an antifoaming agent, a low-foaming surfactant, and an emulsifier.

Description

Technical Field

[0001] This invention relates to the field of amphoteric surfactant technology, specifically to a pyrrolidone amphoteric 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 surfactant products that exhibit low foaming ability in applications such as industrial cleaning. For example, the application of low-foaming amphoteric surfactants (CN112844219A) protects the environment and is beneficial to environmental protection.

[0004] Currently, low-foaming surfactants are mainly commercial products that are composites of multiple surfactants. Very few have independent chemical structures, and they do not necessarily possess antifoaming properties simultaneously; furthermore, their synthesis is technically challenging. Summary of the Invention

[0005] To address the current shortage of low-foaming surfactants, the present invention aims to provide a pyrrolidone amphoteric surfactant, which possesses antifoaming properties, low-foaming properties, and good surface properties.

[0006] The technical solution of this invention is as follows:

[0007] In a first aspect, the present invention provides a pyrrolidone amphoteric surfactant, which is a compound of the formula FM-nX:

[0008]

[0009] Where X is Cl or Br; n = 12, 14, 16 or 18.

[0010] The pyrrolidone amphoteric surfactant is a trihead surfactant, meaning it contains a propanesulfonic acid group, a sodium ethyl sulfonate group, and a carboxyl group on the pyrrolidone ring. This surfactant occupies a large volume, has a wide range of action, and therefore exhibits superior efficacy.

[0011] In the molecular structure design process of this invention, various hydrophilic groups are introduced, such as carboxylic acid groups, sulfonic acid groups, sodium sulfonate groups, pyrrolidone structures, and quaternary ammonium salt groups, and combined with lipophilic groups of different carbon chain lengths (C n H 2n+1 This constitutes a novel pyrrolidone amphoteric surfactant, exhibiting antifoaming, low-foaming properties and good surface activity.

[0012] In a second aspect, the present invention provides a method for preparing the pyrrolidone amphoteric surfactant, comprising the following steps:

[0013] 1) An intermediate GA1-n is obtained by reacting N-alkyl-1,3-propanediamine, an alcohol solvent, and itaconic acid. The structural formula of the intermediate GA1-n is as follows:

[0014]

[0015] Where n = 12, 14, 16 or 18;

[0016] 2) Add 1,3-propanesulfonate lactone to intermediate GA1-n, mix and react to obtain intermediate GA2-n. The structural formula of intermediate GA2-n is:

[0017]

[0018] Where n = 12, 14, 16 or 18;

[0019] 3) Add an aqueous solution of sodium 2-haloethyl sulfonate to the intermediate GA2-n, mix and react to obtain the pyrrolidone amphoteric surfactant product FM-nX; evaporate the alcohol solvent and water from the product FM-nX under normal pressure, and then recrystallize and purify it with organic solvent P to obtain the pure product FM-nX.

[0020] The general reaction formula is as follows:

[0021]

[0022] In some embodiments, the molar ratio of N-alkyl-1,3-propanediamine, alcohol solvent, itaconic acid, 1,3-propanesulfonate lactone, sodium 2-haloethylsulfonate, and water is 1:(9-20):(1.01-1.06):(1.01-1.09):(1.00-1.09):(17-28).

[0023] In some embodiments, in step 1), the N-alkyl-1,3-propanediamine is N-dodecyl-1,3-propanediamine, N-tetradecyl-1,3-propanediamine, N-hexadecyl-1,3-propanediamine, or N-octadecyl-1,3-propanediamine.

[0024] In some embodiments, in step 1), the alcohol solvent is ethanol, propanol, or isopropanol.

[0025] In some embodiments, during step 1), the reaction temperature is 60–80°C and the reaction time is 2.5–5.5 hours during the synthesis of the reaction intermediate GA1-n.

[0026] In some embodiments, during step 2), the reaction temperature is 60–80°C and the reaction time is 2.5–5.5 hours during the synthesis of the reaction intermediate GA2-n.

[0027] In some embodiments, in step 3), during the synthesis of product FM-nX, the reaction temperature is 60–80°C and the reaction time is 7–9 hours.

[0028] In some embodiments, during step 3), in the process of synthesizing product FM-nX, the sodium 2-haloethylsulfonate is sodium 2-chloroethylsulfonate or sodium 2-bromoethylsulfonate.

[0029] In some embodiments, during step 3), in the process of synthesizing product FM-nX, the mass fraction of sodium 2-haloethyl sulfonate in the aqueous solution of sodium 2-haloethyl sulfonate is 25-39%.

[0030] In some embodiments, in step 3), the organic solvent P used for recrystallization separation and purification is methanol, petroleum ether, or ethyl acetate.

[0031] In some embodiments, the preparation method of the above-mentioned pyrrolidone amphoteric surfactant FM-nX specifically includes the following steps:

[0032] (1) Add N-alkyl-1,3-propanediamine to the reaction vessel, then add an alcohol solvent, heat and stir to dissolve; add itaconic acid solid in 4 to 11 batches, and after the addition is complete, stir the reaction at 60 to 80°C for 2.5 to 5.5 hours to obtain intermediate GA1-n;

[0033] (2) Add 1,3-propanesulfonic acid lactone solid to intermediate GA1-n in 4 to 11 batches. After the addition is complete, stir the reaction at 60 to 80°C for 2.5 to 5.5 hours to obtain intermediate GA2-n.

[0034] (3) Add sodium 2-haloethyl sulfonate aqueous solution to intermediate GA2-n in 4 to 11 batches. After the addition is complete, stir the reaction at 60 to 80°C for 7 to 9 hours to obtain pyrrolidone amphoteric surfactant product FM-nX. Evaporate alcohol solvent and water from product FM-nX under normal pressure, and then recrystallize and purify it 3 to 4 times with organic solvent P to obtain pure product FM-nX.

[0035] In a third aspect of the invention, an application of the aforementioned pyrrolidone amphoteric surfactant as an antifoaming agent, a low-foaming surfactant, and an emulsifier is provided. For example, its application in cleaning formulations in the industrial cleaning field can effectively prevent the generation of large amounts of foam.

[0036] The beneficial effects of this invention are:

[0037] (i) In the molecular structure design process of this invention, various hydrophilic groups are introduced, such as carboxylic acid groups, sulfonic acid groups, sodium sulfonate groups, pyrrolidone structures, and quaternary ammonium salt groups, and combined with lipophilic groups of different carbon chain lengths (C n H 2n+1 This constitutes a novel pyrrolidone amphoteric surfactant, exhibiting antifoaming, low-foaming properties and good surface activity.

[0038] (ii) Its reaction temperature is relatively low, and it uses ordinary reaction equipment and operates under normal pressure.

[0039] (iii) The chemical raw materials used are widely available and inexpensive. Attached Figure Description

[0040] 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.

[0041] Figure 1 The infrared spectrum of the pure product FM-18-Cl from Example 1 is shown below.

[0042] Figure 2 The NMR spectrum of the pure product FM-18-Cl from Example 1 is shown below.

[0043] Figure 3 The mass spectrum of the pure product FM-18-Cl from Example 1 is shown below.

[0044] Figure 4 The graph shows the relationship between the surface tension and the concentration of the pure product FM-18-Cl from Example 1. Detailed Implementation

[0045] 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 experimental examples.

[0046] Example 1

[0047] (1) Preparation of pyrrolidone amphoteric surfactant (product FM-18-Cl):

[0048] 1) Add 326.0g N-hydrogenated tallow-1,3-propanediamine and 700.0g isopropanol to a reaction vessel, heat and stir at 75°C, then add 134.0g itaconic acid in 7 batches, stir and react at 75°C for 4 hours to obtain intermediate (GA1-18).

[0049] 2) Add 128.2g of 1,3-propanesulfonate lactone to intermediate (GA1-18) in 7 batches, stir at 75℃ for 4 hours to obtain intermediate (GA2-18).

[0050] 3) Dissolve 197.8 g of sodium 2-chloroethylsulfonate monohydrate (98% purity) in 395.6 g of water to obtain an aqueous solution of sodium 2-chloroethylsulfonate. Add the aqueous solution of sodium 2-chloroethylsulfonate to the intermediate (GA2-18) in 7 batches, and stir at 75°C for 8 hours to obtain the pyrrolidone amphoteric surfactant product (FM-18-Cl). The product (FM-18-Cl) is purified by evaporation of isopropanol and water under normal pressure, and then purified by recrystallization three times with ethyl acetate to obtain the pure product (FM-18-Cl).

[0051] Infrared analysis ( Figure 1 ): 3438cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2922 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2850 cm⁻¹. -1 Peak 3 is the peak of the symmetric stretching vibration of the methylene group, at 1730 cm⁻¹. -1 Peak 4 is the absorption peak of the C=O stretching vibration in the carboxyl group, at 1195 cm⁻¹. -1 Peak 5 is the stretching vibration absorption peak of CN, at 1068 cm⁻¹. -1 Peak 6 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 723 cm⁻¹. -1 (peak 7) represents the in-plane rocking vibration of the methylene group, 611 cm⁻¹. -1 (peak 8) is the absorption peak of SO's stretching vibration.

[0052] 1 H-NMR analysis ( Figure 2 ): 1 H NMR (400MHz, CD3OD), δ: 0.8847-0.9189 (3H, t, J = 6.84Hz, -C H 3), 1.2891(30H,s,CH3(C H 2) 15 CH2CH2-),1.6654-1.7391(2H,m,-CH3(CH2) 15 C H 2CH2-),1.9761-2.0150(2H,m,-NCH2C H 2CH2N-),2.1057-2.1816(2H,m,-NCH2C H2CH2SO3H),2.6761-2.7104(6H,t,J=6.86Hz,CH3(CH2) 15 CH2CH2NC H 2CH2CH2N- and CH3(CH2) 15 CH2C H 2NC H 2CH2CH2SO3H),2.8832-2.9020(2H,d,-NCOC H 2CH-),2.9772-3.0081(2H,t,J=6.18Hz,-NC H 2CH2SO3Na),3.1959-3.2179(2H,t,J=4.4Hz,-NCH2CH2C H 2SO3H),3.6387-3.6704(2H,t,J=6.34Hz,-NCH2C H 2SO3Na),3.8155-3.8374(2H,t,J=4.38Hz,-NCH2CH2C H 2NCO-),4.2808-4.3220(1H,m,-NCOCH2C H -), 4.4342-4.4620(2H,d,-NC H 2CHCOOH)ppm.

[0053] MS analysis ( Figure 3 ): HRMS(ESI)(negative)m / z:[MH + ] - Calcd for C 31 H 59 O9N2S2ClNa,725.3248; Found 725.3841.[M-Na + ] - Calcd for C 31 H 60 O9N2S2Cl,703.3429; Found703.4187.

[0054] The reaction is as follows:

[0055]

[0056] Experimental Example 1

[0057] Take 10 mL of 0.5% (mass fraction) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain amount of the pyrrolidone amphoteric surfactant sample (FM-18-Cl) from Example 1, pour them into a 100 mL stoppered graduated cylinder, stopper the cylinder, shake vigorously 20 times, and record the foam volume. The foam suppression value (X) characterizes the foam suppression ability of the sample (FM-18-Cl).

[0058] X = (V0 - V1) / V0

[0059] V0 is the foam volume (mL) during the blank test; V1 is the foam volume (mL) when the sample (FM-18-Cl) is added.

[0060] The antifoaming properties are shown in Tables 1 and 2. Compared with OP-10, the pyrrolidone amphoteric surfactant (FM-18-Cl) prepared in Example 1 (before and after purification) has a strong antifoaming ability, with X reaching over 0.92.

[0061] Table 1. Antifoaming ability (before purification)

[0062]

[0063] Table 2. Antifoaming ability (after purification)

[0064]

[0065] Experiment Example 2

[0066] Take 20 mL of 0.1% (w / w) aqueous solution of the pure product of pyrrolidone amphoteric surfactant (FM-18-Cl) in Example 1 and 20 mL of liquid paraffin, pour them into a 100 mL stoppered graduated cylinder, stopper the cylinder, shake it vigorously 5 times and let it stand for 1 min. Repeat this process 5 times. The time it took to separate 10 mL of water was 544 seconds, indicating that the sample has a very strong emulsifying ability.

[0067] Experimental Example 3

[0068] Prepare 100 mL of a 0.001 mol / L aqueous solution of the pure product (FM-18-Cl) of the pyrrolidone amphoteric surfactant from Example 1. Transfer 20 mL of this solution into a 100 mL stoppered graduated cylinder and incubate at 25 °C for 10 min. Shake 20 times and let stand, then measure the initial volume of the foam (B0), the volume of the foam after 5 min (B5), and the time (T) for the foam volume to become half of the initial volume.

[0069] The experimental data are shown in Table 3. Compared with sodium dodecylbenzenesulfonate, the B0 of the pure product of pyrrolidone amphoteric surfactant (FM-18-Cl) prepared in Example 1 was 19 mL, which is relatively low, indicating that the pure product of pyrrolidone amphoteric surfactant (FM-18-Cl) prepared in Example 1 is a low-foaming surfactant.

[0070] Table 3 Foaming and Foam Stability

[0071]

[0072] Experimental Example 4

[0073] The surface tension of the pure product (FM-18-Cl) of the pyrrolidone amphoteric surfactant prepared in Example 1 was measured using a surface tension meter, and the surface tension variation diagram was obtained (e.g.) Figure 4 (As shown). The critical micelle concentration (CMC) for obtaining the product (FM-18-Cl) was 2.45 × 10⁻⁶. -3 The surface activity was measured in mol / L, and other surface performance parameters are shown in Table 4. It is evident that the pure product of the pyrrolidone amphoteric surfactant (FM-18-Cl) exhibits superior surface properties.

[0074] Table 4 Surface Properties

[0075]

[0076] Comparative Example 1

[0077] The defoaming properties of the following compounds (pure) were determined:

[0078]

[0079] When 0.1g was added, the foam volume was 72 ml, and the foam suppression value X was 0.14; when 0.05g was added, the foam volume was 81 ml, and the foam suppression value X was 0.04. The foam suppression performance of this compound is poor.

[0080] 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 amphoteric surfactant, characterized in that, Its molecular structural formula FM-nX is: ， Formula FM-nX; Where X is Cl or Br; n = 12, 14, 16 or 18.

2. The method for preparing the pyrrolidone amphoteric surfactant according to claim 1, characterized in that, Includes the following steps: The intermediate GA1-n was obtained by reacting N-alkyl-1,3-propanediamine, an alcohol solvent, and itaconic acid. The structural formula of the intermediate GA1-n is as follows: ， Formula GA1-n; Where n = 12, 14, 16 or 18; 1,3-propanesulfonate lactone was added to intermediate GA1-n, and the mixture was reacted to obtain intermediate GA2-n. The structural formula of intermediate GA2-n is as follows: ， Formula GA2-n; Where n = 12, 14, 16 or 18; An aqueous solution of sodium 2-haloethyl sulfonate was added to the intermediate GA2-n, and the mixture was reacted to obtain the pyrrolidone amphoteric surfactant product FM-nX. The product FM-nX was purified by evaporation of alcohol solvent and water under normal pressure, and then by recrystallization with organic solvent P to obtain the pure product FM-nX. The N-alkyl-1,3-propanediamine is N-dodecyl-1,3-propanediamine, N-tetradecyl-1,3-propanediamine, N-hexadecyl-1,3-propanediamine, or N-octadecyl-1,3-propanediamine; In the process of synthesizing product FM-nX, the sodium 2-haloethylsulfonate is sodium 2-chloroethylsulfonate or sodium 2-bromoethylsulfonate.

3. The preparation method according to claim 2, characterized in that, The molar ratio of N-alkyl-1,3-propanediamine, alcohol solvent, itaconic acid, 1,3-propanesulfonate lactone, sodium 2-haloethylsulfonate, and water is 1:9-20:1.01-1.06:1.01-1.09:1.00-1.09:17-28.

4. The preparation method according to claim 2, characterized in that, The alcohol solvent is ethanol, propanol, or isopropanol.

5. The preparation method according to claim 2, characterized in that, During the synthesis of the reaction intermediate GA1-n, the reaction temperature is 60~80℃ and the reaction time is 2.5~5.5 hours; Alternatively, during the synthesis of the reaction intermediate GA2-n, the reaction temperature is 60~80℃ and the reaction time is 2.5~5.5 hours; Alternatively, in the process of synthesizing the product FM-nX, the reaction temperature is 60~80℃ and the reaction time is 7~9 hours.

6. The preparation method according to claim 2, characterized in that, In the process of synthesizing product FM-nX, the mass fraction of sodium 2-haloethyl sulfonate in the aqueous solution of sodium 2-haloethyl sulfonate is 25-39%.

7. The preparation method according to claim 2, characterized in that, The organic solvent P used for recrystallization separation and purification is methanol, petroleum ether, or ethyl acetate.

8. The preparation method according to claim 2, characterized in that, Specifically, the steps include the following: N-alkyl-1,3-propanediamine was added to a reaction vessel, followed by an alcohol solvent, and the mixture was heated and stirred to dissolve. Solid itaconic acid was added in 4 to 11 batches. After the addition was complete, the mixture was stirred at 60 to 80°C for 2.5 to 5.5 hours to obtain intermediate GA1-n. 1,3-propanesulfonate solid was added to intermediate GA1-n in 4 to 11 batches. After the addition was complete, the mixture was stirred at 60 to 80 °C for 2.5 to 5.5 hours to obtain intermediate GA2-n. Add sodium 2-haloethyl sulfonate aqueous solution to intermediate GA2-n in 4 to 11 batches. After the addition is complete, stir the reaction at 60 to 80°C for 7 to 9 hours to obtain pyrrolidone amphoteric surfactant product FM-nX. Evaporate the alcohol solvent and water from product FM-nX under normal pressure, and then recrystallize and purify it 3 to 4 times with organic solvent P to obtain pure product FM-nX.

9. The use of the pyrrolidone amphoteric surfactant of claim 1 as an antifoaming agent, a low-foaming surfactant, and an emulsifier.

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