Amphoteric heterocyclic surfactant, its preparation and use
By designing amphoteric heterocyclic surfactants and introducing various hydrophilic groups and carbon chains, the problems of limited variety and complex synthesis of existing low-foaming surfactants have been solved, achieving low-cost, high-efficiency foam suppression and low-foaming performance, and expanding the application range.
Patent Information
- Application Number
- CN202310349596.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-03-30
- Publication Date
- 2026-01-30
- Estimated Expiration
- 2043-03-30
AI Technical Summary
There are few existing low-foaming surfactant varieties, their technical performance still needs improvement, their synthesis methods are cumbersome and costly, and their application areas are limited.
A novel amphoteric heterocyclic surfactant was designed by introducing a heterocyclic structure, quaternary ammonium salt group, hydroxyl group, carboxylic acid group, sodium sulfonate and amide hydrophilic group on the ring into the molecular structure, combined with a carbon chain lipophilic group of a certain length, and synthesizing the novel molecular structure using a simple preparation method.
It achieves good antifoaming and low-foaming performance, has low production cost, and is suitable for antifoaming agents, low-foaming surfactants and emulsifiers, with a wide range of applications.
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Figure CN116813520B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of fine chemical technology, specifically to an amphoteric heterocyclic 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] Existing literature [Wang Ziqian. Types and Applications of Low-Foaming Surfactants. Chemical Technology and Development, 2013, 42(4):28-32.] introduces the properties, production, and applications of several low-foaming surfactants, including EO / PO block polyethers, ethoxylated fatty acid methyl ester derivatives, isooctanol phosphate derivatives, and polyether-modified organosilicones. Currently, most low-foaming surfactants are composite chemical products, with very few products having independent chemical compositions. Secondly, the synthesis methods of low-foaming surfactants are cumbersome, the products are expensive, and their application areas are limited. Summary of the Invention
[0004] In view of the shortcomings of existing low-foaming surfactant products, such as limited variety, need for improvement in technical performance, and cumbersome product preparation processes and methods, the present invention aims to provide an amphoteric heterocyclic surfactant that exhibits antifoaming and low-foaming properties and has excellent surface activity.
[0005] The second objective of this invention is to provide a preparation technique and method for the above-mentioned amphoteric heterocyclic surfactant, which has the advantages of low production cost and simple operation.
[0006] The third objective of this invention is to provide a method for using the above-mentioned amphoteric heterocyclic surfactant as a defoaming agent, a low-foaming surfactant, and an emulsifier.
[0007] To achieve the aforementioned objectives, the technical solution of this invention is as follows:
[0008] In a first aspect of the invention, an amphoteric heterocyclic surfactant is provided, the general molecular formula (DF-n) being:
[0009]
[0010] In the formula DF-n, n is 12, 14, 16 or 18; M is Na or K.
[0011] In the molecular structure design concept of this invention, a heterocyclic structure was designed. The heterocyclic pyrrolidone ring has a large volume, resulting in greater steric hindrance, which means that the hydrophilic group has a large volume and a wide range of action space. Furthermore, quaternary ammonium salt groups, hydroxyl groups, carboxylic acid groups, sodium sulfonate, and amide hydrophilic groups on the ring were introduced, along with a carbon chain lipophilic group of a certain length, to form a novel amphoteric heterocyclic surfactant (DF-n). Practice has shown that it has good surface properties.
[0012] In a second aspect, the present invention provides a method for preparing the amphoteric heterocyclic surfactant (DF-n), comprising the following steps:
[0013] 1) Long-chain alkylamine, alcohol solvent, and itaconic acid solid are added sequentially to a reactor, stirred, and mixed to obtain reaction intermediate GH-n. The general structural formula of reaction intermediate GH-n is:
[0014]
[0015] Where n is 12, 14, 16 or 18; M is Na or K;
[0016] 2) Dissolve 3-chloro-2-hydroxypropyl sulfonate in water to obtain an aqueous solution of 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-n, stir, and mix to obtain the amphoteric heterocyclic surfactant product DF-n; evaporate the alcohol solvent from product DF-n under normal pressure, and then recrystallize and purify it with organic solvent P to obtain the pure product DF-n.
[0017] The reaction formula is:
[0018]
[0019] In one specific embodiment, the molar ratio of the long-chain alkylamine, alcohol solvent, itaconic acid, 3-chloro-2-hydroxypropyl sulfonate, and water is 1:(6-18):(1.01-1.08):(1.01-1.08):(18-32).
[0020] In one specific embodiment, the long-chain alkylamine is octadecylamine, hexadecylamine, tetradecylamine, or dodecylamine.
[0021] In one specific embodiment, in step 1), during the preparation of the reaction intermediate GH-n, the alcohol solvent is ethanol and / or isopropanol.
[0022] In one specific embodiment, in step 1), during the preparation of the reaction intermediate GH-n, the reaction temperature is 62–82°C and the reaction time is 3.5–5.5 h.
[0023] In one specific embodiment, in step 2), the 3-chloro-2-hydroxypropyl sulfonate is sodium 3-chloro-2-hydroxypropyl sulfonate or potassium 3-chloro-2-hydroxypropyl sulfonate.
[0024] In one specific embodiment, in step 2), during the preparation of product DF-n, the reaction temperature is 62–82°C and the reaction time is 7.5–9.5 h.
[0025] In one specific embodiment, in step 2), the organic solvent P used for recrystallization separation and purification is one or more of petroleum ether, methanol, and ethyl acetate.
[0026] In one specific embodiment, the preparation method of the above-mentioned amphoteric heterocyclic surfactant (DF-n) specifically includes the following steps:
[0027] (1) Add long-chain alkylamine and alcohol solvent to the reactor in sequence, heat and stir to dissolve, then add itaconic acid solid in 4-9 batches. After the addition is complete, stir the reaction at 62-82℃ for 3.5-5.5h to obtain reaction intermediate GH-n.
[0028] (2) Dissolve 3-chloro-2-hydroxypropyl sulfonate in water to obtain an aqueous solution of 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-n in 4 to 9 batches. After the addition is complete, stir the reaction at 62 to 82 °C for 7.5 to 9.5 h to obtain the amphoteric heterocyclic surfactant product DF-n; evaporate the alcohol solvent from the product DF-n under normal pressure, and then recrystallize and purify it 3 to 4 times with organic solvent P to obtain the pure product DF-n.
[0029] In a third aspect of the invention, an application of the amphoteric heterocyclic surfactant (DF-n) described in the first aspect is provided as an antifoaming agent, a low-foaming surfactant, and an emulsifier. For example, its application in cleaning agent formulations during industrial cleaning can prevent material spillage and waste.
[0030] This invention uses long-chain alkylamines as reactants for amphoteric heterocyclic surfactants (DF-n). In the preparation process of amphoteric heterocyclic surfactants (DF-n), itaconic acid solid, 3-chloro-2-hydroxypropyl sulfonate and water are added sequentially to introduce heterocyclic structures, quaternary ammonium salt groups, hydroxyl groups, carboxylic acid groups, sodium sulfonate and various hydrophilic groups on the ring into the molecular structure, thereby improving the antifoaming, low foaming and surface properties.
[0031] The specific embodiments of the present invention have the following beneficial effects:
[0032] (i) This invention provides a series of amphoteric heterocyclic surfactants (DF-n), which combine heterocyclic structures, quaternary ammonium salt groups, hydroxyl groups, carboxylic acid groups, sodium sulfonate, and various hydrophilic groups of cyclic amides with lipophilic groups of a certain length of carbon chain to form novel molecular structures, namely amphoteric heterocyclic surfactants (DF-n). They have good antifoaming properties, low foaming performance, and surface activity.
[0033] (ii) The amphoteric heterocyclic surfactant (DF-n) of the present invention does not require high temperature and high pressure reaction, and has low production cost. Attached Figure Description
[0034] 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.
[0035] Figure 1 The infrared spectrum of the pure product DF-12 from Example 1 is shown.
[0036] Figure 2 The NMR spectrum of the pure product DF-12 from Example 1 is shown.
[0037] Figure 3 The mass spectrum of the pure product DF-12 from Example 1 is shown.
[0038] Figure 4 The infrared spectrum of the pure product DF-14 from Example 2 is shown.
[0039] Figure 5 The NMR spectrum of the pure product DF-14 from Example 2 is shown.
[0040] Figure 6 The mass spectrum of the pure product DF-14 from Example 2 is shown.
[0041] Figure 7 The infrared spectrum of the pure product DF-16 from Example 3 is shown.
[0042] Figure 8 The NMR spectrum of the pure product DF-16 from Example 3 is shown.
[0043] Figure 9 The mass spectrum of the pure product DF-16 from Example 3 is shown.
[0044] Figure 10 The infrared spectrum of the pure product DF-18 from Example 4 is shown.
[0045] Figure 11 The NMR spectrum of the pure product DF-18 from Example 4 is shown.
[0046] Figure 12 The mass spectrum of the pure product DF-18 from Example 4 is shown.
[0047] Figure 13 The graph shows the surface tension and concentration of the pure product DF-12 from Example 1.
[0048] Figure 14 The graph shows the surface tension and concentration of the pure product DF-14 from Example 2.
[0049] Figure 15 The graph shows the surface tension and concentration of the pure product DF-16 from Example 3.
[0050] Figure 16 The graph shows the surface tension and concentration of the pure product DF-18 from Example 4. Detailed Implementation
[0051] 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.
[0052] Example 1
[0053] (1) Preparation of amphoteric heterocyclic surfactants (product DF-12):
[0054] 1) Add 185.35g of dodecylamine and 500g of isopropanol to a three-necked flask, heat and stir to dissolve, then add 134.0g of itaconic acid solid in 6 batches, stir at 75℃ for 4 hours to obtain reaction intermediate GH-12.
[0055] 2) Dissolve 207.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (purity 98.5%) in 415.2 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-12 in 6 batches. After the addition is complete, stir and react at 75 °C for 8 hours to obtain the amphoteric heterocyclic surfactant product DF-12; evaporate the solvent isopropanol from the product DF-12 under normal pressure, and then purify it by recrystallization three times with ethyl acetate to obtain the pure product DF-12.
[0056] The pure product DF-12 was analyzed by FTIR, NMR and mass spectrometry.
[0057] FTIR analysis ( Figure 1 ): 3363cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2958 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of methyl groups, at 2922 cm⁻¹.-1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2850 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1718 cm⁻¹. -1 Peak 5 is the stretching vibration peak of the carboxyl group C=O, at 1637 cm⁻¹. -1 Peak 6 is the absorption peak of the C=O stretching vibration of the amide ring, at 1201 cm⁻¹. -1 Peak 7 is the absorption peak of the stretching vibration of CN, at 1053 cm⁻¹. -1 Peak 8 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 727 cm⁻¹. -1 (peak9) represents the in-plane rocking vibration of the methylene group, 630 cm⁻¹ -1 (peak 10) is the absorption peak of SO's stretching vibration.
[0058] 1 H-NMR analysis ( Figure 2 ): 1 H NMR(400MHz,CD3OD),δ:0.8831-0.9170(3H,t,J=6.78Hz,-CH3),1.2915(18H,s,CH3(CH2)9CH2CH2-),1.6150-1.6731 (2H,m,-CH3(CH2)9CH2CH2-),2.9543-2.9701(2H,d,-COCH2CH-),2.9892-3.0050(2H,d,-CH2SO3Na),3.0966-3.1314 (2H,t,J=6.96Hz,CH3(CH2)9CH2CH2-),3.6128-3.6452(1H,m,-CHCOOH),3.6890-3.7031(2H,d,-NCH2CH(OH)-),3.7755-3.7855(2H,d,-NCH2CHCOOH),4.2487-4.3032(1H,m,-NCH2CH(OH)-)ppm. 3.3103ppm is the solvent peak of deuterated methanol; 4.8812ppm is the water peak of deuterated methanol.
[0059] Mass spectrometry analysis ( Figure 3 ): HRMS(ESI)(negative)m / z:[MH + ]-Calcd for C 20 H 36 O7NSNaCl,492.1799; Found 492.2493.[M-Na + ]-Calcd for C 20 H37 O7NSCl,470.1979; Found 470.2516.[M-Cl--Na + -H + ]-Calcd for C 20 H 36 O7NS,434.2212; Found 434.2727.
[0060] Reaction formula:
[0061]
[0062] Example 2
[0063] (1) Preparation of amphoteric heterocyclic surfactants (product DF-14):
[0064] 1) Add 213.4g of tetradecylamine and 500g of isopropanol to a three-necked flask, heat and stir to dissolve, then add 134.0g of itaconic acid solid in 6 batches, stir at 75℃ for 4 hours to obtain reaction intermediate GH-14.
[0065] 2) Dissolve 207.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (purity 98.5%) in 415.2 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-14 in 6 batches. After the addition is complete, stir and react at 75 °C for 8 hours to obtain the amphoteric heterocyclic surfactant product DF-14; evaporate the solvent isopropanol from the product DF-14 under normal pressure, and then purify it by recrystallization three times with ethyl acetate to obtain the pure product DF-14.
[0066] The pure product DF-14 was analyzed by FTIR, NMR and mass spectrometry.
[0067] FTIR analysis ( Figure 4 ): 3356cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2958 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of methyl groups, at 2920 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2850 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1718 cm⁻¹. -1 Peak 5 is the stretching vibration peak of the carboxyl group C=O, at 1635 cm⁻¹. -1 Peak 6 is the absorption peak of the C=O stretching vibration of the amide ring, at 1201 cm⁻¹. -1Peak 7 is the absorption peak of the stretching vibration of CN, at 1053 cm⁻¹. -1 Peak 8 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 727 cm⁻¹. -1 (peak9) represents the in-plane rocking vibration of the methylene group, 629 cm⁻¹ -1 (peak 10) is the absorption peak of SO's stretching vibration.
[0068] 1 H-NMR analysis ( Figure 5 ): 1 H NMR(400MHz,CD3OD),δ:0.8834-0.9176(3H,t,J=6.84Hz,-CH3),1.2904(22H,s,CH3(CH2) 11 CH2CH2-),1.6108-1.6864(2H,m,-CH3(CH2) 11 CH2CH2-),2.9550-2.9709(2H,d,-COCH2CH-),2.9899-3.0058(2H,d,-CH2SO3Na),3.0969-3.1317(2H,t,J=6.96Hz,CH3(CH2) 11 (CH2CH2-), 3.6110-3.6404 (1H,m,-CHCOOH), 3.6885-3.7027 (2H,d,-NCH2CH(OH)-), 3.7733-3.7834 (2H,d,-NCH2CHCOOH), 4.2489-4.3034 (1H,m,-NCH2CH(OH)-) ppm. 3.3103 ppm is the solvent peak of deuterated methanol; 4.8796 ppm is the water peak of deuterated methanol.
[0069] Mass spectrometry analysis ( Figure 6 ): HRMS(ESI)(negative)m / z:[MH + ]-Calcd for C 22 H 40 O7NSNaCl,520.2112; Found 520.2443.[M-Na + ]-Calcd for C 22 H 41 O7NSCl,498.2292; Found 498.2708.[M-Cl--Na + -H + ]-Calcd for C 22 H 40O7NS,462.2526; Found 462.2913.
[0070] Reaction formula:
[0071]
[0072] Example 3
[0073] (1) Preparation of amphoteric heterocyclic surfactants (product DF-16):
[0074] 1) Add 241.46g of cetylamine and 500g of isopropanol to a three-necked flask, heat and stir to dissolve, then add 134.0g of itaconic acid solid in 6 batches, stir at 75℃ for 4 hours to obtain reaction intermediate GH-16.
[0075] 2) Dissolve 207.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (purity 98.5%) in 415.2 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-16 in 6 batches. After the addition is complete, stir and react at 75 °C for 8 hours to obtain the amphoteric heterocyclic surfactant product DF-16; evaporate the solvent isopropanol from the product DF-16 under normal pressure, and then purify it by recrystallization three times with ethyl acetate to obtain the pure product DF-16.
[0076] The pure product DF-16 was analyzed by FTIR, NMR and mass spectrometry.
[0077] FTIR analysis ( Figure 7 ): 3357cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2960 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of methyl groups, at 2920 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2848 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1635 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of the amide ring, at 1201 cm⁻¹. -1 Peak 6 is the stretching vibration absorption peak of CN, at 1051 cm⁻¹. -1 Peak 7 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 (peak 8) represents the in-plane rocking vibration of the methylene group, 622 cm⁻¹. -1 (peak 9) is the absorption peak of SO's stretching vibration.
[0078] 1 H-NMR analysis ( Figure 8 ): 1 H NMR(400MHz,CD3OD),δ:0.8830-0.9172(3H,t,J=6.84Hz,-CH3),1.2883(26H,s,CH3(CH2) 13 CH2CH2-),1.6120-1.6837(2H,m,-CH3(CH2) 13 CH2CH2-),2.9554-2.9714(2H,d,-COCH2CH-),2.9902-3.0063(2H,d,-CH2SO3Na),3.0965-3.1314(2H,t,J=6.98Hz,CH3(CH2) 13 (CH2CH2-), 3.6065-3.6385 (1H,m,-CHCOOH), 3.6868-3.7009 (2H,d,-NCH2CH(OH)-), 3.7694-3.7796 (2H,d,-NCH2CHCOOH), 4.2490-4.3036 (1H,m,-NCH2CH(OH)-) ppm. 3.3100 ppm is the solvent peak of deuterated methanol; 4.8639 ppm is the water peak of deuterated methanol.
[0079] Mass spectrometry analysis ( Figure 9 ): HRMS(ESI)(negative)m / z:[MH + ]-Calcd for C 24 H 44 O7NSClNa,548.2425; Found 548.2855.[M-Na + ]-Calcd for C 24 H 45 O7NSCl,526.2605; Found 526.2900.[M-Na + -Cl--H + ]-Calcd for C 24 H 44 O7NS,490.2839; Found 490.3427.
[0080] Reaction formula:
[0081]
[0082] Example 4
[0083] (1) Preparation of amphoteric heterocyclic surfactants (product DF-18):
[0084] 1) Add 269.51g of octadecylamine and 500g of isopropanol to a three-necked flask, heat and stir to dissolve, then add 134.0g of itaconic acid solid in 6 batches, stir at 75℃ for 4 hours to obtain reaction intermediate GH-18.
[0085] 2) Dissolve 207.6 g of sodium 3-chloro-2-hydroxypropyl sulfonate (purity 98.5%) in 415.2 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate; add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate GH-18 in 6 batches. After the addition is complete, stir and react at 75 °C for 8 hours to obtain the amphoteric heterocyclic surfactant product DF-18; evaporate the solvent isopropanol from the product DF-18 under normal pressure, and then purify it by recrystallization from methanol 3 times to obtain the pure product DF-18.
[0086] The pure product DF-18 was analyzed by FTIR, NMR and mass spectrometry.
[0087] FTIR analysis ( Figure 10 ): 3361cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2960 cm⁻¹. -1 Peak 2 is the absorption peak of the asymmetric stretching vibration of methyl groups, at 2922 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2850 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1631 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of the amide ring, at 1195 cm⁻¹. -1 Peak 6 is the stretching vibration absorption peak of CN, at 1053 cm⁻¹. -1 Peak 7 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 721 cm⁻¹. -1 (peak 8) represents the in-plane rocking vibration of the methylene group, 622 cm⁻¹. -1 (peak 9) is the absorption peak of SO's stretching vibration.
[0088] 1 H-NMR analysis ( Figure 11 ): 1 H NMR(400MHz,CD3OD),δ:0.8830-0.9170(3H,t,J=6.8Hz,-CH3),1.2875(30H,s,CH3(CH2) 15CH2CH2-),1.6130-1.6887(2H,m,-CH3(CH2) 15 CH2CH2-),2.9561-2.9722(2H,d,-COCH2CH-),2.9910-3.0071(2H,d,-CH2SO3Na),3.0964-3.1313(2H,t,J=6.98Hz,CH3(CH2) 15 (CH2CH2-), 3.6222-3.6477 (1H,m,-CHCOOH), 3.6864-3.7004 (2H,d,-NCH2CH(OH)-), 3.7680-3.7783 (2H,d,-NCH2CHCOOH), 4.2493-4.3039 (1H,m,-NCH2CH(OH)-) ppm. 3.3100 ppm is the peak for deuterated methanol solvent; 4.8585 ppm is the peak for deuterated methanol water.
[0089] Mass spectrometry analysis ( Figure 12 ): HRMS(ESI)(negative)m / z:[M-Na + ]-Calcd for C 26 H 49 O7NSCl,554.2918; Found 554.3339.[M-Na + -Cl--H + ]-Calcd for C 26 H 48 O7NS,518.3152; Found518.3760.
[0090] Reaction formula:
[0091]
[0092] Experimental Example 1
[0093] The foam suppression performance of the amphoteric heterocyclic surfactants (product DF-n) synthesized in Examples 1-4 was tested: 10 mL of 0.5% (mass fraction) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain amount of sample (DF-n) were added to a 100 mL stoppered graduated cylinder, the stopper was sealed, and the cylinder was shaken vigorously up and down 20 times. The total foam volume (V1) was recorded, and the foam suppression value (X) was calculated.
[0094] X = (V0 - V1) / V0
[0095] Where V0 is the foam volume in the blank test, in mL. V1 is the foam volume when the sample (product DF-n) is added, in mL.
[0096] The defoaming properties of each product before and after purification, as well as OP-10 (industrial grade), are shown in Tables 1 and 2. It can be seen that the amphoteric heterocyclic surfactants (product DF-n) synthesized in Examples 1-4 have very high defoaming capabilities.
[0097] Table 1. Antifoaming properties of each sample (product DF-n) and OP-10 before purification.
[0098]
[0099] Table 2. Antifoaming properties of each sample (product DF-n) and OP-10 after purification.
[0100]
[0101]
[0102] Experiment Example 2
[0103] The emulsifying ability of the amphoteric heterocyclic surfactants (pure product DF-n) synthesized in Examples 1-4 was tested: 20 mL of 0.1% sample aqueous solution (pH adjusted to 11 with NaOH) and 20 mL of liquid paraffin were measured into a 100 mL stoppered graduated cylinder, and the mixture was shaken vigorously 5 times and allowed to stand for 1 minute. This process was repeated 5 times, and the time required to separate 10 mL of water was measured.
[0104] The emulsifying abilities of each sample (pure product DF-n) are shown in Table 3. It can be seen that the amphoteric heterocyclic surfactants (product DF-n) synthesized in Examples 1-4 all exhibited excellent emulsifying abilities.
[0105] Table 3 Emulsifying ability (after purification)
[0106] product Water separation time (s) Example 1 (DF-12) 308 Example 2 (DF-14) 505 Example 3 (DF-16) 838 Example 4 (DF-18) 170 OP-10 684
[0107] Experimental Example 3
[0108] The foaming and foam stability of the amphoteric heterocyclic surfactants (pure product DF-n) synthesized in Examples 1-4 were tested: 120 mL of a sample aqueous solution with a molar concentration of 0.001 mol / L was prepared. 20 mL of the solution was placed in a 100 mL stoppered graduated cylinder and kept at a constant temperature of 25°C for 15 min. After 20 vigorous shaking, the initial volume of foam (H0) was recorded immediately, and the volume of foam (H5) was recorded again after 5 min. The time (t) for the foam volume to decay to half of the initial volume was also recorded. 1 / 2 (i.e., half-life).
[0109] The experimental data are shown in Table 4. The amphoteric heterocyclic surfactants (pure product DF-n) synthesized in Examples 1-4 have low foaming properties but good foam stabilization properties, indicating that the product (DF-n) belongs to low-foaming surfactants.
[0110] Table 4. Foaming and foam-stabilizing properties of various surfactants (pure product DF-n)
[0111]
[0112] Experiment Example 4
[0113] Sample: Surface tension of the pure product (DF-n) of the amphoteric heterocyclic surfactant was measured at room temperature.
[0114] Methods: Surface tension was measured using a JHZL type fully automatic interfacial tensiometer (manufactured by Yangzhou Junhao Electric Co., Ltd.) using the platinum ring method. The surface tension ~ log c curve was obtained (see...). Figures 13-16 The critical micelle concentration (CMC) and the surface tension at CMC (γ) were obtained. CMC C 20 pC 20 and CMC / C 20 (See Table 5). It can be seen that the pure product (DF-n) has better surface properties.
[0115] Table 5 Surface properties of the pure product (DF-n)
[0116]
[0117] 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. An amphoteric heterocyclic surfactant characterized in that, The molecular structure general formula is: ， General formula DF-n, In the general formula DF-n, C n H 2n+1 is dodecyl, tetradecyl, hexadecyl or octadecyl; M is Na or K.
2. The method for preparing the amphoteric heterocyclic surfactant according to claim 1, characterized by, The method comprises the following steps: 1) sequentially adding long carbon chain alkyl amine, alcohol solvent and itaconic acid solid in a reactor, stirring, mixing and reacting to obtain reaction intermediate GH-n, wherein the structure general formula of the reaction intermediate GH-n is: ， n is 12, 14, 16 or 18; The long carbon chain alkyl amine is octadecylamine, hexadecylamine, tetradecylamine and dodecylamine; 2) dissolving 3-chloro-2-hydroxypropyl sulfonate in water to obtain 3-chloro-2-hydroxypropyl sulfonate aqueous solution; adding the 3-chloro-2-hydroxypropyl sulfonate aqueous solution into the reaction intermediate GH-n, stirring and mixing to obtain amphoteric heterocyclic surfactant product DF-n; evaporating the alcohol solvent from the product DF-n under normal pressure, and then purifying the product DF-n by recrystallization with organic solvent P to obtain pure product DF-n. The 3-chloro-2-hydroxypropyl sulfonate is sodium 3-chloro-2-hydroxypropyl sulfonate or potassium 3-chloro-2-hydroxypropyl sulfonate.
3. The production method according to claim 2, wherein The molar ratio of the long carbon chain alkyl amine, alcohol solvent, itaconic acid, 3-chloro-2-hydroxypropyl sulfonate, water is 1:6-18:1.01-1.08:1.01-1.08:18-32.
4. The production method according to claim 2, wherein In step 1), the alcohol solvent is ethanol and / or isopropyl alcohol in the process of preparing the reaction intermediate GH-n.
5. The production method according to claim 2, wherein In step 1), the reaction temperature is 62-82℃ and the reaction time is 3.5-5.5 h in the process of preparing the reaction intermediate GH-n.
6. The production method according to claim 2, wherein In step 2), the reaction temperature is 62-82℃ and the reaction time is 7.5-9.5 h in the process of preparing the product DF-n. In step 2), the organic solvent P for recrystallization separation and purification is one or more of petroleum ether, methanol and ethyl acetate.
7. The production method according to claim 2, wherein Specifically comprising the following steps:
8. The production method according to claim 2, wherein (1) sequentially adding long carbon chain alkyl amine and alcohol solvent in a reactor, heating and stirring to dissolve, then adding itaconic acid solid in 4-9 batches, stirring and reacting at 62-82℃ for 3.5-5.5 h to obtain reaction intermediate GH-n; (2) dissolving 3-chloro-2-hydroxypropyl sulfonate in water to obtain 3-chloro-2-hydroxypropyl sulfonate aqueous solution; adding the 3-chloro-2-hydroxypropyl sulfonate aqueous solution into the reaction intermediate GH-n in 4-9 batches, stirring and reacting at 62-82℃ for 7.5-9.5 h to obtain amphoteric heterocyclic surfactant product DF-n; evaporating the alcohol solvent from the product DF-n under normal pressure, and then purifying the product DF-n by recrystallization with organic solvent P for 3-4 times to obtain pure product DF-n.
9. Application of the amphoteric heterocyclic surfactant in claim 1 as foam inhibitor, low-foam surfactant and emulsifier.