A cyano-containing surfactant, its preparation method and application

Abstract

This invention belongs to the field of fine chemical technology, and relates to a cyanide-containing surfactant, its preparation method, and its application. The molecular structure of the cyanide-containing surfactant is as follows: The raw material ratio for the preparation process of this cyanide-containing surfactant is: N-hydrogenated tallow-1,3-propylene diamine, alcohol solvent, acrylonitrile, sodium 2-chloroethylsulfonate monohydrate, and water in a molar ratio of 1:(10-25):(3.01-3.13):(1.01-1.08):(14-31). The cyanide-containing surfactant of this invention can be applied to antifoaming agents, low-foaming surfactants, and / or emulsifiers.

Description

Technical Field

[0001] This invention relates to the field of fine chemical technology, specifically to a cyano-containing 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] Currently, low-foaming surfactants face the following technical challenges: (i) Most commercially available low-foaming surfactants are compound chemical products, with few reports on products consisting of independent or single components. For example, Chinese patent CN111117803 A discloses a low-foaming surfactant composition comprising the following components: 70-80 parts of sodium fatty acid methyl ester ethoxylate sulfonate, 8-10 parts of N,N'-dispalmitoyl-p-phenylenediamine diethyl sulfonate, 5-7 parts of cellulose-based surfactant, 1-3 parts of amino silicone oil, 1-3 parts of dicetyl phosphate, 0.5-2 parts of oil displacement agent, 0.1-1 part of chelating agent, and 10-20 parts of anhydrous ethanol. (ii) The preparation process and methods for low-foaming surfactants are complex and cumbersome, resulting in high product prices and limited application scenarios. Summary of the Invention

[0004] In view of the drawbacks of existing preparation processes and methods, such as limited product variety, need for improved product performance, and numerous preparation steps, the present invention aims to provide a cyanide-containing surfactant that exhibits antifoaming properties, low foaming properties, and good surface activity.

[0005] The second objective of this invention is to provide a method for preparing the above-mentioned cyano-containing surfactant, which has a simple process.

[0006] The third objective of this invention is to provide an application of the above-mentioned cyano-containing surfactant as an antifoaming agent, a low-foaming surfactant, and / or an emulsifier.

[0007] To achieve the above-mentioned objectives, the technical solution of this invention is as follows:

[0008] In a first aspect of the present invention, a cyano-containing surfactant is provided, the molecular structural formula (T) of which is:

[0009]

[0010] In the research process of this invention, if quaternary ammonium salt groups, cyano groups, sodium sulfonate hydrophilic groups, and carbon chain lipophilic groups of a specific length are introduced into the surfactant molecular structure to form a novel cyano-containing surfactant (T), its surface activity is better.

[0011] In a second aspect, the present invention provides a method for preparing the above-mentioned cyano-containing surfactant (T), comprising the following steps:

[0012] 1) N-hydrogenated tallow-1,3-propanediamine, an alcohol solvent, and acrylonitrile are mixed and reacted to obtain intermediate M. The structural formula of intermediate M is as follows:

[0013]

[0014] 2) Dissolve sodium 2-chloroethylsulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate M, mix and react to obtain product T containing cyano surfactant; evaporate the alcohol solvent from product T under normal pressure, and then recrystallize and purify it with organic solvent A to obtain pure product T.

[0015] In one specific embodiment, the molar ratio of N-hydrogenated tallow-1,3-propanediamine, alcohol solvent, acrylonitrile, sodium 2-chloroethylsulfonate monohydrate, and water is 1:(10-25):(3.01-3.13):(1.01-1.08):(14-31).

[0016] In one specific embodiment, in step 1), during the preparation of intermediate M, the alcohol solvent is isopropanol and / or ethanol.

[0017] In one specific implementation, in step 1), during the preparation of intermediate M, the reaction temperature is 62–82°C and the reaction time is 4–6 h.

[0018] In one specific implementation, in step 2), during the preparation of product T, the reaction temperature is 62–82°C and the reaction time is 7–10 h.

[0019] In one specific embodiment, in step 2), the organic solvent A used for recrystallization separation and purification is petroleum ether, ethyl acetate, or methanol.

[0020] In one specific embodiment, the preparation method of the above-mentioned cyano-containing surfactant (T) specifically includes the following steps:

[0021] (1) Add N-hydrogenated tallow-1,3-propanediamine to the reactor, continue to add alcohol solvent, heat and stir, add acrylonitrile in 6 to 10 batches, and after the addition is complete, stir the reaction at 62 to 82°C for 4 to 6 hours to obtain intermediate M;

[0022] (2) Dissolve sodium 2-chloroethylsulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate M in 6 to 10 batches. After the addition is complete, stir and react at 62 to 82°C for 7 to 10 hours to obtain product T containing cyano surfactant; evaporate the alcohol solvent from product T under normal pressure, and then recrystallize and purify it 3 to 4 times with organic solvent A to obtain pure product T.

[0023] In a third aspect of the invention, an application of the above-mentioned cyano-containing surfactant (T) as a defoamer, a low-foaming surfactant, and / or an emulsifier is provided. For example, its application as a cleaning agent in industrial cleaning can avoid material spillage and environmental pollution caused by excessive foaming.

[0024] This invention uses N-hydrogenated tallow-1,3-propanediamine as the main chemical raw material for cyano-containing surfactant (T). In the preparation technology of cyano-containing surfactant (T), acrylonitrile and sodium 2-chloroethyl sulfonate monohydrate are added sequentially to introduce quaternary ammonium salt group, cyano group and sodium sulfonate hydrophilic group into the surfactant molecular structure, thereby improving the antifoaming property, low foaming property and surface properties.

[0025] The specific embodiments of the present invention have the following beneficial effects:

[0026] (a) The present invention provides a molecular structure of a cyano-containing surfactant (T), which combines a quaternary ammonium salt group, a cyano group, a sodium sulfonate hydrophilic group with a carbon chain lipophilic group of a specific length to form a novel molecular structure of a cyano-containing surfactant (T), which has antifoaming properties, low foaming properties and surface activity.

[0027] (b) The cyano-containing surfactant (T) of the present invention has a low production cost and does not require high-temperature reaction, and the operation control is simple. Attached Figure Description

[0028] 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.

[0029] Figure 1 The infrared spectrum of intermediate M in Example 1 is shown.

[0030] Figure 2 The NMR spectrum is that of intermediate M in Example 1.

[0031] Figure 3 This is the mass spectrum of intermediate M from Example 1.

[0032] Figure 4 The image shows the infrared spectrum of pure product T from Example 1.

[0033] Figure 5 The NMR spectrum of pure product T from Example 1 is shown.

[0034] Figure 6 This is the mass spectrum of pure product T from Example 1.

[0035] Figure 7 The graph shows the surface tension and concentration of the pure product T from Example 1. Detailed Implementation

[0036] 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.

[0037] Example 1

[0038] (1) Preparation of cyano-containing surfactants (product T):

[0039] 1) Add 326g of N-hydrogenated tallow-1,3-propanediamine and 900g of isopropanol to the reactor, heat to dissolve, then add 164.5g of acrylonitrile in 8 batches, stir at 75℃ for 5h to obtain intermediate M.

[0040] Intermediate M was purified by evaporation of isopropanol under normal pressure, followed by recrystallization from ethyl acetate three times to obtain pure intermediate M.

[0041] The pure intermediate M was analyzed by FTIR, NMR and MS.

[0042] FTIR analysis ( Figure 1 ): 2923cm -1 Peak 1 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2852 cm⁻¹. -1 Peak 2 is the peak of the symmetric stretching vibration of the methylene group, at 2248 cm⁻¹. -1 Peak 3 is the absorption peak of the C≡N stretching vibration, at 1469 cm⁻¹. -1 Peak 4 is the absorption peak of the asymmetric bending vibration of the methylene group, at 1134 cm⁻¹. -1 Peak 5 is the stretching vibration absorption peak of CN, at 721 cm⁻¹. -1 (peak 6) represents the in-plane rocking vibration of the methylene group.

[0043] 1 H-NMR analysis ( Figure 2 ): 1 H NMR(400MHz,CD3OD),δ:0.8858-0.9200(3H,t,J=6.84Hz,-CH3),1.2917(30H,s,CH3(CH2)15 CH2CH2-),1.4640-1.5386(2H,m,CH3(CH2) 15 CH2CH2-),1.6379-1.7064(2H,m,-NCH2CH2CH2N-),2.4500-2.4868(2H,t,J=7.36Hz,CH3(CH2) 15 (CH2CH2-), 2.5225-2.5566 (4H,t,J=6.82Hz,-NCH2CH2CH2N-), 2.5900-2.6242 (4H,t,J=6.84Hz,2×-NCH2CH2CN(tail end)), 2.6734-2.7080 (2H,t,J=6.92Hz,-NCH2CH2CN), 2.7293-2.7626 (2H,t,J=6.66Hz,-NCH2CH2CN), 2.8520-2.8864 (4H,t,J=6.88Hz,2×-NCH2CH2CN(tail end)) ppm. 3.3104ppm is the deuterated methanol solvent peak; 4.8649ppm is the deuterated methanol water peak.

[0044] Mass spectrometry analysis ( Figure 3 ): HRMS(ESI)(Positive)m / z:[M+H + ] + Calcd for C 30 H 56 N5,486.4536; Found 486.4528.

[0045] 2) Dissolve 197.8g of sodium 2-chloroethylsulfonate monohydrate (purity 98%) in 396g of water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate M in 8 batches. After the addition is complete, stir and react at 75℃ for 9h to obtain product T containing cyano surfactant; evaporate isopropanol from product T under normal pressure, and then purify it by recrystallization from methanol 3 times to obtain pure product T.

[0046] The pure product T was analyzed by FTIR, NMR and MS.

[0047] FTIR analysis ( Figure 4 3614cm -1 Peak 1 is the absorption peak of the OH stretching vibration, at 2920 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 2247 cm⁻¹. -1Peak 4 is the absorption peak of the C≡N stretching vibration, at 1207 cm⁻¹. -1 Peak 9 is the stretching vibration absorption peak of CN, at 1062 cm⁻¹. -1 Peak 6 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 719 cm⁻¹. -1 (peak 7) represents the in-plane rocking vibration of the methylene group, 607 cm⁻¹. -1 (peak 8) is the absorption peak of SO's stretching vibration.

[0048] 1 H-NMR analysis ( Figure 5 ): 1 H NMR (400MHz, CD3OD), δ: 0.8844-0.9186 (3H, t, J = 6.86Hz, -C H 3), 1.2900(30H,s,CH3(C) H 2) 15 CH2CH2-),1.4317-1.5342(2H,m,CH3(CH2) 15 C H 2CH2-),1.6254-1.6903(2H,m,-NCH2C H 2CH2N-),2.4616-2.4982(2H,t,J=7.32Hz,CH3(CH2) 15 CH2C H 2-),2.5809-2.6114(4H,t,J=6.1Hz,-NC H 2CH2C H 2N-),2.7506-2.7839(4H,t,J=6.66Hz,-NC H 2CH2SO3Na and-NC H 2CH2CN),2.8164-2.8496(4H,t,J=6.64Hz,2×-NC H 2CH2CN (tail end)), 3.1930-3.2151 (6H,t,J=4.42Hz,3×-NCH2C) H 2CN),3.8136-3.3.8357(2H,t,J=4.42Hz,-NCH2C H The peaks at 2SO3Na ppm and 3.3102 ppm represent the solvent peak of deuterated methanol; the peak at 4.8580 ppm represents the water peak of deuterated methanol.

[0049] Mass spectrometry analysis ( Figure 6 ): HRMS(ESI)(negative)m / z:[M-Na + ]- Calcd for C 32 H 59 O3N5SCl,628.4027; Found 628.4340.

[0050] Reaction formula:

[0051]

[0052]

[0053] Experimental Example 1

[0054] The foam suppression performance of the cyano-containing surfactant (T) prepared in Example 1 was analyzed: 10 mL of 0.5% (mass fraction) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain amount of sample were added to a 100 mL stoppered graduated cylinder, the stopper was closed, the cylinder was shaken vigorously twenty times, the foam volume (V1) was recorded, and the foam suppression value (J) was calculated.

[0055] J = (V0 - V1) / V0

[0056] Where V0 is the volume of foam in the blank test, mL; V1 is the volume of foam when the sample (product T) is added, mL.

[0057] The defoaming properties of sample T before and after purification, as well as OP-10 (industrial grade), are summarized in Tables 1 and 2. It can be seen that the cyano-containing surfactant (product T) prepared in Example 1 has certain defoaming properties.

[0058] Table 1. Antifoaming properties of the sample before purification (product T) and OP-10

[0059]

[0060] Table 2. Antifoaming properties of purified sample (product T) and OP-10

[0061]

[0062] Experiment Example 2

[0063] The emulsifying ability of the cyano-containing surfactant (product T) prepared in Example 1 was analyzed: 20 mL of 0.1% aqueous sample solution and 20 mL of liquid paraffin were placed in a 100 mL stoppered graduated cylinder, shaken vigorously five times, and allowed to stand for 1 minute. This process was repeated five times, and the time required to separate 10 mL of water was measured.

[0064] The emulsifying ability of the sample (product T) is shown in Table 3. The cyano-containing surfactant (product T) prepared in Example 1 has excellent emulsifying properties.

[0065] Table 3 Emulsifying ability (after purification)

[0066] product Water separation time (s) Example 1(T) 152 OP-10 684

[0067] Experimental Example 3

[0068] The foaming and foam stability of the cyano-containing surfactant (product T) synthesized in Example 1 were analyzed: 100 mL of a 0.001 mol / L sample aqueous solution was prepared. 20 mL of this solution was placed in a 100 mL stoppered graduated cylinder and kept at 25°C for 15 min. The mixture was vigorously shaken twenty times, and the initial foam volume (H0) was measured. After 5 min, the foam volume (H5) was measured, and the time (t) for the foam volume to decrease to half of its initial volume was determined. 1 / 2 (defined as half-life).

[0069] The experimental results are shown in Table 4. In comparison, the cyano-containing surfactant (product T) synthesized in Example 1 had lower foaming properties (4 mL) but better foam stability. This indicates that product (T) is a low-foaming surfactant.

[0070] Table 4. Foaming and foam-stabilizing properties of the purified surfactant (product T)

[0071]

[0072] Experiment Example 4

[0073] Surface tension (γ) and critical micelle concentration (CMC) of pure products (T) containing cyano surfactants were analyzed using the platinum ring method, yielding γ-log c curves. Figure 7 ), calculate CMC, and the surface tension (γ) at CMC. CMC C 20 pC 20 and CMC / C 20 (Table 5). The pure product (T) has better surface properties.

[0074] Table 5 Surface properties of pure product (T)

[0075]

[0076] 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 cyano-containing surfactant, characterized in that, Its molecular structural formula is: ， Formula T.

2. A method for preparing a cyano-containing surfactant according to claim 1, characterized in that, Includes the following steps: 1) N-hydrogenated tallow-1,3-propanediamine, an alcohol solvent, and acrylonitrile are mixed and reacted to obtain intermediate M. The structural formula of intermediate M is as follows: ； 2) Dissolve sodium 2-chloroethylsulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate M, mix and react to obtain cyano-containing surfactant product T; evaporate the alcohol solvent from product T under normal pressure, and then recrystallize and purify it with organic solvent A to obtain pure product T.

3. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, The molar ratio of N-hydrogenated tallow-1,3-propanediamine, alcohol solvent, acrylonitrile, sodium 2-chloroethylsulfonate monohydrate, and water is 1:10-25:3.01-3.13:1.01-1.08:14-31.

4. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, In step 1), during the preparation of intermediate M, the alcohol solvent is isopropanol and / or ethanol.

5. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, In step 1), during the preparation of intermediate M, the reaction temperature is 62–82℃ and the reaction time is 4–6h.

6. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, In step 2), during the preparation of product T, the reaction temperature is 62–82℃ and the reaction time is 7–10h.

7. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, In step 2), the organic solvent A used for recrystallization separation and purification is petroleum ether, ethyl acetate, or methanol.

8. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, In step 2), recrystallization and purification are performed 3 to 4 times.

9. The method for preparing a cyano-containing surfactant as described in claim 2, characterized in that, Specifically, the steps include the following: (1) Add N-hydrogenated tallow-1,3-propanediamine to the reactor, continue to add alcohol solvent, heat and stir, add acrylonitrile in 6 to 10 batches, and after the addition is complete, stir the reaction at 62 to 82°C for 4 to 6 h to obtain intermediate M; (2) Dissolve sodium 2-chloroethylsulfonate monohydrate in water to obtain an aqueous solution of sodium 2-chloroethylsulfonate; add the aqueous solution of sodium 2-chloroethylsulfonate to intermediate M in 6 to 10 batches. After the addition is complete, stir and react at 62 to 82°C for 7 to 10 h to obtain product T containing cyano surfactant; evaporate the alcohol solvent from product T under normal pressure, and then recrystallize and purify it 3 to 4 times with organic solvent A to obtain pure product T.

10. The application of the cyano-containing surfactant as described in claim 1 as a defoaming agent or a low-foaming surfactant.

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