Cyano-containing quaternary ammonium salt type surfactant as well as preparation method and application thereof

Abstract

The invention discloses a cyano-containing quaternary ammonium salt type surfactant as well as a preparation method and application thereof, and belongs to the technical field of fine chemical engineering. The structural formula of the cyano-containing quaternary ammonium salt type surfactant provided by the invention is # imgabs0, and the cyano-containing quaternary ammonium salt type surfactant is prepared by the following steps: reacting N-octadecyl-1, 3-propylene diamine with acrylonitrile in a solvent to prepare a reaction intermediate, and then adding a 3-chloro-2-hydroxy propyl sodium sulfonate aqueous solution for reaction. The cyano group-containing quaternary ammonium salt type surfactant provided by the invention combines cyano groups, quaternary ammonium salt groups, sodium sulfonate, hydroxyl hydrophilic groups and lipophilic groups with certain lengths together, has good foam inhibition, low-foam property and surface activity, is simple in preparation method and low in price, and can be widely applied to the field of low-foam surfactants or emulsifiers.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and particularly to a cyano-containing quaternary ammonium salt type surfactant, a preparation method thereof and an application thereof. Background Art

[0002] The information disclosed in the background art of the present invention is only intended to enhance the overall understanding of the present invention, and is not necessarily regarded as an admission or an indication in any form that this information constitutes the prior art already known to those of ordinary skill in the art.

[0003] A surfactant is a substance that can significantly change the interfacial state of its solution system when added in a small amount. It has an amphiphilic structure and can reduce the surface tension. Low-foaming surfactants are a type of surfactants with low foaming performance during application, and they play an important role in industry. For example, in the production processes such as textile dyeing and finishing, industrial cleaning, polymer polymerization, and biological fermentation, if a large amount of foam is generated during operations such as stirring and aeration, it will bring many inconveniences to on-site operations, such as consuming the actual installed capacity of equipment, being unable to be applied to automatic metering devices, prolonging the sewage treatment time, etc., and even affecting the quality of the finished product. Therefore, it is necessary to effectively inhibit foam generation during the production process.

[0004] Currently, low-foaming surfactants are often mixtures of various surfactants and defoamers. For example, Patent CN113583762 A (Publication Date: November 2, 2021) discloses a high-alkali-resistant low-foaming surfactant and a preparation method thereof, which includes isomeric tridecyl alcohol polyoxyethylene ether 10-15%, isomeric decyl alcohol polyoxyethylene ether 25-30%, fatty alcohol polyoxyethylene ether 7-30%, dispersant 6-9%, penetrant 1-3%, defoamer 5-8%, and the balance is industrial pure water. A defoamer FAG470 is introduced into this surfactant. However, during use, the defoaming ability of the defoamer will continuously decline until there is finally no defoaming effect. Therefore, it is necessary to continuously supplement the defoamer to achieve continuous defoaming and foam suppression, which will lead to an increase in cost and also affect the continuous stability of the production process due to different amounts of foam before and after.

[0005] The most fundamental way to reduce foam is that the surfactant itself is a low-foam product, which fundamentally solves the problem of foam; currently, there are limited products of low-foaming surfactants, and the preparation methods are cumbersome and expensive; therefore, it is necessary to develop new low-foaming surfactants with low prices and simple production processes. Summary of the Invention

[0006] In view of this, the present invention provides a cyanide group-containing quaternary ammonium salt type surfactant, a preparation method thereof and an application thereof. The cyanide group-containing quaternary ammonium salt type surfactant provided by the present invention has good foam suppression performance and emulsification performance, can be used as a low-foam surfactant, and has a simple preparation process and low price.

[0007] In the first aspect, the present invention provides a cyanide group-containing quaternary ammonium salt type surfactant, and its structural formula is shown as follows:

[0008]

[0009] In the second aspect, the present invention provides a preparation method of the above cyanide group-containing quaternary ammonium salt type surfactant, comprising the following steps:

[0010] (1) React N-octadecyl-1,3-propanediamine with acrylonitrile in a solvent to prepare reaction intermediate A, and the chemical structural formula of the reaction intermediate A is:

[0011]

[0012] (2) Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate A, and mix and react to obtain the product.

[0013] In the third aspect, the present invention provides an application of the above cyanide group-containing quaternary ammonium salt type surfactant or the cyanide group-containing quaternary ammonium salt type surfactant prepared by the above preparation method as a low-foam surfactant or an emulsifier.

[0014] Compared with the prior art, the present invention has achieved the following beneficial effects:

[0015] (1) The cyanide group-containing quaternary ammonium salt type surfactant provided by the present invention combines a cyanide group, a quaternary ammonium salt group, a sodium sulfonate group, a hydroxyl hydrophilic group and a lipophilic group with a certain length, has good foam suppression property, low-foam property and surface activity, and can be widely used in the field of low-foam surfactants or emulsifiers;

[0016] (2) The preparation method of the cyanide group-containing quaternary ammonium salt type surfactant of the present invention is simple, has a low price, and has good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The specification drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. Obviously, for those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0018] Figure 1It is the infrared spectrum of the pure cyanide group-containing quaternary ammonium salt surfactant in Example 1 of the present invention;

[0019] Figure 2 It is the proton nuclear magnetic resonance spectrum of the pure cyanide group-containing quaternary ammonium salt surfactant in Example 1 of the present invention in the range of 0.8 - 2.4 ppm;

[0020] Figure 3 It is the proton nuclear magnetic resonance spectrum of the pure cyanide group-containing quaternary ammonium salt surfactant in Example 1 of the present invention in the range of 2.4 - 4.9 ppm;

[0021] Figure 4 It is the mass spectrum of the pure cyanide group-containing quaternary ammonium salt surfactant in Example 1 of the present invention;

[0022] Figure 5 It is the surface tension-concentration relationship diagram of the pure cyanide group-containing quaternary ammonium salt surfactant in Example 1 of the present invention. Detailed implementation manners

[0023] It should be noted that the following detailed description is exemplary and is intended to provide further illustration of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0024] The present invention provides a cyanide group-containing quaternary ammonium salt surfactant, and its structural formula is shown as follows:

[0025]

[0026] The present invention effectively combines a cyanide group, a quaternary ammonium salt group, a sodium sulfonate group, a hydroxyl hydrophilic group and a lipophilic group with a certain length to jointly form a surfactant with the above structure. This surfactant exhibits good surface activity, and the critical micelle concentration (CMC) is 1.17×10 -4 mol·L -1 , and the surface tension value γ CMC at CMC is 39.0 mN·m -1 ; at the same time, it has good low-foaming performance, foam-stabilizing performance and foam-suppressing performance.

[0027] The present invention also provides a preparation method of the above cyanide group-containing quaternary ammonium salt surfactant, including the following steps:

[0028] (1) React N-octadecyl-1,3-propylenediamine with acrylonitrile in a solvent to prepare reaction intermediate A, and the chemical structural formula of the reaction intermediate A is:

[0029]

[0030] (2) Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to reaction intermediate A and carry out a mixing reaction to obtain the product.

[0031] In some embodiments, in step (1), the solvent is a lower-carbon-number alcohol solvent; preferably, the lower-carbon-number alcohol solvent includes one or both of ethanol and isopropanol.

[0032] In some embodiments, the molar ratio of N-octadecyl-1,3-propanediamine, acrylonitrile, and sodium 3-chloro-2-hydroxypropyl sulfonate is 1:3 to 3.2:1 to 1.1. Using the above ratio can ensure less by-product formation and high yield and purity.

[0033] In some embodiments, the mass ratio of N-octadecyl-1,3-propanediamine to the solvent is 1:2 to 5; the mass concentration of the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is 20 to 40%. Under the above ratio, an appropriate reaction rate can be ensured to guarantee the purity of the product.

[0034] In some embodiments, in step (1), the reaction temperature is 60 to 80 °C and the reaction time is 3 to 6 h.

[0035] In some embodiments, in step (2), the reaction temperature of the mixing reaction is 60 to 80 °C and the reaction time is 8 to 12 h.

[0036] In some embodiments, after the mixing reaction in step (2), it further includes a step of purification by recrystallization with an organic solvent. Further, the organic solvent includes one or more of petroleum ether, methanol, and ethyl acetate; the recrystallization purification step is repeated 2 to 4 times.

[0037] The present invention also provides the use of the above-mentioned cyano-containing quaternary ammonium salt type surfactant or the cyano-containing quaternary ammonium salt type surfactant prepared by the above-mentioned preparation method as a low-foaming surfactant or an emulsifier.

[0038] The technical solution of the present invention will be further described below in conjunction with specific embodiments. The reagents in the following embodiments are all obtained through commercial channels, and the present invention does not make special restrictions on this.

[0039] Example 1

[0040] This example provides a preparation method of a cyano-containing quaternary ammonium salt type surfactant, and the reaction equation is as follows:

[0041]

[0042] (1) Add 163 g of N-octadecyl-1,3-propanediamine (0.499 mol) and 450 g of isopropanol into a three-necked flask, heat to dissolve, and then add 82.25 g of acrylonitrile (1.55 mol) in 6 batches. Stir and react at 70 °C for 4.5 h to obtain reaction intermediate A. The structural formula of reaction intermediate A is as follows:

[0043]

[0044] (2) Dissolve 102.8 g of sodium 3-chloro-2-hydroxypropyl sulfonate (0.51 mol) in 205.6 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate with a mass concentration of 33 wt%. Add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to reaction intermediate A in 6 batches. After the addition is complete, stir and react at 70 °C for 9.5 h to obtain a crude product of cyanide-containing quaternary ammonium salt type surfactant; distill off isopropanol and water, and further purify by recrystallization with methanol 3 times to obtain a pure product of cyanide-containing quaternary ammonium salt type surfactant.

[0045] Figure 1 is the infrared spectrum of the pure product of cyanide-containing quaternary ammonium salt type surfactant, 3357 cm -1 (peak 1) is the stretching vibration absorption peak of O-H, 2922 cm -1 (peak 2) is the asymmetric stretching vibration absorption peak of methylene, 2854 cm -1 (peak 3) is the symmetric stretching vibration peak of methylene, 2247 cm -1 (peak 4) is the stretching vibration absorption peak of C≡N, 1174 cm -1 (peak 5) is the stretching vibration absorption peak of C-N, 1051 cm -1 (peak 6) is the asymmetric stretching vibration absorption peak of sulfonic group S=O, 721 cm -1 (peak 7) is the in-plane rocking vibration of methylene, 621 cm -1 (peak8) is the stretching vibration absorption peak of S-O.

[0046] Figure 2 and Figure 3 is the nuclear magnetic resonance hydrogen spectrum of the pure product of cyanide-containing quaternary ammonium salt type surfactant ( 1 H NMR, 400 MHz, CD3OD), and the analysis is as follows: δ: 0.8845 - 0.9187 (3H, t, J = 6.84 Hz, -C H 3), 1.2901 (30H, s, CH3(C H 2) 15 CH2CH2-), 1.4552 - 1.5130 (2H, m, CH3(CH2)15 C H 2CH2-), 1.6096 - 1.6790(2H, m, -NCH2C H 2CH2N-), 2.4657 - 2.5022(2H, t, J = 7.3Hz, CH3(CH2) 15 CH2C H 2-), 2.5603 - 2.5975(4H, t, J = 7.44Hz, -NC H 2CH2C H 2N-), 2.6140 - 2.6418(2H, d, J = 5.56Hz, -NC H 2CH(OH)CH2SO3Na), 2.7545 - 2.7878(2H, t, J = 6.66Hz, -NC H 2CH2CN), 2.8164 - 2.8494(4H, t, J = 6.6Hz, 2× - NC H 2CH2CN(tail end)), 2.9691 - 3.0039(6H, t, J = 6.96Hz, 3× - NCH2C H 2CN), 3.1304 - 3.1449(2H, d, -C H 2SO3Na), 3.4741 - 3.4907(1H, m, -NCH2C H (OH)CH2SO3Na) ppm. The solvent peak of deuterated methanol is at 3.3100 ppm; the water peak of deuterated methanol is at 4.8641 ppm.

[0047] Figure 4 This is the mass spectrum of the pure cyanide - containing quaternary ammonium salt surfactant, and the analysis is as follows: HRMS(ESI)(negative) m / z: [M - Na + - Calcd for C 33 H 61 O4N5SClNa, 658.4133; Found 658.4704.

[0048] Example 2

[0049] This example provides a preparation method of a cyanide - containing quaternary ammonium salt surfactant, including the following steps:

[0050] (1) Add 163 g of N - octadecyl - 1,3 - propanediamine (0.499 mol) and 450 g of absolute ethanol into a three - necked flask, heat to dissolve, and then add 82.25 g of acrylonitrile (1.55 mol) in 6 batches, stir and react at 70 °C for 4.5 h to obtain reaction intermediate A. The structural formula of reaction intermediate A is as follows:​

[0051]

[0052] (2) Dissolve 102.8 g of sodium 3-chloro-2-hydroxypropyl sulfonate (0.51 mol) in 205.6 g of water to obtain an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate with a mass concentration of 33 wt%. Add the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to the reaction intermediate A in 6 batches. After the addition is complete, stir and react at 70 °C for 9.5 h to obtain a crude product of the cyanide-containing quaternary ammonium salt type surfactant. Distill off ethanol and water, and further purify it by recrystallization from methanol 3 times to obtain a pure product of the cyanide-containing quaternary ammonium salt type surfactant.

[0053] Test Example

[0054] 1. Determination of the foam suppression performance of the cyanide-containing quaternary ammonium salt type surfactant:

[0055] Take 10 mL of a 0.5% (w / w) aqueous solution of sodium dodecylbenzenesulfonate (LBS) and a certain mass of the cyanide-containing quaternary ammonium salt type surfactant and add them to a 100 mL stoppered graduated cylinder. Plug the stopper and shake vigorously 20 times to measure the foam volume (V1) and calculate the foam suppression value (P).

[0056] P = (V0 - V1) / V0

[0057] Among them, V0 is the foam volume in the blank test, in mL; V1 is the foam volume when the cyanide-containing quaternary ammonium salt type surfactant is added, in mL.

[0058] The foam suppression properties of the cyanide-containing quaternary ammonium salt type surfactant before and after purification and OP-10 are shown in Table 1 and Table 2. It can be seen from Table 1 and Table 2 that when the addition amount of OP-10 is 0.05 - 0.2 g, the foam suppression value is below 0.1, while for the pure product of the cyanide-containing quaternary ammonium salt type surfactant prepared in Example 1 of the present invention, when the addition amount is 0.1 g, the foam suppression value can reach above 0.5, indicating that it has good foam suppression performance.

[0059] Table 1 Foam suppression properties of the cyanide-containing quaternary ammonium salt type surfactant before purification in Example 1

[0060]

[0061] Table 2 Foam suppression properties of the cyanide-containing quaternary ammonium salt type surfactant after purification in Example 1

[0062]

[0063] 2. Determination of the emulsifying ability of the cyanide-containing quaternary ammonium salt type surfactant in Example 1:

[0064] Take 20 mL of an aqueous solution of a cyanide-based quaternary ammonium salt surfactant pure product with a mass fraction of 0.1% and 20 mL of liquid paraffin in a 100 mL stoppered graduated cylinder. Vigorously shake it 5 times and let it stand for 1 minute, and repeat 5 times. Measure the time required to separate 10 mL of water. Compare it with the OP-10 surfactant. OP-10 is one of the surfactants with the best emulsifying performance currently recognized.

[0065] After measurement, the water separation time of the cyanide-based quaternary ammonium salt surfactant pure product is 103 seconds, and the water separation time of OP-10 is 684 seconds. This shows that the cyanide-based quaternary ammonium salt surfactant prepared in Example 1 has good emulsifying performance.

[0066] 3. Determination of the foaming and foam stability of the cyanide-based quaternary ammonium salt surfactant in Example 1:

[0067] Prepare 100 mL of an aqueous solution of a cyanide-based quaternary ammonium salt surfactant pure product with a concentration of 0.001 mol / L. Take 20 mL and place it in a 100 mL stoppered graduated cylinder, and keep it at a constant temperature of 25 °C for 15 minutes. Vigorously shake it 20 times and measure the initial volume of the foam (K0). Measure the volume of the foam (K5) after 5 minutes, and the time (t 1 / 2 ) when the foam volume decays to 1 / 2 of the initial volume. Compare it with the commonly used surfactant sodium dodecylbenzenesulfonate under the same conditions. The results are shown in Table 3. It can be seen from Table 3 that the cyanide-based quaternary ammonium salt surfactant prepared in the present invention has good low-foaming and foam-stabilizing properties and can be used as a low-foaming surfactant.

[0068] Table 3 Foaming and foam stability of the cyanide-based quaternary ammonium salt surfactant pure product prepared in Example 1

[0069]

[0070] 4. Determination of the surface activity data of the cyanide-based quaternary ammonium salt surfactant pure product in Example 1:

[0071] Figure 5 is the change curve of the surface tension and the logarithm of the concentration (γ-log c) of the cyanide-based quaternary ammonium salt surfactant. According to this curve, CMC, γ CMC , C 20 , pC 20 and CMC / C 20 are obtained. As shown in Table 4, it can be seen that the cyanide-based quaternary ammonium salt surfactant pure product prepared in the present invention has good surface activity.

[0072] Table 4 Surface activity data of the cyanide-based quaternary ammonium salt surfactant in Example 1

[0073] sample <![CDATA[CMC (mol·L -1 )]]> <![CDATA[γ CMC (mN·m -1 )]]> <![CDATA[C 20 (mol·L -1 )]]> <![CDATA[pC 20 > <![CDATA[CMC / C 20 > Example 1 <![CDATA[1.17×10 -4 > 39.0 <![CDATA[4.61×10 -5 > 4.34 2.54

[0074] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various modifications and variations can be made to the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A cyanide-containing quaternary ammonium salt type surfactant, characterized in that, The structural formula of the cyanide group-containing quaternary ammonium salt type surfactant is as shown in the following formula:

2. The preparation method of the cyanide group-containing quaternary ammonium salt type surfactant according to claim 1, characterized in that, It includes the following steps: (1) React N-octadecyl-1,3-propanediamine with acrylonitrile in a solvent to prepare reaction intermediate A, and the chemical structural formula of the reaction intermediate A is: (2) Add an aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate to reaction intermediate A and carry out a mixed reaction to obtain it.

3. The preparation method according to claim 2, characterized in that, In step (1), the solvent includes one or two of ethanol or isopropanol.

4. The preparation method according to claim 2, wherein, The molar ratio of the N-octadecyl-1,3-propanediamine, acrylonitrile, and sodium 3-chloro-2-hydroxypropyl sulfonate is 1:3 to 3.2:1 to 1.

1.

5. The preparation method according to claim 2, wherein, The mass ratio of the N-octadecyl-1,3-propanediamine to the solvent is 1:2 to 5; the mass concentration of the aqueous solution of sodium 3-chloro-2-hydroxypropyl sulfonate is 20 to 40%.

6. The preparation method according to claim 2, wherein In step (1), the reaction temperature is 60 to 80 °C and the reaction time is 3 to 6 h.

7. The preparation method according to claim 2, characterized in that, In step (2), the reaction temperature of the mixed reaction is 60 to 80 °C and the reaction time is 8 to 12 h.

8. The preparation method according to claim 2, characterized in that, In step (2), after the mixed reaction, it further includes a step of recrystallization purification with an organic solvent.

9. The preparation method according to claim 8, characterized in that, The organic solvent includes one or more of petroleum ether, methanol, and ethyl acetate; the recrystallization purification step is repeated 2 to 4 times.

10. The application of the cyanide group-containing quaternary ammonium salt type surfactant according to claim 1 or the cyanide group-containing quaternary ammonium salt type surfactant prepared by the preparation method according to any one of claims 2 to 9 as a low-foaming surfactant or an emulsifier.

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