A tertiary amine amide sulfonic acid type surfactant, its preparation method and application

Abstract

The application provides a tertiary amide sulfonic acid type surfactant, a preparation method and application thereof. The tertiary amide sulfonic acid type surfactant is formed by combining a sulfonic acid group, an amide group and a tertiary amine group hydrophilic group with a lipophilic group, and has a novel structure and good surface activity. The raw material for preparing the tertiary amide sulfonic acid type surfactant is an alkyl amine, which is cheaper than the raw material used in the current sulfonic acid type surfactant, and the production cost is lower. The preparation method of the tertiary amide sulfonic acid type surfactant is simple and does not need high-temperature reaction.

Description

Technical Field

[0001] This invention relates to the field of fine chemical technology, specifically to a tertiary amine sulfonic acid type surfactant, its preparation method, and its application. Background Technology

[0002] The information disclosed in the background section of this invention is intended only to enhance the 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] Surfactants, due to their asymmetric molecular structure, exhibit self-assembly behavior and reduce the surface tension of aqueous solutions, playing a significant role in industrial and agricultural production and daily life. Low-foaming surfactants are those exhibiting low-foaming properties in industrial applications. Currently, the development of sulfonic acid surfactants is relatively limited, and their price is also relatively high, thus restricting their widespread application. Furthermore, the inventors have discovered that existing surfactants also suffer from poor anti-foaming, low-foaming, and emulsifying properties, as well as complex preparation processes and methods. Summary of the Invention

[0004] To address the shortcomings of current sulfonic acid surfactant production technologies, such as limited variety, insufficient performance improvement, and complex preparation methods, this invention provides a tertiary amine amide sulfonic acid surfactant, its preparation method, and its applications. The tertiary amine amide sulfonic acid surfactant of this invention exhibits surface properties such as antifoaming and low-foaming properties, and its preparation method is simple, with widely available raw materials and low production costs. The tertiary amine amide sulfonic acid surfactant of this invention can be used as an antifoaming agent, a low-foaming surfactant, or an emulsifier.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows:

[0006] In a first aspect of the present invention, a tertiary amine sulfonic acid type surfactant is provided, the general molecular structural formula of which is:

[0007]

[0008] n is 12, 14, 16, or 18;

[0009] C n H 2n+1 It is a straight-chain alkyl group;

[0010] Specifically, the tertiary amine sulfonic acid type surfactant is selected from the following structures:

[0011] Formula Y-12:

[0012] Formula Y-14:

[0013] Formula Y-16:

[0014] Formula Y-18:

[0015] Experiments show that if sulfonic acid groups and amide groups are introduced into the molecular structure of surfactants to form novel tertiary amine amide sulfonic acid surfactants, they have good emulsifying and antifoaming properties.

[0016] In a second aspect, the present invention provides a method for preparing the tertiary amine sulfonic acid type surfactant described in the first aspect, comprising the following steps:

[0017] 1) By reacting an alkylamine, an alcohol solvent, and 2-acrylamide-2-methylpropanesulfonic acid (AMPS), reaction intermediate M can be obtained. The general structural formula of reaction intermediate M is:

[0018] C n H 2n+1 NHCH2CH2CONHC(CH3)2CH2SO3H;

[0019] n is 12, 14, 16, or 18;

[0020] C n H 2n+1 It is a straight-chain alkyl group;

[0021] 2) Add acrylamide to reaction intermediate M and react to obtain tertiary amine amide sulfonic acid type surfactant product Y. Evaporate the solvent from product Y under normal pressure and continue to recrystallize and purify it with organic solvent to obtain pure tertiary amine amide sulfonic acid type surfactant Y (Y-12, Y-14, Y-16 or Y-18).

[0022] The reaction formula is:

[0023] C n H 2n+1 NH2+CH2=CHCONHC(CH3)2CH2SO3H

[0024] →C n H 2n+1 NHCH2CH2CONHC(CH3)2CH2SO3H (1)

[0026]

[0027] In one or more embodiments, the molar ratio of the alkylamine, alcohol solvent, AMPS, and acrylamide is 1:(7.5-15.5):(1.00-1.06):(1.00-1.09).

[0028] In one or more embodiments, in step 1), the alkylamine is dodecylamine, tetradecylamine, hexadecylamine, or octadecylamine.

[0029] In one or more embodiments, in step 1), the alcohol solvent may be any one or both of ethanol and isopropanol.

[0030] In one or more embodiments, in step 1), the reaction temperature is 65–80°C and the reaction time is 3–5 hours.

[0031] In one or more embodiments, in step 2), the organic solvent used for recrystallization separation and purification is methanol, petroleum ether, or ethyl acetate.

[0032] In one or more embodiments, in step 2), the reaction temperature is 65–80°C and the reaction time is 2–4 hours.

[0033] In a preferred embodiment, the preparation method of the above-mentioned tertiary amine sulfonic acid surfactant Y specifically includes the following steps:

[0034] (1) Add alkylamine to the reactor, add alcohol solvent, heat and stir at 65-80℃ to dissolve, then add 2-acrylamide-2-methylpropanesulfonic acid (abbreviated as AMPS) in batches. After the addition is complete, stir the reaction at 65-80℃ for 3-5 hours to obtain reaction intermediate M.

[0035] (2) Add acrylamide to reaction intermediate M. After the addition is complete, stir the reaction at 65-80℃ for 2-4 hours to obtain tertiary amine sulfonic acid type surfactant product Y. Evaporate the solvent from product Y under normal pressure, and continue to recrystallize and purify it 3-5 times with organic solvent to obtain pure tertiary amine sulfonic acid type surfactant Y (Y-12, Y-14, Y-16 or Y-18).

[0036] A third aspect of the invention provides an application of the tertiary amine sulfonic acid type surfactant described in the first aspect as an antifoaming agent, a low-foaming surfactant, and an emulsifier. For example, its application in industrial cleaning.

[0037] This invention uses alkylamine as the raw material for tertiary amine amide sulfonic acid type surfactants. In the preparation of tertiary amine amide sulfonic acid type surfactants, sulfonic acid groups and amide groups are introduced into the surfactant molecules by sequentially adding 2-acrylamido-2-methylpropanesulfonic acid (abbreviated as AMPS) and acrylamide, thereby giving it surface activity.

[0038] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0039] (1) The present invention combines hydrophilic groups of sulfonic acid, amide and tertiary amine with lipophilic groups to form a novel tertiary amine amide sulfonic acid surfactant with good surface activity.

[0040] (2) The raw material for preparing tertiary amine sulfonic acid type surfactants in this invention is alkylamine, which is cheaper than the raw materials used in current sulfonic acid type surfactants and has a lower production cost.

[0041] (3) Existing technologies use chlorosulfonic acid, concentrated sulfuric acid, fuming sulfuric acid, or SO3 as sulfonating agents to prepare sulfonate surfactants through sulfonation reactions. These sulfonation reactions involve high temperatures, complex processes, and are highly hazardous and corrosive. The tertiary amine amide sulfonate surfactant preparation method of this invention is simple and does not require high-temperature reactions. Attached Figure Description

[0042] 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.

[0043] Figure 1 The infrared spectrum of product Y-12 from Example 1 is shown.

[0044] Figure 2 The infrared spectrum of product Y-14 from Example 2 is shown.

[0045] Figure 3 The infrared spectrum of product Y-16 from Example 3 is shown.

[0046] Figure 4 The infrared spectrum of product Y-18 from Example 4 is shown.

[0047] Figure 5 The graph shows the relationship between the surface tension and the concentration of product Y-14 from Example 2.

[0048] Figure 6 The graph shows the relationship between the surface tension and the concentration of product Y-16 from Example 3. Detailed Implementation

[0049] It should be noted that the following detailed descriptions are exemplary and intended to provide further illustration of the invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0050] Example 1

[0051] (1) Preparation of tertiary amine sulfonic acid type surfactant (product Y-12):

[0052] 1) Add 185.35g dodecylamine and 550g isopropanol to the reactor, heat and stir at 75°C to dissolve, then add 215.6g AMPS in 4 batches, stir and react at 75°C for 3 hours to obtain reaction intermediate M-12.

[0053] 2) 74.6g of acrylamide was added to reaction intermediate M-12 in 4 batches. After the addition was completed, the mixture was stirred at 75℃ for 3 hours to obtain tertiary amine amide sulfonic acid type surfactant product Y-12. The solvent of product Y-12 was evaporated under normal pressure, and it was further purified by recrystallization from methanol 3 times to obtain pure tertiary amine amide sulfonic acid type surfactant Y-12.

[0054] FTIR analysis of pure Y-12 ( Figure 1 ): 3431cm -1 Peak 1 (3215 cm⁻¹) is the stretching vibration peak of the OH group in the sulfonic acid group. -1 Peak 2 is the stretching vibration peak of amide NH, at 2928 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2855 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1672 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of amide, at 1557 cm⁻¹. -1 Peak 6 is the absorption peak of the deformation vibration of NH, at 1456 cm⁻¹. -1 (peak 7) represents the asymmetric bending vibration of the methylene group, 1213 cm⁻¹. -1 Peak 8 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1040 cm⁻¹. -1 Peak 9 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 941 cm⁻¹. -1 Peak 10 is the absorption peak of the out-of-plane bending vibration of the methylene group, at 721 cm⁻¹. -1 Peak 11 is the absorption peak of the in-plane rocking vibration of the methylene group, at 629 cm⁻¹. -1 Peak 12 is the absorption peak of SO stretching vibration, at 525 cm⁻¹. -1 (peak 13) is the absorption peak of the bending vibration of OH in the sulfonic acid group.

[0055] The reaction formula is:

[0056] C 12 H 25 NH2+CH2=CHCONHC(CH3)2CH2SO3H→C12 H 25 NHCH2CH2CONHC(CH3)2CH2SO3H (3)

[0057]

[0058] Example 2

[0059] (1) Preparation of tertiary amine sulfonic acid type surfactant (product Y-14):

[0060] 1) Add 213.4g tetradecylamine and 550g isopropanol to the reactor, heat and stir at 75°C to dissolve, then add 215.6g AMPS in 4 batches, stir and react at 75°C for 3 hours to obtain reaction intermediate M-14.

[0061] 2) 74.6g of acrylamide was added to reaction intermediate M-14 in 4 batches. After the addition was completed, the mixture was stirred at 75℃ for 3 hours to obtain tertiary amine amide sulfonic acid type surfactant product Y-14. The solvent of product Y-14 was evaporated under normal pressure, and it was further purified by recrystallization from methanol 3 times to obtain pure tertiary amine amide sulfonic acid type surfactant Y-14.

[0062] FTIR analysis of pure Y-14 ( Figure 2 ): 3447cm -1 Peak 1 (3215 cm⁻¹) is the stretching vibration peak of the OH group in the sulfonic acid group. -1 Peak 2 is the stretching vibration peak of amide NH, at 2929 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2855 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1655 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of the amide, at 1558 cm⁻¹. -1 Peak 6 is the absorption peak of the deformation vibration of NH, at 1458 cm⁻¹. -1 (peak 7) represents the asymmetric bending vibration of the methylene group, 1219 cm⁻¹. -1 Peak 8 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1040 cm⁻¹. -1 Peak 9 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 955 cm⁻¹. -1 Peak 10 is the absorption peak of the out-of-plane bending vibration of the methylene group, at 721 cm⁻¹. -1 Peak 11 is the absorption peak of the in-plane rocking vibration of the methylene group, at 631 cm⁻¹. -1 Peak 12 is the absorption peak of SO stretching vibration, at 534 cm⁻¹.-1 (peak 13) is the absorption peak of the bending vibration of OH in the sulfonic acid group.

[0063] The reaction formula is:

[0064] C l4 H 29 NH2+CH2=CHCONHC(CH3)2CH2SO3H→C 14 H 29 NHCH2CH2CONHC(CH3)2CH2SO3H (5)

[0065]

[0066] Example 3

[0067] (1) Preparation of tertiary amine sulfonic acid type surfactant (product Y-16):

[0068] 1) Add 241.46g of cetylamine and 550g of isopropanol to the reactor, heat and stir at 75°C to dissolve, then add 215.6g of AMPS in 4 batches, stir and react at 75°C for 3 hours to obtain reaction intermediate M-16.

[0069] 2) 74.6g of acrylamide was added to reaction intermediate M-16 in 4 batches. After the addition was complete, the mixture was stirred at 75℃ for 3 hours to obtain tertiary amine amide sulfonic acid type surfactant product Y-16. The solvent of product Y-16 was evaporated under normal pressure, and it was further purified by recrystallization from methanol 3 times to obtain pure tertiary amine amide sulfonic acid type surfactant Y-16.

[0070] FTIR analysis of pure Y-16 ( Figure 3 ): 3433cm -1 Peak 1 is the stretching vibration peak of the OH group in the sulfonic acid group, at 3202 cm⁻¹. -1 Peak 2 is the stretching vibration peak of amide NH, at 2922 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2853 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1670 cm⁻¹. -1 Peak 5 is the absorption peak of the C=O stretching vibration of the amide, at 1558 cm⁻¹. -1 Peak 6 is the absorption peak of the deformation vibration of NH, at 1470 cm⁻¹. -1 (peak 7) represents the asymmetric bending vibration of the methylene group, 1213 cm⁻¹. -1 Peak 8 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1040 cm⁻¹. -1Peak 9 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 941 cm⁻¹. -1 Peak 10 is the absorption peak of the out-of-plane bending vibration of the methylene group, at 723 cm⁻¹. -1 Peak 11 is the absorption peak of the in-plane rocking vibration of the methylene group, at 621 cm⁻¹. -1 Peak 12 is the absorption peak of SO stretching vibration, at 528 cm⁻¹. -1 (peak 13) is the absorption peak of the bending vibration of OH in the sulfonic acid group.

[0071] The reaction formula is:

[0072] C 16 H 33 NH2+CH2=CHCONHC(CH3)2CH2SO3H→C 16 H 33 NHCH2CH2CONHC(CH3)2CH2SO3H (7)

[0073]

[0074] Example 4

[0075] (1) Preparation of tertiary amine sulfonic acid type surfactant (product Y-18):

[0076] 1) Add 269.51g of octadecylamine and 550g of isopropanol to the reactor, heat and stir at 75°C to dissolve, then add 215.6g of AMPS in 4 batches, stir and react at 75°C for 3 hours to obtain reaction intermediate M-18.

[0077] 2) 74.6g of acrylamide was added to reaction intermediate M-18 in 4 batches. After the addition was completed, the mixture was stirred at 75℃ for 3 hours to obtain the tertiary amine sulfonic acid surfactant product Y-18. The solvent of product Y-18 was evaporated under normal pressure, and it was further purified by recrystallization from methanol 3 times to obtain the pure tertiary amine sulfonic acid surfactant Y-18.

[0078] FTIR analysis of pure Y-18 ( Figure 4 ): 3447cm -1 Peak 1 is the stretching vibration peak of the OH group in the sulfonic acid group, at 3192 cm⁻¹. -1 Peak 2 is the stretching vibration peak of amide NH, at 2920 cm⁻¹. -1 Peak 3 is the absorption peak of the asymmetric stretching vibration of the methylene group, at 2855 cm⁻¹. -1 Peak 4 is the peak of the symmetric stretching vibration of the methylene group, at 1670 cm⁻¹. -1Peak 5 is the absorption peak of the C=O stretching vibration of the amide, at 1553 cm⁻¹. -1 Peak 6 is the absorption peak of the deformation vibration of NH, at 1472 cm⁻¹. -1 (peak 7) represents the asymmetric bending vibration of the methylene group, 1217 cm⁻¹. -1 Peak 8 is the absorption peak of the symmetric stretching vibration of the sulfonic acid group S=O, at 1042 cm⁻¹. -1 Peak 9 is the absorption peak of the asymmetric stretching vibration of the sulfonic acid group S=O, at 949 cm⁻¹. -1 Peak 10 is the absorption peak of the out-of-plane bending vibration of the methylene group, at 725 cm⁻¹. -1 Peak 11 is the absorption peak of the in-plane rocking vibration of the methylene group, at 633 cm⁻¹. -1 Peak 12 is the absorption peak of SO stretching vibration, at 532 cm⁻¹. -1 (peak 13) is the absorption peak of the bending vibration of OH in the sulfonic acid group.

[0079] The reaction formula is:

[0080] C 18 H 37 NH2+CH2=CHCONHC(CH3)2CH2SO3H→C 18 H 37 NHCH2CH2CONHC(CH3)2CH2SO3H (9)

[0082]

[0083] Experimental Example 1

[0084] The antifoaming performance of the pure tertiary amine sulfonic acid surfactant Y (Y-12, Y-14, Y-16, or Y-18) prepared in Examples 1-4 was tested: At room temperature, 10 mL of 0.5% (mass fraction) sodium dodecylbenzenesulfonate (LBS) aqueous solution and a certain amount of sample were poured into a 100 mL stoppered graduated cylinder, the stopper was sealed, and the cylinder was shaken vigorously up and down 20 times. The volume of foam produced was recorded. The antifoaming value (T) indicates the antifoaming ability of the sample.

[0085] T = (V0 - V1) / V0

[0086] Where V0 is the foam volume (mL) during the blank test; V1 is the foam volume (mL) when the sample is added.

[0087] The antifoaming properties of pure tertiary amine sulfonic acid surfactants Y (Y-12, Y-14, Y-16, or Y-18) and OP-10 (commercial product) are compared and are shown in Table 1. It is concluded that the tertiary amine sulfonic acid surfactants Y prepared in Examples 1-4 have better antifoaming ability.

[0088] Table 1. Defoaming performance of the samples

[0089]

[0090] Experiment Example 2

[0091] Emulsifying ability test method: At room temperature, take 20 mL of 0.1% (mass fraction) pure aqueous solution of tertiary amine sulfonic acid surfactant Y (Y-12, Y-14, Y-16 or Y-18) prepared in Examples 1-4 or aqueous solution of OP-10 (commercial product) and 20 mL of liquid paraffin, pour them into a 100 mL stoppered graduated cylinder, stopper the cylinder, shake vigorously 5 times, let stand for 1 min, repeat 5 times, and record the time when 10 mL of water is separated.

[0092] The experimental results are shown in Table 2. It is concluded that the tertiary amine sulfonic acid type surfactants Y (Y-12, Y-14, Y-16 or Y-18) synthesized from Examples 1-4 have good emulsifying ability.

[0093] Table 2 Emulsifying ability of samples

[0094] product Water separation time (s) Product Y-12 185 Product Y-14 329 Product Y-16 318 Product Y-18 256 OP-10 684

[0095] Experimental Example 3

[0096] Foaming and foam stability tests: Prepare 80 mL of an aqueous solution of product Y (Y-12, Y-14, Y-16, or Y-18) at a concentration of 0.001 mol / L at room temperature. Take 20 mL of this solution and place it in a 100 mL stoppered graduated cylinder, incubating at 25°C for 10 min. Vigorously shake 20 times, then allow it to stand in the water bath. Record the initial foam volume (H0), the foam volume after 5 min (H5), and the time required for the foam volume to decrease to half of its initial volume (t). 1 / 2 ,half life).

[0097] The experimental results are shown in Table 3. Compared with sodium dodecylbenzenesulfonate, product Y (Y-12, Y-14, Y-16 or Y-18) has low foaming properties but good foam stability. This indicates that the tertiary amine sulfonic acid type surfactant Y (Y-12, Y-14, Y-16 or Y-18) is a low-foaming surfactant.

[0098] Table 3. Foaming and foam stability of the samples

[0099]

[0100] Experiment Example 4

[0101] Surface tension was measured using the platinum ring method, and the surface tension (γ)-log c variation curve was obtained (see...). Figure 5 and Figure 6 As shown), and the critical micelle concentration (CMC), and the surface tension at CMC (γ). CMC C 20 pC 20 and CMC / C 20 (Table 4). It can be seen that the surface properties of product Y (Y-12, Y-14, Y-16 or Y-18) are better.

[0102] Table 4 Surface property parameters

[0103] product <![CDATA[CMC(mol·L -1 )]]> <![CDATA[γ CMC (mN·m -1 )]]> <![CDATA[C 20 (mol·L -1 )]]> <![CDATA[pC 20 ]]> <![CDATA[CMC / C 20 ]]> Product Y-12 <![CDATA[9.33×10 -5 ]]> 57.8 - - - Product Y-14 <![CDATA[2.74×10 -5 ]]> 25.1 <![CDATA[1.53×10 -5 ]]> 4.82 1.79 Product Y-16 <![CDATA[2.34×10 -5 ]]> 25.6 <![CDATA[8.19×10 -6 ]]> 5.09 2.86 Product Y-18 <![CDATA[9.55×10 -5 ]]> 56.5 - - -

[0104] 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 tertiary amine sulfonic acid type surfactant, characterized in that, Its general molecular formula is: n is 12, 14, 16, or 18; C n H 2n+1 It is a straight-chain alkyl group.

2. The method for preparing the tertiary amine sulfonic acid type surfactant according to claim 1, characterized in that, Includes the following steps: 1) An alkylamine, an alcohol solvent, and 2-acrylamide-2-methylpropanesulfonic acid are mixed and reacted to obtain reaction intermediate M. The general structural formula of reaction intermediate M is: C n H 2n+1 NHCH2CH2CONHC(CH3)2CH2SO3H; n is 12, 14, 16, 18; C n H 2n+1 It is a straight-chain alkyl group; 2) Acrylamide is added to reaction intermediate M and mixed to obtain tertiary amine amide sulfonic acid type surfactant product Y; the solvent of product Y is evaporated under normal pressure, and it is further purified by recrystallization with organic solvent to obtain the tertiary amine amide sulfonic acid type surfactant.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the alkylamine, alcohol solvent, 2-acrylamide-2-methylpropanesulfonic acid, and acrylamide is 1:(7.5-15.5):(1.00-1.06):(1.00-1.09).

4. The preparation method according to claim 2, characterized in that, In step 1), the alcohol solvent is any one or both of ethanol and isopropanol.

5. The preparation method according to claim 2, characterized in that, In step 1), the reaction temperature is 65–80°C and the reaction time is 3–5 hours.

6. The preparation method according to claim 2, characterized in that, In step 2), the organic solvent used for recrystallization separation and purification is methanol, petroleum ether, or ethyl acetate.

7. The preparation method according to claim 2, characterized in that, In step 2), recrystallization and purification are performed 3 to 5 times.

8. The preparation method according to claim 2, characterized in that, In step 2), the reaction temperature is 65–80°C and the reaction time is 2–4 hours.

9. The application of the tertiary amine sulfonic acid type surfactant as described in claim 1 as an antifoaming agent, a low-foaming surfactant, and an emulsifier.

10. The application according to claim 9, characterized in that, Applications in industrial cleaning.

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