Gemini type carboxylic acid-based surfactant as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of fine chemical engineering, and relates to a Gemini-type carboxylic acid-based surfactant and a preparation method and application thereof, the Gemini-type carboxylic acid-based surfactant is a compound with a molecular structure as shown in formula I or a salt thereof; in the formula, n is equal to 12, 14, 16 or 18. The Gemini type carboxylic surfactant is prepared from the following raw materials: cocamidopropyl dimethyl tertiary amine, fatty amine, acrylic acid, epoxy chloropropane and hydrochloric acid in a molar ratio of 1: (1.00-1.06): (2.00-2.25): (1.0-1.2): (1.0-1.2). The Gemini type carboxylic acid-based surfactant provided by the invention can be used as a foam inhibitor and a low-foam surfactant.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemicals, and particularly relates to a Gemini-type carboxylic acid-based surfactant, a preparation method thereof, and an application thereof. Background Art

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

[0003] Among current low-foaming surfactants, Chinese Patent CN112844219A discloses a low-foaming amphoteric surfactant, which includes the following steps: (1) Crude oil treatment: Among them, the crude oil treatment is preferably with n-alkanes > 98%, carbon numbers being C 13 -C 17 is appropriate, the aromatic hydrocarbon content ≤ 0.06%, the iodine value < 5 g / 100 g, the moisture content < 0.03%, and the oxygen content in chlorine and sulfur dioxide gases should < 0.2%; (2) Chlorosulfonation reaction: In order to avoid the influence of reaction heat on the preparation process during the ultraviolet lamp reaction, an internal cooling method is adopted to ensure the stability of raw materials. Internal cooling means using a cooling pipe for cooling, with good cooling effect and stable reaction temperature; (3) Degassing and saponification; (4) Oil and salt removal.

[0004] It can be seen that in the prior art, chlorine and sulfur dioxide gases are used for the chlorosulfonation reaction to prepare low-foaming surfactants, and its production process is very dangerous and the preparation technology is complex. In addition, currently, most low-foaming surfactants are compound products, and there are few single components. Summary of the Invention

[0005] Aiming at the disadvantages existing in the prior art, the first object of the present invention is to provide a Gemini-type carboxylic acid-based surfactant, and the Gemini-type carboxylic acid-based surfactant has foam suppression property, low-foaming property, and good emulsifying performance.

[0006] The second object of the present invention is to provide a preparation method of the Gemini-type carboxylic acid-based surfactant, and this process method is simple and has low production cost.

[0007] The third object of the present invention is to provide an application of the Gemini-type carboxylic acid-based surfactant as a foam suppressant and a low-foaming surfactant.

[0008] In order to achieve the above technical objects, the technical solution of the invention is as follows:

[0009] In the first aspect of the present invention, there is provided a Gemini-type carboxylic acid-based surfactant, which is a compound having the molecular structure shown in Formula I or a salt thereof;

[0010]

[0011] Among them, n = 12, 14, 16 or 18.

[0012] In some embodiments, the salt is a carboxylate salt. Preferably, the carboxylate salt is a sodium carboxylate salt, and more preferably a disodium carboxylate salt. Among them, after the two carboxylic acid groups of the compound having the molecular structure shown in Formula I are converted into two sodium carboxylate groups, its disodium carboxylate salt is obtained.

[0013] In the second aspect of the present invention, a preparation method of the Gemini-type carboxyl surfactant described in the first aspect is provided, including the following steps:

[0014] 1) Add fatty amine, organic solvent A and acrylic acid to a reactor, mix and react to obtain intermediate M1, and the chemical structural formula of the intermediate M1 is:

[0015] CnH2n+1N(CH-CHC00H2;

[0016] Among them, n = 12, 14, 16 or 18;

[0017] 2) Add epichlorohydrin and hydrochloric acid to intermediate M1, mix and react to obtain intermediate M2, and the chemical structural formula of the intermediate M2 is:

[0018]

[0019] Among them, n = 12, 14, 16 or 18;

[0020] 3) Add coconut oil amide propyl dimethyl tertiary amine to intermediate M2, mix and react to obtain a Gemini-type carboxyl surfactant.

[0021] The reaction general formula is:

[0022]

[0023] In some embodiments, the molar ratio of the coconut oil amide propyl dimethyl tertiary amine, fatty amine, acrylic acid, epichlorohydrin, and hydrochloric acid is 1:1.00 - 1.06:2.00 - 2.25:1.0 - 1.2:1.0 - 1.2.

[0024] In some embodiments, the mass ratio of the coconut oil amide propyl dimethyl tertiary amine to the organic solvent A is 1:3 - 9.

[0025] In some embodiments, in step 1), the organic solvent A is ethanol or isopropanol.

[0026] In some embodiments, in step 1), the fatty amine is octadecylamine, hexadecylamine, tetradecylamine or dodecylamine.

[0027] In some embodiments, in step 1), during the preparation of intermediate M1, the reaction temperature is 60 - 82 °C and the reaction time is 2 - 4 h.

[0028] In some embodiments, in step 2), during the preparation of intermediate M2, the reaction temperature is 60 - 82 °C and the reaction time is 4 - 6 h.

[0029] In some embodiments, in step 3), during the preparation of the Gemini - type carboxyl - based surfactant, the reaction temperature is 60 - 82 °C and the reaction time is 3 - 6 h.

[0030] In some embodiments, after the preparation of the Gemini - type carboxyl - based surfactant in step 3), a purification step is further included: evaporating the organic solvent A, and then recrystallizing and purifying 2 - 3 times with organic solvent B to obtain the pure product; preferably, the organic solvent B is methanol, petroleum ether or ethyl acetate.

[0031] In some embodiments, the preparation method of the above - mentioned Gemini - type carboxyl - based surfactant specifically includes the following steps:

[0032] (1) Add fatty amine and organic solvent A into a reactor, heat and stir, then add acrylic acid, and stir and react at 60 - 82 °C for 2 - 4 h to obtain intermediate M1;

[0033] (2) Add epichlorohydrin and hydrochloric acid to intermediate M1, and stir and react at 60 - 82 °C for 4 - 6 h to obtain intermediate M2;

[0034] (3) Add coconut oil amide propyl dimethyl tertiary amine to intermediate M2, and stir and react at 60 - 82 °C for 3 - 6 h to obtain the Gemini - type carboxyl - based surfactant product; evaporate the organic solvent A, and recrystallize and purify 2 - 3 times with organic solvent B to obtain the pure product of the Gemini - type carboxyl - based surfactant.

[0035] In the third aspect of the present invention, there is provided an application of the Gemini - type carboxyl - based surfactant described in the first aspect as an antifoaming agent, a low - foaming surfactant and / or an emulsifier.

[0036] The specific embodiments of the present invention have the following beneficial effects:

[0037] (1) The present invention discloses the molecular structure of a Gemini-type carboxylic acid-based surfactant with a novel structure, which is composed of two lipophilic groups, a linking group, and multiple hydrophilic groups. The hydrophilic groups include quaternary ammonium salts, amide groups, carboxyl groups, and hydroxyl groups. This Gemini-type carboxylic acid-based surfactant has foam suppression properties, low foam properties, and excellent emulsifying properties.

[0038] (2) The raw materials of the present invention are inexpensive, and the production cost is low.

[0039] (3) The preparation method of the present invention is simple, avoiding the chlorosulfonation reaction using chlorine and sulfur dioxide gases. The production process is safe and the energy consumption is low. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The specification drawings forming 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 to the present invention.

[0041] Figure 1 The infrared spectrum of the pure product of the Gemini-type carboxylic acid-based surfactant prepared in Example 1.

[0042] Figure 2 The graph of the relationship between the surface tension and the logarithm of the concentration of the pure product of the Gemini-type carboxylic acid-based surfactant prepared in Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0043] In order to enable those skilled in the art to more clearly understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below in combination with specific examples and experimental examples.

[0044] Example 1

[0045] (1) Preparation of the Gemini-type carboxylic acid-based surfactant product:

[0046] 1) Add 277.6 g (1.03 mol) of octadecylamine and 1500 g of isopropanol to the reactor, heat and stir, and add 152.0 g (2.11 mol) of acrylic acid in 6 batches. Stir and react at 75 °C for 3 h to obtain intermediate M1.

[0047] 2) Add 100.8 g (1.09 mol) of epichlorohydrin in 6 batches to intermediate M1, and add 107.4 g of 37% concentrated hydrochloric acid (1.09 mol) in 6 batches. Stir and react at 75 °C for 5 h to obtain intermediate M2.

[0048] (3) 284.5 g (1.00 mol) of cocoamidopropyl dimethyl tertiary amine was added to the intermediate M2 in 6 batches, and the mixture was stirred at 75 °C for 4 h to obtain the Gemini-type carboxyl surfactant product. Isopropanol was distilled off, and the product was recrystallized from ethyl acetate three times to obtain the pure Gemini-type carboxyl surfactant product.

[0049] The pure product was subjected to infrared spectroscopy ( Figure 1 ): 3417 cm -1 (peak 1) is the stretching vibration peak of O-H, 3325 cm -1 (peak 2) is the symmetric stretching vibration peak of N-H, 2918 cm -1 (peak 3) is the asymmetric stretching vibration peak of methylene, 2852 cm -1 (peak 4) is the symmetric stretching vibration peak of methylene, 1716 cm -1 (peak 5) is the stretching vibration absorption peak of carboxylic C=O, 1650 cm -1 (peak 6) is the stretching vibration absorption peak of amide C=O, 1587 cm -1 (peak 7) is the asymmetric stretching vibration peak of C-O, 1467 cm -1 (peak 8) is the asymmetric bending vibration peak of methylene, 1390 cm -1 (peak 9) is the symmetric bending vibration peak of methylene, 719 cm -1 (peak 10) is the in-plane rocking vibration peak of methylene.

[0050] The reaction is as follows:

[0051]

[0052]

[0053] Example 2

[0054] (1) Preparation of Gemini-type carboxyl surfactant product:

[0055] 1) 277.6 g (1.03 mol) of octadecylamine and 1500 g of absolute ethanol were added to a reactor, heated and stirred, and 152.0 g (2.11 mol) of acrylic acid was added in 6 batches. The mixture was stirred at 75 °C for 3 h to obtain the intermediate M1.

[0056] 2) 100.8 g (1.09 mol) of epichlorohydrin was added to the intermediate M1 in 6 batches, and 107.4 g of 37% concentrated hydrochloric acid (1.09 mol) was added in 6 batches. The mixture was stirred at 75 °C for 5 h to obtain the intermediate M2.

[0057] 3) 284.5 g (1.00 mol) of coconut oil amido propyl dimethyl tertiary amine was added to the intermediate M2 in 6 batches, and the mixture was stirred and reacted at 75 °C for 4 h to obtain the Gemini carboxylic acid surfactant product. Ethanol was distilled off, and the product was recrystallized and purified 3 times with ethyl acetate to obtain the pure Gemini carboxylic acid surfactant product.

[0058] Experimental Example 1

[0059] The defoaming performance of the Gemini carboxylic acid surfactant product and the pure product prepared in Example 1 was tested:

[0060] 10 mL of an aqueous solution of sodium dodecylbenzenesulfonate (LBS) with a mass fraction of 0.5% and a certain amount of Gemini carboxylic acid surfactant were placed in a 100 mL stoppered graduated cylinder. The stopper was plugged, and the mixture was shaken vigorously 20 times, and the foam volume (mL) was measured. The defoaming value (T) was calculated:

[0061] T = (V 0 - V 1 ) / V 0

[0062] In the formula, V 0 is the foam volume (mL) in the blank test; V 1 is the foam volume (mL) when the Gemini carboxylic acid surfactant is added.

[0063] The data are shown in Table 1 and Table 2. It is concluded that the Gemini carboxylic acid surfactant product and the pure product prepared in Example 1 have certain defoaming ability.

[0064] Table 1 Defoaming ability (product before purification)

[0065]

[0066] Table 2 Defoaming ability (product after purification)

[0067]

[0068] Experimental Example 2

[0069] Emulsifying performance test of the pure Gemini carboxylic acid surfactant product prepared in Example 1: 20 mL of an aqueous solution of the pure Gemini carboxylic acid surfactant product with a mass fraction of 0.1% (pH value adjusted to 11.0 with NaOH) or an aqueous solution of OP-10 and 20 mL of liquid paraffin were transferred into a 100 mL stoppered graduated cylinder. The stopper was plugged, and the mixture was shaken vigorously 5 times, allowed to stand for 1 min, and repeated 5 times. The time required to separate 10 mL of water, i.e., the water separation time, was measured.

[0070] The water separation time of OP-10 was measured to be 684 s. The water separation time of the pure product of the Gemini-type carboxyl surfactant prepared in Example 1 (without adjusting the pH value with NaOH) was 13 s. The water separation time of the pure product of the Gemini-type carboxyl surfactant prepared in Example 1 (adjusting the pH value to 11.0 with NaOH) was 690 s, and its performance was superior to that of OP-10.

[0071] When the pH value of the pure product of the Gemini-type carboxyl surfactant prepared in Example 1 was adjusted to 11.0 with NaOH, the following reaction occurred:

[0072]

[0073] When the pH value was adjusted to 11.0 with NaOH, two carboxyl groups in the product molecule were converted into two sodium carboxylate groups.

[0074] It can be seen that when there were two carboxyl groups in the product molecule, the water separation time was only 13 s, and its emulsifying performance was very poor. However, when the two carboxyl groups in the product molecule were converted into two sodium carboxylate groups, the water separation time was 690 s, and its emulsifying performance was greatly improved. The reason is that the emulsifying ability of the sodium carboxylate (-COONa) group is greater than that of the carboxyl group (-COOH) or the amide group (-CONH 2 )).

[0075] It can be seen that the pure product of the Gemini-type carboxyl surfactant prepared in Example 1 showed good emulsifying ability.

[0076] Experimental Example 3

[0077] Measurement of the foaming property and foam stability of the pure product of the Gemini-type carboxyl surfactant prepared in Example 1: Prepare 100 mL of an aqueous solution of the Gemini-type carboxyl surfactant 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 10 min. Shake it 20 times, let it stand, and measure the initial foam volume (J 0 ), the foam volume at 5 min (J 5 ), and the time (t 1 / 2 ) required for the foam volume to become half of the original initial volume.

[0078] The experimental data are shown in Table 3. Compared with sodium dodecylbenzenesulfonate, it shows that the pure product of the Gemini-type carboxyl surfactant prepared in Example 1 is a low-foaming surfactant.

[0079] Table 3 Foaming property and foam stability

[0080]

[0081] Experimental Example 4

[0082] Measurement of the surface tension (γ) of the pure product of the Gemini carboxylate surfactant prepared in Example 1: Obtain the γ-log c change graph (see Figure 2 ), and obtain the critical micelle concentration (CMC), the surface tension at CMC (γ CMC ), C 20 , pC 20 and CMC / C 20 (see Table 4). It can be seen that the surface properties of the pure product of the Gemini carboxylate surfactant in Example 1 are good.

[0083] Table 4 Surface properties of the pure product

[0084] 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 > Example 1 <![CDATA[1.78×10 -4 > 41.4 <![CDATA[1.60×10 -5 > 4.80 11.13

[0085] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A Gemini type carboxylic acid-based surfactant, characterized in that: The general formula of its molecular structure is: It is a compound having a molecular structure shown in Formula I or a salt thereof; Wherein, n=12, 14, 16 or 18.

2. The Gemini type carboxylic acid-based surfactant according to claim 1, characterized in that The salt is a carboxylate; preferably a sodium carboxylate; more preferably a sodium dicarboxylate.

3. A method for preparing the Gemini type carboxylic acid-based surfactant according to claim 1, characterized in that: The steps include: 1) Adding fatty amine, organic solvent A and acrylic acid into a reactor, mixing and reacting to obtain an intermediate M1, the chemical structural formula of the intermediate M1 is: C n H 2n+1 N((CH2CH2COOH)2; Wherein, n=12, 14, 16 or 18; 2) Add epichlorohydrin and hydrochloric acid to the intermediate M1, mix and react to obtain the intermediate M2, the chemical structure of the intermediate M2 is: Wherein, n=12, 14, 16 or 18; 3) Adding cocamidopropyl dimethyl tertiary amine to the intermediate M2, mixing and reacting, to obtain a Gemini type carboxylic acid-based surfactant.

4. The preparation method according to claim 3, characterized in that: The molar ratio of the cocamidopropyl dimethyl tertiary amine, fatty amine, acrylic acid, epichlorohydrin and hydrochloric acid is 1:1.00-1.06:2.00-2.25:1.0-1.2:1.0-1.2; the mass ratio of the cocamidopropyl dimethyl tertiary amine to the organic solvent A is 1:3-9.

5. The preparation method according to claim 3, characterized in that: In step 1), the organic solvent A is ethanol or isopropanol; Or, in step 1), the fatty amine is octadecylamine, hexadecylamine, tetradecylamine or dodecylamine.

6. The preparation method according to claim 3, characterized in that: In step 1), during the preparation of intermediate M1, the reaction temperature is 60-82°C and the reaction time is 2-4h; In step 2), during the preparation of intermediate M2, the reaction temperature is 60-82°C and the reaction time is 4-6h; In step 3), during the preparation of the Gemini-type carboxylic acid-based surfactant, the reaction temperature is 60-82° C. and the reaction time is 3-6 h.

7. The preparation method according to claim 3, characterized in that: In step 3), after the Gemini-type carboxylic acid-based surfactant is prepared, a purification step is also included: evaporating the organic solvent A, and then recrystallizing and purifying it with organic solvent B for 2 to 3 times to obtain a pure product.

8. The preparation method according to claim 7, characterized in that: The organic solvent B is methanol, petroleum ether or ethyl acetate.

9. The preparation method according to claim 3, characterized in that: The specific steps include: (1) Add aliphatic amine and organic solvent A to a reactor, heat and stir, then add acrylic acid, stir and react at 60-82° C. for 2-4 hours to obtain intermediate M1; (2) Add epichlorohydrin and hydrochloric acid to the intermediate M1, and stir the mixture at 60-82° C. for 4-6 hours to obtain the intermediate M2; (3) Adding cocamidopropyl dimethyl tertiary amine to the intermediate M2, stirring the reaction at 60-82° C. for 3-6 hours to obtain a Gemini-type carboxylic acid-based surfactant product; evaporating the organic solvent A, and purifying by recrystallization with organic solvent B for 2-3 times to obtain a pure Gemini-type carboxylic acid-based surfactant product.

10. Use of the Gemini carboxylic acid-based surfactant according to claim 1 as a foam suppressor, a low-foaming surfactant and / or an emulsifier.

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