A five-membered heterocyclic surfactant containing a carboxyl group, its preparation method and application

Abstract

The present invention discloses a five-membered heterocyclic surfactant containing a carboxyl group, a preparation method thereof and an application thereof. The general molecular structure formula is as follows: in the general formula PS-n, n = 12, 14, 16 or 18. In the present invention, carboxyl groups, tertiary amine groups and amide groups on the ring as hydrophilic groups are connected in a certain manner, and are combined with lipophilic groups with different carbon chain lengths to form a novel five-membered heterocyclic surfactant PS-n containing a carboxyl group. The five-membered heterocyclic surfactant PS-n containing a carboxyl group has many hydrophilic groups and good product performance.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants, and particularly relates to a carboxylic acid group-containing five-membered heterocyclic surfactant, a preparation method thereof, and an application thereof. Background Art

[0002] The statements herein only provide background art related to the present invention and do not necessarily constitute prior art.

[0003] Currently, low-foaming surfactants and medium-foaming surfactant products face the following problems to be solved: (1) Low-foaming surfactants and medium-foaming surfactant products are mainly compounded products, and there are few surfactants with independent or single chemical compositions. For example, a surfactant with no foam and low surface tension disclosed in Chinese Patent Publication No. CN109845731A is a compounded product. (2) Their preparation methods are complex and the product prices are expensive, which limits their popularization and application. Summary of the Invention

[0004] In view of the disadvantages in the current technology that there are not many low-foaming surfactants and medium-foaming surfactant products, the performance indicators need to be improved, and the synthesis and preparation methods are complex, a first object of the present invention is to provide a carboxylic acid group-containing five-membered heterocyclic surfactant, which has foam suppression properties, low-foam and / or medium-foam properties, and good surface activity.

[0005] A second object of the present invention is to provide a preparation method of the carboxylic acid group-containing five-membered heterocyclic surfactant, which is simple and has low raw material costs.

[0006] To achieve the above objects, the present invention is realized through the following technical solutions:

[0007] In the first aspect, the present invention provides a carboxylic acid group-containing five-membered heterocyclic surfactant, and its molecular structure general formula is:

[0008]

[0009] In the general formula PS-n, n = 12, 14, 16 or 18.

[0010] In the second aspect, the present invention provides a preparation method of the carboxylic acid group-containing five-membered heterocyclic surfactant, including the following steps:

[0011] 1) React long-chain alkyl-1,3-propylenediamine, organic solvent (I), and itaconic acid to obtain a reaction intermediate MT-n, and the structural general formula of the reaction intermediate MT-n is:

[0012]

[0013] In the general formula MT-n, n = 12, 14, 16, 18;

[0014] 2) Acrylic acid is added to the reaction intermediate MT-n, and the mixture is reacted to obtain the carboxylic acid group-containing five-membered heterocyclic surfactant product PS-n. The organic solvent (I) is distilled off from the product PS-n under normal pressure, and then recrystallized and purified with the organic solvent (II) to obtain the pure product PS-n.

[0015] In a third aspect, the present invention provides an application of the carboxylic acid group-containing five-membered heterocyclic surfactant PS-n described in the first aspect in an antifoaming agent, a low-foaming or medium-foaming surfactant, or an emulsifier.

[0016] The beneficial effects obtained by one or more of the above embodiments of the present invention are as follows:

[0017] (1) In the present invention, the hydrophilic groups of carboxylic acid groups, tertiary amine groups, and amide groups on the ring are connected in a certain manner, and are combined with lipophilic groups of different carbon chain lengths to form a novel structure of carboxylic acid group-containing five-membered heterocyclic surfactant (PS-n). The carboxylic acid group-containing five-membered heterocyclic surfactant (PS-n) has many hydrophilic groups and good product performance.

[0018] (2) The raw material of the carboxylic acid group-containing five-membered heterocyclic surfactant (PS-n) of the present invention is long-chain alkyl-1,3-propylenediamine, which has a wide source and low cost.

[0019] (3) The synthesis technology is simple, does not require reaction at high temperature, has low energy consumption, and is easy to promote and apply. Description of the Drawings

[0020] 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.

[0021] Figure 1 It is the infrared spectrum of the product (PS-n) of Example 1.

[0022] Figure 2 It is the nuclear magnetic spectrum of the product (PS-n) of Example 1.

[0023] Figure 3 It is the mass spectrum (positive) of the product (PS-n) of Example 1.

[0024] Figure 4 It is the mass spectrum (negative) of the product (PS-n) of Example 1.

[0025] Figure 5 It is the graph of the surface tension and the logarithm of the concentration of the product (PS-n) of Example 1. Detailed Embodiments

[0026] It should be noted that the following detailed description is illustrative and aims to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention pertains.

[0027] In the first aspect of the present invention, a five-membered heterocyclic surfactant containing a carboxyl group is provided, and the general formula of its molecular structure can be represented as:

[0028]

[0029] In the general formula PS-n, n = 12, 14, 16, 18;

[0030] That is, the five-membered heterocyclic surfactant containing a carboxyl group (PS-n) is:

[0031] Formula PS-12:

[0032] Formula PS-14:

[0033] Formula PS-16:

[0034] Formula PS-18:

[0035] In the second aspect of the present invention, a preparation method of the five-membered heterocyclic surfactant containing a carboxyl group (PS-n) described in the first aspect is provided, including the following preparation steps:

[0036] 1) React long-chain alkyl-1,3-propylenediamine, organic solvent I, and itaconic acid to obtain a reaction intermediate MT-n, and the general formula of the reaction intermediate MT-n is:

[0037]

[0038] In the general formula MT-n, n = 12, 14, 16, 18;

[0039] 2) Add acrylic acid to the reaction intermediate MT-n and carry out a mixed reaction to obtain the five-membered heterocyclic surfactant product PS-n containing a carboxyl group. The organic solvent I is distilled off from the product PS-n under normal pressure, and then recrystallized and purified with organic solvent II to obtain the pure product PS-n.

[0040] The reaction general formula is as follows:

[0041]

[0042] In some embodiments, the molar ratio of the long-chain alkyl-1,3-propylenediamine, organic solvent I, itaconic acid, and acrylic acid is 1:9-19:1.01-1.05:1.01-1.09.

[0043] In some embodiments, in step 1), the organic solvent I is ethanol or / and isopropanol.

[0044] In some embodiments, in step 1), during the synthesis of the intermediate MT-n, the reaction temperature is 62-82 °C and the reaction time is 3-5 h.

[0045] In some embodiments, in step 2), during the synthesis of the product PS-n, the reaction temperature is 62-82 °C and the reaction time is 2-4 h.

[0046] In some embodiments, in step 2), the organic solvent II for recrystallization separation and purification is any one or more of methanol, petroleum ether, and ethyl acetate.

[0047] In some embodiments, the preparation method of the above-mentioned carboxylic acid group-containing five-membered heterocyclic surfactant PS-n specifically includes the following steps:

[0048] (1) Add the long-chain alkyl-1,3-propylenediamine to a reactor, add the organic solvent I, heat and stir to dissolve, add itaconic acid in 5-8 batches, and after adding, stir and react at 62-82 °C for 3-5 h to obtain the reaction intermediate MT-n;

[0049] (2) Add acrylic acid to the reaction intermediate MT-n in 5-8 batches, stir and react at 62-82 °C for 2-4 h to obtain the carboxylic acid group-containing five-membered heterocyclic surfactant product PS-n; the organic solvent I is distilled off from the product PS-n under normal pressure, and then recrystallized and purified 3-4 times with the organic solvent II to obtain the pure product PS-n.

[0050] In the third aspect of the present invention, there is provided an application of the carboxylic acid group-containing five-membered heterocyclic surfactant (PS-n) described in the first aspect as an antifoaming agent, a low-foam (or medium-foam) surfactant, and an emulsifier. For example, as an application in industrial cleaning agents.

[0051] The present invention uses long-chain alkyl-1,3-propylenediamine as the main raw material of the carboxylic acid group-containing five-membered heterocyclic surfactant PS-n, and forms carboxylic acid groups, tertiary amine groups, and amide groups on the ring hydrophilic groups in the surfactant molecular structure by sequentially adding itaconic acid and acrylic acid during the preparation process of the carboxylic acid group-containing five-membered heterocyclic surfactant PS-n, improving the antifoaming property, foam property, and surface property.

[0052] The present invention will be further described below with reference to embodiments.

[0053] Example 1

[0054] (1) Preparation of pentacyclic heterocyclic surfactant containing carboxyl group (PS-18):

[0055] 1) Add 326 g of octadecyl-1,3-propylenediamine and 690 g of isopropanol into the reaction vessel, heat and stir to dissolve at 75 °C, add 134.0 g of itaconic acid in 6 batches, and stir and react at 75 °C for 4 h to obtain reaction intermediate (MT-18).

[0056] 2) Add 75.7 g of acrylic acid into the reaction intermediate (MT-18) in 6 batches, stir and react at 75 °C for 3 h to obtain the pentacyclic heterocyclic surfactant product containing carboxyl group (PS-18).

[0057] The solvent isopropanol in the product (PS-18) is distilled off under normal pressure, and then recrystallized and purified 3 times with a mixed solvent of methanol and ethyl acetate to obtain the pure product (PS-18).

[0058] The pure product (PS-18) is subjected to structural analysis.

[0059] FTIR analysis( Figure 1 ): 3450 cm -1 (peak 1) is the stretching vibration absorption peak of O-H, 2918 cm -1 (peak2) is the asymmetric stretching vibration absorption peak of methylene, 2850 cm -1 (peak 3) is the symmetric stretching vibration absorption peak of methylene, 1732 cm -1 (peak 4) is the stretching vibration absorption peak of C=O in carboxyl group, 1683 cm -1 (peak 5) is the stretching vibration peak of C=O of amide, 1558 cm -1 (peak 6) is the asymmetric stretching vibration absorption peak of C-O, 1469 cm -1 (peak 7) is the asymmetric bending vibration of methylene, 1396 cm -1 (peak 8) is the symmetric bending vibration of methylene, 1205 cm -1 (peak 9) is the stretching vibration absorption peak of C-N, 721 cm -1 (peak 10) is the in-plane rocking vibration absorption peak of methylene.

[0060] 1 H-NMR analysis( Figure 2 ): 1 H NMR(400MHz,CD 3 OD),δ:0.8851-0.9193(3H,t,J=6.84Hz,-CH 3 ), 1.2897 (30H, s, CH 3 (C H 2 ) 15 CH 2 CH 2 -), 1.6428 - 1.7775 (2H, m, CH 3 (CH 2 ) 15 C H 2 CH 2 -), 2.0914 - 2.1445 (2H, m, -NCH 2 C H 2 CH 2 N-), 2.4682 - 2.4998 (2H, t, J=6.32Hz, CH 3 (CH 2 ) 15 CH 2 CH 2 NC H 2 -), 2.5466 - 2.5841 (2H, t, J=7.5Hz, -CH 2 C H 2 COOH), 2.6547 - 2.6738 (2H, d, -COC H 2 -), 2.9677 - 3.0037 (2H, t, J=7.2Hz, CH 3 (CH 2 ) 15 CH 2 C H 2 N-), 3.1077 - 3.1409 (2H, t, J=6.64Hz, -NCH 2 CH 2 C H 2 NCO-), 3.4786 - 3.5572 (1H, m, -C H COOH), 3.6440 - 3.6719 (2H, d, -CONC H 2 CH-), 3.7805 - 3.8121 (2H, t, J=6.32Hz, -C H 2 CH 2COOH) ppm. 3.3104 ppm is the deuterated methanol solvent peak; 4.8935 ppm is the deuterated methanol water peak.

[0061] Mass spectrometry ( Figure 3 ): HRMS (ESI) (positive) m / z: [M+H + + Calcd for C 29 H 55 N 2 O 5 , 511.4111; Found 511.4183.

[0062] Mass spectrometry ( Figure 4 ): HRMS (ESI) (negative) m / z: [M-H + - Calcd for C 29 H 53 O 5 N 2 , 509.3954; Found 509.4511.

[0063] The reaction is as follows:

[0064]

[0065] Experimental Example 1

[0066] The defoaming performance of the carboxylic acid group-containing five-membered heterocyclic surfactant product (PS-18) prepared in Example 1 was measured: At room temperature, 10 mL of a 0.5% (w / w) aqueous solution of sodium dodecylbenzenesulfonate (LBS) and a certain mass of the sample were placed in a 100 mL stoppered graduated cylinder. The stopper was plugged, and it was shaken vigorously up and down 20 times. The foam volume was recorded. The defoaming value (E) was calculated to characterize the defoaming ability of the sample.

[0067] E = (V 0 -V 1 ) / V 0

[0068] Among them, V 0 is the foam volume in the blank test, mL; V 1 is the foam volume when the product (PS-18) is added, mL.

[0069] By comparing the carboxylic acid group-containing five-membered heterocyclic surfactant product (PS-18) with OP-10 (commercial product), its defoaming performance is shown in Table 1 and Table 2. It can be seen that the carboxylic acid group-containing five-membered heterocyclic surfactant product (PS-18) prepared in Example 1 has very good defoaming ability.

[0070] ​​Table 1 Foam Suppression Performance (Before Purification)

[0071]

[0072] Table 2 Foam Suppression Ability (After Purification)

[0073]

[0074] Experimental Example 2

[0075] Sample: The pure product of the five-membered heterocyclic surfactant containing carboxyl group prepared in Example 1 (PS-18), and the pH value of the pure product (PS-18) was adjusted to 11.0 with an aqueous NaOH solution.

[0076] Method: At room temperature, 20 mL of a 0.1% (w / w) aqueous solution of the sample or an aqueous solution of OP-10 (commercial product) and 20 mL of liquid paraffin were transferred into a 100 mL stoppered graduated cylinder. The stopper was plugged, and it was shaken vigorously up and down 5 times, allowed to stand for 1 minute, and repeated 5 times. The time to separate 10 mL of water was recorded.

[0077] The experimental data are shown in Table 3. The pure product of the five-membered heterocyclic surfactant containing carboxyl group prepared in Example 1 (PS-18) has good emulsifying ability.

[0078] Table 3 Emulsifying Performance

[0079]

[0080]

[0081] Experimental Example 3

[0082] Sample: The pure product of the five-membered heterocyclic surfactant containing carboxyl group prepared in Example 1 (PS-18), and the pH value of the pure product (PS-18) was adjusted to 11.0 with an aqueous NaOH solution.

[0083] Method: 100 mL of an aqueous solution of the sample with a concentration of 0.001 mol / L was prepared. 20 mL was pipetted into a 100 mL stoppered graduated cylinder and kept at a constant temperature of 25 °C for 10 min. The solution was shaken vigorously up and down 20 times, and the initial volume of the foam (H 0 ), the volume of the foam after 5 min (H 5 ), and the time (t 1 / 2 , half-life) required for the foam volume to decrease to half of the original initial volume were recorded.

[0084] The experimental data are shown in Table 4. By comparing with sodium dodecylbenzenesulfonate, the H 0It is 10 mL, with a relatively low value, indicating that the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18) is a low-foaming surfactant.

[0085] The HLB value of the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18) (adjusted to pH 11.0 with NaOH) 0 is 45 mL, with a medium value, indicating that the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18) (adjusted to pH 11.0 with NaOH) is a medium-foaming surfactant.

[0086] The foam stability of the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18) is relatively good.

[0087] Table 4 Foaming property and foam stability

[0088]

[0089] Experimental Example 4

[0090] For the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18), using a JHZL type full-automatic surface and interfacial tension meter (Yangzhou Junhao Electric Co., Ltd.), the surface tension (γ) was measured, and a surface tension-logc change relationship graph was obtained (see Figure 5 ), and the critical micelle concentration (CMC), the surface tension at CMC (γ CMC ), C 20 , pC 20 and CMC / C 20 were calculated (see Table 5). Explanation: The surface properties of the pure product of the carboxylic acid group-containing five-membered heterocyclic surfactant prepared in Example 1 (PS-18) are relatively good.

[0091] Table 5 Surface property parameters of the pure product (PS-18)

[0092]

[0093] 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 modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. Application of a five-membered heterocyclic surfactant PS-n containing a carboxyl group in defoamers, low-foam or medium-foam surfactants, and emulsifiers. The general formula of its molecular structure can be expressed as: General formula PS-n; In the general formula PS-n, the C n H 2n+1 is octadecyl.

2. The application according to claim 1, characterized in that: The preparation method of the five-membered heterocyclic surfactant PS-n containing a carboxyl group includes the following preparation steps: 1) React long-chain alkyl-1,3-propylenediamine, organic solvent I, and itaconic acid to obtain a reaction intermediate MT-n. The general formula of the reaction intermediate MT-n is: ； The long-chain alkyl-1,3-propylenediamine is octadecyl-1,3-propylenediamine; 2) Add acrylic acid to the reaction intermediate MT-n and mix and react to obtain the five-membered heterocyclic surfactant product PS-n containing a carboxyl group. The organic solvent I is distilled off from the product PS-n under normal pressure, and then recrystallized and purified with organic solvent II to obtain the pure product PS-n.

3. The application according to claim 2, characterized in that: The molar ratio of the long-chain alkyl-1,3-propylenediamine, organic solvent I, itaconic acid, and acrylic acid is 1:9-19:1.01-1.05:1.01-1.09; The long-chain alkyl-1,3-propylenediamine is octadecyl-1,3-propylenediamine.

4. The application according to claim 3, characterized in that: The molar ratio of the long-chain alkyl-1,3-propylenediamine, organic solvent I, itaconic acid, and acrylic acid is 1:10-15:1.01-1.05:1.01-1.09; The long-chain alkyl-1,3-propylenediamine is octadecyl-1,3-propylenediamine.

5. The application according to claim 2, characterized in that: In step 1), the organic solvent I is ethanol or / and isopropanol.

6. The application according to claim 2, characterized in that: In step 1), during the synthesis of the intermediate MT-n, the reaction temperature is 62-82 °C and the reaction time is 3-5 h.

7. The application according to claim 2, characterized in that: In step 2), during the synthesis of the product PS-n, the reaction temperature is 62-82 °C and the reaction time is 2-4 h.

8. The application according to claim 2, characterized in that: In step 2), the organic solvent II for recrystallization separation and purification is any one or more of methanol, petroleum ether, and ethyl acetate.

9. The application according to claim 2, characterized in that: Specifically, it includes the following steps: (1) Add long-chain alkyl-1,3-propylenediamine to a reactor, add organic solvent I, heat and stir to dissolve, add itaconic acid in 5-8 batches. After adding, stir and react at 62-82 °C for 3-5 h to obtain the reaction intermediate MT-n; The long-chain alkyl-1,3-propylenediamine is octadecyl-1,3-propylenediamine; (2) Acrylic acid was added to the reaction intermediate MT-n in 5 to 8 batches, and the mixture was stirred and reacted at 62 to 82 °C for 2 to 4 h to obtain the carboxylic acid group-containing five-membered heterocyclic surfactant product PS-n; the organic solvent I was distilled off from the product PS-n under normal pressure, and then recrystallized and purified 3 to 4 times with the organic solvent II to obtain the pure product PS-n.

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