A carboxylate heterocyclic surfactant, its preparation method and application

Abstract

The present invention belongs to the technical field of surfactants in fine chemicals, and relates to a carboxylate heterocyclic surfactant, its preparation method and application. The general molecular structure formula of the carboxylate heterocyclic surfactant is as follows: The carboxylate heterocyclic surfactant is prepared from raw materials in the following molar ratios: the molar ratio of N-alkyl-1,3-propylenediamine, alcohol solvent, itaconic acid, basic compound, and water is 1:(10-21):(2.00-2.10):(3.05-3.30):(8-25). The carboxylate heterocyclic surfactant of the present invention can be used as an antifoaming agent, a low-foaming surfactant or an emulsifier.

Description

Technical Field

[0001] The present invention relates to the technical field of surfactants in fine chemicals, and particularly relates to a carboxylate heterocyclic 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] Surfactants are an important type of fine chemical product and play a very important role in people's daily lives. There are many types of surfactants, and the demand for surfactant functions is also getting higher and higher. Usually, compounding is used to meet the requirements. If a surfactant with multiple functions can be prepared, the complexity of the formulation will be greatly simplified.

[0004] Low-foaming surfactants are products that exhibit low foam performance in industrial spray cleaning, cleaning agents, or other application sites.

[0005] In the current prior art methods, there is a method for a low-foaming nonionic surfactant, its preparation method and application (CN108654512A) which discloses: providing a nonionic surfactant with the general formula (1), its preparation method and application, especially in the presence of catalysts such as alkoxylation and addition reactions in the presence of alkaline, acidic or double metal cyanide catalysts, and the method for preparing the composition, and its application as a nonionic surfactant. In particular, the disclosed composition is applied in the textile, industrial and public cleaning, and daily chemical industries. Another study discloses a protein-based surfactant for skin and hair cleaning and care and its preparation method (CN108143641B): pretreating natural proteins, adding alkaline protease and catalase to the pretreated natural protein raw materials for enzymatic hydrolysis and enzyme inactivation to obtain an enzyme-inactivated protein hydrolysate. Purifying and purifying the enzyme-inactivated protein hydrolysate, then removing moisture and drying to obtain collagen. Using a microreactor, carrying out amidation reaction on collagen and diethanolamine to generate collagen polypeptide amide, and then carrying out esterification reaction on collagen polypeptide amide and lauric acid to obtain a protein-based surfactant.

[0006] In the current technology, the development of low-foaming surfactants mainly focuses on the compounding of various surfactants, formulation research, and research ideas on composition combinations. There are few research reports on surfactants with single or independent chemical compositions, and there are also confusions in the synthetic preparation process technology. Summary of the Invention

[0007] In view of the deficiencies in the current production technologies and methods, such as the limited variety of low-foaming surfactants, the performance that needs to be further improved, and the cumbersome and complex preparation methods, one object of the present invention is to provide a carboxylate heterocyclic surfactant, and the carboxylate heterocyclic surfactant exhibits foam suppression and low-foam properties, etc.

[0008] Another object of the present invention is to provide a preparation method for the above-mentioned carboxylate heterocyclic surfactant. The preparation method is simple, the raw materials are widely available, and the production raw material cost is relatively low.

[0009] A third object of the present invention is to provide an application of the above-mentioned carboxylate heterocyclic surfactant as a foam suppressant, a low-foam surfactant, an emulsifier, etc.

[0010] To achieve the above objects, the technical solution of the present invention is as follows:

[0011] In the first aspect of the present invention, a carboxylate heterocyclic surfactant is provided, and the general formula of its molecular structure can be expressed as:

[0012]

[0013] n is an even number not less than 12; preferably, n can be selected as 12, 14, 16 or 18;

[0014] C n H 2n+1 is a straight-chain alkyl group;

[0015] M is Na + , K + or NH 4 + .

[0016] During the research and development process of the present invention, if a carboxylate heterocyclic group is designed and introduced into the molecular structure of the surfactant, and further combined with hydrophilic groups such as carboxylate, tertiary amine group, and amide group in the ring, as well as a long carbon chain lipophilic group, a carboxylate heterocyclic surfactant product with a new structure is formed. This surfactant product exhibits foam suppression properties, low-foam properties, and outstanding surface performance.

[0017] In the second aspect of the present invention, a preparation and synthesis method for the above-mentioned carboxylate heterocyclic surfactant is provided, including the following steps:

[0018] 1) React N-alkyl-1,3-propylenediamine, an alcohol solvent, and itaconic acid to obtain an intermediate Q, and the general formula of the intermediate Q is:

[0019]

[0020] n is an even number not less than 12; preferably, n can be selected as 12, 14, 16 or 18;

[0021] C n H 2n+1 is a straight-chain alkyl group;

[0022] 2) Add an aqueous solution of an alkaline compound to the above intermediate Q, mix and react to obtain a carboxylate heterocyclic surfactant product T; the solvent is distilled off from the product T under normal pressure, and then recrystallized and separated and purified with an organic solvent to obtain a pure carboxylate heterocyclic surfactant T.

[0023] The reaction formula is as follows:

[0024]

[0025] In one or more embodiments, the molar ratio of the N-alkyl-1,3-propylenediamine, alcohol solvent, itaconic acid, alkaline compound, and water is 1:(10-21):(2.00-2.10):(3.05-3.30):(8-25).

[0026] Through a large number of experiments and analysis and verification, the above raw materials with the above molar ratios can synthesize the carboxylate heterocyclic surfactant of the present invention, and its performance is good. Unsuitable molar ratios cannot synthesize the carboxylate heterocyclic surfactant.

[0027] In one or more embodiments, in step 1), the N-alkyl-1,3-propylenediamine is N-dodecyl-1,3-propylenediamine, N-tetradecyl-1,3-propylenediamine, N-hexadecyl-1,3-propylenediamine, N-octadecyl-1,3-propylenediamine (for example, N-hydrogenated tallow-based 1,3-propylenediamine).

[0028] In one or more embodiments, in step 1), the alcohol solvent can be selected from any one or more of ethanol and isopropanol.

[0029] In one or more embodiments, in step 1), the reaction temperature is 60-80°C and the reaction time is 3-6 hours.

[0030] In one or more embodiments, in step 2), the alkaline compound is sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, potassium carbonate, ammonium carbonate, etc.

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

[0032] In one or more embodiments, in step 2), the reaction temperature is 60-80°C and the reaction time is 1-2 hours.

[0033] In a preferred embodiment, the synthetic preparation method of the above carboxylate heterocyclic surfactant T specifically comprises the following steps:

[0034] (1) Add N-alkyl-1,3-propylenediamine to a reactor, add an alcohol solvent, heat and stir to dissolve it, then add itaconic acid in batches. After adding, stir and react at 60-80 °C for 3-6 hours to obtain intermediate Q;

[0035] (2) Dissolve the basic compound in water to obtain an aqueous solution of the basic compound, add the aqueous solution of the basic compound to the above intermediate Q. After adding, stir and react at 60-80 °C for 1-2 hours to obtain the carboxylate heterocyclic surfactant product T; the solvent of the product T is distilled off under normal pressure, and then recrystallized and separated and purified 3-5 times with an organic solvent to obtain the pure carboxylate heterocyclic surfactant T.

[0036] In the third aspect of the present invention, a carboxylate heterocyclic surfactant obtained by the above preparation method is provided.

[0037] In the fourth aspect of the present invention, an application of the above carboxylate heterocyclic surfactant as an antifoaming agent, a low-foaming surfactant or an emulsifier is provided.

[0038] In the above applications, for example, in the fields of industrial cleaning and cleaning agents, the foam generated during production will make control difficult, cause material overflow and waste, and lead to environmental pollution.

[0039] The present invention uses N-alkyl-1,3-propylenediamine as the raw material of the carboxylate heterocyclic surfactant. In the synthesis and preparation of the carboxylate heterocyclic surfactant, itaconic acid and basic compound are added in sequence, and carboxylate, tertiary amine group and amide hydrophilic group in the ring are designed and introduced into the surfactant molecular structure, so that it has antifoaming property, low-foaming property and surface activity.

[0040] The specific embodiments of the present invention have the following beneficial effects:

[0041] (a) The present invention designs and gives the molecular structure of the carboxylate heterocyclic surfactant. In the research idea, the carboxylate, tertiary amine group and amide hydrophilic group in the ring are combined with long carbon chain hydrophobic groups of different lengths, thereby forming a carboxylate heterocyclic surfactant with a new chemical structure, so that its antifoaming property, low-foaming property and surface property are better.

[0042] (b) The raw material for synthesizing and preparing the carboxylate heterocyclic surfactant in the present invention is alkyl diamine, which is cheap, easy to obtain and has low cost.

[0043] (c) The preparation method of the present invention has a simple process. It only needs to carry out chemical reactions in sequence at a relatively low reaction temperature, with low energy consumption.

[0044] (d) The operation of the present invention is simple and easy to learn, with high technical practicability. Description of the Drawings

[0045] Figure 1 It is the infrared spectrum of product T in Example 1.

[0046] Figure 2 It is the nuclear magnetic spectrum of product T in Example 1.

[0047] Figure 3 It is the mass spectrum of product T in Example 1.

[0048] Figure 4 It is the graph of the relationship between the surface tension and the logarithm of the concentration of product T in Example 1. Detailed Embodiments

[0049] The following detailed description is illustrative. 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 conjunction with specific examples and experimental examples.

[0050] Example 1

[0051] (1) Synthesis and preparation of the carboxylate heterocyclic surfactant (product T):

[0052] 1) Add 326 g of N-hydrogenated tallow-1,3-propylene diamine and 700 g of isopropanol to the reactor, heat and stir to dissolve at 75 °C, and then add 264.1 g of itaconic acid in 5 batches, and stir and react at 75 °C for 4 h to obtain intermediate Q.

[0053] 2) Dissolve 128.0 g of sodium hydroxide in 256.0 g of distilled water to obtain an aqueous sodium hydroxide solution, and then add the aqueous sodium hydroxide solution to intermediate Q in 5 batches, and stir and react at 75 °C for 1 h to obtain the carboxylate heterocyclic surfactant product T; the solvent of product T is distilled off under normal pressure, and then it is recrystallized and separated and purified 3 times with methanol to obtain pure product T.

[0054] Perform FTIR, 1 1H-NMR and MS analysis on pure product T.

[0055] FTIR analysis ( Figure 1 ): 2918 cm -1 (peak 1) is the asymmetric stretching vibration absorption peak of methylene, 2850 cm -1 (peak 2) is the symmetric stretching vibration absorption peak of methylene, 1651 cm-1 (Peak 3) is the absorption peak of C=O stretching vibration, 1469 cm -1 (Peak 4) is the absorption peak of asymmetric bending vibration of methylene, 1398 cm -1 (Peak 5) is the absorption peak of C-O stretching vibration, 954 cm -1 (Peak 6) is the out-of-plane bending vibration absorption peak of methylene, 721 cm -1 (Peak 7) is the in-plane rocking vibration of methylene.

[0056] 1 H-NMR analysis( Figure 2 ): 1 H NMR(400 MHz, CD 3 OD), δ: 0.8843 - 0.9186(3H, t, J = 6.86 Hz, -C H 3 ), 1.2882(32H, s, CH 3 (C H 2 ) 16 CH 2 N-), 1.6137 - 1.6691(2H, m, -NCH 2 C H 2 CH 2 N-), 1.9152 - 1.9521(2H, t, C 18 H 37 NC H 2 CH 2 CH 2 N-), 2.6280 - 2.6664(2H, t, CH 3 (CH 2 ) 16 C H 2 N-), 2.8366 - 2.8746(2H, m, -NCOC H 2 -), 2.9148 - 2.9511(2H, t, -CHC H 2 COONa), 3.0573(1H, m, -NCH 2 C H (COONa)CH 2 COONa), 3.2153(4H, m, -NC H 2 CH(COONa)CH 2 COONa and C 18H 37 NCH 2 CH 2 C H 2 N-), 3.3487(1H, m, -NCOCH 2 C H (COONa)-), 3.6041 - 3.6574(2H, m, C 18 H 37 NCH 2 CH 2 CH 2 NC H 2 -) ppm. 3.3099 is the solvent peak of deuterated methanol. 4.9030 is the water peak in the deuterated methanol solvent.

[0057] Mass spectrometry ( Figure 3 ):HRMS(ESI)(Negative) m / z: [M - 3Na + 2H + - Calcd for C 31 H 55 O 7 N 2 , 567.4009; Found 567.4501.

[0058] The reaction formula is:

[0059]

[0060] Experimental Example 1

[0061] The defoaming performance of the carboxylate heterocyclic surfactant T prepared in Example 1 was tested.

[0062] Method: At room temperature, 10 mL of a 0.5% (mass fraction) aqueous solution of sodium dodecylbenzenesulfonate (LBS) and a certain amount of the sample were taken and poured into a 100 mL stoppered graduated cylinder. After plugging the stopper, it was shaken vigorously up and down by hand 20 times, and the foam volume produced was immediately recorded. The defoaming value (X) can reflect the defoaming ability of the sample.

[0063] X = (V 0 - V 1 ) / V 0

[0064] In the formula, V 0 is the foam volume (mL) produced in the blank test; V 1 is the foam volume (mL) produced when the sample is added.

[0065] ​The carboxylate heterocyclic surfactant T was compared and analyzed with OP-10 (industrial product) on the market, and the defoaming performance data are shown in Table 1. It can be concluded that the carboxylate heterocyclic surfactant T prepared in Example 1 has better defoaming performance.

[0066] Table 1 Defoaming performance of samples

[0067]

[0068] Experimental Example 2

[0069] Emulsifying ability test method: At room temperature, take 20 mL of 0.1% (mass fraction) aqueous solution of the sample (adjust the pH value to 11 with NaOH) or the aqueous solution of OP-10 (industrial product) on the market and 20 mL of liquid paraffin, and pour them into a 100 mL stoppered graduated cylinder. After that, after plugging the stopper, shake it vigorously up and down by hand 5 times, then let it stand for 1 min, repeat 5 times continuously, and immediately record the time required to separate 10 mL of water.

[0070] The experimental data are shown in Table 2. It can be concluded that the carboxylate heterocyclic surfactant T synthesized in Example 1 has good emulsifying performance.

[0071] Table 2 Emulsifying ability of samples

[0072] Product Water separation time (s) Product T 366 OP-10 684

[0073] Experimental Example 3

[0074] Foaming and foam stability test method: At room temperature, prepare 80 mL of an aqueous solution of product T with a concentration of 0.001 mol / L (adjust the pH value to 11 with NaOH). Take 20 mL of the solution and place it in a 100 mL stoppered graduated cylinder, and keep it at a constant temperature of 25 °C in a constant temperature water bath for 10 min. Then shake the constant temperature solution vigorously up and down 20 times, and then let it stand in the water bath. Immediately record the initial volume of the generated foam (H 0 ), record the volume of the foam after 5 min (H 5 ), and record the time required for the foam volume to decay to 1 / 2 of the initial volume (denoted as t 1 / 2 , that is: half-life).

[0075] The experimental data of foaming and foam stability are shown in Table 3. It can be concluded that compared with sodium dodecylbenzenesulfonate, the foaming property of product T is not high, but the foam stability is better. It shows that the carboxylate heterocyclic surfactant T is a low-foaming surfactant.

[0076] Table 3 Foaming and foam stability of samples

[0077]

[0078] Experimental Example 4

[0079] Test method for surface tension and critical micelle concentration (CMC): Select a JHZL type fully automatic surface and interfacial tension meter (manufactured by Yangzhou Junhao Electric Co., Ltd.) for testing. The platinum ring method is used to measure the surface tension (γ), and the surface tension (γ)-logc change curve is obtained (see Figure 4 as shown). The surface performance parameters CMC, surface tension at CMC (γ CMC ), C 20 , pC 20 and CMC / C 20 can be obtained (as shown in Table 4). It can be seen that the surface performance of product T is relatively excellent.

[0080] Table 4 Surface performance parameters

[0081] 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 T <![CDATA[1.09×10 -4 > 39.0 <![CDATA[2.90×10 -5 > 4.54 3.76

[0082] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. 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. A carboxylate heterocyclic surfactant, characterized in that, the general formula T of its molecular structure is: wherein, n is 18; C n H 2n+1 is a straight-chain alkyl group; M is Na + , K + or NH 4 + .

2. The preparation method of the carboxylate heterocyclic surfactant according to claim 1, characterized in that, it comprises the following steps: 1) React N-hydrogenated tallow-based 1,3-propylenediamine, an alcohol solvent, and itaconic acid to obtain intermediate Q, and the general formula of the structure of the intermediate Q is: wherein, n is 18; C n H 2n+1 is a straight-chain alkyl group; 2) Add an aqueous solution of a basic compound to the above intermediate Q, and carry out a mixing reaction to obtain the carboxylate heterocyclic surfactant product T; the solvent is distilled off from the product T under normal pressure, and then recrystallized and separated and purified with an organic solvent to obtain the pure carboxylate heterocyclic surfactant T.

3. The preparation method according to claim 2, characterized in that, the molar ratio of the N-hydrogenated tallow-based 1,3-propylenediamine, the alcohol solvent, itaconic acid, the basic compound, and water is 1:10 - 21:2.00 - 2.10:3.05 - 3.30:8 - 25.

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

5. The preparation method according to claim 2, characterized in that, in step 1), the reaction temperature is 60 - 80 °C and the reaction time is 3 - 6 hours.

6. The preparation method according to claim 2, characterized in that, in step 2), the basic compound is at least one of sodium hydroxide, potassium hydroxide, ammonia water, sodium carbonate, potassium carbonate, and ammonium carbonate.

7. The preparation method according to claim 2, characterized in that, in step 2), the organic solvent for recrystallization separation and purification is any one or more of methanol, petroleum ether, and ethyl acetate; or, the reaction temperature is 60 - 80 °C and the reaction time is 1 - 2 hours.

8. The preparation method according to claim 2, characterized in that, specifically comprises the following steps: (1) Add N-hydrogenated tallow-based 1,3-propylenediamine to a reactor, add an alcohol solvent, heat and stir to dissolve it, and then add itaconic acid in batches. After adding, stir and react at 60 - 80 °C for 3 - 6 hours to obtain intermediate Q; (2) Dissolve the basic compound in water to obtain an aqueous solution of the basic compound, add the aqueous solution of the basic compound to the above intermediate Q. After adding, stir and react at 60 - 80 °C for 1 - 2 hours to obtain the carboxylate heterocyclic surfactant product T; the solvent is distilled off from the product T under normal pressure, and then recrystallized and separated and purified with an organic solvent 3 - 5 times to obtain the pure carboxylate heterocyclic surfactant T.

9. The application of the carboxylate heterocyclic surfactant according to claim 1 as an antifoaming agent, a low-foaming surfactant, or an emulsifier.

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