Quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition and preparation method thereof

Abstract

The invention discloses a quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition and a preparation method thereof, and relates to the technical field of polyoxyethylene ether materials. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition is prepared from the following raw materials in parts by weight: 20 to 30 parts of quaternary ammonium salt type pyrrolidine polyoxyethylene ether, 0.5 to 1 part of antioxidant and 25 to 35 parts of deionized water. According to the invention, cyanuric chloride and amino decaglycol monomethyl ether react to generate a monosubstituted compound, and the monosubstituted compound and 3, 5-di-tert-butyl-4-hydroxybenzylamine react to generate the antioxidant. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition prepared by the invention has good surface tension and oxidation resistance.

Description

Technical Field

[0001] This invention relates to the field of polyoxyethylene ether materials technology, specifically to a quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition and its preparation method. Background Technology

[0002] Quaternary ammonium salt surfactants are widely used in fabric care, personal hygiene, cosmetics, oilfield chemicals, and materials processing due to their excellent softening, antistatic, emulsifying, bactericidal, and strong adsorption properties to negatively charged surfaces. Among them, polyoxyethylene ether compounds based on the pyrrolidine structure have attracted much attention due to their good hydrophilicity and biodegradability. The polyoxyethylene ether structure has good hydrophilicity and flexibility, which can effectively improve the water solubility, low-temperature stability, and compatibility with different systems of quaternary ammonium salt surfactants. Compared with traditional straight-chain alkyl tertiary amines or imidazole rings, the pyrrolidine ring structure, due to the conformational restriction of its ring structure, can form more stable and sterically more rationally oriented cationic centers. This not only enhances the chemical stability of the molecule but also improves its packing efficiency at the interface, thereby improving surface activity. However, the pyrrolidine structure and the numerous ether bonds present in the polyoxyethylene ether segments are prone to oxidative degradation under heat, oxygen, and long-term storage conditions, leading to molecular structure destruction and performance degradation, which has become an important factor limiting the further application of this type of surfactant. Therefore, it is crucial to prepare a quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition with low surface tension and excellent antioxidant stability.

[0003] Chinese invention patent CN120271997A discloses a pyrrolidine compound polyoxyethylene ether composition and its preparation method. This invention further accelerates the reaction rate and prevents the oxidation and discoloration of N-hydroxyethylpyrrolidine by using a negative pressure feeding method in the reactor, thereby increasing the yield of N-hydroxyethylpyrrolidine. The pyrrolidine compound polyoxyethylene ether composition is prepared by mixing pyrrolidine polyoxyethylene ether with different polymerization numbers, sodium pyrrolidine polyoxyethylene ether sulfate, and sodium pyrrolidine polyoxyethylene ether carboxylate in a certain mass ratio. This composition can adjust the proportion of pyrrolidine polyoxyethylene ether with different lengths to change its hydrophilicity and hydrophobicity balance, so as to have excellent hydrophobic-hydrophilic, dispersion, and wetting properties, but its antioxidant properties still need to be improved. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition and its preparation method.

[0005] To achieve the above objectives, the present invention provides the following technical solution: A quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition comprising the following raw materials in parts by weight: 20-30 parts of quaternary ammonium salt type pyrrolidine polyoxyethylene ether, 0.5-1 part of antioxidant, and 25-35 parts of deionized water; The quaternary ammonium salt type pyrrolidine polyoxyethylene ether is prepared by the following method: S1: 1,16-Di(pyrrolidin-1-yl)hexadecane reacts with 5-bromopentanoic acid to form a quaternary ammonium salt compound; the reaction equation is shown below:

[0006] S2: Quaternary ammonium salt compounds react with lauryl alcohol polyoxyethylene ether to generate quaternary ammonium salt-type pyrrolidine polyoxyethylene ether; the reaction equation is shown below.

[0007] The antioxidant is prepared by the following method: N1: Cyanurium chloride reacts with aminodecaglycol monomethyl ether to form a monosubstituted compound; the reaction equation is shown below.

[0008] N2: Monosubstituted compounds react with 3,5-di-tert-butyl-4-hydroxybenzylamine to generate antioxidants; the reaction equation is shown below:

[0009] In step S1, the molar ratio of 1,16-bis(pyrrolidine-1-yl)hexadecane to 5-bromopentanoic acid is 1:2.01.

[0010] In step S2, the molar ratio of the quaternary ammonium salt compound to lauryl alcohol polyoxyethylene ether is 1:2.02.

[0011] In step N1, the molar ratio of cyanuric chloride to aminodeglycol monomethyl ether is 1:(1.01-1.02).

[0012] In step N2, the molar ratio of the monosubstituted compound to 3,5-di-tert-butyl-4-hydroxybenzylamine is 1:(2.02-2.04).

[0013] The reaction solvent in step S1 is isopropanol.

[0014] The reaction solvent in step S2 is tetrahydrofuran.

[0015] The reaction solvent in step N1 is anhydrous acetonitrile.

[0016] The reaction solvent in step N2 is anhydrous acetonitrile.

[0017] A method for preparing a quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition includes the following steps: (1) Weigh out the following by weight: 20-30 parts of quaternary ammonium salt type pyrrolidine polyoxyethylene ether, 0.5-1 part of antioxidant, and 25-35 parts of deionized water; (2) Stir and mix the quaternary ammonium salt type pyrrolidine polyoxyethylene ether, antioxidant and deionized water to obtain the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition.

[0018] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include: The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition prepared by this invention has good surface tension and antioxidant capacity. Detailed Implementation

[0019] The following description, in conjunction with specific embodiments, provides further details, but the present invention is not limited to these embodiments.

[0020] Example 1: Preparation of Antioxidants N1: Under nitrogen protection, 350 ml of anhydrous acetonitrile, 0.1 mol of cyanuric chloride, and 0.101 mol of aminodecaethylene glycol monomethyl ether were stirred and mixed. 0.1 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 0 °C for 6 h. Then, 400 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly before filtration. The filter cake was washed with deionized water until neutral and dried under vacuum at 60 °C for 8 h to obtain the monosubstituted compound. Its 1H NMR spectrum data are as follows: 1 H NMR (400 MHz, DMSO- d 6 ) δ 7.35 (s, 1H), 3.70 (d, J = 3.5 Hz, 2H), 3.61-3.52 (m, 38H), 3.30 (s, 3H); HRMS (m / z):619.2438[M+H] + ; Under nitrogen protection, 600 ml of anhydrous acetonitrile, 0.1 mol of the monosubstituted compound, and 0.202 mol of 3,5-di-tert-butyl-4-hydroxybenzylamine were stirred and mixed thoroughly. Then, 0.2 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 25 °C for 8 h. The temperature was then increased to 60 °C and reacted for 10 h. 650 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly before filtration. The filter cake was washed with deionized water until neutral and then dried under vacuum at 60 °C for 8 h to obtain the antioxidant. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d) δ 7.05 (t, J= 5.0 Hz, 4H), 6.09 (d, J = 3.5 Hz, 1H), 5.91 (d, J = 4.5 Hz, 2H), 5.58 (s,2H), 4.53 (q, J = 4.9 Hz, 4H), 3.79-3.64 (m, 2H), 3.63-3.55 (m, 38H), 3.32(s, 3H), 1.41 (s, 36H); HRMS (m / z):1017.6779[M+H] + .

[0021] Example 2 Preparation of Antioxidant N1: Under nitrogen protection, 350 ml of anhydrous acetonitrile, 0.1 mol of cyanuric chloride, and 0.1015 mol of aminodecaethylene glycol monomethyl ether were stirred and mixed. 0.1 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 0°C for 6.5 h. 400 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 60°C for 8 h to obtain the monosubstituted compound. Under nitrogen protection, 600 ml of anhydrous acetonitrile, 0.1 mol of the monosubstituted compound, and 0.203 mol of 3,5-di-tert-butyl-4-hydroxybenzylamine were stirred and mixed. Then, 0.2 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 25 °C for 8 h. The temperature was then increased to 60 °C and reacted for 10 h. 650 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and then dried under vacuum at 60 °C for 8 h to obtain the antioxidant.

[0022] Example 3 Preparation of Antioxidant N1: Under nitrogen protection, 350 ml of anhydrous acetonitrile, 0.1 mol of cyanuric chloride, and 0.102 mol of aminodecaethylene glycol monomethyl ether were stirred and mixed. 0.1 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 0°C for 7 h. 400 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 60°C for 8 h to obtain the monosubstituted compound. Under nitrogen protection, 600 ml of anhydrous acetonitrile, 0.1 mol of the monosubstituted compound, and 0.204 mol of 3,5-di-tert-butyl-4-hydroxybenzylamine were stirred and mixed. Then, 0.2 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 30 °C for 7 h. The temperature was then increased to 65 °C and reacted for 9 h. 650 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 60 °C for 8 h to obtain the antioxidant.

[0023] Example 4 Preparation of Quaternary Ammonium Salt Type Pyrrolidine Polyoxyethylene Ether S1: Under nitrogen protection, 350 ml of isopropanol and 0.1 mol of 1,16-di(pyrrolidone-1-yl)hexadecane were stirred and mixed thoroughly. 0.201 mol of 5-bromopentanoic acid was added in five equal batches, with a 10-min interval between batches. The mixture was refluxed for 48 h, cooled to room temperature, and distilled under reduced pressure at 50 °C for 1 h. The mixture was recrystallized using 300 ml of acetone and dried under vacuum at 50 °C for 12 h to obtain the quaternary ammonium salt compound. Its 1H NMR data are as follows: 1 H NMR (400 MHz, Chloroform- d ) δ 11.49 (s, 2H), 3.61-3.45 (m, 16H), 2.30 (m, 4H), 1.98-1.67 (m, 20H), 1.43-1.24 (m, 24H); HRMS (m / z): 283.2509[M-2Br] 2+ ; S2: Under nitrogen protection, 180 ml of tetrahydrofuran, 0.01 mol of quaternary ammonium salt compound, 0.021 mol of dicyclohexylcarbodiimide, and 0.004 mol of 4-dimethylaminopyridine were mixed and stirred for 15 min. Then, 0.0202 mol of lauryl polyoxyethylene ether (molecular weight 1199.56) was added, and the mixture was reacted at 25 °C for 18 h. After filtration, the mixture was distilled under reduced pressure at 40 °C for 1 h. The crude product was purified by silica gel column chromatography (V... 二氯甲烷 :V 甲醇 The distillation at 30°C under reduced pressure for 1 hour yielded a quaternary ammonium salt type pyrrolidine polyoxyethylene ether (r=10:1). Its 1H NMR data are as follows: 1 HNMR (400 MHz, Chloroform- d ) δ 4.20 (s, 4H), 3.63-3.52 (m, 192H), 3.49 (m,8H), 2.32 (m, 4H), 1.96 (m, 8H), 1.91-1.69 (m, 12H), 1.54-1.25 (m, 64H), 0.90(t, J = 6.3 Hz, 6H).; HRMS (m / z):1464.5436[M-2Br] 2+ .

[0024] Example 5 Preparation of Quaternary Ammonium Salt Type Pyrrolidine Polyoxyethylene Ether Composition (1) Weigh the following by weight: 20g of quaternary ammonium salt type pyrrolidine polyoxyethylene ether (prepared in Example 4), 0.5g of antioxidant (prepared in Example 1), and 25g of deionized water; (2) Mix quaternary ammonium salt type pyrrolidine polyoxyethylene ether, antioxidant and deionized water, and stir at 300 rpm for 20 min to obtain quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition.

[0025] Example 6 Preparation of Quaternary Ammonium Salt Type Pyrrolidine Polyoxyethylene Ether Composition (1) Weigh the following by weight: 25g of quaternary ammonium salt type pyrrolidine polyoxyethylene ether (prepared in Example 4), 0.8g of antioxidant (prepared in Example 2), and 30g of deionized water; (2) Mix quaternary ammonium salt type pyrrolidine polyoxyethylene ether, antioxidant and deionized water, and stir at 300 rpm for 20 min to obtain quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition.

[0026] Example 7 Preparation of Quaternary Ammonium Salt Type Pyrrolidine Polyoxyethylene Ether Composition (1) Weigh the following by weight: 30g of quaternary ammonium salt type pyrrolidine polyoxyethylene ether (prepared in Example 4), 1g of antioxidant (prepared in Example 3), and 35g of deionized water; (2) Mix quaternary ammonium salt type pyrrolidine polyoxyethylene ether, antioxidant and deionized water, and stir at 300 rpm for 20 min to obtain quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition.

[0027] Comparative Example 1 The raw material composition and preparation method of the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition are basically the same as those in Example 6, except that the antioxidant is replaced with an equal weight of antioxidant prepared by the following method: The preparation method of the antioxidant is basically the same as that in Example 2, except that the aminodeglycol monomethyl ether in step N1 is replaced with an equimolar amount of aminotetraglycol monomethyl ether.

[0028] Comparative Example 2 The raw material composition and preparation method of the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition are basically the same as those in Example 6, except that the antioxidant is replaced with an equal weight of antioxidant prepared by the following method: N1: Under nitrogen protection, 350 ml of anhydrous acetonitrile, 0.1 mol of cyanuric chloride, and 0.1015 mol of aminodecaethylene glycol monomethyl ether were stirred and mixed. 0.1 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 0℃ for 6-7 h. 400 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 60℃ for 8 h to obtain the monosubstituted compound. Under nitrogen protection, 500 ml of anhydrous acetonitrile, 0.1 mol of the monosubstituted compound, and 0.103 mol of 3,5-di-tert-butyl-4-hydroxybenzylamine were stirred and mixed. Then, 0.1 mol of N,N-diisopropylethylamine was added, and the mixture was reacted at 25 °C for 8 h. 600 ml of 0.1 M hydrochloric acid was added, and the mixture was stirred thoroughly and filtered. The filter cake was washed with deionized water until neutral and dried under vacuum at 60 °C for 8 h to obtain the antioxidant.

[0029] Comparative Example 3 The raw material composition and preparation method of the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition are basically the same as those in Example 6, except that the quaternary ammonium salt type pyrrolidine polyoxyethylene ether is replaced with an equal weight of quaternary ammonium salt type pyrrolidine polyoxyethylene ether prepared by the following method: The preparation method of quaternary ammonium salt type pyrrolidine polyoxyethylene ether is basically the same as that in Example 4, except that 1,16-bis(pyrrolidine-1-yl)hexadecane in step S1 is replaced with an equimolar amount of 1,2-bis(pyrrolidine)-ethane.

[0030] The quaternary ammonium salt type pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 and Comparative Examples 1-3 were tested, and the test results are shown in Table 1.

[0031] Surface tension test: The surface tension of the quaternary ammonium salt pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 and Comparative Examples 1-3 was tested using a surface tension meter.

[0032] Antioxidant performance test: The DPPH free radical scavenging ability of the quaternary ammonium salt pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 and Comparative Examples 1-3 was determined. The quaternary ammonium salt pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 and Comparative Examples 1-3 were diluted to a concentration of 0.1 mol / L. 2 ml of each composition solution was placed in a beaker, and 2 ml of DPPH solution (concentration 0.1 mol / L) was added to each (group A1). 2 ml of anhydrous ethanol was added to each (group A2). The blank group A0 was set to 4 ml of anhydrous ethanol. Each group of solutions was placed in the dark for 30 min, and then the absorbance was measured at a wavelength of 517 nm. The absorbance was calculated according to the formula... Calculate the DPPH radical scavenging rate, repeat three times and take the average value.

[0033] Table 1 Performance Test Data

[0034] As can be seen from Table 1, the quaternary ammonium salt type pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 of this application have good surface tension and antioxidant capacity.

[0035] The quaternary ammonium salt-type pyrrolidine polyoxyethylene ether compositions prepared in Examples 5-7 of this application possess both excellent surface tension regulation and antioxidant properties, primarily due to the synergistic effect between molecular structures. Specifically, the quaternary ammonium salt structure introduced into the quaternary ammonium salt-type pyrrolidine polyoxyethylene ether molecule endows the molecule with stable positive charge characteristics, significantly enhancing its solubility in the aqueous phase and its interfacial directional adsorption capacity. The pyrrolidine ring structure improves the molecule's structural rigidity and interfacial anchoring ability, enabling it to form a dense and ordered adsorption layer at solid-liquid and gas-liquid interfaces. Long-chain alkyl groups, as hydrophobic groups, help reduce the system's free energy at the interface, thereby effectively reducing surface tension. Simultaneously, the long, flexible polyoxyethylene ether segments in the molecule possess both good hydrophilicity and spatial compliance, improving the molecule's dispersion stability in the aqueous phase and promoting its rapid spreading at the interface. Furthermore, the triazine ring structure in the antioxidant molecules added to the composition serves as a stable backbone unit, contributing to improved thermal stability and structural durability. The long, flexible ether chain enhances the compatibility and dispersibility of the antioxidant in the composition system. The hindered phenolic structure efficiently captures free radicals generated in the system, inhibiting the occurrence of oxidative chain reactions. After the quaternary ammonium salt-type pyrrolidine polyoxyethylene ether molecules are compounded with the antioxidant molecules, the surface-active components form a stable adsorption layer at the interface, while the antioxidant is uniformly distributed throughout the system, continuously exerting its free radical inhibition effect. This allows the composition to significantly improve its overall antioxidant capacity while reducing surface tension, ensuring its performance stability during use.

[0036] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. However, any modifications, alterations, and variations made by those skilled in the art without departing from the scope of the present invention based on the disclosed technical content are equivalent embodiments of the present invention. Furthermore, any modifications, alterations, and variations made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the present invention.

Claims

1. A quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition, characterized in that, The ingredients include the following parts by weight: 20-30 parts of quaternary ammonium salt type pyrrolidine polyoxyethylene ether, 0.5-1 part of antioxidant, and 25-35 parts of deionized water; The quaternary ammonium salt type pyrrolidine polyoxyethylene ether is prepared by the following method: S1: 1,16-Di(pyrrolidone-1-yl)hexadecane reacts with 5-bromopentanoic acid to form a quaternary ammonium salt compound. S2: Quaternary ammonium salt compounds react with lauryl alcohol polyoxyethylene ether to generate quaternary ammonium salt type pyrrolidine polyoxyethylene ether; The antioxidant is prepared by the following method: N1: Cyanuric chloride reacts with aminodecaglycol monomethyl ether to form a monosubstituted compound. N2: Monosubstituted compounds react with 3,5-di-tert-butyl-4-hydroxybenzylamine to generate antioxidants.

2. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, In step S1, the molar ratio of 1,16-bis(pyrrolidine-1-yl)hexadecane to 5-bromopentanoic acid is 1:2.

01.

3. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, In step S2, the molar ratio of the quaternary ammonium salt compound to lauryl alcohol polyoxyethylene ether is 1:2.

02.

4. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, In step N1, the molar ratio of cyanuric chloride to aminodeglycol monomethyl ether is 1:(1.01-1.02).

5. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, In step N2, the molar ratio of the monosubstituted compound to 3,5-di-tert-butyl-4-hydroxybenzylamine is 1:(2.02-2.04).

6. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction solvent for step S1 is isopropanol.

7. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction solvent in step S2 is tetrahydrofuran.

8. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction solvent in step N1 is anhydrous acetonitrile.

9. The quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to claim 1, characterized in that, The reaction solvent in step N2 is anhydrous acetonitrile.

10. A method for preparing the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Weigh out the following by weight: 20-30 parts of quaternary ammonium salt type pyrrolidine polyoxyethylene ether, 0.5-1 part of antioxidant, and 25-35 parts of deionized water; (2) Stir and mix the quaternary ammonium salt type pyrrolidine polyoxyethylene ether, antioxidant and deionized water to obtain the quaternary ammonium salt type pyrrolidine polyoxyethylene ether composition.

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