阅读说明：本技术 一种两性离子表面活性剂及其制备方法 (Zwitterionic surfactant and preparation method thereof ) 是由 任雁鹏 郭胜利 于 2020-04-26 设计创作，主要内容包括：本发明公开了一种两性离子表面活性剂及其制备方法,该两性离子表面活性剂通过以下步骤制备：在装有长链不饱和脂肪酸反应瓶中滴加定量的1-取代氮丙啶反应物进行第一步氮丙啶开环反应；在弱碱性条件下,向上述反应物中加入定量的3-氯-2-羟丙基-三甲基氯化铵水溶液进行第二步季胺化反应,最后向上述反应物中加入亚硫酸盐水溶液对双键进行磺化反应,获得一种两性离子表面活性剂,其分子结构式为：<Image he="189" wi="700" file="DDA0002467068780000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中,n为7～8,m为7～11；R<Sub>1</Sub>-为<Image he="164" wi="582" file="DDA0002467068780000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention discloses a zwitterionic surfactant and a preparation method thereof, wherein the zwitterionic surfactant is prepared by the following steps: dropwise adding a quantitative 1-substituted aziridine reactant into a reaction bottle filled with long-chain unsaturated fatty acid to perform a first-step aziridine ring-opening reaction; under the condition of alkalescence, adding a certain amount of 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant to carry out second-step quaternization reaction, and finally adding sulfite aqueous solution into the reactant to carry out sulfonation reaction on double bonds to obtain the zwitterionic surfactant, wherein the molecular structural formula of the zwitterionic surfactant is shown in the specification： Wherein n is 7-8, and m is 7-11; r 1 -is of)

1. A zwitterionic surfactant characterized by: the molecular structural formula is as follows:

wherein n is 7-8, and m is 7-11; r₁-is of

2. The method for producing a zwitterionic surfactant according to claim 1, wherein: the molecular structural formula is realized by the following two-step reaction: dropwise adding a quantitative 1-substituted aziridine reactant into a reaction bottle filled with long-chain unsaturated fatty acid to perform a first-step aziridine ring-opening reaction, wherein the molar ratio of the long-chain unsaturated fatty acid to the 1-substituted aziridine is 1: 1; adding a quantitative 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant under the alkaline condition of pH 7-9 to perform a second quaternization reaction, wherein the molar ratio of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to the 1-substituted aziridine is 2: 1; and finally, adding a sodium bisulfite aqueous solution into the reactant to carry out sulfonation reaction on double bonds, wherein the molar ratio of the sodium bisulfite to the long-chain unsaturated fatty acid is 1:1, so as to obtain the zwitterionic surfactant, wherein the synthesis equation is as follows:

wherein n is 7-8, and m is 7-11; r₁-is of

3. The method for producing a zwitterionic surfactant according to claim 2, wherein: the long-chain unsaturated fatty acid is long-chain monoenoic acid; the 1-substituted aziridine is aziridine-1-carboxylic acid methyl ester or aziridine-1-carboxylic acid tert-butyl ester.

4. The method for producing a zwitterionic surfactant according to claim 3, wherein: the long-chain monoenoic acid is oleic acid or erucic acid.

5. The method for producing a zwitterionic surfactant according to claim 2, wherein: the method comprises the following specific steps:

dissolving long-chain unsaturated fatty acid into an N-methyl pyrrolidone solution, wherein the mass concentration of the long-chain unsaturated fatty acid is 30-50%, adding the solution into a reaction bottle provided with a reflux condensing device, dropwise adding a 1-substituted aziridine reactant into the reaction solution to perform a first step aziridine ring-opening reaction, wherein the molar ratio of the 1-substituted aziridine reactant to the long-chain unsaturated fatty acid is 1:1, and reacting at 60-90 ℃ for 5-10 hours; then the reaction solution is added with Na₂CO₃Adjusting the pH value to be 7-9, adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to perform a second-step quaternization reaction, wherein the molar ratio of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to the 1-substituted aziridine is 2:1, and reacting at 50-80 ℃ for 5-8 hours; finally, adding a sodium bisulfite water solution with the mass concentration of 40% to perform sulfonation reaction, wherein the molar ratio of sodium bisulfite to long-chain unsaturated fatty acid is 1:1, and reacting for 5-9 h at 100-140 ℃; removing insoluble substances after the reaction is finished, concentrating the reaction solution, purifying and separating the product by using a toluene column chromatography, and drying in vacuum until the weight is constant to obtain the product.

Technical Field

The invention relates to a surfactant, in particular to a zwitterionic surfactant and a preparation method thereof, and belongs to the field of chemical synthesis.

Background

The amphoteric surfactant has many excellent characteristics such as low irritation and low toxicity, because it simultaneously carries anions and cations, unlike conventional anionic and cationic surfactants; resistance to hydration and high concentration electrolytes; the degradation capability, bactericidal property and bacteriostatic property, good wettability, good compatibility with other types of surfactant products, synergistic effect and the like. At present, the types of amphoteric surfactants are not many, the price of the amphoteric surfactants limits the wide application of the amphoteric surfactants, but the unique advantages displayed in the using process of the amphoteric surfactants can be sufficiently compensated for the defect that the price of the amphoteric surfactants is too high in some occasions, and in recent years, the synthetic design work of the amphoteric surfactants is also increased by domestic scientific research workers, so that more economic raw material substitutes are searched, and the more reasonable and more environment-friendly surfactant route is designed, which has very important significance.

Disclosure of Invention

In order to solve the existing problems, the invention aims to provide a zwitterionic surfactant. The second purpose of the invention is to provide a preparation method of the surfactant. The third purpose of the invention is to provide an economic, reasonable in structure and more environment-friendly zwitterionic surfactant.

The technical scheme of the invention is as follows: a zwitterionic surfactant has a molecular structural formula:

wherein n is 7-8, and m is 7-11; r₁-is of

Further, the molecular structural formula is realized by the following two-step reaction: dropwise adding a quantitative 1-substituted aziridine reactant into a reaction bottle filled with long-chain unsaturated fatty acid to perform a first-step aziridine ring-opening reaction, wherein the molar ratio of the long-chain unsaturated fatty acid to the 1-substituted aziridine is 1: 1; adding a quantitative 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution into the reactant under the alkaline condition of pH 7-9 to perform a second quaternization reaction, wherein the molar ratio of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to the 1-substituted aziridine is 2: 1; and finally, adding a sodium bisulfite aqueous solution into the reactant to carry out sulfonation reaction on double bonds, wherein the molar ratio of the sodium bisulfite to the long-chain unsaturated fatty acid is 1:1, so as to obtain the zwitterionic surfactant, wherein the synthesis equation is as follows:

wherein n is 7-8, and m is 7-11; r₁-is of

Further, the long-chain unsaturated fatty acid is long-chain monoenoic acid; the 1-substituted aziridine is aziridine-1-carboxylic acid methyl ester or aziridine-1-carboxylic acid tert-butyl ester.

Further, the long-chain monoenoic acid is oleic acid or erucic acid.

Further, the preparation method of the zwitterionic surfactant comprises the following specific steps:

dissolving long-chain unsaturated fatty acid into an N-methyl pyrrolidone solution, wherein the mass concentration of the long-chain unsaturated fatty acid is 30-50%, adding the solution into a reaction bottle provided with a reflux condensing device, dropwise adding a 1-substituted aziridine reactant into the reaction solution to perform a first step aziridine ring-opening reaction, wherein the molar ratio of the 1-substituted aziridine reactant to the long-chain unsaturated fatty acid is 1:1, and reacting at 60-90 ℃ for 5-10 hours; then the reaction solution is added with Na₂CO₃Adjusting the pH value to be 7-9, adding 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to perform a second-step quaternization reaction, wherein the molar ratio of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride to the 1-substituted aziridine is 2:1, and reacting at 50-80 ℃ for 5-8 hours; finally, adding a sodium bisulfite water solution with the mass concentration of 40% to perform sulfonation reaction, wherein the molar ratio of sodium bisulfite to long-chain unsaturated fatty acid is 1:1, and reacting for 5-9 h at 100-140 ℃; removing insoluble substances after the reaction, concentrating the reaction solution, and purifying by toluene column chromatographySeparating the product by chemical separation, and drying in vacuum to constant weight to obtain the product.

The invention has the advantages that: the invention introduces hydrophilic sulfonate group into the hydrophobic chain, and the structure endows the surfactant with excellent water solubility and salt tolerance. Because the hydrophilic head group of the surfactant contains multi-quaternary ammonium salt groups, the surfactant can be used as a cross-linking agent of an anion thickening agent to be applied to oil field fracturing through electrostatic attraction, and a hydrophobic chain of the surfactant contains hydrophilic sulfonic groups, so that weak gel formed by the cationic surfactant and the anion thickening agent in a cross-linking mode can be ensured to have good water solubility, and the phenomenon of precipitation after the existing cationic surfactant and the anion thickening agent are cross-linked can be overcome. In addition, the zwitterionic surfactant prepared by the method has the advantages of low cost, convenient and simple preparation process, easy amplification production and the like.

Detailed Description