油脂基酰胺基表面活性剂的设计、短流程合成及多官能团交互作用研究

Oil derived amide surfactants are generally synthesized by means of high-pressured hydrolysis of oil and fat, acyl chloride reaction and condensation reaction. These process require long flow and need the use of high pressure installs,corrosive and irritative raw materials. On the other hand, the products obtained from these methods are limited to use in narrow fields because of side products. In this project, novel oil derived amide surfactants whth multi-functional groups exist in the moleculars plan to be synthesized through N-acylation reaction of natural oils with various kinds of amino compounds, which would reduce the response flow, raises the atomic use factor. Specifically, several aspects will be researched in detail as followes. Firstly, the reaction laws of natural oils with amino compounds. Secondly, the design and synthesis of about 50 oil derived amide surfactants with surface activity, which belong to 14 series. Thirdly, the relationship of structure with assembling behaviour and property. Based on formulation theory of surfactants, cooperativity effects can be acquired from effective combination. The target products of this project are homologues with the hydroxyl, the amido linkage, the duplet bond and the carboxyl group and other active functional groups, which probably possess better interfacial properties. The central idea of this project is in accordance with green chemistry, taking advantage of renewable resources instead of toxic and harmful raw materials, to obtain environmentally friendly and secure surfactants. The research achievements of this project would contribute to the green synthesis and enrich the formulation theory of surfactants, which provide ideas and theory support for the study of novel oil derived amide surfactants.

油脂制备表面活性剂一般要经高压水解、酰氯化、缩合、还原等过程，流程长、副产物多，需使用高压装置或有强腐蚀性及刺激性原料。本项目研究设计以国产非食用油脂与氨基酸、醇胺、多元胺等进行反应的短流程合成方法，探讨油脂与氨基化合物反应的调控与规律，以减少反应步骤，提高原子经济性，降低进口食用油脂消耗。以该思路为指导，将羟基、酰胺键、双键及胺基等基团通过共价键连接引入目标分子，设计合成4类50余个新型油脂基酰胺基表面活性剂。研究分子结构与自组装行为的关系，探究多官能团交互作用及同系物协同效应在分子聚集中发挥驱动效果的调控与规律，阐明两亲分子排列及有序组合体的构筑规律，找出分子结构与性能的关系，发现性能更好的两亲分子。项目是依据绿色化学主体思想，利用生物资源代替有毒害原料，合成环境友好、安全性高的产品。项目有助于发展绿色合成方法，丰富表面活性剂构效及复配理论，为油脂基表面活性剂研究提供新思路和理论支持。

研究开发高效、绿色、安全的油脂基酰胺基表面活性剂具有重要的科学理论意义和实际应用价值。油脂基酰胺基表面活性剂的传统制备工艺为酰氯法，需使用三氯化磷或氯化亚砜及脂肪酰氯等强刺激性及腐蚀性原料，环境污染严重、产品质量较差，严重限制了该类表面活性剂的发展与应用。本项目以蓖麻油、棉籽油等国产非食用油脂为原料，直接与氨基酸、多元胺等氨基化合物进行酰胺化反应，通过优化反应条件，建立了绿色合成方法，并设计合成了油脂基酰基氨基酸盐、油脂基酰胺基甜菜碱、油脂基酰胺基氧化铵、油脂基酰胺基季铵盐等4大类50余个油脂基酰胺基表面活性剂。此方法具有反应物绿色安全、反应路线短、反应条件环境友好、产品质量高等优点。通过现代波谱分析技术对制得的产品进行了结构表征，通过胶体与界面化学仪器，对产品的自组装行为、表/界面性质、泡沫性能、乳化性能、抗硬水能力、抑菌性能及去污力等性能进行了评价。结果表明，合成的油脂基酰胺基表面活性剂均具有表面活性剂的典型特征及优异的表/界面活性和自组装能力。作为生物质资源，天然油脂的组成和结构丰富多样，赋予了油脂酰胺基表面活性剂丰富的物理化学性质。通过对植物油脂的脂肪酸组成进行分析，将油脂基结构归纳为三类特征因素：疏水基碳链长度的差异、疏水基双键数目的差异以及羟基等亲水基团，研究结果揭示了油脂基的特征结构与表面活性剂自组装行为的关系。本项目的研究为油脂基酰胺基表面活性剂的绿色合成开辟新的途径，揭示了植物油脂组成和结构对表面活性剂物理化学性质和应用性能的影响规律，不仅丰富表面活性剂的理论，也为新型油脂基酰胺基表面活性剂的分子设计和应用开发奠定了研究基础。