【作者】 翟兆兰； 宋湛谦； 商士斌； 饶小平；

【Author】 Zhai Zhaolan;Song Zhanqian;Shang Shibin;Rao Xiaoping;Institute of Chemical Industry of Forest Products,CAF, Key Lab.of Biomass Energy and Material, Jiangsu Province, Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Jiangsu Province, Key Lab.of Chemical Engineering of Forest Products,National Forestry and Grassland Administration, National Engineering Lab.for Biomass Chemical Utilization;

【机构】 中国林业科学研究院林产化学工业研究所江苏省生物质能源与材料重点实验室江苏省林业资源高效加工利用协同创新中心国家林业草原局林产化学工程重点实验室生物质化学利用国家工程实验室；

【摘要】 近年来,石油资源枯竭、环境污染严重,以天然可再生资源代替石油产品生产绿色表面活性剂已成为表面活性剂发展的必然趋势[1]。松香是我国重要的生物质资源,其主要成分树脂酸含有独特的三环二萜刚性结构,具有明显的疏水性。并且松香树脂酸的结构中含有双键和羧基两个反应活性中心,易于进行化学改性,所以松香是制备绿色表面活性剂的重要原料[2]。本文以松香为初始原料合成了疏水基为全刚性的松香基pH响应型表面活性剂4-马来海松酸酰亚胺偶氮苯钠(Na-MPA-AZO-Na,分结构式如图1所示)。当pH由12.35降为9.31,再降至5.90时,Na-MPA-AZO-Na由Bola型表面活性剂转变为单头单尾的普通表面活性剂,最后转变为完全疏水的结构。Na-MPA-AZO-Na与十六烷基三甲基溴化铵(CTAB)复配可自组织形成蠕虫胶束。研究了Na-MPA-AZO-Na(12 mM)/CTAB(60 mM)溶液的p H响应性的结果表明,在pH 2.62时,Na-MPA-AZO-Na/CTAB复配体系具有良好的粘弹性,溶液中的聚集体为截面直径约10 nm的蠕虫胶束(图2a)。在p H 12.35时,复配体系的粘弹性变差,溶液中的聚集体为球状胶束和棒状胶束(图2b)。通过调节溶液的p H值可实现蠕虫胶束和球状胶束的可逆转变。更多还原

【Abstract】 The recent pressure from the diminishing petroleum oil resources and serious environmental pollution has been driving many scientists and researchers to focus on the sustainable development of the chemical industry. The preparation of green surfactants from natural products is an important development direction of surfactants. Rosin is an abundantly biomass resource, its main ingredient is abietic acid. The molecule of abietic acid is composed of a large rigid tricyclic hydrophenanthrene structure, which is extremely hydrophobic. In addition, the molecular structure of abietic acid contains a carboxyl group and a conjugated double bond, it can be easily modified. Thus, rosin is an available raw material for the synthesis of green surfactants. Herein, sodium N-azobenzenemaleimidepimaric carboxylate(Na-MPA-AZO-Na, Fig.1) was synthesized using rosin as the starting material. Na-MPA-AZO-Na is a pH-responsive surfactant, and its hydrophobic group is completely composed by rigid group. When the aqueous pH decreases from 12.00 to 9.31 to 5.90, Na-MPA-AZO-Na transforms from a Bola surfactant to a traditional surfactant containing a hydrophobic group and a hydrophilic group, then a completely hydrophobic structure. The aggregates in the mixed systems of Na-MPA-AZO-Na and cetyltrimethylammonium bromide(CTAB) are wormlike micelles. The pH-responsiveness of the Na-MPA-AZO-Na(12 m M)/CTAB(60 m M) system have been studied. When the pH is 2.62, the Na-MPA-AZO-Na/CTAB system can form viscoelastic solutions, the aggregates are wormlike micelles with a cross-sectional diameter of 10 nm. When the pH is 12.00, the Na-MPA-AZO-Na/CTAB system show poor viscoelasticity and the aggregates are spherical micelles and rod-like micelles. The wormlike micelles and spherical micelles can be transformed by altering the pH.更多还原