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十二胺功能化石墨烯量子点的合成及其在苯乙烯乳液聚合中的稳定剂应用。

Synthesis of dodecylamine-functionalized graphene quantum dots and their application as stabilizers in an emulsion polymerization of styrene.

机构信息

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, China.

Key Laboratory of Synthetic and Biological Colloids, Ministry of Education, China; School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, China.

出版信息

J Colloid Interface Sci. 2017 Nov 1;505:847-857. doi: 10.1016/j.jcis.2017.06.091. Epub 2017 Jun 27.

Abstract

Pickering emulsions have attracted considerable interest due to their potential applications in many fields, such as the food, pharmaceutical, petroleum and cosmetics industries. The study reports the synthesis of dodecylamine-functionalized graphene quantum dots (d-GQDs) and their implementation as stabilizers in an emulsion polymerization of styrene. First, d-GQDs are prepared by thermal pyrolysis of citric acid and dodecylamine in 0.1M ammonium hydroxide. The resulting d-GQDs consist of small graphene sheets with abundant amino, carboxyl, acylamino, hydroxyl and alkyl chains on the edge. The amphiphilic structure gives the d-GQDs high surface activity. The addition of d-GQDs can reduce the surface tension of water to 30.8mNm and the interfacial tension of paraffin oil/water to 0.0182mNm. The surface activity is much better than that of previously reported solid particle surfactants for Pickering emulsions and is close to that of sodium dodecylbenzenesulfonate, which is, a classical organic surfactants. Then, d-GQDs are employed as solid particle surfactants for stabilizing styrene-in-water emulsions. The emulsions exhibit excellent stability at pH 7. However, stability is lost when the pH is more than 9 or less than 4. The pH-switchable behaviour can be attributed to the protonation of amino groups in a weak acid medium and dissociation of carboxyl groups in a weak base medium. Finally, 2,2'-azobis(2-methylpropionitrile) is introduced into the Pickering emulsions to trigger emulsion polymerization of styrene. The as-prepared polystyrene spheres display a uniform morphology with a narrow diameter distribution. The fluorescent d-GQDs coated their surfaces. This study presents an approach for the fabrication of amphiphilic GQDs and GQDs-based functional materials, which have a wide range of potential applications in emulsion polymerization, as well as in sensors, catalysts, and energy storage.

摘要

Pickering 乳液由于其在食品、制药、石油和化妆品等领域的潜在应用而引起了相当大的关注。本研究报告了十二胺功能化石墨烯量子点(d-GQDs)的合成及其在苯乙烯乳液聚合中的应用。首先,通过柠檬酸和十二胺在 0.1M 氨水中的热解制备 d-GQDs。所得 d-GQDs 由小的石墨烯片组成,边缘有丰富的氨基、羧基、酰氨基、羟基和烷基链。两亲性结构赋予 d-GQDs 高表面活性。添加 d-GQDs 可将水的表面张力降低至 30.8mNm,将石蜡油/水的界面张力降低至 0.0182mNm。表面活性优于之前报道的用于 Pickering 乳液的固体颗粒表面活性剂,接近于经典有机表面活性剂十二烷基苯磺酸钠。然后,将 d-GQDs 用作稳定苯乙烯/水乳液的固体颗粒表面活性剂。乳液在 pH 7 时表现出优异的稳定性。然而,当 pH 值大于 9 或小于 4 时,稳定性会丧失。这种 pH 开关行为可归因于弱酸性介质中氨基的质子化和弱碱性介质中羧基的离解。最后,将 2,2'-偶氮二(2-甲基丙腈)引入 Pickering 乳液中引发苯乙烯的乳液聚合。所制备的聚苯乙烯球具有均匀的形态和较窄的粒径分布。荧光 d-GQDs 涂覆其表面。本研究提出了一种制备两亲性 GQDs 和基于 GQDs 的功能材料的方法,该方法在乳液聚合以及传感器、催化剂和储能等领域具有广泛的潜在应用。

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