基于ARGET-ATRP方法制备石墨烯平面聚合物刷

Graphene has emerged to be a promising material due to its unique two-dimensional structure, excellent chemical and physical properties. It has a wide application in the field of electronics, materials, catalysis and biomedicine. However, single graphene platelets tend to undergo agglomeration easily due to strong interactions, which significantly compromises the final material properties. The improvement of the dispersity is a major obstacle to be resolved in both academia and industry. Additionally, how to adjust the structures and properties of the materials in a controlled manner is also an urgent problem confronting researchers. In order to address these problems, activators regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP) covalent modification combined with polydopamine noncovalent modification was used to obtain the controlled polymer brush modified graphene. Polymer brushes would be grafted on graphene by coating the sheets with polydopamine as a reactive under-layer and sequential surface-initiated ARGET-ATRP polymerization of monomers. With the target of preparation of well-controlled polymer brush covalent modification graphene and in-situ fabrication of the graphene nanocomposites in a highly effectively manner, reaction conditions would be detailed discussed. Additionally, the relationship between structure and property of the materials would also be explored. The target of this project is to provide a more conveniently, efficiently and environmental friendly method to conduct modification of graphene with polymer brush in a well-controlled way. Moreover, this subject would provide theoretical and experimental support in research of the relationship between structure and property of the modified graphene.

石墨烯作为一种具有优异物理化学性能的二维纳米材料，在电子、材料、催化、生物医药等领域具有广阔的应用前景。但由于石墨烯片层极容易团聚，影响其独特性能的发挥，故需要对其进行表面改性。目前，ATRP作为一种制备聚合物刷共价修饰石墨烯的方法被广泛采用。但传统ATRP存在反应操作繁琐以及催化剂污染等问题，因而选用一类新的引发体系应用于石墨烯改性具有非常重要的意义。此外，在聚合物刷共价修饰石墨烯的研究中，如何直接精确地对聚合物刷结构进行表征是有待解决的另一关键问题。针对如上问题，本项目拟将ARGET-ATRP共价修饰与聚多巴胺非共价修饰相结合，原位聚合制备石墨烯平面聚合物刷材料，并对表面聚合物刷的结构进行表征。通过本项目的研究，为可控聚合物刷共价修饰石墨烯提供一种简便、高效且环境友好的活性/可控自由基聚合方法，并为研究表面聚合物刷结构与改性石墨烯性能的关系提供实验结果及理论支持。

石墨烯作为一种具有优异物理化学性能的二维纳米材料，在电子、材料、催化、生物医药等领域具有广阔的应用前景。但由于石墨烯片层极容易团聚，影响其独特性能的发挥，故需要对其进行表面改性。基于电子转移活化再生催化剂原子转移自由基聚合（ARGET-ATRP）及多巴胺化学对材料表面修饰改性的优点，本项目首次将ARGET-ATRP共价修饰与聚多巴胺非共价修饰相结合，原位聚合制备石墨烯平面聚合物刷。首先通过多巴胺（DA）对GO进行表面涂覆，制备rGO/PDA。利用rGO/PDA与溴代异丁酰溴反应，制备rGO/PDA-Br。之后以rGO/PDA-Br为引发剂，采用ARGET-ATRP方法表面引发MMA、St、DMAEMA、DEAEMA、GMA及HFMA等多种单体的聚合，制备了不同种类的石墨烯平面聚合物刷，并对其结构及性能进行了表征与测试。其中，制备的PS及PMMA聚合物刷修饰的石墨烯材料可用于填充在PS或PMMA中，以提高基体的耐热性及导热性。经过胺基功能化后PGMA聚合物刷修饰的石墨烯材料对于藏红、孔雀石绿及亚甲基蓝等染料有较好的吸附效果，在水污染处理等方面有较好的研究及应用价值。PDEAEMA及PDMAEMA聚合物刷修饰的石墨烯具有良好的有酸碱响应性，所合成的pH响应型石墨烯聚合物刷在药物载体及响应性释放等领域具有潜在应用价值。将PGMA-r-PHFMA聚合物刷修饰的石墨烯与环氧树脂混合，并喷涂于 Q235碳钢表面，实验结果标明，掺杂有石墨烯聚合物刷的环氧树脂涂层与纯环氧树脂比较，拥有更好的防腐性能。此外，本项目还探讨了将ARGET-ATRP共价修饰与聚多巴胺非共价修饰相结合的方法用在了钛片、不锈钢片等其它固体基质的表面修饰。实验结果表明，经过两种技术相结合所制备的季铵化PDMAEMA及PDEAEMA聚合物刷修饰的钛片表面抗菌效率可达90%，为制备其它生物材料的抗菌涂层，提供了较好的策略。通过本项目的研究，为结构可控聚合物刷共价修饰石墨烯或其它固体基质的修饰提供一种简便、高效且环境友好的活性/可控自由基聚合方法，并为研究表面聚合物刷结构与材料性能的关系提供实验结果及理论支持，且所制备材料具有一定的研究及应用价值。