摘要
石墨烯是由单层sp2杂化碳原子紧密堆积成二维蜂窝状晶格结构碳材料。石墨烯特殊的单原子层结构决定了其独特的物理性质,如高强度,高模量,高导热性能,高电子迁移率,高比表面积和高阻隔性能等。石墨烯表现出来的独特电子与物理特性,使其在聚合物复合材料中具有重要的应用前景。石墨烯的表面修饰是制备聚合物/石墨烯复合材料的关键。通过氧化石墨烯的还原和改性是制备修饰石墨烯最有效的方法之一。天然植物提取物中有许多化学物具有特殊的还原特性,且绿色环保,在修饰石墨烯的制备上具有独特的优势。本研究采用天然的绿茶提取物——茶多酚(TP)作为石墨烯的修饰剂,制备了多酚及其衍生物修饰的石墨烯。深入研究了这些功能化石墨烯的制备方法,修饰机理和微观结构。将这些功能化石墨烯与橡胶复合制备了橡胶/石墨烯复合材料,详细研究了这些功能化石墨烯对橡胶力学性能、导电性能的影响。这些研究对石墨烯功能材料和橡胶材料的增强和功能化具有重要的理论意义和实践价值。
作为一类环境友好、低成本的植物单宁,TP被证实是氧化石墨烯(GO)的有效还原剂和理想修饰剂。这种方法制备的修饰石墨烯(TPG)具有制备工艺简单,可放大制备,价格低廉和绿色环保等优点。TPG具有很高的导电性,且能够稳定分散在水、醇类和一些极性溶剂中。揭示了TP还原GO和稳定石墨烯的机理。TP中B环和C环的没食子单元与GO经两步亲核加成反应和消除反应之后,将GO的环氧基修复为双键结构,同时没食子单元被氧化为邻醌类没食子衍生物结构。TP稳定石墨烯的机理主要是TP与石墨烯之间通过的π-π相互作用和空间位阻效应。
通过TPG表面的邻醌与巯基之间的Michael加成反应,进一步制备了具有硫醚结构的STPG。详细研究了STPG的制备条件、反应机理和结构。结果表明STPG具有更加宽泛的有机溶解性;利用TPG表面的酚结构单元与胺/甲醛之间的Mannich反应,在TPG表面引入了聚醚胺低聚物,制得了Mannich缩合物(醛胺聚合物)修饰的石墨烯JTPG。JTPG具有极优异的水溶性和有机溶解性。通过真空辅助抽滤,可以将JTPG加工成石墨烯杂化膜材料,这种石墨烯杂化膜表现出极高的综合性能,拉伸强度达到275MPa,断裂伸长率8%,导电率约为700S/m。
采用乳液共混法制备了丁苯吡橡胶(VPR)/TPG和丁苯橡胶(SBR)/TPG复合材料。研究发现,TPG可以高效地增强VPR和SBR。TPG还可以高效提高SBR的耐磨性,表现出对VPR的自硫化作用。通过溶液法制备了JTPG母料,并通过熔体加工(开炼)制备了SBR/JTPG和NBR/JTPG复合材料。通过溶液法制备了过氧化物和硫黄硫化的NBR/JTPG复合材料。详细研究了这些复合材料的结构和性质。通过溶液法制备的硫黄硫化NBR/JTPG复合材料具有更明显更优异的分散,也表现出更高的增强效率。通过溶液法制备的过氧化物硫化NBR/JTPG复合材料具有优异的导电性能,其导电阈值低至0.23vol%。
Graphene, composed of single-layer sp~2hybridized carbon atoms, is a carbonaceousmaterial with two-dimensional honeycomb lattice structure. For it’s special single carbonatomic layer structure, graphene possesses a number of unique physical properties, such ashigh strength, high modulu, high thermal conductivity, high electron mobility, high specificsurface area and high barrier performance, and such exceptional performance makes grapheneespecially promising in the fabrication of the polymer composites. One of the key issues infabricating the polymer/graphene composites is the surface functionalization for graphene.While the reduction and decoration of graphene oxide (GO) is one of the most effectivemethods for the fabrication of the functionalized graphene. In this study, tea polyphenols (TP)which is the extract of natural green tea, was used as both reducer and modifier for GO topreparing the functionalized graphene (TPG). We have investigated the preparation process,functionalized mechanism and microstructure of TPG. Then, TPG was used to fabricate therubber/TPG composites. The mechanical properties and electrical conductivity of rubber/TPGcomposites were studied. These studies are believed to be of great importance theoreticallyand practically in view of the reinforcement and functionlization of the rubber materials.
As a kind of plant-based tannin, the low cost and environmentally friendly TP wasverified to be effective reducer and modifier for GO. This method possesses many attractingcharacteristics such as facile process, scalable, low cost and environmentally friendly. TPGexhibits considerably high electrical conductivity and excellent dispersity in water, alcoholsand some other polar solvents. The reduction mechanism of TP towards GO was disclosed.The B ring and C ring in the galloyl units of TP are oxidized to orthoquinone through a twostep SN2nucleophilic reaction followed by one-step elimination. At the same time, the epoxygroups in GO are repaired to carbon-carbon double bond. The main stabilization mechanismsof TPG are disclosed to be the π-π interaction and the steric hindrance provided by the TP ongraphene layer.
Through the Michael addition between orthoquinones on TPG and a thiol, STPG whichconsisting sulfide structures was prepared. The preparation condition, reaction mechanism and mircrostructure of STPG were investigated. The results show that STPG has a broaderspectrum of solubility than TPG. In addition, taking advantage of the polyphenol group onTPG, the Mannich condensation between TPG and Jeffamine/formaldehyde was performed.JTPG decorated with the Mannich condensate was accordingly resulted. Except for theexcellent solubility in both water and organic solvent, JTPG can also be fabricated intopaper-like materials by vaccum-assisted filtration. The resulted hybrid film exhibits superiorperformance combination. For example, the tensile strength, break strain and electricalconductivity were measured to be275MPa,8%and700S/m, respectively.
Butadiene-styrene-vinyl pyridine rubber (VPR)/TPG composites and styrene-butadienerubber (SBR)/TPG composite were prepared by latex co-coagulation method. TPG wasdemonstrated to be very effective in strengthening the VPR and SBR. TPG was found to beespecially effective in endowing SBR with unusual abrasion resistance. Interestingly,VPR/TPG composites may be vulcanized in absence of additional curing agents. TheSBR/JTPG and NBR/JTPG composites were prepared by melt compounding the gums with aJTPG master batch which was prepared by mixing JTPG and NBR in acetone. TheNBR/JTPG composites could also be prepared by blending JTPG and NBR in acetone,followed by curing with peroxide or sulfur. The structures and properties of these compositeswere investigated. For the NBR/JTPG systems, the composites prepared by solution methodpossess much better dispersion of graphene and consequently much higher reinforcingefficiency. The solution processed NBR/JTPG composites cured with peroxide exhibitsignificantly increased electrical conductivity. The percolation threshold of these compositeswas determined to be as low as0.23vol%。
引文
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