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HBPE-b-PMMA嵌段共聚物的合成及其在甲苯中非共价剥离石墨制备石墨烯溶液的研究 被引量:1

Synthesis of HBPE-b-PMMA Block Copolymer and Its Application in Preparing Graphene Solution by Noncovalent Exfoliation of Graphite in Toluene
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摘要 首先利用功能化α-二亚胺钯催化剂催化乙烯进行链"行走"配位聚合,获得含有2-溴代异丁酰溴末端基团的超支化聚乙烯(HBPE-Br),然后以其为大分子引发剂引发甲基丙烯酸甲酯(MMA)进行原子转移自由基聚合(ATRP),获得HBPE-b-PMMA嵌段共聚物,并对其在甲苯中非共价剥开天然石墨获得石墨烯甲苯溶液的能力进行了考察.氢核磁共振(1H-NMR)和凝胶渗透色谱(GPC)分析证实,已将PMMA嵌段引入HBPE结构中;紫外-可见光谱(UV-Vis)分析表明,所得共聚物在甲苯中可有效剥开天然石墨获得稳定的石墨烯甲苯溶液,石墨烯浓度可高达0.071 mg/mL;高分辨透射电镜(HRTEM)、原子力显微镜(AFM)和拉曼光谱分析共同表明:所获得的石墨烯结构完整、表面缺陷少,厚度为2~4层.该方法所得石墨烯甲苯溶液可望在聚合物/石墨烯纳米复合材料领域获得应用。 A hyperbranched polyethylene-b-poly( methyl methacrylate) block copolymer( HBPE-b-PMMA)was synthesized herein via a tandem polymerization process,in which chain walking ethylene coordination polymerization was first carried out with a functionalized Pd-diimine catalyst to give a telechelic HBPE covalently tethered with a 2-bromoisobutyryl end group( HBPE-Br),then atom radical transfer radical polymerization( ATRP) of MMA was initiated using the HBPE-Br as a macromolecular initiator,rendering the HBPE-b-PMMA copolymer. The ability of the as-synthesized copolymer to noncovalently exfoliate natural graphite( NG) leading to stable graphene solutions in toluene was further examined. The presence of PMMA blocks in the copolymer is well confirmed by the results from proton nuclear magnetic resonance(1H-NMR)and gel permeation chromatography( GPC) analysis. As indicated by UV-Vis spectroscopy test,the resulting copolymer can effectively exfoliate NG in toluene under the assistance of ultrasonication to render stable solutions of graphene with high concentrations up to 0. 071 mg /mL. The results from high-resolution transmittance electron microscopy( HRTEM),atomic force microscopy( AFM) and Raman spectroscopy commonly show that the resulting graphene nanosheets are free of structural defects,with a thickness of 2 ~ 4layers. These high-quality,stable graphene solutions in toluene are potentially useful for the preparation and applications of polymer-based graphene nanocomposites.
作者 程飞 王海平 叶誉贤 梁静静 徐立新 Fei Cheng, Hai-ping Wang, Yu-xian Ye, Jing-jing Liang, Li-xin Xu(College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014)
出处 《高分子学报》 SCIE CAS CSCD 北大核心 2014年第7期1002-1009,共8页 Acta Polymerica Sinica
基金 国家自然科学基金(基金号21074117) 浙江省科技厅创新团队(项目号2011R09004-04)资助项目
关键词 超支化聚乙烯 聚甲基丙烯酸甲酯 嵌段共聚物 石墨烯溶液 甲苯 非共价 Hyperbranched polyethylene Poly(methyl methacrylate) Block copolymer Graphene solution Toluene Noncovalent
作者简介 通讯联系人,E-mail:gcsxlx@zjut.edu.cn
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