基于超支化梳形多臂共聚物的石墨烯多功能薄膜制备研究  

Multifunctional Graphene Films Based on Designer Hyperbranched Comb-like Multi-arm Copolymers

作　　者：王敏 何杰 柴园园 叶会见 周洪涛 严维力 徐立新 Min Wang;Jie He;Yuan-yuan Chai;Hui-jian Ye;Hong-tao Zhou;Wei-li Yan;Li-xin Xu(College of Materials Science and Engineering,Zhejiang University of Technology,Hangzhou 310014;Pinghu Institute of Advanced Materials,Zhejiang University of Technology,Pinghu 314200)

机构地区：[1]浙江工业大学材料科学与工程学院,杭州310014 [2]浙江工业大学平湖新材料研究院,平湖314200

出　　处：《高分子学报》2024年第12期1716-1729,共14页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21474091,51707175)资助项目.

摘　　要：通过简单的工艺制备高性能、多功能石墨烯薄膜是石墨烯研究领域的重要课题.本研究利用链行走聚合和原子转移自由基聚合方法相结合的方法,以乙烯和丙烯酸十六烷基酯(HDA)为主要单体设计合成了超支化梳形多臂共聚物HBPE@PHDA,利用其辅助天然石墨液相剥离制得石墨烯分散液,进一步经真空抽滤获得不同组成比例的石墨烯复合薄膜(Graphene/HBPE@PHDA);利用凝胶渗透色谱(GPC)、氢核磁共振(1H-NMR)和熔融流变分析对所得共聚物的结构、组成进行了表征,并对所得石墨烯复合薄膜的微观结构、导热、力学和形状记忆性能进行了评价.研究表明,所得共聚物由近似球形的超支化聚乙烯(HBPE)核和多重的梳形聚合物侧链聚丙烯酸十六烷基酯(PHDA)构成;该共聚物作为分散助剂可有效促进石墨烯在普通低沸点有机溶剂中液相剥离,获得由该共聚物非共价稳固修饰的低缺陷石墨烯,同时在所得的石墨烯薄膜中可通过其侧链PHDA进行结晶,使所得石墨烯复合薄膜同时呈现优异的力学、各向异性导热和形状记忆性能;以石墨烯比例为60 wt%的样品为例,所得薄膜的拉伸强度可达3.0 MPa,平面热导率达29.4 W‧m‧K^(−1),各向异性比例达36.8.本研究为柔性、高强、多功能石墨烯薄膜的简单制备提供了新思路.It is highly desirable to produce high-performance,multifunctional graphene films through relatively simple process.Herein,a hyperbranched comb-like multi-arm copolymer,HBPE@PHDA,was designed and synthesized by combining the chain walking ethylene polymerization and atomic transfer radical polymerization of hexadecyl acrylate(HDA).The HBPE@PHDA noncovalently functionalized graphene was further obtained by exfoliating graphite in chloroform under sonication with the copolymer as stabilizer,and subsequently HBPE@PHDA/Graphene composite films were fabricated from the resultant graphene dispersion via vacuum filtration.The structure and composition of the HBPE@PHDA were characterized by gel permeation chromatography(GPC),proton nuclear megnetic resonance(1H-NMR)and melt rheological measurements,and the performance of the resultant graphene composite films was evaluated.It is confirmed that the HBPE@PHDA consists of a hyperbranched polyethylene(HBPE)core and multiple comb-like poly(hexadecyl acrylate)(PHDA)side chains,and as a stabilizer,the copolymer can effectively promote the exfoliation of graphite in chloroform,rendering the HBPE@PHDA-functionazlied graphene free of structural defects.And meanwhile,the copolymer can crystallize through the PHDA side chains in the resultant graphene composite film system,which simultaneously imparts the latter with excellent mechanical,anisotropically thermal transfer,and shape memory performance.As an example,the composite film with 60 wt%graphene exhibits a tensile strength,3.0 MPa,a thermal conductivity in plane,29.4 W·m·K^(−1)with an anisotropical ratio,36.8.This work provides a new simple way for producing flexible,high-strength,multifunctional graphene films.

关 键 词：超支化 梳形多臂 石墨烯薄膜 各向异性导热 形状记忆 

分 类 号：TB383.2[一般工业技术—材料科学与工程] TQ127.11[化学工程—无机化工]