氧化石墨烯/微孔聚合物复合微球的制备研究

Preparation of Graphene Oxide/Hyper-crosslinked Microporous Polymer Composite Microspheres

首先以苯乙烯(St)、二乙烯基苯(DVB)以及二甲基二烯丙基氯化铵(DADMAC)为单体,通过无皂乳液聚合制备了交联微球,然后以1,2-二氯乙烷(DCE)为溶胀剂,二甲氧基甲烷(FDA)为外交联剂,在三氯化铁(Fe Cl3)催化作用下经傅克烷基化反应编织微孔结构,最后通过静电作用将氧化石墨烯包覆在微孔微球表面,得到氧化石墨烯/微孔聚合物复合微球。扫描电镜与Zeta电位及粒度分析结果发现,微球单分散性良好,表面带正电;氮气吸附脱附曲线及孔径分布曲线结果表明,微孔聚合物中含有大量微孔,比表面积达到902m2/g;透射电镜、拉曼光谱及X射线光电子能谱分析结果显示,氧化石墨烯成功包覆在微孔微球表面。

Crosslinking microspheres were firstly synthesized through emulsifier-free emulsion polymerization with styrene （St）, divinylbenzene （DVB） and dimethyl diallyl ammonium chloride （DADMAC） as the monomers. Futhermore, microporous structure in the polymer microspheres were knitted via Friedel-Craft acylation＇s reaction with 1, 2- dichloroethane as swelling agent, formaldehyde dimethyl acetal （FDA） as external crosslinker, and ferric trichloride （FeCl4） as catalyst. Finally, graphene oxide/microporous polymercomposite microspheres （GO/HCMPs） were prepared via cladding GO to HCMPs by means of electrostatic interactions. Scanning electron microscope （SEM） images, Zeta- potential and particle size analysis results show the surface of the microsphere is positive and the particle size of microspheres is monodisperse. Nitrogen sorption isotherm and pore size distribution indicate that HCMPs combine massive micropores and its specific surface area is as high as 902m2/g. Transmission electron microscope （TEM） images, Raman spectra and X-ray photoelectron spectroscopy （XPS） show that GO sheets are successfully coated on the surface of HCMPs.