锰-二茂铁基配位聚合物微球的制备与表征  

SYNTHESIS AND CHARACTERIZATION OF MANGANESE-BASED FERROCENYL COORDINATION POLYMER MICROSPHERES

作　　者：霍甲[1] 王立[1] 俞豪杰[1] 范登森[1] 

机构地区：[1]化学工程国家重点实验室(浙江大学)浙江大学化学工程与生物工程学系,杭州310027

出　　处：《高分子学报》2011年第9期1033-1039,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20772108和20802067);科技部项目(项目号2009DFR40640);教育部博士点基金(基金号200803350118);宁波市科技计划项目(项目号2009D10005)资助

摘　　要：采用溶剂热法制得了一系列锰-二茂铁基配位聚合物微球,系统研究了反应时间、反应物浓度等因素对配位聚合物微球的形貌和尺寸的影响规律,采用SEM、TEM、PXRD、EDX和FTIR等方法研究了微球的形貌、尺寸和结构等.发现通过调节反应时间,可使微球的尺寸约在4～9μm范围内变化,提高反应物浓度可使微球从光滑的球形结构向核壳结构转变.基于PXRD、FTIR和EDX的研究,我们认为锰-二茂铁基配位聚合物具有三明治型层状晶体结构,骨架中存在两种不同配位模式的Mn,每两个Mn(1)和一个Mn(2)与一个氧桥连接形成一个MnO内层,二茂铁二甲酸基的两个环戊二烯环呈顺式重叠构型在MnO内层两侧交替排布形成了外层,从而形成2D三明治型层状配位聚合物.TGA研究表明锰-二茂铁基配位聚合物微球具有较好的热稳定性.A series of manganese-based ferrocenyl coordination polymer microspheres were prepared by solvothermal reactions,the influence of reaction time and reagent concentration on the morphology and diameters of microspheres was investigated systematically,and the morphology,diameters and crystal structure of manganese-based ferrocenyl coordination polymer microspheres were characterized by scanning electron microscopy（SEM）,transmission electron microscopy（TEM）,powder X-ray diffraction（PXRD）,energy dispersive X-ray spectrometry（EDX） and Fourier-transform infrared spectroscopy（FT-IR）.By adjusting the reaction time from 8 h,12 h to 24 h,the diameters of microspheres increased from 4 μm to 9.4 μm;on the contrary,the increase of reagent concentration decreased the size of particles from 11.4 μm to 9.4 μm at the tested range,and,at the same time,spheres were transformed from smooth spherical structures into core-shell structures.PXRD showed that manganese-based ferrocenyl coordination polymers crystallized into sandwich layered crystal structure with the possible formula of Mn4（OH）4（OOCC5H4FeC5H4COO）2.Within the framework,two kinds of different manganese atoms in a distorted octahedral geometry were incorporated into the layers and the ferocenedicarboxylato group existed as a synperiplanar conformation and tridentate-bridging mode connecting three manganese atoms.Manganese atoms were connected with oxygen atoms to form a two-dimensional inner layer with the ferrocenyl groups arranged along two sides of the inner layer,thus forming the sandwich-like coordination polymers.EDX indicated the microspheres contained Mn,Fe,C and O,and C-O stretching frequency shifting from 1687 cm-1 for the precursor to 1581.7 cm-1 for the product from FT-IR spectra confirmed the formation of coordination polymer.TGA showed the coordination polymer microspheres had good thermal stability up to at least 319℃.

关 键 词：配位聚合物 微球 二茂铁 锰 

分 类 号：O634[理学—高分子化学]