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浙江工业大学材料科学与工程学院,杭州,310014
纸质出版日期:2015-8-20,
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梁静静, 叶誉贤, 王海平, 王陈旻, 徐立新. 核壳型Fe3 O4@SiO2磁性纳米粒子表面超支化聚乙烯共价接枝研究[J]. 高分子学报, 2015,(8):941-949.
Jing-jing Liang, Yu-xian Ye, Hai-ping Wang, Chen-min Wang, Li-xin Xu. Covalently Grafting Hyperbranched Polyethylenes onto Core-Shell Fe3O4@SiO2 Magnetic Nanoparticles[J]. Acta Polymerica Sinica, 2015,(8):941-949.
梁静静, 叶誉贤, 王海平, 王陈旻, 徐立新. 核壳型Fe3 O4@SiO2磁性纳米粒子表面超支化聚乙烯共价接枝研究[J]. 高分子学报, 2015,(8):941-949. DOI: 10.11777/j.issn1000-3304.2015.14447.
Jing-jing Liang, Yu-xian Ye, Hai-ping Wang, Chen-min Wang, Li-xin Xu. Covalently Grafting Hyperbranched Polyethylenes onto Core-Shell Fe3O4@SiO2 Magnetic Nanoparticles[J]. Acta Polymerica Sinica, 2015,(8):941-949. DOI: 10.11777/j.issn1000-3304.2015.14447.
报道了一种利用超支化聚乙烯(HBPE)对磁性纳米粒子表面进行共价修饰的方法.首先通过反相微乳液法合成表面包覆SiO2的磁性Fe3O4纳米粒子(Fe3O4@SiO2
简记为FS)
并利用偶联剂3-丙烯酰基氧基丙基三氯硅烷对其进行改性
然后与-二亚胺钯催化剂(Pd-diimine
1)反应
获得磁性粒子共价负载型催化剂(FS-Pd);进一步以所得催化剂在0.1 MPa和15 ℃下催化乙烯聚合
获得一系列表面HBPE共价接枝的磁性复合粒子(FS-HBPE).通过红外光谱(FTIR)、热重分析(TGA)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射(XRD)、氢核磁共振波谱(1H-NMR)和凝胶渗透色谱(GPC)等技术对所得磁性复合粒子的结构和形貌进行了表征
并对其磁性能进行了评价.结果表明:通过表面引发/催化的链行走乙烯聚合
可成功实现HBPE在磁性纳米粒子表面共价接枝
通过聚合时间的改变
可对表面HBPE接枝率进行有效调控;所得FS-HBPE复合粒子呈超顺磁特征
借助HBPE的作用
可稳定分散于多个有机溶剂中
同时可实现快速磁控分离.基于上述优点
所得FS-HBPE磁性复合粒子可望用作贵金属催化剂载体
在相关有机反应中获得应用.
A strategy is reported herein to covalently graft hyperbranched polyethylenes (HBPEs) onto magnetic nanoparticles(NPs).Core-shell Fe3O4@SiO2 magnetic NPs (FS) were first synthesized via a reverse microemulsion method and then surface modified with a coupling agent
3-acryloxypropyltrichlorosilane
to render acryloyl-functionalized FS (FS-Acryl).The resulting FS-Acryl was further reacted with a Pd-diimine catalyst
[(ArN C(Me)-(Me)C NAr)Pd(Me)(NCMe)]+SbF6- (1)
to give a FS-supported Pd-diimine catalyst (FS-Pd).Surface-initiated/catalytic ethylene polymerization was then carried out with the FS-Pd at 0.1 MPa/15 ℃ for different periods
finally rendering a series of HBPE-grafted FS hybrids (FS-HBPE).The structure and morphology of the as-synthesized FS-HBPE were characterized with Fourier-transformed infrared (FTIR) spectroscopy
thermogravimetry analysis (TGA)
transmission electron microscopy (TEM)
scanning electron microscopy (SEM)
wide-angle X-ray diffraction (WAXRD)
proton nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC)
and their magnetic performance was also evaluated.It is well confirmed that HBPE can be successfully grafted onto FS via the surface-initiated/catalytic chain walking ethylene polymerization
with effectively adjustable polymer grafting ratio simply by changing polymerization time.The resulting FS-HBPE is found to be superparamagnetic and can be stably dispersed in a series of organic solvents at room temperature
with excellent magnetic reponse performance.With these advantages
the resulting FS-HBPE nanocomposites could be potentially used as catalyst supports for various organic reactions.
磁性纳米粒子超支化聚乙烯表面共价接枝-二亚胺钯催化剂磁控响应性能
Magnetic nanoparticlesHyperbranched polyethyleneSurface covalent graftPd-diimine catalystMagnetic response performance
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