Development of Fluorinated Polymeric Functional Materials Using Fluorinated Organic Peroxide as Key Material
Development of Fluorinated Polymeric Functional Materials Using Fluorinated Organic Peroxide as Key Material
复制标题
DOI：
10.1295/polymj.pj2006242
复制
发表时间：
2007-07
期刊：
影响因子：
2.8
通讯作者：
H. Sawada
中科院分区：
文献类型：
--
作者：
H. Sawada
氟代过氧化烷酰[RF-C（=O）OO（O=）C-RF]通过三键自由基的协同断裂均裂，选择性地生成氟代烷基自由基（RF·），而相应的过氧化烷酰[R-C（=O）OO（O=）C-R]通过逐步自由基的断裂均裂，生成酰氧基自由基[R-C（=O）O·]和烷基自由基[R·]。将氟代烷酰基过氧化物的这种分解应用于乙烯基硅烷低聚物和（甲基）丙烯酸酯低聚物的两个末端位点的直接氟烷基化。将所得氟烷基封端的三甲氧基乙烯基硅烷低聚物[RF-（CH_2CH_Si（OMe）_3）_n-RF]应用于玻璃和传统有机聚合物如PMMA和橡胶的表面改性，不仅表现出强的疏水性，而且具有良好的氟赋予的疏油性，在其表面具有极高的粘合性能。氟烷基封端的丙烯酸酯和甲基丙烯酸酯低聚物显示出与低分子量含氟表面活性剂相同的氟赋予的表面活性性质，并且这些含氟低聚物在水和有机介质中形成纳米尺寸控制的自组装分子聚集体。这些氟化分子聚集体与各种客体分子如低分子生物杀灭剂、富勒烯和碳纳米管相互作用，以提供相应的氟化低聚物/客体分子纳米复合物。将这些含氟低聚物应用于制备含氟低聚物/硅胶纳米复合材料和交联含氟低聚物纳米颗粒。
Fluoroalkanoyl peroxide [RF-C(=O)OO(O=)C-RF] decomposes homolytically through concerted three bond radical fission to afford fluoroalkyl radical (RF·) selectively, although the corresponding alkanoyl peroxide [R-C(=O)OO(O=)C-R] decomposes homolytically through stepwise radical fission to afford acyloxy radical [R-C(=O)O·] and alkyl radical [R·]. This decomposition of fluoroalkanoyl peroxide was applied to the direct fluoroalkylation of two end-sites of vinylsilane oligomers and (meth)acrylate oligomers. Fluoroalkyl end-capped trimethoxyvinylsilane oligomers [RF-(CH2CHSi(OMe)3)n-RF] thus obtained were applied to the surface modification on glass and traditional organic polymers such as PMMA and rubbers to exhibit not only strong hydrohobicity but good oleophobicity imparted by fluorine with extremely higher adhesive property on their surface. Fluoroalkyl end-capped actylate and methacrylate oligomers exhibited surface active properties imparted by fluorine, the same as for low-molecular weight fluorinated surfactants, and these fluorinated cooligomers formed the nanometer size-controlled self-assembled molecular aggregates in aqueous and organic media. These fluorinated molecular aggregates interacted with a variety of guest molecules such as low molecular biocides, fullerenes, and carbon nanotubes to afford the corresponding fluorinated oligomers/guest molecules nanocomposites. These fluorinated oligomers were applied to the preparation of fluorinated oligomers/silica gel nanocomposites and cross-linked fluorinated oligomeric nanoparticles.