Development of Fluorinated Polymeric Functional Materials Using Fluorinated Organic Peroxide as Key Material

Abstract

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.