Synthesis of self-assembled fluoroalkyl end-capped oligomeric aggregates—Applications of these aggregates to fluorinated oligomeric nanocomposites

Abstract

Fluoroalkanoyl peroxide is a useful tool for the preparation of ABA triblock-type fluoroalkylated oligomers [R F–(M) n –R F] by the reaction of the peroxide with a wide variety of radical polymerizable monomers under very mild conditions. Fluoroalkanoyl peroxide is also applied to the preparation of new dendritic fluoroalkyl end-capped polymers. Usually, it is well known that longer fluoroalkylated compounds exhibit a strong repellent property against water or hydrocarbons owing to the strong electronegativity of fluorine; however, end-capped fluoroalkyl groups in these fluorinated oligomers could aggregate easily each other rather than have repellent interactions in aqueous or organic media to afford nanometer size-controlled self-assembled molecular aggregates in these media. Interestingly, these fluorinated molecular aggregates could interact with a variety of guest molecules such as organic dyes, low-molecular biocides, metal nanoparticles, calcium carbonates, fullerenes, single-walled carbon nanotubes, nanodiammond and magnetites to afford stable fluorinated molecular aggregates-guest molecules nanocomposites. More interestingly, these fluorinated nanocomposites were applied to the surface modification of traditional organic polymers such as poly(methyl methacryalte) (PMMA) to exhibit not only a good surface active property imparted by fluorine but also a unique characteristic related to the guest molecules on their surface. Additionally, fluoroalkyl end-capped oligomers were applied to the preparation of fluoroalkyl end-capped oligomers-silica nanoparticles by the reactions of the corresponding oligomers with tetraethoxysilane and silica nanoparticles under alkaline conditions.