Synthesis and Properties of Novel Cross‐Linked Fluoroalkyl End‐Capped Oligomeric Nanoparticles Containing Adamantane Units

Abstract

AbstractFluoroalkyl end‐capped cooligomers that contain both oxime‐blocked isocyanato and hydroxyadamantyl segments are prepared by the cooligomerization of fluoroalkanoyl peroxide with the corresponding monomers under mild conditions. This fluorinated cooligomer affords new cross‐linked fluoroalkyl end‐capped cooligomeric nanoparticles that contain adamantane segments by the deprotecting reaction of oxime‐blocked isocyanato segments in cooligomers in excellent to moderate isolated yield. A variety of cross‐linked fluoroalkyl end‐capped cooligomeric nanoparticles that contain adamantane segments are also prepared by similar deprotecting reactions with this fluorinated cooligomer in the presence of adamantane‐1,5‐diol. Furthermore, we have prepared cross‐linked fluoroalkyl end‐capped cooligomers that contain oxime‐blocked isocyanato segments by the use of 2‐hydroxyethyl acrylate and poly(ethylene glycol)‐containing methacrylate monomer as comonomers, respectively. However, the deprotecting reactions of the oxime‐blocked isocyanato segments in the cooligomers do not afford the expected nanoparticles, and these cross‐linked cooligomers are found to show a gelling characteristic. The thermal stability of these cross‐linked fluorinated cooligomeric nanoparticles that contain adamantane segments increases significantly compared to that of the parent fluorinated cooligomer. More interestingly, the thermal stability of these cross‐linked fluorinated nanoparticles is almost the same as that of the fluoroalkyl end‐capped acrylic acid oligomer/SiO2 nanocomposites (content of SiO2 in composites: 70%). In addition, these cross‐linked fluorinated nanoparticles have been applied to the surface modification of traditional organic polymers such as poly(methyl methacrylate) to exhibit a good oleophobicity imparted by fluorine on their surface.magnified image