Modularly prepared segmented fluorinated silicones and their anomalous microstructure dependent flow behavior†

Octafluorocyclopentene was used as a coupling reagent by undergoing a series of efficient and regio-controlled addition–elimination reactions with eugenol and alkyldiols/bisphenols to prepare terminally unsaturated monomers. Structural characterization revealed these high molecular weight monomers can be obtained with high purity and in multi-gram quantities with minimal purification. The eugenolic-based monomers underwent Pt-catalyzed hydrosilylations with hydride-terminated polydimethylsilane oligomers to prepare a versatile pool of segmented fluorosilicones. Polymer characterization included molecular weight determination, calorimetric studies, thermo-gravimetric analysis, and rheology. Of particular interest as next-generation lubricants for in-space applications, these fluorosilicones possess adaptable structure–property relationships by nature of the segment substitution.