Synthesis and application of novel fluoroalkyl end-capped cooligomers having adamantane as a pendant group

Abstract

Fluoroalkyl end-capped cooligomers having adamantane as a pendant group [RF-(Ad-HAc)x–(Co-M)y-RF] were prepared by the reactions of fluoroalkanoyl peroxide with 3-hydroxy-1-adamantylacrylate (Ad-HAc) and comonomers (Co-M) such as acrylic acid (ACA), N,N-dimethylacrylamide (DMAA), and acryloylmorpholine (ACMO) under mild conditions. Thermogravimetric analyses (TGA) showed that thermal stability of RF-(Ad-HAc)x–(Co-M)y-RF was superior to that of the corresponding fluoroalkyl end-capped cooligomers having adamantane in the main chains [RF-(Ad)x–(Co-M)y-RF] and the fluoroalkyl end-capped homooligomers possessing no adamantyl segments [RF-(M)n-RF]. It is interesting to note that fluoroalkyl end-capped Ad-Hac–DMAA cooligomer [RF-(Ad-HAc)x–(DMAA)y-RF] was found to form the nanometer size-controlled cooligomeric aggregates which consist of around 16 fluorinated cooligomeric molecules in methanol/water mixed solvents. Furthermore, these fluorinated cooligomeric aggregate could occupy around 320 ADMDD [5-(2-adamantylidene)-2,2-dimethyl-1,3-dioxane-4,6-dione] molecules as guest molecules per aggregate core, although ADMDD could not be encapsulated into the RF-(Ad)x–(Co-M)y-RF cooligomeric and RF-(M)n-RF homooligomeric aggregate cores under similar conditions.