Synthesis and properties of novel fluoroalkyl end-capped oligomers containing phosphorus segments

Abstract

New fluoroalkyl end-capped oligomers containing pendant phosphoric acid groups wereprepared by the reactions of the corresponding monomer with fluoroalkanoyl peroxides. It was demonstrated that not only strong aggregations of fluoroalkyl segments but also hydrogen bonding could interact synergistically to form the highly viscoelastic fluids (gel-like fluids) in aqueous solutions of these new fluoroalkyl end-capped oligomers containing pendant phosphoric acid groups. Furthermore, these oligomers were able to reduce the surface tension of water effectively to exhibit a clear breakpoint resembling a CMC, and the modified stainless-steel surface treated with these oligomers was shown to possess an excellent property imparted by fluorine. More interestingly, these oligomers were found to be potent and selective inhibitors against HIV-1 replication in vitro. New fluoroalkyl end-capped phosphonic acid and phosphonate oligomers were also prepared by the reactions of the corresponding phosphonic acid and phosphonate monomers, respectively, by the use of fluoroalkanoyl peroxides. These new fluoroalkyl end-capped phosphonic acid and phosphonate oligomers were found to have a higher solubility in not only water but also in common organic solvents than that of the corresponding fluorinated oligomers containing pendant phosphoric acid groups, and these new oligomers were able to reduce the surface tension of these solvents quite effectively. Thus, these oligomers are expected to develop as new fluorinated oligosurfactants. Moreover, the modified poly(methyl methacrylate) surface treated with these phosphonate oligomers was clarified to exhibit a good oil-repellency imparted by fluorine. In addition, fluoroalkyl end-capped phosphonate homo- and cooligomers were found to form monomolecular films at the air–water interface. Therefore, these fluorinated oligomers are suggested to have high potential for new functional materials through not only their excellent properties imparted by both fluorine and phosphorus, but also through their biological properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 228–245, 2001