Novel thermoresponsive fluorinated double-hydrophilic poly{[N-(2,2-difluoroethyl)acrylamide]-b-[N-(2-fluoroethyl)acrylamide]} block copolymers

Novel thermoresponsive double‐hydrophilic fluorinated block copolymers were successfully synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Poly[N‐(2,2‐difluoroethyl)acrylamide] (P2F) was synthesized via RAFT polymerization of N‐(2,2‐difluoroethyl)acrylamide (M2F) using 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methylpropionic acid (DMP) as the chain transfer agent (CTA) and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. The resulting P2F macroCTA was further chain extended with N‐(2‐fluoroethyl)acrylamide (M1F) to yield poly{[N‐(2,2‐difluoroethyl)acrylamide]‐b‐[N‐(2‐fluoroethyl)acrylamide]} (P2F‐b‐P1F) block copolymers with different lengths of the P1F block. Molecular weight and molecular weight distribution were determined by gel permeation chromatography. The average molecular weight (Mn) of the resulting polymers ranged from 2.9 × 104 to 5.8 × 104 depending on the length of the P1F block. The molecular weight distribution was low (Mw/Mn = 1.11–1.19). Turbidimetry by UV‐Visble (UV‐Vis) spectroscopy, dynamic light scattering, and in situ temperature‐dependent 1H NMR measurements demonstrated that the P2F block underwent a thermal transition from hydrophilic to hydrophobic, which in turn induced self‐assembly from unimers to aggregates. Transmission electron microscopy studies demonstrated that polymeric aggregates formed from an aqueous solution of P2F‐b‐P1F at 60 °C were disrupted by cooling down to 20 °C and regenerated by heating to 60 °C. Temperature‐triggered release of a model hydrophobic drug, coumarin 102, was also demonstrated. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 Novel thermoresponsive double‐hydrophilic fluorinated block copolymers, poly{[N‐(2,2‐difluoroethyl)acrylamide]‐b‐[N‐(2‐fluoroethyl)acrylamide]} (P2F‐b‐P1F), were successfully synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Mono‐fluorine substituted poly[N‐(2‐fluoroethyl)acrylamide] (P1F) is water‐soluble while di‐fluorine substituted poly[N‐(2,2‐difluoroethyl)acrylamide] (P2F) exhibits an LCST in water around 26–28 °C. Temperature‐induced formation and disruption of nanoaggregates were achieved by virtue of the thermoresponsive nature of the P2F block. Temperature‐triggered release of a model hydrophobic drug, coumarin 102, was also demonstrated.