Syntheses and Specific Interactions of Poly( ε ‐caprolactone)‐ block ‐poly(vinyl phenol) Copolymers Obtained via a Combination of Ring‐Opening and Atom‐Transfer Radical Polymerizations

Summary: A series of PCL‐ b ‐PVPh diblock copolymers were prepared through combinations of ring‐opening and atom‐transfer radical polymerizations of ε ‐caprolactone and 4‐acetoxystyrene, and subsequent selective hydrolysis of the acetyl protective group. This PCL‐ b ‐PVPh diblock copolymer shows a single glass transition temperature over the entire composition range, indicating that this copolymer is able to form a miscible amorphous phase due to the formation of intermolecular hydrogen bonding between the hydroxyl of PVPh and the carbonyl of PCL. In addition, DSC analyses also indicated that the PCL‐ b ‐PVPh diblock copolymers have higher glass transition temperatures than their corresponding PCL/PVPh blends. FT‐IR was used to study the hydrogen‐bonding interaction between the PVPh hydroxyl group and the PCL carbonyl group at various compositions.FT‐IR spectra in the 1 680–1 780 cm −1 for PCL‐ b ‐PVPh copolymers with various PVPh contents.