Summary: Solketal acrylate (SA) was homopolymerized by atom transfer radical polymerization (ATRP) using CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine as the catalyst and cyclohexanone as the solvent with controlled molecular weights and low polydispersities. The prepared bromine‐terminated homopolymers, PSA, were used as macroinitiators to initiate polymerization of tert‐butyl acrylate (tBA) under similar ATRP conditions to produce diblock copolymers, PSA‐b‐PtBA, with controlled molecular weights and low polydispersities. ATRP of SA using bromine‐terminated PtBA as the macroinitiator was also carried out and diblock copolymers, PtBA‐b‐PSA, were obtained. The PSA block was selectively hydrolyzed by stirring for 3 h in 6 N HCl/THF (1/9, v/v) at room temperature to form a poly(glycerol monoacrylate) block. Both blocks of PSA and PtBA were hydrolyzed by stirring in anhydrous trifluoroacetic acid (TFA)/dichloromethane for 4 h, then adding water to the system and stirring for another 3 h to form corresponding diblock copolymers of glycerol monoacrylate and acrylic acid.
Kinetic plot for the atom transfer radical polymerization of solketal acrylate at 90 °C.
