Atom transfer radical polymerization of solketal acrylate using cyclohexanone as the solvent

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 NHCl/THF (1/9, v/v) at room temperature to form a poly(glycerol mono-acrylate) 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.