The Baylis–Hillman reaction,
which is a carbon–carbon
bond forming reaction between an aldehyde and an activated alkene,
was utilized to prepare densely functionalized monomers suitable for
chain and step polymerization. By reacting formaldehyde with various
alkyl acrylates, a series of alkyl α-hydroxymethyl acrylate
monomers were synthesized. These monomers efficiently underwent RAFT
polymerization to provide α-hydroxymethyl-substituted polyacrylates
with well controlled molecular weight and low polydispersity. The
resulting homopolymers were also efficient macro-chain transfer agents
for further RAFT polymerization. The Baylis–Hillman reaction
was also utilized to synthesize alkene functionalized diols which
underwent step-growth polymerization to provide polyesters and poly(ester
urethane)s. Furthermore, it was demonstrated that the alkene group
can be quantitatively functionalized by thiol–ene click chemistry
to provide a series of polymers with diverse physical properties.