In this thesis, the author describes versatile and easy-to-use
methods to control the properties of thermoresponsive
polyacrylamides by developing novel synthetic methods for
end-functionalized poly(N-isopropylacrylamide) (PNIPAM) and block
copolymers of poly(N,N-diethylacrylamide) (PDEAA). The synthesis of
various urea end-functionalized PNIPAMs was achieved by the atom
transfer radical polymerization (ATRP) and the click reaction. The
phase transition temperature of PNIPAM in water was controlled
depending on the strength of the hydrogen bonding of the urea
groups introduced at the chain end of the polymer. Novel living
polymerization methods for N,N-dimethylacrylamide and
N,N-diethylacrylamide were developed by group transfer
polymerization (GTP) using a strong Brønsted acid as a precatalyst
and an amino silyl enolate as an initiator. This process enabled
the precise synthesis of PDEAA and its block copolymers—namely,
thermoresponsive amphiphilic block copolymers and
double-hydrophilic block copolymers.
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