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α-Functionalized acrylamides have not been considered as an effective monomer design due to their poor polymerizability, although the analogues, α-functionalized acrylates, are attractive monomers of which polymers exhibit characteristic properties. In this article, we report the first example of radical polymerization of α-functionalized N , N -disubstituted acrylamide affording thermo-responsive hydrophilic polymers. N , N -dimethyl-α-(hydroxymethyl)acrylamide (DMαHAA) was (co)polymerized with N , N -diethylacrylamide (DEAA). Although the homopolymerization did not afford a polymeric product, the copolymerizations with various feed ratios yielded a series of the copolymers containing 0%⁻65% of DMαHAA units. The obtained copolymers exhibited a lower critical solution temperature (LCST) in water; the cloud points ( T  c s) were linearly elevated as the contents of DMαHAA units from 32 to 64 °C, indicating that DMαHAA functioned as a more hydrophilic monomer than DEAA. The linear relationship between T  c and DMαHAA content suggests that the homopolymer, poly(DMαHAA), should have T  c at ca. 80 °C, although it is not available by direct radical homopolymerization.

Synthesis of Thermo-Responsive Polymer via Radical (Co)polymerization of N,N-Dimethyl-α-(hydroxymethyl)acrylamide with N,N-Diethylacrylamide