Thermoresponsive properties of 3-, 4-, 6-, and 12-armed star-shaped poly[2-(dimethylamino)ethyl methacrylate]s prepared by core-first group transfer polymerization

The t-Bu-P4-catalyzed group transfer polymerization (GTP) of 2-(dimethylamino)ethyl methacrylate (DMAEMA) using multi-functional GTP initiators that bear multiple silyl ketene acetal moieties (MTS3, MTS4, MTS6, and MTS12) homogeneously proceeded and rapidly completed to afford well-defined star-shaped poly[2-(dimethylamino)ethyl methacrylate]s (s-PDMAEMAs) with relatively narrow polydispersities. The molecular weights (MWs) of s-PDMAEMAs were well-controlled by optimizing the molar ratios of the monomer to initiators. For the structural analyses, the arm number and length uniformity of each s-PDMAEMA were then investigated by arm cleavage experiments using a transesterification method. The thermoresponsive properties in an aqueous solution of the resulting s-PDMAEMAs together with their analogous linear PDMAEMAs (l-PDMAEMAs), in terms of polymer concentration, molecular weight, and arm number, were eventually elucidated based on turbidimetry curves.