Aggregation Behavior of Nonsymmetrically End-Capped Thermoresponsive Block Copolymers in Aqueous Solutions: Between Polymer Coils and Micellar States

The thermosensitive aggregation behavior in an aqueous solution of a library of amphiphilic BAB* copolymers is studied, where "A" represents a long permanently hydrophilic poly(N,N-dimethylacrylamide) (pDMAm) block, "B" represents a permanently hydrophobic end with an n-dodecyl chain, and "B*" represents a thermoresponsive (TR) block featuring a lower critical solution temperature (LCST). Four polyacrylamides are employed for B*, namely, poly(N-n-propylacrylamide) (pNPAm), poly(N-isopropylacrylamide) (pNiPAm), poly(N,N-diethylacrylamide) (pDEAm), and poly(N-acryloylpyrrolidine) (pNAP), which differ with respect to the hydrophilicity of their amide side chains and LCST behavior. While blocks A and B were kept constant, the lengths of the TR blocks were varied systematically. These amphiphilic copolymers were studied as a function of concentration and temperature via light and neutron scattering (static light scattering (SLS), dynamic light scattering (DLS), small-angle neutron scattering (SANS)). For sufficiently long pNiPAM and pDEAm blocks (DPn > 40), a pronounced hydrophobic effect at temperatures above the LCST transition results in well-structured, ordered aggregates. Thus, the aggregation can be controlled by the choice and length of the TR block, thereby elucidating a so far hardly explored class of temperature-sensitive polymeric amphiphiles.