Hyperbranched Multiarm Copolymers with a UCST Phase Transition: Topological Effect and the Mechanism.

A novel thermoresponsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly[3-ethyl-3-(hydroxymethyl)oxetane] core and many poly(acrylamide- co-acrylonitrile) (P(AAm- co-AN)) arms was for the first time synthesized through a reversible addition-fragmentation chain-transfer polymerization. These copolymers show reversible, sharp, and controlled temperature-responsive phase transitions at the upper critical solution temperature (UCST) in water and electrolyte solution. It is the first report on the hyperbranched copolymers with a UCST transition. Two series copolymers with variable AN content (series A) and variable arm length (series B) were synthesized to study the influence of molecular structure on the UCST transition. It was found that the UCST of copolymers could be raised by increasing the AN content or decreasing the arm length. Most interestingly, the amplification effect of the hyperbranched topological structure leads to a broad change of the UCST from 33.2 to 65.2 °C with the little change of AN content (5.9%). On the basis of variable temperature nuclear magnetic resonance, dynamic light scattering, and transmission electron microscopy, a UCST transition mechanism, in combination with hydrophilic/hydrophobic balance and multimicelle aggregate (MMA), was proposed. This work enriches the UCST copolymer topology and may extend the knowledge on the structure-activity relationship as well as the mechanism of the UCST polymers.