The thermoresponsive behavior of a poly(2-oxazoline)-based molecular brush is investigated in aqueous solution. The molecular brush under study, PiPOx 100-g-PEtOx 17 , has a poly(2-isopropenyl-2-oxazoline) (PiPOx) backbone grafted with thermoresponsive poly(2-ethyl-2-oxazoline) (PEtOx) side chains. Since the backbone degree of polymerization is only a factor of~6 higher than the ones of the side chains, it features an architecture between a star-like polymer and a comb-like polymer. Its aqueous solution exhibits lower critical solution temperature (LCST) behavior with a cloud point temperature T cp = 40.5°C at 30 g L −1. The temperature-dependent structural evolution is disclosed using dynamic light scattering (DLS) and small-angle neutron scattering (SANS). An increase of the molecular brush size is found upon heating from room temperature to T cp , which is attributed to the extension of the backbone resulting from the dehydration and collapse of the side chains. Above T cp , the size decreases again, which indicates the collapse of the whole molecular brush. Large aggregates are found to be present in the solution in the temperature range 25-50°C. These become more compact, as the temperature is increased across T cp .
The structures of a molecular brush in a good solvent are investigated using synchrotron small-angle X-ray scattering in a wide range of concentrations. The brush under study, PiPOx 239 -g-PnPrOx 14 , features a relatively long poly(2-isopropenyl-2-oxazoline) (PiPOx) backbone and short poly(2-n-propyl-2-oxazoline) (PnPrOx) side chains. As a solvent, ethanol is used. By model fitting, the overall size and the persistence length as well as the interaction length and interaction strength are determined. At this, the interplay between form and structure factor is taken into account. The conformation of the molecular brush is traced upon increasing the solution concentration, and a rigid-to-flexible transition is found near the overlap concentration. Finally, the results of computer simulations of the molecular brush solutions confirm the experimental results.
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