Influence of gradient strength and composition profile on the onset of the cloud point transition in hydroxyethyl methacrylate/dimethylaminoethyl methacrylate gradient copolymers

We examined the onset of the cloud point in dilute aqueous solutions of gradient copolymers of 2-hydroxyethyl methacrylate and dimethylaminoethyl methacrylate. Dynamic Light Scattering (DLS) and transmittance measurements both indicate that the copolymer solution cloud point decreases with increasing copolymer gradient strength, defined as the largest difference in the instantaneous composition along the copolymer. While transmittance measurements suggest that macroscopic clouding does not set in until 30% of the polymer chain becomes insoluble, DLS experiments, which are more sensitive to the onset of aggregation, indicate that the onset of aggregation occurs at the point where the least soluble polymer chain end becomes insoluble. Collectively, our data indicate that the macroscopic cloud point transition is highly sensitive to co-monomer sequence distribution of the copolymers, with its onset and transition breadth tunable through copolymer gradient strength.