Is a “Cloud-Point Curve” in Aqueous Poly(N-isopropylacrylamide) Solution Binodal?

Transmittance of light passing through an aqueous solution of a linear poly(N-isopropylacrylamide) (PNIPA) sample synthesized by living anionic polymerization was examined in detail in the vicinity of its cloud point. It is found that the transmittance approaches a constant value between 0 and 100% even at a temperature slightly higher than the cloud point, indicating that macroscopic phase separation does not take place at the cloud point in the solution and therefore the cloud-point curve dose not correspond to the binodal. Static and dynamic light scattering measurements were then carried out for aqueous solutions of the linear sample and also of another one synthesized by radical polymerization, which has random-branched structure, at some temperatures considerably lower than the cloud point. It was found that both the PNIPA samples in aqueous solutions form aggregates even at such temperatures, and the number, size, and density profile of the aggregates depend on the kind of chain end group and also on the primary structure.