Architectural Effects on the Solution Behavior of Linear and Star Polymers in Propane at High Pressures

A star polymer with a divinylbenzene core and statistically random methacrylate copolymer arms is synthesized with reversible addition–fragmentation–transfer method and fractionated with supercritical carbon dioxide and propane to obtain fractions with low molecular weight polydispersity. The phase behavior and density behavior are experimentally determined in supercritical propane for fractionated star polymers and the corresponding linear copolymer arms at temperatures to 423 K and pressures to 210 MPa. Experimental data are presented on the impact of the number of arms, the backbone composition of the lauryl and methyl methacrylate repeat units in the copolymer arms, and the divinylbenzene core on the polymer–propane solution behavior. The star polymer is significantly more soluble because of its unique structure compared with the solubility of the linear copolymer arms in propane. The resultant phase behavior for the two homopolymers and the copolymer arms in propane are modeled using the perturbed ch...