Thermodynamics of Chain Architecture in Acrylic Block Terpolymers

• Published in: Macromolecules Vol. 47; no. 17; pp. 5960 - 5970
• Main Authors: Bergman, James A, Hernández, Nacú B, Cochran, Eric W, Heinen, Jennifer M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 09.09.2014
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma500905n

In this article, we report the manipulation of block terpolymer morphology through control of the segment distribution. We consider a model system comprised of three acrylic monomers: hydrophilic poly(hydroxyethyl acrylate) (H), hydrophobic poly(octyl acrylate) (O), and polar poly(methyl acrylate) (M). For each of four chemical compositions, we altered the M segment distribution in four terpolymer architectures with reversible addition–fragmentation chain transfer (RAFT) polymerization to yield: two triblock terpolymer architectures, HOM and HMO, and two diblock terpolymer architectures, HM/O and H/MO, where the M segments are statistically distributed in the O or H blocks, respectively. Using a combination of small-angle X-ray scattering and dynamic shear rheology, we illustrate how the monomer distribution can be used to manipulate the thermodynamic behavior of terpolymers at constant chemical composition. These results will be of use to those wishing to partially decouple the formulation of a block copolymer from its morphology.