Patterning on Nonplanar Substrates: Flexible Honeycomb Films from a Range of Self-assembling Star Copolymers.

graphical abstract
Connal, Luke A.; Vestberg, Robert; Gurr, Paul A.;, Hawker, Craig J.; Qiao, Greg G.;
24, 556-562.

The effect of glass transition temperature, Tg, on the self-assembly of “honeycomb” microstructures on nonplanar substrates was probed by the synthesis of a library of core cross-linked star polymers with different arm compositions. Star polymers based on poly(dimethyl siloxane), poly(ethyl acrylate), poly(methyl acrylate), poly(tert-butyl acrylate), and poly(methyl methacrylate) were synthesized by the “arm first” strategy using atom-transfer radical polymerization. Reaction conditions were optimized, and a series of high molecular weight star polymers were prepared in high yield. The glass transition temperature of the star polymers ranged from −123 to 100 °C which allowed the suitability for the formation of porous honeycomb-like films via the “breath figure” technique on nonplanar surfaces to be investigated. All star compositions successfully formed ordered films on flat surfaces. However, only star polymer compositions with a Tg below 48 °C could form homogeneous honeycomb coatings on the surface of nonplanar substrates.