Connal, Luke A.Vestberg, RobertGurr, Paul A.Hawker, Craig J.Qiao, Greg G.2025-12-182025-12-180743-7463WOS:000252208200034PubMed:18081331ORCID:/0000-0001-7519-977X/work/167653507https://hdl.handle.net/1885/733796675The effect of class transition temperature, T., 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 degrees 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 T-g below 48 degrees C could form homogeneous honeycomb coatings on the surface of nonplanar substrates.7enLiving radical polymerizationGlass-transition temperaturesCross-linking macromonomersThin-filmsBlock-copolymersPolymersMicrogelsLithographyPolystyreneMembranes2008-01-1510.1021/la702495p38749152414