• atom transfer radical polymerization;
  • theoretical modeling coupled with experimental approachest;
  • fluorinated copolymers;
  • thermal property;
  • micellization;
  • surface property

Theoretical modeling coupled with an experimental study is presented for the preparation and characterization comparison of the amphiphilic copolymers of 2, 2, 3, 3, 4, 4, 4-heptafluorobutyl methacrylate (HFBMA) and 2-hydroxyethyl methacrylate (HEMA) to achieve a multiscale generalization of the polymeric system. A series of amphiphilic copolymers having different chain structures with HFBMA as the hydrophobic component and HEMA as the hydrophilic component was first synthesized through atom transfer radical copolymerization (ATRcoP) or model-based semibatch ATRcoP. Theoretical modeling is used to optimize the macromolecular structure and experimental approaches that are used to prepare copolymers of HFBMA and HEMA with some tailor-made polymer properties. Furthermore, a systematic comparison of major properties (i.e., thermal, micellization, and surface properties) of these fluorinated copolymers (i.e., random, block, linear gradient, and inverse linear gradient copolymers) was carried out. The results show that these fluorinated copolymers with different chain structures have dissimilar properties. The results also demonstrate that the approach of coupling theoretical modeling with an experimental study can be used to guide a multiscale generalization of the polymeric system for practical application. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3019–3033, 2013