Architecture of rod–brush block copolymers synthesized by a combination of coordination polymerization and atom transfer radical polymerization

A combination of coordination polymerization and atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod–brush block copolymers. The procedure included the following steps: (1) the monoesterification reaction of ethylene glycol with 2‐bromoisobutyryl bromide (BIBB) yielded the bifunctional initiator monobromobutyryloxy ethylene glycol and (2) a trichlorocyclopentadienyl titanium (CpTiCl 3 ; bifunctional initiator) catalyst was prepared from a mixture of CpTiCl 3 and bifunctional initiator. The coordination polymerization of n ‐butyl isocyanate initiated by such a catalyst provided a well‐defined macroinitiator, poly( n ‐butyl isocyanate)–bromine (PBIC–Br). (3) The ATRP method of 2‐hydroxyethyl methacrylate initiated by PBIC–Br provided rod [poly( n ‐butyl isocyanate) (PBIC)]–coil [poly(2‐hydroxyethyl methacrylate) (PHEMA)] block copolymers with a CuCl/CuCl 2 /2,2′‐bipyridyl catalyst. (4) The esterfication of PBIC‐ block ‐PHEMA with BIBB yielded a block‐type macroinitiator, and (5) ATRP of methyl methacrylate with a block‐type macroinitiator provided rod–brush block copolymers. We found from the solution properties that such rod–brush block copolymers formed nanostructured macromolecules in solution. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008