Combination of coordination polymerization and atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod‐coil block copolymers. The procedure included the following steps: (1) monoesterification reaction of ethylene glycol with 2‐bromoisobutyryl bromide yielded a α‐bromo, ω‐hydroxy bifunctional initiator, (2) CpTiCl3 (bifunctional initiator) catalyst was prepared from a mixture of trichlorocyclopentadienyl titanium (CpTiCl3) and bifunctional initiator. Coordination polymerization of n‐butyl isocyanate initiated by such catalyst provided a well‐defined macroinitiator, poly(n‐butyl isocyanate)‐Br (PBIC‐Br), and (3) ATRP method of vinyl monomers using PBIC‐Br provided rod (PBIC)‐coil block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4037–4042, 2007

Well-defined poly(ethylene oxide)-blockpoly(n-butyl isocyanate) (PEO-block-PBIC; AB) diblock copolymers were prepared with trichloropentadienyl titanium (IV) (CpTiCl 3 ) catalyst. Ordered microporous films (hexagonal pattern) were constructed by emulsion micelles of A 110 B 230 diblock copolymer (the subscript indicates the degree of polymerization of each block component) formed from CHCl 3 /H 2 O/tetrahydrofuran (THF) 5 100/5/10 (v/v) solution. The addition of THF promoted uniform micelles in immiscible CHCl 3 /H 2 O mixed solvent as well as the effect of phase transfer catalyst. Diblock copolymers formed spherical micelles, consisting of a PEO core and a PBIC corona. At some concentration, interaction between micelles forced a disorder-order transition, resulting in freezing of micelles in some superlattice. Subsequently, the leaving gaps among micelles were filled by PBIC block chains on a corona through the evaporation of organic solvents. At last, water within hydrophilic PEO core was vomited through the film matrix. We also constructed the microporous films using A 110 B 230 diblock copolymer by the current water-assisted method.

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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 0 -bipyridyl catalyst. (4) The esterfication of PBICblock-PHEMA with BIBB yielded a block-type macroinitiator, and (5) ATRP of methyl methacrylate with a blocktype macroinitiator provided rod-brush block copolymers. We found from the solution properties that such rodbrush block copolymers formed nanostructured macromolecules in solution.