Atom transfer radical polymerization (ATRP) was applied to the synthesis of
amphiphilic cylindrical polymer brushes by using the "grafting from" techn
ique. The procedure included the following steps: (1) ATRP of 2-hydroxyethy
l methacrylate (HEMA) gave well-defined poly(HEMA), (2) subsequent esterifi
cation of the pendant hydroxy groups of poly(HEMA) with 2-bromoisobutyryl b
romide yielded a polyinitiator, poly(2-(2-bromoisobutyryloxy)ethyl methacry
late (PBIEM), (3) ATRP of various monomers (tent-butyl acrylate, or styrene
) using PBIEM as polyinitiator yielded cylindrical brushes with homopolymer
side chains, (4) addition of a second monomer (styrene or tent-butyl acryl
ate) formed the cylindrical brushes with diblock copolymer side chains (cor
e-shell cylinders), and (5) hydrolysis of the poly(tert-butyl acrylate) (Pt
BA) block of the side chains to poly(acrylic acid) (PAA) formed amphiphilic
core-shell polymer brushes. By using this technique, well-defined core-she
ll cylindrical polymer brushes with polystyrene (PS), PtBA, PS-b-PtBA, PtBA
-b-PS, PS-b-PAA, or PAA-b-PS as side chains were successfully synthesized.
The molecular weights and radii of gyration of the polymer brushes were obt
ained by static light scattering in THF. The absence of inter/intra-macromo
lecular coupling reactions during ATRP synthesis was confirmed by GPC, NMR,
and MALDI-TOF analyses of the side chains and scanning force microscopy (S
FM). Single wormlike unimolecular nanocylinders are clearly visualized on a
mica surface while aggregates are usually observed on a SiOx surface. The
brushes with PS-b-PtBA side chains were hydrolyzed to PS-b-PAA side chains
forming unimolecular wormlike micelles. These unimolecular micelles showed
a unique response to solvent quality, as indicated by H-1 NMR and dynamic l
ight scattering.