Synthesis of polyethylene oxide end‐capped with perfluoroalkyl groups/polystyrene prototype brushes

Polystyrene (PS)/poly(ethylene oxide) (PEO) prototype brushes were prepared by alternating free‐radical copolymerization of methacryloyl‐terminated PS and α‐vinylbenzyl‐ω‐hydroxy or α‐vinylbenzyl‐ω‐perfluoroalkyl (R f ) PEO macromonomers with the addition of Lewis acid (SnCl 4 ). It was found from their dilute‐solution properties that PS/PEO end‐capped with R f (PBR f ), and PS/PEO having OH groups at terminal ends (PBOH) prototype brushes formed a single molecule in benzene and aggregates in chloroform, respectively. However, the brush PBOH formed a single molecule in N,N‐ dimethylformamide. Such aggregation behaviors seemed to be caused by the interaction between hydroxy groups of PEO chain ends. The brush PBOH was also converted into PBR f ‐type brush by chemical modification, using corresponding acid chloride. The substitution of R f groups was ∼70% due to slipping of terminal hydroxy groups into PEO internal domains. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 772–778, 2006