A series of poly(sodium 4-styrenesulfonate) (NaPSS) combs has been synthesized. Architecturally and molecularly well-defined polystyrene combs were initially produced with the branch molecular mass fixed at 30,000 g/mol, the average number of branches being the major variable. Conditions were established whereby linear polystyrene (PS) synthesized via anionic polymerization was chloromethylated using zinc (11) chloride, side-reactions such as Friedel-Crafts alkylation being suppressed. An excess of diphenylethylene-capped polystyryllithium (PSLi) was then reacted with the functionalized backbone to yield materials having long chain branches. The polystyrene combs were then reacted with sulfuric acid to yield water-soluble poly (styrenesulfonic acid) combs and subsequently neutralized with sodium hydroxide to give the corresponding sodium 4-styrene sulfonate species. The extent of sulfonation was determined via titration and nuclear magnetic resonance spectroscopy (NMR). Aqueous triple-detector size exclusion chromatography (SEC) was used to characterize the sulfonated combs. Although the SEC traces were monomodal and the M-n values agreed well with the expected values, an increase in the polydispersity index compared to the polystyrene combs may reflect the susceptibility of the sulfonation reaction to cross-linking. (c) 2006 Elsevier Ltd. All rights reserved.