Abstract: | An amphiphilic styrenic block copolymer, polystyrene‐block‐polybutadiene‐block‐poly[oxymethylene‐alt‐oligo(oxyethylene)] (PS‐b‐PB‐b‐POME), was synthesized through a polycondensation reaction of low molecular weight poly(ethylene glycol) and dichloromethane in the presence of hydroxypropylated polystyrene‐block‐polybutadiene (PS‐b‐PB‐OH) used as a monofunctional chain‐capping reagent. PS‐b‐PB‐OH was in turn prepared via an anionic synthesis of PS‐b‐PB followed by oxetane capping and methanol quenching. Although PS‐b‐PB‐OH has insignificant hydrophilicity, PS‐b‐PB‐b‐POME containing both the hydrophobic PS‐b‐PB segment and the hydrophilic POME segment had an improved emulsifying capability and effectively decreased the interfacial tension between water and toluene. The hydrophile–lipophile balance value of this amphiphilic PS‐b‐PB‐b‐POME copolymer, consisting of 86 wt % of the POME segment and 14 wt % of the PS‐b‐PB segment, was 17.2. The molecular weight of the copolymer molecule was determined by gel permeation chromatography–multi‐angle laser light scattering, and the microstructure was analyzed using 1H NMR. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2625–2632, 2001 |