Synthesis of an oligo(ethylene glycol)‐based third‐generation thermoresponsive dendronized polymer

An improved strategy to synthesize oligo(ethylene glycol)‐based secondary generation (G2) dendron is presented. The overall synthesis efficiency increased by 50% when comparing to the previous method, and the product purification by column chromatography becomes much easier. Based on this approach, the synthesis of the third‐generation (G3) dendrons and the corresponding methacrylate‐based G3 macromonomer becomes feasible. Because of the oil characteristics of this macromonomer, its polymerization was able to be conducted in bulk with AIBN as the initiator. The polymerization degree of the third‐generation dendronized polymer ( PG3 ) was found to be around 16 based on GPC measurement. The thermally induced dehydration processes of this polymer were monitored by temperature‐varied proton NMR spectroscopy, and its thermoresponsive behaviors were investigated with turbidity measurements using UV–vis spectroscopy. Similar to the lower generation counterparts, this threefold branched dendronized polymer also shows characteristic fast and sharp phase transitions around its apparent lower critical solution temperature. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6630–6640, 2009