Brønsted acid‐catalyzed polymerization of ε‐caprolactone in water: A mild and straightforward route to poly(ε‐caprolactone)‐graft‐water‐soluble polysaccharides

The polymerization of e-caprolactone (e-CL) has been assessed in water using various Bronsted acids as catalysts. The reaction was found to be quantitative at 100 °C, leading to number–average molecular weights up to 5000 g mol−1. The Bronsted acid-catalyzed polymerization of e-CL in water was further conducted in the presence of water-soluble polysaccharides thereby affording graft copolymers. The approach enables an easy, mild access to dextran hydroxyesters. For low degree of substitution, the latter self-assembles in water to form nanoparticles. Poly(e-CL)-graft-methylcellulose copolymers can also be obtained via a similar approach. It is noteworthy that the methodology reported herein is a one-step route to poly(e-CL)-graft-water-soluble polysaccharides, operating in mild conditions, that is, at low temperatures, using readily available metal-free catalysts and water as a solvent. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2139–2145

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