Mild and Efficient Preparation of Block and Gradient Copolymers by Methanesulfonic Acid Catalyzed Ring-Opening Polymerization of Caprolactone and Trimethylene Carbonate

• Published in: Macromolecules Vol. 46; no. 11; pp. 4354 - 4360
• Main Authors: Couffin, Aline, Delcroix, Damien, Martín-Vaca, Blanca, Bourissou, Didier, Navarro, Christophe
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 11.06.2013
• Subjects: Applied sciences; Copolymerization; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; Catalytic reaction; Mild operating conditions; Solution copolymerization; Acid catalysis; Experimental study; Sulfonic acid; Primary alcohol; Triblock copolymer; Caprolactone copolymer; Preparation; Diblock copolymer; Carbonate copolymer; Ring opening copolymerization; Aliphatic copolymer
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma400916k

Polycaprolactone/polytrimethylene carbonate copolymers of different microstructures have been prepared in toluene solution under mild conditions by controlled ring-opening polymerization of ε-caprolactone and trimethylene carbonate with methanesulfonic acid as catalyst. Sequential addition of the monomers led to the formation of well-defined di- and tri-block copolymers, demonstrating the ability of the catalytic system to cross-propagate. Simultaneous copolymerization yielded gradient copolymers as a result of the different copolymerization reactivity ratios and absence of undesirable redistribution reactions. DSC analyses showed a noticeable impact of the copolymer microstructure on the thermal properties.