Synthesis of PCL-b-PVAc block copolymers by combination of click chemistry, ROP, and RAFT polymerizations

• Published in: Polymer bulletin (Berlin, Germany) Vol. 68; no. 3; pp. 607 - 621
• Main Authors: Glaied, Olfa, Delaite, Christelle, Riess, Gérard
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer-Verlag 01-02-2012; Springer; Springer Nature B.V; Springer Verlag
• Subjects: Addition polymerization; Alkynes; Anionic polymerization; Applied sciences; Block copolymers; Chain transfer; Characterization and Evaluation of Materials; Chemical Sciences; Chemical synthesis; Chemistry; Chemistry and Materials Science; Complex Fluids and Microfluidics; Copolymers; Exact sciences and technology; Hydroxyl groups; Initiators; Molecular weight; NMR; Nuclear magnetic resonance; Organic Chemistry; Organic polymers; Original Paper; Physical Chemistry; Physicochemistry of polymers; Polycaprolactone; Polymer Sciences; Polymerization; Polymers; Polyvinyl acetates; Preparation, kinetics, thermodynamics, mechanism and catalysts; Ring opening polymerization; Size exclusion chromatography; Soft and Granular Matter; Termination (polymerization); Vinyl acetate; Poly(ε-caprolactone); ROP; RAFT; Click chemistry; Block copolymers; Poly(vinyl acetate); Ring opening polymerization; 1,3-Dipolar cycloaddition; Lactone copolymer; Vinyl ester copolymer; Experimental study; Lactone polymer; Initiator polymer; Free radical polymerization; Chain transfer; Vinyl acetate copolymer; Caprolactone copolymer; Vinyl acetate polymer; Aliphatic polymer; Preparation; Anionic polymerization; Polycaprolactone; Vinyl ester polymer; Block copolymer; copolymers; click chemistry; polymerizations; PCL-b-PVAc
• ISSN: 0170-0839; 1436-2449
• DOI: 10.1007/s00289-011-0557-1

The synthesis of new poly(ε-caprolactone)(PCL)-
b
-poly(vinyl acetate)(PVAc) block copolymers was investigated using different combinations of click chemistry, reversible addition-fragmentation transfer (RAFT), and ring opening polymerization (ROP) techniques. Two approaches, “coupling” and “macroinitiator” routes were studied. For the coupling approach, a chain transfer agent comprising an azide function was synthesized and used as initiator for the VAc polymerization. PCL containing an alkyne termination was obtained from a bifunctional initiator bearing an alkyne function and an hydroxyl group. These two functionalized precursors, PVAc and PCL, were coupled by a 1,3 cyclo addition reaction “click chemistry” in order to obtain the corresponding block copolymer. For the macroinitiator approach, PCL-
b
-PVAc block copolymers were synthesized using a two-step procedure: at first, a PCL macroinitiator with a xanthate end group was prepared by coordinated anionic polymerization of ε-caprolactone; then, the RAFT polymerization of VAc was initiated from the PCL, for the preparation of PCL-
b
-PVAc block copolymers. Whatever the method used, no detectable quantities of unreacted PVAc or PCL were observed.
1
H NMR and size exclusion chromatography analyses indicated successful synthesis of the block copolymers with well-defined structures.
Graphical abstract