3 years ago

Norbornene-functionalized PEO-b-PCL: A versatile platform for mikto-arm star, umbrella-like, and comb-like graft copolymers

Norbornene-functionalized PEO-b-PCL: A versatile platform for mikto-arm star, umbrella-like, and comb-like graft copolymers
Duc Anh N'Guyen, Laurent Fontaine, Sagrario Pascual, Sandie Piogé, Véronique Montembault
Well-defined in-chain norbornene-functionalized poly(ethylene oxide)-b-poly(ɛ-caprolactone) copolymers (NB-PEO-b-PCL) were synthesized from a dual clickable containing both hydroxyl- and alkyne-reactive groups, namely heterofunctional norbornene 3-exo-(2-exo-(hydroxymethyl)norborn-5-enyl)methyl hexynoate. A range of NB-PEO-b-PCL copolymers were obtained using a combination of orthogonal organocatalyzed ring-opening polymerization (ROP) and click copper-catalyzed azide–alkyne cycloaddition (CuAAC). Ring-opening metathesis polymerization (ROMP) of NB-PEO-b-PCL macromonomers using ruthenium-based Grubbs' catalysts provides comb-like and umbrella-like graft copolymers bearing both PEO and PCL grafts on each monomer unit. Mikto-arm star A2B2 copolymers were obtained through a new strategy based on thiol–norbornene photoinitiated click chemistry between 1,3-propanedithiol and NB-PEO-b-PCL. The results demonstrate that in-chain NB-PEO-b-PCL copolymers can be used as a platform to prepare mikto-arm star, umbrella-, and comb-like graft copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017. Well-defined in-chain norbornene-functionalized poly(ethylene oxide)-b-poly(ɛ-caprolactone) copolymers (NB-PEO-b-PCL) are used as a platform to prepare mikto-arm star, umbrella-, and comb-like graft copolymers using ring-opening metathesis polymerization (ROMP) and thiol–norbornene photoinitiated click chemistry.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/pola.28876

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