title: Functional Degradable Polymers by Radical Ring-Opening Copolymerization of MDO and Vinyl Bromobutanoate: Synthesis, Degradability and Post-Polymerization Modification.
abstract: The synthesis of vinyl bromobutanoate (VBr), a new vinyl acetate monomer derivative obtained by the palladium-catalyzed vinyl exchange reaction between vinyl acetate (VAc) and 4-bromobutyric acid is reported. The homopolymerization of this new monomer using the RAFT/MADIX polymerization technique leads to the formation of novel well-defined and controlled polymers containing pendent bromine functional groups able to be modified via postpolymerization modification. Furthermore, the copolymerization of vinyl bromobutanoate with 2-methylene-1,3-dioxepane (MDO) was also performed to deliver a range of novel functional degradable copolymers, poly(MDO-co-VBr). The copolymer composition was shown to be able to be tuned to vary the amount of ester repeat units in the polymer backbone, and hence determine the degradability, while maintaining a control of the final copolymers' molar masses. The addition of functionalities via simple postpolymerization modifications such as azidation and the 1,3-dipolar cycloaddition of a PEG alkyne to an azide is also reported and proven by (1)H NMR spectroscopy, FTIR spectroscopy, and SEC analyses. These studies enable the formation of a novel class of hydrophilic functional degradable copolymers using versatile radical polymerization methods.
authors.affiliation: †Department of Chemistry, University of Warwick, Gibbet Hill, Coventry, CV4 7AL, United Kingdom.
authors.forename: Guillaume G
authors.initials: GG
authors.lastname: Hedir
authors.affiliation: †Department of Chemistry, University of Warwick, Gibbet Hill, Coventry, CV4 7AL, United Kingdom.
authors.forename: Craig A
authors.initials: CA
authors.lastname: Bell
authors.affiliation: †Department of Chemistry, University of Warwick, Gibbet Hill, Coventry, CV4 7AL, United Kingdom.
authors.forename: Rachel K
authors.initials: RK
authors.lastname: O'Reilly
authors.affiliation: †Department of Chemistry, University of Warwick, Gibbet Hill, Coventry, CV4 7AL, United Kingdom.
authors.forename: Andrew P
authors.initials: AP
authors.lastname: Dove
mesh_terms: D001672:Biocompatible Materials / Q000138:chemical synthesis* / Q000737:chemistry; D061565:Cycloaddition Reaction; D015394:Molecular Structure; D010082:Oxepins / Q000737:chemistry*; D058105:Polymerization; D014753:Vinyl Compounds / Q000737:chemistry
chemical_list: C000605740:2-methylene-1,3-dioxepane; D001672:Biocompatible Materials; D010082:Oxepins; D014753:Vinyl Compounds; C011566:vinyl acetate