Controlling the synthesis of degradable vinyl polymers by xanthate-mediated polymerization

The copolymerization of vinyl acetate (VAc) and 2-methylene-1,3-dioxepane (MDO), as well as the homopolymerization of MDO in the presence of a p-methoxyphenyl xanthate chain transfer agent (CTA) is reported and comparison of the homopolymerization of MDO with other known xanthates was also investigated. In depth investigation showed loss of the xanthate functionality was a result of Z-group fragmentation leading to the formation of carbonodithioate groups, as confirmed by 13C NMR spectroscopy. The use of the xanthate with a substituted phenyl Z-group drastically reduces fragmentation through the Z-group and hence significantly increases chain-end retention during the polymerization using the RAFT/MADIX technique. Post-polymerization modification of the chain-end of poly(MDO) was achieved by in situ aminolysis and base-catalyzed Michael addition of propargyl methacrylate onto the terminal thiol to form alkyne functional poly(MDO)

Controlling the synthesis of degradable vinyl polymers by xanthate-mediated polymerization

The copolymerization of vinyl acetate (VAc) and 2-methylene-1,3-dioxepane (MDO), as well as the homo-polymerization of MDO in the presence of a p-methoxyphenyl xanthate chain transfer agent (CTA) is reported and comparison of the homopolymerization of MDO with other known xanthates was also investigated. In depth investigation showed loss of the xanthate functionality was a result of Z-group fragmentation leading to the formation of carbonodithioate groups, as confirmed by C-13 NMR spectroscopy. The use of the xanthate with a substituted phenyl Z-group drastically reduces fragmentation through the Z-group and hence significantly increases chain-end retention during the polymerization using the RAFT/MADIX technique. Post-polymerization modification of the chain-end of poly(MDO) was achieved by in situ aminolysis and base-catalyzed Michael addition of propargyl methacrylate onto the terminal thiol to form alkyne functional poly(MDO)

Functional Degradable Polymers by Xanthate-Mediated Polymerization

Herein we report the first example of the controlled synthesis of linear and hyperbranched copolymers of 2-methylene-1,3-dioxepane (MDO) with functional vinyl monomers to deliver a range of functional, degradable polymers by reversible deactivation radical polymerization. The copolymerization was able to be tuned to vary the incorporation of degradable segments to create degradable materials with predictable molar mass, low dispersity values while also featuring side-chain functionality. The formation of nanoparticles by the addition of divinyladipate to form degradable hyperbranched copolymers was proven by DLS and TEM analyses

Functional Degradable Polymers by Xanthate-Mediated Polymerization

Herein we report the first example of the controlled synthesis of linear and hyperbranched copolymers of 2-methylene-1,3-dioxepane (MDO) with functional vinyl monomers to deliver a range of functional, degradable polymers by reversible deactivation radical polymerization. The copolymerization was able to be tuned to vary the incorporation of degradable segments to create degradable materials with predictable molar mass, low dispersity values while also featuring side-chain functionality. The formation of nanoparticles by the addition of divinyladipate to form degradable hyperbranched copolymers was proven by DLS and TEM analyses