TY - JOUR
T1 - Synthesis of methacrylate-terminated block copolymers with reduced transesterification by controlled ring-opening polymerization
AU - Ruiz-cantu, Laura A.
AU - Pearce, Amanda K.
AU - Burroughs, Laurence
AU - Bennett, Thomas M.
AU - Vasey, Catherine E.
AU - Wildman, Ricky
AU - Irvine, Derek J.
AU - Alexander, Cameron
AU - Taresco, Vincenzo
PY - 2019/1
Y1 - 2019/1
N2 - This work presents a robust method to achieve the synthesis of low molecular weight polyesters via ring‐opening polymerization (ROP) initiated by 2‐hydroxyethyl‐methacrylate (HEMA) when using triazabicyclodecene (TBD) as catalyst. The effect that the HEMA:TBD ratio has upon the final reaction rate and final polymer molecular architecture is discussed. The optimum HEMA:TBD ratio and reaction conditions required to minimize competing transesterification reactions are determined, in order to synthesize successfully the target ROP macromonomer species containing only a single 2‐methacryloyloxyethyl end‐group. Additionally, to confirm the terminal end‐group fidelity of the product macromonomers and confirm TBD utility for block copolymer manufacture, a small series of di‐block polyesters are synthesized using TBD and shown to exhibit good control over the final polymer structure whilst negating the side transesterification reactions, irrespective of the monomers used.
AB - This work presents a robust method to achieve the synthesis of low molecular weight polyesters via ring‐opening polymerization (ROP) initiated by 2‐hydroxyethyl‐methacrylate (HEMA) when using triazabicyclodecene (TBD) as catalyst. The effect that the HEMA:TBD ratio has upon the final reaction rate and final polymer molecular architecture is discussed. The optimum HEMA:TBD ratio and reaction conditions required to minimize competing transesterification reactions are determined, in order to synthesize successfully the target ROP macromonomer species containing only a single 2‐methacryloyloxyethyl end‐group. Additionally, to confirm the terminal end‐group fidelity of the product macromonomers and confirm TBD utility for block copolymer manufacture, a small series of di‐block polyesters are synthesized using TBD and shown to exhibit good control over the final polymer structure whilst negating the side transesterification reactions, irrespective of the monomers used.
KW - hydroxyethyl‐methacrylate‐initiated
KW - monofunctional‐methacrylate polyesters
KW - ring‐opening polymerization
KW - triazabicyclodecene catalyst
UR - http://www.scopus.com/inward/record.url?scp=85057305567&partnerID=8YFLogxK
U2 - 10.1002/macp.201800459
DO - 10.1002/macp.201800459
M3 - Article
SN - 1022-1352
VL - 220
JO - Macromolecular Chemistry and Physics
JF - Macromolecular Chemistry and Physics
IS - 2
M1 - 1800459
ER -