Radical addition-fragmentation chemistry in polymer synthesis

Cyclic monomers bearing either vinyl or exomethylene groups have the ability to be polymerized through a radical pathway via a ring-opening mechanism (addition–fragmentation process), leading to the introduction of functionalities in the polymer backbone. Radical ring-opening polymerization (rROP) combines the advantages of both ring-opening polymerization and radical polymerization, that is the preparation of polymers bearing heteroatoms in the backbone but with the ease and robustness of a radical process. This current review presents a comprehensive description of rROP by detailing: (i) the various monomers that polymerize through rROP; (ii) the main parameters that govern the rROP mechanism; (iii) the copolymerization by conventional or controlled/living radical polymerization between rROP monomers and traditional vinyl monomers to obtain copolymers with advanced properties; (iv) the different applications (low shrinkage materials and preparation of (bio)degradable materials) of rROP monomer-containin...

Radical Ring-Opening Polymerization: Scope, Limitations, and Application to (Bio)Degradable Materials

Chemistry, chances and limitations of the radical ring-opening polymerization of cyclic ketene acetals for the synthesis of degradable polyesters

Tailor-made ABA triblock copolymers (poly(furfuryl methacrylate)-b-poly(2-ethylhexyl acrylate)-b-poly(furfuryl methacrylate) (FEF)) bearing a reactive pendant furfuryl group were successfully synthesized by atom transfer radical polymerization. The chemical compositions were calculated by 1H NMR, and molecular weights and molecular weight distributions were determined by gel permeation chromatography analysis. The tensile properties of the triblock copolymers such as tensile strength, elongation at break, and tension set were studied. Differential scanning calorimetry (DSC) analysis and dynamic mechanical analysis (DMA) show the existence of two glass transition temperatures (Tg) and thereby the presence of well-defined soft and hard phase. Thermoreversible self-healing material was successfully prepared by using Diels−Alder reaction between this reactive furfuryl group (diene) of the ABA triblock copolymer and a bismaleimide (dienophile). Thermoreversible property of the polymer was confirmed by FTIR and...

Smart “All Acrylate” ABA Triblock Copolymer Bearing Reactive Functionality via Atom Transfer Radical Polymerization (ATRP): Demonstration of a “Click Reaction” in Thermoreversible Property

Jin-Ying Yuan

Papers

“Living” free radical ring-opening copolymerization of 4,7-dimethyl-2-methylene-1,3-dioxepane and conventional vinyl monomers

Block copolymerization of 5,6-benzo-2-methylene-1,3-dioxepane with conventional vinyl monomers by ATRP method