Piezoelectrically Mediated Reversible Addition-Fragmentation Chain Transfer Polymerization

A well-controlled piezoelectrically mediated reversible addition-fragmentation chain transfer polymerization (piezo-RAFT) was carried out under ultrasound agitation with piezoelectric ZnO nanoparticles as the mechano-chemical trans-ducer. The resulting polymer had predictable molecular weight, high end-group fidelity, low dispersity, and capacity for chain extension. This chemistry was further adopted in curing composite resins to circumvent the light penetration limit of UV curing. This work opened a new avenue of piezoelectrically mediated chemistry and showed its good potential in curing applications.

RAFT aqueous dispersion polymerization of 4-hydroxybutyl acrylate: effect of end-group ionization on the formation and colloidal stability of sterically-stabilized diblock copolymer nanoparticles

Poly(2-hydroxyethyl acrylate)-poly(4-hydroxybutyl acrylate) nano-objects are prepared by aqueous polymerization-induced self-assembly (PISA) using an ionic RAFT agent.

Removal of Trithiocarbonyl End Group of RAFT-Polymerized Poly(stearyl acrylate) and Effect of the End Group on Thermal and Structural Properties

The effect of a long alkyl end group on the thermal and structural properties of RAFT (reversible addition-fragmentation chain transfer)-polymerized poly(stearyl acrylate) (PSA) was investigated. RAFT-polymerized PSA was prepared using 2-cyano-2-[(dodecylsulfanylthiocarbonyl) sulfanyl] propane (CDTP) with long alkyl group as a chain transfer agent and azobisisobutyronitrile (AIBN) as an initiator. The RAFT polymerization resulted in the polymerized structure having trithiocarbonyl (TTC) at one end and isobutyronitrile at the other end. RAFT-polymerized PSA was prepared with two different molecular weights. The TTC end group was replaced by isobutyronitrile using radical reaction with AIBN through optimization of the conditions, which resulted in isobutyronitrile at both ends. The effect of the end group on the thermal and structural properties was investigated using differential scanning calorimetry and X-ray diffraction, and the results indicated that the long alkyl group from TTC lowers the melting point and semi-crystalline structure in the case of low molecular weight PSA.

Reversing RAFT Polymerization: Near-Quantitative Monomer Generation via a Catalyst-Free Depolymerization Approach

The ability to reverse controlled radical polymerization and regenerate the monomer would be highly beneficial for both fundamental research and applications, yet has remained very challenging to achieve. Herein, we report a near-quantitative (up to 92%) and catalyst-free depolymerization of various linear, bulky, crosslinked, and functional polymethacrylates made by reversible addition-fragmentation chain-transfer (RAFT) polymerization. Key to our approach is to exploit the high end-group fidelity of RAFT polymers to generate chain-end radicals via thermal homolytic cleavage of carbon-sulfur bond of the RAFT end-group at 120 °C. These radicals trigger a rapid unzipping of both conventional (e.g. poly(methyl methacrylate)) and bulky polymers (e.g. poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA)). Importantly, the depolymerization product can be utilized to either reconstruct the linear polymer or create an entirely new insoluble gel that can also be subjected to depolymerization. This work expands the potential of polymers made by CRP, pushes the boundaries of depolymerization, offers intriguing mechanistic aspects, and enables new applications.