Reversible Deactivation Radical Polymerizations (RDRP) are polymerization techniques which have many of the characteristics of living polymerizations. Reversible Addition – fragmentation chain transfer (RAFT) and ATRP (Atom Transfer Radical Polymerization) can be considered as the most common and powerful RDRP techniques for synthesizing complex polymers. Both RAFT and ATRP polymerization gives low molar mass dispersity and highly precise molecular weight polymers. It is well known as controlled radical polymerization. Chain transfer agent (CTA) plays an important role in the RAFT polymerization which controls the chain length of the polymer. According to the mechanistic pathway, once the propagating radicals formed, they undergo cascade reactions and reach into a chain transfer step. This chain transfer step is degenerative and made up from CTA and monomers. In a normal system, CTAs diffuse within the system to locate monomers and then exchange to form linear polymer chain. However, when the crosslinking happens between polymer chains, the diffusion of the polymers is reduced but the free radical can continue to add monomers as it does in normal systems. With comparison to RAFT polymerization, ATRP consists with a transition metal (typically copper) mediated mechanism based on inner sphere electron transfer process. It involves halogen transfer between a dormant species (R-X or R-P<sub>n</sub>-X) and a transition metal complex. The main purpose of this study it to compare the outcome of these two polymerization techniques in the presence of a crosslinker. In this study, DSDA (Disulfide-Based Diacrylate) use as the crosslinker and HEA (Hydroxy Ethyl Acrylate) use as the monomer. Gel Permeation Chromatography and Rheology used to characterize materials.

Are RAFT and ATRP universally interchangeable polymerization methods in network formation?

ACS Fall 2021

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