Abstract
RAFT polymerization has emerged as one of the most versatile reversible deactivation radical polymerization techniques and is capable of polymerizing a wide range of monomers under various conditions.
Highlights
The large commercial demand for acrylic polymers has prompted research toward improving processes for the polymerization of acrylates
In order to gain a greater insight into the effects of chain transfer reactions and intermediate radicals on the product distribution in Reversible Addition–Fragmentation chain Transfer (RAFT) polymerization of acrylates, in this work we study in detail poly(n-butyl acrylate) produced using a trithiocarbonate RAFT agent in solution and in bulk by means of MALDI-TOF MS combined with other techniques including Nuclear Magnetic Resonance (NMR) and Size Exclusion Chromatography coupled with a Multi Angle Light Scattering detector (SEC/multi angle light scattering (MALS))
In order to demonstrate the effect of transfer to solvent on the livingness and molecular weight distribution of polymers produced by RAFT we first synthesized a low molecular weight pBA polymer in ethanol, a known transferring solvent which has been used in the synthesis of multiblock BA/acrylic acid (AA) copolymers.[28,29,30]
Summary
The large commercial demand for acrylic polymers has prompted research toward improving processes for the polymerization of acrylates. Most poly(acrylates) are produced by free radical polymerization that, in comparison to anionic and cationic polymerizations, provides poor control of the polymerization.[1] Reversible deactivation radical polymerization techniques[2,3,4,5,6,7,8] allow a much better control of this microstructure Most of these methods utilize a dynamic equilibrium between the growing radicals and dormant species. Standard free radical initiators are used to generate radicals which react with the thiocarbonylthio compound to generate an intermediate radical, as can be seen in Scheme 1 This intermediate radical fragments via a β-scission process which results in reformation of the thiocarbonylthio group at the dormant chain end and an active, propagating radical. Through this reversible addition–fragmentation process an equilibrium between dormant and active chains is established and control over molecular weight and end group functionality can be achieved
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