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Monomer to RAFT reagent: gives the expected degree of polymerization (that is, the number of monomer units in each polymer chain) and can be used to estimate the molecular weight of the polymer by Equation (1) (see below). [12] [14] RAFT reagent to initiator: determines the end groups on the polymer chains.
RAFT is a degenerative chain transfer process and is free radical in nature. RAFT agents contain di- or tri-thiocarbonyl groups, and it is the reaction with an initiator, usually AIBN, that creates a propagating chain or polymer radical. This polymer chain then adds to the C=S and leads to the formation of a stabilized radical intermediate.
To initiator: a polymer chain reacts with an initiator, which terminates that polymer chain, but creates a new radical initiator (Figure 21). This initiator can then begin new polymer chains. Therefore, contrary to the other forms of chain transfer, chain transfer to the initiator does allow for further propagation.
The chelate initiators have a high potential for living polymerizations because the ancillary ligands can be designed to discourage or inhibit chain termination pathways. Chelate initiators can be further broken down based on the ancillary ligands; ansa-cyclopentyadienyl-amido initiators, alpha-diimine chelates and phenoxy-imine chelates. [5]
4,4′-Azobis(4-cyanopentanoic acid) (ACPA) is a free radical initiator used in polymer synthesis. [1] ACPA is a water-soluble initiator used in both heterogeneous and homogeneous free-radical polymerizations. It is used as an initiator in reversible addition−fragmentation chain transfer polymerization (RAFT).
The initiator of the polymerization is usually an organohalogenid and the dormant state is achieved in a metal complex of a transition metal (‘radical buffer’). This method is very versatile but requires unconventional initiator systems that are sometimes poorly compatible with the polymerization media.
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Controlled radical polymerization, namely reversible addition−fragmentation chain-transfer polymerization (RAFT), is a common method for the polymerization of acrylates, methacrylates and acrylamides. Usually, a thiocarbonate is used in combination with an effective initiator for RAFT. The thiocarbonate moiety can be functionalized at the R ...