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In polymer chemistry, radical polymerization (RP) is a method of polymerization by which a polymer forms by the successive addition of a radical to building blocks (repeat units). Radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules .
Living free radical polymerization is a type of living polymerization where the active polymer chain end is a free radical. Several methods exist. Several methods exist. IUPAC recommends [ 1 ] to use the term " reversible-deactivation radical polymerization " instead of "living free radical polymerization", though the two terms are not synonymous.
Reversible-addition-fragmentation chain-transfer polymerization (RAFT polymerization, RAFT): Degenerate-transfer radical polymerization in which chain activation and chain deactivation involve a degenerative chain-transfer process which occurs by a two-step addition-fragmentation mechanism. Note 1: Examples of RAFT agents include certain ...
The first strategy involves a reversible trapping mechanism in which the propagating radical undergoes an activation/deactivation (i.e. Atom-transfer radical-polymerization) process with a species X. The species X is a persistent radical, or a species that can generate a stable radical, that cannot terminate with itself or propagate but can ...
In free radical polymerization, radicals formed from the decomposition of an initiator molecule are surrounded by a cage consisting of solvent and/or monomer molecules. [6] Within the cage, the free radicals undergo many collisions leading to their recombination or mutual deactivation. [5] [6] [9] This can be described by the following reaction:
Radical polymerisation of unsaturated monomers is generally propagated by C-radicals. These can be effectively terminated by combining with other radicals to form neutral species and many true inhibitors operate through this mechanism. In the simplest example oxygen can be used as it exists naturally in its triplet state (i.e. it is a diradical).
The termination steps of free radical polymerization steps are of two types: recombination and disproportionation. [2] In a recombination step, two growing chain radicals (denoted by •) form a covalent bond in a single stable molecule. For the example of a vinyl polymer,
The expression ‘controlled radical polymerization’ is sometimes used to describe a radical polymerization that is conducted in the presence of agents that lead to e.g. atom-transfer radical polymerization (ATRP), nitroxide-(aminoxyl) mediated polymerization (NMP), or reversible-addition-fragmentation chain transfer (RAFT) polymerization.