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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.
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:
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,
RAFT is a type of living polymerization involving a conventional radical polymerization which is mediated by a RAFT agent. [8] Monomers must be capable of radical polymerization. [9] There are a number of steps in a RAFT polymerization: initiation, pre-equilibrium, re-initiation, main equilibrium, propagation and termination.
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.
In chain-growth (or chain) polymerization, the only chain-extension reaction step is the addition of a monomer to a growing chain with an active center such as a free radical, cation, or anion. Once the growth of a chain is initiated by formation of an active center, chain propagation is usually rapid by addition of a sequence of monomers.