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In polymer chemistry, free-radical polymerization (FRP) is a method of polymerization by which a polymer forms by the successive addition of free-radical building blocks (repeat units). Free 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.
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 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,
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.
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:
IUPAC recommends to further simplify "chain-growth polymerization" to "chain polymerization". It is a kind of polymerization where an active center (free radical or ion) is formed, and a plurality of monomers can be polymerized together in a short period of time to form a macromolecule having a large molecular weight.
Branching sometimes occurs spontaneously during synthesis of polymers; e.g., by free-radical polymerization of ethylene to form polyethylene. In fact, preventing branching to produce linear polyethylene requires special methods. Because of the way polyamides are formed, nylon would seem to be limited to unbranched, straight chains.