In 1953, Paul Flory first classified polymerization as "step-growth polymerization" and "chain-growth polymerization". 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. In addition to the regenerated active sites of each monomer unit, polymer growth will only occur at one (or possibly more) endpoint.
Many common polymers can be obtained by chain polymerization such as polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), poly(methyl methacrylate) (PMMA), polyacrylonitrile (PAN), polyvinyl acetate (PVA).
Typically, chain-growth polymerization can be understood with the chemical equation:
In this equation, P is the polymer while x represents degree of polymerization, * means active center of chain-growth polymerization, M is the monomer which will react with active center, and L may be a low-molar-mass by-product obtained during chain propagation. For most chain-growth polymerizations, there is no by-product L formed. However there are some exceptions, such as the polymerization of amino acid N-carboxyanhydrides to oxazolidine-2,5-diones.
This type of polymerization is described as "chain" or "chain-growth" because the reaction mechanism is a chemical chain reaction with an initiation step in which an active center is formed, followed by a rapid sequence of chain propagation steps in which the polymer molecule grows by addition of one monomer molecule to the active center in each step. The word "chain" here does not refer to the fact that polymer molecules form long chains. Some polymers are formed instead by a second type of mechanism known as step-growth polymerization without rapid chain propagation steps.