Free Radical Polymerization

FRP is a standard and facile method for the polymerization of a great variety of monomers
with unsaturated carbon–carbon bonds. It starts with an initiator molecule that is thermally or
by UV radiation decomposed into free radical(s) and that subsequently reacts with monomers
bearing carbon–carbon double bonds such as vinyl, acrylate, or methacrylate groups [37]. In
the next step, radical-containing moieties react with a next monomer molecule, resulting in
chain propagation until termination of chain growth occurs when two free radical-containing
molecules react with each other. PNIPAM was first synthesized in the 1950s by this
conventional polymerization method [3]. Although the molecular weight distribution obtained
using FRP is rather broad, it is up to today a very versatile and frequently used polymerization
technique, which can be performed in different organic solvents as well as in aqueous media.
Common organic solvents used for this polymerization are methanol, benzene, acetone, THF,
t-butanol, dioxane, and chloroform as well as mixtures of these solvents [37]. Typically, the
preferred initiator is azobisisobutyronitrile (AIBN) although also other initiators have been
used. Polymeric chains can inherit chain ends from the initiator depending on the type of
initiator used. For instance, England and Rimmer [38] used 1-phenyl(trimethylsiloxy)ethylene
as an initiator for polymerization of NIPAM and in this way obtained phenyl-derivatised
PNIPAM.

FRP is a standard and facile method for the polymerization of a great variety of monomers
with unsaturated carbon–carbon bonds. It starts with an initiator molecule that is thermally or
by UV radiation decomposed into free radical(s) and that subsequently reacts with monomers
bearing carbon–carbon double bonds such as vinyl, acrylate, or methacrylate groups [37]. In
the next step, radical-containing moieties react with a next monomer molecule, resulting in
chain propagation until termination of chain growth occurs when two free radical-containing
molecules react with each other. PNIPAM was first synthesized in the 1950s by this
conventional polymerization method [3]. Although the molecular weight distribution obtained
using FRP is rather broad, it is up to today a very versatile and frequently used polymerization
technique, which can be performed in different organic solvents as well as in aqueous media.
Common organic solvents used for this polymerization are methanol, benzene, acetone, THF,
t-butanol, dioxane, and chloroform as well as mixtures of these solvents [37]. Typically, the
preferred initiator is azobisisobutyronitrile (AIBN) although also other initiators have been
used. Polymeric chains can inherit chain ends from the initiator depending on the type of
initiator used. For instance, England and Rimmer [38] used 1-phenyl(trimethylsiloxy)ethylene
as an initiator for polymerization of NIPAM and in this way obtained phenyl-derivatised
PNIPAM