3.

1 Radical Homopolymerization 167

Table 3.5 Some common oxidizing and reducing agents that are suitable for initiating radical
polymerization by redox reactions
Oxidizing agents Reducing agents
Hydrogen peroxide Ag+, Fe2+, Co2+, Ti3+
Peroxodisulfates Hydrogen sulfites, sulfites, thiosulfates, mercaptans, sulfinic acids
Diacyl peroxides Amines (e.g. N,N-dimethylaniline), certain sugars
Hydroperoxides Benzoin/Fe2+
Peracid ester Hydrogen sulfite/Fe2+

reduced again to the iron(II) state by the hydrogen sulfite, so that only a very small
amount of iron(II) ions is required.
Table 3.5 lists some suitable oxidizing and reducing agents.
In a redox system consisting of a peroxo compound and an iron(II) salt, the
initiating radicals are formed by electron transfer from Fe2+ to the peroxo com-
pound, causing the peroxy link to be cleaved, with simultaneous formation of a
radical and an anion. In a second step, the oxidized metal reacts with another
hydroperoxide to form a peroxy radical and a proton:
R O 2+
R-O + OH + Fe3+
O H + Fe

R O 3+
R-O-O +H + Fe2+
O H + Fe

It must be emphasized that, in contrast to the initiation of polymerization with

peroxo compounds or azo compounds, not every redox system is suitable for
initiating polymerization of every unsaturated monomer. Before attempting to
polymerize a new compound with a redox system it is, therefore, advisable first
to test its radical polymerizability with dibenzoyl peroxide.
Furthermore, the effectiveness of a redox system is influenced by a number of
factors, and the redox components must be carefully balanced in order to attain
optimum polymerization conditions. The most favorable conditions do not always
correspond to a stoichiometric ratio of oxidizing and reducing agents. However, at
constant molar ratio of oxidizing agent to reducing agent it is generally the rule that
the rate of polymerization increases, and the mean degree of polymerization
decreases, with increasing initiator concentration (see Example 3.11). The order
of addition of the components can also be important; while it is normal to add the
reducing agent first (in order to remove any oxygen which may be present), with
subsequent dropwise addition of the oxidizing agent, there are cases where the
reverse order must be applied. In aqueous medium, the pH value is also important;
if it is necessary to work in alkaline medium, iron salts can only be used in
combination with complexing agents such as sodium pyrophosphate (Na4P2O7).
Redox polymerizations are usually carried out in aqueous solution, suspension,
or emulsion; rarely in organic solvents. Their special importance lies in the fact that
they proceed at relatively low temperatures with high rates and with the formation
of high molecular weight polymers. Furthermore, transfer and branching reactions