Polymerization of methyl methacrylate in the presence of P-H acids, such as
bis(pirocatechol)hydrospirophosphorane and bis(2,3-butanediol)hydrospiroph
osphorane as well as ethylene-bis[thio(1,3,2-phosphothiolane)], was studied
. It was shown that phosphorus compounds are involved in the redox initiati
on of polymerization, although the activity of phosphorus-containing redox
initiating systems is appreciably lower, as compared to nitrogen- and sulfu
r-containing compounds. It was demonstrated that the peculiarities of perox
ide-initiated polymerization in the presence of ethylene-bis[thio(1,3,2-pho
sphothiolane)] are accounted for by the structure of its molecule, in which
a phosphorus atom is shielded by three sulfur atoms attached to this phosp
horus. The behavior of initiating systems based on this compound is determi
ned for the most part by the presence of sulfur atoms rather than by phosph
orus ones.