Photoinitiierte Polymerisation mit Dialkoxythiocarbonyldisulfiden – eine Polymerisationsreaktion mit Primärradikalabbruch

Abstract

Photoinitiated Polymerization with Dialkoxy Thiocarbonyl Disulfides – a Polymerization Reaction with Primary Radical TerminationThe photoinduced free radical polymerization of methyl methacrylate (MMA) and some other vinyl monomers using dialkoxy thiocarbonyl disulfides (1–4) as photoinitiators was studied. The photolysis of these initiators leads to cleavage of the SS bond, which was determined by spin trapping experiments with phenyl tert‐butyl nitrone. No evidence was found for a further thermal decomposition of the primary alkoxy thiocarbonyl sulfide radicals (R·) at room temperature. In the absence of scavengers the primary radicals react back exclusively to the initial compounds, due to a strong cage effect. By means of UV spectroscopic measurements and in the presence of MMA the quantum yields of the initiator decomposition were detected to be 0.8. The polymerization of acrylic and methacrylic derivatives can be initiated by the R·, contrary to the situation with fumarates and maleates. The mechanism of MMA polymerization depends on the light intensity absorbed by the initiators. At high intensities the combination of primary and polymer radicals terminates the chain reaction. This follows from the measured monomer exponent of α = 2, the light intensity exponent of β = 0,2 and the number of thiocarbonyl end groups of 2 in the polymers isolated. Contrary to this, in the low intensity region the experimental data obey the ideal kinetic equation. Kinetic modelling gives evidence for an interaction of the monomer with the cage radicals.