Polymers from non-homopolymerizable monomers by free radical processes

There are many monomers known that do not homopolymerizable, but which may be copolymerized. This report deals with the free radical polymerization to alternating copolymers of systems of two, three or four non-homopolymerizable electron-rich (donor) and electron-poor (acceptor) monomers, which always contain 50 mol% donor and acceptor monomer units each. The measured copolymer compositions and the overall polymerization rates can be explained by free-monomer model, penultimate-unit model and charge transfer (CT) model. Measurements of the overall polymerization rate vp and rate coefficient kp are described to distinguish between the simultaneous participation of free monomers and CT complexes in the polymerization process. Generally, at low monomer concentrations the polymerization rate is dominated by the content of free monomers, whereas at high monomer concentrations the much higher reaction rates of the CT complexes are responsible for the overall polymerization rate and the composition of the copolymers. Most copolymers from non-homopolymerizable monomers show high decomposition and glass temperatures.