Radical polymerizations of some vinyl alkyl carbonates

• Published in: Polymer (Guilford) 1994-01, Vol.35 (22), p.4819-4822
• Main Authors: Ebdon, John R., Aukrust, Inger Reidun F., Redford, Keith, Solberg, Jan
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; kinetics; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical polymerization; vinyl carbonates
• ISSN: 0032-3861; 1873-2291
• DOI: 10.1016/0032-3861(94)90738-2

Some simple experiments have been carried out to assess the kinetics of the radical polymerizations of vinyl ethyl, vinyl tert-butyl, vinyl phenyl and vinyl benzyl carbonates at temperatures between 30°C and 60°C. It is shown that, contrary to some impressions given in the literature, the vinyl alkyl carbonates can be polymerized readily to give polymers of high molecular weight with conventional radical initiators (i.e. benzoyl peroxide and azoisobutyronitrile) provided that it is recognized that they polymerize relatively slowly owing, probably, to them having relatively low values of k p k 1 2 t . Therefore radical initiators must be used with these monomers at temperatures at which they will have relatively long half-lives. It is further shown that the low-temperature initiator, dicyclohexylperoxydicarbonate (DCHPC), favoured by previous workers for the polymerization of these monomers, offers no obvious advantages over the use of the more conventional initiators at higher temperatures, and that an alternative low temperature initiator, tert-butylperoxyneodecanoate, polymerizes vinyl alkyl carbonates with a facility equal to that of DCHPC.