| Abstract: | Isothermal differential scanning calorimetry (photocalorimetry) enables real‐time measurements of rates of polymerisation as functions of irradiation time to be made. Since it is possible to stop initiation at any point in a reaction (by cutting off the light) and to monitor the dark reaction, this method has been widely used for determinations of the (apparent) rate constants of polymerisation of multifunctional monomers at various degrees of double bond conversion. The work reported here presents the results of photocalorimetric studies of polymerisation kinetics of six related acrylates and methacrylates. Two main topics are discussed: the effects of sulphide and ether groups present in the monomers on network formation, and the determination of polymerisation rate constants according to three termination models (monomolecular, bimolecular and mixed). |
