THERMODYNAMICS OF CYCLOALKENES, OF THEIR BULK-POLYMERIZATION IN THE PRESENCE OF METATHESIS CATALYSTS AND OF POLYALKENES

Principal regularities of the thermodynamics in ring-opening bulk polymerization of cycloalkenes (cyclononene, cyclodecene, cycloundecene, cyclododecene, cyclotridecene, cyclotetradecene and cyclopentadecene) as established from precise calorimetric studies are considered. For all monomers and polymers studied the temperature dependence of the heat capacity was investigated in the range of 5 K to 400 K, and the temperatures and enthalpies of physical transitions were determined. The enthalpies of combustion of a number of monomers and polymers were measured, and for some monomers direct calorimetric measurements of enthalpies of polymerization were made. From the data obtained the thermodynamic functions H-0(T) - H-0(0), S0(T), G0(T) - H-0(0) were calculated for all compounds under study in the range from 0 to 400 K and for some monomers and polymers the enthalpies of formation at T = 298,15 K and pressure p = 101,325 kPa. For monomers in the glassy state zero entropies S(gl)0(0) were estimated and the difference in zero enthalpies of polymers in the glassy and the crystalline state H(gl)0(0) - H(cr)0(0) was determined. Enthalpies, entropies and Gibbs functions of polymerization were calculated between 0 and 400 K at standard pressure.