Rate of Polymerization

In chain polymerization, the rate at which the monomer (M), of concentration [M], is converted to polymer, −d[M]/dt. Since the rate of propagation occurs hundreds of times more frequently than initiation, rates of polymerization and propagation are the same and the symbol R_p is used for both (Odian GC (2004) Principles of polymerization. Wiley, New York; Connors KA (1990) Chemial kinetics. Wiley, New York; Solomon DH (1969) Kinetics and mechanisms of polymerization series, vol 2 – Ring opening and vol 3 – step growth. Marcel Dekker, New York). For a steady-state chain polymerization reaction, R_p is defined by the following equation

$${\rm R}_{\rm p} = {\rm k}_{\rm P} \left[ {\rm M} \right]\left( {{\rm R}_{\rm i} /2{\rm k}_{\rm t} } \right)^{1/2} $$

Where k_p is the rate constant, R_i is the rate of initiation, and k_t is the termination rate constant. In free radical polymerization initiated by thermal decomposition of initiator I with rate constant k_dand initiator efficiency f, the...