Probability theory of asymmetric chain growth in polymerization

Probability theory of Markov chains has been applied to the chain propagation step of binary and multicomponent copolymerizations. General equations are presented for the calculation of the fractional distribution of monomer units in linear copolymers of any arbitrary degree of polymerization. It is shown that in ordinary Markov processes, the effect of initiation progressively becomes unimportant as the chain length increases and that the polymer composition approaches its stationary limit determined by the transition probabilities alone. The possibility of preparing optically active polymers is discussed in the light of the theoretical results obtained.