Chain statistics and heat of reaction in random copolymerization

Copolymer chain-statistics and other properties including the heat of copol ymerization are derived using the joint concepts of the mean-length of the sequences of each species along the copolymer chain and the number of trans itions from sequences of one species to the other. The approach originated in papers of Smoluchowski going back to 1915. By systematic use of the appr oach, classical relationships are derived for both the terminal and the pen ultimate models of copolymerization. Relationships are given for the heat o f copolymerization and the spectroscopic determination of the monomer react ivity ratios. The simultaneous use of the terminal and penultimate models f or specific comonomer species is discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.