Interpretation of rates of polymer‐polymer reactions in terms of statistical thermodynamics of dilute polymer solutions

The influence of long‐range polymer interactions on intermolecular polymer reactions is studied for those cases where the rate‐determining step is not diffusion‐controlled but chemical process controlled. Rate consants are derived for the reaction between a reactive group linked to the l 1 th segment of polymer 1 and a ractive group linked to the m 2 th segment of polymer 2 as well as for the reaction between polymers 1 and 2 carrying both randomly distributed reactive groups. The rate constant is closely related to the second virial coefficient in the latter case. After formation of the bond between polymers 1 and 2, the second reaction is assumed to take place between the remaining reactive groups A and B within the two linked chains. The apparent second‐order rate constant of this reaction is predicted to increase with decreasing concentration of the reactive groups.