Epoxy‐functionalized,low‐glass‐transition‐temperature latex. II. Interdiffusion versus crosslinking in the presence of a diamine

This article describes the results of experiments examining the competition between the polymer diffusion rate and the crosslinking rate in low‐glass‐transition‐temperature, epoxy‐containing latex films in the presence of a diamine. We examined films formed from donor‐ and acceptor‐labeled poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate) copolymer latex and studied the influence of several parameters on the growth rate of gel content and the rate of polymer diffusion. These factors include the molecular weight of the latex polymer, the presence or absence of a diamine crosslinking agent, and the cure protocol. The results were compared to the predictions of a recent theory of the competition between crosslinking and polymer diffusion across interfaces. In the initially formed films, polymer diffusion occurs more rapidly than the chemical reaction rate. Therefore, these films fall into the fast‐diffusion category of this model. In our system (unlike in the model), the latex polymer has a broad distribution of molecular weights and a distribution of diffusivities. The shortest chains contribute to the early time diffusion that we measure. At later stages of our experiment, slower diffusing species contribute to the signal that we measure. The diffusion time decreases substantially, and we observe a crossover to a regime in which the chemical reaction dominates. The increases in chain branching and gel formation bring polymer diffusion to a halt. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4098–4116, 2002