Intra- vs Intermolecular Cross-Links in Poly(methyl methacrylate) Networks Containing Enamine Bonds

The molecular dynamics of a copolymer composed of methyl methacrylate (MMA) and (2-acetoacetoxy)ethyl methacrylate (AEMA) monomers and the influence on it of intra-to intermolecular cross-links of AEMA units with ethylenediamine (EDA) was studied by combining dielectric relaxation experiments and thermal investigations. The dielectric spectra of the non-cross-linked copolymer show three dynamical processes: a slow relaxation (alpha) and a faster (beta), both dominated by the MMA dynamics, and an even faster secondary relaxation (gamma) reflecting the AEMA dynamics. Already for low cross-linking densities, the gamma process is very much affected and eventually disappears, increasing the cross-linking density. The secondary beta relaxation however was nearly unaffected by cross-linking. The effect of cross-linking on the alpha relaxation was very pronounced with an important increasing of the glass transition temperature Tg. There was also an increase of the dynamic heterogeneity and the relaxation intensity when increasing the cross-linking density (up to the maximum explored, 9 mol % EDA). The quality of the average time scale and Tg value have similarities in behavior for intra-and intermolecular cross linking, but clear differences in the dynamic heterogeneities where observed. These differences can be interpreted in connection with the sparse internal structure of the collapsed single chains obtained by intramolecular cross-linking.

Automated summary

The molecular dynamics of a copolymer composed of methyl methacrylate (MMA) and (2-acetoacetoxy)ethyl methacrylate (AEMA) monomers and the influence of intra-to intermolecular cross-links of AEMA units with ethylenediamine (EDA) were studied. The results showed that cross-linking had a significant impact on the copolymer's dynamic processes, glass transition temperature Tg, and dynamic heterogeneity, while having minimal effect on the secondary relaxation process.