Interestingly, our aromatic system showed slightly higher energetic barriers compared to the aliphatic model systems used by Ehlers et al., suggesting an overall slower reaction. The differences between our calculated energetic barriers for primary and secondary aromatic amines are very small (5.4 and 3.6 kJ mol -1 for the stepwise and stepwise/alcohol-catalyzed pathways, respectively). Such energetic differences are even smaller or close to the typical errors expected for computed energy barriers at this level of theory. Thus we decided to neglect these small differences in the kinetic constants for primary and secondary amines and assumed identical reactivity of the two in our simulations. Furthermore, as already mentioned, we introduced an alchemical reaction modelling, which neglected any transition states and intermediates in the actual curing simulation by updating the MD topology from reactants to products based on a distance cut-off. This approach has been shown to yield reasonably cured systems. It has been recognized that the energetic barriers of the individual reactions are very prohibitive for time scales observable with MD simulations and anyways would need to be artificially smoothed out or boosted to allow any reaction to take place. Scheme 5 Reaction site templates for the first (left) and the second (right) curing reaction. Situation before (top) and after (bottom) the reaction are presented. "Reacting", "initiator" and "edge" atoms are indicated.