| Summary: | A challenge in the field of polymer network synthesis by a step-growth mechanism is the quantification of the relative importance of inter- vs. intramolecular reactions. Here we use a matrix-based kinetic Monte Carlo (<i>k</i>MC) framework to demonstrate that the variation of the chain length distribution and its averages (e.g., number average chain length <i>x<sub>n</sub></i>), are largely affected by intramolecular reactions, as mostly ignored in theoretical studies. We showcase that a conventional approach based on equations derived by Carothers, Flory and Stockmayer, assuming constant reactivities and ignoring intramolecular reactions, is very approximate, and the use of asymptotic limits is biased. Intramolecular reactions stretch the functional group (FG) conversion range and reduce the average chain lengths. In the likely case of restricted mobilities due to diffusional limitations because of a viscosity increase during polymerization, a complex <i>x<sub>n</sub></i> profile with possible plateau formation may arise. The joint consideration of stoichiometric and non-stoichiometric conditions allows the validation of hypotheses for both the intrinsic and apparent reactivities of inter- and intramolecular reactions. The <i>k</i>MC framework is also utilized for reverse engineering purposes, aiming at the identification of advanced (pseudo-)analytical equations, dimensionless numbers and mechanistic insights. We highlight that assuming average molecules by equally distributing A and B FGs is unsuited, and the number of AB intramolecular combinations is affected by the number of monomer units in the molecules, specifically at high FG conversions. In the absence of mobility constraints, dimensionless numbers can be considered to map the time variation of the fraction of intramolecular reactions, but still, a complex solution results, making a <i>k</i>MC approach overall most elegant.
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