Two polymer molecules of the same length (n) and the same number of branch points (N) can have different properties, since they may possess distinct architectures. In this paper we present a conditional Monte Carlo algorithm for the virtual synthesis of metallocene‐catalyzed polyethylene (PE) in a continuous stirred tank reactor (CSTR). The condition for the Monte Carlo method consists of a fixed chain length distribution (CLD) and a degree of branching distribution (DBD). These distributions are calculated with a Galerkin finite element method. The synthesis method is a recursive algorithm that subsequently creates insertions of sub‐structures containing numbers of branch points according to a certain probability density function. This provides an adjacency matrix describing the connectivity between the branch points, while separately a vector containing the length of segments between branch points and terminal segments is generated. Characterization of the architectures proceeds by rheological features, seniorities and priorities, and molecular properties like the radius of gyration. Comparing the radii of gyration of metallocene polyethylene and low density PE (ldPE) shows the former to possess a more comb‐like structure on average. This is confirmed by the rheological characterization. The found bivariate seniority/priority distribution agrees well to the results of an analytical study of the same chemical system.
