Kinetic Monte Carlo Modeling of the Sulfinyl Precursor Route for Poly(p-phenylene vinylene) Synthesis

Abstract

A kinetic Monte Carlo modeling study is presented for precursor polymer formation via the sulfinyl precursor route. The premonomer, 1-(chloromethyl)-4-[(n-octylsulfinyl)methyl]benzene, is subjected to a NatBuO induced 1,6-elimination in sBuOH yielding the actual p-quinodimethane monomer that leads, via a radical polymerization, to the precursor polymer. The kinetic Monte Carlo model is able to predict the experimental trends in yield, mass averaged molar mass and structural defect content. The effect of radical recombination and cyclization is modeled and found to be negligible. The effect of the initial base and premonomer concentration on the polymer properties is investigated. Simulation results indicate a maximum in the polymer yield and chain length for initial [base]/[premonomer] = 1 and that the molecular properties of the precursor polymers can be varied by as much as 50% by an appropriate choice of initial [base]/[premonomer]. The kinetic Monte Carlo model is used to determine reaction conditions to achieve targeted polymer yields, chain lengths and structural defect contents.

An Update on the Pivotal Role of Kinetic Modeling for the Mechanistic Understanding and Design of Bulk and Solution RAFT Polymerization

“…Finally, so‐called hybrid methods have also been developed which combine deterministic and stochastic elements. For example, Konkolowicz et al have calculated the change of the RAFT polymerization CLD for a given time step by integrating moment equations and subsequent sampling of the polymeric reaction events to construct the CLD.…”

A Theoretical Exploration of the Potential of ICAR ATRP for One‐ and Two‐Pot Synthesis of Well‐Defined Diblock Copolymers

“…For a detailed description of the kinetic model, the reader is referred to Van Steenberge et al [48,74] Besides the conversion profile and the evolution of average polymer properties, such as the number average chain length (x n ), the polydispersity index (PDI), and the end-group functionality (EGF) with conversion, the kMC model allows the explicit representation of the copolymer composition along the polymerization, i.e., for a representative number of polymer chains the monomer sequence can be tracked. Based on a benchmarking of the simulations starting from a sufficiently high number of monomer molecules ( %10 7 ), 10 000 to 20 000 polymer chains have to be typically tracked to obtain reliable results in ICAR ATRP.…”

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

“…Furthermore, in the present work, the <GD> value is calculated without accounting for possible losses of low-quality oligomeric chains upon polymer isolation. For more details on the mathematical aspects of the applied kMC modeling approach, the reader is referred to Van Steenberge et al [26,32,34].…”