Dynamic Monte Carlo Simulation of ATRP in a Batch Reactor

Abstract

A dynamic MC model was developed to simulate the polymerization kinetics and the detailed microstructure of copolymers made with ATRP in a batch reactor. The model was used to predict monomer conversion, average molecular weight, polydispersity index, and copolymer composition as a function of polymerization time. The model can also predict the distribution of molecular weight, chemical composition, and comonomer sequence length at any polymerization time or comonomer conversion. The simulation was used to explore the effects of rate constants and reactant stoichiometry on the microstructure of chains. Two copolymerization systems were chosen to demonstrate the effect of reactivity ratios and comonomer feed compositions on the final chemical composition distribution.magnified image

Gradient Copolymers by ATRP in Semibatch Reactors: Dynamic Monte Carlo Simulation

“…Figure 12–17 clearly show that St diads and triads increase with increase in time for all initial monomer concentrations. Comparing these results with those reported in our batch polymerization simulation paper,40 remarkable improvement in the formation of St diads and triads are inferred. The batch results show no formation of gradient polymers at all concentrations used while our results predict the formation of gradient polymers for all the concentrations.…”

“…We have shown in a previous paper that St‐MMA gradient polymers are not produced effectively in batch reactors because of their similar reactivity ratios (Table 1). 40 In this case, the only resource is the use of semibatch reactors with the continuous feed of at least one of the comonomers.…”

From Molecular to Plant‐Scale Modeling of Polymerization Processes: A Digital High‐Pressure Low‐Density Polyethylene Production Paradigm

“…Based on Tobita's approach, Inkson [46] developed a stochastic algorithm to simulate the kinetic and molecular developments in a time-varying catalytic olefin polymerization system. Similarly, stochastic simulations were employed to calculate the compositional changes in copolymerization systems [47][48][49][50][51][52][53].…”

Simulating Controlled Radical Polymerizations with mcPolymer—A Monte Carlo Approach

“…If a number is chosen which is too small, the simulation will lead to incorrect results, while a large model will increase the computation time and memory consumption. The ATRP polymerization [14], optionally with a bifunctional ATRP initator [15], ATRP copolymerization [16], RAFT polymerization [17,18], NMP homopolymerization [19], NMP copolymerization [20], and gradient copolymerization with tracking the sequence distribution [21,22] are examples of the application of the Monte Carlo simulation.…”