Model-based design of the polymer microstructure: bridging the gap between polymer chemistry and engineering

Abstract

The performance of polymeric materials depends strongly on the control over the polymer microstructure during the synthesis step. In this review, attention is paid to the potential of microkinetic modelling to facilitate the identification of optimal reactants and reaction conditions to design the polymer microstructure in bulk and solution (post) polymerisation processes. Focus is on living polymerization, reversible deactivation radical polymerization (RDRP) and "click" chemistry techniques, covering both batch and continuous synthesis approaches. A description according to the increasing level of macromolecular detail and thus modelling complexity is provided, including not only the characterization of the polymer microstructure via a finite number of variates (e.g. chain length, overall composition and branching content) but also its explicit visualisation by the simulation of the architecture and monomer sequences of a representative number of individual polymer chains. Several complementary case studies are included to demonstrate the high relevance of model-based design for the development of improved and novel synthetic protocols for precision control

Simulation of the Degradation of Cyclic Ketene Acetal and Vinyl‐Based Copolymers Synthesized via a Radical Process: Influence of the Reactivity Ratios on the Degradability Properties

“…These methods are usually based on a matrix representation of the propagation event history of a representative number of macrospecies along the polymerization, following a kinetic Monte Carlo ( k MC) algorithm . With this approach, the theoretical degradation of the polymer chains could thus be investigated at the molecular level.…”

Rapid, Regioselective Living Ring‐Opening Metathesis Polymerization of Bio‐Derivable Asymmetric Tricyclic Oxanorbornenes

“…The molecular microstructure of polymer materials (i.e., sequence and tacticity) is intimately linked to their physicochemical and thermomechanical properties and as such dictates their performance in specific applications. Variations in the synthetic methodology used for the preparation of polymeric materials can lead to stark differences in properties at both the molecular and macroscopic levels …”

How to Fight Kinetics in Complex Radical Polymerization Processes: Theoretical Case Study of Poly(divinyl ether‐alt‐maleic anhydride)

“…Diffusion factors were taken into account as some addition reactions in the DVEMAN copolymerization were found to be low barrier . Diffusion effects were explored via the coupled encounter pair model that was found to be applicable for rough estimation of diffusion in polymerization processes . The coupled encounter pair model considers that, in order for chemical equilibrium to be established, a series of resistances need to be overcome, both in the forward and in the backward direction.…”

“…Recent progress in different modeling techniques amplified with development of computational resources and methods and in conjunction with experimental field advancements enabled theoretical investigation of polymerization on different scale, for example, polymer molecular scale or micro‐, meso‐, and macroscales . Application of the modeling methods to the investigation of regulation factors of structural and stereoisomerism of DVEMAN is a novel area that can give necessary theoretical ground for applied research.…”