From time dependent incorporation of molecular building blocks to application properties for inorganic and organic three-dimensional network polymers

Abstract

The three-dimensional configurational arrangement of natural and synthetic network materials determines their application range. Control of the real time incorporation of each building block, hence, all functional groups is desired so that we can regulate macroscopic properties from the molecular level onwards. Here we interconnect kinetic Monte Carlo simulations from the field of chemical kinetics and molecular dynamic simulations from the field of physics. We visualize for (in)organic network material synthesis how the initial building blocks interact timewise and spatially, accounting for variations in inter- and intramolecular chemical reactivity, diffusivity, segmental compositions, branch/network point locations, and defects. We use the kinetic and three-dimensional structural information to construct structure-property relationships based on molecular descriptors such as the molecular pore size or dangling chain distribution, differentiating between ideal and non-ideal structural elements. The generic nature is illustrated by constructing such relationships for the synthesis of organosilica, epoxy-amine and Diels-Alder based networks.

Gillespie-Driven kinetic Monte Carlo Algorithms to Model Events for Bulk or Solution (Bio)Chemical Systems Containing Elemental and Distributed Species

“…One of the main areas of application for kMC modeling involving distributed systems is PRE, which is the main application field in the present contribution, although also examples from other fields such as the biological one are included. The ever-increasing amounts of memory in desktop computers combined with kMC modeling tools specifically allowed to store more molecular information such as monomer sequences , and the location of branching points for individual copolymer chains. , Over the last 20 years, kMC has been applied successfully to model a wide variety of polymerization mechanisms such as (i) FRP; − (ii) reversible deactivation radical polymerization (RDRP) including atom transfer radical polymerization (ATRP), ,− nitroxide-mediated polymerization (NMP), ,,− reversible addition–fragmentation chain transfer (RAFT) polymerization; ,,,,− (iii) radical photopolymerization; ,− (iv) coordination polymerization; − (v) free radical-induced grafting (FRIG) and cross-linking; ,,− (vi) polymer star and network formation; − (vii) ring-opening polymerization (ROP) and cationic ring-opening polymerization (CROP); − (viii) (reversible) living radical polymerization; , and (vi) step-growth or self-condensing vinyl polymerization. ,,−<...…”

Flame Retardant Coatings: Additives, Binders, and Fillers

“…Epoxy resin is an organic macromolecule that can be inter- and intramolecularly crosslinked to form a three-dimensional (3D) polymer network, making it the most adaptable type of thermoset polymer [ 194 ]. Generally, epoxy resin is used in a wide range of applications, ranging from general use to high-performing materials, such as adhesives and protective and decorative coatings [ 195 ], owing to their high versatility from a chemical and processing standpoint and ability to be tailored for particular required properties [ 196 , 197 ].…”

Computer aided recipe design: optimization of polydisperse chemical mixtures using molecular descriptors

“…This examples shows an alternative approach to address the issue of polydispersity and a different level of connection of scales in order to generate structure-activity relationships for polymer properties, however without the primary focus on solving an inverse design problem. 20 In the field of lignin research, a few approaches have been developed which systematically generate lignin oligomer and polymer structures by kinetic Monte Carlo simulation, 21 or other Monte Carlo approaches, 22,23 to match several structural quantities derived from experiments. The idea is to get representative computational models/structure libraries for the rather complicated, source dependent lignin compositions.…”