Synergy of Advanced Experimental and Modeling Tools to Underpin the Synthesis of Static Step-Growth-Based Networks Involving Polymeric Precursor Building Blocks

• DOI: 10.1021/acs.macromol.1c01476
• Publication Date: 2021-10-14T13:04:31Z
• Authors: Lies De Keer; Federica Cavalli; Diego Estupiñán; Andreas J. D. Krüger; Susana Rocha; Paul H. M. Van St...; Marie-Françoise R...; Laura De Laporte; Johan Hofkens; Leonie Barner; Dagmar R. D’hooge
• Keywords: Molar mass

The strength of combining experimental design and advanced kinetic Monte Carlo (kMC) modeling to understand step-growth network synthesis, commencing with a linear/star polymeric precursor, is illustrated considering three chemistries: (i) para-fluoro-thiol reaction (PFTR); (ii) nitrile imine-mediated tetrazole-ene cycloaddition (NITEC); (iii) star poly(ethylene oxide-stat-propylene oxide) (sPEG)-amine-epoxy click reaction. Chemical parameters are determined based on small-molecule systems (monofunctional analogues) diffusion literature data higher-network-yield data. Overall model validation performed molar mass spectroscopic As basic support, kMC provides the evolution complete size exclusion chromatography trace for both soluble insoluble fraction at any time. In more detail, allows one construct, whenever desired, two-dimensional traces such as distribution species given number cross-linking points (CPs) type (e.g., least cross-links), still differentiating between fractions. Ultimately, postprocessing results calculate distributions regarding distances specific functional groups molecular pore upon three-dimensional representation buildup individual molecules. Also, (relative) importance pathways can be assessed. It is, instance, shown that diffusional limitations intermolecular reactions determine how far polymer yield pushed, strong effect due an intrinsically fast maleimide incorporation step, specifically NITEC. Too long linear precursor building blocks should avoided they induce too prominent limitations. short promote intramolecular reactions. With sPEG blocks, well-defined structure obtained, confirmed by narrow dye molecules added in polymerization recipe.