Engineering solvation in initiated chemical vapour deposition for control over polymerization kinetics and material properties
Nature Synthesis, ISSN: 2731-0582, Vol: 2, Issue: 4, Page: 373-383
2023
- 5Citations
- 12Captures
- 15Mentions
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Article Description
Organic solvents are widely used in polymer synthesis, despite their use lengthening purification steps and generating chemical waste. All-dry synthesis techniques, such as initiated chemical vapour deposition polymerization, eliminate the use of solvents; however, only a narrow palette of material properties are accessible. Inspired by the principles of solvent engineering in solution synthesis, we report a strategy to broaden this palette by vapour phase complexing (namely, vapour phase solvation) mediated by hydrogen bonding. Broad ranges of polymer chain length, as well as the mechanical strength and variety of film surface morphology, are demonstrated using this strategy. We further achieve an unprecedented solvation modality; more specifically, interfacial solvation. The molecular interactions, locations of solvation and kinetics of the coupled solvation–adsorption–polymerization process are investigated using molecular dynamics simulations and experimental validation of a theoretical kinetics model. The strategy can be applied to various methacrylate and vinyl monomers. Solvation in all-dry polymerization offers a concept in polymer design and synthesis with improved environmental benignness, pointing to accelerated discovery of polymer thin films by simply introducing active solvents in the vapour phase. [Figure not available: see fulltext.]
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