Engineering solvation in initiated chemical vapour deposition for control over polymerization kinetics and material properties
Engineering solvation in initiated chemical vapour deposition for control over polymerization kinetics and material properties
复制标题
DOI：
10.1038/s44160-023-00242-5
复制
发表时间：
2023-02
期刊：
影响因子：
--
通讯作者：
Pengyu Chen;Zheyuan Zhang;Zachary W Rouse;S. Baker;Jingjie Yeo;Rong Yang
中科院分区：
文献类型：
--
作者：
Pengyu Chen;Zheyuan Zhang;Zachary W Rouse;S. Baker;Jingjie Yeo;Rong Yang
有机溶剂在聚合物合成中被广泛使用，尽管它们的使用延长了纯化步骤并产生了化学废物。全干法合成技术，如引发的化学气相沉积聚合，消除了溶剂的使用；然而，只有狭窄的材料特性调色板可用。受溶液合成中溶剂工程原理的启发，我们报道了一种通过氢键介导的汽相络合(即汽相溶剂化)来拓宽这一调色板的策略。使用这一策略可以展示广泛的聚合物链长范围，以及机械强度和薄膜表面形态的多样性。我们进一步实现了前所未有的溶剂化形式；更具体地说，界面溶剂化。通过分子动力学模拟和理论动力学模型的实验验证，研究了溶剂化-吸附-聚合耦合过程中的分子相互作用、溶剂化位置和动力学。该策略可应用于各种甲基丙烯酸酯和乙烯基单体。全干聚合中的溶剂化在聚合物设计和合成中提供了一个概念，改善了环境友好性，指出只需在汽相中引入活性溶剂就可以加速发现聚合物薄膜。
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.