Exploration of vinylcyclopropane-amides as fast polymerizable, low volume shrinking H-bonded preordered monomers: Comprehensive studies regarding synthesis, characterization and modularly combined polymer networks

本提案旨在全面了解乙烯基环丙烷（VCP-酰胺）的合成、性质和开环聚合（ROP）行为，以及聚酰亚胺（VCP-酰胺）的结构和物理性质。快速聚合、单体完全转化、低至无体积收缩、易于调制、多功能、稳定性、低粘度、易于合成等特性的结合，使得液体光交联单体（一种（光）抗蚀剂）具有精确的结构，使得研究这种新型一体化光树脂具有意义和必要性。寻找新体系的主要挑战在于获得低体积收缩率、高单体反应性、聚合过程中单体完全转化和易于调节的机械性能的组合。在此基础上，我们提出了一种新的vcp衍生物亚类，即单官能团和双官能团的乙烯基环丙烷酰胺（VCP-amides），其在聚合过程中开环可以提供较小的体积收缩，而通过酰胺单元的h键预组织单体可以使反应性可聚合的乙烯基在近距离内进行增殖反应，从而提高聚合速率。此外，双功能vcp -酰胺的间隔基团和单功能vcp -酰胺酰胺键上的取代基将控制单体和聚合物的性质，并且可以很容易地调节。我们的目标是提供与vcp酰胺（包括单功能和双功能）的合成，结构表征和通过h键的预组织，光聚合（在本体和溶剂中均聚和共聚），聚合物的性能评估以及通过3D打印精确结构的初步实验相关的基础研究。

The proposal aims at comprehensive understanding of synthesis, properties and ring-opening polymerization (ROP) behaviour of vinylcyclopropane (VCP-amides), a promising subclass of VCP derivatives and structural and physical properties of poly (VCP-amides). The combination of properties ranging from fast polymerization, complete monomer conversion, low-to-no volume shrinkage, easy modulation in properties, multi-functionality, stability, low viscosity, easy synthesis required in liquid photo cross-linkable monomers (one-type of (photo)resists) for precise structuring, make the research for new such all-in-one photoresins meaningful and required. The main challenge in searching for new systems lies in obtaining a combination of low volume shrinkage with high monomer reactivity and complete monomer conversion during polymerization and easily tuneable mechanical properties. Inspired by our previous findings, we propose to study a new sub-class of VCP-derivatives, mono- and bifunctional vinyl cyclopropane amides (VCP-amides) in which the ring-opening during polymerization will provide low volume shrinkage while preorganization of the monomers by H-bonding via amide units should bring the reactive polymerizable vinyl groups for propagation reaction in the close proximity, thereby enhanced rate of polymerization. Further, the spacer group in bifunctional VCP-amides and the substituents at the amide bond in mono-functional VCP-amides would control monomer and polymer properties and can be easily modulated. We aim to provide basic studies related to the synthesis of VCP-amides (both monofunctional and bifunctional), structural characterization and pre-organization via H-bonding, photo-polymerization (homo-and co-polymerization in bulk and solvents), properties evaluation of polymers and preliminary experiments for precise structuring by 3D printing of this new sub-class of VCPs.