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

该建议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，VCP-酰胺是VCP衍生物的一个有前途的亚类，以及聚VCP-酰胺的结构和物理性质。液体光致交联型单体(一种光致抗蚀剂)具有快速聚合、完全单体转化、体积收缩低或无体积收缩、性能易于调节、多功能、稳定性、低粘度、易于合成等一系列性能，使研究新型一体化光敏树脂变得有意义和必要。寻找新体系的主要挑战在于获得低体积收缩、高单体反应性和聚合过程中完全的单体转化以及易于调节的机械性能的组合。受我们以前的发现启发，我们建议研究一类新的VCP-衍生物，单官能团环丙烷酰胺(VCP-amide)，其中聚合过程中的开环将提供低体积收缩，而单体通过酰胺单元的氢键预组织将使反应性可聚合的乙烯基团接近，从而提高聚合速度。此外，双功能VCP-酰胺中的间隔基和单功能VCP-酰胺中的酰胺键上的取代基将控制单体和聚合物的性质，并且易于调节。我们的目标是提供与VCP-酰胺(包括单官能团和双官能团)的合成、通过氢键进行的结构表征和预组织、光聚合(在本体和溶剂中均聚和共聚)、聚合物的性能评价以及通过3D打印精确构建这一新的亚类VCP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.