无机离子聚合与交联及其应用

Polymerization and Crosslinking of Inorganic Ionic Oligomers for Material Construction

传统无机材料合成遵循经典晶体生长方式,常以粉末颗粒形式存在,极大地限制了无机材料的性能.高分子材料通过单体的可控聚合与交联实现了材料的连续、可塑制备,极大地扩大了材料的应用范围.借鉴高分子化学中的封端策略,我们将无机离子寡聚体作为无机单体,替代了传统的离子前驱体,实现了无机离子化合物的聚合与交联,从而能够“像制造高分子一样制造无机物”.本文从材料合成的角度出发,介绍了无机、高分子反应前驱体及材料制备模式,重点介绍了无机离子寡聚体及其聚合与交联过程,进一步展开介绍了基于无机离子聚合与交联在材料合成与应用方面的成果.无机离子聚合与交联反应体系的提出,在材料合成方面促进了高分子与无机化学的融合,一定程度上打破对传统无机材料合成的认知,为新型功能材料的合成提供新的思路.

This review introduces the discovery of inorganic ionic oligomers and their controllable polymerization and crosslinking for materials preparation.It is well recognized that classical nucleation and crystal growth commonly lead to the formation of inorganic particles,rather than continuously structured bulks,limiting the properties of many inorganic materials.It is due to the participation of inorganic ions as the classical precursors,which are less controllable in the process of material synthesis.Although numerous non-classical precursors,such as pre-nucleation clusters,dense liquid phases and polymer-induced liquid precursors have been discovered,they are still uncontrollable during non-classical crystallization.In contrast,polymers can be continuously and malleably constructed through controllable polymerization and crosslinking of their monomer precursors,which expand the applications of polymeric materials.It indicates that a controllable inorganic precursor is the key to regulating the synthesizing process of a material.Inspired by the capping strategy in polymer chemistry,the hydrogen-bond based capping strategy on inorganic ionic oligomers is established.Typically,the calcium carbonate(CaCO_(3))ionic oligomers end-capped by triethylamine(TEA)is presented,and these oligomers have 3−11 repeated CaCO_(3)units with an average length of~1.2 nm.The CaCO_(3)ionic oligomers can act as the inorganic monomers to replace traditional ions as precursors.And the removal of TEA initiates the polymerization and crosslinking of inorganic ionic substances.This strategy has generality and this achievement can be used to produce inorganic materials in a way analogous to polymers.The polymerization and crosslinking of inorganic ionic oligomers can be the fundamental way for advanced material preparation.It demonstrates the moldable construction of inorganic materials from nano-scales to macro-scales,and even the building of single crystals.And it is readily for the reconstruction of hierarchical structured bio-tissues,such as sea urchin spine and human enamel.Moreover,the organic-inorganic co-polymerization is established by using inorganic ionic oligomers,which enables the doping of molecular scaled inorganics into organic polymers.The incorporation of inorganic ionic oligomers into organic polymers enables the construction of biomimetic hybrid materials,improving the functions of polymers.The establishment of polymerization and crosslinking of inorganic ionic oligomers promote the fusion of polymer and inorganic chemistry.However,this is a newly raised field in chemistry,which needs further detailed investigations.It is believed that this achievement will provide more strategies for functional material production in the future.