无机离子聚合与交联及其应用

方威风; 唐睿康; 刘昭明

doi:10.11777/j.issn1000-3304.2021.21034

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无机离子聚合与交联及其应用

专论 | 更新时间：2021-11-03

- 无机离子聚合与交联及其应用
- Polymerization and Crosslinking of Inorganic Ionic Oligomers for Material Construction
- 高分子学报 2021年52卷第6期页码：617-633
- 作者机构：
  
  浙江大学化学系　杭州 310027
- 作者简介：
  
  [ "刘昭明，男，1991年生. 浙江大学化学系研究员，2013和2017年于浙江大学化学系分别获得理学学士、理学博士学位. 2017年至今先后为浙江大学化学系博士后、助理研究员、特聘副研究员、百人计划研究员. 2020年获得国家自然科学基金优秀青年科学基金支持，目前主要从事无机离子聚合的机理与应用研究" ]
- 基金信息：
  
  国家自然科学基金(基金号 22022511，21805241)资助项目
- DOI：10.11777/j.issn1000-3304.2021.21034
  中图分类号：
- 纸质出版日期：2021-6-3，
  
  网络出版日期：2021-5-11，
  
  收稿日期：2021-1-28，
  
  修回日期：2021-4-7，
扫描看全文
方威风, 唐睿康, 刘昭明. 无机离子聚合与交联及其应用[J]. 高分子学报, 2021,52(6):617-633.

Wei-feng Fang, Rui-kang Tang, Zhao-ming Liu. Polymerization and Crosslinking of Inorganic Ionic Oligomers for Material Construction[J]. Acta Polymerica Sinica, 2021,52(6):617-633.
方威风, 唐睿康, 刘昭明. 无机离子聚合与交联及其应用[J]. 高分子学报, 2021,52(6):617-633. DOI： 10.11777/j.issn1000-3304.2021.21034.

Wei-feng Fang, Rui-kang Tang, Zhao-ming Liu. Polymerization and Crosslinking of Inorganic Ionic Oligomers for Material Construction[J]. Acta Polymerica Sinica, 2021,52(6):617-633. DOI： 10.11777/j.issn1000-3304.2021.21034.

摘要

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.

Abstract

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

) ionic oligomers end-capped by triethylamine (TEA) is presented

and these oligomers have 3−11 repeated CaCO

units with an average length of ~1.2 nm. The CaCO

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.

关键词

反应前驱体无机离子寡聚体聚合与交联有机-无机复合仿生材料

Keywords

PrecursorsInorganic ionic oligomersPolymerization and crosslinkingOrganic-inorganic compositeBiomimetic materials

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