基于炔类单体的点击聚合制备超支化聚合物

黄蝶; 秦安军; 唐本忠

doi:10.11777/j.issn1000-3304.2017.16275

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基于炔类单体的点击聚合制备超支化聚合物

专论 | 更新时间：2021-05-18

- 基于炔类单体的点击聚合制备超支化聚合物
- Hyperbranched Polymers Prepared by Alkyne-based Click Polymerization
- 高分子学报 2017年第2期页码：178-199
- 作者机构：
  
  1.华南理工大学发光材料与器件国家重点实验室广州 510640
  2.香港科技大学化学系国家人体组织功能重建工程技术研究中心香港分中心香港
- 作者简介：
  
  秦安军，男，1977年10月生.华南理工大学材料科学与工程学院发光材料与器件国家重点实验室教授、博士生导师. 1999年本科毕业于山西大学；2004年获中科院化学所理学博士学位；之后分别在香港科技大学和浙江大学从事Research Associate和博士后工作；2008年12月起先后任浙江大学副研究员、副教授；2013年9月起到华南理工大学发光材料与器件国家重点实验室工作. 2015年获国家杰出青年科学基金资助，并入选中组部“万人计划”青年拔尖人才支持计划；2012年获国家自然科学基金优秀青年科学基金资助.主要研究方向为基于三键的高分子合成化学和有机/聚合物光电功能材料. E-mail:msqinaj@scut.edu.cn An-jun Qin, E-mail:msqinaj@scut.edu.cn
  唐本忠，男，1957年2月生.华南理工大学双聘院士、香港科技大学张鉴泉理学教授. 1982年本科毕业于华南理工大学. 1985年和1988年分别从日本京都大学获得硕士、博士学位，之后到加拿大多伦多大学从事博士后研究. 1994年加盟香港科大化学系，2008年晋升为讲座教授. 2009年当选中国科学院院士，2013年荣升英国皇家化学会Fellow.现为科技部973计划项目首席科学家、国家自然科学基金重大项目主持人、广东省第三批引进科研创新团队带头人、华南理工大学发光材料与器件国家重点实验室学术委员会主任. 2014年获第27届夸瑞兹密国际科学奖，2012年获美国化学会高分子学术报告奖，2007年获裘槎高级研究成就奖、国家自然科学二等奖、中国化学会高分子基础研究王葆仁奖.主要研究方向为高分子化学和聚集诱导发光. E-mail: tangbenz@ust.hk Ben Zhong Tang, E-mail:tangbenz@ust.hk
- 基金信息：
  
  国家自然科学基金(21525417);国家自然科学基金(21490571);国家重点基础研究发展计划973计划(2013CB834702);中组部青年拔尖人才支持计划、中央高校基本科研业务费(2015ZY013);广东省引进创新科研团队(201101C0105067115)
- DOI：10.11777/j.issn1000-3304.2017.16275
  中图分类号：
- 纸质出版日期：2017-2-20，
  
  收稿日期：2016-9-6，
  
  修回日期：2016-9-29，
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黄蝶, 秦安军, 唐本忠. 基于炔类单体的点击聚合制备超支化聚合物[J]. 高分子学报, 2017,(2):178-199.

Huang Die, Qin An-jun, Zhong Tang Ben. Hyperbranched Polymers Prepared by Alkyne-based Click Polymerization[J]. Acta Polymerica Sinica, 2017,(2):178-199.
黄蝶, 秦安军, 唐本忠. 基于炔类单体的点击聚合制备超支化聚合物[J]. 高分子学报, 2017,(2):178-199. DOI： 10.11777/j.issn1000-3304.2017.16275.

Huang Die, Qin An-jun, Zhong Tang Ben. Hyperbranched Polymers Prepared by Alkyne-based Click Polymerization[J]. Acta Polymerica Sinica, 2017,(2):178-199. DOI： 10.11777/j.issn1000-3304.2017.16275.

摘要

超支化聚合物由于其独特的树枝状结构和物理化学性质，已经得到了广泛关注及应用.而基于炔类单体的点击聚合作为一类简单、高效的聚合反应已被广泛用于超支化聚合物的制备.本文对近5年利用叠氮-炔和巯基-炔点击聚合制备超支化聚合物的工作进行了简要综述.其中，Cu（Ⅰ）催化的叠氮-炔点击聚合可制备1

4-立构规整的超支化聚三唑；Ru（Ⅱ）催化的叠氮-炔点击聚合可制备1

5-立构规整的超支化聚三唑；活化的炔类单体和叠氮单体的无金属催化点击聚合可得到1

4-异构体含量高（高达91.7%）的超支化聚合物；而光引发、热引发及自发的巯基-炔点击聚合可制备含硫的超支化聚合物.此外，对所制备的超支化聚合物的功能和应用进行了简单介绍，最后还简单讨论了点击聚合制备超支化聚合物方面的可能发展方向.

Abstract

Hyperbranched polymers

as one kind of three dimensional macromolecules with globular and dendritic architectures

have unique properties of good solubility

low viscosity

topological structure

a lot of functional groups

etc

. Over the past decades

the hyperbranched polymers have attracted more and more attention and been widely applied in diverse areas including coatings

additives

biomaterials

supramolecular chemistry

nanoscience and technology

photoelectricmaterials

and so on. Click polymerization with the advantages of facile monomers accessibility

mild reaction conditions and high reaction efficiency has been developed into a sort of powerful polymerization tool for the synthesis of polymers with well-defined molecular structures and advanced functional properties. This method has also been extensively used in the synthesis of hyperbranched polymers. This review mainly summarizes the progress on the synthesis of the hyperbranched polymers

via

alkyne-based click polymerizations in the last 5 years. The Cu (Ⅰ)-catalyzed azide-alkyne click polymerization could readily produce 1

4-regioregular hyperbranched polytriazoles

whereas the Ru (Ⅱ)-catalyzed azide-alkyne click polymerization could generate 1

5-regioregular hyperbranched polytriazoles. Meanwhile

the azide-alkyne click polymerizations under metal-free conditions were also developed through the ingenious design of monomers. Metal-free click polymerization of activated alkyne and azide monomers could efficiently produce hyperbranched polytriazoles with fraction of 1

4-isomers up to 91.7%. The obtained polytriazoles are thermally stable and well soluble in most common solvents

such as tetrahydrofuran

dichloromethane

-dimethyl formamide

dimethyl sulfoxide. Moreover

the photo-and thermo-initiated as well as spontaneous thiol-yne click polymerizations could be used to facilely prepare sulfur-containing hyperbranched polymers. The thiol-yne addition process could be fine-tuned by the control of the polymerization condition

and hyperbranched polymers with diverse topological structures could be provided. The properties and applications including aggregation-induced emission

sensitive explosive detection

self-healing

high refractive index and fluorescent patterning etc

of resultant hyperbranched polymers were also briefly reviewed. In addition

the promising opportunities and directions in this area were also discussed.

关键词

超支化聚合物点击聚合区域选择性功能化

Keywords

Hyperbranched polymersClick polymerizationsRegioselectivityFunctionalization

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