开环易位聚合(ROMP)在星型聚合物合成中的应用进展

doi:10.6023/A21100479

化学学报 ›› 2022, Vol. 80 ›› Issue (2): 229-236.DOI: 10.6023/A21100479 上一篇

综述

开环易位聚合(ROMP)在星型聚合物合成中的应用进展

周楚璐^a^,^b^,^c, 侯翠苹^b, 陈伟^a, 王立杰^a, 程建华^b^,^c^,^*()

a 中国电建集团中南勘测设计研究院有限公司长沙 410014
b 中国科学院长春应用化学研究所高分子物理与化学国家重点实验室长春 130022
c 中国科学技术大学合肥 230026

投稿日期:2021-10-26 发布日期:2021-12-21
通讯作者: 程建华

作者简介:

周楚璐, 中国电建集团中南勘测设计研究院有限公司博士后. 2015年本科毕业于湘潭大学. 2020年在中国科学院长春应用化学研究所(系中国科学技术大学应用化学与工程学院)获得博士学位. 主要从事新型过渡金属烯烃催化剂的设计与合成, 以及星形钌烯烃复分解催化剂的合成与应用.

侯翠苹, 中国科学院长春应用化学研究所博士研究生. 2015年本科毕业于中国矿业大学. 2021年在中国科学院长春应用化学研究所(系中国科学技术大学应用化学与工程学院)获得博士学位. 研究方向为非线性聚合物的拓扑结构设计与可控合成.

程建华, 中国科学院长春应用化学研究所研究员. 1997年本科毕业于吉林大学南岭校区(原吉林工业大学). 2003年毕业于中国科学院长春应用化学研究所, 获博士学位. 2003年至2013年在加拿大阿尔伯塔大学化学系、日本理化学研究所从事博士后研究和特别研究员. 2013年3月入职中国科学院长春应用化学研究所. 主要从事金属有机化学研究, 包括: 碱土金属、f-区金属配合物的合成以及反应性的研究、新型过渡金属烯烃催化剂的设计与合成、以及通过“先核后臂”的方法合成多嵌段、星形多臂等拓扑结构可控的功能化聚合物材料.

基金资助:
国家自然科学基金(21971232)

Progress of Application of Ring-Opening Metathesis Polymerization (ROMP) in the Synthesis of Star Polymers

Chulu Zhou^a^,^b^,^c, Cuiping Hou^b, Wei Chen^a, Lijie Wang^a, Jianhua Cheng^b^,^c()

a Power China Zhongnan Engineering Corporation Limited, Changsha 410014, China
b State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
c University of Science and Technology of China, Hefei 230026, China

Received:2021-10-26 Published:2021-12-21
Contact: Jianhua Cheng
Supported by:
National Natural Science Foundation of China(21971232)

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摘要/Abstract

开环易位聚合(ROMP)是一种单环或多环烯烃进行开环聚合反应形成功能化聚合物的方法, 已经发展成为一种合成先进聚合物材料的高效方法之一. 而星型聚合物由于特殊的结构和性能将在学术和工业的材料科学和纳米技术领域中发挥越来越重要的作用. 本综述从聚合方法、聚合单体、引发剂、交联剂等方面讨论了ROMP在星型聚合物合成中的应用, 并介绍了ROMP合成的星型聚合物的应用领域和前景, 客观地评价了各种ROMP方法的优势和局限性. 这项工作旨在促进ROMP在合成星型聚合物的研究, 为合成功能性复杂星型聚合物提供新的科学研究途径, 为加快星型聚合物材料商业化的脚步添砖加瓦.

关键词: 开环易位聚合(ROMP), 星型聚合物, 多功能引发剂, 先臂后核法, 先核后臂法, 串联ROMP法

Ring-opening metathesis polymerization (ROMP) is a strategy in which monocyclic or polycyclic olefins undergo ring-opening polymerization to form functionalized polymers. ROMP has been recognized as a powerful synthetic strategy for the synthesis of advanced polymeric materials. Recently, star polymers are receiving intense interests in materials science and nanotechnology in both academic and industrial fields due to the unique structure and property. In this review, the applications of ROMP in the synthesis of star polymers are discussed in terms of methods of polymerization, monomers, initiators and crosslinking agents. Moreover, the application fields and prospects of the ROMP synthesized star polymers, and the advantages and limitations of various ROMP methods are also presented. This work aims to promote development of ROMP in the synthesis of star-shaped polymers, provide a new scientific research approach for the synthesis of functionally complicated star-shaped polymers, and contribute to the acceleration of the commercialization of star-shaped polymer materials.

Key words: ring-opening metathesis polymerization (ROMP), star polymer, multifunctional initiator, arm-first, core-first, tandem ROMP

引用此文

周楚璐, 侯翠苹, 陈伟, 王立杰, 程建华. 开环易位聚合(ROMP)在星型聚合物合成中的应用进展[J]. 化学学报, 2022, 80(2): 229-236.

Chulu Zhou, Cuiping Hou, Wei Chen, Lijie Wang, Jianhua Cheng. Progress of Application of Ring-Opening Metathesis Polymerization (ROMP) in the Synthesis of Star Polymers[J]. Acta Chimica Sinica, 2022, 80(2): 229-236.

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图/表 14

图1. 多官能降冰片烯交联剂

Figure 1. Multifunctional norbornene crosslinking agents

图2. 在亚烷基钼催化下依次加入降冰片烯与交联剂合成星型ROMP聚合物

Figure 2. Synthesis of star-shaped ROMP polymers by sequential addition of norbornene and cross-linker in the presence of molybdenum- alkylidene catalyst

图3. 可降解低聚(大分子单体)臂和大分子梯状交联核的星型聚合物, 在臂降解后产生可溶性微孔微凝胶

Figure 3. Star polymers with degradable oligo(macromonomer) arms and a core crosslinked by macromolecular ladders, which give soluble microporous microgels after degradation of arms

图4. 一锅法制备具有pH、CO2和金属离子响应和聚集诱导发光效应的星型聚合物

Figure 4. One-pot preparation of an aggregation-induced emission star polymer with pH, CO2 and metal ion responsive fluorescence

图5. 通过1引发的大单体2的接枝开环易位聚合合成聚(乙二醇)刷型臂星型聚合物, 然后通过先臂后核法与3进行交联. 这些BASP的硝基苄氧羰基核可以在紫外光条件下降解

Figure 5. Synthesis of poly(ethylene glycol) brush-arm star polymers via graft-through ring-opening metathesis polymerization of macromonomer 2 initiated by 1, followed by arm-first cross-linking with 3. The nitrobenzyloxycarbonyl cores of these BASPs degrade under ultraviolet light

图6. 通过将短(DP=7) PEG刷型(共)聚合物与AcXL交联来合成BASP(刷型臂星型聚合物). 缩醛核(灰色)在酸性环境下可以发生降解反应

Figure 6. The synthesis of BASPs (brush-arm star polymers) by cross-linking short (DP?=?7) PEG-based bottlebrush (co)polymers with AcXL. The acetal core (gray) can undergo degradation reactions in an acidic environment

图7. 树枝状降冰片烯大分子单体在三功能化Blechert催化剂引发下, 通过先核后臂法制备三臂星型聚合物

Figure 7. The dendritic norbornene macromonomer is initiated by the trifunctional Blechert’s catalyst to prepare a three-arm star polymer through core-first strategy

图8. 一锅法制备接枝密度可控的星型梯度共聚物

Figure 8. One-shot synthesis of star gradient copolymers with controllable graft density

图9. (a) γ-CD-Nb8, Nb-HEG和Nb-PEG相应的结构式和卡通图. (b) 通过先核后臂/接枝法制备双嵌段刷型臂星型共聚物(DBASCs) (CD-(HEGm-PEGn)8)

Figure 9. (a) Chemical structures and corresponding cartoon representations of γ-CD-Nb8, Nb-HEG and Nb-PEG. (b) Core-first/graft-from synthetic strategy for DBASCs (CD-(HEGm-PEGn)8)

图10. 合成四功能化复合物单体{[Zn2(L)4Ln(OAc)2](NO3)},以及PNBE支撑的金属聚合物, 聚{[Zn2(L)4Ln(OAc)2](NO3)}-co-NBE)

Figure 10. Reaction scheme for the synthesis of tetraallyl-functionalized complex monomers {[Zn2(L)4Ln(OAc)2](NO3)} and their PNBE supported metallopolymers poly({[Zn2(L)4Ln(OAc)2](NO3)}-co-NBE)

图11. ROMP制备的低聚合度刷型聚合物, 与含端炔基团的聚合物发生反应, 进行自组装后, 形成一种不对称杂臂星型聚合物

Figure 11. Low polymerization degree ROMP brush polymer reacts with alkyne-terminated polymer, followed by self-assembly, and forms an asymmetric miktoarm star polymers

图12. 合成热响应的光学活性星型嵌段共聚物

Figure 12. Synthesis of thermoresponsive optically active star block copolymer

图13. 采用叠氮化物末端官能化ROM聚合物(PNEONI-N3)和Cu催化1,3-偶极环加成制备三臂星型聚合物

Figure 13. Preparation of three-arm star polymers employing the Cu-catalyzed 1,3-dipolar cycloaddition of azide end-functionalized ROM polymers (PNEONI-N3)

图14. 通过ROMP、ROP和ADMET聚合的顺序组合合成ABC杂臂星型三聚磷酸酯的合成路线

Figure 14. Synthetic routes to ABC miktoarm star terpolyphosphoesters via sequential combination of ROMP, ROP and ADMET polymerization

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开环易位聚合(ROMP)在星型聚合物合成中的应用进展

Progress of Application of Ring-Opening Metathesis Polymerization (ROMP) in the Synthesis of Star Polymers

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