基于链转移反应的聚合物端基功能化研究进展

韩明阳; 秦亚伟; 常添笑; 张瑜菲; 陈商涛; 叶海木

doi:10.14028/j.cnki.1003-3726.2025.25.013

您当前的位置：

首页 >

文章列表页 >

基于链转移反应的聚合物端基功能化研究进展

综述 | 更新时间：2025-05-23

- 基于链转移反应的聚合物端基功能化研究进展
- Research Progress of Chain Transfer Reactions on End-functionalized Polymers
- 高分子通报 2025年38卷第6期页码：880-892
- 作者机构：
  
  1.中国石油天然气股份有限公司石油化工研究院，北京 102206
  2.中国石油大学（北京）新能源与材料学院，北京 102249
- 作者简介：
  
  *秦亚伟，E-mail: qinyawei010@petrochina.com.cn；陈商涛，E-mail: chenst7890@petrochina.com.cn
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2025.25.013
  中图分类号：
- 收稿日期：2025-01-09，
  
  录用日期：2025-03-06，
  
  网络出版日期：2025-04-16，
  
  纸质出版日期：2025-06-20
- 稿件说明：
移动端阅览
韩明阳, 秦亚伟, 常添笑, 张瑜菲, 陈商涛, 叶海木. 基于链转移反应的聚合物端基功能化研究进展. 高分子通报, 2025, 38(6), 880-892.

Han, M. Y.; Qin, Y. W.; Chang, T. X.; Zhang, Y. F.; Chen, S. T.; Ye, H. M. Research progress of chain transfer reactions on end-functionalized polymers. Polym. Bull. (in Chinese), 2025, 38(6), 880-892.
韩明阳, 秦亚伟, 常添笑, 张瑜菲, 陈商涛, 叶海木. 基于链转移反应的聚合物端基功能化研究进展. 高分子通报, 2025, 38(6), 880-892. DOI： 10.14028/j.cnki.1003-3726.2025.25.013.

Han, M. Y.; Qin, Y. W.; Chang, T. X.; Zhang, Y. F.; Chen, S. T.; Ye, H. M. Research progress of chain transfer reactions on end-functionalized polymers. Polym. Bull. (in Chinese), 2025, 38(6), 880-892. DOI： 10.14028/j.cnki.1003-3726.2025.25.013.

摘要

通过链转移反应向聚合物大分子链端引入功能性基团，实现聚合物端基功能化，这是赋予聚合物新性能的有效途径。本文综述了链转移反应在聚合物端基功能化方面的研究进展，以聚合反应机理为基础，分别介绍了链转移剂种类及其在自由基聚合反应、配位聚合反应和阳离子聚合反应中的作用机理。旨在总结分析制备端基功能化聚合物的方法，讨论端基功能化聚合物在生物医用材料和智能材料等领域的应用，提出当前制备端基功能化聚合物面临的关键问题，为后续研究提供思路及建议。

Abstract

The preparation of chain end functionalized polymers

via

chain transfer reactions represents a highly effective strategy for imparting novel properties to polymers. This paper reviews the current status and progress of chain transfer reactions on end-functionalized polymers. Based on the principle of polymerization

this review introduces a classification of chain transfer agents and their roles in free radical polymerization

coordination polymerization

and cationic polymerization. Additionally

this review aims to summarize and analyze effective approaches for the preparation of end-functionalized polymers and discuss the applications of end-functionalized polymers in fields such as biomedical materials and smart materials. It also highlights the key challenges that need to be solved in current research on chain end functionalized polymers and provides insights and suggestions for subsequent research.

关键词

Keywords

references

Hadjichristidis, N. ; Pispas, S. ; Pitsikalis, M . End-functionalized polymers with zwitterionic end-groups . Prog. Polym. Sci. , 1999 , 24 ( 6 ), 875 – 915 .

Kim, J. ; Jung, H. Y. ; Park, M. J . End-group chemistry and junction chemistry in polymer science: past, present, and future . Macromolecules , 2020 , 53 ( 3 ), 746 – 763 .

Madkour, A. E. ; Koch, A. H. R. ; Lienkamp, K. ; Tew, G. N . End-functionalized ROMP polymers for biomedical applications . Macromolecules , 2010 , 43 ( 10 ), 4557 – 4561 .

Mao, Z. H. ; Vakhshouri, K. ; Jaye, C. ; Fischer, D. A. ; Fernando, R. ; DeLongchamp, D. M. ; Gomez, E. D. ; Sauvé, G . Synthesis of perfluoroalkyl end-functionalized poly(3-hexylthiophene) and the effect of fluorinated end groups on solar cell performance . Macromolecules , 2013 , 46 ( 1 ), 103 – 112 .

Jasinska-Walc, L. ; Bouyahyi, M. ; Duchateau, R . Potential of functionalized polyolefins in a sustainable polymer economy: synthetic strategies and applications . Acc. Chem. Res. , 2022 , 55 ( 15 ), 1985 – 1996 .

张勇杰 , 樊明帅 , 李晓佩 , 李化毅 , 王书唯 , 祝文亲 . 含硅功能化聚烯烃: 合成及应用 . 化学进展 , 2020 , 32 ( 1 ), 84 – 92 .

Zhou, D. ; Zhu, L. W. ; Wu, B. H. ; Xu, Z. K. ; Wan, L. S . End-functionalized polymers by controlled/living radical polymerizations: synthesis and applications . Polym. Chem. , 2022 , 13 ( 3 ), 300 – 358 .

Pino-Ramos, V. H. ; Ramos-Ballesteros, A. ; López-Saucedo, F. ; López-Barriguete, J. E. ; Varca, G. H. C. ; Bucio, E . Radiation grafting for the functionalization and development of smart polymeric materials . Top Curr Chem Cham , 2016 , 374 ( 5 ), 63 .

Flory, P. J . The mechanism of vinyl polymerizations . J. Am. Chem. Soc. , 1937 , 59 ( 2 ), 241 – 253 .

Farina, M . Chemistry and kinetics of the chain transfer reaction . Makromol. Chem. Macromol. Symp. , 1987 , 10-11 ( 1 ), 255 – 272 .

Lee, Y. ; Boyer, C. ; Kwon, M. S . Photocontrolled RAFT polymerization: past, present, and future . Chem. Soc. Rev. , 2023 , 52 ( 9 ), 3035 – 3097 .

Zhao, B. Y. ; Wilson, P . Recent progress and applications enabled via electrochemically triggered and controlled chain-growth polymerizations . Polym. Chem. , 2023 , 14 ( 17 ), 2000 – 2021 .

Rajasekhar, T. ; Singh, G. ; Kapur, G. S. ; Ramakumar, S. S. V . Recent advances in catalytic chain transfer polymerization of isobutylene: a review . RSC Adv. , 2020 , 10 ( 31 ), 18180 – 18191 .

Uchiyama, M. ; Satoh, K. ; Kamigaito, M . Cationic RAFT and DT polymerization . Prog. Polym. Sci. , 2022 , 124 , 101485 .

Li, Y. ; Zhang, Y. J. ; Li, Q. ; Li, H. Y. ; Zheng, S. R. ; Hu, Y. L . Synthesis of novel chain-end-functionalized polyethylenes via thiol-ene click chemistry . Macromol. Chem. Phys. , 2015 , 216 ( 5 ), 569 – 581 .

Altintas, O. ; Josse, T. ; de Winter, J. ; Matsumoto, N. M. ; Gerbaux, P. ; Wilhelm, M. ; Barner-Kowollik, C . Ready access to end-functional polystyrenes via a combination of ARGET ATRP and thiol–ene chemistry . Polym. Chem. , 2015 , 6 ( 39 ), 6931 – 6935 .

Liu, H. Z. ; Maugein, V. A. ; Haddleton, D. M . Radical polymerisation and thiol-ene post-polymerisation functionalisation of terpenoid acrylates in conventional and renewably sourced organic solvents . Polym. Chem. , 2024 , 15 ( 28 ), 2862 – 2872 .

Yhaya, F. ; Sutinah, A. ; Gregory, A. M. ; Liang, M. T. ; Stenzel, M. H . RAFT polymerization of vinyl methacrylate and subsequent conjugation via enzymatic thiol-ene chemistry . J. Polym. Sci. Part A Polym. Chem. , 2012 , 50 ( 19 ), 4085 – 4093 .

Lowe, A. B . Thiol-ene “click” reactions and recent applications in polymer and materials synthesis . Polym. Chem. , 2010 , 1 ( 1 ), 17 – 36 .

Perrier, S. ; Takolpuckdee, P. ; Westwood, J. ; Lewis, D. M . Versatile chain transfer agents for reversible addition fragmentation chain transfer (RAFT) polymerization to synthesize functional polymeric architectures . Macromolecules , 2004 , 37 ( 8 ), 2709 – 2717 .

Coskun, H. I. ; de Luca Bossa, F. ; Hu, X. L. ; Jockusch, S. ; Sobieski, J. ; Yilmaz, G. ; Matyjaszewski, K . ATRP with ppb concentrations of photocatalysts . J. Am. Chem. Soc. , 2024 , 146 ( 42 ), 28994 – 29005 .

Kwak, Y. ; Nicolaÿ, R. ; Matyjaszewski, K . A simple and efficient synthesis of RAFT chain transfer agents via atom transfer radical addition-fragmentation . Macromolecules , 2009 , 42 ( 11 ), 3738 – 3742 .

Albanese, K. R. ; Morris, P. T. ; Read de Alaniz, J. ; Bates, C. M. ; Hawker, C. J . Controlled-radical polymerization of α -lipoic acid: A general route to degradable vinyl copolymers . J. Am. Chem. Soc. , 2023 , 145 ( 41 ), 22728 – 22734 .

Han, X. W. ; Daugulis, O. ; Brookhart, M . Unsaturated alcohols as chain-transfer agents in olefin polymerization: synthesis of aldehyde end-capped oligomers and polymers . J. Am. Chem. Soc. , 2020 , 142 ( 36 ), 15431 – 15437 .

Han, X.-W. ; Daugulis, O. ; Brookhart, M . Synthesis of end-functionalized poly(norbornenes) and poly(ethylidene norbornenes) using a pd(ii) catalyst in combination with chain transfer agents . Organometallics , 2021 , 40 ( 15 ), 2709 – 2715 .

Yang, G. W. ; Xie, R. ; Zhang, Y. Y. ; Xu, C. K. ; Wu, G. P . Evolution of copolymers of epoxides and CO 2 : catalysts, monomers, architectures, and applications . Chem. Rev. , 2024 , 124 ( 21 ), 12305 – 12380 .

Yang, G. W. ; Xu, C. K. ; Xie, R. ; Zhang, Y. Y. ; Lu, C. J. ; Qi, H. ; Yang, L. ; Wang, Y. H. ; Wu, G. P . Precision copolymerization of CO 2 and epoxides enabled by organoboron catalysts . Nat. Synth. , 2022 , 1 ( 11 ), 892 – 901 .

Zhang, Y. Y. ; Yang, G. W. ; Xie, R. ; Zhu, X. F. ; Wu, G. P . Sequence-reversible construction of oxygen-rich block copolymers from epoxide mixtures by organoboron catalysts . J. Am. Chem. Soc. , 2022 , 144 ( 43 ), 19896 – 19909 .

Makiguchi, K. ; Satoh, T. ; Kakuchi, T . Synthesis of various end-functionalized polyesters by controlled/living ring-opening polymerization of lactones using pentafluorophenylbis(triflyl)methane . J. Polym. Sci. Part A Polym. Chem. , 2011 , 49 ( 17 ), 3769 – 3777 .

Obenauf, J. ; Kretschmer, W. P. ; Bauer, T. ; Kempe, R . An efficient titanium amidinate catalyzed version of ziegler's “aufbaureaktion” . Eur. J. Inorg. Chem. , 2013 , 2013 ( 4 ), 537 – 544 .

Pillai, S. K. T. ; Kretschmer, W. P. ; Trebbin, M. ; Förster, S. ; Kempe, R . Tailored nanostructuring of end-group-functionalized high-density polyethylene synthesized by an efficient catalytic version of ziegler's “aufbaureaktion” . Chem. , 2012 , 18 ( 44 ), 13974 – 13978 .

Mundil, R. ; Bravo, C. ; Merle, N. ; Zinck, P . Coordinative chain transfer and chain shuttling polymerization . Chem. Rev. , 2024 , 124 ( 1 ), 210 – 244 .

Lin, F. ; Liu, Z. H. ; Wang, M. Y. ; Liu, B. ; Li, S. H. ; Cui, D. M . Chain transfer to toluene in styrene coordination polymerization . Angew. Chem. Int. Ed. , 2020 , 59 ( 11 ), 4324 – 4328 .

Santoro, O. ; Piola, L. ; Cabe, K. M. ; Lhost, O. ; Den Dauw, K. ; Vantomme, A. ; Welle, A. ; Maron, L. ; Carpentier, J. F. ; Kirillov, E . Long-chain branched polyethylene via coordinative tandem insertion and chain-transfer polymerization using rac -{EBTHI}ZrCl 2 /MAO/Al-alkenyl combinations: an experimental and theoretical study . Macromolecules , 2020 , 53 ( 20 ), 8847 – 8857 .

Santoro, O. ; Piola, L. ; Mc Cabe, K. ; Lhost, O. ; Den Dauw, K. ; Vantomme, A. ; Welle, A. ; Maron, L. ; Carpentier, J. F. ; Kirillov, E . Al-alkenyl-induced formation of long-chain branched polyethylene via coordinative tandem insertion and chain-transfer polymerization using (nBuCp) 2 ZrCl 2 /MAO systems: An experimental and theoretical study . Eur. Polym. J. , 2021 , 154 , 110567 .

Göttker-Schnetmann, I. ; Kenyon, P. ; Mecking, S . Coordinative chain transfer polymerization of butadiene with functionalized aluminum reagents . Angew. Chem. Int. Ed. , 2019 , 58 ( 49 ), 17777 – 17781 .

German, I. ; Kelhifi, W. ; Norsic, S. ; Boisson, C. ; D’Agosto, F . Telechelic polyethylene from catalyzed chain-growth polymerization . Angew. Chem. Int. Ed. , 2013 , 52 ( 12 ), 3438 – 3441 .

Belaid, I. ; Poradowski, M. N. ; Bouaouli, S. ; Thuilliez, J. ; Perrin, L. ; D’Agosto, F. ; Boisson, C . Dialkenylmagnesium compounds in coordinative chain transfer polymerization of ethylene. reversible chain transfer agents and tools to probe catalyst selectivities toward ring formation . Organometallics , 2018 , 37 ( 10 ), 1546 – 1554 .

Norsic, S. ; Thomas, C. ; D’Agosto, F. ; Boisson, C . Divinyl-end-functionalized polyethylenes: ready access to a range of telechelic polyethylenes through thiol-ene reactions . Angew. Chem. Int. Ed. , 2015 , 54 ( 15 ), 4631 – 4635 .

Nzahou Ottou, W. ; Norsic, S. ; Belaid, I. ; Boisson, C. ; D’Agosto, F . Amino end-functionalized polyethylenes and corresponding telechelics by coordinative chain transfer polymerization . Macromolecules , 2017 , 50 ( 21 ), 8372 – 8377 .

Baulu, N. ; Poradowski, M. N. ; Verrieux, L. ; Thuilliez, J. ; Jean-Baptiste-dit-Dominique, F. ; Perrin, L. ; D’Agosto, F. ; Boisson, C . Design of selective divalent chain transfer agents for coordinative chain transfer polymerization of ethylene and its copolymerization with butadiene . Polym. Chem. , 2022 , 13 ( 14 ), 1970 – 1977 .

Minyaev, M. E. ; Komarov, P. D. ; Roitershtein, D. M. ; Lyssenko, K. A. ; Nifant’ev, I. E. ; Puntus, L. N. ; Varaksina, E. A. ; Borisov, R. S. ; Dyadchenko, V. P. ; Ivchenko, P. V . Aryloxy alkyl magnesium versus dialkyl magnesium in the lanthanidocene-catalyzed coordinative chain transfer polymerization of ethylene . Organometallics , 2019 , 38 ( 15 ), 2892 – 2901 .

Georges, S. ; Bonnet, F. ; Roussel, P. ; Visseaux, M. ; Zinck, P . β -Diketiminate-s upported magnesium alkyl: Synthesis, structure and application as co-catalyst for polymerizations mediated by a lanthanum half-sandwich complex . Appl. Organomet. Chem. , 2016 , 30 ( 1 ), 26 – 31 .

Wallace, M. A. ; Burkey, A. A. ; Sita, L. R . Phenyl-terminated polyolefins via living coordinative chain transfer polymerization with ZnPh 2 as a chain transfer agent . ACS Catal. , 2021 , 11 ( 16 ), 10170 – 10178 .

Lee, H. J. ; Baek, J. W. ; Kim, T. J. ; Park, H. S. ; Moon, S. H. ; Park, K. L. ; Bae, S. M. ; Park, J. ; Lee, B. Y . Synthesis of long-chain branched polyolefins by coordinative chain transfer polymerization . Macromolecules , 2019 , 52 ( 23 ), 9311 – 9320 .

Makio, H. ; Ochiai, T. ; Mohri, J. I. ; Takeda, K. ; Shimazaki, T. ; Usui, Y. ; Matsuura, S. ; Fujita, T . Synthesis of telechelic olefin polymers via catalyzed chain growth on multinuclear alkylene zinc compounds . J. Am. Chem. Soc. , 2013 , 135 ( 22 ), 8177 – 8180 .

Sun, L. X. ; Szuromi, E. ; Karjala, T. ; Zhou, Z. ; Carnahan, E . Synthesis of chain shuttling organometallic compounds capable of producing triblock polyolefins . Macromolecules , 2020 , 53 ( 24 ), 10796 – 10802 .

Gies, A. P. ; Zhou, Z. ; Sun, L. X. ; Szuromi, E. ; Huang, T. Z. ; Krasovskiy, A. ; Mukhopadhyay, S. ; Herceg, E. ; Kobylianskii, I. ; Shi, Z. ; Reyes, J. C. P . Microstructure characterization of functionalized ethylene/propylene polyolefins . Macromolecules , 2022 , 55 ( 7 ), 2542 – 2556 .

Han, X. W. ; Zhang, X. ; Zhou, Y. Y. ; Maimaitiming, A. ; Sun, X. L. ; Gao, Y. S. ; Li, P. Z. ; Zhu, B. Y. ; Chen, E. Y. ; Kuang, X. K. ; Tang, Y . Circular olefin copolymers made de novo from ethylene and α-olefins . Nat. Commun. , 2024 , 15 ( 1 ), 1462 .

Yu, Z. L. ; Han, X. W. ; Li, P. Z. ; Zhao, Y. N. ; Zhang, X. ; Sun, X. L. ; Gao, Y. S. ; Zhou, Y. Y. ; Tang, Y . Synthesis of telechelic isotactic polypropylenes for circular polypropylene-like materials via chain transfer polymerization . J. Am. Chem. Soc. , 2025 , 147 ( 5 ), 3931 – 3936 .

Zhang, L. ; Jiang, K. M. ; Shen, X. W. ; Gu, Y. ; Lin, X. R. ; Chen, M . Thienyl chloride initiated living cationic polymerization: a general and efficient access toward terminally functionalized poly(vinyl ether)s . Macromolecules , 2020 , 53 ( 5 ), 1536 – 1542 .

Belay, T. A. ; Chen, J. P. ; Xu, H. ; Zhang, S. W. ; Chen, S. L. ; Li, X. F . Functionalization methodology for synthesis of silane-end-functionalized linear and star poly(aryl isocyanide)s by combination of cationic polymerization and hydrosilylation reaction . Macromolecules , 2021 , 54 ( 19 ), 9007 – 9018 .

Uchiyama, M. ; Ohira, N. ; Yamashita, K. ; Sagawa, K. ; Kamigaito, M . Proton transfer anionic polymerization with C―H bond as the dormant species . Nat. Chem. , 2024 , 16 ( 10 ), 1630 – 1637 .

Motoyanagi, J. ; Fujishima, A. ; Minoda, M . Controlled synthesis and photoresponsive properties of spiropyran end-functionalized poly(vinyl ether)s . Crystals , 2022 , 12 ( 5 ), 742 .

Fuchise, K. ; Sato, K. ; Igarashi, M . Precise synthesis of linear polysiloxanes end-functionalized with alkynylsilyl groups by organocatalytic ring-opening polymerization of cyclotrisiloxanes . Macromolecules , 2021 , 54 ( 12 ), 5765 – 5773 .

Kottisch, V. ; Supej, M. J. ; Fors, B. P . Enhancing temporal control and enabling chain-end modification in photoregulated cationic polymerizations by using iridium-based catalysts . Angew. Chem. Int. Ed. , 2018 , 57 ( 27 ), 8260 – 8264 .

Johnson, H. C. ; Cueny, E. S. ; Landis, C. R . Chain transfer with dialkyl zinc during hafnium-pyridyl amido-catalyzed polymerization of 1-octene: relative rates, reversibility, and kinetic models . ACS Catal. , 2018 , 8 ( 5 ), 4178 – 4188 .

Zhang, X. ; Jiang, Y. ; Ma, Q. ; Hu, S. P. ; Liao, S. H . Metal-free cationic polymerization of vinyl ethers with strict temporal control by employing an organophotocatalyst . J. Am. Chem. Soc. , 2021 , 143 ( 17 ), 6357 – 6362 .

Mandsberg, N. K. ; Aslan, F. ; Dong, Z. Q. ; Levkin, P. A . 3D printing of reactive macroporous polymers via thiol-ene chemistry and polymerization-induced phase separation . Chem. Commun. , 2024 , 60 ( 45 ), 5872 – 5875 .

Sun, X. ; Huang, D. ; Li, G. Q. ; Sun, J. ; Zhang, Y. Y. ; Hu, B. ; Xie, M. B. ; Zhao, M. D. ; Zhang, X. C. ; Yu, J. ; Li, G . Artificial heart valve reinforced with silk woven fabric and poly(ethylene glycol) diacrylate hydrogels composite . Int. J. Biol. Macromol. , 2024 , 260 , 129485 .

Chu, S. L. ; Shi, X. L. ; Tian, Y. ; Gao, F. X . pH-responsive polymer nanomaterials for tumor therapy . Front. Oncol. , 2022 , 12 , 855019 .

Ju, H. K. ; Kim, S. Y. ; Lee, Y. M . pH/temperature-responsive behaviors of semi-IPN and comb-type graft hydrogels composed of alginate and poly( N -isopropylacrylamide) . Polymer , 2001 , 42 ( 16 ), 6851 – 6857 .

Ye, H. Q. ; Kwon, H. J. ; Ryu, K. Y. ; Lu, Y. F. ; Choi, H. H. ; Nam, S. Y. ; Feng, Z. X. ; Park, J. ; Mo, J. ; Zhang, H. J. ; Lee, J. ; Kong, H. ; Kim, S. H . Fluorinated polymeric insulating layer surface advancement by fluorine based cross-linking for high-performance organic electronic applications . J. Mater. Chem. C , 2024 , 12 ( 42 ), 17223 – 17232 .

Mastrangelo, F. ; Fioravanti, G. ; Quaresima, R. ; Vinci, R. ; Gherlone, E . Self-assembled monolayers (SAMs): which perspectives in implant dentistry ? J. Biomater. Nanobiotechnol. , 2011 , 2 ( 5 ), 533 – 543 .

Stadermann, J. ; Komber, H. ; Erber, M. ; Däbritz, F. ; Ritter, H. ; Voit, B . Diblock copolymer formation via self-assembly of cyclodextrin and adamantyl end-functionalized polymers . Macromolecules , 2011 , 44 ( 9 ), 3250 – 3259 .

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

单萜烯可持续聚合物的研究进展

1,3-双取代吲哚基稀土金属配合物的合成及催化异戊二烯聚合研究

乳液型原油降凝剂的制备及其降凝性能研究

聚合物反应挤出过程数值模拟进展