Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly

Yue-Xi Zhan; Li Zhang; Chun Feng; Jian-Bo Tan

doi:10.1007/s10118-025-3275-0

Your Location：

Home >

Browse articles >

Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly

RESEARCH ARTICLE | Updated：2025-02-25

- Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly
- Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly
- 高分子科学（英文） 2025年43卷第3期页码：429-438
- Affiliations：
  
  a.Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
  b.Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou 510006, China
  c.Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  cfeng@ecust.edu.cn (C.F.)
  tanjianbo@gdut.edu.cn (J.B.T.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22171055 and 52222301), the Guangdong Natural Science Foundation for Distinguished Young Scholar (No. 2022B1515020078), and the Science and Technology Program of Guangzhou (No. 2024A04J2821). They would like to thank Wei Song of Analysis and Test Center of Guangdong University of technology for DLS measurement.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-025-3275-0.
- DOI：10.1007/s10118-025-3275-0
  中图分类号：
- 收稿：2024-10-28，
  
  修回：2024-11-16，
  
  录用：2024-11-21，
  
  网络首发：2025-01-20，
  
  纸质出版：2025-03-01
- Accepted：
Scan QR Code
Zhan, Y. X.; Zhang, L.; Feng, C.; Tan, J. B. Structural difference in the core-forming block reshapes RAFT-mediated polymerization-induced self-assembly. Chinese J. Polym. Sci. 2025, 43, 429–438

Yue-Xi Zhan, Li Zhang, Chun Feng, et al. Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly[J]. Chinese Journal of Polymer Science, 2025, 43(3): 429-438.
Zhan, Y. X.; Zhang, L.; Feng, C.; Tan, J. B. Structural difference in the core-forming block reshapes RAFT-mediated polymerization-induced self-assembly. Chinese J. Polym. Sci. 2025, 43, 429–438 DOI： 10.1007/s10118-025-3275-0.

Yue-Xi Zhan, Li Zhang, Chun Feng, et al. Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly[J]. Chinese Journal of Polymer Science, 2025, 43(3): 429-438. DOI： 10.1007/s10118-025-3275-0.

摘要

Effects of the core-forming structure on polymerization-induced self-assembly as well as the morphology of block copolymer nanoparticles are investigated. It was found that the branched core-forming structure favored the formation of lower-order morphologies while the brush-like core-forming block favored the formation of higher-order morphologies.

Abstract

Polymerization-induced self-assembly (PISA) has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies. However

the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored. Herein

a series of multifunctional macromolecular chain transfer agents (macro-CTAs) were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers (CTMs). These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of styrene (St) to prepare block copolymers with different core-forming block structures and the assemblies. The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail. Transmission electron microscopy (TEM) analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies

while the branched core-forming block structure favored the formation of lower-order morphologies. Moreover

it was found that using macro-CTAs with a shorter length also promoted the formation of higher-order morphologies. Finally

structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs. We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.

关键词

Keywords

references

Wan, W. M.; Hong, C. Y.; Pan, C. Y. One-pot synthesis of nanomaterials via RAFT polymerization induced self-assembly and morphology transition. Chem. Commun. 2009 , 39 , 5883−5885..

Liu, C.; Hong, C. Y.; Pan, C. Y. Polymerization techniques in polymerization-induced self-assembly (PISA). Polym. Chem. 2020 , 11 , 3673−3689..

Zhang, W. J.; Hong, C. Y.; Pan, C. Y. Polymerization-induced self-assembly of functionalized block copolymer nanoparticles and their application in drug delivery. Macromol. Rapid Commun. 2019 , 40 , 1800279..

Zhu, R. M.; Chang, Z. X.; Zhang, W. J.; Hong, C. Y. Polymerization-induced self-assembly with assistance of aromatic in teractions facilitates the formation of polymeric nanotubes. Macromolecules 2023 , 56 , 3296−3303..

Kadirkhanov, J.; Yang, C. L.; Chang, Z. X.; Zhu, R. M.; Pan, C. Y.; You, Y. Z.; Zhang, W. J.; Hong, C. Y. In situ cross-linking polymerization-induced self-assembly not only generates cross-linked structures but also promotes morphology transition by the cross-linker. Polym. Chem . 2021 , 12 , 1768–1775..

An, Z.; Shi, Q.; Tang, W.; Tsung, C. K.; Hawker, C. J.; Stucky, G. D. Facile RAFT precipitation polymerization for the microwave-assisted synthesis of well-defined, double hydrophilic block copolymers and nanostructured hydrogels. J. Am. Chem. Soc. 2007 , 129 , 14493−14499..

Lv, F.; An, Z.; Wu, P. Efficient access to inverse bicontinuous mesophases via polymerization-induced cooperative assembly. CCS Chem. 2020 , 3 , 2211−2222..

Zhu, A.; Lv, X.; Shen, L.; Zhang, B.; An, Z. Polymerization-induced cooperative assembly of block copolymer and homopolymer via RAFT dispersion polymerization. ACS Macro Lett. 2017 , 6 , 304−309..

Wang, X.; Shen, L.; An, Z. Dispersion polymerization in environmentally benign solvents via reversible deactivation radical polymerization. Prog. Polym. Sci. 2018 , 83 , 1−27..

Li, S.; Han, G.; Zhang, W. Cross-linking approaches for block copolymer nano-assemblies via RAFT-mediated polymerization-induced self-assembly. Polym. Chem. 2020 , 11 , 4681−4692..

Pang, B.; Liu, Y.; Cao, R.; Zhang, W. Hybrid nanoscale vesicles of polyhedral oligomeric silsesquioxane-based star block copolymers for thermal insulation applications. ACS Appl. Nano Mater. 2022 , 5 , 7042−7050..

Huang, J.; Guo, Y.; Gu, S.; Han, G.; Duan, W.; Gao, C.; Zhang, W. Multicompartment block copolymer nanoparticles: recent advances and future perspectives. Polym. Chem. 2019 , 10 , 3426−3435..

Wang, L.; Ding, Y.; Liu, Q.; Zhao, Q.; Dai, X.; Lu, X.; Cai, Y. Sequence-controlled polymerization-induced self-assembly. ACS Macro Lett. 2019 , 8 , 623−628..

Cao, L.; Zhao, Q.; Liu, Q.; Ma, L.; Li, C.; Wang, X.; Cai, Y. Electrostatic manipulation of triblock terpolymer nanofilm compartmentalization during aqueous photoinitiated polymerization-induced self-assembly. Macromolecules 2020 , 53 , 2220−2227..

Wang, Y.; Li, C.; Ma, L.; Wang, X.; Wang, K.; Lu, X.; Cai, Y. Interfacial liquid-liquid phase separation-driven polymerization-induced electrostatic self-assembly. Macromolecules 2021 , 54 , 5577−5585..

Ding, Y.; Cai, M.; Cui, Z.; Huang, L.; Wang, L.; Lu, X.; Cai, Y. Synthesis of low-dimensional polyion complex nanomaterials via polymerization-induced electrostatic self-assembly. Angew. Chem. Int. Ed. 2018 , 57 , 1053−1056..

Guan, S.; Chen, A. Influence of spacer lengths on the morphology of biphenyl-containing liquid crystalline block copolymer nanoparticles via polymerization-induced self-assembly. Macromolecules 2020 , 53 , 6235−6245..

Li, Y.; Li, Y.; Yan, R.; Zhang, L.; Liu, H.; Tan, J. Chain architecture as an orthogonal parameter to tune morphologies of polymer assemblies: efficient synthesis and self-assembly of linear -branched block copolymers via RAFT dispersion polymerization. Macromolecules 2024 , 57 , 5175−5188..

Cao, J.; Li, Y.; Tan, Y.; Zhang, L.; Tan, J. From RAFT emulsion polymerization to RAFT dispersion polymerization: a facile approach to tuning dispersities and behaviors of self-assembled block copolymers. Polym. Chem. 2024 , 15 , 106–117..

Li, Z.; Wang, R.; Luo, X.; Zhang, L.; Tan, J. ABC or ACB triblock copolymers? Changing the RAFT group position in diblock copolymer macro-RAFT agents leads to different PISA behaviors in RAFT dispersion polymerization. Polym. Chem. 2024 , 15 , 1736−1747..

Niu, B.; Huang, H.; Zhang, L.; Tan, J. Grafting block copolymer nanoparticles to a surface via aqueous photoinduced polymerization-induced self-assembly at room temperature. ACS Macro Lett. 2024 , 13 , 577−585..

He, J.; Chen, Y.; Zhang, L.; Tan, J. Oxidation-responsive framboidal triblock copolymer vesicles prepared by photoinitiated RAFT seeded emulsion polymerization. Chin. Chem. Lett. 2023 , 34 , 107344..

Zhao, S.; Zhang, L.; Tan, J. In situ synthesis of branched block copolymer assemblies via raft dispersion polymerization using branched macro-RAFT agents. Chin. J. Chem . 2023 , 41 , 1517–1525..

Zhou, J.; Huang, Q.; Zhang, L.; Tan, J. Exploiting the monomer-feeding mechanism of RAFT emulsion polymerization for polymerization-induced self-assembly of asymmetric divinyl monomers. ACS Macro Lett. 2023 , 12 , 1457−1465..

Canning, S. L.; Smith, G. N.; Armes, S. P. A critical appraisal of RAFT-mediated polymerization-induced self-assembly. Macromolecules 2016 , 49 , 1985−2001..

Penfold, N. J. W.; Yeow, J.; Boyer, C.; Armes, S. P. Emerging trends in polymerization-induced self-assembly. ACS Macro Lett. 2019 , 8 (8), 1029–1054..

Warren, N. J.; Armes, S. P. Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization. J. Am. Chem. Soc. 2014 , 136 , 10174−10185..

Yeow, J.; Boyer, C. Photoinitiated polymerization-induced self-assembly (photo-PISA): new insights and opportunities. Adv. Sci. 2017 , 4 , 1700137..

Lin, D.; Zhang, L.; Tan, J. Room-temperature heterogeneous reversible deactivation radical polymerization. Acta Polymerica Sinica (in Chinese) 2023 , 54 , 761–777..

Xiang, J. Y.; Zhang, W. L.; Li, H. T.; He, Y. N. pH induced self-assembly of AIE fluorescent probe for tumor imaging. Chinese J. Polym. Sci . 2024 , 42 , 7–13..

Du, J.; Tang, Y.; Lewis, A. L.; Armes, S. P. pH-sensitive vesicles based on a biocompatible zwitterionic diblock copolymer. J. Am. Chem. Soc . 2005 , 127 , 17982–17983..

Du, J.; Sun, H. Polymer/TiO 2 hybrid vesicles for excellent uv screening and effective encapsulation of antioxidant agents. ACS Appl. Mater. Interfaces 2014 , 6 , 13535−13541..

Gao, Y.; Qiu, H.; Zhou, H.; Li, X.; Harniman, R.; Winnik, M. A.; Manners, I. Crystallization-driven solution self-assembly of block copolymers with a photocleavable junction. J. Am. Chem. Soc. 2015 , 137 , 2203−2206..

Song, Y.; Xiang, B.; Huang, X. Y.; Lu, G.-L.; Feng, C. Living crystallization-driven self-assembly of oligo(p-phenylene vinylene)-containing block copolymers: impact of branched structure of alkyl side chain of π -conjugated segment. Chinese J. Polym. Sci. 2023 , 41 , 574−584..

Blanazs, A.; Ryan, A. J.; Armes, S. P. Predictive phase diagrams for RAFT aqueous dispersion polymerization: effect of block copolymer composition, molecular weight, and copolymer concentration. Macromolecules 2012 , 45 , 5099−5107..

Tan, J.; Liu, D.; Bai, Y.; Huang, C.; Li, X.; He, J.; Xu, Q.; Zhang, X.; Zhang, L. An insight into aqueous photoinitiated polymerization-induced self-assembly (photo-PISA) for the preparation of diblock copolymer nano-objects. Polym. Chem. 2017 , 8 , 1315−1327..

Tan, J.; Bai, Y.; Zhang, X.; Zhang, L. Room temperature synthesis of poly(poly(ethylene glycol) methyl ether methacrylate)-based diblock copolymer nano-objects via photoinitiated polymerization-induced self-assembly (photo-PISA). Polym. Chem. 2016 , 7 , 2372−2380..

Jones, E. R.; Semsarilar, M.; Blanazs, A.; Armes, S. P. Efficient synthesis of amine-functional diblock copolymer nanoparticles via RAFT dispersion polymerization of benzyl methacrylate in alcoholic media. Macromolecules 2012 , 45 , 5091−5098..

He, J.; Liu, D.; Tan, J.; Zhang, L. Sodium bis(acyl)phosphane oxide (SBAPO): an efficient photoinitiator for blue light initiated aqueous RAFT dispersion Polymerization. Polymer 2018 , 145 , 70−79..

Ma, Y.; Gao, P.; Ding, Y.; Huang, L.; Wang, L.; Lu, X.; Cai, Y. Visible light initiated thermoresponsive aqueous dispersion polymerization-induced self-assembly. Macromolecules 2019 , 52 , 1033−1041..

Blackman, L. D.; Doncom, K. E. B.; Gibson, M. I.; O’Reilly, R. K. Comparison of photo- and Thermally Initiated Polymerization-induced self-assembly: a lack of end group fidelity drives the formation of higher order morphologies. Polym. Chem. 2017 , 8 , 2860−2871..

Luo, X.; Zhao, S.; Chen, Y.; Zhang, L.; Tan, J. Switching between thermal initiation and photoinitiation redirects RAFT-mediated polymerization-induced self-assembly. Macromolecules 2021 , 54 , 2948−2959..

Gao, C.; Zhou, H.; Qu, Y.; Wang, W.; Khan, H.; Zhang, W. In Situ synthesis of block copolymer nanoassemblies via polymerization-induced self-assembly in poly(ethylene glycol). Macromolecules 2016 , 49 , 3789−3798..

Lv, F.; An, Z.; Wu, P. What determines the formation of block copolymer nanotubes. Macromolecules 2020 , 53 , 367−373..

Jones, E. R.; Semsarilar, M.; Wyman, P.; Boerakker, M.; Armes, S. P. Addition of water to an Alcoholic RAFT PISA formulation leads to faster kinetics but limits the evolution of copolymer morphology. Polym. Chem. 2016 , 7 , 851−859..

Wang, X.; Figg, C. A.; Lv, X.; Yang, Y.; Sumerlin, B. S.; An, Z. Star architecture promoting morphological transitions during polymerization-induced self-assembly. ACS Macro Lett. 2017 , 6 , 337−342..

Zhang, Y.; Cao, M.; Han, G.; Guo, T.; Ying, T.; Zhang, W. Topology affecting block copolymer nanoassemblies: linear block copolymers versus star block copolymers under PISA conditions. Macromolecules 2018 , 51 , 5440−5449..

Cao, M.; Han, G.; Duan, W.; Zhang, W. Synthesis of multi-arm star thermo-responsive polymers and topology effects on phase transition. Polym. Chem. 2018 , 9 , 2625−2633..

Zhang, Y.; Guan, T.; Han, G.; Guo, T.; Zhang, W. Star Block Copolymer Nanoassemblies: Block Sequence Is All-Important. Macromolecules 2019 , 52 , 718−728..

Liu, D.; Chen, Y.; Zhang, L.; Tan, J. Efficient preparation of branched block copolymer assemblies by photoinitiated RAFT self-condensing vinyl dispersion polymerization. Macromolecules 2020 , 53 , 9725−9735..

Cai, W.; Yang, S.; Zhang, L.; Chen, Y.; Zhang, L.; Tan, J. Efficient synthesis and self-assembly of segmented hyperbranched block copolymers via RAFT-mediated dispersion polymerization using segmented hyperbranched macro-RAFT agents. Macromolecules 2022 , 55 , 5775−5787..

Liu, D.; Yang, S.; Peng, S.; Chen, Y.; Zhang, L.; Tan, J. Simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature via photoinitiated RAFT dispersion polymerization. Macromol. Rapid Commun. 2022 , 43 , 2100921..

Wu, J.; Zhang, L.; Chen, Y.; Tan, J. Linear and star block copolymer nanoparticles prepared by heterogeneous RAFT polymerization using an ω , ω -heterodifunctional macro-RAFT agent. ACS Macro Lett. 2022 , 11 , 910−918..

Lin, W.; Jia, S.; Li, Y.; Zhang, L.; Liu, H.; Tan, J. Aqueous RAFT dispersion polymerization mediated by an ω , ω -macromolecular chain transfer monomer: an efficient approach for amphiphilic branched block copolymers and the assemblies. ACS Macro Lett. 2024 , 13 , 1022−1030..

Wang, R.; Zhu, W.; Zhang, L.; Sheng, X.; Tan, J. Synthesis of self-assembled star/linear block copolymer blends via aqueous RAFT dispersion polymerization. Chin. J. Chem. 2024 , 42 , 1606−1614..

Xie, G.; Wu, J.; Zhang, L.; Tan, J. Efficient synthesis of μ -A(BC)C miktoarm star polymer assemblies via aqueous photoinitiated polymerization-induced self-assembly. Langmuir 2024 , 40 , 17098−17108..

Ferji, K.; Venturini, P.; Cleymand, F.; Chassenieux, C.; Six, J. L. In situ glyco-nanostructure formulation via photo-polymerization induced self-assembly. Polym. Chem. 2018 , 9 , 2868−2872..

Georgiou, P. G.; Kontopoulou, I.; Congdon, T. R.; Gibson, M. I. Ice recrystallisation inhibiting polymer nano-objects via saline-tolerant polymerisation-induced self-assembly. Mater. Horiz. 2020 , 7 , 1883−1887..

Zeng, R.; Chen, Y.; Zhang, L.; Tan, J. R-RAFT or Z-RAFT? Well-defined star block copolymer nano-objects prepared by RAFT-mediated polymerization-induced self-assembly. Macromolecules 2020 , 53 , 1557−1566..

Shanmugam, S.; Cuthbert, J.; Kowalewski, T.; Boyer, C.; Matyjaszewski, K. Catalyst-free selective photoactivation of RAFT polymerization: a facile route for preparation of comblike and bottlebrush polymers. Macromolecules 2018 , 51 , 7776−7784..

Chen, K.; Hu, X.; Zhu, N.; Guo, K. Design, synthesis, and self-assembly of Janus bottlebrush polymers. Macromol. Rapid Commun. 2020 , 41 , 2000357..

Yang, S.; Zhang, L.; Chen, Y.; Tan, J. Combining green light-activated photoiniferter RAFT polymerization and RAFT dispersion polymerization for graft copolymer assemblies. Macromolecules 2022 , 55 , 8472−8484..

Gody, G.; Zetterlund, P. B.; Perrier, S.; Harrisson, S. The limits of precision monomer placement in chain growth polymerization. Nat. Commun. 2016 , 7 , 10514..

Doncom, K. E. B.; Blackman, L. D.; Wright, D. B.; Gibson, M. I.; O’Reilly, R. K. Dispersity effects in polymer self-assemblies: a matter of hierarchical control. Chem. Soc. Rev. 2017 , 46 , 4119−4134..

Gao, C.; Li, S.; Li, Q.; Shi, P.; Shah, S. A.; Zhang, W. Dispersion RAFT polymerization: comparison between the monofunctional and bifunctional macromolecular RAFT agents. Polym. Chem. 2014 , 5 , 6957−6966..

Blanazs, A.; Madsen, J.; Battaglia, G.; Ryan, A. J.; Armes, S. P. Mechanistic insights for block copolymer morphologies: how do worms form vesicles. J. Am. Chem. Soc. 2011 , 133 , 16581−16587..

Tan, J.; Xu, Q.; Li, X.; He, J.; Zhang, Y.; Dai, X.; Yu, L.; Zeng, R.; Zhang, L. Enzyme-PISA: an efficient method for preparing well-defined polymer nano-objects under mild conditions. Macromol. Rapid Commun. 2018 , 39 , 1700871..

Liu, D.; Cai, W.; Zhang, L.; Boyer, C.; Tan, J. Efficient photoinitiated polymerization-induced self-assembly with oxygen tolerance through dual-wavelength type I photoinitiation and photoinduced deoxygenation. Macromolecules 2020 , 53 , 1212−1223..

浏览量

129

Downloads

CSCD

文章被引用时，请邮件提醒。

Submit

工具集

关联资源

Organic Brønsted Acid-Catalyzed Stereoselective Cationic RAFT Polymerization: The Effect of RAFT Agents

Conventional Radical and RAFT Alternating Copolymerizations of Hydroxyalkyl Vinyl Ethers and Dialkyl Maleates

Architecting Branch Structure in Terpolymer of CO2, Propylene Oxide and Phthalic Anhydride: An Enhancement in Thermal and Mechanical Performances

Topology-regulated Co-assembly of Single Chain Polymer Nanoparticles and Block Copolymers into Hierarchical Micelle@Vesicle Composite Structures

From Molecular Defect to Macroscopic Performance: Manipulating Dichroism and Mechanics in Iodine-doped Poly(vinyl alcohol) via Ethylene Incorporation