Uniform Branched Polymer Microspheres <italic style="font-style: italic">via</italic> Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization

Chao-Jian Luo; Li Zhang; Jian-Bo Tan

doi:10.1007/s10118-026-3600-2

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Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization

RESEARCH ARTICLE | Updated：2026-07-01

- Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization
- Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2153-2166
- 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
- Author bio：
  
  tanjianbo@gdut.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 52573005). We would like to thank Weitian Lin at the Analysis and Test Center of Guangdong University of Technology for assistance with the ultramicrotomy.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3600-2.The related data of this paper is data that should not be shared, and can be obtained from the author for reasonable reasons. The author’s contact information: tanjianbo@gdut.edu.cn.
- DOI：10.1007/s10118-026-3600-2
  中图分类号：
- 收稿：2026-01-06，
  
  修回：2026-01-26，
  
  录用：2026-01-28，
  
  网络首发：2026-05-09，
  
  纸质出版：2026-07-05
- Accepted：
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Luo, C. J.; Zhang, L.; Tan, J. B. Uniform branched polymer microspheres via reversible addition-fragmentation chain transfer dispersion self-condensing vinyl polymerization. Chinese J. Polym. Sci. 2026, 44, 2153–2166

Chao-Jian Luo, Li Zhang, Jian-Bo Tan. Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2153-2166. DOI: 10.1007/s10118-026-3600-2.
Luo, C. J.; Zhang, L.; Tan, J. B. Uniform branched polymer microspheres via reversible addition-fragmentation chain transfer dispersion self-condensing vinyl polymerization. Chinese J. Polym. Sci. 2026, 44, 2153–2166 DOI： 10.1007/s10118-026-3600-2.

Chao-Jian Luo, Li Zhang, Jian-Bo Tan. Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2153-2166. DOI: 10.1007/s10118-026-3600-2. DOI：

摘要

This study reports a reversible addition-fragmentation chain transfer (RAFT) dispersion self-condensing vinyl polymerization platform using a chain-transfer monomer and macro-RAFT agent for the one-pot synthesis of monodisperse microspheres composed of well-defined branched (multi)block copolymers.

Abstract

We report a reversible addition-fragmentation chain transfer (RAFT) dispersion self-condensing vinyl polymerization (SCVP) platform using a chain-transfer monomer (CTM) and macro-RAFT agent for the one-pot synthesis of monodisperse microspheres composed of well-defined branched (multi)block copolymers. Under RAFT dispersion polymerization conditions

the CTM functions as both a comonomer and branching RAFT site

affording polymer microspheres containing branched polymers while maintaining narrow particle size distributions. The preserved RAFT end-groups on the branches enabled seeded chain extension to give branched diblock and multiblock copolymer microspheres with methyl methacrylate (MMA) and a range of second monomers

while retaining microsphere monodispersity. Using styrene (St) as the second monomer yielded nanostructured branched PMMA-

-PSt microspheres

whose internal morphologies underwent a sphere-to-cylinder transition as the branching degree in the PMMA block was decreased at a fixed composition. These results establish the branching degree in the branched block as an effective parameter to manipulate intraparticle phase behavior and demonstrate RAFT dispersion SCVP as a scalable route to sequence-controlled

topologically complex polymer microspheres with tunable internal

nanostructures.

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references

Gao, C.; Yan, D. Hyperbranched polymers: from synthesis to applications. Prog. Polym. Sci. 2004 , 29 , 183−275..

Li, Y.; Beija, M.; Laurent, S.; Elst, L. vander; Muller, R. N.; Duong, H. T. T.; Lowe, A. B.; Davis, T. P.; Boyer, C. Macromolecular ligands for gadolinium MRI contrast agents. Macromolecules 2012 , 45 , 4196−4204..

Pal, S.; Hill, M. R.; Sumerlin, B. S. Doubly-responsive hyperbranched polymers and core-crosslinked star polymers with tunable reversibility. Polym. Chem. 2015 , 6 , 7871−7880..

Konkolewicz, D.; Monteiro, M. J.; Perrier, S. Dendritic and hyperbranched polymers from macromolecular units: elegant approaches to the synthesis of functional polymers. Macromolecules 2011 , 44 , 7067−7087..

[Polymeropoulos, G.; Zapsas, G.; Ntetsikas, K.; Bilalis, P.; Gnanou, Y.; Hadjichristidis, N. 50th anniversary perspective : polymers with complex architectures. Macromolecules 2017 , 50 , 1253–1290..

Zhang, M.; Liu, H.; Shao, W.; Ye, C.; Zhao, Y. Versatile Synthesis of multiarm and miktoarm star polymers with a branched core by combination of menschutkin reaction and controlled polymerization. Macromolecules 2012 , 45 , 9312−9325..

Wu, W.; Tang, R.; Li, Q.; Li, Z. Functional hyperbranched polymers with advanced optical, electrical and magnetic properties. Chem. Soc. Rev. 2015 , 44 , 3997−4022..

Zheng, Y.; Li, S.; Weng, Z.; Gao, C. Hyperbranched polymers: advances from synthesis to applications. Chem. Soc. Rev. 2015 , 44 , 4091−4130..

Fréchet, J. M. J.; Henmi, M.; Gitsov, I.; Aoshima, S.; Leduc, M. R.; Grubbs, R. B. Self-condensing vinyl polymerization: an approach to dendritic materials. Science 1995 , 269 , 1080−1083..

Vogt, A. P.; Sumerlin, B. S. Tuning the temperature response of branched poly(N-Isopropylacrylamide) prepared by RAFT polymerization. Macromolecules 2008 , 41 , 7368−7373..

Bektas, S.; Ciftci, M.; Yagci, Y. Hyperbranched Polymers by visible light induced self-condensing vinyl polymerization and their modifications. Macromolecules 2013 , 46 , 6751−6757..

[A. Alfurhood, J.; R. Bachler, P.; S. Sumerlin, B. Hyperbranched polymers via RAFT self-condensing vinyl polymerization. Polym. Chem. 2016 , 7 , 3361–3369..

Sun, H.; Kabb, C. P.; Sumerlin, B. S. Thermally-labile segmented hyperbranched copolymers: using reversible-covalent chemistry to investigate the mechanism of self-condensing vinyl copolymerization. Chem. Sci. 2014 , 5 , 4646−4655..

Gaynor, S. G.; Edelman, S.; Matyjaszewski, K. Synthesis of Branched and hyperbranched polystyrenes. Macromolecules 1996 , 29 , 1079−1081..

Sims, M. B.; Patel, K. Y.; Bhatta, M.; Mukherjee, S.; Sumerlin, B. S. Harnessing imine diversity to tune hyperbranched polymer degradation. Macromolecules 2018 , 51 , 356−363..

Wang, X.; Gao, H. Recent progress on hyperbranched polymers synthesized via radical-based self-condensing vinyl polymerization. Polymers 2017 , 9 , 188..

Min, K.; Gao, H. New method to access hyperbranched polymers with uniformstructure via one-pot polymerization of inimer in microemulsion. J. Am. Chem. Soc. 2012 , 134 , 15680−15683..

Graff, R. W.; Wang, X.; Gao, H. Exploring self-condensing vinyl polymerization of inimers in microemulsion to regulate the structures of hyperbranched polymers. Macromolecules 2015 , 48 , 2118−2126..

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..

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..

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..

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..

Yin, R.; Tarnsangpradit, J.; Gul, A.; Jeong, J.; Hu, X.; Zhao, Y.; Wu, H.; Li, Q.; Fytas, G.; Karim, A.; Bockstaller, M. R.; Matyjaszewski, K. Organic Nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP. Proc. Natl. Acad. Sci. 2024 , 121 , e2406337121..

[Liu, D.; He, J.; Zhang, L.; Tan, J. 100th anniversary of macromolecular science viewpoint: heterogenous reversible deactivation radical polymerization at room temperature. recent advances and future opportunities. ACS Macro Lett . 2019 , 8 , 1660–1669..

Zetterlund, P. B.; Thickett, S. C.; Perrier, S.; Bourgeat-Lami, E.; Lansalot, M. Controlled/living radical polymerization in dispersed systems: an update. Chem. Rev. 2015 , 115 , 9745−9800..

Zetterlund, P. B.; Kagawa, Y.; Okubo, M. Controlled/living radical polymerization in dispersed systems. Chem. Rev. 2008 , 108 , 3747−3794..

Koker, S. D.; Lambrecht, B. N.; Willart, M. A.; Kooyk, Y. van; Grooten, J.; Vervaet, C.; Remon, J. P.; Geest, B. G. D. Designing polymeric particles for antigen delivery. Chem. Soc. Rev. 2010 , 40 , 320−339..

Campos, E.; Branquinho, J.; Carreira, A. S.; Carvalho, A.; Coimbra, P.; Ferreira, P.; Gil, M. H. Designing polymeric microparticles for biomedical and industrial applications. Eur. Polym. J. 2013 , 49 , 2005−2021..

Ugelstad, J.; Berge, A.; Ellingsen, T.; Schmid, R.; Nilsen, T.-N.; Mørk, P. C.; Stenstad, P.; Hornes, E.; Olsvik, Ø. Preparation and application of new monosized polymer particles. Prog. Polym. Sci. 1992 , 17 , 87−161..

Abdelrahman, A. I.; Dai, S.; Thickett, S. C.; Ornatsky, O.; Bandura, D.; Baranov, V.; Winnik, M. A. Lanthanide-containing polymer microspheres by multiple-stage dispersion polymerization for highly multiplexed bioassays. J. Am. Chem. Soc. 2009 , 131 , 15276−15283..

Feng, M.; Chen, J.; Xun, J.; Dai, R.; Zhao, W.; Lu, H.; Xu, J.; Chen, L.; Sui, G.; Cheng, X. Development of a sensitive immunochromatographic method using lanthanide fluorescent microsphere for rapid serodiagnosis of COVID-19. ACS Sens. 2020 , 5 , 2331−2337..

Zhu, W.; Ye, Y.; Zhang, L.; Zhao, G.; Tan, J. Molecular bottlebrush-stabilized polymeric microspheres by photoinitiated RAFT dispersion polymerization for bead-based immunoassays. Biomacromolecules 2026 , 27 , 822−834..

Ye, Y.; Zhu, W.; Zhang, L.; Tan, J. Combining RAFT dispersion polymerization and surface-initiated ATRP for surface engineering of polymeric microspheres. ACS Macro Lett. 2025 , 14 , 1852−1860..

Ha, S.; La, Y.; Kim, K. T. Polymer cubosomes: infinite cubic mazes and possibilities. Acc. Chem. Res. 2020 , 53 , 620−631..

Guo, Q.; Xue, R.; Zhao, J.; Zhang, Y.; van de Kerkhof, G. T.; Zhang, K.; Li, Y.; Vignolini, S.; Song, D. P. Precise tailoring of polyester bottlebrush amphiphiles toward eco-friendly photonic pigments via interfacial self-assembly. Angew. Chem. Int. Ed. 2022 , 61 , e202206723..

Liu, Q. J.; Liu, Q.; Zhang, J.; Zhang, C.; Qian, L.; Qi, H.; Li, Y. S.; Song, D. P. Photonic microspheres for high-capacity dna data storage: robust, straightforward, and scalable random access via nonfading indexes. Sci. Adv. 2025 , 11 , eadw2613..

Wong, C. K.; Qiang, X.; Müller, A. H. E.; Gröschel, A. H. Self-assembly of block copolymers into internally ordered microparticles. Prog. Polym. Sci. 2020 , 102 , 101211..

Zhang, Y.; Liu, X.; Yan, N.; Hu, Y.; Li, H.; Zhu, Y. Confined self-assembly of block copolymers within the three-dimensional soft space. Prog. Chem. 2018 , 30 , 166−178..

Zhang, M.; Xu, Y.; Zhu, J.; Xu, J. Responsive surfactant-driven morphology transformation of block copolymer microparticles. Chem. Eur. J. 2025 , 31 , e202404245..

Wang, Y.; Liu, S.; Yan, N.; Ma, T.; Zhu, Y. Recent advancements in the precise engineering of block copolymer microparticles via confined assembly in emulsion droplets. Nanoscale 2025 , 17 , 27667−27684..

Wang, Z.; Chan, C. L. C.; Zhao, T. H.; Parker, R. M.; Vignolini, S. Recent advances in block copolymer self-assembly for the fabrication of photonic films and pigments. Adv. Opt. Mater. 2021 , 9 , 2100519..

Jennings, J.; Beija, M.; Richez, A. P.; Cooper, S. D.; Mignot, P. E.; Thurecht, K. J.; Jack, K. S.; Howdle, S. M. One-pot synthesis of block copolymers in supercritical carbon dioxide:a simple versatile route to nanostructured microparticles. J. Am. Chem. Soc. 2012 , 134 , 4772−4781..

Alauhdin, M.; Bennett, T. M.; He, G.; Bassett, S. P.; Portale, G.; Bras, W.; Hermida-Merino, D.; Howdle, S. M. Monitoring morphology evolution within block copolymer microparticles during dispersion polymerisation in supercritical carbon dioxide: a high pressure SAXS study. Polym. Chem. 2019 , 10 , 860−871..

Bennett, T. M.; He, G.; Larder, R. R.; Fischer, M. G.; Rance, G. A.; Fay, M. W.; Pearce, A. K.; Parmenter, C. D. J.; Steiner, U.; Howdle, S. M. Clean block copolymer microparticles from supercritical CO 2 : universal templates for the facile and scalable fabrication of hierarchical mesostructured metal oxides. Nano Lett. 2018 , 18 , 7560−7569..

Song, J.-S.; Winnik, M. A. Monodisperse, micron-sized reactive low molar mass polymer microspheres by two-stage living radical dispersion polymerization of styrene. Macromolecules 2006 , 39 , 8318−8325..

Min, K.; Matyjaszewski, K. Atom transfer radical dispersion polymerization of styrene in ethanol. Macromolecules 2007 , 40 , 7217−7222..

Liu, C.; Li, H.; Zhang, L.; Tan, J. Efficient preparation of monodisperse block copolymer microsphe res via one-pot RAFT dispersion polymerization. Macromolecules 2025 , 58, 13276−13287..

Deng, Z.; Liu, S. Emerging trends in solution self-assembly of block copolymers. Polymer 2020 , 207 , 122914..

Gao, Y.; Deng, H.; Li, W.; Qiu, F.; Shi, A. C. Formation of nonclassical ordered phases of $AB$-type multiarm block copolymers. Phys. Rev. Lett. 2016 , 116 , 068304..

Tan, J.; Rao, X.; Jiang, D.; Yang, J.; Zeng, Z. One-stage photoinitiated RAFT dispersion polymerization — reaction parameters for achieving high particle size uniformity. Polymer 2014 , 55 , 2380−2388..

Li, H.; Liu, C.; Zhang, L.; Tan, J. High-temperature photoinitiated RAFT dispersion polymerization: a light-mediated approach for controlled synthesis of well-defined polymeric microspheres. ACS Appl. Polym. Mater. 2026 , 8 , 292−305..

Zheng, Z.; Luo, C.; Zhang, L.; Tan, J. Scalable preparation of well-defined hierarchical colloidal materials by heterogeneous orthogonal RAFT Polymerization in water. ACS Macro Lett. 2025 , 14 , 1299−1306..

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..

Yu, L.; Dai, X.; Zhang, Y.; Zeng, Z.; Zhang, L.; Tan, J. Better RAFT control is better? insights into the preparation of monodisperse surface-functional polymeric microspheres by photoinitiated RAFT dispersion polymerization. Macromolecules 2019 , 52 , 7267−7277..

Xiao, M.; Zhang, L.; Tan, J. Transitioning from photoinitiation to thermal initiation in RAFT dispersion polymerization via a small modification of the macro-RAFT agent: a scalable approach for monodisperse surface-functional polymeric microspheres. Macromolecules 2023 , 56 , 7675−7688..

Niu, B.; Huang, H.; Luo, L.; Zhang, L.; Tan, J. Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chin. Chem. Lett. 2025 , 36 , 110431..

Pacheco, A. A. C.; Filho, A. F. da S.; Kortsen, K.; Hanson-Heine, M. W. D.; Taresco, V.; Hirst, J. D.; Lansalot, M.; D’Agosto, F.; Howdle, S. M. Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2. Chem. Sci. 2021 , 12 , 1016−1030..

Li, L.; Dong, Q.; Li, W. Stabilize various novel network structures via the alternate arrangement of A/C domains in close contact by tailoring ABC miktoarm star architectures. Macromolecules 2024 , 57 , 409−419..

Dong, Q.; Li, W. Effect of molecular asymmetry on the formation of asymmetric nanostructures in ABC-Type Block Copolymers. Macromolecules 2021 , 54 , 203−213..

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..

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

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Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization

Uniform Branched Polymer Microspheres via Reversible Addition-fragmentation Chain Transfer Dispersion Self-condensing Vinyl Polymerization

DOI：10.1007/s10118-026-3600-2

摘要

Abstract

关键词

Keywords

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