

FOLLOWUS
a.Faculty of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China
b.College of Chemistry, Xiangtan University, Xiangtan 411105, China
c.Guangdong Provincial Key Laboratory of Luminescence from Molecular Aggregates, South China University of Technology, Guangzhou 510640, China
msjpzhao@scut.edu.cn
Received:14 June 2026,
Accepted:20 July 2026,
Online First:14 October 2026,
Published:2026-09
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Li, H.; Xia, Y. N.; Liu, L. J.; Zhao, J. P. Urea-welded anionic vinyl-addition and ring-opening polymerizations for one-pot hybrid block copolymer synthesis. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3823-2
Heng Li, Ye-Ning Xia, Li-Jun Liu, et al. Urea-welded Anionic Vinyl-addition and Ring-opening Polymerizations for One-pot Hybrid Block Copolymer Synthesis[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8.
Li, H.; Xia, Y. N.; Liu, L. J.; Zhao, J. P. Urea-welded anionic vinyl-addition and ring-opening polymerizations for one-pot hybrid block copolymer synthesis. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3823-2 DOI:
Heng Li, Ye-Ning Xia, Li-Jun Liu, et al. Urea-welded Anionic Vinyl-addition and Ring-opening Polymerizations for One-pot Hybrid Block Copolymer Synthesis[J/OL]. Chinese Journal of Polymer Science, 2026, 441-8. DOI: 10.1007/s10118-026-3823-2.
Structural and functional diversity of block copolymers can be vastly expanded by combining carbon-chain and heterochain segments. However
options for one-pot controlled synthesis of such hybrid block copolymers remain scarce. Herein
we report a tandem anionic polymerization strategy that addresses this challenge. Classic anionic vinyl-addition polymerization of isoprene or styrene is performed first
followed by end-capping with ethylene oxide to generate a macromolecular lithium alkoxide. A
N
N’
-disubstituted (thio)urea is then introduced to interact with the alkoxide
creating an ionic initiating/catalytic system through exchange of proton and lithium cation. The
in situ
generated bifunctional catalytic species allows the ring-opening polymerization (ROP) of the subsequently added
ε
-caprolactone (CL) to occur with markedly enhanced selectivity. Well-defined hybrid block co- and ter-polymers are obtained even at full CL conversion. Urea with medium acidity (p
K
a
) and structural symmetr
y is shown optimal mediator to achieve both high efficiency and good control of the ROP step.
Bates, F. S.; Hillmyer, M. A.; Lodge, T. P.; Bates, C. M.; Delaney, K. T.; Fredrickson, G. H. Multiblock polymers: Panacea or Pandora’s box. Science 2012 , 336 , 434−440..
Matyjaszewski, K. Architecturally complex polymers with controlled heterogenei ty. Science 2011 , 333 , 1104−1105..
Lee, S.; Bluemle, M. J.; Bates, F. S. Discovery of a Frank-Kasper σ phase in sphere-forming block copolymer melts. Science 2010 , 330 , 349−353..
Bates, F. S.; Fredrickson, G. H. Block copolymer thermodynamics: theory and experiment. Annu. Rev. Phys. Chem. 1990 , 41 , 525−557..
[Bates, C. M.; Bates, F. S. 50th anniversary perspective: block polymers—pure potential. Macromolecules 2017, 50 , 3−22..
Gaitzsch, J.; Huang, X.; Voit, B. Engineering functional polymer capsules toward smart nanoreactors. Chem. Rev. 2016 , 116 , 1053−1093..
Hamley, I. W. Nanostructure fabrication using block copolymers. Nanotechnology 2003 , 14 , R39−R54..
Bates, F. S.; Fredrickson, G. H. Block copolymers—designer soft materia ls. Phys. Today 1999 , 52 , 32−38..
Hillmyer, M. A.; Tolman, W. B. Aliphatic polyester block polymers: Renewable, degradable, and sustainable. Acc. Chem. Res. 2014 , 47 , 2390−2396..
Woodruff, M. A.; Hutmacher, D. W. The return of a forgotten polymer—polycaprolactone in the 21st century. Prog. Polym. Sci. 2010 , 35 , 1217−1256..
Labet, M.; Thielemans, W. Synthesis of polycaprolactone: a review. Chem. Soc. Rev. 2009 , 38 , 3484−3504..
Drumright, R. E.; Gruber, P. R.; Henton, D. E. Polylactic acid technology. Adv. Mater. 2000 , 12 , 1841−1846..
Li, C.; Li, Q.; Kaneti, Y. V.; Hou, D.; Yamauchi, Y.; Mai, Y. Self-assembly of block copolymers towards mesoporous materials for energy storageand conversion systems. Chem. Soc. Rev. 2020 , 49 , 4681−4736..
Mai, Y.; Eisenberg, A. Self- assembly of block copolymers. Chem. Soc. Rev. 2012 , 41 , 5969−5985..
Dau, H.; Jones, G. R.; Tsogtgerel, E.; Nguyen, D.; Keyes, A.; Liu, Y.-S.; Rauf, H.; Ordonez, E.; Puchelle, V.; Basbug Alhan, H.; Zhao, C.; Harth, E. Linear block copolymer synthesis. Chem. Rev. 2022 , 122 , 14471−14553..
Truong, N. P.; Jones, G. R.; Bradford, K. G. E.; Konkolewicz, D.; Anastasaki, A. A comparison of RAFT and ATRP methods for controlled radical polymerization. Nat. Rev. Chem. 2021 , 5 , 859−869..
Yildirim, I.; Weber, C.; Schubert, U. S. Old meets new: combination of PLA and RDRP to obtain sophisticated macromolecular architectures. Prog. Polym. Sci. 2018 , 76 , 111−150..
Matyjaszewski, K. Advanced materials by atom transfer radical polymerization. Adv. Mater. 2018 , 30 , 1706441..
[Perrier, S. 50th anniversary perspective: RAFT polymerization—a user guide. Macromolecules 2017, 50 , 7433−7447..
Lutz, J.-F.; Ouchi, M.; Liu, D. R.; Sawamoto, M. Sequence-controlled polymers. Science 2013 , 341 , 628−636..
Li, H.; Zeng, W.; Li, Z.; Zhao, J.; Zhang, G. One-step hybrid block copolymerization by organocatalysis. Prog. Polym. Sci. 2025 , 163 , 101955..
[Hadjichristidis, N.; Pispas, S.; Floudas, G. in Block copolymers . John Wiley & Sons: Hoboken, 2003 ..
Hillmyer, M. Block copolymer synthesis. Curr. Opin. Solid State Mater. Sci. 1999 , 4 , 559−564..
Lu, Y.; Hu, Y.; Chung, T. C. M. Syntheses of diblock copolymers polyolefin- b -poly( ε -caprolactone) and their applications as the polymeric compatilizer. Polymer 2005 , 46 , 10585−10591..
Barbier-Baudry, D.; Bonnet, F.; Dormond, A.; Finot, E.; Visseaux, M. Diene/polar monomer copolymers, compatibilisers for polar/non-polar polymer blends. A controlled block copolymerisation with a single-site component samarocene initiator. Macromol. Chem. Phys. 2002 , 203 , 1194−1200..
Hsieh, H. L. Styrene–diene–lactone block copolymers. J. Appl. Polym. Sci. 2010 , 22 , 1119−1127..
Buzdugan, E.; Ghioca, P.; Stribeck, N.; Beckman, E. J.; Şerban, S. Synthesis and properties of some ε -caprolactone-based di- and triblock polymers by anionic polymerization. Macromol. Mater. Eng. 2001 , 286 , 497−505..
Rozenberg, B. A.; Estrin, Y. I.; Estrina, G. A. Synthesis and characterization of di- and triblock copolymers of ε -caprolactone and 1,3-butadiene. Macromol. Symp. 2000 , 153 , 197−208..
Balsamo, V.; von Gyldenfeldt, F.; Stadler, R. Synthesis of SBC, SC and BC block copolymers based on polystyrene (S), polybutadiene (B) and a crystallizable poly( ε -caprolactone) (C) block. Macromol. Chem. Phys. 1996 , 197 , 1159−1169..
Liu, L.; Li, H.; Zhang, P.; Zhou, Y. ; Zhao, J.; Zhang, G. Hybrid anionic block copolymerization: from organocatalysis-streamlined crossover to internally microphase-separated aggregates. Aggregate 2024 , 5 , e541..
Zhang, Y. Y.; Yang, G. W.; Lu, C.; Zhu, X. F.; Wang, Y.; Wu, G. P. Organoboron-mediated polymerizations. Chem. Soc. Rev. 2024 , 53 , 3384−3456..
Zhang, C.; Geng, X.; Zhang, X.; Gnanou, Y.; Feng, X. Alkyl borane-mediated metal-free ring-opening (co)polymerizations of oxygenated monomers. Prog. Polym. Sci. 2023 , 136 , 101644..
Xu, J.; Wang, X.; Liu, J.; Feng, X.; Gnanou, Y.; Hadjichristidis, N. Ionic H-bonding organocatalysts for the ring-opening polymerization of cyclic esters and cyclic carbonates. Prog. Polym. Sci. 2022 , 125 , 101484..
Zhu, N.; Hu, X.; Fang, Z.; Guo, K. Chemoselective polymerizations. Prog. Polym. Sci. 2021 , 117 , 101397..
Hu, S.; Zhao, J.; Zhang, G.; Schlaad, H. Macromolecular architectures through organocatalysis. Prog. Polym. Sci. 2017 , 74 , 34−77..
Zhou, Y.; Chen, X.; Zhao, J.; Zhang, G. Ionized H-donors as simple and diverse organobase catalysts for selective and versatile ethoxylation. Macromolecules 2025 , 58 , 12539−12551..
Geng, X.; Liu, X.; Yu, Q.; Zhang, C.; Zhang, X. Advancing H-bonding organocatalysis for ring-opening polymerization: intramolecular activation of initiator/chain end. J. Am. Chem. Soc. 2024 , 146 , 25852−25859..
Jiang, Z.; Zhao, J.; Zhang, G. Ionic organocatalyst with a urea anion and tetra- n -butyl ammonium cation for rapid, selective, and versatile ring-opening polymerization of lactide. ACS Macro Lett. 2019 , 8 , 759−765..
Jiang, Z. L.; Zhao, J. P.; Zhang, G.-Z. Readily prepared and tunable ionic organocatalysts for ring-opening polymerization of lactones. Chinese J. Polym. Sci. 2019 , 37 , 1205−1214..
Lin, B.; Hedrick, J. L.; Park, N. H.; Waymouth, R. M. Programmable high-throughput platform for the rapid and scalable synthesis of polyester and polycarbonate libraries. J. Am. Chem. Soc. 2019 , 141 , 8921−8927..
Lin, B.; Waymouth, R. M. Urea anions: Simple, fast, and selective catalysts for ring-opening polymerizations. J. Am. Chem. Soc. 2017 , 139 , 1645−1652..
Zhang, X. Y.; Jones, G. O.; Hedrick, J. L.; Waymouth, R. M. Fast and selective ring-opening polymerizations by alkoxides and thioureas. Nat. Chem. 2016 , 8 , 1047−1053..
Lin, B.; Waymouth, R. M. Organic ring-opening polymerization catalysts: Reactivity control by balancing acidity. Macromolecules 2018 , 51 , 2932−2938..
Liu, Y.; Wang, X.; Li, Z.; Wei, F.; Zhu, H.; Dong, H.; Chen, S.; Sun, H.; Yang, K.; Guo, K. A switch from anionic to bifunctional H-bonding catalyzed ring-opening polymerizations towards polyether–polyester diblock copolymers. Polym. Chem. 2018 , 9 , 154−159..
Xu, S.; Sun, H.; Liu, J.; Xu, J.; Pan, X.; Dong, H.; Liu, Y.; Li, Z.; Guo, K. Internal Lewis pair enhanced H-bond donor: boronate-urea and tertiary amine co-catalysis in ring-opening polymerization. Polym. Chem. 2016 , 7 , 6843−6853..
Xia, Y.; Chen, Y.; Song, Q.; Hu, S.; Zhao, J.; Zhang, G. Base-to-base organocatalytic approach for one-pot construction of poly(ethylene oxide)-based macromolecular structures. Macromolecules 2016 , 49 , 6817−6825..
Datta, P. P.; Pothupitiya, J. U.; Kiesewetter, E. T.; Kiesewetter, M. K. Coupled equilibria in H-bond donating ring-opening polymerization: The effective catalyst-determined shift of a polymerization equilibrium. Eur. Polym. J. 2017 , 95 , 671−677..
Pearson, R. G. Acids and bases. Science 1966 , 151 , 172−177..
Pearson, R. G. Hard and soft acids and bases. J. Am. Chem. Soc. 1963 , 85 , 3533−3539..
Blain, M.; Yau, H.; Jean-Gérard, L.; Auvergne, R.; Benazet, D.; Schreiner, P. R.; Caillol, S.; Andrioletti, B. Urea- and thiourea-catalyzed aminolysis of carbonates. ChemSusChem 2016 , 9 , 2269−2272..
Dharmaratne, N. U.; Pothupitiya, J. U.; Bannin, T. J.; Kazakov, O. I.; Kiesewetter, M. K. Triclocarban: Commercial antibacterial and highly effective H-bond donating catalyst for ring-opening polymerization. ACS Macro Lett. 2017 , 6 , 421−425..
Fastnacht, K. V.; Spink, S. S.; Dharmaratne, N. U.; Pothupitiya, J. U.; Datta, P. P.; Kiesewetter, E. T.; Kiesewetter, M. K. Bis- and tris-urea H-bond donors for ring-opening polymerization: unprecedented activity and control from an organocatalyst. ACS Macro Lett. 2016 , 5 , 982−986..
Stevels, W. M.; Ankoné, M. J. K.; Dijkstra, P. J.; Feijen, J. Kinetics and mechanism of ε -caprolactone polymerization using yttrium alkoxides as initiators. Macromolecules 1996 , 29 , 8296−8303..
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