Cost-effective Synthesis of Bottlebrush Block Copolymers from <italic style="font-style: italic">endo</italic>-<italic style="font-style: italic">exo</italic> Mixture Macromonomers

Jia-Qi Sun; Zan Gao; Bang-Bang Wang; Yue-Sheng Li; Dong-Po Song

doi:10.1007/s10118-026-3731-5

Your Location：

Home >

Browse articles >

Cost-effective Synthesis of Bottlebrush Block Copolymers from endo-exo Mixture Macromonomers

RESEARCH ARTICLE | Updated：2026-09-23

- Cost-effective Synthesis of Bottlebrush Block Copolymers from endo-exo Mixture Macromonomers
- Chinese Journal of Polymer Science Vol. 44, Issue 10, Pages: 3398-3407(2026)
- Affiliations：
  
  a.Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
  b.State Key Laboratory of High Performance Roll Materials and Composite Forming, School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China
- Author bio：
  
  dongpo.song@tju.edu.cn
- Funds：
- DOI：10.1007/s10118-026-3731-5
  CLC：
- Received：04 April 2026，
  
  Accepted：29 April 2026，
  
  Online First：09 July 2026，
  
  Published：05 October 2026
- Accepted：
Scan QR Code
Sun, J. Q.; Gao, Z.; Wang, B. B.; Li, Y. S.; Song, D. P. Cost-effective synthesis of bottlebrush block copolymers from endo-exo mixture macromonomers. Chinese J. Polym. Sci. 2026, 44, 3398–3407

Jia-Qi Sun, Zan Gao, Bang-Bang Wang, et al. Cost-effective Synthesis of Bottlebrush Block Copolymers from endo-exo Mixture Macromonomers[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3398-3407. DOI: 10.1007/s10118-026-3731-5.
Sun, J. Q.; Gao, Z.; Wang, B. B.; Li, Y. S.; Song, D. P. Cost-effective synthesis of bottlebrush block copolymers from endo-exo mixture macromonomers. Chinese J. Polym. Sci. 2026, 44, 3398–3407 DOI： 10.1007/s10118-026-3731-5.

Jia-Qi Sun, Zan Gao, Bang-Bang Wang, et al. Cost-effective Synthesis of Bottlebrush Block Copolymers from endo-exo Mixture Macromonomers[J]. Chinese Journal of Polymer Science, 2026, 44(10): 3398-3407. DOI: 10.1007/s10118-026-3731-5. DOI：

摘要

Bottlebrush block copolymers are rapidly synthesized from low-cost

endo

exo

macromonomer mixtures in ethyl acetate at 60 °C

enabling complete conversion in 15 min and producing structurally colored eco-friendly photonic pigments.

Abstract

The synthesis of bottlebrush block copolymers (BBCPs)

via

ring-opening metathesis polymerization (ROMP) typically relies on

exo

-norbornene-terminated macromonomers to achieve high polymerization rates. However

norbornene derivatives synthesized

via

the Diels-Alder reaction were obtained as mixtures of

exo

and

endo

isomers

with the

endo

isomer predominating. This presents a significant challenge for the preparation of well-defined BBCPs from such mixtures because of the inherently low ROMP reactivity of

endo

-norbornene. Here

we demonstrate that polymerization kinetics are strongly influenced by the solvent

temperature

and configuration of the norbornene end group. By optimizing these parameters

the complete conversion of

endo

exo

macromonomer mixtures can be achieved within a short time

enabling the efficient synthesis of well-defined BBCPs. The resulting BBCPs exhibited self-assembly behavior comparable to those prepared from purely

exo

-norbornene-terminated macromonomers

forming structurally colored polymer microspheres that function as eco-friendly photonic pigments. This study provides an efficient and cost-effective strategy for the synthesis of BBCPs using commercially available norbornene derivatives.

关键词

Keywords

references

Saha, D.; Witt, C. L.; Fatima, R.; Uchiyama, T.; Pande, V.; Song, D.-P.; Fei, H. F.; Yavitt, B. M.; Watkins, J. J. Opportunities in bottlebrush block copolymers for advanced materials. ACS Nano 2025 , 19 , 1884−1910..

Verduzco, R.; Li, X.; Pesek, S. L.; Stein, G. E. Structure, function, self-assembly, and applications of bottlebrush copolymers. Chem. Soc. Rev. 2015 , 44 , 2405−2420..

Fu, X.; Park, J.-M.; Liang, R.; Xue, Y.; Zhong, M. Hierarchically structured materials derived from synthetic polymers: design and bulk self-assembly strategies. Prog. Polym. Sci. 2025 , 170 , 102027..

Zhulina, E. B.; Sheiko, S. S.; Borisov, O. V. Theoretical advances in molecular bottlebrushes and comblike (co)polymers: solutions, gels, and self-assembly. Soft Matter 2022 , 18 , 8714−8735..

Kim, K. H.; Nam, J.; Choi, J.; Seo, M.; Bang, J. From macromonomers to bottlebrush copolymers with sequence control: synthesis, properties, and applications. Polym. Chem. 2022 , 13 , 2224−2261..

Kim, K. H.; Huh, Y.; Song, I.; Ryu, D. Y.; Son, J. G.; Bang, J. Recent advances in block copolymer self-assembly: from the lowest to the highest. J. Polym. Sci. 2024 , 62 , 679−693..

Guo, J.; Wang, J.; Wang, F.; Qiao, S.; Yang, Y.; Zhang, C.; Yu, H. Recent progress in block copolymer self-assembly for the fabrication of structural color pigments. Macromol. Rapid Commun. 2025 , 46 , 2400839..

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..

Hu, K.; Mu, R.; Ma, Z.; Li, B. Bottlebrush polymers: from synthesis to properties and applications. Macromol. Rapid Commun. 2025 , 46 , 2500215..

Liberman-Martin, A. L.; Chu, C. K.; Grubbs, R. H. Application of bottlebrush block copolymers as photonic crystals. Macromol. Rapid Commun. 2017 , 38 , 1700058..

Stefik, M.; Guldin, S.; Vignolini, S.; Wiesner, U.; Steiner, U. Block copolymer self-assembly for nanophotonics. Chem. Soc. Rev. 2015 , 44 , 5076−5091..

Steiner, U.; Dodero, A. Block copolymer-based photonic pigments: towards structural non-iridescent brilliant coloration. Chimia 2022 , 76 , 826−832..

Miyake, G. M.; Piunova, V. A.; Weitekamp, R. A.; Grubbs, R. H. Precisely tunable photonic crystals from rapidly self-assembling brush block copolymer blends. Angew. Chem. Int. Ed. 2012 , 51 , 11246−11248..

Macfarlane, R. J.; Kim, B.; Lee, B.; Weitekamp, R. A.; Bates, C. M.; Lee, S. F.; Chang, A. B.; Delaney, K. T.; Fredrickson, G. H.; Atwater, H. A.; Grubbs, R. H. Improving brush polymer infrared one-dimensional photonic crystals via linear polymer additives. J. Am. Chem. Soc. 2014 , 136 , 17374−17377..

Liberman-Martin, A. L.; Chang, A. B.; Chu, C. K.; Siddique, R. H.; Lee, B.; Grubbs, R. H. Processing effects on the self-assembly of brush block polymer photonic crystals. ACS Macro Lett. 2021 , 10 , 1480−1486..

Chae, C. G.; Yu, Y. G.; Seo, H. B.; Kim, M. J.; Grubbs, R. H.; Lee, J. S. Experimental formulation of photonic crystal properties for hierarchically self-assembled POSS-bottlebrush block copolymers. Macromolecules 2018 , 51 , 3458−3466..

Yavitt, B. M.; Fei, H.; Kopanati, G.; Li, R.; Fukuto, M.; Winter, H. H.; Watkins, J. J. Long-range lamellar alignment in diblock bottlebrush copolymers via controlled oscillatory shear. Macromolecules 2020 , 53 , 2834−2840..

Yavitt, B. M.; Fei, H.-F.; Kopanati, G. N.; Winter, H. H.; Watkins, J. J. Power law relaxations in lamellae forming brush block copolymers with asymmetric molecular shape. Macromolecules 2019 , 52 , 1557−1566..

Fei, H.-F.; Yavitt, B. M.; Nuguri, S.; Yu, Y.-G.; Watkins, J. J. Ultrafast self-assembly of bottlebrush statistical copolymers: well-ordered nanostructures from one-pot polymerizations. Macromolecules 2021 , 54 , 10943−10950..

Yavitt, B. M.; Gai, Y.; Song, D.-P.; Winter, H. H.; Watkins, J. J. High molecular mobility and viscoelasticity of microphase-separated bottlebrush diblock copolymer melts. Macromolecules 2016 , 49 , 9243−9251..

Chen, X.; Yang, X.; Song, D. P.; Men, Y. F.; Li, Y. Discovery and insights into organized spontaneous emulsification via interfacial self-assembly of amphiphilic bottlebrush block copolymers. Macromolecules 2021 , 54 , 3668−3677..

Song, D. P.; Zhao, T. H.; Guidetti, G.; Vignolini, S.; Parker, R. M. Hierarchical photonic pigments via the confined self-assembly of bottlebrush block copolymers. ACS Nano 2019 , 13 , 1764−1771..

Guo, Q.; Li, Y.; Liu, Q.; Li, Y.; Song, D.-P. Janus photonic microspheres with bridged lamellar structures via droplet-confined block copoly mer co-assembly. Angew. Chem. Int. Ed. 2022 , 61 , e202113759..

Xu, J.; Wu, Y.; Xia, Y.; Fatima, R.; Li, Y.; Song, D.-P. Photonic pigments of polystyrene- block -polyvinylpyrrolidone bottlebrush block copolymers via sustainable organized spontaneous emulsification. ACS Macro Lett. 2024 , 13 , 495−501..

Zhao, T. H.; Jacucci, G.; Chen, X.; Song, D.-P.; Vignolini, S.; Parker, R. M. Angular-independent photonic pigments via the controlled micellization of amphiphilic bottlebrush block copolymers. Adv. Mater. 2020 , 32 , 2002681..

Li, X.; Xia, B.; Song, Y.; Zheng, M.; Huang, C.; Li, Y.; Song, D.-P. Light-controlled interfacial self-assembly of bottlebrush amphiphiles toward highly tunable photonic materials. Macromolecules 2024 , 57 , 7915−7925..

Jeon, S.; Kamble, Y.; Xu, Z.; Khasbaatar, A.; Hwang, C.; Lee, J.-H.; Shi, J.; Rogers, S. A.; Guironnet, D.; Diao, Y. Large modulation of the bottlebrush diblock copolymer morphology and structural color through solvent selectivity. Soft Matter 2025 , 21 , 2217−2229..

Roeven, E.; Kuzmyn, A. R.; Scheres, L.; Baggerman, J.; Smulders, M. M. J.; Zuilhof, H. PLL-poly(HPMA) bottlebrush-based antifouling coatings: three grafting routes. Langmuir 2020 , 36 , 10187−10199..

Mukumoto, K.; Li, Y.; Nese, A.; Sheiko, S. S.; Matyjaszewski, K. Synthesis and characterization of molecular bottlebrushes prepared by iron-based ATRP. Macromolecules 2012 , 45 , 9243−9251..

Pesek, S. L.; Li, X.; Hammouda, B.; Hong, K.; Verduzco, R. Small-angle neutron scattering analysis of bottlebrush polymers prepared via grafting-through polymerization. Macromolecules 2013 , 46 , 6998−7005..

Radzinski, S. C.; Foster, J. C.; Matson, J. B. Synthesis of bottlebrush polymers via transfer-to and grafting-through approaches using a RAFT chain transfer agent with a ROMP-active Z-group. Polym. Chem. 2015 , 6 , 5643−5652..

Radzinski, S. C.; Foster, J. C.; Matson, J. B. Preparation of bottlebrush polymers via a one-pot ring-opening polymerization (ROP) and ring-opening metathesis polymerization (ROMP) grafting-through strategy. Macromol. Rapid Commun. 2016 , 37 , 616−621..

Wang, B.; Mi, Y.; Wang, B.; Pan, L.; Li, Y.; Song, D.-P. Synthesis of multiblock bottlebrush copolymers with well-defined arbitrary monomer sequences: key factors influencing catalytic stability. Macromolecules 2024 , 57 , 1770−1778..

Wang, B.; Zhang, K.; Pan, L.; Li, Y.; Song, D.-P. Scalable and precise synthesis of structurally colored bottlebrush block copolymers: enabling refined color calibration for sustainable photonic pigments. Angew. Chem. Int. Ed. 2025 , 64 , e202421653..

Radzinski, S. C.; Foster, J. C.; Scannelli, S. J.; Weaver, J. R.; Arrington, K. J.; Matson, J. B. Tapered bottlebrush polymers: cone-shaped nanostructures by sequential addition of macromonomers. ACS Macro Lett. 2017 , 6 , 1175−1179..

Wolf, W. J.; Lin, T. P.; Grubbs, R. H. Examining the effects of monomer and catalyst structure on the mechanism of ruthenium-catalyzed ring-opening metathesis polymerization. J. Am. Chem. Soc. 2019 , 141 , 17796−17808..

Hyatt, M. G.; Walsh, D. J.; Lord, R. L.; Andino Martinez , J. G.; Guironnet, D. Mechanistic and kinetic studies of the ring opening metathesis polymerization of norbornenyl monomers by a Grubbs third generation catalyst. J. Am. Chem. Soc. 2019 , 141 , 17918−17925..

Miyasako, N.; Matsuoka, S.-i.; Suzuki, M. Ring-opening metathesis polymerization of endo - and exo -norbornene lactones. Macromol. Rapid Commun. 2021 , 42 , 2000326..

Pollino, J. M.; Stubbs, L. P.; Weck, M. Living ROMP of exo -norbornene esters possessing Pd II SCS pincer complexes or diaminopyridines. Macromolecules 2003 , 36 , 2230−2234..

Alaboalirat, M.; Qi, L.; Arrington, K. J.; Qian, S.; Keum, J. K.; Mei, H.; Littrell, K. C.; Sumpter, B. G.; Carrillo, J. M. Y.; Verduzco, R.; Matson, J. B. Amphiphilic bottlebrush block copolymers: analysis of aqueous self-assembly by small-angle neutron scattering and surface tension measurements. Macromolecules 2019 , 52 , 465−476..

Wang, Z. H.; Xu, H.; Wang, T.; Yang, S. Z.; Ding, Y. S.; Wei, H. B. NMR spectroscopic studies on ( exo, endo ) C-2 monosubstituted norbornene derivatives. Chin. J. Magn. Reson. 2021 , 38 , 323−335..

[Walsh, D. J.; Lau, S. H.; Hyatt, M. G.; Guironnet, D. Kinetic study of living ring-opening metathesis polymerization with third-generation Grubbs catalysts. J. Am. Chem. Soc . 2017 , 139, 13644-13647..

Blosch, S. E.; Alaboalirat, M.; Eades, C. B.; Scannelli, S. J.; Matson, J. B. Solvent effects in grafting-through ring-opening metathesis polymerization. Macromolecules 2022 , 55 , 3522−3532..

Masgrau, L.; González-Lafont, À.; Lluch, J. M. The curvature of the Arrhenius plots predicted by conventional canonical transition-state theory in the absence of tunneling. Theor. Chem. Acc. 2003 , 110 , 352−357..

Barther, D.; Moatsou, D. Ring-opening metathesis polymerization of norbornene-based monomers obtained via the passerini three component reaction. Macromol. Rapid Commun. 2021 , 42 , 2100027..

Jiang, L.; Nykypanchuk, D.; Ribbe, A. E.; Rzayev, J. One-shot synthesis and melt self-assembly of bottlebrush copolymers with a gradient compositional profile. ACS Macro Lett. 2018 , 7 , 619−623..

[Tsai, S. D.; Register, R. A. Endo / Exo reactivity ratios in living vinyl addition polymerization of substituted norbornenes. Macromol. Chem. Phys . 2018 , 219 , 1800059..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

Highly Regio- and trans-Selective Ring-opening Metathesis Polymerization of Chiral Aza-norbornene with a Simple Phenylimido-Tungsten Catalyst

Synthesis of Polydicyclopentadiene Thermosets with High Stretchability and Self-healing Properties via Ring-opening Metathesis Polymerization

End-to-End Neuron-inspired Signal Transduction Using Organic Electrochemical Transistors

Molecularly Engineered Polyimide Films with Switchable Cavitation for Bidirectional Passive Thermal Regulation

Bioinspired Zinc-doped Nano Hydroxyapatite Reinforced Poly(lactic acid) Composites for Bone Repair

Related Author

Wei You

Yu Wang

Jing Bai

Xun Ci

Gui-Fu Si

Meng-He Xu

You-Gui Li

Da-Wei Zhang

Related Institution

University of Chinese Academy of Sciences

Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences

Hefei National Laboratory for Physical Sciences at the Microscale, Department of Polymer Science and Engineering, University of Science and Technology of China

School of Chemistry and Chemical Engineering, Hefei University of Technology

School of Environmental and Chemical Engineering, Wuyi University

⁰

Cost-effective Synthesis of Bottlebrush Block Copolymers from endo-exo Mixture Macromonomers

DOI：10.1007/s10118-026-3731-5

摘要

Abstract

关键词

Keywords

references