A Paradigm for BF<sub>3 </sub>co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

Yi-Meng Liu; Yu Zhu; Bo-Yu Xu; Zi-Lin Xu; Xing-Long Zhang; Hui Li; Qiang Liu; Shou-Ke Yan

doi:10.1007/s10118-026-3714-6

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A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

RESEARCH ARTICLE | Updated：2026-07-25

- A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-12(2026)
- Affiliations：
  
  a.Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-Plastics, Qingdao University of Science and Technology, Qingdao 266042, China
  b.State Key Laboratory of Advanced Optical Polymer and Manufacturing Technology, Qingdao 266042, China
  c.College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
- Author bio：
  
  liuqiang@qust.edu.cn (Q.L.)
- Funds：
- DOI：10.1007/s10118-026-3714-6
  CLC：
- Received：09 February 2026，
  
  Accepted：14 April 2026，
  
  Online First：24 July 2026，
  
  Published：2026-06
- Accepted：
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Liu, Y. M.; Zhu, Y.; Xu, B. Y.; Xu, Z. L.; Zhang, X. L.; Li, H.; Liu, Q.; Yan, S. K. A paradigm for BF₃co-initiated cationic polymerization with low dispersity: introducing acetonitrile and lowering the reaction temperature. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3714-6

Yi-Meng Liu, Yu Zhu, Bo-Yu Xu, et al. A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature[J/OL]. Chinese Journal of Polymer Science, 2026, 441-12. DOI: 10.1007/s10118-026-3714-6.
Liu, Y. M.; Zhu, Y.; Xu, B. Y.; Xu, Z. L.; Zhang, X. L.; Li, H.; Liu, Q.; Yan, S. K. A paradigm for BF₃co-initiated cationic polymerization with low dispersity: introducing acetonitrile and lowering the reaction temperature. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3714-6 DOI：

Yi-Meng Liu, Yu Zhu, Bo-Yu Xu, et al. A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature[J/OL]. Chinese Journal of Polymer Science, 2026, 441-12. DOI: 10.1007/s10118-026-3714-6. DOI：

摘要

Abstract

Non-metallic cationic polymerization of low-reactivity styrene (St) derivatives remains challenging due to broad molecular weight distributions and rapid deactivation of active species. Here we show that adding only a minor amount of CH

CN (

3/97) to the conventional BF

·OEt

/COH/CH

/St system affords polystyrene with narrow dispersity (

≈ 1.3). Notably

the

increases linearly with conversion and closely matches the

n.calcd

H-nuclear magnetic resonance (

H-NMR) analysis and comparative experiments with the BF

·CH

CN co-initiation system indicate CH

CN does not coordinate strongly with BF

compared to diethyl ether (OEt

); however

it stabilizes the propagating carbocation and decreases the the propagation rate constant (

)

which leads to a narrower dispersity in the product. Lowering the temperature to −25 °C further extends the active-chain lifetime. This strategy is also effective for other low-reactivity styrene monomers

including

-chlorostyrene (

ClSt) and

-chloromethylstyrene (

CMSt)

and is even applicable to the relatively more reactive

-methylstyrene (

MeSt)

offering a versatile metal-free route to the synthesis of styrenic polymers with a narrow dispersity.

关键词

Keywords

references

Miyamoto, M.; Sawamoto, M.; Higashimura, T. Living polymerization of isobutyl vinyl ether with hydrogen iodide/iodine initiating system. Macromolecules 1984 , 17 , 265−268..

Faust, R.; Kennedy, J. Living carbocationic polymerization: III. Demonstration of the living polymerization of isobutylene. Polym. Bull. 1986 , 15 , 317−323..

[Kennedy, J.; Ivan, B. Designed polymers by carbocationic macromolecular engineering. 1992 .

Aoshima, S.; Kanaoka, S. A renaissance in living cationic polymerization. Chem. Rev. 2009 , 109 , 5245−5287..

Higashimura, T.; Kishimoto, Y.; Aoshima, S. Living cationic polymerization of vinyl monomers by organoaluminum halides: 2. EtAlCl2/dioxane initiating system for living polymerization of isobutyl vinyl ether. Polym. Bull. 1987 , 18 , 111−115..

Kaszas, G.; Puskas, J. E.; Chen, C. C.; Kennedy, J. P. Electron pair donors in carbocationic polymerization: I. Introduction into the synthesis of narrow molecular weight distribution polyisobutylenes. Polym. Bull. 1988 , 20 , 413−419..

Wu, Y.; Tan, Y.; Wu, G. Kinetic investigation of the carbocationic polymerization of isobutylene with the H2O/TiCl4/ED initiating system. Macromolecules 2002 , 35 , 3801−3805..

Aoshima, S.; Higashimura, T. Living cationic polymerization of vinyl monomers by organoaluminum halides. 3. Living polymerization of isobutyl vinyl ether by ethyldichloroaluminum in the presence of ester additives. Macromolecules 1989 , 22 , 1009−1013..

Fodor, Z.; Gyor, M.; Wang, H.-C.; Faust, R. Living carbocationic polymerization of styrene in the presence of proton trap. J. Macromol. Sci., Part A: Pure Appl. Chem. 1993 , 30 , 349−363..

Thomas, L.; Polton, A.; Tardi, M.; Sigwalt, P. " Living" cationic polymerization of indene. 1. Polymerization initiated with cumyl methyl ether/titanium tetrachloride and cumyl methyl ether/n-butoxytrichlorotitanium initiating systems. Macromolecules 1992 , 25 , 5886−5892..

Matyjaszewski, K.; Sigwalt, P. Unified approach to living and non-living cationic polymerization of alkenes. Polym. Int. 1994 , 35 , 1−26..

Storey, R. F.; Curry, C. L.; Hendry, L. K. Mechanistic role of lewis bases and other additives in quasiliving carbocationic polymerization of isobutylene. Macromolecules 2001 , 34 , 5416−5432..

Ishihama, Y.; Sawamoto, M.; Higashimura, T. Living cationic polymerization of styrene by the methanesulfonic acid/tin tetrachloride initiating system in the presence of tetra-n-butylammonium chloride. Polym. Bull. 1990 , 23 , 361−366..

Ishihama, Y.; Sawamoto, M.; Higashimura, T. Living cationic polymerization of styrene by the 1-phenylethyl chloride/tin tetrachloride initiating system in the presence of tetra-n-butylammonium chloride. Polym. Bull. 1990 , 24 , 201−206..

Kaszas, G.; Puskas, J.; Kennedy, J.; Hager, W. Polyisobutylene-containing block polymers by sequential monomer addition. I. The living carbocationic polymerization of styrene. J. Polym. Sci., Part A: Polym. Chem. 1991 , 29 , 421−426..

Higashimura, T.; Ishihama, Y.; Sawamoto, M. Living cationic polymerization of styrene: new initiating systems based on added halide salts and the nature of the growing species. Macromolecules 1993 , 26 , 744−751..

[Lin, C. H.; Xiang, J. S.; Matyjaszewski, K. " Living" cationic polymerization of styrene in the presence of tetrabutylammonium salts. Macromolecules 1993 , 26 , 2785–2790..

Kwon, O. S.; Kim, Y. B.; Kwon, S. K.; Choi, B. S.; Choi, S. K. Living cationic polymerization of styrene by 1-chloroethylbenzene/ tin (IV) chloride in chloroform. Makromol. Chem. 1993 , 194 , 251−257..

Kwon, O. S.; Gho, C. G.; Choi, B. S.; Choi, S. K. Living cationic polymerization of styrene by the bifunctional initiating system 1, 4-bis (1-chloroethyl) benzene/SnCl4 in the presence of 2, 6-di-tert-butylpyridine. Macromol. Chem. Phys. 1994 , 195 , 2187−2194..

Hasebe, T.; Kamigaito, M.; Sawamoto, M. Living cationic polymerization of styrene with TiCl3 (O i Pr) as a lewis acid activator. Macromolecules 1996 , 29 , 6100−6103..

Puskas, J.; Kaszas, G. Living carbocationic polymerization of resonance-stabilized monomers. Prog. Polym. Sci. 2000 , 25 , 403−452..

Kostjuk, S. V. Investigation of the TiCl4 reaction order in quasiliving styrene polymerization with 1-phenylethyl chloride/TiCl4/Bu2O. Polym. Bull. 2004 , 51 , 277−283..

Banerjee, S.; Paira, T. K.; Kotal, A.; Mandal, T. K. Room temperature living cationic polymerization of styrene with HX-styrenic monomer adduct/FeCl3 systems in the presence of tetrabutyl ammonium halide and tetraalkylphosphonium bromide salts. Polymer 2010 , 51 , 1258−1269..

Frolov, A. N.; Kostjuk, S. V.; Vasilenko, I. V.; Kaputsky, F. N. Controlled cationic polymerization of styrene using AlCl3OBu2 as a coinitiator: toward high molecular weight polystyrenes at elevated temperatures. J. Polym. Sci., Part A: Polym. Chem. 2010 , 48 , 3736−3743..

[Leushukou, A.; Horetski, M.; Vaitusionak, A.; Baravoi, H.; Nikishau, P.; Liu, W.; Vasilenko, I. V.; Hulnik, M.; Kostjuk, S. V. Step toward cationic RAFT polymerization of less reactive monomers: dithiobenzoates bearing electron-withdrawing groups as chain-transfer agents. Macromolecules 2026 , 59 , 986–999.

Kanazawa, A.; Hashizume, R.; Kanaoka, S.; Aoshima, S. Design of benign initiator for living cationic polymerization of vinyl ethers: facile in situ generation of vinyl ether–hydrogen halide adducts and subsequent controlled polymerization without a Lewis acid catalyst. Macromolecules 2014 , 47 , 1578−1585..

Uchiyama, M.; Satoh, K.; Kamigaito, M. Thioether-mediated degenerative chain-transfer cationic polymerization: a simple metal-free system for living cationic polymerization. Macromolecules 2015 , 48 , 5533−5542..

Perkowski, A. J.; You, W.; Nicewicz, D. A. Visible light photoinitiated metal-free living cationic polymerization of 4-methoxystyrene. J. Am. Chem. Soc. 2015 , 137 , 7580−7583..

Sugihara, S.; Okubo, S.; Maeda, Y. Metal-free RAFT cationic polymerization of p-methoxystyrene with HCl· Et 2 O using a xanthate-type RAFT cationogen. Polym. Chem. 2016 , 7 , 6854−6863..

Kottisch, V.; O’Leary, J.; Michaudel, Q.; Stache, E. E.; Lambert, T. H.; Fors, B. P. Controlled cationic polymerization: single-component initiation under ambient conditions. J. Am. Chem. Soc. 2019 , 141 , 10605−10609..

Haraguchi, R.; Nishikawa, T.; Kanazawa, A.; Aoshima, S. Metal-free living cationic polymerization using diaryliodonium salts as organic Lewis acid catalysts. Macromolecules 2020 , 53 , 4185−4192..

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

Chen, Y.; Zhang, L.; Jin, Y.; Lin, X.; Chen, M. Recent advances in living cationic polymerization with emerging initiation/controlling systems. Macromol. Rapid Commun. 2021 , 42 , 2100148..

Kottisch, V.; Jermaks, J.; Mak, J. Y.; Woltornist, R. A.; Lambert, T. H.; Fors, B. P. Hydrogen bond donor catalyzed cationic polymerization of vinyl ethers. Angew. Chem. Int. Ed. 2021 , 60 , 4535−4539..

Lin, X.; Li, J.; Zhang, J.; Liu, S.; Lin, X.; Pan, X.; Zhu, J.; Zhu, X. Living cationic polymerization of vinyl ethers initiated by electrophilic selenium reagents under ambient conditions. Polym. Chem. 2021 , 12 , 983−990..

Lin, X.; Li, J.; Pan, X.; Zhang, Z.; Zhu, J. Controlled cationic polymerization using RAFT agents with selenonium cations as metal-free Lewis acids: from homogeneous to heterogeneous catalysis. Polym. Chem. 2022 , 13 , 2757−2763..

Shankel, S. L.; Lambert, T. H.; Fors, B. P. Moisture tolerant cationic RAFT polymerization of vinyl ethers. Polym. Chem. 2022 , 13 , 5974−5979..

Li, M.; Zhang, Z.; Yan, Y.; Lv, W.; Li, Z.; Wang, X.; Tao, Y. Anion-binding catalysis enables living cationic polymerization. Nature Synthesis 2022 , 1 , 815−823..

Li, J.; Chen, M.; Lin, X.; Pan, X.; Zhang, Z.; Zhu, J. Controlled microflow cationic polymerization of vinyl ethers under ambient conditions. Chem. Eng. J. 2022 , 435 , 134828..

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

Uchiyama, M.; Satoh, K.; Kamigaito, M. Cationic RAFT polymerization using ppm concentrations of organic acid. Angew. Chem. 2015 , 127 , 1944−1948..

Hasegawa, T.; Takagi, K. Pnictogen bonding-mediated controlled cationic polymerization of styrene derivatives: Catalytic activity investigation using non-ionic and ionic pnictogen compounds. J. Polym. Sci. 2023 , 61 , 2655−2664..

Cao, L.; Chen, H.; Fu, H.; Xian, J.; Cao, H.; Pan, X.; Wu, J. Bidentate selenium-based chalcogen bond catalyzed cationic polymerization of p-methoxystyrene. Chem. Commun. 2024 , 60 , 1321−1324..

Li, M.; Ma, X.; Tao, Y. Unlocking hexafluoroisopropanol as a practical anion-binding catalyst for living cationic polymerization. Angew. Chem. 2025 , 137 , e202425178..

Shu, W.; Zhu, Y.; Guo, P.; Li, J.; Zhang, J.; Zhu, J. Living cationic polymerization of p-methoxystyrene catalyzed by benzoselenium salt under ambient conditions. J. Polym. Sci. 2025 , 63 , 3957−3962..

Satoh, K.; Nakashima, J.; Kamigaito, M.; Sawamoto, M. Novel BF3OEt2/R− OH initiating system for controlled cationic polymerization of styrene in the presence of water. Macromolecules 2001 , 34 , 396−401..

Kostjuk, S. V.; Ganachaud, F. Cationic polymerization of styrene in solution and aqueous suspension using B(C 6 F 5 ) 3 as a water-tolerant Lewis acid. Macromolecules 2006 , 39 , 3110−3113..

Vijayaraghavan, R.; Macfarlane, D. R. Organoborate acids as initiators for cationic polymerization of styrene in an ionic liquid medium. Macromolecules 2007 , 40 , 6515−6520..

Radchenko, A. V.; Kostjuk, S. V.; Vasilenko, I. V.; Ganachaud, F.; Kaputsky, F. N. Controlled/living cationic polymerization of styrene with BF 3 OEt 2 as a coinitiator in the presence of water: Improvements and limitations. Eur. Polym. J. 2007 , 43 , 2576−2583..

Kuznetsov, D. M.; Tumanov, V. V.; Smit, W. A. Cationic polymerization of styrenes under essentially neutral conditions. J. Polym. Res. 2013 , 20 , 128..

[Satoh, K.; Kamigaito, M.; Sawamoto, M. Direct living cationic polymerization of p-hydroxystyrene with boron trifluoride etherate in the presence of water1. Macromolecules 2000 , 33 , 5405–5410..

Kostjuk, S. V.; Radchenko, A. V.; Ganachaud, F. Controlled/living cationic polymerization of p-methoxystyrene in solution and aqueous dispersion using tris(pentafluorophenyl)borane as a lewis acid: acetonitrile does the job†. Macromolecules 2007 , 40 , 482−490..

Kostjuk, S. V. Cationic polymerization of p-methoxystyrene co-initiated by B(C6F5) 3 : effect of acetonitrile and proton traps. Eur. Polym. J. 2020 , 129 , 109632..

Takeshima, H.; Satoh, K.; Kamigaito, M. R–Cl/SnCl4/n-Bu4NCl-induced direct living cationic polymerization of naturally-derived unprotected 4-vinylphenol, 4-vinylguaiacol, and 4-vinylcatechol in CH3CN†. Polym. Chem. 2019 , 10 , 1192−1201..

Kamigaito, M.; Nakashima, J.; Satoh, K.; Sawamoto, M. Controlled cationic polymerization of p-(chloromethyl)styrene: BF 3 -catalyzed selective activation of a C−O terminal from alcohol. Macromolecules 2003 , 36 , 3540−3544..

Müller, A. H.; Litvinenko, G.; Yan, D. Kinetic analysis of “living” polymerization systems exhibiting slow equilibria. 4.“dissociative” mechanism of group transfer polymerization and generation of free ions in cationic polymerization. Macromolecules 1996 , 29 , 2346−2353..

Saitoh, R.; Kanazawa, A.; Kanaoka, S.; Aoshima, S. Cationi c polymerization of p-methylstyrene using various metal chlorides: design rationale of initiating systems for controlled polymerization of styrenes. Polym. J. 2016 , 48 , 933−940..

Verebélyi, K.; Iván, B. Cationic polymerization of styrene by the TiCl4/N, N,N′,N′-tetramethylethylenediamine (TMEDA) catalyst system in benzotrifluoride, an environmentally benign solvent, at room temperature. Polymer 2012 , 53 , 3426−3431..

Storey, R. F.; Curry, C. L.; Brister, L. B. Carbocation rearrangement in controlled/living isobutylene polymerization. Macromolecules 1998 , 31 , 1058−1063..

Kolishetti, N.; Faust, R. Structure−reactivity scales in carbocationic polymerizations. Macromolecules 2008 , 41 , 9025−9029..

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⁰

A Paradigm for BF3 co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature

DOI：10.1007/s10118-026-3714-6

摘要

Abstract

关键词

Keywords

references

A Paradigm for BF₃co-initiated Cationic Polymerization with Low Dispersity: Introducing Acetonitrile and Lowering the Reaction Temperature