Zwitterionic polymerization of glycidyl monomers to cyclic polyethers with B(C6F5)3

Asenjo-Sanz, Isabel; Veloso, António; Miranda, José I.; Pomposo, José A.; Barroso‐Bujans, Fabienne

doi:10.1039/c4py00574k

Cited by 53 publications

(59 citation statements)

References 33 publications

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“…In 2014, Barroso‐Bujans and coworkers demonstrated the first successful example of EZROP by showing that glycidyl phenyl ether (GPE) undergoes polymerization in the presence of a Lewis acid such as B(C 6 F 5 ) 3 to generate cyclic poly(ether)s (Fig. ) . Cyclic products of M n = 3∼12 kDa were generated with typically broader PDIs of 1.5–1.9 and up to 94% cyclic content.…”

Section: Ring‐expansion Polymerizationmentioning

confidence: 95%

“…8). 80 Cyclic products of M n 5 3$12 kDa were generated with typically broader PDIs of 1.5-1.9 and up to 94% cyclic content. The addition of water generated linear poly(ether)s of notably lower molecular weights and low yields, suggesting that water not only promotes the formation of linear chains but can form hydrates of borane species to inhibit the polymerization.…”

Section: Electrophilic Zropmentioning

confidence: 99%

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Recent progress on the synthesis of cyclic polymers via ring‐expansion strategies

Chang

Waymouth

2017

J. Polym. Sci. Part A: Polym. Chem.

129

125

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Cyclic polymers are the simplest topological isomers of linear macromolecules, but exhibit properties that differ from linear chains in ways that remain imperfectly understood. The difficulty of synthesizing appropriately pure and high molecular weight cyclic samples has hindered experimental studies. Ringclosure methods, while versatile, are inherently limited in the range of molecular weights that can be achieved. Ringexpansion methods are a much more promising strategy toward obtaining high molecular weight cyclic polymers. The current review focuses on recent developments in ring-expansion polymerization strategies toward the synthesis of high molecular weight cyclic polymers. Significant progress in the last decade has made the synthesis of cyclic polymers possible by a variety of methods, such as ruthenium-and tungsten-catalyzed ringexpansion metathesis polymerization, organocatalytic and Lewis acid-catalyzed zwitterionic polymerization, RAFT and nitroxidemediated radical polymerization, among many others. While the study of cyclic polymers has long been hampered by synthetic challenges, the recent resurgence of interest in this field presents an exciting opportunity for chemists. V C 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2892-2902 KEYWORDS: cationic polymerization; cyclic polymers; cyclopolymerization; Grubbs catalyst; macrocycles; macrocyclic polymerization; metathesis polymerization; ring-expansion polymerization; zwitterionic polymerization INTRODUCTION Most of our knowledge of the physical and dynamic properties of polymers derives from investigations of linear chain macromolecules. Cyclic polymers, topological isomers of linear chains, differ from their linear congeners by only one bond, and yet this topological difference leads to behavior that, in many respects, remains poorly understood. Early heroic synthetic efforts to generate and investigate high molecular weight cyclic macromolecules 1-4 were compromised by the dramatic influence of even minor amounts of linear contaminants on the properties (esp. rheological properties) of cyclic chains. 1,[5][6][7] The synthesis of cyclic macromolecules of sufficient quantity and purity has proven to be a formidable challenge and has imposed a significant limitation on the study of their behavior as a function of molecular weight. Until recently, only a limited number of different classes of cyclic polymers have been prepared and investigated. Nevertheless, these pioneering studies have shown that cyclic polymers behave in a way that can be quite different from their linear counterparts despite their nearidentical chemical compositions. Cyclic polymers, for instance, cannot reptate or entangle 3,5,7,8 in the same way that linear polymers do and have a smaller radius of gyration in solution, leading to lower solution viscosities. 1,6

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Section: Ring‐expansion Polymerizationmentioning

confidence: 95%

Section: Electrophilic Zropmentioning

confidence: 99%

Recent progress on the synthesis of cyclic polymers via ring‐expansion strategies

Chang

Waymouth

2017

J. Polym. Sci. Part A: Polym. Chem.

129

125

View full text Add to dashboard Cite

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“…8 Termination of the reaction may be caused by the presence of a protic nucleophile or by a charge cancellation step of the highly polar dimer leading to linear and cyclic structures, respectively. 9 While neutral electrophiles have already been used in ZROP, [10][11][12] zwitterionic polymerizations typically employ neutral nucleophiles that react with heterocyclic monomer to in situ produce the zwitterionic initiator (Scheme 1.1).…”

Section: Definition Of Zropmentioning

confidence: 99%

Nucleophilic Catalysts and Organocatalyzed Zwitterionic Ring-opening Polymerization of Heterocyclic Monomers

Coulembier

2018

Organic Catalysis for Polymerisation

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“…This crossover reactions were previously thought to be incompatible with respect to intrinsic monomer reactivity difference . Barroso‐Bujans and coworkers reported B(C 6 F 5 ) 3 could catalyze the polymerization of glycidyl phenyl ethers (GPE) and produce cyclic polyethers with high molecular weight . They proposed the formation of zwitterionic GPE–borane intermediate, and macro‐zwitterions were produced upon nucleophilic attack of other GPE molecules .…”

Section: Introductionmentioning

confidence: 99%

“…Barroso‐Bujans and coworkers reported B(C 6 F 5 ) 3 could catalyze the polymerization of glycidyl phenyl ethers (GPE) and produce cyclic polyethers with high molecular weight . They proposed the formation of zwitterionic GPE–borane intermediate, and macro‐zwitterions were produced upon nucleophilic attack of other GPE molecules . This zwitterionic polymerization strategy can be extended to produce copolymers of GPE and tetrahydrofuran (THF) .…”

Section: Introductionmentioning

confidence: 99%

Zwitterionic Copolymerization of β‐Butyrolactone with Styrene

Xiao

Jiang

Zhang

et al. 2018

Macro Chemistry & Physics

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/macp.201800189. Biodegradable PolymersThe hybrid copolymerization of vinyl monomers with cyclic esters endows the formed copolymers new features, such as biodegradability and functionality. However, the recently reported hybrid copolymerizations are mainly based on polar vinyl monomers and cyclic esters catalyzed by organocatalysts. The copolymerization of non-polar vinyl monomers with cyclic esters is still a challenge. In this work, the copolymerization of β-butyrolactone (β-BL) with styrene catalyzed by B(C 6 F 5 ) 3 in the absence of coinitiators is reported. The density functional theory studies suggest the formation of zwitterion between β-BL and B(C 6 F 5 ) 3 . It is found that β-BL and styrene are concurrently copolymerized through the macro-zwitterion intermediates. The obtained copolymers are carefully examined by 1 H NMR, 2D 1 H-13 C HMBC, differential scanning calorimetry, thermogravimetric analysis, hydrolysis experiments, as well as Brady's reagents.

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Zwitterionic polymerization of glycidyl monomers to cyclic polyethers with B(C₆F₅)₃

Abstract: Glycidyl monomers react with B(C6F5)3 to generate cyclic polyethers decorated with functional groups.

Cited by 53 publications

References 33 publications

Recent progress on the synthesis of cyclic polymers via ring‐expansion strategies

Recent progress on the synthesis of cyclic polymers via ring‐expansion strategies

Nucleophilic Catalysts and Organocatalyzed Zwitterionic Ring-opening Polymerization of Heterocyclic Monomers

Zwitterionic Copolymerization of β‐Butyrolactone with Styrene

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