Dynamic covalent exchange induced cyclization in poly(methacrylic anhydride)

Santefort, Arielle L.; Yuya, Philip A.; Shipp, Devon A.

doi:10.1039/d2py00488g

Cited by 7 publications

(6 citation statements)

References 47 publications

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“…This is consistent with observations of radical polymerization of MAA in nondiluted conditions which yield low conversions. 23 Contrarily, cPMAA showed no signal from an ene group, indicating that all of the ene reactive groups had been consumed. We note that the FT-IR signals of cPMAA synthesized with and without CoBF (Figure S4 -ene peak at 1635 cm −1 which originates from the unsaturated end group of each polymer chain made with CoBF (vide infra).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…The xPMAA also displayed a significant signal from the ene group; this is likely due to the residual unreacted CC units that are rendered unreactive because of vitrification. This is consistent with observations of radical polymerization of MAA in nondiluted conditions which yield low conversions . Contrarily, cPMAA showed no signal from an ene group, indicating that all of the ene reactive groups had been consumed.…”

Section: Resultsmentioning

confidence: 99%

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Synthesis of Soluble Poly(methacrylic anhydride) by Radical Cyclopolymerization

Sivabalan,

Kozody,

Yuya

et al. 2024

Macromolecules

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Cyclopolymerization of methacrylic anhydride (MAA) by conventional radical polymerization using cobaloxime boron fluoride (CoBF) as a chain transfer agent allows high conversion synthesis of fully soluble cyclopoly(methacrylic anhydride) (PMAA). Specifically, soluble PMAA was attainable even at moderate MAA concentrations with no cross-linking in the presence of CoBF. This was achieved by studying various MAA concentrations and temperatures with and without CoBF and examining these parameters' impact on the PMAA microstructure, including the acyclic, cyclic, and cross-linked forms. Infrared and 1 H nuclear magnetic resonance (NMR) spectroscopy confirmed the formation of cyclic anhydride groups and the presence of unsaturated end groups created in the presence of CoBF. The molecular weight of the synthesized PMAA decreased with an increase in CoBF concentration. 13 C NMR spectra of PMAA confirmed the cyclization through the presence of a single peak in the carbonyl region. Importantly, the nondiluted MAA polymerization in the presence of CoBF led to the production of cyclic six-membered soluble polymers. On the other hand, cross-linked PMAA resulted from the polymerization of MAA at 3.4 M monomer concentration in the absence of CoBF.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Synthesis of Soluble Poly(methacrylic anhydride) by Radical Cyclopolymerization

Sivabalan,

Kozody,

Yuya

et al. 2024

Macromolecules

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“…Consequently, the densely distributed methacrylic groups on the CD structure may have reacted with each other. Furthermore, cyclization between these methacrylic groups could induce dimer formation [11] . To prevent these side reactions, temperatures over 90 °C should be avoided.…”

Section: Resultsmentioning

confidence: 99%

“…Furthermore, cyclization between these methacrylic groups could induce dimer formation. [11] To prevent these side reactions, temperatures over 90 °C should be avoided. Therefore, the reactions of [3]rotaxane were carried out at 80 °C (Table 2, entries 5 and 6).…”

Section: Methacrylation With An Excess Amount Of the Reagentmentioning

confidence: 99%

O‐Acylative Vinylation of Cyclodextrin‐Based [3]Rotaxane Towards Rotaxane Crosslinkers

Akae

Takata

2023

Eur J Org Chem

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The acylation of a cyclodextrin-based [3]rotaxane was implemented with anhydride reagents following a facile procedure. Methacrylic anhydride facilitated the introduction of a vinylgroup into the rotaxane structure toward achieving a crosslinker. Interestingly, only a few methacrylic units were attached to the cyclodextrin at reaction temperatures of up to 60 °C even with an excess amount of the reagent, probably due to steric hindrance. Therefore, the number of vinyl groups on the [3]rotaxane framework was easily controlled to be approximately two units via a simple random acylation, which worked effectively as a facile synthesis route for the rotaxane crosslinker. The acylation behavior was investigated in detail by NMR and MALDI-TOF-MS analyses. Such a proposed approach will help overcome the trade-off between convenience and utility associated with the mono-modification of cyclodextrins.

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“…[2][3][4] Due to this inherent unrecyclability of thermosets, they typically meet their end-of-life fate in the form of landfilling, incineration, or as devalued filler materials. 5,6 To tackle this issue of unrecyclability, a new class of polymer materials called covalent adaptable networks (CANs) [7][8][9][10][11][12] was introduced, providing both cross-linked structures at use conditions and malleability owing to their external stimuli-based reversible covalent bonds. 13,14 A range of functional groups, such as esters, 15 silyl ethers, 16,17 siloxanes, 18,19 amides, 20 β-amino esters, 21 and others, [22][23][24][25][26][27][28] have been used as reversible or dynamic covalent bonds in CANs.…”

Section: Introductionmentioning

confidence: 99%