Dynamic covalent exchange in methacrylic anhydride copolymers

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

doi:10.1016/j.polymer.2023.126120

Cited by 3 publications

(3 citation statements)

References 39 publications

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“…11−14 Such monomers include methacrylic anhydride (MAA) and diacrylate anhydride (AA). 9,15,16 In particular, MAA, a 1,6-divinyl compound, is known to undergo cyclopolymerization in dilute solutions via radical polymerization to produce soluble polymers. 17,18 Butler and co-workers made significant contributions to the development of anhydride-based cyclic polymers, particularly the radical homo-and copolymerization of MAA and AA.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Anhydride-based divinyl monomers can undergo cyclopolymerization, the products of which have potential biomedical applications due to their ability to undergo surface erosion. − Such monomers include methacrylic anhydride (MAA) and diacrylate anhydride (AA). ,, In particular, MAA, a 1,6-divinyl compound, is known to undergo cyclopolymerization in dilute solutions via radical polymerization to produce soluble polymers. , Butler and co-workers made significant contributions to the development of anhydride-based cyclic polymers, particularly the radical homo- and copolymerization of MAA and AA. The main challenge in each of these systems was the relative suppression of the often-predominant cross-linking that occurs during radical polymerization of divinyl monomers under commonly used conditions. ,, In order to achieve cyclopolymers of MAA, the polymerization of this monomer needs to be controlled such that cyclopropagation is significantly greater than intermolecular propagation, which leads to cross-linking even at low conversion.…”

Section: Introductionmentioning

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: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of Soluble Poly(methacrylic anhydride) by Radical Cyclopolymerization

Sivabalan,

Kozody,

Yuya

et al. 2024

Macromolecules

Self Cite

View full text Add to dashboard Cite

show abstract

“…2–4 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) 7–12 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, 22–28 have been used as reversible or dynamic covalent bonds in CANs.…”

Section: Introductionmentioning

confidence: 99%

BiTEMPS methacrylate dynamic covalent cross-linker providing rapid reprocessability and extrudability of covalent adaptable networks: high-yield synthesis with strong selectivity for disulfide linkages

Debsharma,

Purwanto,

Fenimore

et al. 2024

Polym. Chem.

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Exchangeable Liquid Crystalline Elastomers: Enabling Rapid Processing and Enhanced Actuation Stability through On-Demand Deactivation

Liu,

Dong,

Wang

et al. 2024

Macromolecules

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Exchangeable liquid crystalline elastomers (xLCEs) bearing dynamic covalent bonds are promising candidates for soft actuators due to their unique capability to adjust both network structure and liquid crystalline (LC) alignment after polymerization. While current xLCEs with low exchange temperatures are convenient for processing, they suffer from issues such as creep and loss of LC alignment during repeated thermal actuation. Herein, we present an effective solution using dynamic anhydride chemistry within a thiol-ene-based xLCE. This approach enables a catalystfree, low-temperature bond exchange of the xLCE after polymerization, allowing for the adjustment of LC orientation under mild conditions. More importantly, it enables on-demand deactivation of the bond exchange via anhydride hydrolysis, effectively eliminating creep and enhancing actuation stability for over 100 cycles. Furthermore, the hydrolysis process results in the formation of carboxylic acid groups, which can be converted into carboxylates via alkali treatment, thereby providing the xLCE with humidity responsiveness. These findings highlight the use of dynamic anhydride bonds in the fabrication and optimization of xLCEs with enhanced durability and functionality, which is expected to facilitate significant advancements in their applications in soft actuators and robotics.

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Dynamic covalent exchange in methacrylic anhydride copolymers

Cited by 3 publications

References 39 publications

Synthesis of Soluble Poly(methacrylic anhydride) by Radical Cyclopolymerization

Synthesis of Soluble Poly(methacrylic anhydride) by Radical Cyclopolymerization

BiTEMPS methacrylate dynamic covalent cross-linker providing rapid reprocessability and extrudability of covalent adaptable networks: high-yield synthesis with strong selectivity for disulfide linkages

Exchangeable Liquid Crystalline Elastomers: Enabling Rapid Processing and Enhanced Actuation Stability through On-Demand Deactivation

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