Insertion of Degradable Thioester Linkages into Styrene and Methacrylate Polymers: Insights into the Reactivity of Thionolactones

Rix, Matthew F. I.; Collins, Kyle; Higgs, Samuel J.; Dodd, Eleanor M.; Coles, Simon J.; Bingham, Nathaniel M.; Roth, Peter J.

doi:10.1021/acs.macromol.3c01811

Cited by 6 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[74] In order to expand the library of thionolactones able to efficiently undergo rROP and improve copolymerization with less activated monomers, the phenyl group in alpha position to the thiocarbonyl was substituted with alkyl chains yielding 3,3dimethyl-2,3-dihydro-5H-benzo- [1,4]dioxepine-5-thione (DBT). [75] Later, Destarac [76] and Guillaneuf [77] replaced the aryl groups with alkyl chains to obtain ɛ-thionocaprolactone (thCL) and decathionolactone (thDL) (Figure 3). In all cases, copolymerization with less activated monomers was achieved albeit with higher incorporation rate of the thionolactone, leading to compositional drift in the resulting polymer.…”

Section: Thionolactonesmentioning

confidence: 99%

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Sbordone,

Frisch

2024

Chemistry A European J

View full text Add to dashboard Cite

Radical polymerization is the most widely applied technique in both industry and fundamental science. However, its major drawback is that it typically yields polymers with non‐functional, non‐degradable all‐carbon backbones—a limitation that radical ring‐opening polymerization (rROP) allows to overcome. The last decade has seen a surge in rROP, primarily focused on creating degradable polymers. This pursuit has resulted in the creation of the first readily degradable materials through radical polymerization. Recent years have witnessed innovations in new monomers that address previous design limitations, such as ring strain and reactivity ratios. Furthermore, advances in integrating rROP with reversible deactivation radical polymerization (RDRP) have facilitated the incorporation of complex, customizable chemical payloads into the main polymer chain. This short review discusses the latest developments in monomer design with a focused analysis of their limitations in a broader historical context. Recently evolving strategies for compatibility of rROP monomers with RDRP are discussed, which are key to precision polymer synthesis. The latest chemistry surveyed expands the horizon beyond mere hydrolytic degradation. Now is the time to explore the chemical potential residing in the previously inaccessible polymer backbone.

show abstract

Section: Thionolactonesmentioning

confidence: 99%

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Sbordone,

Frisch

2024

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…TLs have proven to be successful as CCs for various vinyl polymers. A notable example is the TL molecule dibenzo[c,e]oxepine-5(7H)-thione, commonly referred to as “DOT,” which has demonstrated favorable copolymerization reactivity with various acrylate, ,− acrylamide, ,, and styrenic ,− , monomers; however, there have been no successful instances of TLs copolymerizing with methacrylates without exhibiting negligible reactivity or pronounced compositional gradients, which can be attributed to their reactivity ratios being far from optimal.…”

Section: Introductionmentioning

confidence: 99%

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate)

Ko,

Lundberg,

Johnson

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for the introduction of backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues for the selective deconstruction of multiple classes of vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize with methacrylates to an appreciable extent to enable polymer deconstruction. Here, we overcome this challenge through the design of a new class of benzyl-functionalized thionolactones (bDOTs). Guided by detailed mechanistic analyses, we find that the introduction of radical-stabilizing substituents to bDOTs enables markedly increased and tunable copolymerization reactivity with methyl methacrylate (MMA). Through iterative optimizations of the molecular structure, a specific bDOT, F-p-CF 3 PhDOT, is discovered to copolymerize efficiently with MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, M n > 120 kDa) with low percentages of F-p-CF 3 PhDOT (1.8 and 3.8 mol%) are prepared using industrially relevant bulk free radical copolymerization conditions. The thermomechanical properties of dPMMA are similar to PMMA; however, the former is shown to degrade into low molar mass fragments (<6.5 kDa) under mild aminolysis conditions. This work presents the first example of a radical ring-opening CC capable of nearly random copolymerization with MMA without the possibility of cross-linking and provides a workflow for the mechanism-guided design of deconstructable copolymers in the future.

show abstract

“…Thionolactones are a new class of monomers that ring-open to introduce thioester functions along the polymer backbone via thiocarbonyl radical addition-ring-opening (TARO) polymerization. This approach was reported independently by Roth and Gutekunst via the use of biphenylic cyclic thionolactone (dibenzo[ c , e ]oxepane-5-thione, DOT) as a comonomer in the copolymerization with acrylates, , acrylamides, styrene, − acrylonitrile, and maleimides . DOT inhibits the copolymerization of less activated monomers such as vinyl acetate (VAc) .…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

Vu,

Ivanchenko,

Baffie

et al. 2024

Macromolecules

View full text Add to dashboard Cite

We report the synthesis of PE and poly(ethylene-covinyl acetate) (EVA) bearing a low content of in-chain thioester functions introduced via a co-or terpolymerization approach involving ethylene (E), vinyl acetate (VAc), and ε-thionocaprolactone (TCL). To achieve homogeneous incorporation of thioester functions along the chains resulting from the ring opening of TCL, a semibatch process with an adjusted feed of TCL was employed. Characterizations of the polymers were conducted by a combination of size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) analyses. The chemically induced degradability of the obtained polymers was assessed by SEC.

show abstract

Insertion of Degradable Thioester Linkages into Styrene and Methacrylate Polymers: Insights into the Reactivity of Thionolactones

Cited by 6 publications

References 42 publications

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Plenty of Space in the Backbone: Radical Ring‐Opening Polymerization

Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate)

Synthesis of Degradable Polyethylene and Poly(ethylene-co-vinyl acetate) by Radical Co- and Terpolymerization of Ethylene, ε-Thionocaprolactone, and Vinyl Acetate

Contact Info

Product

Resources

About