RSC Applied Polymers, Journal Year: 2024, Volume and Issue: 2(2), P. 275 - 283
Published: Jan. 1, 2024
Efficient, fast and versatile depolymerization of bromine-terminated polymers.
Language: Английский
Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(39), P. 21146 - 21151
Published: Sept. 22, 2023
A photocatalytic ATRP depolymerization is introduced that significantly suppresses the reaction temperature from 170 to 100 °C while enabling temporal regulation. In presence of low-toxicity iron-based catalysts and under visible light irradiation, near-quantitative monomer recovery could be achieved (up 90%), albeit with minimal control. By employing ppm concentrations either FeCl2 or FeCl3, during dark periods completely eliminated, thus control possibility modulate rate by simply turning "on" "off". Notably, our approach allowed preservation end-group fidelity throughout reaction, carried out at high polymer loadings 2M), was compatible various polymers sources. This methodology provides a facile, environmentally friendly, temporally regulated route chemically recycle ATRP-synthesized polymers, opening door for further opportunities.
Language: Английский
Citations
52
Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)
Published: July 31, 2023
Although controlled radical polymerization is an excellent tool to make precision polymeric materials, reversal of the process retrieve starting monomer far less explored despite significance chemical recycling. Here, we investigate bulk depolymerization RAFT and ATRP-synthesized polymers under identical conditions. RAFT-synthesized undergo a relatively low-temperature solvent-free back thanks partial in situ transformation end-group macromonomer. Instead, can only depolymerize at significantly higher temperatures (>350 °C) through random backbone scission. To aid more complete even lower temperatures, performed facile quantitative modification strategy which both ATRP end-groups were successfully converted macromonomers. The macromonomers triggered temperature with onset 150 °C yielding up 90 % regeneration. versatility methodology was demonstrated by scalable (≈10 g polymer) retrieving 84 intact could be subsequently used for further polymerization. This work presents new low-energy approach depolymerizing creates many future opportunities as high-yielding, methods are sought.
Language: Английский
Citations
49
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6217 - 6224
Published: Feb. 21, 2024
In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk method exhibits exceptional efficiency, even high-molecular-weight polymers, including ultrahigh-molecular-weight (10
Language: Английский
Citations
37
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(19)
Published: March 11, 2024
Abstract Photocatalytic upcycling and depolymerization of vinyl polymers have emerged as promising strategies to combat plastic pollution promote a circular economy. This mini review critically summarizes current developments in the degradation including polystyrene poly(meth)acrylates. Of these material classes, polymethacrylates possess unique possibility undergo photocatalytic back monomer under thermodynamically favourable conditions, thus presenting significant advantages over traditional thermal strategies. Our perspective on formidable challenges potential future directions are also discussed.
Language: Английский
Citations
34
European Polymer Journal, Journal Year: 2024, Volume and Issue: 211, P. 113001 - 113001
Published: March 30, 2024
Atom transfer radical polymerization (ATRP) is one of the most often used controlled techniques. It employs very small amounts (ppm) Cu complexes in presence various chemical reducing agents but also external stimuli such as light, electrical current or mechanical forces. can be carried out bulk, solution, and dispersed media. ATRP has been successfully to prepare polymers with architecture well-defined topology, composition, functionality, well bioconjugates organic–inorganic hybrids. This article summarizes status an outlook for ATRP.
Language: Английский
Citations
23
Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(9), P. 2803 - 2841
Published: Aug. 12, 2024
Language: Английский
Citations
22
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 5786 - 5792
Published: Feb. 21, 2024
To mitigate pollution by plastic waste, it is paramount to develop polymers with efficient recyclability while retaining desirable physical properties. A recyclable poly(methyl methacrylate) (PMMA) synthesized incorporating a minimal amount of an α-methylstyrene (AMS) analogue into the polymer structure. This P(MMA-
Language: Английский
Citations
21
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9142 - 9154
Published: March 25, 2024
The development of cleavable comonomers (CCs) with suitable copolymerization reactivity paves the way for introduction backbone deconstructability into polymers. Recent advancements in thionolactone-based CCs, exemplified by dibenzo[c,e]-oxepine-5(7H)-thione (DOT), have opened promising avenues selective deconstruction multiple classes vinyl polymers, including polyacrylates, polyacrylamides, and polystyrenics. To date, however, no thionolactone CC has been shown to copolymerize methacrylates an appreciable extent enable polymer deconstruction. Here, we overcome this challenge through design a new class benzyl-functionalized thionolactones (bDOTs). Guided detailed mechanistic analyses, find that radical-stabilizing substituents bDOTs enables markedly increased tunable methyl methacrylate (MMA). Through iterative optimizations molecular structure, specific bDOT, F-p-CF3PhDOT, is discovered efficiently MMA. High molar mass deconstructable PMMA-based copolymers (dPMMA, Mn > 120 kDa) low percentages F-p-CF3PhDOT (1.8 3.8 mol%) are prepared using industrially relevant bulk free radical conditions. thermomechanical properties dPMMA similar PMMA; former degrade fragments (<6.5 under mild aminolysis This work presents first example ring-opening capable nearly random MMA without possibility cross-linking provides workflow mechanism-guided future.
Language: Английский
Citations
19
Science, Journal Year: 2025, Volume and Issue: 387(6736), P. 874 - 880
Published: Feb. 20, 2025
The reversion of vinyl polymers with carbon-carbon backbones to their monomers represents an ideal path alleviate the growing plastic waste stream. However, depolymerizing such stable materials remains a challenge, state-of-the-art methods relying on "designer" that are neither commercially produced nor suitable for real-world applications. In this work, we report main chain-initiated, visible light-triggered depolymerization directly applicable commercial containing undisclosed impurities (e.g., comonomers, additives, or dyes). By in situ generation chlorine radicals from solvent, near-quantitative (>98%) polymethacrylates could be achieved regardless synthetic route radical ionic polymerization), end group, and molecular weight (up 1.6 million daltons). possibility perform multigram-scale depolymerizations confer temporal control renders methodology versatile general recycling.
Language: Английский
Citations
6
Nature Reviews Methods Primers, Journal Year: 2025, Volume and Issue: 5(1)
Published: Jan. 9, 2025
Language: Английский
Citations
4