Functional Group Transformation Approach to Chemically Recyclable Polymers from Ultra-Low to Moderate Strain Monomers DOI Creative Commons
Tarek Ibrahim,

Kaia Kendzulak,

Angelo Ritacco

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: 58(8), P. 3898 - 3905

Published: April 11, 2025

Ring-opening metathesis polymerization (ROMP) has been widely used for the synthesis of functional polymers. However, most ROMP-derived polymers are nondepolymerizable, limiting their sustainability and eco-friendiness. While recent advances in designing low-strain cyclic olefin monomers have enabled ROMP depolymerizable polyolefins, scope these remains limited due to narrow range ring strain energies (RSEs = 4.7-5.4 kcal/mol) required allow both depolymerization a closed-loop recycling process. Herein, we present new class chemically recyclable polyolefins based on cycloheptene derivatives with RSEs ranging from 3.8 7.2 kcal/mol. The wide establishment structure-polymerizability-depolymerizability relationship, shedding light role RSE depolymerization. A group transformation (FGT) strategy, harnessing reversible ketone-to-acetal chemistry, was developed overcome low polymerizability moderate depolymerizability made moderate-strain monomers. This FGT approach not only enhanced chemical moderately but also provided access highly that challenging synthesize through direct ultralow Moreover, thermal properties this study tunable, broad glass transition temperatures (-7 104 °C), highlighting potential various applications.

Language: Английский

Catalytic Upcycling of Polyolefins DOI Creative Commons
Jia‐Kai Sun,

Jinhu Dong,

Lijun Gao

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(16), P. 9457 - 9579

Published: Aug. 16, 2024

The large production volumes of commodity polyolefins (specifically, polyethylene, polypropylene, polystyrene, and poly(vinyl chloride)), in conjunction with their low unit values multitude short-term uses, have resulted a significant pressing waste management challenge. Only small fraction these is currently mechanically recycled, the rest being incinerated, accumulating landfills, or leaking into natural environment. Since are energy-rich materials, there considerable interest recouping some chemical value while simultaneously motivating more responsible end-of-life management. An emerging strategy catalytic depolymerization, which portion C-C bonds polyolefin backbone broken assistance catalyst and, cases, additional molecule reagents. When products molecules materials higher own right, as feedstocks, process called upcycling. This review summarizes recent progress for four major upcycling strategies: hydrogenolysis, (hydro)cracking, tandem processes involving metathesis, selective oxidation. Key considerations include macromolecular reaction mechanisms relative to mechanisms, design transformations, effect conditions on product selectivity. Metrics describing critically evaluated, an outlook future advances described.

Language: Английский

Citations

37
Photocatalytic Upcycling and Depolymerization of Vinyl Polymers DOI Creative Commons
Kostas Parkatzidis, Hyun Suk Wang, Athina Anastasaki

et al.

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
Recent advances in oxidative degradation of plastics DOI Creative Commons
Sewon Oh, Erin E. Stache

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(14), P. 7309 - 7327

Published: Jan. 1, 2024

Oxidative degradation is a powerful method to degrade plastics into oligomers and small oxidized products. While thermal energy has been conventionally employed as an external stimulus, recent advances in photochemistry have enabled photocatalytic oxidative of polymers under mild conditions. This tutorial review presents overview degradation, from its earliest examples emerging strategies. briefly discusses the motivation development with focus on underlying mechanisms. Then, we will examine modern studies primarily relevant catalytic degradation. Lastly, highlight some unique using unconventional approaches for polymer such electrochemistry.

Language: Английский

Citations

32
Atom transfer radical polymerization DOI
Simon Harrisson, Richard Whitfield, Athina Anastasaki

et al.

Nature Reviews Methods Primers, Journal Year: 2025, Volume and Issue: 5(1)

Published: Jan. 9, 2025

Language: Английский

Citations

5
Modeling the depolymerization of plastics DOI Creative Commons

Alexander K. Best,

Ananthula Raghu,

P. Majumdar

et al.

Nature Chemical Engineering, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 27, 2025

Language: Английский

Citations

3
Thermally Stable and Chemically Recyclable Poly(ketal-ester)s Regulated by Floor Temperature DOI
Xianbin Meng, Tong Zhou, Chun Yang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15428 - 15437

Published: May 25, 2024

Chemical recycling to monomers (CRM) offers a promising closed-loop approach transition from current linear plastic economy toward more sustainable circular paradigm. Typically, this has focused on modulating the ceiling temperature (Tc) of monomers. Despite considerable advancements, polymers with low Tc often face challenges such as inadequate thermal stability, exemplified by poly(γ-butyrolactone) (PGBL) decomposition ∼200 °C. In contrast, floor (Tf)-regulated polymers, particularly those synthesized via ring-opening polymerization (ROP) macrolactones, inherently exhibit enhanced thermodynamic stability increases. However, development Tf regulated chemically recyclable remains relatively underexplored. context, judicious design and efficient synthesis biobased macrocyclic diester monomer (HOD), we developed type -regulated poly(ketal-ester) (PHOD). First, entropy-driven ROP HOD generated high-molar mass PHOD exceptional Td,5% reaching up 353 Notably, it maintains high 345 °C even without removing catalyst. This contrasts markedly PGBL, which spontaneously depolymerizes back above its in presence Second, displays outstanding chemical recyclability at room within just 1 min tBuOK. Finally, copolymerization pentadecanolide (PDL) high-performance copolymers (PHOD-co-PPDL) tunable mechanical properties both components.

Language: Английский

Citations

18
Degradable π-Conjugated Polymers DOI
Azalea Uva,

Sofia Michailovich,

Nathan Sung Yuan Hsu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12271 - 12287

Published: April 24, 2024

The integration of next-generation electronics into society is rapidly reshaping our daily interactions and lifestyles, revolutionizing communication engagement with the world. Future promise stimuli-responsive features enhanced biocompatibility, such as skin-like health monitors sensors embedded in food packaging, transforming healthcare reducing waste. Imparting degradability may reduce adverse environmental impact lead to opportunities for monitoring. While advancements have been made producing degradable materials encapsulants, substrates, dielectrics, availability conducting semiconducting remains restricted. π-Conjugated polymers are promising candidates development conductors or semiconductors due ability tune their stimuli-responsiveness, mechanical durability. This perspective highlights three design considerations: selection π-conjugated monomers, synthetic coupling strategies, degradation polymers, generating electronics. We describe current challenges monomeric present options circumvent these issues by highlighting biobased compounds known pathways stable monomers that allow chemically recyclable polymers. Next, we strategies compatible synthesis including direct arylation polymerization enzymatic polymerization. Lastly, discuss various modes depolymerization characterization techniques enhance comprehension potential byproducts formed during polymer cleavage. Our considers parameters parallel rather than independently while having a targeted application mind accelerate discovery high-performance organic

Language: Английский

Citations

17
Photoiniferter Polymerization: Illuminating the History, Ascendency, and Renaissance DOI
Rhys W. Hughes, Megan E. Lott,

Rebecca A. Olson S

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: 156, P. 101871 - 101871

Published: Aug. 22, 2024

Language: Английский

Citations

13
Industrial and Laboratory Technologies for the Chemical Recycling of Plastic Waste DOI Creative Commons

Mason T. Chin,

Tianning Diao

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12437 - 12453

Published: Aug. 5, 2024

Synthetic polymers play an indispensable role in modern society, finding applications across various sectors ranging from packaging, textiles, and consumer products to construction, electronics, industrial machinery. Commodity plastics are cheap produce, widely available, versatile meet diverse application needs. As a result, millions of metric tons manufactured annually. However, current approaches for the chemical recycling postconsumer plastic waste, primarily based on pyrolysis, lag efficiency compared their production methods. In recent years, significant research has focused developing milder, economically viable methods commodity plastics, which involves converting waste back into monomers or transforming it other valuable chemicals. This Perspective examines both cutting-edge laboratory-scale contributing advancements field recycling.

Language: Английский

Citations

12
Ultrafast Thermal RAFT Depolymerization at Higher Solid Contents DOI Creative Commons

Dimitra Mantzara,

Richard Whitfield, Hyun Suk Wang

et al.

ACS Macro Letters, Journal Year: 2025, Volume and Issue: unknown, P. 235 - 240

Published: Feb. 10, 2025

Although thermal solution RAFT depolymerization has recently emerged as an efficient chemical recycling methodology, current approaches require specialized solvents (i.e., dioxane), typically suffer from extended reaction times, and operate exclusively under highly dilute conditions 5 mM repeat unit concentration). To circumvent these limitations, a commercial radical initiator is introduced to kinetically untrap the promote chain-end activation. By varying concentration, remarkable rate acceleration (up 72 times faster) can be observed, enabling completion of within min. Notably, 20-fold increase in concentration did not appreciably compromise final yield, while very high percentages monomer could recovered wide range solvents, including dimethyl sulfoxide, anisole, xylene, acetonitrile, toluene, trichlorobenzene. Our findings only offer intriguing mechanistic aspects, but also significantly expand scope applications depolymerization.

Language: Английский

Citations

2