Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms DOI Creative Commons

David Lundberg,

Landon Kilgallon,

Julian Cooper

et al.

Published: Jan. 22, 2024

An understanding of monomer sequence is required to predict and engineer the properties copolymers. Typically, comonomer inferred or determined from reactivity ratios, which are measured through copolymerization experiments. The accurate determination ratios copolymerizations where one both monomers undergo reversible propagation, however, has been complicated by difficulty in solving underlying population balance equations, presence myriad copolymer equations literature derived under varying assumptions simplifications, lack an easy fit integrated model. Here, we rectify assert consistency between previously reported disparate form, introduce a new method explicitly solve perform stochastic simulations evaluate ability these three methods produce consistent consumption predictions fits simulated data. We find that all given same input parameters, implies accuracy precision when modeling copolymerization, fitting experimental data, making sequence. Considering this consistency, make recommendation use numerical integration appropriate equation real data due its ease implementation single subjective parameter for implementation. further identify minimum number parameters suggest ways measure other information ex situ expediate fitting. Finally, practical utility developed herein demonstrated seven distinct datasets span wide range reactivities.

Language: Английский

The thermodynamics and kinetics of depolymerization: what makes vinyl monomer regeneration feasible? DOI Creative Commons
Victoria Lohmann, Glen R. Jones, Nghia P. Truong

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(3), P. 832 - 853

Published: Dec. 5, 2023

Insight into the thermodynamics and kinetics of depolymerization to understand barriers that prevent effective monomer regeneration from vinyl polymers, an exploration overcoming these limitations.

Language: Английский

Citations

41
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
Design of depolymerizable polymers toward a circular economy DOI Creative Commons
Julian F. Highmoore, Lasith S. Kariyawasam, Scott R. Trenor

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(5), P. 2384 - 2420

Published: Jan. 1, 2024

While our society is facing the challenge of accumulating plastic waste, this review discusses recent advances towards polymer circularity with an emphasis on manipulations monomer–polymer equilibrium to create chemically recyclable polymers.

Language: Английский

Citations

16
Recent Advances in Stimuli-Responsive Self-Immolative Polymers for Drug Delivery and Molecular Imaging DOI
Yuce Li,

Jixiu Liu,

Jing He

et al.

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(9), P. 4054 - 4077

Published: April 18, 2024

Stimuli-responsive self-immolative polymers (SIPs) represent a unique class of that can undergo controlled, sequential head-to-tail depolymerization upon specific stimuli. Since their inception, they have evolved over two decades to become one the most attractive polymer types. With characteristic feature "one stimulus, multiple responses", SIPs inherently possess ability serve as chemical amplifiers, which amplify weak or biological signals. This promises higher stimulus sensitivity, greater selectivity for microenvironments, and potential generate more persistent, extensive, significant responses while consuming fewer stimuli sources. Review summarizes latest research advancements in stimuli-responsive drug delivery molecular imaging past five years. Regarding structure SIPs, we briefly overview updates self-immolation units, end-cap moieties, sequence SIPs. In terms applications, focus on possible applications disease treatment methods. Finally, provide brief perspective future directions these applications.

Language: Английский

Citations

11
Harnessing Non-Thermal External Stimuli for Polymer Recycling DOI Creative Commons
Glen R. Jones, Richard Whitfield, Hyun Suk Wang

et al.

Macromolecules, Journal Year: 2025, Volume and Issue: 58(5), P. 2210 - 2223

Published: Feb. 18, 2025

Polymeric materials have become indispensable due to their versatility and low cost, yet environmental impact presents a significant global challenge. Traditional chemical recycling methods typically rely on heat as stimulus; for instance, pyrolysis is popular methodology which faces limitations high energy consumption, product selectivity, the generation of undesirable byproducts. In response, recent advances in promotion depolymerization degradation through alternative stimuli such light, electrochemistry, mechanical force, shown promising potential more efficient selective polymer breakdown, yielding either starting monomers or valuable small molecules. This perspective explores key examples these emerging strategies, highlighting improve upon current protocols offer pathways under milder conditions, while identifying challenges that future research must address translate chemistry into viable broadly applicable strategies.

Language: Английский

Citations

2
Chemical recycling of bromine-terminated polymers synthesized by ATRP DOI Creative Commons
Stella Afroditi Mountaki, Richard Whitfield, Kostas Parkatzidis

et al.

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

Citations

9
Self‐Assembly of Rod‐Coil Bottlebrush Copolymers into Degradable Nanodiscs with a UV‐Triggered Self‐Immolation Process DOI Creative Commons
Haoxiang Zeng, Xiaoli Liang, Derrick A. Roberts

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 7, 2024

Abstract Polymer nanodiscs, especially with stimuli‐responsive features, represent an unexplored frontier in the nanomaterial landscape. Such 2D nanomaterials are considered highly promising for advanced biomedicine applications. Herein, we designed a rod‐coil copolymer architecture based on amphiphilic, tadpole‐like bottlebrush copolymer, which can directly self‐assemble into core–shell nanodiscs aqueous environment. As side chains made of amorphous, UV‐responsive poly(ethyl glyoxylate) (PEtG) chains, they undergo rapid end‐to‐end self‐immolation upon light irradiation. This triggered nanodisc disassembly be used to boost small molecule release from core, is further aided by morphological change discs spheres.

Language: Английский

Citations

9
Recycling of Post-Consumer Waste Polystyrene Using Commercial Plastic Additives DOI Creative Commons
Sewon Oh, Hanning Jiang, Liat H. Kugelmass

et al.

ACS Central Science, Journal Year: 2024, Volume and Issue: 11(1), P. 57 - 65

Published: Nov. 25, 2024

Photothermal conversion can promote plastic depolymerization (chemical recycling to a monomer) through light-to-heat conversion. The highly localized temperature gradient near the photothermal agent surface allows selective heating with spatial control not observed bulk pyrolysis. However, identifying and incorporating practical agents into plastics for end-of-life have been realized. Interestingly, containing carbon black as pigment present an ideal opportunity recycling. Herein, we use visible light depolymerize polystyrene styrene monomers by using dye in commercial plastics. A model system is evaluated synthesizing polystyrene-carbon composites depolymerizing under white LED irradiation, producing monomer up 60% yield. Excitingly, unmodified postconsumer samples are successfully depolymerized without adding catalysts or solvents. Using focused solar yields 80% just 5 min. Furthermore, combining multiple types of small percentage enables full mixture. This simple method leverages existing additives actualize closed-loop economy all-colored

Language: Английский

Citations

9
Accurate Determination of Reactivity Ratios for Copolymerization Reactions with Reversible Propagation Mechanisms DOI

David Lundberg,

Landon J. Kilgallon, Julian C. Cooper

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(14), P. 6727 - 6740

Published: July 9, 2024

An understanding of monomer sequence is required to predict and engineer the properties copolymers. In stochastic polymerizations involving more than one monomer, typically inferred or determined from reactivity ratios, which are measured through copolymerization experiments. The accurate determination ratios copolymerizations where both monomers undergo reversible propagation, however, has been complicated by difficulty in solving underlying population balance equations, presence myriad copolymer equations literature derived under varying assumptions simplifications, lack an easy-to-fit integrated model. Here, we rectify assert consistency between previously reported disparate forms, introduce a new method explicitly solve perform simulations evaluate ability these three methods produce consistent comonomer consumption predictions fits simulated data. We find that all given same input parameters, implies accuracy precision when modeling copolymerization, fitting experimental data, making sequence. Considering this consistency, make recommendation use numerical integration appropriate equation fit real data due its ease implementation. further identify minimum number parameters for suggest ways measure other information ex situ expedite fitting. Finally, practical utility developed herein demonstrated seven distinct sets, span wide range reactivities.

Language: Английский

Citations

8
Polymer-mediated protein/peptide therapeutic stabilization: Current progress and future directions DOI

P S Rajalakshmi,

Katherine Snell,

Grace E. Kunkel

et al.

Progress in Polymer Science, Journal Year: 2024, Volume and Issue: 156, P. 101867 - 101867

Published: Aug. 8, 2024

Language: Английский

Citations

7