RAFT-Mediated 3D Printing of “Living” Materials with Tailored Hierarchical Porosity DOI
Mitra Asadi‐Eydivand, Trevor C. Brown, Ali Bagheri

et al.

ACS Applied Polymer Materials, Journal Year: 2022, Volume and Issue: 4(7), P. 4940 - 4948

Published: June 28, 2022

Applications of reversible addition–fragmentation chain-transfer (RAFT) polymerization in three-dimensional (3D) printing have recently expanded the scope light-based 3D technologies through manufacturing "living" materials. In this study, we report RAFT-mediated, computer-controlled layer-by-layer scaffolds with tailored hierarchical porosities and highly resolved micro- macroscale features. Our system offers precise control over internal external architectures porous materials, including pore size, which is not attainable using conventional techniques where achievable complexity fabricated limited. RAFT-mediated supports a variety structural designs enables open-porous materials controlled variation porosity (e.g., ranging from 23 to 70% porosity). The RAFT-based formulation also allowed original computer-aided design (CAD) models, were designed MATLAB and/or SolidWorks, showing well-defined features throughout continuous architecture. As an application example, triply periodic minimal surface (TPMS) structures 3D-printed digital light processing (DLP) printer. An additional advantage these that they show character so can be modified patterned post-manufacturing step reactivation dormant network-bound RAFT functionalities. This research further broadens RAFT-driven may implications molecular separation, catalysis, energy storage, tissue engineering, drug delivery.

Language: Английский

Photocontrolled RAFT polymerization: past, present, and future DOI Creative Commons

Yungyeong Lee,

Cyrille Boyer, Min Sang Kwon

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(9), P. 3035 - 3097

Published: Jan. 1, 2023

In this review, we provide a brief history, progress, and applications, discuss the remaining challenges of photocontrolled reversible addition-fragmentation chain transfer (RAFT) polymerization (i.e., photoinduced electron/energy transfer-RAFT (PET-RAFT), photoiniferter, photomediated cationic RAFT polymerization). Among these, visible-light-driven has attracted particular attention in recent years due to its benefits, including low energy consumption safe reaction procedure. Moreover, incorporation visible-light photocatalysis conferred attractive features, such as spatiotemporal control oxygen tolerance; however, clear understanding mechanism not been completely provided. We also present research efforts elucidate mechanisms with aid quantum chemical calculations combined experimental evidence. This review offers an insight into better design systems for desired applications helps realize full potential both academic- industrial-scale applications.

Language: Английский

Citations

140
Cleavable Comonomers for Chemically Recyclable Polystyrene: A General Approach to Vinyl Polymer Circularity DOI

Gavin R. Kiel,

David Lundberg,

Elisabeth Prince

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(28), P. 12979 - 12988

Published: June 28, 2022

Many common polymers, especially vinyl are inherently difficult to chemically recycle and environmentally persistent. The introduction of low levels cleavable comonomer additives into existing polymerization processes could facilitate the production deconstructable recyclable variants with otherwise equivalent properties. Here, we report thionolactones that serve as for chemical deconstruction recycling polymers prepared through free radical polymerization, using polystyrene (PS) a model example. Deconstructable PS different molar masses (∼20-300 kDa) bearing varied amounts statistically incorporated thioester backbone linkages (2.5-55 mol %) can be selectively depolymerized yield well-defined thiol-terminated fragments (<10 suitable oxidative repolymerization generate recycled nearly identical mass parent material, in good yields (80-95%). A theoretical is provided generalize this memory effect. Notably, thermomechanical properties 2.5 % its product similar those virgin PS. were also shown effective cross-linked styrenic copolymer polyacrylate, suggesting comonomers may offer general approach toward circularity many (co)polymers.

Language: Английский

Citations

101
Bulk depolymerization of poly(methyl methacrylate) via chain-end initiation for catalyst-free reversion to monomer DOI Creative Commons
James B. Young, Rhys W. Hughes,

A. Tamura

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2669 - 2682

Published: Aug. 7, 2023

Language: Английский

Citations

78
Degradation of Polyacrylates by One-Pot Sequential Dehydrodecarboxylation and Ozonolysis DOI

Angie B. Korpusik,

Alafate Adili,

Kamal Bhatt

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(19), P. 10480 - 10485

Published: May 8, 2023

We establish a synthetically convenient method to degrade polyacrylate homopolymers. Carboxylic acids are installed along the polymer backbone by partial hydrolysis of ester side chains, and then, in one-pot sequential procedure, carboxylic converted into alkenes oxidatively cleaved. This process enables robustness properties polyacrylates be maintained during their usable lifetime. The ability tune degree degradation was demonstrated varying acid content polymers. is compatible with wide range polymers prepared from vinyl monomers through copolymerization acrylic different including acrylates, acrylamides, styrenics.

Language: Английский

Citations

52
Controlled-Radical Polymerization of α-Lipoic Acid: A General Route to Degradable Vinyl Copolymers DOI Creative Commons
Kaitlin R. Albanese,

Parker T. Morris,

Javier Read de Alaniz

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22728 - 22734

Published: Oct. 9, 2023

Here, we present the synthesis and characterization of statistical block copolymers containing α-lipoic acid (LA) using reversible addition-fragmentation chain-transfer (RAFT) polymerization. LA, a readily available nutritional supplement, undergoes efficient radical ring-opening copolymerization with vinyl monomers in controlled manner predictable molecular weights low molar-mass dispersities. Because lipoic diads resulting include disulfide bonds, these materials efficiently rapidly degrade when exposed to mild reducing agents such as tris(2-carboxyethyl)phosphine (Mn = 56 → 3.6 kg mol-1). This scalable versatile polymerization method affords facile way synthesize degradable polymers architectures, weights, dispersities from acid, commercially renewable monomer.

Language: Английский

Citations

50
Recyclable/degradable materials via the insertion of labile/cleavable bonds using a comonomer approach DOI Creative Commons
Catherine Lefay, Yohann Guillaneuf

Progress in Polymer Science, Journal Year: 2023, Volume and Issue: 147, P. 101764 - 101764

Published: Nov. 15, 2023

Language: Английский

Citations

49
Light-driven polymer recycling to monomers and small molecules DOI Creative Commons
Laura Wimberger,

Gervase Ng,

Cyrille Boyer

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: March 20, 2024

Abstract Only a small proportion of global plastic waste is recycled, which most mechanically recycled into lower quality materials. The alternative, chemical recycling, enables renewed production pristine materials, but generally comes at high energy cost, particularly for processes like pyrolysis. This review focuses on light-driven approaches chemically recycling and upcycling waste, with emphasis reduced consumption selective transformations not achievable heat-driven methods. We focus challenging to recycle backbone structures composed mainly C‒C bonds, lack functional groups i.e., esters or amides, that facilitate e.g., by solvolysis. discuss the use light, either in conjunction heat drive depolymerization monomers via photocatalysis transform polymers valuable molecules. structural prerequisites these are outlined, highlighting their advantages as well limitations. conclude an outlook, addressing key challenges, opportunities, provide guidelines future photocatalyst (PC) development.

Language: Английский

Citations

35
Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Poly(methyl methacrylate) DOI
Kwangwook Ko,

David Lundberg,

Alayna M. Johnson

et al.

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

18
Photocatalytic Direct Decarboxylation of Carboxylic Acids to Derivatize or Degrade Polymers DOI

Alafate Adili,

Angie B. Korpusik,

Daniel Seidel

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(40)

Published: Aug. 22, 2022

Visible light-mediated direct decarboxylation of carboxylic acids with an acridine photocatalyst is a convenient and powerful method to generate carbon-centered radicals in polymer chains. Advantageously, this process proceeds under mild conditions, without preactivation the acid groups. We utilize presence hydrogen atom donor form statistical acrylate-ethylene acrylate-propylene copolymers, which are challenging obtain by polymerization. additionally show that methacrylic units within polymethacrylates can trigger degradation backbones. Moreover, dual catalytic approach, combines function cobaloxime catalyst, leveraged furnish unique copolymers pendent alkenes. Our work indicates versatile technique for synthesis functional materials tailored compositions properties.

Language: Английский

Citations

70
Facet-Engineering of Materials for Photocatalytic Application: Status and Future Prospects DOI
Xiaomei Cheng, Jing Zhao, Wei‐Yin Sun

et al.

EnergyChem, Journal Year: 2022, Volume and Issue: 4(5), P. 100084 - 100084

Published: July 23, 2022

Language: Английский

Citations

59