Progress and Perspectives Beyond Traditional RAFT Polymerization

Advanced Science, Journal Year: 2020, Volume and Issue: 7(20)

Published: Aug. 26, 2020

Abstract The development of advanced materials based on well‐defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible‐deactivation chain growth procedures now routinely leveraged prepare exquisitely precise polymer products. Reversible addition‐fragmentation transfer (RAFT) powerful protocol within this domain, where the unique chemistry thiocarbonylthio (TCT) compounds can harnessed control vinyl polymers. With intense recent focus RAFT, new strategies for initiation external have emerged that paving way preparing polymers demanding applications. In work, cutting‐edge innovations in RAFT opening up technique broader suite researchers explored. Emerging activating TCTs surveyed, which providing access into traditionally challenging environments polymerization. latest advances future perspectives applying RAFT‐derived also shared, goal convey rich potential an ever‐expanding range high‐performance

Language: Английский

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Porphyrinic Zirconium Metal–Organic Frameworks (MOFs) as Heterogeneous Photocatalysts for PET‐RAFT Polymerization and Stereolithography

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(10), P. 5489 - 5496

Published: Nov. 12, 2020

Abstract In this study, porphyrinic zirconium (Zr) MOFs were investigated as heterogeneous photocatalysts for photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization of various monomers under a broad range wavelengths, producing polymers with high monomer conversions, narrow molecular weight distributions, low dispersity and good chain‐end fidelity. Screening Zr‐MOFs (Zn) containing Zn‐metalled ligands demonstrated that MOF‐525 the smallest size had best photocatalytic activity in PET‐RAFT polymerization, due to enhanced dispersion light penetration. Oxygen tolerance temporal control also during MOF catalysed PET‐RAFT. Results suggested rates significantly affected by changing surface area MOFs, could be easily separated recycled up five independent polymerizations without an obvious decrease efficiency. Finally, utilized create three‐dimensional polymeric objects resolution via visible mediated stereolithography open‐air environment.

Language: Английский

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Photocontrolled RAFT polymerization: past, present, and future

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

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Rapid High‐Resolution 3D Printing and Surface Functionalization via Type I Photoinitiated RAFT Polymerization

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(16), P. 8839 - 8850

Published: Jan. 15, 2021

Abstract RAFT facilitated digital light projection 3D printing of polymeric materials provides a convenient and facile route for inducing post‐fabrication transformations via reactivation dormant chain transfer agents. In this work, we report the use Norrish type I photoinitiator in conjunction with agent to produce variety open‐air printable resins that rapidly cure under visible irradiation. The photoinitiator‐RAFT system polymerizes extremely quickly high build rates up 9.1 cm h −1 , representing 7‐fold increase compared previous mediated systems. printed containing thiocarbonylthio groups can be also produced using low concentrations divinyl comonomers initial resins, which has not been successfully achieved other photocontrolled polymerization techniques. Interestingly, inclusion agents significantly improves resolution formulations without agent, allowing fabrication intricate complex objects. Spatiotemporally controlled surface modifications objects from on material surfaces were performed one two‐pass configurations, multiple successive post‐printing same object.

Language: Английский

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Photo‐Iniferter RAFT Polymerization

Macromolecular Rapid Communications, Journal Year: 2021, Volume and Issue: 43(1)

Published: Nov. 9, 2021

Light-mediated polymerization techniques offer distinct advantages over reactions fueled by thermal energy, such as high spatial and temporal control well the possibility to work under mild reaction conditions. Reversible addition-fragmentation chain-transfer (RAFT) is a highly versatile radical method that can be utilized variety of monomers produce vast number complex macromolecular structures. The use light drive RAFT-polymerization possible via multiple routes. Besides photo-initiators, or photo-catalysts, direct activation chain transfer agent controlling RAFT process in photo-iniferter (PI) an elegant way initiate reactions. Within this review, PI-RAFT its conventional are discussed detail.

Language: Английский

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Precision polymer synthesis by controlled radical polymerization: Fusing the progress from polymer chemistry and reaction engineering

Progress in Polymer Science, Journal Year: 2022, Volume and Issue: 130, P. 101555 - 101555

Published: May 7, 2022

Language: Английский

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Ultrasonics in polymer science: applications and challenges

Progress in Materials Science, Journal Year: 2023, Volume and Issue: 136, P. 101113 - 101113

Published: March 22, 2023

Language: Английский

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Preparation of Polymerized High Internal Phase Emulsion Membranes with High Open-Cellular Extent and High Toughness via RAFT Polymerization

Polymers, Journal Year: 2025, Volume and Issue: 17(4), P. 515 - 515

Published: Feb. 17, 2025

Porous polymer membranes with highly interconnected open-cellular structure and high toughness are crucial for various application fields. Polymerized internal phase emulsions (polyHIPEs), which usually exist as monoliths, possess the advantages of porosity good connectivity. However, it is difficult to prepare due brittleness easy pulverization. Copolymerizing acrylate soft monomers can effectively improve polyHIPEs, but cause emulsion instability pore collapse. In this paper, stable HIPEs a content butyl (41.7 mol% 75 based on monomers) be obtained by using composite emulsifier (30 wt.% consisting Span80/DDBSS (9/2 in molar ratio) adding 0.12 mol·L-1 CaCl2 according aqueous concentration. On basis, polyHIPE extent firstly prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. The addition RAFT agent significantly improves mechanical properties without affecting structure. polymerization enhanced compared conventional free radical When ratio acrylate/styrene/divinylbenzene 7/4/1, membrane presents plastic deformation during tensile test. modulus reaches 93.04 ± 12.28 kJ·m-3 while 92.35%, also has excellent thermal stability.

Language: Английский

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Thermo-Responsive Poly (N-isopropyl acrylamide-b-vinylimidazole)/Pd Catalyst: Catalytic Application of Suzuki–Miyaura Coupling Reaction in Water

Catalysis Surveys from Asia, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Language: Английский

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Metal-Free Cationic Polymerization of Vinyl Ethers with Strict Temporal Control by Employing an Organophotocatalyst

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(17), P. 6357 - 6362

Published: April 26, 2021

By virtue of spatiotemporal control over the chain propagating, visible-light-regulated organocatalytic photoredox cationic polymerization provides an appealing approach for construction metal-free, well-defined polymers and materials. However, so far, organic photocatalysts capable mediated vinyl ethers are quite limited, photocontrol or efficiency is often eroded due to difficulty in achieving a good activation–deactivation balance, which greatly dependent on redox property catalyst. Here, we introduce new type photocatalysts, bisphosphonium salts, show high performance photoregulated reversible addition–fragmentation transfer allow synthesis poly(vinyl ethers) with predictable molecular weights narrow dispersities at low ppm catalyst loadings under visible light. In particular, tunable potential excellent stability endow salts strict temporal control, thus enabling metal-free halt long dark period.

Language: Английский

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