100th Anniversary of Macromolecular Science Viewpoint: Achieving Ultrahigh Molecular Weights with Reversible Deactivation Radical Polymerization

An, Zesheng

doi:10.1021/acsmacrolett.0c00043

Cited by 59 publications

(77 citation statements)

References 69 publications

(109 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The fabrication of controlled UHMW polymers (defined by M n > 10 6 g mol −1 ) is a promising technique for preparing materials with outstanding mechanical properties. [ 146 ] Key to the preparation of UHMW polymers is the application of a highly living propagation process, where a low instantaneous radical concentration is maintained throughout the polymerization so that bimolecular termination events can be minimized and chain growth can continue to beyond 10,000 repeat units. Sumerlin and co‐workers pioneered the synthesis of controlled UHMW acrylamido polymers by exploiting the high livingness of photoRAFT, which was recently extended to low k p monomers in organic solvents.…”

Section: Advanced and Emerging Applications Of Raftmentioning

confidence: 99%

Progress and Perspectives Beyond Traditional RAFT Polymerization

et al. 2020

View full text Add to dashboard Cite

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

show abstract

Section: Advanced and Emerging Applications Of Raftmentioning

confidence: 99%

Progress and Perspectives Beyond Traditional RAFT Polymerization

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Among the metal‐free polymerization, organo‐initiated methyl methacrylate (MMA), an industrially important class of monomer, has a wide range of applications. Up to now, there are several approaches to achieve the polymerization of MMA, which include anionic polymerization, 7,8 radical polymerization, 9–12 group transfer polymerization (GTP), 13 coordination addition polymerization 14 and Lewis pair polymerization 15 . The anionic polymerization of MMA is a powerful but challenging topic, which features a high degree of complexity of initiation and propagation kinetics, frequent occurrence of side reactions and aggregation of active chain ends as well as the resulting equilibria between different types of aggregates and ion pairs 16–18 .…”

Section: Introductionmentioning

confidence: 99%

Synthetic and mechanistic aspects of anionic polymerization of methyl methacrylate using tetrabutyl ammonium thioimidate

Zhang

Wang

2021

Journal of Polymer Science

View full text Add to dashboard Cite

The tetrabutylammonium salts of ionic organo‐initiator containing N,N'‐diisopropylthiourea (TUA‐1) or N,N'‐diethylthiourea (TUA‐2) serve as inexpensive initiators for the anionic polymerization of methyl methacrylate (MMA) at room temperature. The molecular weights of obtained polymers are in the range of 1500–22,700 g mol−1 and the molecular weight distributions are fairly broad (Đ = 1.9–2.5) in optimized cases. The molar ratio of monomer to initiator can be achieved up to 800. Side‐reactions, for example, backbiting, transfer reactions result in the polymerization being a non‐living manner, thus leading to broad molecular weight distributions of the resulting polymers. The effects of counterion nature were also studied from the polymerization of MMA using TUA‐1 anion with sodium or potassium salts as counterions under identical conditions. Detailed investigation indicates that the polymerization proceeds via a sulfur anion initiated repeated 1,4‐Machael addition. In general, thioimidate initiators induced MMA polymerization feature certain induction periods, which is ascribed to slow addition thioimidate to CC double bond of MMA as a result of low initiator efficiency.

show abstract

“…[5] In addition, the X-Mt m salt is sensitive to oxygen, therefore, several cycles of freeze-pump-thaw usually used to be conducted to remove oxygen from monomer solution before polymerization reaction. [9,10] With the development to overcome its drawbacks, ATRP now can be carried out with low ppm levels of catalysts using some new reversibledeactivation radical polymerization approaches, such as initiator for continuous activator regeneration (ICAR), electrochemically mediated ATRP (eATRP), supplemental activator and reducing agent (SARA), photoinduced (photo-ATRP) and activators regenerated by electron transfer (ARGET). [11][12][13][14][15][16] It was reported that ARGET and electrochemically mediated ATRP (eATRP) or simplified eATRP approaches allow ATRP starts with the catalyst in oxidatively stable state and the presence of limited amounts of oxygen (or air).…”

Section: Introductionmentioning

confidence: 99%

Synthesis and characterization of star‐shaped PMMA using low‐ppm ARGET ATRP approach and changing to rigid powder for bone cement

Huynh

Linh

Huy

et al. 2021

Vietnam Journal of Chemistry

View full text Add to dashboard Cite

Some low‐ppm concentrations of CuII complex catalyst (15, 30 and 60 ppm) were used for synthesis of 4‐arm star PMMA (4sPMMA) via Atom Transfer Radical Polymerization using Activators Regenerated by Electron Transfer approach (ARGET ATRP). CuBr2/pentamethyldiethylene triamine and tin(II) 2‐ethylhexanoate were used as a complex catalyst and reducing agent, respectively. Characterization of 4sPMMA samples was performed by using conversion measurement, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC). The obtained results demonstrated that the concentration of CuII of 30 ppm was suitable to prepare 4sPMMA with high monomer conversion up to 93.9 % at 80 °C for 24 hours (MnGPC = 29.7 kDa with target Mn of 30 kDa) for our case. Selected product of 4sPMMA in porous powder was next changed to rigid powder. Scanning electron microscopy measurement showed random‐shape morphology of the powder with bead size in the range of 5‐110 μm. Energy dispersive X‐ray analysis indicated that no traces of Cu and Sn metals were detected. The 4sPMMA beads can be prospectively used as a prepolymer component for acrylic bone cement.

show abstract

100th Anniversary of Macromolecular Science Viewpoint: Achieving Ultrahigh Molecular Weights with Reversible Deactivation Radical Polymerization

Cited by 59 publications

References 69 publications

Progress and Perspectives Beyond Traditional RAFT Polymerization

Progress and Perspectives Beyond Traditional RAFT Polymerization

Synthetic and mechanistic aspects of anionic polymerization of methyl methacrylate using tetrabutyl ammonium thioimidate

Synthesis and characterization of star‐shaped PMMA using low‐ppm ARGET ATRP approach and changing to rigid powder for bone cement

Contact Info

Product

Resources

About