Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization

Carmean, R. Nicholas; Sims, Michael B.; Figg, C. Adrian; Hurst, Paul Joshua; Patterson, Joseph P.; Sumerlin, Brent S.

doi:10.1021/acsmacrolett.0c00203

Cited by 96 publications

(84 citation statements)

References 34 publications

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“…While writing this Perspective, the Sumerlin group published the synthesis of a range of UHMW polymer classes in organic solvents, thus, showing great promise toward this direction. 43 UHMW block copolymers maintaining high end-group fidelity are also difficult to produce, although some examples were recently demonstrated. 40 It should also be highlighted that the characterization of such materials is not trivial, thus, limiting further research in the area.…”

Section: Uhmw Polymersmentioning

confidence: 99%

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Parkatzidis

Wang

Truong

et al. 2020

Chem

376

304

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This perspective summarizes the latest exciting developments in controlled radical polymerization during the last decade (2010)(2011)(2012)(2013)(2014)(2015)(2016)(2017)(2018)(2019)(2020). Our focus is to critically highlight strengths and weaknesses of recent achievements and portray how these discoveries have expanded the scope of tailor-made polymeric materials. Our perspective on remaining future challenges and where we expect the field to grow toward in the next decade will also be discussed.100 years have passed since the landmark publication by Hermann Staudinger in 1920, after which the field of polymer chemistry was founded. One major revolution in the field has been controlled radical polymerization (CRP), also referred to as reversibledeactivation radical polymerization (RDRP), as it grants users the ability to regulate molecular weight, dispersity (Ð), composition, architecture, and end-group fidelity of vinyl polymers. Currently, numerous CRP techniques are available, most famously atom transfer radical polymerization (ATRP), 1 nitroxide-mediated polymerization (NMP), 2 and reversible addition-fragmentation chain-transfer (RAFT) polymerization. 3 Importantly, polymers synthesized by CRP find use as emulsifiers, dispersants, electrolytes, rheology, and surface modifiers and are applied in commercial products related to home care, beauty, health, paint, energy, and electronics. 4 The focus of this perspective is to acknowledge and critically review recent developments in the area of CRP (decade 2010-2020) (Figure 1). The order in which the developments are presented is not associated to their significance or date of their original report. USING LIGHT AS AN EXTERNAL STIMULUSAmong various stimuli, light is perhaps the most attractive due to its abundance, wide availability, mild nature, low cost, and environmental benignity while it offers tremendous possibilities for temporal and spatial control. In addition, light-mediated polymerizations might offer additional opportunities as they do not require high temperatures, which may facilitate side reactions and/or depolymerization. At the same time, however, light-mediated polymerizations suffer from limited depth penetration and scalability issues, although these have been considerably addressed through the development of flow photochemistry, which allows for faster polymerizations, enhanced control over the molecular weight distributions, and the possibility to be combined with on-orin-line monitoring characterization techniques (the reader is referred to a recent review in flow chemistry polymerization). 5 Furthermore, certain wavelengths and intensities may be disadvantageous for various biological systems. Currently, there are two main developments in this area, namely photo-ATRP (including metal-mediated and metal-free ATRP) and photoinduced electron transferThe Bigger Picture Challenges and opportunities:Universal catalysts compatible with a range of monomers and stimuli are urgently required to produce materials with enhanced control over monomer seq...

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Section: Uhmw Polymersmentioning

confidence: 99%

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Parkatzidis

Wang

Truong

et al. 2020

Chem

376

304

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“…We proposed this mechanism of polymerization to be similar to a photoiniferter polymerization. [35][36][37] However, using the electron beam to control chemical reactions is challenging due to potential radiolysis side products 38 and concentration gradients resulting from the spatially confined irradiation of the sample. Moreover, it is not directly analogous to reactions occurring during normal benchtop syntheses.…”

Section: Progress and Potentialmentioning

confidence: 99%

Probing Thermoresponsive Polymerization-Induced Self-Assembly with Variable-Temperature Liquid-Cell Transmission Electron Microscopy

Scheutz

Touve²,

Carlini

et al. 2021

Matter

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“…but different spacer groups exhibit different tendencies towards intermolecular crosslinking, and a satisfactory model accounting for this phenomenon has yet to be established. Finally, efforts at accessing architectures that push the limit of ultrahigh molecular weights 95,99 challenge current purification and characterization techniques. Water-soluble CCSs are currently able to be very quickly purified by tangential flow filtration, but the purification of hydrophobic or water-sensitive architectures requires the use of either dialysis (for which an appropriate molecular weight cutoff may not exist) or tedious fractionation.…”

Section: Discussionmentioning

confidence: 99%

Controlled radical copolymerization of multivinyl crosslinkers: a robust route to functional branched macromolecules

Sims

2020

Polymer International

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Controlled radical polymerization (CRP) has both revolutionized the synthesis of linear polymers and enabled unprecedented topological complexity. While the synthesis of many polymeric architectures requires careful planning and specialized precursors, branched macromolecules such as segmented hyperbranched polymers (SHPs), knotted polymers, core-crosslinked stars (CCSs), and more can be synthesized through the copolymerization of vinyl monomers and divinyl crosslinkers in only a few steps. In the nearly two decades since its discovery, this strategy has helped elucidate the fundamental polymerization behavior of crosslinkers and also yielded a variety of functional and stimuli-responsive materials. The purpose of this mini-review is to therefore overview critical fundamental aspects of CRP of crosslinkers and materials derived therefrom. The process by which both SHPs and CCS polymers are synthesized, the effect of key reaction parameters and intriguing recent advances are described with the intent of both educating new researchers and inspiring new directions in this area.

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Ultrahigh Molecular Weight Hydrophobic Acrylic and Styrenic Polymers through Organic-Phase Photoiniferter-Mediated Polymerization

Cited by 96 publications

References 34 publications

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Probing Thermoresponsive Polymerization-Induced Self-Assembly with Variable-Temperature Liquid-Cell Transmission Electron Microscopy

Controlled radical copolymerization of multivinyl crosslinkers: a robust route to functional branched macromolecules

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