Controlling polymer properties through the shape of the molecular-weight distribution

Gentekos, Dillon T.; Sifri, Renee J.; Fors, Brett P.

doi:10.1038/s41578-019-0138-8

Cited by 172 publications

(174 citation statements)

References 125 publications

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“…Fors' and Boyer's groups have introduced different strategies to achieve such control. [171,172] More recent work by Anastasaki and co-workers into tailoring polymer dispersity by mixing high-and low-activity TCT compounds also holds considerable promise for tuning the bulk physical properties of RAFT-derived polymers. [173] Furthermore, the effect of instantaneous initiator-derived radical concentrations on RAFT has received scant attention, which may reveal opportunities for improving traditional initiation systems.…”

Section: Future Outlookmentioning

confidence: 99%

Progress and Perspectives Beyond Traditional RAFT Polymerization

et al. 2020

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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.

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Section: Future Outlookmentioning

confidence: 99%

Progress and Perspectives Beyond Traditional RAFT Polymerization

et al. 2020

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“…In anionic polymerization as much as in RDRP both features go typically skewness of a distribution must also be taken into account. [14] Last but not least, also the concept of modality is not easily applied since the difference between a mono-and multimodal distribution may simply be a question of resolution power of the analytical method applied or of the type of distribution examined (number, weight or log-weighted distribution). [15] Yet, first very promising advances have been made toward controlling the broadness of molecular weight distributions.…”

Section: Doi: 101002/macp202000234mentioning

confidence: 99%

Polymers in the Blender

Junkers

2020

Macro Chemistry & Physics

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Ever since the birth of controlled polymerizations, polymer synthesis always strived toward distributions that are as narrowly dispersed as possible. Yet, such polymers are not always advantageous, and only recently methods have started to develop that allow to create polymers with controllable molecular weight and dispersity. Stretching beyond that, there are also now tools to create distributions of any shape. This level of control, even if this is just the start of these endeavors, has tremendous potential for developing materials with superior and more precise physical properties. The principles for the synthesis of different molecular weight distributions shapes are introduced and discussed.

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“…Such structural uniformity should be a direct result of the BCO monodispersity. stability-by tuning the constitutional-block dispersities 18,[41][42][43][44][45] . Thus, we hypothesized that BCO mixtures with different numbers of glucose units could further expand the morphologies, features, and sizes accessible from the current BCO system.…”

Section: Synthesismentioning

confidence: 99%

Rapid access to discrete and monodisperse block co-oligomers from sugar and terpenoid toward ultrasmall periodic nanostructures

et al. 2020

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Discrete block co-oligomers (BCOs) are gaining considerable attention due to their potential to form highly ordered ultrasmall nanostructures suitable for lithographic templates. However, laborious synthetic routes present a major hurdle to the practical application. Herein, we report a readily available discrete BCO system that is capable of forming various self-assembled nanostructures with ultrasmall periodicity. Click coupling of propargyl-functionalized sugars (containing 1–7 glucose units) and azido-functionalized terpenoids (containing 3, 4, and 9 isoprene units) afforded the discrete and monodisperse BCOs with a desired total degree of polymerization and block ratio. These BCOs microphase separated into lamellar, gyroid, and cylindrical morphologies with the domain spacing (d) of 4.2–7.5 nm. Considering easy synthesis and rich phase behavior, presented BCO systems could be highly promising for application to diverse ~4-nm nanofabrications.

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Controlling polymer properties through the shape of the molecular-weight distribution

Cited by 172 publications

References 125 publications

Progress and Perspectives Beyond Traditional RAFT Polymerization

Progress and Perspectives Beyond Traditional RAFT Polymerization

Polymers in the Blender

Rapid access to discrete and monodisperse block co-oligomers from sugar and terpenoid toward ultrasmall periodic nanostructures

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