An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

Yang, Xuejin; Gitter, Sean R.; Roessler, Allison G.; Zimmerman, Paul M.; Boydston, Andrew J.

doi:10.1002/ange.202016393

Cited by 6 publications

(3 citation statements)

References 47 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Judicious choice of initiator structure and counterion was determined to drastically improve tacticity control of poly(norbornene). 80 Whereas linear pDCPD has historically been difficult to produce with transition metal catalysts owing to their high reactivity, its synthesis was recently achieved in a metal-free system, enabling access to a manifold of unexplored ROMP polymer structures. 81 This could enable the synthesis of elusive macromonomers for viscosity and shrinkage control in ROMP-based AM systems.…”

Section: Metal-free Rompmentioning

confidence: 99%

PhotoROMP: The Future Is Bright

Greenlee,

Weitekamp,

Foster

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

Since the earliest investigations of olefin metathesis catalysis, light has been the choice for controlling the catalyst activity on demand. From the perspective of energy efficiency, temporal and spatial control, and selectivity, photochemistry is not only an attractive alternative to traditional thermal manufacturing techniques but also arguably a superior manifold for advanced applications like additive manufacturing (AM). In the last three decades, pioneering work in the field of ring-opening metathesis polymerization (ROMP) has broadened the scope of material properties achievable through AM, particularly using light as both an activating and deactivating stimulus. In this Perspective, we explore trends in photocontrolled ROMP systems with an emphasis on approaches to photoinduced activation and deactivation of metathesis catalysts. Recent work has yielded a myriad of commercial and synthetically accessible photosensitive catalyst systems, although comparatively little attention has been paid to achieving precise control over polymer morphology using light. Metal-free, photophysical, and living ROMP systems have also been relatively underexplored. To take fuller advantage of both the thermomechanical properties of ROMP polymers and the operational simplicity of photocontrol, clear directions for the field are to improve the reversibility of activation and deactivation strategies as well as to further develop photocontrolled approaches to tuning cross-link density and polymer tacticity.

show abstract

Section: Metal-free Rompmentioning

confidence: 99%

PhotoROMP: The Future Is Bright

Greenlee,

Weitekamp,

Foster

et al. 2024

ACS Catal.

View full text Add to dashboard Cite

show abstract

“…In recent work, it has been found that the counter ion of the catalyst affects the stereoscopic regularity of the polymer. Using BF 4 − , PF 6 − , and BArF 4 − as counter ions, the trans‐polyolefin content of the polynorbornene decreased from 79% to 58% 88,89 . Solvents and temperatures also affect the stereoregularity of the polynorbornene produced by the ring‐opening metathesis reaction.…”

Section: Visible Light Controlled Cationic Living Polymerizationmentioning

confidence: 99%

“…Using BF 4 À , PF 6 À , and BArF 4 À as counter ions, the trans-polyolefin content of the polynorbornene decreased from 79% to 58%. 88,89 Solvents and temperatures also affect the stereoregularity of the polynorbornene produced by the ring-opening metathesis reaction. >98% trans-polyolefin can be obtained using dichloromethane as catalyst at low temperatures (À76 C).…”

Section: Development Of Photo-redox Catalysts In Photo-controlled Cat...mentioning

confidence: 99%

Recent advances on visible light induced cationic polymerization

Feng

Liu

et al. 2023

Journal of Polymer Science

View full text Add to dashboard Cite

Cationic polymerization is an important branch of polymer chemistry. Traditional cationic polymerization must be carried out in anhydrous and low temperature environment, with harsh operating conditions, high operating costs and high energy consumption. Visible light induced cationic polymerization is simple, environmentally friendly, and low‐cost, so it has become a research hotspot of living cationic polymerization. This paper gives an overview of the recent advances (mainly from 2015 to 2023) on visible‐light‐induced cationic polymerization, with a focus on visible‐light‐initiated and visible‐light‐controlled cationic polymerization. On the basis of controlling cationic polymerization to achieve macromolecular reaction engineering, the realization of temporal scale control will be the main development direction in the future.

show abstract

The Limited Palette for Photonic Block‐Copolymer Materials: A Historical Problem or a Practical Limitation?

et al. 2022

View full text Add to dashboard Cite

Block‐copolymer self‐assembly has proven to be an effective route for the fabrication of photonic films and, more recently, photonic pigments. However, despite extensive research on this topic over the past two decades, the palette of monomers and polymers employed to produce such structurally colored materials has remained surprisingly limited. In this Scientific Perspective, the commonly used block‐copolymer systems reported in the literature are summarized (considering both linear and brush architectures) and their use is rationalized from the point of view of both their historical development and physicochemical constraints. Finally, the current challenges facing the field are discussed and promising new areas of research are highlighted to inspire the community to pursue new directions.

show abstract

An Ion‐Pairing Approach to Stereoselective Metal‐Free Ring‐Opening Metathesis Polymerization

Cited by 6 publications

References 47 publications

PhotoROMP: The Future Is Bright

PhotoROMP: The Future Is Bright

Recent advances on visible light induced cationic polymerization

The Limited Palette for Photonic Block‐Copolymer Materials: A Historical Problem or a Practical Limitation?

Contact Info

Product

Resources

About