Perylene as an Organic Photocatalyst for the Radical Polymerization of Functionalized Vinyl Monomers through Oxidative Quenching with Alkyl Bromides and Visible Light

Miyake, Garret M.; Theriot, Jordan C.

doi:10.1021/ma502044f

Cited by 320 publications

(341 citation statements)

References 63 publications

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“…Significant advancements have enabled the use of lower levels of transition metal catalysts 10–13 and increased ability for polymer purification, 14–16 while recently organocatalyzed ATRP (O-ATRP) has risen as an approach to entirely eliminate metal contamination of the polymer product. 17–22 …”

Section: Introductionmentioning

confidence: 99%

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

et al. 2017

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Organocatalyzed atom transfer radical polymerization (O-ATRP) has emerged as a metal-free variant of historically transition-metal reliant atom transfer radical polymerization. Strongly reducing organic photoredox catalysts have proven capable of mediating O-ATRP. To date, operation of photoinduced O-ATRP has been demonstrated in batch reactions. However, continuous flow approaches can provide efficient irradiation reaction conditions and thus enable increased polymerization performance. Herein, the adaptation of O-ATRP to a continuous flow approach has been performed with multiple visible-light absorbing photoredox catalysts. Using continuous flow conditions, improved polymerization results were achieved, consisting of narrow molecular weight distributions as low as 1.05 and quantitative initiator efficiencies. This system demonstrated success with 0.01% photocatalyst loadings and a diverse methacrylate monomer scope. Additionally, successful chain-extension polymerizations using 0.01 mol % photocatalyst loadings reveal continuous flow O-ATRP to be a robust and versatile method of polymerization.

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Section: Introductionmentioning

confidence: 99%

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

et al. 2017

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“…31,32 More recently, an important development of light-induced living polymerization was presented almost simultaneously by Hawker and coworkers and Miyake et al, which realized a metal-free ATRP with an organic visible-light photocatalyst. 36,37 In traditional Cu-mediated ATRP, Guan and Smart discovered that the rate and livingness of ATRP can be significantly improved under visible light irradiation. 39 Yagci and coworkers reported UV light-induced ATRP of MMA through directly reduction of Cu II X 2 /L to Cu I X/L complex.…”

Section: Introductionmentioning

confidence: 99%

An old kinetic method for a new polymerization mechanism: Toward photochemically mediated ATRP

Zhou

Luo

2015

AIChE Journal

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in Wiley Online Library (wileyonlinelibrary.com) With the idea of "an old method for a new mechanism," a detailed kinetic insight into photochemically mediated atomtransfer radical polymerization (photo ATRP) was presented through a validated comprehensive model. The simulation mimics the experimental results of the model system using optimized photochemically mediated radical generation rate coefficients. The activator and radical (re)generated from the photo mediated reactions endow the photo ATRP with unique features, such as rapid ATRP equilibrium and quick consumption of initiator with a small amount of residual. The effect of the reaction parameters on ATRP behaviors was also investigated. Results showed that the acceleration of polymerization rate follows the square root law in the following three cases: the overall photochemically mediated radical generation rate coefficients (k r ), the free ligand concentration, and the initiator concentration. However, the independence of the apparent propagation rate coefficient (k app p ) on the square root of catalyst concentration might be attributed to the result of the synergy between the activators regenerated by electron-transfer ATRP and the initiators for continuous activator regeneration ATRP mechanism. The photo ATRP is able to design and prepare various polymers by carefully tuning the conditions using the model-based optimization approach.

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“…Very recently, photochemistry was applied to ATRP in the presence of organic catalysts such as derivatives of perylene and phenothiazine (50,51). It is interesting to observe that phenothiazine is used as a very efficient inhibitor of polymerization of acrylic acid but N-phenyl phenothiazine (52) is an excellent photocatalysts in polymerization of methacrylates (51).…”

Section: Figure 1 Results Of Scifinder Search On Various Crp Systemsmentioning

confidence: 99%

Controlled Radical Polymerization: State-of-the-Art in 2014

Matyjaszewski

2015

ACS Symposium Series

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Perylene as an Organic Photocatalyst for the Radical Polymerization of Functionalized Vinyl Monomers through Oxidative Quenching with Alkyl Bromides and Visible Light

Cited by 320 publications

References 63 publications

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

An old kinetic method for a new polymerization mechanism: Toward photochemically mediated ATRP

Controlled Radical Polymerization: State-of-the-Art in 2014

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