Experimental and computational investigation of oxidative quenching governed aqueous organocatalyzed atom transfer radical polymerization

Bian, Chao; Zhou, Yin‐Ning; Deetz, Joshua D.; Luo, Zheng‐Hong

doi:10.1016/j.cej.2019.01.087

Cited by 27 publications

(29 citation statements)

References 71 publications

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“…This behavior may be occurring because the increase in the catalyst ratio contributes to the generation of catalysts of excited state ( C * ) and oxidized state ( C *+ ), leading to higher activation and deactivation rates, as reported in literature. [ 24,33,55 ] Thus, the equilibrium is accelerated and the process control is improved.…”

Section: Resultsmentioning

confidence: 99%

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

Silva

Vieira

2020

Macro Chemistry & Physics

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Limonene is a potential candidate for the synthesis of polymers from renewable and non-toxic sources. The synthesis of poly(limonene) via controlled photopolymerization is studied for the first time, both at an experimental and computational level. A kinetic modeling is developed and all unknown parameters are estimated by adjusting them to the experimental data (conversion, molar mass, and dispersity). The reasonable model fit indicates that the proposed mechanism can be considered valid for this process simulation. In that fashion, different reagent ratios are evaluated, as well as simulations for long polymerization times. The experiments provide less than 10% monomer conversion at 40 °C, and short times. However, it is possible to identify a reasonable polymerization control (dispersities <1.5). In a complementary way, the simulations allowed to identify a threshold of reagent ratios in order to maintain the polymerization control for conversions around 20%, and at the same time enable monomer conversions at the same level as traditional thermally-initiated radical polymerizations at high temperatures. Therefore, this new route can be a promising alternative for the synthesis of limonene-based polymers.

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Section: Resultsmentioning

confidence: 99%

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

Silva

Vieira

2020

Macro Chemistry & Physics

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“…(2019) demonstrated for the first time the use of a water‐soluble catalyst to 3,7‐methoxypolyethylene glycol 1‐naphthalene‐10‐phenoxazineand obtained excellent results for the polymerization of monoethyl ether methacrylate (ethylene glycol) (PEGMA). [ 48 ]…”

Section: Components Of O‐atrpmentioning

confidence: 99%

“…[ 96 ] In 2019, the polymerization of different monomers in aqueous media through the oxidative quenching pathway was proposed for the first time reaching great results. [ 48 ]…”

Section: Components Of O‐atrpmentioning

confidence: 99%

Metal‐Free Organocatalyzed Atom Transfer Radical Polymerization: Synthesis, Applications, and Future Perspectives

Gonçalves

Rodrigues

Vieira

2021

Macromol. Rapid Commun.

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Reversible deactivation radical polymerization (RDRP) is a class of powerful techniques capable of synthesizing polymers with a well‐defined structure, properties, and functionalities. Among the available RDRPs, ATRP is the most investigated. However, the necessity of a metal catalyst represents a drawback and limits its use for some applications. O‐ATRP emerged as an alternative to traditional ATRP that uses organic compounds that catalyze polymerization under light irradiation instead of metal. The friendly nature and the robustness of O‐ATRP allow its use in the synthesis of tailorable advanced materials with unique properties. In this review, the fundamental aspects of the reductive and oxidative quenching mechanism of O‐ATRP are provided, as well as insights into each component and its role in the reaction. Besides, the breakthrough recent studies that applied O‐ATRP for the synthesis of functional materials are presented, which illustrate the significant potential and impact of this technique across diverse fields.

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“…External stimuli, such as light and electrical current, have been proved to be a powerful protocol in controlled radical polymerization (CRP) or reversible deactivation radical polymerization (recommended by IUPAC) by manipulating the electron transfer process . Recent advances in ultrasound as external stimuli for CRP offer a promising approach to synthesize well‐defined polymers under mild conditions and scale‐up of CRP .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic and kinetic investigation of Cu(II)‐catalyzed controlled radical polymerization enabled by ultrasound irradiation

2019

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Controlled radical polymerization (CRP) under external field has been an attractive research area in these years. In this work, a new electron transfer mechanism, that is, sonochemically induced electron transfer (SET) was introduced to mediate polymerization for the first time. The activator Cu I X/L complex was (re)generated from Cu II X 2 /L in dimethylsulfoxide (DMSO) by the SET process in the presence of free ligand tris (2-dimethylaminoethyl)amine (Me 6 TREN). The investigation of polymerization including the mechanistic insights and effect of experimental conditions on the rate of reaction has been undertaken. Kinetics of Cu(II)-catalyzed CRPs via SET under different conditions (i.e., Me 6 TREN concentration, catalyst loading, targeted degree of polymerization, and sonication power) were conducted in an unprecedentedly controlled manner, yielding polymers with predetermined molar masses and low dispersities (Đ < 1.12). Attractively, the polymerization can be performed without the piezoelectric nanoparticles and exogenous reducing agent. Contamination by nonliving chains formed from sonochemically generated radicals is avoided as well. All of these results supported that Cu(II)-based catalyst activation enabled by ultrasonication has a promising potential in scale-up of CRP.

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Experimental and computational investigation of oxidative quenching governed aqueous organocatalyzed atom transfer radical polymerization

Cited by 27 publications

References 71 publications

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

An Experimental and Computational Approach on Controlled Radical Photopolymerization of Limonene

Metal‐Free Organocatalyzed Atom Transfer Radical Polymerization: Synthesis, Applications, and Future Perspectives

Mechanistic and kinetic investigation of Cu(II)‐catalyzed controlled radical polymerization enabled by ultrasound irradiation

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