Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

Ramsey, Bonnie L.; Pearson, Ryan M.; Beck, Logan R.; Miyake, Garret M.

doi:10.1021/acs.macromol.6b02791

Cited by 120 publications

(87 citation statements)

References 47 publications

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“…For this type of polymerization, flow chemistry is an excellent tool for the kinetic assessment of the reaction, but serves only poorly as a method of production. The general observations made herein are generally in good agreement with the study by Miyake and co‐workers . No further optimization of the flow process was hence made, as the data gathered were sufficient for transfer of reaction conditions to surface grafting.…”

Section: Resultssupporting

confidence: 89%

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

Ramakers

Krivcov

Trouillet

et al. 2017

Macromol. Rapid Commun.

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The organocatalyzed photo-atom transfer radical polymerization (photoATRP) using 10-phenylphenothiazine as catalyst is studied toward its use in methacrylic acid (MAA) polymerization and surface grafting. The organocatalyzed photoATRP of methyl methacrylate (MMA) is first optimized for continuous flow synthesis in order to assess the livingness of the polymerization. MMA can be polymerized in batch and in flow; however, conversions are limited by the loss of bromine functionality and hence high conversions have to be traded in with increasing dispersities. Also, MAA is polymerized successfully in continuous flow with similar limitations. Flow conditions are transferred to surface grafting from silanized silicon wafers. The presence of ATRP initiators after silanization is confirmed by secondary ion mass spectrometry and X-ray photoelectron spectroscopy. Dense polymethacrylic acid brush films are successfully produced, which is not directly accessible via classical copper-mediated ATRP techniques.

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Section: Resultssupporting

confidence: 89%

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

Ramakers

Krivcov

Trouillet

et al. 2017

Macromol. Rapid Commun.

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“…It offers a fascinating avenue to fabricate tailor‐made polymers without metal residue . Miyake and co‐workers firstly transferred O‐ATRP from the batch reactor to the flow mode. The proposed polymerization mechanism, PCs and photoflow reactors were shown in Figure .…”

Section: Continuous Flow Photoinduced Reversible Termination Rdrpmentioning

confidence: 99%

Continuous Flow Photoinduced Reversible Deactivation Radical Polymerization

Zhu

Fang

et al. 2018

ChemPhotoChem

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Photoinduced reversible deactivation radical polymerization (RDRP) is a versatile and robust method to yield well‐defined polymers under mild conditions with additional advantages of spatial and temporal control. The process and scalability of photoinduced RDRP in the batch mode, however, are limited by the inherent light gradient effect according to the Beer–Lambert law. The continuous flow technique, as an alternative methodology, provides a solution to improve the irradiation efficiency and scale up the polymerization. This Minireview highlights recent progress in continuous flow photoinduced RDRP since 2016. Reversible termination RDRP, degenerative transfer RDRP and others are reviewed in consecutive order. An outlook for continuous flow photoinduced RDRP is also discussed.

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“…On the basis of the excellent control at high monomer conversion and the successful chain extension, we anticipated that ac ontinuous-flow strategy [16] would be practical to streamline the synthesis of semifluorinated polymers.F urthermore,o wing to the high surface-to-volume ratio in microchannels,t he photoreaction would be efficiently accelerated under flow conditions. [16,17] We began the flow synthesis of ablock copolymer with the setup depicted in Scheme 3. Thereaction solution of HFBA, TTC-2F,and PTH-2 ([HFBA]/[TTC-2F]/[PTH-2] = 20/1/0.05) in DMSO was injected into al ight-permeable tubing reactor (R1), which was wrapped around glassware equipped with white LEDs inside (see Figure S85).…”

Section: Communicationsmentioning

confidence: 99%

Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light

et al. 2017

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Fluorinated polymers are important materials that are widely used in many areas.Herein, we report the development of ametal-free photocontrolled radical polymerization of semifluorinated (meth)acrylates with an ew visible-lightabsorbing organocatalyst. This method enabled the production of av ariety of semifluorinated polymers with narrowm olarweight distributions from semifluorinated trithiocarbonates or perfluoroalkyl iodides.T he high performance of "ON/OFF" control and chain-extension experiments further demonstrate the utility and reliability of this method. Furthermore,t o streamline the preparation of semifluorinated polymers,ascalable continuous-flowapproach has been developed. Given the broad interest in fluorinated materials and photopolymerization, we expect that this method will facilitate the development of advanced materials with unique properties.The development of synthetic methods to prepare semifluorinated polymers is of great interest because these materials often possess interesting characteristics,s uch as high hydrophobicity,t unable lipophilicity,a nd improved thermal and chemical stability. [1,2] As ar esult, av ariety of methods have been developed for the preparation of such polymers. [3] Controlled/living radical polymerization (CRP), [3a] which enables the operationally simple polymerization of semifluorinated (meth)acrylates,isamong the most useful synthetic methods.[3] Fore xample,a tom-transfer radical polymerization (ATRP) [4] and its variants, [5] reversible addition-fragmentation chain transfer (RAFT) polymerization, [6] and nitroxide-mediated polymerization (NMP; [7] Scheme 1A,t op) have shown promising results for the preparation of precisely fluorinated materials.H owever,i n contrast to the CRP of nonfluorinated monomers, [4a,6a, 7a] most methods suffer from one or several of limitations,i ncluding 1) decreased control over molecular-weight distribution () at high conversion;2 )the use of af luorinated solvent; 3) undesired side reactions (e.g.,t ransesterification);o r 4) the use of am etal catalyst. Furthermore,c ontrol of the polymerization of semifluorinated monomers with an external stimulus, [8] such as visible light, has rarely been possible.[5]Recently,p hotoredox catalysis has found widespread application in ATRP, [9] RAFT/iniferter polymerization, [10] ring-opening metathesis polymerization, [11] and cationic polymerization, [12] thus providing arange of photo-CRP methods with excellent spatiotemporal control over chain growth. [13] Forthese processes,(meth)acrylates,acrylamides,and styrene derivatives are the most frequently investigated monomers. [13] Hawker and co-workers recently reported the precise synthesis of semifluorinated poly(meth)acrylates from activated alkyl bromides by the copper-catalyzed photo-ATRP method.[5] In their study,ametal catalyst and UV light were used to ensure efficient polymerization. Additionally,asemifluorinated tertiary alcohol solvent was required to suppress the transesterification.[5] Am etal-free method usi...

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Photoinduced Organocatalyzed Atom Transfer Radical Polymerization Using Continuous Flow

Cited by 120 publications

References 47 publications

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

Organocatalyzed Photo‐Atom Transfer Radical Polymerization of Methacrylic Acid in Continuous Flow and Surface Grafting

Continuous Flow Photoinduced Reversible Deactivation Radical Polymerization

Organocatalyzed Photocontrolled Radical Polymerization of Semifluorinated (Meth)acrylates Driven by Visible Light

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