Hydrated Clay for Catalyst Removal in Copper Mediated Atom Transfer Radical Polymerization

Munirasu, Selvaraj; Deshpande, A. B.; Baskaran, Durairaj

doi:10.1002/marc.200800240

Cited by 30 publications

(18 citation statements)

References 34 publications

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“…43–49 Currently, however, several catalyst (re)-generation methods allow performing ATRP reactions with low ppm levels of catalysts; these techniques include activators regenerated by electron transfer (ARGET) ATRP, 50–58 initiators for continuous activator regeneration (ICAR) ATRP, 50,59–65 supplemental activator and reducing agent (SARA) ATRP, 66–73 photoinduced ATRP (photoATRP), 74–85 85 and electrochemically mediated ATRP ( e ATRP, the method used in this work). 86–97 …”

Section: Introductionmentioning

confidence: 99%

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

et al. 2016

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An electrochemical approach was used to control atom transfer radical polymerization (ATRP) of n-butyl acrylate (BA) in miniemulsion. Electropolymerization required a dual catalytic system, composed of an aqueous phase catalyst and an organic phase catalyst. This allowed shuttling the electrochemical stimulus from the working electrode (WE) to the continuous aqueous phase and to the dispersed monomer droplets. As aqueous phase catalysts, the hydrophilic Cu complexes with the ligands N,N-bis( 2-pyridylmethyl)-2-hydroxyethylamine (BPMEA), 2,2′-bipyridine (bpy), and tris(2-pyridylmethyl)amine (TPMA) were tested. As organic phase catalysts, the hydrophobic complexes with the ligands bis(2-pyridylmethyl)-octadecylamine (BPMODA) and bis[2-(4-methoxy-3,5-dimethyl)-pyridylmethyl]octadecylamine (BPMODA*) were evaluated. Highest rates and best control of BA electropolymerization were obtained with the water-soluble Cu/BPMEA used in combination with the oil-soluble Cu/BPMODA*. The polymerization rate could be further enhanced by changing the potential applied at the WE. Differently from traditional ATRP systems, reactivity of the dual catalytic system did not depend on the redox potential of the catalysts but instead depended on the hydrophobicity and partition coefficient of the aqueous phase catalyst.

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Section: Introductionmentioning

confidence: 99%

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

et al. 2016

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“…While liquid/liquid systems can be expensive to use, catalyst recovery and recycling is possible which gives it an advantage over absorption. Alternatively, the catalyst can be precipitated from solution after polymerization through an additive such as precipitons,18 organic clay19 or even more copper catalyst 20. Finally, solid supported catalyst, a strategy commonly used in the chemical industry, has been explored for ATRP.…”

Section: Conventional Atrpmentioning

confidence: 99%

Reducing ATRP Catalyst Concentration in Batch, Semibatch and Continuous Reactors

Chan

Cunningham

Hutchinson

2010

Macro Reaction Engineering

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An overview of solution ATRPs carried out in batch, semibatch and continuous tubular and stirred‐tank reactor systems is presented. Initial work using a heterogeneous catalyst system with copper to polymer chain ratios of close to unity demonstrated the versatility of ATRP in producing homopolymer and copolymer at reasonable rates with good MW control and narrow polydispersity. The significant drawbacks of low catalyst solubility and high copper levels are now being addressed through use of the ARGET ATRP chemistry. Nearly colorless acrylate and methacrylate polymers have been produced with copper catalyst levels below 50 ppm (relative to monomer), with excellent control of MW obtained both in batch and continuous systems.

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“…It should be noted that variants of ATRP like SET‐LRP and ARGET employ < 50 ppm quantities of Cu catalyst with nearly colorless resins have been shown and in the case of SET‐LRP, monomers used for photoresists were applied. Indeed, metallic catalyst concentration in optoelectronic materials is generally required to be below 1 ppm to avoid unfavorable photochemical effects …”

Section: Introductionmentioning

confidence: 99%

Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

Wang

Wylie

Marić

2016

Macro Reaction Engineering

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ArF candidate photoresist polymers have been synthesized by nitroxide mediated polymerization (NMP). Statistical copolymerizations of α‐gamma butyrolactone methacrylate, 3‐hydroxy‐1‐adamantyl methacrylate, and 2‐methyl 2‐adamantyl methacrylate with 5–10 mol% of controlling comonomers (i.e., styrene, p‐acetoxystyrene, 2‐vinyl naphthalene, acrylonitrile, and pentafluorostyrene), which are necessary for controlled polymerization of methacrylates by NMP with the unimolecular alkoxyamine initiator BlocBuilder, have been used. As little as 5 mol% controlling comonomer in the feed is demonstrated to be sufficient to produce linear evolution of number average molecular weight against conversion (X) up to X = 0.7 for relatively low target degrees of polymerization. All of the resulting copolymers have relatively low dispersities (trueM¯normalw/trueM¯normaln≈1.4) and show relatively low absorbance at 193 nm, comparable to other 193 nm candidate photoresists reported previously, with the exception of VN‐containing copolymer.

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Hydrated Clay for Catalyst Removal in Copper Mediated Atom Transfer Radical Polymerization

Cited by 30 publications

References 34 publications

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

Electrochemical Atom Transfer Radical Polymerization in Miniemulsion with a Dual Catalytic System

Reducing ATRP Catalyst Concentration in Batch, Semibatch and Continuous Reactors

Synthesis of Narrow Molecular Weight Distribution Copolymers for ArF Photoresist Materials by Nitroxide Mediated Polymerization

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