Predicting the Limit of Control in the ATRP Process: Results from Kinetic Simulations

Bergenudd, Helena; Jönsson, Mats; Malmström, Eva

doi:10.1002/mats.201100031

Cited by 11 publications

(8 citation statements)

References 50 publications

(65 reference statements)

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“…It was as if the substrate 6 and its product 6a were incompatible with the catalytic system. ATRP has already come across situations of this type 14d,30. When this occurs, less active systems have to be used.…”

Section: Resultsmentioning

confidence: 99%

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

et al. 2013

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The cyclisation of N-allyl-N-substituteda-\ud polychloroamides is efficiently obtained through\ud a copper-catalysed activators regenerated by electron\ud transfer–atom transfer radical cyclisation process,\ud with a metal load of only 0.5 mol%. The redox\ud catalyst is introduced in its inactive form as copper(\ud II) chloride/[nitrogen ligand] complex, and continuously\ud regenerated to the active copper(I) chloride/[\ud nitrogen ligand] species by ascorbic acid. To\ud preserve the catalyst integrity, the hydrochloric\ud acid, released after each regeneration cycle, has\ud been quenched by carbonate. The choice of the solvent\ud is critical, the best performance being observed\ud in ethyl acetate-ethanol (3:1)

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Section: Resultsmentioning

confidence: 99%

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

et al. 2013

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“…where k p is the propagation rate constant, and C M and C RX are monomer and initiator concentrations. Therefore, information on kact values is important for choosing the optimal experimental conditions [9], e.g. for selecting the best catalyst/initiator couple in a specific polymerization system.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical approaches to the determination of rate constants for the activation step in atom transfer radical polymerization

Fantin

Isse

Bortolamei

et al. 2016

Electrochimica Acta

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Direct determination of ATRP activation rate constant, kact, is typically limited to slow or moderately fast reactions: kact< 102 mol1dm3 s1 were determined by classical techniques, such as chromatography, spectrophotometry, NMR, etc. Therefore, these techniques are inadequate to study the fastest, and most useful, ATRP systems, such as the most frequently used Cu complexes with tris[2-(dimethylamino)ethyl] amine (Me6TREN), tris(2-pyridylmethyl)amine (TPMA) and substituted TPMA. In this study, electrochemical methods have been used to investigate the kinetics of activation of a series of typical ATRP initiators (RX) by [CuIL]+ (L = Me6TREN, TPMA or N,N,N0,N00,N0 0-pentamethyldiethylenetriamine, (PMDETA) in MeCN. Both high (>104 mol1dm3 s1) and low kact values have been measured. Analysis of the collected data showed that kact depends on E of the catalyst, molecular structure of RX, and nature of the halogen atom. Although usually values of kact increase with decreasing standard reduction potential of [CuIIL]2+, there is no well-defined correlation between the two parameters. Instead, kact gives good and\ud useful linear correlations with the standard reduction potential of [XCuIIL]+, and with KATRP or Gibbs free energy of C-X bond dissociation

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“…The polymer MWD can be better understood and controlled by using mathematical models that describe its evolution during the synthesis reaction. Previous mathematical modeling of ATRP has been done by a number of research groups, but most of that research focused on previous versions of ATRP, especially early works trying to better understand the kinetics and mechanism of these processes. In contrast, a few have been done on the modeling of ICAR and ARGET systems, which have greater industrial potential.…”

Section: Introductionmentioning

confidence: 99%

Mathematical modeling of the full molecular weight distribution in ATRP techniques

et al. 2016

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In this work the molecular weight distribution (MWD) of several atom transfer radical polymerization (ATRP) techniques has been derived and solved using the Reduced Stiffness by Quasi Steady State Approximation (RSQSSA) methodology. The Quasi Steady State Approximation has been validated on the living radicals for normal, Simultaneous Reversible and Normal Initiation and Activators Regenerated by Electron Transfer (ARGET), and it is shown that the information lost due to its application is negligible. According to these results, RSQSSA shows the best performance in terms of wall-clock time and required memory in comparison to implicit techniques and Predici. In the case of the ARGET technique, the model predictions show good agreement with experimental data. Finally, an analysis on the impact of the slow and fast activation of the initiator on the MWD using ARGET has been carried out, indicating that the optimal initiator to control the MWD should exhibit activation-deactivation rates very similar to those of the polymeric equilibrium.

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Predicting the Limit of Control in the ATRP Process: Results from Kinetic Simulations

Cited by 11 publications

References 50 publications

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

Efficient and Green Route to γ‐Lactams by Copper‐Catalysed Reversed Atom Transfer Radical Cyclisation of α‐Polychloro‐N‐allylamides, using a Low Load of Metal (0.5 mol%)

Electrochemical approaches to the determination of rate constants for the activation step in atom transfer radical polymerization

Mathematical modeling of the full molecular weight distribution in ATRP techniques

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