Temperature Effect on Activation Rate Constants in ATRP: New Mechanistic Insights into the Activation Process

Seeliger, Florian; Matyjaszewski, Krzysztof

doi:10.1021/ma101043n

Cited by 16 publications

(29 citation statements)

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“…chapter 13.2) as well as ATRP equilibrium constants (K ATRP , cf. chapter 13.1) also increase with temperature, [394,396] backbiting, cf. chapter 13.10), whereas styrene tends to self-initiate polymerization, [451,452] and methacrylates can depropagate.…”

Section: Effect Of Temperaturementioning

confidence: 96%

“…[154,213,392] It is worthwhile noting that rate coefficients of alkyl halide activation by Cu I /L are often expressed as apparent rate coefficients, without consideration of speciation. The effect of solvent, [306,391,394,402,403] temperature, [396] monomer, [402] counterion, [402][403][404] Cu II /L concentration, [393] penultimate unit, [405] and [ligand]/[Cu I ] ratio [394,402,403] were meticulously evaluated. The values typically range from as low as 10 -5 M -1 s -1 up to 10 5 M -1 s -1 .…”

Section: Activation (K Act )mentioning

confidence: 99%

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Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

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213

142

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This review encompasses the fundamentals of kinetics of atom transfer radical polymerization (ATRP). ATRP is a versatile reversible-deactivation radical polymerization (RDRP) technique, frequently utilized to synthesize advanced functional materials. Detailed mechanistic investigations over the past two decades allowed for an in-depth understanding of the underlying processes and rational design of the reaction conditions. Various aspects of ATRP kinetics are reviewed such as initiation modes, methods allowing to decrease catalyst concentration, influence of the initiator, catalyst (transition metal, ligand, counterion), solvent, additives, type of monomer, and effect of temperature and pressure. Techniques utilized to determine kinetic parameters of catalytic systems are discussed. Finally, guidelines for synthesis of polymers with targeted architectures, predetermined molecular weights, narrow molecular weight distributions, and high retained chain end functionality are presented.

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Section: Effect Of Temperaturementioning

confidence: 96%

Section: Activation (K Act )mentioning

confidence: 99%

Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

Self Cite

213

142

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“…1 L mol −1 s −1 can be identified in Figure in order to achieve a good microstructural control, i.e., a good control over dispersity and EGF, while still maintaining a reasonable polymerization rate. Therefore, a tertiary R 0 X (yellow spheres) such as methyl 2‐bromoisobutyrate is put forward in the present work to be most suited (

k_{a 0}^{c h e m}

= 4.1 × 10 2 L mol −1 s −1 ) . In contrast, a secondary R 0 X (white crosses in Figures a, b;

k_{a 0}^{c h e m}

= 3.0 × 10 −1 L mol −1 s −1 ) 64 leads to too high dispersities (>1.6) despite that the polymerization time is significantly reduced (<8 h).…”

Section: Resultsmentioning

confidence: 93%

“…Moreover, the temperature dependency of the reactivity ratios is rarely taken into account and often values are employed which have been obtained at a different temperature than the actual polymerization temperature considered in the kinetic modeling study. In general, it can be expected that this is a too strong simplification, in particular for reactions with a wide range of activation energies …”

Section: Introductionmentioning

confidence: 99%

“…In a first stage, grid simulations are performed at 363 K to identify a suited ICAR ATRP initiation system to ensure a sufficiently high batch polymerization rate and control over the polymer properties with an acceptable Cu ppm level. These simulations involve the consideration of several ATRP initiators ( R 0 X ) with reported ATRP activation rate coefficients (

k_{a 0}^{c h e m}

) ranging from 3.0 × 10 −1 to 4.1 × 10 2 L mol −1 s −1 and several conventional radical initiators ( I 2 ) for which the reported dissociation rate coefficient (

k_{d i s}^{c h e m}

) varies between 6.3 × 10 −6 and 2.5× 10 −4 s −1 . For simplicity the corresponding deactivation rate coefficients (

k_{d a 0}^{c h e m}

) are not altered, as preliminary simulations showed that this parameter is kinetically less significant (see Supporting Information).…”

Section: Introductionmentioning

confidence: 99%

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How penultimate monomer unit effects and initiator influence ICAR ATRP of n‐butyl acrylate and methyl methacrylate

et al. 2017

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The relevance of penultimate monomer unit (PMU) effects and the selection of the correct initiator species under typical reversible deactivation radical copolymerization conditions is illustrated, using matrix‐based kinetic Monte Carlo simulations allowing the visualization of all monomer sequences along individual chains. Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) is selected as illustrative polymerization technique with n‐butyl acrylate and methyl methacrylate as comonomers, aiming at the synthesis of well‐defined gradient copolymers. Using literature based model parameters, in particular temperature dependent monomer and radical reactivity ratios, it is demonstrated that PMU effects on propagation and ATRP (de)activation cannot be ignored to identify the most suited ICAR ATRP reactants (e.g., tertiary ATRP initiator) and reaction conditions (e.g., feeding rates under fed‐batch conditions). The formulated insights highlight the need for further research on PMU effects on all reaction steps in radical polymerization. © 2017 American Institute of Chemical Engineers AIChE J, 2017

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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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Temperature Effect on Activation Rate Constants in ATRP: New Mechanistic Insights into the Activation Process

Cited by 16 publications

References 0 publications

Kinetics of Atom Transfer Radical Polymerization

Kinetics of Atom Transfer Radical Polymerization

How penultimate monomer unit effects and initiator influence ICAR ATRP of n‐butyl acrylate and methyl methacrylate

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

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