Compartmentalization Effects on Bimolecular Termination in Atom Transfer Radical Polymerization in Nanoreactors

Zetterlund, Per B.

doi:10.1002/mats.201100025

Cited by 16 publications

(9 citation statements)

References 47 publications

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“…As outlined above, in both NMP and ATRP, the kinetic effect of compartmentalization is typically manifested as the segregation effect on termination and the confined space effect on deactivation. From the perspective of rationalizing such effects, NMP and ATRP can be treated under a single umbrella given that both are based on the persistent radical effect. , The same kinetic treatment applies to both NMP ,,,,− and ATRP ,− if one simply replaces “ k act ” in NMP by “ k act [Cu(I)]” (illustrated with Cu(I) as the activating complex in ATRP). In what follows, compartmentalization effects are first explained within the framework of miniemulsion NMP with possible thermal self-initiation ( k i,th ; styrene (St) case (L 2 mol –2 s –1 )) and ignoring exit/entry events.…”

Section: Compartmentalization In Nmp and Atrpmentioning

confidence: 99%

The Nanoreactor Concept: Kinetic Features of Compartmentalization in Dispersed Phase Polymerization

Zetterlund

D’hooge

2019

Macromolecules

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Compartmentalization refers to the physical confinement of reactants within confined space of nanosize dimensions and is a concept exploited by nature for the synthesis of various biomolecules. In the field of synthetic polymer chemistry, compartmentalization mainly refers to the “segregation effect” with two species located in different nanoparticles being unable to react and the “confined space effect” with two species in the same particle reacting faster for a smaller nanoparticle size. Compartmentalization kinetic effects on conventional radical (emulsion) polymerization kinetics have been relatively well understood for some time, whereas the influence in reversible deactivation radical polymerization (RDRP) is considerably more complex and remains an active area of research. This Perspective provides a concise overview of compartmentalization kinetic effects at sufficiently low particle sizes (e.g., below 100 nm) on conventional radical polymerization, RDRP, cross-linking polymerization, and nonradical polymerization reactions. It is demonstrated that the phenomenon of compartmentalization can be exploited as a means of exerting influence on the polymerization kinetics without manipulating the fundamental chemistry of the polymerization, provided that sufficient attention is paid to interphase exit and entry mass transfer events.

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Section: Compartmentalization In Nmp and Atrpmentioning

confidence: 99%

The Nanoreactor Concept: Kinetic Features of Compartmentalization in Dispersed Phase Polymerization

Zetterlund

D’hooge

2019

Macromolecules

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“…has explored the use of bifunctional initiators and its implications in the synthesis of triblock copolymers . Other works have investigated the effects of compartmentalization on kinetics and control in disperse systems containing nanometric particles as reaction sites (e.g., miniemulsion and microemulsion ATRP polymerizations) . D'hooge et al have reported an interesting methodology to study normal ATRP, based on an extension of the moments method, using the Quasi Steady State Approximation (QSSA) for the active polymer chains and computing the diffusional limitations by using the average apparent rate constants .…”

Section: Introductionmentioning

confidence: 99%

“…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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“…During the last decades, the design of well-tailored polymers molecules with predetermined number average chain length, high end-group functionality (EGF), controlled topology and low dispersity has been the topic of many research activities [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. These advanced macromolecular architectures are typically acquired via controlled radical polymerization (CRP), which is also known as reversible deactivation radical polymerization (RDRP).…”

Section: Introductionmentioning

confidence: 99%

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

et al. 2014

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Based on kinetic Monte Carlo simulations of the monomer sequences of a representative number of copolymer chains (≈ 150,000), optimal synthesis procedures for linear gradient copolymers are proposed, using bulk Initiators for Continuous Activator Regeneration Atom Transfer Radical Polymerization (ICAR ATRP). Methyl methacrylate and n-butyl acrylate are considered as comonomers with CuBr 2 /PMDETA (N,N,N′,N′′,N′′-pentamethyldiethylenetriamine) as deactivator at 80 °C. The linear gradient quality is determined in silico using the recently introduced gradient deviation () polymer property. Careful selection or fed-batch addition of the conventional radical initiator I 2 allows a reduction of the polymerization time with ca. a factor 2 compared to the corresponding batch case, while preserving control over polymer properties ( ≈ 0.30; dispersity ≈ 1.1) . Fed-batch addition of not only I 2 , but also comonomer and deactivator (50 ppm) under starved conditions yields a below 0.25 and, hence, an excellent linear gradient quality for the dormant polymer molecules, albeit at the expense of an increase of the overall polymerization time. The excellent control is confirmed by the visualization of the monomer sequences of ca. 1000 copolymer chains.

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Compartmentalization Effects on Bimolecular Termination in Atom Transfer Radical Polymerization in Nanoreactors

Cited by 16 publications

References 47 publications

The Nanoreactor Concept: Kinetic Features of Compartmentalization in Dispersed Phase Polymerization

The Nanoreactor Concept: Kinetic Features of Compartmentalization in Dispersed Phase Polymerization

Mathematical modeling of the full molecular weight distribution in ATRP techniques

Fed-Batch Control and Visualization of Monomer Sequences of Individual ICAR ATRP Gradient Copolymer Chains

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