Sequence‐Controlled Multiblock Copolymers via RAFT Polymerization: Modeling and Simulations

Zetterlund, Per B.; Gody, Guillaume; Perrier, Sébastien

doi:10.1002/mats.201300165

Cited by 71 publications

(93 citation statements)

References 51 publications

(80 reference statements)

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“…In this work, we further demonstrate the high versatility and robustness of the RAFT process by increasing reaction temperature to 100 °C, with the effect of shortening reaction times to 3 minutes, and by performing the polymerization in presence of air, keeping monomer conversion over 98% (Scheme 1). 41,42,44 Rapid polymerization is further enabled by the use of acrylamide monomers (i.e. 54 Since the rate of polymerization is directly proportional to the k p of the monomer and the concentration of propagating radicals (R p = k p [M][P • ]), RAFT polymerization can be accelerated by increasing the reaction temperature (and thus the k p of the monomer) and by using a thermal initiator that decomposes very quickly at this temperature, to generate a large amount of radicals, thus raising the concentration of propagating radical ([P • ]).…”

Section: Scheme 1 Strategy For the Preparation Of Multiblock Copolymmentioning

confidence: 99%

Ultrafast RAFT polymerization: multiblock copolymers within minutes

et al. 2015

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The synthesis of multiblock copolymers is often considered as synthetically challenging and time consuming. In this contribution, the development of a remarkably efficient and versatile procedure to access multiblock copolymers via reversible addition-fragmentation chain transfer (RAFT) polymerization is reported. The robustness and versatility of the RAFT process is demonstrated in this report by preparing multiblock copolymers using uncommon experimental conditions. The synthesis of each block was performed in the presence of air and only required 3 minutes to reach >98% monomer conversion. This approach removes the necessity to deoxygenate the solution and permits access to complex copolymer structures in very short time periods. For example, this process allowed the preparation of a heptablock homopolymer with a well-defined architecture in just 21 minutes. We also discuss the limitations inherent to this approach. This strategy is shown to be particularly efficient when blocks with low degrees of polymerization (DP < 20) are targeted. For blocks with higher DPs (DP > 50), the procedure is typically limited to the preparation of di-or triblock copolymers.Functional block copolymers are fascinating architectures with unique properties that render them particularly attractive for applications ranging from medicine, 1,2 materials, 3 energy 4 and nanotechnology. 5,6 The access to such synthetically demanding architectures was greatly facilitated with the advent of controlled/"living" radical polymerization techniques, also known as reversible deactivation radical polymerization (RDRP), 7 such as atom transfer radical polymerization (ATRP), 8,9 nitroxide-mediated radical polymerization (NMP), 10,11 reversible addition-fragmentation chain transfer (RAFT) 12-15 and macromolecular design via interchange of xanthates (MADIX) 16-18 polymerizations. These methods enable the production of well-defined polymeric materials with predetermined molar masses, narrow molar mass distributions, chainend functionality, and they can be coupled with efficient post-polymerization modification strategies (e.g. 'click' chemistry). [19][20][21][22][23][24][25] Despite the relative ease of preparing block copolymers (i.e., di-or triblock copolymers) via RDRP methods in comparison with, for example, ionic living polymerizations, the production of multiblock copolymers still remains a challenging and time consuming task. This is mainly due to the necessity to remove any unreacted monomer before the subsequent block is synthesized, 26-31 as the non-removal of monomer would lead to the synthesis of quasi-block copolymers. 32Additional issues include a decrease in chain-end fidelity with increasing the number of blocks.Recently, Cu(0)-mediated radical polymerization 33-38 and RAFT polymerization 39-44 have demonstrated great potential to produce well-defined, multiblock architectures, in particular by reaching full monomer conversion, thus avoiding tedious, intermediate purification steps.

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Section: Scheme 1 Strategy For the Preparation Of Multiblock Copolymmentioning

confidence: 99%

Ultrafast RAFT polymerization: multiblock copolymers within minutes

et al. 2015

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“…Among these techniques, reversible-addition fragmentation chain transfer (RAFT) polymerization is attractive because it has the advantage of being compatible with a wide range of monomers 9 , notably including acidic monomers, and it can be performed in an extensive range of solvents and under a broad range of conditions. In addition, recent work has highlighted the potential of RAFT polymerization for the synthesis of multiblock copolymers due to the high living fraction of polymer chains that can be obtained by exploiting the degenerative transfer mechanism of the polymerization 10,11 . In RAFT polymerization, thiocarbonylthio compounds with generic formula R-S-(C=S)-Z (referred to as RAFT agents) are employed as highly active chain transfer agents which allow for growth of all chains throughout the polymerization.…”

Section: Introductionmentioning

confidence: 99%

Determining the effect of side reactions on product distributions in RAFT polymerization by MALDI-TOF MS

et al. 2015

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Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization has emerged as one of the most versatile reversible deactivation radical polymerization techniques and is capable of polymerizing a wide range of monomers under various conditions. One of the most important factors governing the success of a RAFT polymerization is the fraction of living chains at the end of the reaction, which can be maximized by using a low amount of initiator. From the point of view of the process, it is tempting to perform the polymerization in solution, which allows a better mixing. However, in this work it is shown that this choice may be negative for the quality of the polymer. Detailed analysis using Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectrometry (MALDI-TOF MS) of poly(nbutyl acrylate) (pBA) obtained at high conversion in the RAFT solution polymerization revealed that in addition to the polymer chains, formed by the RAFT mechanism, there were two distinct populations resulting from chain transfer to solvent and transfer to polymer followed by β-scission. Complementary results from Size Exclusion Chromatography coupled with Multi Angle Light Scattering detector (SEC/MALS), quantum chemical calculations, and a mathematical model that predicts product distributions, were also used to further confirm the assigned structures. The results highlight the scope and limitation on the living fraction of chains due to chain transfer events using RAFT polymerization and reversible deactivation radical polymerizations in general, and furthermore, yielded information about the fate of midchain radicals formed by intramolecular transfer to polymer.

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“…Thus, under comparable conditions (rate, MW, conversion), chain end functionality is best preserved in polymerization of acrylates or acrylamides (highest k p /k t ), in polar and viscous media, at higher temperature and also in confined media (32). This research direction is among the most rapidly developing in CRP (33)(34)(35).…”

Section: Introductionmentioning

confidence: 93%

Controlled Radical Polymerization: State-of-the-Art in 2014

Matyjaszewski

2015

ACS Symposium Series

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Sequence‐Controlled Multiblock Copolymers via RAFT Polymerization: Modeling and Simulations

Cited by 71 publications

References 51 publications

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Determining the effect of side reactions on product distributions in RAFT polymerization by MALDI-TOF MS

Controlled Radical Polymerization: State-of-the-Art in 2014

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