Exploitation of the Degenerative Transfer Mechanism in RAFT Polymerization for Synthesis of Polymer of High Livingness at Full Monomer Conversion

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

doi:10.1021/ma402286e

Cited by 144 publications

(226 citation statements)

References 45 publications

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“…Since a decrease in the block DP leads to a higher fraction of living chains per cycle, 43 we initially targeted a high number of blocks (i.e., 7), each block with a low relative degree of polymerization (DP = 10), [PNAM 10 ] 7 (Scheme 3, multiblock a, Table 1 and Table S1). Since a decrease in the block DP leads to a higher fraction of living chains per cycle, 43 we initially targeted a high number of blocks (i.e., 7), each block with a low relative degree of polymerization (DP = 10), [PNAM 10 ] 7 (Scheme 3, multiblock a, Table 1 and Table S1).…”

Section: Effect Of Number Of Cyclesmentioning

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: Effect Of Number Of Cyclesmentioning

confidence: 99%

Ultrafast RAFT polymerization: multiblock copolymers within minutes

et al. 2015

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“…45 The dead chain fraction was very low. We noticed that the monomer employed was acrylamide, which has very high propagation rate constants (k p ).…”

Section: Introductionmentioning

confidence: 98%

Tailor-made compositional gradient copolymer by a many-shot RAFT emulsion polymerization method

et al. 2014

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A many-shot RAFT emulsion polymerization method is proposed to synthesize gradient copolymers with high molecular weight and a tailor-made compositional gradient. In this method each shot consisting of comonomers with pre-set different fractions and targeting the molecular weight of 10 000 g mol À1 was added in a stepwise manner during the reaction. High conversions over 95% were achieved in 35 min after each shot. The compositional variation along the polymer chain was then directly determined by the comonomer fractions added at each shot. Styrene/n-butyl acrylate gradient copolymers (including linear and V-shaped gradient) with molecular weights as high as 90 000 g mol À1 were prepared by this method. The composition profiles along the polymer chains agreed well with the theoretical predictions, and the composition distribution among the polymer chains was narrow. The gradient copolymers showed different thermal and phase separation properties from their block counterparts, as expected.These results demonstrated the successful tailor-making of the gradient copolymers. The current strategy will act as a facile method to prepare tailor-made gradient copolymers with high molecular weights and within a short time.

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“…These side reactions include hydrolysis of the monomer to form ammonia, which causes unwanted aminolysis of the CTAs, slow polymerisation rate and poor monomer conversion (< 28%). [35][36][37] Aiming to minimise such side reactions, we opted for a trithiocarbonate CTA, PABTC, to mediate the polymerization, as it has better hydrolytic stability even at temperatures as high as 70 °C, 24 and the polymerisations were undertaken in 40% in volume dioxane, in order to limit AAm hydrolysis. Furthermore, dioxane also facilitates the solubilisation of both PABTC and styrene monomer at the chain extension Conversion and DP of styrene were determined from 1 H-NMR in situ ( Figure S4).…”

Section: Ultraviolet-visible (Uv-mentioning

confidence: 99%

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

et al. 2016

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Permanent WRAP URL:http://wrap.warwick.ac.uk/83846 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Biomacromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher.To access the final edited and published work see http://dx.doi.org/10.1021/acs.biomac.5b01633 A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. AbstractWe present the preparation of 11 nm polyacrylamide-stabilised polystyrene latex particles for conjugation to a microRNA model by surfactant-free RAFT emulsion polymerisation. Our synthetic strategy involved the preparation of amphiphilic polyacrylamide-block-polystyrene copolymers, which were able to self-assemble into polymeric micelles and 'grow' into polystyrene latex particles. The surface of these sterically stabilised particles was postmodified with a disulfide-bearing linker for the attachment of the microRNA model, which can be released from the latex particles under reducing conditions. These nanoparticles offer the advantage of ease of preparation via a scaleable process, and the versatility of their synthesis makes them adaptable to a range of applications.

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Exploitation of the Degenerative Transfer Mechanism in RAFT Polymerization for Synthesis of Polymer of High Livingness at Full Monomer Conversion

Cited by 144 publications

References 45 publications

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Ultrafast RAFT polymerization: multiblock copolymers within minutes

Tailor-made compositional gradient copolymer by a many-shot RAFT emulsion polymerization method

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

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