From one-pot stabilisation to in situ functionalisation in nitroxide mediated polymerisation: an efficient extension towards atom transfer radical polymerisation

Petton, Lionel; Ciolino, Andrés Eduardo; Dervaux, Bart; Prez, Filip Du

doi:10.1039/c2py00444e

Cited by 20 publications

(15 citation statements)

References 65 publications

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“…This could potentially enable faster polymerization of a broader range of monomers, under milder conditions and correspondingly diminish the occurrence of the undesired side-reactions that occur at high temperatures. Moreover, the polymer chains so formed will be capped with a pH-sensitive nitroxide, potentially useful for postfunctionalization 26 via nitroxide radical coupling (NRC) 27 or binding to various bioactive substrates. 28 To date our experimental studies have focussed on the performance of the commercially available reagent 4-carboxy-TEMPO.…”

Section: Introductionmentioning

confidence: 99%

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Gryn’ova

Smith

Coote

2017

Phys. Chem. Chem. Phys.

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In the present work we use accurate quantum chemistry to evaluate several known and novel nitroxides bearing acid-base groups as pH-switchable control agents for room temperature NMP. Based on G3(MP2,CC)(+)//M06-2X/6-31+G(d) calculations with UAKS-CPCM/M06-2X/6-31+G(d) solvation corrections, a number of novel nitroxides are predicted to be suitable for controlled polymerization of bulk styrene at room temperature when deprotonated (i.e. negatively charged), while remaining inert when neutral. These include an α-ethyl analogue of 3-carboxy-PROXYL and novel derivatives of 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) that have been modified to include acidic groups. Among the other species evaluated, 3,4-dicarboxy-PROXYL, α-carboxylated PROXYL and the phosphoric acid derivative of N-(2-methylpropyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (SG1) are predicted to undergo suitable pH-switching at around 60 °C, and may also be fitting for some applications.

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Section: Introductionmentioning

confidence: 99%

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Gryn’ova

Smith

Coote

2017

Phys. Chem. Chem. Phys.

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“…). The bromide end‐group of an ATRP polymer can, therefore, be converted into a chain‐end suitable for NMP (halide to alkoxyamine) or RAFT (halide to thiocarbonate), and conversely, the alkoxyamine chain‐ends that remains after NMP can be converted to ATRP and RAFT macroinitiators. Interestingly, while it is possible to prepare a NMP macroinitiator from a RAFT polymer chain‐end, the conversion of a RAFT polymer chain‐end to a bromide, suitable for ATRP or direct nucleophilic substitution, to the best of our knowledge has not been shown.…”

Section: Discussionmentioning

confidence: 99%

Established and emerging strategies for polymer chain‐end modification

Lunn

Discekici

Alaniz

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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The development of "controlled" and "living" polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chainend functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods.

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“…The polymer containing ATRP initiator was used to prepare PS‐ b ‐PMMA block copolymer by ATRP. Furthermore, the versatility of SG1 chain‐end modification was expanded for the synthesis of PMMA‐Br, PBA‐Br, and PS‐Br using CBr 4 instead of EBiB and the chain extensions by ATRP were successfully achieved …”

Section: Transformations From Nmpmentioning

confidence: 99%

Polymer Synthesis with More Than One Form of Living Polymerization Method

Guo

Choi

Feng

et al. 2018

Macromol. Rapid Commun.

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Controlled radical polymerization (CRP) or controlled/living radical polymerization has revolutionized the polymer industry as a tool for the preparation of a wide variety of polymers. This process enables the preparation of polymers with good control of molecular weight, narrow polydispersity, and a range of architectures including block and graft copolymers, star polymers, and other functional polymers. The mechanistic transformation reaction provides a great opportunity to tune chemical and physical properties of copolymers. It can be applied to combine different homopolymers using post‐modification techniques or by the use of a dual initiator, allowing the combination of mechanistically distinct polymerization reactions. This review will cover CRP transformations including the synthesis of block copolymers with both linear structures (AB, ABA, (AB) n , multiblocks, etc.) and branched macromolecular architectures (graft, miktoarm star, and dendritic‐like), which are obtained by a combination of more than one form of living polymerization reaction.

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From one-pot stabilisation to in situ functionalisation in nitroxide mediated polymerisation: an efficient extension towards atom transfer radical polymerisation

Cited by 20 publications

References 65 publications

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Computational design of pH-switchable control agents for nitroxide mediated polymerization

Established and emerging strategies for polymer chain‐end modification

Polymer Synthesis with More Than One Form of Living Polymerization Method

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