New Variants of Nitroxide Mediated Polymerization

Audran, Gérard; Bagryanskaya, Elena G.; Marque, Sylvain R. A.; Postnikov, Pavel

doi:10.3390/polym12071481

Cited by 32 publications

(21 citation statements)

References 104 publications

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“…As shown in Figure 1, the core reaction of NMP involves a reversible homolytic cleavage of alkoxyamine, generating a propagating alkoxy radical (P • ) and a stable nitroxide radical (X • ). 40,41 Four essential steps with associated rate coefficients, (1) the dissociation of alkoxyamine, (2) the combination of alkyl radical and nitroxide, (3) propagation, and (4) bimolecular termination, as listed in Table 1, are widely acknowledged to describe an NMP system. 42 The kinetics of NMP initiated by a mono-molecular initiator system are described as two typical cases.…”

Section: Theoretical Fundamentals and Methodsmentioning

confidence: 99%

“Living” Polymer Dispersity Quantification for Nitroxide-Mediated Polymerization Systems by Mimicking a Monodispersed Polymer Blending Strategy

Wang

Luo

et al. 2020

Macromolecules

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The quantification of dispersity is an indispensable part of characterizing polymers. In this work, general dispersity equations for “living” polymers obtained by nitroxide-mediated polymerization (NMP), reflecting the contribution of dead polymeric chains to the overall dispersity, are presented. Derivation of new dispersity equations is inspired by the monodispersed polymer blending strategy, which is confirmed by experimental data in accordance with a Gaussian distribution. The accuracy and applicability of the newly derived equations are validated by comparative studies with those by the conventional equations through an in silico simulation benchmark and experimental data gathered from literature studies. Moreover, the dissociation and combination reaction rate coefficients are also successfully estimated by the combination of kinetic and as-developed dispersity equations under actual polymerization conditions. The new dispersity equations can be used as dispersity modulation tools in combination with the Gaussian distribution function and can also be effective tools beyond the experimentation to predict accurate dispersity for living polymers and to estimate rate coefficients.

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Section: Theoretical Fundamentals and Methodsmentioning

confidence: 99%

“Living” Polymer Dispersity Quantification for Nitroxide-Mediated Polymerization Systems by Mimicking a Monodispersed Polymer Blending Strategy

Wang

Luo

et al. 2020

Macromolecules

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“…It provides a new way to activate chemical transformations, which can be used for instance in surface‐assisted polymerization at ambient temperature. [ 100 ] The group of Baumberg presented an example of employing plasmon energy for polymerization in 2018. [ 94 ] Polymer brushes were grown via plasmon‐induced polymerization with nanoscale precision.…”

Section: Cans Based On Dynamic Alkoxyamine Bondsmentioning

confidence: 99%

Covalent Adaptable Networks Based on Dynamic Alkoxyamine Bonds

Jia

Delaittre

Tsotsalas

2022

Macro Materials & Eng

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Covalent adaptable networks (CANs) introduce a new paradigm to polymer science, by making static network polymers dynamic and thereby recyclable, reprocessable, and self‐healing. The critical feature in CANs is the presence of dynamic covalent linkages within the network structure. A variety of such linkages are introduced into CANs, making the respective networks responsive to various stimuli, such as light, temperature, or pH. Here, CANs based on alkoxyamines as dynamic covalent bonds are reviewed. Alkoxyamines uniquely combine the ability to dynamically form, break, and reform covalent bonds with the possibility to initiate reversible‐deactivation radical polymerization. Polymer networks based on alkoxyamines are therefore both adaptive and quasi‐living, able to remodel the network structure by nitroxide‐exchange reactions (NER) and extend the network structure by nitroxide‐mediated polymerization (NMP). In this review, the concepts behind CANs are first introduced and the properties of nitroxides and derived alkoxyamines are discussed. A special focus is set on the ability to tune the response of alkoxyamines to different stimuli, through alteration of their structure. In addition, possible side reactions during dynamic bond exchange and limitations for polymerization are critically reviewed. Subsequently, examples of alkoxyamine‐based CANs responsive to different stimuli, such as temperature, light, or chemical triggers, are discussed. Properties and applications of CANs based on alkoxyamines are then discussed. Finally, an outlook is provided on challenges that need to be addressed as well as opportunities that lie within these “living” CANs.

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“…It suffers from several limitations, due to the high temperatures that may be required to reactivate the radical dormant species, especially when it is unconjugated. Still, these limitations have been dealt with through several variants of NMP 63,64 . Furthermore, when seeking block copolymer synthesis, nitroxide chain end can be exchanged with a halogen atom for ATRP chain elongation or with a dithiobenzoate to form a RAFT macro‐chain transfer agent (CTA) (Scheme 3).…”

Section: Background: Matching Building Block Studs For Specific Compositions Architectures and Functionsmentioning

confidence: 99%

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

D’Acunzo

Masci

2021

Journal of Polymer Science

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In this review article, we survey the 2016–June 2021 scientific literature on the synthesis of multi‐stimuli responsive (MSR) polymers, the main focus being on reversible deactivation radical polymerization techniques (RDRPs, also known as controlled radical polymerizations). In fact, along more than 40 years of extensive research, RDRPs have boosted the synthesis of stimuli‐responsive polymers. RDRPs are now robust, versatile, relatively user‐friendly and even interconvertible, thus allowing control over composition, sequence, and topology of polymers. Such control can afford materials with well‐defined responses to physical, chemical, and biological external stimuli. Furthermore, “click” reactions are used to combine macromolecular precursors or to introduce specific functional groups in the target structure. As a result, MSR polymers are obtained from diverse combinations of commercial or specially synthesized building blocks arranged at will into desired sequences and architectures. Thanks to this versatility, self‐assembling polymeric structures are designed either to respond to triggers and perform specific applicative tasks, or to investigate the influence of structural variables on the responsivity of polymers. The “green” trend emerging in the field of responsive polymers and RDRPs is also briefly discussed.

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New Variants of Nitroxide Mediated Polymerization

Cited by 32 publications

References 104 publications

“Living” Polymer Dispersity Quantification for Nitroxide-Mediated Polymerization Systems by Mimicking a Monodispersed Polymer Blending Strategy

“Living” Polymer Dispersity Quantification for Nitroxide-Mediated Polymerization Systems by Mimicking a Monodispersed Polymer Blending Strategy

Covalent Adaptable Networks Based on Dynamic Alkoxyamine Bonds

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

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