Exploitation of the Nanoreactor Concept for Efficient Synthesis of Multiblock Copolymers via MacroRAFT-Mediated Emulsion Polymerization

Clothier, Glenn K. K.; Guimarães, Thiago R.; Khan, Murtaza; Moad, Graeme; Perrier, Sébastien; Zetterlund, Per B.

doi:10.1021/acsmacrolett.9b00534

Cited by 75 publications

(101 citation statements)

References 40 publications

(67 reference statements)

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“…50 More recently, Zetterlund and co-workers employed sulfur RAFT emulsion polymerization to also produce methacrylic multiblock copolymers in a controlled fashion. 51 A critical work in the area was published by Harrisson and co-workers who showed that the statistical nature of CRP may limit the control possible in sequence-controlled multiblocks. In particular, his study concluded that for lower DP multiblocks (<6 units per block), defective chains dominate and thus the purity of the materials is compromised.…”

Section: Sequence-controlled Multiblock Copolymersmentioning

confidence: 99%

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Parkatzidis

Wang

Truong

et al. 2020

Chem

376

304

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This perspective summarizes the latest exciting developments in controlled radical polymerization during the last decade (2010)(2011)(2012)(2013)(2014)(2015)(2016)(2017)(2018)(2019)(2020). Our focus is to critically highlight strengths and weaknesses of recent achievements and portray how these discoveries have expanded the scope of tailor-made polymeric materials. Our perspective on remaining future challenges and where we expect the field to grow toward in the next decade will also be discussed.100 years have passed since the landmark publication by Hermann Staudinger in 1920, after which the field of polymer chemistry was founded. One major revolution in the field has been controlled radical polymerization (CRP), also referred to as reversibledeactivation radical polymerization (RDRP), as it grants users the ability to regulate molecular weight, dispersity (Ð), composition, architecture, and end-group fidelity of vinyl polymers. Currently, numerous CRP techniques are available, most famously atom transfer radical polymerization (ATRP), 1 nitroxide-mediated polymerization (NMP), 2 and reversible addition-fragmentation chain-transfer (RAFT) polymerization. 3 Importantly, polymers synthesized by CRP find use as emulsifiers, dispersants, electrolytes, rheology, and surface modifiers and are applied in commercial products related to home care, beauty, health, paint, energy, and electronics. 4 The focus of this perspective is to acknowledge and critically review recent developments in the area of CRP (decade 2010-2020) (Figure 1). The order in which the developments are presented is not associated to their significance or date of their original report. USING LIGHT AS AN EXTERNAL STIMULUSAmong various stimuli, light is perhaps the most attractive due to its abundance, wide availability, mild nature, low cost, and environmental benignity while it offers tremendous possibilities for temporal and spatial control. In addition, light-mediated polymerizations might offer additional opportunities as they do not require high temperatures, which may facilitate side reactions and/or depolymerization. At the same time, however, light-mediated polymerizations suffer from limited depth penetration and scalability issues, although these have been considerably addressed through the development of flow photochemistry, which allows for faster polymerizations, enhanced control over the molecular weight distributions, and the possibility to be combined with on-orin-line monitoring characterization techniques (the reader is referred to a recent review in flow chemistry polymerization). 5 Furthermore, certain wavelengths and intensities may be disadvantageous for various biological systems. Currently, there are two main developments in this area, namely photo-ATRP (including metal-mediated and metal-free ATRP) and photoinduced electron transferThe Bigger Picture Challenges and opportunities:Universal catalysts compatible with a range of monomers and stimuli are urgently required to produce materials with enhanced control over monomer seq...

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Section: Sequence-controlled Multiblock Copolymersmentioning

confidence: 99%

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Parkatzidis

Wang

Truong

et al. 2020

Chem

376

304

View full text Add to dashboard Cite

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“…We decided to use a so-called 'surfactant-free system' [28][29][30][31][32][33] that in our case comprised an amphiphilic poly(N,N-dimethyl acrylamide)-block-poly(butyl acrylate) (PDMAm-b-PBA, 2; refer to Scheme 2) macroRAFT agent. This non-ionic macroRAFT agent was chosen so as to be unlikely to be electrochemically active under the polymerization conditions (a hypothesis confirmed in the present experiments).…”

Section: Raft Free From Exogenous Initiatorsmentioning

confidence: 99%

Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers

Bray

Postma

et al. 2021

Aust. J. Chem.

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We report on two important advances in radical polymerization with reversible addition–fragmentation chain transfer (RAFT polymerization). (1) Electrochemically initiated emulsion RAFT (eRAFT) polymerization provides rapid polymerization of styrene at ambient temperature. The electrolytes and mediators required for eRAFT are located in the aqueous continuous phase separate from the low-molar-mass-dispersity macroRAFT agent mediator and product in the dispersed phase. Use of a poly(N,N-dimethylacrylamide)-block-poly(butyl acrylate) amphiphilic macroRAFT agent composition means that no added surfactant is required for colloidal stability. (2) Direct photoinitiated (visible light) RAFT polymerization provides an effective route to high-purity, low-molar-mass-dispersity, side chain liquid-crystalline polymers (specifically, poly(4-biphenyl acrylate)) at high monomer conversion. Photoinitiation gives a product free from low-molar-mass initiator-derived by-products and with minimal termination. The process is compared with thermal dialkyldiazene initiation in various solvents. Numerical simulation was found to be an important tool in discriminating between the processes and in selecting optimal polymerization conditions.

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“…This batch process without any intermediate purification steps performed in environmentally friendly solvent (water), would be very attractive to the industry. [ 201 ] Later the same authors also showed that this strategy could be used to prepare nanoparticle from commodity monomers (methacrylates, acrylates, and styrene) ( Figure ). High molecular weight (up to 140 000 g mol −1 ) multiblock copolymers were prepared in short time periods (up to 3 h) by exploiting the segregation effect (compartmentalization) within the polymeric nanoparticles.…”

Section: Novel (Co)polymers By Raft and Their Propertiesmentioning

confidence: 99%

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

Semsarilar

Abetz

2020

Macro Chemistry & Physics

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Reversible addition–fragmentation chain transfer (RAFT) polymerization is an increasingly popular method of controlled radical polymerization and remarkable advances is made in recent years. This polymerization technique offers great chances for more sustainable routes to obtain tailor‐made polymers with high precision. This article may be of interest not only for readers familiar with the technique, but also to newcomers to the field or colleagues, who are looking for more sustainable or safer polymerization techniques to obtain an extensive number of possible polymer structures. After an introduction to RAFT polymerization, different novel paths to carry out RAFT polymerization are discussed in terms of their potential and also advancements in the polymerization technology such as polymerization induced self‐assembly or carrying out the polymerization in continuous flow reactors are highlighted. At the end some upcoming application areas of polymers prepared by RAFT are presented.

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Exploitation of the Nanoreactor Concept for Efficient Synthesis of Multiblock Copolymers via MacroRAFT-Mediated Emulsion Polymerization

Abstract: Please refer to published version for the most recent bibliographic citation information. If a published version is known of, the repository item page linked to above, will contain details on accessing it.

Cited by 75 publications

References 40 publications

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Recent Developments and Future Challenges in Controlled Radical Polymerization: A 2020 Update

Initiation of RAFT Polymerization: Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

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