Recent progress in switchable RAFT agents: Design, synthesis and application

Opiyo, George Ouma; Jin, Jianyong

doi:10.1016/j.eurpolymj.2021.110713

Cited by 15 publications

(10 citation statements)

References 114 publications

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“…Due to the advantages of its mild reaction conditions, wide range of monomer selection, and strong molecular design ability, it has developed into one of the most versatile and powerful polymerization technologies. 55,56 The whole reaction was carried out in an N 2 atmosphere. Monomer 1 (2.1 g, 6 mmol), DMAEMA (0.339 g, 2.16 mmol), and HEMA (0.280 g, 2.16 mmol) were dissolved in 30 mL of THF, and 1 mL of free radical stabilizer was added after the solution was completely dissolved.…”

Section: Synthesis Of Photon and Ph Dual-stimulus-responsive Polymersmentioning

confidence: 99%

Synthesis and Characteristics of Smart Coating Materials for Reversible Double Stimulus-Responsive Oil–Water Separation

Zhang,

Wang,

Qiu

et al. 2024

ACS Appl. Polym. Mater.

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The developed smart coating for water−oil separation, characterized by its mild separation conditions, ease of control, and absence of secondary pollution, holds promising potential for applications in controlled liquid transmission, oil−water separation, smart textiles, and biosensing films. This work focused on synthesizing copolymers that respond to both photon and pH stimuli. Initially, 4-trifluoromethoxy-4′-methacryloxyazobenzene (FMAB) and similar monomers, serving as photon-responsive units with varying carbon chain lengths, were synthesized using different synthetic routes. Such a design approach also aimed to enhance the hydrophobic characteristics of the photoresponsive segments to a certain degree. Theoretically, the impact of the carbonyl position on nucleophilic substitution reactions was investigated through density functional theory (DFT) calculations. These monomers were subsequently copolymerized individually with dimethylaminoethyl methacrylate (DMAEMA), which acts as a pH-responsive unit, using the reversible addition−fragmentation chain transfer (RAFT) technique in a one-step copolymerization process. The polymers were subsequently coated onto glass slides to form films, the contact angles of which could be modulated in response to both light and pH stimuli. To be highlighted, the maximum contact angle change can reach 131°under double stimulation. To ultimately showcase its oil−water separation capabilities, the polymer was combined with a nonwoven fabric to create a membrane. This membrane is capable of reversibly transitioning between hydrophilic−lipophobic and hydrophobic− lipophilic states, demonstrating substantial potential for future advancements in efficient water−oil separation.

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Section: Synthesis Of Photon and Ph Dual-stimulus-responsive Polymersmentioning

confidence: 99%

Synthesis and Characteristics of Smart Coating Materials for Reversible Double Stimulus-Responsive Oil–Water Separation

Zhang,

Wang,

Qiu

et al. 2024

ACS Appl. Polym. Mater.

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“…This was attributed to the nature of the solvent which does not allow for the sufficient protonation of the RAFT agent. [59,60] To bypass this, we sought to increase the monomer concentration from 20% v/v to 50% v/v and indeed by minimizing the solvent content, a lower Ɖ could be achieved when identical acid equivalents were employed (when using 6 equivalents of acid the lowest Ɖ at 20% v/v was 1.31 and the value was further decreased to 1.23 at 50% v/v monomer concentration, Figure S3a&c, Table S4&S8). To fully circumvent this issue, we replicated the experiments in aqueous media (at 20% v/v).…”

Section: Effect Of Targeting Various Degrees Of Polymerizationmentioning

confidence: 99%

Controlling polymer dispersity using switchable RAFT agents: Unravelling the effect of the organic content and degree of polymerization

Antonopoulou

Whitfield

Truong

et al. 2022

European Polymer Journal

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“…Reversible deactivation radical polymerization (RDRP) techniques have revolutionized polymer synthesis since their conception in the late 20th century. − They enable the synthesis of well-defined vinyl (co)polymers with targeted molecular weight and low molar mass dispersity ( Đ ) without the need for stringent synthetic procedures associated with techniques such as living anionic polymerization. The three most studied RDRP techniques, atom transfer radical polymerization (ATRP), ,, nitroxide mediated polymerization (NMP), − and reversible addition fragmentation chain transfer (RAFT), ,− all have well-studied and well-understood mechanisms, , with pseudo-first-order kinetics, a linear evolution in number-average molecular weight ( M n ) with conversion (α), and resulting low- Đ polymers (typically < 1.20). These properties are a result of the equilibrium between the dormant species and propagating radicals; in the absence of this (for FRP), broader statistical distributions of molecular weights are observed …”

Section: Introductionmentioning

confidence: 99%

Development and Experimental Validation of a Dispersity Model for In Silico RAFT Polymerization

et al. 2023

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The exploitation of computational techniques to predict the outcome of chemical reactions is becoming commonplace, enabling a reduction in the number of physical experiments required to optimize a reaction. Here, we adapt and combine models for polymerization kinetics and molar mass dispersity as a function of conversion for reversible addition fragmentation chain transfer (RAFT) solution polymerization, including the introduction of a novel expression accounting for termination. A flow reactor operating under isothermal conditions was used to experimentally validate the models for the RAFT polymerization of dimethyl acrylamide with an additional term to accommodate the effect of residence time distribution. Further validation is conducted in a batch reactor, where a previously recorded in situ temperature monitoring provides the ability to model the system under more representative batch conditions, accounting for slow heat transfer and the observed exotherm. The model also shows agreement with several literature examples of the RAFT polymerization of acrylamide and acrylate monomers in batch reactors. In principle, the model not only provides a tool for polymer chemists to estimate ideal conditions for a polymerization, but it can also automatically define the initial parameter space for exploration by computationally controlled reactor platforms provided a reliable estimation of rate constants is available. The model is compiled into an easily accessible application to enable simulation of RAFT polymerization of several monomers.

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Recent progress in switchable RAFT agents: Design, synthesis and application

Cited by 15 publications

References 114 publications

Synthesis and Characteristics of Smart Coating Materials for Reversible Double Stimulus-Responsive Oil–Water Separation

Synthesis and Characteristics of Smart Coating Materials for Reversible Double Stimulus-Responsive Oil–Water Separation

Controlling polymer dispersity using switchable RAFT agents: Unravelling the effect of the organic content and degree of polymerization

Development and Experimental Validation of a Dispersity Model for In Silico RAFT Polymerization

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