Continuous flow synthesis of poly(acrylic acid) via free radical polymerisation

Brocken, Laurens; Price, Paul D.; Whittaker, Jane; Baxendale, Ian R.

doi:10.1039/c7re00063d

Cited by 27 publications

(25 citation statements)

References 46 publications

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“…An and co-workers took the enzymatic cascade system in which GOx was replaced with pyranose oxide (P2Ox, a homotetrameric flavoprotein found in root fungi) due to its higher enzymatic efficiency to synthesize hydrophilic multiblock and ultra-high molecular weight (UHMW) polymers via the RAFT process in reaction vessels exposed to air (Scheme 5). [29] They successfully synthesized sequentially controlled multiblock copolymers up to 10 blocks with M n ,100 kDa, and also formed controlled UHMW polymers with M n ,2.3 million Da (MDa) with near-quantitative monomer conversion and low values (, 1.5 for the copolymers and , 1.4 for the UHMW homopolymers). RAFT Polymerization Initiated by Fenton Chemistry…”

Section: Redox Pairs For Raft Initiationmentioning

confidence: 99%

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Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Reyhani

McKenzie

et al. 2019

Aust. J. Chem.

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Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.

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Section: Redox Pairs For Raft Initiationmentioning

confidence: 99%

“…Schematic illustration of oxygen-tolerant P2Ox-HRP-meditaed RAFT polymerization and chemical structures of the CTA and monomers (M) employed. [29] H 2 O 2 injection decreases the unwanted radical 'wasting' reac-…”

Section: Redox Pairs For Raft Initiationmentioning

confidence: 99%

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Reyhani

McKenzie

et al. 2019

Aust. J. Chem.

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“…Free radical polymerization (FRP) has been widely used to synthesize different types of hydrophilic and hydrophobic synthetic polymers in aqueous and organic media . The mechanism of consists of three fundamental steps: i) Initiation , that is, the formation of an active radical followed by its addition to a vinyl monomer; ii) Propagation , that is, the rapid and progressive subsequent addition of monomer molecules to the growing polymer chain; and iii) Termination , that is, the destruction of the active radical species, usually via bimolecular combination or disproportionation .…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

“…In fact, RAFT CTAs aid in achieving control of the radical polymerization via reversible addition of the thiocarbonylthio group and rapid fragmentation reactions . Therefore, relatively analogous activation/initiation systems such as thermal, photo, enzyme, and redox based radical formation can be employed to initiate both FRP and RAFT processes. Despite the huge advances made in this field, new techniques that can overcome some of the drawbacks of these systems are continuously sought.…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

“…Redox‐initiated RAFT polymerization of the hydrophobic monomers methyl methacrylate (MMA), methyl acrylate (MA), and styrene (St) in bulk (or THF solution) were demonstrated at room temperature by using a traditional redox system: BPO and N , N ‐dimethylaniline . An and co‐workers have reported a RAFT polymerization based on a H 2 O 2 /AsAc redox pair for the generation of hydroxyl radicals. H 2 O 2 was generated via an enzymatic process, consisting of glucose oxidase (GOx), β‐D‐glucose (DG), and dissolved oxygen.…”

Section: Redox Reaction In Initiating Polymerizationsmentioning

confidence: 99%

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Fenton‐Chemistry‐Mediated Radical Polymerization

Reyhani

McKenzie

et al. 2019

Macromol. Rapid Commun.

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have been developed for the synthesis of polymers with diverse structures (linear, star, cyclic, etc.), compositions ( • mopolymer, gradient, alternating, block, etc.), and functionalities (thiol, amine, etc.). [11] The main mechanism of RDRP which results in controllable polymerization is the establishment of a dynamic equilibrium between the propagating radicals (active polymers) and the dormant species via a reversible activation-deactivation process with rate constants k act. and k deact. , respectively. [7,12] With the emergence of RDRP methods such as atom transfer radical polymerization (ATRP), [13][14][15] nitroxide-mediated polymerization (NMP), [16] and reversible addition-fragmentation transfer (RAFT) [11,17,18] there has been significant effort to control these techniques via different physical and chemical stimuli. [19][20][21][22][23][24][25][26][27] Of these, RAFT holds particular promise due to its compatibility with a diverse range of solvents, monomers, and operating conditions. [11,24,[28][29][30][31][32][33][34][35] Among RDRP methods, one might argue that RAFT is the most similar to traditional FRP, with the simple addition of a thiocarbonylthio-containing compound chain transfer agent (CTA, termed as RAFT agent) [36] that can mediate the polymerization, allowing the synthesis of well-defined polymers (Scheme 1). In fact, RAFT CTAs aid in achieving control of the radical polymerization via reversible addition of the thiocarbonylthio group and rapid fragmentation reactions. [37,38] Therefore, relatively analogous activation/initiation systems such as thermal, [4,11,[28][29][30][31][39][40][41] photo, [2,24,[32][33][34][42][43][44][45][46][47][48][49] enzyme, [5,23,[50][51][52][53][54] and redox [3,[55][56][57][58][59] based radical formation can be employed to initiate both FRP and RAFT processes. Despite the huge advances made in this field, new techniques that can overcome some of the drawbacks of these systems are continuously sought. For example, using a thermal initiator requires a high operating temperature, limiting the possibility for in situ FRP/RAFT methods in biological systems, where temperature control is limited. The rate of visible light-activated RAFT polymerization without using photocatalysts is relatively slow, [34,60] while photocatalysts, e.g. iridium and rutheniumbased ones, [24,61] employed in photo-activated processes are expensive. Moreover, photo-mediated polymerization faces difficulties in terms of the equipment requisite to perform photoinitiation at scale. [29] Redox-responsive polymerization systems have many advantages, including a low activation energy (40-85 kJ mol −1 ), easy and facile control over the polymerization at ambient temperatures, very short induction periods, etc. [56,62] Polymerizations initiated by a redox reaction between an oxidizing and a reducing agent are referred to as "redox polymerizations." [63] Use of Radical PolymerizationIn this review, the power of a classical chemical reaction, the Fenton reaction for initiating radical polymeriza...

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Investigation of a hybrid binder system for large scale 3D printing

Remke,

Sant,

Gädt

2023

ce papers

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Large‐scale additive manufacturing of reactive suspensions, such as concrete, is being developed to freely create objects without the constraints of a formwork. One challenge in printing suspensions is the precise spatio‐temporal control over their rheological properties. For extrusion‐based processes the material must be pumpable to the nozzle of the printer, while once it has passed the nozzle, it must maintain its shape under the increasing pressure of subsequent layers. Therefore, it is beneficial if the material exhibits an appropriately designed rheology change at the nozzle. The objective of this work is to develop a printing suspension which achieves a rheological step change at the nozzle. Therefore, we create a hybrid binder system comprising of a fast, reactive organic component, which can be activated by heat and a second inorganic binder components, in our system the carbonation of calcium hydroxide, which delivers the final strength.The temperature dependent stiffening of the model suspensions is studied by oscillatory rheology at temperatures between 20 °C to 80 °C. For mechanical testing purposes, cuboid shaped samples are obtained by microwave heating followed by carbonation under ambient conditions. For the given porosity, the material reaches a compressive strength of up to 0.39 MPa in 10 seconds or up to 1.94 MPa in 10 minutes depending on the heating program. Subsequent carbonation for 7 days under ambient conditions gives a strength of up to 4.76 MPa.

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Continuous flow synthesis of poly(acrylic acid) via free radical polymerisation

Abstract: The free radical polymerisation of aqueous solutions of acrylic acid (1) has been studied using a continuous flow reactor to quickly screen reaction parameters such as temperature, residence time, monomer- and initiator concentration.

Cited by 27 publications

References 46 publications

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

Fenton‐Chemistry‐Mediated Radical Polymerization

Investigation of a hybrid binder system for large scale 3D printing

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