Mediated Atom Transfer Radical Polymerization Research Articles

Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current.

Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square-wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low-activity Cu/2,2-bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain-end fidelity of the produced polymers, yielding functional and high molecular-weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

Electrochemically Mediated Atom Transfer Radical Polymerization Driven by Alternating Current

Alternating current (AC) and pulsed electrolysis are gaining traction in electro(organic) synthesis due to their advantageous characteristics. We employed AC electrolysis in electrochemically mediated Atom Transfer Radical Polymerization (eATRP) to facilitate the regeneration of the activator CuI complex on Cu0 electrodes. Additionally, Cu0 served as a slow supplemental activator and reducing agent (SARA ATRP), enabling the activation of alkyl halides and the regeneration of the CuI activator through a comproportionation reaction. We harnessed the distinct properties of Cu0 dual regeneration, both chemical and electrochemical, by employing sinusoidal, triangular, and square‐wave AC electrolysis alongside some of the most active ATRP catalysts available. Compared to linear waveform (DC electrolysis) or SARA ATRP (without electrolysis), pulsed and AC electrolysis facilitated slightly faster and more controlled polymerizations of acrylates. The same AC electrolysis conditions could successfully polymerize eleven different monomers across different mediums, from water to bulk. Moreover, it proved effective across a spectrum of catalyst activity, from low‐activity Cu/2,2‐bipyridine to highly active Cu complexes with substituted tripodal amine ligands. Chain extension experiments confirmed the high chain‐end fidelity of the produced polymers, yielding functional and high molecular‐weight block copolymers. SEM analysis indicated the robustness of the Cu0 electrodes, sustaining at least 15 consecutive polymerizations.

Enhanced stability of gold nanoparticles capped with double hydrophilic block copolymers synthesized by eATRP

AbstractIn this study, the gold nanoparticles (Au NPs) are capped with a novel, well‐defined double hydrophilic block copolymer, poly (ethylene glycols)‐block‐poly(mono‐2‐(methacryloyloxy) ethyl succinate) (PEG‐b‐PSEMA). The PEG‐b‐PSEMA, with long side chains and relatively narrow dispersity index, is successfully prepared by aqueous electrochemically mediated atom transfer radical polymerization using a PEG‐Br macroinitiator (Mn≈2000 g mol−1). By simply mixing PEG‐b‐PSEMA and Au precursor before adding reductants, coulombic interactions occur between the Au precursor and the carboxylate group of the PSEMA, as a result dense Au NPs are formed. This enables the Au NPs to remain dispersed even in the presence of temperature variations, pH adjustments, and incubation in organic solvents. Au NPs were endowed by PEG‐b‐PSEMA with more remarkable catalytic activity in organic solvents of 4‐nitrophenol into 4‐aminophenol than by sodium citrate (Au@citrate) and MeO‐PEG‐OH (Au@PEG). In addition, PEG‐b‐PSEMA‐stabilized Au NPs (Au@PEG‐b‐PSEMA) were also tested for the dye degradation property against Rhodamine‐B in only pH 10 basic solution, and over 99% of dye degradation can be achieved in 9 min. PEG‐b‐PSEMA induces coulombic interactions with Au NPs, providing outstanding stability for catalytic applications in organic or specific acidic‐base environments.

Hybridization chain reaction-enhanced electrochemically mediated ATRP coupling high-efficient magnetic separation for electrochemical aptasensing of cardiac troponin I

The sensitive and accurate detection of cardiac troponin I (cTnI) as a gold biomarker for cardiovascular diseases at an early stage is crucial but has long been a challenge. In this study, we presented such an electrochemical (EC) aptasensor by combining hybridization chain reaction (HCR)-enhanced electrochemically mediated atom transfer radical polymerization (eATRP) amplification with high-efficient separation of magnetic beads (MBs). Aptamer-modified MBs empowered effective recognition and separation of cTnI from complex samples with high specificity. The specific binding of cTnI and aptamer could release triggered DNA (T-DNA) into solution to drive an HCR process, which produced plentiful active sites for eATRP initiators labeling followed by initiating eATRP process. With the development of eATRP, a great many of electroactive polymer probes were continually in situ formed to generate amplified current output for signal enhancement. Compared to no amplification, HCR-enhanced eATRP promoted the signals by ∼10-fold, greatly improving detection sensitivity for low-abundant cTnI analysis. Integrating MBs as capture carriers with HCR-enhanced eATRP as amplification strategy, this EC aptasensor achieved a low detection limit of 10.9 fg/mL for cTnI detection. Furthermore, the reliable detectability and anti-interference were confirmed in serum samples, indicating its promising application toward early diagnosis of cardiovascular diseases.

Solution and Film Self-Assembly Behavior of a Block Copolymer Composed of a Poly(ionic Liquid) and a Stimuli-Responsive Weak Polyelectrolyte.

Cu(0)-mediated atom transfer radical polymerization was used to synthesize a poly(ionic liquid), poly[4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PVBBImTf2N), a stimuli-responsive polyelectrolyte, poly[2-(dimethylamino)ethyl methacrylate] (PDMAEMA), and a novel block copolymer formed from these two polymers. The synthesis of the block copolymer, poly[2-(dimethylamino) ethyl methacrylate]-block-[poly(4-vinylbenzyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide] (PDMAEMA-b-PVBBImTf2N), was examined to evaluate the control of "livingness" polymerization, as indicated by molecular weight, characterizations of degree of polymerization, and 1HNMR spectroscopy. 2D DOSY NMR measurements revealed the successful formation of block copolymer and the connection between the two polymer blocks. PDMAEMA-b-PVBBImTf2N was further characterized for supramolecular interactions in both the bulk and solution states through FTIR and 1H NMR spectroscopies. While the block copolymer demonstrated similar intermolecular behavior to the PIL homopolymer in the bulk state as indicated by FTIR, hydrogen bonding and counterion interactions in solution were observed in polar organic solvent through 1H NMR measurements. The DLS characterization revealed that the PDMAEMA-b-PVBBImTf2N block copolymer forms a network-like aggregated structure due to a combination of hydrogen bonding between the PDMAEMA and PIL group and electrostatic repulsive interactions between PIL blocks. This structure was found to collapse upon the addition of KNO3 while still maintaining hydrogen bonding interactions. AFM-IR analysis demonstrated varied morphologies, with spherical PDMAEMA in PVBBImTf2N matrix morphology exhibited in the region approaching the film center. AFM-IR further revealed signals from silica nano-contaminates, which selectively interacted with the PDMAEMA spheres, demonstrating the potential for the PDMAEMA-b-PVBBImTf2N PIL block copolymer in polymer-inorganic nanoparticle composite applications.

Driving Polymer Brushes from Synthesis to Functioning.

The great success of controlled radical polymerizations has encouraged researchers to develop more facile and robust approaches for surface-initiated polymerizations (SIPs) to fabricate polymer brushes, even for non-experts. In recent years, external-stimuli-mediated radical polymerization methods have come to the fore as SIPs because of their less rigorous synthetic procedures and high controllability, which expand the opportunities for synthesizing macromolecules with desired chemical compositions and structures, as well as tailor-made polymers and bioconjugates that show broad applicability and physiological compatibility. This review discusses the latest developments in surface-initiated polymerization methods, in particular, external-stimuli mediated atom transfer radical polymerization (ATRP), photo-induced polymerizations, and reversible addition-fragmentation chain transfer (RAFT) polymerization, as well as other methods and their combination for the application in surface grafting. The implementation of these methods is of great interest due to their unique possibilities to temporally control a polymerization process, fast and straightforward polymerization, and environmentally benign features, which lead to established and emerging applications in biolubrication, antifouling, and biosensing.

Driving Polymer Brushes from Synthesis to Functioning

AbstractThe great success of controlled radical polymerizations has encouraged researchers to develop more facile and robust approaches for surface‐initiated polymerizations (SIPs) to fabricate polymer brushes, even for non‐experts. In recent years, external‐stimuli‐mediated radical polymerization methods have come to the fore as SIPs because of their less rigorous synthetic procedures and high controllability, which expand the opportunities for synthesizing macromolecules with desired chemical compositions and structures, as well as tailor‐made polymers and bioconjugates that show broad applicability and physiological compatibility. This review discusses the latest developments in surface‐initiated polymerization methods, in particular, external‐stimuli mediated atom transfer radical polymerization (ATRP), photo‐induced polymerizations, and reversible addition‐fragmentation chain transfer (RAFT) polymerization, as well as other methods and their combination for the application in surface grafting. The implementation of these methods is of great interest due to their unique possibilities to temporally control a polymerization process, fast and straightforward polymerization, and environmentally benign features, which lead to established and emerging applications in biolubrication, antifouling, and biosensing.

An electrochemically mediated ATRP synthesis of lignin-g-PDMAPS UCST-thermoresponsive polymer

It is a promising idea to graft zwitterionic polymers onto lignin and prepare lignin-grafted-poly [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (Lignin-g-PDMAPS) thermosensitive polymer with the upper critical solution temperature (UCST). In this paper, an electrochemically mediated atom transfer radical polymerization (eATRP) method was used to prepare Lignin-g-PDMAPS. The structure and property of the Lignin-g-PDMAPS polymer were characterized by the fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), X-ray electron spectroscopy (XPS), dynamic light scattering (DLS), differential scanning calorimeter (DSC). Furthermore, the effect of catalyst structure, applied potential, amount of Lignin-Br, Lignin-g-PDMAPS concentration, NaCl concentration on UCST of Lignin-g-PDMAPS were investigated. It was worth noting that polymerization was well controlled when the ligand was tris (2-aminoethyl) amine (Me6TREN), applied potential was −0.38 V and the amount of Lignin-Br was 100 mg. And the UCST of the Lignin-g-PDMAPS aqueous solution (1 mg/ml) was 51.47 °C, the molecular weight was 8987 g/mol, and the particle size was 318 nm. It was also found that the UCST increased and the particle size decreased with the Lignin-g-PDMAPS polymer concentration increased, and the UCST decreased and the particle size increased with the NaCl concentration increases. This work investigated UCST-thermoresponsive polymer which possessed lignin main chain combining the zwitterionic side chain, and provided a new way for development of lignin based UCST-thermoresponsive materials and medical carrier materials, in addition to expand the scope of eATRP.

In-depth mechanistic and kinetic investigation of sonochemically mediated atom transfer radical polymerization using modeling approach

Mechano/sonochemically mediated reversible deactivation radical polymerization has attracted great attention because of the novel electron transfer regulation process and high-efficient process intensification on mass transfer. Herein, a multi-scale modeling strategy combining quantum chemical calculation and kinetic modeling was developed for sonochemically induced electron transfer controlled atom transfer radical polymerization (SET-ATRP) to study the complicated SET process and its effects on polymerization. At the molecular scale, density functional theory (DFT) calculations were used to acquire the electron characteristic and structure–reactivity of the reactants, intermediates and products during SET process, which provides guideline to figure out the underlying mechanism. Results showed that DMSO•• generated under ultrasonication could react with free Me6TREN to induce electron transfer for the reduction of CuIIBr/L+ to produce CuI/L+, which is the key step for a successful polymerization. The corresponding elementary reaction rate coefficients were calculated by thermodynamic formulae combining transition state theory and Marcus theory. At the micro-scale, kinetic modeling based on method of moment was established to account for the role of SET process in regulating polymerization. Good agreements between the simulation results and experimental data confirmed the reliability of the as-developed multi-scale modeling strategy. More Me6TREN and CuIIBr/L+ resulted in more electron transfer and faster polymerization rate. This work provides an in-depth mechanism insights and kinetic understanding for SET-ATRP, which has a promising potential to promote its progress of application.

Nitroxide-containing amphiphilic polymers prepared by simplified electrochemically mediated ATRP as candidates for therapeutic antioxidants

Nitroxide-containing amphiphilic polymers for therapeutic use were prepared in two-step procedure. Firstly, amphiphilic copolymers composed of hydrophobic poly(n-butyl acrylate) (PnBA) and hydrophilic poly[oligo(ethylene glycol) methyl ether acrylate] (POEGA) or poly(2-hydroxyethyl acrylate) (PHEA) were synthesized by simplified electrochemically mediated atom transfer radical polymerization (seATRP). Due to the precisely-controlled structure of each polymer block proved by narrow dispersity (Mw/Mn < 1.19), chain-end halide functionality of macromolecules was preserved. Therefore, it was possible to efficiently convert the halide atom at the end of the chain to stable radicals via the amination of the polymer with 4-amino-2,2,6,6-tetrametylopiperydynyloksyl (4-amino-TEMPO, 4-AT). The prepared polymers are able to self-assemble in an aqueous solution into micelles with a hydrodynamic diameter of approximately 31 nm measured by dynamic light scattering (DLS) analysis. The susceptibility of the prepared micelles for biomedical applications was studied by evaluation of the effect on erythrocytes and fibroblasts and their antioxidant properties by testing of inhibition of oxidation reactions – oxidation of dihydrorhodamine 123 (DHR 123), induced by biologically relevant oxidants. The antioxidant effects of polymeric micelles were compared with those of free 4-AT. Prepared TEMPO-containing micelles exhibited biocompatibility in interaction with human erythrocytes and fibroblasts and exerted antioxidant effects. Therefore, the micelles are potentially good candidates for in vivo applications.

Dually Amplified Electrochemical Aptasensor for Endotoxin Detection via Target-Assisted Electrochemically Mediated ATRP.

As the entering of bacterial endotoxin into blood can cause various life-threatening pathological conditions, the screening and detection of low-abundance endotoxin are of great importance to human health. Taking advantage of signal amplification by target-assisted electrochemically mediated atom transfer radical polymerization (teATRP), we illustrate herein a simple and cost-effective electrochemical aptasensor capable of detecting endotoxin with high sensitivity and selectivity. Specifically, the aptamer receptor was employed for the selective capture of endotoxin, of which the glycan chain was then decorated with ATRP initiators via covalent coupling between the diol sites and phenylboronic acid (PBA) group, followed by the recruitment of ferrocene signal reporters via the grafting of polymer chains through potentiostatic eATRP under ambient temperature. As the glycan chain of endotoxin can be decorated with hundreds of ATRP initiators while the further grafting of polymer chains through eATRP can recruit hundreds to thousands of signal reporters to each initiator-decorated site, the teATRP-based strategy allows for the dual amplification of the detection signal. This dually amplified electrochemical aptasensor has the ability to sensitively and selectively detect endotoxin at a concentration as low as 1.2 fg/mL, and its practical applicability has been further demonstrated using human serum samples. Owing to the simplicity, high efficiency, biocompatibility, and inexpensiveness of the teATRP-based amplification strategy, this electrochemical aptasensor holds great application potential in the sensitive and selective detection of low-abundance endotoxin and many other glycan chain-containing bio-targets.

Fluorescent nano‐particles prepared by eATRP combined with self‐assembly imprinting technology

AbstractA novel amphiphilic photoreactive block copolymer was synthesized by electrochemically mediated atom transfer radical polymerization (eATRP) of glycidyl methacrylate (GMA), N‐vinyl carbazole (VK) with polyethylene glycol‐based initiator (PEG‐Br). And then the double bond and the boric acid group were introduced through the epoxy group. Fluorescent molecularly imprinted nanoparticles (nano‐FMIPs) were prepared using self‐assembly imprinting technology with PEG‐b‐P(GMA‐co‐VK) as a functional monomer and sialic acid (SA) as a template molecule. The nano‐FMIPs prepared by this method have the advantages of uniform size and small particle size, which greatly improves their recognition performance. It is found that the SA template can significantly quench the fluorescence intensity of nano‐FMIPs linearly within a concentration range of 4 × 10−4–4 × 10−6 mol L−1, which is well described by Stern–Volmer equation. The nano‐FMIPs can selectively and sensitively detect down to 2.9 μM of SA concentration. This study provides a new and general strategy for the preparation of nano‐MIPs with high selective recognition ability in aqueous media, which has good application prospects in biomedicine.

Process intensification of continuous-flow seATRP by a sonicated multi-reactor setup.

Simplified electrochemically mediated atom transfer radical polymerization (seATRP) is a versatile technique for synthesizing polymers with precise control and complex architecture. Continuous-flow seATRP has recently been realized by using a sonicated microreactor but still faces limitations such as relatively low conversion and difficulties in synthesizing polymers with high molecular weight. Herein, a novel multi-reactor setup is demonstrated. By tuning the currents applied to different reaction stages in the setup, 90% conversion can be achieved while maintaining relatively low dispersity (<1.35). Meanwhile, the unique design enables a wider processing window for sonication due to greater viscous attenuation in the second reactor, thus largely addressing the problem associated with high viscosity during the synthesis of high molecular weight polymers. The developed setup also offers an alternative strategy for future scale-up of continuous-flow seATRP.

Scaling-Up an Aqueous Self-Degassing Electrochemically Mediated ATRP in Dispersion for the Preparation of Cellulose-Polymer Composites and Films.

Electrochemically mediated atom transfer radical polymerization (eATRP) is developed in dispersion conditions to assist the preparation of cellulose-based films. Self-degassing conditions are achieved by the addition of sodium pyruvate (SP) as a ROS scavenger, while an aluminum counter electrode provides a simplified and more cost-effective electrochemical setup. Different polyacrylamides were grown on a model cellulose substrate which was previously esterified with 2-bromoisobutyrate (-BriB), serving as initiator groups. Small-scale polymerizations (15 mL) provided optimized conditions to pursue the scale-up up to 1000 mL (scale-up factor ~67). Cellulose-poly(N-isopropylacrylamide) was then chosen to prepare the tunable, thermoresponsive, solvent-free, and flexible films through a dissolution/regeneration method. The produced films were characterized by Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), dynamic scanning calorimetry (DSC), and thermogravimetric analysis (TGA).

Improvement of electrochemically mediated atom transfer radical polymerization: Use of aluminum as a sacrificial anode in water

The simplest electrolytic devices are undivided electrochemical cells without any separator between anodic and cathodic compartments. These simple yet efficient electrochemical cells often require the use of sacrificial metal counter electrodes, which, however, are incompatible with many electrocatalytic systems. In this article, we investigate the effect of the presence of an Al anode on an electrocatalytic reaction in water, namely electrochemically-mediated atom transfer radical polymerization (eATRP) catalyzed by common Cu complexes with amine ligands. It was found that the sacrificial anode could undermine the reactivity of the aqueous Cu catalysts in two ways: i) protonation of the amine ligand promoted by the release of acidic Al3+ ions; ii) spontaneous deposition of Cu0 on the Al metal surface. Both pathways led to decomposition of the original copper catalyst. To avoid undesired side reactions arising from the Al anode, simple strategies involving the use of appropriate amine ligands and pH buffers are described.

Dual-signal amplified electrochemical biosensor based on eATRP and PEI for early detection of lung cancer

Carcinoembryonic antigen (CEA), a lung cancer marker with high sensitivity and specificity, plays vital roles in the early diagnosis of lung cancer. In this paper, an electrochemical biosensor for highly sensitive detection of CEA was constructed, which based on dual signal amplification of electrically mediated atom transfer radical polymerization (eATRP) and polyethyleneimine (PEI) for the first time. Firstly, CEA was captured in a specific recognition manner with CEA aptamer 1 (Apt1), which self-assembled on the electrode via “Au-S” bond. After that, CEA aptamer 2-PEI (Apt2-PEI) was recognized by CEA to form an Apt-antigen-Apt sandwich structure. Next, multiple initiation sites were introduced for the eATRP reaction by the amide reaction. Finally, numerous electroactive monomers, ferrocene methacrylate (FMMA), were grafted onto the modified electrode by eATRP. Under the optimized conditions, there was a wide linear detection range of 10-3 ∼ 102 ng·mL−1, and the limit of detection (LOD) was 70.17 fg·mL−1. Compared to other reported sensors, this electrochemical biosensor used a simpler and more environmentally friendly eATRP, and the use of PEI increased the electron transfer rate. Moreover, the biosensor showed superior analytical performance in the clinical serums and has great promise for early lung cancer diagnosis applications.

The scale-up of electrochemically mediated atom transfer radical polymerization without deoxygenation

The scale-up of Atom Transfer Radical Polymerization (ATRP) from 15 mL to 15 L (scale-up factor 1000) by galvanostatic simplified electrochemically mediated ATRP (seATRP) is disclosed. An electrochemical O2 scavenging cycle was embedded in the ATRP equilibrium to allow self-degassing of the mixture and avoid impractical deoxygenation procedures. Low volume seATRP of acrylamide in water was optimized by studying various reaction parameters, including the concentrations of scavenger, supporting electrolyte, type of initiator and ligand, and catalyst loading. The target reaction was scaled up from 0.015 L to 15 L. At all volumes and up to 15 L, polymerizations were relatively fast and produced well-defined polyacrylamide with narrow molecular weight (MW) distributions. All reactions were powered by renewable electricity, obtained from a photovoltaic plant. Several water-soluble monomers, including (meth)acrylic acid and methacrylamide, were polymerized at pH ranging from 1.0 to 7.4, without compromising the self-degassing mechanism. These results show a feasible scale-up of seATRP and could foster its adoption by polymer industries promoting a more widespread use of controlled radical polymerizations.

Galvanic-Replacement-Assisted Surface-Initiated Atom Transfer Radical Polymerization for Functional Polymer Brush Engineering.

Here we present a facile and robust strategy, namely, galvanic-replacement-assisted surface-initiated Cu(0)-mediated atom transfer radical polymerization (gr-SI-Cu0ATRP, or gr-SI-Cu0CRP) for polymer brush engineering under ambient conditions. In gr-SI-Cu0ATRP, highly active and nanostructured Cu(0) surfaces are obtained by a simple galvanic replacement on zinc/aluminum surfaces in dilute Cu2+ solution. Polymer brush growth rate is extremely high (up to ∼904 nm in 30 min polymerization); meanwhile, both nano Cu(0) surfaces and Cu2+ solution can be reused multiple times without losing grafting efficiency. We also demonstrate that the gr-SI-Cu0ATRP is advantageous for polymer brush engineering on arbitrary substrates, including flexible (polyethylene terephthalate), curved (polycarbonate), and porous (anodic aluminum oxide), and endow the substrates with various functionalities, for example, anti-icing, antifogging, and ion selectivity.

Polymer-grafted-carbon assembled via an electrochemically-aided atom transfer radical polymerization: Towards improved energy storage electrode

We are exploring a simplified electrochemically mediated atom transfer radical polymerization method (se-ATRP), allowing us to create new carbon-grafted polymer assemblies with improved charge storage capabilities. These molecularly imprinted conjugations serve as an active component of a supercapacitor electrode that displayed a capacitance value 46.5% larger than that of pure polypyrrole and seemed to double the stability at select voltages. Furthermore, after more than 5000 charge/discharge cycles, 98.97% of the capacitance was retained. This capacitance enhancement is owned to the morphology the polymer represented by nano-ribbons and nanoparticles that are evenly wrapped around carbon nanotubes. This favours charge transfer associate with redox activity of the polymer during electrode’s charge–discharge life cycle. Moreover, carbon demonstrates dual functionality as a charge transport facilitator at first, and also as the stabilizing backbone for the polymer. The later results in improved lifetime of the electrode upon applied potential, which is always the most sought-after feature of polymer-based energy materials.

Continuous-flow self-supported seATRP using a sonicated microreactor.

Continuous-flow simplified electrochemically mediated atom transfer radical polymerization (seATRP) was achieved for the first time without supporting electrolytes (self-supported) using a novel sonicated tubular microreactor. Polymerizations of different acrylic monomers were carried out under different applied currents. The reaction was fast with 75% conversion achieved at ambient temperature in less than 27 minutes. Results also showed good evolution of molecular weight and maintained narrow molecular weight distribution. The reaction rate can be further manipulated by tuning the applied current. Sonication under proper conditions was found to be able to significantly improve both reaction rate and controllability. Self-supported reactions also enable more environmentally friendly and cost-effective operations.