Electrochemically mediated atom transfer radical polymerization (eATRP)

Chmielarz, Paweł; Fantin, Marco; Park, Sangwoo; Isse, Abdirisak Ahmed; Gennaro, Armando; Magenau, Andrew J. D.; Sobkowiak, Andrzej; Matyjaszewski, Krzysztof

doi:10.1016/j.progpolymsci.2017.02.005

Cited by 311 publications

(266 citation statements)

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“…Today, a series of reactions including Huisgen type Cu(I) catalyzed cycloaddition (CuAAC) [27,28], thiol-ene [29][30][31] and Diels-Alder [32] are recognized as well-known click chemistry reactions [33]. Modification of polymers with CuAAC click reaction is very general, robust and particularly simple compared to other click chemistry reactions [34][35][36][37]. During the recent years, these reactions have been extensively applied for the modification of commercially available polymers such as PVC [38][39][40][41], polyethylene [42] and polypropylene [43,44].…”

Section: Introductionmentioning

confidence: 99%

Polypropylene-based graft copolymers via CuAAC click chemistry

Açık¹,

Sey²,

Taşdelen³

2018

Express Polym. Lett.

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Abstract. Graft copolymers from commercial chlorinated polypropylene (PP-Cl) possessing either poly(ethylene glycol) (PEG) or poly(ɛ-caprolactone) (PCL) grafts are synthesized by copper (I)-catalyzed azide-alkyne cycloaddition 'click' reaction (CuAAC). For this purpose, azido-functional polypropylene is prepared by nucleophilic substitution of chlorine groups of PP-Cl with azidotrimethylsilane-tetrabutylammonium fluoride. Whereas, the clickable alkyne end-functional PEG and PCL are independently synthesized by esterification reaction of poly(ethylene glycol) methyl ether with 4-pentyonic acid at room temperature and ring-opening polymerization of ε-caprolactone using stannous octoate as catalyst and propargyl alcohol as initiator. Finally, the corresponding graft copolymers, PP-g-PEG and PP-g-PCL, with different surface properties were successfully synthesized by CuAAC 'click' reaction under mild condition. Spectral, chromatographic and thermal analyses at various stages prove the formation of desired polypropylene-based graft copolymers with well-defined properties. Furthermore, the water contact angle values of PP-Cl, PP-g-PEG and PP-g-PCL are found as 90±1°, 78±1.8° and 83±2.1°, respectively.

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Section: Introductionmentioning

confidence: 99%

Polypropylene-based graft copolymers via CuAAC click chemistry

Açık¹,

Sey²,

Taşdelen³

2018

Express Polym. Lett.

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“…Then, the current approaches a low and constant value as the deactivator/activator, fixed by the selected E app , is reached. Meanwhile, the multi‐step constant current approach provides a relevant advantage of carrying out an electrolysis, because it requires only a two‐electrode system and a simple current generator . The rate of the polymerizations was controlled by applying adequate E app values thereby preventing star–star coupling possibility.…”

Section: Resultsmentioning

confidence: 99%

“…Atom transfer radical polymerization is one of the most extensively applied techniques because of its ability to control on molecular weight distribution ( M w / M n , MWD, Ð ), degrees of polymerization, and structure of wide range of polymers . The new low ppm ATRP method, simplified electrochemically mediated ATRP ( se ATRP), offers more environmentally benign and industrially favored reaction conditions by elimination of chemical reducing agents, creation catalyst recycle opportunity, and provides an option to prepare polymers with designed Ð. The concept of se ATRP technique is that the activator/deactivator concentration ratio is precisely controlled by electrochemistry, the reason for the rapid development of this method …”

Section: Introductionmentioning

confidence: 99%

Synthesis of pyridoxine‐based eagle‐shaped asymmetric star polymers through seATRP

Chmielarz

2017

Polymers for Advanced Techs

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The vitamin B 6 -based macroinitiator was prepared for the first time by the transesterification reaction of pyridoxine with 2-bromoisobutyryl bromide. A pyridoxine-based star-shaped block copolymer with a hydrophilic pyridoxine core and a dual hydrophilic poly(2-(dimethylamino)ethyl methacrylate)-block-poly(N-isopropylacrylamide) arms was synthesized for the first time via a simplified electrochemically mediated atom transfer radical polymerization, utilizing only 20 ppm of catalyst complex. The rate of the polymerizations was controlled by applying appropriate potential/current values during electrolysis to prevent the possibility of intermolecular coupling of the polymer stars. The asymmetric star polymers showed narrow molecular weight distribution (Đ = 1.09-1.13).1 H NMR spectral results confirm the formation of star-like block (co)polymers. These new vitamin B 6 -based eagle-shaped star (co)polymers may find biomedical and biosensor applications as pH-sensitive and thermo-sensitive drug delivery systems.

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“…Polymerization techniques for the sequential synthesis of BCPs include ionic polymerizations (anionic, cationic, ring‐opening) and – for a little more than 20 years – controlled radical polymerizations such as atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer polymerization (RAFT), and nitroxide mediated polymerization (NMP) . Over the years, these techniques have advanced and new variations emerged, e. g., allowing to switch the polymerization “on and off” using light, electrochemistry, and sonochemistry, to name a few. BCPs can be equipped with functionalities as side groups (monomer) or at the chain ends (initiator, endcapper, polymer analogue reactions) .…”

Section: Introductionmentioning

confidence: 99%

Self‐Assembly of Multiblock Copolymers

Qiang

Chakroun

Janoszka

et al. 2019

Israel Journal of Chemistry

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Block copolymers (BCPs) are a subclass of soft matter extensively used in materials science and nanomedicine. They consist of two or more incompatible segments and are prone to self‐assemble into nanostructures with a characteristic size of 10–100 nm. BCPs thus naturally address the structural dimension between molecular and colloidal scales. This review gives a brief overview of recent developments in BCP self‐assembly under various conditions. Special emphasis is put on linear BCPs with three or more sequentially linked blocks, i. e. ABC triblock terpolymers, ABAC tetrablock terpolymers, and so on. We discuss their microphase separation in bulk, in the confinement of nanoemulsion droplets, and their hierarchical self‐assembly to multicompartment nanostructures in selective solvents. Regarding applications, block copolymers are widely used in templating and drug delivery, but their inherent asymmetry is also particularly useful for the synthesis of Janus nanoparticles.

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Electrochemically mediated atom transfer radical polymerization (eATRP)

Cited by 311 publications

References 259 publications

Polypropylene-based graft copolymers via CuAAC click chemistry

Polypropylene-based graft copolymers via CuAAC click chemistry

Synthesis of pyridoxine‐based eagle‐shaped asymmetric star polymers through seATRP

Self‐Assembly of Multiblock Copolymers

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