End group modification of poly(acrylates) obtained via ATRP: a user guide

Anastasaki, Athina; Willenbacher, Johannes; Fleischmann, Carolin; Gutekunst, Will R.; Hawker, Craig J.

doi:10.1039/c6py01993e

Cited by 59 publications

(51 citation statements)

References 45 publications

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“…[327,328] ATRP can also be efficiently combined with other polymerization or post-polymerization methods for preparation of copolymers with complex architectures. [329][330][331] Click chemistry was successfully employed for preparation of a variety of macrocyclic, block, star, and graft copolymers. [161,[332][333][334][335][336][337][338][339][340] Concurrent or consecutive ATRP and ring-opening, [341][342][343][344] ringopening metathesis, [345] or cationic [346,347] polymerization reactions were reported.…”

Section: Copolymerizationmentioning

confidence: 99%

Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

200

138

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This review encompasses the fundamentals of kinetics of atom transfer radical polymerization (ATRP). ATRP is a versatile reversible-deactivation radical polymerization (RDRP) technique, frequently utilized to synthesize advanced functional materials. Detailed mechanistic investigations over the past two decades allowed for an in-depth understanding of the underlying processes and rational design of the reaction conditions. Various aspects of ATRP kinetics are reviewed such as initiation modes, methods allowing to decrease catalyst concentration, influence of the initiator, catalyst (transition metal, ligand, counterion), solvent, additives, type of monomer, and effect of temperature and pressure. Techniques utilized to determine kinetic parameters of catalytic systems are discussed. Finally, guidelines for synthesis of polymers with targeted architectures, predetermined molecular weights, narrow molecular weight distributions, and high retained chain end functionality are presented.

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Section: Copolymerizationmentioning

confidence: 99%

Kinetics of Atom Transfer Radical Polymerization

Krys

2017

European Polymer Journal

200

138

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“…The ‐CH 3 protons (j) of the butyl moiety appeared at 0.88–0.9 ppm. Also, the protons of SCH 2 CH 2 CH 2 (h and i) and CH 2 S CH 2 (f and g) appeared at 1.214–1.340 and 2.432–2.645 ppm, respectively (Figure ) . The M n calculated from GPC was 3454 g/mol, and that calculated from 1 H‐NMR was 2300 g/mol.…”

Section: Resultsmentioning

confidence: 92%

“…1 H‐NMR of PIII displayed new additional peaks at 2.48–2.65 ppm due to the protons of the methyl group (SCH 2 CH 3 ) that interfered with the other methyl group of PHB and 2.76–2.81 ppm due to the C H 2 SC H 2 protons (f and g, Figure ) . The sulfur content of PIII was 0.91% (Table ).…”

Section: Resultsmentioning

confidence: 99%

Functionalization of poly(3‐hydroxybutyrate) with different thiol compounds inhibits MDM2–p53 interactions in MCF7 cells

Abdelwahab

El‐Barbary

El-Said

et al. 2018

J of Applied Polymer Sci

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High-molecular-weight poly(3-hydroxybutyrate) (PHB) has a low reactivity toward its terminal functional groups. Thus, the chemical reactivity of PHB was enhanced by the chemical degradation that occurred via β-elimination through the functionalization of PHB with ethylene glycol to give a low-molecular-weight PHB-diol. The reaction of PHB-diol with acryloyl chloride gave PHB-diacrylate, which was grafted by thiol compounds, such as ethane dithiol, 2-mercaptoethanol, ethane thiol, dithiothreitol, butane thiol, and thioglycolic acid, via a Michael-type addition reaction. The chemical and thermal properties of the functionalized PHB-thiol products were characterized with Fourier transform infrared spectroscopy, 1 H-NMR, gel permeation chromatography, differential scanning calorimetry, and thermogravimetric analysis techniques. X-ray diffraction showed that the PHB-thiol polymers had slight differences in crystallinity compared with neat PHB. The biological activities of the neat polymer and new PHB-thiol polymers, including the antibacterial and anticancer activities, were tested, and some of these products showed antibacterial and anticancer activities. These anticancer activities were attributed to the ability of these PHB-thiol polymers to induce apoptosis (as revealed by the higher expression of Bax and caspase 9 and the lower expression of Bcl2) and cell-cycle arrest in the G0/G1 phase, which is associated with the higher expression of p53 and p21 and the lower expression of the p53 inhibitor, MDM2. Thus, the anticancer effect of these PHB-thiol polymers may have been due to their ability to inhibit MDM2-p53 interactions.

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“…By far the majority of these modifications rely on straightforward substitution reactions with a range of nucleophiles, including azides, amines, carboxylic acids, phosphines, and thiols . Encompassing many of the pathways available for the modification of terminal bromides, a user guide for the chain‐end functionalization of poly(acrylates) prepared via ATRP was recently reported . Through the optimization of existing protocols based on simple small molecule transformations, the bromide end‐group ofpoly(methyl acrylate) can be quantitatively converted to a range of other functionalities, incorporating nucleophilic, electrophilic, hydrophobic, hydrophilic and charged moieties under mild, non‐inert conditions.…”

Section: Discussionmentioning

confidence: 99%

Established and emerging strategies for polymer chain‐end modification

Lunn

Discekici

Alaniz

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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The development of "controlled" and "living" polymerization processes with high end-group fidelity has enabled an unprecedented range of polymeric materials with specific chainend functionality to be prepared. This highlight provides an overview of available strategies and evaluation of recent approaches for the chain-end functionalization of polymers prepared through controlled chain-growth polymerizations. As a tribute to Professor Robert B. Grubbs on the occasion of his 75th birthday, we also take this opportunity to highlight methods for the chain-end modification of polymers prepared by ring-opening metathesis polymerization within the broader context of functional group tolerant, living polymerizations. Finally, we focus attention toward new directions in polymer chain-end modifications, describing existing gaps in current strategies, and detailing recently reported protocols that show significant improvements over traditional methods.

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End group modification of poly(acrylates) obtained via ATRP: a user guide

Abstract: The versatile and high yielding end-functionalization with a varienty of functional groups is presented for poly(acrylates) obtained by ATRP.

Cited by 59 publications

References 45 publications

Kinetics of Atom Transfer Radical Polymerization

Kinetics of Atom Transfer Radical Polymerization

Functionalization of poly(3‐hydroxybutyrate) with different thiol compounds inhibits MDM2–p53 interactions in MCF7 cells

Established and emerging strategies for polymer chain‐end modification

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