Facile and efficient bromination of hydroxyl-containing polymers to synthesize well-defined brominated polymers

Zhou, Haihua; Chen, Yi; Plummer, Christopher M.; Huang, Hui; Chen, Yongming

doi:10.1039/c7py00283a

Cited by 17 publications

(11 citation statements)

References 40 publications

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“…The synthesis of terminally brominated mPEG (mPEG–Br) derivatives was achieved by milling of mPEG–OTs with LiBr ( Scheme 1 ). Analysis of the milled reaction mixture by 1 H NMR revealed the appearance of a new triplet resonance centered at about 3.45 ppm in CDCl 3 , consistent with the methylene germinal to Br in mPEG–C H 2 -Br (Figure S2, Supporting Information File 1 ) [ 34 – 35 ]. 1 H NMR yields of 58% and 65% were obtained for reactants mPEG 750 and mPEG 2000 , respectively ( Table 2 , entries 1 and 2).…”

Section: Resultsmentioning

confidence: 91%

“…2D-HSQC was performed to validate terminal bromo functionality showing a cross-peak at 1 H, 13 C = 3.45 ppm, 30.10 ppm (Figure S3, Supporting Information File 1 ). These results are exciting given that PEG bromination is often performed under harsh conditions either via radical intermediates or using bromoacyl halides, which introduces unnecessary ester groups instead of direct bromine substitution onto the polymer chain [ 34 , 36 – 37 ].…”

Section: Resultsmentioning

confidence: 99%

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Solid-state mechanochemical ω-functionalization of poly(ethylene glycol)

Malca¹,

Ferko²,

Friščić³

et al. 2017

Beilstein J. Org. Chem.

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Poly(ethylene glycol) (PEG) is a linear polymer with a wide range of applications in chemical manufacturing, drug development and nanotechnology. PEG derivatives are being increasingly used to covalently modify small molecule and peptide drugs, as well as bioactive nanomaterials in order to improve solubility in biological serum, reduce immunogenicity, and enhance pharmacokinetic profiles. Herein we present the development of mechanochemical procedures for PEG functionalization without the need for bulk solvents, offering a cleaner and more sustainable alternative to existing solution-based PEG procedures. The herein presented mechanochemical procedures enable rapid and solvent-free derivatization of PEG with tosyl, bromide, thiol, carboxylic acid or amine functionalities in good to quantitative yields and with no polymer chain oligomerization, proving the versatility of the method.

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Section: Resultsmentioning

confidence: 91%

Section: Resultsmentioning

confidence: 99%

Solid-state mechanochemical ω-functionalization of poly(ethylene glycol)

Malca¹,

Ferko²,

Friščić³

et al. 2017

Beilstein J. Org. Chem.

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“…The values of the protons CH 2 bound to oxygen and CH 2 bound to OH, are approximately 4 and 3.9 ppm, respectively. The chemical shift value of the peak of OH was seen at 5 ppm 34,35 . Aliphatic chain protons on the allyl isothiocyanate group appear between 1.5 and 2.0 ppm.…”

Section: Resultsmentioning

confidence: 95%

“…The chemical shift value of the peak of OH was seen at 5 ppm. 34,35 Aliphatic chain protons on the allyl isothiocyanate group appear between 1.5 and 2.0 ppm. The chemical shift value of the nitrogen-bound CH 2 group is expected to be between 3.5 and 3.7 ppm, but the H 2 O peak of the DMSO solvent shields this value.…”

Section: Adsorption Experimentsmentioning

confidence: 99%

Synthesis of a new adsorbent poly(allylisothiocyanate‐co‐hydroxyethylmethacrylate‐co‐vinylimidazole) via photopolymerization: Characterization and investigation of heavy metal adsorption capacity

Saltan

2022

J of Applied Polymer Sci

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We report the copolymerization synthesis of novel poly(allylisothiocyanate‐co‐hydroxyethylmethacrylate‐co‐vinylimidazole) (PAHV) adsorbents for potential applications in the heavy metal removals. In the present study, the copolymerization reaction was introduced by photopolymerization using benzophenone as the photoinitiator. The chemical structure in the PAHV adsorbents was monitored and evaluated by Fourier transform infrared spectroscopy, 1H‐nuclear magnetic resonance, andX‐ray photoelectron spectroscopy measurements. Surface analysis and molecular weight distribution of PAHV adsorbents were performed by scanning electron microscopy and gel permeation chromatography analysis, respectively. The adsorption method, which is one of the most effective techniques, was used for the elimination of heavy metal ions from aqueous solutions in this study. In order to understand the adsorption capacity and removal efficiency of heavy metal ions by PAHV, the effects of pH value and monomer ratio in the adsorbents were investigated. Inductively coupled plasma mass spectrometry device was used for these analyses. The optimum pH values for adsorption capacity and removal efficiency of heavy metal ions have been 6–8. The removal efficiency of heavy metal ions by the various PAHV adsorbents decreased in the order: Cd2+ > Pb2+ > Co3+ > Cr3+ > Ni2+ > Cu2+.

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“…The intensities of the signals at δ = 0.95 ppm for the terminal CH 3 group and of the signal at δ = 3.38 ppm for the CH 2 group next to the trithiocarbonate match well with the expectations proving the excellent retention of the RAFT end group. Recent studies showed the synthesis of a similar polymer named poly(2‐bromoethyl methacrylate) by postmodification of poly(2‐hydroxyethyl methacrylate) with a mixture of various chemicals . Our study represents a more effective approach due to the lack of postbromination procedures and the introduction of the bromide directly to the monomer circumventing the requirement for additional tedious modification steps.…”

Section: Resultsmentioning

confidence: 96%

RAFT polymerization and thio‐bromo substitution: An efficient way towards well‐defined glycopolymers

Pröhl

Englert

Gottschaldt

et al. 2017

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

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Despite an increasing effort to design well-defined glycopolymers, the convenient synthesis of polymers with higher DPs (>100) and without tedious protection and deprotection steps remains a challenge. Combining the reversible addition fragmentation transfer (RAFT) polymerization and the efficient substitution of primary bromo groups by thiols, we were able to synthesize a set of well-defined glycopolymers with DPs of up to 115. With the polymerization of the highly reactive monomer (2-bromoethyl)-acrylate polymers with low dispersities were obtained that could efficiently be functionalized with various sugar thiol(ate)s. In particular, derivatives of D-glucose, D-galactose, and D-mannose gave excellent degrees of functionalization close to quantitative conversion using only a slight excess of the thiol. This atom efficient synthesis can even be applied for copolymers with acid or base labile components due to the use of unprotected sugar moieties and, hence, the lack of further deprotection steps. Binding studies with the lectin concanavalin A and the subsequent competition studies with a-D-methyl-mannopyranose (aMeMan) proved the effective binding of these derivatives and revealed a DP-and carbohydrate-dependent clustering and dissolution.

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Facile and efficient bromination of hydroxyl-containing polymers to synthesize well-defined brominated polymers

Abstract: This article demonstrates a new post-modification method to synthesize well-defined brominated polymers based on the bromination of hydroxyl-containing polymers.

Cited by 17 publications

References 40 publications

Solid-state mechanochemical ω-functionalization of poly(ethylene glycol)

Solid-state mechanochemical ω-functionalization of poly(ethylene glycol)

Synthesis of a new adsorbent poly(allylisothiocyanate‐co‐hydroxyethylmethacrylate‐co‐vinylimidazole) via photopolymerization: Characterization and investigation of heavy metal adsorption capacity

RAFT polymerization and thio‐bromo substitution: An efficient way towards well‐defined glycopolymers

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