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Experimental determination of activation rate constant and equilibrium constant for bromo substituted succinimide initiators for an atom transfer radical polymerization process

  • Chetana Deoghare EMAIL logo
Published/Copyright: March 17, 2022
Pure and Applied Chemistry
From the journal Pure and Applied Chemistry Volume 94 Issue 7

Abstract

Alkyl bromides are used as initiators in most of the atom transfer radical polymerization (ATRP) process and play an important role for controlling the ATRP equilibrium. In this work, the effect of solvent on equilibrium constant of ATRP (K ATRP) and rate constant of activation (k act) of three isomeric alkyl bromides [namely, N-phenyl(3-bromo-3-methyl)succinimide, N-phenyl(3-bromo-4-methyl)succinimide, and N-phenyl(3-bromomethyl)succinimide] is reported. The k act and K ATRP values of alkyl bromide are determined experimentally using UV–Vis-NIR spectrometry. The termination rate constant for model compound is calculated using DOSY NMR spectroscopy. The k act and K ATRP values for the mentioned alkyl bromides are determined in five different polar solvent and the effect of polarity is observed. The obtained values of k act and K ATRP of N-phenyl(3-bromo-3-methyl)succinimide in acetonitrile at 25 °C is 6.60 × 10−2 L mol−1 s−1 and 1.42 × 10−9, respectively. These values are quite comparable with the experimentally determined reported k act and K ATRP of values of acrylates and benzyls initiators. Alternatively, the investigation of possible chain initiation activity for the ATRP process for the mentioned alkyl bromides is carried out theoretically using density functional theory (DFT) method [B3LYP/6-31+G(d) level]. A good correlation is obtained between the experimentally determined and theoretically calculated K ATRP values of studied alkyl bromides in chosen solvents. Significantly, it is found that the values of k act and K ATRP of alkyl bromides is solvent dependent and the magnitude values of the k act and K ATRP increases with increasing the solvent polarity. The proposed bromo substituted succinimides can be used as the initiator for the polymerization of acrylates, benzyls, maleimides, and itaconimides monomer under the selected solvent system.

Keywords: ATRP; chemistry and its applications; density functional theory; DOSY NMR; equilibrium constant; rate constant of activation; VCCA-2021
Corresponding author: Chetana Deoghare, Department of Chemistry, Indus Institute of Sciences, Humanities and Liberal Studies, Indus University, Rancharda, Via Thaltej, Ahmedabad 382115, Gujarat, India, Phone: +91 2764 263414, e-mail:

Article note: A collection of invited papers based on presentations at the Virtual Conference on Chemistry and its Applications (VCCA-2021) held on-line, 9–13 August 2021.

  1. Research funding: This study was supported by Birla Institute of Technology and Science, Pilani – K. K. Birla Goa Campus, Goa, India.

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Supplementary Material

The online version of this article offers supplementary material (https://doi.org/10.1515/pac-2021-2012).

Published Online: 2022-03-17
Published in Print: 2022-07-26

© 2022 IUPAC & De Gruyter. This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License. For more information, please visit: http://creativecommons.org/licenses/by-nc-nd/4.0/

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https://doi.org/10.1515/pac-2021-2012
Keywords for this article
ATRP; chemistry and its applications; density functional theory; DOSY NMR; equilibrium constant; rate constant of activation; VCCA-2021

Articles in the same Issue

  1. Frontmatter
  2. In this issue
  3. Editorial
  4. The virtual conference on chemistry and its applications, VCCA-2021, 9–13 August 2021
  5. Conference papers
  6. Hexabenzocoronene functionalized with antiaromatic S- and Se-core-modified porphyrins (isophlorins): comparison with the dyad with regular porphyrin
  7. Bonding analysis of the C2 precursor Me3E–C2–I(Ph)FBF3 (E = C, Si, Ge)
  8. Supporting the fight against the proliferation of chemical weapons through cheminformatics
  9. Disinfecting activity of some diphenyltin(IV) benzoate derivative compounds
  10. HCV genotype-specific drug discovery through structure-based virtual screening
  11. ExcelAutomat 1.4: generation of supporting information
  12. Use of Circular Dichroism in the characterization of the fusion protein SARS-CoV-2 S protein (RBD)-hFc
  13. Experimental determination of activation rate constant and equilibrium constant for bromo substituted succinimide initiators for an atom transfer radical polymerization process
  14. Degradation of o-, m-, p-cresol isomers using ozone in the presence of V2O5-supported Mn, Fe, and Ni catalysts
  15. The beginnings of chemistry: from ancient times until 1661
  16. Chemical substitution in processes for inherently safer design: pros and cons
  17. Experimental and theoretical study of the dye-sensitized solar cells using Hibiscus sabdariffa plant pigment coupled with polyaniline/graphite counter electrode
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