Homopolymer bifunctionalization through sequential thiol-epoxy and esterification reactions

An optimization, quantification, and structural elucidation study

Ikhlas Gadwal, Mihaiela C. Stuparu, Anzar Khan

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

In this study, we probe various aspects of a post-polymerization double-modification strategy involving sequential thiol-epoxy and esterification reactions for the preparation of dual-functional homopolymers. For this, a general reactive scaffold, poly(glycidyl methacrylate), carrying an aromatic end-group was prepared through an atom transfer radical polymerization (ATRP) process. The glycidyl side-chains of this polymer were subjected to a base-catalyzed ring opening reaction with the thiol nucleophiles. A systematic variation in the catalyst type, catalyst loading, reaction medium, reaction temperature, and reaction time suggested that the choice and amount of catalyst had a significant impact on the outcome of the thiol-epoxy reaction. End-group analysis by 1H-NMR spectroscopy was employed to quantify the degree of the epoxy group conversion into the corresponding thio-ether moiety. The secondary hydroxyl groups generated as a result of the first functionalization reaction were then employed in the anchoring of a second functional group to the polymer repeat unit through an esterification reaction. Quantification studies suggested that an excess of the activated acid molecules was necessary to observe quantitative functional group transformation. Elemental analysis confirmed the chemical composition of the functionalized polymers. The obtained bi-functionalized polymers could be converted into a water soluble amphipathic structure in which each polymer repeat unit was substituted with a hydrophilic ammonium cation and a hydrophobic alkyl chain. Besides these, a carefully planned model compound study was also conducted to examine the regio-chemical aspects of the prepared polymers. This journal is

Original languageEnglish
Pages (from-to)1393-1404
Number of pages12
JournalPolymer Chemistry
Volume6
Issue number8
DOIs
Publication statusPublished - 2015 Feb 28
Externally publishedYes

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Esterification
Homopolymerization
Sulfhydryl Compounds
Polymers
Polymerization
Functional groups
Catalysts
Nucleophiles
Atom transfer radical polymerization
Chemical analysis
Ammonium Compounds
Scaffolds
Hydroxyl Radical
Ether
Nuclear magnetic resonance spectroscopy
Cations
Ethers
Magnetic Resonance Spectroscopy
Positive ions
Molecules

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Biomedical Engineering
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Homopolymer bifunctionalization through sequential thiol-epoxy and esterification reactions : An optimization, quantification, and structural elucidation study. / Gadwal, Ikhlas; Stuparu, Mihaiela C.; Khan, Anzar.

In: Polymer Chemistry, Vol. 6, No. 8, 28.02.2015, p. 1393-1404.

Research output: Contribution to journalArticle

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