Efficient Post-Polymerization modification of pendant aldehyde functional polymer via reductive etherification reaction

Akar E., Kandemir D., Lüleburgaz S., Kumbaracı İ. V., Durmaz H.

EUROPEAN POLYMER JOURNAL, vol.177, 2022 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 177
  • Publication Date: 2022
  • Doi Number: 10.1016/j.eurpolymj.2022.111440
  • Journal Name: EUROPEAN POLYMER JOURNAL
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Aerospace Database, Chemical Abstracts Core, Communication Abstracts, INSPEC, Metadex, Civil Engineering Abstracts
  • Keywords: Reductive etherification reaction, Aldehyde, Post -polymerization modification, Chlorodimethylsilane, ALKYLENE BIS(TRIMETHYLSILYL) ETHERS, SIDE-CHAINS, SIMULTANEOUS CONSTRUCTION, SILANE REDUCTIONS, ACIDIC MEDIA, UGI-REACTION, 3-COMPONENT POLYCONDENSATION, SYMMETRICAL ETHERS, CARBONYL-COMPOUNDS, DIALDEHYDES
  • Istanbul Technical University Affiliated: Yes

Abstract

The aldehydes have always been a privilege in polymer science since the aldehyde carbonyl readily undergoes several reactions efficiently under mild conditions, ranging from non-aldol reactions to multicomponent reactions, mostly without any additive. In the current study, the versatility of the aldehyde group has been further exploited using the reductive etherification reaction (RER), which has proven to be a useful synthetic strategy to convert aldehyde or ketone carbonyls to ethers in the presence of organosilane compounds. For this purpose, a polymer platform containing pendant aldehyde units was synthesized via free radical polymerization (FRP) and modified with a variety of alcohols using chlorodimethylsilane (CDMS) as the reducing agent. The spectroscopic analyses indicated that pendant aldehydes successfully turned to corresponding ethers with quantitative or near quantitative RER efficiencies. The proposed strategy was also extended to thiols and the resultant polymers were found to be in thioacetal and/or thioether pendant forms. Given the growing demand for the development of new synthetic methodologies that can be adapted to the macromolecular level, a new insight into the modification of aldehyde-functionalized polymers has been introduced in this study.