Ultrafast synthesis of phosphorus-containing polythioethers in the presence of TBD

Daglar O., Alkan B., Günay U. S., Hızal G., Tunca Ü., Durmaz H.

EUROPEAN POLYMER JOURNAL, vol.162, 2022 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 162
  • Publication Date: 2022
  • Doi Number: 10.1016/j.eurpolymj.2021.110931
  • Journal Name: EUROPEAN POLYMER JOURNAL
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Aerospace Database, Chimica, Communication Abstracts, Compendex, INSPEC, Metadex, Civil Engineering Abstracts
  • Keywords: Phosphorus polymer, Polythioether, Phosphothioester, Thiol-yne, Ultrafast polymerization, YNE CLICK POLYMERIZATION, THIOL-MICHAEL REACTIONS, FLAME RETARDANTS, POWERFUL, TOOL, POLY(PHOSPHOESTER)S, POLYPHOSPHOESTERS
  • Istanbul Technical University Affiliated: Yes

Abstract

Phosphorus-based polymers have gained much interest in recent years due to the phosphorus atoms that impart polymers interesting properties. Thus, the synthesis of phosphorus-containing polymers in practical and feasible ways is highly desirable in synthetic polymer chemistry. In this study, we report a new method based on the ultrafast thiol-yne reaction between dithiol-functionalized phosphothioester compounds and electron-deficient alkyne compounds to prepare phosphorus-containing polymers. For this purpose, two dithiol-functionalized phosphothioester compounds were synthesized and reacted with seven structurally different electron-deficient alkyne compounds in chloroform (CHCl3) in 1 min using an organocatalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). The polymerizations proceeded successfully and fourteen phosphothioester-containing polythioethers were achieved with reasonable molecular weights and high yields. The resulting polymers were characterized in detail by NMR, GPC, and DSC measurements. Given the above-mentioned demands in the preparation of phosphorus-containing polymers, the proposed approach in this study offers a rational, robust, time- and energy-saving solution to this aim. More importantly, the proposed method does not require harsh conditions, metal, acid, or base additives.