Imide-yne click polymerization: a new and versatile tool for the toolbox of X-yne click polymerization


Aslanturk O., Sagdic G., ÇAKMAKÇI E., Durmaz H., Günay U. S.

Polymer Chemistry, cilt.15, sa.39, ss.3991-4004, 2024 (SCI-Expanded) identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 15 Sayı: 39
  • Basım Tarihi: 2024
  • Doi Numarası: 10.1039/d4py00918e
  • Dergi Adı: Polymer Chemistry
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Biotechnology Research Abstracts, Chemical Abstracts Core, Chimica, Compendex, INSPEC
  • Sayfa Sayıları: ss.3991-4004
  • Marmara Üniversitesi Adresli: Evet

Özet

The Michael reaction, a cornerstone in organic chemistry, continues to revolutionize the field with its unparalleled versatility in forming carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-sulfur bonds, paving the way for groundbreaking advancements in complex molecule and macromolecule construction. In this study, imide-yne reaction was employed at the macromolecular level for the first time to prepare linear poly(imide ester)s. A wide range of bisimides and dipropiolates were reacted through imide-yne click polymerization in the presence of 1,4-diazabicyclo[2.2.2] octane (DABCO) at room temperature. The polymerizations proceed in an anti-Markovnikov fashion, yielding the E-isomer as the major product. Polymers were obtained in high yields and their molecular weights were found to be in the range of 5.64-12.67 kDa. The remaining unreacted double bonds in the linear polymers were found to undergo further functionalization with thiols using a strong organocatalyst 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), which was also supported by a model study. Post-polymerization modification study prompted us to prepare imide-yne monomers that can react with dithiols to synthesize poly(imide thioether)s through nucleophilic thiol-ene click reaction using TBD as the catalyst. The obtained polymers displayed a wide range of glass transition temperatures and thermal stability. Thus, it can be said that the proposed method enables the synthesis of new polyimide-based structures with tailorable thermal properties. It is believed that the proposed strategy will make a significant contribution to expanding the versatility of active alkyne chemistry at the macromolecular level.