Person: ÇAKMAKÇI, EMRAH
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ÇAKMAKÇI
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EMRAH
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Publication Metadata only New horizon in phospha-michael reaction: Ultrafast double addition of P-H bond-bearing nucleophiles to alectron-deficient triple bonds and its use for functional monomer synthesis and polymer modification(2023-01-01) ÇAKMAKÇI, EMRAH; FINDIK, VOLKAN; ERDEM, SAFİYE; Sagdic G., Daglar O., ÇAKMAKÇI E., FINDIK V., ERDEM S., Tunca Ü., Günay U. S., Durmaz H.In this work, a novel, straightforward, robust, fast, and organocatalyst-mediated phospha-Michael reaction (OCPMR) was developed for the addition of phosphorus nucleophiles to electron-deficient alkynes. Several P-H bond-bearing compounds with either fully aliphatic or aromatic units were utilized for this newly developed reaction, and it was found that phosphorous species containing only aromatic groups reacted with activated alkynes within 5 min at room temperature. The reaction led to a fast double-addition of the phosphorous compounds to the triple bond of the alkynes. An in-depth analysis of the reaction mechanism and selectivity of this OCPMR was performed using computational methods. Using the developed method, double-phosphorylated allyl-functional monomers were synthesized and subsequently used for the synthesis of linear and crosslinked polymers via thiol-ene photopolymerization. The thermoset materials exhibited LOI values as high as 26.4%. We also showed that polyesters having electron-deficient triple bonds could be easily functionalized with the P-H bond-bearing compounds. The synthetic method proposed herein promises easy and fast P-C bond formation under mild reaction conditions, and it is a straightforward method for the synthesis of phosphorus-containing monomers, linear or crosslinked polymers, and for polymer post-functionalization. We believe this feature will be of great interest not only to material chemists and polymer scientists but also to organic chemists, pharmaceutical researchers, etc.Publication Metadata only POSS—Thermosetting polymer nanocomposites(Elsevier Science, Oxford/Amsterdam , 2021-03-01) ÇAKMAKÇI, EMRAH; Çakmakçı E.Publication Metadata only Imide-yne click polymerization: a new and versatile tool for the toolbox of X-yne click polymerization(2024-01-01) ÇAKMAKÇI, EMRAH; Aslanturk O., Sagdic G., ÇAKMAKÇI E., Durmaz H., Günay U. S.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.