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

New Horizon in Phospha-Michael Reaction: Ultrafast Double Addition of P–H Bond-Bearing Nucleophiles to Electron-Deficient Triple Bonds and Its Use for Functional Monomer Synthesis and Polymer Modification

“…An extended and much more detailed parametric study is still in progress, and the effects of other parameters are part of another ongoing study. Within the scope of this work, we preferred TBD as the catalyst due to its outstanding performance in Michael reactions. − ,, Finally, for simplicity, the parametric studies were conducted by using DMAD, and the results obtained from these studies are collected in Table .…”

“…In recent years, electron-deficient alkyne-containing monomers/polymers have gained much interest to prepare new polymeric materials due to the excellent reactivity of such alkynes toward sulfur-, nitrogen-, and oxygen-based nucleophiles. Indeed, reactions between such nucleophiles and electron-deficient alkynes have proven to proceed rapidly under mild conditions, with high efficiency and without the need to use metal catalysts. − In this regard, our group has demonstrated the feasibility of the synthesis and modification of these monomers/polymers for various applications such as phase change materials, flame-retardant thermosets, hydrophobic coatings, and composites. − We have previously shown that the acetylenedicarboxylic acid-based polyesters can be easily modified via aza-Michael, thio-Michael, and azide-alkyne click cycloaddition reactions in the absence of a metal catalyst. Thiol compounds, organic azides, and primary and secondary amines were easily attached to these polyester backbones in a matter of seconds. − Furthermore, we prepared acetylenedicarboxylic acid diallyl ester (ACDAE) and functionalized this monomer via the aforementioned click reactions with either perfluorinated chains or phosphorus- or amine-containing groups .…”

Ultrafast Poly(disulfide) Synthesis in the Presence of Organocatalysts

“…Moreover, neither altering the solvent nor diluting the reaction medium yielded a soluble polymer, indicating highly rigid polymeric structures. In addition to commercially available dithiols, a synthetic dithiol having a phosphorus unit was also examined in this study. The poly­(disulfide) (P11) synthesized from this structure gave a moderate molecular weight of 10.2 kDa.…”

Propiolated Castor Oil: A Novel and Highly Versatile Bio-Based Platform for Extremely Fast, Catalyst-, and Solvent-Free Amino-yne Click Reactions

“…Recently, our group has been interested in the metal-free click reactions, modifications, and polymerization of electron-deficient triple bond-containing monomers such as acetylene dicarboxylic acid and its derivatives. − We have shown that polyesters containing acetylene dicarboxylate on their backbone can be easily modified with aza-Michael and thiol-Michael reactions under benign conditions, in the absence of metal catalysts, and in high yields. − We have demonstrated that diallyl esters of acetylene dicarboxylic acid can be functionalized similarly. , In light of the studies in the literature and foresights that we have gained with our studies on electron-deficient triple bond-containing monomers, we speculated that the activated triple bond-containing castor oil could be a versatile platform for the synthesis of bio-based functional materials and thermoset polymers. Here, we present the synthesis of propiolated castor oil and demonstrate its subsequent functionalization with a series of primary and secondary amines (Scheme ).…”