A polyester containing electron deficient internal alkyne units derived from acetylene dicarboxylic acid in the main backbone was employed as a polymeric platform in copper free cycloaddition reactions.

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This study describes a straightforward post-polymerization modification (PPM) methodology from polyketone via chlorodimethylsilane (CDMS)-mediated reductive etherification reaction (RER). The polyketone platform was prepared via acyclic diene metathesis (ADMET) polymerization and reacted with a variety of alcohols in the presence of CDMS to create a wide range of polymers possessing pendant functional-alkoxy structures under mild conditions. The effect of parameters such as solvents and the amount of reactants on RER were studied. We have also explored the effect of other silane compounds on RER, none of which provided as high efficiency as the CDMS-mediated one. It has been found that the primary alcohols yielded corresponding alkoxy structures in high efficiencies, high isolated yields, and a wide range of functional group tolerance. It was also found that the formation of polyalcohol was inevitable, to some extent, during the RERs in addition to the alkoxy-functional polymers. All the polymers obtained were characterized in detail by various spectroscopic measurements, and a mechanistic aspect was also presented to evaluate the product distributions. Since operationally simple chemical methods, with a high yield and functional group tolerance, that can be easily adapted to the macromolecular level are always desired in synthetic polymer chemistry, this study promises remarkable opportunities for synthesizing functional polymers and may pave a way for the development of a novel metal-free PPM method.

Polyethers have always been privileged compounds in polymer chemistry and have found extensive applications in both academic research and industry. However, the currently employed strategies for their synthesis require harsh conditions such as ionic polymerizations together with limited precursor monomer options. In this study, a chlorodimethylsilane (CDMS)-mediated reductive etherification reaction was introduced as a versatile strategy for polyether synthesis. Accordingly, terephthalaldehyde (TPA) and 1,4-butanediol were first reacted at room temperature in the presence of CDMS using nitromethane as the polymerization solvent to reveal the optimum conditions for the proposed system. Subsequently, a variety of diols ranging from linear to sterically congested diols were reacted with TPA (and its isomers) under the optimized conditions to create a polyether library. Meanwhile, in addition to polyether having the expected alternating units, the formation of polyether stem from the self-condensation of TPA was found to be inevitable in all cases. From the proposed strategy, polyethers with a molecular weight of up to 110.4 kDa and a high alternating unit of up to 93% were obtained. The versatile and robust character of the presented strategy was supported by a model end-group study, and the polymerization behavior was examined mechanistically. It is anticipated that the presented method might be a strong candidate for polyether synthesis with different backbones, given the unlimited sources of diols.