1,4:3,6-Dianhydrohexitols: Original platform for the design of biobased polymers using robust, efficient, and orthogonal chemistry*

Dianhydrohexitols (DAHs) are nontoxic and sustainable diols that have been extensively applied as monomers for the preparation of polymer materials by step- growth polymerization processes. The presence of two reactive alcohol groups was exploited to design a library of symmetric and asymmetric stereocontrolled alkyne- and/or azide-func- tionalized AA/BB and AB monomers suitable for thermal or copper(I)-catalyzed azide- alkyne cycloaddition (TAAC and CuAAC). Step-growth polymerization of these monomers yielded a series of linear polytriazoles as well as partially biosourced networks using a com- bination of AB + A 2 B 2 derivatives. Characterization of the resulting materials allowed for the establishment of a thorough structure-property relationship emphasizing the impact of monomer stereo chemistry and cycloaddition regioselectivity on materials properties.