Preparation and Single Crystal Structure Determination of the First Biobased Furan-Polydiacetylene Using Topochemical Polymerization

• Main Authors: Yves L. Dory, Mia Caron, Vincent Olivier Duguay, Lucas Chicoine-Ouellet, Daniel Fortin, Pierre Baillargeon
• Format: Article
• Language: English
• Published: MDPI AG 2019-08-01
• Series: Crystals
• Subjects: biopolymer; sustainable materials; polydiacetylene; furan; Single Crystal X-ray Diffraction (SCXRD); carbamate; hydrogen bond; topochemical polymerization; diacetylene
• Online Access: https://www.mdpi.com/2073-4352/9/9/448

Crystal structure elucidations of bio-based polymers provide invaluable data regarding structure−property relationships. In this work, we achieved synthesis and Single Crystal X-ray Diffraction (SCXRD) structural determination of a new furan-based polydiacetylene (PDA) derivative with carbamate (urethane) functionality. Firstly, diacetylene (DA) monomers were found to self-assemble in the crystalline state in such a way that the polymerization theoretically occurred in two different directions. Indeed, for both directions, geometrical parameters for the reactive alignment of DA are satisfied and closely related with the optimal geometrical parameters for DA topochemical polymerization (d(1) = 4.7−5.2 Å, d(2) ≤ 3.8 Å, θ ≈ 45°). However, within the axis of hydrogen bonds (HB), the self-assembling monomers display distances and angles (d(1) = 4.816 Å, d(2) = 3.822 Å, θ = 51°) that deviate more from the ideal values than those in the perpendicular direction (d(1) = 4.915Å, d(2) = 3.499Å, θ ≈ 45°). As expected from these observations, the thermal topochemical polymerization occurs in the direction perpendicular to the HB and the resulting PDA was characterized by SCXRD.