Simple and Efficient Approach toward Photosensitive Biobased Aliphatic Polycarbonate Materials

Abstract

Fatty acids were used as precursors for the synthesis of photo-sensitive polycarbonate materials. In order to avoid multi-step reactions, a simple and straightforward methodology toward the synthesis of photo-sensitive monomers has been developed. Hence, a fatty acid-based cyclic carbonate bearing an unsaturation was synthesized and subsequently polymerized in a controlled manner (Ɖ=1,07) by organo-catalyzed ring-opening polymerization (ROP). A thio-cinnamate derivative was then readily synthesized via a one-pot reaction and grafted onto the polycarbonate backbone by thiol-ene reaction. The content of photo-responsive cinnamoyl moiety grafted on the polycarbonate was tunable with the reaction time. Such functionalized polycarbonates could be cross-linked (by UV irradiation at 365 nm) and de-cross-linked (irradiated at 254nm) and exhibit versatile properties ranging from rather tough materials to elastomeric networks with respect to the content of the photo-sensitive cinnamoyl moiety grafted on the polymer.

Versatile cross-linked fatty acid-based polycarbonate networks obtained by thiol–ene coupling reaction

“…We previously reported the synthesis of a bio-based polycarbonate containing dangling unsaturations. 5 Since the pendent olen groups are reasonably distributed throughout the polymer structure, we aimed at examining the photoinduced cross-linking of these polycarbonate precursors via thiol-ene chemistry, to prepare bio-based polycarbonate materials with improved thermal and mechanical properties. Indeed, such synthetic methodology was already reported for the functionalization of linear polymers but also as a mean to form cross-linked materials.…”

“…1). 5 In order to enhance the thermo-mechanical properties of these aliphatic polycarbonates, the present work is dedicated to the synthesis of versatile networks from these linear polycarbonate precursors.…”

Bio-Based Thermo-Reversible Aliphatic Polycarbonate Network

“…The solvents were of reagent grade quality and they were purified whenever necessary according to the methods reported in the literature. The polycarbonate, P(NH-Und-6CC) has been synthesized, as previously described [21].…”

“…Aliphatic polycarbonate P(NH-Und-6CC) was used as the starting materials, since its synthesis by ROP of NH-Und-6CC is well-controlled and it can be performed on a multi-gram scale according o already published protocols (see Supplementary Materials for the full protocols) [16,21]. Therefore, the first task was the preparation of a furan-functionalized polycarbonate.…”

“…However, the main disadvantage of these cross-linked materials is their inability to be reformed or recycled. As a result, the development of self-healing polymers has been a very active area of research over the last decade [17][18][19][20][21]. In 2013, the World Economic Forum even named self-healing materials among the top 10 emerging technologies and could be of interest in many areas, such as protective coatings, biomedical applications, piping, and electronics [18,22].…”