Radical ring-opening polymerization of sustainably-derived thionoisochromanone

Abstract

We demonstrate computational insight and radical ring opening polymerization of a fungi-derived thionolactone, thionoisochromanone (TIC), to create homo-, block-, and statistical copolymers under entirely free radical conditions.

Development of an Efficient Thionolactone for Radical Ring-Opening Polymerization by a Combined Theoretical/Experimental Approach

“…In this study, we only focused on structures that undergo efficient ring-opening, and thus, we discarded TLD , and TIC that showed moderate to high ring-retaining propagation. We thus applied the same methodology on three of the six originally prepared thionolactones to validate our approach (Table ).…”

“…The 1 H NMR spectra before and after polymerization are depicted in Figure a with the structure of the polymer obtained after the rROP of POT with the vinyl comonomer (styrene or methyl acrylate). It is worth noting that there is no signal originating from ring-retaining polymerization (no 13 C signal between 60 and 100 ppm). − The degradation of these two preliminary copolymers was then studied by using accelerated conditions.…”

“…We showed, in particular, the negative Arrhenius behavior of such a ratio that was experimentally proven in the case of the DOT/styrene copolymerization. 22 In this study, we only focused on structures that undergo efficient ring-opening, and thus, we discarded TLD 28,29 and TIC 30 that showed moderate to high ring-retaining propagation. We thus applied the same methodology on three of the six originally prepared thionolactones to validate our approach (Table 1).…”

“…This compound copolymerizes with styrene and acrylate derivatives but with a high proportion of ring-retained moieties in the backbone. Reineke and co-workers also reported a six-membered thionolactone, thionoisochromanone ( TIC , Figure ), that not only copolymerizes with styrene but also has an undesired ring-retaining mechanism.…”

Precise construction of weather-sensitive poly(ester-alt-thioesters) from phthalic thioanhydride and oxetane

“…Incorporating sulfur atoms into the polymer main chain rationally introduces unique material properties and functions compared to their all oxygen counterparts. 1–12 In particular sulfuration renders polymers more susceptible to photolysis and oxidation although investigations are usually limited to artificial conditions involving irradiation of polymer solution with intense UV light or exposure to excess chemical agents. 13–16 Sulfur containing polymers such as polythioesters are usually synthesized via polycondensation routes or ring-opening polymerisation (ROP), yet these methods only give access to a limited number of polymer structures.…”