Original Fluorinated Non-Isocyanate Polyhydroxyurethanes

HIGHLIGHTS: What are the main findings? Fluorinated telechelic bis(cyclocarbonate) was synthesized through carbonylation of a fluorinated diepoxide. Fluorinated polyhydroxyurethanes (FPHUs) with different molar masses were synthesized through polyaddition reaction. Analysis showed that the FPHUs have higher molar mass, glass transition, and decomposition temperatures compared to their hydrogenated homologues. What is the implication of the main finding? New non-isocyanate polymers with improved properties. The synthesized FPHUs are potential candidates for applications requiring materials with these properties (E.g., adhesives). ABSTRACT: New fluorinated polyhydroxyurethanes (FPHUs) with various molar weights were synthesized via the polyaddition reaction of a fluorinated telechelic bis(cyclocarbonate) (bis-CC) with a diamine. The fluorinated bis-CC was initially synthesized by carbonylation of a fluorinated diepoxide, 1,4-bis(2′,3′-epoxypropyl)perfluorobutane, in the presence of LiBr catalyst, in high yield. Then, several reaction conditions were optimized through the model reactions of the fluorinated bis-CC with hexylamine. Subsequently, fluorinated polymers bearing hydroxyurethane moieties (FPHUs) were prepared by reacting the bis-CC with different hexamethylenediamine amounts in bulk at 80 °C and the presence of a catalyst. The chemoselective polymerization reaction yielded three isomers bearing primary and secondary hydroxyl groups in 61–82% yield. The synthesized fluorinated CCs and the corresponding FPHUs were characterized by (1)H, (19)F, and (13)C NMR spectroscopy. They were compared to their hydrogenated homologues synthesized in similar conditions. The gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) data of the FPHUs revealed a higher molar mass and a slight increase in glass transition and decomposition temperatures compared to those of the PHUs.