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Inexpensive dyes available at the industrial scale, namely, rhodamine B (RhB), rhodamine 6G (Rh6G) and methylene blue (MB), were investigated as organocatalysts for the cycloaddition of CO2 to styrene oxide to yield styrene carbonate under solvent-free conditions (80 °C, 10 bar CO2, 24 h). Each of these dyes consists of a bulky cation, and a chloride anion that can act as a nucleophilic catalytic species in the target reaction. In order to prepare additional catalysts, the Cl− containing dyes were ion-exchanged with KX (X = Br, I) to afford their counterparts with Br− or I− as the anion. Among this set of nine organocatalysts (three dyes, each with three types of halide), the highest yield of styrene carbonate was obtained with Rh6G-I, and trends were identified based on the nature of the organic cation and halide, with the latter having a much larger impact on the activity (I− > Br− > Cl−). Additionally, we explored the effect of adding H2O as a green, inexpensive hydrogen bond donor acting as a co-catalyst, further optimising the styrene carbonate yield (96% with RhB-I and Rh6G-I in the presence of 50 mg H2O). However, the activity of these organocatalysts was only modest if the reaction temperature was decreased to 45 °C. To tackle this limitation, we designed a tailored yet straightforward modification of RhB-I to synthesise a bifunctional organocatalyst bearing a hydrogen bond donor in proximity of the iodide anion (RhB-EtOH-I). This strategy proved successful and the RhB-EtOH-I catalyst achieved a major increase in styrene carbonate yield (29% after 18 h at 45 °C, 10 bar CO2) compared to the RhB-I/H2O catalytic system (7%). The RhB-EtOH-I catalyst was also versatile and promoted the conversion of a broad scope of epoxides with good to high cyclic carbonate yields under relatively mild reaction conditions (60 °C, 10 bar, 24 h). Although these dye organocatalysts were homogeneous, RhB-EtOH-I could be easily recovered by precipitation with diethyl ether and reused without any loss of catalytic activity. Additionally, we demonstrated that nanofiltration was an effective technique for removing the dye organocatalysts from the cyclic carbonate, affording a high purity product (≤0.1 ppm of RhB in propylene carbonate). The metal-free nature of the optimum organocatalyst (RhB-EtOH-I), its facile preparation and the low cost and commercial availability of its precursors, its promising activity under mild reaction conditions and its reusability are all assets in the context of green chemistry and for potential large-scale applicability. [ABSTRACT FROM AUTHOR]

Inexpensive dyes available at the industrial scale, namely, rhodamine B (RhB), rhodamine 6G (Rh6G) and methylene blue (MB), were investigated as organocatalysts for the cycloaddition of CO2 to styrene oxide to yield styrene carbonate under solvent-free conditions (80 °C, 10 bar CO2, 24 h). Each of these dyes consists of a bulky cation, and a chloride anion that can act as a nucleophilic catalytic species in the target reaction. In order to prepare additional catalysts, the Cl− containing dyes were ion-exchanged with KX (X = Br, I) to afford their counterparts with Br− or I− as the anion. Among this set of nine organocatalysts (three dyes, each with three types of halide), the highest yield of styrene carbonate was obtained with Rh6G-I, and trends were identified based on the nature of the organic cation and halide, with the latter having a much larger impact on the activity (I− > Br− > Cl−). Additionally, we explored the effect of adding H2O as a green, inexpensive hydrogen bond donor acting as a co-catalyst, further optimising the styrene carbonate yield (96% with RhB-I and Rh6G-I in the presence of 50 mg H2O). However, the activity of these organocatalysts was only modest if the reaction temperature was decreased to 45 °C. To tackle this limitation, we designed a tailored yet straightforward modification of RhB-I to synthesise a bifunctional organocatalyst bearing a hydrogen bond donor in proximity of the iodide anion (RhB-EtOH-I). This strategy proved successful and the RhB-EtOH-I catalyst achieved a major increase in styrene carbonate yield (29% after 18 h at 45 °C, 10 bar CO2) compared to the RhB-I/H2O catalytic system (7%). The RhB-EtOH-I catalyst was also versatile and promoted the conversion of a broad scope of epoxides with good to high cyclic carbonate yields under relatively mild reaction conditions (60 °C, 10 bar, 24 h). Although these dye organocatalysts were homogeneous, RhB-EtOH-I could be easily recovered by precipitation with diethyl ether and reused without any loss of catalytic activity. Additionally, we demonstrated that nanofiltration was an effective technique for removing the dye organocatalysts from the cyclic carbonate, affording a high purity product (≤0.1 ppm of RhB in propylene carbonate). The metal-free nature of the optimum organocatalyst (RhB-EtOH-I), its facile preparation and the low cost and commercial availability of its precursors, its promising activity under mild reaction conditions and its reusability are all assets in the context of green chemistry and for potential large-scale applicability. [ABSTRACT FROM AUTHOR]

We report the fixation of carbon dioxide (CO2) into novel rubber polymers based on polycarbonate domains. Our strategy consisted in the atom-efficient terpolymerisation of CO2 with a long-alkyl-chain epoxide and an unsaturated epoxide to obtain polycarbonates with a glass transition temperature (Tg) below room temperature and with pendant double bonds along the backbone to enable peroxide-promoted cross-linking, thus generating an elastic rubber. First, a wide range of epoxides with long alkyl chains (C6-C12) were coupled with CO2 to give polycarbonates with high yields, using a binary catalytic system consisting of an aluminium amino-tris(phenolate) complex and bis(triphenylphosphoranylidene) ammonium chloride (PPNCl). The synthesised polycarbonates were characterised using FTIR and NMR spectroscopy to determine yields and selectivity, using DSC to measure the Tg, and using GPC to obtain the molecular weight distribution. Next, the terpolymerisation was carried out by including allyl glycidyl ether (AGE) in the reaction mixture together with a long-alkyl-chain epoxide and CO2. Almost complete epoxide conversions (81-100%) and extremely high selectivity (>97%) towards the desired polycarbonates were achieved, with only traces of the cyclic carbonate side-products. The obtained polycarbonates displayed a Tg < 0 °C and thus behave as low-viscosity fluids at room temperature. The pendant unsaturated groups introduced with the AGE monomers allowed cross-linking of the terpolymers with dicumyl peroxide, leading to an elastic rubber-like behaviour as witnessed by their markedly decreased solubility in gel-content tests and by their storage modulus, loss modulus, and Tg, which were determined by dynamic mechanical analysis (DMA). In summary, we have successfully demonstrated that the terpolymerisation of long-chain epoxides, AGE and CO2 yields polycarbonates that can be cross-linked to obtain elastic rubber properties, thus opening the prospects for a new range of applications for CO2-based green polycarbonates. [ABSTRACT FROM AUTHOR]