Life Cycle Assessment for the Organocatalytic Synthesis of Glycerol Carbonate Methacrylate

Abstract

Bifunctional ammonium and phosphonium salts have been identified as potential organocatalysts for the synthesis of glycerol carbonate methacrylate (GCMA). Three of these catalysts showed high efficiency and allowed the conversion of glycidyl methacrylate with CO2 to the desired product in >99 % conversion and selectivity. Subsequently, immobilized analogues of selected catalysts were prepared and tested. A phenol‐substituted phosphonium salt on a silica support proved to be a promising candidate in recycling experiments. The same catalyst was used in 12 consecutive runs, resulting in GCMA yields of up to 88 %. Furthermore, a life cycle assessment was conducted for the synthesis of GCMA starting from epichlorohydrin (EPH) and methacrylic acid (MAA). For the functional unit of 1 kg GCMA, 15 wt % was attributed to the incorporation of CO2, which led to a reduction of the global warming potential of 3 % for the overall process.

Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol‐Functionalized Phosphonium Salts

“…Thus, the use of glycerol as the feedstock for the preparation of value‐added products is an attractive goal. Moreover, the use of this biobased material can lead to a significant reduction in the carbon footprint, for example, in the synthesis of carbonates, compared to their production from fossil resources [6a] . Glycidol ( 11 c ) and its derivatives can be obtained from glycerol [41] .…”

Recent developments in organocatalysed transformations of epoxides and carbon dioxide into cyclic carbonates

“…In 2019, Werner et al synthesised polystyrene-supported bifunctional ammonium and phosphonium salts, which gave 95-99% isolated yields for converting glycidyl methacrylate into the corresponding cyclic carbonate, an important monomer in polymer synthesis. 145 By using 2 mol% of catalyst, at 90 o C and 10 bar of carbon dioxide for 2 h over 12 runs, isolated yields remained higher than 60% but slightly declined after each use. The activity of the catalyst against other epoxides was not tested.…”

Recent progress in the catalytic transformation of carbon dioxide into biosourced organic carbonates

“…185,186 Importantly, the latter processes have received increasing attention in recent years, 118,187,188 as they enable the integration between highly sought-after recycling of CO 2 into chemicals, [189][190][191] and the use of renewable substrates as building blocks for commodity chemicals with a low(er) carbon footprint. 24,192,193 In this section, we review the catalytic processes that have been developed (mostly in the last decade) for the cycloaddition of CO 2 to EFAs and EVOs providing oleochemical carbonates. For the sake of clarity, terminal cyclic carbonates prepared from epoxidized fatty acid derivatives are initially discussed whereas the carbonation of internal epoxides present in fatty acids and vegetable oils is discussed separately.…”