Polyhydroxyurethanes from Biobased Monomers and CO₂: A Bridge between Sustainable Chemistry and CO₂ Utilization^†

Abstract

Comprehensive SummaryPolyhydroxyurethanes (PHUs) have received considerable attention in the last decade as potential alternatives to traditional phosgene‐based polyurethanes (PUs). The development of suitable 5CC (five membered‐ring cyclic carbonate) precursors bearing multiple carbonate moieties (multi‐5CCs) is a key requisite for preparing PHUs by polyaddition reaction with bis‐ or polyamines. Producing sustainable PHUs from CO2‐based five‐membered cyclic carbonates (5CCs) obtained from biobased epoxides is a valuable strategy to bridge CO2 utilization and the upcycling of renewable substrates. In this context, while many multi‐5CC monomers reported in the literature are oil‐based, recent efforts have led to the development of a large variety of multifunctional 5CCs that are produced by the combination of CO2 and renewable resources such as fatty acids and vegetable oils, lignin, terpenes, and sugars. In this work, recent crucial advances (2019—2023) on PHUs prepared from bis‐ and multi‐5CCs produced from CO2 and (partially/potentially) biobased substrates are reviewed with respect to their synthesis, thermal and mechanical properties, and their recent, emerging applications.

Facile synthesis of polycarbonates from biomass-based eugenol: catalyst optimization for selective copolymerization of CO2 and eugenol to achieve polycarbonates

“…Nevertheless, we acknowledge the fact that we have not at this stage designed a strategy for making this process truly sustainable by avoiding all petroleum-based reagents. 47 Several of these complexes afford high levels of copolymers or cyclic carbonates depending on the electron density at the metal center. Included in these studies is the synthesis of a triblock polymer of PEGC- b -PEuC- b -PEGC which upon undergoing thiol–ene click chemistry with mercaptoacetic acid and deprotonation with NH 4 OH, provides nano-micelles in water.…”

Catalytic Strategies for the Cycloaddition of CO2 to Epoxides in Aqueous Media to Enhance the Activity and Recyclability of Molecular Organocatalysts

“…In a different work, Mazo and Rios [119] applied the methodology developed by Sun et al [113] for the challenging carbonation of epoxidized soybean oil (ESBO) [120][121][122]. The cyclic carbonate product (CSBO) is a crucially important precursor for the synthesis of non-isocyanate polyurethanes in the form of PHUs [29,30,32]. The addition of 33 mol% water relative to the epoxide accelerated the cycloaddition reaction of CO 2 to ESBO at 120 • C catalyzed by TBAB under a continuous CO 2 flow leading to a reduction in the t 1/2 (time for the conversion of 50% epoxides in ESBO to cyclic carbonate moieties) of 70%.…”

“…Indeed, ethylene carbonate is produced in the Asahi-Kasei process as a precursor of linear carbonates during the phosgene-free synthesis of polycarbonates [27,28]. A variety of compounds containing multiple cyclic carbonate groups has been investigated for the synthesis of polyhydroxy urethanes (PHUs) by step-growth polymerization with polyamines leading to increasingly viable isocyanate-free routes towards traditional polyurethane replacements [29][30][31][32][33]. Other important applications of cyclic organic carbonates are as solvents [34,35], surfactants [36], demulsifiers [37], and precursors of more complex molecules [38,39].…”

“…Molecules 2024, 29, x FOR PEER REVIEW 2 of 21 polyurethane replacements [29][30][31][32][33]. Other important applications of cyclic organic carbonates are as solvents [34,35], surfactants [36], demulsifiers [37], and precursors of more complex molecules [38,39].…”

Revisiting the Potential of Group VI Inorganic Precatalysts for the Ethenolysis of Fatty Acids through a Mechanochemical Approach

“…Recent years have seen a growing interest in the development of a broad portfolio of bioderived compounds as alternatives to the traditional fossil fuel-derived chemicals. − Naturally available vegetable oils (VOs) are a major feedstock for biorefineries, , leading to a variety of so-called oleochemicals with ramifications in the synthesis of surfactants, , lubricants, polymers, − and other useful compounds such as carbonated vegetable oils. ,− An important class of oleochemicals is represented by functional olefins such as 9-decenoic acid methyl ester (9-DAME), which is a valuable fine chemical with potential application for the preparation of biodiesel surrogates, , bioaviation fuel, and as a starting material for the preparation of diverse functional compounds. − 9-DAME can be obtained from the ethenolysis (metathetic cleavage with ethene) of oleic fatty acid ester chains derived from VO transesterification leading to the formation of an equivalent of 1-decene, a valuable α-olefin used for the synthesis of polymers and food additives just to cite some applications. The catalytic ethenolysis of oleic fatty acids to produce 9-DAME and 1-decene has been studied in the past. ,, Homogeneous ruthenium alkylidene complexes are powerful catalysts for the ethenolysis of methyl oleate, showing high catalytic turnover at moderate methyl oleate conversion under 10 bar ethylene. , However, given the high cost of ruthenium-based catalysts and the geographically restricted availability and critical resource status of ruthenium, there has been an increasing interest toward alkylidene complexes of inexpensive and ubiquitously available metals such as molybdenum. , A homogeneous molybdenum imido alkylidene monoaryloxide monopyrrolide complex was reported to carry out the ethenolysis of methyl oleate with high yields and selectivity at room temperature under 10 bar ethylene .…”