Polymers of Limonene Oxide and Carbon Dioxide: Polycarbonates of the Solar Economy

Abstract

Limonene epoxide (1,2-limonene oxide) readily reacts with carbon dioxide inserted in a ring-opening copolymerization reaction and forms polycarbonates of exceptional chemical and physical properties. Both poly(limonene carbonate) and poly(limonene dicarbonate) can be synthesized using low-cost Zn or Al homogeneous catalysts. This study addresses selected relevant questions concerning the technical and economic feasibility of limonene and carbon dioxide polymers en route to the bioeconomy.

CO2-fixation into cyclic and polymeric carbonates: principles and applications

“…[301][302][303][304][305] For all these bio-based resources, a challenge might be represented by their availability (and cost), which should match the desired market size of the targeted application of the cyclic or polymeric carbonate product. 306 Although the utilisation of bio-based epoxides increases the renewable character of CO 2 -based cyclic and polymeric carbonates, the hazards originating from the high toxicity of epoxides are still a concern (Table 9). A solution would be to directly synthesise the CO 2 -based carbonates from the alkene from which the epoxides are generally prepared.…”

Biobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis

“…In Southeast USA, α-pinene (60-75%) and β-pinene (20-25%) are more common, whereas turpentine from Scandinavia and Russia contains considerable amounts of (+)-3carene (40%) 21 . Chemically functionalized terpenes used for polyolefins, polyesters, polycarbonates, polyacrylates, and others with promising properties have been reported, underlining their enormous potential for bio-polymers [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37] . However, terpene-based polyamides are still rare.…”

Across the Board: Arjan Kleij

“…As for polycarbonates, polyesters based on biomonomers, such as terpene oxides, would be useful alternatives but important issues remain to be examined, including their biodegradation potential, an assessment of their mechanical properties under industrial conditions, and scaling up of their synthesis while meeting economic requisites. This also raises the question how to produce large amounts of terpene precursors; biocatalysis could offer the necessary technology to advance the development of sustainable platform molecules for the polymer industry . The typical functional character of the terpene‐based polycarbonates and polyesters allows for the creation of new and improved properties through cross‐linking, chemical derivatization, or blending.…”