Use of Limonene Epoxides and Derivatives as Promising Monomers for Biobased Polymers

Abstract

(R)‐Limonene, a renewable terpene, and its epoxidized derivatives, i. e. limonene epoxides, have prompted growing attention over the last decade as building blocks for the synthesis of biobased monomers and polymers. With the goal of replacing petroleum‐based polymers several polymerization techniques have been applied on limonene oxide and limonene dioxide monomers. This paper aims to contribute to the literature by presenting a review dedicated to limonene oxide and dioxide as raw monomers of renewable origin for the development of biobased polymers. The polymerization techniques described are namely the homopolymerization, the copolymerization with carbon dioxide and anhydrides, and the copolymerization of limonene epoxide‐based monomers. Limonene oxide polymerizations will be investigated first, followed by limonene dioxide polymerizations.

Nitrogen‐Containing Polymers Derived from Terpenes: Possibilities and Limitations

“…It can be industrially gained as a waste product from citrus fruit peel. [ 71 ] Due to its availability, it found application as greener solvent, replacing fossil alternatives, [ 72 ] but it can be also used for polymer synthesis, [ 33,73 ] for example for the production of poly(limonene carbonate). [ 74 ] The two double bonds have been subject to many derivatizations, [ 75 ] also including the introduction of amine units.…”

4D Photopolymers Derived From Ring-Opening Copolymerization of Cyclic Anhydrides and Limonene Oxide

“…39,43−58 Limonene oxide is one of the most interesting moieties because of its possession of both an epoxide and an alkene and has been the subject of a wide range of studies. 37,40,44,52,54,56,59,60 It also has found use in coatings, while limonene dioxide, which possesses two epoxides and no alkenes, has been demonstrated in low-viscosity 3D printing resins after functionalization with methacrylate moieties as a substitute for bisphenol A containing polycarbonates. 50,51,61 Limonene oxide has further been incorporated into co-and terpolymers, with the residual alkene side chains leveraged for thiol−ene functionalization postpolymerization to tailor glass transition temperature (T g ) or physical properties.…”

“…Terpene oxides offer a route toward degradable polymers with the added benefit of other potential functional groups. − Numerous reported examples include limonene oxide, elemene oxide, fatty acid oxides, castor oil epoxides, and pinene oxide, among others, for the incorporation into polyesters or polycarbonates. ,− Limonene oxide is one of the most interesting moieties because of its possession of both an epoxide and an alkene and has been the subject of a wide range of studies. ,,,,,,, It also has found use in coatings, while limonene dioxide, which possesses two epoxides and no alkenes, has been demonstrated in low-viscosity 3D printing resins after functionalization with methacrylate moieties as a substitute for bisphenol A containing polycarbonates. ,, Limonene oxide has further been incorporated into co- and terpolymers, with the residual alkene side chains leveraged for thiol–ene functionalization postpolymerization to tailor glass transition temperature ( T g ) or physical properties. ,,, …”

Versatile Heterogeneous Catalytic System for the Selective Synthesis of Limonene Epoxide and Diepoxide

“…More than 15 million tons of orange peel waste are generated annually, from which approximately 60,000 tons of R-(+)-limonene can be extracted. 9,10 Limonene can be used directly in industrial applications such as aromas, cosmetics, additive foods, and cleaning materials, but it has also been extensively used as a precursor for the synthesis of high-added-value products based on oxygenated compounds such as epoxides, diepoxides, ketones, alcohols, aldehydes, and acids. 11 The oxidation route of limonene can occur toward two competitive pathways (Figure 1): (i) double bond epoxidation yielding limonene-1,2epoxide, limonene-8,9-epoxide, limonene diepoxide, and limonene glycol, and (ii) allylic oxidation yielding carveol, carvone, and perillyl alcohol; the predominance of each pathway depends on the oxidizing agent, the catalyst, and the reaction conditions.…”

“…Although the physicochemical characteristics of citrus peel waste, such as high water content and low pH, make it difficult to handle, its valorization through essential oil extraction with R -(+)-limonene, the main compound, is a promising green process. More than 15 million tons of orange peel waste are generated annually, from which approximately 60,000 tons of R -(+)-limonene can be extracted. , …”