Limonene dioxide as a building block for 100% bio-based thermosets

Abstract

This study valorises the benign epoxidation of (R)-(+)-limonene to generate novel bio-resourced limonene dioxide monomers. Without additional steps of separation or functionalization, the racemic limonene dioxide was cured with glutaric...

Novel Biobased Epoxy Thermosets and Coatings from Poly(limonene carbonate) Oxide and Synthetic Hardeners

“… 2 , 3 , 5 , 6 , 16 − 19 One well-known, low-cost sustainable raw material is limonene, which is extracted from citrus fruit peels and can be used as a monomer in the production of several polymers and blends. 20 , 21 One promising example is the work developed by Mija et al, 22 who used limonene dioxide and glutaric anhydride to obtain fully biobased thermoset materials. Moreover, polycarbonates and crosslinked polymers are other alternatives with potential applications in the coating and adhesive industry.…”

A Biosourced Epoxy Resin for Adhesive Thermoset Applications

“…This is clearly evidenced when comparing our thermoset with similar biobased thermosets made from limonene-derived small organic molecules. For instance, Mija et al [5] were able to obtain a high elastic modulus (726 � 81 MPa) and tensile strength (34 � 3.5 MPa) for a fully biobased thermoset, which was prepared from limonene dioxide (LDO) and glutaric acid (GA). However, the elongation at break (5.44 � 0.69 %) was much lower than that found for the 1 : 1 PCO:Jeff thermoset (20.8 � 9.7 MPa).…”

“…[2][3][4] However, for the moment the development of more sustainable epoxy thermosets has received comparatively little attention. Mija et al [5] were the first to report a fully biobased thermoset composed of limonene dioxide and several biosourced anhydrides. Although there has been some recent development on the use of renewable epoxy derivatives, [6][7][8] most of the examples focused on the utilization of vegetable oils such as linseed oil, soybean, and castor oil among other, [9][10][11] and carbohydrates including isosorbide and itaconic acid.…”

“…However, for the moment the development of more sustainable epoxy thermosets has received comparatively little attention. Mija et al [5] . were the first to report a fully biobased thermoset composed of limonene dioxide and several biosourced anhydrides.…”

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

“…The obtained material presents T g of 90 °C, a high degradation temperature (270 °C) and good mechanical properties: σ = 27 MPa; ɛ = 3,5 %; E = 1150 MPa; E' = 1650 MPa, SD = 78. [50] Following these results, we recently investigated the influence of cis-and trans-LDO stereochemistry on copolymerization with GA. For the first time we found that the cis-LDO generates thermosets with high mechanical properties (tan δ = 116 °C, σ = 43 MPa; ɛ = 4.56 %; E = 1.36 GPa; E' = 1.68 GPa, Shore D hardness = 81). [51]…”