This work reports for the first time the copolymerization studies of 11 newly synthesized epoxidized vegetable oils (EVOs) that reacted with a disulfide-based aromatic dicarboxylic acid (DCA) to produce thermoset materials with recyclability properties. These new EVOs' reactivity and properties were compared with those of the two commercial references: epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO). The structure−reactivity correlation is proposed by differential scanning calorimetry (DSC) analysis, corroborating the epoxy content of EVO monomers, the initiator effect, the copolymerization reaction enthalpy, and the temperature range. The thermomechanical properties of the obtained thermosets were evaluated and discussed in correlation with the structure and reactivity of monomers by dynamic mechanical analysis (DMA), tensile testing, and thermogravimetric analysis (TGA). It has been found that the higher the EVO functionality, the higher is the reactivity, cross-linking density, and final performances, with tan δ values ranging from 34 to 111 °C. This study investigates the chemical recycling and the solvent resistance of these vitrimerlike materials that have a high bio-based carbon content, from 58 to 79%, with potential application in coating or composite materials in the automotive sector.
The preparation of thermosets based on epoxidized vegetable oils (EVOs) involved a peculiar attention in recent years; however, most of them cannot be recycled once cross-linked. In the present work, epoxy thermosetting resins like-vitrimers with dynamic disulfide covalent bonds were prepared by copolymerizing twelve EVOs with 2,2′-dithiodibenzoic acid, as hardener. Here, we show for the first time the reprocessability, repairability, and recyclability properties of EVOs thermosets. The 3R abilities were evaluated in correlation with the EVO epoxy contents, which influence the final thermo-mechanical properties of the recycled material. The virgin versus recycled materials' comparison was studied by FT-IR, DSC, TGA, and DMA, also comparing their swelling ability and high gel content. The study investigates, in addition, the excellent shape memory properties of the reprocessed EVOs/disulfide materials.
Beyond the need to find a non-toxic alternative to DiGlycidyl Ether of Bisphenol-A (DGEBA), the serious subject of non-epichlorohydrin epoxy resins production remains a crucial challenge that must be solved for the next epoxy resin generations.
Epoxy vitrimers encompass many advantages compared to traditional epoxy materials such as recyclability, repairability, and reprocessability. These properties are induced by the incorporation of dynamic reversible covalent bonds. Recently, the incorporation of aromatic disulfide bridges that are dynamic has expanded the development of new eco-friendly epoxy materials. Herein, we studied a bio-based aliphatic disulfide based on cystamine as a hardener with a vanillin-derived biosourced epoxy to prepare fully bio-based epoxy vitrimers. This article provides a comparative study between cystamine and an aromatic disulfide benchmark hardener issued from petrol resources. This work demonstrated that the presence of this aliphatic hardener has a significant influence not only on the reactivity, but most importantly on the resulting dynamic properties. An interesting yet counterintuitive accelerating effect of the dynamic exchanges was clearly demonstrated with only 2 to 20% of molar fraction of cystamine added to the aromatic disulfide formulation. A similar glass transition was obtained compared to the purely aromatic analogue, but relaxation times were decreased by an order of magnitude.
Epoxy resins are widely used in the composite industry due to their dimensional stability, chemical resistance, and thermo-mechanical properties. However, these thermoset resins have important drawbacks. (i) The vast majority of epoxy matrices are based on non-renewable fossil-derived materials, and (ii) the highly cross-linked molecular architecture hinders their reprocessing, repairing, and recycling. In this paper, those two aspects are addressed by combining novel biobased epoxy monomers derived from renewable resources and dynamic crosslinks. Vanillin (lignin) and phloroglucinol (sugar bioconversion) precursors have been used to develop bi- and tri-functional epoxy monomers, diglycidyl ether of vanillyl alcohol (DGEVA) and phloroglucinol triepoxy (PHTE) respectively. Additionally, reversible covalent bonds have been incorporated in the network by using an aromatic disulfide-based diamine hardener. Four epoxy matrices with different ratios of epoxy monomers (DGEVA/PHTE wt%: 100/0, 60/40, 40/60, and 0/100) were developed and fully characterized in terms of thermal and mechanical properties. We demonstrate that their performances are comparable to those of commonly used fossil fuel-based epoxy thermosets with additional advanced reprocessing functionalities.
The radical‐induced cationic frontal photopolymerization (RICFP) of fully biobased epoxy composites is successfully demonstrated. This curing strategy considerably reduces the curing time and improves the efficiency of the composite fabrication. Two different natural fiber fabrics made of cellulose and flax fibers are embedded in two epoxy matrices, one derived from vanillin (diglycidylether of vanillyl alcohol‐DGEVA) and the other from petroleum (3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexanecarboxylate‐CE). After RICFP the composites are characterized by means of dynamic mechanical thermal analysis and tensile tests. The mechanical properties improved with increasing fiber content, confirming a strong adhesion between the matrix and the reinforcing fiber fabrics, which is further evidenced by scanning electron microscopy analyses of the fracture surfaces. Furthermore, these fully bio‐based composites possess comparable or even higher mechanical strength compared with the corresponding epoxy composites fabricated with conventional CE resin. A promising facile route to high‐performing natural fiber‐biobased epoxy resin composites is presented.
The
end-of-life of thermoset materials is a real issue that confronts
our society, and the strategy of introducing dynamic reversible bonds
can be a sustainable solution to overcome this problem. This study
shows an efficient way to produce biobased and recyclable thermosets,
for a circular use. To reduce the production costs linked to energy
and duration, an improved curing process is proposed by combining
aromatic and aliphatic diacid hardeners containing dynamic S–S
bonds. The work demonstrates the increased reactivity of epoxidized
vegetable oil reacted with the two diacids. The structural evolutions
during the exchange reactions that allow the recyclability were followed
by Fourier transformed-infrared and nuclear magnetic resonance spectroscopies,
high-performance liquid chromatography, and mass spectroscopy. The
curing process was studied by differential scanning calorimetry and
kinetic study.
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