Development of high‐performance partially biobased thermoset polyester using renewable building blocks from isosorbide, 1,3‐propanediol, and fumaric acid

Abstract

Research on biobased thermoset resins has been overlooked when compared with the rapid progress on biobased thermoplastics. The objective of this work was to develop unsaturated polyester prepolymers based on building blocks derived from renewable raw materials, namely, biobased isosorbide, 1,3-propanediol, and fumaric acid, with petroleum-derived phthalic anhydride. The prepolymers developed herein behaved as low-molecular weight macromolecules (oligoesters), with M n varying between 1.2 and 1.5 kDa, but achieved a high bio-content of up to 87.1 wt%. The prepolymers were incorporated into reactive diluents comprising a blend of 2-hydroxyethyl methacrylate and styrene, formulated to be eco-friendlier and less toxic than typical styrene-only incorporation approach, thus resulting in resins with viscosities between 750 and 950 cP. These resins are suitable for use in various fiber-reinforced polymer production techniques, such as manual lamination, vacuum infusion, and pultrusion, having the benefit of presenting over 50 wt% of bio-content in some formulations. Moreover, the crosslinked polyester resins (thermosets) exhibit comparable mechanical and thermomechanical behavior to their petrochemical-based counterparts, with modulus of elasticity and tensile strength of up to 3.9 GPa and 62.1 MPa, respectively, and glass transition temperatures of up to 106 C, making them greener alternatives for high-performance structural applications.

Engineering an All-Biobased Solvent- and Styrene-Free Curable Resin

“…The starting degradation temperature (T onset ) and temperature with the highest degradation rate (T max ) were higher for the biobased resin (T onset = 137.0−181. 4 2, entry 6). The residual at 600 °C was slightly higher for the cured biobased resin (7.1%) prepared according to the best of the studied parameter settings than VER (4.5 and 5.1%).…”

“…29 Various physical, 30 chemical, 31,32 and biological processes 33,34 have been developed to extract useful biobased monomers from lignocellulosic biomass. 35−37 This article is licensed under CC-BY 4 The family of polyesters has several advantages in providing macromolecular components in thermoset resins, such as facile preparation, 38 low cost, potential biodegradability, 39 and tunable properties. 40 There have been several reports demonstrating the development of entire biobased resins; for instance, Brannstrom et al used itaconic acid (IA), succinic 41 Nevertheless, the cured resin demonstrated increased T g ∼ 12 to ≤100 °C.…”

“…The current environmental and greenhouse gas emissions challenges promote the advancement of renewable technologies and products . The employment of biobased feedstocks is instrumental in battling the environmental challenges we are facing. – These renewable resources will have tremendous importance in their usage for fabricating biobased polymers and materials for various unmet needs and substitution in existing applications. , In this context, resins such as vinyl esters used as high-performance thermoset resins are very useful components for various applications such as coatings, electrical insulation systems, buildings, and matrices in fiber-reinforced composites for a range of engineering applications . In 2020, the worldwide market size of vinyl ester was assessed at $1.1 billion, and it is anticipated to grow to $2.1 billion by the year 2030 .…”

Evaluation of 2,5‐Furandicarboxylic Acid as Building Block for Unsaturated Polyester Resins

“…vitrimers) which render re-processable thermosets possible [20][21][22] (for general readings on thermosets composed of dynamic networks see [23][24][25][26]). We will not review the literature on bio-based UPR here in detail, but we note that while all efforts remain as an excellent proof of concept, the detailed inspection of the accounts revealed only a handful contributions [27][28][29][30][31][32][33][34][35][36][37] which reported mechanical properties in agreement with industrial standards [38,39] (For a comprehensive overview of bio-based UPR see Supporting Information). These include, for example, studies with modified soybean oil [31][32][33][34], which led to UPR possessing an E-modulus of about 2.5 GPa, tensile strengths of 44 MPa, and flexural strengths of 80 MPa.…”

“…vitrimers) which render re‐processable thermosets possible [20–22] (for general readings on thermosets composed of dynamic networks see [23–26]). We will not review the literature on bio‐based UPR here in detail, but we note that while all efforts remain as an excellent proof of concept, the detailed inspection of the accounts revealed only a handful contributions [27–37] which reported mechanical properties in agreement with industrial standards [38, 39] (For a comprehensive overview of bio‐based UPR see Supporting Information).…”