Synthesis Of Biobased Epoxy Resins Research Articles

Recent Development of Functional Bio-Based Epoxy Resins

The development of epoxy resins is mainly dependent on non-renewable petroleum resources, commonly diglycidyl ether bisphenol A (DGEBA)-type epoxy monomers. Most raw materials of these thermoset resins are toxic to the health of human beings. To alleviate concerns about the environment and health, the design and synthesis of bio-based epoxy resins using biomass as raw materials have been widely studied in recent decades to replace petroleum-based epoxy resins. With the improvement in the requirements for the performance of bio-based epoxy resins, the design of bio-based epoxy resins with unique functions has attracted a lot of attention, and bio-based epoxy resins with flame-retardant, recyclable/degradable/reprocessable, antibacterial, and other functional bio-based epoxy resins have been developed to expand the applications of epoxy resins and improve their competitiveness. This review summarizes the research progress of functional bio-based epoxy resins in recent years. First, bio-based epoxy resins were classified according to their unique function, and synthesis strategies of functional bio-based epoxy resins were discussed, then the relationship between structure and performance was revealed to guide the synthesis of functional bio-based epoxy resins and stimulate the development of more types of functional bio-based epoxy resins. Finally, the challenges and opportunities in the development of functional bio-based epoxy resins are presented.

Functional Management of Waste Wood Flour as an Example of a 'Greener' Approach towards the Synthesis of Bio-Based Epoxy Resins.

Nowadays, in the era of growing ecological awareness, composites based on synthetic or bio-based polymers and fillers of natural origin find various potential applications. Plant-based materials are obtained using plant-derived materials, such as e.g., vegetable oil or wood fillers. Such synthesis of polymer composites allows for the selection of the reactants in terms of the potential requirements of the application. In the presented research polymer composites were obtained using bio-based high molecular-weight epoxy resins of hydroxylated soybean oil (SMEG) and a low-molecular-weight epoxy resin (EPR 0162) filled with the oak wood flour waste from the production of parquet flooring. To increase the poor compatibility between the highly hydrophilic wood fibers and the hydrophobic polymer matrix, waste wood flour (WF) was subjected to chemical modifications (mercerization, acetylation, and diisocyanate modification). Based on performed FT-IR and SEM analysis of wood flour, it was found that, among all performed modifications, the acetylation allows for the hydroxyl groups removal to the greatest extent. As a result of sequence synthesis including (1) the synthesis of SMEG_EPR polyaddition product, (2) the introduction of WF followed by its (3) curing with diisocyanate, obtained wood/polymer composites contain about 40% of raw materials of natural origin. As a consequence of the carried out modification of the wood waste flour, the compatibility of the filler and the bio-based polymer matrix was improved, resulting in an improvement in compressive strength by 3.51 MPa (SMEG_EPR_2% WF-10% NaOH) and 2.19 MPa (SMEG_EPR_2% A-WF) compared to samples containing unmodified wood flour. Additionally, concerning the results registered for pure SMEG_EPR composition, the introduction of 2 wt.% of wood filler resulted in a three/fourfold increase in the elongation at the break of the composition containing unmodified and chemically modified wood flour (10.99%-SMEG_EPR_2%WF; SMEG_EPR_2%WF-5%NaOH-10.36%; SMEG_EPR_2%WF-10%NaOH-9.54%, and 12.15%-SMEG_EPR_2%A-WF). Moreover, the incorporation of wood filler increased the value of the compression set of samples (2.40%-SMEG_EPR_2%WF, 2.39%-SMEG_EPR_2%WF-5%NaOH, and 2.34% for SMEG_EPR_2%WF-10%NaOH compared with 2.32%-SMEG_EPR).

Biobased Epoxy Synthesized from a Vanillin Derivative and Its Reinforcement Using Lignin-Containing Cellulose Nanofibrils

A simple and rapid synthesis of biobased epoxy resin derived from vanillyl alcohol was performed, and its chemical structure was confirmed by FTIR and 1H and 13C NMR spectroscopies. Vanillin-based epoxy resin (VE) was further reinforced by lignin-containing cellulose nanofibrils (LCNFs) with different weight ratios. Characteristics of the resin and the nanocomposites, including the curing process, chemical structure, morphology, mechanical performance, thermo-mechanical properties, and thermal degradation behavior, were studied. A significant improvement in the mechanical performance of the nanocomposites was achieved with a low level of nanofibril addition. Tensile strength and toughness increased by 81% and 185%, respectively, when 1 wt % of LCNFs were used. The nanocomposite also showed an increase in thermo-mechanical properties as measured by dynamic mechanical analysis (DMA) and increased resistance to thermal degradation as shown by higher onset temperature and final char value in thermogravimetric analysis (TGA). This study showcased a promising approach to make environmentaly friendly sustainable biobased epoxy products with superior performance.

Synthesis of bio-based epoxy resin from gallic acid with various epoxy equivalent weights and its effects on coating properties

The bio-based epoxy resins for coating application were synthesized from gallic acid (GA) in various molar ratios with epichlorohydrin (ECH). The reaction was carried out in the presence of sodium hydroxide (NaOH) and phase-transfer catalyst tetrabutylammonium bromide. The reaction progress rate at various molar ratios as 1:8, 1:12, and 1:16 with respect to time was monitored by calculating the epoxy content. The epoxy content value increases in the product as the molar ratio of GA to ECH increases. Epoxy equivalent weight of products was evaluated by physiochemical method and structure illustrated by Fourier transform infrared and 1H-nuclear magnetic resonance spectroscopy. This bio-based epoxy resin was cured with polyamide hardener, and the coating properties such as mechanical, chemical, and solvent resistance were studied. The cured films have been evaluated for glass transition temperature (T g) and thermal behavior by a differential scanning calorimeter and thermogravimetric analysis, respectively. The bio-based epoxy coatings show interesting mechanical, chemical, and thermal properties as compared to the conventional epoxy resin. The gel and water absorption of polyamide-cured coatings has also been evaluated.

Functionalization of the active ingredients of Japanese green tea (Camellia sinensis) for the synthesis of bio-based epoxy resin

The active ingredients of Japanese green tea (Camellia sinensis) were utilized to synthesize bio-based epoxy resin. The catechin compounds in the aqueous extract of green tea were functionalized with epichlorohydrin under alkaline conditions in the presence of tetramethylammonium chloride (TMAC), a water soluble phase transfer catalyst. A good yield of resin was synthesized, and curing was performed with methanol soluble lignin extracted from eucalyptus. The epoxy networks, so synthesized, were compared with bisphenol-A (BPA)-derived epoxy network. The thermal and mechanical properties of the bio-based resin were assessed through thermogravimetric, flexural strength, and glass transition (Tg) analyses. Catechin-based epoxy networks were found to exhibit good thermal and mechanical properties, rendering them potential BPA substitutes. The thermal decomposition temperature resulting in 5% weight loss (Td5) of synthesized epoxy resin was found to be above 300°C, which is slightly lower than that of BPA-derived epoxy resin. The synthesized bio-based resins meet the requirement for the dip-shoulder resistant temperature (250–280°C), with Tg values ranging from 155 to 178°C, highlighting their potential use as one of the most suitable BPA substituents as well as their use in electronic materials.

Epoxy resin synthesis using low molecular weight lignin separated from various lignocellulosic materials

A low molecular weight lignin from various lignocellulosic materials was used for the synthesis of bio-based epoxy resins. The lignin extracted with methanol from steam-exploded samples (steaming time of 5min at steam pressure of 3.5MPa) from different biomasses (i.e., cedar, eucalyptus, and bamboo) were functionalized by the reaction with epichlorohydrin, catalyzed by a water-soluble phase transfer catalyst tetramethylammonium chloride, which was further reacted with 30wt% aqueous NaOH for ring closure using methyl ethyl ketone as a solvent. The glycidylated products of the lignin with good yields were cured to epoxy polymer networks with bio-based curing agents i.e., lignin itself and a commercial curing agent TD2131. Relatively good thermal properties of the bio-based epoxy network was obtained and thermal decomposition temperature at 5% weight loss (Td5) of cedar-derived epoxy resin was higher than that derived from eucalyptus and bamboo. The bio-based resin satisfies the stability requirement of epoxy resin applicable for electric circuit boards. The methanol-insoluble residues were enzymatically hydrolyzed to produce glucose. This study indicated that the biomass-derived methanol-soluble lignin may be a promising candidate to be used as a substitute for petroleum-based epoxy resin derived from bisphenol A, while insoluble residues may be processed to give a bioethanol precursor i.e., glucose.

Synthesis and Properties of a Bio‐Based Epoxy Resin with High Epoxy Value and Low Viscosity

A bio-based epoxy resin (denoted TEIA) with high epoxy value (1.16) and low viscosity (0.92 Pa s, 258C) was synthesized from itaconic acid and its chemical structure was confirmed by 1H NMR and 13C NMR spectroscopy. Its curing reaction with poly(propylene glycol) bis(2-aminopropyl ether) (D230) and methyl hexahydrophthalic anhydride (MHHPA) was investigated. For comparison, the commonly used diglycidyl ether of bisphenol A (DGEBA) was also cured with the same curing agents. The results demonstrated that TEIA showed higher curing reactivity towards D230/MHHPA and lower viscosity compared with DGEBA, resulting in the better processability. Owing to its high epoxy value and unique structure, comparable or better glass transition temperature as well as mechanical properties could be obtained for the TEIA-based network relative to the DGEBA-based network. The results indicated that itaconic acid is a promising renewable feedstock for the synthesis of bio-based epoxy resin with high performance.