Ester polyurethane (PU) foam waste was reacted at atmospheric pressure in an autoclave and using microwaves with diethylene glycol (DEG) at different PU/DEG ratios in the presence of diethanolamine as a catalyst to find the glycolysis conditions that allow for the improved recovery of the PU foam waste and enable the recycling of the whole glycolysis product in foam formulations suitable for industrial application. The recycled polyol was characterized by dynamic viscosity, hydroxyl number, water content, and density, while thermal stability was assessed using thermogravimetric analysis. In the PU foam formulation, 1% and 5% of the glycolyzed material was reused. The relationship between the reuse level of the recycled polyol and the physical properties of the foam was thoroughly investigated. It was observed that both hardness and air flow decreased with increasing recycled polyol content, particularly for the polyester type foam, while tensile strength and compression strength increased. Depending on the amount of recycled polyol and catalyst used, polyether-based foams could be obtained with a low air permeability, needed in special applications as sealed foams, or with higher air permeability desirable for comfort PU foams. The results open the way for further optimization studies of industrial polyurethane foam formulations using a glycolysis process without any separation stage.
An industrially manufactured recycled polyol, obtained by acidolysis process, was for the first time proved to be a possible replacement of the reference fossil-based polyol in a low-density formulation suitable for industrial production of flexible polyurethane foams. The influence of increasing recycled polyol amounts on the properties of the polyurethane foam has been studied, also performing foam emission tests to evaluate the environmental impact. Using 10 pbw recycled polyol in the standard formulation, significant differences of the physical properties were not observed, but increase of the recycled polyol amount to 30 pbw led to a dramatic decrease of the foam air flow and a very tight foam. To overcome this drawback, N,N′-bis[3-(dimethylamino)propyl]urea was selected as tertiary amine catalyst, enabling the preservation of foam properties even at high recycled polyol level (30 pbw). Foam emission data demonstrated that this optimized foam formulation also led to an important reduction of volatile organic compounds. The results open the way for further optimization studies in low-density flexible polyurethane foam formulations, to increase the reutilization of the polyurethane waste and reduce the amount of petroleum-based raw materials.
Following the latest developments, bio-based polyesters, obtained from renewable raw materials, mainly carbohydrates, can be competitive for the fossil-based equivalents in various industries. In particular, the furan containing monomers are valuable alternatives for the synthesis of various new biomaterials, applicable in food additive, pharmaceutical and medical field. The utilization of lipases as biocatalysts for the synthesis of such polymeric compounds can overcome the disadvantages of high temperatures and metal catalysts, used by the chemical route. In this work, the enzymatic synthesis of new copolymers of ε-caprolactone and 5-hydroxymethyl-2-furancarboxylic acid has been investigated, using commercially available immobilized lipases from Candida antarctica B. The reactions were carried out in solvent-less systems, at temperatures up to 80 °C. The structural analysis by MALDI TOF-MS, NMR, and FT-IR spectroscopy confirmed the formation of cyclic and linear oligoesters, with maximal polymerization degree of 24 and narrow molecular weight distribution (dispersity about 1.1). The operational stability of the biocatalyst was explored during several reuses, while thermal analysis (TG and DSC) indicated a lower thermal stability and higher melting point of the new products, compared to the poly(ε-caprolactone) homopolymer. The presence of the heterocyclic structure in the polymeric chain has promoted both the lipase-catalyzed degradation and the microbial degradation. Although, poly(ε-caprolactone) is a valuable biocompatible polymer with important therapeutic applications, some drawbacks such as low hydrophilicity, low melting point, and relatively slow biodegradability impeded its extensive utilization. In this regard the newly synthesized furan-based oligoesters could represent a “green” improvement route.
The purification of used oils and their introduction into production cycles lead to reduction in environmental contamination. A simulation was conducted to study the thermal degradation of sunflower oil under varying temperatures over time. In the purification process of used cooking oil, an adsorption technique using zeolite and eggshell as an adsorbent (5, 10, 20, and 30 g/100 mL used oil) was applied. To optimize purification, different doses of thermally and chemically activated adsorbents were used, at different temperatures (30 and 80 °C). Therefore, this study was conducted in batch operations to determine the effect of suitable adsorption for a contact time of the adsorbent of 2 h. In comparison, the purification of used vegetable oils was achieved using a saline solution. The adsorption capacity was evaluated by determining the physicochemical parameters of the oils before and after purification. The characterization of natural adsorbents was carried out using scanning electron microscopy (SEM) and X-ray fluorescence spectrometry (XRF). The results showed that the adsorbent in a dose of 30 g of zeolite activated with NaOH and heat-treated eggshell, respectively, exhibited a larger surface area and greater adsorption capacity. Adsorption increased with contact time. The FT-IR spectra of the oils showed the IR bands at 1097, 1160, and 1237, corresponding to the presence of the ester C-O-, 1743 for C=O ester, 2853, 2922 for (CH2, CH3), and 3008 for (C=C). The acidity and peroxide values decreased with increasing dose and contact time with zeolite or eggshell. Together, our result strongly suggests that natural adsorbents contribute to the purification of used oils.
Glucosinolates-rich extracts of some Brassicaceae sources, such as broccoli, cabbage, black radish, rapeseed, and cauliflower, were obtained using an eco-friendly extraction method, in a microwave field, with 70% ethanol, and evaluated in order to establish their in vitro antioxidant activities and anticorrosion effects on steel material. The DPPH method and Folin-Ciocâlteu assay proved good antioxidant activity (remaining DPPH, 9.54–22.03%) and the content of total phenolics between 1008–1713 mg GAE/L for all tested extracts. The electrochemical measurements in 0.5 M H2SO4 showed that the extracts act as mixed-type inhibitors proving their ability to inhibit corrosion in a concentration-dependent manner, with a remarkable inhibition efficiency (92.05–98.33%) achieved for concentrated extracts of broccoli, cauliflower, and black radish. The weight loss experiments revealed that the inhibition efficiency decreased with an increase in temperature and time of exposure. The apparent activation energies, enthalpies, and entropies of the dissolution process were determined and discussed, and an inhibition mechanism was proposed. An SEM/EDX surface examination shows that the compounds from extracts may attach to the steel surface and produce a barrier layer. Meanwhile, the FT-IR spectra confirm bond formation between functional groups and the steel substrate.