Open-Cell Spray Polyurethane Foams Based on Biopolyols from Fruit Seed Oils.

Natural oils from watermelon, cherry, black currant, grape and pomegranate fruit seeds were applied in the synthesis of biopolyols using the transesterification reaction. In this manuscript, the preparation possibility of open-cell foams from a polyurethane system in which petrochemical polyol was fully replaced with biopolyols is analyzed. Firstly, polyurethane foam systems were developed on a laboratory scale, and they were next tested under industrial conditions. It was shown that the foaming method has a significant impact on the foaming process and the cell structure of obtained foams as well as their thermal insulation properties. Based on the conducted research, it was found that the method of processing the polyurethane system has a significant impact on the properties of open-cell spray foams. Foams produced under industrial conditions have a much higher cell density, which has a positive effect on their selected physical-mechanical properties compared to foams produced on a laboratory scale. The open-cell biofoams obtained using a high-pressure machine had apparent densities 12-17 kg/m3, thermal conductivity coefficients 35-37 mW/m·K, closed-cell contents < 10% and were dimensionally stable at low and high temperatures.

From Bioresources to Thermal Insulation Materials: Synthesis and Properties of Two-Component Open-Cell Spray Polyurethane Foams Based on Bio-Polyols from Used Cooking Oil.

Open-cell spray polyurethane foams are widely used as highly efficient thermal insulation materials with vapor permeability and soundproofing properties. Unfortunately, for the production of commercial foams, mainly non-renewable petrochemical raw materials are used. The aim of this study was to determine the possibility of completely replacing petrochemical polyols (the main raw material used in the synthesis of polyurethanes, alongside isocyanates) with bio-polyols obtained from used cooking oils, classified as waste materials. The research consisted of three stages: the synthesis of bio-polyols, the development of polyurethane foam systems under laboratory conditions, and the testing of developed polyurethane spray systems under industrial conditions. The synthesis of the bio-polyols was carried out by using two different methods: a one-step transesterification process using triethanolamine and a two-step process of epoxidation and opening oxirane rings with diethylene glycol. The obtained bio-polyols were analyzed using gel chromatography and nuclear magnetic resonance spectroscopy. The developed polyurethane foam formulations included two types of fire retardants: halogenated tris(1-chloro-2-propyl) phosphate (TCPP) and halogen-free triethyl phosphate (TEP). In the formulations of polyurethane systems, reactive amine catalysts were employed, which become incorporated into the polymer matrix during foaming, significantly reducing their emission after application. The foams were manufactured on both a laboratory and industrial scale using high-pressure spray machines under conditions recommended by commercial system manufacturers: spray pressure 80-100 bar, component temperature 45-52 °C, and component volumetric ratio 1:1. The open-cell foams had apparent densities 14-21.5 kg/m3, thermal conductivity coefficients 35-38 mW/m∙K, closed-cell contents <5%, water vapor diffusion resistance factors (µ) <6, and limiting oxygen indexes 21.3-21.5%. The properties of the obtained foams were comparable to commercial materials. The developed polyurethane spray systems can be used as thermal insulation materials for insulating interior walls, attics, and ceilings.

Cork Porous Biocomposites with Polyurethane Matrix Modified with Polyol Based on Used Cooking Oil.

Renewable materials are materials that are replenished naturally and can be used again and again. These materials include things such as bamboo, cork, hemp, and recycled plastic. The use of renewable components helps to reduce the dependence on petrochemical resources and reduce waste. Adopting these materials in various industries such as construction, packaging, and textiles can lead to a more sustainable future and decrease the carbon footprint. The presented research describes new porous polyurethane biocomposites based on used cooking oil polyol (50 per hundred polyol-php) modified with cork (3, 6, 9, and 12 php). The research described here demonstrated that it is possible to replace some petrochemical raw materials with raw materials of renewable origin. This was achieved by replacing one of the petrochemical components used for the synthesis of the polyurethane matrix with a waste vegetable oil component. The modified foams were analyzed in terms of their apparent density, coefficient of thermal conductivity, compressive strength at 10% of deformation, brittleness, short-term water absorption, thermal stability, and water vapor permeability, while their morphology was examined using scanning electron microscopy and the content of closed cells. After the successful introduction of a bio-filler, it was found that the thermal insulation properties of the modified biomaterials were comparable to those of the reference material. It was concluded that it is possible to replace some petrochemical raw materials with raw materials of renewable origin.

Application of Modified Seed Oils of Selected Fruits in the Synthesis of Polyurethane Thermal Insulating Materials.

The use of alternative raw material sources in polyurethane chemistry is necessary given the limited supply of fossil fuels, their rising prices and the concern for sustainability. The production of biopolyols from edible vegetable oils such as rapeseed oil, soybean oil or sunflower oil is often proposed. In order to avoid conflict with the global food economy, non-edible or waste oils are hoped to find application in chemical synthesis. The possibility of using oils from selected fruit seeds to obtain biopolyols is analyzed in this manuscript. Five biopolyols were obtained from watermelon, cherry, black currant, grape and pomegranate fruit seeds using the transesterification reaction of the oils with triethanolamine. Thermal insulating polyurethane foams were then obtained by replacing 75% of petrochemical polyol with the biopolyols in polyurethane systems. Based on an analysis of the foaming process, it was found that the incorporation of triethanolamine molecules into the biopolyols causes a catalytic effect. The use of such biopolyols allows eliminating the catalyst from a polyurethane foam formulation. The polyurethane biofoams obtained with the pomegranate-seed-based biopolyol were characterized by the highest content of closed cells (45 vol.%). The lowest content was found for the foams containing the currant-seed-based biopolyol (9%). The foams were characterized by thermal conductivity coefficients between 32 and 35 kW/m·K and densities of approximately 40 kg/m3. Good dimensional stability and compressive strength between 100 and 250 kPa make them suitable for use in construction.

Impact of Various Catalysts on Transesterification of Used Cooking Oil and Foaming Processes of Polyurethane Systems.

The search for new sources of raw materials that can be used in the synthesis of polyurethanes and other polymer groups is extremely important. Currently, according to the principles of green chemistry and a circular economy, waste materials with a high reuse potential are being sought. This article presents a way of obtaining used-cooking-oil-based compounds capable of participating in the reaction of polyurethane creation. The transesterification reaction can be carried out using a variety of homo- and heterogeneous acid or base catalysts. Here, we looked at the impact of selected catalysts on the course of transesterification reactions, the composition of the post-reaction mixture and the possibility of using the products in polyurethane foam synthesis. The raw materials and the products were analyzed by means of gel permeation chromatography, FTIR spectroscopy and 1H NMR. The polyurethane foam formation process was analyzed using a FOAMAT® apparatus.

The Effect of a Chemical Foaming Agent and the Isocyanate Index on the Properties of Open-Cell Polyurethane Foams.

This article presents an ecological approach based on climate neutrality to the synthesis of open-cell polyurethane foams with modified used cooking rapeseed oils. Water was used as a chemical blowing agent in the amount of 20-28 wt.% in relation to the weight of the bio-polyol. The influence of water on the physical and mechanical properties of the synthesized foams was investigated. The resultant porous materials were tested for the content of closed cells, cell structure, apparent density, thermal conductivity, compressive strength, and dimensional stability. It was found that the apparent density decreased in the range of 11-13 kg/m3 when the amount of the foaming agent was increased. In the next step, a foam with a water content of 22% was selected as having the most favorable physico-mechanical properties among all the foams with various water contents. The isocyanate index of the selected foam was then changed from 0.6 to 1.1 and it was observed that the compressive strength increased by an average of 10 kPa. The thermal conductivity coefficients of the final materials with different water contents and isocyanate indices were comparable and in the range of 40-43 mW/m·K.

New Thermo-Reflective Coatings for Applications as a Layer of Heat Insulating Materials.

This paper presents new thermo-reflective coatings with different properties. Basic, anti-corrosion and self-extinguishing coatings were analyzed. The coatings were obtained with a thickness varying from 1 to 3 mm. The coatings were subjected to detailed tests assessing their physical-mechanical properties, i.e., tensile strength, abrasion, pull-off test, water absorption, vapor permeability and thermal properties, i.e., the thermal performance of the reflective coatings, thermal transmittance, thermogravimetric analysis, differential scanning calorimetry, as well as thermomechanical analysis and thermal conductivity. In addition, the possibility of using such coatings in a wide range of temperatures and during application to various materials used as a substrate, i.e., concrete, metal and rigid polyurethane foam, was tested. The thermal analysis of coatings revealed that materials are stable to temperatures above 200 °C, there are no thermal transitions in the negative temperature region and shrinking in low temperatures is minimal (less than 0.5%). From the data obtained within the framework of this study, it can be concluded that anticorrosive, basic and self-extinguishing coatings are eligible for thermo-insulation applications in temperatures up to 200 °C.

Vegetable Fillers and Rapeseed Oil-Based Polyol as Natural Raw Materials for the Production of Rigid Polyurethane Foams.

The reported study concerns the introduction of renewable raw materials into the formulation of rigid polyurethane foams in the quest for the sustainable development of polymer composites. In this study, rigid polyurethane foam composites were prepared using 75 wt.% of rapeseed oil-based polyol and 15 parts per hundred parts of polyol (php) of natural fillers such as chokeberry pomace, raspberry seeds, as well as hazelnut and walnut shells. The influence of the used raw materials on the foaming process, structure, and properties of foams was investigated using a FOAMAT analyzer and a wide selection of characterization techniques. The introduction of renewable raw materials limited reactivity of the system, which reduced maximum temperature of the foaming process. Moreover, foams prepared using renewable raw materials were characterized by a more regular cell structure, a higher share of closed cells, lower apparent density, lower compressive strength and glass transition temperature, low friability (<2%), low water absorption (<1%), high dimensional stability (<±0.5%) and increased thermal stability. The proper selection and preparation of the renewable raw materials and the rational development of the polyurethane recipe composition allow for the preparation of environmentally-friendly foam products with beneficial application properties considering the demands of the circular economy in the synthesis of rigid foams.

Development and Characterization of "Green Open-Cell Polyurethane Foams" with Reduced Flammability.

This work presents the cell structure and selected properties of polyurethane (PUR) foams, based on two types of hydroxylated used cooking oil and additionally modified with three different flame retardants. Bio-polyols from municipal waste oil with different chemical structures were obtained by transesterification with triethanolamine (UCO_TEA) and diethylene glycol (UCO_DEG). Next, these bio-polyols were used to prepare open-cell polyurethane foams of very low apparent densities for thermal insulation applications. In order to obtain foams with reduced flammability, the PUR systems were modified with different amounts (10-30 parts per hundred polyol by weight-php) of flame retardants: TCPP (tris(1-chloro-2-propyl)phosphate), TEP (triethyl phosphate), and DMPP (dimethyl propylphosphonate). The flame retardants caused a decrease of the PUR formulations reactivity. The apparent densities of all the foams were comparable in the range 12-15 kg/m3. The lowest coefficients of thermal conductivity were measured for the open-cell PUR foams modified with DMPP. The lowest values of heat release rate were found for the foams based on the UCO_TEA and UCO_DEG bio-polyols that were modified with 30 php of DMPP.

A Pathway toward a New Era of Open-Cell Polyurethane Foams-Influence of Bio-Polyols Derived from Used Cooking Oil on Foams Properties.

In order to create greener polyurethane (PUR) foams, modified used cooking oils (UCO) were applied as starting resources for the synthesis of bio-polyols. The bio-polyols were produced using transesterification of UCO with diethylene glycol (UCO_DEG) and triethanolamine (UCO_TEA). Next, open-cell PUR foams were synthesized by replacing 20, 40, 60, 80 and 100% of the petrochemical polyol with the bio-polyol UCO_DEG or UCO_TEA. It was observed that an increasing bio-polyol content (up to 60%) led to an increase of the closed cell content. However, a further increase in the bio-polyol content up to 100% resulted in foam cell opening. The bio-foams obtained in the experiment had an apparent density of 13-18 kg/m3. The coefficient of thermal conductivity was determined at three different average temperatures: 10, 0 and -10 °C. The PUR bio-foams modified with bio-polyol UCO_TEA had lower values of thermal conductivity, regardless of the average temperature (35.99-39.57 mW/m·K) than the foams modified with bio-polyol UCO_DEG (36.95-43.78 mW/m·K). The compressive strength of most of the bio-foams was characterized by a higher value than the compressive strength of the reference material (without bio-polyol). Finally, it was observed that the bio-materials exhibited dimensional stability at 70 °C.

Implementation of Circular Economy Principles in the Synthesis of Polyurethane Foams.

The main strategy of the European Commission in the field of the building industry assumes a reduction of greenhouse gas emissions by up to 20% by 2020 and by up to 80% by 2050. In order to meet these conditions, it is necessary to develop not only efficient thermal insulation materials, but also more environmentally friendly ones. This paper describes an experiment in which two types of bio-polyols were obtained using transesterification of used cooking oil with triethanolamine (UCO_TEA) and diethylene glycol (UCO_DEG). The bio-polyols were next used to prepare low-density rigid polyurethane (PUR) foams. It was found that the bio-polyols increased the reactivity of the PUR systems, regardless of their chemical structures. The reactivity of the system modified with 60% of the diethylene glycol-based bio-polyol was higher than in the case of the reference system. The bio-foams exhibited apparent densities of 41-45 kg/m3, homogeneous cellular structures and advantageous values of the coefficient of thermal conductivity. It was observed that the higher functionality of bio-polyol UCO_TEA compared with UCO_DEG had a beneficial effect on the mechanical and thermal properties of the bio-foams. The most promising results were obtained in the case of the foams modified in 60% with the bio-polyol based on triethanoloamine. In conclusion, this approach, utilizing used cooking oil in the synthesis of high-value thermal insulating materials, provides a sustainable municipal waste recycling solution.