This paper presents research into the preparation of rigid polyurethane foams with bio-polyols from rapeseed and tall oil. Rigid polyurethane foams were designed with a cryogenic insulation application for aerospace in mind. The polyurethane systems containing non-renewable diethylene glycol (DEG) were modified by replacing it with rapeseed oil-based low functional polyol (LF), obtained by a two-step reaction of epoxidation and oxirane ring opening with 1-hexanol. It was observed that as the proportion of the LF polyol in the polyurethane system increased, so too did the apparent density of the foam material. An increase in the value of the thermal conductivity coefficient was associated with an increase in the value of apparent density. Mechanical tests showed that the rigid polyurethane foam had higher compressive strength at cryogenic temperatures compared with the values obtained at room temperature. The adhesion test indicated that the foams subjected to cryo-shock obtained similar values of adhesion strength to the materials that were not subjected to this test. The results obtained were higher than 0.1 MPa, which is a favourable value for foam materials in low-temperature applications.
The increasing interest in polyurethane materials has raised the question of the environmental impact of these materials. For this reason, the scientists aim to find an extremely difficult balance between new material technologies and sustainable development. This work attempts to validate the possibility of replacing petrochemical polyols with previously synthesized bio-polyols and their impact on the structure and properties of rigid polyurethane-polyisocyanurate (PUR-PIR). To date, biobased polyols were frequently used in the manufacturing of PU, but application of bio-polyols synthesized via solvothermal liquefaction using different chains of polyethylene glycol has not been comprehensively discussed. In this work, ten sets of rigid polyurethane foams were synthesized. The influence of bio-polyols addition on foam properties was investigated by mechanical testing, thermogravimetric analysis (TGA), and cone calorimetry. The structure was determined by scanning electron microscopy (SEM) and a gas pycnometer. The tests revealed a significant extension of foam growth time, which can be explained by possible steric hindrances and the presence of less reactive secondary hydroxyl groups. Moreover, an increase average size of pores and aspect ratio was noticed. This can be interpreted by the modification of the cell growth process by the introduction of a less reactive bio-polyol with different viscosity. The analysis of foams mechanical properties showed that the normalized compressive strength increased up to 40% due to incorporation of more cross-linked structures. The thermogravimetric analysis demonstrated that the addition of bio-based polyols increased temperature of 2% (T2%) and 5% (T5%) mass degradation. On the other hand, evaluation of flammability of manufactured foams showed increase of total heat release (HRR) and smoke release (TSR) what may be caused by reduction of char layer stability. These findings add substantially to our understanding of the incorporation of bio-polyols into industrial polyurethane systems and suggest the necessity of conducting further research on these materials.
Sawdust, microcellulose and nanocellulose and their silanized forms were used to reinforce rigid polyurethane (PU) foam composites. The concentration of fillers was varied in the range of 0.5–1.5%. For rigid PU foam formulations, three polyols from recycled and renewable materials were used, among other components. Polyols were obtained from rapeseed oil, tall oil fatty acids and recycled polyethylene terephthalate. As rigid PU foam composites in literature have been described as appropriate thermal insulation material, the appliance of obtained composites for cryogenic insulation was investigated by determining the various physical-mechanical properties of composites. The physical-mechanical properties, such as the modulus of elasticity, compressive and tensile strength in both 293 K and 77 K, adhesion measurements with and without cryo-shock, apparent density, thermal conductivity coefficient, and safety coefficient were measured. The results showed that the addition of fillers did not give a significant improvement of characteristics.
Developing polyols from biomass sources contributes to a more circular economy by replacing petroleum-based polyols in the vast production of polyurethanes (PUR). One such potential biomass source could be leftover birch bark from which suberinic acids (SA) can be obtained. The purpose of this study was to identify the best synthesis routes for novel SA-based polyols, obtain rigid PUR foams, and evaluate their competitiveness and potential suitability as thermal insulation material. Novel polyols were synthesized from depolymerized SA by esterification with various functionality and molecular weight alcohols in several molar ratios. The moisture content, hydroxyl and acid values, and apparent viscosity were tested. Free-rise rigid PUR foams from the most suitable SA-based polyol and tall oil-based polyol were successfully prepared, reaching ~20 wt.% total renewable material content in the foam. The obtained rigid PUR foams’ morphological, mechanical, and thermal properties were investigated and compared to present foam materials, including commercial foams. The apparent density (~33 kg/m3), as well as the closed cell content (~94%), compression strength (0.25 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), approved the competitiveness and potential ability of SA-based rigid PUR foam production as thermal insulation material.
Cryogenics is the science and technology of very low temperatures, typically below 120 K. The most common applications are liquified natural gas carriers, ground-based tanks, and propellant tanks for space launchers. A crucial aspect of cryogenic technology is effective insulation to minimise boil-off from storage tanks and prevent frost build-up. Rigid closed-cell foams are prominent in various applications, including cryogenic insulation, due to their balance between thermal and mechanical properties. Polyurethane (PU) foam is widely used for internal insulation in cryogenic tanks, providing durability under thermal shocks and operational loads. External insulation, used in liquified natural gas carriers and ground-based tanks, generally demands less compressive strength and can utilise lower-density foams. The evolution of cryogenic insulation materials has seen the incorporation of environmentally friendly blowing agents and bio-based polyols to enhance sustainability. Fourth-generation physical blowing agents, such as HFO-1233zd(E) and HFO-1336mzz(Z), offer low global warming potential and improved thermal conductivity. Additionally, bio-based polyols from renewable resources like different natural oils and recycled polyethylene terephthalate (PET) are being integrated into rigid PU foams, showing promising properties for cryogenic applications. Research continues to optimise these materials for better mechanical performance and environmental impact.
In present work the BIOLIGNIN{trade mark, serif} obtained in the result of wheat straw organosolv processing in CIMV pilot plant (France) was investigated as a component of rigid polyurethanes (PUR) foam systems. Different separate approaches of lignin introduction into PUR foam system were studied: as filler without chemical preprocessing and as liquid lignopolyol obtained by lignin oxypropylation in alkali conditions. The incorporation of increasing amount of lignin as filler into reference PUR foam systems on the basis of mixture of commercial polyethers Lupranol 3300 and Lupranol 3422 steadily decreased the compression characteristics of foams, their dimensional stability and hydrophobicity. The complete substitution of Lupranol 3300 by lignopolyol increases its cell structure uniformity and dimensional stability and does not reduce the physical-mechanical properties of foam. In both cases the incorporation of lignin into PUR foam leads to the decreasing of maximum values of thermodegradation rates. The lignin filler can be introduced into lignopolyol based PUR foam in higher quantity than in the reference Lupranol based PUR without reduction of compression characteristics of material. In this work the optimal lignin content in the end product - PUR foam as both polyol and filler is 16%.