Rigid Polyurethane Foams' Development and Optimization from Polyols Based on Depolymerized Suberin and Tall Oil Fatty Acids.

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40-44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

Effect of bio-polyol molecular weight on the structure and properties of polyurethane-polyisocyanurate (PUR-PIR) foams.

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.

Influence of Long-Term Storage and UV Light Exposure on Characteristics of Polyurethane Foams for Cryogenic Insulation.

Rigid polyurethane (PUR) foams have been the most effective insulation material used in space launchers since the beginning of cryogenic fuel use, due to their outstanding thermal and mechanical properties. In this study, spray-applied PUR foams using different ratios of amine-based catalysts were produced. Due to climate change, several restrictions have been made regarding the usage of blowing agents used for PUR foam production. Lately, hydrofluoroolefins (HFOs) have been suggested as an alternative for PUR foam production due to their low global warming potential (GWP) and ozone depletion potential (ODP), replacing the hydrofluorocarbons (HFCs) so far used. This change in blowing agents naturally altered the usage of catalysts. Reactive amine-based catalysts are less hazardous because of their low volatility and ability to react successfully with isocyanate or polyols. Spray-applied PUR foams with a potential application for cryogenic insulation were produced and tested for long-term storage, analyzing parameters such as the pH value of polyol composition, foaming kinetics (trise, tcream), etc. Athermal analysis (TG, DSC) was also applied to developed materials, as well as artificial ageing by exposing samples to UV light. It was discovered that PUR foams obtained using reactive amine-based catalysts, such as Polycat 203 and 218, have a higher integral heat capacity, but polyol mixtures containing these catalysts cannot exceed a storage time of more than 4 months. It was also observed from artificial ageing tests of PUR cryogenic insulation by exposure to UV light that the thickness of the degraded layer reached 0.8 mm (after 1000 h), but no significant destruction of cellular structure deeper in the material was observed.

Rigid Polyurethane Foams as Thermal Insulation Material from Novel Suberinic Acid-Based Polyols.

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.

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.

Polyurethane Foam Composites Reinforced with Renewable Fillers for Cryogenic Insulation.

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.

Natural Oil-Based Rigid Polyurethane Foam Thermal Insulation Applicable at Cryogenic Temperatures.

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.

A Review of Wood Biomass-Based Fatty Acids and Rosin Acids Use in Polymeric Materials.

In recent decades, vegetable oils as a potential replacement for petrochemical materials have been extensively studied. Tall oil (crude tall oil, distilled tall oil, tall oil fatty acids, and rosin acids) is a good source to be turned into polymeric materials. Unlike vegetable oils, tall oil is considered as lignocellulosic plant biomass waste and is considered to be the second-generation raw material, thus it is not competing with the food and feed chain. The main purpose of this review article is to identify in what kind of polymeric materials wood biomass-based fatty acids and rosin acids have been applied and their impact on the properties.