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.

Characteristics of Components and Density of Rigid Nanoclay-Filled Medium-Density Polyurethane Foams Produced in a Sealed Mould.

The characteristics of rigid, nanoclay-filled, medium-density NEOpolyol-380 polyurethane foams components can be estimated when two conditions are met: (1) the foam blocks are produced in a sealed mould; and (2) the mass of the reacting mixture is kept constant. It was shown that, with an increase in filler concentration, the total mass of the filled polymeric network stays constant, but the total volume reduces; the higher the ratio of density of the exfoliated nanoclay platelets and polymer, the higher the volume reduction of the polymeric network. Experimental data of polyurethane foam block mass were acquired at concentrations η = 0%, 0.25%, 0.5%, 1%, 2%, 3% and 5% from the mass of a filled reacting mixture. Foam-density dependence in the uniform zone and in the side-sections of the produced blocks on the: (1) mass of the blocks; and (2) the concentration of the filler was analysed. The study demonstrated that the correlation of the specimens' density with the foam block mass is much higher than that of the filler concentration.

Anisotropy and Mechanical Properties of Nanoclay Filled, Medium-Density Rigid Polyurethane Foams Produced in a Sealed Mold, from Renewable Resources.

Medium-density rigid polyurethane (PU) foams are often produced in sealed molds; therefore, the processes inside the mold and structure of the produced foam blocks need to be understood. The structural and mechanical anisotropy is shown to be the third variable along with (1) concentration of the nanoclay filler and (2) density, to determine the mechanical properties of the filled PU foam composites produced in a sealed mold. The varying anisotropy of the specimens hinders the accurate evaluation of the filling effect. The methodology for the estimation of the anisotropy characteristics of specimens from different locations within the nanoclay filled PU foam blocks is elaborated. A criterion, based on analysis of Poisson's ratios, is formulated for the selection of specimens with similar anisotropy characteristics. The shear and bulk moduli are estimated theoretically, dependent on the filler's concentration, using the experimentally determined constants.

Rapeseed Oil as Feedstock for Bio-Based Thermoset Foams Obtained via Michael Addition Reaction.

Rapeseed oil was used to develop thermoset foams via Michael addition reaction by mixing two liquid components, Michael donor and Michael acceptor. The foaming of the curing thermoset was achieved by the physical blowing agent which expanded from the reacting foam mass due to an exothermic curing reaction. The influence of the rapeseed oil-based Michael donor functionality on the foaming process and the characteristics of the obtained thermoset foams was studied. The 1,1,3,3-tetramethylguanidine catalyst's influence on the foaming process kinetics was studied using FOAMAT equipment. The curing of the bio-based thermoset was analysed using a dielectric polarisation sensor. The morphology of the developed thermoset foam was analysed using a scanning electron microscope and the obtained foams were characterized using TGA, DSC, DMA and mechanical analysis tests. A direct correlation between the thermoset foam polymer crosslinking density and foaming reactivity, mechanical properties and glass transition temperature were determined. Obtained rapeseed oil based thermoset foams had a relatively low thermal conductivity of 33.9-35.4 mW/(m·K) which allows their use as thermal insulation material in civil engineering applications.

Bio-Based Polymer Developments from Tall Oil Fatty Acids by Exploiting Michael Addition.

In this study, previously developed acetoacetates of two tall-oil-based and two commercial polyols were used to obtain polymers by the Michael reaction. The development of polymer formulations with varying cross-link density was enabled by different bio-based monomers in combination with different acrylates-bisphenol A ethoxylate diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. New polymer materials are based on the same polyols that are suitable for polyurethanes. The new polymers have qualities comparable to polyurethanes and are obtained without the drawbacks that come with polyurethane extractions, such as the use of hazardous isocyanates or reactions under harsh conditions in the case of non-isocyanate polyurethanes. Dynamic mechanical analysis, differential scanning calorimetry, thermal gravimetric analysis, and universal strength testing equipment were used to investigate the physical and thermal characteristics of the created polymers. Polymers with a wide range of thermal and mechanical properties were obtained (glass transition temperature from 21 to 63 °C; tensile modulus (Young's) from 8 MPa to 2710 MPa and tensile strength from 4 to 52 MPa). The synthesized polymers are thermally stable up to 300 °C. The suggested method may be used to make two-component polymer foams, coatings, resins, and composite matrices.

The Synthesis of Bio-Based Michael Donors from Tall Oil Fatty Acids for Polymer Development.

In this study, the synthesis of a Michael donor compound from cellulose production by-products-tall oil fatty acids-was developed. The developed Michael donor compounds can be further used to obtain polymeric materials after nucleophilic polymerization through the Michael reaction. It can be a promising alternative method for conventional polyurethane materials, and the Michael addition polymerization reaction takes place under milder conditions than non-isocyanate polyurethane production technology, which requires high pressure, high temperature and a long reaction time. Different polyols, the precursors for Michael donor components, were synthesized from epoxidized tall oil fatty acids by an oxirane ring-opening and esterification reaction with different alcohols (trimethylolpropane and 1,4-butanediol). The addition of functional groups necessary for the Michael reaction was carried out by a transesterification reaction of polyol hydroxyl groups with tert-butyl acetoacetate ester. The following properties of the developed polyols and their acetoacetates were analyzed: hydroxyl value, acid value, moisture content and viscosity. The chemical structure was analyzed using Fourier transform infrared spectroscopy, gel permeation chromatography, size-exclusion chromatography and nuclear magnetic resonance. Matrix-assisted laser desorption/ionization analysis was used for structure identification for this type of acetoacetate for the first time.

Thermal Insulating Rigid Polyurethane Foams with Bio-Polyol from Rapeseed Oil Modified by Phosphorus Additive and Reactive Flame Retardants.

In this article, rigid polyurethane foams obtained with the addition of a bio-polyol from rapeseed oil, were modified with the dimethyl propane phosphonate as additive flame retardant and two reactive flame retardants diethyl (hydroxymethyl)phosphonate and diethyl bis-(2-hydroxyethyl)-aminomethylphosphonate. The influence of used flame retardants on the foaming process and characteristic processing times of tested polyurethane systems were determined. The obtained foams were tested in terms of cell structure, physical and mechanical properties, as well as flammability. Modified foams had worse mechanical and thermal insulation properties, caused by lower cellular density and higher anisotropy coefficient in the cross-section parallel to the foam rise direction, compared to unmodified foam. However, the thermal conductivity of all tested foam materials was lower than 25.82 mW/m∙K. The applied modifiers effectively reduced the flammability of rigid polyurethane foams, among others, increasing the oxygen index above 21.4 vol.%, reducing the total heat released by about 41-51% and the rate of heat release by about 2-52%. A correlation between the limiting oxygen index values and both total heat released parameters from the pyrolysis combustion flow calorimetry and cone calorimetry was observed. The correlation was also visible between the value of the heat release capacity (HRC) parameter obtained from the pyrolysis combustion flow calorimetry and the maximum average rate of heat emission (MARHE) from the cone calorimeter test.

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.

Scale-Up and Testing of Polyurethane Bio-Foams as Potential Cryogenic Insulation Materials.

This article compares the properties of closed-cell PUR bio-foams produced on a laboratory scale and on an industrial scale. In the formulation used, the polyol premix contained 40 wt.% of a bio-polyol based on rapeseed oil. Selected useful properties of the foams obtained on the two scales and the use of one-step and spraying methods were compared. In the case of the spraying method, the experimental system was compared to a commercial one. Given the possibility of applying the bio-foams in insulation systems for cryogenic and liquefied natural gas (LNG) applications, a compressive strength analysis of the foams was carried out at room temperature as well as at -196 °C. It was found that the foams modified with the bio-polyol were characterized by a higher compressive strength at low temperatures than commercial foams based on a petrochemical polyol.

Light Microscopy of Medium-Density Rigid Polyurethane Foams Filled with Nanoclay.

Practical applications and mathematical modelling of the physical and mechanical properties of medium-density rigid polyurethane foams require knowledge of their structure. It is necessary to determine structural characteristics without destroying the foams and measuring each element. A methodology is described for the use of light microscopy on environmentally sustainable, medium-density rigid polyurethane foams (in the density region of ≈210-230 kg/m3), by the analysis of two types of light microscopy images: (1) Cutting surface images; and (2) Through-cutting surface images. The dimensions of structural elements of polyurethane foams, filled with the nanoclay Cloisite-30B at concentrations of 0.0%, 0.25%, 0.50%, 1.0%, 2.0%, 3.0%, and 5.0% from the mass of the filled reacting mixture, are estimated. Probability density functions of projections of bubbles' diameters and struts' length are determined using images in three mutually perpendicular planes. A mathematical model is developed for the restoration of the actual dimensions of bubbles' diameters using data of cutting circles' diameters. Intercalation and exfoliation of the filler's Cloisite-30B mono-layers is evaluated via the basal spacing by X-ray diffraction at a 5 wt.% concentration of nanoclay.

The Effect of Manufacture Process on Mechanical Properties and Burning Behavior of Epoxy-Based Hybrid Composites.

The production of hybrid layered composites allows comprehensive modification of their properties and adaptation to the final expectations. Different methods, such as hand lay-up, vacuum bagging, and resin infusion were applied to manufacture the hybrid composites. In turn, fabrics used for manufacturing composites were made of glass (G), aramid (A), carbon (C), basalt (B), and flax (F) fibers. Flexural, puncture impact behavior, and cone calorimetry tests were applied to establish the effect of the manufacturing method and the fabrics layout on the mechanical and fire behavior of epoxy-based laminates. The lowest flammability and smoke emission were noted for composites made by vacuum bagging (approximately 40% lower values of total smoke release compared with composites made by the hand lay-up method). It was demonstrated that multi-layer hybrid composites made by vacuum bagging might enhance the fire safety levels and simultaneously maintain high mechanical properties designed for, e.g., the railway and automotive industries.

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.

Characterization of Birch Wood Residue after 2-Furaldehyde Obtaining, for Further Integration in Biorefinery Processing.

Latvia is a large manufacturer of plywood in Eastern Europe, with an annual production of 250,000 m3. In Latvia's climatic conditions, birch (Betula pendula) is the main tree species that is mainly used for plywood production. A significant part of the processed wood makes up residues like veneer shorts, cores, and cut-offs (up to 30%), which have a high potential for value-added products. The aim of this research was to comprehensively characterize lignocellulosic (LC) biomass that was obtained after 2-furaldehyde production in terms of further valorization of this resource. The polymeric cellulose-enriched material can be used in the new biorefinery concept for the production of 2-furaldehyde, acetic acid, cellulose pulp, thermomechanical (TMP) and an alkaline peroxide mechanical (APMP) pulping process. In addition, we experimentally developed the best 2-furaldehyde production conditions to optimize the purity and usability of cellulose in the leftovers of the LC material. The best experimental results in terms of both 2-furaldehyde yield and the purity of residual lignocellulose were obtained if the catalyst concentration was 70%, the catalyst amount was 4 wt.%, the reaction temperature was 175 °C,and the treatment time was 60 min. After process optimization with DesignExpert11, we concluded that the best conditions for maximal glucose content (as cellulose fibers) was a catalyst concentration of 85%, a catalyst amount of 5 wt.%, a temperature of 164 °C, and a treatment time of 52 min.

Suberinic Acids as a Potential Feedstock for Polyol Synthesis: Separation and Characterization.

Global sustainability challenges prompt the world to modify its strategies and shift from a fossil-fuel-based economy to a bio-resources-based one and to the production of renewable biomass chemicals. Depolymerized suberinic acids (SA) were considered as an alternative resource to develop bio-polyols that can be further used in polyurethane (PU) material production. Birch (Betula pendula) outer bark was used as a raw material to obtain the SA, extracted with ethanol, and depolymerized with potassium hydroxide ethanol solution. By acidifying the filtrate to pH 5.0, 3.0, and 1.0 and drying it at 50 °C and 130 °C, 12 different SA potential feedstocks were obtained and characterized using chemical (total phenolics content, solubility in DMSO, acid, hydroxyl, and saponification number) and instrumental analytical methods (GC-MS, SEC-RID, DSC, and FTIR). Several bio-polyols were synthesized from the SA sample acidified to pH 1 and dried at 130 °C. Acid number and hydroxyl number values, the apparent viscosity and moisture content were measured. It was concluded that SA have a high enough saponification and acid value to investigate the polyol synthesis route via the esterification reaction. Moreover, SA had OH groups in their structure, which can be exploited for PU material development. The majority of SA compounds had relatively low molecular weight with <1300 Da that are suited for bio-polyol synthesis applied for rigid PU foam development. The synthesized bio-polyols had high hydroxyl number values necessary for bio-polyols to be used for rigid PU foam production.

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.

Residual Birch Wood Lignocellulose after 2-Furaldehyde Production as a Potential Feedstock for Obtaining Fiber.

From birch wood, it is possible to obtain both acetic acid and 2-furaldehyde as valuable value-added products. The main objective of this study was to develop a new wasteless technology for obtaining 2-furaldehyde, acetic acid, and lignocellulose (LC) residue usable as feedstock in further processing such as thermomechanical (TMP), alkaline peroxide mechanical (APMP), and sulfate pulping processes. To achieve this objective several screening tests were performed, and a further experimental plan was developed using DesignExpert11. Process yields were analyzed both in terms of total yield and at individual time increments. In addition, the obtained LC residue was also characterized. A unique bench-scale reactor system was used to obtain an LC material without pentoses and with maximum preservation of cellulose fiber for further research. Studies on the deacetylation and dehydration of birch wood hemicelluloses of pentose monosaccharides to 2-furaldehyde and acetic acid using orthophosphoric acid as a catalyst were carried out. Results showed that, depending on the used pre-treatment conditions, the 2-furaldehyde yield was from 0.04% to 10.84% oven dry mass (o.d.m.), the acetic acid yield was from 0.51% to 6.50% o.d.m., and the LC residue yield was from 68.13% to 98.07% o.d.m. with minimal content of admixtures. Process optimization using DesignExpert11 revealed that the main pre-treatment process parameters that influenced the yield of 2-furaldehyde in the pre-treatment process were process temperature (53.3%) and process duration (29.8%).

Impact of Different Epoxidation Approaches of Tall Oil Fatty Acids on Rigid Polyurethane Foam Thermal Insulation.

A second-generation bio-based feedstock-tall oil fatty acids-was epoxidised via two pathways. Oxirane rings were introduced into the fatty acid carbon backbone using a heterogeneous epoxidation catalyst-ion exchange resin Amberlite IR-120 H or enzyme catalyst Candida antarctica lipase B under the trade name Novozym® 435. High functionality bio-polyols were synthesised from the obtained epoxidated tall oil fatty acids by oxirane ring-opening and subsequent esterification reactions with different polyfunctional alcohols: trimethylolpropane and triethanolamine. The synthesised epoxidised tall oil fatty acids (ETOFA) were studied by proton nuclear magnetic resonance. The chemical structure of obtained polyols was studied by Fourier-transform infrared spectroscopy and size exclusion chromatography. Average molecular weight and polydispersity of polyols were determined from size exclusion chromatography data. The obtained polyols were used to develop rigid polyurethane (PU) foam thermal insulation material with an approximate density of 40 kg/m3. Thermal conductivity, apparent density and compression strength of the rigid PU foams were determined. The rigid PU foams obtained from polyols synthesised using Novozym® 435 catalyst had superior properties in comparison to rigid PU foams obtained from polyols synthesised using Amberlite IR-120 H. The developed rigid PU foams had an excellent thermal conductivity of 21.2-25.9 mW/(m·K).

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.

Reinforcement Efficiency of Cellulose Microfibers for the Tensile Stiffness and Strength of Rigid Low-Density Polyurethane Foams.

Rigid low-density closed-cell polyurethane (PU) foams are widely used in both thermal insulation and structural applications. The sustainability of PU foam production can be increased by using bio-based components and fillers that ensure both enhanced mechanical properties and higher renewable material content. Such bio-based foams were produced using polyols derived from rapeseed oil and microcrystalline cellulose (MCC) fibers as filler. The effect of MCC fiber loading of up to 10 wt % on the morphology, tensile stiffness, and strength of foams has been evaluated. For estimation of the mechanical reinforcement efficiency of foams, a model allowing for the partial alignment of filler fibers in foam struts was developed and validated against test results. It is shown that although applying MCC fibers leads to modest gains in the mechanical properties of PU foams compared with cellulose nanocrystal reinforcement, it may provide a higher content of renewable material in the foams.