Fabrication of High-Performance Polyisocyanurate Aerogels through Cocyclotrimerization of 4,4'-Methylene Diphenyl Diisocyanate and Its Mono-Urethane Derivatives.

Aromatic polyisocyanurate (PIR) aerogels are recognized as advanced porous materials and extensively studied due to their lightweight nature, high porosity, and specific surface area, which attribute to their outstanding thermal insulation properties. The inherent thermal stability of the PIR moieties, combined with great insulating performance, renders PIR aerogels highly suitable for building insulation applications. Nevertheless, materials containing isocyanurate obtained through direct trimerization of aromatic isocyanates exhibit brittleness, resulting in inferior mechanical performance. In order to enhance the processability of the PIR aerogels, we propose a cocyclotrimerization approach involving mixtures of mono- and difunctional aromatic isocyanates. This approach is designed to develop a PIR network with decreased cross-linking density and brittleness. Herein, we developed an array of PIR aerogels from different alkyl chain-modified isocyanate mixtures. The resulting PIR aerogels exhibited high porosity (>89%), a large surface area (∼300 m2/g), superinsulating performance with ultralow thermal conductivity (∼16.8 mW m-1 K-1), notable thermal stability (Td5% ∼ 250 °C), improved mechanical performance, and intrinsic hydrophobicity without the need for postmodification. These high-performance organic aerogels hold significant promise for applications requiring superinsulating materials.

Methods to Increase or Decrease Resistance to Photodegradation and Biodegradation of Polyurethane/Polyisocyanurate (PU/PIR) Foams.

Two series of rigid polyurethane-polyisocyanurate (PU/PIR) foams were obtained. They were modified using powder fillers, such as industrial food cocoa (K5-K15 foam) and instant freeze-dried coffee (KR-KR15) added in amounts of 5, 10 and 15 wt.%. W foam (reference) was obtained without filler. The foams were degraded in a climate chamber for 1 week, 2 weeks or 3 weeks. Appropriate temperature, humidity and UV radiation were set in the chamber, which did not change throughout the degradation process. The foams were also degraded in an oven for two days at 120 °C. The foam tests carried out indicated, among others, on the decrease in compressive strength along with the increase in the residence time of the samples in the chamber. Degraded foams also changed color. Foams containing 5% and 10% of industrial cocoa or freeze-dried coffee were more susceptible to degradation. The addition of 15% coffee or cocoa slows down the degradation process. In the present study, industrial food cocoa and instant freeze-dried coffee were used as modifiers of rigid PU/PIR foam. These fillers have two functions: they accelerate the biodegradation of foams and have antioxidant properties.

Determination of the Long-Term Thermal Performance of Foam Insulation Materials through Heat and Slicing Acceleration.

Foam insulation materials are widely used in the construction industry due to their low thermal conductivity attributable to their microstructures and their low-conductivity blowing agents and affordability. In this study, we evaluate how the thermal performance of foam insulation materials used for the exterior walls of buildings, viz., extruded polystyrene (XPS), polyisocyanurate (PIR), and phenolic foam (PF), age over the life cycle of a building. To compare the aging of thermal performance during the life cycle of a building, each material was tested at 70 and 110 °C and with slicing acceleration according to EN and ISO standards. The thermal conductivity of each foam insulation material was measured using a heat flow meter at an operating temperature of 23 °C and converted into thermal resistance values. Different foam insulation materials have different aging procedures according to material-specific EN standards, while ISO 11561 applies the same procedure to all material classifications. Upon comparing the aged values according to ISO and EN standards to the initial values, the analysis showed a change rate of 23 to 26% in PIR and 18 to 20% in PF. In XPS, a rate of change of 10 to 23.8% was calculated. Our results indicated that the slicing acceleration induced a thermal resistance reduction rate about three times faster than aging at 70 °C. However, the long-term changed thermal resistance values of the foam insulation material applied via the calculating procedure specified in the ISO and EN standards were similar.

Super-Insulating Transparent Polyisocyanurate-Polyurethane Aerogels: Analysis of Thermal Conductivity and Mechanical Properties.

A family of transparent polyisocyanurate-polyurethane (PUR-PIR) aerogels with an interesting combination of physical properties were synthesized. First, their textural properties were analyzed aiming to study catalyst influence on the final porous structures and densities. Their thermal conductivities were measured at different temperatures allowing observation of a clear trend relating the initial formulation with the porous structure and reaching values as low as 12 mW/mK, the lowest found in the literature for aerogels based on this polymer matrix. Contributions to thermal conductivity were calculated, improving the understanding of the porous structure-insulating performance relationship. Moreover, their mechanical properties were studied (elastic modulus, stress at different strains and elastic behavior). The aerogels showed tunable stiffness (elastic modulus from 6.32 to 0.13 MPa) by changing the catalyst concentration and significant elasticity. Thus, super-insulating transparent PUR-PIR aerogels with tailored mechanical properties were obtained opening a wide range of potential applications in the energy, building, automotive and aeronautical sectors, among others. The exceptional insulation of silica aerogels was reached at the same time that their general brittleness was improved while keeping good transparency to visible light (85%, 650 nm). Therefore, these aerogels may constitute an alternative to silica aerogels.

Optical Properties of Polyisocyanurate-Polyurethane Aerogels: Study of the Scattering Mechanisms.

Highly transparent polyisocyanurate-polyurethane (PUR-PIR) aerogels were synthesized, and their optical properties were studied in detail. After determining the density and structural parameters of the manufactured materials, we analyzed their optical transmittance. It was demonstrated that the catalyst content used to produce the aerogels can be employed to tune the internal structure and optical properties. The results show that the employment of lower catalyst amounts leads to smaller particles forming the aerogel and concomitantly to higher transmittances, which reach values of 85% (650 nm) due to aerogel particles acting as scattering centers. Thus, it was found that the lower this size, the higher the transmittance. The effect of the sample thickness on the transmittance was studied through the Beer-Lambert law. Finally, the scattering mechanisms involved in the light attenuation were systematically evaluated by measuring a wide range of light wavelengths and determining the transition between Rayleigh and Mie scattering when the particles were larger. Therefore, the optical properties of polyurethane aerogels were studied for the first time, opening a wide range of applications in building and energy sectors such as glazing windows.

Studying the Suitability of Nineteen Lignins as Partial Polyol Replacement in Rigid Polyurethane/Polyisocyanurate Foam.

In this study, nineteen unmodified lignins from various sources (hardwood, softwood, wheat straw, and corn stover) and isolation processes (kraft, soda, organosolv, sulfite, and enzymatic hydrolysis) were used to replace 30 wt.% of petroleum-based polyol in rigid polyurethane/polyisocyanurate (PUR/PIR) foam formulations. Lignin samples were characterized by measuring their ash content, hydroxyl content (Phosphorus Nuclear Magnetic Resonance Spectroscopy), impurities (Inductively Coupled Plasma), and pH. After foam formulation, properties of lignin-based foams were evaluated and compared with a control foam (with no lignin) via cell morphology, closed-cell content, compression strength, apparent density, thermal conductivity, and color analysis. Lignin-based foams passed all measured standard specifications required by ASTM International C1029-15 for type 1 rigid insulation foams, except for three foams. These three foams had poor compressive strengths, significantly larger cell sizes, darker color, lower closed-cell contents, and slower foaming times. The foam made with corn stover enzymatic hydrolysis lignin showed no significant difference from the control foam in terms of compressive strength and outperformed all other lignin-based foams due to its higher aliphatic and p-hydroxyphenyl hydroxyl contents. Lignin-based foams that passed all required performance testing were made with lignins having higher pH, potassium, sodium, calcium, magnesium, and aliphatic/p-hydroxyphenyl hydroxyl group contents than those that failed.

Effective Halogen-Free Flame-Retardant Additives for Crosslinked Rigid Polyisocyanurate Foams: Comparison of Chemical Structures.

The impact of phosphorus-containing flame retardants (FR) on rigid polyisocyanurate (PIR) foams is studied by systematic variation of the chemical structure of the FR, including non-NCO-reactive and NCO-reactive dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO)- and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing compounds, among them a number of compounds not reported so far. These PIR foams are compared with PIR foams without FR and with standard FRs with respect to foam properties, thermal decomposition, and fire behavior. Although BPPO and DOPO differ by just one oxygen atom, the impact on the FR properties is very significant: when the FR is a filler or a dangling (dead) end in the PIR polymer network, DOPO is more effective than BPPO. When the FR is a subunit of a diol and it is fully incorporated in the PIR network, BPPO delivers superior results.

Effect of New Eco-Polyols Based on PLA Waste on the Basic Properties of Rigid Polyurethane and Polyurethane/Polyisocyanurate Foams.

The aim of the presented research was to obtain two new eco-polyols based on waste polylactide (PLA) and to check the effect on the properties of rigid polyurethane (RPU) foams and, based on these, rigid polyurethane/polyisocyanurate (RPU/PIR) foams. The synthesis of eco-polyols was based on the transesterification reaction of melted PLA with diethylene glycol in the presence of an organometallic catalyst. Properties of the obtained eco-polyols were examined for their potential as raw materials for synthesis of rigid polyurethane and polyisocyanurate foams, i.e., hydroxyl value, acid value, density, viscosity, pH, water content. Spectroscopic studies (FTIR, 1H NMR and 13C NMR) were also carried out. Results of these tests confirmed the assumed chemical structure of the new polyols. RPU and RPU/PIR foam formulations were developed based on the obtained analytical results. Partial replacement of petrochemical polyol by eco-polyols in RPU and RPU/PIR foams decreased the value of apparent density, compressive strength, brittleness and water absorption. Moreover, all foams modified by eco-polyols showed higher resistance to aging. All RPU/PIR foams and most PRU foams modified by eco-polyols from waste PLA had better functional properties than the reference foams based on petrochemical polyol.

Effect of Evening Primrose (Oenothera biennis) Oil Cake on the Properties of Polyurethane/Polyisocyanurate Bio-Composites.

Rigid polyurethane/polyisocyanurate (RPU/PIR) foam formulations were modified by evening primrose (Oenothera biennis) oil cake as a bio-filler in the amount of 5 to 50 wt.%. The obtained foams were tested in terms of processing parameters, cellular structure (SEM analysis), physico-mechanical properties (apparent density, compressive strength, brittleness, accelerated aging tests), thermal insulation properties (thermal conductivity coefficient, closed cells content, absorbability and water absorption), flammability, smoke emission, and thermal properties. The obtained results showed that the amount of bio-filler had a significant influence on the morphology of the modified foams. Thorough mixing of the polyurethane premix allowed better homogenization of the bio-filler in the polyurethane matrix, resulting in a regular cellular structure. This resulted in an improvement in the physico-mechanical and thermal insulation properties as well as a reduction in the flammability of the obtained materials. This research provided important information on the management of the waste product from the edible oil industry and the production process of fire-safe RPU/PIR foams with improved performance properties. Due to these beneficial effects, it was found that the use of evening primrose oil cake as a bio-filler for RPU/PIR foams opens a new way of waste management to obtain new "green" materials.

Smoke toxicity of rainscreen façades.

The toxic smoke production of four rainscreen façade systems were compared during large-scale fire performance testing on a reduced height BS 8414 test wall. Systems comprising 'non-combustible' aluminium composite material (ACM) with polyisocyanurate (PIR), phenolic foam (PF) and stone wool (SW) insulation, and polyethylene-filled ACM with PIR insulation were tested. Smoke toxicity was measured by sampling gases at two points - the exhaust duct of the main test room and an additional 'kitchen vent', which connects the rainscreen cavity to an occupied area. Although the toxicity of the smoke was similar for the three insulation products with non-combustible ACM, the toxicity of the smoke flowing from the burning cavity through the kitchen vent was greater by factors of 40 and 17 for PIR and PF insulation respectively, when compared to SW. Occupants sheltering in a room connected to the vent are predicted to collapse, and then inhale a lethal concentration of asphyxiant gases. This is the first report quantifying fire conditions within the cavity and assessing smoke toxicity within a rainscreen façade cavity.

Burning behaviour of rainscreen façades.

Four reduced-height (5 m) BS 8414-1 façade flammability tests were conducted, three having mineral-filled aluminium composite material (ACM-A2) with polyisocyanurate (PIR) and phenolic (PF) foam and stone wool (SW) insulation, the fourth having polyethylene-filled ACM (ACM-PE) with PIR insulation. Each façade was constructed from a commercial façade engineer's design, and built by practising façade installers. The ACM-PE/PIR façade burnt so ferociously it was extinguished after 13.5 min, for safety. The three ACM-A2 cladding panels lost their structural integrity, and melted away from the test wall, whereupon around 40% of both the combustible PIR and PF insulation burnt and contributed to the fire spread. This demonstrates why all façade products must be non-combustible, not just the outer panels. For the three ACM-A2 tests, while the temperature in front of the cavity was independent of the insulation, the temperatures within it varied greatly, depending on the insulation. The system using PF/A2 allowed fire to break through to the cavity first, as seen by a sharp increase in temperature after 17 min. For PIR/A2, the temperature increased sharply at 22 minutes, as the panel started to fall away from the wall. For SW/A2, no rapid temperature rise was observed.

Highly Insulated Wall Systems with Exterior Insulation of Polyisocyanurate under Different Facer Materials: Material Characterization and Long-Term Hygrothermal Performance Assessment.

The application of exterior insulation in both new construction and retrofits is a common practice to enhance the energy efficiency of buildings. In addition to increased thermal performance, the rigid insulation can serve to keep the sheathing board warm and serve as a water-resistive barrier to keep moisture-related problems due to condensation and wind-driven rain. Polyisocyanurate (PIR) rigid boards have a higher thermal resistance in comparison to other commonly used exterior insulation boards. However, because of its perceived lower permeance, its use as exterior insulation is not very common. In this study, the hygrothermal property of PIR boards with different facer types and thicknesses is characterized. The material data obtained through experimental test and extrapolation is used in a long term hygrothermal performance assessment of a wood frame wall with PIR boards as exterior insulation. Results show that PIR with no facer has the smallest accumulated moisture on the sheathing board in comparison to other insulation boards. Walls with a bigger thickness of exterior insulation perform better when no vapor barrier is used. The PIR exterior insulation supports the moisture control strategy well in colder climates in perfect wall scenarios, where there is no air leakage and moisture intrusion. In cases where there is trapped moisture, the sheathing board has a higher moisture content with PIR boards with both aluminum or fiberglass type facers. An innovative facer material development for PIR boards can help efforts targeting improved energy-efficient and durable wall systems.

Study on the Structure-Property Dependences of Rigid PUR-PIR Foams Obtained from Marine Biomass-Based Biopolyol.

The paper describes the preparation and characterization of rigid polyurethane-polyisocyanurate (PUR-PIR) foams obtained with biopolyol synthesized in the process of liquefaction of biomass from the Baltic Sea. The obtained foams differed in the content of biopolyol in polyol mixture (0-30 wt%) and the isocyanate index (IISO = 200, 250, and 300). The prepared foams were characterized in terms of processing parameters (processing times, synthesis temperature), physical (sol fraction content, apparent density) and chemical structure (Fourier transform infrared spectroscopy), microstructure (computer microtomography), as well as mechanical (compressive strength, dynamic mechanical analysis), and thermal properties (thermogravimetric analysis, thermal conductivity coefficient). The influence of biopolyol and IISO content on the above properties was determined. The addition of up to 30 wt% of biopolyol increased the reactivity of the polyol mixture, and the obtained foams showed enhanced mechanical, thermal, and insulating properties compared to foams prepared solely with petrochemical polyol. The addition of up to 30 wt% of biopolyol did not significantly affect the chemical structure and average cell size. With the increase in IISO, a slight decrease in processing times and mechanical properties was observed. As expected, foams with higher IISO exhibited a higher relative concentration of polyisocyanurate groups in their chemical structure, which was confirmed using principal component analysis (PCA).

Biodegradable, Flame-Retardant, and Bio-Based Rigid Polyurethane/Polyisocyanurate Foams for Thermal Insulation Application.

This article raised the issue of studies on the use of new bio-polyol based on white mustard seed oil and 2,2'-thiodiethanol (3-thiapentane-1,5-diol) for the synthesis of rigid polyurethane/polyisocyanurate (RPU/PIR) foams. For this purpose, new formulations of polyurethane materials were prepared. Formulations contained bio-polyol content from 0 to 0.4 chemical equivalents of hydroxyl groups. An industrial flame retardant, tri(2-chloro-1-methylethyl) phosphate (Antiblaze TCMP), was added to half of the formulations. Basic foaming process parameters and functional properties, such as apparent density, compressive strength, brittleness, absorbability and water absorption, aging resistance, thermal conductivity coefficient λ, structure of materials, and flammability were examined. The susceptibility of the foams to biodegradation in soil was also examined. The increase in the bio-polyol content caused a slight increase in processing times. Also, it was noted that the use of bio-polyol had a positive effect on the functional properties of obtained RPU/PIR foams. Foams modified by bio-polyol based on mustard seed oil showed lower apparent density, brittleness, compressive strength, and absorbability and water absorption, as well as thermal conductivity, compared to the reference (unmodified) foams. Furthermore, the obtained materials were more resistant to aging and more susceptible to biodegradation.

The Use of Waste from the Production of Rapeseed Oil for Obtaining of New Polyurethane Composites.

This article presents the results of research on obtaining new polyurethane materials modified by a by-product from vegetable oils industry-rapeseed cake. The chemical composition of rapeseed cake was examined. Rigid polyurethane-polyisocyanurate (RPU/PIR) foams containing a milled rapeseed cake in their composition were obtained as part of the conducted research. Biofiller was added in amount of 30 wt.% up to 60 wt.%. Effects of rapeseed cake on the foaming process, cell structure and selected properties of foams, such as apparent density, compressive strength, brittleness, flammability, absorbability, water absorption, thermal resistance and thermal conductivity are described. The foaming process of RPU/PIR foams modified by rapeseed cake was characterized by a lower reactivity, lower foaming temperature and decrease in dielectric polarization. This resulted in a slowed formation of the polyurethane matrix. Apparent density of RPU/PIR foams with biofiller was higher than in unmodified foam. Addition of rapeseed cake did not have a significant influence on the thermal conductivity of obtained materials. However, we observed a tendency for opening the cells of modified foams and obtaining a smaller cross-sectional area of cells. This led to an increase of absorbability and water absorption of obtained materials. However, an advantageous effect of using rapeseed cake in polyurethane formulations was noted. Modified RPU/PIR foams had higher compressive strength, lower brittleness and lower flammability than reference foam.

Improving the Flame Retardance of Polyisocyanurate Foams by Dibenzo[d,f][1,3,2]dioxaphosphepine 6-Oxide-Containing Additives.

A series of new flame retardants (FR) based on dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) incorporating acrylates and benzoquinone were developed previously. In this study, we examine the fire behavior of the new flame retardants in polyisocyanurate (PIR) foams. The foam characteristics, thermal decomposition, and fire behavior are investigated. The fire properties of the foams containing BPPO-based derivatives were found to depend on the chemical structure of the substituents. We also compare our results to state-of-the-art non-halogenated FR such as triphenylphosphate and chemically similar phosphinate, i.e. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO), based derivatives to discuss the role of the phosphorus oxidation state.

New Poly(lactide-urethane-isocyanurate) Foams Based on Bio-Polylactide Waste.

The article presents the results of research on the synthesis of a new eco-polyol based on polylactide (PLA) waste and its use for the production of rigid polyurethane-polyisocyanurate (RPU/PIR) foams. The obtained recycling-based polyol was subjected to analytical, physicochemical and spectroscopic tests (FTIR, ¹H NMR, 13C NMR) to confirm its suitability for the synthesis of polyurethane materials. Then, it was used to partially replace petrochemical polyol in polyurethane formulation. The obtained RPU/PIR foams were characterized by lower apparent density, brittleness, and water absorption. In addition, foams modified by eco-polyol had higher flame retardancy, as compared to reference foam. The results of the research show that the use of PLA polyol based on plastic waste may be an alternative to petrochemical polyols. This research matches with the current trends of sustainable development and green chemistry.

Effect of Evening Primrose Oil-Based Polyol on the Properties of Rigid Polyurethane⁻Polyisocyanurate Foams for Thermal Insulation.

The article presents the results of research on the synthesis of a new biopolyol based on evening primrose oil, and its use in the production of rigid polyurethane⁻polyisocyanurate foams intended for thermal insulation. The obtained biopolyol was subjected to analytical, physicochemical, and spectroscopic tests (Fourier transform infrared (FTIR), ¹H NMR, 13C NMR) to confirm its suitability for the synthesis of polyurethane materials. Then, it was used for the partial replacement of the petrochemical polyol in the polyurethane formulation. Obtained rigid polyurethane⁻polyisocyanurate foams are characterized by a lower apparent density, brittleness, water absorption, and thermal conductivity coefficient λ. In addition, foams modified by biopolyols had a higher content of closed cells and higher aging resistance. The results of the conducted research showed that the use of the biopolyol based on evening primrose oil may be an alternative to petrochemical polyols. The research presented herein is perfectly consistent with the trends of sustainable development and the philosophy of green chemistry.

Toxic Combustion Product Yields as a Function of Equivalence Ratio and Flame Retardants in Under-Ventilated Fires: Bench-Large-Scale Comparisons.

In large-scale compartment fires; combustion product yields vary with combustion conditions mainly in relation to the fuel:air equivalence ratio (Φ) and the effects of gas-phase flame retardants. Yields of products of inefficient combustion; including the major toxic products CO; HCN and organic irritants; increase considerably as combustion changes from well-ventilated (Φ < 1) to under-ventilated (Φ = 1⁻3). It is therefore essential that bench-scale toxicity tests reproduce this behaviour across the Φ range. Yield data from repeat compartment fire tests for any specific fuel show some variation on either side of a best-fit curve for CO yield as a function of Φ. In order to quantify the extent to which data from the steady state tube furnace (SSTF [1]; ISO TS19700 [2]) represents compartment fire yields; the range and average deviations of SSTF data for CO yields from the compartment fire best-fit curve were compared to those for direct compartment fire measurements for six different polymeric fuels with textile and non-textile applications and for generic post-flashover fire CO yield data. The average yields; range and standard deviations of the SSTF data around the best-fit compartment fire curves were found to be close to those for the compartment fire data. It is concluded that SSTF data are as good a predictor of compartment fire yields as are repeat compartment fire test data.