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Polyisocyanurate
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Polyisocyanurate (/ˌpɒlɪˌaɪsoʊsaɪˈænjʊəreɪt/), also referred to as PIR, polyol, or ISO, is a thermoset plastic[1] typically produced as a foam and used as rigid thermal insulation. The starting materials are similar to those used in polyurethane (PUR) except that the proportion of methylene diphenyl diisocyanate (MDI) is higher and a polyester-derived polyol is used in the reaction instead of a polyether polyol. The resulting chemical structure is significantly different, with the isocyanate groups on the MDI trimerising to form isocyanurate groups which the polyols link together, giving a complex polymeric structure.[2]
Manufacturing
[edit]The reaction of (MDI) and polyol takes place at higher temperatures compared with the reaction temperature for the manufacture of PUR. At these elevated temperatures and in the presence of specific catalysts, MDI will first react with itself, producing a stiff, ring molecule, which is a reactive intermediate (a tri-isocyanate isocyanurate compound). Remaining MDI and the tri-isocyanate react with polyol to form a complex poly(urethane-isocyanurate) polymer (hence the use of the abbreviation PUI as an alternative to PIR), which is foamed in the presence of a suitable blowing agent. This isocyanurate polymer has a relatively strong molecular structure, because of the combination of strong chemical bonds, the ring structure of isocyanurate and high cross link density, each contributing to the greater stiffness than found in comparable polyurethanes. The greater bond strength also means these are more difficult to break, and as a result a PIR foam is chemically and thermally more stable: breakdown of isocyanurate bonds is reported to start above 200 °C, compared with urethane at 100 to 110 °C.
PIR typically has an MDI/polyol ratio, also called its index (based on isocyanate/polyol stoichiometry to produce urethane alone), higher than 180. By comparison PUR indices are normally around 100. As the index increases material stiffness the brittleness also increases, although the correlation is not linear. Depending on the product application greater stiffness, chemical and/or thermal stability may be desirable. As such PIR manufacturers can offer multiple products with identical densities but different indices in an attempt to achieve optimal end use performance.
Uses
[edit]PIR is typically produced as a foam and used as rigid thermal insulation. Its thermal conductivity has a typical value of 0.023 W/(m·K) (0.16 BTU·in/(hr·ft2·°F)) depending on the perimeter:area ratio.[3] PIR foam panels laminated with pure embossed aluminium foil are used for fabrication of pre-insulated duct that is used for heating, ventilation and air conditioning systems. Prefabricated PIR sandwich panels are manufactured with corrosion-protected, corrugated steel facings bonded to a core of PIR foam and used extensively as roofing insulation and vertical walls (e.g. for warehousing, factories, office buildings etc.). Other typical uses for PIR foams include industrial and commercial pipe insulation, and carving/machining media (competing with expanded polystyrene and rigid polyurethane foams).[citation needed]
Effectiveness of the insulation of a building envelope can be compromised by gaps resulting from shrinkage of individual panels. Manufacturing criteria require that shrinkage be limited to less than 1%[citation needed] (previously 2%[citation needed]).[4] Even when shrinkage is limited to substantially less than this limit, the resulting gaps around the perimeter of each panel can reduce insulation effectiveness, especially if the panels are assumed to provide a vapor/infiltration barrier. Multiple layers with staggered joints, ship lapped or tongue & groove joints greatly reduce these problems.[citation needed]
Polyisocyanurates of isophorone diisocyanate are also used in the preparation of polyurethane coatings based on acrylic polyols[5] and polyether polyols.[6]
Health hazards
[edit]PIR insulation can be a mechanical irritant to skin, eyes, and upper respiratory system during fabrication (such as dust).[7] No statistically significant increased risks of respiratory diseases have been found in studies.[8][better source needed]
Fire risk
[edit]PIR is at times stated to be fire retardant, or contain fire retardants, but these describe the results of "small scale tests" and "do not reflect [all] hazards under real fire conditions";[9][better source needed] the extent of hazards from fire include not just resistance to fire but the scope for toxic byproducts from different fire scenarios.
A 2011 study of fire toxicity of insulating materials at the University of Central Lancashire's Centre for Fire and Hazard Science studied PIR and other commonly used materials under more realistic and wide-ranging conditions representative of a wider range of fire hazard, observing that most fire deaths resulted from toxic product inhalation. The study evaluated the degree to which toxic products were released, looking at toxicity, time-release profiles, and lethality of doses released, in a range of flaming, non-flaming, and poorly ventilated fires, and concluded that PIR generally released a considerably higher level of toxic products than the other insulating materials studied (PIR > PUR > EPS > PHF; glass and stone wools also studied).[10] In particular, hydrogen cyanide is recognised as a significant contributor to the fire toxicity of PIR (and PUR) foams.[11]
PIR insulation board (cited as the FR4000 and the FR5000 products of Celotex, a Saint-Gobain company)[12] was proposed to be used externally in the refurbishment of Grenfell Tower, London, with vertical and horizontal runs of 100 mm and 150 mm thickness respectively;[13] subsequently "Ipswich firm Celotex confirmed it provided insulation materials for the refurbishment."[14] On 14 June 2017 the block of flats, within 15 minutes, was enveloped in flames from the fourth floor to the top 24th floor. The public inquiry into the fire determined that the Celotex Insulation material was a contributory factor to the causes of the rapid spread of the fire. [15]
References
[edit]- ^ Building Science Corporation (January 2007). "Guide to Insulating Sheathing" (PDF). p. 6.
- ^ Merillas B, Martín-de León J, Villafañe F, Rodríguez-Pérez MÁ (April 2022). "Optical Properties of Polyisocyanurate-Polyurethane Aerogels: Study of the Scattering Mechanisms". Nanomaterials. 12 (9): 1522. doi:10.3390/nano12091522. PMC 9100237. PMID 35564231.
- ^ Celotex GA4000 PIR specification
- ^ Riahinezhad M, Hallman M, Masson JF (2021-07-07). "Critical Review of Polymeric Building Envelope Materials: Degradation, Durability and Service Life Prediction". Buildings. 11 (7): 299. doi:10.3390/buildings11070299. ISSN 2075-5309.
- ^ Gite VV, Mahulikar PP, Hundiwale DG (August 2010). "Preparation and properties of polyurethane coatings based on acrylic polyols and trimer of isophorone diisocyanate". Progress in Organic Coatings. 68 (4): 307–312. doi:10.1016/j.porgcoat.2010.03.008.
- ^ Gite VV, Mahulikar PP, Hundiwale DG, Kapadi U (2004). "Polyurethane coatings using trimer of isophorone diisocyanate" (PDF). Journal of Scientific and Industrial Research. 64: 348–354.
- ^ Reinerte S, Jurkjane V, Cabulis U, Viksna A (September 2021). "Identification and Evaluation of Hazardous Pyrolysates in Bio-Based Rigid Polyurethane-Polyisocyanurate Foam Smoke". Polymers. 13 (19): 3205. doi:10.3390/polym13193205. PMC 8512043. PMID 34641023.
- ^ "Household Products Database". hpd.nlm.nih.gov. Archived from the original on 2007-06-13.
- ^ "PIR/ PUR, polyurethane and polyisocyanurate rigid foam datasheet" (PDF). Temati.com. Archived from the original (PDF) on 4 March 2016.
- ^ Assessment of the fire toxicity of building insulation materials - Stec & Hull, 2011; reported in Energy and Buildings jnl, 43 (2-3), pp. 498-506 (2011); doi:10.1016/j.enbuild.2010.10.015
- ^ McKenna ST, Hull TR (2016-04-21). "The fire toxicity of polyurethane foams" (PDF). Fire Science Reviews. 5 (1): 3. doi:10.1186/s40038-016-0012-3. ISSN 2193-0414. S2CID 20589341.
- ^ "The Distinction Between Celotex PIR Insulation Boards". Builders Insulation. Retrieved 2022-09-28.
- ^ Max Fordham LLP (17 August 2012). "Sustainability and Energy Statement. Grenfell Tower Refurbishment" (PDF). p. 6. Celotex say FR5000 has "Class 0 fire performance throughout the product in accordance with BS 476", its "fire propagation [is] Pass" re BS 476 Part 6, and that its "surface spread of flame [is] Class 1" re BS 476 Part 7 (https://www.celotex.co.uk/products/fr5000 - link to Product Data Sheet PDF, August 2016, pp. 1 & 2).
- ^ The Guardian (15 June 2017). "Experts warned government against cladding material used on Grenfell". TheGuardian.com.
- ^ "Grenfell Inquiry: ACM cladding was 'primary cause of fire spread' and tower did not comply with regulations, judge rules".
External links
[edit]- Polyisocyanurate Insulation Manufacturers Association
- Polyisocyanurate Insulation energy savings, by Center for the Polyurethanes Industry
- Continuous Insulation Resources for several types of rigid foam continuous insulation
- Technical guide to Polyisocyanurate insulation — detailed information on composition, thermal performance, and installation methods.
Polyisocyanurate
View on GrokipediaOverview
Definition and Composition
Polyisocyanurate (PIR), also known as polyiso, is a thermoset polymeric foam material distinguished by its rigid structure and use in thermal insulation applications. It forms through the trimerization of isocyanate monomers, creating a cross-linked network of isocyanurate rings that impart superior thermal stability and fire resistance compared to polyurethane foams.[8][9] The primary chemical composition of PIR involves the reaction of polyisocyanates, such as methylene diphenyl diisocyanate (MDI), with polyols at an elevated isocyanate-to-polyol ratio that favors isocyanurate formation over urethane linkages. This process incorporates blowing agents to generate the closed-cell foam structure, catalysts to control reaction kinetics, and flame retardants like tris(1-chloro-2-propyl) phosphate to enhance fire performance. Blowing agents historically included chlorofluorocarbons (CFCs), but modern formulations use hydrocarbons such as pentane to minimize environmental impact while maintaining low thermal conductivity.[3][2] In terms of molecular structure, the isocyanurate rings—cyclic trimers of isocyanate groups—provide a highly stable backbone resistant to degradation at temperatures up to 200°C, enabling PIR's classification as a high-performance insulation with R-values typically ranging from 5.6 to 6.5 per inch. Additives such as surfactants stabilize cell formation, ensuring uniform density, often around 32 kg/m³ for commercial boards.[10][11]Distinction from Related Materials
Polyisocyanurate (PIR) foam differs from polyurethane (PUR) foam primarily in its chemical structure, formed through the trimerization of isocyanate monomers into rigid isocyanurate ring linkages, whereas PUR relies on urethane linkages from the reaction between polyols and isocyanates.[5] [12] This results in PIR employing a higher isocyanate index, typically around 250% compared to 105% for PUR, often using polyester polyols that promote greater crosslinking and rigidity.[9] [13] In terms of performance, PIR exhibits superior fire resistance and thermal stability over PUR due to its more stable ring structure, which resists degradation at elevated temperatures and produces less smoke and fewer toxic gases during combustion.[14] [15] Rigid PUR foams, while effective insulators, are more prone to flammability and dimensional changes under heat, limiting their use in high-risk fire applications.[2] [16] Compared to polystyrene foams such as expanded (EPS) or extruded (XPS), PIR is a thermoset material that maintains structural integrity without melting or dripping under fire exposure, unlike the thermoplastic polystyrene which softens and propagates flames.[17] [18] PIR also offers higher thermal resistance, with R-values around 5.6-6.5 per inch versus 3.8-4.4 for polystyrene, enabling thinner applications for equivalent insulation.[19] [20] Phenolic foams surpass PIR in fire resistance and smoke suppression due to their inherently low flammability and closed-cell structure derived from phenolic resins, but they are more brittle, moisture-sensitive, and costly to produce, whereas PIR balances durability with manufacturability.[21] [22] These distinctions position PIR as a versatile intermediate in insulation hierarchies, prioritizing thermal efficiency and fire safety over the flexibility of PUR or the economy of polystyrene.[23]History
Early Development and Invention
Polyisocyanurate, a thermoset polymer formed primarily through the trimerization of isocyanates, traces its roots to advancements in polyurethane chemistry, which Otto Bayer and his team at IG Farben first synthesized in 1937 via the reaction of polyols with diisocyanates.[10] This foundational work enabled subsequent explorations into isocyanate-derived foams, where trimerization—catalyzed reactions yielding isocyanurate ring structures—emerged as a method to produce materials with enhanced thermal stability and fire resistance compared to standard polyurethanes.[10] Early research in the 1950s focused on rigid polyurethane foams, but limitations in combustibility prompted investigations into polyisocyanurate variants, leveraging the isocyanurate linkages for superior char formation and reduced smoke evolution during fires.[10] By the mid-1960s, urethane-modified polyisocyanurate (PIR) foams were developed as a hybrid class, combining polyurethane's flexibility in formulation with polyisocyanurate's rigidity and low-flammability profile.[10] These materials were introduced in 1967, representing a deliberate engineering improvement over pure polyurethane foams to meet growing demands for safer insulation in construction and industrial applications.[10] The modification involved balancing urethane linkages for processability with isocyanurate cross-linking for structural integrity, achieved through precise catalyst control during foaming.[10] Commercial viability followed swiftly, with Imperial Chemical Industries (ICI) in the United Kingdom pioneering a practical PIR foam formulation in 1968, marketed as Hexafoam for its hexameric isocyanurate emphasis and early adoption in rigid insulation boards.[24] This breakthrough addressed key challenges like dimensional stability under heat, positioning PIR as a candidate for building envelopes where fire codes increasingly mandated non-combustible barriers.[24] Initial production emphasized closed-cell structures with blowing agents like chlorofluorocarbons to achieve high R-values, though environmental concerns later drove reformulations.[3]Commercialization and Adoption
Urethane-modified polyisocyanurate foams were introduced in 1967 as an enhancement to polyurethane foams, incorporating isocyanurate crosslinking for improved thermal stability, dimensional stability, and flame resistance.[10] Commercialization followed in the early 1970s, with initial production focused on rigid foam boards for sidewall and roof insulation in building applications.[25] Early manufacturing employed continuous or batch processes to produce bunstock, prioritizing consistency in density and performance metrics like compressive strength.[10] Adoption gained momentum in the 1970s for low-slope commercial roofing systems, where polyisocyanurate's inherent fire resistance reduced the requirement for supplementary thermal barriers, distinguishing it from polyurethane alternatives.[9] By the 1980s, it had emerged as the dominant insulation in U.S. commercial roofing, achieving greater than 65% market share in new low-slope roof construction and approximately 60% in re-roofing as documented in 2006-2007 surveys.[25] The material also found use in refrigeration, petrochemical facilities, and LNG storage due to its low thermal conductivity and high compressive resistance.[10] Regulatory pressures from the 1987 Montreal Protocol accelerated adaptation, phasing out chlorofluorocarbon blowing agents by 1996 and transitioning to hydrocarbons like pentane by 2002, which preserved environmental compliance without compromising insulation efficacy.[3] This evolution supported sustained growth, with polyisocyanurate comprising over 70% of North American commercial roof insulation by the late 2010s.[3] The Polyisocyanurate Insulation Manufacturers Association, established in 1987, facilitated industry standardization and advocacy amid these changes.[3]Chemistry and Manufacturing
Chemical Reactions Involved
Polyisocyanurate polymers are primarily formed through the cyclotrimerization of isocyanate groups, where three isocyanate moieties (-N=C=O) undergo a stepwise nucleophilic addition to yield a stable six-membered isocyanurate ring consisting of alternating nitrogen and carbonyl units.[26] This reaction is exothermic and typically requires catalysis by strong bases, such as potassium carboxylates (e.g., potassium octoate) or organometallic compounds, which initiate the process by nucleophilic attack on the electrophilic carbon of the isocyanate.[27] The mechanism involves sequential additions: the catalyst adds to one isocyanate, forming an intermediate that reacts with a second isocyanate to produce an imidazolone-like species, followed by cyclization with a third isocyanate to close the ring and regenerate the catalyst.[28] In polyisocyanurate rigid foams (PIR), this trimerization competes with and complements the polyaddition reaction between polyisocyanates, such as polymeric methylene diphenyl diisocyanate (pMDI), and polyols to form polyurethane linkages.[29] Formulations for PIR emphasize excess isocyanate (isocyanate index often exceeding 200) to promote isocyanurate formation over urethane bonds, enhancing cross-linking density and thermal stability.[30] Trimerization catalysts are added alongside urethane catalysts (e.g., amine or tin compounds) and blowing agents to achieve the closed-cell structure during the simultaneous foaming and curing process.[31] The prevalence of isocyanurate linkages distinguishes PIR from polyurethane (PU) foams, contributing to superior fire resistance and char formation due to the aromatic and heterocyclic nature of the rings, which resist depolymerization at elevated temperatures.[29] Experimental studies confirm that higher trimerization extent correlates with reduced smoke production and improved limiting oxygen index values in combustion tests.[30]Production Processes and Raw Materials
Polyisocyanurate (PIR) foam is produced through a chemical reaction emphasizing the trimerization of isocyanates, which forms rigid, closed-cell structures distinct from polyurethane foams. The primary raw materials include polyisocyanates, such as polymeric methylene diphenyl diisocyanate (MDI), which provide the isocyanate (-NCO) groups essential for both urethane linkage and isocyanurate ring formation.[32] Polyols, typically polyester types with hydroxyl numbers exceeding 200 mg KOH/g, serve as co-reactants to initiate the reaction and influence foam density and rigidity.[32] Additional components encompass blowing agents like hydrofluoroolefins (HFOs) or water (which generates CO₂ via reaction with isocyanates), trimerization catalysts such as potassium acetate or quaternary ammonium salts to promote isocyanurate ring cyclization, surfactants for cell stabilization, and flame retardants for enhanced fire performance.[33][32] These materials are stored as liquids in on-site tanks and heated prior to use to optimize viscosity and reaction kinetics.[33] The manufacturing process employs a two-component system: the A-component (isocyanate-rich, often at an isocyanate index of 200–350% relative to polyol stoichiometry to favor trimerization over simple urethane bonds) and the B-component (polyol premix with catalysts, blowing agents, and additives).[34][32] In continuous lamination for insulation boards— the predominant method—facers (e.g., glass-fiber reinforced mats or foil) are unwound to form top and bottom layers. The components are compounded separately, with the polyol heated and mixed with blowing agent, then combined with isocyanate at a high-speed mixing head. The reactive mixture is poured onto the lower facer, covered by the upper facer, and fed into a laminator where exothermic foaming occurs, expanding the material into a rigid core while adhering to the facers.[33] The laminator controls parameters like temperature (typically 140–160°C for curing), conveyor speed, and pressure to achieve uniform cell structure and specified thicknesses, often producing tapered or flat boards.[33][32] Post-lamination, the continuous sheet undergoes trimming, cross-cutting into standard lengths (e.g., 4 ft or 8 ft), and gang sawing for width. The boards are then packaged in plastic film, labeled, and warehoused for further curing to ensure dimensional stability and full reaction completion.[33] Alternative processes include spray foaming or batch molding for non-board applications, where the mixture is applied or poured into molds and cured in ovens, but these are less common for rigid PIR insulation due to challenges in controlling uniformity.[32] Quality control involves testing samples for metrics like R-value, compressive strength, and foam density throughout production.[33]Physical and Thermal Properties
Key Physical Characteristics
Polyisocyanurate foams are characterized by a rigid, closed-cell structure formed through the polymerization of isocyanates, resulting in a thermoset matrix with over 90% closed cells that enhances mechanical integrity and restricts fluid ingress.[35] This structure contributes to the material's high stiffness and resistance to deformation under load, distinguishing it from more flexible open-cell foams.[32] Nominal density for standard polyisocyanurate insulation boards used in building applications typically ranges from 1.8 to 2.5 lb/ft³ (29 to 40 kg/m³), with 2.0 lb/ft³ (32 kg/m³) being common for roofing and wall products; higher densities, such as 6.0 lb/ft³ (96 kg/m³), are available for specialized high-strength uses like pipe supports.[36][37] Compressive strength, evaluated parallel to the foam rise per ASTM D1621, generally falls between 16 and 25 psi (110 and 172 kPa) for Type I and II boards under ASTM C1289 classification, enabling load-bearing capacity in applications like roof decks without significant creep.[38][39] Water absorption remains low due to the closed-cell morphology, typically under 1% by volume after 96-hour immersion per ASTM C272, though immersion values can reach up to 3% in prolonged exposure scenarios, with facers further mitigating uptake.[40] Dimensional stability is favorable, showing linear changes of less than 2% after 7 days at 158°F (70°C) and 97% relative humidity per ASTM D2126, supporting long-term structural performance in varying environmental conditions.[40]| Property | Typical Value | Test Method |
|---|---|---|
| Density | 2.0 lb/ft³ (32 kg/m³) nominal | ASTM D1622 |
| Compressive Strength | 16–25 psi (110–172 kPa) | ASTM D1621 |
| Water Absorption | <1% by volume | ASTM C272 |
| Dimensional Stability | <2% linear change | ASTM D2126 |
Thermal Performance Metrics
Polyisocyanurate rigid foam insulation demonstrates high thermal resistance, with a typical initial thermal conductivity of 0.020 to 0.022 W/m·K under standard laboratory conditions defined in ASTM C518, equating to an R-value of approximately 6.0 per inch (ft²·h·°F/Btu) at a mean temperature of 75°F (24°C).[41][42] This performance stems from its closed-cell structure filled with low-conductivity blowing agents like pentane, which minimize convective and conductive heat transfer.[43] Long-term thermal resistance (LTTR), a predictive metric for aged performance incorporated into ASTM C1289 specifications, adjusts for cell gas diffusion and polymer aging, yielding effective R-values of 5.6 to 5.7 per inch for commercial polyiso boards after simulated five-year exposure.[44][45] LTTR testing involves accelerated aging at elevated temperatures (e.g., 70°C) followed by extrapolation, revealing a 20-25% decline from initial values in polyisocyanurate samples due to replacement of insulating gases with air.[46] Temperature significantly influences metrics; polyiso's thermal conductivity rises at both extremes, decreasing R-value by up to 10% at mean temperatures above 50°C from enhanced gas permeation and by as much as 20% at low temperatures (e.g., -4°C mean) due to reduced blowing agent efficacy and potential cell stiffening effects.[47][48] In roofing assemblies with mean temperatures often exceeding 100°F (38°C), design R-values may require upward adjustment by 10-15% to account for this drift, as validated by field-correlated models.[49][50]| Metric | Typical Value | Test Condition/Standard | Notes |
|---|---|---|---|
| Thermal Conductivity (λ) | 0.020–0.022 W/m·K | ASTM C518 at 75°F mean | Initial value; increases with aging and temperature extremes.[41][43] |
| Initial R-value per inch | R-6.0 | 75°F mean temperature | Laboratory short-term measurement.[42] |
| LTTR per inch | R-5.6 to R-5.7 | ASTM C1289 accelerated aging | Accounts for 5+ years in service; lower for thicker boards due to diffusion gradients.[44][45] |
| Temperature Adjustment | -10% to -20% R-value | >50°C or <0°C mean | Empirical from lab and modeled data; critical for cold climates or hot roofs.[47][49] |