A study of chemical composition and physical-mechanical properties of rigid polyurethane-polyisocyanurate foams changes under conditions of extreme heating
Restricted accessResearch articleFirst published online November, 2024
A study of chemical composition and physical-mechanical properties of rigid polyurethane-polyisocyanurate foams changes under conditions of extreme heating
Polyurethane-polyisocyanurate rigid (PIR) foams are used as thermal insulation materials in a wide range of applications such as construction and pipe insulation. Some of the utilizations require the maximum operating temperature of these materials to reach extremely high temperatures. This work is devoted to the study of changes in the chemical composition and the main physical-mechanical and thermophysical characteristics of PIR foams subjected to prolonged extreme heating in the presence of the material direct contact with air and in its absence. Based on the results obtained, prolonged extreme heating of such materials leads to a significant change in their chemical composition, mainly due to the thermal decomposition of allophanate, urethane and urea linkages, as well as the gradual formation of uretidione, linear carbodiimide polymer and the oxidation of ethers to esters. The relative compressive strength of these materials changes only to a small extent, while the thermal conductivity of these materials increases significantly during heating.
SimonDBorregueroAMde LucasA, et al.Recycling of polyurethanes from laboratory to industry, a journey towards the sustainability. Waste Manag2018; 76: 147–171. DOI: 10.1016/j.wasman.2018.03.041.
2.
StirnaUBeverteIYakushinV, et al.Mechanical properties of rigid polyurethane foams at room and cryogenic temperatures. J Cell Plast2011; 47: 337–355. DOI: 10.1177/0021955X11398381.
3.
DasAMahanwarP. A brief discussion on advances in polyurethane applications. Adv Ind Eng Polym Res2020; 3: 93–101. DOI: 10.1016/j.aiepr.2020.07.002.
4.
LeeJRDhitalD. Review of flaws and damages in space launch vehicle: structures. J Intell Mater Syst Struct2013; 24: 4–20. DOI: 10.1177/1045389X12458041.
5.
StirnaUBeverteIYakushinV, et al.Mechanical properties of rigid polyurethane foams at room and cryogenic temperatures. J Cell Plast2011; 47: 337–355. DOI: 10.1177/0021955X11398381.
6.
DusekKSpirkovaMIlavskyM. Network formation in polyurethanes due to allophanate and biuret formation: gel fraction and equilibrium modulus. Makromol. Chem. Macromolecular Symposia1991; 45: 87–95. DOI: 10.1002/masy.19910450112.
7.
Mohd-RusAZKempTJClarkAJ. Degradation studies of polyurethanes based on vegetable oils. Part 2. Thermal degradation and materials properties. Progr React Kinet Mech2009; 34: 1–41. DOI: 10.3184/146867809X425749.
8.
FrischKCReegenSL. Advances in urethane science and technology. Volume 41st ed.Lancaster: Technomic Publishing, 1976, p. 239p.
9.
LeggeNRHoldenGSchroederHE. Thermoplastic elastomers: a comprehensive review. 1st ed.Orlando: Hanser Publishers, 1987, p. 574p.
10.
ZharkovVVVlasovRR. A quantitative study of the allophanate formation reaction in PIR foams by FT-IR spectroscopy. J Cell Plast2022; 58: 877–891. DOI: 10.1177/0021955X221141544.
11.
Al NabulsiACozzulaDHagenT, et al.Isocyanurate formation during rigid polyurethane foam assembly: a mechanistic study based on in-situ IR and NMR spectroscopy. Polym Chem2018; 9: 4891–4899. DOI: 10.1039/C8PY00637G.
12.
BucklesREMcGrewLA. A kinetic study of the dimerization of phenyl isocyanate. J Am Chem Soc1966; 88: 3582–3586. DOI: 10.1021/ja00967a021.
McKennaSTMcKennaSTHullTR. The fire toxicity of polyurethane foams. Fire Sci Rev2016; 5: 1–27. DOI: 10.1186/s40038-016-0012-3.
15.
ChattopadhyayDKWebsterDC. Thermal stability and flame retardancy of polyurethanes. Prog Polym Sci2009; 34: 1068–1133. DOI: 10.1016/j.progpolymsci.2009.06.002.
16.
ChattopadhyayDKRajuKVSN. Structural engineering of polyurethane coatings for high performance applications. Prog Polym Sci2007; 32: 352–418. DOI: 10.1016/j.progpolymsci.2006.05.003.
17.
VoorheesKJLattimerRP. Mechanisms of pyrolysis for a specifically labeled deuterated urethane. J Polym Sci Polym Chem Ed1982; 20: 1457–1467. DOI: 10.1002/pol.1982.170200608.
18.
MertenVRLauererDBraunG, et al.Über den aufbau von polyurethan-kunststoffen. II. Die struktur von polyurethan-schaumstoffen in abhängigkeit von der temperatur, der zeit und der rezeptur; IR-spektroskopische nachweisgrenzen für urethan-und harnstoffgruppen in polymeren. Makromol Chem1967; 101: 337-366. DOI: 10.1002/macp.1967.021010119. https://onlinelibrary.wiley.com/doi/10.1002/macp.1967.021010119
19.
Dominguez-RosadoELiggatJJSnapeCE, et al.Thermal degradation of urethane modified polyisocyanurate foams based on aliphatic and aromatic polyester polyol. Polym Degrad Stab2002; 78: 1–5. DOI: 10.1016/S0141-3910(02)00086-1.
20.
VitkauskieneIMakuskaRStirnaU, et al.Thermal properties of polyurethane-polyisocyanurate foams based on poly(ethylene terephthalate) waste. Mate Sci2011; 17: 249–253. DOI: 10.5755/j01.ms.17.3.588.
21.
ChenXLiJGaoM. Thermal degradation and flame retardant mechanism of the rigid polyurethane foam including functionalized graphene oxide. Polymers2019; 11: 78. DOI: 10.3390/polym11010078.
22.
ZharkovVV. Kolebatel’nye spektry alkil-N-feniluretanov i analiticheskoe primenenie Ik-spektroskopii pri issledovanii struktury poliuretanovyh elastomerov [Vibrational spectra of alkyl-N-phenylurethanes and analytical application of IR spectroscopy in the study of the structure of polyurethane elastomers]. PhD thesis, Gorkiy. 1966; 251p.
23.
BuistJM. Developments in polyurethane. Volume 11st ed.Amsterdam: Elsevier Science Ltd, 1978, p. 290p.
24.
AouKSchrockAKGinzburgVV, et al.Characterization of polyurethane hard segment length distribution using soft hydrolysis/MALDI and Monte Carlo simulation. Polymer2013; 54: 5005–5015. DOI: 10.1016/j.polymer.2013.07.014.
25.
KennemurJGNovakBM. Advances in polycarbodiimide chemistry. Polymer2011; 52: 1693–1710. DOI: 10.1016/j.polymer.2011.02.040.
26.
ChenALWeiKLJengRJ, et al.Well-defined polyamide synthesis from diisocyanates and diacids involving hindered carbodiimide intermediates. Macromolecules2011; 44: 46–59. DOI: 10.1021/ma1022378.
27.
SuydamFH. The C=N stretching frequency in azomethines. Anal Chem1963; 35: 193–195. DOI: 10.1021/ac60195a024.
28.
RychlyJLattuati-DerieuxALavedrineB, et al.Assessing the progress of degradation in polyurethanes by chemiluminescence and thermal analysis. II. Flexible polyether- and polyester-type polyurethane foams. Polym Degrad Stab2011; 96: 462–469. DOI: 10.1016/j.polymdegradstab.2011.01.012.
29.
ReignierJMechinFSarbuA. Chemical gradients in PIR foams as probed by ATR-FTIR analysis and consequences on fire resistance. Polym Test2021; 93: 106972. DOI: 10.1016/j.polymertesting.2020.106972.
30.
Dement’evAGTarakanovOGBelovaYV. A method of predicting the stability of foamed polyisocyanurate subjected to long-term high temperature ageing. Polym. Sci. U.S.S.R1988; 30: 2030–2037. DOI: 10.1016/0032-3950(88)90056-1.
31.
Santiago-CalvoMTirado-MediavillaJRuiz-HerreroJL, et al.Long-term thermal conductivity of cyclopentane–water blown rigid polyurethane foams reinforced with different types of fillers. Polym Int2019; 68: 1826–1835. DOI: 10.1002/pi.5893.
32.
HasanzadehRAzdastTDoniaviA, et al.Multi-objective optimization of heat transfer mechanisms of microcellular polymeric foams from thermal-insulation point of view. Therm Sci Eng Progr2019; 9: 21–29. DOI: 10.1016/j.tsep.2018.11.002.
33.
GlicksmanLR. Heat transfer and ageing of cellular foam insulation. Cell. Pol1991; 10: 276–293. DOI: 10.1177/026248939101000402.
34.
GlicksmanL. Low density cellular plastics: physical basis of behaviour. 1st ed.Berlin, Germany: Springer, 1994, p. 384p.
35.
LenzJPospiechDPavenM, et al.Influence of the catalyst concentration on the chemical structure, the physical properties and the fire behavior of rigid polyisocyanurate foams. Polym Degrad Stab2020; 177: 109168. DOI: 10.1016/j.polymdegradstab.2020.109168.
36.
MakaveckasTBliudziusRBurlingisA. Determination of the impact of environmental temperature on the thermal conductivity of polyisocyanurate (PIR) foam products. J Build Eng2021; 41: 102447. DOI: 10.1016/j.jobe.2021.102447.
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