Preparation and characterization of low-temperature coal tar toughened phenolic foams
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摘要: 本研究以低温煤焦油为原料，部分替代石油基苯酚制备煤焦油基酚醛泡沫（CPF），对CPFs的化学结构、表观形貌、压缩强度、粉化率、热稳定性、阻燃性能和隔热性能进行了表征。结果表明，CPFs与常规酚醛泡沫的化学结构相似。与常规酚醛泡沫相比，30%CPF和40%CPF的压缩强度分别增加了18.3%和55.9%；且由于脂肪结构如烷基酚的引入，使得泡沫的韧性显著提高，其粉化率分别下降了22.9%和50.8%。此外，CPFs在低温下的热稳定性增加。尽管CPFs的极限氧指数下降，导热系数增加，但依然保持较好的阻燃和隔热性能。这说明低温煤焦油能够高比例地替代苯酚制备出性能优良的酚醛泡沫，为低温煤焦油的高值化利用提供了新的思路。Abstract: In this study, coal tar-based phenolic foam (CPF) was prepared using low-temperature coal tar as raw material to partially replace phenol. The chemical structure, apparent morphology, compressive strength, thermal stability, flame retardancy and thermal insulation properties of CPFs were characterized. The results show that CPFs have similar chemical structures to conventional phenolic foam. Comparing with conventional phenolic foam, the compressive strength of 30%CPF and 40%CPF increases by 18.3% and 55.9%, and the pulverization rate decreases by 22.9% and 50.8%, respectively. The results indicated that toughness was significantly strengthened due to the incorporation of aliphatic structures such as alkylphenols. In addition, the thermal stability of CPFs in the low temperature stage also improves. Although the limited oxygen index of CPFs decreases and thermal conductivity of CPFs increases, they still maintain good flame retardancy and thermal insulation properties. The obtained results prove that low-temperature coal tar can significantly replace phenol to prepare phenolic foam with good performance, which provides a new idea for the high-value utilization of low-temperature coal tar.
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Key words:
- low-temperature coal tar /
- phenolic foams /
- toughness /
- characterization
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Figure 2 Possible ways of some components in coal tar participating in polymerization of phenolic resins
Table 1 Formulations of PR and CPRs with different substitution rates
Substitution rate /% Low-temp. coal tar /g Phenol /g 37% aqueous formaldehyde /g 15% aqueous NaOH /mL 0 0 50 77.54 15 10 5 45 71.34 15 20 10 40 65.13 15 30 15 35 58.93 15 40 20 30 52.73 15 
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Table 2 Basic properties of PR and CPRs
Resin PR 10%CPR 20%CPR 30%CPR 40%CPR Viscosity /(Pa·s) 4.1 6.9 10.4 20.7 48.7 Solid content /% 79.2 77.7 76.6 75.4 74.3
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Table 3 Arenes with RC > 0.2% detected in low-temperature coal tar by GC/MS
Arene RC Arene RC Naphthalene 0.32 2-methyl-9H-fluorene 0.63 5H-benzo[7]annulene 0.60 2,6-dimethylbiphenyl 0.49 2-methylnaphthalene 0.36 2,4,6-trimethylbiphenyl 0.67 1,2,4-trimethyl-5-(prop-1-en-2-yl)benzene 0.21 3,3',4,4'-tetramethylbiphenyl 0.22 2,6-dimethylnaphthalene 0.31 3,4-diethylbiphenyl 0.70 1,7-dimethylnaphthalene 0.75 1a,9b-dihydro-1H-cyclopropa[l]phenanthrene 1.16 3-ethyl-1,2,4,5-tetramethylbenzene 0.43 2,3-dimethylphenanthrene 0.75 1,1,4,5,6-pentamethylindane 0.29 pyrene 0.26 4,6,8-trimethylazulene 0.84 2,3,5-trimethylphenanthrene 1.16 1,6,7-trimethylnaphthalene 0.85 1-methylpyrene 0.46 Phenalene 0.29 2-isopropyl-10-methylphenanthrene 1.22 1-allylnaphthalene 0.28 1-methyl-4-((4-propylphenyl)ethynyl)benzene 0.21 4-methylbiphenyl 0.21 4,8-dimethyl-6-phenylazulene 0.30 3,4'-dimethylbiphenyl 0.42 1,3-dimethyl-8-isopropyl-phenanthrene 0.29 6-isopropyl-1,4-dimethylnaphthalene 0.25 tetracene 0.22 RC: relative content
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Table 4 Other oxygenates with RC > 0.2% detected in low-temperature coal tar by GC/MS
Other oxygenate RC Other oxygenate RC 2-acetyl-2-carene 0.21 1-heneicosyl formate 0.24 2-methylindan-1-ol 0.33 3-hydroxy-estra-1,3,5(10),9(11)-tetraen-17-one 0.40 2,3,4,5-tetramethylbenzaldehyde 0.20 1-heneicosanol 0.52 2-methyl-4-(2,6,6-trimethylcyclohex-1-en-1-yl)but-3-enal 0.31 methyl 3-(3-methylbut-2-en-1-yl)-1,4-dioxo-1,4-dihydronaphthalene-2-carboxylate 0.31 1,2a,3,4,5,7,8,9-octahydro-2H-benzo[cd]pyren-5-ol 0.30 11-methyl-10,11-dihydrotetraphene-10,11-diol 0.29 2,3-diphenylcycloprop-2-en-1-one 0.25 1,2-dimethylnaphtho[2,1-b]furan 0.26 4,6,8-trimethyl-1-azulenecarbaldehyde 0.45
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Table 5 Phenols detected in low-temperature coal tar by GC/MS
Phenols RC Phenol RC With 0 active site 2,3,5-trimethylphenol 0.14 6,6'-methylenebis(2-(tert-butyl)-4-methylphenol) 0.50 2,6-dimethyl-1,4-benzenediol 0.35 With 1 active sites 2,5-dimethyl-1,3-benzenediol 0.04 2,4-xylenol 1.48 2-(2-methylallyl)phenol 0.98 2,3,6-trimethylphenol 0.16 4,5-dimethyl-1,3-benzenediol 0.08 2-allyl-6-cresol 0.01 6-methyl-4-indanol 0.27 2-ethyl-6-cresol 0.34 5,8-dihydronaphthalen-1-ol 0.16 3-methylcatechol 0.30 [1,1'-biphenyl]-2-ol 0.03 2-ethyl-4-cresol 1.26 naphthalen-1-ol 0.61 2,3,6-trimethylphenol 0.23 9H-fluoren-2-ol 0.80 2-ethyl-4,5-xyenol 0.23 5,7-dimethylnaphthalen-1-ol 0.08 6-propyl-2-cresol 0.10 6,7-dimethylnaphthalen-1-ol 1.74 4-methyl-2-(pent-3-en-2-yl)phenol 0.17 2-styrylphenol 0.11 2-methylnaphthalen-1-ol 0.18 4-(cyclohepta-2,4,6-trien-1-yl)phenol 0.17 3,6-dimethyl-2-(2-methylbut-3-en-2-yl)phenol 0.07 4-benzylphenol 0.04 2,5,8-trimethylnaphthalen-1-ol 0.28 dibenzo[b,d]furan-2-ol 0.19 1,2,3,4-tetrahydrophenanthren-9-ol 0.28 4-styrylphenol 0.21 with 2 active sites phenanthren-2-ol 0.22 2-ethylphenol 0.22 1-phenyl-1H-inden-4-ol 0.54 2,5-xyenol 0.44 with 3 active sites 3,4-xyenol 0.39 phenol 0.78 Catechol 0.20 3-cresol 2.84 2-ethyl-5-cresol 0.21 3-ethylphenol 1.52 3,4,5-trimethylphenol 0.41 orcinol 0.09 4-methylcatechol 0.31 3,5-diethylphenol 0.50 Thymol 0.09
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Table 6 Basic characteristics of PF and CPFs
Foam Density /
(kg·m−3)Compressive strength /
MPaPulverization rate /
%Thermal conductivity /
(W·m−1·K−1)PF 50.8 0.172 11.8 0.0391 10%CPF 50.2 0.107 11.6 0.0395 20%CPF 62.4 0.166 9.1 0.0414 30%CPF 93.0 0.268 5.8 0.0443 40%CPF 77.3 0.203 9.1 0.0432
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Table 7 TG and DTG analysis of PF and CPFs
Sample t-5% /°C tmax /°C Residual
mass /%step II step III PF 90.9 288.1 451.5 40.9 10%CPF 96.4 285.2 450.4 39.7 20%CPF 106.2 284.8 451.1 39.6 30%CPF 103.0 286.2 458.3 40.6 40%CPF 123.6 291.4 453.2 43.1
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