Flame Retardancy of Epoxy Resin Enhanced by Intercalation of Magnesium Aluminum Hydrotalcite with Phosphorous Flame Retardants

doi:10.19894/j.issn.1000-0518.240130

Chinese Journal of Applied Chemistry ›› 2024, Vol. 41 ›› Issue (8): 1154-1167.DOI: 10.19894/j.issn.1000-0518.240130

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Flame Retardancy of Epoxy Resin Enhanced by Intercalation of Magnesium Aluminum Hydrotalcite with Phosphorous Flame Retardants

Xue-Yan YANG¹, Jun-Jie SHI¹, Yong-Jun ZHOU², Yu-Mei DAI², Hong-Zhou LI¹()

^1.College of Environmental and Resources，Engineering Research Center of Polymer Green Recycling of Ministry of Education，Fuzhou 350007，China
^2.Minnan Science and Technology University，Quanzhou 362200，China

Received:2024-04-18 Accepted:2024-06-20 Published:2024-08-01 Online:2024-08-27
Contact: Hong-Zhou LI
About author:lihongzhou@fjnu.edu.cn
Supported by:
the National Natural Science Foundation of China(51903049);the Natural Science Foundation of Fujian Province(2021J01198);the Scientific and Technological Project of Quanzhou(2022C008R)

Abstract

Abstract:

Ammonium polyphosphate （APP）， 9，?10-dihydro-9-oxa-10-phosphame-10-oxide （DOPO）， and melamine polyphosphate （MPP） were intercalated into magnesia-aluminum hydrotalcite （MAH） to obtain intercalation complexes （APP-MAH-6H， DOPO-MAH-6H， MPP-MAH-6H）. EP/DOPO-MAH-6H， EP/APP-MAH-6H， and EP/MPP-MAH-6H were prepared by mixing the intercalation complexes and hot curing with epoxy resin （EP）. The structures and properties of EP/DOPO-MAH-6H， EP/APP-MAH-6H， and EP/MPP-MAH-6H were characterized by cone calorimetry， vertical combustion， limiting oxygen index（LOI）， scanning electron microscopy （SEM） and Raman spectrum， and their flame retardant properties were investigated. The experimental results show that： Compared with pure EP， the peak heat release rate（pHRR） of EP/DOPO-MAH-6H， EP/APP-MAH-6H and EP/MPP-MAH-6H decreased from 1079.2 kW/m² to 481.3， 445.7 and 385.8 kW/m²， respectively， and the LOI increased from 25.1% to 32.2%， 32.9% and 33.8%， respectively. In addition， in the UL-94 test of vertical combustion， EP/DOPO-MAH-6H， EP/APP-MAH-6H and EP/MPP-MAH-6H all achieved V-0 levels. According to SEM， the morphologies of char residue for EP/DOP-MAH-6H and EP/APP-MAH-6H are large and continuous， while the morphologies of char residue for EP/MPP-MAH-6H are dense and continuous. The test results of Raman spectrum show that the three EP composites form a continuous， high-quality carbon layer， which can effectively isolate the transfer of oxygen and heat to the internal matrix during the combustion process. Therefore， the addition of the three phosphorus intercalation complexes can greatly improve the flame retardancy of epoxy resin.

Key words: Epoxy resin, 9, 10-Dihydro-9-oxa-10-phosphaphena-nthrene-10-oxide, Ammonium polyphosphate, Melamine polyphosphate, Hydrotalcite intercalation, Flame retardant property

CLC Number:

O632

Xue-Yan YANG, Jun-Jie SHI, Yong-Jun ZHOU, Yu-Mei DAI, Hong-Zhou LI. Flame Retardancy of Epoxy Resin Enhanced by Intercalation of Magnesium Aluminum Hydrotalcite with Phosphorous Flame Retardants[J]. Chinese Journal of Applied Chemistry, 2024, 41(8): 1154-1167.

Figures/Tables 19

Table 1 Formula of EP/DOPO/MAH flame retardant composite

Sample	w（EP）/%	w（DDM）/%	w（MAH）/%	w（DOPO）/%
EP	80	20	0	0
EP/DOPO	76	19	0	5
EP/DOPO+MAH	75	19	1	5
EP/DOPO-MAH-6H	75	19	1	5

Fig.1 Cone calorimeter tests of EP， EP/DOPO， EP/DOPO+MAH and EP/DOPO-MAH-6H

Table 2 The cone calorimeter test （CCT） data of EP， EP/DOPO， EP/DOPO+MAH and EP/DOPO-MAH-6H

Samples	TTI/s	pHRR/（kW·m^-2）	THR/（MJ·m^-2）	pSPR/（m²·s^-1）	TSP/m²	pCOPR/（g·s^-1）	pCO₂PR/（g·s^-1）
EP	97	1 079.2	75.1	0.25	24.9	0.038	0.73
EP/DOPO	86	699.5	57.1	0.39	28.2	0.063	0.39
EP/DOPO+MAH	85	585.8	62.5	0.27	25.3	0.026	0.31
EP/DOPO-MAH-6H	70	481.3	42.3	0.38	26.6	0.054	0.25

Fig.2 UL-94 tests of EP （A）， EP/DOPO （B）， EP/DOPO+MAH （C） and EP/DOPO-MAH-6H （D）

Fig.3 Data of EP， EP/DOPO， EP/DOPO+MAH and EP/DOPO-MAH-6H： FGR and FPI （A）， LOI （B）

Fig.4 Cone calorimeter tests of EP， EP/APP， EP/APP+MAH and EP/APP-MAH-6H

Table 3 The CCT data of EP， EP/APP， EP/APP+MAH and EP/APP-MAH-6H

Samples	TTI/s	pHRR/（kW·m^-2）	THR/（MJ·m^-2）	pSPR/（m²·s^-1）	TSP/m²	pCOPR/（g·s^-1）	pCO₂PR/（g·s^-1）
EP	97	1079.2	75.1	0.25	24.9	0.038	0.73
EP/APP	92	593.1	32.8	0.34	12.3	0.042	0.34
EP/APP+MAH	68	584.9	55.8	0.17	15.3	0.015	0.35
EP/APP-MAH-6H	68	445.7	30.3	0.18	7.9	0.025	0.25

Fig.5 UL-94 tests of EP （A）， EP/APP （B）， EP/APP+MAH （C） and EP/APP-MAH-6H （D）

Fig.6 Data of EP， EP/APP， EP/APP+MAH and EP/APP-MAH-6H： FGR and FPI （A）， LOI （B）

Fig.7 Cone calorimeter tests of EP， EP/MPP， EP/MPP+MAH and EP/MPP-MAH-6H

Table 4 The CCT data of EP， EP/MPP， EP/MPP+MAH and EP/MPP-MAH-6H

Samples	TTI/s	pHRR/（kW·m^-2）	THR/（MJ·m^-2）	pSPR/（m²·s^-1）	TSP/m²	pCOPR/（g·s^-1）	pCO₂PR/（g·s^-1）
EP	97	1 079.2	75.1	0.25	24.9	0.038	0.73
EP/MPP	84	600.6	58.5	0.17	13.4	0.019	0.35
EP/MPP+MAH	67	412.3	73.7	0.14	17.1	0.011	0.22
EP/MPP-MAH-6H	79	385.8	66.6	0.10	16.1	0.007	0.21

Fig.8 UL-94 tests of EP （A）， EP/MPP （B）， EP/MPP+MAH （C） and EP/MPP-MAH-6H （D）

Fig.9 Data of EP， EP/MPP， EP/MPP+MAH and EP/MPP-MAH-6H： FGR and FPI （A）， LOI （B）

Fig.10 Digital photos （A）， SEM images （B） and Raman spectra （C） depicting the char residues of EP， EP/DOPO， EP/DOPO+MAH and EP/DOPO-MAH-6H

Fig.11 SEM-EDS element mapping of EP （A）， EP/DOPO （B）， EP/DOPO+MAH （C） and EP/DOPO-MAH-6H （D）

Fig.12 Digital photos （A）， SEM images （B） and Raman spectra （C） depicting the char residues of EP， EP/APP， EP/APP+MAH and EP/APP-MAH-6H

Fig.13 The SEM-EDS element mapping of EP （A）， EP/APP （B）， EP/APP+MAH （C） and EP/APP-MAH-6H （D）

Fig.14 Digital photos （A）， SEM images （B） and Raman spectra （C） depicting the char residues of EP， EP/MPP， EP/MPP+MAH and EP/MPP-MAH-6H

Fig.15 The SEM-EDS element mapping of EP （A）， EP/MPP （B）， EP/MPP+MAH （C） and EP/MPP-MAH-6H （D）

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Flame Retardancy of Epoxy Resin Enhanced by Intercalation of Magnesium Aluminum Hydrotalcite with Phosphorous Flame Retardants

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