Analysis of Pyrolytic Volatiles and Speculation of Pyrolysis Mechanism of Flame-Retardant Cotton Fabric with Spirocyclophosphamidazole

doi:10.19894/j.issn.1000-0518.220172

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (3): 380-388.DOI: 10.19894/j.issn.1000-0518.220172

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Analysis of Pyrolytic Volatiles and Speculation of Pyrolysis Mechanism of Flame-Retardant Cotton Fabric with Spirocyclophosphamidazole

Xiang-Min XU, Jie DENG, Yu-Qi DU, Hong-Liang SHEN, Ze-Kun AN, Cai-Ying SUN()

Heilongjiang Key Laboratory of Molecular Design and Preparation of Flame Retarded Materials，College of Chemistry，Chemical Engineering and Resource Utilization，Northeast Forestry University，Harbin 150040，China

Received:2022-05-08 Accepted:2022-11-10 Published:2023-03-01 Online:2023-03-27
Contact: Cai-Ying SUN
About author:sundeyee@126.com
Supported by:
the Innovation Training Program for College Students of Northeast Forestry University(202110225448)

Abstract

Abstract:

On the basis of effects of spirocyclophosphoimidazole （Fr） on flame retardance， mechanical properties and fire behavior of cotton fabric， the pyrolysis volatiles of spirocyclophosphoimidazole flame retardant cotton （Fr-cotton） were studied by Thermogravimetric infrared （TG-IR）. The results showed that Fr is a good flame retardant for cotton fabrics， which could reduce the pyrolysisvolatiles， increase limiting oxygen index （LOI） from 18.7% to 36.6%， and increasethe residue at 600 ℃ from 8.6% to 28.5%. Adding ammonium polyphosphate （APP） and CeO₂（MO）， the pyrolysis volatiles of Fr-cotton were further reduced， and the main components were only water and CO₂/CO， the LOI value was further increased to 43%， and the residue at 600 ℃ was increased to 42.6%. This indicates that the flame retardant mainly acts in the solidified phase， increases the amount of residue， reduces the generation of volatiles， and changes the pyrolysis pathway of cotton fabric. Levoglucosan and furans are generated during the pyrolysis of cotton fabric， and then they decompose into small molecule volatiles. The flame retardants directlycatalyze cotton fabric dehydrateand carbonize. This conclusion can provide theoretical support for the selection of flame retardants for cotton fabrics.

Key words: Flame retardant cotton, Pyrolysis volatiles, Pyrolysis mechanism

CLC Number:

O621.2

Xiang-Min XU, Jie DENG, Yu-Qi DU, Hong-Liang SHEN, Ze-Kun AN, Cai-Ying SUN. Analysis of Pyrolytic Volatiles and Speculation of Pyrolysis Mechanism of Flame-Retardant Cotton Fabric with Spirocyclophosphamidazole[J]. Chinese Journal of Applied Chemistry, 2023, 40(3): 380-388.

Figures/Tables 12

Fig.1 Synthesis reaction formula of flame retardants

Table 1 Flame retardant properties and mechanical properties of flame retardant cotton fabrics

Sample	LOI/%	After flame time/s	Smoldering time/s	Broken length/mm	Broken strength/N
Cotton	18.7	33.6	103.0	300	386.8
Fr-cotton	36.6	0	0	68	312.5
Fr-APP-cotton	43.0	0	0	40	332.4
Fr-APP-MO-cotton	42.6	0	0	42	322.5

Fig.2 TG（A）/DTG（B） curves of cotton fabrics before and after flame retardant

Table 2 TG/DTG key dataof the cotton before and after flame retadant

Sample	T_2.5%/℃	First mass loss temperature range/℃	Temperature at maximum mass loss rate/℃	Maximum mass loss rate/（%·min^-1）	Second mass less temperature range/℃	Maximum mass loss rate/（%·min^-1）	Residue at 600 ℃/%
Cotton	255	265~380	345	18.2	-	-	8.6
Fr-cotton	175	210~336	306	13.5	132-210	0.8	28.5
Fr-APP-cotton	225	210~325	295	7.2	360~420	3.2	42.0
Fr-APP-MO-cotton	222	210~325	294	6.9	360-420	3.0	42.6

Fig.3 Infrared 3D images of pyrolysis products of cotton before and after flame retardant

Fig.4 Absorbance of pyrolysis volatiles with time

Fig.5 Infrared spectra of pyrolysis products

Fig.6 Pyrolysis of cellulose produces intermediate products L-glucose and furans

Fig.7 The formation mechanism of levoglucan

Fig.8 Formation mechanism of furans

Fig.9 Acid-catalyzed dehydration of cellulose

Fig.10 Cellulose acid-catalyzed hydrolysis process

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Analysis of Pyrolytic Volatiles and Speculation of Pyrolysis Mechanism of Flame-Retardant Cotton Fabric with Spirocyclophosphamidazole

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