苯基膦酸铈与十溴二苯醚在玻璃纤维增强聚对苯二甲酸乙二酯中的协同阻燃抑烟机理

doi:10.7503/cjcu20160630

摘要/Abstract

摘要：

采用熔融共混法制备了玻璃纤维增强聚对苯二甲酸乙二酯(PET-GF)/十溴二苯醚(DBDPO)/苯基膦酸铈(CeHPP)复合材料, 通过锥型量热仪(Cone)对复合材料的燃烧行为进行综合分析, 采用热失重-红外联用(TG-FTIR)分析了复合材料热降解过程中气体的释放量和主要成分, 并使用扫描电子显微镜(SEM)、能量色散X射线光谱仪(EDX)和X射线光电子能谱(XPS)对复合材料燃烧后的残炭形貌、残炭所含元素及含量等进行表征. 实验结果表明, 当CeHPP与DBDPO两者复配使用时, PET-GF/DBDPO/CeHPP复合材料的热解过程受到抑制, 凝聚相的燃烧减缓, 材料总的热分解量降低, 烟气释放量明显减小. 这主要是由于CeHPP在燃烧过程中形成了连续致密的残炭, 分布于基材和玻璃纤维表面, 将部分DBDPO及其分解产物滞留于凝聚相, 从而实现了气相-凝聚相双重阻燃作用, 有效阻隔了挥发性气体产物的释放.

关键词: 阻燃, 抑烟, 苯基膦酸稀土, 溴系阻燃剂, 聚对苯二甲酸乙二醇酯

Abstract:

Glass fiber reinforced poly(1,4-butylene terephthalate)(PET-GF)/ decabromodiphenyl oxide(DBDPO)/cerium phenylphosphonate(CeHPP) composites were prepared by melt blending. Cone test was employed to investigate the comprehensive combustion behavior and the thermal gravimetric-infrared spectrometry(TG-FTIR) was used to analyze the release amount and component of volatile gases produced during thermal degradation. The scanning electron microtopography(SEM) of char residues was observed, and the elements and contents in char residues were tested by energy dispersive X-ray spectrometer(EDX) and X-ray photoelectron spectroscopy(XPS). The experimental results showed that the compounding of CeHPP and DBDPO in PET-GF restrained the thermo-oxidative degradation of PET-GF/DBDPO/CeHPP composites, retarded the combustion of condensed phases and reduced the smoke release. CeHPP formed the continuous and compact carbon char during combustion, dispersing among the surface of polymer matrix and glass fibers and restricting DBDPO and its decomposition products in condensed phases. Therefore, the synergism flame retardant effects of gaseous phase and condensed phase were achieved, suppressing the smoke release to gaseous phase effectively.

Key words: Flame retardancy, Smoke suppression, Rare earth phenylphosphonate, Brominated flame retardant, Poly(1,4-butylene terephthalate)

中图分类号:

O631.2⁺2

TrendMD:

郭正虹, 方征平, 陈超. 苯基膦酸铈与十溴二苯醚在玻璃纤维增强聚对苯二甲酸乙二酯中的协同阻燃抑烟机理. 高等学校化学学报, 2017, 38(2): 284.

GUO Zhenghong, FANG Zhengping, CHEN Chao. Synergistic Flame Retardant and Suppression Smoke Mechanism of Cerium Phenylphosphonate and Decabromodiphenyl Oxide in Glass-fiber Reinforced Poly(1,4-butylene terephthalate) Composites^†. Chem. J. Chinese Universities, 2017, 38(2): 284.

图/表 13

Table 1 Formulations of PET-GF/DBDPO/ CeHPP composites

Sample	Mass fraction(%)
Sample	PET-GF	DBDPO	CeHPP	Antioxidant
PET-GF	100	0	0	0.3
PET-GF/DBDPO	92	8		0.3
PET-GF/CeHPP	92		8	0.3
PET-GF/DBDPO/CeHPP	92	6	2	0.3

Fig.1 Heat release rate(A) and total heat release(B) of PET-GF/DBDPO/CeHPP composites in the Cone tests a. PET-GF; b. PET-GF/DBDPO; c. PET-GF/DBDPO/CeHPP; d. PET-GF/CeHPP.

Table 2 Cone calorimetric data for PET-GF/DBDPO/CeHPP composites*

Sample	PET-GF	PET-GF/DBDPO	PET-GF/DBDPO/CeHPP	PET-GF/CeHPP
t_ignited/s	199	220	231	219
t_PHRR/s	245	253	261	255
PHRR/(kW·m^-2)	241.8	201.3	193.0	219.3
THR/(MJ·m^-2)	55.0	34.6	28.2	39.0
AMLR/(g·s^-1)	0.071	0.073	0.059	0.066
AEHC/(MJ·kg^-1)	21.6	5.1	16.2	19.3
ASPR/s^-1	3.64	5.56	3.73	3.73
TSP(%)	1235	1776	1135	1172
ASEA/(m²·kg^-1)	320	529	399	435
CO yield(%)	0.051	0.133	0.139	0.078
CO₂ yield(%)	2.911	1.854	1.868	2.318

Fig.2 Mass loss rate(MLR, A) and derive mass(B) of PET-GF/DBDPO/CeHPP composites in the Cone tests a. PET-GF; b. PET-GF/DBDPO; c. PET-GF/DBDPO/CeHPP; d. PET-GF/CeHPP.

Fig.3 Smoke production curves of PET-GF/DBDPO/CeHPP composites in Cone calorimeter (A) CO yield; (B) CO2 yield. a. PET-GF; b. PET-GF/DBDPO; c. PET-GF/DBDPO/CeHPP; d. PET-GF/CeHPP.

Fig.4 FTIR spectra of pyrolysis gaseous products emitted from PET-GF, PET-GF/DBDPO, PET-GF/CeHPP and PET-GF/DBDPO/CeHPP composites at the maximum evolution rate(439 ℃)(A) and total absorbance of gaseous(B) products vs time

Fig.5 Absorbance of pyrolysis products for PET-GF, PET-GF/DBDPO, PET-GF/CeHPP and PET-GF/DBDPO/CeHPP composites vs. time (A) CO; (B) CO2; (C) hydrocarbons; (D) carbonyl compounds.

Fig.6 Digital photographs and mass of residues for PET-GF(A), PET-GF/DBDPO(B), PET-GF/DBDPO/CeHPP(C) and PET-GF/CeHPP(D) composites after cone tests

Fig.7 SEM images of residues for PET-GF/DBDPO(A1, A2), PET-GF/DBDPO/CeHPP(B1, B2) and PET-GF/CeHPP(C1, C2) composites after Cone tests

Fig.8 EDS test area of PET-GF/DBDPO/CeHPP(A1, A2) and PET-GF/CeHPP(B1, B2) (A1, B1) Outer char; (A2, B2) inner char.

Table 3 EDS data of residues for PET-GF/DBDPO/CeHPP and PET-GF/CeHPP composites

Sample	C(%)	O(%)	P(%)	Ce(%)	C/O	P/Ce
Outer char PET-GF/DBDPO/CeHPP	49.68	46.30	3.12	0.95	1.10	3.50
Inner char PET-GF/DBDPO/CeHPP	53.22	43.03	2.80	0.95	1.20	2.90
Outer char PET-GF/CeHPP	64.07	29.17	4.63	2.13	2.20	2.20
Inner char PET-GF/CeHPP	60.17	35.06	3.14	1.63	1.70	1.90

Table 4 XPS data of residues for PET-GF/DBDPO/CeHPP composite after Cone test

Sample	P(%)	Ce(%)	Br(%)	P/Ce
Outer char PET-GF/DBDPO/CeHPP	83.35	15.89	0.76	5.20
Inner char PET-GF/DBDPO/CeHPP	79.66	3.44	16.90	23.10

Scheme 1 Schematic representation of the flame-retardant mechanism of PET-GF/DBDPO(Ⅰ) and PET-GF/DBDPO/CeHPP(Ⅱ)

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