线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

doi:10.19491/j.issn.1001-9278.2020.09.012

中国塑料 ›› 2020, Vol. 34 ›› Issue (9): 66-72.DOI: 10.19491/j.issn.1001-9278.2020.09.012

线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

郭芳¹, 许准², 王晶玉³, 赵晗³, 许博³()

^1.河南省有色金属地质勘查总院，郑州 450052
^2.郑州财税金融职业学院，郑州 450048
^3.北京工商大学化学与材料工程学院，北京 100048

收稿日期:2020-06-30 出版日期:2020-09-26 发布日期:2020-09-25

Study on Application of Linear Phosphorus⁃rich Flame Retardant in Polyurethane Foams

Fang GUO¹, Zhun XU², Jingyu WANG³, Han ZHAO³, Bo XU³()

^1.Henan Nonferous Metals Geological Exploration Institute, Zhengzhou 450052，China
^2.Zhengzhou Vocatinal College of;Finance and Taxation, Zhengzhou 450048，China
^3.College of Chemistry and Materials Engineering of Beijing Technology and;Business University，Beijing 100048，China

Received:2020-06-30 Online:2020-09-26 Published:2020-09-25
Contact: Bo XU E-mail:xubo@btbu.edu.cn

摘要/Abstract

摘要：

通过界面聚合法合成了一种线性富磷化阻燃剂（LPRFR），将LPRFR与可膨胀石墨（EG）复配制备了阻燃聚氨酯泡沫（RPUF），使用红外光谱分析仪、核磁共振分析仪对阻燃剂LPRFR的化学结构进行了表征，并通过极限氧指数仪、锥形量热仪、扫描电子显微镜和红外光谱分析仪对RPUF的燃烧性能、微观形貌和化学结构进行了分析。结果表明，仅10 %（质量分数，下同）的LPRFR 与8 %EG复配后，RPUF的极限氧指数（LOI）便达到26.1 %；LPRFR和EG能大幅降低RPUF的热释放速率，并提高基体的成炭能力； LPRFR参与了燃烧过程中的成炭反应，形成了含P—O—C及P=O结构的高质量炭层，有效隔绝了氧气和热量；LPRFR是一种对于聚氨酯泡沫阻燃性能优异的新型阻燃剂。

关键词: 磷系, 阻燃剂, 聚氨酯泡沫, 膨胀石墨

Abstract:

A linear phosphorus?rich flame retardant (LPRFR) was synthesized by interfacial polymerization, and its chemical structure was characterized by infrared spectroscopy and nuclear magnetic resonance spectroscopy. Flame retardant polyurethane foams (RPUF) were prepared by compounding with LPRFR and expandable graphite (EG). The RPUF achieved a limiting oxygen index of 26.1 vol% when 10 wt% of LPRFR and 8 wt% of EG were added. The cone calorimeter test results indicated that the addition of LPRFR and EG could significantly reduce the heat release of RPUF and improve the carbonization ability of the matrix. In addition, the microstructure and chemical structure of carbon residue were analyzed by scanning electron microscopy and infrared spectroscopy. The results demonstrated that LPRFR involved in the carbonation reaction during the combustion process, leading to the formation of a high?quality carbon layer with P—O—C and P=O structures, which effectively isolated oxygen and heat. Therefore, LPRFR can be taken as a new flame retardant of polyurethane foams with excellent flame retardant properties.

Key words: phosphorus?based flame retardant, rigid polyurethane foams, flame retardancy

中图分类号:

TQ328.06

郭芳, 许准, 王晶玉, 赵晗, 许博. 线性富磷化阻燃剂在聚氨酯泡沫中的应用研究[J]. 中国塑料, 2020, 34(9): 66-72.

Fang GUO, Zhun XU, Jingyu WANG, Han ZHAO, Bo XU. Study on Application of Linear Phosphorus⁃rich Flame Retardant in Polyurethane Foams[J]. China Plastics, 2020, 34(9): 66-72.

图/表 12

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样品	DSU?450L/g	PAPI/g	催化剂/g	阻燃剂		H₂O/g	环戊烷/g	泡沫稳定剂/g
样品	DSU?450L/g	PAPI/g	催化剂/g	EG/g	PCBD?11/g	H₂O/g	环戊烷/g	泡沫稳定剂/g
纯RPUF	72	108	2.16	-	-	0.9	9	2.7
RPUF/ 8 %EG	72	108	2.16	16.93	-	0.9	9	2.7
RPUF /8 %EG /6 %LPRFR	72	108	2.16	18.12	13.59	0.9	9	2.7
RPUF /8 %EG/8 %LPRFR	72	108	2.16	18.55	18.55	0.9	9	2.7
RPUF /8 %EG/10 %LPRFR	72	108	2.16	19.00	23.75	0.9	9	2.7

样品	DSU?450L/g	PAPI/g	催化剂/g	阻燃剂		H₂O/g	环戊烷/g	泡沫稳定剂/g
样品	DSU?450L/g	PAPI/g	催化剂/g	EG/g	PCBD?11/g	H₂O/g	环戊烷/g	泡沫稳定剂/g
纯RPUF	72	108	2.16	-	-	0.9	9	2.7
RPUF/ 8 %EG	72	108	2.16	16.93	-	0.9	9	2.7
RPUF /8 %EG /6 %LPRFR	72	108	2.16	18.12	13.59	0.9	9	2.7
RPUF /8 %EG/8 %LPRFR	72	108	2.16	18.55	18.55	0.9	9	2.7
RPUF /8 %EG/10 %LPRFR	72	108	2.16	19.00	23.75	0.9	9	2.7

样品	T_{d,5 %}/℃	T_max/℃	残炭量/%
样品	T_{d,5 %}/℃	T_max/℃	500 ℃	600 ℃	700 ℃
纯RPUF	251.32	330	19.88	15.14	14.54
RPUF/8 %EG	262.57	330	37.36	33.56	25.32
RPUF/8 %EG/6 %LPRFR	239.38	317	28.82	27.13	26.24
RPUF/8 %EG/8 %LPRFR	242.01	322	37.35	33.67	32.10
RPUF/8 %EG/10 %LPRFR	240.89	335	35.21	31.13	28.44

样品	T_{d,5 %}/℃	T_max/℃	残炭量/%
样品	T_{d,5 %}/℃	T_max/℃	500 ℃	600 ℃	700 ℃
纯RPUF	251.32	330	19.88	15.14	14.54
RPUF/8 %EG	262.57	330	37.36	33.56	25.32
RPUF/8 %EG/6 %LPRFR	239.38	317	28.82	27.13	26.24
RPUF/8 %EG/8 %LPRFR	242.01	322	37.35	33.67	32.10
RPUF/8 %EG/10 %LPRFR	240.89	335	35.21	31.13	28.44

样品	LOI/%	pk?HRR/kW·m^-2	THR/MJ·m^-2	av?CO/kg·kg^-1	av?CO₂/kg·kg^-1	残炭量/%
纯RPUF	18.5	360	30	0.15	2.30	0.1
RPUF /8 %EG	23.5	206	25	0.08	2.74	47
RPUF /8 %EG/6 %LPRFR	24.2	202	25	0.19	2.10	36
RPUF /8 %EG/8 %LPRFR	25.2	201	25	0.18	2.94	33
RPUF /8 %EG/10 %LPRFR	26.1	194	26	0.16	2.81	29

线性富磷化阻燃剂在聚氨酯泡沫中的应用研究

Study on Application of Linear Phosphorus⁃rich Flame Retardant in Polyurethane Foams

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