磷酸三苯酯和甲基八溴醚在阻燃聚苯乙烯中的协同行为研究

doi:10.19491/j.issn.1001-9278.2022.05.007

中国塑料 ›› 2022, Vol. 36 ›› Issue (5): 36-42.DOI: 10.19491/j.issn.1001-9278.2022.05.007

磷酸三苯酯和甲基八溴醚在阻燃聚苯乙烯中的协同行为研究

杨木森¹^,²^,³(), 钱立军¹^,²^,³(), 王靖宇¹^,²^,³, 赵震³^,⁴, 王光禹⁵, 辛晓华⁵

^1.北京工商大学化学与材料工程学院，北京 100048
^2.石油和化工行业高分子材料无卤阻燃剂工程实验室，北京 100048
^3.中国轻工业先进阻燃剂工程技术研究中心，北京 100048
^4.山东省兄弟科技股份有限公司，山东潍坊 262700
^5.山东金海湾材料科技有限公司，山东寿光 262715

收稿日期:2022-02-28 出版日期:2022-05-26 发布日期:2022-05-26
通讯作者: 钱立军（1976—），男，教授，从事环境友好阻燃助剂及其高分子材料的制备及产业化，qianlj@btbu.edu.cn.
E-mail:1930301019@st.btbu.edu.cn;qianlj@btbu.edu.cn
作者简介:杨木森（1996—），男，在读硕士研究生，从事阻燃材料研究，1930301019@st.btbu.edu.cn
基金资助:
山东省重点研发计划（重大科技创新工程）课题(2020CXGC011207)

Synergistic effect of triphenyl phosphate and methyloctabromoether on flame retardancy of polystyrene

YANG Musen¹^,²^,³(), QIAN Lijun¹^,²^,³(), WANG Jingyu¹^,²^,³, ZHAO Zhen³^,⁴, WANG Guangyu⁵, XIN Xiaohua⁵

^1.College of Chemistry and Materials Engineering，Beijing Technology and Business University，Beijing 100048，China
^2.China Light Industry Engineering Technology Research Center of Advanced Flame Retardants，Beijing 100048，China
^3.Petroleum and Chemical Industry Engineering Laboratory of Non?halogen Flame Retardants for Polymers，Beijing 100048，China
^4.Shandong Brothers Technology Co，Ltd，Weifang 262700，China
^5.Shandong Golden Bay New Material Technology Co，Ltd，Shouguang 261000，China

Received:2022-02-28 Online:2022-05-26 Published:2022-05-26
Contact: QIAN Lijun E-mail:1930301019@st.btbu.edu.cn;qianlj@btbu.edu.cn

摘要/Abstract

摘要：

为获得基于甲基八溴醚（MOBE）的高效阻燃聚苯乙烯（PS）复合体系，采用极限氧指数仪、锥形量热仪、热重分析仪（TG）和差示扫描量热仪（DSC）等对纯PS及其复合材料的阻燃性能及机理和热稳定性等进行了测试和表征，探索了MOBE与磷酸三苯酯（TPP）复配阻燃PS的行为规律。结果表明，TPP和MOBE复合体系比二者各自单独作为阻燃剂使用时赋予了PS材料更高的极限氧指数（LOI），PS/3 %（质量分数，下同）TPP/4 %MOBE的LOI可达27.7 %，明显高于PS/4 %MOBE（26.1 %）；3 %TPP/4 %MOBE能够在4 %MOBE的基础上进一步抑制PS复合材料的燃烧强度，降低有效燃烧热，降低热释放速率峰值（PHRR）与总热释放量（THR）；TPP和MOBE能够在PS复合材料热降解时将阻燃元素集中释放，同时发挥气相淬灭效应；此外，TPP的加入能够提高PS复合材料的熔体流动速率，降低其玻璃化转变温度，从而使PS热分解产生的熔滴更快地带走热量，最终使TPP与MOBE发挥更好的阻燃效果。

关键词: 阻燃聚苯乙烯, 磷酸三苯酯, 甲基八溴醚, 协效阻燃

Abstract:

To obtain a high?efficient flame?retardant polystyrene （PS） composite system based on methyloctabromoether （MOBE）， the flame?retardant properties and corresponding mechanisms of the flame?retardant PS compounds with MOBE and triphenyl phosphate （TPP） were investigated using a limiting oxygen index instrument， a cone calorimeter， a thermogravimetric analyzer， and a differential scanning calorimeter. The results indicated that the introduction of TPP and MOBE increased the limited oxygen index （LOI） of PS significantly compared to their use alone. The PS compound containing 3 wt% TPP and 4 wt% MOBE obtained an LOI of 27.7 vol%， which was 26.1 % higher than the compound only containing 4 wt% MOBE. The burning intensity of this PS compound was further depressed， and its effective heat of combustion， peak heat release rate， and total heat release was reduced when compared to those of the compound only containing 4 wt% MOBE. TPP and MOBE could release the flame?retardant elements intensively during the thermal degradation process of PS compounds， exhibiting an efficient gas phase quenching effect. Moreover， the addition of TPP also improved the melt flow rate of PS compounds and reduced their glass transition temperatures. In this case， the generated droplets could take heat away faster from the PS thermal decomposition and finally make TPP and MOBE a better flame?retardant effect.

Key words: flame?retardant polystyrene, triphenyl phosphate, methyloctabromoether, synergistic flame retardancy

中图分类号:

TQ324.24⁺8

杨木森, 钱立军, 王靖宇, 赵震, 王光禹, 辛晓华. 磷酸三苯酯和甲基八溴醚在阻燃聚苯乙烯中的协同行为研究[J]. 中国塑料, 2022, 36(5): 36-42.

YANG Musen, QIAN Lijun, WANG Jingyu, ZHAO Zhen, WANG Guangyu, XIN Xiaohua. Synergistic effect of triphenyl phosphate and methyloctabromoether on flame retardancy of polystyrene[J]. China Plastics, 2022, 36(5): 36-42.

图/表 13

样品名称	MOBE/g	TPP/g	硬脂酸钙/g	PS/g
PS	0	0	0	100
PS/3 %TPP	0	3	0	97
PS/7 %TPP	0	7	0	93
PS/4 %MOBE	4	0	0.13	95.87
PS/7 %MOBE	7	0	0.13	92.87
PS/3 %TPP/4 %MOBE	4	3	0.13	92.87

表1 样品配方

Tab.1 Formula of the samples

样品	LOI/%	UL 94
样品	LOI/%	t₁/s	t₂/s	是否滴落	阻燃等级
PS	19.2	烧夹	-	是	无级别
PS/3 %TPP	20.2	烧夹	-	是	无级别
PS/7 %TPP	21.1	烧夹	-	是	无级别
PS/4 %MOBE	26.1	0	0	是	V⁃2
PS/7 %MOBE	25.5	0	0	是	V⁃2
PS/3 %TPP/4 %MOBE	27.7	0	0	是	V⁃2

表2 PS复合材料的阻燃性能

Tab.2 Flame retardant properties of PS composites

样品	TTI/s	PHRR/kW·m^-2	THR/MJ·m^-2	TSP/m²	av⁃COY/kg·kg^-1	av⁃CO₂Y/kg·kg^-1	av⁃EHC/MJ·kg^-2
PS	35	1 321	134	55.5	0.09	2.48	34.0
PS/4 %MOBE	37	1 006	119	57.9	0.10	2.15	29.8
PS/3 %TPP/4 %MOBE	37	835	105	62.4	0.11	1.89	26.3

表3 PS复合材料的燃烧性能

Tab.3 Combustion properties of PS composites

图1 PS复合材料的HRR曲线

Fig.1 HRR curves of PS composites

图2 PS复合材料的THR曲线

Fig.2 THR curves of PS composites

图3 PS复合材料的TSP曲线

Fig.3 TSP curves of PS composites

图4 PS复合材料的TG和DTG曲线

Fig.4 TG and DTG curves of PS composites

样品	T_{d⁃1 %}/ ℃	T_{d⁃5 %}/ ℃	T_d⁃max/ ℃	MLR/ %·min^-1	R_{600 ℃}/ %
TPP	200	232	304	-48.73	0.51
PS	365	390	430	-54.79	0.96
PS/4 %MOBE	300	351	432	-31.80	0.54
PS/3 %TPP/4 %MOBE	292	329	423	-31.87	0.65

表4 PS复合材料的热稳定性

Tab.4 Thermal stability of PS composites

图5 PS复合材料的离线GC/MS谱图

Fig.5 Offline GC/MS spectra of PS composites

图6 PS复合材料的在线GC/MS谱图

Fig.6 Online GC/MS spectra of the PS composites

图7 PS复合材料的TG?FTIR分析结果

Fig.7 TG?FTIR analysis results of PS composites

图8 PS复合材料 DSC曲线

Fig.8 DSC curves of PS composites

样品	熔体流动速率/g·10 min^-1
PS	2.434
PS/4 %MOBE	2.791
PS/3 %TPP/4 %MOBE	10.758

表5 PS复合材料的熔体流动速率

Tab.5 Melt flow rate of PS composites

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磷酸三苯酯和甲基八溴醚在阻燃聚苯乙烯中的协同行为研究

Synergistic effect of triphenyl phosphate and methyloctabromoether on flame retardancy of polystyrene

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