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To enhance the flame retardancy and smoke suppression performance of EP-CE composites,a novel flame retardant was synthesized using DOPO and BPS as raw materials. The flame-retardant DOPO-BPS/OSEP/EP-CE composites were fabricated by the solution casting method,where DOPO-BPS and OSEP were jointly introduced into EP-CE matrix. Based on Fourier transform infrared spectroscopy (FTIR) analysis,nuclear magnetic resonance (NMR) analysis,thermogravimetric analysis (TGA),limiting oxygen index (LOI) test,UL-94 vertical burning test,and cone calorimeter analysis,the effects of different ratios of DOPO-BPS and OSEP on the flame retardancy and smoke suppression properties of EP-CE composite materials were studied. The results show that the phosphaphenanthrene ring structure of DOPO-BPS could form a stable carbon layer and block the transfer of heat and oxygen. The synergistic effect with OSEP significantly improves the flame retardant effect and smoke suppression performance. When the flame retardant DOPO-BPS and OSEP are added to EP-CE at a mass fraction of 9∶1,the flame retardant performance and smoke suppression performance are the best,the flame retardant performance reaches V-0 level,and the LOI increases to 31.4%. Compared with EP-CE,the peak heat release rate,total heat release and total smoke production decrease by 29.7%,32.2% and 32.7%,respectively.

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为提高环氧树脂(EP)-氰酸酯树脂(CE)复合材料的阻燃与抑烟性能,首先以9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO)与4,4'-二羟基二苯砜(BPS)为原料,合成一种新型阻燃剂DOPO-BPS,通过溶液浇筑法,将DOPO-BPS与有机海泡石(OSEP)共同引入EP-CE基体中,制备阻燃DOPO-BPS/OSEP/EP-CE复合材料;然后在傅里叶红外光谱仪(FTIR)分析、核磁共振(NMR)分析、热重分析(TGA)、极限氧指数(LOI)测试、UL-94垂直燃烧测试和锥形量热仪分析的基础上,研究不同比例的DOPO-BPS与OSEP对EP-CE复合材料阻燃性能和抑烟性能的影响。研究表明:DOPO-BPS的磷杂菲环结构能形成稳定炭层,阻断热氧传递,与OSEP的协同作用显著提升了阻燃效果和抑烟性能。当阻燃剂DOPO-BPS与OSEP以9∶1的质量比添加至EP-CE时,阻燃性能和抑烟性能最佳,阻燃性能达V-0级,LOI增至31.4%,且热释放速率峰值、总热释放量和产烟总量相比于EP-CE,分别降低了29.7%、32.2%和32.7%。

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刘勇 (1984—),男,湖南宁乡人,博士,副教授,主要从事危险化学品道路运输安全、海泡石防火阻燃等方面的研究。E-mail:

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Flame retardant composites formulag

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 EP CE DOPO-
BPS
OSEP
EP-CE 60.0 40.0 0.0 0.0
7DOPO-BPS/3OSEP/EP-CE 54.0 36.0 7.0 3.0
8DOPO-BPS/2OSEP/EP-CE 54.0 36.0 8.0 2.0
9DOPO-BPS/1OSEP/EP-CE 54.0 36.0 9.0 1.0
3OSEP/EP-CE 58.2 38.8 0.0 3.0
10DOPO-BPS/EP-CE 54.0 36.0 10.0 0.0
), ArticleFig(id=1165681896383062451, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=CN, label=表1, caption=

阻燃复合材料配方

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 EP CE DOPO-
BPS
OSEP
EP-CE 60.0 40.0 0.0 0.0
7DOPO-BPS/3OSEP/EP-CE 54.0 36.0 7.0 3.0
8DOPO-BPS/2OSEP/EP-CE 54.0 36.0 8.0 2.0
9DOPO-BPS/1OSEP/EP-CE 54.0 36.0 9.0 1.0
3OSEP/EP-CE 58.2 38.8 0.0 3.0
10DOPO-BPS/EP-CE 54.0 36.0 10.0 0.0
), ArticleFig(id=1165681896433394100, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=EN, label=Table 2, caption=

TGA data of EP-CE and its composites

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 初始失
重温度
t5%/℃
最大失
重速率
温度
tmax/℃
残余物
质量
分数/%
EP-CE 356.7 385.7 15.2
9DOPO-BPS/1OSEP/EP-CE 323.6 395.1 18.0
8DOPO-BPS/2OSEP/EP-CE 329.6 395.1 16.5
7DOPO-BPS/3OSEP/EP-CE 345.6 396.6 16.3
10DOPO-BPS/EP-CE 353.8 394.8 18.9
3OSEP/EP-CE 363.4 401.4 16.0
), ArticleFig(id=1165681896500502965, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=CN, label=表2, caption=

EP-CE及其复合材料的TGA数据

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 初始失
重温度
t5%/℃
最大失
重速率
温度
tmax/℃
残余物
质量
分数/%
EP-CE 356.7 385.7 15.2
9DOPO-BPS/1OSEP/EP-CE 323.6 395.1 18.0
8DOPO-BPS/2OSEP/EP-CE 329.6 395.1 16.5
7DOPO-BPS/3OSEP/EP-CE 345.6 396.6 16.3
10DOPO-BPS/EP-CE 353.8 394.8 18.9
3OSEP/EP-CE 363.4 401.4 16.0
), ArticleFig(id=1165681896576000438, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=EN, label=Table 3, caption=

LOI and UL-94 test data of EP-CE and its composites

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 LOI
/%
等级 滴落 总燃烧
时间/s
EP-CE 24.4 NR >250
7DOPO-BPS/3OSEP/EP-CE 29.8 V-1 134.5
8DOPO-BPS/2OSEP/EP-CE 30.6 V-1 98.5
9DOPO-BPS/1OSEP/EP-CE 31.4 V-0 47.5
10DOPO-BPS/EP-CE 30.9 V-0 46.5
3%OSEP/EP-CE 24.6 NR >250
), ArticleFig(id=1165681896638914999, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=CN, label=表3, caption=

EP-CE及其复合材料的LOI和UL-94测试数据

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 LOI
/%
等级 滴落 总燃烧
时间/s
EP-CE 24.4 NR >250
7DOPO-BPS/3OSEP/EP-CE 29.8 V-1 134.5
8DOPO-BPS/2OSEP/EP-CE 30.6 V-1 98.5
9DOPO-BPS/1OSEP/EP-CE 31.4 V-0 47.5
10DOPO-BPS/EP-CE 30.9 V-0 46.5
3%OSEP/EP-CE 24.6 NR >250
), ArticleFig(id=1165681896689246648, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=EN, label=Table 4, caption=

Heat release characteristics data of EP-CE and its composites

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 PHRR/
(kW·m-2)
THR/
(MJ·m-2)
EP-CE 581.1 100.8
10DOPO-BPS/EP-CE 458.1 73.3
3OSEP/EP-CE 557.7 86.7
9DOPO-BPS/1OSEP/EP-CE 408.5 68.3
), ArticleFig(id=1165681896752161209, tenantId=1146029695717560320, journalId=1146031787341344770, articleId=1148106703108825543, language=CN, label=表4, caption=

EP-CE及其复合材料的热释放特性数据

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 PHRR/
(kW·m-2)
THR/
(MJ·m-2)
EP-CE 581.1 100.8
10DOPO-BPS/EP-CE 458.1 73.3
3OSEP/EP-CE 557.7 86.7
9DOPO-BPS/1OSEP/EP-CE 408.5 68.3
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DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能
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刘勇 1, 2, 3 , 姜一帆 1 , 耿鑫玺 1 , 张焘 4
中国安全科学学报 | 安全工程技术 2025,35(2): 111-117
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中国安全科学学报 | 安全工程技术 2025, 35(2): 111-117
DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能
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刘勇1, 2, 3 , 姜一帆1, 耿鑫玺1, 张焘4
作者信息
  • 1 湖南科技大学 资源环境与安全工程学院,湖南 湘潭 411201
  • 2 地下空间防火防爆材料与装备湖南省工程研究中心,湖南 湘潭 411201
  • 3 火灾爆炸防控与应急技术湖南省普通高等学校重点实验室,湖南 湘潭 411201
  • 4 南京工业大学 安全科学与工程学院,江苏 南京 211816
  • 刘勇 (1984—),男,湖南宁乡人,博士,副教授,主要从事危险化学品道路运输安全、海泡石防火阻燃等方面的研究。E-mail:

Preparation and properties of DOPO-BPS/OSEP/EP-CE flame retardant composite materials
Yong LIU1, 2, 3 , Yifan JIANG1, Xinxi GENG1, Tao ZHANG4
Affiliations
  • 1 College of Resources,Environment and Safety Engineering,Hunan University of Science and Technology,Xiangtan Hunan 411201,China
  • 2 Hunan Engineering Research Center for Fire and Explosion Prevention Materials and Equipment in Underground Spaces,Xiangtan Hunan 411201,China
  • 3 Key Laboratory of Fire and Explosion Prevention and Emergency Technology in Hunan Province,Xiangtan Hunan 411201,China
  • 4 College of Safety Science and Engineering,Nanjing Technology University,Nanjing Jiangsu 211816,China
出版时间: 2025-02-28 doi: 10.16265/j.cnki.issn1003-3033.2025.02.0976
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为提高环氧树脂(EP)-氰酸酯树脂(CE)复合材料的阻燃与抑烟性能,首先以9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO)与4,4'-二羟基二苯砜(BPS)为原料,合成一种新型阻燃剂DOPO-BPS,通过溶液浇筑法,将DOPO-BPS与有机海泡石(OSEP)共同引入EP-CE基体中,制备阻燃DOPO-BPS/OSEP/EP-CE复合材料;然后在傅里叶红外光谱仪(FTIR)分析、核磁共振(NMR)分析、热重分析(TGA)、极限氧指数(LOI)测试、UL-94垂直燃烧测试和锥形量热仪分析的基础上,研究不同比例的DOPO-BPS与OSEP对EP-CE复合材料阻燃性能和抑烟性能的影响。研究表明:DOPO-BPS的磷杂菲环结构能形成稳定炭层,阻断热氧传递,与OSEP的协同作用显著提升了阻燃效果和抑烟性能。当阻燃剂DOPO-BPS与OSEP以9∶1的质量比添加至EP-CE时,阻燃性能和抑烟性能最佳,阻燃性能达V-0级,LOI增至31.4%,且热释放速率峰值、总热释放量和产烟总量相比于EP-CE,分别降低了29.7%、32.2%和32.7%。

环氧树脂(EP)  /  氰酸酯树脂(CE)  /  9,10-二氢-9-氧杂-10-磷杂菲10-氧化物(DOPO)  /  4,4'-二羟基二苯砜(BPS)  /  有机海泡石(OSEP)  /  阻燃  /  复合材料

To enhance the flame retardancy and smoke suppression performance of EP-CE composites,a novel flame retardant was synthesized using DOPO and BPS as raw materials. The flame-retardant DOPO-BPS/OSEP/EP-CE composites were fabricated by the solution casting method,where DOPO-BPS and OSEP were jointly introduced into EP-CE matrix. Based on Fourier transform infrared spectroscopy (FTIR) analysis,nuclear magnetic resonance (NMR) analysis,thermogravimetric analysis (TGA),limiting oxygen index (LOI) test,UL-94 vertical burning test,and cone calorimeter analysis,the effects of different ratios of DOPO-BPS and OSEP on the flame retardancy and smoke suppression properties of EP-CE composite materials were studied. The results show that the phosphaphenanthrene ring structure of DOPO-BPS could form a stable carbon layer and block the transfer of heat and oxygen. The synergistic effect with OSEP significantly improves the flame retardant effect and smoke suppression performance. When the flame retardant DOPO-BPS and OSEP are added to EP-CE at a mass fraction of 9∶1,the flame retardant performance and smoke suppression performance are the best,the flame retardant performance reaches V-0 level,and the LOI increases to 31.4%. Compared with EP-CE,the peak heat release rate,total heat release and total smoke production decrease by 29.7%,32.2% and 32.7%,respectively.

epoxy resin (EP)  /  cyanate ester resin (CE)  /  9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO)  /  bisphenol sulfone (BPS)  /  organic sepiolite (OSEP)  /  flame retardancy  /  composite materials
刘勇, 姜一帆, 耿鑫玺, 张焘. DOPO-BPS/OSEP/EP-CE阻燃复合材料的制备及性能. 中国安全科学学报, 2025 , 35 (2) : 111 -117 . DOI: 10.16265/j.cnki.issn1003-3033.2025.02.0976
Yong LIU, Yifan JIANG, Xinxi GENG, Tao ZHANG. Preparation and properties of DOPO-BPS/OSEP/EP-CE flame retardant composite materials[J]. China Safety Science Journal, 2025 , 35 (2) : 111 -117 . DOI: 10.16265/j.cnki.issn1003-3033.2025.02.0976
环氧树脂(Epoxy Resin,EP)和氰酸酯树脂(Cyanate Ester resin,CE)作为高性能热固性聚合物,被广泛应用于航空航天、汽车制造、电子电器等工业领域,其优异的机械性能和电气性能,使得这类材料成为现代工业不可或缺的重要组成部分。然而,EP-CE复合材料存在阻燃性能差和生烟量大的问题,限制了其应用范围的扩展[1]
添加磷系阻燃剂是提高热固性聚合物阻燃性能的途径之一,例如:LIN Chinghsuan[2]通过将含磷的阻燃剂与CE接枝,再与EP混合,成功提升了混合物的阻燃性。HO Tsunghan等[3]在EP中添加了含磷阻燃剂,使得UL-94垂直燃烧测试达到了V-0等级。而9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(9,10-Dihydro-9-Oxa-10-Phosphaphenan-Threne-10-Oxide,DOPO)作为一种常用的磷系阻燃剂,因其携带的苯环结构能有效提升阻燃剂与EP和CE等基材的相容性,并在聚合物燃烧过程中,在凝聚相上形成炭层,可覆盖于聚合物外表面,能够减缓热量、氧气和可燃气体产物的传递,从而降低可燃性,成为制备高性能阻燃复合材料的有力支持[4]。此外,添加单一元素阻燃剂往往难以满足阻燃需求,研究者们开始探索多元素协同阻燃策略,如于水军[5]、周颖[6]等在EP-CE体系中引入硫、氮元素后,其阻燃效果良好。4,4'-二羟基二苯砜(Bisphenol Sulfone,BPS)作为阻燃材料制备过程中的重要成分,能够在分子结构中提供特定的硫元素,进而提高材料的阻燃能力[7]。而海泡石(Sepiolite,SEP)独特的层链状结构和催化性能,可有效阻碍燃烧反应的发生,改善复合材料的抑烟性能,但分散性不好,与EP-CE的相容性差,发挥协同阻燃效果之前还需进行有机改性[8-9]
基于此,笔者拟引入BPS、改性有机SEP(Organic Sepiolite,OSEP)与磷系阻燃剂DOPO,构建新型多元素协同阻燃体系,通过研究复合材料的热稳定、阻燃和燃烧等性能,探讨DOPO-BPS/OSEP/EP-CE阻燃复合材料的相关作用机制。
试验原料主要有:EP、CE、DOPO、三乙胺、四氯化碳、BPS、γ-缩水甘油醚氧丙基三甲氧基硅烷、二氯甲烷、γ-氨丙基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH560)、SEP、无水乙醇、盐酸、去离子水,均为分析纯。
所用试验仪器主要包括超声波分散机、集热式磁力搅拌器、循环水真空泵、玻璃仪器、电子天平、电热鼓风干燥箱、氧指数测试仪、垂直燃烧测试仪、锥形量热仪、傅里叶红外光谱仪(Fourier Transform Infrared Spectroscopy,FTIR)、核磁共振 (Nuclear Magnetic Resonance,NMR)波谱仪、扫描电镜(Scanning Electron Microscope,SEM)、X射线衍射仪和热重(Thermogravimetric,TG)仪。
取 17.28g的DOPO溶于二氯甲烷,加入12.00g的BPS、9.70g的三乙胺搅拌后,滴加四氯化碳14.76g,反应12h。产物经萃取洗涤、减压蒸馏,得到乳白色DOPO-BPS固体。
通过稀盐酸溶液酸化SEP,搅拌12h后洗涤、干燥得酸改SEP样品(Acid-modified SEP,A-SEP);将硅烷偶联剂KH560在乙醇中水解,与A-SEP混合,经超声分散后,在85℃反应4h;产物经洗涤、80℃真空干燥12h,研磨过筛并保存得到硅烷偶联剂改性OSEP。
按6∶4质量比取EP与CE树脂,先加热EP至80℃后,加入不同比例的DOPO-BPS或OSEP,搅拌1h,再加入CE,并升温至100℃,并搅拌1h。再将混合液浇注到预热模具中,分别在150、180和200℃下固化2h,得到6种样品,见表1
图1为DOPO、BPS和DOPO-BPS的FTIR图,从中可以看出,在特定波段,产物DOPO-BPS在3 060cm-1显示DOPO苯环上的=C-H伸缩振动峰,916、755和600cm-1显示P-O-C、P-C和P=O基团伸缩振动峰,1 286和1 147cm-1为BPS的-SO2-基团拉伸振动峰。原料DOPO的P-H和BPS的-OH伸缩振动峰在产物中消失,表明二者在反应中消耗。这些变化表明DOPO的P-H键与BPS的酚羟基成功反应,产物保留了砜基和含磷基团。因此,可以初步推断产物DOPO-BPS成功合成。
DOPO-BPS的1H NMR图谱和31P NMR图谱如图2所示。由图2a可知:1H NMR谱图化学位移6.8×10-6 ~ 8.05×10-6处归属于苯环,证实DOPO框架保留;化学位移8.79×10-6处P-H共振减弱,表明反应发生。不同质子化学环境的位点被标记并计算面积比,与理论比基本一致,验证了产物结构。此外,1H NMR谱图中化学位移5.0×10-6 ~ 5.5×10-6处为溶剂峰,化学位移1.0×10-6处附近为三乙胺峰;图2b31P NMR谱图在化学位移7.27×10-6处显示强烈信号,归因于DOPO-BPS的磷原子。这些数据与FTIR分析结果相符,共同证实了DOPO-BPS的成功合成。
氮气氛围下6组样品的TG测试数据见表2,TG和微商热重(Differential Thermogravimetric,DTG)曲线如图3所示。当OSEP添加量超过3%质量分数时,SEP在EP-CE复合材料中会发生团聚现象,破坏复合材料的内部联结,故采用3OSEP/EP-CE作为对照组。
表2可以看出,添加10%DOPO-BPS复合材料的残炭量达到了18.9%,相较于EP-CE的15.2%有所提高。这一提升可能与DOPO-BPS本身所具有的P=O和S=O等基团在高温下产生的磷酸盐、多磷酸盐及硫酸盐等酸性物质有关。这些酸性物质催化了熔融物质的形成,促使炭层交联更加致密,起到了隔绝氧气及保护作用;增加3%OSEP复合材料的初始失重温度和最大失重速率温度相较于EP-CE均有所提升,这表明OSEP能够延缓EP-CE的热降解过程。分析不同配比下的DOPO-BPS和OSEP复合阻燃剂对EP-CE复合材料热稳定性能的影响,发现添加DOPO-BPS和OSEP后,复合材料的t5%普遍降低,这可能与阻燃剂在燃烧初期的提前分解,形成炭层以减缓燃烧和烟气释放有关。尽管t5%降低,但复合材料的tmax相较于EP-CE有所提升,最大增幅达12℃,这表明DOPO-BPS和OSEP共同增强了EP-CE的热稳定性。
图3a可知:t5%的变化趋势与阻燃剂的配比密切相关。随着DOPO-BPS含量的减少和OSEP含量的增加,t5%呈现出波动,可能由于SEP添加量影响了聚合物分子链的稳定性[10]。而9DOPO-BPS/1OSEP/EP-CE的t5%最低,达到323.6℃,较EP-CE下降了33.1℃,表明阻燃剂相互作用形成的新化合物可能会影响热稳定性。此外,所有复合材料在热解过程中均呈现单一失重阶段,说明阻燃剂的引入并未改变EP-CE的基本热分解机制。同时,在添加量一定的情况下,随着OSEP含量的增加,残炭量减少,但1%OSEP含量的复合材料在800℃下的残炭量较EP-CE增加2.8%,表明适量添加OSEP有助于提高复合材料的残炭率[11]
EP-CE复合材料的极限氧指数(Limiting Oxygen Index,LOI)和UL-94垂直燃烧试验结果见表3
表3可知:DOPO-BPS阻燃剂的加入使复合材料的燃烧等级从NR提升至V-0,燃烧性能明显改善。并且在特定的混合比例下,复合阻燃剂9DOPO-BPS/1OSEP的阻燃效果优于单一阻燃剂DOPO-BPS和OSEP,这表明DOPO-BPS和OSEP在阻燃EP时具有协同效应,能够有效地提升材料的阻燃性能。并且DOPO-BPS阻燃剂的加入对提升EP-CE复合材料的LOI值起到了显著的作用。特别是在9DOPO-BPS与1OSEP的质量比下,复合材料的LOI值达到了最高的31.4%。
EP-CE、10DOPO-BPS/EP-CE、3OSEP/EP-CE和9DOPO-BPS/1OSEP/EP-CE的锥形量热仪测试结果如图4所示。EP-CE复合材料的点燃时间未因OSEP的添加而发生显著改变,表明DOPO-BPS是影响燃烧性能的因素;DOPO-BPS与OSEP的组合在降低热释放速率(Heat Release Rate,HRR)上有优势,原因在于SEP的束状绞缠结构能吸附燃烧杂质,增强炭层强度,与DOPO-BPS协同作用,抑制燃烧过程[12]
表4给出了EP-CE及其复合材料的峰值放热速率(Peak of Heat Release Rate,PHRR)和总放热量(Total Heat Release,THR)。与EP-CE相比,复合材料的阻燃效果提升显著,其中9DOPO-BPS/1OSEP组合的PHRR和THR降低幅度最大,分别为29.7%和32.2%。
EP-CE及其复合阻燃材料的烟气释放速率(Smoke Production Rate,SPR)和总烟气释放量(Total Smoke Production,TSP)测试结果如图5所示。添加DOPO-BPS、OSEP或DOPO-BPS/OSEP复合阻燃剂的EP-CE复合材料在产烟特性上均有所改善。特别是9DOPO-BPS/1OSEP/EP-CE复合材料展现出更显著的烟雾抑制效果。单独添加DOPO-BPS的EP-CE复合材料的峰值SPR略有上升,可能与气相阻燃作用相关。但加入OSEP后,峰值SPR降低了15.7%,TSP降低了16%,相对于EP-CE则分别从0.235降低了8.5%和32.7%。这表明OSEP的二维结构在高温下促进炭层形成,其层链状结构有效阻碍烟气逸出,提高了阻燃性能并显著减少了烟气生成与释放,对降低烟雾毒性具有实际意义。
EP-CE及其复合阻燃材料的烟气中CO和CO2的生成速率测试结果如图6所示。可以看出,在阻燃剂总添加质量分数为10%时,9DOPO-BPS/1OSEP/EP-CE复合材料的CO生成速率峰值较10DOPO-BPS/EP-CE降低了17.2%,表明OSEP显著减少了CO毒气产生,但是OSEP的加入未明显改变燃烧过程,CO生成速率峰值降低的同时,CO2生成速率峰值升高,这归因于SEP二维结构吸附并催化CO为CO2。因此,SEP与DOPO-BPS复合使用不仅能降低燃烧放热性能,还减少CO产生并促进CO向CO2转化,对提高材料的火灾安全性具有潜在应用价值。
图7为3组阻燃样品燃烧后的残炭SEM谱图。由图7a可知:EP-CE的残炭表面存在大量孔洞,为热量和燃料的传输提供了通道;图7b则是加入DOPO-BPS后,残炭表面变得连续且光滑,这种组织紧密的炭层能够限制热量和易燃化合物的传递;图7c表示进一步加入OSEP后,炭层形貌未发生明显改变,但变得更加连续。残炭中的根状物质为SEP,其作为隔热屏障,减少了热量和氧气的传递;这种紧密的炭层结构进一步增强了复合材料的阻燃性能。
1) 通过物理共混法,将DOPO-BPS和OSEP作为协同阻燃剂引入EP-CE体系,这样有助于EP-CE燃烧过程中形成紧密炭层结构,降低烟气和燃烧热释放量。
2) 协同阻燃体系能有效提高EP-CE的阻燃性能,其中9DOPO-BPS/1OSEP/EP-CE表现最佳,复合材料的最大失重速率温度提高了10℃,LOI达到了31.4%,PHRR、THR和TSP分别比EP-CE降低29.7%、32.2%和32.7%。
3) OSEP的引入弥补了DOPO衍生物抑烟能力的不足,相对于10DOPO-BPS/EP-CE,9DOPO-BPS/1OSEP/EP-CE复合材料的SPR和TSP峰值分别减低15.7%和16%。
  • 湖南省自然科学基金资助(2024JJ8338)
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2025年第35卷第2期
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doi: 10.16265/j.cnki.issn1003-3033.2025.02.0976
  • 接收时间:2024-09-02
  • 首发时间:2025-07-05
  • 出版时间:2025-02-28
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  • 收稿日期:2024-09-02
  • 修回日期:2024-11-11
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湖南省自然科学基金资助(2024JJ8338)
作者信息
    1 湖南科技大学 资源环境与安全工程学院,湖南 湘潭 411201
    2 地下空间防火防爆材料与装备湖南省工程研究中心,湖南 湘潭 411201
    3 火灾爆炸防控与应急技术湖南省普通高等学校重点实验室,湖南 湘潭 411201
    4 南京工业大学 安全科学与工程学院,江苏 南京 211816
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2种不同金属材料的力学参数

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属数
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genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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