膨胀蛭石/酚醛阻燃保温复合材料的制备及性能

以膨胀蛭石为阻燃剂,采用中温发泡方法与酚醛树脂复合制备膨胀蛭石/酚醛阻燃保温复合材料。阻燃保温复合材料通过极限氧指数、锥形量热、导热系数和表观密度分析了发泡温度、固化剂含量、发泡剂含量、表面活性剂含量、固化时间以及蛭石含量对膨胀蛭石/酚醛阻燃保温复合材料阻燃及保温性能的影响。结果表明:以膨胀蛭石为阻燃剂制备的膨胀蛭石/酚醛阻燃保温复合材料的阻燃保温性能优越、表观密度低。单因素实验结果表明,膨胀蛭石/酚醛阻燃保温复合材料的最优条件为发泡温度80℃、固化剂含量10wt%、发泡剂含量10wt%、表面活性剂含量5wt%、固化时间2 h以及蛭石含量60wt%。最优条件下的膨胀蛭石/酚醛阻燃保温复合材料表观密度为190.08 kg/m3、压缩强度为0.32 MPa、导热系数为0.054 9 W/（m·K）、极限氧指数为71.1%、平均热释放速率为15 kW/m2。      

Fire retardant evaluation of carbon nanofiber/graphite nanoplatelets nanopaper-based coating under different heat fluxes

Three types of carbon nanofiber based nanopapers, namely, 1Clay/5CNF/9APP, 1xGnP/5CNF/9APP, and 3xGnP/1CNF/9APP were made and their flame retardant efficiency was compared with thermogravimetric analysis and cone calorimeter test with 50 kW/m² of heat flux. The nanopaper of 3xGnP/1CNF/9APP was selected for experimental study because of its relatively good bonding with underlying structure and flame resistance performance. The fire response of glass fiber reinforced polyester composites with and without the selected nanopaper coating was thoroughly examined with cone calorimeter test using varied heat fluxes. It was found that at higher heat flux, the nanopaper demonstrated better flame retardant efficiency. Specifically, at 100 kW/m² of heat flux, the 1st and 2nd PHRR of the nanopaper-coated sample were more than 32% and 47% lower than the PHRR of control sample, respectively. In order to gain an insight into the pyrolysis process and flame retardation mechanism, the temperature profiles at the middle and back of the samples subjected to different heat fluxes were recorded. At 100 kW/m² of heat flux, the final temperature within the nanopaper-coated sample was roughly 280 ^oC, which is lower than control sample. The degradation rates in flexural moduli of the samples with coupon shape were determined using three-point bending. The three-point bending test results showed when the sample was exposed to 25 kW/m² heat flux for 240 seconds, the flexural modulus of control sample almost reduced to zero, whereas the nanopaper-coated sample still retained a half of its original flexural modulus. Finally, flame retardation mechanism was proposed for the nanopaper-coated composites.     

Fire retardant evaluation of carbon nanofiber/graphite nanoplatelets nanopaper-based coating under different heat fluxes

Three types of carbon nanofiber based nanopapers, namely, 1Clay/5CNF/9APP, 1xGnP/5CNF/9APP, and 3xGnP/1CNF/9APP were made and their flame retardant efficiency was compared with thermogravimetric analysis and cone calorimeter test with 50 kW/m² of heat flux. The nanopaper of 3xGnP/1CNF/9APP was selected for experimental study because of its relatively good bonding with underlying structure and flame resistance performance. The fire response of glass fiber reinforced polyester composites with and without the selected nanopaper coating was thoroughly examined with cone calorimeter test using varied heat fluxes. It was found that at higher heat flux, the nanopaper demonstrated better flame retardant efficiency. Specifically, at 100 kW/m² of heat flux, the 1st and 2nd PHRR of the nanopaper-coated sample were more than 32% and 47% lower than the PHRR of control sample, respectively. In order to gain an insight into the pyrolysis process and flame retardation mechanism, the temperature profiles at the middle and back of the samples subjected to different heat fluxes were recorded. At 100 kW/m² of heat flux, the final temperature within the nanopaper-coated sample was roughly 280 ^oC, which is lower than control sample. The degradation rates in flexural moduli of the samples with coupon shape were determined using three-point bending. The three-point bending test results showed when the sample was exposed to 25 kW/m² heat flux for 240 seconds, the flexural modulus of control sample almost reduced to zero, whereas the nanopaper-coated sample still retained a half of its original flexural modulus. Finally, flame retardation mechanism was proposed for the nanopaper-coated composites.     

笼状季戊四醇磷酸酯-可膨胀石墨协同阻燃天然橡胶

以笼状季戊四醇磷酸酯（PEPA）和可膨胀石墨（EG）构成协同阻燃体系添加到天然橡胶（NR）中制备EG-PEPA/NR复合材料。通过极限氧指数（LOI）和垂直燃烧（UL-94）测试、热失重和锥形量热分析、拉伸测试及残炭的SEM观察和FTIR检测,考察了不同质量配比的PEPA和EG对EG-PEPA/NR复合材料阻燃性能和力学性能的影响。结果表明,当PEPA与EG以33：7的质量比添加到NR中时,EG-PEPA/NR复合材料的阻燃性能和力学性能最好。EG-PEPA/NR复合材料的LOI达到28.1%,UL-94达到V-0级,600℃时残炭量从27.5%提高到33.6%,总热释放量和热释放速率峰值分别为96.2 MJ·m^-2和512.4 kW·m^-2,相比于纯NR分别降低了22.2%和40.3%,拉伸强度和断裂伸长率也分别达到13.8 MPa和368%。     

有机蒙脱土协同含磷木质素基成炭剂阻燃聚乳酸

将自制含磷木质素基成炭剂（Lig-P）和聚磷酸铵（APP）复配用于制备阻燃聚乳酸（PLA）基复合材料,考察了协效阻燃剂有机蒙脱土（OMMT）对阻燃PLA性能的影响。采用极限氧指数（LOI）仪、垂直燃烧（UL-94）测试仪、锥形量热仪、热失重分析仪分别对Lig-P-APP-OMMT/PLA阻燃复合材料的阻燃性能、热稳定性能和燃烧行为进行了研究。结果发现,OMMT与Lig-P-APP存在明显的协同阻燃作用,当OMMT替代3wt%的Lig-P-APP时,Lig-P-APP-OMMT/PLA阻燃复合材料的LOI由27%增加至32%,UL-94等级由V1级提高至V0级;且Lig-P-APP-OMMT/PLA阻燃复合材料的最大热降解速率有所降低,800℃的残炭量提高了将近50%;此外,OMMT的引入使PLA阻燃复合材料的热释放速率明显降低,热释放速率峰值（PHRR）、烟释放速率峰值（PSPR）及总烟释放量（TSR）分别降低了26.4%、60%及26.3%。OMMT可明显提高阻燃PLA炭层的致密度及石墨化程度。      

可膨胀石墨改性APP/PER/EN防火涂料热降解行为

采用可膨胀石墨 (EG) 对APP/PER/EN防火体系进行改性,制备成一种新型EG改性APP/PER/EN防火涂料。运用示差热分析 (DTA) 、热重分析 (TG) 、扫描电镜分析 (SEM) 、能谱分析 (EDS) 和隔热性能试验分析研究APP/PER/EN防火涂料和EG改性防火涂料的热降解行为、残余炭体元素含量、成炭率和隔热性能。EG改性防火涂料的APP-PER-EN之间的化学反应膨胀过程与可膨胀石墨物理膨胀过程作用温度范围接近,能产生很好的协同配合作用。膨胀石墨提高了APP/PER/EN防火涂料炭质层的成炭率、抗氧化性和热稳定性。EG添加量过高 (≥15%) 会造成燃烧后期炭质层脱离基材。10% EG (质量分数) 添加量能有效提高APP/PER/EN防火涂料的隔热防火性能。      

A effective flame retardant for epoxy resins based on poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate)

Poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) (PFR) was synthesized via the reaction between 10-(2,5-dihydroxyl-phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-BQ) and pentaerythritol diphosphonate dichloride (SPDPC). The structures of PFR were characterized by Fourier transformed infrared (FTIR) spectroscopy and ¹H nuclear magnetic resonance (¹H NMR). Thermal degradation behaviors and flame retardant properties of the epoxy resin (ER)/PFR systems were investigated from the thermogravimetric analysis (TGA), UL-94 test and the limiting oxygen index (LOI) test. Moreover, the surface morphology of the char residue was studied by scanning electron microscopy (SEM). When the PFR content reached 10 wt%, the epoxy resin system met the UL-94 V0 classification and the LOI value of 30.2. The microscale combustion calorimetry (MCC) was used to evaluate the combustion behaviors of the ER/PFR. It was found that the addition of PFR obviously decreased the value of peak heat release rate and total heat release of the hybrids. The TGA results showed that the epoxy resin with 10 wt% PFR exhibited high char yields. The high char yields and the high limiting oxygen index values were found to certify the excellent flame retardancy of this phosphorus-containing epoxy resin.     

磷杂菲反应型阻燃多元醇制备聚异氰脲酸酯硬泡及性能

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)、顺丁烯二酸、丙三醇、乙二醇为原料,合成出一种基于磷杂菲基团的新型无卤阻燃多元醇。通过傅里叶变换红外光谱、核磁共振氢谱表征了目标化合物的基本结构,热失重测试表明硬泡的残炭量也随阻燃多元醇的增加而升高,锥形量热测试表明阻燃多元醇的加入,使热释放速率和总热释放量大幅下降,阻燃多元醇制备的硬泡极限氧指数为26.7,达到UL-94V0级,压缩强度测试结果表明阻燃泡沫能满足建筑用聚氨酯硬泡保温材料高承载使用要求。     

Synergistic flame retardancy effect of graphene nanosheets and traditional retardants on epoxy resin

Novel non-toxic halogen-free flame retardants are replacing traditional flame retardants in polymer and polymer matrix composite structures. In this study, graphene nanosheet (GNS) is investigated in combination with traditional layered double hydroxide (LDH), layered rare-earth hydroxide (LRH), and phosphorus-based flame retardant (DOPO) to enhance the flame retardancy of epoxy resin. A synergistic flame retardancy effect is achieved in GNS/LDH and GNS/DOPO systems where combined GNS and LDH increased the viscosity of the epoxy melt, and limited the flame propagation through inhibition of dripping. The limiting oxygen index of epoxy increased from 15.9 to 23.6 with addition of 0.5 wt.% each of GNS and LDH. With the addition of 2.5 wt.% of both GNS and LDH, the total heat release of epoxy resin also reduced from 33.4 MJ/m² to 24.6 MJ/m². The synergistic effect of GNS and DOPO adopted a different mechanism. The addition of 2.5 wt.% of GNS and DOPO reduced the peak heat release rate from 1194 kW/m² to 396 kW/m², and the total heat release rate from 72.5 MJ/m² to 48.1 MJ/m². The synergistic mechanisms of the flame retardants were closely analyzed and correlated with the flame retardant properties.     

无卤阻燃乙烯-醋酸乙烯酯共聚物泡沫复合材料的制备及性能表征

为使得乙烯-醋酸乙烯酯共聚物(EVA)泡沫复合材料具有阻燃功能,分别添加膨胀石墨-聚磷酸铵(EGAPP)和膨胀石墨-聚磷酸铵-热塑性淀粉(EG-APP-TPS)两种不同复配阻燃剂,通过熔融共混和硫化发泡制备了无卤阻燃EVA泡沫复合材料。采用极限氧指数(LOI)、垂直燃烧(UL-94)、热分析质谱联用(TG-MASS)及扫描电镜(SEM)测试等对EG-APP/EVA及EG-APP-TPS/EVA泡沫复合材料进行表征。结果表明:EG-APP复配阻燃剂添加量为30wt%、EG与APP质量比为1∶4时,EG-APP/EVA泡沫复合材料的LOI达28.1%,UL-94为V-1级;而当EG-APP-TPS复配阻燃剂添加量同为30wt%,EG、APP与TPS质量比为1∶4∶1时,EG-APP-TPS/EVA泡沫复合材料的LOI可达29.3%,UL-94为V-0级。TG-MASS和SEM分析表明:EG、APP和TPS在气相和固相中均具有显著的协同阻燃作用。     

Flame-retarded biocomposites of poly(lactic acid), distiller’s dried grains with solubles and resorcinol di(phenyl phosphate)

The distiller’s dried grains with solubles (DDGS) were treated by smashing and water washing processes. The treatment effects on DDGS were analyzed, and the results showed that the thermal stability and the hydrophobicity of DDGS were improved by the treatment processes. The flame retarded biocomposites of poly(lactic acid) (PLA) with DDGS and degradable polymeric flame retardant resorcinol di(phenyl phosphate) (RDP) were prepared. The prepared biocomposites had good mechanical properties and the tensile strength of the biocomposite containing 15 wt% RDP and 15 wt% DDGS reached approximately 53 MPa. Meanwhile, using the limited oxygen index (LOI) and the underwriters laboratory (UL-94) tests, for the biocomposite, the LOI value was approximately 27.5% and V-0 rating in UL-94 was attained. Furthermore, the peak heat release rate of this biocomposite was reduced to 275 kW/m² compared with 310 kW/m² for pure PLA. After burning of the biocomposites, compact and coherent charred layer was formed and the char residues were analyzed in detail.     

三聚氰胺苯基磷酸盐的合成及在硬质聚氨酯泡沫中的应用

以三聚氰胺(MEL)和苯基磷酸(PPA)为原料,合成出一种磷氮类阻燃剂——三聚氰胺苯基磷酸盐(MPP),采用核磁共振磷谱和红外光谱对其结构进行了表征。通过极限氧指数(LOI)、UL 94和锥形量热测试对MPP阻燃的硬质聚氨酯泡沫(RPUF)的燃烧性能进行了研究。结果表明,当MPP添加量为15%(质量分数)时,阻燃RPUF的LOI为27%,达到了UL 94V-0级,其热释放速率峰值(PHRR)相对于未阻燃RPUF降低了约44%。采用热重分析(TGA)研究了阻燃RPUF的热分解特性,结果表明,添加15%MPP的阻燃RPUF的压缩强度和弯曲强度分别比未阻燃RPUF提高了50%和27%。导热系数测试结果表明,添加15%MPP的阻燃RPUF的导热系数稍微有所增加,约为0.025 9 W/(m·K)。     

一种桥链DOPO衍生物的合成及对聚乳酸的阻燃性能

以9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)和乙二醇为主要原料,碘化钠为催化剂,设计合成了一种新型的桥链DOPO衍生物(Di-DOPO)。采用红外光谱、差示扫描量热分析、热重分析、质谱分析、核磁共振等方法对其进行分析表征,确定了其结构。将该化合物与聚乳酸(PLA)共混,通过氧指数(LOI)测试、垂直燃烧、热重分析、锥形量热等手段考察了其对PLA的阻燃性能及热降解行为的影响。结果表明,Di-DOPO质量分数达到10%时就可以使阻燃PLA材料通过UL-94 V-0级,并能有效抑制PLA的熔滴现象,LOI值也由纯PLA的20%提升到36.3%。阻燃剂质量分数为5%,10%和15%时,热释放速率峰值(PHRR)分别降低了5.2%,12.7%,19.6%。当加入Di-DOPO后,阻燃PLA复合材料的热稳定性比纯PLA明显提高。综上,所制备的Di-DOPO阻燃剂对PLA具有很好的阻燃效果。     

Combination effect of carbon nanotubes with graphene on intumescent flame-retardant polypropylene nanocomposites

A novel polypropylene (PP) nanocomposite was fabricated by the incorporation of intumescent flame retardant (IFR), carbon nanotubes (CNTs) and graphene into the PP matrix. Results from TEM indicate that IFR, CNTs and exfoliated graphene nanosheets are dispersed finely in the PP matrix, which is supported by the XRD analysis results. Thermogravimetric (TGA) results show that the addition of IFR, CNTs and graphene improved the thermal stability and the char yields of PP. The PP/IFR/CNTs/RGO nanocomposites, filled with 18 wt% IFR, 1 wt% CNTs and 1 wt% graphene, achieve the limiting oxygen index value of 31.4% and UL-94 V0 grade. Cone calorimeter data reveal that combustion behavior, heat release rate peak (PHRR) and average specific extinction area (ASEA) of PP decrease substantially when combination effects of IFR, CNTs and graphene intervene. For the PP/IFR/CNTs/RGO nanocomposites, the PHRR exhibits an 83% reduction and the time of ignition is delayed 40 s compared with neat PP.     

兼具阻燃和导热性能的环氧树脂复合材料：石墨烯纳米片杂化三聚氰胺磷酸盐的作用

研发制备低成本、少缺陷及高效率的石墨烯纳米片杂化阻燃剂对实现复合材料多功能性具有重要意义。以三聚氰胺为助剥离剂将微粉石墨(GRA)经机械球磨后与磷酸液相反应得到一种阻燃导热的石墨烯纳米片杂化三聚氰胺磷酸盐(GMP),在表征GMP形貌、结构、组成和热稳定性的基础上,研究了添加GMP环氧树脂(EP)复合材料的阻燃、热分解和导热性能。GMP的热失重分析结果表明：与三聚氰胺磷酸盐(MP)相比,初始分解温度提升了29.3℃,与环氧树脂的热分解温度更匹配,有助于提高阻燃效率。氧指数仪、锥形量热仪和导热性能研究表明,GMP添加30wt%时,EP复合材料的极限氧指数达到了30.4%,UL 94垂直燃烧达到V-0级,峰值热释放速率(PHRR)和峰值烟释放速率(PSPR)分别下降69%和74.0%;导热系数提升至2.10 W·m^-1·K^-1,相对于EP提升了708%。这是由于GMP中石墨烯纳米片(GNPs)与MP的相互作用促进了EP形成了致密的膨胀炭层,有效提高了EP复合材料的阻燃性;随着GMP添加量的增加,GNPs和石墨微片传热通道的形成改善了EP复合材料的导...     

介孔分子筛和Cr_2O_3协同膨胀阻燃体系对阻燃天然橡胶性能的影响

用介孔分子筛(MCM-41)和Cr_2O_3协同膨胀型阻燃体系(IFR)对天然橡胶(NR)进行阻燃。为研究MCM-41和Cr_2O_3的阻燃协同作用,使用不同组分的两种协效剂协同IFR阻燃天然橡胶。对阻燃体系分别进行氧指数测试、热重分析、锥形量热分析、拉伸测试和残炭扫描分析。研究结果表明:天然橡胶单纯添加IFR时,其力学性能大幅下降,热学性能也没有显著提升。然而随着Cr_2O_3和MCM-41添加量的增加,橡胶基体的拉伸强度和断裂伸长率均有所改善,在IFR添加量为36%(与天然橡胶的质量比)、MCM-41添加量为1%,Cr_2O_3为3%时,IFR-MCM-41-Cr_2O_3复合阻燃剂的阻燃效果最好,热释放速率峰值和热释放总量均明显下降,IFR-MCM-41-Cr_2O_3/NR复合材料燃烧后,炭层发泡均匀且致密,极限氧指数(LOI)可以达到26.5%,垂直燃烧(UL-94)为V-0级。     

热塑性聚氨酯弹性体对聚对苯二甲酸丁二醇酯基阻燃复合材料性能的影响

以溴化聚苯乙烯(BPS)为阻燃剂,Sb₂O₃纳米颗粒(nano-Sb₂O₃)为协效阻燃剂,聚对苯二甲酸丁二醇酯(PBT)为基体,热塑性聚氨酯弹性体(TPU)为增韧组分,采用球磨分散和熔融共混的方法制备出TPU/nano-Sb₂O₃-BPS-PBT阻燃复合材料。通过DSC、拉伸、冲击和极限氧指数(LOI)等性能测试,研究了TPU质量分数对TPU/nano-Sb₂O₃-BPS-PBT阻燃复合材料力学性能与阻燃性能的影响。研究结果表明:TPU的加入可改善TPU/nano-Sb₂O₃-BPS-PBT阻燃复合材料的韧性;随着TPU质量分数的增加,TPU/nano-Sb₂O₃-BPS-PBT阻燃复合材料的缺口冲击强度上升,当TPU质量分数为9wt%时,其冲击强度相比于纯PBT提高了137%,断裂伸长率相比于纯PBT提高了340%,但该复合材料的拉伸强度有所下降。当TPU质量分数为3wt%时,该复合材料的拉伸强度大于纯PBT,冲击强度相比于纯PBT提高了52%,同时达到了难燃等级。此时,TPU/nano-Sb₂O₃-BPS-PBT阻燃复合材料表现出优异的综合性能。      

硼-氮阻燃剂与氢氧化镁协同阻燃环氧树脂

将硼-氮阻燃剂2,4,6-三(4-硼酸-2-噻吩)-1,3,5-三嗪(3TT-3BA)与Mg(OH)_2进行复配,然后将其添加到环氧树脂(EP)中,通过热重分析、锥形量热、极限氧指数、垂直燃烧等测试方法,研究了3TT-BA/Mg(OH)_2复配体系对EP的阻燃性能。研究发现,3TT-3BA与Mg(OH)_2具有协同阻燃作用,添加10%3TT-3BA/10%Mg(OH)_2到EP中,其极限氧指数达到了32.5%,垂直燃烧达到了UL94 V-0等级。同时,3TT-BA/Mg(OH)_2复配体系还能有效减小EP热释放速率、热释放总量和生烟总量。通过扫描电镜等手段探讨了3TT-BA/Mg(OH)_2复配体系的阻燃机理。     

木质素-木粉/高密度聚乙烯复合材料的制备及阻燃性能

将生物质可再生资源木质素（Lig）和一种P-N-B系阻燃剂单独或复配使用添加到木粉/高密度聚乙烯（WF/HDPE）混合物中,通过挤出成型的方式制备Lig-WF/HDPE复合材料,探究了Lig对阻燃型Lig-WF/HDPE复合材料阻燃性能的影响。锥形量热仪测试结果表明,Lig的加入能有效降低Lig-WF/HDPE复合材料的热释放速率,提高残余物质量。Lig添加量为15wt%时Lig-WF/HDPE复合材料的阻燃效果最佳,但发烟量较大。Lig与P-N-B系阻燃剂复配使用可使（P-N-B）-Lig-WF/HDPE复合材料的发烟量明显降低,阻燃性能进一步提高。Lig添加量为5wt%、P-N-B系阻燃剂添加量为10wt%时,（P-N-B）-Lig-WF/HDPE复合材料的极限氧指数从未添加阻燃剂WF/HDPE复合材料的24.3提高到27.3,且力学性能较两种阻燃剂单独使用时有提升。      

环状磷腈/聚磷酸铵/三聚氰胺膨胀阻燃环氧树脂研究

本文以DOPO衍生物六(4-DOPO羟甲基苯氧基)环三磷腈(DOPOMPC)、聚磷酸铵(APP)以及三聚氰胺(MEL)形成复配膨胀体系(IFR)阻燃环氧树脂.采用极限氧指数(LOI)、水平、垂直燃烧(UL-94)方法研究了IFR体系对环氧树脂体系阻燃性能影响,通过锥形量热(CONE)研究了体系燃烧特性,通过扫描电子显微镜(SEM)对体系成炭情况进行观察.结果表明,IFR膨胀阻燃体系对环氧树脂具有良好的协同阻燃作用,其中8%DOPOMPC/8%APP/4%MEL(EP3)体系LOI值较纯EP(EP0)提高37.8%;各项燃烧参数也得到了改善,热释放速率峰值(pk-HRR)、有效燃烧热平均值(av-EHC)、比消光面积平均值(av-SEA)及一氧化碳释放速率平均值(av-CO)相对于10%DOPOMPC/10%APP/EP(EP1)分别降低了53.8%、84.4%、57.7%和75.8%;拉伸强度、弯曲强度和冲击强度较EP1分别提高了1.3倍、79.4%和2.5倍;宏观拍摄和扫描电镜结果表明EP3膨胀炭层连续、均匀、致密,阻燃效果良好.