用锥形量热仪研究聚氨酯泡沫的阻燃性能

在50 kW/m2辐射功率下,利用锥形量热仪研究了氢氧化铝、卤系阻燃剂、氮系阻燃剂和磷系阻燃剂阻燃聚氨酯泡沫(PUF)的阻燃特性,获得了点燃时间、最大热释放速率、总热释放、比消光面积及质量损失速度等参数。结果表明,将热释放速率、燃烧总释放热和烟气释放量作为材料阻燃性能好坏的评价指标,阻燃剂聚磷酸铵（APP）和三聚氰胺磷酸盐（MP）是PUF的理想阻燃剂。     

PFF与PUF热稳定性及燃烧性能研究

制备了酚醛泡沫和聚氨酯泡沫，并研究了酚醛硬泡与聚氨酯硬泡的热稳定性及燃烧性能。结果表明：和聚氨酯泡沫比较，酚醛泡沫的热失重小，热释放速率和热释放总量低。因此酚醛泡沫的热稳定性和阻燃性能明显优于聚氨酯泡沫。     

Ni-MOF与焦磷酸哌嗪对环氧树脂的协同阻燃及抑烟

将含镍金属有机框架材料（Ni-MOF）与焦磷酸哌嗪（PPAP）复配后添加到环氧树脂（EP）中,通过极限氧指数（LOI）、垂直燃烧（UL 94）及锥形量热（CONE）测试研究了材料的阻燃性能及烟释放行为。结果表明,添加6%（质量分数,下同）的PPAP时,材料的LOI值为27.9%,垂直燃烧测试通过了UL 94 V-0级;当PPAP与Ni-MOF以质量比99∶1混合,总添加量为5%时,材料的LOI值达到29.3%并通过了UL 94 V-0级;极少量Ni-MOF的加入,有效提高了材料的阻燃效率。CONE测试表明,在相同阻燃剂添加量下,EP/PPAP/Ni-MOF材料的热释放速率、总热释放量、烟释放速率及总烟释放量,与EP/PPAP材料相比均得到了明显降低;Ni-MOF的引入,降低了材料的燃烧强度,减少了烟气的释放;Ni离子与PPAP受热分解形成的磷酸及多聚磷酸发生交联,将更多的磷留在了凝聚相中,促进了材料形成更加丰富、强度更高的炭层,有效抑制EP燃烧过程中热量和烟气的释放,从而提高了EP材料的火安全性能。     

聚磷酸铵/可膨胀石墨阻燃环氧树脂的性能

将聚磷酸铵(APP)与可膨胀石墨(EG)进行复配后添加到环氧树脂(EP)中,以间苯二胺(PDA)为固化剂,制备阻燃环氧树脂固化物,通过极限氧指数(LOI)、垂直燃烧(UL-94)和热重分析(TGA)测试研究了材料的阻燃性能、热降解行为,通过锥形量热(CONE)测试研究了材料的燃烧行为,通过扫描电镜(SEM)研究了材料炭层的形貌,同时还研究了APP与EG的不同配比对EP材料阻燃性能的影响。结果表明:当APP与EG的质量比为3∶2、添加量为5%时,阻燃EP材料通过了UL-94 V-0级,LOI值达到了29.0%。TGA测试结果表明:阻燃剂APP及EG的加入明显地改变了材料的热降解行为,促进了环氧树脂材料的提前降解和成炭,降低了材料的热降解速率,材料在700℃时的残炭量由14.6%提高到了29.9%。CONE测试结果表明:阻燃剂的加入明显降低了材料的热释放速率(HRR)和总热释放量(THR)。SEM测试结果表明:阻燃材料燃烧后形成了致密均一的炭层,能很好地阻止氧气和热量进入到材料的内部,同时减少可燃气体的逸出,从而抑制了基体树脂的进一步降解和燃烧,提高了材料的阻燃性能。     

硼酸锌阻燃抑烟PC/ABS的研究

研究硼酸锌在阻燃PC/ABS体系中对材料烟密度及阻燃性能的影响,结果表明,加入一定含量的硼酸锌能显著降低阻燃PC/ABS的烟密度且提高材料的阻燃性能。这是因为硼酸锌高温时释放结晶水并形成粘稠液体延缓了材料燃烧进程,使热释放速率和烟释放率降低及阻燃性能提高;硼酸锌的加入使得阻燃PC/ABS的热稳定性及成炭率有所降低,对阻燃PC/ABS的力学及流动性能也有一定的影响。     

阻燃抑烟剂对软聚氯乙烯材料燃烧性能的影响

针对氢氧化镁、硼酸锌、三氧化二锑等常用的阻燃抑烟剂对在软聚氯乙烯燃烧时的热释放速率和一氧化碳释放量进行了研究 ,发现氢氧化镁和硼酸锌虽然可以降低材料的热释放性能和发烟量 ,但是会大大增加烟气中一氧化碳的释放量 ;而三氧化二锑会增加材料的发烟量 ,但却能大大降低烟气中的一氧化碳的释放量     

聚氨酯／蒙脱土复合阻燃硬质泡沫材料的研究

采用原位聚合法制备了蒙脱土阻燃硬质聚氨酯泡沫材料,并用多种添加型阻燃剂制备了阻燃聚氨酯硬质泡沫,同时尝试有机改性蒙脱土与添加型阻燃剂并用对聚氨酯硬质泡沫进行阻燃。用锥形量热仪测试了阻燃聚氨酯泡沫材料的燃烧性能,结果发现,材料的热释放速率、质量损失速率与纯聚氨酯硬质泡沫相比均显著降低,峰值热释放速率最多降低到纯硬质泡沫的55％,表明制备的泡沫材料具有较好的阻燃性。用X-射线衍射和扫描电镜分析了蒙脱土及有机改性蒙脱土的微观结构。通过分析材料的燃烧性能和燃烧残余物,探讨了其可能的阻燃机理。     

磷/溴单分子阻燃硬质聚氨酯泡沫复合材料制备及阻燃性能

将磷/溴单分子阻燃剂1,3,5-三(5,5-二溴甲基-1,3-二氧杂己内磷酰氧基)苯(FR)作用于硬质聚氨酯泡沫,制备出阻燃复合材料(FR/RPUF),利用极限氧指数、水平燃烧、锥形量热研究FR对硬质聚氨酯泡沫的阻燃性能及火灾燃烧性能的影响。结果发现:当FR添加量为15%时,阻燃聚氨酯泡沫的LOI达到24.1%,水平燃烧达到HF-1级,热释放速率平均值、热释放速率峰值、有效燃烧热及一氧化碳平均释放量分别降低78.7%、78.4%、57.1%和32.2%,硬质聚氨酯泡沫材料火灾危险性大幅度降低。     

氮磷硼共掺杂木质素酚醛泡沫及其阻燃性能研究

采用氮、磷、硼三种阻燃元素共掺杂木质素基酚醛泡沫,通过扫描电镜、热重、锥形量热、拉曼光谱和X射线能谱等分析方法研究了泡沫的形态、性能及阻燃机理。结果表明,与木质素基酚醛泡沫(LPF)相比,添加树脂质量10%的含有氮、磷、硼复合阻燃剂的木质素基酚醛泡沫(NPBLPF)900℃的残炭率达到60.53%,提高了47.20%。总烟释放量和总释放热分别为110.6 m²/m²和10.3 MJ/m²,分别降低了41.14%和64.85%。泡沫残炭表面的磷化合物炭层和硼化合物形成的玻璃态共同提高了残炭的石墨化程度,这是泡沫阻燃性得到提高的主要原因。     

氧化石墨烯对聚氨酯泡沫阻燃性能影响的研究

以多异氰酸酯、组合聚醚为主要原料,以氧化石墨烯为阻燃剂,采用一步法工艺制备氧化石墨烯-聚氨酯泡沫。采用极限氧指数、锥形量热和热重分析三种方法对材料的阻燃性能进行表征。研究结果表明:相比纯聚氨酯泡沫,添加1.0%氧化石墨烯的整体阻燃效果较佳;泡沫材料的氧指数提升0.9个百分点,热释放速率峰值(pHRR)降低55%,总释热量(THR)降低20%;质量损失速率(MLR)、烟释放(SPR)和CO产生速率(COp)等指标均有明显降低。     

Flame retardant,thermal, and mechanical properties of glass fiber/nanoclay reinforced phenol–urea–formaldehyde foam

To increase the toughness, flame retardancy, and compression strength of phenolic foams, glass fiber/nanoclay composites were prepared, and their mechanical property, cellular structure, thermal stability, and flame retardancy were investigated. The results show that the pulverization rate of phenolic foam decreases significantly by adding glass fibers and nanoclay. The impact strength of the composite foam significantly increases with increasing quantities of glass fiber and nanoclay, while the compression strength of the composite foam first increases and then decreases. The microstructure of the composite foam indicates that excessive glass fiber increases the number of open cells, while an appropriate quantity of nanoclay can control the cell size. Further, excessive clay increases the thickness of cell walls and the percentage of open cells. Nanoclay increases the thermal stability of the composite foam; this decreases the maximum heat release rate, total heat release, and total smoke release of the foam, thus reducing its fire hazards. Glass fiber and nanoclay demonstrate good synergistic effects and significantly increase the compression strength, thermal stability, and flame retardancy of the foam. Moreover, the addition of nanoclay and glass fiber–nanoclay decreases the average aperture of the cells. POLYM. COMPOS., 37:2323–2332, 2016. © 2015 Society of Plastics Engineers     

基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料,成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP）,用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性,氮气气氛下的初始分解温度为191.9℃,700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%,最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²,总产烟量从10.5 m²下降到5.3 m²。     

海泡石与APP对PVC/竹粉复合材料的阻燃抑烟机理

将海泡石(SEP)和聚磷酸铵(APP)同时加到聚氯乙烯(PVC)/竹粉复合材料中,考察SEP和APP对复合材料的协效阻燃抑烟作用及力学性能的影响。结果表明,在锥形量热实验中,热释放速率峰值相对减少42.8%,平均热释放速率和总热释放量相对减少29.5%和25.7%,总烟释放量相对降低了12.2%,一氧化碳平均产率相对降低了42.0%;扫描电子显微镜分析发现,APP具有催化成炭并形成膨胀泡沫炭层的作用,而SEP具有吸附聚集诱导成炭的作用;APP的阻燃机理主要属于气相阻燃机理,SEP的阻燃机理主要属于凝聚相阻燃机理;弯曲性能测试结果表明,SEP与APP对PVC/竹粉复合材料具有协同颗粒增强作用;拉伸性能测试结果表明,SEP对PVC/竹粉复合材料的塑性变形能力的损害比APP小。因此,SEP与APP联用能够对PVC/竹粉复合材料进行有效的阻燃抑烟,同时也能增强复合材料的力学性能。     

利用锥形量热仪研究聚氨酯硬泡的燃烧性能

利用锥形量热仪对硬质聚氨酯泡沫(RP UF)的燃烧特性进行了研究.通过对RP UF燃烧过程中的热释放速率、热释放总量、烟生成速率和总产烟量等进行系统性测试,讨论了聚醚多元醇、聚酯多元醇以及异氰酸酯指数(R值)对RP UF热危险性和烟气危险性的影响.结果表明,聚酯多元醇替代聚醚多元醇制备的RP UF燃烧过程中的热释放速率...     

Mechanical and thermal properties of phenolic/glass fiber foam modified with phosphorus‐containing polyurethane prepolymer

Phenolic foam exhibits outstanding flame, smoke and toxicity properties, good insulation properties and low production costs. However, the brittleness and pulverization of phenolic foam have severely limited its application in many fields. In this study, a novel phosphorus‐containing polyurethane prepolymer (DOPU) modifier was firstly synthesized, and then the foaming formula and processing of toughening phenolic foam modified with DOPU and glass fiber were explored. The structure and reactive behavior of prepolymer and phenolic resin were investigated using Fourier transform infrared spectroscopy. The effects of DOPU and glass fiber on the apparent density, compressive strength, bending strength and water absorption were investigated. The results suggested that the apparent density, compressive strength and bending strength of modified phenolic foam tended to increase irregularly with increasing content of DOPU. The addition of DOPU led to lower water absorption of glass fiber‐filled foam. Thermal stability and flame retardancy were examined using thermogravimetric analysis and limiting oxygen index (LOI) tests. It was found that foam with 3% DOPU and 0.5% glass fiber added exhibited good thermal stability and high char yields. The LOI value of modified phenolic foams decreased with increasing DOPU content, but it still remained at 41.0% even if the amount of modifier loaded was 10 wt%. © 2012 Society of Chemical Industry     

聚氯乙烯/竹炭贴面复合材料的燃烧特性研究

以竹炭(BC)和聚氯乙烯(PVC)为原料,通过熔融混炼热压后进行贴面,制备不同贴面PVC/BC复合材料.采用锥形量热、热失重、热重红外联用分析对不同贴面PVC/BC的燃烧行为与烟气生成特性进行表征,综合评价其燃烧安全性.结果表明,PVC单贴面提高材料的热稳定性,600℃时残炭量达67.99％,且HCl及燃烧初期的芳烃生...     

Investigation on flammability of rigid polyurethane foam‐mineral fillers composite

This study investigates the incorporation of castor oil–based rigid polyurethane foam with mineral fillers feldspar or kaolinite clay in order to enhance the mechanical, thermal, and flame retardant properties. Influence of mineral fillers on the mechanical strength was characterized by compressive strength and flexural strength measurement. Thermogravimetric analysis (TGA) was performed to diagnose the changes in thermal properties, while cone calorimeter test was performed to ascertain the flame retardancy of the mineral filler–incorporated rigid polyurethane foam composites. Results showed that the foams incorporated with mineral filler demonstrated up to 182% increase in compressive strength and 351% increase in flexural strength. Thermal stability of these composite foams was also found to be enhanced on the incorporation of kaolinite clay filler with an increase in 5% weight loss temperature (T_5%) from 192°C to 260°C. Furthermore, peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decreased on the incorporation of mineral filler in the rigid polyurethane foam. So mineral fillers are ascertained as a potential filler to enhance the mechanical, thermal, and flame retardant behaviors of bio‐based rigid polyurethane foam composites.     

Lightweight,Elastomeric, and Flame‐Retardant Foams from Expanded Chlorinated Polymers

Intrinsically flame‐retardant polymers based on lightweight and elastomeric microcellular foams are successfully prepared from flexible chlorinated polyethylene (CPE)/chlorinated polyvinylchloride (CPVC) compounds through compression molding foaming technology. The incorporation of CPVC to CPE at once improves the foam characteristics, and enhances the mechanical and fire performances. Due to the plausible intermolecular and intramolecular crosslinking among the polymer chains, the dense network structure of CPE/CPVC with enhanced strength results in increased cell size, reduced cell density, and improved dimensional stability of CPE/CPVC foams (CCFs). These improvements are noticed to be enhanced with increasing CPVC content in the CCF. Also, the flame‐retardant properties of the foams (i.e., limiting oxygen index and cone calorimeter combustion) are found to be increased with the increase of CPVC content. For instance, a highly flame‐retardant CCF at CPE/CPVC ratio of 60/40 shows a shorter combustion period, as derived from the respective heat release rate vs time curve. Corresponding peaks of heat release rate, total heat release rate, peak of mass loss rate, total smoke release, and char residue are recorded to be 8.4%, 5.8%, 3.0%, 6.6%, and 1000.1% of those recorded for the pristine CPE foam.     

Fire performance studies on glass-reinforced plastic laminates

Polyester, epoxy and phenolic glass-reinforced laminates were compared in terms of their fire properties in the cone calorimeter. The presence of a gel coat on the polyester and epoxy products had some effect, mainly in the FR grades. The FR polyester with a brominated flame retardant showed a marked decrease in rate of heat release and in rate of smoke production. Aluminium hydroxide (commonly called alumina trihydrate of ATH) caused a significant delay in ignition time for the epoxy product and some reduction in rate of heat release but rate of smoke release was still relatively high. Phenolic laminates showed a long ignition time and relatively low rate of heat release (RHR). The peak RHR was further reduced by the presence of aluminium hydroxide and by changing the type of glass reinforcement. The influence of thickness was explored for a series of phenolic laminates in both cone calorimeter and the International Maritime Organization (IMO) surface flammability test. Ignition delay time was significantly affected and the cone calorimeter results showed that the shape of the RHR curve was also changed as the thickness increased. However, the heat release measurements in the IMO test were not sensitive enough to pick up the differences in this property. The type of substrate under the laminate significantly altered the burning rate but this may have been because they were not glued or mechanically fixed.     

硼-铝在膨胀型阻燃聚丙烯中的协同作用

通过热分析和锥形量热研究了硼-铝在膨胀型阻燃聚丙烯（PP）中的协同作用。热分析显示膨胀型阻燃剂KDIFR中,引入铝元素,由于催化脱水促进降解的作用,使剩碳率降低至14.6 %;引入硼元素,由于促进可燃小分子的生成,催化降解,也使剩碳率降低至5.9 %;硼铝共存时二者之间的协同作用可以降低在高温区的降解速率,提高剩碳率至19.7 %。PP/KDIFR的锥形量热表明,铝元素增大了热释放速率、释热总量、CO、CO₂和烟释放量;硼元素燃烧前期能减少热释放速率、释热总量、CO和CO₂释放量,有明显的抑烟作用,使阻燃效果略有提高。硼铝共存显著降低热释放速率、释热总量、CO、CO₂和烟释放量,大大提高了阻燃效果。