纳米SiO2与RDP协同阻燃PC/ABS的研究

采用间苯二酚双（二苯基磷酸酯）（RDP）及其与纳米SiO2复配制备双酚A聚碳酸酯/丙烯腈-丁二烯-苯乙烯（PC/ABS）阻燃材料,测定了阻燃PC/ABS的极限氧指数、UL94V阻燃性能及热稳定性,采用扫描电子显微镜(SEM)观察了阻燃PC/ABS于600 ℃热分解残余物的形态,采用锥形量热仪测定了阻燃PC/ABS的释热速率峰值（p-HRR）、释热速率平均值（av-HRR）、总释热量（THR）、平均有效燃烧热（av-EHC）和平均质量损失速度（av-MLR）。结果表明,纳米SiO2与RDP添加量分别为5 %和9 %时,PC/ABS的阻燃性能达UL94V-0级,极限氧指数为29.0 %,且阻燃PC/ABS的p-HRR、av-HRR、THR、av-EHC以及av-MLR分别下降了16.12 %、58.82 %、40.83 %、17.91 %和36.90 %,同时也证明了纳米SiO2与RDP具有非常好的协同阻燃效应。     

芳磺酸盐与BDP协同阻燃聚碳酸酯的性能研究

以芳磺酸盐(KTS)与双酚A双(二苯基磷酸酯)(BDP)作为复配体系,制备了阻燃聚碳酸酯(PC)复合材料。通过极限氧指数(LOI)、垂直燃烧、热失重分析(TGA)、力学性能测试实验研究了复配阻燃剂对PC阻燃性能、热稳定性和力学性能的影响。结果表明:当KTS、BDP用量分别为0.1%和12.5%时,体系的LOI达到最大值37.5%,垂直燃烧等级为UL 94V-0级;KTS与BDP复配使用后,对PC有良好的协同阻燃作用,有利于提高材料的热稳定性,同时提高了阻燃PC复合材料的成炭能力,改善了残炭质量。     

BDP阻燃PC/ABS及其纳米复合材料的阻燃性和热降解动力学

采用双螺杆挤出机挤出造粒制备了苯基双酚A二磷酸酯(BDP)阻燃的聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯(ABS)、PC/ABS有机蒙脱土(OMMT)和PC/ABS有机改性纳米二氧化(SiO2)3种复合材料,采用热重分析探讨了PC/ABS/BDP , PC /ABS/BDP/OMMTPC/ABS/BDP/SiO2复合材料的热降解动力学行为,以此分析其阻燃性能与热降解行为的关系。结果表明,加入纳米材料后,在质量损失8%以前,PC/ABS/BDP/OMMT和PC/ABS/BDP/SiO2纳米复合材料的活化能均低于PC/ABS/BDP的活化能,但质量损失8%以后,PC/ABS/BDP/OMMT和PC/ABS/BDP/SiO2复合材料的活化能均高于阻燃PC/ABS。在质量损失5%-75%范围内,PC/ABS/BDP/OMMT和PC/ABS/BDP/SiO2平均活化能分别为139.39KJ/mol和144.17KJ/mol,均高于PC/ABS/BDP的平均活化能(104.87 kJ /mol),说明添加纳米材料后,由于BDP与OMMT或SiO2的协同阻燃作用,降低了材料的热降解速率,增大了材料的热稳定性,这与氧指数测试、UL94V阻燃性能及热重分析得出的结沦一致。     

溴化聚苯乙烯协同三氧化二锑阻燃PA6的性能

溴化聚苯乙烯(BPS)协同不同粒径的Sb_2O_3复配制备阻燃PA6,研究阻燃PA6的物理机械性能、UL94、LOI、阻燃性能和烟气释放.力学试验结果显示:协同阻燃体系的加入,提高了PA6的热变形温度、邵氏硬度、弯曲强度、弯曲模量和维卡软化点,注塑成型收缩率增加,缺口冲击强度、断裂伸长率和熔体指数下降.当粒径为0.4 μm时,综合力学性能最佳.燃烧性能和CONE测试结果显示:阻燃PA6的燃烧性能提高到ULV-0级,LOI升高,av-HRR、Pk-HRR、Pk-HRR/TTI、THR、EHC显著下降、轰燃时间大幅延长,且Sb_2O_3粒径越小,阻燃效果越好,但av-SEA、av-CO、SPR明显上升,阻燃但不能抑烟.     

磷系阻燃剂对PC/ABS共混物燃烧性能的影响

通过磷系阻燃剂(FR)阻燃聚碳酸酯/丙烯腈-丁二烯-苯乙烯(PC/ABS)共混物,制备阻燃材料,研究磷系阻燃剂对PC/ABS阻燃复合材料的燃烧行为和热稳定性的影响。通过UL94垂直燃烧测试、极限氧指数(LOI)测试、马弗炉测试等表征方法,对PC/ABS阻燃复合材料的燃烧行为进了系统的研究。结果表明,磷系阻燃添加量为15%时,PC/ABS阻燃复合材料能够达到UL94 V-2级,LOI的值为29.3%,高温时的残炭量由11.2%提高到20.8%。其中FR阻燃剂在高温下可以产生磷酸酯类黏稠难燃物质,能够有效地起到凝聚相阻燃作用,提高了PC/ABS共混物材料的阻燃性能,表现出良好的阻燃效果。     

无卤阻燃PC/ABS合金的研制

研究了增容剂苯乙烯-丁二烯-马来酸酐共聚物(MPC 1545R)、四苯基双酚A二磷酸酯(BDP)与磷酸三苯酯(TPP)复配阻燃剂及不同螺杆组合工艺对聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯塑料(ABS)合金性能的影响。通过扫描电子显微镜分析了PC/ABS合金的微观结构。结果表明,MPC 1545R对PC/ABS合金起到了较好的增容效果,单一BDP阻燃剂,BDP与TPP复配阻燃剂均可显著提高PC/ABS合金的阻燃性能,BDP与TPP复配阻燃剂的阻燃效果比单一阻燃剂BDP好,当PC,ABS,MPC 1545R,BDP和TPP用量分别为70,30,5,10,3.5份时,制备的无卤阻燃PC/ABS合金的极限氧指数为27.9%、阻燃等级为UL94 V-0级,综合力学性能最好。适当地降低螺杆的剪切强度,提高螺杆的分散能力,可以获得力学、阻燃性能及外观较好的阻燃PC/ABS合金。     

芳香族双磷酸酯复配体系阻燃PPO/HIPS的制备与阻燃性能

采用芳香族双磷酸酯如双酚A双(二苯基)磷酸酯(BDP)和间苯二酚双(二苯基)磷酸酯(RDP),分别与纳米二氧化硅(n-SiO2)、三聚氰胺氰尿酸盐(MCA)复配制备了阻燃PPO/HIPS和阻燃PPO/HIPS纳米材料.利用氧指数(LOI)、水平垂直燃烧(UL94V)、热失重分析(TGA),锥形量热仪(CONE)等技术探讨了复配体系对PPO/HIPS的阻燃作用和阻燃机理.实验结果证明采用复配体系阻燃的PPO/HIPS取得了很好的效果.在相同添加量的情况下RDP比BDP较优.材料氧指数最高达到了35.0%,具UL944 V-O阻燃级.     

复配磷酸酯阻燃PC／ABS合金的研究

研究了复配磷酸酯阻燃剂对PC/ABS合金材料的性能的影响.探讨了复配磷酸酯阻燃剂阻燃PC/ABS合金材料的力学性能和阻燃性能,复配阻燃剂对PC/ABS合金的阻燃机理.结果表明:在PC/ABS合金(质量比为70/30)体系中,磷酸三苯酯(TPP)和四苯基[双酚-A]二磷酸酯(BDP)按质量比为3:2复配具有协同阻燃作用.加入18份复配阻燃剂后材料的氧指数提高了6个单位,阻燃性能达到了FV-0级,并保持了材料较好的力学性能.     

3-苯磺酰基苯磺酸钾与三苯基氧化膦复配阻燃聚碳酸酯的研究

分别以3-苯磺酰基苯磺酸钾(KSS)和磷酸三苯酯(TPP)复配体系为阻燃剂,制备了聚碳酸酯(PC)复合材料。通过极限氧指数(LOI)、垂直燃烧(UL94)、热失重分析(TGA)实验研究了两种阻燃剂对PC阻燃性能和热稳定性的影响。结果表明,PC/0.1%KSS复合材料的LOI值由PC的25.2%提高到36.1%,UL 94达到V-0级,初始分解温度由406.5℃提高到460.7℃,900℃残炭率由14.7%增加到19.6%;相比PC/0.1%KSS复合材料,PC/0.1%KSS/1%TPP复合材料的LOI降到30.7%,UL94降到V-2级,初始分解温度降到294.7℃,残炭率降到15.4%,由此可知,TPP和KSS具有对抗作用,不适合复配阻燃改性PC。     

磷系阻燃剂FR/APP协效阻燃PP

采用氧指数测定仪、热重分析仪和锥形量热仪研究了磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)和聚磷酸铵(APP)复配体系对聚丙烯(PP)材料阻燃性能的影响.结果表明,FR/APP提高了PP的极限氧指数(LOI)、热稳定性和残炭率,降低了热释放速率.当w(FR)为15%和w(APP)为10%复配阻燃PP时,复合材料的LOI为29.6%.阻燃级别达到UL 94 V-0级.     

Flame retardancy mechanisms of triphenyl phosphate,resorcinol bis(diphenyl phosphate) and bisphenol A bis(diphenyl phosphate) in polycarbonate/acrylonitrile–butadiene–styrene blends

The flame retardancy mechanisms of three aryl phosphates, triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP) and bisphenol A bis(diphenyl phosphate) (BDP), in a polycarbonate/acrylonitrile–butadiene–styrene (PC/ABS) blend are investigated and compared. Further, the influence of polytetrafluorethylene (PTFE) on viscosity and thermal decomposition is discussed in the systems PC/ABS and PC/ABS + BDP. Mechanisms are proposed based on the results of various methods. Thermogravimetric analysis, Fourier transform infrared spectroscopy and kinetics are used to study the pyrolysis. The fire behaviour is studied by means of cone calorimeter measurements at different heat fluxes and the flammability is specified by limiting oxygen index (LOI) and UL 94. Rheology measurements are used to illuminate the changed dripping behaviour due to PTFE. TPP shows only a gas phase action. RDP shows mainly a gas phase action and some condensed phase action. BDP shows a crucial condensed phase action in addition to a gas phase action. TPP and RDP are somewhat superior in terms of flammability (LOI), whereas BDP shows superior performance in forced flaming combustion (cone calorimeter). Synergistic effects between PTFE and BDP are found. Copyright © 2007 Society of Chemical Industry     

Flame‐retardant polycarbonate/acrylonitrile‐butadiene‐styrene based on red phosphorus encapsulated by polysiloxane: Flame retardance,thermal stability,and water resistance

Red phosphorus encapsulated by polysiloxane (MRP) was prepared, and the chemical structure and morphology of MRP were characterized by FTIR and TEM, respectively. A series of flame retardant polycarbonate/acrylonitrile‐butadiene‐styrene containing MRP (PC/ABS/MRP) were prepared via melt‐blending. The flame retardance of PC/ABS/MRP was investigated by limiting oxygen index (LOI) and UL‐94 test. It was shown that the LOI value was increased to 27.7 and UL‐94 achieved a V‐0 rating at a 15 wt % loading of MRP. Cone calorimetric results showed that the peak of heat release rate (PHRR) of PC/ABS/15% MRP decreased from 452.7 to 198.0 kW/m², and the total heat release decreased from 92.9 to 60.7 MJ/m² compared with virgin PC/ABS. Thermal stability analysis showed that the char yield of the PC/ABS/15% MRP increased from 0 to 16.1 wt % under air atmosphere, and from 15.2 to 27.4 wt % under nitrogen atmosphere compared to virgin PC/ABS, respectively. The sample PC/ABS/15% MRP also showed excellent water resistance of flame retardance in 70°C water for 168 h. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

磷酸酯类阻燃剂在PC／ABS合金中的应用

文章研究了磷酸酯类阻燃剂RDP、BDP以及它们与TPP的协同作用对PC／ABS合金的阻燃性能、热失重行为以及力学性能的影响。结果表明,PC／ABS合金的LOI随着阻燃和的增加而增加,当阻燃剂RDP和BDP添加量均为15％时,LOI达到最大值,分别为363％和35．3％,且均达FV-0级。通过热重分析表明,阻燃PC／ABS比纯PC／ABS合金的分解速率小得多。研究还表明,阻燃剂的协同作用使PC／ABS合金的阻燃性能优于添加单一阻燃剂的PC／ABS合金的阻燃性能。     

新型磷系阻燃剂阻燃环氧树脂的应用研究

以新戊二醇、三氯氧磷、1,2,3-三羟基苯为原料合成新型磷系阻燃剂1,2,3－三(5,5－二甲基－1,3－二氧杂己内磷酰氧基)苯(FR),将FR与环氧树脂(EP)熔融混合制备阻燃EP/FR复合材料。采用极限氧指数测试、垂直燃烧实验、热重分析、锥形量热分析、扫描电镜研究了FR对EP的阻燃性能和阻燃机理。结果表明,添加20 % FR的EP/FR复合材料的极限氧指数达到27.8 %,垂直燃烧通过UL94 V-0级,热释放速率平均值和生烟量平均值比未阻燃EP分别降低了77.0 %和82.8 %,扫描电镜分析表明, EP/FR体系燃烧后能形成连续、致密、封闭的焦化炭层。     

新型磷硅阻燃剂的合成及其对PC/ABS的阻燃研究

以三氯氧磷、季戊四醇和二乙氧基氨丙基硅甲烷为原料合成了一种磷硅阻燃剂PN,并通过红外光谱和核磁共振测定了其结构。将PN与聚碳酸酯/(丙烯腈/丁二烯/苯乙烯)共聚物(PC/ABS)体系共混后研究了PN对PC/ABS体系热降解性能、阻燃性能和残炭形貌的影响。结果表明,PN能改善PC/ABS体系的高温热稳定性和残炭量,在燃烧时形成内表面发泡、外表面致密连续的膨胀炭层;且能提高PC/ABS体系的阻燃性能,当PN的添加量从0增加到30份时,PC/ABS共混材料的极限氧指数由21%增加到29%;当PN添加量超过20份后,共混材料的阻燃等级能够达到UL94V-1级。     

Modelling the vertical UL 94 test: competition and collaboration between melt dripping,gasification and combustion

An experimental and numerical investigation of the effect of bisphenol A bis(diphenyl phosphate) (BDP) and polytetrafluoroethylene (PTFE) on the fire behaviour of bisphenol A polycarbonate/acrylonitrile butadiene styrene (PC/ABS) in the vertical UL 94 scenario is presented. Four PC/ABS blends were discussed, which satisfy different UL 94 classifications due to the competing effects of gasification, charring, flame inhibition and melt flow/dripping. For numerical investigation, the particle finite element method (PFEM) is used. Its capability to model the complex fire behaviour of polymers in the UL 94 is analysed. The materials' properties are characterised, in particular the additives impact on the dripping behaviour during thermal exposure. BDP is an efficient plasticiser; adding PTFE prevents dripping by causing a flow limit. PFEM simulations reproduce the dripping and burning behaviour, in particular the competition between gasification and dripping. The thermal impact of both the burner and the flame is approximated taking into account flame inhibition, charring and effective heat of combustion. PFEM is a promising numerical tool for the investigation of the fire behaviour of polymers, particularly when large deformations are involved. Not only the principal phenomena but also the different UL 94 classifications and the extinction times are well predicted. Copyright © 2014 John Wiley & Sons, Ltd.     

改性硅基杂化介孔材料阻燃PC/ABS研究

将自制的9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)接枝硅基杂化介孔材料(DM)、三苯基磷酸酯(TPP)和聚碳酸酯(PC)/丙烯腈-丁二烯-苯乙烯塑料(ABS)共混制得阻燃PC/ABS复合材料。研究表明,当DM和TPP的质量分数为2%和6%时,复合材料的氧指数为28%,并达到UL 94 V-0阻燃级别;锥形量热仪进一步分析证实PC/ABS/TPP/DM体系的最大热释放速率和总热释放量均有大幅度下降;通过对炭层形貌及结构的研究表明,DM和TPP具有很好的协效作用,在燃烧过程中能促进PC/ABS复合材料生成微观致密的炭层,增强了PC/ABS复合材料的热稳定性。     

Effect of a nanoclay/triphenyl phosphate hybrid system on the fire retardancy of polycarbonate/acrylonitrile–butadiene–styrene blend

The effect of a hybrid system of nanoclay and triphenyl phosphate (TPP) on the fire retardancy of a polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) blend was examined in this study. The nanoclay in the polymers decreased the peak heat release rates (PHRRs) with no significant effect on the ease of ignition and times to extinguishment. Improvements in the flame retardancy were observed only when nanoparticles were used with conventional flame‐retardant (FR) additives. Thermogravimetric analysis (TGA), cone calorimetry, and limited oxygen index (LOI)/UL 94 (Underwriters Laboratory) testing were used to investigate the thermal degradation, fire behavior, and flammability of the materials. The results show that when we used a combination of TPP and nanoclay as an FR system, degradation of the polymer blends was reduced as the TGA curves shifted to higher temperatures. PHRR in cone calorimetry testing decreased from 1032 kW/m² for the PC/ABS blend to 300 kW/m² for the PC/ABS/(12% TPP–2% nanoclay) sample, and the LOI increased from 23 to 35%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011