PRPP对PC/ABS复合材料的阻燃性能研究

以聚苯基磷酸间苯二酚酯(PRPP)作为RDP的替代品复配阻燃PC/ABS的阻燃性能和阻燃机理研究未见文献报道,符合当前阻燃技术的发展方向,具有重要的理论意义和实用价值。采用PRPP用于PC/ABS的阻燃,对不同配比的样品进行氧指数、垂直燃烧、热性能等测试。分析得出最优配比。最后,对比RDP和PRPP对PC/ABS阻燃改性。结果表明:PRPP作为固态阻燃剂,与具有相同结构的液态阻燃剂RDP和BDP具有相似的阻燃效果。改性材料的氧指数与未改性材料相比均有提高,它在加工,运输和贮存方面具有液态阻燃剂无可比拟的优势,可以作为RDP和BDP阻燃剂在常规使用范围内的替代品使用。     

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。     

无卤阻燃PC/ABS合金形态结构和动态流变行为研究

将不同用量的有机磷系阻燃剂双酚A-双(磷酸二苯酯)(BDP)和聚碳酸酯(PC)、丙烯腈-丁二烯-苯乙烯(ABS)熔融共混制得无卤阻燃PC/ABS合金,采用扫描电镜和动态流变仪研究PC/ABS/BDP合金的微观结构和BDP用量对合金动态流变性能的影响,分析了微观结构和动态流变行为之间的关系。结果表明,随着阻燃剂用量的增加,PC/ABS合金相界面黏结性、熔体黏度呈下降趋势,且阻燃剂质量分数达到15%以后,降幅在低频时加剧;PC/ABS合金熔体在整个扫描频率区以黏性流动为主,阻燃剂的加入使其黏性特征更加明显。     

PC/ABS阻燃合金的开发及性能研究

利用双螺杆挤出机制备了聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物(PC/ABS)共混合金,并以磷酸三苯酯/热塑性酚醛树脂(TPP/TPPFR)复配体系作为膨胀型阻燃剂(IFR)对其进行阻燃改性。通过拉伸、弯曲、冲击强度测试考察了PC/ABS阻燃合金的力学性能;通过热变形温度(HDT)和熔体流动速率(MFR)测试考察了合金的耐热性能和加工性能;通过极限氧指数(LOI)和垂直燃烧测试考察了合金的阻燃性能。结果表明:当PC与ABS的质量比为4:1,复配阻燃剂TPP/TPPFR的质量比为1:1、添加量为11份时,可得到综合性能优异的PC/ABS阻燃合金。     

纳米SiO2对PC/ABS/RDP阻燃体系的协同作用

采用纳米SiO2作为阻燃协效剂,利用间苯二酚双(二苯基磷酸酯)(RDP)协同阻燃剂,制备具有良好阻燃性能、环境友好型无卤阻燃聚碳酸酯(PC).研究纳米SiO2和RDP的添加量对PC阻燃性能和协效作用的影响.结果表明:通过控制纳米SiO2和RDP的用量,可使PC/ABS阻燃体系达到塑料材料燃烧测试标准的UL94V-0级,极限氧指数(LOI)达到29％以上.通过锥形量热仪及SEM测试表明:加入少量的纳米SiO2能够促进体系成炭,同时也说明SiO2和RDP起到了良好的协同效应,提高了材料的阻燃性能.     

滑石粉和间苯二酚双(二苯基磷酸酯)协效阻燃PC/ABS合金的研究

用γ-氨丙基三乙氧基硅烷表面处理的滑石粉(Talc)与间苯二酚双(二苯基磷酸酯)(RDP)复合阻燃质量比为7∶3的聚碳酸酯(PC)/(丙烯腈-丁二烯-苯乙烯)共聚物(ABS)合金,探讨了两者用量对PC/ABS阻燃性能和耐热性能的影响。研究表明,Talc与RDP有一定的协同阻燃作用,添加13.0 wt%Talc和7.0 wt%RDP后,PC/ABS可通过UL-94 V-0级,极限氧指数(LOI)为31.8%,热变形温度比同样阻燃等级、单独添加16.0wt%RDP的PC/ABS(PC/ABS/R-16)高10℃以上。相比于单独用RDP阻燃,滑石粉与RDP复合后的PC/ABS(PC/ABS/R-7/T-13)热重分析图上残炭率从12.8%提高至24.0%,拉曼图谱表示热重分析的炭层的石墨化程度更高;扫描电镜图显示垂直燃烧后残炭的内层更致密,表明滑石粉的加入主要促进了RDP在凝聚相的阻燃作用,有助于体系生成更连续而致密的炭层。     

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.     

无卤阻燃PC/ABS合金的研究进展

综述了近年来国内外采用无卤阻燃剂阻燃PC／ABS合金的研究进展。介绍了PC／ABS合金无卤阻燃剂的分类、阻燃机理及存在的一些问题和解决方法。重点介绍了有机磷系阻燃剂及其对PC／ABS合金的阻燃性能、热分解和机械性能等的影响,并指出了今后的研究重点和发展方向。     

无卤阻燃PO／ABS合金的研究进展

综述了近年来国内外采用无卤阻燃剂阻燃PC／ABS合金的研究进展。介绍了PC／ABS合金无卤阻燃剂的分类、阻燃机理及存在的一些问题和解决方法。重点介绍了有机磷系阻燃剂及其对PC／ABS合金的阻燃性能、热分解和机械性能等的影响,并指出了今后的研究重点和发展方向。     

磷、溴阻燃剂在PC/ABS合金中的应用

对阻燃PC／ABS合金所用的阻燃剂进行了对比试验。结果表明。当PC／ABS质量比为7：3时，添加阻燃PC／ABS合金量的13％左右的溴系阻燃剂，可使材料的阻燃性能达到UL-94 V-0级（1．6mm）；磷酸酯系阻燃剂由于对ABS的阻燃效果不好，只有在材料中PC质量分数大于70％时，才有阻燃效果；用溴-磷酸酯系阻燃剂，即使在材料中PC质量分数为50％时，也能达到UL-94 V-0级（1.6mm），说明磷与溴在PC／ABS合金中有协效作用，将磷酸酯系阻燃剂与溴系阻燃剂复配使用．在阻燃PC／ABS合金中．亦有类似的效果。     

新型磷系阻燃剂四苯基(双酚-A)二磷酸酯阻燃PC/ABS的研究

利用自制的四苯基(双酚-A)二磷酸酯(BDP)及其复配体系制备了阻燃PC/ABS,研究了阻燃PC/ABS的力学性能、氧指数(LOI)和垂直燃烧测试性能(UL94)、材料的阻燃性能和烟气释放。结果表明:采用15%的BDP阻燃PC/ABS,材料的冲击强度下降了12.82%,LOI达到30.0%,UL94阻燃性能达到V—0级,平均热释放速率(av-HRR)和最大热释放速率(pk-HRR)分别下降了35.84%和31.17%,点燃时间(TTI)延长18s,火势增长指数(FGI)下降了46.72%,比消光面积(SEA)上升了6.68%;采用BDP/APP复配阻燃PC/ABS,材料的冲击强度最大降幅为33.33%,LOI最大可达30.1%,UL94阻燃性能由V—0级降为V—1级,av-HRR和pk-HRR最大分别下降40.89%和31.2%,TTI最大延长20s,FGI最大降幅为50.37%,SEA最大涨幅为11.14%;采用BDP/纳米SiO2复配阻燃PC/ABS,当纳米SiO2的添加量为7%时,材料的冲击强度上升了5.13%,LOI达到31.1%,UL94阻燃性能达到V—0级,av-HRR和pk-HRR分别下降了43.18%和4069%,TTI延长20s,FGI降幅为59.12%,平均比消光面积(av-SEA)涨幅为8.09%,6min内av-SEA下降6.92%,(6min总发烟指数)TSPI6min下降5.54%,阻燃、抑烟效果最佳,对PC/ABS材料的力学性能影响最小。     

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     

无卤阻燃PC/ABS合金的研究

研究了四苯基间苯二酚基二磷酸酷(RDP)和氢氧化铝复配阻燃体系对PC/ABS合金性能的影响;并以马来酸酐接枝丙烯腈-苯乙烯-丁二烯共聚物(ABS-g-MAH)为相容剂,考察了ABS-g-MAH的用量对合金性能的影响.结果表明,复配阻燃体系可显著提高PC/ABS合金的阻燃性能,当RDP为14份、Al(OH)3为6份时,氧指数可达到32%;相容剂的加人能够明显提高合金的力学性能,最佳用量为6%,但使体系的黏度增加,熔体质量流动速率降低.     

无卤阻燃PC/ABS合金的研制及应用

研究了间苯二酚双(二苯基磷酸酯)(RDP)、增容剂和增韧剂对聚碳酸酯(PC)/(丙烯腈/丁二烯/苯乙烯)共聚物(ABS)合金阻燃性能的影响。结果表明,在PC/ABS合金体系中加入14份阻燃剂RDP,并配以适量的增容剂、增韧剂及其它助剂,可制得阻燃性能和力学性能优良的无卤阻燃PC/ABS合金,可满足轨道交通列车用内装饰材料的技术要求。     

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     

有机改性蒙脱土对无卤阻燃PC/ABS合金的影响

研究不同有机改性剂对蒙脱土(MMT)的层间距和热稳定性的影响,以及有机蒙脱土复配磷酸酯阻燃剂对聚碳酸酯/丙烯腈-丁二烯-苯乙烯共聚物(PC/ABS)合金的热稳定性和阻燃性能的影响。结果表明,有机改性剂使蒙脱土的层间距变大,热稳定性能满足加工要求。有机改性蒙脱土在基体中的分散性变好,形成插层结构。氮气氛围下,蒙脱土会促进合金的降解,但不影响最终残炭含量。双酚A(二苯基磷酸酯)(BDP)改性蒙脱土使PC/ABS(80/20)合金的第二个热释放峰值分别降为PC/ABS的66%和PC/ABS/FR16的76%。     

阻燃PC／ABS共混体系的动态力学分析

通过熔融共混法制备了阻燃PC／ABS复合材料,分析了其动态力学性能,探讨不同相容剂、不同ABS组份等因素对复合材料的储存模量（E′）、损耗模量（E″）、损耗因子（tanδ）等动态力学参数的影响。结果发现使用丙烯酸树脂和苯乙烯马来酸酐无规共聚物组成的复合相容剂能够较好地改善阻燃PC／ABS的相容性,在玻璃化温度附近E′和E″适中;材料有着良好的刚性和韧性,综合力学性能优良。研究结果可为进一步优化阻燃PC／ABS产品配方提供依据。     

Thermal degradation behaviors and flame retardancy of PC/ABS with novel silicon‐containing flame retardant

A novel flame retardant (DVN) containing silicon, phosphorus, and nitrogen has been synthesized from the reaction of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO), vinylmethyldimethoxy silane (VMDMS) and N‐β‐(aminoethyl)‐γ‐aminopropyle methyl dimethoxy silane (NMDMS), then incorporated into polycarbonate/acrylonitrile butadiene styrene (PC/ABS) alloy. The flame retardancy of PC/ABS/DVN is evaluated by cone calorimeter and limited oxygen index (LOI) and the thermal degradation behavior is investigated by thermogravimetric analysis under nitrogen and air. The PC/ABS/DVN sample was thermally degraded at 400°C for different amounts of time and studied by Fourier transform infrared spectroscopy to better understand the mechanism of flame retardancy. The results show that the thermal stability and flame retardancy of PC/ABS are improved by incorporation of DVN. Scanning electric microscopy results show that the outer surface of the char layer of PC/ABS/DVN after the LOI test is smooth and the internal structure is like swollen cells, which benefits the flame retardancy of PC/ABS. Copyright © 2007 John Wiley & Sons, Ltd.     

Construction of novel silicon‐phosphorus linear polymers with DDSQ and DOPO derivatives for effective flame retardancy of PC/ABS

Two kinds of novel silicon‐phosphorus linear polymers were synthesized by the hydrosilylation reaction of double‐decker‐shaped silsesquioxane (DDSQ) and 9,10‐dihydro‐9‐oxa‐10‐ phosphaphenanthrene‐10‐oxide (DOPO) derivatives and characterized using ¹H NMR, ³¹P NMR, and ²⁹Si NMR. Flame‐retardant polycarbonate/acrylonitric‐butadiene‐styrene (PC/ABS) blends were prepared with different contents of silicon‐phosphorus linear polymers. The flame‐retardant properties of silicon‐phosphorus linear polymers as well as the morphology were investigated in detail by using thermogravimetric analysis (TGA), limiting oxygen index (LOI), (Underwriters Laboratory) UL‐94, microscale combustion calorimetry (MCC), and scanning electron microscopy (SEM), respectively. The silicon‐phosphorus linear polymers containing DDSQ and DOPO units can synergistically improve the flame retardancy and thermal stability of PC/ABS blends. Flame‐retardant polymers with different linkers between DDSQ and phosphate units show comparable effect on the flame retardancy of PC/ABS.     

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。