新型无卤阻燃剂的研究与应用

介绍了纳米型、膨胀型和磷系三种新型无卤阻燃剂的研究与应用进展。该系列阻燃剂是无卤阻燃剂中的典型代表，其热稳定好、高效、抑烟、阻滴、安全、无毒，对环境基本无污染，在阻燃材料中得到广泛的应用，并将逐渐代替含卤阻燃剂。     

Synergistic effect of a novel charring agent with ammonium polyphosphate on flame retardancy and thermal degradation of acrylonitrile‐butadiene‐styrene copolymer

A novel charring agent poly(1,3‐propylene terephthalamide) (PPTA) was synthesized and characterized by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. This novel charring agent combined with ammonium polyphosphate (APP) was adopted as an intumescent flame retardant (IFR) to impart flame retardance and dripping resistance to acrylonitrile‐butadiene‐styrene copolymer (ABS). Flammability and thermal behaviors of the treated ABS were investigated by limiting oxygen index, vertical burning test and thermogravimetric analysis. The results showed that the IFR with the novel charring agent had both excellent flame retardant and anti‐dripping abilities for ABS. The thermogravimetric analysis curves indicated that there was a synergistic effect between PPTA and APP, which greatly promoted the char formation of IFR‐ABS composites. Meanwhile, the thermal degradation mechanism of PPTA and APP/PPTA was characterized using thermogravimetric analysis/infrared spectrometry. The results demonstrated that APP changed the thermal degradation behavior of PPTA and reacted with PPTA to form a crosslinked structure. Additionally, the structure and morphology of char residues were studied by Fourier transform infrared spectroscopy and scanning electron microscopy. Copyright © 2011 Society of Chemical Industry     

Study of a novel halogen‐free flame retardant system through TGA and structure analysis of polymers

Butadiene‐rubber toughened styrene polymers, such as acrylonitrile‐butadiene‐styrene (ABS) copolymer and high impact polystyrene (HIPS), are noncharring polymers. They are generally blended with polycarbonate (PC) or polyphenyleneether (PPE), which are char forming polymers, to improve char forming ability for styrenic blends containing conventional phosphate flame retardants. To achieve cost effective flame retardant system, PET was selected as a potential char‐source for ABS blends through the thermogravimetric analysis (TGA) and chemical structure analysis of various polymers. PET may contribute to the enhancement of flame retardancy of ABS/PET blends, especially in the presence of small amounts of phenol novolac (PN). The effective flame retardancy of this system is believed to be accomplished through the enhancement of interchain reactions by PN. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

磷酸三苯酯和甲基八溴醚在阻燃聚苯乙烯中的协同行为研究

为获得基于甲基八溴醚（MOBE）的高效阻燃聚苯乙烯（PS）复合体系,采用极限氧指数仪、锥形量热仪、热重分析仪（TG）和差示扫描量热仪（DSC）等对纯PS及其复合材料的阻燃性能及机理和热稳定性等进行了测试和表征,探索了MOBE与磷酸三苯酯（TPP）复配阻燃PS的行为规律。结果表明,TPP和MOBE复合体系比二者各自单独作为阻燃剂使用时赋予了PS材料更高的极限氧指数（LOI）,PS/3 %（质量分数,下同）TPP/4 %MOBE的LOI可达27.7 %, 明显高于PS/4 %MOBE（26.1 %）;3 %TPP/4 %MOBE能够在4 %MOBE的基础上进一步抑制PS复合材料的燃烧强度,降低有效燃烧热,降低热释放速率峰值（PHRR）与总热释放量（THR）;TPP和MOBE能够在PS复合材料热降解时将阻燃元素集中释放,同时发挥气相淬灭效应;此外,TPP的加入能够提高PS复合材料的熔体流动速率,降低其玻璃化转变温度,从而使PS热分解产生的熔滴更快地带走热量,最终使TPP与MOBE发挥更好的阻燃效果。     

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.     

苯乙烯系阻燃塑料合金的研究进展

综述了国内外近年来在苯乙烯系阻燃塑料合金方面的研究进展。主要介绍了高聚物型卤系阻燃剂、磷系阻燃剂、有机硅系阻燃剂的特性及其在提高苯乙烯系塑料合金阻燃性能方面的应用。与目前常用的低分子卤系阻燃剂相比，这些阻燃剂对环境污染小，对塑料基材的机械性能和加工性能损害程度少。此外，还简要介绍了纳米复合技术在提高苯乙烯系塑料阻燃性能中的应用。     

Synthesis,thermal properties,and flame retardancy of phosphorus containing polyimides

Phosphorus containing polyimides were prepared via phosphorylation of organosoluble polyimides. This was achieved by phenoxaphosphine oxide ring formation reaction or esterification with diethylchlorophosphate. The phosphorylation was confirmed by infrared, ³¹P nuclear magnetic resonance, and elemental analysis for phosphorus. Polyimides containing phosphorus of 8.3 and 5.4% by weight were found. Thermal characteristics and decomposition behavior of the resulting polyimides were investigated by differential scanning calorimetry and thermogravimetric analysis. Introduction of phosphorus into polyimides slightly reduced their initial weight loss temperatures and led to high char yields at temperatures higher than 800°C. Limiting oxygen index values higher than 48 were found for the phosphorylated polyimides. Such properties make these polymers useful in flame retardant applications. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 875–882, 1997     

有机阻燃剂最新进展

论述９０年代卤系阻燃剂领域内的关注热点和卤系、磷系、卤－磷系及膨胀型阻燃剂在近几年内的发展动态。     

高回弹聚氨酯软泡的无卤阻燃研究

随着人们环保意识的不断提高,卤系阻燃剂的毒性问题受到越来越多的关注,阻燃剂无卤化已经成为必然趋势。间苯二酚双(二苯基磷酸酯)齐聚物(RDP)阻燃剂是一种无卤添加型阻燃剂,因具有优异的热稳定性和低挥发性而得到广泛应用。实验中分别用它与膨胀石墨来阻燃高回弹聚氨酯软泡并进行了二者协同阻燃聚氨酯软泡的研究。用氧指数仪和民航飞机用垂直燃烧方法测试表征了制备的泡沫样品,并对其阻燃性能进行了研究。     

Butyltriphenylphosphine-based chelate borates influenced on flame retardancy of polystyrene composite containing self-expanded intumescent flame retardants

The polystyrene (PS) composite containing self-expanded intumescent flame retardant (polyphosphate ammonium and expandable graphite) was blended with three butyltriphenylphosphine-based chelate borates, respectively, to evaluate their effect on flame retardancy. The chemical structure of as-prepared three chelate borates was confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectrum (FTIR). The flame retardancy of various PS composites was evaluated by vertical burning test (UL-94), limited oxygen index (LOI), and cone calorimeter (CC). Flammability and combustion results suggested that one of chelate borates, named [BTP][BMB], made PS composite (PS4) obtain V-0 rating, 27.0 ± 0.3% LOI value, and reduction on heat release and smoke production with 17 wt% total flame retardants loading. The combustion residue was analyzed by scanning electron microscope and FTIR, and the pyrolysis gaseous products were investigated by TG-FTIR technique. Besides, complex viscosity of PS composites composed of various chelate borates from a rheology instrument indicated that the improvements of flame retardancy of PS composites depended on the temperature of construction of crosslinked network by expandable graphite, which the chelate borates showed distinctive influence. Accordingly, the flame-retarding mechanism about fast response to flame has been proposed.     

苯乙烯系阻燃塑料合金的研究进展

综述了国内外近年来在苯乙烯系阻燃塑料合金方面的研究进展。主要介绍了高聚物型卤系阻燃剂、磷系阻燃剂、有机硅系阻燃剂等阻燃剂的特性及其在提高苯乙烯系塑料合金阻燃性能方面的应用，这些阻燃剂对环境友好，不仅能显著提高塑料基材的阻燃性能，而且力学性能和加工性能也得到改善。此外，还简要介绍了纳米复合技术在提高苯乙烯系塑料阻燃性能中的应用。     

新阻燃剂SR743在阻燃HIPS中的应用

研究了新阻燃剂SR743在阻燃高抗冲聚苯乙烯中的应用,并与十溴二苯乙烷进行了对比,结果表明SR743非常适用于阻燃高抗冲聚苯乙烯UL94标准V-2级阻燃体系中,阻燃剂用量较小。     

新型含磷阻燃剂的制备及性能

以双三羟甲基丙烷为原料合成一种新型含磷阻燃剂,该阻燃剂分子量较大,具有稳定的环状结构,热稳定性高于常用阻燃剂,阻燃效果好。探讨了原料配比、反应温度、反应时间对产率的影响,考察了目标产物的热稳定性能及其对不同织物的阻燃效果,用傅里叶变换红外光谱仪表征了中间体及目标产物的结构。结果表明,当原料配比为1∶3时,磷化温度为50℃,磷化时间5h,胺化温度为75℃时,反应效果较好,收率可达90%以上。目标产物对于锦纶的阻燃效果比较明显,对涤纶、棉有一定的阻燃效果,对于混纺、腈纶阻燃效果不明显。     

Use of zinc borate as the third component of a traditional brominated flame retardant system in acrylonitrile butadiene styrene

Because zinc borate is an effective smoke suppressant and cheaper than antimony trioxide, the main aim of this study was to investigate usability of zinc borate as the third component of a traditional binary Br/Sb₂O₃ system in acrylonitrile butadiene styrene. Limiting oxygen index, UL‐94, and mass loss cone calorimeter studies indicated that almost all flame retardancy parameters were kept when certain percentages of antimony trioxide were replaced with zinc borate. Residue analysis revealed that the predominant flame retardancy mechanism of the traditional system was gas phase action, whereas zinc borate contributes especially in the condensed phase action by forming thicker and stronger char layer. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation of novel biomass humate flame retardants and their flame retardancy in epoxy resin

Humic acid (HA), a biomass material with plentiful oxygen-containing functional groups, showed huge potential to be considered as a promising charring agent in flame retardancy. In this study, this HA was modified with four different metal ions like Fe²⁺, Mn²⁺, Al³⁺, and Cu²⁺ and finally, introduced into the epoxy resin (EP) to enhance the flame retardancy of the EP and the dispersion of these flame retardants into the EP matrix. When 10 wt% of HA-Fe and HA-Mn were incorporated into EP matrix, the limiting oxygen index (LOI) was increased from 21.2% for EP to 26.6 and 25.3% for the EP composites and the peak heat release rate (pHRR) was reduced by 36 and 35.5%, respectively. Such a significant improvement in flame retardancy was attributed to the catalytic charring of HA in the presence of metal ions, which ultimately increased the residual char formation and produced compact char layers during the combustion process to retard the transfer of heat and combustible gases between the EP composites and the flame zone. Finally, this kind of application provided a feasible way for the development of an environmentally friendly flame retardant with high efficiency, which improved the fire safety of EP matrix.     

New developments in flame retardancy of glass‐reinforced epoxy composites

This work involves the development of novel glass fiber–reinforced composite materials containing a commercially available epoxy resin, a phosphate‐based intumescent, and inherently flame‐retardant cellulosic (Visil, Sateri) and phenol–formaldehyde (Kynol) fibers. The intumescent and flame‐retardant fiber components were added both as additives in pulverized form and fiber interdispersed with the intumescent as a fabric scrim for partial replacement of glass fiber. Thermal stability, char formation, and flammability properties of these novel structures were studied by thermal analysis, limiting oxygen index, and cone calorimetry. The results are discussed in terms of effect of individual additive component on thermal degradation/burning behavior of neat resin. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2511–2521, 2003     

螺环磷酰咪唑酯对棉布阻燃性能和力学性能的影响

采用自制膨胀型阻燃剂螺环磷酰咪唑酯通过浸轧方法对纯棉布进行阻燃整理,考察了阻燃剂、助剂的比例以及焙烘温度对整理棉布的极限氧指数(LOI)的影响。从中选取LOI值超过28%的阻燃棉布共8组,进行垂直燃烧和拉伸性能测试,进一步确定较优的阻燃整理工艺。结果发现,较优的阻燃整理条件为:整理液中w(阻燃剂)=30%,w(催化剂)=1.5%,w(交联剂)=1%,焙烘温度为150℃时,阻燃棉布的LOI值达到33.96%,阻燃等级达到B1级,拉伸性能测得断裂强力为312.50 N;对该条件下阻燃整理的棉布进行热重分析,结果表明,棉布的初始热分解温度提前了100℃,最大热分解速度降低,600℃下的残留量由几乎烧尽提高到30%。说明螺环磷酰咪唑酯阻燃体系对棉布具有很好的阻燃作用。     

ABS树脂阻燃剂的研发进展

介绍了ABS树脂阻燃剂的研究开发进展,指出了其今后的发展趋势。     

高密度聚乙烯阻燃性能的研究

研究了含卤阻燃剂、无机阻燃剂、稳定剂、氯化聚乙烯和不同分子量的基础树脂对高密度聚乙烯的阻燃性和力学性能的影响。     

聚苯乙烯泡沫阻燃研究

从卤系阻燃剂和无卤阻燃剂两方面综述了近几年来国内外阻燃聚苯乙烯(PS)的研究现状。卤系阻燃剂主要介绍了溴化苯乙烯、十溴二苯醚(DPEDB)、溴化环氧树脂等。无卤阻燃剂介绍了膨胀型、金属氢氧化物及黏土类。分析了各类阻燃剂优缺点,未来占据阻燃剂主导地位的应是高效的环境友好型复配无卤阻燃剂。