酚醛泡沫的燃烧行为及阻燃研究进展

酚醛泡沫因兼具优异的保温性能和阻燃性能在工程领域得到广泛应用,但其经高温燃烧后质量残留率很低,炭层疏松、强度低,离开火焰后还易出现阴燃现象。目前有关酚醛泡沫燃烧行为的研究大多集中在如何进一步提高酚醛泡沫塑料的阻燃等级或在改善其脆性的同时不降低固有的阻燃性能,还未见关于酚醛泡沫燃烧全过程行为的综述报道。文章介绍了酚醛泡沫在明火燃烧和阴燃状态的燃烧行为,分析了影响酚醛泡沫燃烧行为的因素,并总结了现有酚醛泡沫阻燃研究的进展。目前酚醛泡沫的燃烧行为及阻燃研究主要集中在泡沫的明火燃烧,对酚醛泡沫阴燃问题的研究重视不足,缺乏针对酚醛泡沫燃烧全过程的行为和机理探究。因此,提出应加大对酚醛泡沫阴燃行为的研究投入,注重对酚醛泡沫燃烧全过程的机理探索与阻燃方案研究,设计并研发出解决酚醛泡沫燃烧全过程问题的有效途径。     

聚氨酯泡沫阻燃材料

介绍了聚氯酯阻燃材料的发展现状和发展趋势。并对聚氨酯阻燃材料的研发原理做了简单介绍。     

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。     

低粘度酚醛环氧阻燃树脂的制备与性能研究

本文制备了一种低粘度的酚醛环氧阻燃树脂,采用FTIR和¹H NMR等对其化学结构进行表征,并重点研究了该树脂的粘度、阻燃性以及力学性能。结果表明,本文制得的树脂产物所测环氧值为0.64,在25℃下所测粘度为15.04 Pa·s,树脂与三乙烯四胺固化物极限氧指数为29%,燃烧等级为UL-94 V-0级,且无熔滴滴落,拉伸强度为49.24 MPa,断裂伸长率为14.13%,弯曲强度为28.48 MPa,冲击强度为36.28 MPa,热变形温度为139.6℃。     

阻燃高分子材料及其阻燃剂研究进展

自1735年Wyld申请了国际上的第一篇关于阻燃剂的专利直到现在,国内外许多科研机构和高等院校都召集科研人员致力于阻燃科学的研究,这在多数工业发达国家尤为显著。其中阻燃高分子材料的研究是阻燃科学研究的其中一个重要内容。本文主要介绍阻燃高分子材料及其阻燃剂的分类、作用机理等。通过分析阻燃剂的发展方向,预测了阻燃高分子材料发展的一些新动向。     

阻燃PET母粒及阻燃涤纶的生产

采用国产磷系阻燃剂制备出阻燃母粒,将母粒与PET切片共混生产阻燃涤纶短纤维,纤维的可纺性优良,断裂强度随阻燃剂加入量的增加有所降低,当母粒中阻燃剂的质量分数在3％～4％时,纤维的综合性能较好,织物的限氧指数(LOI)值高达31。     

阻燃高分子材料及其阻燃剂研究进展

介绍阻燃高分子材料及其阻燃剂的分类、作用机理、作用途径。阐述了聚酯纤维、聚酰胺、热塑性饱和聚酯塑料、聚乙烯、聚丙烯、复合材料及纳米材料等一些常见阻燃高分子材料的现状。通过分析阻燃剂的发展趋向预测了阻燃高分子材料发展的一些新趋向。     

聚磷酸铵改性酚醛泡沫阻燃及耐热性能研究

以苯酚与甲醛为原料合成酚醛树脂,并添加助剂与聚磷酸铵(APP),采用低温模塑发泡法制备改性酚醛泡沫(PF)。采用锥形量热仪、烟密度和热重分析分析不同APP添加量对PF燃烧性能和热稳定性的影响。结果表明：在PF中添加APP可以提高其阻燃性能和耐热性能,在60 kW/m²热辐射强度下热释放速率峰值(PHRR)和总热释放量(THR)随着APP添加比例的提高而降低。当APP添加量为20%时,改性PF的PHRR由90.44 kW/m²下降至11.92 kW/m²。在无焰和有焰两种条件下,改性PF的烟密度随APP添加量增大而提高,透光率降低。升温速率为5℃/min条件下,随着APP添加量的增大,改性PF的热解温度逐渐提高,但APP添加量较低(≤5%)时,不同升温速率下改性PF热解特性均与纯PF无明显差异。升温速率≥30℃/min时,APP与PF热解产物形成的残炭在800℃未发生热解。APP添加量为10%～15%时,改性PF具有良好的阻燃性能和耐火性能。     

橡胶的阻燃与阻燃剂

本章介绍了橡胶燃烧的现象、过程和条件及原材料的选用原则。比较了各类阻燃剂的优缺点和配合要点。文章还叙述了橡胶阻燃性的评价方法与指标。     

Phosphorus-containing epoxy for flame retardant. III: Using phosphorylated diamines as curing agents

Two phosphorus-containing diamine compounds, bis(4-aminophenoxy)-phenyl phosphine oxide and bis(3-aminophenyl)phenyl phosphine oxide, were synthesized for use as curing agents of epoxy resins. Phosphorylated epoxy resins were obtained by curing Epon 828 and Eponex 1510 with these two diamine agents. For raising the phosphorus contents of the resulting epoxy resins, the phosphorus-containing epoxy, bis(glycidyloxy)phenyl phosphine oxide (BGPPO), was also used. These two diamine agents showed similar reactivity toward epoxies. Their reactivities were higher than DDS and lower than DDM. High char yields in TGA evaluation were found for all the phosphorylated epoxy resins, implying their high flame retardancy. The excellent flame-retardant properties of these phosphorylated epoxy resins were also demonstrated by the high limiting oxygen index (LOI) values of 33 to 51. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 895–901, 1997     

软质聚氨酯泡沫塑料无卤阻燃技术研究进展

软质聚氨酯泡沫(FPUF)是聚氨酯材料的主要产品之一,由于其较低的密度和热传导率而易燃,在燃烧过程中会放出大量烟雾和有毒气体,对FPUF进行阻燃处理尤为重要。卤系阻燃剂由于存在潜在的毒性和环境问题而受到限制,因此FPUF的无卤阻燃技术是今后主要的研究方向。本文综述了近年有关软质聚氨酯泡沫无卤阻燃技术的研究进展,包括添加型无卤阻燃剂法、反应型无卤阻燃剂法、层层组装涂层法。指出开发高相对分子质量、含多种阻燃元素的有机添加型阻燃剂和膨胀型阻燃剂以及复配型阻燃剂,解决层层组装涂层法的组装慢等问题将是FPUF无卤阻燃技术的发展趋势。     

阻燃型聚丙烯酸酯橡胶的制备和性能

用共聚法和共混法制得了2种阻燃环氧型聚丙烯酸酯橡胶 (EP -ACM ) ,研究了含磷共聚单体及添加无机阻燃剂对EP -ACM阻燃性能和力学性能的影响。结果表明 ,阻燃剂的引入虽可有效地提高胶料的阻燃性 ,但力学性能均有不同程度的下降。     

Thermal properties and combustion behavior of POSS‐ and bohemite‐finished cotton fabrics

A finishing process with polyhedral oligomeric silsesquioxane (POSS) and bohemite nanoparticles has been exploited for enhancing the thermal stability and flame retardancy of cotton fabrics. The thermal behavior of flame retardant treated cellulosic fabric has been studied by thermogravimetric analyses (TGAs). It has been found that such nanoparticles favor the carbonization of the cellulose and slow down the kinetics of thermo‐oxidation in air. At the same time, the finished fabrics have turned out to be more efficient with respect to neat cotton as far as the flame retardancy is concerned, pointing out an increase of the time to ignition (TTI) and a decrease of the heat release rate (HRR). Furthermore, a comparison between the fire performances of the nanoparticles under study and a commercial phosphorus‐based flame retardant has been investigated. The morphology and elemental composition present in the treated fabrics have been also investigated using scanning electron microscopy (SEM) coupled to the energy dispersive spectroscopy (EDS), and the results have been compared with the untreated fabric. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

阻燃粘胶纤维的热降解性能研究

采用极限氧指数法测定了阻燃粘胶纤维的阻燃性能;采用热重分析法研究了普通粘胶纤维和阻燃粘胶纤维的热稳定性及热降解表观活化能,初步探讨了阻燃粘胶纤维的热降解机理。结果表明,加入阻燃剂后,纤维的极限氧指数由19.5%增加到34.0%,且残留量由6.41%增加到20.67%。阻燃剂在纤维降解中凝聚相作用明显,降解后,阻燃剂主要残留在残渣里。     

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。     

Aryl phosphinate anhydride curing for flame retardant epoxy networks

An aryl phosphinate anhydride (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)-methyl succinic anhydride (DMSA), with a pendent phosphorus group was synthesized and used as a reactive type flame retardant. The structure of DMSA was confirmed by FTIR, mass, elemental analysis, ¹H and ³¹P NMR spectroscopies. The aryl phosphinate anhydride was successfully used to cure some commercial epoxides, such as bisphenol A diglycidyl ether (DGEBA) and epoxy-novolac. The epoxy networks obtained were characterized by dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and the limiting oxygen index (LOI) test. Epoxy resins cured with DMSA exhibit higher LOI values and char yields compared with those cured by commercial anhydrides, such as phthalic anhydride (PA) and hexahydrophthalic anhydride (HHPA). Furthermore, the LOI value and the char yield of the epoxy-resin composites increase with increasing phosphorus content. The flame retardancies of the epoxy-resin composites were significantly improved by using aryl phosphinate anhydride. © 1998 Society of Chemical Industry.     

Synthesis of phosphorus-containing flame retardants and investigation of their flame retardant behavior in textile applications

Flame retardants are a growing area of research interest. Nonhalogenated, durable, and nonleachable flame retardants are one of the main strategies used in the research of flame retardant polymers. In this regard, the covalent attachment of phosphorus-containing flame retardants onto cotton fabric has been developed. Two types of reactive phosphorus-containing flame retardants (MKT-1 and MKT-2) have been synthesized and used as a surface coating for cotton fabric. MKT-1 possesses anhydride and acid functionalities that can react with the  OH functionalities in cellulose. In addition, MKT-2 has both acid and organosilicon groups that can also react with the hydroxy group present in cellulose. The structures of the reactive flame retardants (MKT-1 and MKT-2) were characterized using ¹³C and ³¹P nuclear magnetic resonance spectroscopy. Thermal properties of the coated and uncoated cotton fabrics were investigated using thermogravimetric analysis. Surface characterization was carried out using scanning electron microscopy and X-ray photoelectron spectroscopy. A standard test method used to evaluate the flammability of blankets (BS 5852) was also applied to characterize the fire retardant properties of the coated and uncoated cotton fabrics studied. Different loadings of MKT-1 and MKT-2 on the fabric (10, 20, and 30% by weight in dimethylformamide solution) were applied in the dip coating process. The cotton fabric coated with 30% MKT-2 does not burn after being subjected to a propane burner for 20 s and also produced the highest char yield (36%) at 500 °C. Inductively coupled plasma–optical emission spectrometry showed that MKT-1 contains 8.23 ± 0.33 P% whereas MKT-2 contains 3.88 ± 0.15 P%. Although MKT-1 possess a higher P content than MKT-2, the additive effect caused by the organosilicon and nitrogen groups present in MK-2 enhance its flame retardant properties. Furthermore, the covalently attached flame retardant materials are durable and do not hydrolyze during washing. The mechanical properties of coated fabrics were characterized by a tensile test and significant change in elongation at break was observed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47935.     

硅橡胶阻燃开发研究进展

简单介绍了硅橡胶的燃烧过程及其自身的燃烧特性,并确立了硅橡胶的阻燃研究方向。综述了铝-镁系、磷氮系、硼硅铂系、膨胀型等不同类型阻燃剂在硅橡胶中的实际应用,并对未来阻燃技术进行了展望。