Effect of a novel phosphorous-nitrogen containing intumescent flame retardant on the fire retardancy and the thermal behaviour of poly(butylene terephthalate)

A novel phosphorus-nitrogen containing intumescent flame retardant (P-N IFR) was prepared via the reaction of a caged bicyclic phosphorus (PEPA) compound and 4,4′-diamino diphenyl methane (DDM) in two steps. The product was added to poly(butylene terephthalate) (PBT) to obtain halogen-free flame retarded polyester. UL-94 test, thermogravimetry and in situ infrared spectroscopy were used to characterize the flammability, thermal degradation properties and the char-forming process. It was shown that the phosphorus-nitrogen containing compound could improve both the flame retardancy and thermal stability more effectively than other P-N flame retardants. Furthermore, it was a good char-forming agent incorporated with the co-addition of polyurethane (PU) when the combustion occurred. The formation of P-N structure was incorporated in the char layer.     

N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺的合成、晶体结构及热性能研究

通过二乙氧基硫代磷酰氯与对苯二胺反应生成了标题化合物N,N'-二(二乙氧基硫代磷酰基)-1,4-苯二胺，并应用元素分析, FTIR及¹H NMR对标题化合物进行了表征. 利用X射线单晶衍射测定了其晶体结构, 同时应用TG分析法对其热性能进行了分析. 标题化合物的相对分子质量M_r＝412.42, 为正交晶系, Pbca空间群, 晶胞参数为a＝0.86936(16) nm, b＝1.2787(2) nm, c＝1.8897(3) nm, β＝90°, V＝2.1006(7) nm³, Z＝8, D_c＝1.304 g/cm³, μ(Mo Kα)＝0.425 mm^－1, F(000)＝872, S＝1.052. 最终偏离因子R＝0.0628, wR＝0.1860, 可观测衍射点1852个[I＞2σ(I)]. 该晶体通过对苯二胺连接并以中心对称分布, 并形成层状结构, 且存在弱的分子内氢键N—H…S. TG分析表明该化合物有很好的热稳定性及成炭性, 通过其阻燃聚丙烯腈表明, 该物质是一种高效能的膨胀型阻燃剂.     

Thermal degradation and fire performance of intumescent silicone‐based coatings

This paper deals with the thermal degradation and fire performance of silicone‐based coatings for protecting steel. In this study, the fire performance of silicone coatings as virgin or formulated materials is evaluated using two homemade fire testing methodologies: one similar to the “torch test” fire testing method and the other using a heat radiator test. It was shown that the performance of the silicone‐based coating used as thermal barrier can be improved incorporating a modifier (a mixture of polydimethylsiloxane and silica coated by a silane). In this case, silicone‐based coating swells and exhibits same fire performance as commercial intumescent coating at the torch test. It is shown that the incorporation of modifier in the silicone makes it to swell upon heating resulting in the formation of expanded material exhibiting low heat conductivity. Thermal degradation of the coating is also investigated: it occurs in three main steps leading to the formation of a tridimensional network characterized by the formation of Q⁴ structure at high temperature. Copyright © 2012 John Wiley & Sons, Ltd.     

Poly(vinyl alcohol)/melamine phosphate composites prepared through thermal processing: thermal stability and flame retardancy

Poly(vinyl alcohol)/melamine phosphate composites (PVA/MP) as a novel halogen‐free, flame‐retardant foam matrix were prepared through thermal processing, and then their thermal stability and flame retardancy were investigated by thermo‐gravimetric analysis, micro‐scale combustion calorimeter, cone calorimeter, vertical burning test, and limiting oxygen index (LOI) test. It was found that the thermal stability and combustion properties of the PVA/MP composites could be influenced by the addition of MP. Compared with the control PVA sample (B‐PVA), in the PVA/MP (75/25) composites, the temperature at 5% mass loss (T_5%) decreased about 10°C, the residual chars at 600°C increased by nearly 27%, the temperature at the maximum peak heat release rate (T_P) shifted from 292°C to 452°C, and the total heat released and the heat release capacity (HRC) decreased by 28% and 14%, respectively. Moreover, the PVA/MP composites could reach LOI value up to 35% and UL94 classification V‐0, showing good flame retardancy. At the same time, both Fourier transform infrared and X‐ray photoelectron spectroscopy spectra of the residual chars from the PVA/MP composites demonstrated that the catalytic effect of MP on the dehydration and decarboxylation reactions of PVA, and the chemical reactivity of MP during the chars‐forming reactions could be used to account for the changed thermal stability and flame retardancy of the PVA/MP composites. Copyright © 2012 John Wiley & Sons, Ltd.     

膨胀型类磷酸酯蜜胺盐阻燃剂的合成及应用研究

以双季戊四醇(DPE)、五氧化二磷、水和三聚氰胺为原料,合成了膨胀型环状类磷酸酯蜜胺盐阻燃剂。通过实验提出了合成该阻燃剂的最佳反应条件为：双季戊四醇(DPE)、五氧化二磷、水和三聚氰胺反应物料摩尔配比为1／2．5／2.0／3．45、反应时间4h和反应温度120℃。红外吸收图谱分析表明该阻燃剂具有环状结构,在热重分析和差热分析中该阻燃剂显示出优异的热稳定性和很高的成碳性。以该阻燃剂掺入聚丙烯中,阻燃效果显著,经测试阻燃聚丙烯的极限氧指数(LOI)为33．6,烟密度等级(SDR)为44．25,通过了UL94V-0级。     

N-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能

环状磷酸酯;水合肼;膨胀型阻燃剂;N-(5;5-二甲基-1;3;2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能     

新型膨胀阻燃剂的合成及其在涤纶织物中的应用

氧氯化磷与季戊四醇反应制得双氯螺磷(2);2与三乙醇胺反应合成了新聚合物1,其结构与性能经1H NMR,IR,TG和SEM表征。研究结果表明,1自身具有很好的成炭性,对涤纶织物具有很好的阻燃效果,扩展了涤纶的分解温度范围;通过SEM对经1整理的织物残炭形貌进行分析,证实1是膨胀型的阻燃剂。     

新型单组分磷氮膨胀阻燃剂的合成

以新戊二醇与三氯氧磷为原料,合成了5,5-二甲基-1,3-二氧杂己内磷酰氯;进而将5,5-二甲基-1,3-二氧杂己内磷酰氯分别与苯并咪唑类衍生物反应,得到三种新型单组分磷氮膨胀阻燃剂(Ⅲa-c).利用IR1、HNMR、质谱及元素分析等表征了Ⅲa-c三种化合物的结构;并利用热重分析考察了三种化合物的热稳定性能.结果表明,目标产物Ⅲa-c均有较好的成炭性和热稳定性,600℃时残炭质量分数分别达26.93%、23.62%及18.75%.     

Studies on the properties of polypropylene with a new silicon‐containing intumescent flame retardant

A new intumescent flame retardant (PSiNII), which contains silicon, phosphorus, and nitrogen elements, has been synthesized and incorporated into polypropylene (PP). Its effect on the properties of PP is investigated based on flame retardancy, thermal properties, mechanical properties, and morphologies. The flame retardancy is evaluated by the limiting oxygen index value. The thermal properties (oxidative behaviors and thermal stability) are investigated by thermogravimetric analysis under nitrogen and air atmosphere. The mechanical properties are researched based on the maximum tensile stress and relative strain at break. The morphologies of PP/PSiNII are studied by the scanning electron micrograph. Their flame retardancy and thermal stability are improved by introducing PSiNII. PP/PSiNII blends can achieve high fire performance and keep high mechanical property at the same time. During a fire, the melt‐dripping behaviors of PP‐containing PSiNII are improved. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2548–2556, 2005