新型有机磷系阻燃剂的热稳定性

利用STA490C热分析仪对8种新型有机磷系阻燃剂的热失重过程进行测定和对比，结果表明磷杂螺环阻燃剂3，9-二羟基-2，4，8，10-四氧杂-3，9-二磷杂螺环[5，5]十一烷-3，9-二氧化物和苯基次膦酸类阻燃剂4-甲氧基羟甲基苯基次膦酸热稳定性较好。     

PET纤维及其织物的阻燃技术进展

概述了聚对苯二甲酸乙二醇酯(PET)纤维及其织物的阻燃技术,包括共缩聚阻燃PET纺丝、PET与阻燃剂共混纺丝及PET织物阻燃后处理等。其中,阻燃剂主要有磷系及磷-氮系阻燃剂,如:9,10-二氢-9-氧杂-10-磷杂蒽-10-氧化物(DOPO)衍生物、次膦酸(酯)及其聚合物、氧化膦聚合物、膦酸酯及螺环磷酸酯等。今后应积极开发生态和环境兼容的阻燃PET纤维新技术。     

熔融聚合法制备一种具有双螺环结构的膨胀型阻燃剂及其性能研究

采用3,9二氯-2,4,8,10四氧杂-3,9-二磷杂螺环［5,5］3,9二氧十一烷 (SPDPC)与己二胺,在氮气保护下采用熔融聚合法合成了一种新型膨胀型阻燃剂螺环磷酸酯己二胺共聚物（SPHD）,通过测试特性黏度确定了最佳合成条件为：反应温度165 ℃,n(SPDPC)/n(己二胺)=1/1.1,反应时间约4 h,产率达84 %;采用红外光谱、核磁共振氢谱对共聚物SPHD进行了结构表征,证实了目标产物的成功制备;热重分析显示其具有良好的热稳定性;通过与聚磷酸铵（APP）复配,应用于低密度聚乙烯（PE-LD）中,初步测试了其阻燃性能,当SPHD含量为15 %时,复合材料的氧指数值为27.2 %,UL94达到V-0级。     

氯化螺环磷酸酯的合成及其阻燃性能研究

采用三氯氧磷、季戊四醇、二氯甲烷等制备了氯化螺环磷酸酯阻燃剂。对合成物进行了傅立叶红外光谱分析,确定合成物为所需物质,即3,9-二氯-2,4,8,10-四氧代-3,9二磷螺环-3,9-二氧[5,5]十一烷。通过膨胀性能、热失重、氧指数测试研究了阻燃剂的阻燃性能。结果表明,氯化螺环磷酸酯阻燃剂具有较好的膨胀阻燃性能,经过马弗炉燃烧后,阻燃剂体积膨胀了27倍,并且形成了致密、封闭的焦化炭层;经热重分析800℃残炭量达到16%;经氧指数仪测试,质量分数为10%的阻燃剂处理毛白杨木材,氧指数值达到36%,与素材相比提高了18%。     

新型高效磷酸酯类阻燃剂的合成及应用

以季戊四醇、三氯氧磷和三(五)溴苯酚钠为原料合成了新型高效阻燃剂3,9-双[三(五)溴苯氧基]-2,4,8,10-四氧代-3,9-二磷螺环-3,9-二氧[5.5]十一烷,采用元素分析、熔点、红外等鉴定了它们的结构,并测试了它们对聚丙烯的阻燃性能。     

有机阻燃剂螺磷酸氯的合成

以季戊四醇和三氯氧化磷为原料,合成一种即含磷又含氯的有机阻燃剂,名为螺磷酸氯化合物,又名3,9-二氯-2,4,8,10,-四氧-3,9-二磷螺-[55]-十一烷-3,9二氧化物,其结构为螺旋状化合物,反应式为:     

螺环状磷酸酯的合成及相应磷酰氯酯化反应研究

本文采用新的工艺合成了国内未见报道的螺环状磷酸酯3,9-二氧-3,9-二芳氧(硫)基-2,4,8,10-四氧-3,9-二磷螺[5,5]十一烷1a～d,研究了螺环磷酰氯酯化反应条件。化合物1a～d结构经IR,NMR和TGA等确证。     

磷系阻燃改性共聚酯的热性能研究

选用主链含磷的阻燃剂2-羧乙基苯基次膦酸和侧链含磷的阻燃剂9,10-二氢-9-氧杂-10-[2,3-二(2-羟基乙氧基)羰基丙基]-10-磷杂菲-10-氧化物,在3 L聚合反应釜上分别合成了磷质量分数为0.6%的阻燃改性共聚酯。利用TGA、DSC对其热性能进行了分析,并对其切片干燥和熔融后的黏度降进行了测试。结果表明,随着反应型阻燃剂的添加,阻燃共聚酯的tg,tm下降,而Δt热和Δt冷则呈上升趋势,结晶能力下降;共聚酯的初始热分解温度有所下降,经切片干燥和熔融后的黏度降增大。     

无溶剂法合成PPS-PEPA的研究

在无溶剂条件下,以苯基硫代膦酰二氯(DCPPS)、1-氧基磷杂-4-羟甲基-2,6,7-三氧杂双环[2.2.2]辛烷(PEPA)为原料,合成含硫有机膦阻燃剂PPS-PEPA。通过红外、核磁、热分析、元素分析等对产物进行了表征,并对其阻燃性能进行了研究。     

一种同环双膦阻燃剂的合成及其应用研究

以苯基膦酰二氯及三羟甲基氧化膦为原料,合成了一种高含磷量同环双膦阻燃剂——羟甲基膦酰杂环状苯基膦酸酯(即1,4-二氧-1-苯基-4-羟甲基-2,6-二氧杂-1,4-二磷杂环己烷)。通过考察溶剂、原料物质量比、反应温度及反应时间等对该产物产率的影响,确定了最佳合成条件,同时利用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H-NMR)、热重(TG)分析及极限氧指数(LOI)测试等手段表征了产物的结构及性能。结果表明:当采用乙二醇二乙醚作为溶剂,且苯基膦酰二氯和三羟甲基氧化膦的物质量比为1:1、反应温度为120℃、反应时间为6 h时,产物的产率达到最大值(94.5%)。产物具有较好的热稳定性,当其应用于191不饱和聚酯或聚对苯二甲酸丁二醇酯(PBT)时均表现出了良好的阻燃成炭效果;另外,当其与氰尿酸三聚氰胺盐(MCA)复配用于PBT阻燃时,表现出明显的协同阻燃效应。     

Synthesis and characterization of dicyclic silicon-/phosphorus-grafted alumina and its application in improving flame retardancy of epoxy resin

A new phosphorous/silicon/aluminum hybrid flame retardant (SAlu) was prepared by a surface grafting modification of alumina with a polymer (SDPS). The polymer was prepared by a condensation reaction between 3,9-dichloro-2,4,8,10-tetrahydroxy-3,9-diphosphate heterocyclic-3,9-dioxide [5.5] undecane (SPDPC) and diphenyldisiloxol. The structure of the SAlu was further characterized by Fourier transform infrared spectroscopy, X-ray diffraction, UV–Vis absorption, and particle size analysis. Thermogravimetric analysis showed that SPDS was grafted over 40% of the alumina surface. When introduced into epoxy resin, SAlu effectively improved the thermal stability and carbonization rate of the epoxy composites at high temperature. Carbonization studies showed that SAlu promoted formation of a ceramic-carbon coking structure with a porous morphology of aggregates, which isolate combustible materials, heat, and oxygen. These features improved the flame retardant performance of the composite. The solidified materials were evenly dispersed in the network structure to improve the elastic deformation ability and glass transition temperature of the solidified resin.     

A novel class of halogenated phosphate fire retardants for use in polypropylene

A novel class of 3,9-haloneopentoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dioxides has been synthesized. The method of preparation and physical properties of the compounds are described. The chemicals have been found to be excellent fire retardants for polypropylene. A polypropylene composition meeting the UL-94 V-0 specification can be achieved on both 1/8 and 1/16-in.-thick specimens with as little as 15% addition of one of these compounds. The use of a typical inorganic synergist such as antimony oxide is not required. The spirodiphosphates described exhibit good light, thermal, and hydrolytic stability.     

磷-溴膨胀型阻燃剂的结构表征及在聚丙烯中的应用评价

通过对自行合成的阻燃剂季戊四醇双螺环磷酰双三溴新戊醇酯进行结构分析与应用评价.用红外、元素分析等手段表征了其结构,热失重表明其具有良好的热稳定性.将该阻燃剂与三聚氰胺(Mel)、氧化锑(Sb2O3)等复配后,添加至聚丙烯(PP)中,实验表明:在添加量为17%(质量分数)时,阻燃PP材料的氧指数达到26.4%,垂直燃烧通过UL-94 V-0级.显示了良好的阻燃性.     

SYNTHESIS AND SOLUBILITIES OF 3,9-DIPYROLIDINO-2,4,8,10-TETRAOXA-3,9-DIPHOSPHASPIRO[5.5]UNDECANE-3,9-DIOXIDE IN SELECTED SOLVENTS

A flame retardant with enhanced phosphorus-nitrogen content, 3,9-dipyrolidino-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane-3,9-dioxide (DTDP) was synthesized by the reaction of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (SPDPC) with pyrrole. The structure and the thermal stability of the compound were characterized by infrared spectroscopy (IR), nuclear magnetic resonance (¹H NMR and ¹³C NMR), mass spectroscopy (MS), elemental analysis, and thermogravimetric analysis (TGA). Using a static analytical method, the solubilities of DTDP in N,N-dimethylformamide (DMF) in the temperature range from 302.80 to 362.05 K and in water in the temperature range from 303.65 to 360.75 K were determined. The solubilities of DTDP in ethanol, acetonitrile, acetone, acetic ester, and DMF + water binary mixtures were also measured for comparison. The solubility data were correlated with an empirical equation.     

Thermal degradation behaviors of polypropylene with novel silicon‐containing intumescent flame retardant

The N‐[3‐(dimethoxy‐methyl‐silanyl)‐propyl]‐N′‐ (9‐methyl‐3,9‐dioxo‐2,4,8,10‐tetraoxa‐3,9‐diphospha‐spiro[5.5]undec‐3‐yl)‐ethane‐1,2‐diamine/dimethoxy dimethyl silane copolymer (PSiN II), which simultaneously contains silicon, phosphorus, and nitrogen, is synthesized and incorporated into polypropylene (PP). The flame retardancy is evaluated by the limiting oxygen index value, which is enhanced to 29.5 from 17.4 with 20% total loading of PSiN II. The thermal degradation behavior of PP/PSiN II is investigated by thermogravimetric analysis under N₂ and air. The PP/PSiN II sample degrades at 400°C for different amounts of time, and the process of degradation is studied by Fourier transform IR. The morphology of the char formed at 400°C for 10 min is investigated by scanning electron microscopy. The swollen inner structure, close, and smooth outer surface provide a much better barrier for the transfer of heat and mass during fire and good flame retardancy. The thermal stability of PP is improved by incorporation of PSiN II. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2487–2492, 2005     

Reactive,intumescent, halogen‐free flame retardant for polypropylene

A reactive, intumescent, halogen‐free flame retardant, 2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl)amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecan‐3‐yl}oxy)ethyl methacrylate (EADP), was synthesized through a simple three‐step reaction from phosphorus oxychloride, pentaerythritol, hydroxyethyl methacrylate, and melamine. EADP exhibited excellent thermal stability and char‐forming ability, as revealed by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The TGA results show that the temperature at 5% weight loss was 297.8°C and the char yield at 700°C was 51.75%. SEM observation revealed that the char showed a continuous and compact surface and a cellular inner structure with different sizes. Composite of polypropylene (PP) with a 25 wt % addition of EADP (PP/EADP25) passed the UL‐94 V‐0 rating and showed a limiting oxygen index value of 31.5. Compared with those of neat PP, the flexural strength and modulus values of PP/EADP25 were somewhat improved, the tensile strength was basically unchanged, and the notched Izod impact strength was slightly decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.     

Structural Basis for Intumescence – Part III – Thermal Degradation Study of Intumescent Polymers Containing Spirophosphorus Moiety in the Backbone

3,9-Dichloro-2,4,8,10-tetraoxo-3,9-disphosphaspiro-[5.5]-undecane-3,9-dioxide (spiro) was melt condensed with structurally different dihydric phenols to form poly aromatic spirophosphates. The thermal volatilization analysis showed eruptive release of gases above 300°C and the temperature region of release depends on the nature of the aromatic units incorporated in the polymer backbone. The thermal degradation in nitrogen atmosphere indicated the formation of phenol, substituted phenols, aromatics, alkyl and alkenyl substituted aromatics and condensed aromatics like azulenes, indanes and fluorenes. The source for the formation of these products is the spiropentadiene released from the spiro unit during degradation.     

聚酯高温稳定性的热重-红外光谱联用分析

用热重 -红外光谱联用分析技术 ,研究了高温条件下聚酯 (PET)的热稳定性和热氧稳定性 ,表明由于氧的存在 ,PET的起始失重温度大大地降低 ,以至低于 PET树脂的最低熔融加工温度 ,说明PET的热氧稳定性是直接关系到它的加工和制品质量的重要因素     

加成型硅橡胶的热重法－差热分析

用热重法－差热分析对加成型硅橡胶的热空气老化历程进行了研究，分析了金属氧化物耐热添加剂对提高加成型硅橡胶耐热性的作用机理及复合金属氧化物对提高耐热性的协同作用。