耐高温杂化阻燃剂/改性红磷阻燃半芳香尼龙的研究

将自制的耐高温勃姆石@苯基次膦酸铝杂化阻燃剂(BM@Al-PPi)与市售改性红磷(MRP)复配制得一种可用于半芳香尼龙PA6T/DT(HTN)的耐高温高效阻燃体系.保持阻燃剂15 wt%的总添加量不变时,MRP的添加量仅为5 wt%即可赋予HTN垂直燃烧V-0级别,极限氧指数为29.8%.锥形量热测试及其燃烧残余物研究表明,MRP阻燃HTN材料以气相阻燃作用为主,抑制热释放效果不佳且烟释放明显增加;而BM@Al-PPi的凝聚相交联成炭作用可同时抑制热释放与烟释放.结合裂解气相色谱质谱联用(Py-GC-MS)分析,给出了HTN/BM@Al-PPi/MRP体系的阻燃机理.BM@Al-PPi与MRP结合使得残炭质量显著提高,同时兼具气相作用,达到了较好的阻燃效果.     

微胶囊化超细红磷的制备及其安定性研究

研究了用硝酸铝溶胶凝胶法制备微胶囊化超细红磷的工艺，通过着火点测试研究了包覆材料和包覆工艺以及影响包覆效果的因素，发现以5%氢氧化铝溶胶凝胶制备微胶囊化红磷在150 ℃左右真空干燥得到的样品安定性较好，XPS表明有95.3%的红磷被包覆，透射电镜显示形成一层均匀的包覆层，超细红磷的安定性得到了较大的提高。     

可膨胀石墨阻燃体系在聚丙烯中的作用

采用可膨胀石墨(EG)为主阻燃剂,包裹红磷(MRP)为阻燃协效剂制备阻燃聚丙烯(PP)。在mEG∶mMRP≥2时,阻燃效果最佳。阻燃剂(FR)含量达到30%后,阻燃效果大幅度提高,氧指数大于28。采用热失重和流变学方法分析了炭层质量,探讨了在mEG∶mMRP≥2时,阻燃效率最高的原因。相容剂马来酸酐接枝聚丙烯(PP-g-MAH)能够改善阻燃剂和聚丙烯之间的相容性,提高粘结力,改善炭层质量,提高材料的氧指数,PP-g-MAH用量为30%时,材料的氧指数达到31.4。     

酶解木质素/Mg（OH）2复合材料的合成及阻燃性能研究

以酶解木质素、NaOH和MgSO4·7H2O为原料,制备酶解木质素包覆Mg（OH）2复合材料。通过红外光谱（FT-IR）、热重（TGA-DTA）及透射电镜（TEM）分析对复合材料进行结构表征及包覆形貌观察,结果表明,酶解木质素成功包覆Mg（OH）2,该复合材料在800℃残炭量可达46．24％。研究了复合材料与微胶囊红磷互配添加入丁苯橡胶的阻燃性能,垂直燃烧测试结果表明,当复合材料添加量达到100％时,阻燃级别可达到FV-0级。共混硫化胶燃烧残渣的SEM照片表明,燃烧后胶料的成炭效果很好,炭层连续致密,孔洞很少。     

二元醇改性密胺甲醛树脂包覆红磷

用乙二醇和1,4-丁二醇对密胺甲醛树脂(MF)包覆红磷(MFRP)进行了化学改性,并对改性前后MFRP的磷化氢释放情况进行了比较。 在模拟材料加工条件下,纯红磷(RP)的磷化氢释放量为44.51 mg/L,MFRP磷化氢释放量降低到24.13 mg/L,而二元醇改性包覆红磷,磷化氢释放量降低到8.05 mg/L。 改性包覆效果显著。 用傅里叶红外光谱(FTIR)表征改性前后MFRP的结构,证实改性剂成功介入树脂结构中。 热重分析(TG/DTG)结果表明,改性后,MFRP的初始分解温度由未改性的264 ℃降到182 ℃,最大失重速率由11%/min下降到4.1%/min,800 ℃时,改性前后的MFRP残留量相同,均为11%。     

原位聚合法制备聚磷酸铵微胶囊及其应用的研究进展

以聚磷酸铵微胶囊阻燃剂的包覆壳材料为重点,综述了聚磷酸铵微胶囊阻燃剂的无机材料包覆、有机材料包覆、双层或多层包覆以及纳米材料包覆,总结了国内外关于原位聚合法制备聚磷酸铵微胶囊的最新研究进展。介绍了聚磷酸铵微胶囊形成过程中,包覆壳材料与聚磷酸铵的原位聚合方法及机理。并且提出了聚磷酸铵阻燃剂在材料燃烧过程中存在的协同效应。最后,结合聚磷酸铵微胶囊阻燃剂在阻燃过程中存在的问题,展望了原位聚合在微胶囊阻燃领域中的未来发展方向。     

聚对苯二甲酸丙二醇酯的无卤阻燃化改性

聚对苯二甲酸丙二醇酯作为新型聚酯材料,具有非常优良的性能,但其易燃性很大的限制了它的应用范围。为了提高对苯二甲酸乙二醇酯的阻燃性能,本文以无卤膨胀型EPFR-300A为阻燃改性剂,马来酸酐接枝聚烯烃(POE-g-MAH)弹性体为增韧剂,对聚对苯二甲酸丙二醇酯树脂(PTT)进行阻燃改性。通过热重分析仪(TGA)、示差扫描量热仪(DSC)、扫描电子显微镜(SEM)、力学性能等技术手段研究了阻燃剂和增韧剂对PTT树脂力学、热学和阻燃性能的影响。结果表明,增韧剂POE和POE-g-MAH的添加提高了PTT树脂的综合力学性能。当质量分数相同时,POE-g-MAH对PTT树脂的增韧效果要优于POE,且当POE-g-MAH质量分数为7%时,综合力学性能最佳。当添加相同质量分数增韧剂,EPFR-300A质量分数达到20%时,阻燃PTT材料阻燃性能最佳,极限氧指数(LOI)达到28.0%,垂直燃烧阻燃等级达到UL94 V-0级。EPFR-300A阻燃剂与PTT树脂间相容性良好,可以有效地促进PTT树脂成炭并提高材料的阻燃性能。     

聚乙烯/石墨层间化合物热降解过程的TG-FTIR研究

将含磷化合物插层石墨层间化合物(GIC)用于聚乙烯(PE)的阻燃,采用氧指数(LOI)方法评价了PE/GIC的阻燃性能,并采用热分析-红外光谱联用技术(TG-FTIR)研究了PE/GIC的热降解过程,探讨了GIC的阻燃机理。研究表明,不同含磷化合物插层GIC阻燃聚乙烯的氧指数有显著差别,其中以多聚磷酸铵-GIC的阻燃效果较好,氧指数较高。TG-FTIR研究结果表明,GIC并未显著影响PE的热降解方式,但由于GIC体积膨胀所发生的氧化还原反应导致部分PE热降解提前并发生热氧化降解,促进了后期成炭的石墨化过程。     

纤维级氢氧化镁阻燃体系研究

采用一种天然矿物纤维，经特殊加工改性，制成纤维级氢氧化镁，探讨了其与高分子材料的复合性，阻然，消烟，增强等作用，并以硼酸，硬脂酸和有机硅化物为阻然增效剂，ＬＤＰＥ为基体树脂制作作了低烟阻燃材料，产品性能接近于ＥＷＣＺ－６２８７－１产品指标。     

微胶囊无卤阻燃剂的研究进展

介绍了作为微胶囊芯材的无卤阻燃剂——无机阻燃剂、膨胀阻燃剂、氮磷系阻燃剂的分类及优缺点。以微胶囊阻燃剂的包覆壳材料为重点,综述了阻燃剂的无机包覆、有机包覆、双层或多层包覆和反应生成阻燃剂型包覆的最新研究进展,最后介绍了界面聚合法、原位聚合法、溶胶-凝胶法和超临界法等四种制备微胶囊阻燃剂的方法,并展望了微胶囊阻燃剂的未来发展方向。     

Preparation and characterization of microcapsulated red phosphorus and its multi-step thermal oxidation processes based on kinetic approach

Aluminium hydroxide/melamine–formaldehyde resin microcapsulated red phosphorus (MRP) was successfully prepared by two-step processes. The microcapsulated red phosphorus was characterized with Fouriertransform infrared spectroscopy (FTIR) and scanning electron microscope (SEM). Meanwhile its water absorption, thermostability were also determined. The results show that the MRP exhibited lower water absorption and higher thermostability compared with red phosphorus (RP) itself. Moreover, the thermal oxidative decomposition kinetics of MRP was investigated by TG/DTG and DTA in air atmosphere using non-isothermal experiments. The results show that the MRP’s decomposition consisted of two steps. And the apparent activation energies E_α was determined by applying both the Ozawa–Flynn–Wall (OFW) and Kissinger, Akahira and Sunose (KAS) methods. It was found that the dependence of E_α on α is complex. Both of the steps in this study fitted Sestak–Berggren (SB) model in overall reaction controlled kinetics and the corresponding model parameters, n, m, A were obtained. The simulated curves were fitted to experimental curves by plotting dα/dt vs. temperature at different heating rates.     

Experimental study on liquid fire behavior at different effective ceiling heights in a full-size simulated cargo compartment

A phosphorus-containing maleimide flame retardant (BDMP) was synthesized via the addition reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide and N,N′-bismaleimide-4,4′-diphenylmethane. The structure of BDMP was characterized by Fourier-transform infrared spectroscopy (FTIR), ¹H and ³¹P nuclear magnetic resonance and elemental analysis. The thermal, flame-retardant and mechanical properties of the flame-retardant cyanate ester system were investigated by thermogravimetric analysis (TG), limiting oxygen index (LOI), vertical burning (UL-94), cone calorimeter test and dynamic mechanical analysis. The TG results indicated that the initial decomposition of modified CE resin shifted from 416 to 363 °C, and on the contrary, the char yield increased from 38.8 to 44.5%. The results of combustion tests indicated that the CE with highest phosphorus content acquired LOI value of 37% and achieved a UL-94 V-0 rating. The peak heat release rate, average heat release rate and average of effective heat combustion (av-EHC) of that group decreased by 39.5, 31.2 and 41.8%, respectively. In addition, the increase in phosphorus content led to a decrease in av-EHC and average CO₂ yield, and an increase in average CO yield, indicating that BDMP led to an incomplete combustion of the modified CE system. The flame-retardant mechanism was investigated by TG–FTIR, scanning electron microscope and cone calorimeter. Last but not least, the dielectric constant of modified CE system showed a slight fluctuation from 2.96 to 3.02 at 1 GHz, which was lower than that of neat CE.     

Red phosphorus acts as second acid source to form a novel intumescent-contractive flame-retardant system on ABS

A novel halogen-free flame retardant prepared by poly(p-ethylene terephthalamide) and ammonium polyphosphate (APP) on acrylonitrile–butadiene–styrene (ABS) resin has a good flame retardancy when loading is 30 %; but, once the mass fraction is <30 %, the system does not maintain outstanding flame retardancy. To improve the efficiency of this kind of flame retardant and LOI values, higher thermal stability acid source-red phosphorus is introduced. It is found that a little quantity of red phosphorus will improve the flame retardancy of ABS remarkably and will change the process of charring; when the mass fractions of APP, PPTA, and red phosphorus are only 15, 5, and 2 %, respectively, though the LOI of flame-retardant ABS is 27, UL-94 vertical burning test still reach V-0. Thermogravimetric analysis data show that red phosphorus changes the thermal degradation behavior of IFR-ABS system, shrink digital photo display system, and yield more stable residue at higher temperature; Fourier transform infrared results and scanning electron microscopic micrographs show that red phosphorus can catalyze the charring and form much denser char to improve the flame-retardant performance of the materials.     

膨胀型聚氨酯防火涂料阻燃机理的研究

用自制的新型成炭剂和聚磷酸铵复配作为聚氨酯防火涂料的阻燃体系。采用热失重分析、扫描电镜、红外光谱和元素分析等手段对膨胀型聚氨酯防火涂料的阻燃机理进行了较为深入的研究．     

Inhibition by red phosphorus of unimolecular thermal chain-scission in poly(methyl methacrylate): Investigation by NMR,FT-IR and laser desorption/fourier transform mass spectroscopy

The reaction of red phosphorus with poly(methyl methacrylate) under pyrolysis conditions was investigated with a number of physical techniques. A random methyl methacrylate/cyclic anhydride copolymer is formed from atatic PMMA, whereas a random methyl methacrylate/methacrylic acid copolymer is obtained with isotactic PMMA. The backbones of both these copolymers are more stable toward depolymerization than that of PMMA. The flame-retardant activity of red phosphorus with PMMA may arise in part from stabilization of the polymer toward depolymerization via modification of the sidechains.     

阻燃型含磷环氧树脂体系的研究进展

将磷导入环氧树脂体系而赋予其阻燃性能是目前热门的研究课题。本文简述了含磷阻燃剂的阻燃机理，详细讨论了含磷阻燃环氧的类型及固化物的阻燃特性，以及磷和氮、硅等元素的协同效应。     

A novel flame retardant containing phosphorus,nitrogen, and sulfur

In this article, a novel intumescent flame retardant (IFR) PNSFR containing three flame-retardant elements, phosphorus, nitrogen, and sulfur was designed and synthesized. Then a series of flame-retardant thermoplastic polyurethanes (TPU) were prepared using the PNSFR. The effects of the flame retardant on the flammability of TPU/PNSFR composites were investigated by limited oxygen index (LOI) and UL-94 vertical burning. The results showed that TPU containing 10 mass% PNSFR had the highest LOI value (36) and could reach the V-0 rating. The flame-retardant mechanism of PNSFR in TPU was also disclosed using thermogravimetric analysis (TG), scanning electron micrograph, TG-infared spectrometry, and Fourier transform infrared spectroscopy. The sulfur and phosphorus elements of PNSFR can be kept in residual char. Moreover, an optimal loading amount of the IFR in TPU is in favor of forming dense and continuous char layer to prevent heat transfer and the spread of flammable gases. The IFR PNSFR may find potential use for various flame-retardant polyurethanes.     

Flame-retardant modification of UV-curable resins with monomers containing bromine and phosphorus

UV-curable urethane acrylate resin and oligoester acrylate resin have been effectively flame retarded with vinyl-type flame-retardant monomers containing both bromine and phosphorus atoms. Thermogravimetric analysis indicates that the decomposition temperature of flame-retardant monomer is more closely matched to the decomposition temperature of cured oligoester acrylate resin than to that of cured urethane acrylate resin. The efficiency of each flame-retardant monomer in oligoester acrylate resin is higher than in urethane acrylate resin by a factor of ～ 2.2. The individual and the combined effects of tribromophenyl acrylate and triphenyl phosphate on the oxygen index of UV curable urethane acrylate resin have been studied. The bromine phosphorus synergistic action of the two flame-retardant components is evaluated quantitatively, and a maximum intermolecular bromine phosphorus synergism was observed in a flame-retarded formulation containing a Br/P atom ratio of 2. In the three acrylic monomers containing both bromine and phosphorus atoms, the optimum intramolecular bromine phosphorus synergism was observed at a monomer also containing a Br/P atom ratio of 2.     

Red phosphorus as a flame retardant for a thermoplastic nitrogen-containing polymer

Studies were made of the flame-retardant and smoke-suppressant activity of red phosphorus, in the presence of a brominated (decabromobiphenyl) and/or a nitrogenated (melamine) compound, on acrylonitrile-butadiene-styrene terpolymer. These studies were complemented by simultaneous thermal analyses of the polymeric systems. Red phosphorus is oxidised on heating and the thermal decomposition of any system containing this additive includes a substantial weight gain stage at ca 700 K. Melamine is volatilised very early on and thereafter acts only as a smoke suppressant in the gas phase. Decabromobiphenyl and red phosphorus interact positively in decreasing the flammability of the substrate, particularly at atomic ratios not lower than stoichiometric. The acrylonitrile content in ABS is very important, suggesting that the additives act mainly in the gas phase but that they also form some sort of charry layer on the polymer surface.