无卤阻燃聚丙烯研究进展

综述了目前应用于聚丙烯的铝-镁系阻燃剂、膨胀型阻燃剂、磷系阻燃剂、硅系阻燃剂改善其燃烧性能的研究成果,分析了无卤阻燃剂的加入对聚丙烯阻燃性能、力学性能的影响,总结了无卤阻燃聚丙烯尚待研究的科学技术问题,提出了研究新型无卤阻燃剂和不同阻燃剂复合的协效作用,研制新型表面改性剂和新的表面改性技术,使阻燃剂与聚丙烯有适宜的相容性,构筑适度柔性、结合力强的界面结构,是制备具有优良阻燃性能、力学性能的无卤阻燃聚丙烯努力方向的研究思路.     

磷系阻燃环氧树脂研究

本文对近年来国内外9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）衍生物的合成及其应用于阻燃环氧树脂的方法进行介绍,并对所显示的阻燃性、热性能等作了概述和比较。将反应型磷系阻燃剂DOPO衍生物引入环氧树脂基体结构中形成阻燃持久、无卤、低烟、无毒、热稳定性好的新型含磷环氧树脂。     

磷系阻燃剂阻燃聚碳酸酯研究进展*

磷系阻燃剂具有阻燃效率高、低烟、低毒、与基质材料相容性好等优点,在阻燃高分子材料领域得到广泛应用。本文介绍了磷系阻燃剂的分类及阻燃机理,综述了近年来磷酸酯阻燃剂、膦酸酯阻燃剂、DOPO磷杂菲类阻燃剂、磷腈类阻燃剂和无机磷阻燃剂在阻燃聚碳酸酯领域的研究进展,为新型磷系阻燃剂的研发提供参考。     

EVA基无卤阻燃复合材料的研究进展

分别介绍了采用金属氢氧化物阻燃剂、蒙脱石型阻燃剂、磷系阻燃剂、氮系阻燃剂、膨胀型阻燃剂、有机硅阻燃剂、碱式硫酸镁晶须（MOS）阻燃剂和辐射交联技术制备的无卤阻燃乙烯―乙酸乙烯共聚物（EVA）复合材料的研究开发现状,并展望了无卤阻燃EVA复合材料的发展趋势。     

阻燃改性尼龙研究进展

综述了近年来阻燃改性尼龙材料的研究成果,尤其是现今适用于尼龙阻燃的各类阻燃体系的研究现状,包括溴系阻燃剂、磷系阻燃剂、氮系阻燃剂、磷-氮协效膨胀型阻燃剂、无机阻燃剂以及纳米阻燃协效剂等,并展望了未来阻燃尼龙的发展趋势.卤系阻燃剂将逐渐被替代,无卤环境友好型阻燃剂和膨胀型阻燃体系是未来重点的发展方向,综合改性、复配技术的应用也是未来研究和应用的热点.     

有机磷系及石墨烯阻燃环氧树脂研究进展

环氧树脂作为一种优异的树脂基体,被广泛地应用于众多领域,但因其极易燃烧,所以常常需要对其进行阻燃处理。本文简要综述了近几年有机磷系化合物及石墨烯阻燃环氧树脂的研究进展,其中有机磷系化合物阻燃部分重点介绍了以阻燃剂中间体9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)及其衍生物和聚磷酸铵(APP)为代表的含磷阻燃剂在环氧树脂中的阻燃机理和阻燃进展;同时也介绍了石墨烯及其衍生物在环氧树脂阻燃领域的最新研究进展,并对其发展前景进行了展望。     

三（2，4，6－三溴苯氧基）锑酸酯的合成及其阻燃性能与阻燃机理

合成了三（２，４，６－三溴苯氧基）锑酸酯，通过元素分析和ＩＲ光谱予以表征，并就其对聚乙烯和聚丙烯的阻燃性能与阻燃机理进行了研究。结果表明：这种分子中同时含有溴、锑的阻燃剂，比相应的仅含溴和仅含锑的阻燃剂混合物具有更高的阻燃性能。     

磷系阻燃环氧电子封装材料研究进展

磷系阻燃环氧树脂具有阻燃效率高、制备成本低、环境危害小等显著优点,成为5G通讯、智能电子和半导体等领域的重要封装材料。基于高效磷系阻燃环氧封装材料的性能要求,介绍了磷系阻燃环氧树脂的种类和阻燃机理,总结了当前磷系阻燃环氧树脂在电子封装领域的应用研究进展并对其未来发展趋势进行了展望,指出本征型(反应型)磷系阻燃环氧树脂存在制备困难、有效磷含量低等问题,需要进一步优化工艺并提升封装体系中的磷含量。相比之下,填充型磷系阻燃环氧树脂的制备工艺简单、阻燃剂种类多、磷含量较高,在电子封装领域应用最为广泛。     

硅橡胶复合材料阻燃研究进展

将功能填料引进到硅橡胶及其复合材料中可以获得特定功能的硅橡胶复合材料,已经成为近些年研究热点。目前阻燃剂种类繁多,但是性能比较单一,这已经不能满足人们的需要。人们在关注硅橡胶复合材料阻燃性能的同时,也考虑与其它性能兼备以及成本等问题。因此,本文综述了铂化合物、磷系阻燃剂、阻燃涂层、阻燃填料和微胶囊化阻燃剂等阻燃体系下硅橡胶复合材料的阻燃研究现状,总结了不同阻燃剂的阻燃机理,并且给出了其今后的改进方法,最后对硅橡胶复合材料阻燃研究的发展做了展望。     

聚乙烯醇无卤阻燃研究进展

鉴于环保的压力,无卤阻燃剂逐渐替代含卤阻燃剂,用在聚乙烯醇(Polyvinyl alcohol,PVA)阻燃处理中。本文综述了近年来无卤阻燃PVA的最新研究进展,总结分析了无机型阻燃剂、磷系阻燃剂、氮系阻燃剂、膨胀型阻燃剂及反应型阻燃剂对PVA的阻燃研究现状,介绍了不同类型阻燃剂的阻燃机理、优缺点以及典型阻燃剂对PVA阻燃性质和力学性质的影响;在此基础上讨论了PVA阻燃的独特性,充分利用PVA的结构特征,研制出适合PVA加工方式的阻燃剂复配配方是PVA阻燃研究的主要发展方向。     

Flame retardancy and thermal degradation of halogen-free flame-retardant biobased polyurethane composites based on ammonium polyphosphate and aluminium hypophosphite

In this work, based on castor oil (CO), flame retardant polyurethane sealants (FRPUS) with ammonium polyphosphate (APP) and aluminum hypophosphite (AHP) were prepared. The synergistic flame retardant effects between APP and AHP on flame retardancy, thermal stability, and flame retardant mechanisms of FRPUS were investigated. It was found that when the mass ratio of APP and AHP was 5:1, the limiting oxygen index (LOI) value of FRPUS increased to 35.1%, In addition, at this ratio, the parameters from cone calorimeter testing (CCT) were reduced; these parameters include peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR) and total smoke production (TSP). The thermal decomposition behavior of the FRPUS was investigated by thermogravimetric analysis (TGA). The results showed that AHP improved the thermal stability of the PUS/APP system and increased char residue at high temperatures. Moreover, the residual carbon was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM), gas phase pyrolysis products were investigated by thermogravimetric analysis/infrared spectrometry (TG-IR) and thermogravimetric analysis/mass spectrometry (TG-MS). It was observed that the flame retardant mechanisms of the APP/AHP system was the combination of gas and condensed phase flame retardant mechanisms.     

A mechanistic study of flame retardance of novel copolyester phosphorus containing linked pendant groups by TG/XPS/direct Py-MS

The flame retardant mechanism of the copolyester phosphorus containing linked pendant groups was investigated by thermogravimetric （TG）, X-ray photoelectron spectroscopy （XPS） and direct insertion probe pyrolysis mass spectrometry （DP-MS） technique. TG results show that the incorporation of phosphorus containing unit linked pendant groups can destabilize the copolyester due to the cleavage of P-CH2 bond, and phosphorus containing units cannot promote the char-formation of the copolyester during the thermal degradation of the copolyester. XPS spectra indicate that with the increase of the temperature, the P-CH2 bonds of the copolyester break down gradually, the concentration of phosphorus in the condensed phase products decrease gradually and the chemical state of phosphorus does not change in the temperature of 250-380 ℃. Direct pyrolysis MS suggests that the P-CH2 bonds cleavage occurs at pendant groups and species containing phosphorus can volatilize into the gas phase. A flame retardant mechanism is proposed for the gas phase mode of action of the halogen-free copolyester phosphorus containing linked pendant groups.     

Thermal behaviour of covalently bonded phosphate and phosphonate flame retardant polystyrene systems

Pyrolyses of the reactively flame retarded polystyrene copolymers styrene/diethyl(acryloyloxyethyl)phosphate(S/DEAEP), styrene/diethyl(methacryloyloxyethyl)phosphate(S/DEMEP), styrene/diethyl(methacryloyloxymethyl)phosphonate(S/DEMMP) and styrene/diethyl(acryloyloxymethyl)phosphonate(S/DEAMP) have been investigated with a view to obtaining information pertinent to the mechanism of their flame retardant behaviour. Studies were also carried out on the additive polystyrene systems containing triethylphosphate (TEP) and diethylethylphosphonate (DEEP) for comparison. All the systems contained 3.5 wt% of phosphorus. A range of techniques were used, namely TG with EGA, DSC, SEM, laser and microfurnace pyrolysis mass spectrometry and isothermal pyrolysis/GC-MS, to study the decompositions under a range of conditions. In the case of the additive systems, the additive was shown to be evolved before polymer decomposition occurred. Very little, if any, char residues were observed. Thus the main mechanism of fire retardant action of the phosphorus incorporated into the polystyrene as an additive would occur in the vapour phase. This mechanism prevailed regardless of whether the additive was a phosphate (TEP) or a phosphonate (DEEP). The effectiveness of the fire retardant action would be limited as the fire retardant and fuel did not volatilise together. There was evidence that some interaction occurred in the condensed phase. In all the copolymers the phosphorus content of the char was substantial. This is characteristic of the condensed phase fire retardant action of phosphorus. SEM studies showed the interior of the char to be a network of channels which would give the char a sponge-like interior which would enhance thermal insulation. The surfaces were relatively dense thus providing a barrier to escape for any gaseous products formed in the interior. Char formation and cross-linking are assumed to be the result of the presence of the strong phosphoric and phosphonic acids resulting from initial pyrolysis. Since phosphonic is the weaker acid, the polymer degradation and release of volatile products may be less inhibited in the case of the phosphonate-containing copolymers compared to the phosphate-containing copolymers. This is consistent with their shorter times to ignition. There was also evidence for some potential phosphorus vapour phase fire retardant action as phosphorus-containing species were identified among the pyrolysis products for all samples. The rate of volatile evolution from the copolymers was reduced compared to that of the corresponding additive system.     

Controlled pyrolysis of polyethylene/polypropylene/polystyrene mixed plastics with high impact polystyrene containing flame retardant: Effect of decabromo diphenylethane (DDE)

The pyrolysis of polyethylene(PE)/polypropylene(PP)/polystyrene(PS) mixed with high impact polystyrene (HIPS-Br) containing decabromo diphenylethane (DDE) as a brominated flame retardant with antimony trioxide as a synergist was performed under controlled temperature programmed pyrolysis (two steps) conditions to understand the decomposition behaviour and evolution of brominated hydrocarbons from flame-retardant additives. The liquid products were extensively analyzed by gas chromatographs equipped with FID, ECD, MSD, TCD, AED and FT-IR. The solid residue samples were analyzed by powder X-ray diffraction and combustion followed by ion-chromatography. The controlled pyrolysis of PE/PP/PS/HIPS-Br significantly affected the decomposition behaviour of HIPS-Br and subsequently the formation of decomposition products. GC/ECD analysis confirmed that the brominated hydrocarbons were concentrated in step 1 liquid products leaving less brominated hydrocarbons in the step 2 liquid products, similar to the decabromo diphenyl ether flame retardant containing mixed plastics. The yield of liquid products in step 1 from 3P/DDE-Sb(5) was 5 wt% and from 3P/DDE-Sb(0) was 2.4 wt%. The presence of antimony in the DDE containing plastics affected the yield of liquid, gas and residue products. ECD analysis showed that the presence of antimony increased the Br containing hydrocarbons and step 1 has 3-4 times higher brominated compounds than step 2 hydrocarbons in both the samples.     

Effects of phosphorus-containing thermotropic liquid crystal copolyester on pyrolysis of PET and its flame retardant mechanism

In order to compare their inherent flame retardancy and thermal stability, two phosphorus-containing thermotropic liquid crystalline copolyesters (P-TLCP) were synthesized by melting transesterification. Additionally based on the facts that the P-TLCP can work as a functional additive to enhance the flame retardancy and mechanical property of PET, we further studied the flame retardant mechanism. Scanning Electronic Microscope (SEM) observations show that the char from PET/P-TLCP is more compact, therefore more efficiently resists fire and heat attack than pure PET. Moreover, Fourier Transform Infrared Spectroscopy (FTIR) measurements of evolved gas, indicate that P-TLCP decomposes to produce phosphorus-containing small molecular compounds during the pyrolysis process, such that P-TLCP could play a flame retardant role in vapour phase. Furthermore, P-TLCP strongly inhibits the generation of combustible compounds in the pyrolysis of PET, which also helps to resist fire propagation.     

Hardware components wastes pyrolysis: energy recovery and liquid fraction valorisation

Pyrolysis of hardware components wastes consisting mainly in computers and television components was performed under nitrogen. The degradation products were separated in three fractions, solid, liquid and gaseous. Analyses of the three phases were carried out using gas chromatography (GC), mass spectrometry (MS), thermal analysis and infrared spectroscopy. The energetic content of the gas phase and the economic value of the liquid phase were also determined. The gas fraction produced was rich in light hydrocarbons and hydrogen. Consequently, its calorific value was high and widely sufficient to make the pyrolysis process self-sustained. The main products of the liquid phase were phenol and isopropylphenol (ca. 50–80 wt.%). The presence of Br-based compounds, deriving from the flame retardant employed in hardware components, were also detected. A controlled combustion of the solid phase permitted to obtain the glass fibres unaltered, which can be recycled.     

Synthesis, characterization, flame retardance and thermal properties of halogen-free expandable graphite/PMMA composites prepared from sol-gel method

In this work, silane was grafted on expandable graphite via a free-radical reaction. The modified expandable graphite has an -OEt functional group which reacts with TEOS and PMMA that was modified via a sol-gel reaction using a coupling agent that contains silicon. Synergism between silicon flame retardant and expandable graphite increased the flame retardance of the materials. Expandable graphite was functionalized using a coupling agent to increase the interactive force between the organic and inorganic phases. It enhanced the thermal stability of the composites. SEM was adopted to observe the morphology of the composites, and the behavior associated with expansion after the materials had been burned is elucidated. LOI, TGA and IPDT were employed to calculate the flame retardance and thermal stability. The results indicate that the composites are halogen-free flame retardant organic/inorganic composites. Two methods for elucidating the kinetics of thermal degradation were utilized to measure the activation energy when the composites degraded in the high-temperature atmosphere.     

Flame retardant chemical mechanisms of flame retardant viscose fibres and blends with polyester

A systematic investigation of structurally identical flame retardant viscose, modal and polyester blended fabrics and fibres was carried out in order to develop a chemical basis for more effective products based on organic and inorganic flame retardants. The oxygen indices and chemical compositions of phosphorus-nitrogen flame retardants (P-N) were used in efficiency and synergy evaluations. A new flame retardant viscose fibre containing silicid acid was included in the comparative evaluation procedure. Thermal gravimetry and X-ray diffractometry were used for determine physical factors during pyrolyzing of fibres. Charred residues were analyzed by applying elementary and solid 13-C NMR (CPMAS) spectrometry. The pyrolysis gas-liquid chromatographer connected with a gas phase FT infrared spectrometer was applied to identify the decomposition products of P-N-containing fabrics.     

Preparation of highly efficient flame retardant unsaturated polyester resin by exerting the fire resistant effect in gaseous and condensed phase simultaneously

The unsaturated polyester resins (UPR) were usually applied in electronic equipment, but the intrinsic flammability severely retrained their application. A mono‐component flame retardant poly (piperazine methylphosphonic acid neopentylglycol ester) (PPMPNG) made in our lab was selected and applied to improve their flame retardant performance. The UPR thermosets achieved UL‐94 V‐0 grade during vertical burning tests and the limiting oxygen index was as high as 32.1% when 15 wt% PPMPNG was incorporated. PPMPNG promoted the decomposition and carbonization of UPR materials in advance during heating process, and the residual mass was effectively enhanced at high temperature. The flame retardant mechanism of UPR/PPMPNG thermosets was investigated by pyrolysis‐gas chromatography/mass spectrometry tests, and the measurement of the morphologies and chemical components of the char residue. The phosphine oxygen radical was generated and then quenched the active free radicals in gas phase. Moreover, the av‐EHC of FR‐UPR was declined from 15.8 MJ kg^?1 of pure UPR to 8 9 MJ kg^?1 corresponding a reduction of 43.6%, which also verified the flame retardant effect in gas phase. The compact, integrated, and graphitized char layer was produced on materials surface and then exerted excellent barrier effect in condensed phase. Thus, the UPR/PPMPNG composites were conferred superior flame retardant properties.     

Influence of phosphorus valency on thermal behaviour of flame retarded polyurethane foams

This paper reports decomposition/pyrolysis studies of polyurethane (PU) rigid foams containing phosphinate, phosphonate or phosphate as flame retardant in order to study the effect of phosphorus oxidation state on their gas and/or solid phase action. The flame retardants analyzed were aluminium phosphinate (IPA), dimethylpropanphosphonate (DMPP), triethylphosphate (TEP) and ammonium polyphosphate (APP), which differ in oxidation state and/or decomposition temperature. Gases evolved during TGA analyses as well as solid residues have been studied by means of MS and FTIR.The results show that phosphorus flame retardants which significantly lose weight at temperatures lower than those of neat PU foams act in the gas phase irrespective of their valency: indeed, they are completely volatilized before polymer decomposition starts and thus no interaction between flame retardant and polymer can be expected. The effect of phosphorus oxidation state becomes important when flame retardant decomposition takes place in the same temperatures range as neat polymer. In this case, it seems that at lower P oxidation state (+1) a combined gas and solid phase action takes place while at higher P oxidation state (+5) only solid phase action was observed.