新型树状单分子磷-氮膨胀阻燃剂的合成及阻燃性能研究

以六氯环三磷腈、对羟基苯甲醚、新戊二醇以及三氯氧磷等为原料, 合成一种新型树状单分子磷-氮膨胀阻燃剂六(4-(5,5-二甲基-1,3-二氧杂环己内磷酸酯基苯氧基))环三磷腈(Ⅵ). 标题化合物结构经IR、MS 及¹H NMR 证实. 热失重分析表明标题化合物具有较高的热稳定性和良好的成炭性, 氮气氛下的起始分解温度为270 ℃, 600 ℃时炭残余量达45.2%. 实验表明, 标题化合物对环氧树脂呈现出良好的阻燃效果.     

Synthesis and thermal stability of a novel phosphorus-nitrogen containing intumescent flame retardant

A novel phosphorus-nitrogen containing intumescent flame retardant （P-N IFR） was prepared via the reaction of dichlor-opentate with N-methylaniline. The structure of the product was confirmed by ^1H NMR, ^31p NMR, MS and IR. TGA analysis showed it has effective thermal stability.     

Effect of hybrid phosphorus-doped silica thin films produced by sol-gel method on the thermal behavior of cotton fabrics

The aim of this work was to prepare hybrid organic-inorganic silica thin films to provide cotton fabrics with flame retardant properties and to investigate the films’ influence on the thermal and burning behavior of the treated samples. The fabrics were modified with three different sols in order to study the effect of pure silica sol-gel precursor, γ-aminopropyltriethoxysilane (APTES), and that of the hybrid sols consisting of the APTES and the phosphorus compound diethylphosphite. Furthermore, in order to improve the cross-linking degree and the phosphorus-nitrogen synergistic effect on flame retardancy of the P-doped silica thin film the melamine-based resin was added in the third sol. To evaluate the chemical structure of the coating material, pure xerogels of the treatment solutions were applied to glass slides and tested by ATR FT-IR spectroscopy. The cotton fabrics were impregnated with the sols by a padding-squeezing process and then dried. Thermal behavior of the treated cotton samples was investigated by thermogravimetric/differential scanning calorimetry analysis (TGA-DTG/DSC) and compared to the untreated one. The flame retardancy was tested according to the ASTM D 1230 standard method. The results showed a substantial enhancement of char-forming properties and flame retardancy for the fabrics modified with the thin films.     

Fabrication of halogen-free ammonium phosphate with two components via a simple method and its flame retardancy in polypropylene composites

In this paper, a halogen-free flame retardant with two different functional components was prepared via a simple method. The novelty of this work is the combination of acid source and char-forming agent in one compound simultaneously. And the advantage of this method lies in effectively avoiding the mixture of several components for composites during thermal processing and improving the flame retardancy of polymers. Besides, the chemical structure of modified ammonium phosphate (MAPP) was confirmed by Fourier transform infrared spectra (FTIR) and X-ray diffraction spectra (XRD), respectively. The results indicate that thermal decomposition process of APP after modification is obviously changed. When polypropylene (PP) is composited with 30 phr MAPP, the limiting oxygen index value can reach 28.5 % and pass vertical burning tests (UL-94) V-1 rating. Simultaneously, thermal gravimetric analysis demonstrates that the introduction of diethanolamine can improve the char-forming rate and char residue of PP/APP composites. Except that, the thermal pyrolysis of MAPP detected by FTIR spectra deduces that the char-forming process happens at 350–400 °C. The analysis on char residue after combustion indicates that the cross-linking bonds of P–O–C groups appear. At last, a potential condensed mechanism was primarily proposed.     

表面化学接枝改性阻燃棉织物的制备与性能

采用高碘酸钠对棉织物表面进行选择性氧化生成醛基,选取乙二胺与醛基反应,通过膦氢化加成反应将阻燃剂亚磷酸二甲酯接枝到棉织物表面,最后通过三羟甲基三聚氰胺对棉织物表面进行接枝改性,制备了含三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物.通过傅里叶红外光谱（FTIR）对改性后棉织物的结构进行了表征,通过极限氧指数（LOI）测试研究了其阻燃性能,通过锥形量热测试研究了其燃烧行为,通过在40℃皂水中洗涤10次考察了其耐水性能,通过扫描电子显微镜测试了其表面及燃烧后炭层的形貌.研究结果表明,经表面改性后,棉织物的LOI值由（19.5±1.0）%提高到了（43.1±1.0）%,经耐水洗测试后,LOI值仅下降至（42.6±1.0）%,保持了非常好的阻燃性能,表明通过表面接枝方法制备的三羟甲基三聚氰胺/乙二胺/亚磷酸二甲酯阻燃棉织物具有非常好的耐水洗性能.表面阻燃改性提高了棉织物在燃烧过程中的成炭性能,形成的连续膨胀的炭层较好地保护了内部织物,抑制了织物的降解和燃烧,从而提高了棉织物的阻燃性能.     

Polyamide 6 with a flame retardant encapsulated by polyamide 66: Flame retardation, thermo-decomposition and the potential mechanism

A novel encapsulated flame retardant containing phosphorus-nitrogen(MSMM-Al-P) was prepared by encapsulating with polyamide 66(PA66-MSMM-Al-P) for the flame retardation of polyamide 6(PA6).The structure and thermal properties of PA66-MSMM-Al-P were characterized by Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy and thermogravimetric analysis.The flammability of PA6 containing flame retardants(MSMM-Al -P and PA66-MSMM-Al-P) was investigated by the limiting oxygen index test,vertical burning test and cone calorimeter. The flame retardancy and cone calorimetric analyses suggested a synergistic effect between PA66 and MSMM-Al-P in the flame-retardant PA6.Thermal stability of the flame-retardant PA6 was also investigated.     

阻燃剂二(5,5-二溴甲基-1,3,2-二氧六环磷酰)双酚A的合成

近年来,针对高分子材料易燃进行阻燃化处理,赋予其难燃性和抑烟性,对于有效阻止材料火灾事故发生和抑制火焰传播具有重要意义~([1-2]).磷、溴作为两类重要的阻燃元素,具有各自相应的阻燃机理,能够通过凝聚相和气相共同发挥阻燃作用,降低材料的燃烧性能.     

本质阻燃聚苯乙烯/蒙脱土纳米复合物的制备及性能

通过原位聚合法制备了本质阻燃聚苯乙烯[P(St-co-AEPPA)]/有机改性蒙脱土(OMMT)纳米复合物[P(St-co-AEPPA)/OMMT], 并用普通聚苯乙烯/有机改性蒙脱土(PS/OMMT)复合物作为对比实验, 研究了含磷、氮单体丙烯酸羟乙基-苯氧基-二乙基磷酰胺(AEPPA)和OMMT等添加物对本质阻燃聚苯乙烯性能的影响.用X射线衍射仪(XRD)和透射电子显微镜(TEM)分析了复合材料的结构与形貌, 并对OMMT在基体中的分散机理进行了讨论.用差示扫描量热仪(DSC)、热重分析(TGA)和微型量热仪(MCC)研究了材料的热性能和燃烧性能.结果表明, AEPPA和OMMT能够显著提高基体的热稳定性和阻燃性.     

Preparation of Poly(phosphoric acid piperazine) and Its Application as an Effective Flame Retardant for Epoxy Resin

A phosphorus-nitrogen containing flame retardant additive of poly(phosphoric acid piperazine),defined as PPAP,was synthesized by the salt-forming reaction between anhydrous piperazine and phosphoric acid,and the dehydration polymerization under heating in nitrogen atmosphere.Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy,13C and 31p solid-state nuclear magnetic resonance measurements.The synthesized PPAP and curing agent m-phenylenediamine were blended into epoxy resin (EP) to prepare flame retardant EP thermosets.The effects of PPAP on the fire retardancy and thermal degradation behavior of cured EP/PPAP composites were investigated by limiting oxygen index (LOI),vertical burning (UL-94),thermogravimetric analysis/infrared spectrometry (TG-IR) and cone calorimeter tests.The morphologies and chemical compositions of char residues for cured epoxy resin were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS),respectively.The results demonstrated that the flame retardant EP thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 30.8％ when incorporating 5wt％ PPAP into the EP thermosets.The TGA results indicated that the synthesized PPAP flame retardant additive possessed high thermal stability and excellent charring capability.Meanwhile,the incorporation of PPAP stimulated the epoxy resin matrix to decompose and charring ahead of time due to its catalytic decomposition effect,which led to a higher char yield at high temperature.The morphological structures and the analysis results of XPS for char residues of EP thermosets revealed that the introduction of PPAP benefited the formation of a sufficient,more compact and homogeneous char layer containing phosphorus-nitrogen flame retardant elements on the material surface during combustion.The formed char layer with high quality effectively prevented the heat transmission and diffusion,limited the production of combustible gases,and inhibited the emission of smoke,leading to the reduction of heat and smoke release.     

Poly(lactic acid) nanocomposites with improved flame retardancy and impact strength by combining of phosphinates and organoclay

To minimize the loading level of the char-forming phosphorus based flame retardants in the poly(lactic acid) (PLA) with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blending method incorporating organically modified montmorillonite (OMMT) and aluminium diethylphosphinate (AlPi) additives. The influence of AlPi and OMMT on flame retardancy and thermal stability of PLA was thoroughly investigated by means of the limiting oxygen index (LOI), UL94 test, cone calorimeter, X-ray diffraction (XRD), thermogravimetric analysis and scanning electronic microscopy (SEM). The experimental results show that the PLA/AlPi/OMMT system has excellent fire retardancy. The LOI value increases from 19% for pristine PLA to 28% for the flame-retarded PLA. Cone calorimeter analysis of the PLA/AlPi/OMMT exhibits a reduction in the peak heat release rate values by 26.2%. Thermogravimetric analysis and SEM of cone calorimeter residues indicate that OMMT significantly enhances the thermal stability, promotes char-forming and suppresses the melt dripping. The research of this study implies that the combining of the flame retardant and organoclay results in a synergistic effect. In addition, the flame-retarded PLA nanocomposite also exhibits notable increase in the impact strength and the elongation at break.     

Synthesis and characterizations of novel phosphorous-nitrogen containing poly(ether sulfone)s

The synthesis of novel phosphorus-nitrogen synergism aromatic poly(ether sulfone)s was carried out successfully by using phosphorus-containing and nitrogen-containing biphenol-like monomers, 1,1′-bis(4-hydroxyphenyl)-metheylene-bispheny-1-oxophosphine oxide (DOPO-PhOH) and 1,2-dihydro-4-(4-hydroxyphenyl)phthalazin-1(2H)-one (DHPZ), in the usual synthesis procedure. Polymers with sufficient molecular weights could be obtained. The structure of the phosphorus-nitrogen containing poly(ether sulfone)s was characterized by means of Fourier transform infrared spectra (FTIR) and nuclear magnetic resonance spectroscopy (¹H NMR, ³¹P NMR). The influence of monomer ratio on their thermal stability was also investigated by adjusting the proportion of DOPO-PhOH/DHPZ (mol/mol) from 80/20 to 20/80. The molecular weight and glass-transition temperatures (T_g′s) of the polymers increased with increasing content of the DHPZ monomer. The high thermal stabilities were depended on the different proportion of diol type incorporated.     

含硫环状膦酸酯衍生物的合成及其热性能

以三氯化磷、苯和硫粉为原料,用离子液体法绿色合成了硫代苯基膦酰二氯(3);3与季戊四醇或新戊二醇反应合成了两种新型含硫磷系阻燃剂--2,4,8,10-四氧杂-3,9-二磷杂螺环[5.5]十一烷-3,9-二硫-3,9-二苯(1)或5,5-二甲基-2-苯基-2-硫代-1,3-二氧-2-磷杂环己烷(2).用~1H NMR,IR,DSC和TG对其结构和性能进行了表征.结果表明,1具有良好的成炭性和热稳定性.     

Functionalizing nano-montmorillonites by modified with intumescent flame retardant: Preparation and application in polyurethane

The 2-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)ethy-amino)-N,N,N-triethyl-2-oxoethanaminium chloride (compound c) containing phosphorus-nitrogen structure was synthesized and characterized. A novel intumescent flame retardant, namely montmorillonite (MMT) by modified with compound c (c-MMT), was prepared by ion exchanging of the nanometer Na⁺-montmorillonite (Na-MMT) with compound c. Both FTIR and X-ray diffraction (XRD) indicated that compound c had intercalated with Na-MMT and exfoliated c-MMT/PU nanocomposites have obtained by in-situ polymerization. TEM results further support the formation of the exfoliated nanocomposites. The thermal stability and flammability of c-MMT/PU composites were investigated by thermogravimetric analysis (TGA) and cone calorimeter test respectively. The results showed that the addition of flame retardant c-MMT enhanced the thermal stability and flame retardancy of PU significantly. SEM results indicated that c-MMT can achieve better dispersion in the chars after combustion and the compact and dense intumescent char is formed for c-MMT/PU composites after combustion. It is found that the char structure plays an important role for c-MMT in PU resin. The thermal stability and flame retardancy of PU resin were also significantly improved by an addition of c-MMT in PU resin.     

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。     

Effect of a novel flame retardant containing silicon and nitrogen on the thermal stability and flame retardancy of polycarbonate

A novel flame retardant (PSiN), containing silicon and nitrogen, was synthesized using N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane and diphenylsilanediol through solution polycondensation and it was added to polycarbonate (PC). The structure and thermal properties of PSiN were characterized by fourier transform infrared spectroscopy and thermogravimetric analysis (TG) tests. The effect of PSiN on the flame retardancy and thermal behaviors of PC was investigated by limited oxygen index (LOI), vertical burning test (UL-94), and TG tests. The results showed that the flame retardancy and the thermal stability of PC are improved with the addition of PSiN. When 1 mass% PSiN and 0.5 mass% diphenylsulfone sulfonate (KSS) are incorporated, the LOI value of PC is found to be 46, and class V-0 of UL-94 test is passed. The char structure observed by scanning electron microscopy indicated that the surface of the char for PC/KSS/PSiN system holds a firmer and denser char structure when compared with neat PC and PC/KSS system.     

Thermal and flame retardant properties of novel intumescent flame retardant low-density polyethylene (LDPE) composites

A char-forming agent (CFA) and silica-gel-microencapsulated ammonium polyphosphate (MCAPP) were selected to form novel intumescent flame retardant system (IFRs), and then the influence of this novel IFRs on the thermal and flame retardant properties of low-density polyethylene (LDPE) were studied. The results of cone calorimetry show that the flame retardant properties of LDPE with 30?wt% novel IFR (CFA/MCAPP?=?1:3) improve remarkably. The heat release rate peak, total heat release (THR) decreases, respectively, from 1479.6 to 273.5?kW?m^?2 and from 108.0 to 80.5?MJ?m^?2. The LDPE composite with CFA/MCAPP?=?1:3 has the excellent water resistance, and it can still obtain a UL-94?V-0 rating after treated with water at 70?°C for 168?h.     

Polypropylene composites filled by magnesium hydroxide coprecipitated with foreign ions

Rod‐like magnesium hydroxide (MH) particles were prepared via coprecipitation of the magnesium salt with foreign ions, such as copper(II), zinc(II), iron(III), and nickel(II). Flame retardant polypropylene (PP) composites were fabricated using these particles. The microstructure, flame retardation, mechanical properties, thermal behavior, and oxidation‐induced temperature were characterized. It was found that foreign ion compounds increased the flame retardancy. MH containing a zinc compound presented a similar performance as that of neat MH. The presence of a copper compound decreased the thermal behavior and mechanical properties of the flame retardant composite, while iron and nickel compounds brought some improvements. In addition, the thermal degradation mechanisms of the flame retardant composites were investigated by Fourier transform infrared (FTIR) spectroscopy at different temperatures. Copyright © 2008 John Wiley & Sons, Ltd.     

Char-forming mechanism of a novel polymeric flame retardant with char agent

A novel phosphorus-containing compound, poly(2-hydroxy propylene spirocyclic pentaerythritol bisphosphonate) (PPPBP) has been proved to be an excellent flame retardant for polyethylene terephthalate (PET) fabrics. In order to understand its flame retardant mode, FT-IR and XPS are used to investigate the char-forming mechanism of PPPBP. FT-IR spectra results show that with the increase of temperature, P-O-C group of PPPBP breaks down gradually, and species containing CC double bond appear. XPS spectra indicate that PPPBP produces phosphoric or polyphosphoric acid during thermo-decomposition. In the high temperature range (>400 °C), CC and phosphorus-containing complexes become the major components of the charred residue of PPPBP. Data of XPS and FT-IR spectra give positive evidence that PPPBP yields high amount of carbonaceous chars by producing phosphoric or polyphosphoric acid, which inhibit the oxidation of carbon atoms, and simultaneously impel the formation of carbon and species containing carbon double bond with outstanding heat resistance.     

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