一步法合成低聚磷酸酯阻燃剂RDP

以磷酸三苯酯(TPP)和间苯二酚为原料,采用一步法合成低聚磷酸酯阻燃剂间苯二酚双（二苯基磷酸酯）RDP。研究了反应物原料比、催化剂种类及用量、酯化反应温度和反应时间等因素对反应的影响,并通过高效液相色谱监测反应进程。结果表明：当TPP和间苯二酚摩尔比按2.1:1.0时,催化剂用量为0.010%,在120~130 ℃下进行酯交换反应,反应4 h,RDP单体收率可达到90.7%。产品性能指标优良,热重分析表明其热稳定性符合工程塑料加工要求。     

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%.     

无卤阻燃剂新戊二醇基苯基磷酸酯的合成与性能

采用氯化磷酸单苯酯(MPCP)和新戊二醇(NPG)为原料,以4-二甲氨基吡啶(DMAP)为催化剂,以四氢呋喃为溶剂,合成了一种含有新戊二醇结构的环状磷酸酯无卤阻燃剂新戊二醇基苯基磷酸酯(NGPP),并研究了其对环氧树脂阻燃性能的影响.反应收率可达81.2%.产物的结构经核磁、红外和质谱进行了表征.热分析表明,NGPP的起始热分解温度和最大热分解温度分别为189.0℃和259.4℃.NGPP在不饱和聚酯树脂中表现出较好的阻燃性能,且在添加适量三聚氰胺后阻燃性能进一步提高.     

一步法合成低聚磷酸酯阻燃剂间苯二酚双(二苯基磷酸酯)

以磷酸三苯酯(TPP)和间苯二酚为原料,采用一步法合成低聚磷酸酯阻燃剂间苯二酚双(二苯基磷酸酯)(RDP),利用红外、核磁、ESI-MS对其结构进行表征。研究了催化剂种类及用量、物料比、酯化反应温度和反应时间等因素对反应的影响,并通过高效液相色谱监测反应进程。通过L9(34)正交试验以及单因素法进行优化,得到适宜反应条件。结果表明,当TPP和间苯二酚摩尔比为2.1∶1.0时,以离子液体[Bmim]OH作为催化剂,催化剂用量为0.010(wt)%,在120~130℃下进行酯交换反应,反应4h,所得产品中RDP单体色谱收率可达到90.7%。产品性能指标优良,热重分析表明其热稳定性符合工程塑料加工要求。     

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.     

咔唑-磷酸酯阻燃剂的合成及阻燃聚碳酸酯应用

聚碳酸酯作为一种重要的有机高分子材料,被广泛应用于汽车装饰、电子电器和生活日用品生产中,由于聚碳酸酯自身阻燃性能级别低,因此在实际应用中必须进行阻燃处理.本文针对聚碳酸酯的阻燃需求,设计合成了结构新颖的咔唑-磷酸酯阻燃剂,测试结果显示该阻燃剂具有良好的阻燃性能,能够作为聚碳酸酯阻燃材料使用.     

新型单组分磷-氮膨胀型阻燃剂的合成及其阻燃性能

以氯化螺环磷酸酯(1)和对甲苯胺(2)为原料,经亲核取代反应合成了"三源"一体的新型单分子磷-氮膨胀型阻燃剂——季戊四醇螺环磷酰对甲苯胺(3),其结构经1H NMR和IR表征。考察了溶剂、原料配比、反应温度、反应时间和缚酸剂对3产率的影响。合成3的最佳反应条件为:乙腈为溶剂,三乙胺为缚酸剂,1 10mmol,n(1)∶n(2)=1∶3,于80℃反应4 h,产率79.3%。阻燃性能研究结果表明,3的初始分解温度为220℃,500℃成炭率达43.3%。     

三聚氰胺磷酸盐阻燃剂的合成及性能表征

以新方法合成了三聚氯胺磷酸盐自膨胀阻燃剂(MP)，其结构经元素分析、XRD，TG，DSC，IR等表征。测定了含MP阻燃材料的阻燃性能，讨论了其阻燃机理及特点。用MP对聚丙烯进行阻燃处理后其氧指数可达27．1；徐覆含MP自膨胀防火涂料的五层板在模拟火灾中的耐火极限达39min，发泡倍数为90倍-100倍。     

O,O′-二(2-氯乙基)-O″-[2-二(2-氯乙氧基)磷酰丙基]磷酸酯的合成

报道了以三氯化磷、乙二醇、环氧乙烷、丙酮和氯气等原料合成新型阻燃剂O,O′-二(2-氯乙基)-O″-[2-二(2-氯乙氧基)磷酰丙基]磷酸酯的方法.探讨了反应温度、催化剂以及反应时间等条件对各步反应的影响,产品总收率92%以上.采用元素分析、红外光谱和核磁共振等表征了合成化合物的结构.     

Flame retardancy and thermal degradation of intumescent flame retardant polypropylene with MP/TPMP

The performances of the novel intumescent flame retardant (IFR) polypropylene (PP) composites containing melamine phosphate (MP) and tris(1‐oxo‐2,6,7‐trioxa‐1‐phosphabicyclo[2,2,2]methylene‐4)phosphate (TPMP) were investigated. The flame retardancy of IFR‐PP system was characterized by limiting oxygen index (LOI) and UL 94 and cone calorimeter. The morphology of the char obtained after cone calorimeter testing was studied by scanning electron microscopy (SEM). The thermal oxidative degradation (TOD) of the composites was investigated by using thermogravimetric analysis (TGA) and real‐time Fourier transform infrared spectroscopy (RT‐FTIR). Compared with the PP/ TPMP or PP/ MP binary composite, at the same addition level, the LOI values of the PP/MP/TPMP ternary composites increase and reach V‐0 at the suitable MP/TPMP ratio. The results of TGA and RT‐FTIR showed the existence of the interaction between IFR and PP. Copyright © 2008 John Wiley & Sons, Ltd.     

反应性挤出加工制备无卤阻燃高分子材料

聚合物反应性加工集聚合物加工与化学反应为一体,以聚合物加工装置为反应器,通过聚合物加工过程中的化学反应形成新物质和新结构,实现高分子材料的高性能化和功能化,是高分子材料科学的研究前沿之一.本文简要介绍了我们研究小组近年来采用反应性挤出加工制备高性能无卤阻燃高分子材料方面的研究进展.利用反应性挤出加工剪切力强、温度可控以及易于传质传热的特点实现了常规方法难以合成的高黏阻燃剂三聚氰胺磷酸盐季戊四醇酯（MPP）和三聚氰胺氰尿酸（MCA）的高效合成,制备了综合性能优良的聚丙烯/MPP、尼龙6/MCA等无卤阻燃高分子材料.研究所涉及的化学和物理方法,为聚合物无卤阻燃提供了高效、经济、环保和易于工业化的新技术,并拓宽了聚合物反应性加工的应用领域.     

阻燃剂苯并咪唑的微波合成研究进展

苯并咪唑类化合物广泛应用于医药、农药等领域,也在阻燃剂中具有重要应用.因此,利用微波辅助方法快速、高效地合成苯并咪唑类化合物已成为近年来的研究热点,本文对此进行了综述,并从经济与规模化制备苯并咪唑等方面进行了展望.     

Preparation of high-efficient flame retardant PA6 via DOPO-ITA initiated ring-opening polymerization of caprolactam

It has been a long-term challenge to synthesize intrinsically flame retardant polyamide 6 (FRPA6) with high-molecular weight. In this work, through the ring-opening polymerization of caprolactam initiated by 9,10-dihydro-10-[2,3-di(hydroxycarbonyl)propyl]-10 phosphaphenanthrene-10-oxide (DOPO-ITA), intrinsically flame retardant PA6 with high-molecular weight was successfully prepared. Its chemical structure, thermal stability, mechanical and combustion properties, as well as the retarding mechanism were thoroughly characterized in detail. The FRPA6 containing 3.0% retardant could achieve a V-0 rating with an LOI value of 31.2%. An interesting phenomenon was observed during V-0 tests. The melt drip slowly extended downward to form a long strip after moving fire, which was in favor of its heat release in a short time, thereby effectively prevented it from igniting the cotton. That is, a facile method to prepare intrinsically high-efficiency fire retardant polymer via ring opening and polycondensation was proposed.     

A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties

A novel flame‐retardant epoxy resin, (4‐diethoxyphosphoryloxyphenoxy)(4‐glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epichlorohydrin with (4‐diethoxyphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene and was characterized by Fourier transform infrared, ³¹P NMR, and ¹H NMR analyses. The epoxy resin was further cured with diamine curing agents, 4,4′‐diaminodiphenylmethane (DDM), 4,4′‐diaminodiphenylsulfone (DDS), dicyanodiamide (DICY), and 3,4′‐oxydianiline (ODA), to obtain the corresponding epoxy polymers. The curing reactions of the PPCTP resin with the diamines were studied by differential scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in the following order: DDM > ODA > DICY > DDS. In addition, the thermal properties of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame retardancies were estimated by measurement of the limiting oxygen index (LOI). Compared to a corresponding Epon 828‐based epoxy polymer, the PPCTP‐based epoxy polymers showed lower weight‐loss temperatures, higher char yields, and higher LOI values, indicating that the epoxy resin prepared could be useful as a flame retardant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000     

Manufacturing,thermal stability,and flammability properties of polypropylene containing new single molecule intumescent flame retardant

Melamine salt of pentaerythritol phosphate kaolin (MPPK) was synthesized by the reaction of pentaerythritol phosphate with kaolin (K) and melamine. The structure of MPPK was confirmed by EDXS, ¹H NMR, FTIR, and XRD. MPPK was blended with polypropylene (PP) at different loading levels. Thermogravimetric analysis (TGA) results showed that MPPK improved the thermal stability of PP at high temperatures in all PP composites. Vertical burning rate test manifested that PP composites can achieve V0 at 20% and 25% MPPK loading levels. Cone calorimeter data exhibited that addition of 25% MPPK to PP reduced peak of heat release rate (pHRR) and total heat release (THR) by 86% and 76% and increased the char residue after test to 67%. The results of PP/25% MPPK composite were compared with the data obtained from PP containing 25% K and 25% of traditional intumescent flame retardant composed of melamine phosphate (MP), pentaerythritol (PE), and K. The outcomes indicated that MPPK was more efficient in flame retardancy than the other systems. The digital photographs and SEM images for char residue demonstrated that MPPK succeeded in forming cellular and coherent char layer on the PP surface. The main advantage of adding 25% MPPK to PP was its ability to preserve nearly the inner half of the sample without burning after cone calorimeter test.     

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.     

Synergistic effect of nanoflaky manganese phosphate on thermal degradation and flame retardant properties of intumescent flame retardant polypropylene system

Nanoflaky manganese phosphate (NMP) was synthesized from manganese nitrate and trisodium phosphate dodecahydrate, and used as a synergistic agent on the flame retardancy of polypropylene (PP)/intumescent flame retardant (IFR) system. The thermogravimetric analysis (TGA), real time Fourier-transform infrared (RTFTIR) spectroscopy measurements, cone calorimeter (CONE) and microscale combustion calorimeter (MCC) were used to evaluate the synergistic effects of NMP on PP/IFR system. When IFR + NMP was fixed at 20 wt% in flame retardant PP system, the TGA tests showed that NMP could enhance the thermal stability of PP/IFR system at initial temperature from about room temperature to 440 °C and effectively increase the char residue formation. The RTFTIR results revealed that NMP could clearly change the decomposition behavior of PP in PP/IFR system, which promotes decomposition at the initial temperature from about room temperature to 260 °C and forms more effective barrier layer to protect PP from decomposing at high temperature from about 260 °C to 500 °C. The CONE tests indicated that the addition of NMP in PP/IFR system not only reduced the peak heat release rate (HRR), but also prolonged the ignition time. The MCC results revealed that PP/IFR/NMP system generated less combustion heat over the course of heating than that of PP/IFR system. And scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used to explore the char residues of the PP/IFR systems with and without NMP.     

Flame retardant polystyrene copolymers: preparation,thermal properties,and fire toxicities

A new phosphorous‐ and nitrogen‐containing reactive monomer, DMPMA, was first synthesized by nucleophilic substitution reaction of 2‐(6‐oxido‐6H‐dibenz[c,e][1,2]oxaphos‐phorin‐6‐yl) methanol, N‐hydroxymethyl acrylamide and methyldichlorophosphate. The copolymer of styrene (St) and DMPMA (poly(St‐co‐DMPMA)) was prepared and then characterized by Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis (TGA), microscale combustion calorimeter and steady‐state tube furnace (SSTF). The results proved that poly(St‐co‐DMPMA) was well synthesized, while the glass transition temperature of the copolymer was decreased with increasing DMPMA content. The TGA results showed that the initial degradation temperature of poly(St‐co‐DMPMA) decreased, but its char yield and decomposition temperature improved compared to that of pure polystyrene. After incorporating DMPMA, the fire performance of the copolymer was significantly improved. The results obtained from the SSTF indicated that the carbon monoxide and smoke yield density were increased due to the incomplete combustion of the copolymer. Copyright © 2014 John Wiley & Sons, Ltd.     

Thermal degradation and flame retardancy of epoxy resins containing intumescent flame retardant

Pentaerythritol diphosphonate melamine-urea-formaldehyde resin salt, a novel cheap macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR. Epoxy resins (EP) were modified with IFR to get the flame retardant EP, whose flammability and burning behavior were characterized by UL 94 and limiting oxygen index (LOI). 25 mass% of IFR were doped into EP to get 27.2 of LOI and UL 94 V-0. The thermal properties of epoxy resins containing IFR were investigated with thermogravimetry (TG) and differential thermogravimetry (DTG). Activation energy for the decomposition of samples was obtained using Kissinger equation. The resultant data show that for EP containing IFR, compared with EP, IFR decreased mass loss, thermal stability and R _max, increased the char yield. The activation energy for the decomposition of EP is 230.4 kJ mol⁻¹ while it becomes 193.8 kJ mol⁻¹ for EP containing IFR, decreased by 36.6 kJ mol⁻¹, which shows that IFR can catalyze decomposition and carbonization of EP.