基于环三磷腈磷氮阻燃剂的合成及其在聚氨酯泡沫的应用

以六氯环三磷腈、对羟基苯甲醛、苯胺及亚磷酸二乙酯等原料,成功合成阻燃剂六（4-苯胺基次甲基苯氧基-亚磷酸二乙酯基）环三磷腈（HADPPCP）,用于阻燃基于苹果酸多元醇的聚氨酯硬泡。HADPPCP具有良好的热稳定性和成炭性,氮气气氛下的初始分解温度为191.9℃,700℃时的残炭量高到46.8%（质量）。HADPPCP的加入可以改善聚氨酯硬泡的热稳定性、阻燃性能和燃烧行为。添加25%(质量)的HADPPCP可以将聚氨酯泡沫的氧指数从18%提高到25%,最大热释放速率和总热释放量分别从230 kW/m²和20.1 MJ/m²降低至213 kW/m²和16.6 MJ/m²,总产烟量从10.5 m²下降到5.3 m²。     

聚合磷酸酯阻燃剂的合成及应用研究

以三氯氧磷、乙醇及乙二醇为主要原料,二氯乙烷为溶剂,辛酸亚锡为催化剂,三聚氰胺为缚酸剂,制备了含端羟基的聚合磷酸酯阻燃剂。讨论了反应的主要因素,确定适宜的反应条件为:n(三氯氧磷)∶n(乙醇)∶n(乙二醇)为1∶1∶1.05,0℃滴加入乙醇,反应依次在25℃、45℃、65℃分别保温反应2h、2h和1h。产率89.2%,数均相对分子质量MnGPC=3750,分布指数PD=1.27。用FT IR,1 H NMR表征了产物结构。在聚氨酯硬泡沫中进行了应用实验,极限氧指数达到29,且表现出良好的低温尺寸稳定性。     

新型反应型磷-氮阻燃剂的合成与应用

采用膦酸酐和苯胺为原料,通过一步法合成了一种含N-P的具有反应活性的β-（N-苯基酰胺）乙基甲基次膦酸(CEMP),通过FTIR和1H-NMR对其结构进行了表征。初步探讨了CEMP在环氧树脂(EP)中的应用。结果表明:CEMP是一种有效的EP阻燃剂,当阻燃剂添加量为20 %(质量分数,下同)时即可满足UL94-V0的阻燃等级,极限氧指数达到29.4 %,弯曲强度比未阻燃的EP有了较大的提高,但玻璃化转变温度（Tg)）有所下降。     

含磷阻燃剂DOPO-HQ的合成、表征及应用

对含磷阻燃剂DOPO-HQ的合成条件进行了优化,通过~1HNMR、FTIR及元素分析对合成的DOPO-HQ进行了表征,并以其作为阻燃剂,制备阻燃硬质聚氨酯泡沫(FRPUF),以研究其阻燃性能。结果表明,以四氯化碳为溶剂,在DOPO与对苯醌物质的量比为1.1∶1、反应温度为78℃、反应时间为14 h的最优条件下,成功合成了DOPO-HQ,该工艺操作简单、过程更安全、产品纯度高、收率高。DOPO-HQ的加入能显著提高硬质聚氨酯泡沫的阻燃性能,添加45份DOPO-HQ后,硬质聚氨酯泡沫的垂直燃烧等级可以达到V-0级,极限氧指数(LOI)达到27.0%,属难燃级别,其总热释放明显降低,表现出明显的气相阻燃机理,具有一定应用价值。     

水溶性磷-氮协效膨胀型阻燃剂的制备及应用

采用聚乙烯亚胺与含磷中间体前体为原料,制备了一种用于水发泡软质聚氨酯泡沫材料的水溶性磷-氮协效膨胀型阻燃剂,讨论了阻燃剂结构对阻燃效果的影响。结果表明,在阻燃剂用量6. 67%条件下,可将聚氨酯泡沫的极限氧指数从17%提高至24%,UL94从V-2提高到V-0级,且不影响发泡过程。     

醇-磷酸酯法降解废旧聚氨酯的研究

选用不同的降解剂,采用醇-磷酸酯法降解废旧聚氨酯泡沫,对降解产物进行性能测试。结果表明：以一缩二乙二醇和磷酸三正丁酯为降解剂降解聚氨酯软质泡沫效果较好。以降解产物作为部分原料制备聚氨酯硬质泡沫塑料体,对其性能测试并与不加降解产物制备的聚氨酯硬质泡沫体比较,结果表明：降解产物作为部分原料对聚氨酯硬质泡沫塑料的性能影响不大。     

含磷-溴-氮阻燃剂的合成及应用研究

以三氯氧磷、季戊四醇、2,3-二溴丙醇、2,4,6-三溴苯酚及三聚氰胺等为原料合成了两种含磷-溴-氮阻燃剂,即O-(2,4,6-三氧杂-1-氧基磷杂双环[2.2.2]辛烷-4-亚甲基)-O-2,3-(二溴丙基)磷酸三聚氰胺盐和O-(2,4,6-三溴苯基)磷酸三聚氰胺盐.实验证明这两种阻燃剂对不饱和聚酯树脂具有较好的阻燃作用,且含结炭结构的前者阻燃效果要优于后者.     

次磷酸铝阻燃剂的合成及应用

采用一水次磷酸钠和十八水硫酸铝为原料,合成了一种高效无卤的阻燃剂次磷酸铝(PAH),当反应温度为90℃,次磷酸钠与硫酸铝摩尔比(以下简称物料比)为7.5∶1,反应时间为3 h时,产率可达98.5%,通过红外光谱仪、电感耦合等离子体原子发射光谱仪等对产品结构进行了表征,并研究了PAH在硬质聚氨酯泡沫塑料(PU硬泡)中的应用,结果表明,经阻燃改性的PU硬泡材料氧指数达30,垂直燃烧UL94达V-0级。该方法工艺简便,绿色环保,易工业化。     

Synthesis and characterization of bio-based intumescent flame retardant and its application in polyurethane

A novel bio-based P-N containing intumescent flame retardant melamine starch phytate (PSTM) was prepared via the reaction of phytic acid starch ester with melamine and characterized by Fourier transform infrared, scanning electron microscopy and thermogravimetric analysis (TGA). The effects of PSTM on thermal properties and flammability of rigid polyurethane (PU) foams were analyzed by TGA, limit oxygen index (LOI), vertical burning tests (UL-94) and cone calorimeter measurement. The TGA results demonstrated that the thermal stabilities of PU/PSTM foam at high temperature was enhanced with the increasing additive amount of PSTM. The results showed that PU foam with 30 php PSTM (PU/PSTM-30%) observed an LOI value of 25.9 and a UL-94 rating of V-0. Cone calorimetry data showed that peak heat release rate, total heat release and smoke production rate of PU/PSTM-30% were distinctly lower than that of pure PU. Further experimental results demonstrated that PSTM promotes well charring of PU which could protect the foam from combustion. This work developed a novel bio-based intumescent flame retardant by suing phytic acid and starch as the acid source and carbon source, respectively, which is of great significance to the preparation of environmental-friendly flame retardants.     

反应型含磷阻燃剂的应用研究进展

含磷阻燃剂具有低烟无毒、阻燃效果好的特点,是典型的无卤阻燃剂。本文阐述了含磷阻燃剂的阻燃机理,综述了将反应型含磷阻燃剂引入聚氨酯、环氧树脂和丙烯酸树脂等体系中所采用的不同改性方法,这些反应型阻燃聚合物均是主链或侧链含磷。本文还对近几年来国内外关于含磷阻燃剂在这些体系中的应用研究进展进行了概述,提出未来应加深对阻燃剂协同机理及含磷阻燃剂水性化和光固化的研究。     

反应型磷氮阻燃剂/可膨胀石墨复配阻燃聚氨酯泡沫

将反应型阻燃剂六(4-磷酸二乙酯羟甲基苯氧基)环三磷腈(HPHPCP)和可膨胀石墨(EG)复配,制备了阻燃聚氨酯泡沫,详细研究了复配阻燃剂对聚氨酯泡沫的物理力学性能、热稳定性以及阻燃性能的影响。结果表明,阻燃聚氨酯泡沫的密度和热导率随着复配阻燃剂中EG含量的增加而升高;压缩强度随着EG含量的增加呈现先增加后降低的趋势。热失重表明复配阻燃剂大大提高了聚氨酯泡沫的热稳定性。聚氨酯泡沫的初始分解温度(T_10%)从212.9℃,分别提高到222.0、231.2和243.2℃;700℃残炭量从7.6%分别提高到26.3%、31.6%和37.9%。聚氨酯泡沫的阻燃性能随着复配阻燃剂中EG含量的增加而提高。阻燃聚氨酯泡沫的极限氧指数从19%提高到29%,均能通过UL-94水平燃烧HF-1等级和垂直燃烧V-0等级。     

Synthesis of a novel cross‐linked organophosphorus‐nitrogen containing polymer and its application in flame retardant epoxy resins

A novel cross‐linked organophosphorus–nitrogen polymetric flame retardant additive poly(urea tetramethylene phosphonium sulfate) defined as PUTMPS was synthesized by the condensation polymerization between urea and tetrahydroxymethyl phosphonium sulfate. Its chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, ¹³C and ³¹P solid‐state nuclear magnetic resonance. The synthesized PUTMPS and curing agent m‐phenylenediamine were blended into epoxy resins to prepare flame retardant epoxy resin thermosets. The effects of PUTMPS on fire retardancy and thermal degradation behavior of EP/PUTMPS thermosets were investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), cone calorimeter measurement, and thermalgravimetric analysis (TGA) tests. The surface morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy and X‐ray photoelectron spectroscopy (XPS), respectively. Water resistant properties of epoxy resin thermosets were evaluated by putting the samples into distilled water at 70°C for 168 h. The results demonstrated that the EP/12 wt% PUTMPS thermosets successfully passed UL‐94 V‐0 flammability rating and the LOI value reached 31.3%. The TGA results indicated that the incorporation of PUTMPS promoted epoxy resin matrix decomposed and char forming ahead of time, which led to a higher char yield and thermal stability for epoxy resin thermosets at high temperature. The morphological structures and analysis of XPS for the char residues of the epoxy resin thermosets shown that PUTMPS benefited to the formation of a sufficient, more compact, and homogeneous char layer with rich flame retardant elements on the materials surface during burning, which prevented the heat transmission and diffusion, limited the production of combustible gases, inhibited the emission of smoke, and then led to the reduction of the heat release rate and smoke produce rate. After water resistance tests, EP/12 wt% PUTMPS thermosets still remained excellent flame retardancy. Copyright © 2015 John Wiley & Sons, Ltd.     

Inorganic/organic phosphorus-based flame retardants synergistic flame retardant rigid polyurethane foam

The flame-retardant rigid polyurethane foam (RPUF) composites are fabricated by ammonium polyphosphate (APP) with pentaerythritol phosphate (PEPA), phenoxycycloposphazene (PCP), and aluminum diethylphosphinate (ADP), respectively, which are labeled as RPUF-1, RPUF-2, and RPUF-3. The influence of flame retardants on the apparent density and compressive strength of RPUF is studied. The results reveal that flame retardants not only improve the apparent density, but also improve the compressive strength of RPUF composites. The limiting oxygen index (LOI) results reveal that these inorganic/organic phosphorus-based flame retardants improve the LOI significantly, especially for RPUF-2 and RPUF-3 systems. The cone calorimeter test results suggest that the peak of heat release of RPUF-1, RPUF-2, and RPUF-3 systems decrease by 38%, 41%, and 52% likened to that of pure RPUF. And APP and ADP system performs best in declining the heat release. And APP and PEPA systems perform best in decreasing the smoke release. The flame retardancy mechanism of RPUF composites is analyzed in details.     

新型硅硼磷阻燃剂的合成以及在防火涂料中的应用

以9,10⁃二氢⁃9⁃氧杂⁃10⁃磷杂菲⁃10⁃氧化物（DOPO）、二甲氧基甲基乙烯基硅氧烷（DTTLL）和硼酸［B（OH）₃］合成了一种分子结构中含有硅硼磷的阻燃剂（SiBP）。分别用傅里叶变换红外光谱仪（FTIR）和氢核磁共振光谱仪（¹H⁃NMR）表征了SiBP 的化学结构。用热失重分析仪（TG）表征了SiBP的热稳定性,在氮气氛围下SiBP的起始分解温度为110 ℃,并且在氮气气氛下800 ℃的残炭率高达40 %。以硅丙乳液为基体,通过加入多聚磷酸铵（APP）为协效阻燃剂,SiBP为主阻燃剂,双季戊四醇（Di⁃PE）,三聚氰胺（MEL）,无机填料硅微粉进行复配制备一种防火涂料。利用极限氧指数测定仪（LOI）,UL 94垂直燃烧测试、TG、大木板燃烧实验对其防火性能进行详细的表征和分析,利用扫描电子显微镜观察炭层燃烧后的微观和宏观形貌。通过压缩性能测试仪、电子万能试验机对炭层强度和涂料剥离强度进行表征。结果表明,当APP为10份（质量份,下同）、SiBP为20份、Di⁃PE为4份、MEL为8份、硅微粉为25份时,极限氧指数提高到29.2 %,UL 94达到V⁃0级,残炭率为38.5 %,剥离强度提高到0.325 kN/m,炭层压缩强度增加到1.4 MP,亲水性增加。     

环境友好型阻燃高回弹聚氨酯软泡性能

开发环境友好型聚氨酯是目前聚氨酯（polyurethane,PU）泡沫塑料领域的热点课题。在PU中引入大豆分离蛋白质（soy protein isolate,SPI）,采用阻燃聚醚制备了环境友好型阻燃高回弹聚氨酯软泡。研究了SPI的不同添加方式及用量对聚氨酯软泡物理、力学、阻燃和生物降解性能的影响。结果表明,SPI以添加的方式而不是替代聚醚的方式加入软泡性能更好;少量添加SPI可以提高PU软泡的开孔率、密度、压陷硬度、舒适因子、回弹率和断裂伸长率,对压缩永久变形率、拉伸强度和极限氧指数影响不大。SPI改变了PU的硬段结构,可以有效促进聚氨酯泡沫的生物降解。     

Synthesis and application of a sulfur‐containing phosphoric amide flame retardant for nylon fabric

A sulfur‐containing flame retardant (SFR) was synthesized from polyphosphoric acid, epoxy chloropropane, and thiourea. Using a water‐soluble isocyanate‐terminated (WIT) cross‐linker, the flame retardant was applied as a flame‐retardant finishing on nylon fabric. WIT is a compound that not only cross‐links SFR and nylon cellulose but also contains no formaldehyde. Comparisons of the main performances of SFR with those of N‐methyloldimethylphosphonopropionamide (known as ‘Pyrovatex CP’) and a bicyclic phosphonite (known as ‘Antiblaze 19T’) indicate that the presence of sulfur in SFR plays a crucial role in decreasing the flammability of the nylon fabric. The limiting oxygen index value and damaged carbon length of the finished nylon fabric were 29.4% and 5.7 cm, respectively, when the concentrations of SFR and WIT were 200 and 40 g/L, respectively, and the baking temperature and time were 150 °C and 3 min, respectively. After 10 laundry cycles, the fabric still retains some flame retardancy. Copyright © 2016 John Wiley & Sons, Ltd.     

一种新型含磷阻燃剂的合成

以邻苯基苯酚和三氯化磷为起始原料,路易斯酸为催化剂,合成了新型阻燃剂[(6 氧 6H 二苯并 (c,e)(1,2) 氧磷杂己环 6 酮) 甲基] 丁二酸(DDP),测定了DDP在丙酮 水混合体系中的溶解度。结果表明,质量百分数0.6的丙酮 水溶液是DDP重结晶较为合适的溶剂,为产品的纯化提供了基础数据。