双酚A双(磷酸二苯酯)/聚磷酸铵/酚醛树脂膨胀阻燃剂对ABS阻燃性能研究

通过极限氧指数、水平垂直燃烧、锥形量热和电镜扫描等研究由双酚A双(磷酸二苯酯)(BDP)、聚磷酸铵(APP)及酚醛树脂(PR)组成的膨胀阻燃剂(IFR)对ABS树脂的阻燃作用,研究IFR对ABS树脂的阻燃性能和阻燃机理。结果表明:IFR阻燃剂添加量在30%左右,ABS氧指数达到29.9%,水平垂直燃烧通过UL94 V-0级,平均热释放速率下降50.9%,有效燃烧热平均值下降21.7%。扫描电镜观测发现:IFR阻燃ABS样品燃烧后能够形成连续、致密、封闭、坚硬的焦化炭层。     

一种复合阻燃剂对环氧树脂性能影响的研究

利用聚磷酸铵(APP)、三聚氰胺作为阻燃剂加入环氧树脂中制备出阻燃环氧树脂。通过氧指数仪(LOI)、垂直燃烧仪(UL-94)、热失重分析仪(TGA)研究了阻燃环氧树脂的阻燃性能和热降解行为,以扫描电子显微镜(SEM)研究了阻燃环氧树脂燃烧后炭层的表面形态,用万能拉力机研究了阻燃环氧树脂的力学性能,用差示扫描量热仪(DSC)研究了材料的固化反应动力学。研究结果表明:当加入聚磷酸铵与三聚氰胺复配的阻燃剂质量分数达到25%时,阻燃效果最好。阻燃环氧树脂的极限氧指数达到27.6%,垂直燃烧效果达到V0级,热失重结果表明600℃时残炭量达到29.2%。     

双酚A双(磷酸二苯酯)/SiO2对环氧树脂阻燃性能研究

采用双酚-A双(磷酸二苯酯)(BDP)、纳米SiO2和环氧树脂(EP)制备了阻燃环氧树脂(BDP/EP)和阻燃环氧树脂纳米材料(BDP/SiO2/EP)。结果表明:BDP和BDP/SiO2对EP均有较好的阻燃性,添加15?P和5%纳米SiO2复合体系能使EP氧指数达到30.4%,垂直燃烧通过UL94V-0级,500℃残炭率提高到30.8%,平均热释放速率下降73.1%。电镜分析表明:BDP/SiO2/EP体系能形成致密、光滑、坚硬的炭层。     

新型有机硅阻燃成炭剂的热性能及成炭机理的研究

传统膨胀型阻燃剂(IFR)中的炭源为小分子醇类化合物,因此阻燃剂具有易吸湿、易迁移、与聚合物基体不相容等缺点。为了改进这些缺点,合成了一种新型的含有机硅的三嗪类大分子成炭剂(CA),将其与多聚磷酸铵(APP)复配成膨胀型阻燃剂用于聚丙烯(PP)阻燃。通过红外光谱、热失重分析、极限氧指数、垂直燃烧、锥形量热仪、扫描电子显微镜等手段研究了CA的热性能、燃烧性能、成炭机理以及APP与CA的配比对PP阻燃性能、热稳定性能的影响。结果表明,所合成的CA显示出较好的热稳定性和优异的成炭性,残炭率为25.6%(600℃)。另外,APP与CA在阻燃PP中具有协同阻燃作用;IFR的加入能大幅度降低PP阻燃体系的热释放速率和总释放热,有效地降低烟释放量及烟释放速率,提高PP的阻燃性能。     

新型磷-氮膨胀阻燃剂在改性聚丙烯中的应用研究

采用自制干法合成的磷-氮膨胀型阻燃剂(磷酸酯三聚氰胺盐,IFR)复配聚磷酸胺(APP)和聚四氟乙烯(PT-FE)阻燃改性聚丙烯(PP),利用极限氧指数法、垂直燃烧法分析了阻燃PP的燃烧性能,通过热重分析仪、傅里叶变换红外光谱仪、扫描电子显微镜和X射线光电子能谱对阻燃PP的热降解过程、燃烧性能、残炭结构进行了分析,并研究了燃烧过程中复配阻燃体系对PP的阻燃机理。结果发现,IFR、APP和PTFE之间具有明显的阻燃协效作用;当阻燃剂总添加量为24%(APP为6%、IFR为17.5%、PTFE为0.5%)(质量分数)时,阻燃PP的极限氧指数达到30.1%,垂直燃烧测试达UL 94V-0级;加入阻燃剂还能提高PP的热稳定性。     

聚磷酸酯膨胀阻燃剂复配有机蒙脱土阻燃改性环氧树脂

以间苯二胺为固化剂,聚苯氧基磷酸210氢9氧杂磷杂菲对苯二酚酯（POPP）、聚磷酸铵（APP）为阻燃剂, 复配质量分数为1 %有机蒙脱土（OMMT）为膨胀阻燃体系,对环氧树脂（EP）进行阻燃改性。通过极限氧指数测定仪、垂直燃烧测定仪同步热分析仪、锥形量热等研究改性EP的阻燃性能、热性能和力学性能。结果表明,当膨胀阻燃体系（2.5 %POPP/APP+1 %OMMT）添加量为3.5 %时,改性EP可达UL 94 V-0级,同时LOI为25.2 %;当膨胀阻燃体系添加量为11 %时,改性EP的LOI值进一步升高到31.7 %;阻燃剂的加入,使EP的初始分解温度略有降低,但残炭量明显增加;POPP/APP/OMMT的加入很大程度上降低了EP的热释放速率、烟释放量和平均热释放速率。     

聚磷酸铵/可膨胀石墨阻燃环氧树脂的性能

将聚磷酸铵(APP)与可膨胀石墨(EG)进行复配后添加到环氧树脂(EP)中,以间苯二胺(PDA)为固化剂,制备阻燃环氧树脂固化物,通过极限氧指数(LOI)、垂直燃烧(UL-94)和热重分析(TGA)测试研究了材料的阻燃性能、热降解行为,通过锥形量热(CONE)测试研究了材料的燃烧行为,通过扫描电镜(SEM)研究了材料炭层的形貌,同时还研究了APP与EG的不同配比对EP材料阻燃性能的影响。结果表明:当APP与EG的质量比为3∶2、添加量为5%时,阻燃EP材料通过了UL-94 V-0级,LOI值达到了29.0%。TGA测试结果表明:阻燃剂APP及EG的加入明显地改变了材料的热降解行为,促进了环氧树脂材料的提前降解和成炭,降低了材料的热降解速率,材料在700℃时的残炭量由14.6%提高到了29.9%。CONE测试结果表明:阻燃剂的加入明显降低了材料的热释放速率(HRR)和总热释放量(THR)。SEM测试结果表明:阻燃材料燃烧后形成了致密均一的炭层,能很好地阻止氧气和热量进入到材料的内部,同时减少可燃气体的逸出,从而抑制了基体树脂的进一步降解和燃烧,提高了材料的阻燃性能。     

三聚氰胺包覆聚磷酸铵阻燃环氧树脂的研究

研究了三聚氰胺包覆聚磷酸铵(MPP)与季戊四醇(PER)阻燃环氧树脂的燃烧性能。通过热重分析初步探讨了MPP/PER阻燃剂对环氧树脂的阻燃机理。结果表明:MPP/PER对环氧树脂具有很好的阻燃作用,能有效提高环氧树脂的氧指数和垂直燃烧性能,降低环氧树脂的热释放速率,使燃烧过程变得稳定,降低环氧树脂的火灾危险性。热重分析表明:添加了阻燃剂以后,环氧树脂的初始分解温度降低,残炭量显著增加,阻燃剂发挥了凝聚相阻燃的作用。     

膨胀阻燃线型低密度聚乙烯阻燃性能的研究

为了解决线型低密度聚乙烯(LLDPE)易燃烧的问题,利用聚磷酸铵(APP)、三嗪系成炭剂(CFA)复配成膨胀阻燃剂,乙烯-丙烯酸酯-马来酸酐(EAEM)作为弹性体加入到线型低密度聚乙烯(LLDPE)中,制备成膨胀阻燃聚乙烯材料。研究发现当膨胀阻燃剂添加量达到28%时阻燃效果最好,膨胀阻燃聚乙烯的氧指数达到31.0%,并能通过UL 94V-0级。通过对材料极限氧指数(LOI)、水平垂直燃烧(UL 94)、热失重分析(TG)、锥形量热仪(CONE)、力学性能、扫描电镜(SEM)等分析手段对膨胀阻燃线型低密度聚乙烯的阻燃机理进行了分析。     

微胶囊聚磷酸铵的制备及阻燃环氧树脂的性能研究

采用三聚氰胺甲醛树脂预聚物通过原位聚合法制备了微胶囊聚磷酸铵阻燃剂(MAPP),利用扫描电镜观察到MAPP颗粒表面包覆了一层树脂。采用热重分析法、垂直燃烧法和氧指数法研究了聚磷酸铵(APP)和MAPP阻燃环氧树脂材料的热性能及阻燃性能。结果表明:与APP相比,MAPP阻燃环氧树脂的最大失质量温度、残炭量以及阻燃性能均显著提高。添加10%APP或MAPP的环氧树脂材料的氧指数均大于27.0%,阻燃性能均达到UL 94 V-0级,且MAPP样条燃烧后可形成膨胀炭层。相比于APP,MAPP阻燃材料的力学强度均有所改善,当阻燃剂填充10%时材料的拉伸强度从32.6 MPa提高到35.7 MPa,冲击强度从10.8 kJ/m2提高到11.6 kJ/m2,均高于纯环氧树脂材料的力学强度。     

不同芳基磷酸酯与膨胀型阻燃剂复配阻燃PP的研究

采用间苯二酚双(二苯基)磷酸酯(RDP)、双酚A双(二苯基)磷酸酯(BDP)、磷酸三甲苯酯(TCP)和异丙苯基磷酸酯(IPP)作为阻燃协效剂与膨胀型阻燃剂(IFR)复配阻燃聚丙烯(PP)。研究了芳基磷酸酯的种类对PP/IFR复合材料阻燃性能、热稳定性能和力学性能的影响,并通过热重分析(TGA)、扫描电镜(SEM)等对材料进行了表征。结果表明:芳基磷酸酯对PP/IFR复合材料具有一定的协同阻燃作用。当芳基磷酸酯用量为5.0%时,PP/IFR/TCP、PP/IFR/IPP、PP/IFR/RDP和PP/IFR/BDP复合材料的氧指数(OI)由PP/IFR的28.5%分别提高到29.5%、30.0%、30.5%和29.5%,垂直燃烧级别由UL 94V-1级提升至UL 94V-0级;同时,RDP和BDP可提高PP/IFR复合材料的热稳定性能,500℃时的残余率分别高达15.4%和12.9%。此外,RDP和BDP的加入有利于IFR粒子的分散,从而改善了材料的力学性能。     

EG与IFR复合阻燃ABS协同效应及热失重行为研究

将可膨胀石墨(EG)、P-N型膨胀阻燃(剂IFR)与ABS树脂共混,制作复合阻燃材料。用氧指数(OI)、UL 94测试和锥形量热仪(CONE)探讨了EG与IFR复合阻燃ABS的协同效应。通过热失重分析(TG)研究了阻燃ABS体系的热失重行为。结果表明:EG与IFR协同阻燃ABS,OI达到29%,UL 94为V-0级,热释放速率大幅度降低,EG与IFR复合阻燃ABS具有一定的协同效应;在空气气氛下,EG与IFR可以相互促进成炭,且形成的炭层稳定在,850℃也不会分解。     

A novel intumescent flame‐retardant epoxy resins system

Pentaerythritol diphosphonate melamine–dicyandiamide–formaldehyde resin salt, a novel macromolecular intumescent flame retardants (IFR), was synthesized, and its structure was a caged bicyclic macromolecule containing phosphorus characterized by IR, NMR and element analysis. The flame retardancy and thermal behavior of a new IFR system for epoxy resin were investigated by LOI, UL‐94 test, TG, and IR. Activation energy for the decomposition of samples was obtained using Kissinger equation. 25% of weight of IFR were doped into epoxy resin to get 27.5 of LOI and UL 94 V‐0. The TG curves and IR spectra show that IFR decreases the initial decomposition temperature and the maximum weight loss rate of epoxy resin, and enhances the thermal stability of epoxy resin at high temperatures and char yield. The activation energy for epoxy resin containing IFR was decreased by 44.8 kJ/mol, which shows that IFR can catalyze decomposition of epoxy resin. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

硼硅树脂的合成及其对PE-LD/EVA/IFR复合材料阻燃性能和力学性能的影响

利用二苯基二甲氧基硅烷和苯基三甲氧基硅烷合成了聚硼硅氧烷树脂,并探索了最佳的合成工艺条件。将聚硼硅氧烷树脂添加到低密度聚乙烯/乙烯醋酸乙烯酯共聚物/膨胀型阻燃剂(PE LD/EVA/IFR)复合材料中,以期可以提高膨胀型阻燃剂与聚合物基体的相容性。采用氧指数仪、热重分析仪、力学性能测试等表征手段分析了复合材料的阻燃性能、热性能和力学性能。结果表明,聚硼硅氧烷树脂可提高复合材料的阻燃效果,并且对复合材料的力学性能没有明显的影响。     

Synergistic effect of phosphorus-containing nanosponges on intumescent flame-retardant polypropylene

A novel nanosponge (NS) was synthesized via the crosslinking of β-cyclodextrin with epoxy resin. Subsequently, a phosphorus-containing nanosponge (P–NS) was prepared by the absorbance of resorcinol bis(diphenyl phosphate) into the NS, and it was used as a synergistic agent of intumescent flame retardance in a polypropylene (PP)/melamine pyrophosphate/pentaerythritol composite. The synergistic effect between P–NS and the intumescent flame retardant (IFR) was investigated by thermogravimetry, limiting oxygen index (LOI) testing, vertical burning (UL-94) testing, cone calorimeter testing, and scanning electron microscopy (SEM). The results show that P–NS significantly improved the flame retardancy of the PP/IFR composite. When 3.0 wt % P–NS replaced the same amount of IFR in the composite, the LOI value increased from 29.0 to 32.5%, the UL-94 rating was enhanced from V-1 to V-0, and the peak heat release rate decreased substantially from 343 to 235 kW/m². Simultaneously, the total heat release and mass loss rate decreased dramatically. Furthermore, the SEM results show that the quality of char formation of the PP/IFR/P–NS was superior to that of the PP/IFR composite. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

阻燃剂对热固性酚醛树脂阻燃性能影响的研究

通过氧指数、垂直燃烧等级及产烟率测定研究了氢氧化铝(ATH)、氢氧化镁(MH)、膨胀石墨(EG)、膨胀型阻燃剂(IFR)等以单一或协同复配的形式对酚醛树脂(PF)体系阻燃性能的影响,并采用差热分析(DTA)对体系的微观热行为进行了研究。结果表明,放热量最小的体系为ATH/MH/EG/PF,ATH/MH/EG/IFR/PF体系的氧指数最大,达到96。ATH/MH/PF体系的产烟率最低(72%)。添加阻燃剂后,体系的垂直燃烧等级可提高到UL94V-0级。     

Performance of an intumescent-flame-retardant master batch synthesized by twin-screw reactive extrusion: effect of the polypropylene carrier resin

A novel way of preparing an intumescent flame retardant (IFR) and its master batch by the reactive extrusion of melamine phosphate and pentaerythritol, together with a polypropylene (PP) carrier, in a twin-screw extruder has been established. The effect of the PP carrier resin on the flame retardancy and water resistance of the intumescent-flame-retarding PP materials was investigated by using the limited oxygen index (LOI), UL94 test, elemental analysis (EA), thermogravimetric analysis (TGA) and water solubility testing, respectively. In addition, the mechanism of the carrier effect was analysed by melt flow index (MFI), scanning electron microscopy (SEM), and TGA. The experimental results show that with increasing content of carrier resin (PP) in the IFR master batch from 0 to 15 wt%, the flame retardancy LOI of the PP/IFR (25 wt% loading) blend increased from 29.5 to 32, and the UL94 level at 1.6 mm thickness was improved from failure to a V-0 rating. In addition, the water resistance of a flame-retarded composite at 25 wt% IFR loading was greatly improved, i.e. after treatment with hot water at 70 °C for 168 h, the reducing rate of element N in the IFR/PP blend decreased from 18.3% with 5 wt% carrier resin to 12.9% with 15 wt% carrier resin, and the LOI reduction rate decreased from 15.3% without any carrier resin to 10.9% with 15 wt% carrier resin, while the flame-retarded PP with an IFR master batch containing 10–15 wt% carrier resin maintained its UL94 V-0 rating at 3.2 mm thickness. The improvement in flame retardancy was attributed to the improved flame-retardant (FR) dispersion due to the carrier resin, while the improved water resistance was explained by the lowered water solubility of the IFR, the improved FR dispersion and the improved compatibility of the FR with the matrix resin due to the carrier resin. Reactive extrusion is a novel way to obtain pelletissed IFRs without powder pollution and their corresponding flame-retarding materials with a number of desired properties. Copyright © 2004 Society of Chemical Industry     

Effect of an intumescent flame retardant on the fracture toughness (Mode I), thermal,and flame-retardant properties of continuous glass fibre-reinforced polypropylene composites

To solve the ‘wicking actions’ caused by fibre, intumescent flame retardant (IFR) was introduced into the resin of continuous glass fibre-reinforced polypropylene (CGF/PP) composites. The influence of IFR on the properties of composites were investigated by a double cantilever beam test, thermogravimetric analysis, limiting oxygen index, vertical burning test (UL-94), and cone calorimetric test. The results revealed that when the content of IFR was 15 wt-%, the initial Mode I interlaminar fracture toughness (G_{I init.}) and propagation fracture toughness (G_{I prop.})) were enhanced by 123.2 and 70.26%, respectively, compared to composites with no IFR. The maximum weight loss rate (T_max) was improved to various degrees. Samples could self-extinguish with an oxygen concentration of 32.4% and achieve a UL-94 V-1 rating. Furthermore, the peak of heat release rate, total heat release, fire performance index, and mass loss rate tests indicated that IFR could dramatically enhance the flame retardancy of the composites.     

环氧磷酸的合成及对环氧树脂固化物的阻燃耐热性研究

将环氧树脂和磷酸直接反应,制得了含磷11%、与环氧树脂相容性较好的新型含磷阻燃剂(EPH),用氧指数测定、热重法等方法研究了其对环氧树脂二乙烯三胺固化物阻燃耐热性的影响。实验结果表明该阻燃剂对环氧树脂固化物有较好的阻燃作用,能明显提高树脂固化物的残炭量,主要发挥凝聚相阻燃作用。     

膨胀型阻燃剂NP430对三元乙丙橡胶阻燃性能的影响

采用膨胀型阻燃剂NP430填充三元乙丙橡胶(EPDM),研究其阻燃性能.结果表明:膨胀型阻燃剂NP430对EPDM具有很好的阻燃效果,外加酸源乙烯-醋酸乙烯共聚物(EVA)和碳源高苯乙烯(HS)树脂具有更好的协同阻燃作用.当EPDM/EVA/HS并用比为80/8.6/11.4、膨胀阻燃剂NP430用量为90份时,极限氧指数可达47.6.填充石蜡油会明显降低EPDM的阻燃性能,但不影响燃烧膨胀过程.而填充少量甲基丙烯酸锌、酚醛树脂等有机填料对EPDM的阻燃性能影响很小;填充炭黑、白炭黑、碳酸钙、可膨胀石墨等无机填料会导致燃烧产生的气体逸出,严重不利于膨胀过程,导致膨胀型阻燃剂不能发挥阻燃作用.