膨胀型阻燃剂PEPA/MP阻燃聚丙烯的研究

用季戊四醇磷酸酯(PEPA)作成炭剂,与三聚氰胺磷酸盐(MP)和协效剂按一定比例复配成膨胀型阻燃剂(IFR),用于聚丙烯(PP)的阻燃。研究IFR含量对PP燃烧性能和力学性能的影响,结果表明:IFR添加量为23%时,阻燃PP的氧指数(LOI)为26.3%,阻燃等级达到UL94 V-0级。与PP相比,阻燃PP的拉伸强度、冲击强度降低,弯曲强度提高。采用差示扫描量热仪(DSC)、热失重(TG)、扫描电镜(SEM)等方法对阻燃PP的热性能、成炭性能等进行分析,结果表明:随IFR添加量增大,PP的结晶度增大,起始分解温度降低,高温成炭率提高。阻燃PP燃烧后形成表面致密,内部多孔的膨胀炭层结构。     

KH550改性PEPA对PP/IFR体系阻燃、耐水和力学性能的影响

利用硅烷偶联剂KH550对季戊四醇磷酸酯(PEPA)进行表面改性,得到Si-PEPA,将其与三聚氰胺聚磷酸盐(MPP)复配成膨胀型阻燃剂(IFR)对聚丙烯(PP)进行阻燃改性。研究了KH550改性PEPA对PP/IFR体系阻燃、耐水和力学性能的影响。利用极限氧指数(LOI)仪、垂直燃烧(UL94)仪、锥形量热(CONE)仪对阻燃PP的燃烧性能进行测试,结果表明,当IFR的添加量为20%时,PP/MPP/Si-PEPA体系可以达到UL94 V-0级,氧指数达到32.5%,最大热释放速率(PHRR)和总热释放量(THR)都较PP/MPP/PEPA体系有明显降低。热重分析(TGA)显示,经KH550处理后,PP/IFR材料的热稳定性显著提高。经70℃热水浸泡72 h后,PP/MPP/Si-PEPA材料仍然可以通过UL94 V-1级。同时,KH550对PEPA的表面处理也提高了PP/IFR材料的力学强度。     

膨胀型阻燃剂PEPA/MPP阻燃LGFPP性能研究

将季戊四醇磷酸酯(PEPA)和三聚氰胺聚磷酸盐(MPP)复配成一种膨胀型阻燃剂(IFR),用于对长玻纤增强聚丙烯(LGFPP)进行阻燃。采用极限氧指数测试、垂直燃烧测试、扫描电子显微镜观察、热重分析、力学性能测试等方法探讨了该IFR组成对LGFPP的阻燃性能、热稳定性能以及力学性能的影响。结果表明,IFR的总添加量为20%,当PEPA与MPP质量比为11∶9时,复配阻燃效果最佳,阻燃LGFPP的极限氧指数值为26.1%,UL–94燃烧等级达到V–0级;生成的炭层致密、连续性好且稳定;阻燃LGFPP表现出较好的热稳定性与力学性能。     

IFR/可膨胀石墨及协效剂氧化锌对PP阻燃性能影响的研究

制备了聚丙烯(PP)/有机膨胀型阻燃体系(IFR)、PP/IFR/可膨胀石墨(EG)和PP/IFR/可膨胀石墨(EG)/协效剂氧化锌(ZnO)三种体系,通过力学性能、氧指数(LOI)、垂直燃烧测试及热重分析(TG),探讨了复配膨胀型阻燃体系IFR/EG与协效阻燃剂ZnO之间的协同效应。结果表明,当IFR/EG/ZnO质量比为9.25/9.25/1.5时,阻燃PP的LOI值达到最高,同时阻燃PP的力学性能比不含ZnO的PP有所提高。TG结果表明,ZnO的加入使阻燃PP的热稳定性得到提高,形成了更稳定的保护层,从而提高了PP的阻燃效果。     

硅酮粉与复合膨胀阻燃剂协同作用对聚丙烯阻燃性能的影响

研究了硅酮粉、聚磷酸铵(APP)与季戊四醇(PER)组成的复合膨胀阻燃剂(IFR)协同作用对聚丙烯(PP)热降解及阻燃性能的影响。通过TGA、LOI极限氧指数表征了PP材料热降解及阻燃性能。采用扫描电镜(SEM)表征了燃烧后残留炭层的表面形貌。结果表明:在PP燃烧过程中,硅酮粉能促进形成致密的,紧凑的膨胀阻燃炭层。当阻燃剂用量占体系的30%时,在聚丙烯阻燃体系中,硅酮粉与膨胀性IFR阻燃剂协同阻燃效果比单独使用IFR的阻燃效果好。硅酮粉与膨胀性IFR阻燃剂协同阻燃效果最佳用量为:硅酮粉为2%,IFR为28%。     

一种磷-氮阻燃剂的合成及其在聚丙烯中的应用

采用高温高压溶液聚合法合成了一种新型磷-氮阻燃剂N-对苯二甲酸-N'-(N-亚磷酸-乙二胺)-乙二胺(IFR)。将制得的阻燃剂与聚磷酸铵(APP)进行复配,并与聚丙烯(PP)进行共混,制备了阻燃PP复合物。通过极限氧指数(LOI)测定、垂直燃烧实验(UL94)、热重分析(TG)测试对复合材料的阻燃性能和热稳定性进行了表征,并借助扫描电子显微镜(SEM)表征了残炭表面形态。结果表明,当添加9%IFR和21%APP时,PP/IFR/APP体系的极限氧指数达到最大,为28.8%,并通过了UL94 V-0级。在该比例下燃烧所形成的炭层呈现出膨胀的连续结构,可以很好覆盖于材料表面形成阻隔效果。这表明该阻燃剂与APP复配对PP具有良好的阻燃作用。     

IFR阻燃EVAC燃烧性能的研究

采用不同质量配比的聚磷酸铵(APP)、季戊四醇(PER)、三聚氰胺(MEL)制备磷氮膨胀型阻燃剂(IFR)体系,用以阻燃乙烯-乙酸乙烯酯共聚物(EVAC),探讨了三种组分配比对EVAC阻燃性能和力学性能的影响。用拉伸性能评价IFR与EVAC相容性对力学性能的影响。利用锥形量热仪(CONE)评价IFR用量对EVAC阻燃性能和燃烧火灾性能参数的影响及阻燃机理。结果表明,PER与EVAC的相容性优于APP与EVAC的相容性;在IFR体系添加量为30份,APP∶PER=4∶1时氧指数最高,达到28.5%,材料的垂直燃烧测试可达UL–94 V–0级,水平燃烧测试达到HB级;CONE测试表明当阻燃剂IFR添加量为30%时,EVAC的火灾性能指数提高,生烟速率下降。     

EG与IFR复合阻燃ABS的动态燃烧性和协同效应

将可膨胀石墨(EG)与P-N型膨胀阻燃剂(IFR)复合阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS)树脂,阻燃剂添加量为20%(质量分数,下同),通过极限氧指数(LOI)仪、垂直燃烧测试(UL-94)仪、锥形量热(CONE)仪和扫描电镜(SEM)研究了EG与IFR复合阻燃ABS的协同效应。结果表明,EG/IFR质量比为1/1为最佳配比,阻燃ABS的LOI达到29%,UL-94为V-0级;EG与IFR复合阻燃ABS,表现出一定的协同作用;通过SEM观察ABS/EG/IFR试样燃烧后样品发现,EG与IFR起到协同阻燃作用。     

基于胞苷酸阻燃剂的制备及其对PP阻燃性能的影响

为了提高膨胀阻燃剂(IFR)对于聚丙烯(PP)的阻燃效率,选择具有阻燃潜质的胞苷酸衍生物作为协效剂。胞苷酸与三缩水甘油基异氰尿酸酯反应形成阻燃微球,同时引入镍离子与磷酸基团反应成盐,以提高其热稳定性,得到基于胞苷酸镍的阻燃微球TC-Ni,通过红外光谱研究了其结构。将TC-Ni与膨胀阻燃剂(IFR)复合,通过熔融共混法制备阻燃PP复合材料。通过极限氧指数、垂直燃烧等研究了复合材料的阻燃性能,通过热失重分析测试其热稳定性,采用扫描电镜观察炭层结构。结果表明,添加17%IFR和1%TC-Ni可以使样品通过UL94 V–0级别,并且其LOI提高到29.2%。TC-Ni改善了PP/IFR形成的膨胀炭形态和完整性,使炭层表层炭致密,内层多孔,从而有效地提高了PP/IFR体系的阻燃效率。     

三嗪膨胀阻燃剂/聚苯醚阻燃聚丙烯的性能研究

以三嗪成炭发泡剂(CFA)、聚磷酸铵(APP)及二氧化硅(Si O2)复配制备成三嗪膨胀阻燃剂(IFR);将聚苯醚(PPO)以不同的比例取代IFR体系中的CFA成分,制备出新型膨胀阻燃剂,并将其添加到聚丙烯(PP)中制备阻燃PP材料。通过极限氧指数(LOI)和垂直燃烧(UL 94)测试研究了材料的阻燃性能,通过拉伸性能、弯曲性能和冲击性能测试研究了材料的力学性能,通过热重分析(TGA)测试研究了材料的热稳定性及热降解行为。结果表明:当阻燃剂用量为20%、PPO替换CFA的量为20%时,阻燃PP材料能通过UL 94V-0级,氧指数为31.0%;当阻燃剂用量为22%、PPO替换CFA的量为30%时,阻燃PP材料依然能通过UL 94V-0级,氧指数为30.9%,随着PPO替换比例的增加,材料的阻燃性能逐渐下降。力学性能测试结果表明,与单独添加IFR相比,随着PPO替换量的增加,阻燃材料的力学性能略有下降,但下降幅度不大。TGA测试结果表明,当阻燃剂用量为20%、PPO替换20%的CFA时,对材料的热降解行为和成炭性能几乎没有影响。总之,在保证材料阻燃性能的前提下,用适量PPO替换CFA,在一定程度上降低了三嗪膨胀阻燃剂及膨胀阻燃PP材料的成本,从而提高了产品的市场竞争力。     

纳米Al_2O_3对含磷环氧树脂体系的性能影响

研究了以纳米Al_2O_3作为协同阻燃剂,对EP/DOPO和EP/HPCTP树脂固化物阻燃性能的影响。通过热重分析测试(TGA)、动态热机械分析测试(DMA)、氧指数测定(LOI)及垂直燃烧测试(UL-94)重点探讨了树脂固化物的耐热及阻燃性能。测试结果表明,含磷阻燃剂有助于提高环氧树脂固化物的阻燃性能,但会降低其玻璃化转变温度(Tg)。随着纳米Al_2O_3的加入,残炭率(800℃)、极限氧指数(LOI)得到进一步的提高,并且能够在一定程度上提升树脂固化物的玻璃化转变温度(Tg)和初始热裂解温度(T5%)。     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.     

天然高分子对生物聚酯P(3,4)HB复合材料阻燃性能的影响

以三聚氰胺磷酸盐(MP)和季戊四醇磷酸酯(PEPA)复配的膨胀型阻燃体系阻燃聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3,4)HB], 分别用木质素、壳聚糖和海藻酸钠3种天然高分子作为成炭剂代替部分PEPA, 采用熔融共混法制备P(3,4)HB基阻燃复合材料。通过热重分析仪(TGA)、微型量热仪(MCC)、垂直燃烧仪(UL-94)、极限氧指数仪(LOI)及扫描电镜(SEM)等对其热稳定性、热燃烧性能、阻燃特性及炭渣形貌进行了表征与分析, 对比研究了3种天然高分子对P(3,4)HB基复合材料阻燃性能的影响。结果表明:含有木质素的复合材料体系燃烧后形成了致密而连续的炭层, 且能达到V-0级别, 而含壳聚糖或海藻酸钠的复合材料体系燃烧后形成的炭层结构多孔而疏松, 只能达到V-2级。     

聚乳酸/苯基次膦酸铈复合材料的制备及性能

采用简单方法合成苯基次膦酸铈(CeP),并将其作为阻燃剂加入聚乳酸(PLA)中,通过熔融共混技术制备聚乳酸/苯基次膦酸铈(PLA/CeP)复合材料。通过热重(TG)、极限氧指数(LOI)、UL-94垂直燃烧(UL-94)、微型量热(MCC)研究复合材料的热稳定性、阻燃性能和燃烧性能。通过阻燃测试发现,CeP能够提高复合材料阻燃性能,PLA/CeP20极限氧指数能达到24.3%并通过UL-94 V-2级别。热重分析的结果表明,CeP显著提高了PLA/CeP复合材料初始分解温度和成炭率。MCC测试结果表明,CeP能明显降低PLA/CeP复合材料火灾危险性。PLA/CeP20热释放速率峰值(PHRR)和总热释放(THR)分别为397 W/g和13.6 kJ/g,与纯聚乳酸相比,分别下降了13.9%和28.0%。因此,苯基次磷酸铈对聚乳酸具有良好的阻燃效果。     

Flame retardation and thermal degradation of flame‐retarded polypropylene composites containing melamine phosphate and pentaerythritol phosphate

The flame retardation of polypropylene (PP) composites containing melamine phosphate (MP) and pentaerythritol phosphate (PEPA) was characterized by limiting oxygen index (LOI) and UL 94. The morphology of the char obtained from the combustion of the composites was studied by scanning electron microscopy (SEM). The thermal degradation of the composites was investigated using thermogravimetric (TG) analysis and real‐time Fourier transform infrared (RTFTIR) spectroscopy. It has been found that the PP composites containing only MP do not show good flame retardancy even at 40% additive level. Compared with the PP/MP binary composites, all the LOI values of the PP/MP/PEPA ternary composites at the same additive loading increase, and UL 94 ratings of the ternary composites at suitable MP/PEPA ratios are raised to V‐0 from no rating (PP/MP). The TG and RTFTIR studies indicate that the interaction occurs among MP, PEPA and PP. Copyright © 2008 John Wiley & Sons, Ltd.     

纳米SiO2对PP/MPP/PEPA膨胀阻燃体系的协同作用

以纳米SiO,为阻燃协效剂,采用多聚磷酸蜜胺(MPP)和茏状季戊四醇磷酸酯(PEPA)复配阻燃剂,制备具有良好阻燃性能的无卤阻燃聚丙烯(PP).研究纳米SiO2用量对PP阻燃性能和协效作用的影响.结果表明:添加少量的纳米SiO2可提高PP的阻燃性能;当纳米SiO2添加量为1%时,阻燃PP的氧指数达28.5%.TGA和FTIR分析及SEM和体式显微镜观测结果表明:添加少量的纳米SiO2可促进体系成炭,稳定炭层,从而提高材料的阻燃性能.     

Synergistic effects of aluminium hypophosphite on the flame retardancy and thermal degradation behaviours of a novel intumescent flame retardant thermoplastic vulcanisate composite

ABSTRACT

The synergistic effects of aluminum hypophosphite (AHP) on the flame retardancy, thermal degradation behaviors of a novel intumescent flame retardant thermoplastic vulcanizate (TPV/IFR) composite were investigated. The results showed that the combination of AHP with IFR showed evident synergistic effects on the increase in the LOI value and reduction of the combustion parameters for the TPV/IFR/AHP composites at the optimum weight ratio of IFR/AHP (6/1) as evidenced by LOI, UL-94 and CCT. The TGA data revealed that AHP could change the degradation behavior of TPV/IFR composites and enhance the thermal stability of the TPV/IFR composites at high temperature. The results of FTIR, EDXS, LRS and SEM demonstrated that TPV/IFR/AHP composites could form more continuous, dense and stable char layer on the materials surface, and consequently improving the flame retardancy. Based on these results, the possible condensed flame retardant mechanism of TPV/IFR/AHP composites was concluded in detail.     

磷改性酚醛树脂的制备与性能

通过DOPO(9,10–二氢–9–氧杂–10–磷杂菲–10–氧化物)和多聚甲醛反应制备了含磷单体ODOPM(9,10–二氢–9–氧杂–10–磷杂菲–10–羟甲基–10–氧化物),并用于制备磷改性酚醛树脂。通过差示扫描量热(DSC)仪测试体系DOPO的反应程度,通过红外光谱表征ODOPM的结构,通过热重分析测试改性酚醛树脂体系的热行为,通过极限氧指数和垂直燃烧法测试树脂体系的阻燃性能,通过扫描电子显微镜观察树脂燃烧后残炭的微观形貌,并采用万能试验机测试树脂样条的强度性能。实验结果表明:实验成果制备得到目标产品ODOPM,随着含磷单体ODOPM含量的提高,酚醛树脂的阻燃性能随着提高,酚醛树脂的残炭量也随着提高。酚醛树脂通过凝聚相阻燃机理起到阻燃作用。当磷改性酚醛树脂的ODOPM单体含量为15%时,树脂的LOI值可以达到32.4%,并通过V–0垂直燃烧测试,并且磷改性酚醛树脂保持较好的强度。     

氧化锌对膨胀阻燃聚丙烯的影响

研究了协效剂氧化锌（ZnO）对聚磷酸铵（APP）、季戊四醇（PER）、氰尿酸三聚氰胺（MCA）膨胀阻燃聚丙烯（PP）体系的阻燃协效作用。采用氧指数（LOI）、热失重法（TG）、锥形量热仪（Cone）、红外光谱（FTIR）等手段分析了ZnO对膨胀阻燃PP的影响。结果表明，氧化锌可提高该体系的LOI和阻燃性能，还可促进阻燃体系形成炭层，且可提高其炭层的强度，该体系氧化锌最佳用量应为1．0份。     

Synthesis of novel triazine charring agent and its effect in intumescent flame‐retardant polypropylene

A novel charring agent (CNCA‐DA) containing triazine and benzene ring, using cyanuric chloride, aniline, and ethylenediamine as raw materials, was synthesized and characterized. The effects of CNCA‐DA on flame retardancy, thermal degradation, and flammability properties of polypropylene (PP) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), and cone calorimeter test (CCT). The TGA results showed that CNCA‐DA had a good char forming ability, and a high initial temperature of thermal degradation; the char residue of CNCA‐DA reached 18.5% at 800°C; Ammonium polyphosphate (APP) could improve the char residue of APP/CNCA‐DA system, the char residue reached 31.6% at 800°C. The results from LOI and UL‐94 showed that the intumescent flame retardant (IFR) containing CNCA‐DA and APP was very effective in flame retardancy of PP. When the mass ratio of APP and CNCA‐DA was 2 : 1, and the IFR loading was 30%, the IFR showed the best effect; the LOI value reached 35.6%. It was also found that when the IFR loading was only 20%, the flame retardancy of PP/IFR can still pass V‐0 rating in UL‐94 tests, and its LOI value reached 27.1%. The CCT results demonstrated that IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), and mass loss (ML). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012