疏水膨胀型阻燃聚丙烯的制备及与La2O3的协效阻燃

采用四乙氧基硅烷（TEOS）作为改性修饰剂,分别对季戊四醇（PER）和聚磷酸铵（APP）进行表面改性,制备得到膨胀型阻燃剂（IFR）,对改性后的IFR进行了红外光谱及热失重分析等表征,确认了硅的引入;向改性阻燃剂中加入纳米氧化镧（La2O3）作为阻燃协效剂,然后与聚丙烯（PP）混合,制备了疏水性膨胀型阻燃PP;研究了改性前后复合阻燃剂对PP阻燃性能和力学性能的影响。结果表明,改性后的阻燃体系表现出了较好的疏水性能,加入协效剂La2O3后,材料的阻燃性能和力学性能均较改性之前有所提高。     

磷酸硼协效膨胀型阻燃剂对聚丙烯阻燃性能的研究

在膨胀型阻燃剂（IFR）中添加不同比例的协效剂磷酸硼（BP）制备复合阻燃剂,将复合阻燃剂加入聚丙烯（PP）中,制备阻燃PP复合材料。通过垂直燃烧、极限氧指数测试、锥形量热测试、热重分析和力学性能测试对PP复合材料进行表征。结果表明：BP对IFR具有显著的协同阻燃效果。当添加2%BP和13%IFR时,PP/IFR/BP复合材料（样品4#）阻燃性能最佳,燃烧等级达到V-0,极限氧指数达到30.8%。样品4#的热释放速率峰值、平均热释放速率、总产烟量和总释放热与加入15%IFR的阻燃PP相比,分别降低19.51%、4.40%、34.00%和6.87%,700℃时样品4#的质量保留率增加50%。燃烧过程中,PP/IFR/BP复合材料的硼元素在凝聚相中催化IFR交联成炭,较未添加BP的复合材料,PP/IFR/BP炭层膨胀程度更高且更致密。BP协效剂的添加降低了阻燃剂的添加量,明显提升复合材料的力学性能。     

超疏水三嗪系膨胀阻燃剂的制备及其应用

采用硅树脂对三嗪系膨胀阻燃剂(IFR)进行表面包覆改性,并通过静态接触角测试对其进行了润湿性能表征。然后将改性前后的IFR分别添加到聚丙烯(PP)中制备了阻燃PP材料,并测试研究了该材料的阻燃性能、力学性能及耐水性。结果表明:当硅树脂的包覆量为5%时,改性IFR的接触角由改性前的0°上升到了151.3°,表现出超疏水性能。与未改性IFR阻燃的PP材料相比,由改性IFR得到的阻燃PP材料,其阻燃性能略有降低,但阻燃剂与聚合物的相容性以及阻燃PP的力学性能有所改善;同时阻燃PP的耐水性能显著提高,其阻燃剂的水抽出率大大降低。当阻燃剂添加量为20%时,未改性IFR阻燃的PP材料,其阻燃剂抽出率为3.71%,且耐水性测试后材料的阻燃性能明显下降;而改性IFR阻燃的PP材料,其阻燃剂抽出率仅为0.38%,且耐水性测试后材料的阻燃性能基本保持不变,表现出优良的耐水性能。     

PP/LGF复合材料的膨胀性阻燃与协效阻燃性能

采用膨胀型阻燃剂(IFR)及协效剂海泡石(SP)对长玻璃纤维增强聚丙烯(PP/LGF)复合材料进行阻燃,通过双螺杆挤出机制备了PP/LGF母粒,IFR母粒和SP母粒,然后将这3种母粒通过注塑机制备了PP/LGF/IFR/SP复合材料,通过极限氧指数(LOI)、垂直燃烧测试、锥形量热仪、热重分析、扫描电子显微镜、力学性能测试等表征PP/LGF各阻燃复合体系的性能。结果表明,当IFR质量分数为22%时,PP/LGF/IFR阻燃复合材料的LOI为28.8%,且垂直燃烧等级达到V–0级;锥形量热仪测试结果表明加入IFR及SP后阻燃复合体系的第一热释放速率峰值降低,而第二热释放速率峰消失;SP质量分数为1%,IFR质量分数为21%的PP/LGF/IFR/SP阻燃复合材料LOI为29.6%,垂直燃烧等级达到V–0级,热释放速率峰值和总热释放量得到有效降低,热稳定性最好,且燃烧时产生致密的炭层覆盖于玻璃纤维表面,同时加入1%SP后复合材料的力学性能下降幅度相对较小。     

有机硅改性环糊精在膨胀阻燃聚丙烯中协同作用的研究

以1,1,3,3-四甲基二硅氧烷、烯丙基缩水甘油醚、β-环糊精(β-CD)为原料合成了一种新型有机硅改性环糊精(CDS)。红外光谱测试表明,环糊精接枝到硅氢加成反应制得的聚合物链端。利用热重分析、氧指数测试、垂直燃烧、扫描电镜分析等手段对比探讨聚丙烯(PP) /膨胀阻燃剂(IFR) /β-CD和PP/IFR/CDS复合材料热失重行为、阻燃性能、微观结构及力学性能。结果表明,IFR/CDS具有良好的协同阻燃作用,同时提高了材料的力学性能。当CDS含量为1.5 %（质量分数,下同）时,PP/IFR/CDS复合材料的极限氧指数为35.0 %, 垂直燃烧通过UL94 V-0测试,拉伸强度、弯曲强度和冲击强度分别比PP/IFR/β-CD复合材料提高了8.6 %、16.8 %和70.7 %。     

不同膨胀型阻燃剂改性聚丙烯/聚乳酸复合材料

用两种不同的膨胀型氮磷阻燃剂(IFR1和IFR2)阻燃改性聚丙烯(PP)/聚乳酸(PLA)复合材料。结果表明:两种阻燃剂在PP/PLA基体中都具有良好的分散性和界面粘合性。阻燃剂的加入降低了材料的力学性能,而含有25%阻燃剂的PP/PLA复合材料就能到达垂直燃烧试验(UL-94)的V0等级。燃烧过程中阻燃剂通过在材料表面形成致密的炭层来提高材料的阻燃性,其中IFR1对PP/PLA体系的阻燃改性效果更好。从力学性能和阻燃效果的双重考虑,质量含量25%的阻燃剂适合于PP/PLA材料的阻燃改性。     

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%。     

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。     

新型环保高效膨胀型阻燃剂阻燃聚丙烯

对2个复合体系聚丙烯/膨胀型阻燃剂(PP/IFR)及聚丙烯/聚烯烃弹性体/纳米碳酸钙/膨胀型阻燃剂(PP/POE/nano-CaCO3/IFR)的阻燃性进行研究,通过测试氧指数、水平燃烧速率、烟密度以及燃烧测试后试样的形貌观察,分析了复合体系的阻燃效果及机理。结果表明,PP/IFR复合体系可达到优异的阻燃性能,IFR用量为30份时氧指数达到34.4%,并且可明显改善PP的熔滴现象。而添加POE破坏了阻燃炭层的形成,降低了氧指数,并伴随严重的熔滴,却能明显降低释烟量。     

磷铝分子筛对膨胀阻燃聚丙烯复合材料阻燃与热稳定性能影响

通过水热合成法制备了系列不同结构类型的磷铝分子筛（AlPO⁃n,n=5, 11, 17, 34）,并通过熔融挤出共混,将系列AlPO⁃n分子筛应用到膨胀阻燃聚丙烯（PP/IFR）复合材料中,致力改善其阻燃和热稳定性能。利用极限氧指数仪、水平垂直燃烧仪、锥形量热仪和万能试验机分别测试材料的阻燃性能和力学性能。结果表明,AlPO⁃n分子筛可改善PP/IFR复合材料的相关性能,其中AlPO⁃17（1 %,质量分数,下同）相对其他类型磷铝分子筛能明显改善PP/IFR复合材料的阻燃和热稳定性能,复合材料的极限氧指数和600 ℃的残炭率相对于PP分别提高至34.8 %和14.3 %。     

硅烷偶联剂在膨胀阻燃聚丙烯复合体系中的应用

用乙烯基硅烷偶联剂(A-172)对膨胀阻燃剂(IFR)进行表面改性,研究了该阻燃剂对聚丙烯(PP)体系力学性能和阻燃性能的影响。结果表明:当A-172/IFR/PP为0.5/22.5/77.5时,体系的力学性能基本不变,但阻燃性能得到了改善。其中氧指数同比提高了22.5%,体系的热释放速率峰值和烟释放速率峰值同比分别下降了9.7%和98.75%。     

Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes

Intumescent‐flame‐retarded polypropylene (PP‐IFR) composites were prepared by the incorporation of methyl hydrogen siloxane treated ammonium polyphosphate and dipentaerythritol in a twin‐screw extruder. The effects of zeolite (Z), multiwalled carbon nanotubes (CNTs), and maleic anhydride grafted polypropylene on the flame retardancy, mechanical properties, and thermal stability of PP‐IFR were investigated. The addition of Z and CNT promoted the flame retardancy of PP‐IFR, and the highest limited oxygen index was 35.6%, obtained on PP‐M‐IFR‐2–Z, for which the heat‐release rate, total heat release, and smoke production rate based on cone calorimetry analyses decreased by 45.0, 51.0, and 66.3%, respectively, in comparison with those values of the PP‐IFR composites. Additionally, scanning electron microscopy analyses showed that there was a good interface interaction between the polypropylene matrix and additives. The flexural, tensile, and impact strengths of the PP‐IFR composites were improved significantly with the incorporation of CNT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42875.     

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene (GF-PP) composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers (GF) surface to the flame zone. In this study, dipentaerythritol (DPER), a charring agent, was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER. DPER has a synergistic effect with the intumescent flame retardants (IFR) added in the composites, which can induce interfacial carbonization on the surface of GF, thus transforming the intrinsic smooth GF surface into roughness one. In this way, the negative effect of the wick effect in flame retardancy is weakened. Moreover, the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed. The PP composites with 20 wt% modified glass fiber (M-GF) and 30 wt% IFR can achieve the UL-94V-0, and its limiting oxygen index (LOI) value increased from 16.5% to 29.5%. Simultaneously, the heat release rate (HRR), total heat release (THR) and total smoke release (TSR) decreased significantly, and the peak of heat release rate (PHRR) reduced 60.6% compared with GF-PP.     

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     

An efficient approach to improving fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene composites via incorporating organo‐modified sepiolite

In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.     

少量增容剂对膨胀阻燃PP/POE共混复合体系性能的影响

为提高聚丙烯(PP)材料的热性能和力学性能,选用膨胀型阻燃剂(IFR)对PP/乙烯-辛烯共聚物(POE)共混体系进行阻燃改性,应用双螺杆共混挤出的方法制备了PP/POE/IFR共混复合体系,对共混复合体系的阻燃性能、力学性能、膨胀炭层以及微观相结构进行了研究。结果表明,少量增容剂马来酸酐接枝POE(POE-g-MAH)的加入使得IFR颗粒的分散更加均匀、分散粒径减小,同时颗粒与聚合物基体间的结合更加紧密,从而对共混复合体系的力学和阻燃性能都有明显的提高,特别是提高冲击强度。当PP/POE/IFR/POE-g-MAH配比为80/17/20/3时,共混复合体系的平均热释放速率、热释放速率峰值、比消光面积平均值、总烟释放量较未添加增容剂的共混复合体系(PP/POE/IFR配比为80/20/20)分别下降了22.4%,14.9%,29.2%,21.8%,冲击强度提高了69.6%。     

Synergistic effects of hydroxy silicone oil on intumescent flame retardant polypropylene system

The effects of hydroxy silicone oil as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP), melamine (MEL) and pentaerythritol (PER). The UL 94 rating, thermogravimetric analysis (TGA), cone calorimeter (CONE) and digital photograph were used to evaluate the synergistic effects of hydroxy silicone oil (HSO). It has been found that the PP composite containing only APP, MEL and PER does not show good flame retardancy at 30% additive level. The cone calorimeter results show that the heat release rate, mass loss rate, mass, total heat release, carbon monoxide and carbon dioxide of PP/APP/MEL/PER/HSO composites decrease in comparison with the PP/APP/MEL/PER composite. The digital photographs demonstrated that HSO could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of HSO plays a synergistic effect in the flame retardancy.     

Influence of the pentaerythritol phosphate melamine salt content on the combustion and thermal decomposition process of intumescent flame‐retardant ethylene–vinyl acetate copolymer composites

Pentaerythritol phosphate melamine salt (PPMS) as a single‐molecule intumescent fire retardant was synthesized and characterized. The influence of the PPMS content on the combustion and thermal decomposition processes of intumescent‐flame‐retardant (IFR) ethylene–vinyl acetate copolymer (EVA) composites was studied by limiting oxygen index (LOI) measurement, UL 94 rating testing, cone calorimetry, thermogravimetric analysis, and scanning electron microscopy. The LOI and UL 94 rating results illustrate that PPMS used in EVA improved the flame retardancy of the EVA composites. The cone calorimetry test results show that the addition of PPMS significantly decreased the heat‐release rate, total heat release, and smoke‐production rate and enhanced the residual char fire performance of the EVA composites. The IFR–EVA3 composite showed the lowest heat‐release and smoke‐production rates and the highest char residue; this means that the IFR–EVA3 composite had the best flame retardancy. The thermogravimetry results show that the IFR–EVA composites had more residual char than pure EVA; the char residue yield increased with increasing PPMS content. The analysis results for the char residue structures also illustrated that the addition of PPMS into the EVA resin helped to enhance the fire properties of the char layer and improve the flame retardancy of the EVA composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42148.     

钛酸酯偶联剂在膨胀型阻燃聚丙烯中的偶联作用

研究了钛酸酯偶联剂（TTOPP）对聚丙烯/膨胀型阻燃剂（PP/IFR）复合材料阻燃性能和力学性能的影响,并采用扫描电子显微镜、偏光显微镜和X射线衍射研究了复合材料的微观形态和结晶行为。结果表明,加入TTOPP后,IFR在PP中的分散更加均匀,PP球晶的大小趋于一致,适量的TTOPP改善了IFR与PP间的相容性,促进了IFR对PP形成β晶的诱导作用。当PP/IFR/TTOPP为75/25/0.375时,复合材料的综合性能最佳,自熄时间降到24 s,拉伸强度和冲击强度比PP/IFR分别提高了14.0 %和12.0 %。     

壳聚糖/聚磷酸铵膨胀阻燃PP的阻燃及抑烟性能

为了提高聚丙烯(PP)的阻燃和抑烟性能,将壳聚糖(CS)作为膨胀型阻燃剂的碳源、聚磷酸铵(APP)作为膨胀型阻燃剂的酸源和气源,在此基础上通过熔融共混的方法制备了PP/CS/APP复合材料。采用极限氧指数仪、锥形量热仪等仪器研究了PP/CS/APP复合材料的的抑烟性及阻燃性。研究结果表明:CS/APP添加量为30%时,复合材料的极限氧指数值最大可达28.1%;且复合材料在烟气释放总量、CO和CO_2排放上明显降低,抑烟性得到了提升;热释放速率峰值、平均热释放速率值、平均有效燃烧热值、总热释放量值降低,成炭率升高,PP/CS/APP复合材料更难点燃;火灾性能指数明显提高,阻燃性能得到了大幅度提升,火灾蔓延指数显著减小,同时火灾危险性也相应降低。