Flame retardancy and mechanical properties of thermal plastic composite panels made from Tetra Pak waste and high‐density polyethylene

In this article, flame retardancy thermoplastic composites were developed by extrusion followed by injection molding using recycled Tetra Pak packaging material (TPP) waste and high‐density polyethylene (HDPE) with addition of ammonium polyphosphate (APP) and melamine (MEL) as intumescent flame retardants (FRs). The influences of intumescent FRs on the properties of composites were investigated. FRs loading positively affected flame retardancy, but deteriorated mechanical properties as the loading rate was more than 30 wt%. Considering the fire retardancy and tensile strength (TS), the content of FR should not be more than 30 wt%. When the ratio of APP/MEL was less than 3/1, both combustion behavior and TS of the composites were improved with the increased FR loading, which was supported and verified by the analysis of FTIR spectra and SEM images. The thermogravimetric analysis results indicated that the incorporation APP and/or APP and MEL into composites as FRs into composites promoted char formation and correspondingly improved the thermal stability. The synergistic effect of APP and MEL in the intumescent FR system further improved the flame retardancy of the composites. POLYM. COMPOS., 37:1797–1804, 2016. © 2014 Society of Plastics Engineers     

ZnO、PA6及APP对聚丙烯的协同阻燃作用研究

以苯乙烯-乙烯-丁二烯-苯乙烯接枝马来酸酐(SEBS-g-MAH)为增容剂,研究了氧化锌(ZnO)、聚酰胺6(PA6)及聚磷酸铵(APP)对聚丙烯(PP)的阻燃性能和力学性能的影响,并观察了复合材料的微观结构。结果表明:加入1%的ZnO可以在一定程度上提高APP/PP复合材料的阻燃性,而加入10%的PA6后,APP/ZnO/PP复合材料的氧指数(OI)可提高到36.8%,经5%SEBS-g-MAH增容后,PA6/APP/ZnO/PP复合材料OI值可进一步提高至38.9%;APP的加入明显降低了PP的拉伸强度和冲击强度,但ZnO、PA6和SEBS-g-MAH的加入可以显著改善APP/PP复合材料的力学性能;ZnO的加入提高了PP炭层的致密性,而添加PA6后,炭层呈现明显的片状致密结构。     

无卤膨胀阻燃PP/PA6合金性能研究

研究了以聚磷酸铵（APP）、三聚氰胺（MA）和层状复合金属氢氧化物（LDH）复配得到的膨胀阻燃剂（IFR）对聚丙烯／尼龙6（PP／PA6）合金性能的影响，分析了不同阻燃体系对PP／PA6合金的阻燃性能、力学性能、热性能和微观形态的影响。结果表明，当APP／MA／LDH为21．0／7．5／1．5（质量比）时，PP／PA6合金具有较好的阻燃性能并能保持较高的力学性能。LDH可以提高阻燃材料的热稳定性和残炭量，而且SEM照片显示炭层微观形态为“面包”状的膨松状。     

ABS树脂的无卤膨胀阻燃研究

以聚酰胺6(PA6)为协效成炭剂,将膨胀型阻燃剂聚磷酸铵(APP)应用于ABS树脂,通过氧指数(OI)测定及UL94测定,探讨了PA6、APP含量对阻燃体系阻燃性能的影响;同时,对复合体系进行了热失重分析,并采用扫描电镜(SEM)观察了复合物燃烧后炭层结构。结果表明:PA6的加入明显提升了体系成炭率,降低了最大热失重速率,ABS/PA6/APP体系燃烧表面形成了膨胀、均匀、致密的炭层结构。当PA6/ABS=20/80时,阻燃性能最佳,当APP含量为25%时,OI可以达到30%,UL94测定达V—1级;当APP含量为35%时,UL94测定达V—0级。     

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。     

改性聚磷酸铵对三嗪类膨胀阻燃聚丙烯性能的影响

由改性聚磷酸铵(APP)、自制的三嗪类成炭发泡剂(CFA)等复配制成膨胀型阻燃剂(IFR),以二氧化硅、二氧化钛等为协效剂阻燃聚丙烯(PP)。研究了不同组分的IFR及协效剂对阻燃PP复合材料阻燃性能、力学性能和耐水性能的影响。结果表明:改性APP的亲水性下降;由改性APP/CFA(4/1)、二氧化硅协效剂复配的PP复合材料阻燃性能、力学性能优良,助剂在PP基体中分散性好,热水浸泡后氧指数为32.5%,仍能达到UL94V—1级,失重率为2.92%。     

氧化锌催化膨胀型阻燃剂对PP阻燃及力学性能的影响

研究了氧化锌催化膨胀型阻燃剂(APP/PER)对PP阻燃和力学性能的影响。研究表明,当APP/PER质量比为20/10,ZnO的质量分数为1．3%时,阻燃PP的LOI值达到最大；同时阻燃PP的拉伸强度和冲击强度比不含ZnO的PP有所提高。TG结果表明,ZnO的加入使阻燃PP燃烧时降解过程加快并生成更多的剩炭,形成稳定的保护层,从而提高了PP的阻燃效果。SEN的形貌观察表明,加入ZnO的试样燃烧炭膜孔径较小、孔膜较厚。     

三嗪类成炭剂的制备及其阻燃聚丙烯的研究

以三聚氯氰和4,4’-二氨基二苯醚（ODA）为原料制备了具有三嗪环与苯环交替结构主链的新型三嗪类成炭剂(CA-ODA),并将其与聚磷酸铵（APP）复配,用于阻燃聚丙烯（PP）。采用热失重分析方法和锥形量热仪研究了不同质量配比的APP/CA-ODA阻燃体系对PP热稳定性和阻燃性能的影响。结果表明,CA-ODA自身具有良好的热稳定性和成炭性能,三嗪环和苯环交替结构能够促进PP成炭,从而有效地提高了PP的阻燃性能。当APP/CA-ODA体系总添加量为25%,二者质量配比为2:1时,PP复合材料的热释放速率峰值由1046 kW?m-2降低至334 kW?m-2,并且残炭量高达41.5 %。     

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。     

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。     

Influence of morphology and ammonium polyphosphate dispersion on the flame retardancy of polystyrene/nylon‐6 blends

The influences of the distribution of ammonium polyphosphate (APP) in polystyrene/nylon‐6 [PS/polyamide‐6 (PA6)] blends and the continuity of the (PA6 + APP) phase on flame retardancy were investigated. The flame retardant properties were evaluated by limiting oxygen index (LOI), vertical flammability test and cone calorimeter tests. The results showed that APP is exclusively dispersed in the PA6 phase, and (PA6 + APP) phase formed a continuous state when the content of PA6 in PS/PA6 blends was higher than 32% (w/w). For blends with a continuous (PA6 + APP) phase, the decrease of PA6 content caused an increase in LOI values from 26% to 33% and a reduction of peak heat release rate. The improvement of flame retardancy was attributed to the increase of APP concentration in the PA6 phase, which benefited the fast formation of a continuous intumescent charred layer. The transformation of (PA6 + APP) phase morphology from a continuous state to a discontinuous state at a PA6 content of below 32% (w/w) caused a decrease in LOI. Results of thermo‐gravimetric and cone calorimeter tests indicated that the discontinuous intumescent charred layer thus formed could be responsible for the deterioration of flame retardant properties, which was also confirmed by scanning electron microscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

Flame Retardancy and Thermal Performance of Polypropylene Treated With the Intumescent Flame Retardant,Piperazine Spirocyclic Phosphoramidate

Piperazine spirocyclic phosphoramidate (PSP), a novel halogen‐free intumescent flame retardant, was synthesized and used to improve the flame retardancy and dripping resistance of polypropylene (PP) combined with ammonium polyphosphate (APP) and a triazine polymer charring‐foaming agent (CFA). The optimum flame‐retardant formulation was PSP:APP:CFA = 3:6:2 (weight ratio). The flammability and thermal behavior of the (intumescent flame‐retardant)‐PP (IFR‐PP) were investigated via limiting oxygen index (LOI), vertical burning tests (UL‐94), thermogravimetric analysis, and cone calorimetry (CONE). The results indicated that the IFR‐PP had both excellent flame retardancy and anti‐dripping ability. The optimum flame‐retardant formulation gave an LOI value of 39.8 and a UL‐94 V‐0 rating to PP. Moreover, both the heat release rate and the total heat release of the IFR‐PP with the optimum formulation decreased significantly relative to those of pure PP, according to the cone calorimeter analyses. The residues of IFR‐PP obtained after CONE tests were observed by scanning electron microscopy, and it was found that the char yield was directly related to the flame retardancy and anti‐dripping behavior of the treated PP. J. VINYL ADDIT. TECHNOL., 20:10–15, 2014. © 2014 Society of Plastics Engineers     

新型膨胀型阻燃剂阻燃聚丙烯的研究

通过微胶囊化技术合成了新型磷氮体系无卤膨胀型阻燃剂ANTI-6,用ANTI-6对聚丙烯(PP)进行阻燃改性。研究了阻燃剂ANTI-6中聚磷酸铵的微胶囊包覆;考察了阻燃剂对PP的阻燃性能、力学性能和耐水性等的影响。结果表明:包覆的聚磷酸铵粒度均匀致密,热稳定性提高;PP中添加25%ANTI-6阻燃剂可以获得良好的阻燃效果,氧指数达到30,阻燃性达UL94V-0级,改性PP具有优越的综合性能,耐热水性优于国外同类产品。     

新型磷-氮系复配阻燃剂在聚丙烯中的应用

采用一种新型磷-氮系阻燃剂与聚磷酸铵(APP)复配成膨胀型阻燃剂,对聚丙烯(PP)进行阻燃改性。研究了阻燃PP的阻燃性能、热分解过程及力学性能。结果表明:当复配阻燃剂添加量为30%时,阻燃改性PP的氧指数和垂直燃烧等级分别达到32.3%和UL94 V-0级,拉伸强度为37.4 MPa,缺口冲击强度为39.5 kJ/m2,并且具有很好的热稳定性。     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

微胶囊化多聚磷酸铵的耐水性及其在聚丙烯中的阻燃性能

采用三聚氰胺-甲醛树脂(MF) 为囊材,以多聚磷酸铵（APP）为芯材制得微胶囊化多聚磷酸铵（MAPP）。耐水性及膨胀度试验表明,MAPP为膨胀型阻燃剂,APP/MF =3/1 (质量比,下同)时,MAPP在50 ℃时在水中的溶解度为0.052 g/100 mL,比APP减低了78 ％;膨胀度达到78.6 ㎝3/g。热分析表明,聚丙烯（PP）/MAPP比PP/APP的热降解速度加快,但释热量减小。由于形成蓬松多孔膨胀炭层,PP/MAPP比PP/APP的阻燃性能更佳,PP/MAPP=70/30时,其氧指数增到30.6 %。     

苯基聚硅氧烷微胶囊化聚磷酸铵的制备及其在PP中阻燃性能研究

采用苯基三甲氧基硅烷为前驱体,通过溶胶凝胶法制备出苯基聚硅氧烷微胶囊化聚磷酸铵（MAPP）。将MAPP作为阻燃剂,季戊四醇（PER）作为成炭剂,制备阻燃聚丙烯（PP）。用傅里叶红外光谱、扫描电子显微镜、能谱仪及热重分析仪对MAPP进行表征。结果表明,聚磷酸铵（APP）被苯基聚硅氧烷成功包覆;较之APP,MAPP的热稳定性和疏水性显著提高;MAPP的阻燃性能优于APP,PP/MAPP/PER复合材料达到V-0级别;阻燃剂及成炭剂的加入对PP的结晶行为有促进作用。     

Influence of polyamide 6 as a charring agent on the flame retardancy,thermal, and mechanical properties of polypropylene composites

In this work, polyamide 6 (PA6) as a charring agent has been used in combination with thermoplastic polyurethane (TPU)‐microencapsulated ammonium polyphosphate (MTAPP) forming intumescent flame retardants (IFRs) which applies in polypropylene (PP). The effects of the IFRs on the flame retardancy, morphology of char layers, water resistance, thermal properties and mechanical properties of flame‐retardant PP composites are investigated by limiting oxygen index (LOI), UL‐94 test, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mechanical properties test. The results show that the PP/MTAPP/PA6 composites exhibit much better flame‐retardant performances than the PP/MTAPP composites. The higher LOI values and UL‐94 V‐2 of the PP/MTAPP composites with suitable amount of PA6 are obtained, which is attributed to the thick and compact char layer structure evidenced by SEM. The results from TGA and DSC demonstrate that the introduction of PA6 into PP/MTAPP composites has a great effect on the thermal stability and crystallization behaviors of the composites. Furthermore, the mechanical properties of PP/MTAPP/PA6 composites are also improved greatly due to the presence of PA6 as a charring agent. POLYM. ENG. SCI., 55:1355–1360, 2015. © 2015 Society of Plastics Engineers     

有机化坡缕石黏土-膨胀型阻燃聚丙烯复合材料的制备及性能

制备了优异阻燃性能(LOI36%)兼具良好力学性能的膨胀型阻燃聚丙烯复合材料OPGS/PA-APP/PP。将有机化坡缕石黏土引入到哌嗪-多聚磷酸铵(PA-APP)膨胀型阻燃(IFR)聚丙烯(PP)复合材料中,通过极限氧指数(LOI)、垂直燃烧(UL-94)、热重分析法(TGA)、扫描电子显微镜(SEM)、通用电子万能试验机研究了有机化坡缕石黏土添加量对PA-APP阻燃聚丙烯复合材料阻燃性能和力学性能的影响。结果表明,添加质量分数为2%的有机化坡缕石黏土提高了该复合材料的阻燃性能和力学性能。此外,所制备样品经垂直燃烧测试可达到阻燃V-0级别。实验证明,有机化坡缕石黏土在膨胀型阻燃聚丙烯复合材料中具有明显的协效阻燃作用。     

埃洛石复配阻燃剂对聚丙烯阻燃性能和力学性能的影响

用埃洛石、三聚氰胺作为阻燃剂,制备了无卤阻燃聚丙烯(PP)复合材料。通过氧指数(OI)、垂直燃烧、万能力学仪、扫描电镜分析研究了埃洛石复配阻燃剂对PP阻燃性能、力学性能的影响。结果表明:埃洛石复配阻燃剂可使PP复合材料通过UL94燃烧性能测试,在提高材料OI的同时,保持了其优良的力学性能。