膨胀型阻燃PP纳米复合材料的燃烧性能

将纳米SiO2、磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)和聚磷酸铵(APP)加入聚丙烯(PP)中,制备膨胀型阻燃PP纳米复合材料.采用氧指数测定仪、垂直燃烧测定仪、锥形量热仪对PP纳米复合材料的燃烧性能进行研究.结果表明:FR/APP/SiO2提高了PP的氧指数、垂直燃烧等级和残炭率,降低了热释放速率,燃烧烟气中的CO、CO2浓度.在ω(FR):ω(APP):ω(SiO2)=15:7:3,IFR的含量为25%的情况下,PP的氧指数为29.4%,UL-94等级达到V-0.     

磷系阻燃剂FR/APP协效阻燃PP

采用氧指数测定仪、热重分析仪和锥形量热仪研究了磷系阻燃剂1,3,5-三(5,5-二甲基-1,3-二氧杂环己内磷酸基)苯(FR)和聚磷酸铵(APP)复配体系对聚丙烯(PP)材料阻燃性能的影响.结果表明,FR/APP提高了PP的极限氧指数(LOI)、热稳定性和残炭率,降低了热释放速率.当w(FR)为15%和w(APP)为10%复配阻燃PP时,复合材料的LOI为29.6%.阻燃级别达到UL 94 V-0级.     

PP/纳米SiO2复合材料的阻燃性能研究

将磷系阻燃剂1,3,5-三（5,5-二甲基-1,3-二氧杂环己内磷酸基）苯（FR）、聚磷酸铵（APP）、纳米SiO2复配,制备聚丙烯(PP)纳米复合阻燃材料。采用氧指数测定仪、水平垂直燃烧测定仪、热重分析仪、锥形量热仪对PP纳米复合阻燃材料的阻燃性能进行了研究。结果表明,FR/APP/SiO2提高了PP的氧指数、水平燃烧等级、热稳定性和残炭率,降低了热释放速率。当阻燃剂FR/APP/SiO2的总体含量为25 %,FR/APP/SiO2配比为15/7/3的情况下,PP纳米复合阻燃材料的氧指数为29.4 %,水平燃烧等级为FH-1。     

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。     

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。     

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。     

磷-硅阻燃剂在膨胀型阻燃聚丙烯中的应用研究在

采用一种新型含磷硅高分子阻燃剂(EMPZR)与聚磷酸铵(APP)、多聚磷酸密胺(MPP）复配成膨胀型阻燃剂(IFR),并对聚丙烯(PP)进行阻燃。当APP/MPP/EMPZR质量比为15/10/15时,所制得的复合材料的氧指数达到33.0 %,垂直燃烧达到UL 94 V 0级;与纯PP相比,拉伸强度、弯曲强度和冲击强度都没有下降;热失重分析表明,阻燃PP材料在600 ℃时的残炭量为21.14 %,成炭率显著提高;扫描电镜对残炭形貌的表征以及氧指数测试前后阻燃PP材料的红外图谱分析证实了EMPZR与APP、MPP在PP中有良好的协效阻燃作用。     

笼状磷酸酯微胶囊/聚磷酸铵阻燃聚丙烯

将笼状磷酸酯微胶囊(ET)与聚磷酸铵(APP)复配用于阻燃聚丙烯(PP)。采用氧指数和UL 94评价了阻燃PP的阻燃性能,采用热重分析、扫描电子显微镜照片、傅里叶变换红外光谱及X射线电子能谱研究了阻燃剂的协同效应和阻燃机理。结果表明:ET与APP有较好的复配协同效应,ET/APP的阻燃性能随m(ET)/m(APP)的不同而变化。当m(ET)/m(APP)为1∶2时,阻燃效果最好。w(ET/APP)为30%时,氧指数达29.7%,且达到UL 94 V-0级。     

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 %。     

磷系阻燃剂对PC/ABS共混物燃烧性能的影响

通过磷系阻燃剂(FR)阻燃聚碳酸酯/丙烯腈-丁二烯-苯乙烯(PC/ABS)共混物,制备阻燃材料,研究磷系阻燃剂对PC/ABS阻燃复合材料的燃烧行为和热稳定性的影响。通过UL94垂直燃烧测试、极限氧指数(LOI)测试、马弗炉测试等表征方法,对PC/ABS阻燃复合材料的燃烧行为进了系统的研究。结果表明,磷系阻燃添加量为15%时,PC/ABS阻燃复合材料能够达到UL94 V-2级,LOI的值为29.3%,高温时的残炭量由11.2%提高到20.8%。其中FR阻燃剂在高温下可以产生磷酸酯类黏稠难燃物质,能够有效地起到凝聚相阻燃作用,提高了PC/ABS共混物材料的阻燃性能,表现出良好的阻燃效果。     

Polyamide‐enhanced flame retardancy of ammonium polyphosphate on epoxy resin

An attractive intumescent flame retardant epoxy system was prepared from epoxy resin (diglycidyl ether of bisphenol A), low molecular weight polyamide (cure agent, LWPA), and ammonium polyphosphate (APP). The cured epoxy resin was served as carbonization agent as well as blowing agent itself in the intumescent flame retardant formulation. Flammability and thermal stability of the cured epoxy resins with different contents of APP and LWPA were investigated by limited oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results of LOI and UL‐94 indicate that APP can improve the flame retardancy of LWPA‐cured epoxy resins. Only 5 wt % of APP can increase the LOI value of epoxy resins from 19.6 to 27.1, and improve the UL‐94 ratings, reaching V‐0 rating from no rating when the mass ratio of epoxy resin to LWPA is 100/40. It is much interesting that LOI values of flame retardant cured epoxy resins (FR‐CEP) increase with decreasing LWPA. The results of TGA, FTIR, and X‐ray photoelectron spectroscopy (XPS) indicate that the process of thermal degradation of FR‐CEP consists of two main stages: the first stage is that a phosphorus rich char is formed on the surface of the material under 500°C, and then a compact char yields over 500°C; the second stage is that the char residue layer can give more effective protection for the materials than the char formed at the first stage do. The flame retardant mechanism also has been discussed according to the results of TGA, FTIR, and XPS for FR‐CEP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flame retarded epoxy resins by adding layered silicate in combination with the conventional protection‐layer‐building flame retardants melamine borate and ammonium polyphosphate

The pyrolysis and flammability of phosphonium‐modified layered silicate epoxy resin nanocomposites (EP/LS) were evaluated when LS was combined with two flame retardants, melamine borate (MB) and ammonium polyphosphate (APP), that also act via a surface protection layer. Thermogravimetry (TG), TG coupled with Fourier Transform Spectroscopy (TG‐FTIR), oxygen index (LOI), UL 94 burning chamber (UL 94) and cone calorimeter were used. The glassy coating because of 10 wt % MB during combustion showed effects in the cone calorimeter test similar to nanodispersed LS, and somewhat better flame retardancy in flammability tests, such as LOI and UL 94. Adding APP to EP resulted in intumescent systems. The fire retardancy was particularly convincing when 15 wt % APP was used, especially for low external heat flux, and thus, also in flammability tests like LOI and UL 94. V0 classification is achieved when 15 wt % APP is used in EP. The flame retardancy efficiency of the protection layers formed does not increase linearly with the MB and APP concentrations used. The combination of LS with MB or APP shows antagonism; thus the performance of the combination of LS with MB or APP, respectively, was disappointing. No optimization of the carbonaceous‐inorganic surface layer occurred for LS‐MB. Combining LS with APP inhibited the intumescence, most probably through an increase in viscosity clearly above the value needed for intumescent behavior. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Experimental investigation of flame retardancy and mechanical properties of APP/EG/TPU multilayer composites prepared by microlayer coextrusion technology

In this paper, ammonium polyphosphate(APP)/expandable graphite(EG)/thermoplastic polyurethane (TPU) composites were prepared by microlayer coextrusion technology, APP and EG fillers had good synergistic flame retardancy and excellent dispersion in TPU matrix, which greatly improved the flame retardancy and mechanical properties of multilayer composites. The dispersion of APP and EG in TPU was characterized by using SEM, the flame retardancy of composites was characterized by using UL94 and LOI, the thermal stability of composites was characterized by using TGA and DTG, and tensile test was used to characterized the mechanical properties of composites. SEM showed that the microlayer coextrusion technology significantly improved the dispersion of APP and EG in TPU. As showed by the experimental results, the vertical combustion level of ordinary blended composites reached V-2 after adding only one kind of filler either APP or EG, and the vertical combustion level of ordinary blended composites reached V-0 with APP and EG applied together, while the vertical combustion level of microlayer coextruded composites all reached V-0 when the total addition of APP and EG was 15%. In particular, the LOI value of microlayer coextruded composites was 30.9%, while the LOI value of ordinary blended composites only was 27.9% when APP: EG = 1: 1. At this time, the flame retardancy level of APP/EG/TPU composites was the best. In addition, the thermal stability and mechanical properties of microlayer coextruded composites were far superior to ordinary blended composites. In conclusion, the synergistic flame retardancy of APP and EG fillers and the dispersion of APP and EG fillers in TPU matrix played a significant role in enhancing flame retardancy and mechanical properties.     

木粉及聚磷酸铵对PE-HD木塑复合材料阻燃和力学性能的影响

以高密度聚乙烯(PE-HD)为基体,聚磷酸铵(APP)和木粉(WF)为膨胀型阻燃体系,制备了阻燃木塑复合材料(WPC)。通过极限氧指数、垂直燃烧UL 94、锥形量热分析、热失重分析、红外光谱分析、力学性能等对其进行性能表征。结果表明,与纯PE-HD相比,极限氧指数随着WF含量增加而提高,添加40 %WF时极限氧指数提高到30.5 %,UL 94可达V-0等级,热释放速率峰值和总热释放量降低;APP和WF燃烧过程中发生了化学作用,形成了保护炭层,提高了材料的热稳性,材料的拉伸和弯曲强度得到提高。     

水镁石／ATH／APP复合阻燃剂对UPR的阻燃、抑烟性能的影响

将水镁石、氢氧化铝(ATH)、聚磷酸铵(APP)这3种阻燃剂复配,并应用于不饱和聚酯树脂(UPR),得到阻燃型UPR复合材料。通过氧指数、垂直燃烧(UL94)、烟密度等级(SDR)、DSc-TG对阻燃复合材料的阻燃、抑烟及热稳定性能进行了研究,结果表明,在该复配阻燃体系中,水镁石、ATH、APP三者存在明显的协效作用,在水镁石：ATH：APP为2：1：1(质量比)、复合阻燃剂含量为40%时,复合材料氧指数达33．8%,垂直燃烧达FV-0级,烟密度等级为56．74,满足国家B_1级电器类热固性塑料的使用要求。     

Thermal degradation and combustion behaviors of flame retarded glass fiber reinforced polyamide 6 composites based on cerium hypophosphite

In this work, cerium hypophosphite (CeHP) was synthesized and characterized by scanning electron microscope (SEM) and thermogravimetric analysis (TGA) test. CeHP presented rod‐like morphological feature with good thermal stability. Subsequently, CeHP was added into glass fiber reinforced polyamide 6 (GFPA) to develop flame retardant glass fiber reinforced polyamide 6 composites (FR‐GFPA). The flame retardancy of FR‐GFPA composites was characterized by limiting oxygen index (LOI), Underwriters Laboratories 94 testing (UL‐94), microscale combustion calorimeter, and cone calorimeter test. FR‐GFPA composite with 20 wt% CeHP loading passed UL‐94 V0 rating with a high LOI of 26.5 vol%. Cone Calorimeter test showed that peak of heat release rate (PHRR) and total heat release (THR) of FR‐GFPA composites were reduced 27.1% and 21.1% compared with those of GFPA. The mechanical measurement revealed that the tensile strength first increased and then decreased with the increase of CeHP loading. With 15 wt% CeHP loading, the tensile strength of FR‐GFPA composite was 43.0% higher than GFPA. TGA and char residue characterization revealed that the addition of CeHP could significantly promote the formation of condensed char residue. The FR‐GFPA composites obtained herein exhibited superior combined properties of fire resistance, thermal stability, and mechanical properties, demonstrating that CeHP will be a promising candidate for preparing high performance polyamide composites. POLYM. COMPOS., 37:3073–3082, 2016. © 2015 Society of Plastics Engineers     

The effect of red phosphorus on the fire properties of intumescent pine wood flour – LDPE composites

Red phosphorus (RP) was used to improve the fire performance of wood flour – low density polyethylene (LDPE) composites containing ammonium polyphosphate (APP). The fire performance of LDPE‐based composites was investigated by using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis, and cone calorimeter. The addition of 30 wt% APP increased the LOI value from 17.5 to 24.2 and still burned to clamp (BC) in UL‐94 test. The RP showed beneficial effect when combinedly used with APP. The maximum beneficial effect was seen at ratio of 5:1 (APP : RP) with the highest LOI value of 27.2 and UL‐94 rating of V0. RP showed its beneficial effect via increasing the gas phase action of the flame retardant system. Copyright © 2015 John Wiley & Sons, Ltd.     

新型磷系阻燃剂四苯基(双酚-A)二磷酸酯阻燃PC/ABS的研究

利用自制的四苯基(双酚-A)二磷酸酯(BDP)及其复配体系制备了阻燃PC/ABS,研究了阻燃PC/ABS的力学性能、氧指数(LOI)和垂直燃烧测试性能(UL94)、材料的阻燃性能和烟气释放。结果表明:采用15%的BDP阻燃PC/ABS,材料的冲击强度下降了12.82%,LOI达到30.0%,UL94阻燃性能达到V—0级,平均热释放速率(av-HRR)和最大热释放速率(pk-HRR)分别下降了35.84%和31.17%,点燃时间(TTI)延长18s,火势增长指数(FGI)下降了46.72%,比消光面积(SEA)上升了6.68%;采用BDP/APP复配阻燃PC/ABS,材料的冲击强度最大降幅为33.33%,LOI最大可达30.1%,UL94阻燃性能由V—0级降为V—1级,av-HRR和pk-HRR最大分别下降40.89%和31.2%,TTI最大延长20s,FGI最大降幅为50.37%,SEA最大涨幅为11.14%;采用BDP/纳米SiO2复配阻燃PC/ABS,当纳米SiO2的添加量为7%时,材料的冲击强度上升了5.13%,LOI达到31.1%,UL94阻燃性能达到V—0级,av-HRR和pk-HRR分别下降了43.18%和4069%,TTI延长20s,FGI降幅为59.12%,平均比消光面积(av-SEA)涨幅为8.09%,6min内av-SEA下降6.92%,(6min总发烟指数)TSPI6min下降5.54%,阻燃、抑烟效果最佳,对PC/ABS材料的力学性能影响最小。     

Intumescent Flame Retardation of EVA Using Microencapsulated Ammonium Polyphosphate and Pentaerythritols

With a melamine-formaldehyde (MF) resin coating layer, microencapsulated ammonium polyphosphate (MCAPP) is prepared by in situ polymerization and is characterized by XPS and water leaching test. The microencapsulation of APP with the MF resin leads to a decrease in the particle's water leaching rate. The flame-retardant action of MCAPP and APP in EVA are studied using LOI and UL 94 test, and their thermal stability is evaluated by thermogravimetric analysis (TGA). The LOI value of the EVA/MCAPP composite at the same loading is higher than the value of the EVA/APP composite. In comparison with the EVA/MCAPP composites, it is found that the LOI values of the EVA/MCAPP/PER and EVA/MCAPP/DPER ternary composites at the same additive loading increase, and UL 94 ratings of most ternary composites are raised to V-0. The water-resistant properties of the EVA composites are studied, and the results of the composites containing with APP and MCAPP are compared. Moreover, the peroxide cross-linking of the EVA composites is investigated, and the mechanical properties and thermal stability of the composites increase after the cross-linking.