OMMT与MPP协效阻燃对硅橡胶性能影响

以三聚氰胺磷酸盐（MPP）、有机蒙脱土（OMMT）为协效阻燃剂制备阻燃硅橡胶。通过x射线衍射（XRD）法、垂直燃烧法、热重法（TG）等研究阻燃硅橡胶分散性、燃烧性能和拉伸性能。结果表明,OMMT与MPP具有明显协同阻燃性;当OMMT用量为3质量份、MPP用量为55质量份时,复合材料有焰燃烧时间最短,阻燃效果最好;OMMT用量为3-5质量份时,复合体系的垂直燃烧性能均可达到FV-0级,残碳率最高,且力学性能较好。     

Synergistic flame retardant effect of cerium oxide in ethylene‐vinyl acetate/aluminum hydroxide blends

The flammability characterization and synergistic flame retardant effect of cerium oxide (CeO₂) in the ethylene‐vinyl acetate/aluminum hydroxide blends were studied using limiting oxygen index (LOI), UL‐94 test, and cone calorimeter test (CCT). The results showed that the addition of a given amount of CeO₂ apparently increased the LOI value and UL‐94 rating. The data obtained from the CCT indicated that the addition of CeO₂ greatly decreased the heat release rate and prolonged the combustion time. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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.     

Preparation of a novel synergistic flame retardant and its application in silicone rubber composites

Dehydration condensation product (DHCP) was prepared by addition and dehydration condensation reactions of 9,10-dihydro-9-oxa-10-phenanthrene-10-oxide (DOPO), vinyl trimethoxysilane, and (3-aminopropyl) triethoxysilane. DHCP-PA with high phosphorus content was prepared by reaction between DHCP and phytic acid (PA). It was then compounded with oxidized multi-walled carbon nanotubes (OMWCNTs) to prepare silicone rubber (SR) flame retardant composites. The results showed that the SR with a small amount of DHCP-PA owned good flame retardant effect. The heat release rate (HRR) was decreased from 436 kW/m² for pure SR to 288 kW/m² for the SR with 5 phr DHCP-PA, and the decreasing degree was 33.9%. After mixing 5 phr DHCP-PA with 1 phr OMWCNTs, the HRR of SR composite was decreased from 436 to 251 kW/m², the smoke production rate was decreased from 0.161 to 0.087 m²/s, the limited oxygen index value was increased from 20.4% to 28.4%, and the flame retardant grade can reach UL94 V-0. In addition, the synergistic flame retardant mechanism was researched and analyzed.     

聚磷酸铵/氢氧化镁复配填充阻燃硅橡胶的研究

分别采用聚磷酸铵（APP）、氢氧化铝（ATH）和APP/ATH复配阻燃剂填充甲基乙烯基硅橡胶,制成阻燃型硅橡胶。研究了APP、ATH和APP/ATH用量及复配方式对硅橡胶阻燃性能、介电性能和力学性能的影响。结果表明,硅橡胶的阻燃性能随APP、ATH用量的增加而增加,同等填充量下,APP/ATH复配阻燃剂填充硅橡胶的阻燃性能比单一APP或ATH填充硅橡胶更佳;随着APP/ATH复配阻燃剂用量的增加,硅橡胶的拉伸强度与拉断伸长率降低,邵尔A硬度、介电常数和介质损耗因数增加。当100份硅橡胶中加入80份APP/ATH复配阻燃剂（APP与ATH的质量比为3∶2）时,硅橡胶的氧指数达44%,拉伸强度、拉断伸长率、邵尔A硬度、介电常数及介质损耗因数分别为6.8 MPa、438%、62度、3.92、249%。     

Synergistic effect of ammonium polyphosphate and expandable graphite on flame‐retardant properties of acrylonitrile‐butadiene‐styrene

A new intumescent flame‐retardant (IFR) system consisting of expandable graphite (EG) and ammonium polyphosphate (APP) was applied in acrylonitrile–butadiene–styrene (ABS) resin. A synergistic effect between EG and APP on the flame retardancy of ABS was observed. Fixing the total loading of flame retardant at 15 wt %, the limited oxygen index (LOI) could reach 31 vol % at a weight ratio of 3 : 1 for EG and APP. While LOI values of EG‐ and APP‐filled ABS were only 26.0 and 21.5 vol % at the same loading, respectively. The UL‐94 vertical burning test suggested that samples with different ratios of EG and APP could all pass V‐0 rating while the samples containing EG and APP alone only passed V‐1 rating. Thermogravimetric analysis indicated that the addition of EG and APP (3 : 1 by weight) to ABS led to an increase in the amount of high‐temperature residue by 11.8 wt %, and a decrease of mass loss rate by 0.7%/°C compared with pure ABS. Scanning electronic microscopy revealed a homogeneous compact intumescent char layer of ABS/EG/APP samples. Based on our experiment and combined with others' previous studies, the synergistic mechanism is inferred. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

十溴联苯氧化物/氢氧化铝对丁苯橡胶的阻燃作用

分别将十溴联苯氧化物、氢氧化铝及其混合物作为阻燃剂加入到丁苯橡胶中,讨论了复合体系的最大转矩、固化速率及拉伸性能。结果表明,十溴联苯氧化物是比氢氧化铝更为有效的阻燃剂,能降低复合体系的100%定伸应力,对最大转矩没有影响。氢氧化铝的加入明显增大了丁苯橡胶的最大转矩,降低了100%定伸应力,对固化速率影响较小。两种阻燃剂同时加入到丁苯橡胶中具有协同作用,能提高丁苯橡胶的最大转矩,加快固化速率,对100%定伸应力影响较小。     

Enhanced flame retardancy of unsaturated polyester resin composites containing ammonium polyphosphate and metal oxides

Three metal oxides (MOs) (Fe₂O₃, Sb₂O₃, Al₂O₃) were incorporated into blends of unsaturated polyester resin (UPR)/ammonium polyphosphate (APP) composites with the aim of studying and comparing their synergistic effect on flame retardancy with APP. The UPR-APP/MOs composites were prepared, then the thermal stability and flame-retardant properties of the UPR composites were evaluated by thermogravimetric analysis (TGA), limiting oxygen index (LOI), vertical burning test (UL-94), and cone calorimetry test (CCT). Besides, residues after CCT were characterized by scanning electron microscopy and laser Raman spectroscopy. The LOI values of the UPR composites with 0.5 wt% MOs increased to around 40%. However, the CCT results indicated that the incorporation of Sb₂O₃ brought an increase in the total heat release. Moreover, these three MOs had different effects on the process of thermal degradation of UPR composites from the TGA results. Based on the above results, Al₂O₃ provided a best promotion on flame retardancy among three MOs.     

氢氧化镁协同阻燃剂的研究进展

综述了氢氧化镁阻燃剂的阻燃机理,介绍了Mg(OH)2高效协同阻燃剂的研究现状;展望了氢氧化镁协同阻燃剂未来的发展趋势和研究方向。     

有机硅阻燃剂协同阻燃作用的研究进展

论述了有机硅阻燃剂与卤系[如四溴双酚A双(2,3-二溴丙基)醚]、磷系(如聚磷酸铵)、无机系(如氢氧化铝和氢氧化镁)阻燃剂以及某些非阻燃物质(如硬脂酸盐、沥青、硅酸钾、二碱式亚磷酸铅、三碱式硫酸铅、碳酸钙等)协同阻燃的研究状况、发展趋势和应用前景。     

卡拉胶/金属氧化物协同聚磷酸铵制备阻燃天然橡胶

将卡拉胶(KC)、聚磷酸铵(APP)分别和Fe2O3、CuO、Al2O3、MnO24种金属氧化物(MO)三者复配构成的协同阻燃剂(KC/MO/APP)加入到天然橡胶(NR)中,制备了NR/KC/MO/APP复合材料.通过极限氧指数(LOI)、垂直燃烧(UL-94)、锥形量热(CCT)测试了其阻燃性能.结果表明,NR/KC/MO/APP复合材料的阻燃等级均达到UL-94 V-0级,LOI在26.5％～27.3％之间,具有较好的阻燃性.与NR相比,NR/KC/CuO/APP复合材料的热释放速率峰值和总热释放量分别下降了63.7％和42.0％.同时KC/MO/APP还有抑烟作用,NR/KC/Fe2O3/APP复合材料总烟释放量比NR下降了35.0％,处于最低水平.TGA结果显示,NR/KC/CuO/APP复合材料800℃时的残炭量(W800)达到34.85％,比NR/APP提高了28.7％.NR/KC/MO/APP复合材料炭层更致密,表明KC/MO与APP的协同作用对形成稳定炭层起着重要作用.另外,NR/KC/MnO2/APP复合材料力学性能最优,其拉伸强度和断裂伸长率比NR/APP分别提高32.6％和20.9％,表明MnO2的加入可弥补阻燃剂对NR造成的力学性能损失.     

卡拉胶/金属氧化物协同聚磷酸铵制备阻燃天然橡胶

将卡拉胶（KC）、聚磷酸铵（APP）分别和Fe2O3、CuO、Al2O3、MnO2 4种金属氧化物（MO）三者复配构成的协同阻燃剂（KC/MO/APP）加入到天然橡胶（NR）中,制备NR/KC/MO/APP复合材料。通过极限氧指数（LOI）、垂直燃烧（UL-94）、锥形量热（CCT）测试了复合材料阻燃性能。结果表明,NR/KC/MO/APP复合材料的UL-94均达到V-0等级,LOI在26.5%~27.3%之间,具有较好的阻燃性。与NR相比,NR/KC/CuO/APP复合材料的热释放速率峰值（pHRR）和总热释放量（THR）分别下降了63.7%和42.0%。同时KC/MO/APP还有抑烟作用,NR/KC/Fe2O3/APP复合材料总烟释放量（TSP）比NR下降了35%,处于最低水平。TGA结果显示,NR/KC/CuO/APP复合材料W800达到34.85%,比NR/APP提高了28.7%。SEM分析表明,NR/KC/MO/APP复合材料体系炭层更致密,表明KC/MO与APP的协同作用对形成稳定炭层起着重要作用。DMA和力学性能测试发现,NR/KC/MnO2/APP复合材料力学性能最优,其拉伸强度和断裂伸长率比NR/APP分别提高32.6%和20.9%,表明MnO2的加入可弥补阻燃剂对NR造成的力学性能损失。     

The synergistic effect of aluminum hypophosphide and nanosilica on flame‐retarded ethylene–propylene–diene monomer rubber

The influence of aluminum hypophosphide (AlHPi) and nanosilica on the flame‐retardant and mechanical property of ethylene–propylene–diene monomer (EPDM) rubber was evaluated by limiting oxygen index, and the value of tensile strength and elongation at break. The results show that the introduction of nanosilica into the EPDM/AlHPi blends can not only further improve the flame‐retardant property but also improve the tensile strength and elongation at break significantly, showing a synergistic effect between AlHPi and nanosilica. The flame‐retardant mechanism was further studied by X‐ray diffraction (XRD), thermogravimetric (TG) analysis, differential scanning calorimetry (DSC), and scanning electron microscope (SEM). The results of XRD and TG–DSC indicate that AlHPi will melt along with oxidation at about 337°C, which is helpful to full contact with nanosilica and to enhance the interaction between them; and will further recrystallize above 540°C, which is benefited to enhance the mechanical strength of char layer. The char morphological study by SEM shows that the char layer for the sample with both AlHPi and nanosilica is strong, more uniform and dense, and the scale of the holes in the char layer is smaller compared with the char layer of samples with AlHPi or nanosilica alone. The TG–DSC results show that the sample with both AlHPi and nanosilica has the weakest weight loss rate and heat release rate, compared with the samples with either of them, which is another evidence of the synergistic flame retardant effect between AlHPi and nanosilica. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

氢氧化铝对复合绝缘子用硅橡胶的性能影响研究

研究了氢氧化铝的粒径及填充量对复合绝缘子用热硫化硅橡胶的力学性能、电学性能、阻燃性、憎水性能的影响。实验结果表明：当氢氧化铝粒径为2.4μm时,硅橡胶的力学性能及阻燃性能达到最佳,憎水性及电学性能适中;氢氧化铝填充量为115～125份之间时,硅橡胶综合性能最佳,漏电起痕达到1A4.5,阻燃性能满足FV-0。     

Remarkable effects of silicone rubber on flame retardant property and mechanical properties of crosslinked high-density polyethylene/bio-based magnesium phosphate flame retardant (MHPA) composite

In this paper, a new bio-based flame retardant MHPA was prepared by the reaction of magnesium hydroxide (MH) and phytic acid (PA). Then the crosslinked high-density polyethylene (HDPE) flame-retardant composite was prepared by adding it and silicone rubber (SR) into HDPE and using electron beam irradiation. The test results of limiting oxygen index (LOI) and cone calorimeter test (CCT) show that the combination of MHPA and SR can increase the flame retardancy and smoke suppression performance of HDPE. The LOI of HDPE composite with 10 parts of SR is 28.3%, and its pHRR, THR and TSP values are reduced to 454.1 kW/m², 99.7 MJ/m² and 8.3 m², respectively, which is because MHPA and SR jointly promote the formation of continuous and high-density carbon slag in the combustion process of HDPE and inhibit the penetration of flame. In addition, the HDPE composite with 10 parts of SR has significant tensile strength, elongation breaking strength and tear strength, because SR can produce continuous stable structure with HDPE after irradiation and crosslinking. Therefore, this study verified that MHPA and SR together can effectively improve the flame retardancy, smoke suppression and mechanical properties of HDPE composite.     

Facile preparation and flame retardancy mechanism of cyclophosphazene derivatives for highly flame-retardant silicone rubber composites

A novel and efficient flame retardant cyclophosphazene derivative Hexa (p-acetamidophenoxy) cyclotriphosphazene (HACP) was successfully prepared via a facile one-step reaction. The chemical structure of HACP was characterized and confirmed by FT-IR, ¹H and ¹³C NMR. Then the as-prepared HACP was incorporated into addition-cure liquid silicone rubber (ALSR) matrix to prepare highly flame-retardant rubber composites. It was found that the incorporation of HACP can significantly enhance the flame resistance of ALSR. Typically, the ALSR composites filled with 30 phr HACP achieved UL-94 V-0 rating and meanwhile the total heat release and total smoke release were decreased by 26.9% and 41.5%, respectively. Moreover, the flame-retardant mechanism of ALSR/HACP composites was investigated by TGA, Py-GCMS, FT-IR, SEM and EDX, confirming that HACP plays a significant role in capturing free-radicals and forming protective layers. This work designed a novel cyclophosphazene-based flame retardant to significantly enhance the flame retardancy of ALSR, which may offer some valuable inspiration for the fabrication of highly flame-retardant polymer composites.     

硅橡胶阻燃开发研究进展

简单介绍了硅橡胶的燃烧过程及其自身的燃烧特性,并确立了硅橡胶的阻燃研究方向。综述了铝-镁系、磷氮系、硼硅铂系、膨胀型等不同类型阻燃剂在硅橡胶中的实际应用,并对未来阻燃技术进行了展望。     

Effects of treated waste silicon rubber on properties of poly(lactic acid)/ammonium polyphosphate composites

Considering the massive waste silicone rubber composites (WSiRC) in electrical and electronic engineering industries every year, the utilization of WSiRC is a meaningful and urgent task. In this study, WSiRC was utilized after a simple treatment in the flame retardant polylactic acid (PLA). The TG data in N₂ indicated that the char residues at 700 °C of the PLA/ammonium polyphosphate(APP)/WSiRC samples are improved with the loading of WSiRC, which means that WSiRC could act as the carbonization promoter for the PLA blends. Moreover, it is found in LOI, UL94, and cone tests that WSiRC can only improve the flame retardancy of PLA in an appropriate loading range since the crosslink structure formed by WSiRC may interact with that formed by APP and jointly improve the char‐formation ability of PLA. However, too much WSiRC deteriorated the flame retardancy of PLA because of the effect of WSiRC cluster at its higher loading. The photographs of the char residue after the cone tests also manifested that. The cone data showed that WSiRC could suppress the production of smoke as well. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45231.     

无机阻燃剂对单组分室温硫化硅橡胶性能的影响

试验研究氢氧化镁、氢氧化铝及其复合物对脱酮肟型单组分室温硫化（RTV-1）硅橡胶物理性能和阻燃性能的影响。结果表明，随着氢氧化镁用量的增大，RTV-1硅橡胶的硬度、拉伸强度和氧指数逐渐增大，拉断伸长率逐渐减小，氢氧化镁用量为50份时RTV-1硅橡胶具有阻燃性；氢氧化铝填充RTV1硅橡胶的硬度、拉伸强度和氧指数均高于相同用量氢氧化镁填充胶，氢氧化铝用量为40份时RTV-1硅橡胶具有阻燃性；氢氧化镁／氢氧化铝并用量为30份时RTV-1硅橡胶具有阻燃性，氢氧化镁／氢氧化铝质量比为1：4时其阻燃效果最佳。     

The thermal stability investigation of microencapsulated ammonium polyphosphate/siloxane‐modified epoxy resin composites

In this investigation, epoxy resin composites containing phosphate and silicone were prepared from microencapsulated ammonium polyphosphate (MFAPP) and poly(methylphenyl siloxane) (PMPS). Silicone‐containing epoxy (E‐S) copolymers were gained by the grafting reaction between ? OCH₃ of PMPS and ? OH of E51. And, a fixed weight of MFAPP was introduced to epoxy systems via the physical blending method. The chemical structure of the E‐S copolymer was determined by Fourier transform infrared spectroscopy (FTIR) and ¹H‐NMR. The impact testing results revealed that the impact toughness was improved slightly. The thermogravimetric analysis (TGA) results demonstrated that the thermal degradation property in high temperature region and solid residue yield at 800 °C were enhanced remarkably with increasing PMPS content, whether the testing atmosphere was in nitrogen or oxygen. Moreover, an obvious synergistic effect of silicon and phosphorus on promoting the thermo‐oxidative degradation stability and solid residue at 800 °C was proved. Furthermore, the scanning electron microscope micrographs and FTIR result of residual charred crusts of EA‐S systems after the TGA testing in air manifested that the bubbled charred layer and silicon‐ and phosphorus‐containing residue took chief responsibility for thermo‐oxidative degradation property and solid residue yield. So the MFAPP/siloxane‐modified epoxy resin composites have a significant development prospect in high‐temperature resistant organic adhesives and coatings. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45272.