镁铝羟基磷灰石/磷酸酯/聚苯乙烯复合材料的阻燃及力学性能研究

利用混合酚制备了一种新型阻燃磷酸酯(P),同时采用共沉淀法合成了镁铝羟基磷灰石(LDHs),将LDHS、P和聚苯乙烯(PS)通过熔融共混制备了LDHs/P/PS阻燃复合材料。利用氧指数法(OI)对其燃烧性能进行了表征,探讨了LDHs和磷酸酯两种阻燃剂对聚苯乙烯阻燃及力学性能的影响。结果表明:LDHs和磷酸酯两种阻燃剂对PS的阻燃具有协同增效作用,当固定磷酸酯的份数为10份时,复合材料的氧指数随着LDHs的含量增大而逐渐升高;当LDHs的含量为15份时,氧指数达到23.1%;当固定LDHs的含量为15份时,复合材料的氧指数也随着磷酸酯的加入量增大逐渐升高;当磷酸酯的份数为15份时,氧指数达到23.9%。由于LDHs和磷酸酯的加入,复合材料的力学性能与PS的力学性能相比有所下降。综合考虑阻燃性和力学性能,LDHs含量为10%、磷酸酯含量为10%时复合材料的阻燃以及力学性能较佳。     

Mg(OH)_2-Al(OH)_3-微胶囊红磷协同阻燃POE的研究

以氢氧化镁(MH)、氢氧化铝(ATH)为无卤阻燃剂,微胶囊红磷(MRP)为阻燃增效剂,通过共混挤出制备了一系列的阻燃聚烯烃弹性体(POE)复合材料。采用垂直燃烧、极限氧指数、热失重、傅里叶红外、微型量热分析等方法研究了其阻燃性能及阻燃机理。研究表明,同MH/POE和ATH/POE相比,MH/ATH/POE有较好的阻燃协效性,氧指数达到25.0%,残炭量达到31.7%,但垂直燃烧性能较差(测试无级别)。继续加入6份MRP后,体系的阻燃性能明显提高,其氧指数上升至27.5%,残炭量高达35.2%,垂直燃烧达到V-0级。表明MH/ATH和MRP对POE具有显著的协同阻燃作用。FTIR和TGA实验结果显示,MRP/MH/ATH/POE复合材料燃烧后生成了磷酸及其衍生物,增强了体系的成炭能力,促进了凝聚相阻燃效果,MRP阻燃机理主要表现为凝聚相阻燃。     

棉纤维/氢氧化铝/环氧树脂复合材料制备及性能分析

以硅烷偶联剂氨丙基三乙氧基硅烷(KH550)为改性剂,将改性处理后的棉纤维(CF)与氢氧化铝(ATH)和环氧树脂(EP)共混,制备得到棉纤维/氢氧化铝/环氧树脂(CF/ATH/EP)复合材料。通过测试复合材料的力学性能、剪切强度、极限氧指数(LOI)、热释放速率、抗紫外性能及拉伸断裂面微观形貌,分析了CF/ATH的用量比对复合材料综合性能的影响。结果表明:当CF/ATH的用量比为20/30时,复合材料具有较为优异的性能,LOI达到30.6%,垂直燃烧等级为V-0级,热释放速率为234.35 kW/m~2,剪切强度最佳为19.4 MPa,复合材料具有优良的抗紫外性能,可以制备得到综合性能较佳的高模量阻燃抗紫外纺织服装材料。     

无卤阻燃硅橡胶材料性能研究

考察了无卤阻燃剂氢氧化铝(ATH)、聚磷酸铵(APP)、金属氧化物三氧化二铁(Fe2O3)对甲基乙烯基硅橡胶(MVQ)阻燃性能及拉伸性能的影响。结果表明:硅橡胶中添加30份ATH后,材料氧指数达到32%;在ATH/MVQ(30/100)体系中添加45份APP,即APP/ATH用量比为3:2时,材料的氧指数达到38%,阻燃改性效果最佳;在此基础上添加不同用量的Fe2O3后,材料的氧指数均低于未添加Fe2O3的材料,Fe2O3对ATH/APP复配体系无明显协同阻燃作用。     

水滑石/LLDPE无卤阻燃复合材料的阻燃性

研究了以水滑石(LDHs),微胶囊化红磷(MRP)、三氧化二锑(Sb2O3)和二茂铁(FC)复配得到的复合阻燃剂对线形低密度聚乙烯(LLDPE)复合材料性能的影响.分别通过氧指数、水平燃烧和力学性能测试考察了复合材料的阻燃性能和力学性能.结果表明,当LLDPE/乙烯醋酸乙烯共聚物(EVA)/LDHs/MRP/Sb2O3/FC/过氧化二异丙苯(DCP)质量比为60/40/48/17/5/5/0.7时,复合材料的氧指数达到34.5%,阻燃级别为FH-1;断裂伸长率为225%,拉伸强度达10.9 MPa.     

氢氧化铝/氢氧化镁复配提高乙烯-醋酸乙烯共聚物阻燃性能

研究了不同质量比的氢氧化铝(ATH)和氢氧化镁(MH)对乙烯-醋酸乙烯共聚物(EVA)燃烧性能的影响,通过极限氧指数测试、垂直燃烧测试、热失重分析和锥形量热测试研究了EVA/ATH/MH复合材料的阻燃性能和热稳定性。结果表明,固定ATH和MH的添加量为60%(质量分数,下同),ATH/MH=2/1(质量比,下同)时,EVA/ATH/MH复合材料的阻燃性能最好,极限氧指数从18.3%提高到34.3%,达到UL 94V-2级别,热释放速率和热释放总量均有明显下降。     

基于煤矸石构筑环境友好型阻燃EVA的性能研究北大核心

通过添加不同比例的煤矸石构筑环境友好型阻燃材料类水滑石(LDHs),X射线衍射结果显示LDHs结构完整。以乙烯-乙酸乙烯共聚物(EVA)为基体树脂,LDHs为复配阻燃剂制备EVA/LDHs复合材料。采用极限氧指数仪、锥形量热仪、烟密度测试仪等研究了复合材料的燃烧性能和抑烟性能,并探讨了相应的阻燃及抑烟作用机理。结果表明:EVA3[n(Mg2+)∶n(Al3+)为3∶1]的极限氧指数最高,达到28.30%;与纯EVA相比,EVA/LDHs复合材料的热释放速率、质量损失、烟生成速率均显著降低,表现出良好的阻燃性能;在点火和未点火情况下,复合材料均体现出良好的抑烟性能。     

基于煤矸石构筑环境友好型阻燃EVA的性能研究

通过添加不同比例的煤矸石构筑环境友好型阻燃材料类水滑石(LDHs),X射线衍射结果显示LDHs结构完整。以乙烯-乙酸乙烯共聚物(EVA)为基体树脂,LDHs为复配阻燃剂制备EVA/LDHs复合材料。采用极限氧指数仪、锥形量热仪、烟密度测试仪等研究了复合材料的燃烧性能和抑烟性能,并探讨了相应的阻燃及抑烟作用机理。结果表明:EVA3[n(Mg2+)∶n(Al3+)为3∶1]的极限氧指数最高,达到28.30%;与纯EVA相比,EVA/LDHs复合材料的热释放速率、质量损失、烟生成速率均显著降低,表现出良好的阻燃性能;在点火和未点火情况下,复合材料均体现出良好的抑烟性能。     

类水滑石及其复配阻燃剂阻燃聚丙烯应用研究

以聚丙烯(PP)复合阻燃材料样条的极限氧指数(LOI)为主要考察指标,考察了类水滑石(LDHs)及其与焦磷酸哌嗪(PAPP)、次磷酸铝(AHP)等在不同质量比下复配添加对PP复合材料阻燃性能的影响。实验结果表明:当复配阻燃剂的添加量为40%,LDHs∶PPAP∶AHP质量比为3∶1∶1时,PP复合材料的LOI值由17.6%提高到28.6%,UL-94测试达到V-0级。添加了LDHs、PPAP、AHP的PP复合阻燃材料样条的弯曲和拉伸强度较单独添加LDHs时有所提高,力学性能得到明显改善。通过SEM分析和TG、DTG分析,初步认为不同质量比LDHs/PPAP/AHP的阻燃作用可简要概括为"协效成炭阻燃作用机制"。LDHs/PPAP/AHP的协效添加,明显提高PP复合材料的残炭率,样条燃烧后生成较厚的膨胀残炭层,提高了PP复合材料的阻燃性能。     

TPU/ATH/云母复合材料的制备及阻燃性能研究

以经表面处理或未经表面处理的氢氧化铝(ATH)与云母、热塑性聚氨酯弹性体(TPU)制备复合材料。采用垂直燃烧法和极限氧指数法研究了TPU/ATH和TPU/ATH/云母复合材料的阻燃性能,考察了ATH及云母的用量对复合材料的阻燃性的影响。结果表明：当TPU与ATH质量比为100/（70~80）时,复合材料具有很好的阻燃性能;经表面处理的ATH可以进一步改善复合材料的阻燃性能;云母的加入不影响复合材料的阻燃性能,但能改善其加工性能,降低产品价格。     

Preparation and flame retardancy of a novel flame‐retardant poly(ethylene‐co‐vinyl acetate)/aluminum hydroxide composites containing phosphorus

A novel flame‐retardant (SPDH) containing phosphorus was synthesized through the reaction of 10‐(2,5‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and synthesized intermediate product 3,9‐dichloro‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5] undecane‐3,9‐dioxide, which was used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/aluminum hydroxide (ATH) composites. The microstructure of SPDH was characterized and determined by Fourier transform infrared and nuclear magnetic resonance spectroscopy. Thermogravimetric analysis (TGA) showed that SPDH had good charring effect at high temperature (600°C). The flame retardancy of the optimized EVM/ATH composites by SPDH was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.8%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/ATH composite (EVM‐7) than EVM/ATH composite without SPDH (EVM‐3) with the total loading of additives. The heat release rate decreased and residual mass increased gradually as the loading of SPDH increased for the optimized EVM/ATH composites. There existed distinct synergistic flame‐retardant effect between SPDH and ATH in EVM matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Research on the related properties of EVM/Al(OH)3/SiO2 composites applied for halogen‐free flame retardant cable insulation and jacket

The halogen‐free flame retardant (HFFR) ethylene‐vinyl acetate copolymer (EVM)/ATH/SiO₂ composites have been prepared by melting compounding method, and the flame retardant, thermal stability, rheological, electrical, and mechanical properties have been investigated by cone calorimeter, LOI, UL‐94, TG, FE‐SEM, rotational rheometer, dielectric breakdown, and ultimate tensile. The results indicate that the flame retardant of EVM vulcanizates is improved and the fire jeopardizing is dramatically reduced due to the addition of ATH. It is necessary that sufficient loading of ATH (≥120 phr) is needed to reach essential level (LOI > 30; V‐0 rating) of flame retardant for HFFR EVM/ATH/SiO₂ composites used as cable in industry. The rheological characteristics show that at all the measurement frequencies, the storage and loss modulus of the composites increase monotonously as the concentration of ATH filler increases, while the complex viscosity and tan delta present reverse trend. And also, it has been found that the HFFR composites at high filler concentrations still keep good mechanical and electrical properties, which is very important for practical applications as cable. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

几种成炭性聚合物与红磷对HIPS/OMMT复合材料阻燃性能的影响

选取成炭性聚合物聚苯醚(PPO)、聚碳酸酯(PC)、聚醚酰亚胺(PEI),分别添加到高抗冲聚苯乙烯(HIPS)/有机蒙脱土(OMMT)复合体系中,极限氧指数(LOI)及水平垂直燃烧试验结果表明,复合体系的阻燃性能变化很小。将传统阻燃剂红磷(RP)与成炭性聚合物并用,可使HIPS/OMMT复合体系阻燃性能特别是水平垂直燃烧性能大幅提高。试验结果表明:红磷用量适中,添加较少量的成炭性聚合物,便能使复合体系分别达到水平燃烧FH-1级和垂直燃烧FV-0级。     

膨胀型阻燃剂/二乙基次磷酸铝阻燃改性不饱和树脂基复合材料

采用密胺包覆聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）作为膨胀型阻燃剂（IFR）对不饱和树脂（UP）进行改性,研究了APP、PER和MEL不同复配比例及用量对不饱和树脂基复合材料阻燃性能和力学性能的影响。基于IFR最佳用量,以二乙基次磷酸铝（ADP）为协效剂,研究了ADP用量对IFR/UP阻燃复合材料阻燃性能、力学性能及热稳定性的影响。结果表明,当APP∶PER∶MEL复配比例为4∶1∶1,IFR添加量为15 %（质量分数,下同）时,复合材料综合性能最佳,其极限氧指数为27.4 %,UL 94垂直燃烧达到V?1等级,弯曲强度和冲击韧性分别为100.3 MPa和6.3 kJ/m²;ADP的引入能够进一步提高IFR/UP复合材料阻燃性能,且随着ADP质量分数的增加而增强;当ADP质量分数为2 %时,IFR?ADP/UP复合材料极限氧指数为28.5 %并达到V?0阻燃等级,弯曲强度和冲击韧性分别为110 MPa和7.8 kJ/m²,与IFR/UP复合材料相比,分别提高了9.7 %和23.8 %;ADP能够促进IFR/UP复合材料表面成炭,缓解基体的热降解。     

Effects of ammonium polyphosphate and triphenyl phosphate on the flame retardancy,thermal, and mechanical properties of glass fiber–reinforced PLA/PC composites

The purpose of this study is to increase of the flammability properties of the glass fiber (GF)–reinforced poly (lactic acid)/polycarbonate (PLA/PC) composites. Ammonium polyphosphate (APP) and triphenyl phosphate (TPP) were used as flame retardants that are including the organic phosphor to increase flame retardancy of GF‐reinforced composites. APP, TPP, and APP‐TPP mixture flame retardant including composites were prepared by using extrusion and injection molding methods. The properties of the composites were determined by the tensile test, limiting oxygen index (LOI), differential scanning calorimetry (DSC), and heat release rate (HRR) test. The minimum T_g value was observed for the TPP including PLA/PC composites in DSC analysis. The highest tensile strength was observed in GF‐reinforced PLA/PC composites. In the LOI test, GF including composite was burned with the lowest concentration of oxygen, and burning time was the longest of this composite. However, the shortest burning time was obtained by using the mixture flame retardant system. The flame retardancy properties of GF‐reinforced PLA/PC composite was improved by using mixture flame retardant. When analyzed the results of HRR, time to ignition (TTI), and mass loss rate together, the best value was obtained for the composite including APP.     

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 %。     

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。     

Study on the flame retardancy of EVM/magnesium hydroxide composites optimized with a flame retardant containing phosphorus and silicon

A novel phosphorus‐silicon‐containing flame retardant, spirocyclic pentaerythritol bisphosphorate disphosphoryl chloride/9, 10‐dihydro‐9‐oxa‐10‐phosphaphanthrene‐10‐oxide/vinyl methyl dimethoxysilane (SPDV), was synthesized successfully and used for optimizing the flame retardancy of ethylene‐vinyl acetate copolymer (EVM) rubber/magnesium hydroxide (MDH) composites. The microstructure of SPDV was characterized and determined by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy. Thermogravimetric analysis (TGA) showed that SPDV had good charring effect in air even at high temperature (800°C). The flame retardancy of the optimized EVM/MDH composites by SPDV was investigated by limiting oxygen index (LOI), cone calorimeter, and UL‐94 vertical burning tests. A higher LOI value (29.4%) and better UL‐94 rating (V‐0) can be achieved for the optimized EVM/MDH composite (EVM‐7) than EVM/MDH composite without SPDV (EVM‐3) with the total loading of additives. The HRR decreased and residual mass increased gradually as the loading of SPDV increased for the optimized EVM/MDH composites. There existed distinct synergistic intumescent flame‐retardant effect between SPDV and MDH in EVM matrix. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

氢氧化铝/有机改性蒙脱土复合改性沥青性能研究

采用氢氧化铝(ATH)和两种有机改性蒙脱土(OMMT-C、OMMT-F)对沥青进行阻燃抑烟改性,旨在提高隧道沥青路面的阻燃抑烟性能。通过测试三大指标来评价ATH/OMMT复合改性沥青的常规性能,测试极限氧指数(LOI)与烟密度(SDR)来评价其阻燃抑烟性能,利用动态剪切流变(DSR)试验研究其流变性能。基于综合指数法优选出ATH/OMMT复合改性沥青的最佳复掺配比,通过热重(TG)试验分析了ATH/OMMT复合改性沥青的热解燃烧特性并建立了阻燃性能预测模型。研究结果表明,ATH/OMMT复合阻燃剂提高了沥青的稠度与软化点,降低了沥青的低温性能。当ATH掺量为10%(质量分数),OMMT-C掺量为3%(质量分数)时,复合改性沥青的综合性能最优,其极限氧指数大于23%,符合路用阻燃沥青的标准,同时烟密度相对基质沥青降低了33.9%,初始分解温度较基质沥青提高了3~6 ℃,分解残余量提高率最高可达61.3%。ATH/OMMT-C复合阻燃剂通过阻隔热交换通道提高了沥青的阻燃抑烟性能,通过增加沥青的弹性成分提高了沥青的复数模量与车辙因子,以及高温抗变形能力。     

Preparation of aluminum hydroxide/aluminum phosphinate flame‐retardant poly(vinyl alcohol) foam through thermal processing

A novel flame‐retardant poly (vinyl alcohol) (PVA) composite foam was prepared successfully through thermal processing, which was filled with high content of flame retardant, based on aluminum hydroxide (ATH) and aluminum phosphinate (AlPi) and using water as plasticizer and blowing agent. The flame‐retardant property and mechanism of the prepared foam matrix were studied by vertical burning test, limiting oxygen index (LOI), cone calorimeter, scanning electronic microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The experimental results showed that the PVA/ATH/AlPi (1/1.2/0.05) composite achieved LOI value of 41% and UL94 V‐0 (3.2 mm) rate. The addition of ATH and AlPi into PVA matrix significantly decreased flammability of the composites, because a more compact and continuous char layer of the PVA/ATH/AlPi composite could be formed, due to the involvement of AlPi in the char‐forming reaction. Compared with the pure PVA sample, the peak heat release rate (PHRR) and total heat release (THR) of PVA/ATH/AlPi (1/1.2/0.05) composite were reduced by 76.5% and 58.2%, respectively. Built upon this PVA‐based foam matrix with good flame retardancy, the flame‐retardant PVA‐based foam was successfully prepared through thermal extrusion. In addition, the influence of water content on melt viscosity, foam structure and mechanical strength was also analyzed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42020.