苯并嗪协效二乙基次磷酸铝阻燃PA66的研究

以双酚A型苯并嗪(BOZ)为成炭协效剂,二乙基次磷酸铝(ADP)为阻燃剂,通过熔融共混制备了阻燃尼龙66(PA66)复合材料。通过垂直燃烧测试(UL94)、极限氧指数(LOI)、锥形量热(Cone)、SEM以及TGA等考察了复合材料的协同阻燃性能及作用机制。结果表明:BOZ和ADP具有良好的协同阻燃效应。适量BOZ的引入不但可以提高材料的阻燃性能,还可以改善材料的热稳定性,并且对材料的力学性能影响不大。添加占体系质量分数0.3%BOZ和质量分数7.7%ADP时,ADP/BOZ阻燃PA66复合材料的垂直燃烧达到UL94V-0级,LOI达到了32.8%,拉伸强度、弯曲强度分别为81.52、111.11 MPa。阻燃机理研究表明:ADP/BOZ和ADP都是以气相阻燃作用为主的气相和凝聚相协同阻燃机制。     

次磷酸铝/环氧硅树脂阻燃PA6的性能研究

将次磷酸铝(AHP)和环氧硅树脂(ESR)复配后添加到聚酰胺6(PA6)中制备了阻燃PA6材料。通过极限氧指数(LOI)和垂直燃烧(UL 94)测试研究了该阻燃PA6材料的阻燃性能,利用扫描电子显微镜(SEM)观察了阻燃PA6的残炭形貌,同时还通过拉伸、弯曲和冲击强度测试考察了阻燃PA6的力学性能。结果表明:当AHP用量为24%时,阻燃PA6材料通过了UL 94V-0测试,其LOI值达到25.6%;而以质量比为95:5的复配阻燃剂AHP/ESR对PA6进行阻燃,且阻燃剂用量仅为18%时,阻燃PA6材料通过UL 94V-0测试,其LOI值达到25.8%,这说明AHP与ESR对PA6具有良好的协效阻燃作用。与PA6/AHP复合材料相比,PA6/AHP/ESR复合材料的力学性能有所改善,这说明ESR的加入可提高材料的力学性能。此外,SEM测试结果显示,ESR的加入有助于阻燃PA6材料形成均一、致密的炭层,对下层的材料起到了很好的保护作用,从而提高了材料的阻燃性能。     

新型磷氮阻燃剂对尼龙6的阻燃作用

研究了一种基于烷基次磷酸铝的新型磷氮阻燃剂(OP)对尼龙6(PA6)的阻燃作用。试验结果表明:该阻燃剂对PA6具有良好的阻燃作用,当其添加质量分数为25%时,PA6的氧指数(LOI)大于30%,阻燃级别达到FV-0级,燃烧时材料的热释放速率、质量损失速率和总热释放量明显降低。热重分析结果表明:OP改变了PA6的热降解过程,使之成炭化学反应提前,形成的炭层通过隔热和隔氧而产生阻燃作用。添加OP对材料的机械性能有些影响,如弯曲强度和弯曲模量有所增加,而拉伸强度和冲击功有所下降,但影响不大。     

苯并噁嗪协效二乙基次磷酸铝阻燃PA66复合材料的制备及性能

以双酚A型苯并噁嗪（BOZ）作为成炭协效剂，与二乙基次磷酸铝（ADP）复配,通过熔融共混制备了阻燃尼龙66（PA66）复合材料。通过垂直燃烧测试（UL94）、极限氧指数（LOI）、锥形量热（Cone）、扫描电镜（SEM）以及热分析（TG/DTG）等考察了复合材料的协同阻燃性能及作用机制。结果表明：BOZ和ADP具有良好的协同阻燃效应。适量BOZ的引入不但可以提高材料的阻燃性能，还可以改善材料的热稳定性，并且对材料的力学性能影响不大。添加0.3wt%BOZ和7.7wt%ADP时，ADP/BOZ阻燃PA66复合材料的垂直燃烧达到UL94 V-0级，LOI达到了32.8%，拉伸强度、弯曲强度分别为81.52、111.11MPa。阻燃机理研究表明：ADP/BOZ和ADP都是以气相阻燃作用为主的气相和凝聚相协同阻燃机制。     

PA66/AlPi/PPFBS复合材料的协效阻燃机理

以二乙基次磷酸铝(Al Pi)和全氟丁基磺酸钾(PPFBS)为复配阻燃剂,在密炼机上通过熔融共混的方法制备Al Pi和PPFBS复配阻燃PA66复合材料,并通过热重质谱联用(TG–MS)和扫描电子显微镜(SEM)研究了复配阻燃剂对PA66复合材料阻燃性的影响及其阻燃机理。结果表明,当添加6份Al Pi和0.08份PPFBS的复配阻燃剂时,阻燃PA66复合材料可以通过垂直燃烧测试,阻燃等级达到V–0级,极限氧指数(LOI)为31.1%。复配阻燃体系的加入虽然降低了阻燃PA66复合材料的力学性能,但提高了阻燃PA66复合材料的热稳定性,阻燃PA66复合材料的残炭率由纯PA66的4.1%上升至10.2%,促进了连续、致密炭层的形成,而且燃烧过程中不断释放出不燃性气体。Al Pi和PPFBS复配后兼具凝聚相和气相阻燃机理,表现出良好的协效阻燃效果。     

PA66阻燃改性研究

通过卤系、氮系、磷系等阻燃体系对尼龙（PA）66进行阻燃改性研究，开发出一种赤磷与无机阻燃剂共用的复配阻燃体系。结果表明，当加入 赤磷10份、无机阻燃剂10份、玻纤30份时，利用该阻燃体系阻燃的PA66，其燃烧性能达FV－0级，拉伸强度大于100MPa，缺口冲击强度大于9kJ/m^2，综合性能优良。     

膨胀型阻燃剂对聚丙烯-木粉复合材料阻燃及性能的影响

主要以聚磷酸铵(APP)、季戊四醇(PER)、以及自制的成炭发泡剂(CFA)复配成的膨胀型阻燃剂对聚丙烯-木粉复合材料进行阻燃.并通过一系列的性能实验研究了不同的阻燃剂配方及阻燃剂含量对聚丙烯-木粉复合材料的力学性能、阻燃性能、流变行为以及热降解行为的影响.结果表明,膨胀型阻燃体系可以提高聚丙烯-木粉复合材料的LOI与成炭性,当添加量为25%时,APP与PER复配阻燃的复合材料的LOI可达27.5,800℃时残余炭含量为19.24%.而且该阻燃剂的加入对提高材料的拉伸和弯曲强度有一定作用.     

硼酸锌对氮磷协效阻燃玻纤增强尼龙66性能的影响

为提高三聚氰胺聚磷酸盐(MPP)和二乙基次膦酸盐(OP)协效阻燃玻纤(GF)增强尼龙66(PA66)的综合性能,引入少量的无机阻燃剂硼酸锌(ZB)作为协效剂,系统研究了不同添加量的ZB对阻燃材料的阻燃性能、热稳定性、力学性能和白度的影响。结果表明,当MPP和OP的总添加量为15%,复配0.5%的ZB时,阻燃GF增强PA66的垂直燃烧阻燃等级达到UL94 V–0级,且热释放总量由MPP/OP体系的15.4 k J/g降为13.7 k J/g;ZB的引入促进了连续、致密炭层的形成,增强了凝聚相阻燃;ZB增强了阻燃材料的热稳定性,ZB复配量为1.0%的阻燃材料的初始降解温度提高到了301℃,有效避免了加工过程中的降解;当ZB添加量为1.0%时,阻燃材料的拉伸强度和缺口冲击强度分别为100.9 MPa和4.22 k J/m~2,均优于未添加阻燃剂的纯GF增强PA66;同时,样品的白度得到了明显提升,有利于阻燃GF增强PA66的工业化应用。     

溴化聚苯乙烯协同三氧化二锑阻燃PA6的性能

溴化聚苯乙烯(BPS)协同不同粒径的Sb_2O_3复配制备阻燃PA6,研究阻燃PA6的物理机械性能、UL94、LOI、阻燃性能和烟气释放.力学试验结果显示:协同阻燃体系的加入,提高了PA6的热变形温度、邵氏硬度、弯曲强度、弯曲模量和维卡软化点,注塑成型收缩率增加,缺口冲击强度、断裂伸长率和熔体指数下降.当粒径为0.4 μm时,综合力学性能最佳.燃烧性能和CONE测试结果显示:阻燃PA6的燃烧性能提高到ULV-0级,LOI升高,av-HRR、Pk-HRR、Pk-HRR/TTI、THR、EHC显著下降、轰燃时间大幅延长,且Sb_2O_3粒径越小,阻燃效果越好,但av-SEA、av-CO、SPR明显上升,阻燃但不能抑烟.     

S–N–P阻燃剂对聚碳酸酯性能影响研究

采用S–N–P阻燃剂通过熔融共混法制备了阻燃聚碳酸酯(PC)材料,通过极限氧指数(LOI)仪、垂直燃烧仪、万能电子试验机、冲击试验机和热重(TG)分析仪分别研究了阻燃PC的阻燃性能、力学性能和热性能。结果表明,S–N–P阻燃剂能显著提高PC的阻燃性能,当其质量分数为0.1%时,阻燃PC的LOI值达到35.5%,与纯PC相比提高了43.15%,能通过UL 94 V–0等级,同时拉伸强度相比纯PC提高了17.35%,弯曲强度提高了36.7%,断裂伸长率提高了121.6%,缺口冲击强度仅降低了7.63%;TG分析表明S–N–P阻燃剂能加速PC降解,从而加速炭层的形成起到阻燃作用。     

An easy‐to‐obtain silicone‐containing flame retardant and its effects on the combustion of polycarbonate

A novel silicone‐containing flame retardant (HSOBA) synthesized from hydrogen‐containing silicone oil and Bisphenol A via a simple approach has been incorporated into polycarbonate (PC) matrix to study its effects on the flame retardancy. The flame retardancy of PC/HSOBA composites is investigated by limiting oxygen index (LOI), vertical burning tests (UL‐94), and cone calorimeter measurement. The LOI value of the composites is 31.7 and the UL‐94 rating reaches V‐0, when the content of HSOBA is 3 wt %. Cone calorimeter data confirm that the HSOBA acts as an effective additive functioning both as flame retardants and as smoke suppressant. Evolution of the thermal behaviors of the composites tested by TGA, the morphological structures, and the constituent of char residue after LOI tests characterized by scanning electronic microscopy‐energy‐dispersive X‐ray analysis were used to explain the possible flame‐retardant mode. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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。     

Investigation of flame retardancy and physical–mechanical properties of zinc borate/boric acid polyester composites

The glass fiber reinforced polyester composite materials were prepared with varying contents of boric acid, zinc borate, and magnesium hydroxide as flame retardants to improve the flame retardancy of the composites. Experimental results showed that boric acid exhibited a good flame retardant effect on the polyester composite. When boric acid content is used as 15 wt %, the Limiting Oxygen Index (LOI) value of the composite reached upto 25.3. The increase in boric acid content from 15 to 30 wt %, the LOI values of composite were enhanced from 25.3 to 34.5 by 9.2 units. The LOI values of the composite samples increased with increasing boric acid content. The smoke density results showed that the addition of glass fiber and flame retardants decreased the smoke density of the unreinforced polyester resin. The mechanical properties of the composites have decreased by the addition of flame retardants. The scanning electron micrographs taken from fracture surfaces were examined. The flame retardants, such as boric acid, were well dispersed in the glass fiber reinforced polyester composites and obviously improved the interfacial interaction between glass fibers and polyester composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of phosphorus–nitrogen compound on flame retardancy and mechanical properties of polylactic acid

A phosphorus-nitrogen flame retardant (PN) was synthesized by using cytosine and diphenylphosphinic chloride. The flame retardancy and thermal stability of polylactic acid (PLA)/PN composites were investigated by the UL-94 vertical burning test, limited oxygen index (LOI), cone calorimeter test, and thermogravimetric analysis. The PN performs efficiently on improving the flame retardancy of PLA. The PLA composite achieves the UL-94 V-0 rating and its LOI increases to 30.4 vol% by adding 0.5 wt% PN. The flame retardant mechanism analysis showed that PN catalyzes the degradation of PLA to improve the flame retardancy by melting-away mode. Meanwhile PN reduces the release of flammable gasses during thermal degradation of PLA by promoting the transesterification of PLA, which is helpful for extinguishing flame. Moreover, triglycidyl isocyanurate (TGIC) was used as a micro-crosslinking agent to reduce the loss of mechanical properties of PLA/PN composites caused by degradation. Adding 0.1 wt% TGIC and 1.0 wt% PN into PLA, the tensile strength and elongation at break of PLA/PN are increased to the same level as that of PLA. Therefore, PLA with excellent comprehensive performance can be obtained.     

碱式碳酸镁基复合阻燃剂的制备及其阻燃性能研究

采用硅烷表面处理的碱式碳酸镁纳米片和氢氧化镁以及氢氧化铝为复合阻燃剂,通过密炼模压法制备了一系列复配阻燃剂协效阻燃EVA的复合材料。利用拉伸性能测试仪、熔融指数仪、垂直燃烧测试仪和锥形量热仪分别测试了复合材料的力学性能、加工流动性能和阻燃性能,利用热重分析仪测试了复配阻燃剂的热分解行为。结果表明,复配阻燃剂以适当比例协效阻燃EVA在更宽的燃烧温度范围内发生分解,能够起到更好的阻燃效果。并且复配阻燃剂/EVA复合材料的热释放速率和烟释放率大幅度降低,分别为181.06 kW/m²和0.032 m²/s。另外,复配阻燃剂/EVA复合材料的拉伸强度达到9.73 MPa,断裂伸长率为155.07%,每10 min熔融指数为1.00 g,符合电线电缆行业标准。     

Study on char reinforcing of different inorganic fillers for expandable fire resistance silicone rubber

Sodium silicate monohydrate (NSH), glass frits (GF) and aluminum hydroxide (ATH) were incorporated into room temperature vulcanized (RTV) silicone rubber (SR) as char reinforcing materials to improve the fire resistance of intumescent flame retardant silicone rubber. SR composites containing only intumescent flame retardant such as phosphorus nitrogen composite flame retardant (NH₂-C) and expandable graphite (EG) were used as comparison samples. Limiting oxygen index (LOI) test, vertical burning test (UL-94), flame resistance test, scanning electron microscopy (SEM) and X-ray diffraction spectroscopy tests, as well as volume variation and compression strength of char residues were used to discuss the effects of the above-mentioned fillers on the fire resistance, char residue strength and char integrity of SR composites. The results showed that SR composite filled with only intumescent flame retardants EG and NH₂-C had excellent flame retardancy. After adding ATH, the char residue was relatively dense and had good compressive strength, but its thermal insulation performance was reduced. GF or NSH reduced the flame retardancy of SR composites, but it obviously played a role in binding combustion residues, forming new crystals and improving the stability of char residues.     

Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine

An efficient intrinsic flame retardants composite was prepared by curing epoxy resin with a functional magnesium organic composite salt (FMOCS, 0.685 ± 0.3 nm) and diethylenetriamine (DETA). Curing behavior, thermal and flame‐retardant properties of the cured epoxy resins were systematically investigated by infrared spectrum (FTIR), thermogravimetric analysis (TGA), vertical burning test (UL‐94) and limited oxygen index (LOI) measurement. It was found that flame retardancy and mechanical properties of the cured composite are significantly enhanced compared with DETA/EP. The LOI of the EP reached to 33%, which is much higher than the DETA/EP (19%) or its IFR composite (31%) in the optimal addition of ammonium polyphosphate (APP, 18.69 wt %), pentaerythritol (PER, 6.21 wt %) and FMOCS (3.50 wt %). Furthermore, the mechanical properties of the composite material measurement results to imply that it can enhance tensile strength (150%) and bending strength (88%) rather than DETA/EP, which were tested by impact testing machine and microcomputer control electron universal testing machines. Copyright © 2016 John Wiley & Sons, Ltd.     

Butyltriphenylphosphine-based chelate borates influenced on flame retardancy of polystyrene composite containing self-expanded intumescent flame retardants

The polystyrene (PS) composite containing self-expanded intumescent flame retardant (polyphosphate ammonium and expandable graphite) was blended with three butyltriphenylphosphine-based chelate borates, respectively, to evaluate their effect on flame retardancy. The chemical structure of as-prepared three chelate borates was confirmed by nuclear magnetic resonance (NMR) and Fourier transform infrared spectrum (FTIR). The flame retardancy of various PS composites was evaluated by vertical burning test (UL-94), limited oxygen index (LOI), and cone calorimeter (CC). Flammability and combustion results suggested that one of chelate borates, named [BTP][BMB], made PS composite (PS4) obtain V-0 rating, 27.0 ± 0.3% LOI value, and reduction on heat release and smoke production with 17 wt% total flame retardants loading. The combustion residue was analyzed by scanning electron microscope and FTIR, and the pyrolysis gaseous products were investigated by TG-FTIR technique. Besides, complex viscosity of PS composites composed of various chelate borates from a rheology instrument indicated that the improvements of flame retardancy of PS composites depended on the temperature of construction of crosslinked network by expandable graphite, which the chelate borates showed distinctive influence. Accordingly, the flame-retarding mechanism about fast response to flame has been proposed.     

有机磷阻燃剂HDP与HMP在聚碳酸酯中的应用

研究高熔点环保型有机磷阻燃剂对苯二酚双(二苯基磷酸酯)(HDP)与对苯二酚双[二(1-甲基-2-苯基)磷酸酯](HMP)在聚碳酸酯(PC)中的应用。结果表明,当阻燃剂质量分数为7%时,PC/HDP与PC/HMP的极限氧指数测试(LOI)值分别为30.4与30.6,相对于PC(28.0)有较大提升,并且垂直燃烧测试(UL-94)都通过了V-0级,拉伸强度提升约3.5 MPa,弯曲强度提升约8 MPa。热重(TG)曲线和热重微分(DTG)曲线表明,HDP与HMP都降低了PC材料的最大热分解速率,同时PC/HDP的成碳效果优于PC/HMP。