BPS/有机氮磷复合阻燃增强增韧PA66材料的性能

以溴化聚苯乙烯(BPS)和自制的有机氮磷阻燃剂(NPR)为尼龙(PA)66的阻燃剂,以短切玻璃纤维为增强剂,加入增韧剂三元乙丙橡胶,制备了阻燃增强增韧PA66材料,研究了阻燃剂的加入及复配对材料力学性能、极限氧指数(LOI)、垂直燃烧性能、最大烟密度、热稳定性等性能的影响。结果表明,相对于BPS,NPR对材料力学性能的不利影响更大,单独使用BPS时材料的阻燃效果较差,而单独使用NPR可明显提升材料的阻燃性能,当NPR质量分数为15%时,材料的LOI为34%,垂直燃烧等级达到V–0级,拉伸强度、弯曲强度和缺口冲击强度分别为161,224 MPa和12 kJ/m~2。在阻燃剂总质量分数为15%的条件下,与单独使用NPR相比,BPS与NPR的复配进一步降低了材料的拉伸与弯曲强度,但在保持阻燃性能的同时降低了材料成本。NPR的加入导致材料最大烟密度有所增大,热降解提前,而BPS与NPR的复配进一步增大了材料的最大烟密度,使热降解有所延后。     

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.     

水滑石对PBS/Sb2O3阻燃PA6/GF性能的影响

研究了聚溴化苯乙烯(PBS)对玻纤增强尼龙6(PA6/GF)阻燃和力学性能的影响,并采用锥形量热仪研究了改性水滑石(HT)对PBS/Sb2O3阻燃PA6/GF抑烟作用和燃烧时热释放速率的影响。结果表明,随PBS用量增加,PA6/GF的氧指数增加,阻燃性提高,当PBS质量分数为20%时,PA6/GF的垂直燃烧达到FV-0级;HT燃烧后形成多孔、大比表面积的镁铝复合氧化物,能够有效吸附材料燃烧过程中产生的炭微粒,对PBS/Sb2O3阻燃PA6/GF具有显著的抑烟作用。当HT质量分数为5%时,烟释放速率降低27.6%,且对阻燃PA6/GF的力学性能影响不大。另外,HT使PA6/GF的氧指数和相比漏电起痕指数(CTI)提高。     

三聚氰胺聚磷酸盐/硼酚醛协效体系阻燃PA66/GF复合材料的研究

采用氮磷型阻燃剂三聚氰胺聚磷酸盐(MPP)与硼改性酚醛树脂(BPF)组成的复合阻燃体系对玻纤(GF)增强尼龙66( PA66)复合材料进行阻燃,获得了阻燃性能优异、力学性能良好的增强复合材料,研究了协效阻燃剂BPF/MPP配比、BPF/MPP用量及GF用量对阻燃复合材料阻燃性能的影响,采用微型燃烧量热和质量保持率分析方法研究了阻燃复合材料的燃烧及成炭行为,对复合阻燃剂的协效机理进行了讨论.结果表明,当BPF在BPF/MPP中的质量分数为15％时,添加25％ BPF/MPP复合阻燃剂可使20％ GF增强PA66复合材料达到V-0( 1.6 mm)阻燃级别,极限氧指数增加至25.3％,拉伸强度、弯曲强度、缺口冲击强度分别为116 MPa,132 MPa,7.1 kJ/m2.该复合材料可满足高性能无卤阻燃的使用要求.     

Investigation on phosphorus halogen‐free flame‐retardancy systems in short glass fiber‐reinforced PC/ABS composites under rapid thermal cycle molding process condition

In this study, standard test specimens with flame‐retarded short glass fiber‐reinforced PC/ABS materials were fabricated under rapid thermal cycle injection molding condition by selecting a potassium perfluorobutane sulfonate flame retardant specially used for PC, FR2025, and two kinds of aryl phosphorus halogen‐free flame retardants, UN707 and PX‐220. The flame‐retardancy effect of the above different flame retardants on the studied systems was compared through combustion tests of the specimens. Meanwhile, the thermal and mechanical properties of flame‐retarded composites were studied by using the thermogravimetry analysis, dynamic mechanical thermal analysis (DMTA), and universal testing machine. The results show that the “candlewick effect” of fibers exacerbates the fire behavior of composites. With the increase of the aryl phosphorus halogen‐free flame retardants, the flame‐retardancy effect of composites is obviously improved, and the maximum thermal degradation rate of composites is significantly decreased. The UL94 combustion rating is improved, and the time of residual flame is substantially reduced with the increase of PC content under the same content of flame retardant. The DMTA results show that the flame retardants have a reinforcement action on PC/ABS matrix. However, the macroscopic mechanical properties are slightly decreased in the glass fiber‐reinforced composites because of the destructive effect of the flame retardants on the interface compatibility between matrix and fibers; the scanning electron microscopic micrographs of tensile fracture fully prove this action mechanism of flame retardants. In addition, the addition of toughener and antidripping additive significantly affects the flame retardancy and mechanical properties of composites. POLYM. COMPOS., 36:1653–1663, 2015. © 2014 Society of Plastics Engineers     

氢氧化铝含量对聚酯/玻璃纤维复合材料阻燃性能和力学性能的影响

通过熔融混炼和模压成型工艺,制备含氢氧化铝(ATH)的干式不饱和聚酯/玻璃纤维(UP/GF)共混复合材料。采用氧指数法(LOI)和垂直燃烧法(UL94)表征UP/GF复合材料的阻燃性能,采用DMA研究UP/GF复合材料的动态力学性能,采用静态力学方法研究UP/GF复合材料的冲击和弯曲性能。结果表明:UP复合材料中,ATH的含量在25%时,既能够满足V—0级阻燃级别,氧指数值为28.7%,且材料的冲击和弯曲强度分别为5.66kJ/m2和58.72MPa,同时也有较好的动态力学性能。     

Comparative study on thermal decomposition and combustion behavior of glass‐fiber reinforced poly(1,4‐butylene terephthalate) composites containing trivalent metal (Al,La, Ce) hypophosphite

High fire hazards of glass‐fiber reinforced polymer composites have greatly limited their development and application. To reduce their flammability, the composites have to be treated with flame retardants. This work examines the use of three trivalent metal (Al, La, Ce) hypophosphites as halogen‐free flame retardants for glass‐fiber reinforced poly(1,4‐butylene terephthalate) (GRPBT) composites. The aim of this study is to quantitatively investigate the effect of metal hypophosphites on the thermal decomposition and combustion behavior of GRPBT composites by means of cone calorimeter and thermogravimetry coupled with Fourier transform infrared spectroscopy (TG‐FTIR) techniques. The peak heat release rate and total smoke production of GRPBT/cerium hypophosphite (CHP) composite evaluated by cone calorimeter are reduced, respectively, by around 76 and 44% compared to the results of GRPBT. The volatilized esters measured by TG‐FTIR in the decomposition of GRPBT/CHP are decreased by about 69%. The results showed that rare earth hypophosphites can effectively inhibit the thermal decomposition and combustion behaviors of GRPBT in comparison with aluminum hypophosphite. POLYM. COMPOS., 34:1832–1839, 2013. © 2013 Society of Plastics Engineers     

Preparation and characterization of straw/magnesium cement composites with high-strength and fire-retardant

To fully exploit the abundant bioresource crop straw, a straw-based composite with excellent fire retardant, high strength and dimensional stability was successfully prepared for use in building applications. The subject composite was composed of rice straw/magnesium cement (SMC) adhesive, with glass fiber as a reinforcement agent. The mechanical strength, dimensional stability, flame retardant, smoke suppression, and thermal stability of the material were used to evaluate its performance as a potential construction material. The effect of the addition of glass fiber and the pavement structure of straw and glass fiber were also characterized. The experimental results showed that the mechanical strength and rigidity of SMC composite were increased by the addition of 9% glass fiber to the total mass of the filler. Glass fibers reinforced and reduced the volume of the filler, while increasing the dimensional stability of the composites. The strength of the mixed structural composites was higher than layered structural composites, which is benefits the preparation of the composites. Compared to other straw/cement composites, glass-fiber reinforced SMC composites exhibited better strength, dimensional stability, flame retardant, smoke suppression and thermal stability. These superb properties make these novel composites an ideal candidate for use in the field of interior decoration, particularly in public venues.     

阻燃剂对UP复合材料流变性及磨损性能的影响

制备了含有氢氧化铝(ATH)、三聚氰胺多聚磷酸盐(MPP)及十溴二苯醚(DBDE)等不同阻燃剂的干式不饱和聚酯/玻璃纤维(UP/GF)共混复合材料。研究了不同阻燃剂对UP/GF复合材料的阻燃性能、流动性和磨损性能的影响,并借助SEM观察了采用不同阻燃剂的UP/GF复合材料的磨损面微观形貌。结果表明,ATH的添加质量为30%时,其UP/GF复合材料的阻燃性与DBDE添加量为25%的体系相当,达到UL94 V-0级,OLI值为30.0且具有很好的抑烟和防滴落效果;同时ATH、MPP的加入可适当提高复合材料流动性能,ATH还可以改善复合材料的磨损性能,磨损体积为未添加阻燃剂体系的50%左右。     

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     

阻燃剂与芳纶浆粕对三元乙丙橡胶性能影响的研究

以十溴二苯乙烷(DBDPE)、三氧化二锑和硼酸锌等作阻燃剂,以超细芳纶浆粕短纤维作耐烧蚀材料,通过共混方式制备了EPDM阻燃材料和耐烧蚀材料。研究了EPDM阻燃复合材料的阻燃性能、物理机械性能和燃烧炭化层微观结构形态。结果表明,三氧化二锑/硼酸锌/DBDPE用量分别为8份/20份/20份时,阻燃复合材料极限氧指数可达26.9%,垂直燃烧级别达到UL94—V0级;加入60份DBDPE时,极限氧指数达到36.3%;DBDPE/三氧化二锑/硼酸锌用量分别在60份/15份/20份以下时,对EPDM硫化胶拉伸性能无不利影响;三氧化二锑能明显提高DBDPE的阻燃性能;加入硼酸锌后氧指数略有提高,且明显改善抑烟效果和成炭效果;加入芳纶浆粕短纤维,对阻燃性能影响不大,但能明显改善炭化层致密性。     

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene (GF-PP) composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers (GF) surface to the flame zone. In this study, dipentaerythritol (DPER), a charring agent, was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER. DPER has a synergistic effect with the intumescent flame retardants (IFR) added in the composites, which can induce interfacial carbonization on the surface of GF, thus transforming the intrinsic smooth GF surface into roughness one. In this way, the negative effect of the wick effect in flame retardancy is weakened. Moreover, the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed. The PP composites with 20 wt% modified glass fiber (M-GF) and 30 wt% IFR can achieve the UL-94V-0, and its limiting oxygen index (LOI) value increased from 16.5% to 29.5%. Simultaneously, the heat release rate (HRR), total heat release (THR) and total smoke release (TSR) decreased significantly, and the peak of heat release rate (PHRR) reduced 60.6% compared with GF-PP.     

无卤阻燃聚酯复合材料研究进展

综述了近5年来的无卤阻燃聚酯复合材料的研究进展。讨论了有机阻燃剂（如磷酸盐、磷酸酯等）、无机阻燃剂（如红磷、蒙脱土等）和有机无机配合阻燃体系（如氢氧化铝/聚磷酸铵/可膨胀石墨等）等几大类阻燃体系阻燃聚酯后复合材料的力学性能、热稳定性、相容性、抑烟性以及不同添加量下热释放速率的变化,并对高效、环境友好的无卤阻燃聚酯复合材料的前景进行了展望。     

磷腈/三嗪双基分子复配阻燃聚乳酸

将磷腈/三嗪双基分子阻燃剂（HTTCP）分别与六苯氧基环三磷腈（HPCTP）和季戊四醇磷酸酯（PEPA）按不同配比复配,采用熔融共混法制备了阻燃聚乳酸（PLA）的复合材料。采用热失重分析仪、极限氧指数仪、垂直燃烧试验箱和锥形量热仪研究了2种复配阻燃体系及其配比对PLA阻燃复合材料热稳定性和阻燃性能的影响,并采用扫描电子显微镜对材料的残炭形貌进行了分析,探究了其阻燃机理。结果表明,PEPA/HTTCP复配阻燃剂的阻燃效果优于HPCTP/HTTCP复配阻燃剂。当PEPA/HTTCP的质量比为3/1,总添加量为20 %时,阻燃PLA的极限氧指数最高,为27.2 %,热释放速率峰值、平均热释放速率以及热释放总量达到最小值,且能够达到UL 94 V-0级。     

O–VMT和二乙基次磷酸铝对PBT/GF的阻燃作用

研究了有机蛭石(O–VMT)和二乙基次磷酸铝(ADP)对玻纤(GF)增强聚对苯二甲酸丁二酯(PBT)(PBT/GF)的阻燃作用,对复合材料的极限氧指数(LOI)和UL94阻燃等级进行测试,并用热失重和锥形量热仪进行分析。结果发现,ADP可以很好阻燃PBT/GF,加入19%的ADP,复合材料的LOI为33.5%,阻燃达到UL941.6 mm V–0级,相对PBT/GF,其点燃时间、火灾性能指数(FPI)有所提高,热释放速率峰值(PHRR)、平均热释放速率(AHRR)、总热释放量(THR)及总生烟量(TSR)有所降低。同时加入15%的ADP和2%的O–VMT,复合材料的PHRR,AHRR,THR和TSR相对单独添加17%ADP的材料,分别降低12.8%,9.5%,4.5%和15.9%,FPI提高15.4%,LOI和UL94阻燃也对应提高,O–VMT和ADP在PBT/GF中有协同阻燃作用。     

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     

Polyolefin–wood filler composite. I. Performance of m-phenylene bismaleimide-modified wood fiber in polypropylene composite

The properties of the composite of polypropylene (PP) and chemithermomechanical pulp reactively treated with bismaleimide-modified PP or premodified pulp have been investigated. The results were compared with the properties of unmodified composites of PP and pulp. The effect of some flame retardants on the properties of composites was also studied. Premodifications of PP as well as pulp with m-phenylene bismaleimide provided a positive response with regard to the mechanical properties of the composites. The tensile strength of a 35 wt % pulp-filled PP composite was found to be much higher than that of the strength of pure PP. On the other hand, tensile strength decreased considerably with increase in the chemithermomechanical pulp content if unmodified PP was used. The occurrence of chemical grafting reactions between PP and bismaleimide as well as between pulp and bismaleimide have been suggested, which can explain the aforementioned difference in mechanical properties among different composites. In situ addition of sodium borate, boric acid, or phenolic resin during processing of the composite decreased the rate of burning of PP. © 1994 John Wiley & Sons, Inc.     

Flame retardancy of hollow glass microsphere/rigid polyurethane foams in the presence of expandable graphite

Rigid polyurethane foams (RPUF) filled with various loadings of expandable graphite (EG) or/and hollow glass microspheres (HGM) were prepared by cast molding. The flame retardant properties of these composites were investigated by limiting oxygen index (LOI), horizontal and vertical burning tests. The composite with 10 wt % HGM and 20 wt % EG had the best flame retardant properties, and its LOI value reached 30 vol %. The addition of an appropriate loading of HGM improved the compressive strength and modulus of RPUF and EG/RPUF. When the HGM content arrived at 10 wt %, the compressive strength and modulus of the composites reached the maximum value. The dynamical mechanical analysis (DMA) showed that the addition of EG and HGM made the glass transition temperature shift to a higher temperature, and 10 wt % EG and 10 wt % HGM filled RPUF had the highest storage modulus. The scanning electronic microscope (SEM) observation indicates that the additives led to the decrease in the cell size. In addition, the flame retardant mechanism, the thermal properties, the burned surfaces and the interface surfaces were elucidated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

阻燃玻璃纤维增强PA6的紫外光稳定性

分别将三聚氰胺氰尿酸盐、十溴二苯乙烷、溴化聚苯乙烯和次磷酸盐作为阻燃剂对尼龙6(PA6)进行阻燃玻璃纤维增强改性,采用热失重分析仪、水平垂直燃烧测定仪、分光测色仪对PA6复合材料的热降解行为、阻燃性能和紫外光老化后色差值(△E)进行了分析.结果表明,阻燃剂的引入提升了PA6复合材料的阻燃性能,但是降低了复合材料的热稳定...     

Degradation of nano ZnO‐glass fiber‐unsaturated polyester composites

Degradation behavior of ZnO‐glass fiber‐unsaturated polyester composite under exposure to a metal halide lamp is investigated by means of DSC and FTIR. The FTIR results show that the UV photons can increase the carbonyl group on the surface, but ZnO can decrease the carbonyl content and further contribute to the breaking of single bond of carbon to oxygen on the surface. All of the results indicate that for pure unsaturated polyester under the UV exposure in air, the major reaction is photo‐initiated oxidation, whereas for the composites with ZnO, decarbonylation is the major effect. In addition, when the content of ZnO is not higher than 4 wt %, the composites are still transparent, and its effects on the crosslinking process and thermal stability are insignificant. Thus, ZnO can be used as a stabilizer of unsaturated polyester for the glass fiber reinforced polymer industry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009