膨胀型阻燃剂对PBT阻燃性能及力学性能的影响

通过熔融共混制备出了聚对苯二甲酸丁二醇酯(PBT)/膨胀型阻燃剂(IFR)复合材料,采用UL 94垂直燃烧、极限氧指数测试(LOI)、扫描电子显微镜(SEM)、拉伸和冲击测试来表征其阻燃性能和力学性能;系统地研究了不同含量的IFR对PBT阻燃性能、力学性能的影响。实验结果表明,随着阻燃剂IFR含量的增加,PBT/IFR复合材料的阻燃性能逐渐提高,但其力学性能相应地下降。当阻燃剂质量分数为30%时,达到V-0级,综合性能最佳。     

偏硼酸钡在红磷阻燃增强尼龙中的应用研究

采用熔融共混法制备了尼龙(PA6、 PA66)/红磷母粒/玻纤/偏硼酸钡复合材料。通过力学性能测试、 UL94垂直燃烧法、灼热丝试验、氧指数(LOI)等研究了偏硼酸钡对复合材料力学性能和阻燃性能的影响。力学性能测试结果表明,加入偏硼酸钡不影响复合材料的强度,但会降低缺口冲击强度;阻燃测试结果表明,偏硼酸钡在红磷阻燃尼龙中有良好的协效作用,可使复合材料阻燃性能达到UL94 V-0 (1.6 mm)等级,且灼热丝起燃温度(GWIT)可达750℃;氧指数测试结果表明,加入偏硼酸钡能有效提高复合材料的氧指数。     

膨胀阻燃剂/纳米黏土复配阻燃ABS

通过熔融共混法制备了有机化纳米黏土(OMMT)与膨胀型阻燃剂(IFR)复配阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS),并以苯乙烯/乙烯-丁烯/苯乙烯共聚物接枝马来酸酐(SEBS-g-MAH)作为增容剂。采用冲击和拉伸试验方法对材料的力学性能进行表征,采用极限氧指数(LOI)、垂直燃烧(UL94)和锥形量热(Cone)试验对材料的燃烧行为进行分析。结果发现,加入增容剂SEBS-g-MAH后,膨胀型阻燃剂与ABS的相容性得到提高,力学性能得到大幅提高。例如,5%SEBS-g-MAH加入到ABS/IFR(60/40)复合材料中,冲击强度提高至9 kJ/m~2,与未添加SEBS-gMAH体系相比,冲击强度的提升幅度较大。SEBS-g-MAH对复合材料体系的传统阻燃性能的影响较小。适量纳米黏土与膨胀型阻燃剂的复配可以进一步降低ABS树脂力学性能的损失,对传统阻燃性能(LOI和UL 94垂直燃烧级别)的影响较小,在ABS/IFR/SEBS(75/25/5)复合材料体系中,加入纳米黏土后,高温下可以形成阻隔炭层,隔绝热量和氧气。因此,与纯ABS和ABS/IFR/SEBS(75/25/5)复合材料体系相比,纳米黏土能显著降低ABS树脂在锥形量热测试中的热释放速率、热释放速率的峰值和总的放热量,有利于减缓火灾蔓延的速度。     

膨胀阻燃环氧树脂/有机化凹凸棒土复合材料的制备及性能研究

考察了不同膨胀型阻燃剂(IFR)添加量对环氧树脂(EP)阻燃性能的影响,以及有机化凹凸棒土(OAT)对膨胀阻燃环氧树脂复合材料性能的影响,最后对复合材料的增韧机理及阻燃机理进行了简要分析。结果表明,在环氧树脂中加入25%的IFR,可使复合材料的氧指数(LOI)达到30%,并通过UL94 V-0级测试,但拉伸性能有所降低;在膨胀阻燃环氧树脂体系中,适量添加3%的OAT能使复合材料的力学性能有所提高,对氧指数未见协同改善效果,但都通过了UL94垂直燃烧测试。     

无卤膨胀阻燃长玻纤增强聚丙烯性能研究*

利用无卤膨胀阻燃剂(IFR)阻燃长玻纤增强聚丙烯(LGFPP)复合材料,研究IFR的添加量对复合材料阻燃性能、热稳定性能、燃烧性能和力学性能的影响。结果表明,加入IFR使复合材料燃烧后生成了具有阻燃作用的炭层,显著提高了复合材料的阻燃性能。随IFR添加量的增加,复合材料的极限氧指数(LOI)逐渐提高,热释放速率峰值及其平均值、总热释放速率和生烟速率逐渐降低,力学性能略有下降。当IFR质量分数为20%时,复合材料的LOI和垂直燃烧等级分别达到了24.4%和UL 94 V-0级。     

含磷钛酸酯偶联剂改性膨胀型阻燃剂及其阻燃聚丙烯的研究

采用含磷钛酸酯偶联(剂PTCA)对由三聚氰胺焦磷酸(盐MPP)和季戊四(醇PER)复配组成的膨胀型阻燃(剂IFR)进行表面改性,并用其制备阻燃聚丙烯(PP)。研究了PTCA用量对PP/IFR共混物力学性能和阻燃性能的影响,并通过热重分析和扫描电镜对共混物进行了表征。结果表明:PTCA有效改善了IFR与PP基体的相容性,提高了PP/IFR共混物的力学性能及阻燃性能。当PTCA用量为1.0%时,共混物的拉伸强度和缺口冲击强度为27.3 MPa和3.2 kJ/m2,分别比未改性的PP/IFR提高了18.7%和6.7%;LOI从未改性PP/IFR的28.5%提高到31.5%,且通过UL94 V-0级;此外,共混物的热稳定性也明显提高,700℃时的残炭率由未改性PP/IFR的8.2%提高到12.1%。     

聚磷酸铵和三嗪成炭剂复合聚丙烯在水煮条件下的阻燃和力学性能

将乙二胺代三嗪成炭剂(ETCA)与聚磷酸铵(APP)复配,制备了两种不同质量分数的双组分膨胀型阻燃剂(IFR)阻燃的聚丙烯(PP)材料,分别为23%IFR/PP、27%IFR/PP。通过极限氧指数仪、UL94垂直燃烧仪、锥形量热仪、电子万能试验机和冲击试验机等分别研究了80℃热水处理7 d前后的阻燃聚丙烯复合材料的燃烧性能与力学性能。结果表明,复配膨胀型阻燃剂的加入使PP材料的阻燃性能提高,但力学性能下降;两组双组分阻燃试样23%IFR/PP、27%IFR/PP在80℃热水处理3 d能保持UL94 V-0级别,LOI分别达27.7%和29.0%,3 d之后阻燃级别降为无级别,但是7 d之后LOI值仍能达25.3%和27.0%;水煮之后,相比于未水煮阻燃试样,23%IFR/PP、27%IFR/PP的拉伸强度下降,但冲击强度增加。     

磷系阻燃剂NYP3对PBT阻燃性能影响的研究

经由新型磷系阻燃剂氨基三亚甲基膦酸铝(NYP3)与二乙基次膦酸铝(BEP-22E)复配使用,制备了无卤阻燃的增强PBT复合材料,并研究了材料的阻燃性能和燃烧残余物表面形貌。结果表明,添加质量分数为6%NYP3、10.5%BEP-22E时,材料UL 94垂直燃烧1.5 mm测试可达到V-1,LOI值高达37.1%;添加质量分数为4%NYP3、12.5%BEP-22E时,材料UL 94垂直燃烧1.5 mm测试可达到V-1,LOI值高达39.5%。由锥形量热分析可知,NYP3和BEP-22E复配使用可以有效降低复合材料的HRR及THR值,燃烧时有助于在材料表面形成致密炭层。     

玻纤对阻燃聚甲醛复合材料阻燃性能、力学性能及流变行为的影响研究

采用熔融共混法制备了膨胀型阻燃剂(IFR)和玻纤(GF)增强改性的聚甲醛复合材料,利用垂直燃烧测试、极限氧指数测试、简支梁摆锤冲击试验机及万能力学测试仪考察了阻燃聚甲醛体系的阻燃性能及力学性能,并采用旋转流变仪测定了复合材料的流变性能。结果表明,质量分数为20%GF的加入使聚甲醛(POM)/IFR复合体系的拉伸强度提升15.8%,弯曲强度提升16.0%,冲击性能提升1倍。与未添加GF的复合体系相比,POM/IFR/GF复合材料表现出更高的动态模量和复数黏度。由于GF"烛芯效应"的作用,GF的加入未实现UL94阻燃等级。通过酚醛树脂对GF进行表面改性(m GF)后,POM/IFR/GF复合体系的极限氧指数(LOI)由22.7%提升至34.6%,力学性能略有提升,体系的模量、复数黏度均低于未改性GF增强体系。     

不同含量膨胀性阻燃剂对长玻璃纤维增强PBT复合材料性能的影响

以长玻璃纤维(LGF)/聚对苯二甲酸丁二醇酯(PBT)复合材料为基体,加入膨胀性阻燃剂(IFR),研究了不同含量的IFR对LGF/PBT复合材料的燃烧性能、结晶性能及流变性能的影响。通过垂直燃烧(UL 94)和极限氧指数(LOI)测试得出,在IFR的含量为10%时,LGF/PBT/IFR复合材料通过UL94V-0级且LOI为28.2%;通过差示扫描量热仪、平板流变仪和傅里叶红外光谱分析得出,IFR与基体在熔融挤出后部分发生化学反应,引入极性基团,致使基体分子链运动困难,从而表现出复合材料的结晶度下降,储存模量增大,复合黏度增大,最终影响到复合材料的力学性能。     

超支化三嗪成炭剂阻燃聚丙烯

将自制的超支化三嗪成炭剂（CFA）与聚磷酸铵（APP）以1∶1的比例复配成膨胀型阻燃剂（IFR）,用于聚丙烯（PP）的阻燃。采用冲击实验、拉伸实验、极限氧指数仪、垂直燃烧（UL 94）和扫描电子显微镜 (SEM)等方法表征了PP阻燃复合材料的力学性能、阻燃性能,分析了断面形貌。结果表明,添加阻燃剂后,冲击强度呈先增加后降低的趋势,拉伸强度则随着阻燃剂含量的增加不断下降,但降幅不明显;含有15 % IFR的阻燃复合材料,其垂直燃烧等级即可通过UL 94 V-0级测试,显示出复合IFR具有优秀的阻燃效果。     

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。     

Synergistic effects of molybdenum disulfide on a novel intumescent flame retardant polyformaldehyde system

A novel intumescent flame retardant (IFR) composed of ammonium polyphosphate (APP), benzoxazine containing trialkoxysilane (BA-a-Si) and melamine (ME), is compounded with different specifications of MoS₂ as synergist to flame retard polyformaldehyde (POM). The flame retardancy and mechanism of the composites are analyzed by limiting oxygen index (LOI), vertical combustion (UL-94) and cone calorimeter. At the same time, the mechanical properties and lubricating properties are tested by electromechanical testing machine and wear testing machine. The experimental results show that MoS₂ has a good synergistic effect with IFR, and the smaller the average particle size of MoS₂ is, it seems to be more beneficial to improve the flame retardancy of POM composites. Only a small amount of MoS₂ (0.8 wt%) is needed to synergize with IFR, the flame retardant POM composite (FR-POM) can achieve UL-94 (3.2 mm) V-0 rating, LOI of 62.5%, and heat release rate reduction of 25.3%, total smoke release decreased by 29.5%. In addition, from the mechanical properties analysis, it is found that the microscale MoS₂(M2) can better improve the bending and tensile properties of the FR-POM composites, while the nanoscale MoS₂(N80) is more helpful to improve the lubricating properties.     

Synergistic flame‐retardant effect of halloysite nanotubes on intumescent flame retardant in LDPE

Synergistic flame‐retardant effect of halloysite nanotubes (HNTs) on an intumescent flame retardant (IFR) in low‐density polyethylene (LDPE) was investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimeter (CC) test, and scanning electronic microscopy (SEM). The results of LOI and UL‐94 tests indicated that the addition of HNTs could dramatically increase the LOI value of LDPE/IFR in the case that the mass ratio of HNTs to IFR was 2/28 at 30 wt % of total flame retardant. Moreover, in this case the prepared samples could pass the V‐0 rating in UL‐94 tests. CC tests results showed that, for LDPE/IFR, both the heat release rate and the total heat release significantly decreased because of the incorporation of 2 wt % of HNTs. SEM observations directly approved that HNTs could promote the formation of more continuous and compact intumescent char layer in LDPE/IFR. TGA results demonstrated that the residue of LDPE/IFR containing 2 wt % of HNTs was obviously more than that of LDPE/IFR at the same total flame retardant of 30 wt % at 700°C under an air atmosphere, and its maximum decomposing rate was also lower than that of LDPE/IFR, suggesting that HNTs facilitated the charring of LDPE/IFR and its thermal stability at high temperature in this case. Both TGA and SEM results interpreted the mechanism on the synergistic effect of HNTs on IFR in LDPE, which is that the migration of HNTs to the surface during the combustion process led to the formation of a more compact barrier, resulting in the promotion of flame retardancy of LDPE/IFR. In addition, the mechanical properties of LDPE/IFR/HNTs systems were studied, the results showed that the addition of 0.5–2 wt % of HNTs could increase the tensile strength and the elongation at break of LDPE/IFR simultaneously. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40065.     

Preparation,characterization and properties of a halogen‐free phosphorous flame‐retarded poly(butylene terephthalate) composite based on a DOPO derivative

A phosphorous flame retardant (DOPO‐MAH) was synthesized through the reaction between of 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) and maleic anhydride (MAH) and confirmed by FT‐IR, ¹H NMR, and ³¹P NMR techniques. The obtained flame retardant was then melt blended with poly(butylene terephthalate) (PBT) to prepare flame retardant PBT/DOPO‐MAH composites. The composites were characterized by LOI, UL‐94, and mechanical tests as well as scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry analysis. On adding 20 wt % DOPO‐MAH, LOI increased from 20.9 to 25.7 and the UL‐94 V‐0 rating was achieved, whereas the tensile and flexural properties were notably improved. Torque‐time profile during the melt blending and intrinsic viscosity of the composite indicated that DOPO‐MAH acted as both flame retardant and chain extender for the PBT matrix. The results showed that PBT/DOPO‐MAH composite is a promising material for its good comprehensive properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1301‐1307, 2013     

Synthesis of novel triazine charring agent and its effect in intumescent flame‐retardant polypropylene

A novel charring agent (CNCA‐DA) containing triazine and benzene ring, using cyanuric chloride, aniline, and ethylenediamine as raw materials, was synthesized and characterized. The effects of CNCA‐DA on flame retardancy, thermal degradation, and flammability properties of polypropylene (PP) were investigated by limited oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), and cone calorimeter test (CCT). The TGA results showed that CNCA‐DA had a good char forming ability, and a high initial temperature of thermal degradation; the char residue of CNCA‐DA reached 18.5% at 800°C; Ammonium polyphosphate (APP) could improve the char residue of APP/CNCA‐DA system, the char residue reached 31.6% at 800°C. The results from LOI and UL‐94 showed that the intumescent flame retardant (IFR) containing CNCA‐DA and APP was very effective in flame retardancy of PP. When the mass ratio of APP and CNCA‐DA was 2 : 1, and the IFR loading was 30%, the IFR showed the best effect; the LOI value reached 35.6%. It was also found that when the IFR loading was only 20%, the flame retardancy of PP/IFR can still pass V‐0 rating in UL‐94 tests, and its LOI value reached 27.1%. The CCT results demonstrated that IFR could clearly change the decomposition behavior of PP and form a char layer on the surface of the composites, consequently resulting in efficient reduction of the flammability parameters, such as heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), and mass loss (ML). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic effects of aluminium hypophosphite on the flame retardancy and thermal degradation behaviours of a novel intumescent flame retardant thermoplastic vulcanisate composite

ABSTRACT

The synergistic effects of aluminum hypophosphite (AHP) on the flame retardancy, thermal degradation behaviors of a novel intumescent flame retardant thermoplastic vulcanizate (TPV/IFR) composite were investigated. The results showed that the combination of AHP with IFR showed evident synergistic effects on the increase in the LOI value and reduction of the combustion parameters for the TPV/IFR/AHP composites at the optimum weight ratio of IFR/AHP (6/1) as evidenced by LOI, UL-94 and CCT. The TGA data revealed that AHP could change the degradation behavior of TPV/IFR composites and enhance the thermal stability of the TPV/IFR composites at high temperature. The results of FTIR, EDXS, LRS and SEM demonstrated that TPV/IFR/AHP composites could form more continuous, dense and stable char layer on the materials surface, and consequently improving the flame retardancy. Based on these results, the possible condensed flame retardant mechanism of TPV/IFR/AHP composites was concluded in detail.     

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。     

A novel lanthanum-based phosphorus-containing flame retardant agent and its application in polylactic acid

Currently, intumescent flame retardants (IFR) are often used in the flame retardant modification of polylactic acid (PLA). Due to the high loading, it will weaken the mechanical properties of PLA. In this study, lamellar lanthanum-based DOPO derivative (La@DDP) is prepared by solution method, and it acts as a flame retardant agent was added into PLA with IFR. The results show that PLA composite passes the UL94 V-0 rating with a limiting oxygen index (LOI) of 32.0, in the addition of 4.5 wt% IFR and 1.5 wt% La@DDP. Moreover, the peak heat release rate (PHRR) and total heat release (THR) of the PLA composite reduces by 31.0% and 23.2% compared to pure PLA, respectively. IFR/La@DDP agents assign the PLA composite with excellent thermal stability and carbon-forming ability. Through the analysis of residual char, the synergistic flame retardant mechanism between IFR and La@DDP in PLA composite is discussed. Notably, the tensile strength and elongation at break of the PLA composites are only reduced by 4.03% and 9.51% compared to pure PLA. This work provides a novel lanthanum-based flame retardant agent for designing PLA composites with good fire safety and mechanical properties, and it will broaden the application range of PLA.