柠檬酸改性β型分子筛在膨胀阻燃ABS复合材料中的协同作用研究

采用浸渍法制备了柠檬酸改性的β型分子筛(N-β)。红外光谱测试表明,柠檬酸对β型分子筛具有补铝作用,可使其骨架铝含量增加。利用热重分析、氧指数测试、扫描电镜分析等手段探讨了N-β对丙烯腈-丁二烯-苯乙烯共聚物(ABS) /膨胀型阻燃剂(IFR)复合材料热失重行为、阻燃性能、微观结构及力学、加工性能的影响。结果表明,N-β在含量较低时与IFR具有较好的阻燃协同作用,可促进IFR高温成炭,形成稳定、连续、致密的炭层结构。当N-β量为2%(质量分数,下同)时,ABS/IFR复合材料的极限氧指数为31.3%,残炭量为24. 86%。同时,随着N-β含量的增加,复合材料的冲击强度、拉伸强度呈现出先升后降的趋势。     

膨胀型阻燃剂APP/MPR/PEPA的制备及其在ABS中的应用

用氧代-4-羟甲基-2,6,7-三氧杂-1-磷杂双环[2,2,2]辛烷(PEPA)作为成炭剂,用三聚氰胺酚醛树脂(MPR)作为气源和聚磷酸铵(APP)按一定比例复配成膨胀型阻燃剂(IFR),用于丙烯腈-丁二烯-苯乙烯共聚物(ABS)的阻燃研究。研究IFR的比例和含量对ABS燃烧性能的影响。阻燃实验结果表明,APP/MPR/PEPA质量比按2/1/2和3/3/4比例复配阻燃效果最佳,添加量为30%时,阻燃复合材料燃烧等级达到V-0,氧指数分别为29.4%和29%;热重分析和扫描电镜结果表明,阻燃复合材料热稳定性能较纯ABS有所降低,微观炭层更加致密无孔洞。     

硼酸锌对乙烯-丙烯酸丁酯共聚物力学及阻燃性能的影响

用极限氧指数(LOI)、热重(TGA)和差示扫描量热(DSC)等方法研究了乙烯-丙烯酸丁酯共聚物(E-BA)/硼酸锌(ZB)复合材料的阻燃性能和热降解行为及ZB对EBA力学性能和熔体流动速率的影响。实验结果表明ZB的引入提高了EBA在高温下的热稳定性,恶化了材料的力学性能和加工性能,添加60%材料的LOI可达26.8%,主要通过物理方式在凝缩相和气相中发挥阻燃作用。     

MWNT对长玻纤增强PP/膨胀阻燃剂体系性能的影响

用熔融共混法制备了长玻纤增强聚丙烯/膨胀阻燃剂/多壁碳纳米管(LGFPP/IFR/MWNT)复合材料。通过极限氧指数、垂直燃烧测试、热失重分析、力学性能测试等手段研究了MWNT对LGFPP/IFR的阻燃性能、热性能和力学性能的影响。结果表明,MWNT的加入提高了LGFPP/IFR阻燃体系的阻燃性能,在LGFPP/IFR阻燃体系中添加1%MWNT后,LGFPP/IFR/MWNT复合材料的氧指数提高到23.5%;MWNT可显著增加LGFPP/IFR的热稳定性,添加1%MWNT可使LGFPP/IFR热分解起始温度提高12.34℃;MWNT的加入还提高了LGFPP/IFR阻燃体系的力学性能,在LGFPP/IFR阻燃体系中添加1%MWNT后,LGFPP/IFR/MWNT复合材料的拉伸强度、弯曲强度和冲击韧性分别提高了5.7%、12.7%和1.0%。     

4A分子筛和SiO2对EVA/IFR复合材料性能的影响

以聚磷酸铵(APP)复配季戊四醇(PER)为膨胀型阻燃剂(IFR)制备了无卤阻燃乙烯-醋酸乙烯共聚物(EVA)/IFR复合材料,通过极限氧指数仪、热失重分析仪及扫描电子显微镜研究分析了4A分子筛和SiO2的加入对复合材料阻燃性能、热稳定性能及复合材料残炭表面形貌的影响。结果表明,加入4A分子筛可以明显提高复合材料的极限氧指数,当添加1份4A分子筛时,复合材料的极限氧指数达到31%,比未添加时提高了2%;4A分子筛的加入使复合材料在燃烧过程出现熔融滴落现象;继续加入SiO2可以进一步提高复合材料的极限氧指数,当添加3份SiO2时,复合材料的垂直燃烧测试达到V-0级。     

非对称双螺杆制备ABS/PUR-T/HNTs阻燃复合材料的性能

分别采用自主研制的新型同向非对称双螺杆挤出机以及传统双螺杆挤出机制备了丙烯腈–丁二烯–苯乙烯塑料(ABS)/膨胀型阻燃剂(IFR),ABS/热塑性聚氨酯弹性体(PUR-T)/IFR以及ABS/PUR-T/IFR/埃洛石纳米管(HNTs)等3种阻燃复合材料试样,表征了试样的冲击、拉伸和弯曲强度以及极限氧指数(LOI),同时测试了非对称双螺杆挤出机制备的试样的燃烧性能,分析了PUR-T和HNTs对试样性能的影响。结果表明,相比于传统双螺杆挤出机,自制非对称双螺杆挤出机由于具有更优异的混合性能,所制备的复合材料试样力学性能和LOI均有提高;针对非对称双螺杆制备的试样,加入质量分数为17.5%的PUR-T后,其冲击强度提高,而拉伸和弯曲强度降低,LOI由27%提升至40%,热释放速率峰值(PHRR)、平均热释放速率(MHRR)、总热释放量(THR)和生烟速率(SPR)降低,火灾性能指数(FPI)提高,阻燃效果显著增加;进一步加入2%的HNTs后,试样的冲击、拉伸和弯曲强度得到提高,LOI稍有下降,但仍为37%,MHRR和THR有所增大,但PHRR和SPR进一步降低,且FPI提高,有助于降低火灾危险性。     

膨胀阻燃LLDPE/EVA复合材料的制备及其改性

将预先配制好的膨胀阻燃剂[IFR,聚磷酸铵(APP)/季戊四醇(PER)/硼酸锌(ZB)]与线性低密度聚乙烯(LLDPE)/乙烯-醋酸乙烯共聚物(EVA)进行混和,采用双螺杆挤出机,制备阻燃LLDPE/EVA复合材料。用氧化钙(CaO)、天然石墨(NG)、膨胀石墨(EG)对阻燃LLDPE/EVA复合材料进行改性。结果表明:APP/PER/ZB具有明显的膨胀阻燃作用,同时,发现CaO,NG,EG与IFR有协同作用,提高了膨胀炭层的热稳定性和阻燃效率。     

协效剂在ABS/APP/PETA体系中的阻燃协效性

为了提高苯乙烯一丁二烯一丙烯睛(ABS）/聚磷酸铵(APP)/聚对苯二甲酞乙二胺(PETA)膨胀阻燃体系的阻燃性能,将硼酸锌(ZB）、红磷(RP）添加到ABS/ APP/ PETA膨胀阻燃体系中。采用极限氧指数法、垂直燃烧法、热失重、扫描电镜探讨了不同含量协效剂ZB,RP对不同比例ABS/APP/PETA阻燃体系的协效阻燃效应。结果表明,加人协效剂使ABS/APP/PETA体系的阻燃性能得到显著提高;将2.5份(质量份,下同)ZB和4份RP加人到ABS/APP/PETA( 70/22. 5/7. 5)体系,体系的极限氧指数由未加协效剂的30%提高到41%,UL-94测试也达到V-0级;ZB提高了ABS/APP/PETA体系热稳定性和成炭率,RP能极大地促进成炭;加人ZB和RP ,阻燃体系燃烧表面能够形成更多膨胀、致密的炭层。     

CFA/APP协同阻燃动态硫化热塑性弹性体的制备及其性能

将新型无羟基低聚三嗪衍生物(CFA)作为成炭剂与聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR),并研究了不同含量和比例的IFR对动态硫化热塑性弹性体(TPV)阻燃性能、热稳定性能、流变性能和力学性能的影响。结果表明:IFR对TPV有良好的阻燃作用,当IFR(CFA与APP质量比1∶3)质量分数为40%时,TPV/IFR复合材料具有最佳的阻燃性能,极限氧指数为26.4%,且垂直燃烧测试等级为V-0级;TPV/IFR复合材料的热释放速率峰值与总热释放量均大幅降低;IFR能促使TPV/IFR复合材料形成更多的残炭,积分程序分解温度和表观活化能明显增加,材料的热稳定性显著提高;TPV/IFR复合材料虽然加工性能略有降低,但具有优异的力学性能,能满足加工使用要求。     

4A分子筛对EVA/APP/PETA复合材料阻燃性能的影响

以聚磷酸铵(APP)和聚对苯二甲酰乙二胺(PETA)复配制备了无卤阻燃乙烯-醋酸乙烯共聚物(EVA)/膨胀型阻燃体系(IFR)复合材料,通过极限氧指数仪、热失重分析仪(TG)和扫描电镜(SEM)分析了4A分子筛对复合材料的阻燃性能、热稳定性能和复合材料残炭表面形貌的影响。结果表明,当4A分子筛添加量为2%时,复合材料的极限氧指数达39%,比未添加4A分子筛的提高了4%,垂直燃烧达到V-0级。SEM表明,4A分子筛的加入提高了样品残炭表面致密度。     

聚磷酸铵／季戊四醇复合膨胀型阻燃剂阻燃ABS的研究

通过热重分析、扫描电子显微镜和氧指数等研究了由聚磷酸铵与季戊四醇组成的膨胀型阻燃剂(IFR)对ABS的阻燃作用。与传统的含卤阻燃ABS相比,热失重分析显示,IFR的加入使体系的残炭量显著增加,650℃时ABS的残炭量由不加IFR时的1.9%增至21.32%。扫描电子显微镜观测发现,经IFR阻燃的ABS在燃烧时形成了由无数封闭孔洞构成的蓬松焦化炭层,表明IFR对ABS具有良好的膨胀阻燃效果。在IFR含量为30%时,ABS的氧指数可达27.4%。     

Synergistic Effect of Montmorillonite and Intumescent Flame Retardant on Flame Retardance Enhancement of ABS

The synergistic effects of organic montmorillonite (OMMT) and intumescent flame retardant (IFR) based on the ammonium polyphosphate (APP) and pentaerythritol (PER) on flame retardant enhancement of acrylonitrile-butadiene-styrene copolymer (ABS) were investigated by using the limiting oxygen index (LOI), the UL-94 (vertical flame) test, thermogravimetric analysis (TGA), x-ray diffractometry (XRD) and scanning electron microscopy (SEM). The LOI data and vertical flame tests show that OMMT has a synergistic flame retardant effect with IFR and the LOI value of ABS/OMMT/IFR (96/4/20) reaches 28.7%. The TGA data demonstrate that the incorporation of OMMT and IFR is very effective in enhancing the thermal stability of ABS/OMMT/IFR system at high temperature (T > 500°C). The results of XRD show that the composite of ABS/OMMT is a kind of intercalated nanocomposite and the gallery height of ABS/OMMT nanocomposite is 3.5 nm. The microstructures observed by SEM demonstrate that a suitable amount of OMMT with IFR can promote formation of compact intumescent charred layers in ABS blends.     

OMMT对LGFPP/IFR阻燃性能、燃烧性能及力学性能的影响

采用熔融共混技术制备了长玻璃纤维增强聚丙烯/膨胀阻燃剂/有机蒙脱土(LGFPP/IFR/OMMT)复合材料。利用极限氧指数(LOI)、锥形量热仪(CONE)以及万能力学试验机,表征了LGFPP/IFR/OMMT复合材料的阻燃性能、燃烧性能以及力学性能。氧指数测试结果表明,OMMT使LGFPP/IFR体系的氧指数提高。当添加2%OMMT时,LGFPP/IFR/OMMT复合材料的氧指数提高至24.2%。锥形量热仪测试结果表明,LGFPP/IFR体系的热释放速率峰值(PHRR)、烟雾生产率(THR)及引燃时间(TTI)均由于添加OMMT而大幅度降低。力学性能测试结果表明,LGFPP/IFR体系的拉伸强度、弯曲强度以及缺口冲击强度因OMMT的添加,分别提高了8.15%、9.04%和24%,使LGFPP/IFR体系中由于IFR引起LGFPP力学性能降低的弊端得到了明显改善。     

EG与IFR复合阻燃ABS的动态燃烧性和协同效应

将可膨胀石墨(EG)与P-N型膨胀阻燃剂(IFR)复合阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS)树脂,阻燃剂添加量为20%(质量分数,下同),通过极限氧指数(LOI)仪、垂直燃烧测试(UL-94)仪、锥形量热(CONE)仪和扫描电镜(SEM)研究了EG与IFR复合阻燃ABS的协同效应。结果表明,EG/IFR质量比为1/1为最佳配比,阻燃ABS的LOI达到29%,UL-94为V-0级;EG与IFR复合阻燃ABS,表现出一定的协同作用;通过SEM观察ABS/EG/IFR试样燃烧后样品发现,EG与IFR起到协同阻燃作用。     

Synergistic effect of intumescent flame retardant and zinc borate on linear low-density polyethylene

A series of novel intumescent flame retardant (IFR) based on melamine, neopentyl glycol, and aluminum diethylphosphinate were prepared and tested. In addition, the synergistic effect of the novel IFR and zinc borate (ZB) on the flame retardancy of LLDPE composites was investigated. The structures of novel IFR and ZB were characterized by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The limiting oxygen index (LOI) increased from 19.3% for the pure LLDPE to 27% for the 25 wt% IFR/5 wt% ZB composites and the composites achieved the desired V-0 rating in the UL-94 test. Thermogravimetric analysis showed that the addition of IFR/ZB reduced the pyrolysis rate of the LLDPE composites at high temperatures and increased the amount of the char residues, and the char residue of LLDPE-5 reached 12.1 wt% at 700°C. Cone calorimetry (CCT) data showed that the peak of total heat release, heat release rate, and fire growth index were comparatively reduced, indicating that the addition of IFR/ZB decreased the fire hazard of LLDPE composites. The formation of a compact and thermally stable char layer on the surfaces of LLDPE composites was revealed from the scanning electrone microscopy images and digital photographs of the char residue after the CCT tests.     

Influences of 4ZnO·B2O3·H2O whisker based intumescent flame retardant on the mechanical,flame retardant and smoke suppression properties of polypropylene composites

In this work, the influences of 4ZnO·B₂O₃·H₂O zinc borate (ZB) whisker based intumescent flame retardant (IFR) containing ammonium polyphosphate and dipentaerythritol on the mechanical, flame retardant and smoke suppression properties of polypropylene (PP) composites were characterized by the universal testing machine, UL-94, limiting oxygen index (LOI), and cone calorimeter tests, respectively. The results indicate that only 1 phr of ZB could effectively improve the LOI value and slow down the burning rate of PP composite. The peak heat release rate, average of HRR, total heat release, peak smoke production rate, and total smoke production values are all decreased from 413.8 kW/m², 166.3 kW/m², 82.3 MJ/m², 0.0995 m²/s, and 17.9 m² for PPc/20IFR composite to 267.8 kW/m², 128.3 kW/m², 66.8 MJ/m², 0.0478 m²/s, and 12.6 m² for PPc/20IFR/1ZB composite, respectively. The scanning electron microscopy images, energy dispersive spectrometry, and Raman spectra of char residue reveal that ZB is helpful to form a compact and graphitized intumescent char residue so that the heat diffusion and oxygen transmission are greatly hindered. The thermogravimetry analysis-fourier transform infrared spectroscopy (TGA-FTIR) results show that less combustible volatiles and more H₂O vapor are generated with the appearance of ZB. Hence, the combustion mechanism in gas phase is suppressed.     

Application of a novel halogen‐free intumescent flame retardant for acrylonitrile‐butadiene‐styrene

A novel intumescent flame retardant (IFR), containing ammonium polyphosphate (APP) and poly(tetramethylene terephthalamide) (PA4T), was prepared to flame‐retard acrylonitrile‐butadiene‐styrene (ABS). The flame retardation of the IFR/ABS composite was characterized by limiting oxygen index (LOI) and UL‐94 test. Thermogravimetric analysis (TGA) and TGA coupled with Fourier transform infrared spectroscopy (TG‐FTIR) were carried out to study the thermal degradation behavior of the composite and look for the mechanism of the flame‐retarded action. The morphology of the char obtained after combustion of the composite was studied by scanning electron microscopy (SEM). It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA4T/APP/ABS (7.5/22.5/70) system increasing from 18.5 to 30% and passing UL‐94 V‐1 rating. Meanwhile, the TGA and TG‐FTIR work indicated that PA4T could be effective as a carbonization agent and there was some reaction between PA4T and APP, leading to some crosslinked and high temperature stable material formed, which probably effectively promoted the flame retardancy of ABS. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame‐retarded ABS composite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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。     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.