HIPS/OMMT复合材料炭渣结构对阻燃性能的影响

采用熔融插层法制备了高抗冲聚苯乙烯/有机蒙脱土(HIPS/OMMT)和高抗冲聚苯乙烯/蒙脱土(HIPS/MMT)复合材料,并通过锥形量热仪评价了复合材料的阻燃性能;采用数码相机、扫描电镜(SEM)观察了燃烧残余物结构,对残余物结构进行了热重(TGA)分析。结果表明:OMMT的加入显著提高了复合材料以热释放速率表征的阻燃性能,而HIPS/MMT复合材料的阻燃性能提高不明显;HIPS/OMMT纳米复合材料燃烧热释放速率峰值时形成了皮窝复合炭渣结构,皮层组分主要为硅酸盐及部分难分解的碳质物质,热稳定性较高,窝层起膨胀炭层的作用,二者共同起阻燃作用。     

PVC/montmorillonite nanocomposites based on a thermally stable,rigid‐rod aromatic amine modifier

Two kinds of polyvinyl chloride (PVC)/montmorillonite (MMT) nanocomposites were prepared by the melt intercalation method based on a thermally stable, rigid‐rod aromatic amine modifier and a commonly used 1‐hexadecylamine. The information on morphological structure of PVC/MMT nanocomposites was obtained using XRD and TEM. The mechanical, thermal, and flame retardant properties of the nanocomposites were characterized by universal tester, DMA, TGA, and cone calorimeter. The degree of degradation of PVC was studied by ¹H‐NMR. MMT treated by the aromatic amine exhibited better dispersibility than that treated by 1‐hexadecylamine. The nanocomposites, based on this MMT, consequently exhibited better mechanical, thermal, and flame retardant properties and lower degradation degree than those based on 1‐hexadecylamine‐treated MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 567–575, 2004     

Poly(butylene terephthalate)/Clay Nanocomposites directly Prepared from Pristine Montmorillonite (MMT)

Summary Poly(butylene terephthalate) (PBT)/clay nanocomposites have been prepared by melt intercalation method directly from pristine montmorillonite (MMT), using cetyl pyridinium chloride (CPC) as the polymer/clay reactive compatibilizer. The effect of the reactive compatibilizer (CPC) proportion relative to the clay on the structure and properties of the PBT/clay nanocomposites was studied by XRD, TEM, TGA and cone calorimeter. The results show that such appropriate proportion as 1 wt % CPC to 3 wt % MMT induces well-dispersed intercalated morphology and better thermal and flame retarded properties. At last the intercalation mechanism of the technology was discussed.     

Intumescent flame retardation of melamine‐modified montmorillonite on polyamide 6: Enhancement of condense phase and flame retardance

Melamine‐modified montmorillonite (MA‐MMT) was prepared via cation exchange. The intercalation behavior was investigated by Fourier transform infrared spectrometer (FT‐IR), X‐ray photoelectron spectroscopy (XPS), and X‐ray diffraction (XRD). The results showed that the d‐spacing value increased from 1.25 nm for Na‐montmorillonite (Na⁺MMT) to 1.53 nm for MA‐MMT. Different kinds of montmorillonite combined with melamine pyrophosphate (MPP) were used to prepare flame‐retardant polyamide 6 (FR‐PA6). Flame retardance of FR‐PA6 samples was investigated by limiting oxygen index (LOI), UL‐94 vertical burning method, and cone calorimeter test. Morphology and component of char residues for FR‐PA6 were investigated by scanning electron microscope (SEM) and XPS. It was found that MA‐MMT/MPP system contributed both excellent flame retardance and anti‐dripping ability for PA6. MA‐MMT particles can fill flaws of char residues and strengthen the char layer, leading to form more intumescent char layer. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

PP/纳米蒙脱土复合材料炭层结构对阻燃性能的影响

采用熔融插层法制备了不同纳米蒙脱土含量的聚丙烯(PP)/有机蒙脱土(OMMT)和PP/无机蒙脱土(MMT)复合材料,且评价了复合材料的阻燃性能:采用数码相机、扫描电子显微镜观察了燃烧残余物结构.加入OMMT可显著提高PP/OM MT的阻燃性能:纯PP的热释放速率(HRR)峰值为1 337.59 kW/m2;w(OMMT...     

聚丙烯/尼龙/纳米蒙脱土膨胀型阻燃材料的研究

用尼龙6(PA6)代替季戊四醇(PT)作为成炭剂组成的膨胀型阻燃聚丙烯(PP)有熔滴、阻燃效果差的缺点，加入纳米蒙脱土(nano-MMT)作为阻燃剂的协效剂后可克服以上缺点。研究结果表明：加入质量分数为4％的nano-MMT不仅克服了阻燃体系熔滴的缺点，还使材料的拉伸强度提高了44．3％；热重分析和燃烧测试表明，nano-MMT的加入提高了材料的热稳定性，使剩炭率增加了12％，从而提高了材料的阻燃性能；由扫描电镜(SEM)观察发现：nano-MMT的加入增强了材料的界面粘结力，提高了材料的韧性，起到了一定的增容作用。     

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。     

Effect of Phosphorus-Based Flame Retardants and PA6 on the Flame Retardancy and Thermal Degradation of Polypropylene

The investigation mainly focuses on the effect of polyamide 6 (PA6) and phosphorus based flame retardants (FRs) on improving the flame retardancy of polypropylene (PP). The flame retardant properties have been studied by limiting oxygen index, vertical burning test tests and cone calorimeter testing. The results demonstrate that PA6 and FRs can greatly improve the flame-retardant and thermal properties of PP. It’s found that the addition of PA6/APP/FRs can promote the formation of stable intumescent char layers. Those indicate that the flame retardancy of PA6/APP/FRs/PP composites is improved by the condensed-phase action of PA6/APP/FRs.     

A novel bio-based charcoal-forming agent based on chitosan and phytate@Mg to improve the flame retardancy of poly(lactic acid)

A novel bio-based carbon forming agent (Mg@PA-CS) containing P and N elements was were synthesized using the complexation characteristics of chitosan (CS) and phytate (PA). The flame retardant behavior of poly(lactic acid) (PLA)/Mg@PA-CS/APP composites (addition of 20 wt% of different ratios of Mg@PA-CS and APP to polylactic acid composites) were investigated by the limiting oxygen index (LOI), vertical burning test (UL-94), cone calorimetry test (CCT), and thermogravimetric analysis (TGA). Due to the biphasic flame retardant and synergistic effect, since the 20 wt% flame retardant system (Mg@PA-CS:APP = 1:2), PLA composites passed the UL-94 test V-0 rating, reached 34% LOI value. The peak heat release rate (PHRR) and total heat release rate (THR) were reduced to 1/2 of the pure PLA, char residue could be as high as 11.49% at 800°C. Moreover, the flame-retardant mechanism of PLA composites during thermal decomposition was analyzed using a scanning electron microscope (SEM) and the coupling techniques of TGA linked with FT-IR (TG-FTIR).     

Synergistic effects of fumed silica on intumescent flame‐retardant polypropylene

The synergistic effects of fumed silica on the thermal and flame‐retardant properties of intumescent flame retardant (IFR) polypropylene based on the NP phosphorus‐nitrogen compound have been studied by Fourier transfer infrared (FTIR) spectroscopy, cone calorimeter test (CCT), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), limiting oxygen index (LOI), and UL‐94 tests. The LOI and UL‐94 data show that when ≤1 wt % fumed silica substituted for the IFR additive NP can increase 2 to 4% LOI values of the PP blends and keep the V‐0 rating. The data obtained from the CCT tests indicate the heat release rates (HRR) reduce by about 23% for the PP/NP sample with 0.5 wt % fumed silica, whereas the mass loss rates (MLR) and total heat release (THR) values are much lower than those of the PP/NP samples without fume silica. The TGA data demonstrate that a suitable amount of fumed silica can increase the thermal stability and charred residue of the PP/IFR/SiO₂ blends after 500°C. The morphological structures of charred residues observed by SEM give positive evidence that a suitable amount of fumed silica can promote the formation of compact intumescent charred layers and prevent the charred layers from cracking, which effectively protects the underlying polymer from burning. The dynamic FTIR spectra reveal that the synergistic flame‐retardant mechanism of a suitable amount of fumed silica with IFR additive is due to its physical process in the condensed phases. However, a high loading of fumed silica restricts the formation of charred layers with P? O? P and P? O? C complexes formed from burning of polymer materials and destroys the swelling behavior of intumescent charred layers, which deteriorates the flame retardant and thermal properties of the PP/IFR blends. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of a novel phosphorus‐containing compound on the flame retardancy and thermal degradation of intumescent flame retardant polypropylene

A novel flame retardant, tetra(5,5‐dimethyl‐1,3‐ dioxaphosphorinanyl‐2‐oxy) neopentane (DOPNP), was synthesized successfully, and its structure was characterized by FT‐IR, ¹H NMR, and ³¹P NMR. The thermogravimetric analysis (TGA) results demonstrate that DOPNP showed a good char‐forming ability. Its initial decomposition temperature was 236.4°C based on 1% mass loss, and its char residue was 41.2 wt % at 600°C, and 22.9 wt % at 800°C, respectively. The flame retardancy and thermal degradation behavior of novel intumescent flame‐retardant polypropylene (IFR‐PP) composites containing DOPNP were investigated using limiting oxygen index (LOI), UL‐94 test, TGA, cone calorimeter (CONE) test, and scanning electron microscopy (SEM). The results demonstrate that DOPNP effectively raised LOI value of IFR‐PP. When the loading of IFR was 30 wt %, LOI of IFR‐PP reached 31.3%, and it passed UL‐94 V‐0. TGA results show that DOPNP made the thermal decomposition of IFR‐PP take place in advance; reduced the thermal decomposition rate and raised the residual char amount. CONE results show that DOPNP could effectively decrease the heat release rate peak of IFR‐PP. A continuous and compact char layer observed from the SEM further proved the flame retardance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Influence of morphology and ammonium polyphosphate dispersion on the flame retardancy of polystyrene/nylon‐6 blends

The influences of the distribution of ammonium polyphosphate (APP) in polystyrene/nylon‐6 [PS/polyamide‐6 (PA6)] blends and the continuity of the (PA6 + APP) phase on flame retardancy were investigated. The flame retardant properties were evaluated by limiting oxygen index (LOI), vertical flammability test and cone calorimeter tests. The results showed that APP is exclusively dispersed in the PA6 phase, and (PA6 + APP) phase formed a continuous state when the content of PA6 in PS/PA6 blends was higher than 32% (w/w). For blends with a continuous (PA6 + APP) phase, the decrease of PA6 content caused an increase in LOI values from 26% to 33% and a reduction of peak heat release rate. The improvement of flame retardancy was attributed to the increase of APP concentration in the PA6 phase, which benefited the fast formation of a continuous intumescent charred layer. The transformation of (PA6 + APP) phase morphology from a continuous state to a discontinuous state at a PA6 content of below 32% (w/w) caused a decrease in LOI. Results of thermo‐gravimetric and cone calorimeter tests indicated that the discontinuous intumescent charred layer thus formed could be responsible for the deterioration of flame retardant properties, which was also confirmed by scanning electron microscopy. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and characterization of a novel charring agent and its application in intumescent flame retardant polypropylene system

A novel halogen‐free charring agent bi(4‐methoxy‐1‐phospha‐2, 6, 7‐trioxabicyclo [2.2.2]‐octane‐1‐sulfide) phenylphosphate (BSPPO) was synthesized from phenylphosphonic dichloride (PPDC), and 4‐hydroxymethyl‐1‐phospha‐2, 6, 7‐trioxabicyclo[2.2.2]‐octane‐1‐sulfide (SPEPA) which was synthesized from pentaerythritol and thiophosphoryl chloride in this article. The structure of BSPPO and SPEPA was characterized by Fourier transform infrared (FTIR), ¹H‐NMR, ¹³C‐NMR, and ³¹P‐NMR. Combined with ammonium polyphosphate (APP) and melamine pyrophosphate (MPP), the flame retardance and dripping resistance of BSPPO added in polypropylene (PP) were investigated. The fire performance of the flame retardant PP system was investigated by limiting oxygen index (LOI), vertical burning test (UL‐94), and cone calorimeter. The thermal stabilities of the composites were studied by thermogravimetric analysis (TGA). The flame retardance mechanism was investigated by FTIR and scanning electronic micrograph (SEM). The mechanical properties and water solubility were also investigated. The residue of BSPPO is 40.6% at 600°C, which indicates BSPPO has excellent charring ability. The char residue of the polypropylene intumescent flame retardant (PP‐IFR) system is 22% at 600°C, which suggests that the flame retardation synergy of APP, BSPPO, and MPP is good. With the optimum formulation, the LOI of the IFR‐PP system is 32.0, and the UL‐94 is V‐0 rating. The heat release rate (HRR), total heat release (THR), smoke production rate (SPR), total smoke production (TSP), and mass loss rate (MLR) of IFR‐PP with the optimum formulation decrease significantly comparing to pure PP from cone calorimeter analysis. The FTIR and SEM results indicate that the char properties and the char yield have direct effect on the flame retardance and antidripping behaviors. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

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。     

Condensed‐phase flame retardation in nylon 6‐layered silicate nanocomposites: Films,fibers, and fabrics

Flame‐retardant properties of nylon 6/organically modified montmorillonite (OMMT) thin films, fibers, and fabrics were investigated to determine the efficacy of condensed‐phase flame‐retardant mechanism in relation to montmorillonite concentration, sample geometry, and flame test conditions. Horizontal flame spread conducted on thin films revealed no significant difference in burning behavior between nylon 6 and nanocomposites with 5 wt% OMMT. However, with a higher concentration level of 8–10 wt% OMMT, the films burned without any dripping. The flame spread rate was reduced by 30–40% as compared with nylon 6 films. Cone calorimeter study on nanocomposite films showed that the peak heat release rate of nylon 6 was reduced by 65–67% with 8–10 wt% OMMT. Undrawn nanocomposite monofilaments with 10 wt% OMMT burned slowly and steadily in Bunsen flame without dripping. In cone calorimeter, nanocomposite fabrics with 8 wt% OMMT showed reduced heat release rate and mass loss rate compared to nylon 6 fabrics with increase in fabric tightness factor. The mass loss rate was about 40–60% less when compared with nylon 6 fabrics. The fabric char structure remained intact after burning. This demonstrated the interdependence of fabric tightness factor, OMMT concentration, and source of heat flux in forming a protective char and affecting the flammability of fabrics. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The Effect of New Flame Retardant Systems Containing Montmorillonite-Butyl Acrylate Nanoclay on the Flammability Properties of Polyuerethane Polymer

The montmorillonite (MMT) was modified by butyl acrylate polymer. The newly modified MMT was characterized by TGA and DSC techniques. The modified MMT constitute melamine phosphate and different carbonizing agents and new flame retardant systems for poly urethane (PU) polymer. The flammability properties of the different PU formulations were characterized by cone calorimeter and ISO 1210 tests.The new flame retardant system gave the poly urethane polymer higher fire class, V0 (PU3 & 23). The thermal stability of the PU formulations was also improved.     

Synergist flame retarding effect of ultrafine zinc borate on LDPE/IFR system

The flame retardancy of low‐density polyethylene (LDPE) treated with complex flame retardant composed of ultrafine zinc borate (UZB) and intumescent flame retardant (IFR) have been investigated by limited oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA), cone calorimeter test, scanning electron micrograph (SEM), energy‐dispersive spectrometer (EDS), and X‐ray diffraction (XRD). The results of LOI and UL‐94 test indicate the desired flame retardancy of LDPE is obtained when the mass ratio of UZB to IFR is 4.2 : 25.8 and the complex flame retardant mass content is 30% (based on LDPE). The results of cone calorimeter show that heat release rate (HRR) peak, total heat release (THR), and mass loss of LDPE/IFR/UZB decrease substantially when compared with those of LDPE/IFR. TGA results show that the residue of LDPE/IFR/UZB increases obviously than that of LDPE/IFR when the temperature is above 600°C. SEM indicates the quality of char forming of LDPE/IFR/UZB is superior to that of LDPE/IFR. The results of EDS and XRD indicate that boron orthophosphate (BPO₄) and zinc‐contained compounds are formed in the residual char and these substances may play an important role in stabilizing the intumescent char structure and decrease the degradation speed substantially when subjected to high temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3667–3674, 2007     

PVAc/OMMT纳米复合物的制备及其在阻燃PP中的应用

通过原位乳液插层法制备了有机蒙脱土(OMMT)含量较高的聚醋酸乙烯酯/有机蒙脱土(PVAc/OMMT)纳米复合物,并将其作为阻燃母料与氢氧化镁(MH)复配,与聚丙烯(PP)熔融共混制备了性能良好的无卤阻燃PP,用X射线衍射(XRD)、锥形量热分析(CONE)等对材料进行了表征。结果表明:当OMMT和MH的用量分别为3%和40%时,阻燃PP的热释放速率峰值(PHRR)相比于基体树脂从929.0kW/m2降低至193.7kW/m2,总释放热(THR)从165.2MJ/m2降低到73.6MJ/m2。