Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system

A novel ionic liquid containing phosphorus ([PCMIM]Cl) was synthesized and characterized by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR. Moreover, a new intumescent flame retardant (IFR) system, which was composed of [PCMIM]Cl and ammonium polyphosphate (APP), was used to impart flame retardancy and dripping resistance to polypropylene (PP). The flammability and thermal behaviors of intumescent flame‐retarded PP (PP/IFR) composites were evaluated by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA) and cone calorimeter test. It was found that there was an obvious synergistic effect between [PCMIM]Cl and APP. When the weight ratio of [PCMIM]Cl and APP was 1:5 and the total amount of IFR was kept at 30 wt%, LOI value of PP/IFR composite reached 31.8, and V‐0 rating was obtained. Moreover, both the peak heat release rate and the peak mass loss rate of PP/IFR composites decreased significantly relative to PP and PP/APP composite from cone calorimeter analysis. The TGA curves suggested that [PCMIM]Cl had good ability of char formation, and when combined with APP, it could greatly promote the char formation of PP/IFR composites, hence improved the flame retardancy. Additionally, the rheological behaviors and mechanical properties of PP/IFR composites were also investigated, and it was found that [PCMIM]Cl could also serve as an efficient lubricant and compatibilizer between APP and PP, endowing the materials with satisfying processability and mechanical properties. Copyright © 2013 John Wiley & Sons, Ltd.     

An efficient and convenient strategy toward fire safety and water resistance of polypropylene composites through design and synthesis of a novel mono‐component intumescent flame retardant

A novel mono‐component flame‐retardant additive poly (dimethylol melamine piperazine pyrophosphate) defined as PDMPP was synthesized from formaldehyde, melamine, and piperazine pyrophosphate. Its chemical structure was well characterized by Fourier transform infrared spectroscopy, ¹³C and ³¹P solid‐state nuclear magnetic resonance, and elemental analysis tests. PDMPP was incorporated into polypropylene (PP) matrix, and the fire‐retardant performance, thermal properties, and water resistance of PP composites were investigated in detail. PP/23 wt% PDMPP composites before and after water resistance tests both achieved UL‐94V‐0 grade during vertical burning tests, and the limiting oxygen index was slightly declined from 26.7% to 26.3%. Small amount of PDMPP was extracted by hot water, and the weight loss percentage was 0.67% during water resistance tests. The piperazine and triazine rings in PDMPP contributed to a much better char‐forming capability, and then a greatly expanded and coherent char residue was generated during combustion and exhibited excellent isolation effect. The heat release rate, carbon monoxide production, and smoke production rate of the flame‐retarded PP composites before and after water resistance tests were effectively suppressed to a low level. Consequently, the introduction of PDMPP apparently improved the fire safety of PP composites as well as excellent water‐resistant performance.     

高密度聚乙烯/蒙脱土纳米复合材料膨胀阻燃体系的性能

使用以乙烯/醋酸乙烯共聚物(EVA)为相容剂的高密度聚乙烯/蒙脱土(HDPE/OMT)纳米复合材料作为基体,制备了含不同成炭剂的聚磷酸铵(APP)膨胀阻燃体系,对其阻燃性能进行了比较和研究,并分析了蒙脱土与膨胀阻燃剂协效作用的机理。热重分析(TGA)、垂直燃烧(UL-94)、极限氧指数(LOI)、锥形量热计结果表明:APP/季戊四醇(PER)体系熔融过程较短可形成蒙脱土增强炭层;PER/PA/OMT体系中较高的有机物含量有利于蒙脱土迁移和堆积。     

Micro‐intumescent flame retardant polyamide 6 based on cyclic phosphate grafting phenol formaldehyde

In this paper, thermoplastic phenol formaldehyde (PF) grafted cyclic neopentyl phosphate (PFCP) was synthesized by using PF and 2,2‐dimethyl‐1,3‐propanediol phosphoryl chloride. It was characterized by Fourier transform infrared spectroscopy (FTIR), 1H and 31P nuclear magnetic resonance (NMR). Compared to PF, PFCP shows improved thermal and thermoxidative stability and allows itself to be used in polyamide 6 (PA6). A micro‐intumescent flame retardant system was constructed by using cyclic neopentyl phosphate as acid source, PF as charring agent and PA6 whose decomposition products work as blowing agent. The results showed that PA6/PFCP composite is classified the UL‐94 V‐0 rating and get a LOI value of 35.5% at 25% loading of PFCP. SEM results showed that the outside of char residues is continuous and dense, but the inside is micro‐intumescent and porous. XPS analysis of char revealed that most of phosphorus remained in the char layer. All the results suggest that the mode of flame retardant's action for PA6/PFCP composites is shifted from melting away to charring protection with the content of PFCP increasing. The coherent char generated by the decomposition of PFCP contributes most to flame retardancy of PA6. Copyright © 2016 John Wiley & Sons, Ltd.     

Synergistic effect between a char forming agent (CFA) and microencapsulated ammonium polyphosphate on the thermal and flame retardant properties of polypropylene

The synergistic effect between a char forming agent (CFA) and microencapsulated ammonium polyphosphate (MAPP) on the thermal and flame retardancy of polypropylene (PP) are investigated by limiting oxygen index (LOI), UL‐94 test, cone calorimetry, thermogravimetric analysis (TGA), scanning electron micrograph (SEM), and water resistance test. The results of cone calorimetry show that heat release rate peak (PHRR), total heat release (THR), and the mass loss of PP with 30 wt% intumescent flame retardant (IFR, CFA/MAPP = 1:2) decreases remarkably compared with that of pure PP. The HRR, THR, and mass loss decrease, respectively from 1140 to 100 kW/m², from 96 to 16.8 MJ/m², and from 100 to 40%. The PP composite with CFA/MAPP = 1:2 has the best water resistance, and it can still obtain a UL‐94 V‐0 rating after 168 hr soaking in water. Copyright © 2008 John Wiley & Sons, Ltd.     

膨胀型聚氨酯防火涂料阻燃机理的研究

用自制的新型成炭剂和聚磷酸铵复配作为聚氨酯防火涂料的阻燃体系。采用热失重分析、扫描电镜、红外光谱和元素分析等手段对膨胀型聚氨酯防火涂料的阻燃机理进行了较为深入的研究．     

Effect of Ultrafine Full-Vulcanized Powdered Rubber on the Properties of the Intumescent Fire Retardant Polypropylene

Ultrafine full-vulcanized powdered rubber (UFPR) was added into intumescent fire retardant polypropylene (IFR-PP) composites, and fire retardance, morphology, and properties of the composite were analyzed. Ammonium polyphosphate and pentaerythritol were used as the intumescent fire retardants (IFR). The mechanical properties (elongation at break increased from 70% to 110%) and the melt flowability of IFR-PP improved by adding a small quantity of UFPR (less than 0.5 phr) but decreased when the UFPR was more than 0.5 phr. At the same time, the fire retardance, as measured by the limiting oxygen index and the UL94 vertical test rating, and other mechanical properties decreased appreciably with adding UFPR. The reasons were analyzed by using SEM micrographs, and a model was proposed to explain the reasons.     

Study on fire retardant mechanism of nano-LDHs in intumescent system

This paper investigated the fire-retardant mechanism of the nano-LDHs in the intumescent system by the temperature programmed oxidation (TPO). Researches were also conducted to explore the function of the nano-LDHs in the composite fire-retardant agents in air and nitrogen atmosphere, respectively. The results indicated that the nano-LDHs species were responsible for the catalytic oxidation of the rich-carbon compound in oxygen atmosphere. In addition, the nano-LDHs species and their calcinated products at high temperature could increase the carbonaceous residue-shield of the carbon-rich materials, improve the quality and the graphitization degree of the formed char-layer, and accelerate the intumescence and expansion of the melting carbon-rich materials to a certain degree under the oxygen-free condition, leading to the carbonization and expansion of the intumescent layer.     

Synergistic effect of boron containing substances on flame retardancy and thermal stability of clay containing intumescent polypropylene nanoclay composites

The functions of nanoclay and three different boron containing substances, zinc borate (ZnB), borophosphate (BPO₄), and boron silicon containing preceramic oligomer (BSi), were studied to improve the flame retardancy of polypropylene (PP)‐nanoclay‐intumescent system composed of ammonium polyphosphate (APP) and pentaerythritol (PER). The flame retardancy of PP composites was investigated using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis (TGA), and cone calorimeter. According to the results obtained, the addition of 20 wt% intumescent flame retardant (IFR) improved the flame retardancy by increasing the char formation. Addition of clay slightly increases the LOI value and reduces the maximum heat release rate (HRR). Addition of clay also increases the barrier effect due to intumescent char, especially in thin samples. Boron compounds show their highest synergistic effect at about 3 wt% loading. According to UL‐94 test and LOI test, 3 wt% ZnB containing composite shows the highest rating (V0) and BPO₄ containing sample shows the highest LOI value (26.5). Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and Application of a Novel Charring Agent Poly(p-ethylene terephthalamide)

A novel charring agent poly(p-ethylene terephthalamide) (PETA) was synthesized by using terephthaloyl chloride and ethylenediamine through solution polycondensation at low temperature. Poly(p-ethylene terephthalamide) was used together with ammonium polyphosphate (APP) to prepare a novel intumescent flame retardant (IFR) for acrylonitrile–butadiene–styrene (ABS). The thermal degradation behavior and flame retardancy were investigated by thermogravimetric analysis and limiting oxygen index (LOI) tests, and the morphology and structures of residues generated in different conditions were investigated by scanning electron microscopy and Fourier transform infrared spectra. The results showed that PETA could be effective as a charring agent, the flame retardancy of ABS and the weight of residues improved greatly with the addition of IFR. When the content of APP was 25 wt% and PETA was 12.5 wt%, the LOI value of IFR–ABS system was found to be 33, and class V-0 of UL-94 test was passed. The microstructures observed by scanning electron microscope indicated that the charring agent (PETA) can promote formation of uniform and compact intumescent charred layers in IFR–ABS system after burning.