Intumescent flame retardant–montmorillonite synergism in polypropylene‐layered silicate nanocomposites

Polypropylene/clay nanocomposites have been prepared starting from pristine mont morillonite (MMT) and reactive compatibilizer hexadecyltrimethylammonium bromide (C16). The nanocomposite structure is evidenced by the X‐ray diffraction and high resolution electronic microscopy. Intumescent flame retardant has been added to polypropylene/clay hybrids. Their flammability behaviours have been evaluated using cone calorimetry. Synergy was observed between the nanocomposites and intumescent flame retardant. Copyright © 2003 Society of Chemical Industry     

Thermal stability,flame retardance,and mechanical properties of polyamide 66 modified by a nitrogen–phosphorous reacting flame retardant

Flame‐retardant polyamide 66 (PA66) was prepared by the polymerization between PA66 prepolymer and N‐benzoic acid (ethyl‐N‐benzoic acid formamide) phosphamide (NENP). Compared with the pure PA66, the flame‐retardant PA66 exhibited better thermal stability, as indicated by thermogravimetric analysis results. The limiting oxygen index was 28% and the UL‐94 test results of the flame‐retardant PA66 indicated a V‐0 rating when the content of the NENP prepolymer was 5 wt %. The flammability and flame‐retardant mechanism of PA66 were also studied with cone calorimetry and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, respectively. The mechanical properties results show that the flame‐retardant PA66 resin had favorable mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43538.     

Thermal–oxidative degradation and accelerated aging behavior of polyamide 6/epoxy resin‐modified montmorillonite nanocomposites

Polyamide 6 (PA6) nanocomposites based on epoxy resin‐modified montmorillonite (EP‐MMT) were prepared by melt processing using a typical twin‐screw extruder. X‐ray diffraction combined with transmission electron microscopy was applied to elucidate the structure and morphology of PA6/EP‐MMT nanocomposites, suggesting a nearly exfoliated structure in the nanocomposite with 2 wt % EP‐MMT (PA6/2EP‐MMT) and a partial exfoliated‐partial intercalated structure in PA6/4 wt %EP‐MMT nanocomposite (PA6/4EP‐MMT). The thermogravimetric analysis under air atmosphere was conducted to characterize the thermal–oxidative degradation behavior of the material, and the result indicated that the presence of EP‐MMT could inhibit the thermal‐oxidative degradation of PA6 effectively. Accelerated heat aging in an air circulating oven at 150°C was applied to assess the thermal–oxidative stability of PA6 nanocomposites through investigation of reduced viscosity, tensile properties, and chemical structure at various time intervals. The results indicated that the incorporation of EP‐MMT effectively enhanced the thermal–oxidative stability of PA6, resulting in the high retention of reduced viscosity and tensile strength, and the low ratio of terminal carboxyl group to amino group. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40825.     

Rheology of a low‐filled polyamide 6/montmorillonite nanocomposite

The rheological properties of a polyamide 6/clay nanocomposite with a low loading of clay (1 wt %) were studied. Linear viscoelastic measurements in oscillatory and steady shear with small strain amplitudes were carried out. The nanocomposite exhibited a higher elastic modulus, viscous modulus, and complex viscosity than neat polyamide 6 during dynamic and steady shear tests. Moreover, the addition of clay resulted in a reduction of the critical strain amplitude, an increase of the loss angle, and a reduction of the frequency at the intersection of the elastic and viscous moduli. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

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     

Syntheses and properties of low‐level melamine‐modified urea–melamine–formaldehyde resins

Syntheses of urea–melamine–formaldehyde (UMF) resins were studied using 2–12% melamine levels and UF base resins that were preadvanced to various different extents. The melamine reaction was carried out at pH 6.3 with F/(U + M) mole ratio of 2.1 until a target viscosity of V was reached (Gardener–Holdt) and then the second urea added at pH 8.0 to give a final F/(U + M) mole ratio of 1.15. Analyses with ¹³C‐NMR and viscosity measurements showed that MF components react fast and the UF components very slowly in the melamine reaction. Therefore, as the extent of preadvancement of UF base resin was decreased, the reaction time to reach the target viscosity became longer and the MF resin components showed high degrees of polymerization. The overpolymerization of MF components resulted in increasingly more opaque resins, with viscosity remaining stable for more than a month. As the preadvancement of UF base resin was increased, the extent of advancement of MF components decreased, to give clearer resins, with viscosity slowly increasing at room temperature. Overall, preadvancing the UF base resin components to an appropriate extent was found to be a key to synthesizing various low‐level melamine‐modified UMF resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2559–2569, 2004     

Thermal stability and crystalline of electrospun polyamide 6/organo‐montmorillonite nanofibers

This research is mainly to investigate the thermal and crystalline differences between polyamide 6/montmorillonite (PA6/MMT) and polyamide 6/organo‐montmorillonite (PA6/O‐MMT) nanofibers, which were both prepared by electrospinning under the same process conditions. The structures of PA6/MMT and PA6/O‐MMT nanofibers were observed by scanning electrical microscope. It was identified that the interval between O‐MMT clays was increased in the PA6 matrix compared to that of MMT, which was detected by X‐ray diffraction (XRD). The thermal properties of PA6 nanofibers contained O‐MMT particles were more efficient than PA6/MMT nanofibers, that was verified using thermal gravimetric analysis. The crystalline properties of the electrospun nanofibers was investigated using differential scanning calorimeter and it was found that the degree of crystallinity in the PA6 nanofibers loaded with O‐MMT was much higher than PA6/MMT and PA6 nanofibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Flame retardance and mechanical properties of a polyamide 6/polyethylene/surface‐modified metal hydroxide ternary composite via a master‐batch method

Surface‐modified aluminum hydroxide and magnesium hydroxide mixtures (SAMHs) were filled with linear low‐density polyethylene (LLDPE) with a maleic anhydride grafted polyethylene (PE) compatibilizer to produce a SAMH master batch, which was then dispersed in polyamide 6 (PA6) to yield a PA6/PE/SAMH (50/20/30 by weight ratio) ternary composite. Through such a master‐batch method, an effective flame retardance UL94 V‐0 rating at a 3.2 mm thickness with a 33% limiting oxygen index was achieved. The flame‐retardance mechanism of the ternary composite was investigated by thermogravimetric analysis and scanning electron microscopy/energy dispersive X‐ray spectroscopy analysis. A cocontinuous PA6/PE polymer host and a preferential dispersion of SAMH particles in the matrix induced the formation of a compact flame‐resistant char layer and a high residue rate during burning; this resulted in the desired flame retardance of the ternary composite. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanical and structural characterization of POSS‐modified polyamide 6

This work investigated the mechanical behavior of POSS‐modified polyamide 6 (PA6), containing PA6 chains terminated at one end with aminopropyl‐heptaisobutyl POSS. Three systems with different POSS contents (5.4, 10.8, and 16.2 wt %), each characterized by a specific molecular mass, and the corresponding PA6 neat polymers were examined. The materials were first subjected to morphological and calorimetric analysis by wide‐angle X‐ray diffraction and differential scanning calorimetry, respectively. Tensile tests, performed on the samples in wet conditions, showed that stiffness, strength, and ductility were appreciably modified by the presence of POSS in the polymeric chains. The relationships among these effects and the microstructural characteristics of the systems also were analyzed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3409–3414, 2006     

Pyrolysis and flammability behavior of long (Glass fiber)‐Reinforced polyamide 6 by aluminum alkylphosphinate‐based flame retardants in combination with organic montmorillonite

The pyrolysis and flammability behavior of long (glass fiber)‐reinforced polyamide 6 containing aluminum alkylphosphinate‐based flame retardant in conjunction with montmorillonite or organic montmorillonite (OMMT) were investigated by using thermal gravimetry, limiting oxygen index, vertical burning test, and cone calorimeter measurements. The results revealed that the incorporation of OMMT in (aluminum alkylphosphinate)‐containing long (glass fiber)‐reinforced polyamide 6 did not significantly affect the thermal stability; however, they showed an obvious synergy on the char yield. The components from the flame retardant, especially phosphorus, acted in the gas phase and condensed phase simultaneously. Substitution of part of flame retardants with OMMT helped keep more phosphorus in the solid phase at the expense of gas‐phase activity, as demonstrated in scanning electron microscopy‐energy‐dispersive X‐ray characterization of the residue. This substitution constructed an impermeable barrier on the burning surface, which was responsible for the improvements in the vertical burning test classification and limiting oxygen index test. J. VINYL ADDIT. TECHNOL., 24:27–36, 2018. © 2015 Society of Plastics Engineers     

Hyperbranched polyester‐modified montmorillonite: a novel phase change material for energy storage

Hyperbranched polymer, montmorillonite (MMT) and phase change material (PCM) were used in the preparation of a novel energy storage clay material (H‐PCM). 1,3‐Diamino‐2‐propanol and methyl acrylate were firstly used in the synthesis of an AB2 intermediate. Then, Na‐MMT was modified by an intercalation agent, l‐glutamic acid. Third, hyperbranched polymer‐modified Na‐MMT (H‐MMT) was successfully fabricated using the amino acid‐modified Na‐MMT and AB2 intermediate. Subsequently, liquid paraffin was incorporated into H‐MMT, and non‐corrosive organic H‐PCM was prepared. This H‐PCM was systematically characterized using various methods, such as diffusion‐oozing circle test, differential scanning calorimetry (DSC), thermogravimetric (TG) analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and X‐ray diffraction (XRD). The diffusion‐oozing circle and DSC results revealed that H‐PCM possessed good heat storage and release capacity. In XRD analysis, expansions of the spacings in the plane were observed for all samples. TG analysis of this clay illustrated that it could be suitable for industrial applications due to its high thermal stability. © 2017 Society of Chemical Industry     

Effects of an (Intumescent flame retardant)‐montmorillonite combination on the thermal stability and fire‐retardant properties of LDPE/EVA nanocomposites

The combined effects of an organically modified montmorillonite (OMMT) and an intumescent flame retardant, poly (piperazine spirocyclic pentaerythritol bisphosphonate) (PPSPB), in (low‐density polyethylene)/[ethylene‐(vinyl acetate) copolymer] (LDPE/EVA) nanocomposites were observed. The results from X‐ray diffraction and transmission electron microscopy studies showed that exfoliated LDPE/EVA/PPSPB/OMMT nanocomposites were formed. Thermal stability and flammability properties were investigated by thermogravimetric analysis and cone calorimeter tests. The combination of PPSPB and montmorillonite improved thermal stability and reduced significantly the flammability, including peak heat release rate (PHRR), total heat release, average mass loss rate, etc. The PHRR of LDPE/EVA/PPSPB/OMMT was reduced by about 50% compared to that of an LDPE/EVA blend. The morphology and composition of the residues generated by cone calorimeter tests were investigated by scanning electronic microscopy (SEM) and energy dispersive X‐ray (EDX) analysis. The results of SEM showed that a compact and dense intumescent char was formed from the LDPE/EVA/PPSPB/OMMT nanocomposite upon combustion. The results of EDX examination revealed that the carbon content of this char was increased significantly by the combined effect of PPSPB and montmorillonite. J. VINYL ADDIT. TECHNOL., 19:285–292, 2013. © 2013 Society of Plastics Engineers     

Evaluation of melamine‐modified urea‐formaldehyde resins as particleboard binders

Particleboards bonded with 6 and 12% melamine‐modified urea‐formaldehyde (UMF) resins were manufactured using two different press temperatures and press times and the mechanical properties, water resistance, and formaldehyde emission (FE) values of boards were measured in comparison to a typical urea‐formaldehyde (UF) resin as control. The formaldehyde/(urea + melamine) (F/(U + M)) mole ratio of UMF resins and F/U mole ratio of UF resins were 1.05, 1.15, and 1.25 that encompass the current industrial values near 1.15. UMF resins exhibited better physical properties, higher water resistance, and lower FE values of boards than UF resin control for all F/(U + M) mole ratios tested. Therefore, addition of melamine at these levels can provide lower FE and maintain the physical properties of boards. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study on flame retardance of co‐microencapsulated ammonium polyphosphate and dipentaerythritol in polypropylene

Co‐microencapsulated ammonium polyphosphate and dipentaerythritol [M(A&D)] was prepared using a melamine‐formaldehyde (MF) resin by in situ polymerization method, and characterized by XPS. The co‐microencapsulation of ammonium polyphosphate and dipentaerythritol (DPER) leads to a great improvement in water solubility of the additives. The flame retardant effect of M(A&D) in polypropylene (PP) is evaluated using limiting oxygen index (LOI) and UL 94 test, and the water resistance of the PP/M(A&D) composites is also studied. The flame retardant properties and water resistance of the PP/M(A&D) composites are much better than the ones of the PP/APP/DPER composites. Moreover, the thermal stability of the PP/M(A&D) composites is improved compared with the PP/APP/DPER composites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Phase morphology evolution and compatibilization of immiscible polyamide 6/polystyrene blends using nano‐montmorillonite

Nanocomposites of organic nano‐montmorillonite (nano‐OMMT)‐filled immiscible polyamide 6 (PA6)/polystyrene (PS) blends were prepared by three different processing methods. Masterbatch M1 of OMMT/PA6 and masterbatch M2 of OMMT/PS were prepared as separate masterbatchs by melt mixing with PA6 or PS, and then either mixed together or each mixed individually with appropriate amounts of PS or PA6, respectively. The effects of nano‐OMMT content and processing method on the structure, phase morphology, and mechanical properties of the PA6/PS/OMMT nanocomposites were investigated by X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, and mechanical properties tests. The results showed that the nano‐OMMT by M1 and M2 masterbatches dispersed primarily as exfoliated platelets in the PA6 matrix in the final composites regardless of the method of preparation. A drastic decrease of dispersed PS phase size and a very homogeneous size distribution were observed with the addition of nano‐OMMT. The PA6/PS/OMMT nanocomposites prepared from the M2 displayed the smallest dispersed PS phase size and best distribution of OMMT. The improvement of the mechanical properties of the PA6/PS/OMMT nanocomposites was attributed to the enhanced compatibilization of the immiscible PA6/PS blends by using nano‐OMMT. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Essential work of fracture of rubber‐modified polyamide 6 in impact

In this paper the impact fracture behavior of two commercial, 10% and 25%, rubber‐modified polyamide 6 grades is investigated by the Essential Work of Fracture methodology, which implies the testing of a series of samples of different ligament lengths and the determination of the total fracture energy. The study is based on data obtained from specimens made either from thick injected plates or bars. Tests were carried out under Charpy and Izod configuration. Two modes of fracture were displayed by the blends: ductile fracture or mixed mode depending on rubber content, processing conditions and ligament lengths of the samples. When samples displayed completely stable crack propagation behavior and geometric similarity of load‐displacements diagrams, an essential work of fracture value w_Ie, independent of specimen thickness and testing configuration, could be extrapolated. Polym. Eng. Sci. 44:1707–1715, 2004. © 2004 Society of Plastics Engineers.     

新型磷硅改性环氧树脂阻燃性能研究

采用聚苯基硅氧烷(PPMS)、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)与双酚A型环氧树脂合成了新型的含磷硅环氧树脂(Si-P-EP),通过红外谱确认了其结构。将Si-P-EP与纯环氧树脂复配制备得到复合物Si-P-EP/EP,对其进行了氧指数和水平燃烧测试并通过红外光谱对燃烧后的残炭结构进行了分析。结果表明,Si-P-EP/EP的氧指数有所提高,水平火蔓延速率由27.27 mm/min降低到20.13 mm/min,Si-P-EP/EP燃烧后生成了含磷硅的炭层,从而提高了环氧树脂的阻燃性能。     

Preparation of polyamide resin‐encapsulated melamine cyanurate/melamine phosphate composite flame retardants and the fire‐resistance to glass fiber‐reinforced polyamide 6

In this study, melamine cyanurate (MCA)/melamine phosphate (MP) composite flame retardants were synthesized in the solution of phosphoric acid/polyamide 6 (PA6). Phosphoric acid acted as the solvent of PA6, catalyst of melamine‐cyanurate self‐assembly reaction and reactant of melamine‐phosphoric acid reaction. With the consumption of the acid, the pH value of the system increased, and the solved PA6 precipitated on the surface of the flame retardant particles to form polymeric encapsulation. This technology realized the synthesis and surface modification of the flame retardants in one process. The catalyst and solvent, phosphoric acid, was finally converted into the product MP, and need no an additional removing process. The encapsulated MCA/MP (EMCMP) composite flame retardants were successfully applied in the fire‐resistance to glass fiber (GF)‐reinforced PA6. Because the encapsulated layer of EMCMP was also PA6, good interfacial compatibility and effective dispersion of EMCMP in PA6 resin can be obtained, and the corresponding flame retardant materials showed excellent flame retardancy and mechanical performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1773–1779, 2006     

电子模块灌封用柔性阻燃型改性环氧树脂研究

选用柔性环氧树脂、活性增韧剂、磷系列阻燃剂FR-P和复合阻燃剂FR-A对环氧树脂CYD128进行改性,提高环氧树脂的柔韧和阻燃等性能,取得良好的改性效果,成功制备出柔性阻燃环氧电子灌封材料, 有利于解决环氧树脂在电子工程应用过程中的问题。     

Synthesis of a melamine‐cyclotriphosphazene derivative and its application as flame retardant on cotton gauze

The halogen‐free flame retardance of natural fiber is an everlasting challenge due to the well‐known poor solubility of phosphazene in water. In this case, a new cyclotriphosphazene derivative (MCP) was synthesized. It was etherized hexamethylolmelamine (HMMM) and hexachloro‐cyclotriphosphazene (HCCP) by one pot reaction. It was characterized by ¹H NMR, ¹³C NMR, ³¹P NMR, FT‐IR, TGA, SEM, limited oxygen index (LOI) and vertical flame testing. The MCP has good solubility in water and thermosetting MCP has compact structure which can expand several times after burning. Cotton gauze was soaked in six different concentration of aqueous solutions of MCP (0 wt %, 5 wt %, 10 wt %, 15 wt %, 20 wt % and 25 wt %, respectively) to obtain the flame retardant cloth. The cloth was soaked in 20 wt % MCP solution had higher char yield and LOI. They had no any afterflame and afterglow, and gauze 2‐ gauze 5 cannot be burned out in 12s ignition time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43555.