A novel flame-retardant composite was prepared by introducing a phosphorus-nitrogen flame retardant and DOPO-SiO2 into PA6. DOPO-SiO2 was synthesized successfully in a one-step process. PA6/OP1314/DOPO-SiO2 achieved a UL 94 V-0 rating with an LOI value of 31%. The maximum mass loss rate of decomposition decreased significantly and char residue increased to 11.6 wt % compared with that of pure PA6. The compacted and dense char was formed due to the combination of the P-N flame retardant and DOPO-SiO2. The complex viscosity of PA6/OP1314/DOPO-SiO2 increased considerably which tend to prevent the dripping phenomenon. The flame-retardant mechanism of PA6/OP1314/DOPO-SiO2 was also investigated by Fourier transform infrared spectroscopy FTIR at different temperatures and the pyrolysis products were investigated by pyrolysis gas chromatography/ mass spectrum (Py-GC/MS). It was assumed that DOPO-SiO2 and the hypophosphite of OP1314 possess excellent flame retardancy during the gaseous phase. Meanwhile, melamine and phosphate reacted with the pyrolytic products of PA6 to protect the matrix during the condensed phase. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42932.
In this article, the nanocomposites thermoplastic polyester-ether elastomer (TPEE) with phosphorous–nitrogen (P–N) flame retardants and montmorillonite (MMT) was prepared by melt blending.The fire resistance of nanocomposites was analyzed by limiting oxygen index (LOI) and vertical burning (UL94) test. The result shows that the flame retardants containing P–N increased the LOI of the material from 17.3 to 27%. However, TPEE containing P–N flame retardants just got UL94 V-2 ranking, which resulted in the flaming dripping phenomenon. On the other hand, TPEE containing P–N flame retardant and organic-modified montmorillonite (o-MMT) achieved UL94 V-0 rating for the special microstructure. The XRD and TEM morphology has demonstrated that the formation of multi-ordered structure regarding restricted segmental motions at the organic–inorganic interface and stronger interactions between the clay mineral layers and the polymer chains. The structure was supported by the results of rheological properties and DSC analysis. The thermal degradation and char residue characterization was studied by thermal gravimetric analysis (TGA) and SEM-EDX measurements, respectively. The TGA and SEM-EDX have demonstrated that o-MMT results in the increase of char yield and the formation of the thermal stable carbonaceous char. POLYM. COMPOS., 37:700–708, 2016. © 2014 Society of Plastics Engineers
Polyhedral oligomeric silsesquioxane containing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DP) was used to flame-retard 4,4′-bismaleimidophenyl methane (BDM)/2,2′-dially bisphenol A (DBA) resins, and the integrated properties of the resins were investigated. The fire resistance of BDM/DBA resins containing DP was analyzed by limiting oxygen index (LOI) and vertical burning (UL94) tests. The results show that DP increased the LOI of the resins from 25.3 to 38.5%. The BDM/DBA resins were evaluated to have a UL-94 V-1 rating, which did not satisfy the high standards of industry. On the other hand, BDM/DBA containing DP achieved a UL-94 V-0 rating. The thermal stability and char formation were studied by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy. TGA and scanning electron microscopy–energy-dispersive X-ray spectrometry measurements demonstrated that the DP resulted in an increase in the char yield and the formation of the thermally stable carbonaceous char. The results of Raman spectroscopy showed that the DP enhanced the graphitization degree of the resin during combustion. Moreover, the modified BDM/DBA resins exhibited improved dielectric properties. Specifically, the dielectric constant and loss at 1 MHz of the BDM/DBA/15% DP resin were 3.11 and 0.008, respectively, only about 93 and 73% of those of the BDM/DBA resin. All of the investigations showed that DP was an effective additive for developing high-performance resins with attractive flame-retardant and dielectric properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41545.
In this study, thermoplastic poly(ester ether) elastomer (TPEE) nanocomposites with phosphorus–nitrogen (P–N) flame retardants and montmorillonite (MMT) were prepared by melt blending. The fire resistance of the nanocomposites was analyzed by limiting oxygen index (LOI) and vertical burning (UL 94) tests. The results show that the addition of the P–N flame retardants increased the LOI of the material from 17.3 to 27%. However, TPEE containing P–N flame retardants only obtained a UL 94 V-2 ranking; this resulted in a flame dripping phenomenon. On the other hand, TPEE containing the P–N flame retardant and organically modified montmorillonite (o-MMT) achieved better thermal stability and good flame retardancy; this was ascribed to its partially intercalated structure. The synergistic effect and synergism were investigated by Fourier transform infrared spectroscopy and thermogravimetry. The introduction of o-MMT decreased the inhibition action of the P–N flame retardant and increased the amount of residues. The catalytic decomposition effect of MMT and the barrier effect of the layer silicates are discussed in this article. The residues after heating in the muffle furnace were analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy and laser Raman spectroscopy. It was shown that the intercalated layer silicate structure facilitated the crosslinking interaction and promoted the formation of additional carbonaceous char residues in the formation of the compact, dense, folded-structure surface char. The combination of the P–N flame retardant and o-MMT in TPEE resulted in a better thermal stability and fire resistance because of the synergistic effect of the mixture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41094.
Blends of poly(ethylene terephthalate) and poly(ethylene-2,6-naphthalate) (70 : 30 w/w) were prepared via a melt-mixing process at 280°C with various mixing times. The melt-mixed blends were analyzed by magnetic resonance spectroscopy, differential scanning calorimetry, dynamic mechanical measurements, transmission electron microscopy, and tensile tests. The results indicate that the blends mixed for short times had lower extents of transesterification and were miscible to a limited extent. The blends initially show two glass transitions, which approached more closely and merged gradually with increasing mixing time. A mechanical model was used to help understand the glass-transition behavior. With increasing mixing time, the phase structure of the blends improved, and this led to an increase in the tensile strength. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
A thermoplastic modification method was studied for the purpose of improving the toughness and heat resistance and decreasing the curing temperature of the cured epoxy/4, 4′-diaminodiphenyl sulfone resin system. A polyimide precursor-polyamic acid (PAA) was used as the modifier which can react with epoxy. The effects of PAA on curing temperature, thermal stability and mechanical properties were investigated. The initial curing temperature (Ti) of the resin with 5 wt % PAA decreased about 50°C. The onset temperature of thermal decomposition and 10 wt %-weight-loss temperature for the resin system containing 2 wt % PAA increased about 60°C and 15°C respectively. Besides, the value of impact toughness and plain strain fracture toughness for the modified epoxy resin increased ∼ 190% and 55%, respectively. Those changes were attributed to the outstanding thermal and mechanical properties of polyimide, and more importantly to formation of semi-interpenetrating polymer networks composed by the epoxy network and linear PAA. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
The research focused on the PA66/PC/silicone rubber composites. By adding silicone rubber as a toughener, the composites were prepared via dynamic vulcanization. The morphology and properties of the composites were characterized by FTIR, TEM, SEM, XRD, etc. The FTIR spectrum of the composites presented an increase of the 1730, 1240, and 1450 cm−1 that can be due to the CO interaction and the presence of the OCOO group, and this fact can mean the formation of the PA66–PC copolymer. The crosslinking of silicone rubber in the PA66/PC matrix formed the net-like structure like semi-IPN, which is propitious to enhance the interaction between PA66 matrix and PC and in further makes the PC particles embed in PA66 matrix closely. Novel composites are gained with outstanding mechanical properties and high temperature resistance, so the combine toughening by silicone rubber and PC is an ideal toughening system owing to the synergistic effect. In addition, the PA66/PC/silicone rubber/OMMT composite exhibits better flexile strength and flexile modulus without weakening other mechanical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
The elastomer toughening of PA66/PA6 nanocomposites prepared from the organic modified montmorillonite (OMMT) was examined as a means of balancing stiffness/strength versus toughness/ductility. Several different formulations varying in OMMT content were made by mixing of PA6 and OMMT as a master-batch and then blending it with PA66 and different elastomers in a twin screw extruder. In this sequence, the OMMT layers were well exfoliated in the nylon alloy matrix. The introduction of silicate layers with PA6 induced the appearance of the γ crystal phase in the nanocomposites, which is unstable and seldom appears in PA66 at room temperature and it further affected the morphology and dispersion of rubber phase resulting in much smaller rubber particles. The incorporation of POE-g-MA particles toughened the nanocomposites markedly, but the tensile modulus and strength were both reduced. Conversely, the use of OMMT increased the modulus but decreased the fracture toughness. The nanocomposites exhibited balanced stiffness and toughness. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
To improve the barrier properties of poly(ethylene terephthalate) (PET), PET/poly(ethylene 2,6-naphthalate) (PEN) blends with different concentrations of PEN were prepared and were then processed into biaxially oriented PET/PEN films. The air permeability of bioriented films of pure PET, pure PEN, and PET/PEN blends were tested by the differential pressure method. The morphology of the blends was studied by scanning electron microscopy (SEM) observation of the impact fracture surfaces of extruded PET/PEN samples, and the morphology of the films was also investigated by SEM. The results of the study indicated that PEN could effectively improve the barrier properties of PET, and the barrier properties of the PET/PEN blends improved with increasing PEN concentration. When the PEN concentration was equal to or less than 30%, as in this study, the PET/PEN blends were phase-separated; that is, PET formed the continuous phase, whereas PEN formed a dispersed phase of particles, and the interface was firmly integrated because of transesterification. After the PET/PEN blends were bioriented, the PET matrix contained a PEN microstructure consisting of parallel and extended, separate layers. This multilayer microstructure was characterized by microcontinuity, which resulted in improved barrier properties because air permeation was delayed as the air had to detour around the PEN layer structure. At a constant PEN concentration, the more extended the PEN layers were, the better the barrier properties were of the PET/PEN blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1309–1316, 2006