A Novel Organophosphorus Hybrid with Excellent Thermal Stability: Core-Shell Structure, Hybridization Mechanism, and Application in Flame Retarding Semi-Aromatic Polyamide.
An organophosphorous hybrid (BM@Al-PPi) with unique core-shell structure was prepared through hybridization reaction between boehmite (BM) as the inorganic substrate and phenylphosphinic acid (PPiA) as the organic modifier. Fourier transform infrared spectra (FTIR), solid state (31)P and (27)Al magic angle spinning nuclear magnetic resonance, X-ray diffraction, and element analysis were used to investigate the chemical structure of the hybrids, where the microrod-like core was confirmed as Al-PPi aggregates generated from the reaction between BM and PPiA, and those irregular nanoparticles in the shell belonged to residual BM. Compared with the traditional dissolution-precipitation process, a novel analogous suspension reaction mode was proposed to explain the hybridization process and the resulting product. Scanning electronic microscopy further proved the core-shell structure of the hybrids. BM exhibited much higher initial decomposition temperature than that of Al-PPi; therefore, the hybrid showed better thermal stability than Al-PPi, and it met the processing temperature of semi-aromatic polyamide (HTN, for instance) as an additive-type flame retardant. Limiting oxygen index and cone calorimetric analysis suggested the excellent flame-retardant performance and smoke suppressing activity by adding the resulting hybrid into HTN.
Fire-Resistant, Strong, and Green Polymer Nanocomposites Based on Poly(lactic acid) and Core–Shell Nanofibrous Flame Retardants
Despite extraordinary mechanical properties and excellent biodegradability, poly(lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its wide applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, so far, they normally compromise the mechanical strength of PLA. Herein, we have demonstrated the fabrication of a novel core–shell nanofibrous flame-retardant system, PN-FR@CNF, through in situ chemically grafting the phosphorus–nitrogen-based polymer onto the cellulose nanofiber (CNF) surface. The results show that adding 10 wt % PN-FR@CNF enables PLA to achieve a V-0 flame resistance rating during vertical burning tests and to exhibit a dramatically reduced peak heat release rate in cone calorimetry measurements, indicating a significantly reduced flammability. In addition, the tensile strength of PLA also increases by around 24% (about 72 MPa). This work offers an innovative methodology for th...
A Review of Recent Progress in Phosphorus-based Flame Retardants
Recent patent and technical works indicate a growing interest in halogen-free solutions with the predominance of the literature focusing on phosphorus-based flame retardants. Patents published on the flame retardancy of polycarbonate and its blends significantly exceed the number of patents on flame retardancy of any other polymer. Bridged aromatic diphenyl phosphates, especially resorcinol bis(diphenyl phosphate) and bisphenol A bis(diphenyl phosphate) have found broad application because of their good thermal stability, high efficiency, and low volatility. Another actively reported group of compounds are the metal salts of dialkylphosphonic acid as well as calcium hypophosphite, which have recently been found to be particularly effective in poly(butylene terephthalate) and polycarbonate. These products are synergistic with a number of phosphorus and nitrogen-containing compounds, such as melamine salts, which seem to be very efficient and commercially useful in nylons. Printed wiring boards comprise the largest market for flame-retardant polymeric materials. Recently, there has been a strong interest in halogen free solutions in East Asia and Europe. A recent halogen-free introduction is the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, which can be reacted into epoxies. Another reactive product with some processing and property advantages is poly(m-phenylene methylphosphonate). Because of the banning of pentabromodiphenyl ether in Europe and voluntary withdrawal of this product from the market in the US, the polyurethane (PU) industry is searching for a more environmentally acceptable low-scorch alternative. Both halogenated and halogen-free solutions are being considered but the PU industry seems to have a preference for the halogen-free products, generally containing phosphorus.