Aluminium diethylphosphinate (AlPi-Et) and inorganic aluminium phosphinate with resorcinol-bis(di-2,6-xylyl phosphate) (AlPi-H+RXP) were compared with each other as commercially available halogen-free flame retardants in poly(butylene terephthalate) (PBT) as well as in glass-fibre-reinforced PBT (PBT/GF). Pyrolysis behaviour and flame retardancy performance are reported in detail. AlPi-H+RXP released phosphine at very low temperatures, which can become a problem during processing. AlPi-Et provided better limiting oxygen index (LOI) values and UL 94 ratings for bulk and PBT/GF than AlPi-H+RXP. Both flame retardants acted via three different flame-retardancy mechanisms in bulk as well as in PBT/GF, namely, flame inhibition, increased amount of char, and a protection effect of the char. AlPi-Et was more efficient in decreasing the total heat evolved of PBT in the cone calorimeter test. AlPi-H+RXP reduced the peak heat release rate of PBT more efficiently than AlPi-Et. An optimum loading of AlPi-Et in PBT/GF was found, which was below the supplier's recommendation. This loading provides a maximum increase in LOI and a maximum decrease in total heat evolved.
The flame retardancy of poly(butylene terephthalate) (PBT) containing aluminium diethlyphosphinate (AlPi) and/or nanometric metal oxides such as TiO2 or Al2O3 was investigated. In particular the different active flame retardancy mechanisms were discovered. Thermal analysis, evolved gas analysis (TG-FTIR), flammability tests (LOI, UL 94), cone calorimeter measurements and chemical analyses of residues (ATR-FTIR) were used. AlPi acts mainly in the gas phase through the release of diethylphosphic acid, which provides flame inhibition. Part of AlPi remains in the solid phase reacting with the PBT to phosphinate-terephthalate salts that decompose to aluminium phosphate at higher temperatures. The metal oxides interact with the PBT decomposition and promote the formation of additional stable carbonaceous char in the condensed phase. A combination of metal oxides and AlPi gains the better classification in the UL 94 test thanks to the combination of the different mechanisms.
Copolyesters with an alternating sequence of terephthalic acid and aliphatic dicarboxylic acids were prepared with three different methods. First, dicarboxylic acid dichlorides were reacted with bis(2-hydroxyethyl)terephthalate (BHET) in refluxing 1,2-dichlorobenzene. Second, the same monomers were polycondensed at 0-20 °C in the presence of pyridine. Third, dicarboxylic acid dichlorides and silylated BHET were polycondensed in bulk. Only this third method gave satisfactory molecular weights. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that the copolyesters prepared by the pyridine and silyl methods might have contained considerable fractions of cyclic oligoesters and polyesters despite the absence of transesterification and backbiting processes. The alternating sequences and thermal properties were characterized with 1H NMR spectroscopy and differential scanning calorimetry measurements, respectively. In agreement with the alternating sequence, all copolyesters proved to be crystalline, but the crystallization was extremely slow [slower than that of poly(ethylene terephthalate)]. A second series of alternating copolyesters was prepared by the polycondensation of silylated bis(4-hydroxybut- yl)terephthalate with various aliphatic dicarboxylic acid dichlorides. The resulting copolyesters showed significantly higher rates of crystallization, and the melting temperatures were higher than those of the BHET-based copolyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3371-3382, 2001