A novel phosphorus-containing poly(1,4-cyclohexylenedimethylene terephthalate) copolyester: Synthesis, thermal stability, flammability and pyrolysis behavior

摘要

Poly(1,4-cyclohexylenedimethylene terephthalate) (PCT) is a commercialized semicrystalline high-temperature thermoplastic polyester, but its flammability restricted its applications in some fields. A third monomer, 2-(6-oxido-6H-dibenz < c,e > <1,2> oxaphosphorin-6-yl)-1,4-hydroxyethoxy phe-nylene (DOPO-HQ-HE), was used to synthesize an intrinsic flame-retardant copolyester through trans-esterification and polycondensation. Its chemical structure was confirmed by ~1H NMR and ICP-AES. The crystallization behavior of PCTDs was investigated by DSC and WAXD, and found that the introduction of DOPO-HQ-HE slightly reduced the crystallization ability of PCT. TGA results showed that the incorporation of phosphorus-containing monomer improved the thermal stability of copolyesters both in nitrogen and air. Flynn-Wall-Ozawa method was used to analyze the thermal degradation kinetics of copolyesters, and found that the apparent activation energy was enhanced. The microscale combustion calorimetry (MCC) showed that PCTDs had lower heat release rate and total heat release than PCT. The results of the limiting oxygen index (LOI), the UL-94 vertical and the cone calorimeter test indicated that DOPO-HQ-HE endowed PCTDs with flame-retardant properties to some extent. Besides this, the cone calorimeter results show that the introduction of DOPO-HQ-HE remarkably suppressed the smoke release of PCT. The pyrolysis behaviors of PCT and PCTDs were investigated by Py-GC-MS, and found that the decomposition of PCT chains usually happened at ester bond and followed the random chain scission mechanism. The introduction of DOPO-HQ-HE almost had no effect on the thermal degradation mechanism of PCT.