To obtain industrialized poly(ethylene terephthalate) (PET) composites with highly efficient flame retardancy, a phosphorus-nitrogen (P-N) containing hyperbranched flame retardant additive was synthesized by 9,10-dihydro-9-oxa-10-phospho-phenanthrene-butyric acid (DDP) and tris(2-hydroxyethyl) isocyanurate (THEIC) through high temperature esterification known as hyperbranched DDP-THEIC (hbDT). The chemical structure of the synthesized hbDT was determined by FTIR, ¹H NMR, ¹³C NMR, and GPC, etc. Subsequently, hbDT/PET composites were prepared by co-blending, and the effects of hbDT on the thermal stability, flame retardancy, combustion performance, and thermal degradation behavior of PET were explored to deeply analyze its flame retardant mechanism. The test results showed that hbDT was successfully synthesized, and that hbDT maintained thermal stability well with the required processing conditions of PET as retardant additives. The flame retardant efficiency of PET was clearly improved by the addition of hbDT via the synergistic flame-retardant effect of P and N elements. When the mass fraction of flame retardant was 5%, the LOI of the hbDT/PET composite increased to 30.2%, and the vertical combustion grade reached UL-94 V-0. Compared with pure PET, great decreased total heat release (decreased by 16.3%) and peak heat release rate (decreased by 54.9%) were exhibited. Finally, the flame retardant mechanism of hbDT/PET was supposed, and it was confirmed that retardant effect happened in both the gas phase and condensed phase. This study is expected to provide a new idea for the development of low toxic, environment-friendly and highly efficient flame retardant additive for polyesters in an industry scale.

Abstract

To understand the influence of the construction of pH-responsive glycopolymer carriers on loading and release behaviors of the drug, three types of block glycopolymers with similar compositions but different constructions, PEG-b-P(DEA-co-GAMA), PEG-b-PDEA-b-PGAMA and PEG-b-PGAMA-b-PDEA, were successfully synthesized via atom transfer radical polymerization (ATRP) method. The compositions and structures of the three glycopolymers were characterized using ¹H NMR (nuclear magnetic resonance) and GPC (gel permeation chromatography), while the morphology and size of aggregates from pH-sensitive block glycopolymers were measured using TEM (transmission electron microscopy) and DLS (dynamic light scattering). The results indicated that the micelles prepared from PEG-b-PGAMA-b-PDEA had a more compact shell structure. The drug-loaded micelles were prepared using the diafiltration method at pH 10, and the loading content and loading efficiency were analyzed using a UV-visible spectrophotometer. DOX-loaded micelles formed by PEG-b-PGAMA-b-PDEA with the more compact shell construction showed the highest loading content and loading efficiency (12.0 wt% and 58.0%) compared with the other two micelles. Moreover, the DOX release tests of these micelles were carried out under two PBS conditions (pH 7.4 and pH 5.5), and the DOX release amount in a certain time was analyzed using a UV-visible spectrophotometer. The results showed that the more compact shell construction of the three layered micelle obstructed the diffusion of a proton into the PDEA core at pH 5.5 and delayed the drug from releasing under both conditions. Moreover the two-layered micelle with a PDEA and PGAMA mixed core showed a relatively high release amount owing to the porous core permitting unimpeded releasing at pH 7.4 and promoted the protonation of PDEA at pH 5.5. Insights gained from this study show that the structure of block copolymers, leading to different constructions of micelles, could adjust the drug loading and release behavior to certain extent, thus it may contribute to improving the design of desirable drug delivery systems.