In this work, a novel, effective and simple approach to largely improve the thermomechanical properties and heat distortion resistance of biodegradable poly­(l-lactide) (PLLA) by using a new nucleating agent (NA), i.e., itself high-melting-point homocrystallites (hPLLA crystallites) is reported. Specially, hPLLA crystallites with a melting temperature (T m) of 187 °C were introduced into the PLLA matrix with a lower T m, i.e., 168 °C via simply melt blending at 170 °C which is between the T ms of the two PLLAs. Nonisothermal and isothermal crystallization results reveal that hPLLA crystallite is an efficient nucleating agent for PLLA. Also, hPLLA crystallites show much more prominently promoting effect on the crystallization rate of PLLA in comparison with two widely reported NAs for PLLA, talc and stereocomplex crystallites. Most importantly, this promoting effect is still efficient at very high cooling rate, leading to a crystallinity of 39.1% at a cooling rate of 100 °C/min, which can help to obtain high-crystallinity PLLA products in conventional manufacturing processes. The optical microscopic observation reveals that the remarkable crystallization promotion can be attributed to the outstanding heterogeneous nucleation effect, as a result of both identical chemical constitution and lattice constitution between hPLLA crystallites and PLLA matrix. Further characterizations indicate that the enhancement of PLLA crystallinity by using such a new efficient NA can enhance the thermomechanical properties and heat distortion resistance of PLLA remarkably. For instance, at 80 °C (above T g of PLLA), the elastic modulus increases by 60 times from 8 to 477 MPa with the incorporation of 5 wt % hPLLA.

After the surface silylation with 3-methacryloxypropyltrimethoxysilane, silica nanoparticles were further modified by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The immobilization of DOPO on silica nanoparticles was confirmed by Fourier transform infrared spectroscopy, UV–visible spectroscopy, magic angle spinning nuclear magnetic resonance, and thermogravimetric analysis. By incorporating the DOPO-immobilized silica nanoparticles (5 wt%) into polypropylene matrix, the thermal oxidative stability exhibited an improvement of 62 °C for the half weight loss temperature, while that was only 26 °C increment with incorporation of virgin silica nanoparticles (5 wt%). Apparent activation energies of the polymer nanocomposites were estimated via Flynn–Wall–Ozawa method. It was found that the incorporation of DOPO-immobilized silica nanoparticles improved activation energies of the degradation reaction. Based on the results, it was speculated that DOPO-immobilized silica nanoparticles could inhibit the degradation of polypropylene and catalyze the formation of carbonaceous char on the surface. Thus, thermal stability was significantly improved.

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The synergistic effect of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) immobilized silica (SiO 2 -DOPO) nanoparticles with an intumescent flame retardant (IFR) on the flame retardancy of polypropylene (PP) was investigated by UL 94 vertical tests and limiting oxygen index (LOI) measurements. It was found that the PP/IFR composites (25 wt%) achieved the UL94 V0 grade and LOI increased to 32.1 with an incorporation of 1.0 wt% SiO 2 -DOPO nanoparticles. Based on thermogravimetric analysis, scanning electronic microscopy and rheological analysis, it is speculated that three factors are mainly contributed to the improvement of the flame retardancy. First, the thermal stability of PP/IFR composites was improved by incorporating SiO 2 -DOPO nanoparticles. Second, the presence of SiO 2 -DOPO nanoparticles could induce the formation of a continuous char skin layer during combustion. The compact char layer could effectively impede the transport of bubbles and heat. Third, rheological analysis indicated that SiO 2 -DOPO nanoparticles could increase viscosity of the PP/IFR composites, which was also benefited to increase flame retardancy.