Few-layer black phosphorus (BP)- and red phosphorus (RP)-modified diglycidyl ether of bisphenol A-based epoxy resins (EP) was prepared with 4,4'-diaminodiphenylsulfone as a curing agent. The thermal stability and flame-retardant properties of the modified EPs were compared. Both BP and RP were able to improve the flame-retardant properties of EPs, while the BP showed higher flame-retardant efficiency than RP. As a two-dimensional nanomaterial, BP exhibited good compatibility, high flame-retardant efficiency, and negligible impact on the mechanical and thermal stability of EP. Pyrolysis-gas Fourier-transform infrared spectroscopic analysis of EP showed that the addition of BP significantly inhibited the release of pyrolysis products in the gas phase. The modes of action for flame-retardant BPs in gas phase and condensed phase were proposed.
Polyolefin suffers from degradation during processing and application. To prolong the service life, antioxidants are needed in the packing formula of polyolefin products. The usage of natural antioxidants could avoid potential health hazards aroused by synthetic ones. Pine needles have long lives and hardly rot, suggesting their high resistance to degradation. To provide a new candidate of natural antioxidants and add more value to pine needles, pine needle extracts (PNE) were investigated as the antioxidant of linear low-density polyethylene (LLDPE). PNE-modified LLDPE (PE-PNE) exhibited much better short-term and long-term aging resistance than pure LLDPE (PE): Oxidation induction time (OIT) of PE-PNE was 52 times higher than that of PE, and the increments of carbonyl index (CI) of PE-PNE-1st samples placed under daylight and in the dark were approximately 75% and 63% of PE under the same conditions. It could be attributed to the attractive antioxidant capacity of PNE (IC50 of DPPH radical scavenging was 115 µg/mL). In addition, the PE-PNE sample showed high processing stability and maintenance of the mechanical property during multiple extrusions: only a 0.2 g/10 min decrease in melting flow rate was found after five extrusions; the tensile strength and elongation at break were almost unchanged. All results reveal that pine needle extracts could play a role in LLDPE stabilization. Moreover, as pine needles are mainly considered a kind of waste, the present study would benefit the budget-reducing polyolefin industry.
