Synthesis and Characterization of a Novel DOPO-Based Flame Retardant Intermediate and Its Flame Retardancy as a Polystyrene Intrinsic Flame Retardant.

Abstract

The research on intrinsic flame retardant has become a hot topic in the field of flame retardant. The synthesis of reactive flame-retardant monomer is one of the effective methods to obtain an intrinsic flame retardant. In addition, in view of the small molecular flame retardant easily migrates from the polymer during the use process, which leads to the gradual reduction of the flame retardant effect and even the gradual loss of flame retardant performance, and the advantages of atom transfer radical polymerization (ATRP) technology in polymer structure design and function customization, we first synthesized reactive flame retardant monomer 6-(hydroxymethyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide (FAA-DOPO), then synthesized polystyrene bromine (PS148-Br) macromolecular initiator by ATRP technology, and finally obtained block copolymer polystyrene-b-poly{6-(hydroxymethyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide} (PS-b-PFAA-DOPO) by the polymerization of FAA-DOPO initiated by macromolecular initiator PS148-Br by ATRP technology. The chemical structure of FAA-DOPO was characterized by 1D and 2D NMR (1H, 13C, DEPT 135, HSQC, COSY, NOE, and HMBC) spectra, Fourier transform infrared spectroscopy (FTIR), liquid chromatography-tandem mass spectrometry (LC-MS) and X-ray photoelectron spectroscopy (XPS). The chemical structure and molecular weight of PS-b-PFAA-DOPO were characterized by FTIR and gel permeation chromatography (GPC). The thermal and flame-retardant properties of PS-b-PFAA-DOPO were characterized by thermogravimetry analysis (TG), UL-94, limiting oxygen index (LOI), and microscale combustion calorimetry (MCC). It was found that FAA-DOPO could be used as a monomer for polymerization, although FAA-DOPO had a large steric hindrance from the chemical structure of FAA-DOPO, the UL-94 grade of PS-b-PFAA-DOPO reached the V-0 grade, and the LOI increased by 59.12% compared with PS148-Br.