Polyvinyl Alcohol Composite Films Containing Flame-Retardant DOPO-VTES and α-ZrP

Polyvinyl alcohol (PVA) is used in various fields; however, its highly flammable property greatly limits its application. In order to improve the flame-retardant properties of PVA, one method is by adding flame retardants directly, while another method is through grafting, cross-linking and hydrogen bonding. A flame retardant, 9, 10-dihydro-9, 10-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-vinyltrimethoxysilane (VTES), was synthesized through the addition reaction of a P-H bond on the DOPO and unsaturated carbon-carbon double bonds on the VTES. Then, the DOPO-VTES and zirconium phosphate (α-ZrP) were blended with PVA to cast a film, in which DOPO-VTES was grafted onto the PVA by cross-linking the hydroxyl group in the molecular structure of DOPO-VTES with the hydroxyl group in PVA; α-ZrP was used as a cooperative agent of DOPO-VTES. The cone calorimetry test (CCT) showed a significant reduction in both the heat release rate (HRR) and total heat release rate (THR) for the flame-retardant PVA films compared to pure PVA. Additionally, thermogravimetric analysis (TGA) revealed a higher residual char content in the flame-retardant PVA films than in pure PVA. These findings suggested that the combination of DOPO-VTES and α-ZrP could improve the flame retardancy of PVA. The cooperative flame-retardant mode of action at play was possibly that DOPO in the DOPO-VTES acted as a mainly gas-phase flame retardant, which yielded a PO radical; VTES in the DOPO-VTES produced silicon dioxide (SiO₂), which acted as a thermal insulator; and α-ZrP catalyzed the carbonization of the PVA. By combining DOPO-VTES with α-ZrP, a continuous dense carbon layer was formed, which effectively inhibited oxygen and heat exchange, resulting in a flame-retardant effect. It is expected that flame-retardant films for PVA have a broad development prospect and potential in the fields of packaging materials, electronic appliances, and lithium-ion battery separators.