Facile, one‐pot synthesis of aromatic diamine‐based phosphinated benzoxazines and their flame‐retardant thermosets

Abstract

Three aromatic diamine‐based, phosphinated benzoxazines (7–9) were prepared from three typical aromatic diamines—4,4′‐diamino diphenyl methane (1), 4,4′‐diamino diphenyl sulfone (2), and 4,4′‐diamino diphenyl ether (3) by a one‐pot procedure. To clarify the reaction mechanism, a two‐pot procedure was applied, in which the reaction intermediates (4–6) were isolated for characterization. The structures of intermediates and benzoxazines were confirmed by high resolution mass, IR, and 1D and 2D‐NMR spectra. In addition to self‐polymerization, (7–9) were copolymerized with cresol novolac epoxy (CNE). After curing, the homopolymers of P(7–9) are brittle while the copolymers of (7–9)/CNE are tough. Dynamic mechanical analysis shows the Tgs of (7–9)/CNE copolymers are 187, 190, and 171 °C, respectively. Thermal mechanical analysis shows the CTEs of (7–9)/CNE copolymers are 46, 38, and 46 ppm, respectively. All the (7–9)/CNE copolymers belong to an UL‐94 V‐0 grade, demonstrating good flame retardancy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

High performance benzoxazine/CNT nanohybrid network – An easy and scalable way to combine attractive properties

“…1,4-phenylenediamine 60 g (0.55 mol), finely powdered, was then added into the beaker and immersed in an oil bath preheated at 140°C. The addition of the diamine leads to the gelation of the mixture resulting from the condensation of the aromatic diamine and formaldehyde and the subsequent formation of a triazine network [30,31]. At this temperature, the triaza compound reacts quickly with phenol and the gel is destroyed in 2 min.…”

Syntheses of Two Dopo-Based Reactive Additives as Flame Retardants and Co-Curing Agents for Epoxy Resins

“…4,5 It has been reported that phosphorus-containing compounds able to molecularly incorporate in the resin network are expected to exhibit better flame retardancy. [6][7][8][9][10] As a typical flame retardant (FR) with active phenolic OH groups, 2-(6-oxid-6H-dibenz[c,e][1,2]-oxaphosphorin-6-yl)-1,4-benzenediol embody this incorporation strategy. 11 Another approach to realize this strategy is based on the addition reactions of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and imines, whose products are characteristic of binary functionality of FR and co-curing agent.…”

A facile way to prepare two novel DOPO‐containing liquid benzoxazines and their graphene oxide composites

“…DOPO and its derivatives not only could be used as reactive and additive flame retardant, but also could be used in linear polyester, polyamide, epoxy resin, polyurethane, and other polymer flame retardant processed . Lin prepared three aromatic diamine‐based, phosphinated benzoxazines from three typical aromatic diamines‐4,4′‐diamino diphenyl methane, 4,4′‐diamino diphenylsulfone, and 4,4′‐diamino diphenyl ether by a one‐pot procedure. The results demonstrated that these materials offered high thermal stability and good flame retardancy …”