Influence of Phosphorus Structures and Their Oxidation States on Flame-Retardant Properties of Polyhydroxyurethanes.

This article focuses on the synthesis of polyhydroxyurethane (PHU) materials containing novel phosphorus flame retardants (FR). Four different phosphorus compounds were grafted onto cyclic carbonate: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), diethyl phosphite (DEP), diphenyl phosphite (DPP) and dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO). Thus, three novel phosphorus reactive cyclic carbonates which have never been reported so far were synthetized. Phosphorus FR containing PHU materials were characterized by FTIR to evidence the total conversion of the cyclic carbonate. Moreover, the gel contents up to 80% confirmed the formation of the polymer network. Then, the thermal stability and the flame-retardant properties were investigated by thermogravimetric analyses, cone calorimeter and pyrolysis combustion flow calorimeter. The mode of action of phosphorus compounds, depending on the oxidation state, was especially highlighted. Phosphonate (+III) provided better action in a condensed phase than phosphinate thanks to a more efficient char formation. Among phosphonates, differences were observed in terms of char-formation rate and expansion. DEP provided the best flame-retardant properties, with a reduction of 76% of pHRR with 2 wt% of phosphorus in cone calorimeter analysis. Therefore, this article highlighted the different modes of action of phosphorus flame retardants, depending on the oxidation state of phosphorus, in PHU materials.

Cascade (Dithio)carbonate Ring Opening Reactions for Self-Blowing Polyhydroxythiourethane Foams.

Polyurethane (PU) foams are very common materials that have found many applications over the years. Their use is constantly improving due to their unique physical properties and easy blowing which does not require the addition of a blowing agent. Greener routes have been explored in the recent years to replace isocyanates. One of the most promising routes is leading to polyhydroxyurethanes (PHU). However, with PHUs, external blowing agent are usually required to obtain a foam. Thus, the work focuses on PHU foam synthesis using in situ reaction to produce NIPU foam. Hence, the aminolysis of thiocyclic carbonate triggers Pearson reaction between released thiols and cyclic carbonates which serves as a chemical blowing agent.