Reacting 1-phenyl-2-(diphenylphosphino)ethanone (P 1 ∼OH), 1-tert-butyl-2-(diphenylphosphino)ethanone (P 2 ∼OH) and 1-phenyl-2-(diphenylphosphino)propanone (P 3 ∼OH) with ReOCl 3 (PPh 3 ) 2 and Re(NPh)Cl 3 (PPh 3 ) 2 in toluene and ethanol in the presence of NEt 3 yields complexes in which these ligands bind as monoanionic enolato chelating agents. Bromo and iodo analogues are prepared similarly. The reactions are solvent dependent. The disubstituted ReOCl(P∼O) 2 compounds obtained in toluene adopt the 'twisted' cis-(P,P) octahedral structure. With Re(NPh)Cl 3 -(PPh 3 ) 2 , P 1 ∼OH and P 2 ∼OH give the corresponding Re(NPh)Cl(P∼O) 2 compounds and the trans-(P,P)-trans-(Cl,Cl) isomer of monosubstituted Re(NPh)Cl 2 (PPh 3 )(P∼O) as the major products, together with small amounts of 'twisted' trans-(P,P) Re(NPh)Cl(P∼O) 2 . The monosubstituted complex is the only species isolated with P 3 ∼OH. The major structural difference between the two systems is the small stability gap between the cis-and the trans-(P,P) isomers of the imido complexes. In ethanol, unexpected cis-ethoxo-oxo complexes ReO(OEt)(P∼O) 2 are isolated, resulting from stereoselective substitution of the halide in the 'twisted' cis-(P,P) octahedral complexes. The reactions with Re(NPh)Cl 3 (PPh 3 ) 2 are less selective and give rise to mixtures of complexes. The trans-ethoxo-phenylimido compound Re(NPh)(OEt)(P 1 ∼O) 2 is obtained in good yield. A crystallographic study reveals an unexpected 'equatorial' trans-(P,P) structure with the ethoxo ligand trans to the Re᎐ ᎐ NPh bond. 1 H NMR indicates that the ethoxo ligand acts as an electron reservoir in these complexes, since its protons are strongly deshielded in the cis-oxo-ethoxo species and strongly shielded in the trans-phenylimido-ethoxo complex.

Polyamide 6,6 is used in many industrial fields such as housing materials, transport or electrical engineering applications. Due to its chemical composition, this polymer is easily flammable. As far as the main applications concern electrical and electronic equipments, its flame-retardant properties become an important requirement. The most discriminating tests are the limiting oxygen index, UL94 and glow wire flammability index. The aim is to obtain high limiting oxygen index values, V0 rating at UL94 test for 1.6- or 0.8-mm-thick samples and a validation at 960°C of the glow wire flammability index. The usual way to fire retard polyamide 6,6 consists of incorporating an important loading of fire-retardant additives, which often reduce the intrinsic properties of the polymer. It is also difficult to combine a thin polymer thickness (e.g. 0.8 mm) and a high amount of additives because of processing issues. In this article, we first carried out a rapid screening to determine the best fire retardant for polyamide 6,6 and its optimized amount to achieve the previously defined fire retardant properties. It was shown that an amount of 23% of aluminium diethylphosphinate Exolit OP1230 allows reaching the requirements. Then, carrying out two different surface treatments (coating of polysiloxanes by plasma-enhanced chemical vapour deposition and use of an intumescent waterborne varnish), we have tried to reach the same results. It was shown that the use of surface treatment alone does not allow reaching the objectives. As a consequence, the combination of the bulk approach at low loadings with the surface treatment was investigated. This new route allows the combination of the condensed phase mechanism of the intumescent barrier with the gas phase mechanism of the OP1230 and leads to very good results: the use of 5% of the flame-retardant additives combined with a 100-µm-thick waterborne intumescent varnish leads to better results than a 23% of additive loading.

No abstract

No abstract