Synthese von organophosphorsubstituierten silanen und polysiloxanen

Abstract

ZUSAMMENFASSUNG:Durch Addition von sekundiiren Phosphinen, PhosphinsuEden bzw. Phosphinoxyden an Alkenylsilane, Alkenylalkoxy-, Alkenylchlorsilane oder Polyalkenylpolysiloxane unter UV-Bestrahlung wurden neue organophosphorsubstituierte Silane und Polysiloxane synthetisiert.Aus den zwei hydrolysierbare Gruppen enthaltenden Organophosphinylsilanen werden durch Hydrolyse die entsprechenden Organophosphinylpolysiloxane erhalten. Letztere konnen auch durch Addition von sekundiiren Phosphinen, Phosphinsulfiden bzw. Phosphinoxyden an Polyalkenylpolysiloxane dargestellt werden.Die Verbindungen mit 3-wertigem Phosphor konnen mit Schwefel bzw. Oxydationsmitteln in die entsprechende Phosphinsulfide bzw. -oxyde iibergefiihrt werden. SUMMARY:A method is described by which organophosphorus-substituted silanes and polysiloxanes can be prepared. The method is based on the addition of secondary phosphines, phosphine sulphides or phosphine oxides to alkenyl silanes, alkenyl alkoxysilanes, alkenyl chlorosilanes or polyalkenyl polysiloxanes under the irradiation by ultraviolet light. Fifteen new compounds were synthesised.The organophosphinyl silanes containing hydrolysable groups are converted by hydrolysis to form the corresponding organophosphinyl polysiloxanes. The latter compounds can also be prepared by addition of secondary phosphines, phosphine sulphides or phosphine oxides to polyalkenyl polysiloxanes.Compounds containing three-valent phosphorus can be converted with sulphur or oxidants to the corresponding phosphine sulphides or phosphine oxides.Mit dem Ziel, zu phosphorhaltigen Polysiloxanen zu gelangen l ) , wurde zunachst eine Reihe neuer monomerer phosphororganischer Siliziumverbindungen2) synthetisiert. uber diese und einige erste Polymere sol1 nachstehend berichtet werden.Von Phosphor enthaltenden Polysiloxanen ist gegenuber den normalen Polydimethylsiloxanen Verbesserung einiger Eigenschaften zu erwarten.

Formation and Structure of Porous Gel Networks from Si(OMe)4 in the Presence of A(CH2)nSi(OR)3 (A = Functional Group)

“…The trialkoxysilanes of the type A(CH 2 ) n Si(OR) 3 employed in the present work are shown in Scheme . 2-Phosphinoethyl(trimethoxy)silane and 3-carbamatopropyl(trimethoxy)silane were prepared according to the methods described by Niebergall and Berger . Tetramethoxysilane (TMOS), the silane A(CH 2 ) n Si(OR) 3 (R‘Si(OR) 3 ), and methanol were mixed in a flask.…”

Tetraphenyldiphosphine disulphide (tetraphenyl-1,2-dithioxodi-λ5-phosphane), Ph2P(S)P(S)Ph2

“…Tetraphenyldiphosphine disulphide was prepared as colourless square prismatic, almost cubic, crystals from the reaction of tetraphenyldiphosphine with sulphur under reflux in dry, oxygen-free toluene (Kuchen & Buchwald, 1958;Niebergall & Langenfeld, 1962). Preliminary cell constants were obtained from precession and de Jong-Bouman photographs taken about the long axis of a single crystal.…”

Organofunctional silica aerogels

“…Diphenylphosphinoethyltrimethoxysilane (PhPTMO) was prepared analogous to the method reported by Niebergall by radical addition of diphenylphosphine to vinyltrimethoxysilane [11].…”