172422-37-6Relevant articles and documents
Trialkyl phosphites and diaryliodonium salts as co-initiators in a system for radical-promoted visible-light-induced cationic polymerization(1)
Nalli, Thomas W.,Stanek, Lee G.,Molenaar, Rebekka H.,Weidell, Krysia L.,Meyer, Justin P.,Johnson, Brandon R.,Steckler, Timothy T.,Wackerly, Jay Wm.,Studler, Missy Jo,Vickerman, Kevin L.,Klankowski, Stephen A.
, p. 3561 - 3569 (2013/06/04)
Trialkyl phosphites ((RO)3P) can act as co-initiators for the diaryliodonium-induced cationic polymerization of cyclohexene oxide (CHO) or THF. A radical initiation step is also required, consistent with the essential role of a radical chain reaction of the phosphite with the iodonium salt to form polymerization-starting aryltrialkoxyphosphonium salts (ArP+(OR) 3). We used the visible photolysis of phenylazoisobutyronitrile (PAIBN) as the radical initiation step. The presence of multiple fluorine substituents on the phosphite, as in tris(2,2,2-trifluoroethyl) phosphite (TFP), allows polymerization to proceed with a minimal amount of chain transfer from nucleophilic attack by the phosphite. In a typical experiment, a CHO solution of bis(4-tert-butylphenyl)iodonium hexafluorophosphate (0.05 M), TFP (0.1 M), and PAIBN (0.02 M) was illuminated with a 65-W compact fluorescent bulb for 1 h, resulting in a 78% conversion to poly(cyclohexene oxide) with an average molecular weight (MW) of 25000. We also used competition experiments to determine approximate rate constants for reactions of phenyl radicals with CHO (k = 2 × 106 M-1 s-1) and with TFP (k = 2 × 108 M-1 s-1).
CONCERNING THE FORMATION, HYDROLYSIS AND THERMOLYSIS OF ACYCLIC PHOSPHORANES
Lowther, Nicholas,Crook, Polly,Hall, Dennis
, p. 405 - 408 (2007/10/02)
Kinetic data on the formation, hydrolysis and thermolysis of acyclic phosphoranes is reported and the mechanism of each reaction is discussed.
