Journal of Applied Polymer Science, Vol.66, No.12, 2251-2255, 1997
2-Component Initiator Systems for the Ring-Opening Polymerization of Oligomeric Cyclic Bisphenol-A Carbonates - The in-Situ Cleavage of Disulfides by Triarlyphosphines
A two-component initiator system based on the in situ cleavage of phenyl disulfide by a triarylphosphine has been developed for the ring-opening polymerization of cyclic bisphenol-A (BPA) carbonate oligomers. This development has potential use in composite applications such that the prepolymer can suitably wet the composite material before being converted to high-molecular-weight polymer. The initiator precursors (phenyl disulfide and triphenylphosphine) do not independently initiate significant ring-opening polymerization of the oligomeric cyclic BPA carbonate mixture. A mixture of cyclic BPA carbonate oligomers and one of the initiator components (phenyl disulfide ), combined and heated at 300 degrees C with a mixture of the cyclics and the other initiator component (triphenylphosphine), does produce a high-molecular-weight polymer (M-w = similar to 70,000). The polymerization-initiating species is thought to be thiophenyltriphenylphosphonium thiophenoxide. The effects of concentration of the initiator components, reaction temperature, time, and so forth on polymerization were studied; in general, the degree of polymerization ranged from about 65 to 75%.