CURING REACTIONS IN ACETYLENE-TERMINATED RESINS .4. IR AND NMR-STUDY OF CATALYZED POLYMERIZATION OF ARYL PROP-2-YNYL ETHER-TERMINATED MONOMERS

Partial polymerization of the aryl prop-2-ynyl ether-terminated monomer (pHC=CCH2OC6H4)2CMe2 (1) and complete polymerization of the analogous model monomer pHC=CCH2OC6H4CMe2Ph (2) in the presence of various catalysts afforded soluble polymers, the study of which enabled the effect of catalysts on resin structure to be determined. IR and NMR spectroscopy, in particular the chemical shift of the CH2O protons, showed: (a) (eta-CP)Co(CO)2 gives rise exclusively to acetylene cyclotrimerization; (b) (eta-CP)2Ni and (PPh3)2NiCl2 each result in both cyclotrimerization and non-aromatic polyene formation; (c) (PPh3)3RhCl gives linear polymers with backbone branched enyne groups which act as crosslink sites in further polymerization.