Two model compounds, 3-Phenyl-3,4-dihydro-2H-1,3-benzoxazine (PA) and 6,8-dimethy1-3-(2,4,6-trimethyl-pheny1)-3,4-dihydro-2H-1,3-benzoxazine (s-PA), were successfully synthesized and purificated. Compared with PA, s-PA also catalyzed the polymerization of BADCy even though there was no phenolic hydroxyl in its final ring-opened structures. It was confirmed that the real mechanism of benzoxazine catalyzing the polymerization of cyanate ester is the nucleophilic addition reaction of the oxygen anion on ring-opened benzoxazine to the positively charged carbon atom on cyano group. The catalytic effect also contains the contribution from the phenolic hydroxyl, but it is a secondary factor. (C) 2014 Elsevier B.V. All rights reserved.