| Abstract: | The spontaneous reactions of 1‐(2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione‐5‐ylidene)‐4‐(dicyanomethylene)‐2,5‐cyclohexadiene (QM‐1) with a vinyl ether, butyl vinyl ether (BVE), and a cyclic ketene acetal, 2‐methylene‐1,3‐dioxepane (MDOP), were investigated. The reaction of QM‐1 with BVE produced a terpolymer composed of QM‐1, 7‐butoxy‐8,8‐dicyanoquinodimethane, and BVE units as a hexane‐insoluble product and a one‐to‐one adduct of methylene Meldrum's acid and BVE as a hexane‐soluble product. The spontaneous reaction of QM‐1 with BVE produced, in the presence of 2,2,6,6‐tetramethylpiperidine‐1‐oxy (TEMPO), a terpolymer carrying TEMPO units in the chain ends, and in the presence of methanol, a one‐to‐one‐to‐one adduct of QM‐1, BVE, and methanol was isolated. The spontaneous reaction with bulkier, electron‐donating MDOP produced a low‐molecular‐weight alternating cooligomer of QM‐1 with MDOP. The spontaneous polymerization was proposed to proceed via a zwitterionic intermediate taking two forms, gauche and trans, depending on the bulkiness of the comonomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3800–3811, 2004 |
