MACROMOLECULAR CAVITIES OF CONTROLLED SIZE .1. SYNTHESIS OF MACROTRICYCLIC POLY(CHLOROETHYL VINYL ETHER)S BY LIVING CATIONIC POLYMERIZATION

The preparation of macrotricyclic poly(vinyl ether)s of controlled molar masses and MWD is described. The procedure consists of the synthesis in a first step of a three-arm star-shaped poly(vinyl ether) from a diheterohexafunctional precursor by living cationic polymerization. The cyclization of each star arm is then achieved under highly diluted conditions by the promoted intramolecular addition of the active end groups onto the three remaining head functions. High cyclization yields are obtained without the detectable formation of polycondensates resulting from intermolecular reaction. A series of head functional star-shaped and macrotricyclic poly(chloroethyl vinyl ether)s of various molecular weights was prepared and characterized. The effect of the cyclization on the apparent molar mass and on the glass transition temperature of the macromolecules has been examined by GPC and DSC, respectively. These derivatives can be considered as the first elements of a new family of macromolecules with potential host-guest properties.