Synthesis of monoazacrown ether containing styrene derivatives and monoazacrown ether end‐capped 3‐(or 4‐)vinyl substituted styrene oligomers and polymers

Abstract

AbstractMonoazacrown ether containing styrene derivatives and monoazacrown ether end‐capped 3‐(or 4‐)vinyl substituted styrene oligomers and polymers were synthesized using 1,4,7,10,13‐pentaoxa‐16‐azacyclooctadecane (1a). N‐Lithio‐1,4,7,10,13‐pentaoxa‐16‐azacyclooctadecane (1b) reacts with styrene to form a 1:1 adduct, N‐phenethyl‐1,4,7,10,13‐pentaoxa‐16‐azacyclooctadecane (4). The reactivity of 1b toward styrene, however, is lower than that of other lithium dialkylamides such a lithium diethylamide. 1b reacts also with divinylbenzene to form a 1:1 adduct, N‐(4‐vinylphenethyl)‐1,4,7,10,13‐pentaoxa‐16‐azacyclooctadecane (7), in non‐polar media. The reactivity of 1b toward divinylbenzene is much higher than toward styrene. The yield of the 1:1 adduct 7 was found to attain more than 70% in cyclohexane. In polar media, however, 1b induced a prompt polymerization of divinylbenzene to form a soluble polymer, each molecule of which was found to have one crown ether unit at the end of the polymer chain and a pendant vinyl group on each monomeric unit.