Stereospecificity in the cationic co‐ordinated polymerization of methoxystyrenes

Investigations were performed in order to establish whether the “modified FRIEDEL‐CRAFTS catalysts”, which are stereospecific in the cationic co‐ordinated polymerizations of the vinyl and alkenyl ethers, are stereospecific also when the ether oxygen is not directly bound to the vinyl double bond. For this purpose the polymerization of ortho, meta and para‐methoxy styrenes were studied. Whereas the meta methoxy styrene does not polymerize due to the unfavorable influence of the substituent upon the π‐electrons of the vinyl group, the ortho and para isomers furnish amorphous polymers. By hydrogenating the phenyl groups of the poly ortho methoxy styrene to crystalline poly ortho methoxy vinyl cyclohexane it has been proved that the polymerization of the ortho methoxy styrene is stereospecific and that the mechanism is cationic co‐ordinated.