Vinyl Ether Monomers and Polymers

Abstract The history of vinyl ether homopolymers has been more involved with the progress of polymer science than in the generation of highly successful commercial products. The reason appears to be economic, as less‐expensive monomers such as acrylic and vinyl ester types have dominated end‐use polymer technologies. Copolymers of methyl vinyl ether, especially with maleic anhydride, continue to be important in personal care and pharmaceutical markets. The polymerization of vinyl ethers, because of the strong electron‐donating oxygen, can be readily accomplished with cationic initiators to produce polymers and copolymers having the potential for significant variety. Only poly(methyl vinyl ether), however, achieved commercial success among the homopolymers, though its commercial importance has faded. Divinyl ethers are emerging as important ingredients in radiation‐cured coatings because they are more insensitive than acrylates to atmospheric oxygen present during cationic polymerization. Copolymers based on methyl vinyl ether/maleic anhydride, easily prepared by free‐radical initiation, continue to hold academic interest. The observation in 1949 that isobutyl vinyl ether can be polymerized with stereoregularity ushered in the stereochemical study of polymers, eventually leading to the development of stereoregular polypropylene. In fact, vinyl ethers were key monomers in the early polymer literature. Academic interest in living cationic polymerization and in the unusual compatibility of poly(methyl vinyl ether) with polystyrene continue to demonstrate that vinyl ether‐containing polymers are still valuable for contemporary interest.