Anionic polymerization of aldehydes. V. Block copolymers of formaldehyde with vinyl or diene monomers

Abstract

Abstract Polymerization of formaldehyde with “living polymer” solution was investigated and it was shown that block copolymers of formaldehyde and vinyl or diene monomers such as styrene, α‐methylstyrene, 2‐methyl‐5‐vinylpyridine, butadiene and isoprene can be synthesized. Reactions of polymeric species possessing active alcoholate anions as terminal groups with various reagents were investigated. Successful attempts were made by reacting polymeric species with acetic anhydride in toluene: the thermal stability of the obtained polymers was as good as that of polymers which were acetylated in the conventional way. In order to investigate the mechanism of the initial reaction of the polymerization of formaldehyde, the initial reaction product of formaldehyde with the sodium naphthalene complex was prepared and investigated by means of electronic and infrared spectra. From the fact that the structure of the initial product is considered to be 1,4‐ or 1,2‐ dihydronaphthalene, the initiation of the polymerization seems to be the addition reaction of formaldehyde with sodium naphthalene forming an alcoholate anion, which then is capable of polymerizing formaldehyde to high molecular weight polymer.