Synthesis and radical polymerization of vinyl monomers having oxazolidone moiety

Abstract

AbstractOxazolidone group‐containing vinyl monomers, 4‐(2‐oxo‐3‐oxazolidinyl)methylstyrene (OS) and 4‐[2‐(2‐oxo‐3‐oxazolidinyl)ethoxy]methylstyrene (OES), were synthesized and their polymerization and copolymerization behaviors with styrene (St), p‐methoxystyrene (PMS), and m‐hydroxystyrene (MHS) were investigated. OS was prepared in 70% yield by the reaction of 2‐oxazolidone with p‐chloromethylstyrene in the presence of sodium hydride. OES was obtained by the similar reaction of p‐chloromethylstyrene with N‐hydroxyethyl‐2‐oxazolidone which was prepared by the reaction of 2‐oxazolidone with ethylenecarbonate. Homopolymerization of OS and OES afforded mainly gelled polymers, but also soluble polymers on high dilution. In the copolymerization with styrene derivatives, an alternating nature was suggested from the copolymerization parameters obtained by either the nonlinear least‐squares analysis method or the Fineman–Ross method. The alternating copolymerizability decreased in the following order: MHS > PMS > St. Q−e values of OS and OES were calculated and demonstrated that OS and OES behaved as stronger electron‐accepting monomers in the copolymerization with MHS than in those with St and PMS. The copolymerization behavior of OS (OES) with MHS was compared with those of 4‐(2‐oxo‐1‐pyrrolidinyl)methylstyrene (PS) and 4‐[2‐(2‐oxo‐1‐pyrrolidinyl)ethoxy]methylstyrene (PES). From an IR study examining the shift of carbonyl absorption by addition of MHS, the interaction which contributed to the increase of the alternating copolymerizability in the copolymerization of OS (OES) with MHS was concluded to be based on hydrogen bonding. © 1993 John Wiley & Sons, Inc.