Co-Polymerization of Maleimides and Vinyl Ethers: A Structural Study

We report on the thermally-induced and photoinduced polymerization of the electron-donating divinyl ether di(4-vinyloxybutyl)succinate (DVBS) and the electron accepting 1,5-bis(maleimido)-2-methylpentane (BMMP) and their monofunctional analogues, dodecylvinyl ether (DDVE), N -methylmaleimide (NMM), and N -phenylmaleimide (NPM). We focus on the stoichiometry of the monomer constituents consumed in the polymerization and the structural identity and bonding configuration(s) of the polymer products. For both BMMP−DVBS and NMM−DDVE, FTIR and 1 H NMR data indicate 1:1 stoichiometry for the resulting polymer. For both systems, the polymers are of the alternating donor and acceptor form (DA) n . This result holds for both photoinduced and thermally induced reactions. Structural NMR studies of polymers synthesized from both mono- and difunctional monomers indicate the presence of both cis and trans conformers of the acceptor at the D−A bond. This finding indicates that thermodynamic factors alone are not sufficient to explain the ratio of the conformers and either steric factors or features specific to the transition state play a significant role in determining the conformational distribution of the polymer.