Premium
Synthesis and cationic ring‐opening polymerization of 2‐methylene‐7‐oxabicyclo[2.2.1]heptane
Author(s) -
Bai Ruke,
Li Shihua,
Zou Yinfang,
Pan Caiyuan,
Uryu Toshiyuki
Publication year - 1994
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.1994.021950109
Subject(s) - cationic polymerization , polymer chemistry , chemistry , polymerization , ring opening polymerization , monomer , polymer , methylene , heptane , organic chemistry
A new unsaturated bicyclic ether, 2‐methylene‐7‐oxabicyclo[2.2.1]heptane ( 4 ) was synthesized by successive Diels‐Alder addition of furan to acrylonitrile, hydrogenation of cyano compound 5 , and Hofmann degradation of the quaternary ammonium hydrate 7 derived from the amine 6 . Cationic polymerization of the monomer 4 was carried out in CH 2 Cl 2 using BF 3 · OEt 2 , PF 5 , SbCl 5 and SnCl 4 as catalysts in the temperature range of −20 to −25°C. White or slightly yellow powdery polymers of low molecular weight were obtained with PF 5 and BF 3 · OEt 2 as catalysts, while no polymer was obtained with SbCl 5 and SnCl 4 as initiators. The IR, 1 H and 13 C NMR spectra of the polymers indicated that they consist of three kinds of repeating units, that is, two unsaturated units caused by ring‐opening polymerization and one addition unit. Using proton NMR data of the polymers, the distribution of repeating units was calculated. A polymerization mechanism is proposed. The thermal stability of the obtained polymers is discussed.