Characterization and polymerization of metal complexes of poly(ethylene glycol) diacrylates and the synthesis of polymeric pseudocrown ethers

Polymeric pseudocrown ether networks were formed in situ by the photopolymerization of poly(ethylene glycol) diacrylate (PEGDA)/transition metal complexes. The metal - monomer complex led to a near circular conformation of the monomer in which the two reactive end groups are brought into close proximity; thus, the probability of intramolecular cyclization (i.e., pseudocrown ether formation) is increased. Complexes of cobalt(II), nickel(II), zinc(II), cadmium(II), chromium(III), copper(II), neodymium(III), and lithium were characterized using FTIR and UV - vis spectroscopy. Metal-monomer interactions were characterized and the importance of coordinated water and anions was elucidated. A novel technique of replacing coordinated waters by monomeric ether oxygens was discovered. Pseudocrown ether network formation was confirmed via a study of the polymerization kinetics of cobalt(II): PEGDA systems in which a decrease in autoacceleration was observed with increasing pseudocrown ether formation.