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The influence of charge‐transfer complexes on the copolymerization behavior of cyclic maleic acid derivatives with donor monomers
Author(s) -
SchmidtNaake Gudrun,
Drache Marco,
Leonhardt Katja
Publication year - 1998
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/(sici)1521-3935(19980301)199:3<353::aid-macp353>3.0.co;2-f
Subject(s) - copolymer , monomer , maleic anhydride , polymer chemistry , acrylonitrile , chemistry , acceptor , polymer , materials science , organic chemistry , physics , condensed matter physics
The acceptor monomers maleic anhydride (MSA), itaconic anhydride (ISA), N ‐phenylmaleimide (NPI) and N ‐cyclohexylmaleimide (CMI) were combined with the donor monomers styrene (ST), butyl vinyl ether (BV) and N ‐vinyl‐2‐pyrrolidone (NVP) and studied by means of UV spectroscopy using CT bands. In this manner, the 1:1 stoichiometry of the CT complexes, the equilibrium constant in the range of 20°C to 60°C, and the thermodynamic equilibrium data were determined. Additionally, Monte‐Carlo simulations of the donor‐acceptor combinations in the presence of solvent molecules were run. The cohesion energies calculated from these simulations were used to quantify the donor‐acceptor interactions and showed good agreement with the UV spectral data. The acceptor strength decreases in the order MSA > NPI > ISA > CMI, the donor strength in the order of NVP > ST > BV. In the free radical solution copolymerization of the systems NVP/NPI, BV/NPI, acrylonitrile (AN) AN/CMI, AN/NPI, MSA/CMI and MSA/NPI, the reaction rate and molecular weight dependence on the monomer combination, as well as the r ‐values were determined. Using the K c ‐values, conclusions were drawn concerning the different reaction mechanisms. The properties of the polymers were investigated using differential scanning calorimetry (DSC) and thermogravimetry.