4-(4-Carboxyphenyl)-3,5-dioxo-1,2,4-triazolidin-1-yl moieties resulting from 4-(3,5-dioxo-1,2,4-triazolin-4-yl)benzoic acid (U4A) randomly attached to 1,4-polybutadiene form supramolecular aggregates which act as effective junction zones in new thermoplastic elastomers. Deuteron nuclear magnetic resonance (2H NMR) spectroscopy was used to investigate the molecular dynamics of the polymer backbone and the junction zones in selectively labelled samples. The spectra show motional heterogeneity along the polymer chain as well as in the supramolecular domains. Polybutadiene segments which are adjacent to these polar clusters are restricted in their mobility, even at temperatures 100 K above the …

Supramolecular structures based on 4-(3,5-dioxo-1,2,4-triazolidin-4-yl) benzoic acid (U4A) units act as effective junction zones in functionalized polybutadienes, resulting in the formation of thermoplastic elastomers. The dynamics on a molecular scale of the phenyl rings have been probed by 2H-NMR. In the polymeric system, there are three spatially separated environments, which are reflected in the mobility of the polar units. Phenyl rings which are incorporated in the structures are either rigid or undergo 180° phenyl flips. The small fraction of free functional groups move isotropically and their mobility is coupled to the dynamics of the polybutadiene matrix. In two model compounds, whe…

2H NMR studies of phase behaviour and molecular motions of doped discotic liquid-crystalline systems

Abstract A discotic triphenylene monomer as well as a dimer and a main chain polymer, all substituted with heptyloxy side groups, were doped with an electron acceptor (2,4,7-trinitrofluorenone (TNF)) to give charge transfer complexes. These doped systems were aligned in a magnetic field, thus proving their liquid crystallinity. 2H NMR measurements show that the electron acceptor molecules are incorporated into the columns built of triphenylene cores. In the charge transfer complex with the triphenylene monomer almost all the electron acceptor molecules stack in the columns even close to the clearing temperature T 1, while for the dimer and especially for the polymer a significant fraction o…

Etude de deux systemes differents avec de l'hydroxy-4 benzoate de phenyle comme unite mesogene. Les separateurs sont formes de 6 unites methylene et le squelette est de l'acide poly(meth)acrylique