Thermomechanical Behavior and Local Dynamics of Dendronized Block Copolymers and Constituent Homopolymers

We employ Brillouin light scattering (BLS) and dielectic spectroscopy (DS) to study the phononic behavior, thermomechanical properties, and segmental dynamics of symmetric block copolymers (BCP) constructed from discrete wedge-type repeat units and the corresponding dendronized constituent homopolymers over a broad temperature range. In spite of the sufficiently large elastic contrast between the bulk homopolymers, for the BCPs an absence of a bandgap in the phonon dispersion relation along the periodicity direction implies different modified sound velocities in the photonic BCP lamellar films. The anticipated rich segmental dynamics reveal interfacial mixing as well as confinement effects of the two blocks. This class of amorphous dendronized homopolymers and BCPs reveal strong effects of the wedge-like side groups manifested in the vastly different glass transition temperatures (T_g), free-volume domination of the temperature dependence of the elastic modulus, and heterogeneous segmental dynamics represented by four relaxation processes

Proton NMR Relaxation Study on the Nematic–Nematic Phase Transition in A131 Liquid Crystal

A study of the proton NMR spin–lattice relaxation time, <i>T</i>₁, of the A131 liquid crystal compound as a function of temperature and Larmor frequency, using a combination of fast field-cycling and standard NMR techniques, is presented. The frequency dispersion in a wide range (from 10 kHz to 300 MHz) at different temperatures and the temperature variation of <i>T</i>₁, in several frequency conditions, were analyzed considering the contributions of the molecular movements generally detected in liquid crystals. In the case of nematic phases of calamitic liquid crystals, the nuclear spin relaxation is dominated by collective movements and local molecular reorientations. The experimental results clearly show a transition within the nematic range of this compound, previously identified as one from the uniaxial to the biaxial phase. This transition can be associated with a slowing down of the molecular rotations around the long molecular axis, where the preferred orientation defines the principal director as detected in the <i>T</i>₁ dispersion analysis

Prompt HO 2

The secondary formation of HO(2) radicals following OH + aromatic hydrocarbon reactions in synthetic air under normal pressure and temperature was investigated in the absence of NO after pulsed production of OH radicals. OH and HO(x) (=OH + HO(2)) decay curves were recorded using laser-induced fluorescence after gas-expansion. The prompt HO(2) yields (HO(2) formed without preceding NO reactions) were determined by comparison to results obtained with CO as a reference compound. This approach was recently introduced and applied to the OH + benzene reaction and was extended here for a number of monocyclic aromatic hydrocarbons. The measured HO(2) formation yields are as follows: toluene, 0.42 ± 0.11; ethylbenzene, 0.53 ± 0.10; o-xylene, 0.41 ± 0.08; m-xylene, 0.27 ± 0.06; p-xylene, 0.40 ± 0.09; 1,2,3-trimethylbenzene, 0.31 ± 0.06; 1,2,4-trimethylbenzene, 0.37 ± 0.09; 1,3,5-trimethylbenzene, 0.29 ± 0.08; hexamethylbenzene, 0.32 ± 0.08; phenol, 0.89 ± 0.29; o-cresol, 0.87 ± 0.29; 2,5-dimethylphenol, 0.72 ± 0.12; 2,4,6-trimethylphenol, 0.45 ± 0.13. For the alkylbenzenes HO(2) is the proposed coproduct of phenols, epoxides, and possibly oxepins formed in secondary reactions with O(2). In most product studies the only quantified coproducts were phenols whereas only a few studies reported yields of epoxides. Oxepins have not been observed so far. Together with the yields of phenols from other studies, the HO(2) yields determined in this work set an upper limit to the combined yields of epoxides and oxepins that was found to be significant (≤0.3) for all investigated alkylbenzenes except m-xylene. For the hydroxybenzenes the currently proposed HO(2) coproducts are dihydroxybenzenes. For phenol and o-cresol the determined HO(2) yields are matching the previously reported dihydroxybenzene yields, indicating that these are the only HO(2) forming reaction channels. For 2,5-dimethylphenol and 2,4,6-trimethylphenol no complementary product studies are available