Comparison of electron spin resonance probe and dielectric relaxation in physically and chemically crosslinked polymers

Dielectric relaxation spectroscopy in the frequency range from 10⁻² Hz to 10⁶ Hz and electron spin resonance (ESR) experiments are employed to study the dynamics in chemically and physically crosslinked networks. As examples for physically crosslinked networks ortho- and para-cresol novolacs were investigated. Dielectrically these materials show low-temperature β- and high-temperature α-relaxation. Both relaxation regions differ for both types of novolacs. This is also reflected by the ESR measurements and is discussed in terms of different hydrogen bonds found to be stronger in para-cresol novolac. For the chemically crosslinked poly(triallyl isocyanurate) only a β-peak is found by the dielectric measurements. Also in the ESR experiment the slow motion regime is characterized up to high temperatures. This means that the segmental motion is strongly suppressed by chemical crosslinking. Nevertheless the obtained change in the formal T_50G value can be used to characterize the glass transition in highly crosslinked systems by the ESR method.     

Ultrahigh molecular weight alternating propene/ethene/carbon monoxide terpolymers with elastic properties

Soluble propene/ethene/CO terpolymers (EPEC) with ultrahigh molecular weight (up to 1.2 × 10⁶ g/mol) were prepared by the use of dicationic palladium(II) phosphine catalysts and an optimized amount of water as activator. When the molar ratio of ethene/CO to propene/CO is below 50 mol-%, the terpolymers are thermoplastic elastomers with excellent properties. Above this ratio the terpolymers are crystalline thermoplastics. The ultrahigh molecular weight elastomers are highly soluble in organic solvents such as CH₂Cl₂ and CHCl₃.     

(Diazoalkyl)Phosphoranes from [4 + 1]-cycloadditions of tetrahalo-orthobenzoquinones to (diazoalkyl)phosphanes [1]

The (diazoalkyl)phosphanes 4a–e undergo [4 + 1]-cycloaddition reactions with the tetrahalo-orthobenzoquinones 5a,b to furnish the previously unknown (diazoalkyl)phosphoranes 6a–h . The structure of product 6h has been investigated by X-ray crystallography.