Reinhard Jira

Synthesis of polyarenemethines, a new class of conducting polymers

Abstract Two synthetic routes to form black insoluble and infusable polymers containing polyarenemethine structures are described. The highest conductivity obtained by doping with iodine was 10 −4 S/cm. Syntheses and structures are discussed.

Neuartige basische liganden für die homogenkatalytische methanolcarbonylierung: Teil XX. kinetische untersuchungen der methanolcarbonylierung zu acetaldehyd unter verwendung eines ether-phosphan-modifizierten cobaltkatalysators

Abstract Methanol is hydrocarbonylated to acetaldehyde by means of a catalytic system consisting of CoI2 and [C4H7O2-CH2- P(Ph)-CH2-]2, (C4H7O2 = 1,4-dioxanyl) with synthesis gas. The rate of this reaction in terms of the decrease of the molar fraction of methanol can be expressed by the following equation: The activation energy and the standard activation entropy are 48 kJ mol−1 and −216 J mol−1 K−1, respectively. Whereas excess ligand (CoI2/ ligand = 1 2 ) and admixture of water results in a drastic decrease in the reaction rate, addition of iodide in the form of LiI has no effect on it. The conversions reach approximately 90%. For the industrial application of this process in a continuously working plant, converions of 20 – 30% would be advantageous. In this latter range the selectivities with respect to acetaldehyde including its dimethylacetal (‘total aldehyde’) are higher than 80%. At 270 bar, MeOH/ligand/CoI2 = 800/1/1 and 190 °C, a space-time yield of 6.1 kg of total aldehyde per m3 of MeOH per minute is achieved.