Über einige besonderheiten der polymerisation von 2,3-dimethylbutadien in durch lithiumorganische verbindungen initiierten prozessen

✍ Scribed by Smirnowa, Natalia ;Sgonnik, Vladimir ;Kalninsch, Karl ;Erussalimsky, Boris

• Book ID: 102938214
• Publisher: Wiley (John Wiley & Sons)
• Year: 1977
• Weight: 894 KB
• Volume: 178
• Category: Article
• ISSN: 0025-116X
• DOI: 10.1002/macp.1977.021780315

✦ Synopsis

Abstract

The polymerization of 2,3‐dimethylbutadiene (DMB) induced by butyllithium (BuLi), oligo‐2,3‐dimethylbutadienyllithium (ODMBL), and by the system ODMBL/N,N,N′,N′‐tetramethylethylenediamine (TMD) was investigated in heptane at 60°C. The reaction order with respect to the organolithium compound was found to be for these cases −0,32, 0,28, and 0,56 respectively. The negative reaction order for BuLi is caused by the existence of the mixed associates (BuLi)~x~. (M~n~Li)~y~ which follows from the negative influence of BuLi on the propagation reaction rate in the system DMB/ODMBL. Contrary to butadiene and isoprene, catalytic amounts of TMD decrease the propagation rate of DMB. This phenomenon is ascribed to a weak tendency of the complexes of the DMB‐living chains to dissociate into the monomeric form M~n~Li. TMD. The UV‐ and IR‐spectra of the living DMB‐chains and their complexes with TMD are studied.