The Effect of Carbon Dioxide on the Alkali-Metal Initiation of Polyisoprene

Abstract

Abstract The structures of polymers formed when alkali metals are placed in the vapor phase above isoprene monomer, both in the presence and absence of carbon dioxide, were investigated. In the absence of carbon dioxide, the polymers were all gel-like and soluble. In the presence of carbon dioxide, however, insoluble popcorn polymers were formed. The structures of the soluble polymers varied from primarily cis in the case of lithium to trans for sodium and potassium initiation. In the presence of carbon dioxide the three alkali metals produced polymers having similar structures, predominantly trans. In the absence of carbon dioxide most of the polymerization proceeds anionically with the majority of the free radical sites of the initially formed radical anion being removed by a transfer reaction or by dianion formation. The presence of carbon dioxide, however, leads to the formation of car boxy late ions that prevent anionic polymerization. Then, due to the structural orientation of the radical anion on t...