Relationship between the stereospecificity of lanthanide catalysts and thestructures of active sites and dienes, the nature of a cocatalyst, and preparation conditions
Yb. Monakov et al., Relationship between the stereospecificity of lanthanide catalysts and thestructures of active sites and dienes, the nature of a cocatalyst, and preparation conditions, KINET CATAL, 42(3), 2001, pp. 310-316
Several types of active sites can be formed during the polymerization of di
enes in the presence of lanthanide catalytic systems. These sites differ in
the nearest environment of a lanthanide atom (the numbers of chlorine and
carbon atoms) and in the number of lanthanide-carbon bonds involved in chai
n growth. Quantum-chemical calculation shows that the Is-allyl binding of t
he terminal unit of a growing polymeric chain with the lanthanide atom of a
n active site may be the reason for the cis-stereospecificity of the site.
Therefore, the active sites containing electron-acceptor chlorine atoms tha
t favor pi -allyl binding can form cis-polydienes. Depending on the conditi
ons of catalytic system preparation, primarily on the nature of an organic
compound of a nontransition metal, one or another set of active sites is fo
rmed that can affect its stereospecificity. The quantitative analysis of ki
netic data for diene polymerization shows that the anti-syn isomerization o
f terminal units of growing polymeric chains made a certain contribution to
the formation of trans-1,4 units in the presence of cis-regulating active
sites.