Abstract
The present investigation involves the coordinative chain transfer polymerization (CCTP) of biobased terpenes in order to obtain sustainable polymers from myrcene (My) and farnesene (Fa), using the ternary Ziegler-Natta catalyst system comprising [NdV(3)]/[Al(i-Bu)(2)H]/[Me(2)SiCl(2)] and Al(i-Bu)(2)H, which acts as cocatalyst and chain transfer agent (CTA). The polymers were produced with a yield above 85% according to the monomeric consumption at the end of the reaction, and the kinetic examination revealed that the catalyst system proceeded with a reversible chain transfer mechanism in the presence of 15-30 equiv. of CTA. The resulting polyterpenes showed narrow molecular weight distributions (M(w)/M(n) = 1.4-2.5) and a high percent of 1,4-cis microstructure in the presence of 1 equiv. of Me(2)SiCl(2), having control of the molecular weight distribution in Ziegler-Natta catalytic systems that maintain a high generation of 1,4-cis microstructure.