NEW ELASTOMERIC MATERIALS FROM BIOMASS: STEREOSELECTIVE POLYMERIZATION OF LINEAR TERPENES AND THEIR COPOLYMERIZATION WITH BUTADIENE BY USING A COBALT COMPLEX WITH PHOSPHANE LIGANDS

ABSTRACT The polymerization of bio-renewable terpenes such as β-ocimene (O), β-myrcene (M), and β-farnesene (F) promoted by CoCl2(PCyPh2)2 (1) in combination with modified methylalumoxane at room temperature is reported. Stereoregular polymers of O, M, and F were obtained. 1 also promoted, showing good stereoselectivity, the copolymerization of O and M with butadiene (B) in a wide range of compositions by suitably varying the alimentation feed: up to 67 and 75 mol% of O and M incorporated for poly(ocimene-butadiene) and poly(myrcene-butadiene) copolymers, respectively. These new materials with elastomeric properties (glass transition temperatures observed in the range of −5.7 to −72.5 °C) were fully characterized by differential scanning calorimetry, size exclusion chromatography, and nuclear magnetic resonance spectroscopy (1H, 13C, and two-dimensional experiments).

“Arm-first” approach for the synthesis of star-shaped stereoregular polymers through living coordination polymerization

Stereoregular star polymers were synthesized through an “arm-first” approach via a living coordination polymerization mechanism for the first time using a half-sandwich scandium catalyst system.