Synthesis and properties of biomass eugenol-functionalized isotactic poly(1-butene)s

Functional isotactic poly(1-butene) ( i PB) bearing natural antioxidant has been successfully synthesized via the MgCl 2 -supported TiCl 4 Ziegler-Natta catalyst-mediated copolymerization of 1-butene with a renewable eugenol (EG) comonomer. The incorporated EG contents could be conveniently tailored by changing the comonomer loadings and reaction parameters such as temperature, molar ratio of co-catalyst/main catalyst (Ti), and external electron donor loading, up to 0.62 mol% EG units incorporated into i PB chain. Interestingly, the introduction of EG into the 1-butene polymerization are beneficial for improving the molecular weight of resultant copolymers. EG-functionalized i PB demonstrate a higher thermal-oxidative stability with respect to the pristine PB, nearly being proportional to the EG content, whose oxidation induction time (OIT) of i PB containing 0.62 mol% EG units is prolonged by 25 fold than that of i PB without EG units. Nevertheless, the EG counits in the i PB backbone limit the crystallization rate and suppress the Form II -Form I crystal transformation. A novel biomass eugenol-functionalized isotactic poly(1-butene)s with intrinsic thermo-oxidative resistance nature was obtained. The incorporated EG units into PB backbone stabilize the kinetically favored Form II. • Poly(1-butene)-bonded natural antioxidant phenols. • Synthesis of functional poly(1-butene) with high thermo-oxidative stability. • The eugenol comonomers in the copolymerization benefit the improvement of molecular weight of the resulting PB. • The incorporated EG moieties stabilizing the kinetically favored Form II.