Work

Isospecific Polymerization of 1-Phenyl-1,3-butadiene and Its Copolymerization with Terpene-Derived Monomers

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The transition from fossil-based materials to biobased alternatives has become a critical research focus, particularly in the polymer sector, due to environmental concerns such as rising CO 2 levels and microplastic pollution. This work explores the stereospecific polymerization of 1-phenyl-1,3-butadiene (1PB), a bioderived monomer from cinnamaldehyde, using a titanium [OSSO]-type catalyst activated by MAO. The polymerization exhibited high 3,4-regioselectivity and isotacticity ( mmmm > 99%) with a maximum yield of 65% at 80 °C. Post-polymerization hydrogenation reduced the glass transition temperature ( T g ) from ≈80 °C to ≈17 °C, highlighting the impact of double bond removal on polymer flexibility. Additionally, copolymerizations of 1PB with natural terpenes β-ocimene (O) and S -4-isopropenyl-1-vinyl-1-cyclohexene (IVC) were conducted, yielding multiblock copolymers PPBO and PPBI, respectively, with tunable thermal properties. These copolymers showed partial cross-linking reactions and consequent presence of two glass transition temperatures ( T g ). For PPBO copolymers, the low T g values tended to significantly decrease as the terpene content increased, whereas for the PPBI copolymers, the low T g values showed minimal changes due to the similar T g of their homopolymers. These findings demonstrate the potential of renewable monomers for producing sustainable polymers.

Source: Macromolecules

DOI: 10.1021/acs.macromol.5c00849