Catalytic Installation of Primary Amines Onto Polyolefins for Oligomer Valorization

Polymerization of primary amine-containing monomers is challenging because the amine inhibits polymerization catalyst activity. An alternative approach to access primary amine functionalized polymers is postpolymerization modification. To this end, the hydroaminoalkylation of vinyl-terminated polyolefins with N-(trimethylsilyl)benzylamine is used to prepare primary amine-terminated polyolefins, with the free primary amine substituent being revealed upon hydrolytic work up. These materials are spectroscopically characterized, and an investigation of thermal properties by differential scanning calorimetry and thermogravimetric analysis is completed. These results show that the primary amine substituent increases the glass transition temperature and improves thermal stability. The reactive primary amine functionality is used in the photo-oxidative dimerization of polyolefins to demonstrate how this elusive functionality can be applied in oligomer valorization.