Thermal Analysis of Crystallization and Phase Transition in Novel Polyethylene Glycol Grafted Butene-1 Copolymers

Copolymerization is an effective strategy to regulate the molecular structure and tune crystalline structures. In this work, novel butene-1 copolymers with different polyethylene glycol (PEG) grafts (number-average molecular weight M_n = 750, 2000, and 4000 g/mol) were synthesized, for the first time introducing long-chain grafts to the polybutene-1 main chain. For these PEG-grafted copolymers, crystallization, melting, and phase transition behaviors were explored using differential scanning calorimetry. With respect to the linear homopolymer, the incorporation of a trimethylsilyl group decreases the cooling crystallization temperature (T_c), whereas the presence of the long PEG grafts unexpectedly elevates T_c. For isothermal crystallization, a critical temperature was found at 70 °C, below which all polyethylene glycol-grafted butene-1 (PB-PEG) copolymers have faster crystallization kinetics than polybutene-1 (PB). The subsequent melting process shows that for the identical crystallization temperature, generated PB-PEG crystallites always have lower melting temperatures than that of PB. Moreover, the II-I phase transition behavior of copolymers is also dependent on the length of PEG grafts. When form II, obtained from isothermal crystallization at 60 °C, was annealed at 25 °C, PB-PEG-750, with the shortest PEG grafts of M_n = 750 g/mol, could have the faster transition rate than PB. However, PB-PEG-750 exhibits a negative correlation between transition rate and crystallization temperature. Differently, in PB-PEG copolymers with PEG grafts M_n = 2000 and 4000 g/mol, transition rates rise with elevating crystallization temperature, which is similar with homopolymer PB. Therefore, the grafting of the PEG side chain provides the available method to tune phase transition without sacrificing crystallization capability in butene-1 copolymers.