Despite the development of new catalysts and synthetic strategies to prepare polyolefin elastomers (POEs), less progress has been made in balancing their elastomeric properties with processability and resistance to heat and solvents.
The mutual effects of long-chain branch and ionic functional groups on polybutene-1 (PB-1) phase transition from tetragonal form II into hexagonal form I of polybutene-1 were investigated using differential scanning calorimetry and various thermal protocols. The novel butene-1/11-iodo-1-undecene (PB-IUD) copolymer was synthesized to incorporate the long-chain branches, and its iodine groups were reacted as the active sites to introduce ionic functional groups with BF 4 − , Tf 2 N − , and PF 6 − counterions. To the best of our knowledge, this is the first work to introduce physical ionic bonding into polybutene-1 (PB-1) ionomers and explore the affected phase transition. The results show that compared with the linear homopolymer, the long-chain branch largely retards the II−I phase transition of the PB-IUD copolymer. Unexpectedly, after introducing the ionic functional groups, ionomers have significantly accelerated transition with respect to reference PB-IUD, although they have exactly the same branching densities. This II−I phase transition of the ionomer can even happen at the crystallization temperature, where there is actually no cooling step to provide internal thermal stress. This indicates that additional crystallization-associated internal stress may be generated in ionomers for triggering form I nucleation. Moreover, the correlations of transition kinetics with annealing and crystallization temperatures were explored in depth. Ionomer phase transition can happen in a broad temperature range, which covers from the glass-transition temperature to high temperatures close to the melting region. Utilizing a stepwise annealing protocol, it was found that this broad transition temperature window originates from the persistent nucleation ability at elevated temperatures. On the other hand, ionomer transition kinetics increases with decreasing crystallization temperature, which, however, is opposite to that of the homopolymer. Based on this, a continuous cooling protocol was proposed and verified capable of endowing the branched ionomers with transition faster than the homopolymer.
Macromolecules with unique long-chain architecture can not only crystallize into a thermodynamically stable crystal but also form a kinetically favored crystal, where the latter may subsequently transform into the former to further lower the free energy. Therefore, to obtain the thermodynamically stable crystal, there are in principle two distinct formation pathways including the direct crystallization from the amorphous melt and the indirect phase transition from the initially generated modification, of which both are crucial to the crystal polymorphism. In the present work, a series of butene/pentene copolymers with the broad co-unit range of 4.0−36.1 mol % were synthesized to explore the correlation of crystal polymorphism with the molecular factor and external stimuli employing in situ wide-angle X-ray diffraction. The results show that different from the highly isotactic homopolymer, the incorporation of pentene co-units is able to not only induce the formations of both the thermodynamically stable trigonal phase and the kinetically favored tetragonal phase from the amorphous melt but also accelerate their solid II-I phase transition. As the concentration of pentene co-units reaches 17.6 mol % and higher, the thermodynamically stable phase has two distinct formation pathways, where those trigonal crystallites obtained from the direct melt crystallization and the indirect phase transition were referred to as forms I′ and I, respectively. It is also unexpected to find that different from the quiescent case where cooling is required to generate the thermal stress for triggering form I nucleation, both pathways can occur at the same temperature with the crystallization of the kinetically favored tetragonal phase, which can be facilitated by the increase in pentene incorporation. The elevation of temperature is beneficial to the formation of form I′, while the decrease in temperature facilitates the solid II-I phase transition into form I. Furthermore, flow-induced formation of the trigonal phase was also investigated by examining the correlation between the formation pathways and flow strength. It is interesting to find that the relatively weak flow accelerates the crystallization of both forms II and I′, while the severe flow induces the amorphous melt to completely crystallize into tetragonal crystallites and simultaneously trigger them to quickly transform into the ultimately stable form I.
Flow-induced crystallization of poly(vinylidene fluoride) (PVDF) was investigated for a broad temperature range from 160 to 220 °C by in situ synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS). Unexpectedly, the electroactive β-phase is obtained directly from the melt with an extensional flow at 160–200 °C, which is in contrary to the quiescent crystallization of generating the pure α-phase. For 220 °C, the observation of an equatorial SAXS streak without WAXD signals indicates the generation of fibrillar shish. Second, within the isothermal process after flow, the evolution of the flow-induced structure exhibits a strong temperature dependence. The generated β-phase triggers subsequent crystallite growth at 160–180 °C. However, at 190–220 °C, flow-induced fibrillar shish relaxes partially. Third, cooling triggers the crystallization of the α-phase, which competes with the β-phase to determine the final phase constitute. This work reveals the detailed formation and evolution processes of the flow-induced β-phase, which provides an effective approach to obtain the electroactive PVDF materials.
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