Dramatically Accelerating II−I Crystal Phase Transition of Polybutene‑1 by in Situ Incorporation of H‐Shape Long‐Chain‐Branching Structures

This communication reports an effective strategy helping address the long-troubling melt processing issue of isotactic polybutene-1 (i-PB) caused by its extremely slow II-I crystal phase transition. The solution lies in a facile synthesis of i-PB containing H-shape long-chain-branching structures (LCB-i-PB) by applying a so-called ω-alkenylmethyldichlorosilane copolymerization-hydrolysis (ACH) chemistry to butene-1 polymerization with Ziegler-Natta or metallocene catalysts. It is evident that the H-shape LCB structures effectively enhance chain entanglements of i-PB and induce an over-the-board acceleration of the overall melt crystallization process including nucleation, form II crystallization, and form II-form I phase transition. As i-PB usually requires up to a week to reach equilibrium of the II-I phase transition, it is found that with LCB-i-PB such a transition is almost finished within as short as 24 h to even higher degrees.