A new superbase, the cyclic trimeric phosphazene base (CTPB), was prepared with high yield and purity. In the presence of alcohol, the CTPB serves as a highly efficient organocatalyst for ring-opening polymerization of the "non-polymerizable" γ-butyrolactone to offer well-defined poly(γ-butyrolactone) with high conversions (up to 98 %) at -60 °C. The produced polymers have high molecular weights (up to 22.9 kg mol ) and low polydispersity distributions (1.27-1.50). NMR analysis of initiation process and the structural analysis of resulting polymers by MALDI-TOF suggest a mechanism involving an activating initiator which leads only to linear polymers with BnO/H chain ends.
Phosphazene base
is an important organocatalyst in polymer chemistry
owing to its high activity and versatility. In this contribution,
we demonstrate that cyclic trimeric phosphazene base (CTPB) can catalyze stereoselective ring-opening polymerization (ROP)
of rac-lactide (rac-LA) to produce
isotactic stereoblock PLA (P
i up to 0.93).
The polymerizations are highly controlled, as evidenced by linear
relationship between molecular weights (MW) and monomer conversions
and the narrow dispersity (Đ = M
w/M
n) of the resulted polymers
with high fidelity of end groups. The investigations on polymerization
parameters show that the tacticity of produced PLA depends on the
polymerization temperatures and solvents, while the kinetic studies
reveal a faster rate for ROP of l-LA as compared to rac-LA under same conditions. Based on these results, the
chain end control mechanism is proposed to explain the production
of isotactic stereoblock PLA from rac-LA by an achiral
catalyst.
An ew superbase,t he cyclic trimeric phosphazene base (CTPB), was prepared with high yield and purity.Int he presence of alcohol, the CTPB serves as ah ighly efficient organocatalyst for ring-opening polymerization of the "nonpolymerizable" g-butyrolactone to offer well-defined poly(gbutyrolactone) with high conversions (up to 98 %) at À60 8 8C. The produced polymers have high molecular weights (up to 22.9 kg mol À1 )and low polydispersity distributions (1.27-1.50). NMR analysis of initiation process and the structural analysis of resulting polymers by MALDI-TOF suggest am echanism involving an activating initiator which leads only to linear polymers with BnO/H chain ends.Scheme 1. Synthesis of acyclic trimeric phosphazene base.
The rational synergy of chemical composition and spatial nanostructures of electrode materials play important roles in high‐performance energy storage devices. Here, we designed pea‐like MoS2@NiS1.03–carbon hollow nanofibers using a simple electrospinning and thermal treatment method. The hierarchical hollow nanofiber is composed of a nitrogen‐doped carbon‐coated NiS1.03 tube wall, in which pea‐like uniformly discrete MoS2 nanoparticles are enclosed. As a sodium‐ion battery electrode material, the MoS2@NiS1.03–carbon hollow nanofibers have abundant diphasic heterointerfaces, a conductive network, and appropriate volume variation‐buffering spaces, which can facilitate ion diffusion kinetics, shorten the diffusion path of electrons/ion, and buffer volume expansion during Na+ insertion/extraction. It shows outstanding rate capacity and long‐cycle performance in a sodium‐ion battery. This heterogeneous hollow nanoarchitectures designing enlightens an efficacious strategy to boost the capacity and long‐life stability of sodium storage performance of electrode materials.
TiO2@g-C3N4 core/shell fibers with a continuous g-C3N4 layer packing around exhibit high photocatalytic efficiency toward H2 production and RhB degradation due to the intimate core/shell structure with a high-quality TiO2/g-C3N4 heterojunction.
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