Control of polymer initiation, propagation and termination is important in the development of complex polymer structures and advanced materials. Typically, this has been achieved chemically, electrochemically, photochemically or mechanochemically. Electrochemical control has been demonstrated in radical polymerizations; however, regulation of a cationic polymerization has yet to be achieved. Through the reversible oxidation of a polymer chain end with an electrochemical mediator, temporal control over polymer chain growth in cationic polymerizations was realized. By subjecting a stable organic nitroxyl radical mediator and chain transfer agent to an oxidizing current, control over polymer molecular weight and dispersity is demonstrated and excellent chain end fidelity allows for the synthesis of block copolymers.
The
development of next-generation materials is coupled with the
ability to predictably and precisely synthesize polymers with well-defined
structures and architectures. In this regard, the discovery of synthetic
strategies that allow on demand control over monomer connectivity
during polymerization would provide access to complex structures in
a modular fashion and remains a grand challenge in polymer chemistry.
In this Article, we report a method where monomer selectivity is controlled
during the polymerization by the application of two orthogonal stimuli.
Specifically, we developed a cationic polymerization where polymer
chain growth is controlled by a chemical stimulus and paired it with
a compatible photocontrolled radical polymerization. By alternating
the application of the chemical and photochemical stimuli the incorporation
of vinyl ethers and acrylates could be dictated by switching between
cationic and radical polymerization mechanisms, respectively. This
enables the synthesis of multiblock copolymers where each block length
is governed by the amount of time a stimulus is applied, and the quantity
of blocks is determined by the number of times the two stimuli are
toggled. This new method allows on demand control over polymer structure
with external influences and highlights the potential for using stimuli-controlled
polymerizations to access novel materials.
Developing cathodes that can support high charge–discharge rates would improve the power density of lithium‐ion batteries. Herein, the development of high‐power cathodes without sacrificing energy density is reported. N,N′‐diphenylphenazine was identified as a promising charge‐storage center by electrochemical studies due to its reversible, fast electron transfer at high potentials. By incorporating the phenazine redox units in a cross‐linked network, a high‐capacity (223 mA h g−1), high‐voltage (3.45 V vs. Li/Li+) cathode material was achieved. Optimized cross‐linked materials are able to deliver reversible capacities as high as 220 mA h g−1 at 120 C with minimal degradation over 1000 cycles. The work presented herein highlights the fast ionic transport and rate capabilities of amorphous organic materials and demonstrates their potential as materials with high energy and power density for next‐generation electrical energy‐storage technologies.
Block polymers, macromolecules consisting of two or more regions of unique monomer composition with complex structures are important materials in the development of new technologies. Multiblock polymers can provide unique physical properties on the basis of monomer choice, block length, and the number of polymer blocks. Traditional approaches for generating multiblock copolymers are often arduous, multistep syntheses. We present a facile method where higherorder multiblock copolymers can be synthesized in situ by interconverting the polymerization mechanism using light and electricity.
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