Sequence Control from Mixtures: Switchable Polymerization Catalysis and Future Materials Applications

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(27), С. 10021 - 10040

Опубликована: Июнь 30, 2021

There is an ever-increasing demand for higher-performing polymeric materials counterbalanced by the need sustainability throughout life cycle. Copolymers comprising ester, carbonate, or ether linkages could fulfill some of this as their monomer–polymer chemistry closer to equilibrium, facilitating (bio)degradation and recycling; many monomers are be sourced from renewables waste. Here, efficient broadly applicable route make such copolymers discussed, a form switchable polymerization catalysis which exploits single catalyst, switched between different catalytic cycles, prepare block sequence selective monomer mixtures. This perspective presents principles catalysis, catalyst design criteria, selectivity structural copolymer characterization tools, properties resulting copolymers. Uses thermoplastic elastomers, toughened plastics, adhesives, self-assembled nanostructures, programmed degradation, among others, discussed. The state-of-the-art research into both products, well future challenges directions, presented.

Язык: Английский

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Heterocycle/Heteroallene Ring‐Opening Copolymerization: Selective Catalysis Delivering Alternating Copolymers

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(1)

Опубликована: Май 20, 2021

Heteroatom-containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer-polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, self-assembled nanostructures. Their current future applications span packaging, house-hold goods, clothing, automotive components, electronics, optical materials, sensors, medical products. An interesting route to these is the catalysed ring-opening copolymerisation (ROCOP) of heterocycles heteroallenes. It a living polymerization, occurs with high atom economy, creates precise, new polymer structures inaccessible by traditional methods. In last decade there has been renaissance in research increasing examples commercial products made using ROCOP. better known production polycarbonates polyesters, but also powerful make N-, S-, other heteroatom-containing polymers, including polyamides, polycarbamates, polythioesters. This Review presents an overview different catalysts, monomer combinations, classes that can be accessed heterocycle/heteroallene

Язык: Английский

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Alkyl borane-mediated metal-free ring-opening (co)polymerizations of oxygenated monomers

Progress in Polymer Science, Год журнала: 2022, Номер 136, С. 101644 - 101644

Опубликована: Дек. 30, 2022

Язык: Английский

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Organoboron-mediated polymerizations

Chemical Society Reviews, Год журнала: 2024, Номер 53(7), С. 3384 - 3456

Опубликована: Янв. 1, 2024

The scientific community has witnessed extensive developments and applications of organoboron compounds as synthetic elements metal-free catalysts for the construction small molecules, macromolecules, functional materials over last two decades. This review highlights achievements organoboron-mediated polymerizations in past several decades alongside mechanisms underlying these transformations from standpoint polymerization mode. Emphasis is placed on free radical polymerization, Lewis pair ionic (cationic anionic) polyhomologation. Herein, alkylborane/O

Язык: Английский

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Self-Switchable Polymerization: A Smart Approach to Sequence-Controlled Degradable Copolymers

Macromolecules, Год журнала: 2022, Номер 55(6), С. 1879 - 1893

Опубликована: Март 11, 2022

In the quest for sustainable development, degradable polymers are attractive alternatives to traditional fossil-based plastics. As monocomponent often suffer from unsatisfactory performances, utilization of corresponding copolymers with tailored block compositions is viable improved properties. To this end, emerging field self-switchable polymerization offers a facile access on-demand synthesis controlled sequences, in which polymerizations were regulated by monomers themselves. This Perspective outlines state-of-the-art systems based on ring-opening (co)polymerization various types monomers. The scope catalysts and monomer summarized. Comprehensive comparison between different offered along an outlook possible future.

Язык: Английский

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Borane catalysis for epoxide (co)polymerization

Polymer Chemistry, Год журнала: 2023, Номер 14(16), С. 1834 - 1862

Опубликована: Янв. 1, 2023

This review discusses the impact of borane catalysis on epoxide homo- and copolymerization, focussing polymerization mechanisms catalyst design.

Язык: Английский

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A novel polyurethane-polydimethylsiloxane/polylactic acid electrospinning fiber membrane for oil/water separation

Colloids and Surfaces A Physicochemical and Engineering Aspects, Год журнала: 2023, Номер 668, С. 131445 - 131445

Опубликована: Апрель 11, 2023

Язык: Английский

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Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Дек. 8, 2021

Abstract The synthesis of well-defined block copolymers from a mixture monomers without additional actions (“one-pot/one-step”) is an ideal and industrially valuable method. In addition, the presence controlled alternating sequences in one or both blocks increases structural diversity polymeric materials, but, at same time, synthetic difficulty. Here we show that “one-pot/one-step” ring-opening terpolymerization three ( N -sulfonyl aziridines; cyclic anhydrides epoxides), with tert -butylimino-tris(dimethylamino)phosphorene t -BuP 1 ) as catalyst, results perfect diblock dialternating terpolymers having sharp junction between two blocks, highly-controllable molecular weights narrow weight distributions Ð < 1.08). organocatalyst switches distinct polymerization cycles any external stimulus, showing high monomer selectivity kinetic control. proposed mechanism based on NMR, in-situ FTIR, SEC, MALDI-ToF, reactivity ratios, kinetics studies.

Язык: Английский

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Mechanistic mapping of (CS2/CO2)/epoxide copolymerization catalysis leads to terpolymers with improved degradability

Cell Reports Physical Science, Год журнала: 2023, Номер 4(8), С. 101510 - 101510

Опубликована: Июль 21, 2023

The placement of main-group functionalities within polymers represents a strategy to access wide catalog materials but is limited by poor understanding the catalyst selection criteria and polymerization mechanism when moving down periodic table. Here, we study series new heterobimetallic carbon dioxide disulfide/epoxide copolymerization catalysts that allow for comparative mechanistic two ring-opening processes. We reveal distinct roles each metal plays are preserved from disulfide, maintaining activity selectivity across copolymerizations. Experimental computational studies show can be understood as structurally related insertion events interlinked central oxygen/sulfur scrambling reaction at propagating chain end. This facilitates synthesis dioxide-/carbon disulfide-/epoxide-derived terpolymers with improved degradability over parent dioxide/epoxide copolymers low levels sulfur incorporation.

Язык: Английский

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Influence of catalase encapsulation on Cobalt@Nanoporous carbon with multiwall shell for supercapacitor and polyurethane synthesis using carbon dioxide

Chemical Engineering Journal, Год журнала: 2022, Номер 453, С. 139874 - 139874

Опубликована: Окт. 20, 2022

Язык: Английский

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