Covalent Polymer Research Articles

Microstructure and interaction in aluminum hydrides@polydopamine composites and interfacial improvement with GAP adhesive.

The reduction of interfacial interaction and the deterioration of processing properties of aluminum hydrides (AlH3) is the main challenges preventing its practical application. Here, a simple and effective core-shell structure aluminum hydrides@polydopamine (AlH3@PDA) complex was constructed through in-situ polymerization. The evolution of element states on the surface of AlH3 conducted by X-ray photoelectron spectroscopy indicated the successful introduction of PDA to form the core@shell structure, the thickness of the PDA coated layer increased with the increasing PDA dosage from 0.1 to 1.6% in mass fraction, and the maximum of thickness is 50nm in TEM testing. Py GC/MS results proved that the increase of dopamine concentration leads to higher proportions of self-assemble units, whereas lower dopamine concentrations favor higher levels of chemical bonded components. Regarding whether PDA is a covalent polymer or a noncovalent aggregate of some species, the formation of intermediates, such as dopaminechrome and 5,6-dihydroxyindole played an important role to coordination interaction with AlH3 in FTIR, Raman, and UV-Vis spectra testing. Compared with pure AlH3, the formation of organic PDA coating improved AlH3 heat resistance. The adhesion work with GAP adhesive was also improved from 107.02J/m2 of pure AlH3 to 111.13mJ/m2 of AlH3@PDA-5 complex. This paper provides well support for further practical application of AlH3 in solid propellants.

Dynamic Covalent Amphiphilic Polymer Conetworks Based on End-Linked Pluronic F108: Preparation, Characterization, and Evaluation as Matrices for Gel Polymer Electrolytes.

We present the development of a platform of well-defined, dynamic covalent amphiphilic polymer conetworks (APCN) based on an α,ω-dibenzaldehyde end-functionalized linear amphiphilic poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol) (PEG-b-PPG-b-PEG, Pluronic) copolymer end-linked with a triacylhydrazide oligo(ethylene glycol) triarmed star cross-linker. The developed APCNs were characterized in terms of their rheological (increase in the storage modulus by a factor of 2 with increase in temperature from 10 to 50 °C), self-healing, self-assembling, and mechanical properties and evaluated as a matrix for gel polymer electrolytes (GPEs) in both the stretched and unstretched states. Our results show that water-loaded APCNs almost completely self-mend, self-organize at room temperature into a body-centered cubic structure with long-range order exhibiting an aggregation number of around 80, and display an exceptional room temperature stretchability of ∼2400%. Furthermore, ionic liquid-loaded APCNs could serve as gel polymer electrolytes (GPEs), displaying a substantial ion conductivity in the unstretched state, which was gradually reduced upon elongation up to a strain of 4, above which it gradually increased. Finally, it was found that recycled (dissolved and re-formed) ionic liquid-loaded APCNs could be reused as GPEs preserving 50-70% of their original ion conductivity.

Engineering bifunctional sites in covalent polymers for boosting photocatalytic H2S oxidation

The development of catalyst for photocatalytic hydrogen sulfide (H2S) oxidation with excellent efficiency and regeneration properties is a significant challenge. Herein, the pyridine units as bifunctional sites are incorporated in covalent polymers (CPs) by CN coupling reaction, which exhibit photocatalytic H2S selective oxidation to sulfur conversion (95 %) under visible light in a continuous flow system, more than twice that of the pristine sample (40 %). Meanwhile, the photocatalytic H2S conversion rate had a linear function relationship with pyridinic N content, demonstrating the substantial role of pyridine in photocatalytic H2S oxidation process. According to experimental results, the pyridine unit not only acted as the structural base site to improve the H2S chemisorption, but also served as electron withdrawing unit to construct electron donor-acceptor (D-A) structure with benzene, which optimized the light absorption, charge separation and migration. In addition, series in-situ measurements and electron density difference simulations revealed the significant role of electron D-A structure in H2S adsorption and activation process. By exploring the effect of pyridine unit in CPs on H2S conversion process, this work provides a new idea for the subsequent study of photocatalytic H2S oxidation.

Photoswitchable Cascades for Allosteric and Bidirectional Control over Covalent Bonds and Assemblies.

Studies of complex systems and emerging properties to mimic biosystems are at the forefront of chemical research. Dynamic multistep cascades, especially those exhibiting allosteric regulation, are challenging. Herein, we demonstrate a versatile platform of photoswitchable covalent cascades toward remote and bidirectional control of reversible covalent bonds and ensuing assemblies. The relay of a photochromic switch, keto-enol equilibrium, and ring-chain equilibrium allows light-mediated reversible allosteric structural changes. The accompanying distinct reactivity further enables photoswitchable dynamic covalent bonding and release of substrates bidirectionally through alternating two wavelengths of light, essentially realizing light-mediated signaling cycles. The downfall of energy by covalent bond formation/scission upon photochemical reactions offers the driving force for the controlled direction of the cascade. To show the molecular diversity, photoswitchable on-demand assembly/disassembly of covalent polymers, including structurally reconfigurable polymers, was realized. This work achieves photoswitchable allosteric regulation of covalent architectures within dynamic multistep cascades, which has rarely been reported before. The results resemble allosteric control within biological signaling networks and should set the stage for many endeavors, such as dynamic assemblies, molecular motors, responsive polymers, and intelligent materials.

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia.

In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron-hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high-performance photocathode for multi-electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high-throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly-functionalized covalent networks for boosting eight-electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo-accumulating assembly and multi-electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.

Predicting Organometallic Intermediates in the Surface-Assisted Ullmann Coupling of Chrysene Isomers.

On-surface polymerization of functional organic molecules has been recently recognized as a promising route to persistent low-dimensional structures with tailorable properties. In this contribution, using the coarse-grained Monte Carlo simulation method, we study the initial stage of the Ullmann coupling of doubly halogenated chrysene isomers adsorbed on a catalytically active (111) crystalline surface. To that end, we focus on the formation of labile metal-organic precursor structures preceding the covalent bonding of chrysene monomers. Four monomeric chrysene units with differently distributed halogen substituents were probed in the simulations, and the resulting precursor structures were compared and quantified. Moreover, the effect of (pro)chirality of chrysene tectons on the structure formation was elucidated by running separate simulations in enantiopure and racemic systems. The calculations showed that suitable manipulation of the halogen substitution pattern allows for the creation of diverse precursor architectures, ranging from straight and winded chains to cyclic oligomers with enantiopure, racemic, and nonracemic composition. The obtained findings can be helpful in developing synthetic strategies for covalent polymers with predefined architecture and functionality.

Terphenyl Functionalized Covalent Triazine Polymer as Metal‐Free Photocatalyst for Superior Hydrogen Peroxide Production

AbstractArtificial photosynthesis of H2O2 from H2O and O2 by visible light is a promising approach, but the efficiency is still unsatisfactory because of the inefficient O2 adsorption and proton supply. Here, terphenyl functionalized covalent triazine polymer (CTP‐TD) is prepared for efficient H2O2 production. Experimental and theoretical results show that terphenyl structure can promote O2 adsorption by regulating the oxygen evolution (O2→1O2) and improve proton supply by accelerating water oxidation. The terphenyl structure significantly promotes the singlet oxygen (1O2) production via the intersystem crossing (ISC) process. The electrophilic 1O2 is more easily adsorbed on the catalyst surface than O2. Simultaneously, the accumulated holes at the terphenyl structure lower water oxidation energy barriers and accelerate the water dehydrogenation process. This work provides a valuable reference and new inspiration for the polymer design of efficient H2O2 generation from the perspective of reactant supply.

Dynamic Entwined Topology in Helical Covalent Polymers Dictated by Competing Supramolecular Interactions

AbstractNaturally occurring polymeric structures often consist of 1D polymer chains intricately folded and entwined through non‐covalent bonds, adopting precise topologies crucial for their functionality. The exploration of crystalline 1D polymers through dynamic covalent chemistry (DCvC) and supramolecular interactions represents a novel approach for developing crystalline polymers. This study shows that sub‐angstrom differences in the counter‐ion size can lead to various helical covalent polymer (HCP) topologies, including a novel metal‐coordination HCP (m‐HCP) motif. Single‐crystal X‐ray diffraction (SCXRD) analysis of HCP−Na revealed that double helical pairs are formed by sodium ions coordinating to spiroborate linkages to form rectangular pores. The double helices are interpenetrated by the unreacted diols coordinating sodium ions. The reticulation of the m‐HCP structure was demonstrated by the successful synthesis of HCP−K. Finally, ion‐exchange studies were conducted to show the interconversion between HCP structures. This research illustrates how seemingly simple modifications, such as changes in counter‐ion size, can significantly influence the polymer topology and determine which supramolecular interactions dominate the crystal lattice.

Dynamic Entwined Topology in Helical Covalent Polymers Dictated by Competing Supramolecular Interactions.

Naturally occurring polymeric structures often consist of 1D polymer chains intricately folded and entwined through non-covalent bonds, adopting precise topologies crucial for their functionality. The exploration of crystalline 1D polymers through dynamic covalent chemistry (DCvC) and supramolecular interactions represents a novel approach for developing crystalline polymers. This study shows that sub-angstrom differences in the counter-ion size can lead to various helical covalent polymer (HCP) topologies, including a novel metal-coordination HCP (m-HCP) motif. Single-crystal X-ray diffraction (SCXRD) analysis of HCP-Na revealed that double helical pairs are formed by sodium ions coordinating to spiroborate linkages to form rectangular pores. The double helices are interpenetrated by the unreacted diols coordinating sodium ions. The reticulation of the m-HCP structure was demonstrated by the successful synthesis of HCP-K. Finally, ion-exchange studies were conducted to show the interconversion between HCP structures. This research illustrates how seemingly simple modifications, such as changes in counter-ion size, can significantly influence the polymer topology and determine which supramolecular interactions dominate the crystal lattice.

Porous covalent polymer framework-based molecular platform for polychromatic Vis-to-NIR electrochromic smart window to modulate solar irradiation

Employing advanced electrochromic technology, the low energy-consuming smart windows seamlessly regulate light transmission, optimizing energy efficiency without compromising comfort. This innovation marks a significant stride toward sustainable architecture, offering dynamic control over interior luminosity while reducing reliance on conventional power sources. In that context, a porous perylene diimide (PDI) and triazine-containing covalent polymeric framework, PD-CPF, was synthesized for electrochromic (EC) applications. The PD-CPF-based electrochromic device (ECD) exhibited a multicolored, durable visible-to-NIR electrochromism when used in an ECD. The low-power-consuming (3.05 mW/cm2) electrochromic (EC) smart window remarkably lowered the solar irradiance gain by 68%.

Iminoboronate-based chiral dynamic covalent polymer for selective and sensitive fluoride recognition

The construction of chiral polymers using dynamic covalent chemistry is a convenient and straightforward strategy for obtaining functional materials. In this paper, we report the dynamic covalent polymers DCP1, DCP2, and DCP3 with dual dynamic covalent bonds of imine and boronic ester, and their recognition of fluoride ions. The three polymers are prepared from L-DOPA hexyl ester and 2-, 3-, and 4-formylphenylboronic acids, respectively. Iminoboronate, formed within repeated DCP1 units, results in the formation of a spirochiral structure centered at sp3-B and, consequently, the chiral twist or helix conformation of the polymer backbone. DCP1 exhibits distinctive chiroptical features that distinguish it from DCP2 and DCP3. Due to the strong competitive bonding of fluoride with boron, DCP1 has a low LOD (Limit of detection) for fluoride (0.018 mg/L). DCP1 also has good selectivity for fluoride via the responsive destruction of the spirochiral structure and the chiral conformation of the backbone. The construction of these chiral dynamic polymers provides a rapid and effective approach to designing functional polymers.

Investigating Dynamic Changes in 3D‐Printed Covalent Adaptable Polymer Networks

Abstract3D printing technologies have matured to produce complex structures, still they are often limited to static materials. Introducing alkoxyamine bonds into 3D printed structures offers unprecedented possibilities for post‐synthetic modification through nitroxide exchange reaction and nitroxide‐mediated polymerization. This study provides a comprehensive molecular and macroscopic characterization of 3D‐printed alkoxyamine‐containing dynamic covalent adaptable networks. The study provides new insights into their dynamic structural and mechanical alterations, making them promising candidates for advanced applications ranging from biomedical engineering to flexible electronics.

Double polymer networks comprising covalent and hydrogen-bonded cross-links

We report the investigation of rubbery double networks that are based on poly(n-butyl acrylate) (BA) backbones and feature either non-covalent or covalent cross-links. The polymers for the supramolecular network were prepared by reversible addition−fragmentation chain-transfer polymerization of n-butyl acrylate and up to 10 mol% of the self-complementary hydrogen bonding motif 2-ureido-4[1H]pyrimidinone (UPy), which dimerizes into supramolecular cross-links. The covalent polymer network was synthesized by UV-initiated free-radical polymerization of BA and up to 5 mol% of the difunctional cross-linker 1,4-butanediol diacrylate, either separately, or after imbibing films of the supramolecular network with the reaction mixture for the covalent network. The combination of the two network types affords materials that show features of both single networks. The co-existence of a static and a dynamic network affords materials that owe their high thermal stability and creep resistance to the covalent network, and their high extensibility and healability to the supramolecular network.

Hybrid Dynamic Covalent Network-Based Protecting Layer for Stable Li-Metal Batteries.

Metallic lithium (Li) is considered as the "Holy Grail" anode material for next-generation energy storage systems due to its extremely high theoretical capacity and low electrochemical potential. Before the commercialization of the Li electrode, dendritic Li growth and the unstable solid electrolyte interphase layer should be conquered. Herein, a hybrid covalent adaptable polymer network (HCAPN) is prepared via the random copolymerization of poly(ethylene glycol) methyl ether methacrylate and -acetoacetoxyethyl methacrylate, followed by chemical cross-linking with polyethylenimine (PEI) and amine-modified silicon dioxide (SiO2). Such a hybrid network, where PEI and amine-modified SiO2 formed a vinylogous urethane-based dynamic covalent bond with the copolymer, respectively, shows improved mechanical properties, solvent resistance, and excellent healability/recyclability. As the protecting layer on the Li electrode, the assembled HCAPN@Li||HCAPN@Li symmetric cell shows a long cycle life of 800 h with low overpotential at a current density of 1 mA cm-2, and superior electrochemical performance can be achieved in the HCAPN@Li||LiFePO4 full cell (capacity retention of 77% over 400 cycles at 1.5 C) and HCAPN@Li||NCM811 cell (capacity retention of 79% after 300 cycles). Surface morphology analysis is also performed for physical insight into their role as protecting layer. This work provides a new perspective for constructing a hybrid dynamic covalent network-based polymer protecting layer for inhibiting Li dendrite growth.

Inside Cover: Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid‐state Polymerization (Angew. Chem. Int. Ed. 9/2024)

Inside Cover: Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid‐state Polymerization (Angew. Chem. Int. Ed. 9/2024)

Innentitelbild: Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid‐state Polymerization (Angew. Chem. 9/2024)

Innentitelbild: Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid‐state Polymerization (Angew. Chem. 9/2024)

Viscoelasticity and self-healing property of dynamic covalent polymers: A molecular dynamics simulation

In this work, a coarse-grained model of dynamic covalent polymers (DCP) based on dynamic covalent bonds (DCBs) is first constructed. Then, the dynamics of DCBs is characterized by analyzing the time correlation function where lifetime exhibits an Arrhenius dependence on temperature. Following it, the viscoelasticity of DCP is explored by tuning the number of DCBs and temperature. The storage modulus exhibits a significant decrease at the critical shear strain amplitude (γ0) while the loss modulus reaches the maximum value. This is because of the orientation and stretching of chains as a function of the shear strain amplitude. The decrease magnitude in the storage modulus rises with increasing the number of DCBs. This can be understood well by characterizing the number, lifetime, bond length distribution of DCBs, and bond energy per DCBs at the critical γ0. Furthermore, both the storage modulus and loss modulus decrease with increasing the temperature. This is because the number and lifetime of DCBs are reduced with increasing the temperature while the bond energy per DCBs is improved. Interestingly, the maximum loss modulus peak at the critical γ0 gradually disappears with reducing the temperature. Finally, the self-healing process is quantitatively simulated by analyzing the self-healing degree. The relationship between the characteristic self-healing time and the self-healing temperature follows an Arrhenius behavior. In summary, this work presents a new understanding on the effect of DCBs on the viscoelasticity and self-healing property of DCP at the molecular scale.

Accessing pluripotent materials through tempering of dynamic covalent polymer networks.

Pluripotency, which is defined as a system not fixed as to its developmental potentialities, is typically associated with biology and stem cells. Inspired by this concept, we report synthetic polymers that act as a single "pluripotent" feedstock and can be differentiated into a range of materials that exhibit different mechanical properties, from hard and brittle to soft and extensible. To achieve this, we have exploited dynamic covalent networks that contain labile, dynamic thia-Michael bonds, whose extent of bonding can be thermally modulated and retained through tempering, akin to the process used in metallurgy. In addition, we show that the shape memory behavior of these materials can be tailored through tempering and that these materials can be patterned to spatially control mechanical properties.

Vitrimer Nanocomposites for Highly Thermal Conducting Materials with Sustainability.

Vitrimers, as dynamic covalent network polymers, represent a groundbreaking advancement in materials science. They excel in their applications, such as advanced thermal-conductivity composite materials, providing a sustainable alternative to traditional polymers. The incorporation of vitrimers into composite fillers enhances alignment and heat passway broadly, resulting in superior thermal conductivity compared to conventional thermosetting polymers. Their dynamic exchange reactions enable straightforward reprocessing, fostering the easy reuse of damaged composite materials and opening possibilities for recycling both matrix and filler components. We review an overview of the present advancements in utilizing vitrimers for highly thermally conductive composite materials.

Massive Molecular Motion in Crystal Leads to an Unexpected Helical Covalent Polymer in a Solid-state Polymerization.

We designed a proline-derived monomer with azide and alkene functional groups to enable topochemical ene-azide cycloaddition (TEAC) polymerization. In its crystal, the monomer forms supramolecular helices along the 'a' axis through various non-covalent interactions. Along the 'c' axis, the molecules arrange themselves head-to-tail in a wave-like pattern, positioning the azide and alkene groups of adjacent molecules in close proximity and anti-parallel orientation, complying with Schmidt's criteria for topochemical reaction. This prearranged configuration was expected to facilitate smooth topochemical polymerization, resulting in a 1,4-triazoline-linked polymer. Upon heating, the monomer underwent TEAC polymerization in a remarkable single-crystal-to-single-crystal fashion, but, to our surprise, it yielded an unexpected covalent helical polymer linked by 1,5-disubstituted triazoline units. Remarkably, the crystal avoids the ready-to-react arrangement for polymerization, but connects monomer molecules within the supramolecular helix through the cycloaddition of azide and alkene groups, even though they are not in close proximity nor in the expected orientation. This unexpected path, involving a substantial 134° rotation of the alkene group, yields hitherto unknown 1,5-disubstituted triazoline product regiospecifically. This study serves as a cautionary reminder that relying solely on topochemical postulates for predicting reactivity can sometimes be misleading.