Mechanically Adaptive Polymers Constructed from Dynamic Coordination Equilibria.

Designing materials capable of adapting their mechanical properties in response to external stimuli is the key to preventing failure and extending their service life. However, existing mechanically adaptive polymers are hindered by limitations such as inadequate load-bearing capacity, difficulty in achieving reversible changes, high cost, and a lack of multiple responsiveness. Herein, we address these challenges using dynamic coordination bonds. A new type of mechanically adaptive material with both rate- and temperature-responsiveness was developed. Owing to the stimuli-responsiveness of the coordination equilibria, the prepared polymers, PBMBD-Fe and PBMBD-Co, exhibit mechanically adaptive properties, including temperature-sensitive strength modulation and rate-dependent impact hardening. Benefitting from the dynamic nature of the coordination bonds, the polymers exhibited impressive energy dissipation, damping capacity (loss factors of 1.15 and 2.09 at 1.0 Hz), self-healing, and 3D printing abilities, offering durable and customizable impact resistance and protective performance. The development of impact-resistant materials with comprehensive properties has potential applications in the sustainable and intelligent protection fields.

Directly Using Paraffin as the Toughening Agent of Epoxy Composites: An Experimental and Molecular Dynamics Simulation Study.

It is still a challenge in studying the toughening mechanism by well combining the experimental and atomistic molecular dynamics (MD) simulation study. This article directly introduced eicosane (C20, model compound of paraffin) into the epoxy matrix (DGEBA) by using a special epoxy resin with alkyl side chains (D12) as a compatibilizer, which was synthesized through thiol-ene click chemistry. The toughening mechanism of the ternary DGEBA/D12/C20 (EPDA-X) systems was systematically investigated by experimental and MD simulation methods. Though C20 can be well dispersed in the curing mixture, the huge polarity difference between C20 and DGEBA can be the driving force for C20 to stay away from DGEBA, demonstrating the self-assembly effect of C20 around the alkyl side chains of D12 because of the good compatibility of D12 and C20. The soft alkyl chains of D12 and C20 as well as the self-assembly effect of C20 around the D12 molecules can simultaneously improve the strength, modulus, and toughness of the EPDA-2.5 system. This article not only provides a brand new toughening strategy by directly using nonfunctional alkyl derivatives as the toughening agent of epoxy composites with superior mechanical properties but also provides a systematic MD simulation method to evaluate whether there is the interaction or not and the strength of interaction between different molecular chains so as to provide a theoretical basis for the cause of the microphase separation structure and related toughening mechanism in cross-linking networks on the atomic and molecular levels.

Base-mediated carboxylation of C-nucleophiles with CO2.

Carbon dioxide (CO2) is an available, abundant, and renewable C1 resource, which could be converted into value-added chemicals. Due to its inherent thermodynamic stability and kinetic inertness, it is difficult to realize its efficient utilization. Nevertheless, many elegant strategies for the utilization of CO2 have been developed using Lewis bases, frustrated Lewis pairs, hydroxyl-containing compounds, amino-group-containing compounds or transition metal catalysis. Among them, base-mediated carboxylation of C-nucleophiles is an environmentally friendly strategy for CO2 conversion, which is operationally simple, using low-toxicity bases and economical available promoters, without the use of complex ligands or cocatalysts. This review summarizes related work on the base-mediated carboxylation of C-nucleophiles with CO2, based on the effects of nucleophiles, promoters, additives, and solvents. The types of pronucleophile are categorized as follows: hydrocarbon with C(sp3)-H, C(sp2)-H or C(sp)-H bonds, organosilanes, organotin, organoboron, and N-tosylhydrazones. Typical mechanisms and applications of these carboxylation reactions are also depicted. Moreover, mechanistic comprehension of CO2 activation and conversion at a molecular level aims to further expand the repertoire of carboxylation transformations mediated by bases.

Machine-learning-assisted molecular design of phenylnaphthylamine-type antioxidants.

In this study, a total of 302 molecular structures of phenylnaphthylamine antioxidants based on N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine skeletons with various substituents were modeled by exhaustive methods. Antioxidant parameters, including the hydrogen dissociation energy, solubility parameter, and binding energy, were calculated through molecular simulations. Then, a group decomposition scheme was determined to decompose 302 antioxidants. The antioxidant parameters and decomposition results constituted machine-learning data sets. Using an artificial neural network model, a correlation coefficient between the predicted and true values above 0.88 and an average relative error within 6% were achieved. Random forest models were used to analyze the factors affecting antioxidant activity from chemical and physical perspectives; the results showed that amino and alkyl groups were conducive to improving antioxidant performance. Moreover, substituent positions 1, 7, and 10 of N-phenyl-1-naphthylamine and 3, 7, and 10 of N-phenyl-2-naphthylamine were found to be the optimal positions for modifications to improve antioxidant activity. Two potentially efficient phenylnaphthylamine antioxidant structures were proposed and their antioxidant parameters were also calculated; the hydrogen dissociation energy and solubility parameter decreased by more than 9% and 7%, respectively, whereas the binding energy increased by more than 16% compared with the benchmark of N-phenyl-1-naphthylamine. These results indicate that molecular simulation and machine learning could provide alternative tools for the molecular design of new antioxidants.

A combined experimental and molecular dynamics simulation study of an intrinsic self-healing polyurethane elastomer based on a dynamic non-covalent mechanism.

An intrinsic self-healing polyurethane (PU) elastomer with excellent self-healing efficiency was prepared. The self-healing properties of this elastomer as well as the temperature dependence of self-healing can be tailored by regulating the molar ratio of hard to soft segments. The self-healing efficiency of 92.5% is the highest when the molar ratio of 4,4-methylenedicyclohexyl diisocyanate (HMDI) to polypropylene carbonate polyol (PPC) is 1.3 and the temperature is 25 °C. In situ temperature swing infrared spectra and low-field nuclear magnetic resonance reveal that the soft segment, PPC, endows PU with a dense dynamic hydrogen bond network, and the dissociation and reconstruction of the hydrogen bond network enable the PU to heal. To date, the exchange of hydrogen bonds has not been observed intuitively through experimental means. Therefore, the number, type, strength, lifetime, and the exchange of hydrogen bonds in the self-healing process at different temperatures were investigated by molecular dynamics (MD) simulation. The simulated results show that the type of hydrogen bond exchange between functional groups will be affected by temperature. The hydrogen bonds between urethane and urea groups play a leading role in the self-healing properties due to the high strength and a large number of hydrogen bonds at both 25 and 50 °C. The stronger strength, longer lifetime, and greater number of effective hydrogen bonds at 25 °C make the self-healing efficiency of PU higher than at 50 °C.

Molecular Dynamics Simulation Study on Two-Component Solubility Parameters of Carbon Nanotubes and Precisely Tailoring the Thermodynamic Compatibility between Carbon Nanotubes and Polymers.

Solubility parameters play an important role in predicting compatibility between components. The current study on solubility parameters of carbon materials (graphene, carbon nanotubes, and fullerene, etc.) is unsatisfactory and stagnant due to experimental limitations, especially the lack of a quantitative relationship between functional groups and solubility parameters. Fundamental understanding of the high-performance nanocomposites obtained by carbon material modification is scarce. Therefore, in the past, the trial and error method was often used for the modification of carbon materials, and no theory has been formed to guide the experiment. In this work, the effect of defects, size, and the number of walls on the Hildebrand solubility parameter (δT) of carbon nanotubes (CNTs) was investigated by molecular dynamics (MD) simulation. Besides, three-component Hansen solubility parameters (δD, δp, δH) were transformed into two-component solubility parameters (δvdW, δelec). The quantitative relation between functional groups and two-component solubility parameters of single-walled carbon nanotubes (SWCNTs) was then given. An important finding is that the δT and δvdW of SWCNTs first decrease, reach a minimum, and then increase with increasing grafting ratio. The thermodynamic compatibility between functionalized SWCNTs and six typical polymers was investigated by the Flory-Huggins mixing model. Two-component solubility parameters were proven to be able to effectively predict their compatibility. Importantly, we theoretically gave the optimum grafting ratio at which the compatibility between functionalized SWCNTs and polymers is the best. The functionalization principle of SWCNTs toward good compatibility between SWCNTs and polymers was also given. This study gives a new insight into the solubility parameters of functionalized SWCNTs and provides theoretical guidance for the preparation of high-performance SWCNTs/polymers composites.

Alkyl lithium-catalyzed benzylic C-H bond addition of alkyl pyridines to α-alkenes.

Brønsted base catalyzed C-C bond formation reactions have been extensively utilized as reliable, efficient, and atom economical methods in organic synthesis. However, the electrophiles were mostly limited to polar ones such as imines, carbonyl compounds, α,ß-unsaturated compounds, styrenes and conjugated dienes. The use of α-alkenes as electrophiles in the C-C bond formation reactions always needs transition metal catalysts. Herein, we reported an alkyl lithium-catalyzed benzylic C-H bond addition of alkyl pyridines to α-alkenes. The alkyl lithium catalyst displayed quite different selectivity from those of transition metal catalysts.

Molecular dynamics simulation insight into the temperature dependence and healing mechanism of an intrinsic self-healing polyurethane elastomer.

An intrinsic self-healing polyurethane (PU) elastomer was synthesized in our previous work. In this work, three-dimensional (3D) micro-crack models based on experimental samples were further introduced to investigate their self-healing behavior, mechanism, and temperature dependence by molecular dynamics (MD) simulations. In particular, the number, type, strength, and lifetime of hydrogen bonds as well as the microscopic behavior of molecular diffusion in the self-healing process were investigated. It was found that the self-healing capacity of PU mainly results from intermolecular electrostatic interactions, and the hydrogen bond plays a key role in electrostatic interactions. There is an optimum ratio of soft and hard segments at which the number of hydrogen bonds is appropriate and the self-healing capacity is optimum. Besides, the temperature has an optimal value at which the self-healing rate of PU is the fastest. The exchanges of hydrogen bonds, which endowed PU with self-healing capacity, were further revealed intuitively. We found that the exchanges of hydrogen bonds are reversible and more likely to occur on the urethane groups. This study deepened the understanding of the self-healing character of PU at the molecular level.

Numerical Simulation of Flow Characteristics for Supercritical CO2-Sprayed Polyurethane Resin.

Conventional paint spraying processes often use small molecule organic solvents and emit a large amount of volatile organic compounds (VOCs) that are highly toxic, flammable, and explosive. Alternatively, the spraying technology using supercritical CO2 (scCO2) as a solvent has attracted attention because of its ability to reduce VOC emissions, but the flow characteristics of coatings have not been thoroughly studied. Therefore, we numerically simulate the spraying process based on the actual process of scCO2 spraying polyurethane coatings by computational fluid dynamics (CFD). The effects of inlet pressure and volume fraction of scCO2 on the fluid motion parameters inside the nozzle as well as the atomization effect of droplets outside the nozzle are investigated. The simulated results show that a fluid with a large volume fraction of scCO2 will obtain a smaller density, resulting in a larger velocity and a larger distance for the spray to effectively spray. Higher coating content and bigger inlet pressures will result in higher discrete phase model (DPM) concentrations, and thus a bigger inlet pressure should be used to make the droplets more uniform across the 30° spray range. This study can provide theoretical guidance for the process of scCO2-sprayed polyurethane resin.

Mechanically Robust, Durable, and Multifunctional Hyper-Crosslinked Elastomer Based on Metal-Organic-Cluster Crosslinker: The Role of Topological Structure.

Polymer materials formed by conventional metal-ligand bonds have very low branch functionality, the crosslinker of such polymer usually consists of 2-4 polymer chains and a single metal ion. Thus, these materials are weak, soft, humidity-sensitive, and unable to withstand their shape under long-term service. In this work, a new hyperbranched metal-organic cluster (MOC) crosslinker containing up to 16 vinyl groups is prepared by a straightforward coordination reaction. Compared with the current typical synthesis of metal-organic cages (MOCs) or metal-organic-polyhedra (MOP) crosslinkers with complex operations and low yield, the preparation of the MOC is simple and gram-scale. Thus, MOC can serve as a high-connectivity crosslinker to construct hyper-crosslinked polymer networks. The as-prepared elastomer exhibits mechanical robustness, creep-resistance, and humidity-stability. Besides, the elastomer possesses self-healing and recyclability at mild condition as well as fluorescence stability. These impressive comprehensive properties are proven to originate from the hyper-crosslinked topological structure and microphase-separated morphology. The MOC-driven hyper-crosslinked elastomers provide a new solution for the construction of mechanically robust, durable, and multifunctional polymers.

Stretchable, Ultratough, and Intrinsically Self-Extinguishing Elastomers with Desirable Recyclability.

Advanced elastomers are increasingly used in emerging areas, for example, flexible electronics and devices, and these real-world applications often require elastomers to be stretchable, tough and fire safe. However, to date there are few successes in achieving such a performance portfolio due to their different governing mechanisms. Herein, a stretchable, supertough, and self-extinguishing polyurethane elastomers by introducing dynamic π-π stacking motifs and phosphorus-containing moieties are reported. The resultant elastomer shows a large break strain of ≈2260% and a record-high toughness (ca. 460 MJ m-3 ), which arises from its dynamic microphase-separated microstructure resulting in increased entropic elasticity, and strain-hardening at large strains. The elastomer also exhibits a self-extinguishing ability thanks to the presence of both phosphorus-containing units and π-π stacking interactions. Its promising applications as a reliable yet recyclable substrate for strain sensors are demonstrated. The work will help to expedite next-generation sustainable advanced elastomers for flexible electronics and devices applications.

Direct alkylation of N,N-dialkyl benzamides with methyl sulfides under transition metal-free conditions.

Amides are a fundamental and widespread functional group, and are usually considered as poor electrophiles owing to resonance stabilization of the amide bond. Various approaches have been developed to address challenges in amide transformations. Nonetheless, most methods use activated amides, organometallic reagents or transition metal catalysts. Here, we report the direct alkylation of N,N-dialkyl benzamides with methyl sulfides promoted by the readily available base LDA (lithium diisopropylamide). This approach successfully achieves an efficient and selective synthesis of α-sulfenylated ketones without using transition-metal catalysts or organometallic reagents. Preliminary mechanism studies reveal that the deprotonative aroylation of methyl sulfides is promoted by the directed ortho-lithiation of the tertiary benzamide with LDA.

New Insights into the Quantitative Relationship between Surface Chemistry of Fullerene (C60) and Solubility Parameters and Compatibility with Polymers.

The quantitative relationship between the surface chemistry of carbon materials and the compatibility with polymers is a fundamental and vital physical chemistry problem in the field of polymer nanocomposites. Traditional experimental methods are difficult to solve this problem, so no theory has been formed to guide the functionalization of carbon materials. In this work, the quantitative relationship between functional groups and Hildebrand (δT) and transformed Hansen (δvdW and δele) solubility parameters of fullerene (C60) was determined by molecular dynamics simulation. Besides, which solubility parameter can more accurately predict the compatibility between C60 and three typical polymers with different polarity as a function of grafting ratio is investigated. Very interestingly, no matter which group is grafted, δT and δvdW of C60 show a slight increase first and then a decrease with the grafting ratio, whereas δele first increases abruptly and then decreases slightly. The introduction of polar groups (-OH, -COOH, and -NH2) is conducive to improving the compatibility between C60 and polymers, whereas the introduction of the nonpolar group (-CH3) is not. In terms of predicting compatibility, the Hildebrand solubility parameter is better than the Hansen solubility parameter due to the nonpolar nature of the polymers, even for nitrile butadiene rubber. Finally, the optimum grafting ratios corresponding to the maximum binding energies of C60/polymers mixtures were obtained. This study provides a new understanding of the functionalization of C60 at the molecular level and promotes the development of the theory of the thermodynamics of mixing.

Catalyst-Free Metathesis of Cyclic Acetals and Spirocyclic Acetal Covalent Adaptable Networks.

Due to the exchangeability of dynamic covalent bonds in the covalent adaptable networks (CANs) at elevated temperature, they possess recyclability while still maintaining many of the superior properties of thermosets. The exploration of dynamic covalent chemistry is of great significance to the expansion of CANs library and hence the sustainable development of thermosets. In this work, we discovered that, in absence of catalyst, the direct metathesis of the cyclic acetals proceeds while the acyclic acetals cannot. The metathesis kinetics of the cyclic acetals were fully revealed with model compounds. For the CANs demonstration, a series of cross-linked spirocyclic acetal polymers with excellent reprocessability, high thermal stability, and high refractivity were prepared via thiol-ene click polymerization. We envisage that the uncovering of the catalyst-free metathesis of cyclic acetals will enrich the dynamic chemistry of acetals and greatly promote the development of acetal-based CANs and their potential applications in optical devices.

Highly Efficient, Environmentally Friendly Lignin-Based Flame Retardant Used in Epoxy Resin.

We prepared novel flame retardants with concurrent excellent smoke-suppression properties based on lignin biomass modified by functional groups containing N and P. Each lignin-based flame retardant (Lig) was quantitatively added to a fixed amount of epoxy resin (EP), to make a Lig/EP composite. The best flame retardancy was achieved by a Lig-F/EP composite with elevated P content, achieving a V-0 rating of the UL-94 test and exhibiting excellent smoke suppression, with substantial reduction of total heat release and smoke production (by 46.6 and 53%, respectively). In this work, we characterized the flame retardants and the retardant/EP composites, evaluated their performances, and proposed the mechanisms of flame retardancy and smoke suppression. The charring layer of the combustion residual was analyzed using SEM and Raman spectroscopy to support the proposed mechanisms. Our work provides a feasible method for lignin modification and applications of new lignin-based flame retardants.

Temperature dependence of the interfacial bonding characteristics of silica/styrene butadiene rubber composites: a molecular dynamics simulation study.

Based on our previous studies on the modification of in-chain styrene butadiene rubber (SBR) using 3-mercaptopropionic acid as well as its composites filled with silica, we further constructed two types of models (amorphous and layered) to investigate the temperature dependence of the interfacial bonding characteristics of silica/SBR composites via molecular dynamics (MD) simulation. The competing effects of rubber-rubber interactions and filler-rubber interactions were identified, and the relationship between the competing effects and the temperature was determined. Besides this, the effect of temperature on the mobility and distribution of SBR chains on the surface of silica was investigated. It was found that the stronger the interfacial interactions, the less sensitive the motion of SBR chains to temperature. Finally, the number and length of hydrogen bonds as a function of temperature were analyzed. These simulated results deepened the understanding of interface temperature dependence of the silica/SBR composites and gave a molecular level explanation for the existence of an optimum modifier content (14.2 wt%) that is temperature independent.

Understanding Mechanism of Adsorption in the Decolorization of Aqueous Methyl Violet (6B) Solution by Okra Polysaccharides: Experiment and Theory.

Optimal conditions for ultrasonic-assisted extraction of polysaccharide from Chinese okra were found using response surface methodology. The okra polysaccharide (OPS) was used for the adsorption of methyl violet 6B (MV). Conditions for maximal adsorption efficiency of MV were established. The mechanism of MV adsorption was investigated by the characterization and physicochemical analysis of OPS before and after the adsorption of MV. Both infrared (IR) analysis and molecular dynamics (MD) simulation suggest that MV adsorption by OPS was an electrostatic interaction between MV and oxygen-containing groups of OPS. Further, the results of first-principles calculation were in agreement with IR spectroscopy measurements and MD simulation, which were all consistent with the suggested adsorption mechanism. Optimization of okra extraction conditions, maximized efficiency of MV adsorption by OPS, and the understanding of the adsorption mechanism are the highlights of this work, providing a reference for promising applications of OPS in the treatment of wastewater in textile, paper, and other industries.