Polar Polymers Research Articles

Orthogonal Agent Comprising a Nitrile N-Oxide and a Phenylcarbamate for Facile Molecular Integration on Styrne-Butadiene Resin.

The covalent attachment of poly(ethylene glycol) (PEGylation) to materials minimizes non-specific fouling of the material surface with biocomponents. While the PEGylation reaction on polar surfaces is widely used and regarded as a common technique, the PEGylation on less polar polymers and elastomers is extremely difficult due to the absence of reactive points with PEG terminus. Herein, the design and synthesis of an orthogonal agent with a nitrile N-oxide and a phenyl carbamate that can mediate between an alkene and an amine are reported. The ligation capacity of the orthogonal agent is demonstrated through the model reaction to connect between 1-hexene and 4-methoxybenzylamine and the grafting reaction of PEG onto poly(styrene-co-butadiene) (SB) resin. The surface characteristics of PEGylated SB film are evaluated by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. Because SB resin is frequently used as a 3D-printing polymer, the present study indicates that the orthogonal agent can be applicable to the surface modification of 3D-printed objects precisely manufactured by using a computer-aided design (CAD) file in the future.

Multi-Responsive Polymer Nanoparticles: A Versatile Platform for Double-Security Anticounterfeiting and Smart Food Packaging.

Potential applications of colloidal polymer nanoparticles in the preparation of smart inks are investigated by physical incorporation of the oxazolidine molecules. Precise adjusting the polymer chain flexibility and polarity is achieved by controlling the ratio of methyl methacrylate and butyl acrylate monomers in the polymerization reaction. In addition, nanofibrous indicators of acid-base vapors are prepared from the latex nanoparticles. This can be beneficial for creating materials that sense and respond to environmental changes, such as humidity or moisture and acidity. Thermochromic inks are prepared by microencapsulating crystal violet lactone dye (CVL) in polymer matrices to prevent their release into the aqueous media. Combining two distinct systems with varying triggers, such as light and temperature, provides an effective strategy for double-encryption anticounterfeiting and crack and scratch detection and indication applications. Preparing labels impregnated with double-responsive inks, a novel approach is developed for food spoilage detection and preservation indication. Labels are manufactured using polymer nanoparticles, which contain photoluminescent oxazolidine molecules, as well as a trinary mixture of CVL within core-shell latex particles as the thermochromic dye. The combination of these two responsive elements transforms traditional packaging into a dynamic and interactive sentinel for the food it holds.

Tailoring Polymer Polarity to Regulate Disulfide Accessibility in Redox-Active Particles for Organic Batteries

Tailoring Polymer Polarity to Regulate Disulfide Accessibility in Redox-Active Particles for Organic Batteries

Identifying synthetic variables influencing the reproducible microfluidic synthesis of ZIF nano- and micro-particles

The reproducible synthesis of nano- and -micro particles is a critical step in multiple synthetic and industrial processes. Microfluidic synthesis offers numerous advantages for development of precise, reliable, and industrially useful synthesis protocols. However, the influence of different synthetic variables on reproducibility in microfluidic synthesis is underexplored. In this work, we systematically study the influence of key synthetic parameters on the microfluidic synthesis of four Zeolitic Imidazolate Frameworks (ZIFs): ZIF-7, ZIF-8, ZIF-9, and ZIF-67. Utilizing a coiled tube microfluidic setup, we explore the influence of key synthetic parameters such as reagent concentration, stoichiometry, aging time, and nine modulators (pH-altering agents, surfactants, and polar polymers). Most importantly, we evaluate the impact of these variables in combination with the role of mixing, using the Dean flow model. Lastly, we focus on the reproducibility problems that a coiled reactor presents at specific flowrates and how these problems can be recognized and avoided. Overall, the insights collected from this work inform the design of synthetic protocols and enhance material reproducibility and control in microfluidic nano- and micro-particle synthesis.

Preparation of Self-healing Thermoplastic Polysiloxane-Polyurea/Polyether-Polyurea Elastomer Blends with a Co-continuous Microphase Structure and In-Depth Research on Their Synergistic Effects.

Polymer blending has been an important method to create materials with specific properties that have synergistic effects. However, there are few reports on the mechanism of synergistic effects. It is well known that it is quite difficult to obtain ideal blends composed of nonpolar organosilicon polymers and polar polymers. In this paper, thermoplastic polyurea elastomer blends with a co-continuous microphase structure consisting of polysiloxane-polyurea (PDMS-PUA), polyether amine-polyurea (PEA-PUA), and compatibilizer PDMS-PUA-grafted PEA-PUA (PDMS-PUA-g-PEA-PUA) were prepared for the first time. For the first time, introduction of polysiloxane does not sacrifice mechanical properties of thermoplastic polyurea elastomers. For example, the tensile strength of the elastomer blend with 30 wt % PDMS-PUA content reached 25.7 MPa, which is higher than those of PEA-PUA and PDMS-PUA. The blends also show typical outstanding characters such as exceptional heat and water resistance. The mechanism of the synergistic effect on mechanical properties is revealed based on in-depth studies on mutual interphase interaction. In situ variable temperature infrared spectroscopic analysis (VTIR) shows that compatibilization facilitates the construction of a denser hydrogen bonding network at the blend interface, which is thought to play a key role in the co-continuous microphase structure. Microscopic morphological characterization shows that PDMS-PUA and PEA-PUA phases are deformed and oriented together during the stretching process, thus jointly resisting external forces. Moreover, the blends show an exceptional self-healing ability due to their strong and reversible hydrogen bonding network.

Polystyrene Chain Geometry Probed by Ion Mobility Mass Spectrometry and Molecular Dynamics Simulations.

Polystyrene (PS) is a thermoplastic polymer commonly used in various applications due to its bulk properties. Designing functional polystyrenes with well-defined structures for targeted applications is of significant interest due to the rigid and apolar nature of the polymer chain. Progress is hindered to date by the limitations of current analytical methods in defining the atomistic-level folding of the polymer chain. The integration of ion mobility spectrometry and molecular dynamics simulations is beneficial in addressing these challenges. However, data on gas-phase polystyrene ions are rarely reported in the literature. We herein investigate the gas phase structure of polystyrene ions with different end groups to establish how the nature and the rigidity of the monomer unit affect the charge stabilization. We find that, in contrast to polar polymers in which the charges are located deep in the ionic globules, the charges in the PS ions are rather located at the periphery of the polymer backbone, leading to singly and doubly charged PS ions adopting dense elliptic-shaped structures. Molecular dynamics (MD) simulations indicate that the folding of the PS rigid chain is controlled by phenyl ring interactions with the charge ultimately remaining excluded from the core of the globular ions, whereas the folding of polyether ions is initiated by the folding of the flexible polyether chain around the sodium ion that remains deeply enclosed in the core of the ions.

Synergistically flexible-robust effects mediate the dynamic reconfiguration of perylene diimide polymer to enhance piezo-photocatalytic nitrate reduction

Identifying the spatial dynamic reconstruction of π-conjugated polymers for efficient carrier transport and controlling the intermediate process of the reaction are urgent and formidable challenges. In this study, a fresh perspective has emerged proposing to synergistically enhance the adaptability and resilience of dynamic torsion patterns in π-conjugated polymers to mediate charge separation and molecular activation. Excitingly, the highest flexible-robust structure and polarity of naphthalene-linked perylene diimide polymer (N-PDA) demonstrates a highest nitrate reduction rate of 5.36 mmol g−1 h−1 under light irradiation and ultrasonic condition, which is 7.5 times that of H-PDA. Theoretical calculations and experimental observations indicate that the strongest flexible-robust structure of N-PDA enhances the inclination of the rigid plane and atomic bond length, resulting in an accelerated uneven distribution of charges, molecular polarity, and electronic coupling to facilitate charge separation dynamics. Moreover, it exposes active sites that promote the adsorption and activation of NO3- ions while simultaneously regulating intermediate hydrogenation processes. Our study offers innovative prospects for enhancing catalytic efficiency through the implementation of spatial steric configuration of π-conjugated polymers.

Universal Time and Length Scales of Polar Active Polymer Melts.

We present an in-depth multiscale analysis of the conformations and dynamics of polar active polymers, comparing very dilute and very dense conditions. We unveil characteristic length and time scales, common to both dilute and dense systems, that recapitulate the conformational and dynamical properties of these active polymers upon varying both the polymer size and the strength of the activity. Specifically, we find that a correlation (or looping) length characterizes the polymer conformations and the monomer dynamics. Instead, the dynamics of the center of mass can be fully characterized by the end-to-end mean-square distance and by the associated relaxation time. As such, we show that the dynamics of individual chains in melts of polar active polymers is not controlled by entanglements, but only by the strength of the self-propulsion.

Active polar ring polymer in shear flow-An analytical study.

We theoretically study the conformational and dynamical properties of semiflexible active polar ring polymers under linear shear flow. A ring is described as a continuous semiflexible Gaussian polymer with a tangential active force of a constant density along its contour. The linear but non-Hermitian equation of motion is solved using an eigenfunction expansion, which yields activity-independent, but shear-rate-dependent, relaxation times and activity-dependent frequencies. As a consequence, the ring's stationary-state properties are independent of activity, and its conformations and rheological properties are equal to those of a passive ring under shear. The presence of characteristic time scales by relaxation and the activity-dependent frequencies give rise to a particular dynamical behavior. A tank-treading-like motion emerges for long relaxation times and high activities, specifically for stiff rings. In the case of very flexible polymers, the relaxation behavior dominates over activity contributions suppressing tank-treading. Shear strongly affects the crossover from a tank-treading to a relaxation-dominated dynamics, and the ring polymer exhibits tumbling motion at high shear rates. This is reflected in the tumbling frequency, which displays two shear-rate dependent regimes, with an activity-dependent plateau at low shear rates followed by a power-law regime with increasing tumbling frequency for high shear rates.

Proton transfer induced persistent triplet charge transfer phosphorescence in molecule-doped polymer systems

The intermolecular interactions between small molecules and the matrix in a highly polar environment could easily lead to non-radiative transitions, which significantly hampers the development of high-performance persistent room-temperature phosphorescence (pRTP) materials in such condition. Herein, we introduce a novel strategy that integrates consecutive proton transfer and photo-induced charge transfer to facilitate triplet charge transfer emission in highly polar polymer matrix. In particular, doping aza-arene guests including 1,10-phenanthroline (1,10-Phen), 2,9-dimethyl-1,10-phenanthroline (DM-Phen), and 7,8-benzoquinoline (7,8-BQ) into polyacrylic acid (PAA) resulted in superior pRTP properties compared to other polymer hosts. Spectroscopic investigations and theoretical calculations elucidate that this is attributed to the proton transfer and triplet charge transfer characteristics between the host and guest. Moreover, due to the rigid environment and space confinement provided by PAA, pRTP with the lifetime up to 841 ms is achieved. Capitalizing on the excellent water solubility of the doped PAA films, the inkjet printings have been executed, and showcasing the promising the potential applications of these pRTP materials in the field of information encryption.

Helical peptide structure improves conductivity and stability of solid electrolytes.

Ion transport is essential to energy storage, cellular signalling and desalination. Polymers have been explored for decades as solid-state electrolytes by either adding salt to polar polymers or tethering ions to the backbone to create less flammable and more robust systems. New design paradigms are needed to advance the performance of solid polymer electrolytes beyond conventional systems. Here the role of a helical secondary structure is shown to greatly enhance the conductivity of solvent-free polymer electrolytes using cationic polypeptides with a mobile anion. Longer helices lead to higher conductivity, and random coil peptides show substantially lower conductivity. The macrodipole of the helix increases with peptide length, leading to larger dielectric constants. The hydrogen bonding of the helix also imparts thermal and electrochemical stability, while allowing for facile dissolution back to monomer in acid. Peptide polymer electrolytes present a promising platform for the design of next-generation ion-transporting materials.

Harnessing Polar Interactions Tunes the Stability of Ultrathin Polymer Solution Films.

The stability of ultrathin (<100 nm) polymer films is essential in applications like protective coatings. On the contrary, their instability may actually be desirable for the emergence of self-assembled nanoscale patterns utilized in the fabrication of functional devices. Polymer solution films exhibit two distinct kinds of instabilities, viz., dewetting (long-wave) and decomposition (short-wave). Dewetting refers to the rupture of the continuous film to form isolated domains, while decomposition leads to phase separation within the polymer solution. The focus of this work is on leveraging polar interactions between the solute and solvent molecules to tune the stability of the film. A gradient dynamics-based thin film model is developed to investigate pattern formation in a thin polar polymer solution film. The Flory-Huggins theory is suitably modified by introducing a polar interaction parameter that depends upon the concentration of the polymer and the dipole moments of monomer (μ1) and solvent molecules (μ0). A linear stability analysis is performed to determine the characteristic length scale and growth rate of the instabilities. It is shown that the range of concentration space for the occurrence of the decomposition mode is directly affected by the Flory interaction parameter (χ0), μ0, and μ1, thereby serving as control parameters to tune the width of the concentration range. It is further shown that ignoring polar interactions may lead to incorrect predictions of the instability mode, including a complete loss of the decomposition mode. In addition, the long-wave dewetting length scale is found to decrease due to bulk dipolar interactions at higher polymer concentrations. Finally, numerical simulations are carried out to track the nonlinear evolution of the interface and concentration field for both the decomposition and dewetting modes of instability.

Controllable construction of mesoporous hollow carbon spheres rich in micropores from waterborne benzoxazine and their application in supercapacitors

Mesoporous hollow carbon spheres (MHCSs) with mesoporous channels and nanocages structure have unique advantages in energy storage. However, this structure alone does not significantly enhance the electrochemical double layer capacitance (EDLC). Additionally, the current hydrophobic nature of polymer precursors with high char yield impedes effective binding with templates due to polarity differences. Moreover, the use of toxic organic solvents presents obstacles to further development. So, it remains a challenge to prepare MHCSs rich in micropores using polar polymers with high char yield in green solvent. In this work, we prepared MHCSs rich in micropores (MMHCSs) using waterborne benzoxazine as a carbon sources and dendritic/fibrous nano-silica as a sacrificial hard template using water as the solvent and combined with freeze-drying, curing, carbonization and an activation step. The optimal MMHCSs (MMHCSs306–1–7000.5h) has a large specific surface area (1057 m2 g−1), and has a maximum specific capacitance value near 221.45 F g−1 at 0.5 A g−1 in a three-electrode system, the specific capacitance still reaches 156.66 F g−1 at a high current density (20 A g−1) due to the full utilization of micropores in the presence of mesoporous-shell and hollow-core. When assembled into a symmetrical supercapacitor, the energy density reaches 5.91 Wh kg−1 when the power density is 137.5 W kg−1. The study provides an eco-friendly method for preparing MMHCSs, and the unique structure has potential application in supercapacitors.

Integrating Activated Inorganic Fluoride Nanocrystals with Polar Polymer for Wide-Temperature Solid Lithium Metal Batteries

Integrating Activated Inorganic Fluoride Nanocrystals with Polar Polymer for Wide-Temperature Solid Lithium Metal Batteries

Shear‐Rheological‐Assisted MXene Dispersion in Epoxy Resin for Efficient Electromagnetic Absorption

AbstractMXenes, a burgeoning family of 2D materials with high conductivity and large specific surface area, are ideal electromagnetic absorbing materials. However, the ample polar functional groups lead to poor dispersion in the non‐polar matrix, limiting its application in non‐polar‐polymer‐based composites. With the help of the shear rheological properties of SiO2, the conflict is resolved here by directly dispersing MXene aqueous dispersion into the non‐polar resin. Water is locked dynamically through SiO2 nanoparticles among the MXene@SiO2 nanosheets, suppressing MXene's self‐restacking and aggregation in the resin matrix. Therefore, the fabrication of uniform MXene/non‐polar polymer composites is achieved. Meanwhile, this method allows different nanoparticles (Fe3O4, etc.) to be evenly dispersed among the MXene nanosheets to further improve the composites' electromagnetic parameters. The as‐prepared composites achieve remarkable absorbing performance with a low MXene concentration (≤5 wt.‰). The SMEP‐h achieves the maximum reflection loss value of over 60 dB at 12 GHz (at the thickness of 2.15 mm), and the SMEP‐F possesses a broad effective absorbing bandwidth of over 6.18 GHz (at the thickness of 1.75 mm). The shear‐rheological‐assisted MXene dispersion method in the non‐polar matrix paves an avenue for the design of outstanding MXene‐based electromagnetic absorbing composites.

Prediction of a Novel Electromechanical Response in Polar Polymers with Rigid Backbones: Contrasting Furan-Derived Nanothreads to Poly(Vinylidene Fluoride).

Syn furan nanothreads have all oxygen atoms arranged on one side of the thread backbone; these polar threads present intriguing opportunities in electromechanical response owing to their rigid ladder-like backbone. We retrained a C/H/O reactive force field to simulate their response to external electric field for both end-anchored individual threads and bulk nanothread crystals, contrasting the results to those for poly(vinylidene fluoride) (PVDF) polymer. Whereas the field induces a length-independent torque in PVDF through backbone rotation about σ bonds, furan-derived nanothreads generate a length-dependent torque by progressively twisting their rigid backbone. This mode of response couples the rotational history of the electric field to axial tension in the anchored thread. In simulations of densely packed syn furan nanothread crystals without anchors, the crystals pole in a field (∼3 GV/m at 300 K) similar to that seen in simulations of PVDF, suggesting that crystals of polar nanothreads can be ferroelectric.

A Fluorescent Conjugated Polar Polymer for Probing Charge Injection in Multilayer Organic Light-Emitting Transistors.

Ambipolar organic light-emitting transistors (OLETs) are extremely appealing devices for applications from sensing to communication and display realization due to their inherent capability of coupling switching and light-emitting features. However, their limited external quantum efficiency (EQE) and brightness under ambipolar bias conditions hamper the progress of OLET technology. In this context, it was recently demonstrated in multi-stacked devices that the engineering of the interface between the topmost electron-transporting organic semiconductor (e-OS) and the emission layer (EML) is crucial in optimizing the recombination of the minority charges (i.e., electrons) and to enhance EQE and brightness. Here, we introduce a new light-emitting conjugated polar polymer (CPP) in a multi-stacked OLET to improve the electron injection from e-OS to EML and to study, simultaneously, electroluminescence-related processes such as exciton formation and quenching processes. Interestingly, we observed that the highly polar groups present in the conjugate polymer induced polarization-related relevant charge-trapping phenomena with consequent modulation of the entire electrostatic field distribution and unexpected optoelectronic features. In view of the extensive use of CPPs in OLETs, the use of multifunctional CPPs for probing photophysical processes at the functional interfaces in stacked devices may speed up the improvement of the light-emission properties in OLETs.

Synthetic Design of Dual Polar Side Chain Polymers for Enhancing Electrochromic Performance

Synthetic Design of Dual Polar Side Chain Polymers for Enhancing Electrochromic Performance

Deep-Learning Interatomic Potential Connects Molecular Structural Ordering to the Macroscale Properties of Polyacrylonitrile.

Polyacrylonitrile (PAN) is an important commercial polymer, bearing atactic stereochemistry resulting from nonselective radical polymerization. As such, an accurate, fundamental understanding of governing interactions among PAN molecular units is indispensable for advancing the design principles of final products at reduced processability costs. While ab initio molecular dynamics (AIMD) simulations can provide the necessary accuracy for treating key interactions in polar polymers, such as dipole-dipole interactions and hydrogen bonding, and analyzing their influence on the molecular orientation, their implementation is limited to small molecules only. Herein, we show that the neural network interatomic potentials (NNIPs) that are trained on the small-scale AIMD data (acquired for oligomers) can be efficiently employed to examine the structures and properties at large scales (polymers). NNIP provides critical insight into intra- and interchain hydrogen-bonding and dipolar correlations and accurately predicts the amorphous bulk PAN structure validated by modeling the experimental X-ray structure factor. Furthermore, the NNIP-predicted PAN properties, such as density and elastic modulus, are in good agreement with their experimental values. Overall, the trend in the elastic modulus is found to correlate strongly with the PAN structural orientations encoded in the Hermans orientation factor. This study enables the ability to predict the structure-property relations for PAN and analogues with sustainable ab initio accuracy across scales.

Enhanced energy density in cellulose doped polyimide-based all organic composites for high temperature capacitor applications

Abstract The growing demand for electronic devices has induced a significant requirement for high energy density capacitors. In this investigation, we introduced small groups of cyanoethyl cellulose (CEC) into a polyimide (PI) substrate to create all organic CEC/PI composite films for high energy density capacitor applications. Due to the large dipole moment in C–CN dipoles in CEC groups, the dielectric constant of the CEC/PI-5 (5% CEC) composite increased by 26.3% to 4.31. Compared to the pristine PI film at room temperature, the breakdown field of the CEC/PI-0.5 increased by 4.7% from 502.29 to 526.1 MV m−1 and the energy storage density increased by 95% to 11.70 J cm−3. Furthermore, the CEC/PI-0.5 film exhibited an energy density of 6.39 J cm−3 with the breakdown field of 400 MV m−1 at 150 °C, which is 93.05% higher in energy densities than that of the pristine PI film. Furthermore, simulation results indicate that CEC groups can introduce deep traps in the CEC/PI composite, which can inhibit charge movement in the composite and increase the breakdown field of it. In this study, it was found that by adding small amount of CEC polar group in PI film, the high temperature energy density of CEC/PI composite materials was significantly improved. This study not only makes a significant contribution to the development of high-temperature energy-density capacitors, but also pave a way by using small molecule polar polymers to improve the energy density of dielectric materials at high temperature.