High-performance Copolymer Research Articles

Optimal Toughness in Copolymer Ionogels: Revealing Phase-Separation Evolution via Coarse-Grained Molecular Dynamics Simulation

This study focuses on understanding how the phase-separation process affects the toughness of random copolymer ionogels. Previous research has shown that adjusting the balance between solvophobic and solvophilic monomers within the copolymer can significantly change the mechanical properties of ionogels. This research used coarse-grained molecular dynamics simulations to analyze how phase-separation structure influences the mechanical properties of random copolymer ionogels. The results show that increasing the proportion of solvophobic monomers improves toughness up to a critical point, beyond which toughness declines due to a transition from bi-continuous to macro-phase separation. Additionally, reducing the ionic solvent content generally enhances both strength and toughness, while the ultimate strain remains nearly consistent. Stronger hydrogen bonds between solvophobic polymer segments increase rigidity but decrease toughness. This study provides important insights for designing and synthesizing high-performance copolymer ionogels.

Novel avenues for achieving simultaneous high-efficiency oil removal and sterilization: Designing a quaternary ammonium-hydrophobic ternary template copolymer

In treating complex sewage containing microorganisms, flocculation and disinfection typically occur as distinct stages, involving the addition of flocculants and disinfectants separately. To integrate oil removal and disinfection, a novel quaternary ammonium-hydrophobic ternary template polymer, TPAMA-DA, was engineered with capabilities for both flocculation and sterilization functions. Optimal copolymer characteristics were determined through Response Surface Methodology of the preparation parameters for TPAMA-DA. The copolymer prepared was applied to model wastewater, and the results indicate that, in emulsified oil and E. coli single systems, TPAMA-DA achieved removal rates of 95.71 % and 97.19 % for emulsified oil and OD600 (residual OD600 = 0.0239), respectively, showcasing superior oil removal and antibacterial capabilities compared to TPAMA and PAMA. Meanwhile, TPAMA-DA exhibited excellent oil removal efficiency across a broad range of pH environments, contrasting sharply with its pH-sensitive antibacterial properties. Surprisingly, applying TPAMA-DA to the oil-E. coli binary systems, it not only maintained high efficiency in oil removal but also showed certain pH adaptability in antibacterial activity, suggesting TPAMA-DA’s outstanding ability for simultaneous oil removal and antibacterial action in oil-E. coli binary systems. Impressively, SEM and 3D-EEM analyses confirm that TPAMA-DA disrupts the bacterial cell, resulting in the death of E. coli. These findings may pave the way for new avenues in the development of multi-functional, efficient, low-consumption, and environmentally friendly high-performance copolymers with dual capabilities for oil removal and sterilization.

Thermally Stable and Chemically Recyclable Poly(ketal-ester)s Regulated by Floor Temperature.

Chemical recycling to monomers (CRM) offers a promising closed-loop approach to transition from current linear plastic economy toward a more sustainable circular paradigm. Typically, this approach has focused on modulating the ceiling temperature (Tc) of monomers. Despite considerable advancements, polymers with low Tc often face challenges such as inadequate thermal stability, exemplified by poly(γ-butyrolactone) (PGBL) with a decomposition temperature of ∼200 °C. In contrast, floor temperature (Tf)-regulated polymers, particularly those synthesized via the ring-opening polymerization (ROP) of macrolactones, inherently exhibit enhanced thermodynamic stability as the temperature increases. However, the development of those Tf regulated chemically recyclable polymers remains relatively underexplored. In this context, by judicious design and efficient synthesis of a biobased macrocyclic diester monomer (HOD), we developed a type of Tf -regulated closed-loop chemically recyclable poly(ketal-ester) (PHOD). First, the entropy-driven ROP of HOD generated high-molar mass PHOD with exceptional thermal stability with a Td,5% reaching up to 353 °C. Notably, it maintains a high Td,5% of 345 °C even without removing the polymerization catalyst. This contrasts markedly with PGBL, which spontaneously depolymerizes back to the monomer above its Tc in the presence of catalyst. Second, PHOD displays outstanding closed-loop chemical recyclability at room temperature within just 1 min with tBuOK. Finally, copolymerization of pentadecanolide (PDL) with HOD generated high-performance copolymers (PHOD-co-PPDL) with tunable mechanical properties and chemical recyclability of both components.

Polyaryletherketone Based Blends: A Review.

This review aims to report the status of the research on polyaryletherketone-based thermoplastic blends (PAEK). PAEK are high-performance copolymers able to replace metals in many applications including those related to the environmental and energy transition. PAEK lead to the extension of high-performance multifunctional materials to target embedded electronics, robotics, aerospace, medical devices and prostheses. Blending PAEK with other thermostable thermoplastic polymers is a viable option to obtain materials with new affordable properties. First, this study investigates the miscibility of each couple. Due to different types of interactions, PAEK-based thermoplastic blends go from fully miscible (with some polyetherimides) to immiscible (with polytetrafluoroethylene). Depending on the ether-to-ketone ratio of PAEK as well as the nature of the second component, a large range of crystalline structures and blend morphologies are reported. The PAEK-based thermoplastic blends are elaborated by melt-mixing or solution blending. Then, the effect of the composition and blending preparation on the mechanical properties are investigated. PAEK-based thermoplastic blends give rise to the possibility of tuning their properties to design novel materials. However, we demonstrate hereby that significant research effort is needed to overcome the lack of knowledge on the structure/morphology/property relationships for those types of high-performance thermoplastic blends.

Inclusion/exclusion behavior of comonomer units in isodimorphic crystallization of biobased copolyamides PA6/PA56

A series of semi-crystalline bio-based copolyamides PA6x56y were synthesized via melt polycondensation from caprolactam (6 units) and bio-based Pentamethylene adipamide units (56 units). DSC results show that the melting and crystallization temperature depend on the comonomers composition, and exhibit isodimorphic behavior. Combined with the analysis of WAXD, it is found that the 56 units are more tend to be excluded from rather than incorporated into the PA6 crystals. However, it does not imply a complete exclusion. Unexpectedly, there is a significant relationship between the content of 56 units on the polymorphic crystallization behavior of PA6-type crystals. Moreover, the pseudo-eutectic point appears when 56 units content is 30 mol %, and the spherulite morphology exhibits a strong correlation with the pseudo-eutectic point. In addition, the excess free energy of defects (ε) is calculated by applying the Wending-Suter model, and it is found that the ε-value caused by the insertion of 56 units into the crystal formed by PA6 is higher than that of 6 units into a crystal formed by PA56. Therefore, 6 units are more easily inserted into crystals formed by PA56, i.e., 6 units have better compatibility with PA56 crystals. In summary, this work reveals the involved mechanisms of comonomer units in the crystallization process and provides a potential strategy to guide the development of high-performance copolymers in the future.

Physical Aging Behavior of the Side Chain of a Conjugated Polymer PBTTT

This paper provides a viewpoint of the technology of the fast-scanning calorimetry with the relaxation behavior of disordered side chains of poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C12) around the glass transition temperature of the side chains (Tg,γ). PBTTT is an ideal model of the high-performance copolymer of poly(alkylthiophenes) with side chains. The γ1 relaxation process of the disordered side chains of PBTTT was detected as a small endothermic peak that emerges before the γ2 relaxation process. It shows an increase with increasing temperature as it approaches the glass transition temperature of the disordered side chains of PBTTT. The ductile-brittle transition of PBTTT in low temperatures originating from the thermal relaxation process is probed and illustrated by physical aging experiments. The signature is shown that the relaxation process of the disordered side chain of PBTTT at low temperatures varies from Arrhenius temperature dependence to super Arrhenius temperature dependence at high temperatures. These observations could have significant consequences for the stability of devices based on conjugated polymers, especially those utilized for stretchable or flexible applications, or those demanding mechanical robustness during tensile fabrication or use in a low-temperature environment.

Efficient exploration of compositional space for high-performance copolymers via Bayesian optimization.

The traditional approach employed in copolymer compositional design, which relies on trial-and-error, faces low-efficiency and high-cost obstacles when attempting to simultaneously improve multiple conflicting properties. For example, designing co-cured polycyanurates that exhibit both moisture and thermal resistance, along with high modulus, is a long-term challenge because of the intrinsic trade-offs between these properties. In this work, to surmount these barriers, we developed a Bayesian optimization (BO)-guided method to expedite the discovery of co-cured polycyanurates exhibiting low water uptake, coupled with higher glass transition temperature and Young's modulus. By virtue of the knowledge of molecular simulations, benchmarking studies were carried out to develop an effective BO-guided method. Propelled by the developed method, several copolymers with improved comprehensive properties were obtained experimentally in a few iterations. This work provides guidance for efficiently designing other high-performance copolymers.

Thermal Degradation Studies of High-Performance Copolymer Resin Derived From 8-Hydroxyquinoline, Acrylamide and Furfural

Thermal Degradation Studies of High-Performance Copolymer Resin Derived From 8-Hydroxyquinoline, Acrylamide and Furfural

Micromechanism Study of Molecular Compatibility of PVDF/PEI Blend Membrane.

In this paper, the compatibility of polyetherimide (PEI) with different contents as a high-performance copolymer and polyvinylidene fluoride (PVDF) was studied, and 5%–20% PEI was prepared by the non-solvent-induced phase inversion method. The compatibility of PVDF and PEI was evaluated by analyzing the physical structure and properties of the blend membrane, the microstructure, the glass transition temperature Tg, the enthalpy, and the mechanism of the polymer blend enthalpy change. The results show that the blend membranes have -NH and C=O-N binding energies at X-ray photoelectron spectroscopy (XPS), which preliminarily proves that fluorine–amine bonds are formed between the polymers, and new spectra appeared by Fourier transform infrared (FTIR) and X-ray diffraction (XRD) peaks, which further proves that the two have the formation of fluorine–amine bonds, the Tg and enthalpy of the mixed membrane was increased, and a scanning electron microscope (SEM) observed that the membrane pores changed from finger-like pores to sponge-like macropores. When the content of PEI is 15%, the performance of the blended membrane is the best, the water contact angle increases to 58.5°, the porosity increases to 17.33%, the maximum force increases to 8.04 N, and the elongation at break decreases to 24.26%, the pure water flux is 1870.292 L/m2·h, and the oil rejection is 87%. In addition, the enthalpy change of polymer blending further proves that PEI and PVDF are compatible systems and have a good performance improvement for PVDF.

Formation of boronate-based macroporous copolymer via emulsion-assisted interface self-assembly method for specific enrichment of Naringin

In this paper, the boronate affinity (BA) copolymer sorbents with crosslinked hydrogen bond networks were successfully synthesized by emulsion-induced interface self-assembly and applied in high-performance copolymer materials (BCDPs-CPs-2) for the specific separation and purification of separate cis-diol containing naringin (NRG). A novel solid particle β-cyclodextrins (CDs) based on microporous organic polymers (MOPs) with high surface area were fabricated. As the main solid emulsifier, β-CDs-based MOPs (CDPs) can effectively improve the emulsifying performance of the emulsion droplet, whilst reducing the amounts of surfactant. At the same time, CDPs can effective combined with boronate affinity functioned adamantane (Ad) inclusion derivative were by self-assembly at the two phase interface, which realizes the surface boronic acid functionalities of copolymer materials conveniently. Furthermore, the copolymer materials with crosslinked hydrogen bond networks were obtained via a interface copolymerization between water phase monomer N-(methoxymethyl)-2-methyl-2-propenamide (MMP) and the oil phase monomer methoxyethyl acrylate (MEA). The obtained copolymer materials exhibited stable macroporous structure and shape memory abilities, which effectively improve the regeneration property in practical extract conditions. The combination of excellent performance, BCDPs-CPs-2 showed rapid binding rate (360 min) and high adsorption capacity (3.14 μmol g−1) at 298 K. Moreover, outstanding reusability of 5.34% loss in enrichment performance after five times repeatedly. The NRG component content of the purified samples (approximately 96.67%) was superior to original crude extract (about 75.0%). Additionally, the adsorption mechanism is discussed in detail with the effect of pH, different copolymer materials, and thermodynamics.

Design of simple-structure wide-bandgap conjugated polymers based on BDT for efficient non-fullerene solar cells

The recent evolution of non-fullerene acceptors yields brilliant progress for organic solar cells (OSCs). However, high-performance copolymer donors with simple chemical structures for new acceptors are a few. In this work, a series of donors based on BDT are developed with ester-substituted trithiophene as a repeating acceptor unit. Copolymerized polymers exhibit slightly red-shifted absorption and down-shifted the highest occupied molecular orbital (HOMO) as the side chains turning from alkyl (3TCO-R) and oxyalkyl (3TCO-OR) to thienyl (3TCO-Th) and chlorine-substituted thienyl (3TCO-Th-Cl), respectively. As a result, the corresponding power conversion efficiency (PCE) of 3TCO-Th-Cl based devices shows the most excellent performance (PCE = 7.70%) especially in open-circuit voltage (VOC = 1 V) when blending with ITIC and its PCE makes a breakthrough with Y6 (PCE = 10.30%). Moreover, the fabricated semitransparent OSCs exhibit a rational PCE of 8.16% with average visible transparency of 16.40%.

Studies on the curing behavior, thermal, and mechanical properties of epoxy resin‐co‐amine‐functionalized lead phthalocyanine

AbstractA high performance copolymer was prepared by using epoxy (EP) resin as matrix and 3,10,17,24‐tetra‐aminoethoxy lead phthalocyanine (APbPc) as additive with dicyandiamide as curing agent. Fourier‐transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetric analysis (DSC), and thermogravimetric analysis (TGA) were used to study the curing behavior, curing kinetics, dynamic mechanical properties, impact and tensile strength, and thermal stability of EP/APbPc blends. The experimental results show that APbPc, as a synergistic curing agent, can effectively reduce the curing temperature of epoxy resin. The curing kinetics of the copolymer was investigated by non‐isothermal DSC to determine kinetic data and measurement of the activation energy. DMA, impact, and tensile strength tests proved that phthalocyanine can significantly improve the toughness and stiffness of epoxy resin. Highest values were seen on the 20 wt% loading of APbPc in the copolymers, energy storage modulus, and impact strength increased respectively 388.46 MPa and 3.6 kJ/m2, Tg decreased 19.46°C. TGA curves indicated that the cured copolymers also exhibit excellent thermal properties.

Preparation of high performance copolymer microcapsule encapsulated heat storage material without supercooling

ABSTRACTThe methyl methacrylate (MMA)-based copolymer microcapsules encapsulating Rubitherm®27 (RT27) used as a phase change material were successfully prepared by microsuspension polymerization. The influence of three types of crosslinked comonomers such as ethylene glycol dimethacrylate), trimethylolpropane trimethacrylate, and divinylbenzene (DVB) on the microcapsule formation was studied at various ratios of MMA:crosslinked comonomer. It was found that using MMA:DVB at 70:30 wt% was the optimum ratio. The obtained microcapsules were nonspherical in shape with a dent and high shell strength. In addition, the latent heats of melting and crystallization of the encapsulated RT27 were about 140 J/g-RT27 which were close to those of the original RT27. However, the crystallization temperatures (Tc) of the encapsulated RT27 (14°C) were lower than that of the original RT27 (25°C) which was called supercooling. To prevent supercooling, the effect of nucleating agents (emulgen 150, 1-octadecanol, and RT58) on decreasing supercooling of the encapsulated RT27 was investigated. The results clearly presented that the addition of at least 5 wt% of RT58 significantly increased Tc (25°C) of the encapsulated RT27, whereas the observed latent heats were pretty close to original RT27.

Copolymerization of bisphthalonitrile/benzoxazine blends: Curing behavior, thermomechanical and thermal properties

A high-performance copolymer was successfully prepared by blending bisphenol-A based bisphthalonitrile monomer (BAPh) with phenol-aniline-based benzoxazine monomer (P-a). The obtained copolymers exhibited excellent thermal stability and thermomechanical properties. The Fourier transform infrared (FTIR) spectra of BAPh/P-a 5:5 system at different curing procedure proved the curing reaction mechanism. In addition, differential scanning calorimetry (DSC) curves showed that the curing reaction of the BAPh was induced by the active hydroxyl produced by the ring-opening polymerization of P-a; compared to the neat monomers, the curing temperature of the copolymer decreased and the curing speed improved. The evolution of thermal gravimetric analysis (TGA) curves revealed that the poly(BAPh/P-a)-5:5 displayed highest T5%, T10%, and char yield. The dynamic mechanical analysis (DMA) proved that the glass transition temperature and storage modulus of copolymers with the BAPh monomer as the matrix increased with the content of P-a increase, while copolymers with P-a as the matrix obtained nearly same results. The poly(BAPh/P-a) -5:5 exhibited best thermal and thermomechanical properties among different composition copolymers.

Asymmetric-Indenothiophene-Based Copolymers for Bulk Heterojunction Solar Cells with 9.14% Efficiency.

The first two asymmetric-indenothiophene-based donor-acceptor copolymers (PITBT and PITFBT) are prepared through Stille coupling reactions between distannyl indenothiophene and brominated benzothiadiazole derivatives. The best performing solar cell fabricated from PITFBT exhibits a power conversion efficiency of 9.14% which demonstrates a great potential of the asymmetric indenothiophene for high-performance copolymers.

Synthesis and characterization of novel high-performance polyarylsulfones with 4-(carbazol-9-yl) triphenylamine moieties

A novel homopolyarylsulfone with 4-(carbazol-9-yl) triphenylamine moieties was synthesized successfully through N–C coupling reactions under similar conditions to the synthesis of polyarylsulfones (PSU). By using this simple method and adjusting the feed ratio between 9-(4-aminobenzene) carbazole (NH2–Ar–Cz) and bisphenol A, a series of high-performance copolymers with high molecular weight, good film-reforming ability, great thermal stability, and excellent photoelectric characteristics were also prepared, which have good application potential in the field of organic optoelectronics.

Slot‐Die Coating of a High Performance Copolymer in a Readily Scalable Roll Process for Polymer Solar Cells

Copolymers based on dithieno[3,2‐b:2′,3′‐d]silole (DTS) and dithienylthiazolo[5,4‐d]thiazole (TTz) are synthesized and tested in an all‐solution roll process for polymer solar cells (PSCs). Fabrication of polymer:[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) solar cells is done on a previously reported compact coating/printing machine, which enables the preparation of PSCs that are directly scalable with full roll‐to‐roll processing. The positioning of the side‐chains on the thiophene units proves to be very significant in terms of solubility of the polymers and consequently has a major impact on the device yield and process control. The most successful processing is accomplished with the polymer, PDTSTTz‐4, that has the side‐chains situated in the 4‐position on the thiophene units. Inverted PSCs based on PDTSTTz‐4 demonstrate high fill factors, up to 59%, even with active layer thicknesses well above 200 nm. Power conversion efficiencies of up to 3.5% can be reached with the roll‐coated PDTSTTz‐4:PCBM solar cells that, together with good process control and high device yield, designate PDTSTTz‐4 as a convincing candidate for high‐throughput roll‐to‐roll production of PSCs.

Widhtrawal] Structual Characterization of High-performance Co-polymer Lithium Storage Material by EXAFS and DFT Calculations

Widhtrawal] Structual Characterization of High-performance Co-polymer Lithium Storage Material by EXAFS and DFT Calculations

Critical Role of Side-Chain Attachment Density on the Order and Device Performance of Polythiophenes

High performance, solution processable semiconductors are critical to the realization of low cost, large area electronics. We show that a signature molecular packing motifside-chain interdigitationcorrelates to high performance for a large and important class of organic semiconductors. The side chains of recently developed high performance copolymers of poly(alkylthiophenes) can and do interdigitate substantially, whereas they do not in the most common form of the extensively studied, lower performance poly(alkythiophenes). Side-chain interdigitation provides a mechanism for three-dimensional ordering; without it, poly(alkylthiophenes) are limited to small domains and poor performance. We propose the synthetic design rule that three-dimensional ordering is promoted by side-chain attachment densities sufficiently low to permit interdigitation.