Ternary Copolymers Research Articles

Multicomponent Self-Assembly and Self-Sorting of Polymer Micelles in Water: Selective and Switchable Association by Kinetic or Thermodynamic Control.

Herein, we report multicomponent self-assembly and self-sorting of polymer micelles in water using mixtures of an anionic random copolymer bearing sodium sulfonate and dodecyl groups and random copolymers carrying poly(ethylene glycol) (PEG) and alkyl groups. In pure water, the anionic copolymer is co-self-assembled with the PEG copolymers to form anion/PEG-fused micelles with a controlled aggregation number. By designing the composition or alkyl groups of PEG copolymers, the fused micelle is reversibly self-sorted into discrete anion or PEG micelles in the presence of NaCl. Co-self-assembly of the anionic copolymer and PEG copolymers is kinetically or thermodynamically controlled, depending on the dynamic properties of the PEG copolymer micelles. Thus, the selective self-assembly of ternary copolymers is also controllable and switchable by temperature: A kinetically favored anion/PEG-fused micelle is predominantly formed in the presence of a kinetically frozen PEG micelle at low temperature, whereas the fused micelle is transformed via polymer chain exchange upon heating into a thermodynamically more stable anion/PEG-fused micelle.

Dissipative Particle Dynamics Study on Interfacial Properties of Ternary H-Shaped Copolymer–Homopolymer Blends

Dissipative particle dynamics (DPD) simulations is used to study the effect of Am/2BmAm/2 and H-shaped (Am/4)2Bm(Am/4)2 block copolymers on the interfacial properties of ternary blends. Our simulations show the following: (i) The capacity of block copolymers to diminish interfacial tension is closely linked to their compositions. With identical molecular weights and concentrations, H-shaped block copolymers outperform triblock copolymers in mitigating interfacial tension. (ii) The interfacial tension within the blends correlates positively with the escalation in H-shaped block copolymer molecular weight. This correlation suggests that H-shaped block copolymers featuring a low molecular weight demonstrate superior efficacy as compatibilizers when contrasted with those possessing a high molecular weight. (iii) Enhancing the concentration of H-shaped block copolymers fosters their accumulation at the interface, leading to a reduction in correlations between immiscible homopolymers and a consequent decrease in interfacial tension. (iv) As the length of the homopolymer chains increases, there is a concurrent elevation in interfacial tension, suggesting that H-shaped block copolymers perform more effectively as compatibilizers in blends characterized by shorter homopolymer chain lengths. These findings elucidate the associations between the efficacy of H-shaped block copolymer compatibilizers and their specific molecular characteristics.

In Situ Formation of Acidic Comonomer during Thermal Treatment of Copolymers of Acrylonitrile and Its Influence on the Cyclization Reaction.

Binary and ternary copolymers of acrylonitrile (AN), tert-butyl acrylate (TBA), and n-butyl acrylate (BA) are synthesized through conventional radical polymerization in DMSO in the presence of 2-mercaptoethanol. The thermal behavior of binary and ternary copolymers is studied under argon atmosphere and in air. It is demonstrated that the copolymers of AN contain 1-10 mol.% of TBA split isobutylene upon heating above 160 °C, resulting in the formation of the units of acrylic acid in the chain. The carboxylic groups formed in situ are responsible for the ionic mechanism of cyclization, which starts at lower temperatures compared with pure polyacrylonitrile (PAN) or AN copolymer with BA. The activation energy of cyclization through ionic and radical mechanisms depends on copolymer composition. For the ionic mechanism, the activation energy lies in the range ca. 100-130 kJ/mole, while for the radical mechanism, it lies in the range ca. 150-190 kJ/mole. The increase in the TBA molar part in the copolymer is followed by faster consumption of nitrile groups and the evolution of a ladder structure in both binary and ternary copolymers. Thus, the incorporation of a certain amount of TBA in PAN or its copolymer with BA allows tuning the temperature range of cyclization. This feature seems attractive for applications in the production of melt-spun PAN by choosing the appropriate copolymer composition and heating mode.

Al(SO4)(OH)·5H2O Stemming from Complexation of Aluminum Sulfate with Water-Soluble Ternary Copolymer and further Stabilized by Silica Gel as Effective Admixtures for Enhanced Mortar Cementing.

A water-soluble ternary copolymer bearing carboxyl, sulfonic, and amide functional groups was synthesized using ammonium persulfate-catalyzed free radical polymerization in water, resulting in high monomer conversion. This copolymer was then complexed with aluminum sulfate, forming an admixture containing Al(SO4)(OH)·5H2O, which was subsequently combined with silica gel. Characterization revealed that the synthesized copolymer formed a large, thin membrane that covered both the aluminum compounds and the silica gel blocks. The introduction of this complex admixture, combining the copolymer and aluminum sulfate, not only reduced the setting times of the cement paste but also enhanced the mechanical strengths of the mortar compared to using aluminum sulfate alone. The complex admixture led to the formation of katoite, metajennite, and C3A (tricalcium aluminate) in the mortar, demonstrating significant linking effects, whereas pure aluminum sulfate could not completely transform C3S within 24 h. Further addition of silica gel to the complex admixture further shortened the setting times of the paste, slightly reduced compressive strength, but improved flexural strength compared to the initial complex admixture. The silicon components appeared to fill the micropores and mesopores of the mortar, accelerating cement setting and enhancing flexural strength, while slightly decreasing compressive strength. This study contributed to the development of new cementing accelerators with improved hardening properties.

The Coordination of Aluminum Sulfate with a Water-Soluble Block Copolymer Containing Carboxyl, Amide, Sulfonic and Anhydride Groups Providing Both Accelerating and Hardening Effects in Cement Setting

Two water-soluble block copolymers composed of acrylic acid (AA), 2-acrylamido-2-methylpropane sulfonic acid (AMPS), and optionally maleic anhydride (MAH) were synthesized through ammonium persulfate-catalyzed free radical polymerization in water. The introduction of aluminum sulfate (AS) into the resulting mixtures significantly reduced the setting times of the paste and enhanced the mechanical strength of the mortar compared to both the additive-free control and experiments facilitated solely by pure AS. This improvement was primarily attributed to the inhibition of rapid Al3+ hydrolysis, which was achieved through coordination of the synthesized block copolymers, along with the formation of newly identified hydrolytic intermediates. Notably, the ternary copolymer (AA–AMPS–MAH) exhibited superior performance compared to that of the binary copolymer (AA–AMPS). In the early stages of cement setting, clusters of ettringite (AFt) were found to be immobilized over newly detected linkage phases, including unusual calcium silicate hydrate and epistilbite. In contrast to the well-documented role of polymers in retarding cement hydration, this study presents a novel approach by providing both accelerating and hardening agents for cement setting, which has significant implications for the future design of cement additives.

Synthesis, performance and application of environmental protection scale inhibitorβ-CD-MA-SSS copolymer——in electric power industry

The issue of water scaling in the treatment of cooling water has become an imperative problem that should be solved urgently for the sake of safe operation in large-scale flexible DC converter stations. However, the coexistence of Ca2+ and Mg2+ in high content in this sort of pending raw water is quite hard to tackle. β-CD-MA-SSS, an eco-friendly ternary co-polymer antiscalant with good performance of inhibiting the formation of scale, was applied to address this conundrum in this paper. The efficacy of the antiscalant β-CD-MA-SSS was investigated in cooling water systems under the conditions of low hardness, low alkalinity, a temperature not exceeding 80 °C, and a pH range of 6–8. After optimization, this reagent dem onstrated an excellent scale inhibition rate up to 80% for both calcium carbonate and calcium-magnesium mixed scales. Scanning electron microscopy (SEM) analysis revealed a noticeable reduction in the size of CaCO3 particles when subjected to the action of β-CD-MA-SSS. It was postulated from FTIR analysis that nanoinpurity and chelation effects mainly contributed to the mixed scale inhibition. Further, the effect of β-CD-MA-SSS on the actual production wastewater was comprehensively evaluated from the technical, economic and environmental aspects.

Synthesis and evaluation of a novel ternary quaternary ammonium salts-fluorescent template copolymer: Integrating flocculation, sterilization, and monitoring functions

Developing flocculants with sterilization and monitoring functions is of practical significance for optimizing water treatment agents. In this research, a fluorescent monomer, EtFl, with double bonds was synthesized and copolymerized with acrylamide (AM) and 3-(methacryloyloxy)propyltrimethylammonium chloride (MAPTAC) using a linear anionic template agent. This synthesis successfully produced a multifunctional template copolymer, TP(AM-MAP-EtFl), with flocculation, sterilization and monitoring capabilities. The fluorescence intensity of TP(AM-MAP-EtFl) was measured using a fluorescence spectrophotometer, demonstrating strong performance even with an EtFl monomer mass fraction as low as 0.5 wt‰, resulting in a fluorescence intensity value of 1000 a.u., suitable for analytical detection. In flocculation experiments with simulated wastewater containing E. coli, the introduction of the fluorescent monomer did not affect E. coli flocculation. When flocculation conditions are optimized, the OD600 readings of the clear liquid remaining after treating with TP(AM-MAP-EtFl#0.5) and TP(AM-MAP-EtFl#5) are 0.0297 and 0.0457, respectively, illustrating superior sterilization effects. Interestingly, SEM and 3D-EEM results confirmed TP(AM-MAP-EtFl)’s bactericidal effect on E. coli, with the introduction of the fluorescent monomer not affecting the sterilization capability of quaternary ammonium. This work integrates flocculation, sterilization and fluorescence properties to provide sterilization-type flocculants with monitoring capabilities, enabling accurate calculation of polymer concentration by detecting solution fluorescence intensity, thereby offering potential for online detection and automatic control of water treatment systems, demonstrating good applicability.

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.

Deciphering and Integrating Functionalized Side Chains for High Ion‐Conductive Elastic Ternary Copolymer Solid‐State Electrolytes for Safe Lithium Metal Batteries

AbstractA critical challenge in solid polymer lithium batteries is developing a polymer matrix that can harmonize ionic transportation, electrochemical stability, and mechanical durability. We introduce a novel polymer matrix design by deciphering the structure‐function relationships of polymer side chains. Leveraging the molecular orbital‐polarity‐spatial freedom design strategy, a high ion‐conductive hyperelastic ternary copolymer electrolyte (CPE) is synthesized, incorporating three functionalized side chains of poly‐2,2,2‐Trifluoroethyl acrylate (PTFEA), poly(vinylene carbonate) (PVC), and polyethylene glycol monomethyl ether acrylate (PEGMEA). It is revealed that fluorine‐rich side chain (PTFEA) contributes to improved stability and interfacial compatibility; the highly polar side chain (PVC) facilitates the efficient dissociation and migration of ions; the flexible side chain (PEGMEA) with high spatial freedom promotes segmental motion and interchain ion exchanges. The resulting CPE demonstrates an ionic conductivity of 2.19×10−3 S cm−1 (30 °C), oxidation resistance voltage of 4.97 V, excellent elasticity (2700 %), and non‐flammability. The outer elastic CPE and the inner organic–inorganic hybrid SEI buffer intense volume fluctuation and enable uniform Li+ deposition. As a result, symmetric Li cells realize a high CCD of 2.55 mA cm−2 and the CPE‐based Li||NCM811 full cell exhibits a high‐capacity retention (~90 %, 0.5 C) after 200 cycles.

Deciphering and Integrating Functionalized Side Chains for High Ion-Conductive Elastic Ternary Copolymer Solid-State Electrolytes for Safe Lithium Metal Batteries.

A critical challenge in solid polymer lithium batteries is developing a polymer matrix that can harmonize ionic transportation, electrochemical stability, and mechanical durability. We introduce a novel polymer matrix design by deciphering the structure-function relationships of polymer side chains. Leveraging the molecular orbital-polarity-spatial freedom design strategy, a high ion-conductive hyperelastic ternary copolymer electrolyte (CPE) is synthesized, incorporating three functionalized side chains of poly-2,2,2-Trifluoroethyl acrylate (PTFEA), poly(vinylene carbonate) (PVC), and polyethylene glycol monomethyl ether acrylate (PEGMEA). It is revealed that fluorine-rich side chain (PTFEA) contributes to improved stability and interfacial compatibility; the highly polar side chain (PVC) facilitates the efficient dissociation and migration of ions; the flexible side chain (PEGMEA) with high spatial freedom promotes segmental motion and interchain ion exchanges. The resulting CPE demonstrates an ionic conductivity of 2.19×10-3 S cm-1 (30 °C), oxidation resistance voltage of 4.97 V, excellent elasticity (2700 %), and non-flammability. The outer elastic CPE and the inner organic-inorganic hybrid SEI buffer intense volume fluctuation and enable uniform Li+ deposition. As a result, symmetric Li cells realize a high CCD of 2.55 mA cm-2 and the CPE-based Li||NCM811 full cell exhibits a high-capacity retention (~90 %, 0.5 C) after 200 cycles.

Economic and environmentally friendly anionic flocculant synthesized by starch-acrylic acid-itaconic acid grafting and efficient treatment of cationic dye wastewater

Starch-based flocculants are environmentally friendly and high-performance products, potentially applied in wastewater treatment with low operation cost and ecological risk. In this study, we successfully synthesized a ternary anionic copolymer of starch-acrylic acid-itaconic acid (SAI) through graft copolymerization. The synthesis conditions were optimized based on flocculation efficiency against cationic crystal violet (CV), and subsequent applicability was conducted under various environmental conditions. The results indicate that SAI exhibited outstanding decolorization efficiency under wide scopes of pH, temperature, and ionic strength. Most importantly, SAI achieved a remarkable decolorization rate of 91.2 % for 100 mg/L CV dye at a low concentration of 25 mg/L, accounting for one-fourth of the cost operated with commercial polyacrylamide. Compared to binary flocculants, SAI demonstrates superior flocculation performance too. The flocculation mechanism is primarily attributed to the combined effects of charge neutralization, bridging, and sweeping. SAI flocculants possess characteristics of high efficiency, environmental friendliness, and cost-effectiveness, thus presenting broad prospects for the treatment of dye wastewater.

Facile preparation and application of ternary hybrid of POSS/DOPO/F macromolecular as highly-effective epoxy modifier

In order to easily achieve the multifunctionality of epoxy resin, this paper designs and synthesizes a ternary hybrid copolymer containing POSS/DOPO/F. This method not only facile combines POSS with DOPO, but also introduces F element to further reduce the surface energy of epoxy composite materials. Research has found that the POSS/DOPO/F ternary hybrid copolymer can achieve a UL-94 flame retardant rating of V-0 with just 5 wt% of the modifier, and the limit oxygen index of epoxy composites is 32% (23.1% higher than pure epoxy resin). The residual char after combustion is denser and the carbonization rate is higher. Furthermore, we conducted an in-depth analysis of the flame retardant mechanism of POSS/DOPO/F ternary hybrid copolymer epoxy composites using TGA-FTIR technology and EDS. In addition, the introduction of ternary hybrid polymers effectively improves the mechanical properties of epoxy composite materials and significantly reduces the surface energy of the composite materials.

Versatile preparation of jellyfish-inspired color transition hydrogels via polymerization induced supramolecular geletion (PISG)

Supramolecular hydrogels based on host–guest interactions constitute a class of intriguing soft matter and have attracted great attention due to their unique properties, etc. In this study, we successfully synthesized 4-methylene-7-diethylaminocoumarin methacrylate (DEACMMA) monomer and carried out reversible addition-fragmentation chain transfer (RAFT) polymerization using methylated β-cyclodextrin via a host-guest encapsulation mechanism. This process led to the formation of ternary copolymer hydrogel supramolecular photoresponsive hydrogels through polymerization induced supramolecular gelation (PISG). The encapsulation of coumarin monomers by methylated cyclodextrins was confirmed using 2D ROESY NMR and fluorescence spectroscopy. We have carefully analyzed the microstructure of these supramolecular hydrogels by rheological profiles and scanning electron microscopy (SEM). Stimulated by UV light, the copolymers transition from non-luminescence to a bright fluorescent blue color, which is reminiscent of the self-transforming colors observed in jellyfish. The development of photostimuli-responsive hydrogels based on methylated β-cyclodextrin-coated coumarin esters opens new avenues in the fields of smart materials and clinical medicine.

Constructing the Polymer Molecules to Regulate the Electrode/Electrolyte Interface to Enhance Lithium-Metal Battery Performance.

Lithium-ion batteries, with high energy density and long cycle life, have become the battery of choice for most vehicles and portable electronic devices; however, energy density, safety and cycle life require further improvements. Single-functional group electrolyte additives are very limited in practical applications, a ternary polymer bifunctional electrolyte additive copolymer (acrylonitrile-butyl hexafluoro methacrylate- poly (ethylene glycol) methacrylate- methyl ether) (PMANHF) was synthesized by free radical polymerization of acrylonitrile, 2, 2, 3, 4, 4, 4-hexafluorobutyl methacrylate and poly (ethylene glycol) methyl ether methacrylate. A series of characterizations show that in Li metal anodes, the preferential reduction of PMANHF is conducive to the formation of a uniform and stable solid electrolyte interphase layer, and Li deposition is uniform and dense. At the NCM811 cathode, a film composed of LiF- and Li3N-rich is formed at the cathode-electrolyte interface, mitigating the side reaction at the interface. At 1.0 mA cm-2, the Li/Li cell can be stabilized for 1000 cycles. In addition, the Li/NCM811 cell can stabilize 200 cycles with a cathode capacity of 153.7 mAh g-1, with the capacity retention of 89.93 %, at a negative/positive capacity ratio of 2.5. This study brings to light essential ideas for the fabrication of additives for lithium-metal batteries.

General Entropy Approach Toward Ultratough Sustainable Plastics.

Entropy is a universal concept across the physics of mixtures. While the role of entropy in other multicomponent materials has been appreciated, its effects in polymers and plastics have not. In this work, it is demonstrated that the seemingly small mixing entropy contributes to the miscibility and performance of polymer alloys. Experimental and modeling studies on over 30 polymer pairs reveal a strong correlation between entropy, morphology, and mechanical properties, while elucidating the mechanism behind: in polymer blends with weak interactions, entropy leads to homogeneously dispersed nanosized domains stabilized by highly entangled chains. This unique microstructure promotes uniform plastic deformation at the interface, thus improving the toughness of conventional brittle polymers by 1-2 orders of magnitude without sacrificing other properties, analogous to high-entropy metallic alloys. The proposed strategy also applies to ternary polymer systems and copolymers, offering a new pathway toward the development of sustainable polymers.

Synthesis of modified silica nano as plugging agent for drilling fluid

There are a large number of nano-micron pores on the surface of the rock layer, and during the drilling process, water molecules will penetrate into the formation through these nano-micron pores, causing hydration and expansion of the rock, causing instability of the wellbore and other problems. Nano-micron plugging agents can effectively seal the nano-micron pores in the formation, reducing the hydration and expansion of the formation. This paper synthesized the ternary copolymer (AAK) using modified nano silica (KH-570), acrylamide (AM), and 2-acrylamide-2-methyl-1-propane sulfonic acid (AMPS) as raw materials, and used it as a plugging agent in water-based drilling fluids. The characterization and performance of AAK were studied using Fourier transform infrared spectroscopy, particle size analyzer, transmission electron microscopy, and thermogravimetric experiments. The plugging performance was evaluated using microporous filter membrane temperature and pressure tests, liner swelling tests, immersion test, and contact angle tests. In addition, its tackiness and salt resistance were also tested. The results indicate that the particles of AAK are nanoscale particles, which can effectively seal the nano and micro pores in rock blocks. At the same time, AAK has good temperature and salt resistance. The addition of AAK does not significantly change the rheological properties of the drilling fluid and can be used as a plugging agent in water-based drilling fluids.

Study of the properties of compositions based on mixtures of butadiene-styrene rubber with mechanically modified ternary ethylene-propylene copolymer

Study of the properties of compositions based on mixtures of butadiene-styrene rubber with mechanically modified ternary ethylene-propylene copolymer

Precise design of copolymer-conjugated nanocatalysts for active electron transfer.

A copolymer-conjugated nanocatalytic system has been designed for active electron transfer. To enhance photoinduced H2 generation, we precisely synthesize ternary random copolymers capable of transferring electrons through phase transitions, extending and shrinking in response to viologen's redox changes within 2 nm distance from the surface of the catalytic nanoparticle.

Synthesis and performance evaluation of temperature and salt-resistant organic/inorganic composite copolymers

ABSTRACT Ordinary polymers have poor adaptability in high-temperature and high-salt reservoir environments due to their properties. Organic/inorganic composite copolymer microspheres have the advantages of both of them, which are expected to break through their applicability limitations in such oil reservoirs. Therefore, its preparation and performance have always been of great concern to researchers. In this paper, AM/AMPS/Si-St ternary copolymers were synthesized by precipitation polymerization; then modified nano-silica particles were added to synthesize AM/AMPS/Si-St/g-SiO2 organic/inorganic composite quaternary copolymers. FT-IR and SEM characterized the copolymers to confirm that they were prepared successfully. Experiments were carried out to investigate the concentration and ratio of monomers, which showed that the Weissenberg effect could be avoided. The number of polymer molecules could be stabilized under AM concentration of 12 wt%, AM/AMPS/Si-St ratio of 8:1:1, nano silica of 3.3% and the modification conditions of KH570:SiO2 = 1:1. The experiments of temperature and salt resistance of two copolymers were evaluated and compared were conducted by using viscosity and particle size as parameters. The results showed that quaternary copolymers could increase the viscosity retention rate by about 10% compared with ternary copolymers under high content of Na+ and Mg2+. When the two copolymers were placed at 150°C, the appearance and morphology of the terpolymer changed obviously. Through the SEM image of the quaternary copolymers, it could be seen that although the spherical shape of the microsphere had been gradually lost, no degradation occurred, and the stable time of the modified microspheres had been effectively extended.

Preparation and displacement performance of ternary copolymer (HAPEC)/graphene oxide composites

How to deal with high temperature and high salt reservoirs is a great challenge in the field of polymers. In this paper, a functional monomer (APEC) was homemade, copolymerized with acrylic acid and acrylamide to form a terpolymer, and solution blended with graphene oxide (GO) to prepare a terpolymer/graphene oxide composite (HAPEC/GO). The optimal ratio HAPEC/GO = 20:1 (GH20) was screened. The synthesized materials were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance hydrogen spectroscopy (1H NMR), and electron microscopy (SEM). The temperature sensitivity, salt resistance, rheology, and aging resistance of GH20 were found to be superior to hydrolyzed polyacrylamide (HPAM), as evaluated by the apparent viscosity of the solution. When tested under simulated water conditions of 90 °C and 1.0 × 105 mg/L total mineralization, the GH20 solution demonstrated a further improvement in recovery, reaching 16.99 % compared to water flooding alone. The final recovery was 7.49 % higher than that of HPAM. The results demonstrate that the composite prepared can be effectively utilized in reservoirs with high temperature and high salt conditions, making it a promising method for enhanced oil recovery.