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Comprehensive Summary: Discovery of unprecedented donor‐acceptor patterns can essentially enrich the chemistry of donor‐acceptor cyclopropanes. We herein introduce a concept of vinylogous fluorine stabilizing effect, which guides rational design of a novel donor‐acceptor cyclopropane employing gem‐difluorovinyl group as the electron donor, namely dFVCP. Application of such dFVCPs in a [3+2] cycloaddition with aldehydes and a controlled ring‐opening polymerization by a Mg(OTf)2/DIPEA/C(sp3)‐H initiator system have been demonstrated, providing direct access to fluorine‐containing tetrahydrofurans and all‐carbon main‐chain polymers. [ABSTRACT FROM AUTHOR]

A flexible, shape-editable transparent wood (ATW) composite containing acetal linkages was prepared simultaneously through free radical polymerization and addition reaction between vinyl ether bonds and hydroxyl groups. In this system, the anisotropic hierarchical structure of wood acted as a reinforced skeleton, the flexible chain segment ensured flexibility at room temperature, and the dynamic acetal bonds were responsible for the shape memory and editability under relatively mild conditions, verifying the expanding applications of functionalized wood-based materials. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Discovery of unprecedented donor‐acceptor patterns can essentially enrich the chemistry of donor‐acceptor cyclopropanes. We herein introduce a concept of vinylogous fluorine stabilizing effect, which guides rational design of a novel donor‐acceptor cyclopropane employing gem‐difluorovinyl group as the electron donor, namely dFVCP. Application of such dFVCPs in a [3+2] cycloaddition with aldehydes and a controlled ring‐opening polymerization by a Mg(OTf)2/DIPEA/C(sp3)‐H initiator system have been demonstrated, providing direct access to fluorine‐containing tetrahydrofurans and all‐carbon main‐chain polymers. [ABSTRACT FROM AUTHOR]

Through anionic two‐stage polymerization, block‐type styrene‐butadiene rubber (SSBR) with systematically regulable low‐temperature loss peaks is successfully prepared. The influence of 1,2‐Bd unit in the soft segment of block‐type SSBR on mechanical properties, dynamic mechanical properties, and microscopic morphology is studied, while pressure factors are introduced into dynamic mechanical studies. The block‐type SSBR with a soft segment containing 21.9 wt% of 1,2‐Bd exhibits the highest tensile strength, elongation at break, and tear strength. Under atmospheric pressure, the soft segment 1,2‐Bd unit influences the dynamic mechanical properties by altering the chain segment's motion loss capability. As the mass fraction of 1,2‐Bd increases from 21.9 to 58.6 wt%, tanδmax increases, the glass transition temperature of the soft segment increases from −59.0 to −18.9°C. Additionally, influenced by thermodynamic compatibility, the microscopic morphology transitions from strong separation to weak separation. Pressure affects dynamic mechanical properties by altering the free volume of the chain segments. Pressure reduces tanδmax, increases Tg, and raises the average Tg of the soft segment by 11°C. The K value of the linear equation representing the relationship between the soft segment Tg and the mass fraction of 1,2‐Bd is unaffected by pressure. [ABSTRACT FROM AUTHOR]

To explore the influence of reaction medium on the copolymerization behavior of acrylamide‐based copolymers, three types of copolymers (P(AM‐St)(ILs), P(AM‐MMA)(ILs), and P(AM‐AMPS)(ILs)) were synthesized by combining insoluble, slightly soluble, and easily soluble monomers with acrylamide in the 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([BMIM]BF4) reaction medium. The reactivity ratio, Fourier transform infrared spectroscopy, 1H NMR spectroscopy, elemental analysis, and scanning electron microscopy were employed to characterize the copolymers' properties. The results indicated that in [BMIM]BF4 copolymerization, the reactivity ratio of AM and St in P(AM‐St)(ILs) decreased, the reactivity ratio of AM in P(AM‐MMA)(ILs) will increase. While the reactivity ratio of MMA will decrease. The reactivity ratio of AM in P(AM‐AMPS)(ILs) will increase and the reactivity ratio of AMPS will decrease. The distribution of AM and St segments in P(AM‐St)(ILs) molecular chains is more uniform and compact. When AM polymerizes with hydrophobic monomers (St) in [BMIM]BF4, its copolymer solution exhibits lower viscosity loss rates in temperature, shear, and salt resistance tests. Therefore, ionic liquids are more suitable as reaction media for the synthesis of hydrophobic‐modified polyacrylamides, which facilitate a more uniform distribution of hydrophobic monomers within the copolymer chains and exhibit enhanced resistance to temperature, salt, and shear stresses. [ABSTRACT FROM AUTHOR]

'On‐water' catalysis entails the significant enhancement of a chemical reaction by water, even when those reactions are known to be water‐sensitive. Here, the findings about the anionic ring opening polymerization of epoxides at the static interface between oil and alkaline water are shared. Unexpectedly, high molar mass fractions are observed with the interfacial system presented herein, albeit at very low conversions (< 5%). Styrene oxide, a notably unreactive epoxide, is chosen as the model compound to investigate the influence of several reaction parameters (i.e., pH, type of the initiator salt, polymerization time, interfacial area, solvent, shaking) on the polymerization. Poly(styrene oxide) (PSO) with an Mn of 5300 g mol−1 is observed via MALDI‐ToF MS, with species of at least 8000 g mol−1. The feasibility of expanding the system to (cyclic) aliphatic and aromatic epoxides, and glycidyl ethers is also explored. The system appears to promote polymerization of epoxides that position at the interface, in such a way that initiation and propagation can occur. A mechanistic interpretation of the interfacial polymerization is suggested. The surprising results obtained in this work urge to revisit the role of water in ionic polymerizations. [ABSTRACT FROM AUTHOR]

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo‐)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain‐growth photopolymerization with the thermally initiated anionic step‐growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step‐growth polymerization. Resulting from curing above the TG of the respective anionic step‐growth polymer, materials with outstanding tensile toughness (>5 MJ cm−3) are obtained that result in the manufacture of potential shape‐memory polymers. [ABSTRACT FROM AUTHOR]

Rendering established antibiotics by derivatization or formulation is a promising way to quickly obtain higher active antibiotics and to address antibiotic resistant bacterial strains. The antibiotic ciprofloxacin (CIP) conjugated with amphiphilic blockcopoly(2-oxazoline)s (POx) shows greatly enhanced antimicrobial activity, reduces resistance formation, and is active against CIP-resistant bacterial cells with overexpressed efflux pumps. In order to design CIP conjugates with comparable performance, but higher biocompatibility, the hydrophobic POx-block was substituted by a modified α -Tocopherol (VitE), which is predominantly referred to as vitamin E. Modification of VitE with 4-bromomethylbenzoyl bromide leads to a highly active initiator for POx synthesis. Using this initiator for the living cationic polymerization of 2-methyl-2-oxazoline leads to fully end-group functionalized PMOx. Conjugation of these polymers with CIP results in non-cytotoxic conjugates with improved CIP activity. These VitE-PMOx-EDA-xCIP conjugates enter E. coli cells via their efflux pumps. In case of E. coli with overexpressed efflux pumps (typical for resistant bacteria), the molar activity of the novel CIP conjugates is up to 100 times higher than free CIP, indicating potential of polymer conjugation with antibiotics to overcome bacterial resistances. [ABSTRACT FROM AUTHOR]

Improvement of mechanical stability for porous polymer monoliths is one of the prime concerns as represented by the long‐standing research efforts on resorcinol‐formaldehyde (RF) aerogels. To this end, it is imperative not only to tailor mechanically robust porous morphology but also to design macromolecular structure of polymer scaffolds. Previously, we have developed porous RF gels showing a unique mechanical feature combining high mechanical strength and outstanding flexibility against uniaxial compression. Comparison of mechanical properties between the porous gels with varied morphologies has elucidated the influence of porous structure, whereas effects of macromolecular structure still remain elusive. Herein, we have fabricated a series of macroporous phenolic resins from three types of linear prepolymers with phenol pendant groups, poly(4‐vinylphenol) or poly(4‐hydroxystyrene), which differ in molecular‐weight properties, by the sol–gel process in conjunction with spinodal decomposition. The difference in gelation and phase separation behaviors observed for the discrete systems indicates the dissimilar cross‐linked networks developed in the respective gels, which consequently influence the mechanical strength and flexibility against uniaxial compression. This study also demonstrates the improvement of mechanical features by thermal treatment for the porous monoliths derived from the high‐molecular‐weight prepolymer with a view to the application in mechanical energy absorption. [ABSTRACT FROM AUTHOR]

Fluorosilicone rubber is essential for sealing in extreme temperatures and non‐polar environments due to its exceptional adaptability. However, achieving a high yield of fluorosilicone polymers with medium and high fluorine content remains a challenge. Herein, a facile gradient strategy is developed that involves modifying the method of cyclic monomer addition based on the rate of ring‐opening polymerization (ROP), to improve yield and adjust fluorine content precisely. The polymerization process is designed and tailored based on the reaction rates of anionic ring‐opening polymerization (AROP) and cationic ring‐opening polymerization (CROP) via an efficient gradient strategy. The effects of the polymerization process on the viscosity and yield of vinyl fluorosilicone polymers and hydrofluorosilicone polymers are investigated and optimized. Notably, the as‐prepared vinyl‐terminated fluoromethylsilane with 60% fluorine content (FMS‐Vi‐60F) has a high yield (86.6%) and high viscosity (150 000 mPa·s) in a short reaction time, which is superior to previous methods. Clearly, the gradient ring‐opening method developed in this work provides a facile and efficient synthesis for fabricating fluorosilicone polymers with a high yield and tunable fluorine content. [ABSTRACT FROM AUTHOR]

Living cationic ring‐opening polymerization accompanied by isomerization of cyclic imino ethers is performed at high temperatures that provide access to the synthesis of self‐organizable systems in their isotropic melt or solution state. This Perspective discusses fundamental mechanistic principles of this polymerization and bridges with the polymerization of dendronized cyclic iminoethers forming polymers that self‐organize soft Frank–Kasper and quasicrystal periodic and quasiperiodic arrays. These two fields represent frontiers in macromolecular and supramolecular science. A brief discussion of the impact of this polymerization on biomaterials and how it impacted contemporary mechanistic investigations is also made. Expected impacts via future synthetic developments and mechanistic investigations are discussed. [ABSTRACT FROM AUTHOR]

Liquid crystalline elastomers (LCEs) are a class of shape‐changing polymers with exceptional mechanical properties and potential as artificial muscles/polymer actuators. In this study, multifunctional LCE actuators with strain sensing and joule heating responsivity are developed. LCEs are successfully synthesized using the thiol‐ene two‐staged michael addition polymerization (TMAP) method. The LCE films are further functionalized via sequential polydopamine (PDA) and silver electroless coating. It is found that the PDA coating enabled the anchoring of the Ag particles to the LCE, thereby enabling the electrical conductivity of the Ag‐LCEs (<0.1 Ω cm−1). The studies confirm that the Ag/PDA coated LCEs can sense up to ≈30% strain, sense their own actuation strokes, and actuate at a rate of 1.83% s−1 while lifting a weight ≈50 times its mass in response to a 12 V 2A DC current. [ABSTRACT FROM AUTHOR]

Cycloaliphatic epoxides exhibit post‐light irradiation heat‐induced polymerization, creating warp‐resistant green bodies during sintering. However, their use in light polymerization three‐dimensional (3D) printing is limited by slow photo‐curing speeds. In this study, a photo‐cationic polymerizable ceramic slurry was developed for 3D printing by mixing oxetane with cyclo‐aliphatic epoxide. This mixture improved photo‐curing speed, reduced resin viscosity, and enhanced the ceramic slurry's solid content. Additionally, we optimized the slurry by considering the specific and content ratio of photosensitizers and light absorbers. The optimized slurry polymerized unreacted functional groups in the polymer, improving the fracture strength of the green bodies through enhanced crosslinking density and uniformity in each layer. Ultimately, a sintered body without warpage was produced by the improved green bodies. This approach provides a solution related to controlling the photocuring speed and expands the potential applications of 3D printing in areas where the precision and stability of the printing material are required. [ABSTRACT FROM AUTHOR]

A novel synthetic pathway for synthesizing isocyanate-free polyurethanes is reported here. β-Amino alcohols were efficiently synthesized from the aminolysis of the epoxide ring of (R)-(+)-limonene oxide with different primary amines as nucleophiles and hot water as catalysts. The regio- and diastereoselectivities of the reactions were investigated and supported by computational studies. DFT calculations were performed to understand the experimental results more deeply. It confirmed the crucial roles of water molecules and the nature of the nucleophile in forming the products. The formation of the product is entirely driven by the free energy of activation that affects the reaction rate. Cyclic carbamates were prepared from β-amino alcohols using the dialkyl carbonate (DAC) chemistry. An oligourethane was obtained from Anionic Ring-Opening Polymerization (AROP) of a cyclic carbamate derived from (R)-(+)-limonene-oxide. All the products were characterized by employing 1H and 13C NMR spectroscopies. The assignments of the signals in 1H and 13C NMR spectra were also supported by 2D NMR spectroscopy. [ABSTRACT FROM AUTHOR]

The exothermic nature of acrylate photopolymerizations enables room temperature 3D printing of a quaternary formulation that incorporates an acrylate monomer, and an epoxy/thiol‐ene system (ETES). The latter comprises an epoxy monomer, a multifunctional thiol and a tetraallyl functionalized ditertiary amine curing agent. Pristine ETES necessitates temperatures of 85–95 °C for curing. Several mechanisms operate simultaneously during this process: homopolymerization of acrylates, thiol‐acrylate photopolymerization, thiol‐ene photopolymerization between the double bonds of curing agent and the multifunctional thiol, the Michael addition between thiolates derived from ETES and the double bonds of acrylates, and the anionic polymerization of the epoxy resin via the tertiary amine groups. To optimize the quaternary formulations for printing, parameters, such as reactivity, exothermicity, and viscosity, was explored. Subsequently, the thermal and viscoelastic properties of the printed cross‐linked polymers derived from these formulations were analyzed using Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA) and Thermogravimetric Analysis (TGA). The polymers derived from quaternary formulations exhibited lower crosslinked density compared to those obtained from the pristine acrylates. This reduction in crosslink density contributes to the improved toughness of the hybrid polymers. [ABSTRACT FROM AUTHOR]

In pursuit of high energy density, lithium metal batteries (LMBs) are undoubtedly the best choice. However, leakage and inevitable dendrite growth in liquid electrolytes seriously hinder its practical application. Solid/quasi‐solid state electrolytes have emerged as an answer to solve the above issues. Especially, polymer electrolytes with excellent interface compatibility, high flexibility, and ease of machining have become a research hotspot for LMBs. Nevertheless, the interface contact between polymer electrolyte and inorganic electrode materials and the low ionic conductivity restrict its development. On account of these, in situ polymerized polymer electrolyte is proposed. Polymer solid electrolytes produced through in situ polymerization promote robust interface contact between the electrolyte and electrode while simplifying the preparation steps. This review summarized the latest research progress in in situ polymerized solid electrolytes for LMBs. These electrolytes were divided into three parts according to their polymerization methods: thermally induced polymerization, chemical initiator polymerization, ionizing radiation polymerization, and so on. Furthermore, we concluded the major challenges and future trends of in situ polymerized solid electrolytes for LMBs. It's hoped that this review will provide meaningful guidance on designing high‐performance polymer solid electrolytes for LMBs. [ABSTRACT FROM AUTHOR]

The extensive utilization of plastic, as a symbol of modern technological society, has consumed enormous amounts of finite and non-renewable fossil resources and produced huge amounts of plastic wastes in the land or ocean, and thus recycling and reuse of the plastic wastes have great ecological and economic benefits. Closed-loop recyclable polymers with inherent recyclability can be readily depolymerized into monomers with high selectivity and purity and repolymerized into polymers with the same performance. They are deemed to be the next generation of recyclable polymers and have captured great and increasing attention from academia and industry. Herein, we provide an overview of readily closed-loop recyclable polymers based on monomer and polymer design and no-other-reactant-involved reversible ring-opening and addition polymerization reactions. The state-of-the-art of circular polymers is separately summarized and discussed based on different monomers, including lactones, thiolactones, cyclic carbonates, hindered olefins, cycloolefins, thermally labile olefin comonomers, cyclic disulfides, cyclic (dithio) acetals, lactams, Diels–Alder addition monomers, Michael addition monomers, anhydride–secondary amide monomers, and cyclic anhydride–aldehyde monomers, and polymers with activatable end groups. The polymerization and depolymerization mechanisms are clearly disclosed, and the evolution of the monomer structure, the polymerization and depolymerization conditions, the corresponding polymerization yield, molecular weight, performance of the polymers, monomer recovery, and depolymerization equipment are also systematically summarized and discussed. Furthermore, the challenges and future prospects are also highlighted. [ABSTRACT FROM AUTHOR]

The propagation rate coefficient (kp) is one of the most crucial kinetic parameters in free-radical polymerization (FRP) as it directly governs the rate of polymerization and the resulting molecular weight distribution. The kp in FRP can typically be obtained through experimental measurements or quantum chemical calculations, both of which can be time consuming and resource intensive. Herein, we developed a machine learning model based solely on the structural features of monomers involved in FRP, utilizing molecular embedding and a Lasso regression algorithm to predict kp more efficiently and accurately. The result shows that the model achieves a mean absolute percentage error (MAPE) of only 5.49% in the predictions for four new monomers, which indicates that the model exhibits strong generalization capabilities and provides reliable and robust predictions. In addition, this model can accurately predict the influence of the ester side chain length of (meth)acrylates on kp, aligning well with established scientific knowledge. This approach offers a straightforward and practical model for other researchers to rapidly obtain accurate kp values by employing monomer structural information. The model is sufficiently general to apply to a wide range of (meth)acrylate and butadiene FRP monomers, thereby supporting kinetic modeling of polymerization reactions. [ABSTRACT FROM AUTHOR]

Thermal frontal polymerization (FP) of acrylate monomers mixed with conventional peroxide initiators leads to significant bubble formation at the polymerizing front, limiting their practical applications. Redox initiators present a promising alternative to peroxide initiators, as they prevent the formation of gaseous byproducts during initiator decomposition and lower the front temperature, thereby enabling bubble-free FP. In this study, we investigate the FP of acrylate monomers of varying functionalities, including methyl methacrylate (MMA), 1,6-hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate (TMPTA), using N,N-dimethylaniline/benzoyl peroxide (DMA/BPO) redox couple at room temperature and compare their front behavior, pot life, and bubble formation with those of same resin systems mixed with a conventional peroxide initiator, Luperox 231. The use of redox couples in FP of acrylates shows promise for rapid, energy-efficient manufacturing of polyacrylates and can enable new applications such as 3D printing and composite manufacturing. [ABSTRACT FROM AUTHOR]

Driving a car at extreme speeds, road holding, and sustainability do not go together well. Formula 1 racing is exciting but is not an example of sustainability. The aim of this work was to use materials, suitable for the treads of high-performance racing tyres, that can favour both high performance and sustainability. In particular, the objective was to achieve high dynamic rigidity at high temperatures (>100 °C) and a stable crosslinking network. A copolymer from an industrial waste such as sulphur and a comonomer from a circular biosourced material were used as the crosslinking agent of an elastomer composite based on poly(styrene-co-butadiene) from solution anionic polymerization and a carbon black with a high surface area. The biosourced circular material was 1,6-bis(2,5-dimethyl-1H-pyrrol-1-yl)hexane (HMDP), the di-pyrrole derivative of hexamethylenediamine. Two poly(S-co-HMDP) copolymers, with different S/HMDP ratios (6 and 8.9, Copolymer 1 and Copolymer 2) were carefully characterized by means of 1H-, 13C-, 2D1H-1H-COSY and 2D 1H-13C HSQC NMR. The comparison of the spectra highlighted the substitution with sulphur of the β-position of the pyrrole ring: mono-substitution largely prevailed in Copolymer 1 and also bi-substitution in Copolymer 2. The copolymers were used as additives in the vulcanization system. Compared with a reference composite, they allowed us to achieve more efficient vulcanization, a higher density of the crosslinking network, higher dynamic rigidity, better ultimate tensile properties, and better stability of the crosslinking network at high temperatures. Compared with a traditional oil-based crosslinking agent for elastomer composites with high rigidity and a stable structure at high temperatures, such as the perthiocarbamate 6-((dibenzylcarbamothioyl)disulfaneyl)hexyl 1,3-diphenylpropane-2-sulfinodithioate, the poly(S-co-HMDP) copolymers led to higher dynamic rigidity and better ultimate tensile properties. These improvements occurring simultaneously are definitely unusual. This work paves the way for the upcycling of circular materials in a large-scale application such as in tyres. [ABSTRACT FROM AUTHOR]

The high energy density of lithium metal batteries (LMBs) makes them a promising battery research target. However, the solid electrolyte interphase (SEI) instability causes dendrite formation/growth and short circuits. Electrolyte engineering can regulate the intrinsic properties of the SEI due to the composition and properties of the SEI strongly depend on the electrolyte component. In this work, 2,4,6,8‐tetramethyl‐2,4,6,8‐tetravinylcyclotetra‐siloxane (V4) is paired with vinyl‐triethoxy‐silane (VTEO) to obtain a novel ester‐based electrolyte additive. Decomposition of V4 molecules into silicon‐based polymer‐rich SEI on the Li metal anode surface has been predicted theoretically and verified experimentally. Through ─CH═CH2 addition polymerization on the preformed silicon‐based polymer layers which originates from the decomposition of V4, VTEO molecules can be integrated into SEI films due to their "molecular bridge" structure. The organic functional group (─OCH2CH3) on VTEO molecules promotes Li+ transport kinetics and forms Si─O─Li bonds under the presence of OH−, improving anode interface stability. The experimental results show that the cycle life of the LFP‐Li full batteries is over 1000 and 500 cycles at 5 C and 10 C, respectively. This research elucidates a reliable strategy for constructing SEI film with high adhesion and long‐term viability on the Li metal anode. [ABSTRACT FROM AUTHOR]

AbstractSpecifically, the conventional wood adhesive uses polyvinyl alcohol (PVA) as colloid to stabilise the polyvinyl acetate (PVAc) emulsion. Green materials are being used as a result of recent study on chemicals and alternative sources. This factor has made the substitution of sustainable biopolymers for petrochemicals considerably more important. An emulsifier, sodium lauryl sulphate (SLS), was used during the addition polymerization process to produce a hydroxyethyl cellulose-grafted-poly (vinyl acetate) (HEC-g-P(VAc)) emulsion from HEC and VAc. The purpose of the study was to increase the content of renewable materials in the emulsion. The adhesive films glass transition temperatures (Tg) have been identified via Differential Scanning Calorimetry (DSC). The performance of the PVAc emulsion-based adhesive in accordance with EN 204 and EN 205 standards was evaluated by measuring the tensile shear strength of wood joints under both dry and wet conditions. The viscosity of the adhesives significantly increased along with the addition of HEC. The application of HEC led to an increase in PVAc film hardness, which was confirmed by the film’s glass transition temperature. In an environment that was wet, after 24 h, the tensile strength of the sample containing HEC increased by 54% compared to a pristine sample, as per EN 204 and EN 205. Water resistance significantly increased in sample with HEC, as was found by measuring the water contact angle which is in line with wet strength. The overall study conclusion emphasises the superior water resistance and increased adhesion capabilities of PVAc emulsion-based wood adhesives stabilised by HEC. [ABSTRACT FROM AUTHOR]

The Tarim area, characterized by deep reservoirs, high temperatures, and limited fresh water resources, necessitates a fracturing fluid system that exhibits excellent temperature shear resistance, low friction, and salinity tolerance. This study presents the development of a zwitterionic hydrophobic polymer, HPC-5, as an effective thickener using five types of polymeric monomers, including AM, AA, DMC, AMPS, and a non-ionic hydrophobic monomer. The method employed for synthesis was free-radical polymerization in solution. A series of experiments including viscosity measurement with variation of salinity, solubility and drag reduction test, crosslinking test, thermal and shear resistance, sand-carrying test, gel breaking evaluation, and core damage test were conduct under the simulated reservoir conditions. The zwitterionic design imparts great salt tolerance to HPC-5, and the apparent viscosities of HPC-5 solutions can maintain comparably high values with 10×104 ppm NaCl and CaCl2 concentration. Meanwhile, the molecules of HPC-5 associate with each other to form tight net structures, resulting in an excellent viscoelasticity of the solution. To achieve high pump rate during hydraulic fracturing operation in ultra-deep reservoirs, the delayed crosslinking agent ZDC-L was prepared for forming a delayed crosslinking gel fracturing fluid system using reservoir brine, and the drag reduction rate can reach over 70% before crossing link within 4 min. Under pH = 4 conditions, the crosslinking time can be significantly delayed to over 4 min while maintaining exceptional temperature resistance up to 160 ℃ for the gel. These properties make it highly suitable for hydraulic fracturing operations in ultra-deep wells with temperatures reaching up to 7000 m depth at pump rates of 4~5m3/min. [ABSTRACT FROM AUTHOR]

In this work, blends of monomer‐cast polyamide 6 (MCPA6) and polyurethane (TPU) were prepared by in situ anionic ring‐opening polymerization using caprolactam as the monomer and sodium hydroxide (NaOH) as the initiator. TPU degraded under weakly alkaline conditions to form an isocyanate group, which acted as a macromolecule activator to initiate the growth of the MCPA6 chain, and the formation of TPU‐co‐MCPA6 copolymer in this system, which improves the compatibility between MCPA6 and TPU. The MCPA6/TPU blends were tested for conversion, viscosity, and mechanical properties, and their structures and thermal properties were analyzed and evaluated by characterization techniques such as Fourier transform infrared spectroscopy, differential scanning calorimetry, and scanning electron microscopy. [ABSTRACT FROM AUTHOR]

Simple and commercially available Lewis acids (LAs) are commonly used catalysts in anionic ring‐opening polymerization (AROP) reactions. In particular, for the AROP of epoxides, the addition of a Lewis acid allows the transition from a so‐called end‐chain mechanism to a monomer‐activated mechanism. The presence of the LA simultaneously leads to a decrease in the reactivity of active centers through the formation of a three‐species ate complex and to the activation of the monomer by LA coordination to the oxygen atom of the oxirane ring. These two effects result in both an increase in propagation kinetics and a decrease in transfer reactions, which has enabled the synthesis of high molecular weight polyethers. However, the impact of Lewis acids goes far beyond these classic effects. They have indeed enabled the polymerization of new functional monomers as well as the synthesis of heterotelechelic macromolecules. Also widely used as catalysts in copolymerization reactions (statistical, sequential, and alternating) Lewis acids can strongly influence the composition and sequence of monomer units in macromolecules. Finally, Lewis acids can also significantly influence the architecture of the obtained macromolecules. This review aims to list the various contributions of Lewis acids to macromolecular engineering and illustrate them with well‐chosen examples. [ABSTRACT FROM AUTHOR]

Using a novel technique, crosslinked gel polymer electrolytes (GPEs) designed for lithium-ion battery applications have been created. To form the photo crosslink via free-radical polymerization, a mixture of polyurethane acrylate (PUA), polyurethane methacrylate (PUMA), vinyl phosphonic acid (VPA), and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP) was exposed to ultraviolet (UV) radiation during the fabrication process. The unique crosslinked configuration of the membrane increased its stability and made it suitable for use with liquid electrolytes. The resulting GPE has a much higher ionic conductivity (1.83 × 10−3 S cm−1) than the commercially available Celgrad2500 separator. A crosslinked structure formed by the hydrophilic properties of the PUA-PUMA blend and the higher phosphate content from BMEP reduced the leakage of the electrolyte solution while at the same time providing a greater capacity for liquid retention, significantly improving the mechanical and thermal stability of the membrane. GPP2 shows electrochemical stability up to 3.78 V. The coin cell that was assembled with a LiFePO4 cathode had remarkable cycling characteristics and generated a high reversible capacity of 149 mA h g−1 at 0.1 C. It also managed to maintain a consistent Coulombic efficiency of almost 100%. Furthermore, 91.5% of the original discharge capacity was maintained. However, the improved ionic conductivity, superior electrochemical performance, and high safety of GPEs hold great promise for the development of flexible energy storage systems in the future. [ABSTRACT FROM AUTHOR]

In this study, poly(n-isopropylacrylamide) (PNIPA) has been synthesized by the free-radical polymerization method using azobisisobutyronitrile the initiator. Then, nanoparticle-PNIPA composite is prepared with magnetic iron oxide (Fe3O4) nanoparticles synthesized by co-precipitation. The thermal decomposition kinetics of synthesized PNIPA and nanocoated PNIPA have been investigated. It has been observed that nanocoated PNIPA has a more stable structure at high temperatures than synthesized PNIPA. In the newly improved model equations relate to thermal decomposition kinetics, a special solution has been made with the new approach. Moreover, the calculated activation energies of the samples have been evaluated with response surface methodology (RSM). The ratios required to synthesize nanocoated-PNIPA under the optimum conditions have been determined by RSM. The activation energy of the nanocomposite obtains when 0.3170 g PNIPA is coated with 0.048 g Fe3O4 nanoparticle is determined as 127.757 kJ/mol. In other words, nanocoating has been increased the thermal stability of the synthesized composite. Poly (n-isopropylacrylamide) has been synthesized by free radical polymerization The Fe-O stretching vibration proves the existence of nanoparticle in FTIR spectra The thermal decomposition kinetics of synthesized PNIPA and Fe3O4-PNIPA nanocomposite have been evaluated by RSM. Magnetic nanoparticle reinforcement enhances the thermal stability of PNIPA [ABSTRACT FROM AUTHOR]

The strategy for the preparation of polyisobutylene‐based block copolymers via mechanistic transformation from cationic to radical polymerization is reported. This strategy involves the synthesis of 2‐bromo‐2‐methylpropanoyl‐terminated difunctional polyisobutylene macroinitiator (BiBB‐PIB‐BiBB) via consecutive cationic polymerization, in situ preparation of hydroxyl‐terminated polyisobutylene and its acylation by 2‐bromo‐2‐methylpropanoyl bromide. The Mn2(CO)10−triggered photo‐induced radical polymerization of styrene in bulk using this macroinitiator leads to the formation of multiblock copolymer, while predominantly triblock copolymer is generated during the polymerization of methyl methacrylate. The possibility to functionalize the polyisobutylene by pyrene via photo‐induced radical addition of 1‐bromomethyl pyrene in the presence of Mn2(CO)10 is also demonstrated in this work. [ABSTRACT FROM AUTHOR]

A low viscosity tetra‐functional cyclosiloxane epoxy resins (TGTS) is synthesized via a one‐step hydrosilylation reaction and cured separately with four different aromatic diamines to explore the reaction kinetics, network development, and thermal resistance. The hardeners used are 1,3‐phenylenediamine (PDA), diethyl toluene diamine (DETDA), 4,4‐diaminodiphenylmethane (DDM), and 1,3‐bis(4‐aminophenoxy) benzene, because of their availability and aromaticity. During cure with TGTS they all display autocatalytic behavior, but when compared to a traditional organic epoxy resin, diglycidyl ether of bisphenol A (DGEBA) cured with DDM however, the rate constants are about 3 times slower and less exothermic. The DETDA hardener in particular exhibits significantly slower rates of cure when compared to the other amines, being about an order of magnitude slower compared to the PDA curative. This is attributed to higher steric hindrance, compounded by reduced miscibility. The TGTS‐DDM carbon fiber composite displays the most thermal resistance after extended exposure to 220°C, producing the least mass loss and after combustion of about 12% compared to 20% for the DGEBA cured with DDM. The results presented here, illustrate that a tetrafunctional cyclic siloxane epoxy resin, can exhibit excellent processability, evidenced by very low viscosities and long gelation times, whilst also displaying excellent thermal resistance, whether at elevated temperature, or during combustion. [ABSTRACT FROM AUTHOR]

Amphiphilic block copolymers are promising candidates for the fabrication of ultrafiltration membranes with an isoporous integral asymmetric structure. The membranes are typically fabricated by the combination of block copolymer self‐assembly and the non‐solvent‐induced phase separation (SNIPS) process resulting in isoporous integral asymmetric membranes. Certainly, all these membranes lack thermal and chemical stability limiting the usage of such materials. Within this study, the fabrication of completely cross‐linked isoporous integral asymmetric block copolymer membranes is demonstrated by UV cross‐linking resulting in chemical and thermal stable ultrafiltration membranes. The UV cross‐linking process of PVBCB‐b‐P4VP (poly(4‐vinylbenzocyclobutene)‐b‐poly(4vinylpyridine)) block copolymer membranes in dependency of irradiation time, intensity, distance between membrane and UV source and the wavelength is investigated. Furthermore, it is shown that the penetration depths can be increased by soaking the membranes in wave‐guiding solutions before UV cross‐linking is carried out. Moreover, a completely new and easy cross‐linking strategy is developed based on isorefractive solvents resulting in thermal and chemically stable membranes that are cross‐linked through the whole membrane thickness. Finally, the new cross‐linking strategy in isorefractive solutions is transferred to commercial PVDF and PAN‐co‐PVC polymer membranes paving the way for more stable and sustainable ultrafiltration membranes. [ABSTRACT FROM AUTHOR]

Ni‐rich cathodes have been intensively adopted in Li‐ion batteries to pursuit high energy density, which still suffering irreversible degradation at high voltage. Some unstable lattice O2− species in Ni‐rich cathodes would be oxidized to singlet oxygen 1O2 and released at high volt, which lead to irreversible phase transfer from the layered rhombohedral (R) phase to a spinel‐like (S) phase. To overcome the issue, the amphiphilic copolymers (UMA‐Fx) electrolyte were prepared by linking hydrophobic C−F side chains with hydrophilic subunits, which could self‐assemble on Ni‐rich cathode surface and convert to stable cathode–electrolyte interphase layer. Thereafter, the oxygen releasing of polymer coated cathode was obviously depressed and substituted by the Co oxidation (Co3+→Co4+) at high volt (>4.2 V), which could suppressed irreversible phase transfer and improve cycling stability. Moreover, the amphiphilic polymer electrolyte was also stable with Li anode and had high ion conductivity. Therefore, the NCM811//UMA‐F6//Li pouch cell exhibited outstanding energy density (362.97 Wh/kg) and durability (cycled 200 times at 4.7 V), which could be stalely cycled even at 120°C without short circuits or explosions. [ABSTRACT FROM AUTHOR]

Herein, an anionic polymerization method was employed to synthesize a series of amphiphilic poly(ethylene oxide-b-styrene-b-isoprene-b-styrene-b-ethylene oxide) penta-block copolymers (OSISO). Their molecular structure and properties were comprehensively characterized using GPC,1H-NMR, thermodynamic rheological testing and water contact angle test. Notably, the hydrophilic characteristics exhibited a proportional increase with the rise in poly(ethylene oxide) (PEO) content, ranging from 1.3 to 12.6 wt%. The polystyrene blocks with low number-average molecular weight (2000–3500) reduced the copolymer melt viscosity, surpassing a tenfold decrease than the control sample within the temperature range of 50–150 °C. Resultantly, this series of OSISO copolymers could be used to develop amphiphilic hot-melt pressure-sensitive adhesives (HMPSAs) by low temperature hot-melt processing method (<120 °C). HMPSAs loaded with 2 wt% of geniposide, prepared by an optimized composition formula of OSISO copolymers, tackifiers, and plasticizers (in a ratio of 5:5:2), displayed excellent in vitro drug release performance. Additionally, these adhesives presented impressive 180° peeling strength (0.05–0.14 kN/m) without residues left on the substrate in the 180° peeling tests. The incorporation of PEO block significantly enhanced both the adhesive properties and accumulative drug release. Geniposide showed a burst release behavior with a moderate accumulative drug release (15–30 wt%), attributed to the PEO phase without crystallization behavior of long PEO chains. [ABSTRACT FROM AUTHOR]

Moxifloxacin evaluation in pharmaceuticals and biological fluids is in high demand. It is important to fabricate a simple, sensitive, selective, miniaturized, and cost-effective chemical sensor to detect moxifloxacin in the environment. In this study, an electrochemical sensor based on molecularly imprinted polymer (MIP) was fabricated for the detection of moxifloxacin in which interdigital electrodes (IDEs) were used as transducers. Thermal free-radical bulk polymerization was used to synthesize MIP, methacrylic acid (MAA) was used as a functional monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, azobisisobutyronitrile (AIBN) as a free radical initiator, and dimethyl sulfoxide (DMSO) as a porogenic solvent in a poly (methacrylic acid) system for efficient recognition. The LCR meter was used to measure various electrical properties such as inductance and resistance. A concentration-dependent linear response was observed by the fabricated sensor having a lower limit of detection of 240 and 63 ppb for series and parallel resistance, respectively. Meanwhile, series and parallel inductance had lower detection limits of 48 and 8 ppb, respectively. Furthermore, in the presence of competing agents such as uric acid, ascorbic acid, and paracetamol, the fabricated sensor showed a selective response for moxifloxacin. The fabricated sensor also showed reversible and reproducible response. [ABSTRACT FROM AUTHOR]

This study focused on the thermal stability and the thermal degradation kinetics of two poly(vinyl ethers), PVEs, with different side groups. The objective was to determine how the nature of the side group affects the thermal properties of these materials. Poly(2–Phthalimide Ethyl Vinyl Ether), PPEVE, was derived via zirconocene–mediated cationic homopolymerization, and poly(2–Amino Ethyl Vinyl Ether), PAEVE, was obtained by hydrazinolysis of PPEVE. The thermal stability was investigated by employing thermogravimetric analysis (TGA) and differential thermogravimetry, DTG, at six different heating rates. The thermal decomposition kinetics data were evaluated using the Ozawa–Flynn–Wall, OFW, and Kissinger–Akahira–Sunose, KAS, "model-free" methods to calculate the activation energies, Ea , and subsequently the appropriate mathematical model or mechanism to describe the thermal decomposition process for each individual homopolymer. [ABSTRACT FROM AUTHOR]

In order to provide more evidence to understand the termination mechanism in styrene free‐radical polymerization, (1‐bromoethyl) benzene and polystyrene with bromide end group (PSt‐Br) synthesized by atom transfer radical polymerization (ATRP) were used as the model compound and model polymer to study the termination behavior of styrenic radical by atom transfer radical coupling (ATRC), and then the NMR chemical shifts of the head‐to‐head enchainment from coupling termination were obtained. SEC and different NMR measurement methods were used to analyze and characterize the products. It is confirmed that there is no bimolecular disproportionation termination between styrenic free radicals, but only coupling termination to form the head‐to‐head enchainment. The proton and carbon chemical shifts of the head‐to‐head enchainment from coupling termination for (1‐bromoethyl) benzene are 2.7–2.86 ppm and ~47.3 ppm. As for the polystyrene through ATRC from PSt‐Br, the corresponding chemical shifts are 2.61–3.29 ppm and ~46.4 ppm, respectively, they are almost the same as the data in our previous paper (~3.05 ppm, ~46.6 ppm) for polystyrene initiated by BPO, proving that the chain termination in free‐radical polymerization of styrene initiated by BPO occurs through primary termination between chain radical and primary radical rather than bimolecular termination between chain radicals. [ABSTRACT FROM AUTHOR]

The transition to a sustainable future requires the use of waste‐free technologies for production. Potentially, additive technologies can be a promising approach for accessing circular economy due to the precise amount of feeding materials and the absence of molds. However, the initial feeding materials for additive approaches are often based on non–renewable hydrocarbon sources. This work focused on the use of polymers derived from terpene alcohols to develop a filament suitable for 3D printing. Initially, the vinylation of menthol using calcium carbide was optimized and scaled up, then a series of terpenyl–based vinyl ethers were obtained under optimal conditions. The cationic polymerization of vinyl ethers was also scaled up and resulted in 99 % yield of the polymers, which was subsequently subjected to hot extrusion. The initial terpenol was used as an additive to increase polymer flexibility. The addition of menthol (30 wt %) to polyvinyl menthol led to the suitable filament. Using the filament, a series of objects were 3D printed at 125 °C. The material demonstrated good sinterability and adhesion to glass and shrinkage comparable to that of commercial 3D printing filaments. Furthermore, the polymers obtained were used as additives to enhance the adhesion of commercially available filaments. [ABSTRACT FROM AUTHOR]

Anisotropy in naturally occurring or synthetic microcellular structures is an important feature for the development of materials with high specific stiffness and strength, in addition to creating materials with unique physical properties. Polymeric foams constitute a broad class of materials that are widely used for their advantages of low density, high specific mechanical properties and high insulative properties. Traditional synthetic routes are slow, energy demanding processes that employ the use of high temperature ovens, freezers, or high‐pressure equipment. Herein we present a convenient and energy efficient method to produce anisotropic high performance polymeric foams via rapid radically induced cationic frontal polymerization coupled with chemical blowing agents. The degree of pore orientation and degree of anisotropy are a result of the propagating front working in concert with the foam volume expansion. This paper presents results into FP foam formation to illustrate how changes in boundary conditions and front initiation position affect both the microcellular structure and their resulting physical and mechanical properties. Additionally, results are presented to show how changes in resin formulation, such as the addition of nanoparticles affect both properties as well as the microcellular structure and anisotropy. [ABSTRACT FROM AUTHOR]

Potassium diphenyl phosphide (KPPh2), which forms a highly nucleophilic phosphide anion, was used as an initiator for the anionic ring-opening polymerization of glycidyl phenyl ether (GPE). GPE was selected as a model compound for the practical application of various glycidyl-type epoxy resins. MALDI-TOF MS analysis of the resulting polymer clarified the presence of a diphenyl phosphine moiety at initiation, confirming that the anionic polymerization was initiated by nucleophilic attack of the phosphide anion on the epoxide. In addition, compared to various basic catalysts such as phosphines and amines, KPPh2 catalyzed the ring-opening addition of epoxide with o-cresol much more efficiently, demonstrating its potential for application to epoxy–phenol curing systems. [ABSTRACT FROM AUTHOR]

In this work, FR‐PNX, an alkylphosphate oligomer was introduced into rigid polyurethane foam (RPUF) to fabricate FR‐PNX/RPUF composites. The flame retardancy, thermal stability, and combustion properties of composites were investigated by limiting oxygen index (LOI), thermogravimetric (TG), microcalorimetry (MCC), scanning electron microscopy (SEM), et al. The flame retardancy tests demonstrated that the incorporation of 50 phr of FR‐PNX yielded composites that the highest LOI of 23.6 vol% and achieved a V‐0 rating in the UL‐94 test. TG results indicated that FR‐PNX promoted the decomposition of FR‐RPUF in the process, but enhanced the high‐temperature stability of the composites. MCC analyses revealed that the addition of FR‐PNX suppressed the heat release during combustion, and FR‐PNX50/RPUF exhibited the lowest total heat release of 17.3 MJ/m2, a 35% reduction compared to the pure sample. Moreover, the peak heat release rate was decreased to 83.1 W/g, representing a 46.9% reduction compared to pure RPUF. SEM and Raman analyses of the char residue demonstrated that the incorporation of FR‐PNX facilitated the formation of a dense and continuous char layer in the FR‐RPUF, with increased graphitization degree of the char layer, thereby enhancing the composite's fire resistance through the development of a more stable fire barrier. [ABSTRACT FROM AUTHOR]

Difunctional glycidyl azide polymer (GAP) is an energetic binder promising for propellant formulations. The multifunctional fluorine‐containing GAP has been synthesized to enhance its mechanical properties. This work outlined multifunctional GAP partially grafted with 1,2,3‐triazole‐5‐(α‐hydroxyl)‐fluorinated polyether (GAP‐g‐3F) synthesized by thermal and catalyst‐free azide‐alkyne cycloaddition reaction, in which the azide groups were from GAP and electron‐deficient alkynes from β‐propargyl‐α‐hydroxyl poly (tri‐fluoropropane glycidyl ether) (PHP3F). PHP3F was synthesized via the typical cationic ring‐opening polymerization of 2‐((2,2,2‐trifluoroethoxy) methyl) oxirane and propargyl alcohol as the initiator. The chemical structures, molecular weight, and thermal properties were characterized by FTIR, NMR, GPC, DSC, and TGA, respectively. HNMR results showed that 8 % of total azide groups in GAP were grafted. GAP‐g‐3F had a slightly higher glass transition temperature than that of GAP. The results of TGA showed that GAP‐g‐3F had suitable thermal decomposition resistance up to 200 °C. The thermal properties, mechanical properties, cross‐linking network structures, and microstructures of the polyurethane networks cured with hexamethylene diisocyanate trimer as a crosslinking agent were determined and compared by TGA, universal tensile test, swelling measurement, and SEM, respectively. The initial decomposition temperature of GAP‐g‐3F‐based polyurethane networks (GAP‐g‐3F‐PU) was around 220 °C, thus meeting the requirements for propellants. In addition, GAP‐g‐3F‐PU exhibited superior mechanical properties, showing an almost twelvefold increase in tensile strength to 16.9 MPa compared with difunctional GAP‐PU with 1.4 MPa tensile strength. The results of the swelling measurement revealed that the GAP‐g‐3F‐PU sample showed a higher crosslinking density in comparison to the GAP‐PU sample. SEM results indicated that the multifunctional fluorine‐containing GAP could enhance compatibility between the soft and hard segments of polyurethanes, leading to a decrease in their separation degree. This finding showed that the synthesis of a multifunctional GAP partially grafted with fluorinated polyether via a triazole ring may be a promising solution to decrease the separation degree increase of PUs, thereby improving the mechanical properties. [ABSTRACT FROM AUTHOR]

The utilization of (cationic) reversible addition‐fragmentation chain transfer (RAFT) polymerization in photoinduced three‐dimensional (3D) printing has emerged as a robust technique for fabricating a variety of stimuli‐responsive materials. However, methods for precisely adjusting the mechanical properties of these materials remain limited, thereby constraining their broader applicability. In this study, a facile way is introduced to modulate the mechanical properties of 3D printed objects by mixing two chain transfer agents (CTAs) within a radical‐promoted cationic RAFT (RPC‐RAFT) polymerization‐based 3D printing process. Through systematic investigations employing tensile testing and dynamic mechanical analysis (DMA), the influence of CTA concentration and molar ratio between two CTAs on the mechanical behavior of the printed objects are explored. These findings demonstrate that higher concentrations of CTAs or a greater molar ratio of the more active CTA within the mixed CTAs result in decreased Young's modulus and glass transition temperatures of the printed objects. Moreover, the tensile failure strain increased with the increasing CTA content, i.e., the samples became more ductile. This methodology broadens the toolbox available for tailoring the mechanical properties of 3D printed materials. [ABSTRACT FROM AUTHOR]

Objective: To investigate the expression of mi R-195 and mi R-3653 in glioma tissue and to analyze their relationship with clinicopathological features and prognosis of glioma. Methods: Collected paraffin specimens of 42 glioma patients who underwent surgical resection at The Seventh Affiliated Hospital of Guangxi Medical University from January 2016 to June 2019 as the glioma group, and another 30 patients with traumatic brain injury who underwent surgical treatment during the same period were selected, and the paraffin specimens of the frontal or temporal lobe tissue removed during surgery were used as the control group. The relative expression of mi R-195 and mi R-3653 in glioma group and control group were detected by real-time fluorescent quantitative polymerization chain reaction (qRT-PCR), and the relationship between the expression of mi R-195 and mi R-3653 and the clinicopathological characteristics of glioma were analyzed. The relationship between mi R-195, mi R-3653 expression and prognosis in glioma patients was analysised by Kaplan Meier survival curve. The factors affecting the prognosis of glioma patients were analysised by Multivariate Cox regression. Results: The expression level of mi R-195 and mi R-3653 in glioma group were lower than those in control group (P＜0.001). There were significant differences in mi R-195 expression among patients with different pathological grades and distant metastasis (P ＜0.001). There were significant differences in mi R-3653 expression among patients with different tumor diameter,pathological grade and distant metastasis (P＜0.001). Kaplan-Meier survival curve showed that the three years survival rate of mi R-195and mi R-3653 low expression group were lower than those of mi R-195 and mi R-3653 high expression group (P＜0.05). Multivariate Cox regression analysis showed that distant metastasis, pathological grade III-IV level, low mi R-195 expression, and low mi R-3653expression were risk factors for the prognosis of glioma patients (P＜0.05). Conclusion: The low expression of mi R-195 and mi R-3653 in glioma patients is associated with distant metastasis, pathological grading of grade III-IV level, and low survival rate, mi R-195 and mi R-3653 may become prognostic indicators and therapeutic targets for glioma. [ABSTRACT FROM AUTHOR]

Elastomers based on cross‐linked bottlebrush polymers combine an extreme softness at low strains with a strain‐stiffening effect, which makes them attractive as active components in dielectric elastomer actuators (DEA). Their main disadvantage concerns the small relative permittivity, which is about 3.5, requiring relatively high driving voltage in actuators. We synthesized a bottlebrush polymer elastomer with polar brushes, which exhibit an enhanced dielectric permittivity of 4.4. Anionic ring‐opening polymerization of a polar cyclosiloxane gave telechelic polar brushes, while ring‐opening polymerization of a norbornene macromonomer gave a bottlebrush polymer which was cross‐linked to elastomers by a thiol‐ene reaction. Elastomers with a small elastic modulus below 100 kPa, strain at break exceeding 100 %, attractive elasticity, and small mechanical loss factors (tanδ) were achieved. Temperature‐dependent impedance measurements revealed a transition temperature of −95 °C and an interfacial polarization. The multigram scale synthesis demonstrates the potential for scaling up, which opens the door to broader applications of these materials beyond actuators, such as capacitive sensors, batteries, and electroluminescent devices. Notably, these devices operate at extremely low voltages where the dielectric breakdown does not limit their functionality, but still, the softness and the increased dielectric permittivity are a plus. [ABSTRACT FROM AUTHOR]

As temperature and salt-resistant materials, hydrophobically associating polymers can form a reversible spatial network structure through the interaction between their hydrophobic groups, effectively improve the viscosity of the polymer solution through association, and enhance the temperature and salt resistance of the polymer. Hydrophobically associating monomers have different effects on the properties of polymer solutions. Herein, acrylic acid, acrylamide, and 2-acrylamido-2-methylpropanesulfonic acid were used as hydrophilic monomers. The three hydrophobic monomers with different carbon chain lengths were prepared by the bromination reaction. Hydrophobic associating polymers DQM1-PAM, DQM2-PAM, and DQM3-PAM were prepared by aqueous solution free-radical polymerization. The structure–activity relationship of the hydrophobic monomers with different carbon chain lengths on polymers was studied. It was confirmed by Fourier-transform infrared spectroscopy and 1H-NMR that the target product was successfully synthesized. Scanning electron microscopy revealed that with increasing hydrophobic carbon chain length, the hydrophobic microarea of molecular aggregation increased, forming a closer spatial network structure. Thermogravimetric and fluorescence tests revealed that with increasing hydrophobic carbon chain length of polymer molecules, the polymerization temperature resistance increased, intermolecular association degree increased, and critical association concentration decreased. Rheological property evaluation revealed that the viscosity of 0.5% polymer DQM1-PAM, DQM2-PAM, and DQM3-PAM was 71.32, 100.21, and 118.79 mPa·s after shearing at 120 °C and 170 s−1 for 1 h. With the increase in the carbon chain length, the retention rate of shear viscosity of polymer in a salt solution increased, showing good salt resistance. Concurrently, the molecular aggregation microarea of a solution with 0.5% polymer, degree of molecular chain action, viscoelasticity of the solution (G' > G''), and thixotropic area all increased. The performance of polymer solution can be improved by modifying hydrophobically associating polymers with long carbon chains, which has a broader application. [ABSTRACT FROM AUTHOR]

Polyolefin‐b‐poly(ethylene oxide) (PEO) represents the most widely investigated amphiphilic block copolymers. So far, one‐pot continuous synthesis of such hybrid block copolymers has only been fulfilled by anionic polymerization through sequential addition of vinyl monomers and ethylene oxide (EO). It still remains challenging to achieve altogether high block efficiency, high polymerization efficiency, and high molar mass for PEO. Here, we report a one‐pot hybrid block copolymerization approach to polyisoprene/polystyrene(PI/PS)‐b‐PEO, in which PI/PS are formed by sBuLi‐initiated anionic vinyl‐addition polymerization, then in situ employed as macroinitiators for the anionic ring‐opening polymerization (ROP) of EO aided by an organic Lewis pair. The cooperative (dual‐ion‐complexing) catalytic effect of organobase and triethylborane is proven, for the first time, effective for lithium alkoxide initiator system, allowing to achieve at room temperature high ROP activity (complete EO conversion and PEO of 3–64 kg/mol reached in 1–6 h), narrow molar mass distribution, controlled block lengths and composition. Density functional theory calculation shows that phosphazene bases are particularly effective, compared with N‐heterocyclic bases, for complexing with Li+ and enhancing the nucleophilicity of oxyanion. The rate of ROP is also affected by Li+‐induced aggregation of the chain‐end ion pairs, which though can be offset by adequate catalyst loadings. The versatility of this approach is further demonstrated in the one‐pot synthesis of tri‐/tetrablock ter‐/quaterpolymers constituted by PI, PS, PEO, and poly(propylene oxide). Of great interest, PS‐b‐PI‐b‐PEO triblock terpolymer with a specific composition is found to form internally microphase‐separated micellar aggregates when dispersed in water. [ABSTRACT FROM AUTHOR]

In the current study, a novel radical‐induced cationic frontal polymerization (RICFP) concept capable of rapid curing at room temperature via visible light irradiation is represented. Initially, the optimal formulation, which can be most effectively cured with visible light irradiation, is determined based on thickness, hardness, curing speed, and mechanical properties using FT‐IR, DSC, TGA, and flexural test methods. Subsequently, the viability of the method is illustrated by fabricating glass fiber‐reinforced composites through the hand lay‐up technique, employing the optimized formulation and glass fibers in various forms (chopped strand mat and biaxial). Mechanical properties of the obtained composites, including bending, tensile, and shear tests, are carried out according to relevant international standards and compared with reference composites thermally cured with amine‐based hardener by conventional method. [ABSTRACT FROM AUTHOR]

Polyvinylpyrrolidone (PVP) exhibits remarkable qualities; owing to the strong affinity for water of its pyrrolidone group, which enhances compatibility with aqueous systems, it is effective for stabilizing, binding, or carrying food, drugs, and cosmetics. However, coating the surface of polymeric films with PVP is not practical, as the coatings dissolve easily in water and ethanol. Poly(silane–pyrrolidone) nano/microparticles were prepared by combining addition polymerization of methacryloxypropyltriethoxysilane and N-vinylpyrrolidone, followed by step-growth Stöber polymerization of the formed silane–pyrrolidone monomer. The silane–pyrrolidone monomeric solution was spread on oxidized polyethylene films with a Mayer rod and polymerized to form siloxane (Si-O-Si) self-cross-linked durable anti-fog thin coatings with pyrrolidone groups exposed on the outer surface. The coatings exhibited similar wetting properties to PVP with significantly greater stability. The particles and coatings were characterized by microscopy, contact angle measurements, and spectroscopy, and tested using hot fog. Excellent anti-fogging activity was found. [ABSTRACT FROM AUTHOR]

Herein, a novel, highly branched and photoresponsive polysiloxane is synthesized and studied. The polymer is photoconstructed into a single‐chain nanoparticle loaded with Nile Red and Metformin. Through the photoreversible [2+2] mechanism of the polymer's pendant coumarin moieties, the nanoparticles are de‐crosslinked, and their cargo molecules released. A study of the kinetics of release is undertaken in different solvents, providing insight into the relationship between the cargo's molecular structure and that of the polymer chain. On the whole, this report's study introduces new controlled release and cationic ring‐opening polymerization concepts while providing the first example of a single‐chain polymer nanoparticle based on a photoresponsive polysiloxane. [ABSTRACT FROM AUTHOR]

Liquid marbles (LMs) with a cubic shape are created by using various vinyl monomers as an inner liquid and polymer plates with mm size as a stabilizer. The relationship between the surface tension of the vinyl monomers and formability of the LMs is investigated. LMs can be fabricated using vinyl monomers with surface tensions of 42.7–40.3 mN m−1. The cubic polymer particles are successively synthesized via free‐radical polymerizations by irradiation of the cubic LMs with UV light in a solvent‐free manner. In addition, controlling the number of polymer plates per one LM, the shape of the plate or the coalescence of the LMs can lead to production of polymer particles with desired forms (e.g., Platonic and rectangular solids) that correspond to the shapes of the original LMs. [ABSTRACT FROM AUTHOR]