Imidization Reaction Research Articles

Synthesis of core-functionalised naphthalene diimides from naphthalenetetracarboxylic dianhydride using a vibratory ball mill: bromination, imidization and Heck-type reactions.

The synthesis of 9 core-functionalised naphthalene diimide (c-NDI) residues is reported via a 3-step solvent free synthesis from naphthalenetetracarboxylic dianhydride using only mechanochemical activation. Selective dibromination and subsequent dimidiation were achieved for the first time in a vibratory ball mill, resulting in the key structural intermediate, 2,6-dibromonaphthalenediimide (DBND), which is the basis for elaboration into a multitude of organic electronic materials. Our new synthesis of DBND is achieved in just 5 hours' reaction time over two steps compared to typical solution state times of 24 hours. Subsequent Heck-type cross coupling reactions, with a range of styrene residues, produced a series of c-NDIs in good yields. The Heck-type reactions are rapid (1.5 hours), require no additional heating or solvent and are tolerant of atmospheric moisture and air.

Superhydrophobic Electrospun PI/PTFE Membranes with Ultralow Dielectric Constants for High-Frequency Telecommunication.

High-frequency, high-power, and high-speed telecommunication in a complex environment promotes the development of dielectric materials toward a low dielectric constant, low dielectric loss, good thermal properties, and long-term reliability. Here, polyimide/polytetrafluoroethylene (PI/PTFE) nanofiber membranes with an inherent super hydrophobicity, excellent dielectric properties, good thermal stability, and enhanced tensile strength were prepared via a simple electrospinning strategy and an imidization reaction. The obtained PI/PTFE membranes demonstrate a superlow average dielectric constant of 1.22-1.27 and a dielectric loss of 0.032-0.048 in high frequency, together with an enhanced tensile strength, benefiting from the special nanofiber-bead structure formed in the composite membrane. The mixing of polyamic acid (PAA) and PTFE in the electrospinning solution endows the obtained PI/PTFE nanofiber membrane with a uniform distribution of PTFE and thus an inherent superhydrophobicity with a water contact angle of 156.1 and 159.2° for PI/PTFE-30% and PI/PTFE-40%, respectively. Besides, the hydrophobicity could be kept even after standing more than 10,000 water drops, and the thermal properties exhibited promising results with Tmax = 587 °C and Td5% = 423 °C, rendering these PI/PTFE membranes favorable alternatives for prospective telecommunication.

Robustly Flexible, Highly Transparent, and Polymerization-Regulated Polyimide Aerogel Membranes as Efficient Thermal Insulators for Solar Collection.

Efficient thermal insulators that can maintain their efficacy at extreme temperatures are in pressing demand, particularly in fields such as energy saving, aerospace, and sophisticated equipment. Herein, a novel and facile polymerization-regulated optimal strategy is adapted to realize the comprehensive performance of polyimide (PI) aerogel membranes with mechanical robustness, high flexibility, hydrophobicity, light transmittance, and efficient thermal insulation. Benefiting from the hydrolysis of monomers and chemical imidization reaction process verified by a thermo-chemo-mechanically coupled theoretical model, the viscosity of precursors, shrinkage rate, and microstructure of aerogels are precisely controlled, leading to a low thermal conductivity range of 0.023-0.044 W/(m·K). The fabricated PI aerogel membranes, which undergo a remarkable transformation from their initial brittle and opaque nature to a state of high flexibility and transparency, exhibit a 3.0 times increase in tensile strength (4.6 MPa) and a 8.4 times improvement in elongation at break (20.6%) over previous studies while demonstrating an exceptional light transmittance of 92.5% across a wide spectral range from 500 to 2500 nm. Additionally, the PI aerogel membranes possess superior mechanical properties and a wide temperature resistance range extending from -196 to 300 °C. These flexible PI aerogel membranes can be effectively adjusted to meet the practical application of a circular ring solar thermal collector, which displayed a high solar heat collection temperature of 135 °C at a thickness of 0.5 mm. The coordination between the thermophysical properties and mechanical properties of the PI aerogel membranes in this work holds great promise for application requirements of thermal insulators in optical elements under harsh environments.

Algorithm-Driven Robotic Discovery of Polyoxometalate-Scaffolding Metal-Organic Frameworks.

The experimental exploration of the chemical space of crystalline materials, especially metal-organic frameworks (MOFs), requires multiparameter control of a large set of reactions, which is unavoidably time-consuming and labor-intensive when performed manually. To accelerate the rate of material discovery while maintaining high reproducibility, we developed a machine learning algorithm integrated with a robotic synthesis platform for closed-loop exploration of the chemical space for polyoxometalate-scaffolding metal-organic frameworks (POMOFs). The eXtreme Gradient Boosting (XGBoost) model was optimized by using updating data obtained from the uncertainty feedback experiments and a multiclass classification extension based on the POMOF classification from their chemical constitution. The digital signatures for the robotic synthesis of POMOFs were represented by the universal chemical description language (χDL) to precisely record the synthetic steps and enhance the reproducibility. Nine novel POMOFs including one with mixed ligands derived from individual ligands through the imidization reaction of POM amine derivatives with various aldehydes have been discovered with a good repeatability. In addition, chemical space maps were plotted based on the XGBoost models whose F1 scores are above 0.8. Furthermore, the electrochemical properties of the synthesized POMOFs indicate superior electron transfer compared to the molecular POMs and the direct effect of the ratio of Zn, the type of ligands used, and the topology structures in POMOFs for modulating electron transfer abilities.

Fabrication of liquid-free ionic conductive elastomer (ICE) from cellulose-rosin derived poly(esterimide) towards temperature-tolerant and solvent-resistant UV shadowless adhesive and sensor

Recently, the utilization of the cellulose to fabricate the multifunctional materials with aim to replace the petroleum-based product, is receiving significant attentions. However, the development of cellulose-based multifunctional materials with high mechanical strength and temperature resistance is still a challenge. Herein, the intrinsic feature and property of cellulose and rosin were creatively employed to fabricate a novel cellulose-rosin based poly(esterimide) (PEI) by esterification reaction and imidization reaction, and the obtained cellulose-rosin derived PEI exhibits superior thermal stability. Then the as-prepared cellulose-rosin derived PEI was dissolved in polymerizable deep eutectic solvents (PDES) and in-situ formed the ionic conductive elastomer (ICE) with via UV-induced polymerization. These cellulose-rosin based ICE exhibited excellent mechanical properties, solvent resistance, and temperature tolerance. By adjusting the mass ratio of cellulose-rosin derived PEI and PDES, the as-prepared liquid-free ICE functions as UV shadowless adhesive and wearable sensors. The bonding strength of UV shadowless adhesive could 1.52 MPa, which could be applied to fix the broken glass toy models. Furthermore, wearable sensors based those ICE could monitor the large and subtle movements even under extreme environmental condition, such as being soaked in organic solvent (such as tetrahydrofuran) or at low/high temperature (−25 °C or 80 °C). This work opens a new avenue for the next-generation of multifunctional ICE.

Reduction of 2-phenyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione with NaBH4: Investigation of exo-selectivity and reaction mechanism via theoretical computations

The reaction of the bicyclic imide with NaBH4 afforded acylaminocarbinol and carboxamide derivatives. The exact configuration of acylaminocarbinol 7 was determined by X-ray crystal analysis. Theoretical studies were carried out to explain the mechanism of the exo-selectivity observed in the first step of the reduction reaction and the formation of the secondary product in the second step. According to the obtained findings, i) in the first step of the reaction, the exo-path is kinetically more favorable, and ii) an alternative mechanism has been proposed instead of the mechanism proposed in the literature. The canonical forms of the amide group in the lactam ring were found to make an important contribution to the mechanism. iii) The amount of products formed in the reduction reaction depends on the reaction conditions.

Graphene nanoribbon hydrogel scaffold for highly conductive and robust polyimide nanocomposite

Although highly loaded graphitic nanocarbon materials effectively enhance the electrical, mechanical, and thermal properties of polymeric materials, their practical implementation has been hindered by severe aggregation issues. Here, we propose a method to achieve homogeneous nanocarbon-polyimide (PI) composites by integrating graphene oxide nanoribbons (GONRs) with polyamic acid ammonium (PAA) salt, a precursor of PI. Self-assembled scaffold structure of GONRs hydrogel enables the uniform integration and immobilization of PAA within the GONR scaffold, mitigating aggregation concerns. The resulting GONR/PAA hydrogel, formed through physical interactions, can be coated onto substrates via a shear stress-induced bar coating method due to its viscoelastic rheological properties. Subsequent heat treatment at 400 °C triggers the imidization reaction of PAA and the reduction of GONR, facilitating the formation of uniformly integrated GNR/PI nanocomposite coatings. Under optimized conditions, incorporating a high-loading GONR content in PAA (95 wt% of GONR and 5 wt% of PAA) yielded GNR/PI composites with excellent mechanical properties, exhibiting a hardness of 0.75 GPa and an elastic modulus of 8.3 GPa. Additionally, this GNR/PI composite displayed a good electrical conductivity of 3890 S/m, attributed to the electrical pathways formed by GNRs within the PI matrix.

Glutathione-depleting Liposome Adjuvant for Augmenting the Efficacy of a Glutathione Covalent Inhibitor Oridonin for Acute Myeloid Leukemia Therapy

BackgroundDiscrepancies in the utilization of reactive oxygen species (ROS) between cancer cells and their normal counterparts constitute a pivotal juncture for the precise treatment of cancer, delineating a noteworthy trajectory in the field of targeted therapies. This phenomenon is particularly conspicuous in the domain of nano-drug precision treatment. Despite substantial strides in employing nanoparticles to disrupt ROS for cancer therapy, current strategies continue to grapple with challenges pertaining to efficacy and specificity. One of the primary hurdles lies in the elevated levels of intracellular glutathione (GSH). Presently, predominant methods to mitigate intracellular GSH involve inhibiting its synthesis or promoting GSH efflux. However, a conspicuous gap remains in the absence of a strategy capable of directly and efficiently clearing GSH.MethodsWe initially elucidated the chemical mechanism underpinning oridonin, a diminutive pharmacological agent demonstrated to perturb reactive oxygen species, through its covalent interaction with glutathione. Subsequently, we employed the incorporation of maleimide-liposomes, renowned for their capacity to disrupt the ROS delivery system, to ameliorate the drug’s water solubility and pharmacokinetics, thereby enhancing its ROS-disruptive efficacy. In a pursuit to further refine the targeting for acute myeloid leukemia (AML), we harnessed the maleic imide and thiol reaction mechanism, facilitating the coupling of Toll-like receptor 2 (TLR2) peptides to the liposomes’ surface via maleic imide. This strategic approach offers a novel method for the precise removal of GSH, and its enhancement endeavors are directed towards fortifying the precision and efficacy of the drug’s impact on AML targets.ResultsWe demonstrated that this peptide-liposome-small molecule machinery targets AML and consequently induces cell apoptosis both in vitro and in vivo through three disparate mechanisms: (I) Oridonin, as a Michael acceptor molecule, inhibits GSH function through covalent bonding, triggering an initial imbalance of oxidative stress. (II) Maleimide further induces GSH exhaustion, aggravating redox imbalance as a complementary augment with oridonin. (III) Peptide targets TLR2, enhances the directivity and enrichment of oridonin within AML cells.ConclusionThe rationally designed nanocomplex provides a ROS drug enhancement and targeted delivery platform, representing a potential solution by disrupting redox balance for AML therapy.

Polyacrylonitrile In-Situ reinforced polyimide superhydrophobic porous fibers: A miraculous thermal insulation and flame-retardant material

In response to the demand for safety protective textiles suitable for extreme conditions such as intense heat and humidity, we have innovatively developed a novel approach using polyacrylonitrile (PAN) in-situ reinforced polyimide (PI) superhydrophobic porous fibers. We blended fluorinated polyamic acid (PAA) with PAN and prepared PI/pre-oxidized fiber (panof) porous fibers using a process that includes wet phase separation spinning and integrated synchronous imidization/pre-oxidation. Special emphasis was placed on the chemical mechanisms during the heat treatment stage of the preparation process. The uncapped PAA underwent imidization reactions and also facilitated PAN’s pre-oxidation, which notably enhanced the structural stability of the PI porous fibers. This novel enhancement mechanism effectively addresses the challenges of structural collapse and volume shrinkage encountered in the preparation of traditional PI porous fibers. In addition, our investigation into the impact of thermal imidization temperature on the structure of porous fibers led to the evaluation of PI/panof porous fibers. The PI/panof-320 porous fibers, produced by the combined enhancement effect of fluorinated PI and PAN, showcased exceptional features: superhydrophobicity (water contact angle = 168.9°), low density (0.078 g/cm3), reduced thermal conductivity (0.0251 W/(m·K)), high strength (22.18 MPa), outstanding flexibility (bend radius = 205 μm), and superior flame retardancy and insulation. The outstanding performance of these composite porous fibers paves the way for innovative, comfortable, and safe wearable devices in high heat and humidity environments, highlighting their extensive applicability and potential.

Trivalent Phosphine-Catalyzed [4+1] Spiro-annulation Reaction Using Allenyl Imide and Methylene Cyclocompounds.

The trivalent phosphine-catalyzed [4+1] spiro-annulation reaction of allenyl imide and activated methylene cyclocompounds has been developed for the construction of various spiro-2-cyclopenten-1-ones. Oxindoles, 3-isochromanones, and 2-indanones are selected as 1C synthons to capture the in situ-generated bis-electrophilic α,β-unsaturated ketenyl phosphonium intermediate, affording the corresponding monospiro- and bispiro-cyclopentenones in good to excellent yields (≤91%) under mild conditions. The primary attempt at asymmetric catalysis using monophosphine (R)-SITCP provides promising enantioselectivity (45% ee). A plausible reaction mechanism is also proposed.

Hydrophilic phthalocyanine covalent organic frameworks for enhanced electrocatalytic H2O2 production

The electrocatalytic 2e− oxygen reduction reaction (ORR) is considered as a promising pathway to replace conditional anthraquinone process for hydrogen peroxide (H2O2) manufacture. However, the efficient electrocatalysts towards 2e− ORR remain urgently desired. Herein, hydrophilic two-dimensional cobalt phthalocyanine (CoPc) covalent organic frameworks (COFs), denoted as CoPc-2SO3H-COF and CoPc-SO3H-COF, were afforded via the imidization reaction of 2,3,9,10,16,17,23,24-octacarboxyphthalocyaninato cobalt(II) with hydrophilic building blocks 2,5-diaminobenzenesulfonic acid and 1,4-benzenedisulfonic acid, respectively. Powder X-ray diffraction, transmission electron microscope, and N2 sorption experiment results reveal the crystalline and porous structure of these two COFs. Moreover, the water contact angle and proton conduction measurements demonstrate the hydrophilic properties of these two COFs owing to the introduction of −SO3H into their skeleton. This, in combination with the high-efficiency active Co-N4 sites towards 2e− ORR, endows these two COFs with enhanced 2e− ORR activity in the aqueous electrolyte. In particular, CoPc-2SO3H-COF exhibits outstanding electrocatalytic H2O2 production performance with a stable H2O2 selectivity of 88.3 % under a high current density of 125 mA cm−2 for 20 h in a flow cell.

Phthalocyanine Covalent Organic Frameworks: Dimensionality Effect on Third‐Order Nonlinear Optical Properties

AbstractDimensionality of covalent organic frameworks (COFs), in terms of 2D and 3D, must greatly influence their properties and functionalities due to the different electronic and porous structures, but still less investigated in the 20 years history. Herein, on the basis of the imidization reaction of phthalocyanine‐based tetraanhydride monomers with either 1,4‐phenylenediamine or 1,3,5,7‐tetra(4‐aminophenyl)adamantine, 2D and 3D imide‐bonded COFs with sql and pts topology have been prepared to explore their third‐order nonlinear optical (NLO) properties. In contrast to metal‐free analogues, both 2D and 3D copper‐phthalocyanine COFs have the enhanced NLO behaviors according to the open aperture Z‐scan and optical limiting (OL) results recorded under a nanosecond laser at 532 nm. In particular, 2D COFs with strong π–π staking phthalocyanine units show the NLO property with bigger third‐order nonlinear susceptibility (Imχ(3)) and unique reverse saturation absorption response at 1064 nm than that of 3D species with dispersed conjugated modules. Furthermore, femtosecond transient absorption spectra disclose the longer excited lifetimes of copper COFs than metal free samples, helpful in their NLO property. These findings clearly disclose the materials advantages of 2D phthalocyanine COFs toward the NLO characteristics and provide new candidates for OL application.

LIBS as a novel tool for the determination of the imidization degree of polyimides

Due to their outstanding chemical and physical properties, polyimides are widely used in industrial applications. The degree of imidization of polyimides significantly influences their properties, making it an important factor in tailoring the material for specific applications. Imidization refers to the process of converting a precursor poly(amic acid) by removing water, and it is essential to analyze this process in detail to tune the final structure and properties of the material. Conventional techniques for this task include Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), or differential scanning calorimetry (DSC), but they lack the possibility of spatially and/or depth-resolved analysis or do not enable in-line monitoring capabilities. To overcome these limitations, we propose laser-induced breakdown spectroscopy (LIBS) as a powerful tool for the monitoring of the imidization reaction. To establish a measurement method, a total of 130 in-house prepared, self-synthesized samples were thermally cured to exhibit varying imidization degrees. IR spectroscopy served as a reference technique during method development, and a novel formula for calculating the degree of imidization, based on the C2 and H signal trends, was introduced. The calculated imidization degrees of model thin films based on LIBS were in good accordance with the IR reference method although minor differences between the two methods were expected due to varying information depth and the size of the sampled area. Additionally, the robustness of the procedure was demonstrated by depth profiling of a stacked model polymer, spiking with commercially available additives and, ultimately, by analyzing industry-relevant polymer samples.Graphical

Fabrication of polyethyleneimine grafted maleopimaric acid glycidyl methacrylate ester stationary phase for mixed-mode liquid chromatography

Due to their advantages of low green toxicity, diverse sources, renewable nature, and excellent biocompatibility, natural products have been extensively utilized in the exploration and development of novel stationary phase materials for liquid chromatography. In this study, we fabricated a rosin-based stationary phase material for mixed-mode chromatography by utilizing maleopimaric acid glycidyl methacrylate ester (MPAG) and polyethyleneimine (PEI) as ligands. Initially, silica was functionalized with MPAG through thiol-ene click reaction, followed by the grafting of PEI via an imidization reaction to produce Sil-MPAG-PEI material. This material exhibited both anion exchange and hydrophilic interaction properties due to the presence of PEI, allowing for the switching of its retention mode from reversed-phase mode to a mixed-mode incorporating reversed-phase, hydrophilic interaction and ion-exchange chromatography (RPLC/HILIC/IEC) under different mobile phase conditions. Consequently, Sil-MPAG-PEI demonstrated the ability to provide various interactions, including hydrophobic, π-π, hydrogen bond, hydrophilic, ion exchange, and electrostatic interactions. These interactions enabled selective separation among compounds with different polarities, such as nucleosides/bases, benzoic acids, flavonoids, alkylbenzenes, phenols, anilines, and polycyclic aromatic hydrocarbons (PAHs). Furthermore, Sil-MPAG-PEI demonstrated excellent chromatographic stability, as evidenced by the low relative standard deviations (RSDs) of the retention time for interday precision and interday precision were 0.042 %-0.275 % (n = 10) and 0.159 %-0.932 % (n = 7). The column was also successfully employed for the quantitative determination of evodiamine and rutaecarpine in an extract solution of Evodiae fructus, achieving concentrations of 9.102 and 3.256 mg/g, respectively. These results demonstrate the potential of Sil-MPAG-PEI in the analysis of complexsamples. Briefly, this study investigated and confirmed the potential application of rosin derivatives in mixed-mode liquid chromatography separations has been investigated and verified. The exceptional separation ability of Sil-MPAG-PEI indicates that it is a promising separation material for chromatographic separation.

Unprecedented single-electron-transfer reduction-based N → C acyl migration reactions of imides enabled by redox-neutral photocatalysis

N → C acyl migration: in the absence of a base, redox-neutral photocatalyzed acyl migration reactions have been realized via the reaction of N-vinylimides with alkyl radicals derived from alkyl silicates.

On-water surface synthesis of electronically coupled 2D polyimide-MoS2 van der Waals heterostructure

The water surface provides a highly effective platform for the synthesis of two-dimensional polymers (2DP). In this study, we present an efficient on-water surface synthesis of crystalline monolayer 2D polyimide (2DPI) through the imidization reaction between tetra (4-aminophenyl) porphyrin (M1) and perylenetracarboxylic dianhydride (M2), resulting in excellent stability and coverage over a large area (tens of cm2). We further fabricate innovative organic-inorganic hybrid van der Waals heterostructures (vdWHs) by combining with exfoliated few-layer molybdenum sulfide (MoS2). High-resolution transmission electron microscopy (HRTEM) reveals face-to-face stacking between MoS2 and 2DPI within the vdWH. This stacking configuration facilitates remarkable charge transfer and noticeable n-type doping effects from monolayer 2DPI to MoS2, as corroborated by Raman spectroscopy, photoluminescence measurements, and field-effect transistor (FET) characterizations. Notably, the 2DPI-MoS2 vdWH exhibits an impressive electron mobility of 50 cm2/V·s, signifying a substantial improvement over pristine MoS2 (8 cm2/V·s). This study unveils the immense potential of integrating 2D polymers to enhance semiconductor device functionality through tailored vdWHs, thereby opening up exciting new avenues for exploring unique interfacial physical phenomena.

Transparent and highly organosoluble aromatic polyimides with twisted backbone and bulky side substituents for flexible substrate materials

AbstractIn this study, four novel aromatic polyimides (PIs) with twisted backbone and bulky side substituents were prepared via chemical imidization reaction and two‐step condensation polymerization at reduced reaction temperature. The number‐average and weight‐average molecular weights of the resulting PIs are in the range of 1.98 × 104–4.10 × 104 and 2.66 × 104–5.32 × 104 g mol−1, respectively, while maintaining polydispersity indices consistently below 2.0. In addition, the obtained PIs showed excellent solubility in most common solvents, even in low‐boiling solvents, such as chloroform, dichloromethane, and tetrahydrofuran. The films casted from these PIs also displayed optical transparency with a cutoff wavelength in the range of 335–360 nm. Among the PIs, PAPOT‐OPDA, derived from 3,3′‐Diisopropyl‐4,4′‐diaminodiphenyl‐3″‐phenoxybenzylmethane (PAPOT) and 3,3′,4,4′‐diphenylethertetracarboxylic dianhydride (OPDA), exhibited the highest transparency of T450 = 81% and T500 = 85%, and the best solubility without compromising its thermal properties.

Porphyrin-Anhydride Co-Sensitization Strategy for Enhanced Photovoltaic Performance in DSSC: A Combined Experimental and Theoretical Approach

A new covalently linked porphyrin-based anhydride(C108H86N10O4Zn2) named TPP-PMDI-TPP has been successfully synthesized through a simple thermal imidization reaction of electron-donating Zn(5-(4-aminopheny)-10,15,20-triphenylporphyrin(Zn-ATPP) and electron-accepting pyromellitic dianhydride(PMDA) moieties and tested in the of photovoltaic application. TPP-PMDI-TPP was subjected to comprehensive characterization using various analytical techniques, including FT-IR, 1H NMR, UV–visible, PXRD, cyclic voltammetry, and molecular simulation. Fluorescence studies were also employed to characterize TPP-PMDI-TPP. Excellent fluorescence quenching of 95 % was observed in TPP-PMDI-TPP, indicating remarkable electron transfer from porphyrin to pyromellitic dianhydride within TPP-PMDI-TPP. The cyclic voltammetric analysis provided the HOMO and LUMO values of TPP-PMDI-TPP as −6.172 eV and −4.185 eV, respectively. The investigation of the charge-transfer phenomenon in the entitled compound was assessed using FMOs. Results obtained from cyclic voltammetry and computational calculations for HOMO, LUMO, and band gap (Eg) of porphyrin-based anhydride (TPP-PMDI-TPP) are in well concordance, indicating the practicality of the utilized experimental approach. Global reactivity parameters were obtained by using HOMO–LUMO energies of compounds. The photovoltaic measurements of ITO-coated TPP-PMDI-TPP film was performed to check different photovoltaic parameters (VOC, ISC, FF, and η), showing values of about 0.858 V, 8.1794 mA/cm2, 0.561 and 3.9 % respectively, calculated from current-voltage (I–V) graph. The lower photocurrent and power conversion efficiency in the TPP-PMDI-TPP film is due to the electron withdrawal caused by the dianhydride group, transferring electrons from porphyrin to PMDA. This electron-withdrawing effect leads to imbalanced charge transport, with higher hole mobilities than electron mobilities, resulting in lower efficiency for TPP-PMDI-TPP-based photovoltaic cells.

Conjugated Microporous Polymers Based on Octet and Tetratopic Linkers for Efficient Iodine Capture.

Radioactive iodine from nuclear waste poses a huge threat to public safety and raises concerns about environmental pollution. There is thus a growing demand for developing novel adsorbents for highly effective iodine capture. In this work, we design and synthesize three novel conjugated microporous polymers, namely, TPE-PyTTA-CMP, TPE-TAPP-CMP, and TPE-TPDA-CMP, which are constructed by an imidization reaction based on octet and tetratopic linkers. The iodine vapor adsorption experiments show that the three CMPs have an excellent iodine adsorption capacity as high as 3.10, 3.67, and 4.68 g·g-1 under 348 K and ambient pressure conditions, respectively. The adsorbed iodine in the CMPs can be released into methanol in a dramatically rapid manner, and their excellent iodine adsorption performance can still be maintained after multiple cycles. In addition, the CMPs demonstrate good adsorption performance in an n-hexane solution of iodine, and the kinetic experimental data follow the pseudo-second-order model. The hierarchical porosity, extended π-conjugated skeleton, and rich electron-donor nitrogen sites of the CMPs could contribute to their excellent iodine adsorption performance. The knowledge information obtained in this work could open up new possibilities for designing novel CMPs targeting a wide range of environment-related applications.

Study on high-temperature degradation of acrylamide-based polymer ZP1 in aqueous solution

As exploration of deep and ultra-deep becomes more active, the utilization of acrylamide-based polymers as drilling fluid additives in challenging subsurface conditions, particularly at high temperatures, is growing. In this study, various monomers including acrylamide (AM), 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) and dimethyl diallyl ammonium chloride (DMDAAC) were used to synthesize an acrylamide-based polymer ZP1. Subsequently, 2.5 wt% aqueous solution of polymer ZP1 was subjected to a high-temperature degradation test at temperatures of 150, 180, 200, 220, and 240 °C, respectively. The degradation behavior of the polymer in aqueous solution and drilling fluid was investigated using various analytical techniques, including FT-IR, 1H NMR, XPS, GPC, TG-IR, and SEM. The research results indicate that the degradation temperature of the solid polymer sample was 258 °C, while in the solution at a temperature higher than 200 °C, the hydrolysis and imidation reaction in the polymer molecular chain was accelerated, which caused the main chain of the polymer to break easily. When the molecular weight (Mn) of the polymer decreased to less than 10,000, the protective influence of the polymer on the drilling fluid was lost, resulting in deterioration of the performance of the drilling fluid. However, the functional groups (amide groups, sulfonic acid groups, and quaternary ammonium groups) on the molecular chain of the polymer were retained.