Polymerization Time Research Articles

Synthesis of polyesters derived from glycerol and phthalic anhydride and its application for bitumen modification

AbstractThis study introduces phthalic anhydride (P) and glycerol (G)‐based polyester as an additive for upgrading lower‐grade bitumen to higher‐grade bitumen. The different colorless polyesters were synthesized using polycondensation of P and G as a monomer in the ratio of 1:1 and polymerization time of 1, 3, 5, and 7 h. A rheological analysis was performed on all the synthesized polyesters to check their performance with respect to their use in bitumen modification. The polyesters were blended with base bitumens (VG10) to obtain the modified bitumens that were tested for the rheological and physicochemical properties and to assess the performance based on the grade quality test. The quality test of the modified bitumens includes softening point (SP), penetration (PEN), kinematic viscosity (KV), dynamic viscosity (DV), and rheological properties as per standard ASTM test methods. Based on the performance evaluation, P1G1H3 polyester was found suitable for blending with bitumen, and further study was carried out with blending of P1G1H3 with 3, 6, 10, and 15 wt%. The finding illustrates that 6.0 wt% of polyester‐modified bitumen show an enhanced SP, KV, and DV by 23.6, 86, and 30%, respectively, while decreasing the PEN by 49% with respect to VG10. Polyester blending also improved the rheological parameters in terms of deformation resistance, load‐bearing capacity, and the viscoelastic nature of bitumen. The investigation concluded that 6 wt% P1G1H3 polyester on blending in VG10 meets VG30 bitumen specification as per IS:73:2013.

Molybdenum trioxide/carbon nanotubes/poly (5-carboxylindole) (MoO3/MWCNT-COOH/P5ICA) nanocomposites as an electrode material for high-performance hybrid supercapacitors

Molybdenum trioxide/carboxyl functionalized carbon multi-wall nanotubes/poly(5-carboxylindole) (MoO3/MWCNT-COOH/P5ICA) ternary composites were prepared as supercapacitor electrodes by hydrothermal and electrochemical polymerization methods. When three materials are composite used as electrodes for supercapacitors, the advantages of each material can be effectively integrated, resulting in low impedance and high capacitance characteristics. After optimizing the electrochemical polymerization time of P5ICA, the maximum specific capacitance of the composite electrode can reach 165.6 mF cm−2. The symmetric supercapacitor constructed with composite electrodes demonstrates a maximum specific capacitance of 61.0 mF cm−2, and the area specific capacitance can remain 74 % of the original after 1000 charge and discharge cycles. This study provides a feasible scheme for preparing high performance supercapacitor materials.

Optimizing light and heavy aromatic ratios in fluid catalytic cracking slurry oil for mesophase pitch with wide-area optically anisotropic texture

Aromatics are the preponderant component of fluid catalytic cracking (FCC) slurry oil, with notable differences in molecular structure between the light and heavy aromatics. The effect of these differences on the formation and optically anisotropic texture of mesophase remains elusive, impeding the preparation of high-quality mesophase pitch. This paper aims to regulate the ratio of light to heavy aromatics in the FCC slurry oil for optimizing the optically anisotropic texture of mesophase pitch. The results show that the heavy aromatics possess higher aromaticity, longer alkane side chains, larger molecular size and more reactive structures (methylene bridges, n-alkane structures) compared with the light aromatics. As an “accelerator”, heavy aromatics can form mesophase quickly. Light aromatics not only served as a “diluent,” but also assumed the function of a “lubricant”, which facilitated the orderly arrangement of aromatic molecular lamellar. The system exhibits moderate reactivity that inhibits excessive condensation and modifies the structural orientation of pyrolysis products with the 2/5 ratio of light to heavy aromatics. Under these conditions, a high-quality mesophase pitch (d002 = 3.485 Å, Lc = 19.832 Å) with wide-area optically anisotropic texture, suitable softening point (262 °C) and short polymerization time (t = 5.5 h) was obtained. This work provides theoretical support for the preparation of high-quality mesophase pitch by regulating the components of slurry oil.

PISOX Copolyesters-Bio- and CO2-Based Marine-Degradable High-Performance Polyesters.

Oxalate esters and isosorbide serve as intriguing polymer building blocks, as they can be sourced from renewable resources, such as CO2 and glucose, and the resulting polyesters offer outstanding material properties. However, the low reactivity of the secondary hydroxyl groups makes it difficult to generate high-molecular-weight polymers from isosorbide. Combining diaryl oxalates with isosorbide appears to be a promising approach to produce high-molecular-weight isosorbide-based polyoxalates (PISOX). This strategy seems to be scalable, has a short polymerization time (<5 h), and uniquely, there is no need for a catalyst. PISOX demonstrates outstanding thermal, mechanical, and barrier properties; its barrier to oxygen is 35 times better than PLA, it possesses mechanical properties comparable to high-performance thermoplastics, and the glass transition temperature of 167 °C can be modified by comonomer incorporation. What makes this high-performance material truly exceptional is that it decomposes into CO2 and biomass in just a few months in soil under home-composting conditions and it hydrolyzes without enzymes present in less than a year in 20 °C water. This unique combination of properties has the potential to be utilized in a range of applications, such as biomedical uses, water-resistant coatings, compostable plastic bags for gardening and agriculture, and packaging plastics with diminished environmental impact.

Electrochemical visualization of latent fingerprints using polyphenazine dyes on brass cartridges

This work is focused on the visualization of latent fingerprints left on unfired brass cartridges. Polymer films were prepared from 2 mM neutral red or 5 mM toluidine blue using two different electrochemical methods (cyclic voltammetry or chronoamperometry) with relatively short polymerization times. The conditions for the deposition of conductive polymers, poly(neutral red) and poly(toluidine blue), from a neutral medium (phosphate buffer with 0.1 M KNO3 or 0.1 M KNO3, respectively) were optimized to produce high-quality visualization of the remaining fingerprints on the brass substrates. The surface morphology and quality of the polymer films after the electrochemical deposition of both polyphenazine dyes were characterized by stereomicroscope. Phenazine dyes, which were used for the visualization of fingerprints, have been shown to provide different degrees of homogeneity in the deposited film. Furthermore, the dependence of the stability of the monomer solutions on their age, use, and storage conditions are discussed. Finally, a methodology is proposed for how to apply this technique of visualizing latent fingerprints with observed details of papillary lines in forensic practice.Graphical abstract

Advanced sulfonated polyester nanofiltration membranes for superior dye separation, desalination, and chlorine resistance

This study introduces an innovative thin-film composite (TFC) nanofiltration membrane made from sulfonated polyvinyl alcohol (SPVA)-based polyester, specifically engineered for effective wastewater treatment. This novel membrane is developed through interfacial polymerization on a polysulfone substrate, demonstrating exceptional water permeability and filtration efficiency. It is particularly effective in separating dyes and salts due to its superior hydrophilicity, optimized surface charge, and precisely tailored morphology. Critical fabrication parameters were finely tuned, utilizing a 2 wt% SPVA solution and a 0.35 wt% trimesoyl chloride (TMC) in the organic phase, with both immersion and polymerization times set at 2 min. The performance metrics are outstanding, featuring a water permeance of 97 L m−2 h−1·bar−1, high dye rejection rates (99.51 % for Congo Red and 99.55 % for Brilliant Blue), and significant salt permeability (30.35 % for Na2SO4 and 29.93 % for MgSO4). The membrane also exhibits excellent antifouling properties, robust chlorine resistance (up to 48,000 ppm h), and sustained operational stability, underscoring its industrial viability for dye and textile effluent treatment. The TFC-SPVA membrane addresses critical environmental challenges in wastewater management, marking a significant advancement in membrane technology.

Iodinated Cyanoacrylate-based Novel Liquid Embolic Compositions with Inherent Radiopacity for Endovascular Embolization.

Endovascular embolization is a promising therapeutic approach broadening its application area due to its minimal invasiveness and short operation time, wherein lesional blood vessels are occluded with liquid embolic agents under X-ray imaging guidance. Histoacryl and its composition with Lipiodol are one of the most widely used liquid embolic agents, however, Histoacryl has critical limitations such as lack of innate X-ray visibility and strong adhesion to microcatheter. In this study, three different iodinated cyanoacrylates are newly synthesized as alternatives to Histoacryl and employed to develop liquid embolic compositions. Among them, 4-iodobutyl 2-cyanoacrylate (IBCA) was most preferable with high iodine content (730 mgI/mL) and fast polymerization. The IBCA-based embolic compositions containing ethyl oleate and acetic acid showed moderate viscosity and reduced catheter adhesiveness (∼ 0.80 N), and their polymerization time was freely controllable from 2 to 15 s. In the embolization test with rabbit models, the renal artery was successfully occluded by IBCA-based embolic compositions without vascular recanalization or non-target embolization for 4 w. Their embolic effect was further evaluated using swine models, demonstrating the practical applicability in the clinic. In conclusion, IBCA and its compositions are determined to have great potential as novel liquid embolic agents. This article is protected by copyright. All rights reserved.

Highly Efficient Photoinitiation Systems Based on Dibenzo[a,c]phenazine Sensitivity to Visible Light for Dentistry.

In this work, photoinitiation systems based on dibenzo[a,c]phenazine sensitivity to visible light were designed for their potential application in dentistry. Modification of the structure of dibenzo[a,c]phenazine consisted of introducing electron-donating and electron-withdrawing substituents and heavy atoms into position 11. The synthesized compounds are able to absorb radiation emitted by dental lamps during photoinitiation of the polymerization process. In the presence of acrylates, dibenzo[a,c]phenazines show excellent photoinitiating abilities in systems containing an electron donor or a hydrogen-atom donor as a second component. The developed systems initiate the polymerization process comparable to a commercial photoinitiator, i.e., camphorquinone. Moreover, the performed studies showed a significant shortening of the polymerization time and a reduction in the amount of light absorber. This indicates that polymeric materials are obtained at a similar rate despite a significant reduction in the concentration of the newly developed two-component photoinitiating systems.

Preparation of molecularly imprinted polymer for the specific adsorption and selective extraction of alkylresorcinols from whole wheat flour

Alkylresorcinols are important biomarkers for evaluating whole wheat foods. However, their structures encompass a broad spectrum of homologs, making isolating and analyzing individual alkylresorcinol notably challenging. Herein, we synthesized highly selective molecularly imprinted polymers (MIPs) utilizing a facile and cost-effective precipitation polymerization method and 5-heneicosylresorcinol (ARC21:0) as the template molecule. Various crucial preparation parameters were systematically optimized, such as different porogens, functional monomers, imprinting ratios, and polymerization time. The polymers were characterized through scanning electron microscopy and Fourier transform infrared spectroscopy, and their adsorption performances were thoroughly evaluated. MIPs exhibited a notably enhanced adsorption capacity compared with that of non-imprinted polymers, reaching an optimal adsorption amount of 71.75 mg·mL−1 and imprinting factor of 2.02. Altogether, the synthesized MIPs showed superior affinity and selectivity for ARC21:0, as confirmed by their selective extraction, suggesting their potential applications in the analysis, separation, and monitoring of ARC21:0 in whole wheat foods.

Flexible bistable polymer stabilised cholesteric texture light shutter display

ABSTRACT Bistable cholesteric liquid crystal displays meet various needs such as energy saving, long image storage time, and no backlight; however, their dense polymer network affects the electro-optical performance. In this work, polymer-stabilised cholesteric texture (PSCT) films with polymer spacer columns were prepared by two-step polymerisation using photomask. The effects of crosslinker content and mask polymerisation time on the morphology of the polymer spacer columns and the optoelectronic properties of the PSCT films were investigated. The results suggested that the film showed bistable performance and the formation of polymer spacer columns helped to optimize the contrast ratio of the sample without sacrificing response time. The cyclic experiment indicated that the optimized bistable PSCT film showed good stability. The adhesion strength of the PSCT film to the substrate was essentially the same as that of commercial PDLC. The simple operability and reusability of the process method make it a practical solution for the preparation of bistable PSCT films.

Solvent‐Free Synthesis of PMMA Particles using Tandem Acoustic Emulsification

AbstractPoly(methyl methacrylate) (PMMA) colloidal particles are nowadays extensively used in several applications and more specifically in nanotechnology. Challenges are focused on the green synthesis process leading to size‐controlled particles. In the present work, PMMA particles were successfully synthesized using tandem acoustic emulsification in water without organic solvent, and cross‐linkers. 2,2′‐azobis(2‐methylpropionamidine) dihydrochloride (AIBA) or ammonium persulfate (APS), were used as initiators. Parameters leading to size control were clearly identified. Consequently, the cooling rate of the solution after polymerization time appears dominating. Particle size distribution was monodispersed for both initiators. A nonionic surfactant, Tween 20, was also added, leading to a decrease in size particle and an increase in synthesis yield. Depending on the chemical groups provided by the initiator, PMMA particles appear negatively or positively charged. These charges located on the particle surface led to stable particle dispersion by limiting aggregation phenomena. Tunable surface charge was confirmed across the elaboration of coatings only made of PMMA particles, using conventional techniques wherein charged species are needed (Layer‐by‐Layer assembly and electrophoretic deposition). PMMA particles were also labelled using fluorescent dyes. Fluorescein and Nile Blue A were loaded during the polymerization process to ensure a homogeneous distribution of the dyes within the particles.

Composite aerogel with oriented structure of polyimide@ polypyrrole /MXene for effective shielding against electromagnetic waves and insulation

Although the rapid evolution of electromagnetic wave technology make much progress to society, but has also caused electromagnetic pollution, which poses risks to health, information security, and disrupts communication and device operation. The development of new Electromagnetic Interference (EMI) shielding materials, especially those that are lightweight, easy to process and high shielding efficiency, has become the key to overcoming this challenge. In this study, MXene nanosheets with few layers were fabricated by chemical etching with lithium fluoride (LiF) and hydrochloric acid (HCl). Subsequently, the unidirectional freeze-drying method and vacuum-assisted impregnation method were applied to fabricate polyimide@ polypyrrole/MXene (PI@PPy/MXene) composite aerogel with oriented structure. The electromagnetic shielding properties of the oriented PI@PPy composite aerogel were modulated by changing the polymerization time of PPy to control its conductivity. When the polymerization time was set as 7 h, the oriented PI@PPy composite aerogel showed the highest EMI efficiency, the value of EMI SE was 19.36 dB. With the introduction of MXene, the EMI SE of the PI@PPy/MXene composite aerogel was increased compared to PI@PPy and reached to 32.64 dB. The improvement in electromagnetic shielding performance was attributed to the co-enhancement among the PI aerogel with oriented structure, PPy and MXene, which is the result of the synergisic effect of Multiple reflection losses and polarization losses within the aerogel. The infrared thermography at 200°C showed that with increasing PPy polymerization time, the external temperatures of the samples are 40.3°C, 44.8°C, 51.4°C, 55.4°C and 48.6°C, demonstrating the excellent thermal insulation properties.

Self-blowing, hybrid non-isocyanate polyurethane foams produced at room temperature

Self-blowing polyurethane foams are essential for several everyday applications, yet their traditional production involves fossil-derived products and hazardous isocyanate compounds. Thus, research into isocyanate-free polyurethane foams is receiving considerable attention. However, current approaches often rely on external blowing agents, and/or high temperatures with long polymerization times. This research presents a rapid, self-blowing, partially bio-based non-isocyanate polyurethane (NIPU) foams at room temperature, specifically poly(hydroxy-thio-urethane), with both rigid and flexible configurations. The method involves the partial conversion of an epoxy resin to an oligomer mixture composed of 85% bio-cyclic carbonate and 15% of non-converted epoxide. This oligomer undergoes a fast process, through reactions between the epoxy groups and the reactive components, that is then followed by simultaneous aminolysis and decarboxylation reactions, arising from the interaction of an amine and cyclic carbonate. An in-situ blowing agent (CO2) is generated from the interaction between thiols and cyclic carbonate. The glass transition temperature is modulated by the thiol/amine content in rigid foams and by the addition of aliphatic long chains in flexible foams. With almost 30% renewable carbon content, these foams provide a sustainable alternative to traditional isocyanate-based pathways. The resulting porous materials possessed densities between 0.158 and 0.201 g/cm3. Finally, the foams can be transformed into films, enhancing recyclability and sustainability at the end of their lifecycle. Thus, this development has the potential to facilitate the production of eco-friendly, recyclable polyurethane foams.

Novel Photocatalyst Based on Through‐Space Charge Transfer Induced Intersystem Crossing Enables Rapid and Efficient Polymerization Under Low‐Power Excitation Light

AbstractCurrently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (&lt;50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm.

New fabric phase sorptive extraction for nondestructive analysis of heritage textile samples

Several types of pesticides used in museum collections over time become dangerous for people who may handle textile articles treated with such substances. In the case of the analysis of ancient, modern, and contemporary textile materials, it is particularly important to keep the artifacts intact, as they cannot be replaced. The need to use micro- or nondestructive techniques led to the development of methods such as solid-phase microextraction (SPME), liquid‒liquid dispersive microextraction (DLLME), and single-droplet microextraction (SDME). In this paper is described an optimized extraction method of three pesticides (malathion, methoxychlor, and permethrin) by creating a non-destructive solid phase extraction system on a textile support, abbreviated FPSE – 100 % cotton fabric coated with a sol-gel solution prepared from a polymer (PEG or PDMS). To obtain a suitable FPSE, the following parameters were evaluated: polymer selection (individual or mixture of polymers), acid catalyst (trifluoroacetic acid, acetic acid and hydrochloride acid), amount of polymer (1.0 g, 2.5 g or 5.0 g), polymerization time (30 min, 120 min and 240 min), ultrasonic bath temperature (40 °C and 70 °C), and type of bath to obtain the sol-gel (ultrasonic bath, water bath with stirring and mechanical stirrer). To complete the FPSE optimization, the influence of pesticide extraction time on FPSE and desorption from FPSE in ethyl acetate was also assessed.The pesticides extraction yields obtained for the laboratory textile samples are in the range of 52.7 %–128.0 %. The technique proposed in the manuscript proved to be effective as a nondestructive tool for evaluating and quantifying the presence of pesticides in textile museum collections. The approach described here reduces heritage object damage due to sampling compared to methods commonly employed and may represent a starting point for future research.

Controlled Magnetite Grafted Poly(glycidyl methacrylates) for Heavy Metal Absorption and Recovery via SET-LRP

A versatile magnetite based stringent polymer for effective metal capture was prepared by reacting iron oxide based initiator with glycidyl methacrylate monomer via single-electron transfer living radical polymerization (SET-LRP) technique. The versatile grafted polymer was successfully synthesized by metal catalyzed living radical polymerization using the catalyst system Cu/N,N,N',N'',N'''-pentamethyldiethylenetriamine as the ligand. The structural confirmation of the initiator and the grafted polymer was analyzed by using instrumentation methods such as proton nuclear magnetic resonance spectroscopy, UV-visible, TGA, SEM and gel permeation chromatography for molecular weight measurements. As the polymerization time increased, both the conversion and the molecular weight were observed to increase linearly with time. Narrow dispersed lower polydispersity index (PDI) and dispensable magnetite-g-PGMA was utilized for the extract of toxic lead from the wastewater. Sustained binding was observed due to the presence of epoxide ring in the repeating units of the polymer and recovered by magnetic effect. The material shows good stability as evident by TGA curves and better affinity to toxic lead as observed by UV-visible and SEM techniques.

Antibacterial Zirconia Surfaces from Organocatalyzed Atom-Transfer Radical Polymerization.

Antibacterial coatings are becoming increasingly attractive for application in the field of biomaterials. In this framework, we developed polymer coating zirconia with antibacterial activity using the "grafting from" methodology. First, 1-(4-vinylbenzyl)-3-butylimidazolium chloride monomer was synthesized. Then, the surface modification of zirconia substrates was performed with this monomer via surface-initiated photo atom transfer radical polymerization for antibacterial activity. X-ray photoelectron spectroscopy, ellipsometry, static contact angle measurements, and an atomic force microscope were used to characterize the films for each step of the surface modification. The results revealed that cationic polymers could be successfully deposited on the zirconia surfaces, and the thickness of the grafted layer steadily increased with polymerization time. Finally, the antibacterial adhesion test was used to evaluate the antibacterial activity of the modified zirconia substrates, and we successfully showed the antibacterial activity against Staphylococcus aureus and Pseudomonas aeruginosa strains.

Preparation of robust structural color film on cotton fabrics by caffeic acid

Structural coloration holds significant promise for achieving ecological coloring of textiles. Caffeic acid, a natural plant polyphenol characterized by its cost-effectiveness, environmental friendliness, and non-toxic properties, has been identified as a key player in this context. It is found that caffeic acid can generate a polycaffeic acid (PCfA) nanofilm at the gas-liquid interface under certain conditions. In this work, caffeic acid was utilized to create thin film nanostructures by self-polymerization for the structural coloration of cotton fabrics, where the hue of the structural colors can be adjusted by polymerization time. Additionally, the incorporation of polyvinyl alcohol (PVA) into the system enhances the rubbing and washing fastness of the resultant structural colored fabric. The morphology of the structural color fabric was investigated by scanning electron microscopy (SEM), and the thickness of the films corresponding to the different colors were determined. This innovative approach presents a novel methodology for the development of robust structural color films.

Fabrication of a tailor-made conductive polyaniline/ascorbic acid-coated nanofibrous mat as a conductive and antioxidant cell-free cardiac patch

Polyaniline (PANI) was in-situ polymerized on nanofibrous polycaprolactone mats as cell-free antioxidant cardiac patches (CPs), providing electrical conductivity and antioxidant properties. The fabricated CPs took advantage of intrinsic and additive antioxidant properties in the presence of PANI backbone and ascorbic acid as a biocompatible dopant of PANI. The antioxidant nature of CPs may reduce the serious repercussions of oxidative stress, produced during the ischemia-reperfusion (I/R) process following myocardial infarction. The polymerization parameters were considered as aniline (60 mM, 90 mM, and 120 mM), ascorbic acid concentrations ([aniline]:[ascorbic acid] = 3:0, 3:0.5, 3:1, 3:3), and polymerization time (1 h and 3 h). Mainly, the more aniline concentrations and polymerization time, the less sheet resistance was obtained. 1,1 diphenyl-2-picrylhydrazyl (DPPH) assay confirmed the dual antioxidant properties of prepared samples. The advantage of the employed in-situ polymerization was confirmed by the de-doping/re-doping process. Non-desirable groups were excluded based on their electrical conductivity, antioxidant properties, and biocompatibility. The remained groups protected H9c2 cells against oxidative stress and hypoxia conditions. Selected CPs reduced the intracellular reactive oxygen species content and mRNA level of caspase-3 while the Bcl-2 mRNA level was improved. Also, the selected cardiac patch could attenuate the hypertrophic impact of hydrogen peroxide on H9c2 cells. The in vivo results of the skin flap model confirmed the CP potency to attenuate the harmful impact of I/R.

Inside Back Cover

Polyhydroxyalkanoates with tunable properties can be readily prepared through stereoselective ring‐opening copolymerization of rac‐β‐butyrolactone and β‐propiolactone. By simply adjusting the polymerization conditions, such as the type of initiators and polymerization time, a variety of biodegradable copolyesters spanning from plastics to elastomers can be effectively produced in a one‐pot process. Further insights and details can be found in the article by Tang et al. on page 963—972.image