Vinyl Chloride Research Articles

Comprehensive evaluation of the impact of ionic liquid incorporation on the optical properties, Urbach energy, thin film morphology, and surface roughness of poly(vinyl chloride) based on ionic materials

Abstract A newly synthesis composite thin films of poly(vinyl chloride) has been refinement with ionic liquid, where PVC dissolved in THF with various concentrations of IL by casting method to form the composite thin films, without any reaction and IL dangles within PVC matrix. The thin films were examined by the diffusive reflectance device under the wavelength range (238–1300 nm). The XRD, EDX, and AFM techniques were utilized to discover the structure of the PVC matrix after additive IL. The XRD analysis illustrated the amorphous structure of the films, while the EDS analysis illustrated the main composition of pure PVC and composite PVC/IL. The optical properties and optical parameters were studied. The reflectance, extinction factor, transmittance, and imaginary dielectric constant declined, the absorption value was between (80–89 %), and the refractive index, real dielectric constant, and optical conductivity were increased. The indirect energy gap declined from 4.2 eV to 2.2 eV and the direct energy gap declined from 3.7 eV to 2.6 eV. The Urbach energy was increased from 2.09 eV to 15.45 eV revealing an increase in the disorders of electrons. The E d increased from 23.42 eV to 70.68 eV and E o increased from 7.00 eV to 10.88 eV. AFM analysis illustrated the roughness of the films increased after additive IL to the PVC Matrix from 1.08 nm to 4.45 nm and the root mean square of the particles ranged from 1.57 nm to 5.56 nm. The PVC composite thin films are utilized in solar cell and sodium-ion battery applications.

Challenging design of highly active Pt/CeO2–TiO2/ZSM-5 catalysts for VOCs low-temperature removal

Four Pt/CeO2–TiO2/ZSM-5 catalysts with different Pt species dispersion states and acidic properties were designed, and key factors affecting the oxidation activity of various VOCs (benzene, DCE, ethyl acetate and acetonitrile as typical organic compounds of aromatic hydrocarbon and halogen/oxygen/nitrogen-containing VOCs, respectively) were identified in the present work. The strength of the acid and oxidation sites on the surface of catalysts and their synergistic interaction play a crucial role. Highly dispersed Pt species and its strong redox ability promote low-temperature oxidation of benzene. A synergistic interaction between the acid and oxidation sites is required to achieve high DCE oxidation activity. An abundance of surface acid sites (particularly strong acid sites) favors the adsorption and dechlorination to form vinyl chloride of DCE, and the strong redox ability of oxidation sites would accelerate the deep oxidation of intermediates (such as vinyl chloride and acetic acid, etc.). For ethyl acetate or acetonitrile oxidation, the strong acidic property of the catalyst plays a prior role for their catalytic oxidation, which facilitates the low-temperature hydrolysis of ethyl acetate or acetonitrile. This work provides a significant thought to design and synthesize high activity catalysts for low-temperature oxidation of various VOCs pollutants.

One-Stage Pathway from Hollongdione to C17-Alkyne and Vinyl Chloride Following Mannich Bases and Carboxylic Acid.

Hollongdione is the first recorded example of the occurrence of a dammarane hexanor-triterpene in nature possessing antiviral and cytotoxic activity. Its simple one-stage transformation into compounds with terminal alkyne and vinyl chloride fragments via the interaction with phosphorus halides is reported. The copper(I)-catalyzed Mannich reaction of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20(21)-in 3 led to a series of aminomethylated products, while 17-carboxylic acid was obtained by ozone oxidation of 3-oxo-22,23,24,25,26,27-hexanor-dammar-20-chloro-20(21)-en 4; the following direct amidation of the latter has been developed. The structures of all new molecules were established by spectroscopic studies that included 2D NMR correlation methods; the molecular structures of compounds 2-5 were determined by X-ray analysis.

Lattice-Strain Engineering in Ni-Ru Heterostructures for Efficient Acetylene Hydrochlorination toward Vinyl Chloride.

Ru-based catalysts have emerged as promising alternatives to HgCl2 in vinyl chloride monomer (VCM) production by acetylene hydrochlorination. However, poor C2H2 activation and the generation of key intermediates (*CH2═CH) have posed grand challenges for enhanced catalytic performances. Herein, we synthesized a Ni-intercalated Ru heterostructure using a lattice-strain engineering strategy, resulting in the desired electronic and chemical environments. The collaboration of Ni splits the adsorption centers of C2H2 and HCl by weakening the strong steric hindrance, and it also promotes the activation of the linear C≡C configurations. The well-controlled lattice strain enables strong d-d hybridization interactions between Ni and Ru, resulting in an upshift of the d-band center from -3.72 eV (for Ru/C) to -3.49 eV and electronic delocalization. This optimized local Ni-Ru/C structure thus enhances *H adsorption while weakening the energy barrier for generating *CH2═CH intermediates. Furthermore, the energy barrier for VCM formation was simultaneously reduced. Accordingly, the Ni-Ru/C heterostructures achieve improved performance in pilot-scale trials, with a conversion of >99.2% and stability for over 500 h. These performances significantly surpass most reported Ru-based moieties and the traditional Hg catalysts, offering a promising avenue for C2H2 activation in industrial applications.

Synthesis and Photocatalytic Application of Magnetic CoFe2O4/Conjugated Poly(vinyl chloride) Derivative Nanocomposite.

CoFe2O4 has potential for application as a magnetically recoverable visible-light photocatalyst, but its photocatalytic activity is encumbered by the high recombination probability of its photogenerated holes (h+) and electrons (e-). This work was undertaken to boost the photocatalysis of CoFe2O4 through coupling with conjugated poly(vinyl chloride) derivative (CPVC). An easily implementable solvothermal-liquid solid mixing-evaporation of the solvent-pyrolysis method was exploited to synthesize CoFe2O4/CPVC nanocomposites. The photocatalytic capabilities of the products were assessed through photocatalyzing the reduction of Cr(VI) under visible-light (λ > 420 nm). The results demonstrate that the optimal CoFe2O4/CPVC nanocomposite (CoFe2O4/CPVC-2) has markedly heightened photocatalytic activity (3.6 times that of CoFe2O4) and competent reusability and is magnetically recoverable. Furthermore, CoFe2O4/CPVC-2 also shows superior performance toward photocatalytic treatment of the diluted Cr(VI)-containing passivation solution of copper alloys. It is deduced based on the photoelectricity measurement results that the increased photocatalysis of CoFe2O4/CPVC-2 is chiefly attributed to its p-n heterojunction structure, which greatly elevates the h+-e- separation and transfer efficiency. When waste PVC plastic films (replacing the new pure PVC powder) were utilized for the synthesis, the obtained CoFe2O4/CPVC nanocomposite exhibited even better photocatalytic activity (4 times that of CoFe2O4). This work not only has made a new magnetically recoverable, efficient visible-light photocatalyst for decontamination of Cr(VI) in water but also is inspirational for recycling PVC plastic waste to produce high-valued visible-light photocatalysts.

An experimental and mechanism study on the pyrolysis of sulfur mustard

Experimental studies on the pyrolysis of sulfur mustard (HD) were conducted from 673 to 1473 K using Py-GC/MS combined with two separate columns. The HD pyrolysis rate exceeded 99 % at a pyrolysis time of approximately 2 seconds above 1073 K. The pyrolysis products of HD mainly include ethylene, vinyl chloride, carbon disulfide, thiophene, hydrogen chloride and hydrogen sulfide. The main reaction mechanism of HD pyrolysis was investigated using quantum chemistry methods combined with the TST/VTST theory. At 673 K, the initial reaction pathway of HD primarily involves an intramolecular HCl elimination and the cleavage of the C-S bond. The radical reactions will dominate the pyrolysis of HD once radical pool is formed. The reaction pathways of the important radical intermediates were analyzed, and the formation mechanisms of the main pyrolysis products were investigated. Theoretically, the high-pressure limit rate constants for the major reactions were calculated. This study contributes to a deeper understanding of the HD pyrolysis mechanism and provides a theoretical and data foundation for the destruction of HD.

Cuphea as a Source of Fully Crop-Based Plasticizers for Poly(vinyl chloride)

<i>Cuphea</i> as a Source of Fully Crop-Based Plasticizers for Poly(vinyl chloride)

Research on pollution identification and safety thresholds based on the olfactory effect on a halogenated hydrocarbon contaminated site

To effectively address odor control issues at sites contaminated with halogenated hydrocarbons, it is essential to establish an odor risk prediction system for evaluating potential risks that may impact future planning. This research focuses on a representative halogenated hydrocarbon-contaminated site, examining the spatial and temporal distribution characteristics of key pollutants in soil gas. By analyzing odor contribution rates, the study identifies significant odorants in soil gas, which enables the derivation of both probabilistic and deterministic safety thresholds for soil and groundwater based on olfactory effects. The findings indicate that 1,1-dichloroethylene, vinyl chloride, chloroform, and 1,1-dichloroethane are prevalent throughout the contaminated site, displaying elevated concentration levels and substantially influencing the overall contamination extent. These substances are highlighted as critical pollutants requiring attention. Correlation analysis (P < 0.05) reveals a strong relationship between the concentrations of vinyl chloride, 1,1-dichloroethane, and chloroform with groundwater depth and air temperature. Additionally, the analysis of odor activity values (OAV) identified 1,1-dichloroethene, 1,4-dichlorobenzene, chlorobenzene, chloroform, and vinyl chloride as key olfactory factors at the site. The corresponding probabilistic safety thresholds are 0.68, 1.65, 0.50, 7.87, and 3.72 mg kg−1 for soil, and 9.29, 3.46, and 1.09, 69.55, and 47.01 mg L−1 for groundwater, respectively. Among them, the odor risks of chlorobenzene and 1,1-dichloroethylene warrant more attention than soil contamination risks; regarding 1,4-dichlorobenzene, it is recommended to concurrently consider odor risks during human health risk assessment; as for vinyl chloride and chloroform, their odor risks can be largely eliminated based on human health-oriented pollution management.

Effect of Viscosity and Air Gap within the Spinneret on the Morphology and Mechanical Properties of Hollow-Fiber Polymer Membranes for Separation Performance.

Hollow-fiber membranes for nanofiltration were prepared from the blending of Poly (ethylene glycol) (PEG) with Poly (vinyl chloride) (PVC) with different PEG molecular weights (400 and 4000 g/mol) and PVC via a dry/wet spinning process. In the spinning process, the effects of air gap, wind-up speed, dope extrusion rate, and bore extrusion rate were examined. In addition, the different lengths of the center tube, which acted as the inner-side fiber diameter during the preparation of hollow-fiber membranes, were studied. This research was investigated in order to observe the morphological, dielectric, and dynamic mechanical thermal properties to identify a suitable preparation of a hollow-fiber membrane for feasible applications. The morphology of the PVC-580 blended PEG-400 5 weight percent hollow-fiber membrane was seen to have a dense skin on both the inner and outer fiber surface, along with a suitable dope viscosity. Moreover, it offered finger-like substructures that could provide a high applicable feed-stream permeability and selectivity. Finger-like substructures were present on the near inner fiber surface at the controlled center-tube length of 0.3 cm, more so than at the center tube of 1 cm. This was because the solvent and non-solvent in the lumen tube exchanged more quickly than they did in the coagulant bath. The effect of the wind-up speed during the spinning process was significantly influenced by an affordable hollow fiber that can be indicated by the drawing ratio (λ). It was found that the drawing ratio of 3.3 showed a thickness thinner than 2.6 and 2.0, respectively. In summary, a controlled wind-up speed, an acceptable dope viscosity, and-most importantly-an agglomerated time resulted in membrane preparation.

Preparation of rare-earth LDHs stabilizers and their effects on the thermal stability of poly(vinyl chloride)

Preparation of rare-earth LDHs stabilizers and their effects on the thermal stability of poly(vinyl chloride)

Microplastics Biofragmentation and Degradation Kinetics in the Plastivore Insect Tenebrio molitor.

The insect Tenebrio molitor possesses an exceptional capacity for ultrafast plastic biodegradation within 1 day of gut retention, but the kinetics remains unknown. Herein, we investigated the biofragmentation and degradation kinetics of different microplastics (MPs), i.e., polyethylene (PE), poly(vinyl chloride) (PVC), and poly(lactic acid) (PLA), in T. molitor larvae. The intestinal reactions contributing to the in vivo MPs biodegradation were concurrently examined by utilizing aggregated-induced emission (AIE) probes. Our findings revealed that the intestinal biofragmentation rates essentially followed the order of PLA > PE > PVC. Notably, all MPs displayed retention effects in the intestine, with PVC requiring the longest duration for complete removal/digestion. The dynamic rate constant of degradable MPs (0.2108 h-1 for PLA) was significantly higher than that of persistent MPs (0.0675 and 0.0501 h-1 for PE and PVC, respectively) during the digestive gut retention. Surprisingly,T. molitor larvae instinctively modulated their internal digestive environment in response to in vivo biodegradation of various MP polymers. Esterase activity and intestinal acidification both significantly increased following MPs ingestion. The highest esterase and acidification levels were observed in the PLA-fed and PVC-fed larvae, respectively. High digestive esterase activity and relatively low acidification levels inT. molitor larvae may, to some extent, contribute to more efficient MPs removal within the plastic-degrading insect. This work provided important understanding of MPs biofragmentation and intestinal responses to in vivo MPs biodegradation in plastic-degrading insects.

Asymmetric Ru-In atomic pairs promote highly active and stable acetylene hydrochlorination

Ru single-atom catalysts have great potential to replace toxic mercuric chloride in acetylene hydrochlorination. However, long-term catalytic stability remains a grand challenge due to the aggregation of Ru atoms caused by over-chlorination. Herein, we synthesize an asymmetric Ru-In atomic pair with vinyl chloride monomer yield (>99.5%) and stability (>600 h) at a gas hourly space velocity of 180 h−1, far surpassing those of the Ru single-atom counterparts. A combination of experimental and theoretical techniques reveals that there is a strong d-p orbital interaction between Ru and In atoms, which not only enables the selective adsorption of acetylene and hydrogen chloride at different atomic sites but also optimizes the electron configuration of Ru. As a result, the intrinsic energy barrier for vinyl chloride generation is lowered, and the thermodynamics of the chlorination process at the Ru site is switched from exothermal to endothermal due to the change of orbital couplings. This work provides a strategy to prevent the deactivation and depletion of active Ru centers during acetylene hydrochlorination.

Thermo‐oxidative degradation behavior of poly(vinyl chloride) insulation for new and overloaded wires via TG‐FTIR

AbstractWhen a poly(vinyl chloride) (PVC) wire experiences overload failure, the internal structure of the insulation changes to become overloaded insulation and the fire hazard changes. In this study, the thermo‐oxidative degradation behavior of new and overloaded PVC insulation materials was analyzed using coupled thermogravimetric‐Fourier transform infrared spectroscopy (TG‐FTIR). The thermo‐oxidative degradation results show that the first two stages of thermo‐oxidative degradation of PVC insulation are important stages for measuring fire hazard. In addition, the onset temperature of thermo‐oxidative degradation of overloaded PVC insulation was increased. The activation energies of the first two stages of the overloaded PVC insulation increased by 7.7% and 27.0%, respectively, compared to the new PVC insulation. And the reaction mechanism is changed. The FTIR results indicate that the increased amount of volatile organic compounds and CO2 generated during the pyrolysis of the overloaded PVC insulation may result in the generation of more heat and smoke during combustion, thus increasing the fire hazard.

A General Approach for Photo-Oxidative Degradation of Various Polymers.

The escalating demand for plastics has resulted in a surge of plastic waste worldwide, posing a monumental environmental challenge. To address this issue, a versatile photo-oxidative degradation method applicable to seven distinct polymer families is proposed, comprising poly(isobutyl vinyl ether) (PIBVE), poly(2,3-dihydrofuran) (PDHF), poly(vinyl acetate) (PVAc), poly(n-butyl acrylate) (PBA), poly(methyl acrylate) (PMA), poly(vinyl chloride) (PVC), poly(dimethyl acrylamide) (PDMA), poly(ethylene oxide) (PEO), poly(oligo(ethylene glycol) methyl ether acrylate) (PEGMEA), and even poly(methyl methacrylate) (PMMA). This method employs photo-mediated hydrogen atom transfer (HAT) followed by oxidation to promote polymer degradation. This reaction is carried out under aerobic condition in the presence of iron trichloride (FeCl3) as a photocatalyst in combination with low-intensity purple light irradiation. The process can degrade up to 97% of the polymer in less than 3 h. This degradation process can be easily controlled by switching the light off, which allows for precise modulation of the degradation rate, enhancing the effectiveness of the method. Overall, this method provides a sustainable method for degrading various polymer types with low energy input.

Effect of Plasticizer Type on Polymer Inclusion Membranes Properties and Performance for Zinc Separation

AbstractThe goal of the present study is to evaluate the effect of plasticizer in PIMs properties and performance for zinc separation. Membranes were prepared by casting a solution containing poly (vinyl chloride) (PVC) as base polymer, di (2‐ethylhexyl) phosphoric acid (D2EHPA) as carrier, and 2‐nitrophenyl octyl ether (NPOE) or tris (2‐butoxyethyl) phosphate (TBEP) as plasticizers. The newly developed PIMs transported practically all ZnII ions from a feed phase at pH 5 to a 1 M H2SO4 stripping phase. The results showed that the transport flux and its efficiency depend on the chemical nature of the plasticizer. It can be perceived that NPOE (with dielectric constant of 23.1) produced the highest transport flux of zinc (J0=1.62±0.05 10−5 mol m−2 s−1). The single ion transport of zinc was significantly higher than the binary and ternary mixtures. In ternary solution, the transport efficiency for metal ions was in the order of ZnII&gt;CuII&gt;NiII. The transport efficiency of the PVC/NPOE/D2EHPA membrane remained constant until the seventh use. The findings of this work will allow the invention of advanced separation technology ensuring the sustainability of metal resources.

Synthesis and dielectric properties of polyvinyl chloride/zinc oxide nanocomposites

AbstractBecause of its special structural and functional characteristics, poly(vinyl chloride)/zinc oxide nanocomposite (PVC/ZnO) exhibits great potential in a variety of electrical, optical, water treatment, and medical applications. According to that, this study was carried out to examine the AC electrical properties of the prepared PVC/ZnO nanocomposite films using the AC impedance techniques. The PVC/ZnO nanocomposite films were prepared by casting method by weight% concentrations of 2.5, 5.0, 7.5 and 10.0% ZnO nanoparticle. Each mixture was fabricated in film and casted in 5 cm × 5 cm glass caste. Fourier transform infrared (FTIR) spectroscopy, x‐ray diffraction (XRD), and scanning electron microscopy (SEM) were used to characterize the nanocomposites samples. The results of the FTIR spectroscopy analysis of the PVC/ZnO nanocomposites confirmed the presence of peaks characteristic of the vibration of the ZnO bond. XRD revealed that pure PVC films are partially crystalline with hallow peak but ZnO nanoparticles have wurtzite structure, and the nanocomposite films were almost the same as those of ZnO with decrease in the degree of crystallization, causing increase in the amorphous region. The surface of the films was analyzed by SEM, which becomes rough with some small aggregates compared with pure PVC with good distribution in the entire surface region with bright spots. The electrical properties AC conductivity (), real dielectric constant (), imaginary dielectric constant (), real electrical modulus (), and imaginary electric modulus () were studied in the frequency range 2–6 MHz and temperature range 293–313 K for the prepared film studied. The results showed that the properties of the PVC/ZnO nanocomposite films were found to be dependent on the frequency, and the concentration of the ZnO nanoparticle in the PVC polymer matrix. In addition, the results of the study show that there is a sharp increase in the , with increasing of temperature. In contrast, the other parameters, that is, , , , and are temperature independence.Highlights PVC/ZnO nanocomposite films with different weight% concentrations of ZnO nanoparticle were prepared. AC electrical properties were measured using AC impedance techniques. The nanocomposites samples were characterized using FTIR, XRD, and SEM. Electrical properties , , , , and were found to be frequency and temperature dependences.

Continuous-flow synthesis of di-(2-ethylhexyl) peroxydicarbonate in a packed-bed microreactor: Process optimization and kinetic modeling

Di-(2-ethylhexyl) peroxydicarbonate (EHP) is a low-temperature liquid organic peroxide commonly used as an initiator for polymerization of vinyl chloride and ethylene. The exothermic nature of peroxidation and the instability of this peroxide product pose safety challenges during synthesis. Therefore, batch reaction processes for synthesizing such products often prioritize safety over efficiency. In this work, an efficient and safe protocol was proposed for EHP production with the use of a packed-bed microreactor. Response surface methodology was applied to optimize critical process parameters, resulting in a remarkable yield of 95.48% in a residence time of 23.8 min. It proves that the efficiency was significantly improved by the packed-bed microreactor compared with batch reactors. Additionally, an operational window was established to guide the process development for synthesizing EHP in flow. Finally, a kinetic model was established, which was of crucial theoretical significance and practical value for better understanding peroxidation processes and parameter optimization.

Boosting poly(vinyl chloride) with waste-based plasticizer and green nanofiller

Boosting poly(vinyl chloride) with waste-based plasticizer and green nanofiller

The highly selective green colorimetric detection of yttrium ions in biological and environmental samples using the synergistic effect in an optical sensor.

A new eco-friendly method for creating an optical sensor membrane specifically designed to detect yttrium ions (Y3+) has been developed. The proposed sensor membrane is fabricated by integrating 4-(2-arsonophenylazo) salicylic acid (APASA), sodium tetraphenylborate (Na-TPB), and tri-n-octyl phosphine oxide (TOPO) into a plasticized poly(vinyl chloride) matrix with dimethyl sebacate (DMS) as the plasticizer. In this sensor membrane, APASA functions dually as an ionophore and a chromoionophore, while TOPO enhances the complexation of Y3+ ions with APASA. The composition of the sensor membrane has been meticulously optimized to achieve peak performance. The current membrane exhibits a linear dynamic range for Y3+ ions from 8.0 × 10-9 to 2.3 × 10-5 M, with detection and quantification limits of 2.3 × 10-9 and 7.7 × 10-9 M, respectively. No interference from other potentially interfering cations and anions was observed in the determination of Y3+. The membrane showed strong stability and a swift response time of about 3.0 minutes, with no signs of APASA leaching. This sensor is highly selective for Y3+ ions and can be renewed by treating it with 0.15 M HNO3. It has been effectively applied to measure Y3+ in nickel-based alloys, as well as in biological and environmental samples.

FLEXIBLE DUODENAL MONOCANNULA OF THE NATIONAL AGRICULTURAL AND FOOD CENTRE DESIGN FOR THE DETERMINATION OF INTESTINAL NUTRIENT DIGESTIBILITY IN CATTLE

Research in physiology of ruminant nutrition using the in sacco and mobile bag methods and developing and testing of a duodenal cannula of our own construction including our own surgical application in cattle, led to the intellectual property protection. The duodenal monocannula for determination of nutrient intestinal digestibility in cattle, designed by the National Agricultural and Food Centre (NPPC, Slovak Republic), has been registered by European Union intellectual property office, as a Registered Community Design. The innovativeness of the technical design of the "NPPC cannula" lies in the fact that the cannula is made of one piece of a straight tube with an inner diameter of 22 mm. The tube is smooth, with no additional extensions and glued parts. The operation does not require ligation of the bowel with an arterial prosthesis or a polyurethane felt. The dimensions of the cannula allow the use of the mobile bag method without any problems. The vinyl chloride emulsion was designed to polymerize at the lower temperature, than has been currently used in this procedure (130 °C), and the end used for fixation in the intestine could be shaped after immersion in warm water. During the growth of the animals, the tube length can be prolonged to adapt to the duodenal size. As a result, the life of cannulated animals can be extended without age limitation.