Toluene Diisocyanate Research Articles

Ambient-cured cardanol-derived polyurea coatings for anti-corrosive and anti-bacterial applications

Present work obviates the demand for petroleum products from the coating industry. The current study highlights the potential of bio-based precursor i.e., cardanol for synthesizing solventless coating systems for corrosion inhibition. Initially, prepolymer resin was synthesized from cardanol and was later reacted with toluene diisocyanate (TDI) in different wt% (10, 15, 20, and 25) to obtain an ambient cured polyurea (ACPUrea) resin. The structure of ACPUrea resin was confirmed with the help of FTIR and NMR spectral techniques. The impact of TDI percentage on the coating performance was evaluated in terms of curing behavior, standard phyisco-mechanical characteristics, thermal stability, and chemical resistance as well as wetting behavior. It reveals ACPUrea3 coatings performed better than their other counterparts and 20 wt% TDI is the optimal amount required to fabricate mechanically durable, thermally resistant (>250 °C), hydrophobic (contact angle: 138o), and chemically stable coatings. X-ray diffraction and field emission scanning electron microscopy techniques confirmed the amorphous nature and rough morphology of ACPUrea coating. The bactericidal activities of ACPUrea coatings were also evaluated by standard methods against various gram-positive and gram-negative bacteria, no bacterial growth was observed on and underneath these coatings. Electrochemical impedance spectroscopy suggested outstanding corrosion inhibition efficacy (82 %) of ACPUrea3 coating in harsh corrosive environments. Furthermore, the impedance value observed from the Nyquist plot was found to be steady throughout 15 days of immersion. The overall study emphasizes the utilization of cardanol for synthesizing polyurea coatings with higher thermal stability, excellent corrosion resistance, and strong bactericidal properties.

91 Isocyanates Aerosols Sampling for Occupational Exposures Assessment

Abstract Isocyanate compounds are potent sensitizers, in particular through the development of skin dermatitis and allergies. They are one of the main causes of occupational asthma. None no-adverse-effect level has been establishes for isocyanates, therefore, it is important to measure isocyanates level at workplaces. Most of the time, isocyanates are present in workplaces atmosphere both in gas and particle phase, which makes their quantitative sampling difficult. Actual sampling methods do not fit with individual sampling over 8 hours. The aim of this work was first to characterize the particles size distribution in workplaces, depending on the isocyanate and the process used. Then, we studied the effectiveness of CIP 10-I as a sampling device for four isocyanates, compared to impinger and impregnated filter. Particles size distribution was determined thank to different cascade impactors such as Andersen, DLPI+ and MiniMOUDI-8. The Mass Median Aerodynamic Diameter (MMAD) of 4,4’-MDI (4,4’-diphenylmethane diisocyanate) particles in polyurethane foam projection process was found to be higher than 4 µm. In paint spray process, HDI (hexamethylene diisocyanate) particles MMAD was between 1 and 2 µm. The aerosol generation system was designed to obtain particles sizes closed to those observed in workplaces. The CIP 10-I collection foam was impregnated with the same derivative agent as filters. HDI, 2,4-TDI and 2,6-TDI (Toluene diisocyanate) aerosols were generating at concentrations between 10 and 250 µg/m3 in dry air. Whatever the concentration, CIP 10-I collection efficiency is higher than that of filters. Further investigation are currently performed to investigate CIP 10-I performance for MDI sampling.

Emission and time-resolved migration rates of aromatic diamines from two flexible polyurethane foams.

Performing risk assessments (RA) on household use of flexible polyurethane (PU) foams requires access to reliable data about emission and migration of potential diamine impurities. A toluene diisocyanate (TDI) and a methylene diphenyl diisocyanate (MDI) based foam were thermally treated to enable measurements on samples with defined concentrations of the corresponding diamines, toluene diamine (TDA), and methylene dianiline (MDA). The thermally treated foams used for emission testing contained up to 15mg.kg-1 of TDA and 27mg.kg-1 of MDA. Those used for migration testing contained 5.1mg.kg-1 of TDA and 14.1mg.kg-1 of MDA. Stability of the thermally generated diamines was sufficient for testing over a 37-day period. Analytical techniques that did not decompose the polymer matrix were applied. Emission rates for TDA and MDA isomers were less than the limit of quantitation (LOQ) of 0.008-0.07μg.m-2.h-1. Migration was studied using samples of the same thermally treated foams over a 35-day period. Quantifiable migration of MDA from the MDI-based foam was only observed on Days 1 and 2. From Day 3 onward, migration rates were less than the LOQ. Quantifiable migration of TDA from the TDI-based foam rapidly decreased with time and was only observed on Days 1 thru 3. From Day 4 onward, migration rates were less than the LOQ. Theoretically, the migration rate should be inversely proportional to the square root of time (t) as t-0.5. This relationship was confirmed by the experimental data and enables extrapolating migration values to more extended time periods to conduct RAs.

Sampling chamber with minimal wall surface for simultaneous emission testing of diisocyanates and diamines from polyurethane products

A sampling chamber was developed for emission testing of diisocyanates, methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), and corresponding diamines, methylene diphenyl diamine (MDA), and toluene diamine (TDA) from polyurethane (PU) product surfaces. In addition, a methodology for validation of the sampling chamber was presented, based on the introduction of generated standard atmospheres of the different diisocyanates and diamines to the sampling chamber system. Sampling of diisocyanates and diamines was performed on a circular glass fiber filter (150mm diameter) impregnated with dihexyl amine (DHA) and acetic acid (AA) positioned inside a cylindrical stainless steel sampling chamber. The diisocyanates were immediately derivatized to DHA derivatives, and the amines were derivatized in a subsequent work-up procedure with ethyl chloroformate (ECF). The design of the sampling chamber and the presented methodology allowed for simultaneous sampling and analysis of diisocyanates and diamines of emission from a large surface area with minimal interior wall interaction in the sampling chamber. Performance characteristics of the sampling chamber for different sampling times and air humidity were obtained by determining collected amounts of the diisocyanates and diamines in the different parts of the sampling chamber. The repeatability of the collected amount on the impregnated filters in the sampling chamber was 15% with an overall recovery for 8h of sampling in the range of 61% to 96%. The performance of the sampling chamber was not affected by air humidity (5%-75% RH), and no breakthrough during sampling was observed. LC-MS/MS determinations allowed for emission testing of diisocyanates and diamines on product surfaces as low as 10-30ng m-2 h-1.

Method Development for Detecting Low Level Volatile Organic Compounds (VOCs) among Workers and Residents from a Carpentry Work Shop in a Palestinian Village.

Volatile organic compounds (VOCs) are considered a major public health concern in industrial location areas. The presence of exposure to (VOCs) has raised concern regarding the health effects caused by chronic human exposure as this will increase cancer diseases in the village. An analytical method has been developed and modified to help us detect 38 VOCs in the blood of 38 volunteers who are related to a carpentry shop at the parts-per-trillion level. To measure and evaluate the potential risk, several devices, such as portable passive monitors and air-collected samples, in addition to blood concentration, were used to study three different occupational groups. Ten of the volunteers are employees at the shop, 10 volunteers live very close to the shop, and 10 of them are students in an elementary school very close to the shop. In this study, we developed an automated analytical method using headspace (HS) together with solid-phase microextraction (SPME) connected to capillary gas chromatography (GC) equipped with quadrupole mass spectrometry (MS). The detection limits for the method used were measured in the range from 0.001 to 0.15 ng/L, using linear calibration curves that have three orders of magnitude. The detected concentrations ranged from 3 ng L-1 for trichloroethene to 91 ng L-1 for toluene and 270 ng L-1 for 2,4-diisocyanate, which was derived from the paint solvents used for the wood in the carpentry shop and the paints on the walls. More than half of all assessed species (80%) had mean concentration values less than 50 ng L-1, which is the maximum allowed for most VOCs. The major chemical types among the compounds quantified will be those we found in our previous study in the surrounding air of a carpentry workshop in Deir Ballout in Palestine, which were toluene diisocyanate and butyl cyanate. Some were found to be highly present air. Most of the measurements were below the guidelines of the World Health Organization (WHO). Despite the fact that this study only involved a small number of smokers, smoking was found to be connected with several blood and breath components. This group includes unsaturated hydrocarbons (1,3-butadiene, 1,3-pentadiene, 2-butene), furans (2,5-dimethylfuran), and acetonitrile. The proposed classification of measured species into systemic (blood-borne) and exogenous volatiles is strictly hypothetical, as some species may have several origins.

Quercetin-Induced Enhancement of Nasal Epithelial Cells' Ability to Produce Clara Cell 10-kD Protein In Vitro and In Vivo.

Background: Quercetin, a polyphenolic flavonoid found in various plants and foods, is known to have antioxidant, antiviral and anticancer effects. Although quercetin is well known to exert anti-inflammatory and anti-allergic effects, the precise mechanisms by which quercetin favorably modifies the clinical status of allergic diseases, such as allergic rhinitis (AR), remain unclear. The present study examined whether quercetin could modulate the production of the endogenous anti-inflammatory molecule, Clara cell 10-kD protein (CC10), in vitro and in vivo. Methods: Human nasal epithelial cells (1 × 105 cells/mL) were stimulated with 20 ng/mL of tumor necrosis factor-alpha (TNF) in the presence of quercetin for 24 h. CC10 levels in culture supernatants were examined by ELISA. Sprague Dawley rats were sensitised with toluene 2,4-diisocyanate (TDI) by intranasal instillation of 10% TDI in ethyl acetate at a volume of 5.0 μL once daily for five days. This sensitisation procedure was repeated after an interval of two days. The rats were treated with different dosages of quercetin once daily for five days starting on the 5th day following the second sensitization. Nasal allergy-like symptoms induced by the bilateral application of 5.0 μL of 10% TDI were assessed by counting sneezing and nasal-rubbing behaviours for 10 min immediately after the TDI nasal challenge. The levels of CC10 in nasal lavage fluids obtained 6 h after TDI nasal challenge were examined using ELISA. Results: The treatment of cells with low doses of quercetin (<2.5 μM) scarcely affected TNF-induced CC10 production from nasal epithelial cells. However, the ability of nasal epithelial cells to produce CC10 after TNF stimulation significantly increased on treatment with quercetin doses (>5.0 μM). The oral administration of quercetin (>25 mg/kg) for five days significantly increased the CC10 content in nasal lavage fluids and attenuated the nasal symptoms induced by the TDI nasal challenge. Conclusions: Quercetin inhibits AR development by increasing the ability of nasal epithelial cells to produce CC10.

Mitoquinone ameliorated airway inflammation by stabilizing β-catenin destruction complex in a steroid-insensitive asthma model

Background and purposeMitochondrial dysfunction is an essential part of the pathophysiology of asthma, and potential treatments that target the malfunctioning mitochondria have attracted widespread attention. We have previously demonstrated that aberrant epithelial β-catenin signaling played a crucial role in a toluene diisocyanate (TDI)-induced steroid-insensitive asthma model. The objective of this study was to determine if the mitochondrially targeted antioxidant mitoquinone(MitoQ) regulated the activation of β-catenin in TDI-induced asthma. MethodMice were sensitized and challenged with TDI to generate a steroid-insensitive asthma model. Human bronchial epithelial cells (16HBE) were exposed to TDI-human serum albumin (HSA) and ethidium bromide(EB) to simulate the TDI-induced asthma model and mitochondrial dysfunction. ResultsMitoQ dramatically attenuated TDI-induced AHR, airway inflammation, airway goblet cell metaplasia, and collagen deposition and markedly protected epithelial mitochondrial functions by preserving mass and diminishing the production of reactive oxygen species (ROS). MitoQ administration stabilized β‐catenin destruction complex from disintegration and inhibited the activation of β‐catenin. Similarly, YAP1, an important constituent of β‐catenin destruction complex, was inhibited by Dasatinib, which alleviated airway inflammation and the activation of β‐catenin, and restored mitochondrial mass. In vitro, treating 16HBE cells with EB led to the activation of YAP1 and β-catenin signaling, decreased the expression of glucocorticoid receptors and up-regulated interleukin (IL)-1β, IL6 and IL-8 expression. ConclusionOur results indicated that mitochondria mediates airway inflammation by regulating the stability of the β-catenin destruction complex and MitoQ might be a promising therapeutic approach to improve airway inflammation and severe asthma. Availability of data and materialsThe data that support the findings of this study are available from the corresponding author upon reasonable request. Some data may not be made available because of privacy or ethical restrictions.

Genetic basis for the biodegradation of a polyether-polyurethane-acrylic copolymer by a landfill microbial community inferred by metagenomic deconvolution analysis

Plastic accumulation in the world amounts to approximately 8300 million tons. Polyurethanes (PU) account for 7.7 % of total plastics production worldwide, and their diverse chemical composition makes them highly recalcitrant to biodegradation. Several works have reported polyurethane-degrading microbial communities. However, it is still necessary to learn more about the chemical, biochemical, and genetic bases linked to the polyurethanolytic phenotype and the microbial taxonomic determinants responsible for metabolizing the PU polymer and its associated chemical additives. To shed light on this problem, we applied physical, chemical, biochemical, metagenomic, and bioinformatic analyses to explore the biodegradation capability and related biochemical and genetic determinants of the BP6 microbial community that can grow in PolyLack, a commercial coating containing a polyether polyurethane acrylate (PE-PU-A) copolymer and several additives, as sole carbon source. We observed complete additives (isopropanol, N-methyl-2-pyrrolidone, 2-butoxyethanol, alkyl glycol ethers) biodegradation and the appearance of released polymer components (toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI) derivatives), and multiple degradation products since early cultivation times. The Hi-C metagenomic analysis identified a complex microbiome with 35 deconvolved Metagenome-Assembled Genomes (MAGs) – several new species – and biodegradation markers that suggest the coexistence of hydrolytic, oxidative, and reductive metabolic strategies for degrading the additives and the PU copolymer. This work also provides evidence of the metabolic capability the BP6 community has for biodegrading polyether polyurethane foams. Based on these analyses, we propose a novel metabolic pathway for 4,4′-methylenedianiline (MDA), an initial biodegradation intermediate of MDI-based PU, encoded in the complex BP6 community metagenome and suggest that this community is a potential biotechnological tool for PU bio-recycling.

Superhydrophobic Mn(II)-coordinated technical cashew nut shell liquid-based bactericidal and corrosion-resistant advanced polyurethane coatings

A facile route has been reported to formulate mesoporous and covalently tethered superhydrophobic (160°) metal (Mn(II)) coordinated bio-polyurethane (PU) films/coatings. Technical cashew nut shell liquid-Formaldehyde (TCNSL-F) pre-polymer was used to prepare three different metal-coordinated polyurethane {Mn(II)TCNSL-F-PU20/25/30} films/coatings by using toluene diisocyanate (TDI) (20 %, 25 %, and 30 % w.r.t. polyol) as chain extender. Fourier transform infrared (FTIR) spectroscopy analyzes the chemical structures and changes in functional groups (-OH, >CO, -NCO), while X-ray diffraction (XRD) patterns reveal the amorphous nature of these films. The coordination with metal ions improves the chemical resistance, swelling ability (pH 4, 7.4, and 10), physicomechanical properties (scratch resistance (2.2 lb), impact resistance (150 lb/in.), bending (1/8 in.), adhesion, and gloss (98 GU) of the final coatings. Thermogravimetric analysis and its derivative (TGA and DTA) demonstrate the relatively high thermal stability (up to 200 ℃) and flame retardancy with a limited oxygen index value of 27.58. Optical microscopy, field emission scanning electron (FE-SEM), and transmission electron microscopy (TEM) images confirm the development of a well-patterned spherical nanostructure within the resin. The N2 adsorption/desorption studies reveal that Mn(II)TCNSL-F-PU25 has a Brunauer-Emmett-Teller surface area of 340.783 m2/g with a 3–3.2 nm pore diameter. Electrochemical impedance spectroscopy (EIS) demonstrates (3.5 wt% NaCl solution) a superior anticorrosion performance, protective capabilities, and compactness to a metal-coordinated substrate. The high impedance, solvent resistance, and low capacitance of coatings support the potential protective capabilities of the coating for the given immersion times. In addition, antibacterial activity ascertains the inhibition ability of the coordinated films against various bacterial strains i.e., E. coli, S. aureus, K. pneumonia, and B. subtilis. The formulated Mn(II)-coordinated PU has potential to become multi-functional surface-protective material.

Antimony Compounds Associate with Atopic Dermatitis and Influence Models of Itch and Dysbiosis.

Compared to the myriad of known triggers for rhinitis and asthma, environmental exposure research for atopic dermatitis (AD) is not well established. We recently reported that an untargeted search of U.S. Environmental Protection Agency (EPA) databases versus AD rates by United States (U.S.) postal codes revealed that isocyanates, such as toluene diisocyanate (TDI), are the pollutant class with the strongest spatiotemporal and epidemiologic association with AD. We further demonstrated that (di)isocyanates disrupt ceramide-family lipid production in commensal bacteria and activate the thermo-itch host receptor TRPA1. In this report, we reanalyzed regions of the U.S. with low levels of diisocyanate pollution to assess if a different chemical class may contribute. We identified antimony compounds as the top associated pollutant in such regions. Exposure to antimony compounds would be expected from brake dust in high-traffic areas, smelting plants, bottled water, and dust from aerosolized soil. Like TDI, antimony inhibited ceramide-family lipid production in Roseomonas mucosa and activated TRPA1 in human neurons. While further epidemiologic research will be needed to directly evaluate antimony exposure with surrounding AD prevalence and severity, these data suggest that compounds which are epidemiologically associated with AD, inhibit commensal lipid production, and activate TRPA1 may be causally related to AD pathogenesis.

Blockade of neutrophil extracellular traps ameliorates toluene diisocyanate-induced steroid-resistant asthma.

Toluene diisocyanate (TDI)-induced asthma is characterized by mixed inflammation dominated by neutrophils, and is refractory to steroid treatment. Neutrophil extracellular traps (NETs) play an important role in severe asthma, but their role in TDI-induced asthma models is unclear. This study focused on the role and mechanism of NETs in steroid-resistant TDI-induced asthma. Induced sputum was collected from 85 asthmatic patients and 25 healthy controls to detect eDNA. A murine TDI-induced asthma model was prepared, and asthmatic mice were given dexamethasone or DNase I. In vitro, the human bronchial epithelial cell line HBE was stimulated with NETs or TDI-human serum albumin (TDI-HSA). Asthma patients had higher sputum eDNA compared to healthy subjects. In asthma patients, eDNA was positively correlated with sputum neutrophils, and negatively correlated with FEV1%predicted. Airway inflammation, airway reactivity, Th2 cytokine levels in lymph supernatant, and levels of NETs were significantly increased in the TDI-induced asthmatic mice. These increases were suppressed by DNase I, but not by dexamethasone. Inhibition of NETs improved interleukin (IL)-8 and MKP1 mRNA expression, and reduced phosphorylation of GR-S226 induced by TDI. Inhibition of NETs improved airway epithelial barrier disruption, as well as p38 and ERK signaling pathways in TDI-induced asthmatic mice. In vitro, NETs promoted the expression of IL-8 mRNA in HBE cells, and reduced the expression of MKP1. IL-8 elevation induced by NETs was suppressed by a p38 inhibitor or ERK inhibitor, but not by dexamethasone. Pretreatment with RAGE inhibitor reduced NETs induced p38/ERK phosphorylation and IL-8 levels in HBE cells. Our data suggest that targeting NETs might effectively improved TDI-induced airway inflammation and airway epithelial barrier function. This may potentially be a treatment for patients with steroid-resistance asthma.

A physiologically-based kinetic (PBK) model for work-related diisocyanate exposure: Relevance for the design and reporting of biomonitoring studies

Diisocyanates are highly reactive substances and known causes of occupational asthma. Exposure occurs mainly in the occupational setting and can be assessed through biomonitoring which accounts for inhalation and dermal exposure and potential effects of protective equipment. However the interpretation of biomonitoring data can be challenging for chemicals with complex kinetic behavior and multiple exposure routes, as is the case for diisocyanates. To better understand the relation between external exposure and urinary concentrations of metabolites of diisocyanates, we developed a physiologically based kinetic (PBK) model for methylene bisphenyl isocyanate (MDI) and toluene di-isocyanate (TDI). The PBK model covers both inhalation and dermal exposure, and can be used to estimate biomarker levels after either single or chronic exposures. Key parameters such as absorption and elimination rates of diisocyanates were based on results from human controlled exposure studies. A global sensitivity analysis was performed on model predictions after assigning distributions reflecting a mixture of parameter uncertainty and population variability.Although model-based predictions of urinary concentrations of the degradation products of MDI and TDI for longer-term exposure scenarios compared relatively well to empirical results for a limited set of biomonitoring studies in the peer-reviewed literature, validation of model predictions was difficult because of the many uncertainties regarding the precise exposure scenarios that were used. Sensitivity analyses indicated that parameters with a relatively large impact on model estimates included the fraction of diisocyanates absorbed and the binding rate of diisocyanates to albumin relative to other macro molecules.We additionally investigated the effects of timing of exposure and intermittent urination, and found that both had a considerable impact on estimated urinary biomarker levels. This suggests that these factors should be taken into account when interpreting biomonitoring data and included in the standard reporting of isocyanate biomonitoring studies.

Chronic Exposure to TDI Induces Cell Migration and Invasion via TGF-β1 Signal Transduction

Toluene diisocyanate (TDI) is commonly used in manufacturing, and it is highly reactive and causes respiratory damage. This study aims to identify the mechanism of tumorigenesis in bronchial epithelial cells induced by chronic TDI exposure. In addition, transcriptome analysis results confirmed that TDI increases transforming growth factor-beta 1 (TGF-β1) expression and regulates genes associated with cancerous characteristics in bronchial cells. Our chronically TDI-exposed model exhibited elongated spindle-like morphology, a mesenchymal characteristic. Epithelial-mesenchymal transition (EMT) was evaluated following chronic TDI exposure, and EMT biomarkers increased concentration-dependently. Furthermore, our results indicated diminished cell adhesion molecules and intensified cell migration and invasion. In order to investigate the cellular regulatory mechanisms resulting from chronic TDI exposure, we focused on TGF-β1, a key factor regulated by TDI exposure. As predicted, TGF-β1 was significantly up-regulated and secreted in chronically TDI-exposed cells. In addition, SMAD2/3 was also activated considerably as it is the direct target of TGF-β1 and TGF-β1 receptors. Inhibiting TGF-β1 signaling through blocking of the TGF-β receptor attenuated EMT and cell migration in chronically TDI-exposed cells. Our results corroborate that chronic TDI exposure upregulates TGF-β1 secretion, activates TGF-β1 signal transduction, and leads to EMT and other cancer properties.

Study on GAP Adhesive-Based Polymer Films, Energetic Polymer Composites and Application

To lay the foundation for environmentally friendly energetic polymer composites, GAP (glycidyl azide polymer) adhesive-based polymer films with different curing parameter R (mol ratio of hydroxyl/isocyanate) and energetic polymer composites with different RDX contents were studied. GAP/TDI (toluene diisocyanate)/GLY(glycerol) was selected as the adhesive system. The tensile strength and elongation at the break of the polymer film with R = 2.2, was 14.34 MPa and 176.86%, respectively, as observed by an AGS-J electronic universal testing machine. A relatively complete cross-linking network and high hydrogen bonding interaction were observed by LF-NMR (low-field nuclear magnetic resonance, where the cross-linking density was 11.06 × 10-4 mol/cm3) and FT-IR (fourier transform infrared spectroscopy, where the carbonyl bonding ratio was 64.84%). Forty percent RDX(hexogen) was added into the adhesive system. The tensile strength was 4.65 MPa, and the elongation at the break was 78.49%; meanwhile, the heat of the explosive was 2.87 MJ/kg, and the residue carbon rate was only 2.47%. The tensile cross-sections of energetic polymer composites were observed by SEM (Scanning electron microscopy).

Research on main influencing factors and complete support technology for dynamic pressure and large deformation roadway

To determine the main factors influencing dynamic pressure and large deformation roadways, a targeted set of support technologies was designed. The 2603 air inlet roadway of the Zhangcun coal mine in Lu'an, Shanxi Province, was taken as an example. The influence of the Wenwangshan South normal fault and in situ stress field on the dynamic pressure roadway was analyzed theoretically, and the main factors influencing this dynamic pressure and large deformation roadway under natural geological conditions were determined. The effect of the existing roadway support scheme was evaluated by field test methods such as nondestructive bolt testing. The influence of mining two working faces on the dynamic pressure and large deformation roadway was studied by the FLAC3D numerical simulation method. On this basis, a new grouting material was developed, a complete set of technical schemes of full-section integrated cooperative support of dynamic pressure and large deformation roadways was proposed, and the field application effect was verified. The results showed that under natural geological conditions, the 2603 air inlet roadway was located within the influence range of the Wenwangshan South normal fault, which was significantly affected and controlled by the fault. The included angle between the roadway extension direction and the maximum principal stress was 74°, which was not conducive to the stability of the roadway. The range of the roadway loose zone was large. Under the existing support conditions, the surrounding rock could not form a relatively stable structure, which was one of the main reasons for the large deformation of the surrounding rock in the dynamic pressure roadway. The 2603 air inlet roadway was affected by the mining of both the adjacent working face and the 2603 working face. The stresses were superimposed, and the roadway was greatly deformed and damaged. A new grouting material was developed. A crosslinking agent prepared by toluene diisocyanate and polyether polyol was added to the existing polyurethane material to form a new grouting material, and a complete supporting technical scheme was proposed. The field application results showed that the displacement and floor heave of both sides of the roadway were reduced by approximately 87%, the deformation and failure of the coal and rock mass of the roadway were effectively controlled, and the deformation of the dynamic pressure roadway was greatly reduced.

Diisocyanates influence models of atopic dermatitis through direct activation of TRPA1.

We recently used EPA databases to identify that isocyanates, most notably toluene diisocyanate (TDI), were the pollutant class with the strongest spatiotemporal and epidemiologic association with atopic dermatitis (AD). Our findings demonstrated that isocyanates like TDI disrupted lipid homeostasis and modeled benefit in commensal bacteria like Roseomonas mucosa through disrupting nitrogen fixation. However, TDI has also been established to activate transient receptor potential ankyrin 1 (TRPA1) in mice and thus could directly contribute to AD through induction of itch, rash, and psychological stress. Using cell culture and mouse models, we now demonstrate that TDI induced skin inflammation in mice as well as calcium influx in human neurons; each of these findings were dependent on TRPA1. Furthermore, TRPA1 blockade synergized with R. mucosa treatment in mice to improve TDI-independent models of AD. Finally, we show that the cellular effects of TRPA1 are related to shifting the balance of the tyrosine metabolites epinephrine and dopamine. This work provides added insight into the potential role, and therapeutic potential, or TRPA1 in the pathogenesis of AD.

Synthesis and properties of oligodiuretane diisocyanates and oligotetraurethanes based on a mixture (2.4÷2.6) of toluene diisocyanate

By the reaction of a mixture of isomers (2.4-2.6) of toluene diisocyanate with aliphatic, individual or oligomeric diols (such as polyoxypropylene glycols of different molecular weight) in cyclohexanone, oligodiurethane diisocyanates with the diol component of different nature and length in their structure are synthesized in the first stage. In the second stage, the synthesized oligodiurethane diisocyanates were blocked by monofunctional aliphatic alcohols of normal structure with different lengths of fatty radical. The structure of the latter is confirmed by the absence of absorption bands characteristic of free –NCO groups in the IR spectra. Both series of isolated oligodiureta diisocyanates and oligotetraurethanes are characterized by refractive index and Ubellode drop temperature, molecular weights, content of free –NCO groups, and IR spectra. They are well soluble in esters, ethers, chlorinated and aromatic hydrocarbons, ketones, and aprotic solvents; they are poorly soluble in aliphatic hydrocarbons. The presence in the structure of such compounds of polar urethane groups simultaneously with relatively high molecular weight suggests that they will be useful not only as plasticizers, but also as modifiers of the properties of polymers and composite materials.

Determination of polyurethanes within microplastics in complex environmental samples by analytical pyrolysis

Polyurethanes (PUR) are a group of polymers synthesized from different diisocyanate and polyol monomers resulting in a countless number of possible structures. However, the large market demand, and the variety of application fields justify the inclusion of PUR in microplastic (MP) investigation. This study aimed at providing comprehensive information on PUR within MP analysis by pyrolysis–gas chromatography-mass spectrometry to clarify whether (i) it is possible to make a reliable statement on the PUR content of environmental samples based on a few pyrolysis products and (ii) which restrictions are required in this context. PUR were managed as subclasses defined by the diisocyanates employed for polymer synthesis. Methylene diphenyl diisocyanate (MDI)- and toluene diisocyanate (TDI)-based PUR were selected as subclasses of greatest relevance. Different PUR were pyrolyzed directly and under thermochemolytic conditions with tetramethylammonium hydroxide (TMAH). Distinct pyrolytic indicators were identified. The study supported that the use of TMAH greatly reduced the interactions of pyrolytic MP analytes with the remaining organic matrix of environmental samples and the associated negative effects on analytical results. Improvements of chromatographic behavior of PUR was evidenced. Regressions (1–20 µg) showed good correlations and parallelism tests underlined that quantitation behavior of different MDI-PUR could be represented by the calibration of just one representative with sufficient accuracy, entailing a good estimation of the entire subclass if thermochemolysis were used. The method was exemplary applied to road dusts and spider webs sampled around a plastic processing plant to evaluate the environmental spread of PUR in an urban context. The environmental occurrence of MDI-PUR as MP was highly influenced by the proximity to a potential source, while TDI markers were not observed.Graphical

Molecular Simulation Study on the Aging Mechanism of NEPE Propellant Matrix

Polyethylene glycols (PEG) and toluene diisocyanate (TDI) are often used as the main components of binders and curing agents in solid propellants, and their aging is an important issue in the storage and use of propellants. To study the aging behavior and aging mechanism of nitrate ester plasticized polyether propellant (NEPE) matrix during storage, the transition states of aging reactions of binder and curing agent were optimized at the (U)B3LYP/6-311G(d,p) level of theory, and the rate coefficients over the temperature range of 298-1000 K were calculated by CVT theory. The results showed that there were five kinds of aging reactions for binder, which included decomposition, nitration, H abstraction, oxidation, and crosslinking reactions. Among them, theenergy barriers of oxidation and H abstraction reactions were relatively low (79.3-91.2 kJ·mol-1) and the main reaction types of binder aging. The main aging reaction of curing agent was decomposition. Compared with the aging reactions of binder, the energy barriers of curing agent are higher (196.6-282.7 kJ·mol-1) and the reaction is more difficult to occur. By comparing the energy barriers and rate constants of different reactions, it is found that the aging of NEPE propellant matrix can be divided into two stages. In the first stage, the propellant matrix mainly undergoes H abstraction and oxidation reaction, and as the reaction proceeds, the products crosslink to form -O-O-, -C-C-, and -C-O-C- bonds. At this time, the long chain molecules of the propellant matrix crosslink, and the molecular weight increases. This stage corresponds to the rising stage of mechanical properties in the aging process of the propellant. In the second stage, the propellant matrix mainly undergoes decomposition and nitration, resulting in degradation, the reduction of molecular weights, and the appearance of holes and microcracks in the matrix. This stage corresponds to the decline of mechanical properties in the aging process of the propellant. The above simulation results are in good agreement with the aging experimental phenomena, revealing the microscopic mechanism of the changes in the macroscopic properties of NEPE propellant during the aging process, and providing a theoretical basis for the related research on the aging properties and anti-aging technology of NEPE propellant.

Photocatalytic-proxone process application in the degradation of toluene-diisocyante, and methylene diphenyl diisocyanate from polluted air

Isocyanates are one of the most widely used semi-volatile compounds in various industries, including the polyurethane industry. Applying a hybrid advanced oxidation process to the degradation of toluene diisocyanate (TDI) and methylene diphenyl diisocyanate (MDI) from polluted air were the main aims of the study. The BiOI@MOF/Zeolite nanocomposite was prepared by the solvothermal method. XRD, FT-IR, FESEM, EDAX, EDS element mapping, TEM, BET, XPS, and UV–vis spectra analysis were applied to indicate the nanocomposite characters. The effect of flow, ozone concentration, hydrogen peroxide concentration, initial isocyanates concentration, and relative humidity were investigated. The concentration of isocyanates measurement via NIOSH 5522 standard method. In the optimum conditions of the process, the supplementary studies were done. The results of the analysis of composite structure indicated that well synthesized had been done. Experimental results showed optimal operating conditions could degrade more than 90 % of isocyanates. The synergistic effect coefficient of the mechanisms was 2.03 and 2.34 for TDI and MDI, respectively. The stability of the process was observed in 6 consecutive steps. The residual ozone concentration in the system's outlet was negligible (0.047 mg/l). The CO2 and CO emissions proved that the mineralization of isocyanates occurred. The theoretical mineralization rate was 0.64 and 0.55 reported for TDI and MDI, respectively. The simultaneous presence of MDI and TDI in the reactor decreases the efficiency of the process. The pure oxygen gas, pure nitrogen gas, and atmospheric as a carrier gas showed different performances in the process of isocyanate removal (80.8, 35.4, and 61.7 % degradation in the simultaneous presence of MDI and TDI).