HDI Isocyanurate Research Articles

Viability of cultured human skin cells treated with 1,6-hexamethylene diisocyanate monomer and its oligomer isocyanurate in different culture media

The isocyanate monomer 1,6-hexamethylene diisocyanate (HDI) and one of its trimers, HDI isocyanurate, are airway and skin sensitizers contained in polyurethane paint. The toxic response of cultured skin cells to these compounds was measured by evaluating the isocyanate concentrations at which 50% of the cells die (i.e., lethal concentration 50%, LC50) because the relative toxicity of each form of HDI should be considered when exposure limits of HDI-based paints are set. By using a luminescent ATP-viability assay, we compared the cytotoxic effects of HDI monomer and HDI isocyanurate on cultured human skin cells (keratinocytes, fibroblasts, and melanocytes) after 4-h isocyanate exposures using culture media with varying levels of nutrients in order to also determine the effects of media composition on isocyanate toxicity. Before analysis, experimental wells were normalized to controls containing cells that were cultured with the same vehicle and media. The measured mean LC50 values ranged from 5 to 200 µM across the experimental conditions, in which HDI isocyanurate in protein-devoid media was the most toxic to cells, producing the lowest LC50 values. For HDI monomer, keratinocytes were the most resistant to its toxicity and melanocytes were the most susceptible. However, when exposed to HDI isocyanurate, the opposite was observed, with melanocytes being the most resilient and the keratinocytes and fibroblasts were more susceptible. Depending on the type of skin cells, dose–response data indicated that HDI isocyanurate was 2–6 times more toxic than HDI monomer when using protein-devoid media whereas HDI isocyanurate was 4–13 times more toxic than HDI monomer when protein-rich media was used. Therefore, if the protein-devoid saline medium alone were used for these experiments, then a significant under-estimation of their relative toxicities in protein-rich environments would have resulted. This difference is because HDI monomer toxicity was more attenuated by the presence of protein in the culture media than HDI isocyanurate toxicity. Thus, conclusions based on comparative toxicity studies and consequent inference applied to potential human toxicity can be affected by in vitro culture media conditions. The physiochemical difference in reactivity of the two forms of HDI to biological molecules most likely explains the observed toxicity differences and may have implications for skin penetration, adverse effects like skin sensitization, and systemic responses like asthma. Future studies are warranted to investigate differences in the biological availability, cellular toxicity, and immunologic sensitization mechanisms for HDI monomer and HDI isocyanurate.

Epigenetic Markers Are Associated With Differences in Isocyanate Biomarker Levels in Exposed Spray-Painters.

Isocyanates are respiratory and skin sensitizers that are one of the main causes of occupational asthma globally. Genetic and epigenetic markers are associated with isocyanate-induced asthma and, before asthma develops, we have shown that genetic polymorphisms are associated with variation in plasma and urine biomarker levels in exposed workers. Inter-individual epigenetic variance may also have a significant role in the observed biomarker variability following isocyanate exposure. Therefore, we determined the percent methylation for CpG islands from DNA extracted from mononuclear blood cells of 24 male spray-painters exposed to 1,6-hexamethylene diisocyanate (HDI) monomer and HDI isocyanurate. Spray-painters’ personal inhalation and skin exposure to these compounds and the respective biomarker levels of 1,6-diaminohexane (HDA) and trisaminohexyl isocyanurate (TAHI) in their plasma and urine were measured during three repeated industrial hygiene monitoring visits. We controlled for inhalation exposure, skin exposure, age, smoking status, and ethnicity as covariates and performed an epigenome-wide association study (EWAS) using likelihood-ratio statistical modeling. We identified 38 CpG markers associated with differences in isocyanate biomarker levels (Bonferroni < 0.05). Annotations for these markers included 18 genes: ALG1, ANKRD11, C16orf89, CHD7, COL27A, FUZ, FZD9, HMGN1, KRT6A, LEPR, MAPK10, MED25, NOSIP, PKD1, SNX19, UNC13A, UROS, and ZFHX3. We explored the functions of the genes that have been published in the literature and used GeneMANIA to investigate gene ontologies and predicted protein-interaction networks. The protein functions of the predicted networks include keratinocyte migration, cell–cell adhesions, calcium transport, neurotransmitter release, nitric oxide production, and apoptosis regulation. Many of the protein pathway functions overlap with previous findings on genetic markers associated with variability both in isocyanate biomarker levels and asthma susceptibility, which suggests there are overlapping protein pathways that contribute to both isocyanate toxicokinetics and toxicodynamics. These predicted protein networks can inform future research on the mechanism of allergic airway sensitization by isocyanates and aid in the development of mitigation strategies to better protect worker health.

Influence of Genetic Variance on Biomarker Levels After Occupational Exposure to 1,6-Hexamethylene Diisocyanate Monomer and 1,6-Hexamethylene Diisocyanate Isocyanurate.

We evaluated the impact of genetic variance on biomarker levels in a population of workers in the automotive repair and refinishing industry who were exposed to respiratory sensitizers 1,6-hexamethylene diisocyanate (HDI) monomer and one of its trimers, HDI isocyanurate. The exposures and respective urine and plasma biomarkers 1,6-diaminohexane (HDA) and trisaminohexyl isocyanurate (TAHI) were measured in 33 workers; and genome-wide microarrays (Affymetrix 6.0) were used to genotype the workers’ single-nucleotide polymorphisms (SNPs). Linear mixed model analyses have indicated that interindividual variations in both inhalation and skin exposures influenced these biomarker levels. Using exposure values as covariates and a false discovery rate < 0.10 to assess statistical significance, we observed that seven SNPs were associated with HDA in plasma, five were associated with HDA in urine, none reached significance for TAHI in plasma, and eight were associated with TAHI levels in urine. The different genotypes for the 20 significant SNPs accounted for 4- to 16-fold changes observed in biomarker levels. Associated gene functions include transcription regulation, calcium ion transport, vascular morphogenesis, and transforming growth factor beta signaling pathway, which may impact toxicokinetics indirectly by altering inflammation levels. Additionally, in an expanded analysis using a minor allele cutoff of 0.05 instead of 0.10, there were biomarker-associated SNPs within three genes that have been associated with isocyanate-induced asthma: ALK, DOCK2, and LHPP. We demonstrate that genetic variance impacts the biomarker levels in workers exposed to HDI monomer and HDI isocyanurate and that genetics can be used to refine exposure predictions in small cohorts when quantitative personal exposure and biomarker measurements are included in the models.

Trisaminohexyl Isocyanurate (TAHI) Levels in Plasma and Urine in Workers Exposed to 1,6-Hexamethylene Diisocyanate (HDI) Monomer and HDI Isocyanurate

Identification and quantification of trisaminohexyl isocyanurate (TAHI) as a biomarker of 1,6-hexamethylene diisocyanate (HDI) isocyanurate exposure is a critical step for evaluating the contributions of work environment and personal protective equipment practices in limiting isocyanate exposure. Polymeric HDI isocyanurate is the predominant inhalation and skin exposure in the automotive repair industry, yet, biological monitoring has been limited to metabolites of HDI monomer exposure. We analyzed TAHI and hexamethylene diamine (HDA), a biomarker for HDI monomer exposure, in the plasma and urine of automotive spray-painters. Despite the large number of samples with HDA, daily total urinary HDA and plasma HDA were weakly associated with inhalation exposures to HDI monomer (Urine: r &amp;#61; 0.121, p &amp;#61; 0.1980; Plasma: r &amp;#61; 0.120, p &amp;#61; 0.2146) or HDI isocyanurate (Urine: r &amp;#61; 0.011, p &amp;#61; 0.9112; Plasma: r &amp;#61; 0.065, p &amp;#61; 0.5015). By comparison, correlations for TAHI were strong with both HDI monomer (Urine: r &amp;#61; 0.329, p &amp;#61; 0.0003; Plasma: r &amp;#61; 0.262, p &amp;#61; 0.0062) and HDI isocyanurate inhalation exposures (Urine: r &amp;#61; 0.364, p &amp;#61; &amp;lt;0.0001; Plasma: r &amp;#61; 0.335, p &amp;#61; 0.0004). HDA and TAHI levels in urine and plasma had equally strong correlations with HDI monomer and HDI isocyanurate skin exposures. However, due to the collinearity of HDI monomer (r &amp;#61; 0.475, p &amp;#61; &amp;lt;0.0001) and HDI isocyanurate (r &amp;#61; 0.377, p &amp;#61; &amp;lt;0.0001) inhalation and skin exposures, the contributions of exposure pathways to biological levels is unknown. Workplace factors such as paint-booth type, coverall and glove use, and respirator type may be equally or more important factors for variation in TAHI levels. Using linear mixed modeling in SAS, we are currently investigating the contributions of exposure pathways and workplace factors on HDA and TAHI levels in plasma and urine in this occupationally exposed worker cohort.

Influence of Genetic Variance on Occupational Exposure to 1,6-Hexamethylene Diisocyanate (HDI) and Its Trimer HDI Isocyanurate

Polyurethane spray-painting can result in significant occupational exposure to 1,6-hexamethylene diisocyanate (HDI) monomer and its trimer, HDI isocyanurate. Inter-individual genetic differences ha...

Quantification of Trisaminohexyl Isocyanurate (TAHI) as a Biomarker of HDI Isocyanurate Exposure in the Plasma and Urine of Automotive Spray Painters

Quantification of Trisaminohexyl Isocyanurate (TAHI) as a Biomarker of HDI Isocyanurate Exposure in the Plasma and Urine of Automotive Spray Painters

Trisaminohexyl isocyanurate, a urinary biomarker of HDI isocyanurate exposure

Biological monitoring of occupational exposure to 1,6-hexamethylene diisocyanate (HDI)-containing spray-paints is limited to analysis of metabolites of HDI monomer although polymeric HDI isocyanurate constitutes the predominant inhalation and skin exposure for workers in the automotive paint industry. A novel method using nanoflow ultra-performance liquid chromatography coupled to nano-electrospray ionization tandem mass spectrometry (nano-UPLC-ESI-MS/MS) was developed to quantify trisaminohexyl isocyanurate (TAHI), a hydrolysis product of HDI isocyanurate, in the urine of spray-painters. Analytical and internal standards were synthesized in-house and weighted linear regression calibration curves were generated using spiked control urine from non-exposed persons (0.06–7.98 μg/L; N = 13; w = x−2; r = 0.998). Urine samples collected from 15 exposed workers (N = 111) were subjected to acid hydrolysis and extracted with dichloromethane, then derivatized with acetic anhydride. The derivatized product, trisacetamidohexyl isocyanurate (TAAHI), was analyzed using nano-UPLC-ESI-MS/MS. The protocol was sensitive and specific for analysis of TAHI in the urine of exposed workers with a method detection limit at 0.03 μg/L. TAHI was detected in 33 of 111 urine samples and in 11 of 15 workers. This biomarker for HDI isocyanurate is critical to determine the relative potency and dose-relationships between the monomer and oligomer exposure on the development of diisocyanate induced health effects in future studies.

Reactivity and kinetics of HDI-iminooxadiazinedione: Application to polyurethane synthesis

For many years, intensive research has been carried out for the synthesis of polyurethanes by reaction between diisocyanates and various alcohols, water or amines. However, these reactions present one major drawback: the harmfulness of diisocyanates monomers for human health and environment. Therefore industries developed different routes to avoid the use of diisocyanates. Some of these routes involve oligomers of isocyanates such as isocyanurates (trimers of diisocyanates) which present a low harmfulness. The HDI-iminooxadiazinedione (HDIOD) isocyanate is a new isocyanate trimer recently developed by industry. The main interest of such monomer seems to be its reactivity compared to classical isocyanurates. Consequently, in this study, we compared the reactivity and the kinetic of HDI-isocyanurate (HDII) – the most used isocyanurate, and HDIOD. Firstly, after a structural study, we compared the properties of the polymers obtained. Then, we monitored the reactions of isocyanurates with different alcohols by 1H NMR to determine their kinetics rate constants. Finally, we proposed a mechanism which could explain the difference of reactivity between these monomers.

Isocyanate Exposure Below Analytical Detection When a Paint Brush and Roller Are Used to Apply Moisture-Cure Polyurethane Paint.

Isocyanate exposure is known to be hazardous when polyurethane paints are applied with a spray gun, but less is known of exposure when paint is applied with a paint brush and roller. Concentrations of 1,6-hexamethylene diisocyanate (HDI) monomer and three HDI polymers were assessed when two moisture-cure polyurethane paints containing 31-35% isocyanates were applied with a paint roller and brush. Short-term 15-min samples were taken during paint application in an indoor test environment with no ventilation (n= 12); in an outdoor test environment (n= 11); and in an outdoor in-situ assessment (n= 22). The outdoor in-situ assessment involved the painting of a bus shelter and light poles at a public transit station over two night shifts. All isocyanate samples were below analytical detection. The analytical limits of detection for HDI monomer, HDI biuret, HDI isocyanurate, and HDI uretdione were 0.005, 0.84, 0.87, and 0.88 µg, respectively. The finding that isocyanate concentrations were below detection is attributed to the use of paint roller and brush which minimize paint aerosolization and the paint formulation itself which contained <1% of volatile HDI monomer.

광경화형 PDMS 변성 우레탄 아크릴레이트 올리고머 합성과 경화필름 물성에 관한 연구

Hydrogen terminated PDMS와 allyl alcohol를 Karstedt's 촉매 존재하에서 hydrosilylation 반응을 이용하여 hydroxypropyl terminated PDMS를 합성한 후, 3관능 HDI isocyanurate trimer와 hydroxyethyl methacrylate를 one-pot 반응으로 초분지 형태의 다관능 실리콘 변성 우레탄 아크릴레이트 올리고머(PUA 올리고머)를 합성하였다. 합성된 PUA 올리고머의 특성은 FT-IR과 GPC를 사용하여 분석하였으며, 그들의 중량평균 분자량은 약 9000 g/mol 이었다. 합성된 PUA 올리고머와 반응성 모노머인 phenylthioethyl acrylate를 여러 가지 조성비로 혼합하고 UV-광경화반응을 이용하여 연성 경화물을 제조하였다. 연성 경화물의 굴절률은 phenylthioethyl acrylate 첨가함에 따라 증가하였으나 반응성 모노머 함량과 관계가 없었다. 또한, 연성 경화필름의 광투과도 변화도 없었다. Hydroxypropyl terminated PDMS was synthesized by the hydrosilylation reaction with allyl alcohol in the presence of Karstedt's catalyst. And them, an one-pot reaction with HDI isocyanurate trimer and hydroxyethyl methacrylate was conducted to give a silicone-modified urethane acrylate oligomer (PUA oligomer) having 9000 g/mol, weight average molecular weight. The synthesized PUA oligomer was characterized by using FT-IR and GPC. The UV-curable coatings were prepared by PUA oligomer blending with a reactive monomer (phenylthioethyl acrylate) under the different mole ratios. It was found that the refractive index of cured film increased when the reactive monomer was added but there was no relationship between the refractive index and amount of reactive monomer. Also, their transmittance for cured films was not change as increasing the content of reactive monomer.

Comparison of film properties for crosslinked core–shell latexes

Thermosetting acrylic latexes were synthesized using butyl acrylate (BA), methyl methacrylate (MMA), 2-hydroxyethyl methacrylate (HEMA), and methacrylic acid (MAA) via seeded two-stage process. A 2-level factorial experimental design was employed to investigate the effect of hydroxyl (core phase), carboxylate (shell phase) groups, and type of surfactant (Triton X200, Tergitol XJ) on the mechanical properties of thermosetting latexes. Eight latexes with varying concentration of HEMA, MAA and two types of surfactants were synthesized and crosslinked with three crosslinkers. Latex functionality for crosslinking was located in the core only, the shell only, and both the core–shell with varying concentrations. Melamine-formaldehyde (hexamethoxymethyl melamine) resin was employed to crosslink hydroxyl functionalities in the core. Carboxylic acid groups in the shell were crosslinked with zinc ammonium carbonate. HDI isocyanurate (Desmodur N3300A) were used to crosslink with hydroxyl or carboxyl functional groups in core and shell. The mechanical properties of coatings were evaluated in terms of tensile properties, cross-hatch adhesion, pencil hardness, and impact resistance. Design of experiment (DOE) was utilized to investigate the effect of variables on mechanical properties of crosslinked thermoset films.

Isocyanurate based fluorinated polyurethane dispersion for anti-graffiti coatings

Fluorinated polyurethane dispersions (FPUDs) were synthesized using HDI isocyanurate, polyester polyol and DMPA with varying concentrations of trifluoro ethanol (TFE) in the range of 0–9wt%. Further FPUDs were characterized by FT-IR and 1H NMR for structural elucidation. Effects of trifluoro ethanol on the dispersion were evaluated by particle size analyzer. It was observed that with increase in TFE, particle size increases. Topography and contact angle were studied by atomic force microscopy (AFM) and goniometer, respectively. To gain more insight into the formation of roughness, power spectral density (PSD) analysis was carried out. It was found that with increase in TFE content, surface roughness increases due to migration of fluorinating agent on the coating substrate and consequently water repellency increases. Nano indentation of coating revealed that fluorinated coating possesses less stiffness and elastic modulus, due to the presence of fluorine on the coating. Further, coatings were analyzed for thermal properties by thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) which shows the enhancement in thermal stability and glass transition temperature with increase in TFE content. Anti-graffiti test was carried out which showed improved resistance with increasing fluorine content.

Airborne Isocyanate Exposures in the Collision Repair Industry and a Comparison to Occupational Exposure Limits

Isocyanate exposure was evaluated in 33 spray painters from 25 Washington State autobody shops. Personal breathing zone samples (n = 228) were analyzed for isophorone diisocyanate (IPDI) monomer, 1,6-hexamethylene diisocyanate (HDI) monomer, IPDI polyisocyanate, and three polyisocyanate forms of HDI. The objective was to describe exposures to isocyanates while spray painting, compare them with short-term exposure limits (STELs), and describe the isocyanate composition in the samples. The composition of polyisocyanates (IPDI and HDI) in the samples varied greatly, with maximum amounts ranging from up to 58% for HDI biuret to 96% for HDI isocyanurate. There was a significant inverse relationship between the percentage composition of HDI isocyanurate to IPDI and to HDI uretdione. Two 15-min STELs were compared: (1) Oregon's Occupational Safety and Health Administration (OR-OSHA) STEL of 1000 μg/m3 for HDI polyisocyanate, and (2) the United Kingdom's Health and Safety Executive (UK-HSE) STEL of 70 μg NCO/m3 for all isocyanates. Eighty percent of samples containing HDI polyisocyanate exceeded the OR-OSHA STEL while 98% of samples exceeded the UK-HSE STEL. The majority of painters (67%) wore half-face air-purifying respirators while spray painting. Using the OR-OSHA and the UK-HSE STELs as benchmarks, 21% and 67% of painters, respectively, had at least one exposure that exceeded the respirator's OSHA-assigned protection factor. A critical review of the STELs revealed the following limitations: (1) the OR-OSHA STEL does not include all polyisocyanates, and (2) the UK-HSE STEL is derived from monomeric isocyanates, whereas the species present in typical spray coatings are polyisocyanates. In conclusion, the variable mixtures of isocyanates used by autobody painters suggest that an occupational exposure limit is required that includes all polyisocyanates. Despite the limitations of the STELs, we determined that a respirator with an assigned protection factor of 25 or greater is required to protect against isocyanate exposures during spray painting. Consequently, half-face air-purifying respirators, which are most commonly used and have an assigned protection factor of 10, do not afford adequate respiratory protection.

Penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate monomer in human skin

We investigated penetration patterns of monomeric and polymeric 1,6-hexamethylene diisocyanate (HDI), experimentally and as part of commercial products, in excised full-thickness human skin at 5, 10, 30, or 60 min after exposure. We observed that both monomeric and polymeric HDI were readily absorbed into the skin and that the clearcoat composition affects the penetration rate of the individual isocyanates. The short-term absorption rates for HDI monomer, biuret, and isocyanurate were determined and used to estimate the exposure time required to reach a body burden equal to the American Conference of Governmental Industrial Hygienists (ACGIH) inhalation threshold limit value (TLV) or Oregon State occupational exposure limit (OEL). Oregon is the only government entity in the United States to promulgate a short-term exposure limit (STEL) for HDI-based polyisocyanates biuret and isocyanurate. Based on these absorption rates for a slow-drying clearcoat after 10 min (1.33 μg cm(-2) h(-1)) or 60 min (0.219 μg cm(-2) h(-1)), we calculated that 6.5 and 40 min dermal exposure, respectively, is required to achieve a dose of HDI equivalent to the ACGIH TLV. For biuret, the time to achieve a dose equivalent to the Oregon OEL for slow-drying clearcoat was much shorter (<31 min) than that for fast-drying clearcoat (618 min). Isocyanurate had the shortest skin absorption times regardless of clearcoat formulation (14 s-1.7 min). These results indicate that the dose received through dermal exposure to HDI-containing clearcoats has a significant potential to exceed the dose equivalent to that received through inhalation exposure at established regulatory limits. A critical need exists to monitor dermal exposure quantitatively in exposed workers, to use proper protective equipment to reduce dermal exposure, and to re-evaluate regulatory exposure limits for isocyanates.

Preparation and characterisation of polyurethane coatings based on polyester polyol

Purpose – The purpose of this paper is to describe how to synthesise polyurethane resins by using different polyester polyols and HDI isocyanurate. The polyester polyols were prepared by reacting single diol with different diacids. The effects of these polyester polyols on the performance properties of the coating films are studied.Design/methodology/approach – A series of hydroxyl‐terminated polyester polyols were synthesised by using 1,4‐cyclohexanedimethanol (1,4‐CHDM) with different diacids such as 1,3‐cyclohexanedicarboxylic acid (1,3‐CHDA), 1,4‐CHDA, adipic acid (AA), azelaic acid (AZA), and isophthalic acid (IPA). The general properties including acid number, hydroxyl number average molecular weight, polydispersity index, and viscosity of these polyester polyols were evaluated. Different coating formulations were developed by using polyester polyols and HDI isocyanurate. These coatings were applied on sand blasted mild steel panels and glass panels and were cured in hot air oven. Various mechanical...

The effect of difunctional acids on the performance properties of polyurethane coatings

Hydroxyl-terminated polyesters are the most common polyols that are crosslinked through an isocyanate group. In this study, the polyester polyol resins were synthesized by using 1,4-cyclohexanedimethanol (1,4-CHDM) with the mixture of different diacids as 1,3-cyclohexanedicarboxylicacid (1,3-CHDA), 1,4-cyclohexanedicarboxylicacid (1,4-CHDA), isophthalic acid (IPA), adipic acid (AA), and azelaic acid (AZA). The solubility and viscosity of these polyester polyol resins were determined by using suitable solvent. All the polyester polyols were crosslinked with HDI isocyanurate and IPDI trimer to form polyurethane coating films. These films were evaluated for their mechanical, thermal, and chemical resistance properties. The studies on film characteristics reveal that the cycloaliphatic diacids afforded polyurethane with greater performance properties than that of aromatic and linear aliphatic diacids.

Comparative assessment of early acute lung injury in mice and rats exposed to 1,6-hexamethylene diisocyanate–polyisocyanate aerosols

The aliphatic diisocyanate monomer 1,6-hexamethylene diisocyanate (HDI) is used as a building block for non-volatile polycondensation products, such as HDI-isocyanurate (HDI-IC) and HDI-biuret (HDI-BT). This paper describes the results from acute inhalation studies with these types of polyisocyanate aerosols in OF1 and C57BL/6J mice and in Wistar rats. The modifying role of different concentrations of residual HDI in HDI-BT on pulmonary irritation was also addressed. These data close data gaps for acute mouse inhalation studies in direct comparison with rats. The sensory irritant potency was examined in OF1 mice during a 3 h nose-only exposure to the polyisocyanate aerosols. Concurrent with exposure, breathing patterns suitable to distinguish upper/lower respiratory tract irritation where examined. Functional measurements in barometric plethysmographs (Penh) addressed changes in respiratory function in C57BL/6J mice exposed for 6 h up to 16 h postexposure. These measurements revealed that these polyisocyanates elicit changes slow in onset suggestive of pulmonary irritation rather than upper airway irritation. This conclusion was supported by similarly exposed OF1 mice exposed to non-irritant, surface active respirable particles of amorphous silica. In C57BL/6J mice and Wistar rats, nose-only exposed for 6 h to 10 mg/m 3 of aerosolized HDI-BT HDI (0.1% or 2% residual HDI), the pulmonary irritation potency was comparatively assessed by bronchoalveolar lavage (BAL) on postexposure day 1. Similarly air-exposed animals served as concurrent controls. Most changes in BAL suggestive of acute pulmonary irritation were more pronounced in Wistar rats than in C57BL/6J mice. A conclusive dependence of BAL endpoints on the residual content of residual HDI monomer in the polyisocyanate was not found. The results of this study show that mice may be particularly suitable to functionally analyze at which location of the respiratory tract predominant irritation may occur. However, with regard to analysis of lower respiratory tract irritation, rats were demonstrated to be more susceptible than mice. In summary, this study supports the conclusion that data from rat inhalation studies with these types of isocyanates appear to be more conservative and less variable than the respective data from mice.

Preparation and Characterization of Two-component Waterborne Polyurethane Comprised of Water-soluble Acrylic Resin and HDI Biuret

Abstract A two-component waterborne polyurethane (2K-WPU) was prepared by mixing water-soluble acrylic resin and hexamethylene diisocyanate biuret, and then diluted for phase inversion with water. Compared with water-soluble acrylic resin, the phase inversion of 2K-WPU occurs at lower water content. It is indicated by TEM that 2K-WPU particles show a core-shell structure, in which HDI biuret is encapsulated by hydrophilic acrylic resin. 2K-WPU emulsion with HDI biuret has larger particle size and narrower distribution index, while for 2K-WPU emulsion with HDI isocyanurate, the latex not only has large particle size, but also has two-peak distribution. FTIR shows that the reaction between HDI biuret and acrylic resin can complete in 12h. In addition, studies on effect of composition of acrylic resin on performance of 2K-WPU show that narrowing the polar difference between water-soluble acrylic resin and HDI biuret and improving the miscibility of two components are the key to prepare the transparent and high gloss films with high crosslinking density.

Nanostructured polyurethane ceramer coatings for aircraft

A new low VOC (volatile organic compounds) polyurethane/oligosiloxane coating was formulated using 1,6-hexamethylene diisocyanate (HDI) isocyanurate, alkoxysilane-functionalized HDI isocyanurate, tetraethyl orthosilicate (TEOS) oligomers, and three cycloaliphatic polyesters. One series of polyesters was synthesized using 1,4-cyclohexanedimethanol (CHDM) with 1,4-cyclohexanedicarboxylic acid (1,4-CHDA) and 1,3-cyclohexanedicarboxylic acid (1,3-CHDA). A second series of polyesters was synthesized using 2-butyl-2-ethyl-1,3-propanediol (BEPD) with 1,4-CHDA or 1,4-CHDA, and 1,3-CHDA, respectively. The polyurethane provided the general mechanical properties and the polysiloxane functioned as an adhesion promoter and corrosion inhibitor. The continuous organic polyurethane phase was coupled with the inorganic polysiloxane phase via the alkoxysilane-functionalized HDI isocyanurate. The general coatings, tensile, and viscoelastic properties were evaluated for the ceramer coatings as functions of the polyester and concentration of TEOS oligomers. Damage tolerance was evaluated via fracture toughness and development of the film deformation zone prior to crack propagation. The coatings’ properties were dominated by the organic phase. The film morphology was investigated using the combination of SEM (scanning electron microscope) and X-ray analysis. Phase separation was observed for ceramer coatings resulting in SiO2 particles. The size of the preceramic silicon-oxo-particles was controlled by the Tg of the organic phase and the concentration of TEOS oligomers.

Cycloaliphatic polyester based high solids polyurethane coatings: I. The effect of difunctional alcohols

High-solids polyesters were synthesized with two cycloaliphatic diacids, 1,4- cyclohexanedicarboxylic acid (1,4-CHDA) and 1,3-cyclohexanedicarboxylic acid (1,3-CHDA); and with five diols, 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), hydroxypivalyl hydroxypivalate (HPHP), 2-butyl-2-ethyl-1, 3-propanediol (BEPD), and 1,6-hexanediol (HD). The viscosity of the polyesters was dependent on the structures of diols. The viscosity of polyesters is lower with the diol HD, intermediate with BEPD and HPHP, and higher with the diols CHDM and NPG. The polyesters were crosslinked with hexamethylene diisocyanate isocyanurate (HDI isocyanurate) affording polyurethane coatings. The mechanical properties, tensile properties, fracture toughness, and viscoelastic properties were investigated for the polyurethane films with five different diols. The cyclohexyl structure of the CHDM provides the polyurethane with rigidity which is manifested in high tensile modulus, hardness, and fracture toughness. In contrast, the linear diol, 1,6-hexanediol provides polyurethane with very high flexibility, but these coatings suffer with respect to low hardness and tensile modulus.