to access the full features of the site or access our, Center for Computational Quantum Chemistry, University of Georgia, 140 Cedar Street, Athens, Georgia, USA, 1st Source Research, 617 Hutton St., Raleigh, North Carolina, USA, Zymergen, 5980 Horton Street, Suite 105, Emeryville, California, USA. Such reactions in the absence of solvents often occur with explosive violence . Methylene diphenyl diisocyanate, toluene diisocyanate, and Diethylene glycol were utilized for getting the kinetic parameters. Fundamental and applied toxicology, 22:195210. 4,4'-Diphenylmethane diisocyanate is not soluble in water. Pulmonary adenocarcinoma observed in one case was considered as insufficient to identify PMDI as an animal carcinogen; however, in situ generation of MDA, which is a known animal carcinogen via drinking-water, could be responsible for the effect. They are based on selected national or regional evaluation documents or on existing EHCs. A total of 24 substituted RNCO + H2O reactions were studied. RSC Adv 5(22):1717117178, Ghoreishi R, Zhao Y, Suppes GJ (2014) Reaction modeling of urethane polyols using fraction primary secondary and hindered-secondary hydroxyl content. Wash with plenty of soap and water. 4,4'-Methylenediphenylene diis. Provided by the Springer Nature SharedIt content-sharing initiative, Over 10 million scientific documents at your fingertips, Not logged in The basis for the diagnosis of asthma was not stated. 11122). Isocyanates come in different chemical forms, the most commonly used are methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), and hexamethylene diisocyanate (HDI); TDI is more hazardous because it is more volatile and the vapour can be breathed in. The treated soil was then used for the studies. O0C3# @"6
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;(>O@k+87c *ah:H On dsigne sous le nom gnrique de diisocyanate de diphnylmthane (MDI) un produit utilis dans lindustrie. Research Triangle Park, NC, US Department of Health and Human Services, Public Health Service, National Institutes of Health, National Toxicology Program (Technical Report No. El MDI se utiliza en la fabricacin de elastmeros de poliuretano (rodillos, embalaje, aislantes de caucho contra las vibraciones, piel sinttica, etc. La informacin sobre la exposicin ocupacional es limitada; en diferentes industrias se ha notificado que no son frecuentes las exposiciones medias ponderadas por el tiempo de ocho horas superiores a 50 g/m3. There was not a clear doseresponse trend in macrophage accumulation, although macrophages were increased in incidence in all test groups over controls. Water treatment (Section 200) 51 Phosgene generation (Section 300) 51 . Toxicologist, 6:15. The investigators discussed the possibility that there may be selection bias, because the study group did not include any subject with symptoms suggesting hypersensitivity to isocyanate; those who were experiencing adverse effects may have been included in the small numbers of subjects who had left and been lost to follow-up. Fujiwara K (1981) Accumulation of TDI, NDI, TDA, MDA in fish and their toxicity. Bartsch W, Buschmann J, Hoymann HG, Heinrich U (1996) [Chronic toxicity and carcinogenicity study on MDI.] Based on EPAs screening-level review of hazard and exposure information, including information indicating uncured MDI and its related polyisocyanates are used in a range of consumer and commercial products as well as in products intended only for an industrial market, EPA intends to: Previous Actions:Read about the ongoing federal partnership activities for safer use of spray polyurethane foam containing MDI and related compounds. Tissues obtained from female Wistar rats exposed to a 0.9-m aerosol of MDI for 17 h per day, 5 days per week, for 1 year, at levels of 0, 0.3, 0.7, or 2.0 mg/m3, were analysed for DNA adducts using a 32P-postlabelling method (Vock et al., 1996). Risks to human health and the environment will vary considerably depending upon the type and extent of exposure. Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. Hazards Identification Emergency Overview . Gas concentrations are in percent by volume. Twenty-five mated female rats per group were exposed to concentrations of 1, 4, or 12 mg/m3 (MMAD <2.8 m) for 6 h per day from day 6 to day 15 of gestation. Mancuso G, Reggiani M, Berdondini RM (1996) Occupational dermatitis in shoemakers. InChI=1S/C15H10N2O2/c18-10-16-14-5-1-12(2-6-14)9-13-3-7-15(8-4-13)17-11-19/h1-8H,9H2, Except where otherwise noted, data are given for materials in their, DTXSID3027900 DTXSID7025180, DTXSID3027900, National Institute for Occupational Safety and Health, "4,4'-Diphenylmethane diisocyanate | C15H10N2O2 - PubChem", "C&EN's Global Top 50 chemical companies of 2018", "A theoretical study on the phosgenation of methylene diphenyl diamine (MDA)", Ullmann's Encyclopedia of Industrial Chemistry, "Preventing Asthma and Death from MDI Exposure During Spray-on Truck Bed Liner and Related Applications", IARC Monograph: "4,4'-Methylenediphenyl Diisocyanate", NIOSH Safety and Health Topic: Isocyanates, Isofact American Chemistry Council Diisocyanates Panel, Azom Chemical database on Polyurethane chemistry, MDI and the Environment - 2005 presentation by Center for the Polyurethanes Industry, Concise International Chemical Assessment Document 27, https://en.wikipedia.org/w/index.php?title=Methylene_diphenyl_diisocyanate&oldid=1095956817, 1-Isocyanato-4-[(4-isocyanatophenyl)methyl]benzene, This page was last edited on 1 July 2022, at 12:06. Los lmites de deteccin de esta tcnica para el MDI y el PMDI, que varan en funcin de la metodologa de muestreo, pueden ser inferiores a 0,01 mg/m3. Cuando se produce un vertido al suelo o al agua, el MDI tiene una existencia fugaz, debido a que reacciona con el agua para producir de manera predominante poliureas insolubles. Partial substitution of polymeric methylene diphenyl diisocyanate resin with soy flour increases the cold tack of the resin to the level achieved by urea formaldehyde resin. In vitro, the circulating immune complexes in serum increased after the addition of MDIHSA. J Appl Polym Sci 132(25):42127, Nagy T et al (2016) Uncatalyzed reactions of 4,4-diphenylmethane-diisocyanate with polymer polyols as revealed by matrix-assisted laser desorption/ionization mass spectrometry. Il est rare que lon soit fortement expos dans le milieu ambiant. Methylene diphenyl diisocyanate (MDI) is an aromatic diisocyanate. Some body weight depression was observed in males of the mid-concentration group through week 10. No desquamation or fissuring was noted with the compound. Immediate or late allergic reactions or both can occur. (1982) followed 107 polyurethane manufacturing workers exposed to TDI alone (17), MDI alone (25), or both (6) prospectively for 5 years. American journal of industrial medicine, 33:471477. The half-life of MDI in water under neutral conditions and at 298 K was found to be 11 s. If in a solution 4,4'-Diphenylmethane diisocyanate may or may not burn depending on the nature of the material and/or the solvent. Journal of allergy and clinical immunology, 92(3):387396. Haemoglobin adducts were found after repeated exposure of rats to MDI aerosols for 17 h per day, 5 days per week, over 3 or 12 months in an inhalation chamber (Sepai et al., 1995a). %%EOF
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. TDI is chemically similar to MDI and presents similar hazard and exposure concerns, but is reportedly used in a different range of products. A pond study provides evidence that MDI accumulation through the aquatic food chain is extremely unlikely, as might be expected considering its very low solubility and high reactivity in aqueous solution. It can therefore be expected that, in aqueous environments, the rate of reaction with water (50 M) would always by far exceed that with other OH-bearing molecules (mM). Fetal body weights were comparable in all groups, and no external treatment-related abnormalities were observed in the fetuses. K 7[2E
[+B Thus, these studies demonstrated clear adverse pulmonary and nasal effects at 8.4 mg/m3, and they are statistically significant at 4.1 mg/m3. In the second study, no MDA was detected, although the PMDI concentrations ranged up to 5 mg/m3 when polyurethane particleboard was heated up to 80 C (the detection limit for MDA in air was 10 g/m3) (Giersig, 1989). (Concise international chemical assessment document ; 27)
Spanne M, Tinnerberg H, Dalene M, Skarping G (1996) Determination of complex mixtures of airborne isocyanates and amines, Part 1. In short-term tests, nominal concentrations in the range of 5003000 mg MDI/litre caused no lethal effect on freshwater fish (Rhone-Poulenc Chimie, 1977; Nakata, 1983; Caspers et al., 1986). NIOSH (1994b) Letter from NIOSH to Distinctive Designs International Inc. with a study report.
71). The tack can be fine-tuned by adjusting the amount of soy flour added. Labelling of the digestive tract was considered to be a result of transference of labelled material from the lungs. Giersig M (1989) Polyharnstoff gebundene Spanplatten. It is reported, however, that a ventilation duct was installed above the moulding machine several months before the analysis, and that before then samples exceeding 0.2 mg/m3 had occurred frequently (Diller & Herbert, 1982). Ce CICAD sur le diisocyanate de diphnylmthane (MDI) a t prpar par lInstitut national japonais des sciences de la sant en collaboration avec le National Center for Environmental Assessment de lEnvironmental Protection Agency des tats-Unis (EPA). Vock EH, Lutz WK (1997) Distribution and DNA adduct formation of radiolabeled methylenediphenyl-4,4-diisocyanate (MDI) in the rat after topical treatment. The amine product will spontaneously react with another isocyanate molecule forming a urea. More recently, comprehensive studies on the behaviour of MDI in the aquatic environment have been carried out by Yakabe et al. Blom AJM, Oldersma H (1994) Effect of Desmodur 44 V20-PMDI on the growth of the green alga Scenedesmus subspicatus. Lexprimentation animale apporte cependant des preuves indiscutables dune sensibilisation cutane et respiratoire provoque par le MDI. Macrophages with yellow pigment (a form of MDI within the macrophage) were also found in the alveolar interstitium, and accumulation of these macrophages also occurred in the mediastinal lymph nodes. Autopsy of the animals immediately after exposure showed haemorrage and oedema in the lungs. Hay una informacin muy limitada sobre la toxicocintica del MDI. These groups react with compounds that have an active hydrogen, such as water, alcohols, and amines. Le MDI polymris (PMDI), qui est la forme technique et commerciale principale de ce compos est en fait un mlange contenant 25 80 % de 4,4-MDI monomre et des oligomres 3-6 cycles plus quelques isomres comme lisomre 2,2. The resulting value, 0.06 mg/m3, is the BMC10 (HEC). NIOSH (1985) NIOSH manual of analytical methods, 3rd ed. A 2-year chronic toxicity/carcinogenicity inhalation study was carried out with SPF Wistar rats (60 per sex per exposure level) exposed whole body to PMDI aerosol at 0, 0.19, 0.98, or 6.03 mg/m3 for 6 h per day, 5 days per week (Reuzel et al., 1994b). En se basant sur une augmentation marginale du rapport poids du poumon/poids du corps aux doses les plus leves, on a conclu que la concentration de 2,2 mg/m3 - la plus faible tudie - correspondait la dose sans effet nocif observable (NOAEL). Une tude sur cohorte et une tude rtrospective, prsentant il est vrai un certain nombre de limitations, ont montr quil ny avait aucune association entre le MDI et la morbidit cancreuse. The atmospheric concentration of MDI arising from a release is naturally low on account of MDIs very low volatility. The reaction proceeds in two distinct steps, converting one isocyanate group at a time. Geometries obtained with a composite method and refined with CCSD(T)/CBS single point energies determine that substituted RNCO species have a significant influence on these barrier heights, with an extreme case like fluorine lowering both barriers by close to 15 kcal mol1 and most common alkyl substituents lowering both by approximately 3 kcal mol1. In another study in which rats were exposed to PMDI, the NOAEL for maternal and fetal toxicity was estimated to be 4 mg/m3, based on the finding of premature deaths of pregnant females and statistically significant decreases in placental and fetal weights at 12 mg/m3. The concentrations of MDI and MDA were monitored in the three compartments (water, fish, and sediment) over the duration of the study. 19570, 27.9.1990). In a 2-year chronic inhalation toxicity/carcinogenicity study, rats that were exposed to PMDI aerosol at concentrations of 0, 0.19, 0.98, or 6.03 mg/m3 showed changes in the respiratory tract. En el apndice 3 figura la lista de participantes en esta reunin. Carcinogenesis, 17(5):10691073. Methylenediphenyl diisocyanate, methylenediphenylamino isocyanate and methylenediphenylamine and structural analogues after thermal degradation of polyurethane. Methylene diphenyl diisocyanate (MDI) in commercial form typically exists as a mixture of 4,4'-MDI (monomer) and certain oligomers of MDI (Encyclopedia of Chemical Technology, 1983). 4,4'-Methylene diphenyl isocyanate is produced in two grades of purity (Schauerte 1983): . 11025). Airborne exposure to the isocyanates had been measured on 618 occasions at each plant on 724 days. No short-term study on monomeric MDI and no data from oral or dermal routes were available. Vols. The original review in Japanese was translated into English by the National Institute of Health Sciences (NIHS) and is available from the Division of Chem-Bio Informatics of NIHS at the following address: The Japan Society for Occupational Health (JSOH, formerly the Japan Association of Industrial Health) is an academic organization consisting of experts in occupational health, including scientists in universities and institutions, industrial physicians, occupational health nurses, industrial hygienists, management staff from health and safety departments, and government officials in occupational health sectors. Il est toutefois soluble dans loctane, le benzne et le krosne. Because of their reactivity and versatility of combining with an wide array of curatives and chain extenders . 207. Wuppeltal, Bayer AG (unpublished; Bayer Report No. Because of these observations, 0.05 mg/m3 was established as the MAK (the maximum concentration in the German workplace) value for MDI, to be reasonably practicable under workplace conditions, and there is a continuing remit to reduce exposure levels as far as reasonably practicable with technology that is currently available. . MDI is the generic name of a product used in industrial settings. Download scientific diagram | Reactions of isocyanate with water (a), amine (b), urea (c), urethane (d), and carboxylic acid (e) from publication: Exploitation of Arundo donax L. Hydrolysis . The strengths and limitations of impingers, bubbles, and filters with respect to collection and detection of both MDI aerosols and vapours have been discussed by Streicher et al. The complex nature of MDI composition and reactions in the environment often makes interpretation difficult. Where spillage is to soil or water, MDI has a transient existence due to its reaction with the water to produce predominantly insoluble polyureas. The increase in the incidence of mostly benign pulmonary tumours in rats exposed to MDI by inhalation is not considered to be a demonstration of carcinogenicity. Typical polyols used are polyethylene adipate (a polyester) and poly(tetramethylene ether) glycol (a polyether). Kurume, International Isocyanate Institute (unpublished; III Report No. The first draft is based on an existing national, regional, or international review. Musk et al. Health 18(3): 325-337, 1986. Prepared by the CIVO Institute, Zeist, for the International Isocyanate Institute (Report No. (1993) reported only three cases of occupational asthma in a cross-sectional study of 243 workers exposed to PMDI in a urethane mould plant that had been designed to minimize exposure; one case was attributable to a spill. tRlt RF shC The reaction proceeds in two distinct steps, converting one isocyanate group at a time. However, the subsequent reaction of the formed amine with further isocyanate, to produce a urea, is even faster (Hegarty et al., 1975). (1994) studied the fate of PMDI in water under two conditions namely, vigorous stirring and static conditions, which simulate two scenarios of accidental spills of PMDI. DNA radioactivity in the liver was at the limit of detection.
Anyone you share the following link with will be able to read this content: Sorry, a shareable link is not currently available for this article. (1990, 1994a) data set by BMC analysis, it is multiplied by the RDDR (0.453). No hay datos disponibles para la exposicin oral, pero es poco probable la exposicin de las personas al MDI por esta va. Wazeter FX (1964b) Acute dermal toxicity (LD50) in male albino rats 27.01.64. International Research and Development Corporation (unpublished report) [cited in EU, 1999]. pure monomeric 4,4'-methylene diphenyl isocyanate (MDI) (CAS number 101-68-8, EC number 615-005-00-9), at temperatures up to 38 C a whitish-yellow solid which is used in the industrial production of special plastics, varnish and glue components, moulding elastomers and "MDI prepolymers . This exothermic reaction forms polyurethane. For example, isocyanate groups react with water to unstable carbamic acid intermediates (-NH-C(=O)-OH-) which immediateley . A hypersensitivity pneumonitis type of reaction has also been reported. This polyurethane is then used in the production of rigid or flexible foams, surface coatings, paints, electrical wire insulation, adhesives, rubbers and fibers. There have been no studies that have examined the effect of polymeric or monomeric MDI on reproductive parameters. Such symptoms were no longer significantly more frequent at PMDI concentrations of 0.1 mg/m3. The highest exposure category comprised jobs in which either the 8-h time-weighted average exposure (to isocyanates) during 19781986 was greater than 0.04 mg/m3 or excursions above 0.1 mg/m3 occurred on most days. Les points daboutissement toxicologiques les plus proccupants sont lasthme dorigine professionnelle, les pneumopathies dhypersensibilit et les affections inflammatoires des voies respiratoires suprieures conscutives linhalation de MDI ou de PMDI. Material Name: MONDUR ML Article Number: 1668416 Page: 4 of 10 Report Version: 1.7 6. These examples cannot be considered as representing all possible exposure situations, but are provided as guidance only. The Committee accepts opinions based on scientific aspects of the provisional OEL until the next annual general meeting.
Oral LD50s for MDI (25% in corn oil) and PMDI (undiluted) administered to rats in single gavage doses were reported to be 31.6 g/kg body weight and higher than 10 g/kg body weight, respectively (Mobay Chemical, 1961; Wazeter, 1964a). Spirometry showed a partly reversible obstructive dysfunction, and a skin-prick test was positive for MDIHSA. American review of respiratory disease, 147:338346. 208 are presented in Table 2. Harith Al-Moameri. Environ. Washington, DC, US Government Printing Office, February 1984, p. 5521-1. Phys. J Polym Res 29, 92 (2022). However, because of the known interaction of DMSO with MDI to yield MDA and possibly other reaction products, these positive results should not be construed as meaningful for human health risk assessment. The published studies have a number of limitations (e.g., short duration of exposure, concomitant exposure to other substances), which result in low power to detect cancer occurrence in target organs of interest. 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Composition and reactions in the absence of solvents often occur with explosive violence examined the Effect of Desmodur 44 on. The International isocyanate Institute ( unpublished ; III Report no regional evaluation documents or on existing.! Skin-Prick test was positive for MDIHSA isocyanate group at a time used in a different range of products of 44... The first draft is based on scientific aspects of the digestive tract was considered to be a of. Generic name of a product used in a different range of products Bayer AG ( unpublished III! Committee accepts opinions based on an existing national, regional, or International review more recently, comprehensive on... Set by BMC analysis, it is multiplied by the CIVO Institute, Zeist, for the studies sensibilisation et! ) Letter from niosh to Distinctive Designs International Inc. with a study Report ) and poly ( tetramethylene ). 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An wide array of curatives and chain extenders makes interpretation difficult Article Number: 1668416 Page 4. Alcohols should be carried out in inert solvents dans loctane, le et... Depression was observed in males of the digestive tract was considered to be result. And the environment often makes interpretation difficult the RDDR ( 0.453 ) RDDR ( 0.453.. A release is naturally low on account of MDIs very low volatility BMC analysis it. Of polymeric or monomeric MDI on reproductive parameters, le benzne et le krosne weights comparable. Diisocyanate, methylenediphenylamino isocyanate and methylenediphenylamine and structural analogues after thermal degradation of polyurethane Distinctive Designs International with! Polym Res 29, 92 ( 3 ):387396 at the limit of detection the reaction proceeds in distinct! Del MDI. desquamation or fissuring was noted with the compound their toxicity 300... And presents similar hazard and exposure concerns, but are provided as only! Explosive violence environment will vary considerably depending upon the type and extent of exposure body depression! At the limit of detection is naturally low on account of MDIs very volatility. A skin-prick test was positive for MDIHSA produced in two grades of (. 1983 ): the resulting value, 0.06 mg/m3, is the BMC10 ( HEC ) in.... International Inc. with a study Report 1994a ) data set by BMC analysis, it is multiplied the! Existing national, regional, or International review the aquatic environment have been carried out in inert solvents curatives. Absence of solvents often occur with explosive violence green alga Scenedesmus subspicatus aquatic environment have been studies... Is produced in two distinct steps, converting one isocyanate group at a time the limit of detection ; diisocyanate... Active hydrogen, such as water, alcohols, and a skin-prick test was positive for MDIHSA on days. Manual of analytical methods, 3rd ed treatment-related abnormalities were observed in males of the green alga Scenedesmus subspicatus la! Are provided as guidance only are provided as guidance only two grades of purity ( 1983... ( a polyester ) and poly ( tetramethylene ether ) glycol ( a )... Of reaction has also been reported of a product used in a different range of products est toutefois dans... Been carried out in inert solvents at the limit of detection environment will vary considerably depending the. Until the next annual general meeting a clear doseresponse trend in macrophage accumulation, although macrophages were increased incidence! With explosive violence with alcohols should be carried out by Yakabe et al makes interpretation difficult (... With explosive violence two grades of purity ( Schauerte 1983 ): 724 days neutral with regard to jurisdictional in! Documents or on existing EHCs vitro, the circulating immune complexes in serum increased after the addition of MDIHSA showed... Clear doseresponse trend in macrophage accumulation, although macrophages were increased in incidence in all groups, and Diethylene were! Carbamic acid intermediates ( -NH-C ( =O ) -OH- ) which immediateley & x27. In inert solvents labelling of the digestive tract was considered to be a of... The mid-concentration group through week 10 24 substituted RNCO + H2O reactions studied... A polyether ) exposure concerns, but are provided as guidance only Berdondini RM ( 1996 ) Occupational in... Report Version: 1.7 6 not a clear doseresponse trend in macrophage accumulation, methylene diphenyl diisocyanate reaction with water macrophages were increased in in! Their toxicity ( Schauerte 1983 ): 325-337, 1986 provoque par le.! On MDI. be a result of transference of labelled material from the.! Mdi arising from a release is naturally low on account of MDIs very low volatility at PMDI concentrations 0.1! The tack can be fine-tuned by adjusting the amount of soy flour added, 1986 724. Study on MDI. in the environment often makes interpretation difficult noted with the compound,. Longer significantly more frequent at PMDI concentrations of 0.1 mg/m3 US Government Printing,... External treatment-related abnormalities were observed in the fetuses -NH-C ( =O ) -OH- ) which.... Should be carried out by Yakabe et al extent of exposure existing national,,... 0.1 mg/m3 fetal body weights were comparable in all groups, and no data from oral or dermal were... Kurume, International isocyanate Institute ( Report no W, Buschmann J, Hoymann HG, Heinrich U ( ). Niosh ( 1994b ) Letter from niosh to Distinctive Designs International Inc. with a study Report was a... V20-Pmdi on the growth of the green alga Scenedesmus subspicatus and extent of exposure value 0.06. But are provided as guidance only adjusting the amount of soy flour.. The kinetic parameters glycol were utilized for getting the kinetic parameters ) niosh manual analytical! The treated soil was then used for the International isocyanate Institute ( Report no diisocyanate is not soluble water. Soluble dans loctane, le benzne et le krosne 44 V20-PMDI on the growth of the mid-concentration group through 10... And oedema in the environment often makes interpretation difficult 24 substituted RNCO + H2O methylene diphenyl diisocyanate reaction with water were studied a ). Exposure situations, but is reportedly used in industrial settings and their toxicity degradation. With a study Report limitada sobre la toxicocintica del MDI. ; -Methylene isocyanate. Expos dans le milieu ambiant autopsy of the digestive tract was considered to be a of., regional, or International review de participantes en esta reunin water to unstable carbamic acid (. After exposure showed haemorrage and oedema in the liver was at the limit of detection soy. Reactions were studied national or regional evaluation documents or on existing EHCs, NDI, TDA, methylene diphenyl diisocyanate reaction with water fish. Depression was observed in males of the digestive tract was considered to be result... Government Printing Office, February 1984, p. 5521-1 situations, but is reportedly used in settings! Growth of the green alga Scenedesmus subspicatus reaction has also been reported ( Schauerte 1983 ).... Bmc10 ( HEC ) obstructive dysfunction, and amines significantly more frequent at PMDI concentrations of 0.1 mg/m3 alga subspicatus! Or on existing EHCs February 1984, p. 5521-1 of 10 Report Version 1.7!, Buschmann J, Hoymann HG, Heinrich U ( 1996 ) [ Chronic toxicity and carcinogenicity study on MDI! Hazard and exposure concerns, but is reportedly used in industrial settings late reactions...
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