The flow chart shows the procedures followed to produce a CICAD. In most cases (17 out of 20), the air levels were below detection limits. Waalkens-Berendsen DH, Arts JHE (1992) Report of a developmental toxicity range-finding study of inhaled polymeric MDI aerosol in rats. 4,4'-diphenyl methane diisocyanate (MDI ) / 1,1'-methylenebis(4-isocyanato-benzene) . The mention of specific companies or of certain manufacturers products does not imply that they are endorsed or recommended by the World Health Organization in preference to others of a similar nature that are not mentioned. TDI and MDI are extremely reactive chemicals and do not stay in the environment long. Comments were received from: M. Baril, Institut de Recherche en Sant et en Scurit du Travail du Qubec, Canada, T. Berzins, National Chemicals Inspectorate (KEMI), Sweden, R. Cary, Health and Safety Executive, United Kingdom, Chemical Industries Association (CIA) Isocyanate Producers Sector Group (IPSG), United Kingdom, M. Collins, Gilbert International Limited, United Kingdom, P. Edwards, Department of Health, United Kingdom, T. Fortoul, National University of Mexico, Mexico, R. Hertel, Bundesinstitut fr Gesundheitlichen Verbraucherschutz und Veterinrmedizin, Germany, J. Lesage, Institut de Recherche en Sant et en Scurit du Travail du Qubec, Canada, H. Nagy, National Institute for Occupational Safety and Health, Cincinnati, USA, D. Willcocks, National Industrial Chemicals Notification and Assessment Scheme, Australia, P. Yao, Chinese Academy of Preventive Medicine, Peoples Republic of China, K. Ziegler-Skylakakis, GSF-Forschungszentrum fr Umwelt und Gesundheit GmbH, Germany, Mr H. Abadin, Agency for Toxic Substances and Disease Registry, Centers for Disease Control and Prevention, Atlanta, GA, USA, Dr B. kesson, Department of Occupational & Environmental Health, University Hospital, Lund, Sweden, Dr T. Berzins (Chairperson), National Chemicals Inspectorate (KEMI), Solna, Sweden, Mr R. Cary, Health and Safety Executive, Bootle, Merseyside, United Kingdom, Dr R.S. When PMDI (liquid form; 0, 2.5, 3.9, 6.0, or 9.4 g/kg body weight) was applied to the abraded skin of albino rabbits (2 per sex per group) for 24 h (Wazeter, 1964b), one animal at the highest dose exhibited slight oedema during the first and second days. El diisocianato de difenilmetano (MDI) es el nombre genrico de un producto utilizado en la industria. Signs of less severe respiratory distress were also observed in animals exposed to 8.4 mg/m3. IF IN EYES: Rinse cautiously with water . Three workers had radiographic evidence of pneumoconiosis, and 12 had asthma, defined as the presence of bronchial hyperreactivity, cough, and additional respiratory symptoms, such as wheeze, chest tightness, or breathlessness. One of two workers reacted simultaneously to both MDI and MDA. Female Wistar rats were treated topically (on the back) with 14C-MDI (labelled in the ring) in acetone to investigate the possibility of systemic circulation and DNA-binding potency of MDI (Vock & Lutz, 1997). It is well documented that isocyanates are a cause of occupational asthma (Vandenplas et al., 1993). The conversion factor for MDI is as follows: 1 ppm = 10.4 mg/m3. Analyst, 119:8997. Manchester, International Isocyanate Institute (unpublished; III Report No. Hagmar L, Welinder H, Mikoczy Z (1993a) Cancer incidence and mortality in the Swedish polyurethane foam manufacturing industry. Gross pathological examination remained essentially negative; no data on histological examination were reported. Deutsche Forschungsgemeinschaft, VCH, 8:6595. Available data show that there is no need for concern regarding the effects of MDI on organisms in the environment, although more detailed information regarding the formation of MDA in the environment and its effects on organisms is required before any firm conclusions can be drawn. The finding of placental transfer of MDI and its degradation product from pregnant rats exposed to aerosol to fetuses demands further study on its relevance to human risk assessment. (1998) evaluated whether MDI-specific IgG or IgE could be sensitive biological markers of disease or of MDI exposure. A satellite group of rats (10/sex/exposure level) was exposed Such reactions in the absence of solvents often occur with explosive violence . Additional waters (one or two) are predicted to lower both barriers significantly at the CCSD(T)/aug-cc-pV(T+d)Z level of theory with strongly electron withdrawing RNCO substituents also increasing these effects, similar to the uncatalyzed case. (Methylene Diphenyl Diisocyanate) Land Transport TDG Not regulated as dangerous good. The Committee for the Recommendation of Occupational Exposure Limits of JSOH reviews scientific information on the health effects of chemical substances and physical agents with special reference to exposureeffect and exposureresponse relationships and applies its research to the creation of an Occupational Exposure Limit (OEL) and to the documentation of the reasoning behind the OEL. Although limited in various ways, a cohort study and a retrospective study showed no significant association with cancer morbidity. This study demonstrated that induction of both MDI-specific IgG responses and IgE-mediated respiratory sensitization occurred in a population of workers exposed to MDI in a steel foundry. There was no attempt to identify the nature of the excreted radioactivity. This is a preview of subscription content, access via your institution. All the subjects had worked in a plant where a resin based on MDI was used in the manufacture of wood chipboards. For MDA, IARC (1986) concluded that there were no data in humans and sufficient evidence for carcinogenicity in animals. As of 2019, the largest producer was Wanhua Chemical Group. Methods Objects Chem Anal 15(1):3339, Huang XY, Yu W, Sung CSP (1990) Studies of Model Urethane Reactions and Cure in Polyurethanes by UV Absorption and Fluorescence Spectroscopy. Where spillage is to soil or water, MDI has a transient existence due to its reaction with the water to produce predominantly insoluble polyureas. water, alcohols, and amines) are of significant industrial importance, particularly for the development of novel polyurethanes and other useful polymers. La production annuelle totale de MDI et de PMDI a t denviron 1,2 millions de tonnes en 1991, de 1,5 millions en 1993, de 1,78 millions en 1994 et de 1,95 millions de tonnes en 1996. RSC Adv 6(52):4702347032, Al-Moameri HH, Hassan G, Abdulrehman MA (2020) Predicting The Composition Of Qurna Crude Oil Fraction By Ternary Composition Diagram. Body weight depression was not observed in females. Su presencia en el agua es fugaz; as pues, su solubilidad en agua es puramente terica. Cross-reactivity to toluene diisocyanate (TDI) and other isocyanates was demonstrated. Il se forme galement de la MDA mais sa concentration est toujours faible. These effects correlated with pulmonary function deficits (FEF25 [forced expiratory flow from 25% of the forced vital capacity, or FVC] and carbon monoxide diffusion), particularly in the high-exposure group. @B96@@T `$0xG& BI\Aq4XJ4g!`,ZB3IP%h1$l t42'c|q"D>WG3% *(N"&$$0A *M TDI and MDI can be released into the air, water, and soil at places where they are made or used. 4,4'-methylene diphenyl diisocyanate. US EPA Integrated Risk Information System: Methylene Diphenyl Diisocyanate (monomeric MDI) and polymeric MDI (PMDI) (CASRN 101-68-8, . In contrast to the results reported by Reuzel et al. The mean number of MDI exposure years was 8.6, 1.1, and 0 years for group I, group II, and group III, respectively. The most commonly applied industrial synthesis of 4,4-methylene diphenyl diamine (4,4-MDA), an important polyurethane intermediate, is the reaction of aniline and formaldehyde. International archives of occupational and environmental health, 62:521. endstream endobj startxref No specific fertility studies are available for MDI. Chemical research in toxicology, 10:424431. In contrast, the respiration rate was decreased in a dose-dependent manner in mice exposed to MDI aerosol concentrations between 10.2 and 58.5 mg/m3 (Weyel & Schaffer, 1985). In all tests summarized in this section, MDI was added to the test solution, and no concentration measurements were performed subsequently during exposure. Case reports as well as epidemiological studies have described MDI as a cause of occupational dermatitis, skin sensitization, and asthma. Vols. Day BW, Basalyga DM, Kramarik JA, Karol MH (1997) Formation, solvolysis and transcarbamoylation reactions of bis(S-glutathionyl) adducts of 2,4- and 2,6-diisocyanatotoluene. Support for the chemical stability of MDI is given in one study in which the polyurea formed from the reaction of PMDI with water was stirred at 40 C in aqueous buffer solutions for 14 days. BASF (1994) Prenatal toxicity of polymeric MDI in rats. The method comprises the following steps of: adding the MDI and an organic solvent into a reaction kettle, raising the temperature, dissolving the MDI, stirring uniformly, adding dehydrated polyol, and reacting for 1 to 6 hours at the temperature of between 40 . A similar, smaller difference was seen with non-Hodgkins lymphoma. 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. Sepai et al. D \3 d3@m m y\AI HB(! cIG9O I@RiTe6OTjU:VWU No treatment-related findings in dams and fetuses occurred at 1 and 4 mg/m3. Solitary pulmonary adenomas, described as rare in this strain, were observed in males (6/60) and females (2/59) exposed to 6.03 mg/m3 compared with controls (0/120). MDI-based isocyanates. OSHA Technical Manual (OTM). please go to the Copyright Clearance Center request page. A NIOSH (1994a) report noted skin irritation attributed to MDI. MDI polymerized to inert polyurea and stayed on top of the sediment, forming a hardened layer at the interface of the compound and water. INTRODUCTION Methylenediphenyl diisocyanate (MDI) and toluene di-isocyanate (TDI) are manufactured and used on a large scale, amounting to a total of about 4 million metric tons per year worldwide. Aerosol inhalation. As well as forming isocyanate dimers and trimers . The study provides evidence that MDI accumulation through the aquatic food chain is extremely unlikely, as might be expected considering the very low solubility and high reactivity of MDI in aqueous solution. Therefore, the isocyanate resin-water reaction is considered as the one of the most important reactions when bonding wood composite materials with isocyanate resins. Journal of allergy and clinical immunology, 82(1):5561. The most commonly used isocyanate in urethane adhesives is MDI. Table 2: Toxicity of MDI to terrestrial organisms.a. The fate of the PMDI and ecotoxic effects on the aquatic population were monitored for 112 days. MDI is used for polyurethane elastomers (rollers, packing, rubber vibration insulators, synthetic leather, etc. Hazards Identification Emergency Overview . 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 . The mixture is designated as polymeric MDI Dr Sakurai, who chairs the Committee, peer-reviewed and assisted in the preparation of the draft of the CICAD for MDI. Total world production of MDI and polymeric MDI is over 7.5 million tonnes per year (in 2017). To assist the reader, examples of exposure estimation and risk characterization are provided in CICADs, whenever possible. What action is EPA taking? CICADs are not a summary of all available data on a particular chemical; rather, they include only that information considered critical for characterization of the risk posed by the chemical. Polymeric MDI. The report entitled Toxicological review of methylene diphenyl diisocyanate (MDI) and summary information on IRIS (Integrated Risk Information System) have received peer review both by EPA scientists and by independent scientists external to EPA. Prog Mater Sci 52(6):9151015, Article Gahlmann R (1993) A critical review for the International Isocyanate Institute. In the collective at concentrations below 0.2 mg/m3, no significant changes in lung spirometry were found. Appelman LM, de Jong AWJ (1982) Acute inhalation toxicity study of polymeric MDI in rats. ccq@uga.edu Hydrogenated MDI ( H12MDI or 4,4-diisocyanato dicyclohexylmethane) is an organic compound in the class known as isocyanates. Handling MDI requires strict engineering controls and personal protective equipment. Subsequent to external review and incorporation of comments, this assessment has undergone an agency-wide review process whereby the IRIS Program Manager has achieved a consensus approval among the Office of Research and Development, Office of Air and Radiation, Office of Prevention, Pesticides, and Toxic Substances, Office of Solid Waste and Emergency Response, Office of Water, Office of Policy Planning and Evaluation, and the Regional Offices. Effects on lung function were assessed by DFG (1997) based on the results of nine studies namely, Cavelier et al. British journal of industrial medicine, 42:94100. Adequate time is allowed for the selected experts to undertake a thorough review. The value considered most appropriate as a basis for development of a tolerable concentration (TC) in air is the lower 95% confidence limit on the BMC at the 10% risk level (BMC10) using the Reuzel et al. Tanaka K, Takeoka A, Nishimura F, Hanada S (1987) Contact sensitivity induced in mice by methylene bisphenyl diisocyanate. Using ear thickening as the criterion, transfer of MDI-induced contact sensitivity with or without T-cell deletion by monoclonal anti-Thy-1,2 antibody was studied (Tanaka et al., 1987). COMPARATIVE KINETICS AND METABOLISM IN LABORATORY ANIMALS AND HUMANS, 8. The absolute and relative lung weights in the high-dose group were significantly increased (23%) compared with the sham-treated control animals; this end-point was not examined in the other exposure groups. Although there are no human or animal studies that have examined the oral route of exposure, it is unlikely that humans would be exposed by the oral route. The para-isocyanate moieties were found to be more reactive compared to the ortho-isocyanate moieties. No MDI or MDA was detected in the water (detection limits 4 and 10 g/litre, respectively) or in the fish (detection limits 0.5 and 1.4 mg/kg, respectively). 1st Source Research, 617 Hutton St., Raleigh, North Carolina, USA, c Toxicology and applied pharmacology, 77:427433. 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. CICADs are concise documents that provide summaries of the relevant scientific information concerning the potential effects of chemicals upon human health and/or the environment. (1977), Pham et al. Workers with IgG antibodies specific for one diisocyanateHSA conjugate exhibit cross-reactivity to antigens prepared with other diisocyanates. Such . A hypersensitivity pneumonitis type of reaction has also been reported. Brussels, European Isocyanate Production Association (unpublished report). In water, TDI and MDI react rapidly to On dsigne sous le nom gnrique de diisocyanate de diphnylmthane (MDI) un produit utilis dans lindustrie. Biodegradation in water and sediment: simulation tests; Biodegradation in soil; . {?Fpp#5pv#NCH28-|iJd?`7[km]SN~=}lva9$}HIQdm85X0`mifm/ClIJ(%lTM]j&1nv^S AxJ&>G6L+s 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. Sepai et al. Pour ce qui est de lexposition par la voie respiratoire, on ne dispose que dtudes limites sur le rat. This may take some time to load. Las concentraciones de MDA que se forman en el medio ambiente por la reaccin del MDI con el agua son siempre bajas. These conditions will also form MDA from conjugated MDI. 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