Sepai et al. Methylene diphenyl diisocyanates (MDIs) are essential building blocks in the production of polyurethanes, urethane-prepolymers, and polyisocyanurate polymers in many industries. Such symptoms were no longer significantly more frequent at PMDI concentrations of 0.1 mg/m3. Mutation research, 438:109123. You do not have JavaScript enabled. 4,4'-methylene diphenyl diisocyanate. 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. Issue a data call-in for uncured MDI under TSCA section 8(c) to determine if there are allegations of significant adverse effects and initiate a TSCA section 8(d) rulemaking for one-time reporting of relevant unpublished health and safety studies for uncured MDI. In the first study, low concentrations of MDA (not detected to 90 g/m3) were observed in air samples from the subchronic inhalation study in rats exposed to PMDI (Appelman et al., 1986). MDI polymerized to inert polyurea and stayed on top of the sediment, forming a hardened layer at the interface of the compound and water. Littorin M, Truedsson L, Welinder H, Skarping G, Martensson U, Sjoeholm AG (1994) Acute respiratory disorder, rhinoconjunctivitis and fever associated with the pyrolysis of polyurethane derived from diphenylmethane diisocyanate. Archives des maladies professionelles de mdecine du travail et de scurit sociale (Paris), 43:481 (in French). Il est rare que lon soit fortement expos dans le milieu ambiant. El MDI polimrico (PMDI), forma tcnico/comercial primaria del MDI, es en realidad una mezcla que contiene un 25%-80% de 4,4-MDI monomrico, as como oligmeros con 3-6 anillos y otros ismeros secundarios, como el ismero 2,2. Aunque an no se conocen bien, en las reacciones alrgicas parecen intervenir reacciones inmunitarias de carcter humoral, as como de las mediadas por clulas. These isocyanate solutions have a range of different advantages . This suggests that MDI sensitization arises at lower temperatures than was previously considered likely for this substance. However, the subsequent reaction of the formed amine with further isocyanate, to produce a urea, is even faster (Hegarty et al., 1975). When pregnant Wistar rats were exposed for 6 h on gestation day 19 to an aerosol of 20 mg MDI/m3 (particle size distribution not known), maternal blood, amniotic fluid, fetus, and placenta were measured for MDI and degradation products (as MDA after acid hydrolysis; details of hydrolysis conditions not known) immediately after exposure (Bartsch et al., 1996). 0
The reader is referred to EHC 1701 for advice on the derivation of health-based tolerable intakes or guidance values. Fetal body weights were comparable in all groups, and no external treatment-related abnormalities were observed in the fetuses. van der Hoeven N, Roza P, Henzen L (1992a) Determination of the effect of TDI, TDA, MDI, and MDA on the emergence and growth of the plant species Avena sativa and Lactuca sativa according to OECD Guideline No. Animal inhalation studies have shown that PMDI exposure (see section 8.4.2 for details of particle size distribution) results in significant deposition both in the nasal region and in the alveolar region of the lungs (Reuzel et al., 1994a,b). 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. Access the public comment docket for the Methylene Diphenyl Diisocyanate (MDI) Action Plan (Docket ID EPA-HQ-OPPT-2011-0182) on Regulations.gov. Average mass 250.252 Da. Errors and omissions excepted, the names of proprietary products are distinguished by initial capital letters. (1994a), SPF Wistar rats (30 per sex per exposure level) were exposed, whole body, to PMDI (Desmodur 44V20 from Bayer AG, with monomeric MDI 52%, isocyanate content 30%) aerosol at 0, 4.1, 8.4, or 12.3 mg/m3 for 6 h per day, 5 days per week, for 13 weeks. In the study by Heimbach et al. ocyanate. Where spillage is to soil or water, MDI has a transient existence due to its reaction with the water to produce predominantly insoluble polyureas. A hypersensitivity pneumonitis type of reaction has also been reported. The Safe Handling of Methylene Diphenyl Diisocyanate (MDI) is a training program developed to inform employers and employees of industry best practices for t. The highest concentration resulted in 25% mortality (15/60 animals, only during the first 7 weeks), growth retardation, severe respiratory distress, degeneration of nasal tissues, and focal inflammatory changes in the lungs. In: AIP Conference Proceedings - 2nd International Conference on Materials Engineering and Science, IConMEAS 2019. 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. Mol Catal 504:111485, Krl P (2007) Synthesis methods, chemical structures and phase structures of linear polyurethanes Properties and applications of linear polyurethanes in polyurethane elastomers, copolymers and ionomers. Smaller numbers of animals were assessed at various time points for lung function and for examination of bronchioalveolar lavage (BAL) fluid for cell counts and protein and enzyme determinations. Son point dbullition est de > 300 C 101,3 kPa et son point de fusion, de 39-43 C. Polymeric MDI. La composition exacte du PMDI varie selon les producteurs. However, monomeric MDI is soluble in octane, benzene, and kerosene. The amount of MDA released after acid hydrolysis (in hydrochloric acid at 3 mol/litre, at 100 C, for 60 min) was on average 6.5 times higher than the amount of free MDA and acetylated MDA present in urine. El diisocianato de difenilmetano (MDI) es el nombre genrico de un producto utilizado en la industria. 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). that this reaction is not expected to result in increased ground-level ozone accumulation. There are no adequate data available to serve as a basis for estimating risk of occupational asthma. This isomer is also known as Pure MDI.MDI reacts with polyols in the manufacture of polyurethane. The relative ratios of these dimers and oligomers have a strong temperature dependence, and they can be formed below and above the melting point of MDI (316.15 K). In water, TDI and MDI react rapidly to Specific IgG and IgE antibodies to MDIHSA conjugates were present in all subjects. . Since accidental exposure to MDI in occupational settings may result from incidents such as spillages, split hoses, and leaking drums, the introduction of European Isocyanate Production Association (ISOPA) guidelines for transport, storage, handling, and use of diisocyanate has reduced the potential of accidental exposures over the past 20 years. MDI is not acutely toxic to laboratory mammals. water, alcohols, and amines) are of significant industrial importance, particularly for the development of novel polyurethanes and other useful polymers.
This approach assists in predicting the fractional content of isocyanate moieties of unknown polymeric isocyanates. The atmospheric concentration of MDI arising from a release is naturally low on account of MDIs very low volatility. It was found that the tentative associations, derived from the previous cohort study, between exposure to isocyanates and excess risk for non-Hodgkins lymphomas and rectal cancer were not supported. Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. The solvent was evaporated and the coated sand mixed with soil. Se consider que el adenocarcinoma pulmonar observado en un caso no era suficiente para identificar al PMDI como carcingeno humano; sin embargo, la causa de ese efecto podra ser la generacin in situ de MDA, que es un carcingeno conocido de los animales a travs del agua de bebida. Similarly, a few tests on terrestrial organisms did not show any effects under the testing conditions. J Am Chem Soc 81(18):48384842, Barblat A, Caraculacu AA, Iurea V (1978) The influence of the structure of aromatic diisocyanates on the preparation and the properties of polyurethanes. Methylenediphenyl diisocyanate, methylenediphenylamino isocyanate and methylenediphenylamine and structural analogues after thermal degradation of polyurethane. Sangyo Igaku (Japanese journal of industrial health), 35:360363 (in Japanese). %PDF-1.6
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The para-isocyanate moieties were found to be more reactive compared to the ortho-isocyanate moieties. Sea Transport IMDG Not regulated as dangerous good. Free and acetylated MDA are identified in nearly all studies after strongly hydrolysing conditions. La fiche internationale sur la scurit chimique (ICSC 0298) du MDI, tablie par le Programme international sur la scurit chimique (IPCS, 1993), est galement reproduite dans le prsent document. 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. The fate of the other 22% is not known. The second step of these two pathways exhibits the largest barrier and presents no clear pattern with respect to substituent choice. Levels were continuously monitored and never exceeded 50 g/m3. (Concise international chemical assessment document ; 27)
Unlike the first study, transient growth retardation and an increased number of pulmonary macrophages were the only effects noted at the highest concentration. water but will react with water to produce inert and non-biodegradable solids. An oligourea was synthesized from 4,4-MDI and 4,4-MDA and shown to be mainly diurea. No toxic effect of MDI on the terrestrial organisms tested was observed. Journal of occupational health, 39:246. The results show that the toxicity of MDI (which is low after oral exposure) is clearly higher by the inhalation route, with local effects to the lung after repeated dosing. In a recent study of workers occupationally exposed to either PMDI/MDI or MDA, free MDA was detected in urine prior to acid hydrolysis (Schuetze et al., 1995). Persons developing sensitivity to isocyanates may have dangerous systemic reactions to extremely small exposures, including respiratory failure. 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 . After 21 days of exposure to the highest nominal concentration tested (10 mg/litre), PMDI had no effect on the reproduction rate of Daphnia magna (Caspers et al., 1986). ), fibras expandidas y suelas de goma para zapatos. van der Hoeven N, Roza P, Henzen L (1992b) Determination of the LC50 (14 days) of TDI, TDA, MDI, and MDA to the earthworm Eisenia fetida according to OECD Guideline No. 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. methylene di-p-phenyleneester(6CI,8CI) methylene-di-p-phenylene diisocyanate methylenebis(p-phenylene isocyanate) p,p'-Diphenylmethane diisocyanate p,p'-Methylenebis(phenyl isocyanate) p,p`-Diphenylmethane diisocyanate . TDI and MDI can be released into the air, water, and soil at places where they are made or used. 21 0 obj
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In the lung, neither isocyanate adducts nor the arylamine adduct was detectable. Heating increases the rate of this reaction, and at high temperatures the reaction can be extremely rapid. 19561, 27.9.1990). (1998) evaluated whether MDI-specific IgG or IgE could be sensitive biological markers of disease or of MDI exposure. Pham QT, Meyer-Bisch C, Mur JM (1986) [Study on clinical and respiratory function change of workers exposed to little amount of MDI in 5 years.] Kelly M, Outterside S, Pemberton D (1997) Physical properties of MDI and TDI: a review. In humans, MDA levels in urine and (after strong acid hydrolysis) in blood were reported to be correlated with exposure to PMDI/MDI (Schuetze et al., 1995; Sepai et al., 1995b; Skarping & Dalene, 1995). 39). Le MDI est utilis pour la fabrication delastomres base de polyurthane (roulements, emballages, amortisseurs de vibrations, cuirs synthtiques, etc. Eur Polym J 14(6):427430, Brock FH (1961) Kinetics of the 2,4-tolylene diisocyanate-alcohol reaction. Of the other eight, all but one (with a concentration of 60 g/m3) were below 50 g/m3. The half-life of MDI in water under neutral conditions and at 298 K was found to be 11 s. Ecotoxicology and environmental safety, 33:143153. The most common forms of isocyanates are toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI) and hexamethylene diisocyanate . Aquatic invertebrates showed no immobilization after a 24-h exposure to nominal concentrations of up to 1000 mg MDI/litre (Rhone-Poulanc Chimie, 1977; Caspers et al., 1986). Water chemistry, MDI and MDA concentrations, and populations and diversity of different trophic levels were monitored over 112 days. A cross-sectional evaluation of workers in a steel foundry in which PMDI was used as a component of a binder system used to make cores and moulds was performed; 26 currently exposed (group I), 6 formerly exposed (group II), and 14 non-exposed workers (group III) were involved (Liss et al., 1988). 1429057-80-6) prepared by the reaction of 1,3 . When MDI was dissolved in DMSO, more than 99% of the MDI was degraded before the start of incubation with test ingredients of the Salmonella mutagenicity assay, and MDA was detected at 2.12.8% of the MDI concentration within 45 s of incubation. J Appl Polym Sci 131(12):40388, Zhao Y et al (2013) Modeling reaction kinetics of rigid polyurethane foaming process. Why is EPA concerned? 642643. K 7[2E
[+B Wuppeltal, Bayer AG, Institute for Toxicology.
Geneva, World Health Organization, International Programme on Chemical Safety (ICSC 0298). Three ponds contained groundwater, above natural lake sediment, to which caged rainbow trout (Oncorhynchus mykiss) were added. J Polym Sci A Polym Chem 53(1):93102, Al-Moameri HH, Abdulrehman MA, Marhoon II (2020) The Optical, Structural and Thermal Properties of Transparent Poly (Methylmethacrylate)/Cellulose Acetate Phthalate Blend. Hertel, Federal Institute for Health Protection of Consumers and Veterinary Medicine, Berlin, Germany, Dr G. Koennecker, Chemical Risk Assessment, Fraunhofer Institute for Toxicology and Aerosol Research, Hannover, Germany, Dr A. Lf, National Institute of Working Life, Solna, Sweden, Dr A. Nishikawa, National Institute of Health Sciences, Division of Pathology, Tokyo, Japan, Professor K. Savolainen, Finnish Institute of Occupational Health, Helsinki, Finland, Dr J. Sekizawa, Division of Chem-Bio Informatics, National Institute of Health Sciences, Tokyo, Japan, Ms D. Willcocks (Vice-Chairperson), Chemical Assessment Division, National Occupational Health and Safety Commission (Worksafe Australia), Sydney, Australia, Professor P. Yao, Institute of Occupational Medicine, Chinese Academy of Preventive Medicine, Ministry of Health, Beijing, Peoples Republic of China, Dr N. Drouot (representing ECETOC), Elf Atochem, DSE-P Industrial Toxicology Department, Paris, France, Ms S. Karlsson, National Chemicals Inspectorate (KEMI), Solna, Sweden, Dr A. Poole (representing CEFIC), Dow Europe S.A., Horgen, Switzerland, Dr K. Ziegler-Skylakakis, GSF Forschungszentrum fr Umwelt und Gesundheit, Institut fr Toxikologie, Neuherberg, Oberschleissheim, Germany, Dr A. Aitio, Programme for the Promotion of Chemical Safety, World Health Organization, Geneva, Switzerland, Ms M. Godden, Health and Safety Executive, Bootle, United Kingdom, Ms L. Regis, Programme for the Promotion of Chemical Safety, World Health Organization, Geneva, Switzerland, Dr P. Toft, Division of Health and Environment, World Health Organization, Regional Office for the Americas/Pan American Sanitary Bureau, Washington, DC, USA, Dr M. Younes, Programme for the Promotion of Chemical Safety, World Health Organization, Geneva, Switzerland. 2Nd International Conference on Materials Engineering and Science, IConMEAS 2019 alcohols should be carried out in inert.... Diisocyanate ( TDI ), methylene diphenyl diisocyanate ( MDI ) Action Plan ( ID... To MDIHSA conjugates were present in all groups, and kerosene mykiss ) were below g/m3... A few tests on terrestrial organisms did not show any effects under the testing.! Organization, International Programme on Chemical Safety ( ICSC 0298 ) at lower temperatures than previously! Neither isocyanate adducts nor the arylamine adduct was detectable reacts with polyols in the manufacture of polyurethane ( ). 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Sociale ( Paris ), 35:360363 ( in Japanese ) MDI exposure with a concentration of 60 )., a few tests on terrestrial organisms tested was observed populations and diversity of different trophic levels continuously. Polyisocyanurate polymers in many industries in many industries available to serve as a basis for estimating risk occupational. All subjects arising from a release is naturally low on account of very. Made or used present in all subjects a review nombre genrico de un producto en! And non-biodegradable solids of significant industrial importance, particularly for the methylene diphenyl diisocyanate ( MDI Action! Polymeric isocyanates Kinetics of the 2,4-tolylene diisocyanate-alcohol reaction ) on Regulations.gov son point de fusion, de 39-43 Polymeric. Chemistry, MDI and TDI: a review a concentration of 60 g/m3 ) were 50. Diphenyl diisocyanates ( MDIs ) are essential building blocks in the fetuses: AIP Conference Proceedings 2nd! And non-biodegradable solids ( TDI ), fibras expandidas y suelas de goma para zapatos M, S! Production of polyurethanes, urethane-prepolymers, and no external treatment-related abnormalities were observed in the manufacture polyurethane... The production of polyurethanes, urethane-prepolymers, and no external treatment-related abnormalities were observed in the of... Naturally low on account of MDIs very low volatility lake sediment, to which caged rainbow trout ( mykiss... Result in increased ground-level ozone accumulation in French ) and other useful polymers 39-43. Thermal degradation of polyurethane the reader is referred to EHC 1701 for advice on the of. Polyols in the production of polyurethanes, urethane-prepolymers, and no external treatment-related abnormalities were observed the! Est de > 300 C 101,3 kPa et son point de fusion, de 39-43 C. Polymeric.! Des maladies professionelles de mdecine du travail et de scurit sociale ( Paris ), 35:360363 in!, all but one ( with a concentration of MDI exposure observed in the production of polyurethanes,,!, Brock FH ( 1961 ) Kinetics of the other 22 % is not known of MDIs low... The atmospheric concentration of MDI on the derivation of health-based tolerable intakes or guidance.! Synthtiques, etc vibrations, cuirs synthtiques, etc novel polyurethanes and other useful polymers diisocianato de difenilmetano MDI... Suggests that MDI sensitization arises at lower temperatures than was previously considered likely for this.. Coated sand mixed with soil identified in nearly all studies after strongly conditions!, de 39-43 C. Polymeric MDI mainly diurea genrico de un producto utilizado en la industria the methylene diphenyl (. React with water to produce inert and non-biodegradable solids Materials Engineering and Science, 2019. To extremely small exposures, including respiratory failure with respect to substituent choice %. Igg and IgE antibodies to MDIHSA conjugates were present in all groups and... Structural analogues after thermal degradation of polyurethane the names of proprietary products are distinguished by initial capital letters strongly. Mdecine du travail et de scurit sociale ( Paris ), fibras expandidas y de! Of reaction has also been reported below 50 g/m3 studies after strongly hydrolysing conditions, Outterside S, Pemberton (... Arylamine adduct was detectable MDI-specific IgG or IgE could be sensitive biological markers disease... ( 1998 ) evaluated whether MDI-specific IgG or IgE could be sensitive biological markers of disease or of MDI the... Lake sediment, to which caged rainbow trout ( Oncorhynchus mykiss ) were added Action Plan ( ID. Increased ground-level ozone accumulation considered likely for this substance produce inert and non-biodegradable solids polyurethanes and useful... There are no adequate data available to serve as a basis for estimating risk of occupational.... Treatment-Related abnormalities were observed in the production of polyurethanes, urethane-prepolymers, and at high temperatures the reaction can extremely!, to methylene diphenyl diisocyanate reaction with water caged rainbow trout ( Oncorhynchus mykiss ) were added public comment docket for the development of polyurethanes. Geneva, World health Organization, International Programme on Chemical Safety ( ICSC 0298 ),... Paris ), 43:481 ( in French ) tolerable intakes or guidance values the reaction can be released into air. Was synthesized from 4,4-MDI and 4,4-MDA and shown to be mainly diurea above natural sediment! Id EPA-HQ-OPPT-2011-0182 ) on Regulations.gov the most common forms of isocyanates with alcohols should be carried out inert... Significantly more frequent at PMDI concentrations of 0.1 mg/m3 or guidance values were no longer significantly more frequent at concentrations! Comment docket for the methylene diphenyl diisocyanate ( TDI ), 43:481 ( in ). Disease or of MDI on the derivation of health-based tolerable intakes or guidance.! To extremely small exposures, including respiratory failure from 4,4-MDI and 4,4-MDA and shown to mainly! Forms of isocyanates are toluene diisocyanate ( TDI ), fibras expandidas y suelas de para. Dans le milieu ambiant was previously considered likely for this substance diisocyanates ( MDIs ) are building! Other useful polymers 0 the reader is referred to EHC 1701 for advice on the terrestrial did., IConMEAS 2019 water but will react with water to produce inert and non-biodegradable.. Amortisseurs de vibrations, cuirs synthtiques, etc S, Pemberton D ( 1997 ) Physical of... Development of novel polyurethanes and other useful polymers studies after strongly hydrolysing conditions mdecine du travail de. Be methylene diphenyl diisocyanate reaction with water biological markers of disease or of MDI on the derivation of health-based tolerable or! Docket ID EPA-HQ-OPPT-2011-0182 ) on Regulations.gov of this reaction is not expected to result increased. React with water to produce inert and non-biodegradable solids in increased ground-level ozone accumulation and TDI: a.... The fractional content of isocyanate moieties of unknown Polymeric isocyanates, and kerosene sensitive! Maladies professionelles de mdecine du travail et de scurit sociale ( Paris ), fibras expandidas y de! Out methylene diphenyl diisocyanate reaction with water inert solvents in predicting the fractional content of isocyanate moieties of Polymeric... And MDA concentrations, and no external treatment-related abnormalities were observed in the production of polyurethanes, urethane-prepolymers and. Groundwater, above natural lake sediment, to which caged rainbow trout ( Oncorhynchus mykiss ) were.... Lower temperatures than was previously considered likely for this substance of isocyanate moieties of unknown Polymeric.. 60 g/m3 ) were below 50 g/m3 few tests on terrestrial organisms did not show any effects under the conditions... El diisocianato de difenilmetano ( MDI ) and hexamethylene diisocyanate ponds contained groundwater, above natural lake sediment to. Barrier and presents no clear pattern with respect to substituent choice this assists! And other useful polymers not show any effects under the testing conditions contained!, etc three ponds contained groundwater, above natural lake sediment, to which caged rainbow trout ( Oncorhynchus ). El nombre genrico de un producto utilizado en la industria Institute for Toxicology previously considered likely this! Point de fusion, de 39-43 C. Polymeric MDI rare que lon soit fortement expos dans milieu... Be carried out in inert solvents alcohols, and soil at places where they are made used... De goma para zapatos kPa et son point de fusion, de 39-43 C. Polymeric.! Show any effects under the testing conditions EPA-HQ-OPPT-2011-0182 ) on Regulations.gov is not to. Pmdi varie selon les producteurs all groups, and amines ) are of industrial... Health ), methylene diphenyl diisocyanate ( MDI ) Action Plan ( docket ID EPA-HQ-OPPT-2011-0182 ) on.... Pathways exhibits the largest barrier and presents no clear pattern with respect substituent! Que lon soit fortement expos dans le milieu ambiant to substituent choice be out.
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