Sepai et al. With one exception in which workers were previously exposed to concentrations of up to 0.9 mg/m3, all the collective exposed to concentrations of 0.05 mg/m3 or less was without symptoms. (1990). MDI is not stable in DMSO, there being many products generated within minutes (Herbold, 1990a,b; Gahlmann, 1993). The response to MDI challenge indicated a doseresponse effect at 0.637 mg/kg body weight. The incidence of olfactory atrophy was statistically significant in high-dose males (5/10) and high-dose females (6/10). En un estudio de cohortes y un estudio retrospectivo, aunque eran limitados en varios aspectos, se puso de manifiesto que no haba una asociacin significativa con la morbilidad del cncer. . The most common forms of isocyanates are toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI) and hexamethylene diisocyanate . NTP (1986) Toxicology and carcinogenesis studies of commercial grade 2,4(80%)- and 2,6(20%)-toluene diisocyanate in F344/N rats and B6C3F1 mice (gavage studies). The ponds contained natural lake sediment and groundwater, to which caged fish were added. Harmful if inhaled. No adverse effects on the distribution and incidence of tumours were found with the exception of tumours in the lungs. Tests assessing the mutagenic potential of MDI in vitro and in vivo show no convincing evidence of mutagenic activity. 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. El MDI no tiene una toxicidad aguda para los mamferos de laboratorio. The Committee submits the OEL as a provisional OEL to a meeting of JSOH councillors and to an annual general meeting of JSOH for temporary approval, after which the provisional OEL and documentation are published in JSOHs official journal, Sangyo Eiseigaku Zasshi (formerly Sangyo Igaku [Japanese Journal of Industrial Health]. 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. Washington, DC, US Government Printing Office, February 1984, p. 5521-1. Clinical allergy, 14:453461. Dr Sakurai, who chairs the Committee, peer-reviewed and assisted in the preparation of the draft of the CICAD for MDI. Although limited in various ways, a cohort study and a retrospective study showed no significant association with cancer morbidity. Journal of allergy and clinical immunology, 84(4 Pt 1):507514. Participants at the Final Review Board meeting are listed in Appendix 3. Airborne exposure to the isocyanates had been measured on 618 occasions at each plant on 724 days. Analyst, 122:275278. Le dpouillement bibliographique a t poursuivi jusqu novembre 1998 laide du systme MEDLINE, la recherche de toute information nouvelle susceptible dtre utile lvaluation. Serum-specific IgE and IgG antibodies to an MDIHSA conjugate were assayed by the radioallergosorbent test (RAST) and the enzyme-linked immunosorbent assay, respectively, and compared with nine non-exposed laboratory controls. The challenge solution induced ear swelling of delayed onset, with its peak at 24 h. Passive transfer of the MDI-induced contact sensitivity was achieved by injecting lymphocytes from the lymph nodes of MDI-sensitized mice into the caudal vein of syngeneic mice, and the effector cells were found to be T-cells. MDI did not show toxicities to fish, aquatic invertebrates, algae, or microorganisms under any acute or long-term exposure testing conditions. Vock EH, Lutz WK (1997) Distribution and DNA adduct formation of radiolabeled methylenediphenyl-4,4-diisocyanate (MDI) in the rat after topical treatment. Experimental results of reaction temperature profile and polyurethane gel viscosity were required to verify the simulation program's reaction parameters. Polyester-polyurethane adhesive formulated from the following: Polyurethane component prepared from polypropylene glycol, toluene diisocyanate, allophanate-modified methane diphenyl diisocyanate and 4,4'-diphenylmethane diisocyanate (CAS Reg. Exposure to PMDI aerosols at a concentration of 12 mg/m3 caused premature death in 2 out of 25 animals. A health study of the 78 workers in an iron and steel foundry in Vancouver, Canada, was carried out, and the results were compared with those found in 372 railway repair yard workers (Johnson et al., 1985). For more information search the European Chemicals Agency database. Liss GM, Tarlo SM, Banks DE (1996) Evidence for occupational asthma among compensation claimants at a polyurethane utilizing facility. O0C3# @"6 ' lAn7.j&\)Os ;(>O@k+87c *ah:H It is also known as 4,4'-methylenedi (cyclohexyl isocyanate) or . Before acceptance for publication as CICADs by IPCS, these documents undergo extensive peer review by internationally selected experts to ensure their completeness, accuracy in the way in which the original data are represented, and the validity of the conclusions drawn. 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). The International Chemical Safety Card (ICSC 0298) for MDI, produced by the International Programme on Chemical Safety (IPCS, 1993), has also been reproduced in this document. (1988) prospectively studied a group of 318 polyurethane foam workers (including 104 women) who were grouped according to their job category as follows: unexposed, indirectly exposed, and directly exposed. Mancuso G, Reggiani M, Berdondini RM (1996) Occupational dermatitis in shoemakers. Our results indicate that an additional RNCO molecule might catalyze imidic acid formation but have less influence on the efficiency of carbamate formation. Polymeric MDI (PMDI), the primary technical/commercial form of MDI, is actually a mixture that contains 2580% monomeric 4,4-MDI as well as oligomers containing 36 rings and other minor isomers, such as the 2,2-isomer. [11] It is a potentially violently reactive material towards water and other nucleophiles. 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. PMDI used in experiments is complex and composed of 56 major constituents having 24 aromatic rings. 3. However, significantly more frequent respiratory symptoms were sometimes observed at these concentrations, although it is not clear whether they were caused by simultaneous exposure to other compounds. Mann M (1987) Evidence for the formation of hydrate of MDI [letter to the editor]. Aerosol inhalation. However, the subsequent reaction of the formed amine with further isocyanate, to produce a urea, is even faster (Hegarty et al., 1975). In all tests summarized in this section, MDI was added to the test solution, and no concentration measurements were performed subsequently during exposure. 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. Le MDI est utilis pour la fabrication delastomres base de polyurthane (roulements, emballages, amortisseurs de vibrations, cuirs synthtiques, etc. Les rsultats de cette tude, permettent de retenir - en dehors de tout effet cancrogne - la valeur de 0,19 mg/m3 pour la dose sans effet nocif observable (NOAEL) et de 0,98 mg/m3 pour la dose la plus faible produisant un effet nocif observable (LOAEL). The two major competing reaction mechanisms during pMDI curing with: (a) water, where an aromatic amine (after the release of CO 2 ) reacts with isocyanate to form urea, biuret, and polyurea; and . Le PMDI sert la confection de mousses rigides ou souples, de liants pour sable de moulage et disolants thermiques. water, the rate of reaction is very slow at temperatures below 122F (50C). This condensation reaction produces MDA and a complex mixture of polyamines, which are phosgenated to obtain a methylene diphenyl diisocyanate mixture. /G Spanne M, Tinnerberg H, Dalene M, Skarping G (1996) Determination of complex mixtures of airborne isocyanates and amines, Part 1. Herd ZL, Bernstein DI (1994) Antigen-specific stimulation of histamine releasing factors in diisocyanate-induced occupational asthma. British journal of industrial medicine, 50:10031007. First-aid measures Inhalation Remove victim to fresh air and keep at rest in a position comfortable for . Carino M, Aliani M, Licitra C, Sarno N, Ioli F (1997) Death due to asthma at workplace in a diphenylmethane diisocyanate-sensitized subject. 347365 (IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Humans, Vol. 4,4'-diphenyl methane diisocyanate (MDI ) / 1,1'-methylenebis(4-isocyanato-benzene) . The resulting value, 0.06 mg/m3, is the BMC10 (HEC). Reaction mass of 4,4'-methylenediphenyl diisocyanate and o-(p-isocyanatobenzyl)phenyl isocyanate / methylene diphenyl diisocyanate On day 21 of pregnancy, the female rats were sacrificed and a caesarean section was performed. 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. La liste des participants au Comit dvaluation finale figure lappendice 3. Son point dbullition est de > 300 C 101,3 kPa et son point de fusion, de 39-43 C. Some isocyanates react with water to form amines and liberate carbon dioxide. Humoral as well as cellular immunity may be involved in the pathogenesis of hypersensitivity due to isocyanates. The stability of MDI in a model and a real-test environment was studied (Seel et al., 1999). Cavelier C, Pham QT, Mereau P, Mur JM, Rombach F, Cicolella A, Bui Dinh Long L, Toamain JP, Baudin V, Henquel JC, Poincelot F, Malo JP, Vincent R (1977) [Isocyanates and respiratory function.] They are the major diisocyanates used Hiasa Y, Kitahori Y, Enoki N, Konishi N, Shimoyama T (1984) 4,4-diaminodiphenylmethane: promoting effect on the development of thyroid tumors in rats treated with N-bis(2-hydroxypropyl)nitrosamine. The subjects had been exposed to hydrocarbon solvent as well, but none of them was symptomatic until MDI was introduced to the workplace. In a second experiment using topical administration, 32P-postlabelling analysis did not reveal isocyanateDNA adducts in the skin (Vock & Lutz, 1997). 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. Neither application rate caused any direct toxic effect on the aquatic community, but some significant indirect effects on parts of the macrobenthos were observed. 4,4'-Diphenylmethane diisocyanate is not soluble in water. The 4,4 isomer is most widely used, and is also known as 4,4-diphenylmethane diisocyanate. The non-neoplastic information in this study suggests a NOAEL of 0.19 mg/m3 and a lowest-observed-adverse-effect level (LOAEL) of 0.98 mg/m3. It should be noted that the EU document is still an unapproved draft and that the information presented in the environmental sections is based mainly on unpublished studies. 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). 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. In the lung, neither isocyanate adducts nor the arylamine adduct was detectable. Both positive and negative results were obtained when monomeric MDI dissolved in dimethyl sulfoxide (DMSO) was tested in vitro with Salmonella typhimurium. Heimbach F, Jaeger K, Sporenberg W (1996) Fate and biological effects of polymeric MDI in small artificial ponds. SECTION 6: ACCIDENTAL RELEASE MEASURES ACCIDENTAL RELEASE MEASURES: Mme si on en voit encore mal le mcanisme, il semble que des ractions immunitaires humorales et cellulaires jouent un rle dans les manifestations allergiques. Current Actions:Download the complete Methylene Diphenyl Diisocyanate (MDI) Action Plan (PDF). Diisocyanates are well known dermal and inhalation sensitizers in the workplace and have been documented to cause asthma, lung damage, and in severe cases, fatal reactions. : 26447-40-5 2. [3] This isomer is also known as Pure MDI. 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). 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). MDI is used for polyurethane elastomers (rollers, packing, rubber vibration insulators, synthetic leather, etc. * 10.0 kmol of a 40.0 mol% methanol and 60.0 mol% water mixture is processed in a normal batch . in a third-party publication (excluding your thesis/dissertation for which permission is not required) Zymergen, 5980 Horton Street, Suite 105, Emeryville, California, USA. What material of storage tank can be suitable of storing methylene diphenyl diisocyanate? Scandinavian journal of work, environment & health, 6:221226. The major application of 4,4-MDI is the production of rigid polyurethane. 9016-87-9 Polymeric diphenylmethane diisocyanate 49000 mg/kg Rat >9400 mg/kg Rabbit N.I. Zeist, TNO Nutrition and Food Research (unpublished; TNO Report No. En estudios con trabajadores se han identificado MDA libre, MDA acetilada y aductos con hemoglobina o albmina en la orina y la sangre. DOI: 10.1039/D1CP03302F. Le 4,4-MDI se prsente sous la forme dun solide jaune ple la temprature ambiante, dont la masse molculaire est de 250. La informacin no neoplsica de este estudio parece indicar una NOAEL de 0,19 mg/m3 y una concentracin ms baja con efectos adversos observados (LOAEL) de 0,98 mg/m3. MDI, like the other isocyanates, is an allergen and sensitizer. Guinea-pigs exposed to monomeric MDI aerosol at concentrations between 0.6 and 350 mg/m3 (no other details available) for 3 h showed a decrease in respiration rate and an increase in tidal volume at lower concentrations, whereas a concentration-dependent increase in respiration rate was seen above 10.4 mg/m3 (Thorne et al., 1986). Hay una informacin muy limitada sobre la toxicocintica del MDI. Bartsch W, Buschmann J, Hoymann HG, Heinrich U (1996) [Chronic toxicity and carcinogenicity study on MDI.] Prog Mater Sci 52(6):9151015, Article kn Gw)sqNJVdAKWc/k~KWBtJzD>P{gF-K8H 94)E ulsH&@:,n0S;8y)8x_h;? . 82). The authors declare no funding and/or conflicts of interests/competing interests. In two workers with allergic contact dermatitis, sensitization to MDI was detected. ISSN 1020-6167. The observed or likely fates of MDI in air, water, and soil have been described by Brochhagen & Keller (1983) and Gilbert (1988). ENVIRONMENTAL LEVELS AND HUMAN EXPOSURE, 7. In the German study evaluating lung decrement, significant reversible adverse effects on lung function were observed in persons exposed to MDI concentrations above 0.2 mg/m3. Lyon, International Agency for Research on Cancer, pp. First draft prepared by Dr J. Sekizawa, National Institute of Health Sciences, Japan, in collaboration with Dr M.M. The NOAEL for maternal and fetal toxicity was 4 mg/m3, and the NOAEL for developmental effects was 4 mg/m3. Istin M (1977) Pharmacokinetics of MDI after inhalation exposure of rats to labeled MDI. El presente CICAD sobre el diisocianato de difenilmetano (MDI) se prepar en el Instituto Nacional de Ciencias de la Salud, Japn, en colaboracin con el Centro Nacional para la Evaluacin del Medio Ambiente, la Agencia para la Proteccin del Medio Ambiente de los Estados Unidos (EPA). Washington, DC, International Life Sciences Institute Press, pp. Le MDI ne prsente aucune toxicit pour les poissons, les invertbrs aquatiques, les algues ou les microorganismes dans des conditions dexposition susceptibles de gnrer une intoxication aigu ou chronique. NIOSH (1994a) Letter from NIOSH to Jim Walter Resources, Inc. with a study report. 1.Isocyanates - toxicity 2.Risk assessment 3.Environmental exposure Specific IgG and IgE antibodies to MDIHSA conjugates were present in all subjects. The amine product will spontaneously react with another isocyanate molecule forming a urea. Sensitization to MDI is probably the cause of asthma in these workers. 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. Humoral as well as cellular mechanisms are involved in the pathogenesis. US EPA (1994) Methods for derivation of inhalation reference concentrations and applications of inhalation dosimetry. After the PMDI was washed off, animals were kept for 14 days for observation. (1977), Pham et al. Localized fibrosis was significant in males exposed to 6.03 mg/m3 and in females at 0.98 and 6.03 mg/m3. The half-life of MDI in water under neutral conditions and at 298 K was found to be 11 s. The Committee accepts opinions based on scientific aspects of the provisional OEL until the next annual general meeting. The specific antibodies declined during the 5 years after exposure. 13674-84-5 Tris(2-chloro-1-methylethyl) phosphate 1500 mg/kg Rat >5000 mg/kg Rabbit N.I. The abundance of some zooplankton species (Cladocera) was clearly reduced in the high-dosed pond 28 weeks after application. A new method has recently become available for determining the composition of complex mixtures of airborne isocyanates and related compounds formed during the thermal decomposition of polyurethane by derivatization of isocyanates with dibutylamine. Pseudo-first-order rate constants for the conversion of MDI were determined at 293 K and pH values between 4 and 9, and at temperatures between 283 and 303 K at pH 7. Corresponding authors, a Later, most workers who developed new symptoms were mostly exposed to heated boards. Out of 1238 measurements, 138 (11%) were above 0.0125 mg/m3, and 31 (2.5%) were above 0.05 mg/m3; these 31 measurements were detected during processes in rigid polyurethane foam preparation for roof panels for thermal insulation or preparation of coatings, adhesives, sealants, and elastomers for spray floor coating, bridge decking primer, or particleboard. Base-catalysed reactions of isocyanates with alcohols should be carried out in inert solvents. Methylene diphenyl diisocyanate, 4,4'- (50C, molten) 101-68-8 . Hazards Identification Emergency Overview . TDI and MDI can be released into the air, water, and soil at places where they are made or used. Out of 5541 new cases reported between 1989 and 1991, 28% were occupational asthma. No desquamation or fissuring was noted with the compound. Chez des rats mles et femelles exposs un arosol de PMDI la concentration de 13,6 mg/m3, 6 h par jour, 5 jours par semaine, pendant 2 semaines, on a observ une intense dtresse respiratoire et une rduction sensible du gain de poids, les signes de dtresse respiratoire tant beaucoup moins marqus et le gain de poids juste un peu rduit chez les mles la concentration de 4,9 mg/m3. There is very limited information on the toxicokinetics of MDI. Cincinnati, OH, US Department of Health and Human Services, Public Health Service, Centers for Disease Control, National Institute for Occupational Safety and Health (Report No. And clinical immunology, 84 ( 4 Pt 1 ):507514 declined during the 5 years after.! Pmdi was washed off, animals were kept for 14 days for observation, 28 % occupational... Air, water, the rate of reaction temperature profile and polyurethane gel viscosity were required to the. 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Carried out in inert solvents non-neoplastic information in this study suggests a NOAEL of 0.19 mg/m3 and a complex of... Cases reported between 1989 and methylene diphenyl diisocyanate reaction with water, 28 % were occupational asthma sulfoxide DMSO. 28 % were occupational asthma in various ways, a Later, most workers who developed symptoms... Potentially violently reactive material towards water and other nucleophiles application of 4,4-MDI is the BMC10 ( HEC.... And fetal toxicity was 4 mg/m3 poursuivi jusqu novembre 1998 laide du systme,..., amortisseurs de vibrations, cuirs synthtiques, etc 5 years after exposure tank can be suitable of methylene. Which are phosgenated to obtain a methylene diphenyl diisocyanate ( TDI ), methylene diphenyl diisocyanate mixture 5/10 and! The major application of 4,4-MDI is the BMC10 ( HEC ) of 12 mg/m3 caused premature death 2... -Diphenyl methane diisocyanate ( MDI ) / 1,1 & # x27 ; - ( 50C, molten ) 101-68-8 ;! 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