4,4'-メチレンビス(2-クロロアニリン)

Fires involving this material can be controlled with a dry chemical, carbon dioxide or Halon extinguisher. (NTP, 1992)

Use water spray, dry powder, carbon dioxide.

Fresh air, rest.

Remove contaminated clothes. Rinse and then wash skin with water and soap.

Rinse with plenty of water (remove contact lenses if easily possible).

Rinse mouth. Refer for medical attention .

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.

(General first aid procedures)

PRECAUTIONS FOR "CARCINOGENS": Storage site should be as close as practical to lab in which carcinogens are to be used, so that only small quantities required for ... expt need to be carried. Carcinogens should be kept in only one section of cupboard, an explosion-proof refrigerator or freezer (depending on chemicophysical properties ...) that bears appropriate label. An inventory ... should be kept, showing quantity of carcinogen & date it was acquired ... Facilities for dispensing ... should be contiguous to storage area. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": A high-efficiency particulate arrestor (HEPA) or charcoal filters can be used to minimize amt of carcinogen in exhausted air ventilated safety cabinets, lab hoods, glove boxes or animal rooms ... Filter housing that is designed so that used filters can be transferred into plastic bag without contaminating maintenance staff is avail commercially. Filters should be placed in plastic bags immediately after removal ... The plastic bag should be sealed immediately ... The sealed bag should be labelled properly ... Waste liquids ... should be placed or collected in proper containers for disposal. The lid should be secured & the bottles properly labelled. Once filled, bottles should be placed in plastic bag, so that outer surface ... is not contaminated ... The plastic bag should also be sealed & labelled. ... Broken glassware ... should be decontaminated by solvent extraction, by chemical destruction, or in specially designed incinerators. /Chemical Carcinogens/

Aqueous solution of 1.0 wt % sulfamic acid-0.5 vol % surfactant will decontaminate 4,4'-methylenebis(o-chloroaniline)-contaminated surfaces to below detection limits without flammability hazards.

4,4'-methylenebis(2-chloroaniline) was amenable to biodegradation treatment in continuous flow reactors, designed for the removal of carcinogens and hazardous chemicals from water and wastewater. The ozone and activated carbon processes provided effective treatment.

SMALL SPILLS AND LEAKAGE: Should a spill occur while you are handling this chemical, FIRST REMOVE ALL SOURCES OF IGNITION, then you should dampen the solid spill material with 60-70% ethanol and transfer the dampened material to a suitable container. Use absorbent paper dampened with 60-70% ethanol to pick up any remaining material. Seal the absorbent paper, and any of your clothes, which may be contaminated, in a vapor-tight plastic bag for eventual disposal. Solvent wash all contaminated surfaces with 60-70% ethanol followed by washing with a soap and water solution. Do not reenter the contaminated area until the Safety Officer (or other responsible person) has verified that the area has been properly cleaned.

Generators of waste (equal to or greater than 100 kg/mo) containing this contaminant, EPA hazardous waste number U158, must conform with USEPA regulations in storage, transportation, treatment and disposal of waste.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

PRECAUTIONS FOR "CARCINOGENS": There is no universal method of disposal that has been proved satisfactory for all carcinogenic compounds & specific methods of chem destruction ... published have not been tested on all kinds of carcinogen-containing waste. ... summary of avail methods & recommendations ... /given/ must be treated as guide only. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": ... Incineration may be only feasible method for disposal of contaminated laboratory waste from biological expt. However, not all incinerators are suitable for this purpose. The most efficient type ... is probably the gas-fired type, in which a first-stage combustion with a less than stoichiometric air:fuel ratio is followed by a second stage with excess air. Some ... are designed to accept ... aqueous & organic-solvent solutions, otherwise it is necessary ... to absorb soln onto suitable combustible material, such as sawdust. Alternatively, chem destruction may be used, esp when small quantities ... are to be destroyed in laboratory. /Chemical Carcinogens/

For more Disposal Methods (Complete) data for 4,4'-METHYLENEBIS(2-CHLOROANILINE) (11 total), please visit the HSDB record page.

Personal protection: complete protective clothing including self-contained breathing apparatus. Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations. Do NOT let this chemical enter the environment.

SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. The completeness of the cleaning procedures should be considered before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at the end of shift, but should remain at employee's place of work for cleaning.

SRP: Local exhaust ventilation should be applied wherever there is an incidence of point source emissions or dispersion of regulated contaminants in the work area. Ventilation control of the contaminant as close to its point of generation is both the most economical and safest method to minimize personnel exposure to airborne contaminants. Ensure that the local ventilation moves the contaminant away from the worker.

PRECAUTIONS FOR "CARCINOGENS": Smoking, drinking, eating, storage of food or of food & beverage containers or utensils, & the application of cosmetics should be prohibited in any laboratory. All personnel should remove gloves, if worn, after completion of procedures in which carcinogens have been used. They should ... wash ... hands, preferably using dispensers of liq detergent, & rinse ... thoroughly. Consideration should be given to appropriate methods for cleaning the skin, depending on nature of the contaminant. No standard procedure can be recommended, but the use of organic solvents should be avoided. Safety pipettes should be used for all pipetting. /Chemical Carcinogens/

PRECAUTIONS FOR "CARCINOGENS": In animal laboratory, personnel should remove their outdoor clothes & wear protective suits (preferably disposable, one-piece & close-fitting at ankles & wrists), gloves, hair covering & overshoes. ... clothing should be changed daily but ... discarded immediately if obvious contamination occurs ... /also,/ workers should shower immediately. In chemical laboratory, gloves & gowns should always be worn ... however, gloves should not be assumed to provide full protection. Carefully fitted masks or respirators may be necessary when working with particulates or gases, & disposable plastic aprons might provide addnl protection. If gowns are of distinctive color, this is a reminder that they should not be worn outside of lab. /Chemical Carcinogens/

For more Preventive Measures (Complete) data for 4,4'-METHYLENEBIS(2-CHLOROANILINE) (15 total), please visit the HSDB record page.

Urinary concentrations of 70-1500 ug/L were found in samples from workers in one area of a 4,4'-methylenebis(2-chloroaniline) production facility(1). Between 1980 and 1983, 16.9% of 3,323 urinary samples submitted by 54 US companies contained 4,4'-methylenebis(2-chloroaniline) at concentrations >50 ug/L(1). Process workers at a polyurethane production unit were found to have up to 38 umol/mol creatinine of 4,4'-methylenebis(2-chloroaniline) in their urine at the end of the workshift(2). Smaller quantities were found in the urine of laboratory and supervisory staff, but none was detected in the urine of office and sales staff from an unrelated industry(2). At a commercial manufacturing plant that manufactures polyurethane products, the concentration of 4,4'-methylenebis(2-chloroaniline) in the urine of molders and mixers averaged 28.8 ug/L with maximum concentration of 158.9 ug/L(3). At a polyurethane elastomer factory, the mean urinary 4,4'-methylenebis(2-chloroaniline) levels for works at the beginning and end of the work shift ranged from 3.1-81.5 and 2.4-96.6 ug/g creatinine, respectively(4).

At a commercial manufacturing plant that manufactures polyurethane products, 4,4'-methylenebis(2-chloroaniline) was detected at <0.015 to 0.70 ug/filter(1). At a polyurethane elastomer factory, personal air exposure levels of 4,4'-methylenebis(2-chloroaniline) ranged from 0.2 to 8.9 ug/cu m(2).

MBOCA metabolism is influenced by phenobarbital. In vivo treatment with phenobarbital induced cytochrome P-450 enzymes which resulted in a slight increase in MBOCA hydroxylation. Rats treated with phenobarbital had a 4-8 fold increased metabolic rate for MBOCA. Phenobarbital did not, however, affect adduct formation.

In vivo treatment with P-naphthoflavone did increase the rate of MBOCA-hemoglobin adduct formation in rats treated sc with either 100 or 500 mg/kg/day.

MBOCA metabolism is NADPH-dependent. Moreover, MBOCA hydroxylation is inhibited by 2,4-dichloro-6-phenylphenoxyethylamine, an inhibitor of microsomal mixed function oxidases.

Cysteine and glutathione inhibit invivo hemoglobin adduct formation by N-hydroxy-MBOCA and mononitroso-MBOCA. The most recent findings suggest that binding of N-hydroxy-MBOCA to DNA in rat tissues can be inhibited by ascorbic acid, glutathione, nitrosobenzene, and methyl viologen but not by nitromethane, p-nitrobenzylpyridine, or methionine.

Cancer, Hepatic (Liver), Renal (Urinary System or Kidneys)

Liver, blood, kidneys

TERRESTRIAL FATE: Based on a classification scheme(1), an estimated Koc value of 5700(SRC), determined from a structure estimation method(2), indicates that 4,4'-methylenebis(2-chloroaniline) is expected to be immobile in soil(SRC). Volatilization of 4,4'-methylenebis(2-chloroaniline) from moist soil surfaces is not expected to be an important fate process(SRC) given an estimated Henry's Law constant of 1.1X10-11 atm-cu m/mole(SRC), using a fragment constant estimation method(3). 4,4'-Methylenebis(2-chloroaniline) is not expected to volatilize from dry soil surfaces(SRC) based upon an estimated vapor pressure of 3.9X10-6 mm Hg at 25 °C(SRC), determined from a fragment constant method(4). A 0% of theoretical BOD using activated sludge in the Japanese MITI test(5) suggests that biodegradation is not an important environmental fate process in soil(SRC).

AQUATIC FATE: Based on a classification scheme(1), an estimated Koc value of 5700(SRC), determined from a structure estimation method(2), indicates that 4,4'-methylenebis(2-chloroaniline) is expected to adsorb to suspended solids and sediment(SRC). Volatilization from water surfaces is not expected(3) based upon an estimated Henry's Law constant of 1.1X10-11 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). According to a classification scheme(5), BCFs of 114 to 398 in carp(6), suggest bioconcentration in aquatic organisms is high(SRC). Hydrolysis is not expected to be important for 4,4'-methylenebis(2-chloroaniline) based on a hydrolysis half-life of >800 years at pH 7 and 25 °C(7). A 0% of theoretical BOD using activated sludge in the Japanese MITI test(6) suggests that biodegradation is not an important environmental fate process in water(SRC).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 4,4'-methylenebis(2-chloroaniline), which has an estimated vapor pressure of 3.9X10-6 mm Hg at 25 °C(SRC), determined from a fragment constant method(2), will exist in both the vapor and particulate phases in the ambient atmosphere. Vapor-phase 4,4'-methylenebis(2-chloroaniline) is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be 5.0 hours(SRC), calculated from its rate constant of 7.8X10-11 cu cm/molecule-sec at 25 °C(SRC) that was derived using a structure estimation method(3). Particulate-phase 4,4'-methylenebis(2-chloroaniline) may be removed from the air by wet or dry deposition(SRC). 4,4'-Methylenebis(2-chloroaniline) contains chromophores that absorb at wavelengths >290 nm(4) and, therefore, may be susceptible to direct photolysis by sunlight(SRC).

The substance can be absorbed into the body by inhalation of dust, through the skin and by ingestion.

inhalation, skin absorption, ingestion, skin and/or eye contact

Oral (L891) ; inhalation (L891) ; dermal (L891)

MBOCA's carcinogenicity is thought to be a result of its ability to bind to DNA, hemoglobin, and serum albumin. One metabolite in particular, N-hydroxy-N,N’-diacetyl MBOCA, is known to bind nucleic acids, forming DNA adducts. Other N-oxidized MBOCA metabolites, such as n-hydroxy MBOCA and mononitroso-MBOCA, have been shown to form hemoglobin adducts. (T10, L891)

Cough. Further see Ingestion.

MAY BE ABSORBED!

Redness.

Headache. Dizziness.

hematuria (blood in the urine), cyanosis, nausea, methemoglobinemia, kidney irritation; [potential occupational carcinogen]

The following link will take the user to the National Toxicology Program (NTP) Test Agent Search Results page, which tabulates all of the "Standard Toxicology & Carcinogenesis Studies", "Developmental Studies", and "Genetic Toxicity Studies" performed with this chemical. Clicking on the "Testing Status" link will take the user to the status (i.e., in review, in progress, in preparation, on test, completed, etc.) and results of all the studies that the NTP has done on this chemical.[Available from, as of June 21, 2012: http://ntp-apps.niehs.nih.gov/ntp_tox/index.cfm?fuseaction=ntpsearch.searchresults&searchterm=101-14-4]

U158; As stipulated in 40 CFR 261.33, when 4,4'-methylenebis(2-chloroaniline), as a commercial chemical product or manufacturing chemical intermediate or an off-specification commercial chemical product or a manufacturing chemical intermediate, becomes a waste, it must be managed according to Federal and/or State hazardous waste regulations. Also defined as a hazardous waste is any residue, contaminated soil, water, or other debris resulting from the cleanup of a spill, into water or on dry land, of this waste. Generators of small quantities of this waste may qualify for partial exclusion from hazardous waste regulations (40 CFR 261.5).

Listed as a hazardous air pollutant (HAP) generally known or suspected to cause serious health problems. The Clean Air Act, as amended in 1990, directs EPA to set standards requiring major sources to sharply reduce routine emissions of toxic pollutants. EPA is required to establish and phase in specific performance based standards for all air emission sources that emit one or more of the listed pollutants. 4,4'-Methylenebis(2-chloroaniline) is included on this list.

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 10 lb or 4.54 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).

Used as a curing agent for polyurethanes and epoxy resins; [ACGIH]

Plastic Composites Manufacturing [Category: Industry]

MBOCA has been used principally as a curing agent for polyurethanes and epoxy resins, which are then used in the manufacture of specialized products, particularly integral-skin polyurethane semirigid foam (used for crash padding) and solid urethane rubber molding such as gear blanks and industrial tires. MBOCA has been added to vary the hardness, flexibility, and impact strength of these products. More than 99% of MBOCA has been reported as used to manufacture polyurethanes.

MOCA is used principally as a curing agent for polyurethane prepolymers in the manufacturing of high-performance, specialized, castable urethane rubber products. Mouldings such as industrial tyres and rollers, shock absorption pads and conveyor belting are among the wide variety of uses. A use of MOCA that is specific to Japan and the Far East is as a curing agent in roofing and wood sealing.

In the manufacture of ...gun mounts, jet engine turbine blades, radar systems, and components in home appliances.

Curing agent for polyurethane and epoxy resins. Research tool for studying carcinogens.

Commercial preparations frequently also contain 2-chloroaniline and a compound comprising three 2-chloroaniline moieties joined by methylene groups.

SOME 2-CHLORO-4-METHYLANILINE MIGHT BE PRESENT AS RESULT OF MANUFACTURE.

(1978) 2.01X10+8 G (PRINCPL CUSTMS DISTS)

(1983) 1.51X10+6 lb

More than 1.9 million lb were imported in 1989 /mainly from Japan/.

2023: 1,000,000 - <2,500,000 lb

(1977) AT LEAST 9.08X10+8 G

(1982) NOT PRODUCED COMMERCIALLY IN USA.

4,4'-Methylenebis(2-chloroaniline) is listed as a High Production Volume (HPV) chemical (65FR81686). Chemicals listed as HPV were produced in or imported into the U.S. in >1 million pounds in 1990 and/or 1994. The HPV list is based on the 1990 Inventory Update Rule. (IUR) (40 CFR part 710 subpart B; 51FR21438).

Production volumes for non-confidential chemicals reported under the Inventory Update Rule.[Table#4082]

Production volume for non-confidential chemicals reported under the 2006 Inventory Update Rule. Chemical: 4,4'-Methylenebis(2-chloroaniline). Aggregated National Production Volume: 500,000 to < 1 million lbs.

Commercial-grade MOCA was originally offered in flake form, for a short period in the 1960s; it is currently available as granules (prill), pellets (pastilles) and as a liquid mixture premixed with polyhydric alcohols (polyols). It is available at a purity of 99.7-99.8%.

Commercial preparations frequently also contain 2-chloroaniline and a compound comprising three 2-chloroaniline moieties joined by methylene groups.

Trade names: Bisamine S, Bisamine A, Cuamine M, Cuamine MT, Curalin M, Curalon M, Curene 442, Diamet Kh.

Plastics Material and Resin Manufacturing

Benzenamine, 4,4'-methylenebis[2-chloro-: ACTIVE

Not produced in the United States since 1979.

In 1993, one Tawainese and two Japanese companies manufactured 4,4'-methylenebis(2-chloroaniline).