4,4'-Methylenedianiline CAS 101-77-9
Introduction：Basic information about 4,4'-Methylenedianiline CAS 101-77-9, including its chemical name, molecular formula, synonyms, physicochemical properties, and safety information, etc.
4,4'-Methylenedianiline Basic informationChemical Properties Uses Preparation
| Product Name: | 4,4'-Methylenedianiline |
| Synonyms: | Bis-(4-aMino;methylenebis(aniline);MDA;DIANILINOMETHANE;Di-(4-aminophenyl)methane;DADPM;bis(p-aminophenyl)methane;BIS-(4-AMINOPHENYL)METHANE |
| CAS: | 101-77-9 |
| MF: | C13H14N2 |
| MW: | 198.26 |
| EINECS: | 202-974-4 |
| Product Categories: | Diphenylmethanes (for High-Performance Polymer Research);Functional Materials;Reagent for High-Performance Polymer Research;Aromatic Hydrocarbons (substituted) & Derivatives;Industrial/Fine Chemicals |
| Mol File: | 101-77-9.mol |
4,4'-Methylenedianiline Chemical Properties
| Melting point | 89-91 °C(lit.) |
| Boiling point | 242 °C2 mm Hg(lit.) |
| density | 1.15 |
| vapor pressure | 0Pa at 25℃ |
| refractive index | 1.5014 (estimate) |
| Fp | 430 °F |
| solubility | water: soluble |
| pka | 5.32±0.25(Predicted) |
| color | White to Light yellow |
| Water Solubility | Slightly soluble. <0.1 g/100 mL at 19 ºC |
| Merck | 14,2980 |
| BRN | 474706 |
| Exposure limits | ACGIH: TWA 0.1 ppm (Skin) OSHA: STEL 100 ppb |
| InChI | 1S/C13H14N2/c14-12-5-1-10(2-6-12)9-11-3-7-13(15)8-4-11/h1-8H,9,14-15H2 |
| InChIKey | YBRVSVVVWCFQMG-UHFFFAOYSA-N |
| SMILES | Nc1ccc(Cc2ccc(N)cc2)cc1 |
| LogP | 1.55 at 25℃ |
| CAS DataBase Reference | 101-77-9(CAS DataBase Reference) |
| IARC | 2B (Vol. 39, Sup 7) 1987 |
| NIST Chemistry Reference | Benzenamine, 4,4'-methylenebis-(101-77-9) |
| EPA Substance Registry System | 4,4'-Methylenedianiline (101-77-9) |
Safety Information
| Hazard Codes | T,N |
| Risk Statements | 45-39/23/24/25-43-48/20/21/22-51/53-68 |
| Safety Statements | 53-45-61 |
| RIDADR | UN 2651 6.1/PG 3 |
| WGK Germany | 3 |
| RTECS | BY5425000 |
| TSCA | TSCA listed |
| HazardClass | 6.1 |
| PackingGroup | III |
| HS Code | 29215900 |
| Storage Class | 6.1C - Combustible acute toxic Cat.3 toxic compounds or compounds which causing chronic effects |
| Hazard Classifications | Acute Tox. 3 Oral Aquatic Acute 1 Aquatic Chronic 2 Carc. 1B Muta. 2 Skin Sens. 1 STOT RE 2 STOT SE 1 |
| Hazardous Substances Data | 101-77-9(Hazardous Substances Data) |
| Toxicity | LD50 oral in rabbit: 620mg/kg |
| Chemical Properties | 4,4'-Methylenedianiline is a light brown crystalline solid with a faint amine odor. lt is very slightly soluble in water and soluble in alcohol, benzene,and ether. lt is combustible when exposed to heat or flame. When heated to decomposition，it emits toxic fumes of aniline and nitrogen oxides (NOx). The dihydrochloride is a crystalline solid that is soluble in water. 4,4'-Methylenedianiline is primarily used to produce 4,4-'methylenedianiline diisocyanate and other polymeric isocyanates which are used to manufacture polyurethane foams. |
| Uses | 4,4'-Methylenedianiline is used in the production of polyurethane foams and epoxy resins. Potential contributor in pulmonary arterial hypertension (PAH) in rats through alteration of the serotenergic transport system. Drinking water contaminant candidate list 3 (CCL 3) compound as per United States Environmental Protection Agency (EPA), environmental, and food contaminants. Dyes and metabolites, Environmental Testing. |
| Preparation | 93 g (1 mole) of aniline are dissolved in 96 % alcohol and to the cooled solution with proper stirring 120 g (1 mole) of 40 % formaldehyde solution are gradually added. After the addition is completed a second molecular portion of aniline, 93 g (1 mole) of aniline are added and the reaction is continued until the odor of formaldehyde has disappeared. The complete the reaction the mixture is refluxed for 2 hours. 130 g (1 mole) of aniline hydrochloride are then added, and boiling continued for a further 12 hours. The alcohol is distilled off, the residue made alkaline with the solution of sodium hydroxide and the excess of aniline removed by distillation with superheated steam. The residual oil, which consists of 4,4′-diaminodiphenylmethane, is then purified by solution in dilute hydrochloric acid and reprecipitation with dilute alkali. The 4,4′-diaminodiphenylmethane base is filtered off, washed and dried. Organic medical chemicals, by M. Barrowliff, 188-189, 1921 |
| Description | 4,4'-Methylenedianiline is an industrial chemical that is not known to occur naturally. It is also commonly known as diaminodiphenylmethane or MDA. It occurs as a colorless to pale yellow solid and has a faint odor. 4,4'-Methylenedianiline is used mainly for making polyurethane foams, which have a variety of uses, such as insulating materials in mailing containers. It is also used for making coating materials, glues, Spandex? fiber, dyes, and rubber. 4,4'-Methylenedianiline is also a by-product of azo dyes. It is also possibly formed by hydrolysis of diphenylmethane-4A'-diisocyanate. |
| Chemical Properties | 4,4-Diaminodiphenylmethane is a pale yellow crystalline solid (turns light brown on contact with air) with a faint amine-like odor that is unstable in the presence of light or air and emits toxic fumes of aniline and nitrogen oxides when heated to decomposition. 4,4'-Methylenedianiline is primarily used in industry as a chemical intermediate in the production of 4,4-methylenedianiline diisocyanates and polyisocyanates, but is also used as a cross-linking agent for the determination of tungsten and sulfates, and as a corrosion inhibitor. Exposure to this substance irritates the skin and eyes and causes liver damage. 4,4'-Methylenedianiline is reasonably anticipated to be a human carcinogen. (NCI05) |
| Uses | 4,4'-methylenedianiline be used as organic intermediates. Mainly used for the synthesis of polyimide and as curing agent of epoxy resin. |
| Uses | As chemical intermediate in production of isocyanates and polyisocyantes for preparation of polyurethane foams, Spandex fibers; as curing agent for epoxy resins and urethane elastomers; in production of polyamides; in the determination of tungsten and sulfates; in preparation of azo dyes; as corrosion inhibitor. |
| Uses | 4,4'-Diaminodiphenyl-methane is used in the determination of tungsten and sulfates; in the preparation of azo dyes; cross-linking agent for epoxy resins; in thepreparation of isocyanates and polyisocyanates; in the rubber industry as a curative for neoprene, as an anti-frosting agent (antioxidant)in footwear; raw material in preparation of poly(amide-imide) resins (used in magnet-wire enamels); curing agent for epoxyres ins and urethane elastomers; corrosion inhibitor; rubber additive (accelerator, antidegradant, retarder) in tires and heavy rubberproducts; in adhesives and glues, laminates, paints and inks, PVC products, handbags, eyeglass frames, plastic jewelry, electricencapsulators, surface coatings, spandex clothing, hairnets, eyelash curlers, earphones, balls, shoe soles, face masks. |
| Definition | ChEBI: 4,4'-Methylenedianiline is an aromatic amine that is diphenylmethane substituted at the 4-position of each benzene ring by an amino group. It is primarily used in industry as a chemical intermediate in the production of 4,4-methylenedianiline diisocyanates and polyisocyanates.? |
| General Description | A tan flake or lump solid with a faint fishlike odor. May be toxic by inhalation or ingestion, and may be irritating to skin. Insoluble in water. |
| Air & Water Reactions | Oxidizes slowly in air in a reaction catalyzed by light. Somewhat hygroscopic. Insoluble in water. |
| Reactivity Profile | 4,4'-Methylenedianiline polymerizes if heated above 257° F. Incompatible with strong oxidizing agents. 4,4'-Methylenedianiline is also incompatible with acids. Catalyzes isocyanate-alcohol and epoxide reactions. Flammable gaseous hydrogen may be generated in combination with strong reducing agents, such as hydrides. |
| Health Hazard | TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution. |
| Fire Hazard | Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form. |
| Flammability and Explosibility | Non flammable |
| Safety Profile | Confirmed carcinogenwith experimental tumorigenic data. Humanpoison by ingestion. Poison bysubcutaneous and intraperitoneal routes.Human systemic effects by ingestion:rigidity, jaundice, other liver changes. An eyeirritant. Mutation data reported. It is notrapidly absorbed through the skin.Combustible when exposed to heat orflame. When heated to decomposition itemits highly toxic fumes of aniline and NOx. |
| Potential Exposure | Used as an intermediate and as a curingagent. Approximately 99% of the DDM produced is con-sumed in its crude form (occasionally containing not morethan 50% DDM and ply-DDM) at its production site by reac-tion with phosgene in the preparation of isocyanates and poly-isocyanates. These isocyanates and polyisocyanates areemployed in the manufacture of rigid polyurethane foamswhich find application as thermal insulation. Polyisocyanatesare also used in the preparation of the semiflexible polyure-thane foams used for automotive safety cushioning. DDM isalso used as: an epoxy hardening agent; a raw material in theproduction of polyurethane elastomers; in the rubber industryas a curative for Neoprene and as an antifrosting agent (anti-oxidant) in footwear; a raw material in the production ofQuana nylon; and a raw material in the preparation of poly(amide-imide) resins (used in magnet wire enamels). |
| First aid | If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seekmedical attention immediately. If this chemical contactsthe skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove fromexposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing hasstopped and CPR if heart action has stopped. Transferpromptly to a medical facility. When this chemical hasbeen swallowed, get medical attention. Give large quantities of water and induce vomiting. Do not make an unconscious person vomit. |
| Carcinogenicity | 4,4′-Methylenedianiline and its dihydrochloride salt are reasonably anticipated to be human carcinogens based on sufficient evidence of carcinogenicity from studies in experimental animals. |
| Environmental Fate | MDA is a pale brown crystalline powder with a faint aminelikeodor. Exposure to air and light results in polymerization andoxidation of MDA. When heated, MDA produces toxic fumes ofaniline and nitrogen oxides. Most MDA enters the environment when it is produced orused to make other compounds. Forty-five percent of theproduced compound is released to deep soil, 52.6% to the air,and 2.4% to land and water. Once in the environment, it willbe mainly present as tiny particles in the air and it is removedfrom the atmosphere by dry deposition, rain, and snowscavenging. A small amount is transformed by reaction withhydroxyl radicals. In water, most of MDA will attach toparticles and sediments, and will eventually settle to thebottom. The estimated half-life of biodegradation in surface water,groundwater, and soil is 1–7 days, 2–14 days, and 1–7 days,respectively. With respect to aquatic ecosystems, bioconcentrationfactor values of 3.0–14 suggest that bioconcentrationis low, in addition this compound does not tendto build up in the food chain. When released to soil, it isexpected to have slight to no mobility. Similarly, volatilizationfrom both moist and dry soil surfaces is not expected to beimportant. |
| storage | Color Code—Blue: Health Hazard/Poison: Storein a secure poison location. Prior to working with thischemical you should be trained on its proper handling andstorage. Store in tightly closed containers in a cool, wellventilated area away from strong oxidizers (such as chlorine, bromine, and fluorine). A regulated, marked areashould be established where this chemical is handled, used,or stored in compliance with OSHA Standard 1910.1045. |
| Shipping | UN2651 4,40-Diaminodiphenyl methane, HazardClass: 6.1; Labels: 6.1-Poisonous materials. |
| Purification Methods | Crystallise the amine from water, 95% EtOH or *benzene. [Beilstein 13 IV 390.] |
| Toxicity evaluation | Currently, the mechanism of action is not completely understoodand has been mostly assessed from information onstructurally similar compounds. Many of the toxic properties ofMDA have been attributed to metabolic intermediates, as thesecompounds are metabolically activated by N-oxidation tometabolites, such as N-hydroxymethylenedianiline, that reactwith DNA, RNA, and proteins. Different studies suggest that both liver and thyroid aretargets for MDA toxicity in humans and animals. Livertoxicity has been linked to impair mitochondrial functionand structure, apoptosis, and increased oxidative stress. Itmay be caused by a reactive electrophile formed duringmetabolism since liver has the enzymatic routes necessary forsuch activation. Experimental studies indicate that biliaryepithelial cells are damaged earlier than parenchymal cellsand bile is a major route of exposure to MDA. The mechanismof thyroid toxicity has not yet been resolved. It hasbeen observed that MDA exposure can induce a slightdecrease in thyroid hormones in rats, thus triggering secretionof thyroid-stimulating hormone (TSH), which inducedthyroid hyperplasia. Some of the induced adverse effectsobserved after MDA exposure (e.g., reduced food consumption,lower body weight gain, and effects on red cells,lymphocytes, and clotting parameters) could be explained assecondary responses. MDA is carcinogenic to animals. The mechanism of liver orthyroid tumor development remains unclear. Even if cellinjury may give indications of a nongenotoxic mechanism, itremains still unproved, and there are also positive genotoxicdata in vitro and in vivo which indicate that a genotoxicmechanism may be related to the formation of a reactivemetabolic intermediate cannot be excluded. Regarding thyroidcancer, hypersecretion of TSH may have a contribution totumor formation. |
| Incompatibilities | Dust forms and explosive mixturewith air. May polymerize in temperatures .125℃ . A weakbase. Incompatible with strong oxidizers (chlorates, nitrates,peroxides, permanganates, perchlorates, chlorine, bromine,fluorine, etc.); contact may cause fires or explosions. Keepaway from alkaline materials, strong acids. Flammable gas-eous hydrogen may be generated in combination with strongreducing agents, such as hydrides. |
| Toxics Screening Level | The initial risk screening level (IRSL) for 4,4’-methylenedianiline (CAS # 101-77-9) is 0.022μg/m3 annual averaging time and the secondary risk screening level (SRSL) is 0.22 μg/m3annual averaging time. |
| Waste Disposal | Controlled incineration(oxides of nitrogen are removed from the effluent gas byscrubbers and/or thermal devices). |
4,4'-Methylenedianiline Preparation Products And Raw materials
| Raw materials | Sodium hydroxide-->Hydrochloric acid-->Formaldehyde-->Aniline-->Calcium carbonate-->Styrene-->Benzenesulfonic acid |
| Preparation Products | photosensitive polyimide/SiO2 hybrid mate materials-->Flunarizine dihydrochloride-->2,2'-methylenedianiline-->alpha-(4-aminocyclohexyl)-ptoluidine-->DIPHENYLMETHANE-4,4'-DICARBOXYLIC ACID-->2,4'-DIAMINODIPHENYLMETHANE-->4,4'-Methylenebis(N,N-diglycidylaniline)-->Basic Red 9-->Acid Blue 127:1 |
