101-77-9 Usage
Chemical Properties
Different sources of media describe the Chemical Properties of 101-77-9 differently. You can refer to the following data:
1. 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.
2. 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
Different sources of media describe the Uses of 101-77-9 differently. You can refer to the following data:
1. 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.
2. 4,4'-methylenedianiline be used as organic intermediates. Mainly used for the synthesis of polyimide and as curing agent of epoxy resin.
3. 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.
4. 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 the
preparation 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 epoxy
res ins and urethane elastomers; corrosion inhibitor; rubber additive (accelerator, antidegradant, retarder) in tires and heavy rubber
products; in adhesives and glues, laminates, paints and inks, PVC products, handbags, eyeglass frames, plastic jewelry, electric
encapsulators, surface coatings, spandex clothing, hairnets, eyelash curlers, earphones, balls, shoe soles, face masks.
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.
Definition
ChEBI: An aromatic amine that is diphenylmethane substituted at the 4-position of each benzene ring by an amino group.
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
Nonflammable
Safety Profile
Confirmed carcinogen
with experimental tumorigenic data. Human
poison by ingestion. Poison by
subcutaneous and intraperitoneal routes.
Human systemic effects by ingestion:
rigidity, jaundice, other liver changes. An eye
irritant. Mutation data reported. It is not
rapidly absorbed through the skin.
Combustible when exposed to heat or
flame. When heated to decomposition it
emits highly toxic fumes of aniline and NOx.
Potential Exposure
Used as an intermediate and as a curing
agent. Approximately 99% of the DDM produced is con-
sumed in its crude form (occasionally containing not more
than 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 are
employed in the manufacture of rigid polyurethane foams
which find application as thermal insulation. Polyisocyanates
are also used in the preparation of the semiflexible polyure-
thane foams used for automotive safety cushioning. DDM is
also used as: an epoxy hardening agent; a raw material in the
production of polyurethane elastomers; in the rubber industry
as a curative for Neoprene and as an antifrosting agent (anti-
oxidant) in footwear; a raw material in the production of
Quana nylon; and a raw material in the preparation of poly
(amide-imide) resins (used in magnet wire enamels).
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 aminelike
odor. Exposure to air and light results in polymerization and
oxidation of MDA. When heated, MDA produces toxic fumes of
aniline and nitrogen oxides.
Most MDA enters the environment when it is produced or
used to make other compounds. Forty-five percent of the
produced compound is released to deep soil, 52.6% to the air,
and 2.4% to land and water. Once in the environment, it will
be mainly present as tiny particles in the air and it is removed
from the atmosphere by dry deposition, rain, and snow
scavenging. A small amount is transformed by reaction with
hydroxyl radicals. In water, most of MDA will attach to
particles and sediments, and will eventually settle to the
bottom.
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, bioconcentration
factor values of 3.0–14 suggest that bioconcentration
is low, in addition this compound does not tend
to build up in the food chain. When released to soil, it is
expected to have slight to no mobility. Similarly, volatilization
from both moist and dry soil surfaces is not expected to be
important.
Shipping
UN2651 4,40
-Diaminodiphenyl methane, Hazard
Class: 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 understood
and has been mostly assessed from information on
structurally similar compounds. Many of the toxic properties of
MDA have been attributed to metabolic intermediates, as these
compounds are metabolically activated by N-oxidation to
metabolites, such as N-hydroxymethylenedianiline, that react
with DNA, RNA, and proteins.
Different studies suggest that both liver and thyroid are
targets for MDA toxicity in humans and animals. Liver
toxicity has been linked to impair mitochondrial function
and structure, apoptosis, and increased oxidative stress. It
may be caused by a reactive electrophile formed during
metabolism since liver has the enzymatic routes necessary for
such activation. Experimental studies indicate that biliary
epithelial cells are damaged earlier than parenchymal cells
and bile is a major route of exposure to MDA. The mechanism
of thyroid toxicity has not yet been resolved. It has
been observed that MDA exposure can induce a slight
decrease in thyroid hormones in rats, thus triggering secretion
of thyroid-stimulating hormone (TSH), which induced
thyroid hyperplasia. Some of the induced adverse effects
observed after MDA exposure (e.g., reduced food consumption,
lower body weight gain, and effects on red cells,
lymphocytes, and clotting parameters) could be explained as
secondary responses.
MDA is carcinogenic to animals. The mechanism of liver or
thyroid tumor development remains unclear. Even if cell
injury may give indications of a nongenotoxic mechanism, it
remains still unproved, and there are also positive genotoxic
data in vitro and in vivo which indicate that a genotoxic
mechanism may be related to the formation of a reactive
metabolic intermediate cannot be excluded. Regarding thyroid
cancer, hypersecretion of TSH may have a contribution to
tumor formation.
Incompatibilities
Dust forms and explosive mixture
with air. May polymerize in temperatures .125℃
. A weak
base. Incompatible with strong oxidizers (chlorates, nitrates,
peroxides, permanganates, perchlorates, chlorine, bromine,
fluorine, etc.); contact may cause fires or explosions. Keep
away from alkaline materials, strong acids. Flammable gas-
eous hydrogen may be generated in combination with strong
reducing agents, such as hydrides
.
Check Digit Verification of cas no
The CAS Registry Mumber 101-77-9 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 1 respectively; the second part has 2 digits, 7 and 7 respectively.
Calculate Digit Verification of CAS Registry Number 101-77:
(5*1)+(4*0)+(3*1)+(2*7)+(1*7)=29
29 % 10 = 9
So 101-77-9 is a valid CAS Registry Number.
101-77-9Relevant articles and documents
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Ergozhin et al.
, (1972)
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PROTODEALKYLATION OF BIS(AMINOPHENYL)METHANES
Whitman, Peter J.,Frulla, Floro F.,Temme, George H.,Stuber, Fred A.
, p. 1887 - 1890 (1986)
Contrary to earlier reports, the formation of bis(aminophenyl)methanes in the acid-catalyzed condensation of aniline and formaldehyde can result in carbon-carbon bond cleavage proceeding via an ipso protodealkylation mechanism.
Chemical behaviour of seven aromatic diisocyanates (toluenediisocyanates and diphenylmethanediisocyanates) under in vitro conditions in relationship to their results in the Salmonella/microsome test
Seel,Walber,Herbold,Kopp
, p. 109 - 123 (1999)
There are conflicting results on the mutagenicity of toluenediisocyanate (TDI) and diphenylmethanediisocyanate (MDI). It was found that the organic solvent chosen to dissolve the compounds dictates the outcome of the bacterial tests. The Salmonella/microsome tests showed uniformly mutagenic effects for all the compounds that were predissolved in DMSO. Due to the instability of aromatic diisocyanates in DMSO this solvent was replaced by ethyleneglycoldimethylether (EGDE). TDI and MDI endured the dissolving and were therefore still available for the subsequent bacterial tests. Furthermore, no aromatic diamines (TDA or MDA) could be detected in EGDE prior to the start of the assays. The Salmonella/microsome tests, however, revealed unexpected differences between TDI and MDI. As previously published the four types of MDI showed negative results, whereas the data presented in this paper demonstrated mutagenic effects of all three types of TDI if EGDE is the solvent. To gain deeper insight into the chemical changes that occurred during the Salmonella/microsome test, the possible reactions were modelled in the laboratory by mixing predissolved diisocyanates with a defined surplus of water and monitoring the progress of the chemical reactions by analytical methods. Additionally, the quality of the model was checked by exposing solutions of 2,6-TDI and 4,4'-MDI to the real biological test environment. In both cases, the reaction patterns of TDI were different to those of MDI. Within 1 min, which is the maximum time needed to mix the predissolved compounds with water before they are poured onto the agar plate, the TDI content was reduced in favour of different ureas and TDA. In addition water was replaced by the complete set of test ingredients. While the TDA content remained more or less constant, the amount of residual TDI was reduced considerably. Reactions of MDI were markedly slower than those of TDI. More than 90% of the predissolved MDI remained intact when it was mixed with water. The biological test ingredients accelerated the reduction of the MDI content. Within 45 s, more than two thirds of the MDI disappeared. Evidently, the chemical reactions continue during incubation. It is assumed that the contrasting results of TDI and MDI in the Salmonella/microsome test are due to the different reaction patterns-and reaction products-of the predissolved diisocyanates created under the specific conditions of the test. These findings indicate that the chemical interactions between reactive test compounds and solvents or test media need to be considered in the interpretation of the relevance of test results. Copyright (C) 1999 Elsevier Science B.V.
-
Conover,Tarbell
, p. 3586 (1950)
-
Towards an industrial synthesis of diamino diphenyl methane (DADPM) using novel delaminated materials: A breakthrough step in the production of isocyanates for polyurethanes
Botella,Corma,Carr, Robert H.,Mitchell, Christopher J.
, p. 143 - 149 (2011)
Delaminated materials ITQ-2, ITQ-6 and ITQ-18 are very efficient catalysts of zeolitic nature for the synthesis of diamino diphenyl methane (DADPM), the polyamine precursor in the production of MDI for polyurethanes. The exfoliation process results in excellent accessibility of their active sites to reactant molecules as well as fast desorption of products. These catalysts present higher activity and slower rates of deactivation than their corresponding zeolites. Moreover, the topology of the delaminated structure imposes a precise control of the isomer distribution, offering an additional flexibility in the synthesis of DADPM. By optimizing the process conditions it is possible to achieve final DADPM crude under industrial production specifications with ITQ-18. This catalyst represents a real chance for replacing HCl in the industrial production of DADPM.
Lewis acid solid catalysts for the synthesis of methylenedianiline from aniline and formaldehyde
Cheung, Ka Yan,De Baerdemaeker, Trees,De Vos, Dirk,Gordillo, Alvaro,Marquez, Carlos,Parvulescu, Andrei-Nicolae,Tomkins, Patrick
, p. 114 - 123 (2021)
A catalyst containing Hf4+ and Zn2+ supported on silica has been found to be highly effective for the synthesis of methylenedianiline (MDA), an indispensable precursor in the polyurethane industry. Its performance was further improved when the silica support was replaced by silica-alumina, which resulted in a catalyst that was both active and selective, as indicated by the high MDA yield and high 4,4′–MDA/(2,2′–MDA + 2,4′–MDA) isomer ratio obtained. Furthermore, the catalyst also gave an appreciable oligomeric MDA (OMDA) yield and was noticeably more stable than the zeolites that were used in comparative tests: it could be used in at least five consecutive runs without any significant loss in activity. The combination of Br?nsted and Lewis acidity strongly increases the overall activity and yields a catalyst that represents a remarkably stable and reusable alternative to the commonly studied systems for this reaction.
METHOD OF PRODUCING DIAMINES AND POLYAMINES OF THE DIPHENYLMETHANE SERIES
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Paragraph 0136-0167, (2020/05/02)
The invention relates to a method for producing diamines and polyamines of the diphenylmethane series, by condensing aniline and formaldehyde followed by an acid-catalysed rearrangement at different production capacities with alteration of the content of diamines of the diphenylmethane series (altering the binuclear content). Adapting the molar ratio of the total used aniline to the total used formaldehyde and adapting the reaction temperature allows the rearrangement reaction to be fully completed despite the change in dwell time inevitably associated with a change in production capacity, and allows the formation of undesired by-products to be avoided as far as possible; the intended modification to binuclear content is likewise achieved.
Method for synthesizing 4, 4'-MDA by means of aniline
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Paragraph 0008-0029, (2018/05/16)
The invention discloses a method for synthesizing 4, 4'-MDA by means of aniline. ZrOCl 8HO, Ce(NO) 6HO, nickel nitrate, aniline and formaldehyde are used as main raw materials, the Bronsted-Lewis double-acid functionalized catalyst prepared by means of ZrOCl 8HO and Ce(NO) 6HO has Bronsted acid and Lewis acid sites at the same time, and the feature of double acidity is fused; according to the used raw materials, the mass ratio of aniline to formaldehyde is 6: 1, the mass ratio of N-methylimidazole to ZrOCl 8HO to Ce(NO) 6HO is 2: 3, and the mass ratio of composite oxide to nickel nitrate is 1: 1. According to the 4, 4'-MDA synthesis process, operation is easy, the cost of the catalyst is low, and the applicability is high; compared with traditional solidand liquid acid catalysts, the catalyst has larger development potential and application value, and has an excellent catalytic effect on the MDA synthesis reaction.
