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Aniline Derivatives · CAS 101-77-9

4,4′-Methylenedianiline (MDA) supplier and exporter

4,4′-Diaminodiphenylmethane · DDM · DAPM · Flakes and molten supply

4,4′-Methylenedianiline is an aromatic diamine: two aniline rings joined by a methylene bridge, each carrying a primary amino group in the para position. Four reactive N–H hydrogens on a rigid aromatic backbone make it both the principal precursor to MDI and a high-performance epoxy curing agent that gives glass transition temperatures aliphatic hardeners cannot reach. It is also a substance of very high concern — a category 1B carcinogen, on the REACH Authorisation List — and is supplied only to users with the containment and controls the material requires. Chelora Amines supplies MDA in flake and molten form, with a batch-wise COA and SDS on every dispatch.

Molecular formulaC₁₃H₁₄N₂
Molecular weight198.26 g/mol
Physical stateFlakes / molten solid
Usual technical grade≥ 99.0% 4,4′-isomer
Flake, pastille and molten supply Batch-wise COA with every dispatch Supplied against regulatory and end-use checks
H₂N–C₆H₄–CH₂–C₆H₄–NH₂ CAS 101-77-9 N N C C C C C C C C C C C C C H₂N– –NH₂ 4,4′ — both para methylene bridge rigid backbone, four reactive N–H hydrogens
  • C₁₃ Twelve aromatic carbons in two rings plus one bridging carbon 13 × 12.011
  • H₁₄ Eight ring hydrogens, two on the bridge, four on the amino groups 14 × 1.008
  • N₂ Two primary nitrogens, para to the bridge — four active hydrogens for cure 2 × 14.01

156.14 + 14.11 + 28.01 = 198.26 g/mol

4,4′-Diaminodiphenylmethane, (H₂N–C₆H₄)₂CH₂ — a primary aromatic diamine The single –CH₂– bridge gives just enough rotational freedom for the molecule to pack into a network, while the two aromatic rings keep that network stiff — which is why MDA-cured epoxies reach high glass transition temperatures. Four N–H hydrogens across two primary amines give an amine hydrogen equivalent weight of about 49.6. Hydrogens on ring carbons are omitted from the drawing for clarity.
101-77-9CAS number
2921 59HS / HSN tariff code
≥ 99.0%4,4′-isomer, technical grade
UN 2811Class 6.1, PG III
Annex XIVREACH authorisation list
24 hrsTypical quote response
What it is

4,4′-Methylenedianiline at a glance

4,4′-Methylenedianiline — also called 4,4′-diaminodiphenylmethane, DDM or DAPM — is a primary aromatic diamine formed by joining two aniline molecules through a methylene bridge. The amino groups sit in the para position on each ring, which is what the "4,4′" denotes and what gives the molecule its symmetry. It is a light brown to tan solid supplied as flakes, pastilles or lumps, melting at about 90 °C and handled molten by most large consumers.

Two things define it commercially. First, it is the gateway to MDI: condensing aniline with formaldehyde gives MDA and its oligomers, and converting those amine groups to isocyanate groups gives MDI and polymeric MDI — the basis of rigid polyurethane insulation foam, binders and adhesives. Second, as an isolated pure isomer it is a high-performance epoxy curing agent, delivering glass transition temperatures, chemical resistance and electrical properties that aliphatic and cycloaliphatic hardeners cannot match.

MDA carries a serious health classification. It is a category 1B carcinogen, a suspected mutagen, a skin sensitiser and a known liver toxicant, and it is listed on the REACH Candidate List and Authorisation List. It is supplied here for industrial and professional use under closed handling, with end-use and regulatory checks before an order is accepted.

Why formulators choose MDA

  • High glass transition temperature. MDA-cured bisphenol-A epoxies routinely reach a Tg well above 150 °C, which is why the system persists in aerospace and electrical laminates.
  • Four active hydrogens. An AHEW of about 49.6 means a low mix ratio by weight and a dense crosslink network.
  • Rigid aromatic backbone. Thermal, chemical and solvent resistance that flexible aliphatic amines do not provide.
  • The MDI chain. As an intermediate, MDA is the single largest-volume aromatic diamine in the world because of the polyurethane industry that sits downstream of it.
Identification and physical properties
Chemical name4,4′-Methylenedianiline
Common synonymsMDA, DDM, DAPM, 4,4′-diaminodiphenylmethane, bis(4-aminophenyl)methane, methylenedianiline
CAS number101-77-9
EC / EINECS number202-974-4
HS / HSN code2921 59 (other aromatic polyamines; HSN 2921 59 on Indian invoices)
Molecular formulaC₁₃H₁₄N₂ ((H₂NC₆H₄)₂CH₂)
Molecular weight198.26 g/mol
AppearanceLight brown to tan flakes, pastilles or lumps; pale yellow liquid when molten
OdourFaint amine-like odour
Melting pointAbout 90–92 °C
Boiling pointAbout 398 °C at atmospheric pressure
DensityAbout 1.06 g/cm³
Solubility in waterAbout 1 g/L at 20 °C — slightly soluble; soluble in alcohols, acetone and most polar organics
Amine valueAbout 560–570 mg KOH/g
Amine hydrogen equivalent weightAbout 49.6 (four active hydrogens per molecule)
Flash pointAbout 221 °C (closed cup)
UN numberUN 2811, Toxic solid, organic, n.o.s. (4,4′-methylenedianiline), Class 6.1, Packing Group III
Regulatory statusCLP Carc. 1B; REACH Candidate List (SVHC) and Annex XIV authorisation list

Figures are typical values for the technical grade. High-purity and laboratory grade values may differ. All values for the material you order are stated on its Certificate of Analysis and Safety Data Sheet.

Chemistry and reactivity

How MDA behaves in a formulation or reaction

Two primary aromatic amines on a rigid backbone. Every amine reaction is available twice over, which is what turns MDA from a reagent into a network former.

Epoxy curing

Each N–H adds across an epoxide ring, so one MDA molecule ties four epoxy chains together. The aromatic backbone keeps the resulting network stiff, giving a high glass transition temperature and strong chemical resistance.

AHEW ≈ 49.6 · 4 active H

Conversion to MDI

Converting the two amino groups to isocyanate groups gives MDI and, from the oligomeric MDA fraction, polymeric MDI — by volume the overwhelming industrial outlet for this chemistry.

MDA → MDI (–NH₂ → –NCO)

Polyimide formation

Reaction with aromatic dianhydrides gives poly(amic acid), which is cyclised thermally to a polyimide — the chemistry behind high-temperature films, wire enamels and composite matrices.

MDA + dianhydride → polyimide

Polyurethane chain extension

Used as an aromatic diamine chain extender in polyurethane and polyurea prepolymer systems, giving hard segments with high modulus and heat resistance.

prepolymer–NCO + H₂N–R → urea

Amide and polyamide formation

Condensation with dicarboxylic acids or their chlorides gives aromatic polyamides and polyamide-imides used where thermal stability is the design requirement.

H₂N–R–NH₂ + diacid → polyamide

Ring hydrogenation

Hydrogenating both aromatic rings gives 4,4′-methylenebis(cyclohexylamine), the cycloaliphatic curing agent used where UV stability and low colour matter.

MDA + 6 H₂ → PACM

Diazotisation

Both amino groups diazotise and couple, giving bis-azo dyes and pigment intermediates — a smaller but long-established outlet.

2 × ArNH₂ → bis-diazonium

Salt and complex formation

Reacts with mineral and organic acids to give water-soluble salts, used in some analytical and process applications and as a route to handling MDA in solution.

MDA + 2 HCl → dihydrochloride

Handling note — read before ordering. MDA is a category 1B carcinogen and a liver toxicant, absorbed through skin as well as inhaled as dust or vapour. It should be charged in a closed system or from a melt, never as loose dust in an open workshop. Molten handling lines must be traced above about 100 °C, and both flake and molten material darken on exposure to air and light. Do not accept an MDA process design that relies on operator PPE alone — engineering containment comes first.

Discuss your process
How it is made

From aniline to a finished bag

MDA is made by the acid-catalysed condensation of aniline with formaldehyde. The reaction gives a mixture of isomers and higher oligomers; whether that mixture is separated or kept intact depends on whether the destination is an epoxy hardener or an MDI plant.

Stage 1

Feedstock

Excess aniline and aqueous formaldehyde are specified, with aniline quality controlling the colour of the finished product.

Stage 2

Condensation

Aniline and formaldehyde combine under acid catalysis to give an intermediate that rearranges to the diaminodiphenylmethane skeleton.

Stage 3

Neutralisation

The acid catalyst is neutralised and the organic phase separated and washed, with excess aniline recovered and recycled.

Stage 4

Isomer separation

Vacuum distillation and crystallisation isolate the 4,4′-isomer from the 2,4′ and 2,2′ isomers and the higher oligomers, giving purity above 99%.

Stage 5

Flaking and filling

Molten product is flaked or pastillated under nitrogen and bagged in a contained plant, or loaded hot into heated tankers for molten delivery.

Pure 4,4′-isomer versus polymeric MDA

Isolated 4,4′-MDA at 99% and above is what an epoxy, polyimide or polyurea formulator needs: a defined molecular weight, a known amine hydrogen equivalent weight and a predictable cure. Polymeric MDA — the uncut reaction mixture containing the 2,4′ isomer and a tail of three-ring and four-ring oligomers — is not a formulation product at all; it goes straight into MDI manufacture, where the oligomer distribution determines the functionality of the resulting polymeric MDI. If you are formulating rather than converting, specify the 4,4′-isomer content and the 2,4′ limit explicitly, because the isomer ratio shifts both the mix ratio and the cure profile.

Colour, oxidation and storage

MDA darkens steadily on exposure to air and light, moving from light tan towards brown. The change is a surface oxidation and does not affect amine value in any meaningful way, but it carries into the colour of cured epoxy systems, so colour-sensitive users should specify a Gardner limit and order against their draw-down. In sealed, opaque packaging stored cool and dry, flake MDA normally holds specification for twenty-four months from manufacture. Molten storage should be nitrogen-blanketed and not held hot for extended periods — prolonged hot storage both darkens the product and increases vapour exposure risk.

Grades and specification

Grades matched to your process

The right grade depends on whether you are formulating with a defined diamine or converting a mixture. Isomer purity, amine value and colour are the three parameters that decide it.

≥99.0%

High-purity 4,4′ grade

Isolated 4,4′-isomer in flake or pastille form for epoxy curing agents, polyimides, polyureas and specialty synthesis.

2,4′-isomer
Tightly limited
Packs
Bags, drums
Molten

Bulk molten grade

Same specification, delivered hot in heated road or ISO tankers for continuous consumers with contained melt receipt.

Delivery temp.
Above 100 °C
Blanket
Nitrogen
LR / AR

Laboratory grades

Highest purity for analytical, research and reference use, supplied in small sealed packs with full batch documentation.

Packs
100 g to 1 kg
Docs
Full batch COA
Typical specification — 4,4′-Methylenedianiline, high-purity grade
ParameterTest methodTypical specification
AppearanceVisualLight brown to tan flakes or pastilles
Purity, 4,4′-isomerGC≥ 99.0% w/w
2,4′-isomerGC≤ 0.8% w/w
Free anilineGC≤ 0.1% w/w
Melting rangeCapillary89 – 92 °C
Amine valuePotentiometric titration560 – 570 mg KOH/g
Colour, molten (Gardner)Gardner≤ 8
MoistureKarl Fischer≤ 0.2% w/w
AshGravimetric≤ 0.05% w/w

Indicative specification for planning. The controlling document is the Certificate of Analysis issued for your batch. If your process needs a tighter isomer or colour limit, say so at enquiry stage.

Applications

Where MDA is used

Two quite different worlds use MDA: the bulk polyurethane chain that converts it onwards into MDI, and the high-performance resin world that uses the pure isomer as a curing agent.

MDI and polymeric MDI

The dominant outlet by volume. MDA and its oligomers are converted to MDI, which goes into rigid insulation foam, wood binders, flexible foam, adhesives and elastomers.

Epoxy curing agent

The classical high-Tg hardener for filament-wound pressure vessels, aerospace and tooling laminates, electrical laminates and chemically resistant linings.

Polyimide and polyamide-imide resins

Condensed with aromatic dianhydrides to give polyimides used as magnet wire enamel, high-temperature films, adhesives and composite matrices.

Polyurethane and polyurea

An aromatic chain extender and curative for prepolymer systems, producing hard segments with high modulus, heat resistance and dynamic performance.

Composites and advanced materials

Used where a cured matrix must hold its properties above 150 °C — aerospace structures, pressure vessels, high-temperature tooling and electrical insulation.

Corrosion inhibitors and rubber chemicals

An intermediate for aromatic Schiff bases, inhibitor packages and a small number of rubber processing chemicals.

Dye and pigment intermediates

Bis-diazotisation and coupling give bis-azo dyes and pigment intermediates — a long-established if smaller outlet.

Research and reference use

A standard aromatic diamine in polymer chemistry research, cure kinetics studies and as an analytical reference material under laboratory containment.

Downstream chemistry

What gets made from MDA

From roof insulation panels to aerospace laminates — the value chain downstream of 4,4′-MDA.

Principal derivatives and where they go
DerivativeMade byEnd use
MDI and polymeric MDIConversion of the amino groups to isocyanate groupsRigid and flexible polyurethane foam, binders, adhesives, elastomers
MDA-cured epoxy networksStoichiometric cure of epoxy resin at AHEW ≈ 49.6Aerospace laminates, filament-wound vessels, tooling, electrical laminates
PACM — 4,4′-methylenebis(cyclohexylamine)Hydrogenation of both aromatic ringsLight-stable cycloaliphatic epoxy curing agent
H₁₂MDIConversion of PACM to the diisocyanateAliphatic isocyanate for weatherable coatings and elastomers
Polyimide and polyamide-imide resinsCondensation with aromatic dianhydridesMagnet wire enamel, high-temperature films, composite matrices
MOCA-type elastomer curativesRing chlorination of the MDA backboneCast polyurethane elastomer curing agents
Bis-azo dyes and pigment intermediatesDiazotisation of both amino groups and couplingDyes and organic pigments
Packing and supply

Packs designed to keep the material contained

Every container carries the Chelora Amines label with product name, grade, net weight, batch number, manufacturing date, UN number and hazard pictograms, including the health hazard pictogram. Packs are sealed under nitrogen and designed to be opened once.

25 kg

Bags and drums

PE-lined, heat-sealed bags of flake or pastille product, or lined fibre drums where a rigid pack suits your charging arrangement. Palletised and shrink-wrapped.

500 kg

Jumbo bags

Lined FIBCs with a discharge spout for contained charging into a melt tank, keeping dust exposure to a minimum.

Molten / LR

Tankers and small packs

Heated road and ISO tankers at above 100 °C for continuous consumers; 100 g to 1 kg sealed containers for laboratory use under containment.

Pack choice for MDA is an exposure-control decision, not just a logistics one. Tell us how the material will be charged — manual addition, bulk-bag discharge or molten transfer — and we will recommend the pack that keeps your operators furthest from the dust. Export consignments are packed in UN-specification packaging with full dangerous goods documentation and shipped FOB, CIF or CFR through Nhava Sheva and Mundra.

Plan my supply
Handling, storage and safety

A category 1B carcinogen — containment first

MDA may cause cancer, is suspected of causing genetic defects, may cause damage to the liver through prolonged or repeated exposure, may cause an allergic skin reaction, and is harmful if swallowed or inhaled. It is absorbed through intact skin. Several jurisdictions impose substance-specific occupational standards with exposure limits, medical surveillance and regulated-area requirements. The notes below are a summary for planning only — always work to the Safety Data Sheet, your own site risk assessment and the substance-specific regulations that apply where you operate.

Containment and engineering controls

  • Charge from a closed system, a bulk-bag discharge station or a melt line — never as loose dust in an open area.
  • Local exhaust ventilation at every transfer, sampling and charging point.
  • Designate and sign the handling area; restrict access and control decontamination at the boundary.
  • No eating, drinking or storage of personal items in the handling area.

Storage and molten handling

  • Store cool, dry and dark in sealed, opaque packaging; segregate from oxidisers, acids and food or feed.
  • Hold melt tanks and traced lines above about 100 °C; blanket with dry nitrogen.
  • Do not hold molten material hot for extended periods — colour and vapour exposure both rise.
  • Stainless or carbon steel construction; insulate and label hot lines against thermal burns.

Personal protection and surveillance

  • Impervious chemical-resistant gloves with a defined change-out interval, plus a disposable oversuit.
  • Goggles and face shield; respiratory protection appropriate to the task where dust or vapour may be present.
  • Health surveillance including liver function monitoring where required by local regulation.
  • Eyewash, safety shower and a written decontamination and spill procedure before the material arrives on site.
May cause cancer — Carc. 1B
Suspected of causing genetic defects
May damage the liver through repeated exposure
May cause an allergic skin reaction
UN 2811 · Class 6.1 · PG III
REACH Annex XIV — authorisation required in the EU

Regulatory status. MDA is on the REACH Candidate List as a substance of very high concern and on Annex XIV, the Authorisation List, which means its use in the EU requires an authorisation or an applicable exemption. Several other jurisdictions apply substance-specific occupational standards with exposure limits, regulated areas and medical surveillance. We ask every buyer to confirm the end use and the regulatory basis for it before an order is accepted — not as a formality, but because the obligations sit with the user and we would rather establish them at enquiry stage than at the plant gate.

Confirm compliance
Certificate of Analysis4,4′-Methylenedianiline, high-purity grade · CAS 101-77-9
ParameterSpecificationResult
AppearanceLight brown to tan flakesComplies
Purity, 4,4′-isomer (GC)≥ 99.0%Complies
2,4′-isomer≤ 0.8%Complies
Melting range89 – 92 °CComplies
Amine value560 – 570 mg KOH/gComplies
Moisture (KF)≤ 0.2%Complies
Sample layout. Parameters follow the grade you order.QC passed
Quality and documentation

Every bag traceable to a tested batch

MDA is checked before dispatch. Each consignment leaves with the paperwork your QC, EHS, stores and accounts teams need on day one — including the amine value and isomer figures that set your mix ratio.

COACertificate of Analysis with the test results for your specific batch, including isomer purity and amine value.
SDSSafety Data Sheet covering hazard classification, exposure controls, handling, storage, spill response and first aid.
HSN / HS codeHSN 2921 59 on domestic invoices; matching HS code on export documents.
Batch labelsGrade, net weight, batch number, manufacturing date and full hazard marking on every pack.
Export setCommercial invoice, packing list, certificate of origin, dangerous goods declaration and bill of lading.
On requestSVHC and REACH status statements, and country-specific regulatory declarations.
How ordering works

From enquiry to plant gate

Five steps for a first order of MDA. The end-use and regulatory check in step two is specific to this product.

Step 1

Send your requirement

Grade, quantity, flake or molten, isomer and colour limits, how the material will be charged, and your delivery location.

Step 2

End use confirmed

We confirm the intended use, the destination's regulatory position and — for EU destinations — the authorisation or exemption you are relying on.

Step 3

Quote and batch check

We quote, then the batch is tested — isomer purity, amine value, melting range and moisture — and the COA and SDS are prepared.

Step 4

Packed and dispatched

Sealed, labelled packs move under dangerous goods documentation, or a heated tanker is loaded for molten delivery.

Step 5

Delivered and repeated

Material reaches your gate and repeat dispatches are scheduled to your usage, keeping stored quantities on site to a minimum.

Questions buyers ask

4,4′-Methylenedianiline FAQ

Short answers to what purchase, lab, EHS and plant teams ask us most. Anything else, ask us directly.

What is 4,4′-methylenedianiline used for?
Overwhelmingly as the precursor to MDI and polymeric MDI for the polyurethane industry. The isolated pure isomer is used as a high-temperature epoxy curing agent in aerospace and electrical laminates, filament-wound pressure vessels and tooling resins; as a monomer for polyimide and polyamide-imide resins; as a chain extender in polyurethane and polyurea systems; and as an intermediate for PACM, dyes and corrosion inhibitors.
Is MDA a restricted substance?
Yes. MDA is classified as a category 1B carcinogen, is on the REACH Candidate List as a substance of very high concern and is listed on Annex XIV, the Authorisation List. Its use in the EU requires an authorisation or an applicable exemption. Several other jurisdictions apply substance-specific occupational standards with exposure limits, regulated areas and medical surveillance. Check the position in your own jurisdiction before planning a process around it.
Can you supply MDA into the European Union?
Only where the use is covered by an authorisation or a legitimate exemption, and we will ask you to identify which before accepting an order. This is not a commercial formality — the Annex XIV obligations sit with the user, and it is better for both of us to establish the position at enquiry stage than after a shipment has moved.
What is the AHEW of MDA and how much do I use?
MDA has four active amine hydrogens and a molecular weight of 198.26, so the amine hydrogen equivalent weight is about 49.6. For a stoichiometric cure, parts of MDA per hundred parts of resin equal 49.6 divided by the resin's epoxy equivalent weight, times 100 — so a standard liquid bisphenol-A resin at an EEW of 190 takes roughly 26 phr. Confirm against the resin supplier's data and your own cure trials.
Should I take flake or molten MDA?
Molten supply suits continuous consumers with a contained melt-receiving tank: it removes a melting step, eliminates dust exposure and allows metered dosing, which from an exposure-control point of view is the better arrangement. Flake or pastille in lined bags suits batch users, and bulk bags with a discharge spout keep charging contained. The deciding factor is usually how the material is charged, not the price difference.
What is the difference between 4,4′-MDA and polymeric MDA?
4,4′-MDA is the isolated pure isomer with a defined molecular weight and amine value — what a formulator needs. Polymeric MDA is the uncut condensation mixture containing the 2,4′ isomer and a tail of three-ring and four-ring oligomers, which goes directly into MDI manufacture where the oligomer distribution sets the functionality of the resulting polymeric MDI. If you are formulating, specify the 4,4′ content and the 2,4′ limit explicitly.
Is MDA hazardous to transport?
Yes. It ships as UN 2811, Toxic solid, organic, n.o.s. (4,4′-methylenedianiline), Class 6.1, Packing Group III. Packs carry the toxic and health hazard pictograms and export consignments carry a dangerous goods declaration.
Which pack sizes are available?
25 kg PE-lined bags or lined fibre drums of flake and pastille, 500 kg lined jumbo bags with a discharge spout for contained charging, heated road and ISO tankers for molten delivery above 100 °C, and 100 g to 1 kg sealed containers for laboratory use.
What is the HS code for MDA?
4,4′-Methylenedianiline falls under heading 2921 59 — other aromatic polyamines and their derivatives. HSN 2921 59 appears on Indian invoices, and the matching national code appears on export documents.
Why does MDA darken, and does it matter?
Surface oxidation on exposure to air and light moves the colour from light tan towards brown. Amine value is essentially unaffected, so cure behaviour does not change, but the colour carries into cured epoxy systems. Colour-sensitive users should specify a Gardner limit, keep packs sealed and opaque, and avoid holding molten material hot for long periods.
Do you supply trial quantities?
Yes, subject to the same end-use and regulatory check as a full order. A single bag or a laboratory pack can be arranged for qualification work. Tell us your application, your containment arrangement and any isomer or colour requirement when you ask.
How do I get a price?
Send the grade, form, quantity, pack size, intended end use and delivery location through our contact page, by email to source@cheloraamines.com or by phone on +91 98191 11179. A complete enquiry usually gets a quote within 24 hours.

Order 4,4′-MDA from Chelora Amines

Send the grade, form, quantity, pack size, intended end use and your delivery address or destination port. We come back with a price, the documents that go with the batch and a dispatch or shipping plan, usually within 24 hours.

Contact Chelora Amines

Call us+91 98191 11179 Email ussource@cheloraamines.com
Office102, L1, Ashok Premises, Nicholas Road, Andheri (East), Mumbai 400069