Main-Product

Methylene Diphenyl Diisocyanate (MDI) is a reactive chemical intermediate with the molecular formula C₁₅H₁₀N₂O₂ and molecular weight of 250.25 g/mol. It serves as an essential building block in the production of polyurethanes, urethane-prepolymers, and polyisocyanurate polymers across diverse industries.

Chemical Structure and Isomers

MDI exists in three main isomeric forms based on the positions of the isocyanate groups (-NCO) around the aromatic rings :

• 4,4'-MDI: The most commercially important isomer, also known as Pure MDI or Monomeric MDI (MMDI)
• 2,4'-MDI: Secondary isomer with differential reactivity
• 2,2'-MDI: Less common isomer

The 4,4'-MDI isomer appears as white to light-yellow, odorless flakes at room temperature with a melting point of 38-44°C. It becomes a clear, colorless to yellowish liquid when heated above 37°C.

Commercial Forms and Properties

Pure/Monomeric MDI (MMDI)

• White crystalline solid at room temperature containing >99.8% 4,4'-MDI
• NCO content of 33.6% with functionality of 2.0
• Exhibits high reactivity and linearity, making it ideal for spandex fibers, elastomers, and prepolymers

Polymeric MDI (PMDI)

• Dark brown to viscous liquid at room temperature
• Complex mixture containing 25-80% monomeric 4,4'-MDI plus oligomers with 3-6 aromatic rings
• NCO content of 30-32% with average functionality of 2.7 and viscosity of 150-250 mPa·s at 25°C
• Primary use in rigid and semi-rigid polyurethane foams for construction and insulation applications

Carbodiimide-Modified MDI

• Clear, light yellow liquid with functionality around 2.2 due to trifunctional uretonimine species formation
• Enhanced durability, hydrolysis resistance, and mechanical properties compared to standard MDI
• Used in automotive interior parts, steering wheels, and airbag covers

Production Process

MDI manufacture involves a two-step synthesis :

1. Condensation Step: Aniline condenses with formaldehyde using hydrochloric acid as catalyst to produce methylenedianiline (MDA) and other diamine precursors
2. Phosgenation Step: The diamines react with phosgene in a solvent to form raw MDI mixture, with solvent, excess phosgene, and hydrochloric acid by-products recovered and recycled

• Purification: Fractional distillation, crystallization, or sublimation separates polymeric MDI from pure MDI isomers

Key Physical Properties

Applications and Uses

MDI's versatility enables numerous polyurethane applications:

Foam Applications

• Rigid polyurethane foams for building insulation, appliance insulation, and construction panels
• Flexible foams for automotive seating, furniture cushioning, and mattresses
• Semi-rigid foams for automotive interior panels

Non-Foam Applications

• Coatings, Adhesives, Sealants, and Elastomers (CASE) products
• Thermoplastic polyurethanes (TPU) for automotive and industrial applications
• Spandex fibers and synthetic leather production
• Wood composite binders for particleboard and oriented strand board

Demand

MDI represents the most commercially important diisocyanate globally, with a demand exceeding 8.5 million tonnes annually as of 2024, a 6% increase from 2023, enabling the modern polyurethane industry's diverse applications.

References

1. Methylene Diphenyl Diisocyanate (MDI) - Essential Building Blocks for Polyurethanes. Gantrade
2. 4,4'-Diphenylmethane diisocyanate. ChemicalBook
3. Jul 05, 2022.Polymeric MDI. Green View Technology and Development Co., Ltd.
4. Polyurethane production in plastics & polymers production. KROHNE
5. Jul 21, 2025. Methylene Diphenyl Diisocyanate (MDI) Market. Market Reports World.

Solid