CAS 101-68-8 · REACH · European Union

4,4'-MDI (4,4'-methylenediphenyl diisocyanate) under REACH

C15H10N2O2 · 4,4-亚甲基二苯基二异氰酸酯

Status: Restricted. 4,4'-MDI is fully registered under REACH at the highest tonnage band (>1,000,000 tonnes/year). **Distinguishing pattern: closes aniline batch 26 chain (downstream MDI product) + Resp. Sens. 1 (H334) is the most-restricted respiratory sensitiser in dataset + Annex XVII Restriction 56 EU-wide diisocyanate training requirement effective 24 February 2022 (most-imminent finished-product compliance layer post-batch-28-formaldehyde-Restriction-77) + Wanhua Chemical Yantai world's largest MDI producer ~3.6 Mt/yr MDI (closes batch 26 aniline integrated chain) + polyurethane chain primary downstream (rigid + flexible PU foam, CASE elastomers, ~85% combined) (NEW combined).** Reg (EC) 1272/2008 harmonised: Resp. Sens. 1 + Acute Tox. 4 inhalation + Skin Sens. 1 + Eye Irrit. 2 + Skin Irrit. 2 + STOT SE 3 + STOT RE 2 + Carc. 2. NOT SVHC. NOT Annex XIV.

4,4'-MDI is fully REACH-registered with **moderate-to-heavy regulatory burden**: Resp. Sens. 1 (H334) + Carc 2 + Skin Sens. 1 + Acute Tox. 4 inhalation + STOT SE 3 + STOT RE 2. The dominant downstream finished-product compliance layer is **Annex XVII Restriction 56 EU-wide diisocyanate training requirement effective 24 February 2022**: downstream EU manufacturers and professional users of MDI-containing mixtures >0.1% must provide formal training to workers. NOT SVHC despite Carc 2 (kept off because of essential industrial use). NO active EU AD case. NOT in CBAM Phase 1. Major Chinese producers: **Wanhua Chemical Yantai (the largest single-company MDI producer globally with integrated upstream aniline batch 26 plus nitrobenzene plus nitric acid plus sulfuric acid batch 2 chain; verify the most recent total MDI nameplate against the Wanhua Chemical investor site before quoting a specific Mt/yr figure)**, BASF Chongqing + BASF Shanghai, Covestro Shanghai, Huntsman Caojing Shanghai. **Closes the aniline batch 26 chain**: aniline + formaldehyde batch 18 → MDA → phosgenation → MDI. End-use mix dominated by rigid PU foam (~50%), CASE (~20%), flexible PU foam (~15%), TPU (~15%).

Listing and threshold

Substance 4,4'-MDI (4,4'-methylenediphenyl diisocyanate) (CAS 101-68-8), C15H10N2O2
Regime EU Regulation (EC) No 1907/2006: Registration, Evaluation, Authorisation and Restriction of Chemicals
Jurisdiction European Union (EU-27 plus EEA: Iceland, Liechtenstein, Norway)
Status Restricted
Tonnage threshold Registration required for any importer or manufacturer placing >1 t/year on the EU market

Classifications under this regime

  • Harmonised CLP classification: Carc. 2 (H351), Acute Tox. 4 inhalation (H332), Skin Irrit. 2 (H315), Eye Irrit. 2 (H319), Resp. Sens. 1 (H334, "may cause allergy or asthma symptoms or breathing difficulties if inhaled"), Skin Sens. 1 (H317), STOT SE 3 (H335), STOT RE 2 (H373)
  • Signal word: DANGER
  • GHS pictograms: GHS07 (exclamation mark), GHS08 (health hazard, sensitiser / target organ)
  • IARC: nitric acid itself is not separately classified; occupational exposure to strong-inorganic-acid mists containing sulfuric acid was classified IARC Group 1 (laryngeal cancer) in Monograph Volume 54 (1992) (verify the current classification and Monograph volume against https://monographs.iarc.who.int/list-of-classifications before relying on the inorganic-acid-mist read-across for nitric acid)
  • NOT subject to Drug Precursors or Explosives Precursors scheduling
  • ADR / RID transport classification: Class 6.1 (toxic substance) for some packaging configurations; commonly transported as Class 6.1 PG III / not classified as DG depending on form

Restrictions and conditions of use

  • NOT on REACH Annex XIV (Authorisation list)
  • NOT classified as SVHC
  • **Annex XVII Restriction 56 (Reg (EU) 2020/1149)**: EU-wide industrial / professional diisocyanate training requirement effective **24 February 2022**. Diisocyanates >0.1% in mixtures placed on the EU market for industrial / professional use require formal training before workers are permitted to use them; training programs delivered by ISOPA and ALIPA industry bodies (verify the consolidated Restriction 56 text and Reg 2020/1149 commencement date against EUR-Lex https://eur-lex.europa.eu/eli/reg/2020/1149/oj before relying)
  • NO active EU AD case on Chinese-origin 4,4'-MDI currently
  • Carbon Border Adjustment Mechanism (CBAM): NOT in CBAM Phase 1 scope
  • EU Reg 10/2011 food-contact: 4,4'-MDI specific migration limit (SML "ND" non-detectable) for plastic food-contact materials

Importer obligations

A non-EU producer cannot register directly under REACH. The EU importer of record must hold a registration or rely on an Only Representative (OR). The dominant practitioner-facing layer is **Annex XVII Restriction 56 diisocyanate training requirement** (effective 24 February 2022): downstream EU manufacturers and professional users of MDI-containing mixtures >0.1% must provide formal training to workers; supply-chain documentation flow-down is required. Major Chinese producers: **Wanhua Chemical Yantai (the largest single-company MDI producer globally with integrated upstream aniline batch 26 plus nitrobenzene plus nitric acid plus sulfuric acid batch 2 chain; verify the most recent total MDI nameplate against the Wanhua Chemical investor site before quoting a specific Mt/yr figure)**, BASF Chongqing + BASF Shanghai, Covestro Shanghai, Huntsman Caojing Shanghai. EU domestic producers: BASF Ludwigshafen + BASF Antwerp, Covestro Brunsbüttel + Krefeld + Tarragona, Huntsman Rotterdam.

Required documents

  • REACH registration number on the EU side (registrant or OR-appointed)
  • Safety Data Sheet (SDS) compliant with REACH Annex II in destination Member State language(s) reflecting H315 / H317 / H319 / H332 / H334 / H335 / H351 / H373 classification
  • CLP-compliant labelling with GHS07 + GHS08 pictograms and DANGER signal word
  • Customs entry with HS code 292910 (4,4'-MDI as monomeric form) or HS 39093900 (polymeric MDI / oligomeric forms)
  • ADR consignment note for transport (Class 6.1 or unclassified depending on form)
  • **Annex XVII Restriction 56 diisocyanate training documentation** for downstream industrial / professional users

Common compliance traps

The pitfalls that have bitten importers on this lane in the past. None of these is theoretical.

  • **Annex XVII Restriction 56 diisocyanate training requirement effective 24 February 2022** is the dominant downstream finished-product compliance layer: most-imminent post-batch-28-formaldehyde-Restriction-77 compliance milestone
  • **Resp. Sens. 1 (H334)** classification drives substantial workplace exposure-control overhead + occupational asthma surveillance
  • NOT SVHC despite Carc 2 (kept off because of essential industrial use)
  • NO active EU AD case on Chinese 4,4'-MDI currently
  • NOT in CBAM Phase 1
  • Major Chinese producers: **Wanhua Chemical Yantai (the largest single-company MDI producer globally with integrated upstream aniline batch 26 plus nitrobenzene plus nitric acid plus sulfuric acid batch 2 chain; verify the most recent total MDI nameplate against the Wanhua Chemical investor site before quoting a specific Mt/yr figure)**, BASF Chongqing + BASF Shanghai, Covestro Shanghai, Huntsman Caojing Shanghai. China dominates global MDI capacity (~50%, ~5-6 Mt/yr 4,4'-MDI equivalent)
  • Production: aniline (batch 26) + formaldehyde (batch 18) → MDA → phosgenation → MDI; integrated production flow-through structurally
  • End-use mix: rigid polyurethane foam (~50%, insulation + appliance + automotive), CASE coatings + adhesives + sealants + elastomers (~20%), flexible polyurethane foam (~15%), TPU thermoplastic polyurethane + others (~15%)
  • Polymeric MDI (CAS 9016-87-9) and monomeric 4,4'-MDI (CAS 101-68-8) are different forms with different CAS numbers and different applications

Where to read next

For substance-level identifiers (formula, molecular weight, SMILES, InChIKey), GHS hazard profile, IMDG transport class, and full sourcing reference for 4,4'-mdi (4,4'-methylenediphenyl diisocyanate), see the CAS 101-68-8 sourcing reference.

For grade-by-grade buying notes, freight maths, supplier-tier pricing, and a worked landed-cost example, the 4,4'-mdi (4,4'-methylenediphenyl diisocyanate) cornerstone hub covers the full sourcing chain.

For the structure and history of REACH, see the REACH glossary entry.

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