Toluene diisocyanate

Last updated
Toluene-2,4-diisocyanate
Structural formula of toluene-2,4-diisocyanate.svg
Toluene-2,4-diisocyanate 3D ball.png
Names
Preferred IUPAC name
2,4-Diisocyanato-1-methylbenzene
Other names
Toluene diisocyanate
Toluene-2,4-diisocyanate
Methyl phenylene diisocyanate
Benzylene 2,4-diisocyanate
2,4-Di(nitrogencarbonyl)toluene
Identifiers
3D model (JSmol)
744602
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.008.678 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 2,4:209-544-5
  • 2,6:202-039-0
PubChem CID
RTECS number
  • 2,4:CZ6300000
  • 2,6:CZ6310000
UNII
UN number 2078
  • InChI=1S/C9H6N2O2/c1-7-2-3-8(10-5-12)4-9(7)11-6-13/h2-4H,1H3 Yes check.svgY
    Key: DVKJHBMWWAPEIU-UHFFFAOYSA-N Yes check.svgY
  • 2,4:InChI=1/C9H6N2O2/c1-7-2-3-8(10-5-12)4-9(7)11-6-13/h2-4H,1H3
    Key: DVKJHBMWWAPEIU-UHFFFAOYAL
  • 2,6:InChI=1S/C9H6N2O2/c1-7-8(10-5-12)3-2-4-9(7)11-6-13/h2-4H,1H3
    Key: RUELTTOHQODFPA-UHFFFAOYSA-N
  • 2,4:Cc1ccc(cc1\N=C=O)\N=C=O
  • 2,6:CC1=C(C=CC=C1N=C=O)N=C=O
Properties
C9H6N2O2
Molar mass 174.2 g/mol
AppearanceColorless liquid
Odor sharp, pungent [1]
Density 1.214 g/cm3, liquid
Melting point 21.8 °C (71.2 °F; 294.9 K)
Boiling point 251 °C (484 °F; 524 K)
Reacts
Vapor pressure 0.01 mmHg (25°C) [1]
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-skull.svg GHS-pictogram-exclam.svg GHS-pictogram-silhouette.svg
Danger
H315, H317, H318, H319, H330, H334, H335, H351, H412
P201, P202, P260, P261, P264, P271, P272, P273, P280, P281, P284, P285, P302+P352, P304+P340, P304+P341, P305+P351+P338, P308+P313, P310, P312, P320, P321, P332+P313, P333+P313, P337+P313, P342+P311, P362, P363, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 3: Short exposure could cause serious temporary or residual injury. E.g. chlorine gasFlammability 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g. canola oilInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
3
1
1
Flash point 127 °C (261 °F; 400 K)
Explosive limits 0.9–9.5% [1]
Lethal dose or concentration (LD, LC):
14 ppm (rat, 4 hr)
13.9 ppm (guinea pig, 4 hr)
9.7 ppm (mouse, 4 hr)
11 ppm (rabbit, 4 hr) [2]
NIOSH (US health exposure limits):
PEL (Permissible)
C 0.02 ppm (0.14 mg/m3) [1]
REL (Recommended)
Ca [1]
IDLH (Immediate danger)
Ca [2.5 ppm] [1]
Related compounds
Related isocyanates
Methylene diphenyl diisocyanate
Naphthalene diisocyanate, 1,3-Diisocyanatobenzene
Related compounds
 Polyurethane
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Toluene diisocyanate (TDI) is an organic compound with the formula CH3C6H3(NCO)2. Two of the six possible isomers are commercially important: 2,4-TDI (CAS: 584-84-9) and 2,6-TDI (CAS: 91-08-7). 2,4-TDI is produced in the pure state, but TDI is often marketed as 80/20 and 65/35 mixtures of the 2,4 and 2,6 isomers respectively. It is produced on a large scale, accounting for 34.1% of the global isocyanate market in 2000, second only to MDI. [3] Approximately 1.4 billion kilograms were produced in 2000. [4] All isomers of TDI are colorless, although commercial samples can appear yellow.

Contents

Synthesis

2,4-TDI is prepared in three steps from toluene via dinitrotoluene and 2,4-diaminotoluene (TDA). Finally, the TDA is subjected to phosgenation, i.e., treatment with phosgene to form TDI. This final step produces HCl as a byproduct and is a major source of industrial hydrochloric acid. [4]

TDI-Synthese.svg

Distillation of the raw TDI mixture produces an 80:20 mixture of 2,4-TDI and 2,6-TDI, known as TDI (80/20). Differentiation or separation of the TDI (80/20) can be used to produce pure 2,4-TDI and a 65:35 mixture of 2,4-TDI and 2,6-TDI, known as TDI (65/35).

Applications

The isocyanate functional groups in TDI react with hydroxyl groups to form carbamate (urethane) links. The two isocyanate groups in TDI react at different rates: The 4-position is approximately four times more reactive than the 2-position. 2,6-TDI is a symmetrical molecule and thus has two isocyanate groups of similar reactivity, similar to the 2-position on 2,4-TDI. However, since both isocyanate groups are attached to the same aromatic ring, reaction of one isocyanate group will cause a change in the reactivity of the second isocyanate group. [3] It is also sometimes used in rocket propellants. [5]

It is used in the production of rigid polyurethane foams with a high temperature stability.

Hazards

The LD50 for TDI is 5800 mg/kg for oral contact and LC50 of 610 mg/m3 for the vapour. Despite the indicated low toxicity, TDI is classified as "very toxic" by the European Community. [4]

In the United States, the Occupational Safety and Health Administration has set a permissible exposure limit with a ceiling at 0.02 ppm (0.14 mg/m3), while the National Institute for Occupational Safety and Health has not established a recommended exposure limit, due to the classification of toluene diisocyanate as a possible occupational carcinogen. [6] This chemical was one of many that were stored by the company whose chemical warehouse stationed in Tianjin, China was the site of massive explosions on August 12, 2015. [7]

Information is available on handling, personal protective equipment, exposure monitoring, transport, storage, sampling and analysis of TDI, dealing with accidents, and health and environmental themes. [8] All major producers of TDI are members of the International Isocyanate Institute,[ citation needed ] whose aim is the promotion of the safe handling of TDI in the workplace, community, and environment.

High-level exposure can result in reactive airways dysfunction syndrome.[ citation needed ]

See also

Related Research Articles

<span class="mw-page-title-main">Phosgene</span> Toxic gaseous compound (COCl2)

Phosgene is an organic chemical compound with the formula COCl2. It is a toxic, colorless gas; in low concentrations, its musty odor resembles that of freshly cut hay or grass. It can be thought of chemically as the double acyl chloride analog of carbonic acid, or structurally as formaldehyde with the hydrogen atoms replaced by chlorine atoms. Phosgene is a valued and important industrial building block, especially for the production of precursors of polyurethanes and polycarbonate plastics.

<span class="mw-page-title-main">Polyurethane</span> Polymer composed of a chain of organic units joined by carbamate (urethane) links

Polyurethane refers to a class of polymers composed of organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethane is produced from a wide range of starting materials. This chemical variety produces polyurethanes with different chemical structures leading to many different applications. These include rigid and flexible foams, and coatings, adhesives, electrical potting compounds, and fibers such as spandex and polyurethane laminate (PUL). Foams are the largest application accounting for 67% of all polyurethane produced in 2016.

<span class="mw-page-title-main">Isocyanate</span> Chemical group (–N=C=O)

In organic chemistry, isocyanate is the functional group with the formula R−N=C=O. Organic compounds that contain an isocyanate group are referred to as isocyanates. An organic compound with two isocyanate groups is known as a diisocyanate. Diisocyanates are manufactured for the production of polyurethanes, a class of polymers.

<span class="mw-page-title-main">Methylene diphenyl diisocyanate</span> Aromatic diisocyanate

Methylene diphenyl diisocyanate (MDI) is an aromatic diisocyanate. Three isomers are common, varying by the positions of the isocyanate groups around the rings: 2,2′-MDI, 2,4′-MDI, and 4,4′-MDI. The 4,4′ isomer is most widely used, and is also known as 4,4′-diphenylmethane diisocyanate. This isomer is also known as Pure MDI. MDI reacts with polyols in the manufacture of polyurethane. It is the most produced diisocyanate, accounting for 61.3% of the global market in the year 2000.

<i>p</i>-Xylene Chemical compound

p-Xylene (para-xylene) is an aromatic hydrocarbon. It is one of the three isomers of dimethylbenzene known collectively as xylenes. The p- stands for para-, indicating that the two methyl groups in p-xylene occupy the diametrically opposite substituent positions 1 and 4. It is in the positions of the two methyl groups, their arene substitution pattern, that it differs from the other isomers, o-xylene and m-xylene. All have the same chemical formula C6H4(CH3)2. All xylene isomers are colorless and highly flammable. The odor threshold of p-xylene is 0.62 parts per million (ppm).

<span class="mw-page-title-main">2,4-Dinitrotoluene</span> Organic chemical compound

2,4-Dinitrotoluene (DNT) or dinitro is an organic compound with the formula C7H6N2O4. This pale yellow crystalline solid is well known as a precursor to trinitrotoluene (TNT) but is mainly produced as a precursor to toluene diisocyanate.

<i>o</i>-Xylene Chemical compound

o-Xylene (ortho-xylene) is an aromatic hydrocarbon with the formula C6H4(CH3)2, with two methyl substituents bonded to adjacent carbon atoms of a benzene ring (the ortho configuration). It is a constitutional isomer of m-xylene and p-xylene, the mixture being called xylene or xylenes. o-Xylene is a colourless slightly oily flammable liquid.

<i>m</i>-Xylene Chemical compound

m-Xylene (meta-xylene) is an aromatic hydrocarbon. It is one of the three isomers of dimethylbenzene known collectively as xylenes. The m- stands for meta-, indicating that the two methyl groups in m-xylene occupy positions 1 and 3 on a benzene ring. It is in the positions of the two methyl groups, their arene substitution pattern, that it differs from the other isomers, o-xylene and p-xylene. All have the same chemical formula C6H4(CH3)2. All xylene isomers are colorless and highly flammable.

<span class="mw-page-title-main">Hexamethylene diisocyanate</span> Chemical compound

Hexamethylene diisocyanate (HDI) is the organic compound with the formula (CH2)6(NCO)2. It is classified as an diisocyanate. It is a colorless liquid. It has sometimes been called HMDI but this not usually done to avoid confusion with Hydrogenated MDI.

<span class="mw-page-title-main">Isophorone diisocyanate</span> Chemical compound

Isophorone diisocyanate (IPDI) is an organic compound in the class known as isocyanates. More specifically, it is an aliphatic diisocyanate. It is produced in relatively small quantities, accounting for only 3.4% of the global diisocyanate market in the year 2000. Aliphatic diisocyanates are used, not in the production of polyurethane foam, but in special applications, such as enamel coatings which are resistant to abrasion and degradation from ultraviolet light. These properties are particularly desirable in, for instance, the exterior paint applied to aircraft.

<span class="mw-page-title-main">Crotonaldehyde</span> Chemical compound

Crotonaldehyde is a chemical compound with the formula CH3CH=CHCHO. The compound is usually sold as a mixture of the E- and Z-isomers, which differ with respect to the relative position of the methyl and formyl groups. The E-isomer is more common (data given in Table is for the E-isomer). This lachrymatory liquid is moderately soluble in water and miscible in organic solvents. As an unsaturated aldehyde, crotonaldehyde is a versatile intermediate in organic synthesis. It occurs in a variety of foodstuffs, e.g. soybean oils.

Perchloryl fluoride is a reactive gas with the chemical formula ClO
3F. It has a characteristic sweet odor that resembles gasoline and kerosene. It is toxic and is a powerful oxidizing and fluorinating agent. It is the acid fluoride of perchloric acid.

Xylidine can refer to any of the six isomers of xylene amine, or any mixture of them.

<span class="mw-page-title-main">4-Nitroaniline</span> Chemical compound

4-Nitroaniline, p-nitroaniline or 1-amino-4-nitrobenzene is an organic compound with the formula C6H6N2O2. A yellow solid, it is one of three isomers of nitroaniline. It is an intermediate in the production of dyes, antioxidants, pharmaceuticals, gasoline, gum inhibitors, poultry medicines, and as a corrosion inhibitor.

<span class="mw-page-title-main">4-Nitrochlorobenzene</span> Chemical compound

4-Nitrochlorobenzene is the organic compound with the formula ClC6H4NO2. It is a pale yellow solid. 4-Nitrochlorobenzene is a common intermediate in the production of a number of industrially useful compounds, including antioxidants commonly found in rubber. Other isomers with the formula ClC6H4NO2 include 2-nitrochlorobenzene and 3-nitrochlorobenzene.

ortho-Cresol (IUPAC name: 2-methylphenol, also known as 2-hydroxytoluene or ortho-Toluenol) is an organic compound with the formula CH3C6H4(OH). It is a colourless solid that is widely used intermediate in the production of other chemicals. It is a derivative of phenol and is an isomer of p-cresol and m-cresol.

4,4′-Methylenedianiline (MDA) is an organic compound with the formula CH2(C6H4NH2)2. It is a colorless solid, although commercial samples can appear yellow or brown. It is produced on an industrial scale, mainly as a precursor to polyurethanes.

2-Nitrotoluene or ortho-nitrotoluene is an organic compound with the formula CH3C6H4NO2. It is pale yellow liquid that crystallizes in two forms, called α (−9.27 °C) and β (−3.17 °C). It is mainly a precursor to o-toluidine, which is an intermediate in the production of various dyes.

<span class="mw-page-title-main">2,4-Diaminotoluene</span> Chemical compound

2,4-Diaminotoluene is an organic compound with the formula C6H3(NH2)2CH3. It is one isomer of six with this formula. It is a white solid, although commercial samples are often yellow-tan.

Hydrogenated MDI (H12MDI or 4,4′-diisocyanato dicyclohexylmethane) is an organic compound in the class known as isocyanates. More specifically, it is an aliphatic diisocyanate. It is a water white liquid at room temperature and is manufactured in relatively small quantities. It is also known as 4,4'-methylenedi(cyclohexyl isocyanate) or methylene bis(4-cyclohexylisocyanate) and has the formula CH2[(C6H10)NCO]2.

References

  1. 1 2 3 4 5 6 NIOSH Pocket Guide to Chemical Hazards. "#0621". National Institute for Occupational Safety and Health (NIOSH).
  2. ↑ "Toluene-2,4-diisocyanate". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 Randall, D.; Lee, S. (2003). The Polyurethanes Book. New York: Wiley. ISBN   978-0-470-85041-1.
  4. 1 2 3 Six, C.; Richter, F. "Isocyanates, Organic". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a14_611.{{cite encyclopedia}}: CS1 maint: multiple names: authors list (link)
  5. ↑ "Ababil-100/Al Fat'h". GlobalSecurity.org. Archived from the original on 15 April 2019.
  6. ↑ National Institute for Occupational Safety and Health (May 1994). "Documentation for Immediately Dangerous To Life or Health Concentrations (IDLHs)". Centers for Disease Control and Prevention.
  7. ↑ Ripley, Will; Jiang, Steven; Mullen, Jethro (13 August 2023). "Tianjin explosion: Dozens dead, areas of Chinese port city devastated". CNN. Retrieved 1 October 2023.
  8. ↑ Allport, D. C.; Gilbert, D. S.; Outterside, S. M., eds. (2003). MDI and TDI: Safety, Health and the Environment: A Source Book and Practical Guide. Wiley. ISBN   978-0-471-95812-3.
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