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Page last reviewed: 11/22/2006
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Isocyanates
Isocyanates are compounds containing the isocyanate group (-NCO). They react with compounds containing alcohol (hydroxyl) groups to produce polyurethane polymers, which are components of polyurethane foams, thermoplastic elastomers, spandex fibers, and polyurethane paints. Isocyanates are the raw materials that make up all polyurethane products. Jobs that may involve exposure to isocyanates include painting, foam-blowing, and the manufacture of many Polyurethane products, such as chemicals, polyurethane foam, insulation materials, surface coatings, car seats, furniture, foam mattresses, under-carpet padding, packaging materials, shoes, laminated fabrics, polyurethane rubber, and adhesives, and during the thermal degredation of polyurethane products.
Health effects of isocyanate exposure include irritation of skin and mucous membranes, chest tightness, and difficult breathing. Isocyanates include compounds classified as potential human carcinogens and known to cause cancer in animals. The main effects of hazardous exposures are occupational asthma and other lung problems, as well as irritation of the eyes, nose, throat, and skin.
Isocyanates hazards are addressed in specific standards for the general industry,
shipyard employment, and the construction industry.
OSHA Standards
This section highlights OSHA standards, preambles to final
rules (background to final rules), and standard interpretations (official letters of interpretation of
the standards) related to isocyanates.
Note: Twenty-five states, Puerto Rico and the Virgin Islands have OSHA-approved
State Plans and have adopted their own standards and enforcement
policies. For the most part, these States adopt standards that are
identical to Federal OSHA. However, some States have adopted different
standards applicable to this topic or may have different enforcement
policies.
General Industry (29
CFR 1910)
Shipyard Employment (29
CFR 1915)
Construction Industry (29
CFR 1926)
- 1926 Subpart D, Occupational health and environmental controls
- 1926.55, Gases, vapors, fumes, dusts, and mists
- Appendix A,
Gases, vapors, fumes, dusts, and mists
- 1926.64, Process safety management of highly hazardous chemicals
- Appendix A,
List of highly hazardous chemicals, toxics and
reactives
(Mandatory)
Preambles to Final Rules
Standard Interpretations
Hazards and Solutions
Many workers are unaware of the potential hazards
that chemicals present in their
work environment, which makes them more vulnerable to injury. The following references aid in recognizing and evaluating hazards associated with
isocyanates in the workplace.
-
Right
to Know Hazardous Substance Fact Sheets.
New Jersey Department of Health and Senior Services.
These fact sheets include 1,055 individual hazardous chemicals
with information about acute and chronic health hazards.
At least 100 fact sheets are revised every year
and 235 have been translated into Spanish.
The following fact sheets cover isocyanate
compounds.
- 3-Chloro-4-Methyl Phenyl Isocyanate [32 KB
PDF,
6 pages]. CAS No. 28479-22-3,
(2004, March).
- Hexamethylene Diisocyanate [35 KB
PDF, 6 pages]. CAS No. 822-06-0,
(1999, April).
- Isophorone Diisocyanate [34 KB
PDF, 6 pages]. CAS No. 4098-71-9,
(1999, February).
- Methylene Bisphenyl Isocyanate [33 KB
PDF, 6 pages]. CAS No. 101-68-8,
(1998, June).
- Methyl Isocyanate [36 KB
PDF, 6 pages]. CAS No. 624-83-9,
(2002, April).
- Tolene-2,4-Diisocyanate [37 KB
PDF, 6 pages]. CAS No. 584-84-9,
(2002, April).
- Tolene-2,6-Diisocyanate [35 KB
PDF, 6 pages]. CAS No. 91-08-7,
(2002, March).
-
OSHA Technical Manual (OTM). OSHA
Directive TED 01-00-015 [TED 1-0.15A],
(1999, January 20).
-
Chemical Hazard Communication. OSHA Publication 3084, (1998).
Also available as a 248 KB
PDF, 31 pages.
Addresses the need for chemical hazard communication and
explains why a standard is necessary to minimize workplace hazards.
- Evaluation of the Effectiveness of Air-Purifying Respirator Cartridges in Removing MDI Aerosols from Air.
The Dow Chemical Company, (1997).
Shows that organic vapor cartridges without a particulate filter were not effective at removing
Methylene bisphenyl isocyanate (MDI) aerosols from air,
while
organic vapor cartridges with dust/mist (DM) or high efficiency (HEPA) filters effectively removed greater than 99
percent of MDI aerosol and vapor in all test atmospheres.
- Preventing Asthma and Death from Diisocyanate Exposure.
US Department of Health and Human
Services (DHHS), National Institute for Occupational
Safety and Health (NIOSH) Publication No. 96-111,
(1996). Discusses the recognition, evaluation, and control of diisocyanate exposures.
-
Documentation for Immediately Dangerous to life or Health Concentrations
(IDLHs). National Institute for
Occupational Safety and Health (NIOSH) Chemical Listing and Documentation of Revised IDLH Values, (1994,
March).
- The Environmental Protection Agency (EPA) has prepared four Health Effects Fact Sheets for specific isocyanates.
- The following studies indicate that respiratory sensitivity to isocyanates may be related to previous dermal exposure.
- Kimber, I. "The Role of the Skin in Development of
Chemical Respiratory Hypersensitivity."
Toxicology Letters
86(1996): 89-92.
- Bickis, U., and K. Nakatsu. "A Single Skin Contact with Toluene Diisocyanate (TDI) Causes a One-Year Persistence of Airway Sensitization, Demonstrable in Vivo and in Vitro." (1996). Abstract of platform presentation No. 310 presented at the 1996 American Industrial Hygiene Conference and Exposition.
- Bickis,
U. "Investigation of Dermally Induced Airway
Hyperreactivity to Toluene Diisocyanate in
Guinea Pigs." Ph.D. thesis,
Department of Pharmacology and
Toxicology, Queen’s University,
Kingston, Canada, (1994).
- Karol, M. H., et al.
"Dermal Contact With Toluene Diisocyanate (TDI)
Produced Respiratory Tract
Hypersensitivity in Guinea Pigs." Toxicol. Appl. Pharmacol 58(1981):
221-230.
- Rattray, N. J., et al. "Induction of Respiratory Hypersensitivity to
Diphenylmethane-4,4’-Diisocyanate (MDI) in
Guinea Pigs; Influence of
route of exposure." Toxicology 88(1994):
15-30.
- Deschamps, F., et al. "Mechanisms of Occupational Asthma Induced by Isocyanate." Ann. Occup. Hyg.
42(1998): 33-36.
- Cole, K. C., et al.
"Flexible Polyurethane Foam. I. FTIR
Analysis of Residual Isocyanate." Applied Polymer Science
34(1987): 395-407.
Possible Solutions for Workplace Hazards
- Health Hazard Evaluations. National
Institute for Occupational Safety and Health
(NIOSH). Performs Health Hazard Evaluations (HHEs)
for a wide variety of industries that use
isocyanates to determine whether any substance normally found in the
workplace contains
potentially toxic concentrations. NIOSH
also provides specific control recommendations.
To access the online database, follow the
link and then search the site using the term
"isocyanate." Some HHEs that focus on isocyanates are listed below.
- Isocyanate Exposures From Polyurethane Foam Packaging Operations, General Motors Corporation, Allison Transmission Division, Indianapolis, Indiana [1 MB PDF, 16 pages].
Report No. HETA
99-0065-2780, (1999, December).
- Isocyanate-Containing Compounds During Spray Painting Operations, Lockheed Martin Aeronautical Systems, Marietta, Georgia [2 MB PDF, 21 pages].
Report No. HETA
99-0122-2798, (2000, June).
- Worker Exposure To Methylene-bisphenyl-diisocyanate (MDI) From Foam Spraying Operations In an Adjacent Building, Twin City Fruit, F.L. Thorpe Co., Deadwood, South Dakota [1 MB PDF, 17 pages].
Report No. HETA
89-0278-2035, (1990, April).
- Isocyanates Used In Some Powder Coatings,
Modern Materials Incorporated,
Rochester, Indiana [3 MB PDF, 56 pages].
Report No. HETA
90-0174-2231, (1992, July).
- Possible Isocyanate and Polyamide Imide
Resin Exposures Occurring During Brazing
and Welding Operations, Square D
Company, Oshkosh, Wisconsin [1 MB PDF, 23 pages].
Report No. HETA
94-0312-2512, (1995, June).
- A Summary of Health Hazard Evaluations: Issues Related to Occupational Exposure to Isocyanates, 1989 to 2002 [1 MB PDF, 42 pages].
Report No. HETA 99-0039, (1999, April). Presents some background
information about isocyanate exposures,
health effects, analytical methods, and
general recommendations for most isocyanate-related
HHEs. The major portion of this document
presents the titles and summaries of the
site visits related to isocyantes
conducted between 1989 and 2002.
- PMDI User Guidelines for Chemical Protective Clothing Selection [245 KB
PDF, 6 pages].
Alliance for the Polyurethane Industry (API) Technical Bulletin AX178, (2002, January).
Presents guidelines for selecting the appropriate chemical protective clothing for working with polymeric methylene diisocyanate (polymeric MDI or PMDI) and PMDI-based foam systems.
- TDI User Guidelines for Chemical Protective Clothing Selection [128 KB PDF, 6 pages].
Alliance for the Polyurethane Industry (API) Technical Bulletin AX179, (2001, July). Presents guidelines for selecting appropriate
chemical protective clothing for working with toluene diisocyanate (TDI) and TDI-based
foam systems.
- Use of portable air compressors as a source of air supply for supplied air respirators.
OSHA Hazard Information Bulletin (HIB), (1985). States that under current policy, supplied air
respirators are not to be used in an
atmosphere that is immediately dangerous
to life or health (IDLH) unless the
respirator is
equipped with a self-contained air supply
for escape.
-
Personal Protective Equipment (PPE).
OSHA Safety and Health Topics Page.
Sampling and Analysis
- Chemical Sampling Information. OSHA. The
Chemical Sampling Information file presents,
in concise form, data on a large number of
chemical substances that may be encountered
in industrial hygiene investigations.
Includes information relating to chemical sampling for isocyanates
and contains references to the following isocyanate compounds:
- Evaluation of the Effectiveness of Air-Purifying Respirator Cartridges in Removing MDI Aerosols from Air.
OSHA,
(1997). Describes sampling procedures for using direct reading (colorimetric) wipes and collecting wipe samples for laboratory analysis.
-
Diisocyantes (HDI, 2,4-TDI, 2,6-TDI).
OSHA Method 42, (1989, March).
-
Methylene bisphenyl
isocyanate (MDI). OSHA Method 47, (1989, March).
-
NIOSH Manual of Analytical Methods
(NMAM). US Department of Health and Human
Services (DHHS), National Institute for
Occupational Safety and Health (NIOSH)
Publication No. 2003-154, (2003).
Provides individual analytical
methods, listed by chemical name or method number.
- U.K. Health and Safety Executive Method 25/2
- The following are analysis methods for specific isocyanate compounds. It is often desirable to determine the amount of free isocyanate, not just the specific compound. Several methods have been suggested to accomplish this.
However, all have had serious problems when applied to field sampling.
- Streicher, RP, et al. Investigation of the
ability of MDHS method 25 to
determine urethane-bound isocyanate
groups. American Industrial Hygiene
Association Journal. 1995;56(5):437-42.
- Key-Schwartz, RJ. Analytical problems
encountered with NIOSH method 5521 for
total isocyanates. American Industrial Hygiene Association Journal.
1995;56(5):474-9.
- Maitre, A., et al.
Biological monitoring of occupational
exposure to toluene diisocyanate. Int. Arch. Occup.
Environ. Health. 1993;65:97-100.
- Documentation of the threshold limit
values and biological exposure indices.
American Conference for Government Industrial Hygienists
(ACGIH). 1991;6:1581-9.
- For additional
information, see OSHA's
Sampling and Analysis Safety and Health
Topics Page.
Additional Information
Related Safety and Health Topics Pages
Training
- Isocyanates in Paints [193 KB PDF, 1 page]. Workplace Safety and Health Division of the Manitoba Labour and Immigration, Bulletin 143,
(2008, December). Includes a short summary of hazards and protective measures for workers spraying isocyanate-containing paints.
Accessibility Assistance: Contact the OSHA Directorate of Technical Support and Emergency Management at (202) 693-2300 for assistance accessing PDF materials.
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