1,6-HEXAMETHYLENEDIAMINE

1,6-Hexamethylenediamine (HMDA) is used as a chemical intermediate in the manufacture of resins, such as nylon-type polyamide and nylon. The polyamides formed from HMDA are used in printing inks, dimer acids, paints, and textiles. HMDA is used in the manufacture of oil-modified and moisture-area types of urethane coatings. It is also used to prepare hexamethylene diisocyanate. The diamines, including HMDA, are industrially used as corrosion inhibitors through their application as an additive in oils and lubricants and as curing agents for epoxide resins and plastic articles (ACGIH, 1996; Budavari, 2000; HSDB , 2002; Sittig, 1991a).

FORMS

HMDA is solid (anhydrous) at 15 degrees C and 1 atm. It has a weak, fishy odor similar to piperdine and exists as colorless leaflets or platelets and as long needles from sublimation. It has also been described as a white crystalline solid with an ammonia-type odor. Closer examination of the solid indicates rhombic bipyrimidal plates. Anhydrous HMDA is 99.8% pure, while HMDA in solution is 70% pure. HMDA solution is a clear, colorless liquid (AAR, 2000; ACGIH, 1996; CHRIS, 2002; HSDB , 2002; Lewis, 2000).

SOURCES

Methods of Manufacturing/Derivation:

Reduction of adiponitrile with sodium and alcohol (Budavari, 2000).
HMDA may be formed by reacting catalytic vapor-phase ammonia with adipic acid to yield adiponitrile. This step is then followed by liquid-phase catalytic hydrogenation (Lewis, 2001a).
HMDA may also be formed by chlorinating butadiene, followed by a reaction with sodium cyanide (cuprous chloride catalyst) to produce 1,4-dicyanobutylene, and hydrogenation (Lewis, 2001a).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

1,6-hexamethylenediamine (HMDA) is corrosive to the eyes, skin, and respiratory tract. Inhalation may cause coughing, labored breathing, and shortness of breath. Contact with liquid HMDA may be caustic to the skin and eyes causing redness and pain. First-degree burns may result from short-term exposure to the skin, and prolonged exposure may cause secondary burns. Symptoms of HMDA ingestion may include abdominal cramps and pain.

Chronic or repeated exposure can cause anemia, kidney or liver damage. Other signs and symptoms of prolonged contact may include skin damage, allergic rhinitis, bronchial asthma, impairment of bronchial permeability, toxicoallergic hepatitis, gastritis, colitis, hypergammaglobulinemia, increased transaminase activity, and eosinophilia.

Inhalation may be fatal as a result of spasm, inflammation and edema of the larynx and bronchi, chemical pneumonitis, and acute lung injury.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

TOXIC; inhalation, ingestion or skin contact with material may cause severe injury or death.
Contact with molten substance may cause severe burns to skin and eyes.
Avoid any skin contact.
Effects of contact or inhalation may be delayed.
Fire may produce irritating, corrosive and/or toxic gases.
Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

-FIRST AID

FIRST AID AND PREHOSPITAL TREATMENT

PREHOSPITAL ACTIVATED CHARCOAL ADMINISTRATION

Consider prehospital administration of activated charcoal as an aqueous slurry in patients with a potentially toxic ingestion who are awake and able to protect their airway. Activated charcoal is most effective when administered within one hour of ingestion. Administration in the prehospital setting has the potential to significantly decrease the time from toxin ingestion to activated charcoal administration, although it has not been shown to affect outcome (Alaspaa et al, 2005; Thakore & Murphy, 2002; Spiller & Rogers, 2002).

In patients who are at risk for the abrupt onset of seizures or mental status depression, activated charcoal should not be administered in the prehospital setting, due to the risk of aspiration in the event of spontaneous emesis.
The addition of flavoring agents (cola drinks, chocolate milk, cherry syrup) to activated charcoal improves the palatability for children and may facilitate successful administration (Guenther Skokan et al, 2001; Dagnone et al, 2002).

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device.
Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes.
In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes.
For minor skin contact, avoid spreading material on unaffected skin.
Keep victim warm and quiet.
Effects of exposure (inhalation, ingestion or skin contact) to substance may be delayed.
Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.

FIRST AID

INHALATION EXPOSURE -

INHALATION: Move patient to fresh air. Monitor for respiratory distress. If cough or difficulty breathing develops, evaluate for respiratory tract irritation, bronchitis, or pneumonitis. Administer oxygen and assist ventilation as required. Treat bronchospasm with an inhaled beta2-adrenergic agonist. Consider systemic corticosteroids in patients with significant bronchospasm.
ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of PEEP and mechanical ventilation may be needed.

DERMAL EXPOSURE -

DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
Treat dermal irritation or burns with standard topical therapy. Patients developing dermal hypersensitivity reactions may require treatment with systemic or topical corticosteroids or antihistamines.

EYE EXPOSURE -

DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.

ORAL EXPOSURE -

Because of the potential for gastrointestinal tract irritation, DO NOT induce emesis.
DILUTION: If no respiratory compromise is present, administer milk or water as soon as possible after ingestion. Dilution may only be helpful if performed in the first seconds to minutes after ingestion. The ideal amount is unknown; no more than 8 ounces (240 mL) in adults and 4 ounces (120 mL) in children is recommended to minimize the risk of vomiting.
PREHOSPITAL ACTIVATED CHARCOAL ADMINISTRATION

Consider prehospital administration of activated charcoal as an aqueous slurry in patients with a potentially toxic ingestion who are awake and able to protect their airway. Activated charcoal is most effective when administered within one hour of ingestion. Administration in the prehospital setting has the potential to significantly decrease the time from toxin ingestion to activated charcoal administration, although it has not been shown to affect outcome (Alaspaa et al, 2005; Thakore & Murphy, 2002; Spiller & Rogers, 2002).

In patients who are at risk for the abrupt onset of seizures or mental status depression, activated charcoal should not be administered in the prehospital setting, due to the risk of aspiration in the event of spontaneous emesis.
The addition of flavoring agents (cola drinks, chocolate milk, cherry syrup) to activated charcoal improves the palatability for children and may facilitate successful administration (Guenther Skokan et al, 2001; Dagnone et al, 2002).

ACTIVATED CHARCOAL: Administer charcoal as a slurry (240 mL water/30 g charcoal). Usual dose: 25 to 100 g in adults/adolescents, 25 to 50 g in children (1 to 12 years), and 1 g/kg in infants less than 1 year old.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

ADULT

The minimum lethal human dose to this agent has not been delineated.

MAXIMUM TOLERATED EXPOSURE

ADULT

Upper respiratory tract and eye irritation have been noted at concentrations greater than 100 mg/m(3) (Grant & Schuman, 1993).
Workers handling HMDA in an atmosphere containing 2 to 5.5 mg/m(3) under normal operations and 131.5 mg/m(3) during autoclave operations developed conjunctival and upper respiratory tract irritation. One worker out of 20 studied developed acute hepatitis followed by dermatitis, and the effects were attributed to HMDA. No anemia was observed (Bingham et al, 2001).

Carcinogenicity Ratings for CAS124-09-4 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: 1,6-Hexanediamine
EPA (U.S. Environmental Protection Agency, 2011): Not Listed
IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed
NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed
MAK (DFG, 2002): Not Listed
NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

TOXICITY AND RISK ASSESSMENT VALUES

EPA IRIS

EPA Risk Assessment Values for CAS124-09-4 (U.S. Environmental Protection Agency, 2011):

Not Listed

TOXICITY VALUES

ACGIH, 1996a OHM/TADS, 2002 RTECS, 2002)
- LCLo- (INHALATION)MOUSE:
- LD50- (INTRAPERITONEAL)MOUSE:
- LD50- (INTRAVENOUS)MOUSE:
- LD50- (SUBCUTANEOUS)MOUSE:
- LD50- (SKIN)RABBIT:
- LD50- (INTRAVENOUS)RAT:
- LD50- (ORAL)RAT:
- TCLo- (INHALATION)RAT:
- TDLo- (INTRAPERITONEAL)MOUSE:
- TDLo- (ORAL)RAT:

CALCULATIONS

AMBIENT CONVERSIONS

1 mg/L = 210 ppm (HSDB , 2002)
1 ppm = 4.75 mg/m(3) (HSDB , 2002)

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS124-09-4 (American Conference of Governmental Industrial Hygienists, 2010):

Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.

Adopted Value

1,6-Hexanediamine

TLV:

TLV-TWA: 0.5 ppm
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: Not Listed
Codes: Not Listed
Definitions: Not Listed

TLV Basis - Critical Effect(s): URT and skin irr
Molecular Weight: 116.21

For gases and vapors, to convert the TLV from ppm to mg/m(3):

[(TLV in ppm)(gram molecular weight of substance)]/24.45

For gases and vapors, to convert the TLV from mg/m(3) to ppm:

[(TLV in mg/m(3))(24.45)]/gram molecular weight of substance

AIHA WEEL Values for CAS124-09-4 (AIHA, 2006):

Listed as 1,6-Hexanediamine
1 ppm
Ceiling or Short-term TWA:
Skin Notation: No
Dermal Sensitizer: No
Candidate WEEL: No
WEEL Under Review: No

NIOSH REL and IDLH Values for CAS124-09-4 (National Institute for Occupational Safety and Health, 2007):

Not Listed

OSHA PEL Values for CAS124-09-4 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS124-09-4 (U.S. Occupational Safety and Health Administration, 2010):

Not Listed

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS124-09-4 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS124-09-4 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS124-09-4 (U.S. Environmental Protection Agency, 2010b):

Not Listed
Editor's Note: The D, F, and K series waste numbers and Appendix VIII to Part 261 -- Hazardous Constituents were not included. Please refer to 40 CFR Part 261.

EPA SARA Title III, Extremely Hazardous Substance List for CAS124-09-4 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA SARA Title III, Community Right-to-Know for CAS124-09-4 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Not Listed

DOT List of Marine Pollutants for CAS124-09-4 (49 CFR 172.101 - App. B, 2005):

Not Listed

EPA TSCA Inventory for CAS124-09-4 (EPA, 2005):

Listed as: 1,6-Hexanediamine

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1783 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Hexamethylenediamine solution

Symbol(s): Not Listed
Hazard class or Division: 8

8: Corrosive material. See 49 CFR section 173.136 for definitions.

Identification Number: UN1783
Packing Group: II

II: Packing Group II - indicates the degree of danger presented by the material is medium.

Label(s) required (if not excepted): 8

8: Corrosive.

Special Provisions: IB2, T7, TP2

IB2: Authorized IBCs: Metal (31A, 31B and 31N); Rigid plastics (31H1 and 31H2); Composite (31HZ1). Additional Requirement: Only liquids with a vapor pressure less than or equal to 110 kPa at 50 °C (1.1 bar at 122 °F), or 130kPa at 55 °C (1.3 bar at 131 °F) are authorized.
T7: Minimum test pressure (bar): 4; Minimum shell thickness (in mm-reference steel) (See sxn.178.274(d)): sxn.178.274(d)(2); Pressure-relief requirements (See sxn.178.275(g)): Normal; Bottom opening requirements (See sxn.178.275(d)): sxn.178.275(d)(3).
TP2: a. The maximum degree of filling must not exceed the degree of filling determined by the following: [Degree of filling = 95/1+alpha(tr - tf)], where tr is the maximum mean bulk temperature during transport, tf is the temperature in degrees celsius of the liquid during filling, and alpha is the mean coefficient of cubical expansion of the liquid between the mean temperature of the liquid during filling (tf) and the maximum mean bulk temperature during transportation (tr) both in degrees celsius; and b. For liquids transported under ambient conditions a may be calculated using the formula: [alpha = (d15-d50)/(35 x d50)], where d15 and d50 are the densities (in units of mass per unit volume) of the liquid at 15 degrees C (59 degrees F) and 50 degrees C (122 degrees F), respectively.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: None
Non-bulk packaging: 202
Bulk packaging: 242

Quantity Limitations:

Passenger aircraft or railcar: 1 L
Cargo aircraft only: 30 L

Vessel Stowage Requirements:

Vessel stowage location: A

A: The material may be stowed "on deck" or "under deck" on a cargo vessel and on a passenger vessel.

Vessel stowage other: Not Listed

Hazardous materials descriptions and proper shipping name: Hexamethylenediamine solution

Symbol(s): Not Listed
Hazard class or Division: 8

8: Corrosive material. See 49 CFR section 173.136 for definitions.

Identification Number: UN1783
Packing Group: III

III: Packing Group III - indicates the degree of danger presented by the material is minor.

Label(s) required (if not excepted): 8

8: Corrosive.

Special Provisions: IB3, T4, TP1

IB3: Authorized IBCs: Metal (31A, 31B and 31N); Rigid plastics (31H1 and 31H2); Composite (31HZ1 and 31HA2, 31HB2, 31HN2, 31HD2 and 31HH2). Additional Requirement: Only liquids with a vapor pressure less than or equal to 110 kPa at 50 °C (1.1 bar at 122 °F), or 130 kPa at 55 °C (1.3 bar at 131 °F) are authorized, except for UN2672 (also see Special Provision IP8 in Table 3 for UN2672).
T4: Minimum test pressure (bar): 2.65; Minimum shell thickness (in mm-reference steel) (See sxn.178.274(d)): sxn.178.274(d)(2); Pressure-relief requirements (See sxn.178.275(g)): Normal; Bottom opening requirements (See sxn.178.275(d)): sxn.178.275(d)(3).
TP1: The maximum degree of filling must not exceed the degree of filling determined by the following: [Degree of filling = 97/1+alpha(tr - tf)], where tr is the maximum mean bulk temperature during transport, and tf is the temperature in degrees celsius of the liquid during filling.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: 154
Non-bulk packaging: 203
Bulk packaging: 241

Quantity Limitations:

Passenger aircraft or railcar: 5 L
Cargo aircraft only: 60 L

Vessel Stowage Requirements:

Vessel stowage location: A

A: The material may be stowed "on deck" or "under deck" on a cargo vessel and on a passenger vessel.

Vessel stowage other: Not Listed

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 2280 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Hexamethylenediamine, solid

Symbol(s): Not Listed
Hazard class or Division: 8

8: Corrosive material. See 49 CFR section 173.136 for definitions.

Identification Number: UN2280
Packing Group: III

III: Packing Group III - indicates the degree of danger presented by the material is minor.

Label(s) required (if not excepted): 8

8: Corrosive.

Special Provisions: IB8, IP3, T1, TP33

IB8: Authorized IBCs: Metal (11A, 11B, 11N, 21A, 21B, 21N, 31A, 31B and 31N); Rigid plastics (11H1, 11H2, 21H1, 21H2, 31H1 and 31H2); Composite (11HZ1, 11HZ2, 21HZ1, 21HZ2, 31HZ1 and 31HZ2); Fiberboard (11G); Wooden (11C, 11D and 11F); Flexible (13H1, 13H2, 13H3, 13H4, 13H5, 13L1, 13L2, 13L3, 13L4, 13M1 or 13M2).
IP3: Flexible IBCs must be sift-proof and water-resistant or must be fitted with a sift-proof and water-resistant liner.
T1: Minimum test pressure (bar): 1.5; Minimum shell thickness (in mm-reference steel) (See sxn.178.274(d)): sxn.178.274(d)(2); Pressure-relief requirements (See sxn.178.275(g)): Normal; Bottom opening requirements (See sxn.178.275(d)): sxn.178.275(d)(2).
TP33: The portable tank instruction assigned for this substance applies for granular and powdered solids and for solids which are filled and discharged at temperatures above their melting point which are cooled and transported as a solid mass. Solid substances transported or offered for transport above their melting point are authorized for transportation in portable tanks conforming to the provisions of portable tank instruction T4 for solid substances of packing group III or T7 for solid substances of packing group II, unless a tank with more stringent requirements for minimum shell thickness, maximum allowable working pressure, pressure-relief devices or bottom outlets are assigned in which case the more stringent tank instruction and special provisions shall apply. Filling limits must be in accordance with portable tank special provision TP3. Solids meeting the defnintion of an elevated temperature material must be transported in accordance with the applicable requirements of this subchapter.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: 154
Non-bulk packaging: 213
Bulk packaging: 240

Quantity Limitations:

Passenger aircraft or railcar: 25 kg
Cargo aircraft only: 100 kg

Vessel Stowage Requirements:

Vessel stowage location: A

A: The material may be stowed "on deck" or "under deck" on a cargo vessel and on a passenger vessel.

Vessel stowage other: 12

12: Keep as cool as reasonably practicable.

ICAO International Shipping Name for UN1783 (ICAO, 2002):

Proper Shipping Name: Hexamethylenediamine solution
UN Number: 1783

ICAO International Shipping Name for UN2280 (ICAO, 2002):

Proper Shipping Name: Hexamethylenediamine, solid
UN Number: 2280

LABELS

NFPA

NFPA Hazard Ratings for CAS124-09-4 (NFPA, 2002):

Not Listed

-HANDLING AND STORAGE

SUMMARY

INDUSTRIAL CHEMICALS

HMDA is a corrosive irritant to the eyes, skin, and mucous membranes. It will readily volatilize and forms an explosive mixture with air. Protective clothing and respiratory protection are recommended during material handling. HMDA storage in a tightly closed container in a cool, dry, and preferably inert environment is suggested. The material is combustible when exposed to heat or flame. It can react with oxidizing materials and a number of chemical classes (HSDB , 2002; ITI, 1995; Lewis, 2001; Pohanish & Greene, 1997; Sittig, 1991).

HANDLING

HMDA and other diamines are strong bases and will act as a corrosive irritant to the eyes, skin, and mucous membranes. Vapors cause irritation of the eyes and respiratory tract. The liquid will also irritate the eyes and skin and may cause dermatitis. Solid HMDA may be expected to be strongly irritating or caustic to the eyes due to its alkalinity. Protective clothing such as butyl rubber gloves, overalls, boots, goggles, and a face or universal gas mask are therefore recommended during material handling (CHRIS , 2002; Grant & Schuman, 1993; HSDB , 2002; ITI, 1995; Lewis, 2001; Pohanish & Greene, 1997).

STORAGE

CONTAINER

HMDA should be stored in a tightly closed container as it readily vaporizes. It attacks copper, lead, tin, zinc, and alloys, and contact with metal may evolve flammable hydrogen gas. Metal container compatibility for material storage should be considered. Containers may explode when heated (HSDB , 2002; Pohanish & Greene, 1997; Sittig, 1991).

ROOM/CABINET RECOMMENDATIONS

Containers of HMDA should be stored in a cool, dry location and preferably in an inert atmosphere. Material undergoing shipment can be stored at ambient temperature in an inert atmosphere of nitrogen. Storage considerations should also address that the material is combustible and a slight fire hazard when exposed to heat or flame (CHRIS , 2002; Lewis, 2000; Sittig, 1991; OHM/TADS , 2002).

INCOMPATIBILITIES

HMDA forms an explosive mixture with air. It is a strong reducing agent and therefore can react with oxidizing materials. It attacks copper, lead, tin, zinc, and alloys. HMDA reacts with (HSDB , 2002; NTP , 2002; Pohanish & Greene, 1997):
- ethylene dichloride
- acids
- acid chlorides
- acid anhydrides
- organic anhydrides
- isocyanates
- vinyl acetate
- acrylates
- substituted allyls
- alkylene oxides
- epichlorohydrin
- ketones
- aldehydes
- alcohols
- glycols
- phenols
- cresols
- caprolactum solution
- nitrates
- monomer and chlorinated compounds
- strong oxidizers
The solution of HMDA in water is a strong base, is corrosive, and reacts violently with acid. HMDA attacks many metals in the presence of water (ILO , 1998).

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Wear positive pressure self-contained breathing apparatus (SCBA).
Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
Structural firefighters' protective clothing provides limited protection. fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.

HMDA is moderately toxic by ingestion, inhalation, and skin contact. It is a corrosive irritant to the eyes, skin, mucous membranes, and upper respiratory tract. Due to its corrosivity and irritant properties, full protective clothing and eye protection should be worn when working with HMDA. HMDA readily vaporizes and the vapors should be avoided through the use of a face or universal mask if engineering controls are not in place. Personal protection in a fire or emergency situations should include a positive pressure self-contained breathing apparatus. Protective equipment and clothing should not be subject to attack by caustics (ACGIH, 1996; (CHRIS , 2002; HSDB , 2002; Lewis, 2000; OHM/TADS , 2002).

Wear appropriate chemical protective clothing and equipment when working with or around HMDA to prevent bodily contact with this material; this includes gloves, boots, and eye protection. Do not handle broken packages of HMDA unless wearing adequate protective clothing (AAR, 2000).

If HMDA contacts the skin, wash any affected areas with copious amounts of water or soap and water (AAR, 2000).

EYE/FACE PROTECTION

Goggles should be worn, unless a full face respirator is utilized (CHRIS , 2002; ITI, 1995). Wear appropriate chemical protective goggles to prevent eye contact with HMDA (AAR, 2000).

RESPIRATORY PROTECTION

Appropriate and adequate ventilation should be implemented when handling HMDA or a face or universal gas mask may be used. A positive pressure, self-contained breathing apparatus is recommended for emergency actions and fire situations (AAR, 2000; (CHRIS , 2002; ITI, 1995).

PROTECTIVE CLOTHING

CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 124-09-4.

All data are compiled from published sources and are NOT recommended specifically by Truven Health Analytics. The appearance of specific manufacturers or products in this section does not represent an endorsement by Truven Health Analytics. No attempt has been made to verify the data presented. All product recommendations should be confirmed with the specific manufacturer for verification of product performance.
CLOTHING

Plastic Laminate

DuPont Personal Protection

Tychem 10,000

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: liquid, tested at 45º C
Citation: (DuPont, 2002)

Tychem 7500

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: liquid, tested at 45º C
Citation: (DuPont, 2002)

Tychem 9400

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: liquid, tested at 45º C
Citation: (DuPont, 2002)

Tychem BR

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem LV

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: tested at 45 degrees C
Citation: (DuPont, 2003)

Tychem QC

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: tested at 45º C
Citation: (DuPont, 2002)

Tychem SL

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: liquid, tested at 45º C
Citation: (DuPont, 2002)

Tychem ThermoPro

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.0001
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem TK

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: Not Listed
Citation: (DuPont, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.01
Notes: liquid, tested at 45º C
Citation: (DuPont, 2002)

FOOTWEAR

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GLOVES

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GENERAL INFORMATION

This section provides a compilation of chemical resistance information and test data for specific protective clothing products. Chemical resistance information includes both degradation resistance ratings and permeation resistance data. This information is designed to assist in the selection of appropriate protective clothing. Only data on specific products and manufacturers are included. Generic information or recommendations are not provided since significant differences can exist in the chemical resistance for apparent similar product types.
Specific product information is organized by general product type (gloves, garments, and footwear), material type, and manufacturer. The category 'garments' may include totally encapsulating suits, splash suits, as well as other items (e.g., coveralls, jackets, and aprons). Specific manufacturers should be contacted to determine the features of available styles/models.
In addition to chemical resistance information, there are many critical variables in the selection of protective clothing which cannot be represented in this summary of the literature. Some factors to be considered in choosing protective clothing include, but are not limited to: overall clothing integrity, physical hazard resistance, durability, human factors, ease of decontamination, and cost. Overall clothing integrity refers to a specific design's ability to offer consistent protection for all clothing-covered areas of the body. Physical hazards include resisting the effects of abrasion, cuts, tears, and punctures. Human factors entail effects on wearer mobility, visibility, and hearing for garments; dexterity, tactility, and grip for gloves; ankle support and weight for footwear; and, any effect of the clothing on the function of the wearer. There are several variations in the design for gloves, garments, and footwear that affect these factors. Protective clothing must properly be sized and correctly fit the wearer to ensure its proper use and function.
As required in the U.S.A., protective clothing should be selected based on a risk assessment of the workplace. This risk assessment must account for the identification of existing as well as potential hazards and involve the recommendation of protective clothing appropriate for the identified hazards. Therefore, the recommendations in this section should not be used as the sole basis for decisions on choice of protective clothing, but rather should be used as a tool by qualified occupational health and safety professionals or other technically qualified persons in conjunction with a review of all mitigating factors. Consult the OSHA PPE Standard (29 CFR 1910.132 - 1910.138) for regulations and additional guidance regarding the selection and use of protective clothing and equipment. For general information on protective clothing selection, refer to the "PERSONAL PROTECTIVE EQUIPMENT - OSHA PUB 3077" document.
PROTECTIVE CLOTHING SELECTION

Determine the type of protective clothing item needed based on a risk assessment (e.g., gloves, garments, footwear).
For high risk situations, choose clothing that covers all parts of the body that may be exposed. In many cases, multiple clothing items will be required. Low risk situations may permit partial body protective clothing. Select protective clothing products that have reported chemical resistance data. High risk situations involving full body clothing or extended chemical contact often require permeation resistance data to determine the barrier effectiveness of materials used in the construction of clothing. Relatively low risk situations, where only splash or incidental exposure occur, may allow use of protective clothing based on degradation or penetration resistance data. Specifics on the interpretation of chemical resistance data are presented below.
Other factors must be considered in addition to chemical resistance. The selected chemical protective clothing item should offer the optimal combination of protection against identified hazards while allowing maximum function and comfort.

INTERPRETATION OF DEGRADATION RATINGS

Degradation refers to physical changes in a material as the result of chemical exposure. Degradation may become evident in visible changes, such as discoloration, swelling, delamination, deterioration, or disintegration. Degradation effects may also be measured by weight change or other changes in a material's physical properties (e.g., strength, elasticity, hardness).
Degradation resistance ratings are provided by manufacturers to rate the amount of degradation that occurs for a particular protective clothing material when contacted by a chemical. All degradation ratings are qualitative and include ratings, such as "EXCELLENT," "GOOD," "FAIR," "POOR," and "NOT RECOMMENDED." There is no standard test method for the measurement of chemical degradation resistance; therefore, manufacturer ratings may be based on different testing approaches. This makes comparison of degradation ratings between manufacturers unreliable.
The use of degradation resistance ratings alone to recommend protective clothing, particularly for high hazard situations, should be avoided. Degradation resistance testing does not directly assess the barrier quality of protective clothing, since materials can show relatively little degradation but still allow either permeation or penetration by a chemical. Degradation resistance ratings can be used to exclude protective clothing materials from consideration. Protective clothing materials with a "NOT RECOMMENDED" degradation resistance rating should never be used.
For some products, the rating "NO PENETRATION" is provided. This refers to penetration resistance test results that are based on a different procedure (American Society for Testing and Materials (ASTM) Standard Test Method F 903). Penetration resistance testing involves placing a material sample in a test cell, exposing the exterior side of the material to a chemical, and then observing the interior side of the material for visible signs of liquid penetration. Part of the test is conducted at an elevated pressure. Test results are reported as pass (no penetration) or fail (penetration detected). Unlike degradation testing, penetration testing provides an assessment of protective clothing material barrier performance. Since penetration resistance testing examines only observable amounts of liquid penetration, permeation may still occur. The use of penetration resistance data must be restricted to liquid chemicals, and should be limited to scenarios where there is no reasonable vapor exposure hazard under the conditions of exposure.

INTERPRETATION OF PERMEATION DATA

Permeation is the process of chemical movement through a material on a molecular level. Permeation resistance refers to the ability of a material to retard or prevent chemical movement through it. Permeation may occur without any visible signs of degradation.
Permeation resistance is measured using a test cell which is divided into two halves by a protective clothing specimen. Chemical is placed on the challenge side, while the collection side is periodically monitored for permeating chemical. Permeation data were obtained in accordance with the American Society for Testing and Materials (ASTM) Standard Test Method F 739 (Resistance of Materials Used in Protective Clothing to Permeation by Liquids and Gases), unless stated otherwise. In the case of chemicals that are classified as warfare agents, the data were obtained in accordance with the Military Standard 282 (MIL-STD-282) (Military Standard, Filter Units, Protective Clothing, Gas-Mask Components, and Related Products: Performance Test Methods).
Permeation rate is the amount of chemical that passes through a material for a measured surface area per unit time. In this section, permeation rate is expressed in micrograms per square centimeter per minute (mcg/cm(2)/min). The reported permeation rate is either the steady-state rate or the maximum rate observed during testing. In some cases, very large permeation rates exceed measurement techniques and are reported as ">" (greater than) or "HIGH."
Breakthrough time is the elapsed time, in minutes, from the time the chemical comes in contact with the material exterior surface, to the time that chemical is detected on the interior surface. When no breakthrough is detected, the breakthrough time is report as ">" the testing period. If permeation breakthrough is rapid, results are reported as "<" (less than) the earlier sampling time or as "IMMEDIATELY" (which usually means breakthrough in less than 4 minutes).
The breakthrough time should exceed the expected use period of the selected protective clothing. Additionally, there are several other factors that must be taken into account to provide appropriate protection.
Permeation testing is usually conducted with full strength, undiluted chemical for the duration of the test period. Actual exposures may involve diluted chemical for short or intermittent exposure periods.
Permeation testing is usually conducted at room temperature. Permeation occurs faster at elevated temperatures (short breakthrough times and higher permeation rates) and slower at reduced temperatures (long breakthrough times and lower permeation rates).
Permeation resistance of mixtures cannot usually be determined on the basis of the individual chemicals making up the mixture. Synergistic effects may occur and result in more rapid permeation than accounted for by the individual mixture chemicals.
Permeation rates may be used to calculate potential wearer exposure; however, several assumptions must be made about the extent of exposure and condition of clothing wear. Furthermore, there are few chemicals with dermal exposure limits, making it difficult to determine an acceptable skin exposure level.

COMPANY INFORMATION

DuPont Personal Protection P. O. Box 80705 Wilmington, DE 19880-0705 USA Phone: (302) 774-1000 Toll-Free: (800) 931-3456 Website: http://personalprotection.dupont.com Email: personalprotection@usa.dupont.com

REFERENCES

CHEMICAL PROTECTIVE CLOTHING CITATIONS

The following sources were consulted for chemical protective clothing data:

(Ansell-Edmont, 2001)
(Bata Shoe Company, 1995)
(Best Manufacturing, 2002)
(Best Manufacturing, 2004)
(Boss Manufacturing Company, 1998)
(ChemFab Corporation, 1993)
(Comasec Safety, Inc., 2003)
(Comasec Safety, Inc., 2003a)
(DuPont, 2002)
(DuPont, 2002)
(DuPont, 2003)
(Guardian Manufacturing Group, 2001)
(ILC Dover, Inc., 1998)
(Kappler Inc., 2001)
(Kimberly-Clark, 2002)
(LaCrosse-Rainfair, 1997)
(MAPA Professional, 2003)
(MAPA Professional, 2004)
(Mar-Mac Manufacturing, Inc, 1995)
(Marigold Industrial, 2003)
(Memphis Glove Company, 2001)
(Montgomery Safety Products, 1995)
(Nat-Wear, 2001)
(Neese Industries, Inc., 2003)
(North, 2002)
(North, 2002)
(Playtex, 1995)
(River City, 1995)
(Safety 4, 2002)
(Servus, 1995)
(Standard Safety Equipment, 1995)
(Tingley, 2002)
(Trelleborg-Viking, Inc., 2001)
(Trelleborg-Viking, Inc., 2002)
(Wells Lamont Industrial, 2002)
(Workrite, 1997)

ENGINEERING CONTROLS

Adequate ventilation should be implemented when handling HMDA (ITI, 1995).

-PHYSICAL HAZARDS

FIRE HAZARD

SUMMARY

POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)
- Combustible material: may burn but does not ignite readily.
- When heated, vapors may form explosive mixtures with air: indoors, outdoors and sewers explosion hazards.
- Those substances designated with a "P" may polymerize explosively when heated or involved in a fire.
- Contact with metals may evolve flammable hydrogen gas.
- Containers may explode when heated.
- Runoff may pollute waterways.
- Substance may be transported in a molten form.
HMDA is combustible when exposed to heat or flame. It will burn, but will not readily ignite. Heating of HMDA will release vapors that can form explosive mixtures with air. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated (HSDB , 2002; Lewis, 2000; OHM/TADS , 2002).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS124-09-4 (NFPA, 2002):

Not Listed

FIRE CONTROL/EXTINGUISHING AGENTS

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Dry chemical, CO2 or water spray.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Dry chemical, CO2, alcohol-resistant foam or water spray.
Move containers from fire area if you can do it without risk.
Dike fire control water for later disposal; do not scatter the material.

TANK OR CAR/TRAILER LOAD FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
Do not get water inside containers.
Cool containers with flooding quantities of water until well after fire is out.
Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from tanks engulfed in fire.

NFPA Extinguishing Methods for CAS124-09-4 (NFPA, 2002):

Not Listed

If HMDA material is on fire or involved in a fire, do not extinguish the fire unless flow can be stopped. Fires involving HMDA can be extinguished with water, 'alcohol' foam, dry chemical, or carbon dioxide. Solid streams of water may be ineffective, however. It is suggested to use water in flooding quantities as a fog and cool all affected containers by flooding with quantities of water (AAR, 2000; (CHRIS , 2002; HSDB , 2002).

COMBUSTION TOXICITY

Upon heating of HMDA, or when heated to decomposition, toxic vapors are emitted. Fire may produce irritating, corrosive and/or toxic gases. Thermal decomposition may produce carbon dioxide or carbon monoxide. Toxic oxides of nitrogen are produced during the combustion of HMDA solution (AAR, 2000; (HSDB , 2002; NTP , 2002; OHM/TADS , 2002)

EXPLOSION HAZARD

HMDA readily volatilizes and forms an explosive mixture with air (flashpoint of 176 degrees F or 80 degrees C). When heated, vapors may also form explosive mixtures with air leading to indoor, outdoor, and sewer explosion hazards (HSDB , 2002; Pohanish & Greene, 1997).

DUST/VAPOR HAZARD

Adequate ventilation is recommended when working with HMDA. Vapors cause irritation of the eyes and respiratory tract. It has been reported that concentrations greater than 100 mg/m(3) irritate the eyes and upper respiratory tract. Upon heating of HMDA, or when heated to decomposition, toxic vapors are emitted, and these vapors may also form explosive mixtures with air. Fire may produce irritating, corrosive and/or toxic gases. Toxic oxides of nitrogen are produced during the combustion of HMDA solution (CHRIS , 2002; Grant & Schuman, 1993; HSDB , 2002; ITI, 1995; OHM/TADS , 2002).

REACTIVITY HAZARD

HMDA is a strong reducing agent and therefore can react with oxidizing materials. It attacks copper, lead, tin, zinc, and alloys. The water solution of HMDA is strongly basic and reacts violently with acid. HMDA attacks many metals in the presence of water. It is not, however, directly reactive with water, and flushing with water is an appropriate neutralizing action for caustics, such as HMDA. HMDA reacts with (CHRIS , 2002; HSDB , 2002; ILO , 1998; Pohanish & Greene, 1997):

ethylene dichloride
acids
organic anhydrides
isocyanates
vinyl acetate
acrylates
substituted allyls
alkylene oxides
epichlorohydrin
ketones
aldehydes
alcohols
glycols
phenols
cresols
caprolactum solution
strong oxidizers

EVACUATION PROCEDURES

SUMMARY

Editor's Note: This material is not listed in the Table of Initial Isolation and Protective Action Distances.

SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

Increase, in the downwind direction, as necessary, the isolation distance of at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids in all directions.

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions.

PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)

CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number:

MEXICO:

SETIQ:

01-800-00-214-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5559-1588;
For calls originating elsewhere, call: 011-52-555-559-1588.

CENACOM:

01-800-00-413-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885;
For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.

ARGENTINA:

CIQUIME:

0-800-222-2933 in the Republic of Argentina;
For calls originating elsewhere, call: +54-11-4613-1100.

BRAZIL:

PRÓ-QUÍMICA:

0-800-118270 (Toll-free in Brazil);
For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).

COLUMBIA:

CISPROQUIM:

01-800-091-6012 in Colombia;
For calls originating in Bogotá, Colombia, call: 288-6012;
For calls originating elsewhere, call: 011-57-1-288-6012.

CANADA:

CANUTEC:

613-996-6666 (Collect calls are accepted);
*666 cellular (in Canada only).

UNITED STATES:

CHEMTREC®:

1-800-424-9300 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
703-527-3887 for calls originating elsewhere (Collect calls are accepted).

CHEM-TEL, INC.:

1-800-255-3924 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
813-248-0585 for calls originating elsewhere (Collect calls are accepted).

INFOTRAC:

1-800-535-5053 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
352-323-3500 for calls originating elsewhere (Collect calls are accepted).

3E COMPANY:

1-800-451-8346 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
760-602-8703 for calls originating elsewhere (Collect calls are accepted).

NATIONAL RESPONSE CENTER (NRC):

1-800-424-8802 - (24 hours) (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
202-267-2675 for calls in the District of Columbia.

MILITARY SHIPMENTS:

703-697-0218 - Explosives/ammunition incidents (Collect calls are accepted);
1-800-851-8061 - All other dangerous goods incidents.

NATIONWIDE POISON CONTROL CENTER (United States only):

1-800-222-1222 (Toll-free in the U.S.).

For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions.
As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.
Keep unauthorized personnel away.
Stay upwind.
Keep out of low areas.
Ventilate enclosed areas.

People that are not wearing protective equipment should remain upwind and avoid inhalation of vapors (AAR, 2000; (Sittig, 1991).

AIHA ERPG Values for CAS124-09-4 (AIHA, 2006):

Not Listed

DOE TEEL Values for CAS124-09-4 (U.S. Department of Energy, Office of Emergency Management, 2010):

Not Listed

AEGL Values for CAS124-09-4 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):

Not Listed

NIOSH IDLH Values for CAS124-09-4 (National Institute for Occupational Safety and Health, 2007):

Not Listed

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)
- ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area).
- Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.
- Stop leak if you can do it without risk.
- Prevent entry into waterways, sewers, basements or confined areas.
- Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers.
- DO NOT GET WATER INSIDE CONTAINERS.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 153 (ERG, 2004)
- Wear positive pressure self-contained breathing apparatus (SCBA).
- Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection.
- Structural firefighters' protective clothing provides limited protection. fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible.
Spilled solid material can be covered with sufficient quantities of sodium bisulfite and sprinkled or dampened with water to avoid generation of dust. Spilled material can also be absorbed or covered with dry earth, sand, or other non- combustible material. Wastes generated from the spill should be sealed in vapor-tight plastic bags for eventual disposal. However, do not allow water inside waste storage containers (HSDB , 2002; ITI, 1995; Sittig, 1991).
Environmental considerations for a land spill (AAR, 2000):
- Dig a holding area such as a pond, pit, or lagoon to contain liquid or solid material.
- Surface flow can be diked using soil, sandbags, foamed polyurethane, or foamed concrete.
- Absorb bulk liquid with fly ash, cement powder, or commercial sorbents.
Environmental considerations for a water spill (AAR, 2000):
- Use natural barriers or oil spill control booms to limit spill travel.
- Remove trapped material with a suction hose.
Environmental considerations for an air spill (AAR, 2000):
- Apply a water spray or mist to limit vapors.
Flushing with water is a neutralizing action for caustics, such as HMDA, and acids (CHRIS , 2002).
Remain upwind of HMDA spills, and avoid breathing its vapors (AAR, 2000).

WASTE TREATMENT OPTIONS

CHEMICAL TREATMENT

This material may be neutralized by adding HMDA to a layer of sodium bisulfite and spraying with water (ITI, 1995; HSDB , 2002; OHM/TADS , 2002).
Wastewater treatment of HMDA waste generated from polyamide manufacturing was conducted. A reverse osmosis apparatus with cellulose acetate membranes was studied to determine the effect of HCl addition on transport of components of the solution through a membrane and to assess the possibility of changing the pH of the concentrate formed in the apparatus (HSDB , 2002).
Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.

BIOREMEDIATION

A study was performed that examined the feasibility of microbial decomposition of organic wastes under the conditions present in deep wells. Temperature was not a constraint under aerobic conditions. It was found that thermophilic bacteria will decompose a wide variety of chemical compounds, and growth of thermophilic bacteria is possible with HMDA (HSDB , 2002).

PHYSICAL TREATMENT

In situ amelioration may be accomplished through the application of carbon on alkaline solutions (OHM/TADS , 2002).
The material can be dissolved in a flammable solvent, such as alcohol, and, while remaining upwind and at a safe distance, ignite the material in an open pit or open furnace. This solution could also be incinerated. (ITI, 1995; OHM/TADS , 2002).

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

The production of HMDA and its use as a chemical intermediate in the manufacture of resins (polyamide and nylon) and as a corrosion inhibitor/additive in oils and lubricants may lead to environmental releases through various waste streams. Occupational exposure to HMDA may occur through inhalation and dermal contact at workplaces where it is produced or used (ACGIH, 1996a; Budavari, 2000; HSDB , 2002; Sittig, 1991).

ENVIRONMENTAL FATE AND KINETICS

HMDA is expected to exist as a vapor in the ambient atmosphere, based on its vapor pressure of 0.12 mm Hg at 25 degrees C and from information obtained in modeling applications of gas/particle partitioning of semivolatile organic compounds in the atmosphere (HSDB, 2004).
Atmospheric HMDA will degrade by reaction with hydroxyl radicals. A rate constant for the reaction was estimated to be 6.9 x 10(-11) cm(3)/molecule-sec at 25 degrees C. The corresponding atmospheric half-life was determined to be about 6 hours at an atmospheric concentration of 5 x 10(5) hydroxyl radicals/cm(3) (HSDB, 2004).

WATER

SURFACE WATER
- In an aquatic environment, HMDA will adsorb to suspended solids or sediment or based on the Koc value of 286. It will not significantly dissociate at normal environmental pH levels considering the measured pKa of 11. HMDA is not expected to volatilize from water (Henry's Law constant of 3.2 x 10(-9) atm-m(3)/mol) (HSDB, 2004).
- Degradation rates of 4% and 10% were observed for HMDA (50 ppm) incubated for 3 days in water from the Mino River, Japan and seawater off the coast of Japan (HSDB, 2004).

SOIL

TERRESTRIAL
- HMDA is expected to be moderately to highly mobile in soil based on its estimated Koc value of 286 (and a reported log 10 Koc of 1.387 determined from a measured log Pow of 0.02) (HSDB , 2002).
- HMDA does not readily volatilize from soil and will likely sorb to soil particles. Volatilization from soil surfaces is not expected based on an extrapolated vapor pressure of 0.12 mm Hg at 25 degrees C and an estimated Henry's Law constant of 3.2 x10(-9) atm-m(3)/mole (HSDB, 2004).

ABIOTIC DEGRADATION

HMDA in the environment will undergo adsorption in soil and will adsorb to suspended solids or sediment in aquatic systems. It is not expected to volatilize from water or soil, based on an extrapolated vapor pressure and an estimated Henry's Law Constant. Biodegradation is anticipated to be the most important fate mechanism in soil, but this process occurs slowly in water. It will exist as a vapor in the ambient atmosphere, degrading by reaction with photochemically produced hydroxyl radicals (HSDB, 2004).

An experimental pKa value of 11 indicates that HMDA will not dissociate significantly at environmentally important pH values. It is also not expected to undergo hydrolysis or direct photolysis in the environment due to the lack of functional groups to hydrolyze or absorb UV radiation at environmentally significant wavelengths (HSDB, 2004).

BIODEGRADATION

Biodegradation is expected to be a significant mechanism in the environmental fate of HMDA. It will biodegrade under aerobic conditions based on standard BOD dilution techniques with activated sludge (EPA, 2002g) (HSDB, 2004).

It is considered biodegradable based on theoretical BOD values of 41% to 56%, reported using standard BOD dilution techniques and activated sludge inoculum incubated for 14 days and allowing for acclimation (HSDB, 2004).
In another study, 90% biodegradation was observed in an activated sludge inoculum during a 6 day incubation period with a 3 day acclimation period. An average COD of 26% per day was also reported in this study (HSDB, 2004).
A theoretical oxygen demand between 20% and 60% was observed in a Warburg apparatus during a 5 day incubation period (HSDB, 2004).

Biodegradation is expected to occur slowly in aqueous environments(HSDB, 2004).

Inhibition of biodegradation was evaluated by examining NH3 oxidation by Nitrosomonas species. The following results were reported (Verschueren, 2001):

at 100 mg/L: 52% inhibition
at 50 mg/L: 45% inhibition
at 10 mg/L: 27% inhibition

BIOACCUMULATION

BIOCONCENTRATION FACTOR

Bioconcentration in aquatic organisms is considered low, based on an estimated BCF of 1 (calculated using an estimated log Kow of 0.35 and a recommended regression-derived equation) (HSDB, 2004).

ENVIRONMENTAL TOXICITY

Experiments have shown low to slight acute toxicity to freshwater fish species and moderate acute toxicity to the microcrustaceon Daphnia magna and to the algal species Selenastrum capricornutum. A maximum tolerable concentration (MTC) of 0.148 mg/L was determined using an assessment factor of 100 with the lowest experimentally-derived acute EC50 value (EPA, 2002g).

HMDA is classified as a Class II chemical according to OECD Guidance for Initial Assessment of Aquatic Effects (EPA, 2002g)

EC50 - (WATER) Selenastrum capricornutum: 14.8 mg/L for 96H (EPA, 2002g)

EC50 - (WATER) Daphnia magna: 23.4 mg/L for 48 H (EPA, 2002g)

LC50 - (WATER) Bluegill sunfish: 73.5 mg/L for 48H (EPA, 2002g)

LC50 - (WATER) Fathead minnow: 1825 mg/L for 96H (EPA, 2002g)

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

116.21

DESCRIPTION/PHYSICAL STATE

HMDA is solid (anhydrous) at 15 degrees C and 1 atm. It will absorb water and carbon dioxide from air and is soluble in water, alcohol, benzene, and ether. It has a weak, fishy odor similar to piperdine and exists as colorless leaflets or platelets and as long needles from sublimation. It has also been described as a white crystalline solid with an ammonia-type odor. Closer examination of the solid indicates rhombic bipyrimidal plates. HMDA solution is a clear, colorless liquid (AAR, 2000; (ACGIH, 1996a; CHRIS , 2002; HSDB , 2002; Lewis, 2000).

VAPOR PRESSURE

0.12 mm Hg (at 25 degrees C) (HSDB , 2002)

200 Pa (at 50 degrees C) (ILO , 1998).

SPECIFIC GRAVITY

OTHER TEMPERATURE AND/OR PRESSURE

Anhydrous: 0.799 (at 60 degrees C) (CHRIS , 2002)
Liquid: (70% solution): 0.933 (at 20 degrees C) (CHRIS , 2002)

DENSITY

VAPOR DENSITY

4.01 (air =1) (Verschueren, 2001)

FREEZING/MELTING POINT

FREEZING POINT

(anhydrous) 104.9 degrees F; 40.5 degrees C; 313.7 K (CHRIS , 2002)
(70% solution) 28 degrees F; -2 degrees C; 269 K (CHRIS , 2002)

MELTING POINT

42 degrees C (Ashford, 1994; Budavari, 2000; ITI, 1995)
40.9 degrees C (ACGIH, 1996a)
39 degrees C - 42 degrees C (Sittig, 1991)
39 degrees C - 40 degrees C (Verschueren, 2001)

BOILING POINT

204.4 degrees C (at 760 torr) (ACGIH, 1996a)

205 degrees C (Ashford, 1994; Budavari, 2000; ITI, 1995)

205 degrees C; 401 degrees F; 478 K (at 1 atm) (CHRIS , 2002)

196-205 degrees C (Verschueren, 2001)

FLASH POINT

71 degrees C (Sittig, 1991; ILO , 1998)

160 degrees F (open cup) (CHRIS , 2002)

AUTOIGNITION TEMPERATURE

310 degrees C (ILO , 1998)

EXPLOSIVE LIMITS

LOWER

LEL = 0.7% (Sittig, 1991)

UPPER

UEL = 6.3% (Sittig, 1991)

SOLUBILITY

IN WATER

HMDA is soluble in water and forms an alkaline solution (ACGIH, 1996a; Ashford, 1994; Budavari, 2000; ITI, 1995; OHM/TADS , 2002).
Very soluble in water (ILO , 1998).
1,000,000 ppm (at 25 degrees C) (OHM/TADS , 2002)
2,460,000 mg/l (at 4.5 degrees C) (HSDB , 2002)

IN ORGANIC SOLVENTS

Slightly soluble in alcohol and benzene, and somewhat soluble in ether (ACGIH, 1996a; Ashford, 1994; Budavari, 2000; HSDB , 2002; ITI, 1995).

OCTANOL/WATER PARTITION COEFFICIENT

log Kow = 0.35 (est) (HSDB , 2002)

HENRY'S CONSTANT

3.2 x 10(-9) atm-m(3)/mol (est) (HSDB , 2002)

SPECTRAL CONSTANTS

1392 (Coblentz Society Spectral Collection)(HSDB , 2002)

MASS

440 (Atlas of Mass Spectral Data, John Wiley & Sons, New York) (HSDB , 2002)

OTHER/PHYSICAL

HEAT OF COMBUSTION

(estimated) -12,200 Btu/lb; -6,790 cal/g; -284 x 10(5) J/kg (CHRIS , 2002)

NUCLEAR MAGNETIC RESONANCE

16074 (HSDB , 2002)

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1,6-HEXAMETHYLENEDIAMINE

Classification | Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents

Information to evaluate chemical incidents